CN107847836A - 用于制造具有增强的性能的多孔体的方法 - Google Patents
用于制造具有增强的性能的多孔体的方法 Download PDFInfo
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- CN107847836A CN107847836A CN201680032363.0A CN201680032363A CN107847836A CN 107847836 A CN107847836 A CN 107847836A CN 201680032363 A CN201680032363 A CN 201680032363A CN 107847836 A CN107847836 A CN 107847836A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
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Abstract
用于制备多孔体的前体混合物,其中所述前体混合物包含:(i)具有0.1至6微米的粒径的经研磨的α‑氧化铝粉末,(ii)勃姆石粉末,其用作α‑氧化铝粉末的粘合剂,以及(iii)具有1‑10微米的粒径的燃尽材料。在一些实施方式中,在所述前体混合物中还包括具有10至100微米的粒径的未研磨的α‑氧化铝粉末。本发明还描述了用于制备多孔体的方法,其中上述前体混合物形成给定的成型体并进行热处理步骤,在所述热处理步骤中所形成的成型体被烧结以产生多孔体。
Description
相关申请的交叉引用
本发明要求于2015年6月2日提交的美国临时专利申请No.62/169706和No.62/169766的权益,每个申请的全部内容和公开内容通过引用的方式并入本发明。
技术领域
本发明涉及多孔体,尤其涉及可以在多种应用中使用的多孔体,所述应用包括例如作为过滤器、膜或催化剂载体。
背景技术
在化学工业和化工行业中,经常依赖使用多孔体,包括多孔陶瓷体,它能够执行或促进分离或反应和/或提供用于进行这样的分离和反应的区域。分离或反应的实例包括:气体和液体的过滤、吸附、反渗透、渗析、超滤、或多相催化。虽然这些多孔体的期望的物理和化学性质根据特定的应用而有所变化,但在这些多孔体中存在通常合乎期望的某些性质而不管它们将被使用的最终应用。
例如,多孔体可以是基本上惰性的,使得多孔体本身不参与在它们附近、在它们上或通过它们以不希望的、意外的、或有害的方式进行的分离或反应。在其中希望有穿过多孔体或扩散到多孔体的进行反应或分离的组分的应用中,低扩散阻力(例如,高的有效扩散系数)将是有利的。
在一些应用中,多孔体被设置在反应空间或分离空间中,因此它们具有高孔隙体积和/或高表面积是有利的,以便增大所希望的反应物的装载和分散,并提供在其上能进行反应或分离的增大的表面积。这些应用还需要有足够的机械完整性,以避免在运输或放置过程中受到损坏,即压碎、切损或破裂。然而,因为强度随着孔隙率的增加呈指数下降,在多孔体中高机械强度与高孔隙体积的组合不容易实现。
鉴于上述情况,有必要提供拥有具有增强的流体输送特性特别是气体扩散性质以及高机械完整性的孔结构的多孔体。这样的孔结构可以仅通过本发明中所描述的精确控制多孔体前体混合物和多孔体的制备方法来实现。
发明内容
为了减少多孔体中的缺陷水平,本公开内容涉及用于制备其中这些缺陷可被最小化的多孔陶瓷体的方法。在一些实施方式中,本发明描述的方法提供了具有相当可观的孔隙体积、压碎强度、和/或表面积的多孔体。在其他实施方式中,本发明描述的方法提供具有表现出增强的流体输送特性和高机械完整性的孔结构的多孔体。
本发明的多孔体可以通过首先提供前体混合物来制备,其中所述前体混合物包含:(i)具有0.1至6微米的粒径的经研磨α-氧化铝粉末,(ii)任选地,具有10至100微米的粒径的未研磨的α-氧化铝粉末,(iii)勃姆石粘合剂,优选纳米级的,其中所述勃姆石用作α-氧化铝粉末的粘合剂,(iv)具有1-10微米的粒径的燃尽材料,以及(v)任选地,其它添加剂,例如溶剂和润滑剂。多孔体前体混合物的所有组分均匀混合。
本发明的另一个实施方式涉及用于制备多孔体的方法,其中上述前体混合物形成成型体,并且使形成的成型体进行热处理工艺以除去挥发物(例如,水和燃尽材料)并将所述成型体烧结成多孔体。在具体的实施方式中,制备方法包括:(i)使勃姆石在水中分散,以产生勃姆石的分散体;(ii)将具有0.1至6微米的粒径的经研磨的α-氧化铝粉末加入勃姆石的分散体中,并混合直到获得第一均匀混合物,其中所述勃姆石用作α-氧化铝粉末的粘合剂;(iii)加入具有1至10微米的粒径的燃尽材料,并混合直至获得第二均匀混合物;(iv)形成第二均匀混合物,以形成所述第二均匀混合物的成型体;(v)使所形成的成型体进行在35至900℃的温度范围内的热处理步骤以除去水并燃尽所述燃尽材料以产生预烧制的多孔体;以及(vi)使所述预烧制多孔体进行在900至2000℃的温度范围内的烧结步骤,以产生所述多孔体。
在其它方面,本公开内容还涉及通过上述方法制备的多孔体,以及过滤器、膜、催化剂担体、和类似物,特别是包含上述多孔体(即,载体)以及催化量的银的乙烯氧化(即,环氧化)的催化剂。在一些实施方式中,所得到的环氧化催化剂表现出增强的催化剂活性和/或维持或改善的选择性。
本公开内容还涉及用于通过使用上述催化剂将乙烯气相转化成环氧乙烷(EO)的方法。该方法包括在上述的乙烯环氧化催化剂的存在下使包含乙烯和氧的反应混合物反应。
具体实施方式
在一个方面,本公开内容涉及用于制备多孔体的方法,在其中特制的前体混合物形成为一成型体(shape),并进行热处理步骤,以产生多孔体。在具体的实施方式中,前体混合物至少包括:(i)经研磨的α-氧化铝粉末,其具有0.1至6微米或更典型地0.25至4微米的粒径,(ii)勃姆石粉末,其用作氧化铝粉末α的粘合剂,以及(iii)燃尽材料,其具有1-10微米的粒径。在一些实施方式中,前体混合物还包括具有10至100微米的粒径的未研磨的α-氧化铝粉末,而在其他实施方式中,前体混合物中不包含所述未研磨的α-氧化铝。在其中包含未研磨的α-氧化铝的实施方式中,经研磨的α-氧化铝粉末与未研磨的α-氧化铝粉末的重量比通常是在0.25:1至约5:1的范围内,优选为0.5至4,更优选为,0.75至3。术语“约”通常表示不超过偏离一个数值的±10%,±5%,或±1%。前体混合物还可以包括一种或多种添加剂,如溶剂和/或润滑剂。在一些实施方式中,燃尽材料选自聚烯烃粉末和石墨粉末中的至少一种,或两者。在其中燃尽材料包含聚烯烃和石墨粉末两者的实施方式中,聚烯烃粉末与石墨粉末的重量比通常是在0.25:1至约5:1的范围内,优选在至0.5至4的范围内,并且更优选为0.75至3。通常,勃姆石以占总氧化铝的重量含量的至少10%或25%的量存在。在一些实施方式中,含硅物质基本上从前体混合物中排除。
用于制备多孔体的方法也可以通过在热处理步骤之前至少两个步骤中添加组分来实施。例如,在一些实施方式中,首先制备勃姆石的分散体,即,在步骤(i)中,通过将勃姆石颗粒分散到水中,水可以是中性的水或酸化的水。如本领域中公知的,勃姆石是氢氧化铝氧化物材料,通常被认为是与式γ-AlO(OH)一致。对于本发明的目的,勃姆石颗粒,如在分散体中制备的,优选是纳米级的,例如,达到或小于200纳米(nm),优选小于100nm,并且更优选小于50nm。在酸化水中所用的酸通常为强无机酸,如硝酸、盐酸,或硫酸。所述酸也可以是弱酸,诸如,例如,乙酸。在酸化水中所用的酸可加入中性水或可以从固体颗粒(诸如,例如,勃姆石)溶解。
然后在步骤(ii)将研磨颗粒形式的α-氧化铝加入到勃姆石的分散体中,其中,研磨形式的α-氧化铝通过平均或中值粒径(例如,D50,其中颗粒群的一半低于指示值的粒径)来表征,所述平均或中值粒径的范围为0.1至6微米,并且优选为0.25至4微米。混合勃姆石和经研磨的α-氧化铝的混合物直至获得第一均匀混合物。如本发明中所使用的术语“均匀”表示在该均匀混合物中通常不可检测或不存在混合物(如勃姆石和α-氧化铝)的每种物质的团聚颗粒(即至少为100或200微米)的个别宏观区域,但是团聚颗粒(例如,小于100或200微米)的个别微观区域可以或可以不存在。在均匀混合物中,勃姆石用作α-氧化铝颗粒的粘合剂。在一些实施方式中,α-氧化铝具有非常高的纯度,即约95重量%或98重量%或更高。在一些实施方式中,α-氧化铝是低钠氧化铝或低钠活性氧化铝。如本发明中通常使用的术语“活性氧化铝”表示具有良好的烧结性并具有非常细的粒径(即,一般地,为2微米或更小)的α-氧化铝。一般地,“低钠氧化铝”材料含有0.1%以下的钠含量。良好的烧结性通常源自2微米以下的粒径。
上面给出的粒径可以指其中颗粒是球形的或近似球形的情况下的直径。对于颗粒基本上偏离球形形状的情况,上面给定的粒径基于颗粒的当量直径。如在本领域中已知的,术语“当量直径”用于表示不规则成形的物体的尺寸,其通过以具有与所述不规则成形的物体相同的体积的球体的直径的方式来表示所述物体的尺寸。
在一些实施方式中,步骤(ii)可以包括,在添加和混合经研磨的α-氧化铝粉末的同时或之后,添加具有范围为约10-100微米的D50粒径的未研磨的α-氧化铝粉末,并混合直到获得第一均匀混合物。术语“之后”表示该额外材料(例如,未研磨α-氧化铝)可以被包括在相同的步骤(ii)中或者被包括在成形和烧结步骤(iv)至(ⅵ)之前的后续步骤中。典型地,未研磨的α-氧化铝的D50粒径的范围为10至100微米,并且更优选为25至80微米。
当包括未研磨的α-氧化铝粉末时,获得的第一均匀混合物含有勃姆石、经研磨的α-氧化铝,和未研磨的α-氧化铝的均匀混合物。在一些实施方式中,按总氧化铝的重量计,经研磨的α-氧化铝的重量百分比大于未研磨的α-氧化铝的重量百分比。例如,经研磨和未研磨的α-氧化铝可以以重量比(即,经研磨的氧化铝比未研磨的氧化铝)为约、至少、或大于1.1:1,1.5:1,1.8:1,或2:1,以及达到或小于1.5:1,1.8:1,2:1,或2.5:1存在。在其他实施方式中,按总氧化铝的重量计,未研磨的α-氧化铝的重量百分比大于经研磨的α-氧化铝的重量百分比。例如,未研磨的α-氧化铝和经研磨的α-氧化铝可以以重量比(即,未研磨的氧化铝比经研磨的氧化铝)为至少或大于1.1:1或1.5:1,以及达到或小于1.8:1,2:1或2.5:1存在。在其他实施方式中,经研磨的α-氧化铝比未研磨的α-氧化铝的重量比为约或至少0.25:1或0.5:1和/或约、达到或小于2.5:1或3:1。在一些实施方式中,经研磨的α-氧化铝是在步骤(ii)中使用的仅有的氧化铝,或在所述方法中使用并被掺入多孔体的仅有的氧化铝,即未研磨的α-氧化铝从所述方法中被排除。在其他实施方式中,经研磨的和未研磨的α-氧化铝的组合是在步骤(ii)中使用的仅有的氧化铝,或在所述方法中使用并被掺入多孔体中的仅有的氧化铝。
在一些实施方式中,勃姆石的重量百分比与总氧化铝的重量百分比相比大约相同或更低。例如,勃姆石可以以至少或大于5%或10%的量存在。在一些实施方式中,勃姆石的重量百分比与总氧化铝的重量百分比相比大约相同或更高。例如,按总氧化铝的重量含量计,勃姆石可以以至少或超过25%的量存在。在多孔体前体中的所述方法中使用的总的氧化铝按被掺入多孔体的固体组分的总重量计通常为至少或超过25%或35%。
在步骤(ii)中形成含有勃姆石和α-氧化铝的第一均匀混合物后,将具有1-10微米的粒径的燃尽材料加入并混合到第一均匀混合物,直到获得第二均匀混合物,即,在步骤(iii)中。第二均匀混合物优选包含可以随后形成成型体并烧结的自由流动的颗粒。燃尽材料,其也可以被认为是临时粘合剂,可以是任何本领域中已知的燃尽材料,如粒状聚烯烃(例如,聚乙烯或聚丙烯)、石墨、纤维素、取代的纤维素(例如,甲基纤维素、乙基纤维素和羧乙基纤维)、硬脂酸酯(例如,有机硬脂酸酯,如硬脂酸甲酯或硬脂酸乙酯)、蜡、胡桃壳粉等,其在采用的温度下是可分解的。燃尽材料主要用于赋予多孔体以多孔性,以及确保在未火烧(the green)(即未燃烧阶段)期间保持多孔结构,在该期间所述混合物可通过模塑或挤压工艺被制成颗粒。在所述燃烧期间,燃尽材料通常被基本上或完全除去,以产生所述成品多孔体。在不同的实施方式中,燃尽材料的粒径的范围可为大约,例如,1-10微米,优选1-9微米,更优选1.5-8微米。
在特定的实施方式中,在步骤(iii)中使用的燃尽材料是粒状聚烯烃(例如,聚乙烯),或石墨粉末,或两者。如果使用聚烯烃和石墨两者,它们可以具有相同或不同的粒径,并且它们可以同时或顺序地加入。例如,在一些实施方式中,加入粒状聚烯烃并混合直到获得第二均匀混合物之后,可以随后加入石墨,其中术语“随后”或“顺序地”表示该额外的材料可以包含在相同的步骤(iii)中或者被包含在形成和烧结步骤(iv)至(vi)之前的后续步骤中。在一些实施方式中,按重量计包含的粒状聚烯烃的量大于石墨的量。例如,粒状聚烯烃与石墨的重量比可为0.25:1至约5:1,优选0.75至约3.5。在其他实施方式中,按重量计包含的粒状聚烯烃的量小于石墨的量。例如,石墨与粒状聚烯烃的重量比可为0.25:1至约5:1,优选为1至约2.5。
在一个实施方式中,步骤(i)、(ii)和(iii)是分开并相继进行的,即在步骤(i)中制备勃姆石的分散体,随后在步骤(ii)中制备第一均匀混合物,随后在步骤(iii)中制备第二均匀混合物。步骤(i)、(ii)和(ⅲ)也可反向或以随机顺序进行。在另一个实施方式中,步骤(i)和(ii)可以合并为单一步骤,即勃姆石和氧化铝在酸化水存在下合并以形成勃姆石和氧化铝的分散体,其用作为第一均匀混合物。在又一个实施方式中,步骤(ii)和(iii)可以被合并为单一步骤,即,在制备第一均匀混合物的过程中合并氧化铝和燃尽材料,现在第一均匀混合物也用作第二均匀混合物。在进一步的实施方式中,步骤(i)、(ii)和(iii)可以合并为单一步骤,即勃姆石、氧化铝和燃尽材料可以在酸化水的存在下合并以形成勃姆石、氧化铝和燃尽材料的分散体,其用作为第二均匀混合物。
在一些实施方式中,所述方法还包括(在形成和烧结所述第二均匀混合物之前的任何步骤中)足量的粘合剂材料。永久粘合剂包括,例如,无机粘土型材料,例如二氧化硅和碱金属化合物或碱土金属化合物。可以掺入氧化铝颗粒的方便的粘合剂材料包括勃姆石,稳定的二氧化硅溶胶和任选的碱金属盐或碱土金属盐。在一些实施方式中,用于制备多孔体的方法基本上或完全不含有含硅物质。在多孔体中基本上不包括含硅物质的情况下,来源于用于制备多孔体的原料中的杂质的痕量的硅仍然可以存在于该多孔体中。这样的痕量通常不超过多孔体重量的1%、0.5%、或0.1%。
前体混合物,或在步骤(iii)中形成的所述第二均匀混合物,然后通过本领域公知的方法形成为期望的成型体。形成过程可以通过挤压、压制、制丸、模塑、浇铸等来进行。成形后,所形成的成型体进行热处理步骤,其中它被烧结,以产生多孔体。烧结过程通常使用在约900℃至约2000℃的范围内的温度。烧结步骤也必然起作用以除去诸如水和燃尽材料之类的挥发物。然而,在一些实施方式中,在烧结步骤之前进行的前述较低温度的热处理(在本发明中称为“预烧结步骤”)是为了除去这些挥发物。前述较低温度的热处理通常采用约35℃至约900℃的温度。通常地,使用在0.5-100℃/分钟的范围内,优选1-20℃/分钟,或更优选2-5℃/分钟的加热和/或冷却速率。
为了正确地表征用于过滤器、膜或催化剂载体应用的多孔体,必须确定孔结构以及后续流体输送相关的性质。
曲折度和收缩率是确定输送通过多孔体的扩散气体的非常重要的参数。曲折度由通过多孔体的流动路径的实际长度与穿过多孔体的最短距离的比率来确定(参见,例如,B.Ghanbarian等,Soil Sci.Soc.Am.J.,77,1461-1477(2013))。收缩率与大孔与小孔的面积比呈函数关系。因此,减小曲折度和/或收缩率的值增强了通过多孔材料的扩散输送,即,增大了有效扩散系数,有效扩散率在例如催化应用中是非常重要的。
如果存在跨越多孔体的压降,那么渗透率变得很重要。渗透率表示流体流动穿过多孔体的能力,并且可以通过在式1中所示的达西定律来描述,其中V是流体流速,k是渗透率,μ是流体的动态粘度,ΔP是跨越具有厚度Δx的多孔体的压力差:
因此,较高值的渗透率将增强压力驱动的流体流过多孔体,这在例如吸附、过滤或催化之类的这些应用中是重要的。
令人惊讶地,在文献中没有发现多孔体的上述流体输送决定性质以表征多孔结构,特别是与用于烯烃环氧化的催化剂载体相关的性质。此外,文献中没有指示为能实现增强的性能(特别是关于催化剂性能)的多孔体提供多孔结构的曲折度、收缩率或渗透率的必要的值。本发明提供了拥有具有增强的流体输送特性和高机械完整性的孔结构的多孔体。
除非另有规定,本发明中采用下列测量方法:
在本发明中,多孔体的吸水率通过以下步骤进行测定:将10g多孔体的代表性样品放入烧瓶中,然后抽真空至约0.1托持续5分钟。然后,在保持压力为约0.1托时,使去离子水被吸入抽空的烧瓶以覆盖多孔体。在约5分钟后,将真空释放,恢复环境压强,加速使水完全渗透到孔隙中。随后,将过量的水从该浸渍的样品排出。吸水率通过将孔隙中水的总重量(即,样品的湿质量-样品的干质量)除以在室温下的干样品的重量来计算。
通过汞(Hg)孔隙率测定法(mercury(Hg)intrusion porosimetry)获得多孔体的代表性样本的累积侵入曲线和对数微分侵入曲线,在Lowell等,Characterization ofPorous Solids and Powders:Surface Area,Pore Size and Density,Springer,2006中描述了汞孔隙率测定法的原理。Hg侵入压强的范围为例如介于1.5和60,000psi之间,其对应于介于140微米和3.6纳米之间的孔隙大小。下面Hg参数被用于计算:480达因/厘米的表面张力、13.53克/毫升的密度、和140°的接触角。根据汞侵入数据测量多孔体的孔隙体积,汞侵入数据与吸水率测量结果一致。多孔体的另外的孔结构参数,如曲折度、收缩率和渗透率,也可根据汞侵入数据来计算,如下所述。
曲折度ξ根据式2计算,其中Davg是加权平均孔径,k为渗透率,ρ是真实材料密度,Itot是总的比侵入量(见,例如,AutoPore V Operator Manual,Micromeritics,2014):
收缩率,σ,根据式3计算,其中ξ是曲折度,τ是曲折度因子,根据Carnigilia公式算出(参见,例如,AutoPore V Operator Manual,Micromeritics,2014):
渗透率,由达西定律(公式1,上文)所定义的,可以通过组合达西公式和泊肃叶(Poiseuille)公式计算(参见,例如,Lowell et al.,Characterization of PorousSolids and Powders,Springer,2006)。对于任意孔隙形状因子f,渗透率k由式4表达,其中τ是曲折度因子,P为材料的孔隙率,d为孔径:
一旦曲折度和孔隙体积被测量,有效扩散系数可以从公式5计算出,其中P是材料的孔隙率,D是扩散系数,Deff是有效扩散系数,并且ξ是曲折度[D.W.Green,R.H.Perry,Perry’s Engineering Handbook,8th Edition,McGraw-Hill,2007]
为了计算多孔固体中的有效扩散系数的绝对值Deff,根据公式5除了材料的孔隙率和曲折度以外还必须知道气体扩散系数的绝对值D。然而,为了比较不同的多孔固体(例如,本发明的发明实施例)的有效扩散性能,可以计算归一化成标准材料(本发明的比较例)的有效扩散系数的相对量。假设气体扩散系数D在所有情况下是相同的,仅需要知道多孔材料的孔隙率和曲折度即可(见式6)。
总孔隙率被定义为空隙容积除以样品的总体积。它可以根据汞孔隙率测定法或吸水率,使用载体材料的理论密度进行计算。
本发明的多孔体通常具有0.3mL/g至1.2mL/g的孔隙体积。更典型地,本发明的多孔体具有0.35mL/g至0.9mL/g的孔隙体积。在本发明的一些实施方式中,本发明的多孔体的吸水率为30%至120%,更典型地在35%至90%的范围内。
本发明的多孔体通常具有0.3m2/g至3.0m2/g的B.E.T.表面积。在一个实施方式中,本发明的多孔体具有0.5m2/g至1.2m2/g的表面积。在另一个实施方式中,本发明的多孔体具有1.2m2/g以上至高达并包括3.0m2/g的表面积。本发明描述的B.E.T.表面积可通过任意适当的方法测量,但是更优选通过在Brunauer,S.,等,J.Am.Chem.Soc.,60,309-16(1938)中描述的方法获得。
本发明的多孔体可以是单模态或多模态的,诸如,例如,双模态的。本发明的多孔体具有在0.01微米至100微米的范围内的具有孔的至少一个模态的孔径分布。在本发明的一个实施方式中,多孔体的至少90%的孔隙体积归因于具有20微米以下孔径的孔。在本发明的另一个实施方式中,多孔体的至少85%的孔隙体积归因于具有1微米至6微米的尺寸的孔。在本发明的进一步的实施方式中,多孔体的小于15%(优选小于10%)的孔隙体积归因于具有小于1微米的尺寸的孔。在本发明的又一个进一步的实施方式中,多孔体的至少80%的孔隙体积归因于具有1微米至10微米的尺寸的孔。在本发明的一个具体的方面,基本上不存在小于1微米的孔。
在多模态孔径分布的情况下,每一孔径分布可以单一平均孔径(平均孔径)数值进行表征。因此,针对孔径分布给出的平均孔径数值必须对应于产生所指示的平均孔径数值的孔径范围。在上面提供的任意示例的孔径可替代地被理解为指示孔径平均值(即,平均值或加权平均值)。每一峰值孔径可被认为是在其自身孔径分布(模态(mode))之内,即,(实际上或理论上)在所述分布的每一侧边上的孔径浓度下降至约0的情况。所述多模态孔径分布可以是,例如,双模态的,三模态的,或更多模态的。在一个实施方式中,各自具有峰值孔径的不同的孔径分布通过被大约零的孔隙浓度分隔开而不相重叠(即在基线)。在另一实施方式中,各自具有峰值孔径的不同的孔径分布通过未被大约零的孔隙浓度分隔开而重叠。
在一个实施方式中,本发明的多孔体可以是双模态的,具有0.01微米至1微米的第一组孔和从大于1微米至10微米的第二组孔。在这样的实施例中,第一组孔可以构成多孔体的小于15%的总孔隙体积,而第二组孔可以构成多孔体的85%以上的总孔隙体积。在另一个实施方式中,第一组孔可以构成多孔体的小于10%的总孔隙体积,而第二组孔可构成多孔体的90%以上的总孔隙体积。
本发明的多孔体通常具有55%至83%的总孔隙率。更典型地,本发明的多孔体具有58%至78%的总孔隙率。
本发明的多孔体通常具有10N至150N的平均平板压碎强度。更典型地,本发明的多孔体具40N至105N的平均平板压碎强度。使用用于所形成的催化剂和催化剂载体的单粒团(pellet)压碎强度的标准测试方法(ASTM标准ASTM D4179)测量该多孔体的平板压碎强度。
在一些实施方式中,本发明的多孔体可以具有小于40%,优选小于25%的磨损值。在本发明的一些实施方式,多孔体可具有小于10%的磨损。使用用于催化剂和催化剂载体的磨损和磨耗的标准测试方法(ASTM标准ASTM D4058)进行多孔体的磨损测量。
在本发明的一些实施方式,本发明的多孔体具有初始的低碱金属含量。“低碱金属含量”是指多孔体在其中含有2000ppm以下的、典型地为30ppm至300ppm的碱金属。包含低碱金属含量的多孔体可以通过在多孔体的制造过程中基本上不加入碱金属来获得。“基本上不加入碱金属”是指在多孔体的制造过程中使用仅痕量的碱金属作为来自多孔体的其他成分的杂质。在另一个实施方式中,可以通过对在形成多孔体中所用的多孔体前体材料执行各种洗涤步骤得到具有低碱金属含量的多孔体。该洗涤步骤可包括在碱、水或酸中洗涤。
在本发明的其他实施方式中,该多孔体具有大于上面针对基本上无碱金属含量的多孔体所述的值的碱金属含量。在这样的实施方式中,多孔体通常在其表面上含有可测量水平的钠。在载体的表面上的钠浓度将根据多孔体的不同组分中的钠水平以及其煅烧的细节而有所变化。在本发明的一个实施方式中,相对于多孔体的总质量,多孔体具有2ppm至150ppm的表面钠含量。在本发明的另一个实施方式中,相对于载体的总质量,多孔体具5ppm至70ppm的表面钠含量。上面所述的钠含量表示在载体的表面获得的以及可以被沥滤(即通过例如硝酸除去)的钠(以下称为酸沥滤性钠)含量。
在本发明的多孔体中存在的酸沥滤性钠的量可以在100℃下用去离子水中的10%的硝酸从催化剂或载体中提取。提取方法包括通过使10克的催化剂或载体样品与一份100毫升的10重量%的硝酸煮沸持续30分钟(1个大气压,即101.3kPa)来提取它,并通过使用例如原子吸收光谱(参见例如,美国专利No.5,801,259和美国专利申请公开No.2014/0100379A1)之类的已知方法确定在合并的提取物中相关的金属。
在本发明的一个实施方式中,多孔体可具有的二氧化硅含量以SiO2计量可以为小于0.2重量%,优选小于0.1重量%;以及钠含量,以Na2O计量,可以为小于0.2重量%,优选小于0.1重量%。在一些实施方式中,本发明的多孔体可以具有40ppm或40ppm以下的酸沥滤性钠含量。在本发明的又一实施方式中,多孔体包括按体积计小于20%的含量的具有片状形态的氧化铝微晶。在一些实施方式中,本发明的多孔体中存在按体积计小于10%的含量的具有片状形态的氧化铝微晶。
除了上述物理性质以外,本发明的多孔体具有提供7或7以下的曲折度、4或4以下的收缩率和30毫达西或30毫达西以上的渗透率中的至少一种的孔结构。具有上述孔结构的多孔体具有增强的流体输送特性和高的机械完整性。在一些实施方式中,以及当具有上述孔结构的多孔体用作银基环氧化催化剂的载体时,其可以显示出改进的催化剂性能。通常情况下,本发明的多孔体的孔结构具有7或7以下的曲折度和/或4或4以下的收缩率。
在本发明的一个实施方式中,多孔体具有可提供7或7以下的曲折度的孔结构。在另一个实施方式中,本发明的多孔体具有可提供6或6以下的曲折度的孔结构。在又一个实施方式中,本发明的多孔体具有可提供5或5以下的曲折度的孔结构。在进一步的实施方式中,本发明的多孔体具有可提供3或3以下的曲折度的孔结构。本发明的多孔体的曲折度的下限为1(理论极限)。在一些实施方式中,曲折度可以是介于1和7之间的范围内的任何数值。
在本发明的一个实施方式中,该多孔体具有可提供4或4以下的收缩率的孔结构。在另一个实施方式中,本发明的多孔体具有可提供3或3以下,或甚至2或2以下的收缩率的孔结构。本发明的多孔体的收缩率的下限为1。在一些实施方式中,收缩率可以是介于1和4之间的范围内的任何数值。
在本发明的另一个实施方式中,由于低曲折度和高孔隙率的结合,多孔体的有效气体扩散系数提高2-4倍。
在一个实施方式中,本发明的多孔体具有提供30毫达西以上的渗透率的孔结构。在另一个实施方式中,本发明的多孔体具有提供200毫达西以上的渗透率的孔结构。
所述多孔体可具有任何适当的形状和形态。例如,所述载体可以是颗粒、厚块(chunk)、丸状、环状、球体状、三孔的、汽车车轮状、横向分割的空心圆柱体等等形式,具有优选适合在固定床反应器中应用的尺寸。
在一个实施方式中,多孔体基本上仅包含氧化铝,或氧化铝和勃姆石组分,除了可以存在痕量的其它金属或化合物以外,不存在其他金属或化合物。痕量是痕量物质不显著影响随即制备的催化剂的功能或能力的足够低的量。
在本发明的一个实施方式中,上述的多孔体可以用作催化剂载体(即,催化剂担体),在这种情况中它通常包含布置在多孔体上和/或在多孔体中的一种或多种催化活性材料,典型地为金属。所述一种或多种催化活性材料能够催化特定的反应并在本领域中是公知的。在一些实施方式中,催化活性材料包括来自元素周期表的第3-14族的一种或多种过渡金属和/或镧系元素。在这样的应用中,一种或多种促进物质(即,促进特定的反应的物质)也可以设置在本发明的多孔体上和/或在本发明的多孔体中。一种或多种促进物质可以是,例如,碱金属、碱土金属、过渡金属、和/或来自元素周期表第15-17族的元素。
在多孔体被用作银基环氧化催化剂的载体的具体情况下,所述载体包括在多孔体上和/或在多孔体的中的银。因此,在上述方法中,通常在烧结步骤之后,通过本领域中公知的方法将银掺入在载体上或载体中,所述公知的方法为例如通过银盐浸渍随后如本领域中公知的热处理,如描述于例如美国专利No.4,761,394、No.4,766,105、No.4,908,343、No.5,057,481、No.5,187,140、No.5,102,848、No.5,011,807、No.5,099,041和No.5,407,888中,其全部内容通过引用方式并入本发明中。在所述溶液中银盐的浓度典型地是在约0.1重量%至在所使用的增溶剂中具体银盐的溶解度所允许的最大值的范围内。更典型地,银盐的浓度为按银的重量计约0.5%至按银的重量计45%,甚至更典型地,按银的重量计约5%至按银的重量计35%。前述的量通常也是在热处理后的催化剂中发现的按重量计的量。为适合作为乙烯环氧化催化剂,银的量应该是用于乙烯环氧化的催化有效量,其可以是上述提供的任何量。
除了银,本发明的银基环氧化催化剂还可包含促进量的任何一或多种促进物质。一或多种促进物质可以在银的沉积之前、同时、或之后掺入上述多孔体中。正如本发明所采用的,催化剂的某种成分的“促进量”是指在与不含所述成分的催化剂相比时,该成分的量可有效地提供对所述催化剂的一或多种催化性质的改进。
例如,银基环氧化催化剂可以包括促进量的第1族碱金属或两种以上第1族碱金属的混合物。适当的第1族碱金属促进剂包括,例如,锂、钠、钾、铷、铯或其组合。铯通常是优选的,铯与其他碱金属的组合也是优选的。以总催化剂的重量计,以碱金属表示的碱金属的量的范围典型地为约10ppm至约3000ppm,更典型地为约15ppm至约2000ppm,更典型地为约20ppm至约1500ppm,和甚至更典型地为约50ppm至约1000ppm。
银基环氧化催化剂还可包括促进量的第2族碱土金属或两种以上第2族碱土金属的混合物。适当的碱土金属促进剂包括,例如铍、镁、钙、锶、和钡或其组合。采用的碱土金属促进剂的量类似于上述碱金属促进剂的量。
银基环氧化催化剂还可包括促进量的主族元素或两种以上主族元素的混合物。适当的主族元素包括元素周期表的第13族(硼族)至第17族(卤素族)中的任意元素。在一个实施例中,可以使用促进量的一种或多种硫化合物、一种或多种磷化合物、一种或多种硼化合物或其组合。
银基环氧化催化剂还可以包括促进量的过渡金属或两种以上过渡金属的混合物。适当的过渡金属可以包括例如来自元素周期表的第3族(钪族)、第4族(钛族)、第5族(钒族)、第6族(铬族)、第7族(锰族)、第8-10族(铁、钴、镍族)、和第11族(铜族)的元素,以及它们的组合。更典型地,过渡金属是选自元素周期表的第3族、第4族、第5族、第6族或第7族的前过渡金属,诸如,例如,铪、钇、钼、钨、铼、铬、钛、锆、钒、钽、铌、或它们的组合。
在本发明的一个实施方式中,银基环氧化催化剂包括银、铯和铼。在本发明的另一个实施方式中,银基环氧化催化剂包括银、铯、铼和选自Li、K、W、Zn、Mo、Mn、和S中的一种或多种物质。
该银基环氧化催化剂还可以包括促进量的稀土金属或两种以上稀土金属的混合物。稀土金属包括具有原子序数为57-71的任何元素,钇(Y)和钪(Sc)。这些元素的一些实例包括镧(La)、铈(Ce)和钐(Sm)。
过渡金属或稀土金属促进剂通常存在的量以所述金属表示,为每克总催化剂含有约0.1微摩尔至约10微摩尔,更典型地每克总催化剂含有约0.2微摩尔至约5微摩尔,和甚至更典型地每克总催化剂含有约0.5微摩尔至约4微摩尔。所有上述促进剂,包括所述碱金属,可以是任何适当的形式,包括例如零价金属或更高价的金属离子。
银基环氧化催化剂也可包括一定量的铼(Re),其被认为是用于乙烯环氧化的高选择性催化剂的特别有效的促进剂。催化剂中的铼成分可以是任何适当的形式,但是更通常为一种或多种含铼化合物(例如,氧化铼)或络合物。基于包括担体的总催化剂的重量,以铼金属表示的铼存在的量可以为例如,约0.001重量%至约1重量%。更典型地,铼存在的量可以为例如约0.005重量%至约0.5重量%,并且甚至更典型地,约0.01重量%至约0.05重量%。所有这些促进剂,包括所述碱金属,可以是任何适当的形式,包括例如零价金属或更高价的金属离子。
在用银和任意促进剂浸渍之后,从所述溶液移除经浸渍的载体,并煅烧一定时间,以充分将所述银成分还原成金属银,以及从所述含银担体移除挥发性分解产物。典型地通过加热经浸渍的载体实现所述煅烧,其是优选在约0.5至约35巴的反应压强下以逐渐增大的速率加热至约200℃至约600℃的范围内的温度(更典型地约200℃至约500℃的范围内的温度,更典型地约250℃至约500℃的范围内的温度,更典型地约200℃或300℃至约450℃的范围内的温度)来实施。一般而言,温度越高,所需的煅烧持续时间越短。本领域中已经描述了用于所述经浸渍担体的热处理的宽范围的加热持续时间。可参考例如美国专利US 3,563,914和US 3,702,259,其中在US 3,563,914中表明了加热少于300秒;在US 3,702,259中公开了在100℃至375℃的温度加热2-8小时,以还原在所述催化剂中的银盐。为此,可采用连续或逐步加热方案。在煅烧期间,典型地使所述经浸渍的担体暴露于包含惰性气体(诸如氮气)的气氛。惰性气体也可包括还原剂。
在另一个实施方式中,上述多孔体,也可以用作过滤器,其中液体或气体分子可以通过上述的多孔体的孔扩散。在这样的应用中,多孔体可以沿着液体或气体流的任何部分放置。在本发明的另一个实施方式中,上述的多孔体可以用作膜。
在另一方面,本发明涉及用于通过在氧的存在下使用上述银基环氧化催化剂将乙烯转化成环氧乙烷来进行气相制备环氧乙烷的方法。通常,所述环氧乙烷制备方法通过以下实施:在所述催化剂的存在下、在约180℃至约330℃的温度(更典型的约200℃至约325℃,更典型的约225℃至约270℃)、在可根据所期望的质量流速和生产率在约大气压至约30个大气压的范围内变化的压强下使含氧气体连续接触乙烯。通常采用在约大气压至约500psi范围内的压强。然而,在本发明范围内可采用更高的压强。在大型反应器中的停留时间通常近似于约0.1至约5秒。用于将乙烯氧化成环氧乙烷的典型方法包括利用分子氧、在本发明的催化剂存在于固定床管式反应器中的情况下气相氧化乙烯。传统商购的固定床环氧乙烷反应器典型地为(在适当的壳体内的)多个平行细长管的形式。在一实施方式中,所述管的外径(O.D.)为大约0.7至2.7英寸,内径(I.D.)为大约0.5至2.5英寸,长15-45英尺,并填充有催化剂。
在一些实施方式中,上述银基环氧化催化剂在用分子氧将乙烯氧化成环氧乙烷中显示出高度的选择性。例如,可达到至少约83摩尔%至高达约93摩尔%的选择性值。在一些实施方式中,选择性为约87摩尔%至约93摩尔%。用于在如上所述的银基环氧化催化剂的存在下进行这样的氧化反应的条件大体上包括那些在现有技术中描述的条件。这适用于例如合适的温度、压强、停留时间,稀释材料(例如,氮气、二氧化碳、蒸汽(stream)、氩气和甲烷),存在或不存在调控催化作用的减速剂(moderating agent)(例如,1,2-二氯乙烷、氯乙烯或氯乙烷),采用循环操作或在不同的反应器中应用连续的转化以增加环氧乙烷的产率的可取性,以及任何其它的可在制备环氧乙烷的工艺中选择的特殊条件。
在环氧乙烷的制备中,反应物进料混合物通常包含约0.5%至约45%的乙烯和约3%至约15%的氧气,余量包含相对惰性物质,相对惰性物质包括诸如氮气、二氧化碳、甲烷、乙烷、氩气等物质。在每次通过催化剂时典型地仅一部分乙烯发生反应。在分离所期望的环氧乙烷产物以及移除适当的清除气流和二氧化碳以便防止惰性产物和/或副产物不受控制地积聚之后,未反应的材料典型地被送回至氧化反应器。
为了进一步举例说明本发明,已在下文中阐明实施例。在本发明中阐述的实施例不应以任何方式限制本发明的范围。
实施例
基于氧化铝的多孔担体的制备与表征
本发明的多孔体的前体混合物的典型的组成示于表1。本发明的多孔体在不断搅拌的情况下通过下列步骤典型地制备:(i)在水中分散勃姆石;(ii)添加经研磨和/或未研磨的α-氧化铝粉末;(iii)加入燃尽物1,如果有的话;(iv)加入燃尽物2,如果有的话;以及(v)加入润滑剂。本发明的各前体混合物的特定数量和类型的单个成分示于表1中。随后,将混合物用具有单一模具的2”Bonnot挤压机挤出,产生中空圆柱体形状的挤出物。将挤出物切成相等长度的段,然后在热灯下干燥1小时。随后,经切割和干燥的挤出物被转移到炉中,进行以下的热处理:(i)在800℃下在流动的空气中进行燃尽物的热解,持续16小时,采用23℃/小时的平均加热速度;接着(ii)在1250-1550℃下烧结12小时,采用2.0℃/分钟的加热速度和冷却速度。
下面的组合物被制备和分析,并且结果被提供在下面的表中:
表1.多孔体前体的组合物的范围
表2.不同多孔体的特性比较
尽管已经显示并描述了目前认为是本发明的优选实施方式,但是本领域技术人员应认识的是在不背离本申请所描述的发明的精神和范围的前提下可进行其它的和进一步的实施方式,并且本申请包括落入如本发明所述的权利要求书规定的范围内的所有这样的实施方式。
Claims (38)
1.一种用于制备多孔体的前体混合物,其中所述前体混合物包含:(i)至少一种具有0.1至6微米的粒径的经研磨的α-氧化铝粉末,(ii)勃姆石粉末,其用作α-氧化铝粉末的粘合剂,以及(iii)至少一种具有1至10微米的粒径的燃尽材料。
2.如权利要求1所述的前体混合物,其还包含具有10至100微米的粒径的未研磨的α-氧化铝粉末。
3.如权利要求2所述的前体混合物,其中,经研磨的α-氧化铝粉末与未研磨的α-氧化铝粉末的重量比在0.25:1至约5:1的范围内。
4.如权利要求1所述的前体混合物,其中,所述前体混合物中不含有未研磨的α-氧化铝粉末。
5.如权利要求1所述的前体混合物,其还包含选自溶剂和润滑剂的添加剂。
6.如权利要求1所述的前体混合物,其中,所述燃尽材料选自聚烯烃粉末和石墨粉末中的至少一种。
7.如权利要求1所述的前体混合物,其中,所述燃尽材料选自聚烯烃粉末和石墨粉末两者。
8.如权利要求7所述的前体混合物,其中,所述聚烯烃粉末与石墨粉末的重量比在0.25:1至约5:1的范围内。
9.如权利要求1所述的前体混合物,其中,所述勃姆石以按总氧化铝的重量含量计至少10%的量存在。
10.如权利要求1所述的前体混合物,其中,所述勃姆石以按总氧化铝的重量含量计至少25%的量存在。
11.如权利要求1所述的前体混合物,其中,所述勃姆石是具有分散粒径<100纳米的纳米级粉末。
12.如权利要求1所述的前体混合物,其中,所述经研磨的α-氧化铝粉末具有0.25至4微米的颗粒/微晶尺寸。
13.如权利要求1所述的前体混合物,其中,所述前体混合物基本上不含有含硅物质。
14.如权利要求1所述的前体混合物,其中,所述前体混合物基本上不含有含钠物质。
15.一种用于制备多孔体的方法,所述方法包括:
提供前体混合物,所述前体混合物包含(i)具有0.1至6微米的粒径的经研磨的α-氧化铝粉末,(ii)勃姆石粉末,其用作α-氧化铝粉末的粘合剂,以及(iii)具有1至10微米的粒径的燃尽材料;
形成预定的成型体;以及
使所述成型体进行热处理步骤,在所述热处理步骤中所述成型体被烧结以产生所述多孔体。
16.如权利要求15所述的方法,其还包括在所述前体混合物中具有10至100微米的粒径的未研磨的α-氧化铝粉末。
17.如权利要求16所述的方法,其中,经研磨的α-氧化铝粉末与未研磨的α-氧化铝粉末的重量比在0.25:1至约5:1的范围内。
18.如权利要求15所述的方法,其中,所述前体混合物中不含有未研磨的α-氧化铝粉末。
19.如权利要求15所述的方法,其中所述方法包括:
(i)将勃姆石分散在水中,以产生勃姆石的分散体;
(ii)加入具有0.1至6微米的粒径的经研磨的α-氧化铝粉末至勃姆石的分散体中,并混合直到获得第一均匀混合物,其中所述勃姆石用作α-氧化铝粉末的粘合剂;
(iii)加入具有1-10微米的粒径的燃尽材料,并混合直至获得第二均匀混合物;
(iv)形成第二均匀混合物,以形成所述第二均匀混合物的成型体;以及
(v)使所形成的成型体进行热处理步骤,在所述热处理步骤中所形成的成型体被烧结以产生所述多孔体。
20.如权利要求15的方法,其中所述热处理步骤包括:
(a)使所形成的成型体进行在35-900℃温度范围内的热处理步骤,以除去水和使燃尽材料燃尽以产生预烧制的多孔体;以及
(b)使所述预烧制的多孔体进行在900-2000℃温度范围内的烧结步骤以产生所述多孔体。
21.如权利要求15所述的方法,其中,所述多孔体具有至少30%的吸水率、至少40N的压碎强度,和至少0.3m2/g的BET表面积中的至少一种。
22.如权利要求15所述的方法,其中,所述多孔体具有提供7或7以下的曲折度、4或4以下的收缩率和30毫达西或30毫达西以上的渗透率中的至少一种的孔结构。
23.如权利要求15所述的方法,其中,所述燃尽材料选自聚烯烃粉末和石墨粉末。
24.如权利要求19所述的方法,其中,所述燃尽材料包括聚烯烃粉末,且所述步骤(iii)包括加入具有1至10微米的粒径的聚烯烃粉末,并混合直至获得第二均匀混合物。
25.如权利要求24所述的方法,其中,所述步骤(iii)还包括,在添加和混合所述聚烯烃粉末同时或之后,添加石墨粉末作为额外的燃尽材料,并混合直至获得所述第二均匀混合物,所述第二均匀混合物包括所述石墨粉末。
26.如权利要求25所述的方法,其中,聚烯烃粉末与石墨粉末的重量比在0.25:1至约5:1的范围内。
27.如权利要求25所述的方法,其中,所述石墨粉末具有3至10微米的粒径。
28.如权利要求19所述的方法,其中所述步骤(ii)包括,在添加和混合经研磨的α-氧化铝粉末的同时或之后,加入具有10-100微米的粒径的未研磨的α-氧化铝粉末,并混合直到获得所述第一均匀混合物。
29.如权利要求28所述的方法,其中,经研磨的α-氧化铝粉末与未研磨的α-氧化铝粉末的重量比在0.25:1至约5:1的范围内。
30.如权利要求15所述的方法,其中,所述勃姆石以按总氧化铝的重量含量计至少10%的量存在。
31.如权利要求15所述的方法,其中,所述勃姆石以按总氧化铝的重量含量计至少25%的量存在。
32.如权利要求15所述的方法,其中,所述勃姆石是具有分散粒径小于100纳米的纳米级粉末。
33.如权利要求15所述的方法,其中,产生所述多孔体的方法排除未研磨的α-氧化铝粉末。
34.如权利要求15所述的方法,其中,产生所述多孔体的方法基本上排除含硅物质。
35.如权利要求15所述的方法,其中,所述前体混合物基本上不含有含钠物质。
36.如权利要求15所述的方法,其中,所述方法还包括在形成所述多孔体的所述热处理步骤之后,在所述多孔体上和/或在所述多孔体中沉积银。
37.如权利要求15所述的方法,其中,所述经研磨的α-氧化铝粉末具有0.25至4微米的粒径。
38.如权利要求15所述的方法,其中,所述前体混合物通过挤压或压制中的一种形成。
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