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Fossilize CO2- Make Fuels

[A Green And Black Paper on Soda-Fuel Cycle]

By Neale R. Neelameggham
Abstract:

This paper provides the logic on how we can make fuels at will based on fundamental
concepts used in chemical processes. The proposed approach of Soda-Fuel Cycle using carbon
dioxide and water, can create conventional fuels with better yields, and also help in solving
global warming in a heretofore not thought of fashion. The reasons for bio-fuels giving low
yields are also pointed out.

Fundamentals:

“Energy makes Energy”- Energy conversion makes many things possible. Our efforts
should be in making these fuels synthetically and at any place. The generation of bio-fuels is
only a subset with low yields. We need to absorb pieces of advice from what happened in the
pre-biotic times and from what is happening in nature and increase the fuel yields.

How do we make fuels with better yields? - Soda Fuel Cycle

It is proposed here that we consider an even more basic reaction with applied energy to
react carbon dioxide and water as starting reagents, called Soda Fuel Cycle [carbonated water to
fuel reaction using energy].

The following are some Soda Fuel Reactions:


Carbon Dioxide + Water + Energy = fuels [Carbon/Hydrogen/ hydrocarbon] + Oxygen / oxide
A catalyst may be needed at times.

One subset of this is the following reaction


Carbon dioxide + water + energy = alcohol + oxygen/ oxide

Table 1 compares the minimum external energy required for some possible Soda Fuel
reactions making the fuels. Table 2 shows the weight of different soda-fuels having the same
combustion energy as one unit weight of hydrogen. Table 3 provides a comparison for oxidation
of some common elements with hydrogen. The actual energy used will be more than shown
above when true conversion efficiencies are accounted for.

Another variation of the Soda Fuel cycle is to make methane from carbon dioxide and
water, similar to what happens in nature.
Carbon dioxide + water + energy = methane + oxygen/ oxide

This approach can also handle problems of global warming caused by excessive release
of carbon dioxide without putting a damper on hydrocarbon fuel use. We can even take the
carbon dioxide from the atmosphere in doing this. There are several ways of doing this. One can
use the carbon dioxide that comes along with natural gas to make more product fuels. One can
convert portions of carbon dioxide to carbon and make it available for future use – or in terms of
common parlance “fossilize it.”
Mother nature has been showing the way that there are low temperature conversions to
fuels [marsh gas, peat, etc]. Instead of thinking that these are all biotic reactions, evaluate
prebiotic and abiotic pathways that will give the clue for making fuels at will as well as fossilize
carbon dioxide effectively.

An example of a reaction with carbon dioxide is the production of water aboard


the International Space Station Alpha (ISSA) with the Sabatier Reaction. This is a reaction of
carbon dioxide with hydrogen in the presence of a catalyst to make methane and water. This
reaction uses hydrogen as a reducing agent, which provides the energy.

Why the Soda-Fuel Reactions Are Possible?

Light energy – the input - is absorbed and converted to other usable forms of energy such
as heat, electricity, chemical, biochemical and kinetic energy. These conversions almost always
have a usable as well as a non-readily usable component. The percentage of usable component
compared to the input energy is called efficiency of conversion. These secondary forms of
energy can further be converted to other usable forms of energy resulting in secondary, tertiary,
quaternary conversion efficiencies as well. It is for us to control the conversion efficiency.

The primary form of chemically converted solar energy is called fuels. These fuels such
as carbon and hydrocarbons are almost similar to any other naturally occurring metals or alloys
[hydrocarbon is alloy of hydrogen and carbon]. These fuels create the secondary energy used in
making our lives go around.

Most material found on earth's crust is usually present as oxides, which are in their lowest
state of free energy [or relaxed form]. Many of these are present as oxides - formed by reaction
with naturally occurring oxidant element oxygen. When such a lowest energy state has to be
broken and these oxide compounds have to be converted into useful materials, we know that we
have to use energy to make it happen. For example making iron from iron oxide or aluminum
from aluminum oxide, etc. Worldwide production of iron and steel is over a billion tons per year,
and aluminum is over 50 million tons per year – these definitely use much energy for their
processes. Even the clean fuel hydrogen, does not exist in nature as free molecules, we do have
to spend energy in making this fuel as well as its storage materials, We should note that most of
the 40 million tons a year of hydrogen formed world-wide emit some amount of carbon dioxide.

Once we appreciate this, we should be able to get into a mindset that accepts that we can
create fuels at will. For example, forming carbon and hydrogen from their oxides i.e. carbon
dioxide and water by using energy. This approach will become the basis to formulate
technologies that are more cost effective while allowing our present luxuries and opening up new
luxuries. We can get into a near zero effluent process development which is bound to grow
global economy, not hinder it. This new approach most importantly will make us realize that our
energy supply is unlimited. The idea, the ability to take, make and use, and the fuels -- all these
are out there waiting for us.

How do we do it?

Making hydrogen from water, converting carbon dioxide back to carbon, or changing
water and carbon dioxide mix to hydrocarbons or partly oxygenated hydrocarbons -- these are
not all that bad. The efficiencies of conversion are achievable by using energy from the sun
converted into electrical or kinetic energy, or other forms of stored energy, which is wasted.

Such conversions do not require millions of years to take place as implied by the term
‘fossil fuels.’ It is only a reaction process dictated by certain conditions. Enabling those
conditions is purely a function of the ingenuity in us. The scientific and thermodynamic
reasoning for this concept is presented in this position paper. Development of this line of
thinking will lead to proper reactor design fitting the necessary kinetics. Several thoughts
expressed here have been tried sporadically; with concerted effort from now this idea can be
brought to fruition within a few years.

Thermodynamically, it is said that a reaction will go forward easily, if the free energy of
reaction is negative. The free energy obtained by forming oxides from elements is negative
[lowest energy state]; they create energy in a fashion similar to fuels that react with an oxidant
and release heat or other such energies. Some additional Activation energy is necessary to make
the reaction kinetics work in favor.

On the other hand we have in practice, reactions which yield positive free energies of
reaction that happen by inputting external energy. The external energy added is equal to bringing
the net free energy to zero or to the negative direction at a minimum. For example, the reactions,
to convert alumina into aluminum and oxygen by a process of molten salt electrolysis, has a
positive free energy and positive heat of formation – meaning that we have to input external
energy to make this happen. But this input external energy is not all lost, it stays in the product
aluminum as stored energy for later use in several ways - only the inefficiencies in the
conversion is lost as they are left un-captured.

Let us take a look at making aluminum from aluminum oxide in molten cryolite a
fluoride compound. The melt is necessary to facilitate dissolution of alumina [in molten cryolite
- which has a 3 to 5% solubility of alumina]; aluminum comes to the graphitic floor cathode
forming molten aluminum, which further acts as cathode for added aluminum production.
Melting requires energy, and electrolysis means applying external energy. The oxygen released
at the anode is taken up by consumable anode Carbon [blocks] in aluminum electrolysis Cell
forming carbon dioxide. The free energy of formation is 301.7 kcal/gm. mole of alumina giving
oxygen at anode or 230 kcal/ gm. mole with carbon anode. The actual energy spent is usually
higher due to process inefficiencies.

Why the Yields of Bio-fuels are low?

Most present day frenzied efforts utilize plant matter [such as corn ethanol or cellulosic
ethanol, bio-butanol, etc] instead of water and carbon dioxide as starting material -- truly they are
merely subsets of a main/overall process. One continues to assume that 21st century humanity
will continue to succumb to automotive and electromotive benefits of nineteenth and twentieth
century industrialization.

Corn based ethanol has about a 7 to 9% yield of the corn production mass, if the residues
are not used as fuel. The manufacturing cellulosic ethanol utilizes only 15% to 30% of plant
matter leaving more garbage [unused lignins, ash forming material, etc]; even these release
carbon dioxide as an effluent in the fermentation process. These processes also consume
considerable energies in the several steps of collecting, size reduction, etc of the plant matter.
For instance enzymes are used to degrade part of the cellulose. Jason Hill, et al [1] has compiled
an excellent article on the Environmental, economic, and energetic costs and benefits of
biodiesel and ethanol biofuels. This shows that while ethanol gives 25 % more energy than
processing energy input, biodiesel from seeds give 93% more energy in the combustion of these
products. The author, however, in private communication notes that "you are correct in your
statement about our handling of photosynthetic solar energy input and water energy input used in plant
growth [omitted in the evaluation], although we did include the energy required for irrigation on those
lands that are irrigated". The authors also note that biofuels using food vegetation is not the answer to our
increasing clean energy thirst.

The subject of how fossil fuels are formed can be analyzed by a good analysis of biotic
matter - this is a separate discussion. Average molecular formula for plant organic matter is
(C6H9O4)n, with one nitrogen for every 50 or so carbon atoms as part of the amino acids [in
addition there are other elements and ash forming constituents]. This formula is derived from the
ultimate analysis of all the components of plants - cellulose, hemi-cellulose, and lignin. [2]
Increase of the yields in converting plant matter to hydrocarbons or even oxygenated fuels is
clearly indicated from the formula in that we need hydrogen addition, and minor oxygen
reduction in matching the formulas for hydrocarbons or oxygenated hydrocarbons.

Low temperature hydrogenation usually takes place by using ammonia and or hydrogen
sulfide, in nature. The reason why these reactions take such a long time is not only kinetics but
also insufficient presence of hydrogenating species. When some of these reactions are carried
out using less than needed amount of reactants [sub-stoichiometric] we get lots of other products
such as char, etc.

An example of insufficient amount of reactant[s] is seen every day when the plants wilt
or dry due to lack of water or drought. In nature, ammonia conversion from atmospheric
nitrogen is slow, due to insufficient reactants, but by designing a proper reactor and applying
energy – it was possible to make ammonia at will by the Haber-Bosch synthesis 90 years ago;
this only improved agriculture exponentially rather than hinder it.

Alternate Energy Sources for Soda-Fuel Cycle :

Use of the photosynthetic effect of sunlight or electrolytic energy or electric sparks like in
lightning, should facilitate these reactions, just as they do in nature to form components
cellulose, hemi cellulose and lignin of the plant kingdom. [3], [4], [5]. We can also do this by
chemical reaction energy, as well as biochemical means with proper reagents. Several studies of
cosmic and paleo-geochemistry discuss this. The electrical energy can come from solar, wind,
hydroelectric or other techniques
.
We have to fully exploit the other source of stored chemical energy as shown below. We
all know why the developing global economy and increasing population need more energy. It is
just to make life easier and luxurious. Only a part of the stored energy stays in the non-perished
items in developing the global economy. Other parts of that luxury involve creating more
unwanted or under-used material [garbage, to be simple]. But this garbage material is made
originally using energy - thus becomes a lower cost stored energy which we should use in
fossilizing carbon-dioxide, just like we can use solar energy, etc. This thinking will also help
reengineer how we dispose of garbage in landfills. Present day engineering making methane and
carbon dioixde [landfill gas LFG] is a step in the right direction. But this is a passive approach
without planning for stoichiometric reagent requirements and use, and thus a low yield method
similar to bio-fuel approach. Let us Refocus and use the stored energy in the waste material to
use in remaking fuels in a better active engineered fashion using soda-fuel reaction concepts.

Conclusion:

Let us make fuels at will and fossilize carbon dioxide while doing so. This is for
everyone -- all groups of energy enthusiasts, as well as giant oil companies, which have sources
of more concentrated carbon dioxide that can be put to use. Let us have fun doing them all.

References:

[1] Jason Hill, Erik Nelson, David Tilman, Stephen Polasky, and Douglas Tiffany, Proceedings
of the National Academy of Science - PNAS July 25, 2006 vol. 103 no. 30
[2] Channiwala, S.A. (1992). Ph.D. Thesis, Indian Institute of Technology, Bombay, India
[3] Aurian-Blajeni et al., Photo-reduction of Carbon di-oxide and Water into formaldehyde and
Methanol on semi-conductor material, Solar Energy, vol.25 (1980), pp. 165-170
[4] Hori, Y., Kikuchi K., Murata, A., and Suzuki, S., "Production of Methane and Ethylene in
electrochemical Reduction of Carbon Dioxide at Copper Electrode in Aqueous
Hydrogencarbonate Solution," Chem. Lett., 897 (1986).
[5] Abelson, P. H., Science, 124, 935 (1956).
Table 1
Soda Fuel Cycle Reactions- Energy Required

Reactants [moles] Product Product moles of minimum energy reqd.


Reaction No. CO2 H2O name formula O2 in DHf* DGf*
[Soda Fuel Cycle] Product kcal/ mole of product
A 1 x carbon C 1 94.1 94.3
B 1 2 methane CH4 2 212.8 195.5
C 1 2 methanol CH3OH 1 173.7 167.8
D 2 3 ethanol C2H5OH 3 326.7 317.3
E 4 5 butanol C4H9OH 6 636.7 621.1
F 0 1 hydrogen H2 0.5 68.3 56.7
G 1 y CarbonMonoxide CO 0.5 67.6 61.5
H 1 2.2 SynthesisGas 2.2H2+CO 2.7 217.9 186.2
I 8 9 octane [gasoline] C8H18 12.5 1306.3 1266.5

*The heats [DHf] and free energy of formation[DGf] calculated from values noted
in Handbook of Chemical Engineering, 7th Ed.
Note that reactions A and G can occur in aqueous medium without H2O reacting.
The Oxygen in product does not have to be free O2 - if using chemical energy

Table 2
Mass of Fuel with equivalent energy
expense as Hydrogen
Product Based on Based on Table 3
name DHf DGf M ass of Stored energy
mass mass equivalent as Hydrogen
carbon 4.36 3.61 in Oxide formation
methane 2.57 2.32 Element Mass
methanol 6.3 5.41 hydrogen 1.00
ethanol 4.81 4.11 aluminum 4.62
butanol 3.97 3.38 iron 19.23
hydrogen 1 1 magnesium 5.77
CarbonMonoxide 14.15 12.91 boron 2.45
SynthesisGas 5.08 4.94 carbon 4.36
octane [gasoline] 2.98 2.56 silicon 4.72

Please note that these are mass equivalents of


compounds not the equivalents when considering
the containers needed.
[Author's bio:
Neale R. Neelameggham
9859 Dream Circle, South Jordan, UT 84095
neelameggham@yahoo.com - Tel: 801 253 3592
Neale Neelameggham has a Ph.D. in metallurgy from the University of Utah, and has 33 years of
magnesium and metal industry expertise. This paper is a personal public interest paper. I would
like to acknowledge input and editing efforts by my wife Indra and the encouragement given by
my friends Vinay Kumar Saigal [representative of TOTAL, a French Oil Corporation] and others
with scientific interest on this article's impact to society].

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