Methanol-to-hydrogen multi-channel device based on catalytic oxygen permeation membrane with one sealed end

Abstract

The utility model relates to a methanol hydrogen production multichannel device based on a tubular oxygen permeable membrane with one sealed end, which is characterized in that the upper end of a reactor shell is connected with an upper sealing assembly, the lower end of the reactor shell is connected with a lower sealing assembly, a first sealing chamber, a second sealing chamber and a third sealing chamber are arranged in the upper sealing assembly, and a fourth sealing chamber is arranged in the lower sealing assembly; the first sealing chamber is communicated with the membrane inner side inlet, the second sealing chamber is communicated with the membrane inner side outlet, the third sealing chamber, the reactor shell and the fourth sealing chamber are communicated in sequence, the third sealing chamber is communicated with the membrane outer side outlet, and the fourth sealing chamber is communicated with the membrane outer side inlet; the upper end opening of the tubular oxygen-permeable membrane is arranged in the second sealing chamber, the lower end sealing end is arranged in the reactor shell, the gas-guide tube is arranged in the tubular oxygen-permeable membrane, the upper end of the gas-guide tube extends out of the upper end opening of the tubular oxygen-permeable membrane and is arranged in the first sealing chamber, a water decomposition catalyst is arranged on the outer side of the tubular oxygen-permeable membrane, and a methanol oxidation catalyst is arranged on the inner side of the tubular oxygen-permeable membrane. The oil-water separator has a good separation effect and high stability, and is relatively low in cost.

Description

TECHNICAL FIELD

[0001] The utility model relates to the field of methanol hydrogen production, specifically to a methanol hydrogen production multi-channel device based on one end sealing catalytic oxygen permeable membrane. BACKGROUND

[0002] Methanol is an excellent liquid hydrogen storage and hydrogen carrier. It can realize hydrogen production by 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 gas online for low-temperature fuel cell vehicles, effectively solving the problem of hydrogen storage and transportation, and improving safety.

[0003] However, fuel hydrogen produced in the process of methanol hydrogen production contains impurities such as CO2 and CO, especially trace amounts of CO, which can quickly poison the catalyst of the fuel cell. Therefore, a series of impurity removal processes are needed after the methanol reforming reaction, which limits the promotion and application of methanol in the field of fuel cells. Although Pd membrane reactors can be used to realize in-situ separation and purification of hydrogen, the high cost of Pd as a noble 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 the prior art, the methanol reforming hydrogen production technology based on the mixed conductor oxygen permeable membrane reactor couples and integrates water decomposition reaction and methanol hydrogen production reaction. In the reaction, water is decomposed into oxygen and hydrogen on one side of the membrane, oxygen is transmitted to the other side in the form of ions through the oxygen permeable membrane, and oxidation reaction occurs with the methanol reforming reaction product (or directly with methanol) to generate CO2 and H2O. The use of oxygen ion-electron mixed conductors can achieve 100% selectivity for oxygen, and hydrogen gas without CO can be prepared on the side of the water decomposition reaction in one step. The key to effective methanol hydrogen production lies in the construction of high-efficiency membrane reactors. x

[0005] Currently, sheet-shaped membrane materials are widely studied due to their relatively simple preparation and testing methods. However, sheet-shaped membranes face sealing difficulties 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 difficulties through cold end sealing. Liang et al. used Au paste to seal BaCo x Fe y Zr 1-x-y O 3-δ ​One end of the hollow fiber membrane is sealed, and pure oxygen is successfully prepared (see Ind. Eng. Chem. Res. 2010, 49, 937). In addition, a sleeve sealing method or a rubber ring sealing method can be used to seal the two open ends of the ceramic oxygen permeable membrane away from the high temperature zone (such as Chinese patent CN102284252B, Chinese patent CN101912742A, Chinese patent CN102979981A, etc.). Although this sealing method can avoid the sealing problem of the ceramic oxygen permeable membrane at high temperature, the structure is relatively complex, and the membrane will still generate stress due to thermal expansion under high temperature conditions, which can easily lead to the rupture of the membrane and greatly reduce the use efficiency of the membrane. Content of the utility model

[0006] The utility model discloses a kind of methanol hydrogen production multi-channel devices based on one end sealing catalytic oxygen permeable membrane, it has good separation effect and high stability, and cost is lower.

[0007] The utility model discloses a kind of methanol hydrogen production multi-channel devices based on one end sealing catalytic oxygen permeable membrane, it has good separation effect and high stability, and cost is lower.

[0008] A kind of methanol hydrogen production multi-channel devices based on one end sealing catalytic oxygen permeable membrane, including reactor shell, gas guide pipe and tubular catalytic oxygen permeable membrane, wherein reactor shell upper end connects upper sealing assembly, lower end connects lower sealing assembly, the inside of the upper sealing assembly is equipped with first sealing chamber, second sealing chamber and third sealing chamber from top to bottom in sequence, the inside of the lower sealing assembly is equipped with fourth sealing chamber, the first sealing chamber is communicated with membrane inside import, the second sealing chamber is communicated with membrane inside export, the third sealing chamber, reactor shell, fourth sealing chamber are sequentially communicated, and the third sealing chamber is communicated with membrane outside export, the fourth sealing chamber is communicated with membrane outside import, the upper end of the tubular catalytic oxygen permeable membrane is open, lower end is sealed, and the upper end of the tubular catalytic oxygen permeable membrane is arranged in the second sealing chamber, lower end is arranged in the reactor shell, gas guide pipe is arranged in the tubular catalytic oxygen permeable membrane, and the upper end of gas guide pipe is stretched out from the upper end opening of the tubular catalytic oxygen permeable membrane and placed in the first sealing chamber, water decomposition catalyst is arranged outside the tubular catalytic oxygen permeable membrane, and methanol oxidation catalyst is arranged inside the tubular catalytic oxygen permeable membrane.

[0009] The upper sealing assembly includes upper sealing cover, upper sealing intermediate body and upper sealing seat, which are arranged from top to bottom in sequence, wherein the first sealing chamber is formed between the upper sealing cover and the upper sealing intermediate body, the second sealing chamber is formed between the upper sealing intermediate body and the partition plate, and the third sealing chamber is formed between the partition plate and the upper end of the reactor shell, the upper end of the tubular catalytic oxygen permeable membrane is fixed on the partition plate, and the upper end of the gas guide pipe is fixed on the upper sealing intermediate body.

[0010] The upper sealing cover lower end outer side is provided with an upper sealing cover flange, the upper sealing intermediate body outer side is provided with an intermediate body flange, the upper sealing seat upper end outer side is provided with a sealing seat upper flange, the upper sealing cover flange, intermediate body flange and sealing seat upper flange are fixed by bolts, and the upper sealing cover flange and intermediate body flange and the intermediate body flange and sealing seat upper flange are both provided with a first sealing ring.

[0011] The upper sealing seat lower end forms an upper sealing mounting notch accommodating the reactor shell upper end, and the upper sealing mounting notch lower end outer side is provided with an upper notch flange, the reactor shell upper end is sleeved with an upper compression cover and an upper compression ring, wherein each upper compression ring is sequentially arranged in the gap between the upper sealing mounting notch inner wall and the reactor shell, and the uppermost upper compression ring abuts against the bottom surface of the upper sealing mounting notch, the lowermost upper compression ring is compressed by the upper compression cover, the adjacent upper compression rings are both provided with a second sealing ring, the upper compression cover lower end outer side is provided with an upper compression flange, and the upper compression flange and the upper notch flange are fixed by bolts.

[0012] The partition plate is provided with a plurality of first installation grooves, and the upper end of each tubular catalytic oxygen permeable membrane extends into the corresponding first installation groove, a plurality of first sealing compression rings and third sealing rings sleeved on the upper end of the tubular catalytic oxygen permeable membrane are arranged in the first installation groove, and the third sealing ring is arranged between the adjacent two first sealing compression rings, and the upper side of the partition plate is provided with a first compression plate for ensuring the compression of each group of first sealing compression rings, and the first compression plate and the partition plate are fixed by bolts.

[0013] The upper sealing intermediate body is provided with a plurality of second installation grooves, and the upper end of the gas guide pipe extends into the corresponding second installation groove, a plurality of second sealing compression rings and fourth sealing rings sleeved on the upper end of the gas guide pipe are arranged in the second installation groove, and the fourth sealing ring is arranged between the adjacent two second sealing compression rings, and the upper side of the upper sealing intermediate body is provided with a second compression plate for ensuring the compression of each group of second sealing compression rings, and the second compression plate and the upper sealing intermediate body are fixed by bolts.

[0014] The lower sealing assembly includes a lower sealing seat, and the lower sealing seat upper end forms a lower sealing mounting notch accommodating the reactor shell lower end, the lower sealing mounting notch upper end outer side is provided with a lower notch flange, the reactor shell lower end is sleeved with a lower compression cover and a lower compression ring, wherein each lower compression ring is sequentially arranged in the gap between the lower sealing mounting notch inner wall and the reactor shell, and the lowermost lower compression ring abuts against the bottom surface of the lower sealing mounting notch, the uppermost lower compression ring is compressed by the lower compression cover, the adjacent lower compression rings are both provided with a fifth sealing ring, the lower compression cover upper end outer side is provided with a lower compression flange, and the lower compression flange and the lower notch flange are fixed by bolts.

[0015] The utility model discloses the advantages and positive effect are:

[0016] 1, the utility model discloses a gas pipe, upper seal subassembly, lower seal subassembly and one end sealed tubular catalytic oxygen permeable membrane realize the efficient methanol hydrogen production effect and high stability, wherein the upper seal subassembly of being arranged on the upper end of reactor shell sets up the first seal chamber, second seal chamber and third seal chamber of mutual isolation, sets up the fourth seal chamber in the lower seal subassembly of being arranged in the lower end of reactor shell, and the methanol gas is input in the gas pipe through the first seal chamber, and finally exports by the second seal chamber, and the water vapor as hydrogen source is input by the fourth seal chamber, and after entering the reactor shell, decomposes into hydrogen, oxygen ion and electron under the action of water decomposition catalyst, wherein hydrogen continues to rise and finally exports by the third seal chamber, and oxygen ion penetrates tubular catalytic oxygen permeable membrane and enters the inside reaction of membrane, and the above structure can always guarantee that water decomposition catalyst and water vapor are arranged on the same side when the device is running, and methanol oxidation catalyst is arranged on the same side with methanol steam, and further guarantees the efficient methanol hydrogen production effect.

[0017] 2, the upper seal subassembly of the utility model includes from top to bottom upper seal cover, upper seal intermediate body and upper seal seat, wherein the middle part of upper seal seat is equipped with the baffle, and the first seal chamber is formed between upper seal cover and the upper seal intermediate body, the second seal chamber is formed between the upper seal intermediate body and the baffle, and the upper end of gas pipe is fixed on the upper seal intermediate body, and the upper end of tubular catalytic oxygen permeable membrane is fixed on the upper seal seat, and the above structure facilitates the installation and dismounting of gas pipe and tubular catalytic oxygen permeable membrane, and a proper amount of gas pipe and tubular catalytic oxygen permeable membrane can be flexibly installed according to actual needs.

[0018] 3, the utility model is equipped with the seal compression ring of superposition in the fixed place of the upper end of gas pipe and the fixed place of the upper end of tubular catalytic oxygen permeable membrane, and the seal ring is arranged between the adjacent seal compression ring, then the first compression plate and the second compression plate are used to compress the corresponding seal compression ring and seal ring to guarantee the sealing reliability of the fixed place of the upper end of gas pipe and the fixed place of the upper end of tubular catalytic oxygen permeable membrane, and the utility model is equipped with the compression cover and compression ring in the upper end and the lower end of reactor shell, and the seal ring is also arranged between the adjacent compression ring and is compressed by the corresponding compression cover to guarantee sealing, so that the utility model can guarantee the sealing reliability of each chamber.

[0019] 4, The tubular catalytic oxygen permeable membrane adopts rich membrane material raw materials, low price, easy to prepare, and shows good stability under the atmosphere containing carbon monoxide (CO) and water vapor, and does not occur hydrogen embrittlement, has long service life. The palladium membrane in the prior art is expensive, and the reserves of palladium are limited, which is difficult to be applied on a large scale, and the palladium alloy membrane is strict to the components such as oxygen, water, heavy hydrocarbon, hydrogen sulfide and olefin in the raw material gas. For example, before entering the palladium alloy membrane, the CO content must be reduced to below 0.1ppm, and the water and other impurities must be controlled below 1ppm, in addition, the tubular catalytic oxygen permeable membrane structure of one end sealed and the other end opened adopted by the utility model can effectively avoid the sealing problem of ceramic oxygen permeable membrane at high temperature, and reduce the stress generated by thermal expansion, which easily leads to the rupture of the membrane, thereby improving the use efficiency of the membrane. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 It is a structural schematic diagram of the utility model,

[0021] Figure 2 It is an enlarged view of A in Figure 1

[0022] Figure 3 It is a working principle schematic diagram of the utility model,

[0023] Figure 4 It is an enlarged view of B in Figure 3

[0024] Figure 5 It is a tubular membrane 60wt.%Ce 0.9 Pr 0.1 O 2-δ -40wt.%Pr 0.6 Sr 0.4 Fe 0.6 Al 0.4 O 3-δ The hydrogen production rate in the preparation of high-purity hydrogen without CO in methanol and the hydrogen purity stability test results of 500 hours.

[0025] ​​Wherein, 1 is a gas guide pipe; 2 is a tubular catalytic oxygen permeable membrane; 3 is a reactor shell; 4 is a water decomposition catalyst; 5 is a methanol oxidation catalyst; 6 is a fourth sealing ring; 7 is a third sealing ring; 8 is a second sealing ring; 9 is a first sealing ring; 10 is a membrane inner side inlet; 11 is a membrane inner side outlet; 12 is a membrane outer side inlet; 13 is a membrane outer side outlet; 14 is a lower sealing seat; 15 is a lower pressing cover; 16 is an upper pressing cover; 17 is an upper sealing seat; 1701 is a partition plate; 18 is a first pressing plate; 19 is an upper sealing intermediate body; 20 is a second pressing plate; 21 is an upper sealing cover; 22 is a first sealing chamber; 23 is a second sealing chamber; 24 is a third sealing chamber; 25 is a fourth sealing chamber. DETAILED DESCRIPTION

[0026] The utility model will be further described in connection with the drawings.

[0027] As Figures 1-5 shown, the utility model includes reactor shell 3, gas guide pipe 1 and tubular catalytic oxygen permeable membrane 2, wherein the upper end of reactor shell 3 is connected with upper sealing assembly, and the lower end is connected with lower sealing assembly, the inside of upper sealing assembly is equipped with first sealing chamber 22, second sealing chamber 23 and third sealing chamber 24 in turn from top to bottom, the inside of lower sealing assembly is equipped with fourth sealing chamber 25, first sealing chamber 22 is communicated with membrane inner side inlet 10, second sealing chamber 23 is communicated with membrane inner side outlet 11, third sealing chamber 24, reactor shell 3, fourth sealing chamber 25 are communicated in turn, that is to say, the upper end and the lower end of reactor shell 3 are all equipped with through hole for gas to pass through, third sealing chamber 24 is communicated with membrane outer side outlet 13, fourth sealing chamber 25 is communicated with membrane outer side inlet 12, the upper end of tubular catalytic oxygen permeable membrane 2 is open, and the lower end is sealed, and the upper end opening of tubular catalytic oxygen permeable membrane 2 is arranged in second sealing chamber 23, and the lower end is arranged in reactor shell 3, gas guide pipe 1 is arranged in tubular catalytic oxygen permeable membrane 2, and the upper end of gas guide pipe 1 is stretched out from the upper end opening of tubular catalytic oxygen permeable membrane 2 and is placed in first sealing chamber 22, as Figures 2-3 shown, the outside of tubular catalytic oxygen permeable membrane 2 is equipped with water decomposition catalyst 4, and the inside of tubular catalytic oxygen permeable membrane 2 is equipped with methanol oxidation catalyst 5.

[0028] As Figure 3 shown, the utility model works, the steam as hydrogen source enters fourth sealing chamber 25 from membrane outer side inlet 12, then passes through the through hole of the lower end of reactor shell 3 and enters reactor shell 3, and the steam is decomposed into hydrogen, oxygen ion and electron under the action of water decomposition catalyst 4, wherein as Figure 4As shown, the oxygen ions are conducted to the inner side of the tubular catalytic oxygen permeable membrane 2 through the membrane, while the hydrogen gas that fails to pass through the membrane rises on the outer side of the membrane and enters the third sealed chamber 24 before being output from the outer membrane outlet 13. After heat exchange, the water vapor that has not reacted at low temperature becomes liquid, and the generated gaseous hydrogen is high-purity hydrogen without impurities such as CO. The 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 ions that have passed through 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.

[0029] like Figure 1 As shown, in this embodiment, 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.

[0030] 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.

[0031] like Figure 1 As shown, in this embodiment, 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.

[0032] like Figure 1 As shown, in this embodiment, 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.

[0033] like Figure 1 As shown, in this embodiment, 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, and the first pressing plate 18 is fixedly connected to the partition 1701 by bolts.

[0034] like Figure 1 As shown, in this embodiment, 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.

[0035] like Figure 1 As shown, in this embodiment, 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.

[0036] like Figure 3As shown, the reactor shell 3 is arranged in a high-temperature zone with gradually decreasing temperature along the X direction, so that the sealed end of the tubular catalytic oxygen permeable membrane 2 and the output end of the gas guide pipe 1 are arranged at the high-temperature end of the high-temperature zone, and the open end of the tubular catalytic oxygen permeable membrane 2 and the input end of the gas guide pipe 1 are arranged at the low-temperature end (less than 200℃).

[0037] The tubular catalytic oxygen permeable membrane 2 considers the harsh environment in which the utility model works, and preferably a single-phase and double-phase membrane of iron-based / Ce-based with good stability. In addition, for the same material, the oxygen permeation amount of an asymmetric structure membrane is several times that of a symmetric structure membrane, so a supported oxygen permeable membrane is preferably used to improve the hydrogen production amount.

[0038] The working principle of the utility model is as follows:

[0039] The working principle of the utility model is as follows:

[0040] Example 1:

[0041] Sintered 60wt.%Ce 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) one end sealed tubular catalytic oxygen permeable membrane 2 (in this embodiment, it can be prepared according to patent 202110291242.0 a preparation method of one end sealed tubular ceramic membrane), the outer diameter is 5.0mm, the wall thickness is 0.5mm, and the length is 40cm. The catalyst is filled on both sides of the membrane, and the thickness of the catalytic layer is 20 microns and the length is 6 centimeters. The sealed end of the three tubular catalytic oxygen permeable membranes 2 is placed in the high-temperature zone in the reactor shell 3, and the open end of the tubular catalytic oxygen permeable membrane 2 is placed at the low-temperature end and sealed by a sealing ring. After slowly heating to 950℃, H20 with a flow rate of 100mL min -1 is introduced into one side of the membrane, and methanol with a flow rate of 50mL min -1 is used as a sweeping gas on the other side.

[0042] In this embodiment, the methanol oxidation catalyst 5 uses CPO, and water vapor as the hydrogen source is decomposed into hydrogen, oxygen ions and electrons under the action of 4Ni / CPO. The oxygen ions are conducted to the inside of the membrane through the tubular catalytic oxygen permeable membrane 2. The hydrogen that fails to pass through the tubular catalytic oxygen permeable membrane 2 flows along the outside of the tubular catalytic oxygen permeable membrane 2 and is finally output from the membrane outside outlet 13. After heat exchange, the water vapor that does not react at low temperature becomes liquid, and the gaseous hydrogen is high-purity hydrogen without CO. The methanol vapor reacts with the oxygen ions that pass through the tubular catalytic oxygen permeable membrane 2 under the action of CPO to generate CO2 and water, and is finally output from the membrane inside outlet 11. After heat exchange, the water vapor that does not react at low temperature becomes liquid and is collected, and the gaseous CO2 is high concentration.

[0043] The product on the water decomposition side was detected by Agilent gas chromatography, and it was proved that only hydrogen existed within the detection limit of the chromatogram, and no CO signal was detected, and the hydrogen purity was >6N. The hydrogen yield was 25.4 mL min at 950 degrees. -1 A stability test of 500 h was performed, and the hydrogen yield did not attenuate. Figure 5 Figure 5 The horizontal coordinate is time, and the right vertical coordinate is hydrogen yield, and the left vertical coordinate is hydrogen purity.

[0044] Example 2:

[0045] Sintered 60wt.%Ce 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) one end sealed tubular catalytic oxygen permeable membrane 2 (in this embodiment, it can be prepared according to the patent 202110291242.0 one end sealed tubular ceramic membrane preparation method), the outer diameter is 5.0 mm, the wall thickness is 0.5 mm, and the length is 40 cm. The catalysts are filled on both sides of the membrane, and the thickness of the catalytic layer is 20 microns and the length is 10 centimeters. The sealed end of the three tubular catalytic oxygen permeable membranes 2 is placed in the high temperature zone in the reactor shell 3, and the open end of the tubular catalytic oxygen permeable membrane 2 is placed in the low temperature zone and sealed by a sealing ring. After slow heating to 850℃, H2O with a flow rate of 100 mL min -1 is introduced into one side of the membrane, and methanol with a flow rate of 50 mL min -1 is used as the sweeping gas on the other side.

[0046] ​In this embodiment, the water decomposition catalyst 4 uses 4Ni / CPO, and the methanol oxidation catalyst 5 uses Pd / CPO. After the reaction, the products on the water decomposition side are detected by Agilent gas chromatography, and it is proved that within the detection limit of the chromatograph, only hydrogen exists, and no CO signal is detected, and the purity of hydrogen is > 6N. The hydrogen separation rate is 15.5 mL min -1 . A 200h stability test is performed, and the hydrogen separation performance does not attenuate.

[0047] Example 3:

[0048] sintered 70wt.% Ce 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) one-end-sealed tubular catalytic oxygen permeation membrane 2 (in this embodiment, it can be prepared according to patent 202110291242.0 One-end-sealed tubular ceramic membrane preparation method), the outer diameter is 10.0mm, the wall thickness is 0.5mm, and the length is 40cm. The catalysts are filled on both sides of the membrane, and the thickness of the catalytic layer is 20 microns, and the length is 10 centimeters. The sealed end of the 7 one-end-sealed tubular catalytic oxygen permeation membrane 2 is placed in the high-temperature zone in the reactor shell 3, and the open end of the tubular catalytic oxygen permeation membrane 2 is placed in the low-temperature zone and sealed by a sealing ring. After slowly heating to 850℃, H20 with a flow rate of 200mL min -1 is introduced into one side of the membrane, and methanol with a flow rate of 100mL min -1 is used as the sweeping gas on the other side.

[0049] In this embodiment, the water decomposition catalyst 4 uses Pt / CGO, and the methanol oxidation catalyst 5 uses CGO. After the reaction, the products on the water decomposition side are detected by Agilent gas chromatography, and it is proved that within the detection limit of the chromatograph, only hydrogen exists, and no CO signal is detected, and the purity of hydrogen is > 6N. The hydrogen separation rate is 54.6mL min -1 . A 300h stability test is performed, and the hydrogen separation performance does not attenuate.

[0050] Example 4:

[0051] sintered 60wt.% Ce 0.9 Pr 0.1 O 2-δ -40wt.% Pr 0.6 Sr 0.4 Fe 0.6 Al 0.3 Co 0.1 O3-δ A tubular catalytic oxygen permeable membrane 2 (in this embodiment, it can be prepared according to patent 202110291242.0 Preparation method of one-end sealed tubular ceramic membrane) with one end sealed, with an outer diameter of 5.0 mm, a wall thickness of 0.5 mm, and a length of 40 cm. The catalysts are loaded on both sides of the membrane, and the thickness of the catalytic layer is 10 microns, and the length is 10 cm. The sealed end of the 19 one-end sealed tubular catalytic oxygen permeable membranes 2 is placed in the high-temperature zone in the reactor shell 3, and the open end of the tubular catalytic oxygen permeable membrane 2 is placed in the low-temperature zone and sealed by a sealing ring. After slowly heating to 1000℃, H2O with a flow rate of 1000 mL min -1 is introduced on one side of the membrane, and methanol with a flow rate of 300 mL min -1 is used as a sweeping gas on the other side.

[0052] In this embodiment, the water decomposition catalyst 4 uses 4Ni / CPO, and the methanol oxidation catalyst 5 uses CPO. The products on the water decomposition side are detected by Agilent gas chromatography, and it is proved that within the detection limit of the chromatograph, only hydrogen exists, and no CO signal is detected, and the purity of hydrogen is >6N. The hydrogen separation rate is 186 mL min -1 . The stability test is performed for 500h, and the hydrogen separation performance does not attenuate.

Claims

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

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

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

4. The methanol-to-hydrogen multi-channel device based on one-end-sealed catalytic oxygen-permeable membrane according to claim 2, characterized in that: The upper sealing seat (17) is provided with a plurality of first installation grooves, and the upper end of each tubular catalytic oxygen permeable membrane (2) extends into a corresponding first installation groove. A plurality of first sealing compression rings and third sealing rings (7) are arranged in the first installation grooves and are sleeved on the upper end of the tubular catalytic oxygen permeable membrane (2). The third sealing ring (7) is arranged between two adjacent first sealing compression rings. The upper side of the partition plate (1701) is provided with a first compression plate (18) for ensuring the compression of each group of first sealing compression rings. The first compression plate (18) and the partition plate (1701) are connected by bolts.

5. The methanol-to-hydrogen multi-channel device based on one-end-sealed catalytic oxygen-permeable membrane according to claim 2, characterized in that: The upper sealing intermediate body (19) is provided with a plurality of second installation grooves, and the upper end of each gas guide pipe (1) extends into a corresponding second installation groove. A plurality of second sealing compression rings and fourth sealing rings (6) are arranged in the second installation grooves and are sleeved on the upper end of the gas guide pipe (1). The fourth sealing ring (6) is arranged between two adjacent second sealing compression rings. The upper side of the upper sealing intermediate body (19) is provided with a second compression plate (20) for ensuring the compression of each group of second sealing compression rings. The second compression plate (20) and the upper sealing intermediate body (19) are connected by bolts.

6. The methanol-to-hydrogen multi-channel device based on one-end-sealed catalytic oxygen-permeable membrane according to claim 2, 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 installation recess for accommodating the lower end of the reactor shell (3). The upper end of the lower sealing installation recess is provided with a lower recess flange. The lower end of the reactor shell (3) is sleeved with a lower compression cover (15) and a lower compression ring. Each lower compression ring is arranged in the gap between the inner wall of the lower sealing installation recess and the reactor shell (3) in turn. The lowermost lower compression ring abuts against the bottom surface of the lower sealing installation recess, and the uppermost lower compression ring is compressed by the lower compression cover (15). A fifth sealing ring is arranged between adjacent lower compression rings. The upper end of the lower compression cover (15) is provided with a lower compression flange, and the lower compression flange and the lower recess flange are connected by bolts.

7. The methanol-to-hydrogen multi-channel device based on one-end-sealed catalytic oxygen-permeable membrane according to claim 1, characterized in that: ​

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