CN102020524A - Mlab生产中二烯烃的选择性氢化 - Google Patents
Mlab生产中二烯烃的选择性氢化 Download PDFInfo
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Abstract
本发明涉及MLAB生产中二烯烃的选择性氢化。公开了一种用于将支化二烯烃和乙炔选择性氢化为烯烃的方法。该方法使用具有大孔以及少量微孔的催化剂。催化剂设计为具有通过大孔的极小扩散阻力,以及减少烯烃氢化到链烷烃的氢化。
Description
发明领域
本发明涉及经济上具有吸引力的方法以及用于以单烯烃脂族化合物烷基化芳族化合物的催化剂。特别是,该方法和催化剂涉及在烯烃生产中二烯烃和乙炔的选择性氢化。
背景技术
苯的烷基化生产可发现具有各种工业用途的烷基苯,例如烷基苯可被磺化生产洗涤剂。在烷基化方法中,苯与所需长度的烯烃反应生成所需烷基苯。烷基化条件包括均相或非均相烷基化催化剂如氯化铝、氟化氢或沸石催化剂的存在以及升高的温度。
三十多年前,许多家用衣物洗涤剂由支化烷基苯磺酸盐(BABS)制成。BABS由一种称为支化烷基苯(BAB)的烷基苯制成。烷基苯(苯基烷烃)是指具有与苯基结合的脂族烷基的一类化合物。
石油化学工业使用的用于生产BAB的标准方法由以下步骤组成:将低级烯烃,特别是丙烯低聚为具有10-14个碳原子的支化烯烃,然后在催化剂如HF的存在下,用支化烯烃烷基化苯。BAB的最突出的普通特性为对于BAB的大部分,通常有至少一个烷基支链,更通常3或更多个烷基支链连接BAB的脂族烷基链。因此,BAB的每一脂族烷基具有相对多的伯碳原子。
BAB的另一普通特性为BAB中的苯基可连接至脂族烷基链的任何非伯碳原子。除了由于伯碳正离子的相对不稳定性而已知不期望生成的1-苯基烷烃,以及忽视支化链烷烃的支链的相对小的影响外,低聚步骤产生沿脂族烯基链的长度随机分布的碳-碳双键,并且烷基化步骤几乎将苯基无规地连接至沿脂族烷基链的碳。因此,例如具有含10个碳原子的脂族烷基链的BAB预计将为2-、3-、4-和5-苯基烷烃的随机分布,以及如果分布为完全无规时,对2-苯基烷烃的选择性将为25,但是通常为10-40。
BAB的第三普通特性是脂族烷基的一个碳为季碳。季碳可为或不为在通过碳-碳键连接苯基中碳的脂族烷基中的碳。当烷基侧链上的碳原子不仅连接烷基侧链上的两个其它碳和烷基的碳原子,而且连接苯基的碳原子时,所得烷基苯基烷烃是指“季烷基苯基烷烃”或简称为“季烷”(“quat.”)。
很清楚的是由BABS制成的家用衣物洗涤剂逐步污染江河湖泊。问题的深入研究使人们认识到BABS生物降解缓慢。问题的解决方案引起由直链烷基苯磺酸盐(LABS)制成的洗涤剂的生产,发现其比BABS生物降解更快。今天,由LABS制成的洗涤剂正在全世界范围内生产。LABS是由另一种称为直链烷基苯(LAB)的烷基苯制成。LAB为包含直链脂族烷基和苯基并且具有通式n-苯基-烷烃的苯基烷烃。LAB没有烷基支链,因此直链脂族烷基通常具有两个伯碳原子。通过标准LAB方法生产的LAB的另一特性为LAB中的苯基通常连接直链脂族烷基的任何仲碳原子。在使用HF催化剂生产LAB中,苯基稍微更可能连接与接近直链脂族烷基末端相反的中心附近的仲碳原子,而在通过DetalTM方法生产LAB中,25-35mol%的正苯基烷烃为2-苯基烷烃。US 4,301,316和US 4,301,317教导了LAB的制备。也已发现轻度支化的LAB、或改性LAB(MLAB)具有与LAB类似的或改善的可生物降解特性。
控制MLAB的生产很重要,并且未支化烯烃、或单甲基或单乙基烯烃的生产可改善MLAB的生产。
发明概述
本发明涉及选择性氢化烯烃流中二烯烃和乙炔的方法。该方法包括使烯烃流与这样地设计以最小化扩散限制、并且使正烯烃以及单甲基和单乙基支化二烯烃进入孔中的大孔催化剂接触。催化剂包括微孔体积小于总催化剂孔体积的10%,以及表面积小于150m2/g的低密度载体。
载体包括中值孔径大于1050埃的材料,该孔径用于克服与支化二烯烃的位阻,并且允许支化二烯烃进入孔内部,以保证孔中的二烯烃组成接近二烯烃组成。载体可为γ氧化铝或θ氧化铝并且密度优选小于0.5g/cc以及催化剂中的孔体积大于1.8cc/g。
本发明的其它目的、优点和应用可通过下列详细说明而对本领域技术人员变得显而易见。
发明详述
烷基苯的生产对于许多工业用途非常重要,但是主要用于洗涤剂的生产。烷基苯的生产包括使用烯属烷基化剂烷基化芳香族化合物。烯烃可使用仅轻度支化的链烷烃从链烷烃生产。链烷烃的来源包括从GTL(气体-液体)方法生成的链烷烃、来自Sorbex分离方法的单甲基链烷烃、和轻度支化的链烷烃的其它来源。当烷基苯包括1重量%-70重量%的单甲基和/或单乙基烷基苯,其余包括直链烷基苯时,这些轻度支化的链烷烃的使用是可接受的。
从链烷烃生产MLAB包括脱氢链烷烃形成直链和支化烯烃的步骤。支化烯烃为轻度支化的烯烃并且关于由MLAB制成的洗涤剂的具有良好生物降解性质。部分烯烃进行后续脱氢并且形成二烯烃和乙炔。高质量MLAB的生产需要除去二烯烃和乙炔。二烯烃和乙炔使用适合用于此目的的合适催化剂通过选择性氢化方法除去。催化剂的选择包括在过量烯烃的存在下选择性氢化二烯烃和乙炔、具有将非共轭二烯烃异构化为共轭二烯烃的能力并且具有可促进直链或支链二烯烃的优先去除的极小扩散阻力的催化剂。
烷基苯的生产包括使富烯烃流和包含苯的原料流通过烷基化反应器。烷基化反应器具有包含烷基化催化剂的烷基化反应区,并且在烷基化条件下操作形成包含烷基苯的产品流。本发明产生包含直链烯烃和轻度支化的、或改性的直链烯烃的富烯烃流以生产包含直链烷基苯和改性的直链烷基苯的产品流。苯烷基化的更多细节和说明记载在2009年8月18日公告的US 7,576,247中,并且引入供参考。
在液相中使用的选择性氢化催化剂常常易受到扩散限制。这些限制可表现为差的选择性、或差的烯烃氢化、或在直链和支链组分间的差别。催化剂载体的生产常常产生具有双重孔隙大小分布的催化剂,其中直径小于100埃的孔通常称为微孔,以及直径大于100埃的孔称为中孔和大孔。对本发明而言,术语大孔将同时指中孔和大孔,或者直径大于100埃的孔。当催化剂的空隙组分超过催化剂内总空隙体积的某一比例时,通过微孔扩散控制方法。
长链二烯烃的选择性氢化最常用在氧化铝载体上包含硫化镍的催化剂进行。硫可能有时干涉烯烃的后续加工,因此在没有硫的情况下具有良好性能的选择性氢化催化剂是高度所需的。因而,有许多使用硫化镍催化剂的选择性氢化装置,还需要催化剂具有如它所代替的催化剂相同的工作温度范围。这避免了额外加热或冷却工作流体的需要。
本发明的目的是设计无扩散控制的催化剂,以及在单烯烃存在下选择性氢化二烯烃的混合物减少链烷烃的生成,或减小直链和支化二烯烃之间的差别。二烯烃可为直链和支化、以及共轭和非共轭二烯烃的混合物。混合物还可具有过量的单烯烃,因此单烯烃以二烯烃量的至少十倍量存在。
本发明的催化剂包含由γ氧化铝、θ氧化铝或γ和θ氧化铝的混合物组成的低密度载体,并且微孔体积小于总孔体积的20%,以及优选微孔体积小于总孔体积的10%。另外,催化剂的表面积小于150m2/g以及具有分布在载体上的活性金属,并且优选表面积为30-150m2/g。活性金属包含以催化剂重量的50-5000ppm。
对于催化剂的优选实施方案是具有孔体积大于1.8cc/g的载体。载体设计为具有大孔,并且优选中值孔径为大于1050埃。为了克服扩散限制,大孔容许二烯烃进入孔中,并且载体设计为超过一半的孔体积来自具有大直径或者大于1000埃直径的孔。优选的是具有大于1000埃直径的孔的孔体积部分为大于总孔体积的60%。载体设计为具有少部分的微孔体积,并且优选为小于总孔体积的2%。
在一个实施方案中,优选的载体为密度小于0.5g/cc的θ氧化铝。在载体的制备中,一种方法为使载体达到θ转变温度,并且在加入活性金属前将载体转化为θ氧化铝。在这一实施方案中,活性金属为钯并且以催化剂重量的50-2000ppm的量分布在载体上,优选活性金属以200-2000ppm的量分布,更优选为以200ppm-1000ppm。活性金属优选使用金属非氯化物盐分布在载体上。可供选择的盐的一个实例为钯的硝酸盐。
催化剂在选择性氢化中的使用包括控制催化剂的酸性。催化剂酸性可通过将碱金属负载在载体上来改性。碱金属可选自元素周期表中的IA族金属。优选地,碱金属选自锂(Li)、钠(Na)和钾(K)的至少一种。
碱金属的使用以摩尔浓度这样地表示,即通过氨(NH3)吸附测量的载体酸性。在钾(K)的情况下,钾的量以重量计为小于3000ppm。对于其它金属,存在分子量校正以保持合适的摩尔浓度。对于钠,金属为以重量计小于1800ppm的量,以及对于锂,金属为以重量计小于600ppm的量。
这一催化剂的开发是为了用于包含二烯烃和乙炔的轻度支化的烯烃原料。特别是,这一催化剂开发用于单甲基和单乙基支化的二烯烃。轻度支化的二烯烃需要更大的孔,以允许更大位阻的分子进入孔中,以及克服来自更小孔的扩散限制。因为轻度支化的二烯烃可以不同于直链二烯烃的速率反应,使用大孔催化剂有助于保证孔中的浓度不显著不同于大部分流体中的浓度。催化剂的使用通过最小化微孔的体积分数,或者平均直径小于100埃的孔而是方法成为可能。
本发明的方法为二烯烃和乙炔的选择性氢化,包括使具有烯烃、二烯烃和乙炔的烯烃流与微孔体积小于催化剂孔体积的20%的催化剂接触。烯烃流包含支化二烯烃和直链二烯烃,二烯烃具有单甲基和单乙基支链。催化剂为具有低密度载体和表面积为小于150m2/g的低密度催化剂。优选的低密度载体为γ氧化铝或θ氧化铝,以及载体的密度为小于0.5g/cc。
催化剂包括选自铂族的活性金属,以及优选的金属为钯。活性金属以催化剂总重量计地为50-5000ppm的量沉积在催化剂的载体上,优选的金属量以重量计地为50-1000ppm。
用于选择性氢化方法中的催化剂优选孔体积大于1.8g/cc,以及中值孔径为大于1050埃。1200埃的中值孔径为合乎需要的。对于进入孔中的二烯烃,催化剂设计为超过一半的孔体积来自直径大于1000埃的孔,并且优选超过60%的孔体积来自直径大于1000埃的孔。
尽管本发明已经通过目前考虑的优选实施方案进行了描述,应该理解为本发明不限于公开的实施方案,而是覆盖包括在所附权利要求范围内的不同改性和等同方案。
Claims (10)
1.一种选择性氢化二烯烃和乙炔的方法,包括:使包含烯烃和二烯烃以及乙炔的烯烃流与包含微孔体积小于催化剂孔体积的10%且表面积为30至150m2/g的低密度载体的催化剂接触。
2.根据权利要求1的方法,其中所述烯烃流包含单甲基和单乙基支化二烯烃和直链二烯烃。
3.根据权利要求1的方法,其中所述低密度载体为γ氧化铝、θ氧化铝或γ和θ氧化铝的混合物。
4.根据权利要求3的方法,其中所述载体的密度为小于0.5g/cc。
5.根据权利要求1的方法,其中所述催化剂包含活性金属,所述活性金属为钯,并且其量以重量计为50-5000ppm。
6.根据权利要求1的方法,其中所述催化剂进一步包含碱金属,其中所述碱金属选自锂(Li)、钠(Na)、钾(K)及其混合物组成的组。
7.根据权利要求6的方法,其中所述碱金属为以重量计小于3000ppm的钾。
8.根据权利要求1的方法,其中所述催化剂中的孔体积为大于1.8cc/g。
9.根据权利要求1的方法,其中所述催化剂的中值孔径为大于1050埃。
10.根据权利要求1的方法,其中所述催化剂的微孔体积为小于总孔体积的2%。
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