A proton ceramic membrane reactor and its preparation method and application

Abstract

The present invention belongs to the technical field of resource utilization of methane and carbon dioxide, and specifically relates to a proton ceramic membrane reactor, its preparation method and application. The proton ceramic membrane reactor comprises the following components in parts by weight: a first slurry, a second slurry, a third slurry, and a fourth slurry. The proton ceramic membrane reactor prepared by the present invention can effectively overcome the problems existing in the existing SOEC direct electrolysis of carbon dioxide. It couples the hydrogen production by methane and carbon dioxide reforming reaction with the electrothermal synergistic catalytic carbon dioxide conversion technology, while reducing resource waste and greenhouse effect, and efficiently converting and producing low-carbon alcohols.

Description

Technical Field

[0001] The present invention belongs to the technical field of methane and carbon dioxide resource utilization, and specifically relates to a proton ceramic membrane reactor and a preparation method and application thereof. Background Art

[0002] The development of efficient mining, collection and utilization technologies for coal-based greenhouse gases methane and carbon dioxide is the main means to achieve carbon emission reduction in coal-fired power generation and coal chemical industries, and can significantly reduce greenhouse gas emissions.

[0003] The efficient and clean utilization of coal-based greenhouse gases is actually the conversion and utilization of methane, which is usually converted into synthesis gas, and then the synthesis gas is used to prepare low-value fuels. However, this process is complex and has high technical requirements, making it difficult to achieve. Solid oxide fuel electrolyzers are energy conversion devices that can directly and efficiently convert thermal energy and electrical energy into chemical energy. They have the advantages of high energy density, environmental friendliness, and sustainable operation. They have good application prospects in energy conversion and storage. With the vigorous development of renewable energy, combining electricity generated by renewable energy with solid oxide fuel electrolyzers, high-temperature catalytic dry reforming of methane and carbon dioxide in coal-based greenhouse gases and electrothermal catalytic coupling of carbon dioxide to prepare low-value liquid fuels that are easy to store and transport is an effective way to achieve resource utilization of coal-based greenhouse gases. Summary of the Invention

[0004] The present invention aims to provide a proton ceramic membrane reactor, its preparation method, and its application. This proton ceramic membrane reactor overcomes the difficulties and low efficiency of existing SOEC (solid-organic carbon dioxide electrolysis) methods for direct carbon dioxide electrolysis. By coupling hydrogen production from methane and carbon dioxide reforming reactions with electrothermal synergistic catalytic carbon dioxide conversion technology, it produces low-carbon alcohols while reducing resource waste and greenhouse gas emissions.

[0005] In order to achieve the above object, the present invention adopts the following technical solution: a proton ceramic membrane reactor, comprising the following components in parts by weight:

[0006] First slurry: 35-45 parts NiO, 25-35 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 0.5-1.5 parts dispersant, 5-10 parts binder, 20-30 parts solvent;

[0007] Second slurry: 30-40 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ, 3 to 6 parts of binder, 56 to 59 parts of solvent;

[0008] Third slurry: 20-25 parts NiO, 15-20 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 3 to 6 parts of binder, 56 to 59 parts of solvent;

[0009] Fourth slurry: 35-45 parts M x Ce 1-x O 2-δ (M=Ni,Ru,Fe), 3 to 6 parts of binder, and 56 to 59 parts of solvent.

[0010] Preferably, the proton ceramic membrane reactor comprises at least one of the following items (1) to (3):

[0011] (1) The dispersant in the first slurry is polyvinyl pyrrolidone;

[0012] (2) The binder is at least one of polyvinyl butyral, polyethylene glycol, polyethersulfone resin, and ethyl cellulose;

[0013] (3) The solvent is at least one of 1-methyl-2-pyrrolidone, terpineol, ethanol, butanone, and acetone.

[0014] A method for preparing the proton ceramic membrane reactor comprises the following steps:

[0015] S1. Prepare cathode support voxel embryos from the first slurry by a phase inversion method, and then dry and sinter them to obtain a reactor cathode;

[0016] S2, coating the second slurry on the cathode surface by spin coating, and forming a proton membrane after sintering;

[0017] S3, printing the third slurry on the surface of the proton membrane and sintering to obtain a proton membrane ceramic reactor anode;

[0018] S4, printing the fourth slurry on the anode surface of the proton membrane reactor and sintering to form an anode catalyst layer;

[0019] S5. The Fe-based thermal catalyst solution is impregnated in the cathode of the reactor, pre-fired after each impregnation, and sintered after the impregnation is completed to obtain an impregnated proton membrane ceramic reactor.

[0020] Preferably, the structural layers of the proton ceramic membrane reactor from inside to outside are reactor cathode, proton membrane, proton membrane ceramic reactor anode, and anode catalyst layer.

[0021] Preferably, the preparation method includes at least one of the following (1) to (4):

[0022] (1) In step S1, the sintering temperature is 1000-1100° C., and the sintering time is 2-4 hours;

[0023] (2) In step S2, the sintering temperature is 1400-1500° C., and the sintering time is 6-10 hours;

[0024] (3) In steps S3 and S4, the sintering temperature is 950-1100° C. and the sintering time is 2-4 hours;

[0025] (4) In step S5, the sintering temperature is 700-800° C. and the sintering time is 2-4 hours;

[0026] Preferably, the preparation method includes at least one of the following (1) to (4):

[0027] (1) The thickness of the cathode of the reactor is 600 to 800 μm;

[0028] (2) The thickness of the proton membrane is 8 to 15 μm;

[0029] (3) The thickness of the anode of the proton membrane ceramic reactor is 25 to 35 μm;

[0030] (4) The thickness of the anode catalyst layer is 40 to 60 μm.

[0031] Preferably, the step of impregnating the Fe-based thermal catalyst is:

[0032] a. Weigh 0 to 20 wt% iron nitrate, 0 to 20 wt% copper nitrate, and the remainder cerium nitrate reagent according to weight percentage to prepare an aqueous solution having a concentration of 0.01 to 0.1 mol / L;

[0033] b. The Fe-based catalyst was loaded into the cathode straight-hole microchannels by vacuum adsorption-assisted impregnation for 3 to 10 times. After each impregnation, the battery was pre-calcined at 400 to 600°C for 0.5 to 3 hours to decompose the nitrate, and the change in battery weight was recorded.

[0034] An application of the proton ceramic membrane reactor in preparing low-carbon alcohols, wherein the preparation of low-carbon alcohols comprises the following steps:

[0035] A. Pass hydrogen into the anode of the proton ceramic membrane reactor and reduce it at 600-700℃ for 3-5h;

[0036] B. Prepare a mixture of methane and carbon dioxide as anode fuel;

[0037] C. The prepared anode fuel is introduced into the anode of the proton ceramic membrane reactor, and carbon dioxide is introduced into the cathode of the proton ceramic membrane reactor. At 300-600°C, by applying an external voltage, the hydrogen ions released at the anode pass through the proton membrane to reach the cathode to generate high-purity hydrogen. The thermal catalyst loaded on the cathode straight-hole microchannel uses electric heat to synergistically catalyze the conversion of carbon dioxide into low-carbon alcohols.

[0038] Preferably, the application of the proton ceramic membrane reactor in the preparation of low-carbon alcohols includes at least one of the following (1) to (2):

[0039] (1) The volume content of methane is 10% to 90% of the total volume of the anode fuel;

[0040] (2) The external voltage is 1.2 to 2V.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The present invention adds a layer of fourth slurry on the surface of the anode. Under the action of an external voltage, the proton selective transmission of the proton ceramic membrane reactor is used to achieve efficient hydrogen production. At the same time, it can be coupled with the CO2 at the cathode of the proton ceramic membrane reactor, and under the action of the Fe-based thermal catalyst loaded on the cathode gradient straight hole microchannel, the electrothermal synergistic catalytic CO2 conversion to produce low-carbon alcohols is achieved. By using coal-based greenhouse gases methane and carbon dioxide as fuel, high-value-added utilization of methane and carbon dioxide is achieved, thereby reducing resource waste and greenhouse effect.

[0043] (2) The present invention can effectively improve the efficiency of hydrogen production from methane and carbon dioxide reforming and the stability of the proton ceramic reactor by controlling the ratio of methane and carbon dioxide;

[0044] (3) In the present invention, methane and carbon dioxide produce synthesis gas under the action of catalyst and self-reforming. An external power source dissociates the hydrogen in the synthesis gas into protons, which pass through the proton membrane to reach the cathode side and generate hydrogen under the action of the catalyst, thereby realizing the separation of hydrogen. The hydrogen is then catalyzed by electrothermal synergy with carbon dioxide at the cathode to generate low-carbon alcohols. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is a schematic structural diagram of the proton ceramic membrane reactor of the present invention.

[0046] Figure 2 This is a diagram showing the working principle of the proton ceramic membrane reactor of the present invention for preparing low-carbon alcohols.

[0047] Figure 3 This is a microstructure diagram of the proton ceramic membrane reactor of the present invention.

[0048] Figure 4The products of dry reforming reaction in proton ceramic membrane reactors at different methane and carbon dioxide ratios in Example 1 of the present invention and Comparative Examples 1 to 3 are shown.

[0049] Figure 5 The selectivity of low-carbon alcohols in the proton ceramic membrane reactors of Example 1 of the present invention and Comparative Examples 1 to 3 is shown.

[0050] Among them: 1. Anode catalyst layer; 2. Anode; 3. Proton membrane; 4. Cathode. DETAILED DESCRIPTION

[0051] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0052] In the Examples and Comparative Examples, the experimental methods used are conventional methods unless otherwise specified, and the materials and reagents used are commercially available unless otherwise specified.

[0053] Example 1: Proton ceramic membrane reactor and its preparation method

[0054] Components: First slurry: 41 parts NiO, 27 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 0.5 parts of polyvinyl pyrrolidone, 5 parts of polyethylene glycol, 26 parts of terpineol;

[0055] Second slurry: 38 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 3 parts of polyethylene glycol, 59 parts of terpineol;

[0056] The third slurry: 23 parts NiO, 15 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 3 parts of polyethylene glycol, 59 parts of terpineol;

[0057] Fourth slurry: 38 parts Ni 0.5 Ce 0.5 O 2-δ (NCO), 3 parts of polyethylene glycol, 59 parts of terpineol.

[0058] The Ni0.5 Ce 0.5 O 2-δ Preparation method: 10.443g nickel acetate and 16.3065g cerium nitrate were added to 200g deionized water, stirred evenly, 31.521g citric acid and 25ml nitric acid were added, the pH value was adjusted to 7 with ammonia water, the solution was heated until spontaneous combustion occurred, and the powder obtained after combustion was calcined in an air atmosphere at 1000℃ for 3h to obtain Ni 0.5 Ce 0.5 O 2-δ .

[0059] Preparation method of proton ceramic membrane reactor:

[0060] S1. Prepare cathode support voxel embryos from the first slurry by phase inversion method, dry them, and sinter them at 1050° C. for 3 h to obtain a reactor cathode;

[0061] S2, coating the second slurry on the cathode surface by spin coating, and sintering at 1450° C. for 6 h to form a proton membrane;

[0062] S3, printing the third slurry on the surface of the proton membrane, and sintering at 1000° C. for 3 h to obtain a proton membrane ceramic reactor anode;

[0063] S4, printing the fourth slurry on the anode surface of the proton membrane reactor, and sintering at 1000° C. for 3 h to form an anode catalyst layer;

[0064] S5, Fe-based thermal catalyst solution was impregnated in the cathode of the reactor, pre-fired after each impregnation, and sintered at 800°C for 3h after impregnation to obtain an impregnated proton membrane ceramic reactor.

[0065] Furthermore, the step of impregnating the Fe-based thermal catalyst is:

[0066] a. Weigh 20wt% iron nitrate, 20wt% copper nitrate, and the remainder cerium nitrate reagent according to weight percentage to prepare an aqueous solution having a concentration of 0.03mol / L;

[0067] b. The Fe-based catalyst was loaded into the cathode straight-hole microchannels by vacuum adsorption-assisted impregnation for five times. After each impregnation, the cells were pre-calcined at 500°C for 1 hour to decompose the nitrate, and the battery weight change was recorded.

[0068] Example 2: Proton ceramic membrane reactor and its preparation method

[0069] Components: First slurry: 45 parts NiO, 35 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ, 1.5 parts of polyvinyl pyrrolidone, 10 parts of polyethylene glycol, 30 parts of terpineol;

[0070] Second slurry: 40 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 6 parts of polyethylene glycol, 58 parts of terpineol;

[0071] The third slurry: 25 parts NiO, 20 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 6 parts of polyethylene glycol, 58 parts of terpineol;

[0072] Fourth slurry: 45 parts Ni 0.5 Ce 0.5 O 2-δ , 6 parts of polyethylene glycol, 58 parts of terpineol.

[0073] The Ni 0.5 Ce 0.5 O 2-δ Preparation method: 10.443g nickel acetate and 16.3065g cerium nitrate were added to 200g deionized water, stirred evenly, 31.521g citric acid and 25ml nitric acid were added, the pH value was adjusted to 7 with ammonia water, the solution was heated until spontaneous combustion occurred, and the powder obtained after combustion was calcined in an air atmosphere at 1000℃ for 3h to obtain Ni 0.5 Ce 0.5 O 2-δ .

[0074] Preparation method of proton ceramic membrane reactor:

[0075] S1. Prepare cathode support voxel embryos from the first slurry by phase inversion method, dry them, and sinter them at 1100° C. for 2 h to obtain a reactor cathode;

[0076] S2, coating the second slurry on the cathode surface by spin coating, and sintering at 1500° C. for 8 h to form a proton membrane;

[0077] S3, printing the third slurry on the surface of the proton membrane, and sintering at 1100° C. for 2 h to obtain a proton membrane ceramic reactor anode;

[0078] S4, printing the fourth slurry on the anode surface of the proton membrane reactor, and sintering at 1100° C. for 2 h to form an anode catalyst layer;

[0079] S5, Fe-based thermal catalyst solution was impregnated in the cathode of the reactor, pre-fired after each impregnation, and sintered at 800°C for 2h after impregnation to obtain an impregnated proton membrane ceramic reactor.

[0080] Furthermore, the step of impregnating the Fe-based thermal catalyst is:

[0081] a. Weigh 20wt% copper nitrate according to weight percentage, and the rest is cerium nitrate reagent, configured to a concentration of 0.1mol / L of aqueous solution;

[0082] b. The Fe-based catalyst was loaded into the cathode straight-hole microchannels by vacuum adsorption-assisted impregnation three times. After each impregnation, the cells were pre-calcined at 400°C for 3 h to decompose the nitrate, and the battery weight change was recorded.

[0083] Example 3: Proton ceramic membrane reactor and its preparation method

[0084] Components: First slurry: 35 parts NiO, 25 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 1.0 part polyvinyl pyrrolidone, 7 parts polyethylene glycol, 20 parts terpineol;

[0085] Second slurry: 30 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 5 parts of polyethylene glycol, 56 parts of terpineol;

[0086] The third slurry: 20 parts NiO, 18 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 5 parts of polyethylene glycol, 56 parts of terpineol;

[0087] Fourth slurry: 35 parts Ni 0.5 Ce 0.5 O 2-δ , 5 parts of polyethylene glycol, 56 parts of terpineol.

[0088] The Ni 0.5 Ce 0.5 O 2-δPreparation method: 10.443g nickel acetate and 16.3065g cerium nitrate were added to 200g deionized water, stirred evenly, 31.521g citric acid and 25ml nitric acid were added, the pH value was adjusted to 7 with ammonia water, the solution was heated until spontaneous combustion occurred, and the powder obtained after combustion was calcined in an air atmosphere at 1000℃ for 3h to obtain Ni 0.5 Ce 0.5 O 2-δ .

[0089] Preparation method of proton ceramic membrane reactor:

[0090] S1. Prepare cathode support voxel embryos from the first slurry by phase inversion method, dry them, and sinter them at 1000° C. for 4 h to obtain a reactor cathode;

[0091] S2, coating the second slurry on the cathode surface by spin coating, and sintering at 1400° C. for 10 h to form a proton membrane;

[0092] S3, printing the third slurry on the surface of the proton membrane, and sintering at 950° C. for 4 h to obtain a proton membrane ceramic reactor anode;

[0093] S4, printing the fourth slurry on the anode surface of the proton membrane reactor, and sintering at 950° C. for 4 hours to form an anode catalyst layer;

[0094] S5, Fe-based thermal catalyst solution was impregnated in the cathode of the reactor, pre-fired after each impregnation, and sintered at 700°C for 4h after impregnation to obtain an impregnated proton membrane ceramic reactor.

[0095] Furthermore, the step of impregnating the Fe-based thermal catalyst is:

[0096] a. Weigh 10wt% iron nitrate, 10wt% copper nitrate, and the remainder cerium nitrate reagent according to weight percentage to prepare an aqueous solution having a concentration of 0.01mol / L;

[0097] b. The Fe-based catalyst was loaded into the cathode straight-hole microchannels by vacuum adsorption-assisted impregnation for 10 times. After each impregnation, the cells were pre-calcined at 600°C for 0.5 h to decompose the nitrates, and the battery weight change was recorded.

[0098] Comparative Example 1

[0099] Compared with Example 1, the difference of this comparative example is that the proton ceramic membrane reactor lacks the fourth slurry component.

[0100] For other preparation methods, refer to Example 1.

[0101] Comparative Example 2

[0102] Compared with Example 1, the difference of this comparative example is that the operation of impregnating the Fe-based thermal catalyst is missing in step S5.

[0103] Other components and preparation methods refer to Example 1.

[0104] Comparative Example 3

[0105] Compared with Example 1, the difference of this comparative example is that the fourth slurry component is missing in the proton ceramic membrane reactor, and the operation of impregnating the Fe-based thermal catalyst is missing in step S5.

[0106] Other components and preparation methods are as shown in Example 1.

[0107] Test Example 1

[0108] The proton ceramic membrane reactors prepared in Example 1 and Comparative Examples 1 to 3 were used to measure the products of dry reforming reactions at different methane and carbon dioxide ratios according to the following method.

[0109] Determination method:

[0110] A. Pass hydrogen into the anode of the proton ceramic membrane reactor and reduce it at 600℃ for 4h;

[0111] B. introducing methane and carbon dioxide gases with different volume ratios into the anode chamber of the proton membrane reactor, and applying an external voltage of 1.5 V while continuously introducing carbon dioxide gas into the cathode;

[0112] C. Collect the anode tail gas at 600℃ and perform gas chromatography analysis;

[0113] D. The switching stabilization time between different components is 8h.

[0114] The experimental results are as follows Figure 4 shown.

[0115] The composition of the tail gas from the proton ceramic membrane reactor in a methane and carbon dioxide fuel atmosphere with different anode volume content ratios was analyzed at a test temperature of 800°C. It can be found that Figure 4 As shown in (a), in Comparative Example 3, no Ni was added to the anode. 0.5 Ce 0.5 O 2-δ Reforming layer, and no Fe-based thermal catalyst was impregnated in the cathode, the catalytic reforming performance of the proton ceramic membrane reactor was significantly poor; Comparative Example 2 added Ni 0.5 Ce 0.5 O 2-δReforming layer, but the cathode is not impregnated with Fe-based thermal catalyst, under different volume ratios of methane and carbon dioxide atmosphere, the proportion of hydrogen and carbon monoxide in the anode tail gas will increase, but the effect is worse than that in Example 1. This shows that the addition of the anode catalyst layer helps the reforming reaction of methane and carbon dioxide to produce synthesis gas. However, if Figure 4 As shown in (b), in Comparative Example 1, even though Fe-based thermal catalyst was added to the cathode, the 0.5 Ce 0.5 O 2-δ The reforming layer results in no significant change in the composition of hydrogen and carbon monoxide in the anode tail gas. This is because the process of reforming methane and carbon dioxide to generate synthesis gas mainly occurs on the anode side.

[0116] Test Example 2: Selective Determination of Low-Carbon Alcohols

[0117] The proton ceramic membrane reactors prepared in Example 1 and Comparative Examples 1 to 3 were tested according to the following method to calculate the selectivity of low-carbon alcohols.

[0118] Detection method:

[0119] A. Pass hydrogen into the anode of the proton ceramic membrane reactor and reduce it at 600℃ for 4h;

[0120] B. A methane and carbon dioxide mixture with a volume content of 50% each was introduced into the anode, and carbon dioxide gas was introduced into the cathode while applying an external voltage of 1.5V;

[0121] C. Collect the anode tail gas at 600℃, perform gas chromatography analysis, and calculate the selectivity of low-carbon alcohols.

[0122] The experimental results are as follows Figure 5 As shown. The exhaust gas composition under different temperatures with or without the cathode impregnated with Fe-based thermal catalyst was analyzed. By calculating the exhaust gas composition, it can be found that the cathode impregnated with Fe-based thermal catalyst has better selectivity for low-carbon alcohols at different test temperatures. At the same time, the cathode with or without Ni added 0.5 Ce 0.5 O 2-δ From the test calculations on the cathode low-carbon alcohol selectivity after the catalytic layer, it was found that the addition of the anode reforming layer helps to increase the cathode low-carbon alcohol selectivity. This is because more protons pass through the proton membrane from the anode to the cathode, reacting with carbon dioxide and its products to form low-carbon alcohols.

[0123] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A method for preparing a proton ceramic membrane reactor, characterized in that: The following steps are involved: S1. Prepare cathode support voxel embryos from the first slurry by a phase inversion method, and then dry and sinter them to obtain a reactor cathode; S2, coating the second slurry on the cathode surface by spin coating, and forming a proton membrane after sintering; S3, printing the third slurry on the surface of the proton membrane and sintering to obtain a proton membrane ceramic reactor anode; S4, printing the fourth slurry on the anode surface of the proton membrane reactor and sintering to form an anode catalyst layer; S5, Fe-based thermal catalyst solution is impregnated in the cathode of the reactor, pre-fired after each impregnation, and sintered after the impregnation is completed to obtain an impregnated proton membrane ceramic reactor; the proton membrane ceramic reactor is a process for preparing low-carbon alcohols by coupling methane and carbon dioxide reforming reaction to produce hydrogen and electrothermal synergistic catalytic carbon dioxide conversion technology; The slurry includes the following components in parts by weight: First slurry: 35~45 parts NiO, 25~35 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 0.5~1.5 parts dispersant, 5~10 parts binder, 20~30 parts solvent; Second slurry: 30~40 parts of BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 3~6 parts binder, 56~59 parts solvent; Third slurry: 20~25 parts NiO, 15~20 parts BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ , 3~6 parts binder, 56~59 parts solvent; Fourth slurry: 35~45 parts M x Ce 1-x O 2-δ , 3 to 6 parts of binder, 56 to 59 parts of solvent; the M is any one of Ni, Ru, and Fe.

2. The method for preparing a proton ceramic membrane reactor according to claim 1, wherein: At least one of the following (1) to (3): (1) The dispersant in the first slurry is polyvinyl pyrrolidone; (2) The binder is at least one of polyvinyl butyral, polyethylene glycol, polyethersulfone resin, and ethyl cellulose; (3) The solvent is at least one of 1-methyl-2-pyrrolidone, terpineol, ethanol, butanone, and acetone.

3. The preparation method according to claim 1, wherein The structural layers of the proton ceramic membrane reactor from inside to outside are reactor cathode, proton membrane, proton membrane ceramic reactor anode and anode catalyst layer.

4. The preparation method according to claim 1, wherein At least one of the following items (1) to (4): (1) In step S1, the sintering temperature is 1000-1100°C and the sintering time is 2-4 hours; (2) In step S2, the sintering temperature is 1400-1500°C and the sintering time is 6-10 hours; (3) In steps S3 and S4, the sintering temperature is 950-1100°C and the sintering time is 2-4 hours; (4) In step S5, the sintering temperature is 700-800°C, and the sintering time is 2-4 hours.

5. The preparation method according to claim 1, wherein At least one of the following items (1) to (4): (1) The thickness of the cathode of the reactor is 600-800 μm; (2) The thickness of the proton membrane is 8 to 15 μm; (3) The thickness of the anode of the proton membrane ceramic reactor is 25-35 μm; (4) The thickness of the anode catalyst layer is 40-60 μm.

6. The preparation method according to claim 1, wherein The steps for impregnating the Fe-based thermal catalyst are: a. Weigh 0 to 20wt% of iron nitrate, 0 to 20wt% of copper nitrate, and the remainder of the cerium nitrate reagent to a concentration of 0.01 to 0.1mol / L of aqueous solution; b. The Fe-based catalyst was loaded into the cathode straight-hole microchannels by vacuum adsorption-assisted impregnation, with the number of impregnations ranging from 3 to 10 times. After each impregnation, the battery was pre-calcined at 400-600°C for 0.5-3 hours to decompose the nitrate, and the battery weight change was recorded.

7. Use of a proton ceramic membrane reactor prepared by the preparation method according to any one of claims 1 to 2 in the preparation of low-carbon alcohols, characterized in that: The preparation of low-carbon alcohols comprises the following steps: A. Pass hydrogen into the anode of the proton ceramic membrane reactor and reduce it at 600-700℃ for 3-5h; B. Prepare a mixture of methane and carbon dioxide as anode fuel; C. The prepared anode fuel is introduced into the anode of the proton ceramic membrane reactor, and carbon dioxide is introduced into the cathode of the proton ceramic membrane reactor. At 300~600℃, an external voltage is applied to catalyze the conversion of carbon dioxide at the cathode to produce low-carbon alcohols.

8. The use of the proton ceramic membrane reactor in the preparation of low-carbon alcohols as claimed in claim 7, characterized in that: At least one of the following (1) to (2): (1) The volume content of methane is 10% to 90% of the total volume of the anode fuel; (2) The external voltage is 1.2~2V.

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