CN1263791A - 用于陶瓷离子传输膜的混合式导电立方钙钛矿 - Google Patents
用于陶瓷离子传输膜的混合式导电立方钙钛矿 Download PDFInfo
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- CN1263791A CN1263791A CN00101984A CN00101984A CN1263791A CN 1263791 A CN1263791 A CN 1263791A CN 00101984 A CN00101984 A CN 00101984A CN 00101984 A CN00101984 A CN 00101984A CN 1263791 A CN1263791 A CN 1263791A
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- oxygen
- membrane component
- alloy
- cobalt
- ceramic
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- 239000000919 ceramic Substances 0.000 title claims abstract description 25
- 230000005540 biological transmission Effects 0.000 title description 6
- 238000002156 mixing Methods 0.000 title description 3
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 73
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 19
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- 239000010941 cobalt Substances 0.000 claims abstract description 15
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- -1 oxygen ions Chemical class 0.000 claims abstract description 9
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- 239000011651 chromium Substances 0.000 claims abstract description 8
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
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- 239000000126 substance Substances 0.000 claims description 11
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 5
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010937 tungsten Substances 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 229910000792 Monel Inorganic materials 0.000 claims description 3
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- YOZHDLRXAUXAKJ-UHFFFAOYSA-N [In].[Pr] Chemical compound [In].[Pr] YOZHDLRXAUXAKJ-UHFFFAOYSA-N 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 claims description 2
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- 239000000843 powder Substances 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
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- 239000003610 charcoal Substances 0.000 description 3
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- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011533 mixed conductor Substances 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
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- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 229940068984 polyvinyl alcohol Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 2
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- 208000037656 Respiratory Sounds Diseases 0.000 description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
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Abstract
一种氧分离机用的陶瓷材料由式A1-xAx′B1-yBy′O3-z代表的陶瓷膜元件制成·式中A为镧系元素;A,为镧系元素掺杂剂;B选自钛、钒、铬、锰、铁、钴、镍和锌及其混合物;B′为铜;x为0.4—0.8;y为0.1—0.9;z>0。当B含钴量大于0.1时,铁量应小于0.05。该膜元件能在较低温度下选择性通过膜传输氧离子,测出氧通量。这使氧分离机可在较低温度下工作。往陶瓷中加入第二相可提高其机械稳定性。
Description
本专利申请是1996年12月31日提交的题为“带机械增强构件的固体电解质膜”的美国专利申请系列号08/775 663的部分继续申请。该系列号在本文全文中引入作为参考。
本发明涉及固体电解质离子传输膜(ion transpoft membrane)要用到的陶瓷组合物。更具体地说,本发明涉及含有两种
系元素和两种过渡金属元素的氧化物的钙钛矿结构。该组合物为缺氧型,并在很宽的温度范围内保持着立方结构。
本发明是在美国政府支持下按由“标准和工艺国家研究所”提供的合作协议号70NANB5H1065完成的。美国政府对本发明享受一定的权利。
从含氧气流中分离氧是许多工业化大生产操作中的一项处理步骤。分离氧的一种方法是利用混合导体陶瓷材料。无孔的陶瓷膜元件不能透过其它物种,但能选择性地透过氧离子和电子。适用的陶瓷包括混合导体钙钛矿和双相金属-金属氧化物的结合物。美国专利5,702,959(Mazanec等)、5,712,220(Carolan等)和5,733,435(Prasad等)中公开了一些示例性的陶瓷组合物,所有这些专利的全文在此引入作为参考。
这些膜元件具有氧选择性。“氧选择性”意指只有氧离子能透过膜传输,而排斥其它元素和它们的离子。固体电解质膜是用无机氧化物制造的,典型的无机氧化物是由钙或钇稳定的锆或类似的具有莹石或钙钛矿结构的氧化物。在题为“固体电解质膜气体分离的反应性清洗”的、Prasad等人的欧洲专利申请No.778,069中,描述了这些膜在气体净化中的使用。
在温度范围为450℃至1200℃、氧的分压占优势的情况下,当膜元件两面保持化学电位差时,陶瓷膜元件就有能力传输氧离子和电子。该化学电位差是借助于在离子传输膜两面保持氧分压的正比率而建立起来的。在暴露于含氧气体的膜的阴极侧,氧的分压(PO2)被保持在高于回收传输过来的氧的阳极侧的氧分压。这一PO2的正比率可借助于使传输过来的氧与耗氧过程或燃料气起反应而获得。混合导体钙钛矿陶瓷膜的氧离子传导率,通常在0.01和100S/cm的范围内,其中S(西门子)为欧姆的倒数(1/Ω)。
为有效地使用钙钛矿进行氧分离,须满足多项要求。钙钛矿应具有高的氧通量,这里通量是指氧穿过膜结构传输的速率。钙钛矿在整个工作温度的范围内应具有立方形晶体结构。具有六角晶体结构的钙钛矿不能有效地传输氧。某些钙钛矿在室温(标称20℃)下具有六角形的晶体结构,并在温度更高时发生相变。对这种材料来说,相变温度就代表着含有这种材料作膜元件的氧分离器可以工作的最低温度。钙钛矿结构在工作温度下必须化学稳定,并具有一定的机械稳定度。
有多种混合氧化物钙钛矿显示出可用于作氧分离。这些钙钛矿的典型形式为ABO3,其中A为
系元素,B为过渡金属元素,O为氧。系元素或稀土元素是元素周期表中原子序在57(
)和71(镥)之间的元素,这个名称是国际纯粹化学和应用化学联合会(IUPAC)规定的。通常,钇(原子序39)是被归入
系元素类之内的。过渡金属元素在元素周期表中是在第4周期内II类和III类之间,包括钛、钒、铬、锰、铁、钴、镍、铜和锌。A组分和/或B组分可用别的材料掺杂,以提高其稳定性和实用性。
Mazanec等的美国专利5,648,304公开了一种氧选择性钙钛矿,它以下述化学式来代表:
[A1-xA'x][CO1-y-xByB'z]O3-d
式中A为选自钙、锶和钡;
B为选自铁、锰、铬、钒和钛;
B′选自铜或镍;
x约在0.000l~0.1的范围;
y约在0.002~0.05的范围;
z约在0.0005~0.3的范围;以及
d由金属的化合价来确定。
Mazenac等揭示出,加入较低浓度的特定过渡金属元素可以稳定钙钛矿的立方结构,抑制六角相材料的形成。该晶体结构显示出在25℃至950℃的范围内都是稳定的。
Carolan等的美国专利5,712,220公开了一种对固态氧分离装置有效的钙钛矿,它的结构可用下式代表:
LnxA'x 'A″x″ByB'y'B″y″O3-z
A'是选自第2类;
B、B'和B″是独立地选自d区的过渡金属元素,但钛和铬除外;
0<x<1:
0<x'<1:
0<x″<1;
0<y<1.1;
0<y'<1.1;
0<y″<1.1;
x+x'+x″=1.0;
1.1>y+y'+y″>1.0;以及
z是能使化合物变成电中性的一个数字,其中这些元素是IUPAC所正式通过的元素周期表中的元素。
Carolen等所公开的结构具有的B(过渡金属元素)比例(y+y'+y″/x+x'+x″)大于1。该结构被揭示出在具有高二氧化碳和水蒸汽分压的环境中是很稳定的。
美国专利5,817,597(Carolen等)公开了一种对固态氧分离装置有效的钙钛矿,它的结构可用下式代表:
LnxA'x'CoyFey'Cuy″O3-z
A′可以是锶也可以是钙;
x、y、z均大于0;
x+x′=1
y+y′+y″=1;
0<y″<0.4;以及
z是能使物质组分变为电中性的一个数字。该组分被揭示为在高氧分压条件下能在氧渗透和抗降解方面取得很好平衡的组分。B-部位(B-site)则依靠与铁和铜的结合来加以稳定。
1986年1月30日出版的日本专利公开No.61-21,717中公开了另一种适于用作氧传输膜的钙钛矿结构。该“公开”公开了一种用作氧传输膜的金属氧化物,其代表结构为:
La1-xSrxCo1-yFeyO3-δ
式中x在0.1与1之间;
y在0.05与1之间;以及
δ在0.5与0之间。
Teraoka在Chemistry Letters(化学通讯,日本化学协会出版物,1988)上发表的文章公开了一种适合用作氧传输膜的钙钛矿结构,并讨论了阳离子取代对氧渗透率的影响。一种公开的组分是La0.6Sr0.4Co0.8B′0.2O3,其中B′是选自锰、铁、镍、铜、钴和铬。
在另一个研究领域中,已经发现钙钛矿在接近液氮沸点的温度下有超导性,即具有事实上无阻力地传导电子的能力。Genouel等1995年在Journal of Solid State Chemistry(固态化学杂志)上发表的一篇文章公开了一种缺氧钙钛矿,其代表结构为:
La0.2Sr0.8Cu0.4M0.6O3-y
式中M是选自钴和铁;以及
y在0.3与0.58之间。
Genouel等揭示说,该晶体结构具有高浓度随机分布的氧空穴,(y)大到0.52,而不是化学计算所预计的0。该参考文献揭示说,高电导率是与存在着混合价铜(Cu(II)/Cu(III))有关,并报导其电导率超过1000/T=3(k-1)至1000/T=10(k-1)的范围。60℃至-173℃这一温度范围对高温超导体来说是有代表性的超导起始点。
当上述公开的钙钛矿被用作氧分离机的膜时,分离机通常是工作在900℃至1100℃之间以获得高的氧通量。在这样高的温度下工作对膜以及反应器其它部件的稳定性是有害的。
因此,就需要有一种钙钛矿结构,它能在900℃以下的温度下从含氧气流中有效地分离氧,得到较高的氧通量,同时材料还具有机械稳定性。
本发明的第一个目的是要提供出一种适合在氧分离机中用作膜元件的陶瓷材料。该陶瓷材料具有立方钙钛矿晶体结构,并在温度低到600℃的情况下具有可测出的氧通量。
本发明的第二个目的是要提供出高机械稳定性的陶瓷材料,以避免在应力下破裂。这种应力可能产生于膜元件不同部分之间的温差,也可能产生于在刚启动时膜的阴极侧的氧浓度高于阳极侧的氧浓度。
按照本发明的第一方面,氧分离装置用的陶瓷膜元件基本上是由显著的立方钙钛矿结构构成的。该种结构在空气中在温度范围为25℃~950℃下基本上是稳定的。其结构形式为:
A1-xA'xB1-yB'yO3-z
其中A为
系元素;
B为选自钛、钒、铬、锰、铁、钴、镍和锌以及它们的混合物,条件是钴的含量大于0.1,铁的含量小于0.05;
B'为铜;
x在0.4与0.8之间;
y在0.1与0.9之间;以及
z>0,并根据化学计算来确定。
按照本发明的第二方面,膜元件还包括有能增强机械稳定性的第二相C。第二方面的结构形式为:
A1-xA′xB1-yB′yO3-z+C
其中C为选自银、钯、铂、金、铑、钌、钨、钽、耐热合金、镨-铟混合氧化物、铌-钛混合氧化物、氧化镍、氧化钨、氧化钽、铈土、锆土、镁氧矿,以及它们的合金或混合物。
在该第二方面的一个优选实施方案中,C为Ag和Pd的合金,该合金占组合物重量的3%~50%。在Ag/Pd合金中还包括有10%至95%(重量)的钯。
从下面对优选实施方案和附图的描述中,本技术领域的熟练人员将会联想起其它的目的、特性和优点:
图1示出使用按照本发明的方法制成的膜元件的氧分离机的断面图。
图2为X-射线的衍射模型,它示出本发明的膜元件的立方晶体结构。
图3示出本发明第一种膜元件的氧通量与温度的函数关系。
图4示出本发明第二种膜元件的氧通量与温度的函数关系。
本发明的组合物是混合的离子型陶瓷,它能选择性地传输氧和电子。请参阅图1,陶瓷组合物被制成为膜元件10,它是氧分离装置12的一部分。一种含氧料气14,例如空气,被输入氧分离装置12的第一侧16。膜元件10的一面或两面被涂上多孔的催化剂18,例如烧结的镍或钴。料气14中所含的氧被吸附到多孔催化剂18内部并在膜元件10的阴极侧表面20上离解。氧离子被通过膜元件10从阴极侧表面20传输到阳极侧表面22。在阳极侧表面22上,氧离子重新结合成氧,并在过程中释放出一个电子。这个电子被通过膜元件10从阳极侧表面22转移到阴极侧表面20。重新结合成的氧分子在阳极侧表面22上从多孔催化剂18中解吸,并被从氧分离装置12的第二侧26上作为成品气24被回收。成品气24可以是未反应的氧分子,也可以是与一种过程或燃料气26进行氧化反应的产物。
在本发明的第一实施方案中,膜元件10是一种陶瓷组合物,它具有显著的钙铁矿结构,该结构在空气温度范围为25℃至950℃的范围内是稳定的。该膜元件是ABO类型的,并含有特种掺杂剂。
该组合物以下述结构来代表:
A1-xA'xB1-yB'yO3-z
A'为适当的掺杂剂,并优选为锶;
B为选自钛、钒、铬、锰、铁、钴、镍、锌以及它们的混合物;
B'为铜:
x在0.4~0.8的范围内;
y在0.1~0.9的范围内,以及
由于该组合物缺氧,因此z大于0(用化学计算来确定)。
当B中包含的钴的量大于0.1时,铁的含量应小于0.05,因为增大铁的取代量将会降低膜的氧离子传导率。铁的含量优选不大于杂质的水平。
在本发明的一个优选方面中,x是在0.6和0.8之间,y是在0.1和0.3之间,z是在0.1和0.5之间。
最优选的组合物是
La0.2Sr0.8Co0.9Cu0.1O3-z
尽管本发明的组合物可用任何适当的方法来制得,但改进的Pechini法(液体混合法)是特别适用的。
和锶的碳酸盐在2000ml的烧杯中被溶于40ml的HNO3中。作温和的加热(最高达50℃)和搅拌对促进溶解有利。随后在该溶液中加入铜和钴的硝酸盐溶液。在该过程中加入约20ml的蒸馏水,以把所有痕量反应剂冲洗到该反应容器中。又加入0.3mol的柠檬酸和0.3mol的乙二醇作为配位剂。每批做成0.2mol所要求的陶瓷材料。各种组分的数量和分子量示于表1中。表1.在La0.2Sr0.8Co0.9Cu0.1O3-z合成
中所用各种反应剂的数量
化学式 | 分子量(g/mol) | 加入mol数 | 加入g数 |
La2(CO3)3 | 457.85 | 0.02 | 9.1570 |
SrCO3 | 147.63 | 0.16 | 23.6208 |
硝酸铜 | 1352.15 | 0.02 | 27.0429 |
硝酸钴 | 506.731 | 0.18 | 91.2116 |
然后,该溶液被加热到低于沸点的温度,通常加到约90℃,直到亚硝气开始显现为止。随后该溶液被倒入加过热的瓷盘中并在干燥箱中在180℃下进行干燥至少3小时。这样得到的是一块固体泡沫,将它粉碎成粉末并在振动或磨机中在乙醇介质中磨24小时,并使用二氧化锆作介质。其方法和温度示于表2。
表2.样品的温度处理
处理目的 | 加热速率(℃/分钟) | 保持温度(℃) | 保持时间(小时) |
除去有机物 | 0.5 | 300 | 1 |
煅烧 | 2 | 700 | 4 |
烧结 | 2 | 1030 | 2* |
*在加热和冷却中在300℃时也保持1小时。
在煅烧后,粉末在振动式磨机中干磨4小时。然后该粉末与4%(重量)的聚乙烯醇与水的溶液混合,该溶液用作压片的粘合剂,每10克粉末中加入0.8克的聚乙烯醇溶液。然后该粉末和粘合剂被放入Spex磨机(纽约州Edison的Spex工业公司制造)中磨很短时间,用聚甲基丙烯酸甲酯介质来使溶液分散在粉末中。
使用直径为1.5英寸的不锈钢模子单轴向压制成片。每片使用9克粉末,所用压力为2830磅/平方英寸。这些片随后被用40,000磅/平方英寸的压力进行等压压缩,并在氧气中进行烧结。这样得到的样品片所具有的密度约为理论密度的95%。
虽然第一实施方案的陶瓷材料具有氧分离装置12用的陶瓷膜结构10所需要的许多属性,但它是脆性的,易于破裂。该种陶瓷膜由于陶瓷在热循环中有可能发生结构破裂而限制了它的实际实用。借助于往制作膜元件10的陶瓷中加入延性金属作为第二相,就可提高陶瓷膜的机械性能。
因为高的氧通量是需要的,因此加入金属的量应小于渗滤极限。在此渗滤极限被定义为“为形成从阴极侧表面20延伸至阳极侧表面22的金属通道而必须掺入陶瓷粉末中的金属粉末的理论计算量”。通常,这要求存在的金属第二相的量大于30%(容积),以形成连续的第二相。但是,本发明并不要求有这样的金属通道。
任何具有高于陶瓷处理温度的熔点的导电延性金属都可用作第二相。第二相优选选自银、钯、铂、金、铑、钌、钨、钽、耐热合金如铬镍铁合金、哈斯特洛伊耐蚀镍基合金、蒙乃尔合金和ducrolloy,以及它们的混合物。更优选的第二相金属包括银、银钯合金和耐热合金。最优选的是银和钯的合金,其中该合金占整个组合物重量的3%~50%。更优选,银/钯合金占整个组合物重量的3%~20%。
一种优选的银/钯合金含有10%~95%重量的银。最优选,合金中银的含量在约50%至95%之间。
替代的办法是,第二相可选用陶瓷,例如镨-氧化铟混合物、铌-氧化钛混合物、氧化镍、氧化钨、氧化钽、铈土、锆、镁氧矿,以及它们的混合物。优选的第二相陶瓷是可作为氧化物加入到组合物中而随后借助于在还原气中加热而还原为金属的那些陶瓷。优选的第二相陶瓷的例子有氧化钛和氧化镍。
按照第二实施方案,膜元件组合物可用下述结构来代表:
A1-xA′xB1-yB′yO3-z+C
其中参数A、A′、B、B′、x、y和z与实施方案1相同,C则选自银、钯、铂、金、铑、钌、钨、钽、银、银/钯合金、耐热合金、镨-氧化铟混合物、铌-氧化钛混合物、氧化镍、氧化钨、氧化钽、铈土、锆土、镁氧矿,以及它们的合金或混合物。
一个示例性组合物为
La0.2Sr0.8Co0.9Cu0.1O3-z+20%重量的90%Ag/10%Pd
尽管该组合物可用任何适当的方法来制备,但改进的液体混合法可作为示例性的方法,在该方法中,组分离子的用热解重量分析法进行标准化的碳酸盐和硝酸盐溶液与柠檬酸、乙二醇和水一起加热。
作为方法之一,将9.1570克的La2(CO3)3和23.6208克的SrCO3加入一个2000ml的烧杯中。往该碳酸盐中加入约20ml的蒸馏水,随后再加入约30ml的硝酸,以溶解碳酸盐。配成的溶液被加热到约90℃并加搅拌以加速溶解。在碳酸盐溶解后,立即往烧杯中加入28.7875克的硝酸铜溶液(每mol Cu2+1439.38克溶液)和91.2116克的硝酸钴溶液。然后加入57.6克的柠檬酸和18.6克的乙二醇,并使溶液保持在90℃并加搅拌。该前体溶液保持在90℃直到溶液中的亚硝气全部放出为止,此时该溶液被放进预热到180℃的陶瓷盘中,并保持此温度不变12个小时,以形成半硬的聚合物炭焦。
然后,该炭焦被混和在乙醇中研磨8小时,乙醇在煅烧前挥发掉。煅烧分为二步来做。研磨过的炭焦首先以每分钟0.4℃的速率加热到300℃,在此过程中一些有机物被烧掉,接着以每分钟1.7℃的升温速率加热到700℃,并在700℃下保持4小时以保证相的形成。
钙钛矿加合金的复合组合物用下述方法来制备:用8.0克所产出的陶瓷与2.0克合金,再加0.5克粘合剂(在水中溶有5%重量的聚乙烯醇)放入研钵中用研杆搅和。
大约0.5克的粉末状复合物被放入直径0.5英寸的模具中以5,000磅的压力进行单轴向压缩。这些样品被放在氧化铝耐火垫板顶部预先粗化的La0.2Sr0.8Co0.9Cu0.1O3-z床上,并以每分钟3℃的速率加热到烧结温度。这些材料随后在空气中在940℃和1000℃之间烧结4小时。
加热到940℃进行烧结所得到的密度为6.37g/cm3,带有2.17%的开孔。把烧结温度提高到960℃使密度增大到6.39g/cm3,使开孔减为0.7%。把烧结温度提高到980℃,所得到的密度为6.42g/cm3,带有的开孔为0.6%。但是,有一次烧结温度提高到了1000℃,金属就开始从预先粗化的陶瓷床中沥滤出来,所得到的密度减为6.31g/cm3,而开孔减到0.2%。
如上所指出的,烧结必须在低于熔融金属发生沥滤的温度下进行。
本发明的陶瓷材料用作氧分离机的膜元件的有利之处,从下面的实施例中将会变得更加明显。实施例1
按照上述第一实施方案制成的陶瓷片,用Scintag(加里福尼亚州Cupertino的Scintag公司制造)衍射计(带有高温附件)进行了X-射线衍射(XRD)分析,以分析在各种温度下相的发展情况。如图2所示,在40℃和700℃之间的所有温度下样品都保持在立方结构下没有发生相转化。图2中的硅和铂的峰值分别来自内部标准和样品持有人。
用厚1.0mm、封在带有银糊(silver paste)的氧化铝试验池中的烧结盘来测试样品的氧渗透率。渗透率试验是作为温度的函数来进行,使用的料气为氮中含有20%容积的氧。在料气进入以前先用氦气吹洗。
使用Hewlett Packard 5890气体色谱仪(特拉华州Wilmington的Hewlett Packard公司制造)和Servomex Series 1100氧分析仪(英格兰Sussex Crowborough的Servomex有限公司制造)来分析气体组分和计算氧通量。表3记录了当使用1.0电子伏特的激活能后,氧通量与温度的函数关系。
表3
温度(℃) | 氧通量(标准cm3/cm2) |
600 | 0.2 |
700 | 0.4 |
800 | 0.8 |
900 | 1.5 |
图3对表3所记录的氧通量与现有技术的一种陶瓷膜结构(La.05Sr.95CoO3)进行了比较。现有技术的组合物直到约900℃以前都没有传输出氧。而本发明的组合物在温度低到600℃就己有可测出的氧传输,而且在温度在700和800℃之间就有了商业可用的氧通量。
随后使该陶瓷结构冷却到室温并检测到了陶瓷的裂纹。实施例2
用上述第二实施方案的组合物所做的1mm厚的盘,被封在带有银糊的氧化铝试验池中,并如上述那样进行渗透试验。表4记录着测得的氧通量。
表4
温度(℃) | 氧通量(标准cm3/cm2) |
600 | 0.1 |
700 | 0.3 |
800 | 0.7 |
900 | 1.1 |
图4对按照第2实施方案制作的陶瓷材料所测得的氧通量,与按第1实施方案制作的陶瓷材料以及上述现有技术陶瓷材料的相关氧通量进行了比较。虽然加入金属相使氧通量略有降低,但仍在低到600℃的温度下测到了氧通量,而商业有用的氧通量则在低到800℃的温度下即可获得。有重要意义的是,在冷却后,该样品完整如初,没有裂纹。
Claims (9)
2.权利要求1的膜元件,其中x在0.6与0.8之间,y在0.1与0.3之间,z在0.1与0.5之间。
3.权利要求1的膜元件,其中A为
,A'为锶,B为钴。
4.权利要求3的膜元件,其中x在0.6与0.8之间,y在0.1与0.3之间,z在0.1与0.5之间。
5.权利要求1的膜元件,它还包括以下述结构来代表的C:
A1-xA'xB1-yB'yO3-z+C
其中C选自银、钯、铂、金、铑、钌、钨、钽;耐热合金如铬镍铁合金、哈斯特洛伊耐蚀镍基合金、蒙乃尔合金和ducrolloy;镨-铟混合氧化物、铌-钛混合氧化物、氧化镍、氧化钨、氧化钮、铈土、锆土、镁氧矿;以及它们的混合物。
6.权利要求5的膜元件,其中C为选自银、银/钯合金和耐热合金如铬镍铁合金、哈斯特洛伊耐蚀镍基合金、蒙乃尔合金和ducrolloy。
7.权利要求6的膜元件,其中C为Ag和Pd的合金并占该组合物重量的3%至50%。
8.权利要求7的膜元件,其中C为Ag和Pd的合金并占该组合物重量的3%至20%。
9.权利要求7的膜元件,其中C含有10%至95%重量的钯。
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DE69603762T2 (de) * | 1995-03-13 | 2000-03-09 | Air Prod & Chem | Elektrochemische Membrane auf Basis von Zusammensetzungen mit der Fähigkeit zu funktionieren unter hohen Sauerstoffpartialdrucken zur Verwendung in Feststoffvorrichtungen zur Herstellung von Sauerstoff |
US5837125A (en) | 1995-12-05 | 1998-11-17 | Praxair Technology, Inc. | Reactive purge for solid electrolyte membrane gas separation |
ID19327A (id) * | 1996-12-31 | 1998-07-02 | Praxiar Technology Inc | Membran elektrolit padat dengan unsur pokok pemertinggi secara mekanik dan pemertinggi secara katalitik yang bersifat dapat menyerap |
US5911860A (en) * | 1996-12-31 | 1999-06-15 | Praxair Technology, Inc. | Solid electrolyte membrane with mechanically-enhancing constituents |
-
1999
- 1999-02-02 US US09/241,610 patent/US6235187B1/en not_active Expired - Fee Related
-
2000
- 2000-02-01 CN CN00101984A patent/CN1263791A/zh active Pending
- 2000-02-01 KR KR1020000004824A patent/KR20000076579A/ko not_active Application Discontinuation
- 2000-02-01 BR BR0000233-0A patent/BR0000233A/pt active Pending
- 2000-02-01 MX MXPA00001136A patent/MXPA00001136A/es unknown
- 2000-02-01 EP EP00101979A patent/EP1027916A1/en not_active Withdrawn
- 2000-02-01 CA CA002297578A patent/CA2297578A1/en not_active Abandoned
- 2000-02-01 ZA ZA200000435A patent/ZA200000435B/xx unknown
- 2000-02-01 JP JP2000023737A patent/JP2000233120A/ja not_active Abandoned
- 2000-02-01 AU AU14842/00A patent/AU1484200A/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104529448A (zh) * | 2015-01-23 | 2015-04-22 | 景德镇陶瓷学院 | 一种高孔隙率高渗透性Nb2O5陶瓷膜及其制备方法 |
CN104529448B (zh) * | 2015-01-23 | 2016-03-30 | 景德镇陶瓷学院 | 一种高孔隙率高渗透性Nb2O5陶瓷膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US6235187B1 (en) | 2001-05-22 |
KR20000076579A (ko) | 2000-12-26 |
BR0000233A (pt) | 2000-09-05 |
JP2000233120A (ja) | 2000-08-29 |
CA2297578A1 (en) | 2000-08-02 |
MXPA00001136A (es) | 2002-03-08 |
EP1027916A1 (en) | 2000-08-16 |
AU1484200A (en) | 2000-08-24 |
ZA200000435B (en) | 2000-09-06 |
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