CN111936220A - 用于去除二氧化碳和重烃的分层吸附床 - Google Patents

用于去除二氧化碳和重烃的分层吸附床 Download PDF

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CN111936220A
CN111936220A CN201980022468.1A CN201980022468A CN111936220A CN 111936220 A CN111936220 A CN 111936220A CN 201980022468 A CN201980022468 A CN 201980022468A CN 111936220 A CN111936220 A CN 111936220A
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zeolite
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carbon dioxide
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沙因-杰·董
胥青
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Abstract

一种用于处理天然气流的方法，该方法包括将气流送过至少一个多层吸附床以产生包括甲烷的气流，该吸附床包括至少一个相对于其他杂质优先吸附C8+烃和芳烃的吸附剂层、至少一个相对于其他杂质优先吸附二氧化碳的沸石层和至少一个相对于其他杂质优先去除C7‑烃的沸石层。

Description

用于去除二氧化碳和重烃的分层吸附床
背景技术
在液化天然气(LNG)调峰设备中，变温吸附(TSA)方法已广泛用于从天然气中去除水和二氧化碳以防止LNG生产中的冻结。此类调峰设备用于处理和贮存过剩的天然气以便能够满足寒冷的冬季和夏季最热期间的峰值消耗的要求。用于该应用的典型吸附剂为4A或13X沸石分子筛。由于对二氧化碳的吸附容量远低于对水的吸附容量，因此二氧化碳的去除通常控制着吸附床的设计。在不存在烃(诸如戊烷或具有更高碳数的其他烃)的情况下，13X的二氧化碳吸附容量高于4A。然而，在存在烃的情况下(如在天然气中)，由于这些烃的强竞争性吸附，13X上的吸附容量会低于4A上的吸附容量。然后，合适的吸附剂的选择取决于天然气中烃含量的水平。
环球油品(UOP)的SeparSIV是一种基于吸附的新技术，其涉及液化天然气预处理步骤以去除重烃并防止LNG生产中重烃的冻结。该方法使用大孔吸附剂(诸如硅胶)层来去除大烃分子诸如C8+或BTX(苯、甲苯或二甲苯)，并且使用13X沸石吸附剂层来去除较小的烃分子诸如C5、C6。
然而，由于13X沸石上二氧化碳与烃之间的强竞争性吸附，上述多层床并不适于去除二氧化碳。如果需要在单个吸附单元中去除二氧化碳和烃两者，则需要适当的吸附剂和/或吸附剂构造以有效地在单个单元中去除这两种组分。
附图说明
图1示出了利用两个吸附剂单元用于从气流中去除水、烃和二氧化碳的分层构造。
图2示出了利用单个吸附剂单元用于从气流中去除水、烃和二氧化碳的分层构造。
图3示出具有1％二氧化碳的进料使用4A/13A沸石的二氧化碳吸附产物。
图4示出具有0.2％二氧化碳的进料使用4A/13A沸石的二氧化碳吸附产物。
具体实施方式
本发明使用优先吸附C8+和芳族化合物的吸附剂层、优先吸附二氧化碳的吸附剂层和优先吸附C7-烃的吸附剂层。可使用的吸附剂包括硅胶、A型沸石(诸如4A沸石)、X型沸石(诸如13X沸石)、活性炭、氧化铝、沸石Y、丝光沸石和硅石岩。本发明可使用4A/13X分层吸附器在单个吸附器单元中去除CO2和烃。在存在烃的情况下，本发明的床构造通过4A移除大部分CO2并且通过13X改进CO2组成至低于50ppm。同时，轻质烃(C5-C7)也可通过13X去除以满足烃的产品规格。与单独的4A或13X床相比，该分层床实际上提供了对CO2的最大容量。由于CO2是用于确定床尺寸的主导因素，因此该分层床导致吸附容器的减少。
更重的烃(C8+和BTX)也可如通过向诸如图1A和图2B所示的构型中添加硅胶层来去除，上述附图示出了本发明的两种可能的构型。
本发明按需使用4A和13X吸附剂层以及硅胶和其他吸附剂来移除其他杂质。此类沸石的一个来源是伊利诺伊州德斯普兰斯的环球油品公司(UOP LLC，Des Plaines，Illinois)，该公司以UI-94或UI-900销售4A沸石。13X沸石的对应产物是也由环球油品公司出售的LNG5和H121分子筛。
图1和图2示出了本发明的两层床构造。在图1中，气体进料2进入吸附剂床4，该吸附剂床包含用于去除C8+和BTX烃的硅胶层6和用于去除水的4A吸附剂层8。然后，所得的经部分处理的气体10通到第二吸附剂床12，该第二吸附剂床包含用于去除大部分二氧化碳的4A沸石吸附剂层14和用于去除大部分剩余二氧化碳和C7烃及更低烃而同时保留甲烷的13X沸石层16。将包括甲烷的烃料流18送至设备的液化区段。另外，在20和22处指示的是用于监测吸附剂床4和12的参数的传感器。
图2示出了单个吸附剂床，该吸附剂床具有三层以去除与图1的两个吸附剂床系统中相同的杂质。气体进料40进入吸附剂床46，该吸附剂床具有用于去除C8+和BTX烃的硅胶层44、用于去除水和大部分二氧化碳的4A沸石层42和用于去除剩余二氧化碳和C7烃及更低烃的大部分而同时保留甲烷的的13X沸石层48。将包括甲烷的烃料流50送至设备的液化区段。另外，在52处指示的是用于监测吸附剂床参数的传感器。
上述导管、单元设备、支架、周围环境、区域或类似物均中的任一个可配备一个或多个监测部件，包括传感器、测量设备、数据捕获设备或数据传输设备。信号、工艺或状态测量以及来自监测部件的数据可用于监测工艺设备中、周围和与其有关的条件。由监测部件生成或记录的信号、测量和/或数据可通过一个或多个网络或连接收集、处理和/或传输，所述网络或连接可以是私有或公共的，通用的或专用的，直接的或间接的，有线的或无线的，加密的或未加密的，和/或它们的组合；本说明书并非旨在在这方面进行限制。
由监测部件生成或记录的信号、测量和/或数据可被传输到一个或多个计算装置或系统。计算装置或系统可包括至少一个处理器以及存储计算机可读指令的存储器，该计算机可读指令当由至少一个处理器执行时，使一个或多个计算装置执行可包括一个或多个步骤的工艺。例如，可配置一个或多个计算装置以从一个或多个监测部件接收与至少一件与该工艺相关联的设备相关的数据。一个或多个计算装置或系统可被配置为分析该数据。根据数据分析，一个或多个计算装置或系统可被配置为确定对本文所述的一个或多个工艺的一个或多个参数的一种或多种推荐调整。一个或多个计算装置或系统可被配置为传输加密或未加密的数据，其包括对本文所述的一个或多个工艺的一个或多个参数的一种或多种推荐调整。
本发明涉及通过吸附剂4A沸石(UI-94)和13X沸石(LNG5)的组合去除二氧化碳，其中总体的吸附床尺寸相同并且所使用的两种类型的沸石之间的分流比不同。模拟结果示出，对于二氧化碳去除，存在优选的4A沸石(UI-94)与13X沸石(LNG5)比率。研究案例的进料包含6600ppm的C3-C6，其分别具有1％和0.2％二氧化碳。在1％二氧化碳的情况下，最佳吸附床包含90％的4A和10％的13X(图3)。在0.2％的CO2的情况下，最佳吸附床包含85％的4A和15％的LNG5(图4)。与单独的4A或13X床相比，分层床实际上提供了最佳CO2去除性能。0.2％的CO2的情况要求比1％的CO2的情况更多的LNG5。这表明在低CO2组成下，烃共吸附对LNG5的影响降低。在产品端添加LNG5或13X层不仅用于去除轻质烃，还有助于将CO2削减到50ppm以下。
具体的实施方案
虽然结合具体的实施方案描述了以下内容，但应当理解，该描述旨在说明而不是限制前述描述和所附权利要求书的范围。
本发明的第一实施方案是一种用于处理天然气流的方法，该方法包括将气流送过至少一个多层吸附床以产生包括甲烷的气流，该吸附床包括至少一个相对于其他杂质优先吸附C8+烃和芳烃的吸附剂层、至少一个相对于其他杂质优先吸附二氧化碳的沸石层和至少一个相对于其他杂质优先去除C7-烃的沸石层。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其中该至少一个优先吸附C8+烃和芳烃的吸附剂层包括硅胶。本发明的一个实施方案是本段中的一个、任一个或所有先前实施方案直到本段中的第一实施方案，其中该至少一个优先吸附二氧化碳的沸石层是A型沸石。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其中该至少一个优先吸附二氧化碳的沸石层是4A型沸石。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任何或所有实施方案，其中该至少一个优先去除C7-烃的沸石层为X型沸石。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其中该至少一个优先去除C7-烃的沸石层为13X型沸石。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的任一个或所有实施方案，其包括将该气流送至包括三个吸附剂层的一个吸附床。本发明的一个实施方案是本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其包括将气流按顺序送过两个吸附床。本发明的一个实施方案是本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其中该气流首先被送过第一吸附床，与硅胶层接触，并且之后与4A沸石层接触；然后气流被送过第二吸附床，首先与第二4A沸石层接触，然后与13X沸石层接触，从而产生包括甲烷的气流。本发明的一个实施方案为本段的第一实施方案至本段的先前实施方案中的一个、任一个或所有实施方案，其中包括甲烷的气流被送去液化。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其中芳烃选自由苯、甲苯和二甲苯构成的组。本发明的一个实施方案为本段中的先前实施方案至本段中的第一实施方案中的一个、任一个或所有实施方案，其中4A沸石层除去水和大部分二氧化碳。本发明的一个实施方案是本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案，其中13X沸石层除去C7-和二氧化碳，从而允许甲烷加入包括甲烷的气流。本发明的一个实施方案为本段的第一实施方案至本段的先前实施方案中的一个、任一个或所有实施方案，其中气流包括按摩尔计小于50ppm的二氧化碳。本发明的实施方案是本段中的先前实施方案至本段中的第一实施方案中的一个、任何或所有实施方案，还包括以下项中的至少一项：感测所述方法的至少一个参数并且从所述感测生成信号；感测所述方法的至少一个参数并且从所述感测生成数据；生成并传输信号；生成并传输数据。
本发明的第二实施方案是一种用于处理天然气的系统，该系统包括至少一个吸附床，该吸附床包括吸附剂层，其中第一层包括硅胶层，第二层包括4A沸石层，并且第三层包括13X沸石层。本发明的一个实施方案为本段中的先前实施方案至本段中的第二实施方案中的一个、任一个或所有实施方案，其包括串联的一个或多个吸附床，其中在该吸附床内放置有至少一个优先去除C8+烃和芳烃的吸附剂层、至少一个优先吸附二氧化碳的吸附剂层和至少一个优先吸附C7-烃的吸附剂层。

Claims (10)

1.一种用于处理天然气流的方法，所述方法包括将所述气流送过至少一个多层吸附床以产生包括甲烷的气流，所述吸附床包括至少一个相对于其他杂质优先吸附C8+烃和芳烃的吸附剂层、至少一个相对于其他杂质优先吸附二氧化碳的沸石层和至少一个相对于其他杂质优先去除C7-烃的沸石层。
2.根据权利要求1所述的方法，其中所述至少一个优先吸附C8+烃和芳烃的吸附剂层包括硅胶。
3.根据权利要求1所述的方法，其中所述至少一个优先吸附二氧化碳的沸石层是A型沸石。
4.根据权利要求1所述的方法，其中所述至少一个优先吸附二氧化碳的沸石层是4A型沸石。
5.根据权利要求1所述的方法，其中所述至少一个优先去除C7-烃的沸石层为X型沸石。
6.根据权利要求1所述的方法，其中所述气流首先被送过第一吸附床，与硅胶层接触，并且之后与4A沸石层接触；然后所述气流被送过第二吸附床，首先与第二4A沸石层接触，然后与13X沸石层接触，从而产生包括甲烷的气流。
7.根据权利要求1所述的方法，其中所述气流包括按摩尔计小于50ppm的二氧化碳。
8.根据权利要求1所述的方法，还包括以下项中的至少一项：
感测所述方法的至少一个参数并且从所述感测生成信号；
感测所述方法的至少一个参数并且从所述感测生成数据；
生成并传输信号；
生成并传输数据。
9.一种用于处理天然气的系统，所述系统包括至少一个吸附床，所述吸附床包括吸附剂层，其中第一层包括硅胶层，第二层包括4A沸石层，并且第三层包括13X沸石层。
10.根据权利要求9所述的系统，所述系统包括串联的一个或多个吸附床，其中在所述吸附床内放置有至少一个优先去除C8+烃和芳烃的吸附剂层、至少一个优先吸附二氧化碳的吸附剂层和至少一个优先吸附C7-烃的吸附剂层。
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