CN115105970A - Preparation method of tubular ceramic membrane with one sealed end - Google Patents

Preparation method of tubular ceramic membrane with one sealed end Download PDF

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Publication number
CN115105970A
CN115105970A CN202110291242.0A CN202110291242A CN115105970A CN 115105970 A CN115105970 A CN 115105970A CN 202110291242 A CN202110291242 A CN 202110291242A CN 115105970 A CN115105970 A CN 115105970A
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membrane
tubular
ceramic
precursor
sealing
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江河清
梁方义
胡天淼
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to the field of gas separation, relates to a preparation method of a tubular ceramic membrane, and particularly relates to a method for preparing a tubular ceramic membrane with one sealed end. One opening end of the ceramic tubular membrane precursor tube body and a section of ceramic solid rod precursor are sealed through extrusion, and then the ceramic tubular membrane precursor tube body and the section of ceramic solid rod precursor are sintered into a compact structure at a high temperature, so that the tubular ceramic membrane with the end sealed at one end is obtained, and the sealing of the ceramic membrane in a high-temperature area is realized. The method has simple flow and good sealing performance, and fundamentally solves the problems that the sealing material and the membrane material are easy to react with each other, the thermal expansion is not matched and the like, which can cause unexpected characteristic change or leakage of the gas separation membrane; meanwhile, the technical problems of complex sealing process and the like of the tubular membrane caused by large size are solved, and the stable sealing effect is maintained, meanwhile, the structure is simple, and the operation is convenient.

Description

Preparation method of tubular ceramic membrane with one sealed end
Technical Field
The invention belongs to the field of gas separation, relates to a preparation method of a tubular ceramic membrane, and particularly relates to a preparation method of a tubular ceramic membrane with one sealed end.
Background
The most commonly used mixed conductor membrane is a novel ceramic membrane materialThe material has the conductivity of electrons and ions or electrons and protons, and can be used as an oxygen permeable membrane material or a hydrogen permeable membrane material. For example, as an oxygen permeable membrane material, under high temperature conditions (usually above 600 ℃), when there is a difference in oxygen partial pressure across the membrane, oxygen passes through oxygen vacancies in the membrane material crystal lattice in the form of oxygen ions, and is conducted from the high oxygen partial pressure side to the low oxygen partial pressure side, while electrons are conducted in the opposite direction by hopping between valence-variable metal ions, so that electroneutrality of the oxygen permeation process is achieved. Therefore, the membrane material can realize the oxygen transfer process without an external circuit, the oxygen conduction is carried out in a lattice vibration mode, theoretically, the oxygen selectivity of the oxygen permeable membrane is 100 percent, and the preparation of pure oxygen or ultra-pure oxygen can be realized. Besides being widely used for air separation and hydrogen purification, the ceramic mixed conductor membrane is applied to industrial processes of continuous oxygen consumption (such as methane partial oxidation reaction, oxidative coupling reaction and the like) and oxygen product separation (such as H) 2 O、CO 2 And the decomposition reaction of nitrogen oxides, etc.), and consumption of pure oxygen-oxygen separation coupling industrial processes (coupling ethane dehydrogenation to ethylene and water decomposition to hydrogen, coupling methane partial oxidation and nitrogen oxide degradation, etc.), etc. show great application potential.
The working temperature range of the ceramic membrane material is usually 600-1000 ℃, and the high-temperature sealing technology of the membrane is one of the key technologies which need to be solved urgently for realizing large-scale industrial application. The tubular ceramic oxygen permeable membrane is sealed by using a sealing material such as ceramic or glass cement, and the problems of mutual reaction, mismatch of thermal expansion and the like of the sealing material and a mixed conductor membrane material exist, so that membrane cracking and leakage are easily caused. If a high-temperature sealing is performed using a noble metal such as gold, silver, copper, etc., the cost increases and the sealing process is complicated, for example, Zhu, etc. is filled with Ba using Ag paste 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ One end of the tubular membrane is sealed for the production of high purity oxygen [ j.membr.sci.2009,345,47.]. Liang et al use Au paste on BaCo x Fe y Zr 1-x-y O 3-δ One end of the hollow fiber membrane was sealed and used to prepare pure oxygen [ ind.]. The method of sealing the membrane with the noble metal also has problems such as mismatch with the membrane material [ amongNational patent CN 106065950A; chinese patent CN 102248322A]. In addition, a cutting sleeve sealing mode can be adopted, or two open ends of the ceramic oxygen permeation membrane are sealed by rubber rings at a temperature far away from the high temperature region [ Chinese patent CN 102284252B; chinese patent CN 101912742 a; chinese patent CN 102979981 a; chinese patent CN 109745867A]Although the method can avoid the problem of high-temperature sealing of the ceramic oxygen permeable membrane, the sealing structure is complicated, and the use efficiency of the membrane is greatly reduced.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned disadvantages and drawbacks of the prior art and to providing a method for preparing a tubular ceramic membrane having one end sealed.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing a tubular ceramic membrane with one sealed end comprises the steps of filling a solid ceramic membrane driver with a membrane material the same as or similar to that of a tubular ceramic membrane precursor into one end of an opening of the tubular ceramic membrane precursor, extruding the solid ceramic membrane driver into a whole by using a die, and sintering the extruded solid ceramic membrane driver into a compact tubular ceramic membrane at a high temperature under a gradient temperature rise to obtain the tubular ceramic membrane with one sealed end.
Obtaining a ceramic tubular membrane precursor tube body by a phase inversion method or an extrusion molding method; preparing a ceramic solid rod precursor with the same or similar membrane material as the precursor tube body by extrusion molding, then plugging the solid rod precursor into one end port of the tubular membrane precursor tube body, extruding the solid rod precursor into a whole through a sealing mould, sealing one end of the tubular membrane precursor tube body, keeping the other end of the tubular membrane precursor tube body open, and then sintering at high temperature under gradient temperature rise to obtain the tubular ceramic membrane with one sealed end.
The diameter of the solid rod precursor is smaller than that of the tubular ceramic membrane precursor.
The tubular ceramic membrane with one sealed end can be a single-hole tubular membrane or a porous tubular membrane
The ceramic tubular membrane precursor tube body is a ceramic material with arbitrary mixing conduction of oxygen ions, protons and electrons.
The prepared tubular ceramic membrane precursor can be prepared according to actual requirements, and preferably has an outer diameter of 2-20mm and a tube wall thickness of 0.1-2 mm. The outer diameter of the ceramic solid rod precursor is smaller than the inner diameter of the tubular ceramic membrane precursor, and the ceramic solid rod precursor can be plugged into the ceramic tubular membrane precursor.
The ceramic material can be a single-phase component 1, or a mixture of a phase component 1 and a phase component 2, wherein the mass ratio of the phase component 1 to the phase component 2 is 10-90%;
wherein, phase component 1: a. the 1-x A' x B 1-y-z B' y B” z O 3-δ Wherein A, A' may be the same or different and are selected from Ba, Sr, La, Sm, Pr or Bi; B. b 'and B' may be the same or different and are selected from Fe, Co, Fe, Cu, Ca, Mn, Ga, Ti, Y, Zn, Mo, Ta, Ce, Pr, Gd, or La;
phase component 2: ce 1-x M x O 2-δ Wherein M is selected from Pr, Gd, Ti, Er, Y, Tm, Yb, Tb, Lu, Nd, Sm, Dy, Sr, Hf, Th, Ta, Nb or Pb;
in the two components, x and y are the element composition proportion of A ', B ' or M ', x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and delta is the oxygen vacancy mole fraction in the perovskite ceramic material.
The gradient temperature-rising high-temperature sintering is to sinter at medium temperature, then sinter at high temperature and then reduce the temperature to room temperature in a high-temperature muffle furnace in the atmosphere of air or oxygen-enriched air; specifically, the temperature is 0.5-10 ℃ for min -1 Temperature rise rate (preferably 1-5 ℃ C. for min) -1 ) Heating to 200-500 deg.c (preferably 300-500 deg.c) for 2-5 hr (preferably 3-4 hr); sintering, and roasting at high temperature at 1-10 deg.C for min -1 Temperature rise rate (preferably 2-5 ℃ for min) -1 ) Heating to 900-1600 ℃, and sintering for 2-20h (preferably 10-20 h); sintering at high temperature, and heating at 0.5-10 deg.C for min -1 The temperature reduction rate is reduced to room temperature, and sintering densification is realized.
A sealing die of a sealing method comprises a die plate and a sealing die, wherein the die plate comprises a base 1 and a gland 2, grooves are arranged on the adjacent sides of the gland 2 and the base 1, and a reducing through hole 3 is formed after the grooves are closed.
The inner wall of the reducing through hole 3 is an inclined wall or a stepped wall.
The mould using mode, during extrusion sealing, fills in the port department of tubulose ceramic membrane precursor with the solid stick precursor of pottery, later will fill in tubulose membrane precursor one end of a section solid stick and arrange in the undergauge through-hole 3 and sealed end are located the 3 narrow ends of undergauge through-hole keep tubulose ceramic oxygen permeation membrane under the mould on the central line of notch, then tubulose membrane precursor body and solid stick pass through gland and base 3 compress tightly fixedly.
The sealing mould material can be stainless steel, plastic, wood or ceramic and the like.
The invention has the advantages that:
1. the preparation method of the tubular ceramic membrane for sealing one end is suitable for obtaining the ceramic membrane from any ceramic material, wherein the main body part and the sealing part of the tubular membrane are both composed of membrane materials, thereby fundamentally solving the problems of easy mutual reaction, thermal expansion mismatching and the like of the sealing material and the oxygen permeable membrane material, and effectively solving the high-temperature sealing problem of the tubular ceramic membrane; the tubular membrane with one sealed end can be applied to high-temperature and high-pressure environments.
2. Compared with the method that two opening ends penetrating through the ceramic membrane are sealed by rubber rings far away from the high-temperature area, the tubular ceramic membrane with one sealed end prepared by the method can place the sealed end of the membrane in the high-temperature area to realize sealing, and can effectively improve the use efficiency of the membrane.
3. The invention has simple sealing process and convenient operation, and does not need complex equipment, additional sealing materials and spare parts; the obtained mixed conductor film has good sealing performance at the sealing end.
4. The method has wide applicability, and can be suitable for preparing single-hole tubular membranes or porous tubular membranes with different sizes, including all ceramic membrane materials.
Description of the drawings:
fig. 1A is a schematic structural view of a sealing mold according to an embodiment of the present invention, which includes a base 1, a gland 2, and a reduced diameter through hole 3, wherein an inner wall of the reduced diameter through hole 3 is an inclined wall.
Fig. 1B is a schematic structural view of another sealing mold provided in an embodiment of the present invention, where 1-a base: 2-gland and 3-reducing through hole, wherein the inner wall of the reducing through hole 3 is a step wall.
FIG. 2 is a photograph of a film prepared in example 2 of the present inventionBaFe sealed at one end 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ Structural morphology before and after roasting of the sealed end and the open end of the precursor: wherein (A) and (B) are structural appearances of the tubular film before and after the sealing end is baked; (C) and (D) the structural morphology of the tubular membrane before and after the open end is baked; (E) and (F) is a scanning electron micrograph of the sealed end surface and open end cross section of the tubular film after sintering.
FIG. 3 is a schematic view of a device for testing the sealing performance of the tubular ceramic oxygen permeable membrane used in examples 2, 3 and 4, wherein the device comprises a two-way ferrule adapter with a screw cap, a rubber ring, a stainless steel tube, a pressure gauge and a stop valve.
FIG. 4 shows the preparation of sintered BaFe in example 2 of the present invention 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ XRD results of film powder
FIG. 5 shows BaFe sealed at one end according to an embodiment of the present invention 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ Results of 300-hour airtightness testing of the tubular membranes at 4.2 bar.
FIG. 6 shows one end sealed BaFe prepared in example 2 of the present invention 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ The oxygen permeation amount and the oxygen purity change chart of the tubular membrane in the temperature rise process of preparing oxygen.
FIG. 7 shows BaFe sealed at one end prepared in example 2 of the present invention 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ The oxygen permeability and oxygen purity stability of the tubular membrane in 500 hours of oxygen preparation were tested.
FIG. 8 is a two-phase 60 wt.% Ce seal at one end of an embodiment of the invention 0.9 Pr 0.1 O 2-δ -40wt.％Pr 0.6 Sr 0.4 Fe 0.6 AlCo 0.4 O 3-δ Results of 300-hour airtightness testing of tubular membranes at 5.2 bar.
FIG. 9 is 60 wt.% Ce of one end seal prepared in example 2 of the invention 0.9 Pr 0.1 O 2-δ -40wt.％Pr 0.6 Sr 0.4 Fe 0.6 AlCo 0.4 O 3-δ Preparation of tubular membranesOxygen permeation quantity and oxygen purity change chart in the oxygen temperature rise process.
The specific implementation scheme is as follows:
the embodiments of the present invention will be further described with reference to the accompanying drawings and examples, it being understood that the embodiments described herein are merely for purposes of illustration and explanation and are not intended to limit the invention.
Example 1:
as shown in figure 1, the sealing mould is divided into two parts, namely the mould comprises a base 1 and a gland 2, the adjacent sides of the gland 2 and the base 1 are provided with grooves, and a reducing through hole 3 is formed after the grooves are closed.
The inner wall of the reducing through hole 3 is an inclined wall or a stepped wall;
in the using mode, during extrusion sealing, one end of the tubular ceramic membrane precursor is sealed through the plugged solid rod precursor, then the tubular membrane precursor is placed in the reducing through hole 3, one end plugged into one section of the solid rod is located at the narrow end of the reducing through hole 3, and then the tubular membrane precursor body and the solid rod are compressed, sealed and fixed through the gland and the base 3.
Example 2
1) Tubular ceramic film BaFe 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ (BCFZY) precursor: according to the prior art, BaCO is added 3 ,Fe 2 O 3 ,CO 3 O 4 ,ZrO 2 ,Y 2 O 3 The powder is fully and uniformly mixed according to the molar ratio of metal in a film material, polymer adhesive hydroxypropyl methyl cellulose (HPMC) with the weight percentage of 5 percent of the mixed powder is added after the powder is uniformly mixed, and then glycerin with the weight percentage of 2 percent of the mixed powder and water with the weight percentage of 15 percent of the mixed powder are added to be kneaded into pug. And after vacuum pugging, extruding and forming the pug to prepare a BCFZY tubular ceramic membrane precursor, wherein the outer diameter of the precursor is 7.4mm, the wall thickness of the precursor is 0.7mm, and the precursor is cut into 50cm in length according to needs, as shown in figure 2C.
2) The BCFZY ceramic solid rod precursor is prepared by mixing the BCFZY pug components recorded in the step 1), then extruding and forming, wherein the outer diameter of the precursor is 5.6mm, the length of the precursor is 2.0cm,
3) sealing: inserting a ceramic solid rod precursor into a port of a tubular ceramic membrane precursor, then placing one end of the tubular membrane precursor inserted with a section of solid rod on the narrow end (i.e. small-diameter end) of the reducing through hole 3 in the embodiment 1, keeping the tubular ceramic oxygen permeable membrane on the central line of the lower groove of the mould, then pressing down the upper part of a gland bush of the mould, extruding the upper part of the gland bush into a whole through a sealing mould, obtaining a tubular membrane precursor with one end sealed, keeping the other end of the tubular membrane precursor open, and then drying to obtain the tubular membrane precursor with one sealed end, as shown in fig. 2A.
4) Roasting: placing the formed tubular oxygen permeable membrane precursor with one sealed end into a high-temperature electric furnace, and sintering at high temperature in the air by the following sintering procedures: slowly heating to 400 ℃ at the heating rate of 2 ℃/min, staying for 2 hours to remove organic matters, heating to 1300 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 10 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min to obtain the tubular ceramic oxygen permeable membrane with one end sealed, wherein the outer diameter of the tubular ceramic oxygen permeable membrane is about 5mm, the wall thickness of the tubular ceramic oxygen permeable membrane is about 0.5mm, and the length of the tubular ceramic oxygen permeable membrane is about 36cm (see figures 2 and 4). As can be seen from FIG. 2, BaFe sealed at one end 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ The structural appearances of the sealed end and the open end of the precursor before and after roasting are as follows: wherein (A) and (B) are structural appearances of the tubular film before and after the sealing end is baked; (C) and (D) the structural morphology of the tubular film before and after the open end is baked; (E) and (F) is a scanning electron microscope image of the sealed end surface and the open end cross section of the sintered tubular membrane, which shows that the sealed end of the sintered tubular membrane is compact and can realize the preparation of high purity oxygen. As can be seen from FIG. 4, the sintered BaFe was prepared 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ The XRD result of the film powder shows that the crystal structure of BFCZY is cubic, which is beneficial to obtaining high oxygen permeability.
Example 3
1) Tubular ceramic membrane BaFe 0.4 Co 0.4 Zr 0.15 Y 0.05 O 3-δ (BCFZY) precursor: according to the prior art, 84g of BCFZY powder are dissolved in 90g of N-methylpyrrolidone as solventPreparing a membrane casting solution by using NMP (NMP), 15g of polymer binder polysulfone (PSf) and 1g of dispersant polyvinylpyrrolidone (PVP), preparing a BCFZY tubular ceramic oxygen permeable membrane precursor by using a wet spinning method, wherein the outer diameter of the precursor is 7.4mm, the wall thickness of the precursor is 0.7mm, and cutting the precursor into a length of 50cm according to requirements.
2) The BCFZY ceramic solid rod precursor is prepared by mixing the BCFZY pug components recorded in the step 1), then extruding and forming, wherein the outer diameter of the precursor is 5.6mm, the length of the precursor is 2.0cm,
3) sealing: inserting a ceramic solid rod precursor into a port of a ceramic tubular film precursor, then placing one end of the tubular film precursor inserted into a section of solid rod on the narrow end (namely, the small-diameter end) of the reducing through hole 3 in the embodiment 1, keeping the tubular ceramic film on the central line of the lower groove of the mold, then pressing the upper part of the mold to extrude and divide the tubular ceramic film into a whole through a pressing cover of the sealing mold, obtaining the tubular ceramic film precursor with one end sealed, keeping the other end of the tubular film precursor open, and then drying to obtain the tubular film precursor with one sealed end.
4) Roasting: and (3) placing the formed tubular ceramic membrane precursor with the end socket at one end into a high-temperature electric furnace, and sintering at high temperature in the air by the following sintering procedures: slowly heating to 400 ℃ at the heating rate of 2 ℃/min, staying for 2 hours to remove organic matters, heating to 1300 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 10 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min to obtain the tubular ceramic oxygen permeable membrane with one end sealed, wherein the outer diameter of the tubular ceramic oxygen permeable membrane is about 5mm, the wall thickness of the tubular ceramic oxygen permeable membrane is about 0.5mm, and the length of the tubular ceramic oxygen permeable membrane is about 36 cm.
The tubular ceramic membrane BCFZY with the end socket at one end obtained after roasting has a compact sealing end, and the membrane body is also compact, so that the preparation of high-purity oxygen can be realized.
Example 4
1) Ceramic tubular membranes 60 wt.% Ce 0.9 Pr 0.1 O 2-δ -40wt.％Pr 0.6 Sr 0.4 Fe 0.6 AlCo 0.4 O 3-δ (CP-PSFC) precursor: according to the prior art, SrCO 3 ,Fe 2 O 3 ,CO 3 O 4 ,Pr 6 O 11 ,CeO 2 The powders were mixed well in accordance with the molar ratio of the metals, and then 5 wt% of the above mixed powder of hydroxypropyl methylcellulose (HPMC) as a polymer binder was added, and then 3 wt% of glycerin as the above mixed powder and 15 wt% of water as the above mixed powder were added and kneaded into a paste. And after the pug passes through vacuum annual pug, extrusion forming is adopted to prepare the CP-PSFC tubular ceramic membrane precursor, the outer diameter of the precursor is 7.4mm, the wall thickness of the precursor is 0.7mm, and the precursor is cut into 50cm in length according to requirements. .
2) The CP-PSFC ceramic solid rod precursor is prepared by mixing the CP-PSFC mud components recorded in the step 1), then preparing a BCFZY ceramic solid rod precursor by extrusion molding, wherein the outer diameter of the precursor is 5.6mm, the length of the precursor is 2.0cm,
3) sealing: the method comprises the steps of plugging a ceramic solid rod precursor into a port of a ceramic tubular film precursor, then placing one end of the tubular film precursor plugged with a section of solid rod on the narrow end (namely, a small-diameter end) of the reducing through hole 3 in the embodiment 1, keeping a tubular ceramic film on the central line of a lower groove of a mold, pressing down an upper part of a gland bush of the mold, extruding the upper part of the gland bush into a whole through a sealing mold, obtaining the tubular ceramic film precursor with one end sealed, keeping the other end of the tubular film precursor open, and then drying to obtain the tubular film precursor with one sealed end.
4) Roasting: the formed tubular ceramic oxygen permeable membrane precursor with the end socket at one end is put into a high-temperature electric furnace and is sintered at high temperature in the air through the following sintering procedures: slowly heating to 400 ℃ at the heating rate of 2 ℃/min, staying for 2 hours to remove organic matters, heating to 1400 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 10 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min to obtain the tubular ceramic oxygen permeable membrane with one end sealed, wherein the outer diameter of the tubular ceramic oxygen permeable membrane is about 5.0mm, the wall thickness of the tubular ceramic oxygen permeable membrane is about 0.5mm, and the length of the tubular ceramic oxygen permeable membrane is about 38 cm.
The tubular ceramic membrane CP-PSFC with the end socket at one end obtained after roasting has a compact sealing end, and the membrane body is also compact, so that the preparation of high-purity oxygen can be realized.
Application example 1:
the hermetic seal test was performed on the BFCZY tubular film obtained in example 2 above with one end sealed: the insides of one-end-sealed tubular membranes prepared in the above examples were pressurized to 4.2bar with air, respectively, and maintained for 300 hours (see fig. 5).
The tubular ceramic BCFZY oxygen permeable membrane of example 2 above, sealed at one end, was tested for gas tightness in a sealed test setup (see figure 3). The open end of the tubular ceramic BCFZY oxygen permeable membrane is sealed and fixed in the two-way clamping sleeve joint by using a rubber ring, a stainless steel pipe extrudes the rubber ring by rotating a screw cap to realize the sealing of the open end of the tubular membrane and the stainless steel pipe, the stainless steel pipe is connected with a nitrogen steel cylinder by a stop valve, and a pressure gauge is arranged in the middle of the stainless steel pipe to check pressure change. The sealed end of the tubular ceramic BCFZY oxygen permeable membrane is freely placed in the air, and the mechanical stress generated by the thermal expansion of the membrane tube under the high temperature condition (generally over 600 ℃) in the future can be avoided.
As can be seen from the figure 5, the tubular ceramic BCFZY oxygen permeable membrane is filled with air, pressurized to 4.2bar, the stop valve is closed, the pressure in the membrane is detected by the pressure gauge, the pressure in the membrane is always kept at 4.2bar within 300 hours of the test, the pressure is not reduced, the sealing property is very good, and the preparation method of the tubular ceramic membrane with one sealed end is very effective.
Application example 2:
the tubular ceramic BFCZY oxygen permeable membrane with one sealed end prepared in the above example 2 is used for high-purity oxygen preparation, and the concentration and oxygen permeability of oxygen obtained by air separation in the temperature rise process are examined. The prepared tubular ceramic BFCZY oxygen permeable membrane sealing end with one sealed end is adjusted in a constant temperature area of an electric furnace and freely placed in the air, so that the mechanical stress generated by the thermal expansion of a membrane tube under the high temperature condition (usually over 600 ℃) in the future can be avoided, and the temperature of the electric furnace is adjusted by utilizing a thermocouple and a temperature controller; the open end of the membrane was sealed using the ferrule of application example 1, located outside the electric furnace in the room temperature zone, and 100mLmin was passed over the outside of the tubular membrane -1 The inner side of the tubular membrane is connected to a vacuum pump through a clamping sleeve; the gas drawn off by the vacuum pump was analyzed for purity on-line by gas chromatography, and the tail gas flow rate was measured by a bubble flow meter (see fig. 6).
From the results of oxygen permeation and oxygen concentration of FIG. 6 with temperature change, the stability at each temperature was 1hMeasuring at a stable state, and as shown in FIG. 6, when the temperature is increased from 750 deg.C to 950 deg.C under the conditions of-1 bar vacuum degree and normal air side pressure, the oxygen permeability is increased from 13.98cm 3 min -1 Increased to 28.18cm 3 min -1 (ii) a The oxygen purity is increased from 99.92% to 99.99%, and the oxygen permeability and oxygen purity of the hollow fiber membrane with one sealed end are increased along with the increase of the temperature. The oxygen-permeable membrane of the mixed conductor theoretically has the oxygen selectivity of 100%, but a test system has inevitable trace leakage, so the proportion of the system leakage is gradually reduced along with the increase of the oxygen permeability, and the oxygen purity is gradually increased. Therefore, in practical application, the prepared oxygen can reach the standard of ultra-pure oxygen (the oxygen purity is more than 99.9999 percent) along with the increase of the oxygen permeability by 2 to 3 orders of magnitude.
To examine the stability of the prepared one-end sealed tubular ceramic BFCZY oxygen permeable membrane in preparing pure oxygen, the membrane was subjected to stability experiments at 900 ℃ for more than 500 hours (see fig. 7). Oxygen permeability was maintained at 25cm throughout the 500 hour test 3 min -1 About, the oxygen purity is always stable over 99.98%. The long-term stability of the hollow fiber membrane with one sealed end at high temperature is good, and the membrane characteristic change or leakage caused by the problems that the sealing material and the membrane material are easy to react with each other, the thermal expansion is not matched and the like are successfully avoided in the temperature rising and reducing process and the high-temperature running process.
Application example 3:
the two-phase CP-PSFC tubular oxygen permeable membrane of example 4 above, sealed at one end, was tested for gas tightness in a sealed test setup (see FIG. 3). The detection method is the same as the application example 1, the open end of the biphase CP-PSFC tubular membrane is sealed and fixed in the two-way cutting sleeve joint by using a rubber ring, the stainless steel tube extrudes the rubber ring to realize the sealing of the open end of the oxygen permeable membrane and the stainless steel tube by rotating a screw cap, the stainless steel tube is connected with an air gas steel cylinder by a stop valve, and a pressure gauge is arranged in the middle of the stainless steel tube to check the pressure change.
As can be seen from fig. 8, the ceramic membrane was pressurized to 5.2bar with air, the stop valve was closed, and the pressure in the membrane was measured by the pressure gauge, and the pressure in the membrane was maintained at 5.0bar all the time within 5 hours of the test, which did not decrease, showing that the sealing property was very good, indicating that the two-phase tubular membrane of the present invention, which was sealed at one end, was also very effective.
Application example 4:
the prepared biphase CP-PSFC tubular oxygen permeable membrane with one sealed end is used for preparing high-purity oxygen, the concentration and the oxygen permeability of the oxygen obtained by air separation in the temperature rise process are inspected, and the detection method is the same as the application example 2. The sealed end of the biphase CP-PSFC tubular oxygen permeable membrane with one sealed end is adjusted in a constant temperature area of the electric furnace and freely placed in the air, so that the mechanical stress generated by the thermal expansion of the membrane tube under the high temperature condition (usually over 600 ℃) can be avoided in the future, and the temperature of the electric furnace is adjusted by utilizing a thermocouple and a temperature controller; the open end of the membrane was sealed using the ferrule of application example 1, positioned outside the electric furnace in the room temperature zone, and the outside of the tubular membrane was vented for 300mL min -1 The inner side of the tubular membrane is connected to a vacuum pump through a clamping sleeve; the gas drawn off by the vacuum pump was analyzed for purity by gas chromatography on-line and the tail gas flow rate was measured by a bubble flow meter (see fig. 9).
From the results of oxygen permeation and oxygen concentration of FIG. 9 with temperature change, each temperature was stabilized for 1 hour, and a point was taken for measurement after reaching a stable state, as shown in the figure, under the conditions of a vacuum degree of about-1 bar and an air side pressure of normal pressure, when the temperature was increased from 750 ℃ to 900 ℃, the oxygen permeation was from 6.54cm 3 min -1 Increased to 10.78cm 3 min -1 (ii) a The oxygen purity increased from 99.3% to 99.7%. The oxygen permeability and oxygen purity of the hollow fiber membrane sealed at one end increase with increasing temperature. Therefore, the oxygen permeation quantity and the oxygen concentration of the adopted two-phase CP-PSFC tubular oxygen permeable membrane with one sealed end are increased along with the rise of the temperature, which shows that the tubular ceramic membrane with one sealed end has good long-term stability at high temperature, and the membrane characteristic change or leakage caused by the problems of easy mutual reaction, thermal expansion mismatching and the like of a sealing material and a membrane material are successfully avoided in the temperature rise and fall process.
In conclusion, the tubular ceramic membrane with one sealed end prepared by the invention effectively solves the high-temperature sealing problem of the tubular membrane, has low preparation cost and simple process, and can realize batch preparation; meanwhile, the tubular ceramic membrane with one sealed end can be applied to high-temperature and high-pressure environments, and when the prepared tubular ceramic membrane with one sealed end is applied to the air separation process, high-purity oxygen can be directly obtained by a one-step method. Meanwhile, the technical problems of complex sealing process and the like of the tubular membrane caused by large size are solved, and the stable sealing effect is maintained, and meanwhile, the structure is simple and the operation is convenient.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.

Claims (10)

1. A preparation method of a tubular ceramic membrane with one sealed end is characterized by comprising the following steps: and filling a solid ceramic membrane precursor with a membrane material the same as or similar to the tubular ceramic membrane precursor into one end of the opening of the tubular ceramic membrane precursor, extruding the solid ceramic membrane precursor into a whole by using a die, and sintering the extruded solid ceramic membrane precursor into a compact ceramic membrane at a high temperature under the condition of gradient temperature rise to obtain the tubular ceramic membrane with one sealed end.
2. The method of claim 1, wherein: obtaining a ceramic tubular membrane precursor tube body by a phase inversion method or an extrusion molding method; preparing a ceramic solid rod precursor with the same or similar membrane material as the precursor tube body by extrusion molding, then plugging the solid rod precursor into one end port of the tubular membrane precursor tube body, extruding the solid rod precursor into a whole through a sealing mould, sealing one end of the tubular membrane precursor tube body, keeping the other end of the tubular membrane precursor tube body open, and then sintering at high temperature under gradient temperature rise to obtain the tubular ceramic membrane with one sealed end.
3. The method of claim 2, wherein: the diameter of the solid rod precursor is smaller than that of the tubular ceramic membrane precursor.
4. A method according to claim 1 or 2, characterized in that: the tubular ceramic membrane with one sealed end can be a single-hole tubular membrane or a porous tubular membrane.
5. The method of claim 1, wherein: the ceramic tubular membrane precursor tube body is a ceramic material with arbitrary mixing conduction of oxygen ions, protons and electrons.
6. The method of claim 5, wherein: the ceramic material can be a single-phase component 1, or a mixture of a phase component 1 and a phase component 2, wherein the mass ratio of the phase component 1 to the phase component 2 is 10-90%;
wherein, phase component 1: a. the 1-x A' x B 1-y-z B' y B” z O 3-δ Wherein A, A' can be the same or different and is selected from Ba, Sr, La, Sm, Pr or Bi; B. b 'and B' may be the same or different and are selected from Fe, Co, Fe, Cu, Ca, Mn, Ga, Ti, Y, Zn, Mo, Ta, Ce, Pr, Gd, or La;
phase component 2: ce 1-x M x O 2-δ Wherein M is selected from Pr, Gd, Ti, Er, Y, Tm, Yb, Tb, Lu, Nd, Sm, Dy, Sr, Hf, Th, Ta, Nb or Pb;
in the two components, x and y are the element composition proportion of A ', B ' or M ', x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and delta is the oxygen vacancy mole fraction in the perovskite ceramic material.
7. A method according to claim 1 or 2, characterized in that: the gradient temperature-raising high-temperature sintering is that the mixture is heated to 200-500 ℃ at the temperature-raising speed of 0.5-10 ℃/min in a high-temperature muffle furnace in the atmosphere of air or oxygen-enriched air, and is sintered for 1-5 h; then heating to 900-1600 ℃ at the heating rate of 0.5-10 ℃/min, sintering for 2-20 hours; finally, the temperature is reduced to the room temperature at the cooling speed of 0.5-10 ℃/min, and the sintering densification is realized.
8. A sealing mold for a sealing method according to claim 1, wherein: the membrane tool includes base 1 and gland 2, just gland 2 and the adjacent side of base 1 all are equipped with the recess to form a undergauge through-hole 3 after the recess is closed.
9. A sealing die for use in the sealing method of claim 8, wherein: the inner wall of the reducing through hole 3 is an inclined wall or a stepped wall.
10. A sealing die for use in the sealing method of claim 8, wherein: the mould user mode during extrusion sealing, packs in the port department of tubulose ceramic membrane precursor with the solid stick precursor of pottery, later will pack in one section solid stick's tubulose membrane precursor one end and arrange in reducing through-hole 3 and sealed end are located reducing through-hole 3 narrow end keeps tubulose ceramic oxygen permeation membrane under the mould on the central line of notch, then tubulose membrane precursor body and solid stick pass through gland and base 3 compress tightly fixedly.
CN202110291242.0A 2021-03-18 2021-03-18 Preparation method of tubular ceramic membrane with one sealed end Pending CN115105970A (en)

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CN1676198A (en) * 2005-01-14 2005-10-05 山东理工大学 Ceramic hollow fiber membrane reactor for making oxygen by air separation, and its preparing method and use
US20080164641A1 (en) * 2005-12-09 2008-07-10 Shi-Woo Lee Mold for Ceramic Membrane Tube and Fabrication Method of Ceramic Membrane Tube Using the Same
CN101279205A (en) * 2008-05-30 2008-10-08 山东理工大学 Ceramic hollow fiber oxygen permeable membrane with catalyst supported on surface and manufacture method thereof
CN101318106A (en) * 2008-05-23 2008-12-10 中国科学技术大学 Plate shaped ceramic film composed of multiple hollow fiber ceramic films by parallel connection and preparation thereof
CN101823338A (en) * 2009-03-02 2010-09-08 山东省医疗器械研究所 Rapid forming method of plug at end part of silicon rubber conduit
CN105080359A (en) * 2015-08-07 2015-11-25 天津工业大学 Preparing method for ceramic hollow fiber oxygen permeating membrane bundle
CN109070001A (en) * 2015-11-25 2018-12-21 克拉尔曼合成材料加工有限责任公司 Tubular filter membrane component and its manufacturing method
CN110743388A (en) * 2019-09-20 2020-02-04 三达膜科技（厦门）有限公司 End-capping method for tubular ceramic membrane

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Publication number Priority date Publication date Assignee Title
CN1676198A (en) * 2005-01-14 2005-10-05 山东理工大学 Ceramic hollow fiber membrane reactor for making oxygen by air separation, and its preparing method and use
US20080164641A1 (en) * 2005-12-09 2008-07-10 Shi-Woo Lee Mold for Ceramic Membrane Tube and Fabrication Method of Ceramic Membrane Tube Using the Same
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CN101823338A (en) * 2009-03-02 2010-09-08 山东省医疗器械研究所 Rapid forming method of plug at end part of silicon rubber conduit
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