CN102992265A - 具有集成式蒸汽产生管束的产氢换热器反应器 - Google Patents

具有集成式蒸汽产生管束的产氢换热器反应器 Download PDF

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CN102992265A
CN102992265A CN201210434505XA CN201210434505A CN102992265A CN 102992265 A CN102992265 A CN 102992265A CN 201210434505X A CN201210434505X A CN 201210434505XA CN 201210434505 A CN201210434505 A CN 201210434505A CN 102992265 A CN102992265 A CN 102992265A
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C·布瓦耶
F·吉鲁迪埃
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IFP Energies Nouvelles IFPEN
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Abstract

本发明描述用于进行吸热反应例如油馏分或醇类的蒸汽重整的换热器-反应器，其集成了蒸汽产生管束，从而提高了热效率。公布了图1。

Description

具有集成式蒸汽产生管束的产氢换热器反应器
发明领域
本发明涉及用于进行吸热反应的换热器-反应器(exchanger-reactors)，该反应例如是蒸汽重整油馏分或醇类以生产合成气。
这类反应器是现有技术已知的，可在专利US4919844，US4690690，WO2003031050和WO03/035242中找到。
以图表示的话，这类换热器-反应器的原理包括：使热的、在反应器入口处可达1200℃的烟道气，围绕着其中正在进行一个吸热反应或一系列普通的吸热反应的一组管道运动。这类换热器-反应器的热效率基本上由烟道气的出口温度决定。
本发明的目的是通过在所述换热器-反应器内部集成入经过适当处理的蒸汽产生管束(steam generation bundle)，从而降低烟道气的出口温度，来提高这类换热器-反应器的热效率。
本文的其余部分将参照天然气的蒸汽重整反应实施例进行说明，因为它是本发明的换热器-反应器内可以进行的典型吸热反应。但是，更普遍地，本发明涉及藉由热烟道气进行加热的任何吸热反应。
蒸汽重整反应发生在很高的温度(典型的是900℃)和加压(典型的是20至30bar)下。这意味着反应要在一组管道内进行，因为考虑到材料的机械性能，这是唯一在经济上可行的解决方式。这类催化反应器因此由多个管道组成，典型地，生产100000Nm3/h氢气的单元具有约200至400个管道。
这些管道由换热器-反应器上游例如外燃烧室所产生的热烟道气加热，或由外燃烧室下游的涡轮机所产生的热气加热，如专利FR2852358中描述的换热器-反应器的情况。
管道可为卡口(bayonet)类型以具有在同一端的反应物入口和产品出口。卡口式管道从换热器-反应器的上圆顶(upper dome)悬挂；这便于对热膨胀的管理。
大型换热器-反应器的一个实施例是专利FR2918904中描述的″HyGenSys″反应器。该换热器-反应器包括密封于大直径(若干米)的外壳中个大量(超过50个)管道，并且在工艺侧(或管程)与烟道气侧(或壳程)之间有高的压差。
为了提高烟道气与内部正在进行吸热反应的卡口式管道之间的换热系数，现有一种解决方式，即，具有高的烟道气循环速度，特别是使烟道气围绕处于被称为烟道管，或更简单地称为烟囱(chimney)的管道(tubes)之中的卡口式管道进行传送，每个烟囱均围绕卡口式管道。
现有技术(FR2918904)中，这类烟囱通过水平板固定及支撑，该水平板固定在换热器-反应器的外壳(shell)壁上。所述外壳可传统地从底部或顶部通过横梁加强，以使其厚度最小化。
热烟道气将其部分能量传递给卡口式管道，但在换热器-反应器出口处仍然很烫(在550℃至700℃之间，并典型的在600℃至650℃之间)。因而热效率不是很高，本发明的目的之一是通过降低烟道气的出口温度来提高该类型换热器-反应器的热效率。
现有技术
换热器-反应器包含高压(典型地，相对压力为2-5bar)烟道气时，当烟道气出口温度超过550℃，将很难连接该烟道气出口。现有技术中，管组(pipework)内部应当是绝热的，以便使法兰处于足够低的温度，但该实施方式意味着管径必须更大，而由于换热器-反应器外壳本身也必须保持较低的温度(典型地，低于300℃)以保持经济上可行，所以管径更大将可能导致换热器-反应器外壳的机械故障。
此外，现有技术的解决方式中，要收集经由换热器-反应器顶部离开的烟道气并降至地平面，以供给通常位于地面上的下游设备(二次燃烧室、或膨胀机、或蒸汽发生器)。但是，烟道气下降管路也应该内部绝热，这使其庞大并昂贵。而且是热损失的一个原因，不利于系统的总效率。
本发明可用于省去烟道气下降管路并提高换热器-反应器的热效率。
附图概述
图1为本发明的换热器-反应器的示意图，示出的蒸汽产生管路包括供应加料头(supply feeder head)9、蒸汽产生管束5、上部收集器7和分离鼓6。
图2是换热器-反应器的截面图，示出了用于工艺过程的卡口式管道的中央空间，以及包含蒸汽产生管道的外围空间。
发明概述
本发明可称之为进行吸热反应的换热器-反应器，包括多个卡口式管道，该管道悬挂在所述反应器的上圆顶(2)上并向下底部(3)延伸，该卡口式管道(4)用于进行吸热化学反应并封闭在外壳(1)中，该外壳(1)包括用于供热给卡口式管道(4)的热烟道气的入口管(E)和至少一个用于换热之后排出冷烟道气的出口管(S)；该换热器-反应器进一步地包括蒸汽产生管束，该蒸汽产生管束由多个基本上垂直的蒸发管(5)组成，该蒸发管(5)也悬挂在该换热器-反应器的上圆顶(2)并向下底部(3)延伸，且包含在外围空间(8)内，该外围空间(8)位于基本上平行于该外壳(1)的垂直壁的内挡板(Bi)与所述垂直壁(1)之间。所述的内挡板(Bi)具有至少一个开口(Oi)，用来将烟道气(10)从该反应器中央输送到该外围空间(8)。用于产生蒸汽的垂直管道(5)通过位于该外围空间(8)下部中的下部加料头(9)供水，垂直管道(5)产生的液体-蒸汽混合物藉由位于反应器换热器的上圆顶(2)上方、且基本上与分离鼓(6)处于同一水平的上部收集器(7)收集。
在本发明的换热器-反应器的第一个变化中，每个蒸汽产生管道(5)由可引导该烟道气环绕该蒸汽产生管道周围的管道围绕。
在本发明的换热器-反应器的第二个变体中，固定于外围空间(8)的壁上的折流板系统使得烟道气(10)基本上垂直于垂直管道(5)运动。
优选地，用来将烟道气从反应器的中央输送到外围空间(8)的开口(Oi)位于内挡板(Bi)的上部。
在本发明的换热器-反应器中，外围空间(8)体积的正确尺寸可表示为小于换热器-反应器总体积的10％，优选小于5％。
本发明的换热器-反应器可特别用于进行油馏分或天然气或醇类的蒸汽重整工艺。
此时，外围空间(8)中的烟道气速度通常在20m/s至80m/s范围内，优选30m/s至60m/s范围内。
本说明书的背景中仍然介绍本发明的换热器-反应器用于油馏分或天然气或醇类的蒸汽重整工艺，该工艺中，烟道气在约1200℃的温度下进入换热器-反应器，并在优选低于400℃的温度下离开所述换热器-反应器。
发明详细说明
本发明可称之为具有提高能效的换热器-反应器，这是因为本发明设置了完全集成入所述反应器中的蒸汽产生管束，即，相对于由卡口式管道束占据的反应器中央而言，该蒸汽产生管束位于外围空间中，从而可以更好地利用(exhaust)烟道气。
本发明的解决方式包括，在烟道气与用于进行工艺过程的化学反应的卡口式管道(4)进行第一次交换之后，冷却该烟道气，从而在其离开换热器-反应器(1)之前，在位于换热器-反应器的外围的空间(8)中产生蒸汽。
为此目的(to this end)，将垂直的蒸汽产生管道(5)安装在换热器-反应器(1)外围于外围空间(8)内，该外围空间(8)一方面由从下底部(3)延伸至上圆顶(2)的基本垂直的挡板Bi限定，另一方面由换热器-反应器的外壳(1)的垂直壁限定。
这些垂直的蒸汽产生管道(5)悬挂于反应器的上圆顶(2)，并向下自由延伸。
垂直管道(5)通过下部的环形加料头(9)供应以由蒸汽鼓(6)提供的液体水，优选蒸汽鼓(6)的设置高度高于换热器-反应器(1)的上部水平面的高度。下部的加料头(9)通过基本垂直的水管路(11)供应以分离鼓(6)的水，该水管路(11)位于外围空间(8)内。
在蒸汽产生管道(5)中，所述水通过与从开口Oi进入换热器-反应器(1)的外围空间(8)并流向出口管S的烟道气(10)进行热交换，而部分被蒸发，典型地，被5％-100％蒸发。
蒸汽产生管道(5)的上部连接至反应器外部的上部收集器(7)，以收集蒸汽或水/蒸汽的混合物，然后供给分离鼓(6)。
烟道气(10)随后冷却至低于400℃，优选300℃-350℃，这意味着其可通过至少一个由标准金属(standard metals)例如不锈钢316制成的法兰S离开换热器-反应器(1)。该法兰S(或这些法兰S)优选位于换热器-反应器的下部。
沿着下底部(3)、沿着挡板Bi朝向工艺的管道方向一侧的壁以及沿着外壳(1)的垂直壁，布置有耐火材料R。
由此形成的用于烟道气(10)进入的外围空间(8)意味着热量损失达到最小。而且，外壳(1)附近较低的烟道气温度意味着沿外壳(1)的垂直壁布置的耐火材料R厚度达到最小。
蒸汽产生管道(5)可具有外部翅片，以提高与烟道气的换热系数(coefficient of exchange)。
下部的环形加料头(9)通过管路(11)供应以来自蒸汽鼓(6)的处于泡点的液态水，或者通过热虹吸管(液态水和被部分蒸发的水之间的密度差)或者通过泵(特别是当蒸汽鼓尚未位于足够的高度时)供应。
下部管路14将分离鼓6的液相连接至上部收集器7。
上部管路13将上部收集器7连接至分离鼓6的蒸汽相(vapourphase)。
烟道气从入口管E进入，延伸通过反应器中央到达内挡板Bi，并穿过内挡板Bi上提供的至少一个开口Oi进入含有该蒸汽发生管道5的外围空间8，然后通过位于外壳1下部的出口管S离开所述外围空间8。该开口Oi优选位于挡板Bi上部，如图1所示。
为了实现烟道气10与蒸汽发生管道5之间的强制换热，可安装折流板(图1和2未示出)以迫使烟道气10必须穿越过管道5而不是沿着其运动。
在另一个具体实施方式中，蒸汽发生管道5可自身位于管道组(tubes)(图1和2未示出)中，其引导烟道气10以加速所述烟道气并加强其与蒸汽发生管5的热交换。
换热管束(exchange bundle)5可也用于使蒸汽过热。
发明实施例
实现本发明的实施例之一是生产100,000Nm3/h纯氢气的装置(unit)。为了实现该产量，HyGenSys反应器由301个15米高的催化管组成。
所述管道之间的间距为450mm。工艺所需的部分蒸汽被认为是由连接到蒸汽鼓且用作热虹吸管的反应器的内部换热器所产生的。
蒸发所需热量为30MW。该工艺在反应器入口处产生400T/h流速、3bar绝对压力的烟道气。
在具有催化管道的换热段出口处，烟道气温度为600℃。
该蒸发段出口处的烟道气温度为375℃。
该蒸发段具有50mm的外直径和44mm的内直径。
该蒸发管道位于反应器外围120mm宽的环形区中。所述管道之间的烟道气速度为92m/s。
总体换热系数为285W/m2/℃，并且换热需要提供210个与催化管相同高度的管。
管道之间的间距为134mm。
反应器内直径(不包括耐热材料)为9m，没有蒸发段时为8.76m。因此，通过集成入蒸汽产生管束而带来的额外体积为5.2％，并且直接与烟道气的出口温度相关的能量效率为32％。

Claims (7)

1.进行吸热反应的换热器-反应器，其包含悬挂在所述反应器的上圆顶(2)上并向下底部(3)延伸的多个卡口式管道(4)，该卡口式管道(4)用于进行吸热化学反应并封闭在外壳(1)中；该外壳(1)包含供热给该卡口式管道(4)的热烟道气的入口管(E)和至少一个用于换热之后排出冷烟道气的出口管(S)；该换热器-反应器进一步包含蒸汽产生管束，该蒸汽产生管束由多个垂直管道(5)构成，该垂直管道(5)也悬挂在该换热器-反应器的所述上圆顶(2)上，且包含在外围空间(8)内，该外围空间(8)位于基本上平行于外壳(1)的垂直壁的内挡板(Bi)与所述垂直壁(1)之间；所述的内挡板(Bi)具有至少一个开口(Oi)，用于将烟道气(10)从该反应器的中央输送到该外围空间(8)；用于产生蒸汽的该垂直管道(5)通过位于外围空间(8)下部中的下部加料头(9)供以水，来自所述垂直管道(5)的所述的液体-蒸汽混合物在位于该反应器换热器的上圆顶(2)上方的上部收集器(7)中收集，所述下部管路(14)将分离鼓(6)的液相连接至上部收集器(7)，以及所述上部管路(13)将上部收集器(7)连接至分离鼓(6)的蒸汽相。
2.如权利要求1所述的换热器-反应器，其中每个蒸汽产生管道(5)由具有基本上垂直壁的与所述蒸汽产生管道同轴的管道围绕，以引导烟道气(10)环绕该蒸汽产生管道(5)。
3.如权利要求1所述的换热器-反应器，其中固定于外围空间(8)的壁上的折流板系统使得烟道气(10)基本上垂直于垂直管道(5)运动。
4.如权利要求1所述的换热器-反应器，其中外围空间(8)的体积小于该换热器-反应器总体积的10％，优选小于5％。
5.如权利要求1所述的换热器-反应器，其中用来将烟道气从反应器的中央输送到外围空间(8)中的开口(Oi)位于所述内挡板(Bi)的上部。
6.使用权利要求1所述的换热器-反应器对油馏分或天然气或醇类进行蒸汽重整的方法，其中外围空间(8)中烟道气的速度在20m/s至80m/s范围内，优选在30m/s至60m/s范围内。
7.使用权利要求1所述的换热器-反应器对油馏分或天然气或醇类进行蒸汽重整的方法，其中所述烟道气在约1200℃的温度下进入换热器-反应器，并且在低于400℃的温度下离开所述换热器-反应器。
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