CN112912340A - 高酸度和低二氧化硅与氧化铝比率(sar)的ssz-13沸石的制备方法 - Google Patents
高酸度和低二氧化硅与氧化铝比率(sar)的ssz-13沸石的制备方法 Download PDFInfo
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- CN112912340A CN112912340A CN201980070099.3A CN201980070099A CN112912340A CN 112912340 A CN112912340 A CN 112912340A CN 201980070099 A CN201980070099 A CN 201980070099A CN 112912340 A CN112912340 A CN 112912340A
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- zeolite
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- silica
- metal
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 135
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 119
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 238000003795 desorption Methods 0.000 claims abstract description 7
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- 150000003624 transition metals Chemical class 0.000 claims description 23
- 150000001768 cations Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- -1 adamantyl ammonium hydroxide Chemical compound 0.000 claims description 15
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
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Images
Classifications
-
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Abstract
Description
本公开总体上涉及一种制造显示出低二氧化硅与氧化铝摩尔比率(SAR)和高酸度的SSZ-13沸石的方法、根据所述方法形成的SSZ-13沸石以及由该SSZ-13沸石形成的催化剂。这种催化剂可以用于低温引发或起燃(light-off)NOx转化反应。
本节中的陈述仅仅提供与本公开有关的背景信息,并且可能不构成现有技术。微孔沸石包含三维通道,在对由柴油发动机产生的NOx废气排放物的选择性催化还原(SCR)中起着重要的作用。更具体地,这些沸石被掺入作为SCR催化剂的一部分,该SCR催化剂能够在还原剂(例如,氨)的存在下将NOx气体转化成元素氮(N2)和水(H2O)。在这种SCR过程中,通常将还原剂添加到废气中,然后使废气与SCR催化剂接触。使还原剂吸收至SCR催化剂上,并且NOx还原反应会随着气体通过或越过催化剂而发生。
沸石是具有通过共享氧原子而相互连接的二氧化硅(SiO2)和氧化铝(Al2O3)的晶体骨架的铝硅酸盐材料。因此,沸石可以通过存在于晶体骨架中的SiO2∶Al2O3的比率(SAR)来表征。较高的SAR值通常与表现出较高的水热稳定性的SCR催化剂有关。由于废气中可能包含水蒸气,并且废气在离开发动机时会具有至少500℃的温度,因此在设计催化剂时,SCR催化剂的水热稳定性成为重要的考虑因素。但是,催化剂的设计还必须考虑引发或“起燃”NOx转化所必需的催化剂的低温特性。
发明内容
本公开总体上涉及一种制造具有低二氧化硅与氧化铝比率(SAR)和高酸度的SSZ-13沸石的方法、根据所述方法形成的SSZ-13沸石以及由该SSZ-13沸石形成的催化剂。
根据本公开的一个方面,制造SSZ-13沸石的方法包括以下步骤:a)提供二氧化硅来源;b)提供氧化铝来源;c)提供结构导向剂(SDA);d)任选地,提供碱源;e)提供金属阳离子来源;f)在水中混合所述二氧化硅来源、所述氧化铝来源、所述SDA和所述金属阳离子来源,以形成凝胶组合物;g)将所述凝胶组合物加热至约140℃至约180℃范围的结晶温度;h)将所述凝胶组合物在所述结晶温度保持9小时至24小时的时间段;i)使所述SSZ-13沸石结晶并沉淀;所述凝胶组合物形成所述SSZ-13沸石的结晶沉淀物和母液;以及j)从所述母液中分离出所述结晶沉淀物。
如此形成的所述SSZ-13沸石显示出小于15:1的二氧化硅与氧化铝(SiO2:Al2O3)的摩尔比率。该方法是一种水热合成法,生成的SSZ-13沸石的形态包括立方形、球形或菱形颗粒中的一种或多种;并且其晶体尺寸为约0.1微米(μm)至10μm的范围。SSZ-13沸石还显示出通过氨程序升温脱附法测得的2.0mmol/g至3.4mmol/g范围的酸度。
SSZ-13可以用作在低温NOx转化中使用的催化剂的载体材料。该催化剂可以使用包括以下步骤的方法制备:形成SSZ-13沸石,使其包含一种或多种金属阳离子作为SSZ-13沸石的一部分;提供至少一种过渡金属来源;使所述SSZ-13沸石和所述过渡金属来源经历离子交换、浸渍或同形取代过程。在该方法中,用所述至少一种过渡金属代替SSZ-13沸石中的金属阳离子,从而形成催化剂。催化剂中存在的过渡金属(TM)和铝的含量还由0.5到1范围的TM:Al摩尔比率定义。SSZ-13沸石能够低温引发或“起燃”NOx转化。
对其他领域的适用性将由本文提供的描述而变得显而易见。应当理解,描述和具体实施例仅旨在用于说明的目的,并不旨在限制本公开的范围。
附图说明
为了使本公开易于理解,现在将通过实施例并参考附图的方式描述其各种形式,其中:
图1是新鲜催化剂和用过的催化剂的NOx转化与温度的关系图,显示了起燃温度的定义;
图3是根据本公开的教导的用于制备SSZ-13沸石的方法的流程图;
图4是使用根据图1形成的SSZ-13沸石根据本公开的教导制备催化剂的方法的流程图;
图5是根据本发明的教导形成的SSZ-13沸石的X射线衍射(XRD)光谱;
图6是图4中所述的SSZ-13沸石的扫描电子显微照片(SEM);
图7是提供针对由根据本公开的教导形成的SSZ-13沸石制备的催化剂测量的起燃温度数据的表;和
图8是根据本公开内容的教导制备的催化剂的NOx转化百分比随温度变化的曲线图。
本文描述的附图仅用于说明目的,并且不旨在以任何方式限制本公开的范围。
具体实施方式
以下描述本质上仅是示例性的,绝不旨在限制本公开或其应用或用途。例如,在整个本公开内容中描述了根据本文包含的教导制备和使用的沸石载体以及选择性催化还原(SCR)催化剂,以便更充分地说明其组成和用途。这样的SSZ-13沸石在其他应用(例如吸附剂、离子交换剂、或用作用于其他工业催化剂和/或环境催化剂的载体材料)中的掺入和使用都在本公开的范围内。应当理解,在整个说明书中,相应的附图标记表示相同或相应的部件和特征。
本公开提供了一种用于形成能够低温引发或“起燃”NOx转化的铝硅酸盐SSZ-13沸石的合成方法。根据本公开的教导形成的SSZ-13沸石具有低的SiO2:Al2O3摩尔比率(SAR),例如,SAR小于或等于16,同时表现出高水平的酸度。该方法将结构导向剂(SDA)的使用限制在SDA与SiO2的摩尔比率为约0.03∶1至约0.05∶1。此方法中使用的SDA量少,并且根据该方法形成的SSZ-13沸石的产率高,从而形成了一种廉价的方法,该方法不需要额外的步骤如母液的再利用以降低成本。
根据上述方法形成并在本文中进一步定义的SSZ-13沸石在大多数应用中的使用在经济上是可行的。之前使用形成SSZ-13沸石和/或其他CHA型沸石的常规合成方法限制了此类沸石在成本敏感型应用中的使用,例如用于车辆废气中包含的NOx的选择性还原反应(SCR)的催化剂的载体材料。
根据本公开的一个方面,根据该方法形成的SSZ-13沸石表现出小于15的SiO2/Al2O3摩尔比率,平均颗粒尺寸为0.1微米(μm)至约10.0μm,形态包括立方形、球形或菱形颗粒中的一种或更多种,并且酸度高。如此形成的SSZ-13沸石具有优异的耐久性和耐热性,并且与由常规的菱沸石型沸石形成的含金属的催化剂相比,由其形成的含金属的催化剂在低温下显示出提高的NOx还原率。本公开的SSZ-13沸石有利于在需要低温起燃NOx转化反应的应用中使用。
为了本公开的目的,起燃温度是指引发期望的催化反应的温度。例如,起燃温度可以指但不限于在催化转化器中引发NOx转化的温度。替代地,起燃温度可以定义为其中新鲜催化剂和用过的催化剂体系的NOx转化达到至少50%的温度,如图1所示。
通常,沸石是由重复的TO4四面体单元构成的晶体或准晶体硅铝酸盐,其中T最通常为硅(Si)或铝(Al)。这些重复单元连接在一起以形成晶体骨架或结构,该晶体骨架或结构包括晶体结构内的分子维度的空腔和/或通道。因此,铝硅酸盐沸石至少包含氧(O)、铝(Al)和硅(Si)作为在其骨架结构中掺入的原子。
SSZ-13是一种铝硅酸盐沸石,其展现出的骨架拓扑结构与菱沸石的骨架拓扑结构相同(骨架符号“CHA”)。通常,SSZ-13沸石展现出的组成包含高的二氧化硅与氧化铝比率(SAR),这导致经受阳离子交换的能力低。然而,在本公开中,形成的SSZ-13沸石表现出低的二氧化硅与氧化铝比率(SAR),从而允许相对于阳离子交换的高能力。
符号“CHA”表示由国际沸石协会(IZA)指定的代码,该代码定义了沸石的框架结构。因此,SSZ-13沸石是指其中沸石的主晶相为“CHA”的硅铝酸盐。在本公开的SSZ-13沸石中,在沸石中没有或不存在另一种晶相或骨架结构,例如“FAU”。换句话说,本公开的SSZ-13沸石基本上不含其他晶相,并且不是两种或更多种骨架类型的共生体。
此外,CHA晶体结构的骨架中没有可觉察的磷含量。换句话说,本公开的CHA沸石不包含会影响材料的基本物理和/或化学性质(例如,沸石在宽温度范围选择性还原NOx的能力)的磷含量。
沸石的晶相或骨架结构可以通过X射线衍射(XRD)数据来表征。但是,XRD测量会受多种因素影响,例如沸石的生长方向;构成元素的比例;被吸附物质、缺陷等的存在;以及XRD光谱中每个峰的强度比或位置的偏差。因此,针对IZA提供的定义中所述的CHA结构的每个参数测得的数值的10%或更低的偏差、或者5%或更低的偏差、或者1%或更低的偏差均在预期公差范围内。
根据本公开的一方面,SSZ-13沸石可以包括天然沸石、合成沸石或其混合物。或者,SSZ-13沸石是根据本公开的教导形成的合成沸石。合成沸石在SAR、微晶尺寸和微晶形态方面表现出更好的均一性,并且具有较少且低浓度(less concentrated)的杂质(例如,碱土金属)。
SSZ-13沸石包含平均晶体尺寸为约0.1微米(μm)至约10.0微米(μm)的晶体。或者,晶体尺寸为约0.2μm至约8μm;或者为至少0.25μm且小于7.5μm。SSZ-13沸石中的晶体可以是个体晶体,也可以是团聚的晶体,也可以是两者的组合,前提是与这种团聚相关的平均颗粒尺寸的下限是沸石的平均个体晶体尺寸。
晶体尺寸也可以称为晶体直径,因为它代表晶体的面的一个边缘的长度。除了代替个体晶体的面的边缘,可以以类似的方式定义团聚的晶体的颗粒尺寸,该颗粒尺寸表示团聚的晶体的最长边的长度。如本文所用,与晶体尺寸或颗粒尺寸相关的术语“平均值”旨在表示具有统计学意义的沸石样品的算术平均值。
形成的SSZ-13沸石的平均颗粒尺寸小于50微米(μm)、或小于约20微米、或小于10μm。SSZ-13沸石的平均颗粒尺寸可以使用任何已知的常规方法来测量,包括但不限于激光衍射、动态光散射和筛分。
根据本公开的另一方面,SSZ-13沸石的二氧化硅与氧化铝(SAR)摩尔比率为小于16:1。或者,SSZ-13沸石的SAR为约8:1至约15.5:1、或为约10:1至15.5:1。沸石的二氧化硅与氧化铝(SAR)摩尔比率可以使用任何常规分析方法来确定,例如,X射线荧光(XRF)或电感耦合等离子体(ICP)发射光谱法。SAR比率代表存在于沸石晶体的晶体骨架中的硅与铝原子的比率。
“干燥的”SSZ-13沸石表现出的形态可能类似于立方形、方形薄片、球形颗粒、菱形颗粒、不规则颗粒、或其组合或混合物。或者,SSZ-13沸石的形态包括立方形、球形或菱形颗粒中的一种或多种。
形成的SSZ-13沸石也可以表现出高水平的酸度。所形成的SSZ-13沸石表现出如图2所示的通过氨程序升温脱附测量的范围为2.0mmol/g至3.4mmol/g的酸度。或者,SSZ-13沸石表现出的酸度为约2.5mmol/g至约3.0mmol/g的范围;或者,SSZ-13沸石表现出的酸度可以为约2.7mmol/g至约2.8mmol/g。在图2中,根据本公开的教导形成并测试的两个SSZ-13沸石样品(R-1,R-2)中的每一个均显示出两个NH3脱附峰。在低于200℃的温度出现的NH3脱附峰与弱的酸位点有关,而在高于500℃的温度出现的另一个峰与强的酸位点有关。
现在参考图3,提供了一种用于生产SSZ-13沸石的水热合成方法1,该沸石显示出二氧化硅与氧化铝(SiO2:Al2O3)的比率小于15,晶体尺寸为约0.1微米至10微米的范围,并且其形态包括立方形、球形或菱形颗粒中的一种或多种。
该水热法1通常包括以下步骤:
a)提供5二氧化硅来源;
b)提供10氧化铝来源;
c)提供15结构导向剂(SDA);
d)任选地,提供20碱源(OH-);
e)提供25金属阳离子来源;
f)在水中混合30所述二氧化硅来源、所述氧化铝来源、所述SDA和所述金属阳离子来源以形成凝胶组合物;
g)将所述凝胶组合物加热35至约140℃至约180℃范围的结晶温度;
h)将所述凝胶组合物在所述结晶温度保持40范围为9小时至24小时的时间段;
i)使所述SSZ-13沸石45结晶并从凝胶组合物中沉淀出来;形成结晶沉淀物和母液;和
j)从所述母液中分离出50所述结晶沉淀物。
所述二氧化硅来源可以包括硅酸钠、硅溶胶、胶体二氧化硅、火成二氧化硅、原硅酸四乙酯或其混合物,主要由硅酸钠、硅溶胶、胶体二氧化硅、火成二氧化硅、原硅酸四乙酯或其混合物组成,或由硅酸钠、硅溶胶、胶体二氧化硅、火成二氧化硅、原硅酸四乙酯或其混合物组成。凝胶组合物中存在的二氧化硅的量取决于每种其他原料相对于二氧化硅在本文指定的范围内所需的含量,以提供显示出期望的SiO2:Al2O3比率、晶体尺寸和形态的SSZ-13沸石。二氧化硅来源应选择能够与用于形成凝胶组合物的其他原料均匀混合的形式。
所述铝源可以包括铝金属、氢氧化铝(例如三水铝石、勃姆石等)、硫酸铝、硝酸铝、铝酸钠、氯化铝、硅铝酸盐凝胶、或其混合物中的一种或多种;基本由铝金属、氢氧化铝(例如三水铝石、勃姆石等)、硫酸铝、硝酸铝、铝酸钠、氯化铝、硅铝酸盐凝胶、或其混合物中的一种或多种组成;或由铝金属、氢氧化铝(例如三水铝石、勃姆石等)、硫酸铝、硝酸铝、铝酸钠、氯化铝、硅铝酸盐凝胶、或其混合物中的一种或多种组成。凝胶组合物中存在的氧化铝的量取决于每种其他原料相对于二氧化硅在本文指定的范围内所需的含量,以提供显示出期望的SiO2:Al2O3比率、晶体尺寸和形态的SSZ-13沸石。氧化铝来源应选择能够与用于形成凝胶组合物的其他原料均匀混合的形式。
用于制备AEI型沸石的结构导向剂(SDA)通常是能够引导或定向沸石骨架的分子形状和图案的复杂分子。通常,沸石晶体在SDA周围形成。形成晶体后,将SDA从晶体的内部结构中去除,留下分子多孔的笼状结构。.
用于形成SSZ-13沸石的结构导向剂(SDA)的量由约0.03:1至约0.05:1、或约0.04:1的SDA与二氧化硅摩尔比率(SDA:SiO2)来定义。SDA可以包括但不限于N,N,N-三烷基金刚烷基铵阳离子、N,N,N-三甲基苄基铵阳离子、N-烷基-3-喹核醇阳离子或N,N,N-三烷基外氨基降冰片烷阳离子的氢氧化物、卤化物、碳酸盐、甲基碳酸盐或硫酸盐。或者,SDA是N,N-二甲基-3,5-二甲基哌啶氢氧化物、N,N-二乙基-2,6-二甲基哌啶氢氧化物、四乙基氢氧化膦、或其混合物。
当碱(OH-)衍生自SDA溶于水中时从SDA解离的阴离子时,用于形成所述凝胶组合物的结构导向剂(SDA)的量还可以通过所述凝胶组合物中存在的所述碱(OH-)与二氧化硅的摩尔比率(OH-:SiO2)来表征。OH-:SiO2的摩尔比率可以为0.6:1至1:1的范围、或为约0.7:1至约0.9:1、或为约0.8:1。任选地,可以提供额外的碱(OH-)作为用于形成凝胶组合物的原料,条件是OH-:SiO2的摩尔比率保持在规定的范围内。
用于形成凝胶组合物的水的量可以由范围为约40:1至约50:1的水与二氧化硅的摩尔比率(H2O:SiO2)定义。或者,H2O:SiO2的摩尔比率为42:1至48:1,或H2O:SiO2的摩尔比率为约45:1。
金属(M)离子来源可以包括碱金属、碱土金属或其组合;基本上由碱金属、碱土金属或其组合组成;或由碱金属、碱土金属或其组合组成。碱金属或碱土金属可以独立地选自钠(Na)、钾(K)、钙(Ca)、钡(Ba)或锶(Sr)。碱金属或碱土金属阳离子可以获自金属卤化物、金属氢氧化物、金属碳酸盐、金属碳酸氢盐、金属硝酸盐或金属硫酸盐。凝胶组合物中包含碱金属或碱土金属阳离子有助于通过迫使SDA与铝以优选状态配位来促进结晶。当沸石用作吸附剂或催化剂的载体时,在沸石形成过程中掺入沸石晶体结构中的任何碱金属或碱土原子可通过离子交换机制从晶体结构内去除。离子交换机制能够用氢、铵或任何其他所需的金属离子代替碱金属或碱土金属阳离子。
用于水热合成的反应容器没有特别限制,只要其能抵抗热和压力的施加即可。这种容器的实例包括但不限于高压釜。可以将装入反应容器的原料混合物在加热并暴露于高压之前密封在其中。
图3中方法1的步骤f)中形成的凝胶组合物可以在制备后立即经历水热条件处理,或在经过一段时间的混合后,例如在低温(包括但不限于室温或低于100℃)老化约1小时到大约24小时的时间段后,当需要时再经历水热条件处理。在大规模生产期间,会不希望原料的混合变差,因为必须有足够的掺混状态才能实现SSZ-13沸石的高收率和适当的结晶。
仍然参考图3,在实施方法1期间,使凝胶组合物在预定的结晶温度加热35预定的时间。这种水热合成利用范围为约140℃至180℃、或约150℃至约170℃、或约160℃至约165℃的结晶温度。在其间维持35该温度以使SSZ-13沸石结晶和沉淀的时间段为9小时至24小时、或约12小时至约22小时、或约16小时至约20小时。
水热反应完成后,将结晶沉淀形式的SSZ-13沸石与剩余液体(例如母液)分离。可以丢弃母液,或者在需要时可以将其重新使用,以替代用于制造另一批次的SSZ-13沸石的至少一部分水。该分离可以使用任何已知的常规方法,包括但不限于过滤、倾析或直接干燥(例如蒸发)。
从母液中分离后,会收集到可能包含一些SDA和/或金属阳离子的SSZ-13沸石,任选地用水洗涤,然后干燥。干燥的载体材料可以干燥状态用于某些应用,或者在用于其他应用之前进行煅烧。在高温下(例如,>200℃、>300℃等)煅烧SSZ-13沸石除去存在于多孔结构中的任何残留的SDA。
相对于凝胶组合物中存在的总氧化物,根据该方法形成的SSZ-13沸石的产率大于20%。或者,产率大于30%、或大于40%。因此,本公开的方法不需要再使用母液作为用于形成凝胶组合物的水的一部分以得到高产率。但是,由于母液含有未反应的SDA,因此,需要时,可以使用母液代替其中混合了原料而形成凝胶组合物的水的至少一部分。
本文形成的“干燥的”SSZ-13沸石还可以显示出大于500m2/g、或者至少600m2/g、或者等于或大于700m2/g的BET比表面积。SSZ-13沸石的比表面积可以使用常规的Brunauer-Emmett-Teller(BET)方法进行测量。
根据本公开的方法形成的SSZ-13沸石的用途可以包括但不限于作为催化剂的载体材料、吸收剂或分离材料。“干燥的”SSZ-13沸石可以在煅烧之前或之后使用。
催化剂可以包含具有已与骨架中的原子进行了交换或以其他方式浸渍到沸石的孔和/或腔中的一种或者多种催化金属离子的SSZ-13沸石。如本文所用,术语“交换的金属”和“取代的金属”以类似的方式使用,意指铝或硅骨架原子中的一个或多个已经被取代性金属代替。
可以掺入SSZ-13沸石中的催化金属离子的几个实例包括但不限于过渡金属、铂族金属(PGM)、贵金属(如金或银)、稀土金属、或其混合物的离子。如本文所用,过渡金属是3-12族的元素,其中电子结构在(3-6)d壳层中开始填充电子,而稀土金属是在4f或5f壳层中开始填充电子的元素。这些d区元素通常被称为“过渡金属”,而f区元素通常被称为镧系元素、锕系元素和/或“内部过渡金属”。
过渡金属可以包括铜、镍、锌、铁、钨、钼、钴、钛、锆、铬、锰或锡,基本上由铜、镍、锌、铁、钨、钼、钴、钛、锆、铬、锰或锡组成,或由铜、镍、锌、铁、钨、钼、钴、钛、锆、铬、锰或锡组成。或者,过渡金属包括铁(Fe)、铜(Cu)或锰(Mn),由铁、铜(Cu)或锰(Mn)组成;或基本上由铁(Fe)、铜(Cu)或锰(Mn)组成。铂族金属可以包括但不限于钌、铑、钯、铟和铂。稀土金属包括镧、铈、镨、钕、铕、铽、铒、镱和钇。
根据本公开的另一方面,提供了一种使用SSZ-13沸石作为载体的制备催化剂的方法。现在参考图4,该方法100通常包括以下步骤:根据上文所述并且在本文中进一步定义的方法形成105一种SSZ-13沸石,其包含一种或多种金属阳离子作为SSZ-13沸石的一部分;提供110至少一种过渡金属来源;使SSZ-13沸石和过渡金属来源经历115离子交换、浸渍、或同形取代过程,以使至少一种过渡金属取代SSZ-13沸石中的金属阳离子,由此形成催化剂。
催化剂中存在的催化性过渡金属(M)和铝的量还由0.5:1到1:1范围的取代金属与铝的摩尔比率(M:Al)定义。或者,M:Al的摩尔比率为约0.6:1至0.9:1的范围;或者,M:Al的摩尔比率为约0.7:1至0.8:1。掺入沸石中的催化金属离子的量在至少约210℃、或者至少约220℃、或者至少约230℃、或者至少约250℃、或者至少约270℃的起燃温度,能够实现至少约50%、或者至少约55%、或者至少约60%的NOx转化。
掺入SSZ-13沸石载体中或在SSZ-13沸石载体上的较高的金属负载量通常会得到较高的NOx转化。但是,掺入其中的金属的含量通常取决于沸石中存在的交换位点的数量,而交换位点的数量又取决于沸石的SAR值。通常,低SAR的沸石允许最高的金属负载量,而高SAR的沸石则具有较高的水热稳定性。因此,在对高催化活性与高水热稳定性的需求之间存在矛盾。根据本公开的教导形成的催化剂通常在较低的操作温度(例如低于400℃)显示出高的催化活性,同时保持相当高的水热稳定性。
催化剂可以以涂覆于基底上的载体涂料(washcoat)的形式使用,所述基底例如金属或陶瓷的流通式整体基底或过滤基底。整体基底可以具有蜂窝状几何形状,其包括具有正方形横截面面积的多个相邻的平行通道。整体基底的蜂窝形状提供了具有最小总体尺寸和压降的大催化表面。这种基底的具体实例包括但不限于壁流式过滤器。因此,本公开的另一方面是包含如本文所述的催化剂组分的载体涂料。另外,催化剂载体涂料还可以包含粘合剂材料,例如氧化铝、二氧化硅、(非沸石)二氧化硅-氧化铝、天然粘土、TiO2、ZrO2和SnO2。
根据本公开的另一方面,一种用于减少气流中的NOx排放物的方法,包括使所述排放物与已经在其上沉积了催化剂的基底接触。该催化剂是根据本公开的教导形成的含金属的SSZ-13沸石。当需要时,可以使气流在氨的存在下与废气制品接触,从而提供选择性催化还原(SCR)系统。
给出以下具体实施例以说明本公开,并且不应将其解释为限制本公开的范围。根据本公开,本领域技术人员会理解,在不脱离或不超出本公开的精神或范围的情况下,在本文公开的具体实施方案中可以做许多改变,并仍获得相同或相似的结果。
在以下实施例中,使用HORIBALA-920激光粒度仪测量颗粒尺寸分布,使用RigakuMiniFlex II DESKTOP X射线衍射仪测量相和结晶度,使用Micromeritics TriStar II3020进行BET表面积测量,使用Spectro Analytical Instruments型号FCPSA83D ICP进行化学组成分析,并使用扫描电子显微镜(SEM)测量沸石的形态。
实施例1:一批次SSZ-13沸石的制备和表征
将预定量的硫酸铝(即,氧化铝来源)加入水中以形成澄清溶液。然后将预定量的氢氧化钾(即,金属阳离子来源)和N,N,N-三烷基金刚烷基氢氧化铵(即,结构导向剂,RNOH)加入该溶液中。最后,将胶体二氧化硅添加到该溶液中。将该溶液混合在一起以形成透明的溶胶或凝胶组合物。选择形成上述凝胶的每种材料或组分的量,使得凝胶的最终组成为46K2O:6.5Al2O3:100SiO2:5000H2O:3RNOH。将凝胶组合物转移到高压釜中,加热到165℃,并持续24小时。将形成并沉淀的SSZ-13沸石从母液中滤出,用水洗涤,并在120℃干燥。将收集的SSZ-13沸石储存以进行进一步分析,并标记为R-3。发现收集的SSZ-13沸石(R-3)的SAR值为15.4。
现在参考图5,对在该实施例中收集并干燥的沸石(R-3)测量的X射线衍射(XRD)图200显示了对应于SSZ-13结构或骨架的2个θ峰205。测得的XRD图200进一步证明该SSZ-13沸石基本上不含任何其他类型的结晶沸石相或结构。
现在参照图6,在该实施例中收集并干燥的SSZ-13沸石(R-3)的形态在扫描电子显微照片中显示为主要包括立方结构210,每个立方结构的每一侧的长度(L)为约1200纳米(nm)。
还发现在该实施例中收集并干燥的SSZ-13沸石(R-3)显示出约516m2/g量级的BET比表面积(SSA)和约0.3cm3/g的功率体积(PV)。可以使用Micromeritics TriStar II 3020分析仪测量新鲜和/或老化的沸石样品的Brunauer、Emmett和Teller(BET)表面积、总孔隙率和孔径分布。这样的BET表面积可以为约100m2/g至800m2/g的范围,或者为约200m2/g至600m2/g的范围。SSZ-13沸石的孔体积可以为约0.1cm3/g至2cm3/g的范围,或者为约0.2cm3/g至1.5cm3/g的范围。
实施例2:NOx转化的起燃温度的测量
起燃温度是通过评估50%的NOx已转化为N2或其他氮物质的温度来测量的。通过用铜金属代替SSZ-13沸石(R-3)中的一部分金属阳离子来形成催化剂(R-4)。然后,测量催化剂(R-4)的新鲜样品的起燃温度,然后再次测量在700℃或825℃的温度进行水热老化16小时后的催化剂(R-4)样品的起燃温度。参照图7中所示的表,新鲜的催化剂(R-4)显示的起燃温度为约212℃,而水热老化的催化剂(R-4)显示的起燃温度稍高,为230℃至270℃。
实施例3:NOx转化的测量
使用Micromeritics 2920充当微流反应器和MKS残留气体分析仪测量与含铜催化剂(R-4)相关的NOx转化,该MKS残留气体分析仪在通过样品后进行气体浓度分析。通常使用以下气体浓度测试样品:NO=175ppm;NO2=175ppm;NH3=350ppm;O2=175ppm。样品在50,000-1/hr的空速下进行测试。在稳态反应下,在每个单独的温度测量NOx转化,首先将样品加热至目标温度,然后一旦观察到稳态,则测量NOx转化。通常,在恒定压力下45分钟后,通过MKS残余气体分析仪根据稳态条件计算出的NOx转化数。
现在参考图8,通过用铜金属取代SSZ-13沸石(R-3)中的部分金属阳离子而形成的新鲜的铜催化剂(R-4)在310℃至650℃的较宽温度窗口实现约100%的转化。在700℃水热老化16小时后,催化剂(R-4)在360℃至610℃的温度仍具有大于95%的NOx转化。在825℃水热老化16小时后,催化剂(R-4)仍然有效地用于NOx转化,在约350℃至约550℃的温度具有大于80%的NOx转化。
出于本公开的目的,由于本领域技术人员已知的预期变化(例如,测量的限制和可变性),本文相对于可测量的值和范围使用术语“约”和“基本上”。
出于本公开的目的,本文中陈述为“在[第一数字]和[第二数字]之间”或“从[第一数字]到[第二数字]”的任何参数范围旨在包括所引的数字。换句话说,该范围旨在与被指定为“[第一数字]至[第二数字]”的范围类似地解释。
出于本公开的目的,术语“重量”是指质量值,例如具有克、千克等单位。此外,由端点引出的数值范围包括端点和该数值范围内的所有数字。例如,浓度为40重量%至60重量%的范围包括40重量%的浓度、60重量%的浓度、以及它们之间的所有浓度(例如40.1%、41%、45%、50%、52.5%、55%、59%等)。
出于本公开的目的,术语要素中的“至少一个”和“一个或多个”可以互换使用并且可以具有相同的含义。这些术语表示包括单个要素或多个要素,也可以由要素末尾的后缀“(s)”表示。例如,“至少一种金属”、“一种或多种金属”和“金属(s)”可以互换使用,并且旨在具有相同的含义。
在本说明书中,已经以使得能够写出清楚简洁的说明书的方式描述了实施方式,但是旨在并且将理解的是,在不脱离本发明的情况下,可以对实施方式进行各种组合或拆分。例如,将意识到,本文描述的所有优选特征均适用于本文描述的本发明的所有方面。
根据本公开,本领域技术人员会理解,在不脱离本发明的精神或范围的情况下,在本文公开的具体实施方案中可以做许多改变,并仍获得相同或相似的结果。本领域技术人员将进一步理解,这里报告的任何性质都代表常规测量的性质,可以通过多种不同的方法获得。本文所描述的方法代表一种这样的方法,并且其他方法可以在不超出本公开范围的情况下使用。
已经出于说明和描述的目的提供了本发明的多种形式的前述描述。其并非旨在穷举本发明或将本发明限制于所公开的精确形式。根据以上的教导,许多修改或变化是可能的。选择并描述所讨论的形式是为了最好地说明本发明的原理及其实际应用,从而使本领域的普通技术人员能够以多种形式以适合预期的具体用途的各种修改来最好地利用本发明。当附加权利要求书根据其公正、合法和公平的权利范围进行解释时,所有这些修改和变化都在由附加权利要求确定的本发明的范围内。
Claims (20)
1.一种制造SSZ-13沸石的方法,所述方法包含以下步骤:
a)提供二氧化硅来源;
b)提供氧化铝来源;
c)提供结构导向剂(SDA);
d)任选地,提供碱源(OH-);
e)提供金属阳离子来源;
f)在水中混合所述二氧化硅来源和所述氧化铝来源与所述SDA和所述金属阳离子来源,以形成凝胶组合物;
g)将所述凝胶组合物加热至约140℃至约180℃范围的结晶温度;
h)将所述凝胶组合物在所述结晶温度保持9小时至24小时的时间段;
i)使所述SSZ-13沸石结晶并沉淀;所述凝胶组合物形成所述SSZ-13沸石的结晶沉淀物和母液;以及
j)从所述母液中分离出所述结晶沉淀物;
其中,所形成的SSZ-13沸石显示出小于16:1的二氧化硅与氧化铝(SiO2:Al2O3)的摩尔比率(SAR);
其中,所形成的SSZ-13沸石具有包括立方形、球形或菱形颗粒中的一种或多种的形态。
其中,所形成的SSZ-13沸石显示出约0.1微米(μm)至10μm范围的晶体尺寸。
2.根据权利要求1所述的方法,其中,所述SSZ-13沸石显示出范围为8∶1至15.5∶1的二氧化硅与氧化铝(SiO2:Al2O3)的摩尔比率(SAR)。
3.根据权利要求1或2中任一项所述的方法,其中,所述二氧化硅来源中的至少一个选自硅酸钠、硅溶胶、胶体二氧化硅、火成二氧化硅、原硅酸四乙酯或它们的混合物。
4.根据权利要求1-3中任一项所述的方法,其中,所述氧化铝来源选自由以下组成的组:铝金属、氢氧化铝、硫酸铝、硝酸铝、铝酸钠、氯化铝、硅铝酸盐凝胶、或其混合物。
5.根据权利要求1-4中任一项所述的方法,其中,所提供的所述结构导向剂(SDA)和所述二氧化硅(SiO2)来源的量由范围为0.03至0.05的SDA∶SiO2摩尔比率限定。
6.根据权利要求1-5中任一项所述的方法,其中,所述氧化铝来源选自三水铝石或勃姆石。
7.根据权利要求1-6中任一项所述的方法,其中,所提供的水(H2O)和所述二氧化硅(SiO2)来源的量由范围为40至50的H2O∶SiO2摩尔比率限定。
8.根据权利要求1-7中任一项所述的方法,其中,所提供的所述碱(OH-)源和所述二氧化硅(SiO2)来源的量还由范围为0.6至1.0的(OH-)∶SiO2摩尔比率限定。
9.根据权利要求1-8中任一项所述的方法,其中,所述结构导向剂(SDA)是N,N,N-三烷基金刚烷基氢氧化铵。
10.根据权利要求1-9中任一项所述的方法,其中,所述金属阳离子来源选自碱金属、碱土金属、或其组合。
11.根据权利要求10所述的方法,其中,所述碱金属和碱土金属独立地选自钠(Na)、钾(K)、钙(Ca)、钡(Ba)和锶(Sr)。
13.根据权利要求1-12中任一项所述的方法,其中,将所述凝胶组合物加热至约140℃至约180℃范围的结晶温度。
14.根据权利要求1-13中任一项所述的方法,其中,将所述凝胶组合物保持在所述结晶温度约9小时至约24小时的时间段。
15.根据权利要求1-14中任一项所述的方法,其中,所形成的SSZ-13沸石显示出约0.25微米至7.5微米的平均晶体尺寸。
16.根据权利要求1-15中任一项的方法制备的SSZ-13沸石。
17.一种形成用于低温NOx转化的催化剂的方法,其中所述方法包括以下步骤:
根据权利要求1-15中任一项的方法形成SSZ-13沸石,其包含一种或多种金属阳离子作为所述SSZ-13沸石的一部分;
提供至少一种过渡金属来源;和
使所述SSZ-13沸石和所述过渡金属来源经历离子交换、浸渍或同形取代过程;
其中,用所述至少一种过渡金属取代所述SSZ-13沸石中的所述金属阳离子,从而形成所述催化剂;
其中,所述催化剂中所述过渡金属(TM)和铝的含量还由0.5到1.0范围的TM:Al摩尔比率定义。
18.根据权利要求17所述的方法,其中,所述过渡金属选自铁(Fe)、铜(Cu)、锰(Mn)、或其组合的组。
19.催化剂用于转化NOx排放物的用途,
其中,所述催化剂是根据权利要求17-18中任一项的方法制备的;
其中,所述催化剂在使用期间暴露于等于或高于用于“转化”NOx排放物的“起燃”温度的温度。
20.根据权利要求17-19中任一项的方法制备的催化剂。
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