JP2021509087A - 炭化水素除去システム - Google Patents

炭化水素除去システム Download PDF

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Publication number
JP2021509087A
JP2021509087A JP2020536557A JP2020536557A JP2021509087A JP 2021509087 A JP2021509087 A JP 2021509087A JP 2020536557 A JP2020536557 A JP 2020536557A JP 2020536557 A JP2020536557 A JP 2020536557A JP 2021509087 A JP2021509087 A JP 2021509087A
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Prior art keywords
hydrocarbon
adsorption catalyst
removal system
pore size
hydrocarbon adsorption
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JP2020536557A
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Inventor
チョン ヨン ガン，
チョン ヨン ガン，
チャン ファン キム，
チャン ファン キム，
ジョン ギュ チェ，
ジョン ギュ チェ，
ジャン，ウン−ヒ
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Korea University Research and Business Foundation
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Korea University Research and Business Foundation
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Priority claimed from PCT/KR2018/016906 external-priority patent/WO2019132612A1/ko
Publication of JP2021509087A publication Critical patent/JP2021509087A/ja
Pending legal-status Critical Current

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Abstract

【課題】炭素数が低い炭化水素の通過を抑制して効果的に吸着できる炭化水素除去システムを提供することにある。【解決手段】本発明の一実施例による炭化水素除去システムは、第１気孔大きさを有する第１炭化水素吸着触媒を含む第１領域、第２気孔大きさを有する第２炭化水素吸着触媒を含む第２領域を含み、前記第１気孔の大きさは前記第２気孔大きさより小さく、前記第１炭化水素吸着触媒はＣＨＡ型ゼオライトを含み、前記第２炭化水素吸着触媒はＺＳＭ−５ゼオライトを含むことを特徴とする。【選択図】図４

Description

本発明は、炭化水素除去用触媒を用いた炭化水素除去システムに関する。
大気汚染に関する関心が高まるにつれ、米国、欧州などの国家ではＣＯ、ＮＯｘ、ＨＣ（ｈｙｄｒｏｃａｒｂｏｎ）、ＰＭ（ｐａｒｔｉｃｕｌａｔｅ ｍａｔｔｅｒ）などの自動車排気ガスの規制が強化されている。その中で、ＨＣは三元触媒（ｔｈｒｅｅ−ｗａｙ ｃａｔａｌｙｓｔｓ；ＴＷＣｓ）によりほとんど酸化される。しかし、この三元触媒は約２００〜３００℃以上で活性を現わすが、三元触媒が活性を現わさない低温始動区間で，全体ＨＣ排出量の５０〜８０％に該当するＨＣが排出される。ＨＣ排出を低減させるために炭化水素吸着剤（ＨＣ ｔｒａｐ）に対する研究が進行されている。炭化水素吸着剤とは、低温始動区間で排出されるＨＣを吸着して三元触媒が活性を現わす２００〜３００℃に到達する時に離脱させるものである。
炭化水素吸着剤として高い物理的、化学的安定性を有するゼオライトが多く研究されている。代表的なＨＣ排出物質であるプロペン（ｐｒｏｐｅｎｅ）、トルエン（ｔｏｌｕｅｎｅ）の吸着／離脱測定により炭化水素吸着剤の性能をテストしている。ゼオライト構造およびＳｉ／Ａｌ比、金属含浸の有無による炭化水素吸着剤の性能に関する研究が進行されている。
本発明が解決しようとする技術的課題は、炭素数が低い炭化水素の通過（ｓｌｉｐ）を抑制して効果的に吸着できる炭化水素除去システムを提供することにある。
このような課題を解決するために本発明の実施例による炭化水素除去システムは、第１気孔大きさを有する第１炭化水素吸着触媒を含む第１領域と、第２気孔大きさを有する第２炭化水素吸着触媒を含む第２領域と、を含み、前記第１気孔大きさは前記第２気孔大きさより小さく、前記第１炭化水素吸着触媒はＣＨＡ型ゼオライトを含み、前記第２炭化水素吸着触媒はＺＳＭ−５ゼオライトを含む。
前記第１炭化水素吸着触媒の気孔大きさは、３．０Å〜４．４Åでありうる。
前記第２炭化水素吸着触媒の気孔大きさは、４．５Å〜９．０Åでありうる。
前記炭化水素除去システム内で前記第１炭化水素吸着触媒と前記第２炭化水素吸着触媒の重量比率は、１：９〜５：５でありうる。
本発明の他の一実施例による炭化水素除去システムは、第１気孔大きさを有する第１炭化水素吸着触媒および第２気孔大きさを有する第２炭化水素吸着触媒が混合されており、前記第１気孔大きさは前記第２気孔大きさより小さく、前記第１炭化水素吸着触媒はＣＨＡ型ゼオライトを含み、前記第２炭化水素吸着触媒はＺＳＭ−５ゼオライトを含む。
前記第１炭化水素吸着触媒の気孔大きさは、３．５Å〜４．５Åでありうる。
前記第２炭化水素吸着触媒の気孔大きさは、４．５Å〜９．０Åでありうる。
前記炭化水素除去システム内で前記第１炭化水素吸着触媒と前記第２炭化水素吸着触媒の混合重量比は、１：９〜５：５でありうる。
以上のように炭素数が低い炭化水素の通過を抑制して効果的に吸着できる炭化水素除去用システムを提供する。
本発明の一実施例による炭化水素除去システムを示す図である。 ガソリン車の排気ガスを三元触媒によって浄化する構成を示す図である。 炭化水素吸着剤に吸蔵されない炭化水素の比率を示す図である。 本実施例による炭化水素除去システムを概略的に示す図である。 他の一実施例による炭化水素除去システムを示す図である。 吸着、離脱評価試験の試験温度を示す図である。 具体的な実験条件を示す図である。 実験例１による評価結果を示す図である。 実験例２による評価結果を示す図である。
添付する図面を参照して本発明の実施例を本発明が属する技術分野における通常の知識を有する者が容易に実施できるように詳細に説明する。しかし、本発明は様々な異なる形態に実現することができ、ここで説明する実施例に限定されない。
以下、本発明の実施例による炭化水素除去システムについて図面を参照して詳細に説明する。
図１は本発明の一実施例による炭化水素除去システムを示す図である。図１を参照すると、本実施例による炭化水素除去システムは第１気孔大きさを有する第１炭化水素吸着触媒を含む第１領域Ａ１、第２気孔大きさを有する第２炭化水素吸着触媒を含む第２領域Ａ２を含み、前記第１気孔大きさは前記第２気孔大きさより小さい。一例として、第１炭化水素吸着触媒はＣＨＡ型ゼオライトを含み、第２炭化水素吸着触媒はＺＳＭ−５ゼオライトを含み得る。
本実施例による炭化水素除去システムについてより詳細に説明する。
図２はガソリン車の排気ガスを三元触媒によって浄化する構成を示す図である。図２から考察すると、ガソリン車の排気ガスは三元触媒によって浄化され、触媒の温度が４００℃以上の場合、ほぼ１００％に近い浄化性能を有する。しかし、エンジン始動直後の冷始動区間（Ｃｏｌｓ−Ｓｔａｒｔ）では三元触媒が正常に作動しないことにより排気ガスが浄化されず、大気の中に排出される。特に炭化水素は全体の約７０％が冷始動区間で排出されると知られている。
しかし、本実施例では排気ガスシステムにゼオライト系の炭化水素吸着剤を導入し、三元触媒の温まり完了時点までは冷始動区間に排出される炭化水素を炭化水素吸着剤で吸着した後、三元触媒の温まりが終わる時点で炭化水素吸着剤から離脱された時三元触媒により浄化させることができる。
この過程で炭化水素吸着剤に吸蔵されずエンジン始動と同時に排出される炭素数が低い炭化水素（Ｃ１Ｈｘ〜Ｃ５Ｈｙ）の種類がＴ／Ｐ ＨＣ ＥＭ（Ｔａｉｌ Ｐｉｐｅ Ｈｙｄｒｏｃａｒｂｏｎ Ｅｍｉｓｓｉｏｎ）の全体の約３０％を占める。これを図３に示す。すなわち炭素数が低い炭化水素は吸収されず速やかに排出され、今後の強化した排気規制に対応するためには炭素数が低い炭化水素に対する浄化性能の改善が急がれる。
そこで、本発明は炭化水素吸着剤による化学的吸着が難しい炭素数が低い炭化水素の浄化のために炭化水素が浄化され得る約３５０℃程度のＴＷＣ（三元触媒）活性化時点まで炭素数が低い炭化水素の排出を遅延させるための構成を含んでいる。
すなわち、本発明は互いに気孔大きさが異なる炭化水素除去触媒を混合して使用することによって、炭素数が低い炭化水素が速やかに炭化水素除去システムを抜け出て吸着できなかった問題を解決した。この時、気孔大きさが小さい第１炭化水素吸着触媒が炭素数５以下の炭化水素の流れを遅延させ、炭素数５以下の炭化水素を効果的に吸着するようにする。
図４は本実施例による炭化水素除去システムを概略的に示す図である。図４を参照すると、狭い気孔大きさを有するＣＨＡ型のようなゼオライトが炭素数の小さい炭化水素を吸着する。したがって、このような炭素数が小さい炭化水素、例えばＣ２Ｈ２、Ｃ２Ｈ６、Ｃ４Ｈ８、Ｃ５Ｈ１２の拡散速度を減少させる。また、後面で広い気孔大きさを有するＺＳＭ−５のようなゼオライトが長い鎖を有する炭化水素（炭素数が大きい炭化水素）を吸着する。
すなわち、本発明は冷始動初期の炭化水素吸着剤に吸着されず抜け出る炭素数の小さい炭化水素（Ｃ１Ｈｘ〜Ｃ５Ｈｙ）の排出を低減させるために通過する炭化水素サイズに相応する気孔大きさを有する炭化水素吸着触媒を含む。したがって、相異する気孔を有する２種以上の炭化水素吸着触媒をコーティングまたは混合して１〜２層の構造に配置して使用し、物理的に炭素数が小さい炭化水素（Ｃ１Ｈｘ〜Ｃ５Ｈｙ）の拡散を遅延させることによって、ＥＨＣ（Ｅｌｅｃｔｒｉｃａｌｌｙ Ｈｅａｔｅｄ Ｃａｔａｌｙｓｔ）により活性化したＴＷＣ（三元触媒）で酸化させることによって冷始動区間の炭化水素排出を改善することを特徴とする。
図１は第１領域と第２領域が互いに分離する構成を示したが、図５を参照すると、第１気孔サイズを有する第１炭化水素吸着触媒と第２気孔サイズを有する第２炭化水素吸着触媒を互いに混合して均等に位置させることができる。この場合も図１と同様に炭素数が低い炭化水素の拡散を抑制することができる。図５で気孔大きさが大きい炭化水素吸着触媒と気孔大きさが小さい炭化水素吸着触媒を互いに異なる大きさで示した。
本発明の炭化水素除去システム内で前記第１炭化水素吸着触媒と前記第２炭化水素吸着触媒の重量比率は、１：９〜５：５でありうる。すなわち、同一面積に対して炭化水素吸着触媒がコートされた重量（ｇ／Ｌ）の比率、すなわち第１炭化水素吸着触媒：第２炭化水素吸着触媒の比率が１：９〜５：５であり得る。これは炭素数が低い炭化水素の通過を効果的に抑制できる混合比率の範囲である。このような比率による効果は以下の実験例により説明する。
以下では具体的な実験例により本発明の一実施例による炭化水素除去システムについて詳細に説明する。
実験例１：吸着、離脱性能の評価
本発明に使用されたゼオライトは、ＮＨ４型ゼオライトを大気中で５５０℃、１２時間焼成して製造した。炭化水素吸着剤の吸着／離脱の評価はパウダ形態のＨ−ＣＨＡ／ＺＳＭ−５ゼオライト６０ｍｇを反応管に並列（Ｔａｎｄｅｍ）または混合した後充填、Ｈｅ流れ下に６００℃で３０分間前処理を行った後、７０℃で５分間Ｃ３Ｈ６、Ｃ７Ｈ８、Ｏ２、キャリアガスＡｒ／Ｈｅ混合ガス流れ下で吸着した後、５３℃／ｍｉｎの昇温速度で温度を上げて吸着、離脱性能の評価を行った。
図６は吸着、離脱評価試験の試験温度を示す図であり、図７は具体的な実験条件を示す図である。
実験例１による評価結果を図８に示した。
図８を参照すると、Ｃ３Ｈ６炭化水素はＣＨＡ型ゼオライトでより良い吸蔵性能を示した。ＣＨＡ型ゼオライトの気孔大きさが３．８Åｘ４．２ÅでＺＳＭ−５ゼオライトの気孔大きさ（直径５．６Å）より小さい。吸着対象であるＣ３Ｈ６の分子サイズは４．５ÅでＺＳＭ−５の気孔大きさより小さく、ＣＨＡの気孔大きさと類似するため、ＣＨＡでより良い吸着性能を現わすことを確認することができた。
逆にＣ７Ｈ８分子（５．８５Å）は、ＣＨＡの気孔を通過するのが難しいサイズで、ＣＨＡではほとんど吸着しないことを確認することができた。しかし、類似のサイズのＺＳＭ−５ではＣ７Ｈ８の高い吸蔵性能を示し、離脱温度も高いことがわかる。
実験例２：混合比率による効果
炭素数が高い炭化水素を吸着する炭化水素吸着剤と炭素数が低い炭化水素を吸着する炭化水素吸着剤の混合比率を異なるようにして炭化水素が通過する程度を測定し、実験例２による評価結果を図９に示した。図９を参照すると、高い炭素数を有する炭化水素を吸着する炭化水素吸着剤と低い炭素数を有する炭化水素を吸着する炭化水素吸着剤の混合重量比が９：１〜５：５である時、最も高い初期の炭化水素の通過低減効果があることを確認することができた。
以上、本発明の好ましい実施例について詳細に説明したが、本発明の権利範囲はこれに限定されるものではなく、以下の特許請求の範囲で定義している本発明の基本概念を用いた当業者の様々な変形および改良形態も本発明の権利範囲に属する。

Claims (8)

  1. 第１気孔大きさを有する第１炭化水素吸着触媒を含む第１領域と、
    第２気孔大きさを有する第２炭化水素吸着触媒を含む第２領域と、を含み、
    前記第１気孔大きさは前記第２気孔大きさより小さく、
    前記第１炭化水素吸着触媒はＣＨＡ型ゼオライトを含み、
    前記第２炭化水素吸着触媒はＺＳＭ−５ゼオライトを含む、ことを特徴とする炭化水素除去システム。
  2. 前記第１炭化水素吸着触媒の気孔大きさは、３．５Å〜４．４Åである、ことを特徴とする請求項１に記載の炭化水素除去システム。
  3. 前記第２炭化水素吸着触媒の気孔大きさは、４．５Å〜９．０Åである、ことを特徴とする請求項１に記載の炭化水素除去システム。
  4. 前記炭化水素除去システム内で前記第１炭化水素吸着触媒と前記第２炭化水素吸着触媒の重量比率は、１：９〜５：５である、ことを特徴とする請求項１に記載の炭化水素除去システム。
  5. 第１気孔大きさを有する第１炭化水素吸着触媒および第２気孔大きさを有する第２炭化水素吸着触媒が混合されており、
    前記第１気孔大きさは前記第２気孔大きさより小さく、
    前記第１炭化水素吸着触媒はＣＨＡ型ゼオライトを含み、
    前記第２炭化水素吸着触媒はＺＳＭ−５ゼオライトを含む、炭化水素除去システム。
  6. 前記第１炭化水素吸着触媒の気孔大きさは、３．５Å〜４．５Åである、ことを特徴とする請求項５に記載の炭化水素除去システム。
  7. 前記第２炭化水素吸着触媒の気孔大きさは、４．５Å〜９．０Åである、ことを特徴とする請求項５に記載の炭化水素除去システム。
  8. 前記炭化水素除去システム内で前記第１炭化水素吸着触媒と前記第２炭化水素吸着触媒の混合重量比は、１：９〜５：５である、ことを特徴とする請求項５に記載の炭化水素除去システム。

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