i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 3 9 8 8 e2 3 9 9 5

Available online at www.sciencedirect.com

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Commentary

There are hydrogen production pathways with

better than green hydrogen economic and
environmental costs

Alberto Boretti
Deanship of Research, Prince Mohammad Bin Fahd University, Al Khobar, Saudi Arabia

article info abstract

Article history: While the present hydrogen (H2) is mostly grey, from steam reforming of methane (CH4)
Received 15 April 2021 with direct carbon dioxide (CO2) emission, different pathways have been proposed to
Accepted 25 April 2021 produce H2 more environmentally friendly. Blue H2, adopting carbon capture and storage
Available online 19 May 2021 (CCS), has no direct CO2 emission, but the additional cost to capture and store the CO2.
Thus, green H2, from the electrolysis of the water (H2O) molecule, is becoming the pref-
Keywords: erential pathway for future H2 production. Two additional pathways are proposed for
Hydrogen reduced economic and environmental costs, both free of direct CO2 emissions, based on
Thermochemical splitting the use of concentrated solar energy (CSE). White H2 is produced from the catalytic solar
Water thermochemical splitting of the H2O molecule. Aquamarine H2 is produced from solar
Methane thermochemical CH4 pyrolysis with a carbon catalyst. Here we provide an estimation of
Carbon black costs by 2030 of white and aquamarine H2 lower than the cost of not only green H2 but also
Oxygen grey H2 disregarding the CO2 emission.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

such as methane (CH4) without any direct emission of CO2 or

Direct CO2 emission-free hydrogen production
pathways
Hydrogen is the most common element in the universe (about
75% of all the matter is hydrogen). Molecular hydrogen (H2) is
considered the future fuel, producing water (H2O) when
oxidized, and not carbon dioxide (CO2) as is the case with
carbon and hydrocarbon fuels. In the hydrogen economy
[1e4], most of the energy needs will be covered by H2, with
electricity to cover the rest. One major hurdle towards the
hydrogen economy is the availability of H2 that is freely
available in nature only to a negligible extent. Thus, it must be
produced from feedstocks of molecules containing hydrogens
H2O.
Not all H2 is created equal.
While the present H2 is mostly grey, from steam reforming
of CH4 with direct CO2 emission, different pathways have been
proposed to produce H2 more environmentally friendly.
Grey H2 has a direct CO2 emission of 8 kg of CO2 per kg of
H2, an economic cost of 1.25 $/kg of H2 at 3 $ per thousand
cubic feet of natural gas, and a minimum energy cost of 62 kJ/
mol of H2 [5].
Blue H2, adopting carbon capture and storage (CCS), has no
direct CO2 emission, but the additional cost to capture and
store the CO2 [5].

E-mail address: deanshipofresearch@pmu.edu.sa.

https://doi.org/10.1016/j.ijhydene.2021.04.182
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 3 9 8 8 e2 3 9 9 5
Thus, green H2 [6], from the electrolysis of the H2O mole-
cule, is becoming the preferential pathway for future H2 pro-
duction. Green hydrogen has a minimum energy cost of 286
kJ/mol of H2. Significant research and development (R&D) are
undertaken to reduce the present costs by improving the
technology. There is no direct CO2 emission. Oxygen (O2) is a
by-product. Projection of costs is on average not less than 2
$/kg H2 by 2030, even if there are forecasts of 1.5 $/kg H2 but in
the hypothesis of much better and less expensive electro-
lyzers and a levelised cost of electricity (LCOE) of $20/MWh.
In a hydrogen color palette where lighter colors represent
more environmentally friendly solutions, there are also better
than green colors of hydrogen, and we associate to them the
color “aquamarine” (a light blue-green), to represent a further
evolution of the blue H2, with no need for CO2 capture and
storage, and driven by concentrated solar energy (CSE), and
finally “white”, where the splitting of the H2O molecule is
thermochemical without any intermediate step.
Here we propose these two additional pathways for further
reduced economic and environmental costs, both free of
direct CO2 emissions, based on the use of concentrated solar
energy. Oxygen (O2) is the by-product in the white H2, carbon
black is the by-product in the aquamarine H2.
Concentrating solar power (CSP) is emerging as a signifi-
cant producer of renewable energy with the added value of
dispatchability, and thanks to the thermal energy storage
(TES) and the higher temperature developments [7], there are
synergies with CSE for process heath. While advanced ultra-
supercritical (AUSC) steam Rankine power cycles have been
proposed for temperatures up to 730
C [8e15], supercritical
CO2 Brayton power cycles have been proposed for even higher
temperatures above 800
C [16e20]. For small installations,
Stirling engines are also being considered [21e23], with tem-
peratures up to 850e900
C.
Point solar concentrators such as beam down [21,22], or
even more traditional central receiver solar towers sur-
rounded by a field of heliostats [24] have already delivered
temperatures of the heat transfer fluid (HTF) at the receiver
above 1000
C. Molten salts formulations are being developed
to work well above the 1000
C [25e28]. Thus, there is the
opportunity to use constant, high-temperature CSE to drive
thermal processes for the production of H2.
The two proposed new colors of hydrogen are becoming
more and more relevant. Both are benefiting from synergies
with CSE and based on thermochemical pathways from two
different feedstocks, H2O or CH4, in presence of a catalyst.
Table 1 e Summary of grey, blue, green, aquamarine, and white hydrogen pathways.
H2 color Process
grey steam reforming
blue steam reforming þ CCS
green electrolysis
white solar thermochemical water splitting
aquamarine solar thermal pyrolysis with C catalyst
23989
They are in perspective competitive with the current grey, as
well as the proposed blue and green H2.
Thermal production of hydrogen has advantages vs. elec-
trolysis. If the electricity is provided by solar photovoltaic, this
energy is only ~15% of the solar energy received. Then, the
efficiency of the electrolyzer, hydrogen fuel energy flow out to
electric power input,
m_ H2 ,HHVH2
h¼
Pe
is much less than 80%. This means that less than 12% of the
solar energy received ends up in hydrogen fuel energy. Addi-
tionally, it is not logical to transform solar energy into an
energy carrier, electricity, to be transformed into another en-
ergy carrier, hydrogen, to be transformed again into electricity
in fuel cells, with a further penalty in every conversion (the
additional hydrogen fuel to electricity conversion efficiency in
fuel cells is below 60%). A much better approach is to use CSE
to split the water molecule through a thermochemical water-
splitting cycle. In this case, ~90% of the solar energy received
can be converted to high-temperature thermal energy. As the
efficiency of thermochemical H2O splitting, hydrogen fuel
energy flow out to thermal power input,
m_ H2 ,HHVH2
h¼
Pt
was potentially above 50% already more than a decade ago,
roughly 45% of solar energy can be transformed into hydrogen
fuel energy. The reaction for thermal production of hydrogen
and electrolysis is nominally the same, with the same mini-
mal energy requirement. If with electric energy it has been
possible to achieve efficiencies above 70%, it is reasonable to
assume efficiencies above 50% with thermal energy at the cost
of an affordable R&D.
Different thermochemical pathways have been proposed
for white H2 [29e41], by using different cycles and catalysts, in
different temperature ranges. Because of the availability now
of constant CSE at about 1000
C downstream of the thermal
energy storage (TES), 3-step cycles developed for nuclear
thermal energy before the Fukushima Daiichi nuclear disaster
of 2011, offer the best prospects [39e41].
In the case of areas such as the Eastern Province of the
Kingdom of Saudi Arabia where natural gas is possibly not less
abundant than freshwater, aquamarine H2 produced from
solar thermal CH4 pyrolysis with carbon as a catalyst has also
great merits.
Formula Direct CO2 emission Minimum Co-product
kg/kg H2 energy demand
kJ/mol H2
CH4þ2$H2O/ 8.85 41(62)
4$H2þCO2
CH4þ2$H2O/ 0 41(62)þCCS CO2
4$H2þCO2
2$H2O/2$H2þO2 0 286 O2
2$H2O/2$H2þO2 0 286 O2
CH4/2$H2þC 0 37 carbon
black
23990 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 3 9 8 8 e2 3 9 9 5

Fig. 1 e Prototype small high-temperature solar concentrator with thermal energy storage, and downstream power cycle (a)
or thermochemical hydrogen production block (b) or (c). (a) Concentrated solar energy with thermal energy storage. (b) White
hydrogen from catalytic solar thermochemical water splitting 2 H2O/2·H2þO2. (c) Aquamarine hydrogen from solar thermal
pyrolysis with C catalyst CH4/2·H2þC.
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23992 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 3 9 8 8 e2 3 9 9 5

Splitting of the CH4 molecule in presence of a catalyst has
been proposed by using different methods, and in the case of
catalytic thermal methods, different cycles and catalysts, in
different temperature ranges, have been designed [42e59].
The use of carbon as a catalyst is the solution offering the best
outlook, having a low energy requirement, working well at
affordable temperatures about 1000
C, and having as by-
product carbon black [49e52]. While the market for carbon
black is not expected to be very profitable, there is no doubt
that carbon particles may find much better uses than CO2.
Aquamarine H2 is better produced from solar thermochemical
pyrolysis in a moving carbon bed at temperatures of 1000
C.
Table 1 presents a summary of grey, blue, green, aqua-
marine, and white H2 pathways, while Fig. 1 presents schemes
prototype small high-temperature solar concentrator beam
down with thermal energy storage, and downstream power
cycle (a) or thermochemical hydrogen production block, (b)
and (c). (b) is the white H2 from solar thermochemical water
splitting 2$H2O/2$H2þO2 and (c) aquamarine H2 from solar
thermal pyrolysis with C catalyst CH4/2$H2þC. Small-scale
demonstration plants are essential to quickly develop new
technologies before attempting the design of large-scale
plants. What is needed for the further progress of the
hydrogen economy is to invest in new products, more than
trying to benefit from the sale of existing products, with unfair
competition from established renewable energy businesses
the major hurdle.
The backup heater (HTR) may burn natural gas in air or O2,
or even recycled carbon black in O2, and have the CO2
captured for storage. The HTR may also run on hydrogen. The
HTR is used to address the unlikely occurrence of having no
sunlight for several consecutive days. The fuel energy to
thermal energy efficiency can be more than 95% for the HTR,
with penalties from the capture of the CO2, and advantages
from combustion in O2.
The HTR may also be used more extensively to make
perfectly constant the supply of thermal energy to the ther-
mochemical hydrogen production block over the year, further
accommodating changes in solar irradiance and cloud
coverage, at relatively modest additional costs.
This design can be further complicated, for example add-
ing an electric heater to store excess renewable energy elec-
tricity in the form of thermal energy, similarly to the Azelio
“thermal battery” [60,61].
As there is waste energy from the Stirling engine, or an
alternative supercritical CO2 Brayton cycle, as well as from the
thermochemical hydrogen production block, well above
ambient temperature, it is possible to use this thermal energy
for other uses such as running a chiller or producing hot water
thus improving the global thermodynamic.
Cost estimations have been made for white and aquamarine
H2 by considering a central tower receiver surrounded by a field
of heliostats to deliver a constant 269 MW of thermal power to
the thermochemical plant. The location is Al Khobar, Eastern
Province, Kingdom of Saudi Arabia. The heliostat fields are made
up of 16,000 12.2∙12.2 m2 units. The tower has 200 m in height.
The receiver has a 20.66 m height and 17.04 m diameter. The
thermal storage is 16h or 4304 MWh. The heat transfer/heat
storage fluid is MgCl2/KCl [7]. Simulations are performed by
using NREL SAM [62]. Weather and solar irradiance data are from
climate.onebuilding.org [63]. Fig. 2 presents the operation of this
plant in the case of the temperature of the hot TES 950
C. The
cold TES is 590
C, as needed for white H2 production.
The costs in 2030 of the components upstream of the
thermochemical plant, factoring the expected 46% reduction
of costs from 2021 to 2030 in the LCOE from CSP [62,64], is
estimated at $ 402, 941, 490. This includes site improvement,
heliostats field, tower, receiver, TES.
Presently still at TRL 6 (technology demonstration), as not
that much has been done since 2011, this thermochemical
technology necessitates further R&D. Cost estimations are
difficult. We may assume $ 100, 000, 000 to $ 200, 000, 000 as
the cost of the thermochemical plant in 2030 for the SeI 3-step
thermochemical cycle to produce H2.
By assuming (hydrogen fuel HHV 286 kJ/mol or 141.80 MJ/
kg) a peak h of 52% at 925
C, which is about 1.92 times the
minimum energy requirement, we have an average hydrogen
fuel power of 114 MW. If we consider a lifespan of 30 years as
customary for CSP, we have a total hydrogen fuel energy
production of 30,180 GWh.
By assuming the same as CSP Fixed and Variable operation
and maintenance (O&M) costs related to thermal power, Fixed
O&M costs are $ 151, 200, 000, while Variable O&M costs are $
108, 648, 000.
Total cost 2030e2059 is therefore $ 762, 789, 490 to $ 862,
789, 490, for producing 766, 205, 924 kg of white H2 for a cost of
0.9955e1.1261 $/kg H2.
This estimation excludes the cost of water, but also the
recovery of the waste heat, and O2 as a by-product.
The cost of the aquamarine H2 can be estimated following
the same approach. We neglect the effect of the slightly larger
hot TES temperature, 1025 vs. 950
C, on the cost of the sec-
tions upstream of the thermochemical plant, but we account
for this temperature change in the slightly reduced perfor-
mance of the plant.
By taking the efficiency of this thermochemical plant pro-
portional to the efficiency of the thermochemical plant for the
splitting of the water molecule, with proportionality factor the
ratio of minimum energy requirements, we get a peak h of 52%
∙ (286/37) at 1000
C. This efficiency that is now largely
exceeding unity (the energy of the methane feedstock is not
included in the formula) is still 1.92 times the minimum en-
ergy requirement.
The average hydrogen fuel power is now a much larger
114∙ (286/37) MW. Over a lifespan of 30 years, the produced
hydrogen fuel energy is 29,772∙ (286/37) GWh.

Fig. 2 e Operation of a central tower received surrounded by a field of heliostats. (a) power collected in the receiver (blue) and
to (red) or from (green) the thermal energy storage. (b) power to the thermochemical plant (green) and temperature (black).
Design thermal power to thermochemical plant 269 MW. Design temperature hot thermal storage 950
C. The location for
weather and irradiance is Al Khobar, Eastern Province, Kingdom of Saudi Arabia. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 3 9 8 8 e2 3 9 9 5
By estimating the cost of the upstream sections in 2030 at $
402, 941, 490 and assuming $ 100,000,000 to $ 200,000,000 as
the cost of the thermochemical plant in 2030 for the thermo-
chemical CH4 splitting with a carbon catalyst to produce
hydrogen, Fixed O&M costs of $ 151, 200, 000 and Variable
O&M costs of $ 108,648,000, the Total cost 2030e2059 is $
762,789, 490 to $ 862,789,490 for 755,838,533∙ (286/37) kg of H2.
This cost is therefore 0.1306 to 0.1477 $/kg H2.
The cost of methane has to be added to this cost. If we
consider the cost of natural gas over this century for the
United States [65], the price has been reducing since the year
2000, down to prices in 2020 oscillating from 2.55 to 4.07 $ per
thousand cubic feet. By assuming a price of 3 $ per thousand
cubic feet over the years 2030e2059, the methane cost is thus
4∙0.1613 ¼ 0.6450 $/kg H2, bringing the total cost at 0.7756 to
0.7927 $/kg H2. This cost excludes purification of natural gas,
waste heat recovery, and use of carbon black.
At the same 3 $ per thousand cubic feet of natural gas,
Aquamarine H2 is thus projected to cost ~36e38% less than the
grey H2 even disregarding the cost of the CO2 emission. White
H2 may similarly cost ~10e20% less than the grey H2 not
factoring in any penalty for the CO2 emission. Green H2 has
much higher costs, more than double.
The minimum energy cost of Aquamarine H2 is only 37 kJ/
moll of H2, much less not only of cost for splitting the H2O
molecule but also less than the minimum energy cost of
steam reforming of CH4 without CCS, plays in favor of this
color of hydrogen. On the dark side, the price of natural gas
may easily grow well above the predicted value. Every addi-
tional $ per thousand cubic feet impacts 0.215 $ on the price
per kg of H2. This may give an advantage to the White H2.
Presently at TRL 4 (technology development), aquamarine
H2 certainly needs more R&D than every other environmen-
tally friendly H2, blue, green, or white. Carbon black as a by-
product may have a commercial value. The relative advan-
tage of aquamarine H2 will ultimately depend on the price of
the natural gas.
Conclusions
Green H2 makes sense given current commercial renewable
energy products, photovoltaic solar panels for intermittent
and unpredictable renewable electricity generation, and
electrolyzers. However, it suffers from the fundamental sus-
tainability flaws of too many energy conversions. The pro-
posed pathways, white H2, and aquamarine H2 have better
perspectives. White H2, made by solar catalytic thermo-
chemical water splitting with concentrated solar energy, and
aquamarine H2, made by CH4 solar thermal pyrolysis in
presence of a carbon catalyst, have potentially better eco-
nomic and environmental costs compared to green H₂. These
two pathways have the promise to become the more sus-
tainable producers of the carbon-free fuel of the near future.
Notes
Views expressed in this Perspective are those of the author.
The author declares no competing financial interest.
23993
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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