Method for selecting a target palladium membrane, method for carrying out hydrogen-related reactions, method for determining permeation and diffusion rates, and system

Abstract

The present invention discloses a method for selecting a target palladium membrane, a method for performing a hydrogen-related reaction, and a method and system for determining permeation and diffusion rates. The selection method includes the steps of determining the target lattice parameters and target metal composition and their proportions of the target palladium membrane from the target permeation and diffusion rate of hydrogen gas through the target palladium membrane, the target thickness of the target palladium membrane, and the correspondence between the target permeation and diffusion rate of hydrogen gas through a sample palladium membrane and a specific parameter set of the sample palladium membrane, and selecting a palladium membrane having the target lattice parameters, the target metal composition and its proportions, and the target thickness as the target palladium membrane. The present invention allows for efficient and convenient selection of an appropriate palladium membrane that satisfies the target hydrogen gas permeation and diffusion rate of a hydrogen-related reaction, conveniently measuring the hydrogen gas permeation and diffusion rate of the palladium membrane, and accurately controlling the progress of the hydrogen-related reaction.

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the rights and benefit of Chinese Patent Application No. 202210843326.5, filed on July 18, 2022, the contents of which are incorporated herein by reference. [Technical Field]

[0002] The present invention relates to the technical field of hydrogen gas purification, and more particularly to a method for selecting a target palladium membrane, a method for carrying out a hydrogen-related reaction, and a method and system for determining permeation and diffusion rates. [Background technology]

[0003] Different hydrogen-related reactions require different hydrogen gas permeation and diffusion rates, so the factors that affect the hydrogen gas permeation and diffusion rates are also an important research topic for researchers. Currently, researchers have found that factors that affect the hydrogen gas permeation and diffusion rates include the thickness of the palladium membrane, the porosity of the support, and control of surface defects. However, research questions regarding which influencing factors can more accurately characterize the hydrogen gas permeation and diffusion rates, as well as how to screen appropriate palladium membranes that meet the target hydrogen gas permeation and diffusion rates for hydrogen-related reactions, are particularly important.

[0004] In addition, existing methods for detecting hydrogen gas permeation and diffusion rates are mainly performed using a flow rate calibration method, and the detection steps include the following steps: (1) sealing the palladium membrane to be measured with a graphite ferrule, metal welding, or ceramic glaze seal, and then placing it in a fixed-bed reactor test apparatus to construct a sealed gas permeation and diffusion test device; (2) introducing hydrogen gas from the intake side, maintaining a constant transmembrane pressure, and measuring the flow rate (F) of hydrogen gas that permeates the palladium membrane and reaches the permeation side within a certain time (t) based on Fick's law; and (3) converting the hydrogen gas permeation and diffusion rate (J) (J = F / t).

[0005] In the above test process, different sealing methods and sealing locations during the palladium membrane sealing process can result in different levels of defect exposure in the palladium membrane after sealing. This leads to differences in the hydrogen gas permeation and diffusion rates at the defect locations, thereby affecting the hydrogen gas permeation and diffusion rates. Furthermore, the sealing performance of the entire test device also affects the stability of the transmembrane pressure, which is the driving force behind hydrogen gas permeation and diffusion across the palladium membrane. Therefore, the sealing performance of the equipment and device is also a factor that affects the permeation and diffusion rates of membrane materials.

[0006] In addition, there are large discrepancies between the time and flow rate observed by the tester due to chance. As described above, existing testing systems have many systematic and random errors, which places high demands on devices, raw materials, and testing personnel, making the testing process time-consuming and labor-intensive. Summary of the Invention [Problem to be solved by the invention]

[0007] The object of the present invention is to provide a method for selecting a target palladium membrane, a method for performing a hydrogen-related reaction, a method for determining permeation and diffusion rates, and a system for efficiently and simply selecting an appropriate palladium membrane that satisfies the target hydrogen gas permeation and diffusion rates for a hydrogen-related reaction, a method for simply measuring the hydrogen gas permeation and diffusion rates of a palladium membrane, and a method for accurately controlling the progress of a hydrogen-related reaction so that the hydrogen gas permeation and diffusion rates meet the target values. [Means for solving the problem]

[0008] A first aspect of the present invention provides a method for selecting a target palladium membrane, the method comprising the steps of: determining a target lattice parameter and a target metal composition and its proportion of the target palladium membrane from correspondence relationships between the target permeation / diffusion rate of hydrogen gas through the target palladium membrane, the target thickness of the target palladium membrane, and the permeation / diffusion rate of hydrogen gas through a sample palladium membrane, and a specific parameter set of the sample palladium membrane, the specific parameter set including the lattice parameter, metal composition coefficient, and thickness; and selecting a palladium membrane having the target lattice parameter, the target metal composition and its proportion, and the target thickness as the target palladium membrane.

[0009] Preferably, the correspondence between the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes the following:

[0010]

number

[0011] Preferably, the correspondence between the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes the following:

[0012]

number

[0013] Preferably, A depends on the number of metal species in the sample palladium membrane, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium membrane. Preferably, A is determined by the following formula:

[0014]

number

[0015] Preferably, b depends on the effective atomic radius of the sample palladium film.

[0016] Preferably, when the material of the sample palladium membrane is a PdCu alloy, the value of b is in the range of 1.01 to 2.51; When the material of the sample palladium membrane is a PdAg alloy, the value of b ranges from 1.12 to 2.53; When the material of the sample palladium membrane is a PdAu alloy, the value of b ranges from 1.56 to 3.62; When the material of the sample palladium membrane is a PdCuAg alloy, the value of b ranges from 1.93 to 3.69; When the material of the sample palladium membrane is a PdCuAu alloy, the value of b is in the range of 2.56 to 4.99, or When the material of the sample palladium membrane is a PdCuNi alloy, the value of b ranges from 1.63 to 2.71.

[0017] According to the above technical solution, the present invention innovatively determines the target lattice parameters and target metal composition and their proportions of the target palladium membrane from the target permeation and diffusion rate of hydrogen gas through the target palladium membrane, the target thickness of the target palladium membrane, and the correspondence between the permeation and diffusion rate of hydrogen gas through a sample palladium membrane and a specific parameter set of the target palladium membrane, and then selects a palladium membrane having the target lattice parameters, target metal composition and their proportions, and target thickness as the target palladium membrane. This invention can efficiently and simply select an appropriate palladium membrane that satisfies the target hydrogen gas permeation and diffusion rate for a hydrogen-related reaction.

[0018] A second aspect of the present invention provides a method for performing a hydrogen-related reaction, comprising the steps of selecting a target palladium membrane for the hydrogen-related reaction according to the method for selecting a target palladium membrane for the hydrogen-related reaction, wherein the permeation / diffusion rate of hydrogen gas through the target palladium membrane is the target permeation / diffusion rate, and performing the hydrogen-related reaction using one of the selected target palladium membranes.

[0019] Preferably, the hydrogen-related reaction is a reaction for synthesizing propylene oxide using hydrogen gas, oxygen gas, and propylene as substrates, a reaction for synthesizing hydrogen peroxide using hydrogen gas and oxygen gas as substrates, a reaction for producing hydrogen by reforming alcohol and steam, a hydrogenation reaction of carbon dioxide, a reaction for synthesizing ammonia gas using hydrogen gas and nitrogen gas as substrates, a reaction for dehydrogenating ethane to produce ethylene, a reaction for dehydrogenating propane to produce propylene, a reaction for dehydrogenating butane to form butadiene, and a reaction for dehydrogenating isopentene to form butadiene. the hydrogen-related reaction is a reaction to produce isoprene, the hydrogen-related reaction is a reaction to dehydrogenate ethylbenzene to produce styrene, the hydrogen-related reaction is a reaction to dehydrogenate isobutane to produce isobutylene, the hydrogen-related reaction is a reaction to hydrogenate benzene to produce cyclohexane, the hydrogen-related reaction is a reaction to produce phenol using benzene, hydrogen gas, and oxygen gas as substrates, the hydrogen-related reaction is a reaction to hydrogenate carbon monoxide to produce methanol, the hydrogen-related reaction is a reaction to hydrogenate phenol to produce cyclohexanol, the hydrogen-related reaction is a reaction to hydrogenate and reduce nitrobenzene to produce aniline, or the hydrogen-related reaction is a reaction to dehydrogenate butane to produce butadiene.

[0020] Preferably, the target palladium membrane is produced by alloying a palladium membrane raw material under different alloying treatment conditions, measuring the lattice parameters of the products, creating a fitting curve of the correspondence between the alloying treatment conditions and the lattice parameters, determining target conditions for the alloying treatment from the lattice parameters of the target palladium membrane and the fitting curve, alloying the palladium membrane raw material under the target conditions, and obtaining the target palladium membrane.

[0021] According to the above technical solution, the present invention innovatively selects a target palladium membrane for the hydrogen-related reaction by the method for selecting a target palladium membrane for the hydrogen-related reaction, and then performs the hydrogen-related reaction using one of the selected target palladium membranes, thereby enabling the present invention to accurately control the progress of the hydrogen-related reaction so that the hydrogen gas permeation and diffusion rate meets the target value.

[0022] A third aspect of the present invention provides a method for determining a permeation / diffusion rate, comprising the steps of: measuring the lattice parameter of a palladium membrane; and determining the permeation / diffusion rate of hydrogen gas through the palladium membrane from the correspondence between the lattice parameter of the palladium membrane, the metal composition and its ratio, and the thickness, and from the correspondence between the permeation / diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane, wherein the specific parameter set includes the lattice parameter, metal composition coefficient, and thickness.

[0023] Preferably, the correspondence between the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes the following:

[0024]

number

[0025] Preferably, the correspondence between the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes the following:

number

[0026] Preferably, A depends on the number of metal species in the sample palladium membrane, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium membrane.

[0027] Preferably, A is determined by the following formula:

[0028]

number

[0029] Preferably, b depends on the effective atomic radius of the sample palladium film.

[0030] According to the above technical solution, the present invention innovatively measures the lattice parameters of a palladium membrane, and then determines the hydrogen gas permeation and diffusion rates through the palladium membrane from the lattice parameters, metal composition, ratio, and thickness of the palladium membrane, as well as the correspondence between the hydrogen gas permeation and diffusion rates through the sample palladium membrane and a specific parameter set of the sample palladium membrane, thereby enabling the present invention to efficiently and accurately measure the hydrogen gas permeation and diffusion rates through palladium membranes under non-destructive processing conditions.

[0031] A fourth aspect of the present invention is a method for measuring a hydrogen gas concentration in a sample palladium membrane, comprising: a memory for storing a target permeation / diffusion rate of hydrogen gas passing through the target palladium membrane, a target thickness of the target palladium membrane, and a correspondence relationship between the permeation / diffusion rate of hydrogen gas passing through a sample palladium membrane and a specific parameter set of the sample palladium membrane, the specific parameter set including a lattice parameter, a metal composition coefficient, and a thickness; a processor configured to execute an operation of determining a target lattice parameter and a target metal composition and its ratio of the target palladium film from the target permeation / diffusion rate, the target thickness, and the correspondence relationship, and an operation of selecting a palladium film having the target lattice parameter, the target metal composition and its ratio, and the target thickness as the target palladium film; A target palladium membrane selection system is provided, comprising:

[0032] For specific details and advantages of the target palladium membrane selection system according to the present invention, reference can be made to the above description of the target palladium membrane selection method, and therefore, they will not be described again here.

[0033] A fifth aspect of the present invention provides a system for executing hydrogen-related reactions, comprising: a selection system for target palladium membranes for hydrogen-related reactions as described above for selecting target palladium membranes for the hydrogen-related reactions, wherein the permeation / diffusion rate of hydrogen gas through the target palladium membranes is the target permeation / diffusion rate; and an execution device for executing the hydrogen-related reaction using one of the selected target palladium membranes.

[0034] For specific details and advantages of the system for carrying out hydrogen-related reactions according to the present invention, reference can be made to the above description of the method for carrying out hydrogen-related reactions, and therefore, they will not be described again here.

[0035] A sixth aspect of the present invention is a method for measuring the lattice parameter of a palladium film, comprising: a measuring device for measuring the lattice parameter of a palladium film; a memory for storing the metal composition, the ratio thereof, and the thickness of the palladium film; a processor for determining the permeation and diffusion rate of hydrogen gas through the palladium membrane from the lattice parameters, metal composition, ratio and thickness of the palladium membrane, and a correspondence relationship between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane, the specific parameter set including the lattice parameters, metal composition coefficient and thickness; The present invention provides a system for determining permeation and diffusion rates, including:

[0036] For specific details and advantages of the system for determining permeation and diffusion rates according to the present invention, reference can be made to the above description of the method for determining permeation and diffusion rates, and therefore, they will not be described again here.

[0037] A seventh aspect of the present invention provides a computer-readable storage medium storing a computer program that, when executed by a processor, realizes the method for selecting a target palladium membrane for a hydrogen-related reaction, the method for performing the hydrogen-related reaction, and / or the method for determining permeation and diffusion rates.

[0038] Other features and advantages of the present invention are described in detail in the detailed description section below. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The drawings are used to provide a further understanding of embodiments of the invention, constitute a part of the specification, and, together with the following detailed description, are used to explain, but not to limit, embodiments of the invention. FIG. 1 is a flowchart of a method for selecting a target palladium membrane according to one embodiment of the present invention. [Mode for Carrying Out the Invention]

[0040] Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. It should be understood that the specific embodiments described herein are only used to explain and interpret the present invention, and are not intended to limit the present invention.

[0041] 1 is a flowchart of a method for selecting a target palladium membrane according to one embodiment of the present invention. As shown in FIG. 1, the method for selecting a target palladium membrane includes step S101 of determining a target lattice parameter and a target metal composition and its proportion of the target palladium membrane from a correspondence relationship between the target permeation and diffusion rate of hydrogen gas through the target palladium membrane, a target thickness of the target palladium membrane, and the permeation and diffusion rate of hydrogen gas through a sample palladium membrane and a specific parameter set for the sample palladium membrane, the specific parameter set including the lattice parameter, metal composition coefficient, and thickness; and step S102 of selecting a palladium membrane having the target lattice parameter, the target metal composition and its proportion, and the target thickness as the target palladium membrane.

[0042] Before performing step S101, the method for selecting a target palladium membrane further includes a step of obtaining a correspondence relationship between the permeation and diffusion rate of hydrogen gas through a sample palladium membrane and a specific parameter set of the sample palladium membrane.

[0043] In one embodiment, the correspondence between the hydrogen gas permeation / diffusion rate through a sample palladium membrane and a specific parameter set of the sample palladium membrane may be a one-to-one correspondence between the hydrogen gas permeation / diffusion rate and a specific parameter set, as shown in Table 1, which is shown in tabular form.

[0044] [Table 1]

[0045] After obtaining the correspondence shown in Table 1, the hydrogen gas permeation / diffusion rate and target thickness required for hydrogen-related reactions can be entered into Table 1, and a combination of lattice parameters and metal composition coefficients can be obtained by searching. The combination may be one or more. In the case of one combination, the target metal composition and its proportion can be obtained based on the target metal composition coefficient and the correspondence between the target metal composition coefficient and the metal composition and its proportion, and a palladium membrane having the lattice parameters, the target metal composition and its proportion, and the target thickness can be used as the target palladium membrane. In the case of multiple combinations, the target metal composition and its proportion can be obtained for each combination based on the target metal composition coefficient and the correspondence between the metal composition coefficient and the metal composition and its proportion, and a palladium membrane having the target lattice parameters, the target metal composition and its proportion, and the target thickness can be used as the target palladium membrane. In other words, the target palladium membrane may be a plurality of target palladium membranes. When actually applying this to hydrogen-related reactions, one target palladium membrane can be selected from multiple target palladium membranes and used for the hydrogen-related reaction, or one target palladium membrane can be selected taking other conditions into consideration (details are described in the section below on how to perform hydrogen-related reactions).

[0046] Hydrogen gas permeation and diffusion rate J H2When the lattice constant k is 0.57 and the thickness d is 6 μm, several possible combinations of the lattice parameter k and metal composition coefficient A in Table 1 can be determined. For example, (0.2832, 0.968544 E-15) and (0.2716, 0.928872 E-15) are possible. From the correspondence relationship between A and metal composition shown in Table 1 (the default ratio is 1:1 or 1:1:1), it can be determined that the target lattice constant k is 0.2832, the target metal composition (and its ratio) is a palladium copper (PdCu) ​​alloy (ratio 1:1), and the target lattice constant k is 0.2716, the target metal composition (and its ratio) is a palladium copper nickel (PdCuNi) alloy (ratio 1:1:1). That is, the target palladium membrane is a palladium copper (PdCu) ​​alloy (ratio 1:1) palladium membrane with k = 0.2832 and d = 6 μm, and a palladium copper nickel (PdCuNi) alloy (ratio 1:1:1) palladium membrane with k = 0.2716 and d = 6 μm. Next, when the hydrogen-related reaction is a reaction to synthesize propylene oxide using hydrogen gas, oxygen gas, and propylene as substrates, a palladium copper (PdCu) ​​binary alloy membrane is selected from among them, taking into consideration that the palladium copper (PdCu) ​​binary alloy membrane has excellent sulfur resistance and carbon deposition resistance against propylene in the reaction system and impurities such as trace amounts of propane and sulfur-containing compounds that may be present in propylene.

[0047] In another embodiment, the correspondence between the permeation / diffusion rate of hydrogen gas through the sample palladium membrane and a specific set of parameters of the sample palladium membrane includes:

[0048]

number

[0049] After obtaining Equation 1, the target permeation and diffusion rates and target thickness required for a hydrogen-related reaction can be input into Equation 1 to obtain a combination of lattice parameters and metal composition coefficients. The combination may be one or more. In the case of one combination, the target metal composition and its proportion can be obtained based on the target metal composition coefficient and the correspondence between the metal composition coefficient, the metal composition, and its proportion. A palladium membrane having the target lattice parameters, the target metal composition, its proportion, and the target thickness is designated as the target palladium membrane. In the case of multiple combinations, the target metal composition and its proportion can be obtained based on the target metal composition coefficient and the correspondence between the metal composition coefficient, the metal composition, and its proportion for each combination. A palladium membrane having the target lattice parameters, the target metal composition, its proportion, and the target thickness is designated as the target palladium membrane. In other words, the target palladium membrane may be multiple target palladium membranes. When actually applying the method to a hydrogen-related reaction, one target palladium membrane can be selected from multiple target palladium membranes for use in a hydrogen-related reaction, or one target palladium membrane can be selected taking other conditions into consideration (details are described in the section below titled "Method for Performing a Hydrogen-Related Reaction").

[0050] Hydrogen gas permeation and diffusion rate J H2When the lattice constant k is 0.57 and the thickness d is 6 μm, multiple possible combinations of the lattice parameter k and the metal composition coefficient A can be determined using Equation 1. For example, (0.2832, 0.968544E-15) and (0.2716, 0.928872E-15) are included. From the correspondence between A and the metal composition (the default ratio is 1:1 or 1:1:1) (as shown in Table 1), it can be determined that the target lattice constant k is 0.2832, the target metal composition (and its ratio) is a palladium copper (PdCu) ​​alloy (ratio 1:1), and the target lattice constant k is 0.2716, the target metal composition (and its ratio) is a palladium copper nickel (PdCuNi) alloy (ratio 1:1:1). Next, when the hydrogen-related reaction is a reaction for synthesizing propylene oxide using hydrogen gas, oxygen gas, and propylene as substrates, a palladium copper (PdCu) ​​binary alloy membrane is selected from among them, having a target lattice constant k=0.2832 and a target metal composition (and its ratio) of palladium copper (PdCu) ​​alloy (ratio 1:1), taking into consideration that the palladium copper (PdCu) ​​binary alloy membrane has excellent sulfur resistance and carbon deposition resistance against propylene in the reaction system and impurities such as trace amounts of propane and sulfur-containing compounds that may be present in propylene.

[0051] Specifically, A depends on the number of metal species in the sample palladium membrane, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium membrane.

[0052] For example, A is determined by the following formula:

[0053]

number

[0054] Of course, A is not limited to the above formula 2, and may be a reasonable modification of the above formula 2. For example, a weighting coefficient w is multiplied based on formula 2. Specifically, w may be a value close to 1.

[0055] When the target lattice parameters and target metal composition coefficients are selected, the target metal composition and its proportion may be obtained by Equation 2:

[0056] In yet another embodiment, Equation 1 above may be further optimized by adding a correction factor related to the metal composition of the sample palladium membrane.

[0057] The correspondence relationship between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane includes the following:

[0058]

number

[0059] After obtaining Equation 3, the target permeation and diffusion rates and target thickness required for a hydrogen-related reaction are input into Equation 3 to obtain a combination of lattice parameters and metal composition coefficients. The combination may be one or several. The target metal composition and its proportion can be obtained based on the target metal composition coefficient and the correspondence between the metal composition coefficient, the metal composition, and its proportion. A palladium membrane having the target lattice parameters, the target metal composition, its proportion, and the target thickness is designated as a target palladium membrane. In the case of multiple combinations, the target metal composition and its proportion can be obtained for each combination based on the target metal composition coefficient, the correspondence between the metal composition coefficient, the metal composition, and its proportion. A palladium membrane having the target lattice parameters, the target metal composition, its proportion, and the target thickness is designated as a target palladium membrane. In other words, the target palladium membrane may be multiple target palladium membranes. When actually applying this to a hydrogen-related reaction, one target palladium membrane can be selected from multiple target palladium membranes for use in the hydrogen-related reaction, or one target palladium membrane can be selected taking other conditions into consideration (details are described below in the section "Method for Performing a Hydrogen-Related Reaction").

[0060] Specifically, A depends on the number of metal species in the sample palladium membrane, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium membrane.

[0061] For example, A is determined by the following formula:

[0062]

number

[0063] Of course, A is not limited to the above formula 2, and may be a reasonable modification of the above formula 2. For example, a weighting coefficient w is multiplied based on formula 4. Specifically, w may be a value close to 1.

[0064] When the target lattice parameters and target metal composition coefficients are selected, the target metal composition and its proportion may be obtained by Equation 4:

[0065] Specifically, b depends on the effective atomic radius of the sample palladium membrane. The value of b ranges from 1 to 5.

[0066] The range of the value of b will be explained separately below for each material of the sample palladium membrane. In the present invention, the palladium membrane is a tubular or plate-shaped palladium metal or palladium alloy that is common in the field. Preferably, the palladium membrane contains Pd, a Group IB metal element, and optionally Ni. The molar ratio of the Group IB metal element (or Group IB metal) to Pd may be 0.01 to 10, for example, 0.01, 0.05, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 3, 5, 8, 9, 10, or any value between the above values, but is preferably 0.1 to 1.6, more preferably 0.2 to 0.8.

[0067] In the present invention, the Group IB metal element may be at least one of Cu, Ag, and Au, and preferably, the Group IB metal element is Cu and / or Ag.

[0068] According to a preferred embodiment of the present invention, the palladium membrane contains Ni, and the molar ratio of Ni to Pd is 0.35 to 0.65, for example, 0.35, 0.4, 0.45, 0.5, 0.55, 0.58, 0.6, 0.62, 0.65, or any value between the above values.

[0069] When the material of the sample palladium membrane is a PdCu alloy, the value of b ranges from 1.01 to 2.51, and more preferably, the value of b ranges from 1.55 to 1.94.

[0070] When the material of the sample palladium membrane is a PdAg alloy, the value of b ranges from 1.12 to 2.53, and more preferably, the value of b ranges from 1.71 to 2.2.

[0071] When the material of the sample palladium membrane is a PdAu alloy, the value of b ranges from 1.56 to 3.62, and more preferably, the value of b ranges from 2.01 to 3.37.

[0072] When the material of the sample palladium membrane is a PdCuAg alloy, the value of b ranges from 1.93 to 3.69, and more preferably, the value of b ranges from 2.02 to 3.23.

[0073] When the material of the sample palladium membrane is a PdCuAu alloy, the value of b ranges from 2.56 to 4.99, and more preferably, the value of b ranges from 2.83 to 4.61.

[0074] When the material of the sample palladium membrane is a PdCuNi alloy, the value of b ranges from 1.63 to 2.71, and more preferably, the value of b ranges from 1.96 to 2.51.

[0075] In the present invention, d=0.5 to 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 any value between the above values), more preferably 5 to 15 μm, and even more preferably 6 to 8 μm.

[0076] As a result of the research, the present inventors have unexpectedly found that J H2 , n, M a , M i , ρ a , ρ i, d, and by fitting the experimental data, we obtained the equation shown in Equation 5.

[0077]

number

[0078] Note that if the above parameters do not specify units in the present invention, they default to the corresponding units listed above.

[0079] In the present invention, J H2 (Hydrogen gas permeation / diffusion rate, unit: mol m -2 ·s -1 The test method is to measure the volume (liters) of hydrogen gas permeating through a palladium composite membrane in 1 minute at 20°C and a transmembrane pressure difference of 0.1 MPa, and normalize the hydrogen permeation rate (mol m) according to the membrane area (square meters). -2 ·s -1 ).

[0080] In the present invention, the "lattice parameter k" refers to the physical size of a unit cell in a crystal lattice and represents a fundamental structural parameter of a crystalline material. The lattice parameter k represents the edge length of the unit cell, i.e., the edge length of each parallelepiped cell, and is directly related to the bond energy between atoms. A unit cell in three-dimensional space generally has three lattice parameters, a, b, and c, and is distributed in the form of a Bravais lattice. In the cubic crystal structure of the present invention (body-centered cubic close-packed or face-centered cubic close-packed), these three constants are equal, so the parameter k can be expressed. Changes in k reflect changes in the internal components of the crystal, the state under stress, etc. The lattice parameter k can be measured using X-ray diffraction (XRD) or atomic force microscopy (AFM).

[0081] In the present invention, "body-centered cubic close-packed" refers to one of the closest packing methods in a cubic crystal system, which includes two lattice points, one at a corner and one at the body center, i.e., eight atoms are located at the eight corners of the cube, one atom is located at the center of the cube, and the eight atoms at the corners are each adjacent to the atom at the center.

[0082] In the present invention, "face-centered cubic close-packed" means that the 14 atoms involved in the unit cell belong to four layers, with one vertex angle being layer A, the three face-centered atoms nearest to it and the three vertex angle atoms belong to layer B, the next six atoms belong to layer C, and there is one vertex angle opposite the vertex angle of layer A, which is in layer A of the next cycle.

[0083] When the hydrogen gas permeation and diffusion rate required for hydrogen-related reactions and the required thickness of the palladium membrane are determined, the metal composition and ratio of the palladium membrane and the lattice constant can be selected through the above examples.

[0084] For example, if the hydrogen gas permeation / diffusion rate J = 0.35 and the thickness d = 10 μm, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:32.8:23.4), with a correction factor b = 3.15 and a lattice parameter k = 0.4087; a palladium-gold (PdAu) binary alloy (alloy ratio 100:5.6), with a correction factor b = 3.03 and a lattice parameter k = 0.3836; and a palladium-silver (PdAg) binary alloy (alloy ratio 100:58.7), with a correction factor b = 1.29 and a lattice parameter k = 0.4034. All three combinations of palladium membranes can be determined as target palladium membranes.

[0085] For example, if the hydrogen gas permeation / diffusion rate J = 0.26 and the thickness d = 10 μm, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-gold (PdAu) binary alloy (alloy ratio 75:25), with a correction factor b = 2.01 and a lattice parameter k = 0.4156; a palladium-copper-gold (PdCuAu) ternary alloy (alloy ratio 100:13.5:9.2), with a correction factor b = 3.86 and a lattice parameter k = 0.4062; and a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:19.7:23.5), with a correction factor b = 2.53 and a lattice parameter k = 0.4284. All three combinations of palladium membranes can be determined as target palladium membranes.

[0086] For example, if the hydrogen gas permeation / diffusion rate J = 0.36 and the thickness d = 7.5 μm, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-silver (PdAg) binary alloy (alloy ratio 100:54), with a correction factor b = 1.75 and a lattice parameter k = 0.4125; a palladium-gold (PdAu) binary alloy (alloy ratio 100:8.8), with a correction factor b = 3.36 and a lattice parameter k = 0.3863; and a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:15.3:26.6), with a correction factor b = 2.80 and a lattice parameter k = 0.3953. All three combinations of palladium membranes can be determined as target palladium membranes. For example, if the hydrogen gas permeation / diffusion rate J = 0.58 and the thickness d = 6 μm, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-copper (PdCu) ​​binary alloy (alloy ratio 100:113), with a correction factor b = 1.89 and a lattice parameter k = 0.2768; a palladium-copper-nickel (PdCuNi) ternary alloy (alloy ratio 100:34.5:29.1), with a correction factor b = 2.22 and a lattice parameter k = 0.2716; and a palladium-silver (PdAg) binary alloy (alloy ratio 100:153), with a correction factor b = 1.23 and a lattice parameter k = 0.3319. All three combinations of palladium membranes can be determined as target palladium membranes.

[0087] As described above, the innovative method of the present invention involves first determining the target lattice parameters and target metal composition and their proportions of the target palladium membrane from the target permeation and diffusion rate of hydrogen gas through the target palladium membrane, the target thickness of the target palladium membrane, and the correspondence between the permeation and diffusion rate of hydrogen gas through a sample palladium membrane and a specific parameter set for the sample palladium membrane, and then selecting a palladium membrane having the target lattice parameters, target metal composition and their proportions, and target thickness as the target palladium membrane. The present invention allows for efficient and simple selection of an appropriate palladium membrane that satisfies the target hydrogen gas permeation and diffusion rate for a hydrogen-related reaction.

[0088] One embodiment of the present invention provides a method for performing a hydrogen-related reaction, comprising the steps of selecting a target palladium membrane for the hydrogen-related reaction according to the method for selecting a target palladium membrane for the hydrogen-related reaction, wherein the permeation / diffusion rate of hydrogen gas through the target palladium membrane is a target permeation / diffusion rate; and performing the hydrogen-related reaction using one of the selected target palladium membranes.

[0089] The process of selecting the target palladium membrane for the hydrogen-related reaction can be referred to the relevant description of the method for selecting the target palladium membrane above, so it will not be described again here.

[0090] The hydrogen-related reaction is a reaction for synthesizing propylene oxide using hydrogen gas, oxygen gas, and propylene as substrates.

[0091] The hydrogen-related reaction is a reaction in which hydrogen peroxide is synthesized using hydrogen gas and oxygen gas as substrates.

[0092] The hydrogen-related reaction is a reaction for producing hydrogen by reforming alcohol and steam.

[0093] The hydrogen-related reaction is a hydrogenation reaction of carbon dioxide.

[0094] The hydrogen-related reaction is a reaction in which ammonia gas is synthesized using hydrogen gas and nitrogen gas as substrates.

[0095] The hydrogen-related reaction is a reaction for producing ethylene by dehydrogenating ethane.

[0096] The hydrogen-related reaction is a reaction for producing propylene by dehydrogenating propane.

[0097] The hydrogen-related reaction is a reaction in which butane is dehydrogenated to form butadiene.

[0098] The hydrogen-related reaction is a reaction in which isopentene is dehydrogenated to form isoprene.

[0099] The hydrogen-related reaction is a reaction for producing styrene by dehydrogenating ethylbenzene.

[0100] The hydrogen-related reaction is a reaction for producing isobutylene by dehydrogenating isobutane.

[0101] The hydrogen-related reaction is a reaction for producing cyclohexane by hydrogenating benzene.

[0102] The hydrogen-related reaction is a reaction for producing phenol using benzene, hydrogen gas, and oxygen gas as substrates.

[0103] The hydrogen-related reaction is a reaction for producing methanol by hydrogenating carbon monoxide.

[0104] The hydrogen-related reaction is a reaction for producing cyclohexanol by hydrogenating phenol.

[0105] The hydrogen-related reaction is a reaction in which nitrobenzene is hydrogenated and reduced to produce aniline. The hydrogen-related reaction is a reaction in which butane is dehydrogenated to produce butadiene.

[0106] Once the hydrogen gas permeation and diffusion rates required for hydrogen-related reactions and the required thickness of the palladium membrane are determined, the metal composition and ratio of the palladium membrane and its lattice constant can be selected based on the above examples. Below, several specific hydrogen-related reactions will be described as examples.

[0107] For example, if the hydrogen-related reaction is the hydrogenation of carbon dioxide, and the hydrogen gas permeation / diffusion rate J is 0.35 and the thickness d is 10 microns, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:32.8:23.4), with a correction factor b of 3.15 and a lattice parameter k of 0.4087; a palladium-gold (PdAu) binary alloy (alloy ratio 100:5.6), with a correction factor b of 3.03 and a lattice parameter k of 0.3836; and a palladium-silver (PdAg) binary alloy (alloy ratio 100:58.7), with a correction factor b of 1.29 and a lattice parameter k of 0.4034. Compared with palladium-gold (PdAu) and palladium-silver (PdAg) binary alloys, palladium-copper-silver (PdCuAg) ternary alloy membranes have superior carbon dioxide activation properties and can effectively promote the hydrogenation of carbon dioxide to produce hydrocarbons, a gasoline fraction. Furthermore, compared with palladium-gold and palladium-silver binary alloys, palladium-copper-silver ternary alloy membranes are more resistant to the poisoning of the palladium-based composite membrane body by hydrocarbons, resulting in a longer service life. Thus, palladium-copper-silver (PdCuAg) ternary alloy membranes are more suitable for the process of producing hydrocarbons, a gasoline fraction, through the hydrogenation of carbon dioxide. Therefore, a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:32.8:23.4), a correction factor b of 3.15, and a lattice parameter k of 0.4087 were used.

[0108] For example, if the hydrogen-related reaction is the production of hydrogen by reforming methanol and steam, and the hydrogen gas permeation / diffusion rate J is 0.26 and the thickness d is 10 microns, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-gold (PdAu) binary alloy (alloy ratio 75:25), with a correction coefficient b = 2.01 and a lattice parameter k = 0.4156; a palladium-copper-gold (PdCuAu) ternary alloy (alloy ratio 100:13.5:9.2), with a correction coefficient b = 3.86 and a lattice parameter k = 0.4062; and a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:19.7:23.5), with a correction coefficient b = 2.53 and a lattice parameter k = 0.4284. Palladium-gold (PdAu) binary alloy membranes have better carbon deposition resistance. Compared with palladium-copper-gold (PdCuAu) and palladium-copper-silver (PdCuAg) ternary alloy membranes, palladium-gold binary alloy membranes are less susceptible to poisoning by low-molecular-weight carbon-containing organic compounds such as CO and methanol, as well as water vapor. Palladium-gold (PdAu) binary alloy membranes can efficiently activate reactants such as methanol and water vapor, providing better catalytic activity. Therefore, palladium-gold (PdAu) binary alloy membranes are more suitable for the process of producing hydrogen by reforming alcohols and water vapor. Therefore, a palladium-gold (PdAu) binary alloy (75:25 alloy ratio), a correction coefficient b = 2.01, and a lattice parameter k = 0.4156 are used.

[0109] For example, if the hydrogen-related reaction is the synthesis of hydrogen peroxide using hydrogen gas and oxygen gas as substrates, and the hydrogen gas permeation / diffusion rate J is 0.36 and the thickness d is 7.5 μm, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-silver (PdAg) binary alloy (alloy ratio 100:54), with a correction factor b = 1.75 and a lattice parameter k = 0.4125; a palladium-gold (PdAu) binary alloy (alloy ratio 100:8.8), with a correction factor b = 3.36 and a lattice parameter k = 0.3863; and a palladium-copper-silver (PdCuAg) ternary alloy (alloy ratio 100:15.3:26.6), with a correction factor b = 2.80 and a lattice parameter k = 0.3953. Palladium-silver (PdAg) binary alloy membranes simultaneously activate H2 and O2 molecules, promoting the generation of HOO* and H* free radicals, providing a superior synergistic catalytic effect in the direct synthesis of hydrogen peroxide from hydrogen and oxygen gases. Furthermore, because the direct synthesis of hydrogen peroxide from hydrogen and oxygen is rapid, PdAg binary alloy membranes can generate more free radicals than PdAu binary alloys or PdCuAg ternary alloys, helping to improve the reaction catalytic rate. Therefore, PdAg binary alloy membranes are more suitable for the direct synthesis of hydrogen peroxide from hydrogen and oxygen. Therefore, a PdAg binary alloy (alloy ratio 100:54), correction factor b = 1.75, and lattice parameter k = 0.4125 were used.

[0110] For example, if the hydrogen-related reaction is the synthesis of propylene oxide using hydrogen gas, oxygen gas, and propylene as substrates, and the hydrogen gas permeation / diffusion rate J is 0.58 and the thickness d is 6 microns, the appropriate combination of metal composition, its ratio, and lattice parameter can be determined using Equation 5. This combination includes a palladium-copper (PdCu) ​​binary alloy (alloy ratio 100:113), with a correction factor b of 1.89 and a lattice parameter k of 0.2768; a palladium-copper-nickel (PdCuNi) ternary alloy (alloy ratio 100:34.5:29.1), with a correction factor b of 2.22 and a lattice parameter k of 0.2716; and a palladium-silver (PdAg) binary alloy (alloy ratio 100:153), with a correction factor b of 1.23 and a lattice parameter k of 0.3319. Considering the relatively low reaction temperature (below 200°C) for the direct epoxidation of propylene gas, palladium-copper-nickel (PdCuNi) ternary alloy membranes exhibit a coexistence of α-PdH and β-PdH phases after hydrogen dissolution. The unit cell structures of these two phases are incompatible, making them susceptible to hydrogen embrittlement. Palladium-copper binary alloy membranes (BCC-PdCu), with their body-centered cubic structure, do not exhibit the coexistence of these two crystalline phases under the same operating conditions, reducing the risk of hydrogen embrittlement. Compared with palladium-silver (PdAg) binary alloy membranes, PdCu binary alloy membranes have superior sulfur resistance and carbon deposition resistance to propylene and trace amounts of impurities, such as propane and sulfur-containing compounds, that may be present in propylene. As described above, PdCu binary alloy membranes are more suitable for the direct epoxidation of propylene gas. Therefore, a palladium-silver (PdCu) ​​binary alloy (alloy ratio 100:113), correction factor b = 1.89, and lattice parameter k = 0.2768 are used.

[0111] In one embodiment, the target palladium membrane is produced by: (1) alloying palladium membrane raw materials under different alloying treatment conditions, measuring the lattice parameters of the products, and creating a fitting curve of the correspondence between the alloying treatment conditions and the lattice parameters; (2) determining target conditions for the alloying treatment from the lattice parameters of the target palladium membrane and the fitting curve; and (3) alloying the palladium membrane raw materials under the target conditions to obtain the target palladium membrane.

[0112] According to a preferred embodiment of the present invention, a database of alloying treatment conditions and lattice parameters is created based on a large amount of experiments in step (1), so that alloying treatment conditions corresponding to lattice parameters can be found more quickly and easily.

[0113] According to some embodiments of the present invention, the palladium membrane is a membrane-like material, and the palladium membrane raw material may include a support for supporting the palladium membrane to further ensure the operability of the material. Thus, in step (1), the palladium membrane raw material includes a support, Pd deposited on one or both surfaces of the support, and any other active components.

[0114] According to some embodiments of the present invention, in the palladium membrane raw material, the molar ratio of Pd to other active components is 1:(0.05 to 20), more preferably 1:(0.1 to 5), and even more preferably 1:(0.1 to 2).

[0115] According to some embodiments of the present invention, the other active component is at least one selected from Group IIIA, Group VIII, Group IB and Group IIIB elements, more preferably selected from Group IB and / or Group VIII elements, and even more preferably at least one selected from Cu, Ag, Au and Ni.

[0116] According to some embodiments of the present invention, the metal elements in the palladium film 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.

[0117] According to a preferred embodiment of the present invention, the palladium membrane raw materials in step (1) and step (3) have the same composition.

[0118] According to some embodiments of the present invention, the thickness of the support is 0.1 to 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 consisting of any two of the above), preferably 2 to 5 mm. The support can be made of a material commonly used in the art that can withstand the operating temperature of the present invention without affecting hydrogen permeability, i.e., does not deform at the operating temperature of the present invention and does not affect hydrogen permeability. In order to ensure excellent hydrogen permeability, as well as to obtain better mechanical and thermal stability and reduce the amount of palladium used (reducing costs), the support is preferably a porous support, which may be at least one selected from porous ceramic, porous glass, porous metal (e.g., porous stainless steel), porous quartz, and polymeric polymers, but is more preferably at least one selected from porous ceramic, porous metal, and polymeric polymers. Generally, the support has a porosity distribution range of 15 to 75% and an average pore size of 0.05 to 0.4 μm. To obtain a tubular membrane, the support is preferably a tubular support. Among them, the porous ceramic may be made of γ-Al2O3, which has a porosity distribution range of 25 to 66% and an average pore size of 0.12 to 0.4 μm. The porous stainless steel may be made of 316L (Fe), which has a porosity distribution range of 32 to 71% and an average pore size of 0.08 to 0.36 μm. 69 Cr 17 Ni 12The polymer may be a polyimide material having a porosity distribution range of 15 to 37% and an average pore diameter of 0.05 to 0.22 μm. The "porosity distribution range" can be measured by nitrogen physical adsorption. The "average pore diameter" can be measured by nitrogen physical adsorption.

[0119] According to the present invention, the palladium membrane raw material is preferably produced by depositing Pd and other active components on a support.

[0120] According to some embodiments of the present invention, the deposition method is not particularly limited and may be at least one of vapor deposition (e.g., physical vapor deposition or chemical vapor deposition), electroless plating, electroplating, and electroforming, but is preferably at least one of electroplating and electroless plating. For example, the specific operation method and conditions for the electroplating method are as follows: At a temperature of 10 to 50°C, a conductive layer support is used as the working electrode, a platinum electrode (Pd-plated, Au-plated, Ni-plated), a silver electrode (Ag-plated), and a waveguide with a copper content of 99.999% (Cu-plated) are used as the counter electrode, and a saturated calomel electrode is used as the reference electrode. At a temperature of 30°C, metal ions (Pd 2+ , and other active ingredient metal ions, e.g., Cu 2+ , Au 3+ , Ag + , Ni 2+ The concentration of palladium in the plating solution was 0.01-0.2 mol / L. The electroplating experiments were performed by cyclic voltammetry, with an operating voltage range of -0.60 V to 0.90 V, a scan rate of 0.01 V / s to 0.0075 V / s, a sweep segment range of 200 to 2000, and a sensitivity of 0.001 A / V to 0.0001 A / V. The corresponding metal ions in the plating solution were reduced and deposited on the working electrode to form a dense metal film material (i.e., palladium film raw material).

[0121] In the present invention, the palladium membrane has certain requirements in terms of hydrogen gas permeation / diffusion rate, selectivity, and cost. For example, the total thickness of Pd and other active components deposited on the support in the palladium membrane raw material is 0.5 to 30 μm (e.g., 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, and a range consisting of any two of the above), preferably 5 to 15 μm.

[0122] According to some embodiments of the present invention, in step (1), the alloying treatment conditions include temperature, pressure, time, temperature drop rate, and the like.

[0123] According to the present invention, the alloying treatment method is preferably as follows: the palladium membrane raw material is treated at 300 to 800°C and 0.1 to 1 MPa for 1 to 10 hours, and then the temperature is lowered to 100 to 250°C at a rate of more than 5°C / min, particularly 10 to 200°C / min. More preferably, the alloying treatment method is as follows: the palladium membrane raw material is treated at 350 to 650°C and 0.12 to 0.8 MPa for 2 to 8 hours, and then the temperature is lowered to 120 to 230°C at a rate of 20 to 150°C / min. By performing the alloying treatment in this manner, the crystal stability of the palladium membrane is further improved, and the stability of its hydrogen permeability is further improved (the time from when the hydrogen permeation amount starts to fluctuate until it finally stabilizes is further shortened). In the above-mentioned preferred alloying treatment method, there is no particular limitation on the temperature increase rate of the palladium membrane raw material.

[0124] According to the present invention, the method may further include a step of naturally cooling to room temperature after the alloying treatment to obtain a material for use.

[0125] According to the present invention, the alloying treatment is preferably carried out under an activating atmosphere. The gas providing the activating atmosphere may be any of various gases commonly known in the art that are gaseous under alloying treatment conditions. Preferably, the activating atmosphere is provided by at least one of a rare gas (e.g., Ar), N2, water vapor, H2, an acidic gas (e.g., CO2), and an alkaline gas (which may be an organic alkaline gas or an inorganic alkaline gas such as ethylenediamine and NH3). The addition of an alkaline gas promotes activation of the palladium-based alloy film and further stabilizes the body-centered (or face-centered) cubic crystal structure that is formed. Therefore, the activating atmosphere is more preferably provided by a non-alkaline gas and an alkaline gas.

[0126] According to some embodiments of the present invention, the gas providing the activation 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), more preferably 1:(0.2-0.8):(0.01-0.3).

[0127] According to some embodiments of the present invention, the gas providing the activation atmosphere contains H2 and N2, and the volume ratio of H2 to N2 is 1:(0.1 to 4), more preferably 1:(0.2 to 3.4).

[0128] According to some embodiments of the present invention, the gas providing the activation atmosphere contains H2 and Ar, and the volume ratio of H2 to Ar is 1:(0.1 to 8), more preferably 1:(0.5 to 6).

[0129] In the present invention, in order to verify the accuracy of the fitting curve of the correspondence relationship between the alloying treatment conditions and the lattice parameters in step (1), step (1) may further include a step of testing the hydrogen permeation activation energy of the product and creating a fitting curve of the correspondence relationship between the alloying treatment conditions and the hydrogen permeation activation energy.

[0130] In the present invention, the hydrogen permeation activation energy may preferably be obtained by testing using a palladium membrane hydrogen permeation system.

[0131] According to the present invention, the palladium-based composite alloy material can be covered with a protective layer to further improve its resistance to sulfur, chlorine, and carbon deposition. The protective layer does not affect the hydrogen permeability (hydrogen permeation activation energy) of the palladium-based composite alloy material, and a protective layer commonly used in the field, such as a modified or unmodified molecular sieve, can be used. Here, 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 (e.g., Au), a molecular sieve after silanization, or a molecular sieve modified with an active component layer (e.g., a MoO nanoparticle layer, a Na-FeO nanoparticle layer, etc.). Therefore, the present invention also provides a composite membrane comprising a palladium-based composite alloy material and a protective layer covering the surface of the palladium-based composite alloy material. Therefore, the method for producing the composite membrane can include producing a palladium-based composite alloy material by the above method, and then covering the surface of the palladium-based composite 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 to 50 nm.

[0132] The present invention also provides a method for producing a palladium membrane, which includes depositing Pd and Cu on the support and then alloying the support on which Pd and Cu are deposited, wherein the molar ratio of Pd to Cu is 100:(90-120).

[0133] According to the method for producing a palladium membrane of the present invention, the alloying treatment is preferably as follows: Treatment is performed in an activation atmosphere under conditions of a temperature of 570 to 600°C and a pressure of 0.37 to 0.52 MPa for 4 to 7 hours, followed by cooling to 120 to 180°C at a rate of 55 to 85°C / min (55°C / min, 60°C / min, 65°C / min, 70°C / min, 75°C / min, 80°C / min, 85°C / min, and a range consisting of any two of the above), and the gas providing the activation atmosphere contains H2, N2, and NH3, with the volume ratio of H2, N2, and NH3 being 100:(27 to 77):(1 to 21). The palladium membrane produced by this method exhibits a fast hydrogen gas permeation and diffusion rate. The palladium-copper alloy material obtained by this preferred embodiment has higher hydrogen permeability and stability. Addition of alkaline gas NH3 promotes activation of the palladium-based alloy film, resulting in the formation of a more stable body-centered cubic structure and a smaller half-width of the characteristic peak in the XRD spectrum.

[0134] In the present invention, the pressure of the alloying treatment is generally controlled by adjusting the amount of gas used to provide the activation atmosphere. After the temperature is reduced to 180°C or less at a specific rate, the alloy can be cooled to room temperature at room temperature.

[0135] In the method for producing a palladium membrane according to the present invention, the total thickness of Pd and Cu deposited on the support is preferably 0.5 to 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 consisting of any two of the above), more preferably 5 to 15 μm, and even more preferably 6 to 8 μm.

[0136] According to the method for producing a palladium membrane of the present invention, the thickness of the support is preferably 0.1 to 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 consisting of any two of the above), preferably 2 to 5 mm.

[0137] The present invention will now be described in more detail with reference to the following examples, in which the inner surface of the support was sealed with a polytetrafluoroethylene material, which was then removed prior to use or performance testing. [Example]

[0138] (I) Manufacturing of palladium-based alloy materials Porous stainless steel pipes (tubular, inner diameter: 9.5–10.5 mm, outer diameter: 12.5–13.5 mm, average pore size: 0.25 μm, porosity: 65%) were used as supports. They were first immersed in absolute ethanol for 30 minutes to remove surface contaminants such as dust and oil. The surface and interior of the support were then rinsed with deionized water, placed in warm water, and a vacuum pump was used to remove any remaining ethanol in the channels. Finally, the support was placed in an oven and dried at 423 K for 4 hours. Following Faraday's law, Pd and other active components (at least one of Cu, Ag, Au, and Ni) were deposited onto the support using electroplating. The types and molar ratios of Pd and other active components are shown in Table 2. The effective membrane area was 21–50 cm. 2 Here, the electroplating conditions are as follows: the conductive layer support is the working electrode, the platinum electrode (Pd plating) and other active component electrodes (other active component plating) are the counter electrodes, and the saturated calomel electrode is the reference electrode. At a temperature of 30°C, the metal ions (Pd 2+ , and other active metal ions, e.g., Cu 2+ , Au 3+ , Ag + , Ni 2+The concentrations of ammonium chloride (NH4)2PdCl4) and ethylenediamine (EDA, 99%, analytical grade) were added at 0.05-0.12 ml / min, ethylenediaminetetraacetic acid disodium salt (EDTA-2Na, 99%, analytical grade) at 0.025-0.05 ml / min, and bipyridine (C) were added at 0.025-0.05 ml / min. The electroplating experiments were performed by cyclic voltammetry. The operating voltage range was -0.60 V to -0.90 V, the scan rate was 0.0075 V / s, the scan period was 1000, and the sensitivity was 0.0001 A / V. Simultaneously, a plunger-type constant current pump was used to add a 0.05 mol / L solution of ammonium chloride ((NH4)2PdCl4) at 1-2 ml / min, a salt solution containing other active ingredients at a constant concentration at 0.2-1.5 ml / min, ethylenediaminetetraacetic acid disodium salt (EDTA-2Na, 99%, analytical grade) at 0.025-0.05 ml / min, and bipyridine (C). 10 H8N2 (99%, analytical grade) was added at a rate of 0.01–0.015 ml / min. The plating solution was vigorously stirred (1000 r / min) during the addition of the solution. Every 30 min of electroplating, the working electrode, washed with distilled water, was immersed in a 0.05 mol / L phosphoric acid (H3PO4) solution and a 0.05 mol / L dipotassium hydrogen phosphate (K2HPO4) solution for 10 min each. After the cyclic voltammetry program was completed, the working electrode was treated in distilled water at 80–100°C for 10–15 min before being removed. The support on which Pd and other active components were deposited was subjected to a high-temperature alloying treatment. The alloying treatment method was as follows: In an activating atmosphere, the electrode was treated at a temperature of T1 and a pressure of P for a predetermined time (t), and then cooled to a temperature of T2 at a rate of V. The types and volume ratios of gases providing the activation atmosphere are shown in Table 2, and the gases providing the activation atmosphere are used in amounts such that the pressure of the alloying process is P, and each parameter is detailed in Table 2. By changing the manufacturing conditions, various palladium-based alloy materials were obtained (see Table 2 for details).

[0139] (II) The materials obtained by the alloying treatment in each of the examples and comparative examples were characterized by the following methods, and the crystal structure parameters of the obtained materials are shown in Tables 2 and 3.

[0140] The crystalline phase structure of the material obtained by the alloying process was analyzed using an X'PertPRO / PANalytical automatic X-ray diffractometer manufactured by Philips (Netherlands). α The scanning range of the diffraction angle 2θ was 10 to 90°C. ° The interplanar spacing of the sample was calculated using the Bragg equation.

[0141]

number

[0142] The crystal structure of the material obtained by the alloying process was examined at the European Synchrotron Radiation Center in France (beam BM25A), which has a higher resolution, synchrotron radiation of λ = 0.0618886 nm or 0.077449 ​​nm, and tube pressure of 10.0335 keV. 2 The sample was placed in a quartz capillary tube with a diameter of 2 mm, and both ends of the tube were sealed with quartz wool. The quartz capillary tube was then placed on a rotatable sample stage (ensuring uniform temperature and a larger radiation exposure area). The test temperature range was 298–473 K (heated by a hot air blower), and the pressure range was 10. -4 The pressure was adjusted to about 130 kPa, and hydrogen gas was first introduced as the test atmosphere. After 30 minutes of treatment, the sample was evacuated, and then helium gas was introduced as a protective gas for measurement.

[0143] The test method for the lattice parameters of the material obtained by the alloying process is as follows: By combining with the in-situ XRD test described above, the unit cell parameters of the material obtained by the alloying process (expressed as both the three unit cell constants a, b, c and the intersection angles α, β, γ between the three edges of the unit cell) can be obtained using 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 crystal plane spacing (d1d2d3) of the corresponding characteristic crystal plane was obtained by conversion using the formula: For example, the PdCu alloy material obtained in the present invention belongs to a body-centered cubic packed (BCC) structure, and its characteristic crystal planes include (110), (111), (200), (210), and (211). In addition, the X-ray diffraction results showed a series of different characteristic crystal plane ratios (intensities corresponding to the measured different crystal planes). For example, in the PdCu alloy material obtained in the present invention, the (110) plane has a 2θ=43 o ±1 o The (111) plane corresponds to the characteristic peak at 2θ=53 o ±1 o The (200) plane corresponds to the characteristic peak at 2θ=62 o ±1 o The (210) plane corresponds to the characteristic peak at 2θ=70 o ±1 o The (211) plane corresponds to the characteristic peak at 2θ=79 o ±1 o This corresponds to the characteristic peak in the crystal plane. The lattice parameter k of the corresponding material was obtained by combining and converting the peak intensity of the characteristic crystal planes mentioned above through HighScorePlus analysis software.

[0144] The test method for the thickness of the material obtained by the alloying process was as follows: The alloy film thickness was measured according to the scale bar corresponding to the magnification obtained from the results of a scanning electron microscope (model: JSM-7610F).

[0145] The half-width of the material obtained by alloying treatment was measured as follows: From the XRD spectrum test results, the radian value of the half-width was obtained in combination with HighScorePlus analysis software.

[0146] J H2(Hydrogen gas permeation / diffusion rate, measured value, unit: mol m -2 ·s -1 The test method is to measure the volume (liters) of hydrogen gas permeating through a palladium composite membrane in 1 minute at 20°C and a transmembrane pressure difference of 0.1 MPa, and normalize the hydrogen permeation rate (mol m) according to the membrane area (square meters). -2 ·s -1 ).

[0147] [Table 2]

[0148] [Table 3]

[0149] In each example, when the ratio of the metal composition of the palladium film is not particularly specified, the default ratio is the same (for example, 1:1 or 1:1:1).

[0150] Furthermore, through a large amount of experiments, the present invention has created a database of alloying treatment conditions corresponding to the lattice parameters of palladium membranes, and tested the hydrogen gas permeation and diffusion rates of palladium membranes. As a result, it has been found that the lattice parameters and the hydrogen gas permeation and diffusion rates satisfy a certain relationship (e.g., Equation 5), and the hydrogen gas permeation and diffusion rates calculated by Equation 5 according to the lattice parameters are as shown in "J" in Table 3. H2 The calculated values ​​are shown in the "(Calculated Value)" column, and the deviation between the calculated and measured values ​​is less than 10%. Based on this, the hydrogen gas permeation and diffusion rates can be easily determined. In addition, when selecting different hydrogen gas permeation and diffusion rates, the corresponding lattice parameters can be quickly determined using Equation 5. These lattice parameters can then be entered into a database for screening, allowing the alloying treatment conditions to be quickly determined. This shortens the experimental cycle and significantly improves the efficiency of research, development, and production.

[0151] In this invention, by establishing the correspondence between hydrogen gas permeation / diffusion rate and lattice parameter, hydrogen gas permeation / diffusion rate can be easily detected, with less investment in devices and raw materials, less demand on detectors, ease of implementation, and high accuracy. Furthermore, by selecting alloying treatment conditions according to various needs, a series of palladium membranes with excellent properties that meet various needs, such as excellent hydrogen gas separation ability, high mechanical strength, long life, and excellent stability, can be more easily mass-produced.

[0152] As described above, the present invention innovatively involves first selecting a target palladium membrane for a hydrogen-related reaction using the method for selecting a target palladium membrane for a hydrogen-related reaction, and then conducting a hydrogen-related reaction using one of the selected target palladium membranes, thereby enabling the present invention to accurately control the progress of the hydrogen-related reaction so that the hydrogen gas permeation and diffusion rate meets the target value.

[0153] One embodiment of the present invention provides a method for determining a permeation and diffusion rate, the method including the steps of: measuring the lattice parameter of a palladium membrane; and determining the permeation and diffusion rate of hydrogen gas through the palladium membrane from the lattice parameter, metal composition, ratio, and thickness of the palladium membrane, as well as a correspondence relationship between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane, wherein the specific parameter set includes the lattice parameter, metal composition coefficient, and thickness.

[0154] Specifically, after selecting a target palladium membrane through the various embodiments described above or other methods, the permeation and diffusion rates of hydrogen gas through the target palladium membrane can be tested. First, the lattice parameter k' of the palladium membrane is determined by X-ray diffraction analysis or atomic force microscopy. Next, the metal composition coefficient A' is determined from the metal composition and its proportion in the palladium membrane. For example, A' is determined from the metal composition and its proportion in the palladium membrane in combination with the correspondence between the metal composition, its proportion, and the metal composition coefficient. Next, from k', A', and the thickness d' of the palladium membrane, the correspondence between the permeation and diffusion rates of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane (for example, the permeation and diffusion rates J shown in Table 1) can be determined. H2 , k, d, and A), the hydrogen gas permeation and diffusion rate J through the palladium membrane can be calculated by combining H2 ' can be determined.

[0155] In one embodiment, the correspondence between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes:

[0156]

number

[0157] After selecting a target palladium membrane through the above various embodiments or other methods, the permeation and diffusion rate of hydrogen gas through the target palladium membrane can be tested. After obtaining Equation 1, first determine the lattice parameter k' of the palladium membrane by X-ray diffraction analysis or atomic force microscopy analysis. Then, determine the metal composition coefficient A' from the metal composition and its ratio of the palladium membrane. For example, determine A' from the metal composition and its ratio of the palladium membrane by combining the correspondence between the metal composition, its ratio, and the metal composition coefficient. Next, substitute k', A', and the thickness d' of the palladium membrane into Equation 1 above to calculate the permeation and diffusion rate J of hydrogen gas through the palladium membrane. H2 ' can be determined.

[0158] Specifically, A depends on the number of metal species in the sample palladium membrane, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium membrane.

[0159] For example, A is determined by the following formula:

[0160]

number

[0161] Of course, A is not limited to the above formula 2, and may be a reasonable modification of the above formula 2. For example, a weighting coefficient w is multiplied based on formula 2. Specifically, w may be a value close to 1.

[0162] After selecting a target palladium membrane through the various embodiments described above or other methods, the permeation and diffusion rate of hydrogen gas through the target palladium membrane can be tested. First, the metal composition coefficient A' can be obtained from the metal composition and its ratio of the target palladium membrane using Equation 2. Next, the lattice parameter k' of the palladium membrane is measured using X-ray diffraction analysis or atomic force microscopy, and then k', A', and the thickness d' of the palladium membrane are substituted into Equation 1 above to calculate the permeation and diffusion rate J of hydrogen gas through the palladium membrane. H2 ' can be determined.

[0163] In another embodiment, Equation 1 above may be further optimized by adding a correction factor related to the metal composition of the sample palladium film.

[0164] The correspondence relationship between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane includes the following:

[0165]

number

[0166] Specifically, A depends on the number of metal species in the sample palladium membrane, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium membrane. For example, A is determined by the following formula:

[0167]

number

[0168] Of course, A is not limited to the above formula 4, and may be a reasonable modification of the above formula 4. For example, a weighting coefficient w is multiplied based on formula 4. Specifically, w may be a value close to 1.

[0169] When the target lattice parameters and target metal composition coefficients are selected, the target metal composition and its proportion may be obtained by Equation 4:

[0170] Specifically, b depends on the effective atomic radius of the sample palladium membrane. The value of b ranges from 1 to 5. For the range of the value of b depending on the material, see the relevant explanation of the method for selecting the target palladium membrane above.

[0171] After selecting a target palladium membrane through the various embodiments described above or other methods, the permeation and diffusion rate of hydrogen gas through the target palladium membrane can be tested. First, the metal composition coefficient A' can be obtained from the metal composition and its ratio of the target palladium membrane using Equation 4. Next, the lattice parameter k' of the palladium membrane is measured using X-ray diffraction analysis or atomic force microscopy, and then k', A', and the thickness d' of the palladium membrane are substituted into Equation 3 above to calculate the permeation and diffusion rate J of hydrogen gas through the palladium membrane. H2 ' can be determined.

[0172] Through research, the inventors have discovered that there is a certain correlation between the hydrogen gas permeation and diffusion rate and the lattice parameter of a palladium membrane. The lattice parameter can be measured using a single instrument, the process is simple, and the requirements for the detector are low. Therefore, determining the hydrogen gas permeation and diffusion rate using the lattice parameter greatly simplifies the process of detecting the hydrogen gas permeation and diffusion rate of a palladium membrane.

[0173] As described above, the present invention innovatively measures the lattice parameters of a palladium membrane, and then determines the permeation and diffusion rates of hydrogen gas through the palladium membrane from the lattice parameters, metal composition, ratio, and thickness of the palladium membrane, as well as the correspondence between the permeation and diffusion rates of hydrogen gas through a sample palladium membrane and a specific parameter set for the sample palladium membrane. This allows the present invention to efficiently and accurately measure the permeation and diffusion rates of hydrogen gas through a palladium membrane under non-destructive processing conditions.

[0174] One embodiment of the present invention provides a system for selecting a target palladium membrane, the system including: a memory for storing a correspondence relationship between a target permeation / diffusion rate of hydrogen gas through the target palladium membrane, a target thickness of the target palladium membrane, and the permeation / diffusion rate of hydrogen gas through a sample palladium membrane and a specific parameter set of the sample palladium membrane, the specific parameter set including a lattice parameter, a metal composition coefficient, and a thickness; and a processor configured to perform an operation of determining a target lattice parameter and a target metal composition and its proportion of the target palladium membrane from the target permeation / diffusion rate, the target thickness, and the correspondence relationship; and an operation of selecting a palladium membrane having the target lattice parameter, the target metal composition and its proportion, and the target thickness as the target palladium membrane.

[0175] For specific details and advantages of the target palladium membrane selection system according to the present invention, reference can be made to the above description of the target palladium membrane selection method, and therefore, they will not be described again here.

[0176] One embodiment of the present invention provides a system for performing hydrogen-related reactions, including the above-described system for selecting target palladium membranes for hydrogen-related reactions for selecting target palladium membranes for the hydrogen-related reactions, wherein the permeation / diffusion rate of hydrogen gas through the target palladium membranes is the target permeation / diffusion rate, and an execution device for performing the hydrogen-related reaction using one of the selected target palladium membranes.

[0177] Here, the performing unit may include a hydrogenation reactor, a dehydrogenation reactor, or a hydrogen production reactor. The performing unit may further include a desulfurization and denitrification tower, a light-ends removal tower, a heavy-ends removal tower, a fractionation tower, a catalyst storage tank, a hydrogen storage tank, a heat exchanger, a hydrogen transport pipeline, a mechanical pump, a steam piping network, and / or a large unit (such as a smoke turbine, a fan, or a compressor).

[0178] For specific details and advantages of the system for carrying out hydrogen-related reactions according to the present invention, reference can be made to the above description of the method for carrying out hydrogen-related reactions, and therefore, they will not be described again here.

[0179] One embodiment of the present invention provides a system for determining permeation and diffusion rates, including a measurement device for measuring the lattice parameter of a palladium membrane; a memory for storing the metal composition and its ratio, and the thickness of the palladium membrane; and a processor for determining the permeation and diffusion rates of hydrogen gas through the palladium membrane from the lattice parameter, metal composition and its ratio, and thickness of the palladium membrane, as well as a correspondence between the permeation and diffusion rates of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane, wherein the specific parameter set includes the lattice parameter, metal composition coefficient, and thickness.

[0180] For specific details and advantages of the system for determining permeation and diffusion rates according to the present invention, reference can be made to the above description of the method for determining permeation and diffusion rates, and therefore, they will not be described again here.

[0181] One embodiment of the present invention provides a computer-readable storage medium storing a computer program that, when executed by a processor, realizes the method for selecting a target palladium membrane for a hydrogen-related reaction, the method for performing the hydrogen-related reaction, and / or the method for determining permeation and diffusion rates.

[0182] The ranges and endpoints of any values ​​disclosed herein are not limited to the precise ranges or values, but should be understood to include values ​​approaching such ranges or values. In the case of numerical ranges, the range endpoints, the range endpoints and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges shall be considered to be specifically disclosed herein.

[0183] Although some embodiments of the present invention have been described in detail above with reference to the drawings, the present invention is not limited to the details of the above embodiments, and the technical solutions of the present invention can be easily modified within the technical idea of ​​the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0184] It should be noted that the specific technical features described in the above detailed description can be combined in any suitable manner unless there is a contradiction, and in order to avoid unnecessary repetition, the various possible combinations will not be further described in the embodiments of the present invention.

[0185] Those skilled in the art can understand that all or part of the steps of the methods in the above embodiments can be implemented by instructing relevant hardware through a program, which is stored in a storage medium and includes a plurality of instructions that cause a microcontroller, chip, or processor to execute all or part of the steps of the methods in each embodiment of the present application. The storage medium includes various media that can store program code, such as a USB memory, a mobile hard disk, a read-only memory (ROM), a random access memory (RAM), a magnetic disk, or an optical disk.

[0186] Furthermore, various embodiments of the examples of the present invention can be combined in any manner, and such combinations should also be considered as being disclosed in the examples of the present invention, unless they are contrary to the spirit of the examples of the present invention. [Brief explanation of the drawings]

[0187] [Figure 1] 2 is a flowchart of a method for selecting a target palladium membrane according to one embodiment of the present invention.

Claims

1. A method for selecting a target palladium membrane, comprising the steps of: determining a target lattice parameter and a target metal composition and its ratio of the target palladium membrane from a correspondence relationship between a target permeation / diffusion rate of hydrogen gas through the target palladium membrane, a target thickness of the target palladium membrane, and a specific parameter set of the sample palladium membrane, wherein the specific parameter set includes a lattice parameter, a metal composition coefficient, and a thickness; selecting a palladium film having the target lattice parameters, the target metal composition and its ratio, and the target thickness as the target palladium film.

2. 2. The selection method according to claim 1, wherein the correspondence between the permeation / diffusion rate of hydrogen gas through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes: [Equation 1] (where JH2 is the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane, k is the lattice parameter of the sample palladium membrane, d is the thickness of the sample palladium membrane, and A is the metal composition coefficient of the sample palladium membrane.)

3. 2. The selection method according to claim 1, wherein the correspondence between the permeation / diffusion rate of hydrogen gas through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes: [Equation 2] (where JH2 is the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane, k is the lattice parameter of the sample palladium membrane, d is the thickness of the sample palladium membrane, A is the metal composition coefficient of the sample palladium membrane, and b is a correction coefficient.)

4. 3. The method of claim 2, wherein A depends on the number of types of metals in the sample palladium film, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium film.

5. 5. The method of claim 4, wherein A is determined by the following formula: [Equation 3] (where n is the number of types of metals in the sample palladium membrane, M and ρ are the relative atomic mass and density of the i-th metal in the sample palladium membrane, respectively, and M and ρ are the average relative atomic mass and average density of the sample palladium membrane, respectively).

6. 4. The method of claim 3, wherein b depends on the effective atomic radius of the sample palladium film.

7. When the material of the sample palladium membrane is a PdCu alloy, the value of b ranges from 1.01 to 2.51, When the material of the sample palladium membrane is a PdAg alloy, the value of b ranges from 1.12 to 2.53, When the material of the sample palladium membrane is a PdAu alloy, the value of b ranges from 1.56 to 3.62, When the material of the sample palladium membrane is a PdCuAg alloy, the value of b ranges from 1.93 to 3.69, When the material of the sample palladium membrane is a PdCuAu alloy, the value of b is in the range of 2.56 to 4.99, or 7. The selection method according to claim 6, wherein when the material of the sample palladium membrane is a PdCuNi alloy, the value of b is in the range of 1.63 to 2.

71.

8. 1. A method for conducting a hydrogen-related reaction, comprising: A step of selecting a target palladium membrane for a hydrogen-related reaction by the method for selecting a target palladium membrane for a hydrogen-related reaction according to any one of claims 1 to 7, wherein the permeation / diffusion rate of hydrogen gas through the target palladium membrane is the target permeation / diffusion rate; and performing the hydrogen-related reaction using one of the selected target palladium membranes.

9. The hydrogen-related reaction is a reaction for synthesizing propylene oxide using hydrogen gas, oxygen gas, and propylene as substrates, The hydrogen-related reaction is a reaction for synthesizing hydrogen peroxide using hydrogen gas and oxygen gas as substrates, The hydrogen-related reaction is a reaction for producing hydrogen by reforming alcohol and steam, the hydrogen-related reaction is a hydrogenation reaction of carbon dioxide, The hydrogen-related reaction is a reaction for synthesizing ammonia gas using hydrogen gas and nitrogen gas as substrates, The hydrogen-related reaction is a reaction for producing ethylene by dehydrogenating ethane, The hydrogen-related reaction is a reaction for producing propylene by dehydrogenating propane, The hydrogen-related reaction is a reaction of dehydrogenating butane to form butadiene, The hydrogen-related reaction is a reaction of dehydrogenating isopentene to form isoprene, The hydrogen-related reaction is a reaction for producing styrene by dehydrogenating ethylbenzene, The hydrogen-related reaction is a reaction for producing isobutylene by dehydrogenating isobutane, The hydrogen-related reaction is a reaction for producing cyclohexane by hydrogenating benzene, The hydrogen-related reaction is a reaction for producing phenol using benzene, hydrogen gas, and oxygen gas as substrates, The hydrogen-related reaction is a reaction for producing methanol by hydrogenating carbon monoxide, The hydrogen-related reaction is a reaction for producing cyclohexanol by hydrogenating phenol, The hydrogen-related reaction is a reaction of hydrogenating and reducing nitrobenzene to produce aniline, 9. The method of claim 8, wherein the hydrogen-related reaction is the dehydrogenation of butane to produce butadiene.

10. The target palladium film is The palladium membrane raw material is alloyed under different alloying conditions, the lattice parameters of the products are measured, and a fitting curve of the correspondence between the alloying conditions and the lattice parameters is created. determining target conditions for an alloying treatment from the lattice parameters of the target palladium film and the fitting curve; 9. The method according to claim 8, wherein the target palladium membrane is produced by alloying the palladium membrane raw material under the target conditions to obtain the target palladium membrane.

11. A method for determining a permeation / diffusion rate, comprising: measuring the lattice parameter of the palladium film; determining the permeation and diffusion rate of hydrogen gas through the palladium membrane from the lattice parameter and metal composition, their ratios, and thickness of the palladium membrane, as well as a correspondence between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane, wherein the specific parameter set includes the lattice parameter, metal composition coefficient, and thickness.

12. 12. The method of claim 11, wherein the correspondence between the hydrogen gas permeation / diffusion rate through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes: [Equation 4] (where JH2 is the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane, k is the lattice parameter of the sample palladium membrane, d is the thickness of the sample palladium membrane, and A is the metal composition coefficient of the sample palladium membrane.)

13. 12. The method of claim 11, wherein the correspondence between the hydrogen gas permeation / diffusion rate through the sample palladium membrane and the specific parameter set of the sample palladium membrane includes: [Equation 5] (where JH2 is the permeation / diffusion rate of hydrogen gas passing through the sample palladium membrane, k is the lattice parameter of the sample palladium membrane, d is the thickness of the sample palladium membrane, A is the metal composition coefficient of the sample palladium membrane, and b is a correction coefficient.)

14. 13. The method of claim 12, wherein A depends on the number of metal species in the sample palladium film, the relative atomic masses and densities of the various metals, and the average relative atomic mass and average density of the sample palladium film.

15. 15. The method of claim 14, wherein A is determined by the following formula: [Equation 6] (where n is the number of types of metals in the sample palladium membrane, M and ρ are the relative atomic mass and density of the i-th metal in the sample palladium membrane, respectively, and M and ρ are the average relative atomic mass and average density of the sample palladium membrane, respectively).

16. 14. The method of claim 13, wherein b depends on the effective atomic radius of the sample palladium film.

17. 1. A target palladium membrane selection system comprising: a memory for storing a correspondence relationship between a target permeation / diffusion rate of hydrogen gas through the target palladium membrane, a target thickness of the target palladium membrane, and a specific parameter set of the sample palladium membrane, the specific parameter set including a lattice parameter, a metal composition coefficient, and a thickness; determining the target lattice parameters of the target palladium film and the target metal composition and its ratio from the target permeation / diffusion rates, the target thickness, and the correspondence relationship; and a processor configured to perform the operations of selecting, as the target palladium film, a palladium film having the target lattice parameters, the target metal composition and its proportions, and the target thickness.

18. 1. A system for performing hydrogen-related reactions, comprising:

18. A system for selecting a target palladium membrane for a hydrogen-related reaction according to claim 17, wherein the permeation / diffusion rate of hydrogen gas through the target palladium membrane is a target permeation / diffusion rate; and an execution device for executing the hydrogen-related reaction using one of the selected target palladium membranes.

19. 1. A system for determining permeation and diffusion rates, comprising: a measuring device for measuring the lattice parameter of the palladium film; a memory for storing the metal composition, the ratio thereof, and the thickness of the palladium film; and a processor for determining the permeation and diffusion rate of hydrogen gas through the palladium membrane from the lattice parameter and metal composition, their ratios, and thickness of the palladium membrane, as well as a correspondence between the permeation and diffusion rate of hydrogen gas through the sample palladium membrane and a specific parameter set of the sample palladium membrane, wherein the specific parameter set includes the lattice parameter, metal composition coefficient, and thickness.

20. A computer-readable storage medium storing a computer program that, when executed by a processor, realizes the method for selecting a target palladium membrane for a hydrogen-related reaction according to any one of claims 1 to 7.

21. A computer-readable storage medium storing a computer program that, when executed by a processor, realizes the method for performing a hydrogen-related reaction described in claim 8 above.

22. A computer-readable storage medium characterized by storing a computer program which, when executed by a processor, realizes the method for determining permeation / diffusion rates described in any one of claims 11 to 16 above.

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