CN111295243A - 由烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃的方法 - Google Patents

由烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃的方法 Download PDF

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CN111295243A
CN111295243A CN201880070435.XA CN201880070435A CN111295243A CN 111295243 A CN111295243 A CN 111295243A CN 201880070435 A CN201880070435 A CN 201880070435A CN 111295243 A CN111295243 A CN 111295243A
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catalyst
zeolite
group
metal
salt
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CN111295243B (zh
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C·瓦塔娜科
T·友赛雷卡
A·斯娃赛斯
W·万纳帕克德
P·杜克胡特德
D·苏提帕
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PTT Global Chemical PCL
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Abstract

本发明涉及由具有2至5个碳原子的烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃的方法，其中所述催化剂包括分层沸石纳米片，分层沸石纳米片具有大于120的硅土与矾土(SiO2/Al2O3)比和以重量计0.3％至5％的范围内的X族金属。根据本发明的催化剂提供了前体到产品的转化率和高的烯烃选择性。

Description

由烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃 的方法
技术领域
本发明涉及由烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃的方法。
发明内容
本发明涉及用于由具有2至5个碳原子的烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃的方法，其中所述催化剂包括分层沸石纳米片，分层沸石纳米片具有大于120的硅土与矾土(SiO2/Al2O3)比和以重量计0.3％至5％的范围内的X族金属。
背景技术
众所周知，烯烃(比如丙烯)可以由数种方法(比如丁烷和乙烷的复分解、甲醇转化到烯烃的反应以及烃化合物的分解)制备。然而，由于非复杂的方法和成本竞争力，由烷烃的氢化生产烯烃的方法已被广泛使用。
迄今为止，已有由丙烷氢化生产丙烯的技术的报道，比如来自CB&I Lummus的Catofin processTM(WO1995023123和US5315056)。这种工艺技术使用了在平行固定床反应器中在载体上含有铬金属的矾土催化剂。另外，如在专利文件US8563793中公开的，来自UOP的Oleflex processTM利用在流化床反应器中在载体上包含铂金属和锡的矾土催化剂。
除了上述技术之外，还公开了来自UHDE的STAR(蒸汽活性重整)processTM(US4926005)，其使用了在固定床反应器中包含铂金属和锡的铝酸锌催化剂，以及铝酸钙或铝酸镁作为粘合剂。然而，铬金属被归类为重金属和环境毒物，导致在工业上的应用限制。因此，已经不断尝试开发包含其他金属(尤其是铂金属和锡)的催化剂，以有效用于烯烃生产中烷烃的脱氢。
然而，已经发现丙烯选择性和催化剂的快速分解的局限。这是因为对脱氢具有低反应性的金属烧结会引起不期望的反应，比如裂化反应和焦炭形成。此外，使用矾土作为催化剂载体导致不期望的反应和副产物(比如甲烷和乙烷)。
由于上述所有原因，已经尝试应用沸石作为贵金属的载体，因为沸石具有若干良好的性质，比如化学和热稳定性以及形状选择性。因此，沸石已经广泛用作石油和石化工业中的催化剂。然而，因为传质的局限和沸石结构中非常小的孔(埃单位)，常规沸石具有若干局限，比如其酸性增强裂化反应和快速分解。这导致阻碍前体在催化位点处反应的临界传质条件，并且由于阻塞沸石孔的焦炭积聚而增强了催化剂的分解。此外，常规沸石是大沸石晶体，当用作用于贵金属的载体时，可减慢那些贵金属的反应性；因此降低催化效率。
Liu Hui等人(China Petroleum Processing and Petrochemical Technology，2013，15，54-62)公开了包含铂金属、锡和钠的ZSM-5沸石催化剂(PtSnNa/ZSM-5)，通过研究金属的浸渍对催化剂效率的影响而用于丙烷的氢化。发现所述催化剂提供了不太高的前体到产品的转化率。
US 5516961公开了用于轻质石蜡烃的脱氢(尤其是丁烷转化为丁烷)的催化剂，其中所述催化剂包括ZSM-5沸石，ZSM-5沸石在碱金属与铝的摩尔比在约1至5的范围内时具有由铂和碱金属改善的中级孔。然而，发现丁烷的选择性和前体到产品的转化百分比没有那么高。
US 2012/0083641公开了丙烷氧化脱氢为丙烯的催化剂，其中所述催化剂包括由钒、铝和镍改善的MCM-41沸石。然而，发现所述催化剂提供了不太高的丙烯选择性和前体到产品的转化百分比。
由于以上原因，本发明旨在制备包括X族金属的分层沸石纳米片，用于改善沸石结构，以适合其应用于通过烷烃脱氢的烯烃生产中，以提供前体到产品的高转化百分比和高的烯烃选择性。
附图说明
图1a)和b)分别示出根据发明2的样品的扫描电子显微镜和透射电子显微镜。
图1c)和d)分别示出比较样品B的扫描电子显微镜和透射电子显微镜。
图2示出使用氨程序升温脱附技术的根据发明2的样品和比较样品B的酸度性质。
图3示出根据本发明的沸石样品和用于丙烷的氢化的比较样品的转化百分比。
图4示出根据本发明的沸石样品和用于丙烷的氢化的比较样品的产物选择性百分比。
图5示出根据本发明的沸石样品和用于戊烷的氢化的比较样品的转化百分比。
图6示出根据本发明的沸石样品和用于戊烷的氢化的比较样品的产物选择性百分比。
具体实施方式
本发明涉及由烷烃的脱氢生产烯烃的催化剂和使用所述催化剂生产烯烃的方法，这些将根据以下实施方式描述。
除非另有说明，本文中示出的任何方面旨在包括其在本发明的其他方面的应用。
除非另有说明，本文中使用的技术术语或科技术语具有如由本领域普通技术人员做出的定义。
这里命名的任何工具、设备、方法或化学品意指由本领域普通技术人员通常使用的工具、设备、方法或化学品，除非另有说明它们是仅在本发明中特定的工具、设备、方法或化学品。
在权利要求书或说明书中，使用具有“包括”的单数名词或单数代词意指“一个”且包括“一个或多个”、“至少一个”和“一个或多于一个”。
本申请中公开的所有组合物和/或方法以及权利要求旨在覆盖来自任何行为、性能、修改或调整的实施方式，而无需与本发明显著不同的任何实验，并且得到反对实用性，虽然未在权利要求中具体说明，但根据本领域普通技术人员，获得与本实施方式相同的结果。因此，对本实施方式的可替代的或类似的反对，包括本领域技术人员清楚看到的任何微小的修改或调整，应被解释为保留在如所附权利要求中所示的发明的精神、范围和构思中。
贯穿本申请，术语“约”意指这里出现或示出的因设备、方法或个人使用所述设备或方法的任何误差而变化或偏离的的任何数字。
下文，在无任何意图限制本发明的任何范围的情况下示出发明实施方式。
本发明涉及由具有2至5个碳原子的烷烃的脱氢生产烯烃的催化剂，催化剂包括分层沸石纳米片，分层沸石纳米片具有大于120的硅土与矾土(SiO2/Al2O3)比和以重量计0.3％至5％的范围内的X族金属。
在一个实施方式中，分层沸石纳米片包括：具有0.4nm至0.6nm的范围内的孔径的微孔，具有2nm至50nm的范围内的孔径的中孔，和具有大于50nm的孔径的大孔，其中，中孔和大孔的特征在于占总孔体积的60％或更多。
优选地，具有0.4nm至0.6nm的范围内的孔径的微孔，具有20nm至40nm的范围内的孔径的中孔，和具有大于50nm的孔径的大孔，其中微孔和大孔的特征在于占总孔体积的75％或更多。
在一个实施方式中，X族金属选自铂、钯和镍，优选地为铂。
优选地，根据本发明的催化剂包括分层沸石纳米片，分层沸石纳米片具有大于300的硅土与矾土的摩尔比，和以重量计约0.5％至2％的范围内的X族金属。
最优选地，沸石为硅沸石。
在一个实施方式中，根据本发明的催化剂可通过以下步骤制备：
(a)制备包含用于制备沸石的化合物和软模板的溶液；
(b)使从步骤(a)中获得的混合物在确定的时间和温度下经受水热过程，以使所述混合物形成分层沸石；和
(c)使从步骤(b)中获得的分层沸石与X族金属盐溶液接触；
其中步骤(a)中的软模板为季鏻盐，并且步骤(c)中的X族金属盐包括以重量计占沸石0.3％至5％的X族金属。
在一个实施方式中，季鏻盐为选自下述的四烷基鏻盐：四丁基氢氧化鏻和三丁基十六烷基溴化鏻，优选四丁基氢氧化鏻。
在一个实施方式中，用于制备沸石的化合物为选自异丙醇铝、铝酸钠、硫酸铝的矾土以及选自正硅酸四乙酯、硅酸钠或硅胶的硅土化合物的混合物。
优选地，用于制备沸石的化合物为选自正硅酸四乙酯、硅酸钠或硅胶的硅土化合物，最优选正硅酸四乙酯。
在一个实施方式中，步骤(b)在130℃至180℃的范围内的温度下操作。
在一个实施方式中，步骤(c)包括以重量计占沸石0.5％至2％的比率的X族金属。
在一个实施方式中，X族金属盐选自铂盐、钯盐或镍盐。
在一个实施方式中，X族金属盐选自氯铂酸、四氨合硝酸铂、硝酸钯、氯化钯、氯化镍、硝酸镍和硫酸镍，优选四氨合硝酸铂或氯铂酸。
在一个实施方式中，步骤(c)可通过浸渍进行。
在一个实施方式中，所述催化剂的制备方法可进一步包括煅烧步骤。
干燥可通过使用烘箱的常规干燥方法、真空干燥、搅拌干燥和旋转蒸发干燥来进行。
煅烧可在大气条件下进行约1至10小时，并且温度在约400℃至800℃的范围内，优选约4至6小时和约500℃至600℃的范围内的温度。
在另一实施方式中，本发明涉及使根据本发明的催化剂经受具有2至5个碳原子的烷烃的脱氢以生产烯烃。优选地，烷烃为丙烷或戊烷，最优选丙烷。
在一个实施方式中，可进行脱氢方法，其中具有2至5个碳原子的烷烃的进料线在合适的反应条件下与根据本发明的催化剂接触，该脱氢方法可在固定床系统、移动床系统、流化床系统或间歇系统中操作。
脱氢可在约400℃至650℃的范围内，优选地在约450℃至550℃的范围内的温度下，在大气压至约3,000KPa的压力下，优选地在约100KPa至500KPa的范围内，并且最优选地在大气压下进行。
脱氢中烷烃进料线的重时空速(WHSV)在约1小时-1至30小时-1的范围内，优选地在约3小时-1至10小时-1的范围内。
通常，本领域任何技术人员可以调整脱氢条件以适合进料线、催化剂和反应器系统的类型和组成。
以下实施例仅用于证明本发明的实施方式，而不以任何方式限制本发明的范围。
催化剂的制备
根据本发明制备的催化剂通过以下方法制备。
以确定的硅土与矾土的摩尔比制备包含异丙醇铝正硅酸四乙酯的溶液。四丁基氢氧化鏻用作沸石的模板。然后，使所得的混合物在约130℃至180℃的温度下经受水热约2至4天，以将所述混合物转化为分层沸石。
然后，将所得的分层沸石用去离子水清洗直到清洗液的pH低于9。将所得的物质在100℃至120℃的温度下干燥约12至24小时。在约500℃至650℃的温度下进行煅烧约8至12小时以去除模板。获得白色粉末分层沸石。
通过将约20mL的铂溶液添加到由约1g的上述方法获得的沸石中，通过浸渍使所得的沸石与铂盐溶液接触，其中铂与沸石的比率为以重量计约1％。将所得的混合物搅拌约6至12小时，并且用旋转蒸发器干燥并在约550℃的温度下煅烧约5至10小时。
比较样品Cat A(ZSM5-con-120)
将根据由Hensen等人(Catalysis Today，2011，168，96-111)公开的方法合成的硅土与矾土的摩尔比为约120的所得ZSM-5沸石通过上述方法与铂盐溶液接触。
比较样品Cat B(硅沸石-con)
将在无矾土作为其组成的情况下根据由Hensen等人(Catalysis Today，2011，168，96-111)公开的方法合成的ZSM-5沸石通过上述方法与铂盐溶液接触。
根据本发明的样品Cat 1(ZSM5-NS-120)
使用120的硅土与矾土的摩尔比，将如上所述根据本发明的方法制备的根据本发明的样品Cat 1通过上述方法与铂盐溶液接触。
根据本发明的样品Cat2(硅沸石-NS)
在制备步骤中不使用矾土的情况下，将如上所述根据本发明的方法制备的根据本发明的样品Cat 2通过上述方法与铂盐溶液接触。
脱氢测试
脱氢测试可通过以下条件进行。
使用约0.2g的催化剂在固定床反应中操作脱氢。在反应之前，将催化剂与氮气中以体积计约2％至10％的氢以约10mL/min至50mL/min的流速接触约1至3小时。然后，以约1至3g/小时的流速将具有2至5个碳原子的烷烃进料。反应在约450℃至550℃的温度下在大气压和约5小时-1的重时空速(WHSV)下进行。
然后，反应之后，使用火焰离子化检测器(FID)作为检测器以及HP-AL/S和GASPRO毛细管柱，通过连接至固定床反应器出口的气相色谱法，测量在每次催化后的前体变化和每种组合物的生成，用于分析每种所述组合物。
表1示出根据本发明的分层沸石纳米片和比较样品的物理性质。从表中发现，由本发明制备的沸石包括微孔、中孔和大孔，其中，中孔和大孔大于总孔体积的60％。由本发明制备的沸石的含量显著大于常规沸石。这显示了分层多孔。此外，为了显示晶体结构，所得的物质通过扫描电子显微镜(SEM)和透射电子显微镜(TEM)测试，结果如图1中所示。根据本发明的沸石为粒径在约120nm至200nm的范围内的薄纳米片。还发现，分层沸石纳米片具有比常规沸石载体显著小的铂颗粒，而当在相同测试条件下制备时常规沸石具有大且不规则的铂粒径。
图2示出在酸度测试中使用氨程序升温脱附技术的根据本发明的分层沸石纳米片和常规沸石的酸度性质。发现，如从300℃至500℃的范围内的温度下的峰面积可见，根据本发明的沸石显著减少了强酸位点。所述结果导致减少了副反应，包括焦炭反应和裂化反应，因此减少了副产物形成。
表1：沸石的比表面积和分层性质
Figure BDA0002471223720000061
注意：BET(比表面积)；S外(外表面积)；V总(总孔体积)；V微(微孔体积)；V中+大(大孔和中孔体积)
为了研究分层沸石纳米片结构对作为脱氢催化剂的所述沸石的性能的影响，如图3至图6中所示，将根据本发明的沸石与使用常规沸石的比较样品用于研究。
图3和图4示出作为丙烷的脱氢催化剂的沸石的性能。发现根据本发明的样品Cat1和Cat 2比常规沸石显示出更好的丙烷转化，更高的丙烯选择性和更好的稳定性。
图5和图6示出作为戊烷的脱氢催化剂的沸石的性能。发现根据本发明的样品Cat2比常规沸石显示出更好的戊烷转化和更高的丙烯选择性。
由以上结果可以说，如在本发明的目的中表明的，根据本发明的分层沸石纳米片催化剂对于含有2至5个碳原子的烷烃的脱氢提供了高的转化和高的烯烃选择性。
发明的最佳方式
本发明的最佳方式如在本发明的说明书中所提供的。

Claims (21)

1.一种由具有2至5个碳原子的烷烃的脱氢生产烯烃的催化剂，所述催化剂包括分层沸石纳米片，所述分层沸石纳米片具有大于120的硅土与矾土(SiO2/Al2O3)比和以重量计0.3％至5％的范围内的X族金属。
2.根据权利要求1所述的催化剂，其中所述分层沸石纳米片包括：具有0.4nm至0.6nm的范围内的孔径的微孔，具有2nm至50nm的范围内的孔径的中孔，以及具有大于50nm的孔径的大孔，其中所述中孔和大孔的特征在于占总孔体积的60％或更多。
3.根据权利要求2所述的催化剂，其中所述分层沸石纳米片包括：
具有0.4nm至0.6nm的范围内的孔径的微孔，具有20nm至40nm的范围内的孔径的中孔，以及具有大于50nm的孔径的大孔，其中所述中孔和大孔的特征在于占总孔体积的75％或更多。
4.根据权利要求1所述的催化剂，其中X族金属选自铂、钯和镍。
5.根据权利要求4所述的催化剂，其中X族金属为铂。
6.根据权利要求1所述的催化剂，其中硅土与矾土的摩尔比大于300。
7.根据权利要求1所述的催化剂，其中沸石为硅沸石。
8.根据权利要求1、4或5所述的催化剂，其中所述催化剂包括以重量计0.5％至2％的X族金属。
9.根据权利要求1所述的催化剂，其中所述催化剂通过以下步骤制备：
(a)制备包含用于制备沸石的化合物和软模板的溶液；
(b)使从步骤(a)中获得的混合物在确定的时间和温度下经受水热过程，以使所述混合物形成分层沸石；和
(c)使从步骤(b)中获得的所述分层沸石与X族金属盐溶液接触；
其中步骤(a)中的所述软模板为季鏻盐，并且步骤(c)中的X族金属盐包括以重量计占沸石的0.3％至5％的X族金属。
10.根据权利要求9所述的催化剂，其中所述用于制备沸石的化合物为选自异丙醇铝、铝酸钠、硫酸铝中的矾土以及选自正硅酸四乙酯、硅酸钠或硅胶的硅土化合物的混合物。
11.根据权利要求9所述的催化剂，其中所述用于制备沸石的化合物为选自正硅酸四乙酯、硅酸钠或硅胶的硅土化合物。
12.根据权利要求9所述的催化剂，其中所述季鏻盐为选自四丁基氢氧化鏻和三丁基十六烷基溴化鏻的四烷基鏻盐。
13.根据权利要求12所述的催化剂，其中所述季鏻盐为四丁基氢氧化鏻。
14.根据权利要求9所述的催化剂，其中步骤(b)在130℃至180℃的范围内的温度下操作。
15.根据权利要求9所述的催化剂，其中步骤(c)包括以重量计占沸石的0.5％至2％的X族金属。
16.根据权利要求9所述的催化剂，其中X族金属盐选自铂盐、钯盐或镍盐。
17.根据权利要求15所述的催化剂，其中X族金属盐选自氯铂酸、四氨合硝酸铂、硝酸钯、氯化钯、氯化镍、硝酸镍和硫酸镍。
18.根据权利要求17所述的催化剂，其中X族金属盐为四氨合硝酸铂或氯铂酸。
19.根据权利要求9或15所述的催化剂，其中步骤(c)通过浸渍进行。
20.一种使用根据前述权利要求中任一项所述的催化剂由烷烃的脱氢生产烯烃的方法。
21.根据权利要求20所述的方法，其中所述方法在450℃至550℃的范围内的温度下操作，并且烷烃选自丙烷和戊烷。
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