CN105745019A - 制备加氢处理催化剂的方法 - Google Patents

制备加氢处理催化剂的方法 Download PDF

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CN105745019A
CN105745019A CN201480061233.0A CN201480061233A CN105745019A CN 105745019 A CN105745019 A CN 105745019A CN 201480061233 A CN201480061233 A CN 201480061233A CN 105745019 A CN105745019 A CN 105745019A
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catalyst
phosphorus
molybdenum
nickel
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F·文特
J·A·范威尔塞内斯
M·S·里古托
P·J·A·M·吉尔泰
J·J·M·范维兰德伦
A·阿兹格海
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Shell Internationale Research Maatschappij BV
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Abstract

用于制备加氢处理催化剂的方法，所述加氢处理催化剂包含5wt％?50wt％的钼、0.5wt％?20wt％的镍和0?5wt％的磷，全部基于催化剂的总干重，所述方法包括(a)用钼和镍和基于载体重量1?60wt％的葡萄糖酸，以及任选的磷来处理氧化铝载体，(b)任选地，在40?200℃温度下干燥处理的载体，以及(c)在200?650℃的温度下煅烧处理的且任选干燥的载体，从而获得煅烧的处理的载体。

Description

制备加氢处理催化剂的方法
发明领域
本发明涉及一种用于制备加氢处理催化剂的方法。
发明背景
在烃原料(如原油、馏出油和残留原油馏分)的催化加氢处理中，含有氢化金属的催化剂组合物用于促进脱硫和脱氮反应，并由此提供从烃原料中除去有机硫和有机氮化合物。所述方法涉及在高温和高压下且在氢气存在下，使催化剂颗粒与烃原料接触，以将原料的硫组分转化为硫化氢并且将原料的氮组分转化为氨。随后除去硫化氢和氨，生成加氢处理产物。
加氢处理催化剂包含高熔点氧化物上的氢化金属组分。氢化金属组分通常为第VI族金属组分，例如钼和/或钨，以及第VIII族金属组分，例如镍和/或钴。多孔高熔点氧化物负载材料通常可以是氧化铝。促进剂如磷也可用作加氢处理催化剂的组分。
对进一步改进这些催化剂的性能具有持续兴趣。
可导致改进性能的方法是用含有催化活性金属和有机配体的溶液处理载体，并随后干燥所处理的载体。通过不煅烧这种干燥的催化剂，可获得如出版物例如EP-A-0482818、WO-A-96/41848、WO2009/020913和WO 2012/021389中所述的改进性能。制备仅干燥但不煅烧的催化剂在实际商业实践中是相对复杂且繁琐的。
本发明的目的是寻找一种在低硫低氮燃料如超低硫柴油的生产中相对易于使用同时提供具有良好活性的加氢处理催化剂的方法。
发明概述
已经发现，可通过用进一步包含葡萄糖酸的含金属的浸渍溶液处理载体实现此目的。
因此，本发明涉及一种用于制备加氢处理催化剂的方法，所述加氢处理催化剂包含5wt％-50wt％的钼、0.5wt％-20wt％的镍和0-5wt％的磷，全部基于催化剂的总干重，所述方法包括：
(a)用钼、镍，和基于载体重量1-60wt％的葡萄糖酸，以及任选的磷来处理氧化铝载体，
(b)任选地，在40-200℃的温度下干燥处理的载体，以及
(c)在200-650℃的温度下煅烧所处理的且任选干燥的载体，以获得煅烧处理的载体。
根据本方法，可借助于涉及有限数量的方法步骤的相对简单的方法来制备加氢处理催化剂。除易于生产之外，本发明具有下列优势：发现获得的催化剂在加氢脱硫中具有高活性。
发明详述
本发明的催化剂借助于氧化铝载体制备。优选地，载体由氧化铝组成。更优选地，载体由γ氧化铝组成。
多孔催化剂载体可具有5-35nm范围内的平均孔径，其根据测试ASTM D-4222测量。多孔高熔点氧化物的总孔体积优选在0.2-2ml/g范围内。
多孔高熔点氧化物的表面积，如通过B.E.T.法测量，通常超过100m2/g，并且其一般在100-400m2/g范围内。根据ASTM测试D3663-03，通过B.E.T.法来测量表面积。
催化剂包含载体上的催化活性金属。这些催化活性金属是钼与镍的组合。优选还存在磷。因此，处理的氧化铝载体优选由钼、磷、葡萄糖酸和镍组成。
金属组分可以是金属本身或含有金属的任意组分，包括但不限于金属氧化物、金属氢氧化物、金属碳酸盐和金属盐。
对于镍，金属组分优选选自醋酸盐、甲酸盐、柠檬酸盐、氧化物、氢氧化物、碳酸盐、硝酸盐、硫酸盐，及其两种或更多种。优选地，镍组分是金属硝酸盐。
对于钼，优选的金属盐是钼氧化物和钼硫化物，更优选是还含有铵的盐，例如七钼酸铵和二钼酸铵。
使用的磷化合物优选选自磷的酸(例如偏磷酸、焦磷酸、正磷酸和亚磷酸)以及磷的酸的前体。该前体是能够在水的存在下形成至少一个酸性氢原子的含磷化合物。优选的前体是磷氧化物和磷。优选的磷的酸是正磷酸(H3PO4)。
基于加氢处理催化剂的总干重并基于金属，镍可以以0.5wt％-20wt％、优选1wt％-15wt％、并且最优选2wt％-12wt％范围内的量存在于加氢处理催化剂中。
基于催化剂的总干重并基于金属，钼可以以5wt％-50wt％、优选8wt％-40wt％、并且最优选10wt％-30wt％范围内的量存在于加氢处理催化剂中。最优选地，钼的量为至少11wt％，更特别至少12wt％，更特别至少13wt％，最特别至少14wt％。
基于催化剂的总干重并基于磷，磷可以以0.1wt％-5wt％、优选0.2wt％-5wt％、并且更优选0.5wt％-4.5wt％范围内的量存在于加氢处理催化剂中，。最优选地，磷的量为1.5-3.5wt％，其基于催化剂的总干重。
金属通常以氧化物或硫化物的形式存在。为了确定金属含量，不管其实际形式或状态如何，假设它们以金属本身的形式存在。干重是假设所有挥发性化合物如水和葡萄糖酸已经被除去的重量。可以通过使催化剂保持在400℃温度下至少2小时来确定干重。为了计算磷含量，不管其实际形式如何，假设磷作为元素存在。
葡萄糖酸的量基于干载体的重量优选是2-40wt％葡萄糖酸，更优选3-30wt％，更特别为4-20wt％。
优选地，加氢处理催化剂由在氧化铝载体上的0.5wt％-20wt％的镍、5wt％-50wt％的钼和0.1-5wt％的磷组成，所有金属基于催化剂的总干重，更优选地，载体由γ氧化铝组成。
催化活性金属、葡萄糖酸和磷优选通过用含有这些组分的溶液处理载体来引入到载体中。更优选地，借助于含有这些组分的溶液通过孔体积浸渍添加所述组分。优选所有组分存在于单一溶液中，最优选水溶液。可能并不是所有组分混合在单一浸渍溶液中，例如由于稳定性问题。在此情况下，可优选使用两种或更多种溶液，任选地中间有干燥步骤。
本发明涉及用葡萄糖酸处理载体。这可以是葡萄糖酸或葡萄糖酸的盐或葡萄糖酸的酯，所述酯在溶液中形成葡萄糖酸(盐)(gluconate)。如果溶液用于处理载体，所述溶液通常除了葡萄糖酸本身以外还可能包含葡萄糖酸的盐。对于本发明，用葡萄糖酸的盐处理载体也被认为是用葡萄糖酸处理载体。优选地，通过向溶剂添加葡萄糖酸来制备用于处理载体的溶液。
优选地，葡萄糖酸的重量与沉积于载体上的镍和钼的总重量的比率是0.1-5，更特别0.1-3，更特别0.2-3，更优选0.3-2.5，更优选0.5-2，更优选0.6-1.8，最优选0.7-1.5。
在步骤(b)中，可在步骤(c)的煅烧之前干燥处理的载体。干燥是否确实应该进行，并且如果应该，在什么样的条件下，这取决于存在的挥发性组分的量和随后的煅烧条件。通常，干燥将在40-200℃的温度下进行0.1-6小时，更特别在100-200℃的温度下进行0.5-4小时。最优选地，通过间接加热进行干燥，所述间接加热意味着围绕组合物的环境被加热。间接加热包括使用微波。
步骤(c)的煅烧优选在200-650℃的温度下进行0.1-6小时的期间，更特别在250-600℃、更特别280-550℃的温度下进行0.5-4小时的期间。
不希望受任何理论约束，据信改善的性能是由于催化活性金属、载体和葡萄糖酸之间的相互作用。据信在煅烧作用下，相互作用导致更小的金属氧化物颗粒，在硫化期间维持所述更小的颗粒尺寸。
在用于加氢处理之前，煅烧处理的载体优选被硫化。因此，本发明的方法优选进一步包括：(d)硫化煅烧处理的载体以获得加氢处理催化剂。
硫化之后(所述硫化可原位或非原位进行)，催化剂被认为可易于用于商业用途。
本发明还提供了一种用于加氢处理含硫烃原料的方法，所述方法包括，使烃原料在1-70巴的氢分压和200-420℃的温度下，与根据本发明获得的催化剂接触。
可利用本领域技术人员已知的任何常规方法来进行煅烧处理的载体的硫化。因此，煅烧处理的载体可与包含硫化氢和氢气的气态流接触。在另一个实施方式中，煅烧处理的载体与含硫化合物接触，所述含硫化合物在本发明的接触条件下可分解成硫化氢。此类可分解化合物的实例包括硫醇类、CS2、噻吩类、二甲基硫醚(DMS)和二甲基二硫醚(DMDS)。进一步和优选的选项是通过使组合物在适合的硫化处理条件下与包含含硫化合物的烃原料接触来完成硫化。烃原料的含硫化合物可以是有机硫化合物，特别是通常包含于通过加氢脱硫法生产的石油馏出物中的那种。通常，硫化温度在150-450℃、优选175-425℃、以及最优选200-400℃的范围内。
硫化压力可以在1巴-70巴、优选1.5巴-55巴，以及最优选2巴-45巴的范围内。
本发明更详细地解释于以下实施例中。
实施例
实施例1-含镍/钼催化剂
通过将拟薄水铝石挤成1.3mm三叶型并干燥和煅烧这些以提供如表1所述的氧化铝载体，来制备商业载体。
根据ASTM测试D-4222测量平均孔径。根据ASTM测试D-366303测量表面积。
表1-氧化铝载体性质
性质 载体
煅烧温度(℃) 535
BET表面积(m2/克) 300
平均孔径(nm) 9
通过孔体积浸渍将催化剂的金属组分引入上述载体，以产生以下金属组合物(金属重量基于总催化剂干重)：15％Mo、3.5％Ni、2.2％P。浸渍溶液包括磷酸、氧化镍、三氧化钼和葡萄糖酸。所得溶液的总体积等于氧化铝载体的水孔体积的98％。浸渍溶液中的葡萄糖酸浓度是20wt％，相当于基于载体的葡萄糖酸含量为12.5wt％。
然后在110℃干燥浸渍的载体2小时，并随后在400℃煅烧2小时，以除去葡萄糖酸。
获得以下催化剂。
表2-Ni/Mo催化剂
实施例2-催化剂活性
滴流式微反应器用于测试根据本发明的催化剂相对与商业参考催化剂的脱硫活性。
组合物通过使它们与含有硫增敏剂(spiking agent)的液态烃接触而进行调整和硫化，以提供2.5wt％的硫含量。这些测试中所用的方法条件包括300NI/kg的气-油比、40巴的压力以及1h-1的液时空速。将加权平均床温度(WABT)调节至340-380℃范围内的温度。
用于测试的进料为含有1.28wt％硫的全馏程气油。
方法条件和进料性质代表了典型的超低硫柴油(ULSD)操作。
假设反应级数1.25，确定速率常数。表3给出了获得含10ppm硫的产品所需的温度。实现此硫含量和较高RVA所需的较低温度表明根据本发明的催化剂具有改善的性能。
测定了催化剂1相对于对比商业催化剂的相对体积活性(RVA)，所述对比商业催化剂包含相当量的镍、钼和磷且具有0.74ml/g的压实体积密度，该对比商业催化剂在此后称为对比催化剂。
表4显示了获得含10ppm硫的产品所需的温度。实现此硫含量和较高RVA所需的较低温度表明根据本发明的催化剂具有比对比催化剂改善的性能。
表4-加氢脱硫活性

Claims (8)

1.用于制备加氢处理催化剂的方法，所述加氢处理催化剂包含5wt％-50wt％的钼、0.5wt％-20wt％的镍和0-5wt％的磷，全部基于催化剂的总干重，所述方法包括
(a)用钼和镍和基于载体重量1-60wt％的葡萄糖酸，和任选的磷来处理氧化铝载体，
(b)任选地，在40-200℃的温度下干燥所述处理的载体，和
(c)在200-650℃的温度下煅烧所述处理的且任选干燥的载体，以获得煅烧的处理的载体。
2.根据权利要求1所述的方法，在所述方法中，所述葡萄糖酸的量基于载体的总干重为2-40wt％。
3.根据权利要求1或2所述的方法，其中，所述磷的量基于催化剂的总干重为1.5-3.5wt％。
4.根据权利要求1-3任一项所述的方法，其中，所述加氢处理催化剂由氧化铝载体和1wt％-15wt％的镍、8wt％-40wt％的钼和0.1-5wt％的磷组成，所有金属基于催化剂的总干重。
5.根据权利要求4所述的方法，其中，所述载体是γ-氧化铝。
6.根据前述权利要求任一项所述的方法，其中，葡萄糖酸的重量与沉积在所述载体上的镍和钼的总重量的比率在煅烧之前是0.1-5。
7.根据前述权利要求任一项所述的方法，所述方法进一步包括
(d)硫化所述煅烧的处理的载体，以获得所述加氢处理催化剂。
8.用于加氢处理含硫烃原料的方法，所述方法包括使所述烃原料在1-70巴的氢分压和200-420℃的温度下，与根据权利要求7获得的催化剂接触。
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