CN101142021B - 甲硅烷基改性的催化剂及该催化剂用于将合成气转化为烃类的用途 - Google Patents

甲硅烷基改性的催化剂及该催化剂用于将合成气转化为烃类的用途 Download PDF

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CN101142021B
CN101142021B CN2006800051651A CN200680005165A CN101142021B CN 101142021 B CN101142021 B CN 101142021B CN 2006800051651 A CN2006800051651 A CN 2006800051651A CN 200680005165 A CN200680005165 A CN 200680005165A CN 101142021 B CN101142021 B CN 101142021B
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J·J·H·M·丰特弗赖德
L·T·哈迪
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Abstract

本发明涉及在改性的负载型费-托催化剂组合物存在下，通过加入甲硅烷基化化合物改性剂，优选有机硅化合物如双(三甲基甲硅烷基)三氟乙酰胺，从而将合成气转化为烃类的方法。

Description

甲硅烷基改性的催化剂及该催化剂用于将合成气转化为烃类的用途
本发明涉及合成气向烃类的转化。特别地，本发明涉及合成气向C5+烃类的转化，该烃类特别适合于用作液态发动机燃料。 
公知地，在多种过渡金属催化剂存在下，合成气(即氢气和一氧化碳)可转化为烃类。因而，已知某些第VIII族金属，特别是铁、钴、钌和镍，能催化CO和氢气(也称为合成气)向烃类的转化。这类金属通常称为费-托(Fischer-Tropsch)催化剂。当使用镍时，合成气转化优先生成甲烷；而使用铁、钴和钌时，倾向于产生由碳原子数比甲烷高的烃类构成的混合烃。在较高的反应温度下，所有费-托催化剂倾向于产生气态烃类，且很容易选择加工条件以产生甲烷作为主要产物。然而，在较低的温度下，且通常在高压下，铁、钴和钌产生由更高级的烃类构成的混合烃。该产物通常含有非常长的直链烃分子，该分子倾向于沉淀为蜡状物。这类蜡状材料在远高于发动机燃料沸腾范围的温度下沸腾，且通常构成这类催化转化操作所得产物的很大一部分。因此，费-托催化剂并没有广泛地应用于液态烃发动机燃料的生产中，因为在一方面它们通常产生主要为气态的烃类，而在另一方面它们通常产生含有不可接受的大量蜡状物的烃类。此外，所产生的汽油沸点烃组分具有不可接受的低辛烷值。 
而通过在费-托金属催化剂存在下的合成气转化进行的液态发动机燃料(特别是在汽油沸点范围内沸腾的燃料)生产中存在的另一困难是这类费-托金属特征性地产生直链烃类的倾向，该直链烃类由正链烷烃类(paraffin)和正烯烃类(olefin)的混合物构成。可以理解，所得的实际混合物依赖于具体的金属催化剂及所采用的处理条件。在任何情况下，该转化产物通常都只含有少量的单支链的烃类以及非常少的环烷烃类和芳香烃类，且基本没有多支链的烃类。转化产物中缺乏支链的或芳香族(即环状)烃类导致这类产物含有辛烷值(或O.N.)非常低的汽油组分。如果不增加额外的高成本的精炼步骤，这类组分不适于用作汽油。当然，这类金属催化剂产生的C10-C18范围内的高级正链烷烃类是可加入喷气燃料和柴油机燃料的有用组分。然而，在这类组分中 也需要存在部分支链和芳香族烃类，以增强将原料合成气转化为这类液态发动机燃料的整个过程的热效率，并降低这类燃料的倾点。 
基于以上原因，在本领域中需要开发将合成气转化为液态烃燃料的改进的技术。这类改进的技术将合意地使得可进行这类合成气转化并得到如下结果：(1)与当前的主要为正链烷烃类和正烯烃类的生产相比，增强支链化和芳香化，及(2)通过减少甲烷和沸点超过柴油沸点范围的重烃产物的产生来强化所需液态发动机燃料的生产。同时，所述催化剂组合物必须具有所需程度的活性和稳定性，以使得这类发动机燃料的生产可以在实际的商业实施条件下进行。 
因此，本发明的目的之一是提供用于将合成气转化为液态烃发动机燃料的改进的方法和催化剂组合物。 
本发明的另一目的是提供能增强合成气向这类液态燃料转化的稳定的催化剂组合物。 
本发明的另一目的是提供用于生产液态发动机燃料的方法和费-托催化剂组合物，该液态发动机燃料含有微量的甲烷和沸点超过柴油沸点范围的重烃产物。 
以这些及其它目的为中心，以下将具体描述本发明；在所附权利要求中特别指出了本发明的新特征。 
在本发明的实践中，通过使用包含负载型费-托金属作为组分的改性催化剂组合物，将合成气转化为液态发动机燃料。转化产物含有微量的甲烷和沸点超过柴油沸点范围的重烃产物。 
通过对含有负载型费-托金属的催化剂组合物进行改性，并将其用在合成气向液态烃类的转化中，实现了本发明的目的。与先前使用用于合成气转化的未改性费-托催化剂获得的结果相反，使用这类改性的催化剂组合物有利地产生沸点在喷气燃料沸点范围与柴油沸点范围的合并范围内的液态发动机燃料。由于已发现所述改性的催化剂组合物在连续处理操作过程中具有突出的稳定性，本文所述及要求保护的改性催化剂组合物及其用于合成气转化的方法提供了一种得到所需液态发动机燃料的高度有利的和可行的途径，该液态发动机燃料的沸点在汽油、喷气燃料和柴油的沸点范围内。 
根据本发明实践处理的合成气(或合成气)通常含有氢气与一氧化碳的混合物，然而本领域技术人员公知，该合成气中也可能还有少量 的二氧化碳、甲烷、氮气和其它组分。可使用本领域公知的任何方法来制备该合成气，包括烃类的部分氧化、蒸汽重整、气体加热重整(gasheated reforming)、微槽(microchannel)重整(如例如US6,284,217中所述，本文将其引入作为参考)、等离子体重整、自热重整及其任意组合。在“Hydrocarbon Processing”V78，N.4，87-90，92-93(1999年4月)和“Petrole et Techniques”，N.415，86-93(1998年7-8月)中提供了这些合成气生产技术的探讨。也可以预见，可通过在如“IMRET3：Proceedings of the Third International Conference on MicroreactionTechnology”，编辑W Ehrfeld，Springer Verlag，1999，187-196页中所示的微结构反应器中进行烃类的部分催化氧化可以得到所述合成气。可选择地，如EP0303438中所述，可通过含烃给料的短时接触部分催化氧化得到合成气。优选地，通过“Hydrocarbon Engineering”，2000，5，(5)，67-69；“Hydrocarbon Processing”，79/9，34(2000年9月)；“Today′sRefinery”，15/8，9(2000年8月)；WO99/02254和WO200023689中所述的“紧凑型重整器(Compact Reformer)”方法获得合成气。 
本发明的费-托方法优选在180-280℃的温度下进行，更优选在190-240℃进行。 
本发明的费-托方法优选在5-50巴的压力下进行，更优选在15-35巴进行，通常在20-30巴进行。 
优选地，合成气中氢气对一氧化碳的体积比为20∶1到0.1∶1，特别是体积比5∶1到1∶1，例如体积比2∶1。 
如本文所述用于合成气向液态发动机燃料转化的本发明的改性催化剂组合物含有负载在适当载体上的费-托金属。在本发明的实践中可采用已知能催化合成气向烃类的转化以及通常称为费-托催化剂的各种第VIII族金属，例如铁、钴、钌和镍，以及钼、钨、铼等等。已发现，在整体评价的基础上，使用铁和钴作为催化组合物的费-托金属组分特别适合于本发明的目的。 
本发明的催化剂组合物的第二基本组分是载体，其优选选自氧化铝、二氧化硅、氧化钛、氧化锌或其混合物。已发现，在整体评价的基础上，使用氧化锌作为催化组合物的费-托金属组分的载体特别适合于本发明的目的。 
根据本发明的一个优选实施方案，本发明方法中采用的催化剂是 负载型钴催化剂。优选地，所述钴负载在无机氧化物上。优选的载体包括二氧化硅、氧化铝、二氧化硅-氧化铝、第IVB族的氧化物、氧化钛(主要为金红石型)，且优选氧化锌。所述载体优选具有低于约100m2/g的表面积，更适于低于50m2/g，例如低于25m2/g或约5m2/g。 
通常，存在至少0.1％的钴(基于载体的重量)，优选约0.1-20％，特别优选0.5-5wt％。可向该催化剂中加入助催化剂，且该助催化剂是费-托催化剂领域中公知的。助催化剂可包括钌、铂或钯(当不作为主催化剂金属时)、铝、铼、铪、铈、镧和锆，并且通常以低于钴的量存在(除了钌，其可以同等的量存在)，但助催化剂：金属比例应当为至少1∶10。优选的助催化剂为铼和铪。微粒状的费-托催化剂可具有5-500微米的平均粒度，优选为5-100微米，例如5-40微米。 
本发明催化剂组合物的改性是通过使用甲硅烷基化化合物得到的。该甲硅烷基化化合物可在催化剂制备过程中或者在后处理阶段中使用。根据本发明的一个优选实施方案，用所述甲硅烷基化化合物对所制备的含负载型费-托金属的催化剂组合物进行后处理。 
根据本发明，所采用的甲硅烷基化化合物优选选自有机硅化合物，更优选选自三甲基硅化合物，最优选选自氯化三甲基硅烷、双(三甲基甲硅烷基)三氟乙酰胺、N-甲基-N-(三甲基甲硅烷基)三氟乙酰胺，及其混合物。根据本发明的一个优选实施方案，使用双(三甲基甲硅烷基)三氟乙酰胺作为改性剂。 
申请人预料不到地发现，本发明的改性催化剂显示出提高的活性以及更长的催化剂寿命。 
虽然不希望被特定的理论所限制，申请人相信有机硅化合物的使用使得催化剂发生转变，从而产生疏水/水分散官能性。实际上，公知地，在合成气向烃类的转化过程中产生一些水，且这些水对费-托催化剂的活性和寿命是有害的。因而，本发明的改性催化剂的出人意料的特性可能是在催化剂组合物中引入了具有疏水部分的化学官能团，且该疏水部分能将产生的水从催化剂处分散或驱散从而致使活性提高且催化剂寿命延长的结果。 
以下将参照某些具体实施例来描述本发明，这些实施例用于说明各种实施方案，而不应视为对所附权利要求限定的本发明范围的任何限制。
实施例1疏水催化剂的制备 
将20g Engelhard钴基费-托催化剂B958-30在100℃干燥1小时然后冷却，将其称重置入可密封的玻璃容器中，并加入化学衍生级(derivatization grade)的甲硅烷基化(silating)试剂[双(三甲基甲硅烷基)三氟乙酰胺]至完全浸没所述催化剂。将容器密封并在电冰箱中于约4℃储存过夜。浸泡16小时后，从固体上吸除表面液体，并使处理后的催化剂风干。 
实施例2疏水催化剂的测试 
将10.0ml(14.5g)处理后的催化剂装料入固定床反应器中，并以如下方式活化： 
在反应器中建立GHSV＝1800hr-1的氮气流，该反应器处于环境温度和压力下，随后将反应器温度以1℃每分钟的速度提升至250℃。系统中的压力为克服通过催化剂床层的压力降所需的压力，从反应器排出的气体为常压。当反应器处于250℃时，使催化剂在该温度下驻留1小时，随后将氮气流转换为同样GHSV的一氧化碳流。用一氧化碳对催化剂持续还原3.5小时，随后停止一氧化碳流，并用同样流量的氮气替代以将所有的还原气体清除出系统。当系统不含一氧化碳时，停止氮气流，并用GHSV＝800hr-1的氢气流替代。将氢气还原在250℃下持续进行16小时，随后将对反应器的供热关闭，使催化剂在持续的氢气流中冷却。 
如下所述对活化的催化剂进行测试： 
在活化过程的末尾，使催化剂冷却至低于130℃，同时用气缸(cylinder)供应的合成气(氢气、一氧化碳和氮气的混合物)替代氢气流，该合成气由差异(differential)组分压力产生，以GHSV＝1800hr-1流动，并将系统缓慢加压至430psig。 
随后缓慢提升反应器的温度，监测所述催化剂产生费-托产物的性能。
  
通气流时间(hr) GHSV(hr-1) 温度(℃) 转化率(摩尔％) 对>C5的选择性
18.5 1800 203 37.4 82.2
91.0 1800 208 36.6 76.8
121 1800 208 35.0 76.5
实施例3标准催化剂的测试 
将10ml(14.3g)“刚收到”的Engelhard催化剂B958-30置于固定床反应器中，并用实施例2中所述的方法活化。 
使用实施例2中所述的方法再次进行活化催化剂的测试。 
  
通气流时间(hr) GHSV(hr-1) 温度(℃) 转化率(摩尔％) 对>C5的选择性
8.0 1250 186 15.7 79.6
89.5 1250 206 27.9 74.9
125.5 1250 207 25.2 73.8

Claims (22)

1.改性的催化剂组合物，其含有载体和用于将合成气转化为液态烃类的费-托金属，其特征在于所述催化剂组合物如下制备：在催化剂制备过程中或后处理阶段中，向所述催化剂组合物中加入甲硅烷基化化合物改性剂。
2.根据权利要求1所述的催化剂组合物，其中在催化剂后处理阶段中加入所述甲硅烷基化化合物。
3.根据权利要求1或2所述的催化剂组合物，其中所述甲硅烷基化化合物选自三甲基硅化合物。
4.根据权利要求3所述的催化剂组合物，其中所述甲硅烷基化化合物选自氯化三甲基硅烷、双(三甲基甲硅烷基)三氟乙酰胺、N-甲基-N-(三甲基甲硅烷基)三氟乙酰胺，及其混合物。
5.根据权利要求4所述的催化剂组合物，其中所述甲硅烷基化化合物为双(三甲基甲硅烷基)三氟乙酰胺。
6.根据权利要求1或2所述的催化剂组合物，其中所述费-托金属为第VIII族金属。
7.根据权利要求6所述的催化剂组合物，其中所述费-托金属选自铁、钴、钌、镍、钼、钨和铼。
8.根据权利要求7所述的催化剂组合物，其中所述费-托金属为铁和/或钴。
9.根据权利要求1或2所述的催化剂组合物，其中所述载体选自氧化铝、二氧化硅、氧化钛、氧化锌或其混合物。
10.根据权利要求9所述的催化剂组合物，其中所述载体为氧化锌。
11.根据权利要求1或2所述的催化剂组合物，其含有负载在无机氧化物上的相对于所述载体为0.1-20wt％的钴、以及助催化剂，所述无机氧化物具有低于100m2/g的表面积，所述助催化剂选自钌、铂、钯、铝、铼、铪、铈、镧和锆，其中在钌、铂或钯不作为主催化剂时将其用作助催化剂，并且所述助催化剂以低于钴的量存在，且助催化剂∶金属的重量比为至少1∶10。
12.在权利要求1或2所述的改性的催化剂组合物存在下，将合成气转化为液态烃类的方法。 
13.制备包含负载在载体上的费-托金属的费-托催化剂的方法，其特征在于用甲硅烷基化化合物对所述催化剂进行改性，其中所述甲硅烷基化化合物在催化剂制备过程中或后处理阶段中加入。
14.根据权利要求13所述的方法，其中在所述催化剂的后处理阶段中加入甲硅烷基化化合物。
15.根据权利要求13或14所述的方法，其中所述甲硅烷基化化合物选自三甲基硅化合物。
16.根据权利要求15所述的方法，其中所述甲硅烷基化化合物选自氯化三甲基硅烷、双(三甲基甲硅烷基)三氟乙酰胺、N-甲基-N-(三甲基甲硅烷基)三氟乙酰胺，及其混合物。
17.根据权利要求15所述的方法，其中所述甲硅烷基化化合物为双(三甲基甲硅烷基)三氟乙酰胺。
18.根据权利要求13或14所述的方法，其中所述费-托金属为第VIII族金属。
19.根据权利要求13或14所述的方法，其中所述费-托金属选自铁、钴、钌、镍、钼、钨和铼。
20.根据权利要求19所述的方法，其中所述费-托金属为铁和/或钴。
21.根据权利要求13或14所述的方法，其中所述载体选自氧化铝、二氧化硅、氧化钛、氧化锌或其混合物。
22.根据权利要求21所述的方法，其中所述载体为氧化锌。 
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