ASPEN PLUS Simulation of Green Ammonia

ESCUELA TÉCNICA SUPERIOR DE INGENIEROS
INDUSTRIALES Y DE TELECOMUNICACIÓN
UNIVERSIDAD DE CANTABRIA
Trabajo Fin de Grado
SMALL-SCALE GREEN AMMONIA

PRODUCTION PLANT: PRELIMINARY DESIGN
AND SIMULATION USING ASPEN PLUS
(Planta de producción de amoniaco

sostenible a pequeña escala: diseño
preliminar y simulación en ASPEN Plus)
Para acceder al Título de
GRADUADO EN INGENIERÍA EN
TECNOLOGÍAS INDUSTRIALES
Autor: Juan Lainz Arrarte
05-2022
Juan Lainz Arrarte May 2022
1
Título: Planta de producción de amoniaco sostenible a pequeña escala: diseño

preliminar y simulación en ASPEN Plus.
Autor: Juan Lainz Arrarte
Directores: Berta Galán Corta y Javier R. Viguri Fuente
Palabras clave: Amoniaco, pequeña escala, Aspen Plus, renovable, simulación,

Haber Bosch, hidrógeno, nitrógeno.
Resumen: El presente proyecto tiene como objetivo el diseño preliminar de una

planta de producción (a pequeña escala) de 25 kg/h amoniaco del 98% de pureza a
partir de materias primas y energías renovables. Dicha planta permitirá el suministro
de amoniaco como combustible a buques de carga desde una plataforma flotante en
el puerto de Santander.
Inicialmente se realiza un análisis de alternativas comparando, principalmente, el uso

de hidrogeno y amoniaco como combustibles renovables en transporte marítimo y se
estudia su importancia dentro del panorama internacional a medio y largo plazo para
este tipo de usos.
El análisis del estado del arte de plantas de producción de amoniaco a pequeña

escala, permite seleccionar el proceso Haber-Bosch como el más adecuado en
términos de accesibilidad de materias primas, condiciones de trabajo, eficiencia,
costes y TRL, incluyendo la obtención de hidrógeno a través de electrólisis del agua
de mar y de nitrógeno a partir de separación del aire.
Mediante simulación en ASPEN PLUS se diseña una planta de producción de 25.64

kg/h de amoniaco del 99.3% obteniéndose los requerimientos de materias primas, las
características de las corrientes y las condiciones de trabajo de cada equipo. Esta
información permite el dimensionado de equipos y el establecimiento de un área
global para la plataforma flotante de 300 𝑚2 . La estimación de costes preliminar
mediante métodos modulares permite establecer un Coste Base de Capital de 2.1
MM€.
2
Title: Small-Scale green ammonia production plant: preliminary design and simulation
using ASPEN Plus.
Author: Juan Lainz Arrarte
Supervisor: Berta Galán Corta and Javier R. Viguri Fuente
Keywords: Ammonia, small-scale, ASPEN Plus, renewable, simulation, Haber

Bosch, Hydrogen, Nitrogen.
Abstract: The objective of this project is the preliminary design of a plant for the
production (on a small scale) of 25 kg/h of 98% pure ammonia from raw materials and
renewable energies. This plant will allow the supply of ammonia as fuel to cargo ships
from a floating platform in the port of Santander.
Initially, an analysis of alternative fuels is carried out, mainly comparing the use of
hydrogen and ammonia as renewable fuels in maritime transport, and their importance
in the medium- and long-term international panorama for this type of use is studied.
The analysis of the state of the art of small-scale ammonia production plants allows
the Haber-Bosch process to be selected as the most suitable in terms of accessibility
of raw materials, working conditions, efficiency, costs, and LRT, including the obtaining
of hydrogen through seawater electrolysis and nitrogen from air separation.
Through simulation in ASPEN PLUS, a plant is designed for the production of 25.64
kg/h of 99.3% ammonia, obtaining the raw material requirements, the characteristics
of the streams and the working conditions of each piece of equipment. This information
allows the sizing of equipment and the establishment of an overall area for the floating
platform of 300 sqm. Preliminary cost estimation using modular methods allows a
Base Capital Cost of €2.1 MM to be established.
3
INDEX
LIST OF FIGURES ..................................................................................................... 6
LIST OF TABLES ....................................................................................................... 7
ABBREVIATIONS ...................................................................................................... 8
1 INTRODUCTION ................................................................................................... 10
1.1 CONTEXT ....................................................................................................... 10
1.1.1 Renewable fuels....................................................................................... 10
1.1.2 Marine transport fuels .............................................................................. 12
1.1.3 Floating energy production systems ......................................................... 14
1.1.4 Bahia H2 offshore project ......................................................................... 14
1.2 AMMONIA PRODUCTION PROCESS ........................................................... 17
1.2.1 Ammonia production routes ..................................................................... 20
1.2.2 Conventional Haber Bosch process ......................................................... 21
1.2.3 Sustainable ammonia by Haber Bosch .................................................... 22
1.2.4 Alternatives to the Haber Bosch process ................................................. 24
1.2.5 Discussion of the selected technology ..................................................... 25
1.3. SMALL SCALE HABER BOSCH PLANTS AND PROJECTS USING

RENEWABLE ENERGY ....................................................................................... 28
1.3.1 Proton ventures ........................................................................................ 28
1.3.2 Thyssenkrupp........................................................................................... 30
1.3.3 JGC Holdings ........................................................................................... 32
1.3.4 Siemens ................................................................................................... 34
1.3.5 University of Minnesota ............................................................................ 35
1.4 OBJECTIVE .................................................................................................... 37
2 DESIGN SPECIFICATIONS .................................................................................. 39
2.1 RAW MATERIALS AND PRODUCTS ............................................................. 39
2.2 AIR SEPARATION UNIT................................................................................. 41
4
2.3 DESALINIZATION AND WATER ELECTROLYSIS ........................................ 43
2.4 AMMONIA SYNTHESIS.................................................................................. 45
3 ASPEN PLUS SIMULATION ................................................................................. 48
3.1 INPUT DATA................................................................................................... 49
3.2 FEED AND PRODUCT STREAMS ................................................................. 50
3.3 PROCESS THERMODYNAMICS ................................................................... 51
3.4 EQUIPMENT................................................................................................... 51
3.4.1 Air separation unit .................................................................................... 51
3.4.2 Desalination unit and PEM electrolysis .................................................... 52
3.4.3 Ammonia synthesis unit ........................................................................... 53
3.5 DESIGN SPECIFICATIONS ........................................................................... 54
3.6 PROCESS FLOW DIAGRAM OF THE COMPLETE PROCESS .................... 56
4 RESULTS OBTAINED FROM ASPEN SIMULATION ........................................... 58
4.1 PROCESS CONVERGENCE ......................................................................... 58
4.2 RESULTS OF THE PROCESS STAGES ....................................................... 59
4.2.1 Stage 1: Air separation unit ...................................................................... 59
4.2.2 Stage 2: PEM Electrolysis ........................................................................ 59
4.2.3 Stage 3: Ammonia synthesis .................................................................... 62
4.2.4 General results summary ......................................................................... 63
5. EQUIPMENT SIZING AND COSTING ................................................................. 65
5.1 EQUIPMENT SIZING ...................................................................................... 65
5.2 SIZING RESULTS OF THE AMMONIA PLANT .............................................. 69
5.3 REQUIRED AREA AND PLANT LAYOUT ...................................................... 75
5.4 COST ESTIMATION OF EQUIPMENT ........................................................... 76
6. CONCLUSIONES / CONCLUSSIONS ................................................................. 84
7. BIBLIOGRAPHY................................................................................................... 86
APPENDIX 1: SIMULATION INPUT......................................................................... 90
5
APPENDIX 2: AUTOCAD PLANE .......................................................................... 105
LIST OF FIGURES
Figure 1. Renewable fuels in maritime transport ...................................................... 12
Figure 2. Modules of NH3 manufacturing plant ........................................................ 15
Figure 3. Plant location............................................................................................. 16
Figure 4. World ammonia production ....................................................................... 17
Figure 5. World NH3 capacity by region ................................................................... 18
Figure 6. Ammonia applications ............................................................................... 19
Figure 7. Ammonia production routes ...................................................................... 21
Figure 8. Ammonia production steps and uses ........................................................ 27
Figure 9. Proton Ventures NFUEL ........................................................................... 29
Figure 10. NFUEL size options (Proton Ventures, 2021) ......................................... 30
Figure 11. Thyssenkrupp 5MW ................................................................................ 31
Figure 12. Thyssenkrupp 20MW .............................................................................. 31
Figure 13. JGC plant flow diagram ........................................................................... 32
Figure 14. JGC plant ................................................................................................ 33
Figure 15. JGC plant ................................................................................................ 33
Figure 16. Siemens plant scheme ............................................................................ 34
Figure 17. Siemens plant ......................................................................................... 35
Figure 18. Minnesota West Central Research and Outreach Centre ....................... 36
Figure 19. Air separation unit DS ............................................................................. 41
Figure 20. Desalinization and water electrolysis DS................................................. 43
Figure 21. Ammonia synthesis DS ........................................................................... 45
Figure 22. ASU equipment ....................................................................................... 51
Figure 23. Desalinization and PEM equipment ........................................................ 52
Figure 24. Ammonia synthesis unit equipment ......................................................... 53
Figure 25. ASPEN Process flow diagram of ammonia production ........................... 56
Figure 26. Industrial compressor .............................................................................. 68
Figure 27. Industrial valve ........................................................................................ 68
Figure 28. Flash unit................................................................................................. 69
Figure 29. University on Minnesota Ammonia Reactor Skid .................................... 70
6
Figure 30. Fluitec multitube heat exchanger with mixing elements .......................... 71
Figure 31. Static mixer ............................................................................................. 73
Figure 32. Air Separation Unit prototype .................................................................. 73
Figure 33. Ariema PEM Electrolyzer ........................................................................ 74
LIST OF TABLES
Table 1. Renewable fuels properties ........................................................................ 11
Table 2. Renewable fuels ranking ............................................................................ 11
Table 3. Comparison of Hydrogen and Ammonia .................................................... 13
Table 4. A brief description of various hydrogen production processes (Adapted from
Wijers, 2011; Acar and Dincer, 2018)....................................................................... 22
Table 5. Ammonia production comparison ............................................................... 26
Table 6. Production technologies ranking ................................................................ 26
Table 7. Raw materials and products specifications ................................................ 39
Table 8. Antoine’s equation coefficients ................................................................... 40
Table 9. Feed streams ............................................................................................. 50
Table 10. Design specifications summary ................................................................ 58
Table 11. Breakdown streams summary .................................................................. 58
Table 12. ASU stream results .................................................................................. 59
Table 13. PEM stream results 1 ............................................................................... 60
Table 14. PEM stream results 2 ............................................................................... 61
Table 15. Synthesis stream results .......................................................................... 62
Table 16. Stream results summary .......................................................................... 63
Table 17. Base costs for pressure vessels ............................................................... 66
Table 18. Base costs for process equipment ........................................................... 66
Table 19. Flash unit dimensions ............................................................................... 69
Table 20. Reactor dimensions .................................................................................. 69
Table 21. Heat exchanger dimensions ..................................................................... 70
Table 22. Heaters and cooler dimensions ................................................................ 71
Table 23. Compressors dimensions ......................................................................... 72
Table 24. Mixers and splitter dimensions ................................................................. 72
Table 25. Material and pressure factors for pressure vessels .................................. 77
7
Table 26. Material and pressure factors for Heat Exchangers ................................. 77
Table 27. Materials and pressure factors for Direct Fired Heaters ........................... 78
Table 28. Materials and pressure factors for Refrigeration....................................... 78
Table 29. Materials and pressure factors for Compressors ...................................... 79
Table 30. Cost and size parameters summary ......................................................... 82
ABBREVIATIONS
A, B, C= Antoine coefficients
AIST= Advanced Industrial Science and Technology
AP= Aspen Plus
Ar= Argon
ASU= Air Separation Unit
AWE= Alkaline Water Electrolysis
Ca= Calcium
Cl (-) = Chloride
CTC= Components Technology Centre
DS= Design Specifications
FREA= Fukushima Renewable Energy Institute
H2= Hydrogen
H2O= water
HB= Haber-Bosch
IMO= International Maritime Organization
K= Potassium
Mg= Magnesium
N2= Nitrogen
Na (+) = Sodium ion
NH3= Ammonia
8
P= pressure
PEM = Proton Exchange Membrane
Q= flow rate
SIP= Japanese Strategic Innovation Promotion Program
SO4= Sulfate ion
SQM= Square Meters (m2)
T= Temperature
TRL= Technology Readiness Levels
Vrev= Reversible cell voltage
Process units: shall be named with the corresponding initial followed by a number
according to the order of appearance in the flowchart:
• C= Compressor
• DESAL= Desalination Plant
• F= Flash
• HX= Heat Exchanger
• M= Mixer
• P= Pump
• R= Reactor
• SEP= Separator
• SPLIT= Splitter
Streams: the streams will be named according to the equipment from which they
come; they will be named in the following way:
S (equipment name)-number (according to order of occurrence), example:
Out stream of compressor C1 would be: C1-1
9
1 INTRODUCTION
1.1 CONTEXT
1.1.1 Renewable fuels
It is globally known that emissions of greenhouse gases are increasing every year and
fossil fuels have great impact in this phenomenon. For this reason, many countries
have set out to reduce the emissions of CO2 within the next years by decreasing the
use of conventional fuels, which leave a big carbon footprint in our atmosphere. There
exists also a large list of countries which depend directly on external markets to obtain
products needed in the usage of fossil fuels, such as natural gas or petroleum and this
entails import costs.
For these two reasons the world is experiencing a significant increase in research and
development activities related to alternative fuels industry. In this context, emerging
technologies that enable their obtaining and, therefore, increase their technical-
economic feasibility, play an important and active role at industrial level.
At the moment many projects in search of new energy carriers can be find, defined as
substances or phenomenon which contain energy that can be later converted to other
forms such as mechanical work or heat (ISO 13600). A clear example of a
conventional energy carrier is natural gas, which can be easily stored and afterwards
it can be burnt to release energy.
As said, many development projects have settled the goal of substituting fossil fuels
for other clean and renewable energy sources. Some examples of renewable fuels
being investigated are hydrogen, ammonia, methanol, liquid biomethane or synthetic
diesel (Sea of innovation Cantabria Cluster, 2021). Even though these are some of
the most encouraging alternatives to fossil fuels, many materials and processes are
being investigated and all indications are that this activity will continue to increase,
showing results within the next years.
Table 1 (Sea of innovation Cantabria Cluster, 2021) shows a comparative chart

between the renewable fuels above mentioned and their properties including a
qualitative weighting according to the quality of each property (green=good,
yellow=acceptable, red=bad).
10
Table 1. Renewable fuels properties
Hydrogen Ammonia Methanol Liquid Synthetic

biomethane diesel
Boiling
temperature -253 -33 65 -162 200-385
(ºC)
Energy
density 8,5 12,7 15,5 20,3 36
(MJ/L)
CO2
emissions 0 0 36-46 56 17-109
(kgCO2/GJ)
Cost 110-200 70-150 120-680 60-140 130-770

(€/MWh)
Allocation of points according to the quality of the properties (2=good, 1=acceptable,

0=bad) leads to compare the five fuels in general terms and obtain a preliminary
ranking as shown in Table 2.
Table 2. Renewable fuels ranking
Points
Hydrogen 3
Ammonia 5
Methanol 4
Liquid biomethane 3
Synthetic diesel 4
According to the ranking, ammonia seems to be the best option as a renewable fuel;
in addition, it doesn’t present any problematic property, which makes it an easy
working and transporting component.
11
1.1.2 Marine transport fuels
Exhaust emissions from vessels have increasingly attracted attention in the

continuously growing marine transport world trade market. Although shipping has
proven to be the most energy efficient mode for mass transport, according to the
International Maritime Organization (IMO), emissions from ship engines are harmful
to the environment at both regional and global scales (Estimation of Vessel Emissions
Inventory in Qingdao, 2018). For this reason, different ways of reducing vessel’s
emissions are being investigated and one the most promising solution is the
substitution of conventional fuels for renewable options such as the ones mentioned
in chapter 1.1.1 of the present work.
When comparing ammonia to other renewable fuel options, this component is

considered a balanced solution. Ammonia has a significant higher volumetric energy
and has far more practical storage conditions, considering pressure and temperature
in comparison to liquid hydrogen. Furthermore, ammonia requires clearly less energy
for renewable synthetic production than carbon carriers. These are the main reasons
to further investigate the potential of ammonia as a marine fuel (Vries, 2019).
In addition, according to a study made by the Japanese shipping line “NYK Line”, one
of the biggest transport companies in the world, in the short term will be able to use
electric batteries for small boats, hydrogen fuel cells in medium-sized ships sailing in
relatively near-shore waters and ammonia is postulated as the main fuel for
transoceanic vessels such as container ships, RORO vessels (roll on roll off) or
passenger ships, as shown in Figure 1 (Hydrogen solutions for ocean-going vessels,
2020).
Figure 1. Renewable fuels in maritime transport
12
The difference in the use of hydrogen and ammonia is mainly reflected in the storage
and transport capacity of both fuels. A comparison between these two energy vectors,
showed in Table 3, summarize the results of NYK Line’s study.
Table 3. Comparison of Hydrogen and Ammonia
Hydrogen Ammonia
✓ Raw material for industry. ✓ Raw material for industry and
fertilizer production.
✓ Fuel for rolling vehicles. ✓ Main fuel for ships in 2050
according to IMO
✓ Electricity is produced by means ✓ Electricity produced by ammonia
of a combustion cell.
stacks or ammonia combustion.
 It is a difficult gas to store and ✓ Possibility to convert back to
transport.
hydrogen.
✓ Easy to store and transport.
As indicated in Table 3, hydrogen is a difficult gas to store and transport. Therefore,

according to NYK Line's study, such fuel will be valid for near-shore vessels making
calls to the coast as they do not need to store fuel for an excessively long period of
time and, therefore, refuelling can be carried out in smaller quantities.
However, when it comes to longer journeys, the amount of hydrogen to be stored is

large and this requires a technology which, in its current premature state of
development, includes substantial fuel losses; so, for this type of journey ammonia is
the best option as it is much simpler to store.
An additional positive aspect of ammonia is that it can be used as an energy carrier in

two different ways (Ammonia for power, 2018):
• By combustion in an adapted conventional engine. This is the most viable way

to reconvert already built classical vessels into ammonia powered ships.
• By storing it in a fuel cell. For this option fuel cells must be developed for future
vessels as they will be destined to be ammonia powered ships since their
construction.
In this context, ammonia it is assumed as the near future best option for maritime long-
distance transportation and for that reason, its production way and adaptation to this
specific industry to the new energetic sources is analysed in the present work.
13
1.1.3 Floating energy production systems
In the last decade, technology in the floating device sector has grown rapidly. This is
due to the growing energy race in the offshore wind sub-sector, which has been
focusing on the development and installation of floating windmills instead of
conventional windmills, which has led to the improvement of anchoring and flotation
systems that can be used for windmills but also for any type of floating device.
On the one hand, most marine windmills nowadays are attached to the seabed as
these designs have been implemented since the beginnings of the industry as they
use technologies implemented in inland windmills (monopile, gravity base, Jacket or
Tripod). This type of structures has been designed for many years and for that reason
is optimized and has many available data. The disadvantage they present is that they
are limited to depths above 65 meters as its cost rises exponentially for facilities in
deeper areas.
On the other hand, floating devices are an alternative to this problem. Although its
installation cost is still high, the development of this technology will enable windmills
growth as they can be far from the cost where they have plenty of space and do not
disturb the landscape. Some examples of floating devices are SPAR Buoy, Tension
Leg Platform (TLP), Barge Floater and Semi-submergible platforms.
As mentioned before this technology can be used for any floating device such as
platforms, ports, and artificial islands.
1.1.4 Bahia H2 offshore project
Cantabria aims to become one of the main regions in the development of green
ammonia technology and therefore is committed to the innovative project "Bahía H2
offshore", a green ammonia small-scale production plant, encouraging the
involvement of companies from different industrial sectors in the region
(https://www.aeh2.org/bahia-h2-el-proyecto-con-el-que-cantabria-quiere-obtener-
hidrogeno-verde-en-el-mar/).
The challenge of this project lies not only in designing an energy self-sufficient plant,
but also in being a floating marine device, which increases its design complexity due
to factors such as waves or corrosion inherent to the marine environment. In addition,
14
to obtain a completely clean device, a thorough study of the process must be carried
out in order to optimize its ammonia production without gas emissions.
The "Bahía H2 offshore" project is promoted by the "Sea of innovation Cantabria

cluster", counts on the participation of companies such as the Port of Santander, the
National Hydrogen Centre (CNH2), ARIEMA S.L., the IHCantabria and the
Components Technology Centre (CTC), among others.
In summary, the prototype to be designed under "Bahía H2 offshore" project, consists

of a 500kW floating photovoltaic panel generation system connected to a 25x15 meter
floating platform on which equipment for the production of ammonia by means of the
Haber-Bosch process is to be installed. This plant must be capable of producing
around 25kg/hr. of ammonia with a purity of over 98% in a completely clean manner,
i.e., without polluting gas emissions and from renewable resources.
In order to fulfil the objective, the plant shall include the following modules (Figure 2):
• Module for obtaining H2 from seawater.

• Module for obtaining N2 from air.
• Haber-Bosch module for the transformation of syngas into ammonia.
• Storage tanks.
H2 N2
H2 N2
HB
storage storage
NH3
storage
Figure 2. Modules of NH3 manufacturing plant
15
The location selected for the plant is the Port of Santander (Figure 3) because it shows
the following advantages:
• The bay of Santander is a sheltered place with low waves.

• It is located in one of the main logistical hubs of the region, with a third
generation Port, which facilitates the transport of materials for manufacturing
and the transfer of products.
• The surrounding industrial environment allows its development and continuous
improvement.
• It is easily accessible for periodic inspections and maintenance.
Figure 3. Plant location
16
1.2 AMMONIA PRODUCTION PROCESS
Ammonia is a compound of hydrogen and nitrogen containing 17.65% by weight of H2.

It is frequently used as a fertilizer, providing nitrogen to the fields, and it is a product
of great importance in agriculture. In addition, it is used as a cleaning component and
in the near future it can be used as a renewable motor fuel.
Due to its many uses, ammonia is one of the most highly produced inorganic
chemicals. World demand for ammonia currently exceeds 186 million metric tons per
year (IFA market intelligence, 2021). The largest producer of ammonia is Asia, mainly
China, which currently accounts for 27% of world production, followed by Russia
(10%), the United States (9.3%) and India (8%) (Fig.4) (U.S. Geological Survey, 2021).
Ammonia production
27%
36,50%
10%
9,30%
2,70%
3% 8%
3,50%
China Russia USA India Indonesia Trinidad and Tobago Saudi Arabia Others
Figure 4. World ammonia production
In addition, in the coming years, the emergence of new uses for ammonia and
improved manufacturing technologies are expected to boost ammonia consumption,
which could reach 195 million metric tons per year by 2025 (Fig. 5)
(IFA market intelligence, 2021).
17
Figure 5. World NH3 capacity by region
18
Most of the ammonia (80%) is used in the manufacture of fertilizers (Figure 6), and its
main applications are (Yapicioglu, et al., 2019):
• Ammonium nitrate
• Ammonium salts
• Urea
• Explosives manufacturing
• Caprolactam, nylon
• Polyurethanes
• Cryogenic gas
• Domestic cleaning products
Ammonia applications
Ammonium
Other Compound; 5%
Bicarbonate; 6%
UAN; 5%
DAP; 2%
MAP; 2%
Urea; 42%
Ammonium
Nitrate; 8%
Ammonium
Sulphate; 3%
Calcium-Ammonium
nitrate; 3% Non-Fertiliser
Other; 4%
uses; 15%
Direct Application;
3%
Figure 6. Ammonia applications
Due to the great importance of this product, since the beginning of the 20th century,
improvements have been developed and the efficiency of its production technology
has been increased, mainly the Haber-Bosch process, considered one of the greatest
technological advances of the industrial era. The Haber-Bosch process has become
so important that currently 90% of the ammonia produced globally is obtained in this
way.
19
The process was initially patented by the physic-chemist Fritz Haber. In 1910 Carl
Bosch, working for the chemical company BASF, succeeded in commercializing the
process. Both Haber and Bosch were awarded the Nobel Prize in 1918 and 1931
respectively for overcoming the chemical and engineering problems posed by the use
of large-scale, high-pressure technologies.
We must bear in mind that in today's market ammonia production plants are of
industrial size and seek the highest possible production in order to gain advantage
form the economy of scale, so advances in this technology have not focused on
optimizing the size of the plants. However, process intensification appears last years
as a promising research area that can fulfil the objectives of an offshore ammonia
production.
The main technologies and projects driving the growth of this process, as well as the
introduction of alternative NH3 production technologies, will be briefly described below.
1.2.1 Ammonia production routes
Meanwhile the Nitrogen to produce ammonia is obtained by Air Separation Units

(ASU), the main difference in the way of obtaining ammonia lies in the way of obtaining
the hydrogen for its synthesis (Yapicioglu, et al., 2019):
• Reforming: when the raw material is natural gas or naphtha, the way to obtain
ammonia is by reforming the hydrocarbons to extract hydrogen.
• Partial oxidation: the raw material used can be heavy hydrocarbons or coal.
• By product Hydrogen: hydrogen-rich gas, which is a by-product of some other
process, is introduced directly.
• Electrolytic route: hydrogen is obtained by water electrolysis.
• Biological route: ammonia is obtained by conversion of biological products.
The use of natural gas as a power source has been growing over the years, while the
use of naphtha and other petroleum products has been decreasing. (Kirk-Otmer, 2000)
20
Different ways of obtaining ammonia are shown in the block diagram below (Figure 7):
Figure 7. Ammonia production routes
1.2.2 Conventional Haber Bosch process
Since the beginning of the 20th century, the most industrially used and efficient
practice for obtaining ammonia has been the production of hydrogen by hydrocarbon
reforming.
While it is true that this process is highly effective and produces large amounts of
hydrogen, natural gas is a fossil fuel whose combustion results in a large amount of
CO2 emissions into the atmosphere.
In addition, since these plants are supplied with natural gas, they are totally dependent
on this resource and its supply, so their installation is limited only to onshore sites with
a natural gas distribution network.
The process itself consists of obtaining ammonia (NH3) from nitrogen (N2) and
hydrogen (H2) both in gaseous state, by means of the following reversible exothermic
reaction:
𝑁2 (𝑔) + 3𝐻2 (𝑔) ↔ 2𝑁𝐻3 (𝑔) + ∆𝐻

21
In general terms, this reaction is characterized by being very slow, so it is carried out
over a catalyst (commonly iron, Fe3+); it also takes place under conditions of about
300 bar of pressure and a temperature of approximately 400ºC which avoid to reach
a yield of about 20%, being mandatory a recycle loop in order to obtain industrially
feasible global conversions.
Regarding the adaptation of the Haber-Bosch process to the desired size in this
project, it must be initially considered that the design criteria for small plants are very
different from those of large-scale ammonia production plants. For such small plants,
the economic factor is more critical while the technical and operational factor is less
important. This will be reflected in the process design, which will try to minimize the
number of components, apply standardized equipment and design modules that
minimize plant construction work.
1.2.3 Sustainable ammonia by Haber Bosch
In recent years, restrictions on pollutant gas emissions and new environmental policies
have encouraged new ways of obtaining hydrogen in a clean way, based on the use
of renewable resources and the design of process without emissions.
In this way, numerous advances have been made in obtaining hydrogen by alternative
ways. The main options currently available are shown in Table 4, including energy
inputs, technology based a short description and the associate TRL (Sustainable
Ammonia Production, 2021)
Table 4. A brief description of various hydrogen production processes (Adapted from Wijers, 2011; Acar and Dincer,
2018)
Main energy Technologies Brief description TRL

inputs
Water electrolysis -Direct stream is applied in order Large
to split water into hydrogen
and oxygen.
- The entire process of an CH4 Medium/

CH4 assisted-Solid assisted -SOFEC is based on small
Oxide Fuel Electrolysis substituting high value electricity
Cell with cheaper methane. In
the CH4 assisted-SOFEC,
(SOFEC)/ Natural Gas methane is added to the anode
Electrical Assisted Steam side of the electrolyzer, the
Electrolysis decomposition potential (voltage)
(NGASE) of water is decreased, and this
results in a lower energy
22
usage and higher conversion ratio

of electricity for hydrogen
production.
Large
Plasma arc - Purified natural gas (without
decomposition H2S, CO2, H2O, etc.) is passed
throughout the plasma arc in order
to produce hydrogen and
carbon soot.
High Temperature - Both electrical and thermal

Electrolysis (HTE) energy are utilized in order to Large
initiate, water splitting for
hydrogen production.
Electrical and
thermal - Both electrical and thermal
Hybrid thermochemical energy are utilized in cyclical Medium
cycles reactions
Coal Gasification - Conversion of coal through, Large
thermochemical process into
syngas.
- Fossil fuels are converted into

Fossil fuel reforming hydrogen and carbon dioxide. Large
Thermochemical Thermolysis - Thermal decomposition of steam Large

at temperatures higher
than 2,226.85°C.
-Cyclic reactions (net reaction:

Thermochemical water splitting into hydrogen) Large
processes -Thermo-catalytic conversion
-Biomass conversion into
Hydrogen
Photo-electrochemical - A hybrid cell which generates Small
cells (PEC) voltage and current through
absorption of light simultaneously.
Photonic - Mimicking photosynthesis Small

Artificial process for hydrogen production
photosynthesis
- Direct water splitting via photo- Small
catalyst.
Photo-catalysis
Photonic and Bio-photolysis -Biological processes Small
biochemical (microbes/bacteria, etc.) through
which water dissociates into
hydrogen and oxygen in the
presence of light.
Dark fermentation - Biological processes are utilized Small
Biochemical for hydrogen production in
the absence of light.
- Fermentation process initiates

Photo-fermentation through exposure to light. Small
23
Among the technologies mentioned, the most widely used for sustainable hydrogen
production is water electrolysis, supported by renewable technologies such as solar
or wind energy.
Proton Exchange Membrane (PEM) electrolysis creates a reaction using an ionically

conductive solid polymer, rather than a liquid. When voltage is applied between two
electrodes, negatively charged oxygen in the water molecules gives its electron,
resulting in protons, electrons, and O2 at the anode.
The H+ ions travel through the proton-conducting polymer towards the cathode, where
they take an electron and become neutral H atoms. These combine to make H2 at the
cathode. The electrolyte and two electrodes are sandwiched between two bipolar
plates, which transport water to them, transport product gases away from the cell,
conduct electricity, and circulate a coolant fluid to cool down the process.
1.2.4 Alternatives to the Haber Bosch process
Electrochemical processes
This type of processes can be divided into three major groups based on the
temperatures of the electrochemical cells: low temperature (<100°C), medium
temperature (100-400°C) and high temperatures (400-750°C). The advantages of this
type of process with respect to the Haber Bosch process are mainly the next four
(FUTURE OF AMMONIA PRODUCTION:, 2017):
• Higher efficiency allowing energy savings.

• Lower purity required.
• Lower temperatures and pressures.
• They are modular, which allows their use in small and medium-sized plants.
Non-thermal plasma synthesis
This alternative has the advantage of operating at temperatures around 50ºC and
atmospheric pressure conditions. This solves some of the problems posed by HB
since the reduction of these conditions has a direct impact on the cost of energy and
fossil fuels. However, it comprises two challenges yet to be developed (A review on
the non-thermal plasma-assisted ammonia synthesis, 2018).
• Nitrogen gas fixation
24
• Reverse reactions
In addition, the state of conversion and efficiency still needs to be advanced, so it is in

the small and medium scale development phase.
Functional catalyst with nitrogenase motivated peptide
Ammonia is produced in nature by nitrogenase enzymes with an efficiency of about

75%. Since this percentage is very high, it is intended to use these enzymes for the
industrial production of NH3. This type of ammonia synthesis is very promising but its
low temperatures and working pressures present an efficiency of less than 1%, which
requires catalysts to improve this efficiency (Renner, et al., 2020).
On the other hand, peptide functional catalyst has been developed and tested in anion
exchange-based systems. The materials used for such a catalyst show promising
results compared to conventional catalysts.
1.2.5 Discussion of the selected technology
In accordance with the previous description, different alternatives exist to carry out a
complete and reliable process of ammonia synthesis being necessary to select the
best one in order to suits the proposed project.
First of all, it is necessary to choose the source of the raw materials to convert them
into ammonia. Considering only raw materials obtained in a renewable way and whose
processing does not emit polluting gases, reforming and partial oxidation processes
would be discarded. Although both of them are very efficient ways of NH3 production,
the environmental requirements of the project make them discarded.
The process to be carried out is then selected under qualitative and subjective
comparing different factors that influence production. Based on different articles,
research and reports, using the same weighting technique as in Table 1 and Table 2:
(green=good (2 points), yellow=acceptable (1 point), red=bad (0 points)) results are
obtained in Table 5 and 6:
25
Table 5. Ammonia production comparison
Efficiency Cost P & T conditions TRL

Haber-Bosch
Electrochemical
processes
Non-thermal
plasma
synthesis
Functional
catalyst with
nitrogenase
motivated
peptide
Table 6. Production technologies ranking
Points
Haber-Bosch 6
Electrochemical processes 5
Non-thermal plasma synthesis 4
Functional catalyst with nitrogenase 4
motivated peptide
Once the process to be used has been decided (Haber-Bosch) it is necessary to

determine which technology from Table 4 would be used as the hydrogen source. As
mentioned above, water electrolysis remains the most viable option due to its TRL,
cost and widely investigated and improved technology among the years.
At that point, the technology selected for the whole plant in the present project, as it is
specified in the project objective (section 1.4), will be a Haber Bosch process obtaining
H2 from water by electrolysis and N2 from air in an air separation unit (ASU) (Figure
8).
26
Figure 8. Ammonia production steps and uses
27
1.3. SMALL SCALE HABER BOSCH PLANTS AND PROJECTS USING

RENEWABLE ENERGY
Manufacturing their own ammonia production plant has many advantages, especially
in this case where it is a research and development project. However, it is important
to know the state of the art of similar technologies, either to take advantage of its
strengths for the actual project benefit or to consider the weakest points of the process
in order to avoid problems or possible mistakes.
For this reason, a study of the current market and the development of similar projects
has been carried out, analysing their different characteristics in order to get a global
knowledge of the scope and limitations of this project.
The following are some of the small ammonia plants available on the market as well
as the most promising projects for the future of the sector.
1.3.1 Proton ventures
Proton Ventures offers the possibility of manufacturing small scale ammonia plants
with the named NFUEL units (Figure 10). The electricity used for this plant can come
from renewable sources such as solar turbines or photovoltaic panels. This new
concept allows the production of sustainable ammonia for subsequent use as fertilizer,
energy carrier or fuel. (Proton Ventures, 2021).
Currently they have designed NFUEL units to produce 120kg/h NH3 (Solar to
Ammonia – via Proton’s NFuel units, 2014). As can be seen in Figure 10, the unit is
divided into skids that fit into 40-foot containers, which greatly facilitates transportation
and logistics. Each of these skids is fully automated, remotely operated and
guarantees technical integrity.
Figure 9 shows the NFUEL unit next to a wind farm, but it could also be accompanied
by a photovoltaic farm or any type of energy source that allows obtaining hydrogen by
electrolysis.
28
Figure 9. Proton Ventures NFUEL
The following are some of the plant’s main properties:
• NFUEL units are powered by electricity from renewable energy sources and
are designed to withstand rapid power fluctuations.
• Labour costs are minimal due to remote monitoring and control of the unit via a
secure wireless connection.
• According to the company, NH3 production including compressors and reactors
can operate efficiently for more than 30 years. Electrolyzer and nitrogen
production systems have a lifetime of around 20 years, but this can be extended
by proper operation and maintenance of the system.
• All equipment operating at high pressures in the ammonia synthesis loop is
designed and built to withstand fatigue due to pressurization and
depressurization cycles.
• The interconnection between the different skids is designed on a site-specific
basis and under the required skid layout conditions.
• The N2, H2 and water purification units as well as the main compression system
are equipped with programmable logic controllers.
• It incorporates an emergency shutdown system into the overall control system
design, along with the installation of safety valves, instrumentation and
ammonia, nitrogen and hydrogen and heat detectors located at strategic points
to detect any possible leaks.
29
• The equipment consists of the following units:

o - Nitrogen generation skid.
o - Hydrogen generation skid based on electrolysis.
o - Ammonia compression skid
o - Ammonia synthesis skid
o - Ammonia storage tank
o - Operations skid, control panel and motor control centre
• The service factor is 95% guaranteed and the unit's catalyst is guaranteed to
last 15 years if the manufacturer's protocols are strictly followed.
• The company offers different sizes and based on these, analyses the demand
and energy consumption in the market to install decentralized ammonia plants
(Fig. 10).
Figure 10. NFUEL size options (Proton Ventures, 2021)
1.3.2 Thyssenkrupp
According to the German company, whereas, in conventional ammonia plants,

hydrogen is produced by steam reforming with natural gas, Thyssenkrupp's green
ammonia concept uses AWE (Alkaline Water Electrolysis), while the nitrogen required
for ammonia synthesis is produced by an air separation unit (ASU). AWE is based on
the proven chlor-alkali electrolysis technology developed by Thyssenkrupp Uhde
Chlorine Engineers with its EP(C) technology and execution experience gained from
more than 600 plants with more than 10 GW of installed capacity worldwide.
All necessary for AWE-based green hydrogen production is energy from renewable
sources and water. In addition, AWE is ideal for use in green ammonia plants, as it
can be started in minutes and follows load variations in seconds (Thyssenkrupp,
2021).
30
Thyssenkrupp has developed two production concepts: a 50 mtpd plant based on 5

MW input power and 100% availability (Fig. 11) and a 300 mtpd production plant based
on 20 MW input power (Fig. 12). As the latter approaches industrial scale, it could be
an interesting refurbishment option for greening existing plants. This reduces
engineering and construction costs while facilitating implementation, a fast-track
solution for potential customers.
Figure 11. Thyssenkrupp 5MW Figure 12. Thyssenkrupp 20MW
ThyssenKrupp evaluated the five key factors of feasibility:
• Capital expenditures.
• Availability and cost of renewable energy.
• Potential transportation constraints.
• The cost of ammonia.
• CO2 emission restrictions and taxes.
The conclusion was that in landlocked locations with low energy costs, the installation
of a green ammonia plant may be an interesting option, especially for the chemical or
fertilizer industry. Not surprisingly, economies of scale favour conventional plants with
higher production capacities. But in addition to its economically viable existence as a
niche product, green ammonia is becoming increasingly interesting for renewable
energy producers as a suitable energy carrier and storage medium.
31
1.3.3 JGC Holdings
Under the theme of “Development of ammonia synthesis from CO 2-free hydrogen”

from the Japanese Strategic Innovation Promotion Program (SIP) “Energy Carriers”,
JGC Holdings corporation is developing an advanced ammonia synthesis process
using renewable energy, such as photovoltaic and wind turbine power generation, to
be able to produce “Green” ammonia, aiming to contribute to a low-carbon society.
(Demonstration of CO2-Free Ammonia Synthesis Using Renewable Energy-
Generated Hydrogen, 2018) .
Also, utilizing the catalysts developed by the Japanese National Institute of Advanced
Industrial Science and Technology (AIST), National Institute of Technology Numazu
College and JGC designed and constructed an ammonia synthesis demonstration
plant in FREA, the Fukushima Renewable Energy Institute. From April 2018, the plant
started operation to evaluate the performance of the developed catalysts and acquire
the engineering data for scaling up in the future.
JGC’s plant was constructed according to the flowsheet in Figure 13. Figures 14 and
15 shows the plant working under the specified properties related in (Demonstration
of CO2-Free Ammonia Synthesis Using Renewable Energy-Generated Hydrogen,
2018):
Figure 13. JGC plant flow diagram
32
Figure 14. JGC plant
Figure 15. JGC plant
33
With this project launched in 2018, JGC aims to contribute to decarbonisation and to
improve the energy supply chain.
1.3.4 Siemens
Following the steps of JCG, in June 2018 Siemens launched operations at its Green
Ammonia Demonstrator, at the Rutherford Appleton Laboratory outside Oxford in the
UK. Its aim is to provide insights into the business case for ammonia as a market-
flexible energy storage vector (Green ammonia pilot plants now running, in Oxford and
Fukushima, 2018).
The Siemens demonstrator includes not only storage assets but also combustion
assets: an internal combustion engine adapted to generate electricity using ammonia
as a fuel. The main objective of the plant is to evaluate an all-electric synthesis and
energy storage demonstration system based on Green Ammonia.
Figures 16 and 17 show a scheme of the plant itself and its installation site (Hablutzel,
2019).
Figure 16. Siemens plant scheme
34
Figure 17. Siemens plant
When it comes to logistics, Siemens’s plant distribution looks similar to the Proton
Ventures skids and differ from JCG or Thyssenkrupp’s plants which are more compact
and static (Figures 15-16).
According to Siemens, the main components of this plant are the following:
• 20kW wind turbine.

• 13kW Electrolyzer, producing approx. 2.4 Nm3 /hr H2.
• 7kW ASU (pressure-swing absorption) producing 9 Nm3 /hr N2.
• 30kg / day Haber-Bosch synthesis capacity for NH3 (output limited by H2
production capacity).
• 350kg on-site NH3 storage.
• 30kWe Generator set (reciprocating spark-ignition engine) running on
ammonia.
• Siemens PCS7 Control system for unattended operation.
1.3.5 University of Minnesota
In 2013, a pilot plant was built using electricity from a utility-scale wind turbine to
produce hydrogen by electrolyzing water, nitrogen is separated from air, and then
these gases are combined to produce anhydrous ammonia (Figure 18).
35
Figure 18. Minnesota West Central Research and Outreach Centre
According to the University of Minnesota, “we envision a sustainable energy and

agriculture system in which local production facilities use wind energy to produce
ammonia. The ammonia is then used as fertilizer and fuel. Compared to other energy
storage, ammonia is flexible and has many potential uses. Local smart-grids and
utilities can use ammonia to provide short- and long-term storage to backup
intermittent wind and solar generation. Farmers can produce wind-generated
ammonia to significantly reduce the carbon footprint of their products” (Reese, 2020)
36
1.4 OBJECTIVE
This project focuses on the green production of ammonia and its use as an alternative
fuel, a field of research that is gaining increasing interest. The aim of this project is to
develop an ammonia production plant that can be installed on a floating platform,
powered by solar panels, which produces ammonia using the Haber-Bosch process
and use this product to power cargo ships in a way that is totally free of polluting
emissions: obtaining hydrogen through the electrolysis of seawater and nitrogen from
the separation of air. In this context, this degree final project consists of the preliminary
design, by means of the process simulation in ASPEN Plus, of the equipment
necessary to obtain ammonia in the aforementioned way.
Specific objectives
• Analyse the small-scale Haber Bosch state of art.

• Design a plant capable of producing 25kg/h of ammonia with a purity of 98%.
• Specify dimensions of the plant.
• Make a preliminary cost estimation.
37
38
2 DESIGN SPECIFICATIONS
This section shows the design specifications related to the process, energy and raw
materials surplus and characteristics and the final product properties. The different
subsystems or stages of electrolysis, air separation and ammonia synthesis are
showed with a process flow diagram which includes material and main process
conditions as well as relevant process specifications obtained from previous literature.
2.1 RAW MATERIALS AND PRODUCTS
• Haber Bosch process with the next overall input-output diagram
Air Product
Oxygen
Seawater
H2O
• Raw materials and products: based on conditions of the port of Santander and
product requirements for its future use (Table 7).
Table 7. Raw materials and products specifications
Seawater Air Ammonia

T (ºC) 16.5 13.8
P (bar) 1
Q (kg/h) 25
Composition (%)
H2O 96.4 1
Cl (-) 1.98
Na (+) 1.1
SO4 0.276
Mg 0.13
Ca 0.04
K 0.04
O2 21 0.5
N2 78.05
Ar 0.95
H2 0.5
NH3 98
39
• Properties. Antoine’s equation (Table 8):

Table 8. Antoine’s equation coefficients
A B C
Nitrogen 14.93 588.72 -6.60
Hydrogen 13.63 164.90 3.19
Argon 15.23 700.51 -5.84
Ammonia 16.95 2132.50 -32.98
40
2.2 AIR SEPARATION UNIT
Figure 19. Air separation unit DS
41
• Air separators
Pressure= 7 bar
Temperature= -177ºC
Nitrogen from air: 98%
42
2.3 DESALINIZATION AND WATER ELECTROLYSIS
Figure 20. Desalinization and water electrolysis DS
43
• Electrolyzer:
1
𝐻2𝑂 + ∆𝐻 → 𝐻2 + 𝑂2
2
∆𝐻𝑅 = ∆𝐺𝑅 + 𝑇∆𝑆R
Standard conditions: ∆G˚R = 237 kJ mol-1
∆GR
Vrev = Where z is the number of electrons transferred per
𝑧𝐹
hydrogen molecule produced and F is the Faraday constant
44
2.4 AMMONIA SYNTHESIS
Figure 21. Ammonia synthesis DS
45
• Converter R2:
0.5𝑁2 + 1.5𝐻2 ↔ 𝑁𝐻3
The ammonia production reaction has a conversion rate of 𝓇 = 0.3
P=138 bar
T=498ºC
[inert components] <12% to avoid problems in the reactor as they can
affect temperatures and conversion.
• Flash F3:
Tout=-26ºc
Pin= 138 bar
Pout=17 bar
• Separator SPLIT3:
ε purge= 0.1
[Inert components] <12%
46
47
3 ASPEN PLUS SIMULATION

Several authors modeled and simulated previously ammonia production plants at
industrial scale using Aspen tools as Frattini et al., 2016; Lin et al., 2020; Osman et
al., 2020; Verleysen et al., 2020 among others. Chehade and Dincer, 2021, proposed
and developed a small modular ammonia converter by solving mass and energy
balance in Matlab and Consol In the present work Aspen Plus it will be used to simulate
a small ammonia plant including Nitrogen and Hydrogen obtention.
Sequential modular simulators (SMS) perform flowchart calculations in the following

way:
• Executes each block of unit operations sequentially.

• Uses the output streams calculated in each block as a feed into the next block.
Flow diagrams with recirculation cycles, design specifications and optimization

problems must be solved iteratively. Their solution requires:
• Choose breakthrough streams: a breakthrough stream is a circulating stream

with component molar fluxes, total flux, pressure, and enthalpy determined by
iterations. The breakdown current can be any within the cycle.
• Define convergence blocks to converge breakout streams, design
specifications or optimization problems. Convergence blocks determine how to
update the variables for a breakthrough stream or design specification from
iteration to iteration.
• Determine a sequence that includes all units and convergence blocks.
Among the possibilities offered by a process simulator, as far as convergence is

concerned, the options that can be introduced by the user are, for example, the
creation of different convergence blocks or the change of the order of execution of the
blocks, among others.
A breakthrough stream converges when the following expression is true for all
convergence variables of the breakthrough streams:
(𝑋𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 − 𝑋𝑒𝑠𝑡𝑖𝑚𝑎𝑡𝑒𝑑)
−𝑡𝑜𝑙 ≤ ≤ 𝑡𝑜𝑙
𝑋𝑒𝑠𝑡𝑖𝑚𝑎𝑡𝑒𝑑
48
The default convergence variables are: total molar flux, individual molar fluxes,
pressure and enthalpy.
The complexity of the simulation for the case of an ammonia production plant lies in
the existence of several recycle streams, purge, different design specifications,
specific thermodynamics, and high working pressures.
The simulation of the ammonia production process is then carried out with the Aspen
Plus commercial simulator. As this is a complex process due to the high pressures
and the need for recycling, its simulation will also be complex.
3.1 INPUT DATA
When starting the simulation, it is necessary to specify the units you are going to work
with. In this case the following units were chosen due to the ease of adapting the
information obtained from literature and research:
• Pressure: bar
• Temperature: degrees Celsius
Subsequently, all the components involved in the process are selected from the Aspen
Plus library. The following elements were selected for this process, which are the ones
that interact in the plant:
1. Hydrogen: H2
2. Nitrogen: N2
3. Water: H2O
4. Ammonia: NH3
5. Chlorine: CL-
6. Sodium: Na+
7. Sulphate: SO4
8. Magnesium: MG
9. Calcium: CA
10. Potassium: K
11. Oxygen: O2
12. Argon: AR
49
3.2 FEED AND PRODUCT STREAMS
• Feed streams
Table 9 shows the main feed streams: seawater and air, which are defined by their
molar composition, pressure, and temperature.
Table 9. Feed streams
AIR SEAWATER
T(ºC) 13.5 16.5
P(bar) 1 1
Q(kg/h)
NITROGEN 28.45 0
OXYGEN 8.71 0
ARGON 0.48 0
HYDROGEN 0 0
AMMONIA 0 0
WATER 0 127.69
CHLORINE 0 0.6
SODIUM 0 0.5
SULFATE ION 0 0.23
MAGNESIUM 0 0.04
CALCIUM 0 0.02
POTASIUM 0 0.02
TOTAL 37.65 129.1
• Product streams
In the air separation unit, the SEP2-2 stream, which is an oxygen-rich stream
is obtained after air fractionation. The desalination unit and the PEM
electrolyzer are the equipment that has the most output streams; here there are
the next streams i) the DESAL-2 stream, that contains all the unwanted
impurities in the water since the electrolyzer requires a stream of water with a
high purity, ii) F2-1, which is a mixture of oxygen and water, and iii) SEP4-2,
which contains water mixed with hydrogen and oxygen.
The ammonia synthesis process only has one product stream apart from the
final product, this stream is SEP5-1, and it is one of the most important steps
of the process as it is the purge necessary to ensure that the percentage of
inert components entering the reactor is lower than 12%.
50
3.3 PROCESS THERMODYNAMICS
Finally, before proceeding to build the process flow diagram of the plant itself, the
"Peng-Robinson" thermodynamic package is selected as the most suitable for the
process to be studied and the most used in ammonia synthesis by the Haber-Bosch
process.
3.4 EQUIPMENT
The equipment involved in the simulation of the ammonia production process are
shown in this section following the three subsystems or units of the global process
(ASU unit, Desalination & PEM electrolysis unit and Ammonia synthesis unit).
3.4.1 Air separation unit
In the nitrogen production stage by air separation, only an air stream directly from the
plant's environment is introduced as shown in Figure 22.
Figure 22. ASU equipment
The equipment used is:
• C1: compressor
• HX1: air feed preheater
• The core of air separation equipment is an important system for low
temperature separation. High and low pressure two – stage rectification is
usually adopted. In this case it’s simulated with equipment SEP1 (RadFrac*)
and SEP2
• M1: mixer
51
*The RadFrac model is the main separation block in Aspen Plus. The block can
perform simulation, sizing, and rating of tray and packed columns. The model
specification, done in the Setup form, requires complete specifications of column
configuration, specifications, feed(s), product(s), and any side streams (Hussain,
2006).
3.4.2 Desalination unit and PEM electrolysis
Like the previous stage, this one has only one incoming stream, the seawater, that
must be further purified and from which the feedstock of hydrogen to the ammonia
process is obtained (Fig. 23).
Figure 23. Desalinization and PEM equipment
The equipment in this unit is:
• DESAL: The desalinization unit in this process has been simulated as a

separator which is capable of obtaining a stream of 99.9% water, pure enough
for the stacks to operate properly.
• M2: mixer whose function is to utilize the recycled water streams together with
the incoming water from the desalination unit.
• P1: pump.
• HX3: electrolyzer preheater.
• R1: electrolyzer, modelled as an equilibrium reactor in which water splits into
oxygen and nitrogen.
52
• SEP3: oxygen phase separator. Separates gaseous oxygen from water exiting
the cell stack (ASA, 2022)
• SPLIT1, SPLIT2: splitters
• M3, M4: mixers used to combine the streams coming from the splitters.
• F1: flash unit to separate water from the hydrogen-rich stream.
• F2: flash unit to separate water from the non-hydrogen-rich stream.
• SEP4: Hydrogen phase separator. Separates gaseous hydrogen from water
exiting the cell stack (ASA, 2022)
3.4.3 Ammonia synthesis unit
The output streams from the electrolysis and air separation modules are mixed and
subsequently the main recycle stream is added. At this stage, ammonia synthesis
takes place in the R2 converter (Fig. 24).
Figure 24. Ammonia synthesis unit equipment
The equipment in this unit is:
M5: hydrogen and nitrogen stream mixer.
HX4: preheater to avoid liquid in the compressor C2
C2: compressor of the inlet streams to achieve a similar pressure to recycle stream.
M6: recycle and feed stream mixer.
C3, C4: adiabatic compressors.
53
HX5: shell and tubes heat exchanger that heats the inlet stream by using the reactor’s
hot outlet stream.
HX6: electrical heater to achieve the reactor’s inlet temperature.
R2: ammonia converter at high temperature and pressure.
HX7: cooler.
F3: flash separator in charge of obtaining the ammonia final product with the desired
purity and separating it from hydrogen and oxygen that haven’t reacted.
SPLIT3: the gas outlet of F3 stream is recycled and purged through this equipment in
the appropriate amount to maintain the inert components in the reactor inlet less than
12%.
3.5 DESIGN SPECIFICATIONS
To set up the process, two specifications are implemented: N2/H2 ratio and reactor
inlet inert components concentration.
Design specification 1: DSWATER
The electrolyzer has a water inlet, as a source of hydrogen, whose flow rate will be
affected by a design specification which must be such that the reactor inlet stream has
the correct nitrogen: hydrogen ratio (1:3), given by the ammonia reaction
stoichiometry.
For this purpose, a design specification is created which acts by varying the flow rate
of feed water entering the electrolyzer, depending on the composition of the reactor
inlet stream.
Variables H20 and N20 are created as the mole fraction of the M6-1 hydrogen and
nitrogen stream respectively. It is necessary to relate them by means of a Fortran
sentence forcing to fix this relation in 3.0, the variable that remains free is the flow of
water of entrance, since it was the hydrogen contribution to the process.
• Variable set: nitrogen : hydrogen ratio=3 in stream M5-1.

• Controllable variable: flow rate of water stream.
54
Design specification 2: DSPURGE
In the conversion stage, the percentage of inert components entering the reactor must
be less than 12%, therefore a purge is introduced in the recirculation stream. The
purge rate of which will be indicated by a design specification.
The molar flow rate of argon in the M6-1-1 inlet stream to the converter is defined, by
means of a Fortran sentence this variable is related to another variable also defined
by the user called "TOT" which is the total molar flow rate of the reactor inlet so that
the percentage of inerts can be calculated and given a value. The variable to be left
free is the fraction purged on SPLIT3.
• Variable set: mole fraction of inerts= 0.1 at converter inlet.

• Controllable variable: purge stream flow rate.
55
3.6 PROCESS FLOW DIAGRAM OF THE COMPLETE PROCESS
Figure 25 represents the process flow diagram of the complete process evaluated in Aspen Plus. Appendix 1 shows the ammonia synthesis process ASPEN simulation INPUT.
Figure 25. ASPEN Process flow diagram of ammonia production
56
57
4 RESULTS OBTAINED FROM ASPEN SIMULATION
4.1 PROCESS CONVERGENCE
The resolution of the simulation has been carried out with four "solvers" or
convergence blocks, the following shows the equipment involved in them and the order
carried out to calculate the flow diagram, with the breakdown streams chosen by the
simulator.
• SOLVER01
• SOLVER02 (DS-WATER)
• SOLVER15 (DS-PURGE)
Table 10 shows the convergence blocks of the different design specifications, the
status, the error, the tolerance, the relationship between both and the value of the
manipulated variable.
Table 10. Design specifications summary
Design Spec Status Error Tol Error/ Variable Convergence

Tolerance value block
DS-WATER Conv -0.0026673 0,01 -0.26673 7.088 SOLVER02
DS-PURGE Conv 0.0019484 0,12 0.0162367 0.1 SOLVER03
Table 11 shows the convergence status of the breakdown streams and the variable
checked for convergence with the highest error.
Table 11. Breakdown streams summary
Tear Status Variable max Max error/ Max Absolute Convergence

error Tol relative error block
error
M6-1 Conv N2 0.984015 -9.84 e-5 7.19 e-8 SOLVER01
MOLEFLOW
HX5-1 Conv N2 0.637744 6.37 e-05 4.66e-08 SOLVER01
MOLEFLOW
M2-1 Conv N2 0 0 0 SOLVER01
MOLEFLOW
58
4.2 RESULTS OF THE PROCESS STAGES
4.2.1 Stage 1: Air separation unit
Table 12 shows the results of the streams taking part in the ASU stage:
Table 12. ASU stream results
Units AIRFEED C1-1 HX1-1 SEP1-1 SEP1-2 SEP2-1 SEP2-2 M1-1
Vapor Vapor Vapor Liquid Liquid Vapor Liquid Mixed

Phase
ºC 13.5 290.86 -171.34 -176.64 -172.07 -172.07 -172.07 -176.47
Temperature
Pressure Bar 1 6.5 6.5 6 6.18 6.18 6.18 6
Molar kJ/kmol -343.21 7844.33 -6024.5 -10949 -11270 -6037.7 -11986 -8988
Enthalpy
Mass Flows Kg/hr 37.65 37.65 37.65 16.65 20.99 11.12 9.87 27.77
N2 Kg/hr 28.44 28.44 28.44 16.6 11.85 10.66 1.18 27.26

O2 Kg/hr 8.71 8.71 8.71 1.8e-5 8.71 0.44 8.28 0.44
AR Kg/hr 0.48 0.48 0.48 0.05 0.43 0.02 0.41 0.07
In this stage, air stream is fed to obtain nitrogen by separating it into its different
components. The M1-1 outlet has a nitrogen molar flow rate of 27.77 kg/hr.
4.2.2 Stage 2: PEM Electrolysis
The results of the different streams of the PEM electrolyzer simulation are shown
below in Table 13 and Table 14.
59
Table 13. PEM stream results 1
Units H20FEED DESAL-1 DESAL-2 M2-1 P1-1 HX3-1 R1-1 SEP3-1 SEP3-2
Liquid Liquid Mixed Mixed Liquid Liquid Mixed Vapor Mixed

Phase
ºC 16.5 16.5 16.5 35.63 35.66 80 80 80 80
Temperature
Bar 1 1 1 1 1.5 1.5 1.5 1.5 1.5
Pressure
Molar kJ/kmol -28e4 -28e4 20e4 -28e4 -28e4 -28e4 -10e4 1592 -158715
Enthalpy
Kg/hr 129.1 127.69 1.41 193.35 193.35 193.35 193.35 8.65 184.7
Mass Flows
O2 Kg/hr 0 0 0 4.9e-4 4.9e-4 4.9e-4 85.85 0 85.85
H2 Kg/hr 0 0 0 3e-6 3e-6 3e-6 10.81 8.65 2.16
H2O Kg/hr 127.69 127.69 0 139.35 139.35 139.35 96.67 0 96.67
Cl- Kg/hr 0.6 0 0.6 0 0 0 0 0 0
Na+ Kg/hr 0.5 0 0.5 0 0 0 0 0 0
SO4-- Kg/hr 0.23 0 0.23 0 0 0 0 0 0
Mg Kg/hr 0.04 0 0.04 0 0 0 0 0 0
Ca Kg/hr 0.02 0 0.02 0 0 0 0 0 0
K Kg/hr 0.02 0 0.02 0 0 0 0 0 0
60
Table 14. PEM stream results 2
Units SPLIT1-1 SPLIT1-2 SPLIT2-1 SPLIT2-2 M3-1 M4-1 F1-1 F1-2 F2-1 F2-2 SEP4- SEP4-
1 2
Vapor Vapor Mixed Mixed Mixe Mixe Vapor Liquid Vapor Liquid Vapor Mixed
Phase d d
ºC 80 80 80 80 54.65 76.16 54 54 77 77 54 54
Temperature
Bar 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Pressure
Molar kJ/kmol 1592 1592 -15e4 -15e4 -54e3 -14e4 -20e3 -28e4 -60e3 -28e4 177 -64e3
Enthalpy
Kg/hr 6.92 1.73 36.93 147.75 43.86 149.48 31.77 12.09 95.92 53.56 6.37 25.39
Mass Flows
O2 Kg/hr 0 0 17.17 68.68 17.17 68.68 17.17 1.9e-5 68.68 4.7e-4 0.34 16.83
H2 Kg/hr 6.92 1.73 0.43 1.73 7.36 3.46 7.36 6.6e-7 3.46 2.36e-6 5.88 1.47
H2O Kg/hr 0 0 19.33 77.33 19.33 77.33 7.24 12.09 23.77 53.56 0.14 7.1
Cl- Kg/hr 0 0 0 0 0 0 0 0 0 0 0 0
Na+ Kg/hr 0 0 0 0 0 0 0 0 0 0 0 0
SO4-- Kg/hr 0 0 0 0 0 0 0 0 0 0 0 0
Mg Kg/hr 0 0 0 0 0 0 0 0 0 0 0 0
Ca Kg/hr 0 0 0 0 0 0 0 0 0 0 0 0
K Kg/hr 0 0 0 0 0 0 0 0 0 0 0 0
61
4.2.3 Stage 3: Ammonia synthesis
The results of the core part of the process, the ammonia synthesis, are shown in Table 15:
Table 15. Synthesis stream results
Units M5-1 HX4-1 C2-1 M6-1 C3-1 C4-1 HX5-1 HX6-1 R2-1 HX5-2 HX7-1 F3-1 F3-2 SPLIT3-1 SPLIT3-2
Mixed Vapor Vapor Vapor Vapor Vapor Vapor Vapor Vapor Vapor Mixed Vapor Liquid Vapor Vapor
Phase
ºC -28.3 13.11 151.5 33.98 214.9 389.2 428 438 498 458.05 -26 -26 -26 -26 -26
Temperature
Bar 6 6 17 17 60 138 138 138 138 138 138 17 17 17 17
Pressure
Molar kJ/kmol -2130 -842 3197 -2.6e6 -2.7e6 8.2e6 9.4e6 9.7e6 4.8e6 3.4e6 -1.4e7 -5.7e6 -7.2e7 -5.7e6 -5.7e6
Enthalpy
Kg/hr 34.14 34.14 34.14 109.77 109.7 109.7 109.77 109.77 109.7 109.77 109.77 84.02 25.74 8.4 75.62
7 7 7
Mass Flows
Kg/hr 27.26 27.26 27.26 73.72 73.72 73.72 73.73 73.73 51.62 51.62 51.62 51.61 0.006 5.16 46.45
N2
Kg/hr 0.78 0.78 0.78 7.66 7.66 7.66 7.66 7.66 7.65 7.65 7.65 7.64 0.015 0.76 6.88
O2
Kg/hr 0.07 0.07 0.07 0.68 0.68 0.68 0.68 0.68 0.68 0.68 0.68 0.67 0.003 0.07 0.61
AR
Kg/hr 5.88 5.88 5.88 15.9 15.9 15.9 15.9 15.9 11.13 11.13 11.13 11.13 0.001 1.11 10.02
H2
Kg/hr 0 0 0 11.66 11.66 11.66 11.66 11.66 38.53 38.53 38.53 12.96 25.57 1.29 11.66
NH3
Kg/hr 0.14 1.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 3.3e-6 0.14 3e-7 3e-6
H2O
62
4.2.4 General results summary
Table 16 shows the temperature, pressure and mass flowrate to the input and the final
product streams.
Table 16. Stream results summary
Stream Units H2OFEED AIRFEED NH3 (F3-2)

Temperature C 16.5 13.5 -26
Pressure bar 1 1 17
Mass Flowrate Kg/hr 129.1 37.65 25.64
Purity 99.3%
A flow rate of 25.64 kg/h is obtained with an ammonia richness of 99.3%.The target
was 25kg/hr with a richness higher than 98%, so with the simulation this result can be
achieved.
63
64
5. EQUIPMENT SIZING AND COSTING

Once the mass balances have been solved by means of simulation, the equipment
sizing, and costs can be evaluated using different methods. In this case, manual short-
cut equipment sizing methods were used for this purpose, followed by equipment
costing estimation based on the Guthrie modular method (Biegler, et al., 1997);
(Seider, et al., 2017)
Since this is a process that works under high pressure and temperature conditions,
the cost estimation methods based on modular factor, show lower accuracy than when
applied to estimations under mild conditions. Moreover, as the ammonia converter is
a very special reactor (reactor-exchanger), commonly under proprietary information,
its cost estimation will again be very approximate within this preliminary design.
The equipment to be considered will be, on the one hand, the ASU and the PEM
electrolyze which are sized and estimated their cost specifically as a whole. On the
other hand, the individual components of the synthesis stage, which are the following:
Flash, reactor, shell and tube exchanger, heaters and cooler, three compressors, the
mixer and the splitter.
5.1 EQUIPMENT SIZING
The Guthrie modular method to estimate equipment cost is based on the Williams law,
which depend on the specific equipment capacity to estimate the Base Cost (C or BC)
using the equations showed below and the specific parameters of each unit showed
in Tables 17 and 18. Therefore, the first step would be the equipment sizing, obtaining
the specific capacity that is directly related to the cost.
65
Table 17. Base costs for pressure vessels
Table 18. Base costs for process equipment
Next subsections present an overview of short-cut calculations for equipment sizing

(Biegler, et al., 1997).
66
• Pressure vessels
Flash equipment, separators, condensers, and some single reactors are sized as
pressure vessels, being the volume of the vessel the fundamental variable for their
design. To calculate the vessel’s volume, the following expression is applied:
𝐹𝐿 ∙ 𝜏
𝑉 =2∙
𝜌𝐿
Where:
V= equipment’s volume [m3]
FL= liquid outflow [kg/hr]
𝜏= residence time [hr] (usually taken 5 minutes if we don’t have the information)
𝜌𝐿 =liquid’s density [kg/m3]
For the calculation of the dimensions of the vessel, a cylindrical vessel shape is
assumed and a ratio between the diameter of the tank and its length of L=4D, obtaining
that the diameter of the equipment are:
1
𝑉 3
𝐷=( )
𝜋
If the diameter is less than 1.2 meters, the optimum orientation for the vessel will be
vertical, thus optimizing space occupation and clamping requirements. Minimum
diameter is 1 foot.
• Heat exchangers
To size heat exchangers, the following equation is applied, from which it is possible to
obtain the required heat exchange area:
𝑄 = 𝑈 ∙ 𝐴 ∙ 𝐿𝑀𝑇𝐷
Where:
Q=amount of heat transfer [kW]
LMTD= logarithmic mean temperature difference [ºC], defined as:
[(𝑇𝑖𝑛ℎ𝑜𝑡 − 𝑇𝑜𝑢𝑡𝑐𝑜𝑙𝑑) − (𝑇𝑜𝑢𝑡ℎ𝑜𝑡 − 𝑇𝑖𝑛𝑐𝑜𝑙𝑑)]

𝐿𝑀𝑇𝐷 =
(𝑇𝑖𝑛ℎ𝑜𝑡 − 𝑇𝑜𝑢𝑡𝑐𝑜𝑙𝑑)
ln [ ]
𝑇𝑜𝑢𝑡ℎ𝑜𝑡 − 𝑇𝑖𝑛𝑐𝑜𝑙𝑑
67
U=overall heat transfer coefficient [W/m2K]
Once the exchange area is found, is necessary to calculate the number of tubes of a
given dimension that together add up to that area. Normalized tube dimensions are
taken. We will also decide the distribution of these tubes and the number of passages
through the casing.
Note that if the area needed is over 1000 m3, several heat exchangers will be used,
obtaining the total area as A=A1+A2+…+An.
• Compressors
For compressors (Fig. 26) all we need is the power needed for their use and compare
it with the market’s specifications of power and sizing, as they are very common
products used in various industries. In the present project, this power is given by the
Aspen Plus simulation, so no additional calculations are needed.
Figure 26. Industrial compressor
• Valves
Both the mixer and the splitter are preliminary designed as special valves (Fig. 27)
that, like the equipment mentioned above, they can be easily found on the market or
can be manufactured by a specialized company.
Figure 27. Industrial valve
68
5.2 SIZING RESULTS OF THE AMMONIA PLANT
• Flash unit
Table 19. Flash unit dimensions
Name Flow 𝜌 (kg/m3) 𝜏 (min) Volume Diameter Length

(kg/hr) (m3) (m) (m)
F3 109.77 86.27 5 0.21 0.41 1.63
As its diameter is less than 1.2 m, its orientation will be vertical. Vertical construction
includes shell and two heads, the skirt, base rings and lugs, and possible tray supports,
occupying a space of approximately 1 sqm and with a height of around 2.5 m.
Figure 28. Flash unit
• Reactor
Table 20. Reactor dimensions
Name Flow 𝜌 𝜏 (min) Volume Diameter Length

(kg/hr) (kg/m3) (m3) (m) (m)
R2 109.77 21.51 5 0.85 0.65 2.59
In this case, the reactor has been modelled as a pressure vessel, but as indicated
above, it is a catalytic bed reactor with heat exchange, so its sizing will depend on
reaction kinetic, mass and energy transfer. To stimate its real dimensions and
specifications, a complete study by a specialized company in this type of reactors
69
would be needed. One example of a similar reactor is the one used in the University
of Minnesota’s pilot plant (described in section 1.3.5) and shown in Figure 28.
Figure 29. University on Minnesota Ammonia Reactor Skid
Considering the design of this prototype, it is assumed that the dimensions of the
reactor can be around 5 sqm with a height of 2 m.
• Heat exchanger
Table 21. Heat exchanger dimensions
Name T hot T hot T cold T cold LMTD U A (m2) Q (kW) UA

in (ºC) out in (ºC) out (ºC) (W/m2K) (J/s·K)
(ºC) (ºC)
HX5 498 458.05 389.18 428 69.44 850 0.065 3.85 55.46
70
As mentioned above, the number of tubes of a given dimension must be calculated

using normalized tube dimensions. Both this parameter and the tubes distribution will
be designed by a specialized heat exchanger company optimizing the space to reach
the mentioned exchange area (Fig. 29). It is easy to obtain a particular heat exchanger
through the exchange area and by specifying some design parameters such as the
maximum length and the diameter of the unit. The number of tubes is related to the
exchange area by the following equations:
𝐴 𝑇𝑢𝑏𝑒𝑠=𝜋∙𝐷∙𝐿
𝑁 𝐴
𝑇𝑢𝑏𝑒𝑠=
𝐴𝑇𝑢𝑏𝑒𝑠
Figure 30. Fluitec multitube heat exchanger with mixing elements
• Heaters/Cooler
Both equipment, heaters and the cooler must be electric, in line with the policy of
avoiding direct emissions. They are defined by their operating temperatures and
pressures as well as the inlet flow and the power required which characteristics are
shown in Table 22.
Table 22. Heaters and cooler dimensions
Name Pin (bar) Pout (bar) Tin (ºC) Tout (ºC) F (kg/hr) W (kW)
HX4 6 6 -28.3 13.11 34.14 1.41
HX6 138 138 428 438 109.78 1
HX7 138 138 458 -26 109.78 5.7
71
According to the market, this equipment with the aforementioned characteristics may
have dimensions of around 1sqm and 1.5 m height.
• Compressors
This equipment is defined mainly by its power, although its size and cost also vary
depending on the working pressures and the materials used to withstand high
temperatures.
Table 23. Compressors dimensions
Name Pin (bar) Pout (bar) Tin (ºC) Tout (ºC) F (kg/hr) W (kW)
C2 6 17 13.11 151.46 34.14 4.41
C3 17 60 33.99 214.9 109.78 17
C4 60 138 214.9 389.18 109.78 17
In this case the power of the compressors C3 and C4 is very high (Table 23), reason
way the simulation is carried out by a compressors train, composed by more
compressors with less power.
As a guideline, the size of the three compressors will be around 3 sqm and 1 meter
high.
• Mixers/Splitter
The mixers will be static mixers without moving components, as the one shown in
Figure 30 and will have the following requirements shown in Table 24:
Table 24. Mixers and splitter dimensions
Name F (kg/hr) P (bar) T(ºC)
M5 34.14 6 -28.3
M6 109.78 17 33.99
SPLIT3 84.03 17 -26
72
The size will depend on the desired flow, but all these devices are about 0.5 square
meters in size.
Figure 31. Static mixer
• Air Separation Unit (ASU)

This system consists of separating the air by means of a cryogenic distillation process.
It involves cooling the air until it liquefies and then obtaining the air components to
their corresponding boiling temperature by distillation. It is a relatively simple and
tested process, and there are several products on the market that allow us to perform
this function at different capacities, depending on the volume of nitrogen to be
obtained.
For the requirements of the present project (25 kg/h and a purity of 98.5 % N2) the size
of one of this units designed for other projects are usually around 4 sqm like the one
showed in Figure 31.
Figure 32. Air Separation Unit prototype
73
• PEM Electrolyzer
This equipment consists of a stack of cells assembled under pressure that support the
high pressures generated inside and that, by means of collectors, collect gas prodcuts
in the anode (water and oxygen) and cathode (water and hydrogen) which are later
processed according to the final application of these gases (in this case to obtain
hydrogen).
Some specialized companies such as ARIEMA S.L. offer different variants depending
on the real needs of their customers: from large industrial electrolysis plants to medium
or small plants adapted to the needs of each case, as is the designed ammonia plant
in the present project.
According to the previously observed in other similar plants and projects, as well as in
small hydrogen production plants, it has been shown that the size of this equipment
for the specifications desired in the process (6.3 kg/h and a purity of 99.1 %H2) is
around 4 sqm. Figure 33 shows an example of this type of equipment.
Figure 33. Ariema PEM Electrolyzer
74
• Storage tanks
Additionally, different storage tanks must be included, each one with its own design
requirements depending on its content and the amount stored. The tanks to be placed
in the plant are the following:
o Hydrogen feed tank. Tank designed to store the hydrogen feedstock at

a pressure of 1.5 bar, coming from the PEM electrolyzer and connected
directly to the first mixer of the ammonia synthesis step.
o Nitrogen feed tank. Tank designed to store the nitrogen feedstock at a
pressure of 6 bar, coming from the Air Separation Unit and connected
directly to the first mixer of the ammonia synthesis step.
o Ammonia storage tank. This tank will store the desired product until it is
transported to bigger tanks or directly to the ships to be used as a
renewable fuel
o Purge tank. Since the purge stream contains pollutant components, it
must be stored for subsequent treatment by a company that collects and
recycles toxic waste.
Initially in this previous design, all storage tanks will be assumed to have dimensions
of 9 sqm.
5.3 REQUIRED AREA AND PLANT LAYOUT
As a summary, the estimated total area of the plant has been calculated as the sum
of the area of all its equipment obtaining a value of 60 sqm to which should add space
for pipes, pumps, valves, control and safety systems and space between equipment
in case access to them is necessary. Thus, being conservative it would be possible to
install the plant on a platform with a surface of around 300 sqm.
APPENDIX 2: AUTOCAD PLANE shows a plan drawn in the AutoCAD program and
represents what could be the floor plan layout of the designed equipment. For
convenience, when making repairs it has been decided to place all similar equipment
in the same area, so that compressors, tanks, and separators are grouped into
separated areas.
75
5.4 COST ESTIMATION OF EQUIPMENT
The cost estimation method of Guthrie is used to estimate the updated base module
cost of each equipment. This is a “Preliminary” category of cost estimation, which
could have errors higher than 50%.
The Base Cost of equipment is obtained through the Williams law expression to
pressure vessels, C = BC =Co (L/Lo) (D/Do), or C = BC =Co (S/So) to the rest of
the equipment (Biegler et al., 1997) (Biegler, et al., 1997); Values of base cost and
size as well as exponents are shown in Tables 17 and 18. Purchase costs of other
industrial processing equipment are shown in Process Design bibliography (Seider, et
al., 2017); (Douglas, 1988); (Sinnot, y otros, 2020); (Martín, 2016); (Viguri, et al.,
2017).To update cost from mid-1968 (Co and So), an Update Factor UF, to account
for inflation, is applied.
UF: (Present Cost Index / Base Cost index) = (CI actual) / (CI base), with CI 2021 = 708
708
and CI Base = 115. 𝑈𝐹 = 115 = 6.16
Updated bare (simple) module cost: BMC = UF(BC) (MPF+MF-1), where
MF is the Module Factor, affected by BC, taking into account labor, piping
instruments and accessories among others and are MF 2; MF 4; MF 6; MF 8; MF 10
from Tables 17 and 18. The MPF factor is the Materials and Pressure correction
Factors F (Fd, Fm, Fp, Fo, Ft) which are empirical factors that modified BC and
evaluate particular instances of equipment beyond a basic configuration. This
correlation factors are shown in the Tables 25-29. (Viguri, et al., 2017)
76
Table 25. Material and pressure factors for pressure vessels
Table 26. Material and pressure factors for Heat Exchangers
77
Table 27. Materials and pressure factors for Direct Fired Heaters
Table 28. Materials and pressure factors for Refrigeration
78
Table 29. Materials and pressure factors for Compressors
All the calculations were made using American units as shown in Table 17 and Table
18. The main equivalences we will need are the following: 1m=3.28ft; 1sqm=10.76sqft;
1$=0.92€.
• Pressure vessels
For this cost’s estimation, the flash unit and reactor will be considered as
pressure vessels to simplify calculations, but we must take in account that the
real price will increase when talking about the real equipment.
o Flash unit F3 (Vertical):
5.35 0.81 1.35 1.05
𝐵𝐶 = 1000 ( ) ( ) = 547.23$
4 3
MF=2
From Table 25 the MPF:

Tmin=-14.8F so the material used will be Carbon Steel. Fm=1
P=231.87psig so Fp=1.20
MPF=Fm·Fp=1.20
𝐵𝑀𝐶 = 6.16 · 547.23 · (1.2 + 2 − 1) = 7416.06$
o Reactor R2 (Vertical):
8.5 0.81 2.13 1.05
𝐵𝐶 = 1000 ( ) ( ) = 1285.23$
4 3
MF=2
Tmax=928.4F so the material used will be Carbon Steel. Fm=1
P=1986.82psig so Fp=2.5
MPF=Fm·Fp=2.5
79
𝐵𝑀𝐶 = 6.16 · 1285.23 · (2.5 + 2 − 1) = 27709.56$
• Heat exchanger HX5

3
7 0.024
𝐵𝐶 = 0.3 · 10 ( ) = 301.74$
5.5
MF=1.83
We will suppose that the design type will be Kettle reboiler so
Fd=1.35
P=1986.82psig so Fp=0.55
Shell and tube will be made of carbon steel according to their
temperature and according to the exchanger area Fm=1
MPF=Fm·(Fp+Fd)=1.9
𝐵𝑀𝐶 = 6.16 · 301.74 · (1.9 + 1.83 − 1) = 5074.3$
• Direct fired heaters

o HX4:
4.8 0.77
𝐵𝐶 = 20 · 103 ( ) = 19381.12$
5
MF=2.23
The heater is cylindrical so Fd=1
P=72.18psig so Fp=0
Radiant tube material is made of Carbon Steel so Fm=0
MPF=Fd+Fp+Fm=1
𝐵𝑀𝐶 = 6.16 · 19381 · (1 + 2.23 − 1) = 146845.96$
o HX6:
3.39 0.77
𝐵𝐶 = 20 · 103 ( ) = 14827.81$
5
MF=2.23
The heater is cylindrical so Fd=1
P=1986.83psig so Fp=0.2
Radiant tube material is made of Carbon Steel so Fm=0
MPF=Fd+Fp+Fm=1.2
𝐵𝑀𝐶 = 6.16 · 14827.81 · (1.2 + 2.23 − 1) = 130615.21$
80
• Refrigeration. HX7
3
195.25 0.7
𝐵𝐶 = 60 · 10 ( ) = 58998.91$
200
MF=1.42
Evaporator temperature is -26ºC so MPF=Ft=2.25
𝐵𝑀𝐶 = 6.16 · 58998.91 · (2.25 + 1.42 − 1) = 970366.87$
• Compressors
o C2:
15.03 0.77
𝐵𝐶 = 23 · 103 ( ) = 5345.47$
100
MF=3.11
This first compressor will be a reciprocating- single stage so
according to the Table: MPF=Fd=1.07
𝐵𝑀𝐶 = 6.16 · 5345.47 · (1.07 + 3.11 − 1) = 104711.34$
o C3:
3
59.18 0.77
𝐵𝐶 = 23 · 10 ( ) = 15356.86$
100
MF=3.11
This compressor will be a reciprocating- multistage so according
to the Table: MPF=Fd=1.29
𝐵𝑀𝐶 = 6.16 · 15356.86 · (1.29 + 3.11 − 1) = 321634.08$
o C4:
3
59.15 0.77
𝐵𝐶 = 23 · 10 ( ) = 15350.87$
100
MF=3.11
This compressor will be a reciprocating- multistage so according
to the Table: MPF=Fd=1.29
𝐵𝑀𝐶 = 6.16 · 15350.87 · (1.29 + 3.11 − 1) = 321508.62$
81
Table 30 summarize the sizing parameters related to the cost as well as the estimated
cost of the equipment list of the ammonia plant.
Table 30. Cost and size parameters summary
Type (Unit) Cost. BMC (€) Layout Area Other specifications

(sqm)
ASU 20,000 4
To obtain 27.8 kg/h of
98% N2
PEM Electrolyzer 500,000 4 To obtain 8.7 kg/h of
99.1% H2
Ammonia Synthesis to obtain 31.4 kg/h of 99.1% NH3
Flash F3 6,804.46 2.5
Reactor 25,424.35 5
Heat exchanger 4,655.82 2
HX5
Heater HX4 134,735.57 1
Heater HX6 119,843.37 1
Cooler HX7 890,340.71 1
Compressor C2 96,075.80 3
Ammonia 1,541,218.06 21.5
synthesis plant
TOTAL Plant 2,061,218.06 29.5
82
83
6. CONCLUSIONES / CONCLUSSIONS
En el presente proyecto se ha evaluado y diseñado una planta de producción de
amoniaco (a pequeña escala) de 25 kg/h y 98% de pureza a partir de materias primas
y energías renovables. Dicha planta se diseña con el objetivo de suministrar amoniaco
como combustible a buques de carga desde una plataforma flotante situada en el
puerto de Santander.
Del desarrollo de este trabajo se han obtenido las siguientes conclusiones:
1. Se ha realizado un análisis de la obtención de diferentes combustibles

alternativos y su uso en buques de carga seleccionando el amoníaco como
principal candidato bajo un enfoque de fabricación sostenible utilizando
energía y materias primas renovables.
2. Tras analizar diferentes alternativas de fabricación de amoníaco de

pequeño tamaño, se ha considerado que el proceso Haber-Bosch, con
fuentes de materias primas renovables como el agua de mar y el aire, es la
opción más adecuada en términos de recursos accesibles, eficiencia, coste,
condiciones de presión y temperatura, así como TRL.
3. Se ha realizado un diseño preliminar y una simulación de una planta de

producción de amoníaco mediante el proceso Haber-Bosch a pequeña
escala. Esta simulación se ha realizado mediante la herramienta de
modelización ASPEN Plus, obteniendo los siguientes resultados concretos:
caudal de producto de 25,64 kg/h con una riqueza de amoníaco del 99,3%.
4. El producto amoníaco se obtiene totalmente libre de emisiones

contaminantes debido a la utilización de energía renovable a través de
paneles solares y a la obtención de hidrógeno a través de la electrólisis del
agua de mar y de nitrógeno a partir de la separación del aire.
5. En base a los resultados anteriores, se realiza un estudio preliminar de la

necesidad de superficie para ubicar los equipos que componen la planta.
Siendo conservadores, sería posible instalar la planta en una plataforma
con una superficie de unos 300 𝑚2 . Por lo tanto, se comprueba que es lo
suficientemente pequeña como para ser instalada en un área reducida
como una plataforma flotante.
6. Bajo el mismo enfoque conceptual, se han aplicado a la planta de amoníaco

métodos abreviados para el dimensionamiento de los equipos principales y
métodos modulares para la estimación preliminar de costes, obteniendo un
Coste del Módulo Base de 2,1 MM€.
84
This project has evaluated and designed an ammonia production plant (small scale)
of 25 kg/h and 98% purity from raw materials and renewable energies. This plant is
designed with the aim of supplying ammonia as fuel to cargo ships from a floating
platform located in the port of Santander.
The following conclusions have been drawn from this work:
1. An analysis has been carried out on the production of different alternative fuels
and their use in cargo ships, selecting ammonia as the main candidate under a
sustainable manufacturing approach using renewable energy and raw
materials.
2. After analysing different small size ammonia manufacturing alternatives, the
Haber-Bosch process, with renewable raw material sources as seawater and
air, was considered the most suitable option in terms of accessible resources,
efficiency, cost, pressure, and temperature conditions as well as TRL.
3. A preliminary design and simulation of an ammonia production plant using the
Haber-Bosch process on a small-scale basis have been made. This simulation
has been carried out by the ASPEN Plus modelling tool, obtaining the following
specific results: product flowrate of 25.64 kg/hr with an ammonia richness of
99.3%.
4. The product ammonia is obtained totally free of polluting emissions due to the
use of renewable energy through solar panels and obtaining hydrogen through
the electrolysis of seawater and nitrogen from the separation of air.
5. Based on the previous results, a preliminary study of the area need to allocate
the equipment that make up the plant is done. Being conservative, it would be
possible to install the plant on a platform with a surface of around 300 sqm.
Therefore, it is verified that it is enough small to be installed in a reduced area
such as a floating platform.
6. Under the same conceptual approach, short-cut methods to sizing the main
equipment and modular methods to the preliminary cost estimation have been
applied to the ammonia plant, obtaining a Base Module Cost of €2.1 MM.
85
7. BIBLIOGRAPHY
ASA, 2022. Nel ASA Company. PEM Electrolyser.
https://nelhydrogen.com/product/m-series-3/.
Biegler, L., Grossmann, I., Westerberg, A., 1997. Systematic methods of chemical
process design. Ed. Prentice Hall.
Brown, T., 2018. Green ammonia pilot plants now running, in Oxford and Fukushima.
Ammonia Industry. Demand CO2-free gasoline..it exists now (NH3).
WordPress.com site.
https://co2freefuelexistsnow.wordpress.com/2018/12/02/green-ammonia-pilot-
plants-now-running-in-oxford-and-fukushima/
Chehade, G., Dincer, I., 2021. Advanced kinetic modelling and simulation of a new
small modular ammonia production unit. Chemical Engineering Science
236,116512
Douglas, J., 1988. Conceptual Design of Chemical Processes. Ed. McGraw-Hill.
Fernández, L., 2021. Statista. July 6, 2022. Global ammonia production 2010-2021.
https://www.statista.com/statistics/1065865/ammonia-production-capacity-
globally/.
Frattini, D., Cinti, G., Bidini, G., Cioffi, R., Jannelli, E. 2016. A system approach in
energy evaluation of different renewable energies sources integration in
ammonia production plants. Renewable Energy 99, 472-482
Ghavam, S., Vahdati, M., Grant Wilson, I.A., Styring, P., 2021. Sustainable Ammonia
Production. Frontiers in Energy Research. October 2021, 9:580808.
Hablutzel, M., 2019. Green Ammonia and Hydrogen at scale. Siemens AG 2019.
21pp, https://www.ammoniaenergy.org/wp-content/uploads/2021/06/1.3-
Siemens-ammonia-and-hydrogen-Martin-Hablutzel-publish.pdf
Hussain, Y., 2006. Equilibrium separation columns. pp: 108-125,

https://studylib.net/doc/8227501/equilibrium-separation-
column#google_vignette
86
IFA market intelligence. 2021. Statistical Reports-IFASTAT. World NH3 capacity by

region. International Fertilizer Association (IFA)
https://www.ifastat.org/supply/Nitrogen%20Products/Ammonia
ISO 13600. 1997. ISO 13600. ISO/TC 203 Technical energy systems. Technical
energy systems — Basic concepts. ISO/TC 203 Technical energy systems
Kai, M., Fujimura, Y., Fujimoto, T., Takagi, H., Manaka, Y., Nanba, T., 2018.
Demonstration of CO2-Free Ammonia Synthesis Using Renewable Energy-
Generated Hydrogen. NH3 Fuel Conference 2018 October 31 - November 01,
2018. Pittsburgh, PA, United States.
Lin, B., Wiesner, T., Malmali, M., 2020. Performance of a Small-Scale Haber Process:
A Techno-Economic Analysis. ACS Sustainable Chemistry and Engineering
8(41), 15517-15531
Martín, M., 2016. Industrial Chemical Process Analysis and Design. Ed. Elsevier.
Osman, O., Sgouridis, S., Sleptchenko, A. 2020. Scaling the production of renewable
ammonia: A techno-economic optimization applied in regions with high
insolation. Journal of Cleaner Production 271,121627
Kirk-Othmer, 2000. Kirk-Othmer Enciclopedia of Chemical Technology.

https://onlinelibrary.wiley.com/doi/book/10.1002/0471238961
Patil, A., Laumans, L., Vrijenhoef, H., 2014. Solar to Ammonia – via Proton’s NFuel
units. Procedia Engineering 83, 322-327.
Peng P., Chen, P., Schiappacasse, C., Zhou, N., Anderson, E., Chen, D., Liu, J.,
Cheng, Y., Hatzenbeller, R., Addy, M., Zhang, Y., Liu, Y., Ruan, R., 2018. A
review on the non-thermal plasma-assisted ammonia synthesis. Journal of
Cleaner Production 177, 597-609.
Proton Ventures. 2021. Proton Ventures: An overview of our finished projects.

https://www.protonventures.com/projects/.
Reese, M., 2020. Renewable Energy. West Central Research and Outreach Center.
University of Minnesota, USA.
https://wcroc.cfans.umn.edu/research/renewable-energy/bottling-wind.
87
Renner, J., Greenlee. L., Janik, M., Loney, C., Bakovic, S., Maheshwari, S., 2020.
Peptide Control of Electrocatalyst Surface Environment and Catalyst Structure:
A Design Platform to Enable Mechanistic Understanding and Synthesis of
Active and Selective N2 Reduction Catalysts. Univ. of Arkansas, (United
States). Technical Report of USDOE Office of Science (SC), Basic Energy
Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Sea of innovation Cantabria Cluster. 2021. Presentacion Bahía H2 Offshore. Sea of

Innovation Cantabria Cluster (SICC),
https://cantabriaseaofinnovation.es/bahia-h2/
Seider, W, Lewin, D., Seader, J., Widadgo, S., Gani, R., Ng, K.M., 2017. Product and
Process Design PrincipleS. 4th Ed. John Wiley & Sons.
Sinnot, R., Towler, G., 2020. Chemical Engineering Design. 6th Ed. Coulson &
Richardson´s Chemical Engineering Series Butterworth-Heinemann.
Soloveichik, G., 2017. Future of ammonia production: Improvement of Haber-Bosch

Process or Elecrochemical Synthesis? 2017 AIChE Annual Meeting.
Minneapolis, USA.
Sun, X., Tian, Z., Malekian, R., Li, Z., 2018. Estimation of Vessel Emissions Inventory
in Qingdao. Symmetry, 10(10), 452.
Taruishi, K., 2020. Hydrogen solutions for ocean-going vessels. International

Colloquium on Environmentally Preferred Advanced Power Generation
(ICEPAG) 2020 virtual colloquium. Irvine, California, USA..
Thyssenkrupp, 2021. Insights: Industrial Solutions. https://insights.thyssenkrupp-

industrial-solutions.com/story/small-scale-green-ammonia-plants-open-up-
new-storage-possibilities-for-wind-and-solar-power/.
U.S. Geological Survey. 2021. Mineral Commodity Summaries 2021. U.S. Geological
Survey Report. https://pubs.usgs.gov/periodicals/mcs2021/mcs2021.pdf
Valera-Medina, A, Xiao, H., Owen-Jones, M., David, W., Bowen, P., 2018. Ammonia
for power. Progress in Energy and Combustion Science,69, 63-102.
88
Verleysen, K., Coppitters, D., Parente, A., De Paepe, W., (2020). How can power-to-
ammonia be robust? Optimization of an ammonia synthesis plant powered by
a wind turbine considering operational uncertainties. Fuel, 266,117049
Viguri, J., Cifrian, E., 2017. Chemical Process Design / Diseño de Procesos Químicos.
Open Course Ware. Universidad de Cantabria.
https://ocw.unican.es/course/view.php?id=235.
Vries, N., 2019. Safe and effective application of ammonia as a marine fuel. Master
Thesis. Delft University of Technology. http://resolver.tudelft.nl/uuid:be8cbe0a-
28ec-4bd9-8ad0-648de04649b8.
Yapicioglu, A., Dincer, I., 2019. A review on clean ammonia as a potential fuel for
power generators. Renewable and Sustainable Energy Reviews, 103(C), 96-
108.
89
APPENDIX 1: SIMULATION INPUT

DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS SI MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' &
VOLUME-FLOW='cum/hr' PRESSURE=bar TEMPERATURE=C DELTA-T=C &
PDROP-PER-HT='mbar/m' PDROP=bar SHORT-LENGTH=mm
DEF-STREAMS CONVEN ALL
MODEL-OPTION
DESCRIPTION "
Air Separation Simulation with Metric Units :
C, bar, kg/hr, kmol/hr, Watt, cum/hr.
Property Method: PENG-ROB
Flow basis for input: Mole
Stream report composition: Mole flow
"
DATABANKS 'APV110 PURE28' / 'APV110 AQUEOUS' / 'APV110 SOLIDS' &
/ 'APV110 INORGANIC' / NOASPENPCD
90
PROP-SOURCES 'APV110 PURE28' / 'APV110 AQUEOUS' / &
'APV110 SOLIDS' / 'APV110 INORGANIC'
COMPONENTS
N2 N2 /
O2 O2 /
AR AR /
HYDRO-01 H2 /
AMMON-01 H3N /
H2O H2O /
CL- CL- /
NA+ NA+ /
SO4-- SO4-2 /
MAGNE-01 MG /
CALCI-01 CA /
POTAS-01 K
SOLVE
RUN-MODE MODE=SIM
FLOWSHEET
BLOCK M6 IN=SPLIT3-2 C2-1 OUT=M6-1
BLOCK C4 IN=C3-1 OUT=C4-1
BLOCK HX5 IN=R2-1 C4-1 OUT=HX5-2 HX5-1
BLOCK HX6 IN=HX5-1 OUT=HX6-1
BLOCK R2 IN=HX6-1 OUT=R2-1
91
BLOCK HX7 IN=HX5-2 OUT=HX7-1
BLOCK F3 IN=HX7-1 OUT=F3-1 F3-2
BLOCK C2 IN=HX4-1 OUT=C2-1
BLOCK M5 IN=SEP4-1 M1-1 OUT=M5-1
BLOCK SPLIT3 IN=F3-1 OUT=SPLIT3-2 SPLIT3-1
BLOCK HX4 IN=M5-1 OUT=HX4-1
BLOCK C3 IN=M6-1 OUT=C3-1
BLOCK HX1 IN=C1-1 OUT=HX1-1
BLOCK SEP1 IN=HX1-1 OUT=SEP1-1 SEP1-2
BLOCK M1 IN=SEP1-1 SEP2-1 OUT=M1-1
BLOCK C1 IN=AIRFEED OUT=C1-1
BLOCK SEP2 IN=SEP1-2 OUT=SEP2-1 SEP2-2
BLOCK SEP3 IN=R1-1 OUT=SEP3-1 SEP3-2
BLOCK SEP4 IN=F1-1 OUT=SEP4-1 SEP4-2
BLOCK F1 IN=M3-1 OUT=F1-1 F1-2
BLOCK M3 IN=SPLIT2-1 SPLIT1-1 OUT=M3-1
BLOCK F2 IN=M4-1 OUT=F2-1 F2-2
BLOCK M4 IN=SPLIT1-2 SPLIT2-2 OUT=M4-1
BLOCK SPLIT2 IN=SEP3-2 OUT=SPLIT2-2 SPLIT2-1
BLOCK SPLIT1 IN=SEP3-1 OUT=SPLIT1-2 SPLIT1-1
BLOCK R1 IN=HX3-1 OUT=R1-1
BLOCK HX3 IN=P1-1 OUT=HX3-1
BLOCK P1 IN=M2-1 OUT=P1-1
BLOCK M2 IN=F2-2 F1-2 DESAL-1 OUT=M2-1
BLOCK DESAL IN=H2OFEED OUT=DESAL-1 DESAL-2
92
PROPERTIES PENG-ROB
USER-PROPS PRKIJ 1 2 1
PROP-DATA PRKBV-1
IN-UNITS ENG SHORT-LENGTH=in
PROP-LIST PRKBV
BPVAL N2 O2 -.0119000000 0.0 0.0 -459.6700000 1340.330000
BPVAL O2 N2 -.0119000000 0.0 0.0 -459.6700000 1340.330000
BPVAL N2 AR -2.6000000E-3 0.0 0.0 -459.6700000 1340.330000
BPVAL AR N2 -2.6000000E-3 0.0 0.0 -459.6700000 1340.330000
BPVAL O2 AR .0104000000 0.0 0.0 -459.6700000 1340.330000
BPVAL AR O2 .0104000000 0.0 0.0 -459.6700000 1340.330000
BPVAL N2 HYDRO-01 .1030000000 0.0 0.0 -459.6700000 &
1340.330000
BPVAL HYDRO-01 N2 .1030000000 0.0 0.0 -459.6700000 &
1340.330000
BPVAL N2 AMMON-01 .2193000000 0.0 0.0 -459.6700000 &
1340.330000
BPVAL AMMON-01 N2 .2193000000 0.0 0.0 -459.6700000 &
1340.330000
BPVAL AR AMMON-01 -.1800000000 0.0 0.0 -459.6700000 &
1340.330000
BPVAL AMMON-01 AR -.1800000000 0.0 0.0 -459.6700000 &
1340.330000
BPVAL AMMON-01 H2O -.2589000000 0.0 0.0 -459.6700000 &
93
1340.330000
BPVAL H2O AMMON-01 -.2589000000 0.0 0.0 -459.6700000 &
1340.330000
PROP-SET GASPROPS ZMX VMX VVSTDMX CPCVMX UNITS='cum/hr' &
SUBSTREAM=MIXED PHASE=V
; "Compressibility, volume flow, heat capacity ratio"
STREAM AIRFEED
SUBSTREAM MIXED TEMP=13.5 PRES=1. MOLE-FLOW=1.3
MOLE-FRAC N2 0.78118 / O2 0.2095 / AR 0.00932
STREAM H2OFEED
SUBSTREAM MIXED TEMP=16.5 PRES=1. MOLE-FLOW=1.2
MOLE-FRAC H2O 0.964 / CL- 0.0198 / NA+ 0.011 / SO4-- &
0.00276 / MAGNE-01 0.0013 / CALCI-01 0.0004 / &
POTAS-01 0.0004
BLOCK M1 MIXER
PARAM
BLOCK M2 MIXER
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
94
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar SHORT-LENGTH=mm
PARAM
BLOCK M3 MIXER
PARAM PRES=1.5
BLOCK M4 MIXER
PARAM PRES=1.5
BLOCK M5 MIXER
PARAM PRES=6.
95
BLOCK M6 MIXER
PARAM PRES=-0.01 NPHASE=1 PHASE=V T-EST=0.
BLOCK-OPTION FREE-WATER=NO
BLOCK SPLIT1 FSPLIT
FRAC SPLIT1-1 0.8
BLOCK SPLIT2 FSPLIT
FRAC SPLIT2-2 0.8
BLOCK SPLIT3 FSPLIT
FRAC SPLIT3-1 0.1
BLOCK DESAL SEP
96
PARAM
FRAC STREAM=DESAL-1 SUBSTREAM=MIXED COMPS=H2O CL- NA+ &
SO4-- MAGNE-01 CALCI-01 POTAS-01 FRACS=1. 0. 0. 0. &
0. 0. 0.
BLOCK SEP2 SEP
PARAM
FRAC STREAM=SEP2-1 SUBSTREAM=MIXED COMPS=N2 O2 AR FRACS= &
0.9 0.05 0.05
BLOCK SEP3 SEP
PARAM
FRAC STREAM=SEP3-1 SUBSTREAM=MIXED COMPS=HYDRO-01 FRACS= &
0.8
BLOCK SEP4 SEP
97
PARAM
FRAC STREAM=SEP4-1 SUBSTREAM=MIXED COMPS=O2 HYDRO-01 H2O &
FRACS=0.02 0.8 0.02
BLOCK HX1 HEATER
PARAM PRES=6.5 VFRAC=1. DPPARMOPT=NO
BLOCK HX3 HEATER
PARAM TEMP=80. PRES=1.5 DPPARMOPT=NO
BLOCK HX4 HEATER
PARAM PRES=-0.01 VFRAC=1. DPPARMOPT=NO
BLOCK HX6 HEATER
PARAM TEMP=438. PRES=-0.01 DPPARMOPT=NO
BLOCK HX7 HEATER
PARAM TEMP=-26. PRES=-0.01 DPPARMOPT=NO
98
BLOCK F1 FLASH2
PARAM TEMP=54. PRES=1.5
BLOCK F2 FLASH2
BLOCK F3 FLASH2
PARAM TEMP=-26. PRES=17.
BLOCK HX5 HEATX
PARAM T-COLD=428. CALC-TYPE=DESIGN TYPE=COUNTERCURRE &
PRES-HOT=0. U-OPTION=PHASE F-OPTION=CONSTANT &
CALC-METHOD=SHORTCUT
99
FEEDS HOT=R2-1 COLD=C4-1
OUTLETS-HOT HX5-2
OUTLETS-COLD HX5-1
HOT-SIDE DP-OPTION=CONSTANT DPPARMOPT=NO
COLD-SIDE DP-OPTION=CONSTANT DPPARMOPT=NO
TQ-PARAM CURVE=YES
BLOCK SEP1 RADFRAC
PARAM NSTAGE=60 ALGORITHM=STANDARD MAXOL=25 DAMPING=NONE
COL-CONFIG CONDENSER=TOTAL REBOILER=NONE
FEEDS HX1-1 60 ON-STAGE
PRODUCTS SEP1-2 60 L / SEP1-1 1 L
P-SPEC 1 6.
COL-SPECS D:F=0.4 DP-STAGE=0.003
SPEC 1 MOLE-FRAC 1E-006 COMPS=O2 STREAMS=SEP1-1 &
SPEC-DESCRIP="Mole purity, 1E-006, PRODUCT"
VARY 1 D:F 0.3 0.7
BLOCK R1 RSTOIC
100
STOIC 2 MIXED H2O -2. / HYDRO-01 2. / O2 1.
CONV 2 MIXED H2O 0.5
BLOCK R2 RSTOIC
PARAM TEMP=498. PRES=138.
STOIC 1 MIXED HYDRO-01 -3. / N2 -1. / AMMON-01 2.
CONV 1 MIXED HYDRO-01 0.3
BLOCK P1 PUMP
PARAM PRES=1.5
BLOCK C1 COMPR
PARAM TYPE=ISENTROPIC PRES=6.5 SB-MAXIT=30 SB-TOL=0.0001
BLOCK C2 COMPR
PARAM TYPE=ISENTROPIC PRES=17. NPHASE=2 SB-MAXIT=30 &
SB-TOL=0.0001 MAXIT=100
BLOCK C3 COMPR
101
SB-TOL=0.0001
BLOCK C4 COMPR
SB-TOL=0.0001
DESIGN-SPEC DS-PURGE
DEFINE AR MOLE-FRAC STREAM=M6-1 SUBSTREAM=MIXED &
COMPONENT=AR
DEFINE OX MOLE-FRAC STREAM=M6-1 SUBSTREAM=MIXED &
COMPONENT=O2
DEFINE TOT STREAM-VAR STREAM=M6-1 SUBSTREAM=MIXED &
VARIABLE=MOLE-FLOW UOM="kmol/hr"
SPEC "(AR+OX)/TOT" TO "0"
TOL-SPEC "0.12"
VARY BLOCK-VAR BLOCK=SPLIT3 SENTENCE=FRAC VARIABLE=FRAC &
ID1=SPLIT3-1
LIMITS "0" "1"
DESIGN-SPEC DS-WATER
DEFINE H20 MOLE-FRAC STREAM=M6-1 SUBSTREAM=MIXED &
COMPONENT=HYDRO-01
DEFINE N20 MOLE-FRAC STREAM=M6-1 SUBSTREAM=MIXED &
102
COMPONENT=N2
SPEC "H20/N20" TO "3.0"
TOL-SPEC "0.01"
VARY MOLE-FLOW STREAM=H2OFEED SUBSTREAM=MIXED

COMPONENT=H2O &
UOM="kmol/hr"
LIMITS "0" "30" STEP-SIZE=0.1
EO-CONV-OPTI
CONV-OPTIONS
WEGSTEIN MAXIT=300
STREAM-REPOR MOLEFLOW MOLEFRAC PROPERTIES=GASPROPS
PROPERTY-REP PCES
PROP-TABLE PTENV-1 PTENVELOPE
PROPERTIES PENG-ROB FREE-WATER=STEAM-TA SOLU-WATER=3 &
TRUE-COMPS=YES
STREAM AIRFEED
ENVELOPES VFRAC=1
PARAM MAXPT=50
TABULATE
103
104
APPENDIX 2: AUTOCAD PLANE
105
106

ASPEN PLUS Simulation of Green Ammonia

Cargado por

Copyright:

Formatos disponibles

ASPEN PLUS Simulation of Green Ammonia

Cargado por

Información del documento

Derechos de autor

Formatos disponibles

Compartir este documento

Compartir o incrustar documentos

Opciones para compartir

¿Le pareció útil este documento?

¿Este contenido es inapropiado?

Copyright:

Formatos disponibles

ASPEN PLUS Simulation of Green Ammonia

Cargado por

Copyright:

Formatos disponibles

ESCUELA TÉCNICA SUPERIOR DE INGENIEROS

Trabajo Fin de Grado

SMALL-SCALE GREEN AMMONIA

(Planta de producción de amoniaco

Para acceder al Título de

Autor: Juan Lainz Arrarte

Título: Planta de producción de amoniaco sostenible a pequeña escala: diseño

Autor: Juan Lainz Arrarte

Directores: Berta Galán Corta y Javier R. Viguri Fuente

Palabras clave: Amoniaco, pequeña escala, Aspen Plus, renovable, simulación,

Resumen: El presente proyecto tiene como objetivo el diseño preliminar de una

Inicialmente se realiza un análisis de alternativas comparando, principalmente, el uso

El análisis del estado del arte de plantas de producción de amoniaco a pequeña

Mediante simulación en ASPEN PLUS se diseña una planta de producción de 25.64

Author: Juan Lainz Arrarte

Supervisor: Berta Galán Corta and Javier R. Viguri Fuente

Keywords: Ammonia, small-scale, ASPEN Plus, renewable, simulation, Haber

LIST OF TABLES ....................................................................................................... 7

1.1 CONTEXT ....................................................................................................... 10

1.1.1 Renewable fuels....................................................................................... 10

1.1.2 Marine transport fuels .............................................................................. 12

1.1.3 Floating energy production systems ......................................................... 14

1.1.4 Bahia H2 offshore project ......................................................................... 14

1.2 AMMONIA PRODUCTION PROCESS ........................................................... 17

1.2.1 Ammonia production routes ..................................................................... 20

1.2.2 Conventional Haber Bosch process ......................................................... 21

1.2.3 Sustainable ammonia by Haber Bosch .................................................... 22

1.2.4 Alternatives to the Haber Bosch process ................................................. 24

1.2.5 Discussion of the selected technology ..................................................... 25

1.3. SMALL SCALE HABER BOSCH PLANTS AND PROJECTS USING

1.3.1 Proton ventures ........................................................................................ 28

1.3.3 JGC Holdings ........................................................................................... 32

1.3.4 Siemens ................................................................................................... 34

1.3.5 University of Minnesota ............................................................................ 35

1.4 OBJECTIVE .................................................................................................... 37

2 DESIGN SPECIFICATIONS .................................................................................. 39

2.1 RAW MATERIALS AND PRODUCTS ............................................................. 39

2.2 AIR SEPARATION UNIT................................................................................. 41

2.3 DESALINIZATION AND WATER ELECTROLYSIS ........................................ 43

2.4 AMMONIA SYNTHESIS.................................................................................. 45

3 ASPEN PLUS SIMULATION ................................................................................. 48

3.1 INPUT DATA................................................................................................... 49

3.2 FEED AND PRODUCT STREAMS ................................................................. 50

3.3 PROCESS THERMODYNAMICS ................................................................... 51

3.4.1 Air separation unit .................................................................................... 51

3.4.2 Desalination unit and PEM electrolysis .................................................... 52

3.4.3 Ammonia synthesis unit ........................................................................... 53

3.5 DESIGN SPECIFICATIONS ........................................................................... 54

3.6 PROCESS FLOW DIAGRAM OF THE COMPLETE PROCESS .................... 56

4 RESULTS OBTAINED FROM ASPEN SIMULATION ........................................... 58

4.1 PROCESS CONVERGENCE ......................................................................... 58

4.2 RESULTS OF THE PROCESS STAGES ....................................................... 59

4.2.1 Stage 1: Air separation unit ...................................................................... 59

4.2.2 Stage 2: PEM Electrolysis ........................................................................ 59

4.2.3 Stage 3: Ammonia synthesis .................................................................... 62

4.2.4 General results summary ......................................................................... 63

5. EQUIPMENT SIZING AND COSTING ................................................................. 65

5.1 EQUIPMENT SIZING ...................................................................................... 65

5.2 SIZING RESULTS OF THE AMMONIA PLANT .............................................. 69

5.3 REQUIRED AREA AND PLANT LAYOUT ...................................................... 75