CN1751012A - 生产甲醇的方法及设备 - Google Patents

生产甲醇的方法及设备 Download PDF

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CN1751012A
CN1751012A CNA2004800046334A CN200480004633A CN1751012A CN 1751012 A CN1751012 A CN 1751012A CN A2004800046334 A CNA2004800046334 A CN A2004800046334A CN 200480004633 A CN200480004633 A CN 200480004633A CN 1751012 A CN1751012 A CN 1751012A
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oxygen
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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

一种通过使烃进料(10)与氧气(9)在反应器(11)内反应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)内产生作为最终产物的甲醇的方法，所述转化器在操作压力下工作，在氧气压力下向所述反应器提供所述氧气，所述合成气的生产压力使得合成气在进入转化器之前经历至多一个压缩比为1－1.7的压缩步骤。

Description

生产甲醇的方法及设备
技术领域
本发明涉及生产甲醇的方法和设备。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。
合成气(syngas)可通过用蒸汽重整烃或通过使烃与氧气反应或通过并联或串联方式混合使用这两项技术制备。在合成气生产单元产生的合成气先用合成气压缩机压缩，然后在于80-120巴高压下工作的转化器内转化为甲醇。然后，未反应的合成气在合成气循环压缩机中压缩，与来自合成气生产单元的合成气混合，并且将该混合物流送到甲醇转化器的入口。所得到的甲醇在主要有两个或三个蒸馏塔组成的甲醇回收单元中回收并纯化以达到需要的甲醇纯度。
由于甲醇在65-120巴的高压下生产，主要工艺步骤一般包括合成气的生产，合成气在两级合成气压缩机中压缩，甲醇合成和甲醇回收。当氧气用于生产合成气时，所述合成气生产单元上游存在一个空气分离单元。
现行趋势是以非常大的量生产甲醇，如每天5000吨或更高。大型甲醇厂需要大型合成气生产单元并且发展趋势是使用氧-基技术，以便在单列单元中生产如此大量的合成气并且提高整个甲醇生产过程的能源效率。作为选择，可以不使用氧气，通过将大量二氧化碳注入所述合成气生产单元生产大量合成气。二氧化碳可以来自各种来源，例如存在于甲醇转化器出口的二氧化碳或在附近氨生产单元产生的二氧化碳或天然气中自然存在的二氧化碳。利用大量注入的CO2，可以达到与那些用氧基方案相当的能源效率。
这些方法中多数都使用以高压产生氧气的空气分离单元(ASU)以将天然气转化为合成气，所述合成气被送入单一转化器，在其中转化为甲醇。
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以产生合成气。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巴的压力产生甲醇。
通常，所述合成气压缩机不得不包括两级，因为现行反应器与现行转化器之间的压力差别对于单级压缩机太大以至不能满足压力要求。这些两级压缩机在资金投入和维修保养两方面更昂贵。此外，经常使用两个并联的合成气压缩机以避免维修的问题。
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该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进行其中包含放热反应的转化以在转化器内产生最终产物甲醇的方法中，所述转化器在操作压力下工作，所述氧气以在至少一个空气压缩机压缩后的冷却压缩空气分离后的氧气压力供给所述反应器，该方法的改进之处在于所述合成气在一种压力下产生从而使得合成气从反应器送入转化器至多经过一个压缩比为1-1.7的压缩步骤，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。
关于“至多一个压缩比为1-1.7的压缩步骤”，应当理解为无压缩步骤，或一个压缩比为1-1.7的压缩步骤。该压缩比可通过使用单级压缩机获得。
当不存在压缩步骤时，生产所述合成气的压力在比所述转化器操作压力高至少1巴、可至少高3巴、或甚至至少高5巴。
所述烃进料可以是天然气。
一些二氧化碳可能存在于所述转化器的出口；在这种情况下，二氧化碳在二氧化碳压缩机中压缩后再循环到反应器的入口。
另外，某些未反应的合成气存在于所述转化器的出口并且可以再循环。当合成气不经压缩被送入转化器时，存在于转化器出口的未反应合成气在循环合成气压缩机中压缩后再循环到所述转化器的入口。当合成气在被送入转化器之前在单级合成气压缩机中经历一个压缩步骤时，存在于转化器出口的未反应合成气被循环到所述单级合成气压缩机的入口。
汽轮机可以与循环合成气压缩机、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。当通过反应器产生的合成气不经压缩被送入转化器时，所述合成气压缩机是循环合成气压缩机；当通过反应器产生的合成气在送入转化器之前被压缩时，所述合成气压缩机是单级合成气压缩机，并且通过反应转化器产生的未反应合成气被再循环到所述单级合成气压缩机的入口。
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的压力，所述氧气压力优选比反应器操作压力高至少5巴，甚至可比反应器操作压力高至少3巴，也可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使该进料与氧气反应以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：包括反应器，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的装置，其中转化器在操作压力下工作，所述氧气以空气分离后的氧气压力提供；该设备的改进之处在于：或者使用一个用于压缩由反应器产生并将送入转化器的合成气的单级合成气压缩机，或者不存在用于压缩由反应器产生并将送入转化器的合成气的合成气压缩机。
当由反应器产生的合成气不经历压缩步骤时，所述设备可以包含用于压缩由转化器产生并将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产生并将送入反应器上游的再循环二氧化碳的二氧化碳压缩机。
汽轮机可以与合成气压缩机、二氧化碳压缩机中的至少一个、至少一个用于压缩待分离的空气以生成氧气的压缩机和至少一个空气增压器连接。
附图简要说明
图1是根据本发明的在合成气进入转化器之前不需要压缩的设备简图。
图2是根据本发明的在合成气进入转化器之前在单级压缩机中压缩的设备简图。
发明详述
现在，将对本发明作详细描述。
参照图1。
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。
所述转化器生成作为最终产物17的甲醇。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。
参照图2。
在至少产生液体氧的ASU 3中分离空气1。所述空气在压缩机5中压缩到6巴，在吸收床(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中或至少部分送入低压塔中。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。液体氧9被泵压到41巴的压力并通过与供给空气的热交换汽化。以40巴生产的气态氧(经历在交换器和管道中的压降后)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，进口压力为40巴。天然气10同样以40巴压力供给反应器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33巴并且ΔP应大于0。在其中反应器的操作压力为33巴的情况下，氧气可以在34-80巴之间、优选高于40巴或甚至50巴的压力下产生并以此压力送入反应器。所述氧气可以直接泵压到34至80巴之间的压力并以此压力在热交换主管道中汽化，或者泵压到中等压力，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压缩到34-80巴压力。
合成气在40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，因此其中存在一个用于压缩所述合成气的单级压缩机123，且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入口与压缩机123入口之间存在约1-10巴的压降。
所述转化器生成作为最终产物17的甲醇。未反应的合成气21可以由转化器15的出口再循环到压缩机123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和合成气压缩机123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中所述，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该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进行其中包含放热反应的转化过程以在转化器内产生最终产物甲醇的的方法，其中，所述转化器在操作压力下工作，所述氧气以在至少一个空气压缩机压缩后的冷却压缩空气分离后的氧气压力供给所述反应器，该方法的改进之处在于所述合成气在一种压力下产生从而使得合成气从反应器送入转化器至多经过一个压缩比为1-1.7的压缩步骤，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，其中所述合成气在比所述转化器操作压力高的压力下进入转化器。
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，其中甲醇以及二氧化碳和未反应的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二氧化碳压缩机中压缩后被再循环到反应器的入口。
6.如权利要求5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。
7.如权利要求4所述的方法，其中合成气不经压缩被送入所述转化器，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循环合成气压缩机中压缩后被再循环到转化器的入口。
8.如权利要求4所述的方法，其中合成气在送入所述转化器之前在单级合成气压缩机中经历一个压缩步骤，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被循环到所述单级合成气压缩机的入口。
9.如权利要求7或8所述的方法，其中合成气压缩机、空气压缩机和空气增压机中的至少一个与汽轮机连接。
10.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。
11.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。
12.一种使用烃进料通过使该进料与氧气反应以形成至少包含一氧化碳、二氧化碳和氢气的合成气的设备，包括反应器，将所述进料送入反应器的进料导管，将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转化器内进行其中包含放热反应的转化以产生作为最终产物甲醇的转化器连接，该转化器在操作压力下工作，所述氧气以空气分离后的氧气压力提供；该设备的改进之处在于存在一个用于压缩由反应器产生并将送入转化器的合成气的单级合成气压缩机。
13.如权利要求12所述的设备，其中包括汽轮机和至少下述之一：
-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
-用于将未反应的合成气从所述转化器送入用于压缩从反应器移出的合成气的单级合成气压缩机的上游的导管，
所述汽轮机与所述合成气压缩机和二氧化碳压缩机中的至少一个，以及至少一个空气压缩机和空气增压机连接。
14.一种使用烃进料通过使该进料与氧气反应以形成至少包含一氧化碳、二氧化碳和氢气的合成气的设备，包括反应器，将所述进料送入反应器的进料导管，将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转化器内进行其中包含放热反应的转化以产生作为最终产物甲醇的转化器连接，该转化器在操作压力下工作，所述氧气以空气分离后的氧气压力提供；该设备的改进之处在于不存在用于压缩由反应器产生并将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，其中包括汽轮机和至少下述之一：
-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
-用于压缩从所述转化器移出并送入所述转化器上游的未反应的合成气的循环合成气压缩机，
所述汽轮机与所述合成气压缩机和二氧化碳压缩机中的至少一个，以及至少一个空气压缩机和空气增压机连接。
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