CN101489669B - 用于催化裂化汽油中硫的减少的催化剂添加剂 - Google Patents

用于催化裂化汽油中硫的减少的催化剂添加剂 Download PDF

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CN101489669B
CN101489669B CN2007800240520A CN200780024052A CN101489669B CN 101489669 B CN101489669 B CN 101489669B CN 2007800240520 A CN2007800240520 A CN 2007800240520A CN 200780024052 A CN200780024052 A CN 200780024052A CN 101489669 B CN101489669 B CN 101489669B
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sulfur
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gasoline
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CN101489669A (zh
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C·F·迪恩
M·S·M·阿尔-哈姆迪
K·阿拉姆
M·A·B·西迪奎
S·艾哈麦德
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Saudi Arabian Oil Co
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Abstract

本发明涉及一种新的添加剂组合物，其用于降低催化裂化汽油馏分中的硫含量。所述添加剂组合物包括由具有已掺入的选自第IV族的第一金属和采用选自第II族的第二金属浸渍的多孔粘土组成的载体。优选地，已掺入的第一金属为锆，且浸渍的第二金属为锌。所述的硫减少添加剂在流化催化裂化过程中，以单独粒子的形式与常规流化催化裂化催化剂结合使用，将烃原料转化为汽油和其它液体产物。

Description

用于催化裂化汽油中硫的减少的催化剂添加剂
技术领域
本发明涉及降低流化催化裂化过程中制备的汽油的硫，尤其是涉及一种通过使用含有催化剂的添加剂来降低硫的方法和组合物。
背景技术
流化催化裂化(FCC)是最大的用于生产汽油的炼油过程，其全球产能超过1420万b/d。该过程将重质原料，例如真空馏分、残留物和脱沥青油转化为富含烯烃和芳烃的轻质产品。FCC催化剂通常是细颗粒的固体酸，尤其是沸石(合成Y-八面沸石)，铝硅酸盐，处理过的粘土(高岭土)，铝土矿，和氧化硅-氧化铝。商业FCC催化剂中的沸石含量通常在5-40wt.％范围内，或更高，而余量为氧化硅-氧化铝无定形基质。催化裂化过程中的添加剂含量通常不超过催化剂的10％，并且它们基本上都是用来提高辛烷值，作为金属钝化剂，SOx还原剂，CO氧化以及近来用于汽油的降硫。
针对汽油和尾气排放中硫含量的严格的环保条例正在全球实施。汽油中的硫增加了燃烧气体中的SOx排放，降低了车用催化转化器的活性，并加速了发动机零件的腐蚀。美国和欧盟的汽油中硫含量的上限将很快被设定于30ppm，作为炼油的平均水平。此外，在许多国家已提议2007年采用“无硫燃料”(＜10ppm)。另外，许多亚洲国家最近降低了在运输燃料中所允许的硫规格。
用来减少汽油中硫含量的可行的选择很多。主要的选择有：加氢处理FCC原料、加氢处理石脑油产物、降低FCC汽油的终沸点，以及在FCC催化剂中使用降硫添加剂。前两种选择是高度资本密集的。关于第三种选择的一个缺点在于：除了减少汽油收率外，降低终沸点也将降低辛烷值。从经济的角度来看，最后一个选择是最可取的，因为这将有选择性地脱除汽油馏分中的硫，而无需额外的处理。据报道，通过FCC添加剂或催化剂的降硫方法相比于标准的溶液选择性汽油加氢处理或HDS的方法具有经济优势。(Lesemann and Schult[2003])。
已经开发了在FCC过程用于实现降硫的各种催化材料。降硫的组分可以是FCC催化剂的单独添加剂或FCC降硫催化剂的一部分。然而，汽油中硫含量的水平仍然不够低，并且因此是不能接受的。
Wormbecher在美国专利5,376,608中、以及由Kim在美国专利5,525,210中提出了用于降低FCC汽油裂化产物中的硫含量的催化剂添加剂，在此均作为参考文献引入，为了生产降硫汽油，使用了一种在氧化铝上负载路易斯酸的裂化催化剂添加剂。还公开了该路易斯酸可包含沉积在氧化铝上的Zn，Cu，Ni，Ag，Cd和Ga的组分和化合物。然而，这一体系还没有取得重大的商业成功。
由Ziebarth等在美国专利6,036,847中披露的另一种组合物，将10wt％的包含负载在氧化铝上的锌和二氧化钛的组合物，作为添加剂用于在2.7wt.％的硫真空瓦斯油(VGO)原料的裂化，在此作为参考文献引入。结果表明，氧化铝负载路易斯酸组分和含二氧化钛的组分的结合，相比于单独使用其中的任一组分，导致了更多的硫含量的下降。
另一种添加剂，由Myrstad等在美国专利6,497,811中披露，其在此作为参考文献引入，包括已浸渍路易斯酸的水滑石材料的组合物，和可选择的FCC催化剂。所述的路易斯酸选自过渡金属元素及其化合物，优选Zn，Cu，Ni，Co，Fe和Mn，最优选Zn。
另一种添加剂，由Roberie等在美国专利6,482,315中披露，在此作为参考文献引入，其使用的组合物包含在选自氧化铝，二氧化硅，粘土和其混合物的耐火无机氧化物上负载钒。当使用2wt.％的含钒添加剂时，实现了汽油中的硫减少了33％。
由Andersson，P.等发表在Catalysis Today，53：565(1991)，Beltran F.等发表在Applied Catalysis Environmental，34：137(2001)以及42：145(2003)上的各种论文，只是以非常笼统的方式涉及了本发明的概念。
发明简述
本发明包括一种降低FCC汽油中硫含量的组合物，其中的组合物由催化剂载体和路易斯酸组分组成。优选地，载体材料是无定形的或无机的氧化物，例如，Al2O3，粘土或其混合物。降硫组合物作为单独的添加剂，与常规的流化催化裂化催化剂结合使用，该常规流化裂化催化剂通常是八面沸石，例如Y型沸石，在FCC装置中裂化烃原料，以生产低硫汽油和其它液体裂化产品。
本发明的组合物是一种多孔载体材料，具有在其孔结构中的第一金属组分(a)，其选自元素周期表的第IV族，和沉积在该载体材料表面上的第二金属组分(b)，其选自元素周期表的第II族。
组合物最优选由包含已掺入锆的蒙脱石粘土载体，并在载体上浸渍路易斯酸组分所制成。
本发明一个目的在于提供一种降硫组合物及使用它的方法，相比于在FCC过程中常规使用的FCC催化剂的降硫活性，其提供了一种具有硫含量水平显著降低的汽油。
附图简要说明
图1是常规FCC催化剂，不包含添加剂(参考)，和FCC催化剂/商业添加剂混合物(对比)，得到的产品汽油馏分中的硫含量与百分转化率的关系图。
图2是参考(无添加剂)，对比添加剂，和该新组合物的基体材料(粘土)得到的产品汽油馏分中的硫含量与百分转化率的关系图。
图3是浸渍锌的基体材料，参考材料和对比添加剂得到的产品汽油馏分中的硫含量与百分转化率的关系图。
图4是已掺入锆的基体材料，参考材料和对比添加剂得到的产品汽油馏分中的硫含量与百分转化率的关系图。
图5是该新组合物，参考材料和对比得到的产品汽油馏分中的硫含量与百分转化率的关系图。
发明详述
按照本发明，通过使用含有添加剂的催化剂组合物，将FCC汽油中的硫含量降低至一个较低的水平。优选地，FCC催化剂由粉末制成，并且一般具有在50-100微米范围的平均粒度和在0.5-1.0kg/L范围的堆密度。优选地，本发明的催化剂组合物的粒度、密度和机械强度与要物理混合该组合物的常规FCC催化剂相同。
裂化催化剂颗粒优选包含至少一种裂化催化剂组分，其对于在没有额外氢气存在的条件下具有裂化烃化合物的催化活性。该裂化催化剂组分优选包含沸石，非沸石分子筛，具有催化活性的无定形氧化硅氧化铝组分，或它们的组合。最优选的裂化催化剂组分是选自于Y，USY，(在美国专利3,293,192中所描述的，在此作为参考文献引入)，REY和RE-USY(在美国专利3,607,368和3,676,368中所描述的，在此二者均作为参考文献引入)，以及它们的混合物的Y型沸石。裂化催化剂粒子还可能包含一种或多种基质成分，例如粘土，改性粘土，氧化铝等。裂化催化剂粒子也可能含有粘结剂，例如无机氧化物溶胶或凝胶。裂化催化剂颗粒优选包含至少5wt.％，更优选约5-50wt.％的裂化催化剂组分。
请求保护的组合物中的载体材料优选是蒙脱石粘土，其具有在150-350m2/g范围的表面积。该粘土已在550℃的空气气氛下焙烧，以除去物理吸附的水。在550℃下焙烧没有造成其表面积的大量增加。
粘土材料本身具有相当大的降低汽油馏分中硫含量的能力。然而，苯并噻吩馏分的减少量是最小的。据观察，将路易斯酸组分浸渍到粘土上，既没有显着增加整体降硫能力，也没有显着增加苯并噻吩的减少量。
将锆，即优选的第IV族金属，掺入到目标粘土的孔中，使其表面积增加了约15％至约25％。据观察，将路易斯酸浸渍到已掺入锆的粘土材料中，显著降低了催化裂化的汽油馏分中的硫含量。锆可以掺入到载体材料的孔中，例如，掺入以添加剂总重量计1到5重量％的锆。最优选地，使用包括第II族金属化合物的路易斯酸，优选锌，以实现汽油中硫含量的减少。锌可以浸渍到载体材料的表面上，例如，浸渍以添加剂总重量计1到10重量％的锌。
为了进一步说明本发明以及其优点，给出了下面的具体实施例。这些实施例是请求保护的本发明的具体描述。然而，应该理解本发明并不限于实施例中具体细节的阐述。实施例说明了用来降低催化裂化汽油馏分中硫含量的具体组合物的制备和催化评价。
按照本发明，降硫添加剂的有效浓度，例如，可以为占裂化催化剂总重量的10到20重量％。
实施例
根据ASTM方法D-3907进行FCC催化剂/添加剂混合物的微活性测试(MAT)评价，在反应温度为510℃、30秒的注入时间、催化剂与油的比例在3至5之间，以获得55％至75％的转化率。原料使用的是来自阿拉伯轻质原油的真空瓦斯油。该原料的硫含量是2.5重量％。该原料的其他性质列于表1。使用GC-SCD测量汽油馏分中的硫含量。为了达到对比的目的，在71％转化率的水平下，计算汽油馏分的硫含量。
实施例1
使用常规FCC催化剂得到的汽油馏分中的硫含量
一种蒸汽处理的、常规的商业FCC分子筛催化剂，它是典型的低RE-USY型，可从任何FCC催化剂供应商处得到的，根据ASTM D3907方法在MAT中进行评价。图1给出了汽油硫含量与仅采用常规催化剂而不含有任何添加剂(参考)得到的百分转化率的关系图。该硫含量在此作为参考。
实施例2
使用商业上可用的添加剂组合物降硫
商业上的降硫添加剂，通常可以从典型的催化剂供应商处获得，例如Albemarle、CCIC、Englehard、Grace Davison或Intercat，在表中标识为对比添加剂，将其加入到(10wt.％)相同的经蒸汽处理的常规FCC催化剂——即实施例1中的低RE-USY中，并且在与实施例1相同的条件下在MAT中进行测试。在该实施例中的汽油馏分的硫含量与图1的参考硫含量进行对比。在71％的转化率下，获得的包括苯并噻吩的总硫的减少量为16％。表2列出了所有添加剂的汽油馏分中的硫含量。
实施例3
请求保护的新组合物的基体材料具有相当可观的降低FCC石脑油中的硫含 量的能力
为了测量载体材料降硫的能力，将蒙脱石粘土本身与传统催化剂——可从任何FCC催化剂供应商处得到的典型RE-USY型，混合后并在MAT中进行评价。所得到的结果如图2所示，与参考进行对比。蒙脱石粘土具有可观的降硫的能力。产物汽油馏分的硫含量降低了21％(表2)。
实施例4
通过使用浸渍了锌的粘土所获得的结果
组合物是通过初湿法，将2％的锌浸渍到实施例3所描述的粘土中制备得到的，并且将10重量％的该组合物与相同的商业催化剂混合，并在MAT中进行测试，该商业催化剂为与一种实施例1相同的、可从任何FCC催化剂供应商处得到的典型的低RE-USY型。图3对比了通过实施例4所述组合物得到的汽油与通过使用参考催化剂和对比添加剂得到的汽油中的硫含量。可以看到，该组合物的降硫能力与实施例3所述组合物的类似。在71％的转化率下，相比于单独使用参考催化剂，产物汽油的硫含量降低了21％。
实施例5
将锆掺入粘土孔中的效果
Zr-粘土组合物是通过离子交换，将锆掺入蒙脱石粘土的孔中制备得到的。掺入约2重量％的锆。将该组合物与商业FCC沸石催化剂按1∶10的比例混合，所述商业FCC沸石催化剂为可从任何FCC催化剂供应商处得到的典型的低RE-USY型。
图4显示了对于参考催化剂和Zr-粘土/催化剂混合物的汽油馏分中的硫含量与转化率的关系。采用Zr/粘土组合物添加到商业FCC催化剂中进行的MAT测试显示，与实施例2所述的对比添加剂获得的结果相比，裂化汽油馏分中的硫含量减少了17％(在71％的转化率下)。
实施例6
使用将锌浸渍到已掺入锆的蒙脱石粘土中得到的结果
组合物通过初湿法，将2wt.％的锌浸渍到实施例5所述的组合物(已掺入Zr的粘土)中制备得到。将10wt.％的该材料与可从任何FCC催化剂供应商处得到的典型的低RE-USY型混合，并在与实施例1所描述的相同条件下，在MAT中进行测试。
图5显示了该材料所获得的汽油硫含量与实施例1和2的组合物所得到的汽油硫含量的比较结果。通过使用本实施例的该组合物(Zn浸渍的已掺入Zr的粘土)，汽油中的硫含量降低了28％(表2)。可以看出，本发明的添加剂组合物优于现有技术中的比较添加剂。
实施例7
由锌浸渍的已掺入锆的蒙脱石粘土组成的组合物(硫化合物的分布)
催化裂化汽油中包含不同的硫化合物，例如硫醇，饱和物，噻吩和苯并噻吩。实施例6所获得的产品汽油馏分中的硫化合物分布是通过使用GC-SCD检测的。如表3所示。本发明的组合物对于各种类型的硫化合物，具有不同的减少效果。采用本发明的组合物，对于饱和物和C2-C4的噻吩的降硫是最有效的。
实施例8
汽油收率不受使用新添加剂的影响
表4列出了在71％的转化率下，使用常规催化剂，即低RE-USY对比添加剂和本发明的添加剂组合物所得到的汽油、气体、LCO、HCO和焦炭的产物收率。汽油收率和焦炭收率没有受到使用本发明所述添加剂组合物的影响，分别为50％和3.1％。
表1 真空瓦斯油(VGO)的性能参数
  性质   单位   数值
  密度   g/cc   0.882
  API   29.1
  碳   wt％   85.08
  氢   wt％   12.08
  硫   wt％   2.46
  氮   ppm   960
  起始沸点(IBP)   ℃   214
  终沸点(FBP)   ℃   588
表2 使用参考(无添加剂)、对比添加剂和其它四种添加组合物所获得的汽油馏分的硫含量和硫含量降低的百分比
  添加剂   汽油硫，ppm   降低的百分比
  参考(无添加剂)   659   0
  对比   553   16
  粘土   523   21
  Zn/粘土   520   21
  Zr/粘土   547   17
  Zn-Zr/粘土   472   28
表3 使用参考(实施例1)、对比添加剂(实施例2)和本发明的组合物(实施例3)在转化率为71％的情况下所获得的硫化合物分布，总的汽油的硫和减少百分数。
Figure GSB00000832886400081
表4 使用参考(无添加剂)、对比添加剂和其它四种添加组合物所获得的MAT收率
  添加剂   参考：无添加剂   对比   粘土   Zn/粘土   Zr/粘土   Zn-Zr/粘土
  汽油(wt.％)   50   52   51   51   52   50
  气体   17   15   16   17   15   18
  LCO   17   17   17   17   18   16
  HCO   12   12   12   12   11   13
  焦炭   3.4   3.4   3.6   3.9   3.3   3.1
根据上述教导，对于本发明各种修改都是有可能的。然而，可以理解的是在不背离它的范围下可以作出其它的修改，该范围由后续的权利要求独立地决定。

Claims (15)

1.一种FCC催化裂化混合物，包括FCC裂化催化剂和降硫添加剂，其中降硫添加剂包括多孔载体材料，具有(a)掺入在载体材料的孔结构中的选自元素周期表的第IVB族的第一金属组分，和(b)浸渍在载体材料表面上的选自元素周期表的第IIB族的路易斯酸化合物。
2.根据权利要求1所述的混合物，其中的载体材料为蒙脱石粘土。
3.根据权利要求1或2所述的混合物，其中选自元素周期表第IVB族并掺入到载体材料孔中的第一金属组分为锆。
4.根据权利要求1或2所述的混合物，其中选自元素周期表第IIB族并浸渍在载体材料表面上的路易斯酸化合物为锌。
5.根据权利要求3所述的混合物，其中基于所述添加剂的总重量计，降硫添加剂包含1到5重量％的锆。
6.根据权利要求4所述的混合物，其中基于所述添加剂的总重量计，降硫添加剂包含1到10重量％的锌。
7.根据权利要求1或2所述的混合物，其中降硫添加剂的浓度为占裂化催化剂的10到20重量％。
8.一种降低FCC裂化过程得到的汽油馏分中硫含量的方法，其包括，将烃原料与结合了降硫添加剂组合物的常规FCC裂化催化剂相接触，所述添加剂组合物包括多孔载体材料，该多孔载体材料的孔中已掺入选自元素周期表第IVB族的元素，并且该载体材料的表面采用选自元素周期表第IIB族的路易斯酸化合物浸渍。
9.根据权利要求8所述的方法，其中所述的降硫添加剂作为独立的粒子加入。
10.根据权利要求8所述的方法，其中的载体材料为蒙脱石粘土。
11.根据权利要求8或10所述的方法，其中选自元素周期表第IVB族并掺入到载体材料孔中的第一金属组分为锆。
12.根据权利要求8或10所述的方法，其中选自元素周期表第IIB族并浸渍在载体材料表面上的第二金属组分为锌。
13.根据权利要求11所述的方法，其中基于所述添加剂的总重量计，降硫添加剂包含1到5重量％的锆。
14.根据权利要求12所述的方法，其中基于所述添加剂的总重量计，降硫添加剂包含1到10重量％的锌。
15.根据权利要求8或10所述的方法，其中降硫添加剂的浓度为占裂化催化剂的10到20重量％。
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EP2043777A4 (en) 2009-10-28
US9403155B2 (en) 2016-08-02
JP5511378B2 (ja) 2014-06-04
JP2013150984A (ja) 2013-08-08
WO2008002504A2 (en) 2008-01-03
US20080000807A1 (en) 2008-01-03
EP2043777A2 (en) 2009-04-08
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US20130210613A1 (en) 2013-08-15
EP2497571A1 (en) 2012-09-12
WO2008002504A3 (en) 2008-03-27
EP2495041A1 (en) 2012-09-05
CN101489669A (zh) 2009-07-22
JP2009542845A (ja) 2009-12-03
NO20090097L (no) 2009-03-27
US8409428B2 (en) 2013-04-02

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