Hydrogen production catalysts, methods of making and using the same

Abstract

This application provides a hydrogen production catalyst, its preparation method, and its application. The hydrogen production catalyst includes aluminum particles and a metal salt catalytic material, with the metal salt catalytic material attached to the surface of the aluminum particles. This application uses aluminum particles as a carrier and composites the metal salt catalytic material onto the aluminum particles. The metal salt catalytic material can catalyze the hydrolysis of sodium borohydride to produce hydrogen, and the NaBO2 produced after the hydrolysis of sodium borohydride can catalyze the hydrolysis of the aluminum particles, synergistically producing hydrogen and improving the utilization rate of the material. It features low cost, simple preparation method, low water consumption, and high hydrogen production rate.

Description

Technical Field

[0001] This invention relates to the field of hydrogen technology, and in particular to a hydrogen production catalyst, its preparation method, and its application. Background Technology

[0002] Hydrogen energy resources are abundant and have advantages such as light weight, high calorific value, high energy, cleanliness, environmental friendliness, and high recycling efficiency, making them the best alternative to fossil fuels.

[0003] In traditional technologies, the hydrolysis of sodium borohydride is considered a common method for producing hydrogen. It has a hydrogen storage density of up to 10.8 wt%, the generation rate is easy to control, the hydrogen produced is of high purity and does not require a purification process, making it one of the best hydrogen sources for PEMFCs (proton exchange membrane fuel cells).

[0004] The chemical formula for the reaction of sodium borohydride (NaBH4) with water to produce hydrogen is as follows:

[0005] NaBH4 + 2H2O → NaBO2 + 4H2

[0006] In the process of hydrogen production, noble metal catalysts and non-noble metal catalysts can be used for catalysis, but there are still problems such as high cost, low hydrogen production rate and high water consumption. Summary of the Invention

[0007] Based on this, this application provides a hydrogen production catalyst that can improve the hydrogen production rate of sodium borohydride and reduce water consumption. Furthermore, it provides a method for preparing the hydrogen production catalyst and its application.

[0008] The above-mentioned objectives can be achieved through the following technical solutions.

[0009] In a first aspect, this application provides a hydrogen production catalyst, which includes aluminum particles and a metal salt catalytic material, wherein the metal salt catalytic material is attached to the surface of the aluminum particles.

[0010] In some embodiments, the D50 particle size of the hydrogen production catalyst is 5 μm to 20 μm.

[0011] In some embodiments, the aluminum particles in the hydrogen production catalyst account for 50% to 96% by mass.

[0012] In some embodiments, the mass percentage of the metal salt catalytic material in the hydrogen production catalyst is 2% to 25%.

[0013] In some embodiments, the metal salt catalyst includes at least one of cobalt chloride, ferric chloride, nickel chloride, cobalt bromide, ferric bromide, nickel bromide, cobalt iodide, nickel iodide, ferric iodide, cobalt nitrate, ferric nitrate, nickel nitrate, cobalt sulfate, ferric sulfate, and nickel sulfate.

[0014] In some embodiments, the hydrogen production catalyst also includes an auxiliary agent.

[0015] In some embodiments, the additives include at least one of bismuth powder, cobalt powder, sodium chloride, and lithium aluminum hydride.

[0016] In some embodiments, the mass percentage of the auxiliary agent in the hydrogen production catalyst is 2% to 25%.

[0017] Secondly, this application provides a method for preparing a hydrogen production catalyst as described in the first aspect, the method comprising:

[0018] The hydrogen production catalyst is prepared by ball milling a mixture comprising aluminum particles and metal salt catalyst materials.

[0019] In some embodiments, the diameter of the aluminum particles is 10 μm to 200 μm.

[0020] In some embodiments, the ball mill has a ball-to-material ratio of (5~50):1, a time of 1h~20h, and a rotation speed of 50rpm~400rpm.

[0021] Thirdly, this application provides a hydrogen-generating agent, which includes sodium borohydride and a hydrogen-generating catalyst as described in the first aspect.

[0022] In some embodiments, the sodium borohydride in the hydrogen-generating agent accounts for 50% to 99% by mass.

[0023] In some embodiments, the hydrogen-generating catalyst accounts for 1% to 50% of the mass of the hydrogen-generating agent.

[0024] Fourthly, this application provides an application of the hydrogen-generating agent as described in the third aspect, wherein the hydrogen-generating agent is used for hydrogen production by hydrolysis.

[0025] Compared with traditional technologies, this application has at least the following beneficial effects:

[0026] This application uses aluminum particles as a carrier and composites a metal salt catalytic material on the aluminum particles. The metal salt catalytic material can catalyze the hydrolysis of sodium borohydride to produce hydrogen. Correspondingly, sodium borohydride is also in solid form, which solves the problem of low hydrogen storage density when sodium borohydride reacts in liquid state. In addition, the NaBO2 produced after the hydrolysis of sodium borohydride can catalyze the hydrolysis of aluminum particles, synergistically producing hydrogen, which improves the utilization rate of materials. It has the characteristics of low cost, simple preparation method, low water consumption and high hydrogen production rate. Attached Figure Description

[0027] Figure 1 This is a SEM image of the hydrogen production catalyst prepared in Example 1 of this application.

[0028] Figure 2 The image shows the XRD pattern of the hydrogen production catalyst prepared in Example 1 of this application.

[0029] Figure 3 This is a hydrogen production curve showing the total hydrogen production of the hydrogen-generating agents prepared in Examples 1-7 of this application.

[0030] Figure 4 This is a hydrogen production curve of the hydrogen-generating agent prepared in Examples 1, 2, 3 and 7 of this application with a water volume of 0.6 ml. Detailed Implementation

[0031] The present invention will be further described in detail below with reference to the accompanying drawings, embodiments, and examples. These embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the invention. The purpose of providing these embodiments and examples is to enable a more thorough and complete understanding of the disclosure of the present invention. It should also be understood that the present invention can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present invention, and the equivalent forms obtained also fall within the protection scope of the present invention. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of the present invention. It should be understood that the present invention can be implemented without one or more of these details.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0033] In this invention, "optionally," "optionally," and "optional" mean that they are optional, that is, they are selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent.

[0034] In this invention, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0035] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0036] In this invention, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the distribution of selectable values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every value between these two endpoints. Unless otherwise specified, when the numerical interval refers only to the integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.

[0037] All references to this invention are incorporated herein by reference as if each document were individually incorporated by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, the referenced documents involved in this invention are incorporated in their entirety and for all purposes. When references are made in this invention, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When references are made in this invention, examples and preferred embodiments of the relevant technical features cited may also be incorporated herein by reference, but only to the extent that they enable the implementation of this invention. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptively based on the description in this application.

[0038] Traditional technologies directly use ferric chloride as a catalyst, combining the formation of an Fe-B catalyst with hydrogen production via water electrolysis. This reduces intermediate processes and saves costs, but suffers from low hydrogen production rates (76%) and high water consumption (12 times the theoretical water consumption). In contrast, this application uses aluminum particles as a carrier for the metal salt catalyst, which is placed on the surface of the aluminum particles. During the catalytic hydrolysis of sodium borohydride, the metal salt catalyst reacts with water to synthesize an MB catalyst in situ (M refers to the metal element in the metal salt catalyst), catalyzing the hydrolysis of sodium borohydride to produce hydrogen. The resulting sodium metaborate (NaBO2) is strongly alkaline and can catalyze the hydrolysis of aluminum particles, achieving synergistic hydrogen release with sodium borohydride. The hydrogen production rate can reach 95%, and the water consumption is only three times the theoretical water consumption.

[0039] The first aspect of this application provides a hydrogen production catalyst, which includes aluminum particles and a metal salt catalytic material. The metal salt catalytic material is attached to the surface of the aluminum particles and is used to catalyze the production of hydrogen from sodium borohydride.

[0040] In this application, aluminum particles are used as a carrier to support metal salt catalytic materials. In the catalytic process, the metal salt catalytic materials are synthesized in situ to form MB catalysts, which catalyze the hydrolysis of sodium borohydride to produce hydrogen. Moreover, the sodium metaborate generated by hydrolysis is strongly alkaline and can catalyze the hydrolysis of aluminum particles, achieving a synergistic hydrogen release effect. This not only improves the hydrogen production rate but also reduces the water consumption.

[0041] In some embodiments, the D50 particle size of the hydrogen production catalyst is 5 μm to 20 μm, for example, it can be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm.

[0042] This application controls the particle size of the hydrogen production catalyst to ensure that the catalyst is uniformly dispersed on the surface of aluminum particles, increasing the probability of contact between the catalyst and sodium borohydride. If the particle size of the hydrogen production catalyst is relatively small, there may be safety issues; if the particle size of the hydrogen production catalyst is relatively large, uneven dispersion is likely to occur when mixed with sodium borohydride.

[0043] In some embodiments, the mass percentage of aluminum particles in the hydrogen production catalyst is 50% to 96%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 96%.

[0044] In some embodiments, the mass percentage of the metal salt catalytic material in the hydrogen production catalyst is 2% to 25%, for example, it can be 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24% or 25%.

[0045] In some embodiments, the metal salt catalytic material includes at least one of cobalt chloride, ferric chloride, nickel chloride, cobalt bromide, ferric bromide, nickel bromide, cobalt iodide, nickel iodide, ferric iodide, cobalt nitrate, ferric nitrate, nickel nitrate, cobalt sulfate, ferric sulfate, and nickel sulfate.

[0046] In some embodiments, the hydrogen production catalyst further includes an auxiliary agent.

[0047] In some embodiments, the additives include at least one of bismuth powder, cobalt powder, sodium chloride, and lithium aluminum hydride.

[0048] This application effectively improves the catalytic performance of the catalyst and the hydrogen production performance of aluminum by adding additives. Specifically, the addition of bismuth and cobalt powders not only serves as a grinding aid during ball milling but also allows them to adhere to the surface of aluminum particles. During catalysis, the bismuth powder forms a galvanic cell with the aluminum particles, enhancing the hydrogen production efficiency of aluminum particles through hydrolysis. Furthermore, the addition of lithium aluminum hydride (LDH) not only serves as a grinding aid during ball milling but also decomposes and releases heat during catalysis, further improving the hydrogen production efficiency of aluminum particles through hydrolysis.

[0049] In some embodiments, the mass percentage of the auxiliary agent in the hydrogen production catalyst is 2% to 25%, for example, it can be 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24% or 25%.

[0050] A second aspect of this application provides a method for preparing a hydrogen production catalyst as described in the first aspect, the method comprising:

[0051] The hydrogen production catalyst is prepared by ball milling a mixture comprising aluminum particles and metal salt catalyst materials.

[0052] This application employs ball milling to attach metal salt catalysts to the surface of aluminum particles, which enables the metal salt catalysts to be uniformly dispersed on the aluminum particles, increases the contact probability between the metal salt catalysts and sodium borohydride, and better exerts the catalytic performance of the metal salt catalysts.

[0053] In some embodiments, the diameter of the aluminum particles is 10μm to 200μm, for example, it can be 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm or 200μm.

[0054] This application controls the diameter of aluminum particles to effectively ensure the dispersion of metal salt catalyst materials. If the diameter of aluminum particles is relatively small, there may be problems such as poor safety and high cost; if the diameter of aluminum particles is relatively large, there may be problems with poor dispersion.

[0055] It is understood that this application does not impose specific requirements or special limitations on the ball mill used in the ball milling process. Those skilled in the art can make reasonable selections according to actual needs. For example, a planetary ball mill or a vibratory ball mill can be used.

[0056] In some embodiments, the ball-to-material ratio of the ball mill is (5~50):1, for example, it can be 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1.

[0057] Optionally, the ball milling time is 1h to 20h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or 20h.

[0058] Optionally, the rotational speed of the ball mill is 50 rpm to 400 rpm, for example, it can be 50 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm, 140 rpm, 160 rpm, 180 rpm, 200 rpm, 220 rpm, 240 rpm, 260 rpm, 280 rpm, 300 rpm, 320 rpm, 340 rpm, 360 rpm, 380 rpm or 400 rpm.

[0059] In some embodiments, the hydrogen production catalyst further includes an auxiliary agent, and the preparation method includes:

[0060] The hydrogen production catalyst is obtained by mixing aluminum particles, metal salt catalyst materials, and additives.

[0061] Exemplarily, a method for preparing the above-mentioned hydrogen production catalyst is provided, comprising:

[0062] Aluminum particles, metal salt catalyst and additives are ball-milled and mixed. The ball-milling parameters include: ball-to-material ratio of (5~50):1, time of 1h~20h, and rotation speed of 50rpm~400rpm, to prepare the hydrogen production catalyst.

[0063] A third aspect of this application provides a hydrogen-generating agent comprising sodium borohydride and a hydrogen-generating catalyst as described in the first aspect.

[0064] In some embodiments, the sodium borohydride in the hydrogen-generating agent accounts for 50% to 99% by mass, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%.

[0065] In some embodiments, the mass percentage of the hydrogen-generating catalyst in the hydrogen-generating agent is 1% to 50%, for example, it can be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0066] This application controls the mass ratio of the hydrogen production catalyst in the hydrogen production agent to ensure the hydrogen production rate and hydrogen storage density. If the proportion of the hydrogen production catalyst is relatively low, it may result in a low ratio of catalyst to reactants, affecting the hydrogen production rate; if the proportion of the hydrogen production catalyst is relatively high, it may reduce the hydrogen storage density.

[0067] The fourth aspect of this application provides an application of the hydrogen-generating agent as described in the third aspect, wherein the hydrogen-generating agent is used for hydrogen production by hydrolysis.

[0068] In some embodiments, the method for producing hydrogen from the hydrogen-generating agent includes adding the hydrogen-generating agent to water at a first temperature.

[0069] Optionally, the first temperature is 20℃~90℃.

[0070] The embodiments of the present invention will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this invention, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0071] Example 1

[0072] (1) Hydrogen production catalyst

[0073] Aluminum particles with a particle size of 20 μm, cobalt chloride, and bismuth powder were weighed in a mass ratio of 91:4.5:4.5 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm, and the milling time was 7 hours, thus obtaining the hydrogen production catalyst with a particle size D50 of 10 μm. Figure 1 Here is a SEM image of the hydrogen production catalyst. Figure 2 The image shows the XRD pattern of the hydrogen production catalyst, where Al and bismuth do not form an alloy.

[0074] (2) Hydrogen-generating agent

[0075] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0076] Example 2

[0077] (1) Hydrogen production catalyst

[0078] Aluminum particles with a particle size of 20 μm, cobalt chloride, and sodium chloride were weighed in a mass ratio of 91:4.5:4.5 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm, and the ball milling time was 7 hours, thus obtaining the hydrogen production catalyst with a particle size D50 of 15 μm.

[0079] (2) Hydrogen-generating agent

[0080] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0081] Example 3

[0082] (1) Hydrogen production catalyst

[0083] Aluminum particles with a particle size of 20 μm, cobalt chloride, and cobalt powder were weighed in a mass ratio of 91:4.5:4.5 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm, and the ball milling time was 7 hours to obtain the hydrogen production catalyst with a particle size D50 of 20 μm.

[0084] (2) Hydrogen-generating agent

[0085] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0086] Example 4

[0087] (1) Hydrogen production catalyst

[0088] Aluminum particles with a particle size of 20 μm, ferric chloride and bismuth powder were weighed in a mass ratio of 91:4.5:4.5 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm, and the ball milling time was 7 h, so as to obtain the hydrogen production catalyst with a particle size D50 of 10 μm.

[0089] (2) Hydrogen-generating agent

[0090] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0091] Example 5

[0092] (1) Hydrogen production catalyst

[0093] Aluminum particles with a particle size of 20 μm, nickel chloride, and bismuth powder were weighed in a mass ratio of 91:4.5:4.5 and placed in a vibrating ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm, and the ball milling time was 7 hours to obtain the hydrogen production catalyst with a particle size D50 of 15 μm.

[0094] (2) Hydrogen-generating agent

[0095] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0096] Example 6

[0097] (1) Hydrogen production catalyst

[0098] Aluminum particles with a particle size of 20 μm, cobalt chloride, sodium chloride and bismuth powder were weighed in a mass ratio of 86:8:3:3 and placed in a vibrating ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm and the ball milling time was 7 h, so as to obtain the hydrogen production catalyst with a particle size D50 of 10 μm.

[0099] (2) Hydrogen-generating agent

[0100] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0101] Example 7

[0102] (1) Hydrogen production catalyst

[0103] Aluminum particles with a particle size of 20 μm, cobalt chloride, lithium aluminum hydride and bismuth powder were weighed in a mass ratio of 86:8:3:3 and placed in a vibrating ball mill for ball milling. The ball-to-material ratio was 14:1, the rotation speed was 200 rpm and the ball milling time was 7 h, so as to obtain the hydrogen production catalyst with a particle size D50 of 15 μm.

[0104] (2) Hydrogen-generating agent

[0105] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0106] Example 8

[0107] (1) Hydrogen production catalyst

[0108] Aluminum particles with a particle size of 200 μm, cobalt chloride and bismuth powder were weighed in a mass ratio of 50:25:25 and placed in a vibrating ball mill for ball milling. During the ball milling process, the ball-to-material ratio was 50:1, the rotation speed was 50 rpm, and the ball milling time was 20 h, so as to obtain the hydrogen production catalyst with a particle size D50 of 10 μm.

[0109] (2) Hydrogen-generating agent

[0110] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed in a mass ratio of 50:50.

[0111] Example 9

[0112] (1) Hydrogen production catalyst

[0113] Aluminum particles with a particle size of 100 μm, cobalt chloride, and cobalt powder were weighed in a mass ratio of 96:2:2 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 5:1, the rotation speed was 400 rpm, and the ball milling time was 1 hour, thus obtaining the hydrogen production catalyst with a particle size D50 of 20 μm.

[0114] (2) Hydrogen-generating agent

[0115] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 1:99.

[0116] Example 10

[0117] (1) Hydrogen production catalyst

[0118] Aluminum particles with a particle size of 10 μm, cobalt chloride, and cobalt powder were weighed in a mass ratio of 70:20:10 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 30:1, the rotation speed was 300 rpm, and the ball milling time was 10 h to obtain the hydrogen production catalyst with a particle size D50 of 5 μm.

[0119] (2) Hydrogen-generating agent

[0120] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed in a mass ratio of 4:6.

[0121] Example 11

[0122] (1) Hydrogen production catalyst

[0123] Aluminum particles with a particle size of 10 μm, cobalt chloride, and lithium aluminum hydride were weighed in a mass ratio of 84:10:6 and placed in a planetary ball mill for ball milling. The ball-to-material ratio was 30:1, the rotation speed was 300 rpm, and the ball milling time was 10 h, thus obtaining the hydrogen production catalyst with a particle size D50 of 5 μm.

[0124] (2) Hydrogen-generating agent

[0125] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 20:80.

[0126] Example 12

[0127] The hydrogen production catalyst and hydrogen production agent were prepared according to the method of Example 1, except that the diameter of the aluminum particles was 5 μm during the preparation of the hydrogen production catalyst.

[0128] Example 13

[0129] The hydrogen production catalyst and hydrogen production agent were prepared according to the method of Example 1, except that the diameter of the aluminum particles was 300 μm during the preparation of the hydrogen production catalyst.

[0130] Comparative Example 1

[0131] (1) Hydrogen production catalyst

[0132] Cobalt chloride was used directly as the hydrogen production catalyst.

[0133] (2) Hydrogen-generating agent

[0134] The above-mentioned hydrogen production catalyst and sodium borohydride are mixed at a mass ratio of 2:8.

[0135] Comparative Example 2

[0136] The hydrogen production catalyst and hydrogen production agent were prepared according to the method of Example 1, except that aluminum particles were replaced with nickel particles.

[0137] The hydrogen-generating agents prepared in the above embodiments and comparative examples were subjected to performance tests, and the test methods included:

[0138] (1) Total hydrogen production

[0139] Place 0.2g of hydrogen-generating agent into a flask, heat in a water bath to 80℃, add deionized water to the flask, and collect the produced hydrogen gas using the water displacement method until no more hydrogen gas is produced. The test results are shown in Table 1. Figure 3 The hydrogen production curves are for testing the total hydrogen production in Examples 1-7.

[0140] (2) Hydrogen production with 0.6 ml of water

[0141] Place 0.2g of hydrogen-generating agent into a flask, heat in a water bath to 80℃, add 0.6ml of deionized water to the flask, and collect the produced hydrogen gas using the water displacement method until no more hydrogen gas is produced. The test results are shown in Table 1. Figure 4 The hydrogen production curves are for testing the hydrogen production of 0.6 ml of water in Examples 1, 2, 3 and 7.

[0142] Table 1

[0143]

[0144] As can be seen from the table above:

[0145] (1) Compared with Example 2, it can be seen that by adding bismuth powder and cobalt powder, this application can not only be used as a grinding aid in the ball milling process, but also the bismuth powder and cobalt powder can adhere to the surface of aluminum particles. In the catalytic process, the bismuth powder can form a galvanic cell with the aluminum particles, thereby improving the hydrogen production effect of the aluminum particles through hydrolysis.

[0146] (2) Compared with Examples 12-13, Example 1 shows that the present application controls the diameter of aluminum particles to effectively ensure the dispersion of metal salt catalyst materials. If the diameter of aluminum particles is relatively small, there may be problems such as poor safety and high cost; if the diameter of aluminum particles is relatively large, there may be problems of poor dispersion.

[0147] (3) Compared with Comparative Examples 1-2, it can be seen that in this application, aluminum particles are used as carriers and metal salt catalytic materials are composited on the aluminum particles. The metal salt catalytic materials can catalyze the hydrolysis of sodium borohydride to produce hydrogen. Correspondingly, sodium borohydride is also solid, which solves the disadvantage of low hydrogen storage density when sodium borohydride reacts in liquid state. In addition, NaBO2 produced after the hydrolysis of sodium borohydride to produce hydrogen can catalyze the hydrolysis of aluminum particles and synergistically produce hydrogen, which improves the utilization rate of materials. It has the characteristics of low cost, simple preparation method, low water consumption and high hydrogen production rate.

[0148] (4) Compared with Comparative Examples 1-2, Example 11 of this application shows that by adding lithium aluminum hydride, this application can not only be used as a grinding aid in the ball milling process, but also decompose and exothermic during the catalytic process, thereby improving the hydrolysis hydrogen production effect of aluminum particles and reducing water consumption.

[0149] Based on the above embodiments and comparative examples, this application has at least the following advantages:

[0150] (1) The hydrogen production catalyst prepared in this application is solid, and the corresponding sodium borohydride is also solid, which solves the disadvantage of low hydrogen storage density when liquid sodium borohydride reacts.

[0151] (2) The preparation process of this application is simple. The hydrogen production catalyst can be prepared by ball milling only. There are no steps such as drying, calcination and purification. The cost is low and it can achieve large-scale mass production.

[0152] (3) The raw materials used in this application are inexpensive.

[0153] (4) The hydrogen production catalyst prepared in this application can achieve a hydrogen production rate of 95%, and the water consumption is only 3 times that of the theoretical water consumption, which greatly reduces the water consumption carried in actual applications and indirectly improves the hydrogen storage density of the system.

[0154] (5) In the hydrogen production catalyst of this application, aluminum particles can also participate in the reaction and produce hydrogen, which improves the utilization rate of materials.

[0155] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0156] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A hydrogen production agent, characterized by, The hydrogen-generating agent includes sodium borohydride and a hydrogen-generating catalyst, wherein the mass ratio of the hydrogen-generating catalyst to the sodium borohydride in the hydrogen-generating agent is 20:

80. The hydrogen production catalyst comprises aluminum particles and cobalt chloride, wherein the cobalt chloride is attached to the surface of the aluminum particles; the hydrogen production catalyst further comprises an additive, wherein the additive comprises bismuth powder and lithium aluminum hydride; wherein the mass ratio of the aluminum particles, the cobalt chloride, the lithium aluminum hydride and the bismuth powder in the hydrogen production catalyst is 86:8:3:

3. The D50 particle size of the hydrogen production catalyst is 15 μm.

2. The hydrogen-generating agent as described in claim 1, characterized in that, The method for preparing the hydrogen production catalyst includes: The hydrogen production catalyst is prepared by ball milling a mixture comprising the aluminum particles, the cobalt chloride, and the additive.

3. The hydrogen-generating agent as described in claim 2, characterized in that, The preparation method satisfies at least one of the following conditions: (1) The diameter of the aluminum particles is 20 μm; (2) The ball-to-material ratio of the ball mill is (5~50):1, the time is 1h~20h, and the rotation speed is 50rpm~400rpm.

4. The application of the hydrogen-generating agent according to any one of claims 1-3, characterized in that, The hydrogen-generating agent is used for hydrogen production via hydrolysis.

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