Novel reformer based on coupling of proton conductor and carbonate conductor ceramic membrane

Abstract

The invention discloses a novel reformer based on coupling of a proton conductor and a carbonate conductor ceramic membrane. The novel reformer comprises a tubular reformer and a flat plate pile tower reformer, and each reformer comprises a proton electron mixed conductor ceramic membrane, a carbonate electron mixed conductor ceramic membrane and a reforming chamber; a self-heating reforming chemical reaction is carried out in the reforming chamber, the proton-electron mixed conductor ceramic membrane and the carbonate electron mixed conductor ceramic membrane respectively carry out an electrode reaction, the chemical reaction and the electrode reaction are simultaneously coupled, and the purification of hydrogen and the separation of the product carbon dioxide are realized in one step at a high temperature by utilizing the ceramic membranes. The reformer can solve the problems of methane reforming and hydrogen purification, and is simple to control and easy to obtain pure hydrogen.

Description

Technical Field

[0001] The present invention belongs to the technical field of reformers, and particularly relates to a novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membranes. Background Art

[0002] As an important energy carrier for realizing a low-carbon life, hydrogen energy is receiving increasing attention. However, due to the small volumetric density of hydrogen, it is difficult to store and transport. Converting hydrogen into fuels with high energy density such as methane and methanol that are convenient for transportation, and then obtaining hydrogen by reforming on-site during hydrogen use, is a solution to solve the problem of hydrogen energy transportation. However, the hydrogen obtained on-site needs a gas purification process to remove CO2 or CO therein to facilitate the use of proton exchange membrane fuel cells. This makes the purification of hydrogen very important. Traditional palladium membrane purification devices are expensive and complex to control; pressure swing adsorption devices are large in volume and it is difficult to obtain pure hydrogen. Summary of the Invention

[0003] The purpose of the present invention is to provide a novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membranes, which can solve the problems of methane reforming and hydrogen purification, and has simple control and is easy to obtain pure hydrogen.

[0004] To achieve the above purpose, a novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membranes of the present invention includes a tubular reformer. The tubular reformer includes an outer tube, an inner tube, and the inner tube is sleeved inside the outer tube. The bottoms of both the inner tube and the outer tube are closed. The space between the bottom of the inner tube and the bottom of the outer tube is a reforming chamber cavity. A porous reforming catalyst is filled between the outer surface of the inner tube wall and the inner surface of the outer tube wall. When appropriate methane molecules are mixed with water vapor and oxygen in a certain proportion and enter the space between the inner tube and the outer tube and contact the reforming catalyst, an autothermal reforming chemical reaction will occur. The inner tube is a proton-electron mixed conductor ceramic membrane, and through an electrode reaction, the hydrogen generated in the reforming chamber cavity can be transported into the inner tube to obtain pure hydrogen. The outer tube is a carbonate-electron mixed conductor ceramic membrane, and through an electrode reaction, the carbon dioxide and oxygen generated in the reforming chamber cavity can be transported to the outside of the outer tube, thereby realizing the separation of carbon dioxide.

[0005] As a further aspect of the present invention: For the autothermal reforming chemical reaction, the chemical reaction formula is as follows:

[0006] CH4 + H2O + O2 = 3H2 + CO2 + 0.5O2.

[0007] As a further aspect of the present invention: The electrode reaction occurring on the surface of the proton-electron mixed conductor ceramic membrane close to the reforming chamber cavity, that is, the outer surface of the inner tube, is:

[0008] H2 = 2H + + 2e- ;

[0009] The reverse reaction of the above reaction occurs on the inner surface of the inner tube, thereby obtaining pure hydrogen gas.

[0010] As a further aspect of the present invention: The electrode reaction occurring on the inner surface of the carbonate ion-electron mixed conductor ceramic membrane, which is also the inner surface of the outer tube, is as follows:

[0011] CO2 + H2O + 2e - = H2 + CO3 2- ;

[0012] The hydrogen molecules generated by the above reaction are retained in the reforming chamber; while on the outer surface of the outer tube, the dissociation reaction of carbonate ions occurs, that is:

[0013] CO3 2- = 0.5O2 + CO2 + 2e - .

[0014] As a further aspect of the present invention: The proton-electron mixed conductor ceramic membrane is a dense membrane formed by the mixed sintering of a proton conductor and an electron conductor, and the carbonate ion-electron mixed conductor ceramic membrane is a dense membrane formed by absorbing molten carbonate in a porous membrane formed by the mixed sintering of potassium meta-aluminate and an electron conductor.

[0015] As a further aspect of the present invention: The electron conductor is a conductive ceramic that does not shrink during reduction and is chemically compatible with other materials, or is NiO that shrinks during reduction and is transformed into metal Ni particles during reduction; the composition of the proton conductor is a solid solution of barium zirconate and barium cerate, and can be doped with rare earth ions Y, Yb, Sc, Nb, and Hf.

[0016] As a further aspect of the present invention: The carbonate ion-electron mixed conductor ceramic membrane includes a carbonate ion conductor ceramic membrane, and the composition of the carbonate ion conductor ceramic membrane is a mixture of lithium carbonate, sodium carbonate, and potassium carbonate.

[0017] As a further aspect of the present invention: The reforming catalyst uses a Ni-based alloy catalyst supported on porous γ-alumina, and the working temperature is matched with the working temperatures of the proton conductor and the carbonate ion conductor, that is, 600 - 650 °C.

[0018] A novel reformer based on the coupling of a proton conductor and a carbonate conductor ceramic membrane, comprising a flat-plate stack tower reformer, which is formed by sequentially stacking a plurality of flat-plate stack tower repeating units. Each flat-plate stack tower repeating unit includes, from top to bottom, a carbonate electron mixed conductor ceramic membrane I, a proton electron mixed conductor ceramic membrane I, a carbonate electron mixed conductor ceramic membrane II, and a proton electron mixed conductor ceramic membrane II. The carbonate electron mixed conductor ceramic membrane I and the proton electron mixed conductor ceramic membrane I are connected by a connecting plate II, the proton electron mixed conductor ceramic membrane I and the carbonate electron mixed conductor ceramic membrane II are connected by a connecting plate I, and the carbonate electron mixed conductor ceramic membrane II and the proton electron mixed conductor ceramic membrane II are connected by a connecting plate III. The connecting plate I, the connecting plate II, and the connecting plate III each include a plurality of uniformly distributed ribs. A reforming chamber is formed between the proton electron mixed conductor ceramic membrane I and the carbonate electron mixed conductor ceramic membrane II to carry out the chemical reaction of autothermal reforming. The connecting plate II and the connecting plate III are each composed of two half-connecting plates combined back to back. One side of the half-connecting plate has ribs and the other side is a plane. The plane sides of the two half-connecting plates are in contact with each other to form the connecting plate II or the connecting plate III. The side of the connecting plate II close to the proton electron mixed conductor ceramic membrane I is the pure hydrogen side, and the side close to the carbonate electron mixed conductor ceramic membrane I is the carbon dioxide channel. The side of the connecting plate III close to the proton electron mixed conductor ceramic membrane II is the pure hydrogen side, and the side close to the carbonate electron mixed conductor ceramic membrane II is the carbon dioxide channel.

[0019] As a further solution of the present invention: For the flat-plate stack tower reformer, a raw natural gas inlet, a pure hydrogen outlet, and a carbon dioxide outlet are provided on the end plate of the reformer, and these inlets and outlets can be connected to external pipelines to realize the functions of the reformer.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: The chemical reaction of reforming and the electrode reactions of the proton electron mixed conductor ceramic membrane and the carbonate electron mixed conductor ceramic membrane of the present invention can be coupled and carried out simultaneously. The purification of hydrogen and the separation of the product carbon dioxide are realized in one step at high temperature by using the ceramic membrane. Since a proton electron mixed conductor ceramic membrane is adopted, this reformer only needs heat energy to ensure the working temperature, does not require additional consumption of electrolytic electric energy, is simple to control, is easy to obtain pure hydrogen, has high thermal efficiency, and has a high purity of hydrogen products. The working temperature of the proton conductor ceramic is 600-650°C, which is equivalent to the working temperature of the molten carbonate fuel cell electrolyte, and the coupling is very good, and a suitable gas separation flux can be obtained. Description of the Drawings

[0021] Figure 1 It is a schematic structural diagram of the tubular reformer of the present invention.

[0022] Figure 2 It is a schematic structural view of a flat stack tower - type repeating unit in the present invention.

[0023] Figure 3 It is a schematic structural view of a flat stack tower - type reformer in the present invention.

[0024] In the figure: 1. Outer tube, 2. Reforming chamber cavity, 3. Reforming catalyst, 4. Inner tube, 5. Connecting plate III, 6. Connecting plate I, 7. Connecting plate II, 8. Carbonate - electron mixed - conductor ceramic membrane I, 9. Rib, 10. Proton - electron mixed - conductor ceramic membrane I, 11. Proton - electron mixed - conductor ceramic membrane II, 12. Carbonate - electron mixed - conductor ceramic membrane II, 13. Hydrogen outlet, 14. Natural gas inlet, 15. Carbon dioxide outlet. Detailed implementation mode

[0025] The present invention will be further described below in conjunction with the accompanying drawings.

[0026] As Figure 1 shown, the tubular reformer in the present invention includes an outer tube 1 and an inner tube 4. The inner tube 4 is sleeved inside the outer tube 1. The bottoms of both the inner tube 4 and the outer tube 1 are closed. The reforming chamber cavity 2 is located between the bottom of the inner tube 4 and the bottom of the outer tube 1. Porous reforming catalyst 3 is filled between the outer surface of the inner tube wall and the inner surface of the outer tube wall. When appropriate methane molecules are mixed with steam and oxygen in a certain proportion and enter the space between the inner tube 4 and the outer tube 1 and contact the reforming catalyst 3, an autothermal reforming chemical reaction will occur. The advantage of autothermal reforming is that the endothermic steam reforming reaction and the exothermic partial oxidation reforming reaction occur simultaneously, and the heat is just complementary, making the reaction easy to occur. The inner tube 4 is a proton - electron mixed - conductor ceramic membrane, and through the electrode reaction, the hydrogen generated in the reforming chamber cavity 2 can be transported into the inner tube 4 to obtain pure hydrogen. The outer tube 1 is a carbonate - electron mixed - conductor ceramic membrane, and through the electrode reaction, the carbon dioxide and oxygen generated in the reforming chamber cavity 2 can be transported to the outside of the outer tube 1, thus realizing the separation of carbon dioxide. In the reformer of the present invention, the reforming chemical reaction and the electrochemical reactions of inner and outer tube membrane separation are coupled and carried out simultaneously. By using the proton - electron mixed - conducting ceramic membrane of the inner tube and the carbonate - electron mixed ceramic membrane of the outer tube, the purification of hydrogen and the separation of the product carbon dioxide are achieved in one step at high temperature.

[0027] The reaction formula of the reforming chemical reaction is as follows:

[0028] CH4 + H2O + O2 = 3H2 + CO2 + 0.5O2;

[0029] The electrode reaction occurring on the surface of the proton - electron mixed - conductor ceramic membrane near the reforming chamber cavity 2, that is, the outer surface of the inner tube 4, is:

[0030] H2 = 2H + + 2e- ;

[0031] The reverse reaction of the above reaction occurs on the inner surface of the inner tube 4, thereby obtaining pure hydrogen gas;

[0032] The electrode reaction occurring on the inner surface of the carbonate electron mixed conductor ceramic membrane, which is also the inner surface of the outer tube 1, is:

[0033] CO2 + H2O + 2e - = H2 + CO3 2- ;

[0034] The hydrogen molecules generated by the above reaction are retained in the reforming chamber 2; while on the outer surface of the outer tube 1, the dissociation reaction of carbonate occurs, that is:

[0035] CO3 2- = 0.5O2 + CO2 + 2e - ;

[0036] To facilitate the smooth progress of this carbonate dissociation reaction, air purge can be used when necessary to reduce the CO2 partial pressure on the surface of the carbonate electron mixed conductor ceramic membrane, thereby reducing the chemical potential of carbonate ions on the air side.

[0037] The proton-electron mixed conductor ceramic membrane is a dense membrane formed by the mixed sintering of a proton conductor and an electron conductor. The carbonate electron mixed conductor ceramic membrane is a dense membrane formed by absorbing molten carbonate on a porous membrane formed by the mixed sintering of potassium metaaluminate and an electron conductor.

[0038] The electron conductor is a conductive ceramic that does not shrink during reduction and is chemically compatible with other materials, or it is NiO that shrinks during reduction and transforms into metallic Ni particles during reduction, having high electrical conductivity and thermal conductivity. When using NiO as the raw material of the conductive ceramic to fabricate the proton-electron mixed conductive ceramic membrane, it needs to be sintered in a reducing atmosphere to ensure obtaining a mixed dense membrane of ceramic proton conductor and Ni. When preparing the porous membrane of lithium metaaluminate and Ni electron conductor, it is sintered in an air atmosphere and then reduced. The electrode material can be Ni-BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb1711), Ni-BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ (BZCYYb4411), Ni-BaZr 0.8 Y 0.2 O 3-δ (BZY20), etc.

[0039] The composition of the proton conductor is a solid solution of barium zirconate and barium cerate, and it can be doped with rare earth ions with smaller ionic radii such as Y, Yb, Sc, Nb, and Hf to improve its proton conductivity. The proton electrolytes are: BZCYYb1711, BZCYYb4411, BZY20, BaCe 0.8 Y 0.2 O 3-δ (BCY20), BaZr 0.4 Ce 0.4 Y 0.1 Gd 0.1 O 3-δ (BZCYG4411), where the ratio of Zr ions and Ce ions should fully consider their stability in the reforming gas containing CO2, higher proton conductivity, and good sintering activity.

[0040] The carbonate ion-electron mixed conductor ceramic membrane includes a carbonate conductor ceramic membrane. The composition of the carbonate conductor ceramic membrane is a mixture of lithium carbonate, sodium carbonate, and potassium carbonate. The adjustment of their mutual ratio should take into account both higher carbonate ion conductivity and sufficient viscosity to ensure that under a small pressure difference, the molten carbonate can be maintained inside the pores of the porous lithium metaaluminate by capillary force and maintain airtightness.

[0041] Autothermal reforming is adopted. The reforming catalyst for autothermal reforming is a Ni-based alloy catalyst supported on porous γ-alumina, and its operating temperature is matched with the operating temperatures of the proton conductor and the carbonate ion conductor, that is, 600 - 650 °C.

[0042] An electrocatalyst is provided on the outer surface of the inner tube.

[0043] Example 1

[0044] With Figure 1 the single-tube structure shown, a portable reformer for small-scale hydrogen production can be realized. Among them, the average inner diameter of the inner tube is 20 mm, the average outer diameter of the outer tube is 30 mm, the effective working tube length is 300 mm. By adjusting the wall thicknesses of the inner tube and the outer tube to be less than 100 microns, and the electrocatalyst modified on the outer surface of the inner tube, the hydrogen permeation rate per unit effective area reaches 0.023 ml·cm -2 s -1 (equivalent to a current density of 200 mA·cm -2 ), then 260 ml of hydrogen can be produced per minute, corresponding to the treatment of 86.7 ml of methane, and 86.7 ml of CO2 is collected at the same time.

[0045] Example 2

[0046] As Figure 2The figure shows a schematic cross-section of a flat plate stacked tower repeating unit, which successively includes a carbonate ion-electron mixed conductor ceramic membrane I8, a proton-electron mixed conductor ceramic membrane I10, a carbonate ion-electron mixed conductor ceramic membrane II12, and a proton-electron mixed conductor ceramic membrane II11 from top to bottom. The carbonate ion-electron mixed conductor ceramic membrane I8 and the proton-electron mixed conductor ceramic membrane I10 are connected by a connecting plate II7. The proton-electron mixed conductor ceramic membrane I10 and the carbonate ion-electron mixed conductor ceramic membrane II12 are connected by a connecting plate I6. The carbonate ion-electron mixed conductor ceramic membrane II12 and the proton-electron mixed conductor ceramic membrane II11 are connected by a connecting plate III5. The connecting plate I6, the connecting plate II7, and the connecting plate III5 all include a number of uniformly distributed ribs 9, and the ribs play a role in supporting strength. The connecting plate I6 does not need to isolate gas and is a connecting plate for the reforming chamber. A reforming chamber is formed between the proton-electron mixed conductor ceramic membrane I10 and the carbonate ion-electron mixed conductor ceramic membrane II12 for the chemical reaction of autothermal reforming. The connecting plate II7 and the connecting plate III5 are connecting plates that need to isolate gas. Therefore, the connecting plate II7 and the connecting plate III5 are both composed of two half-connecting plates combined back to back. One side of the half-connecting plate has ribs and the other side is flat. The flat sides of the two half-connecting plates are in contact with each other to form the connecting plate II7 or the connecting plate III5. The side of the connecting plate II7 close to the proton-electron mixed conductor ceramic membrane I8 is the pure hydrogen side, and the side close to the carbonate ion-electron mixed conductor ceramic membrane I10 is the carbon dioxide channel. The side of the connecting plate III5 close to the proton-electron mixed conductor ceramic membrane II11 is the pure hydrogen side, and the side close to the carbonate ion-electron mixed conductor ceramic membrane II12 is the carbon dioxide channel.

[0047] As Figure 3 shown, N flat plate stacked tower repeating units are successively stacked to form a flat plate stacked tower reformer. A raw natural gas inlet 14, a pure hydrogen outlet 13, and a carbon dioxide outlet 15 are provided on the end plate of the reformer. Through these inlets and outlets, connection with external pipelines can be achieved, thereby realizing the function of the reformer. This module can achieve large-scale hydrogen production. If a module containing 100 stacked towers can be integrated, its hydrogen production capacity will reach 41.4 m 3 per hour. This hydrogen production capacity is expected to drive the stable operation of an 80 kW fuel cell stack.

[0048] For a repeating unit with an effective area of 100 cm 2 , using 50 repeating units to form a stacked tower, at the same ion current density as in Example 1, the hydrogen production capacity of this stacked tower can reach 6.9 L per minute, or 0.414 m per hour 3 .

Claims

1. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane, characterized in that: The invention comprises a tubular reformer, wherein the tubular reformer comprises an outer tube (1), an inner tube (4), the inner tube (4) being sleeved inside the outer tube (1), the bottom of the inner tube (4) and the bottom of the outer tube (1) being both closed, a reforming chamber (2) being located between the bottom of the inner tube (4) and the bottom of the outer tube (1), and a porous reforming catalyst (3) being filled between the outer surface of the inner tube wall and the inner surface of the outer tube wall; when appropriate methane molecules are mixed with water vapor and oxygen in a certain proportion and enter the space between the inner tube (4) and the outer tube (1) and contact the reforming catalyst (3), a chemical reaction of autothermal reforming will occur; the inner tube (4) is a proton-electron mixed conductor ceramic membrane, and hydrogen generated in the reforming chamber (2) can be transmitted to the inner tube (4) through electrode reaction to obtain pure hydrogen; the outer tube (1) is a carbonate-electron mixed conductor ceramic membrane, and carbon dioxide and oxygen generated in the reforming chamber (2) can be transmitted to the outside of the outer tube (1) through electrode reaction, thereby realizing the separation of carbon dioxide.

2. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 1, characterized in that: The chemical reaction of the autothermal reforming is as follows: CH4+H2O+O2=3H2+CO2+0.5O2.

3. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 1, characterized in that: The electrode reaction occurring on the surface of the proton-electron mixed conductor ceramic membrane close to the reforming chamber cavity (2), i.e., the outer surface of the inner tube (4) is: <h2 style=";text-align:left;direction:ltr">H2=2H<h2 style=";text-align:left;direction:ltr"> + <h2 style=";text-align:left;direction:ltr"> +2e<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ; The reverse reaction of the above reaction occurs on the inner surface of the inner tube (4), thereby obtaining pure hydrogen.

4. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 1, characterized in that: The electrode reaction occurring on the inner surface of the carbonate electron mixed conductor ceramic membrane, i.e., the inner surface of the outer tube (1), is: <h2 style=";text-align:left;direction:ltr">CO2+H2O+2e<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> (H2+CO3)<h2 style=";text-align:left;direction:ltr"> 2- <h2 style=";text-align:left;direction:ltr"> ; The hydrogen molecules produced by the above reaction are retained in the reforming chamber (2); while on the outer surface of the outer tube (1), a dissociation reaction of carbonate radicals occurs, namely: <h2 style=";text-align:left;direction:ltr">CO3<h2 style=";text-align:left;direction:ltr"> 2- <h2 style=";text-align:left;direction:ltr"> =0.5O2+CO2+2e<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> 。 5. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 1, characterized in that: The proton-electron mixed conductor ceramic membrane is a dense membrane formed by sintering a proton conductor and an electronic conductor, and the carbonate-electron mixed conductor ceramic membrane is a dense membrane formed by sintering a porous membrane formed by absorbing molten carbonate and mixed with potassium aluminate and an electronic conductor.

6. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 5, characterized in that: The electron conductor is a conductive ceramic that does not shrink during reduction and is chemically compatible with other materials, or NiO that shrinks during reduction and is converted into metallic Ni particles during reduction; the proton conductor is a solid solution of barium zirconate and barium cerate, and can be doped with rare earth ions Y, Yb, Sc, Nb, and Hf.

7. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 5, characterized in that: The carbonate electron mixed conductor ceramic membrane comprises a carbonate conductor ceramic membrane, and the carbonate conductor ceramic membrane is a mixture of lithium carbonate, sodium carbonate and potassium carbonate.

8. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 1, characterized in that: The reforming catalyst adopts a Ni-based alloy catalyst supported by porous gamma alumina, and the working temperature matches the working temperature of the proton conductor and the carbonate ion conductor, that is, 600-650°C.

9. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane, characterized in that: The invention also comprises a flat plate stack tower reformer, wherein the flat plate stack tower reformer is formed by stacking a plurality of flat plate stack tower repeating units in sequence, wherein the flat plate stack tower repeating units comprise, from top to bottom, a carbonate electron mixed conductor ceramic membrane I (8), a proton electron mixed conductor ceramic membrane I (10), a carbonate electron mixed conductor ceramic membrane II (12), and a proton electron mixed conductor ceramic membrane II (11), wherein the carbonate electron mixed conductor ceramic membrane I (8) is connected to the proton electron mixed conductor ceramic membrane I (10) via a connecting plate II (7), the proton electron mixed conductor ceramic membrane I (10) is connected to the carbonate electron mixed conductor ceramic membrane II (12) via a connecting plate I (6), the carbonate electron mixed conductor ceramic membrane II (12) is connected to the proton electron mixed conductor ceramic membrane II (11) via a connecting plate III (5), and the connecting plate I (6), the connecting plate II (7), the connecting plate II (8), the connecting plate II (9), the connecting plate II (11), the connecting plate III (12), the connecting plate III (13), the connecting plate III (14), the connecting plate III (15), the connecting plate III (16), the connecting plate II (17), the connecting plate III (18), the connecting plate III (19), the connecting plate III (20), the connecting plate III (21), the connecting plate III (22), the connecting plate III (23), the connecting plate III (24), the connecting plate III (25), the connecting plate III (26), the connecting plate III (27), the connecting plate III (28), the connecting plate III (29), the connecting plate III (30), the connecting plate III (31), the connecting plate III (32), the connecting plate III (33), the connecting plate III (34), the connecting plate III (35), the connecting plate III (36), the connecting plate III (37), the connecting plate III (38), the connecting plate III (39), the connecting plate III (40), the connecting plate III (41), the connecting plate III (42), the connecting plate III (43), the connecting plate III (4 The plates III (5) each include a plurality of uniformly distributed ribs (9); a reforming chamber is formed between the proton-electron mixed conductor ceramic membrane I (10) and the carbonate-electron mixed conductor ceramic membrane II (12) to carry out a chemical reaction of autothermal reforming; the connecting plate II (7) and the connecting plate III (5) are each formed by two half connecting plates assembled back to back, one side of the half connecting plate is provided with ribs and the other side is a plane, the plane sides of the two half connecting plates are in contact with each other to form the connecting plate II (7) or the connecting plate III (5); the side of the connecting plate II (7) close to the proton-electron mixed conductor ceramic membrane I (8) is a pure hydrogen side, and the side close to the carbonate-electron mixed conductor ceramic membrane I (10) is a channel for carbon dioxide; the side of the connecting plate III (5) close to the proton-electron mixed conductor ceramic membrane II (11) is a pure hydrogen side, and the side close to the carbonate-electron mixed conductor ceramic membrane II (12) is a channel for carbon dioxide.

10. A novel reformer based on the coupling of proton conductor and carbonate conductor ceramic membrane according to claim 9, characterized in that: The flat-plate tower reformer is provided with a raw natural gas inlet (14), a pure hydrogen outlet (13), and a carbon dioxide outlet (15) on the end plate of the reformer.

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