CN107500248B - Spherical core-shell type LaNiAl-SiO2Composite hydrogen storage material and preparation method thereof - Google Patents

Spherical core-shell type LaNiAl-SiO2Composite hydrogen storage material and preparation method thereof Download PDF

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CN107500248B
CN107500248B CN201710855071.3A CN201710855071A CN107500248B CN 107500248 B CN107500248 B CN 107500248B CN 201710855071 A CN201710855071 A CN 201710855071A CN 107500248 B CN107500248 B CN 107500248B
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lanial
alloy
sio
hydrogen storage
spherical core
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CN107500248A (en
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程宏辉
徐林华
王葵葵
刘晶晶
韩兴博
严凯
陈东雷
吴瑛
秦康生
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Yangzhou University
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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
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The invention relates to a spherical core-shell suitable for hydrogen separationType LaNiAl-SiO2A composite hydrogen storage material and a preparation method thereof belong to the field of hydrogen storage materials. Wherein the component general formula of the LaNiAl alloy is LaNi5‑xAlxX is more than or equal to 0 and less than or equal to 2. The spherical material has an outer diameter of 4-6 mm, the middle main component is LaNiAl alloy, and the outer surface is porous SiO2The thickness is 1-2 mm. The preparation process of the material comprises the steps of alloy smelting and powder preparation, stirring and mixing of alloy powder and silica sol, granulation, and gas phase SiO2And final aging to remove the hydrothermal treatment. The preparation method of the composite hydrogen storage material has high automation degree, uniform appearance size, small airflow resistance, highest filling amount in a reactor, no crushing, no further pulverization, no filter blockage or self compaction, and greatly reduced CO and O2、NH3、H2S and other impurity gases poison the LaNiAl alloy, so that the service life is greatly prolonged, and the method can be used for a hydrogen separation process.

Description

Spherical core-shell type LaNiAl-SiO2Composite hydrogen storage material and preparation method thereof
Technical Field
The invention relates to a spherical core-shell LaNiAl-SiO suitable for hydrogen separation2A composite hydrogen storage material and a preparation method thereof belong to the field of hydrogen storage materials.
Background
Hydrogen storage alloys are capable of reversible reaction with hydrogen and have been used, in part, in hydrogen separation applications. These alloys can absorb and release large amounts of hydrogen gas at suitable temperatures and pressures. The use of metal hydrides allows for the economical and efficient recovery of hydrogen from a gas mixture in a simple temperature or pressure increase and decrease process. However, the metal hydride is accompanied by a remarkable effect in the process of absorbing and desorbing hydrogenThe change of the volume of the earth lattice generates cyclic internal stress to lead the material to be pulverized into micron-sized particles. These pulverized particles are not suitable for use in large separation columns because they severely restrict gas flow and clog filters, and in addition, build up at the bottom of the vessel tends to create strong stresses on the walls of the vessel causing bulging and even cracking. In addition, metal hydrides are also susceptible to reaction with O2And CO and other common impurity gases react to cause poisoning, so that the reaction with hydrogen cannot be performed. For metal hydrides to be used in hydrogen separation processes on a large scale, they must be in a stable form and not be continuously pulverized, and must be resistant to poisoning by oxygen or other impurity gases.
Various attempts have been made to do this, such as: metal hydride powder and metal (Cu, Al, Ni) powder are mixed, then tableted, and sintered into pellets under vacuum, inert atmosphere, or hydrogen atmosphere. These particles have high mechanical strength and can withstand multiple hydrogen adsorptions without powdering. However, the resistance of hydrogen gas to permeate through these particles is large, and after the hydrogen permeation effect is improved, these particles are not stable, and eventually the metal hydride will come out. Therefore, there is a need to develop better over-fill methods.
Disclosure of Invention
The invention aims to provide a spherical core-shell type LaNiAl-SiO suitable for hydrogen separation2The composite hydrogen storing material is spherical, has LaNiAl alloy as main component and porous SiO as outer surface2The LaNiAl alloy is embedded in the porous SiO with easy activation and stable structure2The spherical shell does not generate the phenomena of alloy pulverization, channeling and self compaction caused by hydrogen absorption and desorption, and the porous SiO2Can effectively block CO and O2，H2S，CH4，CO2And the impurity gases do not cause the poisoning of the LaNiAl alloy, and the method can be well used for a hydrogen separation reactor.
In order to achieve the purpose, the technical scheme of the invention is as follows:
spherical core-shell type LaNiAl-SiO2Composite hydrogen storageThe material is characterized in that the component general formula of the LaNiAl alloy is LaNi5-xAlxWherein x is more than or equal to 0 and less than or equal to 2; the spherical material has an outer diameter of 4-6 mm, the middle main component is LaNiAl alloy, and the outer surface is porous SiO2The thickness is 1-2 mm.
The spherical core-shell type LaNiAl-SiO2The preparation method of the composite hydrogen storage material comprises the following steps:
(1) preparing LaNiAl alloy powder: firstly, smelting LaNiAl alloy by adopting a vacuum induction furnace or an electric arc furnace, wherein the LaNiAl alloy has a general formula of LaNi5-xAlxWherein x is more than or equal to 0 and less than or equal to 2;
(2) fully mixing LaNiAl powder and silica sol: weighing LaNiAl fine powder and acidic silica sol with the concentration of 25-30% and the pH value of 2-4, wherein the weight ratio of the LaNiAl fine powder to the acidic silica sol is 7.5: 2.5 to 7: 3, fully mixing in an electric mixer for 20-30 min, and after mixing, ensuring that the mixture can be formed by kneading with hands;
(3) preparation of lanai pellets: putting the mixture of the LaNiAl and the silica sol prepared in the step 2 into a feed inlet of a full-automatic ball rolling machine, starting the machine to observe a strip outlet to ensure that a strip can be rolled out, granulating once the strip can be stably rolled out, wherein the diameter of a ball rolling die selected in the granulating process is 4-5 mm, and the manufactured spherical particles are received by a stainless steel tray;
(4) cladding and polishing of LaNiAl pellets: mixing the LaNiAl pellets prepared in the step 3 with a specific surface area of 200m2/g～380m2Hydrophilic gas phase SiO of/g2Putting into a disc type granulator, starting the disc type granulator to make the spherulites continuously roll in the granulator, simultaneously adopting a spray can to spray silica sol, and making the outer wall of the LaNiAl spherulites uniformly be full of gas phase SiO in the continuous rolling process2Meanwhile, the outer diameter of the spherulites is continuously increased, and when the outer diameter is 5-6 mm and the surface is smooth, the spherulites are taken out; in this case, the spherical core-shell LaNiAl-SiO containing water2A composite hydrogen storage material;
(5) spherical core-shell type LaNiAl-SiO2Drying and heat treatment of the composite hydrogen storage material: the pellets are dried and heat treated to ensure they are ready for use in the relevant reactorThe spherulites have better strength; firstly, spherical core-shell type LaNiAl-SiO2Placing the composite material in the air for 5-7 days, performing simple natural drying and aging, wherein when the water in the silica sol is evaporated, the colloidal particles are firmly attached to the surface of an object, and silica bonding is formed among the particles, so that the three-dimensional SiO is formed2The skeleton structure has good strength, then the spherulites are placed in a vacuum heat treatment furnace, the temperature is slowly raised to 200-400 ℃, the temperature rising speed is 1-3 ℃/min, vacuum heat treatment is carried out to remove water, meanwhile, the strength of the skeleton is further increased, after the temperature is kept constant at 200-400 ℃ for 3-5 hours, furnace air cooling is carried out, and finally required finished products are obtained.
The spherical core-shell type LaNiAl-SiO2The preparation method of the composite hydrogen storage material comprises the following steps of (1), when smelting LaNiAl alloy, the purity of the used metal is La: 99.3wt%, Ni: 99.9wt%, Al: 99.7 wt%; sealing the alloy ingot in a vacuum quartz tube after smelting, putting the alloy ingot into a heat treatment furnace for homogenization treatment, heating the alloy ingot to 1100 +/-20 ℃ along with the furnace, preserving the heat for 5-7 hours, and then cooling along with the furnace; weighing a heat-treated LaNiAl alloy ingot, mechanically crushing the heat-treated LaNiAl alloy ingot into millimeter-sized particles, performing hydrogen absorption and desorption cycles on a full-automatic Sieverts device for 20-30 times, wherein the hydrogen charging pressure is 1-2 MPa, the water bath temperature is 60-200 ℃, finally, charging high-purity argon gas with the pressure of 0.5-1.5 MPa into the Sieverts device to passivate the high-activity surface of the pulverized LaNiAl alloy, opening a reaction chamber to expose the pulverized LaNiAl alloy in the air, standing for 2-3 days to further passivate the surface of the pulverized LaNiAl alloy, sieving the surface of the pulverized LaNiAl alloy with a 200-300-mesh sieve after the surface is passivated, collecting and storing the sieved fine powder in a sealed container.
The invention has the following advantages and beneficial effects:
1. the invention relates to spherical core-shell type LaNiAl-SiO2The composite hydrogen storage material has uniform appearance size, small error and high automation degree of the preparation method of the composite hydrogen storage material.
2. The composite material of the present invention is spherical, has low resistance to gas flow, has the highest packing amount in the reactor, and is not crushed, further pulverized, blocked in a filter or self-compacted.
3. Composite material of the inventionInternal three-dimensional SiO2The skeleton structure has good strength and can not be crushed when being filled in a reactor.
4. The LaNiAl alloy powder is wrapped in SiO2In the framework, the phenomenon that the LaNiAl powder flows randomly along with the airflow due to further pulverization in the hydrogen absorption and desorption process can be prevented, and a filter cannot be blocked or self-compaction cannot be caused.
5. The LaNiAl alloy powder is wrapped in SiO2In the framework, CO and O can be greatly reduced2、NH3、 H2S and other impurity gases poison the LaNiAl alloy, so that the service life is greatly prolonged, and the method can be used for a hydrogen separation process.
Drawings
FIG. 1 shows spherical core-shell LaNi of the present invention4.25Al0.75-SiO2PCT hydrogen absorption and desorption curves of the composite material.
FIG. 2 shows spherical core-shell LaNi of the present invention4.25Al0.75-SiO2Hydrogen sorption kinetic profile of the composite material.
FIG. 3 shows spherical core-shell LaNi of the present invention4Al-SiO2PCT hydrogen absorption and desorption curves of the composite material.
FIG. 4 shows spherical core-shell LaNi of the present invention4Al-SiO2Hydrogen sorption kinetic profile of the composite material.
FIG. 5 shows spherical core-shell LaNi of the present invention4.5Al0.5-SiO2PCT hydrogen absorption and desorption curves of the composite material.
FIG. 6 shows spherical core-shell LaNi of the present invention4.5Al0.5-SiO2Hydrogen sorption kinetic profile of the composite material.
Detailed Description
In the specific implementation process, the spherical core-shell LaNiAl-SiO provided by the invention2The component general formula of the LaNiAl alloy is LaNi5-xAlxWherein x is more than or equal to 0 and less than or equal to 2. The diameter of the spherical material is 4-6 mm, the middle main component is LaNiAl alloy, and the surface is porous SiO2The thickness is 1-2 mm.
The invention also provides the spherical core shellType LaNiAl-SiO2The preparation method of the composite hydrogen storage material comprises the following steps:
(1) preparing LaNiAl alloy powder: firstly, smelting LaNiAl alloy by adopting a vacuum induction furnace or an electric arc furnace, wherein the LaNiAl alloy has a general formula of LaNi5-xAlxWherein x is more than or equal to 0 and less than or equal to 2. The purity of the metal used is La: 99.3wt%, Ni: 99.9wt%, Al: 99.7 wt%. Sealing the alloy ingot in a vacuum quartz tube after smelting, putting the alloy ingot into a heat treatment furnace for homogenization treatment, heating the alloy ingot to 1100 ℃ along with the furnace, preserving the heat for 6 hours, and then cooling the alloy ingot along with the furnace. Weighing a certain weight of heat-treated LaNiAl alloy ingot, mechanically crushing the heat-treated LaNiAl alloy ingot into millimeter-sized particles, then performing hydrogen absorption and desorption cycles on a full-automatic Sieverts device for 20-30 times, wherein the hydrogen charging pressure is 1-2 MPa, the water bath temperature is 60-200 ℃, finally charging 1MPa high-purity argon (the volume purity is 99.999%) into the Sieverts device to passivate the high-activity surface of the pulverized LaNiAl alloy, then opening a reaction chamber to expose the pulverized LaNiAl alloy in the air, standing for 2-3 days to further passivate the surface of the pulverized LaNiAl alloy, sieving the surface of the pulverized LaNiAl alloy with a 200-300-mesh sieve, collecting sieved fine powder and storing the fine powder in a sealed container.
(2) Fully mixing LaNiAl powder and silica sol: weighing LaNiAl fine powder and acidic silica sol with the concentration of 25-30 wt% and the pH value of 2-4, and mixing the components in a weight ratio of 7.5: 2.5 to 7: and 3, fully mixing in an electric mixer for 20-30 min, and after mixing, ensuring that the mixture can be formed by kneading with hands.
(3) Preparation of lanai pellets: and (3) putting the mixture of the LaNiAl and the silica sol prepared in the step (2) into a feed inlet of a full-automatic ball kneading machine, starting the machine to observe a strip outlet to ensure that a strip can be kneaded out, granulating once the strip can be stably kneaded out, wherein the diameter of a ball kneading die selected in the granulating process is 4-5 mm, and the prepared spherical particles are received by a stainless steel tray.
(4) Cladding and polishing of LaNiAl pellets: mixing the LaNiAl pellets prepared in the step 3 with a specific surface area of 200m2/g～380m2Hydrophilic gas phase SiO of/g2Putting into a disc type granulator, starting the disc type granulator to make the spherulites continuously roll in the granulator and simultaneouslySpraying silica sol into the LaNiAl pellet to make the outer wall of the LaNiAl pellet coated with gas phase SiO during rolling2And simultaneously, the outer diameter of the spherulite is continuously increased, the outer diameter is 5-6 mm, and the spherulite is taken out when the surface is smooth. In this case, the spherical core-shell LaNiAl-SiO containing water2A composite hydrogen storage material.
(5) Spherical core-shell type LaNiAl-SiO2Drying and heat treatment of the composite hydrogen storage material: the pellets should be dried and heat treated to ensure good strength of the pellets before use in the reactor concerned. Firstly, spherical core-shell type LaNiAl-SiO2Placing the composite material in the air for 5-7 days, performing simple natural drying and aging, wherein when the water in the silica sol is evaporated, the colloidal particles are firmly attached to the surface of an object, and silica bonding is formed among the particles, so that the three-dimensional SiO is formed2The skeleton structure has good strength, then the spherulites are put into a vacuum heat treatment furnace, the temperature is slowly raised to 200-400 ℃, the temperature rising speed is 2 ℃/min, vacuum heat treatment is carried out to remove moisture, meanwhile, the strength of the skeleton is further increased, after the temperature is kept constant at 200-400 ℃ for 4 hours, air cooling is carried out along with the furnace, and finally the required finished product is obtained.
The present invention will be described in further detail below with reference to examples.
Example 1
Firstly, adopting a vacuum induction furnace or an electric arc furnace to smelt LaNi4.25Al0.75Alloy, the purity of the metal used is La: 99.3%, Ni: 99.9%, Al: 99.7 percent. Sealing the alloy ingot in a vacuum quartz tube after smelting, putting the alloy ingot into a heat treatment furnace for homogenization treatment, heating the alloy ingot to 1100 ℃ along with the furnace, preserving the heat for 6 hours, and then cooling the alloy ingot along with the furnace. Weighing a certain weight of heat-treated LaNi4.25Al0.75Mechanically pulverizing alloy ingot into millimeter-sized particles, performing hydrogen absorption and desorption cycles on a full-automatic Sieverts device for 20 times, wherein the hydrogen charging pressure is 1MPa, the water bath temperature is 90 ℃, and finally charging 1MPa high-purity argon gas into the Sieverts device to pulverize LaNi4.25Al0.75Passivating the high-activity surface of alloy, opening the reaction chamber and pulverizing LaNi4.25Al0.75The alloy was exposed to air and left for 3 days to further passivate its surfaceAfter the surface is passivated, the powder is sieved by a 220-mesh sieve, and then the sieved fine powder is collected and stored in a sealed container. Weighing LaNi4.25Al0.75Fine powder and 25% concentration acidic silica sol with pH value of 2, according to the weight ratio of 7.5: 2.5 fully mixing in an electric mixer for 20 minutes, and after the mixing is finished, ensuring that the mixture can be kneaded and formed by hands. Then preparing the obtained LaNi4.25Al0.75And putting the mixture of the silicon sol and the silica sol into a feeding hole of a full-automatic ball rubbing machine, starting the machine to ensure that a strip outlet can rub out a long strip stably, then carrying out granulation, wherein the diameter of a ball rubbing die selected in the granulation process is 4mm, and the produced spherulites are caught by a stainless steel tray. Then preparing to obtain LaNi4.25Al0.75Pellets and a specific surface area of 200m2Hydrophilic gas phase SiO of/g2Pouring into a disc type granulator, starting the disc type granulator to ensure that the spherulites continuously roll in the granulator, and continuously spraying silica sol into the granulator through a spray can under the action of the silica sol and LaNi4.25Al0.75Under rolling of the alloy pellets, LaNi4.25Al0.75The outer surface of the alloy spherulite is uniformly adhered with a layer of gas-phase SiO2The gas phase SiO on the outer wall along with the rolling2The thickness of (2) is continuously increased, and the pellets are taken out when the outer diameter becomes about 5mm and the surface is smooth. Spherical core-shell LaNi4.25Al0.75-SiO2Placing the composite material in the air for 6 days, carrying out simple natural drying and aging, then placing the spherulites into a vacuum heat treatment furnace, slowly raising the temperature to 300 ℃, raising the temperature at the speed of 2 ℃/min, carrying out vacuum heat treatment to remove water, further increasing the strength of the framework, keeping the temperature constant at 300 ℃ for 4 hours, and then carrying out furnace air cooling to obtain the final required finished product.
The prepared spherical core-shell LaNi is subjected to particle strength tester4.25Al0.75-SiO2The composite hydrogen storage material is subjected to a compressive strength test, and the result is 3.5MPa, so that the composite hydrogen storage material can completely meet the strength of filling in a reactor. Spherical core-shell LaNi test set by full-automatic hydrogen storage material performance comprehensive tester4.25Al0.75-SiO2The hydrogen storage performance test of the composite hydrogen storage material shows that the initial activation time is only 0.5h at the pressure of 500kPa and the temperature of 110 ℃, which is higher than that of the common LaNi4.25Al0.75The activation time of the alloy is 4 hours shorter. The obtained hydrogen absorption and desorption PCT curve and hydrogen absorption kinetic test are respectively shown in figure 1 and figure 2, which show that the intrinsic property of hydrogen storage is not changed significantly. In addition, LaNi4.25Al0.75Alloy and spherical core-shell LaNi4.25Al0.75-SiO2The composite hydrogen storage material was subjected to hydrogen absorption and desorption cycles of 10 times in hydrogen gas containing 50ppm of CO, respectively, and it was found that the hydrogen storage capacity of the latter was hardly changed, while the hydrogen storage capacity of the former was reduced by 12%. The time from the initiation of hydrogen absorption to saturation in the former was also about 8 times longer than that in the latter, indicating that spherical core-shell LaNi4.25Al0.75-SiO2The composite hydrogen storage material has extremely obvious effect of resisting the poisoning of impurity gas.
Example 2
Firstly, adopting a vacuum induction furnace or an electric arc furnace to smelt LaNi4Al alloy, the purity of the metal used is La: 99.3%, Ni: 99.9%, Al: 99.7 percent. Sealing the alloy ingot in a vacuum quartz tube after smelting, putting the alloy ingot into a heat treatment furnace for homogenization treatment, heating the alloy ingot to 1100 ℃ along with the furnace, preserving the heat for 6 hours, and then cooling the alloy ingot along with the furnace. Weighing a certain weight of heat-treated LaNi4Mechanically pulverizing Al alloy ingot into millimeter-sized particles, performing hydrogen absorption and desorption cycles on a full-automatic Sieverts device for 30 times, wherein the hydrogen charging pressure is 2MPa, the water bath temperature is 110 ℃, and finally charging 1MPa high-purity argon gas into the Sieverts device to pulverize LaNi4Passivating the high-activity surface of Al alloy, opening the reaction chamber and pulverizing LaNi4Exposing the Al alloy in the air, standing for 3 days to further passivate the surface of the Al alloy, sieving the Al alloy with a 250-mesh sieve after the surface is passivated, and collecting fine powder after sieving and storing the fine powder in a sealed container. Weighing LaNi4Al fine powder and acid silica sol with the concentration of 30% and the pH value of 3, wherein the weight ratio of the Al fine powder to the acid silica sol is 7.5: 2.5 fully mixing in an electric mixer for 25 minutes, and after the mixing is finished, ensuring that the mixture can be formed by kneading with hands. Then preparing the obtained LaNi4Of Al and silica solsAnd (3) putting the mixture into a feed inlet of a full-automatic ball rubbing machine, starting the machine to ensure that a strip outlet can rub out a long strip stably, and then performing granulation, wherein a ball rubbing die selected in the granulation process is 4mm in diameter, and the produced spherical particles are received by a stainless steel tray. Then preparing to obtain LaNi4Al pellets and a specific surface area of 380m2Hydrophilic gas phase SiO of/g2Pouring into a disc type granulator, starting the disc type granulator to ensure that the spherulites continuously roll in the granulator, and continuously spraying silica sol into the granulator through a spray can under the action of the silica sol and LaNi4.Under rolling of Al alloy pellets, LaNi4.The outer surface of the Al alloy spherulite is uniformly adhered with a layer of gas-phase SiO2The gas phase SiO on the outer wall along with the rolling2The thickness of (2) is continuously increased, and the pellets are taken out when the outer diameter becomes about 5mm and the surface is smooth. Spherical core-shell LaNi4Al-SiO2The composite material is placed in the air for 5 days, simple natural drying and aging are carried out, then the spherulites are placed in a vacuum heat treatment furnace, the temperature is slowly increased to 400 ℃, the temperature rising speed is 2 ℃/min, vacuum heat treatment is carried out to remove moisture, meanwhile, the strength of the framework is further increased, after the temperature is kept constant at 400 ℃ for 4 hours, the air cooling is carried out along with the furnace, and finally the required finished product is obtained.
The prepared spherical core-shell LaNi is subjected to particle strength tester4Al-SiO2The composite hydrogen storage material is subjected to a compressive strength test, and the result is 4MPa, so that the composite hydrogen storage material can completely meet the strength of filling in a reactor. Spherical core-shell LaNi test set by full-automatic hydrogen storage material performance comprehensive tester4Al-SiO2The hydrogen storage performance test of the composite hydrogen storage material shows that the initial activation time is only 1h at the pressure of 500kPa and the temperature of 90 ℃, which is compared with the common LaNi4The activation time of the Al alloy is shorter than 3.5 h. The obtained hydrogen absorption and desorption PCT curve and hydrogen absorption kinetics test are respectively shown in figure 3 and figure 4, which show that the intrinsic property of hydrogen storage is not changed significantly. In addition, LaNi4Al alloy and spherical core-shell type LaNi4A-SiO2The composite hydrogen storage material was subjected to hydrogen absorption and desorption cycles of 10 times in hydrogen gas containing 60ppm of CO, respectively, and it was found that the latter had almost no hydrogen storage capacityThe former has a 15% reduction in hydrogen storage capacity, and the former has a 10-fold greater time period from the initiation of hydrogen absorption to saturation than the latter, indicating that the spherical core-shell LaNi4Al-SiO2The composite hydrogen storage material has extremely obvious effect of resisting the poisoning of impurity gas.
Example 3
Firstly, adopting a vacuum induction furnace or an electric arc furnace to smelt LaNi4.5Al0.5Alloy, the purity of the metal used is La: 99.3%, Ni: 99.9%, Al: 99.7 percent. Sealing the alloy ingot in a vacuum quartz tube after smelting, putting the alloy ingot into a heat treatment furnace for homogenization treatment, heating the alloy ingot to 1100 ℃ along with the furnace, preserving the heat for 6 hours, and then cooling the alloy ingot along with the furnace. Weighing a certain weight of heat-treated LaNi4.5Al0.5Mechanically pulverizing alloy ingot into millimeter-sized particles, performing hydrogen absorption and desorption cycles on a full-automatic Sieverts device for 30 times, wherein the hydrogen charging pressure is 2MPa, the water bath temperature is 70 ℃, and finally charging 1MPa high-purity argon gas into the Sieverts device to pulverize LaNi4.5Al0.5Passivating the high-activity surface of alloy, opening the reaction chamber and pulverizing LaNi4.5Al0.5Exposing the alloy in air, standing for 2 days to further passivate the surface, sieving with a 300-mesh sieve after surface passivation, collecting the sieved fine powder, and storing in a sealed container. Weighing LaNi4.5Al0.5Fine powder and acid silica sol with the concentration of 30% and the pH value of 3, wherein the weight ratio of the fine powder to the acid silica sol is 7: and 3, fully mixing in an electric mixer for 30 minutes, and after mixing, ensuring that the mixture can be formed by kneading with hands. Then preparing the obtained LaNi4.5Al0.5And putting the mixture of the silicon sol and the silica sol into a feeding hole of a full-automatic ball rubbing machine, starting the machine to ensure that a strip outlet can rub out a long strip stably, then carrying out granulation, wherein the diameter of a ball rubbing die selected in the granulation process is 5mm, and the produced spherulites are caught by a stainless steel tray. Then preparing to obtain LaNi4.5Al0.5Pellets and a specific surface area of 300m2Hydrophilic gas phase SiO of/g2Pouring into a disc type granulator, starting the disc type granulator to ensure that the spherulites continuously roll in the granulator, continuously spraying silica sol into the granulator through a spray can,under the action of silica sol, and LaNi4.5.Al0.5Under rolling of the alloy pellets, LaNi4.5Al0.5The outer surface of the alloy spherulite is uniformly adhered with a layer of gas-phase SiO2The gas phase SiO on the outer wall along with the rolling2The thickness of (2) is continuously increased, and the pellets are taken out when the outer diameter becomes about 6mm and the surface is smooth. Spherical core-shell LaNi4.5Al0.5-SiO2Placing the composite material in the air for 7 days, carrying out simple natural drying and aging, then placing the spherulites in a vacuum heat treatment furnace, slowly raising the temperature to 300 ℃, raising the temperature at the speed of 2 ℃/min, carrying out vacuum heat treatment to remove water, simultaneously further increasing the strength of the framework, keeping the temperature at 300 ℃ for 4 hours, and then carrying out furnace air cooling to obtain the final required finished product.
The prepared spherical core-shell LaNi is subjected to particle strength tester4.5Al0.5-SiO2The composite hydrogen storage material is subjected to a compressive strength test, and the result is 3.8MPa, so that the composite hydrogen storage material can completely meet the strength of filling in a reactor. Spherical core-shell LaNi test set by full-automatic hydrogen storage material performance comprehensive tester4.5Al0.5-SiO2The hydrogen storage performance test of the composite hydrogen storage material shows that the initial activation time is only 1h at the pressure of 1000kPa and the temperature of 90 ℃, which is more than that of the common LaNi4.5Al0.5The activation time of the alloy is 4.5h shorter. The obtained hydrogen absorption and desorption PCT curve and hydrogen absorption kinetics test are respectively shown in figure 5 and figure 6, which show that the intrinsic property of hydrogen storage is not changed significantly. In addition, LaNi4.5Al0.5Alloy and spherical core-shell LaNi4.5A0.5-SiO2The composite hydrogen storage material was subjected to hydrogen absorption and desorption cycles of 10 times in a hydrogen gas containing 65ppm of CO, and it was found that the hydrogen storage capacity of the latter was almost unchanged, and that the hydrogen storage capacity of the former was reduced by 16%, and that the time from the initiation of hydrogen absorption to the saturation of the former was about 9 times longer than that of the latter, indicating that the spherical core-shell LaNi4.5Al0.5-SiO2The composite hydrogen storage material has extremely obvious effect of resisting the poisoning of impurity gas.

Claims (3)

1. Spherical core-shell type LaNiAl-SiO2The composite hydrogen storage material is characterized in that the LaNiAl alloy has the general formula of LaNi5-xAlxWherein x is more than or equal to 0 and less than or equal to 2; the spherical material has an outer diameter of 4-6 mm and an intermediate component of SiO2Skeleton and embedded SiO2The LaNiAl alloy in the framework has porous SiO on the surface2The thickness is 1-2 mm.
2. Spherical core-shell LaNiAl-SiO according to claim 12The preparation method of the composite hydrogen storage material is characterized by comprising the following steps:
(1) preparing LaNiAl alloy powder: firstly, smelting LaNiAl alloy by adopting a vacuum induction furnace or an electric arc furnace, wherein the LaNiAl alloy has a general formula of LaNi5-xAlxWherein x is more than or equal to 0 and less than or equal to 2;
(2) fully mixing LaNiAl powder and silica sol: weighing LaNiAl fine powder and acidic silica sol with the concentration of 25-30% and the pH value of 2-4, wherein the weight ratio of the LaNiAl fine powder to the acidic silica sol is 7.5: 2.5 to 7: 3, fully mixing in an electric mixer for 20-30 min, and after mixing, ensuring that the mixture can be formed by kneading with hands;
(3) preparation of lanai pellets: putting the mixture of the LaNiAl and the silica sol prepared in the step 2 into a feed inlet of a full-automatic ball rolling machine, starting the machine to observe a strip outlet to ensure that a strip can be rolled out, granulating once the strip can be stably rolled out, wherein the diameter of a ball rolling die selected in the granulating process is 4-5 mm, and the manufactured spherical particles are received by a stainless steel tray;
(4) cladding and polishing of LaNiAl pellets: mixing the LaNiAl pellets prepared in the step 3 with a specific surface area of 200m2/g～380 m2Hydrophilic gas phase SiO of/g2Putting into a disc type granulator, starting the disc type granulator to make the spherulites continuously roll in the granulator, simultaneously adopting a spray can to spray silica sol, and making the outer wall of the LaNiAl spherulites uniformly be full of gas phase SiO in the continuous rolling process2Meanwhile, the outer diameter of the spherulites is continuously increased, and when the outer diameter is 5-6 mm and the surface is smooth, the spherulites are taken out; in this case, the spherical core-shell LaNiAl-SiO containing water2A composite hydrogen storage material;
(5) spherical core-shell type LaNiAl-SiO2Drying and heat treatment of the composite hydrogen storage material: before being used in relative reactor, the pellet is dried and heat treated to ensure the pellet has better strength; firstly, spherical core-shell type LaNiAl-SiO2Placing the composite material in the air for 5-7 days, performing simple natural drying and aging, wherein when the water in the silica sol is evaporated, the colloidal particles are firmly attached to the surface of an object, and silica bonding is formed among the particles, so that the three-dimensional SiO is formed2The skeleton structure has good strength, then the spherulites are placed in a vacuum heat treatment furnace, the temperature is slowly raised to 200-400 ℃, the temperature rising speed is 1-3 ℃/min, vacuum heat treatment is carried out to remove water, meanwhile, the strength of the skeleton is further increased, after the temperature is kept constant at 200-400 ℃ for 3-5 hours, furnace air cooling is carried out, and finally required finished products are obtained.
3. The spherical core-shell LaNiAl-SiO of claim 22The preparation method of the composite hydrogen storage material is characterized in that in the step (1), when the LaNiAl alloy is smelted, the purity of the used metal is La: 99.3wt%, Ni: 99.9wt%, Al: 99.7 wt%; sealing the alloy ingot in a vacuum quartz tube after smelting, putting the alloy ingot into a heat treatment furnace for homogenization treatment, heating the alloy ingot to 1100 +/-20 ℃ along with the furnace, preserving the heat for 5-7 hours, and then cooling along with the furnace; weighing a heat-treated LaNiAl alloy ingot, mechanically crushing the heat-treated LaNiAl alloy ingot into millimeter-sized particles, performing hydrogen absorption and desorption cycles on a full-automatic Sieverts device for 20-30 times, wherein the hydrogen charging pressure is 1-2 MPa, the water bath temperature is 60-200 ℃, finally, charging high-purity argon gas with the pressure of 0.5-1.5 MPa into the Sieverts device to passivate the high-activity surface of the pulverized LaNiAl alloy, opening a reaction chamber to expose the pulverized LaNiAl alloy in the air, standing for 2-3 days to further passivate the surface of the pulverized LaNiAl alloy, sieving the surface of the pulverized LaNiAl alloy with a 200-300-mesh sieve after the surface is passivated, collecting sieved fine powder, and storing the fine powder in a sealed.
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