CN112774674A - Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof - Google Patents
Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a supported ruthenium cluster catalyst for ammonia synthesis, a preparation method and application thereof, and belongs to the technical field of preparation of synthetic ammonia catalysts. The supported ruthenium cluster catalyst for ammonia synthesis comprises a carrier and an active component, wherein the carrier is magnesium oxide, the active component is a ruthenium cluster in a highly dispersed form, and the loading amount of ruthenium metal is 0.1-10% of the mass of the magnesium oxide carrier. The preparation method comprises the following steps: the supported ruthenium cluster catalyst for ammonia synthesis is prepared by taking magnesium oxide as a carrier and adopting a precipitation method. The supported ruthenium cluster catalyst prepared by the invention has higher catalytic activity and stability when being used for ammonia synthesis reaction. The preparation method has the advantages of simple and safe preparation process, cheap and easily-obtained raw materials, low preparation cost and easy realization of large-scale preparation.
Description
Technical Field
The application belongs to the technical field of preparation of synthetic ammonia catalysts, and particularly relates to a preparation method and application of a supported ruthenium cluster catalyst for ammonia synthesis.
Background
Ammonia is one of the chemical products with the largest yield in the world, is mainly used for producing products such as chemical fertilizers, nitric acid, ammonium salts, soda ash and the like, and has important application in industries such as chemical fertilizers, plastics, medicines, explosives, metallurgy, environmental protection and the like. The increasing development of society and the growing population make the demand for ammonia and processed products of ammonia larger and larger, and the synthetic ammonia industry has an increasing status in national economy. At present, a molten iron catalyst is widely applied to the synthesis ammonia industry based on the Haber-Bosch process, and the molten iron catalyst needs to be used under the conditions of high temperature (400-500 ℃) and high pressure (10-30 MPa). China is the biggest country for producing synthetic ammonia in the world, and compared with the advanced level in the world, the synthetic ammonia industry has high energy consumption and cost, and CO2Large discharge amount and the like. In recent years, social sustainable development and energy conservation and emission reduction policies become stricter, and the synthetic ammonia industry in China urgently needs to solve the situation of high energy consumption and high cost.
The technical innovation of the ammonia synthesis catalyst is the key for reducing the energy consumption and the cost of the ammonia synthesis industry. In 1992, the successful development of a KAAP ammonia synthesis process based on graphitized carbon supported ruthenium catalysts (Ru/C) was considered to be a major technological revolution in the ammonia synthesis industry. Compared with the traditional molten iron ammonia synthesis catalyst, the ruthenium-based ammonia synthesis catalyst has the advantages of high activity, mild reaction condition, low energy consumption, long service life and the like. In addition, the ruthenium-based catalyst is not sensitive to water and carbon oxides, can greatly reduce the production cost of raw material gas, and is an ideal second-generation high-efficiency ammonia synthesis catalyst. However, under the condition of industrial ammonia synthesis, ruthenium can cause the graphitized carbon carrier to generate methanation reaction to cause catalyst deactivation, thereby limiting the wide application of the Ru/C catalyst. The development of a novel nail-based catalyst with high activity and high stability under mild reaction conditions has important significance for the sustainable development of the synthetic ammonia industry.
Compared with the conventional supported nanoparticle catalyst, the sub-nanocluster (with the size of 0.2-1.0 nm) catalyst has the advantages of high metal dispersion degree, small size, high metal utilization rate and the like, is expected to reduce the consumption of noble metals and reduce the cost, has stronger interaction between metal cluster particles and a carrier, and can greatly modulate the catalytic activity or selectivity of the cluster catalyst.
Unlike common acidic or neutral carriers such as silica and alumina, magnesia is an inorganic oxide material with a basic surface and has wide application as a catalyst and a catalyst carrier. So far, magnesium oxide supported ruthenium cluster ammonia synthesis catalysts with high activity and high stability under relatively mild reaction conditions (250-400 ℃) are reported and need to be further developed.
Disclosure of Invention
The application provides a magnesium oxide supported ruthenium cluster catalyst for ammonia synthesis, which can be used as a catalyst for high-efficiency ammonia synthesis under relatively mild reaction conditions (250-400 ℃), has catalytic activity obviously higher than that of a magnesium oxide supported ruthenium nanoparticle catalyst, and has very high stability.
The supported ruthenium cluster catalyst for ammonia synthesis is characterized by comprising a carrier and an active component;
wherein the carrier is magnesium oxide;
the active component is ruthenium in the form of clusters.
Optionally, the loading amount of the active component ruthenium cluster is 0.1-10% of the mass of the magnesium oxide carrier.
In the present application, the term "ruthenium in clusters" means ruthenium present in the form of sub-nanometer scale metal clusters, sometimes also referred to herein as "ruthenium clusters", both having the same meaning.
Optionally, the ruthenium in cluster form, i.e. the size of the ruthenium cluster, is 0.1-1.5 nm.
Optionally, the ruthenium in cluster form, i.e. the size of the ruthenium cluster, is 0.2-1.0 nm.
The characteristics of a high-resolution transmission electron microscope, X-ray absorption fine structure spectrum (XAFS) and the like show that ruthenium is distributed on the surface of the magnesium oxide carrier in the form of high-dispersion clusters.
Optionally, the supported ruthenium cluster catalyst for ammonia synthesis consists of a magnesium oxide support and an active component ruthenium.
Optionally, the active component is comprised of ruthenium in the form of clusters.
Optionally, the loading amount of the cluster-form ruthenium is 0.1-10% of the mass of the magnesium oxide carrier, and the mass of the active component is calculated by the mass of the active element Ru.
According to another aspect of the present application, there is provided a method for preparing the supported ruthenium cluster catalyst for ammonia synthesis, which requires low cost of raw materials such as magnesium oxide carrier, ruthenium salt and precipitant such as ammonia water, sodium hydroxide, etc. all of which are large commercial products; in addition, the preparation process of the method is simple and safe to operate, and industrial production is easy to realize.
Thus, the present application provides an efficient preparation method of a supported ruthenium cluster catalyst for ammonia synthesis reaction.
The preparation method of the supported ruthenium cluster catalyst for ammonia synthesis is characterized by comprising the following steps:
the supported ruthenium cluster catalyst for ammonia synthesis is prepared by taking magnesium oxide as a carrier and adopting a precipitation method.
Optionally, the method comprises:
(1) adding a precipitator into the solution containing the magnesium oxide and ruthenium precursor, and carrying out precipitation reaction for a certain time at room temperature to obtain a catalyst precursor;
(2) and reducing the catalyst precursor to obtain the supported ruthenium cluster catalyst for ammonia synthesis.
Optionally, the solvent in the solution containing the magnesium oxide and the ruthenium precursor is water.
Optionally, in step (1), magnesium oxide is added to the solution of ruthenium precursor to obtain the solution containing magnesium oxide and ruthenium precursor.
Optionally, the conditions of the reaction include: the reaction temperature is room temperature, and the reaction time is 1-36 hours.
Alternatively, the upper limit of the reaction time is selected from 2 hours, 4 hours, 6 hours, 8 hours, 9 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28.5 hours, 32 hours, or 36 hours; the lower limit is selected from 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 9 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28.5 hours, or 32 hours.
Alternatively, the reaction is carried out under stirring conditions.
Optionally, the material obtained after the reaction is filtered, washed and dried.
Optionally, the drying temperature is 40-200 ℃.
Optionally, the reducing conditions comprise: in a reducing atmosphere, the reducing temperature is 300-600 ℃, and the reducing time is 1-12 hours.
Optionally, the upper limit of the reduction temperature is selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the lower limit is selected from 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C or 550 deg.C.
Alternatively, the upper limit of the reduction time is selected from 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, or 12 hours; the lower limit is selected from 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours.
Optionally, the reducing atmosphere is hydrogen, a mixed gas of hydrogen and argon, or a mixed gas of hydrogen and nitrogen, wherein the volume percentage of hydrogen in the mixed gas is more than or equal to 5%.
Optionally, the volume percentage of hydrogen in the mixed gas is more than or equal to 5% and less than 100%.
Optionally, the ruthenium precursor is selected from at least one of ruthenium salts.
Optionally, the ruthenium salt is selected from at least one of ruthenium chloride, ruthenium nitrosyl nitrate, ruthenium acetylacetonate, and potassium ruthenate.
Optionally, the ratio of the ruthenium in cluster form to the magnesium oxide support is such that: the loading amount of the cluster type ruthenium is 0.1-10% of the mass of the carrier; wherein the mass of the active component is calculated as the mass of the active element ruthenium.
Optionally, the precipitant is added under stirring.
Optionally, the precipitant is selected from at least one of ammonia, potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate.
Optionally, the molar ratio of the precipitant to the ruthenium precursor is 3: 1-30: 1, wherein the mole number of the precipitant is calculated as the mole number of the precipitant itself, and the mole number of the ruthenium precursor is calculated as the mole number of ruthenium element in the ruthenium precursor.
In a specific embodiment, the method comprises the steps of:
(a) preparing a catalyst precursor: adding magnesium oxide into a ruthenium salt aqueous solution, adding a precipitator into the ruthenium salt aqueous solution containing magnesium oxide under the stirring condition, and reacting at room temperature for 1-36 hours to obtain a catalyst precursor;
(b) reduction of a catalyst precursor: and reducing the catalyst precursor for 1-12 hours at 300-600 ℃ in a reducing atmosphere to obtain the supported ruthenium cluster catalyst for ammonia synthesis.
In another aspect of the present application, the supported ruthenium cluster catalyst for ammonia synthesis prepared according to the method or the supported ruthenium cluster catalyst for ammonia synthesis prepared according to the method is used in catalytic reactions for ammonia synthesis.
Optionally, the method for catalytic reaction of synthesis ammonia comprises: heating the supported ruthenium cluster catalyst for ammonia synthesis to 300-600 ℃ at a speed of 1-5 ℃/min in a reducing atmosphere containing hydrogen, reducing at the temperature for 1-12 hours, cooling to a reaction temperature of 250-400 ℃, and carrying out a synthetic ammonia catalytic reaction in a mixed atmosphere of nitrogen and hydrogen to obtain an ammonia product.
Optionally, the volume ratio of nitrogen to hydrogen in the mixed atmosphere is 1: 3-3: 1; the space velocity of the reaction gas is 1000-50000 mL/gcatH; the reaction pressure is 0.1-5.0 MPa.
In a specific embodiment, the supported ruthenium cluster catalyst for ammonia synthesis is heated to 300-600 ℃ at a speed of 1-5 ℃/min in a reducing atmosphere containing hydrogen, reduced at the temperature for 1-12 hours, then reduced to a reaction temperature of 250-400 ℃ in the reducing atmosphere, and the atmosphere is switched to a nitrogen-hydrogen mixed gas, so that an ammonia product can be obtained.
The supported ruthenium cluster ammonia synthesis catalyst for ammonia synthesis has high catalytic activity and good stability. Compared with the prior art, the ruthenium cluster ammonia synthesis catalyst provided by the application has the beneficial effects that:
1) compared with the conventional magnesium oxide supported ruthenium nanoparticle catalyst, the magnesium oxide supported ruthenium cluster catalyst for ammonia synthesis provided by the application has the advantage that the activity of the synthetic ammonia is obviously improved.
2) The supported ruthenium cluster catalyst for ammonia synthesis provided by the application has good stability, and the activity does not change obviously after 60-hour test.
3) According to the preparation method of the supported ruthenium cluster catalyst, the required raw materials such as magnesium oxide, ruthenium salt, a precipitator and the like are large commercial products, and the cost is low.
4) The preparation method of the supported ruthenium cluster catalyst for ammonia synthesis has the advantages of simple and safe preparation process and the like, and is easy to realize large-scale preparation.
Drawings
FIG. 1 is a high-resolution transmission electron micrograph of a 5 wt% Ru clusterings/MgO-1 catalyst in example 1.
FIG. 2 is an X-ray absorption fine structure spectrum of the Ru clusterings/MgO-1 catalysts of different contents in examples 1-3.
FIG. 3 is a high-resolution transmission electron micrograph of the 5 wt% Ru NPs/MgO-1 catalyst of comparative example 1.
FIG. 4 shows 5 wt% Ru clusterings/MgO-1 catalyst from example 1 at a pressure of 1.0bar and a space velocity of 24000mL/gcatH, stability test results of the reaction for the synthesis of ammonia under reaction conditions at a temperature of 400 ℃.
Detailed Description
As previously mentioned, the present application relates to a supported ruthenium cluster catalyst for ammonia synthesis, a method for preparing the same, and applications thereof. The supported ruthenium cluster catalyst is prepared by taking ruthenium clusters as active components and magnesium oxide as a carrier through a precipitation method. Compared with the existing catalyst system, the supported ruthenium cluster catalyst prepared by the method has higher activity and stability and good application prospect.
Unless otherwise indicated, all numbers such as active ingredients, temperature and time, gas conversion, etc. appearing in the specification and claims of this application are to be understood as being absolutely exact, and certain experimental errors in the measured values are inevitable due to standard deviation of the measurement technique.
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials and reagents in the examples of the present application are commercially available.
In the embodiment of the application, the synthetic ammonia reaction is carried out on a fixed bed micro reaction device, a stainless steel reactor is adopted, and a temperature control thermocouple is arranged on the outer wall of the reactor. The components of the reaction gas are analyzed on line by a conductivity meter, the reaction tail gas is introduced into the dilute sulfuric acid solution, the conductivity change of the solution is tracked by the conductivity meter, and finally the ammonia generation rate is deduced and calculated according to the change of the conductivity.
The presence form and size of Ru particles in the catalyst sample were observed by transmission electron microscopy (model: JEOL 2100X, available from JEOL, Japan).
X-ray absorption fine structure spectroscopy (EXAFS) test is acquired at Shanghai Synchrotron Radiation Facility (SSRF) BL14W1 line station, the electron energy is 3.5GeV, and the electron beam intensity is 300 mA.
Example 1
0.0784g of ruthenium nitrosyl nitrate is dissolved in 60mL of water, 0.5g of magnesium oxide is added to the aqueous solution of ruthenium nitrosyl nitrate under stirring, 0.04g of potassium hydroxide is added to the suspension after uniform stirring, and the mixture is stirred and reacted for 6 hours at room temperature. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 60 ℃. The product was dried and reduced with hydrogen at 400 ℃ for 2 hours to obtain a magnesium oxide-supported ruthenium cluster catalyst (5 wt% Ru clusters/MgO-1) with a ruthenium loading of 5 wt%.
FIG. 1 shows the characterization result of a high-resolution transmission electron microscope, and Ru in the 5 wt% Ru clusterings/MgO-1 catalyst is in a high-dispersion state and has no obvious nanoparticles. FIG. 2X-ray absorption fine structure spectroscopy (EXAFS) results show that Ru species in the 5 wt% Ru clusterings/MgO-1 catalyst are mainly in Ru-O form, which indicates that the Ru species are dispersed on the surface of the magnesium oxide carrier in cluster form and have stronger interaction with the carrier through Ru-O bonds.
The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the reaction activity of synthesizing ammonia at 400 ℃ is 3250 mu mol/gcatH, the activity of the reaction for synthesizing ammonia at 300 ℃ is 650. mu. mol/gcat·h。
Example 2
0.047g of ruthenium nitrosyl nitrate is dissolved in 60mL of water, 0.5g of magnesium oxide is added to the aqueous solution of ruthenium nitrosyl nitrate under stirring, 0.08g of potassium hydroxide is added to the suspension after uniform stirring, and the mixture is stirred and reacted for 10 hours at room temperature. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 70 ℃. The product was dried and then treated with H having a hydrogen content of 5 vol.%2the/Ar mixed gas is reduced for 2 hours at 500 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (3 wt% Ru clusters/MgO-1) with the ruthenium load of 3 wt%.
FIG. 2X-ray absorption fine structure spectroscopy (EXAFS) results show that Ru species in the 3 wt% Ru clusterings/MgO-1 catalyst are mainly in Ru-O form, which indicates that the Ru species are dispersed on the surface of the magnesium oxide carrier in cluster form and have strong interaction with the carrier. The obtained catalyst was subjected to evaluation of ammonia synthesis activity in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 5 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH reaction activity of Synthesis of Ammonia at 400 deg.CProperty is 2110 μmol/gcatH, the activity of the reaction for synthesizing ammonia at 350 ℃ is 650 mu mol/gcat·h。
Example 3
0.016g of ruthenium nitrosyl nitrate is dissolved in 60mL of water, 0.5g of magnesium oxide is added into the ruthenium nitrosyl nitrate aqueous solution under stirring, 0.5g of concentrated ammonia water is added into the suspension after uniform stirring, and the mixed solution is stirred and reacted for 10 hours at room temperature. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 70 ℃. The product was dried and then treated with H having a hydrogen content of 5 vol.%2the/Ar mixed gas is reduced for 2 hours at 500 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (1 wt% Ru clusters/MgO-1) with the ruthenium load of 1 wt%.
The result of a high-resolution transmission electron microscope shows that Ru in the 1 wt% Ru clusterings/MgO-1 catalyst is in a high-dispersion cluster state. The X-ray absorption fine structure spectroscopy (EXAFS) results (FIG. 2) show that the Ru species in the 1 wt% Ru clusterings/MgO-1 catalyst are mainly in the Ru-O form, which indicates that the Ru species are dispersed on the surface of the magnesium oxide carrier in the cluster form and have stronger interaction with the carrier through Ru-O bonds. The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 2 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the activity of the reaction for synthesizing ammonia at 400 ℃ is 1280 mu mol/gcat·h。
Example 4
0.1568g of ruthenium nitrosyl nitrate is dissolved in 100mL of water, 0.5g of magnesium oxide is added to the aqueous solution of ruthenium nitrosyl nitrate under stirring, 0.297g of sodium hydroxide is added to the suspension after uniform stirring, and the mixture is stirred at room temperature for reaction for 24 hours. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 60 ℃. The product was dried and reduced with hydrogen at 400 ℃ for 2 hours to obtain a magnesium oxide-supported ruthenium cluster catalyst with a ruthenium loading of 10 wt% (10 wt% Ru clusters/MgO-1).
The high-resolution transmission electron microscope characterization result shows that Ru in the 10 wt% Ru clusterings/MgO-1 catalyst is in a high-dispersion state and has no obvious nanoparticles.
The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the reaction activity of the ammonia synthesis reaction at 400 ℃ is 4050. mu. mol/gcatH, the reaction activity of the ammonia synthesis reaction at 350 ℃ is 3050 mu mol/gcatH. At a reaction pressure of 10.0bar and a reaction gas space velocity of 1000mL/gcatH, the activity of the reaction for synthesizing ammonia at 400 ℃ is 2150 mu mol/gcat·h。
Example 5
0.0016g of ruthenium nitrosyl nitrate is dissolved in 60mL of water, 0.5g of magnesium oxide is added to the aqueous solution of ruthenium nitrosyl nitrate under stirring, 0.16g of concentrated ammonia water is added to the suspension after uniform stirring, and the mixture is stirred and reacted for 10 hours at room temperature. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 70 ℃. The product was dried and then treated with H having a hydrogen content of 5 vol.%2the/Ar mixed gas is reduced for 2 hours at 500 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (0.1 wt% Ru clusters/MgO-1) with the ruthenium load of 0.1 wt%.
The result of a high-resolution transmission electron microscope shows that Ru in the 0.1 wt% Ru clusterings/MgO-1 catalyst is in a high-dispersion cluster state. The X-ray absorption fine structure spectrum (EXAFS) result shows that Ru species in the 0.1 wt% Ru clusterings/MgO-1 catalyst are mainly in a Ru-O form, which indicates that the Ru species are dispersed on the surface of the magnesium oxide carrier in a cluster form and have stronger interaction with the carrier through Ru-O bonds. The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 2 hours at the temperature, and then reducing to the reaction temperature. In thatThe reaction pressure is 1.0bar, and the space velocity of the reaction gas is 24000mL/gcatH, the activity of the reaction for synthesizing ammonia at 400 ℃ is 380. mu. mol/gcat·h。
Example 6
0.103g of ruthenium chloride was dissolved in 80mL of water, 1.0g of magnesium oxide was added to the aqueous ruthenium chloride solution under stirring, 0.593g of sodium hydroxide was added to the suspension after stirring uniformly, and the mixture was stirred at room temperature for 10 hours. Then dried at 80 ℃. The product was dried and then treated with H having a hydrogen content of 30 vol.%2the/Ar mixed gas is reduced for 4 hours at 600 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (5 wt% Ru clusters/MgO-2) with the ruthenium load of 5 wt%.
The result of a high-resolution transmission electron microscope shows that Ru in the 5 wt% Ru clusterings/MgO-2 catalyst is in a high-dispersion cluster state.
The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the reaction activity of ammonia synthesis under the reaction condition of 400 ℃ is 2786 mu mol/gcatH. At the reaction pressure of 10.0bar and the space velocity of reaction gas of 50000mL/gcatH, the activity of the reaction for synthesizing ammonia at 400 ℃ is 18690. mu. mol/gcat·h。
Example 7
0.197g of ruthenium acetylacetonate was dissolved in 100mL of water, 1.0g of magnesium oxide was added to the aqueous ruthenium acetylacetonate solution under stirring, 1.365g of potassium carbonate was added to the suspension after stirring uniformly, and the mixture was stirred at room temperature for reaction for 12 hours. After the reaction, the reaction mixture is filtered, and the product is washed by deionized water until the filtrate is neutral, and then dried at 100 ℃. The product was dried and then treated with H having a hydrogen content of 60 vol.%2the/Ar mixed gas is reduced for 4 hours at 600 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (5 wt% Ru clusters/MgO-3) with the ruthenium load of 5 wt%.
The result of the high-resolution transmission electron microscope shows that,ru in the 5 wt% Ru clusterings/MgO-3 catalyst is in a high-dispersion sub-nanocluster state. The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the reaction activity of the synthetic ammonia at 400 ℃ is 3400 mu mol/gcatH. At the reaction pressure of 5bar and the space velocity of reaction gas of 12000mL/gcatH the activity of the reaction for synthesizing ammonia at 350 ℃ is 8960 mu mol/gcat·h。
Example 8
0.129g of potassium ruthenate was dissolved in 100mL of water, 1.0g of magnesium oxide was added to the aqueous solution of potassium ruthenate with stirring, 0.524g of sodium carbonate was added to the suspension after stirring to homogeneity, and the mixture was stirred at room temperature for 6 hours. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 90 ℃. The product was dried and then treated with H having a hydrogen content of 15 vol.%2the/Ar mixed gas is reduced for 4 hours at 300 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (5 wt% Ru clusters/MgO-4) with the ruthenium load of 5 wt%.
The result of a high-resolution transmission electron microscope shows that Ru in the 5 wt% Ru clusterings/MgO-4 catalyst is in a high-dispersion sub-nanocluster state. The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH the activity of the reaction for synthesizing ammonia at 400 ℃ is 3020. mu. mol/gcat·h。
Example 9
Dissolving 0.077g of potassium ruthenate in 100mL of water, adding 1.0g of magnesium oxide to the aqueous solution of potassium ruthenate with stirring, adding 0.131g of sodium carbonate to the suspension after stirring, mixingThe solution was stirred at room temperature for 6 hours. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 90 ℃. The product was dried and then treated with H having a hydrogen content of 15 vol.%2the/Ar mixed gas is reduced for 4 hours at 300 ℃ to obtain the magnesium oxide supported ruthenium cluster catalyst (3 wt% Ru clusters/MgO-4) with the ruthenium load of 3 wt%.
The result of a high-resolution transmission electron microscope shows that Ru in the 3 wt% Ru clusterings/MgO-4 catalyst is in a high-dispersion sub-nanocluster state. The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH at 400 ℃ the activity of the reaction for synthesizing ammonia is 2830. mu. mol/gcatH. Under the conditions that the reaction pressure is 2.0bar and the space velocity of reaction gas is 36000mL/gcatH at 400 ℃ the activity of the reaction for synthesizing ammonia is 6830. mu. mol/gcatH, the activity of the reaction for synthesizing ammonia at 350 ℃ is 4230 mu mol/gcat·h。
Comparative example 1
0.157g of ruthenium nitrosyl nitrate was weighed out and dissolved in 5mL of water, and after sufficient dissolution, 1.0g of magnesium oxide was added to the aqueous solution of ruthenium nitrosyl nitrate and immersed therein. After the impregnation treatment for 10 minutes, the catalyst was dried at 80 ℃, calcined at 550 ℃ in argon for 2 hours, and then the obtained product was reduced in hydrogen at 550 ℃ for 2 hours to obtain the magnesium oxide supported ruthenium nanoparticle catalyst (5 wt% Ru NPs/MgO-1) prepared by impregnation.
FIG. 3 shows the results of high resolution transmission electron microscopy, in which Ru in the 5 wt% Ru NPs/MgO-1 catalyst is distributed on the surface of a magnesium oxide carrier in the form of nanoparticles with larger sizes.
And (3) carrying out synthetic ammonia reaction activity evaluation on the prepared magnesium oxide supported ruthenium nanoparticle catalyst in an ammonia synthesis device. The catalyst is placed in N2/H2Heating to 500 deg.C at 5 deg.C/min under nitrogen-hydrogen mixed atmosphere with volume ratio of 1:3, reducing at the temperature for 10 hr, and cooling toThe reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH the activity of the reaction for synthesizing ammonia at 400 ℃ is 850. mu. mol/gcat·h。
Comparative example 2
0.197g of ruthenium acetylacetonate was dissolved in 10mL of water, and 1.0g of magnesium oxide was added to the aqueous ruthenium acetylacetonate solution under stirring for impregnation. After 10 minutes of immersion treatment, it was dried at 80 ℃ and then calcined at 550 ℃ for 2 hours under argon and hydrogen at 5 vol.% of H2And reducing the mixture in an Ar mixed gas at 500 ℃ for 4 hours to obtain the magnesium oxide supported ruthenium nanoparticle catalyst (5 wt% Ru NPs/MgO-2) prepared by an impregnation method.
The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH the activity of the reaction for synthesizing ammonia at 400 ℃ is 720. mu. mol/gcat·h。
Comparative example 3
0.103g of ruthenium chloride was weighed out and dissolved in 5mL of water, and after sufficient dissolution, 1.0g of magnesium oxide was added to the aqueous ruthenium chloride solution and immersed. Impregnating for 30 min, drying at 80 deg.C, calcining at 550 deg.C in argon for 2 hr, and adding hydrogen with hydrogen content of 50 vol.% H2the/Ar mixed gas is reduced for 4 hours at 550 ℃ to obtain the magnesium oxide supported ruthenium nanoparticle catalyst (5 wt% Ru NPs/MgO-3) prepared by impregnation.
The obtained catalyst was subjected to evaluation of the activity of the ammonia synthesis reaction in an ammonia synthesis apparatus. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH the activity of the reaction for synthesizing ammonia at 400 ℃ is 360 mu mol/gcat·h。
Comparative example 4
0.0784g of ruthenium nitrosyl nitrate was dissolved in 100mL of water, 0.5g of silica was added to the aqueous solution of ruthenium nitrosyl nitrate under stirring, 0.297g of sodium hydroxide was added to the suspension after stirring, and the mixture was stirred at room temperature for 24 hours. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 60 ℃. The product was dried and reduced with hydrogen at 400 ℃ for 2 hours to give a silica-supported ruthenium catalyst with a ruthenium loading of 5 wt% (5 wt% Ru/SiO)2)。
For the 5 wt% Ru/SiO produced in an ammonia synthesis plant2The catalyst is used for evaluating the reaction activity of the synthetic ammonia. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the activity of the reaction for synthesizing ammonia at 400 ℃ is 150. mu. mol/gcat·h。
Comparative example 5
0.0784g of ruthenium nitrosyl nitrate was dissolved in 100mL of water, 0.5g of alumina was added to the aqueous solution of ruthenium nitrosyl nitrate under stirring, 0.297g of sodium hydroxide was added to the suspension after stirring, and the mixture was stirred at room temperature for 24 hours. After the reaction, the reaction mixture was filtered, and the product was washed with deionized water until the filtrate was neutral, and then dried at 60 ℃. The product was dried and reduced with hydrogen at 400 ℃ for 2 hours to give an alumina-supported ruthenium catalyst with a ruthenium loading of 5 wt% (5 wt% Ru/Al2O3)。
For the 5 wt% Ru/Al produced in an ammonia plant2O3The catalyst is used for evaluating the reaction activity of the synthetic ammonia. The catalyst is placed in N2/H2Heating to 500 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, reducing for 10 hours at the temperature, and then reducing to the reaction temperature. At a reaction pressure of 1.0bar and a reaction gas space velocity of 24000mL/gcatH, the activity of the reaction for synthesizing ammonia at 400 ℃ is 550. mu. mol/gcat·h。
Table 1 shows examples 1 to 9 and pairsThe catalyst in the proportion of 1-5 has the temperature of 400 ℃, the pressure of 1.0bar and the gas space velocity of 24000mL/gcatReaction activity of ammonia synthesis under h conditions. It can be seen that the Ru clusterings/MgO catalyst has much higher activity than the Ru NPs/MgO catalyst at the same ruthenium loading. The activity of 5 wt% Ru clusters/MgO-1 at 400 ℃ is 3.8 times that of 5 wt% Ru NPs/MgO-1. The catalytic activity of the 1 wt% Ru clusterings/MgO-1 with the lower loading at 400 ℃ is equivalent to that of the 5 wt% Ru NPs/MgO-1 with the high loading.
TABLE 1 comparison of ammonia synthesis activities for different cluster catalysts and comparative catalysts
Example 10 stability test of reaction for synthesizing ammonia by using magnesium oxide-supported ruthenium cluster catalyst
The stability of the ammonia synthesis reaction was evaluated in the ammonia synthesis apparatus for the magnesium oxide-supported ruthenium cluster catalyst prepared in the above example. The catalyst is placed in N2/H2Heating to 400 ℃ at the speed of 5 ℃/min under the nitrogen-hydrogen mixed atmosphere with the volume ratio of 1:3, wherein the reaction pressure is 1.0bar, and the gas space velocity is 24000mL/gcatH, temperature 400 ℃ for 60 hours.
The results of the stability test of the 5 wt% Ru clusterings/MgO-1 catalyst of example 1 are shown in FIG. 4. As can be seen from FIG. 4, the 5 wt% Ru clusterings/MgO-1 catalyst has high stability, and the activity is substantially maintained for 60 hours. Similar to the above results, the catalysts prepared in the other examples all had better reaction stability.
Ammonia synthesis reaction activity test of supported ruthenium cluster catalyst under different reaction conditions
The supported ruthenium cluster catalyst prepared in the above example was subjected to a test of ammonia synthesis reactivity under different reaction conditions in an ammonia synthesis apparatus. See table 2 for details.
TABLE 2 reaction activity test of ammonia synthesis under different reaction conditions of supported ruthenium cluster catalyst
As can be seen from Table 2, the magnesium oxide supported ruthenium cluster catalyst has very high catalytic activity under different reaction conditions, and realizes the high-efficiency synthesis of ammonia under relatively mild reaction conditions (250-400 ℃). Similar to the above results, the catalysts prepared in other examples have better catalytic activity under different reaction conditions.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A supported ruthenium cluster catalyst for ammonia synthesis, comprising a support and an active component;
wherein the carrier is magnesium oxide;
the active component is ruthenium in the form of clusters.
2. The supported ruthenium cluster catalyst for ammonia synthesis according to claim 1, wherein the size of the ruthenium in cluster form is 0.2 to 1.0 nm;
preferably, the loading amount of the active component ruthenium cluster is 0.1-10% of the mass of the magnesium oxide carrier; the mass of the active component is calculated as the mass of the active element ruthenium.
3. The method for producing a supported ruthenium cluster catalyst for ammonia synthesis according to claim 1 or 2, characterized by comprising:
the supported ruthenium cluster catalyst for ammonia synthesis is prepared by taking magnesium oxide as a carrier and adopting a precipitation method.
4. The method of claim 3, comprising:
(1) adding a precipitator into the solution containing the magnesium oxide carrier and the ruthenium precursor, and carrying out precipitation reaction at room temperature for a certain time to obtain a catalyst precursor;
(2) and reducing the catalyst precursor to obtain the supported ruthenium cluster catalyst for ammonia synthesis.
5. The method according to claim 4, wherein the ruthenium precursor is selected from at least one of ruthenium salts;
preferably, the ruthenium salt is selected from at least one of ruthenium chloride, ruthenium nitrosyl nitrate, ruthenium acetylacetonate, and potassium ruthenate.
6. The method of claim 4, wherein the precipitating agent is selected from at least one of ammonia, potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate;
preferably, the molar ratio of the precipitant to the ruthenium precursor is 3: 1-30: 1, wherein the mole number of the precipitant is calculated as the mole number of the precipitant itself, and the mole number of the ruthenium precursor is calculated as the mole number of ruthenium element in the ruthenium precursor.
7. The method of claim 4, wherein the reaction conditions comprise: the reaction temperature is room temperature, and the reaction time is 1-36 hours;
the reduction conditions include: under the reducing atmosphere, the reducing temperature is 300-600 ℃, and the reducing time is 1-12 hours;
preferably, the reducing atmosphere is hydrogen, a mixed gas of hydrogen and argon, or a mixed gas of hydrogen and nitrogen, wherein the volume percentage of hydrogen in the mixed gas is more than or equal to 5%.
8. The method according to any one of claims 3 to 7, comprising:
(a) preparing a catalyst precursor: adding magnesium oxide into a ruthenium salt aqueous solution, adding a precipitator into the ruthenium salt aqueous solution containing magnesium oxide under the stirring condition, and reacting at room temperature for 1-36 hours to obtain a catalyst precursor;
(b) reduction of a catalyst precursor: and reducing the catalyst precursor for 1-12 hours at 300-600 ℃ in a reducing atmosphere to obtain the supported ruthenium cluster catalyst for ammonia synthesis.
9. Use of at least one of the supported ruthenium cluster catalyst for ammonia synthesis according to claim 1 or 2, the supported ruthenium cluster catalyst for ammonia synthesis prepared according to the process of any one of claims 3 to 8 in catalytic reactions for ammonia synthesis.
10. The application of claim 9, wherein the supported ruthenium cluster catalyst for ammonia synthesis is heated to 300-600 ℃ at a rate of 1-5 ℃/min in a reducing atmosphere containing hydrogen, reduced at the temperature for 1-12 hours, cooled to a reaction temperature of 250-400 ℃, and subjected to ammonia synthesis catalytic reaction in a mixed atmosphere of nitrogen and hydrogen to obtain an ammonia product;
preferably, the volume ratio of nitrogen to hydrogen in the mixed atmosphere is 1: 3-3: 1; the space velocity of the reaction gas is 1000-50000 mL/gcatH; the reaction pressure is 0.1-5.0 MPa.
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