1 s2.0 S1364032116305366 Main
1 s2.0 S1364032116305366 Main
1 s2.0 S1364032116305366 Main
art ic l e i nf o a b s t r a c t
Article history: Climate change and fossil fuel depletion are the main reasons leading to hydrogen technology. There are
Received 28 September 2015 many processes for hydrogen production from both conventional and alternative energy resources such
Received in revised form as natural gas, coal, nuclear, biomass, solar and wind. In this work, a comparative overview of the major
9 March 2016
hydrogen production methods is carried out. The process descriptions along with the technical and
Accepted 9 September 2016
Available online 18 September 2016
economic aspects of 14 different production methods are discussed. An overall comparison is carried out,
and the results regarding both the conventional and renewable methods are presented. The thermo-
Keywords: chemical pyrolysis and gasification are economically viable approaches providing the highest potential to
Hydrogen production become competitive on a large scale in the near future while conventional methods retain their domi-
Water splitting
nant role in H2 production with costs in the range of 1.34–2.27 $/kg. Biological methods appear to be a
Green hydrogen
promising pathway but further research studies are needed to improve their production rates, while the
low conversion efficiencies in combination with the high investment costs are the key restrictions for
water-splitting technologies to compete with conventional methods. However, further development of
these technologies along with significant innovations concerning H2 storage, transportation and utili-
zation, implies the decrease of the national dependence on fossil fuel imports and green hydrogen will
dominate over the traditional energy resources.
& 2016 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2. H2 production from fossil fuels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1. Hydrocarbon reforming methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
2.1.1. Steam reforming method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
2.1.2. Partial oxidation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
2.1.3. Autothermal reforming method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
2.2. Hydrocarbon pyrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
3. H2 production from renewable sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.1. Biomass process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.1.1. Thermochemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.1.2. Biological processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
3.2. Water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
3.2.1. Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
3.2.2. Thermolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
3.2.3. Photo-electrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
4. Overall comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
5. H2 storage, transportation and utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
n
Corresponding author.
E-mail address: [email protected] (A. Poullikkas).
http://dx.doi.org/10.1016/j.rser.2016.09.044
1364-0321/& 2016 Elsevier Ltd. All rights reserved.
598 P. Nikolaidis, A. Poullikkas / Renewable and Sustainable Energy Reviews 67 (2017) 597–611
Biological Thermochemical
Fig. 2. The types of ideal continuous flows used in membrane-based separations [31].
From methane (by applying n ¼1, m ¼4 to Eq. (8)), the thermal 2.2. Hydrocarbon pyrolysis
efficiency is 60–75%, while the optimum operating value has been
calculated at around 700 °C inlet temperature, for ratios S/C ¼ 1.5 Hydrocarbon (CHs) pyrolysis is a well-known process in which
and O2/C ¼ 0.45 where the maximum hydrogen yield is about 2.8 the only source of hydrogen is the hydrocarbon itself, which un-
[34,41]. In Fig. 8, a simplified flow diagram of the ATR of methane dergoes thermal decomposition through the following general
is available presenting the process explained by Eq. (8). The in- reaction:
vestment costs are about 15–25% and 50% lower than SMR and 1
Cn Hm → nC + mH2
2 (9)
Fig. 8. Flow diagram of the autothermal reforming of methane process. CH1.6-C þ0.8H2 (overall) (12)
602 P. Nikolaidis, A. Poullikkas / Renewable and Sustainable Energy Reviews 67 (2017) 597–611
of 8.86 $/GJ to 15.52 $/GJ (or 1.25 $/kg to 2.20 $/kg), depending on
the facility size and biomass type [56].
Biomass gasification is the thermochemical conversion of bio-
mass into a gaseous fuel (syngas) in a gasification medium such as
air, oxygen and/or steam. It takes place at temperatures between
500 and 1400 °C, operating pressures from atmospheric to 33 bar
depending on the plant scale and the final application of the
produced syngas and the types of the reactor are distinguished
according to the flow and velocity of the gasifying agent [57]. Fixed
bed, fluidized bed and indirect gasifiers are the three main types of
reactors used for biomass gasification, the most common config-
urations of which are shown in Fig. 11. Eqs. (16) and (17), represent
the transformation of biomass into syngas, when it reacts with air
or steam, respectively.
Fig. 12. Flow diagram of the biomass gasification process.
Biomass þ Air-H2 þCO2 þCOþ N2 þCH4 þother
CHs þtar þH2Oþ char (16) 3.1.2. Biological processes
Due to increased attention to sustainable development and
Biomass þ Steam-H2 þCOþCO2 þCH4 þother CHs þ tarþchar (17) waste minimization, research in biological hydrogen production
has substantially increased over the last several years. Most bio-
After the transformation of biomass into syngas, the gas mix- logical processes operate at ambient temperature and pressure,
ture is further treated in the same way as the product gas of the thus less energy intensive. Moreover, they utilize renewable en-
pyrolysis process, as shown in Fig. 12. However, biomass type, ergy resources which are inexhaustible and they contribute to
particle size, temperature, steam-to-biomass ratio and type of waste recycling as they can also use various waste materials as
catalyst used are the main parameters affecting on hydrogen yield feedstock [61].
[54,55]. In steam gasification, the yield of hydrogen is far better The major biological processes utilized for hydrogen gas pro-
than fast pyrolysis while the overall efficiency (thermal-to-hy- duction are direct and indirect bio-photolysis, photo and dark
drogen) can reach up to 52% providing an effective means of re- fermentations, and multi-stage or sequential dark and photo-fer-
newable hydrogen production [52,59]. It is estimated that a typical mentation. The feeds for bio-hydrogen are water for photolysis
route of biomass gasification-steam reforming-PSA, requires 2.4 TJ where hydrogen is produced by some bacteria or algae directly
of primary energy input per TJ of hydrogen [60], and for a plant through their hydrogenase or nitrogenase enzyme system, and
with an expected hydrogen output of 139,700 kg/day and cost of biomass for fermentative processes where the carbohydrate con-
biomass in the range of 46–80 $/dry-ton the hydrogen production taining materials are converted to organic acids and then to hy-
cost is expected to be 1.77–2.05 $/kg [39]. drogen gas by using bio-processing technologies [27,41].
Assuming a very optimistic capital cost for photo-bioreactor of Fig. 14. Flow diagram of the indirect bio-photolysis process.
only 50 $/m2, minimal operating costs at an overall 10% solar
conversion efficiency and many cost components such as en- 4 and 2 mol per mole of glucose in acetate and butyrate type
gineering, gas separation and handling being not included, the fermentation, respectively [29].
hydrogen cost is estimated to 15 $/GJ or 2.13 $/kg of H2 produced
[62]. An increase of 20% of the capital cost implies 33.33% higher C6H12O6 þ2H2O-2CH3COOHþ4H2 þ2CO2 (acetate fermentation)
production cost [56]. (21)
In indirect bio-photolysis, the general reaction for hydrogen
formation from water by cyanobacteria or blue-green algae can be C6H12O6 þ2H2O-CH3CH2CH2COOHþ2H2 þ2CO2 (butyrate fer-
represented by following reactions: mentation) (22)
12H2O þ6CO2 þlight energy-C6H12O6 þ6O2 (19)
Glucose, as the preferred source for this process, is relatively
expensive and is not readily available in high quantities but can be
C6H12O6 þ12H2Oþ light energy-12H2 þ6CO2 (20) obtained from agriculture wastes. Starch containing materials
The schematic diagram of indirect bio-photolysis process can which are abundant in nature, as well as cellulose which is the
be observed in Fig. 14. Hydrogen is produced both by hydrogenase major constitute of plant biomass, can be alternatively used [27].
and nitrogenase enzymes and the production rate is comparable to For the optimal production, pH should be maintained between
hydrogenase-based production by green algae [56]. Although in- 5 and 6 as the amount of H2 production by this process highly
direct bio-photolysis processes are still at the conceptual stage, depends on its value [56]. Another constraint is that the hydrogen
assuming a total capital cost of 135 $/m2 the production cost is must be removed as it is generated because as the pressure in-
estimated to 10 $/GJ or 1.42 $/kg of H2 [62]. Hence, the algal H2 creases the H2 production tends to decrease [41]. However, dark
production could be considered as an economical and sustainable fermentation is realized over a relatively simple process that does
method in terms of water utilization as a renewable source and not rely on the availability of light sources, as can be seen from
CO2 consumption as one of the air pollutants. However, low H2 Fig. 15 [19]. Thus, much land is not a requirement and hydrogen
production potential, the requirement of significant surface area to can be produced constantly through day and night from a wide
collect sufficient light and no waste utilization are the main spectrum of potentially utilizable substrates including refuse and
drawbacks of this bio-hydrogen production method [27,41]. waste products [61].
Fermentations are biochemical processes that take place with The second biochemical process is photo-fermentation which is
or without oxygen and perform microbial transformations of or- realized in deficient nitrogen conditions using solar energy and
ganic feed materials producing alcohols, acetone and H2 in mini- organic acids. Due to the presence of nitrogenase, some photo-
mal amounts as well as CO2. These methods constitute an attrac- synthetic bacteria are capable of converting the organic acids
tive approach for bio-hydrogen production as they utilize waste (acetic, lactic and butyric) into hydrogen and carbon dioxide ac-
materials, providing inexpensive energy generation with simulta- cording to the following reaction [19]. With acetic acid as the re-
neous waste treatment [35]. actant, the overall conversion into H2 is presented below.
Dark fermentation uses primarily anaerobic bacteria on car-
bohydrate rich substrates under anoxic (no oxygen present), dark
conditions. As can be seen from Eqs. (21) and (22), with glucose as
the model substrate, acetic and butyric acids constitute over than
80% of total end-products and theoretically the yields of H2 are Fig. 15. Flow diagram of the dark fermentation process.
P. Nikolaidis, A. Poullikkas / Renewable and Sustainable Energy Reviews 67 (2017) 597–611 605
Table 2
Hydrogen synthesis rate and bio-reactor volume needed for 5 kW PEMFC (adapted
from [41]).
Table 3
Hydrogen production cost of different approaches for electrolysis (adapted from
[39]).
a
Fig. 19. Flow diagram of the water electrolysis process. Based on electrolyzer cost of 500 $/kW.
b
Based on photovoltaic cost varying from 0.75 $/Wpeak to 5 $/Wpeak and an
electrolyzer cost of 450 $/kW.
To date, the developed and commonly used electrolysis technol- c
The cost of 6.61 $/kg assumes the coproduction of electricity along with hy-
ogies are alkaline, proton exchange membrane (PEM) and solid oxide drogen whereas, 6.77 $/kg represents the cost of only hydrogen production.
electrolysis cells (SOEC). In PEM electrolyzer water is introduced at
the anode where it is split into protons (hydrogen ions, H þ ) which in
over 2500 °C, in order the Gibbs function (ΔG) to become zero and
turn travel through membrane to the cathode in order to form H2,
the separation of hydrogen from the equilibrium mixture become
and oxygen which remains back with water. In alkaline and SOEC,
feasible [81]. Since such expenditures of considerable primary
water is introduced at the cathode where it is split into H2 which is
energy could not be achieved by sustainable heat sources, several
separated from water in an external separation unit and hydroxide
thermochemical water-splitting cycles have been proposed to
ions (OH-) which in turn travel through the aqueous electrolyte to
lower the temperature and improve the overall efficiency. Ther-
the anode in order to form O2 [67]. SOEC systems differ in that part of
mochemical cycles consist of a series of chemical reactions at
the electrical energy is replaced with thermal as a result the tem-
different temperatures and constitute one of the most promising
perature increases and consequently, the H2 is left in unreacted
process through which heat is converted into chemical energy in
steam stream [41]. Overall conversions realized to both sides of each
the form of hydrogen [32,49,50]. Two examples of thermo-
individual system can be summarized as follows:
chemical cycle, represented by the chemical reactions (32)–(38)
respectively, are shown below enabling the comparison with the
Alkaline and SOEC:
single-stage water decomposition of Eq. (31).
Anode:
Fig. 20. Flow diagram of the solar-based thermochemical water splitting process.
Table 4
Hydrogen production costs by various approaches for thermochemical water splitting.
Heat source Thermochemical cycle Maximum temperature [°C] Overall eEfficiency [%] Production rate [kg/day] Hydrogen cost [$/kg] Refs.
Table 5
Comparison of the different hydrogen production processes.
SR 74–85 Most developed technology, existing infrastructure. CO2 byproduct, dependence on fossil fuels.
POX 60–75 Proven technology, existing infrastructure. CO2 byproduct, dependence on fossil fuels.
ATR 60–75 Proven technology, existing infrastructure. CO2 byproduct, dependence on fossil fuels.
CHs pyrolysis – Emission-free, reduced-step procedure. Carbon byproduct, dependence on fossil fuels.
Biomass pyrolysis 35–50 CO2-neutral, abundant and cheap feedstock. Tar formation, varying H2 content due to seasonal
availability and feedstock impurities.
Biomass gasification – CO2-neutral, abundant and cheap feedstock. Tar formation, varying H2 content due to seasonal
availability and feedstock impurities.
Bio-photolysis 10 CO2-consumed, O2 is the only byproduct, operation under mild Requires sunlight, low H2 rates and yields, requirement
conditions. of large reactor volume, O2 sensitivity, high raw material
cost.
Dark fermentation 60–80 CO2-neutral, simple, can produce H2 without light, contributes to waste Fatty acids removal, low H2 rates and yields, low con-
recycling, no O2 limitation. version efficiency, requirement of large reactor volume.
Photofermentation 0.1 CO2-neutral, contributes to waste recycling, can use different organic Requires sunlight, low H2 rates and yields, low conver-
wastes and wastewaters. sion efficiency, requirement of large reactor volume, O2
sensitivity.
Electrolysis 40–60 No pollution with renewable sources, proven technology, existing in- Low overall efficiency, high capital costs.
frastructure, abundant feedstock, O2 is the only byproduct, contributes
to RES integration as an electricity storage option.
Thermolysis 20–45 Clean and sustainable, abundant feedstock, O2 is the only byproduct. Elements toxicity, corrosive problems, high capital costs.
Photo-electrolysis 0.06 Emission-free, abundant feedstock, O2 is the only byproduct. Requires sunlight, low conversion efficiency, non-effec-
tive photocatalytic material.
concentration whereas the bio-photolysis is considered as CO2- reactors that already exist and possessing acceptable capital cost.
consumed due to the photosynthesis involved during the process. Due to the still low price of natural gas and coal, and the high
In terms of efficiency, dark fermentation could compete with all efficiency they provide as a feedstock, the final hydrogen pro-
methods listed in Table 5, in contrast to bio-photolysis and photo- duction cost from conventional technologies is quite low (o2 $/
fermentation which require sunlight. Regarding the disadvantages, kg). As can be seen in Table 6, the cost per kilogram of H2 produced
the thermochemical processes suffer from the feedstock im- including and without CCS ranges between 1.34 and 2.27 $ (based
purities and its seasonal availability, with the consequent varying on 2005 values) with the lowest corresponding to CG without CCS
H2 content [102,103]. On the other hand, the biological processes process. Further reduction in H2 cost derived from hydrocarbon
provide low rates and yields, requiring larger reactor volume. pyrolysis is expected, if a market for coal purchase would be found.
Consequently, biomass could contribute in large scale generation Utilizing cheaper energy source and feedstock, thermochemical
only through thermochemical pathways of pyrolysis and gasifica- pyrolysis and gasification of biomass are economically viable as
tion, whereas biological processes may be used in small-scales for they provide similar to conventional technologies production
local H2 production or for centralized waste recycling and costs. Biomass pyrolysis and gasification offer viable approaches
treatment. with production costs in the range of 1.25–2.20 $/kg (based on
Water-splitting pathways occur clean and sustainable, produ- 2004 values) of H2 produced. Although algae constitutes one of the
cing only H2 and O2 from one of the most abundant raw materials most expensive feedstocks, biological processes offer production
in the world. Electrolysis is responsible for the emission of CO2 costs around 2 $/kg, assuming very optimistic capital costs for
only when fossil fuels are used to generate the needed electricity. photo-bioreactor of only 50 $/m2 and 135 $/m2 for direct and in-
From renewable energy sources, such as solar and wind, it is able direct bio-photolysis, respectively. According to a recent study
to produce H2 and improve the load factor of a plant, contributing performed in 2014, biochemical dark and photo-fermentation
to the increase of RES integration. According to Table 5, thermo- produce H2 priced between 2.5 and 2.8 $/kg, mainly due to the low
chemical cycles provide a more efficient way of H2 production rates and yields along with the large reactors needed.
with the main limitations being the toxicity of the elements in- High production cost also stems from water-splitting methods,
volved as well as the separation between them. Due to the lack of particularly from those that use solar or wind technology to pro-
effective photo-catalytic materials, photo-electrolysis is the less vide the needed energy. Both the high capital costs and low con-
efficient process (efficiency of only 0.06%). However, comparing all version efficiencies, lead to increased production cost which in
methods based on their primary energy source, solar-based pro- some cases exceeds 20 $/kg and 8 $/kg for electrolysis and ther-
cesses provide the less conversion efficiency. Following the bio- molysis, respectively. With a production cost higher than 10 $/kg
logical methods which operate under mild conditions, water- of H2 and an efficiency as low as 0.06%, photo-electrolysis is by far
splitting methods provide moderate temperatures and conversion the least cost-effective method currently available. In conclusion,
efficiencies when nuclear is the preferred energy source for both according to the data listed in Tables 5 and 6 together with the
water electrolysis and thermochemical water splitting. above discussion relating to the key parameters outlined, carbon
To qualitatively assess the costs derived from each hydrogen taxes imposition directly influence H2 cost. Apart from this and in
production method, variables such as energy source, feedstock and order for the renewable methods to become competitive in terms
capital investment, have been included in Table 6. As byproducts, of cost-effectiveness, the second step should be the further re-
are considered only those that either infect and must be seized, or search in renewable technologies and development of less ex-
can be used from another process to reduce costs. In this context, pensive equipment able to produce H2 in a more efficient way.
the methods which produce H2 from fossil fuels appear dis-
advantageous as the releasing CO2 from reforming process and 5. H2 storage, transportation and utilization
coal produced by hydrocarbon pyrolysis, constitute expensive
procedures requiring energy-intensive steps of CCS to be ad- Aiming to fulfill the goals of security in the energy supply
dressed. As energy source, the conventional fossil fuels require system, environmental protection and economic growth of
P. Nikolaidis, A. Poullikkas / Renewable and Sustainable Energy Reviews 67 (2017) 597–611 609
Table 6
Summary of the different hydrogen production processes.
Process Energy source Feedstock Capital cost (M$) Hydrogen cost [$/kg] Study year dollars
SMR with CCS Standard fossil fuels Natural Gas 226.4 2.27 2005
SMR without CCS Standard fossil fuels Natural Gas 180.7 2.08 2005
CG with CCS Standard fossil fuels Coal 545.6 1.63 2005
CG without CCS Standard fossil fuels Coal 435.9 1.34 2005
ATR of methane with CCS Standard fossil fuels Natural Gas 183.8a 1.48 2005
Methane Pyrolysis Internally generated steam Natural Gas – 1.59–1.70 1992
Biomass Pyrolysis Internally generated steam Woody Biomass 53.4–3.1b 1.25–2.20 2004
Biomass Gasification Internally generated steam Woody Biomass 149.3–6.4c 1.77–2.05 2004
Direct Bio-photolysis Solar Waterþ Algae 50 $/m2 2.13 2002
Indirect Bio-photolysis Solar Waterþ Algae 135 $/m2 1.42 2002
Dark Fermentation - Organic Biomass – 2.57 2014
Photo-Fermentation Solar Organic Biomass – 2.83 2014
Solar PV Electrolysis Solar Water 12–54.5 5.78–23.27 2007
Solar Thermal Electrolysis Solar Water 421–22.1d 5.10–10.49 2007
Wind Electrolysis Wind Water 504.8–499.6e 5.89–6.03 2005
Nuclear Electrolysis Nuclear Water – 4.15–7.00 2006
Nuclear Thermolysis Nuclear Water 39.6–2107.6f 2.17–2.63 2007
Solar Thermolysis Solar Water 5.7–16g 7.98–8.40 2007
Photo-electrolysis Solar Water – 10.36 2014
a
Based on a 600 MWH2 power plant with a capital cost of 306.35 $/kWH2.
b
The capital cost of 53.4 M$ corresponds to a plant capacity of 72.9 tn/day, 3.1 M$ is referred to a 2.7 tn/day plant output.
c
The capital cost of 149.3 M$ corresponds to a plant capacity of 139.7 tn/day, 6.4 M$ is referred to a 2tn/day plant output.
d
The capital cost of 421 M$ is referred to a power-tower electrolysis plant and 38.4 tn/day of H2, 22.1 M$ corresponds to stirling-dish technology and 1.4 tn/day.
e
The cost of 504.8 M$ assumes the coproduction of electricity along with hydrogen whereas, 499.6 M$ represents the cost of only hydrogen production.
f
The capital cost of 39.6 M$ corresponds to a Cu-Cl plant capacity of 7 tn/day, 2107.6 M$ is referred to a 583 tn/day S-I plant output.
g
The capital cost of 5.7 M$ corresponds to a plant capacity of 1.2 tn/day, 16 M$ is referred to a 6 tn/day plant output.
societies, the introduction of produced H2 as a fuel and energy metals such as Li, Be, Na, Mg, B, and Al, form a large variety of
carrier presents, beyond the undisputed advantages, several pro- metal-hydrogen compounds while a high volumetric density of
blems in developing the required technologies for storage, trans- 150 kg/m3 at ambient temperature and pressure has been
mission and utilization [23]. achieved in Al(BH4)3 [96]. However, the gravimetric density is
At ambient temperature and atmospheric pressure, 1 kg of H2 limited to less than 3 wt% and therefore, intense interest has been
gas occupies a volume of 11 m3. With such a low density of developed in even lighter metals, complex hydrides. Complex
0.09 kg/m3, H2 storage has become one of the key barriers re- hydrides open a new field of hydrogen storage materials, provid-
stricting its wide spread use [95]. The main storage methods en- ing gravimetric densities of up to 18 wt% for LiBH4 [98]. The main
able hydrogen to be stored physically as a gas or liquid, and on the characteristics of the five basic methods which enable reversible
surfaces or within the solids by adsorption and absorption, hydrogen storage are listed in Table 7.
respectively. There are two possible modes for H2 transportation and dis-
High pressure gaseous hydrogen storage is currently the most tribution. The first category regards the bulk transportation sto-
common and mature method, achieving high pressures of up to rage vessel, truck trailers, railway tank cars and containers, while
77 MPa using standard piston-type mechanical compressors [96]. the second includes the pipelines [99]. The low carrying capacity
However, the work needed for the compression is much higher along with the lack of capability to handle H2 through the con-
than 2.21kWh/kg, providing a gravimetric and volumetric density ventional means of first category, results in high delivery costs
of 13 wt% and lower than 40 kg/m3, respectively [97]. Liquid hy- [96]. The future H2 transport and distribution system might look
drogen can be stored in cryogenic tanks through a double-step like current natural gas pipelines and could be envisaged as part of
procedure of compression and cooling in a heat exchanger. Be-
a system of networks, including electricity and natural gas [100].
cause of its low boiling point of 252.87 °C, the work needed is
Consequently, significant innovations are needed as the transport
estimated to 15.2 kWh/kg, achieving 70.8 kg/m3 volumetric den-
losses of methane and electricity over large distances are fairly
sity at atmospheric pressure, while the gravimetric density de-
equal at 5–7%, whereas using the same pipelines for H2 could in-
pends on the tank size. Even with the perfect insulation, the daily
crease to 20% [101].
boil-off losses of releasing H2 into the atmosphere are typically
Beside its use in the chemical and oil industries, H2 can be used
rated at 0.4%, 0.2% and 0.06% for storage volumes of 50 m3, 100 m3
in internal combustion engines, fuel cells, turbines, cookers and
and 20,000 m3, respectively [96].
Solid-state storage occurs more effective at storing large
Table 7
amounts of hydrogen at moderate temperature and pressure. In a The basic hydrogen storage methods.
process of adsorption, a gas molecule interacts with several atoms
at the surface of a solid where it is bonded and reversibly released Storage method ρm (wt%) ρv T (°C) P (MPa)
when needed. Carbon nanotubes are able to store H2 at quite low (kg/m3)
temperatures ( 196.15 °C) and pressures (6 MPa), providing a High pressure gaseous H2 13 40 ambient 77
gravimetric and volumetric density of 10.8 wt% and 41 kg/m3, re- Cryogenic liquid – 70.8 252.87 atmospheric
spectively [97]. The low pressure and cost of the materials in- Adsorbed on carbon nanotubes 10.8 41 196.15 6
volved are key advantages over the quite low temperatures nee- Absorbed to form hydrides 3 150 ambient atmospheric
Absorbed to form complex 18 150 4100 atmospheric
ded. Alternatively, H2 can react at elevated temperatures with
hydrides
many transition metals and their alloys to form hydrides. Light
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