Hydrogen production method and device for microwave-driven slurry hydrogen storage and production material and application

Abstract

The invention discloses a hydrogen production method and device of a microwave-driven slurry hydrogen storage and production material and application, and the hydrogen production method comprises the following steps: mixing the slurry hydrogen storage and production material with a catalyst, adding water, and carrying out a hydrogen production reaction under a microwave condition; wherein the microwave condition is carried out at the temperature of 80-150 DEG C by using microwaves with the power of 300-3000W; the slurry hydrogen storage and production material is composed of an organic liquid hydride and a solid, and the solid comprises at least one of a nanocrystalline metal, a metal hydride and a coordination hydride. According to the invention, the slurry hydrogen storage and production material is rapidly penetrated through microwave heating, the heating is uniform and high in efficiency, and the material can be heated to a proper reaction temperature within a short time, so that the starting time of the hydrogen production reaction is remarkably shortened; in addition, microwaves directly act on the nanoparticles and the slurry material, an oil film formed by the high-viscosity organic liquid hydride is destroyed, the chemical reaction can be effectively accelerated, and the overall hydrogen production efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen storage and production, and in particular to a hydrogen production method, device and application of a microwave-driven slurry hydrogen storage and production material. Background Art

[0002] As a clean, efficient and renewable secondary energy source, hydrogen energy is widely regarded as an important component of the future energy system. However, the efficient storage and transportation of hydrogen is one of the bottlenecks for the large-scale application of hydrogen energy. Due to the low density and easy leakage of hydrogen, its traditional high-pressure gas or low-temperature liquid storage methods have problems such as high energy consumption, complex equipment and safety hazards. Therefore, it is of great significance to study and develop new materials for efficient storage of hydrogen.

[0003] At present, some reports have been made of organic liquid hydrides coated with nanocrystalline aluminum-based powders, coordinated hydrides and metal hydrides to form fluid slurry hydrogen storage materials. Such composite slurry hydrogen storage materials can not only improve the hydrogen storage density and slurry stability, but also use the hydrothermal characteristics of nanocrystalline metal powders, coordinated hydrides and metal hydrides to provide heat for the release of hydrogen from organic liquid hydrides at the liquid-solid interface, thus realizing a continuous and controllable hydrogen process for multi-media composite slurry hydrogen storage materials.

[0004] However, the use of slurry hydrogen storage and production materials to produce hydrogen still has the disadvantages of long start-up time and low hydrogen production efficiency. The main reasons are: 1. In order to start the hydrogen production reaction quickly, the entire slurry needs to be heated between 150-300°C; 2. The viscosity of organic liquid hydride is relatively high. After coating the surface of nanoparticles to form an oil film, it will inhibit the contact between water or water vapor and the surface of nanoparticles, which will not only prolong the start-up time, but also affect the overall hydrogen production efficiency. In this regard, it is necessary to propose corresponding solutions. Summary of the invention

[0005] In order to overcome the problems existing in the prior art, the present invention provides a method for producing hydrogen by microwave-driven slurry hydrogen storage and production materials, comprising:

[0006] After mixing the slurry hydrogen storage and production material with the catalyst, water is added and hydrogen production reaction is carried out under microwave conditions;

[0007] The microwave conditions are as follows: microwave power of 300-3000W at a temperature of 80-150°C;

[0008] The slurry hydrogen storage and production material is composed of organic liquid hydride and solid, and the solid includes at least one of nano-microcrystalline metal, metal hydride, and coordinated hydride.

[0009] Further, the slurry hydrogen storage and production material comprises 60%-99% of organic liquid hydride and 1%-40% of solid in terms of mass percentage;

[0010] Wherein, the solid is one of nanocrystalline metal, coordinated hydride and metal hydride.

[0011] Further, the solid is a mixture of microcrystalline metal and metal hydride;

[0012] In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of microcrystalline metal and 1%-24% of metal hydride.

[0013] Further, the solid is a mixture of microcrystalline metal and coordinated hydride;

[0014] In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of microcrystalline metal and 1%-24% of coordinated hydride.

[0015] Further, the solid is a mixture of metal hydride and coordinated hydride;

[0016] In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of metal hydride and 1%-24% of coordinated hydride.

[0017] Further, the solid is a mixture of nanocrystalline metal, metal hydride and coordinated hydride;

[0018] In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of microcrystalline metal, 1%-24% of metal hydride and 1%-24% of coordinated hydride.

[0019] Preferably, the solid is a mixture of nanocrystalline metal, metal hydride and coordinated hydride, the solid accounts for 24% by mass of the slurry hydrogen storage and production material, and the rest is organic liquid hydride.

[0020] Furthermore, the mass of the catalyst is 0.01-0.2 times that of the slurry hydrogen storage and production material;

[0021] The mass of the water is 1-10 times that of the slurry hydrogen storage and production material;

[0022] The organic liquid hydride comprises at least one of a liquid aromatic compound, a heterocyclic compound, and a fully hydrogenated product of a liquid organic polyol;

[0023] The nanocrystalline metal includes at least one of Group I, Group II and Group III metals, and the particle size of the nanocrystalline metal is 50-1000nm;

[0024] The coordinated hydride includes LiAlH 4 、NaAlH 4 , KAlH 4 Mg(AlH 4 ) 2 、Ca(AlH 4 ) 2 , LiBH 4 , NaBH 4 KBH 4 Mg(BH 4 ) 2 , and Ca(BH 4 ) 2 At least one of;

[0025] The metal hydride includes LiH, KH, NaH, CuH 2 , CaH 2 At least one of;

[0026] The catalyst includes at least one of a Pd-based catalyst and a Pt-based catalyst.

[0027] It should be noted that the specific types of organic liquid hydrides do not need to be strictly limited. For example, the full hydrogenation product of aromatic compounds can be at least one of cyclohexane, methylcyclohexane, dimethylcyclohexane, decane, and decahydronaphthalene; the full hydrogenation product of heterocyclic compounds can be at least one of the full hydrogenation products of dibenzyltoluene, N-ethylcarbazole, N-propylcarbazole, N-methylindole, N-ethylindole, quinoline and the like; the full hydrogenation product of liquid organic polyols can be at least one of methanol, ethanol and isopropanol.

[0028] The present invention also provides a hydrogen production device for microwave-driven slurry hydrogen storage and production materials, comprising a microwave reactor, and a water storage tank and a slurry storage tank respectively connected to the microwave reactor;

[0029] The water storage tank and the slurry storage tank are used to transport a mixture of water, slurry hydrogen storage and production material and catalyst to the microwave reactor respectively;

[0030] The microwave reactor is used to provide microwave conditions so that the slurry hydrogen storage and production material is mixed with the catalyst and then reacts with water to produce hydrogen under microwave conditions. The microwave conditions are carried out at a power of 300-3000W and a temperature of 80-150°C.

[0031] Furthermore, a stirring component and a temperature measuring component are provided in the microwave reactor;

[0032] The microwave reactor is also connected to the separation tank and the recovery tank in sequence;

[0033] The separation tank is used to separate the generated hydrogen and the slurry after the reaction;

[0034] The recovery tank is used to store and recover the slurry after the reaction;

[0035] The separation tank is also connected to a hydrogen storage tank.

[0036] The present invention also provides the application of the above-mentioned hydrogen production method of microwave-driven slurry hydrogen storage and production material in the field of hydrogen storage and production.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] (1) The present invention uses microwave heating to quickly penetrate the slurry hydrogen storage and production material, and the heating is uniform and efficient. The material can be heated to a suitable reaction temperature in a short time, thereby significantly shortening the start-up time of the hydrogen production reaction.

[0039] (2) The present invention directly acts on nanoparticles and slurry materials through microwaves, destroying the oil film formed by high-viscosity organic liquid hydrides, enhancing the contact between water or water vapor and the surface of nanoparticles, effectively accelerating chemical reactions, and improving the overall hydrogen production efficiency.

[0040] (3) The present invention provides a method that combines the advantages of uniform microwave radiation heating and high energy utilization efficiency with the advantages of high hydrogen storage capacity and thermal coupling at the interface of slurry hydrogen storage materials, providing a new idea for the design of new hydrogen storage systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0042] Figure 1 The schematic diagram of the structure of the device for producing hydrogen by using microwave-driven slurry hydrogen storage and production materials according to Example 1 of the present invention is shown;

[0043] Figure 2 A comparison chart of hydrogen production performance of Examples 1-9 and Comparative Example 1 is shown;

[0044] Figure 3 A comparison chart of hydrogen production performance of Examples 10-13 and Comparative Example 2 is shown;

[0045] Figure 4 A comparison chart of hydrogen production performance of Examples 14-17 and Comparative Example 3 is shown;

[0046] Figure 5A comparison chart of hydrogen production performance of Examples 18-22 and Comparative Example 4 is shown;

[0047] Description of reference numerals:

[0048] 10. Microwave reactor; 101. Stirring component; 102. Temperature measuring component; 20. Water storage tank; 30. Slurry storage tank; 40. Separation tank; 50. Hydrogen storage tank; 60. Recovery tank. DETAILED DESCRIPTION

[0049] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0050] The following will be combined with the specific embodiments of the present invention and the drawings of the specification to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0051] Example 1

[0052] like Figure 1 As shown, a microwave-driven hydrogen production device for slurry hydrogen storage and production materials comprises a microwave reactor 10, and a water storage tank 20, a slurry storage tank 30 and a separation tank 40 respectively connected to the microwave reactor 10, and a recovery tank 60 connected to the separation tank 40. The water storage tank 20 and the slurry storage tank 30 are respectively used to transport a mixture of water, slurry hydrogen storage and production materials and a catalyst to the microwave reactor 10; the microwave reactor 10 is used to provide microwave conditions so that the slurry hydrogen storage and production materials are mixed with the catalyst and react with water to produce hydrogen under microwave conditions.

[0053] In order to make the hydrogen production reaction more uniform, a stirring component 101 and a temperature measuring component 102 are also provided inside the microwave reactor 10. The stirring component 101 is used to mix water, slurry hydrogen storage material and catalyst uniformly, and the temperature measuring component 102 can monitor the temperature of the hydrogen production reaction in real time. The discharge port of the microwave reactor 10 is connected to the separation tank 40, and a hydrogen detector and a gas flow meter are provided at the connection to monitor the generation time of hydrogen and the flow rate of the outlet hydrogen. In the present embodiment, the stirring component 101 is a stirring paddle arranged at the bottom of the temperature measuring component 102, and the temperature measuring component 102 is a thermocouple arranged at the top of the temperature measuring component 102.

[0054] The separation tank 40 is used to separate the generated hydrogen and the slurry after the reaction, and the recovery tank 60 is used to store and recover the slurry after the reaction; the separation tank 40 is also connected to a hydrogen storage tank 50 for storing hydrogen.

[0055] It should be noted that the following method embodiments are all carried out using the device of Example 1.

[0056] Example 2

[0057] A method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials, comprising the following steps:

[0058] S1. Weigh the full hydrogenation product of N-methylindole (H-MID) and 100 nm aluminum powder in a mass ratio of 0.76:0.24, then transfer them to a slurry storage tank, and ball mill them to obtain a slurry hydrogen storage material;

[0059] S2, through the slurry storage tank to store slurry hydrogen storage material and Pd / Al 2 O 3 The catalyst mixture was delivered to the microwave reactor at a feed rate of 2 g / min and 0.2 g / min, and stirring was started to make the slurry hydrogen storage material and Pd / Al 2 O 3 The catalysts are mixed uniformly to obtain a mixture;

[0060] S3, adding deionized water having a mass of 6 times the mass of the slurry hydrogen storage and production material to the mixture in the microwave reactor through a water storage tank to obtain a reaction system, and setting the power of the microwave reactor to 3000 W and ensuring that the reaction system performs hydrogen production reaction at a temperature of 120° C.;

[0061] S4. Monitor the gas flow rate at the outlet of the microwave reactor and calculate the conversion rate of the hydrogen production reaction.

[0062] Among them, the calculation formula for the conversion rate of the hydrogen production reaction is:

[0063]

[0064] For Example 2 to Example 22 and Comparative Examples 1-4, please proceed according to the component information of the slurry hydrogen storage and production materials given in Tables 1-3 and the microwave conditions given in Table 2, and refer to the method of Example 1.

[0065] Note: H-NPCZ and H-DBT in Table 1 and Table 4 are the perhydrogenation products of N-propylcarbazole and dibenzyltoluene, respectively.

[0066] Table 1 Composition information of slurry hydrogen storage and production materials of Examples 1-9

[0067]

[0068]

[0069] Table 2 Composition information of slurry hydrogen storage and production materials of Examples 10-22

[0070]

[0071]

[0072] Table 3 Component information of slurry hydrogen storage and production materials of comparative example

[0073]

[0074] According to the theoretical hydrogen storage capacity of organic liquid hydride, as well as nano-Al powder, MgH 2 and NaBH 4 The theoretical hydrogen release by hydrolysis of Al powder with different particle sizes is the same and is not differentiated. These results are shown in Table 4.

[0075] Table 4 Hydrogen release of materials

[0076]

[0077]

[0078] According to Tables 1-4, the theoretical hydrogen release amount of the slurry hydrogen storage and production materials of the embodiments and comparative examples can be calculated.

[0079] Table 5 summarizes the theoretical hydrogen release amount, microwave conditions, effective hydrogen release amount and hydrogen release start-up time of the slurry hydrogen storage and production materials of the above embodiments and comparative examples, and calculates the conversion rate.

[0080] Table 5 Microwave conditions and hydrogen production performance of hydrogen production reaction

[0081]

[0082]

[0083] Based on the hydrogen release data of Examples 1-9 and Comparative Example 1 and Figure 2 It can be seen that by microwave-driven hydrogen release in the Al-organic liquid hydrogen storage (organic liquid hydrogen storage is hereinafter referred to as H-LOHCs) system, the hydrogen release start-up time is reduced from 53min to less than 30min, and the hydrogen production conversion rate is increased from 80.4% to more than 85%. The comprehensive improvement effect is most obvious in Example 7, with a hydrogen release start-up time of only 17.4min and a hydrogen production conversion rate of 97.8%. The hydrogen release effects of Examples 8-9 show that the microwave-driven method also has a positive effect on the release of hydrogen from slurry hydrogen storage materials composed of other structural nitrogen heterocyclics and aromatic rings.

[0084] Based on the hydrogen release data of Examples 10-13 and Comparative Example 2 and Figure 3 , it can be seen that the microwave-driven Al-MgH 2 -H-LOHCs ternary system, the hydrogen release start-up time is reduced from 57min to less than 20min, and the hydrogen production conversion rate is increased from 78.1% to more than 90%. The comprehensive improvement effect is most obvious in Example 12, with a hydrogen release start-up time of only 12.8min and a hydrogen production conversion rate of 97.6%.

[0085] Based on the hydrogen release data of Examples 14-17 and Comparative Example 3 and Figure 4 , it can be seen that the microwave-driven Al-NaBH 4 -H-LOHCs ternary system, the hydrogen release start-up time is reduced from 65.4min to about 15min, and the hydrogen production conversion rate is increased from 79.5% to more than 90%. The comprehensive improvement effect is most obvious in Example 15, with a hydrogen release start-up time of only 15.4min and a hydrogen production conversion rate of 98.6%.

[0086] Based on the hydrogen release data of Examples 18-22 and Comparative Example 4 and Figure 5 , it can be seen that the microwave-driven Al-MgH 2 -NaBH 4 -H-LOHCs quaternary system, the hydrogen release start-up time is reduced from 60.8min to less than 15min, and the hydrogen production conversion rate is increased from 78.70% to more than 90%. The comprehensive improvement effect is most obvious in Example 20, with a hydrogen release start-up time of only 7.6min and a hydrogen production conversion rate of 99.3%.

[0087] The present invention also conducted experiments using 200nm K and Mg under the method of Example 1. The results showed that the start-up time of hydrogen release was significantly shortened under the action of microwaves, and the hydrogen production conversion rate was also above 90%. These results show that microwave heating can quickly penetrate the slurry hydrogen storage and production materials, and the heating is uniform and efficient. The materials can be heated to a suitable reaction temperature in a short time, thereby significantly shortening the start-up time of the hydrogen production reaction; in addition, microwaves directly act on the nanoparticles and slurry materials, destroying the oil film formed by high-viscosity organic liquid hydrides, enhancing the contact between water or water vapor and the surface of the nanoparticles, effectively accelerating the chemical reaction, and improving the overall hydrogen production efficiency. It also shows that the present invention is applicable and has certain application prospects.

[0088] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials, characterized in that: include, After mixing the slurry hydrogen storage and production material with the catalyst, water is added and hydrogen production reaction is carried out under microwave conditions; The microwave conditions are as follows: microwave power of 300-3000W at a temperature of 80-150°C; The slurry hydrogen storage and production material is composed of organic liquid hydride and solid, and the solid includes at least one of nano-microcrystalline metal, metal hydride, and coordinated hydride.

2. The method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials according to claim 1, characterized in that: In terms of mass percentage, the slurry hydrogen storage and production material comprises 60%-99% of organic liquid hydride and 1%-40% of solid; Wherein, the solid is one of nanocrystalline metal, coordinated hydride and metal hydride.

3. The method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials according to claim 1, characterized in that: The solid is a mixture of microcrystalline metal and metal hydride; In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of microcrystalline metal and 1%-24% of metal hydride.

4. The method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials according to claim 1, characterized in that: The solid is a mixture of microcrystalline metal and coordinated hydride; In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of microcrystalline metal and 1%-24% of coordinated hydride.

5. The method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials according to claim 1, characterized in that: The solid is a mixture of metal hydride and coordinated hydride; In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of metal hydride and 1%-24% of coordinated hydride.

6. The method for producing hydrogen using microwave-driven slurry hydrogen storage and production materials according to claim 1, characterized in that: The solid is a mixture of nanocrystalline metal, metal hydride and coordinated hydride; In terms of mass percentage, the slurry hydrogen storage and production material includes 60%-99% of organic liquid hydride, 1%-24% of microcrystalline metal, 1%-24% of metal hydride and 1%-24% of coordinated hydride.

7. The method for producing hydrogen using a microwave-driven slurry hydrogen storage material according to any one of claims 1 to 6, characterized in that: The mass of the catalyst is 0.01-0.2 times that of the slurry hydrogen storage and production material; The mass of the water is 1-10 times that of the slurry hydrogen storage and production material; The organic liquid hydride comprises at least one of a liquid aromatic compound, a heterocyclic compound, and a full hydrogenation product of a liquid organic polyol; The nanocrystalline metal includes at least one of Group I, Group II and Group III metals, and the particle size of the nanocrystalline metal is 50-1000nm; The coordinated hydride includes at least one of LiAlH4, NaAlH4, KAlH4, Mg(AlH4)2, Ca(AlH4)2, LiBH4, NaBH4, KBH4, Mg(BH4)2, and Ca(BH4)2; The metal hydride comprises at least one of LiH, KH, NaH, CuH2, and CaH2; The catalyst includes at least one of a Pd-based catalyst and a Pt-based catalyst.

8. A microwave-driven hydrogen production device for slurry hydrogen storage and production materials, characterized in that: It comprises a microwave reactor, and a water storage tank and a slurry storage tank respectively connected to the microwave reactor; The water storage tank and the slurry storage tank are used to transport a mixture of water, slurry hydrogen storage and production material and catalyst to the microwave reactor respectively; The microwave reactor is used to provide microwave conditions so that the mixture of slurry hydrogen storage and production materials and catalysts reacts with water to produce hydrogen under microwave conditions. The microwave conditions are carried out at a power of 300-3000W and a temperature of 80-150°C.

9. The microwave-driven slurry hydrogen storage and production material hydrogen production device according to claim 8, characterized in that: The microwave reactor is provided with a stirring component and a temperature measuring component; The microwave reactor is also connected to the separation tank and the recovery tank in sequence; The separation tank is used to separate the generated hydrogen and the slurry after the reaction; The recovery tank is used to store and recover the slurry after the reaction; The separation tank is also connected to a hydrogen storage tank.

10. Application of the hydrogen production method of the microwave driven slurry hydrogen storage material as claimed in claims 1 to 7 in the field of hydrogen storage and production.

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