pubs.acs.

org/journal/ascecg Research Article

Achieving +95% Ammonia Purity by Optimizing the Absorption and

Desorption Conditions of Supported Metal Halides
Daniel J. Hrtus, Fouzia Hasan Nowrin, Austin Lomas, Yanick Fotsa, and Mahdi Malmali*

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ABSTRACT: The worldwide push toward the reduction of carbon dioxide emissions has been
the main motivation for finding a sustainable alternative to the conventional Haber−Bosch
ammonia production process that has a significant carbon footprint. In this work, we focused on
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ammonia separation by replacing the condenser with an absorber column packed with metal
halide solid absorbents. These salts had shown promise in selective separation of NH3 in the
past, but more information on the cyclic operation and ammonia desorption conditions was
needed. We used an automated apparatus equipped with an absorption column packed with
either silica, supported CaCl2, or supported MgCl2 to explore the optimal absorption/
desorption conditions (pressure and temperature swings). Primarily, we are reporting on the
working capacity of various sorbents for cyclic ammonia separation. Additionally, we
investigated the effect of sweep gas on the desorption efficiency and compared the absorbent
performance among each other in terms of absorption working capacity and the purity of the
ammonia product stream. We were able to achieve an NH3 stream with a purity of over 95%; in
some of the tests, we achieved a coordination number as high as 2.5 molNH3/molsalt, which is the
highest ever reported for a dynamic flow breakthrough test. Our experiments further prove the significant potential that these salts
possess to replace phase change condensation in the conventional ammonia synthesisnot only in a greener fashion but also more
efficiently with a decreased equipment size, with reduced energy input in smaller scales, and with more flexibility to follow
intermittent renewables.
KEYWORDS: ammonia, support, metal halide, absorption, desorption, purity, distributed manufacturing

■ INTRODUCTION
Ammonia has been the catalyst of the world’s population
encouraged the investment in reducing carbon dioxide
emissions. The first and perhaps the biggest problem with
growth that occurred in the 20th century.1 It is widely accepted the conventional production of ammonia is its reliance on
that without ammonia, a significant portion of the human fossil fuels. Along with cement and steel production, chemical
production is responsible for a significant portion of carbon
population would struggle to survive as it is the main
dioxide emissions.6 Ammonia is the second most-produced
ingredient of a much-needed synthetic fertilizer.2 Other than
chemical;7 its manufacturing takes place in large, centralized
its conventional use, ammonia seems to have a promising
plants far from the end-users. With an energy requirement of
future for indirect hydrogen storage as it has a good hydrogen
30 GJ per ton of ammonia,8 this process accounts for ∼3% of
capacity for implementation in fuel cells.3 Since the beginning
the world’s energy consumption, 5% of natural gas
of the 20th century, ammonia has been produced by the
consumption, and it is responsible for a considerable portion
Haber−Bosch process. The Haber−Bosch process has been
of climate-changing gas emissions.9,10 Some efforts have been
optimized through years of research.4 It has, however, its own
made to make the Haber−Bosh process more sustainable by
flaws that are hard to overlook. This process uses a high-
using pressure swing adsorption to obtain nitrogen from air
temperature catalytic convertor containing an iron-based
and electrolysis of water to produce hydrogen, with both
catalyst to convert a mixture of nitrogen and hydrogen to
processes being powered by wind-generated electricity.11−14
ammonia with relatively low single-pass conversion (10−20%
per pass depending on the convertor’s operating temper-
ature).5 A high temperature is needed to break the stable Received: August 20, 2021
nitrogen−nitrogen bonds, while a high operating pressure Revised: November 18, 2021
(150−200 bar) is required to achieve a reasonable conversion Published: December 17, 2021
for a feasible phase-changing condensation.
The ever-increasing threat of global warming and the
accompanying pressure by the scientific community has

© 2021 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c05668

204 ACS Sustainable Chem. Eng. 2022, 10, 204−212
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Figure 1. Process flow diagram of the experimental setup. Nitrogen and ammonia flow through the mass flow controllers and are mixed before
entering the absorber where ammonia is separated by the sorbent until breaksthrough. The whole process is controlled using LabView. The set
temperature is maintained by the PID controller; pressure, on the other hand, is regulated manually via two valves right before the thermal
conductivity detector.
The idea behind these efforts is that smaller, remotely located
farms might be able to take advantage of stranded renewable
resources to power their own modular ammonia production
plants and use it as a fertilizer for their crops, as a fuel to power
the agricultural machinery, or as an alternative medium for
hydrogen transport.4,11 Although this approach is a step in the
right direction, the green ammonia produced through this
process has been found to cost twice as much as traditional
ammoniaan aspect that is hard to disregard.12 What is more,
wind-generated electricity has its own flaws such as difficulty
with storage and transport and its periodicity. Scientists have
therefore focused their attention on reducing the overall cost of
the process and designing processes that are more flexible with
intermittent renewables. If ammonia production were ever to
happen on a smaller, more particular scale, it would need to
happen under a lower temperature and pressure. Bringing the
operating pressure down would make the whole process more
economically feasible and inherently safer.
The work presented here focuses on the post-reaction
ammonia separation. The Haber−Bosch process traditionally
uses a condenser and therefore requires a chain of heat
exchangers, along with a refrigeration system, to bring the
temperature of the reactor outlet gas down to the ammonia
condensation temperature (−33 °C).15 If the whole con-
densation section were to be replaced by an absorber, such a
change would save a significant portion of capital and
operating costs.16 Our efforts started by making multiple
supported metal halide-based absorbents as these had been
shown to be capable of reproducible separation of ammonia
under cyclic operation.17−19 Supported metal halides selec-
tively separate ammonia; ammonia undergoes a surface solid−
gas reaction and then diffuses into the crystal, while N2 and H2
pass through the column without being absorbed.17 In the
context of this paper, absorption means the reception of
ammonia molecules into the bulk mass of the sorbent material
as opposed to adsorption, which would be the adhesion of a
sorbate to the sorbent active sites. Previous research had
shown that when supported on porous substances, metal
halides exhibit improved capacity as compared to their pure
form.17,18
For any potential scale-up of the proposed absorptive
separation, we are interested in a sorbent material that would
perform consistently under multiple cycles of absorption and
desorption while producing concentrated streams of ammonia.
Consistency in this case means the ability of used salt to take
up and release ammonia in a reasonable time scale in each
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cycle. It is also desirable for the sorbent material to display
longer breakthrough (BT) curves that indicate greater capacity.
The BT time of the first cycle with stable absorbents is the
longest one, and the BT time stabilizes in the subsequent
cycles. This is due to residual ammonia left in the crystals as
fully desorbing it would be costly and inefficient. Therefore,
the initial capacity cannot be used to characterize the sorbents
accurately. It is important to run multiple cycles of absorption
and desorption to gain practical insights into how much of the
initial capacity is lost and what would be the working capacity
of the sorbents.
The experiments that we performed varied in these
conditions: (a) absorption temperature, (b) desorption
temperature, (c) absorption pressure, (d) desorption pressure,
and (e) sweeping gas flow and duration (sweeping gas serves
as a medium to facilitate the transport of the desorbed
ammonia out of the reactor and as a way to decrease ammonia
partial pressure within the column). In the beginning, we
focused on keeping the pressure constant and were only
changing the absorption and desorption temperature
effectively performing a temperature swing absorption
(TSA). Subsequently, the effect of pressure reduction on the
desorption phase was added, therefore performing a pressure
swing absorption (PSA). It is worth noting that pressure was
never the sole changing variable during PSA; therefore,
technically, we were exploring the effect PSA had on TSA as
these two were used together. Lastly, we also included changes
in the sweep time and sweep flow. Three different sorbents
were usedMgCl 2 supported on silica (SiO 2 ), CaCl 2
supported on SiO2, and lastly SiO2 by itself. The comparison
of ammonia uptake and release using different sorbent
materials under similar conditions is a major contribution of
this work. An aspect that is sometimes overlooked in ammonia
absorption studies is the quality of the desorbed gas. In our
work, we were able to achieve an ammonia purity of more than
90%, a number that would help greatly with an argument for
this alternative approach to ammonia synthesis.
The goal of these tests was to observe and define the optimal
conditions for ammonia absorption and desorption using metal
halides. In the past, these materials had shown a potential to be
used in the ammonia production process; however, their
behavior under cyclic conditions has not been described
thoroughly yet, especially the ammonia release. We used an
automated apparatus centered around a packed bed absorber
to perform our experiments. In the following parts of this
paper, we describe how different sorbent materials perform and
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how they compare among themselves. We also show how
changing the parameters of an experiment affects the BT times
and therefore the working capacity of each material.
■ EXPERIMENTAL SECTION
Materials. The sorbent materials used were anhydrous magnesium
chloride (98% purity) and silica gel (60 Å pore size) from Sigma-
Aldrich (St. Louis, MO) and anhydrous calcium chloride (93%
purity) from Alfa Aesar (Haverhill, MA). The ultrahigh purity N2 and
NH3 were purchased from Praxair (Texas City, TX).
Sorbent Impregnation. MgCl2 and CaCl2 were impregnated into
silica gel by a wet impregnation method described before.17 To briefly
describe, 10 g of MgCl2 or CaCl was dissolved in 140 mL of ethanol
in a two-neck round-bottom flask using a magnetic stir bar. The
temperature of the solution was then set to 200 °C and stirred at 600
rpm using an oil bath over a hot plate. A condenser was used to carry
out the impregnation in full recirculation mode. The contents of the
flask were purged with a continuous flow of nitrogen. About 20 g of
SiO2was also dried at 450 °C (ramp: 10 °C/min) under vacuum and
constant N2 flow in a quartz tube. Once dried, the silica was carefully
added to the impregnation solution, and the content was mixed for 2
h. Next, vacuum was pulled over the flask to evaporate the ethanol.
Finally, the impregnated samples were dried in the tube furnace at 450
°C, with a heating rate of 3 °C/min.
Apparatus. The experimental apparatus used in this study is
schematically illustrated in Figure 1. The key component of this setup
is the absorber, which was built from a 1.25 cm OD stainless-steel
Swagelok tubing; the overall length of the column was 30 cm. The
external body of the absorber was wrapped with a flexible heating tape
(Briskheat, Columbus, OH) and insulated using silica insulation tape
(Omega, Norwalk, CT). The temperature inside the column was
measured using a K-type thermocouple (Omega) and was controlled
using an Omega Engineering CN740 proportional integral derivative
(PID) controller. The two inlet gases’ flow rates were controlled using
SLA5850S Brooks Instrument (Hatfield, PA) mass flow controllers.
To control the process pressure, a back-pressure regulator was used
downstream of the absorber column. The pressure was monitored and
recorded using a T2 Ashcroft pressure transducer. Ammonia
concentration in the absorber outlet was recorded using a VICI
Valco TCD-2 thermal conductivity detector (Houston, TX). All the
controlling and instrumentation were connected to National Instru-
ments LabVIEW (Austin, TX) to log data and control the experiment.
Column Packing. 5.4 g of each sorbent was packed into the
column tightly. Two layers of stainless-steel wool were used as the
support on the top and at the bottom to retain the sorbent inside the
column. Next, we installed the column in the flow line. To make sure
that the sorbent was completely dry, the column temperature was
raised to 400 °C with 50 standard cubic centimeters per minute
(SCCM) of N2 sweeping gas to the column for 1 h.
Experimental Procedure. The major variables that were
identified to influence absorption and desorption performance are
temperature, pressure, and sweep gas (N2 in this case) flow. First,
purely TSA tests were designed for each sorbent material separately.
The absorption temperature varied from 25 to 300 °C, while the
desorption temperature extended between 200 and 400 °C. We
selected absorption/desorption temperatures of 100/400 °C and
275.8 kPag (40 psig) for our model experiment. The sweep gas,
introduced to assist with the removal of released ammonia, was
retained at 50 SCCM for 180 s (or 20 SCCM for 60 s in selected
cases). By introducing seemingly short sweep times, we aimed at
exploring the extent to which the column can be regenerated while
keeping the associated operating costs to the minimum. Second, the
TSA/PSA tests were conducted where in terms of absorption/
desorption temperature, the methodology remained the same, while
the pressure of the system was immediately released (from 275.8 to 0
kPag) using the back-pressure regulator. The third round of
experiments was done with a combination of temperature and
pressure swings to further enhance ammonia release. Finally, the effect
of the sweep gas was studied to optimize the ammonia purity.
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Experiment Sequence. A single cycle of our baseline BT
experiment was divided into four phases, as illustrated in Figure 2: (a)
Figure 2. Single absorption/desorption cycle with temperature
depicted vs time. The desorption phase time window is constant
for all experiments and begins with 900 s of temperature ramp-up (b)
until the desorption temperature is reached. This is followed by 900 s
of soaking (c), at the end of which sweep gas flow is introduced to
facilitate ammonia transfer out of the column. The sweep gas varied in
flow rate (50 or 20 SCCM) and time (180 or 60 s). The process ends
with a column cooling (d) during which the sorbent is regenerated.
absorption; (b) temperature ramp-up; (c) soaking; and (d)
temperature ramp-down. Phases (b) through (d) are desorption
phases with 900 s for each experiment. A total of 2700 s was selected
for the ammonia release based on prior results that showed a
reasonable regeneration of the absorbents. In our baseline experiment,
the pressure was set to 275.8 kPa (40 psi). In phase (a), nitrogen and
ammonia flowed through the column at 50 and 10 SCCM,
respectively. Phase (a) ended with the sorbent saturation and,
hence, NH3 BT. Subsequently, the desorption phase (b) began when
the column temperature increased over the 900 s time window until
the desorption temperature was reached. In phase (c), the
temperature was kept constant for another 900 s at the desorption
value. Sweep gas was introduced for either 180 or 60 s at the end of
soaking. Afterward, the last phase of desorption started, and the
temperature was ramped down to the absorption setpoint. The
experiment sequence we described was the TSA. For the PSA, the
pressure was released right after the absorption phase. All the above
describes a single cycle of an experiment. After the cycle, a new cycle
began with the pressure and temperature set to absorption values. A
minimum of five cycles was carried out for each condition to obtain
the initial and working capacities.
Sorption Capacity Calculation. The BT time was defined as the
point at which the ammonia concentration in the outlet stream is 5%
of the inlet stream concentration. Based on BT times, we calculated
the two main characteristics of a sorbent, that is, its coordination
number (molNH3/molsalt) and capacity (mgNH3/gsorbent). The coordi-
nation number can be obtained as follows
̇ )
(BT × VNH3
coordination number = 22 400
ωsalt × msorb
MWsalt (1)
where V̇ is the volumetric flowrate of ammonia in SCCM, ω is the salt
mass fraction in the sorbent, m is the sorbent mass in grams, and MW
is the salt molar mass in g/mol. The coordination number was only
calculated for the metal halide-supported sorbents. Similarly, the
sorbent capacity is defined as follows
̇ )
(BT × VNH
3
× MWNH3
22 400
sorbent capacity =
msorb (2)
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Other than these two parameters mentioned above, the percentage
of ammonia in the desorbed gas (ammonia purity) is an important
parameter reported in our work. During desorption, no gas enters the
column except for the sweeping gas stream (see Figure 4). The
ammonia purity (%) is calculated as follows
̇ × 100
BT × VNH
3
NH3 purity =
̇ ) + (tsw × Vsw
(BT × VNH ̇ ) (3)
3 incomplete regeneration of the absorbent bed, as will be
where tsw is the sweep time in seconds and V̇ sw is the sweep gas
volumetric flow rate in SCCM.
Two types of BT times were observed in each experiment. The first
BT in each test represents the initial capacity of a fully regenerated
column and the highest achievable capacity. After the first cycle, the
BT time tends to decrease as the column may not get fully
regenerated. We repeated the cycling BT tests until steady, and
reproducible BT times were observed. In this article, we use two types
of working capacities: (i) initial capacity, calculated using the 1st
cycle’s BT time using eq 2 and (ii) working capacity that we used to
characterize our sorbents and that is calculated using the 5th cycle’s
BT time in eq 2.
The lag time between the column and the thermal conductivity
detector was approximately 30−90 s depending on the operating
conditions. The column size and the absorber amount were designed
in such way that they would yield higher BT times, therefore negating
the effect of the lag time. The BT times in all the cases were in
thousands of seconds; therefore, the overall lag time led to less than
3% error in BT time. Additionally, such a small error caused by the lag
time translated to a negligible (<1%) difference in the ammonia purity
calculations.
■
RESULTS AND DISCUSSION
In this section, we report the results of our effort to find
conditions that would result in the highest sorbent working
capacity while regenerating the absorber column for cyclic use.
Furthermore, we aimed to achieve higher product gas purity by
optimizing the desorption conditions (temperature, pressure,
and sweep gas flow). Three different sorbent materials were
used, all of which were tested under similar conditions for clear
comparison in performance. An important requirement for
evaluating the sorbents’ performance was the consistency and
reproducibility of the results under cyclic conditions. We
wanted them to display clearly defined and reproducible BT
curves similar to the ones shown in Figure 3. The figure
Figure 3. Relative ammonia concentration profile throughout five
cycles. The conditions were 25/300 °C TSA using supported CaCl2
and sweeping the column at 50 SCCM for 60 s. Cycles 2 through 5
show clear and reproducible BT curves. BT happens at the outlet NH3
concentration equal to 5% of the inlet concentration. While
absorption times were dependent on the absorption parameters and
varied from test to test, the desorption time was fixed at 2700 s for
each test.
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displays five consecutive cycles and BT curves for a 25/300
TSA test using supported CaCl2. Sweep gas parameters were at
50 SCCM for 60 s at the end of the soaking phase. After
breaking through at 6100 s in the initial cycle, the cyclic BT
time decreased and stabilized at around 5000 s, implying a
good absorbent stability under the given conditions. The
reason for the BT time shortening after the initial cycle is an
discussed later. Complete regeneration of the absorbent would
not be feasible due to an extensive TSA and long regeneration
time requirements. As mentioned before, the sorbents studied
here were compared with respect to their cyclic BT rather than
their initial cycle BT. To remain consistent, when reporting
BTs, all experiments continued for at least five cycles, and the
5th cycle’s BT time was used to calculate the working capacity.
Figure 4 illustrates the output information data from a cyclic
TSA test using supported CaCl2 collapsed throughout 40,000
s. The first row shows the cyclic BT times and desorption
stages in one cycle expressed as a fraction of the outlet
ammonia concentration. The second row displays the process
and setpoint values [process value (PV) and set value (SV)]
for the temperatureone can easily see that the temperature
profile (PV) closely follows the designed path shown
previously in Figure 2. As the SV curve shows, the absorption
was carried out at 25 °C, and after the absorption time, the
temperature was stepped up to 100 °C and then ramped up to
300 °C in 900 s. The temperature was held at 300 °C for 900 s
and then stepped down to 250 °C and ramped down to 25 °C
in 900 s at which point the first cycle ended and the next one
began. The PV curves indicate that the column temperature
swiftly followed the SV, only lagging when the temperature
decreased to the ambient temperature in some of the
experiments (no cooling system had been installed). The
third row displays the pressure in the column. The pressure
was maintained at 275.8 kPa g (40 psi g), and it started
dropping as the desorption took place because the N2 inflow
had stopped. Lastly, the fourth row shows the N2 and NH3
flow rate throughout the cyclic operation. In this example, the
N2 sweep gas was set at 20 SCCM for 60 s, and at time = 8800
s, it was introduced to facilitate the desorption. Similarly,
supported MgCl2 and SiO2 yielded repeatable BT profiles.
Focusing on the pressure profile in Figure 4, there are
apparent peaks suggesting the step-wise release of ammonia at
different temperatures, which is typical of materials with
coordination chemistry.20 The detail of these pressure peaks is
shown in Figure 5a. As the arrows indicate on the temperature
axis, the peaks for supported CaCl2 appear at around 90, 140,
230, and 290 °C. Transition temperatures of ammoniated
CaCl2 found in a previous research21 showed desorption at 50,
75, 205, and 250 °C. The two higher desorption points we
observed agree with the reported temperature, with minor
discrepancies. For analysis of the first two desorption peaks (90
and 140 °C), Figure 5c is included as it shows desorption
temperatures from SiO2 saturated with ammonia. For SiO2, the
bulk of ammonia was desorbed at around 165 °C, while a small
release at 75 °C was observed, which was probably caused by
the rapid temperature slope. Circling back to Figure 5a, it is
possible that the two initial releases of ammonia are caused by
or merged with the peak for the ammonia release from SiO2.
This could be also an artifact caused by the fast temperature
ramps and absorber pressure release at the beginning of the
desorption stage. Sørensen et al. reported up to a 50 °C
temperature difference in the gravimetric analysis of the
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Figure 4. Example experiment showing four cycles of a 25/300 TSA test that used supported CaCl2 as the absorbent. The first functionality shows
the actual concentration relative to the maximum concentration. This merit is based on the thermal conductivity detector’s output signal. Following
the line, one can easily spot the BT moment for each cycle. The second dependency shows the temperature profile throughout the experiment,
where PV is the actual sorbent temperature and SV is the designed temperature. The column pressure [kPa gauge] is shown in green, and the
pressure peaks can be interpreted as the ammonia release points. The last functionality shows N2 and NH3 flow in SCCM. The dashed vertical lines
serve only as reference points for easier visual navigation.

Figure 5. (a) Enlarged detail of the pressure profile peaks from Figure 4 showing ammonia release at different stages and their corresponding
process temperature. (b) Ammonia release peaks from a 25/400 supported MgCl2 TSA test (275 kPag with 180 s at a 50 SCCM N2 sweep). (c)
SiO2 absorbent and its ammonia release points (25/200, TSA, 275 kPag, 180 s at 50 SCCM N2 sweep).

amminated metal halide salts when the desorption ramp was
changed from 1 to 5 °C/min (ramp rates in Figure 5 are 37.5
°C/min).21
A previous study reported ammonia desorption peaks from
unsupported MgCl2 at 175, 305, and 400 °C.21 Figure 5b
shows ammonia desorption from supported MgCl2 at 120, 170,
and 380 °Cthe lower temperature again suggests release
from the supporting SiO2 while the other two points match a
208
previous work. Additionally, discrepancies might be caused by
different experimental conditions (especially temperature
ramp). Independently of the four pressure peaks (for CaCl2)
caused by ammonia release, another peak appears (only visible
in Figure 4), caused by the N2 sweep gas in the desorption
stage. This analysis of ammonia release points is crucial in
understanding and optimizing process parameters for ammonia
separation using absorption.
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Figure 6. (a) Ammoniated CaCl2 and (b) ammoniated MgCl2 temperature−pressure-composition diagrams showing their phases with
corresponding coordination numbers.
If we assume that the release temperatures we recorded were
relatively accurate, a major finding of these results is that both
the supported CaCl2 and MgCl2 partially reached their fully
ammoniated form, octa-ammoniated for Ca(NH3)8Cl2 and
hexa-ammoniated for Mg(NH3)6Cl2, suggesting that the
supported absorbents have fast kinetics for ammonia uptake
and release. This finding comes from the stepwise desorption
peaks for both supported salts. The first peak for CaCl2-
supported salt corresponds to the release of 4 mol of NH3, and
formation of Ca(NH3)4Cl2. This structure further breaks down
to Ca(NH3)2Cl2 at 230 °C. At 290 °C, the last mole of NH3 is
released.
It is important to consider whether complete desorption is
possible under the target conditions used. To verify this, the
van’t Hoff equation was used to draw a temperature−pressure-
composition diagram, as illustrated in Figure 6.22 As the
desorption temperature increases, the ammonia is released and
replaces the gas in the absorber column. We assume that by the
end of the temperature ramp-up step [section (b) in Figure 2],
the partial pressure of ammonia is close to the total pressure in
the column. At 100 kPa ammonia partial pressure, the
temperature above 230 °C is sufficient for the ammonia to
be released completely from CaCl2 (Figure 6a). Hence, from a
thermodynamic point of view, ammonia should be released
completely from CaCl2. The same conclusion can be reached
for MgCl2 using the desorption temperatures we used and the
temperature−pressure-composition diagram in Figure 6b. This
suggests that ammonia release from metal halide-supported
salts is kinetically limitedalthough being fast enough to
release a great portion of ammonia in such a short period. This
is probably the major reason why the first BT time was always
longer than the subsequent cycles.
Supported MgCl2 TSA. Most TSA experiments were
performed using supported MgCl2. This is due to the prior
findings by previous reports that studied metal halides and
their ability to absorb ammonia.17,23 Compared to Ca halides,
Mg halide absorbents have shown higher absorption
capacities.11,17 Sorbents will be compared among themselves
later on. There have been doubts cast on the stability of MgCl2
for ammonia uptake and release in multiple cycles and its
degradation after impregnation into porous supports in an
aqueous solution. Prior and current efforts provided by our
team confirm that MgCl2 and supported MgCl2 are chemically
stable, without any change in the chemical structure or
stability.17,18 A prior report found that the degradation CaCl2
in the presence of water vapor is a very slow reaction and
requires several weeks of exposure to humidity.24 It is also
important to note that an ammonia synthesis catalyst is more
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sensitive to water vapor, so there should not be any traces of
water vapor in the gas stream, which satisfies the conditions for
operating MgCl2 salts.
The focus of the results will be initially placed on optimizing
TSA parameters for MgCl2 supported on silica. As seen in
Figure 7, both the initial and the working capacities of the
Figure 7. Effect of absorption and desorption temperatures on the
sorbent capacity in the case of MgCl2 supported on silica. Increasing
the absorption temperature results in lower sorbent capacities
(absorption at 25 °C consistently resulted in the best sorbent
capacities). The figure also provides a look at how much sorbent
capacity was recovered under cyclic useworking vs initial capacity
percentage. In many cases, upward of 50% of the initial capacity was
recovered. The results are ordered based on their working vs initial
capacity percentage.
sorbent increase with a decrease of the absorption temperature.
A lower temperature is thermodynamically more favorable for
ammonia absorption. 21 The best results, hence, were
consistently achieved when the column was operated at 25
°C. It is important to note that a higher temperature is more
advantageous in terms of heat integration (less heat exchanger
surface area). However, ammonia separation at a higher
temperature is not as complete as the separation at 25 °C.
Hence, ammonia is partially recycled back to the reactor, which
reduces the production capacity per unit size of the reactor.
Additionally, the absorbent capacity at 25 °C is significantly
higher than the temperatures above 200 °C.17 Depending on
the choice of the absorber temperature, there is always a trade-
off between the absorbent capacity, the size of the absorber,
the synthesis loop pressure, and the rate of recycle. This is a
multi-objective optimization problem that requires a careful
and dedicated research.
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Again, it is important to distinguish between the initial

capacity (based on the first cycle BT time) and the working
capacity (based on the cyclic BT time). The initial capacity
serves as a basis for how much absorbent capacity can be
recovered after the first cycle. The secondary y-axis in Figure 7
shows the percentage of initial capacity that was recovered.
The results illustrated in Figure 7 show that by decreasing the
absorption temperature toward more thermodynamically
favorable conditions while keeping the desorption temperature
constant at 400 °C, the initial and working capacities can be
improved by at least a factor of 3. The working capacity, on the
other hand, characterizes the performance of the absorbent in
cyclic uptake and regeneration. As expected, the lowest
absorption capacities were achieved at the highest absorption Figure 8. TSA and PSA combined using MgCl2 supported on silica.
The left-hand y-axis shows the sorbent working capacitythat is the
temperature (200 °C). Overall, the sorbent working capacity capacity of whole 5.4 g of the supported sorbent loaded into the
increased by almost threefold when the absorption temper- column and salt working capacityabsorbed ammonia divided by the
ature decreased from 200 to 25 °C (200/400 vs 25/400). salt mass fraction. On the right-hand side y-axis, the coordination
When both absorption and desorption temperature were number is a metric similar to the salt working capacity only expressed
optimized, the working capacity of silica-supported MgCl2 in moles. Experiments with the same temperature parameters are
increased eightfold (200/300 vs 25/350) where the value paired, one without PSA and the other with PSA. The trend is clear
achieved was 147 mgNH3/gsorbent. This improvement in the the introduction of PSA increases the sorbent performance.
loading is primarily attributed to the enhanced driving force for
the ammonia absorption in metal halides at a lower
temperature. According to our thermodynamic calculations
based on the van’t Hoff equation, the required equilibrium
partial pressure to absorb 6 mol of ammonia in MgCl2 is 0.197
and 797 kPa at 25 and 200 °C, respectively. The ammonia
partial pressure in our BT tests was 46 kPa, which exceeded the
equilibrium partial pressure of ammonia to achieve a
hexaammine structure at 25 °C, whereas at 200 °C, the partial
pressure was only sufficient to absorb 2 mol of ammonia. Thus,
the driving force for the absorption dropped significantly when
the absorption temperature increased from 25 to 200 °C.
These results also show that desorption temperatures in the
range of 250−400 °C are viable although there are tradeoffs as
the low temperature (250 °C) results in insufficient ammonia
Figure 9. TSA capacities are compared when experiment parameters
release, while higher desorption temperatures (beyond 400 are maintained but the sorbent material changes. Compared to SiO2
°C) lead to the collapse of the porous structure of the used separately both supported MgCl2 and CaCl2 show drastic
absorbents and reduction in desorption efficiency.25,26 improvements. The salt working capacity is useful to compare salts
Ammonia release from supported MgCl2 shown in Figure 5b among each otherin this case, we saw that MgCl2 showed a slightly
also suggests that ammonia desorption still continues beyond higher working capacity than CaCl2.
300 °C.
Supported MgCl2TSA + PSA. Pressure and temper- TSA tests, we observed a 1.3-fold and a 2-fold increase in the
ature are the two main drivers for ammonia absorption and sorbent working capacity in 100/300 and 25/200 experiments,
desorption. In theory, adding PSA and TSA together should respectively. Both supported metal halide absorbents per-
yield better results than TSA alone. As shown in Figure 8, formed satisfactorily, with MgCl2 showing slightly higher
introducing PSA, in combination with TSA while using working capacities. This is in agreement with the previous
supported MgCl2, increased the sorbent working capacity in findings that Mg-based sorbents are better suited for high-
all the tests. The case of 300/400 is an interesting one as from temperature ammonia absorption when compared to Ca-based
the temperature standpoint, the absorption temperature is ones.21 Overall, the results indicate that the formation of
extremely unfavorable. Still, the introduction of PSA increased strong chemical bonds within the crystal structure of metal
the sorbent working capacity by 1.6-fold. The biggest positive halide salts leads to unparalleled working capacity and
effect was observed in 25/400 where introducing a pressure selectivity at high temperatures, which cannot be achieved
swing led to a 75% increase in all sorption working capacities with adsorbents that rely on weak van der Waals forces.
as compared to the TSA version. In this case, the maximum Unfortunately, very little data are available on dynamic
working capacity achieved was 144 mgNH3/gsorbent. This is a ammonia sorption capacities, and most efforts report static
piece of evidence that combining TSA and PSA has a major (equilibrium) data. None of the data available in the literature
effect on metal halide absorbent performance. report the working capacity of the sorbents and only report the
Different Sorbents Using TSA. Figure 9 confirms that capacity of the fresh (fully desorbed) sorbent. Furtado et al.
metal halides have a remarkable absorption working capacity as reported a dynamic capacity of 150 mgNH3/g for MCM-41
compared to other substances (here, silica was considered for impregnated with ZnCl2 at 298 K.27 The highest static
comparison). With supporting MgCl2 and CaCl2 on silica in (equilibrium) ammonia sorption capacities recorded for
210 https://doi.org/10.1021/acssuschemeng.1c05668
ACS Sustainable Chem. Eng. 2022, 10, 204−212
ACS Sustainable Chemistry & Engineering
various microporous and mesoporous materials are as follows:
301 mgNH3/g for a porous organic polymer at 1 bar,28 208
mgNH3/g for MOF-5 and MOF-177 at 298 K and 1 bar,29 255
mgNH3/g for COF (COF-10) at 298 K and 1 bar,30 and 129
mgNH3/g for an SBA−ionic liquid composite at 1 bar.31 It is
important to note here that metal halides are significantly
cheaper than some of these sophisticated absorbents. In
addition, some of these sorbents have shown a declining
sorption capacity (active surface area) after desorption of NH3.
Designing a support-free stable absorbent for reproducible
performance can further improve the sorption capacity of
metal halides, which is currently a knowledge gap that requires
further investigation.
Sweep Gas Effect. A parameter that has been overlooked
in the past when studying the ammonia absorption and
desorption cycle is the purity of the final product. In most prior
efforts, a continuous flow of sweep gas was used to sweep the
desorbed ammonia from the column.11,32,33 Although
beneficial in enhancing the regeneration of the absorbent,
the use of sweep gas results in dilution of the ammonia product
to concentrations as low as 15%. Figure 10 shows experiments
Figure 10. Desorbed ammonia purity for different temperature
conditions and different sorbents. In most cases, we were able to
achieve 90% + ammonia purity for all the sorbents. Keeping the sweep
time higher and at higher flow rates led to better sorbent regeneration
and a higher working capacity. The tradeoff, however, was that the
final product contained more N2, resulting in a lower NH3 purity.
performed under different absorption−desorption conditions
using all three sorbents and depicts the outlet gas purity, which
was calculated using eq 3. Assuming that the BT time remains
unaffected, with all the absorption and desorption conditions
being similar to those used in 25/300 CaCl2 + SiO2, a
continuous flow of N2 sweep gas during the desorption results
in a final ammonia purity of 26%. The continuous flow of
nitrogen for desorption of supported metal halides has been
utilized in all prior efforts, which can negatively impact the
ammonia purity.11,33 When the sweep time decreased from
2700 to 180 s of sweep gas at 50 SCCM, we were able to
achieve ammonia streams ranging from 70 to 80% purity.
Further decrease of the sweep time and flow rate (20 SCCM
for 60 s) led to even higher outlet ammonia concentrations
above +90% purity (the highest achieved purity was 97.5%).
211
pubs.acs.org/journal/ascecg Research Article
The drawback in further reduction of the sweep gas time and
flowrate is also clear from Figure 10the more we decrease
the sweep gas, the lower the sorbent working capacity
achieved. The sweep gas facilitates the transport of ammonia
out of the column and, at the same time, decreases the
ammonia partial pressure within the column, hence shifting the
desorption toward a more favorable condition. As the sweep
time decreases, the regeneration and release of ammonia are
compromised, thus lowering the sorbent capacity. This tradeoff
must be considered when designing a process and the sweep
gas parameters are going to vary depending on the desired
purity.
■ CONCLUSIONS
This work is a continuation of the effort to find an alternative
to the Haber−Bosch ammonia production process as the
conventional technology heavily relies on fossil fuels and
cannot be integrated with small-scale renewable resources.
Low-pressure reaction−absorption provides a path to small
manufacturing of green ammonia that can match the scale of
commercialized renewable sources. We focused on the post-
reaction part of the reaction−absorption processammonia
separation by absorption. Previously, efforts have been made to
characterize the best materials for ammonia absorption and to
describe the process conditions. While metal halides seem to
be promising candidates, their behavior under cyclic
conditions, particularly sorbent regeneration, needs further
investigation. Our efforts focused on finding the optimal
absorption/desorption parameters for facile ammonia uptake
and release. An automated apparatus for cyclic ammonia
absorption and desorption was designed and built for this
purpose. TSA and PSA experiments with varying temperatures
and pressures were performed to evaluate the sorbent capacity
of three different absorbentsMgCl2 supported on SiO2,
CaCl2 supported with SiO2, and SiO2 on its own. In addition, a
sweep gas (N2) was introduced as another parameter to
facilitate ammonia release from the column. This parameter
was also subject to change because it plays a role in the sorbent
capacity but more importantly in product ammonia purityan
aspect that was rarely considereding previous research. We
were able to achieve more than 90% ammonia purity, a very
promising number. We confirmed that lowering the absorption
temperature and bringing up the desorption temperature yields
the best sorbent capacities. Increasing sweep gas flow and time
is indeed advantageous for obtaining even better sorbent
capacities. However, by doing so, the ammonia purity
decreases. Overall, desorption conditions (temperature,
pressure, and sweep gas) need to be carefully optimized
when designing a cyclic absorption-based process to separate
and purify ammonia.
■
AUTHOR INFORMATION
Corresponding Author
Mahdi Malmali − Department of Chemical Engineering, Texas
Tech University, Lubbock, Texas 79409, United States;
orcid.org/0000-0001-5190-1261; Phone: (806) 834-
8706; Email: mahdi.malmali@ttu.edu; Fax: (806) 742-
3552
Authors
Daniel J. Hrtus − Department of Chemical Engineering, Texas
Tech University, Lubbock, Texas 79409, United States;
https://doi.org/10.1021/acssuschemeng.1c05668
ACS Sustainable Chem. Eng. 2022, 10, 204−212
ACS Sustainable Chemistry & Engineering
Department of Process Engineering, Czech Technical
University in Prague, Prague 6 16607, Czech Republic
Fouzia Hasan Nowrin − Department of Chemical
Engineering, Texas Tech University, Lubbock, Texas 79409,
United States; orcid.org/0000-0003-2787-5985
Austin Lomas − Department of Chemical Engineering, Texas
Tech University, Lubbock, Texas 79409, United States
Yanick Fotsa − Department of Chemical Engineering, Texas
Tech University, Lubbock, Texas 79409, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c05668
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This material is based upon work supported by the U.S.
Department of Energy’s Office of Energy Efficiency and
Renewable Energy (EERE) under the Solar Energy Tech-
nologies Office (SETO) Award Number DE-EE0009802. This
paper describes objective technical results and analysis. Any
subjective views or opinions that might be expressed in the
paper do not necessarily represent the views of the U.S.
Department of Energy or the United States Government.
■
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