CN112281016A - Palladium alloy for hydrogen permeation and preparation method thereof - Google Patents
Palladium alloy for hydrogen permeation and preparation method thereof Download PDFInfo
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- CN112281016A CN112281016A CN202011063228.7A CN202011063228A CN112281016A CN 112281016 A CN112281016 A CN 112281016A CN 202011063228 A CN202011063228 A CN 202011063228A CN 112281016 A CN112281016 A CN 112281016A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
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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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
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Abstract
The invention discloses a palladium alloy for hydrogen permeation and a preparation method thereof, wherein the palladium alloy is a ternary alloy, the first component of the palladium alloy is palladium, the second component of the palladium alloy is yttrium, the third component of the palladium alloy is one of gold, silver, platinum and copper, and the three components account for the following mass percentages respectively: 80 to 90 percent of palladium, 5 to 12 percent of yttrium and 2 to 10 percent of one of gold, silver, platinum and copper; the preparation method comprises the processes of material preparation, mixing, suspension smelting, cooling, heat treatment and the like. The palladium alloy has the characteristics of high hydrogen permeation efficiency, good machinability, strong oxidation resistance and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogen purification, relates to a hydrogen purification material, and particularly relates to a palladium alloy for hydrogen permeation and a preparation method thereof.
Background
In recent years, a reforming hydrogen production technology using liquid fossil fuel such as methanol, gasoline, and diesel oil as a raw material has been attracting much attention. The technology has the characteristics of high hydrogen storage density, compact device structure, good use safety, easy acquisition of raw materials, convenient storage, transportation and supply and the like, and has the defect that the reformed product gas contains impurity gases such as carbon monoxide, carbon dioxide, sulfide and the like and can not be directly supplied to a proton exchange membrane fuel cell system. Therefore, the key to realizing miniaturization and equipment application of the reforming hydrogen production technology is to develop an efficient hydrogen purification technology.
The hydrogen purification technology mainly comprises pressure swing adsorption, low-temperature deep cooling, selective oxidation, palladium membrane separation and the like. The palladium membrane separation technology is characterized in that palladium or palladium alloy is prepared into a membrane shape or a tubular shape by a physical or chemical method, and effective separation of hydrogen molecules and other impurity gas molecules is realized by utilizing the unique selective permeability of palladium to hydrogen at a certain temperature (350-450 ℃). The hydrogen purification technology based on palladium membrane separation has the advantages of small volume of a purification device, simple structure, high separation efficiency and the like, and is applied in small scale in the fields of high-purity hydrogen/ultra-high-purity hydrogen preparation, hydrogen fuel cells, chip manufacturing, optical fiber production and the like.
Through continuous scientific exploration and application research, the palladium membrane material for hydrogen purification is developed from initial pure palladium to multi-component fused palladium alloy. Compared with pure palladium, the palladium alloy has higher hydrogen permeation efficiency, mechanical strength and lower raw material cost. At present, palladium alloy materials such as palladium-silver alloy, palladium-copper alloy, palladium-yttrium alloy and the like are mainly applied and researched. For example, commercial palladium-silver (23wt%) alloys have been achieved that have a hydrogen permeation efficiency of 1.7 times that of pure palladium under the same conditions, palladium-copper (40 wt%) alloys that have a hydrogen permeation efficiency of 1.3 times that of pure palladium under the same conditions, and palladium-yttrium (10 wt%) alloys that have a hydrogen permeation efficiency of 2.4 times that of pure palladium under the same conditions. The comprehensive hydrogen permeability of the palladium alloy material is obviously superior to that of pure palladium, but some palladium alloy materials exist in the practical use processAnd (5) problems are solved. The main problem of palladium-silver alloys is their poor resistance to poisoning by impurity gases, especially in the treatment of H-containing alloys2S、SO2、NO2When the raw material hydrogen of impurities is used, the hydrogen permeation efficiency of the alloy film is rapidly reduced, and the alloy film can lose efficacy in a short time. In comparison, the palladium-copper alloy has better impurity gas poisoning resistance, and the main disadvantage is that the palladium-copper alloy is sensitive to temperature fluctuation, and reversible transformation from body centered cubic lattice (BCC) to face centered cubic lattice (FCC) of the palladium-copper alloy is easy to occur in the process of heating and cooling the palladium-copper alloy film. During the unit cell transformation, the volume size parameter of the unit cell changes inevitably, which leads to the rupture and failure of the palladium-copper alloy film due to the contraction or expansion of the cold and hot stress. The palladium-yttrium alloy has the highest hydrogen permeation efficiency, and the main defects of the palladium-yttrium alloy are that the elastic modulus of the alloy material is low, the processing plasticity is poor, and when the palladium-yttrium alloy is processed into a sheet or tubular palladium alloy film, the film is easy to crack, so that the yield is low, and the application of the palladium-yttrium alloy is limited. In addition, the palladium-yttrium alloy is usually prepared by a vacuum induction melting method, and the component uniformity of the obtained alloy needs to be improved.
Therefore, the development and preparation of palladium alloy materials with the characteristics of high hydrogen permeation efficiency, good processability, strong oxidation resistance and the like are the key points of the hydrogen purification technology research based on palladium membrane separation at present.
Disclosure of Invention
One of the purposes of the invention is to provide a palladium alloy material with high hydrogen permeation efficiency, good machinability and strong oxidation resistance aiming at the defects of the existing palladium alloy material for hydrogen permeation.
The technical scheme adopted by the invention for solving the technical problems is as follows: the palladium alloy for hydrogen permeation is a ternary alloy, the first component of the alloy is palladium, the second component is yttrium, the third component is one of gold, silver, platinum and copper, and the mass percentages of the components are respectively as follows: 80% -90% of palladium; 5 to 12 percent of yttrium; 5 to 10 percent of one of gold, silver, platinum and copper, the raw materials of the three components are all metal simple substances with the purity of 99.9 percent or more, and the granularity of the raw materials is 10 to 100 meshes.
The invention also aims to provide a preparation method of the palladium alloy.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a palladium alloy for hydrogen permeation comprises the following steps:
a) respectively weighing three metal raw materials according to the designed component proportion of the palladium alloy, and mechanically mixing the three metal raw materials;
b) smelting the mixed raw materials by using an electromagnetic suspension smelting furnace under the inert gas protective atmosphere to form an alloy molten mass, and then preserving heat for 3-12 min;
c) casting and cooling the palladium alloy molten mass obtained in the step b) on a water-cooling copper disc under the inert gas protective atmosphere to obtain a solid palladium alloy block;
d) and c), placing the palladium alloy block obtained in the step c) into an atmosphere furnace for heat treatment to obtain the palladium alloy material for hydrogen permeation.
The preparation method of the palladium alloy for hydrogen permeation comprises the steps of b) and c) under the protection atmosphere of inert gas of high-purity argon or helium, wherein the pressure is 0.06 MPa-0.2 MPa (gauge pressure).
The preparation method of the palladium alloy for hydrogen permeation comprises the step b) of an electromagnetic suspension smelting furnace, wherein the mass of the smelted alloy is 10 kg-50 kg per furnace, and the temperature rise speed of the smelting furnace is 200-500 ℃/min.
The preparation method of the palladium alloy for hydrogen permeation comprises the following heat treatment procedures in the step d): heating to 800-1000 ℃ at the speed of 10-50 ℃/min, keeping the temperature for 8-24 h, cutting off the power supply of the atmosphere furnace, and slowly cooling the palladium alloy block body to room temperature along with the furnace.
The invention has the beneficial effects that:
the palladium alloy for hydrogen permeation provided by the invention overcomes the defects of low elastic modulus and poor processing plasticity of the palladium yttrium alloy for hydrogen permeation, and has the characteristics of high hydrogen permeation efficiency, good processability and strong oxidation resistance.
2, the preparation method of the palladium alloy for hydrogen permeation provided by the invention has the characteristics of wide application range, high smelting efficiency, good alloy component uniformity, easiness in realizing automatic operation and the like.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
One basic example of the hydrogen permeable palladium alloy of the present invention: a palladium alloy for hydrogen permeation is a ternary alloy, wherein a first component is palladium, a second component is yttrium, a third component is silver, and the three components account for the following mass percentages respectively:
90 percent of palladium
Yttrium 5%
5 percent of silver
The raw materials of the three components are all metal simple substances, and the purity is 99.9% or more. The granularity of the raw materials of the three components is 10 meshes.
Example 2
Is a further example on the basis of example 1: a palladium alloy for hydrogen permeation is a ternary alloy, wherein a first component is palladium, a second component is yttrium, a third component is gold, and the three components account for the following mass percentages respectively:
80 percent of palladium
Yttrium 12%
8 percent of platinum
The raw materials of the three components are all metal simple substances, and the purity is 99.9% or more. The granularity of the raw materials of the three components is 100 meshes.
Example 3
Further examples on the basis of example 2: a palladium alloy for hydrogen permeation is a ternary alloy, wherein a first component is palladium, a second component is yttrium, a third component is copper, and the three components account for the following mass percentages respectively:
palladium 85%
Yttrium 5%
Copper content is 10%
The raw materials of the three components are all metal simple substances, and the purity is 99.9% or more. The granularity of the raw materials of the four components is 60 meshes.
Example 4
The preparation method of the palladium alloy for hydrogen permeation of the invention is basically as follows: the preparation method of the palladium alloy for hydrogen permeation comprises the following steps
a) Respectively weighing three metal raw materials according to the designed component proportion of the palladium alloy, and mechanically mixing the three metal raw materials;
b) smelting the mixed raw materials at a heating speed of 500 ℃/min by adopting an electromagnetic suspension smelting furnace under the protective atmosphere of inert gas according to the mass of the smelted alloy of 50 kg/furnace to form an alloy molten mass, and then preserving heat for 12 min;
c) casting and cooling the palladium alloy molten mass obtained in the step b) on a water-cooling copper disc under the inert gas protective atmosphere to obtain a solid palladium alloy block; wherein the inert gas protective atmosphere is high-purity argon, and the atmosphere pressure is 0.2MPa (gauge pressure)
d) And c) placing the palladium alloy block obtained in the step c) into an atmosphere furnace for heat treatment: heating to 1000 ℃ at the speed of 100 ℃/min, preserving heat for 10h, cutting off the power supply of the atmosphere furnace, and slowly cooling the palladium alloy block body to room temperature along with the furnace to obtain the palladium alloy material for hydrogen permeation.
Example 5
Is a further example on the basis of example 4. The difference from example 4 is: the preparation method of the palladium alloy for hydrogen permeation comprises the following steps of keeping the temperature for 4min in the step b), smelting the alloy in an electromagnetic suspension smelting furnace by 10 kg/furnace, heating the smelting furnace at a speed of 200 ℃/min, wherein the inert gas protective atmosphere in the steps b) and c) is high-purity helium, the atmosphere pressure is 0.06MPa (gauge pressure), and the heat treatment process in the step d) is as follows: heating to 800 ℃ at the speed of 50 ℃/min, keeping the temperature for 24 hours, cutting off the power supply of the atmosphere furnace, and slowly cooling the palladium alloy block body to room temperature along with the furnace.
Example 6
A preferred embodiment on the basis of embodiment 1 and embodiment 4. The difference is that:
the third component of the palladium alloy for hydrogen permeation is gold, and the three components respectively account for the following mass percent:
88% of palladium
Yttrium 7%
5 percent of gold
The granularity of the raw materials of the three components is 50 meshes.
According to the preparation method of the palladium alloy for hydrogen permeation, the heat preservation time in the step b) is 8min, the inert gas protective atmosphere in the step b) and the step c) is high-purity argon, and the atmosphere pressure is 0.15MPa (gauge pressure).
The electromagnetic suspension smelting furnace in the step b) has the quality of the smelted alloy of 40 kg/furnace and the temperature rise speed of the smelting furnace of 300 ℃/min.
The pressure is 0.06 MPa-0.2 MPa
The heat treatment process in the step d) comprises the following steps: heating to 900 ℃ at the speed of 60 ℃/min, keeping the temperature for 18h, cutting off the power supply of the atmosphere furnace, and slowly cooling the palladium alloy block body to room temperature along with the furnace.
The scope of protection of the claims of the invention is not limited to the embodiments described above.
Claims (5)
1. A palladium alloy for hydrogen permeation characterized in that: the mass percentages of the components are respectively as follows:
80 to 90 percent of palladium
5 to 12 percent of yttrium
5 to 10 percent of one of gold, silver, platinum and copper
Wherein each component is a metal simple substance with the granularity of 10-100 meshes and the purity of 99.9% or more.
2. A method for producing the palladium alloy for hydrogen permeation as set forth in claim 1, comprising the steps of:
a) respectively weighing three metal raw materials, and mechanically mixing;
b) smelting the mixed raw materials by using an electromagnetic suspension smelting furnace under the inert gas protective atmosphere to form an alloy molten mass, and then preserving heat for 3-12 min;
c) casting and cooling the palladium alloy molten mass on a water-cooling copper disc under the inert gas protective atmosphere to obtain a solid palladium alloy block;
d) and placing the palladium alloy block into an atmosphere furnace for heat treatment to obtain the palladium alloy material for hydrogen permeation.
3. The method for preparing a palladium alloy for hydrogen permeation according to claim 2, wherein the inert gas protective atmosphere is high-purity argon or helium, and the pressure is 0.06MPa to 0.2 MPa.
4. The preparation method of the palladium alloy for hydrogen permeation according to claim 2, wherein the mass of the alloy smelted by the electromagnetic suspension smelting furnace is 10 kg-50 kg/furnace, and the temperature rise speed is 200 ℃/min-500 ℃/min.
5. The method for producing a palladium alloy for hydrogen permeation according to claim 2, wherein the heat treatment step is: heating to 800-1000 ℃ at the speed of 10-50 ℃/min, keeping the temperature for 8-24 h, cutting off the power supply of the atmosphere furnace, and slowly cooling to room temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385302A (en) * | 2022-07-28 | 2022-11-25 | 青岛元动芯能源科技有限公司 | Tritium recovery and purification system and method for waste neutron target |
| CN115679144A (en) * | 2022-10-26 | 2023-02-03 | 北京工业大学 | Palladium-based multi-element alloy for hydrogen separation and purification |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385302A (en) * | 2022-07-28 | 2022-11-25 | 青岛元动芯能源科技有限公司 | Tritium recovery and purification system and method for waste neutron target |
| CN115385302B (en) * | 2022-07-28 | 2024-01-02 | 中子时代(青岛)创新科技有限公司 | Tritium recovery and purification system and method for waste neutron target |
| CN115679144A (en) * | 2022-10-26 | 2023-02-03 | 北京工业大学 | Palladium-based multi-element alloy for hydrogen separation and purification |
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Application publication date: 20210129 |