CN103459791A - 废气净化方法及其设备 - Google Patents

废气净化方法及其设备 Download PDF

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CN103459791A
CN103459791A CN2012800159638A CN201280015963A CN103459791A CN 103459791 A CN103459791 A CN 103459791A CN 2012800159638 A CN2012800159638 A CN 2012800159638A CN 201280015963 A CN201280015963 A CN 201280015963A CN 103459791 A CN103459791 A CN 103459791A
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exhaust gas
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日数谷进
清水香奈
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Hitachi Zosen Corp
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Abstract

本发明提供一种能够持续地进行稳定的废气处理的废气净化方法及其设备。其中的废气净化方法，利用SOX吸附剂，对存在NOX和SOX的燃烧废气进行吸附去除SOX的处理，随后，向处理后的气体添加脱硝用还原剂，利用脱硝催化剂进行脱硝处理，其中，设置多个用于由SOX吸附剂吸附去除SOX的SOX吸附塔（7）、（8），通过在一部分装置中进行SOX吸附处理期间，在其他装置中进行SOX吸附剂的再生，交替地进行SOX吸附和SOX吸附剂再生。

Description

废气净化方法及其设备
技术领域
本发明涉及从船舶用发动机等的燃烧废气中去除氮氧化物和硫氧化物进行净化的方法及其设备。
背景技术
作为去除燃烧废气中所含的氮氧化物（以下简称为“NOX”）的方法，已知作为主流方法的氨SCR法。氨SCR法是，在向废气添加作为还原剂的氨后，通过使其接触主要成分为钒、二氧化钛的脱硝催化剂来将NOX分解为无害的N2和H2O的方法。所述方法已作为固定式发电站的脱硝装置而实用化。
在使用重油等含硫燃料的情况下，废气中存在NOX的同时还存在硫氧化物（以下简称为“SOX”）。在SOX存在的情况下，从防止向催化剂上的硫酸铵（以下简称为“硫铵”）析出的观点出发，脱硝设备的运行温度必须等于高于硫铵的析出温度。硫铵的析出温度与废气中的SO3和NH3的浓度有关。所述关系示于图2。如图2所示，可以看出若SO3和NH3的浓度变高，则硫铵的析出温度变高。
在设置有固定式脱硝装置的燃煤锅炉废气中，一般SOX浓度为100ppm，SO3浓度为所述浓度的10%即10ppm。因NOX浓度为500ppm，所以用作还原剂的NH3浓度最大为500ppm。在所述条件下，硫铵的析出温度约为250℃。此时的废气温度通常为300～400℃，比硫铵的析出温度250℃高，因此不会引起向催化剂的硫铵析出，能够维持稳定的催化剂性能。
另一方面，出自将C重油用作燃料的船舶用发动机等的废气，废气中的SOX浓度为1000ppm，NOX浓度也高达1000ppm，硫铵的析出温度高至约280℃。并且，废气温度较低为250℃，因此所述条件下硫铵析出，不能维持稳定的催化剂性能。
为了将氨SCR法适用于存在高浓度的SOX和NOX，且废气温度较低的出自船舶用发动机等的废气，需要将硫铵的析出温度降至等于低于废气温度。如图2所示，硫铵的析出温度由SO3浓度和NH3浓度决定。NH3浓度由废气中的NOX浓度和目标脱硝率决定，因此不能降低所述值，但是通过在脱硝装置上游设置SOX吸附塔，有可能降低SO3浓度。在NOX浓度为1000ppm，废气温度为250℃的情况下，不使硫铵析出的上限SO3浓度约为2ppm。
关于这种废气处理工艺，例如在专利文献1中公开一种干法脱硫脱硝工艺，所述工艺中，在使用了碳质吸附材料的脱硫装置中对含SOX、NOX和催化剂中毒物质的废气进行处理后，添加氨，使其通过填充了TiO2-V2O5类催化剂的低温脱硝装置内以进行脱硝。
专利文献1：特開平07-299331号公報
发明内容
（一）发明要解决的技术问题
一旦SOX吸附剂吸附一定量的SOX，则不可能再吸附等于高于所述量的SOX，因此需要定期地进行再生操作。在专利文献1中，使用碳质吸附材料从上方向下方移动的移动层方式的脱硫反应器以谋求将碳质吸附材料的更换期延长，但是在吸附性能降低的情况下，需要停止上游侧的燃烧设备来进行更换，在应用于不能在停靠港口时以外的时间停止运行的船舶的发动机废气处理时令人不安。
本发明鉴于上述情况而完成，其目的在于提供一种能够持续地进行稳定的废气处理的废气净化方法及其设备。
（二）解决技术问题的手段
为解决上述问题，本发明是一种废气净化方法，由SOX吸附剂对存在NOX和SOX的燃烧废气吸附去除SOX的处理，随后，向处理后的气体添加脱硝用还原剂，使用脱硝催化剂进行脱硝处理，其特征在于，设置多个用于由SOX吸附剂吸附去除SOX的装置，通过在一部分装置中进行SOX吸附处理期间，在其他装置中进行SOX吸附剂的再生，交替地进行SOX吸附和SOX吸附剂再生。
NOX是一氧化氮（NO）、二氧化氮（NO2）、一氧化二氮（N2O）、三氧化二氮（N2O3）、四氧化二氮（N2O4）、五氧化二氮（N2O5）等氮的氧化物的总称。
SOX是一氧化硫（SO）、三氧化二硫（S2O3）、二氧化硫（SO2）、三氧化硫（SO3）、七氧化二硫（S2O7）、四氧化硫（SO4）等硫的氧化物的总称。
作为由SOX吸附剂吸附去除SOX的装置，设想填充有SOX吸附剂的SOX吸附塔。作为SOX吸附剂，列举出例如TiO2、ZrO2或沸石。
上述的SOX再生，可以通过加热至SOX解吸的温度来进行，但是在船舶用发动机中，更优选通过水洗来进行再生。这种情况下，作为水洗用液体优选易获得的海水。
此外，上述方法中，SOX吸附剂再生后、使废气在装填所述SOX吸附剂的SOX吸附去除装置内流通之前，为了去除占据吸附SOX的空间的水分，优选对SOX吸附剂进行干燥。
这种情况下，为了SOX吸附剂的干燥，优选使用与废气进行热交换的加热空气。
通过采用这种再生方法，可以起到不设置新的加热源就可以再生SOX吸附剂的效果。
此外，本发明是一种用于船舶的发动机废气净化设备，其具备脱硝反应器、脱硝用还原剂吹入口、SOX吸附塔，所述脱硝用还原剂吹入口设置在所述反应器上游，所述SOX吸附塔设置在所述吹入口上游，装填有SOX吸附剂，所述废气净化设备的特征在于，并排设置多个所述SOX吸附塔，还包含：用于储存海水以对所述SOX吸附剂进行水洗的海水箱，用于将所述海水供给各SOX吸附塔的泵，用于切换海水流和废气流的阀门，以及热交换器，所述热交换器用于通过使空气与废气进行热交换来加热空气，所述空气用于对通过水洗而再生的SOX吸附剂进行干燥。根据需要可以设置用于海水前处理的设备。
（三）发明效果
本发明设置多个用于由SOX吸附剂吸附去除SOX的装置，通过在一部分装置中进行SOX吸附处理期间，在其他装置中进行SOX吸附剂的再生，交替地进行SOX吸附和SOX吸附剂再生，因此能够提供一种能够持续地、稳定地进行废气处理的废气净化方法及设备。
附图说明
图1为表示本发明的废气净化设备的流程图。
图2为表示硫酸氢铵/硫铵的析出温度与SO3和NH3浓度的关系的图表。
具体实施方式
下面，参照附图，对本发明的废气净化方法及其设备进行详细说明。
图1为表示本发明的废气净化设备的流程图。
从船舶用发动机1排出的含NOX和SOX的废气，经由管路2和从所述管路2分开的管路3、4或5、6，供给第一SOX吸附塔7或第二SOX吸附塔8。废气向第一SOX吸附塔7或第二SOX吸附塔8的分配通过设置在管路3、5上的阀门9、10的打开关闭来控制。也就是说，通过阀门9打开和阀门10关闭，废气只供给第一SOX吸附塔7，通过阀门9关闭和阀门10打开，废气只供给第二SOX吸附塔8。
此外，为了再生第一SOX吸附塔7和第二SOX吸附塔8中的SOX吸附剂，向各SOX吸附塔7、8供给用于进行水洗的海水。储存在海水箱11的海水，通过泵12的驱动海水由管路13通过管路14、4供给第一SOX吸附塔7，且由管路13通过管路15、6供给第二SOX吸附塔8。各管路14、15上分别设置用于打开关闭海水供给的阀门16、17。
此外，为了对由海水进行水洗后的各SOX吸附塔7、8内的SOX吸附剂进行干燥，将加热空气供给各SOX吸附塔7、8。空气是在热交换器18中，通过与已去除SOX和NOX后的净化气体进行热交换而加热后，由管路19经由管路20、4供给第一SOX吸附塔7，由管路19经由管路21、6供给第二SOX吸附塔8。各管路20、21上分别设置用于打开关闭加热空气的流入的阀门22、23。
SOX吸附塔7、8中填充有SOX吸附剂。作为SOX吸附剂，列举出例如TiO2、ZrO2或沸石，但只要能够吸附SOX，则也可以为其他物质。本实施方式中，作为SOX吸附剂填充有TiO2。
从第一SOX吸附塔7下端排出的已去除SOX的废气，经由管路24从所述SOX吸附塔7出来。管路24分开成管路25和26，管路25上设置有阀门27，管路26上设置有阀门28。
从第二SOX吸附塔8下端排出的已去除SOX的废气，经由管路29从所述SOX吸附塔8排出。管路29分开成管路30和31，管路30上设置有阀门32，管路31上设置有阀门33。
管路26和30合流为管路34，在管路34中流通的废气供给脱硝反应器35。
此外，通过管路36向管路34中供给氨。
作为填充于脱硝反应器35的脱硝催化剂，可以列举出例如，TiO2载持钒的催化剂，以及载持钨或钼的催化剂，但只要能够进行NOX的还原处理，则也可以为其他催化剂。本实施方式中，填充了TiO2作为脱硝催化剂的载持钒和钨的催化剂。
从脱硝反应器35出来的已对SOX和NOX进行处理的净化气体，经由管路37通过热交换器18，在这里通过热交换而被冷却后，向外部排出。
接下来，对使用了上述设备的废气处理方法进行说明。
由船舶用发动机1产生的含SOX和NOX的废气，供给第一SOX吸附塔7或第二SOX吸附塔8的任意一个。
第一SOX吸附塔7和第二SOX吸附塔8交替使用，也就是说，在一侧进行SOX吸附期间，另一侧进行SOX吸附剂的再生。
在第一SOX吸附塔7中进行SOX吸附，第二SOX吸附塔8中进行SOX吸附剂再生的情况下，通过打开阀门9，关闭阀门10，废气只供给第一SOX吸附塔7。在此期间，关于第一SOX吸附塔7，阀门16和阀门22关闭。
由第一SOX吸附塔7的SOX吸附剂已去除SOX的废气，通过管路26的阀门28打开，管路25的阀门27关闭，通往脱硝反应器35。
为了第二SOX吸附塔8的再生，通过阀门10、23关闭，阀门17打开，通过泵12的驱动从海水箱中抽出的海水经由管路13、15、16通往第二SOX吸附塔8，通过水洗将第二SOX吸附塔8内的SOX吸附剂的SOX去除。
含SOX的废水经由管路29从第二SOX吸附塔8的下部排出，通过管路30的阀门32关闭，管路31的阀门33打开，经管路31向本废气净化设备外排出，通过未图示的脱硫装置进行脱硫处理后，向外部放出。
通过水洗已去除SOX的第二SOX吸附塔8接下来进行干燥处理。这时，阀门10、17关闭，阀门23打开，经管路19、21、6导入空气。所述空气是通过热交换器18被加热的加热空气，在通过第二SOX吸附塔8内后，经由管路29、31排出。
经过规定时间后切换工序，使第一SOX吸附塔7为再生处理，第二SOX吸附塔8为吸附处理。这时的操作方法根据与上述通过第一SOX吸附塔7进行SOX吸附处理和通过第二SOX吸附塔8进行再生处理相同的操作步骤进行，因此省略详细说明。
出自第一或第二SOX吸附塔7、8的已去除SOX的废气，经由管路36导入氨后，通往脱硝反应器35，在这里进行NOX还原处理。
处理后的净化气体由发热的脱硝反应加热，经由管路37通往热交换器18，在这里通过与用于SOX吸附塔干燥的空气进行的热交换而被冷却，向外部排气。
另外，通过上述内容举例说明了具备两个SOX吸附塔7、8的情况，但也可以同样在具备三个以上的多个SOX吸附塔的情况下使用，属于本发明的范围内。
下面，根据具体实施的实施例对本发明进行以下说明。
实施例1
使用图1所示的测试设备实施废气净化，测定定期进行SOX吸附剂再生时的脱硝率的变化。
使用TiO2作为SOX吸附剂，将TiO2载持钒和钨的催化剂用作脱硝催化剂。以空间速度SV=10,000（1/h）的方式将SOX吸附剂和脱硝催化剂填充至各SOX吸附塔和脱硝反应器，设定SOX吸附塔温度为250℃，设定脱硝反应器温度为220℃。使用海水作为通过水洗再生SOX吸附剂时的液体。为了对水洗后的SOX吸附剂进行干燥使用160℃的空气。
导入SOX吸附塔的气体的组成设为，NO1000ppm、SOX1000ppm、H2O10%、空气平衡。向气体中添加的NH3与NO的比为NH3/NO=0.8。每小时进行一次向各SOX吸附塔的气体切换，测定初始脱硝率和24小时后的脱硝率。
比较例1
图1所示的测试设备中，除了不进行向各SOX吸附塔的气体切换，仅运行一方的SOX吸附塔（没有SOX吸附剂的再生）以外，在与实施例1相同的条件下进行。
结果
初始（测试刚开始后）以及24小时后的脱硝率示于表1中。
表1测试结果
Figure BDA0000389031650000081
可以看出，实施例1中即使是在24小时后也获得了与初始相同的脱硝性能，但是比较例1中在24小时后脱硝性能大大降低。
所述脱硝性能的降低是由于硫铵析出至脱硝催化剂表面，通过本发明抑制硫铵向脱硝催化剂的析出，使获得持续的、稳定的脱硝性能成为可能。
附图标记说明
7、8 SOX吸附塔
35 脱硝反应器

Claims (6)

1.一种废气净化方法，利用SOX吸附剂对存在NOX和SOX的燃烧废气进行吸附去除SOX的处理，随后，向处理后的气体添加脱硝用还原剂，利用脱硝催化剂进行脱硝处理，其特征在于，
设置多个用于由SOX吸附剂吸附去除SOX的装置，通过在一部分装置中进行SOX吸附处理期间，在其他装置中进行SOX吸附剂的再生，交替地进行SOX吸附和SOX吸附剂再生。
2.根据权利要求1所述的废气净化方法，其特征在于，通过水洗再生SOX吸附剂。
3.根据权利要求2所述的废气净化方法，其特征在于，使用海水进行水洗。
4.根据权利要求2或3所述的废气净化方法，其特征在于，SOX吸附剂再生后，使废气在装填所述SOX吸附剂的SOX吸附去除装置内流通之前，使SOX吸附剂干燥。
5.根据权利要求4所述的废气净化方法，其特征在于，在所述干燥中，使用与废气进行热交换的加热空气。
6.一种用于船舶的发动机废气净化设备，其特征在于，具备脱硝反应器、脱硝用还原剂吹入口、SOX吸附塔；所述脱硝用还原剂吹入口设置在所述反应器上游；所述SOX吸附塔设置在所述吹入口上游，装填有SOX吸附剂；
所述SOX吸附塔并排设置多个；
还包含：用于储存海水以对所述SOX吸附剂进行水洗的海水箱，用于将所述海水供给各SOX吸附塔的泵，用于切换海水流和废气流的阀门，以及热交换器，所述热交换器用于通过使空气与废气进行热交换来加热空气，所述空气用于使通过水洗再生的SOX吸附剂干燥。
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