Metal ceramic composite structure membrane as well as preparation method and application thereof

Abstract

The invention discloses a metal ceramic composite structure membrane and a preparation method and application thereof, and belongs to the technical field of composite membrane preparation. The method comprises the following steps: firstly, cutting a foam metal net to a target size, ultrasonically cleaning and drying; then dipping in slurry containing a metal oxide, and airing to obtain a porous metal net of which the surface is covered with the metal oxide; mixing the ceramic powder with a solvent and an adhesive to prepare ceramic powder slurry; and filling pores of a porous metal net with the mixture in a vacuum filtration manner, airing, carrying out dry-pressing molding, and sintering in an inert atmosphere containing hydrogen. According to the prepared metal ceramic composite structure film, on the premise that metal communication is kept, the metal phase volume ratio (lt) is reduced to the maximum extent; the metal ceramic composite structure has high mechanical strength and has a good application prospect in the aspect of mixed conductor membrane reactors due to the fact that the metal ceramic composite structure has high mechanical strength, and the function of a ceramic phase (such as conduction of oxygen ions, protons and the like) is enhanced.

Description

Technical Field

[0001] The invention belongs to the technical field of composite membrane preparation, and in particular relates to a metal-ceramic composite structure membrane and a preparation method and application thereof. Background Art

[0002] Catalytic membrane reactors can achieve reaction-separation coupling, simplify the operation process, reduce production costs, and promote the reaction process. They have the advantages of continuous operation and low energy consumption. According to the different phase compositions of membrane materials, they can be roughly divided into single-phase membrane reactors and two-phase membrane reactors, among which two-phase membrane reactors have higher mechanical strength and chemical stability.

[0003] At present, the dual-phase membrane material is mainly prepared by mechanically mixing the powders of the two phases, and then preparing the dual-phase membrane through processes such as dry pressing or tape casting and sintering. Taking the mixed oxygen ion-electronic conductor oxygen permeable membrane reactor as an example, since the electronic conductivity of the membrane material is generally much higher than the oxygen ion conductivity, in order to improve the permeability of the oxygen permeable membrane, it is necessary to minimize the volume proportion of the electronic conductor phase. In order for the oxygen permeable membrane to work properly, a continuous electronic conductor phase needs to be opened in the membrane phase to balance the charge during the oxygen ion transmission process, so both the electronic conductor phase and the oxygen ion conductor phase materials need to form a continuous conductive phase. Studies have shown that the dual-phase membrane prepared by mechanical mixing method needs each phase to account for more than or equal to 30% of the volume to form a continuous conductive phase. As a result, the volume proportion of the low conductivity phase (such as the oxygen ion conductor phase) in the dual-phase membrane is up to 70%, and when one of the phases accounts for a small proportion, it is easy to form a closed area in the membrane phase, thereby losing part of the conductivity of the dual-phase membrane material. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a metal-ceramic composite structure membrane and its preparation method and application. The present invention directly fills ceramic powder in the pores of foamed metal, and obtains a dense two-phase membrane after dry pressing and sintering. Since the electronic conductivity of metal materials is more than 10,000 times the oxygen ion conductivity of ceramic materials, in order to improve the permeability of the two-phase membrane, the volume proportion of the ceramic phase in the metal-ceramic composite structure membrane of the present invention can be significantly higher than the maximum volume proportion of the ceramic phase in the traditional two-phase membrane preparation method of 70%.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a metal-ceramic composite structure membrane, comprising the following steps:

[0007] (1) cutting the foam metal mesh into a porous metal mesh of a target size, ultrasonically cleaning, and drying;

[0008] (2) immersing the porous metal mesh in step (1) in a slurry containing metal oxide for 5-60 seconds and drying it to obtain a porous metal mesh with a surface covered with metal oxide;

[0009] (3) mixing the ceramic powder with the solvent and the adhesive, heating to 40-80° C., and stirring for 1-4 hours to obtain a ceramic powder slurry;

[0010] (4) filling the ceramic powder slurry in step (3) into the pores of the porous metal mesh in step (2) by vacuum filtration, and obtaining a green embryo after drying;

[0011] (5) The green body obtained in step (4) is dry pressed into shape, and then sintered at 1000-1500° C. in an inert atmosphere containing hydrogen to obtain a dense metal-ceramic composite structure membrane.

[0012] Based on the above technical solution, further, the metal mesh described in step (1) is a nickel mesh, a copper mesh or a stainless steel mesh.

[0013] Based on the above technical solution, further, the metal oxide described in step (2) is nickel oxide, copper oxide, or manganese oxide, and the mass ratio of the metal oxide, polyvinyl butyral, and solvent in the slurry containing the metal oxide is 1:0.5-2:10-100.

[0014] Based on the above technical solution, further, the solvent in step (2) is methanol or ethanol.

[0015] Based on the above technical solution, further, the ceramic powder described in step (3) is yttria-stabilized zirconia or samarium-doped cerium oxide.

[0016] Based on the above technical solution, further, the solvent in step (3) is deionized water.

[0017] Based on the above technical solution, further, the adhesive in step (3) is gum arabic.

[0018] Based on the above technical solution, further, in step (3), the mass ratio of the ceramic powder slurry, the solvent and the adhesive is 1:0.005-0.1:1-10.

[0019] Based on the above technical solution, further, the dry pressing pressure in step (5) is 100-300 MPa.

[0020] Based on the above technical solution, further, the volume percentage of hydrogen in the inert atmosphere containing hydrogen in step (5) is 4-10%.

[0021] Based on the above technical solution, further, in step (5), the sintering time is 2-10 hours.

[0022] Another aspect of the present invention provides a metal-ceramic composite structure membrane obtained by the above preparation method.

[0023] The present invention also provides application of the metal-ceramic composite structure membrane in a mixed conductor membrane reactor.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1) The volume proportion of the metal phase in the metal-ceramic composite structure membrane of the present invention can be reduced to less than 5%, thereby greatly increasing the volume proportion of the ceramic phase and enhancing the comprehensive performance of the mixed conductor membrane reactor.

[0026] 2) The mechanical strength of the metal-ceramic composite structure membrane of the present invention is higher than that of the ceramic-ceramic dual-phase structure membrane. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments, wherein:

[0028] Figure 1 : Schematic diagram of the bulk structure of a conventional two-phase mixed conductor film;

[0029] Figure 2 : Schematic diagram of the metal-ceramic composite structure membrane of the present invention;

[0030] Figure 3 : The cross-sectional microstructure of the metal-ceramic composite structure membrane prepared in Example 1;

[0031] Figure 4 : Surface micromorphology of the metal-ceramic composite structure membrane prepared in Example 1. DETAILED DESCRIPTION

[0032] The present invention is further described in detail below in conjunction with specific embodiments. The given examples are only for illustrating the present invention, but not for limiting the scope of the present invention.

[0033] It is obvious to those skilled in the art that various improvements and changes can be made to the specific implementation methods of the present invention without departing from the design concept of the present invention.

[0034] Example 1

[0035] This embodiment provides a method for preparing a metal-ceramic composite structure membrane, comprising the following steps:

[0036] (1) Cut 1.5 mm thick nickel foam into discs with a diameter of 18 mm, clean them with deionized water and anhydrous ethanol ultrasonically, and then dry them for later use;

[0037] (2) 3.01 g of manganese dioxide powder, 2.41 g of polyvinyl butyral and 54.5 g of ethanol were placed in a magnetic stirrer and stirred for 2 h to obtain a manganese dioxide slurry; the dried nickel foam was immersed in the manganese dioxide slurry for 10 s, taken out and dried;

[0038] (3) 6.01 g of YSZ (yttria-stabilized zirconia) powder, 0.10 g of gum arabic and 14.01 g of deionized water were placed in a magnetic stirrer, the magnetic stirrer was heated to 60 °C, and stirred for 2 h to obtain a YSZ slurry;

[0039] (4) placing the dried nickel foam impregnated with manganese dioxide and YSZ slurry in a Buchner funnel, vacuum filtering, taking out and drying to obtain a nickel foam-YSZ material green body;

[0040] (5) The obtained nickel foam-YSZ material green body is formed under a pressure of 200 MPa, and then placed in a tubular furnace, heated to 1400°C in a 5 vol.% H2-Ar mixed gas at 60 mL / min, and kept warm for 6 h. After cooling, the final nickel foam-YSZ metal ceramic composite structure membrane is obtained.

[0041] The nickel-based catalyst was brushed on both sides of the obtained metal-ceramic composite structure membrane, and 200 mL / min was introduced into the supply side at 900 °C. -1 A mixture of helium and water (10% He, 90% H2O) was introduced into the permeate side at a rate of 100 mL min -1 The hydrogen generation rate of a mixture of argon and hydrogen (50% Ar-50% H2) measured on the supply side was 1.02 mL cm -2 min -1 .

[0042] Example 2

[0043] This embodiment provides a method for preparing a metal-ceramic composite structure membrane, comprising the following steps:

[0044] (1) Cut 1.5 mm thick nickel foam into discs with a diameter of 18 mm, clean them with deionized water and anhydrous ethanol ultrasonically, and then dry them for later use.

[0045] (2) 1.51 g of manganese dioxide powder, 2.41 g of polyvinyl butyral and 54.5 g of ethanol were placed in a magnetic stirrer and stirred for 2 h to obtain a manganese dioxide slurry; the dried nickel foam was immersed in the manganese dioxide slurry for 10 s, taken out and dried;

[0046] (3) 6.01 g of YSZ powder, 0.05 g of gum arabic and 14.01 g of deionized water were placed in a magnetic stirrer, heated to 60 °C, and stirred for 2 h to obtain a YSZ slurry;

[0047] (4) placing the dried nickel foam impregnated with manganese dioxide and YSZ slurry in a Buchner funnel, vacuum filtering, taking out and drying to obtain a nickel foam-YSZ material green body;

[0048] (5) The obtained nickel foam-YSZ material green body is formed under a pressure of 200 MPa, and then placed in a tubular furnace, heated to 1400°C in a 5 vol.% H2-Ar mixed gas at 60 mL / min, and kept warm for 6 h. After cooling, the final nickel foam-YSZ metal ceramic composite structure membrane is obtained.

[0049] The nickel-based catalyst was brushed on both sides of the obtained metal-ceramic composite structure membrane, and 200 mL / min was introduced into the supply side at 900 °C. -1 A mixture of helium and water (10% He, 90% H2O) was introduced into the permeate side at a rate of 100 mL min -1 The hydrogen generation rate of the mixed gas of argon and hydrogen (50% Ar-50% H2) measured on the supply side was 0.79 mL cm -2 min -1 .

[0050] Example 3

[0051] This embodiment provides a method for preparing a metal-ceramic composite structure membrane, comprising the following steps:

[0052] (1) Cut 1.5 mm thick nickel foam into discs with a diameter of 18 mm, clean them with deionized water and anhydrous ethanol ultrasonically, and then dry them for later use;

[0053] (2) 3.01 g of nickel oxide powder, 2.41 g of polyvinyl butyral and 54.5 g of ethanol were placed in a magnetic stirrer and stirred for 2 h to obtain a nickel oxide slurry; the dried nickel foam was immersed in the nickel oxide slurry for 10 s, taken out and dried;

[0054] (3) 6.01 g of SDC (samarium-doped cerium oxide) powder, 0.10 g of gum arabic and 14.01 g of deionized water were placed in a magnetic stirrer, heated to 60 °C, and stirred for 2 h to obtain SDC slurry;

[0055] (4) placing the dried nickel foam impregnated with manganese dioxide and SDC slurry in a Buchner funnel, vacuum filtering, taking out and drying to obtain a nickel foam-SDC material green body;

[0056] (5) The obtained nickel foam-SDC material green body is formed under a pressure of 200 MPa, and then placed in a tubular furnace, heated to 1400°C in a 5 vol.% H2-Ar mixed gas at 60 mL / min, and kept warm for 6 h. After cooling, the final nickel foam-SDC metal ceramic composite structure membrane is obtained.

[0057] The nickel-based catalyst was brushed on both sides of the obtained metal-ceramic composite structure membrane, and 200 mL / min was introduced into the supply side at 900 °C. -1 A mixture of helium and water (10% He, 90% H2O) was introduced into the permeate side at a rate of 100 mL min -1 The hydrogen generation rate of the mixed gas of argon and hydrogen (50% Ar-50% H2) measured on the supply side was 0.92 mL cm -2 min -1 .

Claims

1. A method for preparing a metal-ceramic composite structure membrane, characterized in that: The following steps are involved: (1) cutting the foam metal mesh into a porous metal mesh of a target size, ultrasonically cleaning, and drying; (2) immersing the porous metal mesh in step (1) in a slurry containing metal oxide for 5-60 seconds and drying it to obtain a porous metal mesh with a surface covered with metal oxide; (3) mixing the ceramic powder with the solvent and the adhesive, heating to 40-80° C., and stirring for 1-4 hours to obtain a ceramic powder slurry; (4) filling the ceramic powder slurry in step (3) into the pores of the porous metal mesh in step (2) by vacuum filtration, and obtaining a green embryo after drying; (5) The green body obtained in step (4) is dry pressed into shape, and then sintered at 1000-1500° C. in an inert atmosphere containing hydrogen to obtain a dense metal-ceramic composite structure membrane.

2. The preparation method according to claim 1, characterized in that: The metal mesh described in step (1) is a nickel mesh, a copper mesh or a stainless steel mesh.

3. The preparation method according to claim 1, characterized in that The metal oxide described in step (2) is nickel oxide, copper oxide, or manganese oxide. The mass ratio of the metal oxide to polyvinyl butyral to the solvent in the slurry containing the metal oxide is 1:0.5-2:10-100.

4. The preparation method according to claim 1, characterized in that: The ceramic powders described in step (3) are yttria-stabilized zirconium oxide and samarium-doped cerium oxide; the solvent is deionized water; and the adhesive is gum arabic.

5. The preparation method according to claim 4, characterized in that: The mass ratio of the ceramic powder slurry, the solvent and the adhesive in step (3) is 1:0.005-0.1:1-10.

6. The preparation method according to claim 1, characterized in that: The dry pressing pressure in step (5) is 100-300 MPa.

7. The preparation method according to claim 1, characterized in that: The volume percentage of hydrogen in the inert atmosphere containing hydrogen in step (5) is 4-10%.

8. The preparation method according to claim 1, characterized in that: The sintering time in step (5) is 2-10 hours.

9. The metal-ceramic composite structure membrane obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the metal-ceramic composite structure membrane according to claim 9 in a mixed conductor membrane reactor.

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