A device and method for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials

Abstract

The present invention discloses a device and method for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials. The device includes: a first silo, a second silo, a conveying pipeline, and a control module. A pusher assembly extending to the outer end is provided in the conveying pipeline; the first silo is used to store magnesium-based solid raw materials. The control module controls the discharge of the magnesium-based solid raw materials in the first silo and the inflow of water from an external water source into the conveying pipeline, so that the magnesium-based solid raw materials and water undergo a hydrolysis reaction to produce hydrogen in the conveying pipeline; the control module also controls the pusher assembly to deliver the solid product generated by the hydrolysis reaction to the second silo. The present invention can promptly deliver the solid product generated after hydrolysis and separate it from the unreacted magnesium-based solid raw materials. The physical isolation method prevents the solid product from hindering the hydrolysis of the remaining magnesium-based solid raw materials, thereby achieving the purpose of multiple starts and stops at any time.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen production, and in particular relates to a device and method for producing hydrogen by hydrolyzing magnesium-based hydrogen storage materials. Background Art

[0002] Magnesium-based hydrogen storage materials (such as MgH2) are chemically stable in dry air and can release hydrogen again through thermal decomposition and hydrolysis. Among them, the enthalpy change of hydrogen release from thermal decomposition is relatively high, and a higher temperature is required for dehydrogenation. Even after modification, it is still above 200°C. Compared with thermal decomposition, hydrolysis has the following advantages: the spontaneous exothermic reaction can occur at room temperature, so the device is simple and does not require a separate heat source. In practical applications, the volume of the fuel cell can be reduced; the amount of hydrogen released is greater than that of thermal decomposition, and half of the hydrogen comes from water; the hydrolysis products are environmentally friendly and can be recycled and reused in other fields. The advantages of MgH2 hydrolysis for hydrogen production are significant and have become a research hotspot in recent years. The hydrolysis product Mg(OH)2 is environmentally friendly and easy to recycle, and can be used as a flame retardant, an environmentally friendly water treatment agent, and a pharmaceutical additive.

[0003] However, the hydrolysis product Mg(OH)2 exists as a precipitate and adheres to the surface of the MgH2 particles, forming a dense passivation layer that prevents them from contacting water and severely restricts the further progress of the hydrolysis reaction. Therefore, to improve the hydrolysis performance of MgH2, it is necessary to overcome the limitations of the Mg(OH)2 passivation layer.

[0004] As disclosed in patent CN114906804A, a controllable and continuous hydrolysis system for producing hydrogen from magnesium hydride is provided. The system comprises a hydrogen production reactor and a feed tank, wherein the hydrogen production reactor comprises a hydrogen production reactor and several supporting members, wherein the supporting member is in a porous structure, wherein the supporting member is arranged in the hydrogen production reactor, wherein adjacent supporting members are spaced apart and the space is used to place a magnesium chloride composite material, the hydrogen production reactor has a feed inlet, a liquid inlet, an air outlet and a discharge port, and the feed tank is used to store a hydrolyzate, and the feed tank is connected to the liquid inlet. Although the process of producing hydrogen from magnesium hydride by hydrolysis can be controlled, magnesium hydride can react with water at room temperature and the reaction rate can be controlled by the hydrolyzate flow rate. However, the multiple chambers and porous filter structure provided can only filter and remove the magnesium hydroxide generated by a small part, and the magnesium hydroxide not filtered out will still adhere to the magnesium hydride raw material, gradually forming a dense passivation layer.

[0005] Disclose a kind of continuous controllable hydrolysis hydrogen production system as patent CN114229795A, comprise liquid supply system, hydrolysis reaction system, drainage system and hydrogen purification system, described liquid supply system provides hydrolyzate for the magnesium hydride hydrolysis, described hydrolysis reaction system is the place that magnesium hydride is hydrolyzed and produces hydrogen, described hydrogen purification system is for purification of hydrogen, described drainage system is the discharge of reaction production product, described hydrolysis reaction system end is provided with silica gel column and molecular sieve column and carries out purification of hydrogen, and in described hydrolysis reactor, keeps liquid level constant by inverted U-shaped pipe.Although magnesium hydride, when hydrolysis, by controlling feed rate, can effectively carry out controlled hydrogen release, realizes the continuous and stable release of hydrogen.But after the magnesium hydride flaky particles after the charging are hydrolyzed in hydrolysis reactor, its surface can continue to generate magnesium hydroxide, finally forms dense passivation layer, stops the contact of magnesium hydride flaky particles and water, causes magnesium hydride flaky particles to be unable to be hydrolyzed fully.

[0006] Therefore, exploring a controllable and continuous hydrolysis hydrogen production device to improve the hydrogen production rate of magnesium-based hydrogen storage materials (especially magnesium hydride) is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0007] In response to the above-mentioned defects in the prior art, the present invention provides a device and method for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials. The solid products generated after hydrolysis can be promptly transported out and separated from the unreacted magnesium-based solid raw materials. Physical isolation is used to prevent the solid products from hindering the further hydrolysis of the remaining magnesium-based solid raw materials, thereby achieving the purpose of multiple starts and stops at any time.

[0008] In a first aspect, the present invention provides a device for producing hydrogen by hydrolysis of a magnesium-based hydrogen storage material, comprising: a first silo, a second silo, a delivery pipeline, and a control module, wherein a pusher assembly extending to an outer end is provided in the delivery pipeline;

[0009] The first silo is used to store magnesium-based solid raw materials. The control module controls the discharge of the magnesium-based solid raw materials from the first silo and the inflow of water from an external water source into the conveying pipeline, so that the magnesium-based solid raw materials and water undergo a hydrolysis reaction to produce hydrogen in the conveying pipeline.

[0010] The control module also controls the pushing assembly to deliver the solid product produced by the hydrolysis hydrogen production reaction to the second silo.

[0011] Furthermore, the magnesium-based solid raw material is micron-sized magnesium hydride, the water inlet of the conveying pipeline is high-temperature steam, and the solid products produced by the hydrolysis hydrogen production reaction include magnesium oxide.

[0012] Furthermore, the conveying pipeline extends in a horizontal direction, the first silo is arranged above the conveying pipeline, the second silo is arranged below the conveying pipeline, the first silo and the second silo are respectively arranged at the left and right ends of the conveying pipeline, the connection points between the conveying pipeline and the first silo and the second silo are the first opening and the second opening respectively, and the water inlet position is between the first opening and the second opening of the conveying pipeline.

[0013] Furthermore, the pushing assembly is a screw propeller, which includes a screw push rod, a motor, a thermal insulation coupling and a rotary head. The motor and the first silo are arranged at the same end of the conveying pipeline, and the rotary head and the second silo are arranged at the same end of the conveying pipeline. One end of the screw push rod is connected to the motor through the thermal insulation coupling, the screw push rod extends into the conveying pipeline, and the other end of the screw push rod is connected to the rotary head.

[0014] The delivery pipeline is sleeved and fixed on the outer side of the spiral push rod and the rotary head. The delivery pipeline includes a first shell, a second shell, a third shell and a fourth shell connected in sequence along the horizontal direction. The first shell is sleeved with a fixed rotary head. The second shell is provided with a second opening connected to the second silo and a hydrogen outlet. The fourth shell is provided with a first opening connected to the first silo, and the fourth shell is connected to the thermal insulation coupling.

[0015] The spiral push rod is made of breathable steel, and water enters the conveying pipe through the breathable steel. The surface of the spiral push rod is installed with spiral fins extending from one end to the other end. The spiral push rod includes a first conveying section, a reaction section and a second conveying section connected in sequence along the horizontal direction. The first conveying section is connected to the rotary head, and the second conveying section is connected to the thermal insulation coupling. The diameters of the first conveying section and the second conveying section are both smaller than the diameter of the reaction section.

[0016] Furthermore, the wing pitch of the spiral fins is 10-20 mm, the diameters of the first conveying section and the second conveying section are 10-30 mm, the diameter of the reaction section is 20-40 mm, and the pore diameter of the breathable steel is 0.005-0.035 mm.

[0017] Furthermore, the hydrolysis hydrogen production device also includes a water supply component and a heating component. The external water source is the water supply component, which includes a first water tank and a first water pump. The second silo is placed in the first water tank. The first water pump is connected to the first water tank and the screw propeller to send water in the first water tank into the screw propeller as water inlet of the delivery pipeline.

[0018] The heating assembly includes a heating coil, a battery, a second water pump and a second water tank. The battery is connected to the heating coil, which is wound around the outer surface of the third shell and is perpendicular to the reaction section of the spiral push rod.

[0019] The heating coil is a hollow structure, and the second water tank is connected to the hollow structure inside the heating coil through the second water pump.

[0020] Furthermore, the discharge rate of the magnesium-based solid raw material is 0.3-1.7 g / min, the water inlet rate of the conveying pipeline is 0.2-1.2 g / min, and the pushing speed of the screw push rod is 0.2-4 mm / min.

[0021] Furthermore, the control module determines the hydrogen release rate of the hydrogen production reaction by hydrolysis of the magnesium-based hydrogen storage material based on the obtained hydrogen target flow rate, and gives the discharge rate of the magnesium-based solid raw material in the first silo, the water inlet rate of the conveying pipeline, and the pushing speed of the screw push rod.

[0022] Furthermore, the specific relationship between the hydrogen release rate of the hydrolysis hydrogen production reaction of the magnesium-based hydrogen storage material and the parameters of each component in the hydrolysis hydrogen production device is as follows:

[0023]

[0024] Among them, ρ1 is the density of hydrogen, ρ2 is the density of the magnesium-based solid raw material, M is the relative molecular mass of hydrogen, M1 is the relative molecular mass of the magnesium-based solid raw material, k1 is the stoichiometric ratio of hydrogen to the magnesium-based solid raw material in the hydrolysis hydrogen production reaction, M2 is the relative molecular mass of water, K2 is the stoichiometric ratio of hydrogen to water in the hydrolysis hydrogen production reaction, V is the hydrogen release rate of the hydrolysis hydrogen production reaction, V1 is the discharge rate of the magnesium-based solid raw material, V2 is the water inlet rate of the conveying pipeline, V3 is the pushing speed of the screw push rod, and D is the diameter of the conveying pipeline.

[0025] In a second aspect, the present invention further provides a method for producing hydrogen by hydrolysis using a magnesium-based hydrogen storage material, which comprises the following steps:

[0026] Adding magnesium-based solid raw materials into the first silo;

[0027] The control module determines and provides a discharge rate of the magnesium-based solid raw material in the first silo and a water inflow rate of the external water source into the conveying pipeline;

[0028] The magnesium-based solid raw material and water undergo hydrolysis reaction to produce hydrogen in the transportation pipeline;

[0029] The control module controls the pushing assembly to deliver the solid product produced by the hydrolysis hydrogen production reaction to the second silo.

[0030] The present invention provides a device and method for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials, which has at least the following beneficial effects:

[0031] (1) The first silo and the second silo are connected by a conveying pipe, and water is fed into the conveying pipe from an external water source, so that the magnesium-based solid raw material can react continuously in the conveying pipe. Due to the function of the pushing assembly, the solid product after the reaction in the conveying pipe can be transported to the second silo, thereby preventing the solid product from hindering the further hydrolysis of the remaining magnesium-based solid raw material. In addition, by controlling the water inlet and the pushing assembly, the hydrolysis hydrogen production reaction can be controlled to achieve the purpose of multiple and timely start and stop.

[0032] (2) The magnesium hydride required for the hydrolysis hydrogen production reaction is between the screw push rod and the conveying pipeline. The screw propeller is provided with a screw push rod. The spiral fins on the surface of the screw push rod are equivalent to automatically isolating the reaction area between the screw push rod and the conveying pipeline into an independent chamber; then the water vapor enters through the breathable steel to form a relatively fine high-temperature water vapor, which can make the high-temperature water vapor react quickly with the magnesium hydride, ensuring the rapid reaction rate.

[0033] (3) The hydrogen release rate of the hydrolysis hydrogen production reaction is determined by the required hydrogen flow rate, and then the discharge rate of the magnesium-based solid raw material, the water inlet rate, and the pushing speed of the screw push rod are determined by the hydrogen release rate, so that the hydrogen release rate can be more accurately controlled. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 A schematic structural diagram of a device for producing hydrogen by hydrolysis of a magnesium-based hydrogen storage material provided by the present invention;

[0035] Figure 2 A schematic diagram of an explosion of a device for producing hydrogen by hydrolysis of a magnesium-based hydrogen storage material according to an embodiment of the present invention;

[0036] Figure 3 A schematic cross-sectional view of a device for producing hydrogen by hydrolysis of a magnesium-based hydrogen storage material according to an embodiment of the present invention;

[0037] Figure 4 A schematic structural diagram of a pusher assembly according to an embodiment of the present invention;

[0038] Figure 5 A partial schematic diagram of a pusher assembly according to an embodiment of the present invention.

[0039] Explanation of the accompanying drawings: 1-first silo, 2-second silo, 3-conveying pipeline, 31-first shell, 32-second shell, 33-third shell, 34-fourth shell, 4-pushing assembly, 41-screw push rod, 411-first conveying section, 412-reaction section, 413-second conveying section, 42-motor, 43-thermal insulation coupling, 44-rotating head, 51-first water tank, 6-heating assembly, 61-heating coil, 62-high-frequency heating drive assembly, 63-second water tank, 7-fixed bracket, 71-reinforced fixing plate, 72-bottom plate, 73-support plate, 74-coupling bracket. DETAILED DESCRIPTION

[0040] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0041] The terms used in the embodiments of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The singular forms "a," "an," "the," and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms, and unless the context clearly indicates otherwise, "a plurality" generally includes at least two.

[0042] It should also be noted that the terms "include," "comprises," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a product or device comprising a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such product or device. In the absence of further limitations, an element defined by the phrase "comprises a..." does not exclude the presence of other identical elements in the product or device comprising the element.

[0043] Magnesium-based hydrogen storage materials, especially magnesium hydride (MgH2), can react with water at room temperature and pressure to produce hydrogen and magnesium hydroxide (Mg(OH)2) which is insoluble in water. The reaction equation is as follows:

[0044] MgH2+2H2O→Mg(OH)2↓+2H2↑

[0045] If the amount of water is not large and the temperature is high, the reaction equation is as follows:

[0046] MgH2+H2O→MgO+2H2↑

[0047] These reactions are all exothermic, releasing heat, resulting in a high theoretical hydrogen production of 1703 mL / g. Excluding the mass of water, the mass fraction reaches 15.2 wt%. Half of the hydrogen comes from the water involved in the reaction, resulting in a hydrogen production rate nearly double that of elemental magnesium hydrolysis. However, the hydrolysis product, Mg(OH)₂, forms a precipitate and adheres to the surface of the MgH₂ particles, forming a dense passivation layer that prevents contact with water and severely limits further hydrolysis.

[0048] Based on this, see Figures 1 to 3 As shown, the present invention provides a device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials, comprising: a first silo 1, a second silo 2, a delivery pipeline 3 and a control module (not shown in the figure), wherein a pusher assembly 4 extending to the outer end is provided in the delivery pipeline 3;

[0049] The first silo 1 is used to store magnesium-based solid raw materials. The control module controls the discharge of the magnesium-based solid raw materials from the first silo 1 and the inflow of water from an external water source into the delivery pipe 3, so that the magnesium-based solid raw materials and water undergo a hydrolysis reaction to produce hydrogen in the delivery pipe 3.

[0050] The control module also controls the pushing assembly 4 to deliver the solid product produced by the hydrolysis hydrogen production reaction to the second silo 2 .

[0051] The present invention is connected to the first silo 1 and the second silo 2 through a conveying pipe 3, and water is fed into the conveying pipe 3 through an external water source, so that the magnesium-based solid raw material can continue to react in the conveying pipe 3. Due to the effect of the pusher assembly 4, the reacted solid product can be transported to the second silo 2 in the conveying pipe 3 to prevent the solid product from hindering the further hydrolysis of the remaining magnesium-based solid raw material. In addition, the control of the hydrolysis hydrogen production reaction can be achieved by controlling the water inlet and the pusher assembly 4, so as to achieve the purpose of multiple and at any time starting and stopping. That is, the present invention can timely transport the magnesium oxide generated after hydrolysis and separate it from the unreacted magnesium hydride through the hydrolysis hydrogen production device based on the magnesium-based solid raw material, and prevent the magnesium oxide from hindering the hydrolysis of the remaining magnesium hydride based on the physical isolation method, so as to achieve the purpose of multiple and at any time starting and stopping.

[0052] To avoid the formation of the hydrolysis byproduct Mg(OH)2 and the formation of magnesium oxide (MgO) as a precipitate that adheres to the surface of the MgH2 particles, forming a dense passivation layer that prevents contact with water and limits further hydrolysis, the present invention uses micron-sized magnesium hydride as the magnesium-based solid raw material. This allows the micron-sized magnesium hydride to completely react to form MgO during the reaction, thereby preventing the MgO from precipitating and adhering to the surface of the MgH2 particles, which would result in unreacted magnesium hydride and prevent further reaction. Furthermore, the inlet water of the delivery pipeline 3 is high-temperature water vapor, which satisfies the reaction conditions of a small amount of water and a high temperature for the direct generation of magnesium oxide from magnesium hydride, thereby ensuring that the solid product produced by the hydrolysis hydrogen production reaction includes at least magnesium oxide.

[0053] The conveying pipe 3 of the present invention extends horizontally, the first silo 1 is arranged above the conveying pipe 3, and the second silo 2 is arranged below the conveying pipe 3. The first silo 1 and the second silo 2 are respectively arranged at the left and right ends of the conveying pipe 3, and the connection points between the conveying pipe 3 and the first silo 1 and the second silo 2 are respectively the first opening and the second opening; the position where the external water source enters the conveying pipe 3 is set between the first opening and the second opening of the conveying pipe 3. By arranging the first silo 1 and the second silo 2 above and below the conveying pipe 3, respectively, magnesium hydride and magnesium oxide can be directly introduced into the conveying pipe 3 and the second silo 2, respectively, under the action of gravity, thereby avoiding the need for additional drive structures to drive feeding and discharging; of course, the feeding and discharging methods of the present invention can also be implemented using other drive structures.

[0054] Arranging the conveying pipe 3 to extend horizontally can prevent the magnesium hydride entering the conveying pipe 3 from directly entering the second silo 2 under the action of gravity. In order to prevent the magnesium hydride from directly entering the second silo 2, the present invention can also arrange the conveying pipe 3 to have a certain inclination angle. When the conveying pipe 3 is in an inclined state, the position of the first opening is lower than that of the second opening. In addition, the present invention arranges the first silo 1 and the pushing assembly at the same end, which can prevent the magnesium oxide discharged from the same side as the second silo 2 from having a higher temperature and causing damage to the pushing assembly 4.

[0055] See also Figure 4 and Figure 5As shown, the pushing assembly 4 of the present invention is a screw propeller, which may include a screw pusher 41, a motor 42, a thermal insulation coupling 43 and a rotary head 44. The motor 42 and the first silo 1 are arranged at the same end of the conveying pipe 3, and the rotary head 44 and the second silo 2 are arranged at the same end of the conveying pipe 3. One end of the screw pusher 41 is connected to the motor 42 through the thermal insulation coupling 43, and the screw pusher 41 extends into the conveying pipe 3. The other end of the screw pusher 41 is connected to the rotary head 44; the conveying pipe 3 is sleeved and fixed on the outside of the screw pusher 41 and the rotary head 44, and a reaction zone for conveying magnesium hydride and reacting to generate magnesium oxide is formed by the screw pusher 41 and the conveying pipe 3. The rotary head 44 and the thermal insulation coupling 43 ensure that the screw push rod 41 rotates under the action of the motor 42, and also achieves a seal between the screw push rod 41 and the conveying pipe 3. The motor 42 is connected to the screw push rod 41 through the thermal insulation coupling 43, which can thermally isolate the screw push rod 41 and the motor 42, thereby preventing the high temperature in the conveying pipe 3 from being transmitted to the motor 42 and causing damage to the motor 42. Among them, the thermal insulation coupling 43 can be selected according to different needs. The thermal insulation coupling 43 of this embodiment adopts a magnetic coupling. In addition, the conveying pipeline 3 of the present invention may include a first shell 31, a second shell 32, a third shell 33 and a fourth shell 34 connected in sequence along the horizontal direction, the first shell 31 is provided with a fixed rotary head 44, the second shell 32 is provided with a second opening connected to the second silo 2 and a hydrogen outlet, and the fourth shell 34 is provided with a first opening connected to the first silo 1; by setting the conveying pipeline 3 as a first shell 31, a second shell 32, a third shell 33 and a fourth shell 34, it is convenient to connect the screw push rod 41, the insulation coupling 43 and the rotary head 44, and it is also convenient to set the screw push rod 41 and the rotary head 44 in the conveying pipeline 3. The screw push rod 41 is made of breathable steel, through which water enters the delivery pipe 3. The surface of the screw push rod 41 is equipped with spiral fins extending from one end to the other. The screw push rod 41 includes a first delivery section 411, a reaction section 412, and a second delivery section 413 connected in sequence along a horizontal direction. The first delivery section 411 is connected to the rotary head 44, and the second delivery section 413 is connected to the thermal insulation coupling 43. The diameters of the first delivery section 411 and the second delivery section 413 are both smaller than the diameter of the reaction section 412. The fin pitch of the spiral fins is 10-20 mm, the diameters of the first delivery section 411 and the second delivery section 413 are 10-30 mm, the diameter of the reaction section 412 is 20-40 mm, and the pore diameter of the breathable steel is 0.005-0.035 mm.

[0056] By configuring the screw push rod 41 to be breathable steel, the present invention can control the amount of water vapor entering between the screw push rod 41 and the delivery pipe 3. This allows the present invention to directly convert magnesium hydride into magnesium oxide under conditions of low water volume and high temperature, thereby preventing magnesium hydride from generating magnesium hydroxide and precipitating to clog the area between the screw push rod 41 and the delivery pipe 3. On this basis, the screw push rod 41 of the present invention can also be directly made of an airtight material. In this case, a plurality of air holes are provided on the screw push rod 41, and a filter screen is provided at the air holes. The mesh diameter of the filter screen is smaller than the diameter of the magnesium hydride, thereby ensuring that high-temperature water vapor can only enter the area between the screw push rod 41 and the delivery pipe 3 through the air holes, and preventing magnesium hydride from entering the screw push rod 41.

[0057] In addition, the present invention provides a spiral push rod 41 with a first conveying section 411, a reaction section 412, and a second conveying section 413, and the diameter of the reaction section 412 is larger than the diameter of the first conveying section 411 and the second conveying section 413. This can reduce the space between the spiral fins, thereby allowing the magnesium hydride to fill the area between the spiral fins. Furthermore, the diameter of the reaction section 412 is larger than the diameter of the first conveying section 411 and the second conveying section 413. The corresponding structure is: the two ends of the reaction section 412 are respectively connected to the first conveying section 411 and the second conveying section 413, and the diameter of the reaction section 412 gradually increases from its two ends to the middle portion, thereby achieving the purpose of the diameter of the reaction section 412 being larger than the diameter of the first conveying section 411 and the second conveying section 413.

[0058] When the delivery pipeline 3 of the present invention is filled with water through the breathable steel, the middle part of the screw push rod 41 is a hollow structure, and the hollow structure is a movement space for water or high-temperature water vapor. In order to fill the hollow structure of the screw push rod 41 with water or high-temperature water vapor, a corresponding structure can be set to achieve it. In an actual application scenario, the hydrolysis hydrogen production device can also include a water supply component and a heating component 6. The water supply component includes a first water tank 51 and a first water pump. The second silo 2 is placed in the first water tank 51. The first water pump connects the first water tank 51 and the screw propeller, and the water in the first water tank 51 is sent to the screw propeller as the water inlet of the delivery pipeline 3; the water in the first water tank 51 can be sent into the screw push rod 41 by the first water pump, and the water in the screw push rod 41 can be heated by the heating component 6 to form high-temperature water vapor, so that the high-temperature water vapor can pass through the breathable steel into the area between the screw push rod 41 and the delivery pipeline 3 to achieve a reaction with magnesium hydride. When the first water pump delivers the water in the first water tank 51 into the screw push rod 41 , the water injection operation can be performed through one end of the screw push rod 41 provided with a rotary head 44 .

[0059] In the present invention, since the magnesium oxide generated by the reaction has a high temperature, when it is collected in the second silo 2, in order to improve the utilization rate of heat, the second silo 2 is set in the first water tank 51, and the water entering the screw push rod 41 can be preheated, thereby improving the energy utilization rate of the hydrolysis hydrogen production device and improving the efficiency of converting water to high-temperature water vapor. Among them, the heating component 6 includes a heating coil 61, a battery, a second water pump and a second water tank 63. The battery is connected to the heating coil 61, and the heating coil 61 is wound on the outer surface of the third shell 33; the heating coil 61 is a hollow structure, and the second water tank 63 is connected to the hollow structure inside the heating coil 61 through the second water pump. The setting of the heating coil 61 can heat the water in the screw push rod 41 to form high-temperature water vapor, and pass through the breathable steel to enter the area between the screw push rod 41 and the delivery pipe 3 to react; in order to achieve the purpose of improving the degree of reaction, the position of the heating coil 61 can be set. In actual application scenarios, the heating coil 61 can be set outside the reaction section 412 of the screw push rod 41. Through the diameter-changing effect of the reaction section 412, the contact area between magnesium hydride and high-temperature water vapor is increased, thereby improving the degree of reaction. The present invention can accelerate the rapid cooling of the heating coil 61 through the second water pump and the second water tank 63. Among them, in order to avoid the presence of water vapor in the heating coil 61 when it is in action, causing a safety accident, a high-temperature resistant insulating material layer can be coated on the inner wall of the heating coil 61, thereby avoiding the situation of leakage, and also avoiding the long-term presence of water vapor to corrode the heating coil 61.

[0060] See also Figures 1 to 3As shown, the hydrolysis hydrogen production device of the present invention can also be provided with a fixed bracket 7 to enhance the overall strength and support and fix it. In actual application scenarios, the fixed bracket 7 includes two reinforcing fixing plates 71 arranged at parallel intervals, and a base plate 72, a support plate 73 and a coupling bracket 74 located between the two reinforcing fixing plates 71 and arranged at intervals in sequence; the support plate 73 is slidably fixed to the reinforcing fixing plate 71. Specifically, the reinforcing fixing plate 71 is provided with at least two parallel strip holes, which extend from the base plate 72 to the coupling bracket 74. Two detachable locking members are provided on both sides of the support plate 73. The locking members pass through the strip holes to fix the support plate 73. The locking members can be bolts or other components that can be locked or freely movable with the reinforcing fixing plate 71. The support plate 73 can reciprocate between the base plate 72 and the coupling bracket 74 along the length direction of the strip holes through the locking members. The screw push rod 41, motor 42, thermal insulation coupling 43, rotary head 44 and conveying pipe 3 in the pushing assembly 4 are coaxially arranged. The thermal insulation coupling 43 is fixed in the coupling bracket 74. The motor 42 is fixed to the coupling bracket 74. The first silo 1 is arranged above the pushing assembly 4 and is arranged close to the motor 42. The second silo 2 is arranged below the pushing assembly 4, and the bottom of the second silo 2 is flush with the bottom plate 72. The heating coil 61 is sleeved on the outside of the third shell 33 at a position corresponding to the reaction section 412. The battery is connected to the heating coil 61 and is located below the conveying pipe 3. The second water pump is connected to the heating coil 61 and is located below the conveying pipe 3. The battery and the second water pump are fixed by the fifth shell to form an integrated high-frequency heating drive assembly 62. The second water tank 63 is fixed to the fifth shell and is connected to the second water pump. The second water tank 63 is located below the thermal insulation coupling 43 and the motor 42 and is fixed to the support plate 73. The second water tank 63 can have a certain cooling effect on the thermal insulation coupling 43 and the motor 42. By adjusting the distance between the support plate 73 and the coupling bracket 74, the distance between the second water tank 63 and the thermal insulation coupling 43 can be adjusted, thereby adjusting the heat exchange effect of the second water tank 63 on the thermal insulation coupling 43 and the motor 42. Among them, when the support plate 73 moves, in order to ensure that the heating coil 61 will not move with it, the heating coil 61 can be directly fixed on the third shell 33, and the heating coil 61 and the battery are connected by a flexible wire, and the heating coil 61 and the second water pump are connected by a flexible conduit. This structure will not affect the heating coil 61 when the high-frequency heating drive component 62 and the second water tank 63 move with the support plate 73; in addition, the heating coil 61 and the battery can also be connected in a sliding manner. For example, the battery includes a sliding part that is sleeved on both ends of the heating coil 61. The sliding part is electrically connected to the heating coil 61 and can slide along both ends of the heating coil 61. The sliding direction is consistent with the movement direction of the support plate 73, and the heating coil 61 is connected to the second water pump using a flexible conduit.In addition, the heating coil 61 can also move with the support plate 73, that is, the heating coil 61 is fixed to the high-frequency heating drive assembly 62. When adjusting and calibrating the position of the third shell 33, the high-frequency heating drive assembly 62 and the second water tank 63 can be adjusted through the support plate 73 to achieve adjustment of the heating coil 61.

[0061] When producing hydrogen using magnesium hydride and high-temperature water vapor, the present invention can control the hydrogen production rate through a control module. Specifically, the control module can determine the hydrogen release rate of the hydrolysis hydrogen production reaction based on the obtained hydrogen target flow rate, and provide the discharge rate of the magnesium-based solid raw material in the first silo, the water inflow rate of the conveying pipeline, and the pushing speed of the screw push rod.

[0062] In actual application scenarios, the discharge rate of the magnesium-based solid raw material of the present invention is 0.3-1.7 g / min, the water inflow rate of the delivery pipeline is 0.2-1.2 g / min, and the pushing speed of the screw push rod is 0.2-4 mm / min. When controlling the hydrogen production rate, the specific relationship between the hydrogen release rate of the hydrolysis hydrogen production reaction and the parameters of each component in the hydrolysis hydrogen production device is as follows:

[0063]

[0064] Wherein, ρ1 is the density of hydrogen, (g / L), ρ2 is the density of magnesium-based solid raw material, (g / mm 3 ), M is the relative molecular mass of hydrogen, M1 is the relative molecular mass of the magnesium-based solid raw material, k1 is the stoichiometric ratio of hydrogen to the magnesium-based solid raw material in the hydrolysis hydrogen production reaction, M2 is the relative molecular mass of water, K2 is the stoichiometric ratio of hydrogen to water in the hydrolysis hydrogen production reaction, V is the hydrogen release rate of the hydrolysis hydrogen production reaction, (L / min), V1 is the discharge rate of the magnesium-based solid raw material, (g / min), V2 is the water inlet rate of the conveying pipeline, (g / min), V3 is the pushing speed of the screw push rod, (mm / min), and D is the diameter of the conveying pipeline, (mm).

[0065] For example, the reaction equation for hydrogen production by hydrolysis is: MgH2+H2O→MgO+2H2↑, then M1 is the relative molecular mass of MgH2, 26, and k1 is the stoichiometric ratio of hydrogen to MgH2, 2.

[0066] By understanding the specific relationship between the hydrogen release rate of the hydrolysis hydrogen production reaction and the parameters of each component in the hydrolysis hydrogen production device, precise quantitative control of the hydrogen production rate can be achieved, making the present invention applicable to high-precision hydrogen production scenarios.

[0067] The present invention also provides a method for producing hydrogen by hydrolysis using a magnesium-based hydrogen storage material, which uses the above-mentioned device for producing hydrogen by hydrolysis using a magnesium-based hydrogen storage material, and specifically comprises the following steps:

[0068] Adding magnesium-based solid raw materials into the first silo;

[0069] The control module determines and provides a discharge rate of the magnesium-based solid raw material in the first silo and a water inflow rate of the external water source into the conveying pipeline;

[0070] The magnesium-based solid raw material and water undergo hydrolysis reaction to produce hydrogen in the transportation pipeline;

[0071] The control module controls the pushing assembly to deliver the solid product produced by the hydrolysis hydrogen production reaction to the second silo.

[0072] Although preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they are aware of the basic inventive concepts. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the invention. Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the invention. Thus, the present invention is intended to include such changes and modifications as fall within the scope of the claims and their equivalents.

Claims

1. A device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials, characterized in that: include: A first silo, a second silo, a conveying pipeline and a control module, wherein a pushing assembly extending to an outer end is provided in the conveying pipeline; The first silo is used to store magnesium-based solid raw materials. The control module controls the discharge of the magnesium-based solid raw materials from the first silo and the inflow of water from an external water source into the conveying pipeline, so that the magnesium-based solid raw materials and water undergo a hydrolysis reaction to produce hydrogen in the conveying pipeline. The control module also controls the pushing assembly to deliver the solid product produced by the hydrolysis hydrogen production reaction to the second silo; The conveying pipeline extends in a horizontal direction, the first silo is arranged above the conveying pipeline, the second silo is arranged below the conveying pipeline, the first silo and the second silo are respectively arranged at the left and right ends of the conveying pipeline, the conveying pipeline is connected to the first silo and the second silo through a first opening and a second opening, and the water inlet is located between the first opening and the second opening of the conveying pipeline; The pushing assembly is a screw propeller, which includes a screw push rod, a motor, a thermal insulation coupling and a rotary head. The motor and the first silo are arranged at the same end of the conveying pipeline, and the rotary head and the second silo are arranged at the same end of the conveying pipeline. One end of the screw push rod is connected to the motor through the thermal insulation coupling, and the screw push rod extends into the conveying pipeline. The other end of the screw push rod is connected to the rotary head. The delivery pipeline is sleeved and fixed on the outer side of the spiral push rod and the rotary head. The delivery pipeline includes a first shell, a second shell, a third shell and a fourth shell connected in sequence along the horizontal direction. The first shell is sleeved with a fixed rotary head. The second shell is provided with a second opening connected to the second silo and a hydrogen outlet. The fourth shell is provided with a first opening connected to the first silo, and the fourth shell is connected to the thermal insulation coupling. The spiral push rod is made of breathable steel, and water enters the conveying pipe through the breathable steel. The surface of the spiral push rod is installed with spiral fins extending from one end to the other end. The spiral push rod includes a first conveying section, a reaction section and a second conveying section connected in sequence along the horizontal direction. The first conveying section is connected to the rotary head, and the second conveying section is connected to the thermal insulation coupling. The diameters of the first conveying section and the second conveying section are both smaller than the diameter of the reaction section.

2. The device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials according to claim 1, characterized in that: The magnesium-based solid raw material is micron-sized magnesium hydride, the water inlet of the conveying pipeline is high-temperature water vapor, and the solid products produced by the hydrolysis hydrogen production reaction include magnesium oxide.

3. The device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials according to claim 1, characterized in that: The wing spacing of the spiral fins is 10-20 mm, the diameters of the first conveying section and the second conveying section are 10-30 mm, the diameter of the reaction section is 20-40 mm, and the pore diameter of the breathable steel is 0.005-0.035 mm.

4. The device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials according to claim 1, characterized in that: The hydrolysis hydrogen production device also includes a water supply component and a heating component. The external water source is the water supply component, which includes a first water tank and a first water pump. The second silo is placed in the first water tank. The first water pump is connected to the first water tank and the screw propeller to send water in the first water tank into the screw propeller as water inlet of the delivery pipeline. The heating assembly includes a heating coil, a battery, a second water pump and a second water tank. The battery is connected to the heating coil, which is wound around the outer surface of the third shell and vertically corresponds to the reaction section of the spiral push rod. The heating coil is a hollow structure, and the second water tank is connected to the hollow structure inside the heating coil through the second water pump.

5. The device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials according to claim 1, characterized in that: The discharge rate of the magnesium-based solid raw material is 0.3-1.7 g / min, the water inlet rate of the conveying pipeline is 0.2-1.2 g / min, and the pushing speed of the screw push rod is 0.2-4 mm / min.

6. The device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials as claimed in claim 5, characterized in that: Based on the obtained hydrogen target flow rate, the control module determines the hydrogen release rate of the hydrolysis hydrogen production reaction using the magnesium-based hydrogen storage material, and provides the discharge rate of the magnesium-based solid raw material in the first silo, the water inlet rate of the conveying pipeline, and the pushing speed of the screw push rod.

7. The device for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials as claimed in claim 6, characterized in that: The specific relationship between the hydrogen release rate of the hydrolysis hydrogen production reaction using magnesium-based hydrogen storage materials and the parameters of each component in the hydrolysis hydrogen production device is as follows: Among them, ρ1 is the density of hydrogen, ρ2 is the density of the magnesium-based solid raw material, M is the relative molecular mass of hydrogen, M1 is the relative molecular mass of the magnesium-based solid raw material, k1 is the stoichiometric ratio of hydrogen to the magnesium-based solid raw material in the hydrolysis hydrogen production reaction, M2 is the relative molecular mass of water, K2 is the stoichiometric ratio of hydrogen to water in the hydrolysis hydrogen production reaction, V is the hydrogen release rate of the hydrolysis hydrogen production reaction, V1 is the discharge rate of the magnesium-based solid raw material, V2 is the water inlet rate of the conveying pipeline, V3 is the pushing speed of the screw push rod, and D is the diameter of the conveying pipeline.

8. A method for producing hydrogen by hydrolysis of magnesium-based hydrogen storage materials, characterized in that: The device for producing hydrogen by hydrolysis of a magnesium-based hydrogen storage material as claimed in any one of claims 1 to 7 specifically comprises the following steps: Adding magnesium-based solid raw materials into the first silo; The control module determines and provides a discharge rate of the magnesium-based solid raw material in the first silo and a water inflow rate of the external water source into the conveying pipeline; The magnesium-based solid raw material and water undergo hydrolysis reaction to produce hydrogen in the transportation pipeline; The control module controls the pushing assembly to deliver the solid product produced by the hydrolysis hydrogen production reaction to the second silo.

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