1.

Introduction
The Haber-Bosch process was created in the early 20th century and is used to synthesize more
than 99% of the worlds ammonia.5,6 The reaction uses atmospheric nitrogen and artificial
hydrogen to synthesize ammonia that is a precursor for biofuels, fertilizers, and alternative fuels.6
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 2006.4 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.4 The thermodynamic minimum required for a stoichiometric amount
of ammonia synthesis is 20.9 GJ/Mton.4 In large-scale industry, technological advancements have
lowered the thermodynamic cost to 28 GJ/Mton.4 Any further improvement on the current
technology would be miniscule.4 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 because the worlds population is expected to be around 9 billion by
2050.2 Ammonia can potentially be used as an alternative fuel. Hydrogen gas been proposed as
the leading alternative fuel; however, ammonia carries more hydrogen when compared to liquid
hydrogen and, therefore, has a higher volumetric energy content of 15 and 8 MJ/L, respectively.4
Implementation of alternative hydrogen synthetic routes into current technology would require
2

little modification. Additionally, liquid ammonia would only emit gaseous nitrogen and water
vapor, both of which are not harmful to the environment.4 Although the Haber-Bosch process
provides an ample amount of ammonia, the method is energy inefficient and environmentally
disruptive. This process must be improved to meet the future generations needs of food, fuels, and
environment conservation. In this paper, an analysis of all the proposed improvements to the
Haber-Bosch process is reviewed.

Figure 1. Haber-Bosch ammonia synthetic route.

Commented [JK1]: Find better wording

2. Methods
2.1. Cyanobacterium Production of Ammonia
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
2.2. Renewable Energy Alternative
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. The solar cells were assumed to be
polycrystalline photovoltaic panels with power of 215 W, voltage of 26.6 V, and 14.5%
efficiency.2
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).4
2.3. Biomass Gasification Integration
The Aspen Plus software was used to model the gasification process and ammonia production.
A Mixed Integer Linear Programming software was used to simulate the energy system once
biomass gasification implementation.1
2.4. Alteration of Nitrogen Cycle Impact
The Greater Shanghai Area (GSA) was the location of study. The Nitrogen Cycling Network
Analyzer with data compiled from the government and other published papers was used for
analysis.3
2.5. Plasma-Catalytic Synthesis
Low-temperature plasma-catalytic NOx synthesis was performed in a one-sided dielectric
barrier discharge (DBD) 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.5
Table 1. Properties of Support Materials
Support Type

Surface Area (m2g-1)

Relative dielectric constant

-Al2O3

112

9.3-11.5

-Al2O3

.3

9.3

TiO2

34

85

MgO

.03

9.7

BaTiO3

.1

400-6500

.5

4.6

Quartz Wool
5

Data obtained from Patil.

3. Results and Discussion

3.1. Cyanobacterium Production of Ammonia
Using cyanobacteria to form 1000 kg of liquid ammonia is expected to result in a reduction of
3140 kg CO2 in global warming potential (GWP) and 101,300 MJ in non-renewable energy (NRE)
usage. When changes in the algal slurry concentration are made, there is still a reduction in GWP
and NRE (Table 2). 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. Using cyanobacterium
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 production of ammonia via the HaberBosch 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.6
Table 2. Sensitivity of NRE consumption and GWP to algal productivity parameters.

Scenario

Algal biomass

Algal pond

NRE

GWP (kg CO2

concentration

productivity

consumption

eq)

[g(dry

[g(dry

(MJ

biomass)dm-3]

biomass)m-2d-1]

primary)

1a

.23

23.5

-101,300

-3140

2b

.11

9.4

-95,800

-1850

.23

23.5

-62,700

-1680

Base case, summer

Winter

Data from Razon.6

3.2. Renewable Energy Alternative
The Ibiapaba region has the largest potential for production of solar hydrogen with over 181
tons/km2/year. 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. The coastal region has the largest
potential for production of wind hydrogen with over 400 tons/km2/year. Coastal regions experience
a wind speed above 7.0 m/s at 50 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 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.2

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.2

Figure 2. Map of potential for annual production of ammonia from renewable hydrogen (via
Haber-Bosch process) by each municipality, in tons/km2/yr. Figure obtained from Esteues.2
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. Most wind-ammonia plants have a lower
NPV value except for systems where no integration of an ammonia plant and when the ammonia
plant is not used. 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%. Sensitivity analysis of factors pertaining to the system show
that price of diesel fuel and wind speed were the most sensitive. 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. 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 $10.4

Figure 3. Surf plot of the NPV for all wind turbine and ammonia plant combinations
considered. Figure obtained from Morgan.4
3.3. Biomass Gasification Integration
The integrated PEBG system (Case A) when compared to the stand-alone PEBG (SA) system
had an overall increase in energy efficiency of 10%. 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 Myear-1, 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 10-15%.1

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.1

Commented [JK2]: Not sure if I need this

Figure 4. Comparison of Stand-Alone system and Integrated PEBG system. Figure obtained
from Andersson.1
3.4. Alteration of Nitrogen Cycle Impact
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. 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
gross domestic product (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 onechild 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 million. Considering that smaller families live in smaller households that are
less efficient, these factors correlate to a higher nitrogen input after the implementation of this
policy.3
3.5. Plasma-Catalytic Synthesis
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. 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 NO x 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.5

Figure 5. The effect of catalyst support on NOx concentration. Figure obtained from Patil.5

4. 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 lead to a more environmentally-friendly synthetic process of ammonia.2,4 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.1
Plasma-catalytic 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. 5
However, utilizing cyanobacterium and entirely disregarding the hydrogen production
demonstrates the highest potential for an eco-friendly synthetic pathway for liquid ammonia.6

References
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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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