JP-10 fuel steam reforming catalyst and method for preparing the same

Abstract

The application discloses a JP-10 fuel steam reforming catalyst and a preparation method thereof. The catalyst is composed of aNi-bFe / cSiO2.dMgO; wherein, Ni and Fe are metal active components, a+b=5%, and 3%<=a<=4%; SiO2 and MgO are oxide carriers, c+d=95% and 70%<=c<=80%; the preparation method is as follows: uniformly dispersed composite oxide carriers SiO2.MgO are prepared by mechanically mixing nano-sized SiO2 and MgO by using a rapid mechanical ball milling method; then, an aqueous solution of nickel nitrate and iron nitrate is impregnated into the composite oxide SiO2.MgO in an equal volume; and finally, the catalyst is obtained through programmed temperature drying, calcination and reduction. The catalyst can solve the problems of high metal active component consumption and short catalyst service life in the existing JP-10 fuel steam reforming catalyst, and has significant industrial application value.

Description

Technical Field

[0001] This invention belongs to the field of catalyst formulation and preparation technology, and relates to a JP-10 fuel steam reforming catalyst and its preparation method. Background Technology

[0002] Hydrogen, as a zero-pollution, renewable, and clean energy source, is widely recognized as one of the most promising new energy sources of the 21st century. Catalytic steam reforming boasts advantages such as low energy consumption, low cost, and a wide range of raw materials, making it the most widely used and industrially valuable hydrogen production technology, accounting for over 50% of global hydrogen supply. Methane and methanol are traditional raw materials for catalytic reforming to produce hydrogen, but they generally suffer from low energy density and low hydrogen production per unit volume. JP-10, a classic polycyclic hydrocarbon fuel, offers higher energy density and greater hydrogen production per unit volume compared to traditional reforming feedstocks, making it highly valuable for portable hydrogen production. Furthermore, the JP-10 steam reforming reaction exhibits strong endothermic properties, which are of significant value in the thermal protection of high-speed aircraft used in national defense. Numerous studies have shown that the core of the JP-10 catalytic reforming hydrogen production reaction lies in developing highly active, highly selective, and long-life catalysts.

[0003] The literature "Hao CZ, Zhou RX, Mei Y, et al. Catalytic steam reforming of JP-10 over Ni / SBA-15[J]. International Journal of Hydrogen Energy, 2020, 45(7): 4284-4296" reports a JP-10 fuel steam reforming catalyst Ni / SBA-15. However, this catalyst suffers from high Ni content (up to 8%) and short lifespan (only about 6.5 h), making it difficult to meet the needs of practical industrial applications. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a JP-10 fuel steam reforming catalyst and its preparation method. This catalyst utilizes the synergistic effect between a nickel-based bimetallic compound and a composite metal oxide with a large surface area and high-temperature hydrothermal stability to improve the catalyst's activity, selectivity, and stability, thereby achieving the goal of reducing the amount of metal active components and extending the catalyst's lifespan.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A JP-10 fuel steam reforming catalyst has the following composition: aNi-bFe / cSiO2·dMgO; wherein Ni and Fe are the active metal components, a+b = 5%, and 3% ≤ a ≤ 4%; SiO2 and MgO are the oxide supports, c+d = 95%, and 70% ≤ c ≤ 80%.

[0007] The preparation method of the JP-10 fuel steam reforming catalyst includes the following steps:

[0008] First, SiO2 and MgO were mechanically mixed using a rapid mechanical ball milling method to obtain a uniformly dispersed composite oxide carrier SiO2·MgO.

[0009] Then, an equal volume of aqueous solutions of nickel nitrate and iron nitrate were impregnated onto the composite oxide support SiO2·MgO, mechanically stirred, and finally dried, calcined, and reduced with H2 to obtain the catalyst aNi-bFe / cSiO2·dMgO.

[0010] The present invention also includes the following technical features:

[0011] Specifically, the rotation speed of the rapid mechanical ball milling method is 80-120 rpm; the mechanical mixing time is 1-2 hours.

[0012] Specifically, the particle size of the SiO2 and MgO is 20–40 nm.

[0013] Specifically, the mechanical stirring time is 1 to 2 hours.

[0014] Specifically, the drying temperature and time are 110℃ for 6 to 10 hours.

[0015] Specifically, the roasting temperature and time are 550℃ for 3 to 5 hours.

[0016] Specifically, the flow rate of H2 is 80 mL / min.

[0017] Specifically, the H2 reduction temperature and time are 600℃ for 1 to 2 hours.

[0018] Compared with the prior art, the present invention has the following technical effects:

[0019] (1) The JP-10 fuel steam reforming catalyst aNi-bFe / cSiO2·dMgO of the present invention has a low content of metal active components, and the total content of Ni and Fe bimetallic active components is only 5%, while the content of single metal Ni active components in the comparative literature is as high as 8%.

[0020] (2) The JP-10 fuel steam reforming catalyst aNi-bFe / cSiO2·dMgO of the present invention has excellent stability and a lifespan of 100-120h, while the lifespan of the comparative literature catalyst Ni / SBA-15 is only 6.5h. Detailed Implementation

[0021] This invention provides a JP-10 fuel steam reforming catalyst and its preparation method. The catalyst composition is aNi-bFe / cSiO2·dMgO, wherein Ni and Fe are metallic active components, conforming to a+b=5%, and 2%≤a≤4%, while SiO2 and MgO are oxide supports, conforming to c+d=95%, and 50%≤c≤90%. The preparation method of the catalyst aNi-bFe / cSiO2·dMgO is as follows: First, commercially available nano-sized SiO2 and MgO are directly mechanically mixed using a rapid mechanical ball milling method to obtain a uniformly dispersed composite oxide support SiO2·MgO. Then, an equal volume of aqueous solutions of nickel nitrate and iron nitrate is impregnated into the obtained composite oxide SiO2·MgO. Finally, the catalyst is obtained by programmed temperature drying, calcination, and reduction.

[0022] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention. Specifically, the catalyst performance evaluation method in the following embodiments is consistent with the prior art document "Hao CZ, Zhou RX, Mei Y, et al. Catalytic steamreforming of JP-10 over Ni / SBA-15[J]. International Journal of Hydrogen Energy, 2020, 45(7): 4284-4296".

[0023] Example 1:

[0024] This embodiment provides a JP-10 fuel steam reforming catalyst and its preparation method. First, a commercially available 20-40 nm SiO2 and MgO are mechanically mixed at 80 rpm for 1 hour using a rapid mechanical ball milling method to obtain a uniformly dispersed composite oxide support, SiO2·MgO. Then, an equal volume of a metered aqueous solution of nickel nitrate and ferric nitrate is impregnated onto the prepared composite oxide SiO2·MgO, and the mixture is mechanically stirred for 1 hour. Finally, the catalyst is dried at 110℃ for 6 hours, calcined at 550℃ for 3 hours, and reduced at 600℃ for 1 hour at an H2 flow rate of 80 mL / min to obtain the catalyst.

[0025] 4%Ni-1%Fe / 50%SiO2·45%MgO.

[0026] According to the catalyst performance evaluation method, the conversion rate of JP-10 was 99.5%, the H2 selectivity was 82.1%, and the catalyst lifetime was 102h.

[0027] Example 2:

[0028] This embodiment provides a JP-10 fuel steam reforming catalyst and its preparation method. First, a rapid mechanical ball milling method is used to mechanically mix commercially available 20-40 nm SiO2 and MgO at 120 rpm for 2 hours to obtain a uniformly dispersed composite oxide support, SiO2·MgO. Then, an equal volume of a metered aqueous solution of nickel nitrate and ferric nitrate is impregnated onto the prepared composite oxide SiO2·MgO, and mechanically stirred for 2 hours. Finally, the catalyst is dried at 110℃ for 10 hours, calcined at 550℃ for 5 hours, and reduced at 600℃ for 2 hours at an H2 flow rate of 80 mL / min to obtain the catalyst.

[0029] 1%Ni-4%Fe / 90%SiO2·5%MgO.

[0030] According to the catalyst performance evaluation method, the conversion rate of JP-10 was 99.8%, the H2 selectivity was 82.9%, and the catalyst lifetime was 112h.

[0031] Example 3:

[0032] This embodiment provides a JP-10 fuel steam reforming catalyst and its preparation method. First, a rapid mechanical ball milling method is used to mechanically mix commercially available 20-40 nm SiO2 and MgO at 100 rpm for 2 hours to obtain a uniformly dispersed composite oxide support, SiO2·MgO. Then, an equal volume of a metered aqueous solution of nickel nitrate and ferric nitrate is impregnated onto the prepared composite oxide SiO2·MgO, and mechanically stirred for 2 hours. Finally, the catalyst is dried at 110℃ for 8 hours, calcined at 550℃ for 4 hours, and reduced at 600℃ for 2 hours at an H2 flow rate of 80 mL / min to obtain the catalyst.

[0033] 2%Ni-3%Fe / 80%SiO2·15%MgO.

[0034] According to the catalyst performance evaluation method, the conversion rate of JP-10 was 100%, the H2 selectivity was 82.6%, and the catalyst lifetime was 120h.

[0035] Example 4:

[0036] This embodiment provides a JP-10 fuel steam reforming catalyst and its preparation method. First, a rapid mechanical ball milling method is used to mechanically mix commercially available 20-40 nm SiO2 and MgO at 90 rpm for 1 hour to obtain a uniformly dispersed composite oxide support, SiO2·MgO. Then, an equal volume of a metered aqueous solution of nickel nitrate and ferric nitrate is impregnated onto the prepared composite oxide SiO2·MgO, and mechanically stirred for 2 hours. Finally, the catalyst is dried at 110℃ for 10 hours, calcined at 550℃ for 5 hours, and reduced at 600℃ for 1 hour at an H2 flow rate of 80 mL / min to obtain the catalyst.

[0037] 3%Ni-2%Fe / 70%SiO2·25%MgO.

[0038] According to the catalyst performance evaluation method, the conversion rate of JP-10 was 100%, the H2 selectivity was 82.6%, and the catalyst lifetime was 120h.

[0039] Example 5:

[0040] This embodiment provides a JP-10 fuel steam reforming catalyst and its preparation method. First, a rapid mechanical ball milling method is used to mechanically mix commercially available 20-40 nm SiO2 and MgO at 100 rpm for 2 hours to obtain a uniformly dispersed composite oxide support, SiO2·MgO. Then, an equal volume of a metered aqueous solution of nickel nitrate and ferric nitrate is impregnated onto the prepared composite oxide SiO2·MgO, and mechanically stirred for 1 hour. Finally, the catalyst is dried at 110℃ for 8 hours, calcined at 550℃ for 4 hours, and reduced at 600℃ for 2 hours at an H2 flow rate of 80 mL / min to obtain the catalyst.

[0041] 4%Ni-1%Fe / 60%SiO2·35%MgO.

[0042] According to the catalyst performance evaluation method, the conversion rate of JP-10 was 100%, the H2 selectivity was 82.1%, and the catalyst lifetime was 112h.

[0043] Example 6:

[0044] This embodiment provides a JP-10 fuel steam reforming catalyst and its preparation method. First, a commercially available 20-40 nm SiO2 and MgO are mechanically mixed at 100 rpm for 2 hours using a rapid mechanical ball milling method to obtain a uniformly dispersed composite oxide support, SiO2·MgO. Then, an equal volume of a measured amount of aqueous solutions of nickel nitrate and ferric nitrate is impregnated onto the prepared composite oxide SiO2·MgO, and the mixture is mechanically stirred for 2 hours. Finally, the mixture is dried at 110℃ for 9 hours, calcined at 550℃ for 3 hours, and reduced at 600℃ for 2 hours at an H2 flow rate of 80 mL / min to obtain the catalyst.

[0045] 4%Ni-1%Fe / 80%SiO2·15%MgO.

[0046] According to the catalyst performance evaluation method, the conversion rate of JP-10 was 100%, the H2 selectivity was 82.5%, and the catalyst lifetime was 109h.

[0047] Comparative example:

[0048] This comparative example is the JP-10 fuel steam reforming catalyst Ni / SBA-15 from the existing technical literature Hao CZ, Zhou RX, Mei Y, et al. Catalytic steam reforming of JP-10 over Ni / SBA-15[J]. International Journal of Hydrogen Energy, 2020, 45(7):4284-4296; the catalyst in this comparative example has a high Ni content of 8% and a lifespan of only about 6.5h.

[0049] The JP-10 fuel steam reforming catalyst aNi-bFe / cSiO2·dMgO of the present invention has a low content of metal active components, with the total content of Ni and Fe bimetallic active components being only 5%, and it has excellent stability and a lifespan of 100-120 hours.

Claims

1. A method for preparing a JP-10 fuel steam reforming catalyst, characterized in that, The JP-10 fuel steam reforming catalyst has the following composition: aNi-bFe / cSiO2·dMgO; wherein Ni and Fe are the active metallic components, a+b=5%, and 3%≤a≤4%; SiO2 and MgO are the oxide supports, c+d=95%, and 70%≤c≤80%. Includes the following steps: First, SiO2 and MgO were mechanically mixed using a rapid mechanical ball milling method to obtain a uniformly dispersed composite oxide carrier SiO2·MgO. Then, an equal volume of aqueous solutions of nickel nitrate and iron nitrate were impregnated onto the composite oxide support SiO2·MgO, mechanically stirred, and finally dried, calcined, and reduced with H2 to obtain the catalyst aNi-bFe / cSiO2·dMgO. The rapid mechanical ball milling method has a rotation speed of 80~120 rpm and a mechanical mixing time of 1~2 hours. The particle size of SiO2 and MgO is 20~40nm; The mechanical stirring time is 1-2 hours; The drying temperature and time are 110℃ for 6~10h; The roasting temperature and time are 550℃ for 3~5 hours; The flow rate of H2 is 80 mL / min; The H2 reduction temperature and time are 600℃ for 1~2 hours.