CN110586106A

CN110586106A - Catalyst for catalytic synthesis of ammonia reaction and preparation method thereof

Info

Publication number: CN110586106A
Application number: CN201910863693.XA
Authority: CN
Inventors: 肖松涛; 欧阳应根; 刘协春; 王玲钰; 叶国安
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: 2019-12-20

Abstract

The invention belongs to the technical field of catalysts, and relates to a catalyst for catalyzing ammonia synthesis reaction and a preparation method 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. The catalyst for catalyzing the ammonia synthesis reaction and the preparation method thereof can ensure that the obtained catalyst has better catalytic performance.

Description

Catalyst for catalytic synthesis of ammonia reaction and preparation method thereof

Technical Field

The invention belongs to the technical field of catalysts, and relates to a catalyst for catalyzing ammonia synthesis reaction and a preparation method thereof.

Background

The synthetic ammonia catalyst has been studied for nearly one hundred years and practiced in the related industries, and as can be seen from the current results of research and practice, the synthetic ammonia catalyst mainly comprises an iron catalyst and a ruthenium catalyst.

Iron catalysts for ammonia synthesis are generally characterized by iron ratioThe valence state of iron in the catalyst is due to the fact that the iron ratio has a large influence on the activity of the resulting catalyst, and the iron ratio is preferably in the range of 0.4 to 0.9. And the nature of the variation of the synthetic ammonia iron catalyst is determined by iron oxides (Fe) with different crystal structures₂O₃、Fe₃O₄、Fe_1-xO), when the molecular ratio is 1, namely only one iron oxide and one crystal structure, the molten iron catalyst has high activity.

Currently, the Haber-Bosch process, i.e. the reaction of nitrogen and hydrogen at high temperature and high pressure on the surface of iron catalyst to obtain ammonia, is mainly used in industrial production of synthetic ammonia, and is considered as one of the most important inventions in the 20 th century. For over a century, a great deal of research has been carried out on iron catalysts for ammonia synthesis, and iron catalysts with various formulas have been developed, so that the activity of the iron catalysts for ammonia synthesis is greatly improved, but the iron catalysts are not different from multi-component iron catalysts of Haber and the like in nature, and the ammonia synthesis industry is still in the aspects of high energy consumption and high cost at present.

At present, ICI741, A301, A401, ZA-5 and the like are mainly used as the synthetic ammonia iron catalysts, and the synthetic ammonia iron catalysts are Fe smelted from natural iron ore₃O₄、Fe₂O₃And Fe and other substances which do not change the iron isotopic abundance are used as active ingredients, potassium oxide, aluminum oxide, calcium oxide, rare earth oxide, cobalt oxide and the like which do not change the isotopic abundance are used as promoters, and the promoter is added to change the performance of the iron-based catalyst prepared by a melting method.

Ruthenium catalyst for ammonia synthesis is usually prepared by RuCl₃But the ruthenium catalyst is degraded in performance because a small amount of chloride ions remain.

At present, the key point of the research of the synthetic ammonia catalyst is to improve the activity of the catalyst, the catalytic activity (outlet ammonia concentration) of the existing catalyst is lower than 20 percent under the conditions of 15MPa of pressure, 425 ℃ of temperature, 30000/hour of space velocity and 1.0-1.4mm of granularity, the activity is lower and the reduction speed is slower under lower pressure and lower temperature, so that the occupied non-production time is longer, and the catalytic activity and the reduction performance need to be further improved.

In conclusion, synthetic ammonia is one of the nine major energy-consuming industries, and has a huge energy-saving potential. The development direction of the synthetic ammonia catalyst requires higher catalytic activity at low temperature and low pressure, and the catalyst can be suitable for a low-pressure low-energy-consumption synthetic ammonia process to achieve the purposes of energy conservation and emission reduction. Therefore, the low-temperature catalyst in the ammonia synthesis industry is a core technology, and the low-pressure low-energy-consumption ammonia synthesis process can be realized only by developing the high-activity catalyst at lower temperature.

Disclosure of Invention

The primary object of the present invention is to provide a catalyst for catalyzing the reaction for synthesizing ammonia, so as to have better catalytic performance.

To achieve this object, in a basic embodiment, the present invention provides a catalyst for catalyzing a reaction for synthesizing ammonia, the catalyst comprising a catalytically active substance, the catalytically active substance comprising at least one metal or a compound thereof, the metal element of the metal or the compound thereof being composed of a non-radioactive isotope whose composition and/or abundance is changed from natural, wherein the abundance of at least one non-radioactive isotope is changed from the natural abundance by 1/20 or more and not less than 20%.

In a preferred embodiment, the present invention provides a catalyst for catalyzing a reaction for synthesizing ammonia, wherein the at least one metal or a compound thereof is metallic ruthenium (natural abundance of ruthenium isotope: 5.52% Ru-96, 1.88% Ru-98, 12.7% Ru-99, 12.6% Ru-100, 17% Ru-101, 31.6% Ru-102, 18.7% Ru-104) or metallic iron (natural abundance of iron isotope: 5.8% Fe-54, 91.72% Fe-56, 2.2% Fe-57, 0.28% Fe-58) or a compound thereof.

In a more preferred embodiment, the present invention provides a catalyst for catalyzing a reaction for synthesizing ammonia, wherein the catalytically active material further comprises metallic nickel or a compound thereof, and the mass ratio of metallic ruthenium or metallic iron or a compound thereof to metallic nickel or a compound thereof is 1:0.1 to 10;

the nickel element (the natural abundance of the nickel element isotope: 68.27% Ni-58%, 26.1% Ni-60%, 1.13% Ni-61%, 3.59% Ni-62% and 0.91% Ni-642%) in the metallic nickel or the compound thereof is composed of non-radioactive isotopes, and the composition and/or abundance of various isotopes are the same as or different from those of the natural isotope.

In a more preferred embodiment, the present invention provides a catalyst for catalyzing a reaction for synthesizing ammonia, wherein the catalytically active material further comprises metallic copper or a compound thereof, and the mass ratio of metallic ruthenium or metallic iron or a compound thereof to metallic copper or a compound thereof is 1:0.1 to 10;

the copper element (the natural abundance of the copper element isotope is 69.17 percent for Cu-63 and 30.83 percent for Cu-65) in the metal copper or the compound thereof consists of non-radioactive isotopes, and the composition and/or abundance of various isotopes are the same as or different from those of the natural isotopes.

In a more preferred embodiment, the present invention provides a catalyst for catalyzing the reaction for synthesizing ammonia, wherein the catalyst comprises, by weight: 90-98 parts of ferric oxide, 0-5 parts of aluminum oxide, 0-5 parts of potassium oxide, 0-5 parts of calcium oxide, 0-5 parts of magnesium oxide, 0-5 parts of vanadium oxide, 0-5 parts of tungsten oxide, 0-5 parts of zirconium oxide, 0-5 parts of titanium oxide, 0-5 parts of niobium oxide and 0-5 parts of iridium oxide.

In a preferred embodiment, the present invention provides a catalyst for catalyzing a reaction for synthesizing ammonia, 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 catalyst for catalyzing the reaction for synthesizing ammonia, wherein the catalytic auxiliary substance comprises a promoter selected from one or more of cobalt, gold, palladium and rare earth elements.

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

The second purpose of the present invention is to provide a method for preparing the above catalyst, so as to better prepare the above catalyst, and the prepared catalyst has better catalytic performance.

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

(1) preparation of catalytically active material: preparing the catalytic active substance or the compound thereof with changed isotope composition and/or abundance by using an isotope separation method, an isotope mixing method, a nuclear reaction method or an element artificial production method;

(2) preparation of the catalyst: the catalysts are prepared using the respective catalytically active substances or compounds thereof.

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).

The catalyst for catalyzing the ammonia synthesis reaction and the preparation method thereof have the beneficial effects that the obtained catalyst has better catalytic performance.

Detailed Description

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

Example 1: 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%.

Converting the separated ferric oxide into ferric nitrate and preparing into a 1mol/L solution, converting the nickel oxide with natural isotope abundance into nickel nitrate and preparing into a 1mol/L solution, and preparing the catalyst by a hydrothermal method by using ammonium carbonate as an alkali source, wherein the specific method comprises the following steps:

and (3) taking 20ml of ferric nitrate and nickel nitrate solution respectively, mixing, adding 2.0g of sodium acetate, stirring for 1h, keeping the temperature at 40 ℃ for 2h, and drying at 80 ℃ to obtain a catalyst precursor. Adding the catalyst precursor into 50ml of urea solution with the concentration of 2.0mol/L, carrying out hydrothermal treatment at 130 ℃ for 6h, filtering, washing a precipitate to be neutral, drying at 120 ℃ overnight, and roasting at 550 ℃ for 4h to prepare the Ni/Fe/LDH (LDH full name nickel iron hydrotalcite) catalyst (the mass ratio of Ni to Fe is 7: 3).

Example 2: 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) taking 20ml of ferric nitrate and nickel nitrate solution respectively, mixing, adding 2.0g of sodium acetate, stirring for 1h, keeping the temperature at 40 ℃ for 2h, and drying at 80 ℃ to obtain a catalyst precursor. Adding the catalyst precursor into 50ml of urea solution with the concentration of 2.0mol/L, carrying out hydrothermal treatment at 130 ℃ for 6h, filtering, washing a precipitate to be neutral, drying at 120 ℃ overnight, and roasting at 550 ℃ for 4h to prepare the Ni/Fe/LDH catalyst (the mass ratio of Ni to Fe is 7: 3).

Example 3: 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 4: 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 5: 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 6: 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%.

Example 7: 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%.

Example 8: 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%.

Example 9: 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%.

Example 10: 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.

Example 11: comparative preparation example

Converting iron oxide with natural isotope abundance into ferric nitrate and preparing into 1mol/L solution, converting nickel oxide with natural isotope abundance into nickel nitrate and preparing into 1mol/L solution, and preparing the catalyst by a hydrothermal method by taking ammonium carbonate as an alkali source, wherein the specific method comprises the following steps:

Example 12: comparative preparation example

73.4g of iron oxide with natural isotopic abundance 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. Placing the materials in a blenderMixing, charging into electric furnace, and melting 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 13: preparation examples

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 14: preparation examples

Example 15: preparation examples

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 percent by massThe specific 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 16: preparation examples

Example 17: preparation examples

73.4g of the separated ferric oxide is converted into ferroferric oxide and weighedTaking 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 18: preparation examples

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 19: preparation examples

Example 20: preparation examples

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: iron powder 22.6g, alumina 1.5g, potassium oxide 0.92g, calcium oxide 1.3g, magnesium oxide 1.2g, vanadium oxide 0.8g0.8g 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 21: preparation examples

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 measurement catalysisThe iron oxide in the agent is a Vickers phase (Fe)₁-xO，x＝0.046)。

Example 22: preparation examples

Example 23: 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. Transferring the melt into a cooling tank, cooling to below 200 ℃, crushing, ball-milling and screening the cooled frit to obtain the required granularityCatalyst product (final composition of the catalyst product is controlled by the ratio of the amount of ferrous and ferric iron substances 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 24: 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, 10 g 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 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-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, 10 g 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 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-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 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-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 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-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 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-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%.

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-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, 10 g 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 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-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 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 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 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-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 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 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%.

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 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, 10 g 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 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 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 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 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 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-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, 10 g 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: 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, 10 g 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: 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, 10 g 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 41: 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, 10 g 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 42: examples of catalytic reactions

The catalysts prepared in the previous examples are respectively used for catalyzing 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 1 below.

TABLE 1 results of ammonia synthesis reaction test

Comparing the results of the above synthesis ammonia reaction, it can be seen that:

(1) the synthetic ammonia catalyst constructed based on the Fe source with isotopic abundance different from the natural Fe element has higher ammonia yield under the same conditions, and is beneficial to reducing the cost of synthetic ammonia.

(2) The ruthenium-based catalyst constructed on the basis of the Ru source with isotopic abundance different from that of the natural Ru element has higher ammonia yield under the same conditions, and is beneficial to reducing the cost of ammonia synthesis.

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. A catalyst for catalyzing a reaction for synthesizing ammonia, characterized in that: 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.

2. The catalyst of claim 1, wherein: the at least one metal or compound thereof is metallic ruthenium or metallic iron or a compound thereof.

3. The catalyst of claim 2, wherein:

the catalytic active substance also comprises metallic nickel or a compound thereof, and the mass ratio of metallic ruthenium or metallic iron or the compound thereof to metallic nickel or the compound thereof is 1: 0.1-10;

the nickel element in the metallic nickel or the compound thereof is composed of non-radioactive isotopes, and the composition and/or abundance of various isotopes are the same as or different from those of the natural isotopes.

4. The catalyst of claim 2, wherein:

the catalytic active substance also comprises metallic copper or a compound thereof, and the mass ratio of metallic ruthenium or metallic iron or the compound thereof to metallic copper or the compound thereof is 1: 0.1-10;

the copper element in the metallic copper or the compound thereof consists of nonradioactive isotopes, and the composition and/or abundance of various isotopes are the same as or different from those of the natural isotopes.

5. The catalyst according to claim 2, wherein the catalyst comprises, by weight: 90-98 parts of ferric oxide, 0-5 parts of aluminum oxide, 0-5 parts of potassium oxide, 0-5 parts of calcium oxide, 0-5 parts of magnesium oxide, 0-5 parts of vanadium oxide, 0-5 parts of tungsten oxide, 0-5 parts of zirconium oxide, 0-5 parts of titanium oxide, 0-5 parts of niobium oxide and 0-5 parts of iridium oxide.

6. The catalyst according to any one of claims 1 to 4, wherein: 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 catalyst of claim 6, wherein: the catalytic auxiliary substance comprises a cocatalyst which is selected from one or more of cobalt, gold, palladium and rare earth elements.

8. The catalyst 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.

9. Process for the preparation of a catalyst according to one of claims 1 to 8, comprising the following steps: