CN102159675A - 通过热加压水和采收流体将全原油改质的方法 - Google Patents
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Abstract
将全原油改质的方法,其利用采收流体,以逐步方式将提取的全原油/采收流体混合物减压,随后使至少一部分全原油与超临界水流体接触以制造用作烃原料的具有低硫、低氮和低金属杂质的高价值原油。
Description
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号No.60/990,641;60/990,662;60/990,648;60/990,670;和60/990,658的优先权,它们都全文经此引用并入本文。
发明技术领域
本发明涉及在不使用外部供应的氢的情况下通过利用采收(recovery)流体和在逐步减压步骤后使该采收的原油与超临界水流体接触来将全原油改质以制造用作烃原料的具有低硫、低氮、低金属杂质和高API比重的低倾点高价值原油的方法。
发明背景
全世界对石油产品的需求近年来急剧增长,耗尽了大量已知的高价值轻质原油贮藏。因此,生产公司将兴趣转向使用低价值的重质原油以满足未来日益增长的需求。但是,由于使用重质原油的现有精炼法不如使用轻质原油的有效,由较重原油生产石油产品的炼油厂必须精炼更大体积的较重原油才能获得相同体积的最终产品。但是不幸地,这不能应对未来需求的预期增长。进一步加剧该问题的是,许多国家已经或计划对基于石油的运输燃料的规格执行更严格的规章。因此,石油工业试图找出在精炼之前处理重质原油的新方法以满足对石油原料的日益提高的要求和改进精炼工艺中所用的可得原油的品质。
全原油或未加工的原油是用于由生产井产生在任何精炼工艺之前的原油的一般术语。根据生产井的地理特征,全原油的组成极大地随井而变。不幸地,许多新发现的井往往产生含有提高量的重馏分和除碳和氢外的杂质的全原油。因此,随着更多既有的较有价值的油井被耗尽,我们未来的供应品大多由劣等原油构成。
一般而言,高密度原油提供较低量的较有价值的轻质和中间馏出物。另外,高密度原油通常含有提高量的杂质,如硫、氮和金属,所有这些都要求在加氢处理中使用更高量的氢和能量以符合关于最终产品中的杂质含量的严格规章。
一般而言,重质原油具有低API比重、高沥青质含量、低中间馏出物收率、高硫含量、高氮含量和高金属含量。这些性质导致难以通过传统精炼法精炼重质原油以制造规格符合严格政府规章的最终石油产品。
传统裂化法
低价值的重质原油可以通过使用本领域已知的各种方法裂化重馏分来转化成高价值的轻质原油。传统上,在氢存在下在升高的温度下使用催化剂进行裂化和清洁。但是,这种类型的加氢处理在不使用大量氢和/或催化剂时在加工重质和含硫原油时具有一定限制。
另外,重质原油原料的蒸馏和/或加氢处理产生大量沥青质和重质烃,它们必须进一步裂化和加氢处理才能使用。沥青质和重馏分的传统加氢裂化和加氢处理法还需要高资本投资和显著加工。
许多炼油厂在将原油蒸馏成各种馏分后进行传统加氢处理,各馏分单独加氢处理。因此,炼油厂必须针对各馏分使用复杂的单元操作。此外,在传统加氢裂化和加氢处理工艺中使用显著量的氢和昂贵的催化剂。这些工艺在严苛反应条件下进行以提高从重质原油到更有价值的中间馏出物的收率和除去杂质,如硫、氮和金属。
目前,使用大量的氢来调节由传统精炼法制成的馏分的性质以符合最终产品所需的低分子量规格;除去杂质,如硫、氮和金属;和提高基质的氢/碳比。沥青质和重馏分的加氢裂化和加氢处理是需要大量氢的工艺的实例,这两种工艺都造成催化剂具有降低的周期寿命。
因此,使用有效和低成本的方法仅裂化全原油的重质部分是有益的,以使整个全原油物流由较有价值的轻馏分构成,从而降低下游精炼成本。
水热裂化-超临界水
已经在添加外部氢源的情况下使用超临界水作为烃裂化所用的反应介质。水具有在大约705°F(374℃)和大约22.1MPa的临界点。在这些条件之上,水的液体和气体之间的相界消失,所得超临界水表现出对有机化合物的高溶解度和与气体的高混溶性。
但是,如果全原油含有提高量的重质烃分子,利用超临界水将全原油改质可具有严重的缺点。重质烃分子比它们的较轻对应物慢得多地溶解到超临界水中。此外,具有缠结结构的沥青质分子不容易用超临界水解开。因此,未与超临界水接触的重质烃分子部分自身热分解,造成大量的焦。因此,如果该全原油含有提高量的重质烃,使用目前的方法使该全原油与超临界水反应造成反应器内的焦积聚。
当焦积聚在反应器内时,该焦充当绝热体并有效阻碍辐射热遍布反应器,从而造成提高的能量成本,因为操作者必须提高运行温度以补偿该积聚。此外,积聚的焦也能够提高工艺管线中的压降,造成能量成本的额外提高。
防止焦积聚的另一可能的解决方案是提高全原油在反应器内的停留时间以溶解整个部分的原油和降低该反应器的温度;但是,该工艺的总体经济性和改质性能降低。另外,反应器设计的改进可能有用;但是,这需要设计成本的大支出和可能最终证实不有益。因此,需要促进重油与超临界水的有效接触的方法,其不造成大量焦或运行成本的显著提高。
提高油采收率
提高油采收率(EOR)是提高可从油田采出的油量的技术的一般术语。与使用一次和二次采收时的20-40%相比,使用EOR,可以提取油层的原始油的大约30-60%或更多。用于EOR的典型流体包括气体、液体、水蒸汽或其它化学品,气体注射是最常用的EOR技术。
在气体型EOR中,将气体,如二氧化碳(CO2)、天然气或氮气注入油层,在此其膨胀并由此将更多原油推至生产井眼。此外,该气体溶解在原油中,这降低原油的粘度和改进原油流过传输管的流速。
在足以使其与该油层中的油一样稠密的压力下将CO2泵入油层时,CO2可能变得与油混溶。刚实现可混溶性的压力被称作最低混相压力(MMP)。等于或高于其MMP时,CO2变成油的理想溶剂,因此其比水有效得多地从油层中置换油。其提取较轻烃组分,使油的总体积膨胀并降低其粘度以使其更易流动。
CO2目前是最有前途的原油采收流体之一,因为溶解的CO2容易在生产后通过减压与采收的原油分离。当然,CO2在原油中的溶解度极大取决于压力、温度、气/油比和该原油的组成。但是,控制CO2和原油的相行为的最简单方式是改变压力。在低压下,CO2表现出在原油,特别是重馏分中的极低溶解度。另外,原油中的CO2溶解造成原油膨胀,从而提高原油中可能存在的沥青质的溶解度。
如上所述,高密度全原油与超临界水接触的缺点之一是产生大量低价值焦。这种焦生成是由超临界水无法有效渗透整个高密度全原油,特别是该全原油的重馏分引起的。但是,由于溶解在原油中的CO2使原油膨胀并因此变稀,将CO2 EOR法与超临界水结合能够通过促进重馏分溶解到超临界水中来在不产生显著量焦的情况下将全原油改质。
由于处理量太高,加工整个全原油物流在经济上不可行。因此,在仅接触全原油的重质部分以限制焦转化、提高总油井产量和制造主要是高价值的轻馏分的最终原油的同时将CO2 EOR采收法与超临界水裂化法结合的简单和经济的方法是合意的。
此外,既不需要外部供应氢也不存在外部供应的催化剂的用超临界水流体将全原油改质的改进的方法是合意的。创造能够将全原油而非独立的馏分改质以达到所需品质的方法和装置是有利的,以便可简化精炼工艺和各种辅助设施。
另外,有益的是不需要与需要供氢或除焦系统的其它方法相关的复杂设备或设施的改进的方法,以致该方法可以在产地实施。
发明概述
本发明涉及满足这些需要中的至少一个的方法。本发明提供通过仅使一部分全原油物流与超临界水接触来将一部分全原油物流改质的方法。本发明特别利用EOR法采收全原油,其中采收的全原油以逐步方式减压以使该全原油的重馏分不再与采收流体混溶。随后将该含有少量溶解的采收流体的重馏分物流送往合适的设备,在此使该重馏分物流与水在超临界条件下接触。由于该少量溶解的采收流体使重馏分物流膨胀,该重馏分物流能够更容易用超临界水改质,以致较少成焦和降低运行成本。此外,由于该方法仅将一部分全原油改质,本发明的方法可以应对更大的处理量,以使其可以在产地使用并进一步降低总运行费用。
在本发明的一个实施方案中,将全原油改质的方法可包括在超过采收流体的最低混相压力的压力下向注入井中注入加压的采收流体以使该采收流体可操作为扫过地下岩层(underground formation)以提高生产井的全原油采收率。在从生产井中采收时,该采收流体与全原油密切混合以产生高压物流,其中该全原油包含轻馏分和重馏分。
该高压物流随后在保持小部分采收流体在重馏分内的混溶性的条件下减压,并从该高压物流中分离重馏分以形成轻质原油物流和重馏分物流。该轻质原油物流含有显著部分的采收流体。可以通过任何合适的设备,包括闪蒸器从该轻质原油物流中分离采收流体以形成轻馏分物流。
通过使该重馏分物流与水进料物流在超临界条件下接触,将该重馏分物流重整成重整的重馏分,其中该重整的重馏分与全原油相比具有降低量的含沥青质、硫、氮或金属的物质。
在另一实施方案中,在从轻质原油物流中分离所述显著部分的采收流体后产生的轻馏分物流可以与所述重整的重馏分合并以产生改质全原油,其中该改质全原油具有比全原油更高的API比重和降低量的含沥青质、硫、氮或金属的物质。
在另一实施方案中,该采收流体选自气体、液体、水蒸汽、化学品及其组合。在进一步实施方案中,该气体选自二氧化碳、氮气、天然气及其组合。在进一步实施方案中,二氧化碳是优选气体。对于本发明目的,气体是指在常温常压下既非固体也非液体的物质。
在另一实施方案中,重整该重馏分物流的步骤进一步包括将该重馏分与水进料物流合并以产生混合物,其中在不存在外部供应的氢的情况下产生该混合物。随后改变该混合物的温度以使该混合物在反应区中的温度等于或高于水临界温度,以使该混合物中的至少一部分烃发生裂化以产生热适应的(adapted)混合物。将该热适应的混合物冷却和减压以产生减压的适应的混合物。将该减压的适应的混合物分离成气体部分和液体部分,随后将该液体部分分离成回收的水物流和重整的重馏分。在另一实施方案中,在不存在外部供应的催化剂的情况下产生该混合物。在另一实施方案中,该反应区包含具有内部部分的主反应器,其中该主反应器是垂直取向的反应器,以使该预热混合物向下流经该垂直取向的反应器。在进一步实施方案中,通过压力调节设备将该热适应的混合物减压。该压力调节设备优选是至少一个背压调节器,更优选是以并联方式构造的两个或更多个背压调节器。
在另一实施方案中,重整该重馏分物流的步骤可以包括将水进料物流和重馏分物流的压力提高至超过水临界压力的目标压力。该重馏分物流与水进料物流在略微升高的温度下混合以形成混合物,选择该温度以使混合物在该略微升高的温度下容易泵送。略微升高的温度是与环境温度相比略微升高的温度。示例性的升高温度包括50-150℃的温度。将继续保持在水临界压力之上的该混合物泵送至加热区。在加热区中将该混合物加热到大约150℃至350℃的温度以形成预热混合物。随后将该预热混合物送入反应区。将反应区内的温度提高至等于或高于水临界温度的目标温度,以使该预热混合物的至少一些烃发生裂化,从而形成热适应的混合物,该反应区基本不含外部提供的催化剂和基本不含外部提供的氢源。将该热适应的混合物冷却和减压以形成减压的适应的混合物。使用至少一个分离器将该减压的适应的混合物分离成气体部分和液体部分,随后使用至少一个油-水分离器将该液体部分分离成重整重馏分和回收的水物流。
在另一实施方案中,该回收的水物流可以在超临界条件下氧化以形成处理过的水物流,随后可以通过将该处理过的水物流与水进料物流合并,使该处理过的水物流再循环。在本发明的另一实施方案中,该主反应器可以是垂直取向的反应器,以使该预热混合物向下流经该垂直取向的反应器。在进一步实施方案中,通过压力调节设备将该热适应的混合物减压。该压力调节设备优选是至少一个背压调节器,更优选是以并联方式构造的两个或更多个背压调节器。
在另一实施方案中,重整该重馏分物流的步骤可以包括将水进料物流和重馏分物流的压力提高至超过水临界压力的目标压力。随后将水进料物流加热至升高的温度以形成加热的水物流,以使该加热的水物流处于超临界态。重馏分物流与该加热的水物流在混合区中混合以形成预热混合物,其中该混合区位于反应区附近,以使该预热混合物保持超临界态,随后将该预热混合物进料入反应区。将反应区内的温度提高至等于或高于水临界温度的目标温度,以使该预热混合物的至少一些烃发生裂化,从而形成热适应的混合物,该反应区基本不含外部提供的催化剂和基本不含外部提供的氢源。将该热适应的混合物冷却和减压以形成冷却的适应的混合物。将冷却的适应的混合物减压以形成减压的适应的混合物。使用至少一个液-气分离器将该减压的适应的混合物分离成气体部分和液体部分,并使用至少一个油-水分离器将该液体部分分离成重整重馏分和回收的水物流。
在另一实施方案中,该回收的水物流可以在超临界条件下氧化以形成处理过的水物流,随后可以通过将该处理过的水物流与水进料物流合并,使该处理过的水物流再循环。在本发明的另一实施方案中,该主反应器可以是垂直取向的反应器,以使该预热混合物向下流经该垂直取向的反应器。在进一步实施方案中,通过压力调节设备将该热适应的混合物减压。该压力调节设备优选是至少一个背压调节器,更优选是以并联方式构造的两个或更多个背压调节器。
本发明的方法不要求外部供应氢和/或催化剂来将烃改质。外部催化剂的不存在通过避免催化剂的成本以及使用外部催化剂时的操作缺陷而创造成本有效的方法。与其它热裂化法相比,本发明的方法中的超临界水流体也抑制焦炭的形成,因此提高液体收率。
此外,超临界水流体促进质量传递,这提高反应速度。在一个实施方案中,预热混合物在反应区内的停留时间为0.1至30分钟,更优选5至15分钟。
本发明还提供将全原油改质的装置。在本发明的一个实施方案中,该装置具有注入井、生产井、分馏设备和水热重整设施。在一个实施方案中,该注入井与地下岩层流体连通。此外,该注入井可操作为接收加压的采收流体和将该加压的采收流体引入地下岩层。该加压的采收流体在地下岩层内与全原油密切混合以形成高压物流,该高压物流由采收流体和全原油构成,其中该全原油包含轻馏分和重馏分。在一个实施方案中,该生产井与地下岩层流体连通以使该生产井可操作为从地下岩层产生高压物流。
在本发明的一个实施方案中,该分馏设备与生产井流体连通。该分馏设备可操作为以逐步方式将该高压物流减压,以便从该高压物流中分离重馏分以形成轻质原油物流和重馏分物流,同时小部分采收流体保持在重馏分内的可混溶性,且该轻质原油物流含有显著部分的采收流体。
在本发明的一个实施方案中,该水热重整设施可操作为通过使该重馏分物流与水进料物流在超临界条件下接触来将该重馏分物流重整成重整的重馏分,从而产生与全原油相比具有降低量的重馏分、含沥青质、硫、氮或金属的物质的重整重馏分。在本发明的另一些实施方案中,该水热重整设施具有混合区、预热区、高压泵送工具和反应区。在一个实施方案中,该混合区包括超声波发生器。此外,该混合区可操作为在略微升高的温度下将重油与水进料合并。预热区与混合区流体相连,该预热区可操作为将其内容物加热至最多大约350℃的温度。该高压泵送工具可操作为提高该装置内的压力以超过水的临界压力。该反应区包括主反应器的内部部分,其中该反应区与预热区流体相连,且该主反应器可操作为承受至少与水临界温度一样高的温度。另外,该主反应器可操作为承受超过水临界压力的压力。在本发明的一个实施方案中,该反应区基本不含外部提供的催化剂和基本不含外部提供的氢源。
在本发明的另一些实施方案中,该水热重整设施还可以包括压力调节设备、与该压力调节设备流体相连的液-气分离器、和与该液-气分离器流体相连的水-油分离器。该液-气分离器可操作为产生液体物流和气体物流,且该水-油分离器可操作为产生回收的水物流和改质烃物流。在本发明的另一实施方案中,该水热重整设施还可以包括经由回收的水物流与该水-油分离器流体相连的氧化反应器。该氧化反应器可操作为在该回收的水再循环和与水进料合并之前清洁该回收的水。
另外,本发明的方法和装置可以容易地在全原油的产地使用,因为本发明的各种实施方案不需要与要求供氢或除焦系统的其它方法相关的复杂设备或设施。此外,该低倾点和高API比重原油具有低的硫、氮和金属含量,这提高该原料的价值,因为由此将进一步的昂贵加氢处理尽量降低。
附图简述
参照下列描述、权利要求和附图更好地理解本发明的这些和其它特征、方面和优点。但是,要指出,附图仅例举本发明的几个实施方案,因此不应被视为限制本发明的范围,因为其允许其它同样有效的实施方案。
图1是根据本发明的一个实施方案的工艺图的透视图。
图2是该方法的重整步骤的实施方案的更详细视图。
图3是该方法的重整步骤的另一实施方案的更详细视图。
图4显示轻馏分和重馏分中的二氧化碳溶解度曲线。
详述
本发明提供在不外部供应氢或催化剂的情况下将全原油转化成更有价值的原油原料的方法。该方法大致包括在压力下将采收流体注入至注入井以使该采收流体扫过地下岩层并由此提高生产井的总产量。该方法进一步包括以逐步方式将与采收流体密切混合的采收的全原油减压,以分离构成该全原油的轻馏分和重馏分。随后将该重馏分送往用于重整的水热改质设施。
该重整步骤大致包括使该重馏分与热加压水接触以制造具有比全原油更高的API比重和降低量的含沥青质、硫、氮或金属的物质的重整重馏分。该重整步骤在不存在外加氢的情况下进行。该热加压水在水的临界温度和压力之上并表现出在本发明中用于实现所需最终结果的独特性质。
热加压水通过促进质量扩散、热传递、分子内或分子间氢转移、稳定用于抑制成焦的自由基化合物和除去杂质,如含硫、氮和金属的分子来提供使重质组分裂化成低分子量烃所用的反应介质。尽管尚未确定去除杂质的确切机制,但杂质似乎吸收到水相中或集中在焦或改质产品的重馏分中。通过使用超临界水,从原油中分离这些杂质以避免有害作用。
该方法进一步包括从轻质原油物流中分离采收流体以形成轻馏分物流,并且在一个实施方案中,将该轻馏分物流与重整重馏分合并以形成改质全原油。此外,从该轻质原油物流中分离的采收流体可以回收和再循环以在注射步骤中再使用。
本发明的上述实施方案提供从地下提取全原油和将该全原油的低价值重质组分改质的有效方法,所有这些都在使处理量保持正常水平的同时实现。本发明是有利的,因为其不需要昂贵的催化剂以重整重馏分。此外,本发明提供不使用更传统和更昂贵的蒸馏设备将全原油分馏成重馏分和轻馏分的实用方式。此外,本发明允许生产公司在产地将全原油改质,而非将全原油转移至远程地点进行改质,从而进一步降低成本。
现在参照图1,其代表本发明的一个实施方案,其中二氧化碳是采收流体。将储存在二氧化碳储罐[5]中的二氧化碳压缩和经由压缩二氧化碳管线[7]注入至注入井[15]中。使该压缩二氧化碳的压力保持在最低混相压力(MMP)之上以确保二氧化碳在地下岩层[17]中的全原油中的混溶性。该MMP随井而变;但是,二氧化碳的MMP通常为2000psig至4000psig。因此,该二氧化碳注射的运行压力通常为2000psig至5000psig。水也可以与二氧化碳一起注入以促进原油采收率,这是公知的水气交替设计(WAG),并经此引用并入本文。
该混溶的二氧化碳和全原油经由生产井[25]达到地面,该高压物流[27]随后进入分馏设备[35],其中将压力降至低于MMP,但高于特定值,以使该高压物流的重质部分变得与二氧化碳不混溶。在一个实施方案中,分馏设备[35]的压力保持在接近二氧化碳临界压力(1073psig)的压力范围内。优选的压力范围为500psig至2000psig,更优选1,000psig至1,300psig。分馏设备[35]内的温度保持在0℃至50℃,优选20℃至40℃的范围内。
随后将仍含有少量二氧化碳的被称作重馏分物流[4]的这种重质部分送往水热重整设施[45],由此重馏分物流[4]与水在超临界条件下接触,以产生重整重馏分[92]。重馏分物流[4]内少量二氧化碳的存在提供两种益处。首先,被重馏分物流溶解的二氧化碳降低粘度,以使该物流更容易流动。其次,如上所述,溶解的二氧化碳降低该重馏分的密度,以使超临界水更有效地与重油分子相互作用,这造成更好转化率、降低的焦油生成量和较低的运行成本。
包含显著部分二氧化碳和该全原油的轻馏分的轻质原油物流[37]离开分馏设备[35]和进入二氧化碳分离器[55],其中通过将压力降至大约大气压,除去残留二氧化碳;留下轻馏分物流[59]。该分离的二氧化碳经由再循环二氧化碳管线[57]再循环回二氧化碳储罐[5]。随后将轻馏分物流[59]进料入改质全原油储罐[65],在此其与重整重馏分[92]合并储存。最终产物——改质全原油[96]可随后运输以供进一步精炼。
图2代表水热重整设施[45]的一个实施方案。将水进料物流[2]进料入储水罐[10],在此随后使用高压计量水泵[20]将水进料物流[2]泵送至该方法的混合区[30]。类似地将重馏分物流[4]进料入重馏分储罐[11],在此随后使用高压计量重馏分泵[21]将重馏分物流[4]泵送至该方法的混合区[30]。在混合区[30]之前,重馏分物流[4]处于允许流动的温度;但是,该温度优选不超过150℃。这两个物流在混合区[30]合并形成混合物[32]。随后将混合物[32]进料入加热区[40],在此将该温度提高到在150至400℃,更优选150至350℃范围内的温度以形成预热混合物[42]。
随后将预热混合物[42]进料入主反应器[50],其中温度和压力接近或超过水的临界点,以使预热混合物[42]的至少一些烃发生裂化,以形成热适应的混合物[52],主反应器[50]具有基本不含外部提供的催化剂和基本不含外部提供的氢源的内部部分。随后使用任何可接受的冷却工具[60],优选热交换器冷却热适应的混合物[52],以产生冷却的适应的混合物[62]。冷却的适应的混合物[62]随后通过压力调节设备[70]减压以产生减压的适应的混合物[72]。在一个实施方案中,压力调节设备[70]包含至少两个背压调节器,更优选三个背压调节器[70a,70b,70c](以并联方式连接)。该布置有利地在主背压调节器堵塞的情况下提供继续运行。减压的适应的混合物[72]随后进入液-气分离器[80],在此将减压的适应的混合物[72]分离成气体部分[82]和液体部分[84]。随后将液体部分[84]进料入油-水分离器[90]以产生重整重馏分[92]和回收的水[94]。在另一实施方案中,回收的水[94]可以在储水罐[10]之前或之后再循环和再用作水进料物流[2]。
图3代表在混合区[30]之前将水进料物流[2]预热至超临界条件的一个实施方案。在此实施方案中,将水进料物流[2]进料入储水罐[10],在此随后使用高压计量水泵[20]将水进料物流[2]泵送至该方法。但是,不先与重馏分物流[4]混合,而是将水进料物流[2]在加热区[40]中加热以形成加热的水物流[41],其中加热的水物流[41]处于超临界态。
类似地将重馏分物流[4]进料入高蜡原油储罐[11],在此随后使用高压计量重馏分泵[21]将重馏分物流[4]泵送至该方法的混合区[30]。在混合区[30]之前,重馏分物流[4]处于允许流动的温度;但是,优选不超过150℃。重馏分物流[4]和加热的水物流[41]在混合区[30](其优选接近主反应器[50])合并,以产生预热混合物[42]。
预热混合物[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,以使预热混合物[42]的至少一些烃发生裂化,以形成热适应的混合物[52],主反应器[50]基本不含外部提供的催化剂和基本不含外部提供的氢源。随后使用任何可接受的冷却工具[60],优选热交换器冷却热适应的混合物[52],以产生冷却的适应的混合物[62]。冷却的适应的混合物[62]随后通过压力调节设备[70]减压以产生减压的适应的混合物[72]。在一个实施方案中,压力调节设备[70]包含至少两个背压调节器,更优选三个背压调节器[70a,70b,70c](以并联方式连接)。该布置有利地在主背压调节器堵塞的情况下提供继续运行。减压的适应的混合物[72]随后进入液-气分离器[80],在此将减压的适应的混合物[72]分离成气体部分[82]和液体部分[84]。随后将液体部分[84]进料入油-水分离器[90]以产生重整重馏分[92]和回收的水[94]。在另一实施方案中,回收的水[94]可以在储水罐[10]之前或之后再循环和再用作水进料物流[2]。
图4显示作为压力的函数的二氧化碳的大致溶解度曲线。一般而言,二氧化碳更容易溶解在具有较低分子量的油馏分而非具有较高分子量的油馏分中。曲线1代表二氧化碳溶解到重馏分中的溶解度曲线,而曲线2代表二氧化碳溶解到轻馏分中的溶解度曲线。在本发明中,压力A代表离开生产井的高压物流的压力,压力B是图1中的分馏设备[35]的压力。
如图4中所示,二氧化碳在重馏分中的溶解度比其在轻馏分中的溶解度更快地降低。正是这种溶解度差异允许本发明成功地将重馏分与该高压物流的其余部分分离。实际上,压力A应超过实测或预测的采收流体的MMP。
可以通过进行一系列实验来最佳地选择压力B。直觉上,如果压力B太高,分离较少重馏分,这限制总转化率;但是,如果压力B设置太低,相对显著部分的轻馏分被送入水热重整设施,这需要更大的设备和更多动力以使该额外的轻馏分流贯穿水热设施。在任一情况下,该方法的总效率降低。因此,应该进行实验以优化图1的分馏设备[35]的运行压力,在本领域普通技术人员显而易见的许多其它变量中,尤其将例如所用采收流体的类型、全原油的独特特性、设备特性和所需处理量计入考虑。
尽管仅以其一些形式显示或描述本发明,但本领域技术人员显而易见的是,本发明不限于此,而是可以在不背离本发明范围的情况下作出各种变动。
Claims (20)
1.将全原油改质的方法,该方法包括下列步骤:
在超过采收流体的最低混相压力的压力下向注入井中注入加压的采收流体以使该采收流体可操作为扫过地下岩层以提高生产井的全原油采收率,在从生产井中采收时,该采收流体与全原油密切混合以产生高压物流,其中该全原油包含轻馏分和重馏分;
在保持小部分采收流体在重馏分内的混溶性的条件下将该高压物流减压,并从该高压物流中分离重馏分以形成轻质原油物流和重馏分物流,该轻质原油物流含有显著部分的采收流体;
从该轻质原油物流中分离采收流体以形成轻馏分物流;
通过使该重馏分物流与水进料物流在超临界条件下接触,将该重馏分物流重整成重整重馏分,其中该重整重馏分与全原油相比具有降低量的重馏分、含沥青质、硫、氮或金属的物质。
2.权利要求1的方法,进一步包括将轻馏分物流与重整重馏分合并以产生改质全原油,其中该改质全原油与全原油相比具有降低量的重馏分、含沥青质、硫、氮或金属的物质。
3.权利要求1的方法,其中该采收流体选自气体、液体、水蒸汽、化学品及其组合。
4.权利要求1的方法,其中该采收流体是选自二氧化碳、氮气、天然气及其组合的气体。
5.权利要求1的方法,其中该采收流体是二氧化碳。
6.权利要求1的方法,其中从该轻质原油物流中分离采收流体的步骤包括闪蒸器。
7.权利要求1的方法,其中重整该重馏分物流的步骤进一步包括:
将该重馏分与水进料物流合并以产生混合物,其中在不存在外部供应的氢的情况下产生该混合物;
改变该混合物的温度以使该混合物在反应区中的温度等于或高于水临界温度,以使该混合物中的至少一部分烃发生裂化以产生热适应的混合物;
将该热适应的混合物冷却并减压以产生减压的适应的混合物;
将该减压的适应的混合物分离成气体部分和液体部分;和
将该液体部分分离成回收的水物流和重整重馏分。
8.权利要求7的方法,其中在不存在外部供应的催化剂的情况下产生该混合物。
9.权利要求7的方法,其中该反应区包含具有内部部分的主反应器,该主反应器包含垂直取向的反应器,以使该预热混合物向下流经该垂直取向的反应器。
10.权利要求7的连续方法,其中通过压力调节设备将该热适应的混合物减压,该压力调节设备包含至少一个背压调节器。
11.权利要求10的连续方法,其中该压力调节设备包括以并联方式构造的两个或更多个背压调节器。
12.权利要求1的方法,其中重整该重馏分物流的步骤进一步包括:
将水进料物流和重馏分物流的压力提高至目标压力,该目标压力超过水临界压力;
将该重馏分物流与水进料物流在略微升高的温度混合以形成混合物,选择该温度以使混合物在该略微升高的温度下能够容易地泵送;
在超过水临界压力的压力下将该混合物泵送至加热区;
在加热区中将该混合物加热到大约150℃至350℃的温度以形成预热混合物;
将该预热混合物进料入反应区;
将反应区内的温度提高至等于或高于水临界温度的目标温度,以使该预热混合物的一部分烃发生裂化,以形成热适应的混合物,该反应区基本不含外部提供的催化剂和基本不含外部提供的氢源;
将该热适应的混合物冷却和减压以形成减压的适应的混合物;
使用至少一个分离器将该减压的适应的混合物分离成气体部分和液体部分;和
使用至少一个油-水分离器将该液体部分分离成重整重馏分和回收的水物流。
13.权利要求12的方法,进一步包括:
在超临界条件下氧化该回收的水物流以形成处理过的水物流;和
通过将该处理过的水物流与水进料物流合并,使该处理过的水物流再循环。
14.权利要求1的方法,其中重整该重馏分物流的步骤进一步包括:
将水进料物流和重馏分物流的压力提高至超过水临界压力的目标压力;
将水进料物流加热至升高的温度以形成加热的水物流,以使该加热的水物流处于超临界态;
使重馏分物流与该加热的水物流在混合区中混合以形成预热混合物,其中该混合区位于反应区附近,以使该预热混合物保持超临界态;
将该预热混合物进料入反应区;
将反应区内的温度提高至等于或高于水临界温度的目标温度,以使该预热混合物的至少一些烃发生裂化,以形成热适应的混合物,该反应区基本不含外部提供的催化剂和基本不含外部提供的氢源;
将该热适应的混合物冷却和减压以形成减压的适应的混合物;
使用至少一个液-气分离器将该减压的适应的混合物分离成气体部分和液体部分;和
使用至少一个油-水分离器将该液体部分分离成重整重馏分和回收的水物流。
15.权利要求14的方法,进一步包括:
在超临界条件下氧化该回收的水物流以形成处理过的水物流;和
通过将该处理过的水物流与水进料物流合并,使该处理过的水物流再循环。
16.将全原油改质的装置,该装置包括:
注入井,其与地下岩层流体连通,该注入井可操作为接收加压的采收流体和将该加压的采收流体引入地下岩层,在此该加压的采收流体在地下岩层内与全原油密切混合以形成高压物流,该高压物流包含采收流体和全原油,其中该全原油包含轻馏分和重馏分;
生产井,其与地下岩层流体连通,该生产井可操作为从地下岩层产生高压物流;
分馏设备,其与生产井流体连通,其中该分馏设备可操作为以逐步方式将该高压物流减压,以便从该高压物流中分离重馏分以形成轻质原油物流和重馏分物流,其中小部分采收流体保持在重馏分内的可混溶性,和其中该轻质原油物流含有显著部分的采收流体;和
水热重整设施,其可操作为通过使该重馏分物流与水进料物流在超临界条件下接触来将该重馏分物流重整成重整重馏分,其中该重整重馏分与全原油相比具有降低量的重馏分、含沥青质、硫、氮或金属的物质。
17.权利要求16的装置,其中该水热重整设施包括:
混合区,其可操作为在略微升高的温度接收重馏分与水进料以产生重油/水混合物;
预热区,其与该混合区流体相连,该预热区可操作为将该重油/水混合物加热至最多大约350℃的温度;
高压泵送工具,该高压泵送工具可操作为将该重油/水混合物的压力提高至至少水的临界压力;和
反应区,其与预热区流体相连;该反应区包含主反应器的内部部分,该主反应器可操作为承受至少与水临界温度一样高的温度;该主反应器可操作为承受超过水临界压力的压力,该反应区基本不含外部提供的催化剂和基本不含外部提供的氢源。
18.权利要求17的装置,其中该混合区进一步包括超声波发生器,其可操作为对该重油/水混合物施以空化作用和进一步通过产生亚微乳状液来诱发重油/水混合物的混合。
19.权利要求17的装置,进一步包括:
压力调节设备;
液-气分离器,其与该压力调节设备流体相连,该液-气分离器可操作为产生液体物流和气体物流;和
水-油分离器,其经由液体物流与该液-气分离器流体相连,该水-油分离器可操作为产生回收的水物流和改质烃物流。
20.权利要求19的装置,其中该回收的水物流可以再循环和与水进料合并,且该装置进一步包括与该回收的水物流流体相连的氧化反应器,该氧化反应器可操作为经由氧化来清洁该回收的水物流。
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CN104471187A (zh) * | 2012-06-27 | 2015-03-25 | 国际壳牌研究有限公司 | 石油采收方法和系统 |
CN105403347A (zh) * | 2015-11-27 | 2016-03-16 | 中国石油化工股份有限公司 | Co2驱最小混相压力测定方法及专用装置 |
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CN112175662A (zh) * | 2017-01-03 | 2021-01-05 | 沙特阿拉伯石油公司 | 从石油中去除硫和金属的方法 |
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