JP3582141B2 - Nitrogen oxide removal method - Google Patents
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- JP3582141B2 JP3582141B2 JP08588095A JP8588095A JP3582141B2 JP 3582141 B2 JP3582141 B2 JP 3582141B2 JP 08588095 A JP08588095 A JP 08588095A JP 8588095 A JP8588095 A JP 8588095A JP 3582141 B2 JP3582141 B2 JP 3582141B2
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- 238000000034 method Methods 0.000 title claims description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title description 15
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003463 adsorbent Substances 0.000 claims description 21
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 12
- 229910001923 silver oxide Inorganic materials 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Catalysts (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は大気中あるいは各種煙道排気中に含まれる窒素酸化物、殊に化学的に不活性で処理の困難なＮＯを効率よくＮＯ2 に転換し、これを吸着剤を用いて吸着して、ＮＯを除去する方法に関するものである。詳しくは、高速道路のトンネルや駐車場における自動車の排ガス中のＮＯを酸化、吸着処理をして、許容濃度にまで低減する方法に関する。
【０００２】
【従来の技術】
ＮＯ、ＮＯ2 は代表的な大気汚染物質であり、これまで多くの処理技術が提案されている。活性炭を初めとして、多数の吸着剤が提供されている。公知の吸着剤は、反応性に乏しいＮＯに対してはあまりその効果がないので、ＮＯを一旦酸化し、ＮＯ2 にして吸着除去する方法をとっていた。この際、酸化剤としては主としてオゾンが使用されていたために、オゾン発生装置と吸着の装置、さらに過剰オゾンを分解するためのオゾン分解装置が必要となり、全体として装置が複雑なものとなっていた。
【０００３】
【発明が解決しようとする課題】
本発明はかかる欠点を解消するためなされたものであり、コンパクトな装置を用いて、常温で効率よくＮＯを酸化し、これを効率よく吸着して、効率よく除去する方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明は常温でＮＯを触媒で酸化してＮＯ2 となし、生成したＮＯ2 を酸化ニッケルおよびもしくは酸化銀に吸着させ除去する方法である。
【０００５】
ＮＯは吸着剤に吸着し難いため、従来方法では全てを吸着剤に吸収し易いＮＯ2 の型に酸化し、吸着除去させていたが、本発明に係るＮＯ酸化触媒である比表面積５０ｍ2／ｇ以上で最大強度を示すＸ線回折角度（２θ）が３７±１°のγ−ＭｎＯ2 は、常温でＮＯを効率よく酸化して、ＮＯ2 に変換し、更に、このように変換されたＮＯ2 を、再生時の着火性、吸着速度が遅い等の問題の多い従来の活性炭のＮＯ2 吸着剤に代えて、再生時の着火性に全く問題がなく、しかも高速吸着性に優れた酸化ニッケル及びもしくは酸化銀に吸着させることによって、従来に較べてコンパクトな装置で実施できる利点を有する。
【０００６】
一般にＭｎＯ2 を製する方法は電解法、水酸化マンガン、炭酸マンガンなどのγ−ＭｎＯ2 前駆体を酸化処理して得る方法がある。このようにして製造したγ−ＭｎＯ2 はＮＯをＮＯ2 に酸化する能力はあるが、その能力は最大強度を示すＸ線回折角度（２θ）が３７±１°のγ−ＭｎＯ2 の比表面積に大いに依存している。図２からわかる如く比表面積が５０ｍ2／ｇ以上であれば、効率よくＮＯをＮＯ2 に酸化し、５０ｍ2／ｇ以下であれば、その能力が劣ることが分かった。そこで比表面積が５０ｍ2／ｇ以上のものを製造する方法について検討をした。
【０００７】
そこで我々は研究を重ねたところ、次のような方法によって最大強度を示すＸ線回折角度（２θ）が３７±１°で、比表面積が高く、殊に５０ｍ2／ｇ以上のγ−ＭｎＯ2 を得ることができることがわかった。即ち、
１）一般の炭酸マンガンを焼成温度が２５０℃〜４５０℃において焼成し、酸処理して、γ−ＭｎＯ2 を得る。ここにおいて焼成温度が４５０℃以上であると、シンタリングが起こり、また２５０℃以下では収率が低下する。
【０００８】
２）硝酸マンガンと過マンガン酸カリウムを反応させ、水洗乾燥させることにより、目的のγ−ＭｎＯ2 を得ることができる。このようにして得たγ−ＭｎＯ2 によりＮＯを酸化して得たＮＯ2 及び既存のＮＯ2、Ｎ2Ｏ3（ＮＯx と称する）は酸化ニッケル及びもしくは酸化銀からなる吸着剤で吸着することによって高速で存在するＮＯを除去することができる。
【０００９】
本発明において用いるＮＯ2 吸着剤は酸化ニッケルおよびもしくは酸化銀を主成分とする。酸化ニッケルは炭酸ニッケルを２５０℃〜４００℃にて焼成して得られるＮｉ2Ｏ3 が最も好ましく、この時比表面積は１５０〜２５０ｍ2／ｇであり、塩基性炭酸ニッケルを焼成して得られるＮｉＯも好ましく用いることができる。本発明において用いる酸化銀としては市販の酸化銀を用いることができる。あるいは硝酸銀などの酸化銀前駆体を焼成したものでもよい。本発明による酸化剤あるいはＮＯ2 吸着剤は従来知られている成形方法によってハニカム状、球状等の種々の形状に成形することができる。この成形に際し、成形助剤、成形補強体、無機繊維、有機バインダー等を適宜配合してもよい。またあらかじめ成形された基材上にウオッシュコート法等によって被覆担持させることもできる。さらに従来知られているその他の吸着剤の調製法によることもできる。
【００１０】
【実施例】
以下具体的に実施例により説明する。
実施例１
和光純薬製特級炭酸マンガンを空気中で４００℃にて５時間焼成した。得られた焼成物２００ｇを１／１０Ｎの硝酸水溶液１Ｌに投入し、３０分間攪拌し酸処理を行った。その後、濾過・イオン交換水にて水洗を行った。得られた酸処理物は１５４ｇであった。また比表面積は８２．６ｍ2／ｇであった。また最大強度を示すＸ線回折角度（２θ）は３６．５°であった。
【００１１】
実施例２
和光純薬製特級硝酸マンガン１２１．８ｇを２０ｍＬのイオン交換水に溶解して、硝酸マンガン水溶液を調製した。別に、和光純薬製特級過マンガン酸カリウム４０ｇを２０００ｍＬのイオン交換水に溶解して、過マンガン酸カリウム水溶液を調製した。上記硝酸マンガン水溶液をこの過マンガン酸カリウム水溶液に攪拌下で滴下し、約３０分にて反応を終えた。その後、濾過、イオン交換水にて水洗を行い６１ｇの乾燥物を得た。この時比表面積は２０４ｍ2／ｇであった。また最大強度を示すＸ線回折強度角度（２θ）は３６．９°であった。
【００１２】
実施例３
和光純薬製特級炭酸ニッケル５００ｇを３５０℃にて３時間焼成して酸化ニッケル４１２ｇを得た。得られたＮｉ2Ｏ3 の比表面積は２３５．７ｍ2／ｇであった。
【００１３】
ＮＯ酸化触媒の調製
実施例１、２で得られたγ−ＭｎＯ2 の粉体５０ｇと日産化学製シリカゾル（商品名スノーテックスＤ）３０ｇと水を適宜加えて顆粒状に成形し、２０メッシュアンダー３０メッシュオーバーとした。
【００１４】
実施例４
和光純薬製特級炭酸ニッケル５００ｇを４００℃にて３時間焼成して酸化ニッケル３６６ｇを得た。得られたＮｉＯの比表面積は１３１．４ｍ2／ｇであった。
【００１５】
ＮＯ2 吸着剤の調製
実施例３もしくは４で得た酸化ニッケルおよびもしくは和光純薬製特級酸化銀の粉体５０ｇと日産化学製シリカゾル（商品名スノーテックスＤ）３０ｇと水を適宜加えて顆粒状に成形し、２０メッシュアンダー３０メッシュオーバーとした。
【００１６】
実施例５
実施例３で得た酸化ニッケル５０ｇと日産化学製シリカゾル（商品名スノーテックスＤ）３０ｇと水を適宜加えて顆粒状に成形し、２０メッシュアンダー３０メッシュオーバーとした。
【００１７】
実施例６
実施例４で得た酸化ニッケル５０ｇを用いて、以下実施例５と同様にしてＮＯ2 吸着剤を調製した。
【００１８】
実施例７
実施例３で得た酸化ニッケル４５ｇと和光純薬製特級酸化銀５ｇを用いて、以下実施例５と同様にしてＮＯ2 吸着剤を調製した。
【００１９】
実施例８
実施例３で得た酸化ニッケル２５ｇと和光純薬製特級酸化銀２５ｇを用いて、以下実施例５と同様にしてＮＯ2 吸着剤を調製した。
【００２０】
比較例
実施例１において、焼成温度を５５０℃とした以外、同様の方法にて酸処理物を得た。このとき比表面積は４０．０ｍ2／ｇであった。
【００２１】
評価試験方法
本発明による方法として、上記実施例１又は２によるＮＯ酸化触媒をガス流れの前段に配設すると共に、上記実施例３、５、６、７又は８によるＮＯ2 吸着剤をガス流れの後段に設置し、下記の試験条件にて窒素酸化物含有ガス中の窒素酸化物をＮＯ 2 に酸化し、次いで、これをＮＯ2 吸着剤に吸着させて、ＮＯの除去率（％）を求めた。同様に、上記比較例によるＮＯ酸化触媒をガス流れの前段に配設すると共に、上記実施例３によるＮＯ 2 吸着剤をガス流れの後段に設置し、下記の試験条件にて窒素酸化物含有ガス中の窒素酸化物をＮＯ 2 に酸化し、次いで、これをＮＯ 2 吸着剤に吸着させて、ＮＯの除去率（％）を求めた。また、ＮＯ2 吸着剤の前でもサンプリングを行い、ＮＯのＮＯ2 への酸化率を求めた。
【００２２】
上記評価試験に用いた装置構成を図１に示す。エアー（空気）を入り口より入れ、これにＮＯ濃度が２００ｐｐｍ、バランスが窒素である標準ガスを所定の濃度となるように供給し、酸化触媒及びＮＯ2 吸着剤を通過させ、その後ＮＯ分析計により通過エアー中のＮＯ及びＮＯ2 濃度を測定した。
【００２３】
ＭｎＯ 2 の種々試作品の測定表面積に対してＮＯ除去率をプロットしたものを図２に示す。比表面積が５０ｍ2／ｇあたりで７８％の除去率を示し、それより増加しはじめ、１００ｍ2／ｇを越えたあたりで９０％に達して平坦になっている。
【００２４】
試験条件
（１）ガス組成
ＮＯ：５ｐｐｍ
吸着剤：１０ｍＬ
（２）空間速度
ＮＯ酸化触媒：１００００ｈ -1
ＮＯ2 吸着剤：１００００ｈ -1
（３）反応温度：２５℃
（４）相対湿度：３０％
結果を表１に示す。
【００２５】
【表１】
表１において、ＮＯ吸着率とＮＯ酸化率はそれぞれ以下の算出式から求めた。
【００２７】
【数１】
【発明の効果】
以上のように、本発明の方法によれば、ＮＯを効率よく除去することができる。
【図面の簡単な説明】
【図１】ガス中のＮＯの吸着効果を測定する装置である。
【図２】種々試作品の比表面積に対してＮＯ除去率をプロットしたグラフである。
【符号の説明】
１…ＮＯ標準ガス
２…酸化触媒
３…ＮＯ2 吸着剤
４…ＮＯ分析計[0001]
[Industrial applications]
The present invention is a nitrogen oxide contained in or in a variety of flue exhaust air, in particular to convert difficult NO treatment chemically inert efficiently NO 2, which was adsorbed with an adsorbent And a method for removing NO. More specifically , the present invention relates to a method for oxidizing and adsorbing NO in exhaust gas from automobiles in a tunnel or a parking lot on a highway to reduce the NO to an allowable concentration.
[0002]
[Prior art]
NO, NO 2 is a typical air pollutants, many processing techniques have been proposed heretofore. Numerous adsorbents have been provided , including activated carbon. Known adsorbents, there is no effect thereof much against poor NO reactivity, once oxidized NO, it was taking method for adsorbing and removing in the NO 2. At this time, since ozone was mainly used as the oxidizing agent, an ozone generating device and an adsorbing device, and an ozone decomposing device for decomposing excess ozone were required, and the device was complicated as a whole. .
[0003]
[Problems to be solved by the invention]
The present invention has been made to overcome such drawbacks, aims to use a compact apparatus oxidizes efficiently NO at ambient temperature, which efficiently adsorbed, to provide a method for efficiently removing And
[0004]
[Means for Solving the Problems]
The present invention is a method of oxidizing NO with a catalyst at normal temperature to form NO 2 and adsorbing the generated NO 2 to nickel oxide and / or silver oxide to remove it.
[0005]
Since NO is hardly adsorbed by the adsorbent, all in the conventional method oxidizing the type of absorption easily NO 2 on the adsorbent, had adsorbed removed, a NO oxidation catalyst in accordance with the present invention a specific surface area of 50 m 2 / X-ray diffraction angle (2 [Theta]) is 37 ± 1 ° of the gamma-MnO 2 showing the maximum intensity in g or more, the NO at ordinary temperature efficiently oxidized and converted into NO 2, which is further converted in this way the NO 2, playback of ignitability, instead of the NO 2 absorbent of more conventional activated carbon of problems such as adsorption rate is slow, there is no any problem of ignitability at the time of reproduction, moreover excellent in high speed adsorbing oxide By adsorbing on nickel and / or silver oxide, there is an advantage that it can be carried out in a more compact apparatus than before.
[0006]
The method generally Seisuru the MnO 2 may electrolysis, manganese hydroxide, obtained by oxidizing the gamma-MnO 2 precursor such as manganese carbonate method. The γ-MnO 2 thus produced has the ability to oxidize NO to NO 2 , but the ability is the specific surface of γ-MnO 2 having an X-ray diffraction angle (2θ) showing the maximum intensity of 37 ± 1 °. It depends heavily on the product . If as specific surface area can be seen from Figure 2 is 50 m 2 / g or more, efficiently NO oxidized to NO 2, if 50 m 2 / g or less, it was found that the ability is poor. Therefore, a method for producing a product having a specific surface area of 50 m 2 / g or more was studied.
[0007]
Therefore, we repeated our research and found that the X-ray diffraction angle (2θ) showing the maximum intensity was 37 ± 1 ° and the specific surface area was high, especially γ-MnO 2 of 50 m 2 / g or more by the following method. I found that I could get That is,
1) Firing Temperature manganese carbonate of the general is calcined at 250 ° C. to 450 ° C., and the acid treatment to obtain a γ-MnO 2. Here, if the firing temperature is 450 ° C. or higher , sintering occurs , and if the firing temperature is 250 ° C. or lower, the yield decreases.
[0008]
2) reacting the manganese nitrate and potassium permanganate um, by washing with water drying, it is possible to obtain a gamma-MnO 2 purposes. NO 2 obtained by oxidizing NO with γ-MnO 2 thus obtained and existing NO 2 and N 2 O 3 (referred to as NO x ) are adsorbed by an adsorbent composed of nickel oxide and / or silver oxide. This makes it possible to remove NO present at high speed.
[0009]
The NO 2 adsorbent used in the present invention contains nickel oxide and / or silver oxide as a main component. Nickel oxide is most preferably Ni 2 O 3 obtained by firing nickel carbonate at 250 ° C. to 400 ° C., this time specific surface area of 150 to 250 2 / g, obtained by calcining a basic nickel carbonate NiO can also be preferably used. Commercially available silver oxide can be used as the silver oxide used in the present invention. Alternatively, a material obtained by firing a silver oxide precursor such as silver nitrate may be used. The oxidizing agent or NO 2 adsorbent according to the present invention can be formed into various shapes such as a honeycomb shape and a spherical shape by a conventionally known forming method. In this molding, a molding aid, a molded reinforcing body, an inorganic fiber, an organic binder, and the like may be appropriately blended. Further, it can be coated and supported on a preformed base material by a wash coat method or the like. Furthermore, it can also be based on other conventionally known methods for preparing an adsorbent.
[0010]
【Example】
Hereinafter, a specific example will be described.
Example 1
Special grade manganese carbonate manufactured by Wako Pure Chemical Co., Ltd. was calcined in air at 400 ° C. for 5 hours. 200 g of the obtained baked product was put into 1 L of a 1 / 10N aqueous nitric acid solution, and stirred for 30 minutes to perform an acid treatment. Then, it was washed with filtered and ion-exchanged water. The obtained acid-treated product was 154 g. The specific surface area was 82.6 m 2 / g. The X-ray diffraction angle (2θ) showing the maximum intensity was 36.5 °.
[0011]
Example 2
Produced by Wako Pure Chemical Industries special grade manganese nitrate 121.8g dissolved in ion-exchanged water 20 m L, to prepare an aqueous solution of manganese nitrate. Separately, dissolve the Wako Junyaku Co. special grade permanganate potassium 40g of ion exchange water 2000 m L, to prepare a permanganic acid potassium solution. The aqueous manganese nitrate solution was added dropwise to the aqueous potassium permanganate solution with stirring, and the reaction was completed in about 30 minutes . Thereafter, filtration and washing with ion exchanged water were performed to obtain 61 g of a dried product. At this time, the specific surface area was 204 m 2 / g. The X-ray diffraction intensity angle (2θ) showing the maximum intensity was 36.9 °.
[0012]
Example 3
500 g of special grade nickel carbonate manufactured by Wako Pure Chemical Industries was fired at 350 ° C. for 3 hours to obtain 412 g of nickel oxide. The specific surface area of the obtained Ni 2 O 3 was 235.7 m 2 / g.
[0013]
Preparation of NO Oxidation Catalyst 50 g of the γ-MnO 2 powder obtained in Examples 1 and 2, 30 g of silica sol (trade name: Snowtex D, manufactured by Nissan Chemical Industries, Ltd.) and water are appropriately added, and the mixture is formed into granules, and the mixture is molded into a 20 mesh mesh. The mesh was over 30 mesh.
[0014]
Example 4
500 g of special grade nickel carbonate manufactured by Wako Pure Chemical Co., Ltd. was calcined at 400 ° C. for 3 hours to obtain 366 g of nickel oxide. The specific surface area of the obtained NiO was 131.4 m 2 / g.
[0015]
Preparation of NO 2 adsorbent 50 g of nickel oxide powder obtained in Example 3 or 4 and / or special grade silver oxide manufactured by Wako Pure Chemical Industries, 30 g of Nissan Chemical's silica sol (trade name: Snowtex D) and water are added as needed to obtain a granular form. To form a 20 mesh under 30 mesh over.
[0016]
Example 5
50 g of the nickel oxide obtained in Example 3, 30 g of Nissan Chemical's silica sol (trade name: Snowtex D), and water were appropriately added, and the mixture was formed into a granule to make a 20 mesh under 30 mesh over.
[0017]
Example 6
Using nickel oxide 50g obtained in Example 4, in the same manner as in Example 5 below were prepared NO 2 adsorbent.
[0018]
Example 7
Using nickel oxide 45g and Wako Junyaku Co. special grade silver oxide 5g obtained in Example 3, in the same manner as in Example 5 below were prepared NO 2 adsorbent.
[0019]
Example 8
Using nickel oxide 25g and Wako Junyaku Co. special grade silver oxide 25g obtained in Example 3, in the same manner as in Example 5 below were prepared NO 2 adsorbent.
[0020]
In Comparative Example 1, except that the firing temperature was 550 ° C., to obtain an acid-treated product in the same manner. At this time, the specific surface area was 40.0 m 2 / g.
[0021]
Evaluation test method
As a method according to the present invention, the NO oxidation catalyst according to the above-described
[0022]
FIG. 1 shows the configuration of the apparatus used for the evaluation test. Put from the inlet air (air), this
[0023]
FIG. 2 shows a plot of the NO removal rate against the measured surface area of various prototypes of MnO 2 . The specific surface area represents 78% of the removal rate per 50 m 2 / g, began to increase more, reaching 90% per exceeds 100 m 2 / g are flat.
[0024]
Test conditions (1) Gas composition NO : 5 ppm
Adsorbent : 10 mL
(2) Space velocity NO oxidation catalyst : 10,000 h -1
NO 2 adsorbent : 10,000 h -1
(3) Reaction temperature : 25 ° C
(4) Relative humidity : 30%
Table 1 shows the results.
[0025]
[Table 1]
In Table 1, the NO adsorption rate and the NO oxidation rate were obtained from the following formulas, respectively .
[0027]
(Equation 1)
【The invention's effect】
As described above , according to the method of the present invention, NO can be efficiently removed.
[Brief description of the drawings]
FIG. 1 is an apparatus for measuring the adsorption effect of NO in a gas .
FIG. 2 is a graph in which NO removal rates are plotted against specific surface areas of various prototypes.
[Explanation of symbols]
1: NO standard gas
2. Oxidation catalyst
3 ... NO 2 adsorbent
4: NO analyzer
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08588095A JP3582141B2 (en) | 1995-03-06 | 1995-03-06 | Nitrogen oxide removal method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08588095A JP3582141B2 (en) | 1995-03-06 | 1995-03-06 | Nitrogen oxide removal method |
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| Publication Number | Publication Date |
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| JPH08243356A JPH08243356A (en) | 1996-09-24 |
| JP3582141B2 true JP3582141B2 (en) | 2004-10-27 |
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| JP4715581B2 (en) * | 2006-03-24 | 2011-07-06 | いすゞ自動車株式会社 | Exhaust gas purification system control method and exhaust gas purification system |
| ITMI20120676A1 (en) * | 2012-04-24 | 2013-10-25 | Getters Spa | METHOD AND REGENERABLE PURIFICATION OF AMBIENT TEMPERATURE PURIFICATION FOR DIAZOTO MONOXIDE |
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