AU2008307121A1 - Method and apparatus for performing a chemical reaction - Google Patents

Description

WO 2009/043081 PCT/AU2008/001040 METHOD AND APPARATUS FOR PERFORMING A CHEMICAL REACTION Related Application 5 The present application claims convention priority from Australian Provisional Patent Application No. AU 2007905394 (dated 3 October 2007), the content of which is incorporated herein by reference in its entirety. Field of the Invention 10 The present invention relates to chemical reactions and in particular to a method and apparatus for the synthesis of organic compounds from carbon dioxide and hydrogen. The invention has been developed primarily to synthesise organic compounds using atomic energy, on an industrial scale, and in turn reduce 15 greenhouse gases. However, it will be appreciated that the invention is not limited to this particular field of use. Background of the Invention Any discussion of the prior art throughout the specification should in no 20 way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. The most fundamental means of obtaining carbon monoxide from carbon dioxide is to heat the dioxide molecules to around 2400 "C, in turn producing carbon monoxide and oxygen. Unfortunately, the vast amounts of energy 25 required to effect such a transformation render it unfeasible when applied on an industrial scale. One source of energy is sunlight. Los Alamos Renewable Energy (LARE) have produced a prototype reactor that can funnel sunlight through a chamber window and channel it onto a ceramic rod set which collects heat and raises the 30 temperature within the chamber to around 2400 C. When carbon dioxide comes into contact with the ceramic rods at this temperature, it decomposes, as above, to WO 2009/043081 PCT/AU2008/001040 -2 release carbon monoxide. Notwithstanding the desirability of harnessing the sun's energy, one disadvantage of such a system is the high operating temperature, which may lead to thermal losses, and can reduce efficiency. Another disadvantage is that the equipment required construct and maintain a 5 system capable of withstanding these temperatures is somewhat prohibitive. An alternate method to convert carbon dioxide to carbon monoxide is through a system known as "CR5" (Counter-Rotating Ring Receiver Reactor Recuperator). Whilst this system also utilises the sun's energy, it operates at less extreme temperatures (ca. 1500 C). However, one disadvantage of such a system 10 is that successive heating and cooling cycles of cobalt ferrite ceramic rings is crucial to the process, which imparts undesirable labour intensity upon such a system. Another method is to use sunlight to convert carbon dioxide into a carbon based fuel in an electrochemical cell. However, the so-formed hydrocarbons 15 liberate relatively little energy when used as fuels. Carbon dioxide is seen as the most predominant and damaging greenhouse gas in the earth's atmosphere. Carbon dioxide is an odourless, colourless non flammable gas that is recycled through the atmosphere by the process of photosynthesis, which occurs when green plants and other organisms transform 20 light energy into chemical energy. Light energy is used to convert carbon dioxide, water, and other compounds into oxygen and energy rich organic compounds. Deforestation and burning of fossil fuel results in a large proportion of human-made carbon dioxide emissions. Carbon-containing fossil fuels such as 25 coal, oil and natural gas are used for example to generate electricity, heat houses, power factories and run cars. When they are burned, carbon from these fuels combines with oxygen to form carbon dioxide. Accordingly, over time, the concentration of greenhouse gases in the earth's atmosphere has steadily increased, insulating the earth and causing it to heat up. This, in turn, results in 30 global warming and related problems such as the melting of the polar ice-caps.

WO 2009/043081 PCT/AU2008/001040 -3 Carbon dioxide is currently at a globally averaged concentration of approximately 387 ppm by volume in the earth's atmosphere, although this is steadily increasing due to human activity. Carbon dioxide is an important greenhouse gas because it transmits visible light but absorbs strongly in the 5 infrared and near-infrared. Carbon dioxide is produced by all animals, plants, fungi and microorganisms during respiration and is used by plants during photosynthesis, to make sugars which may either be consumed again in respiration or used as the raw material for plant growth. It is, therefore, a major component of the carbon 10 cycle. Carbon dioxide is generated as a by-product of the combustion of fossil fuels or vegetable matter, among other chemical processes. Some carbon dioxide is output by volcanoes and other geothermal processes such as hot springs. The combustion of all carbon containing fuels, such as methane (natural gas), petroleum distillates (gasoline, diesel, kerosene, propane), but also of coal 15 and wood, will yield carbon dioxide and, in most cases, water. As an example, the chemical reaction between methane and oxygen is:

CH

4 + 202 -> CO 2 + 2H 2 0 20 Carbon dioxide is produced from six principal sources and processes: As a by-product in ammonia and hydrogen plants, where methane is converted to C0 2 ; From combustion of wood and fossil fuels; As a by-product of fermentation of sugar in the brewing of beer, whisky and other alcoholic beverages; From thermal decomposition of limestone, CaCO 3 , in the manufacture of lime; As a by-product 25 of sodium phosphate manufacture; Directly from natural carbon dioxide springs, where it is produced by the action of acidified water on limestone or dolomite. However, the greatest production of CO 2 is not man made but produced by the tectonic movement of the earth's plates. Greenhouse gases reduce the loss of heat into space and therefore 30 contribute to global temperatures through the greenhouse effect. Greenhouse gases are essential to maintaining the temperature of the earth; without them the WO 2009/043081 PCT/AU2008/001040 -4 planet would be so cold as to be uninhabitable. However, an excess of greenhouse gases can raise the temperature of a planet to lethal levels, as on Venus where the 90 bar partial pressure of carbon dioxide contributes to a surface temperature of about 467 'C. 5 Based on ice-core samples and records, current levels of carbon dioxide are approximately 100 ppmv higher than during immediately pre-industrial times, when direct human influence was negligible. Most greenhouse gases have both natural and anthropogenic sources. During the pre-industrial holocene, concentrations of these gases were roughly 10 constant. Since the industrial revolution, concentrations of all the long-lived greenhouse gases have increased due to human actions. Preindustrial Current Increase Gas Level Level since 1750 Carbon dioxide 280 ppm 384ppm 104 ppm Methane 700 ppb 1,745 ppb 1,045 ppb Nitric oxide 270 ppb 314 ppb 44 ppb CFC-12 0 533 ppt 533 ppt Aside from water vapor, which has a residence time of days, most 15 greenhouse gases take many years to leave the atmosphere. Although it is not easy to know with precision how long it takes specific greenhouse gases to leave the atmosphere, there are estimates for the principal greenhouse gases. Greenhouse gases can be removed from the atmosphere by various processes, including but not limited to: 20 1. As a consequence of a physical change (condensation and precipitation remove water vapor from the atmosphere). 2. As a consequence of chemical reactions within the atmosphere. This is the case for methane. It is oxidised by reaction with naturally occurring hydroxyl radicals, OH- and degraded to CO 2 and water vapor at the end of 25 a chain of reactions (the contribution of the CO 2 from the oxidation of WO 2009/043081 PCT/AU2008/001040 -5 methane is not included in the methane Global Warming Potential). This also includes solution and solid phase chemistry occurring in atmospheric aerosols. 3. As a consequence of a physical interchange at the interface between the 5 atmosphere and the other compartments of the planet. An example is the mixing of atmospheric gases into the oceans at the boundary layer. 4. As a consequence of a chemical change at the interface between the atmosphere and the other compartments of the planet. This is the case for C0 2 , which is reduced by photosynthesis of plants, and which, after 10 dissolving in the oceans, reacts to form carbonic acid and bicarbonate and carbonate ions. 5. As a consequence of a photochemical change. Halocarbons are dissociated by UV light releasing C1 and F as free radicals in the stratosphere with harmful effects on ozone (halocarbons are generally too 15 stable to disappear by chemical reaction in the atmosphere). 6. As a consequence of dissociative ionisation caused by high energy cosmic rays or lightning discharges, which break molecular bonds. For example, lightning forms N anions from N 2 which then react with 02 to form NO 2 . 20 The lifetime r of an atmospheric species X in a one-box model is the average time that a molecule of X remains in the box. Mathematically 'r can be defined as the ratio of the mass m (kg) of X in the box to its removal rate, which is the sum of the flow of X out of the box (Fost), chemical loss of X (L), and deposition of X (D) (all in kg/sec). 25 The atmospheric lifetime of a species therefore measures the time required to restore equilibrium following an increase in its concentration in the atmosphere. Individual atoms or molecules may be lost or deposited to sinks such as the soil, the oceans and other waters, or vegetation and other biological systems, reducing the excess to background concentrations. The average time 30 taken to achieve this is the mean lifetime.

WO 2009/043081 PCT/AU2008/001040 -6 The atmospheric lifetime of CO 2 is often incorrectly stated to be only a few years because that is the average time for any CO 2 molecule to stay in the atmosphere before being removed by mixing into the ocean, photosynthesis, or other processes. However, this ignores the balancing fluxes of CO 2 into the 5 atmosphere from the other reservoirs. It is the net concentration changes of the various greenhouse gases by all sources and sinks that determines atmospheric lifetime, not just the removal processes. Examples of the atmospheric lifetime and Global Warming Potential (GWP) for several greenhouse gases include: 10 e CO 2 has a variable atmospheric lifetime, and cannot be specified precisely. Recent work indicates that recovery from a large input of atmospheric

CO

2 from burning fossil fuels will result in an effective lifetime of tens of thousands of years. Carbon dioxide is defined to have a GWP of 1 over all time periods. 15 e Methane has an atmospheric lifetime of 12 ± 3 years and a GWP of 62 over 20 years, 23 over 100 years and 7 over 500 years. The decrease in GWP associated with longer times is associated with the fact that the methane is degraded to water and CO 2 by chemical reactions in the atmosphere. 20 e Nitrous oxide has an atmospheric lifetime of 120 years and a GWP of 296 over 100 years. * CFC-12 has an atmospheric lifetime of 100 years and a GWP of 10600 over 100 years. " HCFC-22 has an atmospheric lifetime of 12.1 years and a GWP of 1700 25 over 100 years. e Tetrafluoromethane has an atmospheric lifetime of 50,000 years and a GWP of 5700 over 100 years. " Sulfur hexafluoride has an atmospheric lifetime of 3,200 years and a GWP of 22000 over 100 years. 30 WO 2009/043081 PCT/AU2008/001040 -7 Accordingly, one will readily appreciate that carbon dioxide is not only the most abundant of greenhouse gases, but also one of the longest-lived. It would thus be desirous to conceive of, establish and implement new technologies that may operate in unison with photosynthesis as means of reducing atmospheric 5 carbon dioxide levels. It would thus be advantageous to have means to utilise carbon dioxide in the atmosphere to produce relatively harmless organic compounds or hydrocarbons. It would be even more advantageous to achieve same on an industrial scale with minimal waste by-products contaminating the environment. 10 It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. It is further conceivable that even where carbon dioxide could be converted to undesirable organics, these too may be in situ, or independently converted to relatively harmless products. 15 To this end, hexaketocyclohexane is a chemical contaminant, found principally in soil. Destruction of this and related contaminants is possible via the use of industrially important enzyme laccase from Coriolus versicolor, as described in US 7,169,965. Attempts to decompose hazardous chemical substances directly in plant 20 cells using transformant plants into which an enzyme gene for decomposing hazardous chemical substances derived from microorganisms are introduced, have been made with respect to 2,4,6-trichlorophenol (Japan Society for Bioscience, Biotechnology, and Agrochemistry, Abstracts for the Annual Meeting, p.16 4 , 1998) or gamma-hexacyclohexane (Japan Society for Bioscience, Biotechnology, 25 and Agrochemistry, Abstracts for the Annual Meeting, p.89, 1997). It has been clarified that laccase can decompose various chemical substances which are not readily degradable. Laccase can oxidatively decompose endocrine disrupting chemicals including chlorophenols, agricultural chemicals, polycyclic aroma hydrocarbons, alkyl phenol, aroma hydrocarbons, and nitro compounds. 30 Accordingly, when genes for phenoloxidase, e.g. laccase, are incorporated and plants which can express a function of the genes are prepared, a method of WO 2009/043081 PCT/AU2008/001040 -8 producing phenoloxidase at high yields and desirable cost levels can be established. Also, it is further possible to accomplish phyto-remediation which is useful for decomposing and removing hazardous chemical substances in the environment. 5 Thorium, as well as uranium and plutonium, can be used as fuel in a nuclear reactor. Although not fissile itself, 232 Th will absorb slow neutrons to produce (233U), which is fissile. Hence, like 238 U, it is fertile. In one significant respect 233U is better than the other two fissile isotopes used for nuclear fuel, 235 U and plutonium-239 ( 239 Pu), because of its higher neutron yield per neutron 10 absorbed. Given a start with other fissile material ( 23 1U or 23 9 Pu), a breeding cycle similar to, but more efficient than that currently possible with the 238 U-to 239 Pu cycle (in slow-neutron reactors), can be set up. The 232 Th absorbs a neutron to become 233 Th which normally emits an electron and an anti-neutrino (ve) by P decay to become protactinium-233 ( 233 Pa) and then emits another electron and 15 anti-neutrino by a second $_ decay to become 23 1U. The irradiated fuel can then be unloaded from the reactor, the 233 U separated from the thorium (a relatively simple process since it involves chemical instead of isotopic separation), and fed back into another reactor as part of a closed nuclear fuel cycle. 20 Problems include the high cost of fuel fabrication due partly to the high radioactivity of 23 3 U which is a result of its contamination with traces of the short lived 232 U; the similar problems in recycling thorium due to highly radioactive 228 Th; some weapons proliferation risk of 2 33 U; and the technical problems (not yet satisfactorily solved) in reprocessing. 25 When 233 U absorbs a neutron, it either fissions or becomes the next heavier isotope, 234U. The chance of not fissioning on absorption of a thermal neutron is about 10% or less, which is less than the corresponding capture/fission ratios for 235 U, 239 Pu or 24 1 Pu. U-234, like most actinide nuclides with an even number of neutrons, is not easily fissionable with slow neutrons, but further 30 neutron capture produces fissile 235 U; if this in turn fails to fission on neutron capture, it will produce 236 U, 237 Np, 238 Pu, and eventually fissile 239Pu. Thus WO 2009/043081 PCT/AU2008/001040 -9 production of heavy transuranic nuclides (the minor actinides other than neptunium) is far less than in the 238

U/

239 P cycle, because 98-99% of thorium cycle fuel nuclei would fission before reaching even 236 U. On the other hand, the thorium cycle produces some 23 1 Pa (half-life 33,000 years) via the (n,2n) reaction 5 on 232 Th. Because the thorium/uranium-233 cycle produces a smaller amount of long-lived actinide isotopes, the long-term radioactivity of the spent nuclear fuel is less. Common fission products have half-lives up to 30 years ( 90 Sr, 137 Cs) or more than 200,000 years ( 99 Tc), and radioactivity in the period intermediate between these two scales is chiefly from actinide wastes. Another positive, if a 10 solid-fuel reactor is used, is that thorium dioxide melts around 3,300 'C compared to 2,800 'C for uranium dioxide cycle. Nevertheless, the thorium fuel cycle, with its potential for breeding fuel without fast neutron reactors, holds considerable potential long-term benefits. Thorium is significantly more abundant than uranium, and is a key factor in 15 sustainable nuclear energy. One of the earliest efforts to use a thorium fuel cycle took place at Oak Ridge National Laboratory in the 1960s. An experimental reactor was built based on Molten Salt Reactor technology to study the feasibility of such an approach, using thorium-fluoride salt kept hot enough to be liquid, thus eliminating the need 20 for fabricating fuel elements. This effort culminated in the Molten-Salt Reactor Experiment that used 2 32 Th as the fertile material and 233 U as the fissile fuel. Due to a lack of funding, the MSR program was discontinued in 1976. Although one skilled in the art will readily appreciate that any energy source is applicable to the present invention, they will also appreciate that atomic 25 energy is preferable due to its relative cost effectiveness, cf e.g. electricity. Of the potential atomic sources, thorium is preferred due to the relatively minimal waste it produces in comparison with uranium and plutonium. Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be 30 construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

WO 2009/043081 PCT/AU2008/001040 - 10 Although the invention will be described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms. 5 Summary of the Invention According to a first aspect of the invention there is provided a method for performing a chemical reaction, said method comprising the steps of: introducing one or more predetermined reactants into a reaction chamber; 10 exciting said one or more reactants with energy derived from a fuel source in an atomic reactor, thereby to initiate said chemical reaction and provide one or more products; and isolating said one or more products; wherein said reaction chamber is in substantially non-dissipating 15 energy communication with said fuel source, thereby to relatively optirnise energy efficiency. In an embodiment, said one or more predetermined reactants comprise greenhouse gases. In another embodiment, said one or more predetermined reactants comprise carbon dioxide and hydrogen. 20 In an embodiment, said one or more predetermined reactants are in one or more state selected from the group consisting of: solid, liquid (e.g. supercritical) and gas. In an embodiment, said atomic reactor is an accelerator driven system (ADS). In another embodiment, said accelerator driven system is a thorium 25 accelerator driven system. In an embodiment, said products comprise one or more aromatic or aliphatic compounds. In an embodiment, said energy is in the form of particle rays. Preferably, said particle rays are secondary particle rays. 30 In an embodiment, the inventive method further comprises the step of providing one or more auxiliary elements selected from the group consisting of: WO 2009/043081 PCT/AU2008/001040 - 11 enzymes, catalysts, heat and pressure, thereby to relatively enhance reaction kinetics and/or effect a predetermined transformation of said one or more reactant species. In an embodiment, said one or more enzymes and said one or more 5 catalysts are selected from the group consisting of: platinum, palladium, niobium, rhodium, ruthenium, earth elements, tin or biological enzymes such as cytochrome P-450, proteasomes, decarboxylase, carbonate dehydratase, biotin as a carboxylase, carbonic anhydrase and carboxylases. In an embodiment, the inventive method further comprises the step of 10 isolating one or more intermediate products for transfer and subsequent reaction to a final product in a secondary reactor. In an embodiment, said intermediate product is hexaketocyclohexane octahydrate (triquinoyl hydrate), and said final product is benzene or cyclohexane. In an embodiment, said method is performed on an industrial scale. In an 15 embodiment, said introducing one or more predetermined reactants into said reaction chamber is performed actively or passively. Preferably, said active introduction of said one or more reactants into said reaction chamber is by means of sequestering. In an embodiment, the inventive method is applicable within a system of 20 "carbon-trading" credits or debits. According to a second aspect of the present invention there is provided one or more products of a chemical reaction, when so-formed by a method according to the first aspect of the present invention. According to a third aspect of the present invention there is provided an 25 apparatus for performing a chemical reaction, said apparatus comprising: means for introducing one or more predetermined reactants into a reaction chamber; means for exciting said one or more reactants with energy derived from a fuel source in an atomic reactor, thereby to initiate said chemical 30 reaction and provide one or more products; and means for isolating said one or more products; WO 2009/043081 PCT/AU2008/001040 - 12 wherein said reaction chamber is in substantially non-dissipating energy communication with said fuel source, thereby to relatively optimise energy efficiency. In an embodiment, said one or more predetermined reactants comprise 5 greenhouse gases. In an embodiment, said one or more predetermined reactants comprise carbon dioxide and hydrogen. In an embodiment, said one or more predetermined reactants are in one or more state selected from the group consisting of: solid, liquid (e.g. supercritical) and gas. 10 In an embodiment, said atomic reactor is an accelerator driven system (ADS). Preferably, said accelerator driven system is a thorium accelerator driven system. In an embodiment, said products comprise one or more aromatic or aliphatic compounds. 15 In an embodiment, said energy is in the form of particle rays. Preferably, said particle rays are secondary particle rays. In an embodiment, the inventive apparatus further comprises means for providing one or more auxiliary elements selected from the group consisting of: enzymes, catalysts, heat and pressure. 20 In an embodiment, said one or more enzymes and said one or more catalysts are selected from the group consisting of: platinum, palladium, niobium, rhodium, ruthenium, earth elements, tin or biological enzymes such as cytochrome P-450, proteasomes, decarboxylase, carbonate dehydratase, biotin as a carboxylase, carbonic anhydrase and carboxylases. 25 In an embodiment, the inventive apparatus further comprises means for isolating one or more intermediate products for transfer and subsequent reaction to a final product in a secondary reactor. In an embodiment, said intermediate product is hexaketocyclohexane octahydrate (triquinoyl hydrate), and said final product is benzene or cyclohexane. 30 In an embodiment, the inventive apparatus is scalable to an industrial scale. In an embodiment, said means for introducing one or more predetermined WO 2009/043081 PCT/AU2008/001040 - 13 reactants into said reaction chamber is active or passive. Preferably, said active means for introduction of said one or more reactants into said reaction chamber is by sequestering. In an embodiment, the inventive apparatus is applicable within a system of 5 "carbon-trading" credits or debits. Accordingly, it will be appreciated that the present invention combines the benefits of an atomic reactor, providing energy through particle rays to convert, for example, carbon dioxide and hydrogen to aromatic and/or aliphatic compounds. The inventive process further provides a partial solution to depletion 10 of oil reserves as energy source and raw material for many chemical compounds. The use of a thorium reactor especially provides synergistic benefits for the environment through the reduction of carbon dioxide and relatively little radioactive waste. Indeed, under the inventive process, the waste generated would need to be contained only for around 500 years, itself only around five 15 percent of the "locked-up" time necessary for most nuclear waste. Any consideration of "carbon trading", i.e. the giving and receiving of "credits" for reduction in carbon dioxide emissions, will enhance the economic potential of the present invention. In the inventive process, carbon dioxide (as gas, liquid (e.g. supercritical) 20 or dry ice) and hydrogen gas are combined with the help of the secondary rays of an atomic reactor to produce useful aliphatic and/or aromatic compounds. Thus, the present invention broadly provides a method for producing/synthesising organic compounds/raw materials from carbon dioxide and hydrogen using high energy radiation from an atomic reactor. 25 Preferably, the atomic reactor is an accelerator driven system (ADS). More preferably, the accelerator driven system is a thorium accelerator driven system. Preferably the organic compounds/raw materials are aromatic and/or aliphatic compounds. 30 Preferably, the method further includes use of enzymatic processes and/or catalyst/s and/or heat and/or pressure to catalyse the initiation and/or enhance the WO 2009/043081 PCT/AU2008/001040 -14 speed of the reaction and to produce a predetermined one or more organic molecules. The catalysts are preferably elements or mixtures of elements such as platinum, palladium, niobium, rhodium, ruthenium, -earth elements, tin or 5 biological enzymes such as cytochrome P-450, proteasomes, decarboxylase, carbonate dehydratase, biotin as a carboxylase, carbonic anhydrase and carboxylases Catalytic and/or enzymatic processes and/or pressure and/or heat can be used to convert carbon dioxide (as gas, liquid (e.g. supercritical), or dry ice) and 10 hydrogen gas into hexaketocyclohexane octahydrate (triquinoyl hydrate), which may, in turn, be reduced to benzene or other useful chemicals. Preferably, the method is performed on an industrial scale. The present invention also broadly provides a method of reducing green house gases comprising sequestering carbon dioxide for use in a method 15 according to the broad form of the invention, as described above. With regard to climate change, the term "sequestration" denotes a technique for the permanent storage of carbon dioxide or other IR active compounds so they will not be released to the atmosphere where they would contribute to the greenhouse gas effect. 20 According to another broad form of the present invention there is provided an atomic reactor system for producing/synthesising organic compounds/raw materials from carbon dioxide and hydrogen, the reactor adapted such that the vessel/chamber for synthesis of the compound is adjacent/in close contact with the fuel of the reactor to receive the necessary density of incident rays. 25 Preferably the atomic reactor is an accelerator driven system (ADS). Even more preferably, the accelerator driven system is a thorium accelerator driven system. The organic compounds/raw materials are preferably aromatic and/or aliphatic compounds. 30 WO 2009/043081 PCT/AU2008/001040 - 15 Preferred Embodiment of the Invention In an especially preferred embodiment, the present invention provides a method and apparatus for synthesising, on an industrial scale, organic compounds from carbon dioxide and hydrogen by using high-energy radiation from a thorium 5 atomic reactor. The use of carbon dioxide and hydrogen in such a method may provide product intermediates similar to the biological process of photosynthesis, which provides material to be used as an energy source or raw material for other organic compounds such as plastics. 10 Those skilled in the art will readily appreciate that depending upon the precise reaction conditions employed (stoichiometric ratio of carbon dioxide to hydrogen, temperature, pressure, catalysis, residence time, etc.), the inventive method and apparatus may give rise to any conceivable oxygen-hydrocarbon product mixture. Most preferably, triquinolyl hexahydrate (C 6

H

6 .6H 2 0) is an 15 intermediate product of the reaction of carbon dioxide with hydrogen, which is itself, conceivably reducable to benzene. The so-formed benzene can be subjected to industrial use, such as in the plastics industry. In particular, the invention concerns the production of aromatic and/or aliphatic compounds from carbon dioxide and hydrogen by using the high energy 20 delta radiation of an atomic reactor, preferably a thorium accelerator driven system (ADS). The use of an atomic reactor provides high-energy rays to enable the reaction to take place. Accelerator-driven systems are safer than normal fission reactors as they are subcritical and stop when the input current is switched off. Such a system 25 may be thorium fueled, although the accelerator-driven system is applicable to other isotopes of uranium, plutonium or any other radioisotope. Thorium cannot maintain criticality on its own, therefore the thorium reactor is "sub-critical". This means it cannot produce a chain reaction that could lead to a meltdown and is thereby a further advantage of the present invention. 30 The starting materials for a thorium reactor are generally a mixture of thorium with plutonium and uranium to provide the necessary neutrons. Alternatively, a WO 2009/043081 PCT/AU2008/001040 -16 particle accelerator, which fires protons into a target such as lead, which in turn releases neutrons that collide with thorium to initiate fission is applicable to the present invention. Additionally, the abundance of minable thorium ore is about 500 times 5 that of 235 U. Australia and India have especially high resources of thorium ore. The present invention prefers a thorium reactor as a source of high energy. The thorium reactor is also less likely to produce radioactivity in the synthesis vessel. A delta ray (sometimes called "secondary radiation") is characterised by very fast electrons produced in quantity by alpha particles or other fast energetic 10 charged particles knocking orbiting electrons out of atoms. Collectively, these electrons are defined as delta radiation when they have sufficient energy to ionise further atoms through subsequent interactions on their own. Delta rays appear as branches in the main track of a cloud chamber. These branches will appear nearer the start of the track of a heavy charged particle, where more energy is imparted 15 to the ionised electrons. Otherwise called a knock-on electron, the term "delta ray" is also used in high-energy physics to describe single electrons in particle accelerators that are exhibiting characteristic deceleration. In a bubble chamber, electrons will lose their energy more quickly than other particles through Bremsstrahlung and will 20 create a spiral track due to their small mass and the magnetic field. The Bremsstrahlung rate is proportional to the square of the acceleration of the electron. The secondary rays have an enormous speed but only a short penetration. The secondary rays activate carbon dioxide and hydrogen to the extent that 25 they react even at room temperature. The reactor provides the energy to produce aromatic and/or aliphatic compounds from carbon dioxide and hydrogen on a large/industrial scale. To enhance the kinetics of the reaction or to achieve a certain outcome of product molecule/s, one can additionally use a catalytic process and/or pressure and/or heat. 30 The catalysts are preferably elements or mixtures of elements such as platinum, palladium, niobium, rhodium, ruthenium, earth elements, tin or WO 2009/043081 PCT/AU2008/001040 -17 biological enzymes such as cytochrome P-450, proteasomes, decarboxylase, carbonate dehydratase, biotin as a carboxylase, carbonic anhydrase and carboxylases. The hydrogen and carbon dioxide can either be produced on site using the reactor's energy or provided from an outside source. 5 To achieve the desired effect, the vessel for the synthesis needs to be in close contact with the fuel of the reactor to achieve the necessary density of rays. This can be achieved by using a design similar to the one shown by Paul Harteck (1960) to produce nitrous oxide from nitrogen and oxygen. The process can produce a mixture of organic compounds obeying the stoichiometric ratios of the 10 reactant molecules, which can be separated by conventional chemical means such as vaporization, distillation or chromatography. The waste from a conventional reactor can reduce the ecological benefit of sequestering or using carbon dioxide to produce raw material for organic compounds. Therefore the preferred reactor type would be a thorium reactor, 15 which produces much less waste and can be better controlled. Examples The following Examples illustrate preferred embodiments in accordance with the present invention. 20 Example 1: Cyclic Molecules from CO 2 The reaction proceeds via the following stoichiometry, in the presence of the thorium reactor's radiation energy, and optionally, one or more selected from the group consisting of: enzyme/catalyst/heat/pressure: 25 6CO 2 + 6H2 -+ C 6 0 6 + 61120 The so-formed hexaketocyclohexane hexahydrate can be removed via conventional processes and subjected to remediation via the process of, for 30 example, US 7,169,965, as discussed above - or else reacted further, be it in WO 2009/043081 PCT/AU2008/001040 - 18 isolation or in situ, in the presence of the thorium reactor's radiation energy, and optionally, one or more selected from the group consisting of: enzyme/catalyst/heat/pressure, to give cyclohexane as per: 5

C

6 0 6 + 12H 2 -+ C 6

H

2 + 6H 2 0 Alternatively, the hexaketocyclohexane can be reacted in similar manner, under different reactor conditions to give benzene for use in the chemical industry to make products such as styrene, cumene, nylon-6 and cyclohexane. 10 The worldwide demand for styrene is approximately 18 million tones per annum; that of cumene is approximately 12 million tonnes per annum; and that of cyclohexane is estimated to reach 500 million gallons for 2008.

C

6 0 6 ± 9H2 -> C 6 11 6 + 6H 2 0 15 Example 2: Aliphatic Molecules from CO 2 The reaction proceeds via the following stoichiometry, in the presence of the thorium reactor's radiation energy, and optionally, one or more selected from the group consisting of: enzyme/catalyst/heat/pressure, to give acetylene, ethane 20 or ethane: Acetylene: 2CO 2 + 5H 2 -> C 2

H

2 + 4H20 Ethene: 2CO 2 + 6H2 - C 2 11 4 + 41120 25 Ethane: 2CO 2 + 7H 2 -> C 2 11 6 + 4H 2 0 Example 3: Sugars from CO 2 The reaction proceeds via the following stoichiometry, in the presence of the thorium reactor's radiation energy, and optionally, one or more selected from 30 the group consisting of: enzyme/catalyst/heat/pressure: WO 2009/043081 PCT/AU2008/001040 -19 6CO 2 + 12H 2 --> C 6

H

12 0 6 + 6H20 The so-formed glucose is applicable to the food industry, for example, in 5 the manufacture of chocolate or other confectionary products. Example 4: Alcohols from CO 2 The reaction proceeds via the following stoichiometry, in the presence of the thorium reactor's radiation energy, and optionally, one or more selected from 10 the group consisting of: enzyme/catalyst/heat/pressure: 2CO 2 + 6H 2 -* C 2

H

5 OH + 3H20 The so-formed ethanol is applicable to the beverage industry, for example, 15 in the distillation of spirits and other alcohol-containing products or as biofiels. Example 5: Carbonyls from CO 2 The reaction proceeds via the following stoichiometry, in the presence of the thorium reactor's radiation energy, and optionally, one or more selected from 20 the group consisting of: enzyme/catalyst/heat/pressure: 2CO 2 + 4H2 -> CH 3

CO

2 H + 21120 The so-formed acetone is applicable to the solvents industry. Other 25 ketones and esters may be applicable to the perfume or paint industries. It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as 30 broadly described. To achieve a certain mix of resulting organic molecules, a change in the radiation energy, catalyst and/or heat and/or pressure can be used.

WO 2009/043081 PCT/AU2008/001040 - 20 The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described 5 in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as 10 would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments. Similarly it should be appreciated that in the above description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, or description thereof for the 15 purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing 20 disclosed embodiment. Thus, the claims following the Preferred Embodiment of the Invention are hereby expressly incorporated into this Preferred Embodiment of the Invention, with each claim standing on its own as a separate embodiment of this invention. Furthermore, while some embodiments described herein include some but 25 not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination. 30 Furthermore, some of the embodiments are described herein as a method or combination of elements of a method that can be implemented by a processor WO 2009/043081 PCT/AU2008/001040 - 21 of a computer system or by other means of carrying out the function. Thus, a processor with the necessary instructions for carrying out such a method or element of a method forms a means for carrying out the method or element of a method. Furthermore, an element described herein of an apparatus embodiment is 5 an example of a means for carrying out the function performed by the element for the purpose of carrying out the invention. In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures 10 and techniques have not been shown in detail in order not to obscure an understanding of this description. As used herein, unless otherwise specified the use of the ordinal adjectives "first", "second", "third", etc., to describe a common object, merely indicate that different instances of like objects are being referred to, and are not intended to 15 imply that the objects so described must be in a given sequence, either temporally, spatially, in ranking, or in any other manner. In the claims below and the description herein, any one of the terms comprising, comprised of or which comprises is an open term that means including at least the elements/features that follow, but not excluding others. 20 Thus, the term comprising, when used in the claims, should not be interpreted as being limitative to the means or elements or steps listed thereafter. For example, the scope of the expression a device comprising A and B should not be limited to devices consisting only of elements A and B. Any one of the terms including or which includes or that includes as used herein is also an open term that also 25 means including at least the elements/features that follow the term, but not excluding others. Thus, including is synonymous with and means comprising. Thus, while there has been described what are believed to be the preferred embodiments of the invention, those skilled in the art will recognise that other and further modifications may be made thereto without departing from the spirit of the 30 invention, and it is intended to claim all such changes and modifications as fall within the scope of the invention. For example, any formulas given above are WO 2009/043081 PCT/AU2008/001040 - 22 merely representative of procedures that may be used. Steps may be added or deleted to methods described within the scope of the present invention. Unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like are to be 5 construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to". Although the invention has been described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms. 10

Claims (38)

1. A method for performing a chemical reaction, said method comprising the steps of: 5 introducing one or more predetermined reactants into a reaction chamber; exciting said one or more reactants with energy derived from a fuel source in an atomic reactor, thereby to initiate said chemical reaction and provide one or more products; and 10 isolating said one or more products; wherein said reaction chamber is in substantially non-dissipating energy communication with said fuel source, thereby to relatively optimise energy efficiency. 15

2. A method according to claim 1, wherein said one or more predetermined reactants comprise greenhouse gases.

3. A method according to claim 1 or claim 2, wherein said one or more predetermined reactants comprise carbon dioxide and hydrogen. 20

4. A method according to any one of the preceding claims, wherein said one or more predetermined reactants are in one or more state selected from the group consisting of: solid, liquid (e.g. supercritical) and gas. 25

5. A method according to any one of the preceding claims, wherein said atomic reactor is an accelerator driven system (ADS).

6. A method according to any one of the preceding claims, wherein said accelerator driven system is a thorium accelerator driven system. 30 WO 2009/043081 PCT/AU2008/001040 - 24

7. A method according to any one of the preceding claims, wherein said products comprise one or more aromatic or aliphatic compounds.

8. A method according to any one of the preceding claims, wherein said 5 energy is in the form of particle rays.

9. A method according to claim 8, wherein said particle rays are secondary particle rays.

10 10. A method according to any one of the preceding claims, further comprising the step of providing one or more auxiliary elements selected from the group consisting of: enzymes, catalysts, heat and pressure.

11. A method according to claim 10, wherein said one or more enzymes and 15 said one or more catalysts are selected from the group consisting of: platinum, palladium, niobium, rhodium, ruthenium, earth elements, tin or biological enzymes such as cytochrome P-450, proteasomes, decarboxylase, carbonate dehydratase, biotin as a carboxylase, carbonic anhydrase and carboxylases. 20

12. A method according to any one of the preceding claims, further comprising the step of isolating one or more intermediate products for transfer and subsequent reaction to a final product in a secondary reactor. 25

13. A method according to claim 12, wherein said intermediate product is hexaketocyclohexane octahydrate (triquinoyl hydrate), and said final product is benzene or cyclohexane.

14. A method according to any one of the preceding claims, wherein said 30 method is performed on an industrial scale. WO 2009/043081 PCT/AU2008/001040 - 25

15. A method according to any one of the preceding claims, wherein said introducing one or more predetermined reactants into said reaction chamber is performed actively or passively. 5

16. A method according to claim 15, wherein said active introduction of said one or more reactants into said reaction chamber is by means of sequestering.

17. A method according to any one of the preceding claims, when applied 10 within a "carbon-trading" credits system.

18. One or more products of a chemical reaction, when so-formed by a method according to any one of the preceding claims. 15

19. An apparatus for performing a chemical reaction, said apparatus comprising: means for introducing one or more predetermined reactants into a reaction chamber; means for exciting said one or more reactants with energy derived 20 from a fuel source in an atomic reactor, thereby to initiate said chemical reaction and provide one or more products; and means for isolating said one or more products; wherein said reaction chamber is in substantially non-dissipating energy communication with said fuel source, thereby to relatively optimise 25 energy efficiency.

20. An apparatus according to claim 19, wherein said one or more predetermined reactants comprise greenhouse gases. 30

21. An apparatus according to claim 19 or claim 20, wherein said one or more predetermined reactants comprise carbon dioxide and hydrogen. WO 2009/043081 PCT/AU2008/001040 -26

22. An apparatus according to any one of claims 19 to 21, wherein said one or more predetermined reactants are in one or more state selected from the group consisting of: solid, liquid (e.g. supercritical) and gas. 5

23. An apparatus according to any one of claims 19 to 22, wherein said atomic reactor is an accelerator driven system (ADS).

24. An apparatus according to any one of claims 19 to 23, wherein said 10 accelerator driven system is a thorium accelerator driven system.

25. An apparatus according to any one of claims 19 to 24, wherein said products comprise one or more aromatic or aliphatic compounds. 15

26. An apparatus according to any one of claims 19 to 25, wherein said energy is in the form of particle rays.

27. An apparatus according to claim 26, wherein said particle rays are secondary particle rays. 20

28. An apparatus according to any one of claims 19 to 27, further comprising means for providing one or more auxiliary elements selected from the group consisting of: enzymes, catalysts, heat and pressure. 25

29. An apparatus according to claim 28, wherein said one or more enzymes and said one or more catalysts are selected from the group consisting of: platinum, palladium, niobium, rhodium, ruthenium, earth elements, tin or biological enzymes such as cytochrome P-450, proteasomes, decarboxylase, carbonate dehydratase, biotin as a carboxylase, carbonic 30 anhydrase and carboxylases. WO 2009/043081 PCT/AU2008/001040 - 27

30. An apparatus according to any one of claims 19 to 29, further comprising means for isolating one or more intermediate products for transfer and subsequent reaction to a final product in a secondary reactor. 5

31. An apparatus according to claim 30, wherein said intermediate product is hexaketocyclohexane octahydrate (triquinoyl hydrate), and said final product is benzene or cyclohexane.

32. An apparatus according to any one of claims 19 to 31, scalable to an 10 industrial scale.

33. An apparatus according to any one of claims 19 to 32, wherein said means for introducing one or more predetermined reactants into said reaction chamber is active or passive. 15

34. An apparatus according to claim 33, wherein said active means for introduction of said one or more reactants into said reaction chamber is by sequestering. 20

35. An apparatus according to any one of claims 19 to 34, applicable within a "carbon-trading" credits system.

36. A method for performing a chemical reaction, said method substantially as herein described with reference to any one of the embodiments of the 25 invention illustrated in the accompanying examples.

37. One or more products of a chemical reaction, when so-formed by a method substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying examples. 30 WO 2009/043081 PCT/AU2008/001040 - 28

38. An apparatus for performing a chemical reaction, said apparatus substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying examples.