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Renewable and Sustainable Energy Reviews 19 (2013) 82–106

Contents lists available at SciVerse ScienceDirect

Renewable and Sustainable Energy Reviews


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

Fighting global warming by photocatalytic reduction of CO2 using giant


photocatalytic reactors
Renaud Kiesgen de_Richter a,n, Tingzhen Ming b, Sylvain Caillol a
a
Institut Charles Gerhardt Montpellier – UMR5253 CNRS-UM2 – ENSCM-UM1–Ecole Nationale Supérieure de Chimie de Montpellier,
8 rue de l’Ecole Normale, Montpellier 34296 Cedex 5, France
b
School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan, China

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

Article history: Over the last decades, fighting global warming has become the most important challenge humanity has
Received 22 November 2011 to face. Therefore technologies of carbon dioxide capture, sequestration and recycling are equally
Received in revised form important in order to tackle the global climate change stakes. Among recycling technologies,
12 October 2012
photocatalytic processes reducing CO2 with H2O back to fuels or to other useful organic compounds,
Accepted 14 October 2012
have the potential to be part of a renewable energy system. Indeed these processes can help to control
Available online 7 December 2012
CO2 emissions and eventually eliminate CO2 in excess.
Keywords: This perspective paper describes a large size device, able simultaneously:
CO2 capture  to proceed to direct air capture (DAC) of CO2;
CO2 reduction
 to transform part of it into useful chemicals, like hydrocarbons or syngas;
Photocatalysis
Photocatalytic reactor
 and to produce renewable energy, thus preventing future CO2 emissions.
Solar chimney power plant Synergies between solar chimney power plants (SCPPs) and semiconductor photocatalysis in order
to create giant photocatalytic reactors for artificial photosynthesis are discussed, as well as scale
economies for unconventional carbon capture directly from the atmosphere.
This paper presents a carbon negative emission technology obtained by coupling SCPPs with DAC
systems which allows many scale economies, and also synergies to proceed to solar-to-chemical
energy-conversion process by photocatalytic reduction of atmospheric CO2 under sunlight.
& 2012 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2. Direct air capture (DAC) or dilute carbon dioxide capture from the atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.1. Rationale for DAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.2. Comparing costs of DAC and CSS. Is the cost of air capture worth it? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.3. Technical differences between DAC and CSS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3. Interest of solar chimney power plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.1. Need to couple DAC with an energy carbon neutral source. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.2. Optimization of plant output. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.3. Base load and peak load . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4. Rationale of coupling DAC with solar chimney power plants SCPPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.1. Synergies of SCPPs coupled with DAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.2. Scale economies of SCPPs coupled with DAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.3. Advantages of DAC under SCPPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4.4. Proximity of SCPPs from disposal sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4.5. Cost reduction potential of SCPP þDAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5. Carbon dioxide recycling or artificial photosynthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.1. Interest of photocatalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.2. Photocatalytic reduction of carbon dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

n
Corresponding author. Tel.: þ33 4 67 52 52 22; fax: þ 33 4 67 14 72 20.
E-mail address: renaud.derichter@gmail.com (R.K. de_Richter).

1364-0321/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.rser.2012.10.026
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 83

5.3. Experimental conditions and yields of CO2 reduction by photocatalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93


5.3.1. Sequential reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.3.2. Temperature effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.3.3. Wavelength effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.3.4. Alkalinity effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.4. Sensitivity analysis of key parameters for SCPP þ photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6. Choice of experimental conditions for large scale tests of photocatalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6.1. Choice of the reaction type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
6.2. Choice of the reactor type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
6.3. Research effort needed. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
6.4. Extrapolation to large scale photocatalytic reactors and photocatalytic performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.5. Synergies from SCPPs coupled with photocatalytic reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.6. Improving the choice of the PCR type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.6.1. Contact time and radiation effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.6.2. Day and night overall performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.7. Sensitivity analysis of key parameters for photocatalytic reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

1. Introduction
Fig. 1a shows the CO2 emissions repartition from the different
Carbon dioxide is increasing in the atmosphere due to defor- sectors (Source IEA [4]), and Fig. 1b shows the CO2 emissions
estation and to fossil fuels use in industry and transportation, growth from different sectors between 2000 and 2005 (source
manufacture of cement, building heating and cooling. World Research Institute [6]).
With a global radiative forcing of 1.74 W m  2, CO2 is the Power plants do not account for all the CO2 emissions: from
largest contributor among well-mixed long-lived greenhouse cars, boats, planes and others. In order to also take into account,
gases, accounting for more than 63% of the total [1]. these diffuse CO2 emissions DAC ideas and materials have been
The potential of photocatalysis to mitigate or remove almost developed by several scientists like professors Zeman [7,8] and
all global warming contributors like CO2, methane CH4, nitrous Lackner [9–11] from Columbia University in New York.
oxide N2O, chlorofluorocarbons (CFC-11, CFC-12 and other Probably new policy instruments will oblige new fossil power
CFCs), tropospheric ozone O3, minor greenhouse gases GHGs plants to install CCS. Current regulatory efforts and proposed
(sulfur hexafluoride SF6 and nitrogen trifloride NF3), and also legislation seek to reduce CO2 as well as make CCS necessary for
black carbon or particulate matter [2] has been reviewed highly pollutant industries or power plants if they do not want to
recently. buy carbon credits on the market.
Carbon capture and storage (CCS) involves collecting and Few innovative solutions to global warming induced by CO2
generating a highly concentrated steam of almost pure CO2, emissions have been proposed. This paper focuses in its first part
transporting and sequestering it in order to avoid atmospheric on the goals of carbon capture and sequestration, storage (CCS) or
entry and contribution to climate change. CCS covers a range of transformation into useful products, in order to prevent the
technologies and techniques that hold the promise of catching accumulation of CO2 in the atmosphere by catching it and
up to 90% of the future CO2 emissions from power stations and converting it back to fuels, or storing it safely and permanently.
industrial sites. Once it has been trapped, CO2 is purified and Then the second and third parts of this article discusses the
compressed to liquid, transported – often for several hundred interest of an unusual renewable energy device (i.e., solar chim-
kilometers – and then either buried in the ocean or in a neys power plants SCPPs) and of the synergies of performing CO2
geological formation suitable for sequestration (deep saline capture directly from air with this SCPPs as many scale economies
aquifers, disused coal deposit), or used for industrial purposes are feasible [12]. The interest of photocatalysis and the possibility
like enhanced oil recovery – which consists to pump CO2 into an to perform the reverse reaction of fuel combustion (i.e., artificial
oil field to help extract more fuel – or transformed into mineral photosynthesis) in synergy with solar light under the SCPPs is
carbonates. The 2005 IPCC Special Report on CCS [3] provides a then addressed in the fourth and fifth parts of this review.
full description of these technologies.
Capturing CO2 at large point sources (flue gas at an operating
coal fuel or gas fired power plant) where it is quite concentrated 2. Direct air capture (DAC) or dilute carbon dioxide capture
makes sense as the power plants and the industry emits, respec- from the atmosphere
tively, 41 and 17% of the CO2 [4]; however, it does not allow the
capture of the CO2 emissions from the transportation sector (23% of 2.1. Rationale for DAC
the emissions) or from residential and commercial sectors (10%).
Direct air capture (DAC) of diffuse CO2 from ambient air is The process of DAC is very similar to the CCS process from
complementary with CCS and can deal with all types of emissions, concentrated CO2 in the flue stack of a power plant: An alkali
even past ones. Maybe DAC can even be cheaper in some cases component is needed to react with weak acidic CO2 in order
than to upgrade and retrofit the oldest conventional pulverized to separate it from neutral gases (nitrogen N2 and oxygen O2).
coal power plants and then transport the compressed CO2 to the Then a regeneration process is needed to liberate the almost pure
storage or disposal site after building hundreds of kilometers of CO2 from the salt formed and recycle the alkali component.
pipelines. Pipelines to transport the CO2 to suitable burial sites Compression and liquefaction of CO2 is then performed for further
could cost more than $1 million per mile [5]. transportation and underground storage.
84 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

government laboratories and industry, the American Physical Society


(APS) released a technical assessment stating that: ‘‘it makes little
sense to ignore the emissions of CO2 in the flue gas from a coal power
plant while removing CO2 from ambient air where it is 300 times
more dilute’’, and that ‘‘CO2 capture from air (air capture) will cost at
least US$ 600 per ton CO2 avoided’’. Therefore DAC would ‘‘play a very
limited role in a coherent CO2 mitigation strategy’’, as by using the
same simplified costing evaluation methodology ‘‘the estimated
avoided cost for ‘post-combustion capture’ of CO2 from the flue gas
of a reference coal power plant is about $80/tCO2’’.
For Ranjan [15,16] ‘‘a conservative estimate for the operating
cost of direct air capture came out to be $420–$630/tCO2’’. This is
only the cost of energy and does not take into account the capital
cost of plants building. Such prohibitive mitigation costs let think
that DAC cannot compete with other viable climate change
mitigation options and for Ranjan cost estimates for DAC found
in the literature are just not believable.
This estimates are considerably higher than the cost estimates by
Keith [17,18]: $140/t CO2, or from Stolaroff [19] for whom the cost of
capturing CO2 with a complete system would fall between 80 and
250$/t CO2 using NaOH spray solution and he thinks this is a viable
sorbent for large scale CO2 capture. For Pielke [20], although cost
assessment is not unambiguous, DAC deserves to be among the
options receiving attention in the international climate policy debate.
For the UK Institution of Mechanical Engineers [21], in the context of
the margins of uncertainty, the costs of air capture and CCS seem to
be of broadly similar magnitude.
The DAC system analyzed by the APS consisted in passing air over
a solution of sodium hydroxide in a counter-current, closed system.
The sodium carbonate formed is then cross-reacted with calcium
hydroxide to form calcium carbonate as a precipitate. The solid
calcium carbonate is then submitted to thermal decomposition with
capture of the CO2 released. The reaction scheme is [7]:

NaOH (solution)þCO2 (air)-Na2CO3 (solution)þH2O (1)

Na2CO3 (solution)þCa(OH)2 (slurry)-CaCO3 (precipitate)


þ2 NaOH (solution) (2)

CaCO3 (solid) þheat-CaO (solid) þCO2 (gas) (3)

CaO (solid)þ H2O-Ca(OH)2 (slurry) (4)

The APS report estimated that to remove CO2 from the atmo-
Fig. 1. (a): CO2 emissions from different sectors (Source IEA [4]), (b): CO2 emissions sphere as fast as a 1 GW coal plant emits it (about 6 Mt CO2 yr  1)
growth from different sectors (source World Research Institute [6]). such a system would have a total length of about 30 km (based on
Source: IEA from international Energy Agency, ‘‘Energy-Related CO2 Emissions by
structures able to capture about 20 t CO2 yr  1 for each square
Sector in the Reference Scenario,’’ Table 4.4, in world Energy Outlook 2009 (Paris:
2009), p. 185. meter of frontal area, 10-m high structures, 2 m s  1 air flow, with
CO2 capture yield of 50%). Large quantities of construction
Both CCS and DAC costs can be split up into several items: materials (Fig. 2) and chemicals would be required and this is
initial equipment investment; CO2 capture with sorbents; CO2 capital-intensive. The APS report ‘‘took into consideration a DAC
release from sorbents; regeneration and recycling of sorbents; with a capacity of 1 Mt CO2/yr and estimated the capital cost to
sorbent loss; CO2 compression; transportation of pressurized CO2, 2.2 billion dollars’’.
geological sequestration; leakage monitoring, infrastructure As an answer to the APS assessment [13], Climeworks [23]
maintenance; environmental impacts; and others. published a statement reminding that thermodynamics reveal that,
while the CO2 concentration differs by a factor of about 300 between
2.2. Comparing costs of DAC and CSS. Is the cost of air capture worth flue gas and air, the minimum energy required to extract pure CO2
it? differs only by a factor of about 3 [9]. According to Climeworks, their
sorbent material achieves similar CO2 loadings in an air capture
The main drawback of CCS is the energy penalty caused by the process as the state of the art sorbent materials achieves for CO2
CO2 separation from other gases. It increases the CO2 avoided cost capture from flue gases. Opposed to the reference DAC system
and is an important driving force to propose new and improved analyzed in the APS report, their system requires more than 95% of
capture methods with lower energy requirements. In this paper its energy input in the form of cheap, low-temperature heat. And for
the comparison focuses on the first part of the process: The CO2 the APS team the costs for DAC will not fall substantially through
capture, as it is assumed that some costs (compression, seques- incremental improvements in current technology.
tration etc.) are identical for conventional CCS or DAC. On the other hand Lackner [9] proposed a different technology
Recently, after a two-year study conducted by Socolow with a where the energy causing the air to move through the contactor
committee of 13 members [13,14] from academia, national or (a small part of the total energy requirement) can be provided by
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 85

done anywhere in the world, near disposal or sequestration


locations, transportation of pressurized CO2 can be reduced to
minimum and there is no need to build CO2 pipelines over long
distances.
This reduced investment and transportation costs will prob-
ably give advantage to DAC over conventional CCS when regula-
tory constraints and binding rules will come into effect.
In the air, CO2 is quite diluted and is a fairly inert component.
How is it possible to separate it from large volumes of atmo-
spheric nitrogen and oxygen?
Solid sorbents in the form of alkali resin polymers (commer-
cially available for water deionization) present a permanent
positive charge on which CO2, a weak acid, can bind. The
discovery by the Lackner team and his associates [24–26] that
humidity can displace CO2 from the resin, thus regenerating the
sorbent, is the key of a new process referred by the authors to as
‘‘a moisture swing absorption system’’. Then the sorbent is dried
and can again absorb CO2 and start another DAC cycle. A first
proof of the concept has been done in 2007 by the Georgia
Institute of Technology and a commercial partnership called
Global Thermostat [27,28]. A cost analysis has been carried out
by the authors: the energy consumption for regenerating this
solid sorbent represents a small part of the usual amount needed
for CCS. According to Lackner and his partners, if mass production
of the device was performed, costs of complete DAC could be
reduced to nearly $30/ton of CO2 instead of the currently
estimated $100/ton with conventional CCS.
The overall process is described in Fig. 3 [29].
The plastic sheets made from dry alkaline resin are exposed
to the wind flow and as air passes trough, the CO2 loads up on
the resin until almost all sites have reached the acid–base salt
Fig. 2. Keith’s DAC facility ([22] US patent 2010/0064890).
state. The device is then isolated in a closed regeneration
chamber where the air is pumped out. Then by wetting the
the wind. Moreover, his devices, an air capture system called resin and warming it up to 40–45 1C the captured CO2 is
‘‘artificial or synthetic tree’’, uses another capture technique in released, and the resin reverts to the base state. The concen-
which the CO2–sorbent interaction is weak and thus the sorbent trated CO2 which has been released will be pumped out and
regeneration and the CO2 release is much less energy consuming compressed into a liquid at more or less 70 atm depending on
than for conventional CCS. Lackner estimates the financial cost of temperature. Compression also will force the residual water
the technology to be $206/t CO2 for immediate small scale vapor to condense: it is withdrawn and reused. Once the resin
implementation; and to be around 30$/t CO2 after widespread has dried, it can begin absorbing CO2 again and a new cycle
mass production rollout. Indeed, the anticipated main economy of can start.
scale is based on the fall in the building costs of the units. Many Energy consumption by the process machines is dominated
other possible scale economies will be discussed later. by two steps. The first step consists in pumping the air out of the
These ‘‘artificial trees’’ mimic the processes or emulate the regeneration chamber. The second step, which demands far
action of natural trees by absorbing CO2 directly from the atmo- more energy, consists in compressing the CO2 from a fraction
sphere using solid alkaline absorbents, relying mainly on wind to of an atmosphere to the pressure required to liquefy it, but this
perform mass transport of air across absorbent. The absorbent is step is similar to conventional CCS. According to Lackner’s
then regenerated by a low temperature process, releasing almost calculations his DAC process collects five times more CO2 than
pure CO2, and this step represent a technological breakthrough it is generated by fossil power plants to provide its energy
comparatively to current CCS for the same step as it requires consumption.
smaller quantities of energy. Therefore the maintenance costs for DAC are reduced com-
paratively to CCS, as the alkali component regeneration is done
2.3. Technical differences between DAC and CSS under mild conditions compared to liquid amines that are
warmed up to 100–140 1C in presence of numerous impurities
Indeed, the main difference between CCS and DAC comes from or pollutants coming from the flue stack (NOx, SOx, soot, heavy
the costs of CO2 release and sorbent recycling and regeneration. metals, etc.).
For flue stack gas scrubbing, the fossil fuel power plants have to A good sorbent should not only be cheap, but also should not
achieve a ‘‘carbon neutrality goal’’. For an almost zero footprint escape from the capture system and should not be environmen-
power plant, carbon capture yields need to be as quantitative as tally hazardous and should withstand many recycling loops.
possible (commonly up to 90%), therefore currently used sorbents Degradation of liquid alkali sorbents requires its replacement
(generally liquid amines) bind very strongly to the CO2, and, as a after some cycles. Solid sorbents may be more resistant, especially
consequence, the energy required for releasing the CO2 and if submitted to milder conditions (i.e., less corrosive pollutants
regenerating the sorbent is quite important. This is the driving and temperatures o50 1C). Operating costs of DAC could thus be
cost of the CSS process. reduced comparatively to CSS, as components such as binding
Concerning DAC, there is no carbon capture yield goal, so 30 or materials, are long lived and retain their effectiveness through a
40% yield can be considered as ‘‘good enough’’. As DAC can be larger number of cycles.
86 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

The SCPP is a renewable energy facility, featuring continuous


power generation 24 h d  1 and low operation costs. The SCPP
technology was experimentally tested at Manzanares in Spain,
where a small prototype of 50 kW was built in 1982 and
successfully tested during 7 years, by the team of Professor
Schlaich [31]. The results of the operation of this demonstration
plant were published by Haaf [32,33], and then by Schlaich in his
1995 book [34].
In the last decades, many researchers have carried out studies
on SCPP. First, authors used thermodynamic analysis in order to
study the performance of power generating system [35–37].
Later, authors focused on costs pre-estimation on large-scale SC
system. Thus, Pasumarthi and Sherif [38,39] established mathe-
matical models, based on experimental devices, describing the
fluid flow and heat transfer features, while the team led by von
Backström [40,41] put emphasis on turbine performance of the
SCPP and Ming [42–44] set up analytical models and performed
numerical simulations on turbine performance and on flow and
heat transfer.
SCPPs are environmentally-friendly compared with existing
coal-fired power stations and with other current renewable
energy power generating technologies. For Bernardes [45]
depending on the power output and on the life expectancy taken
for the SCPP which can be up to more than 100 years, the
environmental analysis results in, respectively approximately
170 and 70 g CO2-equivalents/kW h for 5 and 100 MW SCPP, as
with larger plants the consumption of raw materials and
resources decreases. For Weinrebe [46] the greenhouse gas
emissions form a 200 MW SCPP are almost similar than for wind
turbine or dish sterling, almost 4 times lower than for photo-
voltaic’s, and more than 50 times lower than for an Australian
coal plant, (respectively 18, 16, 21, 84 and 980 g CO2 equivalents/
kW h). Coupled with a CSS or a DAC, SCPP becomes a ‘‘negative
emissions technology’’, which is not the case of coal-fired power
plants associated with CCS.
Moreover, contrary to other thermal power generation technol-
ogies including concentrated solar power (CSP), coal, gas and nuclear
which are water intensive consumers, SCPPs do not use water for
the electricity generation as they do not need any heat sink, this can
be an important factor in regions with water constraints.
At the end of December 2010, the Chinese authorities [47]
announced the construction of a 200 kW SCPP experimental demon-
stration prototype in Bay Area in Wuhai Jinsha Inner Mongolia in
Fig. 3. Overall Lackner’s DAC process (inspired from [29]). China [48] and the project of a 25.1 MW SCPP for 2013, accounting
for desert area of 2.51 km2 and 1.26 billion f (yuan) investment. This
renewed hope in the supporters’ community of this unusual renew-
Regardless of the discussions and controversies on the com- able energy, since the previous serious project dated back in the
parative costs of future CSS and DAC processes, as said by Keith 1980s in Spain. The same happened with the multiple announce-
[30] there is no single ‘‘cost of air capture’’, but rather air capture ments made by the Australian company Enviromission [49]a, b] of
presents a potent opportunity to directly manage atmospheric the La Paz solar tower project in Arizona with the Southern California
CO2 concentrations with a different set of benefits and trade-offs Public Power Authority Power Purchase Agreement approved in
than other emissions mitigation options. Costs depend on design October 2010 [50] for 2014.
specifics, local prices of construction and energy, and on the Several teams analysed the possibilities of building SCPPs in
geographic and economic niches. In this paper reducing DAC costs other places around the world, for instance Dai [51] studied the
by at least a factor of two is explored. possible performance of a SCPP in the north western regions of
China, Zhou [52] did the same for the Qinghai–Tibet region of
China and Larbi [53] in the south western region of Algeria.
3. Interest of solar chimney power plants Mostafa [54] estimated the performance of a solar chimney under
Egyptian weather conditions and Hamdan [55] in the Arabian
A solar chimney power plant (SCPP) consists of a circular Gulf region. Meanwhile Ketlogetswe [56] studied the case of
greenhouse (GH) type collector with a tall chimney at its centre Bostwana, Sangi [57] did it for Iran. Nizetic [58] looked at the
[31]. The air inside the transparent GH roof several meters above feasibility of implementing SCPPs in the Mediterranean region
the ground is heated by the sun. The height of the collector and Bilgen [59] in higher latitudes. Zhou [60] completed an
increases from the exterior to the centre adjacent to the tower exhaustive review of solar chimney power technology and also
base. The hot air rises through the chimney by buoyancy effect performed an economic analysis of the floating SCPP [61] idea
where turbines produce electricity. promoted by Papageorgiou [62]a–d]. Chergui [63] analyzed the
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 87

Table 1 generator to produce electricity. A similar idea of coupling


Typical dimensions and electricity output of different size SCPPs. DAC with energy towers was proposed by Bonnelle [75] and
de_Richter [76]. In 2011, a US patent by Eisenberger [77] men-
Capacity MW 5 30 100 200
tioned a solar heating tower or chimney as a solar driven air
Tower height M 550 750 1000 1000 current source to replace fans for CCS, but did not mention the
Tower diameter M 45 70 110 120 synergies and scale economies that will be discussed later in this
Collector diameter M 1250 2900 4300 7000 paper for SCPPs associated with DAC by artificial trees.
Electricity outputa GW h yr  1 14 99 320 680

a
At a site with an annual global solar radiation of 2300 kW h m  2 yr  1 3.2. Optimization of plant output

In his book, Schlaich [34] indicated that double glazing the


thermo-hydrodynamic aspects and very recently Kasaeian [64]
collector roof can increase annual plant output by 28.6% com-
performed an experimental investigation of the climatic effects on
pared to the same plant with single glazed collector.
the efficiency of a SCPP pilot prototype.
In order to increase the global performance of the solar
Table 1 shows the typical dimensions of SCPPS for several
chimney, several other authors [78–80] have envisioned a double
electricity outputs as calculated by Schlaich [31].
glazing roof to increase the ability of the greenhouse collector to
In order to give an example, for the ‘‘La Paz solar chimney
retain heat, but as the investment cost increases drastically,
project in Arizona’’, literature reports [65] a ‘‘4 square-mile
double-glazing is only envisioned for an area close to the
greenhouse (10.36 km2) directing heat toward a 2400-foot
chimney, where the air temperature under the collector is higher.
(731.5 m) tall concrete chimney’’, the total area available on the
In his PhD thesis, Pretorius [81] found that the effect of double
2 Arizona sites [66] is 5500 acres (22.26 km2) each.
glazing the collector roof can increase of annual plant output up
For a 200 MW SCPP, with a chimney of 120 m diameter, and a
to 32.3%. Pretorius also studied the effect of double glazing only
wind speed of 15 m s  1 [34] the airflow across it is chimney is
certain parts of the collector (the hottest part, near the chimney)
about 14.66 km3 day  1 (5350 km3 yr  1). This huge airflow allows
while the rest of the collector stayed single glazed.
the assimilation of SCPPs to giant atmosphere vacuum cleaners.
Some authors [67] proposed SCPP variants for cleaning urban
atmosphere or removing heat.
Hot air for the solar tower is produced by the greenhouse
effect under the GH collector consisting of a glass or plastic
glazing [68] which admits the solar radiation component and
retains long-wave re-radiation from the heated ground. Thus the
ground under the roof heats up and transfers its heat to the air
flowing radially above it from the outside border to the tower.
Due to the ground thermal storage the SCPP can operate all year
round 24 h d  1 [69] and closed black pockets filled with water
and placed on the ground act as thermal storage.

3.1. Need to couple DAC with an energy carbon neutral source

To achieve the maximum environmental benefits, the electri-


city needs for DAC must be obtained from carbon neutral sources.
Air remediation processes using solar energy has been investi-
gated, for instance by Von Zedtwitz-Nikulshyna [70] using CSP as
the source of a high temperature process heat.
DAC processes using wind energy are mentioned by McGlashan
[71]. The use of wind turbines built adjacently to a fleet of artificial
trees to provide the required electric power seems interesting. Apart
from savings in planning and installation costs, there are some
benefits to this configuration, but wind intermittency is a handicap
and a system driven by wind must operate not only intermittently
but with a very low pressure drop through the contactor.
House [72] proposed using several other non-carbon energy
sources (e.g., nuclear, geothermal, hydro power, wind power)
with a different DAC concept. Any intermittent carbon-free
energy source, like wind or solar thermal or solar electric power,
will poorly match with DAC unless an energy storage system is
included to produce baseload power.
In 2001 Lackner [73] proposed coupling another DAC technol-
ogy to a ‘‘convection tower’’ that could either provide electricity
or CO2 capture. In fact the description he reported corresponds to
the ‘‘energy tower’’ developed by Zaslavsky [74] of Technion
Institute in Israel. This ‘‘energy tower’’ consists in spraying water
Fig. 4. SCPP with inner secondary roof to increase power output, proposed by
inside a tall chimney were the evaporation of water cools the hot Pretorius [81] and the possibility of adding 4 layers of photocatalytic coating (on
dry air, which falls down through the tower as it cools and the ground, on the inside side of the main canopy and on both sides of the inner
becomes more dense, at the bottom of which a turbine drives a roof).
88 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

In order to have some effective control of the SCPP output channels underneath the secondary roof in the collector, as illu-
(mechanism to control the air flow through the plant), Pretorius strated by Fig. 5. These channels can be fully opened or closed off at
studied the effect of a secondary roof (at 3.5 m high) (Fig. 4), and the bottom section outlet, thereby incrementally increasing or
also the effect of a tertiary collector roof (at 2 m high) under the decreasing the collector air-flow area. Papageorgiou [82] proposed
main canopy. During the sorbent regeneration process, the DAC a secondary modular solar collector made by a series of triangular
device can play the role of this control mechanism to regulate warming air tunnels with double glazing transparent roofs.
power output.
Pretorius suggested that the air flows constantly without being
regulated through the top section, while an air-flow regulating 3.3. Base load and peak load
mechanism at the bottom section outlet controls the mass-flow
through the bottom section of the collector. The secondary roof is All electrical needs for the processes: CO2 release and sorbent
expected to confer to the plant the ability to store and then regeneration, 45 1C water vapor steam, CO2 compression, transfer
release energy on demand for peak load consumption from the and transport will be provided by the SCPP and this energy is a
bottom section of the collector in order to regulate or increase the renewable one.
plant power output. On the one hand, this local electricity consumption and also
During base load, at times when less power is required, the the friction losses under the greenhouse, mainly due to the CO2
bottom section is closed and energy is stored in the ground. If more alkaline polymeric absorber (leaves of the artificial tree) and the
power is required, the bottom section is opened in a controlled additional equipment will decrease the overall electrical produc-
manner, which results in an extra air-flow under the secondary roof. tion of the power plant.
This air-flow extracts energy from the ground and subsequently On the other hand, the CO2 capture infrastructure (closed
boosts plant power output. Fig. 5 illustrates schematically the boxes for the regeneration process of the sorbent) will allow a
operation of the plant when introducing a secondary roof. better control of the electrical production during peak load when
A further refinement to achieve additional control which was the electricity prices are much higher than during base load. The
considered by Pretorius is the implementation of multiple radial investment costs for this infrastructure is part of the DAC plant,

Fig. 5. (a) (left): Pretorius proposal of multiple radial channels underneath the collector: fully opened or closed off at they increase or decrease the collector air-flow area,
(b) (right): similar configuration obtained with ‘‘open’’ or ‘‘closed’’ DAC devices under the canopy.

Fig. 6. Analogy between wind turbine and artificial tree.


R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 89

therefore it acts in synergy with the power generation part The resin based CO2 absorbent – currently a specific product –
of the plant. will become cheaper in the future. As the alkaline resin and its
support will become cheaper, it can be anticipated that the ‘‘tree
trunks’’ may still represent more than 25% of the investment costs
4. Rationale of coupling DAC with solar chimney power plants even if it will depend on the eventual ‘tree’ design adopted. The
SCPPs compressors and pumps (as well as, but to a lesser extent the heat
exchangers and the humidity generators) contained in each tree
CO2 capture followed by geological sequestration or transfor- will become the principal capital cost as their price will not fall.
mation associating DAC under the SCPP greenhouse allows Fig. 7 shows a possible implementation of the DAC under the
several scale economies. In fact SCPPs operates both with solar greenhouse of a SCPP.
and ‘‘artificial’’ wind energy and cheap energy storage allows
operation 24 h d  1.
Of course installing CO2 plastic sheet scrubbers under the SCPP 4.2. Scale economies of SCPPs coupled with DAC
canopy will increase air friction and pressure drop, thus reducing
power output production. Also the DAC process will consume Several obvious scale economies are thus possible under a
energy, but as it will be seen later many scale economies and SCPP cover:
synergies arise from the SCPP–DAC coupling.
At a given point under the SCPP cover, the air flow and the  in order to prevent CO2 capture devices downwind from others
temperature are almost constant. As seen previously the airflow to process air already depleted in CO2, by the ones upwind, all
for a model 200 MW SCPP with a 120 m chimney diameter and an the capture units can be located in an optimum perimeter at
inner wind speed of 15 m s  1 is about 5350 km3 yr  1. The daily the same distance from the centre of the SCPP collector, and all
CO2 flow under this SCPP is 11,507 t; the annual CO2 flow is units can capture the same amount of CO2;
4.2 million tons. Even with only a 30% capture yield (i.e.,  no need of high ‘‘trunk’’, no need of deep ‘‘roots’’;
3452 t d  1 or 1.26 Mt yr  1), the comparison is still interesting
with the 680 GW h of renewable electricity produced in one year
by the same SCPP, which allows annual savings of 0.9 million tons
of CO2 emissions [83] and provides enough electricity to about
100,000 American or Australian households.

4.1. Synergies of SCPPs coupled with DAC

In order to be submitted to an adequate wind speed, the


‘‘artificial trees’’ from Lackner [9] need to be quite high to reach a
height where the airflow is sufficient. But even if they are located
high enough, the artificial trees will operate only when wind
velocity exceeds some cut-in value. Analogous rules govern the
operation of wind turbines, where annually averaged wind power
is typically one-third of peak wind power. Under SCPPs there is no
airflow intermittency. Fig. 6 summarizes the analogies between
wind turbines and artificial trees.
Although broad description of the technology is available, the
early-stage proprietary nature of the work means that many
details are not yet in the public domain and in particular the real
costs of the different elements.
Lackner [9] has evaluated the expected financial cost to build
and operate his artificial trees. He estimates that once mass
production has been reached, the individual units of 500 m2 (able
to capture 10 t CO2 d  1) would cost about $20,000 each including
all equipment and material comparatively to $200,000 with
current technology.
The image of artificial trees [84] with trunk, stem, branches,
leaves and roots is interesting to summarize ideas, but it is not so
poetic and the tree trunk is expected to be the shipping container
that will be used as regeneration chamber to release the captured
CO2 and regenerate the resin. It has to be equipped with some
kind of engine and hydraulic cylinders for lifting and lowering the
resin trays, outside or inside the chamber, respectively for carbon
capture and for regeneration purposes.
In the case of wind power, 26% of the cost [85] comes from the
tower and the foundations, 24% of the cost comes for gearbox and
generator and nearly 50% for nacelle, machinery, rotor and blades.
In the case of artificial trees, the ‘‘tree trunks’’ are only useful to
support the active part of the device (the ‘‘leaves’’ made of an
alkali polymeric resin). The roots (foundations) of this ‘‘synthetic
trees’’ are also important as height and resistance to strong winds Fig. 7. Lackner CO2 capture devices, made of alkali polymeric resin for DAC
needs to be high. process under a SCPP cover.
90 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

 no need of engine and hydraulic cylinders for lifting and during electric peak load consumption when selling price is
lowering the DAC devices, each unit having already four closed higher. The SCPP locations close to CO2 disposal or sequestration
faces only two ‘‘doors’’ are needed to close the individual sites drastically decrease infrastructure investments for CO2
boxes needed for the regeneration process; transportation by pipelines, the DAC devices being very close to
 the investment made for the regeneration chambers of the each other, pumps and compressors are shared between several,
DAC process will allow the SCPP to regulate the input and all yields are increased and there is no intermittency in any
output airflow: closing the air entrance during base load process y.
electricity consumption will allow the SCPP to accumulate Matthews and Caldeira [86] have shown that to prevent
solar heat under the canopy and in the energy storage water further warming of our planet reducing CO2 emissions to zero
layer. During the peak load more power output will be would not be sufficient to entail an appreciable cooling, because
obtained at a time when electricity prices are several times CO2 already present in the atmosphere would continue to trap
higher than during base load; heat. Therefore, in order to cause a significant cooling, atmo-
 shorter pipes and pipelines are needed; less infrastructure is spheric greenhouse gas concentrations need to be reduced. SCPPs
required; associated with DAC systems can at the same time provide
 at a given point under the SCPP GH cover the air speed, the renewable energy and remove CO2 from the atmosphere, through
airflow and the temperature are almost constant; under the a viable negative emission technology. SCPPs are robust and long
GH there is no wind intermittency so the DAC can capture the lasting plants and they produce electricity at almost zero cost
same amount of CO2 four times quicker than the same device after the repayment of loans and capital.
submitted to natural wind;
 the SCPP collector will protect the DAC devices from heavy 4.3. Advantages of DAC under SCPPs
rains and from strong winds; operating and maintenance costs
will be reduced and longer service life will be obtained: the DAC can help mitigate emissions from small sources unsuita-
replacement of the ‘‘trees’’ will be done after more years; ble for direct capture. Even old emissions can also be compen-
 more devices can be set up in a smaller area, but still collect sated by DAC. Lackner [9,73] explained that this technology also
more CO2 in a reduced amount of time; as there is no wind separates the source from disposal in a way that for instance CO2
intermittency and airflow speed is in the order of 3 to 4 m s  1, emissions from Europe, China or the USA can be compensated in
more cycles are possible in less time; in other words, four the African Sahara desert without long distance transportation of
cycles can be performed per day, and since the total area of the compressed CO2 by pipelines or without long distance shipping
greenhouse opening is 44,000 m2 (7 km diameter and at least by boats to the disposal site.
2 m high at the external border), nearly 3500 t of CO2 can be New sorbents with better chemical kinetics and lower binding
captured per day with four times less resin scrubber; energies can substantially improve the cost of dilute CO2 capture
 the regeneration process can be quicker (natural drying of the from ambient air, comparatively to CO2 capture from concen-
resin); trated sources in fossil carbon power plant chimneys. But solid
 the heat requested for the humidity production at 40–45 1C sorbents can also be useful for conventional CCS as demonstrated
needed for the CO2 release from the resin can be solar and by the important research efforts is this field [87–89].
renewable. A part of the heat can be given back to the SCPP
after resin regeneration; no heating resistors needed, nor heat 4.4. Proximity of SCPPs from disposal sites
exchangers, as the heat requirements were planned by Lackner
to be supplied from heat recovery in the CO2 compression In order to minimize transport and improve the cost of the
process; overall direct air CCS process as well as several scale economies,
 the heat released by the CO2 compression step can be recycled SCPPs can be built in the vicinity of appropriate sequestration
under the SCPP; sites like geological formations suitable for sequestration (deep
 less compressors, less pumps, which is important as they are saline aquifers) or close to oil wells (for enhanced oil recovery) or
considered to be among the more expensive parts of the mining facilities.
investment after the polymeric resin has entered mass Near abandoned and old underground coal mines are generally
production; millions of tons of coal heaps, coal mine tailing dumps and coal
 reduced set up costs; slurry residues. As albedo of this waste is generally low, spread
 at the locations where the devices will be installed, the below the canopy collector of a solar chimney this waste can help
support structure of the canopy collector can also be used to accumulate heat for night electricity production.
support the resin sorbent (the ‘‘branches, stem and leaves’’ of Transforming acidic CO2 into mineral carbonates by reaction
the artificial trees) with basalt and alkaline rocks has received extensive attention
 the electricity for pumps and compressors can be renewable [90–93] as a way to mitigate CO2 emissions. SCPPs can be built in
energy from the SCPP production; locations containing this type of ultramafic ores.
 if energy is produced with fossil fired power plants an amount Some authors [94] have proposed the production of algae
equivalent to 20% of the CO2 captured is again released in the biodiesel associated with solar chimneys.
production of the electric power needed for the regeneration Among the pros and cons, it can be argued that since the
process of the sorbent. As renewable energy is used to capture Manzanares SCPP Spanish prototype was built in the 1980s, with
CO2 no new CO2 emissions are made, thus the overall yield is a 200 m tall chimney, no industrial scale SCPP with a 700 to
automatically increased by 25%. 1000 m high chimney has been built. There is no financial or
scientific interest to build intermediate prototypes with chimneys
As a summary: for any given process configuration, the cycle from 300 to 600 m. These prototypes would be expensive to build
time would ideally be as short as possible in order to maximize and the electricity produced would not be competitive if it is not
the utilization of installed equipment, this is the case for a DAC subsidized. On the one hand, the fact is that even if the proof of
system under a SCPP. The SCPP investment reduces the infra- the SCPP concept is already done and taken for granted, to be
structure investment for Lakner’s DAC device type, meanwhile the competitive with other power facilities, SCPPs need to be giant
DAC investment allows the SCPP to produce more electricity structures. On the other hand, the scientific proof of the concept
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 91

for a DAC system has also already been done by Lackner and his analysis showed that the most important parameters are the
associates at relatively low cost, and there is no real interest to alkaline solutions concentration (1 or 2 M) in the absorber, the
immediately build a giant DAC facility as the one proposed in this rate of CO2 removal (50 or 80%) and the air-velocity.
paper associated with a SCPP. The financial and industrial proof of Holmes performed his cost optimization on a slab geometry
DAC interest can follow up a classical scale up with progressive contactor that borrows characteristics from gas scrubbing towers
growth of costs from pilot plants to bigger and bigger prototypes. commonly used in the chemical processing industry, and from
In other words, there is a financial risk to build a giant SCPP or a cooling tower designs that are well suited to cost-effective bulk
big DAC facility, today no one will take both risks together. But as air processing. The experts who wrote the APS report studied a
soon as several industrial scale SCPP will be built (for instance in packed tower reference design for a contactor capturing CO2 out
La Paz, Arizona, USA), installing competitive DAC systems will be of air with an estimated overall cost (for the contactor alone) of
possible at lower costs. $180–240 per tonne CO2. According to Holmes, the APS used a
Alternative processes are needed to decrease the level of reference design based on closed counter-flow gas scrubber
atmospheric greenhouse gases. The availability of negative emis- column technology, a more expensive design choice, than the
sion strategies can help to meet 2 1C temperature limits. ‘open’ contactor device derived from cooling tower technology
Making negative emission strategies available will reduce the used by him. As a matter of fact, the Socolow-APS report does
cost of keeping year 2100 CO2 concentrations near their current itself state that such a system ‘would be much less costly’ (APS
level, thus planning to deploy negative emission technologies [14], Section 2.4), and that ‘‘the largest uncertainty in the DAC
should be further considered. cost is the cost of the air contactor’’.
Holmes employs fans already commonly used in forced-
4.5. Cost reduction potential of SCPPþDAC draught cooling towers and for which cost and efficiency are well
known. The energy cost of operating the contactor is determined
The process proposed in this chapter associates a solar updraft by Holmes [97] from the pressure drop and a pressure–volume
chimney with direct air capture as a tool for emissions mitigation work term, as for him the choice of air velocity is one of the many
and fits into the portfolio of technology options for managing trade-offs between capital and operating costs, as high air
emissions and climate risk. In order to ‘‘fight global warming’’ as velocities increase energy consumption, which is a primary
summarized in the title of this paper, in Sections 4 and 5 a contributor to operating costs.
complementary technology will focus on enabling production of In the case of our own proposal with SCPPs, there is no need to
transportation fuels with low carbon intensity. use air-fans (no investment and no electrical consumption), as the
In the literature plenty of data on DAC costs is available and stack effect produces a ‘‘free’’ air-flow with air velocities which
there is a significant variance in them. An article published in can be adjusted in the optimal range 1 to 3 m s  1 as determined
2012 by 6 scientists lead by House [95] estimates that total by Holmes.
system costs of a DAC system will be on the order of US $1000 per Kulkarni [98] carried out an economic analysis to obtain a net
tonne of CO2, based on experience with as-built large-scale trace operating cost for air capture of CO2. His cost estimates do not
gas removal systems. They conclude that their ‘‘empirical’’ ana- include capital expenses necessary to construct or maintain the
lyses of operating commercial processes suggest that the ener- air capture units. He finds that the total energy required is
getic and financial costs of capturing CO2 from the air are likely to dominated by the parasitic losses (sensible heat requirements of
have been underestimated as several published analyses suggest the contactor (40%) and the adsorbent (28%)) and not by the
that DAC systems may only cost a few $100/t CO2. mechanical energy associated with air flow ( 5%). On the basis of
As mentioned in Section 1.2, the 100 pages and two-year study their analysis of factors such as source of electricity, availability of
of the APS conducted by Socolow and 13 scientists [14] concluded low pressure steam, and geographic location, they estimated the
that ‘‘CO2 capture from air (air capture) will cost US $ 600 to $800 net operating cost of capture to be  $100/t CO2.
per tonne CO2 avoided’’. But the authors already cited in refer- The structural cost analysis breakdown of Holmes evaluates to
ences [15–21] found quite different costs ranging from US $120, 19% the cost percentage of fans and labour materials. It also
$250, $420, $630/t CO2 and even $30 as a long terms goal [9]. evaluates to 36% the structural costs for fans, pumps and absorp-
Several sources that performed a sensitivity analysis and implied tion packing. Zeman [7] estimates at 20% the total energy
this APS report was too pessimistic in its assessment were quoted requirements for air movement of DAC and 56% for calcination
by Rudolf [96]. (thermal energy used in his type of regeneration process).
In response to the publication of the APS report, in a 25 pages In this paper we extrapolate some of the already published
article, Holmes [97] proved that the total costs for air contacting reports, and use them as a calculation base for a very conservative
alone (no regeneration) can be of the order of $60 per tonne CO2 and roughly estimate of an approximate ‘‘cost reduction poten-
(between $43 and $95). This estimation is based on real engineer- tial’’ for some steps of the new process proposed in this paper.
ing and cost data derived from studies performed by a company To simplify the life-cycle analysis, the electricity supply needs
named Carbon Engineering Ltd. The regeneration cycle of their of the Holmes process are thermally integrated with the regen-
process was not evaluated, as it is similar to the regeneration eration cycle, and the CO2 from the process is captured as part of
cycle of conventional CCS processes. the regeneration cycle proposed. In the proposal made in this
For comparative purposes, to scale up major equipment costs paper, using CO2-free renewable energy produced by the SCPPs,
to full facility cost estimates Holmes [97] used similar costing there is no more CO2 to capture in order to compensate the power
methods and capital recovery factors (or even more conservative consumption of the fans, thus 25% more CO2 will be captured for
ones) than in the Socolow-APS report on DAC [14]. the same cost (see Section 3.2). If we apply this conservative cost
To explain the four fold discrepancy between their CO2 capture reductions and efficiency increases to the capture part of the
costs evaluation and the evaluation performed by the APS team, process, the $60 per tonne of CO2 found by Holmes fall down to
they emphasize that it did not arise from differences in costing nearly $40 per tonne. The other electricity consummation costs
methodology, but from the APS’s choice of a design, and in the (i.e., pumping and compressing) are not subtracted, as if the DAC
operating differences of the principal parameters issued from the process consumes electricity, the SCPP own revenue is reduced.
sensitivity analysis. For both Socolow and Holmes, a detailed cost In the APS report, on table 2.3 the energy requirements of the
optimization reflects engineering experience and the sensitivity absorber fans per tonne of CO2 captured is 0.63 GJ t  1, and only
92 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

0.07 GJ t  1 for liquid pumping. A similar potential cost reduction, points out that their analyses suggest that with absent radical
although not exactly identical can be applied to the Socolow [14] technological breakthroughs, air capture is unlikely to be a practical
evaluation. According to Desmond [99], if the process power CO2 mitigation technology and that it can only be viable (i.e., CO2
comes from a zero emissions source, thus the cost of CO2 avoided negative) if powered by non-CO2 emitting sources. The SCPP
drops from $610/t to $430/t taking into account the evaluation provides a radical technological breakthrough, is a non-CO2 emitting
performed in the APS report on DAC for the complete process, as source and at the same time its main goal is to produce an unusual
the APS report estimates to 0.7 the avoided CO2 as a fraction of renewable energy, with many synergies and scale economies when
CO2 captured. associated with DAC as proposed in this paper.
Our cost reduction potential is quite conservative, as we do not
take into account the structural cost reductions provided by the
SCPP structure itself, nor the capital charge factor reduction (there 5. Carbon dioxide recycling or artificial photosynthesis
is no investment costs for fans), or the sensible heat provided by
the greenhouse for the regeneration process. The stabilization of the atmospheric levels of CO2 will require
A full CCS process [100,101] also includes: the sorbent regen- the use of carbon neutral technologies and fuels [104]. In a future
eration (which is energy consuming); CO2 transportation till carbon-constrained economy, the production of transportation
disposal site (which requires high investments costs) and storage. fuels from sunlight, at competitive costs with petroleum-based
The scale economies and synergies already described in Sec- fuels, is a formidable challenge facing chemists today. The use of
tion 3 when associating a SCPP and a DAC system reduce the CO2 to synthesize commodity chemicals has been reviewed by
capital cost and the contingency and further decreases the Arakawa [105]. Many reviews describing several methods to
complete DAC and sequestration process. convert CO2 into fuels [106–108] or about the fixation and the
It is not in the scope of this paper to perform a complete transformation of CO2 [109,110], have been published. Lackner
economic evaluation of the proposed process, but one can cite participated to the Graves [111] article which reviews the many
among investment reductions, the fact that when captured at a possible technological pathways for recycling CO2 into fuels using
fossil power plant, the CO2 often needs transportation over long renewable or nuclear energy, considering three stages—CO2
distances, using pipelines costing over $1 million per mile [5], in capture, H2O and CO2 dissociation, and fuel synthesis. Dissocia-
expensive land areas or countries and crossing dense population tion methods include thermolysis, thermochemical cycles, elec-
areas. The installation of large pipeline networks through impassa- trolysis, and photoelectrolysis of CO2 and/or H2O.
ble or populated areas is expensive and poses high risks. Although The Lackner devices are called ‘‘artificial trees’’, because they
the financial evaluation of increased security benefits for humans can withdraw, scrub or scavenge CO2 from the atmosphere. But in
and feedstock is difficult to perform, the CO2 catastrophe that nature, plants use sunlight as energy to combine H2O and CO2 to
suffocated and killed 1,700 people and 3,500 livestock in Lake Nyos form biomass. Combining carbon capture and artificial photo-
nearby’s on August 21, 1986 should be kept in mind. synthesis by photocatalysis might have some interest if synergies
As SCPP will be built in hot deserts, when associated with DAC are possible: the ‘‘fake trees’’ will not appear less ‘‘synthetic’’ but
the location site can be chosen strategically next to the place of at least it would be better than ‘‘robot trees’’ [112].
further CO2 processing, eliminating transportation needs and As energy is required to compress to high pressure the CO2
saving $Millions in pipeline investment and capital charge factor. collected by the DAC devices in order to sequester it, it is
For instance SCPP can be built in close proximity to suitable interesting to try to find if CO2 can be used or transformed on
aquifers for geological disposal, or to oil wells to perform the spot with less energy for some other purpose. Small quantities
enhanced oil recovery [102]. These locations are often far from of CO2 can be used for biodiesel production with algae or for
dense populated areas (reducing risks in case of CO2 leaks) and enhanced oil recovery. Quite often the conversion of CO2 to fuels
the land is usually cheap. by a photo-electro catalytic approach or by the photo-electrolysis
In this Section 3, the SCPP described is associated with the of CO2 are described [113,114], but this article focuses on the
Lakner DAC type process, as more numerous synergies and scale possibilities of conversion of CO2 to fuels by photocatalysis, as
economies appear: the heat needed for the moisture swing under SCPP a huge amount of free solar energy is available and
regeneration process (45 1C) is in the range of the SCPP air- therefore synergies are possible.
temperatures (25–70 1C) and this low temperature heat can be
provided to the DAC under the SCPP greenhouse.
House [95] recognises that the 300-fold concentration differ- 5.1. Interest of photocatalysis
ence of CO2 in flue gas (12%) and air capture (0.04%) causes the
minimum work to increase by only about a factor of three, as Photocatalysis uses photocatalysts under UV or visible light
previously stated by Lackner [9]. Therefore, the drawbacks of the illumination to reduce or to oxidize pollutants to innocuous
high dilution of CO2 in the air can be compensated by other compounds, generally at room temperature and under atmo-
advantages of air capture. Wang [103] performed a thermody- spheric pressure. Photocatalysis is an emerging technology that
namic analysis of several fuel synthesis methods with CO2 has gained much attention in air and water pollution control.
captured from atmosphere and concluded that the efficiency Photocatalytic reaction systems collect great attention because
could be increased by developing technologies with lower elec- the systems need only photons as the process source and the
tricity requirements like solar energy. Wang found that compared photo-induced chemical species have strong oxidation and reduc-
to ‘‘the energy/exergy consumed by electrolysis, the energy/ tion potential. Recent advances in visible-light-responsive photo-
exergy penalty from CO2 capture is insignificant’’. catalysts make this technology even more attractive [2].
DAC is complementary to CCS as it provides a route to manage The ability to coat almost any surface with photoactive materials
CO2 from the transportation sector and allows industrial economies is one of the reasons why photocatalysis has quickly been imple-
of scale to deal with small and mobile emission sources (nearly 60% mented. A large range of applications have already been commer-
of global carbon emissions). Dealing with small and dispersed CO2 cialized and many others are still in the research phase. Some recent
emitters with DAC would make the CO2 collection independent of commercial applications include: indoor air cleaning, process vent
CO2 sources, and the atmosphere could thus been considered as a treatment, groundwater treatment, disinfection of hospital rooms,
means of transporting CO2 emissions to the site of its capture. House self-cleaning lamp covers, antifogging mirrors, etc. and at very large
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 93

scale: self-cleaning paints, self-cleaning glass, and self-cleaning Recently, Zhang [131] selectively produced CH4 from CO2 on
coatings. Pt-loaded TiO2 photo-catalyst; Nasution [132] performed the
synthesis of methanol from CO2 by photocatalytic reduction over
5.2. Photocatalytic reduction of carbon dioxide copper-doped TiO2. Li [133] found that CO was the primary
product of CO2 reduction for TiO2–SiO2 photocatalysts. The addi-
Ganesh [115] presented recently a comprehensive review of tion of Cu2O species increased the overall CO2 conversion effi-
literature reported on conversion of CO2 into methanol following ciency as well as the selectivity to CH4, by preventing the
various routes including catalytic, thermal, biological, electrochemi- electron–hole recombination and enhancing multi-electron reac-
cal and photoelectrochemical. This paragraph briefly reviews the tions. The peak production rates of CO and CH4 reached, respec-
potential application of photocatalysis to recycle CO2 in valued tively 60 and 10 mmol g  1 h  1, for 0.5%Cu/TiO2–SiO2.
chemicals by photocatalytic reduction or artificial photosynthesis,
and then proposes a SCPP implementation. 5.3. Experimental conditions and yields of CO2 reduction by
The reaction scheme of the photocatalytic reduction of CO2 is photocatalysis
the following:

CO2 þH2Oþhu þphotocatalyst-carboneous products þO2 (5) The possible use of heterogeneous photocatalysis to produce
fuels using solar energy to supply clean and renewable energy is a
The reduction reaction requires first (or simultaneously) the very attractive concept. A current research objective in this field is
water-splitting [116,117] to produce hydrogen which will then to develop a stable visible light-responsive photocatalysts capable
react with the CO2. The photocatalytic water-splitting was first of achieving water splitting and/or CO2 reduction (artificial
described in Nature by Fujishima and Honda in [118] and since photosynthesis). In general, it can be achieved when a photo-
then researchers have been investigating semiconductor systems catalyst is modified with a suitable co-catalyst and in the past
for the production of hydrogen from water. Using renewable years, there has been significant progress in this area. To date,
resources for the production of hydrogen and other fuels is more than 100 photocatalytic systems based on metal oxides
attractive as a sustainable non-polluting, long term contribution have been reported to be active for overall water splitting.
to supply portable high-density energy sources. According to Maeda [134] some of these oxides, consisting of
A very complete review of the recent developments in photo- early-transition-metal ions (e.g., Ti4 þ , Nb5 þ , and Ta5 þ ) modified
catalytic water-splitting using TiO2 for hydrogen production has by a reaction promoter such as NiO, exhibit excellent quantum
been made by Ni [119]. Recently Li [120] reviewed the current yields, as high as several tens of percent, without the need for
progress in fuels’ generation directly driven by solar energy. sacrificial electron donors or acceptors.
In 1987, the team of Professor Graetzel [121] reported in As it can be seen in Table 2, numerous photocatalysts have
Nature the photo-methanation of CO2 at room temperature and been developed, and some have achieved high quantum efficien-
atmospheric pressure using dispersed ruthenium and ruthenium cies. Now days many new photocatalysts work both in the
oxides loaded onto titanium dioxide (TiO2). ultraviolet and the visible light region which is the main compo-
Few years later, many other research teams like Anpo nent of the solar spectrum. At present, suitable materials with
[122,123] described photocatalytic reduction of CO2 with water sufficiently small band gap, an appropriate band gap position and
(H2O) on various TiO2 catalysts at room temperature, producing the stability necessary for practical applications are available.
methanol (CH3OH) and carbon monoxide (CO).
Several articles from Wu [124], Roy [125], Usubharatana [126],
5.3.1. Sequential reactions
Magesh [127], Indrakanti [128], reviewed all types of photocatalysts
Several authors, like Sasirekha [135] reported that hydrogen
and methods used for photo-reduction of CO2. The most widely used
levels increase rapidly, while methane contents increase some-
catalyst is TiO2 and the reaction products are generally methane, or
time after those of hydrogen H2, formaldehyde HCHO and formic
methanol. However the photocatalytic conversion of CO2 has been
acid HCOOH and the yields of methanol increase later.
studied using many types of catalysts. Kočı́ [129] reported an
Kočı́ [136] studied the effects of silver doping on TiO2 for the
overview of the literature data from 1994 until 2007 regarding
photocatalytic reduction of CO2: the yields of methane were
CO2 photocatalytic reduction in the presence of TiO2.
negligible during the first 8 h of irradiation in almost all cases.
Kočı́ [130] also studied the effect of temperature, pressure and
A substantial increase of CH4 yield was observed after 8 h of
volume of reactant solution on the photocatalytic reduction of
irradiation. The highest yield of methane was observed for the 7%
CO2 over suspended TiO2 in an annular batch photoreactor. The
Ag doped TiO2 photocatalyst. The hydrogen yields were small
same parameters were also examined in the reviews previously
during the first 13 h of irradiation in all cases. After 15 h the
quoted. Very often the CO2 reduction is conducted over TiO2 with
hydrogen yields increased slowly.
water or water vapor as the reductant.
Kočı́ reported that after several hours the yields of H2 were
The initial step in TiO2 photo-catalysed oxidation is believed to
two orders of magnitude higher than those of methanol CH3OH,
be the formation of both hydroxyl radicals and super oxide radical
(respectively 130 and 1.4 mmol g  1 of catalyst after 16 h of
anions:
irradiation). The observed order of yields (mmol g  1 of catalyst)
TiO2 þhu-e  þh þ (6) order was: H2 4CH4 4CH3OH ZCO.
H2 is generated form H2O; CH4 is obtained from CO2 and H2;

H2Oþ h -OH þH
þ þ
(7) probably in these experimental conditions CH3OH is obtained by
oxidation of CH4 and thus the yields are 5 times lower than those
In the absence of oxygen, OH radical, a strong oxidant and e  ,
of CH4 (6 mmol g  1 of catalyst).
a strong reductant, are the reactive species generated on photo-
The irradiation wavelength and many other parameters are
lysis of TiO2 in aqueous medium. In the presence of an OH or an
not yet optimized. However, all the different photocatalytic
h þ scavenger, it is possible to use TiO2 for photo-reduction
processes described in the literature and reviews quoted herein
processes.
can on the one hand help to remove CO2 from the atmosphere,
In presence of air:
but also on the other hand convert CO2 into some useful

O2 þe  -O2 (8) chemicals including CH4, H2, CO, CH3OH, formaldehyde, ethanol,
94 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

Table 2
Yields obtained for CO2 reduction by photocatalysis (from selected publications).

Photocatalyst Yielda l Light source Main product Comments Year Ref.


mol h  1 g  1of catalyst author

0.5 wt% CeO2 over 2.75 mmol h  1 g  1 for H2 Visible-light Hydrogen and The reaction proceeded through the 1992 [138]
TiO2 methane photodecomposition of H2O followed Ogura
by the methanation of CO2
b
TiO2 suspension 0.28 mmol h  1 g  1 4340 nm 9.6 W cm  2 Xe lamp Formic acid The yield of HCOOH reached a maximum 1997 [139]
in liquid CO2 value after 30 h irradiation and then Kaneko
decreasedc
0.5% TiO2 0.43 mmol h  1 g  1 4340 nm 6.2 W cm  2 Xe lamp Methane High pressure CO2 using suspended TiO2 1998 [140]
suspension powders with 2-propanol as positive hole Kaneco
scavenger
d
TiO2 powders in 1.76 mmol h  1 g  1 4340 nm 9.6 W cm  2 Xe lamp Formic acid At 9.0 MPa and 35 1C. The yield of 1999 [141]
supercritical HCOOH increased linearly with irradiation Kaneco
CO2 fluid time until 5 h and then decreasedc gradually
until 20 h
2% Cu/TiO2 or sol– e19.6 mmol h  1 g  1 254 nm 138 mW cm  2 8 W Hg Methanol Yield was significantly increased by 2002 [142]
gel TiO2 or 0.78 mmol h  1 g  1 lamp adding 0.2M NaOHf (dissolves more CO2 Tseng
Degussa P25 6.36 mmol h  1 g  1, than pure water). In addition, the OH  in
respectively aqueous solution also served as a strong hole
scavenger
g
Pt-K2Ti6O13 32.8 mmol H2 h  1 g  1 Concentrated sunlight between Hydrogen, formic With concentrated sunlight the average 2003 [143]
5.6 mmol HCHO.h  1 g  1 9 h30 and 15 h30 on sunny days acid, formal- temperatureh was 583 K in the Guan
20.6 mmol HCOOH.h  1 g  1 dehyde, methane photoreaction cell
and methanol
0.05% TiO2 2.4 mmol h  1 g  1 350 nm 4.1015 photons. Methane Yield increase 2.5 times in presence of 0.5 M 2004 [144]
2 1
suspension cm s 2-propanol as positive hole scavenger Dey
i 1 1
2% Cu/TiO2 20 mmol h g 254 nm Hg lamp Methanol Switching the irradiation from 254 to 365 nmj 2004 [145]
resulted in a 60 times decrease of the methanol Tseng
yield
k
ZnO or NiO or on average 1500 m Mono-chromatic 355 nm pulsed Methanol The initial yield rate is indicated, but in these 2004 [146]
TiO2 mol h  1 g  1 laser light (8 ns pulse, repetition experimental conditions the yields decreasec Yahaya
rate 10 Hz) after 30 min irradiation.
1.2% Cu/TiO2 0.45 mmol h  1 g  1 365 nm 16 W cm  2 Hg lamp Methanol 1.3 bar CO2 pressure f 5000 s residence time. 2005 [147]
Yield increased with light intensityl Wu
m 1 1
3% CuO/TiO2 442 mmol h g 365 nm 6  10 W Methanol Experiments performed in 1M KHCO3 at 60 1C. 2005 and
2450 mW cm  2 At 100 1C h the yield is 70% higher 2009
[148–149]
Slamet
TiO2 supported on n 40 þ38 þ 31þ 24þ 2 365 nm 1000 W Hg lamp Hydrogen, formic Mixture of products representing a total of 2006 [150]
SiO2 mmol h  1 g  1 H2, acid, methane, 135 mmol h  1 g  1 according to curve. From Sasirekha
HCOOH, CH4, HCHO, CH3OH, form-aldehyde 0.1 to 1% Ru over TiO2 gives similar results.
respectively and methanol
o
Cr doped multi 1284 þ211 þ 265 Xe-lamp Carbon monoxide, Maximum concentration obtained after 2007 and
film layers of mmol h  1 g  1 CO, methane, ethane 72 h of UV illuminationc. 70 (wt)% Cr/Ti 2010
TiO2 CH4, and C2H6, gives the best results [151–154]
respectively Nishimura
p
TiO2 coated on 6.4 mmol broadband 200 W Hg/Xe-lamps Methane and CO and O2 probably formed and not effectively 2008 [155]
sapphire, CH4.h  1 g  1 þ3 mmol hydrogen desorbed from the catalyst surface, so possible Tan
1 1
H2.h g photo-oxidation of CO back into CO2 in the
reverse reaction and thus decreasing reduction
yields
q
N-doped TiO2 6.8 mmol h  1 g  1 Outdoor global AM 1.5 sunlight Methane plus C2- According to the authors, this hydrocarbon 2009 [156]
nano-tubes of a mixture of hydrocarbons 100 mW cm  2 C6 alkanes, olefins yield obtained under outdoor sunlight Varghese
loaded with Cu and branched at 44 1C h is at least 20 times higher than
and/or Pt nano- paraffins previous published reports conducted under
particles laboratory conditions using UV illumination
r
CdSe/Pt/TiO2 0.3 mmol CH4.h  1 g  1 and l 4 420 nm 300 W Xe arc lamp Methane, Visible light photocatalysis. Gas phase product 2010 [157]
hetero- 0.01 mmol CH3OH h  1 g  1 methanol and yields expressed in ppm. C. Wang
structures trace amounts of
CO and H2
Optical fiber 11.1 mmol h  1 g  1 at 25 1C l from 400 to 1100 nm 620 nm Methanol f
0.2 M NaOH solution dissolves more CO2. 2010 [158]
NiO/InTaO4 21.0  mmol h  1 g  1 at 75 1C highest intensity 327 mW cm  2 The OH  ions in aqueous solution also act Z. Wang
11.3 mmol h  1 g  1 at 3 PM 100 W halogen lamp or as strong hole-scavengers.
i
with sunlight concentrated sunlight Production rate increases with sunlight
intensity (maximum reached at 3 PM).
h
Higher production rate at 75 1C than at 25 1C,
possible due to the increased desorption rate
of methanol
s
C doped TiO2 439 mmol h  1 g  1 Simulated daylight lamp Formic acid Carbon doping lowers the band 2011 [159]
gap and expends the absorption Xue
of visible light region

a
In order to allow comparisons yield written in italics are extrapolated values with the assumption of linear kinetics curve, the original data in given forwards.
b
8.4 mmol g  1 cat after 30 h.
c
Yield first increases then decreases, probably by secondary reactions consuming the primary products or reoxidation by the free oxygen generated.
d
8.8 mmol g  1 cat after 5 h.

(Table 2 footnote continued on next page)


R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 95

e
After 6 h: with 2.0 wt% Cu/TiO2 methanol yield was 118 mmol g  1 cat, with sol–gel TiO2 4.7 mmol g  1 cat and with Degussa P25 38.2 mmol g  1 cat.
f
Photoreduction may be accelerated by high concentration of HCO3 obtained by alkali solutions that dissolves more CO2 than does pure water, or by elevated CO2
pressure of the reactor.
g
With concentrated sunlight 197; 34 and 124 mmol h  1 g  1, respectively of H2, HCHO and HCOOH in 6 h; 408 mmol H2 g  1 at ambient temperature with 150 W Hg
lamp irradiation in 6 h.
h
A simultaneous supply of photons and of thermal energy often improves the activity of photocatalysts probably because at low temperatures surface coverage is high
and products do not easily desorb, thus product desorption is rate limiting.
i
600 mmol g  1 after 30 h.
j
More efficient wavelength depending in photocatalyst bandgap.
k
Respectively 160, 150 and 140 mmol of methanol obtained in 20 min with 300 mg of ZnO, or NiO or TiO2 photocatalyst.
l
Increasing light intensity increases photocatalytic yields.
m
2655 mmol g  1 after 6h at 60 1C, in the order of 4500 mmol g  1 after 6 h at 100 1C according to curve).
n
According to curve.
o
After 72 h CO, CH4, and C2H6 concentrations reached, respectively 8306 ppmV (92.5 mmol g  1), 1367 ppmV (15.2 mmol g  1), 1712 ppmV (19.1 mmol g  1).
p
After 7.5 h: 48 mmol CH4.g  1 and 22.5 mmol H2 g  1.
q
The authors measured 5 mg carbon nano tubes for a 1 cm2 membrane of 35 mm length, they calculated an overall hydrocarbon production rate of 160 ml h  1 g  1,
or 0.83 ml cm  2 h  1, or 111 ppm cm  2 h  1, and also 65 ppm H2 ppm cm  2 h  1.
r
48 and 3.3 ppm h  1 g  1. of CH4 and CH3OH, respectively; if Fe used instead of Pt, H2 production is 55 ppm h  1 g  1.
s
2634 mmol g  1 cat after 6 h.

higher hydrocarbons, etc. providing a carbon-neutral energy (254 nm) is significantly more effective (60 times) than with
alternative to fossil fuels. 350 nm wavelength. Koci [164] observed the wavelength effect
But accomplishing this goal in an efficient and a cost-effective on photocatalytic reduction of CO2 by Ag/TiO2 photocatalyst: the
way will be challenging due to the large volumes of air that must main products concentrations (CH4 and CH3OH) were higher with
be processed. Photocatalytic reactors can be modular and operate the 254 nm lamp than with the 365 lamp while no products were
with negligible pressure drop. They have already been scaled up observed with the 400 nm lamp as the catalyst was not active
to suit a wide variety of indoor and outdoor air quality and under visible light.
environmental applications [137–159]. Wang [165] studied visible light photo-reduction of CO2 using
CdSe/Pt/TiO2 catalysts; Zhang [166] demonstrated that iodine-
doped TiO2 nanoparticles are photocatalytically responsive to
5.3.2. Temperature effect
visible light illumination; Ogura [167] worked on a cerium oxide
Several authors reported that increasing the reaction tempera-
CeO2—TiO2 photocatalyst irradiated by visible light and the
ture further increased the rate of CO2 reduction: Anpo [160]
reaction products were H2 and CH4 and Varghese [156] described
observed that the total yields of CH4, CH3OH, and CO are larger at
high rate solar photocatalytic conversion of CO2 and water vapor
323 K than at 275 K.
to hydrocarbon fuels. Copying natural photosynthesis with photo-
Wang [158] obtained almost a double yield of CH3OH when
catalytic CO2 reduction using sunlight could be a direct method to
increasing temperature from 25 to 75 1C. Zhang [166] obtained
both decrease greenhouse gases and supply sustainable energy to
CH4 yields of 0.14 and 0.115 mmol h  1 g  1 at 323 1C, and 0.56 and
mankind. Thus, in order to fully harvest solar energy, visible-light
0.205 mmol h  1 g  1 at 343 1C, respectively for 0.15% Pt/TiO2
driven photocatalysts are highly desired.
nano-tubes and 0.12% Pt/TiO2 nano-particles (quadrupled and
Recently Kin [168] demonstrated that even the NIR energy can
doubled yield depending on the catalyst). Experiments carried out
be used as the driving source for photocatalysis besides the UV
by Saladin and Alxneit [161] showed that the overall reaction rate
and visible energy. Improvements in the photo-efficiency of
of CH4 formation increases when the temperature rises from 25 to
photocatalysts used in these reactions are still needed to prove
200 1C. Slamet [148,149] showed an increase of methanol forma-
feasibility, as well as scaling up the size of the photocatalytic
tion with temperature in experiments performed at 43, 60, 75 and
reactors.
100 1C.
Efforts have to be made to extend the light absorption range of
Quite often thermal energy improves the activity of photo-
TiO2 from UV to visible light and to NIR, and also to improve the
catalysts already activated by photons, for instance when pro-
light absorption in the overall efficiency (kg CO2 converted kg  1
ducts desorption is rate limiting warming will increase the
catalyst) as well as to increase the photocatalytic activity of TiO2
production rate, but an optimum might exist if CO2 and reagents
further by adding noble metals, metal ion doping, anion doping
absorption is important. Higher temperatures might also lead to
and metal ion implantation and even the addition of sacrificial
thermal catalysis, but CO2 reduction might follow other reaction
regents or newer experimental conditions to prevent backward
pathways, modifying selectivity.
reactions.
Studying several Pt/TiO2 photocatalysts, Yang [162] reported
Table 2 gives several selected examples of CO2 reduction
that all the mixtures tested showed visible light response in
experimental conditions and yields. Production rates are often
comparison with pure TiO2 and also that photoproducts deso-
expressed in terms of mmol h  1 g  1 of catalyst as the quantum
rption was the rate-limiting step in the CO2 photoreduction.
yield is still low. In order to allow comparisons although the
Reaction products could act as electron donors for enhancing
kinetics are not linear we calculated h  1 yields, the original data
visible light hydrogen evolution from Pt/TiO2 photocatalysts.
of the authors are given in the notes at the bottom of Table 2.
Yang also investigated the effect of Cu dopant, pH, irradiation
As seen in Table 2, the principal products are methane and/or
time and using Na2SO3 as a sacrificial agent.
methanol, the overall reaction schemes are:

CO2 þ2H2Oþhn2CH4 þ 2O2 (9)


5.3.3. Wavelength effect
Matthews [163] demonstrated that the light wavelength CO2 þ2H2Oþhn2CH3OH þ3/2O2 (10)
influences the photocatalytic yield. Tseng [145] showed that for
the CO2 reduction using TiO2 the light with shorter wavelength In both cases free oxygen is a reaction product.
96 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

If CO and O2 are formed and not effectively desorbed from the As seen previously in Section 4, many types of photocatalysts
catalyst surface photo-oxidation of CO back into CO2 in the and methods are used for photo-reduction of CO2, but the
reverse reaction is possible and thus decreases reduction yields. synthesis of photocatalytic molecules and materials is becoming
Secondary reactions are possible for instance leading to higher increasingly sophisticated and thus expensive. The most widely
molecular-weight hydrocarbons. This explains some cases where used photocatalysts are TiO2 derivatives (Table 2) and the reac-
production rates of lower molecular-weight initial products tion products are generally methane, or methanol with other
increases first and then after some time decreases or reaches a products [122–130].
steady-state. In the scientific literature, photocatalysts are often only
With excess catalyst yields can decrease, for instance in characterized in terms of reactivity, and selectivity, and some-
aqueous solutions when large quantity of catalyst prevents a times stability but quite little is known about the cost of the
good penetration of light in the reactor. photocatalysts or of their preparation.
Many parameters are important for the conversion yield, not
only the size and surface area of the photocatalyst, the doping
5.3.4. Alkalinity effect element, or the co-catalyst, but also for instance the temperature,
With the exception of Rh/TiO2, all these solid materials exhibit the alkalinity and the absorption wavelength. The key parameters
the properties of solid base catalysts; therefore the slightly acidic and driving costs were seen in previous paragraphs of Section 4.
CO2 can be adsorbed on the surface. The adsorption of CO2 on the Increasing the absorption in the visible-light region often
surface is particularly important since CO2, which is a stable and increases the efficiency and quantum yield, but although research
linear molecular, becomes after adsorption an active specie of efforts have resulted in the emergence of new generations of
abundant reactivity for photocatalytic reduction. The reactors are visible-light-active photocatalysts, visible-light driven CO2 reduc-
two-phase systems and can be either gas-catalyzed or liquid- tion is at an even earlier stage of development than water
catalyzed. Generally catalyst are typically on either fluidized or splitting. On Table 2 some examples of the yields that can be
fixed beds. obtained with selected photocatalysts are summarized. Izumi
Adding NaOH or another alkaline solution dissolves more CO2 [172] reviewed in 2012 other CO2 reduction reactions in water
than pure water, and in addition OH  in aqueous solution also or with moisture using semiconductor photocatalysts other than
acts as a strong hole scavenger. Using organic sacrificial hole TiO2 (ZnO, CdS, SiC, etc) with the formation rates of the products
scavengers like 2-propanol decreases profitability. obtained.
In water solution the experimental results of several authors To understand heterogeneous photocatalytic processes, one of
indicate that the products yields increases significantly with the keys is the surface of the active catalytic material since the
increasing CO2 concentration. chemical transformation takes place there. Consequently, the
The influence of water and carbonates has been studied by reactivity of a catalyst scales directly with the number of exposed
Dimitrijevic [169]. active sites at the surface. Furthermore, photocatalysts are often
doped with precious metals, and accordingly it is advantageous to
disperse the photocatalytic active material as nanoparticles, not
5.4. Sensitivity analysis of key parameters for SCPPþphotocatalysis only to maximize the number of active sites and enlarge the range
of wavelength reactivity, but also to keep the manufacturing cost
Artificial photosynthetic systems are promising routes for of the catalyst low. But even if the precious metal co-catalyst is
solar-to-chemical energy-conversion process, but they are still present at only 1% by weight, as the current cost of a gram of Pt,
at the laboratory stage where the principles of their assembly and Rh or Pd is roughly a million times the cost of a gram of fuel [173]
functionality are still being explored. Significant challenges it would account for 98% of the cost of the photocatalyst. The
remain to build efficient devices capable of producing solar- substitution of a base metal instead of precious metals reduces
fuels at a scale and at a cost that can compete with fossil fuels. the cost of the photocatalyst and makes it a possible alternative
The principal interest of photocatalytic processes is mainly due material for the purpose of an industrial application.
to the fact that it can be powered by sunlight and that a For a cost-effective and sustainable large-scale implementa-
photocatalyst like TiO2, is usually cheap, chemically stable, avail- tion, very different issues must be addressed and fulfilled [174],
able and abundant. Moreover photocatalytic reactions often occur including photocatalyst cost, abundance, low toxicity and long-
at room-temperature and at ambient-pressure, with no need of term stability under strong solar irradiation. These crucial
additives or solvents. Dhakshinamoorthy [170] reviewed in 2012 requirements suggest the use of cheap transition metals and
the titanium containing photocatalysts, focusing on pure TiO2 as naturally abundant chemical elements such as iron, titanium,
well as on metal- and non metal-doped titania, noble metals zinc, carbon, nitrogen and sulphur, and avoid using costly sacri-
supported on titania and micro-mesoporous titanosilicates or ficial agents or scavengers.
porous matrices containing titania clusters. Mori [171] reviewed The ideal photocatalyst has a low cost and shows high
the photocatalytic reduction of CO2 with H2O on various titanium performance and effectiveness, but as explained by Grills and
oxide photocatalysts, and noted that the bulk TiO2 powders under Fujita [175], two other important parameters are turnover num-
heterogeneous gas–solid conditions produced CH4 as the major bers and turnover frequencies. For a realistic system life, turnover
product, while the predominant formations of CH3OH as well as numbers should be high and turnover frequencies should be very
CH4 were observed on the highly dispersed titanium oxide moiety fast, and the current state of the art is many orders of magnitude
anchored on zeolites and mesoporous silica materials. away from either target. For each specific and individual photo-
Photosynthetic reactions are determined primarily by three catalyst, synthesized at the laboratory scale for academic research
reaction processes: light-harvesting processes; charge generation purposes, the number of possible photocatalytic cycles is yet
and separation processes; and catalytic reaction processes (Eqs. unknown and currently it is quite difficult to extrapolate large
(6)–(8)). The overall efficiency is determined by the balance of scale production costs.
thermodynamics and kinetics of these processes. In the case of Low-cost fabrication techniques such as hydrothermal and
CO2 photoreduction with water, two or more photocatalysts chemical vapour deposition are now widely used, and often the
might be necessary, as often H2 is generated first form H2O; then active catalytic material is dispersed as nanoparticles onto high
CH4 is obtained both from CO2 and H2. surface area supports such as silica, alumina, carbon or zeolites.
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 97

Photocatalysts anchored to cheap supports have a better chance In order to make this process economically feasible, significant
to be developed in kilogram quantities and employed for practical improvements such as the specific rate of CO2 reduction and the
applications. quantum yield of photoreaction are needed prior to up scaling [182].
Many works report the use of heterogeneous photocatalysis Recent work from Takeda [183] led to the discovery of a
for deodorization and treatment of gas streams and indoor-air, rhenium(I) complex with a very high quantum yield (0.59) for an
and worldwide large scale use of photocatalytic self-cleaning efficient photocatalytic CO2 reduction into CO. But large scale use
glass, paints and coatings demonstrates the interest of photo- and production of this expensive catalyst seems unrealistic, in the
catalysis in industrial applications, and in particular for pollution same manner as using sapphire [155] or nano-tubes [156].
removal [2,176,178]. Experiments carried out in real scale showed This paper does not treat of photo-electro catalysis, but we
that photocatalytic road materials induced a significant reduction report the work of Ichikawa and Doi [184,185] who explored the
in NOx air pollutants. But further research is still strongly hydrogen production from water and the conversion of CO2 to
necessary to investigate long term performances in terms of useful chemicals by room temperature photo-electro catalysis.
economical vantages for the environment. A TiO2 anatase sample tested in a single photo-electro catalysis
Large scale photocatalytic reduction of CO2 to realize carbon- cell unit produced hydrogen at rates of 0.42 1 h  1 m  2 (19 mmol
containing solar fuels is still in the infancy and its industrial H2 h  1 m  2 of irradiated photocatalyst area) under sunlight
application is still probably a decade away from making economic without applied voltage bias and also hydrogen at a rate of 26
sense. Significant advances in efficiency are required before such 1 h  1 m  2 with bias under 500 W mercury lamp. We can calcu-
devices will be able to compete with conventional energy sources. late that if the photocatalyst area under a SCPP is of 1 km2, on a
A further challenge is translating laboratory-scale academic sunny day, without applied voltage bias, the hydrogen evolution
research into scalable, industrial technologies, including consid- rate will only be approximately of 450 kg H2 d  1 km  2, and with
erations of large-area processing and outdoor testing [173] before bias the H2 production can be as high as 27.8 t d  1 km  2. But
large-scale implementation. Whether it is a photocatalyst for air applying a voltage to 1 km2 of photo-electrodes seems tricky.
or water purification, environmental remediation or high-density Although some research work led to very good results at the
fuels production, the cost of the photocatalyst is a major factor in laboratory scale, large scale application seems difficult for several
determining the feasibility of an application. The ideal material reasons.
has a low cost and shows high performance, effectiveness and For instance, Yahaya [186] described the selective laser
stability. Artificial photo-synthesis has the potential to provide enhanced photocatalytic conversion of CO2 into methanol. Opti-
significant economic, environmental and social benefits, provid- mum yield is obtained in just 20 min and is quite high. But in
ing that solar energy-conversion efficiencies increase and produc- order to find synergies with SCPPs, sunlight has to be preferred to
tion/operating costs decrease. The effects of the other process artificial pulsed laser light.
variables although important practical issues appear secondary In experiments conducted by Wang [158] the quantum effi-
and for such large scale PCR the driving parameters will be the ciency of optical-fiber reactor was found to be 14 times higher
photocatalyst cost and lifetimes, quantum yield, visible light than that of the aqueous-phase reactor, because photocatalyst
absorption and reaction rates. film on fiber had superior light-energy utilization. According to
Wang and also to Wu [187], optical-fiber reactors can solve the
difficulty of photon-energy delivery, as they provide a medium to
6. Choice of experimental conditions for large scale tests of transmit light uniformly throughout the reactor, especially for
photocatalysts large-scale design. But a reactor with several km2 of optical fiber
is questionable.
As shown in Table 2, with an increase of the yields by almost A more pragmatic approach could be that of Nishimura
three orders of magnitude, in several reduction products, this last [151,152]. In order to increase the conversion yields, they proposed
20 years of research has performed remarkable progress. a Cr doped multilayer of TiO2 films, coated on a Cu substrate by a
Several large scale tests of photocatalysis for air purification sol–gel and dip-coating technique. The number of film layers tested
have been performed around the world. Many experiments in was 1, 3, 7, and 11. Also, Pathak [188,189] proposed to increase the
Europe, Japan, Hong Kong and in the USA are reported in one quantity of photocatalysts for the reaction by stacking conveniently
recent review [2]. several catalytic films (Fig. 8). TiO2 nano-particles embedded in
At least 50,000 m2 of surface area in Japan has been coated with Nafion membrane films (as in Fig. 8) could be coated with silver
TiO2, and Mo [177] reports that the daily removal rate goes from without neither changing the particle dispersion, nor the optical
0.5 to 1.5 mmol m  2 and that the photocatalytic material can transparency of the catalytic films.
maintain its effectiveness with very little performance deterioration. According to the authors, the translucent Nafion membrane
In many cities in Japan TiO2 has been applied in coatings, such as in films present a major advantage which is their photostability, as
Osaka, Chiba, Chigasaki, Suitama and Shinatoshin. the films exhibited no deterioration in photocatalytic activities
In Japan, Ibusuki [178] carried out tests in a roadside of a over an extended photoirradiation time (at least 50 h) and also as
6 lanes bound highway in Tokyo with an average traffic of
113,000 vehicles a day. Volatile organic compounds VOCs and
sulfur dioxide SO2 were, respectively removed by 17–20% and by
67–78%. The average removal percentage for nitrogen oxides NOx
with windowed panels was 31–69% during the field tests with an
estimated rate of removal of 3 mmol m  2 d  1, and the capacity of
the photocatalytic sheet for NOx removal was 20 mmol m  2.
But, despite these large scale experiments on heterogeneous
photocatalytic destruction of gaseous pollutants (NOx, VOCs) and
also several pilot-scale photoreactor testing [179–181] for water
purification, more research is still needed and the road will be
long before the challenge of producing CO2-free fuel by direct Fig. 8. Tubular reactor with several layers of transparent photocatalytic films
conversion of solar energy into chemical energy is reached. stacked together according to Pathak [188,189].
98 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

after being washed thoroughly with deionized water, they were


reusable several times with similar photoreduction results in
repeated photoreduction reactions of CO2.
The same coating methods may be used in the preparation of
other metal-coated semiconductor nano-particles homoge-
neously dispersed in optically transparent ionomer membrane
films for photocatalysis applications.
A tubular type PCR can also be envisioned for CO2 reduction
under a SCPP. This tubular PCR resting on the ground of the SCPP,
presents several advantages:

 if pressure is needed for the photocatalytic reduction of CO2,


tubular type PCRs will be resistant enough;
 if warming is necessary the PCR can be circular and even
several km long with several spiral loops all around the
chimney, this will also increase contact time;
 they are better suited for a continuous flow process.

At the exit of the PCRs, un-reacted CO2 is separated from the


reaction products and directed towards geological sequestration.
A system of heat exchangers allows recycling heat for SCPP power
generation.
In the case of reaction on the gaseous phase, obtaining alcohols
or olefins should be favored to facilitate separation of gaseous
reactants from liquid products. For the same reasons, when
working in liquid medium, trying to obtain methane or lower
gaseous hydrocarbons and hydrogen could be a good strategy, but
the amount of CO2 dissolved is pressure or pH dependent. High
concentrations of HCO3 accelerate photoreduction, thus elevated
CO2 pressure of the reactor or highly alkaline solutions are used as
they dissolve more CO2.

6.1. Choice of the reaction type

Some authors studied the photocatalytic CO2 reduction in the


presence of hydrogen. Teramura [190] uses H2 gas as the
reductant on the photoreduction of CO2 over a Ga2O3 photocata-
Fig. 9. Different types of PCR according to Zhang et al. [194]: (a) flat, (b) tubular
lyst. Liu [191] obtained 118.5 mmol g  1 h  1 of CH3OH yield with
and (c) honeycomb types.
RuO2/Cu0.30Ag0.07In0.34Zn1.31S2 under hydrogen effect.
In the field of water splitting, many compound oxides are
supercritical CO2, and a photocatalyst as effective as possible but
known to function as an effective photocatalyst and Teramura
also cheap and readily available.
[192] was the first to show that compounds ATaO3 (A¼Li, Na, K)
Several types of photocatalytic reactors (PCR) have been devel-
are photocatalyst oxides candidates for the reduction of CO2, in
oped, and they can be divided in 3 main categories [194]: plate,
the presence of H2. Under photoirradiation only CO gas was
honey-comb or tubular as shown in Fig. 9. Among fixed-bed designs,
generated, the photocatalytic activity was in the order LiTaO3 4-
honeycomb monoliths and annular reactors are the most common
NaTaO3 4KTaO3 and after 24 h of photoirradiation with a 200 W
because of their higher volumes and lower pressure drops.
Hg–Xe lamp the amount of evolved CO reached 0.42 mmol g  1
Kočı́ [195] studied recently the influence of geometry in
over LiTaO3. CO is generated [192] and references cited there in as
annular batch reactors.
a result of the photocatalytic reduction of CO2 in the presence of
H2 or CH4 as a reductant over ZrO2, Rh/TiO2, MgO and Ga2O3.
6.3. Research effort needed

6.2. Choice of the reactor type The intrinsic idea of photocatalytic conversion of carbon
dioxide and water (liquid or vapor) into hydrocarbon fuels is
Performing the CO2 reduction reaction in solution with sus- appealing and even if the process has historically suffered from
pensions or dispersions of photocatalysts (fluidized bed reactor) low conversion rates, rapid advances are made as can be seen in
allows vigorous agitation but presents the disadvantage of ero- Table 2.
sion by abrasion of catalyst particles and attrition of the catalyst. The yield of photo products can be modified substantially under
Milling decreased the size of the TiO2 particles and this led to different experimental conditions such as light wavelengths, light
changes in the optical properties and also in significant deteriora- intensity, sacrificial reagents or additives, temperature, reaction
tion in their photocatalytic activities [193]. media, reaction time and reactor configuration. Other variables, such
Generally, in fixed bed reactors, the fluid flow regime allows as CO2 pressure, pH and oxygen and moisture content are also
achieving high conversion per unit mass of catalyst; and the low important in photocatalytic reduction of CO2. But the efficiency of
pressure drop enables such systems to be operated at reduced photocatalyst is the key parameter to a large extent. The photo-
operating costs. So, a realistic option would be to have an easy catalytic reduction of CO2 is still in its infancy. There are still many
mass transfer i.e., reaction in the gas phase with concentrated or opportunities for further improvements.
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 99

Table 3 shows that reactions can be carried out at room temperature and
Several reactor configurations for solar photocatalytic reactions [198], Fighting atmospheric pressure or under pressure and with water vapor. Some
global warming by photocatalytic reduction of CO2 under giant photocatalytic
research teams work with CO2-saturated aqueous solution (very
reactors.
diluted), some others in the gas phase or in supercritical fluid CO2.
Suspended photocatalyst Supported photocatalyst Best yields are often obtained after 6 to 24 h of illumination in
batch reactors.
Concentrating reactors Upscaling to giant photocatalytic reactors seems difficult since
Parabolic trough reactor Parabolic trough reactor
Falling-film reactor
many of the CO2 reduction reactions described in the literature
Non-concentrating reactors with reflectors cited herein were generally performed in reactors with a volume
Compound parabolic collecting reactor Tubular reactor o1 dm3 and with an amount of catalysts o1 g.
Fiber-optic-cable reactor The challenge of continuous photocatalysis consists in devel-
Non-concentrating reactors without reflectors
oping PCR designs with increased efficiency, up-scalable to an
Flat-plate reactor Flat-plate reactor
Trickle-down flat-plate reactor Trickle-down flat-plate reactor industrial size. The most important parameters are: the catalyst
Solar pond Thin-film fixed-bed reactor specific area and particle size, the catalyst amount; the mass
Inflatable tube reactor transfer rate, the flow rate, the pressure drop; the illuminated
Tubular reactors surface; the light efficiency and the intrinsic reaction kinetics.
Pressurized tube reactor
Double-skin sheet reactor
TiO2 is one of the most efficient photocatalysts and because of
Falling-film reactor its low cost, strong oxidizing power, high stability and non-
toxicity, it is already extensively used for environmental applica-
tions and complete degradation of some pollutants.

6.5. Synergies from SCPPs coupled with photocatalytic reactors


The implementation of a photocatalytic process at an effective
scale requires the use of a photo-reactor, a device which brings For any catalyst to be efficient, large active surface areas are
into contact the reactants with a photocatalyst and with light needed, as well as a potent irradiation source. The SCPPs green-
energy, as well as collecting the reaction products. house collectors have a huge surface exposed to freely available
An ‘‘artificial tree’’ from Lackner can provide the reactants (CO2 sunlight with UV and visible-light irradiation 12 h d  1 and might
and H2O vapor) with synergies and scale economies meanwhile be used as giant photocatalytic reactors (PCRs) for CO2 mitigation
the SCPP can provide the sunlight and the structure for the photo- by photocatalytic reduction.
reactor. The best methanol yield obtained by Slamet [148,149] for the
Photocatalysis offers already good prospects, but more CO2 reduction with H2O and copper doped TiO2, which was of
research is needed before reaching useful giant photocatalytic 2655 mmol g  1 of catalyst after 6 h of irradiation.
reactors [75,12] able to filter several cubic kilometers of air every Thus, upscaling to the size of a SCPP and assuming that two
day, or to transform by photocatalysis several tons of products. cycles of 6 h can be performed per day (12 h sunlight) during 365
Intensified research effort in this direction has to be performed to: days, allows to calculate that 1.938 mol of CO2 (85 g) could be
reduced per gram of catalyst per year (0.234 g CO2 d  1 g  1 of
 develop more efficient photocatalysts with enhanced photo- catalyst). In other terms, as 3452 t of CO2 can be captured daily
catalytic activity and increased specificity, maybe by compo- (nearly 1.26 Mt yr  1), in order to transform back to fuels 5% of
site photocatalysts made of semiconductor oxides and high the CO2 (173 t daily) by a solar tower with an ‘‘artificial tree’’,
surface area adsorbents [196], or by molecular imprinting 737 t of catalyst are theoretically needed (189 m3, as the density
[197] in order to induce selectivity among the products to be of TiO2 is nearly 3900 kg m  3). The projected area under the SCPP
photo-transformed; collector is of 38 km2, if the area of photocatalyst covers 8 km2,
 choose the best photocatalyst among the numerous candi- the amount of catalyst will be of 92 g m  2. This is comparable
dates, which apart from cost also depend on which chemical with commercial photocatalytic coatings or paints which after
reactions are considered and which products are expected; application contain 50 to 100 g m  2 of nano-sized TiO2. The giant
 optimize the different reduction or oxidation processes, mass photocatalytic reactor can be made of 4 double sided layers of
transport, adsorption of reagents, contact time, humidity translucent films or membranes [188,189] or multiple layers of
effects, adhesion of photocatalyst to substrates, photocatalyst metal doped TiO2 films [151,152] and thus can cover only an area
reactivation in case of deactivation; of 1 km2 which gives room to install a second identical PCR and
 select the operating conditions, in liquid or in gaseous phase, double the CO2 transformation yield. Indeed, millions of square
with suspended or with supported photocatalyst; meters of self cleaning glasses, self-cleaning coatings, paints or
 determine how to best organize and use photocatalytic reduc- cement are already in use in the world.
tion or oxidation technology; The rationale of PCR under the SCPP canopies comes from
 ensure that there are no emissions of hazardous by-products synergies, as the current projects for solar chimneys in Australia
and no unexpected environmental consequences from the or Namibia forecast an area of 38 km2 with an irradiation of more
large scale use of these catalysts and processes; than 2200 kW h m  2 yr  1.
 optimize PCR configuration, size and shape. A SCPP equipped with a translucent TiO2 coated glass or
polycarbonate PCR might resolve key difficulties related to the
In Table 3 several PCR configurations are summarized accord- cost and to the scale-up. The shape and length of the PCR where
ing to [198,126]. the catalyst will be fixed can be optimized.
The SCPP provides many things a photocatalytic reactor needs:
6.4. Extrapolation to large scale photocatalytic reactors and
photocatalytic performance  an external structure and an internal framework;
 a support for the PCR;
The performance and product distribution depend on the nature  a way to maximise the area of the photocatalyst illuminated
of the photocatalyst and the reaction conditions. Literature review by the light;
100 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

 an efficient illumination (no need of powerful UV lamps)


natural visible light carries 10 times more energy than UV.

The rationale is that SCPPs are the only objects on earth which
could be:

 in contact with the largest quantity of moving air;


 receiving huge amounts of ‘‘free’’ sunlight;
 being sheltered from rain and dust;
 displayed in synergy for another purpose: production of
renewable electricity.

Although there are no scale economies in terms of infrastruc-


ture for a PCR, synergies are possible as the DAC Lackner device
can provide CO2 and water, and the SCPP disposes of a huge flat
area and of plenty of sunlight and heat.

6.6. Improving the choice of the PCR type

A flat type PCR can be envisioned for CO2 reduction in order to


perform the photo-conversion in between the two components of
double-glazing with a translucent photocatalyst inside, previously
attached. But the volume inside the double glazing should not be
too small.
Connection of several double-glazed panels together might
raise several technical problems as the external borders must be
hermetically closed and their intersection must be open to let
them communicate for CO2 introduction in one side and collec-
tion of the reduced products on the other side. For transparency Fig. 11. Top view and lateral view of tubular type photocatalytic reactor with
as well as for cost reasons it cannot be the double glazing of the translucent photocatalyst inside.
main collector roof, and therefore it should be a secondary
greenhouse installed on the ground as shown in Fig. 10. Artificial lightening at night is feasible, but as there are no
scale economies, only a complete financial study of the invest-
ments amortization of the infrastructure and equipment together
6.6.1. Contact time and radiation effect
with the yields obtained and electricity cost could help to decide
This configuration allows the higher irradiation rate flows for
if the game is worth it. So, an alternative during night is that the
both the roof and for the ground surface where the PCRs are
CO2 captured is sequestered and stored, or sold for industrial
installed. These flat PCRs as in Fig. 11 will have a radial orienta-
applications like enhanced oil recovery. As the SCPPs can be built
tion and if long contact times are needed for a high rate of
close to disposal sites, there is no need to build hundreds of km of
photocatalytic conversion they can work by batch process.
pipelines. All waste heat of the sequestration process, for instance
coming from pumps and from the compression step, can be
6.6.2. Day and night overall performance recycled under the SCPP.
The photocatalytic CO2 conversion into useful reduced com-
pounds can only be done during the day under free sunlight. 6.7. Sensitivity analysis of key parameters for photocatalytic
reactors

As seen previously in this chapter during the examination of


the key PCR parameters, several types of photochemical reactors
are possible (Table 3) and Figs. 10 and 11 illustrate some possible
implementations, but the final choice depends of the process,
itself being photocatalyst dependent. Still very numerous photo-
catalysts can be good candidates and an infinite number of
scenarios are still possible. The efficiency of currently available
TiO2-based photocatalysts is still not sufficient for practical use in
fuels synthesis. Therefore, the development of new ones and
optimization of existing photocatalysts exhibiting activity upon
visible light with surface characteristics of improved performance
and of high chemical and physical stability are crucial for broader
scale utilization of photocatalytic systems in commercial applica-
tions. Once the photocatalyst and the operating conditions will be
chosen, then the products obtained will fix the type of PCR and
only then design specifications and costing assumptions could be
formulated.
Thus, this sensitivity analysis has been limited to the identifica-
Fig. 10. Flat type photocatalytic reactor with translucent photocatalyst inside. tion of the most important PCO parameters as it is still premature
R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106 101

to try to find cost drivers and quantitative trends or to perform a daily air-flow in the chimney, it can be envisioned an optimization
cost sensitivity analysis (i.e., investment discount rate, project life- and synergies to address and mitigate some of the climate change
span, cost/benefits estimates y). Many other technologies have consequences of global warming caused by CO2 and other GHG.
started out at extremely high cost, which has dropped as the We have shown that extensive deployment of SCPP and DAC
technology was refined and mass scale production started. Rarely technology capitalizing on recent scientific developments has the
the commercial viability of a young experimental technology is potential to substantially lower the risks of the anthropogenic
taken into consideration at such an early stage. The critical factors greenhouse gases emissions.
were only mentioned to better understand which parameters affect In this paper a giant photocatalytic reactor is proposed as a
most the process of photocatalytic CO2 reduction to fuels and device able to produce renewable electricity and at the same time
photochemical systems have a long way to go to achieve their full capture CO2 and transform a part of this CO2 back into liquid fuels
potential and thus successfully compete with alternative approaches in order to:
to produce fuels from sunlight.
 reduce some GHGs atmospheric concentration, for instance by
CO2 capture from ambient air followed by geological seques-
tration and/or utilization;
7. Conclusion  provide fuels and/or useful chemicals by photocatalytic reduction
of CO2, taking profit of the very large area of the greenhouse
Solar energy conversion systems fall into three categories collector canopy receiving sunlight with UV and visible-light
according to their primary energy product: solar thermal systems, radiation
solar electricity and solar fuels. The rationale of associating SCPP and  with minimum investment as the SCPP infrastructure can be
photocatalysis is that the three are gathered under the same used as the support for the PCR used for CO2 reduction.
structure. The SCPP greenhouse collects the sunlight, thermal energy
is converted into artificial wind, and turbines transform kinetic Alternative processes are needed to decrease the level of
energy into electricity. The photocatalytic reactor can transform the atmospheric greenhouse gases.
sunlight into fuels by artificial photo-synthesis using CO2 and water. Among the technologies capable of converting solar energy,
As seen in Section 3, many scale economies exist between the DAC CO2 and H2O into easy to use fuels, there is [201] the solar
and the SCPP, so also CO2 could be available for in-place transforma- thermal conversion, the combination of photovoltaic devices and
tion into high density fuels. No scale economies have between electrocatalysis, or the photocatalytic conversions.
described in this paper on the association of the SCPP and the PCR Licht proposes an original process (solar thermal electroche-
system, but some synergies arise from a common sheltered struc- mical production) [202] derived for the solar generation of
ture and a huge area illuminated by ‘‘free’’ sunlight. The availability energetically rich chemicals like iron, aluminum, magnesium or
of a renewable energy to assist in powering the plant can also lithium to proactively convert CO2 into fuels. For instance, as the
reduce operating costs. carbothermal iron production is responsible for 25% of worldwide
The transportation costs can be greatly reduced when the air industrial CO2 emissions, Licht proposes CO2-free production of
capture and fuel synthesis devices are both constructed adjacent iron by STEP. For instance, as the iron ore hematite is soluble in
to renewable energy sources so an integrated process is highly molten Li2O and Li2CO3, Licht proposes using concentrated sun-
desirable. Last but not least, at the final step of DAC, water light to heat at 650 1C molten carbonate and decrease the energy
removal from CO2 might not be necessary and CO2 compression of the electrolysis reaction. Prakash [203] propose carbon capture
neither, as many photocatalytic CO2 reduction processes require and recycling by photocatalysts supported on silica nanosprings.
water and proceed at atmospheric pressure. Sometimes increas- This paper presents a negative emission technology obtained
ing the temperature of photocatalytic reactions accelerates them, by coupling SCPPs with DAC systems which allows many scale
so the final products obtained at the end of the DAC regeneration economies, and the interest of photocatalysis for the reduction of
process might be used as is. CO2.
The SCPP associated with DAC and with photocatalysis pro- To enable the use of these technologies in practice, still many
vides a radical technological breakthrough: producing a CO2-free improvements are necessary in material optimization, as well as
renewable energy and at the same time removing the principal in reactor design and operation. But the perspective of SCPPs
greenhouse gas from the atmosphere and enabling production of development is promising, as each solar chimneys power plant of
high density transportation fuels by artificial photosynthesis. For 200 MW could at the same time:
Goeppert [199], as sunlight delivers to Earth each hour as much
energy as consumed by humankind in an entire year, rather than  produce 680 GW h of renewable electricity per year, which is
an energy problem we have an energy collecting and storage valuated as an annual saving of 0.9 million tons of CO2
problem. This problem could be solved by the integrated process emissions [83] for every SCPP;
proposed in this paper.  deliver non intermittent renewable electricity 24 h a day, 365
For Pearson [200] if CO2 is taken from the atmosphere and days a year, with a delivered power output as constant as
transformed into energy-dense carbonaceous products, a closed- possible, but also that can be controlled in order to be
loop production process for carbon-neutral fuels is possible, increased during peak load and act as a peaking power facility;
improving energy independence. This process can provide che-  drastically reduce the investment costs of Lackner’s DAC
mical energy storage systems, based on the conversion of renew- devices;
able energy into gaseous and/or liquid energy carriers, the latter  increase the yields and drastically reducing the operational
having the higher volumetric and gravimetric energy densities. costs of DAC;
The stored energy can then either be used for power generation or  allow negative emissions energy production;
in other sectors such as for transportation. Both the gaseous and  provide humankind with portable high-density fuels made
the liquid fuel energy carriers are compatible with existing with sunlight artificial photosynthesis by photocatalysis y.
infrastructures and demand.
Taking into account the very large surface area submitted to Fuels from sunlight [204], or converting CO2 back to fuel using
sunlight radiation and occupied by SCPPs, as well as the very large solar energy is not a dream, but a challenge which still requires
102 R.K. de_Richter et al. / Renewable and Sustainable Energy Reviews 19 (2013) 82–106

long-term research to develop the application side. For the References


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