CN103842480A - 用于降低炼厂原料中总酸值的方法 - Google Patents

用于降低炼厂原料中总酸值的方法 Download PDF

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CN103842480A
CN103842480A CN201280046752.0A CN201280046752A CN103842480A CN 103842480 A CN103842480 A CN 103842480A CN 201280046752 A CN201280046752 A CN 201280046752A CN 103842480 A CN103842480 A CN 103842480A
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refinery
raw material
neutralization reaction
caustic alkali
naphthenic acid
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CN103842480B (zh
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A·奥-哈吉
O·R·克塞奥格卢
H·穆勒
H·奥贾瓦德
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Abstract

描述了用于降低炼厂原料的总酸值的方法。在一个实施方案中，在含水苛性碱的存在下使包含环烷酸的炼厂原料与有效量的固体催化剂接触足以中和至少部分原料中的环烷酸的一段时间，其中苛性碱是氢氧化钠或氢氧化钾。其后，将含水相从中和的炼厂原料中分离。在另一个实施方案中使用苛性碱溶液预处理催化剂并且使其与炼厂原料接触以降低总酸值。

Description

用于降低炼厂原料中总酸值的方法
相关申请
本申请要求2011年7月29日提交的美国临时专利申请号61/513,042的权益，其公开内容的全文以引用方式并入本文。
本发明背景技术
本发明领域
本发明涉及提质加工炼厂原料，特别地涉及通过中和环烷酸降低总酸值。
相关技术说明
天然石油或原油的组成基于多个因素(主要是地理来源)明显不同并且甚至在特定区域内，组成也可以不同。对原油的全部来源来说事实上通常存在杂原子，例如硫、氮、镍、钒和其它。一些原油也包含环烷酸化合物。这些杂质以影响原油及其馏分的炼厂加工的量存在。
术语“环烷酸”为源自环烷烃基原油中酸度的第一观测结果(observation)。环烷酸的化学组成极其复杂，并且多种结构和组成落在环烷酸的类别之内。环烷酸主要由使用烷基取代的羧基环脂族酸构成，具有较低比例的非环脂族酸。芳族酸、烯属酸、羟基酸和二元酸可以作为次要组分存在。存在于原油中的环烷酸的分子量，如通过质谱确定的，一般在约120和大于700克每摩尔之间变化。环烷酸化合物的存在促成原油酸度并且是油炼厂中油管线和蒸馏单元中的腐蚀的一个主要原因。因此，认为具有高环烷酸浓度的原油的质量不良并且以较低价格推向市场。
总酸值(“TAN”)是就油酸度而言普遍接受的标准，尽管其与腐蚀行为的关联依然不确定。具体地，TAN表示中和1克油的酸度所需的氢氧化钾的毫克数。一些原油拥有极其高水平的环烷酸度(例如这样的油，其每克要求3和10毫克之间的氢氧化钾以中和这样的酸度)，并且不满足目前的炼厂材料规格。通过替换设备、金属管道等获得工业单元的冶金适当性(metallurgic adequacy)，并且所述冶金适当性是油馏分中环烷酸分布的函数，所述油馏分经历在处理来自新储层的油中的改变。
高酸含量也影响原油的价值和市场性。例如，目前，市场价值因为原油具有大于每克油0.5毫克氢氧化钾的TAN而折价。
此外，羧基的极化特性促进形成乳液，尤其是在较重质烃原料中。这降低了石油的脱盐阶段的效率，使得水/油乳液难以分离。因此，高酸度不仅降低市场价值，但是不利地影响精炼工艺。
认为降低来自炼厂原料的TAN是重质油提质加工中的最重要的工艺之一。一种方法是使具有相对高TAN的原料与具有相对低TAN的原料混合。然而，酸性化合物剩余在共混原料中，并且牺牲了较高市场价值的低TAN烃原料。其它方法包括使用苛性溶液洗涤原料。该处理可以除去环烷酸，但是该方法产生显著量的废水和难以处理的乳液。进一步的方法包括通过具有或不具有催化特性的吸附剂化合物吸附环烷酸或与其它催化剂接触，所述其它催化剂包括加氢处理催化剂。
虽然如此，工业中依然存在对用于以有效和经济可行的方式处理炼厂原料以降低TAN、中和环烷酸和/或破坏或防止形成乳液的改进方法的需要。
发明内容
因此，本发明的目标是有效地和经济地降低包含环烷酸的烃原料的TAN。
本发明的另一个目标是降低TAN，同时破坏乳液或最小化或防止形成其的可能性。
依据一个或多个实施方案，提供用于降低包含环烷酸的炼厂原料的TAN的方法。在含水碱的存在下使包含环烷酸的炼厂原料与有效量的固体非均相催化剂接触足以中和至少部分原料中的环烷酸的一段时间，以产生处理的混合物。将混合物相分离成含水相和中和烃相。
依据一个或多个另外的实施方案，本方法包括：使包含环烷酸的烃原料与有效量的固体催化剂接触，所述固体催化剂已经使用苛性碱预处理足以中和至少部分烃原料中的环烷酸的一段时间，以产生具有降低量的环烷酸的处理的烃原料。
这些示例性方面和实施方案的其它方面、实施方案和优点在以下详细讨论。此外，将要理解上述的信息和以下的详细说明仅仅是各个方面和实施方案的示例性实例，并且旨在提供用于理解要求保护的方面和实施方案的本质和特征的总述和框架。包括了附图以提供各个方面和实施方案的展示和进一步理解，并且并入本说明书中并且组成本说明书的部分。附图和说明书的剩余部分一起，用于解释所描述和要求保护的方面和实施方案的原理和操作。
附图说明
在结合附图阅读时将要最好地理解上述综述以及以下的详细说明。然而，应该理解本发明不限制于所示的精确的排布和设备。
图1为用于降低炼厂原料的TAN的系统的工艺流程图。
具体实施方式
参照图1，图示性展示了用于降低炼厂原料的TAN的系统10。已经省略了例如泵、器械、换热器、锅炉、压缩机和相似硬件的细节，因为其对理解本发明所涉及的技术来说是非关键的。系统10包括中和容器4和分离器罐6。中和容器4包括用于经由导管1接收烃原料和经由导管2接收含水苛性碱的入口3，和用于排出处理的混合物的出口5。分离器罐6包括用于接收处理的混合物的入口11、用于排出中和烃原料的出口7、用于排出含水相的出口8和用于排出轻质气体的出口9。在某些实施方案中，乳液破坏添加剂可以并入分离器罐6中，例如，经由导管12(以虚线显示)。
在本文描述的系统的实践中，将经由导管1引入的包含环烷酸的烃原料与经由导管2引入的含水苛性碱混合。混合物经由入口3加入至中和容器4。中和容器4包含单一催化剂或一组催化剂。将混合物带至与催化剂的接触中并且维持在接触中足以中和烃原料中存在的环烷酸化合物的一段时间。使处理的混合物经由出口5排出并且经由入口11传送至分离器罐6。
将处理的混合物分离成三部分：具有由环烷酸的中和降低的TAN的中和烃原料，其经由出口7作为产物回收；经由出口8排出的包含废苛性碱的含水相；和经由出口9排出的轻质气体，其包括H2S、NH3和轻质烃气体(例如，具有1和4之间的碳数)。
在另外的实施方案中，使用苛性碱(例如氢氧化钠或氢氧化钾)预处理包含于中和容器中的催化剂材料。在该实施方案中，不存在苛性碱和分离器罐。
催化剂预处理可以是原位(例如，在中和容器中)或非原位(例如，在连续管式容器或间歇式设备中)的。在原位催化剂制备的示例性实施方案中，将氧化铝碱催化剂装载至中和容器中，并且将50wt%的苛性碱溶液加热至320℃并且以0.3h-1的液时空速进料通过催化剂床5-10小时。在催化剂预处理之后，可以加入原料，用于中和环烷酸。在非原位制备的示例性实施方案中，在间歇式容器中将丸粒形式的氧化铝催化剂加热至320℃并且然后与50wt%的苛性碱溶液混合3小时。排干苛性碱溶液并且将固体催化剂干燥并且装载至中和容器中。
用于以上描述的设备和方法的炼厂原料可以为获得自各种来源的原油或部分精炼原料或烃产品馏分。炼厂原料来源可以为天然产生的原油、合成原油、沥青、油砂、页岩油、煤合成油或包括上述来源的一者的组合。例如，原料可以为石脑油、粗柴油、减压粗柴油或其它炼厂中间物流，例如减压粗柴油、从溶剂脱沥青工艺获得的脱沥青油和/或脱金属油、从焦化工艺获得的轻质焦化或重质焦化粗柴油、从FCC工艺获得的循环油、从减粘裂化工艺获得的粗柴油或上述的产品的任何组合。虽然如此，本领域技术人员将要理解其它烃物流可以受益于本文描述的系统和方法的实践。
含水苛性碱可以是氢氧化钠或氢氧化钾。在某些实施方案中，通过导管2供应的苛性碱的量为基于催化剂重量的0.05-30wt%。
中和容器4可以固定床、移动床、流化床或摇摆床系统。在某些实施方案中固定床反应器是适合的。一般，中和容器的操作条件包括1-20Kg/cm2，在某些实施方案中1-10Kg/cm2的压力；200℃-600℃，在某些实施方案中300℃-400℃，和在进一步的实施方案中300℃-350℃的温度；和0.1-10h-1，在某些实施方案中0.5-4h-1，和在进一步的实施方案中1-2h-1的炼厂原料液时空速。在某些实施方案中，中和容器内的压力可以由烃压力单独维持，而不供应任何添加的塔顶物质(overhead)或覆盖气体。
中和容器包含具有碱性特性的催化剂。在某些实施方案中催化剂包含至少一种金属氧化物，其选自氧化锌、氧化铝、锌的铝酸盐和包括镁/铝的层状双氢氧化物。催化剂的形式为丸粒、球形或任何其它适合的形状。一般，如本领域中已知的，以如下的方式选择催化剂粒度和形状：用于防止跨越床的过度压降，但是允许反应物适当地扩散至催化剂颗粒内的催化剂表面上的活性位点。
在某些实施方案中，可以将破乳剂添加剂添加至分离器罐6以有效地分离油和水。这些乳液破坏添加剂可以选自三乙醇胺、乙氧基化酚醛树脂、氯化锌和聚合三亚硫酰胺(polymerized trithionylamine)。
本文描述的方法可以在炼厂操作或上游中的各个阶段处进行。例如，可以实施本方法以处理炼厂中的流入原料或其馏分。在替代的实施方案中，本方法可以在粗柴油分离设备上游或其内(例如，脱盐阶段的下游)实施。
以上和附图中已经描述了本文的方法和系统；然而，修改对本领域技术人员来说将是显而易见的并且本发明的保护范围将由以下的权利要求限定。

Claims (33)

1.用于降低包含环烷酸的炼厂原料的总酸值的方法，该方法包括：
在含水苛性碱的存在下使包含环烷酸的炼厂原料与有效量的固体催化剂接触足以中和至少部分炼厂原料中的环烷酸的一段时间，以产生处理的混合物；和
将处理的混合物相分离成含水相和中和的炼厂原料。
2.根据权利要求1的方法，其中固体催化剂为单一或一组催化剂，其展示出碱性特性。
3.根据权利要求1的方法，其中固体催化剂包含至少一种金属氧化物，所述金属氧化物包括一种或多种选自如下的材料：氧化锌、氧化铝、锌的铝酸盐和包括镁/铝的层状双氢氧化物。
4.根据权利要求1的方法，其中炼厂原料包含羧酸。
5.根据权利要求1的方法，其中含水苛性碱为氢氧化钠或氢氧化钾。
6.根据权利要求1的方法，其中炼厂原料使用0.1-10h-1的液时空速供应。
7.根据权利要求1的方法，其中炼厂原料使用0.5-4h-1的液时空速供应。
8.根据权利要求1的方法，其中炼厂原料使用1-2h-1的液时空速供应。
9.根据权利要求1的方法，其中含水苛性碱包含基于催化剂重量的0.05-30wt%的苛性碱。
10.根据权利要求1的方法，其中中和反应在200-600℃的温度下进行。
11.根据权利要求1的方法，其中中和反应在300-400℃的温度下进行。
12.根据权利要求1的方法，其中中和反应在300-350℃的温度下进行。
13.根据权利要求1的方法，其中中和反应在1-20Kg/cm2的压力下进行。
14.根据权利要求1的方法，其中中和反应在1-10Kg/cm2的压力下进行。
15.根据权利要求13的方法，其中压力由炼厂原料压力单独维持，而不供应任何添加的塔顶物质或覆盖气体。
16.根据权利要求1的方法，其进一步包括将乳液破坏添加剂添加至处理的混合物以最小化乳液的形成。
17.根据权利要求16的方法，其中乳液破坏添加剂为三乙醇胺、乙氧基化酚醛树脂、氯化锌或聚合三亚硫酰胺。
18.用于降低包含环烷酸的炼厂原料的总酸值的方法，该方法包括使包含环烷酸的炼厂原料与有效量的固体催化剂接触，所述固体催化剂已经使用苛性碱预处理足以中和至少部分炼厂原料中的环烷酸的一段时间，以产生具有降低的总酸值的处理的产物。
19.根据权利要求18的方法，其中固体催化剂为单一或一组催化剂，其展示出碱性特性。
20.根据权利要求18的方法，其中固体催化剂包含至少一种金属氧化物，所述金属氧化物包括一种或多种选自如下的材料：氧化锌、氧化铝、锌的铝酸盐和包括镁/铝的层状双氢氧化物。
21.根据权利要求18的方法，其中炼厂原料包含羧酸。
22.根据权利要求18的方法，其中苛性碱为氢氧化钠或氢氧化钾。
23.根据权利要求18的方法，其中炼厂原料使用0.1-10h-1的液时空速供应。
24.根据权利要求18的方法，其中炼厂原料使用0.5-4h-1的液时空速供应。
25.根据权利要求18的方法，其中炼厂原料使用1-2h-1的液时空速供应。
26.根据权利要求18的方法，其中中和反应在200-600℃的温度下进行。
27.根据权利要求18的方法，其中中和反应在300-400℃的温度下进行。
28.根据权利要求18的方法，其中中和反应在300-350℃的温度下进行。
29.根据权利要求18的方法，其中中和反应在1-20Kg/cm2的压力下进行。
30.根据权利要求18的方法，其中中和反应在1-10Kg/cm2的压力下进行。
31.根据权利要求29的方法，其中压力由炼厂原料压力单独维持，而不供应任何添加的塔顶物质或覆盖气体。
32.用于降低包含环烷酸的炼厂原料的总酸值的催化剂组分，其包含一种或多种选自如下的材料：氧化锌、氧化铝、锌的铝酸盐和包括镁/铝的层状双氢氧化物，其中催化剂组分已经使用含水苛性碱预处理。
33.根据权利要求32的催化剂组分，其中含水苛性碱包括氢氧化钠或氢氧化钾。
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