CN103688033A - 用于减少内燃机排气中的氮氧化物和硫氧化物的方法 - Google Patents

用于减少内燃机排气中的氮氧化物和硫氧化物的方法 Download PDF

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CN103688033A
CN103688033A CN201280016171.2A CN201280016171A CN103688033A CN 103688033 A CN103688033 A CN 103688033A CN 201280016171 A CN201280016171 A CN 201280016171A CN 103688033 A CN103688033 A CN 103688033A
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ammonia
catalyst system
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combustion engine
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CN103688033B (zh
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J·R·托格森
H·特罗勒
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On Shares LP
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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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    • F01N3/2066—Selective catalytic reduction [SCR]
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—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
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    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
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    • F01N2590/00—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines
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Abstract

本发明提供了从贫燃内燃机的排气中减少氮氧化物和硫氧化物的方法。

Description

用于减少内燃机排气中的氮氧化物和硫氧化物的方法
技术领域
本发明大体涉及利用还原剂例如氨和尿素等减少内燃机排气中存在的氮氧化物和硫氧化物的方法。特别地，本发明致力于从用具有高硫含量的燃料运行的发动机排气中去除该化合物。
背景技术
在固定或汽车(stationary and automotive)应用中的排气的氮氧化物排放长期以来都是主要的环境问题。氮氧化物(NOx)和硫氧化物(SOx)的有害影响是众所周知的。
在电力和汽车工业中，尤其是在贫燃发动机的排气中，NOx至氮气(N2)的还原通常是通过使用氨或尿素作为还原剂利用在所谓的选择催化还原(SCR)中的合适催化剂进行的。
在该还原过程中使用的SCR和催化剂属于现有技术，不需要进一步详细描述。
在过去，很少有关注发动机排气中的硫氧化物的去除，显然因为在排气中的硫含量低于现行的要求。在汽车业中的大多数内燃机是使用脱硫燃料为燃料的，排气中的硫含量低于现行的要求，或者对应于本地燃料油中硫含量的高排放是被接受的。
为此，用于固定应用和海洋船只的船上的大型燃烧发动机仍然以具有高硫含量的燃料运行。
例如，对于SCRDeNOx结合供以硫含量高于1％的重质燃料油(HFO)的内燃机，并没有可操作的技术方案。
那些发动机通常装备以涡轮增压器来提高发动机效率。
涡轮增压的燃烧发动机的排气净化(Exhaust gas cleaning)基于如下的原因是有问题的。
氨，作为用于NOx的SCR中的常用还原剂，与也存在于排气中，尤其是HFO供燃料发动机的排气中的硫氧化物反应。反应产物是硫酸铵或硫酸氢氨，如果排气温度低于一定的限度，它们将冷凝在SCR催化剂上并通过与氨接触抑制催化剂。
所述排气的温度典型地在刚从发动机排出后为330到500℃。此温度刚好高于硫酸盐的冷凝温度。
然而相对高的温度意味着，排气中一些SO2经过SCR被氧化成SO3。生成的SO3和在发动机的排出口排气中已经存在的SO3一起，如果不捕集在排气处理装置系列(equipment train)中，会导致酸烟柱(acid plume)的形成。
在经过涡轮增压器的涡轮机后，排气温度下降到低于所述冷凝温度，就会造成上述问题。
因此，本发明的大致目标是提供不存在上述问题的，联合(combined)还原涡轮增压内燃机的NOx和SOx的方法。
发明内容
本发明的主要特征是使排气中的氨量相对于SCR中的消耗的量过量，以在下游设备系列中捕集作为硫酸铵或硫酸氢氨的SO3，或者投放氨来由SCR生成low slip，使得可以在湿洗涤器中捕集作为H2SO4的SO3。
因此，本发明是从贫燃内燃机的排气中减少氮氧化物和硫氧化物的方法，包括将排气与调整量的氨通过催化剂体系，所述催化剂体系包括一种或多种在氮氧化物生成氮气的反应中为活性的催化剂，所述氨原样引入到排气中或者在引入到排气中后、在将所述排气通过所述催化剂体系之前形成；
将这样处理后的排气通过涡轮增压器的涡轮机；和
在下游的排气处理步骤中除去涡轮增压器排气中存在的三氧化硫和/或铵硫(ammonium sulphur)化合物；其中使排气经过在高于铵硫化合物的冷凝温度的温度下的催化剂体系，所述铵硫化合物通过与在排气中的氨反应生成，且其中在经过催化剂体系后，将排气中的氨量调整到少于2ppm体积或者高于10ppm的体积的量。
在具体应用中，在经过催化剂体系后，氨量可以维持少于0.5ppm体积。
通过提供相对NOx量过量的氨，生成了氨流(slip)，生成的SO3可以作为硫酸氢氨(ABS)或者硫酸铵(AS)被捕集。ABS和AS是水溶性化合物，并且可以轻易地通过在洗涤器中用水洗涤而去除。ABS和AS也可以通过使用烟灰吹除(soot blowing)设备去除。
所述洗涤器优选用于SO3捕集。在一个可选择的工作模式中，氨流被维持在最小量以最小化在下游装备中的结垢。
当SCR的氨流维持高于10ppm体积时，硫酸氢氨和硫酸铵在废热锅炉中冷凝，或者在传热表面或者作为气相中的固体颗粒。下游装置中的表面上形成的沉积物可以通过用水清洗和/或在烟灰吹除过程中去除，而所述颗粒物在下游的SOx洗涤器中被去除。
可选择地，氨流被维持低水平(＜2ppm)，这意味着由ABS或AS造成的下游设备的结垢被最小化。SO3随后可以在优选用于SO3去除的SOX洗涤器中去除。
本发明方法中使用的氨可以以气态氨的形式或者利用尿素溶液提供，所述尿素溶液当注射到排气中后分解为氨。
本发明的方法尤其结合两冲程发动机。这类发动机通常用于海洋船只的船上且供以含硫的重质燃料油为燃料。
具体实施方式
海洋船只上的2冲程发动机排出1500ppm(体积)的NOx，750ppm(体积)的SO2和15ppm的SO3(体积)。在通向SCR单元的入口处的发动机排气温度为330至500℃，压力为2至4bar表压。通过涡轮增压器上游的加压的SCR，NOx含量下降到低于300ppm，而形成了附加的30ppm的SO3。SCR单元之后的氨流调整到高于20ppm，这导致硫酸氢氨和硫酸铵形成，并在涡轮增压器下游的废热锅炉中，或者在传热表面或者作为在气相中的固体颗粒而冷凝。在所述表面上形成的沉淀物可以通过定期使用水来清洗锅炉而去除，而颗粒在下游的SOx洗涤器中去除。可选择地，所述氨流被维持在很低的水平(＜2ppm)，这意味着由ABS和AS造成的废热锅炉结垢被最小化。SO3随后可以在优化用于SO3去除的SOx洗涤器中去除。

Claims (7)

1.减少贫燃内燃机的排气中的氮氧化物和硫氧化物量的方法，该方法包括将所述排气与调整量的氨通过催化剂体系，所述催化剂体系包含一种或多种在氮氧化物生成氮气的反应中为活性的催化剂，所述氨原样引入到排气中或者在引入到所述排气中后在将所述排气通过所述催化剂体系之前形成；
将这样处理后的排气通过涡轮增压器的涡轮机；和
在下游的排气处理步骤中除去涡轮增压器排气中存在的三氧化硫和/或铵硫化合物；其中使排气在高于铵硫化合物的冷凝温度的温度下经过催化剂体系，所述铵硫化合物通过与在排气中的氨反应生成，且其中在经过催化剂体系后，将排气中的氨量调整到导致少于2ppm体积或者高于10ppm的体积的量。
2.如权利要求1所述的方法，其中，在通过所述催化体系后，将所述排气中的氨量调整到导致少于0.5ppm体积的量。
3.如权利要求1或2所述的方法，其中，所述内燃机为两冲程发动机。
4.如权利要求1-3任一所述的方法，其中，所述下游排气处理步骤包括使用水来清洗或者洗涤。
5.如权利要求4所述的方法，其中，所述排气处理步骤在废热锅炉和/或湿洗涤器中进行。
6.如权利要求5所述的方法，其中，所述废热锅炉定期地采用水清洗或者通过烟灰吹除清洁。
7.根据权利要求1-6任意一项所述方法用于减少在海洋船只的船上安装的贫燃内燃机的排气中的氮氧化物和硫氧化物的用途。
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