CN217939770U - Composite hydrogen filtering film with amorphous nickel-tungsten alloy as intermediate diffusion layer - Google Patents
Composite hydrogen filtering film with amorphous nickel-tungsten alloy as intermediate diffusion layer Download PDFInfo
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- CN217939770U CN217939770U CN202221488452.5U CN202221488452U CN217939770U CN 217939770 U CN217939770 U CN 217939770U CN 202221488452 U CN202221488452 U CN 202221488452U CN 217939770 U CN217939770 U CN 217939770U
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Abstract
The utility model relates to a middle diffusion layer is compound hydrogen membrane of straining of amorphous nickel tungsten alloy comprises porous alumina ceramics supporter, pure palladium layer A, amorphous nickel tungsten layer and pure palladium layer B. Wherein the porous alumina ceramic support can be tubular porous alumina ceramic or sheet alumina ceramic. Plating a pure palladium layer A on the surface of the support body by adopting chemical plating, preparing an amorphous nickel-tungsten layer by electroplating, and finally plating a pure palladium layer B on the surface by adopting chemical plating. The pure palladium layer provides dissociation and desorption for hydrogen, the amorphous nickel-tungsten layer provides better strength and ductility on one hand, and ensures the long-time stable work of the composite membrane, and on the other hand, the material with lower price replaces a part of palladium material, so that the manufacturing cost of the composite hydrogen filtering membrane is reduced. Owing to used the lower tungsten element of hydrogen hold-up volume as alloy element, and had unique amorphous structure, made the utility model discloses the amorphous nickel tungsten alloy layer of preparation is difficult for taking place to pile up at the in-process that the hydrogen atom diffuses and causes hydrogen embrittlement.
Description
Technical Field
The utility model relates to a palladium composite hydrogen filtering membrane with an amorphous nickel-tungsten alloy intermediate diffusion layer, belonging to the technical field of hydrogen purification. In particular to a composite hydrogen filtering membrane which takes electroplated amorphous nickel-tungsten alloy as a diffusion layer and chemically plated pure palladium as a hydrogen separation and desorption layer.
Background
With the ever-increasing energy demand of society, hydrogen energy is widely recognized as an effective alternative to traditional fossil energy sources. Compared with traditional fossil energy, hydrogen energy has a higher calorific value, and the same quality can generate higher heat. In addition, with the influence of human activities and climate change on the environment, the pollution problem of the traditional energy is more and more concerned, and hydrogen energy is used as clean energy, only water is generated in the combustion process, so that the environment is hardly polluted, and the hydrogen energy has great application potential.
The traditional hydrogen production mode mainly comprises hydrogen production by fossil fuel, hydrogen production by industrial byproducts, hydrogen production by electrolysis, hydrogen production by biomass and the like, and the produced hydrogen often contains byproducts such as carbon monoxide, carbon dioxide, sulfide and the like, and can not be directly used in a fuel cell system or used as a raw material of a chemical product. Therefore, the development of efficient hydrogen purification technology is one of the key to the realization of hydrogen in energy substitution and chemical applications.
At present, the separation and purification of hydrogen are mainly carried out by pressure swing adsorption, low-temperature distillation and membrane separation. Compared with other two methods, the membrane separation method has the advantages of lower requirement on equipment, smaller required equipment unit and lower energy consumption, is very suitable for producing small-scale high-purity hydrogen, and has higher purity of the hydrogen obtained by the membrane separation method compared with other methods.
Membrane materials commonly used in membrane separation methods can be divided into a support membrane and a self-support membrane, wherein the self-support membrane is generally obtained by a smelting and rolling method; the support film is obtained by depositing a layer of polymer film or metal film on the surface of the support body. The hydrogen permeation efficiency of the self-supporting membrane is limited by the thickness of the membrane, and micron-sized membrane materials are difficult to obtain through rolling; the support membrane can obtain membrane material with micrometer or even nanometer thickness on the surface of the porous support body, so that the blocking effect of the membrane thickness on the hydrogen permeation efficiency is greatly reduced. The polymer support membrane has low selectivity to hydrogen compared with a metal membrane, is difficult to obtain hydrogen with higher purity, has poor mechanical properties compared with the metal membrane, and is difficult to apply in a high-temperature and high-pressure environment.
The commonly used support body materials of the support membrane comprise porous ceramic, porous glass and porous stainless steel, compared with other two materials, the porous ceramic is not easy to diffuse elements and collapse pore structures, and has good thermal stability and chemical stability and good compatibility with a metal membrane. In addition, the forming process of the porous ceramic is relatively simple, and the micro-nano pore size is beneficial to the adhesion of the metal film.
The metal film material on the surface of the support film can be classified into a crystalline type and an amorphous type. At present, the mature palladium silver film, palladium copper film, palladium gold film, palladium ruthenium film and the like belong to crystal type metal films, and the crystal type metal films can show higher hydrogen permeability in application due to higher hydrogen solubility. The permeation of hydrogen depends on the one hand on the solubility of the hydrogen atoms in the metal and on the other hand on the diffusivity of the hydrogen atoms in the metal, whereas amorphous alloys achieve hydrogen permeation by a higher diffusivity of the hydrogen atoms. On the one hand, the amorphous alloy has a unique atom stacking structure and does not have the characteristics of crystalline materials such as crystal grains, crystal boundaries, dislocation and the like; on the other hand, the density of the amorphous alloy is lower than that of the same-composition crystalline material, the atomic packing density of the amorphous alloy is lower than that of the crystalline alloy, and more voids are provided for absorbing hydrogen atoms and providing fast paths for the hydrogen atoms to diffuse in the film.
Amorphous alloys store hydrogen atoms primarily in atomic-packed voids, as compared to vanadium, niobium, tantalum, and alloys thereof, which absorb hydrogen atoms in the form of metal hydrides (M-H) to achieve higher hydrogen solubility. In the using process, although the hydrogen permeation efficiency of crystalline materials such as vanadium, niobium and the like is high, the service life of the crystalline materials is influenced by the phenomenon of severe hydrogen embrittlement. The amorphous material eliminates the defects of crystal boundary, dislocation and the like due to the unique structure, and has good hydrogen embrittlement resistance; in the using process, hydrogen atoms can be enriched in the amorphous alloy to generate lattice expansion, which is beneficial to hydrogen permeation, so that the amorphous alloy has obvious advantages in the aspect of being used as a hydrogen permeation material.
Most of the hydrogen permeable metal films are obtained by smelting, for example, chinese patent (publication No. CN 1990094A) discloses a method for preparing a hydrogen permeable film, wherein a nickel-zirconium alloy ingot is prepared by smelting, then the ingot is remelted and sprayed on a water-cooled copper roller under pressure to form an amorphous nickel-zirconium alloy foil. Chinese patent (publication No. CN 110306096A) discloses a nickel/titanium/vanadium nanowire alloy hydrogen-permeable film, which is also prepared by firstly obtaining an alloy ingot through smelting and then forging and drawing. The smelting process has high energy consumption, high preparation environment risk, difficulty in obtaining micro-nano films and serious obstruction to hydrogen permeation efficiency due to the thickness of the alloy film.
The utility model discloses a chemical plating and electroplating combined method preparation middle diffusion layer is the compound hydrogen membrane of straining of palladium system of amorphous nickel tungsten alloy, and preparation method is simple, and is lower to the equipment requirement, and energy resource consumption is few, and operational environment security is good, through parameters such as control time and electric current, can obtain the film of micro-nano level, has reduced the barrier effect of thickness to hydrogen permeation efficiency, is fit for popularizing and applying.
SUMMERY OF THE UTILITY MODEL
The utility model aims to develop a palladium-nickel tungsten-palladium composite hydrogen filtering membrane which is prepared on the surface of a porous ceramic support body and has an amorphous alloy middle diffusion layer.
To achieve the above object, the present invention comprises the following components:
a composite hydrogen filtering membrane with an amorphous nickel-tungsten alloy intermediate diffusion layer comprises a porous alumina ceramic support, a pure palladium layer A, an amorphous nickel-tungsten layer and a pure palladium layer B; wherein the porous alumina ceramic support body can be tubular porous alumina ceramic or sheet alumina ceramic, the aperture is required to be 30 nm-2 μm, and the porosity is required to be 20-40%; the thickness of the pure palladium layer A and the pure palladium layer B is 0.5-5 μm, the thickness of the amorphous nickel-tungsten layer is 1-20 μm, and the total thickness of the alloy hydrogen filtering film is 2-30 μm.
A preparation method of a composite hydrogen filtering film with an amorphous nickel-tungsten alloy intermediate diffusion layer comprises the following steps:
(1) Surface pretreatment of porous alumina ceramic support
Placing the porous alumina ceramic support body in 5-20 g/L NaOH solution and deionized water in sequence, and ultrasonically cleaning for 2-10 min to remove oil stains and dust on the surface of the ceramic support body;
(2) Sensitization activation treatment of ceramic support
(1) Immersing the pretreated ceramic support body into SnCl 2 Performing ultrasonic treatment in HCl sensitizing solution for 0.5-10 min, sensitizing, then placing in deionized water, and cleaning for 10-60 s at the ultrasonic position, wherein the concentration of the sensitizing solution is as follows:
SnCl 2 ：3～10g/L；HCl：1mL/L；
(2) placing the sensitized ceramic support in PdCl 2 In HCl activation solutionPerforming sound treatment for 0.5-10 min, activating, then placing in deionized water for ultrasonic cleaning for 10-60 s, wherein the concentration of an activating solution is as follows:
PdCl 2 ：0.1～0.5g/L；HCl：2mL/L；
repeating the steps for 3-10 times to ensure that palladium nuclei are uniformly planted on the surface of the ceramic support body, wherein the surface of the ceramic support body presents uniformly distributed dark brown;
(3) Plating palladium on the surface of the activated ceramic support by using a chemical plating method
Putting the ceramic support body treated in the step (2) into a prepared palladium chloride chemical plating solution, putting the ceramic support body into a water bath kettle at the temperature of 40-70 ℃, magnetically stirring, adding a hydrazine hydrate solution every 5-30 min, changing the chemical plating solution after adding hydrazine hydrate for 3-6 times, repeating the operation for 2-10 times, washing the sample with deionized water for 30-90 s after taking out the sample, and drying the sample with cold air for later use; wherein the concentration requirement of the chemical plating solution of palladium is as follows:
PdCl 2 ：1～4g/L；EDTA：25～50g/L；NH 3 ·H 2 o (25-28%): 200-250 mL/L; hydrazine hydrate: 0.05-0.3 mol/L;
(4) Electroplating nickel tungsten on the surface after chemical palladium plating
Putting the sample treated in the step (3) into a nickel-tungsten plating solution, putting the nickel-tungsten plating solution into a water bath kettle at the temperature of 30-70 ℃, using a pure nickel plate as an anode, setting on-off time and current, electroplating for 5-120 min, taking out the sample, washing the sample with deionized water for 30-90 s, and drying the sample with cold air for later use; wherein the concentration requirement of the nickel-tungsten electroplating solution is as follows:
NiSO 4 ·6H 2 O：10～25g/L；Na 2 WO 4 : 30-60 g/L; citric acid monohydrate: 15-80 g/L; NH (NH) 3 ·H 2 O(25～28％)：2～50mL/L；
The current parameter requirements are:
current density: 50-120 mA/cm 2 ；
Selecting current as forward pulse current, and enabling time to be equal to turn-off time: 1-5 ms;
(5) Surface palladium plating
Repeating the steps (2) and (3) on the sample treated in the step (4), and chemically plating palladium on the surface;
(6) Drying process
And (4) putting the sample plated with palladium in the step (5) into a drying box at the temperature of 100 ℃, and drying for 2-4 h to obtain the composite hydrogen filtering film with the middle diffusion layer made of amorphous nickel-tungsten alloy.
Compared with the prior art, the beneficial effects of the utility model are that:
(1) The chemical plating has lower requirements on the substrate, the obtained pure palladium plating layer has higher binding force with the substrate, the concentration of the palladium solution required by the chemical plating is lower, and the utilization rate of the palladium in the solution is higher.
(2) The palladium is only used on two sides of the composite hydrogen filtering membrane and is used for dissociation and desorption of hydrogen, so that the usage amount of expensive palladium elements is effectively reduced, and the manufacturing cost of the composite hydrogen filtering membrane is reduced.
(3) Compared with other metal alloys, hydrogen atoms are not easy to form metal hydride in the amorphous nickel-tungsten layer, the hydrogen retention is less, the hydrogen embrittlement phenomenon is not easy to occur, and the service life of the composite hydrogen filtering film is prolonged.
Drawings
FIG. 1 is a schematic structural diagram of a sheet-shaped composite hydrogen filtration membrane;
FIG. 2 is an SEM photograph of the surface morphology of the electroplated amorphous nickel tungsten layer;
FIG. 3 is an EDS spectrum of an electroplated amorphous nickel tungsten layer;
FIG. 4 is an XRD spectrum of an electroplated amorphous nickel-tungsten layer;
FIG. 5 is an SEM photograph of the surface topography of an electroless pure palladium layer;
fig. 6 is a schematic structural view of a tubular composite hydrogen filter membrane.
Detailed Description
The present invention will be further explained with reference to the accompanying drawings.
The utility model aims at developing a composite hydrogen permeation membrane with an amorphous middle diffusion layer. In order to achieve the purpose, the utility model takes porous alumina ceramics as a support body and adopts an electroplating mode to obtain an amorphous nickel-tungsten intermediate diffusion layer; pure palladium layers are deposited on two sides of the amorphous nickel-tungsten intermediate diffusion layer in a chemical plating mode to serve as dissociation and desorption layers of hydrogen.
The first embodiment is as follows:
a composite hydrogen filtering membrane with an amorphous nickel-tungsten alloy intermediate diffusion layer comprises a porous alumina ceramic support, a pure palladium layer A, an amorphous nickel-tungsten layer and a pure palladium layer B; wherein the porous alumina ceramic support is a sheet alumina ceramic with the diameter of 18mm, the thickness of 2mm, the aperture of 70nm and the porosity of 30 percent; the average thickness of the pure palladium layer A and the pure palladium layer B is 1.2 mu m, the average thickness of the amorphous nickel-tungsten layer is 15 mu m, and the average total thickness of the alloy hydrogen filtering film is 17.4 mu m. The schematic diagram of the sheet-shaped composite hydrogen filtering film with the middle diffusion layer made of amorphous nickel-tungsten alloy is shown in figure 1.
The preparation method of the composite hydrogen filtering film with the intermediate diffusion layer made of amorphous nickel-tungsten alloy comprises the following steps:
(1) Pretreating the surface of the porous alumina ceramic support: sequentially placing a sheet-shaped porous alumina ceramic support with the diameter of 18mm, the thickness of 2mm, the aperture of 70nm and the porosity of 30% in a NaOH solution and deionized water of 10g/L for ultrasonic cleaning for 5min to remove surface impurities and oil stains, and then blowing surface water by cold air for later use;
(2) Ceramic support sensitization activation treatment
50mL of SnCl solution containing 5g/L was prepared with deionized water 2 And 1mL/L HCl sensitizing solution;
25mL of deionized water containing 0.2g/L PdCl 2 And 2mL/L of HCl in an activating solution;
putting the alumina ceramic support body pretreated in the step (1) into a sensitizing solution for ultrasonic treatment for 3min, then taking out and putting into a beaker filled with deionized water for ultrasonic cleaning for 30s, then putting into a prepared activating solution for ultrasonic treatment for 3min, taking out and putting into the beaker filled with deionized water for ultrasonic cleaning for 30s;
repeating the operation for 5 times, wherein the surface of the porous alumina ceramic presents uniform black brown, and uniform palladium cores are obtained.
(3) Plating palladium on the surface of the activated ceramic support body by using a chemical plating method
Preparing 50mL palladium chloride electroless plating solution with concentration of PdCl by using deionized water 2 ：2g/L； EDTA：31.5g/L；NH 3 ·H 2 O(25％～28％)：230mL/L；
Preparing a hydrazine hydrate solution with the concentration of 0.1mol/L by using deionized water;
taking 25mL of prepared palladium chloride chemical plating solution, putting the ceramic support body treated in the step (2) into the plating solution, and heating in water bath to 60 ℃;
adding 0.2mL of 0.1mol/L hydrazine hydrate into the chemical plating solution, and magnetically stirring;
adding 0.1mol/L hydrazine hydrate every 20min, adding 0.2mL each time, changing the plating solution after 5 times, and repeating the operation for 1 time;
and taking out the sample, washing the sample with deionized water for 30s, and drying the surface with cold air for later use.
(4) Electroplating nickel tungsten on the surface after chemical palladium plating
Preparing 100mL of nickel-tungsten plating solution by using deionized water, wherein the concentration is as follows: niSO 4 ·6H 2 O：13.1g/L； NaWO 4 :49.5g/L; citric acid monohydrate: 31.5g/L; NH (NH) 3 ·H 2 O(25～28％)： 20mL/L；
Setting the current density at 100mA/cm 2 The on-time and the off-time are 2ms, the water bath temperature is 60 ℃, and the electroplating is carried out for 90min;
taking out the sample after the electroplating is finished, washing the sample with deionized water for 30s, and drying the surface with cold air for later use;
the SEM photo of the electroplated amorphous nickel-tungsten layer is shown in figure 2, the EDS spectrum is shown in figure 3, and the XRD spectrum is shown in figure 4.
(5) Surface palladium plating
And (3) repeating the steps (2) and (3) on the sample treated in the step (4), and chemically plating palladium on the surface, wherein an SEM (scanning electron microscope) picture of the surface appearance after palladium plating is shown in FIG. 5.
(6) Drying process
And (4) putting the sample plated with palladium in the step (5) into a drying box at the temperature of 100 ℃, drying for 3h, and taking out to obtain the composite hydrogen filtering film with the middle diffusion layer made of amorphous nickel-tungsten alloy.
Example two:
a composite hydrogen filtering membrane with an amorphous nickel-tungsten alloy intermediate diffusion layer comprises a porous alumina ceramic support, a pure palladium layer A, an amorphous nickel-tungsten layer and a pure palladium layer B; wherein the porous alumina ceramic support body is tubular porous alumina ceramic with the outer diameter of 12mm, the inner diameter of 8mm, the length of 10mm, the aperture of 1.5 mu m and the porosity of 37 percent; the average thickness of the pure palladium layer A and the pure palladium layer B is 1.4 mu m, the average thickness of the amorphous nickel-tungsten layer is 13 mu m, and the average total thickness of the composite hydrogen filtering film is 15.8 mu m. Fig. 6 shows a schematic diagram of a tubular composite hydrogen filtering membrane with an amorphous nickel-tungsten alloy intermediate diffusion layer.
The preparation method of the composite hydrogen filtering film with the intermediate diffusion layer made of amorphous nickel-tungsten alloy comprises the following steps:
(1) Pretreating the surface of the porous alumina ceramic support: placing a tubular porous alumina ceramic support body with the outer diameter of 12mm, the inner diameter of 8mm, the length of 10mm, the aperture of 1.5 mu m and the porosity of 37% in a NaOH solution of 15g/L and deionized water in sequence, ultrasonically cleaning for 3min to remove surface impurities and oil stains, blow-drying surface moisture by cold air, and sealing pipe holes at two sides by rubber plugs for later use;
(2) Ceramic support sensitization activation treatment
50mL of SnCl solution containing 7g/L was prepared with deionized water 2 And 1mL/L HCl sensitizing solution;
25mL of deionized water containing 0.3g/L PdCl 2 And 2mL/L HCl in the activating solution;
putting the alumina ceramic support body pretreated in the step (1) into a sensitizing solution for ultrasonic treatment for 2min, then taking out and putting into a beaker filled with deionized water for ultrasonic cleaning for 30s, then putting into a prepared activating solution for ultrasonic treatment for 2min, taking out and putting into the beaker filled with deionized water for ultrasonic treatment for 30s;
repeating the operation for 5 times, wherein the surface of the porous alumina ceramic presents uniform black brown, and uniform palladium cores are obtained.
(3) Plating palladium on the surface of the activated ceramic support by using a chemical plating method
Preparing 50mL palladium chloride electroless plating solution with concentration of PdCl by using deionized water 2 ：3g/L； EDTA：40g/L；NH 3 ·H 2 O(25％～28％)：230mL/L；
Preparing a hydrazine hydrate solution with the concentration of 0.15mol/L by using deionized water;
taking 25mL of prepared palladium chloride chemical plating solution, putting the ceramic support body treated in the step (2) into the plating solution, and heating in water bath to 50 ℃;
adding 0.15mol/L hydrazine hydrate every 15min, adding 0.2mL each time, changing the plating solution after 5 times, and repeating the operation for 1 time;
and taking out the sample, washing the sample with deionized water for 30s, and drying the surface with cold air for later use.
(4) Electroplating nickel tungsten on the surface of the sample after chemical palladium plating
Preparing 100mL of nickel-tungsten plating solution by using deionized water, wherein the concentration is as follows: niSO 4 ·6H 2 O：18.4g/L；NaWO 4 :33g/L; citric acid monohydrate: 21g/L; NH 3 ·H 2 O(25～28％)：20mL/L；
The current density is set to be 80mA/cm 2 The on-time and the off-time are 2ms, the water bath temperature is 60 ℃, and the electroplating is carried out for 90min;
and (4) taking out the sample after the electroplating is finished, washing the sample with deionized water for 30s, and drying the surface with cold air.
(5) Surface palladium plating
And (3) repeating the steps (2) and (3) on the sample treated in the step (4), and chemically plating palladium on the surface.
(6) Drying process
And (4) washing the sample plated with palladium in the step (5) with deionized water for 60s, putting the sample into a drying box at the temperature of 100 ℃, drying for 3h, and taking out the sample to obtain the composite hydrogen filtering film with the intermediate diffusion layer made of amorphous nickel-tungsten alloy.
Claims (1)
1. A composite hydrogen filtering film with an intermediate diffusion layer made of amorphous nickel-tungsten alloy is characterized by comprising a porous alumina ceramic support body, a pure palladium layer A, an amorphous nickel-tungsten layer and a pure palladium layer B; wherein the porous alumina ceramic support body can be tubular porous alumina ceramic or sheet alumina ceramic, the aperture is required to be 30 nm-2 μm, and the porosity is required to be 20-40%; the thickness of the pure palladium layer A and the pure palladium layer B is 0.5-5 μm, the thickness of the amorphous nickel-tungsten layer is 1-20 μm, and the total thickness of the alloy hydrogen filtering film is 2-30 μm.
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