CN110725732A - 一种汽车尾气净化器的改进方法 - Google Patents

一种汽车尾气净化器的改进方法 Download PDF

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CN110725732A
CN110725732A CN201910913678.1A CN201910913678A CN110725732A CN 110725732 A CN110725732 A CN 110725732A CN 201910913678 A CN201910913678 A CN 201910913678A CN 110725732 A CN110725732 A CN 110725732A
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catalyst
phosphorus
sulfur
gas
noble metal
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刘建英
徐成华
田黎霞
杨皓
王娟芸
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/24Exhaust 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
    • F01N3/28Construction of catalytic reactors
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/101Three-way catalysts
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust 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
    • F01N3/18Exhaust 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
    • F01N3/20Exhaust 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/04Sulfur or sulfur oxides
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/08Phosphorus
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Catalysts (AREA)

Abstract

本发明公告了一种汽车尾气净化器的改进方法,在汽车发动机排气管催化组件前端设置50~70%体积的350~1100℃水解催化有机硫、无机硫、有机磷、无机磷转化成硫酸盐、磷酸盐的高效脱除硫、脱除磷固化型催化剂与30~50%体积的贵金属三效催化剂串联工作,经过脱硫、脱磷催化剂后发动机尾气气相总硫磷控制在0.2ppm以下,或总硫磷脱除率达到80%以上,再进入三效催化剂转化其他有害气体;由此,相同使用寿命汽车尾气净化器中贵金属催化剂的使用量减少50%以上,而且相同贵金属量催化剂使用寿命延长到原来的2倍以上。

Description

一种汽车尾气净化器的改进方法
技术领域
本发明涉及冶金、节能、环保领域,是一种有效减少气体废弃物排放、降低资源消耗的方法。
背景技术
中自环保科技股份有限公司王瑞芳等CN108636431A公告了一种壁流式LNT催化剂、制备方法和应用。催化剂涂层包括金属氧化物、镁铝尖晶石、贵金属、碱性元素以及助剂,涂层的涂覆量为80-200g/L,贵金属的涂覆量为5-120g/ft3,载体为SiC、钛酸铝或堇青石材质;本发明制备的催化剂载体采用对称型或非对称型的壁流式载体,载体孔隙率大,孔径分布窄。本发明通过将LNT涂层涂覆于壁流式载体中,一方面具有LNT的处理NOx功能,另一方面壁流式载体对PM具有捕集作用,具有DPF的功能;在LNT高温脱硫再生过程中同时实现DPF中的再生,可降低油耗。由于壁流式载体增加了尾气与涂层的接触时间,可以提高LNT的NOx处理效率。该LNTF具有很好NOx转化效率,很好的耐高温稳定性,操作工艺容易实现,在汽车尾气后处理系统中可应用。
睿仑空气处理技术东台有限公司陈亚芳CN106988831A公开了一种方便安装的小型汽车尾气净化装置,包括净化筒和排气口,净化筒的一端安装有排气口,另一端连接螺纹管,排气口的一端内壁设有竖直放置的隔板,隔板的表面设有多个圆形通孔,螺纹管的一端管口处连接除尘筒,除尘筒的一端表面设有紧固件,除尘筒的内部设有第一过滤层、第二过滤层和第三过滤层,净化筒的内部设有脱硫层,脱硫层的一侧设有脱酸层,整体体积小,而且能够轻松的通过紧固件安装在汽车排气管上,实现了在尾气刚刚产生时就对其净化,通过第一过滤层、第二过滤层和第三过滤层,对尾气中的固体颗粒物有高效的去除效果,再通过脱硫层、脱酸层、脱硝层和活性炭吸附层,对有毒气体进行净化,做到无毒排放。
苏州莲池环保科技发展有限公司孟晓辉CN105214622B一种高活性汽车三元催化器配方的制备方法,其特征在于:包括:80~90wt%的多孔陶瓷、5~10wt%的吸附剂和5~10wt%的催化剂;所述多孔陶瓷包括以下重量份的原料:铝溶胶90~100份、微纳米级α-Al2O3 40~60份、成孔剂20~30份、粘结剂0~5份、粘合剂2~5份和pH为3~4的酸溶液250~350份;所述吸附剂包括磁性壳聚糖纳米粒子。本发明提供的一种高活性汽车三元催化器配方的制备方法,采用磁性壳聚糖纳米粒子代替传统的氧化铝作为吸附剂,磁性壳聚糖纳米粒子吸附汽车尾气分子的能力更强,净化能力是氧化铝的5~10倍,壳聚糖表面的铁具有脱硫活性,有效避免三元催化器硫中毒。
根据以上发明专利可以看出,有意识的脱除硫化物或在催化剂上加载脱硫剂或在三效催化后加脱硫减少环境污染是一个共识。但是以往的专利都没有在三效贵金属催化剂上使用过固硫磷催化剂,由此防护催化剂硫、磷中毒。
实际上,把硫固定在三效催化剂上会消灭贵金属的活性,这个我们在实验中已经验证。
实际上,把磷固定在三效催化剂上也会消灭贵金属的活性,这个我们在实验中已经验证。
本发明人在某工业尾气脱除硫化氢、COS、CS2、有机磷与贵金属催化脱氧工业化过程中发现,当总硫磷含量1ppm进入催化剂时,贵金属钯铂活性只能保持2年,当总硫磷含量为0.2ppm时,贵金属活性能保持8年。据此,本发明人认为当发动机尾气中总硫达到尽可能低,有利于延长三效贵金属催化剂(钯铂为重要活性中心)寿命。
而利用发动机尾气的特性来脱除贵金属有害成分,延长三效催化剂寿命成为一种有效的方法,特发明以下方法。
发明内容
三效催化剂的工作温度为600~900℃,异常工作温度为600~1100℃。以目前国V/VI的汽油10mg/L总硫与润滑油中的磷,导致汽车排放物中总硫磷大约为1ppm。
在汽车发动机排气管催化组件前端设置50~70%体积的600~1100℃水解有机硫、无机硫、有机磷、无机磷转化成硫酸盐、磷酸盐的催化脱除有机硫、有机磷固化型催化剂与30~50%体积的贵金属催化剂三效催化剂组串联工作,经过脱硫、脱磷催化剂后发动机尾气气相总硫磷控制在0.2ppm以下再进入三效催化剂转化其他有害气体,或者将排气中的总硫磷降低80%以上。由此,相同使用寿命汽车尾气净化器中贵金属催化剂的使用量减少50%以上,而且相同贵金属量催化剂使用寿命延长到原来的2倍以上。
脱除硫磷的催化剂组含高温有机硫、磷水解催化剂,先将有机硫磷转化成硫化氢、磷化氢,再将硫化氢、磷化氢转化成金属硫酸盐、磷酸盐,由此固定硫磷,所用催化剂的价格远低于贵金属,催化剂单价大约为贵金属催化剂的五分之一。
具体实施方式
实施例1:国V汽车原发动机设计使用100%三效贵金属催化剂组件净化尾气。改进的方法,在汽车发动机排气管催化组件前端设置50%体积的600~1100℃水解催化有机硫、无机硫、有机磷、无机磷转化成硫酸盐、磷酸盐的高效脱除硫、脱磷固化型催化剂,与50%体积的贵金属三效催化剂串联工作,经过脱硫、脱磷催化剂后发动机尾气气相总硫磷控制在0.15ppm以下,总硫磷脱除率85%,再进入三效催化剂转化其他有害气体;由此,改进型尾气净化器中贵金属催化剂的使用量减少75%,贵金属量催化剂组件使用寿命延长到原来的2.5倍。
实施例2:国V汽车原发动机使用100%三效贵金属催化剂组件净化尾气,改进的方法,在汽车发动机排气管催化组件前端设置30%体积的600~1100℃水解催化有机硫、无机硫、有机磷、无机磷转化成硫酸盐、磷酸盐的高效脱除硫、脱磷固化型催化剂,与70%体积的贵金属三效催化剂串联工作,经过脱硫、脱磷催化剂后发动机尾气气相总硫磷控制在0.2ppm以下,再进入三效催化剂转化其他有害气体;由此,改进型尾气净化器中贵金属催化剂的使用量减少50%,而且贵金属量催化剂组件使用寿命延长到原来的2倍。
实施例3:天然气含总硫磷1ppm的汽车发动机使用100%三效贵金属催化剂组件净化尾气,改进的方法,在汽车发动机排气管催化组件前端设置50%体积的600~1100℃水解催化有机硫、无机硫、有机磷、无机磷转化成硫酸盐、磷酸盐的高效脱除硫、脱磷固化型催化剂,与50%体积的贵金属三效催化剂串联工作,经过脱硫、脱磷催化剂后发动机尾气气相总硫磷控制在0.10ppm以下,再进入三效催化剂转化其他有害气体;由此,改进型尾气净化器中贵金属催化剂的使用量减少68%,而且贵金属量催化剂组件使用寿命延长到原来的2.5倍。

Claims (1)

1.一种汽车尾气净化器的改进方法,其特征在于:在汽车发动机排气管催化组件前端设置50~70%体积的350~1100℃水解催化有机硫、无机硫、有机磷、无机磷转化成硫酸盐、磷酸盐的高效脱除硫、脱除磷固化型催化剂与30~50%体积的贵金属三效催化剂串联工作,经过脱硫、脱磷催化剂后发动机尾气气相总硫磷控制在0.2ppm以下,或总硫磷脱除率达到80%以上,再进入三效催化剂转化其他有害气体;由此,相同使用寿命汽车尾气净化器中贵金属催化剂的使用量减少50%以上,而且相同贵金属量催化剂使用寿命延长到原来的2倍以上。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474531A (zh) * 2009-01-19 2009-07-08 昆明理工大学 黄磷尾气燃气净化方法及其装置
US20130186065A1 (en) * 2012-01-19 2013-07-25 GM Global Technology Operations LLC Sulfur accumulation monitoring systems and methods
CN105315004A (zh) * 2015-10-22 2016-02-10 苏州莲池环保科技发展有限公司 汽车三元催化器具脱硫活性的多孔陶瓷配方及其制备方法
CN105658309A (zh) * 2014-08-29 2016-06-08 马自达汽车株式会社 尾气净化催化装置及尾气净化方法
EP3115566A1 (de) * 2015-07-09 2017-01-11 Volkswagen Aktiengesellschaft Vorrichtung und verfahren zur abgasnachbehandlung einer brennkraftmaschine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474531A (zh) * 2009-01-19 2009-07-08 昆明理工大学 黄磷尾气燃气净化方法及其装置
US20130186065A1 (en) * 2012-01-19 2013-07-25 GM Global Technology Operations LLC Sulfur accumulation monitoring systems and methods
CN105658309A (zh) * 2014-08-29 2016-06-08 马自达汽车株式会社 尾气净化催化装置及尾气净化方法
EP3115566A1 (de) * 2015-07-09 2017-01-11 Volkswagen Aktiengesellschaft Vorrichtung und verfahren zur abgasnachbehandlung einer brennkraftmaschine
CN105315004A (zh) * 2015-10-22 2016-02-10 苏州莲池环保科技发展有限公司 汽车三元催化器具脱硫活性的多孔陶瓷配方及其制备方法

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