CN101568622A - 用于将来自可再生来源的原料转化为高质量柴油燃料基油 - Google Patents

用于将来自可再生来源的原料转化为高质量柴油燃料基油 Download PDF

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CN101568622A
CN101568622A CNA2007800478929A CN200780047892A CN101568622A CN 101568622 A CN101568622 A CN 101568622A CN A2007800478929 A CNA2007800478929 A CN A2007800478929A CN 200780047892 A CN200780047892 A CN 200780047892A CN 101568622 A CN101568622 A CN 101568622A
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N·杜帕修克斯
T·查普斯
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Abstract

本发明涉及用于处理来自可再生来源的原料以制备优异质量的柴油燃料基油的方法。所用的原料可以例如由粗制植物油或之前经过预精炼处理的植物油、动物脂肪或这样原料的混合物构成。本发明还涉及用于由这种原料获得柴油基油高产率的方法。

Description

用于将来自可再生来源的原料转化为高质量柴油燃料基油
发明领域
在欧盟中对燃料(特别是瓦斯油基油(bases gazoles))的需求快速增长为特征的国际背景中，寻找可以整合到传统燃料精炼和还原流程中的新的可再生能源构成了主要的挑战。
在这一点上，因为化石材料成本的提高，使来自于木质纤维素生物质的转化或植物油或动物脂肪的制备的新植物基产物整合到精炼工艺中的益处近年来经历了非常快速的提高。同样，传统生物燃料(主要是乙醇和来自植物油的甲基酯)达到了真正作为燃料总合中对石油类型燃料的补充的地位。此外，迄今为止已知的使用植物油或动物脂肪的工艺都是CO2排放源，其对环境的负面影响是已知的。因此对这些生物来源的更好的使用(例如将其整合到燃料总合(pool carburant)中)将具有一定的优点。
对瓦斯油燃料的强烈需求，和对环境的关心联系在一起，提高了使用来自可再生来源的原料的益处。在这些原料中，例如可以提及无论未经处理或经过预处理的植物油、动物脂肪和这些原料的混合物。这些原料包含甘油三酯、酯或脂肪酸类型的化学结构，后者的烃链的结构和长度都与瓦斯油中存在的烃相一致。
一种可能的方法在于通过酯交换反应转化植物油原料。然后在醇和催化剂存在下将基本上构成所述原料的甘油三酯转化为相应的酯。在该方法的缺点中可以提到：a)NOx排放的升高，因为在酯中存在氧；和b)过高的沸点，约为360℃，这在满足终点规范中可能产生问题。
专利申请EP 1681337A描述了通过脱羧基转化这种原料以生成具有比起始化学结构少一个碳原子的链烷烃。在上述专利中描述的这种方法的优点在于限制了氢的必需消耗量。然而，由此也降低了关于瓦斯油基油的产率。所用的催化剂是金属催化剂。
专利US 4992605和US 5705722描述了制备用于瓦斯油总合的基油的方法，其是由植物油(油菜籽油、棕榈油、大豆油和向日葵油)或木质纤维素生物质在对这些产物本身的加氢处理或加氢精炼之后直接转化成饱和烃的方法。
所述转化方法是在0.48-1.52MPa的压力和350-450℃的温度下进行的，可以得到具有高十六烷值的产物。将得到的该高十六烷添加剂以5-30体积％的含量与瓦斯油混合。
这两份专利都具有由于甲烷化反应或水煤气转化反应而产生的高氢消耗量为主要缺点。此外，甘油三酯中所含的氧通常是通过在加氢处理催化剂存在下的加氢脱氧而被分解，这在氢气方面是昂贵的。
发明目的
本发明涉及用于将来自可再生来源的原料转化为瓦斯油燃料基油的连续方法。
初始原料来自可再生来源，例如植物或动物来源的油和脂肪，或上述原料的混合物，其包含甘油三酯和/或脂肪酸和/或酯。在可能的植物油中，它们可以不加处理或精炼(无论完全或部分)，其由以下植物产生：油菜籽、向日葵、大豆、棕榈、菜棕、橄榄和椰子，该列举并非穷举。在可能的脂肪中，可以提及所有动物脂肪，例如由来自食品工业或来自餐馆工业的残渣构成的脂肪或油脂。
如此限定的原料包含甘油三酯和/或脂肪酸结构，其脂肪链包含8-25的碳原子数。
通过转化起始原料制备的烃的特征在于：
a)如果机理是其中将羧基加氢为烷基的加氢机理，那么碳原子数等于起始脂肪酸链的碳原子数；
b)如果涉及的机理是脱羧基/脱羰基机理，那么烃链具有比起始脂肪酸的链少一个碳原子。
现有技术中已知这两种转化方法通常是共存的。因此本发明所述的方法的目的在于使瓦斯油产率最大化并寻求促进在a)中所述的加氢机理。因此催化剂和操作条件的选择将决定加氢益处的选择性，同时寻求将氢消耗限制为严格所需的量，特别是将导致进行不希望的反应的氢消耗。因此，将氢消耗限制为严格所需的量是通过操作条件的有利组合，特别是通过使与原料混合的氢气的总量最优化而实现的。
制备的瓦斯油基油具有优异质量，因为其具有：
-低的硫、氮和芳香化合物含量；
-优异的十六烷值，因为生成的烃的完全链烷结构；和
-低密度(通常小于800kg/m3)，就其更容易达到瓦斯油总合的密度规格(不超过845kg/m3)方面来讲，这是有利的。
发明概述
本发明涉及处理来自可再生来源的原料的方法，包括以下步骤：
a)在200-450℃的温度，在1MPa-10MPa的压力下，以0.1h-1-10h-1的小时空间速度，在与所述原料混合的其总量使得氢气/原料比为70-1000Nm3氢气/m3原料的氢气存在下，在固定床催化剂存在下加氢处理，所述催化剂包含加氢-脱氢功能(fonction hydro-déshydrogénante)和无定形载体；和
b)从来自步骤a)的流出物中分离氢气、气体(des gaz)和至少一种瓦斯油基油。
发明详述
本发明特别用于使用来自可再生来源的原料制备符合最新环境标准的瓦斯油燃料基油。
这些原料由植物油和动物脂肪的组合构成，其特别地包含甘油三酯和脂肪酸或酯，其中烃脂肪链具有6-25的碳原子数。这些油可以是棕榈油、菜棕油、油菜籽油、蓖麻油和棉籽油、落花生油、亚麻子油和海甘蓝油，和所有来自例如遗传改性或杂交向日葵或油菜籽的油。可以使用榨取油和各种动物油，例如鱼油、牛脂和猪油。
这些油在15℃时的密度为850-970kg/m3，其在40℃时的运动粘度为20-400mm2/s，更通常为30-50mm2/s。
这些原料不含硫、氮和芳香化合物，或具有非常低的其含量：即硫和氮含量通常小于500ppm，芳香化合物含量小于5重量％。
有利地，在依照本发明的方法的步骤a)之前，该原料可经过预处理或预精炼步骤以通过适当的处理除去污染物，例如金属，如在例如离子交换树脂上的碱金属化合物、碱土金属和磷。适当的处理可以例如为本领域技术人员公知的热处理和/或化学处理。
优选地，该任选的预处理包括所述原料的轻度预加氢，以避免双键的副反应。该轻度预加氢有利地是在50-400℃的温度和0.1-10MPa的氢气压力下且优选在150-200℃的温度下进行的。该预加氢催化剂有利地包含VIII族和/或VIB族金属，且优选地该预加氢催化剂是基于负载在氧化铝和/或二氧化硅载体上的钯、铂、镍、镍-钼或基于钴-钼的催化剂。
优选地，在依照本发明的方法中使用预精炼的原料。
步骤a)：来自可再生来源的原料的加氢处理
在依照本发明的方法的步骤a)中，在200-450℃，优选220-350℃，更优选220-320℃，且甚至更优选220-310℃的温度下将任选经过预处理的原料与异质催化剂接触。压力为1MPa-10MPa，优选1MPa-6MPa，甚至更优选1MPa-4MPa。小时空间速度为0.1h-1-10h-1。在氢气存在下将该原料与催化剂接触。与该原料混合的氢气的总量使得该氢气/原料比为70-1000Nm3氢气/m3原料，优选150-600Nm3氢气/m3原料，甚至更优选150-450Nm3氢气/m3原料，因此这相当于添加到目前的原料中的氢气的量为相对于原料的至少0.5重量％。
在依照本发明的方法的步骤a)中，使用至少一个包含加氢-脱氢功能和无定形载体的固定加氢处理催化剂床。使用其载体例如选自由氧化铝、二氧化硅、二氧化硅-氧化铝、氧化镁、粘土和这些矿物的至少两种的混合物组成的组的催化剂将是优选的。这种载体也可以包含其他化合物，例如选自氧化硼、氧化锆、氧化钛和磷酸酐组成的组的氧化物。通常使用氧化铝载体，更佳的是η-、δ-或γ-氧化铝。
该加氢功能有利地是由VIII族和/或VIB族的至少一种金属提供的。
所述催化剂可以有利地为包含来自VIII族的金属(例如镍和/或钴)且通常和至少一种VIB族金属(例如钼和/或钨)相结合的催化剂。例如，可以使用包含在无定形矿物载体上的0.5-10重量％氧化镍(NiO)(优选1-5重量％氧化镍)和1-30重量％的氧化钼(MoO3)(优选5-25重量％的氧化钼)的催化剂，所述百分比都以相对于催化剂总质量的重量％表示。
相对于该催化剂总质量，VIB族和VIII族金属的氧化物在催化剂中的总含量有利地为5-40重量％，优选7-30重量％。
以金属氧化物表示的一种或多种VIB族金属与一种或多种VIII族金属的重量比有利地为20-1，优选地10-2。
依照本发明的方法的步骤a)中所用的所述催化剂理想上必须特征为高加氢能力以尽可能快地将该反应的选择性引向加氢，保持脂肪链的碳原子数，以使与在瓦斯油蒸馏领域中涉及的烃的产率最大化。这就是所述优选的实施方案是在相对低的温度下进行的原因。通过使加氢功能最大化，也可以限制导致生成焦炭的聚合和/或缩合反应，该焦炭将会使催化性能的稳定性降低。优选地，将使用Ni或NiMo型催化剂。
在依照本发明的方法的加氢处理步骤a)中所用的所述催化剂也可以有利地包含例如磷和/或硼的元素。该元素可以被引入到该基体中或优选地被沉积在载体上。也可以将硅本身或与磷和/或硼和/或氟一起沉积在载体上。
所述元素的氧化物的重量含量通常且有利地小于20％，优选小于10％，通常且有利地至少为0.001％。
依照本发明的方法的加氢处理步骤a)中所用的催化剂的金属是硫化金属或金属相。
依照本发明的方法的加氢处理步骤a)中所用的优选的金属催化剂具有20重量％-80重量％，优选55重量％-65重量％的镍含量。所述催化剂的载体有利地选自由氧化铝、氧化镁和二氧化硅的组，该载体有利地由氧化铝构成。
在依照本发明的方法的步骤a)中同时或连续使用单一催化剂或多种不同催化剂也不超出本发明的范围。该步骤可以以工业规模在一个或多个具有一个或多个催化剂床的反应器中以液体的下降流进行。
步骤b)：来自步骤a)的经加氢处理的流出物的分离
在依照本发明的方法的步骤b)中，该经加氢处理的流出物至少部分地且优选全部地经过一种或多种分离。该步骤的目的是将气体和液体相分离，特别是回收可能还包含例如CO和CO2的气体的富氢气体和具有小于10ppm重量的硫含量的至少一种液体瓦斯油基油。将步骤a)过程中可能产生的水至少部分从该烃产物中分离出来。因此分离步骤b)之后可以进行除水步骤。
该任选的除水步骤的目的是至少部分地除去加氢处理过程中产生的水。术语“除水”理解为表示除去由加氢脱氧(HDO)反应产生的水。
根据该催化剂的耐水性，在其中将来自步骤b)的流出物在随后的任选步骤中送到加氢异构化催化剂上的情况下，可以设想更完全的除水。可以通过本领域技术人员已知的任意方法或技术进行除水，例如通过干燥、使通过干燥剂上、闪蒸、滗析等。
在专利申请FR2826971中所述的加氢异构化催化剂存在下，任选地对由步骤b)得到的液体瓦斯油基油的至少一部分进行加氢异构化。
优选的加氢异构化催化剂包含0.05-10重量％的至少一种VIII族贵金属，优选地选自由单独或混合物形式的铂和钯构成的组，其沉积在无定形二氧化硅-氧化铝载体(其优选包含5-70重量％二氧化硅，更优选包含22-45重量％二氧化硅)上，该载体具有100-500m2/g的BET比表面积，该催化剂具有：
-1-12nm的中孔平均直径；
-其直径在前面限定的平均直径减3nm至前面限定的平均直径加3nm之间的孔的孔体积，其大于总孔体积的40％；
-20-100％的贵金属的分散(une dispersion du métal noble compriseentre 20-100％)；和
-大于0.1的贵金属的分布系数。
专利申请FR 2846574中描述了另一种优选的加氢异构化催化剂，其包括：
-至少一种选自由元素周期表的VIB族和VIII族元素构成的组的加氢-脱氢元素；
-基于包含大于10重量％且小于或等于80重量％的量的二氧化硅(SiO2)的二氧化硅-氧化铝的非沸石载体；
-由水银孔率测定法测定的平均孔直径为20-
-由水银孔率测定法测定的总孔体积为0.1ml/g-0.6ml/g；
-由氮孔率测定法测定的总孔体积为0.1ml/g-0.6ml/g；
-BET比表面积为150-500m2/g，
-小于0.1ml/g的由水银孔率测定法测定的在直径大于
Figure A20078004789200092
的孔中的孔体积；
-小于0.1ml/g的由水银孔率测定法测定的在直径大于
Figure A20078004789200093
的孔中的孔体积；
-小于0.1ml/g的由水银孔率测定法测定的在直径大于
Figure A20078004789200094
的孔中的孔体积；且
-小于0.1ml/g且优选小于0.01ml/g的由水银孔率测定法测定的在直径大于
Figure A20078004789200095
的孔中的孔体积。
优选地，该任选的加氢异构化步骤是并流进行的。
进行该任选的加氢异构化步骤的操作条件如下：温度有利地为200-450℃，优选250℃-450℃，更优选300-450℃，甚至更优选320-420℃。压力有利地为0.2-15MPa，优选0.5-10MPa，甚至更优选1-9MPa。小时空间速度有利地为0.1h-1-10h-1，更优选0.2-7h-1，甚至更优选0.5h-1-5h-1。氢气含量有利地为每小时100-2000Nm3/Nm3原料，优选150-1500Nm3/Nm3原料。
实施该方法所用的氢气来自工业重整单元。
气体的处理和再循环
如果需要，在将其再循环到步骤a)中之前，对在步骤b)中分离的含氢气体至少部分地被处理以减少其CO或CO2(优选通过用至少一种胺洗涤)。
可以将一定量的硫化合物(例如DMDS(二甲基二硫醚))添加到该再循环气体中，该化合物通过热分解生成硫化氢H2S。如果需要，该装置可以将催化剂保持在硫化物状态。有利地，引入的硫化合物的量使得该再循环气体中的H2S含量为至少15ppm体积，优选至少0.1体积％，或者甚至至少0.2体积％。
可能是有利的是，将该再循环氢气和进入步骤a)的原料一起引入和/或以在催化剂床之间的冷却氢气的形式引入。
获得的产物
该方法提供的产物具有优良的性质，由此提供高质量的瓦斯油基油：
-其硫含量小于10ppm重量；
-其总芳香化合物含量小于5重量％，多芳香化合物含量小于2重量％；
-十六烷值很好，大于80；
-密度小于840kg/m3，通常小于820kg/m3；
-其在40℃时的运动粘度为2-8mm2/s。
本发明还涉及可以用于实施依照本发明的方法的装置。
在图1中，将来自可再生来源的原料通过管线(1)供给在氢气存在下运行的加氢处理区域(3)，该氢气是通过管道(2)被引入。在加氢处理区域(3)中，如上所述地使该原料与加氢处理催化剂接触。然后将该加氢处理流出物引入分离区域(4)中以分离气体与液体。将富氢气体回收并排放，将液体瓦斯油基油馏分回收并通过管线(5)送到随后的任选的加氢异构化步骤(7)中。在图1中，将该液体瓦斯油基油馏分与通过管线(6)的氢气流一起引入到任选的包含如上所述的加氢异构化催化剂的加氢异构化区域(7)中。
实施例
步骤a)加氢处理
将170g/h的具有920kg/m3的密度且具有小于1ppm的硫含量且具有35的十六烷值的预精炼油菜籽油引入反应器中，该反应器经调节温度以保证等温操作且具有装载190ml基于镍钼的加氢处理催化剂的固定床，该催化剂具有3重量％的氧化镍含量和16重量％的氧化钼含量和6％的P2O5含量，且该催化剂经过预硫化，所述菜籽油的组成详情如下：
  脂肪酸甘油酯   脂肪链的性质   重量％
  棕榈酸甘油酯   C16:0   4
  棕榈油酸甘油酯   C16:1   ＜0.5
  硬脂酸甘油酯   C18:0   2
  油酸甘油酯   C18:1   61
  亚油酸甘油酯   C18:2   20
  亚油酸甘油酯   C18:3   9
  花生酸甘油酯   C20:0   ＜0.5
  顺式9-二十碳烯酸甘油酯   C20:1   1
  山俞酸甘油酯   C22:0   ＜0.5
  芥酸甘油酯(Eurucic)   C22:1   ＜1
将300Nm3氢气/m3原料引入到该反应器中，该反应器保持在300℃和4MPa的压力下。
步骤b)来自步骤a)的流出物的分离
将来自步骤a)的全部加氢的流出物进行分离以回收富氢气体和液体瓦斯油基油。生产出165g/h具有790kg/m3的密度且具有小于0.5ppm的硫含量且具有大于100的十六烷值的瓦斯油基油。
因此依照本发明的方法可以得到符合生效的规格的优异质量的瓦斯油基油。

Claims (10)

1.处理来自可再生来源的原料的方法，包括以下步骤：
a)在200-450℃的温度，在1MPa-10MPa的压力下，以0.1h-1-10h-1的小时空间速度，在与所述原料混合的其总量使得氢气/原料比为150-600Nm3氢气/m3原料的氢气存在下，在固定床催化剂存在下的加氢处理，所述催化剂包含加氢-脱氢功能和无定形载体；和
b)从来自步骤a)的流出物中分离氢气、气体和至少一种具有小于10ppm重量的硫含量的瓦斯油基油。
2.根据权利要求1的方法，其中所述原料由植物油和动物脂肪的组合构成，其包含甘油三酯和脂肪酸或酯，其中脂肪烃链含有6-25的碳原子数。
3.根据权利要求1和2之一的方法，其中该加氢处理步骤a)是在220-320℃的温度，在1MPa-4MPa的压力下，以0.1h-1-10h-1的小时空间速度，和在与所述原料混合的其总量使氢气/原料比为150-450Nm3氢气/m3原料的氢气存在下进行的。
4.根据权利要求1-3之一的方法，其中在步骤a)之前，使该原料经过预处理或预精炼步骤。
5.根据权利要求4的方法，其中所述预处理和预精炼步骤在于除去碱金属、碱土金属和磷化合物。
6.根据权利要求4的方法，其中该预处理或预精炼步骤包括所述原料的轻度预加氢，其是在50-400℃的温度和0.1-10MPa的氢气压力下在包含VIII族和/或VIB族的金属且在氧化铝和/或二氧化硅载体上的催化剂上进行的。
7.根据权利要求1-6之一的方法，其中分离步骤b)之后是通过干燥、使通过干燥剂上或通过闪蒸或通过滗析的除水步骤。
8.根据权利要求1-7之一的方法，其中在加氢异构化催化剂的存在下使由步骤b)得到的液体瓦斯油基油的至少一部分加氢异构化。
9.根据权利要求8的方法，其中该加氢异构化催化剂包含0.05-10重量％的至少一种VIII族贵金属，优选地选自由单独或混合物形式的铂和钯构成的组，其沉积在无定形二氧化硅-氧化铝载体上，该载体具有100-500m2/g的BET比表面积，该催化剂具有：
-1-12nm的中孔平均直径；
-其直径在前面限定的平均直径减3nm至前面限定的平均直径加3nm之间的孔的孔体积，其大于总孔体积的40％；
-20-100％的贵金属的分散；和
-大于0.1的贵金属的分布系数。
10.根据权利要求8的方法，其中该加氢异构化催化剂包括：
-至少一种选自由元素周期表的VIB族和VIII族元素构成的组的加氢-脱氢元素；
-基于包含大于10重量％且小于或等于80重量％的量的二氧化硅(SiO2)的二氧化硅-氧化铝的非沸石载体；
-由水银孔率测定法测定的平均孔直径为
-由水银孔率测定法测定的总孔体积为0.1ml/g-0.6ml/g；
-由氮孔率测定法测定的总孔体积为0.1ml/g-0.6ml/g；
-BET比表面积为150-500m2/g，
-小于0.1ml/g的由水银孔率测定法测定的在直径大于
Figure A2007800478920003C2
的孔中的孔体积；
-小于0.1ml/g的由水银孔率测定法测定的在直径大于的孔中的孔体积；
-小于0.1ml/g的由水银孔率测定法测定的在直径大于
Figure A2007800478920003C4
的孔中的孔体积；和
-小于0.1ml/g的由水银孔率测定法测定的在直径大于
Figure A2007800478920003C5
的孔中的孔体积。
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EP2106428B1 (fr) 2021-06-02
WO2008081101A2 (fr) 2008-07-10
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PT2106428T (pt) 2021-08-16

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