CN112272587A - 结晶金属磷酸盐、其制备方法和用途 - Google Patents
结晶金属磷酸盐、其制备方法和用途 Download PDFInfo
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- CN112272587A CN112272587A CN201980038317.5A CN201980038317A CN112272587A CN 112272587 A CN112272587 A CN 112272587A CN 201980038317 A CN201980038317 A CN 201980038317A CN 112272587 A CN112272587 A CN 112272587A
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
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Abstract
本发明合成了命名为AlPO‑91的一种新的结晶微孔金属磷酸盐家族。这些金属磷酸盐由以下经验式表示:Cc +Aa +Mm 2+EPxSiyOz;其中M为二价骨架金属诸如镁或锌,C为环状有机铵阳离子,A为无环有机铵阳离子,并且E为三价骨架元素诸如铝或镓。AlPO‑91组合物的特征在于新的独特ABC‑6网结构,并且具有适用于执行各种烃转化过程的催化特性,以及适用于在多种应用诸如吸附热泵中有效吸附水蒸气的特性。
Description
背景技术
本发明涉及一种新型金属磷酸盐家族,统称为AlPO-91。它们由以下经验式表示:
Cc +Aa +Mm 2+EPxSiyOz
其中M为二价骨架金属诸如镁或锌,C为环状有机铵阳离子,A为无环有机铵阳离子,并且E为三价骨架元素诸如铝或镓。
分子筛的类别包括结晶磷酸铝、磷酸硅铝或金属磷酸铝组合物,它们是微孔的并且由共角的AlO4/2和PO4/2四面体形成。1982年,Wilson等人首次报道了磷酸铝分子筛,即所谓的AlPO,它是具有许多与沸石相同的特性的微孔材料,但不含二氧化硅(参见美国专利号4,310,440)。随后,经由用SiO4/2四面体替代PO4/2 +四面体以将电荷引入中性磷酸铝骨架,从而产生SAPO分子筛,如Lok等人所述(参见美国专利号4,440,871)。将骨架电荷引入中性磷酸铝的另一种方式是用[Me2+O4/2]2-四面体替代AlO4/2 -四面体,以产生MeAPO分子筛(参见美国专利号4,567,029)。此外,还可以经由同时向骨架中引入SiO4/2和[M2+O4/2]2-四面体来在基于AlPO的分子筛上引入骨架电荷,得到MeAPSO分子筛(参见美国专利号4,973,785)。
在各种工业方法中使用了多种天然存在和合成制备的分子筛。通过合成,这些分子筛经由水热合成制备,所述水热合成采用合适的Si、Al、P、金属源和结构导向剂诸如胺或有机铵阳离子。结构导向剂停留在分子筛的孔中,并且主要负责最终形成的特定结构。这些物质可以平衡与磷酸铝组合物中的硅或其他金属诸如Zn或Mg相关的骨架电荷,并且还可用作空间填料以稳定四面体骨架。分子筛的特征在于具有均匀尺寸的孔开口,具有显著的离子交换容量,并且能够可逆地解吸分散在晶体的整个内部空隙中的吸附相,但不显著地置换构成永久性分子筛晶体结构的任何原子。分子筛可用于分离应用,其中某些种类的混合液体或蒸气流被捕集在分子筛的孔内,并且排除其他种类的混合液体或蒸气流。分子筛还可用作烃转化反应的催化剂,所述烃转化反应可在外部表面上以及孔内的内部表面上发生。
如上所述,分子筛能够可逆地吸附和解吸某些分子,具体取决于被吸附物的尺寸和分子筛的内部孔结构。存在许多期望优选地以可逆方式吸附水蒸气的应用。一种此类应用是吸附热泵,它是可用于从余热或废热中回收能量的装置。因此,吸附热泵可用于以环境友好的方式最大化能量效率。分子筛由于它的高水蒸气容量而可成为用作吸附热泵中的水蒸气吸附剂的可用材料。对于吸附热泵中吸附剂的使用的描述可见于美国专利8,323,747,该专利全文以引用方式并入本文。
吸附热泵中使用的分子筛类型必须满足某些对于最佳性能的要求。高的总体水蒸气容量很重要,但最关键的是,所述分子筛类型应在不高于100℃下完全解吸所有吸附的水。否则,必须施加过多的热量以从微孔中完全去除所吸附的水(即,再生温度过高),因此需要过高的能量输入。大多数铝硅酸盐(即,沸石)在非常低的压力(P/P0)下具有水蒸气的快速吸收,这相反地导致不可接受的高再生温度,但总体水蒸气容量高。磷酸铝和磷酸硅铝已被证明对水蒸气具有更有利的吸附特性(参见例如M.F.de Lange等人,《化学评论》,第115卷,第12205页,2015年(M.F.de Lange et al.Chem.Rev.115,12205(2015));H.vanHeyden等人,《应用热力工程》,第29卷,第1514页,2009年(H.van Heyden etal.Appl.Therm.Eng.29,1514(2009)))。具体地,材料SAPO-34和SAPO-5(分别为类沸石CHA和AFI)已被证明特别可用作吸附热泵中的吸附材料(参见US7422993、US9517942)。
分子筛还适用于分离混合液体或蒸气流内的物质。具体地,烯烃/石蜡分离是工业中的一些最重要但能量最密集的分离。烯烃和石蜡的尺寸通常非常相似,使得难以通过分子筛分效应进行分离。用于烯烃/石蜡分离的许多吸附剂用金属(通常为银)处理,以引起烯烃的优先吸收。已报道经银交换的沸石诸如LTA和FAU优先于石蜡吸收烯烃(参见例如Aguado等人,《美国化学学会刊》,第134卷,第14635页,2012年(Aguado etal.J.Am.Chem.Soc.134,14635(2012)))。然而,在这些吸附剂中银的必要性极大地增加了它们的制造成本。为了使用分子筛令人满意地从石蜡中分离烯烃,必须非常精细地定制孔的尺寸。
发明内容
如上所述,本发明涉及一种新的金属磷酸盐分子筛家族,统称为AlPO-91。因此,本发明的一个实施方案为微孔结晶材料,该微孔结晶材料具有至少EO4/2 -和PO4/2 +四面体单元以及任选地[M2+O4/2]2-和SiO4/2四面体单元中的至少一者的三维骨架以及由以下经验式表示的原位合成态形式的并基于无水的经验组成:
Cc +Aa +Mm 2+EPxSiyOz
其中M为至少一种化合价为+2的金属阳离子,该金属阳离子选自由Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+组成的组,“m”为M与E的摩尔比并且从0至1.0变化,C为环状有机铵阳离子,并且A为无环有机铵阳离子。比率c/a可具有0至1000的值,并且总和(c+a)表示(C+A)与E的摩尔比并且具有0.1至2.0的值。E为选自由铝、镓、铁、硼以及它们的混合物的三价元素,“x”为P与E的摩尔比并且从0.5至2.0变化,“y”为Si与E的摩尔比并且从0至1.0变化,并且“z”为O与E的摩尔比并且具有由以下公式确定的值:
z=(2·m+c+a+3+5·x+4·y)/2
本发明的特征在于其具有x-射线衍射图,该x-射线衍射图至少具有表1中所示的d-间距和强度:
表1
本发明的另一个实施方案为微孔结晶材料,该微孔结晶材料具有至少EO4/2 -和PO4/2 +四面体单元以及任选地[M2+O4/2]2-和SiO4/2-四面体单元中的至少一者的三维骨架以及由以下经验式表示的煅烧形式的并基于无水的经验组成:
HwMm 2+EPxSiyOz
其中“m”、“x”、“y”如上所述,H为质子,w”为H与E的摩尔比并且从0至2.5变化,并且“z”为O与E的摩尔比并且具有由以下公式确定的值:
z=(w+2·m+3+5·x+4·y)/2
并且本发明的特征在于其具有x-射线衍射图,该x-射线衍射图至少具有表2中所示的d-间距和强度:
表2
本发明的另一个实施方案是制备上述结晶微孔金属磷酸盐分子筛的方法。该方法包括形成包含M和Si之一或两者、C、A、E和P的反应性源的反应混合物,并且将该反应混合物在60℃至200℃的温度下加热足以形成分子筛的时间,该反应混合物具有根据下列氧化物摩尔比表示的组成:
aA2O:bC2O:cMO:E2O3:dP2O5:eSiO2:fH2O
其中“a”具有0.01至5的值,“b”具有0.01至5的值,“c”具有0至2的值,“d”具有0.5至8的值,“e”具有0至4的值,并且“f”具有30至1000的值。
本发明的另一个实施方案是使用上述分子筛作为催化剂的烃转化过程。该方法包括在转化条件下使至少一种烃与分子筛接触以生成至少一种转化的烃。
本发明的又一个实施方案是使用结晶AlPO-91材料的吸附方法。该方法可涉及吸附热泵型设备中的AlPO-91上方的水蒸气的吸附和解吸。另选地,该方法可涉及从石蜡中分离烯烃。分子物质的分离可基于分子尺寸(动力学直径)或分子物质的极性程度。可通过与分子筛进行离子交换来去除污染物。
附图说明
图1为根据本文所述的实施方案的示例性AlPO-91材料的透射电子显微镜(TEM)图像。
图2为原位合成态形式的示例性AlPO-91材料的x-射线衍射图。
图3为煅烧形式的示例性AlPO-91材料的x-射线衍射图。
具体实施方式
申请人已制备出拓扑结构独特的金属磷酸盐材料家族。在他们的论文“4-连接的三维网的计数和骨架硅酸盐的分类:ABC-6网的无限集;阿基米德和σ相关的网(Enumeration of 4-connected 3-dimensional nets and classification offramework silicates:the infinite set of ABC-6 nets;the Archimedean and σ-related nets)”中,Smith和Bennett称“大致上,属于ABC-6网家族的所有硅酸盐均具有x-射线衍射图,该x-射线衍射图可在晶格参数为和的六方棱柱晶胞上索引”。(参见《美国矿物学家》,第66卷,第777-788页,1981年(American Mineralogist,66,777-788(1981)))。该发现结果随后被其他人确认(参见例如D.Xie等人,《美国化学学会刊》,第135卷,第10519页,2013年(D.Xie etal.J.Am.Chem.Soc.135,10519(2013))),因为ABC-6家族已扩增。
AlPO-91的一种特定组成在具有晶格参数为和的六方晶型轴的晶胞上索引,这表明ABC-6网结构具有沿着c-轴每16层重复的堆叠序列(p=40.341/2.5=16.14)。这是具有16层重复的ABC-6网结构的第一已知示例;因此,AlPO-91材料家族的拓扑结构是独特的。本发明的微孔结晶材料(AlPO-91)具有由以下经验式表示的原位合成态形式的并基于无水的经验组成:
Cc +Aa +Mm 2+EPxSiyOz
其中M为至少一种骨架二价阳离子并且选自由碱土金属和过渡金属组成的组。M阳离子的具体示例包括但不限于铍、镁、钴(II)、锰、锌、铁(II)、镍以及它们的混合物。C为环状有机铵阳离子,并且A为无环有机铵阳离子。比率c/a可具有0至1000的值,并且总和(c+a)表示(C+A)与E的摩尔比并且具有0.1至2.0的值。“m”的值为M与E的摩尔比并且从0至1.0变化,“x”为P与E的摩尔比并且从0.5至2.0变化。硅与E的比率由从0至1.0变化的“y”表示。E为四面体配位的三价元素,存在于骨架中,并且选自由铝、镓、铁(III)和硼组成的组。最后,“z”为O与E的摩尔比,并且由以下公式给出:
z=(2·m+c+a+3+5·x+4·y)/2。
分子筛材料的合成通常依赖于被称为有机结构导向剂(OSDA)的有机氨基或有机铵模板的使用。虽然简单的OSDA诸如四甲基铵、四乙基铵和四丙基铵是可商购获得的,但通常OSDA是难以合成且合成昂贵的复杂分子。然而,它们的重要性在于它们将其结构特征的各方面赋予分子筛以产生所需孔结构的能力。例如,使用1,4,7,10,13,16-六甲基-1,4,7,10,13,16-六氮杂环十八烷作为OSDA已被证明允许合成STA-7,即SAV类沸石的磷酸铝基材料(Wright等人,《化学学会会刊》,《道尔顿汇刊》,2000年,第1243-1248页(Wrightet.al.J.Chem.Soc.,Dalton Trans.,2000,1243-1248));使用4,7,13,16,21,24-六氧杂-1,10-二氮杂双环[8.8.8]二十六烷(“Kryptofix 222”)导致合成AlPO4-42(Schreyeck等人,《微孔介孔材料》,1998年,第22卷,第87-106页(Schreyecket.al.Micro.Meso.Mater.1998,22,87-106));MAPO-35(具有LEV拓扑结构的磷酸铝镁材料)公开于美国专利号4,567,029中,其中奎宁环用作结构导向剂;并且在美国专利号4,973,785中,公开了MeAPSO组合物CoAPSO-35,该组合物除了Al和P之外还在骨架中包含钴和硅,并且使用甲基奎宁环作为结构导向剂。
本领域清楚地表明,使用复杂的有机铵SDA通常会得到新的分子筛材料。然而,这些复杂的有机铵化合物的合成相当耗时并且需要许多步骤,通常在有机溶剂中进行,从而阻碍新的分子筛材料的开发。通常,即使对于简单的可商购获得的OSDA,OSDA也是用于合成分子筛材料的最昂贵成分。因此,由可商购获得的有机铵SDA或可易于由可商购获得的原料合成的SDA合成新的分子筛将是经济有利的。最近,使用简单的水性化学物质生成衍生自吗啉基化合物的新型有机-1-氧杂-4-氮鎓环己烷化合物家族(US9522896),以简洁的方式证实了这一点。US9522896中所述的程序也可扩展到哌啶基化合物家族。因此,该程序允许以容易且实用的方式由容易获得的起始试剂制备SDA,诸如不常见的季铵盐。由本发明的方法制备的OSDA呈水溶液形式并且不造成气味和闪点担忧。结果得到消除原位沸石反应混合物的制备中通常所需的冷却步骤和避免纯化步骤诸如非原位制备方法中通常所需的有机溶剂蒸发的空前能力。所获得的有机溴化铵盐可通过与Ag2O反应或通过阴离子交换树脂进行离子交换以产生氢氧根形式的有机铵化合物,或直接用作卤素盐。最后,所得的有机铵化合物可用于合成沸石或分子筛。
微孔结晶金属磷酸盐AlPO-91通过反应混合物的水热结晶制备,所述反应混合物通过将M和硅中的一者或两者、C、A、E和磷的反应性源混合而制备。AlPO-91材料的优选形式为E为Al。铝源包括但不限于铝醇盐、沉淀氧化铝、铝金属、氢氧化铝、铝盐和氧化铝溶胶。铝醇盐的具体示例包括但不限于邻仲丁醇铝和邻异丙醇铝。磷源包括但不限于正磷酸、五氧化二磷和磷酸二氢铵。二氧化硅源包括但不限于原硅酸四乙酯、胶态二氧化硅和沉淀二氧化硅。其他E元素源包括但不限于有机硼酸铵、硼酸、沉淀羟基氧化镓、硫酸镓、硫酸铁和氯化铁。M金属源包括相应碱土金属和过渡金属的卤化物盐、硝酸盐、乙酸盐和硫酸盐。
C的一种组分可以是由环状仲胺和有机二卤化物的水性混合物的反应制备的有机铵阳离子。环状仲胺的具体示例包括但不限于哌啶、高哌啶、吡咯烷和吗啉。有机二卤化物的具体示例包括但不限于1,4-二溴丁烷、1,5-二溴戊烷和1,6-二溴己烷。
在一个实施方案中,环状仲胺为哌啶,并且有机二卤化物为1,4-二溴丁烷。在另一个实施方案中,环状仲胺为哌啶,并且有机二卤化物为1,4-二溴戊烷。在另一个实施方案中,环状仲胺为哌啶,并且有机二卤化物为1,5-二溴戊烷。在另一个实施方案中,环状仲胺为吡咯烷,并且有机二卤化物为1,4-二溴丁烷。
A的一种组分可为四烷基铵阳离子,表示为NR4 +。R基团被选择为使得阳离子A为无环的,并且在同一四价氮上可存在多个不同的R基团。特定的R基团可具有式CnH2n+1,其中n为在1至4范围内的整数(包括端值在内)。组分A的非限制性示例包括四甲基铵、乙基三甲基铵、二乙基二甲基铵、甲基三乙基铵、四乙基铵、四丙基铵、丙基三甲基铵、丁基三甲基铵、二丙基二甲基铵和甲基乙基二丙基铵。
包含所需组分的反应性源的反应混合物可通过下式根据下列氧化物摩尔比来描述:
aA2O:bC2O:cMO:E2O3:dP2O5:eSiO2:fH2O
其中“a”具有0.01至5的值,“b”具有0.01至5的值,“c”具有0至2的值,“d”具有0.5至8的值,“e”具有0至4的值,并且“f”具有30至1000的值。如果使用醇盐,则优选包括蒸馏或蒸发步骤以去除醇水解产物。
在自生压力下,使反应混合物在60℃至200℃并且优选125℃至175℃的温度下,在密封反应容器中反应1天至21天的时段并且优选2天至10天的时间。可在搅拌下加热反应容器,在转动状态下加热反应容器,或静音地加热反应容器。在结晶完成后,将固体产物借助于诸如过滤或离心与异质混合物分离,并且然后利用去离子水洗涤并在高达100℃的环境温度处在空气中干燥。可任选地将AlPO-91晶种添加到反应混合物中,以便加速所需微孔组合物的形成。
由上述方法获得的AlPO-91磷酸铝基材料通过至少具有表1中所示的d-间距和相对强度的以下x-射线衍射图表征:
表1
AlPO-91材料可在空气或氮气中煅烧以去除封闭的模板。在本发明的一个实施方案中,AlPO-91在至少550℃的温度下煅烧。在本发明的另一个实施方案中,AlPO-91在至少600℃的温度下煅烧。AlPO-91在煅烧时是热稳定的,并且可通过至少具有下表2中所示的d-间距和相对强度的x-射线衍射图表征:
表2
稳定的经煅烧的AlPO-91材料可基于无水由经验式表征:
HwMm 2+EPxSiyOz
其中M为至少一种化合价为+2的金属阳离子,该金属阳离子选自由Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+组成的组,“m”为M与E的摩尔比并且从0至1.0变化,H为质子,w”为H与E的摩尔比并且从0至2.5变化,E为选自由铝、镓、铁、硼以及它们的混合物组成的组的三价元素,“x”为P与E的摩尔比并且从0.5至2.0变化,“y”为Si与E的摩尔比并且从0至1.0变化,并且“z”为O与E的摩尔比并且具有由以下公式确定的值:
z=(w+2·m+3+5·x+4·y)/2
本发明的结晶AlPO-91材料可用于分离分子物质的混合物,通过离子交换去除污染物和催化各种烃转化过程。分子物质的分离可基于分子尺寸(动力学直径)或分子物质的极性程度。
本发明的AlPO-91组合物还可在各种烃转化过程中用作催化剂或催化剂载体。烃转化过程是本领域熟知的,并且包括裂化、加氢裂化、芳族化合物和异链烷烃两者的烷基化、异构化、聚合、重整、氢化、脱氢、烷基转移、脱烷基化、水合、脱水、加氢处理、加氢脱氮、加氢脱硫、甲醇制烯烃、甲烷化和合成气转变过程。可用于这些方法中的具体反应条件和进料类型在US 4,310,440、US 4,440,871和US 5,126,308中列出,这些专利以引用方式并入。
AlPO-91材料还可用作将甲醇转化成烯烃的催化剂。甲醇可为液相或气相,其中气相是优选的。甲醇与AlPO-91催化剂的接触可以连续模式或成批模式进行,其中连续模式是优选的。甲醇与AlPO-91催化剂接触的时间量必须足以将甲醇转化成所需的轻质烯烃产物。当所述方法以成批方法进行时,接触时间从0.001小时至1小时并且优选从0.01小时至1.0小时变化。在较低温度下使用较长的接触时间,而在较高温度下使用较短的时间。当所述方法以连续模式进行时,基于甲醇的重时空速(WHSV)可从1hr-1至1000hr-1并且优选从1hr-1至100hr-1变化。
一般来讲,所述方法必须在高温下进行,以便以足够快的速率形成轻质烯烃。因此,所述方法应在300℃至600℃、优选400℃至550℃并且最优选435℃至525℃的温度下进行。所述方法可在包括自生压力的宽压力范围内进行。因此,压力可从0kPa(0psig)至1724kPa(250psig)并且优选从34kPa(5psig)至345kPa(50psig)变化。
任选地,甲醇原料可用惰性稀释剂稀释以便更有效地将甲醇转化成烯烃。可用的稀释剂的示例为氦气、氩气、氮气、一氧化碳、二氧化碳、氢气、蒸汽、石蜡烃例如甲烷、芳香烃例如苯、甲苯以及它们的混合物。稀释剂的用量可显著变化,并且通常为原料的5摩尔%至90摩尔%,并且优选25摩尔%至75摩尔%。
反应区的实际构型可以是本领域已知的任何熟知的催化剂反应设备。因此,可使用单个反应区或者串联或并联布置的若干区。在此类反应区中,甲醇原料流过包含AlPO-91催化剂的床。当使用多个反应区时,可串联使用一种或多种AlPO-91催化剂以产生所需的产物混合物。可使用动态床***(例如,流化床或移动床)来代替固定床。此类动态***将有利于可能需要的AlPO-91催化剂的任何再生。如果需要再生,AlPO-91催化剂可作为移动床被连续引入再生区,在该再生区中该催化剂可通过诸如在含氧气氛中氧化的手段再生以去除含碳材料。
本发明的AlPO-91材料还可用作水蒸气的吸附剂。吸附剂可以是吸附热泵设备的组成部分。期望用于吸附热泵目的的吸附剂具有高水蒸气容量以及大晶体学密度。微孔结晶材料的晶体学密度便利地以T-原子/的单位表示。一般来讲,具有低密度的吸附剂可能是有问题的,因为它们将需要大量的材料来吸收给定量的被吸附物。如果应用中的空间有限,则这可能很麻烦。因此值得关注的是,基于体积而不是基于重量来考虑吸收容量。
以下实施例是在本发明的例证中提供的,并且不旨在对如所附权利要求中示出的本发明的一般广泛范围进行不当限制。产物将以包含指示“-91”结构的后缀“-91”和反映产物组成性质的前缀(诸如“SAPO”表示磷酸硅铝,“ZnAPO”表示磷酸铝锌,并且“MgAPSO”表示磷酸硅铝镁等)的名称命名。
通过x-射线分析确定本发明的AlPO-91组合物的结构。以下实施例中呈现的X-射线图使用标准x-射线粉末衍射技术获得。辐照源是高强度的x-射线管,其在45kV和35mA下操作。来自铜K-α辐照的衍射图通过合适的基于计算机的技术获得。在2°至56°(2θ)下连续扫描平坦的压缩粉末样品。由表示为θ的衍射峰的位置获得晶面间距(d),其单位为埃,其中θ是如由数字化数据所观察到的布拉格角。强度由减去背景之后的衍射峰积分面积来确定,“Io”为最强线或峰的强度,并且“I”为其他峰中的每个峰的强度。
如本领域技术人员将理解的,参数2θ的测定经历人为和机械误差两者,所述误差的组合可赋予每个报告的2θ值±0.4°的不确定度。这种不确定度当然也体现在报告的d-间距值,其由2θ值计算。这种不精确性在本领域中普遍存在,并且不足以消除本发明的结晶材料彼此之间以及与现有技术的组合物的分化。在所报告的一些x-射线图中,d-间距的相对强度由符号vs、s、m、w和vw指示,其分别表示非常强、强、中等、弱和非常弱。根据100x I/Io,将上述名称定义为:
vw=0-5;w=5-15;m=15-40:s=40-75并且vs=75-100
在某些情况下,合成产物的纯度可参照其x-射线粉末衍射图来评估。因此,例如,如果样品被描述为纯的,则其仅旨在表示样品的x-射线图不含可归因于结晶杂质的线,不表示不存在无定形物质。
为了更充分地示出本发明,示出了以下实施例。应当理解,这些实施例仅是举例说明的,并且不旨在对如所附权利要求中所示的本发明的宽范围进行过度限制。
实施例1
将117.03g水称量到500cc特氟隆瓶中。添加65.43g 1,4-二溴丁烷(99%),然后将该混合物置于冰浴中。在磁力搅拌下,向上述混合物中添加51.6g哌啶(99%)。水和哌啶混合以形成浑浊相,而更致密的1,4-二溴丁烷保留在底部。将特氟隆瓶置于顶置式混合器下并稍微剧烈搅拌。5分钟后,形成澄清的浅黄色模板溶液。继续反应1小时后,停止搅拌。
实施例2
使1154g得自实施例1的溶液与355.1g Ag2O在圆底烧瓶中接触,将它们混合以形成灰色不透明溶液。将烧瓶置于高速顶置式搅拌器下,以在室温下搅拌1天。过滤样品以去除沉淀的溴化银,并且将最终溶液送至水分析,结果表明该样品由79.7%的水构成。
实施例3
将20.26g的实施例2产物与2.39g四甲基氢氧化铵(TMAOH;25%)混合。然后添加1.96g Al(OH)3(Al=27.9%)。缓慢添加5.40g磷酸(85%)。然后将凝胶剧烈搅拌2小时。将该凝胶混合物倾注到45cc高压釜中,并在160℃下消化4天。在加热期间转动高压釜。之后,将凝胶冷却至室温,通过离心分离产物,并将固体在100℃下干燥过夜。原位合成态材料的XRD分析显示出以下线:
该合成的产物通过XRD被鉴定为AlPO-91。
实施例4
将实施例3的产物在马弗炉中在空气中于600℃下煅烧。该炉以2℃/min的速率升温至目标温度。在600℃下煅烧4小时后,将样品冷却至室温。经煅烧的材料的XRD分析显示出以下线:
经煅烧的AlPO-91的表面积(通过77K下的氮吸附测量)测定为377m2/g,并且微孔体积测定为0.19cm3/g。
实施例5
将实施例4的经煅烧的AlPO-91产物压成粒料,并且装载到McBain重量分析天平中以用于吸附研究。观察到以下吸附特性:
分子 | 压力(托) | 吸收量(重量%) |
H<sub>2</sub>O | 4.6 | 13.9 |
CO<sub>2</sub> | 250 | 0.9 |
C<sub>2</sub>H<sub>4</sub> | 600 | 5.7 |
正丁烷 | 700 | 1.2 |
实施例6
将20.26g的实施例2产物与2.39g四甲基氢氧化铵(TMAOH;25%)混合。然后添加1.96g Al(OH)3(Al=27.9%)。缓慢添加5.40g磷酸(85%)。然后将凝胶剧烈搅拌2小时。将该凝胶混合物倾注到45cc高压釜中,并在160℃下消化3天。之后,将凝胶冷却至室温,通过离心分离产物,并将固体在100℃下干燥过夜。原位合成态材料的XRD分析显示出以下线:
该合成的产物通过XRD被鉴定为AlPO-91,其含有少量AlPO-90杂质。
具体的实施方案
虽然结合具体的实施方案描述了以下内容,但应当理解,该描述旨在说明而不是限制前述描述和所附权利要求书的范围。
本发明的第一实施方案为一种微孔结晶材料,所述微孔结晶材料具有由经验式C+ cA+ aMm 2+EPxSiyOz表示的原位合成态形式的并基于无水的经验组成,其中M为至少一种骨架二价阳离子并且选自由碱土金属和过渡金属组成的组,其中M为选自由铍、镁、钴(II)、锰、锌、铁(II)、镍以及它们的混合物组成的组的阳离子,C为环状有机铵阳离子,A为无环有机铵阳离子,比率(c/a)具有0至1000的值,并且总和(c+a)表示(C+A)与E的摩尔比并且具有0.1至2.0的值,“m”为M与E的摩尔比并且从0至1.0变化,“x”为P与E的摩尔比并且从0.5至2.0变化,硅与E的比率由从0至1.0变化的“y”表示,E为四面体配位的三价元素、存在于骨架中并且选自由铝、镓、铁(III)和硼组成的组,并且“z”为O与E的摩尔比并且由公式z=(2·m+c+a+3+5·x+4·y)/2给出,并且通过至少具有表1中所示的d-间距和相对强度的以下x-射线衍射图表征。
表1
本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中在煅烧所述微孔结晶材料后,所述AlPO-91材料通过至少具有下表2中所示的d-间距和相对强度的x-射线衍射图表征。
表2
本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中所述微孔结晶材料基于无水由经验式HwMm 2+EPxSiyOz表征,其中M为至少一种化合价为+2的金属阳离子,所述金属阳离子选自由Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+组成的组,“m”为M与E的摩尔比并且从0至1.0变化,H为质子,w”为H与E的摩尔比并且从0至2.5变化,E为选自由铝、镓、铁、硼以及它们的混合物组成的组的三价元素,“x”为P与E的摩尔比并且从0.5至2.0变化,“y”为Si与E的摩尔比并且从0.05至1.0变化,“m”+“y”≥0.1,并且“z”为O与E的摩尔比并且具有由公式z=(w+2·m+3+5·x+4·y)/2确定的值。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中所述微孔结晶材料在具有晶格参数为和的六方晶型轴的晶胞上索引,并且具有ABC-6网结构,所述网结构具有沿着c-轴每16层重复的堆叠序列(p=40.341/2.5=16.14)。
本发明的第二实施方案为一种制备AlPO-91微孔结晶材料的方法,所述方法包括制备包含反应性源的反应混合物,所述反应性源根据由式aA2ObC2O cMO E2O3 dP2O5 eSiO2fH2O表示的氧化物摩尔比来描述,其中“a”具有0.01至5的值,“b”具有0.01至5的值,“c”具有0至2的值,“d”具有0.5至8的值,“e”具有0至4的值,并且“f”具有30至1000的值,其中反应性源为M和硅中的一者或两者、C、A、E和磷;使所述反应混合物在60℃至200℃的温度下反应1天至21天的时段;以及从异质混合物中分离固体产物,其中所述AlPO-91微孔材料通过至少具有表1中所示的d-间距和相对强度的以下x-射线衍射图表征。
表1
本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中所述AlPO-91在至少550℃的温度下煅烧并且通过至少具有下表2中所示的d-间距和相对强度的x-射线衍射图表征。
表2
铝源选自由铝醇盐、沉淀氧化铝、铝金属、氢氧化铝、铝盐和氧化铝溶胶组成的组。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中磷源选自由正磷酸、五氧化二磷和磷酸二氢铵组成的组。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中二氧化硅源选自由原硅酸四乙酯、胶态二氧化硅和沉淀二氧化硅组成的组。本发明的实施方案为本段中的先前实施方直案至本段中的第一实施方案中的一个、任一个或所有实施方案,其中E元素源选自由有机硼酸铵、硼酸、沉淀羟基氧化镓、硫酸镓、硫酸铁和氯化铁组成的组。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中M金属源选自由相应碱土金属和过渡金属的卤化物盐、硝酸盐、乙酸盐和硫酸盐组成的组。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中C为由环状仲胺和有机二卤化物的水性混合物的反应制备的有机铵阳离子。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中所述环状仲胺选自由哌啶、高哌啶、吡咯烷和吗啉组成的组。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中A为表示为NR4 +的无环有机铵阳离子。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中R基团独立地为式CnH2n+1的脂族碳链,其中n为在1至4范围内的整数(包括端值在内)。本发明的实施方案为本段中的先前实施方案直至本段中的第一实施方案中的一个、任一个或所有实施方案,其中所述AlPO-91微孔结晶材料在至少600℃的温度下煅烧。
本发明的第三实施方案为一种分离分子物质的混合物、去除污染物或催化烃转化过程的方法,所述方法包括使进料料流与微孔结晶材料接触,所述微孔结晶材料具有由经验式HwMm 2+EPxSiyOz表示的煅烧形式的并基于无水的经验组成,其中M为至少一种化合价为+2的金属阳离子,所述金属阳离子选自由Be2+、Mg2+、Zn2+、Co2+、Mn2+、Fe2+、Ni2+组成的组,“m”为M与E的摩尔比并且从0至1.0变化,H为质子,w”为H与E的摩尔比并且从0至2.5变化,E为选自由铝、镓、铁、硼以及它们的混合物组成的组的三价元素,“x”为P与E的摩尔比并且从0.5至2.0变化,“y”为Si与E的摩尔比并且从0.05至1.0变化,“m”+“y”≥0.1,并且“z”为O与E的摩尔比并且具有由公式z=(w+2·m+3+5·x+4·y)/2确定的值,并且通过至少具有表2中所示的d-间距和相对强度的以下x-射线衍射图表征:
表2
本发明的实施方案为本段中的先前实施方案直至本段中的第二实施方案中的一个、任一个或所有实施方案,其中所述分子物质的分离处于吸附热泵的操作中,其中水蒸气被所述微孔结晶材料吸附。本发明的实施方案为本段中的先前实施方案直至本段中的第二实施方案中的一个、任一个或所有实施方案,其中所述烃转化过程选自由裂化、加氢裂化、芳族化合物和异链烷烃两者的烷基化、异构化、聚合、重整、氢化、脱氢、烷基转移、脱烷基化、水合、脱水、加氢处理、加氢脱氮、加氢脱硫、甲醇制烯烃、甲烷化和合成气转变过程组成的组。本发明的实施方案为本段中的先前实施方案直至本段中的第二实施方案中的一个、任一个或所有实施方案,其中所述分子物质的分离基于分子尺寸(动力学直径)或所述分子物质的极性程度。
Claims (10)
1.一种微孔结晶材料,所述微孔结晶材料具有由以下经验式表示的原位合成态形式的并基于无水的经验组成:
C+ cA+ aMm 2+EPxSiyOz
其中M为至少一种骨架二价阳离子并且选自由碱土金属和过渡金属组成的组,其中M为选自由铍、镁、钴(II)、锰、锌、铁(II)、镍以及它们的混合物组成的组的阳离子,C为环状有机铵阳离子,A为无环有机铵阳离子,比率(c/a)具有0至1000的值,并且总和(c+a)表示(C+A)与E的摩尔比并且具有0.1至2.0的值,“m”为M与E的摩尔比并且从0至1.0变化,“x”为P与E的摩尔比并且从0.5至2.0变化,硅与E的比率由从0至1.0变化的“y”表示,E为四面体配位的三价元素、存在于所述骨架中并且选自由铝、镓、铁(III)和硼组成的组,并且“z”为O与E的摩尔比并且由以下公式给出:
z=(2·m+c+a+3+5·x+4·y)/2
并且通过至少具有表1中所示的d-间距和相对强度的以下x-射线衍射图表征:
表1
3.根据权利要求1所述的微孔结晶材料,所述微孔结晶材料基于无水由以下经验式表征:
HwMm 2+EPxSiyOz
其中M为至少一种化合价为+2的金属阳离子,所述金属阳离子选自由Be2+、Mg2+、Zn2+、Co2 +、Mn2+、Fe2+、Ni2+组成的组,“m”为M与E的摩尔比并且从0至1.0变化,H为质子,w”为H与E的摩尔比并且从0至2.5变化,E为选自由铝、镓、铁、硼以及它们的混合物组成的组的三价元素,“x”为P与E的摩尔比并且从0.5至2.0变化,“y”为Si与E的摩尔比并且从0.05至1.0变化,“m”+“y”≥0.1,并且“z”为O与E的摩尔比并且具有由以下公式确定的值:
z=(w+2·m+3+5·x+4·y)/2。
5.一种制备AlPO-91微孔结晶材料的方法,所述方法包括制备包含反应性源的反应混合物,所述反应性源根据由下式表示的氧化物摩尔比来描述:
aA2O∶bC2O∶cMO∶E2O3∶dP2O5∶eSiO2∶fH2O
其中“a”具有0.01至5的值,“b”具有0.01至5的值,“c”具有0至2的值,“d”具有0.5至8的值,“e”具有0至4的值,并且“f”具有30至1000的值,其中反应性源为M和硅中的一者或两者、C、A、E和磷;使所述反应混合物在60℃至200℃的温度下反应1天至21天的时段;以及从异质混合物中分离固体产物,其中所述AlPO-91微孔材料通过至少具有表1中所示的d-间距和相对强度的以下x-射线衍射图表征:
表1
7.一种分离分子物质的混合物、去除污染物或催化烃转化过程的方法,所述方法包括使进料料流与微孔结晶材料接触,所述微孔结晶材料具有由以下经验式表示的煅烧形式的并基于无水的经验组成:
HwMm 2+EPxSiyOz
其中M为至少一种化合价为+2的金属阳离子,所述金属阳离子选自由Be2+、Mg2+、Zn2+、Co2 +、Mn2+、Fe2+、Ni2+组成的组,“m”为M与E的摩尔比并且从0至1.0变化,H为质子,w”为H与E的摩尔比并且从0至2.5变化,E为选自由铝、镓、铁、硼以及它们的混合物组成的组的三价元素,“x”为P与E的摩尔比并且从0.5至2.0变化,“y”为Si与E的摩尔比并且从0.05至1.0变化,“m”+“y”≥0.1,并且“z”为O与E的摩尔比并且具有由以下公式确定的值:
z=(w+2·m+3+5·x+4·y)/2
并且通过至少具有表2中所示的d-间距和相对强度的以下x-射线衍射图表征:
表2
8.根据权利要求7所述的方法,其中所述分子物质的分离处于吸附热泵的操作中,其中水蒸气被所述微孔结晶材料吸附。
9.根据权利要求7所述的方法,其中所述烃转化过程选自由裂化、加氢裂化、芳族化合物和异链烷烃两者的烷基化、异构化、聚合、重整、氢化、脱氢、烷基转移、脱烷基化、水合、脱水、加氢处理、加氢脱氮、加氢脱硫、甲醇制烯烃、甲烷化和合成气转变过程组成的组。
10.根据权利要求7所述的方法,其中所述分子物质的分离基于分子尺寸(动力学直径)或所述分子物质的极性程度。
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