Apparatus for generating hydrogen-rich ice

Abstract

A system and method for generation of hydrogen-rich ice (HRI) by introducing water that has been mixed with H.sub.2 and CO.sub.2 into the vertical tubes of a tube-ice machine is disclosed. The temperature and pressure within the vertical tubes can be maintained by refrigerant surrounding the vertical tubes to form carbon dioxide clathrate hydrates which entrap hydrogen molecules. The carbon dioxide clathrate hydrates cages with entrapped H.sub.2 are encased, transported and then delivered after HRI discharge Later, when the HRI tube-ice is formed and released from tube-ice machine, it warms whereupon the carbon dioxide clathrate hydrates dissociate and the H.sub.2 is released and used, for example by placement of the tube-ice small cylinders in a glass of water.

Claims

1. A system for generating hydrogen-rich ice (HRI) comprising: an eductor; a hydrogen gas inlet line; a carbon dioxide gas inlet line; a water inlet line; a heat exchanger; a thermal-insulated first container; a plurality of vertical tubes; a coolant container; an insulated blanket surrounding the plurality of vertical tubes; a recycling pump; a first recycling line; an ice cutter; an isolating lock chamber with carbon dioxide overpressure; a first guillotine damper and a second guillotine damper; and an inlet port to the isolating lock chamber with carbon dioxide overpressure, wherein water is introduced into an interior chamber of the eductor, wherein the water comprises a motive fluid causing hydrogen gas and carbon dioxide gas to be drawn and mixed into the interior chamber of the eductor, wherein the water, hydrogen gas and carbon dioxide gas are mixed in the interior chamber of the eductor and thereafter are introduced into an interior chamber of the thermal-insulated first container, wherein the thermal-insulated first container is heated by heat provided by the heat exchanger wherein the mixture of water, hydrogen gas and carbon dioxide gas is thereafter introduced into each of an interior of the plurality of vertical tubes, wherein the plurality of vertical tubes is disposed within an interior of the coolant container, wherein the coolant container comprises a coolant agent, wherein the mixture of water, hydrogen gas and carbon dioxide gas is circulated by the recycling pump multiple times through the interior of the vertical tubes through the first recycling line, wherein the temperature in an interior chamber in each of the plurality of vertical tubes is maintained by the coolant agent at a temperature of between about 232 K to 240 K, wherein when the mixture of water, hydrogen gas and carbon dioxide freeze to form tube-ice in the interior of the plurality of vertical tubes, the tube-ice is released from the interior of the plurality of vertical tubes, wherein the tube-ice is cut into distinct pieces of tube-ice by the cutter upon release from the interior of the plurality of vertical tubes, wherein the cut tube-ice is introduced into an interior of the isolating lock chamber with carbon dioxide overpressure, wherein excess hydrogen gas and carbon dioxide gas that exits the plurality of vertical tubes is recirculated to the eductor, wherein the isolating lock chamber with carbon dioxide overpressure is isolated from external atmosphere by closure of the first guillotine damper at one end of the isolating lock chamber with carbon dioxide overpressure and the second guillotine damper at the opposing end of the isolating lock chamber with carbon dioxide overpressure, wherein the isolating lock chamber with carbon dioxide overpressure is thereafter filled with carbon dioxide gas through the inlet port, wherein thereafter the second guillotine damper is opened and the HRI is removed from the interior chamber of the isolating lock chamber with carbon dioxide overpressure.

2. The system of claim 1, wherein the temperature within the interior of each of the plurality of cooled vertical tubes forms carbon dioxide clathrate hydrate clusters from the mixture.

3. The system of claim 1, wherein the pressure within the interior of the cooled vertical tubes is around atmospheric.

4. The system of claim 1, wherein the coolant comprises anhydrous ammonia refrigerant or R22 refrigerant.

5. The system of claim 1, wherein the water comprises a coloring agent.

6. The system of claim 1, wherein the mixture comprises a relative ratio of around 1 gallon water, 8 scf of CO.sub.2 and 32 scf of H.sub.2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be more readily understood from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings in which:

(2) FIG. 1 depicts a flow diagram of a method for generating hydrogen-rich ice according to one embodiment of the invention.

(3) FIG. 2 depicts a liquid/gas mixer for use in a tube-ice machine according to one embodiment of the invention.

(4) FIG. 3 depicts a tube-ice machine for use in the method according to one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

(5) The invention relates to a method for generating hydrogen-rich ice using a tube-ice machine. In one embodiment, the invention relates to the use of a tube-ice machine that produces ice automatically in vertical tubes, momentarily thaws ice from the tubes, and then cuts the ice tubes into short cylinders [16]. Holes are formed during ice formation as a result of a falling film of water freezing inside the vertical tube of the tube-ice machine.

(6) Under tube-ice machine conditions theory, pressures of around 200 MPa can result when water is cooled without allowing it to expand. Therefore, when water freezes in a pipe, it expands and can exert pressure that can rupture the pipe as the water has no place to expand as it freezes. To ensure correct operation of the method disclosed herein, a hole in the center of the vertical tubes of about 6 mm diameter is maintained.

(7) A mixture of hydrogen and carbon dioxide gas is mixed with water prior to introduction into the vertical tubes of the tube-ice machine. Dissolved CO.sub.2 provides the nucleation of water molecules via heterogeneous nucleation to form carbon dioxide clathrate hydrates [13]. Carbon dioxide clathrate hydrates are solid shaped particles comparable to ice that are formed when carbon dioxide and water combine at low temperature or high pressure. Carbon dioxide clathrate hydrates are complexes typically having 2-40 water molecules approximately [15]. For a tube-ice machine that has capacity of 1.0 gpm water inlet (about 5 ton/day of ice), the inlet water of 1.0 gpm would be mixed with approximately 8 scfm of CO.sub.2 and 32 scfm of H.sub.2.

(8) Experimental data on the kinetics of carbon dioxide clathrate hydrate formation and its solubility in distilled water are reported. The reported experiments were carried at nominal temperatures of 274, 276 and 278 K (5 C.) and at pressure ranging from 1.59 to 2.79 MPa [12]. The rate of hydrate growth from mixtures of CO.sub.2/H.sub.2 gas was found to be faster [13] than a reaction with a CO.sub.2/N.sub.2 mixture [14].

(9) Regular ice texture suggests that original intergranular seed ice porosity persists during carbon dioxide clathrate hydrate synthesis, which pores are about 120 m [15] or about 10 times smaller than formed carbon dioxide clathrate hydrate pores.

(10) Temperature and pressure conditions within the vertical tubes of a tube-ice machine can be conducive to carbon dioxide clathrate hydrate cluster creation. A tube-ice machine can be designed to realize temperatures within the vertical tubes of between 240 K (using anhydrous ammonia refrigerant) and 232 K (using R22 refrigerant) [17]. Carbon dioxide clathrate hydrate clusters can be formed at these temperatures at atmospheric pressure as well.

(11) One volume of carbon dioxide clathrate hydrate (cluster) has a size about 150-212 cubic Angstroms [15] and may entrap (or cage) theoretically up to about 250 hydrogen molecules. Introduction of a gas mixture of hydrogen and carbon dioxide into the vertical tubes of a tube-ice machine at certain temperatures thus may provide for the creation of empty carbon dioxide clathrate hydrate cages that allows for transport of hydrogen gas into the interior carbon dioxide clathrate hydrates [19].

(12) The tube-ice machines suitable for use in the invention are operated such that the pressure in the interior of the vertical tubes where ice with CO.sub.2 clathrate hydrates are formed is close to atmospheric pressure such that the formation of HRI will depend on the freezing temperature only which is equal to the refrigerant boiling point (for anhydrous ammonia240 K or for refrigerant R22232 K [21]). In one embodiment, the central holes are around 6 mm in diameter [18]. Accordingly, conditions within the vertical tubes of the tube-ice machine for HRI formation can be achieved using existing temperature control equipment. In the tube-ice machine suitable for use in the invention, the vertical tubes are designed as typical tube shell heat exchangers and there will not be a significant temperature gradient between the inlet and the outlet of the vertical tubes. Refrigerant is pumped such that it surrounds the vertical tubes.

(13) In one embodiment, H.sub.2 and CO.sub.2 can be mixed with the water prior to introduction into the inlet of the vertical tubes using gas ejectors or liquid power eductors. Ejectors are used in the industry in numerous unique ways. They can be used singly or in stages to create a wide range of vacuum conditions, or they can be operated for mass transfer and mixing operations. Eductors are a simple type of pump which work on the venturi effect to pump out gas or liquid [19]. Eductors require only a motive fluid or driving fluid for operation, which allows for the effective liquid and gas mixing. When the driving fluid is passed through the eductor at the required capacity (which depends on the design of the eductor), a low pressure is created inside it. This low pressure or vacuum enables the eductor to suck and mix gases (for example, here, H.sub.2 and CO.sub.2) and liquid (for example, water) from a certain area. Then this liquid mixed with gases can be pumped out to the vertical tubes of the tube-ice machine.

(14) In one embodiment, the hydrogen-rich ice that is formed is colored to identify it as hydrogen-rich ice (HRI), for example green. In this embodiment, a coloring agent can be mixed with the water prior to introduction of the water/H.sub.2/CO.sub.2 solution into the vertical tubes of the tube-ice machine. In one embodiment, water that has been previously colored can be mixed with the H.sub.2 and CO.sub.2.

(15) Turning to the figures, FIG. 1 depicts a flow diagram of a method for generating hydrogen-rich ice according to one embodiment of the invention where the water is colored prior to freezing. At 100, a colored substance is added to water. At 110, a mixture of carbon dioxide and hydrogen is prepared. At 120, the colored water and carbon dioxide/hydrogen mixture are mixed. At 130, the mixed colored water and carbon dioxide/hydrogen are introduced into the vertical tubes of a tube-ice machine under conditions to prepare hydrogen rich ice.

(16) FIG. 2 depicts a schematic of a liquid/gas mixer 200 for use in a tube-ice machine according to one embodiment of the invention. A driving liquid 201 (such as water) can be introduced into the inlet of an eductor 204. Gases hydrogen and carbon dioxide are introduced into eductor 204 at hydrogen gas inlet 203 and carbon dioxide inlet 202. The water, hydrogen and carbon dioxide mix in the interior of eductor 204 and exit into horizontal tube 205. Horizontal tube 205 is designed as a tube in a tube heat exchanger and can be cooled for example by a blanket of cooling liquid that enters a cooling sleeve at coolant entrance 209 and exits the cooling sleeve at coolant exit 210. The water/hydrogen/carbon dioxide mixture can pass through cooled horizontal tube 205 and can exit horizontal tube 205 into collection tank 207, which can be insulated with an insulated sleeve 206 and connected with the top of a tube-ice machine. The cooled water/hydrogen/carbon dioxide solution can be held in collection tank 207 for introduction into the vertical tubes of a tube-ice machine using inlet 208.

(17) FIG. 3 depicts a tube-ice machine 300 for use in the method of producing hydrogen-rich ice according to one embodiment of the invention. On the top of the tube-ice machine 300 a liquid/gas mixer 200 as described in FIG. 2 can be installed comprising thermally insulated collection tank 207, eductor 204 and horizontal tube 205. The water/hydrogen/carbon dioxide mixture can pass out of collection tank 207 and into inlet 208 of a plurality of vertical tubes 301 which are cooled by a blanket 302 of refrigerant, or coolant agent, surrounding vertical tubes 301. During a freezing cycle, the water/hydrogen/carbon dioxide mixture is circulated by water pump 305 through recirculation pipe 315. As the water/hydrogen/carbon dioxide mixture passes through the vertical tubes 301, hydrogen saturated carbon dioxide clathrate hydrates are entrapped within ice 303 that forms on the interior walls of vertical tubes 301. After the completion of a freezing cycle ice 303 begins thawing which causes ice 303 to drop on a rotating cutter 304 for sizing [18]. Cut ice 303 enters into a collection tank 316 and then enters through an opened first guillotine damper 308 to chamber 319. During this process, excess hydrogen and carbon dioxide gas are suctioned through suction line 307 back to eductor 204. In this embodiment, special instrumentation and control (P&ID and PLC) should be used to monitor and control the hydrogen and carbon dioxide gas concentrations entering eductor 204.

(18) Chamber 319 is an insulated lock chamber to prevent the release of hydrogen to the atmosphere. Chamber 319 is enclosed on either end with first guillotine damper 308 and second guillotine damper 309. While the design of chamber 319 in this embodiment is not part of the process of making HRI, it is a safety system support feature to minimize explosive hydrogen concentration. Once cut ice has entered chamber 319, first guillotine damper 308 and second guillotine damper 309 are closed and carbon dioxide enters through inlet port 306. Then HRI in the form of cut tube-ice is discharged from chamber 319 through exit 311 upon opening of second guillotine damper 309.

(19) As noted, HRI formed as described above has hydrogen saturated carbon dioxide clathrate hydrates entrapped within it. Later, as the HRI is used, for example placed in a glass of water, the HRI begins to melt. This causes the hydrogen saturated carbon dioxide clathrate hydrates to dissociate and release the hydrogen, whereupon the hydrogen can be consumed.

(20) The foregoing description of various embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed and, obviously, many modifications and variations are possible. Such modifications and variations that may be apparent to a person skilled in the art are intended to be included within the scope of the invention as defined by the accompanying claims.

REFERENCES

(21) 1. M. Lemaier et al., Hydrogen: Therapeutic potential in wellness and medicine. Journal of Aging Research & Clinical Practice, vol. 6, 2017, p. 14. 2. Ikuko Kimura, et al., Molecular hydrogen as a preventive and therapeutic medical gas: initiation, development and potential of hydrogen medicine. Pharmacology & Therapeutics, vol. 144, issue 1, October 2014, pages 1-11. 3. Kei Mizno, et al., Hydrogen rich water for improvements of mood, anxiety and autonomic nerve function in daily life. Med. Gas Res. 2017, October-December, 7(4), 245-255, Published online Jan. 22, 2018. 4. Ohsawa et al., Hydrogen acts as therapeutic antioxidant by selectively reducing cytotoxic oxygen radicals. Nat. Med., 2007, 13, pages 688-694. 5. Shigeo Ohta, et al., Resent Progress Toward Hydrogen Medicine. Potential of Molecular Hydrogen for Preventive and Therapeutic Applications. Bentham Science Publishers Curr. Pharm. Des. 2011, July, 1 77(22) pages 2241-2252. 6. Ki-Mun Kang, et al., Effect of drinking hydrogen rich water on the quality of life of patient treated with radiotherapy for liver tumors, Medical Gas Research., 2011 Jun. 7, 1, pages 1-8. 7. Inchol Park et al., Portable Hydrogen-rich Water Generator. US Patent Publication No. 2013/0043124A1, pub. Feb. 21, 2013. 8. Mark Sircus, E-book, Hydrogen Medicine, published January 2018. 9. G. W. C. Kaye et al., Tables of Physical and Chemical Constants 15th ed., Longman, N Y, 1986, p. 219. 10. S. S. Randhava, et al., The hydrogenation of carbon dioxide in parts-per-million levels, Institute of Gas Technology, vol 14-3 1-2018, p. 1-7 (PDF678418282017). 11. R. H. Perry's Chemical Engineers' Handbook Sixth Edition, McGraw Hill 1973, p. 3-102. 12. Jukio Hirose, Active Hydrogen Containing Ice, JP2014016088A, 2017 Jun. 21. 13. Brittany Glatz, et al., Heterogonous Ice Nucleation, Interplay of Surface Properties and their Impact on Water Orientations, Langmuir, 2018, 34 (3), Clemson University, p. 1190-1198. 14. L. Rajnish, et al., Gas hydrate formation from hydrogen/carbon dioxide gas mixtures Chemical Engineering Science, vol. 62, issue 16 Aug. 2007, p. 4268-4276. 15. T. Habteyes et al., Photodissociation of CO.sub.2 in water clusters. The Journal of Chemical Physics 126, 154301, 2007. 16. D. J. Milton et al., Carbon Dioxide Hydrate and Floods on Mars. 17. F. Isquierdo-Ruiz et al. Effect of CO2 Guest Molecule on the sI Clathrate Hydrate Structure Multidisciplinary Digital Publishing Institute (MDPI)m 2016 September 15, DOI: 10.33901/ma 9090777. 18. VOGT P-24A & P34A Tube Ice Machine, Service Manual May 31, 2011. 19. S. Circone et al., CO.sub.2 Hydrate: Synthesis, Composition, and Structure, J. Phys. Chem. B. Vol. 107, issue 23, 2003, page 5529-5539. 20. K. A. Lokshin et al., Storing Hydrogen in Crystalline Molecular Cages of Water, Los Alamos Science, Number 30, 2006. Phys. Rev. Lett, 93, p. 125503-3, 2004. 21. W. P. Payne, Purdue University e-Pub International Refrigeration and Air Conditioning Conference School of Mechanical Engineering, 2002. 22. Duo Sun et al., Preservation of Carbon Dioxide Clathrate Hydrate at Temperature below the water Freezing Point under Atmospheric Pressure. 23. H. D. Nigashima. Preservation of Carbon Dioxide Clathrate Hydrate in the presence of Trehalose under Freezer Conditions, Scientific Reports, v.6. 2016, 19354. 24. G. L. Stevenson et al., Directed multi port eductor and method of use, U.S. Patent Appln. Publn. No. 20110240753A1, Oct. 6, 2011. 25. A. A. Chernov et al., New Hydrate formation Methods in liquid gas medium. Sci Rep. 2017, 7, 40809. Published on line 2017, Jan. 18, doi:10.1038/step 40809. 26. M. Hercher, Clathrate Hydrates Chapter 3. Handbook of Hydrogen Storage, p. 63-70, Willey 2010. 27. G. Roman-Perez et al Stability, Adsorption and Diffusion of CH4m CO2 and H2 in Clathrate Hydrates. Cornell University, Material Science (cond-mat.mtri-sci) DOi. 10.1103/Phys. Letter. 105.145901.