CN107867674A - 用于蒸汽重整的方法和设备 - Google Patents

用于蒸汽重整的方法和设备 Download PDF

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CN107867674A
CN107867674A CN201710888283.1A CN201710888283A CN107867674A CN 107867674 A CN107867674 A CN 107867674A CN 201710888283 A CN201710888283 A CN 201710888283A CN 107867674 A CN107867674 A CN 107867674A
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M·雅罗施
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Abstract

本发明涉及产生包含氢和/或一氧化碳的气体产品(21)的方法和设备，其中将由含烃的起始物质(1)形成的烃进料(5)连同过热蒸汽(13)一起送至在升高的压力下进行的蒸汽重整(D)，以获得包含氢和一氧化碳的合成粗煤气(17)，由此获得气体产品(21)。其特征在于，向锅炉给水(8)在高于其临界压力的压力下输入热量(E1)，以获得超临界水(10)，然后将其至少一部分量(12)在蒸汽喷射泵(V)中用作推进介质，借此压缩烃进料(5)和/或压缩用于形成烃进料的物质。

Description

用于蒸汽重整的方法和设备
技术领域
本发明涉及产生包含氢和/或一氧化碳的气体产品的方法，其中将由含烃的起始物质形成的烃进料连同过热蒸汽一起送至在升高的压力下进行的蒸汽重整，以获得包含氢和一氧化碳的合成粗煤气，由此获得气体产品。此外，本发明还涉及用于实施根据本发明的方法的设备。
背景技术
蒸汽重整是最广泛地推广的在工业上由轻烃生产富含氢的合成气的方法。在此，含烃的起始物质(例如天然气、液化气或石脑油)通过分离出非期望的物质如硫以及可能通过将在该过程中送回的物质流混入进料(烃进料)而进行预处理，其连同工艺蒸汽一起引导通过设置在蒸汽重整器的燃烧室(Feuerraum)中的重整器管。在重整器管中，其内表面具有催化活性或者其完全或至少部分地在燃烧室的范围内用由合适的催化剂材料制成的填充料或催化活性的结构化填充物填充，在吸热重整反应中产生富含氢的、包含一氧化碳的合成粗煤气，由此在后续的工艺步骤中获得包含氢和/或一氧化碳的气体产品，例如纯氢。
通常通过燃烧器提供重整反应所需的能量，其热的烟气被排放至燃烧室中。烟气通过辐射和对流而将一部分在其中所含的热量转至重整器管，然后其虽然进行冷却，但总是仍然以热状态经由烟道(Rauchgaskanal)排出，在其中设置有由多个热交换器组成的废热系统(Abhitzesystem)。经由热交换器由烟气进一步取走热量，例如用于预先加热起始物质，或者用于产生工艺蒸汽，因而在其最终经由烟囱排放至大气时其仅具有在120与200℃之间的温度。
作为工艺蒸汽通常使用过热蒸汽，为了产生过热蒸汽根据现有技术首先将锅炉给水泵送至汽鼓(Dampftrommel)中。预先加热的水通过重力的作用由汽鼓向下流动至设置在蒸汽重整器的烟道中的第一热交换器，并在此与待冷却的烟气方向相反地部分蒸发。在第一热交换器中形成的液体/蒸汽混合物由于其密度较小而向上升高，回到汽鼓中，在其中分离成液态水和饱和蒸汽，其例如以约48巴(a)的压力和260℃的温度存在。将饱和蒸汽继续引导至同样在蒸汽重整器的烟道中但是在第一热交换器上游设置的第二热交换器，可以由此将过热蒸汽作为工艺蒸汽排出。
汽鼓还可以与被称作PGC(工艺气体冷却器)的废热锅炉(Abhitzekessel)相连接，在其中锅炉给水与以热状态由重整器管流出的合成粗煤气方向相反地部分蒸发。
汽鼓是相当大的成本因素，这是因为其必须被构造成压力容器，其在设计、生产和监视方面是复杂的。汽鼓在蒸汽重整器的烟道上方所需的定位导致需要稳定的脚手架构造(Gerüstkonstruktion)，其成本同样归因于汽鼓。
含烃的起始物质通常以不足以被直接送至蒸汽重整器的压力存在。在此情况下，根据现有技术使用机械压缩机，以升高起始物质的压力。
在含烃的起始物质中存在的硫对于用于蒸汽重整的催化剂而言是毒物，因此必须通过分离出硫而对起始物质进行预处理。为此使硫氢化成为硫化氢，然后通过吸附将其去除。为了氢化作用，通常将由合成粗煤气分离出的氢送回，并在用于氢化作用的反应器的上游混入含烃的起始物质。若起始物质处于比送回的氢更高的压力，则必须对送回的物质流进行压缩，为此根据现有技术同样使用机械压缩机。
机械压缩机在购置和运行方面是昂贵的。因为其此外还具有比较高的故障概率并因此冗余地设置，所以其对于蒸汽重整的经济性造成明显负面的影响。
发明内容
本发明的目的是提供所述类型的方法和设备，由此克服现有技术的缺点，以改善蒸汽重整的经济性。
该目的通过以下方式实现，向锅炉给水在高于其临界压力的压力下输入热量，以获得超临界水，然后将其至少一部分量在蒸汽喷射泵(Dampfstrahlpumpe)中用作推进介质，借此压缩烃进料和/或压缩用于形成烃进料的物质。
通过所建议的方法能够，为了压缩烃进料和/或压缩用于形成烃进料的物质，其例如是送回的氢，完全省略掉易出故障、昂贵且通常冗余地设置的机器。蒸汽喷射泵许多年来是现有技术及本领域技术人员已知的。其具有比较简单的构造，不包含可移动的部件，并且是耐用的，因此其能够以比根据现有技术使用的机械压缩机明显更低的成本使用。
用作推进介质的部分的超临界水经由设置在蒸汽喷射泵上游的节流装置或者在蒸汽喷射泵的推进喷嘴(Treibdüse)中减压成为过热蒸汽，其压力能被转换成速度能。针对性地设计和运行蒸汽喷射泵，使得过热蒸汽在推进喷嘴的下游所具有的静压低于烃进料和/或用于形成烃进料的物质的吸入压力，其因此被吸入并且通过由推进喷嘴产生的蒸汽射流进行加速。在紧接着推进喷嘴的扩散器进料锥(Einlaufkonus)中，蒸汽和吸入的物质进行混合，然后在扩散器中使它们重新减速。因为通过减速回收压力能，所以吸入的物质连同过热蒸汽一起以高于其吸入压力的压力离开蒸汽喷射泵。
优选选择用作推进剂的超临界水的压力、温度和质量流量，使得在蒸汽喷射泵中压缩烃进料时形成物质混合物，其由于其组成而满足蒸汽重整的要求和/或具有无需进一步压缩允许被送至蒸汽重整的压力。
为了产生超临界水，可以将锅炉给水的第一部分与热的烟气方向相反地进行加热，其例如由用于蒸汽重整的蒸汽重整器的燃烧室送入，在此其已经放出其一部分明显的热量用于在此处设置的重整器管中进行的吸热重整反应，同时将锅炉给水的第二部分与以热状态由蒸汽重整器流出的合成粗煤气方向相反地进行加热。但是优选全部的锅炉给水在与以热状态由蒸汽重整器流出的烟气的热交换中进行加热。在此情况下有意义的是，将热的合成粗煤气的热量用于预先加热用于在蒸汽重整器中使用的燃烧器的助燃空气(Verbrennungsluft)和/或使在蒸汽喷射泵中压缩时获得的物质混合物过热，然后将其送至蒸汽重整。替代性地或额外地，在蒸汽喷射泵中获得的物质混合物的过热还可以与热的烟气方向相反地进行，其优选为由用于蒸汽重整的蒸汽重整器的燃烧室流出的烟气，然后用于产生超临界水。
用于产生超临界水的设备组件导致比较高的成本，这是因为其必须由高度合金化的特种钢制成，以承受在运行时产生的强大应力，其尤其是通过超临界水的最大压力而增大。为了限制蒸汽重整的成本，建议以超出处于约220巴(a)的锅炉给水临界压力不多于20巴的压力产生超临界水。
在某些情况下，与用于产生过热的用作工艺蒸汽的蒸汽所需相比，为了产生超临界水可以在合适的温度水平提供更多的热量。在此情况下，在根据本发明的方法的改变方案中，将全部可用的热量用于产生超临界水，及将并非用于提供工艺蒸汽所需的部分输出，以将其用于发电和/或用于加热目的(Heizzwecken)和/或用于实施化学反应和/或用作提取剂(Extraktionsmittel)和/或用于消除有毒物质。在根据本发明的方法的另一个实施方案中，将被指定用于输出的部分的超临界水加热至高于被拟定用于获得工艺蒸汽的部分，为此优选使用来自蒸汽重整器的燃烧室的烟气或者热的合成粗煤气。
根据本发明的方法可以用于通过蒸汽重整由许多种含烃的起始物质如天然气、液化气或石脑油获得包含一氧化碳和/或氢的气体产品。
此外，本发明还涉及从由含烃的起始物质形成的烃进料产生包含氢和/或一氧化碳的气体产品的设备，其具有蒸汽重整器以及由锅炉给水产生工艺蒸汽的系统。
所提出的目的是通过以下方式实现的，所述产生工艺蒸汽的系统包括在超临界范围运行的直通锅炉(Zwangsdurchlaufkessel)，其过热器与蒸汽喷射泵相连接，从而可以将在过热器中产生的超临界水作为推进剂在蒸汽喷射泵中用于压缩烃进料和/或压缩用于形成烃进料的物质。
所述蒸汽重整器优选包括具有设置在其中的重整器管的使燃烧器燃烧(brennerbefeuerten)的燃烧室以及烟道，经由烟道可以将冷却的但总是仍然热的烟气由燃烧室排出。针对性地将直通锅炉设置在蒸汽重整器的烟道中，从而可以将由燃烧室排出的烟气的热量用于产生超临界水。
下面应当依照在图1中示意性显示的实施例更详细地阐述本发明。
附图说明
图1所示为其中通过蒸汽重整由含烃的起始物质获得纯氢作为气体产品的设备。
具体实施方式
将含烃的起始物质1，例如天然气、蒸发的液化气或石脑油，分成第一支流2和第二支流3。将第一支流2作为燃料送至蒸汽重整器D用于加热燃烧室F，而将第二支流3与送回的氢4混合并导入处理装置B中，以分离出会在位于下游的设备部件中造成干扰的物质，如硫化合物，并为蒸汽重整器D供应烃进料5。因为烃进料5的压力对于直接导入在约20至30巴(a)下运行的蒸汽重整器D而言过于低，所以将其送至蒸汽喷射泵V以升高压力。
为了产生工艺蒸汽，将去离子水6导入预处理装置(Aufbereitungs-einrichtung)C中，以进行脱气及预处理成为锅炉给水7。随后借助锅炉给水泵P将处于轻微超压下的锅炉给水7施加至超出其临界压力最多20巴的压力，并经由管线8送至设置在蒸汽重整器D的烟道A中的热交换器E1，在此在与热的烟气9的间接热交换中产生超临界水10。将一部分11的超临界水10输出，例如可以在汽轮机(未示出)中用于发电。与此不同，剩余12的超临界水10经由节流装置a减压，其中产生过热蒸汽13，其在蒸汽喷射泵V中用作推进介质，以将烃进料5施加至蒸汽重整所需的压力，同时将其与用作工艺蒸汽的推进介质强烈混合。在此优选以能够以蒸汽重整全部所需的工艺蒸汽量将过热蒸汽13送至蒸汽喷射泵P的压力和温度产生超临界水10，从而可以将离开蒸汽喷射泵V的物质流14无需进一步改变其组成并且仅在与热的烟气15方向相反地在设置在第一热交换器E1上游的第二热交换器E2中过热之后作为过热的进料16导入蒸汽重整器D的重整器管R中。
由在重整器管R中通过蒸汽重整产生的富含氢的合成粗煤气17，在纯化装置G中通过尤其是分离出水和二氧化碳产生主要由氢和一氧化碳组成的合成气18，其在变压吸附器(Druckwechseladsorber)W中分解成纯氢19和主要由一氧化碳组成的残余气20。残余气20在蒸汽重整器D的燃烧室F中燃烧，以提供用于重整反应的能量，而较大部分的纯氢19作为气体产品21排出，将其较小部分4在处理装置B的上游送回起始物质1的第二支流3中。

Claims (10)

1.产生包含氢和/或一氧化碳的气体产品(21)的方法，其中将由含烃的起始物质(1)形成的烃进料(5)连同过热蒸汽(13)一起送至在升高的压力下进行的蒸汽重整(D)，以获得包含氢和一氧化碳的合成粗煤气(17)，由此获得气体产品(21)，其特征在于，向锅炉给水(8)在高于其临界压力的压力下输入热量(E1)，以获得超临界水(10)，然后将其至少一部分量(12)在蒸汽喷射泵(V)中用作推进介质，借此压缩烃进料(5)和/或压缩用于形成烃进料的物质。
2.根据权利要求1的方法，其特征在于，在蒸汽喷射泵(V)中压缩烃进料(5)时形成物质混合物(14)，其由于其组成而满足蒸汽重整(D)的要求和/或其具有无需进一步压缩允许被送至蒸汽重整(D)的压力。
3.根据权利要求1或2的方法，其特征在于，所述锅炉给水(8)在与烟气(9)方向相反的间接热交换中进行加热，预先从该烟气取走热量用于蒸汽重整(D)。
4.根据权利要求1至3之一的方法，其特征在于，在蒸汽喷射泵(V)中压缩烃进料(5)时形成的物质混合物(14)在与烟气(15)方向相反的间接热交换中进行加热，预先从该烟气取走热量用于蒸汽重整反应(D)。
5.根据权利要求1至4之一的方法，其特征在于，以超出锅炉给水(8)的临界压力不多于20巴的压力产生超临界水(10)。
6.根据权利要求1至5之一的方法，其特征在于，将并非作为用于蒸汽喷射泵(V)的推进剂(13)所需部分(11)的超临界水(10)输出，并用于产生电流和/或用于加热目的和/或用于实施化学反应和/或用作提取剂和/或用于消除有毒物质。
7.根据权利要求6的方法，其特征在于，将并非作为用于蒸汽喷射泵(V)的推进介质所需部分(11)的超临界水(10)在其输出之前与待冷却的烟气方向相反地进一步进行加热。
8.根据权利要求1至7之一的方法，其特征在于，使用天然气或蒸发的液化气或蒸发的石脑油作为含烃的起始物质(1)。
9.从由含烃的起始物质(1)形成的烃进料(5)产生包含氢和/或一氧化碳的气体产品(21)的设备，其具有蒸汽重整器(D)以及由锅炉给水(8)产生工艺蒸汽的系统(E1)，其特征在于，所述产生工艺蒸汽的系统包括在超临界范围运行的直通锅炉(E1)，其过热器经由节流装置(a)与蒸汽喷射泵(V)相连接，从而能够将在过热器中产生的超临界水(12)作为推进剂在蒸汽喷射泵(V)中用于压缩烃进料(5)和/或压缩用于形成烃进料的物质。
10.根据权利要求9的设备，其特征在于，所述直通锅炉(E1)被设置在蒸汽重整器(D)的烟道(A)中。
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