CN107847908B - 催化剂以及使用所述催化剂的烃转化方法 - Google Patents
催化剂以及使用所述催化剂的烃转化方法 Download PDFInfo
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- CN107847908B CN107847908B CN201680027012.0A CN201680027012A CN107847908B CN 107847908 B CN107847908 B CN 107847908B CN 201680027012 A CN201680027012 A CN 201680027012A CN 107847908 B CN107847908 B CN 107847908B
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Classifications
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Abstract
本发明涉及烃转化催化剂，所述烃转化催化剂包含i)处于氧化形式的催化剂，其包含金属M1、M2、M3和M4，其中：M1选自Si、Al、Zr以及它们的混合物；M2选自Pt、Cr以及它们的混合物；M3选自W、Mo、Re以及它们的混合物；M4选自Sn、K、Y、Yb以及它们的混合物；和ii)氢清除剂，其选自至少一种碱金属衍生物和/或碱土金属衍生物，优选地，处于金属、氢化物、盐、络合物或合金形式；以及使用这种催化剂的烃转化方法。
Description
技术领域
本发明涉及烃转化催化剂和用于将包含饱和烃化合物的烃进料转化成烯烃产物的方法。
背景技术
烯烃，特别是包括乙烯和丙烯的轻质烯烃(light olefin)，是有价值的烃类产品。它们用于制备多种最终产品，包括环氧乙烷、环氧丙烷、乙基苯、丙酮、苯酚、聚乙烯、聚丙烯、其它聚合物及其它石油化学产品。尽管它们的价格随时间波动，但是产业需求仍持续增长。
为了服务工业需要，多种方法已用于生产烯烃。然而，通常从低附加值原料，如石蜡来生产烯烃在经济上是更有吸引力的。将饱和石蜡转化为烯烃的常规方法是热裂解。这是高度能量密集的方法并且产物选择性难以调节和控制。
催化裂化是新近发展的方法。通过适当的催化材料，通常为基于沸石的材料，烃裂解可以在不太严苛的操作条件下进行。
在本领域中，使用适当的催化剂通过脱氢将饱和石蜡转化为具有相应碳原子数的烯烃的方法也是已知的。脱氢之后可以是适当的反应步骤以进一步将所得烯烃转化为所需产物。例如，脱氢之后可以是复分解(metathesis)步骤以将得自脱氢步骤的烯烃转化为不同的烯烃。
在脱氢和接下来的反应步骤，例如复分解期间可以发生多种副反应，例如，作为乙烷、丙烷或丁烷的脱氢反应的优选最终产物的乙烯、丙烯或丁烯的(再)氢化。换言之，在使所得烯烃进一步反应时，氢的发展(development)可能是缺陷。
发明内容
因此，本发明的一个目标是提供烃转化催化剂和使用它的相应方法，其中可以降低或基本防止氢的副反应。
通过烃转化催化剂实现该目标，所述催化剂包含i)氧化形式的催化剂，其包含金属M1、M2、M3和M4，其中：M1选自Si、Al、Zr以及它们的混合物；M2选自Pt、Cr以及它们的混合物；M3选自W、Mo、Re以及它们的混合物；M4选自Sn、K、Y、Yb以及它们的混合物；其中M1的质量分数在0.1与0.8的范围内；M2的质量分数在0.001与0.2的范围内；M3的质量分数在0.001与0.2的范围内；M4的质量分数在0.0001与0.2的范围内；以及氧的质量分数在0.1至0.8的范围内；以及ii)氢清除剂，其选自至少一种碱金属衍生物和/或碱土金属衍生物，优选地，处于金属、氢化物、盐、络合物或合金形式。
用于将包含饱和烃化合物的烃进料转化成烯烃产物的方法也是根据本发明的，其包括将烃进料流股与本发明的烃转化催化剂接触。
在从属权利要求(sub-claims)中公开了优选实施方式。
在本发明的另一个实施方式中，M1的质量分数在0.2至0.6的范围内，M2的质量分数在0.0015至0.15，优选地0.0015至0.05的范围内，M3的质量分数在0.005至0.15，优选地0.01至0.1的范围内和/或M4的质量分数在0.00015至0.03，优选地0.0003至0.01的范围内。在另一个实施方式中，氧的质量分数在0.2至0.6的范围内。
在另一个实施方式中，M2是Pt和/或M3是W。
在一个实施方式中，本发明所述的烃进料转化的方法是在200-700℃，优选地300-650℃，更优选地400-600℃的范围内的温度下进行的。
在另一个实施方式中，处于氧化形式的所述催化剂还包含金属M5(即化学式M1M2M3M4M5O的催化剂)。
优选地，M5选自Mg、Ca、Mn、Fe、Co、Ni、Cu以及它们的混合物；以及
M5的质量分数优选地在0.005至0.1，更优选地0.005至0.05的范围内。
在本发明所述的催化剂中，M1-M4和O的以及M1-M5和O的质量分数分别地总和最高为1。
在一个实施方式中，所述至少一种碱金属和/或碱土金属选自Li、Na、K、Mg、Ca以及它们的混合物，优选地Na和Mg。
意外地发现在本发明的烃转化催化剂中使用的氢清除剂能够在不希望的情况下清除氢。选择用于本发明的氢清除剂含有一些氢存储能力。所述氢清除剂的氢存储能力可以是可逆的或不可逆的。
可以通过将元素M1至M4或者M1至M5的所有前体混合在一起，然后通过适当的热处理以获得所期望的多金属组合物来制备处于氧化形式的所述催化剂。元素前体是含有所期望的元素的起始化合物，通过适当的热处理，在最终的催化剂中，所述元素可以转化为元素所期望的形式，优选地，氧化物形式。例如，M1至M5的前体可以包括元素的氧化物、卤化物、醇盐、硝酸盐、碳酸盐、甲酸盐、草酸盐、胺或氢氧化物。
可以以干式或湿式进行元素前体的混合。当将它们以干式混合时，所述元素前体可以方便地以粉末形式提供。可以在混合机中通过物理混合容易地混合所述元素前体的粉末。然后，对所述元素前体混合物进行适当的热处理，优选地焙烧以获得处于氧化形式的最终催化剂。当将它们以湿式混合时，所述元素前体可以以溶液和/或混悬液形式提供。然后，干燥元素前体溶液和/或混悬液的混合物以除去溶剂。随后，对干燥混合物进行适当的热处理，优选地焙烧以获得最终催化剂。作为另外一种选择并且优选地，一些元素前体可以以干式提供，而一些元素前体可以以湿式提供。可以通过常规方法，包括浸渍(impregnation)、初湿法(incipient wetness)、离子交换或本领域中已知的其它方法结合干式和湿式元素前体。然后，对所得混合物进行适当的热处理，优选地焙烧以获得最终催化剂。适当的热处理包括能够除去和/或转化至少一部分元素前体至所述最终催化剂中相应元素所期望的形式的所选气氛和所选温度。在所述最终催化剂中元素处于氧化形式是特别优选的。所选气氛可以包括氧化气氛、还原气氛和惰性气氛。在优选的实施方式中，将所制备的催化剂粉末在空气中，在300℃至800℃的范围内的温度下焙烧1至24小时，更优选地在400℃至700℃的范围内的温度下焙烧2至10小时。
还可以通过单独焙烧一种或多种元素前体，然后将相应的氧化的元素前体结合并最终焙烧来制备处于氧化形式的所述催化剂。例如，将氧化锆、氧化铝、二氧化硅和/或沸石(M1)的载体用于单独地或同时地将M2、M3和M4和/或M5浸渍其上。然后，将分别地制备的单独组合物物理混合并最终焙烧。可以将所述氢清除剂加入至这些混合物中的任一种中，或者可以当制备所有金属M1-M5和所述氢清除剂的最终混合物时加入。
在一个优选的实施方式中，通过将处于氧化形式的所述催化剂与所述氢清除剂物理混合来制备所述烃转化催化剂，所述催化剂是焙烧的并处于固体形式的，所述氢清除剂优选地也以固体形式提供。
适合于本发明，所述氢清除剂是碱金属的衍生物和/或碱土金属的衍生物形式，优选地金属、氢化物、盐、络合物、合金或它们的混合物。
优选地，通过对氢清除剂前体进行适当热处理，优选地在300℃至700℃，更优选地400℃至600℃的范围内的温度下焙烧2至24小时来制备所述氢清除剂。
所述氢清除剂前体可以是碱金属和/或碱土金属的化合物，优选地，碱金属和/或碱土金属的盐。
在一个实施方式中，所述氢清除剂前体选自Ca(BH4)2、Mg(BH4)2、Ca(NO3)2、K(NO3)2、Na(NO3)2以及它们的混合物。
发现在适当的热处理温度和/或烃转化温度下，所述氢清除剂前体分解成碱金属和/或碱土金属的衍生物形式。在这点上，在本发明的一个实施方式中，所述氢清除剂在所述烃转化催化剂中不以氧化形式存在，而是以碱金属和/或碱土金属的衍生物形式存在，优选地金属、氢化物、盐、络合物、合金形式或它们的混合物。
在另一个实施方式中，根据本发明所述的烃转化催化剂的制备还可以包括将所述催化剂粉末形成适合于商业反应器的形状。适合于商业反应器的形状可以包括颗粒、挤出物、球等。还可以将足够的粘合材料加入至所述催化剂组合物以有利于形成所述催化剂。
所述烃进料流股与所述催化剂i)和所述氢清除剂ii)的接触可以单独地或同时地进行。在优选的实施方式中，将所述催化剂i)和所述氢清除剂ii)混合，并且同时进行所述烃进料流股与所述催化剂i)和所述氢清除剂ii)的接触。所述催化剂i)和所述氢清除剂ii)的混合可以在微观水平或宏观水平下进行。在一个实施方式中，将所述氢清除剂或其前体加入至所述催化剂i)的制备步骤。优选地，在与所述烃进料流股接触前，将所述催化剂i)和所述氢清除剂ii)的粉末物理混合。可以在与所述烃进料流股接触前，可选地与所添加的适合的粘结剂一起，将所述粉末混合物形成适合的形状。在与所述烃进料流股接触前，将所述催化剂i)和所述氢清除剂ii)以适当重量比物理混合也是优选的。在这点上，催化剂i)和氢清除剂ii)的适合的重量比可以为从1-99至99-1。催化剂i)与氢清除剂ii)的优选的重量比在1-30比1，更优选地2-25比1，更优选地4-20比1甚至更优选地5-15比1的范围内。
为了实现烯烃产物，所述烃进料流股包含石蜡烃是有利的。在优选的实施方式中，所述烃进料流股包含具有2至5个碳原子的石蜡。在更具体的实施方式中，所述烃进料流股包含石蜡，其选自乙烷、丙烷、丁烷、戊烷以及它们的混合物，优选地丙烷、丁烷以及它们的混合物。
可以在宽泛范围内的工作条件下进行所述烃转化方法。然而，操作条件的一些具体范围可以导致高烯烃生产选择性。在一个实施方式中，所述方法是在200℃至700℃，优选地300℃至650℃，更优选地400℃至600℃的范围内的温度下进行的。在另一个实施方式中，所述方法是在0.01至10巴，优选地0.05至5巴的范围内的压力下进行的。获得所期望的烯烃产物得率所需的接触时间依赖于一些因素，如操作温度、操作压力以及催化剂活性。在一个实施方式中，所述方法在0.01至20hr-1，优选地0.05至5hr-1的重量时空速度(WHSV)下进行。可以以分批方式或连续方式实施所述方法。对于工业规模，连续操作所述方法是有利的。可以通过固定床、流化床或本领域中已知的其它技术实施连续操作，其中固定床通常是优选的。
在与所述烃进料流股接触之前，可以可选地对所述催化剂i)和所述氢清除剂ii)进行预处理。所述预处理条件可以包括将所述催化剂i)和所述氢清除剂ii)与惰性气体、氧化气体、还原气体、烃，优选地C2-C6脂肪烃和它们的任何混合物接触。所述预处理可以分成一些步骤，其中每个步骤可以使用不同的条件和气氛。通常优选地，在加热温度，优选地200℃至700℃，更优选地300℃至600℃，更优选地350℃至550℃下进行所述预处理。
在操作条件下与所述烃进料流股接触后，一些有毒物质、重质烃类和焦炭可以沉积在所述催化剂和所述氢清除剂的表面上。这通常影响催化剂混合物的活性，从而所述活性随时间逐渐降低。可以对所述催化剂和氢清除剂的使用过的混合物进行适当再生以恢复其至少一些活性。在一个实施方式中，所述烃转化方法包括再生步骤，其中所述再生步骤包括将所述烃转化催化剂与氧化剂在高温下接触。应小心控制所述再生步骤以避免过度加热和破坏所述催化剂的结构。在一个实施方式中，所述再生步骤是在200℃至700℃，优选地300℃至600℃的范围内的温度下进行的。可以无限制地使用其它已知的再生技术。
根据以上发明公开，已制备和测试了本发明的多种烃转化催化剂。本发明人意外地发现与非本发明的催化剂体系相比，(本发明的催化剂和本发明的氢清除剂的)催化剂体系在特征为更好的催化活性和选择性的权利要求的范围内。
此外，意外地发现根据本发明所述的催化剂体系可以在温和条件下操作，即在显著低于本领域中已知的温度下进行。
具体实施方式
实验结果：
在以下实施例部分中，已使用根据本发明的烃转化催化剂和比较催化剂研究了丙烷向烯烃，优选地乙烯和丁烯的转化。
实施例A
在约500℃、0.1巴和0.2h-1的WHSV下与C3H8接触前，通过在约500℃与空气接触30分钟并且在约500℃与氢气接触90分钟来预处理每个实施例的催化剂。在运行时间(timeon stream)约60-65小时测量结果。将反应流出物导入气相色谱装置以测量它们的化学组成。将流出物所测量的组成用于计算转化率和选择性。通过将反应期间转化的C3H8的重量除以进料流股中C3H8的重量，然后乘以100来计算C3H8转化百分比。还通过将反应产生的特定产物的重量除以反应产生的全部产物的重量，然后乘以100来计算每个其它产物的选择性百分比。根据用于制备所述催化剂的前体的量计算催化剂的组成。可以通过将重量百分比除以100来计算质量分数。
实施例1(比较实施例)
在进行反应测试前，将含有0.811wt％Al、1.792wt％Mg、50.495wt％O、0.501wt％Pt、42.526wt％Si、3.396wt％W、0.076wt％Yb和0.403wt％Zr的催化剂样品在空气中在550℃下焙烧3小时。
该催化剂是不添加氢清除剂的用于将石蜡转化成烯烃的标准催化剂。
实施例2(比较实施例)
通过以下步骤制备所述催化剂样品：
1)提供含有0.810wt％Al、1.789wt％Mg、50.497wt％O、0.5wt％Pt、42.53wt％Si、3.391wt％W、0.076wt％Yb和0.403wt％Zr的粉末催化剂。
2)在空气中，在550℃焙烧步骤中1)所述的粉末催化剂3小时。
3)在空气中，在550℃焙烧NH3BH3 3小时。
4)将80wt％来自步骤2)的所述焙烧催化剂与20wt％来自步骤3)的焙烧NH3BH3物理混合。
该催化剂的使用显示出更高的烯烃选择性，然而似乎NH3BH3抑制W的复分解活性并因此乙烯和丁烯选择性显著降低。
实施例3
通过以下步骤制备所述催化剂样品：
1)提供含有0.811wt％Al、1.791wt％Mg、50.448wt％O、0.501wt％Pt、42.573wt％Si、3.395wt％W、0.076wt％Yb和0.403wt％Zr的粉末催化剂。
2)在空气中，在550℃焙烧步骤中1)所述的粉末催化剂3小时。
3)在空气中，在550℃焙烧Na(NO3)3小时。
4)将80wt％来自步骤2)的所述焙烧催化剂与20wt％来自步骤3)的焙烧Na(NO3)物理混合。
该催化剂的使用可以抑制氢化副反应。这通过与实施例1中的标准催化剂相比，较高的C2H4和C4H8选择性，但较低的C2H6和C4H10选择性所显示。
实施例4
通过与实施例3相同的步骤，但使用了10wt％的Na(NO3)制备所述催化剂样品。
该催化剂的使用可以抑制氢化副反应。这通过与实施例1中的标准催化剂相比，较高的C2H4和C4H8选择性，但较低的C2H6和C4H10选择性所显示。
实施例5
通过与实施例3相同的步骤，但使用10wt％的K(NO3)而不是Na(NO3)制备所述催化剂样品。
该催化剂的使用可以抑制氢化副反应。这通过与实施例1中的标准催化剂相比，较高的C2H4和C4H8选择性，但较低的C2H6和C4H10选择性所显示。
实施例B
在约550℃、0.05-0.1巴和0.4-0.7h-1的WHSV下与C3H8接触前，通过在约500℃与空气接触30分钟并且在约500℃与氢气接触90分钟来预处理每个实施例的催化剂。在运行时间约155-160小时测量结果。
实施例6(比较实施例)
在进行反应测试前，将含有0.324wt％Al、0.715wt％Mg、49.624wt％O、4.277wt％Pt、42.700wt％Si、1.355wt％W、0.390wt％Yb和0.641wt％Zr的催化剂样品在空气中在550℃焙烧3小时。
实施例7
通过以下步骤制备所述催化剂样品：
1)提供含有0.801wt％Al、1.782wt％Mg、49.009wt％O、2.687wt％Pt、41.237wt％Si、3.379wt％W、0.714wt％Yb和0.382wt％Zr的粉末催化剂。
2)在空气中，在550℃焙烧步骤中1)所述的粉末催化剂3小时。
3)在空气中，在550℃焙烧Ca(BH4)2 3小时。
4)将80wt％来自步骤2)的所述焙烧催化剂与20wt％来自步骤3)的焙烧Ca(BH4)2物理混合。
该催化剂的使用可以抑制氢化副反应。这通过与实施例6中的标准催化剂相比，较低的C2H6和C4H10选择性所显示。
实施例8
通过与实施例7相同的步骤，但使用6.5wt％的Mg(BH4)2而不是Ca(BH4)2制备所述催化剂样品。
该催化剂的使用可以抑制氢化副反应。这通过与实施例6中的标准催化剂相比，较低的C2H6和C4H10选择性所显示。
上述说明以及随附权利要求中公开的特征可以单独和以其任意组合作为以多种形式实现本发明的材料。
Claims (10)
1.一种烃转化催化剂，包含处于氧化形式的固体催化剂和固体氢清除剂以4-20:1的重量比的物理混合物，
i）所述处于氧化形式的固体催化剂包含金属M1、M2、M3和M4，其中：
M1选自Si、Al、Zr以及它们的混合物；
M2选自Pt、Cr以及它们的混合物；
M3是W；
M4选自Y、Yb以及它们的混合物；
其中
M1的质量分数在0.1至0.8的范围内；
M2的质量分数在0.001至0.2的范围内；
M3的质量分数在0.001至0.2的范围内；
M4的质量分数在0.0001至0.2的范围内；以及
氧的质量分数在0.1至0.8的范围内；
以及
ii）所述氢清除剂选自至少一种碱金属和/或碱土金属的衍生物。
2.根据权利要求1所述的烃转化催化剂，其中所述氢清除剂处于金属、氢化物、盐、络合物或合金形式。
3.根据权利要求1所述的烃转化催化剂，其中所述至少一种碱金属和/或碱土金属选自Li、Na、K、Mg、Ca以及它们的混合物。
4.根据权利要求1所述的烃转化催化剂，其中所述至少一种碱金属和/或碱土金属选自Na和Mg。
5.根据权利要求1至4中任一项所述的烃转化催化剂，其中M2是Pt，以及M3是W。
6.一种用于将包含饱和烃化合物的烃进料转化成烯烃产物的方法，包括将烃进料流股与权利要求1-5中任一项所述的烃转化催化剂接触。
7.根据权利要求6所述的方法，其中所述烃进料流股包含至少一种具有2至5个碳原子的链烷烃。
8.根据权利要求7所述的方法，其中所述具有2至5个碳原子的链烷烃选自丙烷、正丁烷以及它们的混合物。
9.根据权利要求6至8中任一项所述的方法，还包括所述烃转化催化剂的再生步骤，所述再生步骤包括在200-700℃的温度下将所述烃转化催化剂与氧化剂一起加热。
10.根据权利要求9所述的方法，其中所述氧化剂包括空气或氧气。
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