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Process Integration, Energy and Exergy Analyses

of a Novel Integrated System for Cogeneration of
Liquid Ammonia and Power using Liquefied
Natural Gas Regasification, CO2 Capture Unit and
Solar Dish Collectors

Mostafa Moradi, Bahram Ghorbani, Armin

Ebrahimi, Masoud Ziabasharhagh

PII: S2213-3437(21)01351-8
DOI: https://doi.org/10.1016/j.jece.2021.106374
Reference: JECE106374

To appear in: Journal of Environmental Chemical Engineering

Received date: 28 June 2021
Revised date: 8 September 2021
Accepted date: 11 September 2021
Please cite this article as: Mostafa Moradi, Bahram Ghorbani, Armin Ebrahimi
and Masoud Ziabasharhagh, Process Integration, Energy and Exergy Analyses of
a Novel Integrated System for Cogeneration of Liquid Ammonia and Power
using Liquefied Natural Gas Regasification, CO2 Capture Unit and Solar Dish
Collectors, Journal of Environmental Chemical Engineering, (2021)
doi:https://doi.org/10.1016/j.jece.2021.106374
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Process integration, energy and exergy analyses of a novel integrated system for
cogeneration of liquid ammonia and power using liquefied natural gas
regasification, CO2 capture unit and solar dish collectors
Mostafa Moradia , Bahram Ghorbania, Armin Ebrahimib, Masoud Ziabasharhaghb
a
Faculty of Engineering Modern Technologies, Amol University of Special Modern Technologies, Amol,
Iran
b
Faculty of Mechanical Engineering, K. N. Toosi University of Technology, Tehran, Iran

One of the most common methods of ammonia production used in the last hundred years is the

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Haber-Bosch process. The basis of this process is hydrogen and nitrogen, which must be

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supplied in different ways.

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Abstract
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In the present study, a novel integrated structure for tri-generation of liquid ammonia, carbon
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dioxide, and power through the Haber-Bosch process, amine-based carbon dioxide capture cycle,

and absorption-compression refrigeration cycle is developed. The required nitrogen of this

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process is supplied by the cryogenic air separation system with the help of the liquefied natural

gas regasification process and the required hydrogen is supplied through a steam methane
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reforming process with the help of an amine-based CO2 capture cycle. The needed cooling by the

Haber-Bosch process at -50 °C is also provided by the absorption-compression refrigeration

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cycle. The required power of the whole system is generated through the organic Rankine cycle.

Solar energy heat source and power plant exhaust flue gas are used to supply heat to different

parts of the integrated system. Simultaneous design of units and integration of processes reduces

the number of required equipment and reduces energy consumption, thus increases the system

efficiency. This hybrid structure produces 3.042 kg/s ammonia as the main product, 13300 kW

power, 2.762 kg/s CO2, 3.929 kg/s pure oxygen, and 11.31 kg/s hot water as byproducts. The

total energy and exergy efficiencies of the combined structure are 46.95% and 57.36%,

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respectively. Exergy investigation of the combined system illustrates that the highest rate of

exergy destruction includes heat exchangers (46.18%), collectors (18.45%), and towers (14.97%)

of the total exergy destruction. Sensitivity analysis is performed on the sensitive parameters of

the system and its results are reported.

Keywords:

Liquefied Ammonia; Air separation unit; CO2 capture unit; Solar dish collectors; Absorption-

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compression refrigeration cycle

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1. Introduction

Ammonia is a natural substance that is environmentally friendly. It has excellent thermodynamic

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and thermophysical properties, but has moderate toxicity and is almost flammable. For this
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reason, the necessary precautions must be taken to use it. Ammonia is also a chemical with an
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alkaline property, colorless, lighter than air with a pungent odor, which is widely used in industry

and agriculture. Ammonia is the second most-produced chemical in the world, which can be
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obtained from fossil fuels, biomass, or other renewable sources. Its main advantages are the
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refrigeration effect, lower cost per unit of stored energy, and high bulk energy density, which is
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comparable to gasoline in this regard [1]. More than 200 million tons of ammonia are produced

annually worldwide. About 80% of the produced ammonia worldwide is used to make nitrogen-
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based fertilizers. Global ammonia capacity is projected to increase from 205 million tons in 2010

to about 239 million tons by 2020, representing an increase in production to more than 33

million tons, equivalent to a 16% increase over a decade [2]. Also, because ammonia is a good

source of hydrogen, it has the potential to play an important role in the future hydrogen economy

[3]. Although a large percentage of global ammonia production is currently used in fertilizer

production, it can be used as fuel for vehicles and space heating. Ammonia is an excellent energy

storage medium that has the necessary infrastructure for its transportation and distribution in

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many countries [4]. It is a carbon-free substance and also has a high-octane content; there is now

a greater tendency to use ammonia as a fuel. Zamfirescu et al. [5] analyzed the potential benefits

and technical advantages of using ammonia as a sustainable fuel in vehicles. Also, the cooling

effect of ammonia is a valuable side advantage that shrinks the engine cooling system and

provides air conditioning. Ammonia is a source of promising energy storage that can meet

hydrogen-related challenges. Siddiqui et al. [6] investigated a new ammonia synthesis and solar-

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based fuel cell system. They also used thermodynamic and exergy tools to analyze the system.

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The system uses the extra power generated by a solar photovoltaic system to synthesize

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ammonia, and besides, in the absence of solar radiation, a direct ammonia fuel cell is used to

generate electricity. The total exergy efficiency was in the range of 16.44- 16.67%, while the
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total energy efficiency during the year varies between 15.68 and 15.83%. Ammonia is also
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considered as an energy storage source and hydrogen source because the hydrogen content in

liquid ammonia is 17.6% by weight, which is about 12.5% by weight in methanol [7]. Patil et al.
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[8] proposed a new solution based on ammonia energy buffer to solve the problems caused by
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solar energy rotation and uncertain energy demand and balancing solar energy production. A
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completely environmentally friendly system that is no carbon emissions upstream or

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downstream. If necessary, this ammonia was converted to power through ammonia generators.

Also, excess ammonia can be used directly as chemical fertilizers. Lipman et al. [9] studied the

use of ammonia as a fuel for transport vehicles in an internal combustion engine and concluded

that this fuel has the potential to play an important role in the future hydrogen economy because

ammonia is easily broken down and used to produce hydrogen in fuel cells. Rouwenhorst et al.

[10] compared and evaluated alternatives to hydrogen production, nitrogen production, ammonia

synthesis, ammonia separation, ammonia storage, and ammonia combustion. Also, a conceptual

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process design, based on temperature and pressure optimization on existing and proposed

technologies, is presented for the islanded ammonia energy system. The use of ammonia as fuel

in fuel cells has the advantages of low pollutant emissions and high efficiency. Ammonia is a

carbon-free fuel that emits no carbon dioxide (CO2) during combustion, thus reduces the risk of

NOx emissions in fuel cell applications because no direct mixing between oxygen and ammonia

occurs [11]. Yapicioglu et al. [12] discussed the use of ammonia as a fuel in industrial

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generators. Also, different methods of ammonia production are studied in terms of potential

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benefits and challenges from economic, social, and environmental perspectives. In addition,

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ammonia synthesis methods were compared and evaluated based on technical, economic, and

environmental performance criteria. Anaerobic ammonium oxidation (anammox) can be turned

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into an economical and environmentally friendly technology with a high potential for bioenergy
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recovery. Therefore, Arora et al. [13] thoroughly investigated the inhibition mechanism,

threshold concentration and control strategies to ensure the proper functioning of the anammox
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system. Finally, the main bottlenecks and innovative perspectives for achieving the global
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application of anammox-based technologies were presented.

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For the past hundred years, the Haber-Bosch process has been used to convert nitrogen in the
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atmosphere into ammonia. Although there are many risks to the Haber-Bosch process due to

high temperatures and pressures, the very low cost of iron catalysts makes the Haber-Bosch

process more cost-effective than other processes. Therefore, the usual route of ammonia

production is by the Haber-Bosch process [14]. As a result, NH3 can be produced through the

synthesis of nitrogen and hydrogen in the Haber-Bosch process. The basis of this process is

hydrogen and nitrogen, which must be supplied in different ways [15]. To supply the required

nitrogen in the Haber-Bosch process, it is possible to do so by separating the air, because the

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highest percentage of the constituent elements of the air in the atmosphere are nitrogen and

oxygen. Other elements such as helium, krypton, xenon, argon, and some hydrocarbons are also

reported. Since air is a rich source of nitrogen and oxygen gases, so it can be used to produce

high purity of these compounds for industrial purposes. Inlet pressure and boiling points are the

main and influential factors in the nitrogen separation process. Therefore, nitrogen can be

separated from the airflow by reducing its temperature to the desired boiling point [16]. Giovanni

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et al. [17] designed an innovative system for the production of green ammonia using renewable

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energy sources. In the study, an improved Haber Bosch Reactor was used to produce hydrogen,

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and a solid oxide electrolyzer (SOE) was used to synthesize ammonia. An air separator has also

been introduced to provide pure nitrogen. SOE and HBR both operate at 650 °C. Morgan et al.
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[18] proposed an integrated structure for the production of carbon-free ammonia fuel using wind
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energy on Monhegan Island. In the proposed system, the climate is used directly by traditional

air separation units (ASUs), alkaline electrolyzers, mechanical vapor compression desalination,
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and a Haber-Bosch synthesis ring. Osman et al. [19] simulated an integrated power plant
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including desalination, electrolysis, air separation, refrigeration, and storage in ASPEN PLUS
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software and technically and economically optimized the production of renewable ammonia as a
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promising carrier option. The specific energy consumption and electrical process of this

integrated system were 10.43 kWh/kg-NH3 and 37.4%, respectively.

On the other hand, the required hydrogen for the Haber-Bosch process must be provided. The

most important methods of hydrogen production are water electrolysis, coal decomposition, and

hydrocarbon conversion. Of course, on an industrial scale, the conversion of hydrocarbons to

hydrogen is possible with three methods, which are steam reforming, partial oxidation, and auto

thermal reforming. However, in the past, the main source of hydrogen was coal gasification, but

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the fall in oil prices pushed hydrogen production towards natural gas vapor reform [20]. The

proper efficiency and cheapness feed of this process make it more economical than other

hydrogen production methods [21]. About half of the world's hydrogen is produced by methane

reforming in the presence of water vapor so that in 2007, about 80% of total ammonia synthesis

used natural gas as the main material and the remaining 20% from coal [22]. Ghorbani et al. [23]

developed a new integrated system including air separation units, Fischer-Tropsch synthesis unit,

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steam power plant, and Rankine power generation cycle for producing power and liquid fuels

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using liquefied natural gas regasification and solar collectors. The liquefied natural gas (LNG)

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regasification and solar collectors were used to provide cooling and heating of the integrated

structure, respectively. The integrated system and related processes were simulated and designed
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using HYSYS and TRNSYS software and MATLAB programming. The results showed that the
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integrated structure produced 200.6 MW of power and 78.88 kgmol/h of liquid fuel. In addition,

total thermal efficiency and total exergy efficiency were 42.36% and 64.72%, respectively.
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Andersson et al. [24] conducted a technical and economic evaluation of ammonia production
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through integrated biomass gasification in a pulp mill. In this method, the produced hydrogen
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was provided through biomass gas supply and as a result, ammonia was produced by using the
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synthesis of nitrogen and hydrogen in the Haber-Bosch process. Biomass degassing and

subsequent NH3 production were modeled using ASPEN PLUS software. Emelin et al. [25]

developed the process of bio-ammonia production from syngas resulting from the gasification of

the African Rachis palm and performed its technical and economic evaluation. According to the

results, 1,630,000 metric tons of Rachis palm per year produced a single gas with 99% hydrogen

concentration, which annually generates 35755 million tons of bio ammonia. Hosseini et al. [26]

introduced and developed an integrated system consisting of a molten carbonate fuel cell

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(MCFC) with steam methane reforming (SMR), methanol synthesis process (MSP) with

distillation process, and combined heat and power plant (CHP) including gas turbine, Rankine

cycle (RC), the organic Rankine cycle (ORC) and the Regional Heating Line (DH). In this

system, the SMR unit at 800 kPa and 600 °C was used to generate the required artificial gas by

MCFC and MSP. The simulation was performed by ASPEN HYSYS software. This structure

produced 110544 kW of net power, 271.7 kgmole/h of pure methanol (99.9%), and 65398.7

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kgmole/h of hot water at 80 °C.

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Nowadays, fossil fuels provide about 80% of the world's primary energy sources and generate

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more than 60% of the world's electricity. However, the combustion of fossil fuels leads to the
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emission of air pollutants and the release of large amounts of CO2 into the atmosphere. From a

global environmental perspective, CO2 uptake is critical to reducing the threat of global
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warming. On the other hand, to purify the output hydrogen from the SMR, carbon dioxide must

be adsorbed. The best-known way to capture CO2 is by removing CO2 by adsorbing it to amino
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solutions. Amines are weak alkali compounds that react with CO2 and are easily broken down
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under gentle heat and amine recovery occurs [27, 28]. As regards most of the world's energy is
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still supplied through fossil fuels, the need for sustainable development requires the application
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of effective methods to reduce the environmental impact of fossil fuel use. The CO2 capture and

storage technology is currently one of the best ways to directly reduce carbon dioxide emissions

into the atmosphere [29]. However, carbon dioxide adsorption systems based on the combustion

process are generally divided into three categories: pre-combustion adsorption, post-combustion

adsorption, and oxygen combustion [30, 31]. Liu et al. [32] investigated the aggregation effect

of carbon dioxide absorption and compression system and compression on a natural gas

combined cycle power plant. They reduced the efficiency drop due to systems aggregation to

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1.31% by using a 38% ratio of exhaust gas recirculation system as well as the use of shock wave

ultrasonic compressors and recovering waste heat from the compressors' intermediate coolers.

Daniel et al. [33] evaluated the efficiency, cost of exergy, and cost allocation of CO2 emissions

for an integrated syngas and ammonia production plant. This evaluation was performed from

steam methane modification (SMR), CO2 capture and compression units, as well as ammonia

synthesis and purge gas treatment. The total exergy efficiency of the ammonia project is

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estimated at 66.36% by recovering the fuel and hydrogen-rich gases in the purge gas treatment

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process. Biliyok et al. [34] evaluated the integration of a 440 MW natural gas combined cycle

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with a carbon dioxide capture and compression system. The results showed that by using the

exhaust gas recirculation system with a ratio of 40%, it has recovered 10 MW of power plant
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waste. The use of CO2 as sustainable energy carriers leads to near-zero emissions levels. By
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performing the hydrogenation process, CO2 was converted to methanol, which has many

environmental benefits. Bayomie et al. [35] investigated different process configurations for
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hydrogenation of CO2 to methanol from industrial flue gases. This process was modeled with
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ASPEN HYSYS simulation software. In addition, sensitivity analysis was performed to evaluate
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the effect of different parameters on reactions and total efficiency. Farajollahi et al. [36] used the
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integration of a thermal power plant with carbon dioxide absorption and compression systems to

increase the efficiency of the power plant and also reduced its efficiency loss from 9.29% to

5.1% by applying organic Rankine cycle to recover waste heat sources. Absorption-compression

refrigeration systems were widely applied to use waste heat in industrial processes and produce

cooling and liquefaction. Ghorbani et al. [37] developed an innovative structure including

cryogenic/amine scrubbing biogas upgrading process for cogeneration of CO2 and methane

mixed fluid cascade liquefaction cycle. Thes specific power consumption was 0.476 kWh/kg

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LNG. The thermal energy and exergy efficiencies were 73.11% and 72.58%, respectively. The

return period and prime cost of the product are 3.675 years and 0.2399 US$/kg LNG,

respectively. Han et al. [38] proposed a hybrid absorption-compression refrigeration system

based on the medium temperature waste heat, the fluid of which is water and ammonia. The

novel integrated structure showed proper performance due to the cascading use of waste heat of

subsystems. So that with the same entering waste heat, the proposed system produced 46.7%

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more cooling than conventional water and ammonia absorption refrigeration. Chen et al. [39]

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proposed a low-temperature novel heat-driven absorption-compression refrigeration system,

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including a new water/ammonia power cycle, an ammonia/water absorption refrigeration cycle,

and a CO2 compression refrigeration unit. In recent years, the development of technologies for
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waste heat recovery has accelerated. Exhaust gases are one of the largest sources of waste heat in
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industries. The energy of this type of wasted heat can be recovered and used in three different

ways: 1- energy recovery for electricity generation, 2- heating of buildings and processes through
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heat pumps or heat exchangers, 3- cooling of buildings and refrigeration of processes through
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thermal-driven systems [40]. As a result, the existing flue gas of power plants can be used for
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temperature applications. For this purpose, Zhou et al. [41] studied the launching of the organic
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Rankine cycle using waste heat recovery from flue gas at low temperatures. The results

illustrated that the maximum output power of the expander is 645 W. Also, the cycle and heat

recovery efficiencies were 8.5% and 22%, respectively.

So far, several studies have been performed to produce liquid ammonia using the natural gas

reforming method and the air separation unit. External energy sources are needed to supply

power, heat, and refrigeration to the integrated structure of liquid ammonia production, which

leads to an increase in equipment. The objective of the studies reported in the literature is the

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simultaneous optimization of the required thermal energy consumption, power consumption,

economic price of the hybrid system, and environmental problems. Based on a recent literature

review, so far no comprehensive method has been developed for the production of liquid

ammonia using LNG regasification and renewable energy. This research has developed a new

method for producing liquid ammonia in order to store it for a long time as a clean and portable

fuel to distant places with the methods of thermal integration between processes and pinch

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analysis in heat exchangers. This paper presents a new integrated cycle of ammonia production

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using the Haber-Bosch process, air separation unit, LNG regasification, reforming of natural gas

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obtained from LNG regasification. A carbon dioxide capture (CO2 capture) unit was also

installed to increase the degree of hydrogen purity. Also, the required cooling for ammonia
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liquefaction is provided by the absorption- compression refrigeration cycle, which receives its
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desired heat from the flue gas leaving the power plants.

2. Process description
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The steam methane reforming process and air separation unit are used to supply hydrogen and
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nitrogen in the ammonia production process, respectively. High-temperature hot utility, power,
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and cooling are used in the steam methane reforming process, air separation unit, and ammonia
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liquefaction cycle, respectively. Fig. 1 shows the process flow diagram (BFD) of the novel

integrated structure for the production and liquefaction of ammonia using the Haber-Bosch

process, amine-based carbon dioxide capture cycle, steam methane reforming process, air

separation unit, and absorption-compression refrigeration cycle.

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 O₂ Liquefied Flue
Power Power
NH₃ gas

-50 C, 100 kPa,

26.44 C, 830 kPa, 3.042 kg/s 16417 kW 128100 kW
3.929 kg/s 5302.5 kW 13860 kW
25 C, 101.3 kPa,
20.69 kg/s Pure N₂,
32.37 C, 100 kPa, Absorption Compression
Air 3.017 kg/s 50 C, 100 kPa,
ASU & LNG Haber-Bosch Refrigeration Cycle
Regasification 36.87 kg/s
Process coupled with ORC
Unit
LNG
-165.8 C, 101.4 kPa,
1.037 kg/s 20.34 C, 101 kPa,

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13.7 kg/s

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CH₄ ,
15 C, 250 kPa, Pure H₂, Heat Flow
1.037 kg/s 32.37 C, 100 kPa,
N₂
0.5066 kg/s

2.9 kW Cold Flow

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Steam Methane
Power Reforming CO₂
Power Unit 24.92 C, 112 kPa, Capture Unit
60631 kW
3.371 kg/s Power

2250 kW 12140 kW
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21 C, 180 kPa, 61.4 kW
2.761 kg/s Mass Flow
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10910 kW Power
Organic Rankine Solar Dish
Cycle Collector CO₂
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Fig. 1. Block flow diagram of the developed integrated structure.

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The air separation unit consumes the amount of 20.69 kg/s air, 1.037 kg/s LNG, 5302.5 kW

power, and 917 kW LNG regasification cooling and produces 3.929 kg/s, 13.7 kg/s oxygen, and
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nitrogen, respectively. Also, 3.017 kg/s of nitrogen enters the cycle for the Haber-Bosch process

and ammonia production. On the other hand, to supply the required pure hydrogen, 1.037 kg/s of

methane obtained from LNG regasification enters the steam methane reforming unit. To purify

hydrogen, a CO2 capture plant is used to separate 2.761 kg/s of carbon dioxide and enter 0.5066

kg/s of pure hydrogen into the desired cycle to perform the Haber-Bosch process. Also, for

liquefaction of ammonia from the Haber-Bosch process, the absorption-compression

refrigeration cycle coupled with ORC is used, which itself, by consuming 43650 kW of heat

11
from flue gas power plants, produces 128100 kW of power. In addition, the ACRC cycle

provides 13860 kW of required cooling for the Haber-Bosch process. Solar dish collectors were

used to supplying the required heat to the SMR process and conversion reactor (12140 kW) and

also used to increase the efficiency of the integrated structure, by the first ORC power generation

cycle that produces 2250 kW of power. Finally, 3.042 kg/s of liquid ammonia is introduced as

the final product of the integrated structure. In the following, the subsystems are described in

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detail as shown in Fig. 2.

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 A24 T1 V2 Compressor
(Water) A10 A13
P2 A23 A17
A25 MHX2 A12
T2
(Oxygen) A16
A27 MHX1 A11
COM1 A9 V1 Component
A15
A1 A2 A3 A4 A5 A6
A8
Splitter
A7 A14
(Air)
HX1 COM2 HX2 HX3 A21 A20 A19
A22 A18
A29
P3 Conversion
Air Separation Unit A31 C
A26 COM3
A32 A28 Reactor
& LNG Regasification Unit
(Nitrogen) A33 P1 (LNG)

D3 H1 C15 C18 C19 (CO₂) Condenser

H7 D2
HX12 HX14 X1 C13 C11
H4 H2 J2 J3 C7
H11 T3 C9 Flash Drum
J1 Tur2 C14 C17 C20
(NH3) R2 C HX11
HX10

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H8
J10 C10 C8 C12
H3 J11 J4 Mixer

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C21 C16
P7 C6
C

H10

Tur3
R3
C1 Multi Heat
J8
H9 Exchanger
J9 J5 C2 C3
Haber-Bosch Process
H5 & Organic Rankine Cycle J6 HX9
H6 P5 T4
Unit P8 HX13 Pump
J7

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A30 C5
CO₂ Capture Unit
V4 M15
S15
C4
Plug Flow
M24
Reactor
P6
V5 M23 M26
M31 M30
HX19 HX20 HX21 Reboiler
HX18 V3

M32
COM4
M33
HX23

M28
M25

M22

M29
M14

M13
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V6
M27
P10

M16
S14

D1

S13
S17
S12
HX8
Steam Methane Reforming Unit

S16

S8
Shell and
tube Heat
Exchanger

Tur1 M21 S11 Turbine

HX5
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(Flue gas)

M17 S5
S6 S7
M1

M12 HX4
M7 R1
M6 S10 S18 S4
Tower
HX16 HX24 M10 S2 S3
M20 M18
M2 P4 HX6 HX7
M8
T5 HX22
HX15 S1 S19
S9 Valve
M3 (Water)
M11
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HX17
M9 M19
Solar dish collectors
M5 M4
Absorption Compression Refrigeration Cycle
P9 coupled with ORC Unit
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Fig. 2. Process flow diagram of the developed integrated structure.

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2.1. Air separation cycle & LNG regasification unit

In this section, airflow (streamA1) enters the COM1 compressor in atmospheric conditions with
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a mass flow of 20.89 kg/s and its temperature and pressure reach 143.89 ºC and 268 kPa (stream

A2). The stream reaches the temperature of 30 ºC after passing through the HX1 heat exchanger

and enters the COM2 compressor for recompression, and as a result, stream A4 leaves with a

temperature and pressure of 154.17 ºC and 669 kPa. At this stage, the stream drops to 40.3 ºC

(stream A6) and enters TEE during the passage of two of the HX2 and HX3 heat exchangers.

The output streams from TEE (streams A7 and A8) with a mass flow of 14.7 kg/s and 6.62 kg/s,

enter the MHX1 multi heat exchanger and by losing some of its heat, reaches -164.1 ºC (stream

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A9) and -173 ºC (stream A10), respectively, and enters the T1 distillation column. From below,

the stream A14 with a purity of 35.02 mol% oxygen and a flow rate of 12.22 kg/s is discharged

into the MHX2 multi heat exchanger and by losing a part of its heat in this converter, is cooled to

a temperature of -180.6 ºC (stream A15) and expands by passing through the V1 valve to a

pressure of 106 kPa (stream A16) and finally enters the T2 distillation column. On the other

hand, stream A11 with a purity of 97.79 mol% nitrogen and a mass flow of 8.466 kg/s exists

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from the top of the T1 distillation column. This stream also loses some of its heat by passing

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through the MHX2 multi heat exchanger and is cooled to a temperature of -185.6 ºC (stream

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A12) and finally expands by passing through the V2 valve to a pressure of 106 kPa (stream A13)

and enters the T2 distillation column. From the bottom of that, stream A19 with a purity of
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99.98% oxygen and with a mass flow of 3.929 kg/s reaches a pressure of 235 kPa (stream A20)
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by the P3 pump, and by receiving heat in MHX1 and compression by the COM3 compressor,

and finally passing through the HX3 heat exchanger, oxygen with 99.98 mol% purity,
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temperature and pressure of 26.44 ºC and 830 kPa is introduced as one of the products of
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integrated structure (stream A23). On the other hand, stream A17 with a purity of 94.20 mol%
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nitrogen and with a flow rate of 16.76 kg/s exists from the top of the T2 distillation column, and
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after receiving heat from the MHX1 and MHX2 multi heat exchanger, is heated to a temperature

of 20.34 ºC (stream A31). This stream splits into A32 and A33 after passing through TEE.

stream A32 containing nitrogen with a purity of 94.2 mol% and a flow rate of 13.7 kg/s, is

introduced as another product of integrated structure. Stream A33 containing pure nitrogen with

a flow rate of 3.017 kg/s enters the HBP cycle to react with hydrogen in the Haber-Bosch

process, which is described in the following section.

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It should be noted that stream A28 (LNG) with the -165.7 ºC temperature, 101.4 kPa

pressure,and with 1.037 kg/s flow rate reaches 260 kPa pressure by the P1 pump and enters into

the MHX1 multi heat exchanger (stream A29). The output stream A30, which has reached 15 ºC,

is actually a regasified LNG stream that enters the SMR cycle to convert hydrogen, which is

described in the next section.

2.2. Steam methane reforming unit & Solar dish collector

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At present, the conversion of natural gas to hydrogen in the presence of steam is the most

common and cost-effective industrial method of hydrogen production. In this method, methane is

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heated and sent to the reactor with supersaturated water vapor. The reactions are then performed
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in the presence of a catalyst. The proper efficiency and cheap feed of this process make it more

economical than other hydrogen production methods. The main disadvantage of this method is
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the superheated reactions and the production of carbon dioxide gas [42]. Nearly half of the

world's hydrogen is produced by methane reforming in the presence of water vapor. Hydrogen
al

production by this method consists of three stages [43]:

n
ur

A. Methane conversion in the presence of the catalyst, at high temperature and pressure, which

leads to the production of a mixture of hydrogen gas and carbon monoxide and is known as
Jo

synthesis.

CH 4 ( g )  H 2 ( g )  CO( g )  3H 2 ( g ) (1)

B. Conversion in the presence of a catalyst during which carbon monoxide reacts with water

vapor to produce hydrogen and carbon dioxide. Equation (2) is known as gas water

displacement.

15
CO( g )  H 2O( g )  CO2 ( g )  H 2 ( g ) (2)

CH 4 ( g )  2H 2O( g )  CO2 ( g )  4H 2 ( g ) (3)

C. Purification of hydrogen by adsorption method. This step is specific to processes that require

very pure hydrogen (this uses a carbon dioxide capture unit, which is described in the next

section).

Next, as described in the previous section, stream A30, which is regasified LNG, enters the HX4

f
oo
heat exchanger. The output stream A5 reaches a temperature of 62 ºC and enters the mixer. On

the other hand, stream S1, which contains 100% water, in atmospheric conditions, first enters the

pr
P1 pump and reaches a pressure of 250 kPa (stream S2) and increases to 170 ºC during passage
e-
through the HX6 and HX7 heat exchangers (stream S4) and finally enters the mixer. The stream
Pr
S6 exits the mixer and reaches 600 ºC after passing through the HX5 heat exchanger (stream S7).

This stream enters the R1 plug flow reactor. On the other hand, stream S8 with a purity of 24.85
al

mol% hydrogen and a flow rate of 15.85 kg/s exists. Then, in several stages, by passing through

the heat exchangers HX5, HX6, HX4, and HX8 respectively, it drops to a temperature of 25 ºC
n
ur

(stream S12), afterward enters the D1 separator. The stream S14 exits the top of the separator

with a purity of 78.72 mol% hydrogen. As a result, this stream is passed through the V3 valve to
Jo

purify hydrogen and perform the Haber-Bosch process. The output stream S15 expands to a

pressure of 112 kPa and goes into the CO2 capture cycle, which is described in detail in the next

section. Solar dish collectors transfer the heat received from the sun to the organic Rankine

power cycle and steam methane reforming plant. These collectors track the sun on two axes in

the Bandar Abbas climate zone in Iran. The useful heat delivered by the solar dish, radiation

falling on the receiver, and the total heat loss rate of the receiver are calculated using the m-file

code in MATLAB programming according to the equations in Table A.

16
2.3. Carbon dioxide capture cycle

In this section, stream S15 (with the specifications mentioned in the previous section) is injected

into the T3 absorber column with a flow rate of 3.371 kg/s to perform the process of hydrogen

purification and carbon dioxide absorption. The output stream C2 from the bottom of the column

is pumped to the HX9 heat exchanger. The output stream from this heat exchanger called C3

reaches a temperature of 100 ºC and is finally injected into the T4 distillation column. From the

f
top of the column, stream C16 with a purity of 12.77 mol% carbon dioxide and a flow rate of

oo
10.49 kg/s comes out, which reaches 21 ºC by passing through the HX11 heat exchanger and

pr
finally enters the D2 separator. As a result, the output stream C19 from the top of this separator,

with a purity of 98.39 mol% carbon dioxide and a flow rate of 2.761 kg/s, is introduced as
e-
another product of the integrated structure. On the other hand, from the bottom of the T4 column,
Pr
stream C4 with a purity of 97.25 mol% water and flow rate of 239.1 kg/s was pumped to 394.2

kPa by pump P6 (stream C5) and entered the mixer bypassing the HX9 and HX10 heat
al

exchangers (stream C7) at a temperature of 38 ºC and finally injected into T3 column (stream
n

C9). Also, from the top of this column, stream C13 with a purity of 94.75 mol% hydrogen and a
ur

flow rate of 0.77 kg/s is released, which is passed through the splitter X1 component to increase

the purity and remove impurities. As a result, stream C15 with a purity of 100 mol% hydrogen
Jo

and a flow rate of 0.506 kg/s enters the HBP cycle to perform the Haber-Bosch process and

ammonia formation, which will be discussed in the next section.

2.4. Haber-Bosch process

The Haber-Bosch process is an industrial process for the production of ammonia by the reaction

of nitrogen and hydrogen in the presence of a catalyst. In this process, iron catalysts at high

temperatures and pressures are used to break the triple bond of nitrogen molecules and convert

17
them to ammonia. Fritz Haber first introduced the process in 1908, and later Carl Bosch

developed the process on an industrial scale. This is why the Haber- Bosch process is known.

Ammonia synthesis is an exothermic and reversible process based on the following chemical

reaction [44]:

3H 2 ( g )  N 2 ( g )  2 NH 3 ( g ) (4)
H   45.7kJ / molH 2

f
oo
Distinctive physical aspects of equilibrium reaction, the opposite effect of pressure and

temperature on thermodynamics and kinetics is by the equation (5) [17].

pr
( ) ( e- ) (5)
⁄ ⁄ ⁄ ⁄
Pr
To the left of the equation (5) is a chemical equilibrium constant in which non-ideal fugacity

coefficients are calculated in the term . The term refers to the operating conditions of the
al

reactor, especially the presence of inert species, which can reduce the molar fraction of reactants
n

and thus the production of ammonia. On the other hand, as the total pressure increases, so does
ur

the conversion to ammonia.

Jo

In the present study, the pure stream of hydrogen (stream C15) and the pure stream of nitrogen

(stream A33) are first introduced into the mixer. The mixed output stream H1 enters conversion

the R2 reactor with a temperature and pressure of 32.35 ºC and 100 kPa and flow rate of 3.042

kg/s, after passing through the next mixer. From the top of this reactor, stream H4 with a purity

of 43.81% ammonia enters the HX12 heat exchanger with a flow rate of 36.87 kg/s. The stream

H5 with a temperature of 50 ºC, which leaves this heat exchanger, enters the ACRC cycle and

the HX18 heat exchanger for liquefaction, and the output stream H6 returns to the main cycle

18
with a temperature of -50 ºC on the other side, and through this 13860 kW of cooling is given to

the HBP cycle. Stream H6 enters the D3 separator. From the bottom of this separator, the main

product of the present work and integrated structure, namely, stream H11, which is liquid

ammonia with 100 mol% purity, is discharged with a flow rate of 3.042 kg/s. On the other side

of the output stream from the top of the D3 separator, stream H7, which is a mixed stream with a

purity of 40.26 mol% ammonia, rises to 488.2 ºC by passing through the HX12 heat exchanger

f
and then enters the R3 conversion reactor (stream H8). Finally, stream H10, the output from the

oo
top of this reactor with a purity of 44.58 mol% ammonia and a flow rate of 33.83 kg/s, returns to

pr
the respective mixer to repeat these processes and increase ammonia production.

e-
2.5. Absorption-compression refrigeration cycle coupled with organic Rankine cycle

In this section, the stream M1, which is actually the flue gas of power plants with temperature
Pr
and pressure of 466.5 ºC and 140 kPa, with a flow rate of 338.3 kg/s, passes through heat

exchangers HX15 and HX16, respectively, and leaves the cycle at a temperature of 122.45 ºC
al

(stream M3). This operation triggers an ORC cycle with a net power of 22,383.3 kW. Next, from
n

the HX24 heat exchanger (Cooler), 43650 kW of heat is given to the reboiler of the T5
ur

distillation column. This process itself operates an absorption-compression refrigeration cycle

Jo

with water and ammonia. So that stream M11 (138.26 ºC, 1356 kPa) enters the HX22 heat

exchanger with a flow rate of 182.6 kg/s. The stream M12 exits at a temperature of 59.52 ºC and

reaches a pressure of 217 kPa through the V6 valve (stream M13), then it enters the mixer. The

stream M15 with a flow rate of 222.1 kg/s exits the mixer and after passing through the HX21

heat exchanger reaches a temperature of 35 ºC (stream M16), afterward is pumped into the TEE

(by the pump P10 with a pressure of 1250 kPa) and then It branches into two streams, M18 and

M19. The stream M18 with a flow rate of 133.3 kg/s after passing through the HX22 heat

19
exchanger reaches a temperature of 114.2 ºC and is injected into the T5 column. The stream M19

with a flow rate of 88.72 kg/s reaches the temperature of 128.2 ºC by passing through HX16 and

HX17 heat exchangers and returns to the T5 column. On the other side, stream M21 with 52.19

ºC temperature and 1346 kPa pressure and 39.49 kg/s flow rate leaves the T5 column. This

stream passes through the HX20 and HX23 heat exchangers, respectively, and reaches a

temperature of 15 ºC (stream M23). Then enters the V4 valve, the output stream M24 is reduced

f
to a pressure of 217 kPa and after passing through the HX19 and HX20 heat exchangers, reaches

oo
a temperature of -16.92 ºC and enters the respective mixer (stream M14). This process is

pr
repeated and as a result, provides cooling of 13,860 kW for ammonia liquefaction.

2.6. Validation of the developed hybrid system

e-
To validate the novel integrated structure, its different parts (subsystems) are compared
Pr
separately with similar resources in other references and industrial patents. Information on the

flow and structure of the air separation unit is extracted based on reference [45]. The
al

characteristics of the flow compositions in this paper are compared with the similar streams in
n

reference [45]. One of the main reasons for the low difference in flow characteristics is due to the
ur

operating temperature and pressure conditions of the unit used in the developed integrated
Jo

structure. The comparison results are shown in Table 1a, which indicates the proper agreement of

the results with the reference. More theory and background information on stream methane

reforming can be found in reference [26]. Also, information on the stream and equipment of the

absorption–compression refrigeration system is provided in the references [39, 46]. On the other

hand, more theory and background information on the structure of the CO2 capture cycle can be

determined in references [47, 48]. Table 1b presents the results of the validation of the

adsorption-compression refrigeration cycle developed in this paper with respect to references [39,

20
49]. The results show that the performance coefficient of the absorption-compression

refrigeration unit developed in this structure is significantly different from the references. The

main reason for this difference depends on the temperature conditions of the refrigeration cycle

evaporator.

Table 1a. Validation of the air separation unit.

Present study Ref. [45]
Stream A31 Stream 25

f
Temperature (ºC) 20.34 27

oo
Pressure (kPa) 101.0 101.3
Composition (mol%)
Ar 1.2 1.1

pr
O2 4.6 4.69
N2 94.2 94.21
CH4 0.00 e- 0.00
Present study Ref. [45]
Stream A23 Stream 11
Pr
Temperature (ºC) 26.44 -9.8
Pressure (kPa) 830 410
Composition (mol%)
Ar 0.02 0.01
al

O2 99.98 99.99
N2 0.00 0.00
CH4 0.00 0.00
n

Present study Ref. [45]

ur

Stream A11 Stream 17

Temperature (ºC) -178.6 -178.6
Pressure (kPa) 517 517
Jo

Composition (mol%)
Ar 0.47 0.45
O2 1.74 1.68
N2 97.79 97.87
CH4 0.00 0.00
Present study Ref. [45]
Stream A17 Stream 23
Temperature (ºC) -194.24 -194.2
Pressure (kPa) 106 106
Composition (mol%)
Ar 1.2 1.1
O2 4.6 4.69
N2 94.2 94.21
CH4 0.00 0.00

21
 Table 1a. Validation of the two-stage NH3/H2O refrigeration cycle.
Absorption–compression Refrigerant temperature
Mixture COP
refrigeration cycle (˚C)
This study H2O/ NH3/CO2 0.274 -61.53
Chen et al. [39] H2O/NH3/CO2 0.277 -55.00
Mousavi et al. [49] H2O/NH3/CO2 0.268 -54.62

3. Exergy Analysis

f
oo
Exergy investigation is an engineering tool that is utilized to examine the thermodynamics of the

process and specify the maximum amount of useful work that can be achieved from a certain

pr
amount of input energy. The exergy analysis, irreversibilities that increase the wasted work of

system equipment are identified and their impact on process efficiency is determined. The dead
e-
state is the same environmental conditions that are usually considered to be 25 °C and 1 bar [50,
Pr
51]. The exergy rate of a whole system can be considered as the sum of the following

components [37]:
al

ex  ex ph  exch (6)
n
ur

The physical exergy of streams can be calculated as regards [52]:

ex ph   h  h  T s  s  (7)
Jo

where h and s are the enthalpy and entropy of streams at environment temperature and

pressure, respectively. The chemical exergy for streams is obtained from the following equation

[37]:

ech   ( xi ei )  RT  xi Lnxi  i  ech   ( xi ei )  G  xiGi

(8)

22
To calculate the chemical exergy of the non-ideal mixture of different compounds of each stream

is used HYSYS software and MATLAB programming. Exergy balance can be provided for each

equipment as follows:

Exi  ExQi  Exo  ExQo  Wsh  I (9)

where Exin denotes the input exergy; ExQi expresses the exergy due to the inlet heat; Exout is the

outlet exergy; ExQout refers to the exergy due to the heat loss; Wshaft represents the shaft work; and

f
oo
indicates the irreversibility in the system. Table S3 in supplementary materials presents the

equations required for exergy investigation of the equipment associated with in the structure

pr
[37].

4. Results and discussion

e-
In this paper, an innovative combined structure for the tri-generation of liquid ammonia, carbon
Pr
dioxide, and power using the ammonia production process, amine-based CO2 capture cycle, the
al

cryogenic air separation system based on the LNG regasification, steam methane reforming

plant, and absorption-compression refrigeration unit is developed and exergetically is

n

investigated. Thermal integration is utilized to apply waste heat in the combined structure. Solar
ur

dish collectors based on geographical location in southern Iran and close to the Persian Gulf are
Jo

employed to provide the required hot utility. The introduced hybrid system is simulated through

HYSYS and TRNSYS software, and m-file code in MATLAB. The simulation results as well as

the investigation of the exergy analysis and parametric analysis of the integrated system are

described in this section. Tables S1 and S2 in supplementary materials show the operating

conditions and the percentage composition of each system streams based on the naming of Fig.

2, respectively. The main input of the system is LNG with a mass flow rate of 1.037 kg/s, which

uses its cryogenic energy in the cryogenic air separation cycle to produce 16.76 kg/s pure N2 and

23
 3.929 kg/s pure O2. 5302 kW power is consumed in this cycle. After LNG regasification, it

enters the SMR cycle to produce 3.372 kg/s H2 with a purity of 78.72 mol% (stream S15)

through methane reforming. The required heat for this cycle is 12140 kW, which is supplied by

solar parabolic dish collectors. To remove impurities, then it enters the MEA amine-based CO2

capture cycle to prepare 0.5066 kg/s pure H2 to enter the HB process by separating CO2. The

generated hydrogen and nitrogen enter the HB process to produce 3.042 kg/s liquid ammonia.

f
The required cooling of the cycle is also provided by the absorption-compression refrigeration

oo
cycle in the amount of 13860 kW up to -50 ºC. The required heat and power of the refrigeration

pr
cycle with 58410 kW and 5966 kW, respectively, are provided by hot flue gas using the organic

Rankine cycle. The total power consumption of the integrated system is 11970 kW and the total
e-
production power is 25270 kW, so the produced net power is 13300 kW. According to the
Pr
provided explanations, the total thermal efficiency of the entire integrated system is calculated to

be 46.59%. Tables 2 and 3 show the thermodynamic specifications of system equipment and heat
al

exchangers, respectively. In the following, the results of exergy analysis, parametric study, and
n

solar parabolic dish collectors are reported.

ur

Table 2. Thermodynamic specifications of the system equipment.

Jo

Pump
Parameter Adiabatic Power ΔP P ratio Pressure head Capacity
efficiency
Unit % kW kPa - m m3/h
P1 75 0.4493 158.6 2.564 33.13 7.649
P2 99 13.594 218.7 3.158 26.22 221.54
P3 80 0.4931 129 2.217 10.24 11.009
P4 75 2.9143 148.6 2.467 15.05 52.936
P5 75 56.374 174 2.642 17.28 874.77
P6 75 4.9954 15 1.073 1.598 899.18
P7 85 80.074 1500 2.5 111.1 163.35
P8 85 30.785 920 12.5 60.17 102.4
P9 85 526.72 7400 13.33 1189 217.81
P10 85 407.36 1033 5.76 159 1206.7
Compressor

24
Parameter Adiabatic Polytrophic
Power ΔP P Ratio Operating Mode
Efficiency Efficiency
Unit % kW kPa - - %
COM1 80 2480.66 411 2.593 Centrifugal 82.49
COM2 76 2593.70 1240 3.885 Centrifugal 78.92
COM3 80 213.031 600 3.586 Centrifugal 83.31
COM4 85 5558.65 2071 6.178 Centrifugal 87.60
Expander
Parameter Adiabatic Power ΔP P ratio Polytrophic Outlet
Efficiency Efficiency temperature
Unit % kW kPa - % ˚C

f
Tur1 90 22910 7400 0.075 86.87 172.6

oo
Tur2 90 728.3 1500 0.4 89.69 157.3
Tur3 90 1632 920 0.08 89.27 96

pr
Table 3. Heat exchanger characteristics in the integrated structure.

Parameter Min. approach LMTD

e-
Heat Exchanger
Heat duty UA Cold Pinch
Temp.
Pr
Unit ˚C ˚C kW kJ/h. ˚C ˚C
HX1 3.034 14.31 2385 600000 29.96
HX2 40.27 72.68 1943 96200 21.73
HX3 35.56 68.33 456.4 24000 26.43
al

HX4 11.1 39.70 206 18700 101.14

HX5 10 21.20 14930 2540000 600
n

HX6 75.74 81.36 6756 299000 127

HX7 3 5.81 33820 20900000 127
ur

HX8 1 1.5 29790 71200000 24

HX9 20.46 20.74 60860 10600000 42.27
HX10 13 20.33 24520 4340000 25
Jo

HX11 1 4.59 20470 16000000 20

HX12 46.82 70.08 52110 2680000 488.17
HX13 3 10.67 8661 2920000 25
HX15 1.5 28.66 113300 14200000 465
HX16 7.45 17.92 14760 2960000 115
HX17 1.916 1.251 47230 136000000 35.16
HX18 11.52 33.63 13860 1480000 -61.52
HX19 2.978 35.60 19420 1960000 -16.97
HX20 31.93 41.12 3846 337000 -16.93
HX21 5 7.93 57880 26200000 30
HX22 24.06 24.21 69340 10300000 114.2
HX23 5 8.07 47700 21300000 30
MHX1 1.29 9.20 5197 2033000 -174.16
MHX2 3.13 5.65 340.8 217000 -175

25
4.1. Exergy analysis results

Table S4 in supplementary materials presents the exergy of the system streams the developed

integrated structure. Using these values, as well as the exergy destruction and exergy efficiency

of the system equipment, the exergy efficiency and exergy destruction of each equipment are

calculated (Table 4). Fig. 3a shows the contribution of each section to the total exergy

destruction cycle. According to this figure, the most exergy destruction belongs to the sections of

f
heat exchangers and collectors with values of 53921 kW (with a share of 46.18% of the total)

oo
and 21551 kW (with a share of 18.46% of the total),, respectively. Fig. 3b depicts the exergy

pr
efficiency and exergy destruction of the heat exchangers section separately. Based on the

obtained results, the exergy destruction and exergy efficiency of the whole integrated system are
e-
calculated as 116763 kW and 57.36%, respectively. Fig. 4 illustrates the exergy flow diagram of
Pr
the entire system.

Table 4. The exergy destruction and efficiency of the equipment.

al

̇ ̇ ̇
n

Components (kW) (kW) (kW) Efficiency

HX1 36257.2 35872.6 384.6 0.8388
ur

HX2 37934.9 37496.9 438.0 0.7745

HX3 4716.2 4543.4 172.8 0.6214
Jo

HX4 127803.8 127770.8 33.0 0.8481

HX5 156504.1 156227.7 276.4 0.9815
HX6 86481.9 85652.8 829.1 0.8773
HX7 31692.2 29935.0 1757.1 0.9480
HX8 82616.2 82381.1 235.1 0.9921
HX9 1464866.9 1464139.7 727.1 0.9881
HX10 1435659.8 1420961.0 14698.9 0.4006
HX11 13020.7 12855.2 165.5 0.9919
HX12 1455003.3 1449231.5 5771.8 0.8892
HX13 67344.1 67286.9 57.1 0.9934
HX14 60614.3 57375.7 3238.6 0.5168
HX15 451658.1 440191.3 11466.8 0.8988
HX16 683320.2 682910.7 409.5 0.9722

26
HX17 1004699.8 1004264.6 435.2 0.9908
HX18 776466.9 773392.8 3074.1 0.7782
HX19 832162.0 830197.0 1965.0 0.8988
HX20 1601198.4 1600569.1 629.3 0.8364
HX21 2471767.6 2470152.7 1614.9 0.9721
HX22 1781438.4 1778919.7 2518.7 0.9637
HX23 1523081.2 1522971.1 110.1 0.9977
HX24 377731.4 376108.3 1623.1 0.8496
MHX1 62635.1 61459.7 1175.4 0.7738
MHX2 16904.4 16790.9 113.5 0.6668
Tur1 402408.3 400644.5 1763.9 0.9285

f
oo
Tur2 57375.7 57319.5 56.2 0.9284
Tur3 40179.7 40032.1 147.6 0.9171
COM1 2581.2 2216.1 365.1 0.8528
COM2 4348.5 3898.5 450.0 0.8265

pr
COM3 1335.0 1260.4 74.6 0.6497
COM4 30797.3 30151.9 645.4 0.8839
P1
P2
53722.6
34036.5
e-53722.2
34036.4
0.3
0.1
0.3059
0.9899
P3 2946.7 2946.4 0.3 0.3389
Pr
P4 9631.2 9630.9 0.3 0.9028
P5 709363.3 709340.7 22.6 0.5991
P6 755527.9 755526.2 1.8 0.6497
al

P7 53923.9 53911.9 12.0 0.8507

P8 37897.7 37891.7 6.1 0.8026
n

P9 359254.1 359177.8 76.3 0.8552

P10 1596383.7 1596324.6 59.1 0.8548
ur

V1 8029.8 8121.7 92.0 0.7612

V2 6065.9 6116.4 50.5 0.6312
V3 61542.2 60951.4 590.8 0.6119
Jo

V4 802010.1 802500.1 490.0 0.7895

V5 30736.9 31498.6 761.7 0.7985
V6 808622.3 808895.1 272.8 0.6523
D1 69653.4 69653.4 0.0 1.0000
D2 6367.5 6367.5 0.0 1.0000
D3 748154.2 748154.2 0.0 1.0000
SP 60476.0 60086.2 389.8 0.9936
R1 89085.9 85062.8 4023.0 0.9548
R2 770028.9 760985.3 9043.6 0.9883
R3 707906.6 703501.5 4405.1 0.9938
T1 7365.0 13506.0 6141.1 0.5453
T2 3440.0 951.2 2488.8 0.7235

27
 T3 770566.5 769288.6 1277.9 0.9983
T4 1634606.4 1627024.6 7581.8 0.5037
Collectors 489303.6 467751.9 21551.7 0.3230
Cycle 266520.9 149757.9 116763.0 0.5736

f
oo
pr
e-
Pr

(a)
nal
ur
Jo

28
 f
oo
pr
e-
Pr

(b)
al

Fig. 3. The share of each part of the system exergy destruction

n
ur
Jo

29
 Exergy heat input Turbines Collectors
64795 kW
Pumps Reactors

178.8 1967.5 17471 21551

kW kW kW kW

f
Products

oo
127626 kW
Exergy Streams
189756 kW

pr
e-
Pr
al

1535.1 2647.5 17489 53921 Power

Power kW kW kW kW 25273 kW
11969 kW
n
ur

Compressors Heat exchangers

Separators & Valves Towers

Jo

Fig. 4. Exergy flow diagram of the developed integrated cycle.

4.2. Results of the parametric study

System parametric study is a very widely used tool to study the performance of the system in

different operating conditions and also to find the optimum conditions of the system. In the

present section, the results are reported by changing some of the most important system

parameters.

30
4.2.1. Reformer temperature

The effect of reformer temperature on methane conversion percentage, reformer heat duty,

produced hot water rate, and stream S15 molar flow rate is shown in Fig. 5. According to this

figure, as the reformer temperature increases, the methane conversion increases sharply, meaning

that the greater amount of the incoming methane to this cycle reacts with steam, as a result, more

product is generated, so stream S15, which is the output of the SMR cycle, is strongly increased.

f
On the other hand, the required heat by the reformer enhances with increasing methane

oo
conversion. As the reformer temperature increases, the excess low-value heat of this cycle also

pr
decreases, resulting in a decrease in the amount of produced hot water. Methane conversion

percentage, reformer heat duty, and stream S15 molar flow rate increases from 0.46%, 399 kW,
e-
and 237.2 kmol/h to 100%, 12220 kW, and 1150 kmol/h, respectively by increasing the reformer
Pr
temperature from 400 to 650 ºC and produced hot water rate decreases from 12.94 to 11.34 kg/s.

Rising the reformer temperature not only enhances the rate of the SMR cycle product but also
al

enhances its quality. As shown in Fig. 6, as the reformer temperature increments, the
n

composition of the stream S15 leads to more hydrogen production, so that as the reformer
ur

temperature increases from 400 to 650 ºC, the hydrogen content in the stream S15 increases from
Jo

1.76 to 78.72 mol%. Then, it reaches this constant value almost from a temperature of more than

600 ºC.

31
 Hot Water Flow Rate (kg/s) Stream S15 Molar Flow (kmol/h)
Methane Conversion (%) Reformer Heat Duty (kW)

13.0 100 14000

12000
12.6 80
Hot Water Flow Rate (kg/s)

Refoemer Heat Duty (kW)

Methane Conversion (%)
10000

f
12.2 60

oo
8000

11.8 6000
40

pr
4000
11.4 20 e- 2000
Pr
11.0 0 0
400 450 500 550 600 650
Reformer Temperature (˚C)
n al

Fig. 5. Reformer temperature effects on hot water and stream S15 flow rates, methane conversion, and re
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32
 H2 Content in Stream S15 (mol%) CH4 Content in Stream S15 (mol%)
CO2 Content in Stream S15 (mol%) H2/CO2 Molar Ratio in Steram S15 (-
25.0 80 10

90
70
CO2 Content in Stream S15 (mol%)

20.0 80
H2 Content in Stream S15 (mol%)

60
70

f
oo
50
15.0 60

40 50

pr
10.0 40
30 e- 30
20
Pr
5.0 20
10
10
al

0.0 0 0
400 450 500 550 600 650
n
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Fig. 6. Reformer temperature effects on stream S15 composition.

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4.2.2. Reformer pressure

The temperature of the reformer not only affects the operating conditions of the SMR cycle but

also its pressure. The effect of reformer pressure changes on stream S15 molar flow rate, H 2 and

CO2 contents in stream S15, and H2/CO2 molar ratio, is shown in Fig. 7. According to this figure,

by increasing the reformer pressure from 250 to 750 kPa, the stream S15 molar flow rate

decreases from 1150 to 1139 kmol/h and is approximately constant from 700 kPa. Although

increasing the reformer pressure leads to a slight decrease in the final product rate, it enhances

33
the quality of the final product of this process so that by incrementing the pressure from 250 to

750 kPa, H2 content in the stream S15 rises from 78.72 to 79.51 mol%, but CO2 content in the

stream S15 initially has an increasing trend and then this trend decreases. The H2/CO2 molar

ratio also enhances with increasing reformer pressure.

4.2.3. Solar simulation results

f
In the present work, solar parabolic dish collectors are used to supply the required heat by the

oo
reformer as well as the ORC. Fig. 8 shows the changes in the variables of the current solar system

during the day and night. According to this figure, the changes of useful energy collected,

pr
auxiliary energy, ambient temperature, and solar irradiation during the day and night are shown
e-
so that the maximum values of useful energy collected and solar irradiation are 23557 kW and
Pr
907.3 kW/m2, respectively which happens at noon.
n al
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34
 Stream S15 Molar Flow (kmol/h) H2 Content in Stream S15 (mol%)

CO2 Content in Stream S15 (mol%) H2/CO2 Molar Ratio in Steram S1

19.76 Stream S15 Molar Flow (kmol/h) 1150 79.6

19.74 1148
CO2 Content in Stream S15 (mol%)

H2 Content in Stream S15 (mol%)

79.4

f
19.72

oo
1146
79.2
19.7

pr
1144
19.68
79.0

19.66
1142
e-
Pr
78.8
1140
19.64
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19.62 1138 78.6

250 350 450 550 650
Reformer Pressure (kPa)
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Fig. 7. Reformer pressure effects on stream S15 composition and molar flow rate.
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35
 Ambient Temperature (˚C) Solar Irradiation (W/m²)
Useful Energy Collected (kW) Auxiliary Energy (kW)

40 25000 25000
Useful Energy Collected (kW)

35
20000 20000
Ambient Temperature (˚C)

30

f
oo
15000 15000

25

pr
10000 10000
20

15
5000
e- 5000
Pr
10 0 0
8 10 12 14 16 18
al

Time (h)
n
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Fig. 8. Solar parabolic dish collector simulation results.

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5. Conclusion

In the present work, a novel integrated system for the production of liquid ammonia, power, pure

oxygen, carbon dioxide, and hot water using the Haber-Bosch process, amine-based carbon

dioxide capture cycle, and absorption-compression refrigeration was presented. Liquefied natural

gas was used as the main feed system so that initially its cooling during the regasification process

was applied in the cryogenic air separation unit to produce nitrogen and pure oxygen and then

enters the steam methane reforming cycle to generate hydrogen. The required heat of the

36
developed integrated structure was provided by solar energy. The required cooling of this cycle

is also supplied by the absorption- compression refrigeration system so that the required heat was

provided by the power plant exhaust flue gas. The following materials can be considered as the

achievements of this research.

1. The present integrated system produced 3.042 kg/s ammonia, 3.929 kg/s pure oxygen, 11.31

kg/s hot water, 2.762 kg/s carbon dioxide, and 13300 net power as final products. The total

f
thermal efficiency of the system was calculated at 46.59%.

oo
2. Specific power consumption of the air separation units and coefficient of performance of

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absorption compression refrigeration system were 0.0879 kWh/kg N2 and 0.2793, respectively.
e-
3. The results of the exergy analysis showed that the most exergy destruction of the whole
Pr
system was related to the heat exchangers section, which alone accounts for 46.18% of the total

exergy destruction. The total exergy destruction and the exergy efficiency of the developed
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integrated system were 116763 kW and 57.36%.4. Sensitivity analysis was performed on

important system parameters including reformer temperature and pressure as well as solar
n
ur

parameters and the results were reported. Sensitivity analysis of the integrated system showed

that by increasing the reformer temperature, the output hydrogen and reformer heat duty
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increased. Also, by increasing the reformer pressure from 2.5 bar to 7 bar, the hydrogen content

of the input stream to the amine-based carbon dioxide capture cycle increased from 78.72 to

79.51 mol%.

5. For future works in this field, we can refer to the environmental analysis along with the

economic analysis of the current system. It will also be worthwhile to consider the integration of

various hydrogen and nitrogen production methods to be used in the Haber-Bosch process.

37
 Appendix

The equations needed for solar dish collectors analysis involved in the process [23].

Generated heat of each dish Qs  I s Aa A.1

Energy arrived at the absorber and the Qu  Q r  Q l A.2
energy loss in the absorber
The optical efficiency of the solar dish 0  Q r / Q s A.3
Receiver efficiency r  Qu / Qr A.4
Thermal efficiency of a solar dish c  Qu / Qs

f
A.5

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Optical efficiency 0   cos( ) A.6
Net energy loss from the absorber dish A.7

pr
Nusselt number Nu l  0.106Grl1/3 (Tw / T a )0.18 (4.256Ac / Aw )s h (1 ) A.8
Grashof number Grl  g  (Tw / T a )L3 / v 2
e- A.9
Convection heat transfer coefficient hc  Nu l K / L A.10

Qlc  hc Aw (Tw T a )
Pr
Heat lost from receiver through convection A.11
Heat lost from the receiver through
Q lr  Ac eff  (Tw4 T a4 ) A.12
radiation
al

The surface area of the receiver aperture Ac  Aa / c A.13

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38
Nomenclatures

Acronyms/Abbreviations

ASU Air separation unit

ACRC Absorption-compression refrigeration cycle

HBP Haber-Bosch process

LHV Lower heating value

LMTD Logarithmic mean temperature difference

f
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LNG Liquefied natural gas

MED Multi effect desalination

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ORC Organic Rankine cycle

SMR

SOE
e-
Steam methane reforming

Solid oxide electrolyzer

Pr
Equipment names

COMi Compressor i
al

Di Flash dram i
n

HXi Heat exchanger i

ur

MHXi Multi heat exchanger i

Turi Turbine i
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Ri Reactor i

Ti Tower

Pi Pump

Vi Valve i

Chemical formulas

Ar Argon

CH4 Methane

39
C2H6 Ethane

CO Carbon monoxide

CO2 Carbon dioxide

H2 Hydrogen

H2O Water

N2 Nitrogen

NH3 Ammonia

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CH3OH Methanol

O2 Oxygen

pr
R113 Trichlorotrifluoroethane

Variables/parameters e-
e Specific flow exergy
Pr
Ex Exergy

H Pump head
al

h Enthalpy
n

̇ Mass flow rate (kg/s)

ur

̇ Mole rate of the ith stream (mol/kg)

P Pressure
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Q Volumetric flow rate

̇ Heat transfer rate

Universal gas constant (8.314 J/ mol. K)

T Temperature

Ambient temperature (ºC)

s Entropy

Greek letters/symbols

40
 Efficiency

Superscripts and Subscripts

ch chemical

min minimum

ph physical

Reb reboiler

f
oo
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43
CRediT authorship contribution statement
Mostafa Moradi: Methodology, Investigation, Writing - original draft, Software, Validation.Bahram
Ghorbani: Supervision, Conceptualization, Methodology, Investigation, Software, Validation, Original
draft.Armin Ebrahimi: Methodology, Investigation, Writing - original draft, Software,
Validation.Masoud Ziabasharhagh: Investigation, Methodology, Investigation.

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships

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that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered as
potential competing interests:

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e-
Pr
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Highlights
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 Integrated Haber-Bosch process, steam methane reforming and air separation unit.
 CO2 capture unit were employed to hydrogen purification.
 LNG regasification and solar collectors used to supply the utility of the system.
 This structure produced 3.042 kg/s ammonia, 13300 kW power and 2.762 kg/s CO2.
 Total exergy efficiency & exergy destruction of the system were 57.36% & 116763 kW.

44
Graphical abstract

O₂ Liquefied Flue
Power Power
NH₃ gas

-50 C, 100 kPa,

26.44 C, 830 kPa, 3.042 kg/s 16417 kW 128100 kW
3.929 kg/s 5302.5 kW 13860 kW
25 C, 101.3 kPa,
20.69 kg/s Pure N₂,
32.37 C, 100 kPa, Absorption Compression
Air 3.017 kg/s 50 C, 100 kPa,
ASU & LNG Haber-Bosch Refrigeration Cycle
Regasification 36.87 kg/s
Process coupled with ORC
Unit
LNG
-165.8 C, 101.4 kPa,

f
1.037 kg/s 20.34 C, 101 kPa,

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CH₄ , 13.7 kg/s
15 C, 250 kPa, Pure H₂, Heat Flow
1.037 kg/s 32.37 C, 100 kPa,
N₂
0.5066 kg/s

2.9 kW Cold Flow

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Steam Methane
Power Reforming CO₂
Power Unit 24.92 C, 112 kPa, Capture Unit
60631 kW
3.371 kg/s Power

2250 kW 12140 kW
e-
21 C, 180 kPa,
2.761 kg/s
61.4 kW
Mass Flow
10910 kW Power
Pr
Organic Rankine Solar Dish
Cycle Collector CO₂
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Jo

45