CN101970609A - 通过增压热水改质高蜡原油的方法 - Google Patents
通过增压热水改质高蜡原油的方法 Download PDFInfo
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- C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
高蜡原油的连续改质方法,该方法通过使高蜡原油与超临界水流体接触以产生低倾点、高价值用作烃原料的具有低硫、低氮和低金属杂质的原油。
Description
专利申请
发明人:Ki-Hyouk Choi 文件号:004159.003050
Khalid Ali Al-Majnouni
Ali Al-Shareef
相关申请
本专利申请要求2008年11月28日提交的美国临时专利申请序列号60/990,658;60/990,648;60/990,662;60/990,670和60/990,641的优先权,这些文献都以全文以援引方式引入。
本发明的技术领域
本发明涉及高蜡原油的连续改质方法,该方法通过使高蜡原油与超临界水流体接触以产生低倾点、高价值、用作烃原料的、具有低硫、低氮和低金属杂质的原油。
发明背景
管道和油槽船早已用于长距离输送原油。据认可,常规原油具有足够性能以允许经由这些管道和油槽船传送原油。这些性能包括低倾点、低浊点和低粘度。
对石油原料的增长的需求和可获得常规原油的降低的质量要求其它潜在资源,例如非常规原油的改质,以便用于当前的精制工艺。
高蜡原油认为是非常规原油石油源。高蜡原油含有大量高沸点和高分子量链烷化合物,它们导致高倾点并限制原油经由管道传送的能力。因此,高度希望在经由管道传送之前在生产部位将高蜡原油改质。
此外,原油中芳族和烯属化合物的低水平通常使进一步加氢处理成为必需以便满足燃料规格,例如汽油的辛烷值。许多精制厂在将原油蒸馏成各种馏分后进行加氢处理,这意味着每种馏分必须单独地加氢处理。一般而言,要求大量氢气以调节各种馏分的性能以便满足所要求的规格。
此外,由于非常低的含量的包含在高蜡原油中的不饱和烃,它不足够作为某些精制工艺和石化工艺的原料。例如,得自高蜡原油的直馏石脑油要求严格的重整处理以提高芳族和烯烃含量,以便改进车用汽油的辛烷值。
已经提出了许多方法来改质高蜡原油以提高不饱和烃的含量和产生改进的倾点流动性以便容易传送。例如,高蜡原油的高倾点可以通过热焦化、催化加氢裂化、溶剂脱蜡和/或添加倾点下降剂来降低。
热焦化是改质高蜡原油以改进倾点和流动性以便经由常规管道和油槽船传送的可能方法之一。在热焦化发生的裂化使链烷键断裂以产生低沸点烃和不饱和烃。结果,提高高蜡原油的芳族和烯烃含量并降低倾点。然而,热焦化产生大量为副产物的固体焦,这意味着有价值烃原料的大量损失。此外,将大量高蜡原油转变成低值焦炭,这引起以连续方式进行的操作中的问题。
高蜡原油的改质可以经由常规催化加氢裂化进行。然而,这些处理要求大量的氢气和催化剂的定期置换,导致提高的操作成本。另外,不容易在原油生产点安装这些处理工艺,原因在于工艺设备的复杂性。
溶剂脱蜡法是将蜡状部分与基质分离的熟知方法。甲基乙基酮(MEK)、甲苯和丙烷已经用于蜡分离。然而,溶剂脱蜡要求大量的溶剂和昂贵的溶剂回收和蜡处理系统。
还提出了降低高蜡原油倾点的添加剂。使用倾点下降剂改进高蜡原油的流动性要求高操作成本。此外,倾点下降剂负面影响终产物的质量。
超临界水已经用作在添加外部氢气源情况下的烃裂化的反应介质。水具有大约705°F(374℃)的临界温度和大约22.1MPa的临界压力。在这些条件以上,水的液体和气体间的相边界消失,结果所得的超临界水显示对有机化合物的高溶解度和与气体的高混溶性。另外,超临界水使自由基物质稳定。
然而,按描述为裂化用反应介质的方式利用超临界水具有一些缺点例如形成焦炭,这在烃改质期间在超临界水流体中发生。非蜡原油,或重质原油具有低氢/碳比的基质,这可能产生焦炭。当焦炭在反应器内部积聚时,该焦炭充当隔热体并有效地阻断整个反应器中的热辐射,导致能源成本提高,因为操作者必须提高操作温度以补偿这种聚集。另外,积聚的焦炭还可能提高整个工艺管线中的压降,引起能源成本的进一步增加。虽然由如此改质烃产生的焦炭的量少于通过常规热焦化过程产生的量,但是必须使焦化最小化以提高液体收率和改进工艺操作的总体稳定性。
工业中已知的是,如果仅存在有限可利用的氢,则焦炭形成在使用超临界水的裂化中发生。已经提出了若干建议以将外部氢气提供给用超临界水流体处理的原料烃。例如,可以将氢气直接地添加到原料流中。还可以将一氧化碳直接地添加到原料流中以经由一氧化碳和水之间的水-气转换(WGS)反应产生氢气。还可以将有机物质例如甲酸添加到原料流中以经由与一氧化碳的WGS反应产生氢气,该氢气由所添加的有机物质和水的分解产生。此外,可以将少量氧气包括在原料流中以允许原料基质内的氧化而产生一氧化碳。然后可以将这种一氧化碳用于WGS反应以产生氢气。然而,将任何外部气体供入液流增加成本并增加工艺的复杂性。
高蜡原油含有相当大量的具有提高的沸点和相当大分子量的链烷化合物。这些性能导致高倾点和原油经由管道和油轮传送的能力方面的困难。因此,已经将高蜡原油认为是非常规石油源。
高蜡原油的改质可以经由常规热裂化或催化裂化进行,但是此种处理产生相当大量的焦炭并消耗大量的氢气和催化剂。除了热裂化和催化裂化之外,由高蜡原油的高倾点所引起的问题可以通过溶剂脱蜡和/或添加倾点下降剂减少。然而,所有这些方法有缺点。
如前所述,热焦化产生大量为副产物的固体焦,这是有价值烃原料的损失的指标。催化加氢裂化要求大量的氢气和废催化剂的定期置换。溶剂脱蜡要求蜡处理系统和溶剂回收系统,这增加复杂性和费用。倾点下降剂是昂贵的并以不希望的方法改变终产物。
因此,具有改质和降低高蜡原油的倾点的不要求以下方面的改进方法将是合乎需要的:氢气的外部供应、外部提供的催化剂的存在、溶剂的使用或倾点下降剂的使用。另外,具有不导致产生大量焦炭,以致工艺能连续运行的方法将是合乎需要的。此外,如果该方法能在生产点执行而不使用复杂设备,则将是有利的。
发明概述
本发明涉及满足这些需要中至少一项的连续方法。本发明的一个实施方案提供将高蜡原油转化成低倾点烃原料的连续方法,该低倾点烃原料适合于经由常规管道和油槽船传送。该低倾点原油是通过利用增压热水(也称作超临界水流体)制备的。这在没有氢气的外部供应或外部供应的催化剂的情况下进行。高蜡原油与超临界水的接触导致一些高倾点及其它大链烷组分的裂化,产生与高蜡原油相比具有更低倾点和更低链烷含量的改质油。
在本发明的一个实施方案中,降低高蜡原油的倾点和链烷含量的连续方法可以包括在混合区中将高蜡原油与增压热水混合以形成高蜡原油/水混合物,其中水和高蜡原油在室温下测量的混合比在10∶1wt/wt至1∶10wt/wt的范围内。增压热水的温度经选择使得所得的高蜡原油/水混合物限定的物理性能允许所述高蜡原油/水混合物适合于泵送,其中所述高蜡原油/水混合物的温度不超过150℃。
然后泵送高蜡原油/水混合物经过加热区以产生预热的混合物。然后将这种预热的混合物供入反应区,并提高温度使得所述预热的混合物的至少一些烃经历裂化而产生热改性的混合物。在本发明的一个实施方案中,所述反应区包括第一反应器的内部,所述第一反应器可操作而承受超过水的临界温度和临界压力的温度和压力。在本发明的另一个实施方案中,反应区基本上不含外部提供的催化剂,基本上不含外部提供的氢源和基本上不含外部提供的倾点下降剂。然后从反应区排出热改性的混合物并冷却,然后将它分离成改质油和回收水。所述改质油与所述高蜡原油相比由更低的倾点和/或更低的链烷含量限定,这赋予粗产物改进的流动性以便在管道和油槽船中的更有效传送。有利地,高蜡原油的使用相比重质原油减少焦炭形成,因为高蜡原油的基质的高氢/碳比抑制焦炭由重质原油形成。
在一个可选的实施方案中,反应区还包括第二反应器的内部,该第二反应器可操作以进一步加热所述预热的混合物到等于或高于水的临界温度的温度。在另一个实施方案中,第二反应器可以是夹套管,它是可操作而承受高达1112°F(600℃)的温度同时维持压力大于水的临界压力的导热管。在又一个实施方案中,第一反应器是垂直取向的反应器,使得预热的混合物向下流经该垂直取向的反应器。
在本发明的一个可选实施方案中,降低高蜡原油的倾点和链烷含量的连续方法可以包括在稍微升高的温度下将所述高蜡原油与水原料混合以形成高蜡原油/水混合物,所述温度在使得所述高蜡原油/水混合物在所述稍微升高的温度下能容易地被泵送的范围内选择,其中所述稍微升高的温度不超过150℃,其中水和高蜡原油在室温下测量的混合比在10∶1wt/wt至1∶10wt/wt的范围内。
然后将所述高蜡原油/水混合物泵送到加热区,其中将它加热到大约150℃至350℃的温度以形成预热的混合物。然后将所述预热的混合物供入反应区,其中将温度提高到等于或高于水的临界温度的目标温度,使得所述预热的混合物的至少一些烃经历裂化,从而形成热改性的混合物,所述反应区基本上不含外部提供的催化剂且基本上不含外部提供的氢源;所述热改性的混合物然后被冷却并通过压力调节装置经历压降,从而形成减压的改性混合物。所述压力调节装置优选是回压调节器,更优选是两个或更多个并联的回压调节器。然后使用至少一个液-气分离器将所述减压的改性混合物分离成气体部分和液体部分,并使用至少一个油-水分离器将所述液体部分分离成改质油和回收水。从所述油-水分离器回收的改质油是与所述高蜡原油相比具有降低的倾点的原油。
在一个可选的实施方案中,在超临界条件下将所述回收水氧化以形成经处理的水流,其中然后通过将所述经处理的水流与水原料混合将所述经处理的水流再循环回到工艺中。在一个附加的实施方案中,可以捕获包含在反应区的热改性的混合物和/或氧化步骤的经处理的水流中的热能并使它可操作以便在工艺的其它地方用于热交换。在又一个实施方案中,第一反应器是垂直取向的反应器,使得预热的混合物向下流经该垂直取向的反应器。
在一个可选的实施方案中,可以将水原料加热到升高的温度以形成热水流,使得该热水流处于超临界状态。然后在混合区中将高蜡原油与该热水流混合以形成预热的混合物,其中该混合区处于靠近反应区的位置,使得该预热的混合物保持超临界状态。然后将该预热的混合物供入反应区,将所述反应区内的温度提高到等于或高于水的临界温度的目标温度,使得所述预热的混合物的至少一些烃经历裂化,从而形成热改性的混合物,所述反应区基本上不含外部提供的催化剂且基本上不含外部提供的氢源。所述热改性的混合物然后被冷却并通过压力调节装置经历压降,从而形成减压的改性混合物。所述压力调节装置优选是回压调节器,更优选是两个或更多个并联的回压调节器。然后使用至少一个液-气分离器将所述减压的改性混合物分离成气体部分和液体部分并使用至少一个油-水分离器将所述液体部分分离成改质油和回收水。从所述油-水分离器回收的改质油是与所述高蜡原油相比具有降低的倾点的原油。
在一个可选的实施方案中,在超临界条件下将所述回收水氧化以形成经处理的水流,其中然后通过将所述经处理的水流与水原料混合将所述经处理的水流再循环回到工艺中。在另一个实施方案中,可以捕获从反应区和/或氧化步骤释放的热能并使它可操作以便在工艺的其它地方用于热交换。在又一个实施方案中,第一反应器是垂直取向的反应器,使得预热的混合物向下流经该垂直取向的反应器。
在本发明的其它实施方案中,可以将从液体分离阶段回收的水与增压热水混合。在本发明的又一个实施方案中,可以在氧化反应器中在与增压热水混合之前使用氧化步骤处理该回收水,以致通过除去任何油渣或其它杂质处理该回收水。在本发明的另一个实施方案中,可以捕获包含在反应区的热改性的混合物和/或氧化反应器的经处理的水流中的热能并用于在工艺的其它地方进行热交换。另外,可以在没有任何外部供应的催化剂的帮助下进行该连续方法。
通过本发明获得的低倾点原料具有良好的性能以便用于常规精制工艺以制备石油产品,例如汽油和柴油。另外,本发明提供提高高蜡原油的芳族和烯烃含量以便适合于常规精制产品和石化工艺的常规原料的连续方法。
本发明的连续方法不要求外部供应的氢气和/或催化剂来打断链烷键。不存在外部催化剂通过避免催化剂的成本以及使用外部催化剂的操作缺点产生成本有效的工艺。
此外,本发明连续方法中的超临界水流体与其它裂化方法相比抑制焦炭的形成,结果提高液体收率。另外,超临界水流体促进提高反应速度的传质。在另一个实施方案中,预热的混合物在反应区内的停留时间在0.1至10分钟,更优选1至3分钟之间。
此外,本发明的连续方法可以容易地用在高蜡原油的生产点,因为优选的实施方案不要求与其它要求供氧或焦炭除去系统的工艺相联系的复杂设备或设施。此外,低倾点原油具有高芳族和烯烃含量,连同低水平的硫、氮、金属、焦炭和杂质,这提高原料的价值,因为这样可以避免昂贵的加氢处理。
附图简述
参考以下描述、权利要求和附图,本发明的这些及其它特征、方面和优点将变得更加透彻。然而,应当指出,这些附图仅举例说明本发明的若干实施方案并因此不认为是本发明范围的限制,因为它可以用其它同样有效的实施方案实施。
图1是根据本发明的一个实施方案的连续方法示意图的透视图。
图2是根据本发明的一个可选实施方案的连续方法示意图的透视图。
图3示出了本发明的一个可选实施方案。
详细描述
本发明提供将高蜡原油转化成更有价值原油原料的连续方法,而无需氢气的外部供应。该连续方法一般包括使高蜡原油与增压热水接触以产生具有低倾点、低硫含量、低氮含量、低金属含量、高芳族含量和高烯烃含量的原油原料。这种方法在没有添加氢气的情况下进行。增压热水高于水的临界温度和压力并显示在本发明中用来达到所需最终结果的独特性能。
原料原油通常具有相当大量的高蜡烃。这种蜡烃通常具有高于90°F的倾点并难以经过管道传送到油槽船或场外精制设施。此外,由于低水平的芳族和烯属化合物而对原料原油进行附加的加氢处理通常是必需的,以满足燃料规格(例如汽油的辛烷值)。
在本发明的一个实施方案中,本发明的连续方法包括以下步骤:在混合阶段将高蜡原油与高压水混合以产生高蜡原油/水混合物,此后让该高蜡原油/水混合物经历预热阶段、反应区阶段、冷却阶段和多个分离阶段。或者,本发明的连续方法包括以下步骤:将高蜡原油与水的预热阶段之后的预热、高压水混合以产生预热的混合物,此后让该预热的混合物经历反应区阶段、冷却阶段和多个分离阶段。通过使用适合的经济设备将包含在反应区的热改性的混合物中的热能用来加热原料流。可以用增压热水在氧气存在下完全氧化包括在分离阶段的回收水中的有机化合物以获得用于再循环的清洁水。从该氧化反应释放的热能还可以在工艺中的其它地方用于热交换目的。
增压热水经过促进物质扩散、传热、分子内或分子间氢传送为待裂化成低倾点和低分子量烃的高蜡组分提供反应介质,从而使自由基化合物稳定以便抑制焦炭形成和除去杂质例如含硫、氮和金属的分子。虽然还没有识别杂质除去的确切机理,但是杂质似乎富集在改质产物的焦炭、水或重质馏分中。通过使用超临界水,这些杂质被氧化或改性而避免有害影响。
根据本发明的一个实施方案,在稍微升高的温度下按在室温下测量的10∶1至1∶10的重量比将高蜡原油与水混合。该稍微升高的温度经选择产生可泵送液体。稍微升高的温度是稍微比环境温度高的温度。示例性的升高的温度包括50-150℃的温度。可以使用本领域中已知的换热设备通过高蜡原油流(或水流)与例如,从反应区阶段离开的产物料流的热交换提供高蜡原油/水混合物或水原料的加热。
然后将高蜡原油/水混合物导入预热阶段,该预热阶段优选包括加热器和管子,以将原料流的温度提高至150-350℃。在一个可选的实施方案中,仅将水流导入预热阶段,该预热阶段包括加热器和管子,以将该水流的温度升高至超过水的临界温度的温度。为此的加热可以通过原料流与,例如,反应区阶段的产物料流或氧化反应器的经处理的水流的热交换提供。
然后将该预热的原料流供入反应区。该反应区(被加热器包围)将原料流的温度升高至374-600℃,同时维持压力高于水的临界压力。在反应区中,大蜡分子分解为具有低倾点和流动性良好的小分子。此外,经由发生在该反应区的裂化和氢传送反应提高芳族和烯属化合物的含量。此外,在这一阶段除去杂质,例如含硫、氮和金属的分子。然后将反应区的产物料流(是热改性的混合物)冷却并通过压力调节装置减压,而产生减压的改性混合物,然后通过一系列适合的隔板将该减压的改性混合物分离成气体部分和液体部分。
然后通过油-水分离器将该减压的改性混合物的液体部分分离成改质油和回收水。任选地,在超临界条件下通过氧化反应器用氧处理自该油-水分离器回收的水,以除去包含在该回收水中的油杂质而形成经处理的水流。为此使用的氧可以由氧气、过氧化氢、有机过氧化物和空气提供。离开该氧化反应器的经处理的水流具有源于氧化反应的高热能。因此,该经处理的水流可以与例如,反应区和/或氧化反应器的原料流热交换。
从油-水分离器回收的改质油含有比原料高蜡原油降低量的蜡组分和更大量的芳族和烯属组分。通过本发明还使根据ASTM D-86测量的蒸馏曲线移到更低温度。该改质油含有比高蜡原油原料降低量的硫、氮和金属化合物。因而,该改质油更适合于经由管道和油槽船传送。另外,该改质油是用于精制工艺的高质量原料,因为高含量的烯烃和芳族化合物和降低量的硫、氮和金属化合物。
本发明的连续方法进一步由以下说明性实施方案说明,该说明性实施方案不限制本发明的连续方法。
适用于本发明公开的连续方法的高蜡原油的性能列在表1中。倾点是非常高(即,105°F),这意味着该高蜡原油在室温(20-30℃)下是固态。
表I-说明性实施方案
性质 | 数值 |
比重,°API | 34.3 |
硫,总重量% | 1.8 |
雷德蒸气压psi | 4.1 |
倾点,(上限),°F | 105 |
盐,Lbs.NaCl/1000BBL(PTB) | 1 |
灰分,wt ppm | 33 |
钒,wt ppm | 15 |
微碳残渣,wt% | 3.84 |
镍,wt ppm | 4 |
氮,wt ppm | 542 |
热值,Gross,BTU/Lb | 19091 |
Kin粘度,@70°F,SUS | 55.18 |
Kin粘度,@100°F,SUS | 42.61 |
脱丁烷原油比重,°API | 33.20 |
特性比重,°API | 28.60 |
通过本发明的连续方法加工具有表I的性质的高蜡原油。在一个实施方案中,在加压到大于22.1MPa后将水预加热到450℃。将高蜡原油预加热到150℃并加压到超过22.1MPa。然后通过适合的混合设备,例如三通接头将该热水流和预热高蜡原油混合,然后注入反应区。将反应区的温度和压力分别维持在480℃和25MPa。从该适合的混合设备到反应区将该混合物维持在超过水的临界点的温度和压力。将该混合物在反应区中的停留时间调节到为大约三分钟。通过换热器使用反应区的排出物以将高蜡原油和水预加热。通过压力调节装置,优选回压调节器将换热器的排出物减压到大约0.1MPa。然后将压力调节装置的排出物供入液-气分离器。然后将液-气分离器的液体部分供入油-水分离器。收集和分析该油。总液体收率大于90vol%。液体产物的倾点低于10°F(-12℃)。
反应区中的焦炭形成由于超临界水的存在而最小化,因为该反应区中通过热能产生的自由基被超临界水稳定化。此外,通过维持所述预热的高蜡原油的温度低于150℃进一步使焦炭形成最小化。用超临界水流体改质高蜡原油不要求氢气和/或催化剂的外部供应。超临界水流体还抑制焦炭的形成,结果,提高液体收率。另外,超临界水流体促进传质,这提高反应速度。
图1说明一个实施方案,其中将水原料[2]供入储水槽[10],随后使用高压计量水泵[20]在混合区[30]将水原料[2]泵送入连续方法。同样将高蜡原油[4]供入高蜡原油储槽[11],在那里,随后使用高压计量高蜡泵[21]在混合区[30]将高蜡原油[4]泵送入连续方法。混合区[30]可以简单地是管线中的允许混合的三通接头或本领域中已知的其它混合设备。在混合区[30]之前,高蜡原油[4]处于允许流动的温度;然而,不超过150℃。这两个料流在混合区[30]混合而形成高蜡原油/水混合物[34]。然后将高蜡原油/水混合物[34]供入加热区[40],其中将温度增加到150至350℃的温度以形成预热的混合物[42]。
然后将预热的混合物[42]供入主反应器[50],其中温度和压力接近或超过水的临界点,使得预热的混合物[42]的至少一些烃经历裂化,形成热改性的混合物[52],主反应器[50]具有基本上不含外部提供的催化剂和基本上不含外部提供的氢源的反应区。然后使用任何可接受的冷却装置[60],优选换热器将热改性的混合物[52]冷却,产生冷却的改性混合物[62]。然后通过压力调节装置[70]将冷却的改性混合物[62]减压而产生减压的改性混合物[72]。在另一个实施方案中,压力调节装置[70]包括至少两个回压调节器,更优选按并联方式连接的三个回压调节器[70a、70b、70c]。这种安排在主回压调节器变得堵塞时有利地提供连续操作。减压的改性混合物[72]然后进入液-气分离器[80],其中将减压的改性混合物[72]分离成气体部分[82]和液体部分[84]。然后将液体部分[84]供入油-水分离器[90]而产生改质油[92]和回收水[94]。在一个可选的实施方案中,可以在储水槽[10]之前或之后将回收水[94]再循环并再用作水原料[2]。
图2代表另一个实施方案,其中在混合区[30]之前将水原料[2]预加热到超临界条件。混合区[30]可以简单地是管线中的允许混合的三通接头或本领域中已知的其它混合设备。在这个实施方案中,将水原料[2]供入储水槽[10],在那里,随后使用高压计量水泵[20]将水原料[2]泵送入连续方法。然而,不是首先与高蜡原油[4]混合,而是水原料[2]经历在加热区[40]中的加热以形成热水流[41],其中热水流[41]处于超临界状态。
同样将高蜡原油[4]供入高蜡原油储槽[11],在那里,随后使用高压计量高蜡泵[21]在混合区[30]将高蜡原油[4]泵送入连续方法。在混合区[30]之前,高蜡原油[4]处于允许流动的温度;然而,不超过150℃。高蜡原油[4]和热水流[41]在混合区[30]混合,该混合区[30]优选接近主反应器[50],以产生预热的混合物[42]。
预热的混合物[42]进入主反应器[50],其中温度和压力接近或超过水的临界点,使得预热的混合物[42]的至少一些烃经历裂化,形成热改性的混合物[52],主反应器[50]具有基本上不含外部提供的催化剂和基本上不含外部提供的氢源的反应区。然后使用任何可接受的冷却装置[60],优选换热器将热改性的混合物[52]冷却,产生冷却的改性混合物[62]。然后通过压力调节装置[70]将冷却的改性混合物[62]减压而产生减压的改性混合物[72]。在另一个实施方案中,压力调节装置[70]包括至少两个回压调节器,更优选按并联方式连接的三个回压调节器[70a、70b、70c]。这种安排在主回压调节器变得堵塞时有利地提供连续操作。减压的改性混合物[72]然后进入液-气分离器[80],其中将减压的改性混合物[72]分离成气体部分[82]和液体部分[84]。然后将液体部分[84]供入油-水分离器[90]而产生改质油[92]和回收水[94]。在一个可选的实施方案中,可以在储水槽[10]之前或之后将回收水[94]再循环并再用作水原料[2]。
图3代表本发明的一个可选实施方案。经过加热区[40]供给水原料[2],该加热区[40]优选是换热器,其中加热区[40]使水原料[2]经受超过水的临界点的温度和压力,得到呈超临界状态的热水流[41]。然后在接近主反应器[50]的位置[30]将高蜡原油[4]添加到热水流[41]中,产生预热的混合物[42]。预热的混合物[42]进入主反应器[50],其中主反应器[50]的温度和压力接近或超过水的临界点,使得预热的混合物[42]的至少一些烃经历裂化,形成热改性的混合物[52],主反应器[50]具有基本上不含外部提供的催化剂和基本上不含外部提供的氢源的反应区。热改性的混合物[52]往回经过加热区[40],在那里,它提供加热水原料[2]必要的能量。在穿过加热区[40]后,热改性的混合物[52]冷却,得到冷却的改性混合物[62]。冷却的改性混合物[62]然后穿过压力调节装置[70],得到减压的改性混合物[72]。减压的改性混合物[72]然后进入液-气分离器[80],其中将减压的改性混合物[72]分离成气体部分[82]和液体部分[84]。然后将液体部分[84]供入油-水分离器[90]而产生改质油[92]和回收水[94]。
回收水[94]然后进入氧化前加热器[100],它优选是换热器。回收水[94]然后进入氧化反应器[110]并经历升高的温度和压力,它们优选分别超过705°F(374℃)和22.1MPa。包括在从油-水分离器[90]回收的水[94]中的有机化合物可以在氧存在下用增压热水完全氧化而获得用于再循环的经处理的水流[112]。虚线代表可选实施方案,其中通过加热区[40]而不是氧化前加热器[100]使用经处理的水流[112a]的热能。
本文所使用的术语第一和第二和类似术语应该解释为唯一地区分元件并不意味或约束到元件或步骤的任何特定的顺序。
虽然按本发明的仅有的一些形式显示或描述了本发明,但是对本领域技术人员显而易见的是本发明不如此受到限制,而是对不脱离本发明范围的各种改变敏感。
Claims (30)
1.一种降低高蜡原油的倾点和链烷含量的连续方法,包括以下步骤:
在混合区中将高蜡原油与增压热水混合以形成高蜡原油/水混合物,其中水和高蜡原油在室温下测量的混合比在10∶1wt/wt至1∶10wt/wt的范围内,增压热水具有水温和水压,所述水压和水温经选择使得所得的高蜡原油/水混合物限定了允许所述高蜡原油/水混合物适合于泵送的物理性能,其中所述高蜡原油/水混合物的温度不超过150℃;
将所述高蜡原油/水混合物泵送经过加热区以产生预热的混合物;
将所述预热的混合物供入反应区并升高温度,使得所述预热的混合物的至少一些烃经历裂化而产生热改性的混合物,所述反应区包括第一反应器的内部,所述第一反应器可操作而承受超过水的临界温度和临界压力的温度和压力,所述反应区基本上不含外部提供的催化剂且基本上不含外部提供的氢源;
从所述反应区排出所述热改性的混合物并将所述热改性的混合物冷却以形成冷却的改性混合物;和
将所述冷却的改性混合物分离而产生改质油和回收水,使得所述改质油与所述高蜡原油相比由更低的倾点和/或更低的链烷烃、硫、氮和/或金属杂质含量限定。
2.权利要求1的连续方法,其中所述反应区基本上不含外部提供的倾点下降剂。
3.权利要求1的连续方法,其中所述反应区还包括第二反应器的内部,该第二反应器可操作以进一步加热所述预热的混合物到等于或高于水的临界温度的温度。
4.权利要求1的连续方法,其中所述第一反应器是垂直取向的反应器,使得所述预热的混合物向下流经所述垂直取向的反应器。
5.权利要求1的连续方法,其中水和高蜡原油的混合比的范围是10∶1至1.5∶1。
6.权利要求1的连续方法,其中水和高蜡原油的混合比的范围是1∶2至1∶10。
7.权利要求1的连续方法,其中所述反应区的温度维持在875°F至932°F(468℃至500℃)之间。
8.权利要求3的连续方法,其中所述第二反应器包括夹套管。
9.权利要求8的连续方法,其中所述夹套管包括导热管。
10.权利要求9的连续方法,其中将所述导热管加热到875°F至1112°F(468℃至600℃)的温度,同时维持压力高于水的临界压力。
11.一种降低高蜡原油的倾点的连续方法,该连续方法包括以下步骤:
在稍微升高的温度下将高蜡原油与水原料混合以形成高蜡原油/水混合物,所述温度经选择使得所述高蜡原油/水混合物在所述稍微升高的温度下能容易地被泵送,其中所述稍微升高的温度不超过150℃;
将所述高蜡原油/水混合物泵送到加热区;
在加热区中将所述高蜡原油/水混合物加热到大约150℃至350℃的温度以形成预热的混合物;
将所述预热的混合物供入反应区;
将所述反应区内的温度升高到等于或高于水的临界温度的目标温度,使得所述预热的混合物的至少一些烃经历裂化,从而形成热改性的混合物,所述反应区基本上不含外部提供的催化剂且基本上不含外部提供的氢源;
将所述热改性的混合物冷却和减压以形成减压的改性混合物;
使用至少一个液-气分离器将所述减压的改性混合物分离成气体部分和液体部分;
使用至少一个油-水分离器将所述液体部分分离成改质油和回收水;和
收集从所述至少一个油-水分离器回收的改质油,其中所述油是与所述高蜡原油相比具有降低的倾点的原油。
12.权利要求11的连续方法,还包括
在超临界条件下将所述回收水氧化以形成经处理的水流;和
通过将所述经处理的水流与水原料混合将所述经处理的水流再循环。
13.权利要求11的连续方法,其中所述反应区包括垂直取向的反应器的内部,使得所述预热的混合物向下流经所述垂直取向的反应器。
14.权利要求11的连续方法,其中通过压力调节装置将所述热改性的混合物减压,所述压力调节装置包括至少一个回压调节器。
15.权利要求14的连续方法,其中所述压力调节装置包括并联的两个或更多个回压调节器。
16.权利要求11的连续方法,还包括从所述反应区收集包含在所述热改性混合物中的热能,该热能可操作以便在该方法的其它地方用于热交换。
17.权利要求11的连续方法,其中所述水原料与高蜡原油在室温下测量的重量比在10∶1至1.5∶1的范围内。
18.权利要求11的连续方法,其中所述水原料与高蜡原油在室温下测量的重量比在1∶2至1∶10的范围内。
19.权利要求17的连续方法,其中所述反应区的温度维持在875°F至932°F(468℃至500℃)之间。
20.权利要求18的连续方法,其中所述反应区的温度维持在875°F至932°F(468℃至500℃)之间。
21.一种降低高蜡原油的倾点的连续方法,该连续方法包括以下步骤:
将水原料加热到升高的温度以形成热水流,使得所述热水流处于超临界状态;
在混合区中将高蜡原油与所述热水流混合以形成预热的混合物,其中所述混合区处于靠近反应区的位置,使得所述预热的混合物保持超临界状态;
将所述预热的混合物供入所述反应区;
将所述反应区内的温度升高到等于或高于水的临界温度的目标温度,使得所述预热的混合物的至少一些烃经历裂化,从而形成热改性的混合物,所述反应区基本上不含外部提供的催化剂且基本上不含外部提供的氢源;
将所述热改性的混合物冷却和减压以形成减压的改性混合物;
使用至少一个液-气分离器将所述减压的改性混合物分离成气体部分和液体部分;
使用至少一个油-水分离器将所述液体部分分离成改质油和回收水;和
收集从所述至少一个油-水分离器回收的改质油,其中所述油是与所述高蜡原油相比具有降低的倾点的原油。
22.权利要求21的连续方法,还包括:
在超临界条件下将所述回收水氧化以形成经处理的水流;和
通过将所述经处理的水流与水原料混合将所述经处理的水流再循环。
23.权利要求21的连续方法,其中所述反应区包括垂直取向的反应器的内部,使得所述预热的混合物向下流经所述垂直取向的反应器。
24.权利要求21的连续方法,其中通过压力调节装置将所述热改性的混合物减压,所述压力调节装置包括至少一个回压调节器。
25.权利要求24的连续方法,其中所述压力调节装置包括并联的两个或更多个回压调节器。
26.权利要求21的连续方法,还包括从所述反应区收集包含在所述热改性的混合物中的热能,该热能可操作以便在该方法的其它地方用于热交换。
27.权利要求21的连续方法,其中所述水原料与高蜡原油在室温下测量的重量比在10∶1至1.5∶1的范围内。
28.权利要求21的连续方法,其中所述水原料与高蜡原油在室温下测量的重量比在1∶2至1∶10的范围内。
29.权利要求27的连续方法,其中所述反应区的温度维持在875°F至932°F(468℃至500℃)之间。
30.权利要求28的连续方法,其中所述反应区的温度维持在875°F至932°F(468℃至500℃)之间。
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