Process for carrying out hydrogen involving reactions

Abstract

The present application relates to hydrogen purification technical field, a kind of method for hydrogen reaction, the method comprises: (a) according to the hydrogen permeation diffusion rate J required by hydrogen reaction H2 Determine the lattice parameter k of palladium membrane;(b) provide palladium membrane with the lattice parameter;(c) carry out hydrogen reaction in the presence of provided palladium membrane.The present application can realize the controllable preparation of palladium membrane with different lattice parameters by establishing the correspondence between hydrogen permeation diffusion rate and lattice parameter, that is, the skilled person in the art can select the corresponding alloying treatment conditions based on different needs, and then a series of palladium membranes with excellent performance, such as good hydrogen separation performance, high mechanical strength, long service life and good stability, can be conveniently prepared in large quantities.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen purification, in particular to a method for carrying out hydrogen-related reactions. BACKGROUND

[0002] In the field of high-purity hydrogen production, palladium membrane separation technology has the characteristics of small investment, low energy consumption, high stability, and environmental protection. In view of the problem that trace impurities (such as N2, Ar, CO2, etc.) cannot be completely removed in the traditional pressure swing adsorption process, palladium membrane separation follows the principle of dissolution and diffusion, perfectly solving the above problems, and is a high-purity hydrogen separation and purification process with great application prospect. However, when the temperature is <573K, pure palladium membrane will form two solid solutions with different lattice parameters (a) after dissolving hydrogen, namely α-PdH and β-PdH Two kinds of solid solutions with different lattice parameters (a); this structure will cause uneven shrinkage and expansion of the palladium membrane after multiple dissolution and precipitation cycles, resulting in hydrogen embrittlement and rupture, thereby greatly limiting the application of palladium membrane at low temperature and high pressure. Related studies have shown that palladium-copper alloy membranes with body-centered cubic structure can greatly widen the low-temperature fatigue resistance of the membrane material. At the same time, it also reduces the amount of noble metal palladium and lowers the production cost.

[0003] In recent years, related research reports that alloy membrane materials loaded on porous ceramics, porous stainless steel, high borosilicate heat-resistant glass and other carriers can be obtained by chemical plating, electroplating, chemical vapor deposition and physical vapor deposition. However, the above preparation methods can only adjust the macroscopic factors such as the composition and thickness of the alloy membrane material, and cannot control the microcrystal lattice structure and lattice parameters of the membrane material. The plastic deformation mode of different crystal structures will determine whether the alloy membrane material can exhibit high strength in a wide temperature range and under a large strain state. Therefore, the control of the crystal structure inside the alloy membrane is still a key problem that needs to be solved in the field of metal separation membrane material preparation.

[0004] Different hydrogen-related reactions require different hydrogen permeation and diffusion rates. Researchers pay more attention to the thickness of the palladium membrane, the control of the porosity and surface defects of the carrier, the doping of different metal elements, etc. In fact, how to quickly screen the palladium membrane that meets the requirements, or how to quickly select the palladium membrane with simple preparation process and raw material source to meet the application of different hydrogen-related scenes is also of great significance. SUMMARY

[0005] The purpose of the present application is to overcome the technical problem that the prior art cannot accurately select and quickly prepare palladium membranes with specific hydrogen permeation and diffusion rates, and to provide a method for carrying out hydrogen-related reactions.

[0006] The inventors of the present application found in research that the hydrogen permeation and diffusion rate is related to the lattice parameter of the palladium membrane, the lattice parameter of the palladium membrane is determined according to the required hydrogen permeation and diffusion rate, and then the preparation process or raw material is selected according to the lattice parameter, so that the preparation process and raw material are simplified, and the preparation and application of the palladium membrane are more targeted, therefore, in order to achieve the above purpose, the present application provides a method for carrying out hydrogen-related reactions, which comprises:

[0007] (a) determining the lattice parameter k of the palladium membrane according to the hydrogen permeation and diffusion rate J H2 required by the hydrogen-related reaction;

[0008] (b) providing a palladium membrane with the lattice parameter;

[0009] (c) carrying out the hydrogen-related reaction in the presence of the provided palladium membrane.

[0010] Compared with the prior art, the present application can realize the controllable preparation of palladium membranes with different lattice parameters by establishing the corresponding relationship between the hydrogen permeation and diffusion rate and the lattice parameter, that is, the skilled person can select the corresponding alloying treatment conditions based on different requirements, and then a series of palladium membranes with excellent performance, such as good hydrogen separation performance, high mechanical strength, long service life and good stability, can be conveniently prepared in large quantities. DETAILED DESCRIPTION

[0011] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the present application. The ranges and values should be construed and interpreted as being inclusive of values roughly or approximately around the ranges or values. For numerical ranges, the endpoints are included in the ranges, and the endpoints and individual points are combinable with each other to form new numerical ranges, which should be considered as specifically disclosed herein.

[0012] The present application provides a method for carrying out hydrogen-related reactions, characterized in that the method comprises:

[0013] (a) determining the lattice parameter k of the palladium membrane (composite palladium-based alloy material) according to the hydrogen permeation and diffusion rate J H2 required by the hydrogen-related reaction;

[0014] (b) providing a palladium membrane with the lattice parameter;

[0015] (c) carrying out the hydrogen-related reaction in the presence of the provided palladium membrane.

[0016] In the present application, the hydrogen permeation and diffusion rate of palladium membranes with different thicknesses and lattice parameters is tested, the relationship between the hydrogen permeation and diffusion rate and the lattice parameter is obtained according to the obtained experimental data, and preferably, in step (a), the hydrogen permeation and diffusion rate JH2 satisfies formula I:

[0017]

[0018] In formula I, J H2 has a unit of mol·m -2 ·s -1 ;

[0019] k has a unit of nm;

[0020] n is the number of types of metals contained in the palladium film;

[0021] M a is the average relative atomic mass of the n types of alloys, with a unit of g / mol;

[0022] M i is the relative atomic mass of the i-th metal, with a unit of g / mol;

[0023] ρ a is the average density of the n types of alloys, with a unit of kg / m 3 ;

[0024] ρ i is the density of the i-th metal, with a unit of kg / m 3 ;

[0025] d is the thickness of the palladium film, with a unit of m;

[0026] b is a correction coefficient, and has a value range of 0.5-3.

[0027] The inventors of the present application found, in the research process, that J H2 , n, M a , M i , ρ a , ρ i and d are related, and thus formula I is obtained by fitting the data of the experiment.

[0028] Preferably, when the material of the palladium film is a PdCu alloy, b has a value range of 0.54-1.25.

[0029] Preferably, when the material of the palladium film is a PdAg alloy, b has a value range of 0.61-1.68.

[0030] Preferably, when the material of the palladium film is a PdAu alloy, b has a value range of 0.70-3.

[0031] Preferably, when the material of the palladium film is a PdCuAg alloy, b has a value range of 0.59-1.62.

[0032] Preferably, when the material of the palladium membrane is PdCuAu alloy, the value range of b is 0.75-2.65.

[0033] Preferably, when the material of the palladium membrane is PdCuNi alloy, the value range of b is 0.51-1.22.

[0034] The inventors have further found that, in particular, palladium membranes without Au can meet the formula I.

[0035] In the present application, J H2 The test method of the hydrogen permeation and diffusion rate (unit: mol·m -2 ·s -1 ) is to measure the hydrogen volume (liter) passing through the palladium-based composite membrane per minute at 20℃ and 0.1MPa transmembrane pressure difference, and then normalize it to the hydrogen permeation amount (mol·m -2 ·s -1 ) according to the membrane area (square meter).

[0036] In the present application, the "lattice parameter k" refers to the physical size of the unit cell in the lattice, which represents the basic structural parameter of the crystal material. The lattice parameter k represents the edge length of the unit cell, that is, the edge length of each parallelepiped unit, which is directly related to the binding energy between atoms. The unit cell in three-dimensional space generally has 3 lattice parameters, represented by a, b and c respectively. According to the distribution of Bravais lattices, in the cubic crystal structure (body-centered cubic close packing, face-centered cubic close packing) involved in the present application, the three constants are equal, so the parameter k can be used to represent them. Changes in k reflect changes in composition, stress state, etc. within the crystal. The lattice parameter k can be measured by X-ray diffraction (XRD) or atomic force microscopy (AFM).

[0037] In the present application, "body-centered cubic close packing" refers to a close packing method in cubic crystal system, which contains 2 lattice points, one at the vertex and one at the body center, i.e. eight atoms at the eight vertices of the cube and one atom at the center of the cube, and the eight atoms at the vertices are tangent to the central atom.

[0038] In the present application, "face-centered cubic close packing" refers to a crystal cell involving 14 atoms belonging to 4 layers: one corner is A layer, the three face-centered atoms and three corner atoms most adjacent to it belong to B layer, the next six atoms belong to C layer, and the other corner opposite to the corner of A layer is in the next cycle of A layer.

[0039] In the present application, the hydrogen-involved reaction can be a reaction in which hydrogen gas is used as a substrate and / or a reaction in which hydrogen gas is produced as a reaction product.

[0040] In the present application, the hydrogen-involved reaction can be a reaction in which hydrogen, oxygen and propylene are used as substrates to synthesize propylene oxide.

[0041] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0042] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0043] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0044] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0045] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0046] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0047] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0048] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0049] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0050] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0051] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0052] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0053] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0054] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0055] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0056] In the present application, the hydrogen-related reaction can be a reaction of synthesizing hydrogen peroxide with hydrogen and oxygen as substrates.

[0057] According to the present application, preferably, in step (b), the palladium film having the crystal lattice parameter is provided in the following manner:

[0058] (1) alloying the palladium membrane raw material under different alloying conditions, testing the lattice parameters of the product, and establishing a fitting curve of the corresponding relationship between the alloying conditions and the lattice parameters;

[0059] (2) finding the corresponding alloying conditions in the fitting curve obtained in step (1) based on the required lattice parameters, and alloying the palladium membrane raw material under the conditions to obtain a palladium membrane with the required lattice parameters.

[0060] According to a preferred embodiment of the present application, based on a large number of experiments in step (1), a database of the alloying conditions and the lattice parameters is established, so that the alloying conditions corresponding to the lattice parameters can be found more quickly and conveniently.

[0061] According to some embodiments of the present application, the palladium membrane is a membrane-shaped material, and in order to further ensure the operability of the material, the palladium membrane raw material can include a support body supporting the palladium membrane, and therefore, in step (1), the palladium membrane raw material includes a support body and Pd and optional other active components deposited on the support body (one side or both sides of the surface).

[0062] According to some embodiments of the present application, in the palladium membrane raw material, the molar ratio of Pd to the other active components is 1:(0.05-20), more preferably 1:(0.1-5), and further preferably 1:(0.1-2).

[0063] According to some embodiments of the present application, the other active components are selected from at least one of Group IIIA, Group VIII, Group IB and Group IIIB elements, more preferably from at least one of Group IB and / or Group VIII elements, and further preferably from at least one of Cu, Ag, Au and Ni.

[0064] According to some embodiments of the present application, the metal elements in the palladium membrane include Pd and Cu, or Pd and Ag, or Pd and Au, or Pd, Cu and Au, or Pd, Cu and Ag, or Pd, Cu and Ni.

[0065] According to a preferred embodiment of the present application, the palladium membrane raw material in steps (1) and (2) has the same composition.

[0066] According to some embodiments of the present application, the thickness of the support is 0.1-20 mm (e.g., 0.1 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, and a range between any two of the aforementioned values), preferably 2-5 mm. The support can be provided by a material commonly used in the art that can withstand the operating temperature of the present application and does not affect the hydrogen permeation performance, that is, does not deform and does not affect the hydrogen permeation performance at the operating temperature of the present application. In order to achieve more excellent mechanical stability and thermal stability and reduce the amount of palladium used (reduce cost), preferably, the support is a porous support, which can be selected from at least one of porous ceramic, porous glass, porous metal (e.g., porous stainless steel), porous quartz, and high polymer, more preferably at least one of porous ceramic, porous metal, and high polymer. Generally, the porosity of the support is in the range of 15-75%, and the average pore size is 0.05-0.4 μm. In order to obtain a tubular membrane, the support is preferably a tubular support. The material of the porous ceramic can be γ-Al2O3, the porosity is in the range of 25-66%, and the average pore size is 0.12-0.4 μm. The material of the porous stainless steel can be 316L (Fe 69 Cr 17 Ni 12 Mo2), the porosity is in the range of 32-71%, and the average pore size is 0.08-0.36 μm. The material of the high polymer can be polyimide, the porosity is in the range of 15-37%, and the average pore size is 0.05-0.22 μm. The "porosity range" can be measured by the method of nitrogen physical adsorption. The "average pore size" can be measured by the method of nitrogen physical adsorption.

[0067] According to the present application, preferably, the palladium membrane raw material is prepared by depositing Pd and the other active components on the support.

[0068] There is no particular requirement for the deposition method, according to some embodiments of the present application, the deposition method is at least one of a gas phase deposition method (e.g., physical vapor deposition or chemical vapor deposition), electroless plating, electroplating, and electroforming, preferably at least one of electroplating and electroless plating. For example, the specific operation method and conditions of the electroplating method are as follows: at a temperature of 10-50 °C, using a conductive layer carrier as a working electrode, a platinum electrode (plating Pd, plating Au, plating Ni), a silver electrode (plating Ag), and a waveguide tube with a copper content of 99.999% (plating Cu) as a counter electrode, and a saturated calomel electrode as a reference electrode, at a temperature of 30 °C, the metal ions (Pd 2+ , and other active component metal ions such as Cu 2+ , Au 3+ , Ag+ Ni 2+ ) concentration of 0.01-0.2 mol / L, and the electroplating experiment is carried out by cyclic voltammetry, wherein the working voltage range is -0.60V to -0.90V; the scan rate is 0.01V / s-0.0075V / s; the scan period is 200-2000; and the sensitivity is 0.001A / V-0.0001A / V. The corresponding metal ions in the plating solution are reduced and deposited on the working electrode to form a dense metal film material (i.e., the palladium membrane raw material).

[0069] In the present application, the palladium membrane has certain requirements from the aspects of hydrogen permeation and diffusion rate, selectivity, and cost, etc. For example, the total thickness of Pd and other active components deposited on the support in the palladium membrane raw material is 0.5-30μm (for example, 0.5μm, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 15μm, 20μm, 25μm, 30μm, and a range formed by any two of the above), preferably 5-15μm.

[0070] According to some embodiments of the present application, in step (1), the conditions of the alloying treatment include temperature, pressure, time, cooling rate, etc.

[0071] According to the present application, preferably, the alloying treatment is performed by treating the palladium membrane raw material at 300-800℃, 0.1-1MPa for 1-10h, and then cooling to 100-250℃ at a rate of more than 5℃ / min, particularly 10-200℃ / min. More preferably, the alloying treatment is performed by treating the palladium membrane raw material at 350-650℃, 0.12-0.8MPa for 2-8h, and then cooling to 120-230℃ at a rate of 20-150℃ / min. The alloying treatment in the above manner can further improve the crystal form stability of the palladium membrane, thereby further improving the hydrogen permeation stability (the time for the hydrogen permeation amount to stabilize from fluctuation is further shortened). In the above preferred alloying treatment, the heating rate of the palladium membrane raw material is not particularly limited.

[0072] According to the present application, in order to obtain the material to be used, the alloying treatment can further include a step of naturally cooling to room temperature.

[0073] According to the present application, preferably, the alloying treatment is carried out under an activating atmosphere. The gas providing the activating atmosphere can be any of the commonly used gases in the art which are gaseous under the conditions of the alloying treatment, but preferably, the activating atmosphere is provided by at least one of a noble gas (such as Ar), N2, water vapor, H2, an acidic gas (such as CO2), and a basic gas (such as ethylenediamine and NH3). Among them, the addition of a basic gas can make the palladium-based alloy membrane activate faster and the formed body-centered (or face-centered) cubic structure more stable, so more preferably, the activating atmosphere is provided by a non-basic gas and a basic gas.

[0074] According to some embodiments of the present application, the gas providing the activating atmosphere comprises H2, N2, and NH3, and the volume ratio of H2, N2, and NH3 is 1:(0.1-2.5):(0.01-0.5); further preferably, 1:(0.2-0.8):(0.01-0.3).

[0075] According to some embodiments of the present application, the gas providing the activating atmosphere comprises H2 and N2, and the volume ratio of H2 and N2 is 1:(0.1-4), further preferably, 1:(0.2-3.4).

[0076] According to some embodiments of the present application, the gas providing the activating atmosphere comprises H2 and Ar, and the volume ratio of H2 and Ar is 1:(0.1-8), further preferably, 1:(0.5-6).

[0077] In order to verify the accuracy of the fitting curve of the correspondence between the conditions of step (1) and the lattice parameters, step (1) can further comprise: testing the hydrogen permeation activation energy of the product, and establishing a fitting curve of the correspondence between the conditions of the alloying treatment and the hydrogen permeation activation energy.

[0078] In the present application, preferably, the hydrogen permeation activation energy is obtained by a palladium membrane hydrogen permeation system.

[0079] According to the present application, in order to further improve the anti-sulfur, anti-chlorine and anti-carbon deposition performance of the composite palladium-based alloy material, the composite palladium-based alloy material can be further covered with a protective layer which does not affect the hydrogen permeation performance (hydrogen permeation activation energy) of the composite palladium-based alloy material. The protective layer can be a modified molecular sieve or an unmodified molecular sieve. The molecular sieve can be a titanium-silicon molecular sieve or a silicon-aluminum molecular sieve. The modified molecular sieve can be a molecular sieve doped with a noble metal (such as Au), a silanized molecular sieve, a molecular sieve modified with an active component layer (such as a MoO2 nanoparticle layer or a Na-Fe3O4 nanoparticle layer), etc. Therefore, the present application further provides a composite membrane comprising a composite palladium-based alloy material and a protective layer covering the surface of the composite palladium-based alloy material. Accordingly, a method for preparing the composite membrane can comprise: preparing a composite palladium-based alloy material according to the method described above, and then covering the surface of the composite palladium-based alloy material with a protective layer. The method for covering the protective layer can be an in-situ generation method. The pore size distribution of the protective layer can be 0.5-50 nm.

[0080] The present application further provides a method for preparing a palladium membrane, which comprises: depositing Pd and Cu on a support, and then subjecting the support on which Pd and Cu are deposited to an alloying treatment, wherein the molar ratio of Pd to Cu is 100:(90-120).

[0081] According to the method for preparing a palladium membrane provided by the present application, preferably, the alloying treatment is performed in an activation atmosphere at a temperature of 570-600℃ and a pressure of 0.37-0.52 MPa for 4-7 h, and then the temperature is decreased to 120-180℃ at a rate of 55-85℃ / min (55℃ / min, 60℃ / min, 65℃ / min, 70℃ / min, 75℃ / min, 80℃ / min, 85℃ / min, and a range formed by any two of the above), and the gas providing the activation atmosphere comprises H2, N2 and NH3, and the volume ratio of H2, N2 and NH3 is 100:(27-77):(1-21). The palladium membrane prepared by the method has a high hydrogen permeation and diffusion rate. The palladium-copper alloy material obtained according to the preferred embodiment has higher hydrogen permeation performance or stability. The addition of the alkaline gas NH3 can make the palladium-based alloy membrane activate faster, the formed body-centered cubic structure more stable, and the half-peak width of the characteristic peak in the XRD pattern smaller.

[0082] In the present application, the pressure of the alloying treatment is generally controlled by adjusting the amount of the gas providing the activation atmosphere. After being decreased to below 180℃ at a specific rate, the temperature can be cooled to room temperature for standby use.

[0083] According to the method for preparing a palladium membrane provided by the present application, preferably, the total thickness of Pd and Cu deposited on the support is 0.5-30 μm (for example, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 4 μm, 5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, and a range formed by any two of the above), more preferably 5-15 μm, and further preferably 6-8 μm.

[0084] According to the method for preparing a palladium membrane provided by the present application, preferably, the thickness of the support is 0.1-20 mm (for example, 0.1 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 15 mm, 20 mm, and a range formed by any two of the above), and preferably 2-5 mm.

[0085] The present application will be described in detail below through examples. In the following examples, the inner surface of the support is closed by a polytetrafluoroethylene material, and therefore the polytetrafluoroethylene material is peeled off before application or performance test.

[0086] Example

[0087] A porous stainless steel tube is used as the support (tubular, inner diameter: 9.5-10.5 mm, outer diameter: 12.5-13.5 mm; average pore size: 0.25 μm, porosity: 65%), which is first soaked in anhydrous ethanol for 30 minutes, with the purpose of removing surface dust, grease and other contaminants, and then the surface and inner side of the carrier are washed with deionized water and placed in warm water, and washed with a vacuum pump to wash away the residual ethanol in the pores, and finally dried in an oven at 423 K for 4 h; Pd and other active components (at least one of Cu, Ag, Au and Ni) are deposited on the support by electroplating according to Faraday's law, and the types and molar ratios of Pd and other active components are as shown in Table 1, and the effective membrane area is 21-50 cm 2 ; wherein the plating conditions are as follows: the conductive layer carrier is used as the working electrode, the platinum electrode (plating Pd) and the other active component electrode (plating other active components) are used as the counter electrode, and the saturated calomel electrode is used as the reference electrode, at a temperature of 30°C, and the metal ions (Pd 2+ , and other active component metal ions such as Cu 2+ , Au 3+ , Ag + , and Ni 2+The concentration of the solution was 0.01-0.3 mol / L. Electroplating experiments were conducted using cyclic voltammetry, with a working voltage range of -0.60V to -0.90V, a scan rate of 0.0075V / s, a scan period of 1000, and a sensitivity of 0.0001A / V. Simultaneously, during the electroplating process, a 0.05 mol / L solution of ammonium palladium chloride ((NH4)2PdCl4) was added to the plating solution at a rate of 1-2 ml / min; salt solutions of other active components at a rate of 0.2-1.5 ml / min; ethylenediamine (EDA, 99%, analytical grade) at a rate of 0.05-0.12 ml / min; disodium ethylenediaminetetraacetate (EDTA-2Na, 99%, analytical grade) at a rate of 0.025-0.05 ml / min; and bipyridine (C... 10 H8N2 (99%, analytical grade). The plating bath was vigorously stirred (1000 r / min) while the above solution was added. Every 30 min of electroplating, the working electrode, cleaned with distilled water, was immersed for 10 min in 0.05 mol / L phosphoric acid (H3PO4) solution and 0.05 mol / L dipotassium hydrogen phosphate (K2HPO4) solution, respectively. After the cyclic voltammetry procedure, the working electrode was treated in distilled water at 80-100℃ for 10-15 min before removal. The support with deposited Pd and other active components was subjected to high-temperature alloying treatment. The alloying treatment was carried out in an activating atmosphere at temperature T1 and pressure P for a period of time (t); then the temperature was reduced to T2 at a rate V. The types and volumes of the activating atmosphere gas are shown in Table 1. The amount of activating atmosphere gas provided was such that the alloying pressure was P. Various palladium-based alloy materials were obtained by changing the preparation conditions.

[0088] Test case

[0089] (I) The materials obtained after alloying treatment in each embodiment and comparative example were characterized. The characterization method is as follows, and the crystal structure parameters of the materials are shown in Table 1-2.

[0090] The crystal structure analysis of the alloyed material was performed on an X'PertPRO / PANalytical automated X-ray diffractometer manufactured by Philips, Netherlands. The experimental conditions were Cu K α X-rays (λ = 0.1543 nm), tube voltage 40 kV, current 40 mA, diffraction angle 2θ scan range 10-90°. The interplanar spacing of the sample was calculated using the Bragg equation.

[0091] d=λ / 2sinθ

[0092] where λ is the wavelength of the Cu K α ray, and θ is the angle of the diffraction peak.

[0093] The crystal structure of the material obtained after alloying treatment was tested at the European Synchrotron Center in France (beam BM25A), which has higher resolution, synchrotron radiation λ = 0.0618886 nm or 0.077449 nm, tube pressure 10.0335 keV, first take 10 x 1 mm 2 samples in a quartz capillary with a diameter of 2 mm, two sections are closed with quartz wool, and then the quartz capillary is installed on a sample stage that can be rotated (to ensure uniform temperature and larger radiation area), the test temperature range is 298-473 K (heated by a hot air blower), the pressure range is 10 -4 -130 kPa, and the test atmosphere is first passed through hydrogen, treated for 30 min, then vacuum, and then passed through helium as a protective gas for measurement.

[0094] The test method of the lattice parameters of the material obtained after alloying treatment: in combination with the above in-situ XRD test, the unit cell parameters (represented by a, b, c three unit cell constants and three unit cell angles α, β, γ) of the material obtained after alloying treatment are obtained, and according to the formula d1 = a / (α 2 + β 2 + γ 2 ) 0.5 , d2 = b / (α 2 + β 2 + γ 2 ) 0.5 , d3 = c / (α 2 + β 2 + γ 2 ) 0.5 , the interplanar spacing (d1 d2 d3) of the corresponding characteristic crystal face is converted, for example, the PdCu alloy material obtained in the present application belongs to body-centered cubic packing (BCC) structure, and the characteristic crystal faces include (110), (111), (200), (210), (211); at the same time, according to the X-ray diffraction result, a series of different characteristic crystal face ratios (corresponding to the intensity of different crystal faces) can be obtained, for example, the PdCu alloy material obtained in the present application, the (110) face corresponds to the characteristic peak at 2θ = 43° ± 1°, the (111) face corresponds to the characteristic peak at 2θ = 53° ± 1°, the (200) face corresponds to the characteristic peak at 2θ = 62° ± 1°, the (210) face corresponds to the characteristic peak at 2θ = 70° ± 1°, and the (211) face corresponds to the characteristic peak at 2θ = 79° ± 1°. Through the HighScorePlus analysis software, the peak intensity of the above characteristic crystal face is converted to obtain the lattice parameters k of the corresponding material;

[0095] The test method of the thickness of the material obtained after alloying treatment is obtained by scanning electron microscope (model: JSM-7610F), and the alloy film thickness is determined according to the scale corresponding to the magnification;

[0096] The test method of the half-peak width of the material obtained after alloying treatment is that, according to the XRD spectrum test result, the radian value of the half-peak width is obtained by combining HighScore Plus software analysis.

[0097] J H2 The test method of the hydrogen permeation diffusion rate (unit: mol·m -2 ·s -1 ) is to measure the hydrogen volume (liter) passing through the palladium-based composite membrane per minute under the conditions of 20 DEG C and 0.1 MPa transmembrane pressure difference, and then normalized to the hydrogen permeation amount (mol·m -2 ·s -1 ) according to the membrane area (square meter).

[0098] Table 1

[0099]

[0100]

[0101] Note: BCC+FCC in Table 1 means both body-centered cubic packing and face-centered cubic close packing; “-” means that the parameter is the same as F1.

[0102] Table 2

[0103]

[0104]

[0105]

[0106] Further, the present application establishes a database of the lattice parameters of palladium membranes corresponding to the alloying treatment conditions through a large number of experiments, and tests the hydrogen permeation diffusion rate of the palladium membrane, and finds that the lattice parameters and the hydrogen permeation diffusion rate satisfy a certain relationship (Formula I). Based on this, the person skilled in the art can quickly determine the corresponding lattice parameters when selecting different hydrogen permeation diffusion rates through the formula shown in Formula I, and then input the lattice parameters in the database for screening, so as to quickly determine the alloying treatment conditions, greatly shorten the experimental period, and significantly improve the research and development efficiency.

[0107] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A method of carrying out a hydrogen- involving reaction, characterized by, The method comprises: (a) the hydrogen permeation diffusion rate J required for the hydrogen reaction H2 determining the lattice parameter k of the palladium membrane; (b) providing a palladium membrane with the lattice parameter; (c) performing a hydrogen-involved reaction in the presence of the provided palladium membrane; In step (a), the hydrogen permeation diffusion rate J H2 satisfies equation I with the lattice parameter k: In formula I, J H2 has the unit of mol·m -2 ·s -1 ; k is in nm; n is the number of types of metals contained in the palladium membrane; M a is the average relative atomic mass of the n alloys in g / mol; M i Relative atomic mass of the i-th metal in g / mol; p a is the average density of the n alloys in kg / m 3 ; p i Density of the i-th metal, in kg / m 3 ; d is the thickness of the palladium membrane, in m; b is a correction coefficient, and its value ranges from 0.5 to 3; In step (b), the palladium membrane with the lattice parameter is provided in the following manner: (1) alloying the palladium membrane raw material under different alloying conditions, testing the lattice parameter of the product, and establishing a fitting curve of the corresponding relationship between the alloying conditions and the lattice parameter; (2) based on the required lattice parameter, finding the corresponding alloying conditions in the fitting curve obtained in step (1) and alloying the palladium membrane raw material under the conditions to obtain a palladium membrane with the required lattice parameter; The alloying method is as follows: the palladium membrane raw material is treated at 300-800℃ and 0.1-1MPa for 1-10 hours, and then reduced to 100-250℃ at a rate of greater than 5℃ / min.

2. The method of claim 1, wherein, The hydrogen-involved reaction is a reaction in which hydrogen gas is used as a substrate and / or a reaction in which hydrogen gas is produced as a reaction product.

3. The method of claim 1, wherein, The hydrogen-involved reaction is a reaction in which hydrogen, oxygen and propylene are used as substrates to synthesize propylene oxide; Alternatively, the hydrogen-involved reaction is a reaction in which hydrogen and oxygen are used as substrates to synthesize hydrogen peroxide; Alternatively, the hydrogen-involved reaction is a reaction in which alcohol is reformed with steam to produce hydrogen; Alternatively, the hydrogen-involved reaction is a carbon dioxide hydrogenation reaction; Alternatively, the hydrogen-involved reaction is a reaction in which hydrogen and nitrogen are used as substrates to synthesize ammonia; Alternatively, the hydrogen-involved reaction is a reaction in which ethane is dehydrogenated to produce ethylene; Alternatively, the hydrogen-involved reaction is a reaction in which propane is dehydrogenated to produce propylene; Alternatively, the hydrogen-involved reaction is a reaction in which butane is dehydrogenated to form butadiene; Alternatively, the hydrogen-involved reaction is a reaction in which isopentene is dehydrogenated to form isoprene; Alternatively, the hydrogen-involved reaction is a reaction in which ethylbenzene is dehydrogenated to produce styrene; Alternatively, the hydrogen-involved reaction is a reaction in which isobutane is dehydrogenated to produce isobutene; Alternatively, the hydrogen-involved reaction is a reaction in which benzene is hydrogenated to produce cyclohexane; Alternatively, the hydrogen-involved reaction is a reaction in which benzene, hydrogen and oxygen are used as substrates to produce phenol; Alternatively, the hydrogen-involved reaction is a reaction in which carbon monoxide is hydrogenated to produce methanol; Alternatively, the hydrogen-involved reaction is a reaction in which phenol is hydrogenated to produce cyclohexanol; Alternatively, the hydrogen-involved reaction is a reaction in which nitrobenzene is reduced by hydrogenation to produce aniline; Alternatively, the hydrogen-involved reaction is a reaction in which butane is dehydrogenated to form butadiene.

4. The method of claim 1, wherein, In step (1), the palladium membrane raw material comprises a support and Pd and optional other active components deposited on the support.

5. The method of claim 4, wherein, In the palladium membrane raw material, the molar ratio of Pd to the other active components is 1:(0.05-20); And / or, the other active components are selected from at least one of Group IIIA, Group VIII, Group IB and Group IIIB elements; And / or, the support is selected from at least one of porous ceramic, porous glass, porous metal, porous quartz and polymer.

6. The method of claim 4, wherein, In the palladium membrane raw material, the molar ratio of Pd to the other active components is 1:(0.1-5).

7. The method of claim 4, wherein, The other active components are selected from Group IB and / or Group VIII elements.

8. The method of claim 4, wherein, The support is selected from at least one of porous ceramics, porous metal, and high molecular polymer.

9. The method of claim 4, wherein, The other active component is selected from at least one of Cu, Ag, Au, and Ni.

10. The method of claim 4, wherein, The palladium membrane raw material is prepared by depositing Pd and the other active component on a support.

11. The method of claim 10, wherein, The deposition is at least one of vapor deposition, electroless plating, electroplating, and electroforming.

12. The method of claim 4, wherein, The total thickness of Pd and the other active component deposited on the support in the palladium membrane raw material is 0.5-30 μm.

13. The method of claim 4, wherein, The total thickness of Pd and the other active component deposited on the support in the palladium membrane raw material is 5-15 μm.

14. The method of claim 1, wherein, The alloying treatment is performed at 350-650℃, 0.12-0.8 MPa for 2-8 h, and then decreased to 120-230℃ at a rate of 20-150℃ / min.

15. The method of claim 1, wherein, The alloying treatment is performed in an activating atmosphere.

16. The method of claim 15, wherein, The activating atmosphere is provided by at least one of rare gas, N2, water vapor, H2, acidic gas, and basic gas.

17. The method of claim 15, wherein, The gas providing the activating atmosphere includes H2, N2, and NH3, and the volume ratio of H2, N2, and NH3 is 1:(0.1-2.5):(0.01-0.5). Alternatively, the gas providing the activating atmosphere includes H2 and N2, and the volume ratio of H2 and N2 is 1:(0.1-4). Alternatively, the gas providing the activating atmosphere includes H2 and Ar, and the volume ratio of H2 and Ar is 1:(0.1-8).

18. The method of claim 15, wherein, The gas providing the activating atmosphere includes H2, N2, and NH3, and the volume ratio of H2, N2, and NH3 is 1:(0.2-0.8):(0.01-0.3).

19. The method of claim 15, wherein, The gas providing the activating atmosphere includes H2 and N2, and the volume ratio of H2 and N2 is 1:(0.2-3.4).

20. The method of claim 15, wherein, The gas providing the activating atmosphere includes H2 and Ar, and the volume ratio of H2 and Ar is 1:(0.5-6).

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