Energy 217 (2021) 119384

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Review

A comprehensive review of hydrogen production from methanol

thermochemical conversion for sustainability
Gabriel Garcia a, b, Emmanuel Arriola a, b, Wei-Hsin Chen a, c, d, *, Mark Daniel De Luna b
a
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan, 701, Taiwan
b
Energy Engineering Program, National Graduate School of Engineering, University of the Philippines, Diliman, Quezon City, 1101, Philippines
c
Research Center for Smart Sustainable Circular Economy, Tunghai University, Taichung, 407, Taiwan
d
Department of Mechanical Engineering, National Chin-Yi University of Technology, Taichung, 411, Taiwan

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

Article history: Methanol, a liquid hydrogen carrier, can produce high purity hydrogen when required. This review
Received 19 June 2020 discusses and compares current mainstream production pathways of hydrogen from methanol. Recent
Received in revised form research efforts in methanol steam reforming, partial oxidation, autothermal reforming, and methanol
8 November 2020
decomposition are addressed. Particular attention is paid to catalyst development and reactor technol-
Accepted 18 November 2020
Available online 24 November 2020
ogy. Copper-based catalysts are popular due to their high activity and selectivity towards CO2 over CO but
are easily deactivated and have low stability. Attempts have been made using different metals like zinc,
zirconia, ceria, chromium, and other transition metals. Catalysts with spinel structures can significantly
Keywords:
Hydrogen production
improve activity and performance. Palladium-zinc alloy catalysts also have high selectivity towards H2
Steam reforming and CO2. For reactors, novel structures such as porous copper fiber sintered-felt are prefabricated and
Partial oxidation pre-coated before employment in microreactors. Monolith structures provide maximum surface area for
Autothermal reforming catalyst coatings and lower pressure drops. Membrane reactors drive reactions forward to produce more
Methanol decomposition H2. Swiss-roll reactors achieve heat recovery and energy saving in reactions. In summary, this
Water gas shift reaction comprehensive review of hydrogen production from methanol is conducive to the prospective devel-
opment of a hydrogen-methanol economy.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Current status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Previous reviews . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3. Sustainability of energy systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4. Motivation and novelty statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Sources of methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Methanol as a hydrogen carrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Methanol steam reforming (MSR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Catalyst development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.1. Copper-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.2. Pd-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3. Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Partial oxidation of methanol (POM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

* Corresponding author. Department of Aeronautics and Astronautics, National

Cheng Kung University, Tainan, 701, Taiwan.
E-mail addresses: [email protected], [email protected]
(W.-H. Chen).

https://doi.org/10.1016/j.energy.2020.119384
0360-5442/© 2020 Elsevier Ltd. All rights reserved.
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

4.1. Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2. Catalyst development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.3. Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3.1. Thin-film tubular reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3.2. Structured reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3.3. Swiss roll reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Autothermal reforming of methanol (ATRM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.1. Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.2. Catalyst development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.3. Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6. Methanol decomposition (MD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.1. Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6.2. Catalyst development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7. Perspectives and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

1. Introduction all other storage technologies have low energy efficiencies. Life-
cycle efficiency for chemical hydrides is affected due to by-
1.1. Current status product regeneration off-board. There is also a large energy
requirement for compression and liquefaction for physical storage
There is growing global attention on climate change and air [6].
pollution as evidenced by the formal ratification of the Paris These challenges indicate a demand for a hydrogen carrier that
Agreement in the 21st Conference of Parties in 2015. The agreement can easily be handled using the current oil/gas infrastructure, as
had the ultimate goal of keeping the mean global surface temper- well as technologies to efficiently and economically generate
ature increase to 1.5e2
C compared to pre-industrial levels by hydrogen from this fuel. In this specific regard, methanol as a
2100, increasing global and local focus on the reduction of green- hydrogen-carrier is a great candidate to address these re-
house gas (GHG) emissions [1]. This raises the need for green fuels quirements. Methanol has a high H/C ratio of 4:1, is liquid at room
and low-carbon energy systems, given that the energy sector is the temperature, and can be converted to hydrogen at lower temper-
dominant contributor to a country’s GHG emissions. The energy atures relative to most fuels [7].
sector predominantly uses fossil fuels such as coal, crude oil, and Fig. 1 summarizes the four different thermochemical processes,
natural gas as primary resources to deliver power to many aspects including methanol steam reforming (MSR), partial oxidation of
of human life. In 2018, the global primary use of fossil fuels methanol (POM), autothermal reforming of methanol (ATRM), and
amounted to around 11.7 billion tons of oil equivalent [2]. This methanol decomposition (MD) that can utilize methanol to pro-
equated to 81% of total energy globally. Currently, coal and natural duce hydrogen.
gas are used mainly in generating electricity, while crude oil is
refined predominantly for the transport sector. The burning of fossil
fuels contributes greatly to increasing carbon in the atmosphere 1.2. Previous reviews
and exacerbates climate change. Renewable energy such as solar,
wind, hydro, tidal, geothermal, and biofuels generated 14% of the Interest in methanol as a fuel for hydrogen production has been
total energy mix in 2018 [2]. Solar photovoltaic, solar thermal, and growing in the past two decades. Fig. 2 shows a publication search
wind energy are sustainable sources of energy but are highly var- in Scopus using the keywords “methanol” and “hydrogen produc-
iable and intermittent. These sources of energy lack the reliability tion”. The growing interest mirrors fuel cell research that utilizes
required for power generation. high purity hydrogen.
Hydrogen is identified as a key pathway for deep decarbon- Palo et al. [7] reviewed methanol steam reforming (MSR) for
ization for the energy and transport sectors in various countries [3]. hydrogen production and discussed various developments in MSR
A versatile energy vector that can be generated from various catalysts, reactors and system development, and the specific ad-
renewable (biomass and water) and non-renewable (natural gas, vantages and disadvantages of methanol as a hydrogen vector. They
coal, and hydrocarbons) sources, Hydrogen has better efficiency suggested that methanol’s simplicity would prove advantageous on
than gasoline in terms of energy-to-movement conversion [4]. In the low power side (100e1000 W) as a pre-packaged consumable
addition to better efficiency, the emissions of air pollutants from for reformed methanol fuel cells (RMFC), but would still be disad-
hydrogen are reduced compared to traditional fossil fuels. vantageous in terms of total reformed hydrogen production.
To fully deploy hydrogen in the energy sector, many challenges Sa et al. [9] reviewed catalysts for methanol steam reforming
need to be addressed. In the present state of hydrogen technologies, and summarized recent developments in copper and group VIII to X
the establishment of a hydrogen infrastructure is remarkably metals as active materials. The authors compared both catalyst
expensive, or otherwise excessively complicated [5]. Storage, groups and concluded that copper-based catalysts exhibited higher
handling, transport, and generation of hydrogen is problematic, activity, while group VIII to X metal-based catalysts outperformed
especially when compared to the logistics of conventional liquid copper in thermal and long-term stability. In terms of selectivity,
fuels. The volume and weight of hydrogen storage systems are catalysts with copper, platinum, and palladium as active materials
currently still too high so it detrimentally affects vehicle range and favored the production of H2 and CO2, in contrast with most cata-
lysts based on group VIII to X that favored CO.
2
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

Fig. 1. A schematic of the thermochemical route for hydrogen production from methanol (MSR [8e13], POM [14e20], ATRM [10,21e23], MD [24e27]).

Fig. 2. The number of published articles with keywords of “methanol” and “hydrogen production” taken from Scopus.

Yong et al. [12] looked at the different reaction mechanisms on reforming. They conceded that currently, the surface reaction
the surface of the copper-based catalysts used for methanol mechanisms have not been established owing to complications

3
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

arising from the secondary reactions: total oxidation of methanol Formaldehyde synthesis is the main market for methanol, con-
(TOM), water gas shift reaction (WGSR), and partial oxidations of sisting of 27% of total demand, and other applications include olefin
carbon monoxide (CO) and hydrogen (H2). production, methyl tert-butyl ether (MTBE), and tert-amyl methyl
Iulianelli et al. [28] reviewed and compared hydrogen produc- ether (TAME) production, blending component for gasoline, and
tion from methanol via conventional and membrane steam dimethyl ether (DME) production [7]. To date, the production of
reforming reactors. A reduction of total reactor weight and volume hydrogen from methanol is a niche market and is still in its infancy.
enabled further use in mobile reforming applications, selective
hydrogen in a wide range of pressure and temperature conditions,
and enhancement of methanol conversion by driving the MSR re- 2.1. Sources of methanol
action forward. However, a technology and research gap in the
production of high permeate fluxes in low pressures potentially Commercial methanol is mostly generated from synthesis gas
translates to higher cost and lower stability during scaling up. (syngas) by the catalytic reaction of its components: H2, CO, and
Xu et al. [29] reviewed different catalysts based on copper and CO2. The majority of the commercial methanol produced today
palladium for use in methanol steam reforming. The study reported comes from syngas from fossil fuels, either through the steam
on the comparable performance of Pd/ZnO to copper-based cata- reforming of natural gas or the gasification of coal [34]. Neverthe-
lysts in MSR. Pd/ZnO showed relatively superior CO2 selectivity due less, emerging technologies and new research are looking at syngas
to the formation of PdeZn alloys. Formaldehyde intermediates in from renewable sources such as biomass [35]. Eqs. (1) and (2) show
the MSR reaction were transformed more effectively to H2 and CO2 the reactions to synthesize syngas from methane via steam
over catalysts with PdeZn alloys in contrast with metallic Pd- reforming. Eq. (3) represents the water gas shift (WGS) [36] reac-
dominated catalysts that favored H2 and CO. tion that may occur during syngas formation or utilized in specific
shift reactors to further convert CO and H2O to CO2 and H2,
1.3. Sustainability of energy systems respectively.

There is a need to emphasize the sustainability of hydrogen CH4 þ H2 O4CO þ 3H2 ; DH298 K ¼ þ206 kJmol1 (1)
production systems for energy due to the increasing demand for
clean and green energy. Advanced sustainability tools such as
exergy, exergoenvironmental, and exergoeconomic analyses are CH4 þ 2H2 O4CO2 þ 4H2 ; DH298 K ¼ þ165 kJmol1 (2)
not currently in the scope of this review. However, it is imperative
that these tools are given focus in the future to evaluate the energy CO þ H2 O4CO2 þ H2 ; DH298 K ¼ 41 kJmol1 (3)
systems’ holistic sustainability. Exergy-based methods that couple
life-cycle analysis (LCA) considerations are increasingly popular Eqs. (4) and (5) represent methanol synthesis, usually over the
tools to evaluate several aspects of biofuel energy [30]. Studies like industrial standard catalyst (Cu/ZnO/Al2O3) [37]. In parallel, the
Aghbashlo et al. [31] used exergoenvironmental analysis to eval- reverse of the WGS reaction represented by Eq. (3) occurs.
uate the impact of the generation of the two routes (power gen-
eration and fertilizer production) from anaerobic digestion. This CO2 þ 3H2 4CH3 OH þ H2 O; DH298 K ¼ 50 kJmol1 (4)
type of analysis showcases areas that need improvement in specific
objectives. Another example is a study by Siddiqui and Dincer [32] CO þ 2H2 4CH3 OH; DH298 K ¼ 91 kJmol1 (5)
that investigated a comparative well-to-pump life cycle analysis of
different hydrogen production methods from ethanol and meth- Bio-methanol, or methanol originating from biomass, is gener-
anol. Highlighting the environmental effects of different routes. ated through multiple routes involving various processes. Fig. 3
details the different production routes from the primary source to
1.4. Motivation and novelty statement methanol.

At the time of writing, to the best of the authors’ knowledge,

there is no comprehensive review of hydrogen production from 2.2. Methanol as a hydrogen carrier
methanol looking at different pathways of conversion. The above
reviews deal specifically with MSR, while methanol-specific re- A unique fuel, methanol is advantageous as a hydrogen carrier in
views for POM, ATRM, and MD are not reported. This review aims to many aspects. It has the same H/C ratio as methane (4:1), but is a
address this gap by a comprehensive examination of hydrogen liquid at atmospheric pressure and typical environmental tem-
production from methanol in the current literature. A comparison peratures. Its low boiling point (65
C) allows vaporization in
of four major pathways of methanol conversion is discussed. The roughly the same magnitude as water, and it is miscible in water
purpose is to provide an understanding of recent developments in enabling easier processing and containment [7,40].
the field and compare different generating routes. Within these The conversion of methanol to hydrogen occurs at a lower
specific routes, an overview of catalyst development and reactor temperature range compared to other fuels. This has been attrib-
development is provided. uted to the absence of CeC bonds in methanol that requires a
higher energy input to break allowing a low-temperature operation
2. Methanol leads to low CO levels [33]. Miscibility in water enables simplifies
feed inlet design as water and methanol can be fed together and has
Methanol is a clear and colorless liquid with a sweet pungent anti-freezing properties as a solution.
odor that is soluble in water and a byproduct of the wood distil- An important aspect of using methanol as a hydrogen vector is
lation industry. The first commercial process to produce methanol rapid and efficient conversion to H2 for utilization in energy ap-
was established in 1830, while the first plant was established by plications. The subsequent sections will discuss these processes
BASF in 1923 [33]. At present, methanol is a worldwide chemical with methanol as feed for established thermochemical conversion
commodity with a capacity of 49 million metric tons in 2010 and is processes such as steam reforming, partial oxidation, auto-thermal
projected to reach 95 million metric tons by 2021 [34]. reforming, and methanol decomposition.
4
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

Fig. 3. Production routes from primary feedstock to methanol. (Figures are based on studies of Kamarudin (2013) [38], Shamsul (2014) [35], and Zakaria (2016) [39]).

3. Methanol steam reforming (MSR) convert the remaining CO into H2 and CO2.

Steam reforming is a well-known process of converting hydro- 3.1. Mechanisms

carbons into hydrogen due to its high efficiency and economic
operation [44]. It generates more moles of hydrogen for every mole MSR and MD reactions are expressed in Eqs. (6) and (7),
of methanol compared to the oxidation processes. Fig. 4 shows a respectively. WGSR, Eq. (3) consumes the carbon monoxide
schematic summary of MSR including subsequent steps. The generated by MD to form additional hydrogen molecules. These
reformer is usually coupled with a separator that harvests the high- three reactions depict the evolution of hydrogen from methanol
purity H2 stream for applications such as PEMFCs. If high carbon [28]. Different reaction mechanisms are proposed by multiple
monoxide levels are present, a shift reactor can be added to further researchers.

Fig. 4. A schematic of methanol steam reforming (MSR).

5
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

zinc were also investigated for MSR by Fasanya et al. [55]. The Zn
DH298 ¼ þ50 kJmol1


CH3 OH þ H2 O4CO2 þ 3H2 (6) nano-rods were grown in cordierite before impregnation with Cu.
The nano-catalyst was evaluated for MSR in a fixed bed reactor
between 180 and 350
C. For temperatures at 180e230
C, no CO
DH298 ¼ þ91 kJmol1


CH3 OH 4 CO þ 2H2 (7)
production was observed for the methanol-to-water ratio of 0.8.
The widespread use of copper-based catalysts in MSR extends This shows potential as an effective catalyst for MSR for low CO
from the use of the same catalyst in methanol synthesis [7]. The applications.
following literature investigates mechanisms of MSR over standard Zirconium was also investigated in conjunction with Cu/ZnO
copper-based catalysts as it has widespread applications in in- and was found to enhance performance in multiple instances. The
dustry and research. addition of ZrO2 has been reported to increase the dispersion of Cu
Yong et al. [12] discussed several mechanisms for the MSR re- crystallites within the catalyst. Jeong et al. [56] provided a com-
action over copper-based catalysts. The first proposal was a parison between Cu/ZnO, with and without the addition of Zr and
sequential scheme of methanol decomposition followed by the Al2O3. The highest methanol conversion and lowest CO concen-
water gas shift reaction (MD-WGS). Carbon monoxide was treated tration were observed over the Cu/ZnO/ZrO2/Al2O3 catalyst,
as the primary product, and the observation of low CO was attributing to the role of Zr in enhancing copper dispersion and
attributed to the WGSR achieving equilibrium [45]. In this mecha- forming small copper particles on the catalyst surface. Increased
nism, it was proposed that Eq. (7) occurred first, followed by Eq. (3). activity from the addition of Zr has been investigated by Yao et al.
An alternative proposal suggests that the products were directly [57] using Cu/ZrO2 catalysts via different preparation methods.
generated from methanol dehydrogenation. The MSR mechanism is They reported that using oxalate gel co-precipitation resulted in
still an ongoing endeavor and an active area of research. high component dispersion and smaller copper crystallite size.
Amorphous ZrO2 structure potentially caused the CueZr interac-
3.2. Catalyst development tion that lowers reduction temperature peaks. Sanches et al. [58]
used CueZn catalysts prepared by homogenous precipitation and
Catalysts in MSR are typically composed of active material, a reported that the presence of Zr increased lattice strain, making Cu
promoter, and support. This section will discuss specifically Cu- and crystals more accessible to reactants leading to higher methanol
Pd-based catalysts because of their high activity and selectivity to conversion. Zr also promoted the formation of CueZn alloy that has
the MSR reaction in conjunction with different promoters. been shown to improve methanol conversion. Sanches et al. [59]
further investigated the effect of Zr on Cu/ZnO catalysts. The results
3.2.1. Copper-based catalysts indicated that increased microstrain exposed active CuO sites to
In contrast with most of Group VIII to X metal catalysts that reactants, increasing catalyst reducibility. The authors attributed
favor the production of syngas [46], copper-based catalysts favor the increase in microstrain to the distortion of the crystalline ge-
the production of carbon dioxide and hydrogen, making it favorable ometry of the Cu/ZnO catalyst with the embedding of amorphous
for generating H2 for PEMFC applications. However, challenges Zr.
encountered in the use of copper-based catalysts such as the high Another alkaline oxide, cerium (Ce) has been reported to affect
likelihood of sintering, sensitivity to sulfur and oxygen, and pyro- dispersion, redox behavior, and catalytic activity in copper-based
phoricity can deactivate the catalysts. The effects of various vari- catalysts [7]. Ce can adsorb oxygen as the oxidation state shifts
ables have been investigated in the literature to understand catalyst from Ce (III) to Ce (IV). Oxygen is then released to react with carbon
performance. Reduction temperature, active site dispersion, active in the catalyst surface to suppress coke deposition [22]. This unique
site surface area, promoter addition, and catalyst preparation redox behavior has made ceria an interesting promoter, as evi-
methods are some of the variables investigated in the literature. denced by multiple studies investigating its effect on the activity
The following subsections discuss literature that investigated the and stability of copper-based catalysts. Liu et al. [60] reported that
aforementioned variables. Cu/CeO2 catalysts had better performance than Cu/ZnO. Interaction
Cu/ZnO is an industry-wide catalyst used in low-temperature of CeO2 with Cu/ZnO/Al2O3 enhanced activity and hydrogen
water gas shift, methanol synthesis, and MSR reactions. Conven- selectivity. Zhang et al. [61] tested the performance of various
tionally, the formation of the catalyst starts with co-precipitating catalysts promoters loaded in copper (Cu/ZnO, Cu/ZnO/Al2O3, Cu/
from a mixture of zinc and copper nitrates and sodium carbon- ZnO/CeO2, Cu/ZnO/ZrO2, and Cu/ZnO/CeO2/ZrO2) for steam
ate; this yields an amorphous precipitate that ages to a crystalline reforming, and observed a very stable performance for Cu/ZnO/
precursor. Mixed oxides of CuO and ZnO are obtained after drying CeO2/ZrO2 with no noticeable deactivation in 360 h of operation.
and calcination, and are finally activated after the reduction of Baneshi et al. [62] used a homogenous precipitation method to
copper into its metallic state, usually by passing hydrogen gas as generate a CuO/ZrO2/CeO2/Al2O3 catalyst. The presence of ceria led
pretreatment. This pretreatment process is a difficult operation to to better and more uniform dispersion, smaller Cu particle size,
bring to onboard systems [47]. higher methanol conversion, low CO selectivity, and high stability.
There have been numerous observations of improvement in Wan et al. [63] doped CeO2 into CuO/ZnO/Al2O3 and observed that
catalytic activity when ZnO is present with Cu, empirically con- Ce lowered the activity of the catalyst but decreased CO selectivity.
firming its role as a promoter. However, there is still no consensus In summary, ceria has been reported as advantageous support to
on the promoting mechanism, and is still being investigated at copper-based catalysts. It improves dispersion, particle size, and
present [48]. Burch et al. [49] proposed the spillover model where stability, while suppresses coke formation, making the catalyst
hydrogen was trapped by ZnO and facilitated hydrogenation in active for a long duration. The addition of Ce drives selectivity to-
subsequent reactions. Yoshihara et al. [50], Ovesen et al. [51], wards H2 and CO2, and lowers CO, making it ideal for fuel cell ap-
Hadden et al. [52], and Topsoe et al. [53] suggested that the ZnO plications. However, there are conflicting reports of the effect of Ce
affected the morphology of active sites to. Lastly, Kanai et al. [54] on Cu catalyst activity for MSR. There are cases that the presence of
attributed the promotion effect of ZnO to the CueZn alloy formed Ce lowered activity in the aforementioned studies.
after reduction. Copper-zinc catalysts are also used in conjunction Other metals that are being investigated as promoters or sup-
with other promoters and support; and it is commonly utilized ports for copper-based catalysts, Yang et al. [64] synthesized Cu/
with Zirconia, Ceria, and Alumina. Nano-catalysts of copper and ZneAl catalysts with rare earth metal modifications and a ZneAl
6
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

hydrotalcite precursor. Yttrium (Y), lanthanum (L), cerium (Ce), transfer within the system [77]. A high pressure drop within the
samarium (Sm), and gadolinium (Gd) were investigated. The results reactor increases the pumping power required to keep a steady
showed that Ce, Sm, and Gd addition improved copper dispersion, stream of methanol and water flowing in the reactor, while poor
surface area, and catalyst reducibility in comparison to unmodified heat transfer characteristics produce inefficiencies within the
Cu/ZneAl catalyst with Ce/Cu/ZneAl outperforming all other reactor creating local differences. Microreactors address this by
modified catalysts. Other metals such as Indium were tested by scaling reactor configurations to inner dimensions in the magni-
Matsumura et al. [65]. The addition of In2O3 stabilized the catalyst, tude of millimeters [28,78].
and inhibited CO formation, however, at inferior catalyst activity. Catalyst compatibility, reactant-catalyst contact, and pressure
Gallium (Ga) addition into Cu/ZnO catalyst has been reported to drop are important variables to consider in the design of an MSR
perform well in the catalytic hydrogenation of CO2 to methanol reactor. Fig. 5, based on the study of Iulianelli et al. [28], shows the
[66]. Toyir et al. [13], Pohar et al. [67], and Liu et al. [13] showed that different configurations discussed for conventional MSR reactors.
the presence of Ga increased Cu catalyst activity. Nano-catalysts of Coil-based reactor designs (Fig. 5a) yield high conversions but with
Cu catalysts with other metals are also investigated. Nano-powders trade-offs in pressure drop that can be a restriction for compact
of a catalyst of Cu, Cr, and Fe (CuCr1-xFexO2 at x ¼ 0e1) were applications. In contrast to coil-based reactors, rectilinear channel
investigated by Hwang et al. [68] for MSR at 350
C. The application reactor designs (Fig. 5b) have low pressure drops but have low
of nano-catalysts can be applied to fuel cell vehicles due to its conversions because of sporadic distributions of mass [78]. A
simplicity and high efficiency and stability. pinhole design (Fig. 5c) has the advantages of coil-based reactors in
terms of conversions at lower pressure drops, but has a more
3.2.2. Pd-based catalysts complicated control due to a mass distribution that is dependent on
Group VIII metal-based catalysts (Ni, Rh, Pd, and Pt) have the flow conditions [79]. Lastly, radial reactor designs (Fig. 5d) are
outstanding thermal stability when compared with copper-based highly compatible with MSR due to increasing sectional area when
catalysts, this implies a lower propensity to sinter at tempera- the product gas exits the reactor, lowering the pressure drop in
tures above 300
C (a primary reason for catalyst deactivation). comparison with tubular reactors with a constant velocity profile
However, the aforementioned metals favor the production of syn- [80].
gas (CO and H2) instead of hydrogen (H2 and CO2) in MSR [69]. For There are different strategies used in the design of micro-
MSR, Palladium (Pd) is shown to favor the same intermediary steps reactors. Channel wall coating was explored by Bravo et al. [81]. Cu/
as copper-based catalysts when mixed with ZnO [70]. Ranganathan ZnO/Al2O3 was used to coat a microchannel reactor on quartz and
et al. [71] carried out MSR over Pd/ZnO and Pd/CeO2 and compared fused silica. The microchannel performance was a significant
the effects of Zn against Ce. They accounted for the shift in selec- improvement over the same catalyst in a packed-bed configuration.
tivity on the quantity of acidic or basic active sites where Pd/ZnO Xinxin et al. [82] performed MSR in a wall-coated reactor with a
had more acidic sites, thus favoring CO2 production. In contrast, PdZn/Al2O3/FeCrAl catalyst, and achieved 100% methanol conver-
Chin et al. [72] reported a highly active and selective Pd/Zn catalyst sion and a low CO selectivity at 0.5% in stable operation. Tajrishi
that was able to for PdeZn alloy at moderate temperatures et al. [83] used a wall-coated reactor to carry out MSR to test the
(>300
C) in reducing conditions. Iwasa et al. [73] also attributed performance of Cu/SAB-15-based nanocatalysts. Sanz et al. [77]
the promotion of MSR and increased CO2 selectivity to the alloying compared coated micro-etched and micro-milled plates for MSR.
of Pd with Zn in reductive conditions. They extended experiments They demonstrated high selectivity for H2 (75.0%) and CO2 (23.5%),
to include other metals such as Cd, In, and Ga, and confirmed that and low levels of CH3OH (0.06%) and CO (1.44%), and concluded that
alloying increased MSR activity and selectivity over MD. chemical etching and milling had similar performances but
Iwasa et al. [74] investigated Pd/ZnO, Pd/Al2O3, and Pd/ZrO2 chemical etching had the advantage of easy adaptation to large
catalysts in MSR and showed that Pd was highly affected by the scale production. The key for wall-coated reactors is to have a
choice of support. They reported that using ZrO2 as support best uniform catalyst surface that maximizes surface area and lowers
enhanced the dispersion of Pd within the catalyst, but the Pd/ZnO deposition on corners. Shedding, low adhesion, and high
provided the best selectivity for MSR. Further research of the Pd/ machining costs are barriers to the utilization of wall-coated re-
ZnO catalyst by Iwasa et al. [75] showed that a prior reduction of actors [84].
the catalyst at higher temperatures would result in greater activity. Packed-bed microreactors use conventional catalysts in micro-
They attributed this effect to the formation of more PdeZn alloys reactors. By utilizing conventional catalysts, the set-up of these
during prior reduction that further increased desired behaviors in reactors is simple and economic. Flow plugging and high pressure
the catalyst. drops are the key disadvantages of packed-bed micro-reactors [85].
Kim et al. [76] investigated the effects of Ru addition to Pd/Al2O3 Catalyst structures are employed to minimize pressure drop that
catalysts on MSR. The authors compared the performances of Pd/ can be pre-coated outside the reactor fabrication rendering
Al2O3 and Pd/Ru/Al2O3 catalysts and reported the enhanced activity machining more economical. Zhou et al. [84] investigated the
with Ru addition. The enhanced activity was attributed to alloying performance of porous copper fiber sintered felt (PCFSF) as a
of Pd and Ru that resulted in decreased Pd particle size, and a high catalyst structure for an MSR microreactor. PCFSF was coated with
degree of dispersion throughout the catalyst. Temperature- Cu/Zn/Al/Zr. Zhou et al. [86] further extended the study on PCFSF to
programmed desorption analyses revealed that PdeRu alloying include the effect of fiber material, surface morphology, and
increased the desorption rate of the CO species adsorbed in the Pd different Cu/Al ratios in the support. Their results indicated that a
active site. This step was revealed to be the rate-determining step rough morphology showed better performance in terms of meth-
and consequently increasing the reaction activity of MSR when Ru anol conversion.
was added. Membrane reactors incorporate membrane components that
can be either an extractor, distributor, or contactor [28]. An
3.3. Reactors extractor separates a desired product from the reactor by selective
permeation, a distributor controls the rate of addition of a specific
Traditional MSR reactors are tubular in a design filled with reactant, and a contactor intensifies the interaction and contact of
catalyst particles in a packed-bed configuration. A packed-bed catalyst and reactants. A membrane separator coupled with the
reactor design has high pressure drops and unbalanced heat reformer is an efficient way to address this challenge as well as
7
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

Fig. 5. Reactor designs of (a) coiled, (b) rectilinear, (c) pinhole, and (d) radial structures.

reduce capital and operating costs [87]. The removal of hydrogen way that the amount of oxygen is well below the stoichiometric
within a reactor system will shift the equilibrium in favor of the requirement for full oxidation, resulting in a mixture of hydrogen
forward MSR reaction, and can lower the operating temperature and carbon monoxide, with nitrogen and other trace elements [90].
and increase methanol conversion. Basile et al. [88] investigated Hydrogen and carbon dioxide are formed in a succeeding WGS
MSR in varying water/methanol molar ratios and reaction tem- reactor from water and carbon monoxide from syngas [91].
peratures in a fixed bed reactor coupled to a dense PdeAg mem- MSR is a favored thermochemical pathway to generate
brane over Cu/ZnO/Al2O3/MgO. The setup with the membrane hydrogen because of its high yield. However, MSR requires heat
reactor performed better in terms of methanol conversion and H2 input to proceed because it is an endothermic reaction. On the
production than the fixed bed reactor alone. Ghasemzadeh et al. other hand, POM is an exothermic process that generates heat as
[89] used a silica membrane reactor for carrying out MSR and the reaction moves forward; it is kinetically faster and requires a
developed a one-dimensional isothermal model to assess the ef- smaller reactor vessel in comparison to MSR. Chen et al. [92] cold-
fects of catalyst loading, sweep gas flow rate, and H2 selectivity at started POM using ultra-low weight Pt/Al2O3 and (hexagonal boron
different temperatures and pressures. Catalyst loading and sweep nitride) h-BN-Pt/Al2O3 catalysts, achieving hydrogen production
gas flow rate had a positive correlation with the MR performance, without any preheating done. Temperature control, however, is a
increasing H2 selectivity and yield. focal challenge in highly exothermic conditions. A higher reactor
temperature shifts selectivity towards carbon monoxide and away
4. Partial oxidation of methanol (POM) from hydrogen [93]. Typically, POM has half the hydrogen selec-
tivity of MSR and higher CO.
Partial oxidation occurs when fuel and air are partially reacted Methanol is a favorable feedstock option for partial oxidation
or combusted in a reactor to create hydrogen-rich syngas. Air fed to [94], and several studies have compared its performance with
the reactor is limited to inhibit the total oxidation reaction of hy- methane or higher hydrocarbons. The CeC bond in methanol re-
drocarbons to carbon dioxide and water. It is controlled in such a duces the coke formation that causes deactivation [95]. Operational

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G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

conditions for POM can also be adjusted rapidly, improving control catalysts in POM. The catalysts used demonstrated high activity and
[96]. Catalytic POM has also reported higher conversions at lower selectivity for H2 and CO2. The study reported that the activity of
temperatures than partial oxidation systems using methane. POM increased with the measured Cu metal surface area where
CueZn interfaces play a role in modifying dispersion and particle
4.1. Reactions size of copper. Additionally, the presence of Al in the catalyst
inhibited methanol conversion but improved stability and selec-
The overall POM is a highly exothermic reaction and can be tivity for CO2. Chi et al. [101] investigated the effect of the oxidation
expressed by Eq. (8). state of Cu in the catalyst on the selectivity. The study reported an
increased H2 selectivity with higher amounts of reduced metallic
DH298 ¼ 192 kJmol1


CH3 OH þ 0:5 O2 42 H2 þ CO2 (8) copper (Cu0), while CO2 selectivity is primarily driven by the O2
partial pressure. The results indicated contradicting constraints as
The total system of reactions for POM, however, is more complex an increase in O2 partial pressure in the feed results in the metallic
and involves different pathways for methanol and oxygen [97]. copper to oxidize faster into Cu2O, lowering the H2 selectivity.
Otsuka et al. [98] and Lyubovsky et al. [99] proposed that inter- Presently, a need to further elucidate the activity in different
mediate reactions for POM are: MSR (Eq. (6)), MD (Eq. (7)), WGS oxidation states is needed to determine the most active state of a
(Eq. (3)), methanol combustion (Eq. (9)), methanation (Eqs. (10) metal.
and (11)), and oxidative hydrogenation of methanol (Eq. (12)). Wang et al. [102] evaluated the effects of various noble metal
promoters on Cu/Cr on catalyst performance. The methanol con-
DH298 ¼ 675:4 kJmol1


CH3 OH þ 1:5 O2 4CO2 þ 2 H2 O version, CO selectivity, H2 selectivity, and CO2 selectivity were used
(9) to measure the catalyst performance and are summarized in Fig. 6.
Copper has low stability during operation because of the high
DH298 ¼ 206:2 kJmol1


CO þ 3 H2 4CH4 þ H2 O (10) risk of sintering [100]. Using a similar approach in MSR, Pd-based
catalysts were evaluated for POM due to its high stability and
long operations on-stream. Catalysts based on metallic palladium
DH298 ¼ 164:9 kJmol1


CO2 þ 4 H2 4CH4 þ 2H2 O (11) (Pd0) have been found to favor decomposition products (H2 and CO)
similar to other Group VIII to X metals. PdeZn alloy, however,
DH298 ¼ 157:0 kJmol1


CH3 OH þ 0:5 O2 4HCHO þ H2 O interacted in a way that was found to be selective to reforming
products (H2 and CO2) and offer a high methanol conversion rate in
(12)
POM [103,104]. Pd/Zn catalysts report comparable methanol con-
The aforementioned reactions describe proposed mechanisms version levels to Cu-based catalysts and similar selectivity. Agrell
for POM that are still being explored in literature today. et al. [14] prepared Pd and Pd/ZnO catalysts for use in POM. The
results indicated that Pd/ZnO selectively converted methanol into
4.2. Catalyst development H2 and CO2 but with a higher rate of CO generation when compared
with Cu-based catalysts.
Catalysts employed in POM systems have been categorized Other materials such as silver (Ag) and gold (Au) have been
based on the active materials used and are generally classified into investigated as potential catalysts. Mo et al. [105] found that Ag
noble and non-noble metals. Operating temperatures for POM are supported by ZnO, Al2O3, and ZnOeAl2O3 was active towards POM;
above 200
C to yield a high methanol conversion. The selectivity unfortunately, Ag-catalysts were observed to have low selectivity
for CO2 and H2 in POM is highly dependent on the catalyst. towards hydrogen. Potentially, modifying Ag/ZnO with CeO2 can
Considering various metals, the most extensively used for POM are improve H2 selectivity. Fig. 7 summarizes the performances of
copper-based materials due to their high activity [99]. In this sec- different Ag-based catalyst as investigated by Mo et al. [105].
tion, the literature investigating different active metals, promoters,
and supports for catalytic POM is reviewed.
Cu/Zn is a natural extension for converting methanol into
hydrogen. Huang and Wang [19] first introduced POM using a Cu/
Zn catalyst in 1986. The catalysts were prepared from co-
precipitation in different compositions of Cu and Zn by weight
and underwent activity measurements post-reduction. The study
demonstrated exothermic POM at the optimum composition of
20e40% copper by weight with a promising high rate of hydrogen
production. Alejo et al. [100] observed a positive correlation be-
tween surface area and activity. Increasing copper loading above
40 wt% decreased activity. Chen et al. [18] observed that
temperature-programmed reduction (TPR) peaks of catalysts
increased with higher copper loading. This means that during
reduction pretreatment, higher copper loading required an
increased quantity of hydrogen and a higher temperature to reduce
CuO into active metallic Cu. The study attributed this effect to the
possible increase of Cu crystallite size, lower dispersion of Cu, and
weaker interactions with the supports at higher copper composi-
tions. There is an optimum composition of copper in a Cu/Zn
catalyst. An excess of copper (above 40 %wt.) lowers the metal
surface area and dispersion as observed by the aforementioned
literature. Fig. 6. Performance summary of Cu-based catalyst promoters and supports for partial
Alejo et al. [100] investigated Cu/ZnO and Cu/ZnO/Al2O3 oxidation of methanol.

9
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

configuration contributes to varied heat transfer within the sys-

tem. Similar to MSR, this creates hot spots within the reactor,
creating inefficiencies within the system. Agrell et al. [14] reported
a 60e120 K temperature difference between the furnace wall and
the catalyst bed in a PBR for POM. Additionally, Kulprathipanja and
Falconer [93] observed that the reactor temperature jumped by
100 K during POM set at 565 K. The catalyst bed exhibited bright
orange hot spots and increased CO selectivity. Due to the
exothermic nature of POM, these thermal jumps are uncontrolled
and can disrupt the design for the desired reaction.

4.3.1. Thin-film tubular reactor

To manage temperature jumps, thin-film tubular reactors (TFTR)
were employed by Kulprathipanja and Falconer [93]. An indium
and tin oxide catalyst was prepared by simultaneous precipitation
and mixed with Al2O3. The solution was deposited in a tubular
reactor. The use of TFTR in POM eliminated the thermal jumps that
were observed in PBR. Because of the better temperature control,
CO levels were also minimized. However, due to the geometry of
TFTRs, increasing space time may prove difficult, and may require
Fig. 7. Performance summary of Ag-based catalyst promoters and supports for POM. recirculation to achieve enough contact time between reactants
and catalysts. As observed in the aforementioned study, more
hydrogen was formed at higher space times in TFTR.
Platinum (Pt) has high activity as a catalyst in POM with some
studies reporting low CO product levels [106] (see Table 1). Chen
4.3.2. Structured reactor
et al. [107] utilized an ultra-low composition of platinum (0.2%) in
Porous support structures can be coated with catalysts and used
POM. At a high gas hourly space velocity (GHSV) of 20,000 h1,
in reactors to minimize plugging for POM. With proper design,
hydrogen production was achieved without pre-heating. However,
enough contact can be established between the catalyst and re-
cold starting POM had a lower conversion compared with a set-up
actants by the structure. Kulprathipanja and Falconer [93] tested a
with pre-heating. Table 2 shows a summary of recent studies
monolith tank reactor for POM. The reactor was observed to have a
regarding catalyst development for POM.
temperature difference within the monolith, with the higher
temperature observed nearer the heater. But the geometry of the
4.3. Reactors monolith tank reactor allowed for higher contact between re-
actants and catalysts.
Unlike MSR reactors, the absence of steam simplifies most de-
signs. The conventional design of packed-bed reactors is still the 4.3.3. Swiss roll reactor
least complex. A non-uniform reaction surface in a packed-bed A recent reactor design in POM is the Swiss-roll reactor. Chen

Table 1
Summary of relevant properties of different hydrocarbons for hydrogen production where all values are presented at STP or otherwise stated [41e43].

Property Methanol Ethanol Methane

Molecular formula CH3OH C2H5OH CH4

Other names Methyl alcohol, Wood alcohol, Carbinol Ethyl alcohol, Fermentation alcohol, Marsh gas, Methyl hydride
Spirits of wine
Physical description Transparent, colorless liquid at room Colorless liquid at room temperature. Colorless and odorless gas
temperature. Pungent, alcoholic odor. Mild, rather pleasant odor similar to
wine
Hydrogen content by mass (%) 12.58 13.13 25.13
Oxygen content by mass (%) 49.93 34.73 0
Higher heating value (MJ kg1) 22.88 29.85 55.00
Molecular weight (g mol1) 32.04 46.04 16.04
Density (kg m3) 786.3 785.3 0.65
Boiling point (
C) 64.7 78.2 161.5
Freezing point (
C) 97.6 114.1 182.6
Flash point (
C) 11 13 188
Auto-ignition temperature (
C) 464 363 537
Solubility (mg mL1) 1000 1000 0.022
Human toxicity Ingestion of 30e250 mL is fatal. Ingestion causes gastrointestinal Inhalation in high concentrations may
Causes irritation on contact and inhalation irritation. Causes severe eye irritation cause asphyxiation.
on contact.
Sources Syngas Biomass Natural gas
Carbon dioxide Sugars Biomass
Carbon dioxide
Production processes Catalytic synthesis Fermentation Power-to-methane
Direct liquefaction Anaerobic digestion
Hydrogenation Hydrogenation

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G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

Table 2
Summary of catalyst studies for POM and ATRM found in the literature.

Catalyst Composition Reactor Catalyst Reactor O2/MeOH BET surface MeOH Selectivity Ref.
load (mg) temperature (mol/mol) area (m2g1) conversion
H2 (%) CO (%)
(
C) (%)

Au/TiO2 Au (3%) TiO2 Packed Bed 50 300 0.5 107.2 63 7 59 [93]

Au/ZrO2 Au (3%) ZrO2 Packed Bed 50 300 0.5 76.1 58 91 0 [93]
Au/ZrO2eTiO2 Au (3%) ZrO2eTiO2 Packed Bed 50 300 0.5 102.9 58 2 23 [93]
ITO/Al2O3 ITO (75%) Al2O3 Thin Film Tubular 30 451 0.53 15.7/61.7 58 53 2 [93]
Cu/CeO2 Cu (5%) CeO2 Fixed bed 50 280 0.3 88 70.9 35 <10 [97]
Au/TiO2 Au (2%) TiO2 U-Shaped Microreactor 30 200 0.3 79 60 25 [108]
Cu/TiO2 Cu (2%) TiO2 U-Shaped Microreactor 30 200 0.3 72 68 21 [108]
AueCu/TiO2 Au (1%) Cu (1%) TiO2 U-Shaped Microreactor 30 200 0.3 99.6 98 8 [108]
CueMneZn Cu (30%) Mn (20%) Zn (50%) Micro-reformer with 20 180 55 98 98 [109]
finger shape channels
Au/TiO2eFe2O3 Au (1.37%) TiO2eFe2O3 Fixed bed reactor 275 0.3 45 95 76 0 [110]
Au/TiO2eCo3O4 Au (1.10%) TiO2eCo3O4 Fixed bed reactor 275 0.3 42 52 80 [110]
Au/TiO2eZnO Au (2.18%) TiO2eZnO Fixed bed reactor 275 0.3 41 65 85 [110]
AueRu/Fe2O3 Au (1%) Ru (1%) Fe2O3 U-Shaped Microreactor 40 250 0.5 100 92 25 [90]
Au/ZnO/Al2O3 Au (17%) Zn (83%)* U-Shaped Microreactor 40 250 0.5 98 64 10 [111]
Au/CuO/ZnO Au (3%) Cu (37%) Zn (60%) U-Shaped Microreactor 20 275 0.5 100 97.7 1.5 [112]
Pt/Al2O3 Pt (0.2%) Al2O3 Spray System 300 140e635 0.6 141.66 99 91.3 3.5 [17]
h-BN-Pt/Al2O3 h-BN (0.05%) Pt (0.2%) Al2O3 Spray System 300 226e551 0.6 150.12 100 3.14 [107]
h-BN-Pd/Al2O3 h-BN (0.05%) Pd (0.2%) Al2O3 Spray System 300 253e557 0.6 153.51 100 6.27 [107]

et al. [106] conducted POM in a Swiss-roll reactor using h-BN-Pt/ 5.2. Catalyst development
Al2O3 as the catalyst. The radial design of the reactor makes the
hotter product and cooler reactant streams flow countercurrent to Suitable catalysts for ATRM need to be active for both POM and
each other, improving heat transfer and acting as pre-heating for MSR under oxidation and reduction conditions, simultaneously
the reaction. This is a marked improvement from the heat transfer [60]. Because of the large difference in the reaction rates between
limitations of conventional reactors. Hydrogen production was the endothermic steam reforming reaction and the exothermic
achieved from a cold start using the aforementioned catalyst and methanol oxidation, the primary parameter that needs to be
reactor. The authors concluded that the Swiss roll reactor was a controlled in the reactor is the temperature. Table 3 shows a
capable reactor to simultaneously recover the excess enthalpy summary of the catalysts discussed by Chen et al. [46].
while catering POM with high efficiency for hydrogen production in Cu-based catalysts have high dispersion related to high catalyst
the industry. activity. However, Cu is prone to sintering leading to deactivation
[15]. CeO2 is a viable option supporting Cu in ATRM [121]. The
unique redox property of Ce enables it to be versatile and is suitable
for preventing coking [122]. Hori et al. [123] suggested that Zr is a
5. Autothermal reforming of methanol (ATRM)
compatible dopant to alter the chemical and structural properties
of CueCe, improving stability and activity.
Autothermal reforming is a process involving both partial
Zn-based catalysts for ATRM showed considerable activity. Liu
oxidation and steam reforming reaction systems [44]. The fuel re-
et al. [60] used pelletized ZnOeCr2O3 at relatively high tempera-
acts with both air and steam to produce hydrogen-rich gas. Auto-
tures for ATRM, and showed good activity. Different supports for
thermal reforming of methanol (ATRM) uses sufficient heat
zinc catalyst were evaluated by Liu et al. [60] and is summarized in
generated from exothermic POM to trigger endothermic MSR with
Fig. 8. Based on the evaluation, Cr as support shows the highest
the ideal mixture of air, steam, and fuel. ATRM is ideally operated at
methanol conversion, while Zr shows the highest hydrogen selec-
a thermoneutral point where the system neither release nor
tivity. Table 4 shows additional catalysts in the literature.
consume external energy [113]. This replaces the external heat
input for MSR reactors making ATRM setups relatively simpler with
lower capital costs. Compared to POM, ATRM has better heat re-
5.3. Reactors
covery and increased hydrogen yields.
The majority of hydrogen generated in ATRM comes from MSR
because of the additional hydrogen formed from water [132]. Due
5.1. Reactions to the endothermic nature of MSR, oxygen is added in the reactor to
generate heat chemically via POM [133]. The system then needs an
The system of reactions that describe ATRM is derived from both input of an oxygen carrier, either pure oxygen or more commonly,
Eq. (6) for MSR and Eq. (8) for POM. The reactant ratio is theoret- air [134]. ATRM reactors in the literature show similar strategies as
ically calculated so that the reaction will be thermally neutral [114]. MSR and POM reactor designs. Extensive use of packed-bed re-
But in a general form, ATRM is described by Eq. (13). actors in different geometries represent the bulk of the designs.
Unique packing of catalysts can provide advantages in ATRM.
CH3 OH þ ð1  2rÞ H2 O þ rO2 4ð3  2rÞH2 þ CO2 Richards et al. [135] used a stratified catalyst bed coupled with a
(13) Cu-based catalyst. The reactor showed fairly high methanol con-
DH298 ¼ ð  241:8ð2rÞ þ 49:5Þ KJmol1 ;


0&r&0:5
version at low O2/MeOH ratios compared to conventional packed-
The “r” in the equation represents the ratio between oxygen and bed reactor configuration. Similar to MSR and POM, monolithic
methanol fed to the reaction. structures were used to improve the surface area and pressure
11
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

Table 3
Summary of catalysts in ATRM used in recent studies.

Catalyst Temperature (
C) Highest MeOH conversion (%) Ref.

CuO/MnO 280e320 98 [115]

Cu/ZnO 200e295 95 [116]
ZnOeCr2O3/CeO2eZrO2 500e540 96 [117]
ZnOeZnCr2O4/CeO2eZrO2 427e507 100 [60]
Cu/ZnO/Al2O3 200e400 100 [118]
ZneCreCu 200e400 100 [119]
ZnOe Cr2O3/CeO2eZrO2/Al2O3 280e400 100 [120]
CuO/ZnO/Al2O3 250e300 100 [46]

drops in ATRM. Sanz et al. [136] used a monolithic catalyst that

proved advantageous in providing heat to the downstream pellets.
Novel feeding designs can also improve efficiency and activity.
Johnson Matthey developed a reactor for ATRM over a CueSi
catalyst named “Hot Spot” reactor [127,137]. The reactants were
point injected in the middle of the catalyst bed. They produced a
local high-temperature region that enabled the endothermic
reforming reactions in the rest of the catalyst bed.
Mu et al. [117] had successfully fabricated a mini-reactor
composed of a reforming chamber, a catalytic combustion cham-
ber, and two pre-heating chambers. The mini-reactor could be
started at room temperature by the initial combustion of methanol
to drive ATRM, producing hydrogen. Optimal methanol conversion
achieved was 96.4%, with a reformed gas containing 51.04% H2,
26.68% N2, 2.12% CO, and 20.16% CO2.

6. Methanol decomposition (MD)

Methanol decomposition (MD) is an endothermic reaction that

dissociates methanol into hydrogen and carbon monoxide. MD
occurs to completion at low temperatures but at significantly
Fig. 8. ZnCr/Support with their corresponding methanol conversion, CO, CO2, and H2
slower kinetics than reforming and oxidation. An MD reactor may
selectivity. utilize waste heat from engine exhaust heat in in-situ applications
with higher efficiency than gasoline or direct methanol [138].

Table 4
Summary of ATRM catalysts in literature.

Catalyst Composition Reactor Catalysts Reactor H2O/MeOH O2/MeOH, MeOH Selectivity Ref.
size temperature, mol/mol mol/mol conversion,


C %
H2, % CO, %

Monolithic catalyst Noble Metal catalyst Packed bed reactor 3.81 cm 637.7 1.5 0.30 99.5 75 6 [124]
Monolithic Ceria wafer Platinum group metals Stratified bed reactor 8.763 cm 250 1.5 0.16 35 72 9 [125]
coated with PGM and
Pelletized FCRM - 2
Monolithic catalyst wash 1% Pt/Al2O3, 20% Ceramic microchannel 14 cm 450 1 0.6 90 70 11 [126]
coated with Pt/Al2O3 colloidal alumina network
dispersion
BASF V1765 catalyst CuO/ZnO/Al2O3 catalyst Bench-scale fixed bed 380 g 350 1.5 0.11 95.88 60.37 1.31 [127]
modified with ZrO2 reactor
Annular monolithic catalyst ZnO$Cr2O3/CeO2$ZrO2 Novel mini-reactor 510 1.5 0.27 96.4 51.04 26.68 [117]
Calcium, Gadolinium, and Ce 0.5 Zr 0.33 M 0.17 Packed bed tubular reactor 550 2.6 0.2 84.5 89.2 [128]
Magnesium
FCRM e 2 Catalyst commercially available Packed bed reactor 0.25 cm 280 1.6 0.16 35 72 <1 [129]
Cu/Zn/Al2O3
MDC-3 Catalyst CuO (42 wt%) ZnO Packed bed reactor assisted 15 g 300 1.3 0.5 90 [23]
(47 wt%) Al2O3 (11 wt%) with microwave
ICI 33-5 Catalyst Cu ZnO Al2O3 High conductivity 300 1.4 99 [130]
honeycomb reactor
Cu/SiO2 Catalyst Fixed Bed flow reactor 17.34 g 250 0.1 0.25 94 1.93 [131]
MDC-3 Catalyst CuO (42 wt%) ZnO Packed bed reactor 300 1.5 0.5 97 78 [46]
(47 wt%) Al2O3 (11 wt%)

12
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

Multiple catalysts have been historically investigated for MD; Cu, deactivation of Cu in MD using a Cu/SiO2 catalyst for a long oper-
Ni, group VIII metals, and Zn/Cr catalysts have been evaluated by ation time. Rapid deactivation of catalyst occurred both in the
literature in different structures, preparation methods, and com- initial operation (0e20 h) and the advance stage (200e296 h). The
ponents [27,138]. MD is an attractive option for the production of initial deactivation was attributed to coking and sintering of Cu. The
hydrogen because it can reach a 100% conversion at a temperature final stage was due to loss of the support structure of the catalyst
of 473 K at atmospheric pressure [27]. It has potential applications and was an irreversible degradation of the SiO2 during operation.
as a fuel processor for portable power [139], high-pressure appli- Due to the high deactivation rate of copper and the need for both
cations in gas turbines [140], in-situ reformers in internal com- active and stable catalysts, multiple metals have been evaluated in
bustion engines, and material for chemical and material processing the literature. One of these metals is Nickel (Ni), an active catalyst
[138]. In this section, the discussion will focus on the reaction for MD. Matsumura et al. [26] performed MD over Ni supported by
mechanism (6.1) and catalysts (6.2). silica. An optimal Ni content of 40% showed the highest conversion
rate of around 65% at 250
C. The study reported that the crystal-
6.1. Reactions linity of Ni particles on the surface played a major role in the ac-
tivity of the catalyst. The amount of adsorbed products (CO and H2)
The MD reaction has been described in Eq. (7) and is included in on the surface has been noted to improve activity. Pd and Pt were
the systems of reactions that describe MSR and POM. There is a also investigated for MD. Lee et al. [148] evaluated the activity of Pd
consensus from experimental results that in MD over Cu, Ni, Pt, Pd, and Pt over silica and alumina supports for MD. The catalysts were
and Fe surfaces, that methanol is adsorbed molecularly and forms a active at temperatures 453e573 K. Pd reported a higher activity
methoxy group adsorbed on the metal at higher temperatures than Pt, while alumina-supported catalysts were more active than
[141]. The further decomposition steps of the methoxy group into silica-supported ones. However, alumina-supported catalysts pro-
the final products of CO and H2, however, are still highly debated. duced a dimethyl ether byproduct. Recent work has been reviewed
Zuo et al. [142] identified different reaction pathways for by Araiza et al. [149] on bimetallic catalysts for MD. Bi-metallic
methanol over a Cu surface. Pathways for MD, MSR, and methanol catalysts composed of Cu paired with either Pd, Pt, or Ni was sup-
oxidation were evaluated. For MD, the foremost reaction path ported on nanoceria (CeO2). The addition of another metal influ-
identified was an initial scission of the OeH bond into a methoxy enced the dispersion of the active materials and ultimately
intermediate. The methoxy group underwent abstractions of H into improved activity, regardless of the metal added to Cu.
CH2O, then into CHO, and finally into CO. However, the calculated
rate constants in the temperature range of 473e573 K for the rate- 7. Perspectives and challenges
limiting step of MD are lower relative to MSR and methanol
oxidation, establishing that oxidation and reforming are faster than The methanol economy was conceptualized by Nobel Prize
MD. recipient George A. Olah with the proposal to utilize renewable
A similar path was observed by Huberty et al. [143] for MD over methanol in place of fossil fuel resources. Olah [150] suggested that
a Ni surface, while Tawarah and Hansen [144] reported a similar methanol could be industrially generated by direct oxidative con-
path for MD over ZnO. version of CH4 or reductive conversion of atmospheric CO2 with
hydrogen. Olah’s vision positions methanol as a convenient storage
6.2. Catalyst development medium that can be used either as a fuel in energy applications, or
as a chemical feedstock to generate hydrocarbons.
Initial investigation of MD catalysts was focused on Cu/ZnO China has attempted to build a methanol economy and has been
catalysts due to their effectivity in low-temperature catalysis of the most advanced nation to adopt its energy and chemical in-
methanol synthesis [145]. However, multiple active metals may be dustry as such. Yao et al. [151] investigated the environmental
used: Cu-based catalysts are regarded as low-temperature catalysts implications of the proposed methanol economy in China. The
operating at 200e275
C, Zn/Cr catalysts typically operate at 350
C, current dominant production route based on coal performed worse
while Pt-based catalysts have optimal activity at above 400
C than gasoline in a well-to-wheel perspective. However, methanol is
[140]. largely utilized directly in this study, not as hydrogen. Yang and
Cheng [146] investigated the effect of ZnO and other metal Jackson [152] reviewed the effect of the current methanol policy in
promoters such as Cr, barium (Ba), and manganese (Mn) on Cu- place. The use of methanol-based technologies provides an inex-
based catalysts for MD at 250
C. The study reported that ZnO, a pensive fuel that improves urban air quality. However, the current
highly effective promoter for Cu in methanol synthesis, had a sig- production routes still depend heavily on coal, ultimately
nificant detrimental effect on the activity, selectivity, and stability increasing net GHG emissions, and exacerbate coal market vola-
of the Cu-based catalyst in MD. The presence of Zn in the system tility. Biomass-based methanol was identified by both studies as a
limited the activity of all catalysts to conversions of around 35%, key pathway to lower greenhouse gas emissions, mitigate compe-
while without Zn, the conversion was in the range of 50e85%. The tition for fossil resources, and drastically decrease primary energy
Cu/Cr catalysts also showed high selectivity to CO. The Cr content consumption. However, huge capital considerations make renew-
was also found to promote a reaction pathway to dimethyl ether able methanol uncompetitive in the short term [151], while policy
and was required to be optimized to reduce the loss of selectivity to and government have no concrete plans to support it [152]. Gum-
CO. Cheng [138] further investigated the effect of SiO2, alkali metals, ber et al. [153] compared the methanol and hydrogen economies.
and Mn and Ba oxides on promoting MD over Cu catalysts. Small The key challenge for the application of the methanol economy is
amounts of alkali metals or SiO2 showed increasing dispersion of Cu the cost and complexity of building renewable methanol sources
that helped stabilize and maximize surface area for the reaction. Li and efficient conversion technologies to hydrogen.
et al. [24] used a spinel structure of copper to improve stability in Energy applications post-conversion to hydrogen should be
hydrogen production using MD. Potassium (K) was also added to considered during technology selection. An example is the use of
the catalyst to improve the selectivity to CO and H2. The spinel methanol in internal combustion engines by reforming the meth-
structure (CuAl2O4) acted as a reservoir of the active metal during anol on-board vehicle. This application does not require a low
the process and released Cu gradually, preventing rapid deactiva- selectivity of CO as it can be further combusted in ICEs. Verhelst
tion by sintering. Qing et al. [147] further investigated the et al. [154] pointed out that the gap in future research has to
13
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

address methanol utilization for internal combustion engines. Gaps future. Methanol can also be sourced from atmospheric CO2, mak-
in life cycle assessment of methanol-fueled vehicles, methanol ing it a step closer to an envisioned methanol economy.
engine efficiency, onboard reforming with engine waste heat, and The development of technologies to convert methanol into
cost-effectiveness of methanol-to-movement. Fuel cells such as hydrogen is increasingly important. In this review, methanol steam
PEMFC are clean technologies. However, it requires high purity reforming (MSR), partial oxidation of methanol (POM), autothermal
hydrogen that is still a challenge. Finding methanol-to-hydrogen reforming of methanol (ATRM), and methanol decomposition (MD)
routes that provide high conversion and yield at lower tempera- have been discussed and compared. MSR is featured by its endo-
tures and rapid kinetics is paramount to scale PEMFCs. Alterna- thermic nature, high conversion, selective formation of H2, and low
tively, a combination of scaling purification technologies like semi- CO generation, and easier temperature control. However, MSR is
permeable membranes with highly active catalysts can be explored. sluggish at start-up and requires an additional input of heat to drive
Several pathways have been presented in this study to produce the reaction forward. Catalyst development has been focused on
methanol as well as transforming it into hydrogen for further uti- copper, but there is a growing interest in PdeZn catalysts that offer
lization. The utilization of methanol-hydrogen systems in the a comparable activity and selectivity. Research in reactor design for
future require advanced technologies that deliver increased effi- MSR has been gearing towards microreactors with microchannels
ciencies in the areas of methanol production from biomass or at- and microstructures (monolith, sintered felt, etc.). Membrane re-
mospheric carbon. The future cost of the biomass feedstock should actors for improving kinetics and separation are also a ripe area of
not overly appreciate. The gasification of biomass to methanol can research that may rival the conventional pressure swing adsorption
be further improved by improving gas cleaning, reformers, shift process. POM reaction units can warm up easily by adjusting the
processes, and highly selective separation processes. oxygen flow rate to increase fuel combustion. There is a high risk of
Future hydrogen production from methanol will feature producing CO due to the difficult temperature control, and POM is
improved catalysts that are highly selective to hydrogen and carbon still at lower levels of hydrogen yield compared to reforming. The
dioxide. These catalysts will be stable for long durations of time and rapid start of POM provides easier start-up and changeovers. A key
a wide range of temperature levels. These will likely come from part of recent POM research is the ability to cold start using novel
different catalyst configurations such as spinel catalysts that pro- catalysts and reactor design. Swiss roll reactors improve heat
vide high reactive areas and stable configurations. Synthesizing transfer limitations from conventional reactor designs. However,
active catalysts will also play an important role. Separation pro- activity and selectivity remain an important improvement to be
cesses for H2 will also play an important role in increasing the unlocked for POM. In ATRM, air and water are already fed to the
overall efficiency of the system. Pressure swing adsorption (PSA) reactor, making it simpler and easier to design when it comes to
and ceramic membranes will allow high purity output streams reactor selection. ATRM theoretically run at a thermos-neutral
while driving the reaction towards H2 production. system, it neither uses nor produces external energy. This charac-
teristic of ATR makes it more efficient and with better hydrogen
selectivity compared to POM. At the same time, ATR has a better
8. Conclusions
dynamic response compared to MSR and has the possibility to
accommodate numerous fuels. MD is part of the system of reactions
Deep decarbonization of the energy and transport sector in-
that describe the other modes of hydrogen production. It was
creases the need for the development of hydrogen technologies.
believed to be the initial step for MSR and POM in some reports and
Methanol as a hydrogen carrier addresses multiple problems
has a kinetically slower reaction than MSR and POM. MD generates
associated with the logistics of hydrogen gas for energy applica-
CO and is usually minimized for PEMFC applications. However, it is
tions. Methanol is a future-proof material and is a versatile fuel that
favored in in-situ reforming for internal combustion engines as CO
can be sourced from sustainable. It is in a unique position that can
is combustible. Table 5 compares these four routes of hydrogen
bridge current fuel technology and applications to a sustainable

Table 5
Characteristics of MSR, POM, ATR, and MD.

Process MSR POM ATRM MD

Conversion and hydrogen High conversion of methanol. Low conversion and requires Higher efficiency and hydrogen Conversion is completed at
yield Reforming from both fuel and higher temperatures. concentration than POM. lower temperatures (400 K)
water which results in higher but is kinetically slower
yield. than MSR and POM.
CO selectivity Low temperature process. High CO generation that can High CO concentration of CO selectivity increases.
Low CO generation. poison the downstream syngas produced Potential combustion.
Cu- and Pd- based catalyst processes. Additional clean up before fuel Not ideal for PEMFC due to
compatibility. cell application is catalyst poisoning.
recommended
Process and equipment Well established process. Fast start-up Better dynamic response than Endothermic nature
technology Easy temperature control. More dynamic (higher reaction MSR. requires an initial heat
Endothermic nature of the rate). Greater flexibility to input. Adsorption step into
reaction. No steam generation unit is accommodate multiple fuels. catalyst surface occurs
Requires a steam generation required. Operates ideally at a thermos- early.
unit. Air or oxygen is used as the neutral point. The rate-limiting step of
Requires external input of heat oxidant. Neither consuming nor desorption of CO occurs at a
to drive the reaction. releasing external energy. temperature above 400 K.
Catalyst technology Cu- based catalysts are highly Catalysts able to cold start the Complex catalyst synthesis Catalysts are well
developed. POM process Needs to be active for both SRM established. Cu- based
Vast studies in promoters, Catalysts are stable. and POM catalysts are active for MD.
supporters, preparation -Cr and other promoters
methods, and reaction can be used.
mechanisms.

14
G. Garcia, E. Arriola, W.-H. Chen et al. Energy 217 (2021) 119384

production from methanol. The different processes discussed in CeO2eZrO2catalysts. Int J Hydrogen Energy 2017;42:15073e84.
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this paper help guide the reader to understand the key methanol-
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[23] Chen W-H, Lin B-J. Hydrogen production and thermal behavior of methanol
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Declaration of competing interest ing. Int J Hydrogen Energy 2013;38(24):9973e83.
[24] Li G, Gu C, Zhu W, Wang X, Yuan X, Cui Z, et al. Hydrogen production from
The authors declare that they have no known competing methanol decomposition using Cu-Al spinel catalysts. J Clean Prod 2018;183:
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financial interests or personal relationships that could have [25] Matsumura Y, Tode N. A kinetic study of catalytic methanol decomposition
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[26] Matsumura Y, Tode N, Yazawa T, Haruta M. Catalytic methanol decomposi-
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