CN101147027A - 用于储存气态烃的金属-有机骨架材料 - Google Patents
用于储存气态烃的金属-有机骨架材料 Download PDFInfo
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- CN101147027A CN101147027A CNA2006800089790A CN200680008979A CN101147027A CN 101147027 A CN101147027 A CN 101147027A CN A2006800089790 A CNA2006800089790 A CN A2006800089790A CN 200680008979 A CN200680008979 A CN 200680008979A CN 101147027 A CN101147027 A CN 101147027A
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/50—Stabilized
Abstract
本发明涉及在含有金属-有机骨架材料的容器中储存液化气的方法,装有这种气体的容器,填充容器的方法和使用该容器释放气体的用途。
Description
本发明涉及在含有金属-有机骨架材料的容器中储存液化气的方法,装有这种气体的容器,填充容器的方法和使用该容器释放气体的用途。
液化气,尤其是丙烷或丙烷和丁烷的混合物,常被用作便携燃料供应品。因此,将气体在高到足以将该气体以液态储存在瓶或罐中的压力下储存在耐压瓶或罐中。液化气以大约-50℃至大约10℃的沸点为特征。因此,要将气体在室温下转化成其液态,通常20巴或更高的压力是必需的。
但是,需要在低于上述使气体保持其液态的最小压力的压力下储存通常被视为液化气的气体。最重要的原因之一是由加压容器的安全规定引起的。
传统的瓶子等不能提供足以在低压范围内有效储存气体的空间。
其它储存气体的方式是将所需气体吸收在多孔材料中。这类材料可以是无机性质的,例如沸石,或有机性质的,例如金属有机骨架(MOF)。
US 2003/0148165 A1概括地描述了使用MOFs的气体储存。
非常需要提供适合在低压范围内以气态储存液化气的方法。
因此,本发明的目的是提供在低压范围内以足够高的量以气态储存被称作液化气的气体的方法。
通过下述在容器中储存液化气的方法实现了该目的,该容器具有使液化气进入或离开容器的入口和,任选地,独立的出口,和能够以预定量且在预定压力下将处于气态的液化气保持在容器内的气密保持装置,并含有金属-有机骨架材料(MOF),该金属-有机骨架材料包含至少一种金属离子和至少一种与所述金属离子配位结合的至少双配位的有机化合物,其中容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2。
出乎意料地发现,包含MOF的容器与不使用MOF的情况相比,可以摄取未预料的大量的液化气。这能够使用至少低五分之四的压力在低压范围内储存足量的液化气。
图1显示了在含有MOF(曲线A)和不含MOF(曲线B)的容器中的液化气(这里以丙烷作为例子)摄取的大致曲线演变。
在本发明的含义内,术语“液化气”优选是指根据温度(但是,室温是优选的),可以在最多40巴的压力转化成其液态的气体或不同气体的混合物。此外,根据本发明,术语“液化气”不是自然而然地指液化态下的气体。
工业应用中重要的气体性质、压缩气体、所用气体容器和操作指示可以参看“压缩气体手册”,第三版,Van Nostrand Reinhold,New York,1989,并经此引用并入本文。
优选地,液化气选自由卤化的C1-C10烃、丙烷、丁烷、异丁烷和它们的混合物组成的组。更优选地,液化气是丙烷。
由于根据本发明使用的低压范围,容器的形状和材料不必满足加压容器的要求。优选地,本发明的容器具有非圆柱形。容器材料不必由不锈钢构成。
容器包含使液化气进入或离开容器的入口和,任选地,独立的出口,和能够保持液化气的气密保持装置。优选地,入口和出口同样配有充当气密保持装置的常规阀。
在优选实施方案中,压力大于0.1巴且小于20巴。更优选地,压力大于1巴且小于20巴,更优选大于1巴且小于10巴。
容器内液化气的量为至少2克/升。
容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2。优选地,该比率最多0.1,更优选最多0.05。
本发明的另一方面是装有预定量的和在预定压力下的液化气的容器,该容器具有使液化气进入或离开容器的入口和,任选地,独立的出口,和能够以预定量且在预定压力下将处于气态的液化气保持在容器内的气密保持装置,并含有金属-有机骨架材料(MOF),所述金属-有机骨架材料包含至少一种金属离子和至少一种与所述金属离子配位结合的至少双配位的有机化合物,其中容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2。
本发明的再一方面是用液化气填充容器直至预定量和预定压力的方法,该容器具有使液化气进入或离开容器的入口和,任选地,独立的出口,和能够将液化气以气态保持在容器内的气密保持装置,并含有金属-有机骨架材料(MOF),所述金属-有机骨架材料包含至少一种金属离子和至少一种与所述金属离子配位结合的至少双配位的有机化合物,其中容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2,该方法包括下列步骤:
-使容器入口与液化气瓶接触,该气体处于其液态或压缩态,使得进给容器内的压力超过待填充的容器内的压力。
本发明的再一方面是本发明容器的用途,用于液化气的受控释放。
合适的MOFs是本领域内已知的。它们可以作为粉末使用,但优选地,MOFs作为成型体使用,更优选作为挤出物或小片使用。
含MOF的粉末具有细粉状至粉状粒度,并可以含有微晶(小晶体)或由其构成。根据本发明,术语“粉末”用于指上述所有形式及其混合物。粉末的最大粒度优选在每一方向上小于0.2毫米。
成型体可以具有任何适于预计用途的形式。优选地,其是丸形、片形或条形的。在本发明中,术语“成型体”优选是指在至少一个空间方向上延伸至至少0.2毫米的任何固体。没有施加其它限制,即,成型体可以具有任何可能的形状,并可以在任何方向上延伸任何长度,只要其优选在一个方向延伸至至少0.2毫米即可。在更优选实施方案中,成型体在所有方向上不延伸至超过50毫米,且不小于0.2毫米。在进一步优选实施方案中,该范围限于1毫米至16毫米,优选1.5毫米至5毫米。
至于这些成型体的几何结构,球体或圆柱体也是优选的,还有盘状丸粒或任何其它合适的几何结构,例如蜂窝、网格、中空体、线布设体,等等。
含MOF的粉末包括由金属离子和与所述金属离子配位结合的至少双配位的有机化合物构成的金属-有机骨架结构。这样的MOF包含可以被孔隙到达的空腔。一个空腔由8个通过至少双配位的有机化合物连接在一起的金属离子界定。
如上所述,在例如US 5,648,508,EP-A-0790253,M.O’Keeffe等人,J.Sol.State Chem.,152(2000)第3-20页,H.Li等人,Nature402(1999)第276以下,M.Eddaoudi等人,Topics in Catalysis9(1999)第105-111页,B.Chen等人,Science291(2001)第1021-23而和DE-A-10111230中描述了MOF。
本发明中所用的MOFs包含孔隙,特别是微孔和/或中孔。根据PureApplied Chem.45,第71页以下,特别是在笫79页(1976)中给出的定义,微孔是指直径2毫米或更小的孔隙,中孔是指直径2纳米至50纳米的孔隙。微孔和/或中孔的存在可以通过吸附测量法来监测,其根据DIN 66131和/或DIN 66134测定金属有机骨架材料在77K摄取氮的能力。
例如,等温曲线的I型形式意味着存在微孔[参见,例如,M.Eddaoudi等人,Topics in Catalysis9(1999)的第4段]。在优选实施方案中,根据Langmuir模型(DIN 66131、66134、66135)计算的比表面积优选高于5平方米/克,更优选高于10平方米/克,再优选高于50平方米/克,再更优选高于500平方米/克,更优选高于1000平方米/克,更优选高于1500平方米/克,更优选高于2500平方米/克,并可以增至高于4500平方米/克的范围。
成型体可以具有较低的比表面积,但优选高于10平方米/克,更优选高于50平方米/克,最优选高于500平方米/克。
至于根据本发明使用的骨架材料内的金属组分,特别提到元素周期表的主族元素和副族元素的金属离子,即族Ia、IIa、IIIa、IVa至VIIIa和Ib至Vib。在这些金属组分中,特别提到Mg、Ca、Sr、Ba、Sc、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Si、Ge、Sn、Pb、As、Sb和Bi,更优选提到Zn、Cu、Ni、Pd、Pt、Ru、Rh和Co,最优选Zn和Cu。至于这些元素的金属离子,特别提到:Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo3+、W3+、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3+、In3+、Tl3+、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+、Bi5+、Bi3+和Bi+。
关于优选的金属离子及其进一步细节,特别参看:US 5648508,特别是第11栏,第11至51行,“The Metal Ions”部分,该部分经此引用并入本文。
除EP-A 0790253和US 5648508中公开的金属盐外,可以使用其它金属化合物,例如硫酸盐、磷酸盐和元素周期表主族和副族金属的其它络合的抗衡离子金属盐。有或没有指定的化学计量的金属氧化物、混合氧化物和金属氧化物和/或混合氧化物的混合物是优选的。所有上述金属化合物都可溶或不溶。
至于能够与金属离子配位的至少双配位的有机化合物,原则上可以使用适于此用途并符合上述至少双配位的要求的所有化合物。所述有机化合物必须具有至少两个能够与金属盐的金属离子(特别是与上述类型的金属)配位的中心。至于所述至少双配位的有机化合物,具体提到具有下列亚结构的化合物:
i)含有1至10个碳原子的烷基亚结构,
ii)含有1至5个苯基环的芳基亚结构,
iii)烷基或芳基胺亚结构,由含有1至10个碳原子的烷基或含有1至5个苯基环的芳基构成,
所述亚结构具有与其结合的至少一个至少双配位的官能团“X”,该官能团与所述化合物的亚结构共价键合,且其中X选自CO2H、CS2H、NO2、SO3H、Si(OH)3、Ge(OH)3、Sn(OH)3、Si(SH)4、Ge(SH)4、Sn(SH)3、PO3H、AsO3H、AsO4H、P(SH)3、As(SH)3、CH(RSH)2、C(RSH)3、CH(RNH2)2、C(RNH2)3、CH(ROH)2、C(ROH)3、CH(RCN)2、C(RCN)3,其中R是含有1至5个碳原子的烷基,或由1至2个苯基环构成的芳基,和CH(SH)2、C(SH)3、CH(NH2)2、C(NH2)2、CH(OH)2、C(OH)3、CH(CN)2和C(CN)3。
特别可提到取代或未取代的、单环或多环芳族二羧酸、三羧酸和四羧酸,和取代或未取代的、含至少一个杂原子的芳族二羧酸、三羧酸和四羧酸,其具有一个或多个环。
优选配体是ADC(乙炔二羧酸酯/盐)、NDC(萘二羧酸酯/盐)、BDC(苯二羧酸酯/盐)、ATC(金刚烷四羧酸酯/盐)、BTC(苯三羧酸酯/盐)、BTB(苯三苯甲酸酯/盐)、MTB(甲烷四苯甲酸酯/盐)和ATB(金刚烷三苯甲酸酯/盐)。更优选的双配位配体是1,2,3-和1,3,5-苯三羧酸(BCT)、间苯二酸、对苯二酸、2,5-二羟基-对苯二酸和2,2,-联吡啶-5,5’-二羧酸。
除了所述至少双配位的有机化合物外,根据本发明使用的骨架材料还可以包含一个或多个单齿配体,其优选选自下列单齿物质和/或其衍生物:
a.烷基胺及其相应的烷基铵盐,含有具有1至20个碳原子的直链、支链或环状脂族基团(及其相应的铵盐);
b.含有1至5个苯基环的芳胺及其相应的芳铵盐;
c.烷基鳞盐,含有具有1至20个碳原子的直链、支链或环状脂族基团;
d.具有1至5个苯基环的芳基鏻盐;
e.烷基有机酸和相应的烷基有机阴离子(和盐),含有具有1至20个碳原子的直链、支链或环状脂族基团;
f.具有1至5个苯基环的芳基有机酸及其相应的芳基有机阴离子和盐;
g.脂族醇,含有具有1至20个碳原子的直链、支链或环状脂族基团;
h.具有1至5个苯基环的芳基醇;
i.无机阴离子,选自:
硫酸根、硝酸根、亚硝酸根、亚硫酸根、亚硫酸氢根、磷酸根、磷酸氢根、磷酸二氢根、二磷酸根、三磷酸根、亚磷酸根、氯离子、氯酸根、溴离子、溴酸根、碘离子、碘酸根、碳酸根、碳酸氢根、和上述无机阴离子的相应的酸和盐,
j.氨、二氧化碳、甲烷、氧、乙烯、己烷、苯、甲苯、二甲苯、氯苯、硝基苯、萘、噻吩、吡啶、丙酮、1,2-二氯乙烷、二氯甲烷、四氢呋喃、乙醇胺、三乙胺和三氟甲基磺酸。
关于至少双配位的有机化合物和单齿物质(由其可以衍生出本申请中所用的骨架材料的配体)的进一步细节,可以获自EP-A0790253,其相关内容经此引用并入本申请。
在本申请内,包含Zn2+作为金属离子和衍生自对苯二甲酸的配体作为二齿化合物的本文所述类型骨架材料是特别优选的。所述骨架材料在文献中被称作MOF-5。
在EP-A 0790253、US 5,648,508和DE-A-10111230中特别公开了各自可用于制备本发明中所用的骨架材料的其它金属离子、至少双配位的有机化合物和单齿物质,以及它们的制备方法。
作为特别可用于制备MOF-5的溶剂,除了上述文献中公开的溶剂外,还可以使用二甲基甲酰胺、二乙基甲酰胺和N-甲基吡咯烷酮,它们单独或彼此结合或与其它溶剂结合使用。在骨架材料的制备中,特别是在MOF-5的制备中,使溶剂和母液在结晶之后再循环,以节省成本和材料。
金属-有机骨架的孔径大小可以通过选择合适的有机配体和/或二齿化合物(=连接基)来调节。通常,连接基越大,孔径大小越大。在不存在宿主的情况下和在至少200℃下仍可被MOF支撑的任何孔径大小都是可行的。0.2纳米至30纳米的孔径大小是优选的,0.3纳米至3纳米的孔径大小特别优选。
对于成型体,可以存在其它孔径大小。优选地,总孔隙体积的超过50%、更优选总孔隙体积的超过75%由孔径最多达1000纳米的孔隙构成。
优选地,大部分孔隙体积由来自两种不同的直径范围的孔隙构成。因此,更优选地,总孔隙体积的超过25%、更优选超过50%由直径100纳米至800纳米的孔隙构成,优选地,总孔隙体积的超过15%、更优选超过25%由直径最多10纳米的孔隙构成。通过Hg-孔隙度测定法(DIN 66133)测定孔隙分布。
下面给出金属-有机骨架材料(MOFs)的例子以例证上述一般概念。这些具体例子不是要限制本发明的一般原则和范围。
作为例子,下面给出了已经合成和表征的金属-有机骨架材料的列表。这还包括新型的等网状(isoreticular)金属有机骨架材料(IR-MOFs),其可用在本申请的骨架中。在例如M.Eddouadi等人,Science 295(2002)469中描述了具有相同骨架布局并表现出不同孔径大小和晶体密度的这类材料,其经此引用并入本申请。
所用溶剂对于这些材料的合成特别重要并因此在表中提及。已经通过x-射线衍射获得了晶胞参数值(角度α、β和γ,以及以埃为单位给出的间距a、b和c),它们代表下表中给出的空间群。
MOF-n | 组分摩尔比M+L | 溶剂 | α | β | γ | a | b | c | 空间群 |
MOF-0 | Zn(NO3)2·6H2OH3(BTC) | 乙醇 | 90 | 90 | 120 | 16.711 | 16.711 | 14.189 | P6(3)/Mcm |
MOF-2 | Zn(NO3)2·6H2O(0.246mmol)H2(BDC)(0.241mmol) | DMF甲苯 | 90 | 102.8 | 90 | 6.718 | 15.49 | 12.43 | P2(1)/n |
MOF-3 | Zn(NO3)2·6H2O(1.89mmol)H2(BDC)(1.93mmol) | DMFMeOH | 99.72 | 111.11 | 108.4 | 9.726 | 9.911 | 10.45 | P-1 |
MOF-4 | Zn(NO3)2·6H2O(1.00mmol)H3(BTC)(0.5mmol) | 乙醇 | 90 | 90 | 90 | 14.728 | 14.728 | 14.728 | P2(1)3 |
MOF-5 | Zn(NO3)2·6H2O(2.22mmol)H2(BDC)(2.17 mmol) | DMF氯苯 | 90 | 90 | 90 | 25.669 | 25.669 | 25.669 | Fm-3m |
MOF-38 | Zn(NO3)2·6H2O(0.27mmol)H3(BTC)(0.15mmol) | DMF氯苯 | 90 | 90 | 90 | 20.657 | 20.657 | 17.84 | 14cm |
MOF-31Zn(ADC)2 | Zn(NO3)2·6H2O0.4mmolH2(ADC)0.8mmol | 乙醇 | 90 | 90 | 90 | 10.821 | 10.821 | 10.821 | Pn(-3)m |
MOF-12Zn2(ATC) | Zn(NO3)2·6H2O0.3mmolH4(ATC)0.15mmol | 乙醇 | 90 | 90 | 90 | 15.745 | 16.907 | 18.167 | Pbca |
MOF-20ZnNDC | Zn(NO3)2·6H2O0.37mmolH2NDC0.36mmol | DMF氯苯 | 90 | 92.13 | 90 | 8.13 | 16.444 | 12.807 | P2(1)/c |
MOF-37 | Zn(NO3)2·6H2O0.2mmolH2NDC0.2mmol | DEF氯苯 | 72.38 | 83.16 | 84.33 | 9.952 | 11.576 | 15.556 | P-1 |
MOF-8Tb2(ADC) | Tb(NO3)3·5H2O0.10mmolH2ADC0.20mmol | DMSOMeOH | 90 | 115.7 | 90 | 19.83 | 9.822 | 19.183 | C2/c |
MOF-9Tb2(ADC) | Tb(NO3)3·5H2O0.08mmolH2ADB0.12mmol | DMSO | 90 | 102.09 | 90 | 27.056 | 16.795 | 28.139 | C2/c |
MOF-6 | Tb(NO3)3·5H2O0.30mmolH2(BDC)030mmol | DMFMeOH | 90 | 91.28 | 90 | 17.599 | 19.996 | 10.545 | P21/c |
MOF-7 | Tb(NO3)3·5H2O0.15mmolH2(BDC)0.15mmol | H2O | 102.3 | 91.12 | 101.5 | 6.142 | 10.069 | 10.096 | P-1 |
MOF-69A | Zn(NO3)2·6H2O0.083mmol4,4’BPDC0.041mmol | DEFH2O2MeNH2 | 90 | 111.6 | 90 | 23.12 | 20.92 | 12 | C2/c |
MOF-69B | Zn(NO3)2·6H2O0.083mmol2,6-NCD0.041mmol | DEFH2O2MeNH2 | 90 | 953 | 90 | 20.17 | 18.55 | 12.16 | C2/c |
MOF-11Cu2(ATC) | Cu(NO3)2·2.5H2O0.47mmolH2ATC0.22mmol | H2O | 90 | 93.86 | 90 | 12.987 | 11.22 | 11.336 | C2/c |
MOF-11Cu2(ATC)脱水 | 90 | 90 | 90 | 8.4671 | 8.4671 | 14.44 | P42/mmc | ||
MOF-14Cu3(BTB) | Cu(NO3)2·2.5H2O0.28mmolH3BTB0.052mmol | H2ODMFEtOH | 90 | 90 | 90 | 26.946 | 26.946 | 26.946 | Im-3 |
MOF-32Cd(ATC) | Cd(NO3)2·4H2O0.24mmolH4ATC0.10mmol | H2ONaOH | 90 | 90 | 90 | 13.468 | 13.468 | 13.468 | P(-4)3m |
MOF-33Zn2(ATB) | ZnCl20.15mmolH4ATB0.02mmol | H2ODMFEtOH | 90 | 90 | 90 | 19.561 | 15.255 | 23.404 | Imma |
MOF-34Ni(ATC) | Ni(NO3)2·6H2O0.24mmolH4ATC0.10mmol | H2ONaOH | 90 | 90 | 90 | 10.066 | 11.163 | 19.201 | P212121 |
MOF-36Zn2(MTB) | Zn(NO3)2·4H2O0.20mmolH4MTB0.04mmol | H2ODMF | 90 | 90 | 90 | 15.745 | 16.907 | 18.167 | Pbca |
MOF-39Zn3O(HBTB) | Zn(NO3)2·4H2O0.27mmolH3BTB0.07mmol | H2ODMFEtOH | 90 | 90 | 90 | 17.158 | 21.591 | 25.308 | Pnma |
NO305 | FeCl2·4H2O5.03mmol甲酸86.90mmol | DMF | 90 | 90 | 120 | 8.2692 | 8.2692 | 63.566 | R-3c |
NO306A | FeCl2·4H2O5.03mmol甲酸86.90mmol | DEF | 90 | 90 | 90 | 9.9364 | 18374 | 18.374 | Pbcn |
NO29类MOF-0 | Mn(AC)2·4H2O0.46mmolH3BTC0.69mmol | DMF | 120 | 90 | 90 | 14.16 | 33.521 | 33.521 | P-1 |
BPR48A2 | Zn(NO3)2·6H2O0.012mmolH2BDC0.012mmol | DMSO甲苯 | 90 | 90 | 90 | 14.5 | 17.04 | 18.02 | Pbca |
BPR69B1 | Cd(NO3)2·4H2O0.0212mmolH2BDC0.0428mmol | DMSO | 90 | 98.76 | 90 | 14.16 | 15.72 | 17.66 | Cc |
BPR92A2 | Co(NO3)2·6H2O0.018mmolH2BDC0.018mmol | NMP | 1063 | 107.63 | 107.2 | 7.5308 | 10.942 | 11.025 | P1 |
BPR95C5 | Cd(NO3)2·4H2O0.012mmolH2BDC0.36mmol | NMP | 90 | 112.8 | 90 | 14.460 | 11.085 | 15.829 | P2(1)/n |
CuC6H4O6 | Cu(NO3)2·2.5H2O0.370mmolH2BDC(OHH)20.37mmol | DMF氯苯 | 90 | 105.29 | 90 | 15.259 | 14.816 | 14.13 | P2(1)/c |
M(BTC)类MOF-0 | Co(SO4)H2O0.055mmolH3BTC0.037mmol | DMF | 与MOF-0相同 | ||||||
Tb(C6H4O6) | Tb(NO3)3·5H2O0370mmolH2(C6H4O6)0.56mmol | DMF氯苯 | 104.6 | 107.9 | 97.147 | 10.491 | 10.981 | 12.541 | P-1 |
Zn(C2O4) | ZnCl20370mmol草酸0.37mmol | DMF氯苯 | 90 | 120 | 90 | 9.4168 | 9.4168 | 8.464 | P(-3)1m |
Co(CHO) | Co(NO3)2·5H2O0.043mmol甲酸1.60mmol | DMF | 90 | 91.32 | 90 | 11.328 | 10.049 | 14.854 | P2(1)/n |
Cd(CHO) | Cd(NO3)2·4H2O0.185mmol甲酸0.185mmol | DMF | 90 | 120 | 90 | 8.5168 | 8.5168 | 22.674 | R-3c |
Cu(C3H2O4) | Cu(NO3)2·2.5H2O0.043mmol丙二酸0.192mmol | DMF | 90 | 90 | 90 | 8.366 | 8.366 | 11.919 | P43 |
Zn6(NDC)5MOF-48 | Zn(NO3)2·6H2O0.097mmol14NDC0.069mmol | DMF氯苯H2O2 | 90 | 95.902 | 90 | 19.504 | 16.482 | 14.64 | C2/m |
MOF-47 | Zn(NO3)2·6H2O0.185mmolH2(BDC[CH3]4)0.185mmol | DMF氯苯H2O2 | 90 | 92.55 | 90 | 11.303 | 16.029 | 17.535 | P2(1)/c |
MO25 | Cu(NO3)2.2.5H2O0.084mmolBPhDC0.085mmol | DMF | 90 | 112.0 | 90 | 23.880 | 16.834 | 18.389 | P2(1)/c |
Cu-Thio | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DEF | 90 | 113.6 | 90 | 15.4747 | 14.514 | 14.032 | P2(1)/c |
C1BDC1 | Cu(NO3)2·2.5H2O0.084mmolH2(BDCCl2)0.085mmol | DMF | 90 | 105.6 | 90 | 14.911 | 15.622 | 18.413 | C2/c |
MOF-101 | Cu(NO3)2·2.5H2O0.084mmolBrBDC0.085mmol | DMF | 90 | 90 | 90 | 21.607 | 20.607 | 20.073 | Fm3m |
Zn3(BTC)2 | ZnCl20.033mmolH3BTC0.033mmol | DMFEtOH加碱 | 90 | 90 | 90 | 26.572 | 26.572 | 26.572 | Fm-3m |
MOF-j | Co(CH3CO2)2·4H2O(1.65mmol)H3(BZC)(0.95mmol) | H2O | 90 | 112.0 | 90 | 17.482 | 12.963 | 6.559 | C2 |
MOF-n | Zn(NO3)2·6H2OH3(BTC) | 乙醇 | 90 | 90 | 120 | 16.711 | 16.711 | 14.189 | P6(3)/mcm |
PbBDC | Pb(NO3)2(0.181mmol)H2(BDC)(0181mmol) | DMF乙醇 | 90 | 102.7 | 90 | 8.3639 | 17.991 | 9.9617 | P2(1)/n |
Znhex | Zn(NO3)2·6H2O(0.171mmol)H3BTB(0.114mmol) | DMFP-二甲苯乙醇 | 90 | 90 | 120 | 37.1165 | 37.117 | 30.019 | P3(1)c |
AS16 | FeBr20.927mmolH2(BDC)0.927mmol | 脱水DMF | 90 | 90.13 | 90 | 7.2595 | 8.7894 | 19.484 | P2(1)c |
AS27-2 | FeBr20.927mmolH3(BDC)0.464mmol | 脱水DMF | 90 | 90 | 90 | 26.735 | 26.735 | 26.735 | Fm3m |
AS32 | FeCl31.23mmolH2(BDC)1.23mmol | 脱水DMF乙醇 | 90 | 90 | 120 | 12.535 | 12.535 | 18.479 | P6(2)c |
AS54-3 | FeBr20.927BPDC0.927mmol | 脱水DMF正丙醇 | 90 | 109.98 | 90 | 12.019 | 15.286 | 14.399 | C2 |
AS61-4 | FeBr20.927molm-BDC0.927mmol | 脱水吡啶 | 90 | 90 | 120 | 13.017 | 13.017 | 14.896 | P6(2)c |
AS68-7 | FeBr20.927mmolm-BDC1.204mmol | 脱水DMF吡啶 | 90 | 90 | 90 | 18.3407 | 10.036 | 18.039 | Pca21 |
Zn(ADC) | Zn(NO3)2·6H2O0.37mmolH2(ADC)0.36mmol | DMF氯苯 | 90 | 99.85 | 90 | 16.764 | 9.349 | 9.635 | C2/c |
MOF-12Zn2(ATC) | Zn(NO3)2-6H2O0.30mmolH4(ATC)0.15mmol | 乙醇 | 90 | 90 | 90 | 15.745 | 16.907 | 18.167 | Pbca |
MOF-20ZnNDC | Zn(NO3)2·6H2O037mmolH2NDC0.36mmol | DMF氯苯 | 90 | 92.13 | 90 | 8.13 | 16.444 | 12.807 | P2(1)/c |
MOF-37 | Zn(NO3)2·6H2O0.20mmolH2NDC0.20mmol | DEF氯苯 | 72.38 | 83.16 | 84.33 | 9.952 | 11.576 | 15.556 | P-1 |
Zn(NDC)(DMSO) | Zn(NO3)2·6H2OH2NDC | DMSO | 68.08 | 75.33 | 8831 | 8.631 | 10.207 | 13.114 | P-1 |
Zn(NDC) | Zn(NO3)2·6H2OH2NDC | 90 | 99.2 | 90 | 19.289 | 17.628 | 15.052 | C2/c | |
Zn(HPDC) | Zn(NO3)2·4H2O0.23mmolH2(HPDC)0.05mmol | DMFH2O | 107.9 | 105.06 | 94.4 | 8.326 | 12.085 | 13.767 | P-1 |
Co(HPDC) | Co(NO3)2·6H2O0.21mmolH2(HPDC)0.06mmol | DMFH2O/乙醇 | 90 | 97.69 | 90 | 29.677 | 9.63 | 7.981 | C2/c |
Zn3(PDC)2.5 | Zn(NO3)2·4H2O0.17mmolH2(HPDC)0.05mmol | DMF/CIBzH2O/TEA | 79.34 | 80.8 | 85.83 | 8.564 | 14.046 | 26.428 | P-1 |
Cd2(TPDC)2 | Cd(NO3)2·4H2O0.06mmolH2(HPDC)0.06mmol | 甲醇/CHPH2O | 70.59 | 72.75 | 87.14 | 10.102 | 14.412 | 14.964 | P-1 |
Tb(PDC)1.5 | Tb(NO3)2·5H2O0.21mmolH2(HPDC)0.034mm | DMFH2O/乙醇 | 109.8 | 103.61 | 100.14 | 9.829 | 12.11 | 14.628 | P-1 |
ZnDBP | Zn(NO3)2·6H2O0.05mmol磷酸二苄酯0.10mmol | MeOH | 90 | 93.67 | 90 | 9.254 | 10.762 | 27,93 | P2/n |
Zn3(BPDC) | ZnBr20.021mmol4.4’BPDC0.005mmol | DMF | 90 | 102.76 | 90 | 11.49 | 14.79 | 19.18 | P21/n |
CdBDC | Cd(NO3)2·4H2O0.100mmolH2(BDC)0.401mmol | DMFNa2SiO3(aq) | 90 | 95.85 | 90 | 11.2 | 11.11 | 16.71 | P21/n |
Cd-mBDC | Cd(NO3)2·4H2O0.009mmolH2(mBDC)0.018mmol | DMFMeNH2 | 90 | 101.1 | 90 | 13.69 | 18.25 | 14.91 | C2/c |
Zn4OBNDC | Zn(NO3)2·6H2O0.041mmolBNDC | DMFMeNH2H2O2 | 90 | 90 | 90 | 22.35 | 26.05 | 59.56 | Fmmm |
Eu(TCA) | Eu(NO3)3·6H2O0.14mmolTCA0.026mmol | DMF氯苯 | 90 | 90 | 90 | 23.325 | 23.325 | 23.325 | Pm-3n |
Tb(TCA) | Tb(NO3)3·6H2O0.069mmolTCA0.026mmol | DMF氯苯 | 90 | 90 | 90 | 23.272 | 23.272 | 23.372 | Pm-3n |
甲酸盐 | Ce(NO3)3·6H2O0.138mmol甲酸0.43mmol | H2O乙醇 | 90 | 90 | 120 | 10.668 | 10.667 | 4.107 | R-3m |
FeCl2·4H2O5.03mmol甲酸86.90mmol | DMF | 90 | 90 | 120 | 8.2692 | 8.2692 | 63.566 | R-3c | |
FeCl2·4H2O5.03mmol甲酸86.90mmol | DEF | 90 | 90 | 90 | 9.9364 | 18.374 | 18.374 | Pbcn | |
FeCl2·4H2O5.03mmol甲酸86.90mmol | DEF | 90 | 90 | 90 | 8.335 | 8.335 | 13.34 | P-31c | |
NO330 | FeCl2·4H2O0.50mmol甲酸8.69mmol | 甲酰胺 | 90 | 90 | 90 | 8.7749 | 11.655 | 83297 | Pnna |
NO332 | FeCl2·4H2O0.50mmol甲酸8.69mmol | DIP | 90 | 90 | 90 | 10.0313 | 18.808 | 18355 | Pbcn |
NO333 | FeCl2·4H2O0.50mmol甲酸8.69mmol | DBF | 90 | 90 | 90 | 45.2754 | 23.861 | 12.441 | Cmcm |
NO335 | FeCl2·4H2O0.50mmol甲酸8.69mmol | CHF | 90 | 91.372 | 90 | 11.5964 | 10.187 | 14.945 | P21/n |
NO336 | FeCl2·4H2O0.50mmol甲酸8.69mmol | MFA | 90 | 90 | 90 | 11.7945 | 48.843 | 8.4136 | Pbcm |
NO13 | Mn(Ac)2·4H2O0.46mmol苯甲酸0.92mmol联吡啶0.46mmol | 乙醇 | 90 | 90 | 90 | 18.66 | 11.762 | 9.418 | Pbcn |
NO29类MOF-0 | Mn(Ac)2·4H2O0.46mmolH3BTC0.69mmol | DMF | 120 | 90 | 90 | 14.16 | 33.521 | 33.521 | P-1 |
Mn(hfac)2(O2CC6H5) | Mn(Ac)2·4H2O0.46mmolHfac0.92mmol联吡啶0.46mmol | 醚 | 90 | 95.32 | 90 | 9.572 | 17.162 | 14.041 | C2/c |
BPR43G2 | Zn(NO3)2·6H2O0.0288mmolH2BDC0.0072mmol | DMFCH3CN | 90 | 91.37 | 90 | 17.96 | 6.38 | 7.19 | C2/c |
BPR48A2 | Zn(NO3)2·6H2O0.012mmolH2BDC0.012mmol | DMSO甲苯 | 90 | 90 | 90 | 14.5 | 17.04 | 18.02 | Pbca |
BPR49B1 | Zn(NO3)2·6H2O0.024mmolH2BDC0.048mmol | DMSO甲醇 | 90 | 91.172 | 90 | 33.181 | 9.824 | 17.884 | C2/c |
BPR56E1 | Zn(NO3)2·6H2O0.012mmolH2BDC0.024mmol | DMSO正丙醇 | 90 | 90.096 | 90 | 14.5873 | 14.153 | 17.183 | P2(1)/n |
BPR68D10 | Zn(NO3)2·6H2O0.0016mmolH3BTC0.0064mmol | DMSO苯 | 90 | 95.316 | 90 | 10.0627 | 10.17 | 16.413 | P2(1)/c |
BPR69B1 | Cd(NO3)2·4H2O0.0212mmolH2BDC0.0428mmol | DMSO | 90 | 98.76 | 90 | 14.16 | 15.72 | 17.66 | Cc |
BPR73E4 | Cd(NO3)2·4H2O0.006mmolH2BDC0.003mmol | DMSO甲苯 | 90 | 92324 | 90 | 8.7231 | 7.0568 | 18.438 | P2(1)/n |
BPR76D5 | Zn(NO3)2·6H2O0.0009mmolH2BzPDC0.0036mmol | DMSO | 90 | 104.17 | 90 | 14.4191 | 6.2599 | 7.0611 | Pc |
BPR80B5 | Cd(NO3)2·4H2O0.018mmolH2BDC0.036mmol | DMF | 90 | 115.11 | 90 | 28.049 | 9.184 | 17.837 | C2/c |
BPR80H5 | Cd(NO3)2·4H2O0.027mmolH2BDC0.027mmol | DMF | 90 | 119.06 | 90 | 11.4746 | 6.2151 | 17.268 | P2/c |
BPR82C6 | Cd(NO3)2·4H2O0.0068mmolH2BDC0.202mmol | DMF | 90 | 90 | 90 | 9.7721 | 21.142 | 27.77 | Fdd2 |
BPR86C3 | Co(NO3)2·6H2O0.0025mmolH2BDC0.075mmol | DMF | 90 | 90 | 90 | 18.3449 | 10.031 | 17.983 | Pca2(1) |
BPR86H6 | Cd(NO3)2·6H2O0.010mmolH2BDC0.010mmol | DMF | 80.98 | 89.69 | 83.412 | 9.8752 | 10.263 | 15.362 | P-1 |
Co(NO3)2·6H2O | NMP | 106.3 | 107.63 | 107.2 | 7.5308 | 10.942 | 11.025 | P1 | |
BPR95A2 | Zn(NO3)2·6H2O0.012mmolH2BDC0.012mmol | NMP | 90 | 102.9 | 90 | 7.4502 | 13.767 | 12.713 | P2(1)/c |
CuC6F4O4 | Cu(NO3)2·2.5H2O0370mmolH2BDC(OH)20.37mmol | DMF氯苯 | 90 | 98.834 | 90 | 10.9675 | 24.43 | 22.553 | P2(1)/n |
FeFormic | FeCl2·4H2O0370mmol甲酸0.37mmol | DMF | 90 | 91.543 | 90 | 11.495 | 9.963 | 14.48 | P2(1)/n |
MgFormic | Mg(NO3)2·6H2O0.370mmol甲酸0.37mmol | DMF | 90 | 91.359 | 90 | 11383 | 9.932 | 14.656 | P2(1)/n |
MgC6F4O6 | Mg(NO3)2·6H2O0370mmolH2BDC(OH)2037mmol | DMF | 90 | 96.624 | 90 | 17.245 | 9.943 | 9.273 | C2/c |
ZnC2H4BDCMOF-38 | ZnCl20.44mmolCBBDC0.261mmol | DMF | 90 | 94.714 | 90 | 7.3386 | 16.834 | 12.52 | P2(1)/n |
MOF-49 | ZnCl20.44mmolm-BDC0.261mmol | DMFCH3CN | 90 | 93.459 | 90 | 13.509 | 11.984 | 27.039 | P2/c |
MOF-26 | Cu(NO3)2·5H2O0.084mmolDCPE0.085mmol | DMF | 90 | 95.607 | 90 | 20.8797 | 16.017 | 26.176 | P2(1)/n |
MOF-112 | Cu(NO3)2·2.5H2O0.084mmolo-Br-m-BDC0.085mmol | DMF乙醇 | 90 | 107.49 | 90 | 29.3241 | 21.297 | 18.069 | C2/c |
MOF-109 | Cu(NO3)2·2.5H2O0.084mmolKDB0.085mmol | DMF | 90 | 111.98 | 90 | 23.8801 | 16.834 | 18.389 | P2(1)/c |
MOF-111 | Cu(NO3)2·2.5H2O0.084mmolo-BrBDC0.085mmol | DMF乙醇 | 90 | 102.16 | 90 | 10.6767 | 18.781 | 21.052 | C2/c |
MOF-110 | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DMF | 90 | 90 | 120 | 20.0652 | 20.065 | 20.747 | R-3/m |
MOF-107 | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DEF | 104.8 | 97.075 | 95.206 | 11.032 | 18.067 | 18.452 | P-1 |
MOF-108 | Cu(NO3)2·2.5H2O0.084mmol噻吩二羧酸0.085mmol | DBF/甲醇 | 90 | 113.63 | 90 | 15.4747 | 14.514 | 14.032 | C2/c |
MOF-102 | Cu(NO3)2·2.5H2O0.084mmolH2(BDCCl2)0.085mmol | DMF | 91.63 | 106.24 | 112.01 | 9.3845 | 10.794 | 10.831 | P-1 |
Clbdcl | Cu(NO3)2·2.5H2O0.084mmolH2(BDCCl2)0.085mmol | DEF | 90 | 105.56 | 90 | 14.911 | 15.622 | 18.413 | P-1 |
Cu(NMOP) | Cu(NO3)2·2.5H2O0.084mmolNBDC0.085mmol | DMF | 90 | 102.37 | 90 | 14.9238 | 18.727 | 15.529 | P2(1)/m |
Tb(BTC) | Tb(NO3)3·5H2O0.033mmolH3BTC0.033mmol | DMF | 90 | 106.02 | 90 | 18.6986 | 11.368 | 19.721 | |
Zn3(BTC)2Honk | ZnCl20.033mmolH3BTC0.033mmol | DMF乙醇 | 90 | 90 | 90 | 26.572 | 26.572 | 26.572 | Fm-3m |
Zn4O(NDC) | Zn(NO3)2·4H2O0.066mmol14NDC0.066mmol | DMF乙醇 | 90 | 90 | 90 | 41.5594 | 18.818 | 17.574 | aba2 |
CdTDC | Cd(NO3)2·4H2O0.014 mmol噻吩0.040mmolDABCO0.020mmol | DMFH2O | 90 | 90 | 90 | 12.173 | 10.485 | 7.33 | Pmma |
IRMOF-2 | Zn(NO3)2·4H2O0.160mmolo-Br-BDC0.60mmol | DEF | 90 | 90 | 90 | 25.772 | 25.772 | 25.772 | Fm-3m |
IRMOF-3 | Zn(NO3)2·4H2O0.20mmoIH2N-BDC0.60mmol | DEF乙醇 | 90 | 90 | 90 | 25.747 | 25.747 | 25.747 | Fm-3m |
IRMOF-4 | Zn(NO3)2·4H2O0.11mmol[C3H7O]2-BDC0.48mmol | DEF | 90 | 90 | 90 | 25.849 | 25.849 | 25.849 | Fm-3m |
IRMOF-5 | Zn(NO3)2·4H2O0.13mmol[C5H11O]2-BDC0.50mmol | DEF | 90 | 90 | 90 | 12.882 | 12.882 | 12.882 | Pm-3m |
IRMOF-6 | Zn(NO3)2·4H2O0.20mmol[C2H4]-BDC0.60mmol | DEF | 90 | 90 | 90 | 25.842 | 25.842 | 25.842 | Fm-3m |
IRMOF-7 | Zn(NO3)2·4H2O0.07mmol1,4NDC0.20mmol | DEF | 90 | 90 | 90 | 12.914 | 12.914 | 12.914 | Pm-3m |
IRMOF-8 | Zn(NO3)2·4H2O0.55mmol2,6NDC0.42mmol | DEF | 90 | 90 | 90 | 30.092 | 30.092 | 30.092 | Fm-3m |
IRMOF-9 | Zn(NO3)2·4HX2O0.05mmolBPDC0.42mmol | DEF | 90 | 90 | 90 | 17.147 | 23.322 | 25.255 | Pnnm |
IRMOF-10 | Zn(NO3)2·4H2O0.02mmolBPDC0.012 mmol | DEF | 90 | 90 | 90 | 34.281 | 34.281 | 34.281 | Fm-3m |
IRMOF-11 | Zn(NO3)2·4H2O0.05mmolHPDC0.20mmol | DEF | 90 | 90 | 90 | 24.822 | 24.822 | 56.734 | R-3m |
IRMOF-12 | Zn(NO3)2·4H2O0.017mmolHPDC0.12mmol | DEF | 90 | 90 | 90 | 34.281 | 34.281 | 34.281 | Fm-3m |
IRMOF-13 | Zn(NO3)2·4H2O0.048mmolPDC0.31mmol | DEF | 90 | 90 | 90 | 24.822 | 24.822 | 56.734 | R-3m |
IRMOF-14 | Zn(NO3)2·4H2O0.17mmolPDC0.12mmol | DEF | 90 | 90 | 90 | 34.381 | 34.381 | 34.381 | Fm-3m |
IRMOF-15 | Zn(NO3)2·4H2O0.063mmolTPDC0.025mmol | DEF | 90 | 90 | 90 | 21.459 | 21.459 | 21.459 | Im-3m |
IRMOF-16 | Zn(NO3)2·4H2O0.0126mmolTPDC0.05mmol | DEFNMP | 90 | 90 | 90 | 21.49 | 21.49 | 21.49 | Pm-3m |
ADC 乙炔二羧酸
NDC 萘二羧酸
BDC 苯二羧酸
ATC 金刚烷四羧酸
BTC 苯三羧酸
BTB 苯三苯甲酸酯/盐
MTB 甲烷四苯甲酸酯/盐
ATB 金刚烷四苯甲酸酯/盐
ADB 金刚烷二苯甲酸酯/盐
文献中已知的其它MOFs是MOF-177和MOF-178。
粉末形式的这些材料的合成例子可以例如在:US 5,648,508、J.Am.Chem.Soc.123(2001)第8241页以下或在Acc.Chem.Res.31(1998)第474页以下找到,它们各自的相关内容完全经此引用并入本申请。
骨架材料,特别是MOF-5,与结晶母液的分离可以通过本领域已知的程序实现,例如固液分离、离心、萃取、过滤、膜过滤、交叉流动过滤、使用絮凝助剂(非离子、阳离子和阴离子助剂)的絮凝,或添加pH改变添加剂,例如盐、酸或碱,通过浮选、以及通过母液在升高的温度和/或在真空中的蒸发,和固体的浓缩。
除了MOFs的传统制备方法外,在DE 10355087以及WO-A2005/049892中公开了新的电化学方法。新型MOFs在液化气储存方面表现出优异的性能。因此,优选使用根据本发明的这些MOFs。
本发明的范围内所用的术语“电化学制备”涉及在电荷迁移或电势出现时伴随至少一种反应产物的形成的制备方法。
本发明的范围内所用的和进行MOFs的电化学形成的术语“至少一种金属离子”涉及如下实施方案——根据该实施方案,通过阳极氧化提供金属的至少一种离子、或第一金属的至少一种离子、和至少一种与所述第一金属不同的第二金属的至少一种离子。
相应地,本发明包括如下实施方案——其中经由阳极氧化提供至少一种金属的至少一种离子,并经由金属盐提供至少一种金属的至少一种离子,其中所述金属盐中的至少一种金属和经由阳极氧化作为金属离子提供的至少一种金属可以彼此相同或不同。本发明因此包括,例如,如下实施方案——根据该实施方案,反应介质包含金属的一种或多种不同的盐,并另外经由含有所述金属的至少一个阳极的阳极氧化提供该盐或这些盐中存在的金属离子。同样地,本发明包括如下实施方案——根据该实施方案,反应介质包含至少一种金属的一种或多种不同的盐,并经由阳极氧化提供与这些金属不同的至少一种金属作为反应介质中的金属离子。
根据本发明的优选的并与MOFs的电化学制备有关的实施方案,经由含有至少一种金属的至少一个阳极的阳极氧化提供所述至少一种金属离子,不再经由金属盐提供其它金属。
本发明的范围内所用的、与MOFs的电化学制备有关的术语“金属”包括元素周期表的所有下述元素:可以经由电化学途径经由阳极氧化在反应介质中提供,并能够与至少一种至少双配位的有机化合物形成至少一种金属-有机多孔骨架材料。
如上所述,不论通过传统方法还是电化学方法生成,根据本发明,MOFs以成型体形式使用都是优选的。
模制粉末的适当方法是本领域技术人员已知的,在最广义意义上是指可以将任何粉末、粉状物质、微晶阵列等等成型为在其预期使用条件下稳定的成型体的方法。
除了任选的将含MOF的粉末模制为成型体的步骤外,根据本发明还可以存在下列步骤:
(I)在模制步骤之前的混合步骤,
(II)在模制步骤之前的例如通过添加溶剂、粘合剂或其它附加物质制备含有含MOF的粉末的糊状物或流体的步骤,
(III)在模制步骤之后的修整步骤,特别是干燥步骤。
模制、成型或成形等的转化步骤可以通过技术人员已知的用于实现粉末、悬浮液或糊状物的附聚的任何方法实现。例如,在Ulllmann’sEnzylopadie der Technischen Chemie,第四版,第2卷,第313页及以下,1972中描述了这类方法,它们各自的内容经此引用并入本申请。
一般而言,可以区分下列主要途径:(i)压块,即粉状材料的机械压制,使用或不用粘合剂和/或其它添加剂,(ii)粒化(造粒),即通过使其经受旋转运动,将润湿的粉状材料压实,和(iii)烧结,即对要压实的材料进行热处理。对于本发明的材料,后者略微受到限制,因为有机材料具有有限的温度稳定性(见下文)。
具体而言,本发明的模制步骤优选使用至少一种选自下列类型的方法进行:通过活塞压机压块、通过辊压压块、无粘合剂的压块、带有粘合剂的压块、造粒、配混、熔融、挤出、共挤、旋转、沉积、发泡、喷雾干燥、涂布、粒化,特别是喷雾粒化或根据塑料加工中已知的任何方法粒化,或至少两种上述方法的任何组合。
模制可以通过挤出在传统挤出机中进行,从而产生直径通常大约1至大约10毫米、特别是大约1.5至大约5毫米的挤出物。例如在Ullmann’sEnzylopadieder Technischen Chemie,第四版,笫2卷,笫295页及以下,1972中描述了这类挤出装置。除了使用挤出机外,优选还使用挤压机进行模制。
优选模制方法在升高的压力下进行,即通过含MOF的粉末的加压进行。压力可以从大气压到数百巴。升高的温度(室温至300℃)或在保护气氛(稀有气体、氮气或其混合物)中也是合适的。这些条件的任何组合也是可行的。
可以实施压制的条件取决于,例如压机、填充高度、冲压能力、和成型体的形状。
模制步骤可以在粘合剂和/或使待附聚的材料稳定化的其它附加物质存在下进行。至于所述至少一种任选的粘合剂,可以使用本领域技术人员已知的用于促进待模制的粒子粘结在一起的任何材料。可以在金属-有机骨架材料中添加用于将该材料转化成糊状物的粘合剂、有机增粘化合物和/或液体,然后将混合物在混合或捏和装置或挤出机中压实。然后模制所得塑料,特别是使用挤压机或挤出机,然后对所得模制品进行任选的修整步骤(III),例如干燥。
可以使用许多无机化合物作为粘合剂。非限制性例子包括二氧化钛、水合二氧化钛、水合氧化铝或其它含铝粘合剂、硅和铝化合物的混合物、硅化合物、粘土、烷氧基硅烷和两亲物质。
其它可用的粘合剂原则上是迄今用于实现粉状材料中的粘结的所有化合物。优选使用化合物,特别是硅、铝、硼、磷、锆和/或钛的氧化物。特别可用作粘合剂的是二氧化硅,其中将SiO2以硅溶胶或四烷氧基硅烷的形式引入成型步骤。还可以使用镁和铍的混合物和粘土,例如蒙脱石、高岭土、膨润土、埃洛石、迪开石、珍珠陶土和富硅高岭石作为粘合剂。在本发明中特别使用四烷氧基硅烷作为粘合剂。具体例子是四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷和四丁氧基硅烷、类似的四烷氧基钛和四烷氧基锆化合物和三甲氧基铝、三乙氧基铝、三丙氧基铝和三丁氧基铝,其中四甲氧基硅烷和四乙氧基硅烷特别优选。
粘合剂可以具有0.1至20重量%的浓度。或者,不使用任何粘合剂。
可以存在一种或多种脱模剂作为添加剂。合适的试剂是石墨或MOF材料,其中MOF具有层组成。
此外,可以使用有机增粘物质和/或亲水聚合物,例如纤维素或聚丙烯酸酯/盐。所用有机增粘物质同样可以是适用于此用途的任何物质。优选的是有机的,特别是亲水的聚合物,例如纤维素、淀粉、聚丙烯酸酯/盐、聚甲基丙烯酸酯/盐、聚乙烯醇、聚乙烯基吡咯烷酮、聚异丁烯和聚四氢呋喃。这些物质主要在捏和、模制和干燥步骤中通过连接初级粒子、并确保模制和任选干燥过程中的机械稳定性来促进塑料的形成。
对于任选的混合步骤(I)或对于模制步骤,对可用于制造糊状物的任选液体完全没有限制。除了水外,还可以使用醇,只要它们是水混溶性的即可。因此,可以使用1至4个碳原子的单醇和水混溶性多元醇。特别地,使用甲醇、乙醇、丙醇、正丁醇、异丁醇、叔丁醇和它们中两种或多种的混合物。
可以使用胺或胺类化合物,例如四烷基铵化合物或氨基醇,和含碳酸根的物质,例如碳酸钙,作为其它添加剂。在EP-A 0389041、EP-A 0200260和WO95/19222中描述了这类其它添加剂,它们完全经此引用并入本申请文本。
上述多数(即使不是全部)添加剂物质可以通过干燥或加热,任选在保护气氛或在真空下,从成型体中去除。为了使金属-有机骨架保持完整,成型体优选不暴露在超过300℃的温度下。但是,研究表明,在上述温和条件下的加热/干燥,特别是在真空下,优选远低于300℃下的干燥足以至少将有机化合物从金属-有机骨架的孔隙中去除出来。通常,根据所用添加剂物质调整和选择条件。
组分(任选的溶剂、粘合剂、添加剂、金属-有机骨架材料)的添加顺序不是关键的。可以首先添加粘合剂,然后例如添加金属-有机骨架材料,和如果需要,添加剂,最后添加含有至少一种醇和/或水的混合物,或交换前述任何组分的顺序。
至于例如含有金属-有机骨架的粉末和粘合剂和任选的其它加工材料(=附加材料)的任选的混合步骤(I),可以使用材料加工和装置操作领域的技术人员已知的任何方法。如果在液相中进行混合,搅拌是优选的,如果要混合的物料是糊状的,捏和和/或挤出是优选的,如果要混合的组分都是固体的粉状形态,混合是优选的。如果待使用的组分的状态允许,也可以使用雾化器、喷雾器、扩散器或喷洒器。对于糊状(源自含MOF的粉末)和粉状材料,优选使用静态混合器、行星式混合器、具有旋转容器的混合器、盘式混合器、捏和碾磨机、剪切盘混合机、离心混合机、砂磨机、槽式捏和机、密闭式混合机和连续捏和机。明确地指出,混合方法可能足以实现模制,即混合和模制步骤重合。
实施例
实施例1
图2显示了在有和没有MOF的情况下,在瓶(体积0.5升)中在室温下的丙烷摄取曲线。该实施例中所用的MOF是Zn-MOF-5。在US2003/-148165 A1中描述了该MOF的制备。
在表1中显示了在某些摄取值下在有/没有MOF的情况下的压力比率。
表1
摄取丙烷(没有MOF,克/升容器) | 6.32 | 10.16 | 30.5 |
没有MOF的容器压力(=P空),巴 | 3.244 | 5.036 | 9.808 |
有MOF的情况下相同摄取量必需的容器压力(=PMoF),巴 | 0.107 | 0.161 | 0.324 |
PMOF/P空 | 0.03 | 0.03 | 0.03 |
实施例2
图3显示了在有和没有MOF的情况下,在瓶(体积0.477升)中在室温下的丙烷摄取曲线。该实施例中所用的MOF是IRMOF-8。在WO-A02/088148中描述了该MOF的制备。
在表2中显示了在某些摄取值下在有/没有MOF的情况下的压力比率。
表2
摄取丙烷(没有MOF,克/升容器) | 3.5 | 9.77 | 16.29 | 20.57 |
没有MOF的容器压力(=P空),巴 | 2.023 | 5.121 | 8.012 | 9.681 |
有MOF的情况下相同摄取量必需的容器压力(=PMOF),巴 | 0.090 | 0.203 | O.315 | 0.408 |
PMOF/P空 | 0.04 | 0.04 | 0.04 | 0.04 |
Claims (10)
1.在容器中储存液化气的方法,该容器具有使液化气进入或离开容器的入口和,任选地,独立的出口,和能够以预定量且在预定压力下将处于气态的液化气保持在容器内的气密保持机制,并含有金属-有机骨架材料(MOF),所述金属-有机骨架材料包含至少一种金属离子和至少一种与所述金属离子配位结合的至少双配位的有机化合物,其中容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2。
2.权利要求1的方法,其中所述液化气选自由卤化的C1-C10烃、丙烷、丁烷、异丁烷和它们的混合物组成的组。
3.权利要求2的方法,其中所述液化气是丙烷。
4.权利要求1的方法,其中所述容器是非圆柱形的。
5.权利要求1的方法,其中压力大于0.1巴且小于20巴。
6.权利要求1的方法,其中液化气的量为至少2克/升。
7.权利要求1的方法,其中所述比率最多为0.1。
8.装有预定量的和在预定压力下的液化气的容器,该容器具有使液化气进入或离开容器的入口和,任选地,独立的出口,和能够以预定量且在预定压力下将处于气态的液化气保持在容器内的气密保持机制,并含有金属-有机骨架材料(MOF),所述金属-有机骨架材料包含至少一种金属离子和至少一种与所述金属离子配位结合的至少双配位的有机化合物,其中容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2。
9.用液化气填充容器直至预定量和预定压力的方法,该容器具有使液化气进入或离开容器的入口和,任选地,独立的出口,和能够将处于气态的液化气保持在容器内的气密保持机制,并含有金属-有机骨架材料(MOF),所述金属-有机骨架材料包含至少一种金属离子和至少一种与所述金属离子配位结合的至少双配位的有机化合物,该方法使得容器内的压力与在不含MOF的容器内在相同温度储存相同量的液化气所需压力的比率为最多0.2,包括下列步骤:
-使容器入口与液化气瓶接触,其中该气体处于其液态或压缩态,使得进给容器内的压力超过待填充的容器内的压力。
10.根据权利要求8的容器的用途,用于液化气的受控释放。
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- 2006-02-22 CN CNA2006800089790A patent/CN101147027A/zh active Pending
- 2006-02-22 EP EP14161810.8A patent/EP2749808A1/en not_active Withdrawn
- 2006-02-22 WO PCT/EP2006/060181 patent/WO2006089908A1/en active Application Filing
- 2006-02-22 ES ES06708449.1T patent/ES2478009T3/es active Active
- 2006-02-22 EP EP06708449.1A patent/EP1856440B1/en not_active Not-in-force
- 2006-02-22 CN CN2013100862564A patent/CN103216726A/zh active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103635255A (zh) * | 2011-04-21 | 2014-03-12 | 巴斯夫欧洲公司 | 含有多孔芳族骨架(paf)材料的成型体 |
CN107754775A (zh) * | 2016-08-19 | 2018-03-06 | 福特全球技术公司 | 金属有机骨架材料的溶剂支撑型压实 |
CN107754775B (zh) * | 2016-08-19 | 2022-08-09 | 福特全球技术公司 | 金属有机骨架材料的溶剂支撑型压实 |
CN111094228A (zh) * | 2017-08-22 | 2020-05-01 | 积水化学工业株式会社 | 组合物、成形体的制造方法以及成形体 |
CN111094228B (zh) * | 2017-08-22 | 2024-02-09 | 积水化学工业株式会社 | 组合物、成形体的制造方法以及成形体 |
Also Published As
Publication number | Publication date |
---|---|
CN103216726A (zh) | 2013-07-24 |
EP1856440A1 (en) | 2007-11-21 |
JP2008531939A (ja) | 2008-08-14 |
US7343747B2 (en) | 2008-03-18 |
EP2749808A1 (en) | 2014-07-02 |
EP1856440B1 (en) | 2014-05-07 |
ES2478009T3 (es) | 2014-07-18 |
US20060185388A1 (en) | 2006-08-24 |
WO2006089908A1 (en) | 2006-08-31 |
JP4944801B2 (ja) | 2012-06-06 |
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