CN116323865A - 液化废聚合物的加工处理方法 - Google Patents
液化废聚合物的加工处理方法 Download PDFInfo
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Abstract
本发明涉及用于加工处理包含二烯烃和石脑油的液化废聚合物(LWP；10)的方法。二烯烃的氢化处理A产生通过蒸馏B分离的贫二烯烃LWP进料(20)，以5提供一种或多种馏出物和蒸馏塔底物(50)，该一种或多种馏出物至少包含石脑油馏分(30)、可选的中间馏分(40)。石脑油馏分的加氢处理C提供适合作为蒸汽裂解器D进料的氢化石脑油馏分(60)。蒸馏塔底物(50)和中间馏分(40)能够与原油(70)混合并用于炼油厂，因为它们10基本不含二烯烃。
Description
技术领域
本发明涉及加工处理液化废聚合物的方法，具体而言，涉及包括选择性氢化其中存在的二烯烃的方法。
背景技术
不容易实现使用油蒸馏单元加工处理液化废聚合物(LWP)(如废塑料热解油(WPPO)和水热液化废塑料油)。LWP很容易结垢(foul)，并且包含沸点很宽的不同组分。在原油蒸馏单元中，蒸馏是可行的，但来自原油蒸馏单元的产品通常被引导到并非针对烯烃进料而设计的单元。例如，LWP中存在的二烯烃可能会在针对不包括这些组分的原油衍生石脑油馏分而设计的氢化工艺中引起问题。
LWP还含有不同的元素杂质，这些杂质主要取决于被液化的聚合物废料的来源，并且也取决于所采用的液化技术。例如，在已被确定为聚合物废料的潜在大规模来源的消费后废塑料(回收消费塑料)中，最相关的杂质是氮、氧、硫和氯，但也可能存在其他卤素，如溴和氟。含溴杂质可以主要包含于工业衍生聚合物废料(例如，源自阻燃剂)中。此外，在LWP中也能够检测到金属和其他杂质，如源自添加剂和污染物的准金属。这些杂质对LWP的直接利用具有不利影响。通过热解工艺或水热液化产生的LWP通常含有大量的烯烃和芳烃，其每种都可以导致一些下游工艺出现问题，如高温聚合(或焦化)。
US5849964公开了一种用于加工处理用过的或废弃的塑料材料从而通过将所述用过的材料解聚以回收化学原料和液体燃料组分的方法，这些用过的材料被转化为可泵送相和挥发相。一旦挥发相分离而剩下可泵送相，就进行液相氢化、气化、低温碳化或所述工艺的组合。
WO2016142808公开了一种用于将废塑料转化为最终石化产品的集成工艺方法。该工艺方法允许采用提供同时氢化的加氢处理反应和烃料流各组分的脱氯进行操作，以达到满足蒸汽裂解器要求的规格。
然而，仍然需要加工处理废聚合物的进一步的方法。
发明内容
以下提出了简化的概述，以提供对本发明的各实施方式的一些方面的基本理解。该概述并非本发明的广泛综述。它既不是为了确定本发明的重大或关键要素，也不是为了界定本发明的范围。以下概述仅以简化的形式呈现本发明的一些概念，作为对本发明的示例性实施方式的更详细描述的前奏。
据观察，当LWP在分馏之前进行氢化处理(hydrotreat)时，其结垢倾向显著降低。此外，所得石脑油馏分的加氢处理会更容易，并且所用加氢处理催化剂的寿命更长，因为将会导致催化床堵塞的聚合和其他反应变少。
根据本发明，提供了一种加工处理液化废聚合物(LWP)的新方法，其中该方法包括以下步骤：
a)提供包含二烯烃和石脑油的LWP料流，
b)在氢和一种或多种氢化处理催化剂存在下，使所述LWP料流经受氢化处理反应条件以产生贫二烯烃LWP料流，和
c)蒸馏所述贫二烯烃LWP料流以获得蒸馏塔底物和一种或多种馏出物，所述一种或多种馏出物至少包含在大气压力(atmospheric pressure)下沸点低于180℃的石脑油馏分。
根据本发明，还提供了氢化石脑油作为蒸汽裂解器进料的新用途，其中所述氢化石脑油通过包括以下的方法产生：
a)提供包含二烯烃和石脑油的LWP料流，
b)在氢和一种或多种氢化处理催化剂存在下，使所述LWP料流经受氢化处理反应条件以产生贫二烯烃LWP料流，
c)蒸馏所述贫二烯烃LWP料流以获得蒸馏塔底物和一种或多种馏出物，所述一种或多种馏出物至少包含在大气压力下沸点低于180℃的石脑油馏分，和
d)在氢和一种或多种加氢处理催化剂存在下，使所述石脑油馏分经受加氢处理反应条件。
根据本发明，还提供了原油和步骤c)的蒸馏塔底物的混合物作为原油精炼进料(冶炼厂进料，refinery feed)的新用途。
在所附从属权利要求中描述了本发明的多个举例而非限制性的实施方式。
当结合附图阅读时，本发明的各示例而非限制性实施方式和操作方法及其附加的目的和优点，能够根据以下具体示例性实施方式的描述中获得最佳理解。
在本文件中，动词“包含”和“包括”用作开放限制，既不排除也不要求必须存在未引述的特征。除非另有明确说明，否则从属权利要求中所述的特征可以相互自由组合。此外，还应该理解的是，在整个文件中使用“一”或“一种”，即单数形式，并不排除复数。
作为本文的定义，“加氢处理(hydroprocessing)”是指一系列催化化学工程工艺，包括氢化处理(hydrotreating)和加氢裂解，其中氢的反应用于去除杂质(如氧、硫、氮、磷、硅和金属)，饱和碳-碳键，断裂碳-碳键，降低平均分子量，重排进料的分子结构，或其任何组合。
作为本文的定义，术语“氢化处理(hydrotreating)”是指一种化学工程工艺，其中氢的反应用于去除杂质(如氧、硫、氮、磷、硅和金属)，和/或饱和碳-碳键，特别是作为炼油的部分。
氢化处理能够在一个或多个反应器单元或催化剂床中分一个或几个步骤进行。
附图说明
下面参照附图更详细地解释本发明的示例而非限制性实施方式及其优点，附图显示了用于加工处理包含二烯烃的液化废聚合物10的示例非限制性流程图。
具体实施方式
本发明涉及一种用于加工处理液化废聚合物(LWP)的方法。该方法的原理如图1所示。因此，包含二烯烃和石脑油的LWP料流10被进料到氢化处理单元A，以产生贫二烯烃LWP料流20。当氢化处理反应在氢和一种或多种本领域已知的氢化处理催化剂的存在下以温和方式(优选在液相条件中)进行时，主要只有LWP中存在的二烯烃被还原。用于选择性还原二烯烃的示例性氢化处理反应条件包括：温度120-210℃，和压力1-50巴表压(barg)。示例性的压力为28.5巴表压。液时空速(LHSV)通常为1-5h-1，优选4-4.5h-1。示例性的氢/烃比为15N m3/m3。示例性的氢化处理催化剂包括优选处于载体(support)上的NiMo和CoMo。一种示例性的氢化处理催化剂是NiMo/Al2O3。另一种示例性的氢化处理催化剂是CoMo/Al2O3。
贫二烯烃LWP料流被进料到蒸馏单元B，其中分离出一种或多种馏出物30、40和蒸馏塔底物50。根据一个实施方式，馏出物包含在大气压力下沸点低于180℃的石脑油馏分30。根据该实施方式，蒸馏塔底物50包含在大气压力下沸点高于180℃的材料。
根据另一个实施方式，该蒸馏产生两种馏出物，即在大气压力下沸点低于180℃的石脑油馏分30，和在大气压力下沸点为180℃至360℃的中间馏分40。根据该实施方式，蒸馏塔底物50包含在大气压力下沸点高于360℃的材料。
根据一个实施方式，该蒸馏在大气压力下进行。根据另一个实施方式，该蒸馏在减压下进行。根据还有的另一个实施方式，该蒸馏在过压(余压，excess pressure)下进行。
根据优选的实施方式，石脑油馏分30被进料到加氢处理单元C。加氢处理优选使用NiMo和CoMo型催化剂进行，这会去除石脑油馏分中的杂原子如氯、氧、硫和氮，且同时对其中存在的烯烃和芳烃进行加氢。石脑油的加氢处理通常在氢存在下于升高的温度和压力下气相进行。示例性加氢处理反应条件包括：温度280-350℃，和压力20-100巴表压，优选20-50巴表压。LHSV通常为1-5h-1，且氢/烃比为100-900 Nm3/m3，如360Nm3/m3。示例性的非限制性加氢处理催化剂是CoMo/Al2O3和NiMo/Al2O3。该产物是氢化石脑油馏分60。
已知的是，蒸汽裂解器对进料中的烯烃、芳烃和杂原子含量具有规定。因此，氢化石脑油馏分60适合作为蒸汽裂解器D的进料。
LWP能够在炼油厂与原油一起进行共加工处理。然而，由于来自原油蒸馏单元的产物通常被引导到并非针对烯烃进料而设计的单元，因此无烯烃组分(尤其是二烯烃)的烯烃进料将是有益的。上述限制在设计用于处理直馏石脑油的石脑油加氢处理单元的背景下尤其相关。这种单元通常以气相操作，并且限制了总放热，即由于化学反应释放的热量而在反应器内部发生的温度升高。向这样的反应器中加入烯烃进料会导致总放热显著增加，这进而又可以缩短加氢处理催化剂的寿命。因此，从炼油厂的角度来看，炼油厂的共加工处理之前从LWP中去除石脑油馏分也是有益的。与石脑油馏分相比，在炼油厂对重质LWP馏分的共加工处理麻烦较少，因为针对中间馏分和例如重质气体油或真空气体油而设计的加氢处理单元也适用于处理来自例如减粘裂化或延迟焦化单元的热裂化进料。
根据一个具体实施方式，例如，在混合单元E中将塔底馏分50与原油70混合以形成混合物80，其随后进料至原油蒸馏单元F，在其中所述混合物分离成一种或多种料流90、100。
根据另一个实施方式，例如，在混合单元G中将中间馏分40与原油70混合以形成混合物110，随后将其进料至原油蒸馏单元H，在其中所述混合物分离成一种或多种料流120、130。
根据另一个实施方式，本发明涉及由含二烯烃LWP产生的氢化石脑油作为蒸汽裂解器进料的用途。该蒸汽裂解器进料通过包括以下步骤的方法产生：
a)提供包含二烯烃和石脑油的LWP料流，
b)使该LWP料流经受氢化反应条件以产生贫二烯烃LWP料流，
c)蒸馏该贫二烯烃LWP料流以获得蒸馏塔底物和至少一种在大气压力下沸点低于180℃的石脑油馏分，和
d)使该石脑油馏分经受氢化反应条件以产生氢化石脑油。
本发明的方法适用于加工处理不同类型的液化废聚合物及其混合物，如废塑料热解油(WPPO)和水热液化废塑料油。根据一个实施方式，该液化废聚合物包括WPPO。根据另一个实施方式，该液化废聚合物包括水热液化废塑料油。
以上给出的描述中提供的具体实施例不应该解释为限制所附权利要求的范围和/或适用性。
Claims (18)
1.一种用于加工处理液化废聚合物(LWP)的方法，所述方法包括以下步骤：
a)提供包含二烯烃和石脑油的LWP料流，
b)在氢和一种或多种氢化处理催化剂存在下，使所述LWP料流经受氢化处理反应条件以产生贫二烯烃LWP料流，和
c)蒸馏所述贫二烯烃LWP料流以获得一种或多种馏出物和蒸馏塔底物，所述一种或多种馏出物至少包含在大气压力下沸点低于180℃的石脑油馏分。
2.根据权利要求1所述的方法，包括
d)在氢和一种或多种加氢处理催化剂存在下，使步骤c)的所述石脑油馏分经受加氢处理反应条件以产生氢化石脑油。
3.根据权利要求1或2所述的方法，其中步骤b)的所述氢化处理反应条件包括：温度120-210℃和压力1-50巴表压。
4.根据权利要求3所述的方法，其中所述氢化处理反应条件包括LHSV1-5h-1，优选地4-4.5h-1。
5.根据权利要求1-4中任一项所述的方法，其中所述一种或多种氢化处理催化剂选自CoMo和NiMo。
6.根据权利要求2-5中任一项所述的方法，其中步骤d)的所述加氢处理反应条件包括：温度280-350℃，和压力20-100巴表压，优选地20-50巴表压。
7.根据权利要求6所述的方法，其中所述加氢处理反应条件包括：
LHSV 1-5h-1，和氢/烃比100-900Nm3/m3。
8.根据权利要求2-7中任一项所述的方法，其中所述一种或多种加氢处理催化剂选自CoMo和NiMo。
9.根据权利要求2-8中任一项所述的方法，包括将所述氢化石脑油进料到蒸汽裂解器。
10.根据权利要求1-9中任一项所述的方法，包括将所述蒸馏塔底物与原油混合以形成混合物。
11.根据权利要求10所述的方法，包括将所述混合物进料到原油蒸馏单元。
12.根据权利要求1-11中任一项所述的方法，其中所述一种或多种馏出物包含在大气压力下沸点为180℃至360℃的中间馏分。
13.根据权利要求12所述的方法，包括将所述中间馏分进料到原油蒸馏单元。
14.根据权利要求1-13中任一项所述的方法，其中所述LWP选自废塑料热解油和水热液化废塑料油或它们的混合物。
15.根据权利要求1-14中任一项所述的方法，其中所述LWP包括废塑料热解油。
16.根据权利要求2-8中任一项所产生的氢化石脑油作为蒸汽裂解器进料的用途。
17.原油和步骤c)的蒸馏塔底物的混合物作为原油精炼进料的用途。
18.原油和权利要求12中的所述中间馏分的混合物作为原油精炼进料的用途。
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