CN101970611A - 通过热加压水和超声波发生预混器将重油改质的方法 - Google Patents
通过热加压水和超声波发生预混器将重油改质的方法 Download PDFInfo
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Abstract
通过使用超声波发生器将重油与水物流混合，随后将该混合物的温度和压力提高至接近或超过水临界点的值来将重油改质以制造用作烃原料的具有低硫、低氮和低金属杂质的低倾点高价值油的方法。
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.60/990,648；60/990,662；60/990,658；60/990,670；和60/990,641的优先权，它们都全文经此引用并入本文。
发明技术领域
本发明涉及通过使重油与超临界水流体接触来将重油改质的方法。特别地，通过使用超声波发生器将水和重油预混来加速水热改质法。此外，不使用外部供应的氢进行该方法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。
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油以满足未来日益增长的需求。但是，由于使用重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油的品质。
一般而言，重油提供较低量的较有价值的轻质和中间馏出物。另外，重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。
通常被定义为来自常压和真空蒸馏器的塔底馏分的重油还具有高沥青质含量、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油以制造规格符合严格政府规章的最终石油产品。
低价值的重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加工重油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。
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。
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，但杂质似乎集中在焦或改质产品的重馏分中。通过使用超临界水，将这些杂质氧化或以其它方式改性以避免有害作用。在Kirk Othmer Encyclopedia of Chemical Technology，第3版，John Wiley & Sons，Supplemental Volume，第872-893页(1984)中阐述了超临界流体萃取的基本原理。
但是，利用超临界水将重油改质可具有严重的缺点。重质烃分子与它们的较轻对应物相比更慢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，使用目前的方法使重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。
使用超临界水时成焦的原因之一可归因于氢的有限可供应性。已经提出若干建议以向用超临界水流体处理的进料烃供应外部氢。例如，可以将氢气直接添加到进料物流中。也可以将一氧化碳直接添加到进料物流中以经由一氧化碳和水之间的水煤气变换(WGS)反应生成氢。也可以将有机物质，如甲酸添加到进料物流中以通过由加入的有机物质分解产生的一氧化碳和水的WGS反应生成氢。另外，该进料物流中可包含少量氧以使进料基质内氧化生成一氧化碳。这种一氧化碳可随后用在制氢的WGS反应中。但是，将外部气体和/或有机物质进料入液体物流提高了成本和增加该方法的复杂性。
防止焦积聚的另一可能的解决方案是提高重油在反应器内的停留时间以使所有烃都溶解到超临界水中；但是，该工艺的总体经济性降低。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。
如上所述，焦化由重质烃分子与超临界水的不有效接触造成。因此，为了限制低价值焦的生成，提供提高超临界水与更大部分的重质烃接触的能力的方法是有利的。
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重油改质的改进的方法是合意的。创造能够将重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。本发明包括在不存在外部供应的氢的情况下将重油改质的方法。该方法大致包括在混合区中将重油与水进料合并以形成重油/水混合物并在使用超临界水裂化该重油/水混合物的重质组分之前对该重油/水混合物施以超声波。声波破坏重质烃分子部分并促进与水的混合，从而形成在本文中被称作亚微乳状液(submicroemulsion)的乳液样相。这种亚微乳状液含有通常具有小于1微米的平均直径的油滴，并在没有外部提供的化学乳化剂的情况下产生该亚微乳状液。
在本发明的一个实施方案中，将重油改质的方法包括在混合区中将重油与水进料合并以形成重油/水混合物。在一个实施方案中，该重油/水混合物的温度不超过150℃。该实施方案进一步包括对该重油/水混合物施以声波。超声波将已悬浮在水相内的油滴的尺寸降至小于1微米直径，从而产生亚微乳状液。该亚微乳状液随后使用高压泵送工具泵送经过预热区。在一个实施方案中，该高压泵送工具是高压泵；但是，本领域普通技术人员会认识到其它可接受的工具。该高压泵将该亚微乳状液的压力提高至超过水临界压力的目标压力。在该亚微乳状液在预热区内的同时，对该亚微乳状液施以大约150℃至350℃的第一目标温度，以产生预热的乳状液。该实施方案还包括将该预热的亚微乳状液进料入反应区并对该预热的亚微乳状液施以等于或高于水临界温度的第二目标温度，以使该预热的亚微乳状液的至少一部分烃发生裂化以产生热适应的(adapted)混合物。该反应区包括具有内部部分的主反应器，该主反应器可操作为承受超过水的临界温度和临界压力的温度和压力，且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。因此，该热适应的混合物基本不含外部提供的催化剂和基本不含外部提供的氢源。该实施方案可进一步包括从反应区中取出该热适应的混合物，冷却该热适应的混合物以形成冷却的适应的混合物和分离该冷却的适应的混合物以产生改质油和回收的水，其中该改质油是与重油相比具有降低量的含沥青质、硫、氮或金属的物质的改质重油。
优选地，该回收的水在超临界条件下氧化以形成处理过的水物流，其中随后通过将该处理过的水物流与水进料合并，使该处理过的水物流再循环回该方法。在另一实施方案中，可以捕集来自反应区的热适应的混合物和/或来自氧化步骤的处理过的水物流中所含的热能并可操作为在该方法的可利用热能的其它地方用于热交换。
在本发明的进一步实施方案中，该混合区包含超声波发生器，其优选为棒型(stick-type)超声波发生器、硬币型(coin-type)超声波发生器或其组合。另外，将重油与水进料混合的步骤可包括利用超声波发生器生成的超声波来产生混合作用，其中该超声波以优选大约10至50kHz，更优选大约20至40kHz的频率运行。该重油/水混合物具有优选10至120分钟的在该混合区内的停留时间。在另一进一步实施方案中，该主反应器可以是垂直取向的反应器，以使该预热的亚微乳状液向下流经该垂直取向的反应器。
在本发明的另一实施方案中，在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的方法包括在混合区中将重油与水进料混合以形成重油/水混合物，该重油/水混合物在略微升高的温度下混合，其中该略微升高的温度不超过150℃。可以通过在混合之前加热进料物流或通过在混合区中加热重油/水混合物来实现该略微升高的温度。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。
这种另一实施方案进一步包括对该重油/水混合物施以超声波，由此产生亚微乳状液，在超过水临界压力的压力下将该亚微乳状液泵送至预热区和在该预热区中将该亚微乳状液加热至大约150℃至350℃的第一目标温度以形成预热的亚微乳状液。随后将该预热的亚微乳状液进料入反应区并将反应区内的温度提高至等于或高于水临界温度的第二目标温度。这使该预热的亚微乳状液的至少一些烃发生裂化，以形成热适应的混合物。另外，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。随后将该热适应的混合物冷却并减压，以形成减压的适应的混合物。随后使用至少一个液-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进一步分离成改质油和回收的水物流。收集从该至少一个油-水分离器中回收的改质油，其中该改质油是与重油相比具有降低量的含沥青质、硫、氮或金属的物质的改质重油。
该回收的水在超临界条件下氧化以形成处理过的水物流，其中随后通过将该处理过的水物流与水进料合并，使该处理过的水物流再循环回该方法。在一个实施方案中，可以捕集来自反应区的热适应的混合物和/或来自氧化步骤的处理过的水物流中所含的热能并可在该方法的其它地方用于热交换。
在本发明的进一步实施方案中，该混合区包含超声波发生器，其优选为棒型超声波发生器、硬币型超声波发生器或其组合。另外，将重油与水进料混合的步骤可包括利用超声波发生器生成的超声波来产生混合作用，其中该超声波以优选大约10至50kHz，更优选大约20至40kHz的频率运行。该重油/水混合物具有优选10至120分钟的在该混合区内的停留时间。在另一进一步实施方案中，该反应区包括具有内部部分的主反应器，其中该主反应器包括垂直取向的反应器，以使该预热的亚微乳状液向下流经该垂直取向的反应器。
在本发明的另一实施方案中，在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的方法包括在混合区中将重油与水进料合并以形成重油/水混合物，该重油/水混合物在略微升高的温度下混合，其中该略微升高的温度不超过150℃。对该重油/水混合物施以用于降低该混合物的液滴尺寸的超声波能。随后在等于或高于水临界压力的压力下将该混合物加热至等于或高于水的超临界温度的温度，以使该重油/水混合物中的至少一部分烃发生裂化。随后将可该裂化的重油/水混合物冷却，减压并使用气-液分离器和油-水分离器进一步分离成气相、回收的烃相和回收的水相。该回收的烃相是与重油相比具有降低量的含沥青质、硫、氮或金属的物质的改质油。
本发明还涉及在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的装置。在本发明的一个实施方案中，该装置包括混合区、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。该反应区包括具有内部部分的主反应器，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，该装置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，该装置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。
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是本发明的一个实施方案。
详述
尽管联系几个实施方案描述了本发明，但要理解的是，不是要将本发明仅局限于这些实施方案。相反，旨在涵盖可包含在所附权利要求书规定的本发明的精神和范围内的所有替代、修改和等效方案。
本发明提供在不外部供应氢的情况下将重油转化成更有价值的原油原料的方法。在本发明的一个实施方案中，本发明的方法包括使用超声波发生器混合来重油和水进料以制造重油/水混合物和此后使该重油/水混合物经历预热阶段、反应区阶段、冷却阶段、减压阶段和多个分离阶段的步骤。优选地，通过使用合适的经济设备，来自反应区的产物物流中所含的热能可用于加热进料物流。来自分离阶段的回收的水中所含的有机化合物可以在氧存在下用热加压水充分氧化以获得用于再循环的清洁水。来自氧化反应的产物物流中所含的热能也可用于上游的热交换用途。
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倾点和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，但杂质似乎集中在焦、水或改质产品的重馏分中。通过使用超临界水，将这些杂质氧化或以其它方式改性以避免有害作用。
根据本发明的一个实施方案，将重油和水进料引入保持在略微升高的温度，优选10℃至150℃，更优选30℃至70℃的混合区中。在室温下测得的重油与水的重量比为10∶1至1∶10wt/wt。该混合区包含超声波发生器，其可以是棒型、硬币型或其组合。该超声波发生器优选是棒型。优选将该超声波发生器的频率调节至在10kHz至50kHz，和更优选20kHz至60kHz的范围内。重油/水混合物停留时间可以调节在10分钟至120分钟。
超声波发生器生成的超声波在整个重油/水混合物中反射，以致油滴大体裂开，从而产生水和油的亚微乳状液，由此油滴通常具有小于1微米的平均直径。这种亚微乳状液有利地在超临界条件下反应，因为该亚微乳状液能够改进重质分子和超临界水之间的接触，由此降低低价值焦的总生成量。另外，超声波释放出的一些能量转化成热能，其又使该亚微乳状液的温度提高。因此，该混合区优选包含温度控制器，以使该混合区内的温度保持在上文提到的优选参数内。
随后经由高压泵送工具将该亚微乳状液引入处于超过水临界压力的压力下的预热区中。在本发明的一个实施方案中，该高压泵送工具是高压泵。该预热区(其优选包含加热器和管)对该亚微乳状液施以大约150℃至350℃的第一目标温度以形成预热的亚微乳状液。可以通过使进料物流与例如来自反应区阶段的产物物流或来自氧化反应器的处理过的水物流热交换来提供用于此用途的加热。
随后将该预热的亚微乳状液进料入反应区。在一个实施方案中被加热器围绕的该反应区在保持高于水临界压力的压力的同时将该预热的亚微乳状液的温度提高到374℃至600℃。在该反应区中，大的烃分子分解成较小分子。另外，在此阶段除去杂质，如含硫、氮和金属的分子。随后将来自反应区的产物物流——其是热适应的混合物——冷却并通过压力调节设备减压，以形成减压的适应的混合物，其随后通过一系列合适的分离器分离成气体部分和液体部分。
随后通过油-水分离器将该减压的适应的混合物的液体部分分离成改质油和回收的水。任选地，来自该油-水分离器的回收的水通过氧化反应器在超临界条件下用氧处理以除去该回收的水中所含的油性杂质，从而形成处理过的水物流。用于此用途的氧可以由氧气、过氧化氢、有机过氧化物和空气供应。离开该氧化反应器的处理过的水物流具有由氧化反应产生的高热能。因此，该处理过的水物流可以与例如反应区和/或氧化反应器的进料物流热交换。
从油-水分离器中回收的改质油含有比重油进料更低量的硫、氮和金属化合物。因此，该改质油是用于精炼工艺的高品质原料。
现在参照图1，水进料[2]进入该连续法并进料入储水罐[10]。从储水罐[10]，将水进料[2]进料入混合区[20]并与重油[4]合并形成重油/水混合物。重油[4]从重油储罐[11]进料入混合区[20]。混合区[20]包含超声波发生器，其以10kHz至50kHz的频率向该混合区供应超声波，以进一步混合两种液体，从而产生亚微乳状液[22]。亚微乳状液[22]包含具有小于1微米的平均中值直径的油滴并在不存在外部提供的化学乳化剂的情况下产生。随后经由高压泵[30]将亚微乳状液[22]加压至超过水临界压力的压力并进料入预热区[40]，在此将该温度提高至在150℃至350℃的范围内的第一目标温度，以形成预热的亚微乳状液[42]。
随后将预热的亚微乳状液[42]进料入主反应器[50]，在此使压力保持在水的临界压力之上，并将预热的亚微乳状液[42]加热至至少与水的临界温度一样高的目标温度，以使预热的亚微乳状液[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反应区。随后使用任何可接受的冷却工具[60]，优选热交换器来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]。在另一实施方案中，压力调节设备[70]包含至少两个压力调节阀，更优选三个压力调节阀[70a，70b，70c](以并联方式连接)。该布置有利地在主调节阀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]以产生重整的重馏分[92]和回收的水[94]。在另一实施方案中，回收的水[94a]可优选在储水罐[10]之前再循环回该方法以再用作水进料[2]。
通过下列示例性实施方案进一步验证本发明的方法，这些实施方案不是本发明的方法的限制。
示例性实施方案
通过本发明的方法加工具有根据表I的性质的来自真空蒸馏的残油。首先，进料重油和蒸馏水分别以1升和4升的量装入混合容器中。该混合容器具有8升的容量并配有以30kHz运行的超声均化器。该均化器在500瓦运行1小时，并使该混合器的温度保持在50℃。随后使用高压泵将该混合物进料入预热区，在此将该混合物的温度提高至250℃。随后在保持压力为25MPa的情况下将该加热的混合物引入反应区并加热至450℃的温度大约60分钟。反应区的输出物与预热区的进料热交换，随后通过压力调节设备，优选背压调节器释压至大约0.1Mpa。压力调节设备的输出物随后进料入液-气分离器。来自液-气分离器的液体部分随后进料入油-水分离器。向该液体部分中加入破乳剂以加速相分离。收集并分析该油。总液体收率高于91.5重量％。处理过程中形成的焦和气体的量分别为原料的2.5和6.0重量％。最终油的API比重为12.5，且总硫含量为2.65重量％。几乎完全除去镍和钒，因为它们在最终油中具有可忽略的含量。
表I-示例性实施方案
| 性质 | 值 |
| 密度，°API | 2.6 |
| CCR，重量％ | 29.6 |
| 氮，重量％ | 0.49 |
| 硫，重量％ | 5.5 |
| 钒和镍，wt ppm | 157 |
有利地，本发明无需乳化剂就能制备亚微乳状液。类似地，本发明令人惊讶地产生极少焦或不产生焦。在一个实施方案中，本发明被认为仅产生2.5重量％的焦，与此相比，现有技术中的焦含量高得多。
本文所用的术语第一和第二和诸如此类应被解释为特指要素，而非暗示或局限于要素或步骤的任何特定次序。
尽管已联系其具体实施方案描述了本发明，但本领域技术人员参照上文的描述显然可看出许多替代、修改和变动。因此，旨在包括落在所附权利要求书的精神和宽泛范围内的所有这样的替代、修改和变动。
Claims (20)
1.在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的方法，该方法包括下列步骤：
在混合区中将重油与水进料合并以形成重油/水混合物，其中该重油/水混合物的温度不超过150℃；
对该重油/水混合物施以超声波以产生亚微乳状液；
使用高压泵将该亚微乳状液泵送经过预热区，其中该高压泵将该亚微乳状液的压力提高至等于或高于水的临界压力的目标压力；
将该亚微乳状液加热至第一目标温度以产生预热的亚微乳状液，该第一目标温度为大约150℃至350℃；
将该预热的亚微乳状液进料入反应区；
在该反应区内将该预热的亚微乳状液加热至等于或高于水临界温度的第二目标温度，以使该预热的亚微乳状液中的至少一部分烃发生裂化以产生热适应的混合物，该反应区包括具有内部的主反应器，该主反应器可操作为承受超过水的临界温度和临界压力的温度和压力，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；
从所述反应区中取出该热适应的混合物并冷却该热适应的混合物以形成冷却的适应的混合物；和
分离该冷却的适应的混合物以产生改质油和回收的水，其中该改质油是与重油相比具有降低量的含沥青质、硫、氮或金属的物质的改质重油。
2.权利要求1的方法，其中在不存在外部提供的化学乳化剂的情况下产生该亚微乳状液。
3.权利要求1的方法，其中该亚微乳状液包含具有小于1微米的平均直径的油滴。
4.权利要求1的方法，进一步包括：
在超临界条件下氧化该回收的水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合并，使该处理过的水物流再循环。
5.权利要求1的方法，其中该混合区包含超声波发生器。
6.权利要求5的方法，其中将重油与水进料混合的步骤包括利用超声波发生器生成的超声波来产生混合作用，其中该超声波以一定频率运行。
7.权利要求6的方法，其中由超声波发生器生成的超声波的频率在大约10至50kHz的范围。
8.权利要求7的方法，其中由超声波发生器生成的超声波的频率范围为大约20至40kHz。
9.权利要求1的方法，其中该亚微乳状液具有10至120分钟的在该混合区内的停留时间。
10.在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的方法，该方法包括下列步骤：
在混合区中将重油与水进料混合以形成重油/水混合物，该重油/水混合物在略微升高的温度混合，其中该略微升高的温度不超过150℃，该混合区包含超声波发生器；
在混合区内对该重油/水混合物施以超声波以产生亚微乳状液，从而在不存在外部提供的化学乳化剂的情况下产生该亚微乳状液；
使用高压泵送工具将该亚微乳状液泵送至预热区，其中该高压泵送工具将该亚微乳状液的压力提高至超过水临界压力的目标压力；
在该预热区中将该亚微乳状液加热至大约150℃至350℃的第一目标温度以形成预热的亚微乳状液；
将该预热的亚微乳状液进料入反应区；
将反应区内的温度提高至等于或高于水临界温度的第二目标温度，以使该预热的亚微乳状液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并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；
使用至少一个油-水分离器将该液体部分分离成改质油和回收的水物流；
收集从该至少一个油-水分离器中回收的改质油，其中该改质油是与重油相比具有降低量的含沥青质、硫、氮或金属的物质的改质油；
在超临界条件下氧化该回收的水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合并，使该处理过的水物流再循环。
11.权利要求10的方法，其中该亚微乳状液包含具有小于1微米的平均直径的油滴。
12.权利要求10的方法，其中将所述重油与水物流混合的步骤包括利用超声波发生器生成的超声波来产生混合作用，其中该超声波以一定频率运行。
13.权利要求12的方法，其中由超声波发生器生成的超声波的频率为大约10至50kHz。
14.权利要求13的方法，其中由超声波发生器生成的超声波的频率范围为20至40kHz。
15.权利要求10的方法，其中该超声波发生器选自棒型超声波发生器、硬币型超声波发生器及其组合。
16.权利要求10的方法，其中该亚微乳状液具有10至120分钟的在该混合区内的停留时间。
17.在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的方法，该方法包括下列步骤：
在混合区中将重油与水进料合并以形成重油/水混合物，该重油/水混合物在略微升高的温度混合，其中该略微升高的温度不超过150℃；
对该重油/水混合物施以超声波能；
在等于或高于水临界压力的压力下将该重油/水混合物加热至等于或高于水的超临界温度的温度，以使该重油/水混合物中的至少一部分烃发生裂化；
将该重油/水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；
使用至少一个油-水分离器将该液体部分分离成改质油和回收的水物流；
收集从该至少一个油-水分离器中回收的改质油，其中该改质油是与重油相比具有降低量的含沥青质、硫、氮或金属的物质的改质油。
18.在不含外部供应的催化剂或外部供应的氢源的环境中将重油改质的装置，该装置包括：
混合区，其可操作为在略微升高的温度将重油与水进料合并以产生重油/水混合物，该混合区包含超声波发生器；
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，其包含具有内部部分的主反应器，其中该反应区与所述预热区流体相连；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。
19.权利要求18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，其经由所述液体物流与该液-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能够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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