CN101993322A - 序列分离烃类的方法 - Google Patents

序列分离烃类的方法 Download PDF

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CN101993322A
CN101993322A CN2010102612269A CN201010261226A CN101993322A CN 101993322 A CN101993322 A CN 101993322A CN 2010102612269 A CN2010102612269 A CN 2010102612269A CN 201010261226 A CN201010261226 A CN 201010261226A CN 101993322 A CN101993322 A CN 101993322A
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T·范德
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Abstract

本发明描述了在利用裂解由含有烃类的进料产生烃类的设备中分离烃类的方法，对作为粗煤气2产生的包含气态烃的裂解产品气体1进行压缩和干燥，并作为进料导入分离阶段(前端C3/C4分离)中，在其中将粗煤气2分离成具有最多3个碳原子的烃类馏份C3-和具有至少4个碳原子的烃类馏份C4+，前端C3/C4分离包括C4吸收器9和塔(脱丙烷塔)10，在其中将具有至少4个碳原子的烃C4+作为塔底产品排出。在此C3-馏份在氢化11之后利用第一塔12分离成C2-馏份和C2/C3馏份。在具有2个分离的区段13a、13b的第二塔13中进行进一步分离，上段13a作为脱甲烷塔运行，而下段13b作为脱乙烷塔运行。

Description

序列分离烃类的方法
技术领域
本发明涉及在利用裂解由含有烃类的进料产生烃类的设备中分离烃类的方法，其中对作为粗煤气产生的包含气态烃的裂解产品气体进行压缩和干燥，并作为进料导入分离阶段(前端Front-End C3/C4分离)中，在其中将粗煤气分离成由具有最多3个碳原子的烃组成的烃类馏份和由具有至少4个碳原子的烃组成的烃类馏份，所述前端C3/C4分离包括C4吸收器和塔(脱丙烷塔)，在其中将具有至少4个碳原子的烃作为塔底产品排出。
背景技术
在用于产生烃类的设备即所谓的烯烃设备中，通过含有烃类的进料的裂解产生烃类或烯烃。含有烃类的进料在此以液相或气相存在，并通过热裂解或催化裂解在利用或不用蒸汽的情况下转化成较短链的烃。在裂解中产生的主要由较短链的烯烃组成的混合物称作裂解气或粗煤气。在含有烃类的液态进料的裂解中，粗煤气大多作为进料导入油洗装置中。在油洗装置中，冷却粗煤气，并从粗煤气洗出残留的较长链的烃，例如焦炭颗粒和重的油组分。随后将粗煤气导入水洗装置中以进一步清洁和冷却，并在粗煤气压缩装置中进行压缩。在含有烃类的气态进料的裂解中，通常可以省略掉油洗装置。随后根据现有技术将粗煤气在碱液洗涤装置中去除其他杂质如二氧化碳和硫化氢，并干燥。
经清洁和干燥的粗煤气现在由所期望的烯烃产品和副产物的混合物组成。为了可以利用所期望的烯烃产品，必须将所述混合物分离成单独的烯烃组分。
根据现有技术，用于分离烃类的此类方法以其中将具有最多2个碳原子的烯烃与具有至少3个碳原子的烯烃分离的分离阶段(前端C2/C3分离)开始，或者以其中将具有最多3个碳原子的烯烃与具有至少4个碳原子的烯烃分离的分离阶段(前端C3/C4分离)开始。
若序列分离以前端C2/C3分离开始，则将所产生的具有最多2个碳原子的烯烃馏份(C2-馏份)在催化氢化之后送至低温分离部分以去除乙炔，在此将其分离成单独的馏份。在此，将C2-馏份与甲烷馏份和氢气馏份分离。将残留的由具有至少3个碳原子的烃组成的馏份(C3+馏份)导入分离阶段(脱丙烷塔)中，在其中获得由具有至少4个碳原子的烃组成的馏份(C4+馏份)作为塔底产品。在脱丙烷塔中经由塔顶获得由具有3个碳原子的烃组成的烯烃馏份(C3馏份)。随后同样将C3馏份在其进一步加工之前进行催化氢化。
在本申请的范畴内，将由具有n个碳原子的烃组成的烃类馏份称作Cn馏份。若该烃类馏份由具有至少n个碳原子的烃组成，则该烃类馏份称作Cn+馏份。由具有最多n个碳原子的烃组成的馏份称作Cn-馏份。在此，n代表自然数1、2、3、4……
其中将具有2个或更多个碳原子的烃与具有1个碳原子的烃分离的分离阶段在本申请的范畴内称作脱甲烷塔。将C3+馏份作为塔底产品的分离阶段称作脱乙烷塔。相应地，C4+塔底馏份的分离阶段称作脱丙烷塔。
在根据现有技术以前端C3/C4分离开始的序列分离中，在经压缩的粗煤气的压力下获得C3-馏份和C3+馏份。在完全的粗煤气压力下，根据现有技术无法清晰地分离成C3-馏份和C4+馏份，这是因为若达到如此高的塔底温度则会加剧聚合物的形成，并因此非期望地形成覆盖层。在根据现有技术的其他序列分离中，C3-馏份在催化氢化之后导致C2/C3分离。将C3-馏份分离成C3馏份和C2-馏份。将C4+馏份送至C3/C4分离，在此将其分离成C3馏份和C4+馏份，而产生的C3馏份必须随后进行催化氢化。
因此，根据现有技术，无论在包括前端C2/C3分离的序列分离中还是在包括前端C3/C4分离的序列分离中，需要2个具有相应的管式反应器和固定床反应器的独立的催化氢化阶段。
DE 10 2006 010 519中建议了一种用于分离烯烃的可选择的方法。DE 10 2006 010 519公开了一种序列分离，其包括在完全的粗煤气压力下工作的C4吸收器和脱丙烷塔，其在8至12巴的压力下运行。通过C4吸收器和脱丙烷塔的组合，将烯烃分离成C3-馏份和C4+馏份。然后将C3-馏份完全压缩，并送至催化氢化，同时对C4+馏份进一步加工。C3-馏份在催化氢化之后实施C2/C3分离，并分离成C2-馏份和C3馏份。将C2-馏份作为进料进一步导入低温分离部分，同时对C3馏份进一步加工。
发明内容
本发明的目的在于，提供前述类型的方法，从而使烃类的分离在能量和设备上的消耗最小化。
根据本发明，将由具有最多3个碳原子的烃组成的烃类馏份导入包括第一塔C1/C3分离装置及第二塔C1/C2/C3分离装置的分离阶段中，其中第二塔具有2个分离的区段，在第一塔中将由具有最多2个碳原子的烃组成的烃类馏份作为塔顶产品排出，并送至第二塔的上段，第一塔的塔底产品仅由具有2和3个碳原子的烃组成，并送至第二塔的下段。
根据本发明，将C3-馏份送至第一塔。在该第一塔中，排出C2-馏份作为塔顶产品。换而言之，第一塔的塔顶馏份不含具有3个碳原子的烃。在第一塔中相应地产生不再含有甲烷的塔底馏份。换而言之，获得由具有2或3个碳原子的烃组成的C2+馏份作为塔底馏份。因此，具有2个碳原子的烃分配在第一塔的塔顶产品和塔底产品。根据本发明将第一塔的塔顶产品送至第二塔的上段，同时根据本发明将第一塔的塔底产品送至第二塔的下段。在根据本发明的第二塔中，获得由具有2个碳原子的烃组成的烃类馏份作为上段的塔底产品，并获得由具有3个碳原子的烃组成的烃类馏份作为下段的塔底产品。在此，在第二塔中可以将下段的塔顶产品用作上段的汽提气体，同时将上段的一部分液态塔底产品用作塔下段的回流。因此通过根据本发明在第二塔中将2个塔相结合，可以节省设备，如塔顶冷凝器和煮沸器，以及它们的相应的管道。
C4吸收器优选在11至20巴的压力下运行，脱丙烷塔优选在8至12巴的压力下运行，并将C4吸收器的塔顶产品送入另一个压缩阶段。在本发明的这一实施方案中，来自粗煤气压缩装置的第3或第4阶段的粗煤气在11至20巴的压力下送至C4吸收器。脱丙烷塔优选在8至12巴的压力下运行，从而可以获得C4+馏份作为塔底产品。在本发明的这一实施方案中，前端C3/C4+分离优选设置在四级或五级粗煤气压缩装置的第3或第4阶段之后。在前端C3/C4分离设置在粗煤气压缩装置的第3或第4阶段之后而不是设置在粗煤气压缩装置的最后阶段之后的情况下，能量消耗更加有利。在此，粗煤气在第3或第4阶段之后有利地与冷却水和制冷剂方向相反地冷却至约15℃。将在此形成的冷凝物与气相分离。然后将冷凝物和气相在冷凝物干燥器和气体干燥器中去除水。气相进一步与C4吸收器的塔顶气体产品和塔底产品方向相反地进行冷却，然后将其导入C4吸收器的塔底。将冷凝物在冷凝物干燥器之后直接导入脱丙烷塔中。在C4吸收器中，将粗煤气与具有至少4个碳原子的烃分离。将如此作为塔顶产品产生的C3-馏份在任选地加热之后送至压缩装置的第5阶段以进一步进行压缩。因此不必将所有的粗煤气，而是仅C3-馏份进行完全压缩。C4吸收器的塔底产品在脱丙烷塔中减压。C4吸收器有利地获得所需的来自脱丙烷塔的塔顶产品的回流。在脱丙烷塔中，将具有至少4个碳原子的烃与具有最多3个碳原子的烃分离。获得C4+馏份作为塔底产品，并送入另一分离装置。将C3-馏份在脱丙烷塔的塔顶冷凝器中冷凝，并送回C4吸收器。在本发明的这一实施方案中，以此方式在前端C3/C4分离中即使在所述的高压下仍然实现C3-馏份与C4+馏份的干净分离。
优选将C4吸收器的塔顶产品经由针对具有最多3个碳原子的烃的氢化阶段导入第一塔中。在氢化阶段中，将在具有最多3个碳原子的烃类馏份中所包含的乙炔和特别是甲基乙炔以及丙二烯在一个步骤中在等温反应器中进行氢化。根据本发明的方法能够在压缩装置的最后阶段之后直接实施有利的氢化。直接在压缩之后，C3-馏份的温度适合于下游的氢化，从而在本发明的这一实施方案中，不需要逆流换热器以加热C3-馏份及冷却经氢化的C3-馏份。
有利地，第二塔的上段作为脱甲烷塔运行，而第二塔的下段作为脱乙烷塔运行。在本发明的这一实施方案中，第二塔优选在9至13巴，更优选在9.5巴的压力下运行。在本发明的这一实施方案中，第二塔的下段有利地作为脱乙烷塔运行，从而将来自第一塔的塔底的由具有2个碳原子的烃和具有3个碳原子的烃组成的混合烃类馏份分离成C2馏份和C3馏份。因此在第二塔的下段产生由具有2个碳原子的烃组成的不含具有3个碳原子的烃的烃类馏份以及不含具有2个碳原子的烃的、具有3个碳原子的烃类馏份。在此，将一部分来自第二塔的下段的C2馏份用作第二塔的上段中的汽提气体。将过量部分作为气态C2产品从第二塔的上段的塔底排出。可以将一部分来自上段的液态产品用作第二塔的下段的回流。将过量部分作为液态C2产品从第二塔的上段的塔底排出。
优选将第一塔的塔顶产品送至低温冷却装置，其中在低温冷却装置中获得多至超过90％由甲烷组成的馏份，以及获得主要地及最多95％由氢气组成的馏份，将在低温冷却装置中获得的冷凝物送至第二塔的上段。在低温冷却中优选从第一塔的塔顶产品分离出甲烷和氢气。因此低温冷却收集的冷凝物主要由具有2个碳原子的仍然容易被甲烷和氢气污染的烃组成。在第二塔的上段从由具有2个碳原子的烃组成的烃类馏份汽提出甲烷和氢气的污染。在此有利地使用来自第二塔下段的气体产品作为汽提气体。因此可以有利地获得包含仅具有2个碳原子的烃(乙烯和乙烷)不含甲烷、氢气和具有3个碳原子的烃的烃类馏份作为第二塔上段的塔底产品。
优选将第二塔上段的塔顶产品送回低温冷却装置。在第二塔上段的塔顶产品中主要存在甲烷和氢气。将该塔顶产品加热以在低温冷却中冷却C2-馏份及在预先冷却中冷却C3-馏份，然后用作加热用煤气。
优选将由除了少量乙烷以外还有原本要获得的有价值的产品乙烯组成的第二塔上段的塔底产品导入第三塔(C2分离器)中，在其中获得乙烯作为塔顶产品，及获得乙烷作为塔底产品，并将其作为进料再次送回以进一步裂解。
优选从第二塔下段的塔底排出具有3个碳原子的烃类馏份，并作为进料导入第四塔(C3分离器)中，在其中获得丙烯作为塔顶产品及丙烷作为塔底产品。
除了乙烯以外，还可使用丙烯作为有价值的产品。因此，在C3分离器中将C3馏份分离成丙烯和丙烷。除了有价值的产品丙烯以外还获得的丙烷同样作为进料再次送回以进一步裂解。
优选地在低温冷却装置中所需的制冷是利用乙烯制冷剂及由甲烷和具有2个碳原子的烃组成的返回气体，或者利用由具有1个、2个和3个碳原子的烃组成的混合制冷剂产生的。
根据本发明的分离方法具有一系列的优点。通过在包括前端C3/C4分离的方法中使用包括第一C1/C3塔和第二C1/C2/C3塔的塔系统，可以在设备方面实现许多节约。一方面，根据本发明的方法将在低压下运行的第二C1/C2/C3塔中的两个分离步骤相结合。由此省略了塔的煮沸器和冷凝器。另一方面，仅需对所有的C3-馏份实施氢化。额外地省略了C3馏份的汽提，这是因为可以将来自第二塔下段的塔底产品直接导入C3分离器中。
下面应当依照附图中所示的实施例更详细地阐述本发明。
附图说明
图1所示为根据本发明用于分离烃类的方法的实施例；
图2所示为图1实施例的第二塔。
具体实施方式
图1所示为根据本发明在利用裂解由含有烃类的进料产生烃类的设备中分离烃类的方法的实施方案。图2所示为图1实施方案的第二塔。在本发明的这一实施方案中，含有烃类的液态进料在裂解炉1中裂解成主要由较短链的烃组成的混合物。将作为裂解产品产生的粗煤气2作为进料导入油洗装置3中。在油洗装置3中将粗煤气2冷却，并从粗煤气分离出残留的较长链的烃，例如焦炭颗粒和重的油组分。随后将粗煤气导入水洗装置4中以进一步清洁和冷却，并在紧接着的4级粗煤气压缩装置5a中压缩至约20巴的压力。在4级压缩装置5a之后将粗煤气2导入碱液洗涤装置6中，并去除诸如二氧化碳和硫化氢的组分。随后将粗煤气在预冷装置7中预先冷却，并在两个干燥器8a和8b中进行干燥。随后开始粗煤气2的真正的序列分离。
来自预冷装置7的粗煤气2的气态部分进一步与C4吸收器9的塔顶气体产品和塔底产品方向相反地进行冷却(未示出)，随后将其导入C4吸收器9的塔底，同时将来自预冷装置7的冷凝物经由冷凝物干燥器8b送入脱丙烷塔。在C4吸收器中，将粗煤气与C4+馏份分离，从而产生C3-馏份C3-作为塔顶产品。将其在加热之后送入粗煤气压缩装置5b的第5阶段及最后阶段。C4吸收器9的塔底产品在脱丙烷塔10中减压。C4吸收器9获得所需的来自脱丙烷塔10的塔顶产品的回流。
脱丙烷塔将C4+馏份C4+与C3-馏份C3-分离。将C4+馏份C4+进一步在C4/C5分离装置中分离成馏份。将C3-馏份C3-在脱丙烷塔的塔顶冷凝器中冷凝，并送回C4吸收器。在此，C4吸收器9在约20巴的压力下运行，而脱丙烷塔10在8至12巴的压力下运行。
在粗煤气压缩装置5b的第5阶段中完全压缩之后，将C3-馏份C3-导入催化氢化装置11中。在催化氢化装置11中，使在C3-馏份C3-中存在的乙炔、甲基乙炔及丙二烯氢化，并从C3-馏份C3-分离出。直接在粗煤气压缩装置5b的第5阶段之后，C3-馏份C3-的温度在适合于氢化11的温度范围内。因此可以省略用于C3-馏份C3-的加热和制冷回收的昂贵的逆流换热器或热交换器。
将经氢化的C3-馏份C3-作为进料送至第一塔12，其中获得C2-馏份C2-作为塔顶产品，并送入低温冷却装置。第一塔12的塔底产品C2/C3由具有2个碳原子的烃和具有3个碳原子的烃的混合物组成，并导入第二塔13的下段13b中。因此，具有2个碳原子的烃在第一塔12中分配在该塔的塔顶和塔底中。第一塔12的塔顶馏份C2-不含具有3个碳原子的烃，而塔底馏份C2/C3不再含有甲烷。
来自第一塔12的塔底馏份C2/C3直接在第二塔13的下段13b中减压。第一塔12的塔顶馏份C2-进一步在低温冷却装置14中与冷的产品和制冷剂方向相反地以分级的方式进行冷却，从而仅残留包含最多95％氢气的气体馏份H2。额外地在低温冷却装置中获得多至超过90％由甲烷组成的馏份CH4。将在低温冷却装置14中产生的冷凝物(19，20)C2-馏份送入第二塔13的上段13a。将一部分来自低温冷却装置的液态甲烷馏份用作上段13a的回流。将下段13b的塔底利用粗煤气或者利用热的制冷剂进行煮沸。
第二塔13包括两个区段13a、13b，因此是传统C1/C2分离(脱甲烷塔)13a与C2/C3分离(脱乙烷塔)13b的组合，并在9.5巴的压力下工作。
在第二塔的上段13a中，从在低温冷却装置14中收集的冷凝物汽提出溶解的甲烷和溶解的氢气。将来自下段13b的不含C3的气体产品用作汽提气体。下段13b原则上是脱乙烷塔，在其中将来自第一塔的塔底馏份C2/C3分离成两种馏份。在此产生包含具有最多2个碳原子的烃的馏份和包含具有3个碳原子的烃的馏份C3。在此从第二塔的下段13b获得C3馏份C3作为塔底产品。将一部分来自上段13a的液态C2馏份17用作该区段的回流。塔的塔底利用粗煤气或者利用热的C3制冷剂或者利用热的混合制冷剂进行煮沸。
从第二塔13的上段13a的塔底由侧面作为气体产品16和液态产品17排出的来自第二塔的C2馏份送至第三塔15(C2分离器)。在此获得乙烯作为塔顶产品C2H4。第三塔15的塔底产品C2H6主要由乙烷组成，并作为进料送回以进一步裂解。上段13a的塔顶产品18主要由甲烷组成，并送回至低温冷却装置14。

Claims (10)

1.在利用裂解由含有烃类的进料产生烃类的设备中分离烃类的方法，其中对作为粗煤气(2)产生的包含气态烃的裂解产品气体(1)进行压缩和干燥，并作为进料导入分离阶段(前端C3/C4分离)中，在其中将粗煤气(2)分离成由具有最多3个碳原子的烃组成的烃类馏份(C3-)和由具有至少4个碳原子的烃组成的烃类馏份(C4+)，所述前端C3/C4分离包括C4吸收器(9)和塔(脱丙烷塔)(10)，在其中将具有至少4个碳原子的烃(C4+)作为塔底产品排出，其特征在于，将由具有最多3个碳原子的烃组成的烃类馏份(C3-)导入包括第一塔(12)和第二塔(13)的分离阶段中，其中第二塔(13)具有2个分离的区段(13a，13b)，在第一塔(12)中将由具有最多2个碳原子的烃组成的烃类馏份(C2-)作为塔顶产品排出，并送至第二塔(13)的上段(13a)，将第一塔(12)的塔底产品(C2/C3)送至第二塔(13)的下段(13b)。
2.根据权利要求1的方法，其特征在于，所述C4吸收器(9)在11至20的压力下运行，所述脱丙烷塔(10)在8至12巴的压力下运行，并将C4吸收器(9)的塔顶产品(C3-)送入另一个压缩阶段(5b)。
3.根据权利要求1或2的方法，其特征在于，将所述C4吸收器(9)的塔顶产品(C3-)经由针对具有最多3个碳原子的烃的氢化阶段(11)导入第一塔(12)中。
4.根据权利要求1至3之一的方法，其特征在于，所述第二塔(13)的上段(13a)作为脱甲烷塔运行，而所述第二塔(13)的下段(13b)作为脱乙烷塔运行。
5.根据权利要求1至4之一的方法，其特征在于，所述第二塔(13)在9至13巴的压力，优选在9.5巴的压力下运行。
6.根据权利要求1至5之一的方法，其特征在于，将所述第一塔(12)的塔顶产品(C2-)送至低温冷却装置(14)，其中在低温冷却装置(14)中获得多至超过90％由甲烷组成的馏份(CH4)，以及获得最多95％由氢气组成的馏份(H2)，将在低温冷却装置(14)中获得的冷凝物(19，20)送至所述第二塔(13)的上段(13a)。
7.根据权利要求1至6之一的方法，其特征在于，将所述第二塔(13)的上段(13a)的塔顶产品(18)送回低温冷却装置(14)。
8.根据权利要求1至7之一的方法，其特征在于，将所述第二塔(13)的上段(13a)的塔底产品(16，17)作为进料导入第三塔(C2分离器)(15)中，在其中获得乙烯作为塔顶产品(C2H4)，及获得乙烷作为塔底产品(C2H6)。
9.根据权利要求1至8之一的方法，其特征在于，从所述第二塔(13)的下段(13b)的塔底排出具有3个碳原子的烃类馏份(C3)，并作为进料导入第四塔(C3分离器)中，在其中获得丙烯作为塔顶产品，及获得丙烷作为塔底产品。
10.根据权利要求1至9之一的方法，其特征在于，在所述低温冷却装置(14)中所需的制冷是利用乙烯制冷剂及利用由甲烷和具有2个烃原子的烃组成的返回气体，或者利用由具有1个、2个和3个碳原子的烃组成的混合制冷剂产生的。
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