Introduction

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(Introduce area of research)

The Haber-Bosch process was created in the early 20th century and is used to synthesize more
than 99% of the worlds ammonia. The reaction uses atmospheric nitrogen and artificial
hydrogen to synthesize ammonia that is a precursor for biofuels, fertilizers, and alternative fuels.
(Explain importance of research area)
Using fossil fuels to produce hydrogen has had a large impact on the environment because of the
increasing emissions of CO2. Gasification of coal and steam-reforming of natural gas accounts
for two-thirds of the CO2 emissions from the production of hydrogen as a precursor for
ammonia. The fossil fuels being paired with ammonia, as the second-most industrialized
artificial chemical produced in the world, has led to this industry using 1.6% of the worlds fossil
fuel in 2006. A move away from fossil-fuels will not only benefit the environment by lessening
the ecological footprint, but it will also allow power plants to become energy independent from
the fluctuating prices of natural gas and coal.
(Highlight relevant works)
The thermodynamic minimum required for a stoichiometric amount of ammonia synthesis is
20.9 GJ/Mton. In large-scale industry, technological advancements have lowered the
thermodynamic cost to 28 GJ/Mton. Any further improvement on the current technology would
be miniscule.
(Justify need for current work)
Although the Haber-Bosch process produces ammonia, the method is inefficient and an
environmental hazard. Ammonia plays a large role in todays society and will continue to do so
since the worlds population is expected to be around 9 billion by 2050. Ammonia can

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worlds ammonia. Theisreaction is exothermic and uses
uses atmospheric nitrogen and artificial hydrogen to
synthesize ammonia that carries on to be used as a
feedstocks a precursor for biofuels, fertilizers, and
alternative fuels. More than 99% of the global production of
ammonia can be traced back to the Haber-Bosch process.
Previous literature has analyzed the entire process in attempt
to lessen the energy input required to synthesize ammonia
and to lower the environmental footprint of this industry.
Currently, large amounts of fossil fuels from either the
gasification of coal or steam reforming of natural gas,
contribute the necessary high purity hydrogen for ammonia
synthesis.
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Deleted: amount missions of CO2.
emissionsGasification of coal and steam-reforming of
natural gas accounts for t, which to-thirds of the CO2
emissionscomesfrom the production of hydrogen as a
precursor feedstock or the mmonia synthesis The
production of 1000 kg of liquid ammonia would require
41,000 Mj of energy and would release 1920 kg of CO 2.

...
Deleted: is necessity offossil fuels being paired with
ammonia, being s the second-most industrialized artificial
chemical produced in the world, has led to this industry
contributing sing 1.6% of the worlds wide ossil fuel
usage n 2006. This energy expenditure consumed 1.2% of
the worlds total energy annually.
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potentially be used as an alternative fuel. Hydrogen gas been proposed as the leading alternative

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fuel; however, ammonia carries more hydrogen when compared to liquid hydrogen and,

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therefore, has a higher volumetric energy content. Implementation of ammonia into current

Deleted: Ammonia is a prerequisite for fertilizer

production, contributing nearly to 40% of the worlds access...

technology would require little modification. Additionally, liquid ammonia would only emit

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gaseous nitrogen and water vapor, both of which are not harmful to the environment.

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(Introduction of current work)

Although the Haber-Bosch process provides an ample amount of ammonia, the method is energy

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inefficient and environmentally disruptive. This process must be improved to meet the future

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generations needs of food, fuels, and environment conservation. In this paper, an analysis of all

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the proposed improvements to the Haber-Bosch process is reviewed.

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reviewed articles pertaining to this specific field and will
discuss them in the latter sections.

Methods

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Life Cycle Analysis of an Alternative to the Haber-Bosch Process

Anabaena was cultured in open ponds and their biomass was harvested then converted to biogas.
Ammonia from the biomass will be converted to ammonium sulfate and further processed to
produce liquid ammonia.6

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Wind and Solar Hydrogen for the Potential Production

Development of dynamic mapping of the wind and solar potential in the state of Ceara, Brazil
used MesoMap as a simulation tool that pulled data from the Brazilian Eolic Potential Atlas.
Solar databases were used in simulations provided by the Brazilian Atlas of Solar Energy and
was coanalyzed with the Geographical Information Systems (GIS). The solar cells were assumed
to be polycrystalline photovoltaic panels with power of 215 W, voltage of 26.6 V, and 14.5%
efficiency.
Wind Powered Ammonia Fuel Production for Remote Islands
The case study location is Monhegan Island in Muscongus Bay, Maine and investigated fourteen
different turbines. Comparison of diesel systems to wind-ammonia system used the net present
value (NPV).
Techno-Economic Analysis of Ammonia Production via Integrated
The Aspen Plus software was used to model the gasification process and ammonia production. A
Mixed Integer Linear Programming (MILP) software was used to simulate the energy system
once biomass gasification implementation.

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The Long-Term Impact of Urbanization on Nitrogen Patterns and Dynamics in.

The Greater Shanghai Area (GSA) was the location of study. The Nitrogen Cycling Network
Analyzer (NCNA) with data compiled from the government and other published papers was used
for analysis.
Low Temperature Plasma-Catalytic NOx Synthesis in a packed DBD Reactor
Low-temperature plasma-catalytic NOx synthesis was performed in a one-sided dielectric barrier
discharge plasma reactor. The rate of nitrogen and oxygen were monitored by mass flow
controllers. NOx products were analyzed in a gas cell with CaF2 windows using a FTIR
spectrophotometer.

Results and Discussion

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Life Cycle Analysis of an Alternative to the Haber-Bosch Process

(Results) Using cyanobacteria to form 1000 kg of liquid ammonia is expected to result in a
reduction of 3140 kg CO2 in GWP and 101,300 MJ NRE usage. When changes in the algal slurry
concentration are made, there is still a reduction in GWP and NRE. Variation in the compression
pressure from 25 atm to 17.5 atm accounts for a reduction of -101,300 MJ to 101,310 MJ,
respectively, in overall impact.
(Discussion) The system proposed creates a feedback loop where biogas as a byproduct can be
used as the energy source, thus accounting for 6.5% in NRE usage for biogas compared to
produce ammonia via the Haber-Bosch process. Even with the reduction in GWP from the
Haber-Bosch process, production of agricultural biomass accounts for 1392 kg of the 2000 kg
CO2 expected from generation of 1000 kg of ammonia. Similarly, production of agricultural
biomass accounts for 5800 MJ of the 10900 MJ anticipated from 1000 kg of ammonia.
Production of agricultural biomass accounts for the majority of the NRE usage and GWP that the
changes anticipated in pressure and concentration are minimal.
Wind and Solar Hydrogen for the Potential Production

(Results) The Ibiapaba region has the largest potential for production of solar hydrogen with over
181 tons/km2/year. The coastal region has the largest potential for production of wind hydrogen
with over 400 tons/km2/year. The entire coast and some parts of central Ceara have the potential
to produce renewable ammonia over 1800 tons/km2/year, with some coastal regions having a
potential of 2550 tons/km2/year.
(Discussion) Coastal regions experience a wind speed above 7.0 m/s at 50 m above ground level,

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while the inner portion of Ceara records wind speeds on average of 4.5 m/s. This variance in
wind speeds accounts for the higher hydrogen potential production from wind on the coastline.
The state of Ceara has a larger exposure to solar radiation inland, with areas experiencing up to
5920 Wh/m2/day. The coastline experiences an average of 2407 Wh/m2/day. This difference in
solar radiation accounts for the larger potential of solar hydrogen production reaching 186
tons/km2/year inland rather than on the coast.
Wind turbines from ENERCON brand, model E-70/2.3 MW were assumed to be installed

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every km2 producing 5 MW. Hellmans law and the Weibull distribution were used to calculate
the average wind speed and wind energy, respectively.

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Wind-Powered Ammonia Fuel Production for Remote Islands

(Results) A wind-powered ammonia facility has a lower NPV compared to an all-diesel facility.
An 810 kW turbine demonstrates the lowest NPV of any turbine. Sensitivity analysis of fuel key
parameters suggests that a system with wind speeds of 25-50% increases the relative NPV by
50%. Whereas, a system with wind speeds of 125% decreases relative NPV by 10%.
(Discussion) Most wind-ammonia plants have a lower NPV value except for systems where no

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integration of an ammonia plant and when the ammonia plant is not used. Sensitivity analysis of
factors pertaining to the system show that price of diesel fuel and wind speed were the most
sensitive. Because of the location of Monhegan Island and the need to transport diesel fuel, it is
possible that diesel fuel could fluctuate. It is projected that the ammonia plant would serve better
to use ammonia as a fuel when diesel costs $10. Low wind speeds raise the relative NPV of the
system. Conversely, high wind speeds do not add any benefit because of the electrical heating
that would occur. High wind speeds, therefore, should not be used in this system.
Techno-Economic Analysis of Ammonia Production via Integrated

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(Results)The integrated PEBG system (Case A) when compared to the stand-alone PEBG (SA)
system had an overall increase in energy efficiency of 10%.
Each node in the system simulates a processing unit and the path of which the nodes are
connected to simulate the flow of energy. This model was based on current pressurized entrained
flow gasified (PEBG) technology with each subsequent reaction modeled independently. An acid
gas removal (AGR) and a liquid nitrogen wash were used as final gas cleanings before
proceeding to ammonia synthesis. The model used an iron promoted catalyst and the product was
purified by condensation.
(Discussion) Case A system required two additional product streams of ammonia and tall oil.
These two additional streams required an increase of 50% of biomass. The internal surplus of
biomass and the increased discharge of tall oil lead to more effective system mechanics when
compared to SA. The production costs of Case A and SA, 458 and 523 Myear1-, respectively,
demonstrated a minimal economic advantage in the integrated system. Both systems would
require an increase in the current ammonia selling price to reach an internal rate of return of 1015%.
The Long-Term Impact of Urbanization on Nitrogen Patterns and Dynamics in.
(Results) Nitrogen input from 1952 to 2004 has increased from 57.7 Gg N to 587.9 Gg N,
respectively. Biological nitrogen fixation remained consistent around 20 Gg N year-1. However,
its contribution decreased from 26.2% to 3.1% from the years 1952 to 2004. Human involvement
in the manipulation of the nitrogen cycle have contributed 97% of total nitrogen input in 2004
compared to 73% in 1952.
(Discussion) The GSA has a linear correlation between population and nitrogen input. China had
the Cultural Revolution where the annual population growth decreased from 3% to 0.2% and
GDP growth rate decreased from 13% to 8%. This movement led to a decrease in nitrogen input
of the GSA during 1965. However, China implemented Reform and Opening Up where it
encouraged an increase in the number of households and GDP. Chinas one-child policy led to
higher divorce rates and consequently a decrease in household size from 4.6 persons in 1952 to
2.8 in 2004. Increased divorce rates led to an increase in the number of households by five

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million. Considering that smaller families live in smaller households that are less efficient, these

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factors correlate to a higher nitrogen input after the implementation of this policy.

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The analysis using a coupled human and natural factors (CHANS) approach.

Moved up [1]: Coastal regions experience a wind speed

m above ground level, while the inner portion of Ceara
records wind speeds on average of 4.5 m/s. This variance in
wind speeds accounts for the higher hydrogen potential
production from wind on the coastline. The state of Ceara
has a larger exposure to solar radiation inland, with areas
experiencing up to 5920 Wh/m2/day. The coastline
experiences an average of 2407 Wh/m2/day. This difference
in solar radiation accounts for the larger potential of solar
hydrogen production reaching 186 tons/km2/year inland
rather than on the coast.
Wind turbines from ENERCON brand, model E-70/2.3
MW were assumed to be installed every km2 producing 5
MW. Hellmans law and the Weibull distribution were used
to calculate the average wind speed and wind energy,
respectively.

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Low-Temperature Plasma-Catalytic NOx Synthesis in a packed DBD Reactor

(Results) Analysis of quartz wool, MgO, -Al2O3, -Al2O3, and the blank produced 700 to 3000
ppm of NOx. The -Al2O3 catalyst gave the highest concentration of 3000 ppm of NOx, with
similar concentrations obtained from quartz wool.
(Discussion) Discharge behavior among the support catalysts varied and either suppressed or
improved the formation of microdischarges inside the DBD reactor. Discharge behavior is not
fully understood for its mechanism and the effect on NOx production. However, the data shows
that the formation of microdischarges is essential for NOx production. Surface area corresponds
to higher NOx production. -Al2O3 (112 m2g-1) had the largest surface area of the analyzed
catalysts and had the highest NOx production. The presence of support material allows for
microdischarges to move along the surface and thus a higher frequency of discharges throughout
the DBD reactor, leading to a higher NOx production. BaTiO3 and TiO2 have diaelectric
constants ranging from 600-4500 depending on temperature. Applied electric fields generate an
opposing internal electric field within the catalyst leading to a slower acceleration of electrons
across the surface of the material. This slow acceleration diminishes the microdischarges across
the surface and decreases NOx production. Structure of the catalysts shows a correlation with
higher NOx production. The high curvature of quartz wool and -Al2O3 allows electrons to
accumulate at the rigid surface edges and thus increases the localized electric field at that point.
Thus, rigid structure of a catalyst has demonstrated a positive correlation with higher NOx
production.

Conclusion
In summary, many alternatives to the Haber-Bosch process have been explored and have shown
promising results. Modification of the hydrogen production energy from solar and wind could

Moved up [2]: Most wind-ammonia plants have a lower

for systems where no integration of an ammonia plant and
when the ammonia plant is not used. Sensitivity analysis of
factors pertaining to the system show that price of diesel fuel
and wind speed were the most sensitive. Because of the
location of Monhegan Island and the need to transport diesel
fuel, it is possible that diesel fuel could fluctuate. It is
projected that the ammonia plant would serve better to use
ammonia as a fuel when diesel costs $10. Low wind speeds
raise the relative NPV of the system. Conversely, high wind
speeds do not add any benefit because of the electrical
heating that would occur. High wind speeds, therefore,
should not be used in this system.
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Discussion
Life Cycle Analysis of an Alternative to the Haber-Bosch
Process
The system proposed creates a feedback loop where biogas
as a byproduct can be used as the energy source, thus
accounting for 6.5% of biogas used to produce ammonia via
the Haber-Bosch process. Even with the reduction in GWP
from the Haber-Bosch process, production of agricultural
biomass accounts for 1392 kg of the 2000 kg CO 2 expected
from generation of 1000 kg of ammonia. Similarly,
...
Moved up [3]: The GSA has a linear correlation between
nitrogen input. China had the Cultural Revolution where the
annual population growth decreased from 3% to 0.2% and
GDP growth rate decreased from 13% to 8%. This
movement led to a decrease in nitrogen input of the GSA
during 1965. However, China implemented Reform and
Opening Up where it encouraged an increase in the number
Moved up [4]: Discharge behavior among the support
catalysts varied and either suppressed or improved the
formation of microdischarges inside the DBD reactor.
Discharge behavior is not fully understood for its mechanism
and the effect on NOx production. However, the data shows
that the formation of microdischarges is essential for NOx
production. Surface area corresponds to higher NO x

lead to a more environmentally-friendly synthetic process of ammonia. A complete shift away

from the Haber-Bosch process is economically challenging; therefore, integration of ammonia
plants into current biomass mills could be the bridge needed for a true societal change. Plasmacatalytic synthetic methods also hold potential for replacing the Haber-Bosch process, but more
research is needed to determine the efficiency and implementation of these methods. However,
utilizing cyanobacterium and entirely disregarding the hydrogen production demonstrates the
highest potential for an eco-friendly synthetic pathway for liquid ammonia.

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References

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(1) Andersson, J.; Lundgren, J. Techno-economic analysis of ammonia production via integrated biomass
gasification. Appl. Energy. 2014, 130, 484-490.
(2) Esteues, N. B.; Sigal, A.; Leiva, E.P.M.; Rodriguez, C.R.; Cavalcante, F.S.A.; de Lima, L.C. Wind and solar
hydrogen for the potential production of ammonia in the state of Ceara - Brazil. Int. J. Hydrogen Energy.
2015, 40, 9917-9923.

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(3) Gu, B.; Dong, X.; Peng, C.; Luo, W.; Chang, J.; Ge, Y. The long-term impact of urbanization on nitrogen
patterns and dynamics in Shanghai, China. Environmental Pollution. 2012, 171, 30-37.

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(4) Morgan, E.; Manwell, J.; McGowan, J. Wind-powered ammonia fuel production for remote islands: A case
study. Renewable Energy. 2014, 72, 51-61.

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(5) Patil, B. S; Cherkasov, N.; Lang, J.; Ibhadon, A.O.; Hessel, V.; Wang, Q. Low temperature plasma-catalytic NOx
synthesis in a packed DBD reactor: Effect of support materials and supported active metal oxides. Appl.
Catal., B. 2016, 194, 123-133.
(6) Razon, L. Life Cycle Analysis of an Alternative to the Haber-Bosch Process: Non-Renewable Energy Usage and
Global Warming Potential of Liquid Ammonia from Cyanobacteria. Environ. Prog. Sustainable Energy. 2014,
33, 618-624.

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