Room temperature solid metal alloys for producing water-reactive aluminum compositions

Abstract

Provided herein are water-reactive aluminum compositions comprising aluminum or an alloy thereof and an activated metal alloy (e.g., a non-eutectic activated metal alloy comprising bismuth, tin, indium, and gallium, or an activated metal alloy comprising bismuth, tin, and indium). Some water-reactive aluminum compositions provided herein do not contain gallium. Also provided herein are methods of activating aluminum to provide water-reactive aluminum compositions. Additionally provided are fuel mixtures comprising the water-reactive aluminum compositions described herein and water-reactive aluminum compositions with increased gallium content, and methods of providing hydrogen and / or steam using the water-reactive aluminum compositions described herein.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 480,643, filed January 19, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

[0002] Aluminum is a promising candidate for energy storage due to its high energy density, abundance, low cost, non-toxicity, non-volatility, and non-reactivity when stored. One method of extracting energy from aluminum is to react it with water to form hydrogen and generate heat, as described in Reaction 1 or Reaction 2. ·Al+2H2O→1.5H2+AlO(OH)+Q 反応 (Reaction 1) ·Al+3H2O→1.5H2+Al(OH)3+Q 反応 (Reaction 2)

[0003] Untreated aluminum does not normally react with water due to a highly passivating oxide layer that forms on its surface, but by breaking down the oxide layer with an appropriate catalyst, the aluminum can be activated and made water-reactive.

[0004] Existing catalysts for this purpose are typically gallium or alloys in which gallium is the major component (greater than 50% by mass). Because gallium is an expensive metal and is present in limited amounts, it is desirable to have catalysts with gallium content limited to 10% or less, including gallium-free catalysts. Summary of the Invention [Means for solving the problem]

[0005] In one aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; a non-eutectic activated metal alloy comprising bismuth, tin, indium, and gallium disposed along the microstructure of the aluminum or alloy thereof, the non-eutectic activated metal alloy comprising up to about 10% gallium by mass; When water is introduced into the composition, the aluminum or its alloys disintegrate, exposing the internal volume to water and causing a rapid hydrolysis reaction to occur, providing a water-reactive aluminum composition.

[0006] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; an activated metal alloy comprising at least two metals selected from the group consisting of bismuth, tin, and indium, and disposed along the microstructure of the aluminum or alloy thereof; When water is introduced into the composition, the aluminum or its alloys collapse, exposing the internal volume to water and causing a rapid hydrolysis reaction, The water-reactive aluminum composition is provided as a gallium-free water-reactive aluminum composition.

[0007] In another aspect, provided herein is a method for activating aluminum or an alloy thereof, comprising the steps of: contacting aluminum or an alloy thereof with a non-eutectic activating metal alloy comprising bismuth, tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy and below the melting temperature of aluminum or its alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0008] In another aspect, provided herein is a method for activating aluminum or an alloy thereof, comprising the steps of: contacting aluminum or an alloy thereof with an activated metal alloy comprising tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy and below the melting temperature of aluminum or its alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0009] In another aspect, provided herein is a method for activating aluminum or an alloy thereof, comprising the steps of: contacting aluminum or an alloy thereof with an activating metal alloy comprising at least two metals selected from the group consisting of bismuth, tin, and indium to provide a gallium-free mixture; and heating the mixture at a temperature above the melting temperature of the activated metal alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0010] In another aspect, provided herein is a method of providing hydrogen and / or steam, the method comprising providing hydrogen and / or steam by contacting a water-reactive aluminum composition disclosed herein with water such that a rapid hydrolysis reaction occurs.

[0011] In another aspect, provided herein is a fuel mixture comprising a plurality of water-reactive aluminum compositions disclosed herein and a plurality of water-reactive aluminum compositions comprising aluminum and 0 to about 3% or about 3 to about 6% gallium by mass, wherein the gallium is present in the plurality of compositions in varying amounts, such that when the compositions contact water, a distribution of reaction rates is achieved at a given reaction initiation temperature or steady-state operating temperature. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a diagram illustrating a method for producing a low-melting catalyst. [Figure 2] FIG. 1 is a schematic diagram showing a rotating drum as an example of an aluminum activation process. [Figure 3]1 is an image showing the initiation of reaction of catalytically activated aluminum immediately after exposure to water. [Figure 4] A series of images showing the vigorous nature of the ongoing reaction after some time and / or increased temperature of the water. [Figure 5] 1 is a graph showing hydrogen flow rate (g / hr) and feedstock usage (wt%) over time resulting from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 33% Sample C by mass). [Figure 6] 1 is a graph showing power (kW) as a function of energy produced from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing about 33% Sample C by mass). [Figure 7] 1 is a graph showing power (kW) as a function of feedstock loading (% wt) resulting from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 33% Sample C by mass). [Figure 8] 1 is a graph showing hydrogen flow rate (g / hr) and feedstock usage (% wt) over time resulting from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 50% Sample C by mass). [Figure 9] 1 is a graph showing power (kW) as a function of energy produced from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 50% Sample C by mass). [Figure 10] 1 is a graph showing power (kW) as a function of feedstock loading (% wt) resulting from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 50% Sample C by mass). [Figure 11] 1 is a graph showing hydrogen flow rate (g / hr) and feedstock usage (% wt) over time resulting from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 50% Sample C by mass). [Figure 12]1 is a graph showing power (kW) as a function of energy produced from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 50% Sample C by mass). [Figure 13] 1 is a graph showing power (kW) as a function of feedstock loading (% wt) resulting from the reaction of aluminum (derived from used beverage cans) activated with catalyst Sample C (containing approximately 50% Sample C by mass). DETAILED DESCRIPTION OF THE INVENTION

[0013] The present disclosure provides, in part, novel catalysts (e.g., activated metal alloys) for activating aluminum, and water-reactive aluminum compositions activated with the catalyst compositions disclosed herein. In some embodiments, disclosed herein are activated alloys comprising indium, bismuth, tin, and optionally gallium for catalytically activating aluminum metal. Contemplated catalysts can react aluminum with water or steam as described in Reaction 1 or Reaction 2. In some embodiments, the catalysts described herein have reduced gallium content (e.g., about 10% gallium or less by mass) and low melting points (e.g., less than 200°C, or less than 157°C).

[0014] Also provided herein are activation alloys comprising indium, bismuth, tin, and varying amounts of gallium, where the amount of gallium is varied to alter the water reactivity (e.g., onset temperature and / or reaction rate) of water-reactive aluminum compositions comprising the activation alloy.

[0015] Contemplated catalytic applications may include, but are not limited to, aluminum-water reactors, H2 generation, heat generation, steam generation, AlO(OH) generation, Al(OH)3 generation, and aluminum embrittlement.

[0016] In one aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; a non-eutectic activating metal alloy comprising bismuth, tin, indium, and gallium disposed along the microstructure of the aluminum or alloy thereof; When water is introduced into the composition, the aluminum or its alloys disintegrate, exposing the internal volume to water and causing a rapid hydrolysis reaction to occur, providing a water-reactive aluminum composition.

[0017] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; a non-eutectic activated metal alloy comprising bismuth, tin, indium, and gallium disposed along the microstructure of the aluminum or alloy thereof, the non-eutectic activated metal alloy comprising up to about 10% gallium by mass; When water is introduced into the composition, the aluminum or its alloys disintegrate, exposing the internal volume to water and causing a rapid hydrolysis reaction to occur, providing a water-reactive aluminum composition.

[0018] As used herein, the term "non-eutectic" refers to an alloy in which the melting point of the alloy is higher than the melting point of at least one of the constituent metals.

[0019] As used herein, the term "microstructure" of aluminum refers to the arrangement of crystalline aluminum grains, intermetallic phases, and crystalline defects, with grain boundaries present at the interfaces between individual aluminum grains to form larger aluminum particles or bodies.

[0020] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; an activated metal alloy comprising bismuth, tin, and indium disposed along the microstructure of the aluminum or alloy thereof; When water is introduced into the composition, the aluminum or its alloys collapse, exposing the internal volume to water and causing a rapid hydrolysis reaction, The water-reactive aluminum composition is provided as a gallium-free water-reactive aluminum composition.

[0021] In another aspect, provided herein is a water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; an activated metal alloy comprising at least two metals selected from the group consisting of bismuth, tin, and indium, and disposed along the microstructure of the aluminum or alloy thereof; When water is introduced into the composition, the aluminum or its alloys collapse, exposing the internal volume to water and causing a rapid hydrolysis reaction, The water-reactive aluminum composition is provided as a gallium-free water-reactive aluminum composition.

[0022] In some embodiments, the activation metal alloy comprises bismuth, tin, and indium.

[0023] In some embodiments, the water-reactive aluminum composition is formed by a process comprising contacting aluminum or its alloy with an activated metal alloy, wherein the activated metal alloy is in liquid form and the aluminum or its alloy is in solid form when the aluminum or its alloy contacts the activated metal alloy. In some embodiments, the activated metal alloy is heated above its melting point prior to contacting with the aluminum or its alloy. In some embodiments, the activated metal alloy has a melting point below the melting temperature of the aluminum or its alloy.

[0024] In some embodiments, the activated metal alloy has a melting point less than 200° C. In some embodiments, the activated metal alloy has a melting point less than 157° C. In some embodiments, the activated metal alloy has a melting point less than 150° C. In some embodiments, the activated metal alloy has a melting point less than 100° C.

[0025] In some embodiments, the activated metal alloy is about 2% to about 20%, about 2% to about 18%, about 2% to about 16%, about 2% to about 14%, about 2% to about 12%, about 2% to about 10%, about 2% to about 8%, or about 2% to about 4% of the total weight of the water-reactive aluminum composition. In some embodiments, the activated metal alloy is about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 30%, about 40%, or about 50% of the total weight of the water-reactive aluminum composition.

[0026] In some embodiments, the activated metal alloy is at least about 6% or about 6% of the total mass of the water-reactive aluminum composition.

[0027] In other embodiments, the aluminum or alloys thereof contain one or more alloying elements selected from the group consisting of copper, silicon, iron, manganese, zinc, titanium, magnesium, lithium, cadmium, zirconium, beryllium, scandium, sodium, cerium, yttrium, silver, calcium, boron, chromium, bismuth, lead, vanadium, nickel, cobalt, oxygen, or gallium, which alloying elements collectively comprise from 0 to about 20% of the total mass of the aluminum.

[0028] In some embodiments, the aluminum or alloy thereof does not include gallium, indium, bismuth, and / or tin as alloying elements. In some embodiments, the aluminum or alloy thereof consists essentially of aluminum. In some embodiments, the aluminum or alloy thereof consists of aluminum.

[0029] As used herein, the term "about" means approximately, in the vicinity of, roughly, or around. Unless otherwise specified with a stated numerical value, when the term "about" is used in conjunction with a numerical range, it modifies that range by extending its boundaries above and below the stated numerical value. Unless otherwise specified with a stated numerical value, the term "about" is used herein to modify a numerical value by a variance of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, or 50% above and below the stated value. As a non-limiting example, a range of "about 2 to about 20" can mean 1.98 to 22, or 1 to 30, or other ranges therebetween. Unless otherwise specified with a stated percentage range, when the term "about" is used in conjunction with a percentage range, it modifies that range by extending its boundaries above and below the stated percentage. Unless otherwise specified with respect to a stated percentage, the term "about" is used herein to modify the stated percentage by 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, or 50% above or below the stated percentage (which may be limited as an absolute value, i.e., to 0% as a minimum value), or by 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, or 50% of that percentage. As a non-limiting example, the range "about 2% to about 20%" can mean 1% to 21%, or 0% to 70%, or other ranges therebetween, or 1.98% to 22%, or 1% to 30% (as a percentage of that percentage range). As a non-limiting example, a percentage value of "about 30%" can mean 29% to 31%, or 0% to 80%, or other ranges therebetween, or 27% to 33%, or 15% to 45% (as a percentage of that percentage value), or other ranges therebetween.Unless a numerical range is otherwise stated, numerical ranges recited herein by endpoints include all numbers and fractions subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.90, 4, and 5). It is also understood that all numbers and fractions thereof are presumed to be modified by the term "about."

[0030] In some embodiments, the activated metal alloy consists essentially of bismuth, gallium, indium, and tin. In some embodiments, the activated metal alloy consists essentially of bismuth, gallium, indium, and tin. In some embodiments, the activated metal alloy consists essentially of bismuth, tin, and indium. In some embodiments, the activated metal alloy consists essentially of gallium, tin, and indium. In some embodiments, the activated metal alloy consists essentially of gallium, tin, and indium. In some embodiments, the activated metal alloy consists essentially of gallium, tin, and indium.

[0031] In certain embodiments, the activation metal alloy includes a field metal that includes, by mass, about 51% (e.g., about 51.2%) indium, about 32% (e.g., about 32.0%) bismuth, and about 17% (e.g., about 16.8%) tin.

[0032] In some embodiments, the activation metal alloy comprises about 5% or less gallium by weight. In some embodiments, the activation metal alloy comprises about 10% or less gallium by weight. In some embodiments, the activation metal alloy comprises about 15% or less gallium by weight. In some embodiments, the activation metal alloy comprises about 20% or less gallium by weight. In some embodiments, the activation metal alloy comprises about 25% or less gallium by weight. In some embodiments, the activation metal alloy comprises about 30% or less gallium by weight.

[0033] In some embodiments, the activation metal alloy comprises less than about 10% gallium by mass.

[0034] In some embodiments, the activation metal alloy comprises about 1% gallium by weight. In some embodiments, the activation metal alloy comprises about 2% gallium by weight. In some embodiments, the activation metal alloy comprises about 3% gallium by weight. In some embodiments, the activation metal alloy comprises about 4% gallium by weight. In some embodiments, the activation metal alloy comprises about 5% gallium by weight. In some embodiments, the activation metal alloy comprises about 6% gallium by weight. In some embodiments, the activation metal alloy comprises about 7% gallium by weight. In some embodiments, the activation metal alloy comprises about 8% gallium by weight. In some embodiments, the activation metal alloy comprises about 9% gallium by weight. In some embodiments, the activation metal alloy comprises about 10% gallium by weight. In some embodiments, the activation metal alloy comprises about 15% gallium by weight. In some embodiments, the activation metal alloy comprises about 20% gallium by weight.

[0035] In some embodiments, the activation metal alloy can include about 5 to about 10% gallium by weight, about 1 to about 5% gallium by weight, 0 to about 1% gallium by weight, or 0% gallium by weight.

[0036] In some embodiments, the activation metal alloy comprises about 30% indium by weight. In some embodiments, the activation metal alloy comprises about 35% indium by weight. In some embodiments, the activation metal alloy comprises about 40% indium by weight. In some embodiments, the activation metal alloy comprises about 45% indium by weight. In some embodiments, the activation metal alloy comprises about 50% indium by weight. In some embodiments, the activation metal alloy comprises about 55% indium by weight. In some embodiments, the activation metal alloy comprises about 60% indium by weight. In some embodiments, the activation metal alloy comprises about 65% indium by weight. In some embodiments, the activation metal alloy comprises about 70% indium by weight.

[0037] In some embodiments, the activated metal alloy can include about 46 to about 48% indium by weight, about 48 to about 50% indium by weight, about 50 to about 51% indium by weight, or about 51 to about 53% indium by weight.

[0038] In some embodiments, the activation metal alloy comprises about 10% bismuth by weight. In some embodiments, the activation metal alloy comprises about 15% bismuth by weight. In some embodiments, the activation metal alloy comprises about 20% bismuth by weight. In some embodiments, the activation metal alloy comprises about 25% bismuth by weight. In some embodiments, the activation metal alloy comprises about 30% bismuth by weight. In some embodiments, the activation metal alloy comprises about 35% bismuth by weight. In some embodiments, the activation metal alloy comprises about 40% bismuth by weight. In some embodiments, the activation metal alloy comprises about 45% bismuth by weight. In some embodiments, the activation metal alloy comprises about 50% bismuth by weight.

[0039] In some embodiments, the activation metal alloy can include about 28 to about 30% bismuth by weight, about 30 to about 31% bismuth by weight, about 31 to about 32% bismuth by weight, or about 32 to about 34% bismuth by weight.

[0040] In some embodiments, the activated metal alloy comprises about 5% tin by weight. In some embodiments, the activated metal alloy comprises about 10% tin by weight. In some embodiments, the activated metal alloy comprises about 15% tin by weight. In some embodiments, the activated metal alloy comprises about 20% tin by weight. In some embodiments, the activated metal alloy comprises about 25% tin by weight. In some embodiments, the activated metal alloy comprises about 30% tin by weight. In some embodiments, the activated metal alloy comprises about 35% tin by weight. In some embodiments, the activated metal alloy comprises about 40% tin by weight.

[0041] In some embodiments, the activated metal alloy can include about 15 to about 16% tin by weight, 16 to 16.5% tin by weight, 16.5 to 16.8% tin by weight, or 16.8 to 18% tin by weight.

[0042] In one embodiment, the activation metal alloy includes about 6% gallium, about 48% indium, about 30% bismuth, and about 16% tin.

[0043] In some embodiments, the activation metal alloy includes bismuth, tin, and indium in amounts sufficient to reduce the melting point of the activation metal alloy to below 200° C. when the activation metal alloy includes 10% or less gallium by mass.

[0044] In some embodiments, the activated metal alloy is free of cadmium and / or lead.

[0045] In other embodiments, the activated metal alloy is a solid at room temperature (eg, 20° C.).

[0046] As used herein, the term "room temperature" refers to 20°C.

[0047] In certain embodiments, the activation metal alloy is liquid below the melting point of indium (about 157° C.).

[0048] In another aspect, the present disclosure provides a method for activating aluminum or its alloys, comprising: contacting aluminum or an alloy thereof with a non-eutectic activating metal alloy comprising bismuth, tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0049] In another aspect, the present disclosure provides a method for activating aluminum or its alloys, comprising: contacting aluminum or an alloy thereof with a non-eutectic activating metal alloy comprising bismuth, tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy and below the melting temperature of aluminum or its alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0050] In another aspect, the present disclosure provides a method for activating aluminum or its alloys, comprising: contacting aluminum or an alloy thereof with an activating metal alloy comprising bismuth, tin, and indium to provide a gallium-free mixture; and heating the mixture at a temperature above the melting temperature of the activated metal alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0051] In another aspect, the present disclosure provides a method for activating aluminum or its alloys, comprising: contacting aluminum or an alloy thereof with an activating metal alloy comprising at least two metals selected from the group consisting of bismuth, tin, and indium to provide a gallium-free mixture; and heating the mixture at a temperature above the melting temperature of the activated metal alloy and below the melting temperature of aluminum or its alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0052] In some embodiments, the activation metal alloy comprises bismuth, tin, and indium.

[0053] In another aspect, the present disclosure provides a method for activating aluminum or its alloys, comprising: contacting aluminum or an alloy thereof with an activated metal alloy comprising tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy and below the melting temperature of aluminum or its alloy for a predetermined period of time to provide a water-reactive aluminum composition.

[0054] In some embodiments, the non-eutectic activation metal alloy is bismuth-free.

[0055] In some embodiments, the activation metal alloy comprises bismuth, tin, and indium.

[0056] In some embodiments, the activated metal alloy is an activated metal alloy described herein.

[0057] In some embodiments, contacting the aluminum or alloy thereof with an activating metal alloy comprises melting the activating metal alloy and uniformly applying the activating metal alloy to the surface of the aluminum or alloy thereof.

[0058] In some embodiments, the mixture includes the activated metal alloy in an amount between about 1% and about 10%, between about 10% and about 20%, between about 20% and about 50%, between about 50% and about 100%, between about 100% and about 300%, or between about 300% and about 600% by weight of the aluminum or alloy thereof. In some embodiments, the mixture includes the activated metal alloy in an amount between about 0% and about 3%, between about 3% and about 6%, between about 6% and about 10%, between about 10% and about 100%, or between about 100% and about 700% by weight of the aluminum or alloy thereof. In some embodiments, the mixture includes the activated metal alloy in an amount of about 5% by weight of the aluminum or alloy thereof. In some embodiments, the mixture includes the activated metal alloy in an amount of about 10% by weight of the aluminum or alloy thereof. In some embodiments, the mixture includes the activated metal alloy in an amount of about 20% by weight of the aluminum or alloy thereof. In some embodiments, the mixture includes the activated metal alloy in an amount of about 30% by weight of the aluminum or alloy thereof. In some embodiments, the mixture includes the activated metal alloy in an amount of about 40% by weight of the aluminum or alloy thereof.

[0059] In some embodiments, the predetermined time period is about 1 hour to about 3 hours, or about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 15 hours, about 20 hours, about 30 hours, about 2 days, about 3 days, about 4 days, about 5 days, about 6 days, about 7 days, about 8 days, about 9 days, or about 10 days.

[0060] In certain embodiments, the method further comprises varying the amount of gallium in the activated metal alloy to vary the temperature required for the water-reactive aluminum composition to react with water.

[0061] In other embodiments, the method further comprises varying the amount of gallium in the activated metal alloy such that, upon contact of the water-reactive aluminum composition with water, the temperature at which the reaction rate between the water-reactive aluminum composition and water accelerates to form vapor is varied.

[0062] In some embodiments, the method further comprises varying the amount of gallium in the activated metal alloy such that when the water-reactive aluminum composition is contacted with water, hydrogen gas is produced in the absence of steam.

[0063] In certain embodiments, the method further comprises heating the mixture of aluminum or an alloy thereof and the activated metal alloy at a temperature above the melting point of the activated metal alloy while continuously stirring the mixture in the rotating drum.

[0064] In some embodiments, the mixture is heated to a temperature of 60°C to 100°C, 100°C to 150°C, 150°C to 200°C, or 200°C to 250°C.

[0065] In another embodiment, the mixture is heated with a heating element inside the rotating drum.

[0066] In some embodiments, the mixture is heated with a heating element external to the rotating drum.

[0067] Also provided herein is a method of providing hydrogen and / or steam, the method comprising providing hydrogen and / or steam by contacting a water-reactive aluminum composition disclosed herein with water such that a rapid hydrolysis reaction occurs.

[0068] In some embodiments, the method further comprises recovering at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 99%, at least about 99.9%, or at least about 99.99% of the activated metal alloy after the rapid hydrolysis reaction has occurred. In certain embodiments, the method further comprises recovering at least about 95% of the activated metal alloy after the rapid hydrolysis reaction has occurred.

[0069] Provided herein is a fuel mixture comprising a plurality of water-reactive aluminum compositions described herein and a plurality of water-reactive aluminum compositions comprising aluminum and 0 to about 3% or about 3 to about 6% gallium by mass, wherein the gallium is present in the plurality of compositions in varying amounts, such that a distribution of reaction rates is achieved at a given reaction onset temperature or steady-state operating temperature when the compositions contact water. [Example]

[0070] Example 1: Preparation of activated metal alloy catalyst and its use in activating aluminum The activated metal alloys were prepared by first mixing appropriate amounts of indium, bismuth, tin, and / or gallium in a container suitable for heating, such as glass, steel, or another material. Aluminum containers were not used due to their reactivity with the alloys. As used in the examples, the term "catalyst" refers to the activated metal alloys (e.g., Samples A-F).

[0071] In the experiments described below, power output, energy output, and yield were calculated by measuring the flow rate of hydrogen released during the reaction. The energy released as hydrogen from the reaction of aluminum with water was extrapolated from the hydrogen flow rate using the known higher heating value (HHV) combustion energy of hydrogen. The energy released as heat / steam from the reaction of aluminum with water was extrapolated from the hydrogen flow rate using a fixed ratio of hydrogen (51.2%) to heat (48.8%) released during the reaction of aluminum with water (see Reactions 1 and 2).

[0072] Exemplary compositions of activated metal alloys are shown in Table 1. [Table 1]

[0073] Preparation of Samples A, D, and E The metals were heated in a container to a temperature higher than the melting point of 271°C for bismuth, which has the highest melting point in the group. In this example, a hotplate set at 500°C was used. However, other heating methods, such as an oven, furnace, or gas torch, may also be used. To protect the metals from oxidation, the container was filled with argon during heating. Any inert gas, such as nitrogen, helium, neon, or xenon, may also be used. If an inert gas is not used, bismuth, in particular, may discolor and form a yellow-brown surface layer. Once the indium metal was melted, tin, bismuth, and gallium were stirred together to form a homogeneous liquid metal alloy. Upon cooling to room temperature, the catalyst solidified.

[0074] Samples B and C can be prepared in essentially the same manner as described above.

[0075] Preparation of activated aluminum using sample D and its reaction with water To activate aluminum with Sample D, 4 g of Sample D was heated above its melting point, approximately 60°C. A hot plate set at 200°C was used to dissolve the catalyst, although other forms of heating may also be used. The catalyst and 0.6 g of aluminum were placed in a sealed container. In this example, an excess of catalyst was used; the amount of catalyst was 650% of the mass of the aluminum. The aluminum may also be activated with other mass ratios of catalyst, relative to the mass of the aluminum being activated: 0 to approximately 3%, 3 to approximately 6%, about 6 to approximately 10%, about 10 to approximately 100%, and about 100 to approximately 700%. The container was stirred by shaking until the catalyst covered the aluminum metal. The mixture was heated continuously for 2 to 3 hours by maintaining the container at 200°C on a hot plate; however, the mixture may also be heated for 0 to 240 hours (0 to 10 days).

[0076] The mixture was manually stirred 3-4 times over the course of the heat treatment. Alternatively, the mixture may be continuously stirred, for example, by a rotating drum. The rotating drum may have a heater integrated either inside or outside the drum, for example, as shown in Figure 2.

[0077] Water was added to the catalytically activated aluminum, and bubbles began to form on the surface of the aluminum due to the decomposition of the water into hydrogen gas, as shown in Figure 3. As the reaction progressed, more aluminum surface area was exposed and the temperature increased. After several minutes, the reaction rate increased exponentially, causing the water to boil due to the rate of heat release in the reaction, as shown in Figure 4. The reaction process may also be carried out in vessels other than those shown in Figures 3 and 4, including aluminum-water reactors.

[0078] Because Sample D melts at a temperature of about 60°C, which is above room temperature, mixing this catalyst-containing aluminum fuel with another catalyst composition, for example, an aluminum fuel containing a catalyst composition having a melting point below room temperature, may be beneficial to the initial reaction rate.

[0079] Alternatively, or additionally, it may be beneficial to preheat the water source that is subjected to the aluminum-water reaction to aid in the reaction rate when using this catalyst composition.

[0080] Samples A, B, C and E can be prepared in essentially the same manner as above and used to activate aluminum.

[0081] Preparation of activated aluminum using sample C (33% catalyst by mass) from used beverage cans and its reaction with water Aluminum scrap obtained from shredded used beverage cans (UBC) (2.240 g) was activated with Sample C (1.111 g) and reacted with water using a procedure similar to that described above for Sample D. The amount of catalyst represented approximately 33% by mass of the final water-reactive aluminum composition, and the water was heated to 60° C. before reacting with the activated aluminum.

[0082] The yield of this reaction, expressed as a reaction efficiency (the percentage of energy released as heat and hydrogen relative to the theoretical energy embedded in the aluminum), was 77%. The following power outputs were observed:

[0083] Average output (W): 170.5 Peak power (W): 1257 Average specific output (kW / kg): 76.13 Peak specific power (kW / kg): 561.4

[0084] Figure 5 shows the hydrogen flow rate and the amount of activated aluminum consumed over time during the reaction. Figure 6 shows the relationship between the energy produced by the reaction and the power output. Figure 7 shows the relationship between the amount of activated aluminum consumed by the reaction and the power output.

[0085] Preparation of activated aluminum using sample C (50% catalyst by mass) from used beverage cans and its reaction with water Aluminum scrap obtained from shredded used beverage cans (UBC) (0.742 g) was activated with Sample C (0.739 g) and reacted with water using a procedure similar to that described above for Sample D. The amount of catalyst comprised approximately 50% by mass of the final water-reactive aluminum composition, and the water was heated to 60° C. before reacting with the activated aluminum.

[0086] The yield of this reaction, expressed as a reaction efficiency (the percentage of energy released as heat and hydrogen relative to the theoretical energy embedded in the aluminum), was 98%. The following power outputs were observed: Average output (W): 208.2 Peak power (W): 957.3 Average specific output (kW / kg): 281.7 Peak specific power (kW / kg): 1295

[0087] Figure 8 shows the hydrogen flow rate and the amount of activated aluminum consumed over time during the reaction. Figure 9 shows the relationship between the energy produced by the reaction and the power output. Figure 10 shows the relationship between the amount of activated aluminum consumed by the reaction and the power output.

[0088] Preparation of activated aluminum using sample C (50% catalyst by mass) from used beverage cans and its reaction with water Aluminum scrap obtained from shredded used beverage cans (UBC) was activated with Sample C and reacted with water using a procedure similar to that described above for Sample D. The amount of catalyst comprised approximately 50% by mass of the final water-reactive aluminum composition, and the water was heated to 60°C before reacting with the activated aluminum.

[0089] The yield of this reaction, expressed as a reaction efficiency (the percentage of energy released as heat and hydrogen relative to the theoretical energy embedded in the aluminum), was 94%, and after completion of the reaction, 84% of the initial activated metal alloy catalyst was recovered in its starting state. The following power outputs were observed: Average power (W): 278.6 Peak power (W): 1288 Average specific output (kW / kg): 169.6 Peak specific power (kW / kg): 783.8

[0090] Figure 11 shows the hydrogen flow rate and the amount of activated aluminum consumed over time during the reaction. Figure 12 shows the relationship between the energy produced by the reaction and the power output. Figure 13 shows the relationship between the amount of activated aluminum consumed by the reaction and the power output.

[0091] Preparation of activated aluminum using sample F and its reaction with water To activate the aluminum in Sample F, the catalyst was heated, even though it has a melting point below room temperature. For example, the catalyst was preheated using a hot plate set at 200°C, although other forms of heating may also be used. The aluminum was preheated in an oven at 130°C. The catalyst and aluminum were placed in a sealed container so that the weight percentage of catalyst relative to the total fuel reached 5%. The aluminum may also be activated with other mass ratios of catalyst relative to the mass of aluminum being activated, such as 0 to about 3%, 3 to about 6%, about 6 to about 10%, about 10 to about 100%, and about 100 to about 700%. The container was stirred by shaking until the catalyst covered the aluminum metal. The mixture was continuously mixed and heated for 1 to 2 hours by maintaining the container (e.g., see Figure 2) at 130°C in a rotating oven; however, the mixture may also be heated at temperatures ranging from room temperature to 130°C for 0 to 240 hours (0 to 10 days). The mixture may also be activated manually by stirring the container 3 to 4 times over the course of heating.

[0092] When water was added to the catalytically activated aluminum, the reaction rate proceeded similarly to the results described for Sample D. Typical reaction yields, expressed as reaction efficiencies (the percentage of energy released as heat and hydrogen relative to the theoretical energy embedded in the aluminum), were 86-92%. After the reaction, 90% of the initial catalyst was recovered in its starting state. In another example, shredded used beverage cans (UBCs) were activated in a rotary oven with Sample F, a catalyst weight percentage approaching 20% ​​of the activated aluminum. The reaction yield for this example, expressed as reaction efficiency (the percentage of energy released as heat and hydrogen relative to the theoretical energy embedded in the aluminum), was 64%.

[0093] Equivalents and Scope In the claims, articles such as "a," "an," and "the" may refer to the plural unless otherwise indicated or clear from the context. A claim or description including "or" between one or more members of a group is deemed to be satisfied if one, more than one, or all of those group members are present in, employed in, or otherwise relevant to a given product or process, unless otherwise indicated or clear from the context. Embodiments are provided herein in which exactly one member of a group is present in, employed in, or otherwise relevant to a given product or process. Embodiments are provided herein in which more than one or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[0094] Furthermore, the inventions provided herein encompass all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the enumerated claims are introduced into another claim. For example, any claim dependent on another claim can be amended to include one or more limitations found in any other claim dependent on the same base claim. Where elements are presented as a list, e.g., in Markush group format, each subgroup of elements is also disclosed, and any element(s) can be removed from the group. Generally, when the inventions provided and described herein, or aspects of the inventions described and provided herein, are referred to as comprising certain elements and / or features, etc., it is to be understood that particular embodiments of the invention or aspects of the invention consist of, or consist essentially of, such elements and / or features, etc. For the sake of brevity, these embodiments have not been specifically described in these terms herein. It should also be noted that the terms "comprising" and "containing" are open-ended and intended to allow for the inclusion of additional elements or steps. Where ranges are given, the endpoints are included. Furthermore, unless otherwise specified or otherwise apparent from the context and the understanding of one of ordinary skill in the art, values ​​expressed as ranges can assume any specific value or subrange within such range, up to one-tenth of the unit of the lower limit of such stated range, in different embodiments of the description of the invention described and provided herein, unless the context clearly dictates otherwise.

[0095] This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. In the event of a conflict between any of the incorporated references and this specification, this specification will control. Additionally, any particular embodiment that falls within the prior art may be expressly excluded from any one or more of the claims. Such embodiments are deemed to be known to those of ordinary skill in the art and may be excluded even if the exclusion is not expressly set forth herein. Any particular embodiment may be excluded from any claim for any reason, whether or not related to the existence of prior art.

[0096] Each numerical value provided herein is intended to represent the minimum or maximum value within the range of the corresponding parameter. Thus, when a numerical value is added to a claim, the numerical value provides explicit support for claiming a range that may exist above or below the numerical value in accordance with the teachings of this specification. All values ​​between the minimum and maximum values ​​within each numerical range provided herein (including any minimum, reference, and maximum values ​​listed in any table) are contemplated and expressly supported herein, according to the number of significant digits represented in each particular range. The minimum and reference values, the reference and maximum values, and the ranges between the minimum and maximum values ​​are expressly contemplated in this application.

[0097] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments described herein. The scope of the embodiments of the invention described herein is not intended to be limited to the above description, but is instead set forth in the appended claims. Those skilled in the art will recognize that various changes and modifications to this description can be made without departing from the spirit or scope of the invention, as defined in the following claims.

Claims

1. 1. A water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; a non-eutectic activating metal alloy comprising bismuth, tin, indium, and gallium disposed along the microstructure of the aluminum or alloy thereof, the non-eutectic activating metal alloy comprising up to about 10% gallium by mass; The water-reactive aluminum composition, wherein when water is introduced into the composition, the aluminum or alloy thereof disintegrates, exposing the internal volume to the water and causing a rapid hydrolysis reaction.

2. 1. A water-reactive aluminum composition comprising: aluminum or an alloy thereof having a surface oxide layer, an internal volume, and a microstructure; an activated metal alloy disposed along the microstructure of the aluminum or alloy thereof, the activated metal alloy comprising at least two metals selected from the group consisting of bismuth, tin, and indium; When water is introduced into the composition, the aluminum or its alloy disintegrates, exposing the internal volume to the water and causing a rapid hydrolysis reaction; The water-reactive aluminum composition does not contain gallium.

3. 3. The water-reactive aluminum composition of claim 2, wherein the activating metal alloy comprises bismuth, tin, and indium.

4. 10. The water-reactive aluminum composition of claim 1, wherein the activated metal alloy consists essentially of bismuth, gallium, indium, and tin.

5. 5. The water-reactive aluminum composition of any one of claims 1 to 4, formed by a process comprising contacting the aluminum or alloy thereof with the activated metal alloy, wherein when the aluminum or alloy thereof contacts the activated metal alloy, the activated metal alloy is in liquid form and the aluminum or alloy thereof is in solid form.

6. 6. The water-reactive aluminum composition of claim 5, wherein the activated metal alloy is heated above its melting point prior to contacting the aluminum or alloy thereof.

7. 7. The water-reactive aluminum composition of any one of claims 1 to 6, wherein the activated metal alloy has a melting point lower than the melting temperature of the aluminum or its alloy.

8. 8. The water-reactive aluminum composition of any one of claims 1 to 7, wherein the activated metal alloy has a melting point of less than 200°C.

9. 9. The water-reactive aluminum composition of any one of claims 1 to 8, wherein the activated metal alloy has a melting point of less than 100°C.

10. 10. The water-reactive aluminum composition of any one of claims 1 to 9, wherein the activated metal alloy is at least about 6%, or about 6%, of the total mass of the water-reactive aluminum composition.

11. 11. The water-reactive aluminum composition of any one of claims 1-10, wherein the aluminum or alloy thereof comprises one or more alloying elements selected from the group consisting of copper, silicon, iron, manganese, zinc, titanium, magnesium, lithium, cadmium, zirconium, beryllium, scandium, sodium, cerium, yttrium, silver, calcium, boron, chromium, bismuth, lead, vanadium, nickel, cobalt, oxygen, and gallium, and wherein the alloying elements collectively comprise from 0 to about 20% of the total mass of the aluminum.

12. 11. The water-reactive aluminum composition of any one of claims 1-10, wherein the activated metal alloy comprises a field metal comprising, by mass, about 51.2% indium, about 32.0% bismuth, and about 16.8% tin.

13. 13. The water-reactive aluminum composition of any one of claims 1 to 12, wherein the activated metal alloy comprises less than about 10% gallium by weight.

14. 14. The water-reactive aluminum composition of any one of claims 1 to 13, wherein the activated metal alloy is solid at room temperature (e.g., 20°C).

15. 15. The water-reactive aluminum composition of any one of claims 1 to 14, wherein the activated metal alloy is liquid at a temperature below the melting point of indium (about 157°C).

16. 1. A method for activating aluminum or its alloys, comprising the steps of: contacting the aluminum or alloy thereof with a non-eutectic activating metal alloy comprising bismuth, tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy and below the melting temperature of the aluminum or alloy thereof for a predetermined time to provide a water-reactive aluminum composition.

17. 1. A method for activating aluminum or its alloys, comprising the steps of: contacting the aluminum or alloy thereof with an activating metal alloy comprising tin, indium, and gallium to provide a mixture; and heating the mixture at a temperature above the melting temperature of the non-eutectic activated metal alloy and below the melting temperature of the aluminum or alloy thereof for a predetermined time to provide a water-reactive aluminum composition.

18. 18. The method of claim 17, wherein the non-eutectic activation metal alloy is bismuth-free.

19. 1. A method for activating aluminum or its alloys, comprising the steps of: contacting the aluminum or alloy thereof with an activating metal alloy comprising at least two metals selected from the group consisting of bismuth, tin, and indium to provide a gallium-free mixture; and heating the mixture at a temperature above the melting temperature of the activated metal alloy for a predetermined period of time to provide a water-reactive aluminum composition.

20. 20. The method of claim 19, wherein the activation metal alloy comprises bismuth, tin, and indium.

21. 21. The method of any one of claims 16 to 20, wherein contacting the aluminium or alloy thereof with the activated metal alloy comprises melting the activated metal alloy and applying the activated metal alloy uniformly to the surface of the aluminium or alloy thereof.

22. 22. The method of any one of claims 16 to 21, wherein the mixture comprises the activated metal alloy in an amount of about 30% by mass of the aluminium or alloy thereof.

23. 23. The method of any one of claims 16 to 22, wherein the predetermined time period is from about 2 hours to about 3 hours.

24. 24. The method of any one of claims 16-18 and claims 21-23, further comprising varying the amount of gallium in the activated metal alloy such that the temperature required for the water-reactive aluminum composition to react with water is varied.

25. 24. The method of any one of claims 16-18 and claims 21-23, further comprising varying the amount of gallium in the activated metal alloy such that, upon contact of the water-reactive aluminum composition with water, the temperature at which the reaction rate of the water-reactive aluminum composition with water accelerates to form vapor is varied.

26. 24. The method of any one of claims 16-18 and claims 21-23, further comprising varying the amount of gallium in the activated metal alloy such that when the water-reactive aluminum composition is contacted with water, hydrogen gas is produced in the absence of steam.

27. 27. The method of any one of claims 16 to 26, further comprising heating the mixture of aluminum or an alloy thereof and activated metal alloy at a temperature above the melting point of the activated metal alloy while continuously stirring the mixture in a rotating drum.

28. 28. The method of claim 27, wherein the mixture is heated with a heating element inside the rotating drum.

29. 28. The method of claim 27, wherein the mixture is heated with a heating element external to the rotating drum.

30. 16. A method of providing hydrogen and / or steam, the method comprising providing hydrogen and / or steam by contacting the water-reactive aluminum composition of any one of claims 1 to 15 with water, such that a rapid hydrolysis reaction occurs.

31. 31. The method of claim 30, further comprising recovering at least about 95% of the activated metal alloy after the rapid hydrolysis reaction has occurred.

32. 16. A fuel mixture comprising a plurality of water-reactive aluminum compositions according to any one of claims 1 to 15 and a plurality of water-reactive aluminum compositions comprising aluminum and 0 to about 3% or about 3 to about 6% gallium by mass, wherein the gallium is present in the plurality of compositions in varying amounts, such that when the compositions contact water, a distribution of reaction rates is achieved at a given reaction onset temperature or steady-state operating temperature.

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