CN103638825A - Preparation method and application of integrated three-layer structural inorganic oxygen permeating membrane - Google Patents
Preparation method and application of integrated three-layer structural inorganic oxygen permeating membrane Download PDFInfo
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Abstract
本发明提供了一种新型三层结构无机透氧膜的制备方法及其应用。其制备过程包括：(1)采用传统的固相合成法制备混合导体透氧材料；(2)将透氧材料粉体与粘结剂、增塑剂和溶剂混合制备流延浆料；(3)通过流延法分别制备混合导体透氧膜的致密层和多孔层坯体；(4)按多孔层-致密层-多孔层的顺序将坯体叠放在一起，置于80℃的温等静压机里进行压制，制得一体化三层结构透氧膜前驱体；(5)将三层结构无机透氧膜前驱体进行烧结即得到一体化的三层结构无机透氧膜。本发明操作简单，所制备的致密层厚度很薄，起到了提高透氧膜氧传导能力的作用。这种一体化的三层结构透氧膜可以应用于从含氧混合气中高效选择分离高纯度的氧气。The invention provides a preparation method and application of a novel three-layer structure inorganic oxygen-permeable membrane. The preparation process includes: (1) preparing the mixed conductor oxygen-permeable material by traditional solid-phase synthesis method; (2) mixing the oxygen-permeable material powder with binder, plasticizer and solvent to prepare casting slurry; (3) ) respectively prepare the compact layer and the porous layer body of the mixed conductor oxygen permeable membrane by casting method; Pressing in a static press to obtain an integrated three-layer structure oxygen-permeable membrane precursor; (5) sintering the three-layer structure inorganic oxygen-permeable membrane precursor to obtain an integrated three-layer structure inorganic oxygen-permeable membrane. The invention has simple operation, and the prepared dense layer is very thin, which plays a role in improving the oxygen conduction capacity of the oxygen permeable membrane. This integrated three-layer structure oxygen-permeable membrane can be applied to efficiently select and separate high-purity oxygen from oxygen-containing gas mixture.
Description
(1) technical field
The present invention relates to the inorganic oxygen permeation membrane of novel all-in-one three-decker, relate to specifically preparation method and the application thereof of the inorganic oxygen permeation membrane of a kind of integrated three-decker.
(2) background technology
Industrial oxygenerating is used empty minute conventionally or membrane separation technique obtains oxygen from air.There is the shortcomings such as cost is high, institute's oxygen purity is low in an empty minute technology.Membrane separation technique has that technique is simple, efficiency is high, oxygen purity advantages of higher.Mixed oxygen ion electronic conductor oxygen permeation membrane, without applied voltage, only relies on the partial pressure of oxygen of film both sides to drive hydrogen reduction and oxygen evolution reaction, can further reduce costs.
Hybrid ionic electronic conductor dense ceramic membrane is one to have the new ceramics membrane material of oxygen ionic conductivity and electronic conductivity roughly the same time.These new materials have the characteristic of mixed conductor, simultaneously diversion and electronics, this electron conduction tool plays a very important role, and it can form inner loop in this material, that is to say and does not need electrode and outside loop just can carry out the transmission of ion.If mixed oxygen ion electronic conductor film is placed under a condition with oxygen difference in chemical potential, oxonium ion can be transferred to hypoxemia chemical potential side from hyperoxia chemical potential side, and the charge balance in this process can move by the electronics of mixed conductor membrane inside to compensate.Because being conducts oxygen by oxygen ion vacancy, thereby other gas is not had to permeability, it is selectively 100% to oxygen in theory.Mixed oxygen ion electron conductor material does not need extra external circuit when transmission oxonium ion, this characteristic makes it more convenient than pure ionic conductor material in preparation and application process, therefore use mixed conductor material can reduce operating cost, also obtained more and more researchers' interest.
The oxygen process of osmosis of hybrid ionic electronic conductor oxygen permeation membrane is a complicated physical and chemical process, the rough surface exchange process that can be divided into oxygen and the bulk diffusion process of oxygen.Detailed process is: (1), at high keto sectional pressure end, oxygen molecule is diffused into the surface of oxygen permeation membrane by outside; (2) oxygen molecule physical absorption is on the surface of oxygen permeation membrane; (3) oxygen molecule shifts at film Surface disintegration and electronics, produces chemically adsorbing oxygen; (4) adsorb oxygen enters the Lattice Oxygen room on oxygen permeation membrane surface; (5) by the concentration gradient effect in oxygen room, the directed diffusion in Lattice Oxygen room; (6) electron hole and Lattice Oxygen are transferred to the opposite side of oxygen permeation membrane; (7), at low oxygen partial pressure end, oxonium ion changes into adsorb oxygen series; (8) adsorb the oxygen of nearly state at the low oxygen partial pressure end desorption of oxygen permeation membrane; (9) desorption oxygen enters near the gas phase of low oxygen partial pressure end.
In recent years, the report how research improves composite conductor oxygen-permeating film oxygen infiltration rate is a lot, as the researchs such as Cheng H W add one deck Ce on BCFN film
0.8re
0.2o
2-σ(Re=Sm, Gd), when Re is Gd, oxygen permeating amount is increased to original 1.4 times.A.V.Kovalevsky etc. have studied with Ba
0.5sr
0.5co
0.8fe
0.2o
3-σ(BSCF) be matrix, porous support layer is SrCo
0.8fe
0.2o
3-σoxygen permeation membrane, result shows: the 1.5-1.8 that the thick film oxygen permeating amount containing honeycomb sandwich of 1.32mm is the thick BSCF film of 1mm oxygen permeating amount is doubly.Jung Hoon Park etc. has studied on BSCF tubular type oxygen permeation membrane and has added one deck La
0.6sr
0.4ti
0.3fe
0.7o
3-σcoating, the film oxygen permeating amount that 1mm is thick in the time of 950 ℃ has reached 3mlcm
-2min
-1left and right.
(3) summary of the invention
Preparation method and the application thereof of the inorganic oxygen permeation membrane of the integrated three-decker of a kind of high oxygen permeating amount have been the object of this invention is to provide.
The invention provides the preparation method of the inorganic oxygen permeation membrane of integrated three-decker, adopt solid phase method to prepare powder; By the tape casting, prepare respectively compacted zone and porous layer oxygen permeation membrane, casting slurry preparation process is as follows: in mixed conductor perovskite oxide powder, add ethanol, butanone and castor oil, put into planetary ball mill ball milling 24 hours, then in slurry, add binding agent and plasticizer and a small amount of ethanol and butanone, then be placed in the upper ball milling of shape celestial body mill 24 hours.During curtain coating porous layer, joined and will add pore creating material after slurry and with planetary ball mill ball milling 2 hours.The casting slurry preparing, after deaeration, directly produces curtain coating on casting machine DR-150 in experiment with Japan, is placed to natural drying (room temperature 29-30 ℃) on transport tape; After each surface cleaning of the base substrate that experiment obtains curtain coating, order by porous layer-compacted zone-porous layer stacks, and puts into vacuum packaging bag and vacuumizes, and is then placed in the warm isostatic pressing machine of 80 ℃ and suppresses, dwell pressure is 20MPa, and the dwell time is 10 minutes.The inorganic oxygen permeation membrane of the three-decker of compacting is placed in to 1130 ℃ of sintering and after 6 hours, obtains required product.
In the preparation method of the inorganic oxygen permeation membrane of integrated three-decker provided by the invention, while preparing respectively compacted zone and the inorganic oxygen permeation membrane of porous layer by the tape casting, the binding agent using is one or both in PVA, PVB, and plasticizer is one or more in DMP, DEP, DBP, DCP.
In the preparation method of the inorganic oxygen permeation membrane of integrated three-decker provided by the invention, while preparing the inorganic oxygen permeation membrane of porous layer by the tape casting, the pore creating material of use is one or more in ball-type graphite, soluble starch, active carbon.
In the preparation method of the inorganic oxygen permeation membrane of integrated three-decker provided by the invention, during the inorganic oxygen permeation membrane moulding of three-decker, the temperature of warm isostatic pressing machine is 50-100 ℃, and dwell pressure is 15-25MPa, dwell time is 5-15 minute, and calcining heat is 1100-1200 ℃.
(4) accompanying drawing explanation
Figure 1B a
0.9co
0.7fe
0.2nb
0.1o
3(BCFN) grain size analysis after 1000 ℃ of calcination of powder;
The inorganic oxygen permeation membrane XRD analysis of Fig. 2 three-decker; Wherein (a) is porous layer, is (b) compacted zone;
The inorganic oxygen permeation membrane SEM of Fig. 3 three-decker pattern; Wherein (a), (b) and (c) be respectively and amplify 100 times, 300 times and 2000 times of sections; (d) amplify 1000 times of compacted zone sections;
The impact of Fig. 4 temperature on the inorganic oxygen permeation membrane oxygen permeating amount of three-decker;
The impact of Fig. 5 helium gas flow on the inorganic oxygen permeation membrane oxygen permeating amount of three-decker;
The inorganic oxygen permeation membrane oxygen permeating amount of Fig. 6 three-decker stability.
(5) specific embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
According to the stoichiometric proportion of each content in BCFN, take BaCO
3, Co
3o
4, Fe
2o
3and Nb
2o
5aR, is placed in the polyurethane ball-milling pot that zirconia ball is housed, and with absolute ethyl alcohol, as solvent, wherein wt is 1:2:0.8 than " material: ball: absolute ethyl alcohol ".Place it in ball milling 48h on pulley type ball mill, then in 78 ℃ of baking ovens, oven dry is calcined 24h in being placed on Muffle furnace at 1000 ℃, add as stated above again zirconia ball and absolute ethyl alcohol ball milling 24h, in 78 ℃ of baking ovens, dry again, after crossing 200 mesh sieves, obtain BCFN oxide powder, the particle diameter of gained powder distributes and sees Fig. 1.
By the tape casting, prepare respectively compacted zone and porous layer oxygen permeation membrane, casting slurry preparation process is as follows: in BCFN oxide powder, add ethanol, butanone and castor oil, put into shape celestial body grinding machine ball milling 24 hours, then in slurry, add binding agent PVB and plasticizer (repefral) and a small amount of ethanol and butanone, then be placed in the upper ball milling of shape celestial body mill 24 hours.During curtain coating porous layer, joined and will add pore creating material (spherical graphite) after slurry and with shape celestial body grinding machine ball milling 2 hours.The casting slurry preparing, after deaeration, directly produces curtain coating on casting machine DR-150 in experiment with Japan, is placed to natural drying (room temperature 29-30 ℃) on transport tape, and the XRD figure of porous layer and compacted zone is shown in Fig. 2.
After each surface cleaning of the base substrate that curtain coating is obtained, by the order of porous layer-compacted zone-porous layer, stack, put into vacuum packaging bag and vacuumize, be then placed in the warm isostatic pressing machine of 80 ℃ and suppress, dwell pressure is 20MPa, and the dwell time is 10 minutes.The saturating inorganic oxygen film of the three-decker of compacting is placed in to sintering at 1130 ℃ and within 6 hours, obtains the inorganic oxygen permeation membrane of three-decker, its SEM figure is shown in Fig. 3.
Experiment is carried out at 800-900 ℃, gets a point for every 25 ℃, and heating rate is 2 ℃/min.Oxygen flow diaphragm is placed in to one end of the alumina tube that port polishes smooth, with the sealing of glass envelope material.High keto sectional pressure end passes into synthesis of air (21%O
2+ 79%N
2), low oxygen partial pressure end passes into He gas, with mass flow controller, controls each flow, and measures actual flow with soap film flowmeter, and synthesis of air and He throughput are controlled respectively as 135mlmin
-1, 90mlmin
-1.Exit gas is measured its total flow with soap film flowmeter after gas drying tube, and passes into gas chromatograph (SP3420A) and form and content analysis, and result as shown in Figure 4.As can be seen from Fig., the oxygen permeating amount of film all increases along with the rising of temperature, and when temperature is elevated to 900 ℃ from 800 ℃, the oxygen permeating amount of three-decker film is from 2.52mlcm
-2min
-1be increased to 3.8mlcm
-2min
-1, its oxygen permeating amount is respectively 0.6mm and the thick dense film of 1.0mm 1.5 and 1.9 times.A kind of modification to compacted zone surface can be thought in the porous layer surface of the inorganic oxygen permeation membrane of three-decker.Thick compact oxygen permeable film and the three-decker oxygen permeation membrane of contrast 0.6mm, can know when bulk diffusion speed is no longer the main determining factor of mixed conductor membrane oxygen permeating amount, by changing the surface texture of mixed conductor membrane, can improve greatly its oxygen permeating amount.
Embodiment 3
Experiment is placed in oxygen flow diaphragm one end of the alumina tube that port polishes smooth, with the sealing of glass envelope material.High keto sectional pressure end passes into synthesis of air (21%O
2+ 79%N
2), low oxygen partial pressure end passes into He gas, with mass flow controller, controls each flow, and measures actual flow with soap film flowmeter.Exit gas is measured its total flow with soap film flowmeter after gas drying tube, and passes into gas chromatograph (SP3420A) and form and content analysis.This experiment test at 900 ℃, by changing low oxygen partial pressure side He gas purge flow rate, (He throughput is from 60-210mlmin
-1), the situation of change of having tested the oxygen permeating amount of three-decker oxygen-permeable membrane reactor, result is as shown in Figure 5.As can be seen from the figure along with He throughput is from 60mlmin
-1be increased to 210mlmin
-1time, film oxygen permeating amount is from 3.1mlcm
-2min
-1be increased to 4.92mlcm
-2min
-1.When continuing to increase He throughput to 180mlmin
-1time, the increase of film oxygen permeating amount slows down, and illustrates that at this moment oxygen driving force is not the factor of unique decision film oxygen permeating amount, and oxygen also can affect the oxygen permeating amount of film in low oxygen partial pressure side by oxygen exchange rate.
Embodiment 4
Experiment is placed in oxygen flow diaphragm one end of the alumina tube that port polishes smooth, with the sealing of glass envelope material.High keto sectional pressure end passes into synthesis of air (21%O
2+ 79%N
2), low oxygen partial pressure end passes into He gas, with mass flow controller, controls each flow, and measures actual flow with soap film flowmeter.Exit gas is measured its total flow with soap film flowmeter after gas drying tube, and passes into gas chromatograph (SP3420A) and form and content analysis.At 900 ℃, the stability of the inorganic oxygen permeation membrane oxygen permeating amount of three-decker is evaluated, air mass flow and helium gas flow are respectively 140mlmin
-1and 150mlmin
-1, experimental result as shown in Figure 6.Result shows that the inorganic oxygen permeation membrane oxygen permeating amount of three-decker remains on 4.7mlcm in the test process of 100 hours
-2min
-1left and right is constant, illustrates that the inorganic oxygen-permeable membrane reactor stability of three-decker is better.
Embodiment 5
According to the stoichiometric proportion of each content in BSCF, take BaCO
3, SrCO
3, Co
3o
4and Fe
2o
3aR, is placed in the polyurethane ball-milling pot that zirconia ball is housed, and with absolute ethyl alcohol, as solvent, wherein wt is 1:2:0.8 than " material: ball: absolute ethyl alcohol ".Place it in ball milling 48h on pulley type ball mill, then in 80 ℃ of baking ovens, oven dry is calcined 24h in being placed on Muffle furnace at 1100 ℃, add as stated above again zirconia ball and absolute ethyl alcohol ball milling 24h, then dry in 80 ℃ of baking ovens, excessively after 200 mesh sieves, obtain BSCF oxide powder.
By the tape casting, prepare respectively compacted zone and porous layer oxygen permeation membrane, casting slurry preparation process is as follows: in BSCF oxide powder, add ethanol, butanone and castor oil, put into shape celestial body grinding machine ball milling 24 hours, then in slurry, add binding agent and plasticizer and a small amount of ethanol and butanone, then be placed in the upper ball milling of shape celestial body mill 24 hours.During curtain coating porous layer, joined and will add pore creating material after slurry and with shape celestial body grinding machine ball milling 2 hours.The casting slurry preparing, after deaeration, directly produces curtain coating on casting machine DR-150 in experiment with Japan, is placed to natural drying (room temperature 29-30 ℃) on transport tape.
After each surface cleaning of the base substrate that curtain coating is obtained, by the order of porous layer-compacted zone-porous layer, stack, put into vacuum packaging bag and vacuumize, be then placed in the warm isostatic pressing machine of 80 ℃ and suppress, dwell pressure is 20MPa, and the dwell time is 10 minutes.The saturating inorganic oxygen film of the three-decker of compacting is placed in to sintering at 1100 ℃ and within 6 hours, obtains the inorganic oxygen permeation membrane of three-decker.
Embodiment 6
According to La
0.6sr
0.4co
0.2fe
0.8o
3(LSCF) in, the stoichiometric proportion of each content takes La (NO
3)
3, SrCO
3, Co
3o
4and Fe
2o
3aR, is placed in the polyurethane ball-milling pot that zirconia ball is housed, and with absolute ethyl alcohol, as solvent, wherein wt is 1:2:0.8 than " material: ball: absolute ethyl alcohol ".Place it in ball milling 48h on pulley type ball mill, then in 80 ℃ of baking ovens, oven dry is calcined 24h in being placed on Muffle furnace at 1100 ℃, add as stated above again zirconia ball and absolute ethyl alcohol ball milling 24h, then dry in 80 ℃ of baking ovens, excessively after 200 mesh sieves, obtain LSCF oxide powder.
By the tape casting, prepare respectively compacted zone and porous layer oxygen permeation membrane, casting slurry preparation process is as follows: in LSCF oxide powder, add ethanol, butanone and castor oil, put into shape celestial body grinding machine ball milling 24 hours, then in slurry, add binding agent and plasticizer and a small amount of ethanol and butanone, then be placed in the upper ball milling of shape celestial body mill 24 hours.During curtain coating porous layer, joined and will add pore creating material after slurry and with shape celestial body grinding machine ball milling 2 hours.The casting slurry preparing, after deaeration, directly produces curtain coating on casting machine DR-150 in experiment with Japan, is placed to natural drying (room temperature 29-30 ℃) on transport tape.
After each surface cleaning of the base substrate that curtain coating is obtained, by the order of porous layer-compacted zone-porous layer, stack, put into vacuum packaging bag and vacuumize, be then placed in the warm isostatic pressing machine of 80 ℃ and suppress, dwell pressure is 20MPa, and the dwell time is 15 minutes.The saturating inorganic oxygen film of the three-decker of compacting is placed in to sintering at 1100 ℃ and within 5 hours, obtains the inorganic oxygen permeation membrane of three-decker.
Claims (6)
1. mixed conductor oxygen permeable material is prepared the inorganic oxygen permeation membrane of a kind of integrated three-decker, it is characterized in that: the chemical composition of the inorganic oxygen permeation membrane of three-decker is same mixed conductor oxygen permeable material.
2. the preparation method of the inorganic oxygen permeation membrane of integrated three-decker described in claim 1, is characterized in that:
(1) preparation of casting slurry: add ethanol, butanone and castor oil in mixed conductor perovskite oxide powder, put into shape celestial body grinding machine ball milling 24～48h, then in slurry, add binding agent, with plasticizer and a small amount of solvent, be placed in again the upper ball milling 24-48h of shape celestial body mill, obtain casting slurry.
(2) preparation of compacted zone and porous layer: the casting slurry preparing, after deaeration, directly produces curtain coating on casting machine DR-150 in experiment with Japan, is placed to natural drying (room temperature 29-30 ℃) on transport tape.During curtain coating porous layer, joined and will add pore creating material after slurry and with planetary ball mill ball milling 2 hours.
(3) moulding of the inorganic oxygen permeation membrane of three-decker: after each surface cleaning of the base substrate that curtain coating is obtained, order by porous layer-compacted zone-porous layer stacks, putting into vacuum packaging bag vacuumizes, then be placed in the warm isostatic pressing machine of 80 ℃ and suppress, dwell pressure is 20MPa, and the dwell time is 10 minutes.The saturating inorganic oxygen film of the three-decker of compacting is placed in to sintering at 1130 ℃ and within 6 hours, obtains the inorganic oxygen permeation membrane of three-decker.
3. according to the preparation method of the inorganic oxygen permeation membrane of integrated three-decker described in claim 2, it is characterized in that: the binding agent using in described step (1) is one or both in PVA, PVB, and plasticizer is one or more in DMP, DEP, DBP, DCP.
4. according to the preparation method of the inorganic oxygen permeation membrane of integrated three-decker described in claim 2, it is characterized in that: the pore creating material using in described step (2) is one or more in ball-type graphite, soluble starch starch, active carbon.
5. according to the preparation method of the inorganic oxygen permeation membrane of integrated three-decker described in claim 2, it is characterized in that: in described step (3), the temperature of warm isostatic pressing machine is 50-100 ℃, dwell pressure is 15-25MPa, and the dwell time is 5-15 minute, and calcining heat is 1100-1200 ℃.
6. described in claim 1, the inorganic oxygen permeation membrane of integrated three-decker is applied to oxygen separation from oxygen-containing gas.
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| CN108854585A (en) * | 2018-06-22 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of flat zirconium oxide support type two-phase oxygen permeation membrane of large scale and preparation method thereof |
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| CN109865436B (en) * | 2017-12-01 | 2021-07-27 | 中国科学院大连化学物理研究所 | A kind of preparation method of plate-shaped oxygen-permeable membrane module |
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| CN112892228B (en) * | 2019-11-19 | 2022-07-19 | 中国科学院大连化学物理研究所 | Ni-Zr supported by porous Ni tube for hydrogen production1-xMxO2-x/2Film and method for producing same |
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| CN111085112B (en) * | 2019-12-04 | 2021-10-22 | 昆明理工大学 | A kind of preparation method of gradient porous self-supporting symmetrical ceramic membrane and its application |
| CN114191994A (en) * | 2021-11-22 | 2022-03-18 | 南京理工大学 | Tubular high-temperature solid oxide oxygen permeable membrane and preparation method thereof |
| CN116262667A (en) * | 2021-12-14 | 2023-06-16 | 中国科学院大连化学物理研究所 | A method for preparing porous and dense integrated ceramics using seamless butt joint forming technology |
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