CN103541797A - 检测废气，特别是内燃机废气中所含的含氮化合物的方法 - Google Patents
检测废气，特别是内燃机废气中所含的含氮化合物的方法 Download PDFInfo
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Abstract
本发明涉及检测废气，特别是内燃机废气中所含的含氮化合物的方法，将还原剂注入气体并将其通过催化剂（16）来实现该选择性催化还原处理。根据本发明，该方法包括：向处理单元（24）传输设置在催化剂下游的废气中的气体检测器（18）收集到的信号，该信号代表催化剂出口处的NOx的量（NOx探 测器）；将该信号通过SCR催化剂模型分解成代表催化剂出口处（16）的NOx有效量的值（NOx真实），通过整体模型分解成检测器扰动系数（k）和代表氨的量的值（NH3真实），得到NOx探测器=NOx真实+kNH3真实；从该分解评估系数（k）；当系数（k）大于或等于1时，确定催化剂（16）的下游存在含氮化合物。
Description
技术领域
本发明涉及对废气中所含的含氮化合物进行检测的方法。
更具体地涉及在发动机特别是内燃机的排气管线中循环的废气，但并不限于此。
技术背景
本文所用术语“废气”涵盖了内燃机、固定或安装在机动车辆中的燃料混合物燃烧的结果，以及任意其他类型的燃烧结果，例如来自涡轮或者炉的、在烟囱中循环的烟气。
通常来说，在高温和高氧含量条件下引燃燃料，例如发动机燃料，产生诸如一氧化氮（NO）、二氧化氮（NO2），更通常称作NOx（氮氧化物）之类的气体。
然后这些NOx被排放到大气中，一方面对人体健康有害，另一方面对环境有害，因为它们会导致形成对对流臭氧层产生威胁的烟雾。
因此，需要提供一种方法防止这些NOx排放到大气中，例如在它们形成之后摧毁它们。
已知进行化学处理操作，例如选择性催化还原，称作SCR（选择性催化还原）来摧毁这些NOx。
该操作包括用专用催化剂的还原剂的方法对NOx进行选择性还原。还原被称作选择性的原因在于还原剂还原了NOx，但是不会对要燃烧的混合物中存在的氧气进行还原。
所述还原剂，特别是用于机动车辆内燃机的还原剂，是氨（或者能分解成氨的物质）或者烃类（氧化或未氧化的）或者可部分含有或全部含有一种或多种氧化烃类的烃类混合物。
在采用氨通过SCR对废气进行处理的情况下，所使用的氨基试剂以固体复合物的形式或者以液体前体（例如尿素的水溶液）的形式储藏。
在尿素形式的液体前体的情况下，在催化剂的上游将其注入到废气流中。在注入之后，通过对气体进行加热将尿素中所含的水蒸发掉，尿素分解成氨和异氰酸。
对于采用（氧化或未氧化的）烃类通过SCR进行处理的情况，在排气处注入所述烃类或者由燃烧得到所述烃类，例如在后期后注入的情况下，并且它们与废气中所含的NOx反应。在该反应期间，形成含C、H、N和O的不稳定的复合物，它们理想地分解成二氧化碳、水和双氮。
但是还形成了许多其他化合物，例如在采用乙醇通过SCR进行处理的情况下，形成了例如以不可忽略量存在的氰化氢。
众所周知的是，提供允许对还原剂的注入进行管理的装置，从而确保足量的注入以合适地还原NOx。
在此类装置中，在催化剂出口处设置了对氮氧化物特别灵敏的气体检测器，更常称作NOx探测器，实现对排出的气体量进行测量。
将该检测器的输出信号传送到处理单元，该处理单元用于对还原剂注入功能和/或催化功能进行控制和/或诊断。通过该信号，处理单元确定在催化剂出口处的废气中的NOx含量，然后将该含量与预定模型进行对比。在与所述模型存在差异的情况下，改变还原剂注入设定点，从而减小或消除该差异。
虽然该装置给出了令人满意的结果，但是其涉及几个明显的缺陷。
实际上，该装置无法实现对存在的其他化合物，例如异氰酸或者氰化氢进行检测。
从而处理单元无法得知在催化剂出口处的经处理的废气中是否存在这些化合物以及是否将这些化合物排放到大气中，而它们对于活生物体是有害的。
本发明的目的是通过利用废气管线或者烟囱中已经存在的装置，以一种简单低廉的方式克服前述缺陷。
发明内容
因此，本发明涉及对经过选择性催化还原处理的废气中排放的含氮化合物进行检测的方法，通过将还原剂注入气体并将所述气体通过催化剂来实现所述选择性催化还原处理，其特征在于，该方法包括以下步骤：
－向处理单元输送设置在催化剂下游的废气中的气体检测器（18）收集到的信号，该信号代表了催化剂出口处的NOx的量（NOx探测器），
－将该信号通过SCR催化剂模型分解成代表催化剂出口处的NOx有效量的值（NOx真实），通过整体模型分解成检测器扰动系数（k）和代表氨的量的值（NH3真实），从而得到NOx探测器=NOx真实+kNH3真实，
－从所述分解评估系数（k），
－当系数（k）大于或等于1时，确定催化剂的下游存在含氮化合物。
所述方法可以包括引入氨或者分解成氨的物质作为还原剂。
所述方法可以包括引入尿素作为还原剂。
所述方法可以包括当系数（k）大于或等于1时，并且当还原剂是氨或者分解成氨的物质时，检测出催化剂下游的废气中存在异氰酸。
所述方法可以包括引入烃类作为还原剂。
所述方法可以包括引入氧化的烃类作为还原剂。
所述方法可以包括引入乙醇作为还原剂。
所述方法可以包括当系数（k）大于或等于1时，并且当还原剂是烃类时，检测出存在异氰酸。
所述方法可以包括在检测到这些含氮化合物之后，通过所述单元启动警报程序。
附图说明
通过阅读下文中的非限制性实施例，并参考显示了本发明所用的SCR工艺的NOx处理装置的附图，可以了解本发明的其他特征和益处。
发明详述
附图显示了设置在废气管线12上的SCR工艺10的NOx处理装置。来自静态的或安装在机动车辆中的内燃机（未示出）的废气在所述管线中循环。
在废气流动的方向上，所述装置在进口E和出口S之间包括：还原剂注入装置14、SCR催化剂16以及设置在所述催化剂下游的NOx探测器18的形式的气体检测器。
当然，在例如燃料后注入的情况下，所述还原剂也可以来自发动机的燃烧室，而不背离本发明的范围。
在还原剂并非来自发动机的燃烧室的情况下，所述注入装置包括与注入回路22相连的注射器20，所述注入回路22包含进行注入所需的全部元件（罐、泵等）。所述注射器设置在SCR催化剂上游的废气管线部分，设置的方式使得它的喷嘴在废气管线内打开，用于向所述催化剂喷射还原剂。
优选地，还原剂是氨或者通过分解产生氨的物质，例如尿素，但是也可以采用任意其他试剂，例如氢化或未氢化的烃类。
所述装置还包括用于控制注入回路22的处理和控制单元24，其也与探测器18相连。该控制单元含有SCR催化剂模型的图表，可以知道要注入的还原剂的量，从而在催化剂中获得合适的NOx处理，以及催化剂出口处的氨含量的整体唯象模型。
因此，通过NOx探测器，所述单元24了解任意时刻离开催化剂的NOx的量，因而它可以调节要递送到废气管线中的还原剂的量，从而获得所需的效率。
当然，该单元还与各种其他检测器，例如废气温度检测器（未示出）相连，并接收内燃机运行的信息，从而可以控制注入回路22。
在附图所示装置的测试活动期间，申请人发现NOx探测器对于含氮化合物是灵敏的，特别对于异氰酸（HNCO）和氰化氢（HCN）是灵敏的。
因此，申请人建立了一种鉴别这些含氮化合物并为用户启动信息或警报程序的方法。
对于常规氨SCR处理控制***，已知NOx探测器通过对比该探测器传送的信号与SCR催化剂下游的NOx的预期量，来鉴定NOx排放差异。该预期量可以特别地通过单元24中储存的唯象模型进行估算。
普遍承认的是，NOx探测器设计用于测量NOx值。
但是，它会受到化合物Pi的总和的扰动，根据系数ki，对探测器的所有扰动符合下式：
在会扰动探测器的化合物中，最熟知的是氨（NH3）。扰动能力被申请人观察到的其他化合物是HNCO（异氰酸）和HCN（氰化氢）。
从文献已知，与氨相关的扰动所对应的扰动系数k小于1。
这样一来，对于实际情况，例如在车辆中，我们可以知道：
-Nox探测器：通过探测器22测量或估算的NOx的量，
-NOx真实：通过发动机控制单元或者无扰动探测器或者实验室类型的“柜”测量中的整体模型，由SCR催化剂模型所建立的催化剂16出口处的NOx的有效量，
-NH3真实：通过发动机控制单元或者无扰动探测器或者实验室类型的“柜”测量中的整体模型的氨含量。
如此一来，可以根据下式计算系数k：
NOx探测器＝NOx真实＋kNH3真实。
因此，
如果k<1，则可以认为存在由于氨所导致的扰动。
如果k>1，则单独的氨无法解释探测器的扰动，因此承认在废气中存在含氮化合物的扰动。
因此，
·在用氨（或者可以分解成氨的物质）进行SCR处理的情况下，在催化剂出口处存在不可忽略量的异氰酸（HNCO），
·在用烃类，特别是乙醇进行SCR处理的情况下，存在不可忽略量的氰化氢（HCN）。
在这两种情况下，这些污染排放物可以表示催化剂的NOx处理期间或者递送还原剂之后的明显故障。
因此，处理单元启动一个或多个警报程序以通知用户在废气中存在不合乎希望的含氮化合物，这表明去污染功能的故障。
例如，所述单元向机载计算机（OBD-机载诊断）输送信号以报道该异常情况，这会产生警报指示灯的致动或者要求专家的介入干涉。
因此，应注意的是，考虑异氰酸（HNCO）和氰化氢（HCN）对探测器的扰动，对于诊断采用SCR的NOx的处理功能是有用的。
当然，上述方法还可用于除了来自内燃机的废气之外的其他类型的废气。
还可特别地用于来自其他燃烧，例如来自涡轮或者炉，并在包含SCR10的NOx处理装置的排气烟囱中循环的烟气。
Claims (11)
1.一种对经过选择性催化还原处理的废气中排放的含氮化合物进行检测的方法，通过将还原剂注入气体并将所述气体通过催化剂（16）来实现所述选择性催化还原处理，其特征在于，该方法包括以下步骤：
－向处理单元（24）输送设置在催化剂下游的废气中的气体检测器（18）收集到的信号，该信号代表了催化剂出口处的NOx的量（NOx探测器），
－将该信号通过SCR催化剂模型分解成代表催化剂出口处（16）的NOx有效量的值（NOx真实），通过整体模型分解成检测器扰动系数（k）和代表氨的量的值（NH3真实），得到NOx探测器=NOx真实+kNH3真实，
－从所述分解评估系数（k），
－当系数（k）大于或等于1时，确定催化剂（16）的下游存在含氮化合物。
2.如权利要求1所述的方法，其特征在于，所述方法包括引入氨或者分解成氨的物质作为还原剂。
3.如权利要求1或2所述的方法，其特征在于，所述方法包括引入尿素作为还原剂。
4.如权利要求1-3中任一项所述的方法，其特征在于，所述方法包括当系数（k）大于或等于1时，并且当还原剂是氨或者分解成氨的物质时，检测出催化剂（16）下游的废气中存在异氰酸。
5.如权利要求1所述的方法，其特征在于，所述方法包括引入烃类作为还原剂。
6.如权利要求5所述的方法，其特征在于，所述方法包括引入氧化的烃类作为还原剂。
7.如权利要求5或6所述的方法，其特征在于，所述方法包括引入乙醇作为还原剂。
8.如权利要求1和5-7中任一项所述的方法，其特征在于，所述方法包括当系数（k）大于或等于1并且还原剂是烃类时，检测出存在异氰酸。
9.如前述任一项权利要求所述的方法，其特征在于，所述方法包括在检测出此类含氮化合物之后，通过单元（24）启动警报程序。
10.权利要求1-9中任一项所述的方法用于在发动机，特别是内燃机的废气管线中循环的废气的用途。
11.权利要求1-9中任一项所述的方法用于由燃烧，特别是涡轮或炉中燃烧所得的烟气的用途。
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| CN105545434A (zh) * | 2014-10-28 | 2016-05-04 | 通用电气公司 | 用于燃气涡轮机***中的排放物控制的***和方法 |
| CN110307062A (zh) * | 2014-11-10 | 2019-10-08 | 康明斯排放处理公司 | 包括烃检测发生介质的排气流体过滤器 |
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| FR3069641B1 (fr) * | 2017-07-27 | 2019-07-19 | IFP Energies Nouvelles | Procede et systeme de mesure optique de la concentration d’especes gazeuses de gaz d’echappement |
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| FR2993602A1 (fr) | 2014-01-24 |
| FR2993602B1 (fr) | 2014-07-25 |
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| EP2687698A1 (fr) | 2014-01-22 |
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