Preparation method and application of high-temperature oxygen permeable membrane

Abstract

The application relates to the field of energy technology, and discloses a preparation method of a high-temperature oxygen permeation membrane and application thereof, the method comprising the following steps: step 1, preparing an oxygen permeation membrane embryo; step 2, performing water vapor reduction hydrogen production catalyst coating treatment on one side of the oxygen permeation membrane embryo prepared in step 1 to obtain a primary oxygen permeation membrane embryo; step 3, performing selective oxidation catalyst coating treatment on the uncoated side of the primary oxygen permeation membrane embryo prepared in step 2 to obtain a secondary oxygen permeation membrane embryo; and step 4, performing reduction / blowing / oxidation cycle treatment on the secondary oxygen permeation membrane in step 2 to obtain a high-temperature oxygen permeation membrane, wherein the cycle treatment is performed 5-25 times; in the method, the water vapor reduction hydrogen production catalyst, the selective oxidation catalyst and the reduction / blowing / oxidation cycle treatment process can significantly improve the reaction rate of the high-temperature oxygen permeation membrane; and the application also provides the application of the high-temperature oxygen permeation membrane, and the application has the technical effects of low cost, environmental protection and preparation of low-carbon chemical products by using carbon dioxide and bio-tar.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energy, in particular to a preparation method of high-temperature oxygen permeable membrane and application thereof. BACKGROUND

[0002] The main material of the high-temperature oxygen permeable membrane is perovskite oxide, and the membrane has oxygen ion and electron mixing properties under high-temperature conditions. When there is an oxygen partial pressure gradient between the two sides of the membrane, the oxygen on the high-pressure side is dissociated into oxygen ions and electrons on the surface of the membrane through chemical adsorption and diffuses from the main body of the membrane to the low-pressure side of the membrane, and then recombines and desorbs into the low-oxygen pressure system. Therefore, one end of the high-temperature oxygen permeable membrane forms an oxidizing atmosphere, and the other end forms a strong reducing atmosphere. Therefore, the high-temperature oxygen permeable membrane in the prior art is often applied to the water decomposition coupled with the partial oxidation of methane to produce synthesis gas, which is one of the important forms of natural gas utilization. For example, a perovskite ceramic oxygen permeable membrane material for methane partial oxidation reaction is disclosed in CN101279842B. In this method, a certain amount of Fe elements and Y elements are doped in the B position of BaCoO3 to obtain a new type of oxygen permeable membrane material BaCo 0.7 Fe 0.3-x Y x O 3-δ The tar generated in the biomass gasification process is not easy to utilize in the gasification process, which can cause catalyst poisoning and carbon emission after separation and combustion. The preparation of synthesis gas from biomass tar can reduce carbon emission and efficiently utilize biomass energy.

[0003] The preparation process of the high-temperature oxygen permeable membrane in the prior art mainly focuses on the stability and oxygen permeation rate of the oxygen permeable membrane material, and there is no in-depth research on the preparation process of the high-temperature oxygen permeable membrane. The steps of the preparation process of the high-temperature oxygen permeable membrane in the prior art are mainly to mold the perovskite oxide into a blank and calcine it at high temperature to form an integrated ceramic structure. For example, CN105642131B discloses a method for stabilizing a perovskite structure oxygen permeable membrane with nanoparticles. CN109734438A discloses a titanium-based perovskite ceramic oxygen permeable membrane without cobalt and iron, its preparation method and application. The above-mentioned preparation processes are relatively simple and cannot improve the performance of the oxygen permeable membrane. The reaction conditions and reaction performance requirements of the water reduction hydrogen production side and the selective oxidation side are different, so the single-component oxygen permeable membrane material cannot achieve good reaction efficiency, and the introduction of other catalysts affects the oxygen permeation rate. SUMMARY

[0004] In order to overcome the problems existing in the prior art, the application provides a preparation method of a high-temperature oxygen permeation membrane and application thereof. The high-temperature oxygen permeation membrane component is prepared through three processes of water vapor reduction hydrogen production catalyst coating treatment, selective oxidation catalyst coating treatment and reduction / blowing / oxidation treatment, so that the reaction rate of the high-temperature oxygen permeation membrane is significantly improved. The high-temperature oxygen permeation membrane prepared by the application is a three-layer composite structure with an oxygen permeation membrane layer located at the center of a water vapor reduction hydrogen production layer and a biomass tar oxidation synthesis gas production layer located at the opposite side of the oxygen permeation membrane. The high-temperature oxygen permeation membrane can produce methanol and H2 / CO synthesis gas by using water, carbon dioxide and biomass tar, and has the technical effects of environmental protection, low cost and high utilization rate of carbon dioxide and biomass energy.

[0005] The specific technical scheme of the application is as follows:

[0006] A preparation method of a high-temperature oxygen permeation membrane, comprising the following preparation steps:

[0007] Step 1: preparing an oxygen permeation membrane embryo;

[0008] Step 2: performing water vapor reduction hydrogen production catalyst coating treatment on one side of the oxygen permeation membrane embryo prepared in step 1 to prepare a primary oxygen permeation membrane embryo;

[0009] Step 3: performing selective oxidation catalyst coating treatment on the uncoated side of the primary oxygen permeation membrane embryo prepared in step 2 to prepare a secondary oxygen permeation membrane embryo;

[0010] Step 4: performing reduction / blowing / oxidation cycle treatment on the secondary oxygen permeation membrane prepared in step 3 to prepare a high-temperature oxygen permeation membrane, and the cycle treatment is performed 5-15 times.

[0011] Preferably, the high-temperature oxygen permeation membrane comprises an oxygen permeation membrane layer and a water vapor reduction hydrogen production layer and a biomass tar oxidation synthesis gas production layer arranged on the two sides of the oxygen permeation membrane layer respectively, and the material of the oxygen permeation membrane is a perovskite oxide.

[0012] Preferably, the chemical formula of the perovskite oxide is ABO3, A comprises one or more of La, Sr and Ba, and B comprises one or more of Fe, Co, Ni and Cu.

[0013] Preferably, the perovskite oxide is Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3.

[0014] Preferably, the component of the water vapor reduction hydrogen production layer comprises La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 / CeO2.

[0015] As preferred, the biomass tar oxidation to synthesis gas layer includes Ba 0.3 Sr 0.7 CoO3 / CeO2.

[0016] The application provides a preparation method of high-temperature oxygen permeable membrane. The method comprises a water vapor reduction hydrogen production catalyst coating treatment, a selective oxidation catalyst coating treatment, and a reduction / purging / oxidation treatment to form a high-temperature oxygen permeable membrane. The prepared high-temperature oxygen permeable membrane has a three-layer composite structure with an oxygen permeable membrane layer located in the center of a water vapor reduction hydrogen production layer and a biomass tar oxidation to synthesis gas layer located on the opposite side of the oxygen permeable membrane. The oxygen permeable membrane layer is used to transfer lattice oxygen in the water vapor reduction hydrogen production layer to the biomass tar oxidation to synthesis gas layer. The water vapor reduction hydrogen production layer undergoes a high-temperature water vapor reduction hydrogen production reaction to produce H2. The H2 reacts with carbon dioxide to produce methanol. Oxygen in the water vapor is converted into lattice oxygen and transferred to the biomass tar oxidation to synthesis gas layer through the oxygen permeable membrane layer to react with biomass tar through selective oxidation to produce H2 / CO synthesis gas. The water vapor reduction hydrogen production layer is coated with La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 / CeO2 material on the hydrogen production side of the oxygen permeable membrane layer, and the biomass tar oxidation to synthesis gas layer is coated with Ba 0.3 Sr 0.7 CoO3 / CeO2 material on the oxygen production side of the oxygen permeable membrane layer. The high-temperature oxygen permeable membrane with a three-layer composite structure is formed through several reduction / purging / oxidation treatment cycles. The catalysts on both sides and the oxygen permeable membrane material gradually come into close contact in multiple oxidation-reduction cycles, which reduces the lattice oxygen transfer resistance, improves the oxygen supply rate of the high-temperature reaction, and promotes the water vapor reduction hydrogen production layer and the biomass tar oxidation to synthesis gas layer to exhibit higher catalytic performance. After the reduction / purging / oxidation treatment, the high-temperature oxygen permeable membrane has significantly enhanced oxygen permeation hydrogen production efficiency. At the same time, the water vapor reduction hydrogen production reaction and the biomass tar selective oxidation to synthesis gas reaction are highly efficient, and the reaction yield and stability are significantly improved.

[0017] As preferred, the preparation step of the oxygen permeable membrane blank in step 1 comprises: molding and calcining Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 to form an oxygen permeable membrane blank.

[0018] The molding conditions include: a molding pressure cavity of 3-6 MPa, a molding time of 2-6 h, and a molding filling density of 0.5-2.0 g / cm 2 ;

[0019] The calcination conditions include: increasing the temperature to 1000℃ at a rate of 1℃ / min, and cooling to room temperature at a rate of 1.5℃ / min after constant temperature for 6h.

[0020] As preferred, the step of the water vapor reduction hydrogen production catalyst coating treatment in step 2 includes: coating the hydrogen permeable slurry on one side of the oxygen permeable membrane embryo and drying to make a primary oxygen permeable membrane embryo;

[0021] The water vapor reduction hydrogen production catalyst slurry includes the following components by mass fraction: 10-30 parts of Ba 0.3 Sr 0.7 CoO3, 10-20 parts of CeO2, 0.1-0.5 parts of hydroxypropyl methyl cellulose, 0.1-0.5 parts of glycerol and 49-79.8 parts of water;

[0022] The coating conditions include: the coating density is 1.5-3.5g / cm 2 ;

[0023] The drying conditions include: the drying temperature is 105℃.

[0024] As preferred, the step of the selective oxidation catalyst coating treatment in step 3 includes: coating the selective oxidation catalyst slurry on the uncoated side of the primary oxygen permeable membrane embryo and drying to make a secondary oxygen permeable membrane embryo;

[0025] The selective oxidation catalyst slurry includes the following components by mass fraction: 10-30 parts of La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3, 5-20 parts of CeO2, 0-0.5 parts of hydroxypropyl methyl cellulose, 0-1.0 parts of glycerol and 48.5-85 parts of water;

[0026] The coating conditions include: the coating density is 0.5-2.0g / cm 2 ;

[0027] The drying conditions include: the drying temperature is 105℃.

[0028] As preferred, the step of the reduction / blowing / oxidation cycle treatment in step 4 includes: sequentially performing preheating treatment, reduction treatment, blowing treatment, oxidation treatment and cooling treatment on the secondary oxygen permeable membrane;

[0029] The preheating treatment conditions include: the preheating atmosphere includes nitrogen, the preheating atmosphere flow is 50ml / min*cm 2 , and the temperature is increased to 1000℃ at a rate of 1℃ / min;

[0030] The conditions of the reduction treatment include: the reduction atmosphere includes 1:1 hydrogen and nitrogen by mass fraction ratio, the reduction atmosphere flow rate is 50-120 ml / min*cm2, and the treatment time is 10 min.

[0031] The conditions of the blowing treatment include: the blowing atmosphere includes nitrogen, the blowing atmosphere flow rate is 100 ml / min*cm 2 , and the treatment time is 10 min.

[0032] The conditions of the oxidation treatment include: the oxidation atmosphere includes 1:4 oxygen and nitrogen by mass fraction ratio, the oxidation atmosphere flow rate is 50-120 ml / min*cm 2 , and the treatment time is 10 min.

[0033] The conditions of the cooling treatment include: cooling at a cooling rate of 2℃ / min under the oxidation atmosphere.

[0034] In the present application, a special reduction / blowing / oxidation cycle treatment process is adopted when the water vapor reduction hydrogen production layer, the oxygen permeable membrane layer and the biomass tar oxidation synthetic gas production layer are compounded. After the hydrogen reduction-nitrogen blowing-oxygen oxidation cycle treatment for multiple times, the lattice oxygen diffusion resistance of the water vapor reduction hydrogen production layer-oxygen permeable membrane layer and the oxygen permeable membrane layer-biomass tar oxidation synthetic gas production layer is obviously reduced, so that the oxygen migration ability is improved, and the reaction performance of the prepared high-temperature oxygen permeable membrane is significantly improved.

[0035] A high-temperature oxygen permeable membrane or a preparation method of the high-temperature oxygen permeable membrane is applied to the combined production of biomass tar synthetic gas and carbon dioxide to methanol.

[0036] A methanol / synthetic gas co-production device includes an oxygen permeable membrane reactor and a water vapor generator in communication with the oxygen permeable membrane reactor. The oxygen permeable membrane reactor includes a water hydrogen production end and a selective oxidation end. The water hydrogen production end is in communication with a methanation reactor, and the selective oxidation end is in communication with a synthetic gas / tar separator. The oxygen permeable membrane reactor includes a plurality of stacked synthetic gas / methanol co-production oxygen permeable membranes according to claim 1.

[0037] Compared with the prior art, the present application has the following technical effects:

[0038] (1) The high-temperature oxygen permeable membrane provided by the present application has a three-layer structure, and the middle is an oxygen permeable layer (Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3); one side of the oxygen permeable layer is a water vapor reduction hydrogen production layer (La 0.7 Sr 0.3 Cu 0.2 Fe 0.8On the other side of O3 / CeO2, the components of the syngas layer produced by the oxidation of biomass tar include (Ba 0.3 Sr 0.7 The CoO3 / CeO2) steam reduction hydrogen production layer and the biomass tar oxidation syngas production layer were prepared by coating with a steam reduction hydrogen production catalyst, coating with a selective oxidation catalyst, and a reduction / sweeping / oxidation cycle treatment, which significantly improved the reaction rate of the high-temperature oxygen permeable membrane.

[0039] (2) This application also provides a methanol / syngas co-production device, which has the technical effects of high environmental performance, low raw material cost, high production efficiency and low energy consumption, and can realize the efficient and clean utilization of carbon dioxide and conversion of biomass fuel. Attached Figure Description

[0040] Figure 1 This is a structural schematic diagram of Embodiment 4 of this application.

[0041] Figure 2 This is a process flow diagram of Embodiment 4 of this application.

[0042] In the diagram, there are oxygen-permeable membrane reactor 1, steam generator 2, heat exchanger 3, booster pump 4, methanolization reactor 5, methanol distillation column 6, syngas / tar separator 7, and heat exchanger 8. Detailed Implementation

[0043] The present invention will be further described below with reference to embodiments.

[0044] General Implementation Examples:

[0045] A method for preparing a high-temperature oxygen-permeable membrane includes the following preparation steps:

[0046] Step 1: Prepare an oxygen-permeable membrane embryo;

[0047] A mixed solution of Ba, Sr, Co, Fe nitrate was configured, the molar concentration of Ba, Sr, Co, Fe ions was 0.05 mol / L, 0.05 mol / L, 0.08 mol / L, 0.02 mol / L, then proper citric acid and ethylenediaminetetraacetic acid were added into the nitrate solution to make the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution be 0.3 mol / L and 0.2 mol / L respectively, then ammonia water was added to make the pH value of the mixed solution be 8-9; the mixed solution was heated to about 85℃ under stirring, and heating and evaporation was continued until a sol-like product was formed, the formed sol product was dried at 105℃ to form a gel, then the gel was heated to 400℃ at a heating rate of 10℃ / min under air atmosphere, and was kept at 400℃ for 30 min for calcination, then the temperature was continuously increased to 850℃ at a heating rate of 10℃ / min under air atmosphere, and was kept at 850℃ for 1 h, then the calcined product after cooling was treated by wet ball milling, anhydrous ethanol was used as dispersant, the sample was taken out after ball milling for 5 h and was dried, and Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder was obtained.

[0048] The Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder was laid in a mold at a thickness of 1.0 g / cm 2 , and was molded at a pressure of 4 MPa for 15 h, then the molded oxygen permeable membrane blank was taken out and was heated to 1000℃ at a heating rate of 1℃ / min in a muffle furnace, and was kept at 1000℃ for 6 h, then was cooled to room temperature at a cooling rate of 1.5℃ / min, and an oxygen permeable membrane blank was obtained.

[0049] Step 2: the one side of the oxygen permeable membrane blank prepared in step 1 was subjected to water vapor reduction hydrogen production catalyst coating treatment to obtain a primary oxygen permeable membrane blank.

[0050] A mixed solution of La, Sr, Cu, Fe nitrate is configured, the molar concentration of La, Sr, Cu, Fe ions is 0.07 mol / L, 0.03 mol / L, 0.02 mol / L, 0.08 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added to the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and continues to be heated and evaporated until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 30 min, then continues to be heated to 850℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 1 h, then the calcined product after cooling is treated by wet ball milling, anhydrous ethanol is used as dispersant, the sample is taken out and dried after ball milling for 5 h, and a La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder is obtained; Ba 0.3 S r0.7 CoO3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, and water are mixed to prepare a coating slurry, the coating slurry is used to coat the water reduction hydrogen side of the oxygen permeable membrane, the coating amount is 2.74 g / cm 2 , and the sample after coating is dried at 105℃;

[0051] Step 3: the uncoated side of the oxygen permeable membrane blank prepared in step 2 is subjected to catalyst coating treatment to prepare an oxygen permeable membrane blank;

[0052] A mixed solution of Ba, Sr, Co nitrate is configured, the molar concentration of Ba, Sr, Co ions is 0.03 mol / L, 0.07 mol / L, 0.1 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added into the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and heating and evaporation are continuously performed until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min in an air atmosphere, and is kept at the temperature for 30 min for calcination, then the temperature is continuously increased to 850℃ at a heating rate of 10℃ / min in the air atmosphere, and is kept at the temperature for 1 h for natural cooling, and then the cooled calcined product is subjected to wet ball milling treatment, anhydrous ethanol is used as a dispersant, the sample is taken out and dried after ball milling for 5 h, and a Ba 0.3 Sr 0.7 CoO3 powder is obtained.

[0053] La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, and water are mixed to prepare a coating slurry, and the coating slurry is applied to the biomass tar selective oxidation side of the oxygen permeable membrane, the coating amount is 1.14 g / cm 2 , and the sample is dried at 105℃ after coating.

[0054] Step 3: the secondary oxygen permeable membrane in step 2 is subjected to reduction / purging / oxidation cycle treatment to obtain a high-temperature oxygen permeable membrane, and the cycle treatment is performed 5-25 times.

[0055] The oxygen permeable membrane is placed in a heating furnace, heated to 1000℃ at a heating rate of 1℃ / min under a N2 atmosphere of 50 ml / min*cm 2 , and then subjected to reduction-purging-oxidation cycle treatment, the reduction atmosphere is a 1:1 H2 gas flow and N2 gas flow with a total flow rate of 100 ml / min*cm 2 , the purging atmosphere is a N2 gas flow with a total flow rate of 100 ml / min*cm 2 , and the oxidation atmosphere is a 1:4 O2 gas flow and N2 gas flow with a total flow rate of 100 ml / min*cm 2 , the reaction time of each stage is controlled to be 10 min, and the high-temperature oxygen permeable membrane is obtained after cooling at a cooling rate of 2℃ / min under the oxidation atmosphere.

[0056] Example 1: (cycle treatment 5 times)

[0057] Step 1: Preparation of oxygen permeable membrane embryo

[0058] A mixed solution of Ba, Sr, Co, Fe nitrate was prepared, with the molar concentration of Ba, Sr, Co, Fe ions being 0.05 mol / L, 0.05 mol / L, 0.08 mol / L, 0.02 mol / L, and then appropriate citric acid and ethylenediaminetetraacetic acid were added to the nitrate solution to make the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution be 0.3 mol / L and 0.2 mol / L respectively, and then ammonia water was added to make the pH value of the mixed solution be 8-9; the mixed solution was heated to about 85°C under stirring, and continued to be heated and evaporated until a sol-like product was formed, the formed sol product was dried at a temperature of 105°C to form a gel, and then the gel was heated to 400°C at a heating rate of 10°C / min in an air atmosphere, and was kept at the temperature for 30 min for calcination, and then was continuously heated to 850°C at a heating rate of 10°C / min in an air atmosphere, and was kept at the temperature for 1 h for natural cooling, and then the cooled calcined product was treated by wet ball milling, with anhydrous ethanol as dispersant, and the sample was taken out and dried after ball milling for 5 h, to obtain Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder;

[0059] The Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder was laid in the mold at a thickness of 1.0 g / cm 2 , and was molded at a pressure of 4 MPa for 15 h, and then the formed oxygen permeable membrane blank was taken out and was heated to 1000°C at a heating rate of 1°C / min in a muffle furnace, and was kept at the temperature for 6 h, and then was cooled to room temperature at a cooling rate of 1.5°C / min, to obtain an oxygen permeable membrane embryo;

[0060] Step 2: One-side water vapor reduction hydrogen production catalyst coating treatment was performed on the oxygen permeable membrane embryo prepared in step 1, to obtain a primary oxygen permeable membrane embryo;

[0061] A mixed solution of La, Sr, Cu, Fe nitrate is configured, the molar concentration of La, Sr, Cu, Fe ions is 0.07 mol / L, 0.03 mol / L, 0.02 mol / L, 0.08 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added to the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and continues to be heated and evaporated until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 30 min, then continues to be heated to 850℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 1 h, then the calcined product after cooling is treated by wet ball milling, anhydrous ethanol is used as dispersant, the sample is taken out and dried after ball milling for 5 h, and a La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder is obtained; Ba 0.3 S r0.7 CoO3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, and water are mixed to prepare a coating slurry, and the coating slurry is used to coat the water reduction hydrogen side of the oxygen permeable membrane, the coating amount is 2.74 g / cm 2 , and the sample is dried at 105℃ after coating;

[0062] Step 3: the uncoated side of the primary oxygen permeable membrane blank prepared in step 2 is subjected to selective oxidation catalyst coating treatment to prepare a secondary oxygen permeable membrane blank;

[0063] A mixed solution of Ba, Sr, Co nitrate is configured, the molar concentration of Ba, Sr, Co ions is 0.03 mol / L, 0.07 mol / L, 0.1 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added into the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and heating and evaporation are continuously performed until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min in an air atmosphere, and is kept at the temperature for 30 min for calcination, then the temperature is continuously increased to 850℃ at a heating rate of 10℃ / min in the air atmosphere, and is kept at the temperature for 1 h for natural cooling, and then the cooled calcined product is subjected to wet ball milling treatment, anhydrous ethanol is used as a dispersant, the sample is taken out and dried after ball milling for 5 h, and a Ba 0.3 Sr 0.7 CoO3 powder is obtained.

[0064] La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, and water are mixed to prepare a coating slurry, and the coating slurry is applied to the selective oxidation side of the biomass tar selective oxidation membrane, the coating amount is 1.14 g / cm 2 , and the sample is dried at 105℃ after coating.

[0065] Step 3: The secondary oxygen permeable membrane in step 2 is subjected to reduction / purging / oxidation cycle treatment to obtain a high-temperature oxygen permeable membrane, and the cycle treatment is performed 5 times.

[0066] The oxygen permeable membrane is placed in a heating furnace, heated to 1000℃ at a heating rate of 1℃ / min under a N2 atmosphere of 50 ml / min*cm 2 , and then subjected to reduction-purging-oxidation cycle treatment, the reduction atmosphere is a 1:1 H2 gas flow and N2 gas flow with a total flow rate of 100 ml / min*cm 2 , the purging atmosphere is a N2 gas flow with a total flow rate of 100 ml / min*cm 2 , and the oxidation atmosphere is a 1:4 O2 gas flow and N2 gas flow with a total flow rate of 100 ml / min*cm 2 , the reaction time of each stage is controlled to be 10 min, and the high-temperature oxygen permeable membrane is obtained after cooling at a cooling rate of 2℃ / min under the oxidation atmosphere.

[0067] Example 2: (cycle treatment 15 times)

[0068] Step 1: Preparation of oxygen permeable membrane embryo

[0069] A mixed solution of Ba, Sr, Co, Fe nitrate was prepared, with the molar concentration of Ba, Sr, Co, Fe ions being 0.05 mol / L, 0.05 mol / L, 0.08 mol / L, 0.02 mol / L, and then appropriate citric acid and ethylenediaminetetraacetic acid were added to the nitrate solution to make the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution be 0.3 mol / L and 0.2 mol / L respectively, and then ammonia water was added to make the pH value of the mixed solution be 8-9; the mixed solution was heated to about 85°C under stirring, and continued to be heated and evaporated until a sol-like product was formed, the formed sol product was dried at a temperature of 105°C to form a gel, and then the gel was heated to 400°C at a heating rate of 10°C / min in an air atmosphere, and was kept at the temperature for 30 min for calcination, and then was continuously heated to 850°C at a heating rate of 10°C / min in an air atmosphere, and was kept at the temperature for 1 h for natural cooling, and then the cooled calcined product was treated by wet ball milling, with anhydrous ethanol as dispersant, and the sample was taken out and dried after ball milling for 5 h, to obtain Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder;

[0070] The Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder was laid in the mold at a thickness of 1.0 g / cm 2 , and was molded at a pressure of 4 MPa for 15 h, and then the formed oxygen permeable membrane blank was taken out and placed in a muffle furnace, and was heated to 1000°C at a heating rate of 1°C / min, and was kept at the temperature for 6 h, and then was cooled to room temperature at a cooling rate of 1.5°C / min, to obtain an oxygen permeable membrane embryo;

[0071] Step 2: One-side water vapor reduction hydrogen production catalyst coating treatment was performed on the oxygen permeable membrane embryo prepared in step 1, to obtain a primary oxygen permeable membrane embryo;

[0072] A mixed solution of La, Sr, Cu, Fe nitrate is configured, the molar concentration of La, Sr, Cu, Fe ions is 0.07 mol / L, 0.03 mol / L, 0.02 mol / L, 0.08 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added to the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and continues to be heated and evaporated until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 30 min, then continues to be heated to 850℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 1 h, then the calcined product after cooling is treated by wet ball milling, anhydrous ethanol is used as dispersant, the sample is taken out and dried after ball milling for 5 h, and a La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder is obtained; Ba 0.3 S r0.7 CoO3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, and water are mixed to prepare a coating slurry, the coating slurry is used to coat the water reduction hydrogen side of the oxygen permeable membrane, the coating amount is 2.74 g / cm 2 , and the sample after coating is dried at 105℃

[0073] Step 3: the uncoated side of the primary oxygen permeable membrane blank prepared in step 2 is subjected to selective oxidation catalyst coating treatment to prepare a secondary oxygen permeable membrane blank;

[0074] A Ba, Sr, Co nitrate mixed solution is configured, the molar concentration of Ba, Sr, Co ions being 0.03 mol / L, 0.07 mol / L, 0.1 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added to the nitrate solution so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, and then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90°C under stirring, and heating and evaporation are continuously performed until a sol-like product is formed, the formed sol product is dried at a temperature of 105°C to form a gel, then the gel is heated to 400°C at a heating rate of 10°C / min under air atmosphere, and is kept at the temperature for 30 min for calcination, then the temperature is continuously increased to 850°C at a heating rate of 10°C / min under air atmosphere, and is kept at the temperature for 1 h for calcination, and then the calcined product after cooling is subjected to wet ball milling treatment, anhydrous ethanol is used as dispersant, and the sample is taken out and dried after ball milling for 5 h, to obtain Ba 0.3 Sr 0.7 CoO3 powder;

[0075] La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, water are mixed to prepare a coating slurry, and the selective oxidation side of the biomass tar of the oxygen permeable membrane is coated and treated, the coating amount being 1.14 g / cm 2 , and the sample is dried at 105°C after coating;

[0076] Step 3: the secondary oxygen permeable membrane in step 2 is subjected to reduction / purging / oxidation cycle treatment to prepare a high-temperature oxygen permeable membrane, and the cycle treatment is performed for 10 times;

[0077] The oxygen permeable membrane is placed in a heating furnace, heated to 1000°C at a heating rate of 1°C / min under a N2 atmosphere of 50 ml / min*cm 2 , and then subjected to reduction-purging-oxidation cycle treatment, the reduction atmosphere being a 1:1 H2 gas stream and N2 gas stream with a total flow rate of 100 ml / min*cm 2 , the purging atmosphere being a N2 gas stream with a total flow rate of 100 ml / min*cm 2 , and the oxidation atmosphere being a 1:4 O2 gas stream and N2 gas stream with a total flow rate of 100 ml / min*cm 2 , the reaction time of each stage being controlled to be 10 min, and the high-temperature oxygen permeable membrane is obtained after cooling at a cooling rate of 2°C / min under the oxidation atmosphere.

[0078] Example 3: (cycle treatment for 25 times)

[0079] Step 1: Preparation of oxygen permeable membrane embryo

[0080] A mixed solution of Ba, Sr, Co, Fe nitrate was prepared, with the molar concentration of Ba, Sr, Co, Fe ions being 0.05 mol / L, 0.05 mol / L, 0.08 mol / L, 0.02 mol / L, and then appropriate citric acid and ethylenediaminetetraacetic acid were added to the nitrate solution to make the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution be 0.3 mol / L and 0.2 mol / L respectively, and then ammonia water was added to make the pH value of the mixed solution be 8-9; the mixed solution was heated to about 85°C under stirring, and continued to be heated and evaporated until a sol-like product was formed, the formed sol product was dried at a temperature of 105°C to form a gel, and then the gel was heated to 400°C at a heating rate of 10°C / min in an air atmosphere, and kept at the temperature for 30 min for calcination, and then continued to be heated to 850°C at a heating rate of 10°C / min in an air atmosphere, and kept at the temperature for 1 h for natural cooling, and then the cooled calcined product was subjected to wet ball milling treatment, with anhydrous ethanol as the dispersant, and the sample was taken out and dried after ball milling for 5 h, to obtain Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder;

[0081] The Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 powder was laid in the mold at a thickness of 1.0 g / cm 2 and was molded at a pressure of 4 MPa for 15 h, and then the formed oxygen permeable membrane blank was taken out and placed in a muffle furnace and heated to 1000°C at a heating rate of 1°C / min, and kept at the temperature for 6 h, and then cooled to room temperature at a cooling rate of 1.5°C / min, to obtain an oxygen permeable membrane embryo;

[0082] Step 2: One side of the oxygen permeable membrane embryo prepared in step 1 was subjected to water vapor reduction and hydrogen catalyst coating treatment to obtain a primary oxygen permeable membrane embryo;

[0083] A mixed solution of La, Sr, Cu, Fe nitrate is configured, the molar concentration of La, Sr, Cu, Fe ions is 0.07 mol / L, 0.03 mol / L, 0.02 mol / L, 0.08 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added to the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and continues to be heated and evaporated until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 30 min, then continues to be heated to 850℃ at a heating rate of 10℃ / min in an air atmosphere, and is calcined for 1 h, then the calcined product after cooling is treated by wet ball milling, anhydrous ethanol is used as dispersant, the sample is taken out and dried after ball milling for 5 h, and a La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder is obtained; Ba 0.3 S r0.7 CoO3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, and water are mixed to prepare a coating slurry, the coating slurry is used to coat the water reduction hydrogen side of the oxygen permeable membrane, the coating amount is 2.74 g / cm 2 , and the sample is dried at 105℃ after coating

[0084] Step 3: the uncoated side of the primary oxygen permeable membrane blank prepared in step 2 is subjected to selective oxidation catalyst coating treatment to prepare a secondary oxygen permeable membrane blank;

[0085] A mixed solution of Ba, Sr, Co nitrate is configured, the molar concentration of Ba, Sr, Co ions is 0.03 mol / L, 0.07 mol / L, 0.1 mol / L, then proper citric acid and ethylenediaminetetraacetic acid are added into the nitrate solution, so that the concentration of citric acid and ethylenediaminetetraacetic acid in the mixed solution is 0.3 mol / L and 0.2 mol / L respectively, then ammonia water is added so that the pH value of the mixed solution is 8-9; the mixed solution is heated to about 90℃ under stirring, and heating and evaporation are continuously performed until a sol-like product is formed, the formed sol product is dried at a temperature of 105℃ to form a gel, then the gel is heated to 400℃ at a heating rate of 10℃ / min under air atmosphere, and is kept at the temperature for 30 min for calcination, then the temperature is continuously increased to 850℃ at a heating rate of 10℃ / min under air atmosphere, and is kept at the temperature for 1 h for calcination, and then the calcined product after cooling is subjected to wet ball milling treatment, anhydrous ethanol is used as a dispersant, the sample is taken out and dried after ball milling for 5 h, and a Ba 0.3 Sr 0.7 CoO3 powder is obtained.

[0086] La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 powder, CeO2 (150-200 mesh), hydroxypropyl methyl cellulose, glycerol, water are mixed to prepare a coating slurry, and the coating slurry is applied to the selective oxidation side of the biomass tar selective oxidation membrane, the coating amount is 1.14 g / cm 2 , and the sample is dried at 105℃ after coating.

[0087] Step 3: the secondary oxygen permeable membrane in step 2 is subjected to reduction / purging / oxidation cycle treatment to prepare a high-temperature oxygen permeable membrane, and the cycle treatment is performed for 25 times.

[0088] The oxygen permeable membrane is placed in a heating furnace, heated to 1000℃ at a heating rate of 1℃ / min under a N2 atmosphere of 50 ml / min*cm 2 , and then subjected to reduction-purging-oxidation cycle treatment, the reduction atmosphere is a 1:1 H2 gas flow and N2 gas flow with a total flow rate of 100 ml / min*cm 2 , the purging atmosphere is a N2 gas flow with a total flow rate of 100 ml / min*cm 2 , and the oxidation atmosphere is a 1:4 O2 gas flow and N2 gas flow with a total flow rate of 100 ml / min*cm 2 , the reaction time of each stage is controlled to be 10 min, and the high-temperature oxygen permeable membrane is obtained after cooling at a cooling rate of 2℃ / min under the oxidation atmosphere.

[0089] Example 4

[0090] As Figure 1 shown, a methanol / syngas cogeneration device includes a oxygen permeable membrane reactor 1, a water vapor generator 2, a first heat exchanger 3, a booster pump 4, a methanolization reactor 5, a methanol distillation column 6, a syngas / tar separator 7, a second heat exchanger 8; the oxygen permeable membrane reactor includes a water hydrogen production end and a selective oxidation end; the water hydrogen production end of the oxygen permeable membrane reactor is in communication with the H2O outlet of the water vapor generator and the H2O / H2 inlet of the first heat exchanger respectively; the H2 outlet of the first heat exchanger is in communication with the booster pump, and the H2O inlet of the first heat exchanger is in communication with the methanol distillation column; the booster pump is in communication with the CO2 output device, and the H2 / CO2 output port of the booster pump is in communication with the methanolization reactor; the methanolization reactor is in communication with the methanol distillation column; the selective oxidation end of the oxygen permeable membrane reactor is in communication with the syngas / tar separator, and the syngas / tar separator is in communication with the second heat exchanger.

[0091] As Figure 2 shown, the working process of the above-mentioned methanol / syngas cogeneration device includes: the device heats water to form water vapor through a water vapor evaporator, the water vapor enters the oxygen permeable membrane reactor, the water vapor reacts with the water reduction hydrogen production catalyst on the water hydrogen production end to produce hydrogen, the hydrogen is in communication with the booster pump from the water hydrogen production end, the booster pump increases the generated hydrogen and enters the methanolization reactor together with carbon dioxide, and the methanol is obtained by passing through the methanol distillation column after the reaction; the oxygen in the water is converted into lattice oxygen and transferred to the selective oxidation end, the biomass tar in the selective oxidation end is oxidized to produce syngas, and the selective oxidation catalyst is contained in the syngas layer, and the biomass tar is oxidized by the selective oxidation catalyst to produce H2 / CO syngas;

[0092] The device realizes the combined production of methanol / syngas through the water vapor generator, the oxygen permeable membrane reactor, the methanolization reactor and the syngas / tar separator, and at the same time, the raw materials for production are carbon dioxide, water and biomass tar, which can realize the efficient and clean utilization of carbon dioxide and the conversion of biomass fuel, and the device has the technical effects of high environmental protection performance, low raw material cost, high production efficiency and small energy consumption.

[0093] Comparative Example 1: (without circulating treatment)

[0094] Compared with Example 1, the reduction / blowing / oxidation treatment in Comparative Example 3 is not circulated.

[0095] Application Example:

[0096] The oxygen permeable membrane prepared in the above-mentioned Examples 1-3 and Comparative Example 1 is made into an oxygen permeable membrane reactor, and the oxygen permeable membrane reactor is used in the application of biomass tar to syngas / carbon dioxide to methanol combined production;

[0097] And test the reaction rate of the oxygen permeable membrane;

[0098] Reaction temperature: 850°C, water vapor flow: 4.4 g / (cm 2 *h), tar model compound (toluene) flow 4.4 g / (cm 2 *h), reaction rate calculated in terms of oxygen permeation per unit area.

[0099] Table 1 test results

[0100]

[0101] As shown in Table 1, the above experimental results show that the reaction rates of Example 1, Example 2, Example 3, Comparative Example 1 are 0.941 mmol / (g*min), 1.190 mmol / (g*min), 1.207 mmol / (g*min) and 0.997 mmol / (g*min) in turn, the reaction rates of Example 1, Example 2 and Example 3 are significantly higher than that of Comparative Example 1, and gradually increase with the increase of the number of redox cycle pretreatment, the above results show that the reaction rate of the high-temperature oxygen-permeable membrane of the present application is significantly improved compared with the high-temperature oxygen-permeable membrane without cycle treatment, the reaction rate of Example 3 is increased by 21% compared with Comparative Example 3, and the above results show that the reduction / blow-by / oxidation cycle treatment adopted in the present application can significantly improve the reaction rate of the high-temperature oxygen-permeable membrane.

[0102] The above merely describes the preferred embodiments of the present application, and does not limit the present application in any way, any simple modification, change and equivalent transformation of the above embodiments according to the technical essence of the present application still belong to the protection scope of the technical solutions of the present application.

Claims

1. A method for preparing a high-temperature oxygen-permeable membrane, characterized in that, The preparation steps include the following: Step 1: Prepare an oxygen-permeable membrane embryo; Step 2: Coat one side of the oxygen-permeable membrane preform obtained in Step 1 with a water vapor reduction hydrogen production catalyst to form a primary oxygen-permeable membrane preform. Step 3: Selectively oxidize the uncoated side of the primary oxygen-permeable membrane preform obtained in Step 2 to form a secondary oxygen-permeable membrane preform. Step 4: The secondary oxygen-permeable membrane from Step 3 is subjected to a reduction / purging / oxidation cycle treatment to produce a high-temperature oxygen-permeable membrane. The number of cycles is 5 to 25. The high-temperature oxygen-permeable membrane includes an oxygen-permeable membrane layer and a water vapor reduction hydrogen production layer and a biomass tar oxidation syngas production layer respectively disposed on both sides of the oxygen-permeable membrane layer. The material of the oxygen-permeable membrane layer is a perovskite oxide; the water vapor reduction hydrogen production layer comprises La. 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3 / CeO2; the components of the biomass tar oxidation syngas layer include Ba. 0.3 Sr 0.7 CoO3 / CeO2.

2. The preparation method according to claim 1, characterized in that, The chemical formula of the perovskite oxide is ABO3, wherein A includes one or more of La, Sr and Ba, and B includes one or more of Fe, Co, Ni and Cu.

3. The preparation method according to claim 1, characterized in that, The perovskite oxide is Ba. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3.

4. The preparation method according to claim 1, characterized in that, The preparation steps of the oxygen-permeable membrane embryo in step 1 include: Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 is molded and calcined to produce an oxygen-permeable membrane preform; The molding conditions include: molding cavity pressure of 3~6 MPa, molding time of 2~6 h, and molding filler density of 0.5~2.0 g / cm³. 2 ; The calcination conditions include: heating to 1000 ℃ at a heating rate of 1 ℃ / min, holding at that temperature for 6 h, and then cooling to room temperature at a cooling rate of 1.5 ℃ / min.

5. The preparation method according to claim 1, characterized in that, The step 2 of coating the water vapor reduction hydrogen production catalyst includes: coating a hydrogen permeable slurry onto one side of an oxygen permeable membrane preform and drying it to form a primary oxygen permeable membrane preform; The steam reduction hydrogen production catalyst slurry comprises the following components by mass: 10-30 parts of Ba 0.3 Sr 0.7 CoO3, 10-20 parts CeO2, 0.1-0.5 parts hydroxypropyl methylcellulose, 0.1-0.5 parts glycerol and 49-79.8 parts water; The coating conditions include: a coating density of 1.5~3.5 g / cm³. 2 ; The drying conditions include a drying temperature of 105°C.

6. The preparation method according to claim 1, characterized in that, The selective oxidation catalyst coating process described in step 3 includes: coating the selective oxidation catalyst slurry onto the uncoated side of the primary oxygen permeable membrane preform and drying it to form a secondary oxygen permeable membrane preform; The selective oxidation catalyst slurry comprises the following components by mass parts: 10-30 parts of La 0.7 Sr 0.3 Cu 0.2 Fe 0.8 O3, 5-20 parts CeO2, 0-0.5 parts hydroxypropyl methylcellulose, 0-1.0 parts glycerol and 48.5-85 parts water; The coating conditions include: a coating density of 0.5~2.0 g / cm³. 2 ; The drying conditions include a drying temperature of 105°C.

7. The preparation method according to claim 1, characterized in that, The reduction / purging / oxidation cycle treatment steps in step 4 include: preheating, reduction, purging, oxidation and cooling of the secondary oxygen permeable membrane in sequence; The preheating conditions include: the preheating atmosphere consists of nitrogen, and the preheating atmosphere flow rate is 50 ml / min*cm. 2 The temperature was increased to 1000 ℃ at a rate of 1 ℃ / min. The conditions for the reduction treatment include: a reducing atmosphere comprising hydrogen and nitrogen in a 1:1 mass ratio, and a reducing atmosphere flow rate of 50-120 ml / min*cm. 2 Processing time: 10 minutes; The purging conditions include: the purging atmosphere consists of nitrogen, and the purging atmosphere flow rate is 100 ml / min*cm. 2 Processing time: 10 minutes; The oxidation treatment conditions include: an oxidizing atmosphere comprising oxygen and nitrogen in a mass ratio of 1:4, and an oxidizing atmosphere flow rate of 50~120 ml / min*cm. 2 Processing time: 10 minutes; The cooling conditions include cooling at a rate of 2 °C / min under an oxidizing atmosphere.

8. The application of a method for preparing a high-temperature oxygen-permeable membrane according to any one of claims 1 to 7 in the combined production of biomass tar to syngas / carbon dioxide to methanol.

9. A methanol / syngas co-production unit, characterized in that, The device includes an oxygen-permeable membrane reactor and a steam generator connected to the oxygen-permeable membrane reactor. The oxygen-permeable membrane reactor includes a water reduction hydrogen production end and a selective oxidation end. The water reduction hydrogen production end is connected to a methanolization reactor, and the selective oxidation end is connected to a syngas / tar separator. The oxygen-permeable membrane reactor includes several stacked high-temperature oxygen-permeable membranes as described in any one of claims 1 to 7.

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