CN111992048A - Preparation method of alloy palladium membrane - Google Patents
Preparation method of alloy palladium membrane Download PDFInfo
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- CN111992048A CN111992048A CN202010746607.XA CN202010746607A CN111992048A CN 111992048 A CN111992048 A CN 111992048A CN 202010746607 A CN202010746607 A CN 202010746607A CN 111992048 A CN111992048 A CN 111992048A
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- palladium membrane
- carrier
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- alloy palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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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
Abstract
The invention provides a preparation method of an alloy palladium membrane, which comprises the following steps of S1: placing a porous carrier into at least two metal plating solutions in a rotational flow mode, and depositing at least two metals on the surface of the carrier through a chemical plating method, wherein one of the at least two metals is palladium; s2: repeating the step S1N times, wherein N is an integer and is more than 1; s3: immersing the carrier in deionized water to remove redundant impurities; s4: and placing the finished product after chemical plating into a muffle furnace to fuse the at least two metals. Compared with the prior art, the preparation method of the alloy palladium membrane has the advantages that the prepared alloy palladium membrane is uniformly fused by a circulating chemical plating method, so that the purification effect of the alloy palladium membrane is effectively improved.
Description
Technical Field
The invention belongs to the technical field of hydrogen purification, and particularly relates to a preparation method of an alloy palladium membrane.
Background
In recent years, with the rapid development of industries such as hydrogen fuel cells, steel, semiconductors, microelectronics, petrochemical industry and the like, the demand of high-purity hydrogen is rapidly increased, and the research on the production and separation technology of high-purity hydrogen is strongly promoted. The palladium and palladium alloy membrane has a series of advantages of excellent hydrogen permeation selectivity, good mechanical and thermal stability and the like based on the characteristics of the material, and is deeply and widely researched.
At present, palladium membrane purification technology is widely applied to the preparation of pure hydrogen and high-purity hydrogen. The commercial development of palladium membranes has gone through the process from pure palladium membranes to palladium alloy membranes. Since the tubular palladium membrane has a higher specific separation area than the sheet-shaped palladium membrane, which is advantageous for improving the integration of the palladium membrane module, the shape of the membrane is also developed from the original sheet shape to the now-commonly used tubular shape.
The tubular palladium membrane is divided into an unsupported type and a supported type. The unsupported tubular palladium membrane is prepared mainly through smelting, casting and rolling process, which includes mixing palladium or palladium alloy material in certain proportion, smelting and casting at high temperature to obtain cast ingot, cold and hot forging to form tube blank, and repeated cold rolling and annealing to obtain thin wall tube of required thickness. The unsupported tubular palladium membrane has the advantages of stable performance, good selectivity to hydrogen, poor mechanical strength, low hydrogen permeation rate, large pressure loss of hydrogen and high use cost. The above disadvantages limit the application of unsupported tubular palladium membranes to the technical field of low flow, low pressure, high purity hydrogen purification.
The supported tubular palladium membrane refers to metal palladium or an alloy membrane thereof which is loaded on the surface of a porous tubular support body through a physical or chemical method so as to integrate the metal palladium and the alloy membrane. The support is usually made of tubular porous ceramics, porous stainless steel, porous glass and the like. The preparation method of the supported tubular palladium membrane mainly comprises a physical vapor deposition method, a chemical vapor deposition method, a spray pyrolysis method, electroplating, chemical plating and the like. The support type tubular palladium membrane effectively solves the problem of poor mechanical strength of the palladium membrane tube because the support body is made of porous materials made of metal, ceramic and the like. Meanwhile, the palladium membrane or the palladium alloy membrane obtained by the preparation method has smaller thickness, so that the support type tubular palladium membrane also has the advantages of high hydrogen permeation rate, small hydrogen pressure loss, low use cost and the like.
However, pure palladium membranes are prone to hydrogen embrittlement, and alloy palladium membranes made of palladium and silver are not only not prone to hydrogen embrittlement, but also have good purification effects. However, the palladium-silver alloy membrane manufactured by the existing process is not uniformly fused, so that the purification effect of the palladium-silver alloy membrane is reduced.
In view of the above problems, it is necessary to provide a method for preparing an alloy palladium membrane to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of an alloy palladium membrane, which enables the prepared alloy palladium membrane to be fused uniformly by a circulating chemical plating method, thereby effectively improving the purification effect of the alloy palladium membrane.
In order to achieve the purpose, the invention provides a preparation method of an alloy palladium membrane, which comprises the following steps:
s1: placing a porous carrier into at least two metal plating solutions in a rotational flow mode, and depositing at least two metals on the surface of the carrier through a chemical plating method, wherein one of the at least two metals is palladium;
s2: repeating the step S1N times, wherein N is an integer and is more than 1;
s3: immersing the carrier in deionized water to remove redundant impurities;
s4: and placing the finished product after chemical plating into a muffle furnace to fuse the at least two metals.
As a further improvement of the invention, in step S1, the thickness of the metal plating film deposited on the surface of the carrier is not more than 0.2 μm.
As a further improvement of the invention, the cycle number N is between 15 and 25.
As a further improvement of the present invention, the number of cycles N is 20.
As a further improvement of the present invention, the step S4 further includes a step S42: the temperature in the muffle furnace is gradually increased from 850 ℃ to 1200 ℃.
As a further improvement of the present invention, the step S4 further includes a step S41: and introducing protective gas into the muffle furnace to prevent the metal from being oxidized.
As a further improvement of the invention, the protective gas is nitrogen or hydrogen.
As a further improvement of the invention, the carrier is a stainless steel carrier.
As a further improvement of the present invention, the at least two metal plating solutions include at least one of a silver plating solution, a gold plating solution, and a copper plating solution.
As a further improvement of the invention, the at least two metal plating solutions are uniformly arranged on the periphery of the rotary worktable.
The invention has the beneficial effects that: according to the preparation method of the alloy palladium membrane, the prepared alloy palladium membrane is uniformly fused by a circulating chemical plating method, so that the purification effect of the alloy palladium membrane is effectively improved.
Drawings
FIG. 1 is a schematic flow diagram of the alloy palladium membrane preparation method of the present invention.
Fig. 2 is a schematic view of a rotary table structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Referring to fig. 1, the present invention discloses a method for preparing an alloy palladium membrane, comprising the following steps:
s1: and placing the porous carrier into at least two metal plating solutions in a rotational flow mode, and depositing at least two metals on the surface of the carrier through an electroless plating method, wherein one of the at least two metals is palladium.
In this embodiment, the porous support is a stainless steel support, however, in other embodiments, the porous support may also be a porous ceramic. The at least two metal plating solutions further include at least one of a silver plating solution, a gold plating solution, and a copper plating solution. Of course, in other embodiments, the at least two metal plating solutions may also include other metal plating solutions in addition to the metal plating solution described above. The thickness of the metal coating deposited on the surface of the carrier is not more than 1 micron. Preferably, the thickness of the metal plating film is not more than 0.2 micron. Because the thickness of the metal coating layer is smaller, the adjacent metal coating layers are easy to fuse uniformly, and the hydrogen purification efficiency of the alloy palladium film is effectively improved. Since the deposition thickness of the metal particles is time-dependent, the thickness of the metal coating can be controlled by controlling the time of the stainless steel support in the metal plating solution.
Furthermore, the mass proportion of different metals in the whole plated film can be controlled by controlling the thickness proportion of the plated films of different metals.
S2: repeating the step S1N times, wherein N is an integer and is more than 1.
In the existing preparation method, the time of the carrier in a single metal plating solution is long, so that the thickness of a metal plating film exceeds 1 micron. For example, chinese patent No. 2013107139608 discloses a palladium membrane preparation method, which comprises plating a palladium membrane with a thickness of 3.8 microns on a carrier, and then plating a silver membrane with a thickness of 1.2 microns. The palladium film and the silver film are thicker, so that the palladium film and the silver film are fused unevenly, and the hydrogen purification effect of the alloy palladium film is further reduced. The preparation method of the alloy palladium film provided by the invention enables the total thickness of the plated film on the surface of the carrier to reach the required thickness by a method of circulating chemical plating for N times. Moreover, the thickness of each metal coating is less than 1 micron, so that adjacent metal coatings are easy to fuse uniformly, and the hydrogen purification efficiency of the alloy palladium membrane is effectively improved. When the cycle number N is between 15 and 25, the manufacturing speed of the alloy palladium film and the fusion effect between adjacent metal coating films can be effectively considered. Preferably, the number of cycles N is 20.
S3: the carrier is immersed in deionized water to remove excess impurities.
And when the total thickness of the plated film on the surface of the carrier reaches a preset thickness value, soaking the carrier into deionized water to remove redundant impurities. In this embodiment, the at least two metal plating solutions and the deionized water are uniformly disposed on the periphery of the rotary table, so as to implement the cyclic electroless plating.
FIG. 2 shows a rotary table with palladium, silver and gold films plated on the surface of a carrier. First, the carrier 10 is moved above the rotary table 20. Then, the rotary table 20 is rotated so that the palladium plating solution 21 is positioned below the carrier 10; next, the rotary table 20 is raised so that the support 10 is immersed in the palladium plating solution 21; after the palladium film with a preset thickness value is deposited on the surface of the carrier 10, the rotary table 20 is lowered, and the rotary table 20 is rotated, so that the silver plating solution 22 is positioned below the carrier 10. Then, the rotary table 20 is raised so that the carrier 10 is immersed in the silver plating solution 22; after depositing the silver film with the preset thickness value on the surface of the carrier 10, the rotary table 20 descends, and the rotary table 20 is rotated, so that the gold plating solution 232 is located below the carrier 10. Then, the rotary table 20 is raised so that the carrier 10 is immersed in the gold plating solution 23; after the gold film with a preset thickness value is deposited on the surface of the carrier 10, the rotary table 20 descends. Then, repeating the steps of plating the palladium film, the silver film and the gold film for N times until the total thickness of the plated film on the surface of the carrier 10 reaches the required thickness. Then, the rotary table 20 is rotated such that the deionized water 24 is positioned under the carrier 10, and then the rotary table 20 is raised such that the carrier 10 is immersed in the deionized water 24, thereby removing the excessive impurities.
S4: and placing the finished product after chemical plating into a muffle furnace to ensure that the at least two metals are uniformly fused.
Further, the step S4 further includes the following steps:
s41: and introducing protective gas into the muffle furnace to prevent the metal coating films from being oxidized and prevent impurities from being absorbed when the adjacent metal coating films are fused to influence the strength of the alloy film. The protective gas can be nitrogen or hydrogen.
S42: the temperature in the muffle furnace is gradually increased from 850 ℃ to 1200 ℃. Because the metal coating and the carrier have thermal expansion coefficients, the finished product after chemical plating needs to be gradually heated after being put into a muffle furnace so as to protect the service life of the finished product.
Compared with the prior art, the preparation method of the alloy palladium membrane has the advantages that the prepared alloy palladium membrane is uniformly fused by a circulating chemical plating method, so that the purification effect of the alloy palladium membrane is effectively improved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the alloy palladium membrane is characterized by comprising the following steps:
s1: placing a porous carrier into at least two metal plating solutions in a rotational flow mode, and depositing at least two metals on the surface of the carrier through a chemical plating method, wherein one of the at least two metals is palladium;
s2: repeating the step S1N times, wherein N is an integer and is more than 1;
s3: immersing the carrier in deionized water to remove redundant impurities;
s4: and placing the finished product after chemical plating into a muffle furnace to fuse the at least two metals.
2. The method of preparing an alloy palladium membrane according to claim 1, wherein: in step S1, the thickness of the metal plating film deposited on the surface of the carrier is not more than 0.2 μm.
3. The method of preparing an alloy palladium membrane according to claim 1, wherein: and the cycle number N is between 15 and 25.
4. The method of preparing an alloy palladium membrane according to claim 3, wherein: the number of cycles N is 20.
5. The method of preparing an alloy palladium membrane according to claim 1, wherein: the step S4 further includes a step S42: the temperature in the muffle furnace is gradually increased from 850 ℃ to 1200 ℃.
6. The method of preparing an alloy palladium membrane according to claim 5, wherein: the step S4 further includes a step S41: and introducing protective gas into the muffle furnace to prevent the metal from being oxidized.
7. The method of preparing an alloy palladium membrane according to claim 6, wherein: the protective gas is nitrogen or hydrogen.
8. The method of preparing an alloy palladium membrane according to claim 1, wherein: the carrier is a stainless steel carrier.
9. The method of preparing an alloy palladium membrane according to claim 1, wherein: the at least two metal plating solutions include at least one of a silver plating solution, a gold plating solution, and a copper plating solution.
10. The method of preparing an alloy palladium membrane according to claim 1, wherein: the at least two metal plating solutions are uniformly arranged on the periphery of the rotary worktable.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010746607.XA CN111992048A (en) | 2020-07-29 | 2020-07-29 | Preparation method of alloy palladium membrane |
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| CN202010746607.XA CN111992048A (en) | 2020-07-29 | 2020-07-29 | Preparation method of alloy palladium membrane |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070110991A1 (en) * | 2005-11-15 | 2007-05-17 | Apte Prasad S | Hydrogen transport membrane fabrication method |
| CN102441330A (en) * | 2011-10-24 | 2012-05-09 | 南京工业大学 | Palladium-based dual functional film and its preparation method |
| CN103721576A (en) * | 2013-12-20 | 2014-04-16 | 南京工业大学 | Preparation method of palladium membrane |
| CN106811778A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | The preparation and palladium-copper alloy film and application of component and the controllable palladium-copper alloy film of thickness |
| CN109734052A (en) * | 2019-03-18 | 2019-05-10 | 苏州高迈新能源有限公司 | Hydrogen purification device |
-
2020
- 2020-07-29 CN CN202010746607.XA patent/CN111992048A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070110991A1 (en) * | 2005-11-15 | 2007-05-17 | Apte Prasad S | Hydrogen transport membrane fabrication method |
| CN102441330A (en) * | 2011-10-24 | 2012-05-09 | 南京工业大学 | Palladium-based dual functional film and its preparation method |
| CN103721576A (en) * | 2013-12-20 | 2014-04-16 | 南京工业大学 | Preparation method of palladium membrane |
| CN106811778A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | The preparation and palladium-copper alloy film and application of component and the controllable palladium-copper alloy film of thickness |
| CN109734052A (en) * | 2019-03-18 | 2019-05-10 | 苏州高迈新能源有限公司 | Hydrogen purification device |
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Application publication date: 20201127 |