Multi-channel device and method for hydrogen production from methanol based on one-end sealed catalytic oxygen-permeable membrane

Abstract

The application belongs to the field of hydrogen production from methanol, and in particular to a multi-channel device and method for hydrogen production from methanol based on a one-end sealed catalytic oxygen permeable membrane. The device comprises a reactor shell, a gas guide pipe and a tubular catalytic oxygen permeable membrane. The outer side of the tubular catalytic oxygen permeable membrane is provided with a water decomposition catalyst, and the inner side of the tubular catalytic oxygen permeable membrane is provided with a methanol oxidation catalyst. Water vapor is decomposed into hydrogen, oxygen ions and electrons in the reactor shell under the action of the water decomposition catalyst. The hydrogen is heat-exchanged to obtain high-purity hydrogen. The oxygen ions are transmitted to the inner side of the membrane through the tubular catalytic oxygen permeable membrane and are oxidized to generate CO2 and water in the cavity between the gas guide pipe and the tubular catalytic oxygen permeable membrane under the action of the methanol oxidation catalyst. The application couples and integrates the water decomposition reaction and the hydrogen production reaction from methanol, and utilizes the 100% selectivity of the tubular catalytic oxygen permeable membrane to oxygen to directly produce hydrogen without carbon monoxide (CO) on the side of the water decomposition reaction.

Description

Technical Field

[0001] This invention belongs to the field of methanol-to-hydrogen, specifically a multi-channel device and method for methanol-to-hydrogen based on a catalytic oxygen-permeable membrane with one end sealed. Background Technology

[0002] Methanol is an excellent liquid hydrogen storage and transport carrier. It can be used to produce hydrogen through methanol reforming using Cu, Zn, and Ni-based catalysts, such as methanol steam reforming (CH3OH+H2O→CO2+3H2) and methanol autothermal reforming (2CH3OH+0.5O2+H2O→2CO2+5H2). It can provide hydrogen online to low-temperature fuel cell vehicles, thereby effectively solving the problem of hydrogen storage and transportation and improving safety.

[0003] However, the fuel hydrogen produced during methanol-to-hydrogen production contains impurities such as CO2 and CO. In particular, trace amounts of CO can rapidly poison fuel cell catalysts. Therefore, a series of impurity removal processes are required after the methanol reforming reaction, which limits the promotion and application of methanol in the fuel cell field. Currently, although in-situ separation and purification of hydrogen can be achieved using Pd membrane reactors, the high cost of Pd, as a precious metal, limits the large-scale application of this technology. Therefore, there is an urgent need to develop new, efficient hydrogen production processes and materials to support the high-quality development of the national hydrogen energy and fuel cell industry.

[0004] In existing technologies, methanol reforming for hydrogen production based on a hybrid conductor oxygen-permeable membrane reactor couples and integrates water splitting and methanol-to-hydrogen reactions. During the reaction, water is decomposed into oxygen and hydrogen on one side of the membrane. Oxygen is transported in ionic form through the oxygen-permeable membrane to the other side and undergoes an oxidation reaction with the methanol reforming products (or directly with methanol) to produce CO. x And H2O. However, utilizing an oxygen ion-electron hybrid conductor allows for 100% selectivity for oxygen, enabling the one-step production of CO-free hydrogen from the water splitting reaction. The key to effectively achieving methanol-to-hydrogen production lies in the construction of a high-efficiency membrane reactor.

[0005] Currently, sheet-like membrane materials are widely studied due to their relatively simple preparation and testing methods. However, sheet-like membranes face sealing challenges during assembly, mainly due to the mismatch between thermal expansion and chemical compatibility between the sealant and the membrane material. In contrast, tubular membranes can effectively solve these technical problems through cold-end sealing. Liang et al. used Au slurry to seal BaCo... x Fe y Zr 1-x-y O 3-δOne end of the hollow fiber membrane was sealed, and pure oxygen was successfully produced (see Ind. Eng. Chem. Res. 2010, 49, 937). Alternatively, a ferrule seal can be used, or rubber rings can be used to seal the two open ends of the ceramic oxygen-permeable membrane away from high-temperature areas (e.g., Chinese Patent CN102284252B, Chinese Patent CN101912742A, Chinese Patent CN102979981A, etc.). While this sealing method avoids the sealing problems of ceramic oxygen-permeable membranes at high temperatures, its structure is more complex, and the membrane will still experience stress due to thermal expansion under high-temperature conditions, which can easily lead to membrane rupture and significantly reduce the membrane's efficiency. Summary of the Invention

[0006] The purpose of this invention is to provide a multi-channel methanol-to-hydrogen device and method based on a one-end sealed catalytic oxygen-permeable membrane.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A multi-channel methanol-to-hydrogen device based on a one-end sealed catalytic oxygen-permeable membrane includes a reactor shell 3, a gas delivery pipe 1, and a tubular catalytic oxygen-permeable membrane 2. The reactor shell 3 has an upper sealing assembly connected to its upper end and a lower sealing assembly connected to its lower end. The upper sealing assembly contains, from top to bottom, a first sealing chamber 22, a second sealing chamber 23, and a third sealing chamber 24. The lower sealing assembly contains a fourth sealing chamber 25. The first sealing chamber 22 communicates with the membrane's inner inlet 10, and the second sealing chamber 23 communicates with the membrane's inner outlet 11. The third sealing chamber 24, the reactor shell 3, and the fourth sealing chamber 25 are sequentially connected. Furthermore, the third sealed chamber 24 is connected to the membrane outer outlet 13, and the fourth sealed chamber 25 is connected to the membrane outer inlet 12. The tubular catalytic oxygen permeable membrane 2 is open at the upper end and sealed at the lower end. The upper opening of the tubular catalytic oxygen permeable membrane 2 is located in the second sealed chamber 23, and the lower end is located in the reactor shell 3. The gas guide pipe 1 is located in the tubular catalytic oxygen permeable membrane 2, and the upper end of the gas guide pipe 1 extends out from the upper opening of the tubular catalytic oxygen permeable membrane 2 and is placed in the first sealed chamber 22. A water splitting catalyst 4 is provided on the outside of the tubular catalytic oxygen permeable membrane 2, and a methanol oxidation catalyst 5 is provided on the inside of the tubular catalytic oxygen permeable membrane 2.

[0009] The opening of the lower section of the gas delivery tube 1 is located no more than 1 cm from the lower end of the tubular catalytic oxygen permeable membrane 2.

[0010] The tubular catalytic oxygen permeable membrane 2 has an outer diameter of 2-20 mm, a wall thickness of 0.1-2 mm, and a length of 10-100 cm.

[0011] The lengths of water splitting catalyst 4 and methanol oxidation catalyst 5 are 10-400 mm; the outer diameters of the thicknesses of water splitting catalyst 4 and methanol oxidation catalyst 5 are 5-200 micrometers.

[0012] Water splitting catalyst 4 and methanol oxidation catalyst 5 are placed in a high-temperature zone of 300℃-1000℃.

[0013] The upper sealing assembly includes an upper sealing cover 21, an upper sealing intermediate body 19, and an upper sealing seat 17 arranged sequentially from top to bottom. The upper sealing cover 21 and the upper sealing intermediate body 19 form the first sealing chamber 22. The upper sealing seat 17 is provided with a partition 1701 in the middle. The upper sealing intermediate body 19 and the partition 1701 form the second sealing chamber 23. The partition 1701 and the upper end of the reactor shell 3 form the third sealing chamber 24. The upper end of the tubular catalytic oxygen permeable membrane 2 is fixed to the partition 1701, and the upper end of the gas guide pipe 1 is fixed to the upper sealing intermediate body 19.

[0014] The upper sealing cover 21 is provided with an upper sealing cover flange on the outer side of its lower end, the upper sealing intermediate body 19 is provided with an intermediate body flange on the outer side of its upper end, and the upper sealing seat 17 is provided with a sealing seat upper flange on the outer side of its upper end. The upper sealing cover flange, the intermediate body flange, and the sealing seat upper flange are fixed together by bolts, and a first sealing ring 9 is provided between the upper sealing cover flange and the intermediate body flange, and between the intermediate body flange and the sealing seat upper flange.

[0015] The lower end of the upper sealing seat 17 forms an upper sealing mounting recess for accommodating the upper end of the reactor shell 3, and an upper recess flange is provided on the outer side of the lower end of the upper sealing mounting recess. An upper pressing cover 16 and an upper pressing ring are fitted on the outer side of the upper end of the reactor shell 3. Each upper pressing ring is stacked sequentially in the gap between the inner wall of the upper sealing mounting recess and the reactor shell 3, and the uppermost upper pressing ring abuts against the bottom surface of the upper sealing mounting recess. The lowermost upper pressing ring is pressed by the upper pressing cover 16. A second sealing ring 8 is provided between adjacent upper pressing rings. An upper pressing flange is provided on the outer side of the lower end of the upper pressing cover 16, and the upper pressing flange is fixed to the upper recess flange by bolts.

[0016] The partition 1701 is provided with multiple first mounting grooves, and the upper ends of each tubular catalytic oxygen permeable membrane 2 extend into the corresponding first mounting groove. Multiple first sealing rings and third sealing rings 7 are fitted onto the upper ends of the tubular catalytic oxygen permeable membrane 2 within the first mounting groove, and the third sealing rings 7 are respectively located between two adjacent first sealing rings. A first clamping plate 18 is provided on the upper side of the partition 1701 to ensure that each set of first sealing rings is pressed tightly, and the first clamping plate 18 is fixedly connected to the partition 1701 by bolts. The upper sealing intermediate body 19 is provided with multiple second mounting grooves, and the upper ends of the gas guide pipes 1 extend into the corresponding second mounting grooves. Multiple second sealing rings and fourth sealing rings 6 are fitted onto the upper ends of the gas guide pipes 1 within the second mounting grooves, and the fourth sealing rings 6 are respectively located between two adjacent second sealing rings. A second clamping plate 20 is provided on the upper side of the upper sealing intermediate body 19 to ensure that each set of second sealing rings is pressed tightly, and the second clamping plate 20 is fixedly connected to the upper sealing intermediate body 19 by bolts.

[0017] The lower sealing assembly includes a lower sealing seat 14, and the upper end of the lower sealing seat 14 forms a lower sealing mounting recess for accommodating the lower end of the reactor shell 3. A lower recess flange is provided on the outer side of the upper end of the lower sealing mounting recess. A lower pressing cover 15 and a lower pressing ring are fitted onto the lower end of the reactor shell 3. Each lower pressing ring is stacked sequentially in the gap between the inner wall of the lower sealing mounting recess and the reactor shell 3. The lowermost lower pressing ring abuts against the bottom surface of the lower sealing mounting recess, and the uppermost lower pressing ring is pressed by the lower pressing cover 15. A fifth sealing ring is provided between adjacent lower pressing rings. A lower pressing flange is provided on the outer side of the upper end of the lower pressing cover 15, and the lower pressing flange is fixed to the lower recess flange by bolts.

[0018] The upper and lower sealing assemblies are placed in the low-temperature zone <200℃.

[0019] A method for producing hydrogen using the aforementioned device involves water vapor being decomposed into hydrogen, oxygen ions, and electrons in the outer shell of a reactor under the action of a water splitting catalyst. The hydrogen is then heat-exchanged to obtain high-purity hydrogen. Oxygen ions are conducted to the inner side of a tubular catalytic oxygen-permeable membrane and react with methanol vapor in the cavity between the gas delivery pipe and the tubular catalytic oxygen-permeable membrane under the action of a methanol oxidation catalyst to produce CO2 and water.

[0020] Furthermore, water vapor, serving as the hydrogen source, enters the fourth sealed chamber through the outer inlet of the tubular catalytic oxygen-permeable membrane. It then passes through a through-hole at the lower end of the reactor shell and enters the reactor shell itself. Under the action of the water splitting catalyst 4, the water vapor decomposes into hydrogen, oxygen ions, and electrons. Oxygen ions are conducted to the inner side of the tubular catalytic oxygen-permeable membrane, while hydrogen that fails to pass through rises on the outer side of the membrane and enters the third sealed chamber before exiting through the outer outlet. After further heat exchange, the water vapor becomes liquid, and the gaseous hydrogen is high-purity hydrogen free of impurities such as CO. Methanol vapor, serving as a reducing gas, first enters the first sealed chamber through the inner inlet of the membrane, then enters the gas delivery pipe. After being heated by heat exchange, it exits from the lower end of the gas delivery pipe and folds back upwards into the cavity between the gas delivery pipe and the tubular catalytic oxygen-permeable membrane. Under the action of the methanol oxidation catalyst, it reacts with the oxygen permeating the tubular catalytic oxygen-permeable membrane to generate CO2 and water. CO2 and water then enter the second sealed chamber and are discharged through the inner outlet of the membrane.

[0021] The flow ratio of water vapor to methanol vapor on both sides of the membrane is 2:1 to 9:1, achieving high water decomposition rate and methanol conversion rate.

[0022] The temperature range for steam decomposition is 300℃-1000℃, and the temperature range for methanol oxidation is 300℃-1000℃.

[0023] The water splitting catalyst is a nickel-based catalyst, a ruthenium-based catalyst, a platinum-based catalyst, a rhodium-based catalyst, a cerium-based catalyst, or a biphase catalyst composed of the above.

[0024] The methanol oxidation catalyst is an iron-based catalyst, a cerium-based catalyst, a palladium-based catalyst, or a biphase catalyst composed of the above.

[0025] The tubular catalytic oxygen permeable membrane is a ceramic material, which is a single phase component 1 or a mixture of phase component 1 and phase component 2. When the ceramic material is a mixture of phase component 1 and phase component 2, the mass ratio of phase component 1 is 10-90%, and the corresponding mass ratio of phase component 2 is 10-90%.

[0026] Phase component 1: A 1-x A' x B 1-y-z B' y B” z O 3-δ Where A and A' can be the same or different and are selected from Ba, Sr, La, Sm, Pr or Bi; B, B' and B” can be the same or different and are selected from Fe, Co, Fe, Cu, Ca, Mn, Ga, Ti, Y, Zn, Mo, Ta, Ce, Pr, Gd or La;

[0027] Phase component 2: Ce 1-x Mx O 2-δ M is selected from Pr, Gd, Ti, Er, Y, Tm, Yb, Tb, Lu, Nd, Sm, Dy, Sr, Hf, Th, Ta, Nb or Pb;

[0028] In the two components mentioned above, x and y are the elemental composition ratios of A', B', B” or M', and 0≤x≤1, 0≤y≤1, and δ is the molar fraction of oxygen vacancies in the ceramic material.

[0029] Compared with the prior art, the advantages of the present invention are:

[0030] 1. This invention couples and integrates the water splitting reaction with the methanol-to-hydrogen reaction. Utilizing the 100% selectivity of a tubular catalytic oxygen-permeable membrane for oxygen, carbon monoxide (CO)-free hydrogen can be directly produced on the water splitting side. The method can be carried out at atmospheric pressure, and increasing the pressure will improve the hydrogen production rate. Furthermore, this method is simple and efficient, significantly reducing the steps required to produce CO-free high-purity hydrogen, thereby saving a considerable amount of energy.

[0031] 2. The tubular catalytic oxygen permeable membrane of this invention utilizes abundant and inexpensive raw materials that are easy to prepare. It exhibits good stability in atmospheres containing carbon monoxide (CO) and water vapor, without hydrogen embrittlement, and has a long service life. Furthermore, the tubular catalytic oxygen permeable membrane structure, sealed at one end and open at the other, effectively avoids the sealing problems of ceramic oxygen permeable membranes at high temperatures and reduces stress caused by thermal expansion. These factors can easily lead to membrane rupture, thereby improving the membrane's efficiency.

[0032] 3. The device of the present invention achieves high efficiency and high stability in methanol-to-hydrogen production by utilizing a gas guide pipe, an upper sealing assembly, a lower sealing assembly, and a tubular catalytic oxygen-permeable membrane sealed at one end. The upper sealing assembly, located at the upper end of the reactor shell, contains three mutually isolated sealing chambers: a first sealing chamber, a second sealing chamber, and a third sealing chamber. The lower sealing assembly, located at the lower end of the reactor shell, contains a fourth sealing chamber. Methanol gas is input into the gas guide pipe through the first sealing chamber and output from the second sealing chamber. Water vapor, serving as the hydrogen source, is input through the fourth sealing chamber. After entering the reactor shell, it decomposes into hydrogen, oxygen ions, and electrons under the action of the water splitting catalyst. The hydrogen continues to rise and is finally output from the third sealing chamber, while the oxygen ions permeate through the tubular catalytic oxygen-permeable membrane to react inside the membrane. This structure ensures that the water splitting catalyst and water vapor are always positioned on the same side during device operation, while the methanol oxidation catalyst is positioned on the same side as the methanol vapor, thereby guaranteeing high efficiency in methanol-to-hydrogen production.

[0033] 4. The upper sealing assembly of the device of the present invention includes, from top to bottom, an upper sealing cover, an upper sealing intermediate body, and an upper sealing seat. A partition is provided in the middle of the upper sealing seat, and a first sealing chamber is formed between the upper sealing cover and the upper sealing intermediate body. A second sealing chamber is formed between the upper sealing intermediate body and the partition. At the same time, the upper end of the gas guide tube is fixed on the upper sealing intermediate body, and the upper end of the tubular catalytic oxygen permeable membrane is fixed on the upper sealing seat. The above structure facilitates the installation and disassembly of the gas guide tube and the tubular catalytic oxygen permeable membrane, and an appropriate number of gas guide tubes and tubular catalytic oxygen permeable membranes can be flexibly installed according to actual needs.

[0034] 5. The present invention provides superimposed sealing rings at the fixed position at the upper end of the gas guide tube and at the fixed position at the upper end of the tubular catalytic oxygen permeable membrane, and a sealing ring is provided between adjacent sealing rings. Then, the first and second pressing plates are used to press the corresponding sealing rings and sealing rings to ensure reliable sealing at the fixed position at the upper end of the gas guide tube and the fixed position at the upper end of the tubular catalytic oxygen permeable membrane which is sealed at one end. At the same time, the present invention provides pressing caps and pressing rings at the upper and lower ends of the reactor shell, and a sealing ring is also provided between adjacent pressing rings. The sealing is ensured by pressing with the corresponding pressing caps, which can ensure reliable sealing of each chamber. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the structure of the device of the present invention.

[0036] Figure 2 for Figure 1 Enlarged view of point A in the image.

[0037] Figure 3 This is a schematic diagram illustrating the working principle of the device of the present invention.

[0038] Figure 4 for Figure 3 Enlarged view of point B in the image.

[0039] Figure 5 The results show the hydrogen production rate and the stability of hydrogen purity in the hydrogen production reaction of Example 1 of this invention after 500 hours of testing.

[0040] Wherein, 1 is the gas guide pipe; 2 is the tubular catalytic oxygen-permeable membrane; 3 is the reactor shell; 4 is the water splitting catalyst; 5 is the methanol oxidation catalyst; 6 is the fourth sealing ring; 7 is the third sealing ring; 8 is the second sealing ring; 9 is the first sealing ring; 10 is the inner inlet of the membrane; 11 is the inner outlet of the membrane; 12 is the outer inlet of the membrane; 13 is the outer outlet of the membrane; 14 is the lower sealing seat; 15 is the lower pressure cover; 16 is the upper pressure cover; 17 is the upper sealing seat; 1701 is the partition plate; 18 is the first pressure plate; 19 is the upper sealing intermediate body; 20 is the second pressure plate; 21 is the upper sealing cover; 22 is the first sealing chamber; 23 is the second sealing chamber; 24 is the third sealing chamber; 25 is the fourth sealing chamber. Detailed Implementation

[0041] The invention will now be described in further detail with reference to the accompanying drawings.

[0042] like Figures 1-5 As shown, the multi-channel methanol-to-hydrogen device based on a one-end sealed catalytic oxygen-permeable membrane of the present invention includes a reactor shell 3, a gas guide pipe 1, and a tubular catalytic oxygen-permeable membrane 2. The reactor shell 3 is connected to an upper sealing assembly at its upper end and a lower sealing assembly at its lower end. The upper sealing assembly contains, from top to bottom, a first sealing chamber 22, a second sealing chamber 23, and a third sealing chamber 24. The lower sealing assembly contains a fourth sealing chamber 25. The first sealing chamber 22 communicates with the membrane inner inlet 10, and the second sealing chamber 23 communicates with the membrane inner outlet 11. The third sealing chamber 24, the reactor shell 3, the second sealing chamber 23, and the third sealing chamber 24 are connected to the membrane inner outlet 11. The four sealed chambers 25 are connected in sequence, meaning that the upper and lower ends of the reactor shell 3 are provided with through holes for gas passage. The third sealed chamber 24 is connected to the membrane outer outlet 13, and the fourth sealed chamber 25 is connected to the membrane outer inlet 12. The tubular catalytic oxygen permeable membrane 2 is open at the upper end and sealed at the lower end. The upper opening of the tubular catalytic oxygen permeable membrane 2 is located in the second sealed chamber 23, and the lower end is located in the reactor shell 3. The gas guide pipe 1 is located in the tubular catalytic oxygen permeable membrane 2, and the upper end of the gas guide pipe 1 extends from the upper opening of the tubular catalytic oxygen permeable membrane 2 and is placed in the first sealed chamber 22. Figures 2-3 As shown, a water splitting catalyst 4 is provided on the outer side of the tubular catalytic oxygen permeable membrane 2, and a methanol oxidation catalyst 5 is provided on the inner side of the tubular catalytic oxygen permeable membrane 2.

[0043] The opening of the lower section of the gas delivery tube 1 is located no more than 1 cm from the lower end of the tubular catalytic oxygen permeable membrane 2.

[0044] The tubular catalytic oxygen permeable membrane 2 has an outer diameter of 2-20 mm, a wall thickness of 0.1-2 mm, and a length of 10-100 cm.

[0045] The lengths of water splitting catalyst 4 and methanol oxidation catalyst 5 are 10-400 mm; the outer diameters of the thicknesses of water splitting catalyst 4 and methanol oxidation catalyst 5 are 5-200 micrometers.

[0046] like Figure 3 As shown, when the device of the present invention is working, water vapor, which serves as the hydrogen source, enters the fourth sealed chamber 25 through the inlet 12 on the outside of the membrane, and then enters the reactor shell 3 through the through hole at the lower end of the reactor shell 3. Under the action of the water splitting catalyst 4, the water vapor is decomposed into hydrogen, oxygen ions, and electrons, such as... Figure 4As shown, oxygen ions are conducted to the inner side of the tubular catalytic oxygen permeable membrane 2 through the membrane, while hydrogen gas that fails to pass through the membrane rises on the outer side and enters the third sealed chamber 24 before being output from the outer membrane outlet 13. After heat exchange, the unreacted water vapor at low temperature becomes liquid, and the generated gaseous hydrogen is high-purity hydrogen without impurities such as CO. Methanol vapor, as a reducing gas, first enters the first sealed chamber 22 through the inner membrane inlet 10, and then enters the gas guide pipe 1. After being heated by heat exchange, it is output from the lower end of the gas guide pipe 1 and turns upward back into the cavity between the gas guide pipe 1 and the tubular catalytic oxygen permeable membrane 2. Under the action of the methanol oxidation catalyst 5, it reacts with the oxygen permeating the tubular catalytic oxygen permeable membrane 2 to generate CO2 and water. Then, CO2 and water enter the second sealed chamber 23 and are discharged from the inner membrane outlet 11.

[0047] like Figure 1 As shown, the upper sealing assembly includes an upper sealing cover 21, an upper sealing intermediate body 19, and an upper sealing seat 17 arranged sequentially from top to bottom. The upper sealing cover 21 and the upper sealing intermediate body 19 form the first sealing chamber 22. The upper sealing seat 17 is provided with a partition 1701 in the middle. The upper sealing intermediate body 19 and the partition 1701 form the second sealing chamber 23. The partition 1701 and the upper end of the reactor shell 3 form the third sealing chamber 24.

[0048] like Figure 1 As shown, in this embodiment, the upper sealing cover 21 is provided with an upper sealing cover flange on the outer side of its lower end, the upper sealing intermediate body 19 is provided with an intermediate body flange on the outer side of its upper end, and the upper sealing seat 17 is provided with a sealing seat upper flange on the outer side of its upper end. The upper sealing cover flange, the intermediate body flange, and the sealing seat upper flange are fixedly connected by bolts, and a first sealing ring 9 is provided between the upper sealing cover flange and the intermediate body flange, and between the intermediate body flange and the sealing seat upper flange.

[0049] like Figure 1 As shown, the lower end of the upper sealing seat 17 forms an upper sealing mounting recess for accommodating the upper end of the reactor shell 3, and an upper recess flange is provided on the outer side of the lower end of the upper sealing mounting recess. An upper pressing cover 16 and an upper pressure ring are fitted on the outer side of the upper end of the reactor shell 3. Each upper pressure ring is stacked sequentially in the gap between the inner wall of the upper sealing mounting recess and the reactor shell 3, and the uppermost upper pressure ring abuts against the bottom surface of the upper sealing mounting recess. The lowermost upper pressure ring is pressed by the upper pressing cover 16. A second sealing ring 8 is provided between adjacent upper pressure rings. In addition, an upper pressing flange is provided on the outer side of the lower end of the upper pressing cover 16, and the upper pressing flange is fixed to the upper recess flange by bolts, thereby making the upper pressing cover 16 press and seal each upper pressure ring.

[0050] like Figure 1 As shown, the upper end of the tubular catalytic oxygen permeable membrane 2 is fixed to the partition plate 1701 inside the upper sealing seat 17, and the upper end of the gas guide tube 1 is fixed to the upper sealing intermediate body 19.

[0051] like Figure 1 As shown, the partition 1701 is provided with a plurality of first mounting grooves, and the upper ends of each tubular catalytic oxygen permeable membrane 2 extend into the corresponding first mounting groove. The first mounting groove is provided with a plurality of first sealing pressure rings and third sealing rings 7 fitted onto the upper ends of the tubular catalytic oxygen permeable membrane 2, and the third sealing rings 7 are respectively disposed between two adjacent first sealing pressure rings. The upper side of the partition 1701 is provided with a first pressing plate 18 to ensure that each set of first sealing pressure rings presses the sealing rings tightly, and the first pressing plate 18 is fixedly connected to the partition 1701 by bolts.

[0052] like Figure 1 As shown, the upper sealing intermediate body 19 is provided with a plurality of second mounting grooves, and the upper end of the air guide tube 1 extends into the corresponding second mounting groove. The second mounting groove is provided with a plurality of second sealing pressure rings and fourth sealing rings 6 fitted onto the upper end of the air guide tube 1, and the fourth sealing rings 6 are respectively disposed between two adjacent second sealing pressure rings. The upper side of the upper sealing intermediate body 19 is provided with a second pressing plate 20 to ensure that each set of second sealing pressure rings presses the sealing ring, and the second pressing plate 20 is fixedly connected to the upper sealing intermediate body 19 by bolts.

[0053] like Figure 1 As shown, the lower sealing assembly includes a lower sealing seat 14, and the upper end of the lower sealing seat 14 forms a lower sealing mounting recess for accommodating the lower end of the reactor shell 3. A lower recess flange is provided on the outer side of the upper end of the lower sealing mounting recess. A lower pressing cover 15 and a lower pressing ring are fitted onto the lower end of the reactor shell 3. Each lower pressing ring is stacked sequentially in the gap between the inner wall of the lower sealing mounting recess and the reactor shell 3. The lowermost lower pressing ring abuts against the bottom surface of the lower sealing mounting recess, and the uppermost lower pressing ring is pressed by the lower pressing cover 15. A fifth sealing ring is provided between adjacent lower pressing rings. In addition, a lower pressing flange is provided on the outer side of the upper end of the lower pressing cover 15, and the lower pressing flange is fixed to the lower recess flange by bolts, thereby causing the lower pressing cover 15 to press and seal each lower pressing ring.

[0054] like Figure 3 As shown, the reactor shell 3 is located in a high-temperature zone where the temperature gradually decreases along the X direction. Thus, the sealed end of the tubular catalytic oxygen permeable membrane 2 and the output end of the gas guide pipe 1 are located at the high-temperature end of the high-temperature zone, 300℃-1000℃, while the open end of the tubular catalytic oxygen permeable membrane 2 and the input end of the gas guide tank 1 are located at the low-temperature end, <200℃.

[0055] Example 1

[0056] In the above-mentioned device, the tubular catalytic oxygen-permeable membrane 2 has a Ce content of 60 wt.% 0.9 Pr 0.1 O 2-δ -40wt.%Pr 0.6 Sr 0.4 Fe 0.6 Al 0.3 Co 0.4 O 3-δ (CP-PSFAC was prepared according to Chinese Patent 202110291242.0, a method for preparing a one-end sealed tubular ceramic membrane), with an outer diameter of 5.0 mm, a wall thickness of 0.5 mm, and a length of 40 cm. The water splitting catalyst 4 and the methanol oxidation catalyst 5 are 6 cm long, and the catalytic layer thickness of the water splitting catalyst 4 and the methanol oxidation catalyst 5 is 20 micrometers. The sealed ends of the three tubular catalytic oxygen permeable membranes 2 are placed in the high-temperature zone (950°C) of the reactor shell 3, and the open ends of the tubular catalytic oxygen permeable membranes 2 are placed in the low-temperature zone and sealed with sealing rings. A flow rate of 100 mL / min is introduced into one side of the membrane. -1 Water vapor, on the other side at a flow rate of 50 mL / min -1 Methanol vapor was used as the purging gas.

[0057] Water vapor, serving as the hydrogen source, enters the fourth sealed chamber through the outer inlet of the tubular catalytic oxygen-permeable membrane. It then enters the reactor shell through a through-hole at the lower end of the shell. Under the action of the nickel-based / cerium-based biphase catalyst Ni / CPO (water splitting catalyst), it decomposes into hydrogen, oxygen ions, and electrons. Oxygen ions are conducted to the inner side of the tubular catalytic oxygen-permeable membrane, while hydrogen that fails to pass through flows along the outer side of the membrane and ultimately exits from there. After subsequent heat exchange, the unreacted water vapor at low temperatures liquefies, while the gaseous hydrogen is high-purity hydrogen without CO. Meanwhile, methanol vapor undergoes an oxidation reaction with oxygen permeating the tubular catalytic oxygen-permeable membrane under the action of the cerium-based catalyst CPO (methanol oxidation catalyst), producing CO2 and water, which is ultimately exited from the inner outlet of the membrane. After subsequent heat exchange, the unreacted water vapor at low temperatures liquefies and is collected, while the gaseous CO2 is highly concentrated.

[0058] The products from the water splitting side after the reaction were detected by Agilent gas chromatography, confirming the presence of only hydrogen within the detection limits, with no CO signal detected, and the hydrogen purity >6N. The hydrogen yield at 950℃ was 25.4 mL / min. -1 A 500-hour stability test was conducted, see [link / details]. Figure 5 ( Figure 5The horizontal axis represents time, the vertical axis on the right represents hydrogen yield, and the vertical axis on the left represents hydrogen purity. The hydrogen yield did not decrease.

[0059] Example 2

[0060] In the above-mentioned device, the tubular catalytic oxygen-permeable membrane 2 has a Ce content of 60 wt.% 0.9 Pr 0.1 O 2-δ -40wt.%Pr 0.6 Sr 0.4 Fe 0.6 Al 0.4 O 3-δ (CP-PSFA was prepared according to patent 202110291242.0, a method for preparing a one-end sealed tubular ceramic membrane), with an outer diameter of 5.0 mm, a wall thickness of 0.5 mm, and a length of 40 cm. Catalysts were loaded on both sides of the membrane; the thickness of the catalyst layers for water splitting catalyst 4 and methanol oxidation catalyst 5 was 20 micrometers, and the length of the catalyst layers for water splitting catalyst 4 and methanol oxidation catalyst 5 was 10 cm. The sealed ends of the three tubular catalytic oxygen permeable membranes 2 were placed in the high-temperature zone (850°C) of the reactor shell 3, and the open ends of the tubular catalytic oxygen permeable membranes 2 were placed in the low-temperature zone and sealed with sealing rings. A flow rate of 100 mL / min was introduced into one side of the membrane. -1 Water vapor, on the other side at a flow rate of 50 mL / min -1 Methanol vapor was used as the purging gas.

[0061] Water vapor, serving as the hydrogen source, enters the fourth sealed chamber through the outer inlet of the tubular catalytic oxygen-permeable membrane. It then enters the reactor shell through a through-hole at the lower end of the shell. Under the action of the nickel-based / cerium-based biphase catalyst Ni / CPO (water splitting catalyst), it decomposes into hydrogen, oxygen ions, and electrons. Oxygen ions are conducted to the inner side of the tubular catalytic oxygen-permeable membrane, while hydrogen that fails to pass through flows along the outer side of the membrane and eventually exits from there. After subsequent heat exchange, the unreacted water vapor at low temperatures liquefies, and the gaseous hydrogen is high-purity hydrogen without CO. Meanwhile, methanol vapor undergoes an oxidation reaction with oxygen permeating through the tubular catalytic oxygen-permeable membrane 2 under the action of the palladium-based / cerium-based biphase catalyst Pd / CPO (methanol oxidation catalyst), producing CO2 and water, which is ultimately exited from the inner outlet of the membrane. After subsequent heat exchange, the unreacted water vapor at low temperatures liquefies and is collected, while the gaseous CO2 is highly concentrated.

[0062] The products from the water splitting side after the reaction were detected by Agilent gas chromatography, confirming the presence of only hydrogen within the detection limits, with no CO signal detected, and the hydrogen purity >6N. The hydrogen separation rate at 850℃ was 15.5 mL / min. -1A 200-hour stability test was conducted, and the hydrogen separation performance did not decrease.

[0063] Example 3

[0064] In the above-mentioned device, the tubular catalytic oxygen-permeable membrane 2 has a Ce content of 70 wt.% 0.9 Gd 0.1 O 2-δ -30wt.% Ba 0.6 Fe 0.85 Mg 0.1 Ce 0.05 O 3-δ (CG-BFMC was prepared according to patent 202110291242.0, a method for preparing a one-end sealed tubular ceramic membrane), with an outer diameter of 10.0 mm, a wall thickness of 0.5 mm, and a length of 40 cm. Catalysts were loaded on both sides of the membrane; the thickness of the catalyst layers for water splitting catalyst 4 and methanol oxidation catalyst 5 was 20 micrometers, and the length of the catalyst layers for water splitting catalyst 4 and methanol oxidation catalyst 5 was 10 cm. The sealed ends of the seven tubular catalytic oxygen permeable membranes 2 were placed in the high-temperature zone (850°C) of the reactor shell 3, and the open ends of the tubular catalytic oxygen permeable membranes 2 were placed in the low-temperature zone and sealed with sealing rings. A flow rate of 200 mL / min was introduced into one side of the membrane. -1 Water vapor, on the other side at a flow rate of 100 mL / min -1 Methanol vapor was used as the purging gas.

[0065] Water vapor, serving as the hydrogen source, enters the fourth sealed chamber through the outer inlet of the tubular catalytic oxygen-permeable membrane. It then enters the reactor shell through a through-hole at the lower end of the shell. Under the action of the platinum-based / cerium-based biphase catalyst Pt / CGO (water splitting catalyst), it decomposes into hydrogen, oxygen ions, and electrons. Oxygen ions permeate through the tubular catalytic oxygen-permeable membrane and are conducted to the inner side of the membrane. Hydrogen that fails to pass through the membrane flows along its outer side and eventually exits from the outer side. After heat exchange, the unreacted water vapor at low temperatures liquefies, while the gaseous hydrogen is high-purity hydrogen without CO. Meanwhile, methanol vapor undergoes an oxidation reaction with oxygen permeating through the tubular catalytic oxygen-permeable membrane 2 under the action of the cerium-based catalyst CGO (methanol oxidation catalyst), producing CO2 and water, which is ultimately exited from the inner side of the membrane. After heat exchange, the unreacted water vapor at low temperatures liquefies and is collected, while the gaseous CO2 is highly concentrated. The products from the water splitting side after the reaction were detected by Agilent gas chromatography, confirming the presence of only hydrogen within the detection limits, with no CO signal detected, and the hydrogen purity >6N. The hydrogen separation rate was 54.6 mL / min. -1 A 300-hour stability test was conducted, and the hydrogen separation performance did not decrease.

[0066] Example 4

[0067] In the above-mentioned device, the tubular catalytic oxygen-permeable membrane 2 has a Ce content of 60 wt.% 0.9 Pr 0.1 O 2-δ -40wt.%Pr 0.6 Sr 0.4 Fe 0.6 Al 0.3 Co 0.1 O 3-δ (CP-PSFAC was prepared according to patent 202110291242.0, a method for preparing a one-end sealed tubular ceramic membrane), with an outer diameter of 5.0 mm, a wall thickness of 0.5 mm, and a length of 40 cm. Catalysts were loaded on both sides of the membrane; the thickness of the catalyst layers for water splitting catalyst 4 and methanol oxidation catalyst 5 was 10 micrometers, and the length of the catalyst layers for water splitting catalyst 4 and methanol oxidation catalyst 5 was 10 centimeters. The sealed ends of 19 one-end sealed tubular catalytic oxygen permeable membranes 2 were placed in the high-temperature zone (1000°C) of the reactor shell 3, while the open ends of the tubular catalytic oxygen permeable membranes 2 were placed in the low-temperature zone and sealed with sealing rings. A flow rate of 1000 mL / min was introduced into one side of the membrane. -1 Water vapor, on the other side at a flow rate of 300 mL / min -1 Methanol vapor was used as the purging gas.

[0068] Water vapor, serving as the hydrogen source, enters the fourth sealed chamber through the outer inlet of the tubular catalytic oxygen-permeable membrane. It then enters the reactor shell through a through-hole at the lower end of the shell. Under the action of the nickel-based / cerium-based biphase catalytic Ni / CPO (water splitting catalyst), it decomposes into hydrogen, oxygen ions, and electrons. Oxygen ions are conducted to the inner side of the tubular catalytic oxygen-permeable membrane, while hydrogen that fails to pass through flows along the outer side of the membrane and ultimately exits from there. After subsequent heat exchange, the unreacted water vapor at low temperatures liquefies, while the gaseous hydrogen is high-purity hydrogen without CO. Meanwhile, methanol vapor undergoes an oxidation reaction with oxygen permeating through the tubular catalytic oxygen-permeable membrane 2 under the action of the cerium-based catalyst CPO (methanol oxidation catalyst), producing CO2 and water, which is ultimately exited from the inner outlet of the membrane. After subsequent heat exchange, the unreacted water vapor at low temperatures liquefies and is collected, while the gaseous CO2 is highly concentrated.

[0069] The products from the water splitting side after the reaction were detected by Agilent gas chromatography, confirming the presence of only hydrogen within the detection limits, with no CO signal detected. The hydrogen purity was >6N. The hydrogen separation rate was 186 mL / min. -1 A 500-hour stability test was conducted, and the hydrogen separation performance did not decrease.

[0070] As can be seen from the above embodiments, the method of the present invention utilizes the 100% selectivity of the tubular catalytic oxygen-permeable membrane for oxygen to directly produce hydrogen gas without carbon monoxide (CO), significantly reducing the steps in hydrogen production while having a high hydrogen production rate.

Claims

1. A multi-channel methanol-to-hydrogen device based on a one-end sealed catalytic oxygen-permeable membrane, characterized in that: The reactor includes a reactor shell (3), a gas guide pipe (1), and a tubular catalytic oxygen-permeable membrane (2). The upper end of the reactor shell (3) is connected to an upper sealing assembly, and the lower end is connected to a lower sealing assembly. The upper sealing assembly has a first sealing chamber (22), a second sealing chamber (23), and a third sealing chamber (24) arranged sequentially from top to bottom. The lower sealing assembly has a fourth sealing chamber (25). The first sealing chamber (22) is connected to the membrane inner inlet (10), and the second sealing chamber (23) is connected to the membrane inner outlet (11). The third sealing chamber (24), the reactor shell (3), and the fourth sealing chamber (25) are connected sequentially. The fourth sealed chamber (25) is connected to the membrane outer outlet (13) and the membrane outer inlet (12). The tubular catalytic oxygen permeable membrane (2) is open at the upper end and sealed at the lower end. The upper opening of the tubular catalytic oxygen permeable membrane (2) is located in the second sealed chamber (23) and the lower end is located in the reactor shell (3). The gas guide pipe (1) is located in the tubular catalytic oxygen permeable membrane (2). The upper end of the gas guide pipe (1) extends out from the upper opening of the tubular catalytic oxygen permeable membrane (2) and is placed in the first sealed chamber (22). A water splitting catalyst (4) is provided on the outside of the tubular catalytic oxygen permeable membrane (2), and a methanol oxidation catalyst (5) is provided on the inside of the tubular catalytic oxygen permeable membrane (2).

2. The methanol-to-hydrogen multichannel device based on a one-end sealed catalytic oxygen-permeable membrane according to claim 1, characterized in that: The upper sealing assembly includes an upper sealing cover (21), an upper sealing intermediate body (19), and an upper sealing seat (17) arranged sequentially from top to bottom. The upper sealing cover (21) and the upper sealing intermediate body (19) form the first sealing chamber (22). The upper sealing seat (17) is provided with a partition (1701) in the middle. The upper sealing intermediate body (19) and the partition (1701) form the second sealing chamber (23). The partition (1701) and the upper end of the reactor shell (3) form the third sealing chamber (24). The upper end of the tubular catalytic oxygen permeable membrane (2) is fixed to the partition (1701), and the upper end of the gas guide pipe (1) is fixed to the upper sealing intermediate body (19).

3. The methanol-to-hydrogen multichannel device based on a one-end sealed catalytic oxygen-permeable membrane according to claim 2, characterized in that: The upper sealing cover (21) is provided with an upper sealing cover flange on the outer side of its lower end, the upper sealing intermediate body (19) is provided with an intermediate body flange on the outer side of its upper end, and the upper sealing seat (17) is provided with a sealing seat upper flange on the outer side of its upper end. The upper sealing cover flange, the intermediate body flange and the sealing seat upper flange are fixedly connected by bolts, and a first sealing ring (9) is provided between the upper sealing cover flange and the intermediate body flange and between the intermediate body flange and the sealing seat upper flange.

4. The methanol-to-hydrogen multichannel device based on a one-end sealed catalytic oxygen-permeable membrane according to claim 2, characterized in that: The lower end of the upper sealing seat (17) forms an upper sealing mounting recess for accommodating the upper end of the reactor shell (3), and an upper recess flange is provided on the outer side of the lower end of the upper sealing mounting recess. An upper pressing cover (16) and an upper pressure ring are fitted on the outer side of the upper end of the reactor shell (3). Each upper pressure ring is stacked in sequence in the gap between the inner wall of the upper sealing mounting recess and the reactor shell (3). The uppermost upper pressure ring abuts against the bottom surface of the upper sealing mounting recess, and the lowermost upper pressure ring is pressed by the upper pressing cover (16). A second sealing ring (8) is provided between adjacent upper pressure rings. An upper pressing flange is provided on the outer side of the lower end of the upper pressing cover (16), and the upper pressing flange is fixed to the upper recess flange by bolts.

5. The methanol-to-hydrogen multichannel device based on a one-end sealed catalytic oxygen-permeable membrane according to claim 2, characterized in that: The partition plate (1701) is provided with a plurality of first mounting grooves, and the upper ends of each tubular catalytic oxygen permeable membrane (2) extend into the corresponding first mounting groove. The first mounting groove is provided with a plurality of first sealing rings and third sealing rings (7) fitted onto the upper ends of the tubular catalytic oxygen permeable membrane (2), and the third sealing rings (7) are respectively located between two adjacent first sealing rings. The upper side of the partition plate (1701) is provided with a first pressing plate (18) to ensure that each set of first sealing rings is pressed tightly, and the first pressing plate (18) is fixedly connected to the partition plate (1701) by bolts. The upper sealing intermediate body (19) is provided with a plurality of second mounting grooves, and the upper end of the air guide pipe (1) extends into the corresponding second mounting groove. The second mounting groove is provided with a plurality of second sealing pressure rings and fourth sealing rings (6) fitted onto the upper end of the air guide pipe (1), and the fourth sealing rings (6) are respectively located between two adjacent second sealing pressure rings. The upper side of the upper sealing intermediate body (19) is provided with a second pressing plate (20) to ensure that each set of second sealing pressure rings is pressed tightly, and the second pressing plate (20) is fixedly connected to the upper sealing intermediate body (19) by bolts.

6. The methanol-to-hydrogen multichannel device based on a one-end sealed catalytic oxygen-permeable membrane according to claim 1, characterized in that: The lower sealing assembly includes a lower sealing seat (14), and the upper end of the lower sealing seat (14) forms a lower sealing mounting recess for accommodating the lower end of the reactor shell (3). A lower recess flange is provided on the outer side of the upper end of the lower sealing mounting recess. A lower pressing cover (15) and a lower pressing ring are fitted on the lower end of the reactor shell (3). Each lower pressing ring is stacked in sequence in the gap between the inner wall of the lower sealing mounting recess and the reactor shell (3). The lowermost lower pressing ring abuts against the bottom surface of the lower sealing mounting recess. The uppermost lower pressing ring is pressed by the lower pressing cover (15). A fifth sealing ring is provided between adjacent lower pressing rings. A lower pressing flange is provided on the outer side of the upper end of the lower pressing cover (15). The lower pressing flange is fixed to the lower recess flange by bolts.

7. A method for producing hydrogen using the apparatus according to any one of claims 1-6, characterized in that: Water vapor in the reactor shell is decomposed into hydrogen, oxygen ions and electrons under the action of a water splitting catalyst. The hydrogen is then heat-exchanged to obtain high-purity hydrogen. Oxygen ions are conducted to the inside of the tubular catalytic oxygen-permeable membrane and react with methanol vapor in the cavity between the gas guide tube and the tubular catalytic oxygen-permeable membrane to produce CO2 and water under the action of a methanol oxidation catalyst.

8. The hydrogen production method according to claim 7, characterized in that: The flow ratio of water vapor to methanol vapor is 2:1 to 9:

1.

9. The hydrogen production method according to claim 7, characterized in that: The temperature range for steam decomposition is 300℃-1000℃, and the temperature range for methanol oxidation is 300℃-1000℃.

10. The hydrogen production method according to claim 7, characterized in that: The water splitting catalyst is a nickel-based catalyst, a ruthenium-based catalyst, a platinum-based catalyst, a rhodium-based catalyst, a cerium-based catalyst, or a biphase catalyst composed of the above; the methanol oxidation catalyst is an iron-based catalyst, a cerium-based catalyst, a palladium-based catalyst, or a biphase catalyst composed of the above.

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