CN100422072C - 部分氧化重整器-重整交换器结构 - Google Patents

部分氧化重整器-重整交换器结构 Download PDF

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CN100422072C
CN100422072C CNB2004800068723A CN200480006872A CN100422072C CN 100422072 C CN100422072 C CN 100422072C CN B2004800068723 A CNB2004800068723 A CN B2004800068723A CN 200480006872 A CN200480006872 A CN 200480006872A CN 100422072 C CN100422072 C CN 100422072C
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S·A·克内兹
A·马尔霍特拉
D·P·曼
M·J·范西克尔斯
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Abstract

本发明公开了一种低耗能的氢的生产。重整交换器在具有改善的效率和减少了蒸汽排出的新制氢设备中、或者在现有的制氢设备中与部分氧化反应器并联，其制氢能力可以增加20—30%，而减少了制氢设备的蒸汽排出。

Description

部分氧化重整器-重整交换器结构
发明背景
本发明涉及使用部分氧化(POX)反应器和重整交换器生产合成气。
烃的重整是用于生产含氢合成气体的标准方法，该合成气例如用来生产氨或者甲醇。传统的POX反应器是非填充的(unpacked)、自由流动的非催化气体发生器，向其中供给预热的烃气和氧气，其任选带有温度调节器。然后使该部分氧化反应器的排出物骤冷或者冷却，一般到200-300℃，任选进行清洗以除去烟灰，并通常在高低温转换反应器中进行进一步转化，在该反应器中CO和蒸汽反应以形成额外的氢和CO2。人们特别希望得到具有高氢含量的合成气，用于氨或者其它合成方法，其中氢是来自合成气的主要反应物。在POX反应器进料中蒸汽与烃的重量比通常为0.1-5，在烃中氧与碳的原子比为0.6-1.6，并且反应时间为1-10秒。
POX反应器公开在例如美国专利US 2,896,927；3,920,717；3,929,429；和4,081,253中，在此将它们全文引入作为参考。
在骤冷之前POX反应器产生很高温度，例如1100-1650℃的合成气排出物。这意味着大部分烃进料必须有效地被用作相当昂贵的燃料来预热进料，以及产生高压或中压蒸汽。然而，产生的蒸汽通常远远超过装置的需要量，因此必须将其排出，并且蒸汽常常有很小市场或者没有市场。
在本领域中需要一种改善使用POX反应器的制氢设备的效率并且将减少或消除蒸汽排出的方法。人们也常希望使得现有制氢设备制备的氢最大化或增加；然而POX反应器通常是能力有限的操作。POX反应器不易于扩大增产。
本发明通过把部分冷却的POX反应器工艺排出物供给重整交换器壳侧，以提供用于附加合成气生产的热量。所用重整交换器中自热重整器是已知的，例如参见LeBlanc的美国专利US 5,011,625和5,122,299以及Cizmer等人的US 5,362,454，将所有文献全文在此引入作为参考。这些重整交换器可以以商标为KRES或Kellogg重整交换器体系商购获得。
发明概述
本发明在具有改善效率和减少蒸汽排出的新制氢设备中，或在现有制氢设备中，将重整交换器与部分氧化(POX)反应器并联使用。在一个实施方案中，制氢能力可以增加20-30％，而减少了从制氢设备排出的蒸汽。所得到的方法具有极低的能耗。
本发明提供用于制备合成气的方法。该方法包括：(a)在部分氧化反应器中用氧气把第一烃部分部分氧化，以产生第一反应器排出物；(b)冷却第一反应器排出物到650-1000℃的温度；(c)把第一反应器排出物供给重整交换器；(d)使第二烃部分和蒸汽经过重整交换器中的催化剂区段，以生成第二反应器排出物；(e)从催化剂区段排出第二反应器排出物，以与第一反应器排出物形成混合物；(f)使该混合物经过催化剂区段与之间接换热，以便冷却该混合物而加热催化剂区段；和(g)从重整交换器收集冷却的混合物。
冷却可以包括把水作为骤冷流体引入第一反应器排出物、间接换热、或水骤冷与间接换热相结合。可把间接换热用于预热交叉换热器中的第二烃部分。催化剂区段可以包括催化剂管。该方法还可以包括把第二烃部分供给重整交换器的管侧并使它经过该催化剂管，并且把冷却的第一反应器排出物供给重整交换器的壳侧进口。壳侧进口可以与催化剂管的出口相邻。该方法进一步地包括供给重量比为40∶60-95∶5的第一和第二烃部分。优选，第一和第二烃部分以40∶60-60∶40重量比供给(为了更有效地制造氢)，或80∶20-95∶5(如果想得到更多的CO)。
本发明还提供了一种合成气的生产设备。该设备包括：(a)用于用氧气把第一烃部分部分氧化以产生第一反应器排出物的部分氧化反应器装置；(b)用于把第一反应器排出物冷却到650-1000℃的温度的装置；(c)用于把第一反应器排出物供给重整交换器的装置；(d)用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的装置；(e)用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的装置；(f)用于使混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的装置；和(g)用于从重整交换器收集冷却的混合物的装置。
本发明进一步提供一种用于改进合成气工艺的方法，所述工艺包括用于把第一烃物流转化为第一反应器排出物的部分氧化反应步骤，用于冷却第一反应器排出物并用回收的热量生产蒸汽的热量回收步骤，以及用于回收冷却的反应器排出物并生产具有提高氢含量的合成气产品的下游处理步骤。改进包括：(a)用于把第一反应器排出物部分冷却到650-1000℃的温度的步骤；(b)用于把部分冷却的第一反应器排出物转入重整交换器的步骤；(c)用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的步骤；(d)用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的步骤；(e)用于使该混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的步骤；(f)用于把混合物从重整交换器送入热量回收步骤的步骤。
附图简述
图1是传统的现有技术POX方法的流程简图，其可以根据本发明的一个实施方案进行改进。
图2是根据本发明的一个实施方案的POX反应器和重整交换器集成在一起的合成气工艺的流程简图。
发明详述
本发明的改进装置具有图1表示的总体结构。把来自于管线2的脱硫天然气或其它烃与来自管线4的工艺蒸汽混合，并且把混合物在进料预热交换器(未显示)中预热。把预热的蒸汽-烃混合物经由管线6与氧气10送入一个POX反应器8(或多个POX反应器)中，并且将排放物收集在管线12中，用经由管线14注入的水骤冷，然后提供给下游加工段15，包括转换区段(高温，中温和/或低温转换器)，回收热量，除去CO2(例如，变压吸附或PSA)等等。生产出富氢的合成气流17。
根据如图2所示的本发明的一个实施方案来改进图1的装置，或构建新的装置。POX反应器8和管线2、4、6、10是常规的，如图1所述。将来自POX反应器8的在管线12内的工艺排出物用经由管线14的工艺用水骤冷到700-1100℃，优选750-1000℃，并且将混合物经由管线16供给重整交换器18的壳侧进口。除骤冷管线14之外还可以使用热交换器15，或用其代替骤冷管线14。可以使用热交换器15来预热进料流19。
把在管线19中预热的蒸汽和烃(其可以与管线2中的烃相同或不同)的混合物供给重整交换器18的管侧进口。混合物通过催化剂管20，以形成额外的含氢气体。将来自催化剂管20的出口孔的重整的气体与POX重整装置的排出物混合，并且使混合物通过催化剂管20外围进入壳侧出口，在此将其以常规的方式收集到管线22中。将管线22中的合并的合成气供给如图2的常规的下游加工段24，其包括转换转化器、用于回收热量的热交换单元，并进一步提纯，生产提纯的分子氢。在改进应用中，根据需要可以改造或扩大下游加工单元，以处理经由管线22供给的由添加的重整交换器18产生的额外的合成气。
通过POX反应器排出物的量和温度来满足重整交换器的热量需要。通常，通过管线19输入重整交换器18的进料越多，需要来自POX反应器排出物16的热量越多，以便维持催化剂管20中的通常吸热的重整反应。人们希望重整装置催化剂管排出气体的温度与该重整交换器18的结构材料所允许的温度一样高，例如在标准KRES设备中温度为750-1000℃。如果温度太低，在重整交换器18中会发生不充分的重整；而如果温度过高，则冶金因素将成问题。应当注意保证将温度选择得使金属粉尘化最小。
供给POX反应器8的烃的比例为总量的40-95％，而供给重整交换器18的比例为总烃进料的5-60％。人们希望POX反应器8和重整交换器18之间的进料分配可以使得POX反应器8必须产生合适量的热排出物，以提供重整交换器18所需的热量。分配到POX反应器8的进料为总量的40-60％，这有利于改善能源利用率和使制氢的速率最大，而将总烃进料的80-95％供给POX反应器有利于在合成气中产生更多CO。
通过实施例来说明本发明。将用于按照图2安装的集成的POX-重整交换器单元的基础工艺设计参数基于对图1的典型POX方法进行改进，管线16的物流组成和流速列在下表1中。表1还给出了根据图2结构进行改造的方法中所选物流的组成、性能和流速。
表1.  POX反应器-重整交换器结构
在仅使用POX反应器的基础情况下，由装置的重整区段产生的合成气将具有在管线16中的POX反应器排出物的组成和流速。依据本发明的该实施方案，将重整交换器与POX反应器并联使用，使在管线16中的排出物与从催化剂管20排出的气体混合以获得具有在管线22中的组成的合成气。该实施例表明，集成的POX-重整交换器方法可用于回收重整交换器中的废热并且使氢的生产提高20-25％。以这种方式将工艺热量用于附加的氢生产相应地减少了蒸汽的排出。
在上文中参考非限制性实施例说明了本发明，这些实施例仅是举例说明的目的。本领域技术人员在阅读了上文后，各种改进和变化都是显而易见的。所有这些改进和变化都落入由所附权利要求体现的本发明的范围和精神内。

Claims (15)

1. 一种用于制备合成气的方法，包括：
在非催化部分氧化反应器中用氧气把第一烃部分部分氧化，以产生第一反应器排出物；
冷却第一反应器排出物到650-1000℃的温度；
把冷却的第一反应器排出物供给重整交换器；
使第二烃部分和蒸汽经过重整交换器中的催化剂区段，以生成第二反应器排出物；
从催化剂区段排出第二反应器排出物，以与第一反应器排出物形成混合物；
使该混合物经过催化剂区段与之间接换热，以便冷却该混合物而加热催化剂区段；和
从重整交换器收集冷却的混合物；
其中冷却第一反应器排出物包括把水作为骤冷流体加入第一反应器排出物的直接换热；
所述第一和第二烃部分以重量比40∶60-95∶5来供给。
2. 根据权利要求1的方法，其中冷却第一反应器排出物进一步包括间接换热。
3. 根据权利要求2的方法，其中通过间接换热冷却第一反应器排出物，包括在交叉换热器中加热第二烃部分。
4. 根据权利要求1的方法，其中冷却第一反应器排出物包括换热。
5. 根据权利要求4的方法，其中通过换热冷却第一反应器排出物包括在交叉换热器中间接加热第二烃部分。
6. 根据权利要求1的方法，其中催化剂区段包括催化剂管。
7. 根据权利要求4的方法，其中把第二烃部分供给重整交换器的管侧并且使其通过催化剂管。
8. 根据权利要求4的方法，其中把冷却的第一反应器排出物供给重整交换器的壳侧进口。
9. 根据权利要求6的方法，其中壳侧进口与催化剂管的出口相邻。
10. 根据权利要求1的方法，其中第一和第二烃部分以重量比40∶60-60∶40来供给。
11. 根据权利要求1的方法，其中第一和第二烃部分以重量比95∶5-80∶20来供给。
12. 根据权利要求2的方法，其中在把第二烃部分供给重整交换器之前通过间接换热加热第二烃部分。
13. 根据权利要求12的方法，其中把水加入第一反应器排出物。
14. 根据权利要求13的方法，其中把第二烃部分输入重整交换器的管侧进口。
15. 一种在如权利要求1制备合成气的方法中使用的设备，包括：
用于用氧气把第一烃部分非催化地部分氧化以产生第一反应器排出物的装置，即部分氧化反应器装置；
用于把第一反应器排出物冷却到650-1000℃的温度的装置；
用于把冷却的第一反应器排出物供给重整交换器的装置；
用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的装置；
用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的装置；
用于使混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的装置；和
用于从重整交换器收集冷却的混合物的装置。
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