CN103613410A - Oxygen-permeable membrane surface coating modification material and method for preparing composite oxygen-permeable membrane - Google Patents

Oxygen-permeable membrane surface coating modification material and method for preparing composite oxygen-permeable membrane Download PDF

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CN103613410A
CN103613410A CN201310586021.1A CN201310586021A CN103613410A CN 103613410 A CN103613410 A CN 103613410A CN 201310586021 A CN201310586021 A CN 201310586021A CN 103613410 A CN103613410 A CN 103613410A
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oxygen
mentioned steps
permeable membrane
metal
composite
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CN103613410B (en
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程红伟
鲁雄刚
陶伟
姚为林
李光石
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University of Shanghai for Science and Technology
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Abstract

The invention discloses an oxygen-permeable membrane surface coating modification material. The oxygen-permeable membrane surface coating modification material is formed by loading an active metal on a perovskite-like matrix, and the chemical formula of the material composition of the perovskite-like matrix is REBaCo2-xFexO5+delta, wherein RE is any one or two of Gd, La, Pr and Sm, x is 0-2.0 and the active metal is any one or two of Ag, Ru, Pd, Pt, Ni and Co. The invention further discloses a method for preparing a composite oxygen-permeable membrane. The method comprises the steps of preparing perovskite-like matrix powder by adopting a citric acid complexing method, preparing coating modification slurry by a ball milling method, dipping and smearing the slurry on the permeation side of the oxygen-permeable membrane, and dropping a salt solution of the active metal on a coating to obtain the composite oxygen-permeable membrane after modification. The modification coating disclosed by the invention has a porous microstructure and can be firmly combined with the membrane matrix so as to significantly improve the infiltration capacity and stability of the oxygen-permeable membrane.

Description

Oxygen permeable film surface coating is material modified and prepare the method for composite oxygen penetrating diaphragm
Technical field
The present invention relates to a kind of oxygen permeable film material and preparation method thereof, particularly relate to composite conductor oxygen-permeating film material using in a kind of hydrogen production from coke oven gas and preparation method thereof, be applied to Metallurgical resources comprehensive utilization and function ceramics manufacturing technology field.
Background technology
Oxygen permeable film material is at the need such as the decomposition reaction pure oxygen without interruption of hydro carbons partial oxidation, oxygen-enriched combusting and carbonic acid gas or need to have very tempting application prospect in the separated commercial run of oxygen.For example, referring to Fig. 3, under 750 ℃ of temperature of reaction, at helium gas flow, be 100 mlmin -1with air flow quantity be 300 mlmin -1under condition, BaCo 0.7fe 0.21nb 0.09o 3- y (BCFN) oxygen permeating amount of single oxygen permeable film is 0.82 mlmin -1cm -2, lower than 1.0 ml [STP] min -1cm -2.Under helium/air gradient, only has oxygen permeating amount higher than 1.0 ml [STP] min -1cm -2oxygen permeable film material just may there is actual application value.Meanwhile, oxygen permeable film material must possess structural stability and thermo-chemical stability under various applied environment atmosphere.So when selective oxidation thing composite conductor oxygen-permeating film material, the size of oxygen permeating amount is the factor that first should consider, next is only the problems such as stability, intensity.Although under existing research situation, oxygen-permeable membrane reactor can steady running under methane portion oxidation condition hundreds of hours, but under the strong reducing property atmosphere such as coke-oven gas atmosphere, all can there is significant variation in the configuration of surface of mould material, the Nomenclature Composition and Structure of Complexes, this just makes such oxygen permeable film material be difficult to long term operation.Therefore, film surface is applied to modification, with increase mould material oxygen permeating amount, improve the stability of mould material, this has become the very interested research direction of investigators.
From the oxygen transporting mechanism of composite conductor oxygen-permeating film, the migration of oxygen and transmit need to experience the bulk diffusion process of film inside and at the absorption/desorption on film surface, dissociate/anabolic process.When body is phased while being made as the restricted link that affects oxygen permeating amount size, can better improve oxygen permeating amount by mould material by changing thickness and the exploration of mould material; When surface diffusion is restricted link, can, by applying one deck porous at material surface or thering is the material of catalytic activity, change the oxygen surface exchange performance of material.Research shows, when mould material thickness is 1.0～2.0 mm, the size of oxygen permeating amount is subject to oxygen greatly in the impact of mould material surface exchange process, is also subject to the facies-controlled impact of body simultaneously, thereby the mode that can apply modification by surface improves the oxygen permeating amount of mould material.When oxygen process of osmosis is only subject to surface exchange process control, the modification on mould material per-meate side surface is more remarkable to the raising of oxygen permeability.This is because increased after surface-coated decorative layer, gas-solid interface is transferred to the inside, duct that applies porous layer by film surface, combination/the desorption process of oxygen on infiltration side form surface also moves to the inside, duct of porous layer to carry out, can effectively alleviate so the excessive oxygen loss phenomenon of film surfacing, particularly in the partial oxidation reaction of hydro carbons, the excessive oxygen loss of effectively alleviating film surfacing can guarantee carrying out smoothly of reaction, thereby prevented expansion and the decomposition of infiltration side form surfacing, and then strengthened the stability of film.The oxygen permeating amount of the existing composite conductor oxygen-permeating film adopting for hydrogen production from coke oven gas and stability are desirable not enough.
Summary of the invention
In order to solve prior art problem, the object of the invention is to overcome the deficiency that prior art exists, provide the coating of a kind of oxygen permeable film material modified and prepare the method for composite oxygen penetrating diaphragm, the coating of this oxygen permeable film is material modified can change film surface microstructure, film surface-coated one deck has after the material of vesicular structure, its condition of surface occurs obviously to improve, and can improve the oxygen permeating amount of composite conductor oxygen-permeating film, increases the stability of mould material.After surface coating modified, the gas-solid interface on film surface significantly increases, and has been equivalent to increase the available oxygen exchange area on film surface, for hydrogen production from coke oven gas, can effectively improve oxygen permeable film infiltration capacity and stability, has significant industrial sector and is worth.
For reaching foregoing invention, create object, the present invention adopts following technical proposals:
The surface coating of a kind of oxygen permeable film is material modified, and by being that on perovskite-like mold base, supported active metal forms, the material constitutional chemistry formula of perovskite-like mold base is REBaCo 2- x fe x o 5+ δ , wherein RE is any one or any two kinds in Gd, La, Pr and Sm, wherein xvalue between 0 to 2.0, active metal be any one or any two kinds in Ag, Ru, Pd, Pt, Ni and Co, δfor oxygen room, its value is between 0 to 0.6.
The present invention also provides a kind of method of preparing composite oxygen penetrating diaphragm, has following technological process and step:
1. by two kinds of metal-salts of cobalt salt and molysite or wherein any one metal-salt, rare-earth oxide are dissolved in nitre aqueous acid together with barium salt, the metal salt solution that preparation is mixed by metal ion and nitrate ion is standby, and the rare earth metal containing in rare-earth oxide is any one or any two kinds in Gd, La, Pr and Sm;
2. metal ion in the metal salt solution of 1. preparing in above-mentioned steps in addition: ethylenediamine tetraacetic acid (EDTA) (EDTA): the ratio of citric acid is 1:(1 ~ 2): the amount ratio of (1.5 ~ 2.5), ethylenediamine tetraacetic acid (EDTA) is dissolved in distilled water together with citric acid, heated and stirred, until organism dissolves, is prepared organism solution for standby;
3. by above-mentioned steps 1. in the metal salt solution of preparation and the organic solution of preparing in 2. in above-mentioned steps mix, at 85～95 ℃ of temperature, mixing solutions is stirred, and to make the pH value of mixing solutions be between 5.5～6.5 by dripping ammoniacal liquor, continuous heating is uniformly mixed solution, until mixing solutions is become to molten gelatinoid;
4. by the molten gelatinoid obtaining in 3. in above-mentioned steps at 105～120 ℃ of temperature dry 15～20 hours, after molten gelatinoid is expanded to spongy porosu solid, again by spongy porosu solid material 350～650 ℃ of roasting temperatures 5～9 hours, obtain REBaCo 2- x fe x o 5+ δ coat powder material, wherein RE is rare earth metal, 0≤ x≤ 2.0;
5. be taken at the coat powder material that above-mentioned steps obtains in 4., after 12～24 hours, obtain coating paste with solvent, dispersion agent and pore-forming material mixing and ball milling; Solvent preferably adopts any one in glycerine, Terpineol 350, ether and water, and add-on is 500%～800% of coat powder material weight; Dispersion agent preferably adopts any one in polyoxyethylene glycol, tween and succinate, and add-on is 1%～8% of coat powder material weight; Pore-forming material preferably adopts in sesbania powder, carbon nanofiber, bicarbonate of ammonia powder, paraformaldehyde powder and urea powder any one or any two kinds, and add-on is 1%～8% of coat powder material weight;
6. adopt dipping streak method the coating paste obtaining in 5. in above-mentioned steps to be coated in to the per-meate side surface of composite conductor oxygen-permeating film sheet, after oven dry 800～850 ℃ of roasting temperatures 1～2 hour, per-meate side surface to oxygen flow diaphragm applies modification, then to the salts solution that applies the oxygen flow membrane surface dropping active metal after modification, obtain the composite oxygen penetrating diaphragm after modification; The salts solution of active metal preferably adopts any in nitrate, chlorate and vitriol, and add-on is preferably 0.1～2% of the coated weight of coating paste; Active metal preferably adopt any one or any two kinds in Ag, Ru, Pd, Pt, Ni and Co.The material modified preferably chemical formula of applicable composite conductor oxygen-permeating film sheet of oxygen permeable film of the present invention surface coating is BaCo 0.7fe 0.3- a x a o 3- y , X=Nb wherein, Ta, Zr; 0.05≤ a≤ 0.15, yfor oxygen room, its value is between 0 to 0.5.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the oxygen permeable film surface that the present invention makes applies the material modified porous microtexture that has, in coke-oven gas partial oxidation hydrogen-preparation process, and the material modified oxygen penetrating power that can significantly improve mould material of surface coating;
2. the material modified coating of oxygen permeable film surface coating that the present invention makes has porous microtexture, and it is combined firmly with film matrix, can significantly improve the stability of oxygen flow diaphragm.
Accompanying drawing explanation
Fig. 1 is material modified X-ray diffraction (XRD) figure of the embodiment of the present invention one oxygen permeable film surface coating.
Fig. 2 is surface sweeping Electronic Speculum (SEM) photo of the material modified composite conductor oxygen-permeating film sheet cross section of the coating embodiment of the present invention one oxygen permeable film surface coating.
Fig. 3 is the material modified rear comparison diagram that affects on composite conductor oxygen-permeating film sheet oxygen permeating amount of the coating embodiment of the present invention one oxygen permeable film surface coating.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment mono-:
In the present embodiment, referring to Fig. 1 and Fig. 2, utilize the coating material modified method of preparing composite oxygen penetrating diaphragm in oxygen permeable film surface to there is following technological process and step:
By the Ba (NO of 20.434 mmol 3) 2, 20.434 mmol Co (NO 3) 26H 2fe (the NO of O, 20.434 mmol 3) 39H 2the Gd of O and 10.217mmol 2o 3dissolving in 100 ml concentration is 0.5 molL -1aqueous nitric acid in, stir until dissolve completely; Press metal ion: ethylenediamine tetraacetic acid (EDTA) (EDTA): citric acid amount of substance, than the quality for 1:1:2 accurate weighing EDTA and citric acid, adds deionized water and stir organism is dissolved; Two kinds of solution that obtain are mixed, drip ammoniacal liquor until the pH value of solution is 6.0, keeping the temperature of solution is 90 ℃, until reactant becomes colloidal sol shape.By the molten jelly obtaining 110 ℃ dry, after molten gelatinoid is expanded to spongy porosu solid, take out, 350 ℃ and 650 ℃ of roastings 5 hours and 2 hours, the block after sintering is ground respectively, obtain GdBaCoFeO 5+ δ (GBCF) coat powder material.
Get above-mentioned 5 g coat powders, by coat powder: Terpineol 350: polyoxyethylene glycol: carbon nanofiber mass percent is the quality that 15%:84 %:0.8 %:0.2 % accurate calculation weighs required several materials.Coat powder and Terpineol 350, polyoxyethylene glycol and carbon nanofiber after 24 hours, obtain required coating paste through ball milling.By BaCo 0.7fe 0.21nb 0.09o 3- y (BCFN) diaphragm polishing is that 1.0 mm are thick, with dropper get slurry a little, drip the side at diaphragm, until slurry, after membrane surface is uniformly dispersed, dries, and 800 ℃ of roastings 2 hours, obtain BCFN-GBCF composite membrane; On overlay, drip the silver nitrate solution of 0.1 mmol concentration, be placed on 110 ℃ and be dried, obtain per-meate side, in reaction side, apply the BCFN-GBCF+Ag diaphragm of modification.
In the present embodiment, adopt citric acid complex method to prepare perovskite-like mold base powder, by adding solvent, dispersion agent and pore-forming material ball milling preparation coating modified slurry, slurry is flooded, spread upon after oxygen permeable film per-meate side, drying, roasting, and in coating, drip the salts solution of active metal, obtain the composite oxygen penetrating diaphragm after modification, preparation technology is simple, is easy to control and operation.Referring to Fig. 1 and Fig. 2, in Fig. 1, by the present embodiment, prepare GdBaCoFeO prepared by the method for composite oxygen penetrating diaphragm 5+ δ (GBCF) X-ray diffraction (XRD) of surface coating modified coating material is schemed knownly, and its structure is perovskite-like shaped material.In Fig. 2, from the present embodiment prepare GBCF surface coating prepared by the method for composite oxygen penetrating diaphragm to mould material surface modification after surface sweeping Electronic Speculum (SEM) photo of cross section, the present embodiment surface coating GdBaCoFeO 5+ δ (GBCF) modified coating that is has porous microtexture, at BaCo 0.7fe 0.21nb 0.09o 3- y (BCFN) diaphragm per-meate side, at BaCo 0.7fe 0.21nb 0.09o 3- y (BCFN) duct of diaphragm reaction side porous layer, carry out the inside, duct that makes the combination/desorption process of oxygen on infiltration side form surface also move to porous layer, can significantly improve the infiltration capacity of oxygen flow diaphragm, at the surface-coated porous layer of oxygen permeable film, can significantly improve the rate of exchange of oxygen, thereby reach the object that increases oxygen permeating amount, GdBaCoFeO 5+ δ (GBCF) modified coating that is and BaCo 0.7fe 0.21nb 0.09o 3- y (BCFN) diaphragm matrix, in conjunction with compact and firm, has guaranteed the stability of oxygen flow diaphragm.
embodiment bis-:
The present embodiment and embodiment mono-are basic identical, and special feature is:
In the present embodiment, utilize the coating material modified method of preparing composite oxygen penetrating diaphragm in oxygen permeable film surface to there is following technological process and step:
By the Ba (NO of 20.434 mmol 3) 2, 40.868 mmol Co (NO 3) 26H 2the Gd of O and 10.217mmol 2o 3dissolving in 100 ml concentration is 0.5 molL -1aqueous nitric acid in, stir until dissolve completely; Press metal ion: ethylenediamine tetraacetic acid (EDTA) (EDTA): citric acid amount of substance, than the quality for 1:1:2 accurate weighing EDTA and citric acid, adds deionized water and stir organism is dissolved; Two kinds of solution that obtain are mixed, drip ammoniacal liquor until the pH value of solution is 6.5, keeping the temperature of solution is 95 ℃, until reactant becomes colloidal sol shape.By the molten jelly obtaining 105 ℃ dry, after molten gelatinoid is expanded to spongy porosu solid, take out, 400 ℃ and 600 ℃ of roastings 6 hours and 3 hours, the block after sintering is ground respectively, obtain GdBaCo 2o 5+ δ (GBC 2) coat powder material.
Get above-mentioned 5 g coat powders, by coat powder: Terpineol 350: polyoxyethylene glycol: carbon nanofiber mass percent is the quality that 12%:87 %:0.9 %:0.1 % accurate calculation weighs required several materials.Coat powder and Terpineol 350, polyoxyethylene glycol and carbon nanofiber after 18 hours, obtain required coating paste through ball milling.By BaCo 0.7fe 0.18ta 0.12o 3- y (BCFT) diaphragm polishing is that 1.0 mm are thick, with dropper get slurry a little, drip the side at diaphragm, until slurry, after membrane surface is uniformly dispersed, dries, and 850 ℃ of roastings 1 hour, obtain BCFT-GBC 2composite membrane; On overlay, drip the ruthenium chloride solution of 0.1 mmol concentration, be placed on 110 ℃ and be dried, obtain per-meate side, in reaction side, apply the BCFT-GBC of modification 2+ Ru diaphragm.
embodiment tri-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, utilize the coating material modified method of preparing composite oxygen penetrating diaphragm in oxygen permeable film surface to there is following technological process and step:
By the La (NO of 20.434 mmol 3) 36H 2co (the NO of O, 20.434 mmol 3) 26H 2fe (the NO of O, 20.434 mmol 3) 39H 2the Gd of O and 10.217mmol 2o 3dissolving in 100 ml concentration is in the aqueous nitric acid of 0.5 molL, stirs until dissolve completely; Press metal ion: ethylenediamine tetraacetic acid (EDTA) (EDTA): citric acid amount of substance, than the quality for 1:1:2 accurate weighing EDTA and citric acid, adds deionized water and stir organism is dissolved; Two kinds of solution that obtain are mixed, drip ammoniacal liquor until the pH value of solution is 6.0, keeping the temperature of solution is 90 ℃, until reactant becomes colloidal sol shape.By the molten jelly obtaining 110 ℃ dry, after molten gelatinoid is expanded to spongy porosu solid, take out, 350 ℃ and 650 ℃ of roastings 5 hours and 2 hours, the block after sintering is ground respectively, obtain LaBaCoFeO 5+ δ (LBCF) coat powder material.
Get above-mentioned 5 g coat powders, by coat powder: Terpineol 350: polyoxyethylene glycol: carbon nanofiber mass percent is the quality that 12%:87 %:0.6 %:0.4 % accurate calculation weighs required several materials.Coat powder and Terpineol 350, polyoxyethylene glycol and carbon nanofiber after 15 hours, obtain required coating paste through ball milling.By BaCo 0.7fe 0.2zr 0.1o 3- y (BCFZ) diaphragm polishing is that 1.0 mm are thick, with dropper get slurry a little, drip the side at diaphragm, until slurry, after membrane surface is uniformly dispersed, dries, and 825 ℃ of roastings 2 hours, obtain BCFZ-LBCF composite membrane; On overlay, drip the nickel nitrate solution of 0.1 mmol concentration, be placed on 110 ℃ and be dried, obtain per-meate side, in reaction side, apply the BCFZ-LBCF+Ni diaphragm of modification.
test experiments evaluation of result is analyzed:
Get oxygen flow diaphragm in BCFN, BCFN-GBCF in the embodiment of the present invention one, BCFN-GBCF+Ag tri-and evaluate on micro-reaction equipment, 750～925 ℃ of temperature of reaction, helium gas flow is 100 mlmin -1, air flow quantity is 300 mlmin -1.Experimental result is shown in Fig. 3, and as shown in Figure 3, under 750 ℃ of temperature of reaction, the oxygen permeating amount of BCFN is 0.82 mlmin -1cm -2, under identical experiment condition, the oxygen permeating amount of BCFN-GBCF and BCFN-GBCF+Ag diaphragm is respectively 1.17 and 1.35 mlmin -1cm -2, improved respectively 43% and 65%.Experimental result shows that GBCF system is that a kind of very effective oxygen permeable film per-meate side surface coating is material modified.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; can also make multiple variation according to the object of innovation and creation of the present invention; the change of making under all spirit according to technical solution of the present invention and principle, modification, substitute, combination, simplify; all should be equivalent substitute mode; as long as goal of the invention according to the invention; only material modified and prepare know-why and the inventive concept of the method for composite oxygen penetrating diaphragm otherwise deviate from oxygen permeable film of the present invention surface coating, all belong to protection scope of the present invention.

Claims (6)

1. an oxygen permeable film surface coating is material modified, it is characterized in that: by supported active metal on perovskite-like mold base, form, the material constitutional chemistry formula of described perovskite-like mold base is REBaCo 2- x fe x o 5+ δ , wherein RE is any one or any two kinds in Gd, La, Pr and Sm, wherein xvalue between 0 to 2.0, described active metal is any one or any two kinds in Ag, Ru, Pd, Pt, Ni and Co, δfor oxygen room, its value is between 0 to 0.6.
2. utilize a coating material modified method of preparing composite oxygen penetrating diaphragm in oxygen permeable film surface described in claim 1, it is characterized in that thering is following technological process and step:
1. by two kinds of metal-salts of cobalt salt and molysite or wherein any one metal-salt, rare-earth oxide are dissolved in nitre aqueous acid together with barium salt, the metal salt solution that preparation is mixed by metal ion and nitrate ion is standby, and the rare earth metal containing in described rare-earth oxide is any one or any two kinds in Gd, La, Pr and Sm;
2. metal ion in the metal salt solution of 1. preparing in above-mentioned steps in addition: ethylenediamine tetraacetic acid (EDTA) (EDTA): the ratio of citric acid is 1:(1 ~ 2): the amount ratio of (1.5 ~ 2.5), ethylenediamine tetraacetic acid (EDTA) is dissolved in distilled water together with citric acid, heated and stirred, until organism dissolves, is prepared organism solution for standby;
3. by above-mentioned steps 1. in the metal salt solution of preparation and the organic solution of preparing in 2. in above-mentioned steps mix, at 85～95 ℃ of temperature, mixing solutions is stirred, and to make the pH value of mixing solutions be between 5.5～6.5 by dripping ammoniacal liquor, continuous heating is uniformly mixed solution, until mixing solutions is become to molten gelatinoid;
4. by the molten gelatinoid obtaining in 3. in above-mentioned steps at 105～120 ℃ of temperature dry 15～20 hours, after molten gelatinoid is expanded to spongy porosu solid, again by spongy porosu solid material 350～650 ℃ of roasting temperatures 5～9 hours, obtain REBaCo 2- x fe x o 5+ δ coat powder material, wherein RE is rare earth metal, 0≤ x≤ 2.0;
5. be taken at the coat powder material that above-mentioned steps obtains in 4., after 12～24 hours, obtain coating paste with solvent, dispersion agent and pore-forming material mixing and ball milling;
6. adopt dipping streak method the coating paste obtaining in 5. in above-mentioned steps to be coated in to the per-meate side surface of composite conductor oxygen-permeating film sheet, after oven dry 800～850 ℃ of roasting temperatures 1～2 hour, per-meate side surface to oxygen flow diaphragm applies modification, then to the salts solution that applies the oxygen flow membrane surface dropping active metal after modification, obtain the composite oxygen penetrating diaphragm after modification.
3. prepare according to claim 2 the method for composite oxygen penetrating diaphragm, it is characterized in that: above-mentioned steps 6. in, the salts solution of active metal is any in nitrate, chlorate and vitriol, add-on is 0.1～2% of the coated weight of coating paste.
4. prepare according to claim 3 the method for composite oxygen penetrating diaphragm, it is characterized in that: described active metal is any one or any two kinds in Ag, Ru, Pd, Pt, Ni and Co.
5. prepare according to claim 3 the method for composite oxygen penetrating diaphragm, it is characterized in that: above-mentioned steps 5. in, solvent is any one in glycerine, Terpineol 350, ether and water, add-on is 500%～800% of coat powder material weight; Dispersion agent is any one in polyoxyethylene glycol, tween and succinate, and add-on is 1%～8% of coat powder material weight; Pore-forming material is any one or any two kinds in sesbania powder, carbon nanofiber, bicarbonate of ammonia powder, paraformaldehyde powder and urea powder, and add-on is 1%～8% of coat powder material weight.
6. according to the method for preparing composite oxygen penetrating diaphragm described in any one in claim 1～5, it is characterized in that: above-mentioned steps 6. in, the chemical formula of described composite conductor oxygen-permeating film sheet is BaCo 0.7fe 0.3- a x a o 3- y , X=Nb wherein, Ta, Zr; 0.05≤ a≤ 0.15, yfor oxygen room, its value is between 0 to 0.5.
CN201310586021.1A 2013-11-20 2013-11-20 Oxygen permeable film surface application is material modified and prepare the method for composite oxygen penetrating diaphragm Expired - Fee Related CN103613410B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113511633A (en) * 2021-07-15 2021-10-19 云南安锋气体有限公司 Integrated preparation process of high-purity oxygen

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Publication number Priority date Publication date Assignee Title
CN102603298A (en) * 2012-03-21 2012-07-25 北京科技大学 Method for preparing two-phase compact oxygen permeable material with high oxygen permeability
CN102872727A (en) * 2012-09-28 2013-01-16 中国科学院大连化学物理研究所 Low-temperature stable mixed-conductor oxygen permeable membrane in perovskite type barium-containing iron series
CN103253982A (en) * 2013-05-23 2013-08-21 上海大学 Preparation method of tubular asymmetric oxygen-permeable membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603298A (en) * 2012-03-21 2012-07-25 北京科技大学 Method for preparing two-phase compact oxygen permeable material with high oxygen permeability
CN102872727A (en) * 2012-09-28 2013-01-16 中国科学院大连化学物理研究所 Low-temperature stable mixed-conductor oxygen permeable membrane in perovskite type barium-containing iron series
CN103253982A (en) * 2013-05-23 2013-08-21 上海大学 Preparation method of tubular asymmetric oxygen-permeable membrane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113511633A (en) * 2021-07-15 2021-10-19 云南安锋气体有限公司 Integrated preparation process of high-purity oxygen

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