CN111561376A - 借助多级吸附方法净化来自内燃机的含有硫氧化物的废气的方法和设施 - Google Patents

借助多级吸附方法净化来自内燃机的含有硫氧化物的废气的方法和设施 Download PDF

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CN111561376A
CN111561376A CN202010088381.9A CN202010088381A CN111561376A CN 111561376 A CN111561376 A CN 111561376A CN 202010088381 A CN202010088381 A CN 202010088381A CN 111561376 A CN111561376 A CN 111561376A
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exhaust gas
adsorption
stage
channel
adsorber
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拉尔夫·于尔根斯
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Primorion Ltd
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Primorion Ltd
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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Ocean & Marine Engineering (AREA)
  • Treating Waste Gases (AREA)
  • Exhaust Gas After Treatment (AREA)
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Abstract

本发明涉及借助多级吸附方法净化来自内燃机的含有硫氧化物的废气的方法和设施。根据本发明设置的是，在第一级中让废气与吸附器的固态的吸附介质接触，在其中，尤其是使包括二氧化硫和三氧化硫的酸性有害物质化合，随后将废气流导引通过吸附器的第二级，在第二级中，进行对废气流的精细净化，并且将第二级的吸附介质用作第一级内的吸附介质。

Description

借助多级吸附方法净化来自内燃机的含有硫氧化物的废气的 方法和设施
技术领域
本发明涉及一种用于净化来自以含硫的燃料运行的内燃机的、尤其是以重油运行的船用内燃机的废气流的有害物质的方法和设施。内燃机也可以是经高压增压的内燃机。在下文中主要提及的内燃机不应由此受到限制。
背景技术
根据现有技术，内燃机装备有不同的废气后处理系统，以便降低有害物排放。来自船上运行的内燃机的废气的主要的有害物质为：氮氧化物(NOx)、二氧化硫(SO2)、三氧化硫(SO3)、一氧化碳(CO)、二氧化碳(CO2)、未燃烧的碳氢化合物(HC)(如石蜡、醛、烯烃、芳香族物质以及碳黑微粒，碳黑颗粒包含不仅作为固体物质的而且是形式为所谓的“VolatileOrganic Compound(挥发性有机化合物)”(VOC)的碳。此外细尘颗粒也属于此，根据细尘颗粒的粒径，其作为“PM2.5”和“PM10”是公知的。此外还包含有重金属(如钒，镍，铅，锌和镉)以及铝，镁，钴和硅。
船用内燃机是缓慢转动的二冲程发动机，其使用品质为IFO180(IntermediateFuel Oil，中间燃料油)、IFO380、MDO(Marine Diesel Oil，船用柴油)和MGO(Marine GasOil，船用汽油)的重油运行。这些船用内燃机也可以被构造为以相同的重油运行的四冲程发动机。用于PKW(乘用车辆)和LKW(载重车辆)的燃料目前含有的硫含量为10ppm至50ppm，而用于船用内燃机的燃料，例如重质燃料油(Heavy Fuel Oil)HFO，通常具有经有机化合的硫的份额，其高至1000倍，并且可以达到4.5％的体积百分比。此外，船用发动机内使用的重油每升燃料中含有在毫克范围内的重金属的份额。
世界上约有90％的货运量是由以渣油型燃油燃烧的发动机驱动的大型船舶进行的。在此，燃烧了超过3.5亿吨的推动燃料，这造成了形式为硫氧化物、氮氧化物和颗粒物的排放。对此应降低并且最小化这种对于环境的负担。
2008年10月，国际海事组织(Internationale Maritime Organisation)(IMO)修改了MARPOL协议的附则VI，其目的是以降低这些排放(MARPOL＝InternationalConvention for the Prevention of Marine Pollution from Ships，防止船舶造成海洋污染国际公约)。在此，重点是氮氧化物(NOx)、硫氧化物(SOx)和颗粒物(PM)。自2010年1月1日起生效的欧盟指令2005/33要求在港口实施调动的或在码头停留时间超过两个小时的船舶使用具有低于0.1％的硫的推进燃料。该限值也自2010年1月1日起由加利福尼亚州空气资源委员会(California Air Resources Board(CARB))在加利福尼亚州港口实施，并且自2012年起已扩展到24英里区域。
所有法规(MARPOL附则VI，EU指令2005/33，CARB 1和CARB2)也允许在船上运行废气处理设施，以替代使用含硫低的推进燃料，只要废气处理设施可达到等于使用含硫低的推进燃料的排放等价值。
在化石燃料燃烧时，在燃烧过程期间或在废气流中形成有害物质。在船用发动机中所使用的燃料HFO(Heavy Fuel Oil)是来自矿物油工业的提炼过程的残渣产品，并且根据来源包含不同量的硫、钒、镉、铅和其他重金属。硫含量根据来源地区而异。目前，全世界使用的燃料的平均硫含量大约为2.7％重量百分比。在发动机内的燃烧过程期间，与不同的碳氢化合物化合的硫与氧反应形成SO2(大约95％)和SO3(大约5％)。
此外，在燃烧过程期间形成高浓度的氮氧化物(NO和NO2)。与陆地上的情况不同，在陆地上对于燃煤电厂、垃圾焚烧厂、钢铁和水泥厂以及对于LKW和PKW等不同的排放源，排放限值已于多年前生效，而对于航运排放的限值最近才被通过。在2008年10月的MEPC(海洋环境保护委员会)第58次会议期间，作为EPC.176中的一项决议决定逐渐降低推进燃料中硫含量。替选地，废气后处理系统的运行已经被批准。
不同的废气后处理方法已经用于净化来自船上内燃机的废气。WO 2009/149603 A提出了一种废气清洗方法，CN 000102371101A和WO 2007/054615 A同样如此。所有方法都使用海水来分离SOx排放物。WO 2010/026018 A提出了一种干式的脱硫方法，其中，将在船上所要携带的由氢氧化钙制成的颗粒用于脱硫。DE 10 2010 017 563 A1描述了一种多级方法，其中，每个级中均设有分立的反应器单元，并且因此由多个相继接连的反应器构成，这些反应器也可以相互独立地运行。
上述方法的缺点在于，在超过95％的高分离程度的情况下，吸着介质消耗量成指数增长，并且在推进燃料中的硫含量超过2％m/m(混合物组分的质量份额)的情况下，结构体积和重量也成指数变大，从而使得由于空间和成本原因，让这些方法无法在船上经济地运行。
发明内容
本发明的任务是提供一种用于净化来自船用内燃机的废气的废气后处理方法，该废气后处理方法可以在船上运行，并且通过该废气后处理方法可以遵循所要求的排放极限值。
根据本发明此任务通过如下方式解决，即，在第一级中使废气流与吸附器的固态的吸附介质接触，在该第一级中，尤其是使包括二氧化硫和三氧化硫的酸性的有害物质化合，随后将废气流导引通过吸附器的第二级，在该第二级中，进行对废气流的精细净化，并且将第二级的吸附介质用作第一级内的吸附介质。通过此方法能够实现的是，即使在高SOx浓度的情况下，也以低的吸附介质消耗的经济的方式遵循所要求的排放限值。在第一级中实现吸附介质对有害物质的高的装载，而在方法的第二级中使用尚未负载的吸附介质进行精细净化，由此可以遵循所要求的排放限值。
上面主要提及吸附。实际上，这指的是吸附和吸收。颗粒形的吸附介质具有由微孔、中孔和大孔组成的孔系统，其中首先进行吸附。在颗粒的内部则更确切地说发生吸收。因此在下文中所提提及的吸附在此也应被理解为在颗粒内部进行了吸收。
不同的吸附器和吸收器实施方案，例如固定床吸附器、移动床吸附器或流化床吸附器属于烟气净化中的现有技术。考虑到烟气的流动方向地，这些吸附器实施方案作为交叉流反应器、横向流反应器或作为逆流反应器运行。此处使用的吸附器可以实施为横向流反应器。所使用的吸附介质由包含不同质量份额的氢氧化钙、碳酸钙、碳酸钠和/或碳酸氢钠的颗粒构成。吸附介质可以作为移动层以连续的或不连续的输送量流动通过吸附器。作为颗粒成形的吸附介质可以具有立方形的或球形的或碎片状的形状，其粒径在1.0mm至15.0mm之间，并且优选在2.0mm至10.00mm之间，尤其优选在2.0mm至6.0mm之间。
此外，可以进一步设置的是，固态的吸附介质包含有含碳的添加物，尤其是活性碳和/或平炉焦炭，该添加物尤其是具有0.1％至50％的重量百分比的、优选是1.0％至35％的重量百分比的份额。这进一步支持了对废气的净化。在吸附器中发生的化学反应(化学吸着)中，酸性的废气并且尤其是氮氧化物被化合并且被转化为毒性较小的产物。
新鲜的并且未负载的颗粒由未详细描述的存储仓运送到吸附器内，并且在流过吸附器之后被收集并临时存储在未详细描述的残余物仓内。可以在港口中从暂存器移除吸附料。
有利的是，废气流在进入吸附器的第一级时具有在150℃至450℃之间的温度。在此，化学吸着在有利条件下发生。
吸附介质可以连续地首先被引导通过吸附器的第二级并且随后再被引导通过吸附器的第一级。也可行的是，吸附介质不连续地首先被引导通过吸附器的第二级，并且随后再被引导通过吸附器第一级。在这两种情况中实现的是，在第二级中提供用于化学吸着的未负载的并且新鲜的吸附介质以用于精细净化废气。在第一级中，使用在第二级中仅略微负载的吸附介质以用于预净化废气。
在吸附介质不连续地进料的情况下可以设置的是，当更新颗粒时将一定量的未受负载的颗粒输送给第二级，该量至少相应于第一级的颗粒的量。可以设置的是，在第一级和第二级中存在有相同量的吸附介质。以此实现的是，将相同量的低负载的吸附介质导引到第一级内以用于废气的预净化，然后在该第一级中继续加载废气。尤其保证没有颗粒仅被较少地负载。由此可以保持低的吸附介质消耗。
颗粒在吸附器中的停留时间可以通过用于吸附介质的排出机构的排出量和排出速度来调节。在此，可以使用叶轮闸门(Zellenradschleuse)。
用于净化来自废气流的有害物质的设施具有废气管，其被内燃机的废气流过。设置的是，在废气管内存在有至少有一个截止阀，废气管器壁在沿流动方向位于截止阀之前的第一区域内被穿孔以形成第一吸附级，并且在沿流动方向位于截止阀之后的第二区域内被穿孔以形成第二吸附级，被穿孔的区域由连贯的吸附通道覆盖，并且吸附通道被流动通道覆盖，流动通道的内部的且界定了吸附通道的内部的器壁是被穿孔的。以此提供了针对废气的流动路径，使得废气在截止阀关闭时被导引通过第一区域内的穿孔部且向外通过吸附通道进入到流动通道内并从流动通道向内被导引通过吸附通道并且通过第二区域内的穿孔部被导引回到沿流动方向在截止阀之后的废气管内。吸附通道被填充以吸附介质。形成了废气经过吸附介质的强制流动，从而可以实现对废气的净化。
本发明的设施的废气管在此通常是内燃机的已经存在的废气管，其已被相应地加工。因此，设施也可以被事后安装。但是也可以设置的是，在将废气管装入到船内时，就已经安装好相应地被预加工的管区段。
此外可以设置的是，废气管在第一和第二级之间的具有截止阀的区内是不被穿孔的。原则上，第一和第二级也可以直接相继地联接。然而，通过在第一和第二级之间设有不穿孔的区，避免了废气的短路流。
此外可以设置的是，相应于流动通道的内器壁的吸附通道的外器壁在相应于废气管的不被穿孔的区的区内也是不被穿孔的。以此也有利于废气的所希望的流动穿过因此被分离且间隔开的吸附器的两个级。
根据优选的实施方式设置的是，废气管的第一和第二区域沿其圆周并且沿轴向方向是被穿孔的，并且吸附通道和流动通道以套管方式包围两个区域。因此，吸附器以套环方式包围废气管，以此得到废气后处理的节省空间的结构。
尤其可以设置的是，两个区域和截止阀布置在废气管的竖直延伸的区段中，并且吸附通道能从上方被填充以吸附介质，并且在其下侧具有至少一个用于消耗的吸附介质的排出机构，使得基于重力让吸附介质运输通过吸附通道。通过此布置可以省去让吸附介质通过吸附通道的传送器件。尤其是在船舶的情况中，内燃机通常位于船舶的下部区域内。因此，废气管从下向上延伸通过整个船体，从而在多个位置上存在用于套环形的吸附设备的足够的空间。
此外可以设置的是，包围废气管的第一和第二区域的吸附通道的体积基本上是相同的。以此实现的是，在如此形成的第一和第二级内存在相同量的吸附介质。
在吸附通道下端部上的排出机构可以被构造为叶轮闸门。这种类型的排出机构已被证明合适。
根据本发明的另外的实施方案设置的是，沿流动方向在第一和第二区域之间存在两个截止阀，所述截止阀可以被打开以形成旁路。以此，即使例如当吸附通道被阻塞时，也可以维持船舶运行。例如在燃烧有害物质少的燃料或在大海上时，此船还可以在不进行废气后处理的情况下运行。
所提出的吸附器的结构形式是节省空间的，并且因此可以以有利的方式用于具有仅有限的用于废气后处理系统的空间容量的船舶上。另一优点在于，吸附器的此类布置也可以事后被整合在船上。仅要求废气管具有足够长的自由长度，根据本发明的吸附器可以沿该自由长度安装。由于在吸附通道内总是仅存在相对少量的吸附介质，因此不会损害船舶的稳定性和配平性。
通过在废气管内设置可关闭的截止阀而可行的是，例如当燃烧有害物质少的燃料时，在不要求脱硫或脱氮的情况下，释放来自发动机的未被净化的废气。通过旁路也可以避免在吸附器内的废气背压不允许地升高时损害发动机性能。
附图说明
下文根据示意图更详细地解释本发明。其中：
图1示出穿过具有根据本发明的吸附器的废气管的纵截面；和
图2示出穿过根据本发明的吸附器的废气的流动走向。
具体实施方式
在图中所示的废气设施包括废气管10，未示出的内燃设施中产生的废气沿住流动方向11流动通过该废气管。废气管10至少在一个部分区段中竖直地延伸，例如延伸通过也未示出的船体。
在废气管10中存在有两个沿流动方向11相继地布置的截止阀12a、b，通过截止阀可以关闭废气管。在沿流动方向位于前部的截止阀12a之前的第一区域13内，废气管的器壁14被穿孔地构成。在沿流动方向11位于后部的截止阀12b之后的第二区域15中，废气管10的在那里的器壁也被穿孔地构成。这些穿孔沿流动方向11在废气管的能预设的长度上延伸，并且在第一和第二区域中围绕废气管的整个圆周延伸。
沿流动方向相继布置的两个区域13、15被套管形的吸附通道17包围。该吸附通道17其本身被在横截面中呈环形的流动通道18包围。详细而言，如下这样地提供此布置，即，使吸附通道17从上到下是可通过的，并且被填充以颗粒形的吸附介质19。吸附通道17与外部的流动通道18之间的器壁20在与第一和第二区域13、15对置的区域内沿圆周被穿孔地构成。在布置有截止阀12a、b的区21内，这些器壁未被穿孔。
通过此布置利用简单的器件提供了两级的吸附器。废气流过废气管10，并且当关闭截止阀12a、b时将废气导引通过吸附通道17。吸附介质在此横向于流动方向地被流过。随后，使废气通过吸附通道17的外器壁20内的穿孔进入到流动通道18内，并且流过沿流动方向11位于更后方的穿孔通过位于更上方的新鲜的吸附介质19流回到沿流动方向在后部的截止阀12b之后的废气管内。因此，在第一截止阀12a之前的第一区域13形成第一吸附级，而第二截止阀12b之后的第二区域15形成第二吸附级。
吸附介质通过具有在横截面中呈环形的吸附通道17的上端部上的注入开口22被填充到该吸附通道内。吸附介质基于重力而向下移动，并且在下端部上通过可以被构造为叶轮闸门的排出机构23又从吸附通道17被移除。在紧接在注入开口22之后的上部区域内，吸附通道17不会沿圆周被穿孔，并且因此可以被闭合地构造，以便防止废气流过填充区域。
相应的器壁14、20的经穿孔的区段的孔尺寸被如下这样地测定，即，使颗粒形的吸附介质19被可靠地保持在吸附通道内。例如可以设置1.0mm至3.0mm的孔尺寸。
因此，吸附介质19从上到下连续地或不连续地移动通过吸附通道17，而废气首先从下方在第一区域13内并且随后在上部的第二区域15内流过吸附介质19。以此实现了吸附器的两级的实施方案，其中，在沿流动方向位于前方的第一级13内进行对废气的预净化，而在沿流动方向位于后方的第二区域15内进行对废气的精细净化。此布置是非常节省空间的，并且也可以事后被整合在船结构中。
以吸附介质填充吸附器可以例如通过未示出的气动的传送装置进行，通过该传送装置也可以对吸附器进行排空。
总之，得到了在图2中示意性地示出的废气的流动走向。在吸附通道17内的压力升高得过高的情况中，可以完全地或部分地打开截止阀12a、b。然后，使废气在未被或仅部分地被净化的情况下释放到环境中。截止阀12a、b也可以根据所使用的燃料的类型而被打开或关闭。这些措施是容易的，并且能由船上人员轻松执行，并且可以分别与所使用的燃料匹配。
由于两级方法，使得颗粒形的吸附介质几乎完全被加载以有害物质。在此始终可以使用新鲜的且未经负载的吸附介质进行精细净化，从而可以遵循所希望的排放标准值。在吸附通道17的出口处仅抽出饱和的吸附介质，从而得到了更节省的消耗。因此，可以保持低的吸附介质携带量。

Claims (18)

1.用于净化来自以含硫的燃料运行的内燃机的、尤其是以重油运行的船用内燃机的废气流的有害物质的方法，其特征在于，在第一级(13)中使废气与吸附器的固态的吸附介质(19)接触，在所述第一级中，尤其是使包括二氧化硫和三氧化硫的酸性的有害物质化合，随后将所述废气流导引通过所述吸附器的第二级(15)，在所述第二级中，进行对所述废气流的精细净化，并且将所述第二级(15)的吸附介质用作所述第一级(13)内的吸附介质。
2.根据权利要求1所述的方法，其特征在于，所使用的吸附介质(19)由包含氢氧化钙和/或碳酸钙、碳酸钠和/或碳酸氢钠和/或氧化镁和/或氢氧化镁的颗粒构成。
3.根据权利要求1或2所述的方法，其特征在于，所述固态的吸附介质(19)以颗粒化的散积物的形式存在，所述散积物尤其具有1mm至20mm、优选2mm至8mm的粒径。
4.根据前述权利要求中任一项所述的方法，其特征在于，所述固态的吸附介质(19)包含有含碳的添加物，尤其是活性碳和/或平炉焦炭，所述添加物尤其具有0.1％至50％的重量百分比的、优选是1％至35％的重量百分比的份额。
5.根据前述权利要求中任一项所述的方法，其特征在于，在进入所述吸附器的第一级时，所述废气流具有在150℃至450℃之间的温度。
6.根据权利要求1至5中任一项所述的方法，其特征在于，所述吸附介质(19)连续地首先被引导通过所述吸附器的第二级并且随后被引导通过所述吸附器的第一级。
7.根据权利要求1至5中任一项所述的方法，其特征在于，所述吸附介质(19)不连续地首先被引导通过所述吸附器的第二级并且随后被引导通过所述吸附器的第一级。
8.根据权利要求7所述的方法，其特征在于，在更新颗粒时，将一定量的未经负载的颗粒输送给所述第二级，所述量至少相应于所述第一级的颗粒的量。
9.根据权利要求1至8中任一项所述的方法，其特征在于，在第一和第二级内存在有相同量的吸附介质。
10.根据权利要求1至9中任一项所述的方法，其特征在于，所述颗粒在所述吸附器中的停留时间通过排出机构的排出量和排出速度来调节。
11.用于净化来自以含硫燃料运行的内燃机的、尤其是以重油运行的船用内燃机的废气流中的有害物质的设施，所述设施具有至少一个被所述废气流过的废气管(10)，其特征在于，在所述废气管(10)中存在有至少一个截止阀(12a、12b)，废气管器壁(14)在沿流动方向(11)位于截止阀(12a)之前的第一区域(13)内被穿孔以形成第一吸附级，并且在沿流动方向(11)位于截止阀(12b)之后的第二区域(15)内被穿孔以形成第二吸附级，被穿孔的区域由连贯的吸附通道(17)覆盖，所述吸附通道(17)被流动通道(18)覆盖，所述流动通道的内部的且界定了所述吸附通道的器壁(20)是被穿孔，使得所述废气在所述截止阀(12a、12b)关闭时被导引通过所述第一区域(13)内的穿孔部且向外通过所述吸附通道(17)进入到所述流动通道(18)内并从所述流动通道向内被导引通过所述吸附通道(17)并且通过所述第二区域(15)内的穿孔部被导引回到沿流动方向(11)在所述截止阀(12b)之后的废气管(10)内。
12.根据权利要求11所述的设施，其特征在于，所述废气管(10)在所述第一和第二级之间的具有所述截止阀(12a、12b)的区(21)内是不被穿孔的。
13.根据权利要求11或12所述的设施，其特征在于，所述吸附通道(17)的外器壁(20)在相应于所述废气管(10)的未被穿孔的区(21)的区内是不被穿孔的。
14.根据权利要求11至13中任一项所述的设施，其特征在于，所述废气管(10)的第一和第二区域沿其圆周并且沿轴向方向是被穿孔的，并且所述吸附通道(17)和所述流动通道(18)以套管方式包围这两个区域。
15.根据权利要求11至14中任一项所述的设施，其特征在于，两个区域(13、15)和所述截止阀(12a、12b)布置在所述废气管(10)的竖直延伸的区段内，并且所述吸附通道(17)能从上方被填充以吸附介质(19)，并且在所述吸附通道的下侧具有至少一个用于消耗的吸附介质的排出机构(23)，使得所述吸附介质(19)基于重力被运输通过所述吸附通道(17)。
16.根据权利要求11至15中任一项所述的设施，其特征在于，所述吸附通道(17)的包围所述废气管(10)的第一和第二区域的体积基本上是相同的。
17.根据权利要求11至16中任一项所述的设施，其特征在于，所述排出机构被构造为叶轮闸门。
18.根据权利要求11至17中任一项所述的设施，其特征在于，沿流动方向在所述第一和第二区域之间存在有两个截止阀(12a、12b)，所述截止阀能够被打开以形成旁路。
CN202010088381.9A 2019-02-14 2020-02-12 借助多级吸附方法净化来自内燃机的含有硫氧化物的废气的方法和设施 Pending CN111561376A (zh)

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