Energy Conversion and Management 122 (2016) 400–410

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Thermodynamic assessment of CO2 to carbon nanofiber transformation

for carbon sequestration in a combined cycle gas or a coal power plant
Jason Lau a, Gangotri Dey b, Stuart Licht a,⇑
a
Department of Chemistry, The George Washington University, Washington, D.C. 20052, United States
b
Institute for Massively Parallel Applications and Computing Technology (IMPACT), The George Washington University, Washington, D.C. 20052, United States

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

Article history: Molten carbonate electrolyzers offer a pathway to capture emitted CO2 from the flue gas of the power
Received 10 April 2016 plants and transform this greenhouse gas emission at low energy and high yield instead into a specific,
Received in revised form 1 June 2016 value added, hollow carbon nanofiber product, carbon nanotubes. The present day value of the carbon
Accepted 3 June 2016
nanotubes product is
10,000 that of proposed, or in place, current carbon tax costs of $30 per ton,
strongly incentivizing carbon dioxide removal. The recent progress in high-temperature molten carbon-
ate electrolysis systems for carbon dioxide utilization and the impact these advances have on developing
Keywords:
a CO2-free fossil fuel power plant for electricity generation is presented. A thermodynamic model analysis
Carbon nanofibers
CO2 utilization
is presented for a molten Li2CO3 electrolysis system incorporated within a combined cycle (CC) natural
Molten carbonates gas power plant to produce carbon nanofibers (CNF) and oxygen. Such a CC CNF plant system is shown
Thermodynamic analysis to require 219 kJ to convert one mole of CO2 to carbon, and generates electricity at higher efficiency due
Solar thermal electrochemical process to pure oxygen looped back to the gas turbine input from the CO2 splitting, with the added advantages
CO2 sequestration that (i) the CC CNF plant emits no CO2 and (ii) all CO2 is converted to value added carbon nanotubes useful
for strong, lightweight construction, batteries and nanoelectronics. Converting to power and ton units,
per metric ton of methane fuel consumed the CC CNF plant is thermodynamically assessed to produce
8350 kW h of electricity and 0.75 ton of CNT and emits no CO2, while the CC plant produces
9090 kW h of electricity and emits 2.74 ton CO2. The required energy balance for a carbon nanotube pro-
duction from an analogous coal power plant consumes a larger fraction of the coal energy, and encour-
ages co-generation with renewable electric energy.
Ó 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction to these power plants if CO2 concentration in the atmosphere is

decreased.
In 2014, the United States produced 5209 million metric tons of A promising technology for carbon dioxide transformation is
CO2 from fossil fuel combustion. Fossil fuel combustion is the sin- the electrolytic synthesis of carbon and carbon nanofibers (CNF)
gle largest source of greenhouse gas emissions in the United States, from captured carbon dioxide in molten lithium carbonate [2–9].
and this accounts for more than the rest of the sources combined In this process, voltage is applied to split carbon dioxide in an
[1a]. The largest fraction of this fossil fuel combustion is for electrolysis chamber on a nickel anode and a galvanized steel
electricity generation at stationary power plants. If these power cathode into pure oxygen gas and a solid carbon product. A low
plants are allowed to continue to operate as they have done in energy, high efficiency process when conducted in lithiated molten
the past, the amount of CO2 in the atmosphere will continue to carbonate electrolytes, this electrolysis reaction offers a pathway
increase, driving ongoing climate change around the world. In to transform the greenhouse gas into a high value commodity
2013 the renewable energy share of power generation is 22% [2–10]. The carbonate electrolyte is not consumed and the net
[1b]. Any carbon based fuel sources will produce CO2 during reaction is CO2 splitting into carbon and O2, and as presented here
their combustion, which means that a carbon dioxide using pure Li2CO3 as the carbonate electrolyte:
sequestration and/or transformation technology must be added
Dissolution : CO2 ðgasÞ þ Li2 OðsolubleÞ ! Li2 CO3 ðmoltenÞ

Electrolysis : Li2 CO3 ðmoltenÞ ! CðsolidÞ þ Li2 O ðsolubleÞ

⇑ Corresponding author. þ O2 ðgasÞ
E-mail address: [email protected] (S. Licht).

http://dx.doi.org/10.1016/j.enconman.2016.06.007
0196-8904/Ó 2016 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410 401

Net : CO2 ðgasÞ ! CðsolidÞ þ O2 ðgasÞ ð1Þ One of the principal global emission sources of the greenhouse
gas carbon dioxide is from electrical power plants fueled by fossil
As shown in Fig. 1, CO2 directly from the atmosphere or the CO2
fuels. Presently, the most efficient of these plants in widespread
emission from a combined cycle (CC) natural gas power plant is
use are combined cycle natural gas plants, which nevertheless emit
electrolyzed to produce a variety of value carbon nanomaterials
massive amounts of CO2. Fig. 2 presents the energy distribution of
that have a range of uses. The morphology of the carbon product
a conventional combined cycle power plant [12]. It is evident that
can vary based on diffusions controls of natural abundance CO2
there are several major energy efficiency losses. Recognition of
or C13 (Fig. 1(b) and (c)). High concentrations of lithium oxide
these losses offer opportunities for improvement and for rerouting
can produce a tangled morphology (Fig. 1(d)), while no additional
those energies to simultaneous sequestration, or transformation of
concentration of lithium oxide produces straight nanotubes
CO2. For example, when a CO2 to CNF electrolyzer is added to a CC
(Fig. 1(f)) [2]. The use natural abundance CO2, electrolysis current
power plant, pure oxygen is generated, which can be used to enrich
control and the addition of small quantities of nickel to act as
the oxygen content of the air used for combustion. Enriched oxy-
nucleating agents leads to high yield of a particularly valuable form
gen combustion allows for the combustion chamber to reach
of hollow carbon nanofibers, carbon nanotubes. Due to their supe-
higher temperatures and combustion efficiencies, improving ther-
rior strength, conductivity, flexibility, and durability CNFs have a
mal energy efficiencies of the gas turbine as well as the steam tur-
variety of applications including in nanoelectronics, in Li-ion bat-
bine. Additionally, the system decreases stack heat losses based on
teries, as a material for solar thermal conversion [11], and as a
the diminished volume of N2 in the combustion process compared
principal component in the light-weighting of infrastructure
to conventional CC power plants. The electrolyzer can form a high
construction materials, transportation (air, land, sea) vehicles, con-
yield of a specific form of carbon nanofiber, carbon nanotubes.
sumer electronics, wind turbine blades, and athletic equipment.
Carbon nanotubes (90% industrial grade) are currently valued at

Fig. 1. Scheme for the electrolytic synthesis of carbon nanostructures: (a) source of CO2 as dissolved air or smoke stack concentrations of CO2, (b and c) demonstrate diffusion
controls on formation of carbon nanotubes or nanofibers, high oxide concentration produce tangled morphogies (d) while low concentrations produce straight nanotubes (f),
and (e) nickel nucleation sites, the bright spots, as identified by EDS. Lower panel: The carbon nanofiber and nanotubes provide high conductivity and superior carbon
composite lightweight structural materials for jets, bridges, wind turbines, and electric vehicle bodies and batteries.
402 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410

Fig. 3. Theoretical energy of CNT formation with adsorbed Ni or Zn cluster [9].

Fig. 2. Diagram of energy distribution in a conventional CC power plant reprinted
with permission from Beér [12]. Copyright Elsevier Ltd. 2006.
significant incentive for CO2 removal, while providing an impetus
for CNF and CNT market growth through a decrease in cost. This
study will explore the thermodynamic feasibility of transforming

$300,000 per ton [12]. This value is 10,000 times the estimated
the exhaust CO2 from a combined-cycle natural gas power plant
current cost of carbon tax credits [13].
into a stable, valuable carbon nanofiber product using a lithiated
The cost of STEP (Solar Thermal Electrochemical Process) carbon
carbonate high temperature electrolysis system.
nanofibers and carbon nanotubes produced by molten carbonate
electrolysis can be estimated with a generic electric supply, and
does not include the additional efficiency advantages of the previ- 2. Systems description
ous solar thermal and solar electric supply [2–10,14–16]. Electrol-
ysis costs to produce CNFs, or CNTs, will be similar to 2.1. Conventional combined cycle gas turbine power plant
infrastructure costs associated with chlor-alkali and aluminum
industries, which are the major traditional electrochemical indus- Advanced gas turbine technology stands at the forefront of fos-
tries. The electrical energy costs are low, requiring 0.9–1.4 V, with sil fuel electricity generation as a result of its high efficiency, fast
a high columbic efficiency of 80–100% for the four electrons load-response times, and abundance of fuel (methane). A com-
required to reduce CO2 to CNF or CNT [3]. The energy requirements bined cycle gas turbine power plant utilizes two heat engine forms
for carbon nanotube growth with various nucleation metals has to convert heat energy into mechanical energy, which is then
been explored using first principal Density Functional Theory using transformed into electrical energy. An example of a conventional
quantum espresso packaged with a generalized gradient approxi- combined cycle plant, that utilizes a Brayton combustion cycle sys-
mation with Predew-Burke-Ernzerhof exchange-correlation func- tem to convert heat to mechanical energy, followed by a second
tional using PAW pseudopotentials to identify the most energy steam turbine that uses a Rankine cycle system to convert the
efficient pathway for CNT growth, shown in Fig. 3 [9,17]. A CNT residual heat to mechanical energy, is shown in Fig. 4. While the
adsorbed onto a Ni cluster has the lowest energy state as a result basic scheme of the plant remains the same, the fuel to electrical
of the strong metal-carbon adhesion bonds formed, while Zn has efficiency vary between 50 and 60% with newer plants incorporat-
the highest energy state. A mixture of Ni/Zn metal cluster was ing more efficient technologies [19–23]. These efficiencies can be
found to have the optimized energy per atom ratio required for further improved with new turbine technologies and higher com-
proper carbon nanotube growth [9]. Energy minimization for the bustion efficiencies. In a conventional, contemporary CC gas power
growth of CNT on Ni/Zn cluster, as opposed to Zn alone is pre- plant,
38% and
21% of the available fuel enthalpy are converted
sented in Ref. [9]. to electricity respectively by the gas combustion and steam tur-
Using an electricity cost of $0.10 per kW h, the electrosynthesis bines, for a combined enthalpy to electricity efficiency of
59%;
of CO2 to CNF suggests an equivalent $800 to $1600 per metric ton heat is lost in the steam condenser (
30%), stack (
10%), and
CNF. Lithium carbonate is not consumed during the CO2 electroly- through radiative losses (
1%) [5]. Typical pipeline quality natural
sis and at today’s costs of $6000 per ton, as amortized over ten gas is
93% Methane (CH4),
3% Ethane (C2H6), 0.7% Propane
year’s usage, the electrolyte adds an additional $140 per metric (C3H8),0.4% n-Butane (C4H10),
1% Carbon dioxide (CO2), and
ton of CNF. An alternative less expensive mix of sodium and
1–2% Nitrogen (N2) [24,25]. The natural gas mixture burned at
lithium carbonate is also an effective electrolyte [8]. Additional these plants can vary based on the specific source of natural gas
costs such as nickel and steel electrodes and ancillary equipment used as well as the specific requirements of the power plant.
is low due to the low wear on the system, and is expected to add
a combined upper limit cost of $2000 per metric ton of CNF. These 2.2. Carbon nanofiber combined cycle power plant
costs compared to today’s conventional chemical vapor deposition
or electrospun production costs of
$25,000 per ton of CNF and A conventional CC power plant, offers synergistic opportunities
$200,000–400,000 per metric ton of industrial grade (90% purity) for efficient CO2 mitigation in conjunction with an added high tem-
CNTs [4,18]. The low costs of C2CNT (carbon dioxide to carbon nan- perature electrolysis component to split CO2. A CC power plant
otube) production opens high revenue windows and provides a generates a source of hot CO2 that can be sparged directly into a
 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410 403

Fig. 4. Schematic of a conventional combined cycle power plant which utilizes a gas turbine to convert heat to mechanical energy, followed by a second steam turbine to
convert the residual heat to mechanical energy [26].

molten carbonate electrolyte, rather than emitted into the atmo- The configuration of a CNF CC power plant can utilize the pure
sphere as a greenhouse gas. This CO2 can then be electrolyzed into oxygen produced by the electrolysis, the anodic product of the car-
carbon nanofibers, while remaining other flue gas products, such as bon dioxide splitting, to improve the efficiency of the combustion
nitrogen and steam are insoluble in the molten electrolyte, and can include happen for a variety of reasons, ranging from a decrease
be passed through a heat exchanger to create the steam that will in partial combustion as more oxidant is present, the reduction
be used for the second part of the combined cycle. This carbon of NOx present as less nitrogen is available, and the higher temper-
nanofiber combined cycle (CNF CC) power plant is illustrated in atures reached which allow for improved thermodynamic effi-
Fig. 5. The CNF-CC plant adds an electrolysis chamber absorbing ciency [35–40]. This transition to an oxy-fuel combustion process
hot CO2 from the gas turbine exhaust, which is converted to carbon reduces the impurities in the exhaust gas, which will prevent side
nanofibers and pure O2. The pure oxygen produced through elec- reaction from occurring in the electrolysis chamber. An enhanced
trolysis is cycled back to the combustion chamber to improve effi- temperature will allow for a decrease in the electrolysis potential
ciency, while the recovered heat is passed on to the steam turbine for the electrosynthesis of carbon nanofibers as previously
and the entire process produce valuable carbon nanofiber instead reported, allowing for additional temperature benefits [2–9]. This
of releasing CO2. The carbon nanofibers are easily recovered and increased temperature can impose additional material require-
are more valuable than carbon dioxide. A benefit of this system ments, but has been successful in CC plants utilizing (expensive)
is the ability for the carbon dioxide to be captured without precon- cryogenically isolated pure oxygen as the combustion feed gas,
centration, and sequestered and transformed at high temperature. and an optimization study will need to be performed to ensure
Conventional absorption CCS technologies require an absorption the proper mixture of oxygen and air is used to ensure maximum
material that captures the CO2 at a lower temperature and must performance with cost-effective materials.
be heated to release the CO2 and regenerate the material. A molten In order to demonstrate the synergy of a CNF CC power plant in
carbonate electrolyte can utilize metal oxides such as lithium, comparison to alternative carbon sequestration technology, we
sodium, potassium, calcium, or barium oxide to chemically react will be the CNF CC power plant using thermodynamic calculations.
with CO2 to form a carbonate. This carbonate is than electrolyzed This assessment will compare the energy production of a typical CC
to produce a net reaction shown in Eq. (1). power plant burning pure methane with no sequestration, with
The advantage of using an oxide CO2 absorber is that both the conventional carbon capture sequestration, and with carbon nano-
oxide as well as the CO2 are able to be kept at high temperature, fiber production. Using thermodynamic calculations based on the
preventing the need for thermal cycling as commonly performed fundamental characteristics of the materials involved, the energy
with ionic liquid, amines, and other CCS technologies [27–34]. costs of the electrolysis reaction will be analyzed, while exploring
404 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410

Fig. 5. Schematic of a proposed carbon nanofiber combined cycle power plant [26].

the energy advantages as a result of the coupling with a combined using mixed sodium or potassium carbonates have been found to
cycle power plant. have a lower melting point that pure Li2CO3, however, we have
observed that they are more corrosive to the oxygen anode,
3. Thermodynamic analysis of a CNF CC power plant energy although mixed electrolytes can lead to lower systems costs. While
balance the Li2CO3 is less prevalent and more costly than Na2CO3 or K2CO3,
the amortized lithium carbonate is not high as the electrolyte is not
3.1. The combustion of methane consumed in the CNF production process. As will be shown in this
study, a number of heat sources internal to the CNF CC plant supply
The first section of the thermodynamic assessment will focus on excess of the thermal energy required for the molten Li2CO3 elec-
the energy output of a combined cycle power plant, and makes the trolyte, such as the excess heat of the CO2 from combustion, heat
reasonable assumption that the natural gas fuel may be idealized generated by the dissolution and reaction of the CO2 with oxide
as shown in Eq. (2): in the electrolysis chamber to form carbonate, as well as the heat
exchange of the electrolysis products during recovery. An addi-
CH4 ðgÞ þ 2O2 ðgÞ ! CO2 ðgÞ þ 2H2 OðgÞ þ heat ð2Þ tional fraction of required energy is supplied by the applied elec-
trolysis potential to drive the electrolysis process to produce the
This methane combustion reaction has an enthalpy of
desired carbon nanofiber products.
890 kJ/mol at 25 °C from the thermodynamic data available
through the NIST Webbook and NIST-JANAF Thermochemical
Tables [41,42]. Of this 890 kJ/mol at 59% efficiency, the CC power 3.2.1. Heat released in the carbonate dissolution of hot CO2
plant generates 525 kJ of electricity per mol of methane oxidized. In the CC CNF plant, the first step of the CO2 to CNF technology
utilizes the electrochemically produced metal oxide, in this case
Li2O, to react with the CO2 from the combustion process to produce
3.2. The CO2 to CNF transformation
Li2CO3. This process allows for the removal of the CO2 from hot
exhaust gas without the need for cooling, as the capture process
A variety of carbonate electrolytes may be used in the CO2
produces more energy at higher CO2 temperatures shown in
electrolysis. We have shown that pure Li2CO3 yields a particularly
Fig. 6. The capture process plays an additional role of regenerating
high yield (85–100%) of carbon nanotubes at low energy, and
the Li2CO3 that was lost from the electrolyte during the electrolytic
hence Li2CO3 is used in this thermodynamic assessment. This elec-
formation of carbon nanofiber. The reaction for this capture pro-
trolyte has a melting point of 723 °C and has been shown experi-
cess is shown in Eq. (3).
mentally to require the lower electrolysis potential for the
process than potassium or sodium carbonate electrolytes, which Li2 O þ CO2 ! Li2 CO3 ð3Þ
have a higher melting point [2–10]. Various eutectic mixtures
 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410 405

low temperature and without transition metal nucleation), carbon

nanoparticles (at intermediate temperature and in the presence of
transition metal nucleating agents) or carbon monoxide at higher
temperature. While the CO2 transformation by electrolysis is com-
plex, at low to moderate temperatures (up to
800 °C) the global
lithium carbonate electrolysis process in the absence of added car-
bon dioxide is straightforward; with application of 4 Faraday (1 F
araday = 1 mole of electrons = 96,485 C = 96,485 A s), one mole
of solid carbon (here carbon nanofiber), one mole of Li2O, and
1 mol of oxygen product is generated for each lithium carbonate
consumed, and in the presence of CO2, the generated Li2O regener-
ates the Li2CO3 consumed electrolyte. At
750 °C in the presence of
transition metal nucleating agents, the yield for the production of
carbon nanofibers is high (approaching 100% columbic efficiency)
and the required electrolysis potential is generally low (
1 V)
and falls with increasing concentration of added lithium oxide
[2,44–46].
Fig. 6. The enthalpy for the regeneration of Li2CO3 from Li2O and CO2 from the
temperature variation of the enthalpy CO2, while the temperature of Li2CO3 and Li2 CO3 ! Li2 O þ CðCNFÞ þ O2 ðgÞ ð5Þ
Li2O is held constant at the electrolysis temperature of 750 °C. Calculated using the
individual thermochemical species date in references [41,42]. 750 °C is the typical temperature used to generate carbon nano-
fibers by electrolytes. At this temperature the coulombic efficiency
Fig. 6 presents the variation of enthalpy calculated from the for carbon nanofiber synthesis can approach 100% (that is each four
thermochemical enthalpies of the individual species, for this electrons generates a zero valent carbon from), while at increasing
lithium carbonate formation reaction. As the temperature of the greater temperature the process shifts toward the production of
CO2 increases, the energy gains for the process increases as well. CO, rather than carbon [44–46]. This model does not take into
This suggests that the CO2 capture should occur at the highest pos- account the small solvation energy of the Li2O, which was found
sible temperature, which synergizes well with the increased tem- to be less than 7.8 kJ/mol at 750 °C [3]. A more comprehensive
perature of burning methane in an oxygen-rich environment. The understanding of the effect of temperature on solvation energy is
enthalpy of the solid carbon product and produced O2 gas at required before it can be incorporated. The enthalpy of this reac-
increasing temperature is compared to the enthalpy of the carbon tion at 750 °C is 553 kJ/mol for every mol of carbon nanofibers pro-
and O2 gas when removed from the system at 25 °C. This study duced. This is the energy required to form the Eq. (4) products
assesses the process at the temperature of 750 °C, which is the without cooling. The electrolysis potential varies with the free
experimentally observed temperature for high coulombic effi- energy, rather than the enthalpy, as shown in Fig. 7.
ciency production of CNFs [2–9].
As seen in Fig. 6, the heat generated by CO2 dissolution reaction
3.4. Recycled heat extracted from electrolysis products
is 158 kJ/mol of CO2 captured, at 750 °C. This heat is released
back into the system. Additionally, this CO2 capture process
These oxygen and CNF products generated by Eq. (5), while
decreases the heat lost through the stack of the plant, as rather
formed at high temperature (750 °C), will eventually be used at
than being emitted, the CO2 is kept within the system. In a conven-
room temperature, for combustion (O2) or as a finished, value
tional CC power plant, CO2 accounts for approximately 4–9% of the
added product (carbon nanofibers). With proper heat capture tech-
stack emissions by volume depending if the flue gas is recycled
nology a significant fraction of these product’s heat can be recap-
[43]. As shown in Fig. 2, the stack emissions of contemporary CC
tured back to the steam turbine component of the combined
plants account for
10% of the total energy of the combustion reac-
cycle plant to improve efficiency. The heat released from each
tion and
5% of those stack emissions by volume are from the CO2.
However, due to its higher molecular weight, greater kinetic
energy, and the great heat capacity of CO2 compare to N2 (N2 dom-
inates the composition of contemporary CC stack emissions), the
proportional heat loss by CO2 is greater in the flue gas. We estimate
the percent of the available methane combustion enthalpy lost by
the CO2 stack emission from the relative heat capacities of CO2 and
N2 at the stack temperature of 106 °C, which equals:

ð890 kJÞ ð40:55 kJ=mol of CO2 Þ

10%   5%  ¼ 6:1 kJ=mol ð4Þ
mol 29:55 kJ=mol N2
From Eq. (4), we can estimate that a total of 6.9% of the total
thermal capacity of the stack emissions is from the CO2 that is
not released, meaning that 0.69% of the entire combustion energy
is additionally saved in the system. This energy accounts for 6 kJ
per mol of methane combusted.

3.3. Heat consumed during the transformation of CO2 to value-added

products
Fig. 7. The calculated Gibb’s free energy for the formation of C and CO from CO2 or
The CO2 transformation to products in molten carbonates is Li2CO3 using a 4-electron pathway for the formation of C and a 2-electron pathway
complex and involves the formation of amorphous carbon (at for the formation of CO [41,42].
406 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410

product as a function of temperature is included in Fig. 6. The Prevented Stack Emission Loss : 6:9% CO2 of 10% Stack Emission
enthalpy of the O2 from 750 °C to 25 °C is an energy savings of DH ¼ 6 kJ=mol
24 kJ/mol of O2. The enthalpy of the carbon from 750 °C to
25 °C is an energy savings of 12 kJ/mol of carbon, for a combined
savings of 36 kJ/mol of product. O2 combust enhancement : CH4 þ O2 ðpureÞ þ O2 ðairÞ ! CO2
þ H2 O DH ¼ 134 kJ=mol
3.5. Heat added through improved oxy compared to air combustion
Total enthalpy CO2 to CNF electrolysis in power plant
Fossil fuel power plant energy efficiency can improve by
30–54% by enriched oxygen mixtures, rather than pure air, during DH ¼ 219 kJ=mol ð6Þ
the fuel combustion [5,35,47,48]. These improvements can come in
improved heat transfer properties from the increased temperature
of combustion and the improved heat transfer properties of the 5. CC CNF plant equivalent potential, power and CNT produced
flue gas with the decrease of N2 present. Hurley et al. propose that
a system using a high temperature heat exchanger that is oxygen The thermoneutral potential is the voltage equivalent to the
blown instead of air blown can produce a 50% or greater increase enthalpy associated with the Eq. (1) enthalpy of the n = 4 electron
in the heat recovery rate for the system [49]. Efficiency gains can methane combustion is given using 1 mol of electrons = 1
also be found from the increase in overall combustion efficiency Faraday = 96,485 C = 96.485 V1 kJ/mol:
as well as an increase in heating rate of the combustion system.
A natural gas combustion with 30% oxygen-enriched air process Eðvolts; methane combustionÞ ¼ DH=n
sees a 53.6% decrease in fuel consumption during heating as well
¼ 890 kJ=mole=ð4  FaradayÞ ¼ 2:31 V ð7Þ
as a 26.1% decrease in fuel consumption during constant furnace-
temperature combustion, compared to unenriched 21% oxygen In conventional CC power plants, at 59% heat to electricity
combustions [47]. Furthermore, at even high enriched oxygen conversion efficiency, this is equivalent to the plant operating
levels, there is a continued improvement of combustion efficiency at 0.59 ⁄ 2.31 V = 1.36 V per equivalent of methane combustion.
as Belohradsky shows an increase from 60% to 78% to 82% combus- The modeled CC CNF power plant operating at 79%
tion efficiency when using 21% O2, 38% O2 and 46% O2 respectively conversion efficiency is equivalent to this plant operating at
[35]. 0.579 ⁄ 2.31 V = 1.82 V per equivalent of methane combustion.
The challenge for current implementation of oxygen enriched The calculated total additional enthalpy consumed by the CC
combustion process is the energy required to purify the oxygen, CNF power plant in the production of carbon nanofibers, 219 kJ/mol
for example via cryogenic liquefaction and extraction, the process from Eq. (6), is equivalent to a thermoneutral potential of:
consumes and loses the substantial majority of the energy gained
by improved efficiency, and imposes satellite oxygen purification Eðvolts; CNF plant productionÞ
infrastructure costs. An additional disadvantage is that the higher
¼ 219 kJ=mole=ð4  FaradayÞ ¼ 0:57 V ð8Þ
temperature of pure oxygen combustion poses a material chal-
lenge, and hence a mix of air and pure oxygen to improve efficiency Hence, this assessment yields that per equivalent methane the
had been preferred [4]. Interestingly, the CC CNF plant provides the plant will generate a net of (1.82  0.57) = 1.25 V; that is 482 kJ
oxygen efficiency gains without these drawbacks. The electrolysis of electricity and 12 g of carbon nanotubes per mol of methane oxi-
chamber generates one mole of pure oxygen for each mole of dized. This compares to 1.36 V (525 kJ of electricity and 44 g of CO2
methane consumed, which, as per Fig. 5, may be blended with per mol of methane oxidized) for the conventional CC power plant
air to provide the two moles of O2 per CH4 combustion required with the added advantages that (i) in the CC CNF plant no CO2 is
in Eq. (2). Without the energy loss of other oxy fossil fuel processes, emitted and (ii) all CO2 is converted to value added carbon nan-
we conservatively estimate an absolute efficiency gain of 15%, that otubes. Converting to power and ton units, per metric ton of
is from 59% for the CC power plant to 74% for the CC CNF power methane fuel consumed the CC CNF plant produces 8350 kW h of
plant. This is equivalent to an extractable energy gain from the electricity and 0.75 ton of CNT and emits no CO2, while the CC
methane of 0.15 ⁄ 890 = 134 kJ/mol, that is 659 kJ/mol for the plant produces 9090 kW h of electricity, no CNT and emits 2.74
CC CNF, rather than 535 kJ/mol for the CC power plant. ton CO2. At an estimated $0.1 per kW h and $300 K per ton CNT,
per ton of methane fuel (
$100) the CC CNF plant produces $835
of electricity and $225,000 of CNTs, while the CC plant produces
4. Global enthalpy of CO2 to CNF electrolysis addition to CC $909 of electricity, no CNT and emits 2.74 ton CO2. Even if the mar-
power ket price of CNTs were to fall by two orders of magnitude with
increasing supply, the CC CNF still provides a strong value incen-
tive (CNT product is higher than the electricity product value) for
Li2 Oð750  CÞ þ CO2ðgÞ ð750  CÞ ! Li2 CO3ðlÞ ð750  CÞ carbon dioxide removal.
The required voltage to drive electrolysis between electrodes in
DH ¼ 158 kJ=mol
the electrolysis chamber is constrained by the free energy, DG,
rather than the enthalpy, DH, of the specific electrode reactions
Li2 CO3ðlÞ ð750  CÞ ! Li2 Oð750  CÞ þ CðCNFÞ ð750  CÞ þ O2ðgÞ ð750  CÞ
and isolation of the electrode specific reactions varies with temper-
DH ¼ 553 kJ=mol ature, electrolyte, and electrolyte additives, such as Li2O which
decreases the required voltage [3]. The surplus energy of applied
CðCNFÞ ð750  CÞ þ O2ðgÞ ð750  CÞ ! CðCNFÞ ð25  CÞ þ O2ðgÞ ð25  CÞ voltages of greater than the 0.57 V of Eq. (8), will be recycled from
DH ¼ 36 kJ=mol the electrolysis chamber as heat back into the steam turbine via
the heat exchange loop evident in Fig. 5. The required electrolysis
subtotal : CO2ðgÞ ð750  CÞ ! CðCNFÞ ð25  CÞ þ O2ðgÞ ð25  CÞ potential is generally low (
1 V), and increases with the overpo-
tential necessary to drive CNF production at higher rate (the
DH ¼ 359 kJ=mol
applied potential increases with electrode current density).
 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410 407

5.1. Coal, rather than natural gas, to CNF transformation However, the coal CNF plant is energetically efficient, due to the
low electrolysis voltage and high coulombic efficiency observed
The vast majority of coal power plants combust pulverized coal for the CO2 to CNF transformation, and is further enhanced given
to produce high temperature, which evaporates to produce pres- the opportunities of the CO2 electrolysis chamber to retain heat
surized steam that drives turbines to generate electricity. The within the coal CNF plant, to use the electrolysis generated pure
exhaust of the combustion is generally cleansed of the majority oxygen to increase the coal combustion efficiency, and to use the
of sulfur, heavy metal and particulates and the remaining flue steam condenser heat loss to improve the product extraction and
gas exhaust, which contains a high carbon dioxide content (along heat balance of the electrolysis chamber.
with nitrogen and water vapor) and is emitted directly to the Fig. 9(c) and (d) explores coal power plants that simultaneously
atmosphere. Components of a convention coal power plant are produce electricity and CNFs without CO2 emission, by supple-
illustrated in the top portion of Fig. 8 [50]. Conventional coal elec- menting the coal generated electricity with a non-CO2 electrical
tric power stations emit massive amounts of carbon dioxide to the source. Plant Fig. 9(c) is a renewable/coal plant produces both elec-
atmosphere, which comprises a substantial fraction of the total tricity and CNFs, and uses non-CO2 emitting renewable (or nuclear)
greenhouse gases. Exhaust flue gas volume composition varies power, rather than electricity from the coal plant, to drive the elec-
with plant construction. The flue gas volume is
323 m3/GJ from trolysis. Note, that in Fig. 9(d), the STEP/coal plant has the highest
coal power plants. The flue gas contains a majority of nitrogen, efficiency. The plant uses the full spectrum of sunlight, and pro-
water vapor, and generally 8–9% (between
4 and
13% of CO2 duces both electricity and CNFs; concentrated sunlight is split into
depending on the type of burner and load being used [51]). Addi- two band, the infrared band heats the electrolysis chamber and
tional infrastructure is included to scrub the flue gases of sulfur, directs excess heat into the coal combustion chamber, and the vis-
nitrous oxides and heavy metals. Coal is principally carbon and ible drives photovoltaic power of the electrolysis chamber. Higher
moisture. More specifically for the coals lignite contains 45–55% efficiency is achieved by using the full spectrum of sunlight. As we
carbon and up to 55% moisture, bituminous coal contains 60–82% have previously demonstrated, visible sunlight provides efficient
carbon, while anthracite is 93–95% carbon. The three respectively electrical power and the thermal sunlight provides supplemental
have heat contents of
24–30 kJ/g, 33–40 kJ/g, and 37–39 kJ/g [52]. heating of STEP electrolyses [44–46,54,55]. For example, conven-
There exist a few integrated (coal) gasification combined cycle tional photovoltaics use super-bandgap (visible) radiation, and
(IGCC) power plants, which burn the coal with purified oxygen, cannot use sub-band (thermal energy) as it is not sufficient to drive
rather than air, and can gasify the coal to hydrogen or syngas. An electron/hole separation. For example a conventional efficient (40%
IGCC is illustrated on the bottom panel of Fig. 8 [53]. These IGCC solar to electrical) concentrator photovoltaic, can achieve over 50%
plants have higher energy conversion efficiency (
50% compared solar energy efficiencies [44] when the excess thermal energy is
to
35% for traditional). IGCC plants have the potential to reach directed to heat the chemical and electrical reactions here. The
substantially higher efficiency when the energy penalty to form material in solar thermal conversion has an important role to
the required pure oxygen is circumvented, such as via the in-situ increase the efficiency of STEP. CNT is one of the materials which
electrolysis of CO2 studied herein. Oxy-fuel, rather than air, coal efficiently absorb the full spectrum [56].
plants have several advantages and energy efficiency is higher
due to the higher temperatures achieved with a higher O2 combus-
6. CC CNF thermodynamic assessment refinements
tion and because heat stack losses are less, as the emitted gas vol-
ume is significantly smaller with less N2 from air. Oxy-fuel coal
With scale-up of the CO2 to CNF process ongoing refinements
plants generate a more concentrated carbon dioxide emission than
will be evident. As this refinement occurs, both enhancements
simple coal combustion for heat, which have been explored as
and losses to the total enthalpy estimates of Eq. (6) can be
potential carbon sequestration opportunities for coal plants. Here,
expected. The global efficiency of the CC CNF power plant can be
by integrating the coal plant with the STEP CNF plant, pure oxygen
expected to improve. Today, a large heat loss (30% in Fig. 2) is asso-
from the electrolysis is available to improve coal combustion effi-
ciated with condensation of steam in the steam turbine loop.
ciency without the need for the cryogenic production of pure oxy-
Future refinements may use, rather than lose, a portion of this heat
gen, there is no carbon dioxide emission, heat is retained in the
for example in the CNF extraction process, and developments of
combustion chamber, as there is little excess stack as to exhaust,
this extraction process are of interest. One potential improvement
and a useful, stable product CNFs (and in particular, their more
for the capture of this lost heat is the ability for a direct heat trans-
valuable form as carbon nanotubes) are produced.
fer to be employed for the addition of post-combustion H2O to be
The top corner (panel A) of Fig. 9 simplifies the conventional
added to the water used for the Rankine cycle. As more oxygen-
CO2-emitting coal power plant illustrated in the top of Fig. 8, by
enriched air is used for combustion, the higher the concentration
reducing the plant to its simple functional components. Panels
of water will be in the exhaust gas allowing for larger gains for a
B–D in Fig. 9 present non-CO2 emitting coal combustion plants.
direct heat transfer method opposed to the current indirect heat
Each incorporates an electrolysis chamber, which splits hot CO2
transfer method used now. Conversely, there are enthalpy losses
from the coal combustion into a CNF product and into pure oxygen
not accounted for to be added in further refinements such as the
which is improve the coal combustion. B is a coal CNF plant. C is a
(i) less than ideal heat exchanger losses from the CNF and O2 elec-
coal CNF & electricity plant, and D is a highest efficiency, STEP coal
trolysis products back into the and (ii) heat radiative losses from
CNF & electricity plant that utilizes the full spectrum of sunlight to
the electrolysis chamber.
energize the electrical and CNF production.
The thermodynamic enthalpy available per CO2 emitted from
carbon combustion (394 kJ/mole) is less than that from methane 7. Comparison with conventional carbon extraction technology
(890 kJ/mole) combustion. Coal, compared to natural gas, com-
bustion will generate less excess heat per transformable CO2 to Carbon dioxide removal technology has used been employed at
drive CNF and CNT production product is retained within the sys- pilot plants using an amine-solution absorption trap with 90% CO2
tem at (the electrolysis chamber temperature of) 750 °C, and hence capture rates. These plants have an average energy efficiency loss of
under normal circumstances while a CC CNF plant can co-produce 7%, although combined losses have been estimated as high as 30% in
electricity and CNFs, a coal CNF plant (Fig. 9(b)) will produce only conjunction with CC power plant [57]. The subsequent challenge of
value-added carbon nanotubes, and not surplus electricity. an effective storage of that extracted CO2 was not effectively
408 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410

Fig. 8. Conventional (top) and integrated gasification combined cycle (bottom) coal power plants [50,53]. Key for conventional power plant: 1. Cooling tower, 2. Cooling
water pump, 3. Transmission line (3-phase), 4. Step-up transformer (3-phase), 5. Electrical generator (3-phase), 6. Low pressure steam turbine, 7. Condensate pump, 8. Surface
condenser, 9. Intermediate pressure steam turbine, 10. Steam Control valve, 11. High pressure steam turbine, 12. Deaerator, 13. Feedwater heater, 14. Coal conveyor, 15. Coal
hopper, 16. Coal pulverizer, 17. Boiler steam drum, 18. Bottom ash hopper, 19. Superheater, 20. Forced draught (draft) fan, 21. Reheater 22. Combustion air intake, 23.
Economiser, 24. Air preheater, 25. Precipitator, 26. Induced draught (draft) fan, 27. Flue-gas stack.

addressed, with one principle course of action to pump the sequestration may be a misnomer. Note the CC CNF does not
extracted CO2 to release more fossil fuels. This may raise, rather require a CO2 pre-concentration step to eliminate the CO2 emission.
than lower, the carbon footprint, and the characterization of One benefit of the integrated CC CNF power plant assessed in
concentrating carbon dioxide using amines as carbon capture this study, in addition to CO2 emission elimination and the
 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410 409

Fig. 9. Various plant configurations to transform carbon dioxide emissions from coal combustion into carbon nanofibers/nanotubes using various renewable energy sources.

incentivized transformation into a value-added carbon nanotube reaction of lithium oxide with carbon dioxide to form lithium car-
product, is the ability to absorb the carbon dioxide at a high tem- bonate, the energy from cooling both the carbon and oxygen prod-
perature instead of at a low temperature as performed with con- ucts, the energy saved from preventing emissions of CO2, and the
ventional CCS technology. This additional enthalpy savings is energy gained in the system from capturing hot CO2 instead of cold
shown in Eq. (9). CO2. This energy output is further improved as the secondary pro-
duct of the electrolysis product (in addition to carbon nanotubes)
CO2ðcapturedÞ ð25  CÞ ! CO2ðcapturedÞ ð750  CÞ DH ¼ 35 kJ=mol ð9Þ of pure oxygen is looped back into the CC gas combustion improv-
A summary of all the energy savings compared to that of a con- ing the CC efficiency with an enriched oxy-fuel mixture for
ventional CCS include the energy gained from the reaction of increased efficiency.
lithium oxide with carbon dioxide to form lithium carbonate, the Fossil fuel combustion is the largest anthropogenic source of CO2
energy from cooling both the carbon and oxygen products, the emissions and until renewable energy technologies are fully
energy saved from preventing emissions of CO2, and the energy deployed, continues to play a significant role in the energy portfolio
gained in the system from capturing hot CO2 instead of cold CO2. of the world. A combined cycle, CC, natural gas power plant is
These savings reduce the cost of the electrolysis process to poised to play a continuing role in energy production as a result
312 kJ/mol, allowing for the production of one mol of carbon of the abundance of the fuel source and the high efficiencies of
nanofibers and 213 kJ of additional energy for each mol of CO2 the systems. However, these power plants require some type of
transformed. This energy output is further improved to 357 kJ/mol CO2 capture and sequestration to mitigate climate change. One such
of CO2 transformed when the 15% efficiency benefit is added from system is an alternative carbon nanofiber combined cycle, CC CNF,
the enriched-oxygen combustion. plant. This assessment yields that per equivalent methane the CC
An additional benefit, not measurable in dollars or kilojoules, of CNF plant will generate a net of (1.82  0.57) = 1.25 V. This
the CC CNF plant and/or coal to CNF transformation is that more compares to 1.36 V for the conventional CC power plant with
readily available CNF will positively impact the automobile, airline, the added advantages that (i) in the CC CNF plant no CO2 is
trucking, shipping, etc. industries; especially with respect to the emitted and (ii) all CO2 is converted to value added carbon
reduced weight (and therefore reduced fuel consumption and nanotubes. The CC CNF adds a high-temperature molten Li2CO3
emissions), increased strength and lifespan of the products (which electrolyzer to a CC power plant design to remove exhaust CO2
will reduce the manufacturing use of fossil fuels), etc. and transform it into a valuable carbon nanotube product. The pre-
sent day value of the carbon nanotubes product is
10,000 times
that of proposed, or in place, current carbon tax costs of $30 per
8. Conclusion ton, strongly incentivizing carbon dioxide removal and spur new
public/private investment in this process to convert CO2 into carbon
An assessment of the energy balance of a combined cycle gas nanotubes globally.
plant, which additionally incorporates a molten electrolysis
unit to transform CO2 to carbon nanotubes has been conducted.
The assessment indicates that the electricity and carbon nanotubes Acknowledgement
can be co-generated and that the CO2 emission eliminated. The CC
and electrolysis components act in a complementary/synergistic This work was partially funded by the United States National
manner. The hot product from the gas turbine is an excellent reac- Science Foundation under grant number 1505830. The authors
tant for the molten electrolysis, analyzed with a lithium carbonate are grateful to Jiawen Ren for help with electron microscopy
electrolyte. Energy savings include the energy gained from the associated with Fig. 1.
410 J. Lau et al. / Energy Conversion and Management 122 (2016) 400–410

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