WO2019052120A1

WO2019052120A1 - Magnesium hydride preparation apparatus and magnesium hydride preparation method

Info

Publication number: WO2019052120A1
Application number: PCT/CN2018/076672
Authority: WO
Inventors: 邹建新; 丁文江
Original assignee: 上海镁源动力科技有限公司
Priority date: 2017-09-15
Filing date: 2018-02-13
Publication date: 2019-03-21
Also published as: CN107585742A; JP7013485B2; CN107585742B; JP2020534228A

Abstract

Provided are a magnesium hydride preparation apparatus and a magnesium hydride preparation method. The magnesium hydride preparation device comprises: a transition chamber (1) comprising a feed port (11); a heating chamber (2) connected to the transition chamber (1) by means of a first valve (12); a heating device (6) having an upper end thereof provided with an opening, capably of moving between the transition chamber (1) and the heating chamber (2) by means of the first valve (12), and used for heating, in the heating chamber (2), the magnesium material placed therein; a collecting chamber (4) communicated with the heating chamber (2) by means of a pipe (3) so as to collect magnesium powder; and a reaction chamber (5) communicated with the collecting chamber (4) by means of a second valve (44) so as to receive the magnesium powder and communicated with an external hydrogen source so as to receive hydrogen. Magnesium powder preparation and hydrogenation are integrated in the magnesium hydride preparation apparatus. The magnesium hydride preparation method has simple steps, and the diameter of prepared magnesium hydride particles can be controlled within a range from 1 µm to 60 µm by controlling conditions such as a temperature and a pressure.

Description

Magnesium hydride preparation device and preparation method of magnesium hydride

Technical field

The present invention relates to the preparation of magnesium hydride, and more particularly to a magnesium hydride preparation apparatus and a method for preparing magnesium hydride.

Background technique

Magnesium hydride (MgH2), an off-white powder, is a single light metal hydride with high stability at normal temperature and pressure, a density of 1.45 g/cm3, and a hydrogen storage capacity of 7.6%, much higher than that of magnesium-based hydrogen storage alloys and others. Metal hydride. Magnesium hydride can react with water at room temperature to produce hydrogen. It can also be used as a catalyst, a reducing agent, and the like.

Magnesium-based materials are medium-temperature hydrogen storage alloys, easy to store, mild reaction conditions, and environmentally friendly by-products. They are promising hydrogen storage materials. Compared with other metal hydrogen storage materials, magnesium-based hydrogen storage materials have the following advantages: high hydrogen storage capacity; abundant resources and low price; magnesium-based hydrogen storage materials have good hydrogen absorption and desorption platform, which makes hydrogen utilization higher; The hydrogen release requires a higher temperature, and most of the hydrogen release temperature is above 200 °C.

The preparation method of magnesium hydride comprises the following steps: thermal decomposition of alkyl magnesium to obtain magnesium hydride, magnesium powder catalytically synthesizing magnesium hydride under normal pressure, and heating and hydrogenation using magnesium powder to obtain magnesium hydride.

Commercially available magnesium hydride has a large particle size and is expensive, and it is easy to form a passivation film on the surface of unreacted magnesium hydride when hydrolyzed to produce hydrogen, which hinders the reaction from proceeding and cannot be directly used for hydrogen production. Therefore, magnesium powder prepared by using a magnesium-based metal is considered, and then hydrogenated to obtain magnesium hydride.

The existing preparation method of magnesium hydride is a process of preparing, collecting and hydrogenating powder by using two or more apparatuses or instruments sequentially or simultaneously. For example, the use of the sol-gel method requires operations such as ultrasonication, centrifugation, washing, and heat preservation. Without special instructions and based on existing common sense, we believe that these operations need to be implemented on different functional instruments, such as ultrasonic machines, centrifuges, etc.; after sintering, use ball milling or grinding to obtain the precursors first, then put hydrogen Hydrogenation is achieved in the environment, and the hydrogenation process also needs to be carried out on different instruments, such as ball mills, mortars, tube furnaces, and the like. Either method can not realize the integrated preparation of magnesium hydride powder in a single device, which brings difficulties to processing and production. Therefore, it is particularly necessary to provide a device for integrated powder preparation and hydrogenation.

On the other hand, the magnesium hydride powder prepared by the prior art magnesium hydride preparation method has poor particle uniformity, or the particle size is too large (usually 150 μm or more) or too small (usually 1 μm or less), and the particle size is excessively large. It cannot be directly used for hydrogen production, and if the particles are too small, the yield of magnesium hydride is low and the reaction conditions are harsh and dangerous. Therefore, more sophisticated and advanced preparation techniques and devices are needed to achieve control of the particle size distribution.

Summary of the invention

In order to solve the above technical problems, an aspect of the present invention provides a magnesium hydride preparation apparatus, the magnesium hydride preparation apparatus comprising:

Transition warehouse, transition chamber includes feed port;

a heating chamber, the heating chamber is connected to the transition chamber through the first valve, preferably, the heating chamber further comprises a heating chamber inflation port to flush the inert gas;

a heater, the upper end of the heater is open and movable between the transition chamber and the heating chamber through the first valve, and the heater is used to heat the magnesium material placed in the heater in the heating chamber;

a collection chamber, the collection chamber being connected to the heating chamber through a conduit to collect magnesium powder; and

A reaction chamber, the reaction chamber is in communication with the collection chamber through a second valve to receive magnesium powder, and the reaction chamber is in communication with an external source of hydrogen to receive hydrogen.

In one embodiment, the magnesium hydride preparation apparatus further includes a vacuuming device connected to the transition chamber, and the transition chamber is further provided with a transition chamber inflation port to be filled with an inert gas.

In one embodiment, the magnesium hydride preparation apparatus further includes a guide rail disposed through the first valve in the transition chamber and the heating chamber, and the rail is coupled to the first control power source to deliver the heater.

In one embodiment, the heater comprises:

坩埚, 坩埚 is used to hold a magnesium raw material, preferably, the material of bismuth is one of boron nitride, graphite, magnesium oxide, and stainless steel;

An inductor coil, the inductor coil is disposed around the outside of the crucible to heat the magnesium material; and

The second control power source is connected to the inductor coil line to control the heating temperature.

In one embodiment, one end of the conduit connected to the heating chamber has a first opening having an increasing cross-sectional area, the first opening being disposed toward the upper end of the heater to collect magnesium vapor.

In one embodiment, the outer side of the conduit is provided with a first wire insulation layer and the first wire insulation layer is coupled to the third control power source.

In one embodiment, the collection room further comprises:

The electric brush has an electric rod having a horizontal rod and a vertical rod. The two ends of the horizontal rod are provided with a brush head capable of contacting the inner wall of the collection chamber, and the vertical rod is connected to the midpoint of the horizontal rod so that the horizontal rod can be at the Under the control of the four control power sources, it rotates horizontally around the vertical rod and can move up and down along the axial direction of the vertical rod;

Magnesium powder outlet, the magnesium powder outlet is disposed at the bottom of the collection chamber and is in communication with the second valve;

The cooling layer, the outside of the collection chamber is provided with a cooling layer to cool the magnesium vapor in the collection chamber. Preferably, the cooling layer is a circulating water cooling layer, and the circulating water cooling layer is in communication with the external water source.

In one embodiment, one end of the conduit connected to the collection chamber has a second opening that is continuously enlarged in cross section.

In one embodiment, the reaction chamber further includes a second resistance wire insulation layer, and the second resistance wire insulation layer is coupled to the fifth control power source.

In one embodiment, the magnesium raw material is a combination of one or more of pure magnesium, magnesium aluminum alloy, magnesium-rare earth, magnesium zirconium alloy, magnesium-nickel, magnesium-manganese, and the magnesium content in the magnesium raw material is 60 wt. Between % and 99.999 wt%, other elements are present in an amount between 0.001% and 40% by weight.

According to another aspect of the present invention, there is provided a method for preparing magnesium hydride using the above magnesium hydride preparation apparatus, the magnesium hydride preparation method comprising the steps of:

Transfer the heater to the transition chamber, close the first valve, and put the magnesium material into the heater through the feed port;

Opening the first valve to transfer the heater to the heating chamber, closing the first valve, and heating the magnesium raw material in the heating chamber to generate magnesium steam;

Magnesium vapor enters the collection chamber through the conduit to collect magnesium powder in the collection chamber;

After the collected magnesium powder enters the reaction chamber through the second valve, the heating operation of the heater is stopped, and the second valve is closed;

Hydrogen is introduced into the reaction chamber to react with the magnesium powder to form magnesium hydride particles.

In one embodiment, the transition chamber is coupled to the vacuum pump and the transition chamber further includes a transition chamber inflation port.

The magnesium hydride preparation method further comprises the following steps:

After the magnesium raw material is put into the heater, before the heater is transferred to the heating chamber, the vacuum chamber is used to perform a vacuuming operation on the transition chamber and the transition chamber is filled with an inert gas through the transition chamber inflation port. Preferably, the vacuuming device will transfer the chamber. Vacuuming to a pressure of 10-4Pa-10-2 Preferably, between Pa, the inert gas is argon, and more preferably, the pressure of the inert gas is between 0.005 MPa and 0.1 MPa.

In one embodiment, the heating chamber further includes a heating chamber inflation port, and the magnesium hydride preparation method further comprises the following steps:

After the heater is transferred to the heating chamber and the first valve is closed, the heating chamber is filled with an inert gas through the heating chamber inflation port before heating the magnesium material using the heater. Preferably, the inert gas is argon, preferably, the inert gas is charged. The pressure is between 0.005 MPa and 0.1 MPa.

In one embodiment, the transition chamber and the heating chamber are provided with a guide rail, and the guide rail is connected to the first control power source, and the magnesium hydride preparation method further comprises:

The first control power source sends a control signal to the rail;

The rail transmits the heater to a specific location within the heating chamber under the control of a control signal.

In one embodiment, the heater includes a crucible, an inductor disposed outside the crucible, and a second control power source coupled to the inductor, and the step of heating the magnesium material using the heater further comprises:

The second control power supply supplies power to the inductor such that the heating temperature of the inductor is between 650 ° C and 1100 ° C.

In one embodiment, the outer side of the conduit is provided with a first resistance wire insulation layer, and the first resistance wire insulation layer is connected to the third control power source, and the step of the magnesium vapor entering the collection chamber through the conduit further comprises:

The third control power supply supplies power to the first resistance wire insulation layer such that the insulation temperature of the first resistance wire insulation layer is between 650 ° C and 1000 ° C;

After the collected magnesium powder enters the reaction chamber through the second valve, the third control power source stops supplying power to the first resistance wire insulation layer.

In one embodiment, one end of the conduit connected to the heating chamber has an enlarged cross-sectional opening that is disposed toward the upper end of the heater to collect magnesium vapor.

In one embodiment, the collection chamber further includes an electric paint brush, a magnesium powder outlet, and a cooling layer connected to the fourth control power source, wherein the electric paint brush has a horizontal rod and a vertical rod, and the end of the horizontal rod has a brush head, magnesium powder The outlet is in communication with the second valve, the cooling layer is disposed outside the collection chamber, and the step of collecting magnesium powder in the collection chamber comprises:

Magnesium vapor enters the collection chamber through the conduit;

Opening a cooling layer to condense magnesium vapor into magnesium powder;

Starting the electric paint brush by the fourth control power source, the horizontal rod horizontally rotates around the vertical rod and moves up and down along the axial direction of the vertical rod to clean the magnesium powder attached to the side wall of the collection chamber;

Magnesium powder enters the reaction chamber through the magnesium powder outlet and the second valve.

In one embodiment, the cooling layer is a circulating water cooling layer. Preferably, the circulating water in the circulating water cooling layer has a temperature between 20 ° C and 50 ° C and a pressure between 0.5 MPa and 2 MPa.

In one embodiment, one end of the conduit connected to the collection chamber has an opening that is continuously enlarged in cross section.

In one embodiment, the reaction chamber further includes a second resistance wire insulation layer, and the second resistance wire insulation layer is connected to the fifth control power source, and the step of reacting to form the magnesium hydride particles further comprises:

The fourth control power supply supplies power to the second resistance wire insulation layer such that the insulation temperature of the second resistance wire insulation layer is between 200 ° C and 450 ° C.

In one embodiment, the length of time that hydrogen is reacted with the magnesium powder is between 1 hour and 40 hours.

In one embodiment, the magnesium raw material is a combination of one or more of pure magnesium, magnesium aluminum alloy, magnesium-rare earth, magnesium zirconium alloy, magnesium-nickel, magnesium-manganese, and the magnesium content in the magnesium raw material is 0 wt. Between % and 99.999 wt%, other elements are present in an amount between 0.001% and 40% by weight.

The magnesium hydride preparation device and the magnesium hydride preparation method provided by the invention overcome the problem of powder collection difficulty in the preparation process of the prior magnesium hydride, and the preparation steps are simple, the interval automatically collects the integration of the magnesium powder and the hydrogenation reaction; The heating temperature, the argon pressure of the transition chamber, the holding temperature of the first resistance wire insulation layer outside the conduit, and the cooling temperature of the cooling layer realize the control of the particle size distribution of the magnesium hydride powder, and ensure the preparation by the apparatus and method. The particle size distribution of the magnesium hydride powder is in the range of 1 μm to 60 μm, solving the problem of excessively large and too small particle diameters.

DRAWINGS

1 shows a schematic structural view of a magnesium hydride preparation apparatus according to an exemplary embodiment of the present invention;

2 shows an XRD spectrum of a magnesium hydride powder prepared according to a first embodiment of the present invention;

Figure 3 is a view showing the size distribution of magnesium hydride powder prepared according to the first embodiment of the present invention;

Figure 4 shows an XRD spectrum of a magnesium hydride powder prepared according to a second embodiment of the present invention;

Figure 5 is a view showing the size distribution of magnesium hydride powder prepared according to a second embodiment of the present invention;

Figure 6 shows an XRD spectrum of a magnesium hydride powder prepared according to a third embodiment of the present invention;

Fig. 7 is a view showing the size distribution of magnesium hydride powder prepared according to a third embodiment of the present invention.

Detailed ways

Illustrative, non-limiting examples of the present invention are described in detail below with reference to the accompanying drawings, in which the magnesium hydride preparation apparatus and the magnesium hydride preparation method according to the present invention are further illustrated.

Referring to Figure 1, in accordance with one aspect of the present invention, a magnesium hydride preparation apparatus is provided, the preparation apparatus comprising a transition chamber 1, a heating chamber 2, a heater 6 (including a crucible 61 and an induction coil 62), a collection chamber 4, and a reaction chamber 5, wherein the transition chamber 1 is connected to the heating chamber 2 through the first valve 12, the heating chamber 2 is connected to the collection chamber 4 through the conduit 3, and the collection chamber 4 is connected to the reaction chamber 5 through the second valve 44, the heater 6 can The transition between the transition chamber 1 and the heating chamber 2 is performed to complete the input and heating of the magnesium raw material.

The transition chamber 1 serves as a transition chamber before the heater 6 enters the reaction chamber 5 for completing the charging operation. The transition chamber 1 includes a feed port 11 through which the magnesium raw material is put into a heater 6 parked in the transition chamber 1. In addition, it is also possible to manufacture a vacuum environment and an inert gas atmosphere in the transition chamber 1 to avoid the reaction of magnesium in the magnesium raw material with oxygen in the air, which will be described in detail below. In one embodiment, the magnesium raw material is a combination of one or more of pure magnesium, magnesium aluminum alloy, magnesium-rare earth, magnesium zirconium alloy, magnesium-nickel, and magnesium-manganese, and the magnesium content of the magnesium raw material is Between 60% by weight and 99.999% by weight, the other element content is between 0.001% by weight and 40% by weight. However, it will be understood by those skilled in the art that the magnesium raw material used to prepare the magnesium hydride is not limited to the above list.

The heating chamber 2 is connected to the transition chamber 1 via a first valve 12. Preferably, the heating chamber 2 further includes a heating chamber 2 inflation port (not shown) for charging an inert gas to create an inert atmosphere in the heating chamber 2. After the completion of the loading of the transition chamber 1, the heater 6 enters the heating chamber 2 through the first valve 12, and then the first valve 12 is closed to heat the magnesium material therein in the heating chamber 2.

The heater 6 is a container which can heat the magnesium raw material contained therein, and the upper end of the heater 6 is opened to raise the vaporized magnesium vapor and enter the collection chamber 4 through the conduit 3. In one embodiment, the magnesium hydride preparation apparatus further includes a guide rail 63. A guide rail 63 is disposed in the transition chamber 1 and the heating chamber 2 and passes through the first valve 12. Thus, when the heater 6 needs to be transferred from the transition chamber 1 to the heating chamber 2, a control signal is sent to the guide rail 63 through the first control power source and electric energy is supplied to activate the guide rail 63, and the guide rail 63 transmits the heater 6 to the heating chamber 2, thereby realizing Automatic control.

The collection chamber 4 is in communication with the heating chamber 2 through a conduit 3 to receive magnesium vapor. Magnesium vapor can be gradually condensed in the collection chamber 4 to become magnesium powder, thereby collecting magnesium powder for hydrogenation reaction.

The reaction chamber 5 communicates with the collection chamber 4 through the second valve 44 to receive the magnesium powder, and the reaction chamber 5 communicates with an external hydrogen source (not shown) through the hydrogen inlet 52, and the external hydrogen source can be hydrogenated into the reaction chamber 5. The reaction provides hydrogen and hydrogen pressure adapted to the hydrogenation reaction. The magnesium powder is reacted with hydrogen in the reaction chamber 5 after entering the reaction chamber 5 through the second valve 44 to obtain magnesium hydride particles.

With continued reference to Figure 1, in one embodiment of the invention, the magnesium hydride preparation apparatus further includes a vacuuming device 13 coupled to the transition chamber 1 for vacuuming the transition chamber 1. The transition chamber 1 is also provided with a transition chamber inflation port to flush the inert gas. Thus, after the magnesium material is placed in the heater 6 in the transition chamber 1, the first valve 12 is closed and the vacuum chamber 13 is used to perform a vacuuming operation on the transition chamber 1, and then the inert gas is injected into the transition chamber 1 through the transition chamber inflation port. The gas thereby creates an inert environment within the transition chamber 1 to prevent air from entering the heating chamber 2 from the first valve 12.

In one embodiment, the heater 6 includes a weir 61, an inductive coil 62, and a second control power source (not shown).

The crucible 61 is a container that is open at the upper end and is used to hold a magnesium raw material. The inductor coil 62 is disposed around the outer side of the crucible 61 to electrically inductively heat the magnesium material in the crucible 61 under energization. The second control power source is connected to the inductor coil 62. The second control power source can supply electric energy to the inductor coil 62 according to the temperature required for vaporization of magnesium in the magnesium raw material, thereby realizing automatic control of the heating temperature of the magnesium raw material. The material of the crucible 61 disclosed in the present invention may be one of boron nitride, graphite, magnesium oxide, and stainless steel, but is not limited thereto.

In one embodiment, one end of the conduit 3 connected to the heating chamber 2 has a first opening whose cross-sectional area is constantly expanding, and the first opening is disposed toward the upper end of the heater 6 (opening of the crucible 61) to collect magnesium vapor. Further, one end of the duct 3 connected to the collection chamber 4 has a second opening whose cross section is continuously enlarged. In this way, the first opening which has an ever-increasing cross-sectional area can collect as much as possible the vaporized vapor of magnesium in the heater 6, thereby improving the utilization rate of the magnesium raw material; the second opening which is continuously enlarged in cross-sectional area can accelerate the release of magnesium vapor to the collection. The speed of chamber 4, thereby accelerating the rate of magnesium vapor condensation. Further, in order to ensure that condensation does not occur during the flow of the magnesium vapor from the heating chamber 2 to the collection chamber 4, the first electric resistance wire insulation layer 31 is disposed outside the conduit 3. The first resistance wire insulation layer 31 is connected to a third control power source (not shown), and the third control power source controls the temperature of the first resistance wire insulation layer 31 by controlling the current supplied to the first resistance wire insulation layer 31, In order to ensure that the temperature in the conduit 3 is above the condensation point of the magnesium vapor; in addition, after all the magnesium powder in the collection chamber 4 enters the reaction chamber 5, the third control power source stops supplying power to the first resistance wire insulation layer 31.

With continued reference to FIG. 1, the collection chamber 4 in the magnesium hydride preparation apparatus proposed by the present invention further includes an electric painter 42, a magnesium powder outlet 43, and a cooling layer 41.

The electric paint brush 42 is disposed inside the collection chamber 4 and has a horizontal rod and a vertical rod. The two ends of the horizontal rod are provided with a brush head which can be in contact with the inner wall of the collecting chamber 4; the vertical rod is connected with the midpoint position of the horizontal rod so that the horizontal rod can be controlled by the fourth control power source (not shown) It rotates horizontally around the vertical rod and can move up and down in the axial direction of the vertical rod. Thus, under the control of the fourth control power source, the horizontal rod moves up and down and horizontally around the vertical rod at the same time or at different times to clean the magnesium powder adsorbed on the inner wall of the collection chamber 4, thereby improving the collection efficiency of the magnesium powder. The magnesium powder outlet 43 is disposed at the bottom of the collection chamber 4 and is in communication with the second valve 44. The magnesium powder collected in the collection chamber 4 enters the reaction chamber 5 through the magnesium powder outlet 43 and the second valve 44. At the same time, in order to increase the condensation speed of the magnesium vapor, a cooling layer 41 is provided outside the collection chamber 4. Preferably, the cooling layer 41 is a circulating water cooling layer 41 that communicates with an external water source (not shown).

Referring to Figure 1, the reaction chamber 5 in the magnesium hydride preparation apparatus disclosed herein further includes a second resistance wire insulation layer 51 coupled to a fifth control power source (not shown). Thus, when the magnesium powder in the reaction chamber 5 is hydrogenated with hydrogen, the fifth control power source supplies electric energy to the second electric resistance wire insulation layer 51 according to the temperature required for the hydrogenation reaction to ensure a suitable reaction temperature, thereby achieving an improvement in hydrogenation efficiency. purpose.

It can be seen from the above description that the magnesium hydride preparation device provided by the invention integrates the preparation of magnesium powder and the hydrogenation reaction in the same set of equipment, thereby overcoming the problem of difficulty in powder collection in the conventional preparation process. In addition, the magnesium hydride preparation device has a simple structure, and automatically controls the conditions of temperature, pressure and the like in the steps of preparing the magnesium powder and preparing the magnesium hydride.

According to another aspect of the present invention, a method for preparing magnesium hydride using the above magnesium hydride preparation apparatus is proposed, and the method for preparing magnesium hydride is further described below with reference to the accompanying drawings and examples.

Referring to Figure 1, the magnesium hydride preparation process comprises the following steps.

First, the heater 6 is moved to the transition chamber 1, and the magnesium raw material is introduced into the heater 6 through the feed port 11. During the feeding process, the first valve 12 between the transition chamber 1 and the heating chamber 2 is closed to isolate the transition chamber 1 and the heating chamber 2, thereby reducing the contamination of the gas in the heating chamber 2 by the gas in the transition chamber 1. In order to further reduce the contamination of the heating chamber 2 by the gas in the transition chamber 1, in one embodiment of the invention, the magnesium hydride preparation method further comprises: after the magnesium raw material is put into the heater 6, before the heater 6 is transferred to the heating chamber 2 The vacuum chamber is used to perform a vacuuming operation on the transition chamber 1 and the inertial gas is filled into the transition chamber 1 through the transition chamber inflation port, that is, the gas that may react with the magnesium in the transition chamber 1 is discharged, and the air in the transition chamber 1 is prevented from entering the heating. In chamber 2, magnesium reacts with other gases in the air during the heating of the magnesium raw material, thereby improving the preparation efficiency of the magnesium powder and avoiding contamination of the raw materials. Preferably, the vacuuming device 13 evacuates the transition chamber 1 to a pressure between 10-4 Pa and 10 2 Pa. In one embodiment, the inert gas is argon. Preferably, the pressure of the inert gas is between 0.005 MPa and 0.1 MPa. It will be understood by those skilled in the art that the kind of inert gas charged into the transition chamber 1 is not limited thereto.

The first valve 12 is opened to transfer the heater 6 to the heating chamber 2, and then the first valve 12 is closed, and the heater 6 is used to heat the magnesium raw material in the heating chamber 2 to generate magnesium vapor. In one embodiment, the heater 6 is conveyed by a guide rail 63 disposed in the transition chamber 1 and the heating chamber 2, that is, the first control power source sends a control signal to the rail 63 to cause the rail 63 to convey the heater 6 to the heating chamber 2 A specific position within the interior to achieve automatic control of the transfer process of the heater 6. Further, in order to manufacture an inert gas atmosphere in the heating chamber 2, after the heater 6 is transferred to the heating chamber 2 and the first valve 12 is closed, the heater 6 is used to heat the magnesium raw material, and then passed through the heating chamber inflation port to the heating chamber 2 Inert gas. Preferably, the inert gas is argon. The pressure of the charged inert gas is between 0.005 MPa and 0.1 MPa. In one embodiment of the present invention, the method of heating the magnesium raw material using the heater 6 is to supply power to the inductor 62 through the second control power source, and the second control power source controls the inductor 62 by controlling the current supplied to the inductor 62. The heating temperature is between 650 ° C and 1100 ° C, and the magnesium in the magnesium raw material is vaporized to form magnesium vapor.

The magnesium vapor generated in the heating chamber 2 enters the collection chamber 4 through the conduit 3 and gradually condenses into magnesium powder in the collection chamber 4, thereby collecting magnesium powder in the collection chamber 4. During the flow of magnesium vapor in the conduit 3, in order to ensure that the magnesium vapor does not condense, the first resistance wire insulation layer 31 wrapped around the outside of the conduit 3 is supplied with power through the third control power source to make the first resistance wire insulation layer 31 to the magnesium vapor. It plays the role of heat preservation and improves the utilization efficiency of magnesium steam. The third control power source controls the holding temperature of the first resistance wire insulation layer 31 between 650 ° C and 1000 ° C by controlling the current supplied to the first resistance wire insulation layer 31 . In one embodiment, the step of collecting magnesium powder by the collection chamber 4 further includes: the magnesium vapor enters the collection chamber 4 through the conduit 3; the cooling layer 41 is opened to condense the magnesium vapor into magnesium powder; and the electric paint 42 is activated by the fourth control power source, The horizontal rod is horizontally rotated about the vertical rod or moved up and down along the axial direction of the vertical rod at the same time to clean the magnesium powder adhering to the side wall of the collection chamber 4; the collected magnesium powder is disposed at the bottom of the collection chamber 4 The magnesium powder outlet 43 and the second valve 44 enter the reaction chamber 5. In one embodiment, the temperature of the cooling water flowing into the cooling layer 41 is between 20 ° C and 50 ° C and the pressure is between 0.5 MPa and 2 MPa to achieve the best cooling effect.

After the magnesium powder collected in the collection chamber 4 enters the reaction chamber 5 through the second valve 44, hydrogen gas is introduced into the reaction chamber 5 to react with the magnesium powder to form magnesium hydride particles. During the hydrogenation process, the fifth control power source controls the holding temperature of the second resistance wire insulation layer 51 between 200 ° C and 450 ° C by controlling the current supplied to the second resistance wire insulation layer 51. Further, the reaction time of hydrogen and magnesium powder in the reaction chamber 5 is between 1 hour and 40 hours. In addition, after the magnesium powder collected in the collection chamber 4 enters the reaction chamber 5 through the second valve 44, before the hydrogen is introduced into the reaction chamber 5, the heating of the heater 6 is stopped, and the third control power source is stopped to the first resistance wire insulation layer 31. Powering, stopping the fourth control power supply to the electric paint 42 and closing the second valve 44.

An example of preparing magnesium hydride using the magnesium hydride preparation apparatus and the magnesium hydride preparation method provided by the present invention will be described below with reference to the accompanying drawings.

Embodiment 1

The feed port 11 of the transition chamber 1 is opened, pure magnesium material is introduced into the heater 6 in the transition chamber 1, the feed port 11 of the transition chamber 1 is closed, and the first valve 12 is closed. A vacuum environment was created in the transition chamber 1 using the vacuuming device 13, while argon gas having a pressure of 0.02 MPa was charged into the transition chamber 1 through the transition port inflation port.

The first valve 12 is opened, the guide rail 63 is activated by the first control power source, the heater 6 is moved along the guide rail 63 to the heating chamber 2, and then the first valve 12 is closed. The heating chamber 2 is filled with argon gas having a pressure of 0.02 MPa through the inflation port of the heating chamber 2, and the inductor 62 of the heater 6 is supplied with power through the second control power source to raise the temperature of the crucible 61 of the heater 6 to 800 ° C. The pure magnesium material in 坩埚61 melts and evaporates magnesium vapor.

Magnesium vapor enters the collection chamber 4 through the conduit 3, while circulating cooling water having a temperature of 20 ° C and a pressure of 2 MPa is introduced into the cooling layer 41 to condense the magnesium vapor in the cooling collection chamber 4 into magnesium powder, and is controlled by the fourth control power source. The electric brush 42 is controlled to rotate to collect the magnesium powder.

After the magnesium powder enters the reaction chamber 5 through the second valve 44, the heating of the heater 6 is stopped, the heating and holding of the conduit 3 is closed, the second valve 44 is closed, and the second resistance wire insulation layer 51 is supplied with power through the fifth control power source to cause the reaction. The temperature of the chamber 5 was maintained at 400 ° C while hydrogenation was started by introducing 4 MPa of hydrogen into the reaction chamber 5.

After the hydrogenation reaction for 10 hours, the hydrogen inlet 52 was closed, and the reaction product powder was collected from the reaction chamber 5.

The powder prepared in Example 1 was subjected to XRD test. As shown in FIG. 2, the XRD pattern showed that the powder obtained in Example 1 had a high content of pure magnesium hydride (MgH2), and a characteristic peak of MgH2 crystal face and a small amount of Mg characteristics were observed. peak. The powder obtained in Example 1 was subjected to a nano-grain test. As shown in Fig. 3, the volume average particle diameter of the powder particles was 15.211 μm, which was highly consistent.

Embodiment 2

The feed port 11 of the transition chamber 1 is opened, the magnesium-aluminum alloy raw material is introduced into the heater 6 in the transition chamber 1, the feed port 11 of the transition chamber 1 is closed, and the first valve 12 is closed. A vacuum environment was created in the transition chamber 1 using the vacuuming device 13, while argon gas having a pressure of 0.03 MPa was charged into the transition chamber 1 through the transition port inflation port.

The first valve 12 is opened, the guide rail 63 is activated by the first control power source, the heater 6 is moved along the guide rail 63 to the heating chamber 2, and then the first valve 12 is closed. The heating chamber 2 is filled with argon gas having a pressure of 0.03 MPa through the inflation port of the heating chamber 2, and the inductor 62 of the heater 6 is supplied with power through the second control power source to raise the temperature in the crucible 61 of the heater 6 to 750 ° C. The magnesium-aluminum alloy material in the crucible 61 is melted to generate magnesium vapor.

The first resistance wire insulation layer 31 is supplied with power through the third control power source to maintain the temperature in the conduit 3 at 750 °C. Magnesium vapor enters the collection chamber 4 through the conduit 3, while circulating cooling water having a temperature of 30 ° C and a pressure of 1 MPa is introduced into the cooling layer 41 to condense the magnesium vapor in the cooling collection chamber 4 into magnesium powder, and passes through the fourth control power source. The electric brush 42 is controlled to rotate to collect the magnesium powder.

After the magnesium powder enters the reaction chamber 5 through the second valve 44, the heating of the heater 6 is stopped, the heating and holding of the conduit 3 is closed, the second valve 44 is closed, and the second resistance wire insulation layer 51 is supplied with power through the fifth control power source to cause the reaction. The temperature of the chamber 5 was maintained at 360 ° C while hydrogenation was started by introducing 3 MPa of hydrogen into the reaction chamber 5.

After the hydrogenation reaction for 15 hours, the hydrogen inlet 52 was closed, and the reaction product powder was collected from the reaction chamber 5.

The powder prepared in Example 2 was subjected to XRD test. As shown in Fig. 4, the XRD pattern showed that the powder obtained in Example 2 contained both MgH2 and Mg, and the main component was MgH2. The powder obtained in Example 2 was subjected to a nanoparticle size test. As shown in Fig. 5, the volume average particle diameter of the powder particles was 18.646 μm, and the particle size was normally distributed.

Embodiment 3

The first resistance wire insulation layer 31 is supplied with power through the third control power source to maintain the temperature in the conduit 3 at 750 °C. Magnesium vapor enters the collection chamber 4 through the conduit 3, while circulating cooling water having a temperature of 25 ° C and a pressure of 1 MPa is introduced into the cooling layer 41, condensing the magnesium vapor in the cooling collection chamber 4 into magnesium powder, and passing through the fourth control power source. The electric brush 42 is controlled to rotate to collect the magnesium powder.

After the magnesium powder enters the reaction chamber 5 through the second valve 44, the heating of the heater 6 is stopped, the heating and holding of the conduit 3 is closed, the second valve 44 is closed, and the second resistance wire insulation layer 51 is supplied with power through the fifth control power source to cause the reaction. The temperature of the chamber 5 was maintained at 380 ° C while hydrogenation was started by introducing 3 MPa of hydrogen into the reaction chamber 5.

After the hydrogenation reaction for 5 hours, the hydrogen inlet 52 was closed, and the reaction product powder was collected from the reaction chamber 5.

The powder prepared in Example 3 was subjected to XRD test. As shown in Fig. 6, the XRD pattern showed that the powder obtained in Example 3 was a mixed powder of MgH2 and Mg having a MgH2 content of 95%. The powder prepared in Example 3 was subjected to nanoparticle size measurement. As shown in Fig. 7, the volume average particle diameter of the powder particles was 5.922 μm, and the particle size was normally distributed.

It can be seen from the above embodiments that the magnesium hydride preparation device and the magnesium hydride preparation method proposed by the invention overcome the problem of powder collection difficulty in the preparation process of the prior magnesium hydride, and the preparation steps are simple, and the interval automatically collects the integration of the magnesium powder and the hydrogenation reaction. The control of the particle size distribution of the magnesium hydride powder is achieved by controlling the heating temperature of the magnesium raw material, the argon pressure of the transition chamber, the holding temperature of the first resistance wire insulation layer outside the conduit, and the cooling temperature of the cooling layer. The particle size distribution of the magnesium hydride powder obtained by the apparatus and method is in the range of 1 μm to 60 μm, solving the problem of excessively large and too small particle size.

Claims

A magnesium hydride preparation apparatus, wherein the magnesium hydride preparation apparatus comprises:

a transitional bin, the transitional bin including a feed port;

a heating chamber, wherein the heating chamber is connected to the transition chamber through a first valve, preferably, the heating chamber further includes a heating chamber inflation port to be filled with an inert gas;

a heater having an upper end openable and movable between the transition chamber and the heating chamber through the first valve, the heater being used to heat the heater in the heating chamber Magnesium raw material;

a collection chamber, the collection chamber being in communication with the heating chamber through a conduit to collect magnesium powder; and

a reaction chamber in communication with the collection chamber through a second valve to receive the magnesium powder, and the reaction chamber is in communication with an external source of hydrogen to receive hydrogen.
The magnesium hydride preparation apparatus according to claim 1, wherein said magnesium hydride preparation apparatus further comprises a vacuuming means connected to said transition chamber, and said transition chamber is further provided with a transition chamber charge The mouth is filled with an inert gas.
The magnesium hydride preparation apparatus according to claim 1, wherein the magnesium hydride preparation apparatus further comprises a guide rail, the guide rail is disposed in the transition chamber and the heating chamber through the first valve, and the guide rail A first control power source is coupled to deliver the heater.
The magnesium hydride preparation apparatus according to claim 1, wherein said heater comprises:

The crucible is used for containing a magnesium raw material. Preferably, the crucible is one of boron nitride, graphite, magnesium oxide, and stainless steel;

An inductor coil disposed around an outer side of the crucible to heat the magnesium material; and

A second control power source is coupled to the inductor coil line to control the heating temperature.
The magnesium hydride preparation apparatus according to claim 1, wherein one end of said conduit connected to said heating chamber has a first opening whose cross-sectional area is continuously enlarged, said first opening being disposed toward an upper end of said heater Collect magnesium vapor.
The magnesium hydride preparation apparatus according to claim 5, wherein the outer side of the duct is provided with a first electric resistance wire insulation layer, and the first electric resistance wire insulation layer is connected to the third control power source.
The magnesium hydride preparation apparatus according to claim 1, wherein the collection chamber further comprises:

An electric paint brush having a horizontal rod and a vertical rod, the two ends of the horizontal rod being provided with a brush head capable of contacting an inner wall of the collection chamber, the vertical rod being connected to the horizontal rod a point position such that the horizontal rod can be horizontally rotated about the vertical rod under the control of the fourth control power source and can move up and down in the axial direction of the vertical rod;

a magnesium powder outlet, the magnesium powder outlet being disposed at a bottom of the collection chamber and in communication with the second valve;

The cooling layer is provided with a cooling layer on the outer side of the collection chamber to cool the magnesium vapor in the collection chamber. Preferably, the cooling layer is a circulating water cooling layer, and the circulating water cooling layer is in communication with an external water source.
The magnesium hydride preparation apparatus according to claim 1, wherein one end of the conduit connected to the collection chamber has a second opening whose cross section is continuously enlarged.
The magnesium hydride preparation apparatus according to claim 1, wherein said reaction chamber further comprises a second electric resistance wire insulation layer, and said second electric resistance wire insulation layer is connected to said fifth control power source.
The magnesium hydride preparation apparatus according to claim 1, wherein the magnesium raw material is a combination of one or more of pure magnesium, magnesium aluminum alloy, magnesium-rare earth, magnesium zirconium alloy, magnesium-nickel, magnesium-manganese. And the content of magnesium in the magnesium raw material is between 60% by weight and 99.999% by weight, and the other element content is between 0.001% by weight and 40% by weight.
A method for producing magnesium hydride using the magnesium hydride preparation apparatus according to any one of claims 1 to 10, wherein the magnesium hydride preparation method comprises the following steps:

Transmitting the heater to the transition chamber, closing the first valve, and introducing magnesium material into the heater through the feed port;

Opening the first valve to transfer the heater to the heating chamber, closing the first valve, and heating the magnesium raw material in the heating chamber to generate magnesium vapor;

Magnesium vapor enters the collection chamber through the conduit to collect magnesium powder in the collection chamber;

After the collected magnesium powder enters the reaction chamber through the second valve, stopping the heating operation of the heater, closing the second valve;

Hydrogen is introduced into the reaction chamber to react with the magnesium powder to form magnesium hydride particles.
The method for preparing magnesium hydride according to claim 11, wherein the transition chamber is connected to a vacuum pump, and the transition chamber further comprises a transition chamber inflation port, and the magnesium hydride preparation method further comprises the following steps:

Performing a vacuuming operation on the transition chamber using the vacuum pump and passing the transition chamber inflation port into the transition chamber after the magnesium raw material is introduced into the heater, before the heater is transferred to the heating chamber Filled with an inert gas, preferably, the evacuation device evacuates the transition chamber to a pressure between 10 and 4 Pa-10-2 Pa, preferably the inert gas is argon, more preferably, charged The pressure of the inert gas is between 0.01 MPa and 0.1 MPa.
The method for preparing magnesium hydride according to claim 12, wherein the heating chamber further comprises a heating chamber inflation port, and the magnesium hydride preparation method further comprises the following steps:

After the heater is transferred to the heating chamber and the first valve is closed, the heating chamber is filled with an inert gas through the heating chamber inflation port before heating the magnesium raw material using the heater, preferably, The inert gas is argon, and preferably, the pressure of the inert gas is between 0.005 MPa and 0.1 MPa.
The method for preparing magnesium hydride according to claim 11, wherein the transition chamber and the heating chamber are provided with a guide rail, and the guide rail is connected to a first control power source, and the method for preparing magnesium hydride further comprises:

The first control power source sends a control signal to the rail; and

The rail conveys the heater to a particular location within the heating chamber under control of a control signal.
The magnesium hydride preparation method according to claim 11, wherein the heater comprises a crucible, an inductance coil disposed outside the crucible, and a second control power source connected to the induction coil, the using the heater The step of heating the magnesium raw material further includes:

The second control power source supplies power to the inductor coil such that the heating temperature of the inductor coil is between 650 ° C and 1100 ° C.
The method for preparing magnesium hydride according to claim 11, wherein a first resistance wire insulation layer is disposed on an outer side of the conduit, and the first resistance wire insulation layer is connected to a third control power source, and the magnesium vapor passes The step of entering the conduit into the collection chamber further includes:

The third control power source supplies power to the first resistance wire insulation layer such that the insulation temperature of the first resistance wire insulation layer is between 650 ° C and 1000 ° C;

After the collected magnesium powder enters the reaction chamber through the second valve, the third control power source stops supplying power to the first resistance wire insulation layer.
The method of producing magnesium hydride according to claim 11, wherein one end of the conduit connected to the heating chamber has an opening having an enlarged cross-sectional area, the opening being disposed toward an upper end of the heater to collect magnesium vapor.
The magnesium hydride preparation method according to claim 11, wherein the collection chamber further comprises an electric paint brush, a magnesium powder outlet, and a cooling layer connected to the fourth control power source, wherein the electric paint brush has a horizontal rod and a vertical rod, And the end of the horizontal rod has a brush head, the magnesium powder outlet is in communication with the second valve, the cooling layer is disposed outside the collection chamber, and the magnesium powder is collected in the collection chamber The steps include:

Magnesium vapor enters the collection chamber through the conduit;

Opening the cooling layer to condense magnesium vapor into magnesium powder;

The electric paint brush is activated by the fourth control power source, the horizontal rod horizontally rotates around the vertical rod and moves up and down along an axial direction of the vertical rod to clean and attach the side wall of the collection chamber Magnesium powder; and

Magnesium powder enters the reaction chamber through the magnesium powder outlet and the second valve.
The method for producing magnesium hydride according to claim 18, wherein the cooling layer is a circulating water cooling layer, preferably, the temperature of the circulating water in the circulating water cooling layer is between 20 ° C and 50 ° C, and the pressure is Between 0.5MPa and 2MPa.
The method of producing magnesium hydride according to claim 11, wherein one end of the conduit connected to the collection chamber has an opening whose cross section is continuously enlarged.
The method for preparing magnesium hydride according to claim 11, wherein the reaction chamber further comprises a second electric resistance wire insulation layer, and the second electric resistance wire insulation layer is connected to a fifth control power source, and the reaction generates magnesium hydride particles. The steps also include:

The fourth control power source supplies power to the second resistance wire insulation layer such that the insulation temperature of the second resistance wire insulation layer is between 200 ° C and 450 ° C.
The method of producing magnesium hydride according to claim 11, wherein the reaction time of the hydrogen gas with the magnesium powder is between 1 hour and 40 hours.
The method for preparing magnesium hydride according to claim 11, wherein the magnesium raw material is a combination of one or more of pure magnesium, magnesium aluminum alloy, magnesium-rare earth, magnesium zirconium alloy, magnesium-nickel, magnesium-manganese. And the content of magnesium in the magnesium raw material is between 60% by weight and 99.999% by weight, and the other element content is between 0.001% by weight and 40% by weight.