WO2009043081A1 - Procédé et appareil pour effectuer une réaction chimique - Google Patents

Procédé et appareil pour effectuer une réaction chimique Download PDF

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WO2009043081A1
WO2009043081A1 PCT/AU2008/001040 AU2008001040W WO2009043081A1 WO 2009043081 A1 WO2009043081 A1 WO 2009043081A1 AU 2008001040 W AU2008001040 W AU 2008001040W WO 2009043081 A1 WO2009043081 A1 WO 2009043081A1
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reactants
products
energy
carbon dioxide
reactor
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English (en)
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Hans Klieber
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NOKUTA Pty Ltd
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NOKUTA Pty Ltd
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Priority claimed from AU2007905394A external-priority patent/AU2007905394A0/en
Application filed by NOKUTA Pty Ltd filed Critical NOKUTA Pty Ltd
Priority to AU2008307121A priority Critical patent/AU2008307121B2/en
Publication of WO2009043081A1 publication Critical patent/WO2009043081A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen

Definitions

  • 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 greenhouse gases. However, it will be appreciated that the invention is not limited to this particular field of use.
  • LARE Los Alamos Renewable Energy
  • Another method is to use sunlight to convert carbon dioxide into a carbon- based fuel in an electrochemical cell.
  • the so-formed hydrocarbons 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 nonflammable gas that is recycled through the atmosphere by the process of photosynthesis, which occurs when green plants and other organisms transform light energy into chemical energy. Light energy is used to convert carbon dioxide, water, and other compounds into oxygen and energy rich organic compounds.
  • Carbon-containing fossil fuels such as 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 global warming and related problems such as the melting of the polar ice-caps.
  • 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 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 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.
  • Carbon dioxide is produced from six principal sources and processes: As a by-product in ammonia and hydrogen plants, where methane is converted to CO 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 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 contribute to global temperatures through the greenhouse effect. Greenhouse gases are essential to maintaining the temperature of the earth; without them the 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 0 C.
  • Greenhouse gases can be removed from the atmosphere by various processes, including but not limited to: 1. As a consequence of a physical change (condensation and precipitation remove water vapor from the atmosphere).
  • Halocarbons are dissociated by UV light releasing Cl- and F- as free radicals in the stratosphere with harmful effects on ozone (halocarbons are generally too stable to disappear by chemical reaction in the atmosphere).
  • the lifetime ⁇ of an atmospheric species X in a one-box model is the average time that a molecule of X remains in the box.
  • Mathematically ⁇ 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 (F ou t), chemical loss of X (L), and deposition of X (D) (all in kg/sec).
  • 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 taken to achieve this is the mean lifetime.
  • Examples of the atmospheric lifetime and Global Warming Potential (GWP) for several greenhouse gases include: • CO 2 has a variable atmospheric lifetime, and cannot be specified precisely.
  • Carbon dioxide is defined to have a GWP of 1 over all time periods.
  • 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.
  • 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 over 100 years.
  • 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. 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 carbon dioxide levels.
  • Laccase can oxidatively decompose endocrine disrupting chemicals including chlorophenols, agricultural chemicals, polycyclic aroma hydrocarbons, alkyl phenol, aroma hydrocarbons, and nitro compounds. 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 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. Thorium, as well as uranium and plutonium, can be used as fuel in a nuclear reactor.
  • the 39 Pu cycle in slow-neutron reactors, can be set up.
  • the 232 Th absorbs a neutron to become Th which normally emits an electron and an anti-neutrino (v e -) by ⁇ " decay to become protactinium-233 ( 233 Pa) and then emits another electron and anti-neutrino by a second ⁇ ⁇ decay to become 233 U.
  • 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.
  • Problems include the high cost of fuel fabrication due partly to the high radioactivity of 233 U which is a result of its contamination with traces of the shortlived 232 U; the similar problems in recycling thorium due to highly radioactive 228 Th; some weapons proliferation risk of 233 U; and the technical problems (not yet satisfactorily solved) in reprocessing.
  • U absorbs a neutron, it either fissions or becomes the next heavier isotope, 234 U.
  • any energy source is applicable to the present invention, they will also appreciate that atomic energy is preferable due to its relative cost effectiveness, cf. e.g. electricity.
  • thorium is preferred due to the relatively minimal waste it produces in comparison with uranium and plutonium.
  • a method for performing a chemical reaction comprising the steps of: 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 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.
  • said one or more predetermined reactants comprise greenhouse gases. In another 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.
  • said atomic reactor is an accelerator driven system (ADS).
  • said accelerator driven system is a thorium accelerator driven system.
  • said products comprise one or more aromatic or aliphatic compounds.
  • said energy is in the form of particle rays.
  • said particle rays are secondary particle rays.
  • the inventive method further comprises the step of providing one or more auxiliary elements selected from the group consisting of: enzymes, catalysts, heat and pressure, thereby to relatively enhance reaction kinetics and/or effect a predetermined transformation of said one or more reactant species.
  • 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.
  • the inventive method further comprises the step of isolating one or more intermediate products for transfer and subsequent reaction to a final product in a secondary reactor.
  • said intermediate product is hexaketocyclohexane octahydrate (triquinoyl hydrate), and said final product is benzene or cyclohexane.
  • said method is performed on an industrial scale.
  • said introducing one or more predetermined reactants into said reaction chamber is performed actively or passively.
  • said active introduction of said one or more reactants into said reaction chamber is by means of sequestering.
  • the inventive method is applicable within a system of "carbon-trading" credits or debits.
  • an apparatus for performing a chemical reaction 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 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 energy efficiency.
  • said one or more predetermined reactants comprise greenhouse gases. In an embodiment, said one or more predetermined reactants comprise carbon dioxide and hydrogen.
  • 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.
  • said atomic reactor is an accelerator driven system
  • said accelerator driven system is a thorium accelerator driven system.
  • said products comprise one or more aromatic or aliphatic compounds.
  • said energy is in the form of particle rays.
  • said particle rays are secondary particle rays.
  • the inventive apparatus further comprises means for providing one or more auxiliary elements selected from the group consisting of: enzymes, catalysts, heat and pressure.
  • 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.
  • 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.
  • said intermediate product is hexaketocyclohexane octahydrate (triquinoyl hydrate), and said final product is benzene or cyclohexane.
  • the inventive apparatus is scalable to an industrial scale.
  • said means for introducing one or more predetermined reactants into said reaction chamber is active or passive.
  • said active means for introduction of said one or more reactants into said reaction chamber is by sequestering.
  • the inventive apparatus is applicable within a system of "carbon-trading" credits or debits.
  • 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 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 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.
  • carbon dioxide as gas, liquid (e.g. supercritical) or dry ice
  • hydrogen gas is combined with the help of the secondary rays of an atomic reactor to produce useful aliphatic and/or aromatic compounds.
  • 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.
  • the atomic reactor is an accelerator driven system (ADS).
  • ADS accelerator driven system
  • the accelerator driven system is a thorium accelerator driven system.
  • the organic compounds/raw materials are aromatic and/or aliphatic compounds.
  • 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 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 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 hydrogen gas into hexaketocyclohexane octahydrate (triquinoyl hydrate), which may, in turn, be reduced to benzene or other useful chemicals.
  • carbon dioxide as gas, liquid (e.g. supercritical), or dry ice
  • hydrogen gas hexaketocyclohexane octahydrate
  • triquinoyl hydrate triquinoyl hydrate
  • 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 according to the broad form of the invention, as described above.
  • 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.
  • the atomic reactor is an accelerator driven system (ADS).
  • the accelerator driven system is a thorium accelerator driven system.
  • the organic compounds/raw materials are preferably aromatic and/or aliphatic compounds.
  • 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 atomic reactor.
  • the invention concerns the production of aromatic and/or aliphatic compounds from carbon dioxide and hydrogen by using the high energy delta radiation of an atomic reactor, preferably a thorium accelerator driven system (ADS).
  • an atomic reactor preferably a thorium accelerator driven system (ADS).
  • ADS thorium accelerator driven system
  • 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 may be thorium fueled, although the accelerator-driven system is applicable to other isotopes of uranium, plutonium or any other radioisotope.
  • the starting materials for a thorium reactor are generally a mixture of thorium with plutonium and uranium to provide the necessary neutrons.
  • a 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.
  • the abundance of minable thorium ore is about 500 times 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 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 to the ionised electrons.
  • delta ray is also used in high-energy physics to describe single electrons in particle accelerators that are exhibiting characteristic deceleration.
  • electrons will lose their energy more quickly than other particles through Bremsstrahlung and will 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 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.
  • the catalysts are preferably elements or mixtures of elements such as 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.
  • the hydrogen and carbon dioxide can either be produced on site using the reactor's energy or provided from an outside source.
  • 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 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, which produces much less waste and can be better controlled.
  • the reaction proceeds via the following stoichiometry 5 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:
  • the so-formed hexaketocyclohexane hexahydrate can be removed via conventional processes and subjected to remediation via the process of, for example, US 7,169,965, as discussed above - or else reacted further, be it in 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:
  • 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.
  • 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.
  • 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 or ethane:
  • Acetylene 2CO 2 + 5H 2 ⁇ C 2 H 2 + 4H 2 O
  • the reaction proceeds via the following stoichiometry s 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: 6CO 2 + 12H 2 ⁇ C 6 H 12 O 6 + 6H 2 O
  • the so-formed glucose is applicable to the food industry, for example, in the manufacture of chocolate or other confectionary products.
  • 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:
  • the so -formed ethanol is applicable to the beverage industry, for example, in the distillation of spirits and other alcohol-containing products or as bio fuels.
  • 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:
  • the so -formed acetone is applicable to the solvents industry.
  • Other ketones and esters may be applicable to the perfume or paint industries.
  • any of the claimed embodiments can be used in any combination.
  • some of the embodiments are described herein as a method or combination of elements of a method that can be implemented by a processor of a computer system or by other means of carrying out the function.
  • 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.
  • an element described herein of an apparatus embodiment is an example of a means for carrying out the function performed by the element for the purpose of carrying out the invention.
  • 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.
  • the term comprising, when used in the claims should not be interpreted as being limitative to the means or elements or steps listed thereafter.
  • 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 means including at least the elements/features that follow the term, but not excluding others. Thus, including is synonymous with and means comprising.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention combine les avantages d'un réacteur atomique, fournissant de l'énergie par rayonnements de particules pour convertir, par exemple, du dioxyde de carbone et de l'hydrogène en composés aromatiques et/ou aliphatiques. Dans le procédé de l'invention, le dioxyde de carbone (sous forme de gaz, de liquide (par exemple, supercritique), ou de glace sèche) et de l'hydrogène gazeux sont combinés à l'aide des rayonnements secondaires d'un réacteur atomique afin de produire des composés aliphatiques et/ou aromatiques utiles. De préférence, le réacteur atomique est un système piloté par accélérateur (ADS). Mieux encore, le système piloté par accélérateur est un système au thorium piloté par accélérateur. L'invention présente un double avantage en remplaçant les combustibles fossiles comme source d'énergie et de matières premières limitées de valeur, tout en réduisant la quantité de dioxyde de carbone à effet de serre. De préférence, les composés organiques/matières premières produites sont des composés aromatiques et/ou aliphatiques. L'application de la présente invention à un système d'échange de carbone est envisagée.
PCT/AU2008/001040 2007-10-03 2008-07-17 Procédé et appareil pour effectuer une réaction chimique Ceased WO2009043081A1 (fr)

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Application Number Priority Date Filing Date Title
AU2008307121A AU2008307121B2 (en) 2007-10-03 2008-07-17 Method and apparatus for performing a chemical reaction

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AU2007905394A AU2007905394A0 (en) 2007-10-03 A system to synthesize, on an industrial scale, organic compounds from carbon dioxide (CO2) and hydrogen (H2) by using high energy radiation from an atomic reactor (preferable a thorium reator). This in turn helps to reduce greenhouse gases and global warming and provides valuable raw materials
AU2007905394 2007-10-03

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Cited By (4)

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WO2011060482A1 (fr) * 2009-11-18 2011-05-26 Nokuta Pty Ltd Procédé et appareil permettant de réaliser une réaction chimique
GB2484095A (en) * 2010-09-29 2012-04-04 Kristian La Vda Carbon dioxide recovery method
US20170154691A1 (en) * 2015-02-23 2017-06-01 Harold James Willard, JR. Post-meltdown nuclear power plant recovery system
CN115504846A (zh) * 2022-09-20 2022-12-23 中国工程物理研究院材料研究所 一种利用电离辐射催化二氧化碳合成气制备有机物的方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011060482A1 (fr) * 2009-11-18 2011-05-26 Nokuta Pty Ltd Procédé et appareil permettant de réaliser une réaction chimique
GB2484095A (en) * 2010-09-29 2012-04-04 Kristian La Vda Carbon dioxide recovery method
WO2012044178A1 (fr) 2010-09-29 2012-04-05 Loevdal Kristian Réaction de dioxyde de carbone avec de l'hydrogène pour produire du méthane
US20170154691A1 (en) * 2015-02-23 2017-06-01 Harold James Willard, JR. Post-meltdown nuclear power plant recovery system
CN115504846A (zh) * 2022-09-20 2022-12-23 中国工程物理研究院材料研究所 一种利用电离辐射催化二氧化碳合成气制备有机物的方法

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