Seminar Report

On
Study On: Conversion Of CO2 to Fuels
SUBMITTED BY
Aniket Potdar Chetan Rohida
(Seat No: T150215952) (Seat No: T150215955)

T.E. Chemical
UNDER GUIDANCE OF
Prof.P.S.Tadkar
(Department of Chemical Engineering, AISSMS COE, Pune)

DEPARTMENT OF CHEMICAL ENGINEERING

AISSMS COLLEGE OF ENGINEERING, PUNE -411001
2017 –18
 All India Shri Shivaji Memorial Society’s
College of Engineering, Pune: 411001

Certificate
This is to certify that Mr. Aniket Potdar and Mr. Chetan
Rohida students of third year Chemical Engineering
have successfully completed their seminar report on
“Study On: Conversion of CO2 to Fuels” for the year
2017-18

Prof.P.S.Tadkar Dr. K R Jethani

Guide Head of Department
 ACKNOWLEDGEMENT
We would like to express profound gratitude to our Seminar Guide Prof P S
Tadkar and Head of Department Dr. K R Jethani for their invaluable support,
encouragement, supervision and useful suggestions throughout this seminar
work. There moral support and continuous guidance enabled us to complete
work successfully.

Last but not the least, we are thankful and indebted to all those who helped
directly or indirectly in completion of this Seminar work.

Aniket Potdar Chetan Rohida

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 ABSTRACT
.
The reduction of carbon dioxide to useful chemicals has received a
great deal of attention as an alternative to the depletion of fossil
resources without altering the atmospheric CO2 balance. As the
chemical reduction of CO2 is energetically uphill due to its
remarkable thermodynamic stability, this process requires a
significant transfer of energy. The aim is not to provide an exhaustive
review of the area, but to present general aspects to be considered,
and then to outline which are currently the most efficient
photocatalytic systems.

Keywords: Alternative to the depletion of fossil resources,

thermodynamic stability

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 Table of Contents
Chapter Description Page No
1 Introduction 1
2 Literature Survey
3 Methods of Conversion
3.1
3.2
3.3
3.4
3.5
4 Future Work
5 Conclusion
References

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 Study On: Conversion Of CO2 to Fuels

CHAPTER 1
INTRODUCTION
Due to the shortage in the reserves of oil and natural gas as well as the strong
dependence of developed countries on fossil fuels, there is considerable interest in
the development of renewable energy resources. One of the primary and
inexhaustible energy sources is sunlight reaching the earth’s surface [1]. However,
two of the main problems of sunlight, as a source of energy, are the circadian cycle
between day and night together with the dependence on seasons and weather
conditions and the low sunlight power that makes it necessary to accumulate the
energy for long periods with large surfaces before the use of this energy. In this
regard, considering the problems associated with the direct use of sunlight, there
are two general strategies to use sunlight as a primary energy source, both of them
based on the accumulation of solar energy. The first one consists in converting
photons from the sun into electrical energy that can be stored in batteries or
supercapacitors as well as in any other form of conventional mechanical energy
already existing for electricity storage [2]. Particularly for transportation, where
high energy powers are required, there is a necessity to accumulate sunlight into an
intermediate energy vector that can be, for instance, charge capacitors or batteries
[3]. One of the main problems associated with this strategy is the limited resources
of lithium and other metals that are currently employed in batteries, making
sustainability problematic. An alternative to store sunlight as electrical energy is to
convert photons from the sun into chemical energy. The concept of solar fuels
refers to the production of chemicals that can release chemical energy using
sunlight as a primary energy resource. Among these solar fuels, the one that has
attracted the largest attention has been hydrogen produced from water. While the
US Department of Energy has identified hydrogen as the ideal renewable fuel for
transportation, there is a lack of basic knowledge and technology that still limit the
widespread application of hydrogen as fuel [4]. The advantages of hydrogen are its
high energy power per mass unit and the lack of negative impact on the
environment since water is the only by-product. However, the fact that hydrogen is
a gas that cannot be liquefied is associated with problems related to the storage
under ambient conditions of reasonable volumes of this gas as well as problems
derived from the risk due to flammability and explosion.

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CHAPTER 2
LITERATURE SURVEY
Solar fuels Derived from CO2
While water reduction only affords hydrogen, there are a series of products that
can be formed from CO2 reduction. The list includes oxygenated C1 and C2
compounds, such as oxalic acid, formic acid,
Int. J. Mol. Sci. 2014, 15 5248
formaldehyde, methanol and CO. In addition to these compounds, methane and
C2–C4 saturated and unsaturated hydrocarbons can also be obtained. From
these potential products, the one that would be more valuable as transportation
fuel is methanol, considering the high energy content of this alcohol, the
convenience of using a liquid compound with a relatively high boiling point and
the fact that methanol can even be combined as an additive of fossil fuels used
in standard automotive engines. Methanol has a high octane number and can
even be the precursor of other gasoline additives for octane number boost, such
as methyl tert-butyl ether and methyl tert-amyl ether. The energy content of
oxygenated derivatives decreases as the oxygen percentage in the compound
increases. Equations (1)–(3) summarize the combustion free energy of some
solar fuels, calculated from the data for the gaseous states from ref. [5]. One
point of concern is the so called “carbon footprint” of a process that, in the case
of methanol combustion, would be in principle zero if methanol is obtained
from CO2 reduction by water. The carbon footprint is a quantitative indicator of
the influence of a given process on climate change measured by the release of
CO2 equivalents to the atmosphere. Neglecting the preparation of
photocatalysts and other, in principle minor, contributions due to the
transportation and manipulation of components, the use of methanol as fuel

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would not produce any increase of atmospheric CO2 if this chemical is obtained
from CO2. It should be noted that methanol is far more reactive than CO2 under
photocatalytic conditions, quenching holes and undergoing oxidation to
formaldehyde, formic acid and eventually to CO [6–8]. For this reason, it is
highly unlikely that in batch reactions the concentration of methanol could be
high enough to be valuable, unless special conditions are applied.

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 Study On: Conversion Of CO2 to Fuels

CHAPTER 3
Methods Of Conversion

3.1 Photocatalytic conversion:

Feed tank is preloaded with milk. The feed material is preheated up to 720C by using a steam
jacket. Preheating causes a controlled denaturation of the whey proteins in the milk and it
destroys bacteria, inactivates enzymes, generates natural antioxidants and imparts heat
stability.The preheated feed is given to the separator tower which works as a flash drum with
help of peristaltic pump. This separator is loaded up to 70% of the initial stage.
The liquid from the bottom of separator is given to the bottom of the evaporator through the
centrifugal pump. Steam is introduced in the shell side of the evaporator from top. The flow of
the stream is controlled by globe valve. The product of the evaporator is given to separator
asrecycle line. The flashing of materialtakes place and is separated into vapor & liquid. The
recycle line works until desired concentration is reached. Diaphragm control valve is operated
and with respect to the density and product is collected in product tank.
The vapor from the separator are transferred to the condenser in which water is used as a cooling
agent, latent heat from the vapors is removed and stored in the condensate tank. There is a
vacuum connection at the condenser and hence the whole system is maintained under vacuum.
This vacuum pump takes out the un-condensable gases from the vapors.

3.2 Photosynthesis

The basic process can be split into four steps:

• Generation of charge carriers (electron–hole pairs) upon absorption of photons with
suitable energy from light irradiation
• Charge carrier separation and transportation
• Adsorption of chemical species on the surface of the photocatalyst
• Chemical reactions between adsorbed species and charge carriers

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Scientists have long dreamed of mimicking photosynthesis, by using the energy in sunlight to knit
together hydrocarbon fuels from carbon dioxide (CO2) and water. Now, a cheap new chemical
catalyst has carried out part of that process with record efficiency, using electricity from a solar cell
to split CO2 into energy-rich carbon monoxide (CO) and oxygen. The conversion isn’t yet efficient
enough to compete with fossil fuels like gasoline. But it could one day lead to methods for making
essentially unlimited amounts of liquid fuels from sunlight, water, and CO2, the chief culprit in global
warming.

The new work is “a very nice result,” says John Turner, a renewable fuels expert at the National
Renewable Energy Laboratory in Golden, Colorado.

The transformation begins when CO2 is broken down into oxygen and CO, the latter of which can be
combined with hydrogen to make a variety of hydrocarbon fuels. Adding four hydrogen atoms, for
example, creates methanol, a liquid fuel that can power cars. Over the last 2 decades, researchers
have discovered a number of catalysts that enable that first step and split CO2 when the gas is
bubbled up through water in the presence of an electric current. One of the best studied is a cheap,
plentiful mix of copper and oxygen called copper oxide. The trouble is that the catalyst splits more
water than it does CO2, making molecular hydrogen (H2), a less energy-rich compound, says Michael
Graetzel, a chemist at the Swiss Federal Institute of Technology in Lausanne, whose group has long
studied these CO2-splitting catalysts.

Last year, Marcel Schreier, one of Graetzel’s graduate students, was looking into the details of how
copper oxide catalysts work. He put a layer of them on a tin oxide–based electrode, which fed
electrons to a beaker containing water and dissolved CO2. Instead of splitting mostly water—like the

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copper oxide catalyst—the new catalyst generated almost pure CO. “It was a discovery made by
serendipity,” Graetzel says.

A bright ideaA new catalyst made from copper and tin oxides uses electric current from a solar
cell to split water (H2O) and carbon dioxide (CO2), creating energy-rich carbon monoxide (CO) that
can be further refined into liquid fuels.H2OCOCOOH–O2CO2CO2H+Catalyst-
coveredelectrodesMembraneSolar celle–e–SunlightV. ALTOUNIAN/SCIENCE

The tin, Graetzel adds, seems to deactivate the catalytic hot spots that help split the water. As a
result, almost all the electric current went into making the more desirable CO. Armed with the new
insight, Graetzel’s team sought to speed up the catalyst’s work. To do so, they remade their electrode
from copper oxide nanowires, which have a high surface area for carrying out the CO2-breaking
reaction, and topped them with a single atom-thick layer of tin. As Graetzel’s team reports this week
in Nature Energy, the strategy worked, converting 90% of the CO2 molecules into CO, with
hydrogen and other byproducts making up the rest. They also hooked their setup to a solar cell and
showed that a record 13.4% of the energy in the captured sunlight was converted into the CO’s
chemical bonds. That’s far better than plants, which store energy with about 1% efficiency, and even
tops recent hybrid approaches that combine catalysts with microbes to generate fuel.

Nate Lewis, a chemist at the California Institute of Technology in Pasadena, says the new result
comes on the heels of other recent improvements that use different catalysts to turn CO2 into fuels.
“Together, they show we’re making progress,” Lewis says. But he also cautions that current efforts
to turn CO2 into fuel remain squarely in the realm of basic research, because they can’t generate fuel
at a price anywhere near to that of refining oil.

Still, exploding supplies of renewable electricity now occasionally generate more power than the grid
can handle. So scientists are looking for a viable way to store the excess electricity. That’s likely to
drive further progress in storing energy in chemical fuels, Graetzel says.

3.3 Bacteria

• Chemosynthetic bacteria such as Pyrococcus Furiosus, rushing fireball don’t need

sunlight to convert carbon dioxide into organic compounds, but do so in temperatures
exceeding 800°F on the pitch-black sea floor.
• By tweaking the genetic structure of P. Furiosus, researchers succeeded in using it to
convert carbon dioxide, at much lower temperatures, into 3-hydroxypropionic acid, a
common industrial chemical.
Pyrococcus Furiosus

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3.4 Conversion directly to Gasoline Fuels:

CO can be hydrogenated to hydrocarbons by either direct or indirect route. The
direct CO hydrogenation (CO -FT) is often described as the combination of the
reduction of CO to CO via reverse water-gas shift (RWGS) reaction and subsequent
hydrogenation of CO to hydrocarbons via Fischer–Tropsch synthesis (FTS) . The
indirect route is often performed by using different reactors with syngas (a mixture of
CO and H , derived from coal, natural gas and biomass) and/or methanol intermediate
formation . In contrast, the direct route is more economic and environmentally
benign while this approach usually yields CO and light paraffins as major products
owing to weak CO hydrogenation activity and over-hydrogenation of olefins .
Gasoline-range hydrocarbons are generally produced from refining of petroleum, or
from syngas via FTS process, or from methanol-to-gasoline (MTG) process . So far,
there has been no report on highly selective synthesis of gasoline from direct CO
hydrogenation. The key to this process is to search for a highly efficient catalyst.

Owing to their excellent ability to catalyse both RWGS and FTS processes and high
olefinic nature of obtained products, iron-based catalysts remain the preferred
catalyst candidate for CO -FT process . Furthermore, density functional theory

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calculations have demonstrated that Fe O (111) surface is very capable of activating.

3/12/2018 Directly converting CO2 into a gasoline fuel | Nature Communications

https://www.nature.com/articles/ncomms15174 3/21
CO (refs 20, 21). Typically, iron catalysts need alkali metal promotion to attain desired
activity and selectivity. It was reported that the addition of Na is beneficial to olefin
production . The existence of Na obviously enhances the surface basicity and
carburization of iron-based catalyst, making the catalyst very active for CO
hydrogenation to light olefins . Yet for the conventional iron-based catalysts, the
hydrocarbon products generally follow the Anderson–Schulz–Flory (ASF) distribution,
which is inherently wide and unselective . More unfortunately, these hydrocarbons
comprise mainly olefins and normal paraffins, with low octane number and unsuitable
as gasoline fuel. Considering that zeolites are powerful in
oligomerization/aromatization/isomerization of hydrocarbons due to their unique
shape selectivity and acidity , the combination of an iron-based CO -FT catalyst with

a zeolite into a multifunctional catalyst can shift product distribution towards high-
octane gasoline-range isoparaffins and aromatics. In spite of considerable efforts

made in the development of composite catalysts , the selectivity to C

hydrocarbons, especially centred C –C hydrocarbons, is not high enough owing to
the poor coordination between the components of composite catalysts.

In present work, we report a high efficient multifunctional catalyst comprised of Na–

Fe O nanocatalyst and nanocrystalline HZSM-5 zeolite (Na–Fe O /HZSM-5 catalyst)
for the direct conversion of CO to gasoline-range hydrocarbons. This catalyst
displays record selectivity towards C –C hydrocarbons (78%) as well as low CH and
CO selectivity under industrially relevant conditions. It was also discovered that the
choice of active components and the integration manner of the components are
crucial to control the product selectivity.

3.5 Conversion of CO2 to Methanol:

• Methanol (CH30H) can be turned into a form of bio-diesel fuel and burned in engines.
• This technique uses a thermal process to coat copper oxide (CuO) nanowires with another
form of copper oxide (Cu2O) and submerging them in a solution rich in carbon dioxide.
• The CuO-Cu2O hybrid nanorod arrays are then subjected to sunlight – or simulated
sunlight in the lab – to trigger a chemical reaction and produce liquid methanol.
• The experiments generate methanol with 95 percent electrochemical efficiency and
avoided the excess energy input, also known as overpotential, of other methods.

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Mechanism for conversion to Methanol :

Mechanism A

CO2 + e- .CO2-
.CO2- + .H CO + OH-
CO + e- CO-
.CO- + .H .C +OH-
.C + H+ e- . CH . CH2 .CH3
.CH3 + H+ + e- CH4
.CH3 + .OH CH3OH

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CHAPTER 4
FUTURE WORK
There are some practical and theoretical issues that need to be addressed. The models which we
are trying to do are much with theoretical approach. But things may vary while practical
application of the models.
For working of methods still requires more studies.

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CHAPTER 5
. CONCLUSION

It is clear that the current state of the art is still far from having identified an optimal way for
CO2 reduction which may be applied commercially. Introduction of carbon conversion and
sequestration systems is not meant to shift focus from renewable energy technologies.

In a recent masterly survey of their work over the past 15 years, Olah et al.(2009) expound a
vision that reflects the basis of our present review:

Carbon dioxide ... can be chemically transformed from a detrimental greenhouse gas causing
global warming into a valuable, renewable and inexhaustible carbon source of the future
allowing environmentally neutral use of carbon fuels and derived hydrocarbon products. With
carbon capture and sequestration (storage) becoming a key element in worldwide efforts to
control/minimize emissions, it can be anticipated that large amounts of CO2 will become
available as feedstock for innovative conversions to synthetic fuels. Of course, ‘whole process’
energy balances and economics remain

Phil. Trans. R. Soc. A (2010)

Review. Turning carbon dioxide into fuel 3361 a critical issue—as indeed is the case for any
overall vision of energy futures. It is an obvious, but nevertheless a most potent, fact that any
new fossil fuels can only be formed naturally over geological time scales. The challenge,
therefore, is to achieve such transformations from natural and industrial sources, as well as
human activities, via CO2 capture and subsequent conversion to synthetic fuels over, what one
might term, less demanding time scales! The cycle in figure 12 reflects particularly the tri-
reforming route to a sustainable fuel (§3c). In this work, we have attempted a brief overview of
the current scientific challenges in the area, with an emphasis on the important, underlying
thermodynamic considerations and the urgent agenda for materials research and development
(figure 12). This vision in many ways constitutes humankind’s artificial version of the natural
recycling of CO2 to energy fuels by photosynthesis using sunlight as the primary energy source
(Barber 2009).To bring any, or all, of these innovative approaches into real life, technologies will
require major advances in research and development, as well as significant socio-political
commitments to CO2 capture and utilization. International collaborative research between
developed, and developing countries (figure 2) isalso absolutely critical in such a venture. Our
hope is that this present summary helps to catalyse such a worthwhile development.

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CHAPTER 6
REFERENCES
"Rethinking Carbon Dioxide: From a Pollutant to an Asset" (Yale Environment 360 - Feb 23,
2012).

Yang, H.-C.; Lin, H.-Y.; Chien, Y.-S.; Wu, J.C.-S.; Wu, H.-H. Mesoporous TiO2/SBA-15, and
Cu/TiO2/SBA-15 composite photocatalysts for photoreduction of CO2 to methanol. Catal. Lett.
2009, 131, 381–387.
Martin, O. et al. Indium oxide as a superior catalyst for methanol synthesis by CO
hydrogenation. Angew. Chem. Int. Ed. 55, 6261–6265 (2016).
Graciani, J. et al. Highly active copper-ceria and copper-ceria-titania catalysts for methanol
synthesis from CO . Science 345, 546–550 (2014).
D.E. Robertson et al, “A New Dawn for Industrial Photosynthesis,” Photosynthesis Research,
March 2011, Volume 107, Issue 3, pp 269‐277, DOI 10.1007/s11120‐011‐9631‐7;
http://link.springer.com/content/pdf/10.1007%2Fs11120‐011‐9631‐7.pdf

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