CN111085112B - Preparation method and application of gradient porous self-supporting symmetrical ceramic membrane - Google Patents
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Abstract
The invention relates to a preparation method and application of a gradient porous self-supporting symmetrical ceramic membrane, and belongs to the technical field of membrane separation. The gradient porous self-supporting symmetrical ceramic membrane comprises a dense layer positioned in the middle and gradient porous layers positioned on two sides of the dense layer, wherein the gradient porous layers are of gradient porous structures, and the porosity of the gradient porous structures of the gradient porous layers on each side decreases from the outer side to the inner side. The gradient porous self-supporting symmetrical ceramic membrane can effectively reduce deformation and cracking, enhance the operation stability of the membrane reactor and simultaneously keep higher gas permeation quantity.
Description
Technical Field
The invention relates to a preparation method and application of a gradient porous self-supporting symmetrical ceramic membrane, and belongs to the technical field of membrane separation.
Background
Mixed conductor ceramic membranes have achieved significant progress over the last decades, but still face many challenges for commercial applications. The gas permeation of the mixed conductor ceramic membrane is inversely proportional to the thickness of the membrane, so that in order to obtain a sufficiently high gas permeation, the prepared mixed conductor ceramic membrane must be thin enough, but the mechanical strength of the ceramic membrane must not be reduced too much, which is a challenge to the ceramic membrane preparation technology.
In response to the above challenges, asymmetric ceramic membranes have been developed. The asymmetric ceramic membrane comprises a porous supporting layer for providing mechanical strength and a compact functional layer for playing a role of separation and filtration, and the surface of the compact layer is required to be modified necessarily in order to increase the gas surface exchange specific surface area.
The traditional asymmetric ceramic membrane has the disadvantages of complex preparation process, low yield and low mass production degree, and meanwhile, in the using and operating process, due to the thermal matching problem between the porous layer and the compact layer, layering and cracking are easily caused, and safety accidents are caused.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a preparation method and application of a gradient porous self-supporting symmetrical ceramic membrane. The gradient porous self-supporting symmetrical ceramic membrane can effectively reduce deformation and cracking, and simultaneously keeps higher gas permeation quantity. The invention is realized by the following technical scheme.
A gradient porous self-supporting symmetrical ceramic membrane comprises a dense layer positioned in the middle and gradient porous layers positioned on two sides of the dense layer, wherein the gradient porous layers are of a gradient porous structure, and the porosity of the gradient porous structure of each gradient porous layer decreases from the outer side to the inner side.
The total thickness of the middle dense layer and the gradient porous layer positioned at the two sides of the dense layer is 0.5 mm-1.0 mm.
The thickness of the compact layer is 100µm～200µm。
A preparation method of a gradient porous self-supporting symmetrical ceramic membrane comprises the following steps:
step 1, mixing ceramic powder, deionized water, a dispersing agent, a binder, a plasticizer and a defoaming agent to obtain ceramic slurry, which is defined as slurry I;
step 2, mixing ceramic powder, a pore-forming agent, deionized water, a dispersing agent, a binder, a plasticizer and a defoaming agent to prepare pore-forming ceramic slurry, and preparing pore-forming ceramic slurry II, pore-forming ceramic slurry III and pore-forming ceramic slurry IV according to the mass percentages of the pore-forming agent to ceramic powder and the pore-forming agent to be respectively 10%, 25% and 40%;
step 3, preparing a thin film blank by respectively carrying out tape casting on the slurry I obtained in the step 1 and the pore-forming ceramic slurry II, the pore-forming ceramic slurry III and the pore-forming ceramic slurry IV obtained in the step 2, and sequentially defining the thin film blank as a blank I, a blank II, a blank III and a blank IV;
step 4, sequentially laminating the film blank prepared in the step 3 according to a blank IV, a blank III, a blank II, a blank I, a blank II, a blank III and a blank IV, and preparing a gradient porous ceramic membrane blank by adopting a vacuum hot-pressing process;
and 5, degreasing the gradient porous ceramic membrane blank obtained in the step 4 at the temperature of below 800 ℃, and then sintering the gradient porous ceramic membrane blank at the temperature of 1000-1600 ℃ for 3-5 h to obtain the gradient porous self-supporting symmetrical ceramic membrane.
The ceramic powder in step 1 and step 2 comprises mixed oxygen ion electronic conductive ceramic, such as SrCoO doped with tantalum oxide, niobium oxide and zirconium oxide3Series, LaxSr1-xCoyFe1-yO3, BaxSr1-xCoyFe1-yO3, La0.8Sr0.2CrxFe1-xO3, LaxSr1-xMnO3One or more of (1) and (b) in any ratio; or mixed proton electron conductor ceramics such as transition metal doped BaCeO3And SrCeO3Or a composite ceramic comprising a proton-conducting ceramic phase and an electron-conducting ceramic phase, such as (1-x) (SrZrO)3)-x(SrFeO3)(0<x<1)，(1-x)Sr0.95Ti0.9Nb0.1O3-δ-xBaCe0.2Zr0.7Y0.1O3(0<x<1), (1-x)La27W3.5Mo1.5O55.5-δ-xLa0.87Sr0.13CrO3-δ(0<x<1) One or more of the above mixtures in any proportion; in the step 1, the ceramic powder accounts for 30-50 wt% of the mass of the ceramic slurry; in the step 2, the ceramic powder and the pore-forming agent account for 30wt% of the mass of the porous ceramic slurry.
In the step 2, the pore-forming agent is one or more mixed organic matters with any proportion of graphite, starch and organic matters with the ignition point below 800 ℃.
A gradient porous self-supporting symmetrical ceramic membrane is applied to a membrane reactor to separate oxygen in air.
The invention has the beneficial effects that:
(1) the gradient porous self-supporting symmetrical ceramic membrane can realize the preparation of the gradient porous self-supporting symmetrical flat membrane by a one-step laminating hot-pressing process, thereby simplifying the working procedure and saving the cost;
(2) the porous support structure with gradient change of porosity reduces the thermal shrinkage difference of the blank in the degreasing and sintering processes and the frequent heating and cooling operation processes, reduces deformation and cracking, and improves the yield and the operation stability;
(3) the porous supporting layers on the two sides improve the overall mechanical strength of the membrane, and simultaneously increase the specific surface area of gas surface exchange on the two sides, so that the modification process of the asymmetric membrane on the surface of the dense layer in the later period can be omitted.
Drawings
FIG. 1 is a schematic structural view of a gradient porous self-supporting symmetric ceramic membrane according to the present invention;
FIG. 2 is a schematic view of the porosity gradient of a gradient porous self-supporting symmetric ceramic membrane of the present invention;
FIG. 3 is a schematic view of the application of the gradient porous self-supporting symmetric ceramic membrane of the present invention in oxygen permeation;
FIG. 4 is a schematic diagram of the application of the gradient porous self-supporting symmetric ceramic membrane in hydrogen permeation; .
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in fig. 1 and 2, the gradient porous self-supporting symmetrical ceramic membrane comprises a dense layer positioned in the middle and gradient porous layers positioned on two sides of the dense layer, wherein the gradient porous layers are in a gradient porous structure, and the gradient porous structure porosity of the gradient porous layers on each side decreases from the outer side to the inner side; the total thickness of the middle dense layer and the gradient porous layers positioned at the two sides of the dense layer is 0.5 mm; the thickness of the dense layer is 100µm。
The preparation method of the gradient porous self-supporting symmetrical ceramic membrane comprises the following steps:
step 1, mixing ceramic powder, deionized water (accounting for 61 percent of the mass of the ceramic slurry), a dispersing agent (Darvan-C accounting for 0.5 percent of the mass of the ceramic slurry), a binder (PVA-88 accounting for 6.5 percent of the mass of the ceramic slurry), a plasticizer (PEG-10000 accounting for 1.5 percent of the mass of the ceramic slurry) and a defoaming agent (PPG-2000 accounting for 0.5 percent of the mass of the ceramic slurry),obtaining ceramic slurry, which is defined as slurry I; the ceramic powder is tantalum oxide doped SrCoO3(ii) a The ceramic powder accounts for 30 percent of the mass of the ceramic slurry;
step 2, mixing ceramic powder, a pore-forming agent, deionized water (accounting for 61% of the mass of the ceramic slurry), a dispersing agent (Darvan-C accounting for 0.5% of the mass of the ceramic slurry), a binder (PVA-88 accounting for 6.5% of the mass of the ceramic slurry), a plasticizer (PEG-10000 accounting for 1.5% of the mass of the ceramic slurry), and a defoaming agent (PPG-2000 accounting for 0.5% of the mass of the ceramic slurry) to prepare pore-forming ceramic slurry, and preparing pore-forming ceramic slurry II, pore-forming ceramic slurry III and pore-forming ceramic slurry IV according to the condition that the mass percentages of the pore-forming agent and the ceramic powder are respectively 10%, 25% and 40%; the ceramic powder is tantalum oxide doped SrCoO3(ii) a The pore-forming agent is graphite, and the ceramic powder and the pore-forming agent account for 30% of the mass of the ceramic slurry;
step 3, preparing a thin film blank by respectively carrying out tape casting on the slurry I obtained in the step 1 and the pore-forming ceramic slurry II, the pore-forming ceramic slurry III and the pore-forming ceramic slurry IV obtained in the step 2, and sequentially defining the thin film blank as a blank I, a blank II, a blank III and a blank IV;
step 4, sequentially laminating the film blank prepared in the step 3 according to a blank IV, a blank III, a blank II, a blank I, a blank II, a blank III and a blank IV, and preparing a gradient porous ceramic membrane blank by adopting a vacuum hot-pressing process;
and 5, degreasing the gradient porous ceramic membrane blank obtained in the step 4 at the temperature of below 800 ℃, and then sintering the gradient porous ceramic membrane blank at the temperature of 1000 ℃ for 5 hours to obtain the gradient porous self-supporting symmetrical ceramic membrane.
As shown in fig. 3, the application of the gradient porous self-supporting symmetric ceramic membrane is to perform oxygen permeation on a membrane reactor. Air is swept at one side of the ceramic membrane, oxygen in the air penetrates through the ceramic membrane to reach the other side of the membrane body, the oxygen is carried away from the surface of the membrane body under the sweeping of inert gas, and the oxygen permeation flux reaches 2 ml.min-1·cm-2。
Example 2
As shown in FIGS. 1 and 2, the gradient porous self-supporting symmetric ceramic membrane comprises a plurality of poresThe gradient porous layer is of a gradient porous structure, and the porosity of the gradient porous structure of each side is gradually reduced from the outer side to the inner side; the total thickness of the middle dense layer and the gradient porous layers positioned at the two sides of the dense layer is 1.0 mm; the thickness of the dense layer is 200µm。
The preparation method of the gradient porous self-supporting symmetrical ceramic membrane comprises the following steps:
step 1, mixing ceramic powder, deionized water (accounting for 61% of the mass of the ceramic slurry), a dispersing agent (Darvan-C accounting for 0.5% of the mass of the ceramic slurry), a binder (PVA-88 accounting for 6.5% of the mass of the ceramic slurry), a plasticizer (PEG-10000 accounting for 1.5% of the mass of the ceramic slurry) and a defoaming agent (PPG-2000 accounting for 0.5% of the mass of the ceramic slurry) to obtain ceramic slurry, wherein the ceramic slurry is defined as slurry I; the ceramic powder is yttrium oxide doped BaCeO3(ii) a The ceramic powder accounts for 30wt% of the mass of the ceramic slurry;
step 2, mixing ceramic powder, a pore-forming agent, deionized water (accounting for 61% of the mass of the pore ceramic slurry), a dispersing agent (Darvan-C accounting for 0.5% of the mass of the pore ceramic slurry), a binder (PVA-88 accounting for 6.5% of the mass of the pore ceramic slurry), a plasticizer (PEG-10000 accounting for 1.5% of the mass of the pore ceramic slurry) and a defoaming agent (PPG-2000 accounting for 0.5% of the mass of the pore ceramic slurry) to prepare pore-forming ceramic slurry, and preparing pore-forming ceramic slurry II, pore-forming ceramic slurry III and pore-forming ceramic slurry IV according to the mass percentages of the pore-forming agent, namely the ceramic powder, and the pore-forming agent, of 10%, 25% and 40%, respectively; the ceramic powder is yttrium oxide doped BaCeO3(ii) a The pore-forming agent is starch, and the ceramic powder and the pore-forming agent account for 30wt% of the mass of the ceramic slurry;
step 3, preparing a thin film blank by respectively carrying out tape casting on the slurry I obtained in the step 1 and the pore-forming ceramic slurry II, the pore-forming ceramic slurry III and the pore-forming ceramic slurry IV obtained in the step 2, and sequentially defining the thin film blank as a blank I, a blank II, a blank III and a blank IV;
step 4, sequentially laminating the film blank prepared in the step 3 according to a blank IV, a blank III, a blank II, a blank I, a blank II, a blank III and a blank IV, and preparing a gradient porous ceramic membrane blank by adopting a vacuum hot-pressing process;
and 5, degreasing the gradient porous ceramic membrane blank obtained in the step 4 at the temperature of below 800 ℃, and then sintering the gradient porous ceramic membrane blank at the temperature of 1600 ℃ for 3 hours to obtain the gradient porous self-supporting symmetrical ceramic membrane.
The application of the gradient porous self-supporting symmetric ceramic membrane to a membrane reactor for hydrogen permeation is shown in fig. 4. Purging hydrogen-containing gas at one side of the ceramic membrane, wherein hydrogen permeates the ceramic membrane and reaches the other side of the membrane body, and is carried away from the surface of the membrane body under the purging of inert gas, and the permeation flux of hydrogen reaches 0.02 ml.min-1·cm-2。
Example 3
As shown in fig. 1 and 2, the gradient porous self-supporting symmetrical ceramic membrane comprises a dense layer positioned in the middle and gradient porous layers positioned on two sides of the dense layer, wherein the gradient porous layers are in a gradient porous structure, and the gradient porous structure porosity of the gradient porous layers on each side decreases from the outer side to the inner side; the total thickness of the middle dense layer and the gradient porous layers positioned at the two sides of the dense layer is 0.8 mm; the thickness of the dense layer was 150 aµm。
The preparation method of the gradient porous self-supporting symmetrical ceramic membrane comprises the following steps:
step 1, mixing ceramic powder, deionized water (accounting for 51% of the mass of the ceramic slurry), a dispersing agent (Darvan-C accounting for 0.6% of the mass of the ceramic slurry), a binder (PVA-88 accounting for 6.4% of the mass of the ceramic slurry), a plasticizer (PEG-10000 accounting for 1.5% of the mass of the ceramic slurry) and a defoaming agent (PPG-2000 accounting for 0.5% of the mass of the ceramic slurry) to obtain ceramic slurry, wherein the ceramic slurry is defined as slurry I; the ceramic powder is (1-x) Sr0.95Ti0.9Nb0.1O3-δ-xBaCe0.2Zr0.7Y0.1O3(0<x<1) (ii) a The ceramic powder accounts for 40wt% of the mass of the ceramic slurry;
step 2, ceramic powder, a pore-forming agent, deionized water (accounting for 51 percent of the mass of the porous ceramic slurry), a dispersant (Darvan-C accounting for 0.6 percent of the mass of the porous ceramic slurry), a binder (PVA-88 accounting for the mass of the pores of the ceramic slurry) and a binder (PVA-88)6.4 percent of the mass of the ceramic slurry), plasticizer (PEG-10000, which accounts for 1.5 percent of the mass of the porous ceramic slurry), defoamer (PPG-2000, which accounts for 0.5 percent of the mass of the porous ceramic slurry) are mixed to prepare pore-forming ceramic slurry, and pore-forming ceramic slurry II, pore-forming ceramic slurry III and pore-forming ceramic slurry IV are respectively prepared according to the mass percentages of 10 percent, 25 percent and 40 percent of the pore-forming agent, namely ceramic powder and the pore-forming agent; the ceramic powder is (1-x) Sr0.95Ti0.9Nb0.1O3-δ-xBaCe0.2Zr0.7Y0.1O3(0<x<1) (ii) a The pore-forming agent is starch, and the ceramic powder and the pore-forming agent account for 40wt% of the mass of the porous ceramic slurry;
step 3, preparing a thin film blank by respectively carrying out tape casting on the slurry I obtained in the step 1 and the pore-forming ceramic slurry II, the pore-forming ceramic slurry III and the pore-forming ceramic slurry IV obtained in the step 2, and sequentially defining the thin film blank as a blank I, a blank II, a blank III and a blank IV;
step 4, sequentially laminating the film blank prepared in the step 3 according to a blank IV, a blank III, a blank II, a blank I, a blank II, a blank III and a blank IV, and preparing a gradient porous ceramic membrane blank by adopting a vacuum hot-pressing process;
and 5, degreasing the gradient porous ceramic membrane blank obtained in the step 4 at the temperature of below 800 ℃, and then sintering the gradient porous ceramic membrane blank at the temperature of 1400 ℃ for 4 hours to obtain the gradient porous self-supporting symmetrical ceramic membrane.
The application of the gradient porous self-supporting symmetric ceramic membrane to a membrane reactor for hydrogen permeation is shown in fig. 4. Purging hydrogen-containing gas at one side of the ceramic membrane, wherein hydrogen permeates the ceramic membrane and reaches the other side of the membrane body, and is carried away from the surface of the membrane body under the purging of inert gas, and the permeation flux of hydrogen reaches 0.015 ml.min-1·cm-2。
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (6)
1. A preparation method of a gradient porous self-supporting symmetrical ceramic membrane comprises a dense layer positioned in the middle and gradient porous layers positioned on two sides of the dense layer, wherein the gradient porous layers are of a gradient porous structure, and the gradient porous structure porosity of the gradient porous layer on each side decreases progressively from the outer side to the inner side, and is characterized by comprising the following steps:
step 1, mixing ceramic powder, deionized water, a dispersing agent, a binder, a plasticizer and a defoaming agent to obtain ceramic slurry, which is defined as slurry I;
step 2, mixing ceramic powder, a pore-forming agent, deionized water, a dispersing agent, a binder, a plasticizer and a defoaming agent to prepare pore-forming ceramic slurry, and preparing pore-forming ceramic slurry II, pore-forming ceramic slurry III and pore-forming ceramic slurry IV according to the mass percentages of the pore-forming agent to ceramic powder and the pore-forming agent to be respectively 10%, 25% and 40%;
step 3, preparing a thin film blank by respectively carrying out tape casting on the slurry I obtained in the step 1 and the pore-forming ceramic slurry II, the pore-forming ceramic slurry III and the pore-forming ceramic slurry IV obtained in the step 2, and sequentially defining the thin film blank as a blank I, a blank II, a blank III and a blank IV;
step 4, sequentially laminating the film blank prepared in the step 3 according to a blank IV, a blank III, a blank II, a blank I, a blank II, a blank III and a blank IV, and preparing a gradient porous ceramic membrane blank by adopting a vacuum hot-pressing process;
step 5, degreasing the gradient porous ceramic membrane blank obtained in the step 4 at the temperature of below 800 ℃, and then sintering the gradient porous ceramic membrane blank at the temperature of 1000-1600 ℃ for 3-5 h to obtain the gradient porous self-supporting symmetrical ceramic membrane;
the ceramic powder in the step 1 and the step 2 comprises mixed oxygen ion electronic conductive ceramic, mixed proton electronic conductor ceramic or composite ceramic containing a proton conductive ceramic phase and an electronic conductive ceramic phase; the mixed oxygen ion electronic conductive ceramic comprises tantalum oxide, niobium oxide and zirconium oxide doped SrCoO3Series, LaxSr1-xCoyFe1-yO3, BaxSr1-xCoyFe1-yO3, La0.8Sr0.2CrxFe1-xO3, LaxSr1-xMnO3One or more of the above mixtures in any proportion; the mixed proton electron conductor ceramic comprises transition metal doped BaCeO3And SrCeO3One or more of the above mixtures in any proportion; composite ceramics comprising a proton-conducting ceramic phase and an electron-conducting ceramic phase, such as (1-x) (SrZrO)3)-x(SrFeO3)，0<x<1；(1-x)Sr0.95Ti0.9Nb0.1O3-δ-xBaCe0.2Zr0.7Y0.1O3，0<x<1；(1-x)La27W3.5Mo1.5O55.5-δ-xLa0.87Sr0.13CrO3-δ，0<x<1 in any ratio.
2. The method according to claim 1, wherein the gradient porous self-supporting symmetric ceramic membrane is prepared by: the total thickness of the middle dense layer and the gradient porous layer positioned at the two sides of the dense layer is 0.5 mm-1.0 mm.
3. The method according to claim 2, wherein the gradient porous self-supporting symmetric ceramic membrane is prepared by: the thickness of the compact layer is 100µm～200µm。
4. The method according to claim 1, wherein the gradient porous self-supporting symmetric ceramic membrane is prepared by: in the step 1, the ceramic powder accounts for 30-50 wt% of the mass of the ceramic slurry; in the step 2, the ceramic powder and the pore-forming agent account for 30wt% of the mass of the porous ceramic slurry.
5. The method according to claim 1, wherein the gradient porous self-supporting symmetric ceramic membrane is prepared by: in the step 2, the pore-forming agent is one or more mixed organic matters with any proportion of graphite, starch and organic matters with the ignition point below 800 ℃.
6. Use of a gradient porous self-supporting symmetric ceramic membrane according to claim 1 for the separation of oxygen from air on a membrane reactor.
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