i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

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Review Article

Plasma reforming for hydrogen production:

Pathways, reactors and storage

Neeraj Budhraja*, Amit Pal, R.S. Mishra

Department of Mechanical Engineering, Delhi Technological University, Delhi, 110042, India

highlights

Hydrogen production via the methane reforming pathway is discussed.

Ethanol decomposes into intermediate species that further splits into
H radical

Various plasma reforming reactors for H2 production are discussed.

Influencing parameters in plasma reforming are identified.

Various process parameters affecting H2 production are reviewed.

article info abstract

Article history: Hydrogen is an energy carrier with a very high energy density (>119 MJ/kg). Pure hydrogen
Received 5 August 2022 is barely available; thus, it requires extraction from its compounds. Steam reforming and
Received in revised form water electrolysis are commercially viable technologies for hydrogen production from
10 October 2022 water, alcohols, methane, and other hydrocarbons; however, both processes are energy-
Accepted 16 October 2022 intensive. Current study aims at understanding the methane and ethanol-water mixture
Available online 5 November 2022 pathway to generate hydrogen molecules. The various intermediate species (like CHX,
CH2O, CH3CHO) are generated before decomposing methane/ethanol into hydrogen radi-
Keywords: cals, which later combine to form hydrogen molecules. The study further discusses the
Hydrogen production various operating parameters involved in plasma reforming reactors. All the reactors work
Dielectric barrier discharge on the same principle, generating plasma to excite electrons for collision. The dielectric
Pulsed plasma barrier discharge reactor can be operated with or without a catalyst; however, feed flow
Gliding arc plasma rate and discharge power are the most influencing parameters. In a pulsed plasma reactor,
Microwave plasma feed flow rate, electrode velocity, and gap are the main factors that can raise methane
conversion (40e60%). While the gliding arc plasma reactor can generate up to 50%
hydrogen yield at optimized values of oxygen/carbon ratio and residence time, the
hydrogen yield in the microwave plasma reactor is affected by flow rate and feed con-
centration. Therefore, all the reactors have the potential to generate hydrogen at lower
energy demand.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: [email protected] (N. Budhraja).
https://doi.org/10.1016/j.ijhydene.2022.10.143
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
2468 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2468
Hydrogen production pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2469
Methane pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2469
Alcohol-water mixture pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2470
Plasma reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2471
Dielectric barrier discharge (DBD) plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2473
Pulsed plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2474
Gliding arc plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2475
Microwave (MW) plasma reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2476
Advantages and disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2478
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
Availability of data and material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2479

energy source are the availability of feedstocks, extraction,

Introduction storage systems, and safety concerns.
Hydrogen is plentiful in the environment, but free
Hydrogen is currently the best energy source available due to hydrogen gas is rarely available. Thus, hydrogen extraction is
its exceptional properties and can fulfill the energy re- required from various compounds to get the benefits of
quirements of various sectors, thus, making it a good alter- hydrogen as a fuel. At present, fossil fuels, i.e., natural gas
native to conventional fuels. It has a very high energy density (75%) and coal (20%), along with 2% from water electrolysis,
(>119 MJ/kg) and a longer flammability limit (4e75%) which no meet the utmost global hydrogen demand [7], which con-
other fuel matches [1]. In addition, hydrogen-burning results sumes about 6% natural gas and 2% coal globally, generating
in water vapour (H2O), a harmless and clean product. Thus, approx. 830 Mt-CO2 Equiv. Greenhouse gases (GHG) annually,
hydrogen use can lower greenhouse gas (GHG) emissions, help and only 130 Mt-CO2 is captured annually by the fertilizer
reduce everyday carbon emissions, facilitate a cleaner envi- industries [8]. The hydrogen demand in refining oil (33%),
ronment, and reduce climate change threats [2,3]. Hydrogen ammonia production (27%), alcohol production (11%), steel
can potentially eradicate the mismatch created in the manufacturing (3%), and others have increased drastically,
renewable sources' demand for seasonal and daily supply; its making significantly less space for power generation appli-
usage may extend energy service to rural areas inaccessible to cations [9]. Fig. 1 gives the estimated global hydrogen demand
the grid. Therefore, hydrogen can be envisioned as the future for the next 30 years [8].
fuel, energy storehouse, and long-distance energy carrier Hydrogen is a cleaner fuel because its combustion has
[4e6]. However, the main hurdles to accepting hydrogen as an zero-carbon products; thus, it is currently the most

Fig. 1 e Estimated global hydrogen demand in different sectors.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2469

acceptable fuel for replacing conventional fuels that badly consuming hydrogen storage systems, and the reactors can
pollute the environment with harmful and carcinogenic be installed at the demand site. This will further reduce
emissions [10]. However, conventional hydrogen production transportation issues.
processes like steam methane reforming generate GHG gases In the current study, detailed hydrogen production path-
that harm the environment [11e14]. Many researchers and ways via methane decomposition and ethanol-water decom-
scientists have developed renewable energy integrated de- position are discussed. The study aims to understand the
vices that can efficiently achieve hydrogen production goals working principles of different plasma reactors and discusses
with low emissions generation [15,16], though the availability the various operating parameters in the hydrogen production
of renewable energy sources is dynamic. Therefore, tradi- processes that influence the hydrogen production rate. A
tional methods like natural gas reforming [17,18] and elec- comparative study of the different plasma reactors' advan-
trolysis are the most common techniques being preferred. In tages and disadvantages is determined to understand plasma
contrast, many researchers and scientists also worked on the reactors’ suitability for a particular application. Therefore, a
biological hydrogen production processes that reduce elec- good understanding of different plasma techniques will aid in
tricity dependence, but maintaining the physical environ- determining the most effective plasmolysis process for
ment in the reactor is challenging [3]. Plasmolysis is another hydrogen production in a specific application based on the
technique that may solve on-demand hydrogen production at production rate and purity.
no or significantly less GHG emissions when integrated with The paper initially discusses the pathway of methane and
other renewable energy sources. Plasmolysis is a process of water-alcohol mixture conversion to hydrogen in section 2.
breaking down hydrogen compounds into hydrogen mole- The paths of methane and water-alcohol mixture conversion
cules under the action of a plasma arc. The electrons in the are simplest to understand, and the higher hydrocarbons and
arc zone exist at a very high temperature of about alcohols follow a similar pathway. Section 3 discusses four
15,000e20,000  C; however, the system temperature remains different plasma reforming rectors with diagrams of the
near room temperature. Plasmolysis requires comparatively respective rector. Here, a brief study is performed to under-
less infrastructural capital cost and the compatibility of stand the working and influencing parameters from the works
various feedstocks is an additional advantage in hydrogen of other authors. From all the discussions, various advantages
production. Kheirollahivash et al. [19] examined the methane and disadvantages of different plasma reforming reactor is
decomposition into hydrogen via plasmolysis and studied the determined in section 4 to understand better how to use
effects of multiple parameters. A 6 L/h hydrogen production plasma reactor for a suitable application. Lastly, section 5 is
rate was achieved at a 9 L/h methane flow rate with 26.8 g/ the conclusion of all the discussions.
kWh energy yield and 0.2e3.9s residence time, respectively.
A hydrogen storage system is essential in energy trans-
portation and on-board applications [20]; however, it con- Hydrogen production pathways
sumes about 1/3rd of the system's total energy. Every fuel
requires a safe and easy storage system that helps in the Methane pathway
efficient availability of power for various applications [21,22].
Hydrogen has a very low gas density, making it challenging for The proposed reaction pathway of methane (CH4) decompo-
larger quantity storage. An estimate showed that the hydrogen sition into CHX (CH3, CH2, CH) molecules [26,27] and then into
storage system is more than 3000-fold gasoline, making the hydrogen and carbon inside a plasma reactor is depicted in
whole storage system bulky for on-board hydrogen storage Fig. 2. In a plasma reactor, the electrons get excited when they
[20]. Thus, several kinds of research have been accomplished come into contact with the plasma zone. The high-energy
to develop a safe and lightweight hydrogen storage system in electrons collide with methane molecules, breaking the
the last few years. Metal hydride (MH) has proved to be a methane bonds and creating active species for the standard
promising candidate in this regard [23,24]. MH's hydrogen thermodynamic reactions. The CH4 decomposition results in
storage and release are simpler and less costly [21]. The CH3, CH2, and CH molecules at the various threshold energies
exothermic reaction forms MH at a somewhat higher pressure [28,29] (as described in Table 1) and generates
H radicals. The
during hydrogenation, whereas at elevated temperatures, the minimum amount of energy that transforms the reactant by
endothermic reaction releases hydrogen at comparatively activating the hydrogen atoms is called activation energy. It
lower pressures [25]. enables the reactants to overcome repulsive forces and start
Hydrogen has extensive usage in chemical industries for breaking the bonds to generate
H radicals. These
H radicals
fertilizer production, pharmaceuticals, glass purification, combine to form hydrogen (H2) molecules, while the standard
semiconductor manufacturing, and many others like power thermodynamic reactions produce hydrocarbons (C2). The
generation using fuel cells, engine fuel for automobiles, and methane dissociation results in carbon particle deposition
rocket propulsion in aerospace industries; thus, its safe and inside the reactor, which requires regular removal. Few kinds
easy storage is required. However, the on-board hydrogen of research have used rotating electrodes to remove carbon
production system can overcome the costly and bulky particle deposits, thus, restricting any decline in the reactor's
hydrogen storage system. The hydrogen production from efficiency [26,29]. The process does not require a very high
plasma reactors can achieve the goal of the on-board temperature (except in the plasma-arc zone) as in methane
hydrogen production system. The plasma reactors are steam reforming [30]. Thus, the CHX molecules resulting in
compact, easy to install, and have a quick operation. These dehydrogenation inside the plasma reactor are possible under
advantages will solve the problem of bulky and energy- near-ambient conditions.
2470 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Fig. 2 e Methane decomposition pathway for H2 production.

Alcohol-water mixture pathway

Alcohol-water mixture also has the potential for hydrogen

Table 1 e Dissociation reactions involved in methane
decomposition. production via plasma reforming. The proposed pathway for
ethanol-water decomposition depicting the alcohol-water
Reactions Threshold Activation
energy (eV) energy (eV) dissociation into hydrogen molecules via different interme-
diate species is described in Fig. 3. Initially, the plasma region
e þ CH4 / CH3 þ H þ e 8.8 4.4
excites electrons to higher energy levels of 3e20 eV [17],
e þ CH4 / CH2 þ H2 þ e 9.4 4.7
e þ CH4 / CH þ H2 þ H þ e 12.5 4.5 allowing these excited electrons to collide with the ethanol-
e þ CH4 / C þ 2H2 þ e 14.0 6.0 water mixture. When the high-energy electrons strike
e þ CH3 / CH2 þ H þ e 9.5 4.7 ethanol-water molecules, the water molecules break down
e þ CH3 / CH þ H2 þ e 10.0 5.5 into
H,
O, and
OH radicals [31], while the ethanol molecules
e þ CH3 / C þ H2 þ H þ e 15.0 7.0 decompose into H2, CO, CO2, and C, following the intermediate
e þ CH2 / CH þ H þ e 8.5 4.25
species CH4, CH2O, CH3CHO [32]. The electron collision results
e þ CH2 / C þ H2 þ e 8.2 4.9
in the dehydrogenation of ethanol molecules, generating
H
e þ CH2 / C þ 2H þ e 14.0 6.2
e þ CH/ C þ H þ e 7.0 3.5 radicals that later combine to form H2 molecules [33,34]. The
various dissociation reactions involved in the electron-
ethanol collusion are presented in Table 2 [32,35]. The elec-
trode's carbon deposition significantly reduces reactor

Fig. 3 e Ethanol-Water decomposition pathway for H2 production.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2471

Table 2 e Dissociation reactions involved in ethanol Plasma reforming

decomposition.
Reactions Activation energy (eV) In the plasma zone, the electrons exist at very high temper-

e þ CH3 CH2 OH/ CH4 þ CH2 O þ e 
0.75 atures up to 15,000e20,000  C, and these electrons support
e þ CH3 CH2 OH/ CH3 CHO þ H2 þ e 1.03 decomposing of the organic matter in the feed while inorganic
e þ CH3 CH2 OH/ CH3 þ CH2 OH þ e 4.2 matters deteriorate partially [36,37]. High temperatures
e þ CH3 CH2 OH/ CH3 CHOH þ H þ e 4.3 completely decompose waste plastics and other hydrocarbons
e þ CH3 CH2 OH/ CH3 CH2 þ OH þ e 4.4
into syngas containing H2, CO, and a few higher hydrocarbons;
e þ CH3 CH2 OH/ CH3 CH2 O þ H þ e 4.7
however, the system temperature remains near room tem-
e þ CH3 CHOH/ CH3 CHO þ H þ e 2.11
e þ CH3 CHO/ CH3 CO þ H þ e 3.97 perature, and in some reactors, it may reach 300e400  C [38].
e þ CH3 CO/ CH2 CO þ H þ e 3.14 Putra et al. [39] studied a banana's pseudo-stems hydrogen
e þ CH2 CO/ CH2 þ CO þ e 3.35 production potential using an in-liquid plasma reactor. The
e þ CH2 / CH þ H þ e 4.25 pseudo-stem with long fibers showed 70.7% maximum
e þ CH/ C þ H þ e 3.5 hydrogen yield and 98.8% hydrogen selectivity, making it an
excellent raw material for hydrogen production [39]. Various
plasma reactors used for generating hydrogen are thoroughly
efficiency [31,32]. Researchers have used rotating electrodes to discussed. Dielectric barrier discharge and gliding arc plasma
minimize carbon particle deposition to avoid reactor effi- reactor can be pulsed; however, the study pulsed plasma
ciency decline [26]. reactor is considered separately.

Fig. 4 e Dielectric barrier discharge plasma reactor.

2472 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Table 3 e Plasma reforming studies for H2 production in the Dielectric Barrier Discharge (DBD) Reactor.
Feed Technical Modifications Process parameters H2 rate/yield Highlights Ref.
Methanol Cu/ZnO supported Al2O3 Temperature: 180e250  C e Highest methanol conversion of [31]
catalyst used Feed rate: 0.5e2.0 mL/h 39.1% is achieved by 4.0 kV
Discharge voltage: 0e4.0 kV discharge voltage and 50 kHz
Discharge frequency: 10e50 kHz. discharge frequency at 180  C.
Ethanol Water-ethanol mixture is Discharge power: 10e30 W 137.76 L/h At 20 W, highest H2 energy yield of [40]
preheated to 120  C Water/Ethanol ratio: 1e5 137.76 L/h is obtained with 3 water/
Feed rate: 0.4e1.4 mol/h ethanol ratio and 1.4 mol/h feed
rate.
Maximum ethanol conversion
(71%) is achieved with 5 water/
ethanol ratio at a 0.6 mol/h feed
rate.
Ammonia 10% Ni/Al2O3 catalytic reactor Gas flow rate: 60e300 L/h 120 L/h Maximum H2 production rate is [42]
Power-supply voltage: 90e110 V achieved at 150 L/h of NH3 flow rate
Temperature: 400e800  C at 110 V, and the overall system
obtains 28.5%
Ammonia Non-catalytic plasma Power: 100e400 W 120 L/h Maximum H2 production rate is [43]
membrane reactor for H2 NH3 flow rate: 30e120 L/h obtained by 4.5 gap length and
separation Gap length: 1.5 or 4.5 mm 400 W power with the H2 purity of
100%, and the conversion rate is
24.4%
Methane NiO/g-Al2O3 catalyst with Frequency: 6e14 kHz 28.4% (H2 yield) H2 yield is enhanced from 23.1% to [44]
cordierite honeycomb Feed rate: 1.8e5.4 L/h 28.4% at a 30 mL/min feed rate,
monoliths as substrate CH4/O2 molar ratio: 1e3 CH4/O2 ratio of 1, and discharge
Discharge power: 40e100 W power of 100 W.
Methane conversion increases
from 60.1% to 83.6%.
Water Plate micro-channel reactor Voltage: 14e16 kV 105.5 L/h Maximum H2 flow rate is achieved [47]
(PMCR) with ice trap for H2eO2 Steam flow rate: 0.1e0.2 L/h with a 0.2 L/h steam flow rate at
separation PMCR temperature: 293e403 K 18 kV and 403 K PMCR heating
temperature, while the highest
conversion rate obtained is 42.51%.

Fig. 5 e Pulsed plasma reactor.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2473

Dielectric barrier discharge (DBD) plasma reactor surface stabilizer. It enhances methanol conversion from 5.7%
to 39.1% when raising the electric discharge to 4.0 kV and
In a DBD reactor, an alternating current (AC) potential differ- 50 kHz. The result shows the significance of electric discharge
ence is applied between the electrodes. Here, the dielectric in alcohol decomposition. Likewise, Ulbejczyk et al. [40] per-
barrier that limits charge transport between electrodes covers formed ethanol conversion in a DBD reactor and studied the
at least one of the two electrodes; this counteracts the con- effects of operating parameters on hydrogen production. Re-
version of discharge into a thermal regime transition. The gas sults showed that the discharge power, water/ethanol ratio,
transition requires electrodes in concentric cylindrical config- and feed flow rate influenced the ethanol conversion. At 20 W
urations. Fig. 4 shows an electric discharge and a reforming discharge power, 5 water/ethanol ratio, and 0.6 mol/h feed
membrane used for hydrogen generation in a DBD plasma flow rate, the maximum ethanol conversion (71%) is obtained
reactor [31]. The electric discharge initiates alcohol-water [40]. Zhang et al. [41] used simulated gasoline (n-C5H12) to
dissociation at a comparatively lower temperature [31], and produce hydrogen-enriched syngas. The background temper-
optimization of other operating parameters enhances the ature played a significant role in n-C5H12 conversion, where the
hydrogen production rate. In the optimization process, Lee and conversion increases upto 498K, and then declines at 523K.
Kim [31] examined the effects of various parameters in Hayakawa et al. [42,43] designed a low-temperature
methanol-water decomposition using a hybrid plasma- plasma membrane reactor (PMR) that continuously de-
catalytic (Cu/ZnO supported Al2O3 catalyst) reactor, where composes ammonia (NH3) into high-purity hydrogen gas. The
Copper (Cu) provides active sites and Zinc oxide (ZnO) is a PMR works stage-wise; firstly, plasma decomposes NH3 into

Table 4 e Plasma reforming studies for H2 production in the Pulsed Discharge Reactor.
Feed Reactor Process parameters H2 CH4 Highlights Ref.
selectivity/rate conversion
Methane Continuous rotating Power: 7, 14, 21 W 95% 60% Highest H2 selectivity is [26]
electrodes plasma Flow rate: 3, 6, 9 L/h achieved by 9 L/h CH4 flow rate
reactor Electrode velocity: 0e6000 rpm at 21 W and 2000 rpm electrode
speed.
Energy efficiency of 1.46 mol/kJ
was obtained without a
catalyst.
Methane Reactor with parallel Power: 20 W 97% 47% Highest H2 rate (7.96 L/h) is [27]
screw-type helix and Flow rate: 9 L/h achieved with a 9 L/h CH4 flow
rod-like electrodes Electrode velocity: 200e800 rpm rate at 20 W and 200 rpm, while
a 36.8 g/kWh of energy yield is
obtained.
Methane Non-equilibrium warm Applied Voltage: 15.5e18.5 kV 44.6% 40% At 17.2 kV and 100 SCCM CH4 [29]
plasma reactor Flow rate: 100 & 200 SCCM flow rates, 85.6% and 40% CH4
conversion and H2 selectivity
are obtained.
Higher CH4 conversion (92%)
reduces H2 selectivity to 30.6%
and H2 concentration
percentage to 56%.
Ethanol Pulsed discharge reactor Voltage: 22e30 kV 66 L/h (rate) e Highest H2 flow rate and energy [49]
with needle-ball Discharge frequency: 30 kHz yield are achieved at 30 kV and
configuration Ethanol concentration: 50% 50% ethanol concentration in
Electrode distance: 15 mm water.
Higher voltage helps jumping
electrode balls enhance the
randomness and strength of
discharge.
Bio-oil Solution plasma process Reaction time: 5, 10, 20 min 114.6 L/h (rate) e 1.41 L H2 yield obtained by 1:4 [50]
in quartz reactor Ethanol/bio-oil ratio: 1:0, 1:1, 1:4 ethanol/bio-oil ratio in 20 min.
While at 1:1 ethanol/bio-oil and
5 min, the H2 production
reaches to maximum
containing 65.51% H2 content.
Ethanol Pinhole and plate Voltage: 28 kVe31 kV 7.2 L/h (rate) e H2 and CO consist of about 99% [51]
electrodes Power: 0.25e2.9 MW of syngas.
Electrode distance: 2e10 mm Both high peak voltage and
appropriate electrode distance
increase the H2 yield to the
maximum value.
2474 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Fig. 6 e Gliding arc plasma reactor.

H radicals, then
H radical adsorption and penetration into which break the hydrogen bonds [29,35]. Corona discharge
the membrane surface takes place, and finally, the
H radicals and spark discharge are two pulsed electrode plasma forms
recombine to form hydrogen molecules. The process gener- that depend on the variation in peak voltage. The low voltage
ates hydrogen gas (99.99% pure, which feeds directly to the generates corona discharge which appears as many
fuel cell) at a 1.2 L/h rate at 400 W input power. PMR gap length streamers, while high voltage results in spark discharge,
and gas differential pressure showed a 120 L/h hydrogen flow which appears as a flash between electrodes. The components
rate against a 150 L/h ammonia flow rate at 110 V, giving 28% and working of a fabricated pulsed DC plasma reactor are
energy efficiency. Similarly, Song et al. [44] investigated the given by Morgon and ElSabbagh [29] in Fig. 5. It was observed
hydrogen production potential of a DBD plasma reactor with & that the methane flow rate of 100 standard cubic centimetres
without a NiO/g-Al2O3 catalyst. The DBD plasma and NiO/g- per minute (SCCM) is more effective in CH4 conversion than a
Al2O3 catalyst synergized, resulting in better CH4 conversion 200 SCCM flow rate, while the CH4 conversion raises with
and H2 yield. The results showed improved CH4 conversion applied voltage in both cases. However, the H2 selectivity at
from 60.1% to 83.6% and H2 yield from 21.3% to 28.4% using a low voltage has similar results (as CH4 conversion), and the
honeycomb catalyst. The observation also showed that the opposite results were obtained at a voltage higher than 17 V.
high temperature reduces Nickel oxide (NiO) to Nickel (Ni), The reactor showed 92% CH4 conversion and 44.6% H2 selec-
affecting the catalyst life; thus, a low temperature is favorable tivity at specific input conditions. Thus, the methane flow rate
for longer catalyst life. King et al. [45] determined the and applied voltage directly influence the reactor's CH4 con-
hydrogen production rate from landfill gas/coal mine gas in a version and H2 selectivity. Meanwhile, a valuable by-product
DBD reactor. The catalytic DBD reactor generates about (graphite oxide) is also produced within the reactor by
1456 kL/h H2 at 500  C and near atmospheric pressure. Like- methane decomposition, which can be collected and purified,
wise, Shareei et al. [46] studied the influence of applied voltage for different applications in electronic, optics, chemistry, en-
and Argon flow rate on methane conversion. About 99.9% ergy storage, and biology [48]. In contrast, Xin et al. [35]
methane conversion was observed at 1.84 synthesis gas operated a pulsed discharge reactor with a needle-balls-like
module, and 10 kV applied voltage. Table 3 discusses other electrode configuration, generating hydrogen at a 66 L/h flow
modified DBD reactors, operating parameters, and H2 yield rate and a 141.3 g-(H2)/kWh hydrogen energy yield at 30 kV.
and production rate. The observation shows that the During the discharge shock waves, the jumping of electrode
hydrogen yield is mainly affected by discharge voltage (or balls increases the discharge randomness and strength, giving
power) and feed flow rate, while temperature, electrode gap a higher energy yield. The study also includes pulsed
length, and O/C ratio have a significantly less or negligible discharge through constant rate comparison and found that
impact on hydrogen yield. formaldehyde (CH2O) addition may significantly raise
hydrogen flow rate.
Pulsed plasma reactor Moshrefi and Rashidi [26] investigated the methane con-
version into hydrogen in a rotating plasma electrode reactor at
Pulsed discharge is chemically active and produces high cur- almost ambient temperature and found no COX radicals gen-
rent density, generating reactive ions, electrons, and radicals, eration in the reactor. The method showed about 60% methane
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2475

Table 5 e Plasma reforming studies for H2 production in the Gliding Arc Plasma Reactor.
Feed Process parameters H2 selectivity/yield Conversion Highlights Ref.
percentage
CH4eCO2 CH4/CO2 ratio: 0 to 2.4 16% 48% Highest conversion rate is [54]
Injection gas velocity: 45 obtained by 69.5 m/s injection
e120 m/s gas velocity, 300 L/h CO2 flow
CO2 flow rate: 300e900 L/h rate, and Type 1 orifice baffle at
Orifice baffle: Type 1, 2 and 3 1 CH4/CO2 ratio.
CO2 destruction rates ranged
between 35.7 and 42.6%,
depending upon the various
process parameters.
Methanol O2/C ratio: 0.15e3.0 70% 88% Highest CH4 conversion is [53]
S/C ratio: 0.15e2.0 obtained at 0.3 O2/C ratio, 0.5 S/
Specific energy input: 24e36 kJ/ C ratio, and 24 kJ/mol SEI.
mol A 74% and 0.45 kWh/Nm3 are
the energy efficiency and cost
n-heptane Power: 26e34 W 50.1% (H2 yield) e Highest H2 yield is achieved at [52]
O/C ratio: 0.48 to 1.1 30 W input power, 0.71 O/C
Residence time: 14.8e46.5 s ratios, 6.5 mm discharge gap,
Discharge gap: 3.8e6.5 mm and 24.7 s residence time.
The best H2 energy yield of
94.5 L/kWh is achieved.
Toluene Power: 26e36 W 48.6% (H2 yield) e The ideal H2 yield is achieved [57]
O/C ratio: 0.55 to 1.3 with a 0.68 O/C ratio, 18.4 s of
Residence time: 11.5e35 s residence time with Ar addition
Ar addition: 0e30 vol% of 10 vol% at 32 W.
Methanol Frequency: 84 kHz 97.2% 80.3% Methanol conversion and H2 [59]
Gas flow rate: 2.5 SLM selectivity increased from
Water concentration: 0e95 mol 24.0% to 87.7% to their
% maximum value, and H2O conc.
from 0 to 95 mol%
CH4eCO2 Input voltage: 20e100 V ⁓72% 32.6% (CH4) and 22.5% (CO2) Optimal conversion is obtained [60]
Frequency: 10e30 kHz by 3 mm discharge gap and
Discharge gap: 1e4 mm 20 kHz discharge frequency at
CH4/CO2 ratio: 0.25 to 2.0 60 V.
Higher CH4/CO2 ratio results in
H2 production, but CH4 will
remain unreacted; thus, the
ideal CH4/CO2 ratio is 1e2.
n-heptane Input power: 28e38 W 73.9% 42.6% (CO2) 34.1% peak selectivity and [61]
O/C ratio: 0.55 to 1.2 53.9 L/kWh are achieved at
Residence time: 20.4e66.7 s 36 W.

conversion and 1.46 mol/kJ energy efficiency without any Gliding arc plasma reactor
expensive catalyst, thus, making the process more energy-
efficient than a fixed electrode reactor. Similarly, Kheir- The gliding arc discharge is another plasma technique that
ollahivash et al. [27] developed a screw-type electrode and produces warm plasma at about 1000e3000 K gas temperature
recorded the reactor performance parameters to determine the and, thus, possesses properties between thermal and non-
impacts of arc extension and electrode traveling at different thermal plasmas [52]. It is a transient arc discharge formed
angular velocities. The maximum CH4 conversion, hydrogen between two flat diverging electrodes. The shortest inter-
production rate, and H2 energy yield obtained with the double- electrode space initiates the arc that glides along the elec-
helix electrode are 47%, 7.96 L/h, and 36.8 g/kWh, respectively. trodes due to the gas blast and reaches the larger
At the same time, it showed a 2.1 g/h carbon decomposition interelectrode space before it vanishes; then, a new arc gen-
rate, where carbon has a graphite-like structure. Table 4 gives erates, and the process continues. Fig. 6 shows various gliding
details of other pulsed discharge reactors operating at different arc plasma reactor components and different attachments
parameters for hydrogen production. It was observed from the [53]. Kim and Chun [54] designed a similar gliding arc plasma
study of different pulsed discharge plasma reactors that feed for CO2 decomposition and CH4 steam inflow and measured
flow rate, electrode distance, and electrode velocity (rotating the effects of varying orifice baffles in hydrogen-rich syngas
electrode) play a significant role in hydrogen production. While production. The orifice baffle with the smallest inner diameter
the parameters like power, reaction time, and concentration showed the highest CO2 destruction rate (42.5%) due to higher
have less significance, their optimization will benefit the sig- retention time while achieving 48% methane conversion at a
nificant parameters in the process. 300 L/h CO2 flow rate. In contrast, Lian et al. [53] investigated
2476 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Fig. 7 e Microwave plasma reactor.

the methanol-reforming in a gliding arc plasma reactor and methane reforming. During the process, water plays a ho-
observed an 88% methanol conversion by 0.3 oxygen/meth- mogeneous catalyst and CO oxidant between 33 and 95 mol%
anol ratio, 0.5 steam/methanol ration, and 24 kJ/mol specific content and a side-product below 33 mol% concentration.
energy input, respectively. It gives high energy efficiency with Both a catalyst and an oxidant behavior of water enhanced
low energy costs. Liu et al. [55] investigated ethanol reforming hydrogen production, while the side-product behavior resul-
for hydrogen production in a gliding arc plasma reactor and ted in hydrocarbon formation, drastically reducing hydrogen
achieved 38.6% of the highest H2 yield during the experi- production. Table 5 discusses other gliding arc plasma re-
mentation. In continuation, Wang et al. [52] examined the actors and operating parameters for higher hydrogen yield.
influence of various other operating parameters in continuous The hydrogen yield in the gliding arc plasma reactor depends
n-heptane decomposition at room temperature and achieved on the O/C ratio, power, and feed flow rate. The O/C ratio
50.1% H2 yield and 94.5 L/kWh H2 energy yield at 30 W input between 0.4 and 0.7 at a power input of 30e32W is considered
power, 0.71 O/C ratios, 6.5 mm discharge gap, and 24.7 s favorable for maximum hydrogen production, while in case of
residence time, respectively. Any fluctuation in the above methanol, the power input can reach as high as 120 W for
parameters decreases H2 yield, while CO and CH4 yield in- effective results.
creases drastically.
Piavis and Turn [56] also fabricated a reverse vortex flow Microwave (MW) plasma reactor
plasma reactor and tested the reactor performance for
methane reforming. The reactor achieved 66.5% H2 yield and A microwave (MW) plasma reactor is another plasma tech-
79.8% methane conversion at 43.5% efficiency and 144 kJ/mol nique for hydrogen production that works between 300 MHz
specific energy requirement. In contrast, Song et al. examined and 10 GHz frequency range. It utilizes electromagnetic radi-
the CH4eCO2 decomposition in a rotating gliding arc reactor ation to excite electrons to higher energy levels, and these
and observed a 1e2 CH4/CO2 ratio ideal for hydrogen pro- excited electrons break the hydrogen bonds to form
H radi-
duction, while a higher ratio resulted in incomplete CH4 cals, which later combine to form H2 molecules [62,63]. The
reforming. At the same time, the higher voltage and fre- discharge initiation happens when gas flows through a quartz
quency enhance gas energy yield, whereas overall energy tube and intersects with a rectangular waveguide. The plasma
consumption is improved. Baowei et al. [57] performed the absorbs wave energy, and MWs spread through quartz tubes.
toluene reforming in a gliding arc plasma reactor while add- Czylkowski et al. [62] used a microwave plasma reactor
ing a smaller amount of Argon (Ar) gas. With 10 vol% Ar (shown in Fig. 7) and determined the effects of spraying
addition, the reactor achieved a 48.6% H2 yield and 60.2 L/ ethanol microdroplets into Nitrogen (N2) MW plasma flame at
kWh H2 energy yield, respectively. Ma et al. [58] studied the atmospheric pressure. Direct spraying saved energy re-
potential of n-dodecane for hydrogen production in a gliding quirements for vaporizing ethanol. The results show
arc plasma reactor. The highest n-dodecane conversion of hydrogen concentration and production rate of 28% and
68.1% gives 76.7% H2 selectivity, while the other products 1043 L/h at 3.7 L/h ethanol flow rate and 5 kW microwave
generated are acetylene and ethylene. Both acetylene and power. Wang et al. [64] investigated the liquid-phase methane
ethylene help in the selectivity enhancement of light olefins. reforming for hydrogen production in an MW plasma reactor.
Meanwhile, Lian et al. [59] examined the behavior of water (at The highest H2 yield of 74% was achieved by 94.3% methane
several concentrations) in a gliding arc plasma reactor for conversion and 900W power. In another study, Czylkowski
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2477

Table 6 e Plasma reforming studies for H2 production in the Microwave Plasma Reactor.
Feed Process Parameters H2 production Energy Highlights Ref.
rate (g/h) Yield (g/kWh)
Ethanol Frequency: 2.45 GHz 86.7 17.4 Highest H2 production rate with [62]
Power: 2e5 kW 28% H2 content is achieved by
N2 gas flow rate: 2000e4000 L/h ethanol and N2 gas flow rate of
3.7 L/h and 2700 L/h at 5 kW
power.
Ethanol Frequency: 2.45 GHz 71.9 15.0 Highest H2 production rate with [65]
Power: 2e5 kW 27.6% H2 content is achieved by
Flow rate: 0.14e2.7 kg/h raising microwave power to
5 kW, while the increased
ethanol mass flow rate resulted
in higher hydrogen production
efficiency.
Ethanol Frequency: 2.45 GHz 72.48 48.32 Highest H2 flow rate with 58.1% [67]
Power: 900e1500 W H2 content is achieved at
Ethanol conc.: 10e100 vol% 1500 W and 70 vol% ethanol
concentrations.
Water Frequency: 2.45 GHz 7.6e23.1 13.3 Ceriated tungsten showed [68]
Power: 900 W higher H2 production than pure
Flow rate: 2 bbl/s tungsten. However, the overall
Temperature: 107  C system attained 53% energy
efficiency and 44% exergy
efficiency.
Synthetic Biogas Frequency: 915 MHz 156 21 Highest H2 production rate is [69]
Power: 4.5e7.5 kW achieved with 6000 L/h flow
CH4/CO2 ratio: 0.1e1.0 rate at 7.5 kW; however, the
Flow rate: 3000e9000 L/h peak energy yield of 21 g/kWh is
obtained at 4.5 kW, and
maximum CH4 conversion
(86.5%) is achieved by 3000 L/h
flow rate at 6.5 kW power.
Ethanol Frequency: 2.45 GHz 66.6 41 Ethanol decomposes into [70]
Power: 700e1500 W CH3CHO and H2 by high-energy
Ethanol conc.: 20e100 vol% electrons and produces CH4
Discharge time: 3e15 min. and CH2O.
While H2O decomposes into

OH and
H radicals.
Ethanol Frequency: 2.45 GHz 85.8 57.4 80 PPI Cu foamed metal [71]
Power: 900e1500 W suspended electrode shows a
Flow rate: 660e1800 L/h 31.5% increase in total gas flow
Bubble retention time: 60 rate than no suspended
e90 ms electrode.
Methane Frequency: 915 MHz 2247 70 A 74.6%e97.7% rise in methane [72]
Power: 15e50 kW conversion was observed with
Flow rate: 240e420 L/h an increase in the S/C ratio.
H2O/CH4 molar ratio: 3-6 Hydrogen production rate rises
from 1532 to 2247 g (H2)/h when
the absorbed microwave power
is raised from 27 to 32 kW.

et al. [65] examined the ethanol conversion in a similar MW Sun et al. [67] described a significant hydrogen production
plasma reactor at atmospheric pressure by directly supplying process from ethanol using a microwave discharge plasma
ethanol from the induction vaporizer to the plasma flame. The reactor. H2 and CO are produced in the reactor, while other
experiments showed that microwave power enhanced gases like CH4, C2H2, and CO2 are also in smaller quantities.
hydrogen production rate and volume concentration, while The highest hydrogen concentration and energy yields ob-
the increased ethanol mass flow rate gave higher hydrogen tained are 58.1% and 48.32 g/kWh at 1500 W with 70% ethanol
production efficiency. In comparison, Ogungbesan et al. [66] concentration in the solution. Thus, a feasible on-board
investigated the methane dissociation at atmospheric pres- hydrogen production showed good potential with less en-
sure with a quartz tube to generate an MW plasma torch at ergy demand. Similarly, Chehade et al. [68] designed an MW
2 kW and 2.45 GHz. The temperature caused by the microwave plasma reactor using a commercially available 2.45 GHz mi-
plasma torch is as high as 5000 ± 500 K, which is suitable for crowave oven for water plasmolysis. The steam at 107  C en-
methane decomposition into hydrogen. ters the reactor, having a tungsten electrode with a flow rate of
2478 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2

Table 7 e Advantages and Disadvantages of various plasma reforming reactors.

Gliding Arc Discharge Plasma Reactor Advantages:
1. High-energy efficiency
2. Low operating cost
3. Uses extensive concentration range of volatile organic compound
4. Flexibility of treating various pollutants
Disadvantages:
1. Overall Higher power consumption
2. Unstable plasma discharge
3. Moderate equipment cost
Microwave Plasma Reactor Advantages:
1. Highest hydrogen yield
2. Most efficient and productive
3. Catalyst (both homogeneous and heterogeneous) addition improves hydrogen
selectivity
4. Feedstock flexibility
Disadvantages:
1. Hot spot formation causes uneven temperature distribution within the system
2. Variable penetration depth due to low stability of microwave frequency
3. Microwave generation requires high power consumption
4. Batch-type reactor, not suitable for continuous hydrogen production
Dielectric Barrier Discharge Plasma Reactor Advantages:
1. Require comparatively low-frequency power supply
2. Reactor scalability by integration
3. Quiet and silent discharge process
4. Higher-purity hydrogen gas production
Disadvantages:
1. Not yet achieved economic feasibility
2. Catalyst Sensitivity and cost raise the overall production cost
3. Catalyst deactivation due to by-product contamination may lead to system shutdown
4. Catalyst performance plays a vital role due to plasma-catalyst synergetic effect
Pulsed Plasma Reactor Advantages:
1. Efficiently use of feedstocks like bio-oil and alcohols
2. Produces valuable by-product ‘graphite oxide.’
3. Energy-efficient for radical species and energetic photons production
4. Generate reactive products for the consistent reaction
Disadvantages:
1. Comparatively lower hydrogen yield
2. Carbon deposition on electrodes reduces the system's efficiency
3. Unable to dissipate all energy immediately will result in distortion of pulse and cause
altered polarity
4. Voltage may locally double in amplitude and can damage equipment
5. Propagation of discharge depends on the properties of the source

2 bbl/s, and the effects of pure and ceriated tungsten elec- discussion also shows that the plasma reforming technique is
trodes are examined. The ceriated tungsten sustained a promising and efficient for hydrogen production from multi-
higher H2 rate, and the H2 production rate ranges between 1.65 ple feedstocks, whether alcohol or other hydrocarbons. From
and 4.7 L/h, respectively, while the highest hydrogen energy the above discussion, a summary of the advantages and dis-
yield achieved is 13.3 g/kWh. Therefore, the fabricated mi- advantages of different plasma reforming techniques is pre-
crowave reactor generates hydrogen through water plasmol- pared and is described in Table 7 for better understanding.
ysis making hydrogen production more affordable. More MW Each technique has its advantages and disadvantages
plasma reactors with process parameters to achieve high H2 depending on influencing parameters and feedstocks. A
yield are depicted in Table 6. The MW plasma reactors are gliding arc plasma reactor is energy-efficient and flexible in
based on electromagnetic waves; thus, the frequency of the treating various feedstocks, but it generates unstable plasma
electromagnetic waves, input power, and feed flow rate play a discharge and has a moderate component cost. Similarly,
significant role in hydrogen production rate. microwave plasma rector gives the highest hydrogen yield at
atmospheric pressure, but the hot spot formation within the
reactor results in uneven temperature distribution causing
Advantages and disadvantages stability reduction. DBD plasma reactor requires a low-
frequency power supply and has scalability by numbering
The study enlightens the development of various plasma up, but the use of a catalyst raises the overall cost of the
reforming techniques for hydrogen production. The system, and catalyst sensitivity is also a topic of concern. A
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 2 4 6 7 e2 4 8 2 2479

The influencing parameters in DBD reactors are feed flow

rate and reactor temperature; the hydrogen production
rate is slightly above 100 L/h.

Pulsed plasma reactors show variations in hydrogen yield
by feed flow rate, electrode gap and velocity, and applied
voltage. However, the hydrogen production rate is similar
to DBD reactors.

The H2 selectivity in gliding arc plasma reactors is mainly
influenced by the oxygen-to-carbon (O/C) ratio, power, and
residence time. The hydrogen selectivity in gliding arc
plasma reactor is above 70% and may reach up to 97% in
some cases.

Hydrogen production in MW reactors is mainly influenced
by the frequency, power, and flow rate. These reactors
generate the highest hydrogen yield among all the reactors.

The plasma reactors are comparatively less costly, and

their construction requires less bulky equipment. Therefore, it
will likely replace cumbersome hydrogen storage systems
with compact on-board hydrogen production systems.
Therefore, the study helps understand the plasma reforming
Fig. 8 e Comparison of hydrogen yield by different plasma
techniques and their influencing operating parameters.
reactors.

Funding
pulsed plasma reactor is a continuous hydrogen-producing
This research did not receive any specific grant from funding
technique, generating a valuable by-product (graphite oxide);
agencies in the public, commercial, or not-for-profit sectors.
however, the electrode's carbon deposition requires constant
cleaning to maintain the high system efficiency.
The study also revealed that the microwave plasma re-
Availability of data and material
actors give the highest hydrogen yield, as depicted in Fig. 8,
while the other techniques have other advantages. Plasma
All data generated or analyzed during this study are included
reforming has an additional advantage over conventional
in this published article.
methods because it has a quick ON/OFF mechanism.
Hydrogen fuel is needed for every nation (whether devel-
oped or developing) to cut emissions and meet daily energy
Declaration of competing interest
requirements. Hydrogen production from plasma reforming is
a new process that needs to be set to get maximum benefits.
The authors declare that they have no known competing
Future research may focus on optimizing various influencing
financial interests or personal relationships that could have
parameters for enhanced hydrogen yield. Adding highly effi-
appeared to influence the work reported in this paper.
cient electronic components is another prospect to resource-
fully utilize the electrical energy for plasma generation and
reduce its demand for plasmolysis. references

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