A proton conductor ceramic membrane reactor and its preparation method and application

Abstract

The present invention discloses a proton conductor ceramic membrane reactor and its preparation method and application. The proton conductor ceramic membrane reactor of the present invention comprises an anode, a cathode and a proton conductor ceramic membrane. The anode comprises Pt or Ni and a proton conductor ceramic membrane material. The cathode comprises a Ru / C catalyst and a proton conductor ceramic membrane material. The proton conductor ceramic membrane comprises a proton conductor ceramic membrane material. The chemical formula of the proton conductor ceramic membrane material is Ln x WO 11.25‑δ , where Ln is a lanthanide element, 5.2≤x≤5.8, and 0≤δ≤1. The proton conductor ceramic membrane reactor of the present invention can electrochemically synthesize ammonia under medium temperature conditions, has excellent hydrogen separation efficiency and ammonia synthesis performance, and is suitable for large-scale promotion and application.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochemical catalysis and membrane separation, and in particular to a proton conductor ceramic membrane reactor and a preparation method and application thereof. Background Art

[0002] Ammonia (NH3) is an important chemical raw material and an ideal carbon-free hydrogen storage medium, widely used in agriculture and modern industry. Industrial ammonia is primarily synthesized via the Haber process (N2 + 3H2 → 2NH3). Due to the difficulty and slow kinetics of nitrogen-nitrogen triple bond dissociation, the ammonia synthesis reaction must be carried out under high temperature and high pressure (400°C to 600°C, 200 atm to 400 atm), resulting in high energy consumption (approximately 2% of global energy consumption annually). Furthermore, the hydrogen required for the Haber process is primarily obtained through methane steam reforming, a process that produces large amounts of gases such as carbon dioxide, requiring not only separation and purification operations but also the release of approximately 1% to 2% of global CO2 emissions.

[0003] Therefore, it is of great significance to develop a new technology that can synthesize ammonia under mild conditions to effectively alleviate the growing energy and environmental pressures. Summary of the Invention

[0004] The purpose of the present invention is to provide a proton conductor ceramic membrane reactor and a preparation method and application thereof.

[0005] The technical solution adopted by the present invention is:

[0006] A proton conductor ceramic membrane reactor, comprising an anode, a cathode and a proton conductor ceramic membrane: the anode comprises Pt or Ni and a proton conductor ceramic membrane material; the cathode comprises a Ru / C catalyst and a proton conductor ceramic membrane material; the proton conductor ceramic membrane comprises a proton conductor ceramic membrane material; the chemical formula of the proton conductor ceramic membrane material is Ln x WO 11.25-δ , where Ln is a lanthanide element, 5.2≤x≤5.8, 0≤δ≤1.

[0007] Preferably, the Ln is one of La (lanthanum), Pr (praseodymium), Nd (neodymium), Sm (samarium), Gd (gadolinium), and Er (erbium).

[0008] Preferably, the value range of x is 5.3≤x≤5.6.

[0009] Preferably, the proton conductor ceramic membrane material is prepared by the following method: mixing an Ln source and a W source and then calcining the mixture to obtain the proton conductor ceramic membrane material.

[0010] Preferably, the Ln source is at least one of Ln oxide, Ln nitrate, Ln sulfate, and Ln chloride.

[0011] More preferably, the Ln source is Ln oxide.

[0012] Preferably, the W source is at least one of W oxide and W organic complex.

[0013] More preferably, the W source is W oxide.

[0014] Preferably, the organic complex of W is at least one of tungsten acetate, tungsten propionate, and tungsten valerate.

[0015] Preferably, the mixing method is ball milling.

[0016] Preferably, the ball milling is carried out at a ball mill speed of 300 r / min to 1000 r / min, and the ball milling time is 10 h to 50 h.

[0017] More preferably, the ball milling is carried out at a ball mill speed of 300 r / min to 500 r / min, and the ball milling time is 40 h to 48 h.

[0018] Preferably, the particle size of the powder obtained by ball milling is 1 μm to 50 μm.

[0019] Preferably, the specific operation of the calcination is: heating to 800° C. to 1200° C. at a heating rate of 1° C. / min to 5° C. / min, and then keeping the temperature for 5 h to 20 h.

[0020] Further preferably, the specific operation of the calcination is: heating to 1000° C. to 1200° C. at a heating rate of 1° C. / min to 3° C. / min, and then keeping the temperature for 8 h to 10 h.

[0021] A method for preparing the proton conductor ceramic membrane reactor as described above comprises the following steps:

[0022] 1) dispersing a Pt source or a Ni source in a solvent to prepare a dispersion, mixing the dispersion with a proton conductor ceramic membrane material, drying the dispersion, and reducing the dispersion in a reducing atmosphere to obtain an anode powder; mixing a Ru / C catalyst and the proton conductor ceramic membrane material, ball milling the mixture, drying the mixture, and reducing the mixture in a reducing atmosphere to obtain a cathode powder; pressing the proton conductor ceramic membrane material into a membrane green sheet, and sintering the mixture to obtain a proton conductor ceramic membrane;

[0023] 2) The anode powder and the cathode powder are mixed with ethyl cellulose and terpineol respectively, and then ground to prepare anode slurry and cathode slurry, and then the anode slurry and the cathode slurry are coated on both sides of the proton conductor ceramic membrane respectively, and then dried and sintered to obtain a proton conductor ceramic membrane reactor.

[0024] Preferably, the reducing atmosphere in step 1) is a H2-Ar mixed atmosphere.

[0025] Preferably, the reduction in step 1) is carried out at 450°C to 550°C.

[0026] Preferably, the mass ratio of Ru / C catalyst and proton conductor ceramic membrane material in the cathode powder in step 1) is 1 to 4:1.

[0027] Preferably, the pressing in step 1) is carried out at a pressure of 8 MPa to 20 MPa.

[0028] Further preferably, the pressing in step 1) is carried out at a pressure of 15 MPa to 20 MPa.

[0029] Preferably, the specific operation of the sintering in step 1) is: heating to 1300° C. to 1600° C. at a heating rate of 0.5° C. / min to 3° C. / min, and then keeping the temperature for 8 h to 15 h.

[0030] Further preferably, the specific operation of the sintering in step 1) is: heating to 1300° C. to 1500° C. at a heating rate of 1° C. / min to 2° C. / min, and then keeping the temperature for 10 h to 12 h.

[0031] Preferably, the sintering in step 2) is carried out at 950° C. to 1150° C., and the holding time is 1 hour to 3 hours.

[0032] A method for synthesizing ammonia comprises the following steps: introducing N2 and H2 into the proton conductor ceramic membrane reactor as described above, and applying electricity to carry out reaction to obtain ammonia.

[0033] Preferably, the reaction is carried out at 300°C to 400°C.

[0034] The beneficial effects of the present invention are: the proton conductor ceramic membrane reactor of the present invention can electrochemically synthesize ammonia under medium temperature conditions, has excellent hydrogen separation efficiency and ammonia synthesis performance, and is suitable for large-scale promotion and application.

[0035] Specifically:

[0036] 1) The proton conductor ceramic membrane reactor of the present invention can electrochemically synthesize ammonia at medium temperatures (300°C to 400°C), taking into account both the reaction kinetics and reaction thermodynamics of the ammonia synthesis reaction. Compared with electrochemical ammonia synthesis technology at room temperature, it can greatly facilitate the kinetics of the reaction. At the same time, compared with electrochemical ammonia synthesis technology at high temperatures (>500°C), it can effectively prevent the decrease in ammonia yield caused by the accelerated decomposition of ammonia generated at high temperatures;

[0037] 2) The proton conductor ceramic membrane reactor of the present invention uses a tungstate-based proton conductor membrane material, which has superior hydrogen permeability and chemical stability against carbon dioxide compared to perovskite-type proton conductor membrane materials containing alkaline earth metal elements, fully meeting the application requirements in actual industrial atmospheres;

[0038] 3) The proton conductor ceramic membrane reactor of the present invention can be in-situ coupled with some important hydrogen-related separation processes, and can achieve efficient integration of ammonia synthesis reaction and hydrogen separation and purification, highlighting the high efficiency of the proton conductor ceramic membrane reactor. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 2 are the XRD patterns of LWO in Example 1 and BCZYYb7111 in Comparative Example 1.

[0040] Figure 2 This is the SEM image of the LWO film in Example 1.

[0041] Figure 3 Graph showing the ammonia synthesis performance test results of the proton conductor ceramic membrane reactors in Examples 1 to 3 and the traditional fixed-bed ammonia synthesis reactor in Comparative Example 2.

[0042] Figure 4 This is a graph showing the long-term stability test results of the proton conductor ceramic membrane reactor in Example 1 under a CO2-containing atmosphere. DETAILED DESCRIPTION

[0043] The present invention will be further explained and illustrated below with reference to specific embodiments.

[0044] Example 1:

[0045] A proton conductor ceramic membrane reactor, the preparation method of which comprises the following steps:

[0046] 1) 15.89 g of La2O3 and 4.11 g of WO3 were mixed and added to a ball mill, and then 20 mL of ethanol was added. The speed of the ball mill was adjusted to 400 r / min, and the mixture was ball milled for 48 h. The mixture was then taken out and dried naturally. The obtained mixed powder was then added to a muffle furnace, heated to 1100 ° C at a heating rate of 2 ° C / min, kept warm for 10 h, and then cooled to room temperature at a cooling rate of 2 ° C / min to obtain a proton conductor ceramic membrane material (La 5.5 WO 11.25-δ , δ is the non-stoichiometric ratio, 0≤δ≤1, denoted as LWO);

[0047] 2) 1 g of proton conductor ceramic membrane material was ground and placed in a cylindrical stainless steel grinding tool with an inner diameter of 16 mm. The grinding tool was kept at a pressure of 20 MPa for 10 minutes to obtain a membrane green body.

[0048] 3) placing the membrane embryo in a muffle furnace, heating it to 1400°C at a heating rate of 2°C / min, holding it for 12 hours, and then cooling it to room temperature at a cooling rate of 2°C / min to obtain a proton conductor ceramic membrane (LWO membrane);

[0049] 4) 0.1 g of H2PtCl6·6H2O was dispersed in 2 mL of ethanol, mixed with 0.75 g of proton conductor ceramic membrane material, dried at 80°C for 30 min, and then reduced at 500°C for 2 h in a H2-Ar mixed atmosphere (H2 volume fraction was 8%) to obtain anode powder (Pt / La 5.5 WO 11.25-δ , δ is the non-stoichiometric ratio, 0≤δ≤1);

[0050] 5) 2 g of commercial Ru / C catalyst and 1 g of proton conductor ceramic membrane material were added to a ball mill, and 20 mL of ethanol was added. The speed of the ball mill was adjusted to 400 r / min, and the mixture was ball milled for 48 h. The mixture was dried at 80 ° C for 90 min, and then reduced at 500 ° C for 4 h in a H2-Ar mixed atmosphere (the volume fraction of H2 was 8%) to obtain a cathode powder (Ru / C / La 5.5 WO 11.25-δ , δ is the non-stoichiometric ratio, 0≤δ≤1);

[0051] 6) The LWO membrane was coarsely ground with 400-mesh SiC sandpaper to a thickness of approximately 0.2 mm, and then polished with 800-mesh and 2000-mesh sandpaper in sequence, ultrasonically cleaned, and naturally dried. 0.5 g of anode powder, 0.02 g of ethyl cellulose, and 0.38 g of terpineol were mixed and ground to prepare an anode slurry, and 1 g of cathode powder, 0.04 g of ethyl cellulose, and 0.76 g of terpineol were mixed and ground to prepare a cathode slurry. The anode slurry and cathode slurry were respectively screen-printed on both sides of the pretreated LWO membrane, dried at 80 ° C for 90 min, and sintered at 1000 ° C for 2 h in a nitrogen atmosphere to obtain a proton conductor ceramic membrane reactor (the thickness of the anode was about 10 μm, the thickness of the cathode was about 100 μm, and the effective reaction area was 0.4 cm 2 ).

[0052] Example 2:

[0053] A proton conductor ceramic membrane reactor, the preparation method of which comprises the following steps:

[0054] 1) 1.5 g of commercial Ru / C catalyst and 1.5 g of proton conductor ceramic membrane material (same as in Example 1) were added to a ball mill, and 20 mL of ethanol was added. The speed of the ball mill was adjusted to 400 r / min, and the mixture was ball milled for 48 h. The mixture was dried at 80° C. for 90 min, and then reduced at 500° C. for 4 h in a H2-Ar mixed atmosphere (H2 volume fraction was 8%) to obtain a cathode powder (Ru / C / La 5.5 WO 11.25-δ , δ is the non-stoichiometric ratio, 0≤δ≤1);

[0055] 2) The LWO membrane (same as in Example 1) was coarsely ground with 400-mesh SiC sandpaper to a thickness of approximately 0.2 mm, and then polished with 800-mesh and 2000-mesh sandpaper in sequence, and then ultrasonically cleaned and naturally dried. 0.5 g of anode powder (same as in Example 1), 0.02 g of ethyl cellulose, and 0.38 g of terpineol were mixed and ground to prepare an anode slurry, and 1 g of cathode powder, 0.04 g of ethyl cellulose, and 0.76 g of terpineol were mixed and ground to prepare a cathode slurry. The anode slurry and the cathode slurry were respectively screen-printed on both sides of the pretreated LWO membrane, dried at 80° C. for 90 min, and then sintered at 1000° C. in a nitrogen atmosphere for 2 h to obtain a proton conductor ceramic membrane reactor (the thickness of the anode was about 10 μm, the thickness of the cathode was about 100 μm, and the effective reaction area was 0.4 cm). 2 ).

[0056] Example 3:

[0057] A proton conductor ceramic membrane reactor, the preparation method of which comprises the following steps:

[0058] 1) 1 g of commercial Ru / C catalyst and 2 g of proton conductor ceramic membrane material (same as in Example 1) were added to a ball mill, and 20 mL of ethanol was added. The speed of the ball mill was adjusted to 400 r / min, and the mixture was ball milled for 48 h. The mixture was dried at 80° C. for 90 min, and then reduced at 500° C. for 4 h in a H2-Ar mixed atmosphere (H2 volume fraction was 8%) to obtain a cathode powder (Ru / C / La 5.5 WO 11.25-δ , δ is the non-stoichiometric ratio, 0≤δ≤1);

[0059] 2) The LWO membrane (same as in Example 1) was coarsely ground with 400-mesh SiC sandpaper to a thickness of approximately 0.2 mm, and then polished with 800-mesh and 2000-mesh sandpaper in sequence, and then ultrasonically cleaned and naturally dried. 0.5 g of anode powder (same as in Example 1), 0.02 g of ethyl cellulose, and 0.38 g of terpineol were mixed and ground to prepare an anode slurry, and 1 g of cathode powder, 0.04 g of ethyl cellulose, and 0.76 g of terpineol were mixed and ground to prepare a cathode slurry. The anode slurry and the cathode slurry were respectively screen-printed on both sides of the pretreated LWO membrane, dried at 80° C. for 90 min, and then sintered at 1000° C. in a nitrogen atmosphere for 2 h to obtain a proton conductor ceramic membrane reactor (the thickness of the anode was about 10 μm, the thickness of the cathode was about 100 μm, and the effective reaction area was 0.4 cm). 2 ).

[0060] Comparative Example 1:

[0061] A perovskite-type proton conductor membrane material, the preparation method of which comprises the following steps:

[0062] 12.38g of BaCO3, 7.56g of CeO2, 0.77g of ZrO2, 0.71g of Y2O3, 1.24g of Yb2O3 and 0.2g of NiO were mixed and added to a ball mill, and then 20mL of ethanol was added. The speed of the ball mill was adjusted to 400r / min, and the ball mill was milled for 48h. Then, the mixed powder was taken out and dried naturally. The obtained mixed powder was added to a muffle furnace, heated to 1200℃ at a heating rate of 2℃ / min, kept warm for 10h, and then cooled to room temperature at a cooling rate of 2℃ / min to obtain a perovskite-type proton conductor membrane material (BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ , δ is the non-stoichiometric ratio, 0≤δ≤1, denoted as BCZYYb7111).

[0063] Comparative Example 2:

[0064] A conventional fixed-bed ammonia synthesis reactor, the preparation method of which comprises the following steps:

[0065] 0.6g of cathode powder (same as in Example 1) was placed In the quartz tube, shake it slightly to evenly spread the cathode powder on the bottom of the quartz tube, and then seal it to obtain a traditional fixed-bed ammonia synthesis reactor.

[0066] Performance testing:

[0067] 1) X-ray diffraction (XRD) patterns of LWO in Example 1 and BCZYYb7111 in Comparative Example 1 are shown in FIG. Figure 1 (a is untreated LWO and BCZYYb7111, b is LWO and BCZYYb7111 treated at 500℃ for 100h in CO2 atmosphere).

[0068] Depend on Figure 1 It can be seen that the diffraction peak positions of untreated LWO and BCZYYb7111 are consistent with those of the standard card, and no other impurities are generated, indicating that LWO and BCZYYb7111 are successfully synthesized; after LWO and BCZYYb7111 are treated at 500℃ for 100h in a CO2 atmosphere, BCZYYb7111 shows a characteristic peak of barium carbonate, while LWO does not have other impurity peaks and still maintains a good phase structure, indicating that LWO has good chemical stability against carbon dioxide.

[0069] 2) The scanning electron microscope (SEM) image of the LWO film in Example 1 is as follows: Figure 2 (a is the surface, b is the cross section).

[0070] Depend on Figure 2 It can be seen that the grains on the surface of the LWO film are tightly packed, the grain boundaries are clearly discernible, and the triple boundary angle is close to 120°, indicating that the grains are well developed. The cross-sectional view shows that there are no bubbles or through-holes inside the film. The grains are tightly connected, and gas cannot directly penetrate the lattice inside the film, indicating that the LWO film sintered at 1400℃ is very dense.

[0071] 3) Synthetic ammonia performance test:

[0072] The synthetic ammonia performance test process of the proton conductor ceramic membrane reactor in Examples 1 to 3 is as follows: the anode and cathode of the proton conductor ceramic membrane reactor in Examples 1 to 3 are coated with silver paste (for current collection), sintered at 500°C in air for 30 minutes, and then sealed with sealant. One end of the corundum tube, and then put a The quartz glass tube was used for feeding. After waiting for 24 hours for the sealant to dry completely, the device was fixed in a tube furnace and heated to 80°C at a heating rate of 1°C / min, kept warm for 2 hours, then heated to 150°C at a heating rate of 1°C / min, kept warm for 2 hours, and then heated to the test temperature (300°C, 350°C and 400°C) at a heating rate of 1°C / min. Each test temperature and applied current (1mA / cm 2 ~10mA / cm 2 , each interval 1mA / cm 2 Each test point (a total of 10 test points) must be tested continuously for 1 hour. The flow rate of the gas used in the test is precisely controlled by a mass flow controller. An H2 / CO2 mixture with a volume ratio of 4:1 is introduced into the feed side at a flow rate of 60 mL / min (the flow rate of hydrogen reaching the cathode through the LWO membrane is 0.007 mL / min to 0.07 mL / min). Nitrogen at 15 mL / min is used as a purge gas. The purge tail gas is introduced into a dilute hydrochloric acid absorption solution with a concentration of 0.01 mol / L to absorb the generated ammonia. The absorbance of the absorption solution is quantitatively detected by UV-visible spectrophotometry. Finally, the ammonia yield and the corresponding current Faraday efficiency are calculated based on the ammonia standard curve.

[0073] The ammonia synthesis performance test process of the traditional fixed-bed ammonia synthesis reactor in Comparative Example 2 is as follows: the traditional fixed-bed ammonia synthesis reactor in Comparative Example 2 is heated to the test temperatures (300°C, 350°C and 400°C) at a heating rate of 1°C / min. Each test temperature must be maintained for 1 hour of uninterrupted testing. The flow rate of the gas used in the test is precisely controlled by a mass flow controller, and hydrogen and nitrogen are introduced. The flow rate of hydrogen is 0.07 mL / min, and the flow rate of nitrogen is 15 mL / min. The tail gas is introduced into a dilute hydrochloric acid absorption liquid with a concentration of 0.01 mol / L to absorb the generated ammonia. The absorbance of the absorption liquid is quantitatively detected using UV-visible spectrophotometry. Finally, the ammonia yield is calculated based on the ammonia standard curve.

[0074] The test results of ammonia synthesis performance of the proton conductor ceramic membrane reactor in Examples 1 to 3 and the traditional fixed bed ammonia synthesis reactor in Comparative Example 2 are shown in the figure. Figure 3 (a is a graph showing the ammonia yield test results of the proton conductor ceramic membrane reactor in Example 1, b is a graph showing the current Faraday efficiency test results of the proton conductor ceramic membrane reactor in Example 1, and c is a graph showing the comparative test results of the ammonia yields of the proton conductor ceramic membrane reactors in Examples 1 to 3 and the traditional fixed-bed ammonia synthesis reactor in Comparative Example 2).

[0075] Depend on Figure 3It can be seen that the ammonia yield of the proton conductor ceramic membrane reactor in Examples 1 to 3 is approximately 10 times, 9 times and 8 times that of the traditional fixed-bed ammonia synthesis reactor in Comparative Example 2 (as the Ru / C content in the cathode powder decreases, the ammonia yield of the proton conductor ceramic membrane reactor will also decrease accordingly), indicating that the proton conductor ceramic membrane reactor of the present invention has great advantages in ammonia synthesis.

[0076] 4) Electrocatalytic ammonia synthesis stability test:

[0077] The proton conductor ceramic membrane reactor in Example 1 was placed in a H2-CO2 atmosphere (the volume ratio of H2 to CO2 was 4:1) and subjected to an electrocatalytic ammonia synthesis test at 350°C for 100 hours. The long-term stability test results of the proton conductor ceramic membrane reactor in a CO2-containing atmosphere are shown in the figure. Figure 4 (a is the long-term stability diagram of synthetic ammonia, b is the current density 2.5mA / cm 2 The corresponding applied voltage value is shown in Figure 2, and c is the XRD pattern of the LWO membrane in the proton conductor ceramic membrane reactor before and after the test.

[0078] Depend on Figure 4 It can be seen that after 100 hours of testing, the ammonia yield, current Faraday efficiency, and corresponding voltage value of the proton conductor ceramic membrane reactor in Example 1 did not show obvious fluctuations, and the phase structure of the LWO membrane in the proton conductor ceramic membrane reactor remained basically unchanged before and after the test, indicating that the proton conductor membrane ammonia synthesis reactor of the present invention has excellent operational stability.

[0079] After testing (same as above), the ammonia yield, current Faraday efficiency and corresponding voltage value of the proton conductor ceramic membrane reactors in Examples 2 and 3 did not show obvious fluctuations after 100 hours of testing in a CO2-containing atmosphere. Moreover, the phase structure of the LWO membrane in the proton conductor ceramic membrane reactor remained basically unchanged before and after the test, and also had excellent operational stability.

[0080] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for synthesizing ammonia, characterized in that: The following steps are involved: A H2 / CO2 mixed gas is introduced into the feed side of a proton conductor ceramic membrane reactor, and N2 is used as a purge gas, and electricity is applied to react to obtain ammonia; the composition structure of the proton conductor ceramic membrane reactor includes an anode, a cathode and a proton conductor ceramic membrane; the composition of the anode includes Pt or Ni and also includes a proton conductor ceramic membrane material; the composition of the cathode includes a Ru / C catalyst and a proton conductor ceramic membrane material; the composition of the proton conductor ceramic membrane includes a proton conductor ceramic membrane material; the chemical formula of the proton conductor ceramic membrane material is Ln x WO 11.25-δ , wherein Ln is one of La, Pr, Nd, Sm, Gd, and Er, 5.2≤x≤5.8, 0≤δ≤1; and the reaction is carried out at 300°C to 400°C.

2. The method for synthesizing ammonia according to claim 1, wherein: The value range of x is 5.3≤x≤5.

6.

3. The method for synthesizing ammonia according to claim 1, wherein: The proton conductor ceramic membrane material is prepared by the following method: Ln source and W source are mixed and then calcined to obtain the proton conductor ceramic membrane material.

4. The method for synthesizing ammonia according to claim 3, wherein: The specific operation of the calcination is: heating to 800° C. to 1200° C. at a heating rate of 1° C. / min to 5° C. / min, and then keeping the temperature for 5 h to 20 h.

5. The method for synthesizing ammonia according to claim 1, characterized in that: The proton conductor ceramic membrane reactor is made by a preparation method comprising the following steps: 1) The Pt source or Ni source is dispersed in a solvent to prepare a dispersion, which is then mixed with a proton conductor ceramic membrane material, dried, and then reduced in a reducing atmosphere to obtain an anode powder; The Ru / C catalyst and the proton conductor ceramic membrane material are mixed and ball-milled, then dried, and then reduced in a reducing atmosphere to obtain a cathode powder; the proton conductor ceramic membrane material is pressed into a membrane green embryo, and then sintered to obtain a proton conductor ceramic membrane; 2) The anode powder and cathode powder are mixed with ethyl cellulose and terpineol respectively, and then ground to form anode slurry and cathode slurry, and then the anode slurry and cathode slurry are coated on both sides of the proton conductor ceramic membrane respectively, and then dried and sintered to obtain a proton conductor ceramic membrane reactor.

6. The method for synthesizing ammonia according to claim 5, characterized in that: The reducing atmosphere in step 1) is a H2-Ar mixed atmosphere; the reduction in step 1) is performed at 450°C to 550°C; the mass ratio of Ru / C catalyst and proton conductor ceramic membrane material in the cathode powder in step 1) is 1 to 4:1; the pressing in step 1) is performed under a pressure of 8 MPa to 20 MPa; the specific operation of sintering in step 1) is: heating to 1300°C to 1600°C at a heating rate of 0.5°C / min to 3°C / min, and then keeping warm for 8h to 15h.

7. The method for synthesizing ammonia according to claim 5 or 6, characterized in that: Step 2) The sintering is carried out at 950° C. to 1150° C., and the holding time is 1 hour to 3 hours.

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