CN112337494B - Catalyst for preparing hydrogen by decomposing ammonia and preparation method and application thereof - Google Patents
Catalyst for preparing hydrogen by decomposing ammonia and preparation method and application thereof Download PDFInfo
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Abstract
The catalyst is prepared by a sol-gel method and comprises non-noble metal active components and a BN-rare earth metal oxide composite carrier loading the non-noble metal active components, wherein the mass fraction of the active components in the catalyst is 5-20 wt%, and the mass fraction of the carrier is 80-95 wt%. The catalyst of the invention takes transition metal as active component, BN and metal oxide as composite carrier, has simple preparation process, low cost and excellent catalytic activity of ammonia decomposition reaction, and test results show that the conversion rate of ammonia gas can reach more than 99 percent and the generation rate of hydrogen can reach 33.4 mmol/(g) cat Min) is a novel catalyst for high-efficiency ammonia decomposition hydrogen production.
Description
Technical Field
The invention relates to the field of catalyst preparation and heterogeneous catalysis, in particular to an ammonia decomposition hydrogen production catalyst, a preparation method thereof and application thereof in ammonia decomposition hydrogen production reaction.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) using hydrogen as a raw material have the advantages of high energy conversion rate, no pollution, low working temperature and the like, have great application potential in the aspects of electric automobiles, standby power supplies and the like, and attract extensive attention of the industry and academia. One of the reasons why the large-scale application of PEMFCs is currently limited is that the high-purity hydrogen used as a fuel cannot be supplied on a large scale. Hydrogen is difficult to store and transport due to its low density, flammability, explosiveness, etc., and thus cannot be used as a raw material for large-scale PEMFC. And a matrix containing carbonHydrogen gas produced by the reforming reaction (such as methanol, etc.) inevitably contains CO as a by-product, thereby causing deactivation of the fuel cell electrode. It is relatively more feasible to provide a hydrogen source for the PEMFC through the ammonia decomposition hydrogen production reaction. The ammonia gas has high hydrogen content (17.6 wt%), is easy to liquefy (the liquefying pressure at 20 ℃ is only 8 atmospheric pressures), and is convenient to transport and store. In addition, the ammonia decomposition product is H 2 And N 2 Unreacted NH 3 And can be removed by the adsorbent without adversely affecting the fuel cell. Moreover, the ammonia synthesis process is mature, and the price of hydrogen prepared by taking ammonia as a raw material is relatively low. Therefore, the ammonia decomposition hydrogen production reaction is one of the promising methods for providing hydrogen source for PEMFC.
Currently, the main active components of ammonia decomposition catalysts include Ru, ni, fe, co — Mo alloys, and the like. Among them, the Ru-based catalyst has excellent low-temperature ammonia decomposition reaction activity among a large number of ammonia decomposition catalysts. However, ru as a noble metal has the characteristics of low reserves and high cost, which limits the application of Ru in large-scale industrialization. Among non-noble metal catalysts, ni-based and Co-based catalysts show good ammonia decomposition catalytic activity, have the advantages of easy acquisition and low price, and have great potential in large-scale ammonia decomposition hydrogen production application.
The literature results show that the support of the ammonia decomposition catalyst has a large influence on its catalytic activity. Among the common catalyst supports are Al 2 O 3 、MgO、ZrO 2 、SiO 2 、CeO 2 Activated carbon, carbon nanotubes, and the like. According to reports, ni and Co are combined with most of carriers to show a certain catalytic performance of ammonia decomposition hydrogen production, while higher ammonia decomposition efficiency generally needs to improve the loading capacity of metal components, and the mass fraction of the metal components can reach 10-65 wt%. However, high loadings of metal tend to result in agglomeration during the catalytic reaction, which has disadvantages such as reduced availability and increased cost, which adversely affect the scale application of the catalyst.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst which has strong metal-carrier interaction and is applied to high-efficiency ammonia decomposition hydrogen production reaction and a preparation method thereof.
The invention adopts the following technical scheme:
the catalyst comprises a non-noble metal active component and a BN-rare earth metal oxide composite carrier for loading the non-noble metal active component, wherein the mass fraction of the active component in the catalyst is 5-20 wt%, and the mass fraction of the carrier is 80-95 wt%.
The active component is a transition metal.
Preferably, the active component is one of Ni and Co.
The rare earth metal oxide in the carrier is CeO 2 、Y 2 O 3 To (3) is provided.
The particle size of the catalyst is 60-80 meshes.
A preparation method of a catalyst for hydrogen production by ammonia decomposition comprises the following steps:
s1, surface modification of BN: BN is first mixed with 30% of H 2 O 2 Mixing the solution and stirring for 20-24 h at room temperature to obtain a mixed solution; then placing the mixed solution in a hydrothermal kettle, heating at 120-130 ℃ for 20-24 h, filtering, washing with deionized water, and drying to obtain modified BN with hydroxyl on the surface;
s2, preparing the catalyst by a sol-gel method: putting non-noble metal nitrate and the modified BN prepared in the step S1 into an ethanol water solution, performing ultrasonic treatment for 3-5 h, then adding rare earth metal nitrate and citric acid, stirring for 1-2 h, and heating at 85-90 ℃ until green or red gel is obtained; and grinding the gel into powder, then carrying out heat treatment, raising the temperature to 300 ℃ at a speed of 1 ℃/min, preserving the heat for 2h, then raising the temperature to 450 ℃ at a speed of 2 ℃/min, preserving the heat for 2h, and finally obtaining the non-noble metal/BN-rare earth metal oxide catalyst.
BN and H added in the step S1 2 O 2 The mass-to-volume ratio (g/mL) of the solution is 1 (70-80).
The deionized water washing times in the step S1 are not less than three times; the temperature of the drying treatment is 60-65 ℃, and the drying time is 12-18 h.
The mass ratio of the non-noble metal nitrate, the modified BN, the rare earth metal nitrate and the citric acid added in the step S2 is (0.67-3.2) to 1 (4-5.39) to 5.
The non-noble metal nitrate is one of nickel nitrate and cobalt nitrate, and the rare earth metal nitrate is one of cerium nitrate and yttrium nitrate.
The catalyst is filled in a quartz tube of an ammonia decomposition hydrogen production reaction device, and 50% of H is added before catalytic reaction 2 Reducing at 500 ℃ for 3h under Ar atmosphere, then blowing for 1h under Ar atmosphere, and finally NH at 500 to 750 DEG C 3 The ammonia decomposition hydrogen production reaction is carried out in the atmosphere.
NH 3 The flow rate is 50mL/min, and the catalyst addition is 30000 mL/(g) based on the space velocity of the catalyst cat H), catalyst space velocity = gas flow rate/catalyst mass.
The technical scheme of the invention has the following advantages:
A. the BN and rare earth metal oxide dual-carrier adopted by the catalyst has obviously enhanced metal-carrier interaction, and greatly improves the dispersion degree of metal active components, thereby improving the activity of the ammonia decomposition catalyst and leading NH 3 Can be decomposed into N at lower temperature 2 And H 2 。
B. The invention takes transition metal (Ni or Co) as active component, BN and metal oxide (CeO) 2 Or Y 2 O 3 ) Is a composite carrier and has excellent catalytic activity of ammonia decomposition reaction. Test results show that the conversion rate of ammonia can reach more than 99.5 percent, and the generation rate of hydrogen can reach 33.4 mmol/(g) cat Min). The method has simple preparation process and low cost, shows higher catalytic activity in ammonia decomposition reaction, and is a novel catalyst for preparing hydrogen by decomposing ammonia.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts.
FIG. 1 is a graph showing NH in the decomposition reaction of ammonia in catalysts prepared in example 1 and comparative example 1 of the present invention 3 A conversion plot;
FIG. 2 is a graph showing NH content of catalysts prepared in examples 2 and 3 of the present invention and comparative examples 2 and 3 applied to decomposition reaction of ammonia 3 A conversion plot;
FIG. 3 shows NH in decomposition reaction of ammonia in catalysts prepared in examples 4 and 5 of the present invention and comparative examples 4 and 5 3 The conversion profile.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a catalyst for preparing hydrogen by decomposing ammonia, which is obtained by loading non-noble metal active components on a BN-rare earth metal oxide composite carrier, wherein the mass fraction of the active components in the catalyst is 5-20 wt%, and the mass fraction of the carrier is 80-95 wt%. The active component is transition metal, preferably one of Ni and Co, and the rare earth metal oxide in the carrier is CeO 2 、Y 2 O 3 One kind of (1). The particle size of the catalyst is 60-80 meshes.
The invention also provides a preparation method of the catalyst for preparing hydrogen by decomposing ammonia, which comprises the following steps:
s1, surface modification of BN: BN is first mixed with 30% of H 2 O 2 Mixing the solution and stirring for 20-24 h at room temperature to obtain a mixed solution; the mixed solution is then placed in a hydrothermal kettle at 120 deg.fHeating at 130 ℃ for 20-24 h, filtering, washing with deionized water, and drying to obtain modified BN with hydroxyl on the surface; wherein BN and H are added 2 O 2 The mass volume ratio (g/mL) of the solution is 1 (70-80), the washing times of deionized water are not less than three times, the temperature of drying treatment is 60-65 ℃, and the drying time is 12-18 h.
S2, preparing a catalyst by a sol-gel method: putting non-noble metal nitrate and the modified BN prepared in the step S1 into an ethanol water solution, performing ultrasonic treatment for 3-5 h, then adding rare earth metal nitrate and citric acid, stirring for 1-2 h, and heating at 85-90 ℃ until green or red gel is obtained; and grinding the gel into powder, then carrying out heat treatment, raising the temperature to 300 ℃ at a speed of 1 ℃/min, preserving the heat for 2h, then raising the temperature to 450 ℃ at a speed of 2 ℃/min, preserving the heat for 2h, and finally obtaining the non-noble metal/BN-rare earth metal oxide catalyst. The mass ratio of the added non-noble metal nitrate, the modified BN, the rare earth metal nitrate and the citric acid is (0.67-3.2) to 1 (4-5.39) to 5, the non-noble metal nitrate is one of nickel nitrate and cobalt nitrate, and the rare earth metal nitrate is one of cerium nitrate and yttrium nitrate.
The BN and rare earth metal oxide dual-carrier adopted by the catalyst has obviously enhanced metal-carrier interaction, and greatly improves the dispersion degree of metal active components, thereby improving the activity of the ammonia decomposition catalyst and leading NH 3 Can be decomposed into N at lower temperature 2 And H 2 。
In addition, the present invention also provides the application of the catalyst for ammonia decomposition hydrogen production in the ammonia decomposition hydrogen production reaction, wherein the prepared catalyst is filled in a quartz tube of an ammonia decomposition hydrogen production reaction device, and the content of H is 50% before the catalytic reaction 2 Reduction at 500 ℃ for 3h under Ar atmosphere, subsequent purging for 1h under Ar atmosphere, and finally NH at 500-750 DEG C 3 The ammonia decomposition hydrogen production reaction is carried out in the atmosphere. The adding amount of the catalyst is 30000 mL/(g) based on the airspeed of the catalyst cat H), catalyst space velocity = gas flow rate/catalyst mass, NH 3 The flow rate was 50mL/min.
The present invention will be described in detail below by way of specific examples.
Example 1:
10wt％Ni/BN-CeO 2 preparation of catalyst for ammonia decomposition hydrogen production:
s1, with H 2 O 2 Preprocessing BN: 1g BN with 70mL 30% H 2 O 2 The solution was mixed and stirred at room temperature for 24h; heating the mixed solution in a hydrothermal kettle at 120 ℃ for 24 hours; filtering and washing with deionized water for three times, and drying at 60 ℃ for 12 hours to obtain pretreated modified BN;
s2, preparing the catalyst by a sol-gel method: 1.42g of nickel nitrate and 1g of the pretreated modified BN were placed in an aqueous ethanol solution (50 mL of water +25mL of ethanol) and subjected to ultrasonic treatment for 3 hours, followed by addition of 4g of cerium nitrate and 5g of citric acid, stirring for 1 hour, and heating at 85 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, and maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain 10wt% of Ni/BN-CeO 2 A catalyst, wherein the mass fraction of Ni is 10wt%.
Example 2
10wt％Co/BN-CeO 2 Preparation of catalyst for hydrogen production by ammonia decomposition:
s1, with H 2 O 2 Preprocessing BN: 1g BN with 70mL 30% H 2 O 2 The solution is mixed and stirred for 24 hours at room temperature; placing the mixed solution in a hydrothermal kettle, and heating for 24 hours at 120 ℃; filtering and washing the mixture for three times by using deionized water, and drying the mixture for 16 hours at the temperature of 60 ℃ to obtain pretreated modified BN;
s2, preparing a catalyst by a sol-gel method: 1.42g of cobalt nitrate and 1g of the pretreated modified BN were sonicated in aqueous ethanol (50 mL of water +25mL of ethanol) for 3h, followed by addition of 4g of cerium nitrate and 5g of citric acid, stirring for 1h, and heating at 85 ℃ until a pink gel was obtained. Grinding the gel into powder, heat treating, maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2h respectively to obtain 10wt% Co/BN-CeO 2 Catalyst, wherein the mass fraction of Co is 10wt%.
Example 3
10wt％Ni/BN-Y 2 O 3 Preparation of catalyst for ammonia decomposition hydrogen production:
s1, with H 2 O 2 Preprocessing BN: 1g BN with 70mL 30% H 2 O 2 Mixing the solution and stirring at room temperature for 24h; heating the mixed solution in a hydrothermal kettle at 120 ℃ for 24 hours; filtering and washing the mixture for three times by using deionized water, and drying the mixture for 18 hours at the temperature of 60 ℃ to obtain pretreated modified BN;
s2, preparing the catalyst by a sol-gel method: 1.42g of nickel nitrate and 1g of the pretreated modified BN were placed in an aqueous ethanol solution (50 mL of water +25mL of ethanol), sonicated for 3h, followed by addition of 5.39 g of yttrium nitrate and 5g of citric acid, stirred for 1h, and heated at 85 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain a final content of 10wt% Ni/BN-Y 2 O 3 The catalyst comprises 10wt% of Ni.
Example 4
5wt％Ni/BN-CeO 2 Preparation of catalyst for hydrogen production by ammonia decomposition:
s1, with H 2 O 2 Preprocessing BN: 1g BN with 80mL 30% H 2 O 2 The solution was mixed and stirred at room temperature for 20h; placing the mixed solution in a hydrothermal kettle, and heating at 130 ℃ for 20h; filtering and washing with deionized water for three times, and drying at 65 ℃ for 16h to obtain pretreated modified BN;
s2, preparing the catalyst by a sol-gel method: 0.67g of nickel nitrate and 1g of the pretreated modified BN were put in an aqueous ethanol solution (50 mL of water +25mL of ethanol), sonicated for 5 hours, followed by addition of 4g of cerium nitrate and 5g of citric acid, stirred for 1 hour, and heated at 90 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, and maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain 5wt% of Ni/BN-CeO 2 The catalyst comprises 5wt% of Ni.
Example 5
20wt％Ni/BN-CeO 2 Preparation of catalyst for ammonia decomposition hydrogen production:
s1, with H 2 O 2 Preprocessing BN: 1g BN with 70mL 30% H 2 O 2 Mixing the solution and stirring at room temperature for 24h; will be provided withThe mixed solution is placed in a hydrothermal kettle and heated for 24 hours at 120 ℃; filtering and washing the mixture for three times by using deionized water, and drying the mixture overnight at 60 ℃ to obtain pretreated modified BN;
s2, preparing the catalyst by a sol-gel method: 3.2g of nickel nitrate and 1g of the pretreated modified BN were placed in an aqueous ethanol solution (50 mL of water +25mL of ethanol), sonicated for 3h, followed by addition of 4g of cerium nitrate and 5g of citric acid, stirred for 1h, and heated at 85 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, and maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain 2 wt% Ni/BN-CeO 2 A catalyst, wherein the mass fraction of Ni is 20wt%.
To further illustrate the important role of BN in the present invention, catalysts without added BN were selected for comparison.
Comparative example 1
10wt％Ni/CeO 2 Preparation of catalyst for ammonia decomposition hydrogen production:
preparing a catalyst by a sol-gel method: 1.42g of nickel nitrate was dissolved in 25mL of water and sonicated for 3h, followed by 6.5g of cerium nitrate, 5g of citric acid and 25mL of water, stirred for 1h, and heated at 85 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, and maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain 10wt% of Ni/CeO 2 The catalyst comprises 10wt% of Ni.
Comparative example 2
10wt％Co/CeO 2 Preparation of catalyst for hydrogen production by ammonia decomposition:
preparing a catalyst by a sol-gel method: 1.42g of cobalt nitrate was dissolved in 25mL of water and sonicated for 3h, followed by addition of 6.5g of cerium nitrate, 5g of citric acid and 25mL of water, stirred for 1h, and heated at 85 ℃ until a pink gel was obtained. Grinding the gel into powder, then carrying out heat treatment, and carrying out heat preservation for 2h under the conditions that the temperature is increased to 300 ℃ at the rate of 1 ℃/min and the temperature is increased to 450 ℃ at the rate of 2 ℃/min to finally obtain 10wt% Co/CeO 2 The catalyst comprises 10wt% of Co.
Comparative example 3
10wt％Ni/Y 2 O 3 Preparation of catalyst for hydrogen production by ammonia decomposition:
preparing a catalyst by a sol-gel method: 1.42g of nickel nitrate was dissolved in 25mL of water and sonicated for 3h, followed by addition of 8.75g of yttrium nitrate, 5g of citric acid and 25mL of water, stirred for 1h, and heated at 85 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, keeping the temperature at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2h respectively to obtain 10wt% Ni/Y 2 O 3 The catalyst comprises 10wt% of Ni.
Comparative example 4
5wt％Ni/CeO 2 Preparation of catalyst for ammonia decomposition hydrogen production:
preparing a catalyst by a sol-gel method: 0.67g of nickel nitrate was dissolved in 25mL of water and sonicated for 5h, followed by the addition of 6.5g of cerium nitrate, 5g of citric acid and 25mL of water, stirring for 1h, and heating at 90 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, and maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain 5wt% of Ni/CeO 2 The catalyst comprises 5wt% of Ni.
Comparative example 5
20wt％Ni/CeO 2 Preparation of catalyst for hydrogen production by ammonia decomposition:
preparing a catalyst by a sol-gel method: nickel nitrate (3.2 g) was dissolved in 25mL of water and sonicated for 3h, followed by the addition of cerium nitrate (6.5 g), citric acid (5 g) and 25mL of water, stirred for 1h, and heated at 85 ℃ until a green gel was obtained. Grinding the gel into powder, heat treating, and maintaining at 1 deg.C/min to 300 deg.C and 2 deg.C/min to 450 deg.C for 2 hr to obtain 2 wt% Ni/CeO 2 Catalyst, wherein the mass fraction of Ni is 20wt%.
Test example 1
This test example 10wt% of Ni/BN-CeO obtained in inventive example 1 2 1% by weight of the catalyst and comparative example 1 Ni/CeO 2 The catalyst is used for ammonia decomposition hydrogen production activity test, and the specific test method and the result are as follows:
the activity test of the catalyst is carried out on a gas chromatography equipped ammonia decomposition hydrogen production reaction device, 0.1g of the catalyst (60-80 meshes) is filled in a quartz tube, and 50 percent of the catalyst is used before the catalytic reactionH 2 Reduction at 500 ℃ for 3h under Ar atmosphere, subsequent purging for 1h under Ar atmosphere, and finally NH at 500-750 ℃ 3 Evaluation of Activity in atmosphere, NH 3 The flow rate was 50mL/min. The results of the performance tests of the catalysts prepared in inventive example 1 and comparative example 1 are shown in FIG. 1, in which the catalyst NH prepared in inventive example 1 is carried out at 650 deg.C 3 Conversion 98.1%, H 2 The yield was 32.8 mmol/(g) cat Min) higher than the catalyst NH prepared in comparative example 1 according to the invention 3 Conversion 90.3%, and H thereof 2 The yield was 30.2 mmol/(g) cat ·min)。
Test example 2
This test example 10wt% of Co/BN-CeO obtained in example 2 of the present invention 2 1% by weight of Co/CeO obtained from catalyst and comparative example 2 2 Catalyst, and 10wt% Ni/BN-Y from inventive example 3 2 O 3 Catalyst and 10wt% obtained in comparative example 3 2 O 3 The catalyst is used for carrying out ammonia decomposition hydrogen production activity test and comparison, and the specific test method and result are as follows:
the activity test of the above catalyst was carried out on a gas chromatograph equipped with an ammonia decomposition hydrogen production reaction apparatus, and 0.1g of the catalyst (60 to 80 mesh) was packed in a quartz tube and 50% by volume before the catalytic reaction 2 Reduction at 500 ℃ for 3h under Ar atmosphere, subsequent purging for 1h under Ar atmosphere, and finally NH at 500-750 DEG C 3 Evaluation of Activity in atmosphere, NH 3 The flow rate was 50mL/min. The results of the performance test of the catalysts prepared in inventive example 2 and comparative example 2, and in inventive example 3 and comparative example 3 are shown in FIG. 2, in which NH of the catalyst prepared in inventive example 2 is measured at 650 deg.C 3 Conversion 96.1%, H 2 The yield was 32.2 mmol/(g) cat Min) higher than the catalyst NH prepared according to comparative example 2 of the invention 3 Conversion 92.7%, and H thereof 2 The yield was 31.0 mmol/(g) cat Min); catalyst NH obtained in example 3 of the invention 3 Conversion 98.4%, H 2 The yield was 33.0 mmol/(g) cat Min) higher than the catalyst NH prepared in comparative example 3 of the invention 3 Conversion 93.8%, and H thereof 2 The yield was 31.4 mmol/(g) cat ·min)。
Test example 3
This test example 5wt% Ni/BN-CeO obtained in inventive example 4 2 5wt% Ni/CeO of catalyst and comparative example 4 2 Catalyst, and 20wt% Ni/BN-CeO prepared in inventive example 5 2 Catalyst and 20wt% obtained in comparative example 5 Ni/CeO 2 The catalyst is used for carrying out ammonia decomposition hydrogen production activity test and comparison, and the specific test method and result are as follows:
the activity test of the above catalyst was carried out on a gas chromatograph equipped with an ammonia decomposition hydrogen production reaction apparatus, and 0.1g of the catalyst (60 to 80 mesh) was packed in a quartz tube and 50% by volume before the catalytic reaction 2 Reduction at 500 ℃ for 3h under Ar atmosphere, subsequent purging for 1h under Ar atmosphere, and finally NH at 500-750 ℃ 3 Evaluation of Activity in atmosphere, NH 3 The flow rate was 50mL/min. The results of the performance tests of the catalysts prepared in inventive example 4 and comparative example 4, and in inventive example 5 and comparative example 5 are shown in FIG. 3, in which the catalyst NH prepared in inventive example 4 was maintained at 650 deg.C 3 Conversion 92.4%, H 2 The yield was 30.9 mmol/(g) cat Min) higher than the catalyst NH prepared in comparative example 4 of the invention 3 Conversion 84.6%, and H thereof 2 The yield was 28.3 mmol/(g) cat Min); catalyst NH prepared in example 5 of the invention 3 Conversion 99.5%, H 2 The yield was 33.4 mmol/(g) cat Min) higher than the catalyst NH prepared according to inventive comparative example 5 3 Conversion 98.3%, and H thereof 2 The yield was 32.9 mmol/(g) cat ·min)。
The invention is applicable to the prior art.
It should be understood that the above-described embodiments are merely examples for clarity of description and are not intended to limit the scope of the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This list is neither intended to be exhaustive nor exhaustive. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. The catalyst for hydrogen production through ammonia decomposition is characterized by comprising a non-noble metal active component and a BN-rare earth metal oxide composite carrier loading the non-noble metal active component, wherein the mass fraction of the active component in the catalyst is 5-20 wt%, and the mass fraction of the carrier is 80-95 wt%;
the active component is one of Ni and Co;
the rare earth metal oxide in the carrier is CeO 2 、Y 2 O 3 One of (a) and (b);
the preparation method of the ammonia decomposition hydrogen production catalyst comprises the following steps:
s1, surface modification of BN: BN is first mixed with 30% of H 2 O 2 Mixing the solutions and stirring at room temperature for 20-24 h to obtain a mixed solution; then placing the mixed solution in a hydrothermal kettle, heating for 20-24 h at 120-130 ℃, filtering, washing with deionized water, and drying to obtain modified BN with hydroxyl on the surface;
s2, preparing the catalyst by a sol-gel method: putting non-noble metal nitrate and the modified BN prepared in the step S1 into an ethanol water solution, carrying out ultrasonic treatment for 3 to 5 hours, then adding the rare earth metal nitrate and citric acid, stirring for 1 to 2 hours, and heating at 85 to 90 ℃ until green or red gel is obtained; grinding the gel into powder, then carrying out heat treatment, raising the temperature to 300 ℃ at a speed of 1 ℃/min, carrying out heat preservation for 2h, then raising the temperature to 450 ℃ at a speed of 2 ℃/min, and carrying out heat preservation for 2h respectively to finally obtain the non-noble metal/BN-rare earth metal oxide catalyst;
BN and H added in the step S1 2 O 2 The mass-to-volume ratio (g/mL) of the solution is 1 (70 to 80);
the mass ratio of the non-noble metal nitrate, the modified BN, the rare earth metal nitrate and the citric acid added in the step S2 is (0.67 to 3.2): 1 (4 to 5.39) to 5;
the non-noble metal nitrate is one of nickel nitrate and cobalt nitrate, and the rare earth metal nitrate is one of cerium nitrate and yttrium nitrate.
2. The catalyst for ammonia decomposition hydrogen production according to claim 1, wherein the particle size of the catalyst is 60 to 80 mesh.
3. The catalyst for ammonia decomposition hydrogen production according to claim 2, wherein the deionized water is washed not less than three times in step S1; the temperature of the drying treatment is 60 to 65 ℃, and the drying time is 12 to 18 hours.
4. The application of the catalyst for ammonia decomposition hydrogen production in the ammonia decomposition hydrogen production reaction is characterized in that the catalyst of any one of claims 1 to 3 is filled in a quartz tube of a reaction device for ammonia decomposition hydrogen production, and 50% of H is generated before the catalytic reaction 2 Reducing at 500 ℃ for 3h under Ar atmosphere, then blowing for 1h under Ar atmosphere, and finally NH at 500 to 750 DEG C 3 The ammonia decomposition hydrogen production reaction is carried out in the atmosphere.
5. Use according to claim 4, characterised in that NH 3 The flow rate is 50mL/min, and the catalyst addition is 30000 mL/(g) based on the space velocity of the catalyst cat H), catalyst space velocity = gas flow rate/catalyst mass.
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