Non-precious metal selective hydrogenation catalyst Ni3InN, its preparation method and application

Abstract

The application discloses a kind of efficient non-noble metal selective hydrogenation catalyst Ni3InN and its preparation method and application, belong to supported metal catalyst technical field.The preparation of catalyst is by impregnation method to load nickel salt and indium salt on nano carrier, then in ammonia-containing atmosphere is heated to prepare Ni3InN catalyst.Performance test shows that Ni3InN catalyst exhibits excellent performance in selective hydrogenation reaction.In 1,3-butadiene hydrogenation reaction, its selectivity reaches more than 90%, far higher than Ni catalyst.At the same time, its activity is about 2 and 5 times higher than Ni and Ni3In catalyst respectively.

Description

Technical Field

[0001] This invention relates to the field of supported metal catalyst technology, specifically to a highly efficient non-precious metal selective hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Selective hydrogenation is an important class of catalytic reactions in industrial catalysis. During the catalytic cracking of naphtha to produce monoolefins, small amounts of alkyne hydrogen and dienes are typically generated. These impurities can poison and deactivate the polymerization catalyst during olefin polymerization; therefore, the content of alkynes and dienes must be reduced to below 3-5 ppm before polymerization. In industrial applications, due to the need to process large quantities of feed gas in a short time, catalysts with high activity and high selectivity are required. Highly efficient but expensive palladium-based catalysts are commonly used to remove alkyne hydrogen and dienes from the feed gas via hydrogenation. Similar to palladium, abundant and inexpensive non-precious metal nickel has been widely used in selective hydrogenation reactions due to its good hydrogenation performance. However, nickel catalysts have several major problems in this type of reaction: insufficient selectivity, prone to over-hydrogenation and polymerization, thus reducing the selectivity of the target olefin; oligomers generated by polymerization can coat the catalyst surface, blocking active sites and leading to catalyst deactivation; and its activity is much lower than that of palladium-based catalysts. Although previous studies have attempted to improve the selectivity and stability of nickel catalysts in selective hydrogenation reactions through various methods, this usually further reduces the catalyst activity. Therefore, how to improve activity while enhancing selectivity is a challenge in the design and development of non-precious metal selective hydrogenation catalysts. Summary of the Invention

[0003] The purpose of this invention is to provide a highly efficient non-precious metal selective hydrogenation catalyst, its preparation method, and its application. A supported Ni3InN catalyst was prepared using non-precious metals, replacing the precious metal palladium-based catalyst. This not only effectively reduces catalyst costs but also demonstrates superior performance in selective hydrogenation reactions. In the hydrogenation reaction of 1,3-butadiene, its activity and selectivity are significantly higher than those of the supported Ni catalyst.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A non-precious metal selective hydrogenation catalyst is disclosed, which is formed by supporting a bimetallic nitride active component on a nanosupport. The bimetallic nitride is Ni3InN, with Ni loading ranging from 0.1 to 50 wt.% and an atomic ratio of Ni to In of 1:10 to 10:1. In the bimetallic nitride Ni3InN, the atomic ratio of Ni to N is 3:1.

[0006] The preparation method of the non-precious metal selective hydrogenation catalyst involves first loading nickel and indium salts onto a nanosupport via impregnation, followed by nitriding treatment in an ammonia-containing atmosphere to obtain a Ni3InN supported catalyst, which is the non-precious metal selective hydrogenation catalyst. The method includes the following steps:

[0007] (1) Dissolve nickel salt and indium salt in an appropriate amount of solvent, then add nanocarrier, stir ultrasonically for 1 to 3 hours to ensure uniform dispersion, and then remove the solvent by rotary evaporator to obtain composite material loaded with nickel salt and indium salt.

[0008] (2) The composite material loaded with nickel salt and indium salt obtained in step (1) is placed in an oven for drying treatment at a temperature of 50 to 300°C for 1 to 24 hours.

[0009] (3) The composite material of nickel salt and indium salt after step (2) is subjected to nitriding treatment in an atmosphere containing ammonia. Ammonia drives the formation of Ni3InN structure to obtain Ni3InN supported catalyst.

[0010] In step (1) above, the nanocarrier material is boron nitride, alumina, carbon nanotubes, activated carbon, carbon nanofibers, silicon dioxide, diatomaceous earth, or graphene, etc.

[0011] In step (1) above, the nickel salt is selected from one or more of nickel acetate, nickel chloride, nickel nitrate, nickel carbonate, nickel sulfate, and nickel acetylacetonate; the indium salt is selected from one or more of indium chloride, indium acetate, indium nitrate, indium sulfate, indium carbonate, and indium acetylacetonate; and the solvent is water, ethanol, or methanol.

[0012] In step (1) above, the weight ratio of nickel salt to indium salt is 1:10 to 10:1; the ratio of nickel salt to nanocarrier is determined by the required loading amount.

[0013] In step (3) above, the nitriding treatment is one or more of the following treatment conditions: the composite material loaded with nickel salt and indium salt is first reduced in a mixed atmosphere of hydrogen and inert gas to obtain Ni3In catalyst, and then nitrided in a mixed atmosphere of ammonia and inert gas; the composite material loaded with nickel salt and indium salt is directly nitrided in a mixed atmosphere of ammonia and inert gas; or the composite material loaded with nickel salt and indium salt is directly nitrided in a mixed atmosphere of ammonia, hydrogen and inert gas, with ammonia driving the generation of Ni3InN catalyst.

[0014] In step (3) above, when a mixed atmosphere of hydrogen and inert gas is used for treatment, the flow rate of the mixed gas is 1-1000 mL / min, the volume ratio of hydrogen in the mixed atmosphere is 0.1-100 vol.%, the treatment temperature is 300-1000℃, and the treatment time is 1-24 hours; when a mixed atmosphere of ammonia and inert gas is used for treatment, the flow rate of the mixed gas is 1-1000 mL / min, the volume ratio of ammonia in the mixed atmosphere is 0.1-100 vol.%, the treatment temperature is 300-1000℃, and the treatment time is 1-24 hours; when a mixed atmosphere of ammonia, hydrogen, and inert gas is used for treatment, the flow rate of the mixed gas is 1-1000 mL / min, the volume ratio of ammonia in the mixed atmosphere is 0.1-99.9 vol.%, the volume ratio of hydrogen is 0.1-99.9 vol.%, the treatment temperature is 300-1000℃, and the treatment time is 1-24 hours.

[0015] The catalyst of this invention is applied to the selective hydrogenation reaction of 3-butadiene or the selective hydrogenation reaction of acetylene, with the following application conditions: for the selective hydrogenation reaction of 1,3-butadiene, the gas composition is 1.0–99.0 vol.% H2, 0.1–99.0 vol.% 1,3-butadiene, and helium as the balance gas; for the selective hydrogenation reaction of acetylene, the gas composition is 1.0–99.0 vol.% H2, 0.1–99.0 vol.% C2H2, and helium as the balance gas; the gas flow rate is 1–1000 mL / min, and the reaction temperature is 10–300 °C.

[0016] Catalyst pretreatment before application:

[0017] A mixture of ammonia and helium (0.1-100 vol.%, preferably 40-60 vol.%) is introduced into a reaction tube containing a supported Ni3InN catalyst, and the catalyst is nitrided for 1-24 hours (preferably 1-6 hours) at a processing temperature of 300-1000°C (preferably 400-600°C).

[0018] Performance tests show that the Ni3InN catalyst exhibits excellent performance in selective hydrogenation reactions. In the hydrogenation of 1,3-butadiene, its selectivity reaches over 90%, significantly higher than that of the Ni catalyst. Furthermore, its activity is approximately 2 and 5 times higher than that of the Ni and Ni3In catalysts, respectively.

[0019] The present invention has the following advantages and beneficial effects:

[0020] 1. This invention utilizes dual non-precious metal nitrides to replace precious metals, significantly reducing the cost of selective hydrogenation catalysts.

[0021] 2. The Ni3InN catalyst prepared in this invention exhibits excellent selectivity in selective hydrogenation reaction performance tests. In the hydrogenation reaction of 1,3-butadiene, the butene selectivity reaches as high as 93.19% at a conversion rate of 97.81%. Furthermore, the specific activity of the Ni3InN catalyst is 2 and 5 times that of the Ni and Ni3In catalysts, respectively. Moreover, its selectivity for ethylene is also significantly improved in the selective hydrogenation reaction of acetylene. In addition, after 50 hours of selective hydrogenation testing of 1,3-butadiene, the catalyst activity and selectivity remain essentially unchanged, indicating that this catalyst possesses excellent selectivity and stability in selective hydrogenation reactions.

[0022] 3. This invention prepares supported Ni3InN catalysts through a simple impregnation method and an ammonia gas-driven strategy. The synthesis strategy is not only simple, but also easy to scale up for industrial production. Attached Figure Description

[0023] Figure 1 The images show the XRD patterns, transmission electron microscopy (TEM) images, and particle size distributions of four catalysts—Ni3In / BN, Ni3InN / BN, Ni3InN / Al2O3, and Ni3InN / oCNT—in Example 1 and Comparative Example 1. Specifically: (a) and (e) are the XRD pattern and TEM image of Ni3In / BN, respectively; (b) and (f) are the XRD pattern and TEM image of Ni3InN / BN, respectively; (c) and (g) are the XRD pattern and TEM image of Ni3InN / Al2O3, respectively; (d) and (h) are the XRD pattern and TEM image of Ni3InN / oCNT, respectively; and the insets show the particle size distributions of the active components in the corresponding catalysts.

[0024] Figure 2 High-resolution transmission electron microscopy (TEM) images of the Ni3In / BN and Ni3InN / BN catalysts in Example 1 and Comparative Example 1 are shown. (a) and (e) are high-resolution images of the Ni3In and Ni3InN structures, respectively; (b) and (f) are unit cell models and unit cell parameters of the Ni3In and Ni3InN structures, respectively; (c) and (g) are magnified views of the marked regions in (a) and (e) and corresponding atomic model overlays, respectively; (d) and (h) are fast Fourier transform diagrams of the Ni3In and Ni3InN structures.

[0025] Figure 3 The selective hydrogenation performance of 1,3-butadiene by Ni / BN, Ni3In / BN and Ni3InN / BN catalysts at 180 °C is shown in Example 1 and Comparative Examples 1-2.

[0026] Figure 4The selective hydrogenation performance of Ni / BN, Ni3In / BN and Ni3InN / BN catalysts at 200 °C is shown in Example 1 and Comparative Examples 1-2.

[0027] Figure 5 The mass ratio activity of the Ni / BN, Ni3In / BN, and Ni3InN / BN catalysts in Example 1 and Comparative Examples 1-2 is given.

[0028] Figure 6 This is a long-term stability test of the Ni3InN / BN catalyst in Example 1 during the selective hydrogenation reaction of 1,3-butadiene. Detailed Implementation

[0029] This invention utilizes non-precious metals to replace precious metals, and prepares a supported Ni3InN catalyst through impregnation and ammonia treatment. The invention is further illustrated below with reference to embodiments and accompanying drawings.

[0030] Example 1

[0031] The process for preparing the supported Ni3InN catalyst in this embodiment is as follows:

[0032] 1. Impregnation method: Dissolve 99.10 mg of nickel nitrate hexahydrate and 34.17 mg of indium nitrate hydrate in 40 mL of ethanol, then add 165.78 mg of carrier (BN, Al2O3 and oCNT respectively), sonicate and stir for about 1 hour to ensure uniform dispersion, then remove the solvent ethanol by rotary evaporator (temperature 40℃), and keep warm in 100℃ oven for 2 hours.

[0033] 2. The sample treated in step 1 was subjected to reduction treatment in a mixed atmosphere of hydrogen and argon. The flow rate of the mixed gas was 100 mL / min, and the volume ratio of hydrogen in the mixed gas was 50 vol.%. During the reduction treatment, the temperature was increased to 500℃ at a heating rate of 5℃ / min and kept at that temperature for 2 hours. The temperature was then lowered to room temperature to obtain the supported Ni3In catalyst.

[0034] 3. After purging with helium for 30 min, switch to a mixture of ammonia and helium at a flow rate of 40 mL / min, with ammonia at a vol.% concentration. After being treated at 500℃ for 2 hours, the mixture was cooled to room temperature to obtain supported Ni3InN catalysts (Ni3InN / BN, Ni3InN / Al2O3, and Ni3InN / oCNT, respectively).

[0035] In the supported Ni3InN catalyst prepared in this embodiment, the Ni loading is 10 wt.%.

[0036] Comparative Example 1

[0037] The process and conditions are the same as in Example 1, except that step 3 is omitted, and a Ni3In / BN catalyst with a Ni loading of 10 wt.% is obtained.

[0038] Comparative Example 2

[0039] The process and conditions are the same as in Example 1. The difference from Example 1 is that in step 1, the impregnation method involves dissolving 99.10 mg of nickel nitrate hexahydrate in 40 mL of ethanol and then adding 180 mg of support; step 3 is omitted to obtain a Ni / BN catalyst with a Ni loading of 10 wt.%.

[0040] The XRD patterns, transmission electron microscopy images, and particle size distributions of the supported Ni3InN and Ni3In catalysts prepared in Example 1 and Comparative Example 1 are shown below. Figure 1 High-resolution transmission electron microscopy images of Ni3InN and Ni3In catalysts are shown below. Figure 2 As shown in the figure, XRD and HRTEM results indicate that Ni and In elements exist in the form of Ni3In alloy under reducing atmosphere. Furthermore, nitrogen atoms adsorbed and dissociated from the nickel surface enter the interstices of nanoparticles, forming a Ni3InN interstitial nitride structure modified with subsurface nitrogen atoms.

[0041] Example 2

[0042] The Ni3InN, Ni3In, and Ni catalysts prepared in Example 1 and Comparative Examples 1-2 were applied to selective hydrogenation reactions, respectively. The application process is as follows:

[0043] Take 2 mg of the 10% loaded Ni3InN, Ni3In and Ni catalysts obtained above and add them to the quartz reaction tube. Fix the catalysts in the middle temperature zone of the reaction bed by quartz wool.

[0044] First, preprocessing is performed:

[0045] A mixture of hydrogen and helium (50 vol.% hydrogen) was introduced into a reaction tube containing a supported Ni catalyst, and the catalyst was reduced at 500°C for 2 hours. The gas flow rate was controlled at 20 mL / min using a mass flow meter.

[0046] A mixture of hydrogen and helium (50 vol.% hydrogen) was introduced into a reaction tube containing a supported Ni3In catalyst. The catalyst was reduced at 500°C for 2 hours, and the gas flow rate was controlled at 20 mL / min using a mass flow meter.

[0047] A mixture of ammonia and helium (50 vol.% ammonia) was introduced into a reaction tube containing a supported Ni3InN catalyst. The catalyst was nitrided at 500°C for 2 hours, and the gas flow rate was controlled at 20 mL / min using a mass flow meter.

[0048] After pretreatment, the temperature was lowered to 150℃, and then the catalyst performance was tested. Specifically, the gas composition for the selective hydrogenation reaction of 1,3-butadiene was 8.0 vol.% H2, 1.0 vol.% 1,3-butadiene, and the remainder was helium as a balance gas; the gas composition for the hydrogenation reaction of acetylene was 10.0 vol.% H2, 1.0 vol.% C2H2, and the remainder was helium as a balance gas. The above gases were introduced into the reaction tube at a flow rate of 50 mL / min.

[0049] Selective hydrogenation reaction performance test results (reference) Figure 3-6 ):

[0050] When the Ni3InN catalyst prepared in Example 1 was applied to the selective hydrogenation of 1,3-butadiene, the selectivity for butene was significantly improved, reaching approximately 93%. Furthermore, under the same reaction conditions, the specific activity of the Ni3InN catalyst was 2 times that of the Ni catalyst and 5 times that of the Ni3In catalyst. In the selective hydrogenation of acetylene, its selectivity for ethylene was also significantly improved (~80%). Moreover, after a 50-hour stability test, the activity and selectivity of the Ni3InN catalyst remained essentially unchanged, indicating that this catalyst possesses excellent selectivity and stability in selective hydrogenation reactions.

[0051] The Ni3In catalyst prepared in Comparative Example 1 showed the following selectivity for the target product in the two selective hydrogenation reactions: approximately 46% for butene and approximately 40% for ethylene.

[0052] The Ni3In catalyst prepared in Comparative Example 2 showed the following selectivity for the target product in the two selective hydrogenation reactions: approximately 14% for butene and approximately 14% for ethylene.

[0053] The above description is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of a non-precious metal selective hydrogenation catalyst, characterized in that, This catalyst is used in the selective hydrogenation of 1,3-butadiene or the selective hydrogenation of acetylene. The catalyst is formed by supporting a bimetallic nitride active component on a support. The bimetallic nitride is Ni3InN, and the loading of Ni is 5-12 wt.%.

2. The application of the non-precious metal selective hydrogenation catalyst according to claim 1, characterized in that, The catalyst support material is one or more of boron nitride, alumina, carbon nanotubes, activated carbon, carbon nanofibers, silicon dioxide, diatomaceous earth, or graphene.

3. The application of the non-precious metal selective hydrogenation catalyst according to claim 1, characterized in that: The catalyst is prepared by first loading nickel salt and indium salt onto a support by impregnation, and then performing nitriding treatment in an atmosphere containing ammonia to obtain a Ni3InN supported catalyst, which is the non-precious metal selective hydrogenation catalyst.

4. The application of the non-precious metal selective hydrogenation catalyst according to claim 3, characterized in that: The preparation method includes the following steps: (1) Dissolve nickel salt and indium salt in solvent, then add carrier, and ultrasonically stir for 1 to 3 hours to ensure uniform dispersion. After removing solvent, obtain composite material loaded with nickel salt and indium salt. (2) The composite material loaded with nickel salt and indium salt obtained in step (1) is placed in an oven for drying treatment at a temperature of 50~300℃ for 1~24 hours. (3) The composite material of nickel salt and indium salt after step (2) is subjected to nitriding in an atmosphere containing ammonia. Ammonia drives the formation of Ni3InN structure to obtain Ni3InN supported catalyst.

5. The application of the non-precious metal selective hydrogenation catalyst according to claim 4, characterized in that, In step (1), the nickel salt is selected from one or more of nickel acetate, nickel chloride, nickel nitrate, nickel carbonate, nickel sulfate, and nickel acetylacetonate; the indium salt is selected from one or more of indium chloride, indium acetate, indium nitrate, indium sulfate, indium carbonate, and indium acetylacetonate; and the solvent is selected from one or more of water, ethanol, or methanol. The solvent removal process is completed using a rotary evaporator at a temperature of 30-60℃.

6. The application of the non-precious metal selective hydrogenation catalyst according to claim 4, characterized in that, In step (3), the nitriding treatment is performed under one or more of the following conditions: The composite material loaded with nickel salt and indium salt was first reduced in a mixed atmosphere of hydrogen and inert atmosphere to obtain Ni3In catalyst, and then nitrided in a mixed atmosphere of ammonia and inert atmosphere. Alternatively, the composite material loaded with nickel salt and indium salt can be directly nitrided in a mixed atmosphere of ammonia and inert atmosphere. Alternatively, the composite material supported on nickel salt and indium salt can be directly nitrided in ammonia, hydrogen, or a mixed atmosphere containing or without an inert atmosphere, with ammonia driving the generation of Ni3InN catalyst. The inert atmosphere is one or more of nitrogen, helium or argon.

7. The application of the non-precious metal selective hydrogenation catalyst according to claim 6, characterized in that, Nitriding treatment conditions: When a catalyst with a mass of 0.1 mg to 100 g is treated with a mixed atmosphere of hydrogen and inert atmosphere, the flow rate of the mixed atmosphere is 1 to 1000 mL / min; the volume ratio of hydrogen in the mixed atmosphere is 40 to 60 vol.%; the treatment temperature is 400 to 600℃; and the treatment time is 2 to 4 hours. When a catalyst with a mass of 0.01 mg to 100 g is treated with a mixed atmosphere of ammonia and an inert atmosphere, the flow rate of the mixed atmosphere is 1 to 1000 mL / min; the volume ratio of ammonia in the mixed atmosphere is 40 to 60 vol.%, the treatment temperature is 400 to 600℃, and the treatment time is 2 to 4 hours. When a catalyst with a mass of 0.01 mg to 100 g is treated with ammonia, hydrogen, or a mixed atmosphere containing or without an inert atmosphere, the flow rate of the mixed atmosphere is 1 to 1000 mL / min; the volume ratio of ammonia in the mixed atmosphere is 40 to 60 vol.%, the volume ratio of hydrogen is 40 to 60 vol.%, the treatment temperature is 400 to 600℃, and the treatment time is 2 to 4 hours.

8. The application of the non-precious metal selective hydrogenation catalyst according to claim 1, characterized in that, The application conditions are as follows: the gas composition of the selective hydrogenation reaction of 1,3-butadiene is: 75~95 vol.% H2, 5~25 vol.% 1,3-butadiene, with or without helium as the balance gas; The gaseous components of the selective hydrogenation reaction of acetylene are: 5~25 vol.% H2, 5~25 vol.% C2H2, with or without helium as the balance gas; The catalyst has a mass of 0.01 mg to 100 g, the gas flow rate is 1 to 1000 mL / min, and the reaction temperature is 120 to 200℃.

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