Received: 26 October 2020 Revised: 16 January 2021 Accepted: 31 January 2021

DOI: 10.1002/amp2.10077

RESEARCH ARTICLE
Futures

Rapid pressure swing adsorption for small scale ammonia

separation: A proof-of-concept

Bosong Lin | I-Min Hsieh | Mahdi Malmali

Department of Chemical Engineering,

Texas Tech University, Lubbock,
Texas, USA
Correspondence
Mahdi Malmali, Department of Chemical
Engineering, Texas Tech University,
807 Canton Avenue, Lubbock, TX 79409,
USA.
Email: mahdi.malmali@ttu.edu
Abstract
In a typical Haber-Bosch process, a gas stream containing 15–20 mol%
ammonia is obtained from the reactor effluent, and ammonia is then partially
separated in a phase-changing condensation unit. When operating at lower
pressure for distributed manufacturing, the single-pass conversion drops to less
than 10 mol%, which makes the condensation more cost-intensive. A small
adsorber is proposed for concentrating ammonia through rapid pressure swing
adsorption (RPSA) that fits the small-scale processing. A mathematical model
is developed to evaluate the feasibility of the RPSA process for ammonia sepa-
ration with high recovery. The ideal adsorbed solution theory, based on the
Freundlich single-component isotherm model, is proposed to predict binary
isotherms for various commercially available adsorbents. The performance of
the RPSA-assisted adsorber is then studied at different process conditions for
concentrating ammonia. The effect of various operating variables such as
exhaust flow rate, cycle time, and feed pressure, is investigated. The proposed
numerical model shows that nearly pure ammonia can be continuously pro-
duced at optimized conditions, with more than 95% recovery. This low-
pressure RPSA-assisted adsorber can be used to design modular ammonia
devices for distributed manufacturing. Our proposed technology can be further
extended to concentrate other dilute gas mixtures, such as carbon dioxide.

KEYWORDS
ammonia separation, Haber-Bosch process, ideal adsorbed solution theory, low-pressure
manufacturing, modular adsorption processes, rapid pressures swing adsorption

1 | INTRODUCTION efficiency of the HB process and to lowering the capital

1.1 | Small-scale ammonia production
The emergence of the Haber-Bosch (HB) process made a
significant impact on the production of agricultural fertil-
izers over the last century. The increase in synthetic fer-
tilizer production dramatically boosted food production
and is currently responsible for feeding nearly half of
the world's population.[1] A century of research and
development has been dedicated to improving the
and operating expenses.[2] The state-of-the-art, large-scale
ammonia process relies on steam methane reforming
(SMR) and cryogenic air sepration to produce hydrogen
and nitrogen, respectively. Ammonia is then produced at
high temperatures (400–500
C) and high pressures (150–
300 bar). High temperature is needed to accelerate reac-
tion kinetics while high pressure is required to increase
the single-pass conversion. Although extensively opti-
mized, the SMR-based ammonia is still energy- and
capital-intensive. In order to reduce the overall costs,

J Adv Manuf Process. 2021;3:e10077. wileyonlinelibrary.com/journal/amp2 © 2021 American Institute of Chemical Engineers 1 of 15
https://doi.org/10.1002/amp2.10077
2 of 15
ammonia manufacturing takes place in large, centralized
plants far from the end-users, with an approximate
energy requirement of 28 GJ per ton of ammonia.[3] This
key process consumes 2% of the global natural gas pro-
duction and generates 1.2% of the global anthropogenic
CO2 emissions.[4,5]
Recently, green ammonia produced from renewable
resources has been considered as an alternative to the con-
ventional fossil-based technology. Not only is ammonia a
pathway for distributed fertilizer production in remote
locations, but it is also proposed as a medium for short-
and long-term energy storage. It is particularly interesting
because of its high hydrogen content (17.7 wt.%) and
exceptional gravimetric energy density (3 kWh/kg).[6]
Since renewable resources are available in small scale and
are geographically distributed, distributed ammonia
manufacturing in milder conditions has become an area of
interest. Renewable and decentralized ammonia produc-
tion can be a cost-effective path for sustainable fertilizer
production and thermochemical energy storage of renew-
able resources based on the extensive knowledge available
for this chemical process, its lower module costs, and sav-
ings in transportation and distribution when deployed
locally.[7–9]
1.2 | State-of-the-art ammonia
separation technology
The single-pass conversion in a conventional ammonia
convertor is only about 15%–20%[2]; thus, to improve the
yield, it is necessary to separate ammonia from the reac-
tor effluent and recycle unreacted nitrogen and hydrogen
back to the convertor. In conventional ammonia produc-
tion, ammonia is separated using phase-changing con-
densation at high pressure (300 bar) and low temperature
(25
C) with water cooling. For lower pressure
manufacturing (150 bar), a refrigeration system is
required to achieve the lower condensation temperature
necessary to condense ammonia.[10] Since gas compres-
sion and refrigeration are two major contributors to the
total energy consumption in ammonia manufacturing,
there is a critical need for designing separation processes
that reduce the process energy consumption.[2,10,11] One
approach can be to replace phase-changing separation
with a more energy-efficient unit operation. It is widely
accepted that exploiting separations which obviate the
phase-changing can lead to energy savings up to one
order of magnitude.[12]
Few attention has been directed toward exploring
alternative separation methods for small-scale ammonia
manufacturing.[13] Unconventional methods for ammo-
nia separation can be classified into two groups based on
LIN ET AL.
the underlying separation mechanisms: ammonia adsorp-
tion and ammonia absorption.[9,14–17] In either methods,
the selected adsorbents and absorbents should have
excellent ammonia selectivity over other gases present in
the multicomponent mixture (hydrogen and nitrogen),
and sorbents should be regeneratable through pressure or
temperature swings, or a combination thereof.[18] Pres-
sure swing adsorption (PSA) methodologies developed in
the 1960s have been widely used for the separation and
purification of gas mixtures, and it consists of four
major steps: pressurization, adsorption, blowdown, and
purge.[19] For instance, Knaebel and Cussler established
and proposed a multistep PSA scheme for ammonia sepa-
ration, in which an enriched ammonia stream was used
to push the unabsorbed gas in the bed to obtain pure
ammonia during desorption.[17] Later, more advanced
concepts were proposed which focused on combining
PSA methodologies with a reaction. A reaction-
adsorption process that incorporated a synthesis reactor
and multiple adsorption units was demonstrated for
continuous ammonia synthesis and recovery.[20] Matito-
Martos et al. used Monte Carlo simulations and inte-
grated ammonia synthesis and adsorption, showing that
confinement of the ammonia synthesis reactor by adsor-
bents improved the ammonia synthesis conversion and
rates.[21] Some of the recent efforts toward enhanced
ammonia synthesis have been dedicated to low-pressure
ammonia manufacturing that can reduce capital and
operating costs.[10] Recently, an innovative, but simple,
reaction-absorption process is proposed that enables
ammonia production at 10–20 times lower pressure while
producing ammonia at rates comparable to those of con-
ventional process operating at high pressure.[22,23] A
major feature of the absorption-based separation is that
the absorber column, which is packed with metal halide
absorbents, can separate ammonia more completely at
significantly lower ammonia concentrations.[9,24] Rapid
separation achieved at fast recycle rates in the reaction-
absorption process can compensate for the reduction in
the reaction rates due to lower pressure processing.
Unlike adsorption, which is a surface-based phenome-
non, absorption relies on gas–solid reactions followed by
bulk diffusion within the solid absorbents. Therefore, it
allows separation at higher temperature with 100% selec-
tivity for ammonia.[23,25]
1.3 | Scope of this study: Rapid pressure
swing adsorption-assisted adsorber
Extensive efforts have been reported on ammonia synthe-
sis at milder conditions. Novel promoted Ru-based cata-
lysts can produce ammonia at pressures as low as 1 bar
LIN ET AL.
and 573 K.[26,27] Although operating at lower tempera-
tures, the single-pass conversion is typically very low,
which makes it impractical to retrieve ammonia from the
reactor effluent using conventional separation processes.
PSA-based technologies can be applied for separation of
dilute ammonia. Various PSA technologies, such as dual-
reflux PSA and rectifying PSA, have been applied to con-
centrate dilute gas streams.[28–31] Intensified PSA technol-
ogies, such as rapid pressure swing adsorption (RPSA),
can be utilized to obtain shorter cycle times and a higher
productivity. RPSA has been widely applied in gas sepa-
rations due to fast cycling and efficient separation.[32] For
instance, Turnock and Kadlec proposed rapid oscillating
adsorption for separating nitrogen from methane.[33]
Later, piston-driven RPSA was introduced by Eriksson[34]
and was then extended to dual-piston assisted RPSA by
Keller and Kuo.[35] This work is focused on evaluating a
conceptual scheme of RPSA-assisted adsorber for separat-
ing ammonia from a dilute gas mixture exiting the HB
reactor.
The purpose of this work is to demonstrate the feasi-
bility of the RPSA-assisted adsorber, which can be even-
tually adopted for small-scale ammonia production. We
developed a detailed mathematical model for the pro-
posed technology, using binary adsorption isotherms
determined by the ideal adsorbed solution theory
(IAST). We investigated the performance of the RPSA
process for ammonia separation in terms of several
important process variables. Results suggest that con-
centrated ammonia streams (+95 mol%) can be
obtained from the synthesis gas using ammonia-
selective adsorbents. The RPSA-assisted adsorber
enables continuous ammonia production when inte-
grated with a modular ammonia reactor for distributed
manufacturing. Our proposed RPSA process can be fur-
ther extended and utilized for concentrating other
dilute gas mixtures (e.g., CO2).
2 | METHOD OLOG Y
This modeling effort seeks to design a small RPSA-
based process for simultaneous separation and concen-
tration of ammonia produced from a low-pressure HB
reactor. The gas mixture in the reactor exhaust is com-
posed of nitrogen and hydrogen in stoichiometric ratio
and approximately 10 mol% ammonia. For the simplic-
ity of the modeling approach, we assumed that hydro-
gen interaction with adsorbents is weak and similar to
that of nitrogen. Hence, hydrogen was presumed to be
approximated by nitrogen. Such assumption is not far
from reality as prior literature suggests that both hydro-
gen and nitrogen are less competitively adsorbed
3 of 15
(compared to ammonia) in the adsorbents selected for
this work. A report by Matito-Martos et al. suggests that
the loading of hydrogen on commonly used adsorbents
such as 4A and Faujasite (FAU) is much lower than
that of nitrogen and almost negligible compared to that
of ammonia.[21] In addition, experimental studies on
hydrogen separation from gas mixtures using activated
carbon (AC) and zeolites suggests that hydrogen is the
least adsorbed component .[36,37] Therefore, for simplifi-
cation of the modeling approach, we only considered
the mixture of nitrogen and ammonia for the RPSA
process.
2.1 | Single-component adsorption
isotherm
Adsorption isotherms of NH3 and N2 are already
investigated and reported for various adsorbents. Sev-
eral zeolites (13X, 4A, 5A, and FAU), silica gel (Si),
and AC were chosen as the candidates for RPSA stud-
ies in this work. The adsorption isotherms of pure
NH3 and N2 at 298 K were obtained from the litera-
ture and are illustrated as markers in Figure 1.[21,38–
42]
The data points obtained from experimental and
simulation results can be well represented by the
Freundlich model:
N i = k i P1=ni ð1Þ
where Ni (mol/kg) and P (bar) are the amount of gas
adsorbed in the adsorbent and the equilibrium pres-
sure, respectively. ki and ni are Freundlich isotherm
constants for component i. After fitting the data from
the literature, ki and ni were found and are summa-
rized in Table 1 for the six adsorbents selected for this
study.
The adsorption isotherms of NH3 and N2 displayed in
Figure 1 suggest that the adsorption capacity for NH3 is
significantly higher than that of N2 at the same tempera-
ture and pressure. Table 1 shows that the sorption uptake
capacity on 4A at 298 K reaches 9.83 mol NH3/kg and
0.41 mol N2/kg at 1.5 bar and further increases to
10.9 mol NH3/kg and 0.64 mol N2/kg at 3 bar. The 4A
zeolite adsorbent is interesting, as it shows the largest dif-
ference between the ammonia and nitrogen equilibrium
capacity at any specific condition. As displayed in Fig-
ure 1, 13X displays the largest ammonia uptake among
six adsorbents at lower ammonia partial pressure. Hence,
13X was chosen as the model adsorbent for this work to
evaluate the performance of the RPSA process at different
process parameters.
4 of 15 LIN ET AL.

F I G U R E 1 Adsorption
isotherms of (A) NH3 and (B) N2 at
298 K. Data points were extracted
from references: NH3,[38] N2 -
13X,[39] 4A,[40] 5A,[41] Si,[42] AC,[39]
and FAU.[21] The fitted Freundlich
isotherm models displayed with
solid lines predict the uptake of
gases adsorbed on six adsorbents

T A B L E 1 Fitting parameters for

Adsorbent ki ni Uptake at 1.5 bar Uptake at 3.0 bar
the Freundlich isotherms of pure NH3
NH3[38] and N2 on 13X, 4A, 5A, Si, AC, and
13X 9.77 7.69 10.3 11.3 FAU at 298 K
4A 9.25 6.71 9.83 10.9
5A 7.91 8.76 8.28 8.97
Si 6.42 4.07 7.09 8.41
AC 4.40 1.61 5.66 8.71
FAU 1.73 2.06 2.11 2.95
N2
13X[39] 0.73 1.63 0.93 1.43
4A[40] 0.31 1.56 0.41 0.64
[41]
5A 0.76 3.19 0.86 1.07
[42]
Si 0.06 1.00 0.08 0.17
AC[39] 0.41 1.21 0.57 1.02
[21]
FAU 0.23 1.26 0.32 0.56

2.2 | Binary adsorption by IAST component i at the mixture sorption conditions (T and
π).[43] The spreading pressure can be obtained by inte-
The IAST model was applied to obtain the Freundlich grating Equation (5):
binary adsorption isotherms based on the Freundlich
single-component adsorption model.[43] Using the anal- Pði 0

0  RT N i ðPi Þ
ogy of Raoult's law for vapor–liquid equilibria, the IAST π Pi = dPi ð5Þ
model leads to: A Pi
0

Pyi = Pi = x i P0i ðπ Þ for i = 1, 2 ð2Þ

x1 + x2 = 1
y1 + y2 = 1
where xi and yi are mole fractions of component i in the
adsorbed phase and gas phase, respectively; P is the total
pressure in the gas phase; Pi is the partial pressure of
component i; and P0i ðπ Þat the corresponding temperature.
Thus, P0i ðπ Þ is the pure adsorbate vapor pressure for the
where the spreading pressure π is a thermodynamic vari-
ð3Þ able and can be calculated from the experimental adsorp-
tion isotherm. R is the gas constant, and A is the specific
ð4Þ area of the adsorbent. Integration of Equation (5) at the
lower limit (p = 0 Pa) is undefined, so our calculations
used an approximation at p = 0.0001 Pa.
For a given total pressure (P) and mole fraction in the
gas phase of component i (yi), five equations were
obtained from Equations (2), (3), and (5) for a binary sys-
tem. This resulted in five unknowns—x1, x2, P01 , P02 , and
π. Solving these equations numerically gave a solution
LIN ET AL.
for the unknowns, from which the total amount of the
adsorbate (Nt) can be calculated:
1 x1 x2
=
 +
0
N t N 1 P01 N 2 P2

 Nt is the total amount of gases adsorbed and
where
N i P0i is the amount of the component i adsorbed at the
spreading pressure π and temperature T, in the absence
of the other component in a binary mixture.
The relative volatility (α1,2) and selectivity coefficient
(S2,1) for binary mixtures is defined as:
y1=y 1
α1,2 = 2
= = S2,1
x 1=x S1,2
2
where α1,2 is equal to S2,1 which is defined as the selec-
tivity coefficient for the more adsorbed gas with respect
to the other less adsorbed component. In this work, pure
adsorption isotherms of NH3 and N2 on six adsorbents at
298 K were used to calculate Freundlich binary adsorp-
tion isotherms using the aforementioned equations.
2.3 | RPSA process description
The RPSA-assisted adsorber consists of a fixed bed
column in which a certain component can be selec-
tively adsorbed and separated from a gas mixture.
Unlike a four-step Skarstrom cycle,[19] the RPSA-
assisted adsorber involves only rapid adsorption and
desorption cycles inducing the separation of gas mix-
ture. A schematic diagram of the RPSA-assisted
adsorber is shown in Figure 2. A three-way solenoid
valve at the adsorber inlet regulates the gas flow at
the feed and product ends, and an orifice at the
exhaust end allows adjustment of the exiting gas flow
rate. A gas mixture of 10 mol% NH3 and 90 mol% N2
is supplied to the RPSA system at a certain pressure
during the first half cycle. Due to the small pressure
difference along the bed, the gas mixture flows from
the feed end toward the exhaust end with a small resi-
dence time in the adsorber. NH 3 is preferentially
retained in the adsorbed phase at higher adsorber
pressure while N 2 is being concentrated along the bed
to flow gradually toward the exhaust end. In the sec-
ond half cycle, the three-way valve actuates to the
product line where the adsorber pressure drops, and
the ammonia in the adsorbent phase is released,
expanded, and flows toward the product end. The
rapid operation of these half cycles could eventually
separate the desired gas (NH 3) from the feed after a
series of quick, continuous cycles.
5 of 15
ð6Þ
ð7Þ F I G U R E 2 Schematic of the RPSA-assisted adsorber. Feed gas
mixture of 10 mol% NH3 and 90 mol% N2 enters the adsorber in the
first half cycle (left-hand side). The less adsorbed gas (N2) leaves the
bed from the exhaust end while the more adsorbed gas (NH3) is
enriched at the product end. A concentrated ammonia stream
leaves the adsorber through the product line in the second half
cycle (right-hand side). The blue line denotes adsorption while the
orange line represents desorption. Two steps run consecutively in a
rapid manner
2.4 | Model equations
For the mathematic model of the RPSA-assisted adsorp-
tion process, the following assumptions are considered:
1. Idea gas behavior is considered.
2. An instantaneous equilibrium adsorption model is
considered.
3. Axial dispersion is negligible (Pe > 100, see details in
Appendix A).[44]
4. Adsorption equilibrium can be well predicted by
Freundlich isotherm.
5. The IAST model accurately predicts binary adsorp-
tion of NH3 and N2.
6. Darcy's law characterizes the gas flow along the bed
(see details in Appendix B).
7. Particle size and bed voidage are uniform for all the
adsorbent selected.
8. Gas viscosity is independent of the pressure and
composition.
9. Selectivity coefficient is constant.
10. Separating ammonia from the mixture by RPSA is
assumed to be isothermal due to its small scale
nature.
The model equations for the RPSA are already com-
prehensively derived by Turnock and Kadlec.[33] The
governing equations for the overall and single-
component material balances are given in Appendix C,
6 of 15 LIN ET AL.


which can be formulated in the dimensionless form p2F =p2a , 0 < θ≤1=2
shown below. Pð0,θÞ = ð13Þ
1, 1=2 < θ≤1
The dimensionless variables are defined as follows:
 
KA ∂PðX, θÞ V pa ∂Pð1, θÞ
2
P = PðX, θÞ = ½pðX, θÞ =p2a ð8Þ − = CQe +
2V m μLT ∂θ X =1 2RTλPð1, θÞ 1=2 ∂θ

X = l=L ð9Þ
For 0 ≤ X ≤ 1,
θ = t=λ ð10Þ
PðX, 0Þ = 1:0, for the 1st cycle: ð14Þ

where X and θ are the dimensionless length and time var- PðX, 0Þ for the mth cycle = PðX, 1Þ for the ðm −1Þth cycle:
iables, respectively.
The overall material balance can be given: The overall governing equation is a second-order par-
tial differential equation (PDE), which was converted
∂ 2 PðX, θÞ ∂PðX, θÞ into a set of ordinary differential equations (ODEs) using
= F ðθ Þ ð11Þ
∂X 2
∂θ the method of lines.[45] The set of ODEs was then solved
numerically by ODE45 in MATLAB® to obtain the pres-
where F(θ) is defined as a function of process parameters sure profile along the adsorber bed at any instant of the
formulated as: cyclic operation.
The oscillating pressure profile along the adsorber
 
TμV m L2 Aϕ 1 kW ð1=n − 1Þ 1 bed obtained from solving Equation (11) was used to cal-
F ðθ Þ = + p ð12Þ
T a KAλ RT P1=2 nL a Pð1 − 1=2nÞ culate the molar gas flow rate (qm) using Darcy's law,
outlined as follows:

where T is the temperature; μ is the gas viscosity, Vm is the T a p KA 1 dp

qm = − ð15Þ
molar volume; L is the bed length, Ta is the reference tem- T pa μ V m dl
perature, pa is the reference pressure, K is the permeability
of the bed, A is the cross-sectional area, λ is the cycle where dpdl represents the pressure gradient in the axial
time of the RPSA process, ϕ is the bed voidage, W is the direction of the adsorber column. Here, qm can be
weight of the adsorbent, and Nt is the total amount of obtained from the dimensionless discretized form as:
gases adsorbed. k and n are the Freundlich binary adsorp-
 
tion isotherm constants defined in Equation (1). They T a KA Pð1 −ΔX,θÞ −Pð1, θÞ
qm ð1,θÞ = ð16Þ
were obtained by solving the IAST model at various pres- 2Tpa μLV m ΔX
sures based on single-component adsorption isotherms at
298 K and the target feed composition. k and n for differ- where qm(1, θ) is the molar gas flow rate at the adsorber
ent adsorbent are summarized in Table 2. end (X = 1). P(1 − ΔX, θ) and P(1, θ) are the dimension-
The boundary and initial conditions used to solve the less pressure at the last two nodes of the adsorber outlet.
governing equation are given: The qm(X, θ) at any adsorber location can be calculated
from the integration of Equation (17):

ð1
T A B L E 2 Fitting parameters for the Freundlich binary ∂PðX, θÞdX
qm ðX,θÞ = qm ð1, θÞ + GðX, θÞ ð17Þ
isotherms for 10 mol% NH3-90 mol% N2 on 5A, 4A, 13X, Si, AC, ∂θ
and FAU at 298 K X

Adsorbent k n
where G(X, θ) can be calculated as follows:
5A 6.1 8.7
" #
4A 6.6 6.7 L Aϕpa kW pa 1=2
GðX, θÞ = + ð18Þ
13X 7.3 7.6 2λ RTPðX, θÞ1=2 n L PðX, θÞð1 − 1=2nÞ
Si 3.7 4.0
AC 1.2 1.5
Similarly, considering single component adsorption
FAU 0.6 1.9
from the gas mixture, the use of relative volatility (α)
LIN ET AL. 7 of 15

defined in Equation (7) can facilitate the computation of Similarly, the N2 Recovery and purity in the exhaust
single-component material balance in the system as line are defined:
follows:
Total moles of N2 in the exhaust line in one cycle
RN2 , E =
∂yðX, θÞ ∂yðX, θÞ Total moles of N2 in the feed line in one cycle
qm ðX, θÞ + f ðX, θÞ + hðX, θÞyðX, θÞ = 0
∂X ∂θ × 100%
ð19Þ ð26Þ

where f(X, θ) and h(X, θ) can be defined as a function of

Total moles of N2 in the exhaust line in one cycle
the process parameters: PN2 , E =
Total moles of gases in the exhaust line in one cycle
" # × 100%
1=n
1 ALϕPðX, θÞ1=2 pa pa PðX, θÞ1=2n Wkα
f ðX, θÞ = + ð27Þ
λ RT ½α − ðα−1ÞyðX,θÞ2
ð20Þ To evaluate the performance of various adsorbents
for NH3 recovery, the adsorbent productivity was
 
pa PðX, θÞð1=2n − 1Þ Wk
1=n
1 calculated[47]:
hðX, θÞ = −1
2λn α − ðα−1ÞyðX, θÞ
∂PðX, θÞ Productivity
∂θ Total moles of NH3 in the product line in one cycle
=
ð21Þ Volume of adsorbent × Total cycle time
The boundary and initial conditions are given: ð28Þ

yð0, θÞ = yf ð22Þ
3 | RESULTS A ND DISCUSSION
For 0 ≤ X ≤ 1:
The IAST was used to predict the binary adsorption iso-
yðX,0Þ = 1:0 for the 1st cycle: ð23Þ therms of six adsorbents for the NH3-N2 mixture. The iso-
therms were then incorporated into the process model.
yðX, 0Þ for the mth cycle = yðX, 1Þ for the ðm −1Þth cycle: The 13X adsorbent was chosen as the model adsorbent to
conduct a more comprehensive analysis of the effect of
The calculated cyclic steady-state pressure profile P important process variables on the performance of the
(X, θ) and the molar gas flow rate qm(X, θ) were used to proposed RPSA process.
calculate the gas phase composition y(X, θ). The gas
phase composition is a first-order parabolic partial differ-
ential equation that can be solved by the method of 3.1 | Binary adsorption
characteristics.[46]
Predicted binary isotherms for six adsorbents at different
pressures are shown in Figure 3. It is important to note
2.5 | Performance metrics that both NH3 and N2 equilibrium loadings are plotted
versus mole fraction of NH3 in the gas mixture for the
To evaluate the performance of the designed RPSA, the NH3 ease of comparison. A key finding from the binary iso-
recovery and purity in the product line are formulated: therms is that the adsorbents are more selective toward
ammonia and have a higher ammonia adsorption uptake
Total moles of NH3 in the product line in one cycle at similar conditions. This is favorable for our proposed
RNH3 , P =
Total moles of NH3 in the feed line in one cycle RPSA process, as ammonia is the desired compound to
× 100% be separated from the gas mixture. When considering the
ð24Þ composition of the gas effluent from an HB reactor
(10 mol% NH3), it can be found that the amount of
Total moles of NH3 in the product line in one cycle ammonia adsorbed on 13X will be about 200 times
PNH3 , P =
Total moles of gases in the product line in one cycle greater than that of nitrogen, indicating that nearly 99%
× 100% of adsorbed gas is ammonia. Among isotherms predicted
ð25Þ for the NH3-N2 binary system, 13X displayed the highest
8 of 15
F I G U R E 3 Amount of NH3 and N2 on six adsorbents at 298 K and different pressures (A) 1.5 bar, (B) 3 bar, (C) 6 bar, and (D) 12 bar.
13X (green), 4A (red), 5A (black), Si (blue), AC (cyan), and FAU (magenta)
ammonia sorption capacity of 7.64 mol/kg. Similar to
13X, other adsorbents are more selective for ammonia at
1.5 bar. Results indicate that the loading of ammonia in
the adsorbents decreases in the following order:
13X > 4A > 5A > Si > AC > FAU.
Table 2 summarizes the Freundlich binary isotherm
parameters, k and n, for different adsorbents selected for
this work. These parameters were obtained from solving
the IAST model at various pressures based on single-
component adsorption isotherms at 298 K and feed com-
position of 10 mol% NH3. The binary adsorption model
for six adsorbents will be used in the simulation of the
proposed RPSA process.
Another important observation from the predicted
binary isotherms is that increasing the total pressure sacri-
fices the ammonia selectivity as the nitrogen uptake
increases more significantly, while leading to higher
adsorption capacities for both gases. Results suggest that
the increase in the pressure more notably influences the
NH3 and N2 adsorption capacities in AC. Overall, it can be
deducted that lower pressure is more favorable for ammo-
nia recovery. Therefore, we proceeded with 1.5 and 3 bar
as our target operating pressures, which are within the
range we envision for small, distributed ammonia
production.
For NH3-N2 binary system, the selectivity for the
more adsorbed gas was calculated using Equation (7),
and the results are displayed in Figure 4. Notably, the
LIN ET AL.
ammonia selectivity decreases as the ammonia mole frac-
tion in the gas phase increases. For instance, the selectiv-
ity of 5A decreases from 5 × 104 to nearly one at 298 K.
This is primarily attributed to the fact that the nominator
in Equation (7) remains constant, while the denominator
exponential increases as ammonia concentration
increases. Overall, selectivity results suggest that FAU
and AC have relatively lower ammonia selectivity than
other adsorbents. The ammonia selectivity of these adsor-
bents is in the following descending order:
5A > 4A > 13X ≈ Si > AC ≈ FAU. It should be noted
that there is a possibility that IAST overestimate the
adsorption selectivity. Hence, experimental work on the
binary adsorption isotherms will be required to confirm
the predicted results.
3.2 | RPSA cyclic profile
The adsorber column design parameters for the proposed
RPSA process are summarized in Table 3. The column
length was considered to vary between 0.05 and 0.09 m
with a fixed diameter of 0.021 m. The column voidage
and average adsorbent size were estimated, and bed per-
meability was calculated from Kozeny–Carman equa-
tion.[48] The effect of a few important variables, such as
the exhaust flow rate and cycle time on the performance
of the RPSA, were investigated.
LIN ET AL. 9 of 15

F I G U R E 4 Selectivity of
ammonia over nitrogen for six
adsorbents at (A) 1.5 and (B) 3 bar
and 298 K. 5A (black), 4A (red),
13X (green), Si (blue), AC (cyan),
and FAU (magenta)

T A B L E 3 Characteristics of the RPSA-assisted adsorber for

ammonia separation from a dilute gas mixture

Parameter Symbol Value/range

Column voidage ϕ 45%
−4
Adsorbent size (×10 m) dp 1.25
−11 2
Permeability (×10 m) K 2.50
Column diameter (m) D 0.021
Temperature (K) T 298
Parameters investigated
Exhaust flow (×10−6 m3/s) QE 4.75–11.0
Column length (m) L 0.05–0.09
Feed pressure (bar) P 1.5–3.0
Cycle time (s) λ 2.0–14

The set of PDEs proposed for the RPSA process in

Section 2.4 was solved for the six adsorbents selected,
with the base operating conditions being P = 1.5 bar,
T = 298 K, QE = 4.75 × 10−6 m3/s (1.93 × 10−4 mol/s),
λ = 10 s, L = 0.05 m, and yNH3 = 10 mol%. Figure 5 illus-
trates the overview of simulation results for the RPSA
process using 13X adsorbent, during operation in three
consecutive cycles. Figure 5A displays the pressure pro-
file within the adsorber at the feed and exhaust ends. The
pressure in the bed is controlled by switching the inlet
three-way valve which periodically introduces the feed to
the adsorber during the first half cycle. Ammonia is pref-
erentially adsorbed at higher pressure during the first
half cycle, while nitrogen is being gradually transported
to the exhaust end due to the pressure difference across
the adsorber packed bed. The first half cycle is followed
by the release of the pressure caused by switching the
three-way valve to the product line. Ammonia is then
desorbed at lower pressure in the second half cycle. The
pressure profile suggests that the pressure instantly
F I G U R E 5 Overview of the cyclic response of the proposed
RPSA-assisted adsorber packed with 13X at the base condition of
P = 1.5 bar, T = 298 K, QE = 4.75 × 10−6 m3/s, λ = 10 s, and
L = 0.05 m. (A) Pressure profile at the feed and exhaust ends;
(B) Molar flow rate of the gas mixture at the feed and exhaust ends
(the red and blue lines denote the cyclic profile at the feed and
exhaust end, respectively); and (C) average flow rate (magenta) and
ammonia mole fraction (black) at the feed (product) end
increases and then decreases right after the three-way
valve switches. The pressure at the exhaust end reaches
nearly 1.5 bar at a time constant of about 1 s (time con-
stant defined as the time required to achieve 63.2% of the
overall change of a variable).
Figure 5B shows the cyclic changes in the molar flow
rate of the gas mixture at the adsorber feed and exhaust
10 of 15
ends. The pulse denotes the highest instantaneous molar
flow rate of 0.065 mol/s at the beginning of the half cycle,
followed by a rapid change in the flow at the inlet. As the
gas mixture moves from the inlet toward the exit, the
molar flow rate decreases due to the shrinking pressure
gradient along the column, as displayed in Figure 5A.
Figure 5C displays the calculated average volumetric flow
rate at the inlet of the absorber, which was obtained by
integrating the flow rate over time. The data reveal that
the average inlet flow rate of the pulse during the adsorp-
tion is about 1.12 × 10−5 m3/s, and it decreases to
6.42 × 10−5 m3/s during desorption. The decrease in the
flow rate on the inlet side of the adsorber is because of
the release of a portion of the nitrogen from the exhaust
line. A 10 mol% NH3 was fed to the adsorber, and the
ammonia purity in the product stream increased to about
17.5% at the base conditions, at time that steady state was
achieved.
3.3 | Effect of exhaust flow and
cycle time
Figure 6 illustrates the effect of the exhaust volumetric flow
rate on the performance of the RPSA adsorber at different
cycling times. 13X adsorbent was used for this analysis.
Since 13X zeolite has excellent ammonia selectivity over
nitrogen, more than 95% of ammonia can be potentially
recovered from the gas stream at optimized conditions,
which can subsequently lead to producing a highly concen-
trated N2 gas (>99%) stream in the exhaust line. The purity
of NH3 in the product line and the recovered N2 in the
exhaust line versus the exhaust flow rate at different cycle
times are displayed in Figure 6A,B. It is apparent that
increasing the exhaust flow rate (from 4.75 × 10−6 to
1.1 × 10−5 m3/s) and the cycle time (from 2 to 14 s) results
in an increase in NH3 purity in the product line and N2
recovery in the exhaust line. The best performance can be
achieved when QE = 1.1 × 10−5 m3/s and λ = 14 s, which
concentrates ammonia from 10 mol% to above 99 mol%,
LIN ET AL.
indicating that ammonia can be completely separated from
the dilute gas mixture. It was found that the performance
of the RPSA-assisted adsorber improves at higher exhaust
flow rates because more ammonia is introduced to the bed
that is adsorbed on 13X. Once depressurized, more ammo-
nia is subsequently released and collected in the product
line. Therefore, it results in reduced nitrogen content in the
column, hence avoiding the ammonia product being
diluted with the nitrogen in the bulk phase. Increasing the
cycle time also extends adsorption time, which is in favor
of the ammonia adsorption. Hence, the ammonia concen-
tration will increase in the product line at longer
cycle time.
3.4 | Effect of adsorber length
One of the parameters with a major influence on the per-
formance of the proposed RPSA-driven adsorber is its vol-
ume. The major parameter of interest that should be
optimized is the adsorber length while the diameter was
F I G U R E 7 Effect of the bed length on the performance of the
RPSA-assisted adsorber in terms of NH3 purity in the product line
using 13X zeolite. (A) L = 0.05, (B) L = 0.07, and (C) L = 0.09 m at
T = 298 K, P = 1.5 bar, and QE = 4.75–11.0 m3/s
F I G U R E 6 Effect of exhaust
flow rate and cycle time on the
performance of the RPSA-assisted
adsorber using 13X zeolite.
(A) NH3 purity in the product line
and (B) N2 recovery in the exhaust
line, both operating at T = 298 K,
P = 1.5 bar, and L = 0.05 m
LIN ET AL.
kept constant. Figure 7 shows the effect of the adsorber
length on the performance of the ammonia separation
using 13X adsorbent. We conducted the sensitivity analysis
on NH3 purity with respect to major design parameters
and operating conditions, with the most important ones
being feed and exhaust flow rates, cycle time, and bed
length. To capture the effect of all these parameters in a
single graph, dimensionless form of the flow is used as the
x-axis while having the effect of other major parameters,
and results are illustrated Figure 7 for different bed lengths
and cycle times. The major emphasis is to study the effect
of these parameters on NH3 purity. Figure 7A was adapted
from Figure 6A at the condition of T = 298 K, P = 1.5 bar,
and L = 0.05 m. As illustrated, the NH3 purity in the prod-
uct stream versus the exhaust-to-feed ratio (QE/QF) col-
lapses on a curve for all cycle times, with the highest
purity achieved with 14 s cycle time. Increasing the QE/QF
leads to higher ammonia purity in the product line, since
almost all nitrogen is being directed toward the exhaust
line. Thus, the RPSA separation is at its peak performance
when exhaust flow approaches the feed flow: that is, when
the amount of product produced is small. This results in
higher ammonia purity in the product line where ammo-
nia is being desorbed in the second half cycle and leaving
the adsorber through the product line. Note that
NH3 purity decreases from 99% to 47% and 32% when the
adsorber length increases from 0.05 m to 0.07 and 0.09 m
long at similar operating conditions, respectively. As the
adsorber length increases from 0.05 to 0.09 m, the purity
obtained in the product line decreases due to
the ammonia product dilution by the nitrogen retained in
the adsorber bed. It is important to observe that the QE/QF
ratios are obtained from solving the set of PDEs.
3.5 | Effect of feed pressure
Rapid pressure increase and decrease in the proposed
adsorber is the primary mechanism of separation and
F I G U R E 8 Effect of feed
pressure on the performance of the
RPSA-assisted adsorber packed with
13X zeolite in terms of (A) NH3
purity in the product and (B) N2
recovery in the exhaust at
T = 298 K, L = 0.05 m, and λ = 10 s
11 of 15
concentration of ammonia. Hence, the feed pressure
majorly influences the ammonia purity and nitrogen
recovery. The effect of the feed pressure on the perfor-
mance of the RPSA-assisted adsorber is depicted in
Figure 8. The ammonia purity in the product line and
nitrogen recovery in the exhaust line are displayed with
respect to QE at different feed pressures. Results suggest
that separation efficiency is decreasing as the feed pres-
sure increases. The highest separation performance is
achieved when the feed pressure of 1.5 bar and large
exhaust flow rate are considered, as displayed in
Figure 8A. Increasing the feed pressure to 2 and 3 bar
results in a severe decrease in ammonia purity (30% and
19%, respectively). The same trend is also observed in the
nitrogen recovery profile. The separation performance
decline at higher pressure which is due to the presence of
more gases in the void fraction of the adsorber column at
higher pressure. This decline in the ammonia purity in
the product line is also partially attributed to the fact that
the increase in the feed pressure leads to a slight decrease
in the ammonia selectivity on 13X adsorbent, displayed
in Figure 4A. For instance, the ammonia selectivity over
nitrogen decreases from 1732 to 1093 as the feed pressure
increases from 1.5 to 3 bar.
3.6 | Productivity of adsorbents
Table 4 shows the comparison of the productivity of
adsorbents given that an adsorbent column can obtain
nearly 99% NH3 with the ammonia recovery rate of
2.5 × 10−5 mol NH3/s. Notice that adsorbents need differ-
ent bed volumes for the same ammonia recovery rate via
the RPSA process, as summarized in Table 4. The
adsorber packed with FAU requires the largest volume,
that is, 3.5 × 10−5 m3, while the adsorber packed with 4A
is about twice smaller. Overall, the productivity of adsor-
bents follows this descending order 4A > Si > 13X >
5A > AC > FAU. Nonetheless, it should be noted that
12 of 15
T A B L E 4 Comparison of bed volume and ammonia
productivity for different adsorbents. (a) Bed volume needed and
(b) productivity for different adsorber beds. Condition: T = 298 K,
P = 1.5 bar, λ = 14 s, and QE = 1.1 × 10−5 m3/s. The total amount
adsorbed was 3.5 × 10−4 mol per cycle
Adsorbent volume Productivity
Adsorbents (10−6 m3) (mol/s m3)
13X 10.2 2.43
4A 9.65 2.59
5A 13.3 1.89
Si 9.84 2.55
AC 16.1 1.55
FAU 35.0 0.71
the proposed RPSA-assisted adsorber with the specifica-
tions designed here is just for the modeling purpos and
has a relatively small throughput.
3.7 | The potential application for
distributed ammonia manufacturing
The single-column, RPSA-assisted adsorptive separation
proposed in this study has the potential to be integrated
with a low-pressure HB reactor for small, distributed
manufacturing of ammonia. Our proposed design
includes a number of adsorber columns (e.g., 20) bundled
together. A schematic of the proposed integrated design
is shown in Figure 9, in which each column is packed
with zeolite 4A. This adsorbent was selected as it dis-
played the highest ammonia productivity, in comparison
to other adsorbents considered in this study (see Table 4).
At any half cycle, half of the RPSA-assisted adsorber col-
umns are in the adsorption (charging) mode while the
other half adsorber columns are in the desorption
(ammonia discharge) mode. When the three-way valve
switches, the feed flow will be directed to the other
adsorber columns that were previously in the
desorption mode.
The zeolite 4A adsorber makes the proposed process
economically affordable due to the relatively lower cost.
Each of the adsorbers displayed in Figure 9 can separate
2.5 × 10−5 mol NH3/s from the gas mixture on the basis
of 3.5 × 10−4 mol NH3 per cycle per column (Table 4).
For NFUEL ammonia plants with a production rate of
120 kg/h NH3,[49] the number of adsorber bundles
needed is about 4760 adsorber columns. The most prom-
ising feature of using an RPSA-assisted process for
ammonia separation is that dilute ammonia can be
LIN ET AL.
F I G U R E 9 Schematic of an RPSA-assisted ammonia
adsorption module with 20 adsorber mini columns packed with
zeolite 4A. Each column is 0.021 m in diameter and 0.05 m in
length. Ten of the adsorbers are in the adsorption cycle (first half
cycle) while the other 10 are in the desorption cycle (second half
cycle)
completely separated from the reactor effluent at nearly
atmospheric pressure, which can help with efforts
directed toward low-pressure ammonia production. The
proposed RPSA-assisted adsorber well fits the require-
ments for low-pressure ammonia production due to low
operating pressure and easy deployment.
4 | CONCLUSION
An RPSA-assisted adsorber is proposed for the separa-
tion of dilute ammonia from the effluent of the HB
reactor. For the proof-of-concept, a mathematical
model is proposed to study the effect of different pro-
cess variables on the performance of the RPSA-assisted
adsorber. The results suggest that high-purity ammonia
can be obtained by adjusting the exhaust flow rate,
cycle time, feed pressure, and bed length. Six different
adsorbents with relatively high ammonia selectivity
were studied, and it was found that 4A displayed the
best performance (more than 95% ammonia purity).
The proposed design can be further intensified for the
heat management of adsorption and desorption cycles
when multiple mini adsorbers are bundled together.
The proposed RPSA-based separation has the potential
for implementation in other dilute gas mixture separa-
tions, such as carbon dioxide capture from the flue gas
given that adsorbents with high selectivity for CO2 are
identified. Since simulations were carried out based on
the predicted Freundlich binary isotherm models by
IAST, there is a possibility that adsorbent capacity and
selectivity be overestimated. Experimental evaluation of
binary adsorption will be useful in validating the pro-
posed design.
LIN ET AL. 13 of 15

NO TATIO N ORCID
Latin symbols Mahdi Malmali https://orcid.org/0000-0001-5190-1261
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How to cite this article: Lin B, Hsieh I-M,

Malmali M. Rapid pressure swing adsorption for
small scale ammonia separation: A proof-of-
concept. J Adv Manuf Process. 2021;3:e10077.
https://doi.org/10.1002/amp2.10077 F I G U R E B 1 Velocity, Reynolds number, and pressure profile
along the bed length. (Darcy's law vs. Ergun equation)
LIN ET AL. 15 of 15

Darcy's equation is typically valid for Re < 10 (laminar Boundary conditions for Equation (1,C1):
flow) whereas Ergun's equation can predict the pressure At l = 0,
drop and flux in wider range Re.[54] To verify that Darcy's

law is applicable to our case, we compared the pressure pF , 0 < t≤λ=2
pð0, t Þ = ðC4Þ
drop/velocity calculated by Darcy's law and Ergun equa- 1, λ=2 < t≤λ
tion, and results are illustrated in Figure B1. Our calcula-
tions suggest that Re within the packed absorber column
ranges from 3 to 10, thus the flow tends to be in laminar At l = L,
mode. Comparison of results suggests that both Ergun
equation and Darcy's law are capable of predicting flow V ∂pðL, tÞ Qp
= qm − ðC5Þ
characteristics within the range studied for RPSA process. RT a ∂t Vm
We adopted Darcy's law to characterize the interstitial
gas velocity based on the local pressure gradient, as Initial condition for Equation (1,C1) (for 0 ≤ l ≤ L):
suggested by prior reports.[52,53]
pðl,0Þ = pF , for the 1st cycle: ðC6Þ

A P P EN D I X C : D I M EN SI O N A L F O RM O F
pðl,0Þ for the mth cycle = pðl,λÞ for the ðm −1Þth cycle:
E Q U A T IO N S

Overall mass balance: Boundary conditions for Equation (2,C2):

For 0 ≤ t ≤ λ/2,
Aϕ ∂p ∂q W ∂N t
=− m− ðC1Þ
RT ∂t ∂l L ∂t yð0, t Þ = yF ðC7Þ

Component mass balance:

Initial condition for Equation (2,C2) (for 0 ≤ l ≤ L):
Aϕ ∂ ðypÞ ∂ ðyqm Þ W ∂ ðxN t Þ
=− − ðC2Þ
RT ∂t ∂l L ∂t yðl,0Þ = yF , for the 1st cycle: ðC8Þ

Momentum equation: yðl,0Þ for the mth cycle = yðl,λÞ for the ðm −1Þth cycle:

1 T a p KA ∂p All the parameters and variables are defined in the

qm = − ðC3Þ
V m T pa μ ∂l notation list.