CN104128189B - 用于加氢处理或加氢裂化的基于钼的催化剂的制备方法 - Google Patents
用于加氢处理或加氢裂化的基于钼的催化剂的制备方法 Download PDFInfo
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- CN104128189B CN104128189B CN201410179710.5A CN201410179710A CN104128189B CN 104128189 B CN104128189 B CN 104128189B CN 201410179710 A CN201410179710 A CN 201410179710A CN 104128189 B CN104128189 B CN 104128189B
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- molybdenum
- oet
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
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- 239000011733 molybdenum Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 67
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
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- 239000002184 metal Substances 0.000 claims description 30
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- 238000004073 vulcanization Methods 0.000 claims description 24
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Abstract
本发明涉及要用于加氢处理或加氢裂化工艺的基于钼的催化剂的制备方法。本发明涉及用于实施加氢处理和加氢裂化工艺中的氢化反应的催化剂的制备方法。所述催化剂由至少一种基于钼(Mo)、为其单体或二聚形式、具有至少一个Mo=O或Mo‑OR键或至少一个Mo=S或Mo‑SR键的单核前体—其中[R=CxHy,其中x≥1且(x‑1)≤y≤(2x+1),或R=Si(OR')3或R=Si(R')3,其中R'=Cx'Hy',其中x'≥1且(x'‑1)≤y'≤(2x'+1)]——和任选由至少一种第VIII族元素促进剂制成。所述前体沉积到适合其所用工艺的氧化物载体上,所述催化剂在低于200°C的温度下干燥,然后有利地在用于所述工艺前硫化。
Description
发明领域
本发明描述了在加氢处理和加氢裂化工艺中涉及的氢化反应中以及在加氢裂化工艺中固有涉及的加氢裂化反应中特别有效的基于钼(Mo)的催化剂的制备方法。
本发明还涉及所述催化剂在加氢处理和/或加氢裂化工艺中的用途。
现有技术
关于用于烃进料的加氢处理(HDT)和加氢裂化(HCK)的催化剂的总论
在下列著作中分别充分描述了用于烃进料的加氢处理和加氢裂化的催化剂的组成和用途:"Catalysis by transition metal sulphides, From Molecular Theory toIndustrial Application", 2013, H. Toulhouat, P. Raybaud和"HydrocrackingScience and Technology", 1996, J. Scherzer, A. J. Gruia, Marcel Dekker Inc。
因此,精炼工艺中所用的催化剂——无论意在用于加氢处理还是加氢裂化反应,通常以由基于元素周期表的至少一种第VIB族的金属和任选至少一种第VIII族的金属的活性相的存在提供的加氢脱氢功能为特征。最常见的配方是钴-钼(CoMo)、镍-钼(NiMo)和镍-钨(NiW)类型。这些催化剂可以为本体形式(对加氢处理催化剂具有特定价值)或为负载态,在这种情况中使用不同性质的多孔固体。在该后一情况中,该多孔载体通常是非晶或低结晶氧化物(氧化铝、硅铝酸盐等),任选与沸石或非沸石材料结合。在制备后,构成所述催化剂的至少一种第VIB族的金属和任选至少一种第VIII族的金属通常以氧化形式存在。由于用于加氢裂化工艺(HCK)和加氢处理(HDT)工艺的活性和稳定形式是硫化形式,因此这些催化剂必须经过硫化步骤。这可以在与工艺相关的装置中(被称作器内硫化)或在将催化剂装入该装置之前(被称作器外硫化)进行。
技术人员通常知道上述应用领域中的良好催化性能是如下因素的作用:1) 待处理的烃进料的性质,2) 所用方法,3) 所选功能的操作条件,和4) 所用催化剂。在后一情况中,具有高催化潜力的催化剂还已知具有下列特征:1) 优化的加氢脱氢功能(相关的活性相理想地分散在载体表面并具有高活性相含量)和2) 在使用HCK反应的工艺的特定情况中,所述加氢脱氢功能与裂化功能之间的良好平衡。还应该指出,理想地,无论待处理的烃进料的性质如何,在开发高活性表面积的同时,催化剂的活性位点必须为试剂和反应产物可达,这导致所述催化剂的组成氧化物载体的结构和质地方面的特定约束。
形成加氢处理和加氢裂化催化剂的加氢脱氢相的普通方法由如下组成:使用“干浸渍”技术将包含至少一种第VIB族的金属和任选至少一种第VIII族的金属的前体沉积到氧化物载体上,接着熟化、干燥和任选煅烧的步骤,以致形成所用的所述金属的氧化物形式。接着最终硫化步骤,以生成如上所述的活性加氢脱氢相。
已经广泛研究了由这些“传统”合成程序获得的催化剂的催化性能。特别地,已经表明,在相对较高的金属含量下,在煅烧步骤后形成难硫化的相(烧结现象)(H.Toulhouat, P. Raybaud "Catalysis by transition metal sulphides, FromMolecular Theory to Industrial Application", 2013)。例如,在负载在氧化铝性质的载体上的CoMo或NiMo类型的催化剂的情况中,这些是1) 具有足以通过XRD检测的尺寸的MoO3、NiO、CoO、CoMoO4或Co3O4的微晶,和/或2) Al2(MoO4)3、CoAl2O4或NiAl2O4类型的物类。含有元素铝的上文列举的三种物类是技术人员公知的。它们起因于氧化铝载体与活性加氢脱氢相的溶液中的前体盐之间的相互作用,这尤其导致从氧化铝基质中提取的Al3+离子与所述盐之间的反应以形成式[Al(OH)6Mo6O18]3-的Anderson 杂多阴离子,其本身是难硫化的相前体。这组物类的存在导致相关催化剂的催化活性的间接的不可忽略的损失,因为由于其一部分固定在无活性或低活性物类中,属于至少一种第VIB族的金属和任选至少一种第VIII族的金属的元素没有完全以其最大潜力利用。
上述传统催化剂的催化性能可因此特别是通过开发此类催化剂的新型制备方法而改进,其可以:
1) 确保加氢脱氢相的良好分散,特别是在高金属含量下(例如通过控制基于过渡金属的粒子的粒度,在硫化前的热处理后保持这些粒子的性质,等等);
2) 限制难硫化的物类的形成,例如通过更好地控制活性加氢脱氢相(和/或其前体)与所用多孔载体之间的相互作用,或通过获得构成活性相的过渡金属之间的更好协同效应,等等;
3) 在保持开发出的高活性表面积的同时确保试剂和反应产物的良好扩散(优化多孔载体的化学、质地和结构性质)。
NiMo配对被认为是最适合芳烃氢化以及加氢脱氮(它们是加氢处理反应中或用于加氢裂化的关键功能)的第VIB和VIII族金属的配对。尽管使用普通前体(H3PO4、MoO3 Ni(OH)2或七钼酸铵和硝酸镍)通过“传统”途径在载体上沉积大量NiMo和尽管有关于制备步骤的参数研究,但我们还不能1) 控制片材的分散和形态,和2) 优化在载体上生成的活性相的促进程度:这些是基本增强活性相的氢化力并由此在加氢处理工艺中实施所需氢化反应和/或在加氢裂化工艺中提高中间馏分的收率中的关键要素。对意在用于加氢处理和加氢裂化的催化剂而言,近年来的科学挑战之一是优化沉积在各种载体上的氢化相。
因此,发现可用于获得具有改进的性能的新型催化剂的制备加氢处理催化剂的方式显然是有利的。现有技术表明研究人员已转向各种方法,包括使用许多和各种多金属氧酸盐,添加掺杂元素,添加具有许多和各种性质(溶剂化、络合等)的有机分子或最后,但在较低程度上由于在使用中的困难而使用单核前体。
由多金属氧酸盐(POM)制备加氢处理和加氢裂化催化剂
在现有技术中已经提到多金属氧酸盐的优点。例如,文献US 2 547 380提到第VIII族金属的杂多酸盐,如磷钼酸或硅钼酸的钴或镍盐的有益用途。在该专利中,杂多酸仍含有磷或硅,该后一元素是该结构的中心原子。此类化合物的缺点在于产生受到限制的原子比(第VIII族元素/第VI族元素)。例如,磷钼酸钴具有0.125的Co/Mo比。
专利FR 2 749 778描述了通式MxAB12O4的杂多阴离子的优点,其中M是钴或镍,A是磷、硅或硼且B是钼或钨;如果A是磷,x的值为2或更大,如果A是硅,x为2.5或更大,如果A是硼,x为3或更大。这些结构优于文献US 2 547 380中公开的结构的优点在于获得更高的原子比(第VIII族元素/第VI族元素)并由此产生表现更好的催化剂。借助如在例如磷钼酸、磷钨酸、硅钼酸或硅钨酸的组成中出现的至少一部分具有低于其正常值6的化合价的钼或钨的存在获得该比率的这种提高。
专利FR 2 764 211描述了式MxAB11O40M'C(Z-2x)的杂多阴离子的合成和用途,其中M是钴或镍,A是磷、硅或硼且B是钼或钨,M’是钴、铁、镍、铜或锌,且C是H+离子或烷基铵阳离子,x的值为0至4.5,z的值为7至9。因此,这种式对应于发明FR 2 749 778中要求保护的式,但其中一个M’原子被B原子取代。该后一式的优点在于使得第VIII族元素与第VIB族元素之间的原子比可能高达0.5并由此更好地促进活性相。
专利FR 2 315 721证实使用式Nix+y/2AW11-yO39-5/2y. zH2O的杂多化合物,更特别使用式Ni4SiW11O39和式Ni5SiW9O34的杂多化合物的优点,在加氢裂化和加氢处理过程中带来出乎意料的催化性能。
在所有情况中,通过使用杂多钼酸盐或杂多钨酸镍盐,这些团队研究了通过使它们处于相同分子体中而促进金属-促进剂(promoter)相互作用,这意味着可以控制硫化的催化剂的促进程度并由此可以提高活性位点数。
最后,在专利FR 2 969 647和FR 2 969 645中还揭示了使用截留在介孔结构二氧化硅中的这些多金属氧酸盐。本发明的催化剂与以传统方式(将多金属氧酸盐浸渍到介孔载体上)制成的催化剂相比在瓦斯油加氢处理和加氢裂化中表现出非常有意义的性能。
通过添加有机分子制备加氢处理或加氢裂化催化剂
将有机化合物添加到加氢处理催化剂中以改进它们的活性如今是技术人员公知的。许多专利保护各种系列的有机化合物,如可任选醚化的单醇、二醇或多元醇的用途(WO96/41848、WO 01/76741、US 4 012 340、US 3 954 673、EP 0 601 722)。在专利申请EP 0466 568和EP 1 046 424中描述了用C2-C14单酯改性的催化剂,但这样的改性并非总是为其充分提高该催化剂的性能以符合对炼油商而言不断变得更严格的关于燃料硫含量的规范。
为了克服这一点,专利FR 2 880 823描述了包含第VIB族和第VIII族金属、作为载体的难熔氧化物和包含至少2个式R1-O-CO-R2-CO-O-R1或R1-CO-O-R2-O-CO-R1的酯羧酸官能的有机化合物或在专利FR 2 953 740中确切地为琥珀酸C1-C4二烷基酯与乙酸的催化剂的用途。
现有技术中的其他专利描述了例如如KK Japan Energy的公开号为JP1995-136523的专利申请中所述与在加氢处理催化剂上联合使用有机酸或醇相关联或如专利2963 360中与环状低聚糖的使用相关联的活性增加。
尽管有时对活性增加的解释不足,不再必须证实在加氢处理和加氢裂化催化剂的制备过程中使用有机分子的意义,但所述制备仍受步骤数和受要浸渍的有机分子不可溶于常用水溶液限制。
使用单核前体(在其结构中仅含一个金属原子的前体)制备加氢处理和加氢裂化
催化剂
由在其结构中只有单个钼或钨原子的不同多金属氧酸盐前体制备负载型催化剂早已为人所知但仍少见。
自二十世纪80年代以来,已经表明,可以使用沉积在SiO2上的基于烯丙基类型的Mo或W(WR4,其中R = C4H7)的有机金属前体生成NiW或NiMo催化剂,其在加氢脱硫中的固有活性(相对于Mo或W原子计的活性)比以更传统方式制备的催化剂的固有活性高最多4倍(在由Mo或钨酸制备的催化剂的情况中使用七钼酸铵(NH4)6Mo7O24.6H2O,在由W制备的催化剂的情况中使用H2WO4)(Yermakov等人, Journal of Molecular Catalysis, 1981, 205-214,Yermakov, Journal of Molecular Catalysis, 21, 1983, 35-55和Yermakov等人,Applied Catalysis 11, 1984, 1-13)。但是,由有机金属前体在二氧化硅上制备的催化剂的活性仍高于在氧化铝上制备的催化剂(相对于Mo或W原子计的活性)。
在二十世纪90年代,由硫代钼酸盐(四硫代钼酸双(四丁基铵)(TBA)2MoS4)制备氧化铝载CoMo类型的催化剂,并证实了在加氢脱硫用途中使用它们的重要性(Halbert等人Journal of Catalysis 130, 1991, 116-129)。
在2008年,证实了使用有序介孔氧化铝上的二氧代二乙酰丙酮酸钼制备加氢处理催化剂的优点(Kaluza等人, Applied Catalysis A: General, 351, 2008, 93-101)。这些研究随后表明,由这种前体制成的CoMo和NiMo催化剂比商业催化剂对加氢脱硫更有效。专利EP 0 178 711描述了在腈型溶剂(还另外任选含有氯化溶剂)中在镍和/或钴卤化物,分别优选为氯化镍和/或氯化钴六水合物NiCl2(H2O)6和CoCl2(H2O)6存在下由含有卤化钼,优选MoCl5的溶液制备在二氧化硅上的加氢处理催化剂。
专利US 5 137 859描述了由溶解在选自醇、醚、酮和芳族化合物的有机溶剂中的选自醇盐或螯合化合物或钼或铬二醇盐(glycoxides)的化合物和选自醇盐或螯合化合物或镍或钴 二醇盐的化合物制备在氧化铝载体上的用于烃油馏分的加氢脱硫的催化剂。新浸渍的氧化物催化剂随后必须经过在存在或不存在氧的情况下在大约150℃的温度下干燥的步骤和必须经过在含氧气氛中在至少200℃的温度下煅烧的步骤。此类处理可能促进通过煅烧含碳部分接枝的前体的变性并可能造成醇盐类的缩聚(归因于热处理气体中存在的水或归因于在碳质基团的煅烧过程中释放的水)。因此,可以估计,在完好物类的接枝过程中最初提供的分散损失并在硫化后在表面上生成较少活性位点。
申请人的研究由此引向由钼和任选至少一种第VIII族元素,特别是镍制备氢化催化剂——改变活性相的金属物类前体的化学和结构组成以改变载体与这些前体之间的相互作用以更好地硫化被认为难硫化的钨以及改变载体与该催化剂的活性硫化物相之间的相互作用以使其更好地分散。特别地,申请人的研究已引向使用单体或二聚形式的具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的基于钼的单核前体——其中[R = CxHy,其中x ≥ 1且(x-1) ≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1)]——作为根据本发明在烃进料的加氢处理工艺和加氢裂化工艺中的氢化反应中所用的催化剂的活性相的特定前体。
申请人由此证实,根据特定制备模式由至少一种其单体或二聚形式并具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的基于Mo的单核前体——其中[R = CxHy,其中x ≥ 1且(x-1) ≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x'≥ 1且(x'-1) ≤ y' ≤ (2x'+1)]——制成的负载型催化剂与由标准前体,如多金属氧酸盐制成的催化剂相比表现出改进的硫化和改进的催化活性,所述催化剂已有利地预硫化,然后用于加氢处理或加氢裂化工艺。
发明描述
发明目的
本发明涉及由至少一种基于钼、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体——其中[R = CxHy,其中x≥ 1且(x-1) ≤ y ≤(2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤(2x'+1)]——和任选至少一种第VIII族元素制备负载型催化剂的方法。
本发明还涉及通过所述制备方法能够制成的催化剂。
最后,本发明涉及可以以这种方式制成的所述催化剂在氢化反应中,特别是在加氢处理和加氢裂化工艺中的用途。
发明概述
本发明涉及包含至少一种载体、任选至少一种元素周期表第VIII族的金属和至少钼的催化剂的制备方法,其中:
·在有机溶剂A中,以至少一种基于Mo、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体化合物——其中[R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1)]——的形式将钼引入载体上,
·和通过在低于200℃的温度下干燥进行由此浸渍的载体的热处理。
所述干燥可以在无水气氛中或在低真空或高真空下或在惰性气流下进行。
所述干燥优选在真空下和在环境温度下进行。
第VIII族的金属有利地选自钴、铁和镍。
第VIII族的金属优选是镍。
钼前体有利地是以其单体或二聚形式使用的下式的基于Mo的单核前体
Mo(=O)n(=S)n'(OR)a(SR')b(L1)c(L2)d(L3)e(L4)f(L5)g
其中R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或 R = Si(OR'')3或R = Si(R'')3,其中R'' = Cx''Hy'',其中[x'' ≥ 1且(x''-1) ≤ y'' ≤ (2x''+1)],
其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1),或R' = Si(OR''')3或R' = Si(R''')3,其中R''' = Cx'''Hy''',其中[x''' ≥ 1且(x'''-1) ≤ y''' ≤(2x'''+1)],
其中0 ≤ n+n' ≤ 2且0 ≤ n ≤ 2且0 ≤ n' ≤ 2,
其中,如果n = n' = 0,则(a≠0或b≠0)且[(a+b+c+d+e+f+g = 6且0 ≤ a ≤ 6,0 ≤ b ≤ 6,0 ≤ c ≤ 6,0 ≤ d ≤ 6,0 ≤ e ≤ 6,0 ≤ f ≤ 6,0 ≤ g ≤ 6),或(a+b+c+d+e+f+g = 5且0 ≤ a ≤ 5,0 ≤ b ≤ 5,0 ≤ c ≤ 5,0 ≤ d ≤ 5,0 ≤ e ≤5,0 ≤ f ≤ 5,0 ≤ g ≤ 5),或(a+b+c+d+e+f+g = 4且0 ≤ a ≤ 4,0 ≤ b ≤ 4,0 ≤c ≤ 4,0 ≤ d ≤ 4,0 ≤ e ≤ 4,0 ≤ f ≤ 4,0 ≤ g ≤ 4)],
其中,如果[(n=1且n' = 0)或(n' = 1且n = 0)],则[(a+b+c+d+e+f+g = 4且0 ≤a ≤ 4,0 ≤ b ≤ 4,0 ≤ c ≤ 4,0 ≤ d ≤ 4,0 ≤ e ≤ 4,0 ≤ f ≤ 4,0 ≤ g ≤4)]或 [(a+b+c+d+e+f+g = 3且0 ≤ a ≤ 3,0 ≤ b ≤ 3,0 ≤ c ≤ 3,0 ≤ d ≤ 3,0≤ e ≤ 3,0 ≤ f ≤ 3,0 ≤ g ≤ 3)],
其中,如果[n+n'=2且0 ≤ n ≤ 2且0 ≤ n' ≤ 2],则(a+b+c+d+e+f+g = 2且0≤ a ≤ 2,0 ≤ b ≤ 2,0 ≤ c ≤ 2,0 ≤ d ≤ 2,0 ≤ e ≤ 2,0 ≤ f ≤ 2,0 ≤ g≤ 2),
其中(L1)、(L2)、(L3)、(L4)和(L5)选自THF、二甲基醚、二甲基硫醚、P(CH3)3、烯丙基、芳基、卤素/含卤有机化合物、胺、乙酸根/乙酸盐、乙酰丙酮酸根/乙酰丙酮酸盐、卤离子/卤代烃/卤代芳烃、氢氧根/氢氧化物、-SH类型的配体或技术人员已知的任何其它配体。
该钼前体优选选自Mo(OEt)5、Mo(OEt)6、Mo(=O)(OEt)4、Mo(=S)(OEt)4、Mo(=S)(SEt)4、Mo(=O)2(OEt)2、Mo(OC6H5)6、Mo(SEt)5、Mo(SEt)6、Mo(OEt)(SEt)4、Mo(OEt)2(SEt)3、Mo(OEt)3(SEt)2、Mo(OEt)4(SEt)、Mo(=O)(OEt)3(acac)其中Et = CH2CH3(乙基)且acac =(CH3COCHCOCH3)-(乙酰丙酮酸根),为它们的单体或二聚形式。
可以同时或相继引入钼和任选的一种或多种第VIII族金属。
有利地,该制备方法包括至少一个器内和/或器外进行的用于气相硫化的最终步骤。
更特别地,该制备方法可包括至少下列步骤:
a) 通过使包含有机溶剂A和至少所述基于钼、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体——其中[R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1)]——的溶液S与已在低真空或高真空下或在惰性气流下煅烧的多孔矿物载体接触,进行浸渍;
b) 在无水气氛中熟化;
c) 在无水气氛中或在低真空或高真空下或在惰性气流下在低于200℃的温度下干燥所述浸渍的载体;
d) 在混合物中含有至少5体积% H2S的H2S/H2或H2S/N2混合物中在等于或高于环境温度的温度下器外硫化。
任选的第VIII族金属可以在步骤a)中在与钼前体相同的溶液S中,或在干燥c)后在后浸渍步骤a2)中借助使用有机溶剂B的溶液,或在硫化步骤d)后在后浸渍步骤a3)中借助水溶液或有机溶液引入。
本发明还涉及根据所述方法能够制备的催化剂。
所述催化剂优选包含占总催化剂重量的4重量%至30重量%的钼含量和0.1重量%至8重量%的一种或多种第VIII族金属含量。
本发明还涉及所述催化剂在用于烃进料的氢化,优选用于加氢处理或加氢裂化的反应中的用途。
发明详述
本发明涉及用于实施加氢处理和加氢裂化工艺中的氢化反应的催化剂的制备方法,其由至少一种基于钼、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体——其中[R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或R =Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1)]——和任选至少一种第VIII族元素制成。所述前体使用技术人员已知的任何方法沉积到适合其所用工艺的氧化物载体上,所述催化剂在低于200℃的温度下干燥并和有利地在用于所述工艺前硫化。
本发明的优点之一因此在于基于钼的加氢处理催化剂的创新性制备,其能通过将前体接枝和保存到载体表面上,甚至保存到二氧化硅载体上而实现更好的分散。这些改进意味着可能可以生成硫化物类型的更具活性的相,并因此可能可以生成用于实施所需的氢化或加氢裂化反应的更具活性的位点,因此可以实现比文献中的那些高的本发明的催化剂的活性,或可以生成与传统催化剂相同的活性但催化剂上的金属原子数减半。
所述制备方法优选包括至少下列步骤:
a) 通过使包含有机溶剂A和至少一种基于Mo、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体——其中[R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1)]——的溶液与多孔矿物载体接触来进行浸渍的步骤,所述多孔矿物载体有利地已在低真空或高真空下或在惰性气流下煅烧以排走可能物理吸附在所述载体上的水;
b) 熟化步骤;
c) 在无水气氛中或在低真空或高真空下或在惰性气流下在低于200℃的温度下干燥所述浸渍的载体的步骤;
d) 硫化步骤,优选在混合物中含有至少5体积% H2S的H2S/H2或H2S/N2混合物中在等于或高于环境温度的温度下器外进行。
任选的一种或多种第VIII族元素——下文称作促进剂,可以在溶液中如下引入:
i) 在浸渍步骤a),与基于钼的单核前体共浸渍;
ii) 在干燥步骤c)后,在被称作后浸渍a2)的步骤中借助使用有机溶剂B的溶液。在这种情况中,第二熟化步骤b2)和在低于200ºC的温度下的第二干燥步骤c2)是必须的并可以在与步骤b)和c)的过程中所述的条件相同的条件下进行;
iii) 在步骤d)后,在后浸渍步骤a3)中借助水溶液或有机溶液。在这种情况中,在根据本发明在加氢处理或加氢裂化工艺中使用催化剂之前必须增加新的熟化步骤b3)、在低于200ºC的温度下的新的干燥步骤c3)和新的硫化步骤d2)。
根据本发明以其单体或二聚形式使用的基于Mo的单核前体有利地具有式:
Mo(=O)n(=S)n'(OR)a(SR')b(L1)c(L2)d(L3)e(L4)f(L5)g
其中R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或 R = Si(OR'')3或R = Si(R'')3,其中R'' = Cx''Hy'',其中[x'' ≥ 1且(x''-1) ≤ y'' ≤ (2x''+1)],
其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1),或R' = Si(OR''')3或R' = Si(R''')3,其中R''' = Cx'''Hy''',其中[x''' ≥ 1且(x'''-1) ≤ y''' ≤(2x'''+1)],
其中0 ≤ n+n' ≤ 2且0 ≤ n ≤ 2且0 ≤ n' ≤ 2,
其中,如果n = n' = 0,则(a≠0或b≠0)且[(a+b+c+d+e+f+g = 6且0 ≤ a ≤ 6,0 ≤ b ≤ 6,0 ≤ c ≤ 6,0 ≤ d ≤ 6,0 ≤ e ≤ 6,0 ≤ f ≤ 6,0 ≤ g ≤ 6),或(a+b+c+d+e+f+g = 5且0 ≤ a ≤ 5,0 ≤ b ≤ 5,0 ≤ c ≤ 5,0 ≤ d ≤ 5,0 ≤ e ≤5,0 ≤ f ≤ 5,0 ≤ g ≤ 5),或(a+b+c+d+e+f+g = 4且0 ≤ a ≤ 4,0 ≤ b ≤ 4,0 ≤c ≤ 4,0 ≤ d ≤ 4,0 ≤ e ≤ 4,0 ≤ f ≤ 4,0 ≤ g ≤ 4)],
其中,如果[(n=1且n' = 0)或(n' = 1且n = 0)],则[(a+b+c+d+e+f+g = 4且0 ≤a ≤ 4,0 ≤ b ≤ 4,0 ≤ c ≤ 4,0 ≤ d ≤ 4,0 ≤ e ≤ 4,0 ≤ f ≤ 4,0 ≤ g ≤4)]或 [(a+b+c+d+e+f+g = 3且0 ≤ a ≤ 3,0 ≤ b ≤ 3,0 ≤ c ≤ 3,0 ≤ d ≤ 3,0≤ e ≤ 3,0 ≤ f ≤ 3,0 ≤ g ≤ 3)],
其中,如果[n+n'=2且0 ≤ n ≤ 2且0 ≤ n' ≤ 2],则(a+b+c+d+e+f+g = 2且0≤ a ≤ 2,0 ≤ b ≤ 2,0 ≤ c ≤ 2,0 ≤ d ≤ 2,0 ≤ e ≤ 2,0 ≤ f ≤ 2,0 ≤ g≤ 2),
其中(L1)、(L2)、(L3)、(L4)和(L5)是技术人员公知的配体并且为THF、二甲基醚、二甲基硫醚、P(CH3)3、烯丙基、芳基、卤代(选自氟代、氯代和溴代)/含卤有机化合物、胺、乙酸根/乙酸盐、乙酰丙酮酸根/乙酰丙酮酸盐、卤离子/卤代烃/卤代芳烃、氢氧根/氢氧化物、-SH等类型。配体优选选自乙酰丙酮酸根、THF和二甲基醚。
根据本发明的前体优选不含配体(L1)、(L2)、(L3)、(L4)和(L5)。
根据本发明的前体优选选自下列化合物:Mo(OEt)5、Mo(OEt)6、Mo(=O)(OEt)4、Mo(=S)(OEt)4、Mo(=S)(SEt)4、Mo(=O)2(OEt)2、Mo(OC6H5)6、Mo(SEt)5、Mo(SEt)6、Mo(OEt)(SEt)4、Mo(OEt)2(SEt)3、Mo(OEt)3(SEt)2、Mo(OEt)4(SEt)、Mo(=O)(OEt)3(acac)其中Et = CH2CH3(乙基)且acac = (CH3COCHCOCH3)-(乙酰丙酮酸根),为它们的单体或二聚形式。
根据本发明的前体更优选是Mo(OEt)5。
钼Mo的量通常为在最终制备步骤后获得的在将其用于加氢处理工艺或加氢裂化工艺之前的最终催化剂的 4重量%至30重量%,优选为最终催化剂的7重量%至25重量%。
表面密度——相当于载体的每单位表面积沉积的钼原子Mo的量——有利地为0.5至8个Mo原子/平方纳米载体,优选为1至7个Mo原子/平方纳米载体。
用于使溶液和载体接触的步骤a)是浸渍。浸渍是技术人员公知的。本发明的浸渍方法选自干浸渍、过量浸渍和连续浸渍。有利地使用被称作干浸渍的方法。
步骤a)中所用的有机溶剂A通常是烷烃、醇、醚、酮、氯化溶剂或芳族化合物。优选使用环己烷和正己烷。
步骤b)是旨在使物类向载体核心扩散的熟化步骤。其有利地在环境温度下在无水气氛中(无水)进行优选30分钟至24小时。该气氛应该优选无水以便不会使预浸渍的前体缩聚。
步骤c)过程中进行的干燥旨在除去浸渍溶剂A。该气氛应优选无水(没有水)以使所述预浸渍的前体不会缩聚。温度绝不能超过200℃以使接枝或沉积在载体表面上的所述前体保持完好。该温度优选不超过120℃。非常优选在真空下在环境温度下进行干燥。或者,可以通过经过惰性气体进行这一步骤。
硫化步骤d)有利地使用在混合物中含有至少5体积% H2S的H2S/H2或H2S/N2气体混合物在环境温度或更高的温度下在等于或高于1巴的总压力下器外进行至少2小时。硫化温度优选为250℃。硫化温度非常优选为350℃。
硫化步骤d)也可以,或除器外进行的步骤d)外,在使用该催化剂的催化工艺,例如加氢处理或加氢裂化工艺一开始实施时使用技术人员公知的如上所述的任何硫化法器内进行。
优选的第VIII族元素是非贵金属元素:它们选自Ni、Co和Fe。第VIII族元素优选是钴和镍。第VIII族元素非常优选是镍。第VIII族金属以盐、螯合化合物、醇盐或二醇盐的形式,优选以乙酰丙酮酸盐或乙酸盐的形式引入。
如果该促进剂如本发明中所述在i)和ii)中引入,含有第VIII族元素的化合物优选是含硫化合物、含氧化合物、螯合化合物、醇盐和二醇盐。其优选以乙酰丙酮酸盐或乙酸盐的形式引入。
如果该促进剂如本发明中所述在iii)中引入,含有第VIII族元素的化合物 可以以盐、含硫化合物、含氧化合物、螯合化合物、醇盐和二醇盐的形式引入。其优选以乙酰丙酮酸盐或乙酸盐的形式引入。
可以有利地以盐形式使用的第VIII族元素源是技术人员公知的。它们选自硝酸盐、硫酸盐、氢氧化物、磷酸盐和卤化物(选自氯化物、溴化物和氟化物)。
第VIII族元素促进剂有利地以在最终制备步骤后获得的在将其用于加氢处理工艺或加氢裂化工艺之前的最终催化剂的0.1重量%至8重量%,优选0.5重量%至5重量%的量存在于该催化剂中。
在步骤c)后在被称作后浸渍的步骤中引入促进剂时使用的有机溶剂B通常是烷烃、醇、醚、酮、氯化化合物或芳族化合物。优选使用甲苯、苯、二氯甲烷、四氢呋喃、环己烷、正己烷、乙醇、甲醇和丙酮。
在步骤iii)的情况中用于促进剂(第VIII族元素)的浸渍的溶剂在使用非盐水前体和水的情况中对应于有机溶剂B,或在前体是盐水时对应于醇。
通过钼和任选通过至少一种第VIII族元素确保所述催化前体的加氢脱氢官能。有利地,加氢脱氢功能选自下列元素的组合形成的组:镍-钼或钴-钼或镍-钴-钼。
本发明的催化剂的载体是有利地包含至少铝和/或至少硅的多孔矿物载体。
所述载体优选包含至少一种氧化铝或至少一种氧化硅。有利地,所述载体可以是或不是酸性的。有利地,所述载体可以是或不是介孔结构的。
所述多孔矿物载体可以有利地选自单独或混合物形式的过渡氧化铝类、掺杂氧化铝类(优选被磷、硼和/或氟掺杂)、硅质岩和二氧化硅类、硅铝酸盐类(优选非晶或低结晶度)、结晶非沸石分子筛,如硅铝磷酸盐类、铝磷酸盐类、铁硅酸盐类、硅铝酸钛类(titaniumsilicoaluminates)、硼硅酸盐类、铬硅酸盐类(chromosilicates)和过渡金属铝磷酸盐类。
在所述多孔矿物载体选自过渡氧化铝类、硅质岩和二氧化硅类,如介孔二氧化硅的情况下,例如,所述载体不是酸性的。术语“过渡氧化铝”是指例如α相氧化铝、δ相氧化铝、γ相氧化铝或这些各种相的氧化铝的混合物。
在所述多孔矿物载体选自硅铝酸盐(优选非晶或低结晶度)、非沸石结晶分子筛如硅铝磷酸盐类、铝磷酸盐类、铁硅酸盐类、硅铝酸钛类、硼硅酸盐类、铬硅酸盐类和过渡金属铝磷酸盐类、掺杂氧化铝类(优选被磷、硼和/或氟掺杂)的情况下,所述载体是酸性的。技术人员已知的任何已知的二氧化硅-氧化铝或任何硅铝酸盐适用于本发明的上下文。
当所述多孔矿物载体被称为介孔结构时,其随之包含本发明的材料的以介孔规模组织的基本粒子,即具有1.5至50纳米,优选1.5至30纳米,再更优选4至20纳米的均匀直径并以均匀和规则方式分布在各所述粒子中的孔隙规模的有序多孔性(介孔结构化)。位于基本介孔结构粒子的介孔之间的材料是非晶的并形成厚度为1至30纳米,优选1至10纳米的壁或隔断。壁厚度相当于第一介孔与第二介孔的间距,第二介孔是最靠近所述第一介孔的孔隙。上述介孔性的组织使得所述载体的所述组成粒子的结构可能是六边形、蠕虫形或立方形,优选六边形。所述介孔结构的多孔矿物载体优选选自二氧化硅和二氧化硅-氧化铝。
除上文列举的至少一种氧化物化合物外,本发明的多孔矿物载体,无论是否酸性,是介孔结构的还是非介孔结构的,都包含至少一种沸石,特别但不限于"Atlas of ZeoliteFramework types", 第6次修订版, 2007, Ch. Baerlocher, L. B. L.McCusker, D. H.Olson"中列举的那些。沸石晶体可选自沸石IZM-2、ZSM-5、ZSM-12、ZSM-48、ZSM-22、ZSM-23、ZBM-30、EU-2、EU-11、硅质岩、Beta、沸石A、八面沸石、Y、USY、VUSY、SDUSY、丝光沸石、NU-10、NU-87、NU-88、NU-86、NU-85、IM-5、IM-12、IM-16、镁碱沸石和EU-1。非常优选地,该沸石晶体可选自结构类型MFI、BEA、FAU和LTA的沸石。在构成本发明的材料的多孔矿物载体中可能存在不同的沸石晶体,特别是具有不同结构类型的沸石。特别地,本发明的多孔矿物载体可以有利地包含至少第一沸石晶体(其沸石选自沸石IZM-2、ZSM-5、ZSM-12、ZSM-48、ZSM-22、ZSM-23、ZBM-30、EU-2、EU-11、硅质岩、Beta、沸石A、八面沸石、Y、USY、VUSY、SDUSY、丝光沸石、NU-10、NU-87、NU-88、NU-86、NU-85、IM-5、IM-12、IM-16、镁碱沸石和EU-1,优选选自结构类型MFI、BEA、FAU和LTA的沸石)和至少第二沸石晶体(其沸石不同于第一沸石晶体并选自沸石IZM-2、ZSM-5、ZSM-12、ZSM-48、ZSM-22、ZSM-23、ZBM-30、EU-2、EU-11、硅质岩、Beta、沸石A、八面沸石、Y、USY、VUSY、SDUSY、丝光沸石、NU-10、NU-87、NU-88、NU-86、NU-85、IM-5、IM-12、IM-16、镁碱沸石和EU-1,优选选自结构类型MFI、BEA、FAU和LTA的沸石)。该沸石晶体有利地包含至少一种完全硅质的或除硅外还含有至少一种选自铝、铁、硼、铟、镓和锗,优选铝的元素T的沸石。
除上文列举的至少一种氧化物化合物外,该多孔矿物载体还可有利地包含至少一种二八面体2:1页硅酸盐或三八面体3:1页硅酸盐类型的简单的合成或天然粘土,如高岭石、叶蛇纹石、温石棉、蒙脱石、贝得石、蛭石、滑石、锂蒙脱石、皂石或锂皂石。这些粘土也可任选已脱层。
所述多孔矿物载体优选选自单独或作为混合物使用的介孔氧化铝和二氧化硅-氧化铝,或单独或作为混合物使用的介孔结构二氧化硅类和二氧化硅-氧化铝类。
该催化剂可以以技术人员已知的任何形式使用:其可以是粉末形式,珠粒形式或圆柱形、三叶形或四叶形挤出物形式。可以混合不同形状。
根据本发明,所述催化剂有利地在用于本发明的加氢处理或加氢裂化工艺之前借助该制备法的步骤d)中描述的至少一个气相硫化步骤部分硫化。步骤d)中描述的这种硫化步骤部分生成活性硫化物相,但其可用于防止与要处理的烃进料接触或可能与硫化进料接触的金属前体的浸出(leaching)。所得催化剂用在加氢处理或加氢裂化装置中,在此其可发生在原样引入或由选自二甲基二硫醚(DMDS)、二甲基硫醚、正丁基硫醇和多硫化物化合物的有机含硫化合物的分解获得的氢和硫化氢(H2S)存在下借助要处理的进料进行的器内硫化。使用技术人员公知的方法在200℃至600℃,优选300℃至400℃的温度下进行这种硫化。
加氢处理和加氢裂化工艺,以及进料
最后,本发明还涉及本发明的催化剂在油馏分的加氢处理和加氢裂化工艺中的用途。
用本发明的方法制成的催化剂可有利地用于技术人员已知的需要烃馏分和优选催化裂化的汽油馏分的氢化反应的任何工艺中。本发明的加氢处理和加氢裂化工艺可以有利地在以固定床或移动床或沸腾床模式运行的任何类型的反应器中进行。所述加氢处理工艺或所述加氢裂化工艺优选在以固定床模式运行的反应器中进行。
通过本发明的制备方法获得的催化剂有利地用于烃进料,如油馏分、获自煤的馏分或由天然气产生的烃的加氢处理反应,更特别是需要氢化反应:芳烃的氢化、烃进料的加氢脱氮、加氢脱硫、加氢脱金属或加氢裂化是可以举出的反应。
也可以有利地在催化裂化进料或渣油的加氢脱硫或瓦斯油(ULSD或超低硫柴油)的强加氢脱硫的进料的预处理过程中使用这些催化剂。
加氢处理工艺中所用的进料的实例是单独或作为混合物使用的汽油、瓦斯油、真空瓦斯油、常压渣油、减压渣油、常压馏分、真空馏分、重质燃料、油、蜡和石蜡、废油、渣油或脱沥青原油或衍生自热或催化转化工艺的进料。处理的进料,特别是上文列举的那些通常含有杂原子,如硫、氧和氮,对于重质进料,它们通常还含有金属。
利用上述烃进料的加氢处理反应的工艺中所用的操作条件通常如下:温度有利地为180℃至450℃,优选250℃至440℃,压力有利地为0.5至30 MPa,优选1至18 MPa,时空速度有利地为0.1至20 h-1,优选0.2至5 h-1,以在常温和常压条件下测得的氢体积/液体进料体积表示的氢/进料比有利地为50 L/L至2000 L/L。
加氢裂化反应中所用的进料的实例是LCO(轻循环油(获自催化裂化装置的轻瓦斯油))、常压馏分、真空馏分,例如获自原油直馏或转化装置,如FCC、焦化或减粘裂化装置的瓦斯油、衍生自芳烃萃取装置的进料、润滑基础油或由润滑基础油的溶剂脱蜡获得的基料、衍生自固定床或沸腾床脱硫或加氢转化工艺的馏分、常压渣油和/或减压渣油和/或脱沥青油,或该进料可以是脱沥青油或包含植物油,或衍生自获自生物质的进料的转化。在本发明的加氢裂化工艺中处理的所述烃进料也可以是如上列举的所述进料的混合物。所述进料中存在的烃进料是芳族化合物、烯烃化合物、环烷化合物和/或链烷化合物。
所述烃进料有利地包含杂原子。所述杂原子选自氮、硫和这两种元素的混合物。当在待处理的所述进料中存在氮时,氮含量为500 ppm或更大,其优选为500至10000重量ppm,更优选700至4000重量ppm,再更优选1000至4000 ppm。当在待处理的所述进料中存在硫时,硫含量为0.01%至5重量%,优选0.2重量%至4重量%,再更优选0.5重量%至3重量%。
所述烃进料可以任选有利地含有金属,特别是镍和钒。使用本发明的加氢裂化工艺处理的所述烃进料的累计镍和钒含量优选小于1重量ppm。所述烃进料的沥青质含量通常小于3000 ppm,优选小于1000 ppm,再更优选小于200 ppm。
本发明的加氢裂化工艺涵盖从温和加氢裂化到高压加氢裂化的压力和转化领域。术语“温和加氢裂化”是指导致通常小于40%的中等转化并在通常2 MPa至10 MPa的低压下运行的加氢裂化。本发明的加氢裂化工艺在至少一种根据本发明的加氢处理催化剂或加氢裂化催化剂存在下进行。本发明的加氢裂化工艺可以在一个或两个步骤中进行,独立于所述工艺的实施压力。其在配有一个或多个反应器的一个或多个反应装置中在使用上述制备方法获得的一种或多种催化剂存在下进行。
本发明的加氢裂化工艺中所用的操作条件可根据进料性质、所需产物的品质和炼油商可得到的设施而千差万别。根据本发明的加氢裂化工艺,有利地使所述加氢裂化催化剂在大于200℃,通常250℃至480℃,有利地320℃至450℃,优选330℃至435℃的温度下在大于1 MPa,通常2至25 MPa,优选3至20 MPa的压力、0.1至20 h-1,优选0.1至6 h-1,再更优选0.2至3 h-1的空间速度(进料的体积流速除以催化剂的体积)下在氢存在下与所述烃进料接触,引入的氢的量使得氢的升数/烃的升数的体积比为80至5000 L/L,通常100至2000 L/L。
本发明的加氢裂化工艺中所用的这些操作通常可用于实现大于15%,再更优选20%至95%的转化成沸点最多370℃,有利地最多340℃的产物的每道转化率。
实施例
为举例说明提供下列实施例;它们证实与现有技术催化剂相比根据本发明的方法制成的催化剂的活性的大量提高,并详细说明本发明而不以任何方式限制其范围。
实施例1: 负载在氧化铝上的NiMo催化剂,表面密度为3 Mo/nm²且Ni/Mo = 0.3(at/at)(根据本发明)
将钼在严格无水介质中干浸渍到通过煅烧铝盐的凝胶合成的商业γ氧化铝型载体(287平方米/克)上。该载体最初在300℃下在空气中在大气压下煅烧6小时。然后在高真空(10-5毫巴)下将其加热至300℃持续14小时,接着储存在手套箱中的惰性介质中。钼前体是五乙醇钼Mo(OC2H5)5。使用干脱气的环己烷作为溶剂。将由1.18克前体制成的1.96毫升浸渍溶液浸渍到2.58克干燥载体上。调节钼的量以获得3 Mo/nm2。在熟化15小时后,挤出物在环境温度下在真空(10-5毫巴)下干燥2小时。这种非硫化催化剂由常用符号Mo/Al2O3规定。
然后将双乙酰丙酮酸镍Ni(acac)2的溶液浸渍到这种催化剂上。使用干脱气的甲苯作为溶剂。首先将镍前体溶解在热甲苯中,然后将含有0.41克前体的2.45毫升溶液浸渍到大约3.76克Mo/Al2O3上。在熟化15小时后,挤出物在环境温度下在真空(10-5毫巴)下干燥3小时。对于这种非硫化NiMo/Al2O3催化剂,钼和镍含量分别为11.60重量%和2.21重量%,这相当于3.0 Mo/nm²的实际表面密度和0.30的Ni/Mo原子比。这种催化剂C1是根据本发明的。
实施例2: 负载在氧化铝上的NiMo催化剂,表面密度为3 Mo/nm²且Ni/Mo=0.3(at/at)(不根据本发明)
将钼和镍在水介质中干共浸渍到通过煅烧铝盐的凝胶合成的商业γ氧化铝型载体(289平方米/克)上。钼前体是七钼酸铵(NH4)6Mo7O24. xH2O。镍前体是硝酸镍Ni(NO3)2.xH2O。调节前体的量以获得3 Mo/nm²和Ni/Mo=0.30 (at/at)。在熟化15小时后,挤出物在120℃下干燥15小时。它们随后在空气流中在450℃下煅烧2小时。这种非硫化NiMo/Al2O3催化剂的钼和镍含量分别为11.75重量%和2.12重量%,这相当于3.0 Mo/nm²的实际表面密度和0.29的Ni/Mo原子比。这种催化剂H1不根据本发明。
实施例3: 在苯胺存在下的甲苯(芳族模型分子)氢化的试验
在苯胺存在下的甲苯氢化的试验旨在评估负载型或本体硫化催化剂在H2S存在下和在氢压下的氢化活性。苯胺的存在、低温和/或在更高温度下NH3(由苯胺的分解获得)的存在抑制具有催化剂的酸官能特征的异构化。苯胺和/或NH3会通过酸-碱反应与载体的酸性位点反应。随后不存在载体的酸性的特征异构化反应。
我们在相同的催化试验装置上小心地进行催化剂的比较以便不会使用可能产生非常规结果的不同催化试验工具干扰该比较。
在固定床横贯的(traversed)反应器中在气相中进行催化试验。该试验可分成两个不同的阶段——硫化和催化试验。在60巴下进行试验。
催化剂首先在气相((H2S/H2混合物),其中H2S的量为15体积%)中在350℃的温度下器外硫化2小时。
活化阶段:
在Flowrence型中试装置(来自Avantium)的固定床横贯的管反应器中在受试进料下对催化剂施以升温,流体从上向下流动。在达到试验温度后立即进行氢化活性的测量。
催化试验:
试验进料由二甲基二硫醚(DMDS)、甲苯、环己烷和苯胺构成。
在350℃的温度下测量等体积催化剂(450微升)的稳定化催化活性。
该试验的操作条件如下(假设全部汽化和理想气体定律):
对于Ptot = 60 bar和T = 350℃:
PpH2 = 36.62巴
PpNH3 = 0.09巴
PpH2S = 2.16巴
Pp甲苯 = 3.75巴
Pp环己烷 = 15.22巴
在活化阶段中HSV = 4 L/L/h,在试验阶段中HSV = 2 L/L/h和H2/进料 = 450 L/L。
通过气相色谱法分析流出物样品。使用相应的氢化活性使用一级动力学表示该催化剂的催化性能:
%HYD甲苯相当于氢化甲苯的百分比。
催化性能显示在表1中。
表1: 催化剂C1和H1的相对氢化活性
这些表示为相对活性,假设催化剂H1等于100。
催化剂 | 相对于H1的氢化活性 |
C1(根据本发明) | 145 |
H1(不根据本发明) | 100 |
表1显示根据本发明要求保护的在氧化铝上制备的催化剂(C1)获得的氢化力的极大提高。根据本发明由钼前体Mo(OEt)5制成的催化剂C1在氢化中的活性大于配方一致但通过传统途径使用杂多阴离子盐制成的催化剂(H1)。
Claims (7)
1.包含至少一种载体、任选至少一种元素周期表第VIII族的金属和至少钼的催化剂的制备方法,所述方法的特征在于:
·在有机溶剂A中,以至少一种基于Mo、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体化合物——其中R = CxHy,其中x≥ 1且(x-1)≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1)≤ y' ≤ (2x'+1)——的形式将钼引入载体上,
·和通过在环境温度下干燥进行由此浸渍的载体的热处理,所述干燥在真空下进行;
· 在含有至少5体积% H2S的H2S/H2或H2S/N2混合物中在等于或高于250°C的温度下进行器外气相硫化的最终步骤,
其中所述钼前体选自Mo(OEt)5、Mo(OEt)6、Mo(=O)(OEt)4、Mo(=S)(OEt)4、Mo(=S)(SEt)4、Mo(=O)2(OEt)2、Mo(OC6H5)6、Mo(SEt)5、Mo(SEt)6、Mo(OEt)(SEt)4、Mo(OEt)2(SEt)3、Mo(OEt)3(SEt)2、Mo(OEt)4(SEt)、Mo(=O)(OEt)3(acac),其中Et = CH2CH3(乙基)且acac =(CH3COCHCOCH3)-(乙酰丙酮酸根),为它们的单体或二聚形式。
2.如权利要求1所述的方法,其中第VIII族的金属选自钴、铁和镍。
3.如权利要求2中所述的方法,其中第VIII族的金属是镍。
4.如权利要求1至3之一中所述的方法,其中所述钼前体是以其单体或二聚形式使用的下式的基于Mo的单核前体
Mo(=O)n(=S)n'(OR)a(SR')b(L1)c(L2)d(L3)e(L4)f(L5)g
其中R = CxHy,其中x≥ 1且(x-1) ≤ y ≤ (2x+1),或 R = Si(OR'')3或R = Si(R'')3,
其中R'' = Cx''Hy'',其中x'' ≥ 1且(x''-1) ≤ y'' ≤ (2x''+1),
其中R' = Cx'Hy',其中x' ≥ 1且(x'-1) ≤ y' ≤ (2x'+1),或R' = Si(OR''')3或R'= Si(R''')3,其中R''' = Cx'''Hy''',其中x''' ≥ 1且(x'''-1) ≤ y''' ≤ (2x'''+1),
其中0 ≤ n+n' ≤ 2且0 ≤ n ≤ 2且0 ≤ n' ≤ 2,
其中,如果n = n' = 0,则a≠0或b≠0,且
a+b+c+d+e+f+g = 6且0 ≤ a ≤ 6,0 ≤ b ≤ 6,0 ≤ c ≤ 6,0 ≤ d ≤ 6,0 ≤ e≤ 6,0 ≤ f ≤ 6,0 ≤ g ≤ 6,或
a+b+c+d+e+f+g = 5且0 ≤ a ≤ 5,0 ≤ b ≤ 5,0 ≤ c ≤ 5,0 ≤ d ≤ 5,0 ≤ e≤ 5,0 ≤ f ≤ 5,0 ≤ g ≤ 5,或
a+b+c+d+e+f+g = 4且0 ≤ a ≤ 4,0 ≤ b ≤ 4,0 ≤ c ≤ 4,0 ≤ d ≤ 4,0 ≤ e≤ 4,0 ≤ f ≤ 4,0 ≤ g ≤ 4,
其中,如果n=1且n' = 0,或n' = 1且n = 0,则a+b+c+d+e+f+g = 4且0 ≤ a ≤ 4,0≤ b ≤ 4,0 ≤ c ≤ 4,0 ≤ d ≤ 4,0 ≤ e ≤ 4,0 ≤ f ≤ 4,0 ≤ g ≤ 4,或
a+b+c+d+e+f+g = 3且0 ≤ a ≤ 3,0 ≤ b ≤ 3,0 ≤ c ≤ 3,0 ≤ d ≤ 3,0 ≤ e≤ 3,0 ≤ f ≤ 3,0 ≤ g ≤ 3,
其中,如果n+n'=2且0 ≤ n ≤ 2且0 ≤ n' ≤ 2,则a+b+c+d+e+f+g = 2且0 ≤ a ≤2,0 ≤ b ≤ 2,0 ≤ c ≤ 2,0 ≤ d ≤ 2,0 ≤ e ≤ 2,0 ≤ f ≤ 2,0 ≤ g ≤ 2,
其中(L1)、(L2)、(L3)、(L4)和(L5)选自THF、二甲基醚、二甲基硫醚、P(CH3)3、烯丙基、芳基、卤素、胺、乙酸根/乙酸盐、乙酰丙酮酸根/乙酰丙酮酸盐、卤离子/卤代烃、氢氧根/氢氧化物和-SH类型的配体。
5.如权利要求1至3之一中所述的催化剂制备方法,其中同时或相继引入钼和任选的一种或多种第VIII族金属。
6.如权利要求1至3之一中所述的催化剂制备方法,其包括至少下列步骤:
a) 通过使包含有机溶剂A和至少所述基于钼、为其单体或二聚形式、具有至少一个Mo=O或Mo-OR键或至少一个Mo=S或Mo-SR键的单核前体——其中R = CxHy,其中x≥ 1且(x-1)≤ y ≤ (2x+1),或R = Si(OR')3或R = Si(R')3,其中R' = Cx'Hy',其中x' ≥ 1且(x'-1)≤ y' ≤ (2x'+1)——的溶液S与已在低真空或高真空下或在惰性气流下煅烧的多孔矿物载体接触,进行浸渍;
b) 在无水气氛中熟化;
c) 在无水气氛中或在低真空或高真空下或在惰性气流下在环境温度的温度下干燥所述浸渍的载体;
d) 在含有至少5体积% H2S的H2S/H2或H2S/N2混合物中在等于或高于250°C的温度下器外硫化。
7.如权利要求6中所述的催化剂制备方法,其中任选的第VIII族金属在步骤a)中在与钼前体相同的溶液S中,或在干燥c)后在后浸渍步骤a2)中借助使用有机溶剂B的溶液,或在硫化步骤d)后在后浸渍步骤a3)中借助水溶液或有机溶液引入。
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FR1353940A FR3004967B1 (fr) | 2013-04-30 | 2013-04-30 | Procede de preparation d'un catalyseur a base de molybdene utilisable en hydrotraitement ou en hydrocraquage |
FR1353940 | 2013-04-30 |
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CN107090004B (zh) * | 2017-05-31 | 2019-03-01 | 张卫东 | 一种有机钼润滑油脂添加剂及其制备方法 |
FR3073429B1 (fr) | 2017-11-15 | 2022-01-07 | Ifp Energies Now | Procede de reduction photocatalytique du dioxyde de carbone mettant en œuvre un photocatalyseur a base de sulfure de molybdene ou de sulfure de tungstene supporte |
RU2698265C1 (ru) * | 2018-11-27 | 2019-08-26 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН) | Бифункциональный катализатор защитного слоя для переработки тяжелого нефтяного сырья и способ его приготовления |
FR3089132A1 (fr) * | 2018-11-30 | 2020-06-05 | IFP Energies Nouvelles | Procédé de préparation d’un matériau catalytique pour des réactions de réduction électrochimique comportant un métal du groupe VI et du groupe VIII obtenu par réduction chimique |
FR3089135A1 (fr) * | 2018-11-30 | 2020-06-05 | IFP Energies Nouvelles | Procédé de préparation d’un matériau catalytique à base de précurseur mononucléaire de type W ou Mo pour des réactions de réduction électrochimique |
FR3089134B1 (fr) * | 2018-11-30 | 2020-11-13 | Ifp Energies Now | Procédé de préparation d’un matériau catalytique d’électrode pour des réactions de réduction électrochimique préparé par électroréduction. |
FR3089133B1 (fr) * | 2018-11-30 | 2024-04-19 | Ifp Energies Now | Procédé de préparation d’une couche active d’électrode pour des réactions de réduction électrochimique |
CN112090443B (zh) * | 2019-06-17 | 2023-03-10 | 中国石油化工股份有限公司 | 加氢脱氧催化剂及其应用和环己烷的制备方法 |
CN112044450B (zh) * | 2020-07-17 | 2021-06-15 | 昆明理工大学 | 一种酸碱双功能生物质碳基催化剂及其制备方法 |
US11911750B1 (en) * | 2022-12-07 | 2024-02-27 | Saudi Arabian Oil Company | Slurry-phase catalyst compositions and methods of making the same |
CN116948703B (zh) * | 2023-09-21 | 2023-11-28 | 弘润石化(潍坊)有限责任公司 | 一种催化裂化柴油加氢生产清洁汽油的方法 |
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EP2799131A1 (fr) | 2014-11-05 |
FR3004967B1 (fr) | 2016-12-30 |
CA2850161A1 (fr) | 2014-10-30 |
IN2014CH02101A (zh) | 2015-07-03 |
KR20140130057A (ko) | 2014-11-07 |
BR102014009715A2 (pt) | 2015-10-13 |
FR3004967A1 (fr) | 2014-10-31 |
BR102014009715B1 (pt) | 2020-11-03 |
JP2014217839A (ja) | 2014-11-20 |
JP6454479B2 (ja) | 2019-01-16 |
CN104128189A (zh) | 2014-11-05 |
US9839903B2 (en) | 2017-12-12 |
US20140323780A1 (en) | 2014-10-30 |
KR102198661B1 (ko) | 2021-01-06 |
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