Overview of h2 Prod Status Potential and Challenges
Overview of h2 Prod Status Potential and Challenges
Overview of h2 Prod Status Potential and Challenges
Fuel
journal homepage: www.elsevier.com/locate/fuel
A R T I C L E I N F O A B S T R A C T
Keywords: Hydrogen as an energy carrier can provide a long term solution to the problem of sustainable supply of cleaner
Hydrogen energy and environmentally friendly fuel. Hydrogen finds extensive use s in petroleum, chemical synthesis and treated
Green technology as a zero-emission fuel for transportation as well. It could also be used to produce power. Especially, in the
Plasmolysis
remote areas away from main cities where electrification cost would be significantly higher. A hydrogen based
Current status
Potential
decenteralized system could be developed where the “surplus” power generated by a renewable source could be
Challenges stored as chemical energy in the form of hydrogen. 80% of the whole hydrogen produced is by steam methan
reforming at an energy efficiency of 74–85%. However, steam methane reforming and other fossil fuel based
technologies are neither green nor sustainable. Hydrogen, could only be counted as a renewable and clean fuel if
the required power to produce hydrogen comes from a renewable source such as wind or solar power. Using a
renewable source, hydrogen could be produced by electrolysis, biohydrogen, thermochemical cycles, photo
catalysis, and plasmolysis. Amongst hydrogen production technologies, electrolysis contributes the highest 4% of
the total world’s energy demand. The production cost and energy efficiency estimated for electrolysis are 10.3
$/kg and 52%, respectively. Electrolysis, an energy-intensive process for hydrogen production, is still con
fronting challenges to manifest itself economically. While, the production rate of 20 g/kWh with predicated cost
and efficiency 0.09 €/kWh or 6.36 $/kg and 79.2%, respectively, has been reported that depicts plasmolysis
competitive on par with electrolysis with the advantage of low power consumption, reduced equipment size and
principle cost. This review highlights the current status, potential, and challenges of both renewable and non-
renewable hydrogen production. A new strategy for simultaneous hydrogen production and separation by
microplasmas and microbubble mediated mass transfer has been proposed. A decenterlaized system for hydrogen
generation by combining the proposed strategy with solar energy has been suggested to reduce the carbon
footprints.
1. Introduction fossil fuels, which are being dwindled dramatically [1]. Energy gener
ation through fossil fuels has a significant increase in greenhouse gases
The continuous urbanization and growth of the world’s population and CO2 in the environment, causing adverse climate changes [2,3]. The
and economy have led to a considerable increase in energy demand. To depletion of non-renewable energy resources and their impacts on the
date, around 80% of the global consumption of energy is fulfilled by environment. The researchers have developed their interest in
Abbreviations: AC, Alternating Current; AD, Anaerobic Digestion; AGIG, Australian Gas Infrastructure Group; CCS, CO2 Capturing and Storage; DBD, Dielectric
Barrier Discharge; DC, Direct Current; DF, Dark Fermentation; Et-OH, Ethanol; GHG, Green House Gases; GWP, Global Warming Potential; HC, Hydrocarbon; HV,
High Voltage; IEA, International Energy Agency; INL, Idaho National Laboratory; IR, Infrared; JAEA, Japan Atomic Energy Agency; LCA, Life Cycle Analysis; LCD,
Liquid Crystal Display; LED, Light Emitting Diode; LEL, Lower Explosive Limit; PACT, Plasma and Catalyst integrate Technology; PEM, Proton Exchange Membrane;
PEMFC, Proton-exchange Membrane Fuel Cell; PF, Photo Fermentation; PKR, Pakistan Rupees; PMCR, Plate Micro Channel Reactor; PPM, Parts Per Millions; PSRM,
Photocatalytic Steam Reforming of Methane; PV tech, Photovoltaic Technology; R&D, Research and Development; RF, Radio Frequency; RS, Reducing Sugar; SESR,
Sorption Enhanced Steam Reforming; SMR, Steam Methane Reforming; SOFC, Solid Oxide Fuel Cell; SOSE, Solid Oxide Electrolysis; SS, Stainless Steel; STH, Solar to
Hydrogen; HTE, High-temperature Electrolysis; TOC, Total Organic Contents; USD, United States Dollar; UV, Ultra Violet; VFA, Volatile Fatty Acids; VOC, Volatile
Organic Compounds; WW, Wastewater.
* Corresponding author.
E-mail address: frehman@cuilahore.edu.pk (F. Rehman).
https://doi.org/10.1016/j.fuel.2022.123317
Received 5 December 2021; Received in revised form 11 January 2022; Accepted 16 January 2022
Available online 11 February 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
M. Younas et al. Fuel 316 (2022) 123317
sustainable and green energy systems because fossil fuels dwindled batteries could enhance the distribution system’s reliability, energy ef
dramatically and their environmental consequences [4,5]. ficiency control, and energy quality [16]. However, the battery energy
Researchers have established energy-related networks and can storage system has its limits and challenges. Batteries’ overall weight
forecast future patterns and thus represent the energy crises. By 2060, as and high initial purchasing cost, driving range, thermal control, and
per World Energy Council statistics, the leading energy source will be battery life span are significant issues and challenges [15]. As a result,
only renewable source of energy [6]. Current consumption rates are the most often used lead-acid batteries have the most significant market
estimated to keep the world’s oil, gas, and coal reserves going for about share in sales and MWh generation. Batteries confront lead production
200, 40, and 60 years, respectively. The peak rates of liquid fuel and gas challenges with severe environmental implications, and recycling is
production appear to occur between 2015 and 2030. After that, the total necessary to lessen their impact [16].
resources will be in decline. Due to its depleted nature, conventional The solution may be the exquisite concept of storing renewable en
fuel’s sustainability has been a significant concern [7]. Thus, decar ergy in an energy carrier, such as hydrogen, that can be transported,
bonizing energy through alternative sustainable, green and renewable stored, and used. Fuel cell and other storage systems based on hydrogen
energy is critical for future energy management and sustainable devel are gaining importance for large-scale export, storage, and transport
opment [8-10]. [17]. Hydrogen can be derived from different pathways, technologies,
Currently, around 23.7% of the world’s total energy demand is ful and an immense range of feedstocks, including non-renewable and
filled by renewable sources such as solar, hydropower, wind, and bio renewable resources. Several technologies based on different pathways,
masses [11]. Hydropower, wind, solar energy is considered intermittent. feedstocks, and renewable or non-renewable sources are mentioned in
Several quality issues will be initiate when the generator is attached to Fig. 1. section-1. Emerging issues about the emissions of greenhouse
the grid. These issues include voltage dip during linkage to the gener gases (GHGs) have emphasized alternative energy sources for hydrogen
ator, supply unpredictability, unbalanced and distorted power supply. production. Water electrolysis is among the most efficient methods for
Humans have used biomass as an energy source for thousands of years. It producing sustainable hydrogen, accounting for 4–5% of global
is estimated that 80% of the overall renewable fuel supply is provided by hydrogen production [18]. Recently, different research groups have
traditional biomass energy [12]. The use of biomass for energy aims done work on plasmolysis to produce hydrogen. Rincon used a micro
could give humankind a new starting point. However, it requires over wave reactor to produce a 0.3007 g/kWh yield of hydrogen with 0.93%
coming the problems regarding biomass utilization for energy produc EtOH and 82.5% hydrogen selectivity with a power consumption of 300
tion, primarily hydrogen. The main issues are increasing food prices, kW power at the frequency of 2.45 GHz with ethanol and argon in feed
especially in developed countries, and a substantial increase in bio-crops [19]. Chehade has used the microwave reactor to create 13.3 g/kWh of
does not entirely solve environmental damage threats [13]. Another Hydrogen energy with 900 W of water as feed. [20]. Kirkpatrick has also
issue about biomass logistics is storage use, especially availability, reported a 0.25 g/kWh yield of hydrogen by using electrical corona
which is a characteristic of the feedstock [14]. discharges [21]. Rehman et al. [22] reported hydrogen production up to
Power storage is another challenge to increase energy efficiency 20 g/kWh using water vapor as a feed using Corona-DBD hybrid
control, reliability, and energy quality. A power storage system like micoreactor. The results demonstrated that the energy yield of hydrogen
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M. Younas et al. Fuel 316 (2022) 123317
2. Methods of hydrogen production CH4 + 2H2 O→CO2 + 4H2 (H298K = 165.1kJmol− 1 ) (4)
Hydrogen production pathways have been divided into two CO + H2 O→CO2 + H2 (H298K = − 41.2kJmol− 1 ) (5)
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M. Younas et al. Fuel 316 (2022) 123317
Noble metals such as platinum (Pt) and rhodium (Rh) or non- using steam methane reforming for hydrogen production is CO2 emis
precious metal catalysts like nickel (Ni) or noble metals such as plat sion [26]. CO2 capturing and Storage (CCS) helps maintain hydrogen
inum and rhodium could be used to carry out the reaction. The most production efficiency, however it can not provide a longterm solution. A
efficient catalysts are nickel-based catalysts, which do not restrict the 90% conversion peak has been reported using SMR via solar integration.
process and are less expensive [25]. Above 90% of the hydrogen purity is Wang et al. [46] compared hydrogen production based on fossil fuels
obtained using the potassium-doped lithium silicate (K-doped Li4SiO4) and solar energy and analyzed CO2 mitigation. Hydrogen production
in two parallel reactors, and sorption enhanced steam reforming [33]. using solar energy from the SMR process could reduce CO2 emission by
Using Ni-Co/CaO–Ca12Al14O33 (SESR), the maximum concentration of 0.315 mol, equivalent to a 24% reduction of CO2. However, renewable-
hydrogen is 82.23% and yield 2.31 L/g at 650◦ C [34]. Lithium zirconate based hydrogen production methods have problems of low efficiency,
is the catalyst used for CO2 adsorbent at high temperatures, and 97% intermittence, and output pressure that need to be optimized [47].
product concentration is possible by equilibrium limits and gas–water Methane and water could be used to produce hydrogen photo-
shift reaction[35]. It has been reported as 96% purity is achieved by catalytically by using semiconductor photocatalysts. The photo
MgO-modified Ni/CaO with the help of sorption enhanced steam catalytic steam reforming of CH4 (PSRM), as demonstrated in Fig. 3, is
reforming [36]. challenging because it requireshigh photocatalytic oxidative activity to
The hydrogen production from 1975 to 2018 extended to 115 Mton/ break the CH bond of CH4 and a strong reductive capability to split
year. Nowadays, Over 90% of the hydrogen produced from fossil fuels is water. As a result, wide bandgap semiconductors with high redox po
recovered, and obviously, about 830 million tonnes of carbon dioxide tentials should be investigated for PSRM [48–50].
are released annually [37]. SMR, oil fraction, coal gasification, and SMR is well developed mature technology for hydrogen production
electrolysis could produce 48%, 30%, 18%, and 4% hydrogen, respec which produces about 80% of total worldwide hydrogen production.
tively [38]. However, on a commercial scale, hydrogen production by Due to vast experiences at commercial scale as well as development in
SMR is still expensive than biomass gasification [39-41]. this technology has reduced production cost (2.9 $/kg) and enhanced
Steam ethanol reforming (SRE) placed an immense focus on yield efficiency (74–85 %) [45]. However, SMR requires complex cat
hydrogen (6 mol of H2 per mole of ethanol feed) because of the possible alytic processes as well as high temperature (700–1000◦ C). SMR pro
hydrogen yield. Making SRE cost-effective is challenging for the duces hydrogen by using non-renewable feedstocks such as liquefied
hydrogen production and purification system [36]. The cost of the SRE petroleum gas, Methanol, naphtha, jet fuel and biodiesel which are
in 2013 was calculated as 0.27 US$/kWh for an efficiency of 94.95% gradually depleting because world energy demand. SMR produces CO2
[42,43]. The cost of hydrogen production using SMR in 2008 was which is major cause for global warming potential [51]. An investigation
calculated as 1.28 ($/kg) with maintenance and the operational cost 3%. for hydrogen production into life cycle analysis (LCA) through SMR
The total capital cost is 150 million (Rs.) and obtaining the hydrogen found that GWP for fossil fuels was 9.46 kg CO2 / kg H2 [52]. Additional
purity 97% and system efficiency is 80% [44]. Currently, hydrogen equipment and energy are required to capture CO2 from exhaust gases
produced from SMR has a market value of about 2.9 $/kg [45]. and 100% CO2 can’t be captured [53]. In the present situation, clean and
SMR is the big CO2 emitter estimated to be nearly 2% of global CO2 green energies are getting attention. The green or renewable source will
emissions in 2015, based on 65 million tons of H2 production per year. It be a prominent source of electricity by 2060 [6]. SMR is a mature
has been reported that a strategy to scale up renewable power capacity technology. However, it contributes to global warming and fossil fuel
from 1.5 GW in 2015 to>15 GW in 2050 [45]. The great challenge of depletion, because it is neither green nor sustainable. Therefore, world is
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M. Younas et al. Fuel 316 (2022) 123317
Table 1 The syngas goes through the water gas shift reaction to increase H2
Coal gasification-based hydrogen production and coal gasification based mul yield. The gas product may be washed if it is appropriate to extract
tigeneration system. elemental sulfur or sulfuric acid [61]. There are many studies on
Coal gasification system Energy Exergy References hydrogen-based production on coal gasification and the multi-
efficiency efficiency generative system based on coal gasification, as shown in Table 1.
Trigeneration system 56.7% 45.05% [62] Coal gasification is also a huge source of CO2. Furthermore, Kothari
Combined coal gasification and 58% 55% [63] et al. [68] reported 29.33 kg CO2/kg H2 from a coal gasification system
alkaline water electrolysis system with 75% efficiency. CCS technology is used to capture CO2, but it is not
Integrated underground coal 29.2% 26% [64]
considered an appropriate solution on a large scale [69]. Moreover, the
gasification with SOFC fuel cell
system world’s coal reserves are expected to last for 150 years at current pro
Coal gasification-based co-generation 38.1% 27% [65] duction rates [70]. The environmental impact and reserve depletion are
system tending attention towards renewable feedstocks to produce hydrogen in
Coal gasification-based cogeneration – 54.3% [66] the future.
system
The integrated coal-based gasification 41% 36.5% [67]
In recent decades, biomass gasification has been widely used to form
system CO2, H2, CH4, CO, and other hydrocarbons as shown in Fig. 5. Biomass
Gasification, thermochemical water 51.3% 47.6% [57] gasification is performed in 700–1200◦ C using steam, oxygen, air, or
decomposition, and hydrogen mixture. Steam processing increases H2 and produces high-value nitro
compression systems
gen-free gas. [71]. The catalysts play a vital role in biomass gasification
to improve hydrogen yield. The effect of various catalysts on hydrogen
shifting towards renewable production pathways for environmental yield can be seen in Table 2. It has been reported as nickel-based cata
sustainability as well as alternative for fossil fuel depletion. lysts are considered most favorable. They are inexpensive and widely
used in industries for H2 production in biomass gasification [72]. The
2.1.2. Gasification: summary of different feedstock undergoing gasification with other
Gasification is an old-developed technology for hydrogen produc gasifying agents and catalysts for the hydrogen yield is given in Table 2.
tion. A carbonaceous feedstock is transformed into a gaseous product Gasification of biomass is more cost-effective than coal gasification.
with a useful chemical heating value [54]. Usually, three types of re It is estimated that 1 MW biomass gasification system costs around 367
actors- entrained flow, a fixed bed, and a fluidized bed- are used to gasify USD/kW, less than 720 USD/kW for a small-scale coal gasification plant.
biomass, among which the fluidized beds are considered the best. Flu [78].
idized bed reactors (FBRs) have substantial heat transfer and mas The future cost prediction via biomass gasification ranges of 13–17
stransfer capability between solid and liquid phases, better temperature $/GJ in 2030 [79]. The fluidized bed biomass gasification technology
controllability, and high stability [55]. sells hydrogen for 0.3 $/kg H2, less than the entrained flow reactor.
The most commercially viable feedstocks for efficient hydrogen However, coal is a significant source of greenhouse gas emissions and
production in gasification processes are coal [56-58] and biomass also causes acid rain. Co-gasification of coal and biomass is considered a
[59,60]. Coal is feasible for large-scale hydrogen production economi promising research field. Biomass has a lower energy content than coal
cally and physically through gasification. In gasification, coal is partly and helps to prevent the release of greenhouse gases. When two fuels are
oxidized by steam and O2, producing primarily CO and H2 merged with co-gasified, the overall emissions are reduced without reducing the en
CO2 and steam (syngas) in the high pressure and temperature reactor, as ergy content of the gas produced [80]. It has been reported that adding a
shown in Fig. 4. minute amount of biomass (up to 10 wt%) in gasification leads to higher
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M. Younas et al. Fuel 316 (2022) 123317
Table 2
Different feedstock with different gasifying agents and catalysts to produce hydrogen yield via biomass gasification.
Feedstock Gasifying agent Catalyst Temperature H2 concentration Reactor References
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M. Younas et al. Fuel 316 (2022) 123317
Table 3
Summary of investigations on pyrolysis of biomass for hydrogen production.
Biomass Reactor type Catalyst Temperature 0(◦ C) H2 content References
Wet Sludge Packed bed reactor Blast furnace slag 600–1000 1.71Nm3/kg [102]
Sawdust Fixed bed reactor Fe-Al 700 217 mL/g [103]
Rice Husk Fixed bed reactor Ni impregnation on char 500–700 315.3 mL/g [104]
Coconut Shell Fixed bed reactor NiAl2O3 550–750 22.11 mmol/g [105]
Sugar Cane Fixed bed reactor NiAl2O3 550–750 22.96 mmol/g [105]
Palm Kernel Shell Fixed bed reactor NiAl2O3 550–750 25.35 mmol/g [105]
Cotton Stalk Fixed bed reactor NiAl2O3 550–750 20.74 mmol/g [105]
Wheat Straw Fixed bed reactor NiAl2O3 550–750 16.38 mmol/g [105]
Sawdust Batch fixed bed reactor Without catalyst 500–850 45 wt% [93][93]
Cr2O3 48 wt%
MnO 47.6 wt%
FeO 45.8 wt%
Al2O3 45.6 wt%
CaO 46.6 wt%
CuO 45 wt%
Rice Straw Batch Fixed bed reactor No catalyst 500–850 44.2 wt%
Cr2O3 49.3 wt%
MnO 48.5 wt%
FeO 47.3 wt%
Al2O3 45 wt%
Glycerol Fixed bed microreactor No catalyst 650–800 (◦ C) 2.33 vol% [106]
Further, the consistency(quality) and purity of the substance can proton exchange membrane (PEM) fuel cells. Carbon byproduct is
differ considerably; thus, a purification unit is also required [84]. The helpful for raw or carbon/air fuel cell [95]. The thermal decomposition
presence of tar is one of the leading technological hindrances for the of natural gas has great potential in hydrogen production, eliminating
development of gasification. The presence of moisture content in CO2 and CO contaminants. Still, it can’t be easy potentially and
biomass gasification reduces process efficiency. More research is needed economically viable unless designing an efficient way to dispose of the
to improve catalyst utilization and reactor performance to overcome tar carbon by-product production during the reaction [95]. The hydrogen
and char disposal problems. Ash-like problems, including erosion, sin production capital investment for a large plant is 25–30% less than the
tering, agglomeration, and corrosion, make the gasification process vapor conversion or partial oxidation process [24]. The energy
economically non-viable [85]. Gasification can be a good solution for requirement for natural gas-led hydrogen production is 37.6 kJ/mol,
energy production from renewable sources, but there are some chal lower than SMR (63.3 kJ /mol) [96]. Since, fossil fuel reserves are being
lenges to explore at a large scale. Aggressive conditions in the gasifica depleted, and attention has been given to biomass pyrolysis for renew
tion process cause a significant problem in the gasifier. Depending on able and sustainable purposes. This renewable source can produce
how severe conditions are in gasifiers, feed injectors, protective coat hydrogen without greenhouse gas emissions [97]. Hence, hydrogen
ings, and tools such as thermocouples involving the gasifier have a short production from biomass pyrolysis is considered a long-term sustainable
life span. These problems in the gasifier reduce the average operating process.
time and demand another gasifier in series for continuous operation. Investigations on reactor types to increase hydrogen production ef
These issues and hurdles could severely affect the cost of the plant [86]. ficiency have got more attention nowadays. A fluidized bed reactor is
considered the most efficient to produce hydrogen economically. It re
2.1.3. Pyrolysis duces the production of tar and the coke and coal are deposited on the
Pyrolysis produces syngas, solid charcoal, and liquid fuel by heating catalysts, reducing the catalytic efficiency and delaying the production
organic materials in the absence of oxygen [87]. Pyrolysis can be clas of hydrogen. The coke and coal are deposited on the catalysts and reduce
sified based on operating conditions into slow [88], fast [89], and flash the pyrolysis reactor’s steam reforming performance [98]. Yeboah et al.
pyrolysis [90], which vary in heating intensity, reaction temperature, [99] reported a production rate of 250 kg H2 /day in a fluidized bed
and time of residence [91]. The high moisture content, a longer resi reactor. H2 production values in pyrolytic reforming, in fluidized bed
dence time, small particle sizes favor hydrogen production [92]. reactor, of different plastics like polyolefin, polystyrene, and poly
Hydrogen concentration can be notably increased by peak temperature ethylene terephthalate has been reported 34.8, 37.3, 29.1, and 18.2% by
or introducing catalyst [93], as shown in Fig. 6. In fast pyrolysis, high weight, respectively [100]. The cost through biomass production is ex
temperatures are suitable for rich-hydrogen production. Therefore, high pected to be 8.86–15.52 $/GJ, which highly depends on the type of
heating rates and relatively long residence time are optimal conditions biomass [24]. European Commission is paying attention to encourage
for synthesizing a high concentration of hydrogen [94]. The addition of and develop lower-level readiness technologies, including pyrolysis, in
catalysts significantly improves the rate of hydrogen production. Several the future.
researchers illustrated in Table 3 have reported investigations on suit Recent advancements have directed attention towards two-step py
able catalysts for hydrogen production. Noble metals such as Rh and Ru rolysis of biomass to achieve better efficiency. The first step involves
have significant catalytic viability; however, these are rare and expen converting biomass into gas, charcoal and bio-oil via rapid pyrolysis,
sive enough, making the process uneconomical, Using Ni and zeolite- followed by steam catalytic reforming of the bio-oil [101]. After CO is
based catalysts from biomass maximum gas production can be ach converted into CO2 and H2, hydrogen is purified by pressure swing
ieved [5,92]. It has been reported as Ni-based catalyst has been acquired adsorption. Furthermore, water gas shift reaction is applied to increase
for 45.33% conversion efficiency and 850◦ C is required [89]. hydrogen supply [27] as shown in Fig. 6. Some of the current in
To use fossil fuel/hydrocarbon for hydrogen production is consid vestigations to make pyrolysis economically viable are summarized in
ered conventional technique. Natural gas transformation into hydrogen Table 3.
and basic carbon through direct pyrolysis could be marketable because The hydrogen production from biomass can significantly reduce CO2
natural gas and greenhouse gas-free products are easily available. This emissions compared to the conventional SMR technique. Steam
process eliminates the cleaning stage, making it readily useable in reforming for hydrogen production was investigated by LCA, in which
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M. Younas et al. Fuel 316 (2022) 123317
feedstock was vegetable oil and fossil fuel. The global warming potential
range was from 3.3 kg CO2/kg H2-9.46 kg CO2/kg H2 for fossil fuels
[52]. Pyrolysis is cheaper than SMR. In addition, hydrogen production
costs can be reduced by increasing the system’s efficiency; biomass costs
are lowering due to the efficient use of biomass. [1]. The renewable
sources of energy for the pyrolysis of biomass may be considered cost-
effective and more efficient. Among renewable energy sources, solar-
driven pyrolysis is regarded as the most efficient for biomass pyroly
sis. Fahmy et al. studied a comparison of conventional pyrolysis with
solar-assisted pyrolysis and reported 25% energy saving in the case of
solar-assisted pyrolysis [94]. Co-pyrolysis is another method to enhance
H2 production efficiency as well. Zhang et al. [107] reported that the co-
pyrolysis of sewage and biomass increases the gas product directly
related to hydrogen production.
Pyrolysis is still in its initial phases of development. A lot of chal
lenges are to be confronted before its commercialization. The major
limitation of pyrolysis is char and tar deposition on the catalyst surface,
which reduces hydrogen production and causes catalyst deactivation. As
co-feeding of the system could minimize char and tar deposition on the
catalyst surface. Studies done over co-feeding found that carbon depo
sition could be suppressed. But, hydrogen production is reduced, and Fig. 7. Alkaline water electrolysis for hydrogen production.
CO2 concentration increases [108]. Limitations of biomass to hydrogen
are its high handling cost as well as seasonal availability. Process limi been reported that hydrogen can be produced at low voltage and low
tations of biomass to hydrogen that need to be overcome are pressure consumption cost by proceeding with the electrolysis of aqueous
resistance, corrosion, and hydrogen aging [92]. methanol, but carbon dioxide, a greenhouse gas, is emitted. The effi
Another major problem is the quality of the end product due to ciency of H2 production in electrolysis highly depends upon the feed
contaminants. Therefore, the most significant challenge may be stock. [120]. However, since methanol is produced from biomass, this
installing auxiliary equipment to make the end product contaminant- method is slow and energy-intensive. Water electrolysis is regarded as a
free [109]. The literature review depicts that several barriers and viable method of producing hydrogen. As hydrogen and oxygen evolve
challenges must surpass to make pyrolysis economically efficient. at different electrodes, one of the main advantages of electrolysis is that
However, volatile nature, segregation (due to low partial pressure) and there is no need for external separation sources and pure hydrogen can
purification ( high-temperature affect the membrane durability), be obtained. However, drawback of this method is that the energy
manufacturing costs, the selection of desired catalyst, availability of consumption is considerably high compared to other electrolysis
renewable biomass are all barriers in pyrolysis for hydrogen production methods. It has been reported that commercial water electrolyzer has an
[92]. energy consumption of about 4.5–5 kWh/Nm3, which is much greater
than other methods. However, its energy efficiency could be increased if
2.2. Renewable technologies energy is supplied through renewable sources like wind and light (PV
electrolysis) [68].
2.2.1. Electrolysis Net decomposition reaction of the hydrogen and oxygen conversion
Electrolysis is a non-spontaneous chemical decomposition technique is as follows.
in an electrolyzer (electrolyte, anode–cathode electrodes and separator,) 1
when an electric current is transmitted to an ion-containing solution H2 O + ElectricalEnergy→H2 + O2 (6)
2
[110]. Alkaline water electrolysis, Solid oxide electrolysis (SOES), PEM
electrolysis, High-temperature water electrolysis are the various In general, electrolyzers use energy from power grids, which are
methods that could be used for hydrogen production using electrolysis primarily powered by coal combustion, which is inefficient and eco-
[111-116]. The alkaline water and PEM electrolyzers operate at mod belligerent [121]. Electrolysis of alkaline water shown in Fig. 7 is
erate temperatures (373 K), but the SOSE electrolyzer operates at high considered to be more advantageous as compared to other methods of
temperatures (800–1273 K) [116]. The electrochemical breakdown of electrolysis.
steam at high temperatures has two benefits over the low temperature Alkaline water electrolysis is currently the cheapest way to produce
electrolysis technique. First, a high temperature electrolysis method is electrolytic grade hydrogen (~700–800 € / kW). While PEM and SOES
more efficient than typical room-temperature electrolysis because the are still expensive (~1000–1500 € / kW) and (~2800–5600 € / kW)
energy provided as heat is less expensive than electrical power. Second, respectively [122]. According to “IEA (2020), HYDROGEN REPORT,”
due of the low theoretical breakdown voltage at high steam tempera the number of projects and installed electrolyzers has been increased,
tures, the expended energy in high temperature electrolysis is minimal from less than 1 MW in 2010 to 25 MW in 2019. A 10 MW project in
[117]. The main disadvantage of hydrogen generation by electrolysis is Japan has started operations in 2020, while a 20 MW plant in Canada is
its high cost in comparison to the SMR technique. To deal with the high now under construction [123]. There have also been several an
SOSE operating temperature and huge thermal energy, a high-cost metal nouncements for large-scale projects with hundreds of megawatts of
oxide electrolyte is required [118]. The electrical power consumption of capacity projected to start functioning in the early 2020 s. The cost of
the process decreases as the SOSE working temperature rises, whereas two established technologies for 10 MW systems have been estimated to
the necessary thermal energy rises [119]. Because, SOSEs operate at be 0.7–1.4 EUR/W for alkaline water electrolysis and 0.8–2.2 EUR/W
high temperatures, costly catalysts are not required; nonetheless, certain for PEM electrolysis, respectively [124]. Idaho National Laboratory
chemical, thermal, and structural conditions must be satisfied [118]. (INL) has developed a 25 kW test facility for high-temperature elec
The cost of energy consumption determines the cost of hydrogen gen trolysis (HTE), intending to advance state-of-the-art HTE technology.
eration. Water electrolysis gives 4% of the world’s hydrogen demand [125].
[68]. Before SMR, water electrolysis was used extensively to produce
The electrolysis of aqueous methanol can produce hydrogen. It has hydrogen [126]. SMR is a well-known way to produce a large quantity of
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M. Younas et al. Fuel 316 (2022) 123317
3000 1200
Range1 Range2
2500 1000
Long Term (USD/kW)
2000 800
2030 (USD/kW)
1500 600
1000 400
500 200
0 0
Alkaline water PEM SOE
electrolyzer
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M. Younas et al. Fuel 316 (2022) 123317
Table 6
Biohydrogen potential for several industrial wastewaters as potential substrate reported in various studies.
Type of wastewater Reactor type Microbial culture Operating conditions H2 yield References
Brewery WW Batch reactor Klebsiella pneumoniae PH:6T:37 ◦ C 0.70 mol H2/mol glucose [148]
Textile WW Batch reactor Bacteria inoculum PH:7T:37 ◦ C 0.23 L H2/L-d [149]
Sugar beet WW Batch reactor Mixed culture PH:6.8 ± 0.3,T: 37 ◦ C 197.9 mL H2/g TOC [150]
Rice mill WW Glass reactor Enterobacter aerogenes PH:7,T:33 ± 2 ◦ C 1.74 molH2/mol RS [151]
Dairy WW Fluidized bed reactor Fermentation biomass T:24 ~ 30 ◦ C; OLR:28.7 ± 8.9gCOD/L-d 2.56 ± 0.62molH2/mol CH [152]
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M. Younas et al. Fuel 316 (2022) 123317
economic viability via dark fermentation is unfavorable because the reactors design may be helpful to overcome the low substrate conver
formation of metabolites volatile fatty acids (VFA’s) suppresses H2 yield sion and low hydrogen yield [166]. Biohydrogen is lab-scale technology,
and substrate degradation efficiency [155]. Biohydrogen production is still in the R&D stage, and additional research and advancements are
plagued by two major issues: limited substrate conversion and low needed to introduce it commercially.
productivity [153]. Therefore, researchers are making progress to
overcome these issues by developing validated integrated systems. 2.2.3. Photocatalysis
Integrating dark fermentation with other biological processes (such as Hydrogen produced by water using a catalyst and solar irradiation is
photo fermentation, MEC, and anaerobic digestion) could be viable for the promising method because the energy source is clean and perpetual
value-added fermentative biohydrogen production [156]. The dark (Solar) or photon-based technology. However, mostly water is used as a
fermentation (DF) integrated with biological hydrogen production renewable source that is environmentally safe without by-products or
processes is considered most prominent because of less energy con emissions, and valuable hydrogen energy production from photochem
sumption by dark fermentation [157]. ical conversion [167]. As a clean, safe, and renewable technology,
Integrated systems of dark fermentation with biological processes photocatalysis has been used for selective organic synthesis, CO2
are represented in Fig. 10. reduction, bacterial disinfection, pollutant degradation, and water
DF integrated with anaerobic digestion (AD) is efficient for energy splitting [167,168]. Photocatalytic water splitting to produce hydrogen
recovery as well as for the CO2 reduction phenomenon. In this tech is cost-effective and paid great interest in the past few decades
nique, H2/CH4 are produced in separate reactors in two steps. The main [169,170]. Fig. 11 shows water splitting into H2 and O2. Three main
limitation of this process for long-term operation is its monitoring and steps are involved for photocatalysis on semiconductor particles.
maintenance cost. Moreover, nitrogen and ammonia accumulation 1) Photons absorption with energies exceeding the semiconductor’s
of>800 mg/L can be detrimental for both approaches [158]. When the bandgap, leading in semiconductor particles to produce electron and
acid-hydrolysate pretreatment process is used then resulting in a nega hole pairs in the semiconductor particles.
tive net energy balance [159]. DF integrated with microbial electrolysis 2) The migration of photogenerated carriers in the semiconductor
cells (MEC) can increase energy recovery efficiency as well as bio particles carries charge separation.
hydrogen yield [160]. Therefore, methanogens produced in the second 3) Surface chemical reactions with different compounds (e.g., H2O)
stage of MEC suppresses biohydrogen yield. However, research is still in between these carriers. Electrons and holes can also be recombined
progress to reduce methanogens to make integration viable [161]. without any chemical reactions [171].
DF combined with PF can theoretically produce 12 mol of bio Photo-induced charge carrier recombination is relatively high in
hydrogen per mole of hexose [156]. In comparison, dark fermentation semiconductors like TiO2, and solar energy efficiency is low [172,173].
can theoretically produce only 4.2 mol of hydrogen per mole hexose Therefore, heterojunction of the semiconductor is made with another
[162]. Therefore, coupling DF with PF increases biohydrogen efficiency semiconductor with lower bandgap, metals, and electron mediators that
as VFA’s produced during DF are efficiently converted into further facilitate the reduction in energy barrier for H2 evolution, separation of
biohydrogen production [152]. But it confronts difficulty for large-scale photoinduced charges, and inhibit recombination of charges [174].
processes due to continuous light source requirements [163]. Noble metals are the most efficient co-catalyst to be used but because of
The two-step processes are considered efficient for biohydrogen the tradeoff between high cost and low abundance, non-noble metal co-
production but encounter high monitoring and maintenance costs catalysts are still in great demand [175].TiO2 has been widely employed
[158]. DF is thought to be more effective for the processing of bio for photocatalytic cleavage of water since it was one of the earliest
hydrogen but needs a constant light source that is energy-intensive on a semiconductors photocatalysts. UV light irradiation is used due to the
commercial scale [163]. The worldwide food shortage is another chal large bandgap of 3.2 eV [176,177]. Different semiconducting materials,
lenge to equilibrate between food and bio-energy [164]. Moreover, gas including oxides [178,179], (oxy) sulfide [180] and (oxy) nitrides
separation and purification are also required, making the process even [181], etc. have been developed in the last few decades. As, under
costly. Give higher income due to their application and pure gas value visible irradiation due to the low bandgap, CdS is considered more
[165]. Biohydrogen production confronts the main challenges of limited efficient with negative conduction band edge [176]. Several photo
substrates conversion and low productivity/low rates. Because of the catalysts with their co-catalyst are employed widely for the breakdown
low production rates of hydrogen, a large volume of reactors is required. of water to produce hydrogen. Several studies with different photo
So, the selection of suitable organisms, optimizing environmental con catalysts have been reported with their corresponding yield, illustrated
ditions, the extraordinary light utilization efficiency, and efficient bio- in Table 7.Table 8.Table 9.Table 10.
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M. Younas et al. Fuel 316 (2022) 123317
Table 7
Summary of photocatalysts for water splitting:
Feed stock Irradiation Photocatalyst Co- Yield References
catalyst
Table 8 Table 9
Summary of promising well-known thermochemical hydrogen-producing cycles. Several thermochemical water-splitting cycles with challenges and advantages:
Production routes Energy source H2 cost Overall References Thermochemical Advantages Main challenges References
efficiency cycles
S-I cycle Nuclear 14.62 $/kg 32.76% [217] S-I cycle • High thermal • High SO3 reduction [211,235]
ZnO/Zn cycle Solar 5 $/kg – [218] efficiency temperature
S-I cycle 70% solar/ 7.53 $/kg – [219] • No harm by • Corrosive materials
30% fossil products
S-I cycle Nuclear 4.87–6.09 36% [220] Cu-Cl cycle • Maximum • Recovering heat from [236,237]
(VHTR) $/kg process molten CuCl because
S-I cycle Nuclear 1.93 $/kg 52% [221] temperature of of phase change and
(MHR) 500–550◦ C solidification
S-I cycle Nuclear 1.85 $/kg 52% [221] • All reactions • Corrosive working
(VHTR) have been fluids
S-I cycle Nuclear 2.63 $/kg 38.1% [222] proven in the
(HTGR) laboratory
S-I cycle Nuclear (GT- 2.46 $/kg 11.6% [222] • No significant
HTR) side reactions
S-I cycle Nuclear (HTR- 3.78 $/kg 32.6% [222] ZnO/Zn cycle • Hydrogen • Separation of zinc [196,238]
PM) production in from oxygen
Mg-Cl hybrid Solar – 16.31% [223] two steps • Slow kinetics
cycle(4-step) integrated • No by-products • Back reactions
Mg-Cl hybrid Nuclear 3.67 $/kg 44.30% [224] • High-cost material for
cycle(4-step) (SCWR) high-temperature
HYS Solar thermal 3.19 $/kg 33% [225] solar reactor
Cu-Cl hybrid Nuclear – 45% [226] Mg-Cl cycle • Maximum • Mg compounds react [236,239]
cycle(5-step) process even an impenetrable
Cu-Cl hybrid Nuclear 2.31 $/kg 52% [227] temperature at layer of reaction
cycle(5-step) (SWCR) about 550◦ C products cover the
Cu-Cl hybrid Nuclear 2.02 $/kg 52% [227] surface
cycle(5-step) (VHTR) HYS cycle • Inexpensive • High temperature [211,240]
HYS Nuclear 1.77 $/kg 48.8% [228] material (>800◦ C) H2SO4
(MHR) • SO2 as an only decomposition
Cu-Cl Grid + 3.3 $/kg 40.4% [229] intermediate • Corrosive material
Thermal • Two steps to get
H2
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M. Younas et al. Fuel 316 (2022) 123317
Table 10
Summary of different plasma reactors with potential.
Feedstock T(K) V f(Hz) Power H2 yield Analyzer Reactor type References
(kV) (W)
Ethanol + >4500 – 2.45 GHz 300 0.3007 g/kWh yield of H2 with 0.93% EtOH and mass spectrometer Microwave [19]
Ar 82.5% hydrogen selectivity
H2O 300 – 2.45 GHz 900 The energy yield of H2 is reported 13.3 g/kWh Hydrogen catalytic Microwave [20]
sensor
H2O 573 18 10 kHz 120 Efficiency is reported to 49.32% GC-TCD PMCR [255]
H2O 373 4 36.74 10.5 20 g/kWh yield is predicted with 78.8% energy Indirect method DBD-Corona Hybrid [22]
kHz efficiency
H2O 3 60 Hz 37 0.25 g/kWh yield of H2 is predicted GC-TCD Corona Electrical [21]
discharge
glucose 433 – 29 kHz 150 The highest yield is reported 72% GC-TCD Rf [256]
H2S 430 – 50–150 It is possible to achieve H2 production at 300 kJ/mol GC-TCD DBD-Reactor [257]
Hz H2, which is less than SMR
Natural gas 373 – 1–10 kHz The production of H2 concentrations in natural gas up GC-TCD PDR [258]
to 45 vol% is reported
EtOH+N2 – – 2.45 GHz 2000 14.8 g/kWh H2 production is reported GC-TCD Microwave [259]
co-catalyst
utilisation
hetero nano-
junction structure
formation design
strategies to
enhance
catalytic
activity
doping and
dye defect
sensitisation control
surface
plasmonic
enhancement
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M. Younas et al. Fuel 316 (2022) 123317
splitting cycles for H2 production. When thermochemical cycle steps are terms of its great ability to integrate hydrogen generation processes with
increased, the required temperature decreases, and the process becomes a high-temperature reactor, thermochemical cycles of the sulfur family
economical [135]. (S-I and HYS). ZnO/Zn is also a viable solution in integrating the solar
As part of the technically possible thermochemical cycles, sulfur (S- reactor at high temperatures for thermochemical hydrogen production
I), hybrid (HYS), copper chloride, and magnesium chloride are investi [211]. Thermochemical cycles are not yet seen as competitive compared
gated. Specific thermochemical cycles include other types of energy and to traditional methods, while adequate integration with concentrated
thermal and chemical energy, such as photochemical, electrochemical, solar or nuclear reactors is required for further improvement [230].
or radiochemical cycles. Electrochemical cycles are most developed Hybrid cycles can achieve an efficiency of 52%, as shown in
among these all. The most advanced electrochemical and medium Japan Atomic energy Agency (JAEA) reported hydrogen production
temperature cycles are hybrid sulfur (HYS) and Cu-Cl cycles [134,216]. with the rate of 100 NL/h utilizing a test apparatus consisting of glass
The hydrogen prices and capacity for integration with industrial and fluorescent material through the sulfur-iodine cycle [231]. JAEA
waste heat at relatively low temperatures encourage Cu-Cl and Mg-Cl. In produced 10 L/h H2 in February 2016 for 8 h with the sulfur
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M. Younas et al. Fuel 316 (2022) 123317
iodine thermochemical water splitting [232]. as plasma reforming, occurs in particular plasma and catalyst integrated
As concerned with potential, thermochemical water splitting cycles technology (PACT) [244]. A quartz tube encompasses a tubular PACT
for hydrogen production, using the S-I cycle, are considered cost- reactor with two electrodes: mostly, the inside of the tube is made of
effective with nuclear or solar coupling point of view. It is reported as catalytically active metal such as Ru, Au, Pd, Ni, Rh and the outside is
the lowest cost is achieved for the S-I cycle on par with PEM electrolysis, made of aluminum electrode. Several feed gases could be used to carry
considering the same capacity and capacity factor. On par with other out the plasmolysis process. Hydrogen can be produced by using various
renewable hydrogen-producing technologies, S-I cycles and electrolysis feedstock such as water or its vapors and several hydrocarbons like
are considered cost-effective (10 $/kg H2) using solar irradiation [134]. methanol [245], ethanol [19], ethylene, acetylene [246] as well as
Thermochemical cycles coupling with nuclear is considered more kerosene oil [247].
environmentally benign than other hydrogen-producing technologies Typically, corona discharges that produce radicals with streamers of
coupling with nuclear reactors [233]. For sustainable hydrogen pro high-energy electrons are widely used for chemical synthesis. However,
duction, thermochemical water splitting cycles coupling with nuclear corona discharges are limited because of low power input feasibility. An
and solar encounter several predominant issues. The nuclear coupling increase in power leads toward arcing. So, dielectric barrier discharges
cycle is still in the R&D stage commercially [234]. Solar coupled cycles are considered most prominent to run a reactor at the higher power
have intermittency as well as low-efficiency issues. So, The capacity input to overcome arcing [22,248]. Hybrid reactor is considered most
factor of the plant is estimated to be 28%, and the solar to hydrogen efficient for chemical synthesis To make good use of corona and DBD
efficiency is estimated to be 20% [134]. However, R&D for thermo [248,249].
chemical water splitting is in progress to make it commercially as well as Recently, it has been reported that Lozano-Parada et.al has shown
economically viable. As concerned with challenges, recently verified production of ozone at 170 V AC using a micro reactor compared to
well-developed cycles encounter several issues. R&D is in progress to kilowatts used for a conventional ozone generator. Micro reactor’s other
mitigate these issues. benefit is that fluid dynamics can be tailored with highly brief gradients
gives elaboration of several challenges as well advantages. which are especially considered electronically controlled and precise as
Thermochemical cycles are cost-effective compared to conventional well [250]. Miniaturized corona DBD hybrid reactor gives the best op
methods. Integration with solar and nuclear reactors is necessary for portunity for optimized large-scale exposure with less input energy
further improvement, which is still in the R&D stage [241]. One of the required [248,250] that could prove itself further as micro-plasma
most significant challenges is thermal efficiency, which is directly required less interelectrode distance that leads to less ambipolar diffu
related to hydrogen production. [242]. Thermochemical cycles require sion and minimizes energy cost of ozone production to make it
high temperatures for hydrogen production to achieve higher effi economically viable with reasonable efficiency [251]. Battery sources
ciencies. These thermochemical cycles require a high-temperature can also be used to ignite the plasma microreactor [252]. Hydrogen can
resistant reactor constructed with chemically inert material. The be locally produced by coupling power supplies to distribute to con
economically feasible production of this material is a significant chal sumers. The hydrogen production and delivery to the fueling cell,
lenge for thermochemical processes [243]. The reactor design and harsh reactor, and combustion plant can be instantaneous. The use of
conditions (T, P, and corrosion) that have yet to be solved are still in hydrogen as a transport fuel becomes particularly important. This
their research phase. advancement could fix the ’hydrogen storage problems,’ one of the main
obstacles to hydrogen consumption, in light and heavy vehicles [253]. A
2.2.5. Plasmolysis lot of plasma reactors are available for hydrogen production using
Plasmolysis is carried out when water or its vapors are passed different feedstock and power consumption. Several plasma reactors
through the reactor, resulting in plasma formation. Plasmolysis, known with different feedstocks and potential are listed in
15
M. Younas et al. Fuel 316 (2022) 123317
Fig. 17. A proposed strategy for hydrogen production by water vapor splitting plasmolysis.
Micro-plasma use is one of the latest developments [254]. Micro- ultrasound to induce local cavities in the ultrasonic waves. These tech
plasma and low power consumption provide better process control niques require high power densities for microbubble formation [265].
than traditional plasma reactors [250]. Battery sources can also be used The third-class uses mechanical vibration or fluidic oscillations to
to ignite the plasma microreactor [252]. Hydrogen can be local oscillate the fluids [264].
ly produced by coupling power supplies to distribute to consumers. The The smallest possible volume of bubbles in the shape of a hemisphere
hydrogen production and delivery to the fueling cell, reactor, and could be produced by a fluidic oscillator [265]. It is considered the
combustion plant can be instantaneous. The use of hydrogen as a cheapest and low maintenance is required since there is no moving
transport fuel becomes particularly important. This advancement could component within itself. It could produce microbubble in the range of
fix the ’hydrogen storage problems which is considered one of the main 80–120 μm with observed about 55% mass transfer co-efficient
obstacles to hydrogen consumption in light and heavy vehicles [253]. A compared with the steady flow that produces bubbles approximately
lot of plasma reactors are available for hydrogen production using 1 mm with the same diffuser [264]. So, increasing mass transfer co-
different feedstock and power consumption. Several are listed in efficient helps overcome the dissolution problem [266].
Hydrogen production through plasmolysis confronts several prob Oxygen and hydrogen are produced in plasma reactors and need to
lems. Dissolution is one of the major problems affecting hydrogen pro be separated. Therefore, in cold conditions, the separation of outlet
duction efficiency [244]. Several kinetic models are developed to steam dissociation species is made by an ice trap in which frozen liquid
enhance dissolution and hence system efficiency. Chen et al. reported is filled − 1.5 to − 2◦ C [255]. The recombination of H2 and O2 could be
the conversion of 0.32 mol % of hydrogen. This conversion could obtain avoided by the condensation of un-condensed water. Then water could
when plasma was ignited at 2.5 kV with 14.2% water concentration in be separated and dry gas could be produced. The dry gases flow through
argon [260]. When methanol concentration in nitrogen was 5% and the the condenser outlet to the flow meter and catalytic hydrogen sensor
gas temperature was between 27 and 77 ◦ C, a high conversion was [20]. Inert argon gas could be recycled as the proposed strategy is shown
achieved (up to 87.1% methanol) [261]. Separation is another major in Fig. 17.
problem in hydrogen production by water vapor plasmolysis. H2 is The storage of H2 is another obstacle to the economic feasibility of
separated by different techniques like compression, heat exchange, plasmolysis at a large scale. Several storage methods were presented as
cryogenic distillation and pressure swing adsorption (PSA) [262]. different, safe, effective hydrogen energy carriers, including Porous H2
However, these techniques are cost-intensive and result in high capital Storage Materials [267], ammonia liquid carrier, intermetallic hydrides,
costs of the hydrogen production system [262]. Membrane separation is quite high entropy alloys, complex metal hydrides and liquid hydrogen
another technique used for hydrogen separation, but selectivity, carriers. The international hydrogen energy industry regards the liquid
permeability, and aging problems make separation less efficient [263]. state as a suitable option for hydrogen transport and storage at large
Considering these limitations, membrane exposure for hydrogen sepa scale [268]. The latest dramatic decrease in the electricity auction prices
ration is unreliable for the long term [263]. The separation of H2 could in areas with favorable wind and solar conditions for green energy in
be made efficient and cost-effective by introducing microbubbles in the stallations occurred [269]. The cheap prices advantage highlighted the
system, which leads to the increased mass transfer co-efficient. As, ox possibility of energy supply chains transporting green energy from the
ygen is 25 times more soluble in water in comparison to hydrogen. affluent renewable areas through a carrier. Renewable energy con
Therefore, if the product gases could be entered through large reactor version into hydrogen and long-distance transportation of this hydrogen
column through the microbubble process, hydrogen-rich gas would in the form of liquid is considered a way of transporting energy with an
yield from the top side [264]. In general, microbubble generation could economical fashion [270]. It could be a viable choice for remote areas
be discussed by three ways. Compression and release of gas by using air without direct grid links, with a high renewable power generation
stream compression through a nozzle. The second class uses power capacity.
16
M. Younas et al. Fuel 316 (2022) 123317
Table 11
advantages, disadvantages, cost and efficiency for all prescribed hydrogen production technologies.
Hydrogen Advantages Disadvantages Cost Efficiency References
production ($/kg)
methods
Non-Renewable pathways
SMR ▪ Low production cost ▪ Higher temperature requirements 2.9 74–85% [51,52]
▪ High yield efficiency ▪ Complex catalytic processes
▪ Fossil fuel depletion
▪ Global warming potential
Gasification ▪ Low production cost ▪ Higher temperature requirements 1.91 35% [85,277]
▪ Higher energy and exergy efficiency ▪ Aggressive nature
▪ Co-gasification yields more hydrogen ▪ Tar production
production, less carbon footprints ▪ Gasifier short life span
▪ Fossil fuel depletion
▪ Global warming potential
Pyrolysis ▪ Cheaper than SMR ▪ High temperature requirement 1.6 42.5% [92,108,277]
▪ Co-pyrolysis produces more hydrogen yield, ▪ Char deposition on catalyst surface
less footprints ▪ Still in initial stage
▪ Higher energy yield ▪ Requirements of auxiliary equipments
▪ Char and Tar deposition are less than for purification
gasification ▪ High handling cost of biomass
▪ Seasonal availability
▪ Fossil fuel depletion for coal pyrolysis
▪ Global warming potential
Renewable pathways
Electrolysis ▪ Considered effective method for hydrogen ▪ Energy intensive process 10.3 70% [9,61,139,243]
production from renewables ▪ High principal and maintenance cost
▪ Produces 4% of total hydrogen produced
worldwide
▪ No auxiliary equipment is required for
separation
▪ Feedstock is cheap and easily available
Bio-hydrogen ▪ Feasible from the perspective of GHG ▪ Food vs energy problems 2.83 0.1% [164,166,277]
emissions and net energy ▪ High moisture content
▪ Cheap feedstocks ▪ Purity issues
▪ It converts waste into valuable product, ▪ Low hydrogen energy yield
beneficial for environmental sustainability ▪ Low substrate conversion
▪ Less energy requirement than SMR
Photocatalysis ▪ Low principal cost Developing low-cost semiconducting material is 9 0.06% [171,203,277]
▪ Photonic (solar-based catalysis) is the best hardCatalysts are expensive and regeneration is
option for all environmental performance, difficultHigh energy band gap is a major
ranking on par with biological, thermal, and issueStill in R&D stage
electrical-based hydrogen technologies
Thermochemical ▪ Reuse of chemicals within cycle High temperature requirementLow thermal 2.31 52% [25,138,221,227,278]
cycles ▪ Lowest cost is achieved for the S-I cycle on efficiencyComplex reactor design
par with PEM electrolysis
▪ Cost effective
▪ Energy efficiency is good
Plasmolysis ▪ Separation of hydrogen from oxygen is an ▪ Low principal cost 6.36 79.2% [22]
issue ▪ Low operational cost
▪ Still R&D stage ▪ Simple reactor design
▪ Less power consumption
▪ High energy yield
▪ High thermal efficiency
▪ High energy efficiency
It has been reported that electrolysis could produce 4% of globally processing of hydrogen by water vapor plasmolysis is expected to prove
produced hydrogen, which is considered green and prevents GHG cheaper and more cost-effective [274]. Integrating plasma microreactor
emissions [18]. From these mentioned green technologies, electrolysis is with solar energy may increase the process efficiency to produce steam
considered an emerging technology on a commercial scale. But the and required hydrogen. Secondly the biggest attraction could be the low
electrolysis is regarded as an energy-intensive process. On par with capital cost as well as low maintenance cost of miniaturized plasma
electrolysis, Rehman et al. [271] reported that by using a Corona-DBD reactors [251]. Multiplexing plasma micro rectors will boost the output
hybrid reactor, having flow channel 2.48 mm and radial gap of 1.24 of hydrogen that is cheaper in terms of costs than electrolysis for large-
mm, hydrogen production rate of 20 g/kWh could be achieved with the scale hydrogen production [274] . Hydrogen fuel produced from solar
predicated cost of 0.09 €/kWh that is competitive to electrolysis and energy would be renewable and green.
beneficial because of reduced equipment size, less maintenance cost and
less power consumption [22]. 3. Comparison of plasmolysis with other methods for hydrogen
In developing the hydrogen economy, hydrogen production pro production
cesses are critical, producing hydrogen at comparable expenses and
being environmentally friendly to fossil fuels [272]. The chemical The production of hydrogen pathways has been divided into two
plasma conversion processes are gaining interest due to their inherent categories; Non-Renewable and Renewable hydrogen production sour
versatility and their direct use of (potentially renewable) electricity ces. Considering Non-Renewable hydrogen production pathways, SMR
[273]. Together with recent advances in plasma technology, the is considered a well-established and widely used process that
17
M. Younas et al. Fuel 316 (2022) 123317
Fig. 18. Comparison of hydrogen production pathways via efficiency and cost.
gives>80% of globally produced hydrogen [275]. Although SMR is a effectively, overcoming the energy-intensive process, and meeting the
mature technology, major problems confronting it are global warming compatible capital and maintenance cost. Plasmolysis is another
potential and fossil fuel utilization. Additional equipment and energy renewable hydrogen production pathway and proposed strategy of this
are required to capture CO2 from exhaust gases, and that 100% CO2 review article. The hydrogen production rate of 20 g/kWh with the
cannot be captured [53]. Gasification is one of the developed techniques predicated cost of 0.09 €/kWh has been reported by [22]. This depicts
to produce hydrogen. Co-gasification is much more efficient than indi plasmolysis competitive on par with electrolysis as reduced equipment
vidually coal or biomass gasification, leading to higher H2 and CO size and low power consumption are the major benefits [22]. Hydrogen
production [81]. However, tar formation is still a big challenge [72]. production through plasmolysis could be considered highly efficient in
Aggressive gasifier conditions cause major problems and demand comparison to other existing technologies. Rehman et al. [22,271] re
another gasifier in series for operation [86]. It also has global warming ported 79.2% energy efficiency in comparison to other technology. The
potential and fossil fuel depletion problems as well. Pyrolysis is also an literature depicts that hydrogen production through plasmolysis is more
old hydrogen production pathway but is still at early stage of its expo energy efficient with reasonable cost that makes it competitive to most
sure for large scale. It may confront a lot of problems for its widespread appropriate electrolysis pathway.
production, such as low hydrogen yield, separation and purification is Hydrogen production by water vapor plasmolysis could potentially
sues, food vs energy problems, tar deposition, and production cost [92]. be cheaper and economically viable [274]. While still in the R&D stage,
Installation of auxiliary equipment to make end product contaminant hydrogen production faces the challenges of separation and storage but
free is also another major challenge of this technology [109]. could produce hydrogen efficiently at reasonable cost in comparison to
While, considering Renewable pathways, the Biohydrogen process is fossil fuels and would be environmentally viable [272]. Table 11 shows
pollution-free and eco-hostile and can be easily produced at atmospheric advantages, disadvantages, cost and efficiency for all prescribed
pressure and temperature with high energy content (120 kJ/g) [140]. hydrogen production technologies.
DF integrated with PF is considered the most efficient route for bio Table 11 depicts that maximum hydrogen energy efficiency,
hydrogen production, but it requires a continuous light source, making it 74–85%, could be obtained from SMR [52]. However, fossil fuel
less suitable for large-scale applications [276]. Biohydrogen production depletion and global warming potential directed world to pay attention
confronts low hydrogen yield [166], high moisture content, separation towards renewable energy resources. From renewable energy resources,
and purity issues, and food vs energy issues [164,165]. Biohydrogen is electrolysis yields energy efficiency up to 52% with corresponding cost
still in the R&D stage, and additional research and advancements are 10.3 $/kg [9]. However, trailing behind electrolysis, Corona-DBD
needed to introduce it commercially. Photocatalysis is another tech hybrid micro reactor was used by Rehman et al. [22] to investigate
nique to produce hydrogen which depends on photons generation, It is hydrogen energy yield, energy efficiency and production cost 20 g/kWh,
clean and environmentally safe. However, the technology encounters 79.2% and 6.36 $/kg, respectively. Fig. 18 shows comparison for pre
many challenges, such as developing low-cost semiconducting catalytic scribed hydrogen production technologies regarding their cost and ef
material with high energy bandgap, expensive catalysts, and difficulties ficiency. Furthermore, it is envisaged that integration of solar energy to
in catalyst regeneration [171,167]. This technology is also still in R&D produce steam and produce the required hydrogen with plasma micro-
to prepare a less expensive and abundant semiconducting material with reactor technology can increase the efficiency of the process. Secondly
the sacrificial agent [203]. Thermochemical cycles are cost-effective the biggest attraction could be the low capital cost as well as low
compared to previously discussed techniques. Still, it has high- maintenance cost of miniaturized plasma reactors [251]. Multiplexing of
temperature requirements, low thermal efficiency and a complex plasma micro-reactors could increase hydrogen production, which may
reactor design [243,241]. Water electrolysis is considered one of the be cheaper than electrolysis in terms of cost for commercial-scale pro
major renewable hydrogen production pathways. The most significant duction facilities [274].
advantage of this technology is that it does not require H2 separation.
Water electrolysis gives about 4% of the world’s hydrogen demand [68].
However, electrolysis’s main challenges are producing hydrogen cost-
18
M. Younas et al. Fuel 316 (2022) 123317
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