CN102686315B - 加氢和脱氢催化剂的制备 - Google Patents
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Abstract
在用于生产适合于实现烃加氢和/或脱氢反应的含金属的催化剂组合物的方法中,将包含与无定形粘结剂组合的多孔结晶材料的催化剂载体用能够与载体表面和与金属组分结合的锚定材料进行处理。此外,金属组分的前体被沉积在催化剂载体的表面上,接着具有沉积在其上的前体的处理过的催化剂载体被暴露于有效条件下以将前体转化成金属组分并导致锚定材料与载体表面和与金属组分结合。
Description
技术领域
本发明涉及适合于实现加氢和/或脱氢反应的催化剂的制备。
背景技术
在精炼和石油化学工业中,烃的加氢和脱氢是重要的反应。这种反应的非限制性实例包括重整、脱蜡、加氢裂化、加氢处理、和加氢精制。许多这样的反应采用包含贵金属组分的催化剂,所述贵金属组分被沉积在由与无定形粘结剂组合的多孔结晶材料构成的载体上。
目前,大多数贵金属催化剂是通过将铂和/或钯络合物浸渍到催化剂载体上而制得的。然后干燥所述催化剂以去除水,并在空气中煅烧以分解金属络合物从而在载体表面上留下高度分散的铂和/或钯氧化物。然后,通过在氢存在下还原贵金属氧化物以产生活性铂和钯位点来活化催化剂。然而,在催化剂活化(特别是在水蒸气存在下)和投入生产的操作这两者期间,催化剂活性由于金属烧结而下降,金属烧结出现在细分散的铂和钯粒子聚集并且活性金属表面降低时。
本发明试图通过提供新方法来解决该问题,所述新方法是通过预处理将贵金属锚定剂添加到催化剂载体表面上并由此降低对金属烧结的倾向并显著改善催化剂的稳定性。尽管改善了稳定性,但添加贵金属锚定剂对初始催化剂活性或选择性似乎没有可测量的负面影响。
美国专利5,041,401公开了沸石催化剂组合物,所述组合物包含(a)沸石组分,(b)占据了沸石孔的非构架的多价金属氧化物组分,所述非构架的多价金属氧化物通过包括在含有约百万分之1至100份水的气氛中在至少约600℃的温度下煅烧的方法掺入到沸石组分的孔中,和(c)贵金属组分。据称,金属氧化物组分(b)的存在赋予了操作中贵金属组分(c)显著增加的抗聚集和/或迁移性,但将金属氧化物掺入到沸石孔中有望改变催化剂成品的活性和选择性。
在应用催化A:总则308(2006)(AppliedCatalysisA:General308(2006)),111-118页,Kanda等人的题为“铝改性对用于噻吩氢硫化的负载在MCM-41上的Pt的催化性能的影响(EffectofaluminummodificationoncatalyticperformanceofPtsupportedonMCM-41forthiophenehydrosulfurization)”的文章中公开了MCM-41的氧化铝改性改善了Pt/MCM-41加氢脱硫催化剂的Pt分散和催化活性。然而,在该文章中没有公开或建议铝改性会提高沉积在结合的MCM-41催化剂上的贵金属的抗聚集性。
发明内容
在一方面,本发明涉及用于生产适合于实现烃加氢和/或脱氢反应的含金属的催化剂组合物的方法,该方法包括:
(a)提供包含与基本上无定形的粘结剂组合的多孔结晶材料的催化剂载体;
(b)用能够与载体表面和与金属组分结合的锚定材料处理催化剂载体;
(c)将所述金属组分的前体沉积在催化剂载体的表面上;然后
(d)将具有沉积在其上的所述前体的处理过的催化剂载体暴露于有效条件下以将所述前体转化成金属组分并导致所述锚定材料与载体表面和与金属组分结合。
适当地,所述多孔结晶材料是硅酸盐或硅铝酸盐。
在一个实施方式中,所述多孔结晶材料是中孔材料,例如选自MCM-41、MCM-48、MCM-50、及其混合物的中孔材料。
适当地,所述无定形粘结剂是无机氧化物材料。
在一个实施方式中,所述锚定材料选自氧化磷、磷含氧酸、氧卤化磷、及其混合物。
在另一个实施方式中,所述锚定材料是选自元素周期表第4和13族的金属的硝酸盐,例如硝酸铝、硝酸锆、及其混合物。
适当地,所述金属组分包括至少一种选自元素周期表第6至10族的金属及其化合物和混合物,例如铂、钯、及其化合物和混合物。
适当地,所述前体包括所述金属组分的络合物,并且所述沉积(c)通过浸渍或离子交换来进行。
适当地,(d)包括在含氧气氛中加热处理过的催化剂载体以将前体转化成金属组分的氧化物,以及然后在含氢气氛中加热处理过的催化剂载体以将氧化物转化成金属组分。
在其它方面,本发明涉及通过本文中描述的方法生产的含金属的催化剂组合物,以及该催化剂组合物在降低芳族化合物在含芳族化合物的烃进料中的浓度的方法中的用途。
附图说明
图1是将用实施例1的Pt/PdSi-MCM-41催化剂在加氢精制加氢处理过的600N脱蜡油中获得的相对于投入生产的时间的总芳族化合物浓度与用实施例2的磷酸共浸渍的Pt/PdSi-MCM-41催化剂所获得结果进行比较的图。
具体实施方式
本文中所描述的是用于生产适合于实现烃加氢和/或脱氢反应的含金属的催化剂组合物的方法。所述方法采用包含与无定形粘结剂组合的多孔结晶材料的催化剂载体,并且最初涉及用能够与载体表面和与金属组分结合的锚定材料处理催化剂载体。在用锚定材料处理催化剂载体后或同时,金属组分的前体被沉积在催化剂载体的表面上。此后,具有沉积在其上的金属前体的处理过的催化剂载体被暴露于有效条件下的一个或多个加热步骤以将前体转化成金属组分并导致锚定材料与载体表面和与金属组分结合。由此产生的催化剂与除了没有贵金属锚定剂以外相同的催化剂相比,表现出类似的初始催化活性但改善的抗金属聚集性。
所产生的催化剂组合物能用在各种过程中,包括脂族和芳族两种烃的加氢和/或脱氢。适当的实例包括重整、脱蜡、加氢裂化、和加氢处理。然而,具体来说,本发明被用于生产加氢精制催化剂,所述加氢精制催化剂被用于减少润滑剂和燃料的芳族化合物含量。
用于生产本发明含金属的催化剂组合物的催化剂载体包含与基本上无定形的粘结剂组合的多孔结晶材料。所述多孔结晶材料通常是硅酸盐或硅铝酸盐,并且取决于催化剂组合物的目的用途,可以是微孔材料或中孔材料。在本文中使用时,术语微孔用于表示具有小于1.5nm直径的孔的材料,以及中孔用于表示具有1.5nm至50nm直径的孔的材料。
适当的微孔材料的实例是沸石,特别是约束指数(如在美国专利4,016,218中定义的)为约1至12并通常被称为中等孔径沸石的那些,以及约束指数小于1并通常被称为大孔径沸石的那些。
适当的中孔分子筛包括ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35、和ZSM-48。ZSM-5被详细描述在美国专利3,702,886和Re.29,948中。ZSM-11被详细描述在美国专利3,709,979中。ZSM-12被描述在美国专利3,832,449中。ZSM-22被描述在美国专利4,556,477中。ZSM-23被描述在美国专利4,076,842中。ZSM-35被描述在美国专利4,016,245中。ZSM-48被更具体地描述在在美国专利4,234,231中。采用中孔分子筛的催化剂组合物在诸如重整和脱蜡的反应中是特别有用的。
适当的大孔分子筛包括沸石β、沸石Y、超稳Y(USY)、脱铝Y(DealY)、丝光沸石、ZSM-3、ZSM-4、ZSM-18、ZSM-20、以及MCM-22和它的相关分子筛。沸石ZSM-14被描述在美国专利3,923,636中。沸石ZSM-20被描述在美国专利3,972,983中。沸石β被描述在美国专利3,308,069和Re.28,341中。低钠超稳Y分子筛(USY)被描述在美国专利3,293,192和3,449,070中。脱铝Y沸石(DealY)可通过在美国专利3,442,795中建立的方法来制备。沸石UHP-Y被描述在美国专利4,401,556中。丝光沸石是天然存在的材料,但也能以合成形式得到,例如TEA-丝光沸石(即从包含四乙铵导向剂的反应混合物中制备的合成丝光沸石)。TEA-丝光沸石被公开在美国专利3,766,093和3,894,104中。MCM-22被描述在美国专利4,954,325中。采用大孔分子筛的催化剂组合物在诸如加氢裂化和加氢处理的反应中是特别有用的。
适当的中孔材料的实例是M41S族材料,M41S族材料的制备被进一步描述在J.Amer.Chem.Soc.(美国化学会志),1992,114,10834中。在M41S族中的材料的实例包括MCM-41、MCM-48、和MCM-50。这类的优选成员是MCM-41,MCM-41的制备被描述在美国专利5,098,684中。MCM-41是无机、多孔、不分层的相,其具有大小均匀的孔的六角形排列。MCM-41的物理结构类似一捆麦秆,其中麦秆的开孔(孔腔直径)为1.5至10nm。MCM-48具有立体对称性并被描述在美国专利5,198,203中,而MCM-50具有层状结构并被描述在美国专利5,304,363中。采用中孔分子筛的催化剂组合物在加氢精制反应中是特别有用的。
在本发明的催化剂组合物中,将多孔结晶材料与基本上无定形的粘结剂复合,所述粘结剂对催化剂在使用中所经历的温度和其它条件具有抗性。适当的粘结剂材料包括无机氧化物例如氧化铝、二氧化硅、二氧化硅-氧化铝、氧化锆、二氧化钛、氧化镁、或这些和其它氧化物的混合物。后者可以是天然存在的或者是凝胶状沉淀或凝胶的形式,包括二氧化硅和金属氧化物的混合物。粘土也可以与氧化物型粘结剂一起被包括进来以改变催化剂的机械性能,或者在它的制造中给予帮助。与分子筛联合使用本身具有催化活性的材料,即与其结合或者在它的合成期间存在,可以改变催化剂的转化率和/或选择性。无活性的材料适当地起到稀释剂的作用以控制转化量,使得产物可以被经济且有序地获得,而不用采用其它手段来控制反应速率。这些材料可以被掺入到天然存在的粘土例如膨润土、高岭土中,从而改善催化剂在工业操作条件下的抗压强度并起到催化剂的粘结剂或基质的作用。分子筛和无机氧化物粘结剂的相对比例变化广泛,筛含量为约1至约90重量%,并且更通常在约2至约80重量%的复合物的范围内。
本发明的催化剂组合物还包括加氢/脱氢金属组分,所述金属组分通常包括至少一种选自元素周期表第6至10族的金属及其化合物和混合物。更具体地,加氢/脱氢金属组分通常包括至少一种选自元素周期表第8至10族的贵金属及其化合物和混合物,例如铂、钯、及其化合物和混合物。在本文中使用时,周期表族的编码制是如ChemicalandEngineeringNews(化学和工程新闻),63(5),27(1985)中公开的。
通常,加氢/脱氢金属组分以总催化剂组合物的约0.2重量%和约3.0重量%之间的量存在于催化剂组合物中。在一个实际的实施方式中,其中催化剂组合物旨在被用在加氢精制润滑剂和燃料中,加氢/脱氢金属组分包含铂和钯两者,铂和钯两者分别以总催化剂组合物的约0.1重量%至约1.0重量%以及约0.1重量%至约2.0重量%的量存在。
为了在活化和操作期间提高它的稳定性并降低对金属烧结和聚集的倾向,本发明的催化剂组合物还包含与金属和与载体化学结合的金属锚定剂。这些金属锚定剂被认为附着到催化剂载体的无定形组分上,并且显然不与多孔结晶组分相互作用,因为催化剂的选择性通常不受锚定剂的存在的影响。
通过用能够与催化剂载体表面和与催化剂的金属组分结合的锚定材料处理催化剂载体通常通过浸渍来产生金属锚定剂。适当的锚定材料包括氧化磷、磷含氧酸、氧卤化磷、及其混合物,其通常是在水溶液中。其它适当的锚定材料包括来自元素周期表第4和13族的金属硝酸盐例如硝酸铝、硝酸锆、及其混合物的水溶液。在用锚定材料处理后或同时,催化剂的金属组分的前体被沉积在催化剂载体的表面上。所述前体通常是各催化剂金属的络合物例如胺络合物的水溶液,并且通常通过浸渍或离子交换被沉积在催化剂载体上。
将锚定材料和一种或多种金属前体沉积在催化剂载体上后,催化剂组合物被暴露于一个或多个热处理步骤以将前体转化成所需要的具有催化活性的金属组分(即将催化剂活化)并导致锚定材料与催化剂载体表面和与金属组分结合。适当的热处理步骤包括(i)在含氧气氛例如空气中加热处理过的催化剂载体以将一种或多种金属前体转化成各金属组分的氧化物,以及然后(ii)在含氢气氛中加热处理过的催化剂载体以将一种或多种氧化物转化成一种或多种金属组分。所述加热(i)通常在约250℃至约350℃的温度下进行约0.5至约4.0小时,而所述加热(ii)通常在150℃至约300℃的温度下进行约0.5至约4.0小时。
本发明的催化剂组合物可用于催化各种烃加氢和脱氢反应,包括许多具有商业/工业重要性的那些。实例包括:
(a)含芳族化合物的润滑剂和燃料的加氢精制,反应条件包括温度为约150℃至约400℃,氢分压为约740至约20786kPa(100至3000psig),液时空速(LHSV)为约0.1至约10hr-1,以及氢与进料的比率为约89至约1780m3/m3(500至10000scf/B);
(b)石蜡族进料的脱蜡,反应条件包括温度为约200℃至约450℃,压力为约0至1000psig,WHSV为约0.2hr-1至约10hr-1,以及氢/烃摩尔比为约0.5至约10;
(c)初沸点为至少345℃的重质烃馏分的加氢裂化,反应条件包括温度为约290℃至约440℃,压力为约2860至约10445kPa,液时空速(LHSV)为约0.1至约10hr-1,以及氢循环率为250至1000m3/m3(约1400至5600SCF/桶);和
(d)石脑油流的重整,反应条件包括温度在约400℃至600℃的范围内,压力在约大气压至约40巴的范围内,以及液时空速(LHSV)在约0.1至约15hr-1的范围内。
(e)润滑剂基础油的加氢处理以降低氮和/或硫杂质的水平,反应条件包括温度为约150至400℃,氢分压为1480至20786kPa(200至3000psig),空速为0.1至10hr-1,以及氢与进料的比率为89至1780m3/m3(500至10000scf/B)。
现在参考以下非限制性实施例和附图更具体地描述本发明。
实施例1:基础实例
将约100克与35重量%氧化铝结合的Si-MCM-41荷载到浸渍圆锥体中。将含有7.8克四氨合硝酸铂溶液(4重量%铂)和25.86克四氨合硝酸钯(3.64重量%铂)的溶液用水稀释至142ml。在圆锥体以8RPM旋转的同时将溶液喷洒到Si-MCM-41载体上。然后将载体在空气中干燥,并在马弗炉中在580℉(304℃)下煅烧1小时。由此产生的催化剂的性能显示在表1中。
实施例2:用磷酸共浸渍MCM-41
将约100克与35重量%氧化铝结合的Si-MCM-41荷载到浸渍圆锥体中。将含有7.8克四氨合硝酸铂溶液(4重量%铂)、25.86克四氨合硝酸钯(3.64重量%铂)、和0.23克磷酸的溶液用水稀释至142ml。在圆锥体以8RPM旋转的同时将溶液喷洒到Si-MCM-41载体上。然后将载体在空气中干燥,并在马弗炉中在580℉(304℃)下煅烧1小时。由此产生的催化剂的性能显示在表1中。
实施例3:用硝酸铝预处理
将约100克与35重量%氧化铝结合的Si-MCM-41荷载到浸渍圆锥体中。通过将7.3克硝酸铝添加到142ml水中来制备溶液。然后在圆锥体以8RPM旋转的同时将该溶液喷洒到Si-MCM-41载体上。然后将载体在空气中干燥,并在马弗炉中在1000℉(538℃)下煅烧3小时。将含有7.8克四氨合硝酸铂溶液(4重量%铂)和25.86克四氨合硝酸钯(3.64重量%铂)的第二个溶液用水稀释至142ml。在圆锥体以8RPM旋转的同时将该溶液喷洒到Si-MCM-41载体上。然后将载体在空气中干燥,并在马弗炉中在580℉(304℃)下煅烧1小时。由此产生的催化剂的性能显示在表1中。
实施例4:硝酸锆预处理
将约100克与35重量%氧化铝结合的Si-MCM-41荷载到浸渍圆锥体中。通过将4.8克锆添加到142ml水中来制备溶液。然后在圆锥体以8RPM旋转的同时将该溶液喷洒到Si-MCM-41载体上。然后将载体在空气中干燥,并在马弗炉中在约1000℉(538℃)下煅烧3小时。将含有7.8克四氨合硝酸铂溶液(4重量%铂)和25.86克四氨合硝酸钯(3.64重量%铂)的第二溶液用水稀释至142ml。在圆锥体以8RPM旋转的同时将该溶液喷洒到Si-MCM-41载体上。然后将载体在空气中干燥,并在马弗炉中在580℉(304℃)下煅烧1小时。由此产生的催化剂的性能显示在表1中。
表1
*O/M=氧化学吸附(如下所定义)
实施例5:Pt/Pd催化剂的烘蒸
将来自实施例1至4的约10克催化剂荷载到样品皿中,并在石英管炉中在100%蒸汽的气氛中在500℉(260℃)下放置约3小时。将来自实施例1至4的第二批10克催化剂荷载到样品皿中,并在石英管炉中在100%蒸汽的气氛中在800℉(427℃)下放置约3小时。这些烘蒸被用于模拟在启动和投入生产的操作中会出现的贵金属聚集。金属表面积的损失通过氧化化学吸附(O/M)来测定,即在还原后能够被吸收到烘蒸过的金属表面上的氧的量。结果总结在表2中。
表2
如表2所示,通过预浸渍或共浸渍在Si-MCM-41/粘结剂载体表面上添加这些贵金属锚定剂位点显著降低了金属烧结,并且将改善催化剂的稳定性。
实施例6:催化性能
评估实施例1和2的各催化剂用于加氢精制加氢处理过的600N脱蜡油的性能。脱蜡油先被加氢处理以将硫含量降低到约200ppm并将总芳族化合物含量降低到约415毫摩尔/kg从而模拟第II组基础油。约5cc的各催化剂被荷载到升流式微型反应器中。约3cc的80至120目砂被添加到催化剂中,以确保均匀的液体流。在用氮和氢进行压力试验后,将催化剂在氮中在260℉(127℃)下干燥约3小时,冷却至室温,在氢中在约260℃下活化8小时,然后冷却至150℃。向反应器进给油进料,并将温度升高到275℃,然后保持恒定约7至10天。氢纯度为100%,并且没有使用气体回收。
每天监测通过芳族化合物、硫、氢、和氮含量定义的产物质量。芳族化合物通过UV吸收来测定(毫摩尔/kg)。总芳族化合物含量作为投入生产的时间的函数被显示在图1中,从中可以看出,在金属浸渍期间用磷酸共浸渍Si-MCM-41载体对催化剂性能没有显著影响,但改善了催化剂对贵金属烧结的抗性。
尽管已通过参考具体实施方式描述和说明了本发明,本领域普通技术人员将明白,本发明赋予其本身不一定在本文中说明的变体。于是,因为这个原因,出于确定本发明的真正范围的目的,只应参考所附权利要求。
Claims (11)
1.用于生产适合于实现烃加氢和/或脱氢反应的含金属的催化剂组合物的方法,该方法包括:
(a)提供包含与无定形粘结剂组合的多孔结晶材料的催化剂载体,其中所述多孔结晶材料是中孔材料;
(b)用能够与载体表面和与金属组分结合的锚定材料处理催化剂载体,其中所述锚定材料选自氧化磷、磷含氧酸、氧卤化磷、及其混合物;
(c)将所述金属组分的前体沉积在催化剂载体的表面上;和
(d)将具有沉积在其上的所述前体的处理过的催化剂载体暴露于有效条件下以将所述前体转化成金属组分并导致所述锚定材料与载体表面和与金属组分结合,从而与没有(b)步骤的情况下生产的催化剂相比,降低了所述金属组分的烧结,如通过在步骤(d)之后测量的氧化学吸附的增加所示出的。
2.权利要求1的方法,其中所述多孔结晶材料是硅酸盐或硅铝酸盐。
3.权利要求1的方法,其中所述中孔材料选自MCM-41、MCM-48、MCM-50、及其混合物。
4.权利要求1的方法,其中所述无定形粘结剂是无机氧化物材料。
5.权利要求1的方法,其中所述金属组分包括至少一种选自元素周期表第6至10族的金属及其化合物和混合物。
6.权利要求1的方法,其中所述金属组分包括铂、钯、及其化合物和混合物。
7.权利要求1的方法,其中所述前体包括所述金属组分的络合物。
8.权利要求1的方法,其中所述沉积(c)通过浸渍或离子交换来进行。
9.权利要求1的方法,其中所述处理(b)和所述沉积(c)被同时进行。
10.权利要求1的方法,其中(d)包括在含氧气氛中加热处理过的催化剂载体以将前体转化成金属组分的氧化物,以及然后在含氢气氛中加热处理过的催化剂载体以将氧化物转化成金属组分。
11.权利要求1的方法,其中:所述中孔材料选自MCM-41、MCM-48、MCM-50、及其混合物;所述金属组分包括铂和/或钯;和所述锚定材料选自氧化磷、磷含氧酸、氧卤化磷、及其混合物。
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JP5432386B2 (ja) | 2014-03-05 |
CA2784472A1 (en) | 2011-07-07 |
CN102686315A (zh) | 2012-09-19 |
CA2784472C (en) | 2016-04-05 |
KR20120098879A (ko) | 2012-09-05 |
WO2011081785A1 (en) | 2011-07-07 |
EP2512672A1 (en) | 2012-10-24 |
US8546286B2 (en) | 2013-10-01 |
US20110139685A1 (en) | 2011-06-16 |
KR101635249B1 (ko) | 2016-06-30 |
JP2013513479A (ja) | 2013-04-22 |
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