CN107198973B - 一种可提高co2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法 - Google Patents
一种可提高co2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法 Download PDFInfo
- Publication number
- CN107198973B CN107198973B CN201710438698.9A CN201710438698A CN107198973B CN 107198973 B CN107198973 B CN 107198973B CN 201710438698 A CN201710438698 A CN 201710438698A CN 107198973 B CN107198973 B CN 107198973B
- Authority
- CN
- China
- Prior art keywords
- permeable membrane
- oxygen
- iron
- hours
- oxygen permeable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 69
- 239000001301 oxygen Substances 0.000 title claims abstract description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 239000000919 ceramic Substances 0.000 title claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 229960002303 citric acid monohydrate Drugs 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229960001484 edetic acid Drugs 0.000 claims description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 229960004106 citric acid Drugs 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 2
- 229910002560 FeO3−δ Inorganic materials 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 239000011533 mixed conductor Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- -1 oxygen ion Chemical class 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052923 celestite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
-
- 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
-
- 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
- B01D71/024—Oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种可提高CO2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法,其化学组成为Pr0.6Sr0.4Fe1‑x X x O3‑δ ,其中X为Nb,Al中任一种,化学计量比为0≤x≤0.15。本发明中Nb的掺入能有效提高材料的耐CO2性能;Al掺杂可以得到对称性好的立方钙钛矿结构材料。本发明的制备方法为:将各种金属硝酸盐溶解在去离子水中并与乙二胺四乙酸和一水柠檬酸混合,用氨水将其PH值调至7~8,待水分挥发,经两次焙烧,得到Pr0.6Sr0.4Fe1‑x X x O3‑δ 粉体,研磨后,在一定压力下成型,在1200~1400°C焙烧8小时得到致密的透氧膜片。Pr0.6Sr0.4Fe0.925Nb0.075O3‑δ 透氧膜在900°C纯CO2气氛下保持长时间稳定,其稳定的透氧量为0.11 ml·min‑1·cm‑2左右。
Description
技术领域
本发明公开了一种可提高CO2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法。具体涉及一种B位元素掺杂得到新的透氧膜材料的方法。
背景技术
混合导体透氧膜由于同时具有电子和氧离子导电性可以用作透氧膜材料,在一定温度下,当膜的两侧存在氧浓度梯度时,氧会以氧离子的形式通过氧空位,理论上,致密陶瓷透氧膜具有100%的氧透过选择性。
混合导体透氧膜可用于高纯氧制备,富氧燃烧,天然气部分氧化制合成气或选择性氧化膜反应器等领域有着优良的应用前景。对于混合导体透氧膜材料而言,目前存在的最主要的问题就是膜材料在高温及膜反应气氛下,尤其是在CO2气氛下不够稳定,因此,提高膜材料在酸性气氛和还原性气氛下的稳定性是实现工业化的关键。
目前状况,提高透氧稳定性的方法主要有以下几种:1)A,B位元素掺杂,如Ta,Zr等。2)双相透氧膜材料。技术文献[Solid State Ionics.2011,196,30-33] 和[Chem.Mater.2012,24,2148-2154]中分别利用以上方法有效的稳定了材料在 CO2气氛下的稳定性。
在透氧膜材料中,无Co透氧膜相比于含Co透氧膜,其透氧量较低但稳定性好。技术文献[J.Mater.Chem.A,2014,2,7780]中报道,与Co基透氧膜材料相比,铁基透氧膜材料稳定性较好。因此,我们选用Pr0.6Sr0.4FeO3-δ为基体材料,用高价态的Nb少量取代B位Fe元素,得到耐二氧化碳性能良好的新材料。
通过检测发现Pr0.6Sr0.4Fe1-xNbxO3-δ均为正交结构并且其透氧量相对较低,技术文献[Journal of Membrane Science.2011,383,235-240]中报道,可以通过元素掺杂来改变材料相结构,因此,我们用少量Al取代Pr0.6Sr0.4FeO3-δ中部分Fe,最终得到透氧性能良好的立方钙钛矿透氧膜材料。
发明内容
本发明的目的是提供一种可提高CO2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法。其特征在于,该铁基陶瓷透氧膜具有如下的化学式:
Pr0.6Sr0.4Fe1-xXxO3-δ,其中X为Nb,Al中一种,
所述的化学计量比x的取值范围为:0≤x≤0.15。
本发明一种可提高CO2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法,其特征在于具有以下的工艺过程和步骤:
a)根据Pr0.6Sr0.4Fe1-xXxO3-δ的化学计量比将一定量的硝酸镨,硝酸锶,硝酸铁,草酸铌或硝酸铝溶入去离子水中,加热并搅拌直至完全溶解;按总金属离子:乙二胺四乙酸:柠檬酸物质量比为1:1:1.5的比例,精确称量乙二胺四乙酸,一水柠檬酸的质量,将其加入至装有去离子水的烧杯中,加热搅拌至完全溶解;
b)将此两种溶液混合,并在80℃~120℃搅拌,通过滴加氨水,使溶液的 PH值在7~8间,不断加热搅拌,直至溶液变为黑色溶胶状;将所得凝胶在 140℃~180℃干燥20~24小时,直至其膨胀疏松得多孔固体;
c)将上述b)步骤中所得黑色多孔固体在300℃~400℃加热10~12小时,得到黄色粉末,该粉末研磨后,在700℃~950℃保温5~8小时,得到黑色 Pr0.6Sr0.4Fe1-xNbxO3-δ粉体,将所得粉体在研钵中研磨2~3小时,使得粉体颗粒大小相对均匀,向粉体中加入油酸和粘结剂,在200~300MPa压力下成型,所得片状坯体在1200~1400℃焙烧5~8小时,得到铁基陶瓷导体透氧膜。
附图说明
图1为Pr0.6Sr0.4FeO3-δ,Pr0.6Sr0.4Fe0.9Nb0.1O3-δ,Pr0.6Sr0.4Fe0.9Al0.1O3-δ透氧膜片的X射线衍射(XRD)谱图。
图2为Pr0.6Sr0.4FeO3-δ,Pr0.6Sr0.4Fe0.9Nb0.1O3-δ,Pr0.6Sr0.4Fe0.9Al0.1O3-δ在纯He气氛下透氧量随温度的变化图。
图3为Pr0.6Sr0.4FeO3-δ,Pr0.6Sr0.4Fe0.925Nb0.075O3-δ在900℃纯CO2气氛下长时间的透氧量。
图4为Pr0.6Sr0.4FeO3-δ,Pr0.6Sr0.4Fe0.925Nb0.075O3-δ透氧膜片100小时纯CO2气氛吹扫后吹扫侧表面的X射线衍射(XRD)谱图。
具体实施方式
下面的实施例将对本发明予以进一步的说明,但并不因此限制本发明。
实施例1
将23.36g Pr(NO3)3·6H2O,7.58g Sr(NO3)2,36.16g Fe(NO3)3·9H2O溶解在去离子水中,取52.32g乙二胺四乙酸和56.43g柠檬酸溶解在另一装有一定量去离子水的烧杯中,将上述两溶液混合,并加热至95℃,通过滴加氨水使溶液的PH值为7,继续加热直至获得溶胶状物质。将所得溶胶状物在150℃干燥,直至其膨胀为海绵状多孔固体后取出,在380℃焙烧10小时,随后在950℃焙烧5小时,即得到Pr0.6Sr0.4FeO3-δ粉体,在研钵中研磨3小时,使其颗粒大小均匀,向所得粉体中加入适量油酸,并在300MPa压力下成型,所得片状坯体在1400℃焙烧8小时,即得到Pr0.6Sr0.4FeO3-δ单相混合导体透氧膜,也即铁基陶瓷透氧膜。
实施例2
将23.08g Pr(NO3)3·6H2O,7.48g Sr(NO3)2,33.04g Fe(NO3)3·9H2O,3g草酸铌溶解在去离子水中,取51.67g乙二胺四乙酸和55.74g柠檬酸溶解在另一装有一定量去离子水的烧杯中,将上述两溶液混合,并加热至95℃,通过滴加氨水使溶液PH值为8,继续加热直至获得溶胶状物质,将所得溶胶状物在160℃干燥,直至10小时。随后在950℃焙烧8小时,即得到Pr0.6Sr0.4Fe0.925Nb0.075O3-δ粉体,在研钵中研磨3小时,使其颗粒大小均匀向所得粉体中加入适量油酸,并在300MPa压力下成型,所得片状坯体在1350℃焙烧8小时,即得到Pr0.6Sr0.4Fe0.925Nb0.075O3-δ单相混合导体透氧膜,也即铁基陶瓷透氧膜。
实施例3
将22.98g Pr(NO3)3·6H2O,7.45g Sr(NO3)2,32.01g Fe(NO3)3·9H2O,3.98 g草酸铌溶解在去离子水中,取51.46g乙二胺四乙酸和55.51g柠檬酸溶解在另一装有一定量去离子水的烧杯中,将上述两溶液混合,并加热至100℃,通过滴加氨水使溶液PH值为8,继续加热直至获得溶胶状物质,将所得溶胶状物在 160℃干燥,直至10小时。随后在950℃焙烧8小时,即得到Pr0.6Sr0.4Fe0.9Nb0.1O3-δ粉体,在研钵中研磨3小时,使其颗粒大小均匀向所得粉体中加入适量油酸,并在300MPa压力下成型,所得片状坯体在1400℃焙烧8小时,即得到Pr0.6Sr0.4Fe0.9Nb0.1O3-δ单相混合导体透氧膜,也即铁基陶瓷透氧膜。
实施例4
将23.67g Pr(NO3)3·6H2O,7.68g Sr(NO3)2,32.97g Fe(NO3)3·9H2O,3.4g Al(NO3)3·9H2O溶解在去离子水中,取53g乙二胺四乙酸和57.17g柠檬酸溶解在另一装有一定量去离子水的烧杯中,将上述两溶液混合,并加热至80℃,通过滴加氨水使溶液PH值为8,继续加热直至获得溶胶状物质,将所得溶胶状物在160℃干燥,直至10小时。随后在950℃焙烧8小时,即得到 Pr0.6Sr0.4Fe0.9Al0.1O3-δ粉体,在研钵中研磨3小时,使其颗粒大小均匀向所得粉体中加入适量油酸,并在250MPa压力下成型,所得片状坯体在1400℃焙烧8小时,即得到Pr0.6Sr0.4Fe0.9Al0.1O3-δ单相混合导体透氧膜,也即铁基陶瓷透氧膜。
测试实验结果评价分析
如图1所示,将本发明实施例1,例3,例4制备的Pr0.6Sr0.4FeO3-δ,Pr0.6Sr0.4Fe0.9Nb0.1O3-δ,Pr0.6Sr0.4Fe0.9Al0.1O3-δ进行X射线衍射实验,Nb掺杂不改变材料相结构,与Pr0.6Sr0.4FeO3-δ均为正交结构,然而Pr0.6Sr0.4Fe0.9Al0.1O3-δ为立方结构。说明稳定价态元素Al掺杂可以得到对称性好的立方钙钛矿结构。
如图2所示,Pr0.6Sr0.4Fe0.9Al0.1O3-δ膜片在He气氛下透氧量高于 Pr0.6Sr0.4FeO3-δ,Pr0.6Sr0.4Fe0.9Nb0.1O3-δ。立方钙钛矿结构对称性好,便于氧离子的传输,进一步说明Al掺杂改变了Pr0.6Sr0.4FeO3-δ材料相结构。
如图3所示,将本发明实施例2制备的Pr0.6Sr0.4Fe0.925Nb0.075O3-δ单相混合导体透氧膜在温度为900℃,空气流量为300ml·min-1和CO2流量为100ml·min-1条件下进行透氧量测试,其稳定的透氧量为0.11ml·min-1·cm-2左右,而相比于技术文献[J.Chem.Mater.2010,22,6246]中所述的透氧膜材料在CO2气氛下进行测试,其透氧量几乎为0。PSF和PSFNb0.075对比发现一定量Nb掺杂在一定程度上提高了材料在纯CO2气氛下的稳定性以及透氧性能。由此可见,Nb掺杂能提高单相混合导体透氧膜在CO2气氛下的稳定性。
如图4所示,本发明实例1,例2制备的Pr0.6Sr0.4FeO3-δ, Pr0.6Sr0.4Fe0.925Nb0.075O3-δ膜片经长时间纯CO2气氛吹扫后,将其吹扫测进行XRD 检查,发现Pr0.6Sr0.4FeO3-δ吹扫侧表面有SrCO3和SrSO4生成,而 Pr0.6Sr0.4Fe0.925Nb0.075O3-δ吹扫侧表面表现出良好的相结构稳定性。S元素是由化学试剂不纯引入。说明Nb掺入不仅提高了材料的耐CO2性能,同时抑制了S元素的迁移以及在膜片吹扫侧表面富集。
Claims (1)
1.一种可提高CO2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法,其特征在于,该铁基陶瓷透氧膜具有如下的化学式:
Pr0.6Sr0.4Fe1-xXxO3-δ,其中X为Nb,
所述的化学计量比x的取值范围为:0.075≤x≤0.15;
所述可提高CO2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法具有以下的工艺过程和步骤:
a)根据Pr0.6Sr0.4Fe1-xXxO3-δ的化学计量比将一定量的硝酸镨,硝酸锶,硝酸铁,草酸铌溶入去离子水中,加热并搅拌直至完全溶解;按总金属离子:乙二胺四乙酸:柠檬酸物质量比为1:1:1.5的比例,精确称量乙二胺四乙酸,一水柠檬酸的质量,将其加入至装有去离子水的烧杯中,加热搅拌至完全溶解;
b)将此两种溶液混合,并在80℃~120℃搅拌,通过滴加氨水,使溶液的PH值在7~8间,不断加热搅拌,直至溶液变为黑色溶胶状;将所得凝胶在140℃~180℃干燥20~24小时,直至其膨胀疏松得多孔固体;
c)将上述b)步骤中所得黑色多孔固体在300℃~400℃加热10~12小时,得到黄色粉末,该粉末研磨后,在700℃~950℃保温5~8小时,得到黑色Pr0.6Sr0.4Fe1-xNbxO3-δ粉体,将所得粉体在研钵中研磨2~3小时,使得粉体颗粒大小相对均匀,向粉体中加入油酸和粘结剂,在200~300MPa压力下成型,所得片状坯体在1200~1400℃焙烧5~8小时,得到铁基陶瓷导体透氧膜。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710438698.9A CN107198973B (zh) | 2017-06-12 | 2017-06-12 | 一种可提高co2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710438698.9A CN107198973B (zh) | 2017-06-12 | 2017-06-12 | 一种可提高co2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107198973A CN107198973A (zh) | 2017-09-26 |
CN107198973B true CN107198973B (zh) | 2020-04-03 |
Family
ID=59907819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710438698.9A Expired - Fee Related CN107198973B (zh) | 2017-06-12 | 2017-06-12 | 一种可提高co2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107198973B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109351134A (zh) * | 2018-09-07 | 2019-02-19 | 上海大学 | 单相混合导体非对称透氧膜及其制备方法 |
CN112473678B (zh) * | 2020-11-26 | 2023-01-17 | 上大新材料(泰州)研究院有限公司 | 用于湿法熄焦蒸气混合重整甲烷的催化剂及其制备方法 |
CN112457012B (zh) * | 2020-11-30 | 2023-05-16 | 上海大学 | 热化学分解水制氢用萤石-钙钛矿型双相混合导体膜材料及其制备方法 |
CN112624751B (zh) * | 2020-11-30 | 2023-04-18 | 上海大学 | 热化学分解水制氢用铁基钙钛矿混合导体透氧膜材料及其制备方法 |
CN116514549B (zh) * | 2023-05-05 | 2024-08-23 | 上海大学 | 一种三相混合导体透氧膜材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1203831A (zh) * | 1998-05-06 | 1999-01-06 | 南京化工大学 | 一种混合导电型致密透氧膜材料 |
CN1698939A (zh) * | 2005-04-06 | 2005-11-23 | 南京工业大学 | 氧化铝掺杂的混合导电型致密透氧膜材料 |
CN101596414A (zh) * | 2009-06-26 | 2009-12-09 | 华南理工大学 | 一种含钽钙钛矿混合导体透氧膜及其制法和应用 |
JP2015171984A (ja) * | 2013-08-27 | 2015-10-01 | 国立大学法人東京工業大学 | 結晶性無機化合物 |
CN106083045A (zh) * | 2016-06-12 | 2016-11-09 | 上海大学 | 一种抗co2腐蚀的双相混合导体透氧膜材料及其制备方法 |
-
2017
- 2017-06-12 CN CN201710438698.9A patent/CN107198973B/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1203831A (zh) * | 1998-05-06 | 1999-01-06 | 南京化工大学 | 一种混合导电型致密透氧膜材料 |
CN1698939A (zh) * | 2005-04-06 | 2005-11-23 | 南京工业大学 | 氧化铝掺杂的混合导电型致密透氧膜材料 |
CN101596414A (zh) * | 2009-06-26 | 2009-12-09 | 华南理工大学 | 一种含钽钙钛矿混合导体透氧膜及其制法和应用 |
JP2015171984A (ja) * | 2013-08-27 | 2015-10-01 | 国立大学法人東京工業大学 | 結晶性無機化合物 |
CN106083045A (zh) * | 2016-06-12 | 2016-11-09 | 上海大学 | 一种抗co2腐蚀的双相混合导体透氧膜材料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
Oxygen Permeation Of Pr0.7Sr0.3Fe0.8Al0.2O3-δ;H.Takamura etc;《Solid State Ionics》;20041231;全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN107198973A (zh) | 2017-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107198973B (zh) | 一种可提高co2气氛下透氧稳定性的铁基陶瓷透氧膜的制备方法 | |
Baiker et al. | Influence of the A-site cation in ACoO3 (A= La, Pr, Nd, and Gd) perovskite-type oxides on catalytic activity for methane combustion | |
Niwa et al. | Sintering temperature dependence of conductivity, porosity and specific surface area of LaNi0. 6Fe0. 4O3 ceramics as cathode material for solid oxide fuel cells—Superiority of Pechini method among various solution mixing processes | |
WO2000059613A1 (en) | Catalytic membrane reactor materials for the separation of oxygen from air | |
Ishihara et al. | Mixed conductivity and oxygen permeability of doped Pr2NiO4-based oxide | |
Holt et al. | Defects and transport in SrFe 1− x Co x O 3− δ | |
JP2001093325A (ja) | LaGaO3系電子−酸素イオン混合伝導体及びそれを用いた酸素透過膜 | |
CN105642131A (zh) | 一种纳米粒子稳定钙钛矿结构透氧膜的方法 | |
CN103052433B (zh) | Co2-耐受性混合导电氧化物及其用于氢气分离的用途 | |
JPH0450055B2 (zh) | ||
CN103602105B (zh) | 一种用于透氧膜表面改性的萤石型涂层材料及其制备方法 | |
CN109836153A (zh) | 一种CeO2基混合导体材料及其在氢分离膜反应器中的应用 | |
CN109734438A (zh) | 一种不含钴和铁的钛基钙钛矿型陶瓷透氧膜及其制备方法和应用 | |
JP6680180B2 (ja) | 低温作動可能なペロブスカイト型酸化物およびその製造法 | |
CN104258740A (zh) | B位掺杂Ca元素的BaFeO3-δ基陶瓷透氧膜材料 | |
KR20130026639A (ko) | Lstf 산화물로 코팅된 bscf 관형 산소 분리막 및 이의 제조방법 | |
CN106966728A (zh) | 一种阴离子掺杂的K2NiF4型混合导体透氧膜材料及其制备方法与应用 | |
Łańcucki et al. | Impact of calcium doping on structure, catalytic and conductive properties of lanthanum strontium iron oxide | |
Lu et al. | Structure, chemical stability and electrical conductivity of perovskite La0. 6Sr0. 4M0. 3Fe0. 7O3− δ (M= Co, Ti) oxides | |
JP2005507308A (ja) | 固体多成分混合のプロトンおよび電子伝導膜 | |
CN104860667B (zh) | 一种双金属掺杂的混合导体透氧膜及其制备方法和应用 | |
CN113121231A (zh) | 一种具有良好稳定性的含铝双相混合导体透氧膜材料及其制备方法 | |
Wang et al. | The superior NO oxidation activity over La 2 CoMnO 6 double perovskite to that of La 2 GaMnO 6: effects of magnetic Co 3+ and nonmagnetic Ga 3+ | |
CN113264768A (zh) | 一种高透氧量的铜基双相混合导体透氧膜材料及其制备方法 | |
CN1128005C (zh) | 具有高氧空穴浓度的混合导体透氧膜 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200403 |
|
CF01 | Termination of patent right due to non-payment of annual fee |