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Recent Progress on Ammonia Cracking Technologies for Scalable Hydrogen

Production

Article in Current Opinion in Green and Sustainable Chemistry · June 2024

DOI: 10.1016/j.cogsc.2024.100945

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Recent Progress on Ammonia Cracking Technologies for Scalable Hydrogen

Production

Korawich Trangwachirachai, Kevin Rouwenhorst, Leon Lefferts, Jimmy A. Faria

Albanese

PII: S2452-2236(24)00066-X
DOI: https://doi.org/10.1016/j.cogsc.2024.100945
Reference: COGSC 100945

To appear in: Current Opinion in Green and Sustainable Chemistry

Received Date: 2 March 2024

Revised Date: 3 May 2024
Accepted Date: 5 June 2024

Please cite this article as: K. Trangwachirachai, K. Rouwenhorst, L. Lefferts, J.A. Faria Albanese,
Recent Progress on Ammonia Cracking Technologies for Scalable Hydrogen Production, Current
Opinion in Green and Sustainable Chemistry, https://doi.org/10.1016/j.cogsc.2024.100945.

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 1 Recent Progress on Ammonia Cracking Technologies for Scalable Hydrogen Production
2 Korawich Trangwachirachai,1 Kevin Rouwenhorst,1,2,3 Leon Lefferts,1 Jimmy A. Faria
3 Albanese1,*
1
4 Catalytic Processes & Materials, MESA+ Institute for Nanotechnology, University of Twente,
5 P.O. Box 217, 7500 AE Enschede, The Netherlands
2
6 Ammonia Energy Association, 77 Sands Street, 6th Floor, Brooklyn, NY 11201, USA
3
7 Koolen Industries, Europalaan 202, 7559 SC Hengelo, The Netherlands
8
9 *Corresponding Author: Jimmy A. Faria Albanese
10
11 Abstract

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12 The global energy transition necessitates the development of technologies enabling cost-

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13 effective and scalable conversion of renewable energies into storable and transportable forms.

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14 Green ammonia, with its high hydrogen storage capacity, emerges as a promising carbon-free
15 hydrogen carrier. This article reviews recent progress in industrially relevant catalysts and
16
17
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technologies for ammonia cracking, which is a pivotal step in utilizing ammonia as a hydrogen
storage material. Catalysts based on Ru, Ni, Fe, Co, and Fe-Co are evaluated, with Co-based
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18 catalysts showing exceptional potential for ammonia cracking. Different reactor technologies
19 and their applications are briefly discussed. This review concludes with perspectives on
overcoming existing challenges, emphasizing the need for catalyst development, effective
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20
21 reactor design, and sustainable implementation in the context of the energy transition.
22 Introduction
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23 The energy transition will hinge on technologies that allow cheap and scalable conversion of
24 variable renewable energies into chemical vectors that can be easily stored, transported, and
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25 transformed back into energy on demand. Green ammonia is a zero-carbon fuel and hydrogen
26 carrier [1-3], thanks to its high hydrogen storage capacity (17.8 % hydrogen by weight [4]), its
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27 simple liquefication at low pressures (8.6 bar) at 20 °C, or even atmospheric pressure at -33°C
28 [5], and the large infrastructure available for its production, storage, and transportation around
29 the globe. Ammonia catalytic dehydrogenation or cracking, however, has been confined to
30 niche applications in the metallurgical industry [6], production of heavy water [7], and, more
31 recently, backup power generation in fuel cells [8]. In this context, the widespread
32 implementation of ammonia as hydrogen storage material will be limited primarily by the
33 capacity for dehydrogenation at an industrial scale. Several perspectives on hydrogen
34 production and storage [9,10], catalyst design [11-13], and process design [14] for ammonia
35 decomposition were published. Direct utilization of ammonia as hydrogen storage [10,15,16],
36 fertilizer production [17,18], Solid Oxide Fuel Cell (SOFC) technology [19], primary fuel [20],
37 thermal power generation [21], and combustion/spark ignition engines [21,22] were also
38 evaluated. To the best of our knowledge, there are few studies focused on the industrial use of
39 hydrogen produced from the ammonia cracker. This mini review discusses the main advances
40 in industrially relevant catalysts and technologies for ammonia cracking and the future
41 opportunities and challenges in the field.
42 Ammonia cracking is an endothermic reaction (see Eq. 1) [23] that requires temperatures above
43 180 °C to be thermodynamically feasible (Figure 1a). The equilibrium conversion of ammonia
44 reaches values above 99% at 400 °C at ambient pressure [24-27] (Figure 1b). Detailed

1
45 thermodynamic calculation can be found in Supporting Information. Industrially, it would be
46 desirable to operate at high pressure as this can reduce the reactor footprint. Unfortunately, the
47 reaction is thermodynamically hindered as pressure increases, which forces the utilization of
48 even higher temperatures to achieve sufficiently high single-pass conversion.
3 1
49 NH3 ⇌ H2 + N2 (H0rxn = 45.9 kJ mol-1 ) [28] Eq. 1
2 2
50
a b

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51 Figure 1. (a) Standard Gibbs free energy profile of ammonia cracking, and (b) equilibrium
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52 NH3 conversion at 0.1, 1, 10, and 50 bar.

53 To conduct this reaction at sufficiently high rates it is essential to employ a catalyst, that is
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54 often based on metal nanoparticles supported on high surface area metal oxide. Exceptions
55 include Fe-based catalysts and Fe-Co alloy-based ammonia cracking catalysts, due to the
56 relatively low cost of Fe. These catalysts are typically bulk-based catalysts [29].
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57 The simplest description that one could use to model reaction kinetics would be a power-law
58 equation, which offers high accuracy for predicting the catalyst performance within the
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59 operational window explored for regressing the kinetic constants and reaction orders (see Eq.
60 1) [11]. In this reaction, the ammonia cracking rate (𝑟𝑁𝐻3 ) is enhanced by the concentration of
61 ammonia ([𝑁𝐻3 ]), while nitrogen ([𝑁2 ]) and hydrogen ([𝐻2 ]) concentrations hinder the rate.
62 Here, the kinetic constant (𝑘) and the reaction orders (a, b, and c) are determined by regression
63 using experimental data. While these models are simple to derive, there is no mechanistic
64 information that can be derived from the regressed orders of reaction and kinetic constants. For
65 this reason, their application is restricted to the operational window in which the data has been
66 collected. In contrast, Langmuir-Hinshelwood kinetics and micro-kinetic models are better
67 suited to extract mechanistic information that can guide catalyst development.
[𝑁𝐻3 ]𝑎
68 𝑟𝑁𝐻3 = 𝑘 × [𝐻 𝑏 𝑐 Eq. (1)
2 ] [𝑁2 ]

69 Hydrogen production from ammonia cracking occurs via sequential dehydrogenation and
70 nitrogen coupling reactions [30], step (1)-(6) below. Here, the reaction proceeds by the
71 adsorption of ammonia on the active sites, followed by a successive N−H bond scission, and
72 then recombination to H2 and N2. The reaction rate is dependent on the adsorption strength of
73 ammonia on metal active sites (referred to as M − N). Broadly speaking, strong M − N
74 interaction promotes the N−H activation. However, if the interaction is too strong, then product

2
 75 desorption from the catalyst surface becomes the limiting step. Weaker M−N interaction could
76 accelerate product desorption but hinder the N−H activation step [31]. In this sequence, there
77 are two steps proposed to possibly be the rate-determining step (RDS), including (i) the first
78 N−H bond scission (step (2)) or (ii) the N* recombination (step 6). The degree of rate control
79 of each one of these steps will depend on the binding strength of the N adatoms to the catalyst
80 surface (step (2)) [32-35]. It has been discovered that the RDS of ammonia decomposition
81 changes with operating temperature [36,37]. At low temperatures (300-500 °C), the RDS is N*
82 recombination, while at higher temperatures the RDS switches to the first N−H cleavage. At
83 these conditions, the surface coverage decreases, due to ammonia desorption, which eventually
84 offsets the enhancements in the N−H bond dissociation rate [38].
85
86 (1) Ammonia adsorption: NH3 (g) + * ⇌ NH3* (ads)
87 (2) 1st N−H cleavage: NH3* (ads) + * → NH2* (ads) + H* (ads)

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88 (3) 2nd N−H cleavage: NH2* (ads) + * → NH* (ads) + H* (ads)

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89 (4) 3rd N−H cleavage: NH* (ads) + * → N* (ads) + H* (ads)

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90 (5) H2 recombination: 2H* (ads) → H2 (g) + 2*
91 (6) N2 recombination: -p
2N* (ads) → N2 (g) + 2*
where * is the active surface site.
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92
93 In industrial applications, ammonia cracking is operated at nearly complete conversion at
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94 elevated temperatures and moderate pressures, increasing the contribution of the reverse
95 reaction (i.e. ammonia synthesis) in the kinetics. To account for these effects, Sayas et al.
96 proposed a kinetic model derived from the power-law model [39] (Eq. 2) in which the
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97 decomposition rate is hindered by the reverse reaction [40-42].

3
𝑎 1 𝑃𝑁2 𝑃𝐻
98 𝑟𝑁𝐻3 = 𝑘 × 𝑃𝑁𝐻 𝑃𝑏 (1 − ( 2
)) Eq. 2
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3 𝐻2 𝐾𝑒𝑞 2
𝑃𝑁𝐻 3

99 In this scenario, one could operate the reactor at even higher pressures to maximize the
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100 hydrogen productivity per active site. However, the resulting lower conversion per pass [39]
101 will require a larger recycle stream and ammonia recovery systems, increasing operational and
102 capital expenditures [43].
103 To activate this reaction, one can resort to supported transition metals, metal alloys, and metal
104 compounds such as metal oxides hydrides, carbides, nitrides, amides, or imides [11,31,44].
105 Among those, transition metals such as Ru, Ni, Fe, and Co have been widely studied as catalytic
106 centers for ammonia decomposition [45]. Ru-based materials provide the highest reactivity,
107 especially at low pressures [46]. Here, it has been proposed that B5-type surface sites on Ru
108 control the observed activity [47], which is linked to nitrogen recombination as a rate-
109 determining step [48]. These sites are present in larger concentrations on Ru nanoparticles of
110 ca. 2 nm [49]. The density of B5 sites can be further increased by tailoring the shape of the
111 nanoparticles. For instance, Karim et al. [50] reported that hemispherical Ru with an average
112 size of ca. 2.4 nm has the highest activity due to the larger concentration of B5 sites. Similar
113 results were reported by Zheng et al. [51] on Ru nanoparticles of ca. 2.2 nm. Unfortunately,
114 Ru-based catalysts are expensive and prone to H2 inhibition due to the low dissociation barrier
115 of hydrogen. It was found that the coverage of H2* and H* species increases with the partial
116 pressure of H2, together with the decrease in vacant sites [52]. The dissociation of H2* to H* is
117 typically rapid on Ru surfaces which suppresses the NHx dehydrogenation and, thus, ammonia
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118 decomposition rate, leading to lower catalyst utilization at high conversion levels and at
119 elevated pressures [53]. Thus, finding alternatives to Ru is key for large-scale implementation
120 of ammonia cracking.
121 Nickel is a promising candidate for ammonia dehydrogenation due to its abundance, acceptable
122 activity, and high resistance to the 0.2-0.5 wt.% H2O in commercial-grade anhydrous ammonia.
123 For reference, Fe- and Fe-Co alloy-based catalysts suffer from H2O inhibition [54], preventing
124 their use based on commercial-grade anhydrous ammonia. Nickel has a lower cost than cobalt
125 and is currently used for steam methane reforming (a similar catalyst formulation). The small
126 amount of water contamination could possibly be present due to its hydroscopic character,
127 which leads to water adsorption during storage, transportation or transfer[55]. Nevertheless,
128 the presence of small water content (~0.5%) in ammonia significantly reduces its corrosiveness
129 [55], in which copper, brass, and zinc-alloys are highly reactive towards ammonia [56].
130 Therefore, these materials must be avoided for the ammonia cracking system, while aluminum,
131 cast iron, carpenter 20, and stainless steel (304 or 316) are recommended due to their higher
stability.

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132

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133 N-containing compounds, such as metal imides or amides, were found to be effective materials

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134 for ammonia cracking. They can also be used as a support to promote the activity of non-noble
135 metal catalysts [57-62]. However, they are very sensitive to water. In this case, oxynitrides,
136
137
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which are stable in water, would be more promising. Previous studies reported that the N-
containing materials that can form N-vacancies are likely to be active for ammonia
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138 decomposition [63]. Hence, perovskite-type oxynitrides were developed for ammonia
139 cracking.
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140 On commercial catalysts, Ni clusters are supported on -Al2O3, CaAl2O4, or MgAl2O4,

141 providing excellent heat and mechanical stability during reactions at high temperatures [1].
142 More recently, Co-based catalysts have been shown to achieve surprisingly high activities that
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143 surpassed those observed on conventional Ni and Ru catalysts. To illustrate the evolution of
144 the catalyst developments over the last decade, we have summarized in Figure 2, the activity
of the catalysts based on Ru [39,64-81], Ni [63,65,82-101], Fe [93,102-104], Co [88,93,104-
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145
146 113], bimetallic [114-116] and compound [117,118] as a function of the year of publication.
Detailed operating conditions and conversion levels can be found in Table S2 in the Supporting
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147
148 Information. One could use this analysis to identify the most promising candidates for ammonia
149 dehydrogenation at a large scale. In this line, one can see in Figure 2a that Ru- (entries 2 and
150 8, Trxn = 400−500 °C) and Ni-based (entries 32, 37, 43, and 45, Trxn = 600−650 °C) catalysts
-1
151 have shown high hydrogen productivities with values c.a. 100 tonH2 ton-1 cat day , until 2012
152 when Co-based catalysts (entry 72, Trxn = 600 °C) were reported by the group of Kaykac et al.
153 [105]. These cobalt catalysts have shown excellent hydrogen productivity with values of c.a.
-1
154 300 tonH2 ton-1
cat day . This three-fold increase in productivity has positioned these materials
155 as one of the frontrunners for large-scale ammonia cracking. Interestingly, hydrogen
156 productivity obtained by ammonia cracking has surpassed that of the steam reforming of
-1
157 methane (c.a. 65tonH2 ton-1 cat day ) [119,120]. In the past two years (Figure 2b), Ni-based
158 catalysts (entries 46 − 58, Trxn = 500 − 600 °C) have become more attractive in catalyst
159 development for ammonia cracking. A 10% Ni/CeO2 (entry 52) provided the highest H2
-1
160 productivity at 115.5 tonH2 ton-1 cat day at 550 °C. Nevertheless, Co-based catalysts are still
161 more active. For instance, K-promoted Co loaded on MgO-CeO2-SrO (entry 76) exhibited
-1
162 166.2 tonH2 ton-1cat day H2 production at 500 °C. In addition, bimetallic, such as Ni-Co (entry
163 84), and perovskite La0.5Sr0.5NiO3-δ (entry 92) catalysts have also shown a promising H2
-1
164 productivity of 93.5 and 84.7 tonH2 ton-1 cat day at 650 °C and 550 °C, respectively.
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165
a b

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166 Figure 2. Summarized H2 productivity over Ru, Ni, Fe, and Co active sites from (a) 2010 to

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167 2021 and (b) 2022 to 2024 (including bimetallic and compound catalysts) at ambient pressure.
168 The numbers shown in the Figure are the entries of the references presented in supplementary
169
170 Ammonia cracking technology
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Table S2. The detailed table can also be found in Table S2 in the Supporting Information.
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171 The successful implementation of ammonia cracking will require careful selection of the
catalyst formulation and reactor technology. The elevated temperatures, moderate pressures,
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172
173 and endothermicity restrict the available options for conducting this process to multi-tubular
174 reactors with hydrogen and/or ammonia burners or electrical heaters, and, more recently,
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175 membrane reactors. The schematic diagram of a typical ammonia cracking process is shown in
176 Figure 3.
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177
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178
179 Figure 3. Schematic diagram of ammonia cracking process [121].
180 In the following section, we briefly discuss the main challenges and opportunities of these
181 strategies.
182 Multi-tubular reactor with hydrogen and ammonia burners
183 The reactor setup is similar to that of a steam methane reformer. The feedstock is replaced by
184 ammonia, and the reactor is equipped with external burners where ammonia and part of
185 produced hydrogen are used as fuels [122]. The reactor is loaded with Ni-, Fe-Co-, or Ru-based
186 catalysts, allowing the ammonia to crack inside the tubular reactor. Heat integration with the
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187 downstream H2 purification unit is also possible [122,123], and the pilot plant is planned to be
188 operational in 2024 [124]. Furthermore, energy losses to the environment are quite substantial,
189 leading to specific energy inputs (SEI) of ca. 10.1 kWh kg-1
H2
[125-127]. The high temperatures
190 inside the furnace lead to substantial NOx and N2O emissions (global warming potential, GWP,
191 of -10 to 542 for NOx [128] and nearly 300-fold for N2O [129], compared to that of CO2),
192 which further increase the environmental impact of the technology. This technology is currently
193 used for producing heavy water on a large scale as will be discussed later [130], reaching more
194 than 1000 tonNH3 day-1 , albeit with natural gas burners and Fe-Co alloy-based catalysts.
195 Therefore, several companies have been developing ammonia burners with reduced heat losses
196 and low nitrogen oxide emissions [131,132]. Also, DeNOx technology such as selective
197 catalytic reduction (SCR) can be utilized to reduce nitrogen oxide emissions [133].
198 Multi-tubular reactor with electric heater
199 The electrical heating reactor has been commercially operated in small-scale applications (1500
kgH day-1 ) [134], such as metallurgy and stationary power generation. The major difference is

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200

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201 that the reactor is electrified to provide heat instead of gas-firing. The benefits of electric

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202 heating are faster on/off responses, uniform heating, and pollutant-free [135], as compared to
203 the gas-firing one, allowing it to follow fluctuating renewable electricity or fluctuating demand.
204
205
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AFC has disclosed the first modular ammonia cracker that is purely electrically operated
[136,137]. The cracker could be fully operated within 10 minutes from room temperature and
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206 achieved 9.5 kWh electrical power consumption per kilogram of produced hydrogen. A
207 drawback of the electrical heater is that heat integration between the reactor and H2 purification
is not feasible, limiting the energy efficiency of the process, if pure H2 is required. Moreover,
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208
209 there will be a limitation of the electrically heated reactor. For instance, in the Siemens reactor,
210 silicon rods are used and heated by passing the direct current through the rods [138]. The
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211 temperature at the center of the rod must be below its melting temperature, in this case 1687 K
212 is the maximum value that can be reached before structural failure [139]. Thus, electrically
213 heated reactors are industrially scalable even for high-temperature applications.
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214 Membrane reactor

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215 Ammonia cracking via membrane technology has been operated to generate highly purified
216 hydrogen for a proton-exchange membrane (PEM) fuel cell. The reactor allows for H2
217 purification through permeation by a Pd membrane concurrently with an ammonia cracking
218 reaction at 500-600 °C [53,140]. However, pure Pd membranes normally encounter H2
219 embrittlement at temperatures and pressures lower than 300 °C and 2 MPa, respectively [141].
220 Moreover, defects can be formed at temperatures higher than 550 °C, suppressing the
221 permeation selectivity. Therefore, precise temperature control is required for the pure Pd
222 membrane system. The process is applicable to small-scale hydrogen production only due to
223 the high cost of the palladium membrane. Furthermore, long-term testing and minimization of
224 the Pd loading should be achieved to enable commercial implementation. For instance,
225 microporous ceramic membranes are more cost-effective [142]. However, their porous
226 structure frequently leads to H2 with insufficient purity [143-147]. In this case, dense ceramic
227 membranes (such as perovskites, pyrochlores, and tungstates) could be more suitable [148].
228 These types usually require elevated temperatures (> 400 °C) [149] for better H2 conductivity,
229 which is also favorable for ammonia cracking. The major drawback of the dense ceramic
230 membranes is its poor H2 flux. Distinct techniques, such as doping trivalent ions to perovskites
231 [150-152], dispersing metal (e.g., Pd) to the ceramic matrix (so called cermet) [153-155], or
232 blending two ceramic membranes (namely cercer) [156-159], can be applied for higher H2 flux.
233 Alternatively, Pd-coated on V membrane shows the ability to permeate H2 without inhibition
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234 by N2 or NH3 [160,161]. An example is the demonstrator of the Australian company CSIRO,
235 using a commercial Ru-based catalyst and vanadium membrane [162].
236 Commercial applications of ammonia cracking
237 Metallurgy industry
238 There is a current commercial application of an ammonia cracker unit in the metallurgy
239 industry for welding, brazing, and nitriding [6]. Ammonia is preheated and fed through the
240 reactor loaded with Ni-based catalyst. The process is generally operated at high temperatures
241 of 850-1000 °C to ensure full conversion. Small units are heated electrically, while large units
242 use a gas-burning heater. The hydrogen productivity of these crackers is in the range of 1-1500
243 kgH day-1 , with a typical energy efficiency of 30-60% [134]. The energy efficiency is defined
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244 by the energy content of hydrogen at the outlet divided by the energy of the inlet stream:
𝑚𝐻2 ,𝑜𝑢𝑡 × 𝐿𝐻𝑉𝐻2
245 𝐸𝑛𝑒𝑟𝑔𝑦 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 =
(𝑚𝑁𝐻3 ,𝑖𝑛 × 𝐿𝐻𝑉𝑁𝐻3 ) + 𝐸𝑓𝑢𝑒𝑙𝑠 + 𝐸𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦

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246 Where 𝑚𝐻2 ,𝑜𝑢𝑡 is the mass of hydrogen at the outlet, 𝑚𝑁𝐻3,𝑖𝑛 is the mass of ammonia at the

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247 inlet, 𝐸𝑓𝑢𝑒𝑙𝑠 and 𝐸𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 are the energy input from other fuels and electricity, respectively,
248 and LHV is the lower heating value, in which the 𝐿𝐻𝑉𝐻2 and 𝐿𝐻𝑉𝑁𝐻3 are 120 𝑀𝐽 𝑘𝑔𝐻−12 and
249 18.646 𝑀𝐽 𝑘𝑔𝑁𝐻 −1
3
, respectively.
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250 Heavy water production
251 The production of heavy water by cracking ammonia has been operated since the 1960s, with
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252 current facilities operational in Thal Vaishet (India) and Arroyito (Argentina). The deuterated
253 ammonia is produced via the H/D exchange reaction with HD and liquid NH3 at low
254 temperature (15 K) [163] or the reaction of deuterium gas (D2) with nitrogen at elevated
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255 temperature (400-600 °C) and pressure (10-30 MPa) [164]. In this way, deuterium is enriched
256 in deuterated ammonia (NH3-xDx, where x = 1 or 2) [7]. The cracking unit with a Co-Fe
bimetallic catalyst is fed deuterated ammonia at high pressure (120-150 bar) to produce a
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257
258 mixture of deuterium gas (D2), hydrogen-deuterium gas (HD), and N2 [165,166]. The
productivity of hydrogen from this ammonia cracker is 30000-425000 kgH day-1 . The heavy
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259
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260 water is obtained by combusting the gas mixture produced from the ammonia cracker.
261 Stationary power (low-temperature fuel cell)
262 Ammonia is used as a carbon-free hydrogen storage/carrier for off-grid fuel cells operation
263 [167,168]. Ammonia crackers are currently commercially available for stationary power
264 generation in low-temperature alkaline fuel cells [169]. Vaporized ammonia is passed through
265 an electrically heated ammonia cracker at temperatures below 700 °C [170]. The outlet mixture
266 (approximately 75% H2 and 25% N2 with trace amounts of residual NH3 and water) can be
267 directly fed to the fuel cell without purification. Moreover, a portion of the electricity produced
268 by the fuel cell is allocated to power the electric heating system for the ammonia cracker. The
269 present ammonia cracking technology with alkaline fuel cells yields a power output ranging
270 from 5-600 kW [171,172], corresponding to a hydrogen production capacity spanning from 12-
271 1410 kgH day-1 at 35% efficiency. However, capturing and utilizing the heat waste from the
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272 hot product stream remains challenging [173].
273 Pipeline-grade H2
274 Gaseous ammonia is fed through a heat exchanger prior to entering the cracking unit, which is
275 generally operated at 600-900 °C and 10-80 bar. The ammonia cracker comprises of a multi-
7
276 tubular reactor with burners loaded with supported Ni catalysts. The downstream hydrogen will
277 be purified using a pressure swing adsorption (PSA) technique. The cracking unit has been
278 aimed to produce pipeline-grade hydrogen in 2026 in Port of Rotterdam [174]. The productivity
279 of hydrogen is approximately 10000-500000 kgH day-1 with an energy efficiency of 85-90%.
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280 Conclusions and perspectives

281 Catalytic dehydrogenation of ammonia can be readily accomplished on a variety of metal-
282 supported catalysts with sufficient activity for large-scale deployment. While Ru-based
283 catalysts have served as the benchmark for hydrogen productivity, their high cost induces
284 limited industrial application. Despite their lower activity, Ni-based materials have become the
285 standard formulation for industrial ammonia cracking thanks to their robust performance and
286 lower costs. Additionally, the advent of Co-based materials has changed this picture. These
287 materials have shown excellent performance at industrially relevant operating conditions,
288 making them an excellent candidate for large-scale ammonia cracking. Coupling the correct
289 catalyst and reactor technologies is essential to ensure stable operation of the process at large

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290 scale. While gas-fired crackers have been demonstrated at large scale for ammonia
291 dehydrogenation, their low efficiency, large carbon footprint, and NOx/N2O emission will

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292 complicate adoption in the framework of the energy transition. Electrical heating offers a
293 unique opportunity to decarbonize heat generation and to improve the flexibility of ammonia
294
295
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crackers, which is mostly applicable to processes that do not require purified hydrogen. Finally,
membrane-based reactors offer a unique opportunity to conduct reaction and separation,
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296 producing high-purity hydrogen in a single step. However, the use of expensive palladium
297 membranes and complex operations hinders the scalability of this technology.
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298 In this context, the utilization of highly active catalysts with electrically heated crackers will
299 be key to ensuring fast commercial uptake of the ammonia dehydrogenation technology at a
large scale. This will require additional research to develop catalysts with improved tolerance
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300
301 to hydrogen poisoning, water resistance, and high activity to enable operation at high pressures
302 and low temperatures. Next to this, regarding carbon and NOx/N2O emissions from the gas-
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303 fired ammonia crackers, developing electrified fixed bed reactors with high energy efficiency
304 will enable substantial reductions in the polluted gas of the process.
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305
306 Credit authorship contribution statement
307 Korawich Trangwachirachai: Literature review, data processing, and writing of the original
308 draft. Kevin H.R. Rouwenhorst: formal analysis, writing review, and editing, and visualization.
309 Leon Lefferts: formal analysis, writing review, and editing, and visualization. Jimmy Faria
310 Albanese: Conceptualization of the scope, supervision, project administration, editing and
311 review of the manuscript, and funding acquisition.
312
313 Declaration of Competing Interest
314 The authors declare that they have no known competing financial interests or personal
315 relationships that could have appeared to influence the work reported in this paper.
316
317 Acknowledgements

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318 The research project was funded by The Nederlandse Organisatie voor Wetenschappelijk
319 Onderzoek (NWO) Project NWOCA.2019.027 called RESILIENT-ISLAND and the U.S.
320 Navy Research Lab Global Project N62909-23-1-2047.
321
322 Supporting Information.
323 Supplementary data Supplementary material related to this article can be found in the online
324 version.
325
326
327
328

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 Declaration of interests

☐ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☒ The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

Jimmy A. Faria A. reports financial support was provided by The Nederlandse Organisatie voor
Wetenschappelijk Onderzoek (NWO) Project NWOCA.2019.027 called RESILIENT-ISLAND and the U.S.
Navy Research Lab Global Project N62909-23-1-2047.

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