CN106762041A - 具有NOx捕集功能的船舶柴油机催化还原装置 - Google Patents
具有NOx捕集功能的船舶柴油机催化还原装置 Download PDFInfo
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- 238000006722 reduction reaction Methods 0.000 claims abstract description 24
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
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- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 claims 1
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
- F01N3/0842—Nitrogen oxides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
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- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
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- Y02T10/12—Improving ICE efficiencies
Abstract
一种具有NOx捕集功能的船用柴油机催化还原装置，包括上游进气管、下游进气管、排气管、NOx捕集器、出气装置、尿素喷管和选择催化还原罐体，本发明无须通过外部热源对催化还原装置进行加热，解决了船舶柴油机在起动初期和低负荷工况下NOx排放的问题。
Description
技术领域
本发明涉及柴油机排放污染控制，特别是一种能够减少船舶柴油机在起动初期或低负载工况下NOx排放的催化还原装置。
背景技术
船舶发动机主要以柴油机为主，虽然柴油机的快速发展促使国际远洋航运业迅速壮大，但是船舶柴油机排放物造成的污染对全球环境造成了很大破坏。因此国际海事组织对于船舶柴油机排放的要求日趋严格，尤其是NOx。目前减少船舶NOx排放的主要方法有如下几种：一是燃油控制技术，二是燃烧控制技术，三是进气控制技术，四是选择催化还原技术(Selective Catalytic Reduction,以下简称为SCR)。其中第四项技术属于机外净化技术，被广泛用于船舶柴油机的尾气后处理。
选择催化还原技术是指利用催化剂在氧气存在的情况下，使用还原剂有选择的将废气中的NOx还原成N2和H2O以减少NOx排放。目前绝大多数的SCR系统使用尿素作为还原剂，通过尿素溶液的蒸发、热解和中间产物HNCO的水解形成NH3来还原NOx。
但是，该技术使用的催化还原材料最佳反应温度一般在280～420℃的范围内，在船舶柴油机起动初期或低负载工况下，SCR装置往往无法达到这个温度。以MAN公司某6S350MEB柴油机为例，其25％负荷下排气温度为280℃，仅仅达到催化剂活化阈值温度，因此在起动初期无法使SCR装置发挥作用，未被净化的NOx将直接排入大气中。如若使用加热炉帮助SCR装置快速升温，则需要考虑额外的装置布局，同时增加能量消耗。
发明内容
本发明的目的在于，克服上述现有船舶柴油机SCR技术的不足，提供一种具有NOx捕集功能的船舶柴油机催化还原装置，以减少船舶柴油机起动初期或低负载工况下NOx的排放。
本发明是通过以下技术方案来实现的：
一种具有NOx捕集功能的船用柴油机催化还原装置，其特点在于包括上游进气管、下游进气管、排气管、NOx捕集器、出气装置、尿素喷管和选择催化还原罐体，所述的NOx捕集器和出气装置上下地被封装在选择催化还原罐体的中间底部，所述的NOx捕集器经所述的出气装置与所述的选择催化还原罐体相通，所述的尿素喷管均匀布置在所述的选择催化还原罐体的下底面上，所述的上游进气管和下游进气管相连后穿过所述的选择催化还原罐体的顶部并与所述的NOx捕集器连通，所述的排气管与所述的选择催化还原罐体的顶部连通，所述的选择催化还原罐体内部布置若干层催化剂。
所述的下游进气管具有较高的导热系数，能够将尾气中的热量迅速传递给催化还原罐体中的催化剂。
所述的NOx捕集器内部装有高效吸脱的BaZSM-5或NaZSM-5分子筛为载体，该NOx捕集器的内壁上涂有吸附剂涂层能够在低温时快速地吸附NOx，并在高于280℃的温度下脱附NOx。
所述的尿素喷管在所述的NOx捕集器达到脱附温度时，将向选择催化还原罐体中喷射尿素溶液。
将上下游进气管与NOx捕集器封装在选择催化还原罐体底部，柴油机起动初期的高温尾气从上下游进气管进入NOx捕集器的过程中，对选择催化还原罐体内的催化剂进行加热，助其迅速达到最佳催化温度；同时NOx捕集器对尾气中的NOx进行吸附，并且捕集器的温度也同时提升，当达到合适温度时，捕集器中的NOx脱附，并与尿素溶液热解气体NH3进入达到活化温度的催化剂中，完成催化还原反应，最终达到船舶柴油机起动初期或低负载工况下减少NOx排放的目的。
本发明的NOx捕集技术原理是：使用BaZSM-5或NaZSM-5分子筛为载体，这类分子筛具有均匀的微孔、较大的比表面积和孔容积，微孔孔径大约为NOx分子直径的2～6倍，且具有碱性离子Ba2+或Na+，使其在30℃～350℃都能对NOx进行较好的吸附；重要的是，这类分子筛由于吸附能力较强，所以脱附温度也往往高于催化剂的活化温度(280℃)。另外，可在载体上增加吸附剂涂层以提高分子筛对NOx的吸附性能，吸附剂涂层可考虑使用诸如CaO-Beta之类可在较低温度下针对NOx进行物理和化学吸附的材料。
本发明的积极效果在于：
利用分子筛和吸附剂涂层可捕集NOx排放，并利用尾气温度加热选择催化还原反应所需的催化剂温度，以及合理匹配尿素溶液喷射时刻来减少船舶柴油机起动初期或低负载工况下的NOx排放，与普通的SCR装置相比，有着结构简单、成本低、不需要额外能耗的优点。
附图说明
图1是本发明船舶柴油机催化还原装置外观示意图；
图中：1-上游进气管、3-排气管、6-尿素喷管(下端)、7-选择催化还原罐体。
图2是本发明船舶柴油机催化还原装置内部结构示意图；
图中：2-下游进气管、4-NOx捕集器、5-出气装置、6-尿素喷管(整体)、8-催化剂。
图3是分子筛吸附NOx示意图；其中(a)是吸附质分子在粒子表面的流体界面膜中扩散，(b)是吸附质分子的细孔扩散和表面扩散，(c)是吸附质分子被吸附在细孔内的吸附点上。
图4是分子筛或催化剂载体和涂层结构示意图。
图中：9-BaZSM-5或NaZSM-5分子筛载体、10-吸附剂涂层
具体实施方式
以下结合说明书附图，对本发明做进一步的详细说明。
图1是本发明船舶柴油机催化还原装置外观示意图，图2是本发明船舶柴油机催化还原装置的内部结构示意图，由图可见，本发明具有NOx捕集功能的船用柴油机催化还原装置，包括上游进气管1、下游进气管2、排气管3、NOx捕集器4、出气装置5、尿素喷管6和选择催化还原罐体7，所述的NOx捕集器4和出气装置5被封装在所述的选择催化还原罐体7中底部，所述的NOx捕集器4经所述的出气装置5与所述的选择催化还原罐体7相通，所述的尿素喷管6均匀布置在所述的选择催化还原罐体7的下底上，所述的上游进气管1和下游进气管2穿过选择催化还原罐体7的顶部并与所述的NOx捕集器4连通，所述的排气管3与所述的选择催化还原罐体7的顶部连通，所述的选择催化还原罐体7中内部布置若干层催化剂8。
上游进气管1、排气管3和尿素喷管6被密封安装在选择催化还原罐体7上，尾气经过下游进气管2后进入NOx捕集器4中，两者的外部材料都具有良好的导热性，可使尾气在流动的同时快速加热选择催化还原罐体7中的催化剂8，此时流出NOx捕集器4的气体中不含有NOx，并且也能够对催化剂8进行加热。NOx捕集器4的脱附温度一般在350℃以上，此时催化剂8的温度与之近似，介于催化剂最佳反应温度区间内；此时从NOx捕集器4中脱附的NOx流经所述的出气装置5，与尿素喷管6喷出的尿素溶液相遇；尿素溶液在高温尾气的作用下主要发生下列(1)～(4)化学反应，反应后大量的NOx被净化，经排气管3进入增压器中。
(1)尿素溶液蒸发：
(NH2)2CO(aq)→(NH2)2CO(l or g)+6.9H2O(g)
(2)尿素热解：
(NH2)2CO(l or g)→NH3(g)+HNCO(g)
(3)氢氰酸水解：
HNCO(g)+H2O(g)→NH3(g)+HNCO(g)
(4)催化还原反应：
4NH3+4NO+O2→4N2+6H2O
4NH3+2NO+2NO2→4N2+6H2O
4NH3+6NO→5N2+6H2O
4NH3+3NO2→3.5N2+6H2O
图3是分子筛吸附NOx示意图，吸附主要分为三个基本阶段：
(a)是吸附质分子在粒子表面的流体界面膜中扩散；
(b)是吸附质分子的细孔扩散和表面扩散，细孔扩散是吸附质分子在细孔的内部扩散，表面扩散是在孔壁上的吸附质分子在孔内的壁面上从一个吸附位转移到相邻的吸附位上；
(c)是吸附质分子被吸附在细孔内的吸附点上。
图4是分子筛或催化剂载体和涂层结构的示意图，图中9为BaZSM-5或NaZSM-5分子筛载体，10为吸附剂涂层，上方图为蜂窝孔型，其吸附剂涂覆在载体孔的内壁，这种蜂窝状通道大大增加了废气与吸附剂的接触，并减小了背压，具有较好的净化性能；下方图为球体颗粒型，其吸附剂涂敷在球状颗粒载体的表面，这种球状颗粒比表面积较大，易于填装，价格也较为低廉。在实际中常使用这两类方式布置捕集器或催化还原器，不过需要考虑两种填充床产生的气阻进行合理设计。
Claims (4)
1.一种具有NOx捕集功能的船用柴油机催化还原装置，其特征在于包括上游进气管(1)、下游进气管(2)、排气管(3)、NOx捕集器(4)、出气装置(5)、尿素喷管(6)和选择催化还原罐体(7)，所述的NOx捕集器(4)和出气装置(5)被封装在所述的选择催化还原罐体(7)的中间底部，所述的NOx捕集器(4)经所述的出气装置(5)与所述的选择催化还原罐体(7)相通，所述的尿素喷管(6)均匀布置在所述的选择催化还原罐体(7)的下底面上，所述的上游进气管(1)和下游进气管(2)穿过选择催化还原罐体(7)的顶部并与所述的NOx捕集器(4)连通，所述的排气管(3)与所述的选择催化还原罐体(7)的顶部连通，所述的选择催化还原罐体(7)中内部布置若干层催化剂(8)。
2.根据权利要求1所述的船用柴油机催化还原装置，其特征在于所述的下游进气管(2)具有较高的导热系数，能够将尾气中的热量迅速传递给所述的催化还原罐体中的催化剂。
3.根据权利要求1所述的船用柴油机催化还原装置，其特征在于所述的NOx捕集器(4)内部装有高效吸脱功能的BaZSM-5或NaZSM-5分子筛载体(9)，该NOx捕集器(4)的内壁上涂有吸附剂涂层(10)，能够在低温时快速地吸附NOx，并在高于280℃的温度下脱附NOx。
4.根据权利要求1所述的船用柴油机催化还原装置，其特征在于所述的尿素喷管在所述的NOx捕集器达到脱附温度时，将向所述的选择催化还原罐体中喷射尿素溶液。
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