CN110072613B - 催化剂体系和用于使用该催化剂体系转化烃进料的方法 - Google Patents
催化剂体系和用于使用该催化剂体系转化烃进料的方法 Download PDFInfo
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- CN110072613B CN110072613B CN201780076953.8A CN201780076953A CN110072613B CN 110072613 B CN110072613 B CN 110072613B CN 201780076953 A CN201780076953 A CN 201780076953A CN 110072613 B CN110072613 B CN 110072613B
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Abstract
本发明涉及一种催化剂体系和使用这种催化剂体系转化烃进料的方法,该催化剂体系包含:i.烃转化催化剂的第一层,烃转化催化剂包含:第一组合物,其包含固体载体上的铂族金属;和第二组合物,其包含无机载体上的过渡金属;ii.包含裂化催化剂的第二层。
Description
技术领域
本发明涉及催化剂体系,以及将包含饱和烃化合物的烃进料转化为烯烃产物的方法。
背景技术
烯烃,尤其是包括乙烯和丙烯的轻质烯烃,是有价值的烃产物。它们可用于制备各种最终产品,包括环氧乙烷、环氧丙烷、乙苯、丙酮、苯酚、聚乙烯、聚丙烯、其他聚合物以及其他石化产品。尽管它们的价格随着时间的推移而波动,工业上的需求仍在不断增长。
为了满足工业需要,已经使用许多方法来生产烯烃。然而,使用较低价值的原料如链烷烃来生产烯烃通常更具经济吸引力。将饱和链烷烃转化为烯烃的常规方法是热裂化。这是一种高能耗的方法,并且产品选择性难以调节和控制。
催化裂化是后来开发的方法。采用合适的催化材料,通常是基于沸石的材料,烃裂化可以在不太苛刻的操作条件下发生。
在本领域中,还已知使用适当的催化剂,通过脱氢将饱和链烷烃转化为烯烃的方法。脱氢之后可以进行适当的复分解步骤,以便最终提供满足最高工业需求的烯烃分布。
这种加氢转化方法的缺点是它倾向于产生大量的高级烯烃(例如丁烯),但是低级烯烃(例如乙烯)往往更具商业吸引力。
发明内容
因此,本发明的一个目的是提供一种催化剂体系和利用它来转化烃的方法,其中作为产物的高级烯烃的量减少,但低级烯烃,尤其是乙烯的量增加。
该目的通过催化剂体系实现,该催化剂体系包含:
i.烃转化催化剂的第一层,该烃转化催化剂包含:
含有固体载体上的脱氢活性金属的第一组合物;以及
含有无机载体上的过渡金属的第二组合物;以及
ii.包含裂化催化剂的第二层。
在烃转化催化剂中,可以提供与第二组合物不同的第一组合物。同样地,包含在第一组合物中的固体载体可以与包含在第二组合物中的无机载体不同。类似地,包含在第一组合物中的脱氢活性金属优选不同于包含在第二组合物中的过渡金属。
可以提供不包含脱氢活性金属的第二组合物,特别是第二组合物不包含铂、钯、铑、铬或它们的混合物。
在另一个实施方式中,包含在第二组合物中的无机载体包含SiO2、HY-沸石或它们的混合物,并且包含在第一组合物中的固体载体包含二氧化硅与氧化锆的混合物。
在一个实施方式中,裂化催化剂用于裂化烯烃,优选用于将丁烯裂化成乙烯。
在一个实施方式中,裂化催化剂包含分子筛,优选沸石和/或硅沸石。
在另一个实施方式中,裂化催化剂由分子筛优选沸石和/或硅沸石组成。
分子筛是本领域公知的材料,其具有非常小的精确和均匀尺寸的孔,其会选择性地吸收可以通过孔的分子。一些实施例包括活性炭、硅胶、硅沸石和天然或合成沸石。
沸石是众所周知的天然或合成的水合铝硅酸盐化合物,其具有完全确定的晶体结构和笼状空腔。沸石的结构基于二氧化硅和氧化铝四面体的三维框架。
在一个实施方式中,沸石选自ZSM-5、ZSM-11、SAPO-11和它们的混合物,优选ZSM-5。
在另一个实施方式中,ZSM-5具有20-1500,更优选200-800范围内的二氧化硅与氧化铝之比(Si/Al)。
硅沸石是二氧化硅的多晶型物,具有类似于沸石的结构。
根据本发明的催化剂体系可以改变烃转化方法的产物分布,特别是减少高级烯烃和增加低级烯烃,即使存在非常小部分的第二层也是如此。然而,由于平衡限制,催化剂体系中的第二层的更大部分并不总是导致高级烯烃的更多的减少。
在一个实施方式中,催化剂体系中第一层与第二层的重量比为50:1至1:20,优选为40:1至1:1。
脱氢活性金属是指对烃的脱氢有效的一组金属。脱氢是氢从分子中脱离出来的反应。在一个实施方式中,脱氢活性金属选自铂、钯、铱、铬和它们的混合物,优选为铂。
在一个实施方式中,固体载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、氧化镁、氧化钙和它们的混合物。
在另一个实施方式中,固体载体包含混合的镁-铝氧化物和/或钙-铝氧化物。
用于增强该第一组合物的催化活性的另外的活性金属,例如钾、锡、镧、铟、钇、镱、铼和它们的混合物,也可存在于第一组合物中,优选锡、铟和它们的混合物。
在一个实施方式中,基于第一组合物的总重量,第一组合物含有0.01至25wt%的脱氢活性金属,优选为0.05至20wt%的脱氢活性金属,更优选为0.1至5wt%的脱氢活性金属。
在一个实施方式中,铂是脱氢活性金属,Al2O3是固体载体,并且锡和/或钾是第一组合物中的另外的活性金属。
在另一个实施方式中,铂是脱氢活性金属,SiO2和ZrO2是固体载体,并且钇和/或镱是第一组合物中的另外的活性金属。
在又一个实施方式中,铂是脱氢活性金属,混合的镁-铝氧化物和/或混合的钙-铝氧化物是固体载体,并且铟和/或锡是第一组合物中的另外的活性金属。
在一个实施方式中,第一组合物中的混合的镁-铝氧化物和混合的钙-铝氧化物来源于镁-铝或钙-铝层状双氢氧化物,其可优选通过使镁-铝或钙-铝层状双氢氧化物经受600-700℃范围内的温度,更优选600-650℃超过2小时而获得,更优选3-10小时。
优选地,基于第一组合物的总重量,第一组合物包含0.005至2wt%的另外的活性金属。还优选地,另外的活性金属负载在固体载体上。
优选地,第一组合物中存在的脱氢活性金属、固体载体和另外的活性金属的总量为第一组合物重量的至少90%,更优选至少95%。在一个具体的实施方式中,第一组合物由脱氢活性金属、固体载体和任选的另外的活性金属组成。在一个实施方式中,第二组合物的过渡金属选自钼、钨、铼和它们的混合物。
过渡金属优选为钨,更优选为氧化钨的形式。
在一个实施方式中,无机载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、沸石和它们的混合物,优选二氧化硅或二氧化硅和沸石的混合物。
在一个实施方式中,第二组合物包含在无机载体上的钨,无机载体包含二氧化硅和沸石的混合物。
优选地,沸石选自ZSM-5、X-沸石、Y-沸石、β-沸石、MCM-22、镁碱沸石和它们的混合物,更优选Y-沸石。
在另一个优选的实施方式中,第二组合物还包含混合的金属氧化物,更优选混合的镁-铝氧化物、混合的钙-铝氧化物或它们的混合物,其中混合的金属氧化物优选与无机载体上的过渡金属物理混合。
在特别优选的实施方式中,第二组合物含有在无机载体上的氧化钨,无机载体包含与混合的镁-铝氧化物物理混合的二氧化硅和Y-沸石的混合物。
甚至更优选的是来源于镁-铝层状双氢氧化物前体的混合的镁-铝氧化物。
在一个实施方式中,基于第二组合物的总重量,第二组合物包含1至15wt%的过渡金属,甚至更优选5至10wt%的过渡金属。
在一个实施方式中,第二组合物还包含选自锌、镓、铟、镧和它们的混合物的掺杂剂。优选地,掺杂剂负载在无机载体上。
优选地,基于第二组合物的总重量,掺杂剂在第二组合物中以0.1-10wt%的量存在,更优选为1-5wt%的量。
优选地,存在于第二组合物中的过渡金属、无机载体、混合的金属氧化物和任选的掺杂剂的总量为第二组合物重量的至少90%,更优选至少95%。在一个具体的实施方式中,第二组合物由过渡金属、无机载体、混合的金属氧化物和任选的掺杂剂组成。优选通过在固体载体上负载脱氢活性金属和任选的另外的活性金属的所有元素前体,然后进行适当的热处理来制备第一组合物。
类似地,优选通过在无机载体上负载过渡金属和任选的掺杂剂的所有元素前体,然后进行适当的热处理来制备第二组合物。
元素前体是含有所需元素的起始化合物,其可通过适当的热处理转化成最终的烃转化催化剂中的所需形式的元素。例如,元素前体可包括元素的氧化物、卤化物、醇盐、硝酸盐、碳酸盐、甲酸盐、氧化物、胺或氢氧化物。
更优选地,通过在固体载体上浸渍,优选同时(共浸渍)浸渍以溶液形式提供的脱氢活性金属和任选的另外的活性金属的元素前体,然后煅烧来制备第一组合物。煅烧优选在氧化气氛中,在300-800℃范围内的温度下进行1-24小时,甚至更优选在400-600℃的温度下进行2-10小时。
还更优选地,通过在无机载体上浸渍,优选顺序地浸渍以溶液形式提供的过渡金属和任选的掺杂剂的元素前体,然后煅烧来制备第二组合物。煅烧优选在氧化气氛中,在300-800℃范围内的温度下进行1-24小时,甚至更优选在400-600℃的温度下进行2-10小时。
由上述制备方法得到的第一和第二组合物通常为粉末形式,具有小于800微米的平均粒径。
在一个实施方式中,物理混合第一组合物和第二组合物,优选第一组合物与第二组合物的重量比为1:10至10:1,更优选1:5至5:1,甚至更优选1:3至3:1,甚至更优选1:2至2:1,以形成烃转化催化剂。
在一个实施方式中,烃转化催化剂可以是粉末形式。在另一个实施方式中,烃转化催化剂也可以形成更适合工业应用的形状,例如丸、片、挤出物或球。
第一和第二组合物的物理混合可在烃转化催化剂成形之前或之后进行。
在一个实施方式中,将第一组合物和第二组合物分别形成所需形状,然后将所需形状的第一组合物和形成所需形状的第二组合物物理混合,以获得烃转化催化剂。
在更优选的实施方式中,将第一组合物的粉末和第二组合物的粉末物理混合以获得烃转化催化剂,然后可以将所得的烃转化催化剂形成任何所需的形状。
在第一组合物、第二组合物或烃转化催化剂的成型中,可以加入粘合材料以促进粉末形成所需的形状。可以使用本领域已知的任何粘合材料。
在另一个实施方式中,以宏观规模的层形式提供第一和第二组合物也是可能的,其中第一组合物和第二组合物在固定床反应器中作为单独的层排列,其中第二组合物的层插入在第一组合物层和包含裂化催化剂的第二层之间。
包含分子筛的裂化催化剂也形成层结构。本领域技术人员将容易地知道如何在反应器中制备和布置各个层。
最优选的是通过反应器的烃进料流首先与烃转化催化剂接触,随后与裂化催化剂接触。
在一个实施方式中,烃转化催化剂的第一层和包含裂化催化剂的第二层布置在同一反应器中,更优选是固定床反应器。
有利的是,当烃转化催化剂的第一层和包含裂化催化剂的第二层布置在同一反应器中时,它们被惰性材料隔开以防止两种材料的非故意混合。
根据本发明,还有一种将包含饱和烃化合物的烃进料转化为烯烃产物的方法,其包括使烃进料流与根据本发明的催化剂体系接触。
在一个实施方式中,烃进料流通过首先与烃转化催化剂接触,然后与裂化催化剂接触而通过催化剂体系。
在另一个实施方式中,烃进料流包含选自乙烷、丙烷、丁烷、戊烷和它们的混合物的链烷烃(paraffin),优选丙烷、丁烷和它们的混合物,甚至更优选地,烃进料流是丙烷。
根据本发明的工艺可以在广泛的操作条件下操作。然而,一些特定范围的操作条件可导致高烯烃生产选择性。
在一个实施方式中,用于烃进料的转化的方法在200-800℃的范围内,优选在350-700℃,甚至更优选在450-650℃的温度下进行。
在另一个实施方式中,该方法在0.01至10巴表压的范围内,优选0.05至5巴表压的范围内的压力下进行。
获得烯烃产物所希望的收率所需的接触时间取决于若干因素,例如操作温度、操作压力和催化剂活性。在一个实施方式中,该方法在0.01至20hr-1范围内的重量时空速度(WHSV)下进行,优选0.05至5hr-1范围内。
该方法可以间歇方式或连续方式进行。对于商业规模,有利的是连续操作该方法。连续操作可以用固定床、流化床或本领域已知的其它技术进行,通常优选固定床。
在与烃进料流接触之前,任选地预处理催化剂体系。预处理条件可包括使催化剂体系与惰性气体、氧化性气体、还原性气体或它们的混合物在升高的温度下接触,优选在250℃至850℃,更优选在400℃至750℃,甚至更优选500℃至700℃。在一个优选的实施方式中,预处理条件包括使催化剂与还原性气体,更优选与氢气在500-700℃范围内的温度下接触约0.5-8小时。
在操作条件下与烃进料流接触后,一些有毒物质、重质烃和焦炭可能沉积在催化剂体系的表面上。这通常会影响催化剂混合物的活性,从而其随时间逐渐下降。可以对用过的催化剂体系进行适当的再生以恢复其至少一些活性。
在一个实施方式中,烃转化方法包括再生步骤,其中再生步骤包括在高温下使催化剂体系与氧化剂接触。应小心控制再生步骤,以避免过度加热催化剂并且破坏催化剂的结构。在一个实施方式中,再生步骤在200℃至700℃范围内的温度下进行,优选在300℃至600℃。可以使用其他已知的再生技术而没有限制。
令人惊讶地发现,本发明的催化剂体系显著降低了烃转化方法中高级烯烃的量,而特别是作为高价值产物的乙烯的量增加了。
已经制备了多种根据本发明的催化剂体系和一种没有裂化催化剂的对照例。本发明人惊奇地发现,根据本发明的催化剂体系显示出高级烯烃,尤其是丁烯的选择性显著降低,但乙烯的选择性提高。
具体实施方式
实验结果
在下面的实施例部分中,已经使用根据本发明的催化剂体系和一个对照例研究了丙烷向烯烃,优选乙烯和丁烯的转化。
对于每个试验,设置反应区,使裂化催化剂位于烃转化催化剂的下游。烃转化催化剂与所用的裂化催化剂的重量比约为40:1。C3H8被进料,并首先与烃转化催化剂接触,然后与裂化催化剂接触。反应区保持在约485至490℃,0.1巴表压,WHSV约0.15至0.2h-1。结果在大约115-120小时的运行时间测量并在下表中示出。
对于实施例中使用的烃转化催化剂,催化剂已经与第一和第二组合物一起使用。
通过将氯铂酸六水合物的溶液和三硝酸镱溶液浸渍到SiO2-ZrO2混合物粉末上,然后将所得材料在100℃下干燥2小时,接着在空气气氛下在700℃下煅烧3个小时,从而制备出在SiO2-ZrO2载体上的含有5wt%铂和1.4wt%镱的第一组合物。
对于含有7wt%W、4wt%Y-沸石,9wt%Mg-Al氧化物和余量SiO2的第二组合物,通过将偏钨酸铵水合物溶液浸渍在SiO2和Y-沸石的混合物上,然后在110℃下干燥3小时。然后将所得材料与Mg-Al-CO3层状双氢氧化物混合,接着在空气气氛下在550℃下煅烧2小时而制备得到。
将1重量份的第一组合物和1重量份的第二组合物物理混合在一起,以形成烃转化催化剂。
如下文所示,在每个实施例中使用不同的裂化催化剂。
实施例1(对照例):不使用裂化催化剂
实施例2(对照例):使用SiO2和Al2O3的混合物
实施例3:使用Si/Al比为500的ZSM-5沸石
实施例4:使用硅沸石
实施例5:使用SAPO-34沸石
实施例6:使用SAPO-11沸石
实施例7:使用β-沸石
表1
从上述结果可以看出,当催化剂体系包括沸石或硅沸石作为下游层时,与不使用裂化催化剂或使用SiO2-Al2O3的常规混合物作为催化剂体系的下游层相比,丁烯选择性降低而乙烯选择性增加。
可以进一步注意到,当ZSM-5用作裂化催化剂时,乙烯选择性的增加最高。当使用β-沸石时,乙烯选择性增加但丁烯选择性没有降低。当使用硅沸石时,丁烯选择性降低,乙烯选择性增加,然而,也产生更多的C5+,其通常是不希望的副产物。在前面的描述和权利要求中公开的特征可以单独地和以其任何组合用于以各种形式实现本发明的材料。
在前面的描述和权利要求中公开的特征可以单独地和以其任何组合用于以各种形式实现本发明的材料。
Claims (10)
1.催化剂产品,包含:
i.烃转化催化剂的第一层,所述烃转化催化剂包含:
含有在固体载体上的脱氢活性金属的第一组合物,所述脱氢活性金属选自铂、钯、铱、铬或它们的混合物;以及
含有在无机载体上的过渡金属的第二组合物,所述过渡金属选自钼、钨、铼或它们的混合物;以及
ii.包含裂化催化剂的第二层,
其中所述裂化催化剂包含分子筛;
其中所述分子筛是沸石和/或硅沸石;并且
其中所述沸石选自具有在20-1500范围内的二氧化硅与氧化铝之比的ZSM-5。
2.根据权利要求1所述的催化剂产品,其中所述第一层与所述第二层的重量比为50:1至1:20。
3.根据权利要求1所述的催化剂产品,其中所述固体载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、氧化镁、氧化钙或它们的混合物。
4.根据权利要求1所述的催化剂产品,其中所述无机载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、沸石或它们的混合物。
5.根据权利要求1所述的催化剂产品,其中所述第二组合物还包含混合的镁-铝氧化物或混合的钙-铝氧化物。
6.用于将包含饱和烃化合物的烃进料转化为烯烃产物的方法,包括使烃进料流与根据权利要求1-5中任一项所述的催化剂产品接触。
7.根据权利要求6所述的方法,其中所述烃进料流包含选自乙烷、丙烷、丁烷、戊烷或它们的混合物的链烷烃。
8.根据权利要求6所述的方法,其中所述方法在200-800℃范围内的温度下进行。
9.根据权利要求6所述的方法,其中所述烃进料流通过首先与所述烃转化催化剂接触,然后与所述裂化催化剂接触而通过所述催化剂产品。
10.根据权利要求6所述的方法,其中在与所述烃进料流接触之前,通过使所述催化剂产品与惰性气体、氧化性气体、还原性气体或它们的混合物在250℃至850℃范围内的温度下接触来预处理所述催化剂产品。
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