WO2023195908A1

WO2023195908A1 - Method and apparatus for producing hydrogen from water and carbon monoxide by ionizing radiation

Info

Publication number: WO2023195908A1
Application number: PCT/SE2023/050317
Authority: WO
Inventors: Mats Hedman
Original assignee: Ase, Alternative Solar Energy Engine Ab
Priority date: 2022-04-06
Filing date: 2023-04-05
Publication date: 2023-10-12

Abstract

There is provided a method of producing hydrogen from water and carbon monoxide irradiated by an ionizing radiation device (7). Further, there is provided an apparatus for producing hydrogen from water and carbon monoxide.

Description

METHOD AND APPARATUS FOR PRODUCING HYDROGEN FROM WATER AND CARBON MONOXIDE BY IONIZING RADIATION

TECHNICAL FIELD

The present invention relates to a method of producing hydrogen, and more specifically to a method of producing hydrogen from water and carbon monoxide. Additionally, the present invention further relates to an apparatus for producing hydrogen from water and carbon monoxide.

BACKGROUND

Today, pure hydrogen is usually produced from natural gas or by electrolysis of water which are energy-intensive methods and therefore are expensive methods.

World-wide experiments are under way to use artificial photosynthesis to split water into oxygen and hydrogen ions (protons) as in Photosystem II, the first stage of photosynthesis, a photolysis in which water molecules are split into hydrogen ions and oxygen. However, a suitable catalyst has not yet been found.

If hydrogen could be produced from water in an energy-efficient way at low cost, there is an inexhaustible source of energy.

SUMMARY OF INVENTION

It would be advantageous to provide an improved method for producing hydrogen from water which method is energy efficient.

This object is achieved by a method according to the present invention as defined in the appended claims, which are directed to a method for producing hydrogen from water and carbon monoxide.

In an aspect the present disclosure relates to a method of producing hydrogen from water and carbon monoxide, comprising the steps of mixing water and a gas comprising carbon monoxide to provide a mixture, and radiating the mixture with ionization radiation using at least one ionization radiation device. For example, the at least one ionization radiation device is a lamp or an X-ray tube.

The invention is based on the insight that hydrogen can be produced from water by using photolysis and carbon monoxide. In the present disclosure, the term "photolysis" means a chemical reaction in which an inorganic chemical is broken down by photons and is the interaction of one or more photons with one target molecule.

Furthermore, autoprotolysis of water involves the continuous decomposition of part of the water net into hydrogen ions (H+) and hydroxide ions (OH-) and the re-formation of water by fusion of the ions. This process can be stimulated by ionization light adding the energy of the photons to the internal energy of the atoms (electrons are excited). If carbon monoxide (CO), a highly reactive gas, is added to water, carbon dioxide (CO2) and hydrogen (H2) are formed. Ionization light may be added at low cost via e.g. lamps. Since water autoprotolysis already occurs, this contributes to a method of production of hydrogen which is energy efficient.

According to SMHI, the Swedish Metrological and Hydrological Institute, (http://www.smhi.se/reflab/om-luftfororeningar/luftfororeningar/kolmonoxid-l.19669), "Carbon monoxide reacts with OH radicals and forms a hydrogen radical and carbon dioxide according to CO + OH -> H + C02". In the atmosphere, the reaction takes place through existing ionization radiation. According to the present invention, water is radiated with ionization radiation including the following reactions: OH + CO -> C02 + H and thus 2*(0H + CO) -> 2 C02 + H2. The hydrogen radicals formed combine to form hydrogen H2. For each molecule of CO, a hydrogen molecule is thus formed.

In the present disclosure, the reaction CO + OH -> H + C02 takes place by mixing a gas comprising CO and water and radiate the mixture with ionization radiation. Thus, the method requires water, carbon monoxide and ionization radiation. Ionization radiation is advantageously added via light from e.g. lamps and/or X-ray tubes. Preferably, the water and carbon monoxide is exposed to photons via photolysis.

An advantage with the present method utilizing ionization radiation is that the ionization radiation does not split the water into molecular hydrogen and oxygen, as in electrolysis and radiolysis, but stops at the formation of hydrogen radicals H and hydroxyl radicals 0H-. The present method is less energy consuming than known methods for splitting water, such as electrolysis. In particular, H20-> H-radical + OH-radical, whereby 56.84 KJ/mol is required.

Decomposition of water via electrolysis: H20-> H2+0, whereby 285.83 KJ/mol is required. Thus, in order to split water into H and OH- less than 1/5 of the energy necessary for splitting water into hydrogen and oxygen via electrolysis is needed. Furthermore, the method in accordance with the present disclosure is exotermic and heat is generated. This provides a method for producing hydrogen which is considerably less energy-intensive that known methods for producing hydrogen and thus cost-saving.

In another aspect the present disclosure relates to an apparatus for producing hydrogen from water, wherein the apparatus comprises a container for water; at least one feeding means for providing water into the container; at least one feeding means for providing a gas into the container such as to mix said gas into the water to provide a mixture of gas in water; at least one ionization radiation device for providing ionization radiation to the mixture of gas in water in the container; and at least one discharging means for removing hydrogen and carbon dioxide from the container, wherein the gas comprises carbon monoxide.

An advantage with the present apparatus for producing hydrogen is that hydrogen may be produced efficiently and with low energy. In yet another aspect the present disclosure relates to a hydrogen fuel cell comprising an apparatus for producing hydrogen in accordance with the present disclosure.

An advantage with the present hydrogen fuel cell is that hydrogen may be produced just before being used in the hydrogen fuel cell. The hydrogen may not be stored for a long time. Instead, the hydrogen may be used instantly.

The global transport needs of goods and people, among others, must be met with minimal emissions of carbon and nitrogen oxides and particulate matter. Phasing out internal combustion engines is considered an important measure to achieve climate goals. Fuel cells for the energy conversion of hydrogen into electricity have been highlighted as a future technology for solving transport needs through electrically powered vehicles. Hydrogen fuel cells are more efficient than current internal combustion engines and produce only water vapor in addition to heat. In the EU, there is a political orientation towards meeting society's energy needs with hydrogen.

In one embodiment the present disclosure relates to a method according to the present disclosure wherein the mixture is radiated with photons.

In one embodiment the present disclosure relates to a method according to the present disclosure wherein the lamp is a LED lamp, preferably a UV-C LED lamp or a UV-B LED lamp.

In another embodiment the present disclosure relates to a method according to the present disclosure wherein the X-ray tube is a cold-cathode X-ray tube.

Lamps, such as LED lamps, such as UV-B and UV-C, and X-ray tube have, in that order, increasingly shorter wavelength and provide powerful ionization radiation. This ionization radiation is able to knock out electrons in water molecules (=photolysis). The ionization radiation provides energy enough for breaking bonds in the water molecule. For avoidance of doubt, in accordance with the present disclosure the energy of photons is utilized.

In another embodiment the present disclosure relates to a method according to the present disclosure wherein the water is water vapor.

In another embodiment the present disclosure relates to a method according to the present disclosure wherein the gas is carbon monoxide.

In one embodiment the present disclosure relates to an apparatus according to the present disclosure wherein the at least one ionization radiation device is a lamp or an X-ray tube.

In another embodiment the present disclosure relates to an apparatus according to the present disclosure, wherein the X-ray tube is a cold-cathode X-ray tube.

In another embodiment the present disclosure relates to an apparatus according to the present disclosure wherein the lamp is a LED lamp preferably a UV-C LED lamp or a UV-B LED lamp. In another embodiment the present disclosure relates to an apparatus according to the present disclosure, wherein the water is water vapor.

In another embodiment the present disclosure relates to an apparatus according to the present disclosure, wherein the gas is carbon monoxide.

In another embodiment the present disclosure relates to an apparatus according to the present disclosure, wherein the apparatus further comprises at least one mirror inside the container for reflecting ionization radiation.

In another embodiment the present disclosure relates to an apparatus according to the present disclosure, wherein the apparatus further comprises at least one collecting device such as to collect hydrogen and carbon dioxide from the at least discharging means.

Those skilled in the art realize that different features of the present invention can be combined to create embodiments other than those described in the following.

BRIEF DESCRIPTION OF THE DRAWINGS

The above, as well as additional objects, features and advantages of the present invention, will be better understood through the following illustrative and non-limiting detailed description of preferred embodiments of the present invention, with reference to the appended drawings, wherein:

Fig. 1, a schematic illustration of an apparatus for producing hydrogen from carbon monoxide and water;

Fig. 2, a schematic illustration of an apparatus for producing hydrogen from carbon monoxide and water;

Fig. 3, a schematic illustration of an apparatus for producing hydrogen from carbon monoxide and water vapor;

Fig. 4, a schematic illustration of an apparatus for production of hydrogen from water vapor to be used in e.g. a fuel cell.

All the figures are schematic, not necessarily to scale, and generally only show parts which are necessary in order to elucidate the invention, wherein other parts may be omitted or merely suggested.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method and apparatus for producing hydrogen from water. In particular, hydrogen and carbon dioxide are produced from water and carbon monoxide.

The present disclosure provides a method of producing hydrogen from water, comprising the steps of mixing water and a gas comprising carbon monoxide to provide a mixture, and radiating the mixture with ionization radiation using at least one ionization radiation device, wherein the at least one ionization radiation device is a lamp or an X-ray tube. In one example, the method of producing hydrogen from water comprises the steps of mixing water and a gas comprising carbon monoxide to provide a mixture and radiating the mixture with photons using at least one ionization radiation device, wherein at least one ionization radiation device is a lamp or an X-ray tube.

The lamp may be a LED lamp, such as a UV-B LED lamp or a UV-C LED lamp. The X-ray tube may be a cold-cathode X-ray tube.

Carbon monoxide, CO, may be found in e.g. combustion gases and synthesis gases. Carbon monoxide may e.g. be produced by oxygen-deficient combustion. Carbon monoxide can be produced at low cost e.g. by pyrolysis of biomass. In one example, the gas comprising carbon monoxide is carbon monoxide.

Water can be in a liquid form or in a gaseous form. For example, water may be in the form of water vapor. The method of producing hydrogen from water according to the present disclosure is exothermic and the heat generated may be used to create water vapor of water. Water vapor may be used in the method according to the present disclosure.

For example, water vapor may be formed by boiling water with heat generated performing the method in accordance with the present disclosure.

Carbon dioxide, CO2, can be separated from hydrogen by centrifugation.

The method in accordance with the present disclosure may be performed at a temperature from 0 to 100°, preferably at room temperature. The method in accordance with the present disclosure may be performed at 1 bar.

The method of the present disclosure may be utilized in an apparatus in accordance with the present disclosure. An apparatus for producing hydrogen from water, wherein the apparatus comprises a container for water; at least one feeding means for providing water into the container; at least one feeding means for providing a gas into the container such as to mix the gas into the water to provide a mixture of gas in water; at least one ionization radiation device for providing ionization radiation to the mixture of gas in water in the container; and at least one discharging means for removing hydrogen and carbon dioxide from the container.

The gas may comprise carbon monoxide. In other examples, the gas is carbon monoxide.

In one embodiment, the container for water is a closed compartment. For example, the container can be made of steel. In one example, the container for water has a reflective surface for ionization radiation. In one example, the material of the container for water is blocking ionization radiation to pass through the walls of the container.

The water may be added to the container with a feeding means, for example an inlet. The inlet may be a pipe. The container may have at least one feeding means, such as at least two, such as at least three, such as at least four, such as at least ten feeding means for providing water into the container.

The at least one ionization radiation device may be a lamp or an X-ray tube. The container may have at least one, such as at least two, such as at least three, at least four, or such as at least ten ionization radiation devices.

In one embodiment, the container for water comprises at least one mirror for reflecting ionization radiation.

According to the present disclosure, when exposing water and carbon monoxide in a container with ionization radiation, hydrogen and carbon dioxide are produced. The apparatus comprises at least one discharging means for removing hydrogen and carbon dioxide from the container. The apparatus comprises at least two, such as at least three, such as at least four, such as at least ten discharging means for removal of hydrogen and carbon dioxide. The hydrogen and carbon dioxide may be removed with the same discharging means. In another example, the hydrogen and carbon dioxide are removed with separate discharging means. In one example, the discharging means is an outlet. The outlet may be a pipe.

The apparatus may further comprise at least one collecting device for collecting hydrogen and carbon dioxide. The apparatus may comprise at least two, such as at least three, such as at least four, such at least ten collecting devices. The hydrogen and carbon dioxide may be collected in the same collecting device. In another example, the hydrogen and carbon dioxide are collected in separate collecting devices.

The collecting device may be a container.

In one embodiment, water in the container is circulated through the ionization radiation device, producing OH and H radicals. CO is introduced via a feeding means, for example an inlet, and atomised via at least one nozzle to form microbubbles into the water as it enters the container. The OH radicals react with CO and thus CO2 and H radicals are formed. Two H radicals combine to form H2. The water in the container is not pressurised and the CO2, like the H2, bubbles up to a space above the water surface and on to a gas separator (for example a centrifuge) where the H2 is separated from the CO2 and each gas is compressed and taken to its respective collecting device, for example respective container.

The method of the present disclosure may be used to produce hydrogen which hydrogen may be utilized in a vehicle drive system, such as a hydrogen-electric vehicle drive system. For example, such vehicle drive system may comprise a container for water, a container for carbon monoxide, an electric battery, a device for scattering ionization radiation, a fuel cell for generating electricity from hydrogen, an electric motor for moving a vehicle and a collecting device for formed carbon dioxide. Thus, the hydrogen may be used in a fuel cell to generate electricity to a vehicle. For example, the electricity may be used to both drive the vehicle and to charge an electric battery on the same vehicle. For example, the hydrogen may be produced and used on board of a vehicle.

In accordance with the present disclosure, a fuel cell may emit water vapor from which H2 can be recovered via ionization radiation and addition of CO. The H2 may then be further used in the same fuel cell. In one example, carbon monoxide may be used as an alternative fuel for hydrogen fuel cells.

Furthermore, the water formed during the generation of electricity by the fuel cell may be returned to the container for water. For example, hydrogen may be produced from water vapor produced in a hydrogen fuel cell. Hydrogen formed in accordance with the present disclosure may be fed to a fuel cell, such as a hydrogen fuel cell, or stored for later use in e.g. a fuel cell.

The description above and the appended drawings are to be considered as non-limiting examples of the invention. The person skilled in the art realizes that several changes and modifications may be made within the scope of the invention.

Fig. 1 shows schematically an embodiment of the present invention. A source where carbon monoxide is formed 1, a pipe 3 for gas comprising carbon monoxide leads from the source 1 to a space 4 with gas purification which may for example consist of a particle filter and a catalyst for converting nitrogen oxides into nitrogen and water. From the space 4 the gas is led via a pipe 31 to a space 5 with water where the gas is dispersed in the water. In the space 5 there is at least one source 7 for dispersing ionization radiation e.g. red light from a LED lamp into the water with the gas comprising carbon monoxide, whereby carbon dioxide and hydrogen are produced. In the last part of the pipe 32, there is a collector 8 of carbon dioxide and hydrogen which is separated in the following steps (not shown in the figure).

Fig 2. shows schematically an embodiment of the present invention. A source where carbon monoxide is formed or exists 1, a pipe 3 for a gas comprising carbon monoxide leads from the source 1 to a space 4 with gas purification which may, for example, comprise a particle filter and a catalyst for converting nitrogen oxides into nitrogen and water. From the space 4, the gas is led via a pipe 31 to a space 5 with water where the gas is dispersed in the water. In the space 5 there is at least one pipe 6 with ionization apparatus 7 for dispersing and circulating ionized water with the gas comprising carbon monoxide whereby carbon dioxide and hydrogen are formed. From the space 5, the gas is passed on via a pipe 8 after which carbon dioxide and hydrogen are separated and disposed in subsequent steps (not shown). Certain other accessories such as a device for supplying water and a circulation pump are considered obvious and are not shown in the figure.

Fig. 3 shows schematically an embodiment of the present invention; a device, a reactor for the production of hydrogen from water 1. The reactor comprises two containers, a lower container 2 containing a gas mixture of water vapor and carbon monoxide and an upper container of water 3. The lower container comprises at least one device for scattering ionization radiation 4 in the gas mixture and its walls comprise mirrors for the reflection of the radiation and has an outlet, a conduit 8 for the gas formed, hydrogen and carbon dioxide. The upper container has an inlet, a conduit 6 for supplying water and carbon monoxide. The water in the container 3 is heated to boil by an exothermic reaction in the lower container 2 whereby water vapor is formed and mixed with added carbon monoxide in a space 5 above the water in the container 3. A conduit 7 for transporting the gas mixture, water vapor and carbon monoxide, leads from the upper container 3 to the lower container 2. When the gas mixture of water vapor and carbon monoxide is radiated from a device for scattering ionization radiation 4, hydrogen and carbon dioxide are formed in an exothermic reaction where the heat is used to bring the water in the upper container 3 to the boil to generate water vapor. The hydrogen and carbon dioxide are discharged via the outlet 8 for further disposal (not shown).

Fig. 4 shows schematically an embodiment of the present invention; a device, a reactor 1 for the production of hydrogen from water vapor. The reactor comprises a container 2 containing a gas mixture of water vapor and carbon monoxide. The container includes diffusers of ionization radiation 4 into the gas mixture and its walls include mirrors to reflect the radiation and thereby make it more effective. The container further has a conduit 8 for the discharge of formed gas consisting of hydrogen and carbon dioxide. The container has two inlets, an inlet 6 for the supply of carbon monoxide and an inlet 7 for the supply of water vapor. When the gas mixture of water vapor and carbon monoxide is radiated by a device for scattering by ionization radiation 4, hydrogen and carbon dioxide are formed in an exothermic reaction where the heat can be utilized for e.g. heating a room or producing more water vapor for further hydrogen production if water is available. The hydrogen and carbon dioxide are discharged via outlet 8, after which the gases are separated (with any known technology). The hydrogen is passed to a fuel cell for electricity generation or stored in a tank for later use. The carbon dioxide can be released into the air if it is based on biomass or passed on for other disposal.

The invention is not limited to the embodiments shown in the figures, but modifications can be made within the framework of the following claims.

Claims

1. A method of producing hydrogen from water, comprising the steps of mixing water and a gas comprising carbon monoxide to provide a mixture, and radiating said mixture with ionization radiation using at least one ionization radiation device, wherein said at least one ionization radiation device is a lamp or an X-ray tube.

2. A method according to claim 1, wherein said mixture is radiated with photons.

3. A method according to any of the preceding claims, wherein said lamp is a LED lamp, preferably a UV-C LED lamp or a UV-B LED lamp.

4. A method according to any of the preceding claims, wherein said X-ray tube is a cold-cathode X-ray tube.

5. A method according to any of the preceding claims, wherein said water is water vapor.

6. A method according to any of the preceding claims, wherein said gas is carbon monoxide.

7. An apparatus for producing hydrogen from water, wherein said apparatus comprises a container for water; at least one feeding means for providing water into said container; at least one feeding means for providing a gas into said container such as to mix said gas into said water to provide a mixture of gas in water; at least one ionization radiation device for providing ionization radiation to said mixture of gas in water in said container; and at least one discharging means for removing hydrogen and carbon dioxide from said container, wherein said gas comprises carbon monoxide.

8. An apparatus according to claim 7, wherein said at least one ionization radiation device is a lamp or an X-ray tube.

9. An apparatus according to claim 8, wherein said X-ray tube is a cold-cathode X-ray tube.

10. An apparatus according to any of claims 7-9, wherein said lamp is a LED lamp preferably a UV-C LED lamp or a UV-B LED lamp.

11. An apparatus according to any of claims 7-10, wherein said water is water vapor.

12. An apparatus according to any of claims 7-11, wherein said gas is carbon monoxide.

13. An apparatus according to any one of claims 7-12, wherein said apparatus further comprises at least one mirror inside said container for reflecting ionization radiation.

14. An apparatus according to any one of claims 7-13, wherein said apparatus further comprises at least one collecting device such as to collect hydrogen and carbon dioxide from said at least discharging means.

15. A hydrogen fuel cell comprising an apparatus according to any one of claims 7-14.