CN111111463A - Finger-type palladium-based composite membrane with gap structure and preparation and application thereof - Google Patents
Finger-type palladium-based composite membrane with gap structure and preparation and application thereof Download PDFInfo
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- CN111111463A CN111111463A CN201811293519.8A CN201811293519A CN111111463A CN 111111463 A CN111111463 A CN 111111463A CN 201811293519 A CN201811293519 A CN 201811293519A CN 111111463 A CN111111463 A CN 111111463A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
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- 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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- 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
- C01—INORGANIC CHEMISTRY
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- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/001—Physical processing by making use of membranes
- C01B2210/0012—Physical processing by making use of membranes characterised by the membrane
Abstract
The invention relates to a preparation method of a finger-type palladium-based composite membrane with a gap structure. Comprises a palladium membrane or a palladium alloy membrane deposited on a porous material, wherein the palladium-based composite membrane is of a finger-type structure, and a gap exists between the palladium-based membrane and the porous material. The preparation method comprises the following steps: carbonate nano particle suspension is used for modifying surface defects and pinholes of the porous material, a palladium or palladium alloy membrane is prepared on the surface of the porous metal by a chemical plating method or a method combining chemical plating and electroplating, and then a gap structure is formed between the palladium-based membrane and the porous material by high-temperature treatment and carbonate decomposition. The finger-type structure palladium-based composite membrane can realize free expansion and contraction of the palladium membrane in the process of rapid temperature rise and drop, and the gap structure can avoid direct contact between the palladium-based membrane and the surface of the porous material, thereby improving the stability of the palladium-based composite membrane. The finger-type structure palladium-based composite membrane has mature preparation process, is simple and feasible, and can be used for ultra-pure hydrogen separation, ammonia decomposition or methanol steam reforming palladium membrane reactors and the like to provide hydrogen sources for fuel cells.
Description
Technical Field
The invention relates to a preparation method of a palladium-based composite membrane, in particular to a preparation method of a palladium-based composite membrane with a finger-type structure, which is particularly suitable for preparing the finger-type palladium-based composite membrane with a gap structure.
Background
Hydrogen energy is an ideal clean energy and is known as the secondary energy with the most development prospect in the 21 st century. Rapid development of electronic information, semiconductors, LEDs, optical fibers, and large-scale integrated circuits, promoting ultra-high purity hydrogen gas: (>99.9999%) and also promotes the development of hydrogen production technology and hydrogen separation and purification technology. At present, the source of hydrogen is mainly converted from fossil fuels such as coal, petroleum or natural gas, and the converted hydrogen generally contains CO and CO2And the impurities need to be separated and purified to obtain hydrogen with different purities. Common separation methods are Pressure Swing Adsorption (PSA), cryogenic separation and membrane separation. Compared with pressure swing adsorption and cryogenic separation, the membrane separation has the characteristics of low investment, simple equipment, low energy consumption, small volume, safety, no environmental pollution and the like.
The palladium and its alloy membrane has the characteristics of good hydrogen permeability and high temperature resistance, and thus has attracted much attention in the aspects of hydrogen separation and purification. At present, the commercialized palladium membrane is almost a self-supporting palladium tube, and due to the limitations of mechanical strength, ductility and the like, the thickness of the palladium membrane is generally required to be more than 100 μm, so that a large amount of noble metal palladium is needed, and the hydrogen permeation amount is low. In order to overcome the defect, people develop a metal palladium composite membrane, namely a metal palladium layer is deposited on the surface of a porous carrier, the thickness of the supported palladium membrane is generally several microns to dozens of microns, and compared with a palladium tube with the thickness of hundreds of microns, the supported palladium membrane not only saves a large amount of noble metal palladium, but also improves the hydrogen permeation amount and enhances the mechanical strength.
The porous carrier mainly comprises a porous ceramic pipe and a porous stainless steel pipe, and the porous ceramic pipe and the porous stainless steel pipe are most widely applied. The palladium membrane carriers involved in the prior documents and patent reports are almost all of the single channel type, and the palladium membrane is formed on the outer side or the inner side of the tubular carrier. Because the membrane area of each single-channel palladium composite membrane is limited, in practical application, a large number of single-channel membrane tubes are usually required to be used for keeping a certain membrane area, so that the structure of the membrane separator is extremely complex, the volume of the membrane separator is large, the equipment investment is improved, and the palladium/ceramic membrane tubes are complex and fragile in sealing connection, so that much inconvenience is brought to transportation and practical application. Compared with the porous ceramic tube, the porous stainless steel tube has the advantages of simple sealing (welding), capability of realizing tight accumulation, higher mechanical strength and more compact structure of the reactor.
The surface of the porous stainless steel carrier has larger defects and pinholes and has larger roughness, so that the continuous and compact palladium membrane is difficult to directly prepare on the surface, the surface defects and the pinholes of the porous carrier generally need to be modified before the palladium membrane is chemically plated, but an intermediate layer is formed between the palladium membrane and the carrier, so that the hydrogen diffusion resistance is increased. There is a report in the literature that a new method of combining organic and inorganic phases (ding Jianhua, Su linking, Kenji Haraya, Hiroyuki Suda, chem. commun.,2006, 1142-1144) is used, and a palladium membrane prepared by the method can prevent resistance of an intermediate layer to gas diffusion due to the formation of a gap between the palladium membrane and a support, prevent alloy formation by interdiffusion between the palladium membrane and a porous metal support at a high temperature to reduce the stability of the palladium membrane, and prevent the palladium membrane from being peeled off from the porous ceramic support when used at a high temperature. The palladium membrane prepared by the method can obtain higher hydrogen permeability, infinite hydrogen selectivity and better stability. Therefore, when the palladium-based composite membrane is prepared, a gap is formed between the palladium membrane and the surface of the porous carrier, so that the stability of the palladium membrane can be improved.
Disclosure of Invention
The invention aims to solve the technical problem of how to improve the stability of a palladium composite membrane and the structural compactness of a palladium membrane reactor, and provides a method for preparing a 'finger-type' palladium-based composite membrane with a gap structure.
The specific technical scheme of the invention is as follows:
a 'finger-type' palladium-based composite membrane with an interstitial structure, which comprises a palladium membrane or a palladium alloy membrane deposited on the surface of a porous material, and is characterized in that: the palladium-based composite membrane is of a finger-type structure, and discontinuous contact points exist between the palladium-based membrane and the porous material, and the rest are gaps.
The porous material is tubular, porous ceramic or porous stainless steel, and the average pore diameter of the surface of the porous material is 0.1-50 mu m.
The finger-shaped structure is a hollow tubular structure with one end sealed and the other end open, the sealed end is a hollow hemispherical structure, the diameter of the hemisphere is the same as that of the hollow tube, the porous material is the same from the open end to the sealed end, the open end is connected with the extension tube, if the porous ceramic material is adopted, the outer wall of the extension tube is coated with the high-temperature sintered glass glaze, if the porous metal material is adopted, the extension tube is a compact stainless steel tube sintered with the porous material at one time, or the compact stainless steel tube is connected with the porous metal material in a welding mode, and the diameter of the finger-shaped porous material is 2-20 mm.
The gap is formed between the palladium-based membrane and the porous material by decomposing carbonate during high-temperature treatment and has discontinuous contact points. The existence of the gap structure can avoid direct contact between the palladium membrane and the porous material and get rid of the influence caused by the difference of thermal expansion coefficients of different materials.
The invention also relates to a preparation method of the finger-type palladium-based composite membrane with the gap structure, which comprises the following steps:
a) modifying the surface defects and pinholes of the porous material by adopting a carbonate nano-particle suspension, and then drying;
b) preparing a palladium or palladium alloy film on the outer surface of the modified porous material by adopting a chemical plating method or a method combining chemical plating and electroplating;
c) under the protection of pressure, carbonate is decomposed through high-temperature treatment, and a gap structure is formed between the palladium-based membrane and the porous material.
The carbonate is one or more of manganese carbonate, nickel carbonate, copper carbonate, calcium carbonate, zinc carbonate and magnesium carbonate, the size of carbonate particles is 5-500nm, the porous material modified by carbonate nanoparticle suspension is dried at the temperature of 100-150 ℃.
In the literature, there are many methods for preparing the metal palladium composite membrane, such as chemical plating, electroplating, chemical vapor deposition, physical vapor deposition, magnetron sputtering, plasma spraying, and photocatalytic methods, and chemical plating is generally known as the most successful process for preparing the dense palladium membrane. The method can deposit the palladium membrane with uniform thickness on the surface of the carrier with a complex shape, and has simple operation and good membrane forming compactness. The chemical plating process generally comprises four steps of pretreatment of a carrier, surface activation sensitization, chemical plating, post-treatment and the like. The surface sensitization activation method is many, most of the methods are to deposit metal palladium particles on the surface of a carrier, and the commonly used method is SnCl2/PdCl2The method is carried out. The palladium membrane is prepared by adopting a chemical plating method, and the typical plating solution comprises the following components: [ Pd (NH)3)2]Cl2(1～8g/L)，EDTA·2Na(20～90g/L)，NH2-NH2·H2O(0.2～1g/L),NH3·H2O (28%) (100-500 ml/L) and the balance of deionized water, wherein the pH value is 9-11.
The palladium alloy membrane is prepared by preparing the palladium membrane by adopting a chemical plating method, depositing at least one other metal on the surface of the palladium membrane by adopting chemical plating or electroplating, and carrying out alloying treatment. Many palladium alloy films reported in the literature include two-phase alloys and three-phase alloys, and the two-phase alloy films include palladium-silver, palladium-copper, palladium-gold, palladium-ruthenium, and the like, and the three-phase alloysThe gold film includes palladium-copper-silver alloy, palladium-gold-copper alloy, and the like. The common preparation method can adopt the steps of firstly plating palladium chemically, then depositing other metals on the surface of the palladium film by a chemical plating or electroplating method, and finally alloying. For example, an electroless plating method is used to prepare a palladium-ruthenium film, and the composition of the ruthenium plating solution used is as follows: RuCl3·3H2O(0.2-0.77g/L)，NH3·3H2O(28wt％)(50-300ml/L)，HCl(37wt％)(0.2-1.2ml/L)，NH2-NH2·H2O (0.2-1.5 g/L), Polyetheneimine (1-20mg/L) and the balance of deionized water, wherein the pH value is 9-11, and the temperature is 50-85 ℃. The typical alloying treatment method is as follows: under an inert atmosphere (e.g., N)2) The film is heated to 400 ℃, then is switched to hydrogen, is kept at 800 ℃ of 500-: n is a radical of2) And cooling to room temperature to obtain the palladium alloy membrane.
The chemical plating method is adopted, a palladium membrane is formed on the surface of the porous material modified by the carbonate nano particle suspension, high-temperature treatment is needed, the treatment temperature is 400-600 ℃, carbonate is decomposed, carbon dioxide generated by the decomposition of the carbonate reacts on the palladium membrane, and the palladium membrane is locally broken, so that certain pressure needs to be applied to the surface of the palladium membrane to protect the palladium membrane, and the protection pressure is 0.1-1.0 MPa.
Has the advantages that:
compared with the existing preparation method of the palladium membrane, the finger-type palladium-based composite membrane with the gap structure provided by the invention has the advantages that the gap exists between the palladium membrane and the porous carrier, so that the direct contact between the palladium membrane and the porous material can be avoided, and the design of the finger-type porous carrier can realize the free expansion and contraction of the palladium membrane along the axial direction of the tubular porous carrier in the rapid temperature rise and drop process, so that the influence caused by the thermal expansion difference among different materials is avoided, and the stability of the palladium membrane is improved.
The present invention will be described in detail with reference to specific examples. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
Description of the drawings:
FIG. 1 is a schematic representation of a palladium membrane of the "finger" structure.
Fig. 2 is a cross-sectional SEM image of the palladium-based composite membrane having a gap structure prepared in example 1.
Detailed Description
A method for preparing a finger-type palladium-based composite membrane with a gap structure comprises the step of depositing a palladium membrane or a palladium alloy membrane on the surface of a porous material, and the specific preparation method comprises the following steps:
example 1
1) Finger-type porous stainless steel with the average pore diameter of 0.5 mu m and the maximum pore diameter of 20 mu m is selected as a carrier of the palladium membrane, the outer diameter is 6mm, the inner diameter is 4mm, and the length of the porous carrier is 5 cm.
2) Pretreatment of a carrier: soaking a finger-shaped porous stainless steel carrier in 5 wt% of dilute hydrochloric acid for 10 minutes at normal temperature, and cleaning with deionized water for 5 minutes by adopting a vacuumizing method; soaking in absolute ethyl alcohol for 20 minutes, and washing with deionized water for 5 minutes under the condition of vacuum pumping; soaking in dilute potassium hydroxide solution (4 wt%) for 10 min, vacuum cleaning with deionized water until the residual liquid is neutral, and drying at 120 deg.C.
3) And (3) carrying out surface defect modification on the carrier: immersing the pretreated carrier in 200ml suspension containing 5g manganese carbonate particles (50nm) under vacuum condition, keeping for 30 seconds, taking out, mechanically polishing the surface of the porous carrier by using a film, washing the surface by using a large amount of deionized water, and finally drying at 120 ℃.
4) Activation and sensitization: soaking the carrier with surface defect in deionized water, and adding SnCl2The solution (6g/L) was sensitized for 5 minutes and rinsed with deionized water in PdCl2The solution (0.4g/L) was activated for 5 minutes and rinsed with deionized water, and after 5 repeated sensitization-activation, it was rinsed with deionized water for 5 minutes under vacuum.
5) Chemical plating: immersing the sensitized and activated carrier into a palladium plating solution to carry out chemical palladium plating. The composition of the plating solution is [ Pd (NH)3)2]Cl2(4g/L)，EDTA·2Na(65g/L)，NH2-NH2·H2O(0.6g/L),NH3·H2O(28％)(300ml/L)，，The balance of deionized water, and the pH value is 10.
6) And electroless plating for 5 hours.
7) The prepared palladium membrane was washed thoroughly with deionized water and then dried overnight at 120 ℃. The total thickness of the palladium membrane is about 8.5 μm. The permeability of the palladium membrane at room temperature is measured by adopting nitrogen, and the nitrogen permeation quantity is close to 0 under the pressure of 0.1 MPa.
8) Heat treatment and hydrogen permeability of palladium membranes: heating to 450 deg.C in nitrogen according to a certain heating program, measuring nitrogen and hydrogen permeability under 0.1MPa, and separating factor (H)2/N2) Is measured by using the ratio of the hydrogen permeation quantity/the nitrogen permeation quantity at 450 ℃ and under the pressure difference of 0.1 MPa. From the experimental data, it can be seen that a dense metal palladium composite membrane is formed.
Example 2:
1) finger-type porous stainless steel with the average pore diameter of 0.2 mu m and the maximum pore diameter of 15 mu m is selected as a carrier of the palladium membrane, the outer diameter is 8mm, the inner diameter is 5mm, and the length of the porous carrier is 10 cm.
2) Pretreatment of a carrier: soaking a finger-shaped porous stainless steel carrier in 5 wt% of dilute hydrochloric acid for 10 minutes at normal temperature, and cleaning with deionized water for 5 minutes by adopting a vacuumizing method; soaking in absolute ethyl alcohol for 20 minutes, and washing with deionized water for 5 minutes under the condition of vacuum pumping; soaking in dilute potassium hydroxide solution (4 wt%) for 10 min, vacuum cleaning with deionized water until the residual liquid is neutral, and drying at 120 deg.C.
3) And (3) carrying out surface defect modification on the carrier: the pretreated support was immersed in 200ml of a suspension containing 3g of copper carbonate particles (25nm) under vacuum for 60 seconds, taken out and mechanically polished with a thin film on the porous support surface, then the surface was rinsed with a large amount of deionized water and finally dried at 120 ℃.
4) Activation and sensitization: soaking the carrier with surface defect in deionized water, and adding SnCl2The solution (4g/L) was sensitized for 5 minutes and rinsed with deionized water in PdCl2The solution (0.6g/L) was activated for 5 minutes and rinsed with deionized water, and after 5 repeated sensitization-activation, it was rinsed with deionized water for 5 minutes under vacuum.
5) Chemical plating: immersing the sensitized and activated carrier into a palladium plating solution to carry out chemical palladium plating. The composition of the plating solution is [ Pd (NH)3)2]Cl2(3g/L)，EDTA·2Na(45g/L)，NH2-NH2·H2O(0.4g/L),NH3·H2O (28%) (300ml/L), the remainder deionized water, pH ═ 10.
6) And electroless plating for 5 hours.
7) The prepared palladium membrane was washed thoroughly with deionized water and then dried overnight at 120 ℃. The total thickness of the palladium membrane is about 8.1 μm. The permeability of the palladium membrane at room temperature is measured by adopting nitrogen, and the nitrogen permeation quantity is close to 0 under the pressure of 0.1 MPa.
8) Heat treatment and hydrogen permeability of palladium membranes: heating to 450 deg.C in nitrogen according to a certain heating program, measuring nitrogen and hydrogen permeability under 0.1MPa, and separating factor (H)2/N2) Is measured by using the ratio of the hydrogen permeation quantity/the nitrogen permeation quantity at 450 ℃ and under the pressure difference of 0.1 MPa. From the experimental data, it can be seen that a dense metal palladium composite membrane is formed.
Example 3:
1) finger-type porous ceramic with the average pore diameter of 0.5 mu m and the maximum pore diameter of 30 mu m is selected as a carrier of the palladium membrane, the outer diameter is 12mm, the inner diameter is 7mm, and the length of the porous carrier is 10 cm.
2) Pretreatment of a carrier: soaking a finger-shaped porous stainless steel carrier in 5 wt% of dilute hydrochloric acid for 10 minutes at normal temperature, and cleaning with deionized water for 5 minutes by adopting a vacuumizing method; soaking in absolute ethyl alcohol for 20 minutes, and washing with deionized water for 5 minutes under the condition of vacuum pumping; soaking in dilute potassium hydroxide solution (4 wt%) for 10 min, vacuum cleaning with deionized water until the residual liquid is neutral, and drying at 120 deg.C.
3) And (3) carrying out surface defect modification on the carrier: immersing the pretreated carrier into 200ml of suspension containing 3g of calcium carbonate particles (25nm) and 2g of magnesium carbonate particles (50nm) under vacuum, keeping for 60 seconds, taking out, mechanically polishing the surface of the porous carrier by using a film, washing the surface by using a large amount of deionized water, and finally drying at 120 ℃.
4) Activation and sensitization: soaking the carrier with surface defect in deionized water, and adding SnCl2The solution (4g/L) was sensitized for 5 minutes and rinsed with deionized water in PdCl2The solution (0.6g/L) was activated for 5 minutes and rinsed with deionized water, and after 5 repeated sensitization-activation, it was rinsed with deionized water for 5 minutes under vacuum.
5) Chemical plating: immersing the sensitized and activated carrier into a palladium plating solution to carry out chemical palladium plating. The composition of the plating solution is [ Pd (NH)3)2]Cl2(3g/L)，EDTA·2Na(45g/L)，NH2-NH2·H2O(0.4g/L),NH3·H2O (28%) (300ml/L), the remainder deionized water, pH ═ 10.
6) And electroless plating for 5 hours.
7) The prepared palladium membrane was washed thoroughly with deionized water and then dried overnight at 120 ℃. The total thickness of the palladium membrane is about 8.1 μm. The permeability of the palladium membrane at room temperature is measured by adopting nitrogen, and the nitrogen permeation quantity is close to 0 under the pressure of 0.1 MPa.
8) Heat treatment and hydrogen permeability of palladium membranes: heating to 450 deg.C in nitrogen according to a certain heating program, measuring nitrogen and hydrogen permeability under 0.1MPa, and separating factor (H)2/N2) Is measured by using the ratio of the hydrogen permeation quantity/the nitrogen permeation quantity at 450 ℃ and under the pressure difference of 0.1 MPa. From the experimental data, it can be seen that a dense metal palladium composite membrane is formed.
Example 4
1) Finger-type porous stainless steel with the average pore diameter of 0.5 mu m and the maximum pore diameter of 45 mu m is selected as a carrier of the palladium membrane, the outer diameter is 8mm, the inner diameter is 5mm, and the length of the porous carrier is 10 cm.
2) Pretreatment of a carrier: soaking a finger-shaped porous stainless steel carrier in 5 wt% of dilute hydrochloric acid for 10 minutes at normal temperature, and cleaning with deionized water for 5 minutes by adopting a vacuumizing method; soaking in absolute ethyl alcohol for 20 minutes, and washing with deionized water for 5 minutes under the condition of vacuum pumping; soaking in dilute potassium hydroxide solution (4 wt%) for 10 min, vacuum cleaning with deionized water until the residual liquid is neutral, and drying at 120 deg.C.
3) And (3) carrying out surface defect modification on the carrier: immersing the pretreated carrier in 200ml suspension containing 3g of manganese carbonate particles (25nm) and 5g of zinc carbonate particles (100nm) under vacuum for 60 seconds, taking out, mechanically polishing the surface of the porous carrier by using a film, washing the surface by using a large amount of deionized water, and finally drying at 120 ℃.
4) Activation and sensitization: soaking the carrier with surface defect in deionized water, and adding SnCl2The solution (8g/L) was sensitized for 5 minutes and rinsed with deionized water in PdCl2The solution (0.65g/L) was activated for 5 minutes and rinsed with deionized water, and after 5 repeated sensitization-activation, it was rinsed with deionized water for 5 minutes under vacuum.
5) Chemical plating: immersing the sensitized and activated carrier into a palladium plating solution to carry out chemical palladium plating. The composition of the plating solution is [ Pd (NH)3)2]Cl2(5g/L)，EDTA·2Na(70g/L)，NH2-NH2·H2O(0.7g/L),NH3·H2O (28%) (300ml/L), the remainder deionized water, pH ═ 10.
6) And electroless plating for 5 hours.
7) And (4) fully washing the prepared palladium membrane by using deionized water, and repeating the operation of the step 4).
8) Chemical plating of ruthenium: and immersing the sensitized and activated carrier into ruthenium plating solution to carry out chemical plating of ruthenium film. The composition of the plating solution is RuCl3·3H2O(0.5g/L)，NH3·3H2O(28wt％)(150ml/L)，HCl(37wt％)(0.5ml/L)，NH2-NH2·H2O (0.5g/L), Polyetheneimine (3mg/L) and the balance of deionized water, wherein the pH value is 9-11, and the temperature is 50-80 ℃.
9) Electroless plating was performed for 0.5 hour.
10) The prepared palladium-ruthenium film was thoroughly washed with deionized water and then dried at 120 ℃ overnight. The total thickness of the palladium membrane is about 8.1 μm. The permeability of the palladium membrane at room temperature is measured by adopting nitrogen, and the nitrogen permeation quantity is close to 0 under the pressure of 0.1 MPa.
11) Heat treatment and hydrogen permeability of palladium membranes: heating to 450 deg.C in nitrogen according to a certain heating program, switching to hydrogen, heating to 650 deg.C, maintaining for 8 hr, alloying, cooling to 450 deg.C in hydrogen atmosphere, measuring permeability of hydrogen and nitrogen under 0.1MPa, and separating factor (H)2/N2) Is measured by using the ratio of the hydrogen permeation quantity/the nitrogen permeation quantity at 450 ℃ and under the pressure difference of 0.1 MPa. From the experimental data, it can be seen that a dense metal palladium composite membrane is formed.
Example 5
1) Finger-type porous stainless steel with the average pore diameter of 0.5 mu m and the maximum pore diameter of 40 mu m is selected as a carrier of the palladium membrane, the outer diameter is 10mm, the inner diameter is 7mm, and the length of the porous carrier is 15 cm.
2) Pretreatment of a carrier: soaking a finger-shaped porous stainless steel carrier in 5 wt% of dilute hydrochloric acid for 10 minutes at normal temperature, and cleaning with deionized water for 5 minutes by adopting a vacuumizing method; soaking in absolute ethyl alcohol for 20 minutes, and washing with deionized water for 5 minutes under the condition of vacuum pumping; soaking in dilute potassium hydroxide solution (4 wt%) for 10 min, vacuum cleaning with deionized water until the residual liquid is neutral, and drying at 120 deg.C.
3) And (3) carrying out surface defect modification on the carrier: immersing the pretreated carrier into 200ml of suspension containing 3g of manganese carbonate particles (15nm) and 5g of nickel carbonate particles (500nm) under vacuum, keeping for 60 seconds, taking out, mechanically polishing the surface of the porous carrier by using a film, washing the surface by using a large amount of deionized water, and finally drying at 120 ℃.
4) Activation and sensitization: soaking the carrier with surface defect in deionized waterWet, then separately in SnCl2The solution (8g/L) was sensitized for 5 minutes and rinsed with deionized water in PdCl2The solution (0.85g/L) was activated for 5 minutes and rinsed with deionized water, and after 5 repeated sensitization-activation, it was rinsed with deionized water for 5 minutes under vacuum.
5) Chemical plating: immersing the sensitized and activated carrier into a palladium plating solution to carry out chemical palladium plating. The composition of the plating solution is [ Pd (NH)3)2]Cl2(6g/L)，EDTA·2Na(50g/L)，NH2-NH2·H2O(0.7g/L),NH3·H2O (28%) (350ml/L), balance deionized water, pH ═ 10.
6) And electroless plating for 5 hours.
7) The prepared palladium membrane was thoroughly washed with deionized water.
8) Electroplating copper on the surface of the palladium film: the composition of the copper plating solution is Cu (NO)3)2·3H2O(9.6g/L)，Na2EDTA(29.8g/L)，NaOH(11g/L),K4[Fe(CN)6]·3H2O (3g/L), 2-2 bipyridine (20mg/L) and the balance of deionized water, the temperature is 25 ℃, and the current density is 2 ASD.
9) And electroless plating for 1 hour.
10) The prepared palladium-copper film was thoroughly washed with deionized water and then dried at 120 ℃ overnight. The total thickness of the palladium membrane is about 9.2 μm. The permeability of the palladium membrane at room temperature is measured by adopting nitrogen, and the nitrogen permeation quantity is close to 0 under the pressure of 0.1 MPa.
11) Heat treatment and hydrogen permeability of palladium membranes: heating to 450 deg.C in nitrogen according to a certain heating program, switching to hydrogen, heating to 650 deg.C, maintaining for 8 hr, alloying, cooling to 450 deg.C in hydrogen atmosphere, measuring permeability of hydrogen and nitrogen under 0.1MPa, and separating factor (H)2/N2) Is measured by using the ratio of the hydrogen permeation quantity/the nitrogen permeation quantity at 450 ℃ and under the pressure difference of 0.1 MPa. From the experimental data, it can be seen that a dense metal palladium composite membrane is formed.
The finger-type structure palladium-based composite membrane can realize free expansion and contraction of the palladium membrane along the axial direction in the rapid temperature rise and drop process, and the gap structure can avoid direct contact between the palladium-based membrane and the surface of the porous material, thereby improving the stability of the palladium-based composite membrane. The finger-type structure palladium-based composite membrane has mature preparation process, is simple and feasible, and can be used for ultra-pure hydrogen separation, ammonia decomposition or methanol steam reforming palladium membrane reactor and the like to provide hydrogen sources for fuel cells.
Claims (10)
1. A finger-type palladium-based composite membrane with a gap structure comprises a palladium membrane or a palladium alloy membrane deposited on the outer surface of a hollow finger-type porous material, and is characterized in that: the palladium-based composite membrane is of a hollow finger-shaped structure, discontinuous contact points exist between the palladium-based membrane and the porous material, and gaps exist among the palladium-based membrane and the porous material.
2. The palladium-based composite membrane according to claim 1, wherein: the porous material is tubular porous ceramic or tubular porous stainless steel with one end open and the other end provided with a hemispherical plug protruding away from the open end, and the average pore diameter of the outer surface of the porous material is 0.1-50 mu m.
3. The palladium-based composite membrane according to claim 1 or 2, characterized in that: the finger-shaped structure is a hollow tubular structure with one end provided with a hemispherical plug protruding away from the opening end and the other end provided with an opening, the plug end is a hollow hemispherical structure, the diameter of the hemisphere is the same as that of the hollow tube, the same porous material is arranged from the opening end to the plug end, and the outer diameter of the hollow tube is 2-20 mm.
4. The palladium-based composite membrane according to claim 1, wherein: the gap is formed between the palladium-based membrane and the porous material during high-temperature treatment and has discontinuous contact points.
5. A method for preparing a 'finger-type' palladium-based composite membrane with a gap structure according to any one of claims 1 to 4, comprising the steps of:
1) under the condition of vacuumizing the interior of the hollow finger-shaped porous material, modifying the outer surface defects and pinholes of the hollow finger-shaped porous material by soaking in a carbonate nano particle suspension, and then drying;
2) preparing a palladium or palladium alloy film on the outer surface of the modified porous material by adopting a chemical plating method or a method combining chemical plating and electroplating;
3) under the pressure protection, the carbonate is decomposed through high-temperature treatment, and an interstitial structure with discontinuous contact points is formed between the palladium-based membrane and the porous material.
6. The method for preparing a finger-type palladium-based composite membrane with a gap structure according to claim 5, wherein the method comprises the following steps: the carbonate in the step 1) is one or more than two of manganese carbonate, nickel carbonate, copper carbonate, calcium carbonate, zinc carbonate and magnesium carbonate;
the size of the carbonate nano particles in the step 1) is 5-500 nm;
the drying temperature in the step 1) is 100-150 ℃.
7. The method for preparing a finger-type palladium-based composite membrane with a gap structure according to claim 5, wherein the method comprises the following steps: in the step 2), a chemical plating method is adopted to prepare the palladium membrane, and the plating solution comprises the following components: [ Pd (NH)3)2]Cl2(1～8g/L)，EDTA·2Na(20～90g/L)，NH2-NH2·H2O(0.2～1g/L),NH3·H2O (28%) (100-500 ml/L) and the balance of deionized water, wherein the pH value is 9-11.
8. The method for preparing a 'finger-type' palladium-based composite membrane with a gap structure according to claim 5 or 7, wherein the method comprises the following steps: in the step 2), a chemical plating method is adopted to prepare the palladium membrane, then at least one other metal is deposited on the surface of the palladium membrane by chemical plating or electroplating, the palladium alloy membrane is prepared after alloying treatment, the other metal is one or more than two of gold, silver, copper, ruthenium, platinum and the like, and the corresponding other metal source in the plating solution is one or more than two of metal chloride, nitric acid compound or acetic acid compound.
9. The method for preparing a finger-type palladium-based composite membrane with a gap structure according to claim 5, wherein the method comprises the following steps: the protective pressure in the step 3) is 0.1-1.0 MPa;
the treatment temperature in the step 3) is 400-.
10. Use of a "finger-type" palladium-based composite membrane having a gap structure according to any one of claims 1 to 4 in hydrogen separation.
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