CN116514549A - 一种三相混合导体透氧膜材料及其制备方法 - Google Patents
一种三相混合导体透氧膜材料及其制备方法 Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 89
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 89
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000011533 mixed conductor Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 16
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010436 fluorite Substances 0.000 claims abstract description 10
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 7
- 239000011029 spinel Substances 0.000 claims abstract description 7
- 235000015895 biscuits Nutrition 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 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
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 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 description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 7
- 150000001213 Praseodymium Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 159000000008 strontium salts Chemical class 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 52
- 239000001569 carbon dioxide Substances 0.000 abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 26
- 239000007789 gas Substances 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 10
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 5
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 5
- 229960002303 citric acid monohydrate Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- -1 oxygen ion Chemical class 0.000 description 5
- LXXCECZPOWZKLC-UHFFFAOYSA-N praseodymium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LXXCECZPOWZKLC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 229960004106 citric acid Drugs 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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Abstract
本发明涉及一种三相混合导体透氧膜材料及其制备方法，该材料包括萤石相、钙钛矿相和尖晶石相三型，组成及重量百分比具体为：Ce0.9Pr0.1O2‑δ氧化物x wt.％、Pr0.6Sr0.4Fe0.9M0.1O3‑δ氧化物y wt.％和NiFe2O4氧化物100‑x‑y wt.％，其中0<x<100，0<y<100，M包括Fe、Co和Ni中的至少一种。与现有技术相比，本发明采用溶胶凝胶法一锅制备粉体，研磨后干压成型，再将获得的素坯烧结得到透氧膜材料，三相相容性好，无杂相生成，结构致密，机械强度高，在二氧化碳和还原性气体等腐蚀性气体环境中保持化学稳定性。
Description
技术领域
本发明属于冶金资源综合利用和陶瓷制造技术领域，涉及一种三相混合导体透氧膜材料及其制备方法。
背景技术
在社会经济快速发展的短期内，化石燃料仍将是主要能源，而大量使用化石燃料导致温室气体的排放增加，二氧化碳排放造成了超过60％的温室效应，使全球变暖继续加剧。在二氧化碳减排背景下，减少二氧化碳排放并回收利用具有极其重要的理论研究意义和实际应用价值。碳捕集与利用(CCU)技术被认为是减少二氧化碳排放和减缓气候变化的有效策略。其中二氧化碳热分解该技术能够将二氧化碳转化为更有价值的一氧化碳，因为一氧化碳是甲醇和碳氢化合物等重要化学产品的反应物。该技术在有效减少燃煤电厂二氧化碳排放方面受到了广泛关注。然而，二氧化碳分解需要较高的能量，高昂的技术成本一直是制约二氧化碳热分解技术商业化的关键因素。
混合导体透氧膜是一类在高温(尤其是>700℃)同时具有氧离子和电子导电性能的致密陶瓷膜，在两侧存在一定的氧浓度差时，氧气以离子的形式通过氧空位从透氧膜的高氧分压侧传递至低氧分压侧，具有100％的氧离子选择性和连续传输氧能力，在高温下可从二氧化碳中分离氧气。透氧膜技术与二氧化碳热分解技术相结合，使其在CCU过程中具有经济、方便、实用的特点，具有广阔的研究前景。
然而，由于二氧化碳热分解过程中的恶劣环境(如高浓度的二氧化碳、甲烷和少量的一氧化碳、氢气等)对透氧膜材料的稳定性有很高的要求。单相钙钛矿型混合导体透氧膜材料由于组成简单且具有较高的透氧量而受到越来越多的关注，但是耐二氧化碳性和稳定性严重限制了其在二氧化碳热分解工业中实际应用。为了获得高性能的混合导体透氧膜，特别是抗二氧化碳性能，选择合适的钙钛矿材料，并引入另一不与二氧化碳反应的新组分相制备双相或多相混合导体透氧膜对二氧化碳热分解工艺至关重要。
专利CN110092664A公开了一种自分相混合导体三相膜材料及其制备方法与应用，膜材料由以质子导电为主的钙钛矿相、以氧离子导电为主的萤石相和以电子导电为主的钙钛矿相三相组成。但该专利较高的钙钛矿相含量使其在甲烷、二氧化碳等多组源复杂气氛下容易被腐蚀，使稳定性下降。
专利CN112457012A公开了一种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，采用溶胶凝胶法分别制备出萤石相、钙钛矿相前驱体材料，通过球磨机使两相材料均匀地混合在一起，并成型获得坯体，接着焙烧，即得到双相陶瓷透氧膜片。但该专利萤石相的加入使膜材料电子导电性能降低。
专利CN112624751A公开了一种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，属能源制备技术和陶瓷制造技术领域。采用溶胶-凝胶法制备Pr0.6Sr0.4Fe1-xMxO3-δ粉体，研磨后压制成型，获得坯体，接着在1250-1400℃焙烧6-10h，得到铁基钙钛矿混合导体透氧膜片。但该专利的透氧膜材料耐二氧化碳和还原性气体腐蚀的性能较差。
发明内容
本发明的目的就是为了克服上述现有技术存在的至少一种缺陷而提供一种三相混合导体透氧膜材料及其制备方法，本发明三相相容性好，无杂相生成，结构致密，机械强度高，在二氧化碳和还原性气体等腐蚀性气体环境中保持化学稳定性。
本发明的目的可以通过以下技术方案来实现：
本发明的技术方案之一在于，提供一种三相混合导体透氧膜材料，该材料包括萤石相、钙钛矿相和尖晶石相三型，组成及重量百分比具体为：Ce0.9Pr0.1O2-δ氧化物x wt.％、Pr0.6Sr0.4Fe0.9M0.1O3-δ氧化物y wt.％和NiFe2O4氧化物100-x-y wt.％，其中0<x<100，0<y<100，M包括过渡金属Fe、Co和Ni中的至少一种。
萤石相具有较高的氧离子导电能力，钙钛矿相具有氧离子和电子导电能力，而尖晶石相具有较高的电子导电能力，三相材料混合制备混合导体透氧膜可保证较高的混合离子-电子导电能力，且萤石相和尖晶石相同时引入可增强材料在二氧化碳和还原性气体等腐蚀性气体环境中的化学稳定性。
进一步地，所述的材料中，30<x<70，30<y<70。
本发明的技术方案之一在于，提供一种三相混合导体透氧膜材料的制备方法，该方法包括以下步骤：
(1)根据所述的材料化学式计算并精确称量所需的铈盐、镨盐、锶盐、铁盐、金属M盐和镍盐，将铈盐、镨盐、锶盐、铁盐、金属M盐和镍盐加入水中，加热搅拌直至完全溶解，得到金属离子溶液；精确称量乙二胺四乙酸和柠檬酸，将乙二胺四乙酸和柠檬酸加入水中，加热并搅拌均匀，得到酸溶液；
(2)将上述完全溶解的金属离子溶液倒入酸溶液中继续加热搅拌，然后滴加氨水调节pH；继续加热搅拌至溶液形成溶胶状，将溶胶干燥形成黑褐色多孔固体；多孔固体取出后进行简单破碎研磨，然后焙烧，将焙烧后的疏松粉末状物体均匀研磨，焙烧，得到透氧膜粉体；
(3)向透氧膜粉体中滴加适量的粘结剂，研磨后使其均匀混合，称量透氧膜粘结粉末，向透氧膜粘结粉体中加入适当油酸，并干压成型，将获得的素坯烧结，得到透氧膜材料。
作为优选的技术方案，步骤(1)中柠檬酸采用一水合柠檬酸。
进一步地，步骤(1)中铈盐、镨盐、锶盐、铁盐、金属M盐和镍盐包括硝酸盐或硫酸盐。
作为优选的技术方案，步骤(1)中铈盐采用六水合硝酸铈(Ce(NO3)3·6H2O)，镨盐采用六水合硝酸镨(Pr(NO3)3·6H2O)，锶盐采用硝酸锶(Sr(NO3)2)，铁盐采用九水合硝酸铁(Fe(NO3)3·9H2O)，镍盐采用六水合硝酸镍(Ni(NO3)2·6H2O)，金属M盐采用九水合硝酸铁、六水合硝酸钴(Co(NO3)2·6H2O)和六水合硝酸镍中的至少一种。
进一步地，步骤(1)中金属盐金属离子、乙二胺四乙酸与柠檬酸摩尔比为1:(0.5-1.5):(1-2)，金属离子溶液摩尔浓度为0.7-1.0mol/L，酸溶液摩尔浓度为0.4-0.6mol/L。
进一步地，步骤(1)中金属离子溶液和酸溶液加热温度为40-60℃，搅拌速度为100-200rpm，时间为5-10min。
进一步地，步骤(2)中调节pH前加热温度为40-60℃，搅拌速度为100-200rpm，时间为5-10min，pH为7-9；
调节pH后加热温度为80-100℃，搅拌速度为100-200rpm，时间为15-20h，干燥温度为120-150℃，时间为24-48h。
进一步地，步骤(2)中多孔固体焙烧温度为350-400℃，时间为10-15h，
疏松粉末研磨时间为3-5min，焙烧温度为650-950℃，时间为4-8h。
进一步地，步骤(3)中粘结剂包括聚乙烯醇(PVA)、聚乙烯缩丁醛(PVB)或石蜡，透氧膜粉体与粘结剂质量比为1:(0.05-0.1)，透氧膜粘结粉体与油酸质量比为1:(0.05-0.1)。
进一步地，步骤(3)中研磨时间为1-2h，干压压力为100-200MPa，保压时间为2-5min，烧结温度为1250-1450℃，时间为6-10h。
与现有技术相比，本发明具有以下优点：
(1)本发明三相相容性好，无杂相生成，颗粒均匀分布且晶界清晰，结构致密，机械强度高，在二氧化碳分解反应器组件中具有应用潜力；
(2)本发明采用溶胶凝胶法一锅制备粉体，研磨后干压成型，再将获得的素坯烧结得到透氧膜材料，方法工艺简单，成本低，适合推广使用；
(3)本发明透氧量随着甲烷浓度升高而逐渐增大，且不随时间变化，是一种在甲烷、二氧化碳等多组源复杂气氛下化学稳定性较高、具有应用潜力的混合导体透氧膜材料。
附图说明
图1为本发明实施例1中三相混合导体透氧膜材料的一锅法制备工艺流程图；
图2为本发明实施例1中三相混合导体透氧膜材料的粉末及膜片的X射线衍射(XRD)图；
图3为本发明实施例1中三相混合导体透氧膜材料的扫描电子显微镜(SEM)及元素面扫分析图；
图4为本发明实施例1中三相混合导体透氧膜材料的随甲烷浓度变化的透氧性能图；
图5为本发明实施例1中三相混合导体透氧膜材料的随时间变化的透氧性能图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
下述各实施例中所采用的设备如无特别说明，则表示均为本领域的常规设备；所采用的试剂如无特别说明，则表示均为市售产品或采用本领域的常规方法制备而成，以下实施例中没有做详细说明的均是采用本领域常规实验手段就能实现。
实施例1：
一种三相混合导体透氧膜材料及其制备方法，如图1所示，具体步骤如下：
称量13.62g六水合硝酸铈(Ce(NO3)3·6H2O)、3.85g六水合硝酸镨(Pr(NO3)3·6H2O)、0.76g硝酸锶(Sr(NO3)2)、10.51g九水合硝酸铁(Fe(NO3)3·9H2O)、2.48g六水合硝酸镍(Ni(NO3)2·6H2O)溶解在装有100mL去离子水的烧杯中，使得金属离子溶液摩尔浓度为0.8mol/L，在40℃和100rpm下加热搅拌5min，再称量22.90g乙二胺四乙酸和24.69g一水合柠檬酸溶解在另一装有400mL去离子水的烧杯中，使得酸溶液摩尔浓度为0.5mol/L，在40℃和200rpm下加热搅拌10min，将完全溶解的金属离子溶液倒入酸溶液中在40℃和150rpm下加热搅拌10min，然后滴加氨水调节pH至8，继续加热至80℃并在150rpm下搅拌15h至溶液形成溶胶状，将所得粘性凝胶在150℃下干燥24h形成黑褐色多孔固体粉末；多孔固体取出后进行简单破碎研磨，然后在380℃下焙烧10h，得到疏松粉末前驱体，均匀研磨5min后在950℃焙烧5h，即得到60Ce0.9Pr0.1O2-δ-20Pr0.6Sr0.4FeO3-δ-20NiFe2O4三相混合导体透氧膜粉体；
向所得的10g透氧膜粉体中滴加0.8g聚乙烯醇(PVA)粘结剂，研磨1h后使其均匀混合，称量1.8g三相混合导体透氧膜粘结粉末加入0.1g油酸并在200MPa压力下干压2min成型，将获得的素坯在1400℃的温度下烧结8h，便得到60Ce0.9Pr0.1O2-δ-20Pr0.6Sr0.4FeO3-δ-20NiFe2O4三相混合导体透氧膜膜片材料。
如图1所示，本实施例采用改进的溶胶凝胶法一锅制备三相混合导体透氧膜片，该方法在简化制备工艺的同时，也使得所制备的三相混合导体透氧膜片颗粒分布更加紧密和均匀。
如图2所示，对本实施例所制备的三相混合导体透氧膜的粉末及膜片进行了X射线衍射(XRD)测试分析，膜片及粉末均仅含有萤石(CP)相、钙钛矿(PSF)相和尖晶石(NF)相特征衍射峰且未有杂峰出现，说明烧结后的膜片没有杂相产生。
如图3所示，对本实施例所制备的三相混合导体透氧膜进行了扫描电子显微镜(SEM)及元素面扫分析，在膜表面可以清晰地观察到三种晶粒，颗粒均匀分布且晶界清晰，根据面扫结果可知，浅灰色颗粒为CP相，深灰色颗粒为PSF相，黑色颗粒为NF相，三相紧密结合形成了致密且连通性良好的微观组织。
如图4所示，对本实施例所制备的三相混合导体透氧膜进行了甲烷浓度透氧性能测试，进料侧和吹扫侧分别通入流量为100mL·min-1的二氧化碳和100mL·min-1的5-30％甲烷。三相膜片的透氧量随着甲烷浓度的升高而逐渐增大，厚度为1mm的膜片在950℃下透氧量可达到0.3557mL·cm-2·min-1。
如图5所示，对本实施例所制备的三相混合导体透氧膜进行了长时间透氧性能测试，进料侧和吹扫侧分别通入流量为100mL·min-1的二氧化碳和100mL·min-1的30％甲烷。三相膜片的透氧性能在50h的长时间测试中维持稳定，无明显衰退现象。
实施例2：
一种三相混合导体透氧膜材料及其制备方法，与实施例1基本相同，不同之处在于，六水合硝酸铈9.08g，六水合硝酸镨6.46g，硝酸锶1.77g，九水合硝酸铁15.34g，六水合硝酸镍2.48g，乙二胺四乙酸26.48g，一水合柠檬酸29.10g，便得到40Ce0.9Pr0.1O2-δ-40Pr0.6Sr0.4FeO3-δ-20NiFe2O4三相混合导体透氧膜膜片材料。
实施例3：
一种三相混合导体透氧膜材料及其制备方法，与实施例1基本相同，不同之处在于，六水合硝酸铈13.62g，六水合硝酸镨3.76g，硝酸锶0.73g，九水合硝酸铁10.03g，六水合硝酸镍2.73g，乙二胺四乙酸22.69g，一水合柠檬酸24.48g，便得到60Ce0.9Pr0.1O2-δ-20Pr0.6Sr0.4Fe0.9Ni0.1O3-δ-20NiFe2O4三相混合导体透氧膜膜片材料。
实施例4：
一种三相混合导体透氧膜材料及其制备方法，与实施例1基本相同，不同之处在于，六水合硝酸铈13.62g，六水合硝酸镨3.87g，硝酸锶0.76g，九水合硝酸铁10.17g，六水合硝酸镍2.48g，六水合硝酸钴(Co(NO3)2·6H2O)0.26g，乙二胺四乙酸22.93g，一水合柠檬酸24.73g，便得到60Ce0.9Pr0.1O2-δ-20Pr0.6Sr0.4Fe0.9Co0.1O3-δ-20NiFe2O4三相混合导体透氧膜膜片材料。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种三相混合导体透氧膜材料，其特征在于，该材料包括萤石相、钙钛矿相和尖晶石相三型，组成及重量百分比具体为：Ce0.9Pr0.1O2-δ氧化物x wt.％、Pr0.6Sr0.4Fe0.9M0.1O3-δ氧化物y wt.％和NiFe2O4氧化物100-x-y wt.％，其中0<x<100，0<y<100，M包括Fe、Co和Ni中的至少一种。
2.根据权利要求1所述的一种三相混合导体透氧膜材料，其特征在于，所述的材料中，30<x<70，30<y<70。
3.一种如权利要求1或2任一项所述的三相混合导体透氧膜材料的制备方法，其特征在于，该方法包括以下步骤：
(1)将铈盐、镨盐、锶盐、铁盐、金属M盐和镍盐加入水中，加热搅拌，得到金属离子溶液；将乙二胺四乙酸和柠檬酸加入水中，加热搅拌，得到酸溶液；
(2)将金属离子溶液倒入酸溶液中继续加热搅拌，然后滴加氨水调节pH；继续加热搅拌至溶液形成溶胶状，将溶胶干燥形成多孔固体；多孔固体取出后进行破碎研磨，然后焙烧，将焙烧后的疏松粉末研磨，焙烧，得到透氧膜粉体；
(3)向透氧膜粉体中滴加粘结剂，研磨，向透氧膜粘结粉体中加入油酸，并干压成型，将获得的素坯烧结，得到透氧膜材料。
4.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(1)中铈盐、镨盐、锶盐、铁盐、金属M盐和镍盐包括硝酸盐或硫酸盐。
5.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(1)中金属盐金属离子、乙二胺四乙酸与柠檬酸摩尔比为1:(0.5-1.5):(1-2)，金属离子溶液摩尔浓度为0.7-1.0mol/L，酸溶液摩尔浓度为0.4-0.6mol/L。
6.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(1)中金属离子溶液和酸溶液加热温度为40-60℃，搅拌速度为100-200rpm，时间为5-10min。
7.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(2)中调节pH前加热温度为40-60℃，搅拌速度为100-200rpm，时间为5-10min，pH为7-9；
调节pH后加热温度为80-100℃，搅拌速度为100-200rpm，时间为15-20h，干燥温度为120-150℃，时间为24-48h。
8.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(2)中多孔固体焙烧温度为350-400℃，时间为10-15h，
疏松粉末研磨时间为3-5min，焙烧温度为650-950℃，时间为4-8h。
9.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(3)中粘结剂包括聚乙烯醇、聚乙烯缩丁醛或石蜡，透氧膜粉体与粘结剂质量比为1:(0.05-0.1)，透氧膜粘结粉体与油酸质量比为1:(0.05-0.1)。
10.根据权利要求3所述的一种三相混合导体透氧膜材料的制备方法，其特征在于，步骤(3)中研磨时间为1-2h，干压压力为100-200MPa，保压时间为2-5min，烧结温度为1250-1450℃，时间为6-10h。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617147A (zh) * | 2012-04-17 | 2012-08-01 | 江苏科技大学 | 钙钛矿型结构铝酸盐基混合导电陶瓷及其制备方法 |
| CN107198973A (zh) * | 2017-06-12 | 2017-09-26 | 上海大学 | 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 |
| CN110092664A (zh) * | 2018-01-31 | 2019-08-06 | 中国科学院青岛生物能源与过程研究所 | 一种自分相混合导体三相膜材料及其制备方法与应用 |
| CN112457012A (zh) * | 2020-11-30 | 2021-03-09 | 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 |
| CN112647089A (zh) * | 2020-12-15 | 2021-04-13 | 中国科学院大连化学物理研究所 | 一种固体氧化物电解池三元复合阳极的制备方法 |
| CN114349508A (zh) * | 2022-01-14 | 2022-04-15 | 中国科学院青岛生物能源与过程研究所 | 一种具有氧化物薄层的多层陶瓷膜制备方法和应用 |
| KR20220139612A (ko) * | 2021-04-08 | 2022-10-17 | 한국전력공사 | 고투과성 산소 투과 분리막 및 이의 제조방법 |
-
2023
- 2023-05-05 CN CN202310495466.2A patent/CN116514549A/zh active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617147A (zh) * | 2012-04-17 | 2012-08-01 | 江苏科技大学 | 钙钛矿型结构铝酸盐基混合导电陶瓷及其制备方法 |
| CN107198973A (zh) * | 2017-06-12 | 2017-09-26 | 上海大学 | 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 |
| CN110092664A (zh) * | 2018-01-31 | 2019-08-06 | 中国科学院青岛生物能源与过程研究所 | 一种自分相混合导体三相膜材料及其制备方法与应用 |
| CN112457012A (zh) * | 2020-11-30 | 2021-03-09 | 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 |
| CN112647089A (zh) * | 2020-12-15 | 2021-04-13 | 中国科学院大连化学物理研究所 | 一种固体氧化物电解池三元复合阳极的制备方法 |
| KR20220139612A (ko) * | 2021-04-08 | 2022-10-17 | 한국전력공사 | 고투과성 산소 투과 분리막 및 이의 제조방법 |
| CN114349508A (zh) * | 2022-01-14 | 2022-04-15 | 中国科学院青岛生物能源与过程研究所 | 一种具有氧化物薄层的多层陶瓷膜制备方法和应用 |
Non-Patent Citations (4)
| Title |
|---|
| KAVEH PARTOVI等: "Effect of the B-Site Composition on the Oxygen Permeability and the CO2 Stability of Pr0.6Sr0.4CoxFe1−xO3−δ(0.0≤x≤1.0) Membranes", CHEMISTRY OF MATERIALS, vol. 27, no. 8, 31 March 2015 (2015-03-31), pages 2911 - 2919 * |
| MARÍA BALAGUER等: "Fast Oxygen Separation Through SO2- and CO2‑Stable Dual-Phase Membrane Based on NiFe2O4−Ce0.8Tb0.2O2-δ", CHEMISTRY OF MATERIALS, vol. 25, no. 24, 26 November 2013 (2013-11-26), pages 4986 - 4993 * |
| 潮洛蒙;丁铁柱;王晓波;范文亮;张磊;闫祯;: "钙钛矿氧化物(La_(1-x)Pr_x)_(0.6)Sr_(0.4)Co_(0.8)Fe_(0.2)O_(3-δ)氧化学扩散性能的研究", 稀有金属材料与工程, no. 2, 15 July 2011 (2011-07-15) * |
| 王舒等: "CO_2稳定的双相混合导体透氧膜材料的研究进展", 科学通报, no. 16, 15 April 2019 (2019-04-15) * |
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