Separation and Purification Technology 142 (2015) 215–226

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Ammonia sorbent development for on-board H2 purification

Bart A. van Hassel a,⇑, Jagadeswara R. Karra a, Jose Santana a, Salvatore Saita a, Allen Murray a,
Daniel Goberman a, Richard Chahine b, Daniel Cossement b
a
United Technologies Research Center, 411 Silver Lane, East Hartford, CT, USA
b
Hydrogen Research Institute, Université du Québec à Trois-Rivières, Trois-Rivières, QC G9A 5H7, Canada

a r t i c l e i n f o a b s t r a c t

Article history: The application of chemical hydrides (e.g. ammonia borane) and amide-based hydrogen storage materials
Received 11 July 2013 would benefit from an effective means to remove ammonia, which is an impurity that is detrimental to
Received in revised form 5 November 2014 the performance of a PEM fuel cell. One option is to adsorb ammonia on a sorbent with high capacity that
Accepted 9 December 2014
would also be regenerable. Such a sorbent was developed by impregnating super activated carbon with
Available online 23 December 2014
metal chlorides (MgCl2, ZnCl2, MnCl2). The sorbent was characterized through static and dynamic adsorp-
tion experiments. It was shown to have a good cyclic stability. The filter weight, volume and pressure
Keywords:
drop appears reasonable for an onboard vehicle application when it would be replaced/regenerated every
Ammonia
Adsorbent
1800 miles, similar to an oil change.
Capacity Ó 2015 United Technologies Corporation. Published by Elsevier B.V. All rights reserved.
Dynamic adsorption
Isotherm
Super activated carbon

1. Introduction is based on ammonia borane [5,40]. The adsorbent is also applica-

On-board materials-based hydrogen storage systems for light-
duty vehicles need to meet stringent targets in order to be able
to compete with physical storage systems. A comprehensive set
of such targets has been developed by U.S.DRIVE, a government-
industry partnership between the U.S. Department of Energy
(DOE), U.S. automobile manufacturers, and energy and utility com-
panies [1]. This set of targets serves as the technical targets of the
DOE-funded Hydrogen Storage Engineering Center of Excellence
(HSECoE). The HSECoE focuses on materials-based hydrogen
storage systems that use on-board reversible metal hydrides,
off-board regenerable chemical hydrogen storage materials and
cryo-adsorbents. All three DOE supported materials-based hydro-
gen storage centers of excellence [2–4] have suggested promising
materials to the HSECoE.
This paper focuses on the development of ammonia (NH3)
adsorbents for a chemical hydrogen storage material system that
Abbreviations: HSECoE, Hydrogen Storage Engineering Center of Excellence;
DAQ, data acquisition; DOE, US Department of Energy; DOT, US Department of
Transportation; UQTR, Université du Québec à Trois-Rivières; UTRC, United
Technologies Research Center, East Hartford, Connecticut.
⇑ Corresponding author.
E-mail address: vanhasba@utrc.utc.com (B.A. van Hassel).
ble to some reversible metal hydride materials, such as in the Li–
Mg–N–H system [6,7,29]. The ammonia impurity in hydrogen that
is released from these storage materials needs to be removed in
order to protect the fuel cell system from degradation [8,9]. The
SAE J2719 Hydrogen Purity guideline [10] specifies an upper
ammonia limit of 0.1 ppm, in order to achieve that goal. NH3 is
not the only impurity in hydrogen that is released during the ther-
molysis of ammonia borane and a different separation needs to be
performed in order to remove the other impurities as well. Hydro-
gen from these storage systems tends to be anhydrous, which
needs to be taken into account when selecting adsorbent materials
with a high gravimetric and volumetric capacity.
Activated carbon plays an important role as an adsorbent to
protect people from ammonia exposure [11,12] and to purify pro-
cess streams [13,14]. Adsorbents are an important stepping block
for the development of on-board H2 purification for a chemical
hydrogen storage material system. Commercially available adsor-
bents have been reported [11] to have a limited gravimetric capac-
ity (1–5 wt.%), especially under dry conditions. Recent sorbent
development work [15–17] has focused on the increase of acidic
surface oxides through activation with mineral acids. The resulting
combination of physisorption and chemisorption yielded adsor-
bents with high gravimetric capacity (4–14 wt.%). Their capacity

http://dx.doi.org/10.1016/j.seppur.2014.12.009
1383-5866/Ó 2015 United Technologies Corporation. Published by Elsevier B.V. All rights reserved.
216 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226
exceeds the capacity of activated carbons that have not been
impregnated with mineral acids.
Metal–organic frameworks (MOF’s) have been proposed by Brit
et al. [18] as high capacity and selective adsorbents for removing
harmful gases. They reported high capacity MOF’s for NH3 adsorp-
tion (8.7–10.5 wt.% in 9900 ppm NH3 in N2). The results show
sharp breakthrough curves, indicating an efficient mass transfer
and high rate of adsorption. UTRC’s measurements confirmed the
high sorption capacity of MOF-199 (HKUST-1 or Cu-BTC) but the
sorbent could not be regenerated, which was also reported by Petit
et al. [19]. MOF-5 and MOF-177 frameworks also get destroyed
upon ammonia exposure according to Saha and Deng [20]. Glover
et al. [21] reported ammonia adsorption by MOF-74 up to
12.9 wt.% by having coordinatively unsaturated (open) metal sites
but they do not report whether this MOF can be regenerated.
Ammonia adsorption by MOF-199 creates a distinct color change,
which can be used as a visual indicator for NH3 breakthrough when
deployed downstream of a main ammonia scrubber. This is similar
to the visual indicator that has been reported by Wilkes [31], Long
et al. [32] and Schmidt [33].
Surprisingly, little work has been reported about the use of
metal chlorides as active phase of an ammonia sorbent material
[22–25], despite the abundant data on the thermodynamic stabil-
ity of metal chlorides in their ammoniate forms [26,27] and ease
of impregnation. Sharonov and Aristov [22] reported the ammonia
capacity of alumina impregnated with alkaline-earth metal chlo-
rides (BaCl2, CaCl2 and MgCl2). Bandosz and Petit [23] reported that
a coal based activated carbon reached a dynamic sorption capacity
of 6–7 wt.% at an ammonia inlet concentration of 1000 ppm in air
after impregnation with either zinc chloride or copper chloride.
Fortier et al. [24] and Furtado et al. [25] reported a high capacity
ammonia sorbent that was prepared by impregnating ZnCl2 in
either activated carbon or in a siliceous material (MCM-41).
This paper focuses on the selection of metal chlorides for
chemisorption of ammonia, the impregnation in super activated
carbon (IRH-33 from the Institut de recherche sur l’hydrogène,
Université of Québec à Trois-Rivières) and the characterization of
the resulting composite material as a regenerable ammonia sor-
bent for onboard fuel cell vehicle applications.
2. Experimental
2.1. Materials
Helium (5.0 UHP grade) and Nitrogen (5.0 UHP grade) were pur-
chased from Praxair (U.S.A). Anhydrous pure ammonia (Ammo-
nia > 99.9992%, Carbon Dioxide < 1 ppm, Carbon
Monoxide < 0.1 ppm, Methane < 0.1 ppm, Nitrogen < 2 ppm, Oxy-
gen < 1 ppm, Water < 2 ppm), ammonia nitrogen gas mixture
(10,200 ppm NH3 in N2) were purchased from Matheson. Anhy-
drous magnesium(II) chloride (MgCl2), anhydrous zinc(II) chloride
(ZnCl2) and anhydrous manganese(II) chloride (MnCl2) were pur-
chased from Sigma Aldrich. Ammonasorb II (<20 wt.% phosphoric
acid in activated carbon (Calgon Carbon)), Kuraraycoal T-B
(27 wt.% phosphoric acid in activated carbon (Kuraray Chemical
Co., LTD)), Selexsorb CD (BASF), Chemsorb (Molecular Products),
Basolite C 300 (Sigma Aldrich), Vermiculite, and activated carbon
SG6 (Cameron carbon) were kindly provided as samples by the
vendors.
2.2. Synthesis
2.2.1. IRH-33 Preparation
Raw material is a commercial activated carbon named CNS-201
(AC-Carbon company) and the pilot oven (Pyradia) for activation is
a 100 L rotary kiln externally heated with electrical resistances
(36 kW). CNS-201 has a bulk density of 0.45 g/ml and a BET surface
area of 1400 m2/g. Activation agent is CO2 and activation tempera-
ture is fixed to 900 °C. This is a batch production with an initial
mass of 10–11 kg of raw material and the CO2 flow rate is fixed
to around 4.0 L STP/min. To reach a bulk density of 0.20 g/ml, acti-
vation duration is around 80 h. Final production is between 4 and
5 kg. The super-activated carbon IRH 33 was used in a granular
form. The weight fraction of +20 mesh was 71.4%, the weight frac-
tion from 20 mesh to +35 mesh was 26.2% and the weight frac-
tion from 35 mesh to +70 mesh was 2.4%. No change was
observed in the sorbent granularity before and after MnCl2 impreg-
nation and drying and before and after NH3 adsorption, indicating
that the IRH33 material could handle the volumetric expansion of
the MnCl2 upon NH3 adsorption.
2.2.2. Impregnated IRH-33 Preparation
Sorbents were prepared in batches of 36 g. The desired amount
of metal chloride salt was transferred into a 200 ml of ethanol filled
two-neck round bottom flask placed over a heating mantle. The
solvent was refluxed and the solution was stirred continuously
under nitrogen environment for about 20 min at 90 °C until all
the salts dissolved in the solvent. The desired amount of IRH-33
was loaded into the round bottom flask and refluxed for about
4 h. The solvent was removed by rotary evaporation using a BUCHI
Rotovapor R-205. The sample was dried in a vacuum oven at 200 °C
under vacuum overnight. Table 1 summarizes the samples pre-
pared using this technique. As verification, MnCl2 that had been
impregnated in IRH-33 was dissolved in ethanol in a soxhlet appa-
ratus. The weight loss of the sorbent was consistent with the
intended amount of MnCl2. The loading of the IRH-33 with impreg-
nates is high as that yielded the highest dynamic sorption capacity.
2.3. Characterization
2.3.1. SEM measurements
A scanning electron microscope (JEOL Model 6335F) with a
Thermo Fisher EDS system was used to image the samples.
2.3.2. Tap density
Tap densities were measured manually by measuring the mass
and volume of the tapped sorbent loaded in a 10 ml graduated cyl-
inder. The results are reported in Table 6.
2.3.3. X-ray Photoelectron Spectroscopy
X-ray photoelectron spectra (XPS) were acquired with a Physi-
cal Electronics VersaProbe XPS System equipped with a monochro-
matic Al K (a) X-ray source (E = 1486.6 eV). Spectra were collected
with survey scan settings of 117.4 eV pass energy, 20 ms dwell
time, 1.0 eV/step and high-resolution settings of 29 eV pass energy,
50 ms dwell time and 0.1 eV/step. Both argon ion and electron neu-
tralization were utilized to mitigate the effects of sample charging.
Sample powders were sprinkled onto carbon tape, placed into the
sample introduction chamber which was evacuated with a turbo-
molecular pump for 1 h prior to introduction to the main chamber
and analysis. The data was analyzed using a software package
called CasaXPS Version 2.3.15 Dev 36. Survey spectra were utilized
Table 1
Composition of impregnates in the sample studied in this work.
Sample description wt.% metal chloride
MgCl2 on IRH-33 50
ZnCl2 on IRH-33 50
MnCl2 on IRH-33 30, 40, 50, 60, 70
 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226
Fig. 1. Diagram of the experimental setup for dynamic ammonia adsorption experiments. TC = thermocouple, MFC = mass flow controller, 3WV = 3 way valve, 4WV = 4 way
valve, NV = needle valve, V = ball valve, PRV = pressure relief valve, BPR = back pressure regulator, DAQ = data acquisition, P = pressure gauge, B&K = 1412 Innova photo-
acoustic NH3 analyzer.
to confirm elemental composition. High Resolution scans of the
main elemental peaks were fit with a Shirley background, height
averaged over three data points at each end of the region. Peaks
data was deconvoluted using Gaussian–Lorentzian (30) artificial
peaks using a fixed full-width at half height for each set of element
peaks, allowing the CasaXPS software to iterate peak area (inten-
sity) and position to optimize the fit to the raw data.
2.3.4. Nitrogen and ammonia adsorption equilibrium measurements
A Micrometrics volumetric adsorption instrument (ASAP 2020)
was used to measure the nitrogen adsorption equilibrium isotherm
at 77 K. Prior to nitrogen gas adsorption experiments, the sample
was degassed at 90 °C for 15 min and then heated to 200 °C over-
night under vacuum. Helium gas was used to measure the free space
volume of the sample holder. Typically about 40 mg of sample was
loaded in the glass sample holder used for this instrument. No differ-
ence was observed between tests with 40 mg or 100 mg of sample,
but the measurement time was shorter for the 40 mg sample in the
small dose mode of the instrument. The specific surface areas were
estimated from the nitrogen adsorption equilibrium data using the
BET model within the P/Po range from 0 to 0.03. Pore size distribu-
tion was calculated by using the density functional theory (DFT).
Few modifications were made on the low-pressure volumetric
gas adsorption apparatus (Micromeritics) for performing anhy-
drous ammonia gas adsorption equilibrium measurements. The
standard liquid N2 dewar (4 L), for the sample tube bath, was
replaced with a dewar (1 L) containing a copper coil through which
a 50% propylene glycol/water thermal fluid (temp. range 30 °C to
+105 °C) was pumped from a Julabo FP50 refrigerating circulator.
An ammonia gas detection system (Draeger Polytron) and safety
controls were put in place in order to reduce the risks of working
with anhydrous ammonia. Ammonia adsorption equilibrium iso-
therm measurements were performed at 20, 0, 20, 50, and 77 °C.
217
2.3.5. Dynamic adsorption breakthrough experiment
A process flow diagram of the experimental set up for dynamic
adsorption breakthrough experiments is depicted in Fig. 1. Nitro-
gen was used as a surrogate in these experiments for hydrogen
in order to minimize risk. A gas mixture containing 10,200 ppm
ammonia in nitrogen and in-house nitrogen were used for dynamic
breakthrough experiments. The sample was loaded in a 11.5 cm
long and 1.12 cm inner diameter stainless steel sample column
with glass wool at the bottom and the top to hold the sample. Typ-
ically 4–9 g of sorbent was filled in the sample column, depending
on the tap density of the sorbent. A K-type thermocouple was posi-
tioned at the center on the outer surface of the column. Experi-
ments with the thermocouple in the stated position revealed a
peak temperature rise of 3–7 °C, which was followed by a gradually
decline back to the starting temperature. Inserting the thermocou-
ple inside the small diameter sorbent bed (ID = 1.12 cm) could
have caused channeling of the impurity through the bed, which
the authors wanted to avoid. The gas flow rates were controlled
by mass flow controllers (Brooks, USA). Rotameters (Matheson,
USA) were used as flow indicators. Ammonia pressure relief valves
and safety controls were put in place to reduce the risk of working
with anhydrous ammonia. Back pressure regulators were used to
maintain a constant pressure. At the column outlet, the ammonia
and water vapor concentration in the effluent gas stream were
monitored by flowing the effluent gas stream through a 1412
Innova photo-acoustic field gas monitor (Air Tech Instruments).
Prior to testing, the photo-acoustic field gas monitor was calibrated
over a range of concentrations in order to correct for non-linearity
at higher concentrations. In order to meet the flow rate require-
ment of the analyzer, the effluent stream was diluted with a N2
gas stream at a flow rate of 2 SLPM.
Prior to all measurements, the sample was dried at 200 °C under
2 SLPM nitrogen flow overnight. First N2 was allowed to pass
218 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226

through the column at 2 SLPM and it was pressurized up to the ammonia adsorption capacities and binds ammonia strongly over
desired pressure with the backpressure regulator (BPR1) while a wide range of temperatures even at low partial pressures.
the mixed gas stream in the bypass of the column was set with
the second backpressure regulator (BPR2) to the same pressure 3.2. Ammonia isotherm models
with the NH3/N2 mixture at gas flow rate of 2 SLPM. After obtaining
a good baseline for NH3 and water vapor concentrations, the N2 3.2.1. Activated carbon
stream was switched to the NH3/N2 mixture and the NH3 concen- The Dubinin–Ashtakov (DA) model was used to model NH3 iso-
tration was monitored vs.time well beyond the actual break- therm for IRH-33, as shown in Eq. (2) [34–37].
through time.   m 
A
The breakthrough time was defined as the time at which the qAC ðpÞ ¼ xo exp  ð2Þ
E
NH3 concentration started to exceed 0.1 ppm which is the upper  
limit according to the SAE J2719 APR2008 H2 purity guideline Ps
where A ¼ DG ¼ RT ln ð3Þ
[10]. The dynamic sorption capacity was calculated from the P
 r
breakthrough time, impurity concentration, flow rate and sorbent T
and P s ¼ Pc ð4Þ
amount. The sample in the column was subjected to several cycles Tc
to test the stability of the sorbent material. Between each cycle,
regeneration of the column was performed at 200 °C under N2 flow where qAC(p) is the measured gravimetric adsorption amount (g
with a flow rate of 2 SLPM. NH3/g adsorbent), xo is the maximum amount adsorbed (g NH3/g
adsorbent), A is the adsorption potential (J/mol NH3), E is the char-
acteristic energy of adsorption (J/mol NH3), m is the structural het-
2.3.6. Nitrogen permeability measurements erogeneity parameter, Ps is the virtual saturation vapor pressure of
The same experimental apparatus used for dynamic adsorption the adsorbate (Pa), r is a constant, Tc and Pc are critical temperature
breakthrough experiments was used to conduct the permeability (K) and pressure (Pa) of the adsorbate. UTRC evaluated several
experiments with NH3 adsorbents (MnCl2 supported on IRH-33) adsorption isotherm models (Toth, Langmuir, Langmuir Fruendlich,
using nitrogen gas at 20 °C. The inlet pressure was measured by DR, and DA) and the DA isotherm model resulted in the lowest sum
a pressure gauge and the pressure drop across the bed was mea- of squares of errors in the studied range of NH3 partial pressure and
sured by a differential pressure gauge. The permeability measure- temperature.
ments were performed with N2 gas at a flow rate in the range of 1
to 10 SLPM using the mass flow controller (Brooks, USA). Taking 3.2.2. Impregnated activated carbon
into account the inlet pressure, pressure drop and the mass flow The enthalpy of ammoniate formation for each of the three
rate measurements, the permeability of nitrogen gas in the sorbent reactions in Table 5 was assumed to have a Gaussian distribution.
bed was calculated using the expression obtained from the Darcy This causes a log-normal distribution of the NH3 equilibrium pres-
equation for compressible fluids. sure (Fig. 3), which gave a better fit between the model and the
  experimental results.
Rg T l:Q
P21  P22 ¼ 2  Z  ð1Þ The mean value of the NH3 equilibrium pressure for each of the
M K:A
three reactions in Table 5 can be calculated from the enthalpy and
where K is the permeability (m2), l is the dynamic viscosity of entropy of ammoniate formation, as shown in Eq. (5). The contri-
nitrogen gas (kg/m s), Q is the mass flow rate (kg/s), T is the operat- bution to the total ammonia uptake by each of the three reactions
ing temperature (K), M is the molecular weight of N2, Z is the length can be calculated with Eq. (6).
h i
of the sorbent bed (m), Rg is the ideal gas constant (J/mol/K), P1 and
li ¼ log expððDHi  TDSi Þ=RTÞ  105 ð5Þ
P2 are the upstream and downstream pressure across the sorbent   qffiffiffiffiffiffiffiffiffi
bed (Pa). 1
qi ðpÞ ¼ 1 þ erf ðlog p  li Þ 2r2i hi ð6Þ
2
3. Theory Total ¼ q1 ðpÞ þ q2 ðpÞ þ q3 ðpÞ þ qAC ðpÞ ð7Þ

3.1. Metal chlorides selection

Selection of composite adsorbents for this application required

the selection of a metal chloride salt and a porous support. Metal
chlorides (MCl2) can be used to reversibly adsorb NH3 according
to the following exothermic chemical reaction:

MCl2  xNH3 þ yNH3 ¼ MCl2  ðx þ yÞNH3

The heat released in this reaction is yDHr, where DHr the reaction
enthalpy on a per mole NH3 basis (J/mol NH3). The equilibrium is
monovariant, which means that by specifying the temperature,
the equilibrium NH3 partial pressure will be fixed. The basic ther-
modynamic properties [26] of some working pairs are shown in
Fig. 2. MgCl2, ZnCl2 and MnCl2 were selected as they enable an
NH3 equilibrium concentration below 0.1 ppm up to an operating
temperature of 60 °C and because they can be regenerated by heat- Fig. 2. Equilibrium NH3 partial pressure for various ammoniate forming metal
ing the adsorbent to modest temperatures (180–200 °C). Among chlorides as a function of temperature. The designator y–x behind each metal
chloride (e.g. MnCl2 2–1, y = 2, x = 1) indicates the number of NH3 molecules before
these three metal chlorides, ZnCl2 has been widely used as impreg- (x) and after (y) NH3 adsorption as each equilibrium reaction has its own
nant in porous materials (MCM-41, activated carbons) for ammonia equilibrium partial pressure [26], as calculated from –RgT ln(PNH3/Pa) = DHi  TDSi,
removal applications in the literature [23–29] as it exhibits high using literature values of Table 5.
 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226 219

Fig. 3. Probability density function and cumulative distribution function as a function of ammonia equilibrium pressure for different MnCl2 ammoniates.

where qi is the ammonia uptake at a specific ammonia pressure p

(bar) for reaction i, DHi, DSi is the enthalpy and entropy of ammo-
niate formation for reaction i, li and ri is the mean and standard
deviation of the log-normal distribution for reaction i, hi is the max-
imum uptake of the manganese chloride ammoniate for reaction i.
The adsorption isotherm at 20 C indicated the presence of a sepa-
rate step that can be associated with a hypothetical MnCl24NH3
phase and the estimated thermodynamic properties were added
to Table 5 for clarity.
A constraint that has been applied is that the maximum uptake
of MnCl2 to form MnCl21NH3 is equal to that of the maximum
uptake of MnCl21NH3 to form MnCl22NH3 and the maximum
uptake of MnCl22NH3 to form MnCl26NH3is four times the max-
imum uptake of MnCl2 or MnCl21NH3, due to the stoichiometry of
the reactions. The sum of the contributions represents the full
model, given by Eq. (7).

4. Results and discussion

4.1. Rationale for Selection of IRH-33 as a porous support

Fig. 4. Comparison of the dynamic sorption capacity of three regenerable NH3
The impregnated metal chloride expands substantially upon adsorbent materials: (1) 50 wt.% MgCl2 on IRH-33 (light blue),(2) 50 wt.% MgCl2 on
ammoniate formation. This requires a strong support material in Cameron activated carbon (dark blue), (3) 50 wt.% MnCl2 on Vermiculite (red). The
measurements were performed with 2 SLPM of 10,200 ppm NH3 in N2 gas mixture
order to prevent the formation of fines that reduce the permeabil-
at 5 bar absolute pressure and room temperature. (For interpretation of the
ity of the packed bed. Cameron activated carbon and Vermiculite references to color in this figure legend, the reader is referred to the web version of
were not strong enough supports as cycle tests had to be stopped this article.)
prematurely as the pressure drop across the packed bed became
very high (30 psid). This effect is similar to what has been reported
by Wilkes [31], Long et al. [32] and Schmidt [33]. On the other
hand, the super activated carbon (SAC) IRH-33 yielded after
impregnation with metal chlorides not only a sorbent with a supe-
rior capacity but also a packed bed with a pressure drop that
stayed constant at about 11 psi during seven cycles (50 wt.% load-
ing of MgCl2 on IRH-33), as shown in Fig. 4. Therefore IRH-33 was
selected as porous support for the other metal chlorides that were
tested (ZnCl2, MnCl2). Actual strength measurements of the sor-
bent granules have not been performed as part of this study.

4.2. Nitrogen adsorption–desorption equilibrium measurements

The dispersion of the metal chlorides for a high ammonia

adsorption rate and capacity requires a porous support with a high
specific surface area and pore volume, which were measured by
nitrogen adsorption/desorption equilibrium measurements at
77 K (see Section 2.3.4). Those measurements were performed on
four samples (Table 2): (1) pristine IRH-33, (2) 40 wt.% MnCl2
loaded on IRH-33 before NH3 exposure, (3) IRH-33 prepared by dis-
solving 40 wt.% MnCl2 loaded on IRH-33 in ethanol and filtering
ethanol solution from the super activated carbon in a soxhlet appa-
ratus, (4) 40 wt.% MnCl2 loaded on IRH-33 that had been exposed
to 12 ammonia adsorption–desorption cycles in a dynamic adsorp-
tion breakthrough column.
Fig. 5. Nitrogen adsorption–desorption isotherms of different samples at 77 K.
Figs. 3 and 4 show the experimental nitrogen adsorption–
desorption isotherms at 77 K and DFT pore size distribution for
all four samples. The BET surface areas and DFT total pore volumes
derived from the nitrogen isotherms for these samples are given in
Table 2.
All the isotherms in Fig. 5 show Type I behavior. A small hyster-
esis is seen for these samples with the desorption isotherms due to
220 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226
Fig. 6. Pore size distribution of different samples.
Fig. 7. Fit of DA equation to the NH3 adsorption isotherms of IRH-33 at 20, 0, and
20 °C.
the capillary condensation of nitrogen in the few mesopores
(between 20 and 500 Å). Fig. 6 shows the pore size distribution
of the samples. Pore size for all these samples varies between 5
and 50 Å. The pore size distribution has a maximum in the range
from 20 to 50 Å, well above the size of the ammonia molecule
(3 Å).
Upon impregnation of the salt into the pores of super activated
carbon, the BET surface areas dropped from 2157 to 903 m2/g and
the pore volume dropped down from 1.296 cm3/g to 0.59 cm3/g.
The loading of MnCl2 did not cause any damage to the microstruc-
ture of super activated carbon. This is evident from the N2 adsorp-
tion isotherm of sample 3 as there is no significant change in
surface area and DFT pore volume between sample 1 and sample
3, e.g. after dissolving the MnCl2. Ammonia adsorption and regen-
eration only causes a slight reduction in the surface area and pore
volume, as indicated by the results for sample 4 in comparison to
sample 2.
4.3. NH3 Adsorption Isotherms on IRH-33
Fig. 7 shows the experimental NH3 adsorption isotherms at
20, 0 and 20 °C for super activated carbon IRH-33. Several
adsorption isotherm models (Toth, Langmuir, Langmuir Freund-
lich, DR and DA) were evaluated and the DA isotherm model
resulted in the lowest sum of squares of errors in the studied range
of NH3 partial pressure and temperature. DA fit parameters of
super activated carbon IRH-33 are shown in Table 3. The model fits
Table 2
BET surface areas and DFT pore volume of super activated carbon and its different
modified versions.
Sample Sample description BET SA DFT total pore
no (m2/g) volume (cm3/g)
1 Pristine IRH-33 2157 1.296
2 40 wt.% MnCl2 on IRH-33 903 0.59
before NH3 exposure
3 IRH-33 after MnCl2 dissolution 2001 1.209
4 40 wt.% MnCl2 on IRH-33 862 0.539
after NH3 exposure
Table 3
DA fit parameters of super activated carbon.
Parameter Value
xo (gNH3/g adsorbent) 2.616
r 8.914
E (J/mol) 509.697
m 0.622
Pc(bar) 112.9
Tc(K) 405.5
well to the experimental data with a slight deviation at lower pres-
sures for 20 °C.
4.4. NH3 adsorption isotherms on MnCl2 impregnated IRH-33
Figs. 8 and 9 show the experimental ammonia adsorption iso-
therms at 20, 0, 20, 50 and 77 °C for 40 wt.% MnCl2 loaded on
IRH-33. The experimental data are shown as symbols. In order to
fit a model through the experimental data, contributions were con-
sidered of various MnCl2 ammoniate formation steps (Table 4) as
wells as the AC, as explained in Section 3.2. The temperature range
was selected in order to be consistent with the operating ambient
temperature range (40 °C to +60 °C) that is targeted by the US
DOE for fuel cell vehicles and the maximum delivery temperature
of hydrogen gas to the fuel cell (85 °C) [1]. The dashed vertical line
indicates the inlet NH3 partial pressure of most of the dynamic NH3
adsorption experiments (i.e. 10,000 ppm NH3 at 5 bar).
The NH3 adsorption isotherm at 20 °C (Fig. 8) shows that
MnCl2 takes up 1 mol of ammonia first (dark red) at very low
pressures (105 – 104 bar), then picks up another mole of
ammonia (green) at pressures between 104 and 103 bar and
then takes up the remaining 4 mol of ammonia (purple) at pres-
sures between 102 and 101 bar. The activated carbon contribu-
tion is indicated by the orange line. It shows that the AC
contributes to the overall ammonia uptake at higher pressures.
The full NH3 adsorption model at 20 °C, given by Eq. (7) in Sec-
tion 3.2.2, is displayed in Figs. 8 and 9 as a solid blue1 line. Similar
trends were seen at 50 and 77 °C (Fig. 10). The MnCl2 ammoniate
formation for the three reactions occur at slightly higher pressures
compared to MnCl2 ammoniate formations at 20 °C, as the ammo-
niate formation reaction is exothermic. The stepwise adsorption of
ammonia is consistent with the model that was described in
Section 3.2.2.
The fit parameter values are shown in Table 4 in comparison to
literature values for bulk MnCl2 (e.g. not supported on a porous
support). Table 4 shows that the adsorption enthalpy values for
each of the ammoniate forming reactions of MnCl2 in IRH-33, but
especially step 1 and 2, are lower than reported in literature. The
modified thermodynamics may result from the finely dispersed
1
For interpretation of color in Figs. 8 and 9, the reader is referred to the web
version of this article.
 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226 221

character of MnCl2 in the IRH-33 super activated carbon in combi-

nation with the large volumetric expansion of MnCl2 upon ammo-
niate formation [27]. Such effects have been observed in the field of
metal hydrides [38,39].
The ammonia adsorption isotherm at 20 °C, 50 °C and 77 °C look
similar and have only shifted to higher NH3 partial pressure as the
adsorption process is exothermic. The ammonia adsorption iso-
therms at 0 °C and 20 °C look different from the adsorption iso-
therm at 20 °C. The step height at an NH3 partial pressure of
0.002 bar is only halve as high as the corresponding step height
at 20 °C. This suggest a reaction sequence in which MnCl2.2NH3
reacts with 2 NH3 molecules under the formation of MnCl2.4NH3,
which subsequently reacts with an additional 2 NH3 molecules
under the formation of the final product (MnCl26NH3). The exis-
tence of MnCl24NH3 at 20 °C requires further crystallographic
verification, as such a phase has not yet been reported in literature.
Lepinasse and Spinner do report ZnCl24NH3, and Zn is located in
the same row as Mn in the periodic table of the elements. Fig. 10
shows a tentative phase diagram with the MnCl24NH3 phase only
Fig. 8. Isotherms of ammonia sorption on 40wt.% MnCl2 supported on IRH-33 at occurring at low temperature. Adding the hypothetical formation
20 °C.
of MnCl24NH3 to the adsorption isotherm model at low tempera-
ture (20 °C) improves the overall fit of the model to the experi-
mental data, as shown in Fig. 11. The estimated thermodynamic
enthalpy and entropy of the ammoniate formation are shown in
Table 5.
Another possible explanation of the shape of the isotherm at
0 °C and 20 °C is that the MnCl26NH3 formation rate has become
very slow at those low temperatures and that equilibrium was not
reached during the isotherm measurement. This could result from
a slow diffusion of NH3 through a skin of MnCl26NH3 around a
core of MnCl22NH3. Dynamic adsorption experiments also indicate
that MnCl26NH3 formation tends to be slow, possibly due to a
mass transfer issue that is related to the swelling of the metal chlo-
ride salt.

4.5. Dynamic adsorption breakthrough

4.5.1. Effect of temperature, pressure and flow rate

Fig. 9. Isotherms of ammonia sorption on 40 wt.% MnCl2 supported on IRH-33 at
20, 0, 20, 50 and 77 °C.
The dynamic ammonia adsorption capacities of 50 wt.% MgCl2,
50 wt.% ZnCl2, 40 and 50 wt.% of MnCl2 on IRH-33, at elevated tem-
peratures are compared in Fig. 12a. Characterizing the sorbent over
this temperature range is important as the DOE requires any H2
storage system to operate between 40 °C and +60 °C. The
dynamic ammonia sorption capacity drops with an increase in

Table 4
Thermodynamic values [27] and model fit parameters of enthalpy and entropy of ammoniate formation along with the standard deviation and maximum uptake of MnCl2xNH3
(x = number of moles of NH3) for different reaction steps.

i Reaction Thermodynamics [26] Model fit to equilibrium isotherm

Enthalpy Entropy h (g NH3 adsorbed)/g Enthalpy Entropy DS Standard deviation h (g NH3 adsorbed)/g
DH (J/mol) DS (J/mol/K) adsorbent) DH (J/mol) (J/mol/K) r of 10 log(Peq) adsorbent)
1 MnCl2 + NH3 = MnCl2NH3 84,202 233 0.054 65,021 224 1.719 0.0555
2 MnCl2NH3 + NH3 = MnCl22NH3 71,019 232 0.054 61,608 232 0.6390 0.0555
3 MnCl22NH3 + 4NH3 = MnCl26NH3 47,416 228 0.217 40,908 210 0.3144 0.2218

Table 5
Estimated adsorption enthalpy and entropy values along with the standard deviation and maximum uptake of the reactions observed at sub-ambient temperature.

i Reaction Thermodynamics [26] Model fit to equilibrium isotherm

Enthalpy Entropy h (g NH3 adsorbed)/g Enthalpy Entropy Standard deviation h (g NH3 adsorbed)/g
DH (J/mol) DS (J/mol/K) adsorbent) DH (J/mol) DS (J/mol/K) r of 10log (Peq) adsorbent)
4 MnCl22NH3 + 2NH3 = MnCl24NH3 56,089 265 0.2791 0.108
5 MnCl24NH3 + 2NH3 = MnCl26NH3 19,902 142 0.3189 0.108
222 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226
Fig. 10. Tentative phase diagram of the MnCl2 ammoniates with MnCl24NH3 only
forming at low temperature. The points indicate the location of steps in the
ammonia adsorption isotherm.
Fig. 11. Isotherms of ammonia sorption on 40 wt.% MnCl2 supported on IRH-33 at
20, 0, 20, 50 and 77 °C.
temperature, as expected. The dynamic ammonia adsorption
capacity of MnCl2 supported on IRH-33 was higher than the other
metal chlorides at elevated temperatures (50 and 80 °C).
The dynamic ammonia sorption capacities of 40 wt.% MnCl2 on
IRH-33 was close to the expected sorption capacity from the equi-
librium adsorption isotherm measurement at 50 and 80 °C
(11 wt.%). The dynamic ammonia sorption capacities of 40 wt.%
MnCl2 on IRH-33 at 20 °C was lower than the expected sorption
capacity from the equilibrium adsorption isotherm measurement
(22 wt.%). This could be due to the slow formation of MnCl26NH3
species, perhaps due to a mass transfer limitation. There is a sub-
stantial expansion during the formation of MnCl26NH3 from
MnCl22NH3, which can block pores and prevent access of NH3 to
the core of the adsorbent granule. Another reason for the discrep-
ancy is that a 3 °C rise in temperature in the packed bed results in a
2 wt.% loss in the equilibrium sorption capacity at an NH3 partial
pressure of 0.05 atm as the adsorption isotherm is very steep in
that NH3 partial pressure range.
Fig. 12b and c shows the effect of flow rate and pressure on the
breakthrough curve. An increase in flow rate of the ammonia–
nitrogen gas mixture resulted in a decrease of the dynamic ammo-
nia adsorption capacities, which may be related to a slow forma-
tion of MnCl26NH3 species and the blocking of macro pores
when the MnCl2 phase expands. A decrease in pressure of ammo-
nia–nitrogen gas mixture resulted in drop of ammonia adsorption
Fig. 12. Effect of temperature, pressure and flow rate of 10,200 ppm of NH3 in N2
gas for different metal chlorides impregnated on IRH-33 at different operating
conditions.
capacities as MnCl26NH3 would no longer form and the drop in
sorption capacity of activated carbon at lower pressures.
4.5.2. Optimizing salt loading on IRH-33
Samples with 30, 40, 50, 60 and 70 wt.% MnCl2 on IRH-33 were
prepared in order to determine the optimum MnCl2 loading on
both a gravimetric and volumetric basis. Table 6 shows the tap
density of the sorbents and their nitrogen gas permeability in the
form of a packed bed. The higher tap density of the sorbent with
50 wt.% MnCl2 resulted in a higher volumetric capacity, which
was important for reducing the size of the filter (Section 4.7).
The measured dynamic adsorption capacities at room tempera-
ture and at elevated temperatures are shown in Fig. 13. SEM
images of the sorbent (Figs. 14 and 15) show that the salt particles
are loaded on the surface as well as in the pores of super-activated-
carbon IRH-33. Fig. 14 shows that there is no significant change
between the fresh and ammonia exposed samples. Fig. 16 shows
large salt crystals on the outside of super activated carbon after
impregnation with 70 wt.% MnCl2. These agglomerates appear to
block ammonia access to MnCl2 that was deposited into deeper
layers of the adsorbent. Similar trends of sorption capacities with
metal chloride loading on porous supports were reported in the lit-
erature [24,25].
 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226 223

13% under the conditions of the dynamic sorption experiments than

22 C under the conditions of the equilibrium adsorption measurements.
Dynamic Ammonia Sorpon Capacity

12%
50 C
80 C 4.5.3. Regeneration/cyclability
11%
Fig. 16 shows the ammonia dynamic sorption capacity at room
10% temperature of 50 wt.% loading of MgCl2 on IRH-33, 50 wt.% load-
(wt. %)

ing of MnCl2 on IRH-33, and 50 wt.% loading of ZnCl2 on IRH-33 as

9%
8%
7%
6%
30 40 50 60
Wt.% MnCl2 on IRH-33
Fig. 13. Comparison of the dynamic sorption capacity (7th cycle) of MnCl2 on IRH-
33 at three different temperatures and an absolute pressure of 5 bar (2 slpm of
10,200 ppm NH3 in N2).
All five adsorbents show high adsorption capacities, good rege-
nerability and follow similar trends with an increase in tempera-
ture. It is evident from Fig. 13 that 40 wt.% MnCl2 on IRH-33 has
the highest gravimetric ammonia adsorption capacity. 50 wt.%
MnCl2 on IRH-33 was found to be better on a volumetric basis
due to the higher tap density (Table 6). The dynamic NH3 sorption
capacity of about 12.5 wt.% at 22 °C for 40 wt.% MnCl2 on IRH-33 is
below the 21 wt.% sorption capacity that was measured by the
equilibrium adsorption isotherm measurements. Hence a smaller
fraction of the MnCl22NH3 was able to convert to MnCl26NH3
a function of the number of adsorption/desorption cycles.
The dynamic adsorption capacity of MnCl2 supported on IRH-33
was higher compared to MgCl2 and ZnCl2 supported on IRH-33
during the first adsorption/desorption cycle but then dropped to
a similar value (11 wt.%) as the other two metal chlorides. All
these three adsorbents show high adsorption capacities, good rege-
nerability and good stability. The pressure drop across the adsor-
70
bent bed stayed constant at about 8 psi for 50 wt.% loading of
ZnCl2 on IRH-33, 13 psi for 50 wt.% loading of MnCl2 on IRH-33
and 11 psi for 50 wt.% loading of MgCl2 on IRH-33 during those
seven cycles at atmospheric pressure. MnCl2 is preferable over
ZnCl2 as an impregnant on IRH-33 due to its lower cost (e.g. $30/
kg MnCl2 vs. $160/kg ZnCl2) and toxicity (NFPA health rating – 2/
MnCl2 vs. 3/ZnCl2).
Cycling of the adsorbent causes a drop of the dynamic sorption
capacity, as illustrated in Fig. 16. One possible cause is that the
regeneration process is performed at a relatively high temperature
(200 °C) and this may have reduced hydroxyl groups present on
IRH-33 which would tend to bind ammonia favorably and this
may have caused a slight loss in BET surface area and DFT pore vol-
ume as shown for sample 4 in Table 2. Salt agglomeration is
another possible cause. However, SEM images did not show signif-
icant differences between fresh and used samples (Fig. 15).

Fig. 14. SEM images of 50 wt.% MnCl2 on IRH-33. Top row (fresh sample), Bottom row (sample after regeneration).

Fig. 15. SEM images of 70 wt.% MnCl2 on IRH-33.

224 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226

Table 6
Tap densities and nitrogen gas permeability of the column loaded with sorbents 30,
40, 50, 60, and 70 wt.% MnCl2 on IRH-33 at 20 °C.

wt.% MnCl2 on IRH-33 Tap density (g/cm3) Permeability (m2)

30 0.41 ± 0.02 (1.2 ± 0.3)  1010
40 0.47 ± 0.01 (1.2 ± 0.3)  1010
50 0.72 ± 0.02 (1.2 ± 0.3)  1010
60 0.67 ± 0.06 (1.3 ± 0.3)  1010
70 0.61 ± 0.03 (1.2 ± 0.3)  1010

Table 7
Pure MnCl2 XPS peak positions in comparison to MnCl2 after it had been exposed to
anhydrous NH3 and thermally regenerated (200 °C in N2).

Name Pure MnCl2 MnCl2 after NH3 Difference (eV)

adsorption and
desorption
Position (eV) Area % Position (eV) Area %
2p3/2 – 1 641.58 30.4 641.96 32.7 0.38
Fig. 16. Comparison of the dynamic sorption capacity of three regenerable NH3
2p3/2 – 2 642.81 25.1 643.17 28.6 0.36
adsorbent materials: (1) 50 wt.% ZnCl2 on IRH-33 (green), (2) 50 wt.% MgCl2 on
2p3/2 – 3 644.12 14.1 644.38 15.3 0.26
Cameron activated carbon (blue), (3) 50 wt.% MnCl2 on IRH-33 (purple). The
measurements were performed at 5 bar absolute pressure and room temperature. Satellites:
(For interpretation of the references to color in this figure legend, the reader is 2p3/2 – 4 645.74 6.5 645.93 6.2 0.19
referred to the web version of this article.) 2p3/2 – 5 647.11 10.2 647.49 10.5 0.38
2p3/2 – 6 648.52 13.7 648.86 6.8 0.34

thermal regeneration under the conditions of this study did not

cause reduction of the MnCl2 phase, which is important for the lon-
gevity of the sorbent.

4.6. Comparison with commercially available adsorbents

The dynamic sorption capacities of the 50 wt.% MnCl2 sup-

ported on IRH-33 adsorbent was compared with commercially
available NH3 adsorbents as shown in Fig. 18. Although, the MOF
Cu-BTC exceeded the dynamic NH3 sorption capacities of MnCl2/
IRH-33, the MOF material could not be regenerated after ammonia
exposure. The dynamic sorption capacity of the MnCl2/IRH-33
adsorbents are about a factor 6 higher than that of the commer-
cially available NH3 adsorbents (e.g. Calgon Ammonasorb, Kuraray,
BASF Selexsorb CD, Molecular Products) that were found to have a
dynamic sorption capacity of about 2 wt.% under dry conditions.
This enables a reduction of the size of the ammonia filter or a
longer operating period before it needs to be regenerated.

4.7. Filter sizing

Fig. 17. XPS Mn 2p3/2 spectra of pure and treated (ammonia exposed and desorbed)
MnCl2 samples.
4.5.4. Stability of MnCl2 during regeneration
Aidoun and Ternan [41] raised the concern that metal chlorides
could get reduced during regeneration in the presence of N2 and
NH3. This would cause a degradation of the ammonia sorption
capacity with time and number of cycles. This phenomena was
observed in their study of CoCl2xNH3 salt in a chemical heat pump
application. Therefore the chemical stability of MnCl2 in nitrogen
and ammonia was assessed by studying the manganese oxidation
state with X-ray Photo-electron Spectroscopy (XPS). The XPS Mn
2p3/2 spectra of MnCl2 before and after ammonia adsorption and
desorption are shown in Fig. 17. The deconvoluted XPS peak posi-
tions are reported in Table 7. Manganese is present in the 2+ oxi-
dation state before and after regeneration. The results therefore
show that exposure of MnCl2 to anhydrous NH3 and subsequent
One of the HSECoE goals for on-board hydrogen purification
was to develop a full scale ammonia filter with a minimum
replacement interval of 1800 miles of driving resulting in a maxi-
mum ammonia outlet concentration of 0.1 ppm (inlet concentra-
tion = 500 ppm) having a maximum mass of 1.2 kg and a
maximum volume of 1.6 L.
The experimentally determined dynamic sorption capacities
and tap densities of MnCl2 on IRH-33 were used for determining
the weight and volume of a full scale ammonia filter. An underlying
assumption was that the vehicle would have a fuel economy of 60
miles per kilogram of H2. An ammonia filter with 40 wt.% MnCl2 on
IRH-33 showed the lowest weight while an ammonia filter with
50 wt.% MnCl2 on IRH-33 showed the lowest volume, due to tap
density differences, as shown in Fig. 19. The ammonia filter with
50 wt.% MnCl2 on IRH-33 can have a weight of 1.1 kg and a volume
of 1.6 L at 20 °C and 5 bar (abs.). This meets the weight and volume
targets of the HSECoE project. A higher weight and volume will be
required when the filter would have to operate at 80 °C.
 B.A. van Hassel et al. / Separation and Purification Technology 142 (2015) 215–226
Fig. 18. Comparison of the dynamic sorption capacity of regenerable NH3 adsorbent
50 wt.% MnCl2 on IRH-33 (purple) with commercially available adsorbents under
dry conditions. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
Fig. 19. Required ammonia adsorbent weight and volume for different loadings of
MnCl2 on IRH-33 for a filter that would need to be replaced every 1800 miles
(assuming 60 miles/kg H2 and an NH3 inlet concentration of 500 ppm). The dynamic
adsorption capacities of the sorbent are the values of the seventh cycle.
Fig. 20. Pressure drop and bed length for different loadings of MnCl2 on IRH-33 at
20 °C. The filter has a fixed internal diameter (D) of 9.16 cm.
Commercial DOT compliant sample pressure cylinders are
available in different sizes and UTRC selected one with an internal
diameter of 9.16 cm [30] in order to obtain a filter with an aspect
ratio in the range of 2–3. The length of the filter was calculated
based on the required adsorbent volume for a full scale ammonia
filter. Pressure drop is an important design consideration. The pres-
sure drop across the full scale ammonia filter was estimated from
Darcy’s equation (Eq. (1)) using the measured permeability values
as shown in Table 7. Among all these sorbents, 50 wt.% MnCl2 on
IRH-33 shows the lowest pressure drop and smallest column
length, followed by 40 wt.% MnCl2 on IRH-33 as the next best sor-
bent (as shown in Fig. 20).
225
5. Conclusions
A high capacity, stable and regenerable ammonia sorbent that is
comprised of metal chlorides deposited on super-activated carbon
IRH-33 from UQTR was prepared and characterized in this work for
removal of ammonia impurity in H2 produced from the thermoly-
sis of ammonia borane.
The dynamic sorption capacity of the developed sorbent is a fac-
tor of 6 higher than that of commercially available ammonia sor-
bents under dry conditions. Among the metal chlorides deposited
on the IRH-33, MnCl2 provided the highest ammonia adsorption
capacities over a wide temperature range compared to ZnCl2 and
MgCl2. 50 wt.% MnCl2 supported on IRH-33 provided the highest
volumetric capacity while 40 wt.% MnCl2 supported on IRH-33 pro-
vided the highest gravimetric capacity.
The filter was sized taking into account the HSECoE goals for the
development of an ammonia scrubber for on-board hydrogen puri-
fication: (1) a minimum replacement interval of 1800 miles of driv-
ing, (2) a maximum ammonia outlet concentration of 0.1 ppm
(inlet concentration = 500 ppm), (3) a maximum mass of 1.2 kg,
(4) a maximum volume of 1.6 L. The filter with 50 wt.% MnCl2 sup-
ported on IRH-33 had a mass of 1.1 kg and a volume of 1.6 L, meet-
ing the HSECoE goal for an on-board ammonia scrubber.
Acknowledgements
This paper was prepared as an account of work supported by
EERE (Energy Efficiency and Renewable Energy) and the FCTO (Fuel
Cell Technologies Office) of the U.S. Department of Energy under
Contract No. DE-FC36-09GO19006. Neither the United States Gov-
ernment nor any agency thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal lia-
bility or responsibility for the accuracy, completeness, or useful-
ness of any information, apparatus, product, or process disclosed,
or represents that its use would not infringe privately owned
rights. Reference herein to any specific commercial product, pro-
cess, or service by trade name, trademark, manufacturer, or other-
wise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government
or any agency thereof. The views and opinions of authors
expressed herein do not necessarily state or reflect those of the
United States Government or any agency thereof.
The authors would like to thank all members of the HSECoE for
stimulating discussions and Ned Stetson, Jesse Adams and Bob
Bowman for their outstanding support.
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