METHOD FOR PRODUCING A HYDROGEN-GENERATING FUEL, HYDROGEN-GENERATING FUEL OBTAINED, METHOD FOR PRODUCING HYDROGEN FROM THE FUEL, DEVICE FOR CARRYING OUT THE PRODUCTION METHOD, METHOD FOR OPERATING THE DEVICE, AND HYDROGEN-BASED FUEL OBTAINED BY MEANS OF THE HYDROGEN PRODUCTION METHOD

Abstract

Disclosed is a method for producing a hydrogen-generating fuel, the hydrogen-generating fuel obtained, a method for producing hydrogen from the fuel, a device for carrying out the production method, a method for operating the device, and a hydrogen-based fuel obtained by use of the production method. The production method is characterized in that it consists in mixing, in a liquid, particles of one or more metals which are corrodible by a basic chemical substance or an acidic chemical substance for the purpose of producing hydrogen, the particles being kept in suspension in the liquid, and the mixture composed of the liquid and the particles being chemically stabilized so as to prevent chemical reaction between the liquid and the particles.

Claims

1. A method for producing a hydrogen-generating fuel, comprising mixing in a liquid, particles of one or more metals which are corrodible by a basic chemical substance or an acidic chemical substance for the purpose of producing hydrogen, said particles being kept in suspension in said liquid and the mixture made up of the liquid and said particles being chemically stabilized so as to prevent chemical reaction between the liquid and said particles.

2. The method for producing a fuel according to claim 1, wherein the size of the particles of one or more metals is between 0.001 micron and 1000 microns and can be of different sizes.

3. The method for producing a fuel according to claim 1, wherein said liquid is a mineral liquid or an organic liquid or a mixture of both.

4. The method for producing a fuel according to claim 1, wherein the particles are kept in suspension in the liquid using at least one of the following methods: by mechanical agitation of the mixture made up of the liquid and the particles, by forced circulation of the mixture made up of the liquid and the particles using a pump, by addition to the liquid before mixing with particles of one or more anti-sedimentation chemical substances, by addition to the mixture made up of the liquid and the particles of one or more anti-sedimentation chemical substances, by addition to the mixture made up of the liquid and the particles of one or more particle anti-caking chemical substances.

5. The method for producing a fuel according to claim 4, wherein the anti-sedimentation chemical substance is a liquid-thickening substance of the mineral-type and/or of the organic-type.

6. The method for producing a fuel according to claim 4, wherein the anti-sedimentation and the liquid-thickening chemical substance is magnesium aluminum silicate.

7. The method for producing a fuel according to claim 1, wherein the mixture made up of the liquid and the particles is chemically stabilized so as to prevent or reduce the chemical reaction between the liquid and the particles.

8. The method for producing a fuel according to claim 1, wherein the particles are encapsulated with chemical substances of mineral-type or of organic-type, which substances are non-reactive with the liquid so as to prevent or reduce the chemical reaction between the liquid and the particles.

9. The method for producing a fuel according to claim 7, wherein the stabilization of the mixture made up of the liquid and the particles is carried out by at least one of the following methods: by maintaining the pH of the liquid before mixing with the particles between 1 and 7 or between 7 and 9 depending on the chemical nature of the metals corrodible by a basic substance or an acidic substance, by maintaining the pH of the mixture made up of the liquid and the particles between 1 and 7 or between 7 and 9 depending on the chemical nature of the metals corrodible by a basic substance or an acidic substance, by maintaining the pH of the mixture made up of the liquid, the anti-sedimentation agent and the particles between 1 and 7 or between 7 and 9 depending on the chemical nature of the metals corrodible by a basic substance or an acid substance, by maintaining the pH of the mixture made up of the liquid, the anti-sedimentation agent, the anti-caking agent and the particles between 1 and 7 or between 7 and 9 depending on the chemical nature of the metals corrodible by a basic substance or an acid substance.

10. The method for producing a fuel according to claim 9, wherein maintaining the pH between 1 and 7 is achieved by adding an acid substance of the H2SO4 or HCl or H3PO4 or CO2 type or any type of mineral or organic acid.

11. The method for producing a package according to claim 9, wherein maintaining the pH between 7 and 9 is achieved by adding a basic substance of NaOH or KOH type, or sodium silicate or sodium metasilicate or sodium ethanolate or potassium ethanolate or lithium ethanolate or sodium methanolate or potassium methanolate or lithium methanolate or any type of mineral or organic base.

12. The method for producing a fuel according to claim 1, wherein one or more metals which are corrodible by an acidic substance or by a basic substance is chosen from the following list: Aluminum Aluminum alloy, Zinc, Zinc alloy, Iron, Iron alloy, Copper, Copper alloy, Magnesium, Magnesium alloy.

13. The method for producing a fuel according to claim 1, wherein the mass percentage of the particles in the liquid is between 1 and 99%.

14. The method for producing a fuel according to claim 3, wherein the liquid is water.

15. The method for producing a fuel according to claim 3, wherein the liquid is a volatile and/or combustible organic liquid of the methanol or ethanol or butanol or propanol or gasoline or diesel type, or of any type of fuel used in land or air or sea vehicles.

16. The method for producing of a fuel according to claim 15, wherein the liquid is a volatile and/or combustible organic liquid whose evaporation temperature is between 60 and 100° C. or between 80 and 150° C. or between 100 and 200° C.

17. The method for producing a fuel according to claim 3, wherein the liquid contains an antifreeze.

18. Hydrogen-generating fuel obtained by the production method according to claim 1, wherein the hydrogen-generating fuel comprises: particles of one or more metals which are corrodible by a basic chemical substance or an acidic chemical substance for the purpose of hydrogen production, a liquid, which particles are suspended in said liquid and the mixture made up of the liquid and said particles is chemically stabilized so as to prevent the chemical reaction between the liquid and said particles.

19. The method for the production of hydrogen from the fuel of claim 18, wherein the generation of hydrogen takes place by the addition to the fuel of one or more chemical substances of the acid-type or of the base type, which acid-type or base-type substance forming a corrosion medium is at a concentration suitable to cause immediate corrosion of particles of one or more metals in the fuel and release of hydrogen.

20. The method for the production of hydrogen according to claim 19, wherein the acid-type chemical substance which attacks the particles by corrosion of one or more metals in the fuel corresponds to any type of mineral acid or organic acid or to a mixture of said types.

21. The method for the production of hydrogen according to claim 19, wherein the base-type chemical substance which attacks the particles by corrosion of one or more metals in the fuel by corrosion corresponds to any type of mineral base or organic base or to a mixture of said types.

22. The method for the production of hydrogen according to claim 19, wherein the acid-type or base-type chemical substance which attacks the particles by corrosion of one or more metals in the fuel is in solution in a mineral-type and/or organic-type liquid or in a mixture of said types.

23. The method for the production of hydrogen according to claim 19, wherein the acid-type or base-type chemical substance which attacks the particles by corrosion of one or more metals in the fuel is partially dissolved with the undissolved part in suspension or is in suspension in a mineral-type or organic-type liquid or in a mixture of said types.

24. The method for the production of hydrogen according to claim 19, wherein the chemical substance of the acid-type or of the base type which attacks the particles by corrosion of one or more metals in the fuel is completely dissolved in a mineral-type or organic-type liquid or a mixture of said types.

25. The method for the production of hydrogen according to claim 22, wherein the acid-type or base-type chemical substance which attacks the particles by corrosion of one or more metals in the fuel is in solution in a liquid at a mass concentration of between 1 and 50%.

26. The method for the production of hydrogen according to claim 22, wherein the liquid in which the chemical substance of the acid-type or of the base type which attacks the particles by corrosion is in solution, is water.

27. The method for the production of hydrogen according to claim 19, wherein the acid-type or base-type chemical substance which attacks the particles by corrosion is contained in a gas.

28. The method for the production of hydrogen according to claim 19, wherein the acid-type or base-type chemical substance is in solution or is partially dissolved or is suspended in an organic liquid or in a mixture of organic liquid and water, which organic liquid is of the methanol or ethanol or butanol or propanol or gasoline or diesel type or of any type of fuel used in land or air or sea vehicles or mineral liquid of the ammonia NH4OH type.

29. The method for the production of hydrogen according to claim 28, wherein the chemical reaction developed during the generation of hydrogen and during the temperature rise of the reaction medium during this hydrogen generation reaction as well that the by-products resulting from the reaction, cause a partial or total cracking into hydrogen of the organic liquid of the methanol or ethanol or butanol or propanol or gasoline or diesel type or of any type of fuel used in land or air or sea vehicles or mineral liquid of the ammonia NH4OH type.

30. The method for the production of hydrogen according to claim 27, wherein the acid-type or base-type chemical substance is contained in a gas, which gas is water vapor or air or nitrogen or ammonia (NH3).

31. The method for the production of hydrogen according to claim 19, wherein the non-volatile residue from the hydrogen-generating reaction contains compounds of the corrodible metal(s) composed of hydroxide or oxide of these metals, which compounds are recycled and regenerated by electrolysis to produce again corrodible metals.

32. The method for the production of hydrogen according to claim 31, wherein the non-volatile residue from the hydrogen-generating reaction contains aluminum hydroxide or alumina, which hydroxide of aluminum or which alumina is recycled and regenerated by electrolysis to produce again metallic aluminum.

33. The method for the production of hydrogen according to claim 19, wherein said corrosion reaction is activated and catalyzed, by galvanic contact of a first metal with a second metal selected so that its standard electrode potential is greater than the standard electrode potential of the first metal and that of hydrogen, which first metal has a surface smaller than the surface of the second metal with which the first metal is in contact, which second metal does not react or hardly reacts when contacted with the acid-type or base-type substance contained in the fluid corrosion medium, which production of hydrogen takes place both on the first metal and on the second metal.

34. The method for the production of hydrogen according to claim 19, wherein one or more acid-type or base-type chemical substances are present in a medium, selected from the following: wet gas, water vapor flowing liquid, viscous liquid, pasty liquid, two-phase medium (liquid containing a dissolved base or acid-type substance+undissolved base or acid-type substance), three-phase medium (gas+liquid containing a dissolved base or acid-type substance+undissolved base or acid-type substance).

35. The method for the production of hydrogen according to claim 33, wherein the second metal is in the form of granules.

36. The method for the production of hydrogen according to claim 19, wherein a first metal is in the form of particles or microparticles suspended in an aqueous medium, which aqueous medium contains one or a plurality of chemical agents for preventing agglomeration and sedimentation of the particles of the first metal, which aqueous medium and which anti-caking and anti-sedimentation agents are chosen so that they do not react chemically or react weakly with the particles of the first metal.

37. The method for the production of hydrogen according to claim 36, wherein one or more chemical agents making it possible to prevent the agglomeration and the sedimentation of the particles of a first metal, are associated with an acid compound if the presence of said chemical agent(s) makes the solution basic or to a basic compound if the presence of said chemical agent(s) makes the solution acidic.

38. The method for the production of hydrogen according to claim 19, wherein a first metal is in the form of solid microparticles or solid particles or solid powder encapsulated in an envelope of chemical nature of mineral-type and/or organic in suspension in an aqueous medium, which envelope is impermeable to the aqueous medium and to the acidic or basic substance, which envelope is also non-reactive or weakly reactive with respect to the aqueous medium.

39. The method for the production of hydrogen according to claim 19, wherein the acidic or basic substance is in the form of solid microparticles or solid particles or microdroplets or droplets or microgels encapsulated in an envelope of chemical nature of mineral and/or organic-type in suspension in an aqueous medium, which envelope is impermeable to the aqueous medium and to the acidic or basic substance, which envelope is also non-reactive or weakly reactive with respect to the aqueous medium.

40. The method for the production of hydrogen according to claim 19, wherein the acidic or basic substance is in the form of solid microparticles or solid particles or microdroplets or droplets or microgels encapsulated in an envelope of chemical nature of mineral and/or organic-type in suspension in an aqueous medium, which envelope is impermeable to the aqueous medium and to the acidic or basic substance, which envelope is also non-reactive or weakly reactive with respect to the aqueous medium and which aqueous medium contains one or more chemical agents making it possible to prevent agglomeration and sedimentation of the encapsulated acidic or basic substance, which aqueous medium and which anti-caking and anti-sedimentation agents are chosen so that they do not react on the chemical or react weakly with the encapsulation envelope of the acidic or basic substance.

41. The method for the production of hydrogen according to claim 39, wherein the release of the encapsulated acidic or encapsulated basic substance or of the first encapsulated metal in the corrosion medium takes place by mechanical rupture of the encapsulation envelope or by thermal rupture of the encapsulation envelope by increasing the temperature of the corrosion medium.

42. The method for the production of hydrogen according to claim 19, wherein a first metal is preconditioned in the form of grains of different grain sizes G1, G2, . . . , Gn with G1<G2<G3< . . . <Gn and with the mass concentration corresponding to each well-defined grain size.

43. The method for the production of hydrogen according to claim 33, further comprising in activating the production of hydrogen by bringing the first metal to an electric potential higher than zero volts and lower than the electric production potential of dioxygen and connecting the second metal to the positive pole of a direct current electric generator.

44. The method for the production of hydrogen according to claim 42, wherein the electrical activation consists in enclosing the grains of first metal between two electrodes made of second metal with the grains of the first metal in contact with each other and a part of these grains of the first metal in contact with the electrodes of the second metal.

45. The method for the production of hydrogen according to claim 43, further comprising, prior to electrical activation: forming a mixture of a first and a second galvanic metal, activating said mixture by reacting the mixture with a fluid corrosion medium, draining said activated mixture after reaction and storing the activated mixture in wet or dried form or draining the mixture after reaction, washing the mixture and storing the mixture in wet or dried form.

46. The method for the production of hydrogen according to claim 44, further comprising enclosing the granules of first metal in a cage having a porous or non-porous wall made of a second metal with the granules of the first metal in contact with each other and in contact with the wall of the porous metal cage made of the second metal, in bringing the grains of first metal to an electric potential greater than zero volts and lower than the electric potential for the production of dioxygen and in connecting this metal cage to the positive pole of a direct current electric generator by connecting the negative pole to another plate of a porous or non-porous second metal, which plate is separated from the porous metal cage enclosing the grains of the first metal via the corrosion medium.

47. The method for the production of hydrogen according to claim 19, wherein said acidic substance is selected from the following list: CO.sub.2 sulfuric acid, hydrochloric acid, nitric acid, sodium hydrogen sulphate.

48. The method for the production of hydrogen according to claim 19, wherein said basic substance is selected from the following list: sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate.

49. The method for the production of hydrogen according to claim 19, wherein the basic substance is selected from the following list: sodium hydroperoxide (NaHO2), potassium hydroperoxide (KHO2), lithium hydroperoxide (LiHO2), calcium hydroperoxide (CaHO2).

50. The method for the production of hydrogen according to claim 19, wherein one or more chemical substances of the acid-type or of the base type are in a medium consisting of a mixture of a solution of sodium hydroxide or potassium hydroxide or lithium hydroxide and a solution of hydrogen peroxide.

51. The method for the production of hydrogen according to claim 19, wherein the corrosion medium consists of a mixture of a solution of the acidic substance and a solution of the hydrogen peroxide.

52. The method for the production of hydrogen according to claim 19, wherein the reactions produce water vapor containing dihydrogen, which water vapor is cooled and condensed so as to remove water and acidic or basic substance.

53. The method for the production of hydrogen according to claim 33, wherein the first and the second metal are in the form of granules, the granules of the first metal have dimensions identical to or less than those of the granules of the second metal.

54. The method for the production of hydrogen according to claim 33, wherein the first and second metals are mixed before contact with one or more acid-type or base-type chemical substances.

55. The method for the production of hydrogen according to claim 19, wherein the acid or base-type substance is packaged in a solid form in the form of flakes or in the form of pellets placed in dissolution cartridges inside which a liquid circulates before being in contact with one or more metals.

56. Device for carrying out the method for producing hydrogen according to claim 19 comprising: particles of one or more metals which are corrodible by a basic chemical substance or an acidic chemical substance for the purpose of producing hydrogen and a liquid, the generation of hydrogen being carried out by the addition to the fuel of one or more chemical substances of acid-type or base-type, which acid-type or base-type substance forming a corrosion medium causes corrosion of particles of one or more metals in the fuel and release of hydrogen, wherein the device comprises a reactor-tank in which the corrosion reaction is carried out, said reactor-tank being supplied by a metallic suspension tank and by a corrosion medium tank.

57. Device for carrying out the method for producing hydrogen according to claim 33, further comprising one or more electrodes called anodes, one or more electrodes called cathodes, the so-called anode electrodes are separated from the so-called cathode electrodes by a solid, liquid and gaseous three-phase electrolyte comprising the first metal which is a solid reactive to the corrosion medium, the liquid of the corrosion medium and the gas produced by the various reactions.

58. Device for carrying out the method for producing hydrogen according to claim 33, wherein the second metal is preformed in the form of a metal tank containing the grains of the first metal and inside which the corrosion medium is located or circulates.

59. Device according to claim 58, wherein the tank made of second metal comprises several vertical fins of the same chemical nature as the second metal and welded to the inner wall of the tank so as to increase the contact surface between the second metal and the corrosion medium and also between the second metal and the grains of the first metal.

60. Device according to claim 58, wherein the tank is preformed to have several non-communicating compartments with each other in the lower part of the tank and communicating with each other in the upper part of the tank.

61. Device according to claim 60, wherein the compartments are independent tanks with the same features as the compartments described in claim 60 but installed in parallel, the outputs of which are installed in parallel and combined into a single output.

62. Device according to claim 60, wherein each compartment comprises an inlet for metal filling, an inlet for filling a corrosion liquid medium in the compartment, an outlet for emptying the fluid corrosion medium and/or for emptying the metal and fluid mixture resulting from the reaction.

63. Device according to claim 56, wherein the device is directly connected to a fuel cell so as to produce electric current for the purpose of propelling vehicles.

64. Device according to claim 56, wherein the device is connected to one or more fuel cells via one or more buffer tanks, which buffer tank acts as a hydrogen accumulator.

65. The method of operating a dihydrogen production device according to claim 60, further comprising increasing or decreasing the number of compartments in operation in order to respectively increase or decrease the production capacity.

66. The method of operating a dihydrogen production device according to claim 60, further comprising increasing or decreasing the level of the fluid corrosion medium in each compartment in order to respectively increase or decrease production capacity.

67. The method of operating a dihydrogen production device according to claim 60, further comprising operating each compartment one after the other or a group of compartments one after the others and at time ranges proportional to the duration of the rise in power of each chemical reaction with the first metal.

68. A hydrogen-based fuel obtained by the hydrogen production method according to claim 19, wherein the generated hydrogen also contains water vapor resulting from the vaporization of water by the heat of the fuel activation reaction.

69. A fuel obtained by the hydrogen production method according to claim 19, wherein the generated hydrogen also contains water vapor and vapors of volatile and/or combustible organic liquid, which vapors of water and volatile and/or combustible organic liquid result from the vaporization of the water and the volatile and/or combustible organic liquid by the heat of the fuel activation reaction.

70. A hydrogen-based fuel obtained by the hydrogen production method according to claim 19, having the following composition: a. Hydrogen with a volume concentration in the mixture ranging from 8 to 95% b. Water vapor with a volume concentration in the mixture ranging from 5 to 92%.

71. A hydrogen-based fuel obtained by the hydrogen production method according to claim 19, having the following composition: a. Hydrogen with a volume concentration in the mixture ranging from 8 to 95%, b. Water vapor with a volume concentration in the mixture ranging from 5 to 92%, c. Hydroxide ions (OH—).

72. A hydrogen-based fuel obtained by the hydrogen production method according to claim 19, having the following composition a. Hydrogen with a volume concentration in the mixture ranging from 8 to 95%, b. Water vapor with a volume concentration in the mixture ranging from 5 to 92%, c. Oxygen with a volume concentration in the mixture between 1 and 40%.

73. A hydrogen-based fuel obtained by the hydrogen production method according to claim 19, having the following composition: a. Hydrogen with a volume concentration in the mixture ranging from 8 to 95%, b. Water vapor with a volume concentration in the mixture ranging from 5 to 92%, c. Oxygen with a volume concentration in the mixture between 1 and 40%, d. Hydroxide ions (OH—), e. Hydrogen peroxide with a volume concentration in the mixture between 0 and 10%.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0307] FIG. 1 is a schematic drawing of a first embodiment of a hydrogen production device according to the invention;

[0308] FIG. 2 is a schematic drawing of a second embodiment of a hydrogen production device according to the invention;

[0309] FIG. 3 is a schematic drawing of one embodiment of a power and maintenance station for the hydrogen generating devices of FIG. 1 and FIG. 2.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0310] As shown in FIG. 1, the device denoted D as a whole ensures the production of hydrogen, for example for setting a vehicle (not shown) in motion in accordance with the method according to the invention.

[0311] This device D comprises a plurality of containers R.

[0312] R1 is the container called reactor defining an internal volume in which the corrosion reaction takes place, i.e. where the dihydrogen (or dihydrogen and dioxygen) is produced. Reactor R1 is supplied: [0313] with a solution containing a suspension of first metal M1 by being connected to a tank R3 which stores said suspension, [0314] with a solution containing a basic or acidic substance capable of reacting with metal M1 by being connected to a tank R4 which stores said solution.

[0315] A plurality of valves and pumps manage this supply.

[0316] R1 is also connected to a tank R2 of rinsing liquid for the purpose of cleaning its internal volume.

[0317] At the outlet, reactor R1 rejects dihydrogen to tank R6. It is also equipped with an outlet valve V1 and a reaction residue withdrawal pipe C1 which connects R1 to another tank R5 which stores the reaction residue.

[0318] Each tank R actually comprises an inlet and an outlet. The storage tanks R2, R3, R4 and R5 communicate with the service station ensuring supply and maintenance shown by FIG. 3 and denoted S as a whole.

[0319] This station includes a service nozzle 100 managing the connection of four pipes to the device D. Each pipe is connected to a station tank RS2, RS3, RS4 and RS5 respectively providing storage: [0320] of rinsing liquid for RS2 to supply tank R2, [0321] of metallic suspension for RS3 to supply R3, [0322] of liquid containing a basic or acidic substance for RS4 to supply R4, [0323] of reaction residue for RS5 to discharge R5 An example of the steps of the operation carried out is described below.

[0324] Step 1—filling the R3, R3, R4 tanks: [0325] connection of service nozzle 100 to ports 01, 02, 03 and 04, [0326] opening of valves V9, V10, V11, [0327] closure of valves V17 and V18, [0328] opening of valves V13, V14, V16, [0329] start of pumps P5, P6 and P8.

[0330] Step 2—filling of hydrogen production tank R1: [0331] closing of valves V4, V5 and V6; [0332] opening of valves V1, V2 and V3, [0333] start of pumps P1 and P2, [0334] at the end of filling: [0335] stop pumps P1 and P2, [0336] closing of valves V1, V2 and V3, [0337] opening of valves V4 and V5.

[0338] Step 3—dihydrogen production reaction in R1: [0339] in R1, the corrosion medium containing the acidic substance or the basic substance coming from R4 is in contact with the suspension of metal M1 coming from R3; [0340] the dihydrogen-producing reaction operates for a fixed period of time.

[0341] Step 4—withdrawal of reaction residues: [0342] once the reaction is complete in R1, opening of valve V12 and start of pump P4, [0343] opening of the valve V1,

[0344] filling the tank R5, [0345] at the end of the withdrawal of reaction residues:

[0346] stop of P4 Pump

[0347] closing of the valve V1,

[0348] closing of the valve V12

[0349] Step 5—cycle repeat from step 1.

[0350] Step 6—draining of tank R5 and storage of the reaction residue: [0351] implementation of step 1 with in addition opening of valve V12 at the start of withdrawal (opening of valve V12 at the same time as opening of valves V9, V10 and V11) and closing of the valve V12 at the same time as valves V9, V10, V11 at the end of withdrawal.

[0352] FIG. 2 shows a device D′ which can also be supplied and maintained by the station S and which differs from the device D only in that the tank R1′ where the reaction for the production of hydrogen (or dihydrogen and oxygen) is divided into two reactors: [0353] a primary reactor R1a′ and a secondary reactor R2b′.

[0354] The compartmentalization facilitates the recovery of the reaction residue, in particular by the P9 pump.

[0355] It is understood that the methods and devices which have just been described and represented above have been described for the purpose of disclosure rather than limitation. Of course, various adjustments, modifications and improvements may be made to the above examples, without departing from the scope of the invention.