Catalyst for preparing hydrogen deuteride as well as preparation method and application of catalyst

Abstract

The invention provides a catalyst for preparing deuteride and a preparation method and application thereof.The catalyst comprises a carrier, an active component, an auxiliary A, an auxiliary B and a modifier, the carrier is selected from a metal organic framework compound, the active component and the auxiliary A are both selected from VIII-group transition metal, the auxiliary B is selected from lanthanide series metal elements, and the modifier is selected from one or more metal elements. The regulator is selected from a nitrogen-containing organic compound. The catalyst provided by the invention can catalyze H2 and D2 gas to generate HD, and high-purity HD is obtained through temperature regulation and control and separation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of preparing deuterium hydride, and further relates to a catalyst for preparing deuterium hydride, a preparation method and application thereof. BACKGROUND

[0002] Deuterium hydride (HD) is a special hydrogen (H2) molecule containing one hydrogen atom (H) and one hydrogen isotope deuterium (D). In the study of the relationship between catalyst structure and performance, HD is an important probe molecule, which can be used to study the dissociation ability and dissociation hydrogen type of catalyst supported metal to hydrogen.

[0003] HD was first prepared by Scott and Brickwedde in the 1930s, who passed a mixture of hydrogen and deuterium through heated metal wires and then fractionated the equilibrium mixture at liquid hydrogen temperature, which contained about 50% molar deuterium hydride.

[0004] HD can also be obtained by reacting H2 with heavy water (D2O) or D2 with H2O. Generally, the yield of HD obtained by this method is higher. Norton (F.J. Norton, Science 111, 202 (1950)) treated boron hydride (B2H6) with deuterium gas and then reacted with water to obtain an isotopic mixture of hydrogen containing 85% HD. The hydride of Li can also react with heavy water to obtain high-purity HD (Journal of Research of the National Bureau of Standards, Vol. 47, No. I, July 1951, Research Paper 2224), and the purity can reach 99% by repeated distillation, but the reaction conditions are harsh.

[0005] Paul P. Hunt used gas chromatography to separate and analyze the components of hydrogen-deuterium mixture at 77K (J. Phys. Chem. 1961, 65, 1, 87-89), and the carrier gas was neon, and the chromatographic column was coated with chromium on alumina. Separation can be achieved on a laboratory scale.

[0006] Through research on the prior art, the synthesis of HD more often uses H2 and heavy water (D2O) or D2 and H2O, or heavy water (D2O) and Li hydride. The purification of HD more often uses low-temperature distillation, which has harsh reaction conditions, low reaction temperature, high energy consumption, and only meets the preparation and use on a laboratory scale.

[0007] Therefore, a simple and efficient method for preparing deuterium hydride still needs to be further developed. SUMMARY

[0008] To address the aforementioned problems, this invention provides a catalyst for preparing hydrogen deuteride and a method for preparing the same. The catalyst of this invention is used to catalyze the generation of hydrogen deuteride (HD) from H2 and D2 gases, and the gases are adsorbed onto the catalyst surface. High-purity HD is obtained by separating the gases through temperature control.

[0009] Firstly, one of the objectives of this invention is to provide a catalyst for the preparation of hydrogen deuteride.

[0010] The catalyst includes a support, an active component, an auxiliary agent A, an auxiliary agent B, and a regulator. The support is selected from metal-organic framework compounds, the active component and auxiliary agent A are both selected from group VIII transition metals, auxiliary agent B is selected from lanthanide metals, and the regulator is selected from nitrogen-containing organic compounds.

[0011] It is worth mentioning that the catalyst provided by the present invention can catalyze the formation of HD from H2 and D2 at a certain temperature, and HD, H2 and D2 are adsorbed on the catalyst surface at low temperature. By adjusting the surface temperature of the catalyst, HD, H2 and D2 are desorbed at different temperatures. Therefore, by selecting an appropriate desorption temperature, high-purity HD can be separated.

[0012] Furthermore, the catalyst provided by this invention has a specific surface area of ​​400–1500 m². 2 / g, preferably 800-1400m 2 / g.

[0013] Furthermore, the catalyst provided by this invention has a pore volume of 0.3–0.7 cm³. 3 / g, preferably 0.42~0.7cm 3 / g.

[0014] Furthermore, in the catalyst provided by the present invention, based on a total catalyst weight of 100 wt%, the weight percentage of the support is 78-98 wt%, preferably 85-96 wt%; the weight percentage of the active component is 0.05-1 wt%, preferably 0.1-0.5 wt%; the weight percentage of additive A is 0.05-1 wt%, preferably 0.1-0.5 wt%; the weight percentage of additive B is 0.5-10 wt%, preferably 1-8 wt%; and the weight percentage of the regulator is 0.5-10 wt%, preferably 1-8 wt%.

[0015] Furthermore, the metal-organic framework compound comprises a central metal ion and an organic ligand; wherein the central metal ion is selected from at least one of Mg and Zn metal ions; the organic ligand is selected from phthalic acid and its derivatives; preferably from terephthalic acid and its derivatives; particularly preferably from one or a combination of terephthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyterephthalic acid, and 2,3-dihydroxyterephthalic acid.

[0016] Furthermore, the active component is selected from one or a combination of Pd and Pt metals; auxiliary A is selected from one or a combination of Rh and Ir metals; auxiliary B is selected from one or a combination of La and Ce metal elements; and the nitrogen-containing organic compound is selected from one or a combination of imidazole, pyrazole, pyrimidine, and pyridazine.

[0017] Secondly, another objective of the present invention is to provide a method for preparing the catalyst, which is one of the objectives of the present invention.

[0018] Specifically, the method includes the following steps:

[0019] Step 1: Add the precursor of the central metal ion and the organic ligand to solvent one, reflux, separate, wash with solvent two, and dry to obtain the metal-organic framework compound.

[0020] Step 2: Add the metal-organic framework compound to an organic solvent, add a regulator and stir, then add the active component precursor, auxiliary agent A precursor and auxiliary agent B and stir. The separated solid is reduced and dried to obtain the catalyst.

[0021] More specifically, it includes the following steps:

[0022] Step 1: Preparation of metal-organic framework compounds: At room temperature, the precursor of the central metal ion and the organic ligand are added to solvent one, stirred and refluxed, centrifuged, washed with solvent two, and dried under vacuum to obtain metal-organic framework compounds.

[0023] Step 2, Catalyst Preparation: At room temperature, the metal-organic framework compound is placed in an organic solvent, and a regulator is added while stirring. After stirring for a certain period of time, the active component precursor, auxiliary agent A precursor, and auxiliary agent B are added. After stirring for a certain period of time, the solid obtained is separated by centrifugation and reduced with hydrogen gas. Then, it is dried under vacuum to obtain the catalyst.

[0024] Furthermore, in step one, the reflux time is 0.5 to 2 hours, preferably 1 to 1.5 hours; the drying temperature is 200 to 300°C, preferably 240 to 280°C; and the drying time is 4 to 8 hours, preferably 5 to 6 hours.

[0025] Furthermore, in step one, the precursor of the central metal ion is selected from the acetates of Mg and Zn metal ions; the organic ligand is selected from one or a combination of terephthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyterephthalic acid, and 2,3-dihydroxyterephthalic acid; solvent one is selected from one or a combination of N,N-dimethylformamide, anhydrous ethanol, and deionized water; and solvent two is selected from one or a combination of methanol and deionized water.

[0026] Further, in step two, a regulator is added and stirred for 12 to 24 hours, preferably 15 to 20 hours; an active component precursor, an auxiliary agent A precursor, and an auxiliary agent B are added and stirred for 0.5 to 4 hours, preferably 1 to 2 hours.

[0027] Furthermore, in step two, hydrogen is used for the reduction treatment, the treatment temperature is 80–120°C, preferably 80–100°C, and the time is 0.5–2 h, preferably 1–2 h.

[0028] Furthermore, in step two, the drying temperature is 100–130°C, preferably 110–120°C; the drying time is 4–8 hours, preferably 5–7 hours.

[0029] Furthermore, in step two, the organic solvent is selected from one or a combination of anhydrous dichloromethane and anhydrous trichloromethane; the modifier is selected from one or a combination of imidazole, pyrazole, pyrimidine, and pyridazine; the active component precursor is selected from one or a combination of Pd and Pt metal oxides; the auxiliary agent A precursor is selected from one or a combination of Rh and Ir metal oxides; and the auxiliary agent B is selected from one or a combination of La and Ce metal oxides. The particle size of the active component precursor, auxiliary agent A precursor, and auxiliary agent B is all less than or equal to 0.15 mm. This invention uses relatively stable oxides in the preparation process, which on the one hand is more conducive to the dispersion of each component on the carrier, and on the other hand avoids high-temperature treatment.

[0030] Thirdly, a third objective of the present invention is to provide the application of the catalyst described in one of the objectives of the present invention.

[0031] Specifically, the catalyst provided by this invention is used to catalyze the generation of HD from H2 and D2 gases, and utilizes the different adsorption and desorption temperatures of HD, H2 and D2 by the catalyst to separate high-purity HD.

[0032] Furthermore, the catalyst of the present invention is applied to a device for catalyzing the generation of HD from H2 and D2 gases, wherein the device includes a gas cylinder, a switching valve, a heat-insulating sealing plug, a sample bottle, a temperature controller, a pressure gauge, a limiting valve, a vacuum pump exhaust gas collection device, and a vacuum pump.

[0033] The catalyst is placed in a sample bottle, and the bottle opening is sealed with a heat-insulating sealing plug. The sample bottle is connected to a gas cylinder and a vacuum pump through a switch valve and a limit valve, respectively. The vacuum pump is connected to a vacuum pump exhaust gas collection device. The sample bottle is also equipped with a pressure gauge and a temperature controller.

[0034] Furthermore, the step of catalyzing H2 and D2 to generate HD gas using the above-described apparatus is as follows:

[0035] S1. Keep the switch valve and the limiting valve closed, put the catalyst into the sample bottle, seal the heat-insulating plug, and set the temperature controller to room temperature;

[0036] S2. Open the limiting valve and evacuate at a decreasing rate of 5-20 mmHg / s until the pressure gauge pressure is less than 30-100 μmHg. Maintain this for 20-60 minutes, then close the limiting valve.

[0037] S3. Open the switch valve and introduce H2-D2 gas (volume ratio 1:1). When the pressure gauge reaches 700-800 mmHg, close the switch valve and maintain it for 0.5-2 hours.

[0038] S4. Control the temperature of temperature controller 5 to 78-80K and maintain it for 0.5-2 hours;

[0039] S5. Open the limiting valve and evacuate at a decreasing rate of 5-20 mmHg / s until the pressure gauge pressure is less than 30-100 μmHg, and maintain for 20-60 minutes.

[0040] S6. Close the limiting valve and control the temperature of temperature controller 5 to 85-95K for 20-60 minutes.

[0041] One of the methods for removing HD from the sample vial is the extraction method.

[0042] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0043] The catalyst provided by this invention catalyzes the reaction of H2 and D2 to generate HD at a certain temperature. HD, H2 and D2 can be adsorbed on the catalyst surface at low temperature. By controlling the temperature of the catalyst surface, HD, H2 and D2 can be desorbed at different temperatures. By setting an appropriate desorption temperature, high-purity HD can be separated. Attached Figure Description

[0044] Figure 1 This is a graph showing the adsorption performance of the catalyst provided in Example 1 of the present invention for different gases;

[0045] Figure 2 This is a graph showing the adsorption performance of the catalyst provided in Example 2 of the present invention for different gases;

[0046] Figure 3 This is a graph showing the adsorption performance of the catalyst provided in Example 3 of the present invention for different gases;

[0047] Figure 4 This is a graph showing the adsorption performance of the catalyst provided in Example 4 of the present invention for different gases;

[0048] Figure 5 This is a graph showing the adsorption performance of the catalyst provided in Example 5 of the present invention for different gases;

[0049] Figure 6 This is a graph showing the adsorption performance of the catalyst provided in Example 6 of the present invention for different gases;

[0050] Figure 7 This is a graph showing the adsorption performance of the catalyst provided in Example 7 of the present invention for different gases;

[0051] Figure 8 This is a gas composition analysis diagram of the sample bottle in Example 8 of the present invention;

[0052] Figure 9 This is a gas composition analysis diagram of the sample bottle in Example 9 of the present invention;

[0053] Figure 10 This is a gas composition analysis diagram of the sample bottle in Example 10 of the present invention;

[0054] Figure 11 This is a gas composition analysis diagram of the sample bottle in Example 11 of the present invention;

[0055] Figure 12 This is a gas composition analysis diagram of the sample bottle in Example 12 of the present invention;

[0056] Figure 13 This is a gas composition analysis diagram of the sample bottle in Example 13 of the present invention;

[0057] Figure 14 This is a gas composition analysis diagram of the sample bottle in Example 14 of the present invention;

[0058] Figure 15 This is a graph showing the adsorption performance of the comparative agent provided in Comparative Example 1 of the present invention for different gases.

[0059] Figure 16 This is a graph showing the adsorption performance of the comparative agent provided in Comparative Example 2 of the present invention for different gases.

[0060] Figure 17 This is a graph showing the adsorption performance of the comparative agent provided in Comparative Example 3 of the present invention for different gases.

[0061] Figure 18 This is a graph showing the adsorption performance of a blank sample tube for different gases according to the present invention.

[0062] Figure 19 This is a gas composition analysis diagram of the sample bottle in Comparative Example 5 of the present invention;

[0063] Figure 20 This is a gas composition analysis diagram of the sample bottle in Comparative Example 6 of the present invention;

[0064] Figure 21 This is a gas composition analysis diagram of the sample bottle in Comparative Example 7 of the present invention;

[0065] Figure 22 This is a schematic diagram of the apparatus used for catalytic reaction in Example 8 of the present invention;

[0066] The attached figures are labeled as follows:

[0067] 1-Gas cylinder, 2-Switch valve, 3-Insulating sealing plug, 4-Sample bottle, 5-Temperature controller, 6-Pressure gauge, 7-Limiting valve, 8-Vacuum pump exhaust gas collection device, 9-Vacuum pump. Detailed Implementation

[0068] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0069] The raw materials used in this invention are all commercially available. Among them, the metal oxides need to be ground and sieved through a 100-mesh sieve before use.

[0070] The test methods used in the following embodiments are as follows:

[0071] 1. Determination of catalyst specific surface area and pore volume

[0072] Accurately weigh a certain mass of sample and place it into a sample tube. Place the sample tube in a fully automated physical adsorption instrument for degassing. Then, place the sample tube in the analysis station for analysis, performing a full analysis using nitrogen adsorption-desorption isotherms. The specific surface area of ​​the catalyst (p / p0 range 0.001–0.01) is calculated using the BET method, and the pore volume of the catalyst (p / p0 = 0.995) is calculated using the single-point method.

[0073] 2. Methods for determining the content of catalyst support, active component, additive A, and additive B.

[0074] The weighed sample is placed in a tablet press and compressed into tablets. The compressed sample is then placed in an X-ray fluorescence spectrometer (XRF) using Cu Kα rays. The tube voltage and tube current are set to determine the metal element content in the support, the metal content of the active component, the metal content of additive A, and the metal element content of additive B. The contents of the support, active component (metal), additive A (metal), and additive B (metal oxide) in the catalyst are then calculated based on the chemical formula.

[0075] 3. Method for determining the content of catalyst regulators

[0076] A certain amount of sample is accurately weighed using a balance and placed into a fully automatic elemental analyzer. The instrument is set to CHN analysis mode, with helium as the carrier gas and reference gas, and oxygen as the combustion-supporting gas. The instrument automatically tests and obtains the content of C, H, and N elements, and calculates the content of the regulator based on its chemical formula.

[0077] 4. Determination of the hydrogen and deuterium adsorption performance of the catalyst

[0078] Accurately weigh a certain amount of sample and place it in a sample tube. Place the sample in the adsorption instrument and raise it to 373 K at 10 K / min under N2 purging conditions. Hold for 30 min and lower it to 80 K. Change the gas to a mixture of 1% H2, 1% D2, 2% HD, and 96% N2 (volume fraction). Adsorb for 30 min and then change back to N2 purging for 1 h. Use mass spectrometry to detect the signals of H2 (m / z = 2), D2 (m / z = 4), and HD (m / z = 3). Raise the K to 150 K at 5 K / min.

[0079] 5. Composition testing of the prepared gas

[0080] The preparative gas was extracted and introduced into the mass spectrometer via an autosampler. The carrier gas was N2, and the signals of H2 (m / z=2), D2 (m / z=4), and HD (m / z=3) were detected by the mass spectrometer.

[0081] Example 1

[0082] This example illustrates the preparation of the catalyst, and the specific preparation method is as follows:

[0083] Step 1: At room temperature, 0.86 g (4 mmol) Mg(CH3COO)2·4H2O and 0.4 g (2 mmol) 2,5-dihydroxyterephthalic acid were added to 50 ml of deionized water. After stirring and refluxing for 1 h, the mixture was centrifuged to obtain solid A. Solid A was washed three times with deionized water, then three times with methanol, and heated at 250 °C under vacuum for 5 h to obtain solid B, which is the metal-organic framework material.

[0084] Step 2: At room temperature, 0.91g of solid B was placed in 50ml of anhydrous dichloromethane. 0.03g of imidazole was added with stirring. After stirring for 15h, 3.5mg PdO, 3.7mg Rh2O3, and 0.03g La2O3 were added. After stirring for another 1h, the mixture was centrifuged to obtain solid C. Solid C was placed in a quartz tube and reduced by passing hydrogen gas through it at 100℃ for 1h. Solid D was then removed and dried under vacuum at 120℃ for 5h to obtain the finished catalyst 1.

[0085] The content of each component of the catalyst, specific surface area, pore volume, and results are shown in Table 1.

[0086] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 1 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb at around 90 K.

[0087] Example 2

[0088] This example illustrates the preparation of the catalyst, and the specific preparation method is as follows:

[0089] Step 1: At room temperature, add 0.88 g (4 mmol) Zn(CH3COO)2·2H2O and 0.33 g (2 mmol) terephthalic acid to 50 ml of deionized water. After stirring and refluxing for 1 h, centrifuge to obtain solid A; wash solid A three times with deionized water, then wash three times with methanol, and heat at 250 °C under vacuum for 5 h to obtain solid B, i.e., the metal-organic framework material;

[0090] Step 2: At room temperature, 0.91g of solid B was placed in 50ml of anhydrous chloroform. 0.03g of pyrazole was added with stirring. After stirring for 15h, 3.5mg of PtO2, 3.5mg of IrO2 and 0.03g of CeO2 were added. After stirring for another 1h, the mixture was centrifuged to obtain solid C. Solid C was placed in a quartz tube and reduced by passing hydrogen gas through it at 90℃ for 1h. Solid D was then removed and dried under vacuum at 120℃ for 5h to obtain the finished catalyst 2.

[0091] The content of each component of the catalyst, specific surface area, pore volume, and results are shown in Table 1.

[0092] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 2 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb at around 90 K.

[0093] Example 3

[0094] This example illustrates the preparation of the catalyst, and the specific preparation method is as follows:

[0095] Step 1: At room temperature, 0.86 g (4 mmol) Mg(CH3COO)2·4H2O and 0.36 g (2 mmol) 2-hydroxyterephthalic acid were added to 50 ml of deionized water. After stirring and refluxing for 1 h, the mixture was centrifuged to obtain solid A. Solid A was washed three times with deionized water, then three times with methanol, and heated under vacuum at 250 °C for 5 h to obtain solid B, which is the metal-organic framework material.

[0096] Step 2: At room temperature, 0.91 g of solid B was placed in 50 ml of anhydrous dichloromethane. 0.03 g of pyridazine was added with stirring. After stirring for 15 h, 3.5 mg PtO2, 3.7 mg Rh2O3, and 0.03 g CeO2 were added. Stirring continued for 1 h, followed by centrifugation to obtain solid C. Solid C was placed in a quartz tube and reduced by passing hydrogen gas through it at 110 °C for 1 h. Solid D was then removed and dried under vacuum at 120 °C for 5 h. The final catalyst 3 was obtained.

[0097] The content of each component of the catalyst, specific surface area, pore volume, and results are shown in Table 1.

[0098] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 3 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb at around 90 K.

[0099] Example 4

[0100] This example illustrates the preparation of the catalyst. The difference between this example and Example 1 is the content of the components. The specific preparation method is as follows:

[0101] Step 1: At room temperature, 0.86 g (4 mmol) Mg(CH3COO)2·4H2O and 0.4 g (2 mmol) 2,5-dihydroxyterephthalic acid were added to 50 ml of deionized water. After stirring and refluxing for 1 h, the mixture was centrifuged to obtain solid A. Solid A was washed three times with deionized water, then three times with methanol, and heated at 250 °C under vacuum for 5 h to obtain solid B, which is the metal-organic framework material.

[0102] Step 2: At room temperature, 0.80 g of solid B was placed in 50 ml of anhydrous dichloromethane. 0.08 g of imidazole was added while stirring. After stirring for 15 h, 10.5 mg of PdO, 11 mg of Rh2O3, and 0.08 g of La2O3 were added. After stirring for another h, the mixture was centrifuged to obtain solid C. Solid C was placed in a quartz tube and reduced by passing hydrogen gas through it at 100 °C for 1 h. Solid D was then removed and dried under vacuum at 120 °C for 5 h to obtain the finished catalyst 4.

[0103] The content of each component, specific surface area, pore volume, and results of the catalyst are shown in Table 1. Compared with catalyst 1, the content of the metal-organic framework support decreased, while the contents of active metal Pd, promoter Rh, promoter La2O3, and regulator imidazole increased, resulting in a significant decrease in specific surface area and pore volume.

[0104] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 4 H2 showed no desorption peak between 80 and 150 K, HD completely desorbed at around 90 K, and D2 began to desorb from around 95 K. Compared with catalyst 1, the desorption amounts of HD and D2 were relatively small.

[0105] Example 5

[0106] This example illustrates the preparation of the catalyst. The difference between this example and Example 1 is the content of the components. The specific preparation method is as follows:

[0107] Step 1: At room temperature, 0.86 g (4 mmol) Mg(CH3COO)2·4H2O and 0.4 g (2 mmol) 2,5-dihydroxyterephthalic acid were added to 50 ml of deionized water. After stirring and refluxing for 1 h, the mixture was centrifuged to obtain solid A. Solid A was washed three times with deionized water, then three times with methanol, and heated at 250 °C under vacuum for 5 h to obtain solid B, which is the metal-organic framework material.

[0108] Step 2: At room temperature, 0.95g of solid B was placed in 50ml of anhydrous dichloromethane. 0.015g of imidazole was added with stirring. After stirring for 15h, 1.1mg PdO, 1.2mg Rh₂O₃, and 0.015g La₂O₃ were added, and stirring continued for 1h. The mixture was then centrifuged to obtain solid C. Solid C was placed in a quartz tube and reduced by passing hydrogen gas through it at 100℃ for 1h. Solid D was then removed and dried under vacuum at 120℃ for 5h. The final catalyst, 5, was obtained.

[0109] The content of each component, specific surface area, pore volume, and results of the catalyst are shown in Table 1. Compared with catalyst 1, the content of the metal-organic framework support increased, while the contents of active metal Pd, promoter Rh, promoter La2O3, and regulator imidazole decreased, resulting in a significant increase in specific surface area and pore volume.

[0110] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 5 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb from around 86 K.

[0111] Example 6

[0112] This embodiment is used to illustrate the preparation of the catalyst. The preparation method of this embodiment is basically the same as that of Example 1, except that: in step one, the catalyst is stirred and refluxed for 1.5 h; and heated under vacuum at 280 °C for 6 h to obtain the finished catalyst 6.

[0113] The results of component content, specific surface area, pore volume, and acid content of the catalyst are shown in Table 1. Compared with catalyst 1, the component content did not change significantly, while the specific surface area and pore volume increased slightly but not by much.

[0114] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 6 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb at around 90 K.

[0115] Example 7

[0116] This embodiment is used to illustrate the preparation of the catalyst. The preparation method of this embodiment is basically the same as that of Example 1, except that: in step 2, imidazole is added and stirred for 20 h; PdO, Rh2O3 and La2O3 are added and stirred for another 2 h; hydrogen is introduced at 80 °C for reduction, and the reduction time is 1.5 h; solid D is dried under vacuum at 110 °C for 7 h to obtain the finished catalyst 7.

[0117] The content of each component, specific surface area, pore volume, and acidity of the catalyst are shown in Table 1. Compared with catalyst 1, the content of each component, specific surface area, and pore volume did not change significantly.

[0118] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 7 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb at around 90 K.

[0119] Example 8

[0120] This embodiment is used to illustrate the use of the catalyst prepared in Example 1 to catalyze the generation of HD from H2 and D2 gases.

[0121] Specifically, catalysts are applied to Figure 22 In the device shown, by Figure 22 It is known that the device includes a gas cylinder 1, a switch valve 2, a heat-insulating sealing plug 3, a sample bottle 4, a temperature controller 5, a pressure gauge 6, a limiting valve 7, a vacuum pump exhaust gas collection device 8, and a vacuum pump 9.

[0122] The catalyst is placed in the sample bottle 4, and the bottle mouth is sealed with a heat-insulating sealing plug 3. The sample bottle 4 is connected to the gas cylinder 1 and the vacuum pump 9 through the switch valve 2 and the limiting valve 7 respectively. The vacuum pump 9 is connected to the vacuum pump exhaust gas collection device 8. The sample bottle 4 is also equipped with a pressure gauge 6 and a temperature controller 5.

[0123] pass Figure 22 The specific steps of the device for catalytically generating HD from H2 and D2 gases are as follows:

[0124] S1. Keep the switch valve 2 and the limiting valve 7 closed, put the catalyst into the sample bottle 4, plug the heat-insulating sealing plug 3, and set the temperature controller 5 to room temperature.

[0125] S2. Open the limiting valve 7 and evacuate at a decreasing rate of 10 mmHg / s until the pressure in the pressure gauge 6 is less than 50 μmHg. Maintain this for 30 minutes and then close the limiting valve 7.

[0126] S3. Open valve 2 and introduce H2-D2 gas (volume ratio 1:1). When the pressure in pressure gauge 6 reaches 760 mmHg, close valve 2 and maintain for 1 hour.

[0127] S4. Set the temperature of temperature controller 5 to 80K and maintain it for 1 hour.

[0128] S5. Open the limiting valve 7 and evacuate at a decreasing rate of 10 mmHg / s until the pressure in the pressure gauge 6 is less than 50 μmHg, and maintain this for 30 minutes.

[0129] S6. Close the limiting valve 7 and control the temperature of the temperature controller 5 to 90K for 30 minutes.

[0130] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 8 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0131] Example 9

[0132] This embodiment illustrates the use of the catalyst prepared in Example 2 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0133] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 9 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0134] Example 10

[0135] This embodiment illustrates the use of the catalyst prepared in Example 3 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0136] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 10As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0137] Example 11

[0138] This embodiment illustrates the use of the catalyst prepared in Example 4 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0139] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 11 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0140] Example 12

[0141] This embodiment illustrates the use of the catalyst prepared in Example 5 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8, except that in step S6, the temperature of the temperature controller 5 is 85K.

[0142] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 12 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0143] Example 13

[0144] This embodiment illustrates the use of the catalyst prepared in Example 6 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0145] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 13 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0146] Example 14

[0147] This example illustrates the use of the catalyst prepared in Example 7 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0148] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 14 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. At this time, the gas in sample bottle 4 is high-purity hydrogen deuteride.

[0149] Comparative Example 1

[0150] The preparation method of this comparative example is basically the same as that of Example 1, except that in step 2, 0.94g of solid B is placed in 50ml of anhydrous dichloromethane at room temperature, and no modifier imidazole is added, that is, the composition of the catalyst does not contain the modifier imidazole, thus obtaining comparative agent 1.

[0151] The content of each component, specific surface area, and pore volume of the catalyst are shown in Table 1. Compared with catalyst 1, the specific surface area and pore volume have increased significantly.

[0152] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 15 H2 shows no desorption peak between 80 and 150 K, HD completely desorbs at around 95 K, and D2 begins to desorb from around 82 K. Separation of D2 and HD is relatively difficult.

[0153] Comparative Example 2

[0154] The preparation method of this comparative example is basically the same as that of Example 1, except that in step two, the step of "adding 3.5 mg PdO and 3.7 mg Rh2O3" is not included, that is, the composition of the catalyst does not contain the active component Pd and the auxiliary agent Rh, thus obtaining comparative agent 2.

[0155] The content of each component, specific surface area, pore volume, and results of the catalyst are shown in Table 1. Compared with catalyst 1, the specific surface area and pore volume remained basically unchanged.

[0156] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 16 H2 has no desorption peak between 80 and 150 K, HD completely desorbs at around 90 K, and D2 begins to desorb at around 90 K.

[0157] Comparative Example 3

[0158] The preparation method of this comparative example is basically the same as that of Example 1, except that in step 2, 0.74g of solid B is placed in 50ml of anhydrous dichloromethane at room temperature, and 0.2g of imidazole is added while stirring for 15h. That is, the contents of the carrier and the regulator imidazole are different, and the content of the regulator imidazole is higher, thus obtaining comparative agent 3.

[0159] The content of each component, specific surface area, and pore volume of the catalyst are shown in Table 1. Compared with catalyst 1, the specific surface area and pore volume decreased significantly, and both were relatively low.

[0160] The spectra of the catalyst's hydrogen and deuterium adsorption performance are shown in [reference needed]. Figure 17 H2 showed no desorption peak between 80 and 150 K, while the desorption amounts of HD and D2 were significantly reduced.

[0161] Comparative Example 4

[0162] This comparative example is a control experiment, used to illustrate the hydrogen and deuterium adsorption performance spectra of an empty sample tube after it is placed in the adsorption analyzer without adding a catalyst. (See attached image.) Figure 18 .

[0163] Comparative Example 5

[0164] This comparative example illustrates the use of the comparative agent prepared in Comparative Example 1 to catalyze the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0165] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 19 As shown, H2 has almost no peaks, but there are D2 and HD signal peaks, indicating that the catalyst has difficulty separating D2 and HD.

[0166] Comparative Example 6

[0167] This comparative example illustrates the use of the comparative agent prepared in Comparative Example 2 for catalyzing the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0168] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 20 As shown, D2, H2, and HD have almost no peaks. Since contrast agent 2 does not contain the active component Pd and the auxiliary agent Rh, H2 and D2 gases did not react to generate HD.

[0169] Comparative Example 7

[0170] This comparative example illustrates the use of the comparative agent prepared in Comparative Example 3 for catalyzing the generation of HD from H2 and D2 gases. The apparatus and preparation method used are the same as in Example 8.

[0171] The gas in sample bottle 4 was analyzed using test method 5, and the analysis results are as follows: Figure 21 As shown, there is an HD signal peak, while H2 and D2 have almost no peaks. Due to the high imidazole content in contrast agent 3, the specific surface area and pore volume decrease significantly, resulting in a significant reduction in the amount of HD adsorbed on the catalyst.

[0172] Table 1 shows the content, specific surface area, and pore volume of each component in the catalysts prepared in the above examples and comparative examples.

[0173] Table 1:

[0174]

[0175] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst for preparing hydrogen deuteride, characterized in that: The catalyst comprises a support, an active component, an auxiliary agent A, an auxiliary agent B, and a regulator. The support is selected from a metal-organic framework compound, the active component and auxiliary agent A are both selected from group VIII transition metals, the auxiliary agent B is selected from lanthanide metals, and the regulator is selected from nitrogen-containing organic compounds.

2. The catalyst for preparing hydrogen deuteride according to claim 1, characterized in that, The catalyst has a specific surface area of ​​400–1500 m². 2 / g, preferably 800-1400m 2 / g; and / or, the catalyst has a pore volume of 0.3–0.7 cm³. 3 / g, preferably 0.42~0.7cm 3 / g.

3. The catalyst for preparing hydrogen deuteride according to claim 1, characterized in that, In the catalyst, based on a total catalyst weight of 100 wt%, The carrier accounts for 78–98 wt% by weight, preferably 85–96 wt%; and / or, The active component has a weight percentage of 0.05–1 wt%, preferably 0.1–0.5 wt%; and / or, The weight percentage of the additive A is 0.05–1 wt%, preferably 0.1–0.5 wt%; and / or, The weight percentage of the auxiliary agent B is 0.5–10 wt%, preferably 1–8 wt%; and / or, The regulator has a weight percentage of 0.5–10 wt%; preferably 1–8 wt%.

4. The catalyst for preparing hydrogen deuteride according to claim 1, characterized in that, The metal-organic framework compound comprises a central metal ion and an organic ligand; the central metal ion is selected from at least one of Mg and Zn metal ions; and / or, the organic ligand is selected from phthalic acid and its derivatives.

5. The catalyst for preparing hydrogen deuteride according to claim 1, characterized in that, The active component is selected from one or a combination of Pd and Pt metals; and / or, the auxiliary agent A is selected from one or a combination of Rh and Ir metals; and / or, the auxiliary agent B is selected from one or a combination of La and Ce metals; and / or, the nitrogen-containing organic compound is selected from one or a combination of imidazole, pyrazole, pyrimidine, and pyridazine.

6. A method for preparing the catalyst according to any one of claims 1 to 5, comprising the following steps: Step 1: Add the precursor of the central metal ion and the organic ligand to solvent one, reflux, separate, wash with solvent two, and dry to obtain the metal-organic framework compound. Step 2: Add the metal-organic framework compound to an organic solvent, add a regulator and stir, then add the active component precursor, auxiliary agent A precursor and auxiliary agent B and stir. The separated solid is reduced and dried to obtain the catalyst.

7. The method for preparing the catalyst according to claim 6, characterized in that, In step one, the precursor of the central metal ion is selected from acetates of Mg and Zn metal ions; and / or, the organic ligand is selected from one or a combination of terephthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyterephthalic acid, and 2,3-dihydroxyterephthalic acid; and / or, solvent one is selected from one or a combination of N,N-dimethylformamide, anhydrous ethanol, and deionized water; and / or, solvent two is selected from one or a combination of methanol and deionized water.

8. The method for preparing the catalyst according to claim 6, characterized in that, In step one, the reflux time is 0.5 to 2 hours, preferably 1 to 1.5 hours; and / or the drying temperature is 200 to 300°C, preferably 240 to 280°C; and the drying time is 4 to 8 hours, preferably 5 to 6 hours.

9. The method for preparing the catalyst according to claim 6, characterized in that, In step two, the organic solvent is selected from one or a combination of anhydrous dichloromethane and anhydrous trichloromethane; and / or, the modifier is selected from one or a combination of imidazole, pyrazole, pyrimidine, and pyridazine; and / or, the active component precursor is selected from one or a combination of Pd and Pt metal oxides; and / or, the auxiliary agent A precursor is selected from one or a combination of Rh and Ir metal oxides; and / or, the auxiliary agent B is selected from one or a combination of La and Ce metal oxides.

10. The method for preparing the catalyst according to claim 6, characterized in that, In step two, the reaction conditions are as follows: Add the regulator and stir for 12–24 hours, preferably 15–20 hours; and / or, Add the active component precursor, auxiliary agent A precursor, and auxiliary agent B, and stir for 0.5–4 h, preferably 1–2 h; and / or, The reduction treatment uses hydrogen gas, with a treatment temperature of 80–120°C, preferably 80–100°C; a treatment time of 0.5–2 hours, preferably 1–2 hours; and / or, The drying temperature is 100–130℃, preferably 110–120℃; the drying time is 4–8 hours, preferably 5–7 hours.

11. The method for preparing the catalyst according to claim 6, characterized in that, The particle size of the active component precursor, the auxiliary agent A precursor, and the auxiliary agent B is less than or equal to 0.15 mm.

12. The application of the catalyst according to any one of claims 1 to 5, for catalyzing the generation of HD from H2 and D2 gases; and / or, for separating high-purity HD by adsorption and desorption.

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