CN101331081A - 冷却热烟气流的方法 - Google Patents

冷却热烟气流的方法 Download PDF

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CN101331081A
CN101331081A CNA2006800472398A CN200680047239A CN101331081A CN 101331081 A CN101331081 A CN 101331081A CN A2006800472398 A CNA2006800472398 A CN A2006800472398A CN 200680047239 A CN200680047239 A CN 200680047239A CN 101331081 A CN101331081 A CN 101331081A
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W·J·德维里德
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Abstract

用于冷却包含水蒸汽和二氧化碳的热烟气流的方法，该方法包括：(a)在热烟气流和冷却水流之间进行换热，使热烟气流冷却为在其温度下其中至少部分水蒸汽冷凝的冷却气流，和使冷却水流升温；(b)将冷凝的水蒸汽和冷却水流混合，得到混合水流；(c)使冷却气流与混合水流分离；(d)通过与来自大气中的空气接触以及通过蒸发部分混合水流，冷却该混合水流；(e)使用混合水流中任意未蒸发的且经过冷却的水的至少一部分作为在步骤(a)中用于冷却热烟气流的冷却水流的至少一部分；和(f)将步骤(e)中未使用的混合水流的任意未蒸发的且经过冷却的水储存起来，以及随后使用该储存水作为步骤(a)中冷却水流的至少一部分。

Description

冷却热烟气流的方法
技术领域
本发明提供了冷却包含水蒸汽和二氧化碳的热烟气流的方法，特别是来自蒸汽甲烷重整器的热烟气流，更特别但并非唯一地是来自费-托工艺中所用的蒸汽甲烷重整器的热烟气流。
背景技术
费-托工艺可以用于将烃质原料转化为液态和/或固态烃。该原料(例如天然气、伴生气和/或煤层甲烷、残余(粗)油馏分或煤)在气化器中(任选与重整单元相结合)转化为氢气和一氧化碳的混合物。该混合物通常称作合成气体或合成气。
然后将该合成气进料到费-托反应器中，在其中在一个步骤中经适合的催化剂在高温和高压下转化为范围为甲烷到包含最多200个碳原子或者在特定情况下甚至更多个碳原子的高分子量化合物的链烷烃化合物。
费-托反应器中生成的烃通常进入加氢单元，任选地进入加氢异构化/加氢裂化单元，然后进入蒸馏单元。
气化器产生的氢气与一氧化碳之比通常小于费-托反应器中优选的最佳比值。可以通过例如将甲烷和蒸汽转化为氢气：一氧化碳之比为约5∶1-7∶1的合成气的蒸汽甲烷重整器(SMR)来提高气化器合成气中的氢气浓度。该SMR合成气可以用于在来自气化器的合成气进入费-托反应器之前提高其相对氢气含量。通常，SMR还为用于与费-托工艺集成或相关的其它单元或工艺(例如加氢单元)提供足够的氢气。
该蒸汽重整反应是吸热反应，该反应所需的热量通常由燃料气体燃烧提供。由此生成燃烧废气或烟气。由蒸汽甲烷重整器或燃气轮机生成的烟气通常包含水蒸汽、二氧化碳、一氧化碳、氮气、任选的少量C2-C6烃和其它气体。可以从该烟气中将各组分特别是二氧化碳分离出来用于后面的隔离。
在现有技术中，描述了很多用于从烟气或燃烧废气中分离二氧化碳的方法。例如在EP551876中描述了用于从离开锅炉的燃烧废气中除去并回收二氧化碳的方法。EP551876中的方法旨在减少由于二氧化碳的回收导致的总发电效率的降低。
在分离二氧化碳或其它组分之前，通常使用水冷却该烟气。该冷却方法导致水蒸发，因此必须连续添加纯的补充水。补充水的供应为该方法增加了成本，特别是在水的获得有限的炎热气候中。
发明内容
本发明的一个目的是降低用于冷却热烟气的方法中水的消耗。
因此，本发明提供了用于冷却包含水蒸汽和二氧化碳的热烟气流的方法，该方法包括：
(a)在热烟气流和冷却水流之间进行换热，使热烟气流冷却为在其温度下其中至少部分水蒸汽冷凝的冷却气流，和使冷却水流升温；
(b)将冷凝的水蒸汽和冷却水流混合，得到混合水流；
(c)使冷却气流与混合水流分离；
(d)通过与来自大气中的空气接触以及通过蒸发部分混合水流，冷却该混合水流；
(e)使用混合水流中任意未蒸发的且经过冷却的水的至少一部分作为在步骤(a)中用于冷却热烟气流的冷却水流的至少一部分；和
(f)将步骤(e)中未使用的混合水流的任意未蒸发的且经过冷却的水储存起来，以及随后使用该储存水作为步骤(a)中冷却水流的至少一部分。
使用本发明的方法，在空气温度相对较低时(例如在夜晚)，可以得到多余的未蒸发的水并将其储存，当空气温度相对较高时(例如在白天)可以将其使用。因此本发明提供的方法节省了水的消耗，这在炎热气候中是特别有用的。
附图说明
在图1中，示出了用于蒸汽甲烷重整烟气的冷却回路的流程图。
具体实施方式
在本发明的方法的步骤(a)中，通过热烟气流和冷却水流之间的换热，使该热烟气流冷却为在其温度下至少部分其中的水蒸汽冷凝的冷却气流，和使冷却水流升温。
该热烟气流可以是任意烟气流，优选是选自燃气轮机烟气、炉子烟气、热油炉烟气、预热器烟气或重整器烟气的烟气流，更优选为蒸汽甲烷重整器烟气。
该热烟气流优选具有在120-360℃范围内的温度，更优选在160-200℃范围内。
该热烟气流通常包含2-30％的二氧化碳，优选3-15％的二氧化碳。该热烟气流中二氧化碳的比例随至少部分燃烧以产生热烟气流的燃料气体混合物中二氧化碳的比例变化。例如，可以将来自变压吸附单元的废气(其包含二氧化碳)添加或不添加到燃料气体中，如果添加，通常将会提高燃料气体混合物中所含的二氧化碳的比例，因此也提高了热烟气流中二氧化碳的比例。
优选地，步骤(a)中的换热是通过热烟气流和冷却水流的直接接触实现的。替代地，可以应用间接冷却。
优选地，该冷却水流基本为水，更优选为100％的水。在与热烟气换热之前，该冷却水流优选处于环境温度下。
将换热步骤(a)中冷凝的水蒸汽与加热的冷却水流混合，生成混合水流和冷却气流。步骤(b)中生成的混合水流优选具有在30-80℃范围内的温度，更优选在40-70℃范围内。
在本发明的方法的步骤(d)中，通过使混合水流与来自大气中的空气接触，并通过该混合水流的部分蒸发，来冷却该混合水流。优选地，步骤(d)中的冷却是通过将混合水流与空气在冷却塔中直接接触而实现的。
在冷却步骤(d)中未蒸发的混合水流的至少一部分用作步骤(a)中冷却水流的至少一部分。将该混合水流中多余的经过冷却的未蒸发的水(即未用作步骤(a)中冷却水流的部分)储存起来，和随后用作步骤(a)中冷却水流的至少一部分。
通常在步骤(a)中冷凝的水蒸汽量大于步骤(d)中蒸发的水量的情况下，将该混合水流中一部分未蒸发的且经过冷却的水储存在储罐中，通常适于在从热烟气流中冷凝的水蒸汽量小于步骤(d)中蒸发的水量的时候使用。
通常，步骤(d)中蒸发的水量取决于空气的温度，和该空气温度取决于任何特定时刻的主要天气条件和白天时间。特别地，通常在24小时周期内空气温度从夜晚时相对冷的温度变化到白天时相对热的温度。这种轮流变化又会造成蒸发的水量的变化。在一些气候中白天和夜晚的温差可能大于20℃，有时大于30℃，有时大于40℃。因此，在夜晚时间蒸发的水量通常小于在白天时间蒸发的水量。
因此，通常可以在具有相对低的空气温度的时间段内生成多余的未蒸发水并将其储存起来，并可以在空气温度相对高的时间段内使用。
优选地，该方法是至少24小时的连续工艺，其应当优选至少包括白天和晚上。
可以向该方法中添加水以补充蒸发的水。添加的水量可以根据热烟气流中的水量以及根据储罐中的水量而变化。通常，在可获得时，优先使用来自该罐的水添加到该工艺中。
在步骤(c)中与混合水流分离的冷却气流可以进一步处理，以除去和回收其二氧化碳含量。优选地，该二氧化碳作为包含至少80％二氧化碳、更优选包含至少90％二氧化碳的浓缩物流回收。
为了回收冷却气流中的二氧化碳含量，例如可以使用溶剂萃取技术。使用有机溶剂或有机溶剂的水溶液用于从气流中除去二氧化碳是已知的。例如参见A.L.Kohl和F.C.Riesenfeld，1974，GasPurification，2nd edition，Gulf Publishing Co.Houston and R.N.Maddox，1974，Gas and Liquid Sweetening，Campbell PetroleumSeries及EP551876。优选地，在连续工艺中使用可再生的吸收溶剂。
冷却气流(特别是作为浓缩的二氧化碳流回收的二氧化碳)可以用于强化的油采收，以从地下储层中采收烃。替代地，从冷却气流中回收的二氧化碳可以隔离在地下地层中。
通常，在用于从地下储层中采收烃或隔离之前，升高该回收的二氧化碳流的压力。优选地，将该压力升高到足以使该二氧化碳流进入地下地层的水平。通常，在增压过程中将该捕集的二氧化碳流进一步冷却。
本发明的冷却方法有利地用于冷却来自蒸汽甲烷重整单元的烟气，该蒸汽甲烷重整单元用于在费-托装置中由蒸汽和甲烷制备富含氢气的合成气。
费-托合成是本领域技术人员所公知的，和包括通过将氢气和一氧化碳的气态混合物在反应条件下与费-托催化剂接触而由该混合物合成烃。
附图详述
现在将仅以实施例的方式参照图1对本发明的方法进一步描述。图1是描述蒸汽甲烷重整烟气的冷却回路的流程图。
在图1中，示出了包含第一冷却器11、冷却塔12和储罐13的冷却回路10。该冷却回路10用于冷却包含二氧化碳和水蒸汽的热蒸汽甲烷重整(SMR)烟气14。如下面更详细描述的，烟气中的大部分水从烟气流中除去，留下温度降低的包含二氧化碳、其它气体和少量水的物流15。然后物流15可以进入二氧化碳除去和回收工艺(未示出)，例如使用包含胺的溶剂的溶剂萃取工艺。
使用水来冷却SMR烟气，使得其处于适用于二氧化碳捕集的温度。水也会从冷却回路10中损失，特别是从冷却塔12中损失，因此会必须添加补充水16。从冷却塔12中损失的水量随着主要温度而变化，因为与在温度通常达到最大值的白天冷却塔12中损失的水量相比，在温度通常为最小值时的夜晚在冷却塔12中损失的水要更少。因此，在冷却塔12的下游提供储罐13，用于储存通常在较冷的夜晚时间增加的任何多余水。然后在较热的白天时间可以使用该水，因此节约了所需的补充水16的量。
本发明的方法特别适用于淡水提供昂贵且24小时周期内的温度变化较大的炎热气候中。
仅为了解释的目的，将冷却回路10上不同点处存在的水用系数p和u及变量a和b清楚表示。
参照图1，将包含水蒸汽和二氧化碳的SMR烟气引入第一冷却器11中。通常，该SMR烟气也包含其它气体，例如丁烷、丙烷、一氧化碳和惰性气体例如氮气。该SMR烟气在进入该第一冷却器11之前的温度通常约为160-200℃，和压力约为1-2巴。将温度约为20-60℃的包含uH2O的冷却水流与SMR烟气混合，使SMR烟气中存在的大部分水(pH2O)冷凝，并将SMR烟气冷却到约40-60℃。将冷却的SMR烟气与大部分水分离，尽管会剩余少量水，然后可以进行CO2回收工艺(未示出)。
混合水流(p+u)H2O进入冷却塔12。在到达冷却塔12之前，混合水流(p+u)H2O的温度在30-80℃范围内，优选40-70℃。
在冷却塔12中，通过使用来自大气中的空气17，将混合水流(p+u)H2O冷却到在30-60℃范围内的温度。混合水流(p+u)H2O的一部分a(p+u)H2O蒸发，使剩余的混合水流冷却。从冷凝塔12中蒸发的水的部分a(p+u)H2O取决于来自大气中空气的温度，该空气温度又取决于特定时刻的外部温度。混合水流的一部分b(p+u)H2O在冷却塔12中未蒸发，和进入储罐13。因此a和b的相对值根据空气温度变化，因此在24小时周期内变化，但a+b＝1。
在较冷的时间内，通常在夜晚，冷却塔12中蒸发的水量a(p+u)H2O可能小于在第一冷却器11中从SMR烟气中冷凝的水蒸汽量pH2O。因此，在冷却回路10中将有多余水，可以将其储存在水罐13中。当注入该冷却塔12中的空气的温度较高时，则从冷却塔12中损失的水量a(p+u)H2O可能大于从SMR烟气中冷凝的水量pH2O。因此，需要向冷却回路中添加水。在可获得时该水可以从储罐13取出，仅在储罐13变干或水量不足时才需要添加补充水16，即小于冷却水流所需的量uH2O。
因此，b(p+u)H2O水量进入储罐13，和储存在罐13中的水用作冷却水流并引入第一冷却器11。在储罐13中没有水或水量不足(即小于uH2O)的情况下，将补充水16添加到冷却水流中。
因此，本发明的实施方式的优点在于在24小时周期内需要较少的补充水16。

Claims (11)

1.用于冷却包含水蒸汽和二氧化碳的热烟气流的方法，该方法包括：
(a)在热烟气流和冷却水流之间进行换热，使热烟气流冷却为在其温度下其中至少部分水蒸汽冷凝的冷却气流，和使冷却水流升温；
(b)将冷凝的水蒸汽和冷却水流混合，得到混合水流；
(c)使冷却气流与混合水流分离；
(d)通过与来自大气中的空气接触以及通过蒸发部分混合水流，冷却该混合水流；
(e)使用混合水流中任意未蒸发的且经过冷却的水的至少一部分作为在步骤(a)中用于冷却热烟气流的冷却水流的至少一部分；和
(f)将步骤(e)中未使用的混合水流的任意未蒸发的且经过冷却的水储存起来，以及随后使用该储存水作为步骤(a)中冷却水流的至少一部分。
2.权利要求1的方法，其中所述热烟气流是燃气轮机烟气、炉子烟气、热油炉烟气、预热器烟气、重整器烟气中的任意一种，优选为蒸汽甲烷重整器烟气。
3.权利要求1或2的方法，其中所述热烟气流具有在120-360℃范围内的温度，优选在160-200℃范围内。
4.前述权利要求中任一项的方法，其中步骤(b)中生成的混合水流具有在30-80℃范围内的温度，优选在40-70℃范围内。
5.前述权利要求中任一项的方法，其中在冷却塔中将混合水流与空气直接接触。
6.前述权利要求中任一项的方法，其中在步骤(a)中冷凝的水蒸汽量大于步骤(d)中蒸发的水量的情况下，将混合水流中一部分未蒸发的且经过冷却的水储存在储罐中。
7.权利要求6的方法，其中在步骤(a)中冷凝的水蒸汽量小于步骤(d)中蒸发的水量时使用至少一部分储存在储罐中的水。
8.前述权利要求中任一项的方法，其是经过至少一个夜晚小时和至少一个白天小时、优选经过至少24小时的连续方法。
9.前述权利要求中任一项的方法，其中对冷却气流进行处理以回收其二氧化碳。
10.权利要求9的方法，其中所述二氧化碳被隔离在地下地层中。
11.权利要求9的方法，其中所述二氧化碳用于强化的油采收，以从地下储层中采收通常为液态的烃。
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