CN110743538A

CN110743538A - Preparation method of catalyst

Info

Publication number: CN110743538A
Application number: CN201910863694.4A
Authority: CN
Inventors: 肖松涛; 欧阳应根; 叶国安; 刘协春; 王玲钰
Original assignee: China Institute of Atomic of Energy
Current assignee: China Institute of Atomic of Energy
Priority date: 2019-09-12
Filing date: 2019-09-12
Publication date: 2020-02-04

Abstract

The invention belongs to the technical field of catalysts, and relates to a preparation method of a catalyst. The preparation method comprises the following steps: (1) preparation of catalytically active material: preparing a catalytically active substance or compound thereof with altered isotopic composition and/or abundance by a suitable method; (2) preparation of the catalyst: the catalyst is prepared by utilizing each catalytic active substance or a compound thereof, the catalyst comprises the catalytic active substance, the catalytic active substance comprises at least one metal or a compound thereof, the metal element in the metal or the compound thereof is composed of non-radioactive isotopes with the composition and/or the abundance changed from natural, wherein the abundance of at least one non-radioactive isotope is changed by more than 1/20 and not less than 20 percent on the basis of the natural abundance. By utilizing the preparation method of the catalyst, the obtained catalyst has better catalytic performance.

Description

Preparation method of catalyst

Technical Field

The invention belongs to the technical field of catalysts, and relates to a preparation method of a catalyst.

Background

Catalyst materials and catalytic technology are one of the fundamental and critical materials and technologies for the development of the chemical industry today. In modern industry, the production value produced by catalytic technology accounts for about 30% of the total value of national economy.

In the catalyst:

the platinum catalyst is mainly used in the fields of inorganic chemical industry, petroleum refining, organic chemical industry, C1 chemical industry, fine chemical industry, purification and treatment of automobile exhaust and industrial gas, fuel cells, sensors and the like, so the platinum catalyst has very important position in the aspects of industrial catalysis, environmental protection and green energy technology and shows wide application prospect.

Ruthenium catalysts are relatively inexpensive, have a wide range of applications, and stand out in catalysts, especially in the petrochemical and chemical industries. At present, the ruthenium catalyst has good catalytic performance in many fields of hydrogenation, oxidation, hydrogenolysis, ammonia synthesis, hydrocarbon synthesis, hydroformylation and the like, has the characteristics of high activity, good stability, reaction energy consumption reduction and the like, and has wide application prospect.

Palladium is a silver-white transition metal of platinum group elements, and the types of palladium-containing catalysts are various, and the palladium-containing catalysts are mostly applied to reaction processes such as catalytic hydrogenation, catalytic oxidation and the like in petrochemical industry, such as reaction processes for preparing acetaldehyde, pyridine derivatives, vinyl acetate and various chemical products. In particular, a palladium catalyst is commonly used in hydrogenation reaction, alumina platinum, palladium or platinum-rhodium-palladium is commonly used as a catalyst for purifying automobile exhaust, a palladium-containing platinum net catalyst is commonly used in the ammoxidation reaction of nitric acid production, and a palladium/carbon catalyst is used for hydrogenation and disproportionation of rosin.

The molybdenum catalyst is relatively cheap, but has good catalytic activity, is various and has wide application range, and has prominent position in the catalyst, especially in petrochemical industry and chemical industry. The molybdenum catalyst is widely used for producing acrylonitrile and methacrylonitrile or preparing acrylic acid and butenoic acid by hydrofining, hydrodesulphurization, hydrodenitrification, ammoxidation of propane and isobutane of petroleum or preparing maleic anhydride (CHCO) by oxidizing butane₂)₂Oxidative dehydrogenation of O and 1-butylene to produce 1, 3-butadiene, production of ethanol or C1-C4 mixed alcohol by using synthesis gas, production of carbon fiber or single-wall carbon nanotube by catalytic pyrolysis of carbon-containing gas source, hydrogen production by reforming synthesis gas and production of fuel cell, liquefaction of lignite, NO-containing_XExhaust gas purification and gas phaseOxidation of acrolein to produce acrylic acid and the like.

Ag in the silver catalyst is the cheapest noble metal. The silver catalyst is relatively cheap and has good hydrogenation activity, and due to the advantages of good catalytic activity, high mechanical strength, insensitivity to poison, good thermal conductivity and the like, the silver catalyst is not only applied to hydrogenation of various unsaturated hydrocarbons, but also is a good catalyst in certain conversion processes such as dehydrogenation, oxidative dehalogenation, desulfurization and the like, and is a unique industrial catalyst for preparing ethylene oxide by directly oxidizing ethylene. And the silver catalyst has low preparation cost and is easy to obtain, and has potential in industrial application prospect.

The nickel catalyst is relatively cheap and has good hydrogenation activity, and due to the advantages of good catalytic activity, high mechanical strength, insensitivity to poison, good thermal conductivity and the like, the nickel catalyst is not only applied to hydrogenation of various unsaturated hydrocarbons, but also is a good catalyst in certain conversion processes such as dehydrogenation, oxidative dehalogenation, desulfurization and the like. And the nickel-based catalyst has low preparation cost and is easy to obtain, and has potential in industrial application prospect.

The copper is used as a catalyst, has the advantages of low price, low toxicity and the like, and is mild and simple in ligand. Because of this, the use of Cu for catalytic chemical reactions is a very popular area today.

Iron is a transition metal element, has wide distribution and occupies 4.75 percent of the shell content, and can be used for preparing catalysts, catalyzing and synthesizing ammonia, electrocatalysis, photocatalysis, reducing carbon dioxide, hydrogenation and other reactions.

Titanium catalysts have been widely used in the fields of organic synthesis and polymer materials, and another catalytic field of titanium catalysts is the field of photocatalysis. Titanium dioxide (TiO)₂) After photon energy of irradiation light with a certain frequency is absorbed, electrons on a valence band of the irradiation light jump to a conduction band, so that the irradiation light has strong reduction performance, holes are left in an original valence band, positive charges are carried, and strong oxidation performance is achieved. Both the photogenerated electrons and the photogenerated holes are extremely unstable and can reduce or oxidize the surrounding medium. Based on the mechanism, the titanium catalyst is widely applied to the aspects of treating environmental pollution by photocatalytic degradation, sterilizing, self-cleaning, decomposing water to produce hydrogen and the like.

However, these catalysts tend to produce carbon deposits during the reaction, resulting in deactivation and poor stability at high temperatures. In response to these problems, a great number of researchers worldwide have been devoted to developing novel catalysts to improve the catalytic activity, selectivity and lifetime of the catalysts.

Disclosure of Invention

The invention aims to provide a preparation method of a catalyst, so that the obtained catalyst has better catalytic performance.

To achieve this object, in a basic embodiment, the present invention provides a method for preparing a catalyst, the method comprising the steps of:

(1) preparation of catalytically active material: preparing a catalytically active substance or compound thereof with altered isotopic composition and/or abundance by a suitable method;

(2) preparation of the catalyst: the catalyst is prepared by utilizing each catalytic active substance or the compound thereof,

the catalyst comprises a catalytic active substance, wherein the catalytic active substance comprises at least one metal or a compound thereof, the metal element in the metal or the compound thereof is composed of a non-radioactive isotope with the composition and/or the abundance changed from the natural abundance, and the abundance of the at least one non-radioactive isotope is changed by 1/20 or more and not less than 20 percent on the basis of the natural abundance.

In a preferred embodiment, the present invention provides a method for preparing a catalyst, wherein the suitable method is an isotope separation method, an isotope mixing method, a nuclear reaction method or an elemental artificial production method.

Isotope separation methods can be mainly divided into chemical methods and physical methods, wherein the chemical methods include amalgam exchange methods, ion exchange chromatography, extraction methods and the like; physical methods include electromagnetic methods, molten salt electrolysis methods, electron transfer, molecular distillation, laser separation, and the like (see: Yangzhou, Zeng's title, stable isotope separation, atomic energy Press, first edition 1989, full book, especially page 23).

The isotope mixing method is to mix isotopes with different abundances to prepare isotopes with specified abundances, and mix the isotopes uniformly by a roller or the like.

The nuclear reaction method is a method of bombarding a nuclear nucleus with particles generated by a reactor or an accelerator, and mainly includes primary decay of (n, γ), (n, p), (n, d) (n,2n), (n, f), and target nuclides (see (U.S.) c.b. moore, eds. laser photochemical and isotope separation, atomic energy press, first edition 1988, full book, especially page 18) can be generated by combining the (n, p), (n, d), (n,2n) reaction and the secondary reaction (p, n), (p, d), (t, n), (t, 2 n).

The element artificial production method is to produce a new nuclide by nuclear fission or nuclear fusion (see (U.S.) Benedict (Benedict, M.) and the like, nuclear chemical engineering, atomic energy press, first edition 2011, full book, especially page 169).

In a preferred embodiment, the present invention provides a method for producing a catalyst, wherein the metal element of the at least one metal or the compound thereof is composed of a non-radioactive isotope whose composition and/or abundance is changed from natural, wherein the abundance of the at least one non-radioactive isotope is changed from 1/10 or more and not less than 20% based on the natural abundance.

In a preferred embodiment, the present invention provides a method for producing a catalyst, wherein the metal element of the at least one metal or the compound thereof is composed of a non-radioactive isotope whose composition and/or abundance is changed from natural, wherein the abundance of the at least one non-radioactive isotope is changed from 1/5 or more and not less than 20% based on the natural abundance.

In a preferred embodiment, the present invention provides a method for producing a catalyst, wherein the metal element of the at least one metal or the compound thereof is composed of a non-radioactive isotope whose composition and/or abundance is changed from natural, wherein the abundance of the at least one non-radioactive isotope is changed from 1/2 or more and not less than 20% based on the natural abundance.

In a preferred embodiment, the present invention provides a method for preparing a catalyst, wherein the catalyst further comprises a catalytic auxiliary substance, and the mass ratio of the catalytically active substance to the catalytic auxiliary substance is 1: 0.1-10.

In a more preferred embodiment, the present invention provides a process for the preparation of a catalyst wherein the catalytic auxiliary comprises a promoter.

In a more preferred embodiment, the present invention provides a method for preparing a catalyst, wherein the catalytic auxiliary material comprises a catalyst carrier selected from one or more of activated carbon, silicon carbide, alumina, graphene, silica and zeolite.

The preparation method has the beneficial effects that the catalyst obtained by the preparation method has better catalytic performance.

Detailed Description

The following examples further illustrate specific embodiments of the present invention.

Example 1: preparation examples

Based on the principle of isotope separation method, natural metal platinum powder (natural abundance of platinum isotope: Pt-190 is 0.01%, Pt-192 is 0.79%, Pt-194 is 32.9%, Pt-195 is 33.8%, Pt-196 is 25.3%, and Pt-198 is 7.2%) is separated by CAE-1 type magnetic separation device of nuclear technology institute of atomic energy science, China, and the specific operating conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-195-98. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-194 is 1.5%, the abundance ratio of Pt-195 is 98% and the abundance ratio of Pt-196 is 0.5% through ICP-MS detection.

Adding conductive graphite with the mass of 4 times of that of the separated platinum as a carbon source, and preparing the Pt/C catalyst with the mass fraction of Pt of 20% by a hydrothermal method (weighing salt of a catalytic active substance, dissolving the salt in deionized water, adding carrier conductive graphite, soaking for 1h, keeping the temperature at 40 ℃ for 2h, and drying at 80 ℃ to obtain a catalyst precursor, adding a small amount of urea solution into the prepared catalyst precursor, carrying out hydrothermal treatment at 130 ℃ for 6h, then filtering, washing to be neutral, drying at 120 ℃ overnight, and roasting at 550 ℃ for 4h to obtain the required catalyst).

Example 2: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-190-20. And collecting the separated platinum at a discharge port, wherein the abundance ratio of Pt-190 is 20%, the abundance ratio of Pt-194 is 50% and the abundance ratio of Pt-198 is 30% through ICP-MS detection.

Example 3: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-190-. The separated platinum is collected at a discharge port, and the abundance ratio of Pt-190 is 100 percent through ICP-MS detection.

Adding conductive graphite with the mass 4 times that of the separated platinum as a carbon source to prepare the Pt/C catalyst with the Pt mass fraction of 20%, wherein the preparation method comprises the following steps:

preparation of metal Pt into H₂PtCl₆Solution is prepared into 1mol/L H₂PtCl₆. Adding conductive graphite, stirring uniformly, adopting NaOH as a precipitator, adjusting the pH value to 7.5, obtaining a black precipitate through centrifugal washing, and calcining the black precipitate at 500 ℃ under the condition of hydrogen to obtain the catalyst.

Example 4: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-192-100. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-192 is 100 percent through ICP-MS detection.

Example 5: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-194-100. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-194 is 100 percent through ICP-MS detection.

Example 6: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-195-100. The separated platinum was collected at the outlet and the abundance of Pt-195 was 100% by ICP-MS.

Example 7: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-196-100. The separated platinum was collected at the outlet and the abundance of Pt-196 was 100% by ICP-MS.

Example 8: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-198-100. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-198 is 100 percent through ICP-MS detection.

Example 9: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-192-20. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-192 is 20 percent, the abundance ratio of Pt-194 is 50 percent and the abundance ratio of Pt-196 is 30 percent through ICP-MS detection.

Example 10: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-194-20. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-194 is 20%, the abundance ratio of Pt-195 is 50% and the abundance ratio of Pt-196 is 30% through ICP-MS detection.

preparation of metal Pt into H₂PtCl₆Solution is prepared into 1mol/L H₂PtCl₆. Incorporating electrical conductivityGraphite is evenly stirred, NaOH is used as a precipitator, the pH value is adjusted to 7.5, black precipitate is obtained by centrifugal washing, and the black precipitate is calcined under the condition of hydrogen gas at 500 ℃ to obtain the catalyst.

Example 11: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-194-31. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-194 is 31 percent, the abundance ratio of Pt-192 is 19 percent and the abundance ratio of Pt-195 is 50 percent through ICP-MS detection.

Example 12: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-194-35. And collecting the separated platinum at a discharge port, wherein the abundance ratio of Pt-194 is 35%, the abundance ratio of Pt-192 is 30% and the abundance ratio of Pt-196 is 35% through ICP-MS detection.

Example 13: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-195-20. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-195 is 20 percent, the abundance ratio of Pt-192 is 20 percent and the abundance ratio of Pt-194 is 60 percent through ICP-MS detection.

Example 14: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-195-31. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-195, Pt-192 and Pt-194 is 31%, 30% and 39% respectively through ICP-MS detection.

Example 15: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-195-35.5. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-195 is 35.5%, the abundance ratio of Pt-192 is 20% and the abundance ratio of Pt-194 is 44.5% through ICP-MS detection.

Example 16: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-196-20. And collecting the separated platinum at a discharge port, wherein the abundance ratio of Pt-196 is 20%, the abundance ratio of Pt-192 is 10%, the abundance ratio of Pt-194 is 20% and the abundance ratio of Pt-195 is 50% through ICP-MS detection.

Example 17: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-196-23. The separated platinum is collected at the discharge port, and the abundance ratio of Pt-196 is 23%, the abundance ratio of Pt-195 is 37% and the abundance ratio of Pt-198 is 40% through ICP-MS detection.

Example 18: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-196-27.5. The separated platinum was collected at the outlet and found by ICP-MS to have an abundance of Pt-196 of 27.5%, an abundance of Pt-195 of 50% and an abundance of Pt-198 of 22.5%.

Example 19: preparation examples

The method is characterized in that natural metal platinum powder is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science, China, based on the principle of an isotope separation method, and the specific operation conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter is Pt-198-20. The separated platinum is collected at the discharge hole, and the abundance ratio of Pt-198, Pt-195 and Pt-196 is 20%, 50% and 30% respectively, which are detected by ICP-MS.

Example 20: comparative preparation example

Adding conductive graphite with the mass of 4 times of that of natural metal platinum powder as a carbon source, and preparing the Pt/C catalyst with the mass fraction of Pt of 20% by a hydrothermal method (weighing salt of a catalytic active substance, dissolving the salt in deionized water, adding carrier conductive graphite, soaking for 1h, keeping the temperature at 40 ℃ for 2h, and drying at 80 ℃ to obtain a catalyst precursor, adding a small amount of urea solution into the prepared catalyst precursor, carrying out hydrothermal treatment at 130 ℃ for 6h, then filtering, washing to be neutral, drying at 120 ℃ overnight, and roasting at 550 ℃ for 4h to obtain the required catalyst).

Example 21: examples of catalytic reactions

Each of the catalysts prepared in the foregoing examples 1 to 20 was used as an oxygen reduction catalyst and supported on a glassy carbon electrode to prepare a working electrode (cathode) at 0.1M HClO₄And carrying out an electrocatalytic oxygen reduction reaction test in the electrolyte by using a rotating disc electrode. The loading amount of the catalytic active substance on the glassy carbon electrode is 7.65 mu g cm^-2The rotation speed is 1600 rpm. Oxygen is continuously introduced in the test process, and the scanning rate of the linear scanning voltammetry is 5mV^-1. The test results are shown in table 1 below.

TABLE 1 electrocatalytic oxygen reduction test results

Example 22: comparative preparation example

The method comprises the steps of converting ruthenium with natural isotopic abundance into ruthenium nitrate, converting nickel oxide with natural isotopic abundance into nickel nitrate, and taking active carbon (Xc-72) with natural isotopic abundance as a carbon source and potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and the mixture is stirred for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tubular furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-K/C catalyst.

Example 23: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-96-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-96 is 20%, the abundance ratio of Ru-98 is 40%, and the abundance ratio of Ru-99 is 40%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-58-20. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-58 is 20%, the abundance ratio of Ni-60 is 40%, and the abundance ratio of Ni-61 is 40% through ICP-MS detection.

And converting the separated ruthenium into ruthenium nitrate, converting the separated nickel oxide into nickel nitrate, and taking the activated carbon (Xc-72) with natural isotopic abundance as a carbon source and taking the potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and the mixture is stirred for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tubular furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-K/C catalyst.

Example 24: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-96-100. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-96 is 100%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-58-65. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-58 is 65%, the abundance ratio of Ni-60 is 20% and the abundance ratio of Ni-61 is 15% through ICP-MS detection.

Example 25: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-98-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-98 is 20%, the abundance ratio of Ru-99 is 40%, and the abundance ratio of Ru-100 is 40%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-58-71. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-58 is 71%, the abundance ratio of Ni-60 is 16% and the abundance ratio of Ni-61 is 13% through ICP-MS detection.

Example 26: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-98-100. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-98 is 100%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-58-100. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ni-58 is 100%.

Example 27: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-99-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-99 is 20%, the abundance ratio of Ru-100 is 40%, and the abundance ratio of Ru-101 is 40%.

And (2) converting the separated ruthenium into ruthenium nitrate, converting the nickel oxide with natural isotopic abundance into nickel nitrate, and taking the activated carbon (Xc-72) with natural isotopic abundance as a carbon source and the potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and the mixture is stirred for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tubular furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-K/C catalyst.

Example 28: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-99-100. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-99 is 100%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-63-20. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 20 percent and the abundance of Cu-65 is 80 percent.

And converting the separated ruthenium into ruthenium nitrate, converting the separated copper oxide into copper nitrate, and taking activated carbon (Xc-72) with natural isotopic abundance as a carbon source and potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and the mixture is stirred for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Cu-K/C catalyst.

Example 29: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-100-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-100 is 20%, the abundance ratio of Ru-101 is 40%, and the abundance ratio of Ru-102 is 40%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-63-65.5. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 65.5%, and the abundance of Cu-65 is 34.5%.

Example 30: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-100-. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-100 is 100%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-63-72.6. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 72.6 percent and the abundance of Cu-65 is 27.4 percent.

Example 31: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-101-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-101 is 20%, the abundance ratio of Ru-102 is 40%, and the abundance ratio of Ru-104 is 40%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-63-100. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 100%.

Example 32: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ru-101-. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-101 is 100%.

And (2) converting the separated ruthenium into ruthenium nitrate, converting the copper oxide with natural isotopic abundance into copper nitrate, and taking the activated carbon (Xc-72) with natural isotopic abundance as a carbon source and taking the potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and the mixture is stirred for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Cu-K/C catalyst.

Example 33: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-102-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-101 is 40%, the abundance ratio of Ru-102 is 20% and the abundance ratio of Ru-104 is 40%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-60-20. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ni-60 is 20%, the abundance of Ni-61 is 40% and the abundance of Ni-62 is 40%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-65-20. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 80 percent and the abundance of Cu-65 is 20 percent.

And converting the separated ruthenium into ruthenium nitrate, converting the separated nickel oxide into nickel nitrate, converting the separated copper oxide into copper nitrate, and taking the activated carbon (Xc-72) with natural isotope abundance as a carbon source and the potassium hydroxide with natural isotope abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and stirring is carried out for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-Cu-K/C catalyst.

Example 34: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-102-29.5. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-101 is 35%, the abundance ratio of Ru-102 is 29.5%, and the abundance ratio of Ru-104 is 35.5%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-60-24. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ni-60 is 24%, the abundance of Ni-61 is 38% and the abundance of Ni-62 is 38%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-65-29.3. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 70.7 percent and the abundance of Cu-65 is 29.3 percent.

Example 35: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ru-102-33.5. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-101 is 31%, the abundance ratio of Ru-102 is 33.5%, and the abundance ratio of Ru-104 is 35.5%.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-60-28. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-60 is 28%, the abundance ratio of Ni-61 is 38% and the abundance ratio of Ni-62 is 34% through ICP-MS detection.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-63-32.4. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Cu-63 is 32.4%, and the abundance of Cu-65 is 67.6%.

Example 36: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ru-102-. The separated ruthenium is collected at a discharge port, and the abundance ratio of the Ru-102 is 100 percent through ICP-MS detection.

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-60-100. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ni-60 is 100%.

And converting the separated ruthenium into ruthenium nitrate, converting the separated nickel oxide into nickel nitrate, converting the natural isotopic abundance copper oxide into copper nitrate, and taking the natural isotopic abundance activated carbon (Xc-72) as a carbon source and the natural isotopic abundance potassium hydroxide as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and stirring is carried out for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-Cu-K/C catalyst.

Example 37: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ru-104-20. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-101 is 40%, the abundance ratio of Ru-102 is 40%, and the abundance ratio of Ru-104 is 20%.

The method is characterized in that copper oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Cu-65-100. And collecting the separated copper oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Cu-65 is 100%.

And converting the separated ruthenium into ruthenium nitrate, converting the nickel oxide with natural isotopic abundance into nickel nitrate, converting the separated copper oxide into copper nitrate, and taking the activated carbon (Xc-72) with natural isotopic abundance as a carbon source and taking the potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and stirring is carried out for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-Cu-K/C catalyst.

Example 38: preparation examples

Based on the principle of an isotope separation method, ruthenium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy research institute, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ru-104-. And collecting the separated ruthenium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ru-104 is 100%.

And (2) converting the separated ruthenium into ruthenium nitrate, converting the nickel oxide with natural isotopic abundance into nickel nitrate, converting the copper oxide with natural isotopic abundance into copper nitrate, and taking the active carbon (Xc-72) with natural isotopic abundance as a carbon source and taking the potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and stirring is carried out for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-Cu-K/C catalyst.

Example 39: comparative preparation example

The method comprises the steps of converting ruthenium with natural isotopic abundance into ruthenium nitrate, converting nickel oxide with natural isotopic abundance into nickel nitrate, converting copper oxide with natural isotopic abundance into copper nitrate, and taking active carbon (Xc-72) with natural isotopic abundance as a carbon source and potassium hydroxide with natural isotopic abundance as a K source. 1g of ruthenium nitrate, 1g of nickel nitrate, 1g of copper nitrate, 10g of activated carbon and 5g of potassium hydroxide are weighed and dispersed in 50ml of distilled water to form a mixed solution, 10ml of absolute ethyl alcohol is added, and stirring is carried out for 30 min. The mixed solution is subjected to rotary evaporation for 1h in a rotary evaporator under the water bath of 80 ℃ and the vacuum degree of 0.08 MPa. Filtering, drying the precipitate at 80 ℃ for 4h, drying the precipitate at 120 ℃ for 8h, then putting the precipitate into a tube furnace, and reducing the precipitate at 450 ℃ for 4h at a hydrogen flow rate of 45mL/min to obtain the Ru-Ni-Cu-K/C catalyst.

Example 40: examples of catalytic reactions

The catalysts prepared in the previous examples 22-39 are respectively used for catalyzing the reaction of synthesizing formic acid by hydrogenating carbon dioxide, and the specific method is as follows:

adding catalyst (containing catalytic active substance 2.0g) into high-pressure reaction kettle, and reacting raw material CO₂Directly enters the reaction kettle from the steel cylinder in a gas-liquid coexisting mode. CO 2₂When the pressure in the reactor reaches 6.5MPa, the valve of the hydrogen cylinder is opened, and hydrogen is introduced into the reactor until the total pressure reaches 13.5 MPa. And starting a GCF controller, setting the stirring speed to be 360r/min, and adjusting the voltage to heat the reaction kettle. When the temperature in the reaction kettle rises to 80 ℃, the total pressure in the reaction kettle reaches 15.8MPa, and the reaction starts. After the reaction, the reaction vessel was cooled to 25 ℃ with ice water, and the filtered liquid product was quantitatively analyzed by high performance liquid chromatography using the number of moles of conversion of the reactant (TOF) as an index for evaluating the catalytic activity (number of moles of conversion of the reactant (TOF) ═ number of moles of conversion of the reactant/number of moles of the catalyst). The test results are shown in table 2 below.

Table 2 reaction test results for synthesizing formic acid by hydrogenation of carbon dioxide

Sources of catalyst	TOF/h^-1
		Example 22	40.3
Example 23	42.6
		Example 24	45.7
Example 25	46.9
		Example 26	41.8
Example 27	43.6
		Example 28	45.2
Example 29	47.8
		Example 30	51.36
Example 31	47.73
		Example 32	53.75
Example 33	47.84
		Example 34	47.96
Example 35	47.65
		Example 36	47.96
Example 37	48.07
		Example 38	55.63
Example 39	41.69

Comparing the results of the mole number conversion of the reactant of the above reaction, it can be seen that the ruthenium-based catalyst constructed based on the Ru source having isotopic abundance different from that of the natural Ru element has a higher mole number of reactant conversion under the same conditions.

Example 41: comparative preparation example

Palladium with natural isotope abundance (isotope natural abundance of palladium element: Pd-92: 14.84%, Pd-94: 9.25%, Pd-95: 15.92%, Pd-96: 16.68%, Pd-97: 9.55%, Pd-98: 24.13%, Pd-100: 9.63%) was converted into chloropalladate and prepared into a solution. 6.5g of Xc-72 activated carbon was taken, and 60mL of deionized water and a chloropalladate solution corresponding to 0.07g of palladium were added. And heating to 80 ℃, stirring for 2h, then cooling to 40 ℃, adding 3mL of formaldehyde solution with the volume concentration of 36%, stirring for 0.5h, dropwise adding NaOH solution (4mol/L) until the pH value is 8-9, keeping for 0.5h, heating to 80 ℃, and keeping for 1.0h (in the heat preservation period, the NaOH solution is required to be supplemented to ensure the pH value to be constant). Filtering, and fully washing a filter cake by using deionized water to obtain the Pd/C catalyst.

Example 42: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-102-20. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-102 is 20%, the abundance ratio of Pd-104 is 40%, and the abundance ratio of Pd-105 is 40%.

The separated palladium is converted into palladium chloride acid and prepared into a solution. 6.5g of Xc-72 activated carbon was taken, and 60mL of deionized water and a chloropalladate solution corresponding to 0.07g of palladium were added. And heating to 80 ℃, stirring for 2h, then cooling to 40 ℃, adding 3mL of formaldehyde solution with the volume concentration of 36%, stirring for 0.5h, dropwise adding NaOH solution (4mol/L) until the pH value is 8-9, keeping for 0.5h, heating to 80 ℃, and keeping for 1.0h (in the heat preservation period, the NaOH solution is required to be supplemented to ensure the pH value to be constant). Filtering, and fully washing a filter cake by using deionized water to obtain the Pd/C catalyst.

Example 43: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-102-100. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-102 is 100%.

Example 44: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-104-20. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-104 is 20%, the abundance ratio of Pd-105 is 40%, and the abundance ratio of Pd-106 is 40%.

Example 45: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-104-100. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance of Pd-104 is 100%.

Example 46: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-105-25. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-105 is 25%, the abundance ratio of Pd-106 is 38%, and the abundance ratio of Pd-108 is 37%.

Example 47: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-105-100. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-105 is 100%.

Example 48: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-106-20. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance of Pd-106 is 20%, the abundance of Pd-108 is 40% and the abundance of Pd-110 is 40%.

Example 49: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-106-25. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-106 is 25%, the abundance ratio of Pd-108 is 38%, and the abundance ratio of Pd-110 is 37%.

Example 50: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-106-30. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance of Pd-106 is 30%, the abundance of Pd-108 is 35%, and the abundance of Pd-110 is 35%.

Example 51: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-106-. The separated palladium is collected at a discharge port, and the abundance ratio of the Pd-106 is 100 percent through ICP-MS detection.

Example 52: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-108-20. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance of Pd-106 is 40%, the abundance of Pd-108 is 20% and the abundance of Pd-110 is 40%.

Example 53: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-108-24. And collecting the separated palladium at a discharge port, and detecting through ICP-MS, wherein the abundance ratio of Pd-106 is 38%, the abundance ratio of Pd-108 is 24%, and the abundance ratio of Pd-110 is 38%.

Example 54: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-108-29. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-106 is 36%, the abundance ratio of Pd-108 is 29% and the abundance ratio of Pd-110 is 35%.

Example 55: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-108-. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Pd-108 is 100%.

Example 56: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-110-20. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance of Pd-106 is 40%, the abundance of Pd-108 is 40% and the abundance of Pd-110 is 20%.

Example 57: preparation examples

The method is characterized in that palladium with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Pd-110-100. And collecting the separated palladium at a discharge port, and detecting by ICP-MS, wherein the abundance of Pd-110 is 100%.

Example 58: examples of catalytic reactions

The catalysts prepared in the previous examples 41 to 57 are respectively used for catalyzing the reaction of hydrogenating o-nitrochlorobenzene to prepare 2, 2-dichlorohydrazobenzene, and the specific method is as follows:

a1000 mL high-pressure reaction kettle is added with a catalyst (containing 2.0g of a catalytic active substance), 150g of o-nitrochlorobenzene, 150mL of toluene, 150mL of NaOH solution (with the mass percent concentration of 25%), 1g of sodium dodecyl benzene sulfonate and 0.55g of promoter naphthoquinone. After the reaction kettle is sealed, H is used₂Displacing air for 4 times, starting stirring and heating, heating to 65 deg.C, regulating rotation speed to 600r/min, introducing H with pressure of 0.4MPa into the reaction kettle₂. Measuring the time delta t required for the pressure in the reaction kettle to reduce by 0.1MPaH in the reaction kettle₂When the pressure no longer drops, the hydroprocessing is stopped. Taking out the reacted material liquid, filtering to remove catalyst, and analyzing the content of o-nitrochlorobenzene and 2, 2-dichlorohydrazobenzene in the separated organic phase by high performance liquid chromatography. The hydrogenation activity of the catalyst for o-nitrochlorobenzene was evaluated in terms of the yield of 2, 2-dichlorohydrazobenzene. The test results are shown in Table 3 below (yield of 2, 2-dichlorohydrazobenzene ═ n)_{(2, 2-Dichlorohydrazobenzene molar number)}/n_{(molar quantity of o-nitrochlorobenzene)}×100％)。

TABLE 3 reaction test results of hydrogenation of o-nitrochlorobenzene to prepare 2, 2-dichlorohydrazobenzene

Sources of catalyst	Yield (%)
		EXAMPLE 41	29.6
Example 42	34.5
		Example 43	35.7
Example 44	34.9
		Example 45	36.1
Example 46	35.2
		Example 47	36.7
Example 48	35.4
		Example 49	35.6
Example 50	35.7
		Example 51	36.9
Example 52	35.8
		Example 53	35.9
Example 54	36.3
		Example 55	37.2
Example 56	36.1
		Example 57	37.9

Compared with the yield results of the 2, 2-dichlorohydrazobenzene obtained by the reaction of preparing the 2, 2-dichlorohydrazobenzene by catalytic hydrogenation of the o-nitrochlorobenzene, it can be seen that the palladium-based catalyst constructed on the basis of the Pd source with isotopic abundance different from the natural Pd element has higher yield of the 2, 2-dichlorohydrazobenzene under the same conditions.

Example 59: comparative preparation example

Molybdenum oxide with natural isotopic abundance (natural isotopic abundances of molybdenum elements: 14.84% for Mo-92, 9.25% for Mo-94, 15.92% for Mo-95, 16.68% for Mo-96, 9.55% for Mo-97, 24.13% for Mo-98, and 9.63% for Mo-100) is converted into molybdenum nitrate, and 1.0g and 50g of aluminum nitrate with natural isotopic abundance are weighed and dissolved in distilled water to form mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain MoO/Al₂O₃A catalyst.

Example 60: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-94-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Mo-94 is 20%, the abundance of Mo-95 is 40%, and the abundance of Mo-96 is 40%.

And (3) converting the separated molybdenum oxide into molybdenum nitrate, weighing 1.0g of the molybdenum nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain MoO/Al₂O₃A catalyst.

Example 61: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-94-100. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-94 is 100%.

Example 62: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-95-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Mo-95 is 20%, the abundance of Mo-96 is 40%, and the abundance of Mo-97 is 40%.

And (3) converting the separated molybdenum oxide into molybdenum nitrate, weighing 1.0g of the molybdenum nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. The mixture is filtered and then is filtered,drying at 80 deg.C for 4 hr and at 120 deg.C for 20 hr in oven, placing the obtained dried product in muffle furnace, and calcining at 400 deg.C in static air for 2 hr to obtain MoO/Al₂O₃A catalyst.

Example 63: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-95-100. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-95 is 100%.

Example 64: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-96-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-96 is 20%, the abundance ratio of Mo-97 is 40%, and the abundance ratio of Mo-98 is 40%.

And (3) converting the separated molybdenum oxide into molybdenum nitrate, weighing 1.0g of the molybdenum nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃In a molar amount equal to the metal ionTotal molar amount of the components) and absolute ethyl alcohol, stirring for 30min, and then performing rotary evaporation in a rotary evaporator for 1h in a water bath at 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain MoO/Al₂O₃A catalyst.

Example 65: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-96-100. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-96 is 100%.

Example 66: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-97-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-97 is 20%, the abundance ratio of Mo-98 is 40%, and the abundance ratio of Mo-100 is 40%.

And (3) converting the separated molybdenum oxide into molybdenum nitrate, weighing 1.0g of the molybdenum nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. In the mixing ofAdding (NH) to the solution₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain MoO/Al₂O₃A catalyst.

Example 67: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-97-100. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-97 is 100%.

Example 68: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-98-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-97 is 40%, the abundance ratio of Mo-98 is 20%, and the abundance ratio of Mo-100 is 40%.

Oxidizing the separated oxideMolybdenum is converted into molybdenum nitrate, and 1.0g of the molybdenum nitrate and 50g of aluminum nitrate with natural isotope abundance are weighed and dissolved in distilled water to form mixed liquid. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain MoO/Al₂O₃A catalyst.

Example 69: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-98-22. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-97 is 39%, the abundance ratio of Mo-98 is 22% and the abundance ratio of Mo-100 is 39%.

Example 70: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-98-26. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-97 is 36%, the abundance ratio of Mo-98 is 26% and the abundance ratio of Mo-100 is 38%.

Example 71: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-98-100. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Mo-98 is 100%.

Example 72: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-100-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Mo-96 is 30%, the abundance of Mo-97 is 30%, the abundance of Mo-98 is 20%, and the abundance of Mo-100 is 20%.

Example 73: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-100-. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Mo-100 is 100%.

Example 74: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-92-20. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-92 is 20%, the abundance ratio of Mo-94 is 40%, and the abundance ratio of Mo-95 is 40%.

Example 75: preparation examples

The method is characterized in that molybdenum oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Mo-92-100. And collecting the separated molybdenum oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Mo-92 is 100%.

And (3) converting the separated molybdenum oxide into molybdenum nitrate, weighing 1.0g of the molybdenum nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and standing in static air at 400 deg.CRoasting for 2h to obtain MoO/Al₂O₃A catalyst.

Example 76: examples of catalytic reactions

The catalysts prepared in the previous examples 59 to 75 are respectively used for catalyzing the hydrogenation reaction of the electro-thiophene, and the specific method is as follows:

adding H with the pressure of 3.0MPa and the temperature of 400 ℃ into a reactor₂Preactivating catalyst (containing 1.0g of catalytic active substance) in airflow for 2H, adjusting temperature to 300 deg.C, pumping cyclohexane solution of thiophene with volume fraction of 5%, and introducing H₂The catalyst and cyclohexane solution are reacted for 2 hours under the pressure of 3.0MP and the volume ratio of 500: 1. The on-line analysis is carried out by a gas chromatograph, and the conversion rate of the thiophene is used as an index for measuring the HDS activity of the catalyst. The test results are shown in Table 4 below (thiophene conversion: X)_Thiophene(s)([ thiophene) ]]₀- [ thiophene₁]/([ thiophene)]₀)×100％)。

TABLE 4 hydrogenation of electrothiophene test results

Comparing the thiophene conversion reaction results, it can be seen that the Mo-based catalyst constructed based on a Mo source having isotopic abundance different from that of the natural Mo element has a higher thiophene conversion rate at the same temperature.

Example 77: comparative preparation example

Natural silver (natural abundance of silver isotope: 51.84% for Ag-107, 41.86% for Ag-109) was converted to silver nitrate, and 10.0g was weighed and dispersed in distilled water together with 50g of commercially available mordenite to form a mixed solution. Adding (NH) to the mixture₄)₂C₂O₄Solution ((NH)₄)₂C₂O₄The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. The mixture is filtered and then is filtered,drying at 80 ℃ for 4h and at 120 ℃ for 10h in an oven, putting the obtained dried product into a muffle furnace, and introducing a mixture of the components with the volume ratio of 1: h of 25₂/N₂Reducing and roasting the mixed gas for 4 hours at 400 ℃ to obtain the Ag/mordenite catalyst.

Example 78: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ag-107-20. And collecting the separated silver at a discharge port, and detecting through ICP-MS, wherein the abundance of Ag-107 is 20 percent and the abundance of Ag-109 is 80 percent.

The separated silver was converted to silver nitrate and 10.0 grams was weighed and dispersed in distilled water along with 50 grams of commercially available mordenite to form a mixed solution. Adding (NH) to the mixture₄)₂C₂O₄Solution ((NH)₄)₂C₂O₄The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in an oven at 80 ℃ for 4h and 120 ℃ for 10h, putting the obtained dried product into a muffle furnace, and introducing a mixture of the components in a volume ratio of 1: h of 25₂/N₂Reducing and roasting the mixed gas for 4 hours at 400 ℃ to obtain the Ag/mordenite catalyst.

Example 79: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ag-107-49. And collecting the separated silver at a discharge port, and detecting by ICP-MS, wherein the abundance of Ag-107 is 49 percent, and the abundance of Ag-109 is 51 percent.

Example 80: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ag-107-55. And collecting the separated silver at a discharge port, and detecting through ICP-MS, wherein the abundance of Ag-107 is 55 percent, and the abundance of Ag-109 is 45 percent.

Example 81: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ag-107-100. And collecting the separated silver at a discharge port, and detecting the silver by ICP-MS, wherein the abundance ratio of the Ag-107 is 100%.

The silver separated above was converted to silver nitrate and 10.0 grams was weighed and dispersed in distilled water along with 50 grams of commercially available mordeniteTo form a mixed solution. Adding (NH) to the mixture₄)₂C₂O₄Solution ((NH)₄)₂C₂O₄The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in an oven at 80 ℃ for 4h and 120 ℃ for 10h, putting the obtained dried product into a muffle furnace, and introducing a mixture of the components in a volume ratio of 1: h of 25₂/N₂Reducing and roasting the mixed gas for 4 hours at 400 ℃ to obtain the Ag/mordenite catalyst.

Example 82: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ag-109-20. And collecting the separated silver at a discharge port, and detecting through ICP-MS, wherein the abundance of Ag-107 is 80 percent, and the abundance of Ag-109 is 20 percent.

Example 83: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ag-107-45.5. And collecting the separated silver at a discharge port, and detecting through ICP-MS, wherein the abundance of the Ag-107 is 45.5 percent, and the abundance of the Ag-109 is 54.5 percent.

Example 84: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter Ag-109-50.5. The separated silver is collected at the discharge hole, and the abundance of the Ag-107 is 49.5 percent and the abundance of the Ag-109 is 50.5 percent through ICP-MS detection.

Example 85: preparation examples

The method is characterized in that natural metal silver is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ag-109-100. And collecting the separated silver at a discharge port, and detecting by ICP-MS, wherein the abundance of Ag-109 is 100%.

Example 86: examples of catalytic reactions

The catalysts prepared in the previous examples 77-85 are respectively used for catalyzing the reaction of synthesizing ethylene oxide from ethylene, and the specific method is as follows:

weighing a catalyst sample (containing 40 g of catalytic active substances), putting the catalyst sample into a stainless steel reaction tube with the inner diameter of 8mm, sealing the reaction tube, heating the reaction tube to 220 ℃, and introducing N into the reaction tube₂A mixture of balance gases (volume composition: C)₂H₄28.0% of O₂7.5% of CO₂2.5% of N₂62.0 percent) and space velocity of 4200h^-1Under the condition of (1), adopting an on-line gas chromatograph to measure the volume fraction of the ethylene oxide in the gas at the outlet of the reaction tube

The measurement results are shown in table 5 below.

TABLE 5 ethylene Synthesis of ethylene oxide reaction assay results

Sources of catalyst	Percent volume of ethylene oxide in the vent gas (%)
		Example 77	2.71
Example 78	3.86
		Example 79	3.13
Example 80	3.41
		Example 81	4.87
Example 82	3.75
		Example 83	3.24
Example 84	3.31
		Example 85	4.73

Example 87: comparative preparation example

Nickel oxide with natural isotope abundance (natural isotope abundance of nickel element: Ni-58: 68.27%, Ni-60: 26.1%, Ni-61: 1.13%, Ni-62: 3.59%, Ni)0.91% for-642) was converted to nickel nitrate and 1.0g was weighed out along with 50g of natural isotopically enriched aluminum nitrate and dissolved in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and at 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain NiO/Al₂O₃A catalyst.

Example 88: preparation examples

And (3) converting the separated nickel oxide into nickel nitrate, weighing 1.0g of nickel nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and at 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain NiO/Al₂O₃A catalyst.

Example 89: preparation examples

Example 90: preparation examples

Example 91: preparation examples

Example 92: preparation examples

Example 93: preparation examples

Example 94: preparation examples

And (3) converting the separated nickel oxide into nickel nitrate, weighing 1.0g of nickel nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and 120 deg.CDrying for 20h, placing the obtained dried product into a muffle furnace, and roasting at 400 ℃ in static air for 2h to obtain NiO/Al₂O₃A catalyst.

Example 95: preparation examples

Example 96: preparation examples

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-61-20. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-61 is 20%, the abundance ratio of Ni-62 is 40% and the abundance ratio of Ni-64 is 40% through ICP-MS detection.

And (3) converting the separated nickel oxide into nickel nitrate, weighing 1.0g of nickel nitrate and 50g of aluminum nitrate with natural isotope abundance, and dissolving the mixture in distilled water to form a mixed solution. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃In a molar amount equal to the total molar amount of metal ions) and anhydrous ethanol,stirring for 30min, and rotary evaporating in a rotary evaporator for 1h in water bath at 80 deg.C and vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and at 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain NiO/Al₂O₃A catalyst.

Example 97: preparation examples

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-61-100. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ni-61 is 100%.

Example 98: preparation examples

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-62-20. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-61 is 40%, the abundance ratio of Ni-62 is 20% and the abundance ratio of Ni-64 is 40% through ICP-MS detection.

Example 99: preparation examples

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-62-100. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ni-62 is 100%.

Example 100: preparation examples

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-64-20. And collecting the separated nickel oxide at a discharge port, wherein the abundance ratio of Ni-61 is 40%, the abundance ratio of Ni-62 is 40% and the abundance ratio of Ni-64 is 20% through ICP-MS detection.

Converting the separated nickel oxide into nickel nitrate, and weighing1.0 grams was dissolved in distilled water along with 50 grams of natural isotopically enriched aluminum nitrate to form a mixed liquor. Adding (NH) to the mixture₄)₂CO₃Solution ((NH)₄)₂CO₃The molar weight of the metal ions is equal to the total molar weight of the metal ions) and absolute ethyl alcohol, stirring for 30min, and then carrying out rotary evaporation for 1h in a rotary evaporator in a water bath at the temperature of 80 ℃ and under the vacuum degree of 0.08 MPa. Filtering, drying in oven at 80 deg.C for 4 hr and at 120 deg.C for 20 hr, placing the obtained dried product in muffle furnace, and calcining in static air at 400 deg.C for 2 hr to obtain NiO/Al₂O₃A catalyst.

Example 101: preparation examples

The method is characterized in that nickel oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ni-64-100. And collecting the separated nickel oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ni-64 is 100%.

Example 102: examples of catalytic reactions

The catalysts prepared in the previous examples 87-101 are respectively used for catalyzing the catalytic reforming reaction of ethanol, and the specific method is as follows:

weighing 0.10g of catalyst with the particle size of 40-60 meshes, diluting and mixing with a proper amount of quartz sand, placing in a reactor, and pretreating the prepared catalyst sample (N)₂Purging 3Introducing V (H) at 550 deg.C for 0min₂):V(N₂) 3:7 in a gas mixture at a gas flow rate of 70ml/min for 2 h). The temperature of the reaction bed is adjusted to 400 ℃, reactant water and ethanol (the mol ratio is 6) enter a vaporization chamber at a constant flow rate of 0.075ml/min to be vaporized at 120 ℃, and are mixed with carrier gas N₂After mixing, the mixture enters a reaction system for reaction. The gas product and ethanol concentration after reaction were analyzed by an on-line gas chromatograph. The test results are shown in table 6 below.

TABLE 6 catalytic reforming reaction of ethanol test results

Sources of catalyst	Ethanol conversion (%)
		Example 87	58
Example 88	61
		Example 89	62
Example 90	62.5
		Example 91	63
Example 92	62
		Example 93	62.9
Example 94	63.2
		Example 95	64
Example 96	63
		Example 97	65
Example 98	64
		Example 99	66
Example 100	65
		Example 101	67

Compared with the results of the ethanol catalytic reforming reaction, the nickel-based catalyst constructed on the Ni source with isotopic abundance different from that of the natural Ni element has higher conversion rate at the same temperature, which shows that the catalyst has more excellent activity and is beneficial to reducing the catalytic reforming cost.

Example 103: comparative preparation example

Converting copper oxide with natural isotopic abundance (natural isotopic abundance of copper element: 69.17% for Cu-63, 30.83% for Cu-65) into copper nitrate, and preparing the catalyst together with zinc nitrate with natural isotopic abundance and silicon dioxide (carrier) by a coprecipitation method, wherein the specific method comprises the following steps:

copper nitrate and zinc nitrate are weighed and added into distilled water to prepare mixed solutions of 1.0mol/L respectively. At 65 ℃, a 10% (m/v) silica suspension and 40ml of a 1mol/L sodium carbonate solution were added to 20ml of the mixed solution successively to bring the pH to 7 for coprecipitation. After the precipitation is finished, the aging is continued for 1h, and then the precipitation is filtered, washed and dried. Calcining the precipitate at 350 ℃ to obtain Cu/Zn/SiO₂A catalyst.

Example 104: preparation examples

Converting the separated copper oxide into copper nitrate, and preparing the catalyst together with natural isotopic abundance zinc nitrate and silicon dioxide (carrier) by a coprecipitation method, wherein the specific method comprises the following steps:

Example 105: preparation examples

Example 106: preparation examples

Example 107: preparation examples

Example 108: preparation examples

Example 109: preparation examples

Example 110: preparation examples

Example 111: preparation examples

Example 112: examples of catalytic reactions

The catalysts prepared in the previous embodiment 103-111 are respectively used for the catalysis of the reaction for synthesizing methanol from dimethyldichlorosilane, and the specific method is as follows:

10.0g of silicon powder and a catalyst (containing 1.0g of a catalytically active substance) are mixed and ground in a crucible for more than 5min in advance to uniformly disperse and eliminate agglomeration among catalyst particles. And introducing nitrogen into the reaction system (containing silicon powder and the catalyst) for 0.5h, heating to 325 ℃ (the nitrogen flow rate is 25mL/min), and switching the nitrogen to the chloromethane (the flow rate is 25mL/min) for reaction. The reaction product was collected with toluene by condensing the circulating water (5 deg.C), reacted for 24h, the methyl chloride was turned into nitrogen and the reactor was purged for 0.5h to cool to 20 deg.C. The reactor was opened, and the reaction residue was collected and weighed, and the mass of the mixture of dimethyldichlorosilane and catalyst before and after the reaction was calculated, and the conversion of silicon powder (silicon powder conversion ═ 1-mass of silicon powder after reaction/mass of silicon powder before reaction) × 100%) was calculated. The test results are shown in table 7 below.

TABLE 7 reaction test results for dimethyldichlorosilane to methanol

Comparing the reaction results of synthesizing methanol from dimethyldichlorosilane, it can be seen that the catalyst constructed based on a Cu source with isotopic abundance different from that of natural Cu element has higher silicon powder conversion rate under the same conditions.

Example 113: comparative preparation example

73.4g of iron oxide with natural isotopic abundance (natural isotopic abundance of iron element: 5.8% of Fe-54, 91.72% of Fe-56, 2.2% of Fe-57 and 0.28% of Fe-58) is converted into ferroferric oxide, and the following substances with natural isotopic abundance are weighed: 20.1g of iron powder, 2.2g of aluminum oxide, 0.7g of potassium oxide, 2.5g of calcium oxide, 0.4g of magnesium oxide and 0.7g of tungsten oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺Is 4.6, and the mass percentage content is as follows: 93.5% of iron oxide, 2.2% of aluminum oxide, 0.7% of potassium oxide, 2.5% of calcium oxide, 0.4% of magnesium oxide and 0.7% of tungsten oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.082))。

Example 114: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-54-20. And collecting the separated iron oxide at a discharge hole, and detecting through ICP-MS, wherein the abundance ratio of Fe-54 is 20%, the abundance ratio of Fe-56 is 70%, and the abundance ratio of Fe-57 is 10%.

And (3) converting the separated ferric oxide into ferroferric oxide, weighing 73.4g of the ferroferric oxide, and weighing the following substances with natural isotopic abundance: 20.1g of iron powder, 2.2g of aluminum oxide, 0.7g of potassium oxide, 2.5g of calcium oxide, 0.4g of magnesium oxide and 0.7g of tungsten oxide. The substances are mixed inMixing in a stirrer, charging into an electric melting furnace, and directly melting at atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺Is 4.6, and the mass percentage content is as follows: 93.5% of iron oxide, 2.2% of aluminum oxide, 0.7% of potassium oxide, 2.5% of calcium oxide, 0.4% of magnesium oxide and 0.7% of tungsten oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO， x＝0.082))。

Example 115: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-54-100. And collecting the separated iron oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Fe-54 is 100%.

And (3) converting the separated ferric oxide into ferroferric oxide, weighing 73.4g of the ferroferric oxide, and weighing the following substances with natural isotopic abundance: 20.1g of iron powder, 2.2g of aluminum oxide, 0.7g of potassium oxide, 2.5g of calcium oxide, 0.4g of magnesium oxide and 0.7g of tungsten oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺Is 4.6, and the mass percentage content is as follows: 93.5% of iron oxide, 2.2% of aluminum oxide, 0.7% of potassium oxide, 2.5% of calcium oxide, 0.4% of magnesium oxide and 0.7% of tungsten oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO， x＝0.082))。

Example 116: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-56-20. And collecting the separated iron oxide at a discharge hole, and detecting through ICP-MS, wherein the abundance ratio of Fe-56 is 20%, the abundance ratio of Fe-57 is 40% and the abundance ratio of Fe-58 is 40%.

Example 117: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-57-20. And collecting the separated iron oxide at a discharge hole, and detecting through ICP-MS, wherein the abundance ratio of Fe-56 is 45%, the abundance ratio of Fe-57 is 20% and the abundance ratio of Fe-58 is 35%.

Example 118: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-58-20. And collecting the separated iron oxide at a discharge hole, and detecting by ICP-MS, wherein the abundance ratio of Fe-56 is 50%, the abundance ratio of Fe-57 is 30% and the abundance ratio of Fe-58 is 20%.

Example 119: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-56-100. And collecting the separated iron oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Fe-56 is 100%.

69.8g of the separated ferric oxide is converted into ferroferric oxide, and the weight is as followsNatural isotopic abundance of substances: 22.6g of iron powder, 1.5g of aluminum oxide, 0.92g of potassium oxide, 1.3g of calcium oxide, 1.2g of magnesium oxide, 0.8g of vanadium oxide, 0.8g of tungsten oxide, 0.5g of zirconium oxide, 0.3g of titanium oxide and 0.3g of iridium oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺9.4, mass percent: 92.4% of iron oxide, 1.5% of aluminum oxide, 0.92% of potassium oxide, 1.3% of calcium oxide, 1.2% of magnesium oxide, 0.8% of vanadium oxide, 0.8% of tungsten oxide, 0.5% of zirconium oxide, 0.3% of titanium oxide and 0.3% of iridium oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.046))。

Example 120: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-57-100. And collecting the separated iron oxide at a discharge hole, and detecting by ICP-MS, wherein the abundance ratio of Fe-57 is 100%.

And (3) converting the separated ferric oxide into ferroferric oxide, weighing 69.8g of the ferroferric oxide, and weighing the following substances with natural isotopic abundance: 22.6g of iron powder, 1.5g of aluminum oxide, 0.92g of potassium oxide, 1.3g of calcium oxide, 1.2g of magnesium oxide, 0.8g of vanadium oxide, 0.8g of tungsten oxide, 0.5g of zirconium oxide, 0.3g of titanium oxide and 0.3g of iridium oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺9.4, mass percent: 92.4% of iron oxide, 1.5% of aluminum oxide, 0.92% of potassium oxide, 1.3% of calcium oxide, 1.2% of magnesium oxide, 0.8% of vanadium oxide and oxygen0.8% of tungsten oxide, 0.5% of zirconium oxide, 0.3% of titanium oxide and 0.3% of iridium oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.046))。

Example 121: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-58-100. And collecting the separated iron oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Fe-58 is 100%.

And (3) converting the separated ferric oxide into ferroferric oxide, weighing 69.8g of the ferroferric oxide, and weighing the following substances with natural isotopic abundance: 22.6g of iron powder, 1.5g of aluminum oxide, 0.92g of potassium oxide, 1.3g of calcium oxide, 1.2g of magnesium oxide, 0.8g of vanadium oxide, 0.8g of tungsten oxide, 0.5g of zirconium oxide, 0.3g of titanium oxide and 0.3g of iridium oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺9.4, mass percent: 92.4% of iron oxide, 1.5% of aluminum oxide, 0.92% of potassium oxide, 1.3% of calcium oxide, 1.2% of magnesium oxide, 0.8% of vanadium oxide, 0.8% of tungsten oxide, 0.5% of zirconium oxide, 0.3% of titanium oxide and 0.3% of iridium oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.046))。

Example 122: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-56-87.1. And collecting the separated iron oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Fe-56 is 87.1%, the abundance ratio of Fe-57 is 8% and the abundance ratio of Fe-58 is 4.9%.

Separating the above69.8g of iron oxide is converted into ferroferric oxide, and the following substances with natural isotopic abundance are weighed: 22.6g of iron powder, 1.5g of aluminum oxide, 0.92g of potassium oxide, 1.3g of calcium oxide, 1.2g of magnesium oxide, 0.8g of vanadium oxide, 0.8g of tungsten oxide, 0.5g of zirconium oxide, 0.3g of titanium oxide and 0.3g of iridium oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺9.4, mass percent: 92.4% of iron oxide, 1.5% of aluminum oxide, 0.92% of potassium oxide, 1.3% of calcium oxide, 1.2% of magnesium oxide, 0.8% of vanadium oxide, 0.8% of tungsten oxide, 0.5% of zirconium oxide, 0.3% of titanium oxide and 0.3% of iridium oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.046))。

Example 123: preparation examples

The method is characterized in that natural iron oxide is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Fe-56-96. And collecting the separated iron oxide at a discharge hole, and detecting by ICP-MS, wherein the abundance ratio of Fe-56 is 96 percent and the abundance ratio of Fe-58 is 4 percent.

And (3) converting the separated ferric oxide into ferroferric oxide, weighing 69.8g of the ferroferric oxide, and weighing the following substances with natural isotopic abundance: 22.6g of iron powder, 1.5g of aluminum oxide, 0.92g of potassium oxide, 1.3g of calcium oxide, 1.2g of magnesium oxide, 0.8g of vanadium oxide, 0.8g of tungsten oxide, 0.5g of zirconium oxide, 0.3g of titanium oxide and 0.3g of iridium oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺9.4, mass percent: 92.4% of iron oxide and 1% of aluminum oxide.5%, potassium oxide 0.92%, calcium oxide 1.3%, magnesium oxide 1.2%, vanadium oxide 0.8%, tungsten oxide 0.8%, zirconium oxide 0.5%, titanium oxide 0.3%, iridium oxide 0.3%. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.046))。

Example 124: comparative preparation example

Converting iron oxide with natural isotopic abundance into ferroferric oxide, weighing 69.8g, and weighing the following substances with natural isotopic abundance: 22.6g of iron powder, 1.5g of aluminum oxide, 0.92g of potassium oxide, 1.3g of calcium oxide, 1.2g of magnesium oxide, 0.8g of vanadium oxide, 0.8g of tungsten oxide, 0.5g of zirconium oxide, 0.3g of titanium oxide and 0.3g of iridium oxide. The materials are mixed in a stirrer, then put into an electric melting furnace and melted directly under atmospheric pressure. Cooling the melt in a cooling tank to below 200 deg.C, crushing, ball milling and sieving the cooled melt to obtain the catalyst product with required granularity (final component of the catalyst product is controlled by the ratio of ferrous iron to ferric iron Fe²⁺/Fe³⁺9.4, mass percent: 92.4% of iron oxide, 1.5% of aluminum oxide, 0.92% of potassium oxide, 1.3% of calcium oxide, 1.2% of magnesium oxide, 0.8% of vanadium oxide, 0.8% of tungsten oxide, 0.5% of zirconium oxide, 0.3% of titanium oxide and 0.3% of iridium oxide. XRD determination that the oxide of iron in the catalyst is a Vickers phase (Fe)₁-xO，x＝0.046))。

Example 125: examples of catalytic reactions

The catalysts prepared in the previous embodiment 113-124 are respectively used for the catalysis of the ammonia synthesis reaction, and the specific method is as follows:

0.1g of catalyst (the catalyst particle size is 1.0-1.4mm, and is in accordance with normal distribution) is placed in a reactor, the pressure is 15MPa, the temperature is 425 ℃, and the space velocity is 3.0 multiplied by 10⁴h^-1、H₂/N₂The synthetic ammonia reaction was carried out under the condition that the molar ratio was 3, and the concentration of organic substances such as ammonia at the outlet of the reactor was analyzed on line by a gas chromatograph.

The test results are shown in table 8 below.

TABLE 8 results of ammonia synthesis reaction test

Sources of catalyst	Reactor outlet ammonia volume percent concentration (%)
		Example 113	18.61
Example 114	19.82
		Example 115	20.59
Example 116	20.12
		Example 117	20.27
Example 118	20.38
		Example 119	20.89
Example 120	20.97
		Example 121	21.19
Example 122	20.67
		Example 123	20.75
Example 124	17.31

Comparing the results of the synthetic ammonia reaction, it can be seen that the synthetic ammonia catalyst constructed based on the Fe source having isotopic abundance different from that of the natural Fe element has higher ammonia yield under the same conditions, which is beneficial to reducing the cost of synthetic ammonia.

Example 126: preparation examples

Based on the principle of an isotope separation method, titanium oxide with natural isotope abundance (the natural abundance of titanium isotope is 8 percent of Ti-46, 7.3 percent of Ti-47, 73.8 percent of Ti-48, 5.5 percent of Ti-49 and 5.4 percent of Ti-50) is separated by an F-3 type magnetic separation device of the Chinese atomic energy scientific research institute), and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-46-20. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ti-46 is 20%, the abundance ratio of Ti-47 is 40%, and the abundance ratio of Ti-48 is 40%.

Converting the separated titanium oxide into titanium tetrachloride. Dripping titanium tetrachloride into nitric acid under nitrogen atmosphere, adding NH after titanium tetrachloride is completely hydrolyzed₄VO₄(natural isotope abundance) and urea, and after the urea is completely dissolved, quickly roasting for 5min at 500 ℃ to obtain the V-Ti catalyst.

Example 127: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-46-100. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ti-46 is 100%.

Converting the separated titanium oxide into titanium tetrachloride.Dripping titanium tetrachloride into nitric acid under nitrogen atmosphere, adding NH after titanium tetrachloride is completely hydrolyzed₄VO₄(natural isotope abundance) and urea, and after the urea is completely dissolved, quickly roasting for 5min at 500 ℃ to obtain the V-Ti catalyst.

Example 128: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-47-20. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-47 is 20%, the abundance of Ti-48 is 40% and the abundance of Ti-50 is 40%.

Example 129: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-47-100. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance ratio of Ti-47 is 100%.

Example 130: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-48-20. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-48 is 20%, the abundance of Ti-49 is 40% and the abundance of Ti-50 is 40%.

Example 131: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-48-70. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-48 is 70 percent and the abundance of Ti-50 is 30 percent.

Example 132: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-48-77.5. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-48 is 77.5 percent and the abundance of Ti-50 is 22.5 percent.

Example 133: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-48-100. And collecting the separated titanium oxide at a discharge hole, and detecting by ICP-MS, wherein the abundance ratio of Ti-48 is 100%.

Example 134: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-49-20. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-46 is 40%, the abundance of Ti-49 is 20% and the abundance of Ti-50 is 40%.

Example 135: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-49-100. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-49 is 100%.

Converting the separated titanium oxide into titanium tetrachloride. Dropping titanium tetrachloride in nitrogen atmosphereAdding into nitric acid, adding NH after titanium tetrachloride is completely hydrolyzed₄VO₄(natural isotope abundance) and urea, and after the urea is completely dissolved, quickly roasting for 5min at 500 ℃ to obtain the V-Ti catalyst.

Example 136: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-50-20. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-46 is 40%, the abundance of Ti-49 is 40% and the abundance of Ti-50 is 20%.

Example 137: preparation examples

The method is characterized in that titanium oxide with natural isotope abundance is separated by an F-3 type magnetic separation device of the Chinese atomic energy science research institute according to the principle of an isotope separation method, and the specific operation conditions are as follows: the temperature is 2000 ℃, the magnet power supply is 500A multiplied by 100V, the ion source voltage is 30-35kV, and the magnetic separation parameter is Ti-50-100. And collecting the separated titanium oxide at a discharge port, and detecting by ICP-MS, wherein the abundance of Ti-50 is 100%.

Example 138: comparative preparation example

Converting the natural isotopically abundant titanium oxide to titanium tetrachloride. Dripping titanium tetrachloride into nitric acid under nitrogen atmosphere, adding NH after titanium tetrachloride is completely hydrolyzed₄VO₄(natural isotopic abundance) and urea, 50 after it is completely dissolvedAnd (3) rapidly roasting at 0 ℃ for 5min to obtain the V-Ti catalyst.

Example 139: examples of catalytic reactions

The catalysts prepared in the foregoing example 126-138 are respectively used for the catalysis of the oxidation reaction of methanol to dimethoxymethane, and the specific method is as follows:

a normal pressure continuous flow fixed bed reactor was charged with a catalyst (containing 1.0g of a catalytically active substance) and 10% O was introduced₂Activation for 1h at 400 ℃ of/Ar (volume fraction). Introducing raw material gas (composition of V (Ar): V (O)) into the reactor₂):V(CH₃OH) 85:10:5)400 ℃, and the outlet gas was analyzed on-line by gas chromatography, using a TCD detector and a FID detector, respectively, for detection. The test results are shown in table 9 below.

TABLE 9 results of the oxidation of methanol to dimethoxymethane reaction

Sources of catalyst	Dimethoxymethane (DMM) yield (%)
		Example 126	31.57
Example 127	30.99
		Example 128	31.24
Example 129	32.02
		Example 130	31.15
Example 131	31.89
		Example 132	31.12
Example 133	31.02
		Example 134	32.00
Example 135	31.71
		Example 136	31.25
Example 137	31.43
		Example 138	29.95

Compared with the result of the reaction of catalyzing methanol to be oxidized into dimethoxymethane by the titanium-containing catalyst, the catalyst constructed on the basis of the Ti source with isotopic abundance different from that of the natural Ti element has higher hydrogen yield and more excellent catalytic effect under the same reaction condition.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.

Claims

1. The preparation method of the catalyst is characterized by comprising the following steps:

2. The method of claim 1, wherein: the suitable method is an isotope separation method, an isotope mixing method, a nuclear reaction method or an element artificial production method.

3. The method of claim 1, wherein: the metal element in the at least one metal or the compound thereof is composed of non-radioactive isotopes with the composition and/or the abundance changed from the natural abundance, wherein the abundance of the at least one non-radioactive isotope is changed by more than 1/10 and not less than 20 percent on the basis of the natural abundance.

4. The method of claim 1, wherein: the metal element in the at least one metal or the compound thereof is composed of non-radioactive isotopes with the composition and/or the abundance changed from the natural abundance, wherein the abundance of the at least one non-radioactive isotope is changed by more than 1/5 and not less than 20 percent on the basis of the natural abundance.

5. The method of claim 1, wherein: the metal element in the at least one metal or the compound thereof is composed of non-radioactive isotopes with the composition and/or the abundance changed from the natural abundance, wherein the abundance of the at least one non-radioactive isotope is changed by more than 1/2 and not less than 20 percent on the basis of the natural abundance.

6. The production method according to any one of claims 1 to 5, characterized in that: the catalyst also comprises a catalytic auxiliary substance, and the mass ratio of the catalytic active substance to the catalytic auxiliary substance is 1: 0.1-10.

7. The method of claim 6, wherein: the catalytic auxiliary substance comprises a cocatalyst.

8. The method of claim 6, wherein: the catalytic auxiliary substance comprises a catalyst carrier which is selected from one or more of active carbon, silicon carbide, aluminum oxide, graphene, silicon dioxide and zeolite.