EP-4736991-A1 - METHOD AND DEVICE FOR BREAKING DOWN CARBON DIOXIDE

Abstract

The present invention relates to a method and device for transforming carbon dioxide (CO 2 ) into its elements, C and O 2 , by means of the combined use of laser irradiation (4) and dielectric barrier discharge plasma (1) which are applied to high-melting-point ceramic or metallic substrate catalysts in a chamber (2). In this way, laser radiation increases the temperature only in the area in which it is applied, to the catalysts, in order for the emission plasma to reach a temperature close to 3400 K, capable of breaking down CO 2 , only in that area and not in the entire plasma reactor chamber.

Inventors

• MORO FRANCO, EUSEBIO
• DE LA FUENTE LEIS, Germán
• MOLINA MANSILLA, RICARDO
• NUÑEZ COELLO, Pedro Felipe
• ANGUREL LAMBAN, Luis Alberto

Assignees

• CO2 Breakers, S.L.
• Consejo Superior de Investigaciones Científicas (CSIC)
• Universidad De Zaragoza
• Universidad de la Laguna

Dates

Publication Date

20260506

Application Date

20230628

Claims (16)

1. Method for transforming carbon dioxide (CO 2 ) into its elements, C and O 2 , by the combined use of laser irradiation and dielectric barrier discharge (DBD) plasma, on high melting point ceramic substrate catalysts, applied in a chamber (2).
2. The method according to claim 1, wherein the laser irradiation occurs with IR, Visible, or UV sources and using lasers emitting in nanosecond (ns), picosecond (ps), or femtosecond (fs) pulse regime, or in continuous mode (cw).
3. Method according to claim 1, wherein the plasma is produced by electric discharge, microwaves, or other mechanisms, in various geometries based on dielectric barrier discharge (DBD) technology.
4. Method according to claim 3, in which the plasma is used with an output voltage between 100 V and 10 kV, an output frequency between 1 kHz and 100 kHz, an output power between 0.5 W and 10 kW, using one or more dielectric materials located between the electrodes.
5. Method according to claim 3, wherein the plasma type generated is thermal (thermodynamic equilibrium) or non-thermal (non-thermodynamic equilibrium).
6. Method according to claim 1, wherein as a catalyst, ceramic substrates containing Zirconium, Aluminum, Titanium, Barium, Cerium oxides and other rare earths, as well as alkaline earth oxides, transition metals and group 13 metals are used.
7. Method according to claim 6, wherein the catalysts are metal oxides based on Ceria (cerium dioxide CeO 2 ), doped with one or more transition metal oxides (Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper and Zinc; Yttrium, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium, Podium, Palladium, Silver and Cadmium; Hafnium, Tantalium, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold and Mercury) and/or group 13 oxides (Boron, Aluminum, Gallium, Indium, Thallium).
8. Method according to claim 1, wherein the catalysts are made up of a combination of two or more transition metal oxides (Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper and Zinc; Yttrium, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium, Rhodium, Palladium, Silver and Cadmium; Hafnium, Tantalium, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold and Mercury) and group 13 oxides (Boron, Aluminum, Gallium, Indium, Thallum).
9. Method according to any of claims 7 or 8, wherein the catalysts are used with promoters of alkali and/or alkaline earth metal oxides (Lithium, Sodium, Potassium, Rubidium, Cesium, Beryllium, Magnesium, Calcium, Strontium, Barium).
10. Method for breaking down carbon dioxide (CO 2 ) into CO and O 2 , by the combined use of laser and plasma irradiation on high melting point ceramic substrates, applied in a continuous flow reactor.
11. Device for breaking down carbon dioxide (CO 2 ) into its elements, C and O 2 , comprising: - a dielectric barrier discharge (DBD) type-plasma reactor (1), which is applied over a high melting point catalyst, said plasma reactor (1) being integrated inside a chamber provided with windows (8) suitable for laser radiation transmission (4), and gas inlets (6) and outlets (7); - a laser device (5), integrated with the plasma reactor (1); - high melting point ceramic substrate catalysts, on which the plasma and laser radiation (4) are applied, located in a window (3) of a chamber (2); and - a chamber (2), around the plasma reactor (1), provided with a window (3) in which the laser radiation (4) of the laser device (5) is applied; wherein the laser radiation increases the temperature only in the zone in which it is applied, on the catalysts, so that the emission plasma reaches a temperature close to 3400 K, capable of achieving CO 2 breaking down, only in that zone and not in the entire chamber of the plasma reactor.
12. Device according to claim 11, wherein the laser employs IR, Visible, or UV sources, and emits in pulsed mode with nanosecond (ns), picosecond (ps), or femtosecond (fs) pulse widths, emits in continuous mode (cw).
13. Device according to claim 11, wherein the laser radiation (4) illuminates the ceramic substrate surface in planar or complex geometry, by using conventional optics or by a beam movement system.
14. Device according to claim 11, wherein the laser exclusively illuminates a substrate with one or more catalysts of a ceramic nature, complemented by a plasma unit not coupled to the laser-irradiated catalyst.
15. Device according to claim 11, wherein the plasma is produced by electric discharge, microwaves, or other mechanisms, in various geometries based on dielectric barrier discharge (DBD) technology and using plasma power sources with continuous (DC) or alternating (AC) input voltage.
16. Device according to claim 11, in which the plasma is used with an output voltage between 100 V and 10 kV, an output frequency between 1 kHz and 100 kHz, an output power between 0.5 W and 10 kW, using one or more dielectric materials located between the electrodes.

Description

TECHNICAL SECTOR The invention relates to the chemical processes sector in general to react gaseous media, as well as apparatus specially adapted for this, as well as in the physical processes sector. More specifically, the invention aims to a method and equipment for breaking down carbon dioxide (CO2) into its elements. PRIOR ART There is currently an emergency situation in the world, already scientifically verified in numerous publications, with evidence of climate change in which the human factor is decisive and is associated with greenhouse gas emissions from the fossil combustion. One of the possible solutions to mitigate this destructive phenomenon is the reduction of carbon dioxide (CO2) emissions emanating from many industrial processes, which generates very high environmental and economic costs, both for society in general and for the involved industries, whose activity is vital to maintain the present and economic future of our environment. In this regard, there are a number of important industries, such as ceramics or cement, whose control of CO2 emissions is vital to maintain its leading position. On the other hand, there are passenger and goods transport means whose contribution to greenhouse gas emissions represents a significant percentage of the total. These include air and sea transport vehicles, which surpass other land freight transport means, all based on technologies that make use of fossil fuels. Among the technologies under development for reduction of carbon dioxide (CO2) emissions, those based on the use of plasmas to break chemical bonds stand out (Y. Yin et al., Phys. Chem. Chem. Phys., 2021, 23, 7974-7987). In principle, the selection of the plasma type is decisive to avoid recombination reactions that substantially decrease the cleavage process efficiency towards desirable products. These can include C and O2, or organic products (alcohols and other synthetic fuels) and O2, for example. Apparently, according to these authors, the maximum cleavage efficiency is obtained by combining a suitable emission plasma with high temperatures, in about 3400 K. One of the most relevant problems when applying this new technology in the industry is that of scaling-up, since the results obtained in research laboratories suggest the existence of scaling-up limits that can only be exceeded with new designs and innovative geometries, accompanied by complementary technologies to avoid high costs that prevent its large-scale implementation. The combination of plasmas based on dielectric discharge barriers with catalysts has already been proven, leading to a slight increase in the cleavage efficiency of CO2 molecule [R. H. Rad et al., Chemical Enginneering Journal 456 (2023) 141072; X. Gao et al., Catalysts 2022, 12, 66]. However, although this combination implies certain improvements, it is not yet sufficient to achieve the cleavage objectives that can be scaled up to an attractive industrial system from the point of view of process efficiency. On the other hand, the laser is a tool that, according to its emission characteristics, can generate local plasmas and temperatures that are located in the maximum efficiency zone, since it allows to select the plasma type and local temperature at the interface with a suitable substrate, at the same time offering a spatial and temporal control unmatched by any other technology. Likewise, laser technology has been used to promote phenomena in liquids, including molecule transformation from CO2 to CO [Yan et al., Joule 6, 2735-2744 (2022)]. Therefore, there is a need to develop alternative technologies that can facilitate the scaling-up of these technologies in a little more than experimental state, with an acceptable cost. In turn, these technologies would open the way to a more than likely integration of systems in large facilities, such as industrial chimneys and large ships. EXPLANATION OF THE INVENTION In order to achieve the proposed objectives, mentioned in the previous section, the invention proposes a method for breaking down carbon dioxide, having the characteristics of claim 1. It has been found that the laser is also very attractive to promote greater efficiency in phenomena of heterogeneous catalysis, activating the catalysts surface with optimal wavelength for this purpose. For this reason, a new method has been developed and tested for breaking down CO2 using refractory ceramics with electro and photocatalytic properties as a catalyst, to develop dielectric barrier discharge (DBD) type-integrated plasma devices, with geometries adapted to in-line laser scans that facilitate maximum interaction with the gas flow to be transformed. In summary, the present invention starts from the premise of the combined use of laser irradiation, on high melting point catalysts, in a plasma reactor, for breaking down CO2 into C and O2; the integration of laser in the plasma reactor allows not having to work at very high temperatures, since the laser radiation incre