CN100439310C - 二甲醚的生产方法及设备 - Google Patents

二甲醚的生产方法及设备 Download PDF

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CN100439310C
CN100439310C CNB200480004632XA CN200480004632A CN100439310C CN 100439310 C CN100439310 C CN 100439310C CN B200480004632X A CNB200480004632X A CN B200480004632XA CN 200480004632 A CN200480004632 A CN 200480004632A CN 100439310 C CN100439310 C CN 100439310C
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A·吉亚尔
E·施密特
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

一种使用烃进料通过使进料(10)与氧气(9)在反应器(11)内反应以形成至少包含一氧化碳、二氧化碳和氢气的合成气并使该合成气进行其中包含放热反应的转化以在转化器(15)内产生二甲醚的方法，所述转化器在操作压力下工作，所述氧气在氧气压力下供给所述反应器，所述合成气在高于转化器操作压力的压力下产生。

Description

二甲醚的生产方法及设备
技术领域
本发明涉及生产二甲醚(DME)的方法和设备。本文中提及的所有压力均为绝对压力。
发明背景
甲醇通过使至少包含一氧化碳、二氧化碳和氢气的合成气与催化剂接触制备。该合成气在独立容器内转化为甲醇。
DME可以通过直接方法或间接(两步)方法制备。
所述直接方法将合成气转化为甲醇，然后在同一转化器内将甲醇转化为DME。
所述两步法包括传统两步法，其中甲醇在催化固定床容器内脱水，对该容器的流出物进行冷却和蒸馏处理以产生DME和甲醇，其中甲醇再循环到转化器中。
Lurgi Mega DME方法使用天然气生产甲醇，然后在容器内处理所生产的甲醇以产生DME、水和其他烃的混合物。然后蒸馏该混合物。
Haldor Topsoe DME方法将合成气转化为甲醇，然后在固定床容器内将甲醇转化为DME。
大多数这些方法都使用空气分离单元(ASU)以高压产生氧气，将天然气转化为合成气，所述合成气或者被送入单一转化器，以直接方法在其中转化为甲醇，然后转化为DME，或者以两步法被送入第一转化器转化为甲醇，然后甲醇转化为DME。
如US-A-6117916所述，ASU以40巴的压力产生氧气，并且所述氧气在部分氧化反应器内与蒸汽和天然气反应产生合成气。然后将压力40巴的合成气压缩到70巴并送入甲醇反应器，从而以66巴压力生产甲醇。
一般使用两个并联的合成气压缩机以避免维修的问题。这些压缩机在资金投入和维修保养两方面都是昂贵的。
发明概述
根据本发明的一个目的，在一种使用烃进料通过使进料与氧气在反应器内反应以形成至少包含一氧化碳、二氧化碳和氢气的合成气并使该合成气在转化器内进行其中包含放热反应的转化以产生二甲醚的方法中，所述转化器在操作压力下工作，供给所述反应器的氧气的压力为经过至少一个空气压缩机压缩的冷却压缩空气分离后的氧气压力，该方法的改进之处在于在一种压力下生产所述合成气，从而使得所述合成气不经过压缩步骤从反应器送入转化器，并且空气分离单元以高于反应器操作压力的氧气压力为反应器提供氧气。
所述合成气的生产压力比所述转化器操作压力高至少1巴、可至少3巴、甚至至少5巴。
所述烃进料可以是天然气。
甲醇、二氧化碳和未反应的合成气中的至少一种可能存在于所述转化器的出口。
二甲醚，通过放热反应产生，可以通过直接方法或通过间接方法，即通过将合成气转化为甲醇，然后减甲醇转化为二甲醚来生产。
例如，所述转化器可以产生甲醇和二甲醚的混合物，分离该混合物以产生基本纯的二甲醚和基本纯的甲醇，并且将基本纯的甲醇再循环到所述转化器的入口。所述转化器的出口也可能存在一些二氧化碳；在这种情况下，二氧化碳经二氧化碳压缩机压缩后被再循环到反应器的入口。另外，一些未反应的合成气存在于所述转化器的出口，可以经循环合成气压缩机压缩后再循环到所述转化器的入口。
可以将汽轮机与再循环合成气压缩机、二氧化碳压缩机、空气增压器和空气压缩机中的至少一个连接。
所述反应器可以是部分氧化反应器或自热反应器。
所述空气分离单元产生的氧气的压力高于反应器操作压力，所述氧气压力优选比反应器操作压力高至少5巴，也可以比反应器操作压力高至少3巴，甚至可以比反应器操作压力高至少1巴。
根据本发明的另一方式，在一种使用烃进料通过在反应器内使该进料与氧气反应形成至少包含一氧化碳、二氧化碳和氢气的合成气的设备中；有反应器，将所述进料和氧气送入反应器的装置，将合成气从反应器移出的装置，使合成气在转化器内进行其中包含放热反应的转化以产生二甲醚的装置，转化器在操作压力下工作，通过空气分离后氧气的压力提供所述氧气，该设备的改进之处在于不存在用于压缩由反应器产生并送入转化器的合成气的合成气压缩机。
所述设备可以包含用于压缩由转化器送入该转化器上游的再循环合成气的循环合成气压缩机。
所述设备可以包含用于压缩由转化器送入反应器上游的再循环二氧化碳的循环二氧化碳压缩机。
可以将汽轮机与合成气压缩机、二氧化碳压缩机中的至少一个、至少一个用于压缩空气以分离形成氧气的空气压缩机和至少一个空气增压器连接。
附图简要说明
图1是根据本发明的设备的简图。
发明详述
现在，参照附图对本发明作详细描述。
在至少产生液体氧的ASU 3中分离空气1。可以使用如Arpentinier等人《The Technology of Catalytic Oxidations》，技术版(EditionsTechnip)，2001或Hausen Linde的《Tieftemperaturtechnik》所述的采用通过与供给空气热交换的汽化液氧步骤的任何设备。所述空气在压缩机5中压缩到6巴，在吸附床(未显示)纯化，然后部分送入ASU的塔中。另一部分压缩空气在增压器7中压缩到压力70巴。所述空气膨胀，然后部分液化并且如所示全部送入中压塔或至少部分送入低压塔。为了简化，常规的回流物流没有显示。热交换器用来加热来自所述塔的气态物流(未显示)以及至少一种液体物流9。所述液氧9被泵压到61巴的压力并通过与供给空气的热交换汽化。以60巴生产的气态氧(经历热交换器和管道中压降后)被送入反应器11，该反应器可以是部分氧化反应器或自热反应器，具有60巴的进口压力。天然气10同样以60巴供给反应器11。
其中反应器的操作压力是P，氧气在P+ΔP压力下产生并送入反应器，P优选是至少49巴并且ΔP应大于0。在其中反应器操作压力为49巴的情况下，氧气可以在50-80巴之间、优选高于60巴或甚至70巴的压力下产生并以此压力送入反应器。可以将所述氧气直接泵压到50-80巴的压力，然后在该压力下在热交换主管道中汽化，或者将其泵压到中等压力，在中等压力下在热交换主管道中汽化，然后在氧气压缩机中将其压缩到50-80巴的压力。
合成气在60巴压力下产生并以此压力通过导管13送入转化器15。由于转化器15在50巴的进入压力下工作，因此不存在压缩所述合成气的压缩机。由于存在用于产生蒸汽的锅炉和其他设备(未显示)，反应器11入口与转化器15入口之间存在约1-10巴的压降。
所述转化器产生DME作为最终产物19。在其中DME是最终产物或最终产物之一的情况下，所述转化器可以按照上述单步法或两步法工作。
在某些方法中，从通过转化器产生的DME中除去甲醇并再循环到转化器的入口(例如Lurgi DME方法和NKK浆体相(slurry phaseprocess)方法)。未反应的合成气21可以经压缩机23压缩后由转化器15的出口再循环到转化器15的入口。通常将二氧化碳27经压缩机29压缩后由转化器15的出口再循环到反应器11的入口。优选地，压缩机5、增压器7、二氧化碳循环压缩机29和循环合成气压缩机23都由单一的汽轮机25驱动，其中所述蒸汽来源于放热过程。
如果不是这样，至少某些上述压缩机通过汽轮机驱动。EP-A-1102953描述了一种用于驱动主空气压缩机和空气增压器的汽轮机。当然可以由单独汽轮机驱动循环合成气压缩机、二氧化碳循环压缩机和一个或两个空气压缩机。增压器7不是空气分离单元3的必要元件；正如EP-A-0504029所述，例如空气压缩机5可以将所有空气压缩到汽化氧气需要的汽化压力。由于转化过程是高放热的，因此该方法或所述合成气可用来产生用于汽轮机25的蒸汽。

Claims (15)

1.一种使用烃进料通过使进料与氧气在反应器内反应以形成至少包含一氧化碳、二氧化碳和氢气的合成气并使该合成气在转化器内进行其中包含放热反应的转化以产生二甲醚的方法中，所述转化器在操作压力下工作，供给所述反应器的氧气的压力为经过至少一个空气压缩机压缩的冷却压缩空气分离后的氧气压力，该方法的改进之处在于在一种压力下生产所述合成气，从而使得所述合成气不经过压缩步骤从反应器送入转化器，并且空气分离单元以高于反应器操作压力的氧气压力为反应器提供氧气。
2.如权利要求1所述的方法，其中在比转化器操作压力高至少1巴的压力下产生所述合成气。
3.如权利要求1所述的方法，其中所述烃进料是天然气。
4.如权利要求1所述的方法，其中二甲醚以及甲醇、二氧化碳和未反应合成气中的至少一种存在于所述转化器的出口。
5.如权利要求4所述的方法，其中所述放热反应通过直接法产生二甲醚。
6.如权利要求4所述的方法，其中所述放热反应通过间接法产生二甲醚，将合成气转化为甲醇，然后将甲醇转化为二甲醚。
7.如权利要求4所述的方法，其中所述转化器产生甲醇和二甲醚的混合物，分离该混合物以产生基本纯的二甲醚和基本纯的甲醇，并且将基本纯的甲醇再循环到所述转化器的入口。
8.如权利要求4所述的方法，其中二氧化碳存在于所述转化器的出口，由所述转化器产生的二氧化碳在经过二氧化碳压缩机压缩后被再循环到反应器的入口。
9.如权利要求8所述的方法，其中二氧化碳压缩机、空气压缩机和空气增压机中的至少一个与汽轮机连接。
10.如权利要求4所述的方法，其中未反应的合成气存在于所述转化器的出口，由所述转化器产生的未反应的合成气在经过循环合成气压缩机压缩后被再循环到转化器的入口。
11.如权利要求10所述的方法，其中循环合成气压缩机、空气压缩机和空气增压机中的至少一个与汽轮机连接。
12.如权利要求1所述的方法，其中所述烃进料在部分氧化反应器内与氧气反应。
13.如权利要求1所述的方法，其中所述烃进料在自热反应器内与氧气反应。
14.一种使用烃进料通过在反应器内使该进料与氧气反应形成至少包含一氧化碳、二氧化碳和氢气的合成气的设备，其中包含反应器，将所述进料送入反应器的进料导管，将所述氧气送入反应器的氧气导管，将合成气从反应器移出的合成气移出导管，所述合成气移出导管与使合成气在其中进行包含放热反应的转化以产生二甲醚的转化器连接，该转化器在操作压力下工作，通过空气分离后氧气的压力提供所述氧气，该设备的改进之处在于不存在用于压缩由反应器产生并送入转化器的合成气的合成气压缩机。
15.如权利要求14所述的设备，其中包含汽轮机和下述至少一种：至少一个用于压缩待分离的空气以形成氧气的空气压缩机，至少一个用于进一步压缩待分离的空气以形成氧气的空气增压机，用于压缩由转化器送入反应器的二氧化碳的二氧化碳压缩机和用于压缩由转化器送入转化器上游的循环合成气的循环合成气压缩机；所述汽轮机与所述循环合成气压缩机、二氧化碳压缩机中的至少一个和至少一个空气压缩机和空气增压机连接。
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