CN117800288A - Preparation process and preparation device of solid magnesium hydride based on multi-gap magnesium - Google Patents
Preparation process and preparation device of solid magnesium hydride based on multi-gap magnesium Download PDFInfo
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- CN117800288A CN117800288A CN202410218104.3A CN202410218104A CN117800288A CN 117800288 A CN117800288 A CN 117800288A CN 202410218104 A CN202410218104 A CN 202410218104A CN 117800288 A CN117800288 A CN 117800288A
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 251
- 239000007787 solid Substances 0.000 title claims abstract description 167
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 156
- 239000011777 magnesium Substances 0.000 title claims abstract description 156
- 229910012375 magnesium hydride Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 167
- 239000001257 hydrogen Substances 0.000 claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000010438 heat treatment Methods 0.000 claims abstract description 82
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 3
- 230000002596 correlated effect Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 238000001595 flow curve Methods 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 12
- 238000005265 energy consumption Methods 0.000 description 10
- 230000000875 corresponding effect Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 3
- -1 multi-gap magnesium) Chemical compound 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001295 No alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Sorption Type Refrigeration Machines (AREA)
Abstract
The invention relates to the technical field of magnesium hydride preparation, in particular to a solid magnesium hydride preparation process based on multi-gap magnesium, which comprises the steps of pressing strip-shaped magnesium sheets in a regular cavity to form solid magnesium, wherein a gap space for storing heat is formed in the solid magnesium; heating the solid magnesium in a sealed reaction space which is higher than normal pressure, introducing hydrogen to contact the solid magnesium, and combining the solid magnesium with the hydrogen in a set time to obtain the solid magnesium hydride. The device comprises a reaction kettle, a heating frame, a temperature detection device, a pressure detection device, a control module, a heat exchange system and a gas pipeline system. The preparation device of the solid magnesium and the solid magnesium hydride reduces the problem of large power consumption required by the traditional magnesium hydride manufacture, does not need to add any alloy in magnesium to promote the reaction, can effectively utilize energy, reduces heat energy loss and has stable control.
Description
Technical Field
The invention relates to the technical field of magnesium hydride preparation, in particular to a solid magnesium hydride preparation process and a preparation device based on multi-gap magnesium.
Background
As one of the means of storing hydrogen, there is a metal hydride which is magnesium hydride MgH 2 . As the metal hydride, the hydrogen storage in a special state such as ultra-high pressure and ultra-low temperature is not needed, so the operation is easy and the safety is highBut also has the excellent feature of a higher hydrogen storage per unit volume.
The traditional magnesium hydride preparation method has two modes, one is that magnesium is ground into powder, the powder magnesium is combined with high-temperature high-pressure hydrogen in high-pressure equipment, the reaction pressure is generally kept between 6 and 8MPa, the reaction temperature is controlled to be higher than 650 ℃, the temperature in the whole reaction kettle is stabilized to be higher than the reaction temperature, the high-temperature high-pressure reaction condition ensures higher energy consumption, the combination rate is reduced along with the reaction, and the preparation purity can reach 95 to 98 percent; in the other mode, magnesium hydrogen is combined through the condensation process of vaporized magnesium, the energy consumption is higher, but the purity can reach 98% -99%, in order to optimize the reaction, some alloys are mixed in the magnesium in the current mode, the utilization rate of the magnesium to heat energy is increased, and the intervention of other alloys can cause complicated working procedures. Therefore, aiming at the problems in the prior art, the invention develops a preparation process and a preparation device of solid magnesium hydride based on multi-gap magnesium.
Disclosure of Invention
The invention aims at: the preparation process and the preparation device of the solid magnesium hydride based on the multi-gap magnesium are provided, so that the problems that in the process of preparing the magnesium hydride by adopting powdered magnesium or vaporized magnesium in the prior art, the energy consumption is too high, and other alloys are required to be added to promote the reaction to influence the process and the cost are solved.
The technical scheme of the invention is as follows: a process for preparing solid block magnesium hydride based on multi-gap magnesium comprises the following steps:
pressing and forming the strip-shaped magnesium sheet in a regular cavity to obtain solid magnesium, wherein a clearance space for storing heat is formed in the solid magnesium;
heating the solid magnesium in a reaction space which is higher than normal pressure and is sealed, introducing hydrogen to contact the solid magnesium, detecting the temperature and pressure change trend in the reaction space in the process, and adjusting the temperature and the pressure according to the change trend;
and combining the solid magnesium with hydrogen in a set time to obtain the solid magnesium hydride.
Preferably, in the reaction space, the working temperature is not lower than 340 ℃, and the working pressure is not lower than 0.6MPa.
Preferably, the thickness of the strip-shaped magnesium sheet is lower than 200 μm, and under the preset specific hydrogenation rate, the thickness of the strip-shaped magnesium sheet is positively correlated with the working temperature and the working pressure.
Preferably, the density of the solid magnesium is 70-80% of that of solid magnesium.
Preferably, the solid magnesium is arranged on a heating frame in the reaction space, and the bonding amount of line contact exists between the solid magnesium and the heating frame, so that heat of the heating frame is transferred upwards to the solid magnesium.
Preferably, the hydrogen gas flows in the reaction space based on a pressure difference or a temperature difference, and is in full contact with the solid magnesium in a flowing state.
The invention also develops a solid block magnesium hydride preparation device, which comprises:
the reaction space is formed in the reaction kettle, and the reaction kettle is provided with at least two air ports which are respectively positioned at the top and the bottom of the reaction kettle;
the heating frame comprises a fixed seat and a heating rod arranged on the fixed seat; each layer of heating frame is provided with at least two heating rods, heating wires are arranged in the heating rods, and the heating rods are used for supporting the solid magnesium and transmitting heat;
the temperature detection device and the pressure detection device are arranged on the reaction kettle and are respectively used for detecting the temperature and the pressure in the reaction kettle;
the control module is used for adjusting the temperature and the pressure in the reaction kettle based on the detection data of the temperature detection device and the pressure detection device;
and a gas pipeline system for realizing the circulation of gas in the reaction kettle.
Preferably, a fan device for enabling hydrogen to flow based on pressure difference is arranged in the reaction kettle;
or, a high-temperature device for enabling hydrogen to flow based on temperature difference is arranged at the bottom of the reaction kettle, and the high-temperature device is independent of the space in the reaction kettle.
Preferably, the gas pipeline system comprises a high temperature resistant pipe body, a high temperature and high pressure resistant valve body, an oxygen content sensor, a hydrogen flow sensor, a pressure relief device and a vacuumizing device, wherein the pressure relief device and the vacuumizing device are connected with the reaction kettle;
the high temperature resistant pipe body is connected with the gas ports at the top and the bottom of the reaction kettle, and the high temperature resistant valve body, the oxygen content sensor and the hydrogen flow sensor are all arranged on the high temperature resistant pipe body and are used for monitoring the hydrogen flow and the oxygen flow at the gas ports.
Preferably, the heat exchange system further comprises a heat exchange system, wherein the heat exchange system adopts a cooling coil; the cooling coil is arranged in the reaction space or in a partition space at the bottom of the reaction kettle.
Compared with the prior art, the invention has the advantages that:
(1) The solid magnesium hydride is prepared by adopting the solid magnesium formed by pressing the strip magnesium sheet, the continuity of temperature transmission is ensured under the heating condition based on the structure of the solid magnesium, and meanwhile, the internal clearance space is beneficial to the heat storage and is not easy to run off; the solid magnesium formed by the structure is granular, can be conveniently placed on a heating frame for heating, and can be directly transferred to the solid magnesium.
(2) The solid magnesium is matched with the solid magnesium hydride preparation device, so that relatively low-temperature and low-pressure reaction is realized, the problem of high power consumption required by the traditional magnesium hydride preparation is solved, no alloy is added into magnesium to promote the reaction, the energy can be effectively utilized, the heat energy loss is reduced, and the control is stable; on the other hand, the temperature is reduced during the reaction of the solid magnesium hydride, so that the overall temperature is controlled below the ignition point of the hydrogen, and the use safety of the hydrogen and the safety of the preparation of the solid magnesium hydride are improved.
(3) Because the fixed magnesium has the subsidence of certain line contact with the heating frame to the heating frame is in the below of fixed magnesium, and then the heat can upwards directly transfer to fixed magnesium, does not need to guarantee the temperature stability in the whole reation kettle, only needs to guarantee that the temperature of heating frame self can reach appointed height, and the heat just can effectually make the whole reaction temperature that reaches of fixed magnesium, further makes preparation facilities's control easier, has also avoided the fixed magnesium to be heated uneven problem. Meanwhile, the line contact between the solid magnesium and the heating frame can not only meet the heat transfer, but also avoid the defect that the solid magnesium cannot be fully contacted with hydrogen due to surface contact.
(4) Compared with the traditional preparation method, the method can prepare the purity of the magnesium hydride to more than 99.6% under the conditions of low use pressure and low temperature, so that the preparation temperature and pressure required for preparing the solid magnesium hydride with lower purity requirement are lower, and the applicability of the preparation of the solid magnesium hydride with lower purity requirement is higher.
(5) The solid magnesium hydride preparation device can be used for preparing hydrogen reversely, and achieves the effect of one machine for two purposes by adjusting the change of the environmental conditions in the reaction space; the solid magnesium hydride is placed in the reaction kettle, the release of hydrogen is realized by controlling the temperature in the reaction space under normal pressure or negative pressure, and the heat continuity and the good heat storage performance in the inside can be ensured based on the structure of the solid magnesium hydride in the process.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a schematic diagram of a solid block magnesium hydride manufacturing device according to the present invention;
FIG. 2 is a schematic view of a structure of the fixed magnesium placed on a heating rack according to an embodiment of the present invention;
FIG. 3 is a schematic view of a structure of the fixed magnesium on a heating rack according to another embodiment of the present invention;
FIG. 4 is a flow curve corresponding to example 5 of the present invention.
Wherein: 1. fixing magnesium;
2. the heating rack, 21, the fixing seat, 22 and the heating rod;
3. a reaction kettle 31, a reaction space 32, an air port 33, a partition space 34, an opening and closing device 35 and an observation port;
4. the heat exchange system, 4a, the cooling coil, 41, the water inlet pipe, 42 and the water outlet pipe;
5. a fan device;
6. a high temperature device.
Detailed Description
The following describes the present invention in further detail with reference to specific examples:
for the convenience of understanding, it should be noted that the primary solution in the present application is to combine solid magnesium with hydrogen to prepare solid magnesium hydride for realizing the storage of hydrogen energy; in the prior art, in the process of preparing magnesium hydride by adopting powdered magnesium or vaporized magnesium, the reaction pressure and the reaction temperature are too high, so that the energy consumption is too high, and other alloys are required to be added to promote the reaction to influence the process and the cost, so that the preparation process and the preparation device of the solid magnesium hydride are developed for solving the problems.
Example 1
A process for preparing solid block magnesium hydride based on multi-gap magnesium comprises the following steps:
(1) The strip-shaped magnesium sheet with the thickness of 300 mu m and formed by cutting is pressed and molded in a die with a regular cavity to obtain solid magnesium (namely multi-gap magnesium), and the solid magnesium is in a large granular shape and can be configured into a column shape or other shapes.
The solid magnesium is internally provided with a clearance space, the clearance space belongs to a micro-space structure, the heat storage is facilitated in the subsequent heating process, the heat is not easy to run off, the temperature stability is better than that of the traditional magnesium powder magnesium block, the heat energy utilization rate is higher, and the energy consumption is lower; the density of the pressed solid magnesium can be controlled to be 70-80% of the density of the solid magnesium based on the existence of the clearance space; the solid magnesium is microscopically distinguished from powder or magnesium blocks pressed from powder, and is a coherent long strip after being disassembled, and the temperature transmission is continuous. Meanwhile, after the solid magnesium is pressed and formed, the solid magnesium is also convenient to place in the subsequent heating process.
(2) The method comprises the steps of placing solid magnesium on a heating frame in a reaction space, heating the solid magnesium in the sealed reaction space, setting the initial pressure in the reaction space to be 1MPa, setting the initial temperature to be 360 ℃, introducing hydrogen to contact the solid magnesium, and combining the solid magnesium with the hydrogen in a set time to obtain the solid magnesium hydride.
(3) In the process of the reaction of the solid magnesium and the hydrogen, the temperature in the reaction space can be controlled by the temperature rise and fall of the heating frame, and the pressure in the reaction space is controlled by the amount of the introduced hydrogen. Because the introduced hydrogen needs to react with the solid magnesium, hydrogen is continuously introduced into the reaction space in the reaction process. In the reaction process, detecting the change trend of the temperature and the pressure in the reaction space compared with the initial pressure and the initial temperature, and adjusting the temperature and the pressure according to the change trend, when the temperature in the reaction space is lower than the initial temperature, increasing the temperature of the heating frame, otherwise reducing the temperature; when the pressure in the reaction space is lower than the initial pressure, the hydrogen gas inlet amount is increased, and conversely, the hydrogen gas inlet amount is reduced; and the hydrogen flow sensor is used for judging the amount of hydrogen entering the reaction space along with the time in the reaction process, the hydrogen flow is related to the reaction speed of the solid magnesium, and a flow curve of the hydrogen entering amount and the reaction time is obtained. And under different time, the hydrogen flow sensors are respectively corresponding to flow data, and the flow curve can be obtained based on the time and the flow data.
Example 2
A process for preparing solid block magnesium hydride based on multi-gap magnesium comprises the following steps:
(1) The strip-shaped magnesium sheet with the thickness of 200 μm and formed by cutting is pressed and molded in a die with a regular cavity to obtain solid magnesium (namely multi-gap magnesium), and the solid magnesium is in a large granular shape and can be configured into a column shape or other shapes.
(2) The method comprises the steps of placing solid magnesium on a heating frame in a reaction space, heating the solid magnesium in the sealed reaction space, setting the initial pressure in the reaction space to be 1MPa, setting the initial temperature to be 360 ℃, introducing hydrogen to contact the solid magnesium, and combining the solid magnesium with the hydrogen in a set time to obtain the solid magnesium hydride.
(3) In the process of reacting solid magnesium with hydrogen, detecting the change trend of the temperature and the pressure in the reaction space compared with the initial pressure and the initial temperature, and adjusting the temperature and the pressure according to the change trend; and the hydrogen flow sensor is used for judging the amount of hydrogen entering the reaction space along with the time in the reaction process, the hydrogen flow is related to the reaction speed of the solid magnesium, and a flow curve of the hydrogen entering amount and the reaction time is obtained.
Example 3
The difference between this example and example 1 is that in step (1), a strip-shaped magnesium sheet having a thickness of 150 μm and formed by cutting is press-formed in a mold having a regular cavity and a solid magnesium is obtained; other reaction conditions were the same as in example 1.
Example 4
The difference between this example and example 1 is that in step (1), a strip-shaped magnesium sheet having a thickness of 100 μm and formed by cutting is press-formed in a mold having a regular cavity to obtain a solid magnesium; other reaction conditions were the same as in example 1.
Table 1: hydrogenation rate data table for the reactions in examples 1-4;
first, the method for calculating the hydrogenation rate is as follows:
hydrogenation ratio = (actual mass after reaction-actual mass before reaction)/(theoretical mass after reaction-theoretical mass before reaction) ×100%
In Table 1, "mass before reaction" is both the actual mass before reaction and the theoretical mass before reaction;
the "post-reaction mass" is the actual mass after reaction;
the theoretical mass after the reaction is calculated based on the molar mass of magnesium and magnesium hydride and is as follows:
theoretical mass before reaction/theoretical mass after reaction = molar mass of magnesium/molar mass of magnesium hydride
The molar mass of magnesium was 24.3g/mol and the molar mass of magnesium hydride was 26.3g/mol.
Thus, taking example 1 as an example, the theoretical mass after the reaction is 6.7276g, and the final calculated hydrogenation ratio is (6.601-6.216)/(6.7276-6.216) ×100% = 75.254%.
According to Table 1, it is known that the smaller the thickness of the strip-shaped magnesium sheet is, the higher the hydrogenation rate is, mainly because when the strip-shaped magnesium sheet with an excessive thickness is used for compression molding, the internal gap space is increased, the heat loss is fast, the specific surface area is reduced, the contact surface of the chemical reaction is fewer, and the reaction rate is low. Therefore, under the conditions of the working temperature and the working pressure provided by the embodiment, the thickness of the strip magnesium sheet is controlled below 100 mu m, so that the performance of the solid magnesium in the heating process can be ensured. However, in practical application, when the thickness of the strip-shaped magnesium sheet is increased, the performance of the solid magnesium in the heating process can be still ensured by increasing the working temperature and the working pressure. In addition, the thickness of the strip-shaped magnesium sheet is controlled below 200 mu m, and the thickness of the strip-shaped magnesium sheet always meets the positive correlation with the working temperature and the working pressure under the preset specific hydrogenation rate condition.
Based on the above embodiment, in the reaction process under any condition, a set of hydrogenation rate data is correspondingly obtained, whether the reaction meets the expectations (whether the hydrogenation rate reaches more than 99%) is judged, and when the reaction does not meet the expectations, the regulation of the internal environment of the reaction kettle is realized by reducing the temperature and the pressure or raising the temperature and the pressure; the energy consumption is reduced to a certain extent, and the accurate control of the energy consumption is increased.
Example 5
A process for preparing solid block magnesium hydride based on multi-gap magnesium comprises the following steps:
(1) The strip-shaped magnesium sheet with the thickness of 100 μm and formed by cutting is pressed and molded in a die with a regular cavity to obtain solid magnesium (namely multi-gap magnesium), and the solid magnesium is in a large granular shape and can be configured into a column shape or other shapes.
(2) The method comprises the steps of placing solid magnesium on a heating frame in a reaction space, heating the solid magnesium in the sealed reaction space, setting the initial pressure in the reaction space to be 1MPa, setting the initial temperature to be 400 ℃, introducing hydrogen to contact the solid magnesium, and combining the solid magnesium with the hydrogen in a set time to obtain the solid magnesium hydride.
(3) In the process of reacting solid magnesium with hydrogen, detecting the change trend of the temperature and the pressure in the reaction space compared with the initial pressure and the initial temperature, and adjusting the temperature and the pressure according to the change trend; and in the reaction process, the hydrogen flow sensor is used for judging the amount of hydrogen entering the reaction kettle along with the time, the hydrogen flow is related to the reaction speed of the solid magnesium, and a flow curve of the hydrogen entering amount and the reaction time is obtained.
Example 6
This example differs from example 5 in that in step (2): the method comprises the steps of placing solid magnesium on a heating frame in a reaction space, heating the solid magnesium in the sealed reaction space, setting the initial pressure in the reaction space to be 0.6MPa, setting the initial temperature to be 400 ℃, introducing hydrogen to contact the solid magnesium, and combining the solid magnesium with the hydrogen in a set time to obtain the solid magnesium hydride.
Table 2: hydrogenation rate data table for the reactions in examples 5-6;
as is clear from Table 2, the hydrogenation rate gradually increased with the increase of the pressure in the reaction space. In the practical application process, the method has the advantages that the minimum required pressure of the solid magnesium is ensured to be 0.6MPa, the purity can be relatively improved by improving the pressure on the basis of the minimum required pressure, and the reaction time and the energy consumption can be reduced to a certain extent. However, the potential safety hazard of hydrogen can be raised by higher pressure, and the manufacturing cost of the preparation device is increased, so that the ideal working pressure is set to be 0.8-1 MPa.
It is understood from the combination of tables 1 and 2 that in examples 4 and 5, the higher the temperature in the reaction space, the higher the hydrogenation rate, with other conditions unchanged. In the practical application process, the minimum required temperature of the solid magnesium is ensured to be 340 ℃, the activity of magnesium and hydrogen can be increased by increasing the temperature, the reaction time is reduced, but correspondingly, higher temperature can also cause higher energy consumption, the ignition point of hydrogen is closer to that of the hydrogen, the potential safety hazard is increased, in order to eliminate the interference of instability of a heating device, the continuity of the reaction is ensured, the ideal temperature is between 350 and 450 ℃, the normal operation of the reaction can be ensured, and the energy waste is reduced.
Based on the various embodiments provided in the present application, the hydrogenation rate in embodiment 5 can meet the expectations, so the flow curve in embodiment 5 (as shown in fig. 4) is set as the flow curve of the initial theoretical reaction, and in the subsequent series of reaction processes, the environmental conditions of the reaction space can be directly set according to the temperature and the pressure corresponding to the optimal embodiment, and the reaction parameters can be adjusted in real time according to the fitting of the flow curve of the initial theoretical reaction, so that the solid magnesium can react with the hydrogen in the optimal working environment. When the flow curve is used for fitting, as the hydrogen flow and the reaction speed of the solid magnesium are in correlation, the flow curve feeds back the reaction performance of the solid magnesium, and factors affecting the reaction performance generally comprise temperature and pressure, and in the subsequent reaction process, when the real-time flow is lower than the flow curve, the temperature can be increased, or the pressure in the reaction space can be increased, and meanwhile, the temperature and the pressure can be synchronously increased. Understanding with "rising temperature", when real-time flow is less than flow curve value, prove that the reaction of solid magnesium can not reach the expectations, through rising temperature, promote the reaction rate of solid magnesium, corresponding also accelerated the flow of hydrogen, and then guarantee that real-time flow can approach the corresponding value of flow curve.
Therefore, based on the structure of the solid magnesium, and the solid magnesium is directly placed on a heating frame in a reaction space to react with hydrogen, under the condition of ensuring the purity preparation requirement, the working pressure reaches 0.8-1 MPa, the working temperature reaches 350-450 ℃, the purity of the finally prepared solid magnesium hydride can still reach more than 99.6%, lower temperature and pressure can be provided compared with the traditional preparation method, and the characteristics of low energy consumption and high performance are satisfied. Compared with the traditional process for preparing magnesium hydride by using powdered magnesium and vaporized magnesium, the method has obvious advantages in working temperature and working pressure.
By integrating the above, in the application, the reaction of the solid magnesium and hydrogen at relatively low temperature and low pressure can be realized without alloy matching, so that the problem of high power consumption required by the traditional magnesium hydride manufacturing is solved, the reaction is promoted without adding any alloy into the solid magnesium, the energy can be effectively utilized, the heat energy loss is reduced, and the control is stable; on the other hand, the temperature during the reaction of the solid magnesium hydride is reduced, so that the overall temperature is controlled below the ignition point of the hydrogen, and the use safety of the hydrogen and the safety of the preparation of the solid magnesium hydride are improved.
Based on the above preparation process of solid magnesium hydride, it can be known that the heating of the solid magnesium hydride is necessary to depend on the preparation device, so the invention also develops a solid magnesium hydride preparation device, as shown in fig. 1, comprising a reaction kettle 3, a heating frame 2, a heat exchange system 4, a gas pipeline system, a temperature detection device, a pressure detection device and a control module.
A reaction space 31 is formed in the reaction kettle 3, and is provided with at least two air ports 32, wherein the two air ports 32 are respectively positioned at the top and the bottom of the reaction kettle 3; the reaction kettle 3 is made of 316L stainless steel, can also adopt other high temperature and high pressure resistant materials suitable for hydrogen to prepare, and be provided with opening and closing device 34 and viewing port 35, the solid magnesium 1 of its inside of opening and closing device 34 is convenient for can easily take out, and viewing port 35 is used for observing the operating condition in the reaction space 31, and the operator of being convenient for in time carries out manual adjustment.
A plurality of heating frames 2 are installed in the reaction space 31 and stacked in layers. As shown in fig. 2, the heating rack 2 includes a fixing base 21, and a heating rod 22 mounted on the fixing base 21; each layer of heating frame 2 is provided with at least two heating rods 22, heating wires capable of controlling temperature are arranged in the heating rods 22, opening and closing time and power can be set, and a temperature control interval is set to be +/-15 ℃; the two heating rods 22 form a group, namely the two heating rods can be used for supporting the solid magnesium 1, so that the joint amount of line contact exists between the heating rods 22 and the solid magnesium 1, and the heating rods 22 must have enough strength and cannot deform; when the heating rod 22 is supported below the solid magnesium, the upward transfer of temperature is facilitated.
In an embodiment, as shown in fig. 2, two heating rods 22 are combined to form a U-shaped structure, and the end parts of the two heating rods are fixedly connected with a fixed seat 21, so that the bonding amount of line contact between the fixed magnesium 1 and the heating rods 22 is met, and the heat of the heating frame 2 is transferred upwards to the fixed magnesium 1.
In other embodiments, as shown in fig. 3, two heating rods 22 are installed in parallel, two ends of each heating rod are fixedly connected with a fixing seat 21, and two adjacent heating rods 22 form a group and are used for placing the solid magnesium 1.
It should be noted that when the solid magnesium 1 is supported on the heating frame 2, a surface contact mode cannot be adopted, otherwise, the contact surface of the solid magnesium 1 cannot be fully contacted with hydrogen for reaction; therefore, by providing the heating rod 22, the amount of adhesion in which the heating rod 22 and the solid magnesium 1 are in line contact can be ensured.
In the invention, the heating frame 2 and the solid magnesium 1 have the bonding quantity, so the heating frame 2 is not required to ensure the temperature in the whole reaction kettle 3 to be stable, and the heat can be effectively transferred to the solid magnesium 1 so as to ensure that the solid magnesium 1 completely reaches the reaction temperature as long as the self temperature reaches the designated height. Furthermore, the preparation device is easier to control, and the problem of uneven heating of the solid magnesium 1 is not needed to be considered.
The heat exchange system 4 is used for realizing cooling in the reaction kettle 3, and aims to provide a set of safety guarantee for the reaction kettle 3 and prevent the safety problem caused by temperature loss, but the heat exchange system does not influence the use of the reaction kettle, and can be selected and installed in the actual application scene. In one embodiment, the heat exchange system 4 may be formed by a cooling coil 4a installed in the reaction space 31, where the cooling coil 4a is connected to a water inlet pipe 41 and a water outlet pipe 42 installed at the bottom of the reaction kettle 3; in other embodiments, a partition space 33 may be formed below the reaction vessel 3, and a water-cooling coil 4a may be provided in the partition space 33.
The gas pipeline system comprises a high temperature resistant pipe body, a high temperature and high pressure resistant valve body, an oxygen content sensor, a hydrogen flow sensor, a pressure relief device and a vacuumizing device, wherein the pressure relief device and the vacuumizing device are connected with the reaction kettle 3. The high temperature resistant pipe body is connected with the gas ports 32 at the top and the bottom of the reaction kettle 3, and the high temperature resistant valve body, the oxygen content sensor and the hydrogen flow sensor are all arranged on the high temperature resistant pipe body and are used for monitoring the hydrogen flow and the oxygen flow at the gas ports 32. The pressure relief device can adopt a burst valve and is arranged at the top of the reaction kettle 3 for preventing the air pressure in the reaction kettle 3 from being too high. Because the reaction kettle 3 is used for the reaction between solid and gas, and the hydrogen quality is lower, the layering gas can be better in early stage through the means of standing, other impurity gases are discharged through the gas port 32 at the bottom, and the use safety of the hydrogen is ensured to the greatest extent by adopting a vacuumizing device and a vacuumizing means.
The temperature detection device and the pressure detection device are respectively used for detecting the temperature and the pressure in the reaction kettle 3, wherein the temperature detection device can adopt temperature sensors, and by setting temperature measuring points at different positions of the reaction space 31, the temperature measuring points are generally set to be not less than four, and the temperature sensors are correspondingly arranged at different temperature measuring points; the pressure detecting device can adopt a pressure sensor, and one pressure sensor can be arranged and installed at a position far away from the air port 32; the data of the temperature sensor and the pressure sensor can be fed back to the control module, and then the control module adjusts the temperature and the pressure in the reaction kettle 3 based on the detection data of the temperature sensor and the pressure sensor, and the temperature in the reaction kettle 3 is respectively heated and cooled through the heating frame 2 and the heat exchange system 4.
In order to enable the hydrogen to fully contact with the solid magnesium 1, in one embodiment, a fan device 5 for enabling the hydrogen to flow based on pressure difference is arranged in the reaction kettle 3; the fan device 5 is installed at one side of the reaction space 31, and the hydrogen gas flows in the reaction space 31 by turning on the fan device 5, so that the contact with the solid magnesium 1 is quickened.
In other embodiments, a high temperature device 6 for flowing hydrogen based on temperature difference is arranged at the bottom of the reaction kettle 3, and the gas at the bottom of the reaction kettle 3 is quickly heated to diffuse to form convection due to the influence of the temperature difference, so that the hydrogen flows. It should be noted that the high temperature device 6 needs to be independent from the space in the reaction kettle 3, so as to prevent the high temperature from affecting the hydrogen, reduce the potential safety hazard, and in one embodiment, the high temperature device 6 may be disposed in the isolation space 33.
Based on the structural characteristics of the solid magnesium and the solid magnesium hydride preparation device, the reaction under the condition of relatively low temperature and low pressure can be realized, and the purity of the solid magnesium hydride can be ensured to be higher. Therefore, when the preparation of the solid magnesium hydride with lower purity requirement is required in application scenes, the temperature and pressure required for the preparation are lower, and the applicability of the solid magnesium hydride preparation device is higher.
As a further optimization, the solid block magnesium hydride preparation device can also be used for reversely preparing hydrogen and is constructed into a hydrogen generation device; the concrete working principle is that solid magnesium hydride is placed on a heating frame, the temperature is controlled to be more than 280 ℃, under normal pressure or negative pressure, the solid magnesium hydride is decomposed into hydrogen and solid magnesium consisting of continuous strip magnesium sheets, when a heating wire is heated to 300 ℃, the solid magnesium hydride can stably release the hydrogen, the heat of the solid magnesium hydride can be effectively utilized due to the structural continuity, and the internal clearance space of the solid magnesium hydride can store heat energy better. In the process, two gas ports at the top and the bottom of the reaction kettle are used for exhausting gas at the bottom of the initial stage, and hydrogen is discharged from the gas port at the top, which is equivalent to a purification means of hydrogen.
Because the hydrogen is discharged from the top gas port, and the temperature in the reaction kettle is higher than 300 ℃, a cooling spiral metal sheet is arranged at the top gas port, so that the temperature is controlled, the hydrogen temperature is reduced, and scalding or hydrogen spontaneous combustion is prevented.
In summary, the solid magnesium hydride preparation device achieves the aim of one machine for two purposes, can stably prepare and obtain the solid magnesium hydride, can stably release hydrogen in the solid magnesium hydride, can collect the hydrogen in more places with waste hydrogen in application scenes, and can safely transport to areas with high hydrogen demand under low pressure and release the hydrogen again. The heating frame and the solid magnesium hydride can be taken out and transported independently, so that the transportation cost of the hydrogen is reduced to a certain extent, and the use convenience of the hydrogen is improved.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same according to the content of the present invention, and are not intended to limit the scope of the present invention. It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore desired that the present invention be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A process for preparing solid magnesium hydride based on multi-gap magnesium is characterized by comprising the following steps:
pressing and forming the strip-shaped magnesium sheet in a regular cavity to obtain solid magnesium, wherein a clearance space for storing heat is formed in the solid magnesium;
heating the solid magnesium in a reaction space which is higher than normal pressure and is sealed, introducing hydrogen to contact the solid magnesium, detecting the temperature and pressure change trend in the reaction space in the process, and adjusting the temperature and the pressure according to the change trend;
and combining the solid magnesium with hydrogen in a set time to obtain the solid magnesium hydride.
2. The process for preparing solid magnesium hydride based on multi-gap magnesium according to claim 1, wherein the process comprises the following steps: in the reaction space, the working temperature is not lower than 340 ℃, and the working pressure is not lower than 0.6MPa.
3. The process for preparing solid magnesium hydride based on multi-gap magnesium according to claim 1, wherein the process comprises the following steps: the thickness of the strip-shaped magnesium sheet is lower than 200 mu m, and the thickness of the strip-shaped magnesium sheet is positively correlated with the working temperature and the working pressure under the preset specific hydrogenation rate.
4. A process for preparing solid magnesium hydride based on multi-gap magnesium according to claim 3, wherein: the density of the solid magnesium is 70-80% of that of the solid magnesium.
5. The process for preparing solid magnesium hydride based on multi-gap magnesium according to claim 1, wherein the process comprises the following steps: the solid magnesium is arranged on the heating frame in the reaction space, the joint amount of line contact exists between the solid magnesium and the heating frame, and the heat of the heating frame is transferred upwards to the solid magnesium.
6. The process for preparing solid magnesium hydride based on multi-gap magnesium according to claim 1, wherein the process comprises the following steps: the hydrogen flows in the reaction space based on pressure difference or temperature difference and is fully contacted with the solid magnesium in a flowing state.
7. A solid magnesium hydride manufacturing apparatus based on a process for manufacturing a solid magnesium hydride based on multi-gap magnesium as claimed in any one of claims 1 to 6, characterized by comprising:
the reaction space is formed in the reaction kettle, and the reaction kettle is provided with at least two air ports which are respectively positioned at the top and the bottom of the reaction kettle;
the heating frame comprises a fixed seat and a heating rod arranged on the fixed seat; each layer of heating frame is provided with at least two heating rods, heating wires are arranged in the heating rods, and the heating rods are used for supporting the solid magnesium and transmitting heat;
the gas pipeline system realizes the circulation of gas in the reaction kettle;
the temperature detection device and the pressure detection device are arranged on the reaction kettle and are respectively used for detecting the temperature and the pressure in the reaction kettle;
and the control module is used for adjusting the temperature and the pressure in the reaction kettle based on the detection data of the temperature detection device and the pressure detection device.
8. The apparatus for preparing solid magnesium hydride according to claim 7, wherein: a fan device for enabling hydrogen to flow based on pressure difference is arranged in the reaction kettle;
or, a high-temperature device for enabling hydrogen to flow based on temperature difference is arranged at the bottom of the reaction kettle, and the high-temperature device is independent of the space in the reaction kettle.
9. The apparatus for preparing solid magnesium hydride according to claim 7, wherein: the gas pipeline system comprises a high-temperature-resistant pipe body, a high-temperature-resistant high-pressure-resistant valve body, an oxygen content sensor, a hydrogen flow sensor, a pressure relief device and a vacuumizing device, wherein the pressure relief device and the vacuumizing device are connected with the reaction kettle;
the high temperature resistant pipe body is connected with the gas ports at the top and the bottom of the reaction kettle, and the high temperature resistant valve body, the oxygen content sensor and the hydrogen flow sensor are all arranged on the high temperature resistant pipe body and are used for monitoring the hydrogen flow and the oxygen flow at the gas ports.
10. The apparatus for preparing solid magnesium hydride according to claim 7, wherein: the heat exchange system adopts a cooling coil; the cooling coil is arranged in the reaction space or in a partition space at the bottom of the reaction kettle.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109250683A (en) * | 2018-09-30 | 2019-01-22 | 武汉市能智达科技有限公司 | It is a kind of using magnesium hydride as the hydrogen production process of hydrogen storage material and device |
| CN113620246A (en) * | 2021-09-23 | 2021-11-09 | 上海氢投捷能科技有限公司 | Method for preparing granular magnesium hydride |
| CN114195095A (en) * | 2021-12-22 | 2022-03-18 | 艾氢技术(苏州)有限公司 | Novel high-temperature continuous solid block hydrogen generation device hydrogen generation control system |
| CN115916691A (en) * | 2020-06-19 | 2023-04-04 | 生物焦炭技术研究株式会社 | Magnesium hydride production device and magnesium hydride production method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109250683A (en) * | 2018-09-30 | 2019-01-22 | 武汉市能智达科技有限公司 | It is a kind of using magnesium hydride as the hydrogen production process of hydrogen storage material and device |
| CN115916691A (en) * | 2020-06-19 | 2023-04-04 | 生物焦炭技术研究株式会社 | Magnesium hydride production device and magnesium hydride production method |
| CN113620246A (en) * | 2021-09-23 | 2021-11-09 | 上海氢投捷能科技有限公司 | Method for preparing granular magnesium hydride |
| CN114195095A (en) * | 2021-12-22 | 2022-03-18 | 艾氢技术(苏州)有限公司 | Novel high-temperature continuous solid block hydrogen generation device hydrogen generation control system |
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