Carbon-based fuel reforming catalytic hydrogen production catalyst, preparation method thereof and reforming catalytic hydrogen production method

Abstract

The invention provides a carbon-based fuel reforming catalytic hydrogen production catalyst and a preparation method thereof, and the preparation method comprises the following steps: A) carrying out extrusion molding on a ceramic material containing a catalytic active component to obtain a ceramic green body with an airflow channel inside; b) sintering the ceramic green body at high temperature to obtain a catalyst main body; then naturally cooling to room temperature; and C) covering the outer surface of the catalyst main body with a barrier film to obtain the carbon-based fuel reforming catalytic hydrogen production catalyst. According to the invention, the ceramic material containing the catalyst active component is prepared into the support body structure, no extra catalyst is needed, the working temperature of the support body structure can reach 750-1000 DEG C, the phenomenon of catalyst deactivation caused by structural collapse does not exist, and the conversion rate of the catalyst is high. The invention also provides a method for hydrogen production through reforming catalysis.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalytic reforming for hydrogen production, and particularly relates to a catalyst for catalytic hydrogen production by reforming carbon-based fuels, a preparation method thereof, and a method for reforming catalytic hydrogen production. Background Art

[0002] In today's world, there is huge pressure on carbon emission reduction, prominent environmental pollution problems, and the handling of energy problems is imminent. As a result, the global trend of green and low-carbon transformation of energy has emerged. Hydrogen, as an absolutely clean and renewable energy, stands out in the competition. Firstly, its transportable characteristics can realize the redistribution of unevenly distributed renewable energy. Secondly, the application fields of hydrogen energy are very broad and can be applied in industrial, transportation, construction, and power industries. In the industrial field, it can be used in steelmaking, ammonia synthesis, coal-to-methanol / ethylene glycol, and as industrial fuel. In the construction aspect, it can be used in natural gas pipeline hydrogen blending, household combined heat and power, and district combined heat and power. In the power aspect, it can be used as distributed power sources, centralized power stations, and coal blending with ammonia. In the transportation aspect, it can be used for commercial vehicles, passenger vehicles, trams, ships, drones / aircraft. It can be said that it plays a great role in all walks of life.

[0003] In all current industrial methods for producing hydrogen, hydrogen is mainly produced from raw materials such as natural gas, naphtha, heavy oil, coal, coke, and coke oven gas. Among them, in industrial hydrogen production from natural gas, synthesis gas containing components such as hydrogen and carbon monoxide is usually obtained by reacting with steam at high temperature. However, the temperature of natural gas hydrogen production is usually 750 - 920°C, and the existing catalyst structure is prone to fragmentation under high temperature and high pressure, thus losing its catalytic activity. Summary of the Invention

[0004] The purpose of the present invention is to provide a catalyst for catalytic hydrogen production by reforming carbon-based fuels, a preparation method thereof, and a method for reforming catalytic hydrogen production. The catalyst for catalytic hydrogen production by reforming carbon-based fuels in the present invention solves the technical problem of deactivation due to structural collapse.

[0005] The present invention provides a preparation method for a catalyst for catalytic hydrogen production by reforming carbon-based fuels, comprising the following steps:

[0006] A) Extruding and molding a ceramic material containing a catalytic active component to obtain a ceramic green body with an air flow channel inside;

[0007] B) Subjecting the ceramic green body to high-temperature sintering to obtain a catalyst main body;

[0008] The procedure of the high-temperature sintering is as follows:

[0009] Heat from room temperature to 110 - 130°C within 45 - 55 minutes, then heat to 240 - 260°C within 375 - 385 minutes and hold for 35 - 45 minutes, heat to 290 - 310°C within 355 - 365 minutes and hold for 55 - 65 minutes, heat to 340 - 360°C within 355 - 365 minutes and hold for 55 - 65 minutes, heat to 390 - 410°C within 295 - 305 minutes and hold for 55 - 65 minutes, heat to 1180°C within 635 - 645 minutes and hold for 175 - 185 minutes, heat to 1200 - 1300°C within 355 - 365 minutes and hold for 300 - 480 minutes, and then cool naturally to room temperature;

[0010] C) Coat a barrier film on the outer surface of the catalyst body to obtain a carbon-based fuel reforming hydrogen production catalyst.

[0011] Preferably, the ceramic material containing catalytically active components is one or more of Ni-YSZ, Cu-YSZ, Cu-GDC, and Ni-GDC.

[0012] Preferably, in the ceramic material containing catalytically active components, the mass fraction of the catalytically active components is 20 - 30%.

[0013] Preferably, the high-temperature sintering procedure is as follows:

[0014] Heat from room temperature to 115 - 125°C within 50 minutes, then heat to 245 - 255°C within 380 minutes and hold for 40 minutes, heat to 295 - 305°C within 360 minutes and hold for 60 minutes, heat to 345 - 355°C within 360 minutes and hold for 60 minutes, heat to 395 - 405°C within 300 minutes and hold for 60 minutes, heat to 1180°C within 640 minutes and hold for 180 minutes, heat to 1200 - 1300°C within 360 minutes and hold for 360 minutes, and then cool naturally to room temperature.

[0015] Preferably, the high-temperature sintering procedure is as follows:

[0016] Heat from room temperature to 120°C within 50 minutes, then heat to 250°C within 380 minutes and hold for 40 minutes, heat to 300°C within 360 minutes and hold for 60 minutes, heat to 350°C within 360 minutes and hold for 60 minutes, heat to 400°C within 300 minutes and hold for 60 minutes, heat to 1180°C within 640 minutes and hold for 180 minutes, heat to 1200 - 1300°C within 360 minutes and hold for 360 minutes, and then cool naturally to room temperature.

[0017] Preferably, the barrier film is made of YSZ.

[0018] The present invention provides a carbon-based fuel reforming catalytic hydrogen production catalyst prepared by the preparation method as described above, including a catalyst main body and a barrier film coated on the outer surface of the catalyst main body;

[0019] An air flow channel is arranged in the catalyst main body.

[0020] Preferably, the carbon-based fuel reforming catalytic hydrogen production catalyst has a porous structure, with a porosity of 18-22% and a pore diameter of 5-15 μm.

[0021] The present invention provides a method for reforming catalytic hydrogen production. Carbon-based fuel and water vapor are introduced into the air flow channel of the carbon-based fuel reforming catalytic hydrogen production catalyst as described above, and reforming catalytic hydrogen production is carried out to obtain hydrogen.

[0022] Preferably, the carbon-based fuel is natural gas, and the temperature of the reforming catalytic hydrogen production is 700-800 °C.

[0023] The present invention provides a preparation method of a carbon-based fuel reforming catalytic hydrogen production catalyst, including the following steps: A) Extruding and molding a ceramic material containing a catalytic active component to obtain a ceramic green body with an air flow channel inside; B) Performing high-temperature sintering on the ceramic green body to obtain a catalyst main body; the program of the high-temperature sintering is as follows: heating from room temperature to 110-130 °C within 45-55 min, then heating to 240-260 °C within 375-385 min and holding for 35-45 min, heating to 290-310 °C within 355-365 min and holding for 55-65 min, heating to 340-360 °C within 355-365 min and holding for 55-65 min, heating to 390-410 °C within 295-305 min and holding for 55-65 min, heating to 1180 °C within 635-645 min and holding for 175-185 min, heating to 1200-1300 °C within 355-365 min and holding for 300-480 min, and then naturally cooling to room temperature; C) Coating a barrier film on the outer surface of the catalyst main body to obtain a carbon-based fuel reforming catalytic hydrogen production catalyst. The present invention prepares a ceramic material containing a catalyst active component into a support structure, without the need to additionally add a catalyst, and its own working temperature can reach 750-1000 °C, and there is no catalyst deactivation phenomenon due to structural collapse. Moreover, the catalyst in the present invention has a high conversion rate. Description of the Drawings

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on the provided drawings.

[0025] Figure 1 It is a schematic structural diagram of the carbon-based fuel reforming catalytic hydrogen production catalyst in the embodiment of the present invention;

[0026] Figure 2 It is a schematic structural diagram of a side piece of the carbon-based fuel reforming catalytic hydrogen production catalyst in the embodiment of the present invention;

[0027] Figure 3 It is a process flow chart for the preparation of the carbon-based fuel reforming catalytic hydrogen production catalyst of the present invention;

[0028] Figure 4 It is the content of the tail gas components at the beginning of the operation of the natural gas hydrogen production catalytic converter in Embodiment 1 of the present invention;

[0029] Figure 5 It is the content of the tail gas components after the natural gas hydrogen production catalytic converter in Embodiment 1 of the present invention has run for 214 hours;

[0030] Figure 6 It is the content of the tail gas components when 0.5 L / min of CH4 is introduced into the three-piece catalytic reactor SMR at 800 °C after the natural gas hydrogen production catalytic converter in Embodiment 1 of the present invention has run for 264 hours;

[0031] Figure 7 It is the CH4 conversion rate, CO selectivity and H2 yield curves when 0.5 L / min of CH4 is introduced into the three-piece catalytic reactor SMR at 800 °C after the natural gas hydrogen production catalytic converter in Embodiment 1 of the present invention has run for 264 hours;

[0032] Figure 8 It is the content of the tail gas components when 0.5 L / min of CH4 is introduced into the three-piece catalytic reactor SMR at 750 °C under the carbon deposition condition after the natural gas hydrogen production catalytic converter in Embodiment 1 of the present invention has run for 336 hours;

[0033] Figure 9 It is the CH4 conversion rate, CO selectivity and H2 yield curves when 0.5 L / min of CH4 is introduced into the three-piece catalytic reactor SMR at 750 °C under the carbon deposition condition after the natural gas hydrogen production catalytic converter in Embodiment 1 of the present invention has run for 336 hours;

[0034] Figure 10 It is the change of CH4 conversion rate and content in Embodiments 1-9 of the present invention;

[0035] Figure 11 The strength of the hydrogen production catalyst from natural gas prepared in Example 1 of the present invention;

[0036] Figure 12 Comparison chart of methane conversion rate, hydrogen yield, and carbon monoxide selectivity of the hydrogen production catalyst from natural gas in Example 1 at 800 °C under different inlet gas contents;

[0037] Figure 13 Performance comparison chart of the hydrogen production catalyst from natural gas in Example 1 of the present invention at 750 °C under different water-carbon ratios;

[0038] Figure 14 Performance comparison chart of the hydrogen production catalyst from natural gas in Example 1 of the present invention at 800 °C under different water-carbon ratios. Detailed implementation method

[0039] The present invention provides a preparation method of a carbon-based fuel reforming catalytic hydrogen production catalyst, including the following steps:

[0040] A) Extruding and molding a ceramic material containing catalytically active components to obtain a ceramic blank with an air flow channel inside;

[0041] B) High-temperature sintering the ceramic blank to obtain a catalyst main body;

[0042] The procedure of the high-temperature sintering is as follows:

[0043] Heating from room temperature to 110 - 130 °C within 45 - 55 min, then heating to 240 - 260 °C within 375 - 385 min and holding for 35 - 45 min, heating to 290 - 310 °C within 355 - 365 min and holding for 55 - 65 min, heating to 340 - 360 °C within 355 - 365 min and holding for 55 - 65 min, heating to 390 - 410 °C within 295 - 305 min and holding for 55 - 65 min, heating to 1180 °C within 635 - 645 min and holding for 175 - 185 min, heating to 1200 - 1300 °C within 355 - 365 min and holding for 300 - 480 min, and then naturally cooling to room temperature;

[0044] C) Coating a barrier film on the outer surface of the catalyst main body to obtain a carbon-based fuel reforming catalytic hydrogen production catalyst.

[0045] In the present invention, the catalytically active component in the ceramic material containing the catalytically active component is a component capable of playing a catalytic role in the catalytic hydrogen production reaction by natural gas reforming in the art, such as Ni, Cu, etc. Preferably, the ceramic material containing the catalytically active component is preferably one or more of Ni-YSZ (Ni-doped yttrium-stabilized zirconia material), Cu-YSZ (Cu-coated YSZ particle material), Cu-GDC, and Ni-GDC. In the ceramic material containing the catalytically active component, the mass fraction of the catalytically active component is 20-30%, preferably 25-28%.

[0046] In the present invention, the extrusion molding is a conventional molding method in the art, and the present invention will not elaborate here.

[0047] After obtaining the ceramic green body, the present invention performs high-temperature sintering on the ceramic green body according to the following heating program to obtain the catalyst main body.

[0048] In the present invention, the program of the high-temperature sintering is as follows:

[0049] Heat from room temperature to 110-130 °C within 45-55 min, then heat to 240-260 °C within 375-385 min and hold for 35-45 min, heat to 290-310 °C within 355-365 min and hold for 55-65 min, heat to 340-360 °C within 355-365 min and hold for 55-65 min, heat to 390-410 °C within 295-305 min and hold for 55-65 min, heat to 1180 °C within 635-645 min and hold for 175-185 min, heat to 1200-1300 °C within 355-365 min and hold for 300-480 min, and then cool naturally to room temperature.

[0050] Through the high-temperature sintering of the above program, an appropriate porosity can be formed in the ceramic green body, so that after the raw material gas and water vapor are introduced into the catalyst through the gas flow channel, they diffuse and fill the entire catalyst through the pore structure in the catalyst, and redox reactions occur inside the catalyst. According to the Arrhenius formula, the activation energy of the reaction is reduced during the operation process, the reaction pathway is changed, and the reaction rate is increased; at the same time, it is also necessary to ensure that the catalyst has sufficient support strength after high-temperature sintering.

[0051] Preferably, the program of the high-temperature sintering is as follows:

[0052] Heat from room temperature to 115 - 125°C within 50 min, then heat to 245 - 255°C within 380 min and hold for 40 min, heat to 295 - 305°C within 360 min and hold for 60 min, heat to 345 - 355°C within 360 min and hold for 60 min, heat to 395 - 405°C within 300 min and hold for 60 min, heat to 1180°C within 640 min and hold for 180 min, heat to 1200 - 1300°C within 360 min and hold for 360 min, then cool naturally to room temperature.

[0053] More preferably, the procedure for high-temperature sintering is as follows:

[0054] Heat from room temperature to 120°C within 50 min, then heat to 250°C within 380 min and hold for 40 min, heat to 300°C within 360 min and hold for 60 min, heat to 350°C within 360 min and hold for 60 min, heat to 400°C within 300 min and hold for 60 min, heat to 1180°C within 640 min and hold for 180 min, heat to 1200 - 1300°C within 360 min and hold for 360 min, then cool naturally to room temperature.

[0055] After obtaining the catalyst body, a barrier film is composited on the outer surface of the catalyst body in the present invention to prevent the raw gas or water vapor diffusing into the catalyst from the gas flow channel from escaping from the inside of the catalyst. In the present invention, the barrier film is preferably YSZ (yttria-stabilized zirconia); the thickness of the barrier film is preferably < 10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, and is preferably a range value with any of the above values as the upper or lower limit.

[0056] The present invention also provides a carbon-based fuel reforming hydrogen production catalyst, which includes a catalyst body and a barrier film coated on the outer surface of the catalyst body; an air flow channel is provided inside the catalyst body. The carbon-based fuel reforming hydrogen production catalyst is prepared according to the preparation method described above.

[0057] The present invention has no special restrictions on the number and size of the air flow channels, which can be set according to actual needs.

[0058] In the present invention, the porosity of the carbon-based fuel reforming hydrogen production catalyst is preferably 18 - 22%, more preferably 19 - 21%, and most preferably 20%; the pore diameter is preferably 5 - 15 μm, more preferably 8 - 12 μm, and most preferably 10 - 11 μm.

[0059] In the present invention, the strength of the carbon-based fuel reforming hydrogen production catalyst is 119.59 MPa.

[0060] The present invention also provides a method for reforming catalytic hydrogen production. Carbon-based fuel and water vapor are introduced into the gas flow channel of the carbon-based fuel reforming catalytic hydrogen production catalyst described above, and reforming catalytic hydrogen production is carried out to obtain hydrogen.

[0061] In the present invention, the carbon-based fuel is preferably natural gas or methane, and the molar ratio of the carbon-based fuel to water vapor is preferably 1:(2 - 4), more preferably 1:3; the temperature of the reforming catalytic hydrogen production is preferably 700 - 800 °C.

[0062] The present invention provides a preparation method of a carbon-based fuel reforming catalytic hydrogen production catalyst, including the following steps: A) Extruding and molding a ceramic material containing catalytically active components to obtain a ceramic green body with a gas flow channel inside; B) Subjecting the ceramic green body to high-temperature sintering to obtain a catalyst main body; the procedure of the high-temperature sintering is as follows: heating from room temperature to 110 - 130 °C within 45 - 55 min, then heating to 240 - 260 °C within 375 - 385 min and holding for 35 - 45 min, heating to 290 - 310 °C within 355 - 365 min and holding for 55 - 65 min, heating to 340 - 360 °C within 355 - 365 min and holding for 55 - 65 min, heating to 390 - 410 °C within 295 - 305 min and holding for 55 - 65 min, heating to 1180 °C within 635 - 645 min and holding for 175 - 185 min, heating to 1200 - 1300 °C within 355 - 365 min and holding for 300 - 480 min, and then naturally cooling to room temperature; C) Coating a barrier film on the outer surface of the catalyst main body to obtain a carbon-based fuel reforming catalytic hydrogen production catalyst. The present invention prepares a ceramic material containing catalytically active components into a support structure, without the need to additionally add a catalyst, and its own working temperature can reach 750 - 1000 °C, and there is no catalyst deactivation phenomenon due to structural collapse. Moreover, the catalyst in the present invention has a high conversion rate.

[0063] In order to further illustrate the present invention, the following describes in detail a carbon-based fuel reforming catalytic hydrogen production catalyst provided by the present invention, its preparation method and the method for reforming catalytic hydrogen production in combination with examples, but it should not be construed as a limitation to the protection scope of the present invention.

[0064] Example 1

[0065] Ni and YSZ materials are extruded and molded to obtain a Ni-YSZ green body containing 50% Ni.

[0066] The Ni-YSZ green body is subjected to high-temperature sintering according to the following heating procedure to obtain a catalyst main body.

[0067] Heat from room temperature to 120 °C within 50 min, then heat to 250 °C within 380 min and hold for 40 min, heat to 300 °C within 360 min and hold for 60 min, heat to 350 °C within 360 min and hold for 60 min, heat to 400 °C within 300 min and hold for 60 min, heat to 1180 °C within 640 min and hold for 180 min, heat to 1250 °C within 360 min and hold for 360 min, and then naturally cool to room temperature.

[0068] Composite YSZ barrier films on the upper and lower surfaces of the catalyst body to obtain a reforming hydrogen production catalyst. The structure is as Figure 1 and 2 shown, with a porosity of 20%.

[0069] Adopt Figure 2 in the natural gas hydrogen production catalyst and assemble it with the air electrode and fuel electrode into a natural gas hydrogen production catalytic converter. Pass natural gas into a water bath so that natural gas serves as a carrier gas to bring water vapor into the natural gas hydrogen production catalytic converter. Carry out the process at 800 °C. No gas is passed into the air electrode, and 0.2 L / min of CH4 is passed into the fuel electrode. Carry out the process when the water-gas ratio is 75%. In the catalytic converter, natural gas and water vapor will decompose into carbon monoxide and hydrogen, and carbon monoxide will further react with water vapor to produce carbon dioxide and hydrogen.

[0070] The results are as Figures 4 - 5 shown, Figure 4 is a comparison chart of the tail gas content when the natural gas hydrogen production catalytic converter just starts to operate, Figure 5 is a comparison chart of the tail gas content when the natural gas hydrogen production catalytic converter operates for 214 hours and undergoes one heat cycle, Figure 4 and Figure 5 list the tail gas contents of a single-piece catalytic converter (using one of the above natural gas hydrogen production catalysts) and a three-piece catalytic stack (using three of the above natural gas hydrogen production catalysts) respectively. It can be seen from Figures 4 - 5 that after the catalyst operates for 214 hours, at 800 °C and with a methane input of 0.4 L / min, the methane conversion rate can reach the highest point of 98.507%. The methane conversion rate decays by 0.004% / h, indicating that the catalytic performance at 800 °C is good and stable, and it can also prove that the catalytic converter in the present invention is not easily deactivated and is stable.

[0071] See Figures 6 - 7 , Figure 6 and Figure 7 are comparison charts of passing 0.5 L / min of CH4 into the three-piece catalytic stack SMR at 800 °C after operating for 264 hours. It can be seen from Figure 6 and Figure 7It can be seen that at the same water-carbon ratio after running for 214 hours, the methane conversion rate does not decrease but rather increases slightly, and the hydrogen yield decreases by about 0.5%. This directly proves that the natural gas catalytic hydrogen generator in the present invention has good stability and self-repair ability.

[0072] See Figures 8 - 9 , Figure 8 and Figure 9 are the comparison diagrams of the three catalytic reactors SMR when 0.5 L / min CH4 is introduced at 750 °C under the conditions of three thermal cycles and carbon deposition after running for 336 hours. From Figure 8 and 9 it can be seen that after three thermal cycles and running for 336 hours, when the catalytic reformer is placed under harsh conditions - carbon deposition conditions, in the GC tail gas analysis, the content of hydrogen always remains stable. When the water-carbon ratio is 3:1, the hydrogen content in the tail gas can still reach 70%, indicating that the catalytic converter in the present invention has high catalytic activity stability during operation.

[0073] Examples 2 - 9

[0074] Catalytic hydrogen production was carried out according to the method in Example 1, except that the catalytic reforming temperatures in Examples 2 - 9 were 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 650 °C, 700 °C, and 750 °C respectively.

[0075] The sum of the methane conversion rates and their content changes in Examples 1 - 9 are as Figure 10 shown. From Figure 10 it can be seen that a relatively high CH4 conversion rate is achieved between 700 - 800 °C.

[0076] The strength of the natural gas hydrogen production catalyst prepared in Test Example 1 was tested, and the results are as Figure 11 shown. Figure 11 is the strength of the natural gas hydrogen production catalyst prepared in Example 1 of the present invention. From Figure 11 it can be seen that the flexural strength is 119.59 Mpa.

[0077] Figure 12 is the comparison diagram of the methane conversion rate, hydrogen production rate, and carbon monoxide selectivity of the natural gas hydrogen production catalyst in Example 1 at 800 °C under different inlet gas contents. From Figure 12It can be seen that (a)-(e) are bar charts showing the changes in the corresponding conversion rates, carbon monoxide selectivities, and hydrogen yields of the structural support at different temperatures and different methane input amounts, where the steam-carbon ratio is fixed at 3:1 and the methane flow rates are 0.2 - 1.4 SLM. The results show that in the low-temperature regions of 600°C and 650°C, at the same temperature, the selectivity of CO decreases as the natural gas input amount increases. In the high-temperature region of 700 - 800°C, the selectivity of CO is relatively stable. At 800°C, when 1.4 SLM of CH4 is introduced, the corresponding carbon monoxide selectivity reaches the optimal value of 84.44%. It can also be seen from the figure that the hydrogen yield decreases as the natural gas input amount increases at the same temperature, and when 0.3 SLM of CH4 is introduced at 800°C, the hydrogen yield reaches the maximum of 77.46%.

[0078] Figure 13 This is a performance comparison chart of the natural gas hydrogen production catalyst in Example 1 of the present invention at 750°C under different steam-carbon ratios. From Figure 13 it can be seen that when the steam-carbon ratio is 3, the conversion rate of methane reaches 96.76%, the content of the fuel-rich atmosphere reaches 85%, the selectivity of hydrogen reaches 75.18%, and the hydrogen production amount reaches 1.45 SLM. The results in the figure also show that when the CH4 inlet flow rate is 0.5 SLM, the selectivity of H2 and the conversion rate of methane increase as the steam-carbon ratio increases, and the contents of the fuel-rich atmosphere H2 and CO are always greater than 81%. Therefore, it can be found that when the steam-carbon ratio increases from 1 to 3, for every increase of 0.5, the methane conversion rate increases by 5.98% and the hydrogen production rate increases by 7.6%. However, from Figure 4 it can be seen that when the steam-carbon ratio increases and the hydrogen production rate increases, the corresponding stack voltage decays, that is, when the steam-carbon ratio is decreased, the stack voltage will increase significantly. Generally speaking, when the steam-carbon ratio is not less than 2 and not more than 3 at 750°C, the comprehensive performance is the best.

[0079] Figure 14 This is a performance comparison chart of the natural gas hydrogen production catalyst in Example 1 of the present invention at 800°C under different steam-carbon ratios. From Figure 14 it can be seen that when the steam-carbon ratio > 2, the conversion rate of methane is stable > 98%, the content of the fuel-rich atmosphere reaches 85%, and the selectivity of hydrogen > 75.18%. When the steam-carbon ratio increases and the hydrogen production rate increases, the corresponding stack voltage decays, that is, when the steam-carbon ratio is decreased, the stack voltage will increase significantly. Generally speaking, when the steam-carbon ratio is not less than 2 and not more than 3 at 800°C, the comprehensive performance is the best.

[0080] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a catalyst for carbon-based fuel reforming to produce hydrogen, comprising the following steps: A) Extruding and molding a ceramic material containing catalytically active components to obtain a ceramic blank with an air flow channel inside; B) Subjecting the ceramic blank to high-temperature sintering to obtain a catalyst main body; The procedure of the high-temperature sintering is as follows: Raise the temperature from room temperature to 110 - 130°C within 45 - 55 min, then raise the temperature to 240 - 260°C within 375 - 385 min and hold for 35 - 45 min, raise the temperature to 290 - 310°C within 355 - 365 min and hold for 55 - 65 min, raise the temperature to 340 - 360°C within 355 - 365 min and hold for 55 - 65 min, raise the temperature to 390 - 410°C within 295 - 305 min and hold for 55 - 65 min, raise the temperature to 1180°C within 635 - 645 min and hold for 175 - 185 min, raise the temperature to 1200 - 1300°C within 355 - 365 min and hold for 300 - 480 min, and then naturally cool to room temperature; C) Coating a barrier film on the outer surface of the catalyst main body to obtain a catalyst for carbon-based fuel reforming to produce hydrogen.

2. The preparation method according to claim 1, wherein The ceramic material containing catalytically active components is one or more of Ni-YSZ, Cu-YSZ, Cu-GDC, and Ni-GDC.

3. The preparation method according to claim 2, characterized in that, In the ceramic material containing catalytically active components, the mass fraction of the catalytically active components is 20 - 30%.

4. The preparation method according to claim 1, characterized in that, The procedure of the high-temperature sintering is as follows: Raise the temperature from room temperature to 115 - 125°C within 50 min, then raise the temperature to 245 - 255°C within 380 min and hold for 40 min, raise the temperature to 295 - 305°C within 360 min and hold for 60 min, raise the temperature to 345 - 355°C within 360 min and hold for 60 min, raise the temperature to 395 - 405°C within 300 min and hold for 60 min, raise the temperature to 1180°C within 640 min and hold for 180 min, raise the temperature to 1200 - 1300°C within 360 min and hold for 360 min, and then naturally cool to room temperature.

5. The preparation method according to claim 4, characterized in that, The procedure of the high-temperature sintering is as follows: Raise the temperature from room temperature to 120°C within 50 min, then raise the temperature to 250°C within 380 min and hold for 40 min, raise the temperature to 300°C within 360 min and hold for 60 min, raise the temperature to 350°C within 360 min and hold for 60 min, raise the temperature to 400°C within 300 min and hold for 60 min, raise the temperature to 1180°C within 640 min and hold for 180 min, raise the temperature to 1200 - 1300°C within 360 min and hold for 360 min, and then naturally cool to room temperature.

6. The preparation method according to claim 1, characterized in that, The barrier film component is YSZ.

7. A catalyst for carbon-based fuel reforming to produce hydrogen prepared by the preparation method according to any one of claims 1 - 6, comprising a catalyst main body and a barrier film coated on the outer surface of the catalyst main body; An air flow channel is provided inside the catalyst main body.

8. The hydrogen production catalyst for carbon-based fuel reforming according to claim 6, characterized in that, The catalyst for carbon-based fuel reforming to produce hydrogen has a porous structure, with a porosity of 18 - 22% and a pore diameter of 5 - 15 μm.

9. A method for reforming catalysis to produce hydrogen, characterized in that, Carbon-based fuel and steam are introduced into the gas flow channel of the carbon-based fuel reforming hydrogen production catalyst according to claim 7 or 8, and reforming catalytic hydrogen production is carried out to obtain hydrogen.

10. The method according to claim 9, wherein The carbon-based fuel is natural gas, and the temperature of the reforming catalytic hydrogen production is 700-800 °C.

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