JP4014412B2 - Organohalogen decomposition catalyst and process for producing the same - Google Patents
Organohalogen decomposition catalyst and process for producing the same Download PDFInfo
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- JP4014412B2 JP4014412B2 JP2002018401A JP2002018401A JP4014412B2 JP 4014412 B2 JP4014412 B2 JP 4014412B2 JP 2002018401 A JP2002018401 A JP 2002018401A JP 2002018401 A JP2002018401 A JP 2002018401A JP 4014412 B2 JP4014412 B2 JP 4014412B2
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- 239000003054 catalyst Substances 0.000 title claims description 89
- 238000000354 decomposition reaction Methods 0.000 title claims description 53
- 238000000034 method Methods 0.000 title description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 36
- 150000002367 halogens Chemical class 0.000 claims description 36
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- -1 amine compound Chemical class 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- 150000002013 dioxins Chemical class 0.000 description 22
- 150000002896 organic halogen compounds Chemical class 0.000 description 19
- 239000007789 gas Substances 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AQBOUNVXZQRXNP-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.N.N.Cl[Pd]Cl AQBOUNVXZQRXNP-UHFFFAOYSA-L 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、主として焼却炉の排ガス処理に使用される有機ハロゲン分解触媒及びその製造方法に関するものである。
【０００２】
【従来の技術】
都市ごみや産業廃棄物の焼却炉から発生する有機ハロゲン化合物の低減対策には、燃焼条件の改善と排ガス処理の高度化とがある。一般に有機ハロゲン化合物のような有機物質の完全酸化分解を燃焼プロセスで行なうには、１０００℃以上の高温維持が必要とされる。しかし、炉壁の損傷を避けるために焼却炉の燃焼温度は８００〜９００℃とされるのが普通であり、燃焼条件の改善によって有機ハロゲン化合物の完全酸化分解を行なうことは容易でない。
【０００３】
また、炉内に局所的な低温部すなわち不完全燃焼部が発生しやすいストーカ炉では、有機ハロゲン化合物の完全酸化分解を行なわせるためには再燃焼部を設ける必要があるが、排ガス総量の増加や再燃焼用燃料によるランニングコストの増加という問題がある。
【０００４】
近年、廃棄物の焼却工程や排ガス処理工程で生じるダイオキシン類や臭素化ダイオキシン類などの有機ハロゲン化合物が人の健康に及ぼす影響や、その発生過程に関する研究が活発化しており、これらの物質は燃焼過程で生成されるのみならず、完全燃焼せずに残留した未燃炭素や、ベンゼン環を持った前駆物質から２００〜５００℃前後の広い低温度域で再合成されることが明らかになっている。
【０００５】
したがって、仮に燃焼プロセスにおいてダイオキシン類や臭素化ダイオキシン類などの有機ハロゲン化合物の低減を図っても、その後の段階でこれらの物質が再合成される可能性があり、排ガス中の有機ハロゲン化合物を安定的に低濃度に維持するためには、排ガス処理による有機ハロゲン化合物の除去が必要となる。
【０００６】
排ガス処理による有機ハロゲン化合物の除去処理方法としては、活性炭による吸着法と、触媒による分解法とが挙げられる。このうち吸着法は有機ハロゲン化合物の除去処理方法の主流を占めているが、コスト高であるうえ有機ハロゲン化合物を吸着させた活性炭が二次廃棄物となり、その後の処理が問題となっている。このため、二次廃棄物が発生しない有機ハロゲン分解触媒による触媒分解法が注目されている。
【０００７】
有機ハロゲン分解触媒としては、Ｖ2Ｏ5-ＴｉＯ2系やＶ2Ｏ5-ＷＯ-ＴｉＯ2系の脱硝触媒に代表される卑金属触媒が主流である。しかしこれらの触媒は集塵機の後段で２５０〜３５０℃の温度域で使用する必要があるため、排ガスの再加熱を必要とする。そこで近年、Ｐｔ／ＴｉＯ2系やＰｄ／ＴｉＯ2系等の貴金属系触媒に関する研究が進められている。ＰｔやＰｄは最も活性の高い貴金属であり、２５０℃以下の低温度域でも活性を発揮することができる。
【０００８】
Ｐｔ／ＴｉＯ2系やＰｄ／ＴｉＯ2系の有機ハロゲン分解触媒を製造するために考えられる従来の一般的な方法は、ＴｉＯ2粉末またはその燒結体に、Ｐｔ及び／またはＰｄの塩の水溶液をコーティングまたは含浸させ、加熱分解してＰｔ及び／またはＰｄを析出させ、最終的に還元処理を行って活性を生じさせる方法である。この場合、触媒形状としてはハニカム型やペレット型が代表的であるが、その形状強度を保つために有機バインダー、有機チタン化合物、有機貴金属化合物等を助剤として原料中に混合させることが多い。
【０００９】
また還元処理の方法としては、水蒸気や水素による方法、ＮａＢＨ4のような還元剤を用いる方法が考えられるが、前者は爆発の危険性があり、後者は残留するＮａが触媒活性を低下させるため好ましくない。このため実用的には、ポリエチレン化合物などの有機物を使用した還元処理が行なわれる。
【００１０】
このように、従来法で製造された有機ハロゲン分解触媒は、有機物を大量に含む原料や助剤を使用したり、有機物を使用した還元処理を施すことによって残留炭素が触媒表面に析出する。ところが本発明者等の研究によれば、これらの残留炭素は触媒の表面を覆って活性を低下させるのみならず、これらの残留炭素が未燃炭素と同様の効果を生じ、ダイオキシン類や臭素化ダイオキシン類などの有機ハロゲン化合物を再合成して逆に増加させてしまう可能性があることが判明した。
【００１１】
【発明が解決しようとする課題】
本発明は上記した問題点を解決し、２５０℃以下の低温度域でも有機ハロゲン化合物を分解処理することができ、しかもダイオキシン類や臭素化ダイオキシン類などの有機ハロゲン化合物を再合成するおそれのない有機ハロゲン分解触媒及びその製造方法を提供するためになされたものである。
【００１２】
【課題を解決するための手段】
上記の課題を解決するためになされた請求項１の有機ハロゲン分解触媒は、アナターゼ型ＴｉＯ2粉末に、Ｐｔ及び／またはＰｄを担持させた触媒であって、触媒中の炭素含有量を０.１重量％以下としたことを特徴とするものである。また請求項２の有機ハロゲン分解触媒は、セラミック基材の表面に、アナターゼ型ＴｉＯ2粉末と、Ｐｔ及び／またはＰｄをコーティングした触媒であって、セラミック基材及び触媒中の炭素含有量を０.１重量％以下としたことを特徴とするものである。
【００１３】
また請求項３の有機ハロゲン分解触媒の製造方法は、請求項１記載の有機ハロゲン分解触媒を製造する方法であって、アナターゼ型ＴｉＯ2粉末を成形した後、その成形体の表面にＰｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物を担持させ、酸化雰囲気中で加熱することによって活性を発揮させることを特徴とするものである。また請求項４の有機ハロゲン分解触媒の製造方法は、請求項１記載の有機ハロゲン分解触媒を製造する方法であって、アナターゼ型ＴｉＯ2粉末と、Ｐｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物とを混合した後、成形し、酸化雰囲気中で加熱することによって活性を発揮させることを特徴とするものである。触媒成形助剤として、ＴｉＯ2ゾルを用いることが好ましい。
【００１４】
さらに請求項５の有機ハロゲン分解触媒の製造方法は、請求項２記載の有機ハロゲン分解触媒を製造する方法であって、セラミック基材の表面に、アナターゼ型ＴｉＯ2粉末をコーティングした後、Ｐｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物を担持させ、酸化雰囲気中で加熱することによって活性を発揮させることを特徴とするものである。また請求項６の有機ハロゲン分解触媒の製造方法は、請求項２記載の有機ハロゲン分解触媒を製造する方法であって、アナターゼ型ＴｉＯ2粉末と、Ｐｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物とを混合した後、セラミック基材の表面にコーティングし、酸化雰囲気中で加熱することによって活性を発揮させることを特徴とするものである。触媒コーティング助剤として、ＴｉＯ2ゾルを用いることが好ましい。
【００１５】
本発明の有機ハロゲン分解触媒は、比表面積の大きいアナターゼ型ＴｉＯ2粉末に活性の高いＰｔ及び／またはＰｄを担持させたものであるから、２５０℃以下（好ましくは２００℃以上）の低温度域でも有機ハロゲン化合物を分解処理することができる。また触媒中の炭素含有量を０.１重量％以下としたので、触媒活性が低下することがないうえ、残留炭素によってダイオキシン類や臭素化ダイオキシン類などの有機ハロゲン化合物が再合成されることもない。また本発明の製造方法によれば、有機物を含まない原料や助剤を用い、還元を行なうことなく触媒活性を発揮させるようにしたため、炭素含有量を０.１重量％以下とした有機ハロゲン分解触媒を製造することができる。
以下に本発明の好ましい実施形態を示す。
【００１６】
【発明の実施の形態】
（第１の実施形態：表面担持）
第１と第２の実施形態は、請求項１の有機ハロゲン分解触媒の製造に関するものである。第１の実施形態では、図１に示すように有機分を含まないアナターゼ型ＴｉＯ2粉末に、触媒成形助剤として有機分を含まない無機増強剤であるＴｉＯ2ゾルを添加して所定形状に成形する。アナターゼ型ＴｉＯ2粉末を用いるのは比表面積が大きく処理対象となる排ガスとの接触面積が広くなるためであり、その粒径は１〜１００μｍ程度とすることが好ましい。またＴｉＯ2ゾルの混合量は、５〜１５％程度とすることが好ましい。成形形状は任意であるが、例えばハニカム状、粒状等とすることができる。
【００１７】
次にその成形体の表面に、Ｐｔ及び／またはＰｄの塩、あるいはＰｔ及び／またはＰｄのアミン化合物を担持させる。Ｐｔの塩としては例えば、塩化白金酸、塩化白金酸６水和物を用いることができる。Ｐｄの塩としては例えば、塩化パラジウム、硝酸パラジウムを用いることができる。Ｐｔのアミン化合物としては例えばジニトロジアミン白金（II）、テトラアンミンジクロロ白金、塩化白金酸アンモニウムを用いることができる。Ｐｄのアミン化合物としては例えばジニトロジアンミンパラジウム（II）、ジクロロジアンミンパラジウム、テトラアンミンパラジウム（II）ジクロライドを用いることができる。
【００１８】
成形体の表面に上記の塩やアミン化合物を担持させる方法としては、例えば、上記の塩やアミン化合物の溶液に成形体を含浸させ乾燥させる方法、もしくは、単位体積の成形体表面に、所定量の貴金属を含んだ塩やアミン化合物の溶液を流下させ乾燥させる方法を採用することができる。
【００１９】
上記のようにして成形体の表面にＰｔ／Ｐｄの塩、あるいはＰｔ／Ｐｄのアミン化合物を担持させたうえ、従来のような還元を行なわず、空中などの酸化雰囲気中で３００℃程度に加熱する。この結果、触媒中の炭素含有量を０.１重量％以下とした有機ハロゲン分解触媒を得ることができる。しかもこの有機ハロゲン分解触媒は酸化雰囲気で使用するため、還元を行わなくてもＣＯやダイオキシン類に対して十分な力を発揮することが確認されている。なお後記する実施例に示すように、触媒中の炭素含有量が０.１重量％を越えるとダイオキシン類等を再合成する可能性が生ずるので好ましくない。
【００２０】
（第２の実施形態：プレドープ）
第２の実施形態では図２に示されるように、上記したと同じアナターゼ型ＴｉＯ2粉末と、Ｐｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物とを予め均一に混合した後、所定形状に成形する。この場合にも触媒成形助剤として有機分を含まない無機増強剤であるＴｉＯ2ゾルを添加し、形状強度を保持させることが好ましい。その後、酸化雰囲気中で加熱することによってＰｔ／Ｐｄの活性を発揮させる。この結果、触媒中の炭素含有量を０.１重量％以下とした有機ハロゲン分解触媒を得ることができる。
【００２１】
（第３の実施形態：表面担持）
第３と第４の実施形態は、請求項２の有機ハロゲン分解触媒の製造に関するものである。第３の実施形態では図３に示すように、先ずセラミック基材の表面に、前記したアナターゼ型ＴｉＯ2粉末をコーティングする。このとき触媒コーティング助剤として、ＴｉＯ2ゾルを５〜１５重量％程度混合することが好ましい。セラミック基材の種類は特に限定されるものではないが、例えば１０００℃以上焼成したムライトやコージェライトを用いることができる。
【００２２】
その後、第１の実施形態と同様にＰｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物を担持させ、酸化雰囲気中で加熱することによって活性を発揮させる。この結果、セラミック表面にコーティングされ、かつ触媒中の炭素含有量を０.１重量％以下とした有機ハロゲン分解触媒を得ることができる。
【００２３】
（第４の実施形態：プレドープ）
第４の実施形態では図４に示すように、アナターゼ型ＴｉＯ2粉末と、Ｐｔ及び／またはＰｄの塩あるいはＰｔ及び／またはＰｄのアミン化合物とを予め混合した後、セラミック基材の表面にコーティングし、酸化雰囲気中で加熱することによって活性を発揮させる。この場合にもＴｉＯ2ゾルを５〜１５重量％程度混合することにより、コーティング強度を高めることが好ましい。この結果、セラミック表面にコーティングされ、かつ触媒中の炭素含有量を０.１重量％以下としたプレドープ型の有機ハロゲン分解触媒を得ることができる。
【００２４】
上記の各実施形態の方法により製造された本発明の有機ハロゲン分解触媒は、２５０℃以下の低温度域でも活性を発揮することができ、焼却炉の排ガス処理に使用する場合にも、排ガスを加熱する必要がない。また触媒中の炭素含有量を０.１重量％以下としたので、ダイオキシン類などの有機ハロゲンを再合成するおそれがない。さらに還元処理を行わないので、還元用の有機物が残留炭素となって触媒の表面を覆うこともなく、触媒活性の低下が防止される。
【００２５】
【実施例】
（実施例１）
実施形態１に記載の方法で製造したＰｔ系の有機ハロゲン分解触媒を直列に接続された８本のガラス管内に充填し、全体を２５０℃に維持した。この流路内に、その量が微量であるにもかかわらず、比較的毒性の高い化合物として代表的な有機ハロゲン化合物であるダイオキシン類を含有させた試験用ガスを流し、入口、中間（４本目と５本目の間）、出口の３箇所でガスを同時にサンプリングしてダイオキシン類濃度を測定した。ＳＶは触媒中間で４０００（ｈ-1）、出口で２０００（ｈ-1）になるように流量を設定した。また比較のために、従来法により製造されたＰｔ系の有機ハロゲン分解触媒を用いて同じ条件で実験を行なった。なお、触媒中の炭素含有量は本発明の触媒では０.０５５重量％であり、従来法により製造された触媒中では０.１３％であった。
【００２６】
その結果、従来法により製造されたＰｔ系の有機ハロゲン分解触媒を用いたときには、入口で１.８６(ngTEQ/m3N)であったダイオキシン類濃度は中間で９.７３(ngTEQ/m3N)、出口で１３.５４(ngTEQ/m3N)であり、有機ハロゲン分解触媒を通すことにより却って増加する傾向が見られた。これは有機ハロゲン分解触媒によりダイオキシン類の再合成が行なわれたことを示している。
【００２７】
これに対して、本発明のＰｔ系の有機ハロゲン分解触媒を用いたときには、入口で２.２４(ngTEQ/m3N)であったダイオキシン類濃度は中間で１.２４(ngTEQ/m3N)、出口で０.１５(ngTEQ/m3N)となり、有機ハロゲン分解触媒を通すことによりダイオキシン類が確実に分解処理されたことが確認された。
【００２８】
（実施例２）
実施形態２に記載の方法で製造したＰｄ系の有機ハロゲン分解触媒を直列に接続された８本のガラス管内に充填し、他の条件は実施例１と同一として実験を行なった。その結果、従来法により製造されたＰｄ系の有機ハロゲン分解触媒を用いたときには、入口で０.９３(ngTEQ/m3N)であったダイオキシン類濃度は中間で２.６４(ngTEQ/m3N)、出口で２.４８(ngTEQ/m3N)であり、有機ハロゲン分解触媒を通すことによりダイオキシン類の再合成が行なわれる傾向が見られた。
【００２９】
これに対して、本発明のＰｄ系の有機ハロゲン分解触媒を用いたときには、入口で１.１９(ngTEQ/m3N)であったダイオキシン類濃度は中間で０.１６(ngTEQ/m3N)、出口で０.０７(ngTEQ/m3N)となり、有機ハロゲン分解触媒を通すことによりダイオキシン類が確実に分解処理されたことが確認された。
【００３０】
【発明の効果】
以上に説明したように、本発明の有機ハロゲン分解触媒及びその製造方法によれば、２５０℃以下の低温度域でも有機ハロゲン化合物を確実に分解処理することができ、しかも有機ハロゲン化合物の中でも、ダイオキシン類を再合成するおそれのない触媒を得ることができる。この触媒は焼却炉の排ガス中のダイオキシン類処理に、好適なものであるが、その他の用途にも適用できることはいうまでもない。
【図面の簡単な説明】
【図１】第１の実施形態を示すブロック図である。
【図２】第２の実施形態を示すブロック図である。
【図３】第３の実施形態を示すブロック図である。
【図４】第４の実施形態を示すブロック図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic halogen decomposition catalyst mainly used for exhaust gas treatment of an incinerator and a method for producing the same.
[0002]
[Prior art]
Measures to reduce organic halogen compounds generated from incinerators for municipal waste and industrial waste include improved combustion conditions and advanced exhaust gas treatment. In general, in order to perform complete oxidative decomposition of an organic substance such as an organic halogen compound by a combustion process, it is necessary to maintain a high temperature of 1000 ° C. or higher. However, in order to avoid damage to the furnace wall, the combustion temperature of the incinerator is usually set to 800 to 900 ° C., and it is not easy to perform complete oxidative decomposition of the organic halogen compound by improving the combustion conditions.
[0003]
In addition, in a stoker furnace where local low-temperature parts, that is, incomplete combustion parts are likely to occur in the furnace, it is necessary to provide a re-combustion part in order to perform complete oxidative decomposition of organic halogen compounds, but this increases the total amount of exhaust gas. In addition, there is a problem of increased running costs due to fuel for reburning.
[0004]
In recent years, research on the effects of organic halogen compounds such as dioxins and brominated dioxins generated in waste incineration and exhaust gas treatment processes on human health and the process of their generation has become active. It is not only generated in the process, but also recombined from unburned carbon remaining without complete combustion and precursors with benzene rings in a wide low temperature range around 200-500 ° C. Yes.
[0005]
Therefore, even if organic halogen compounds such as dioxins and brominated dioxins are reduced in the combustion process, these substances may be re-synthesized at a later stage, which stabilizes the organic halogen compounds in the exhaust gas. In order to maintain a low concentration, it is necessary to remove the organic halogen compound by exhaust gas treatment.
[0006]
Examples of the organic halogen compound removal treatment method by exhaust gas treatment include an adsorption method using activated carbon and a decomposition method using a catalyst. Of these, the adsorption method occupies the mainstream of the organic halogen compound removal treatment method. However, the cost is high and activated carbon on which the organic halogen compound is adsorbed becomes secondary waste, and the subsequent treatment becomes a problem. For this reason, a catalytic decomposition method using an organic halogen decomposition catalyst that does not generate secondary waste is attracting attention.
[0007]
As the organic halogen decomposition catalyst, a base metal catalyst typified by a V 2 O 5 —TiO 2 -based or V 2 O 5 —WO—TiO 2 -based denitration catalyst is mainly used. However, since these catalysts need to be used in the temperature range of 250 to 350 ° C. after the dust collector, it is necessary to reheat the exhaust gas. In recent years, research on noble metal catalysts such as Pt / TiO 2 and Pd / TiO 2 has been conducted. Pt and Pd are the most active noble metals and can exhibit activity even in a low temperature range of 250 ° C. or lower.
[0008]
A conventional general method that can be considered for producing a Pt / TiO 2 -based or Pd / TiO 2 -based organic halogen decomposition catalyst is that an aqueous solution of a salt of Pt and / or Pd is added to TiO 2 powder or a sintered body thereof. In this method, coating or impregnation is performed, thermal decomposition is performed to precipitate Pt and / or Pd, and finally reduction treatment is performed to generate activity. In this case, the catalyst shape is typically a honeycomb type or a pellet type, but in order to maintain the shape strength, an organic binder, an organic titanium compound, an organic noble metal compound, or the like is often mixed into the raw material as an auxiliary agent.
[0009]
Further, as a method of the reduction treatment, a method using water vapor or hydrogen and a method using a reducing agent such as NaBH 4 are conceivable, but the former has a risk of explosion, and the latter is because residual Na lowers the catalytic activity. It is not preferable. For this reason, reduction treatment using an organic substance such as a polyethylene compound is practically performed.
[0010]
Thus, the organic halogen decomposition catalyst manufactured by the conventional method uses the raw material and auxiliary agent which contain organic substance in large quantities, or residual carbon precipitates on the catalyst surface by performing the reduction process using organic substance. However, according to the study by the present inventors, these residual carbons not only cover the surface of the catalyst and reduce the activity, but these residual carbons produce the same effect as unburned carbon, dioxins and bromination It was found that organic halogen compounds such as dioxins could be re-synthesized and increased in reverse.
[0011]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems, can decompose organic halogen compounds even in a low temperature range of 250 ° C. or lower, and does not cause the possibility of re-synthesizing organic halogen compounds such as dioxins and brominated dioxins. The present invention has been made to provide an organic halogen decomposition catalyst and a method for producing the same.
[0012]
[Means for Solving the Problems]
The organohalogen decomposition catalyst according to claim 1, which has been made to solve the above-mentioned problems, is a catalyst in which Pt and / or Pd is supported on anatase TiO 2 powder, and the carbon content in the catalyst is reduced to 0.5. It is characterized by being 1% by weight or less. The organohalogen decomposition catalyst according to claim 2 is a catalyst in which the surface of a ceramic base material is coated with anatase TiO 2 powder and Pt and / or Pd, and the carbon content in the ceramic base material and the catalyst is reduced to 0. .1% by weight or less.
[0013]
The method for producing an organic halogen decomposition catalyst according to claim 3 is a method for producing the organic halogen decomposition catalyst according to claim 1, wherein after anatase-type TiO 2 powder is formed, Pt and / or Alternatively, a salt of Pd or an amine compound of Pt and / or Pd is supported, and the activity is exhibited by heating in an oxidizing atmosphere. The method for producing an organic halogen decomposition catalyst according to claim 4 is a method for producing the organic halogen decomposition catalyst according to claim 1, wherein the anatase TiO 2 powder and a salt of Pt and / or Pd or Pt and / or After mixing with an amine compound of Pd, it is molded, and the activity is exhibited by heating in an oxidizing atmosphere. It is preferable to use a TiO 2 sol as a catalyst forming aid.
[0014]
Furthermore, the method for producing an organohalogen decomposition catalyst according to claim 5 is a method for producing the organohalogen decomposition catalyst according to claim 2, wherein the surface of the ceramic base material is coated with anatase TiO 2 powder, Pt and It is characterized by supporting activity by supporting a salt of Pd or / or an amine compound of Pt and / or Pd and heating in an oxidizing atmosphere. The method for producing an organic halogen decomposition catalyst according to claim 6 is a method for producing the organic halogen decomposition catalyst according to claim 2, wherein the anatase TiO 2 powder and a salt of Pt and / or Pd or Pt and / or After mixing with an amine compound of Pd, the surface of the ceramic base material is coated, and the activity is exhibited by heating in an oxidizing atmosphere. It is preferable to use a TiO 2 sol as a catalyst coating aid.
[0015]
The organohalogen decomposition catalyst of the present invention is such that anatase-type TiO 2 powder having a large specific surface area is loaded with highly active Pt and / or Pd, and therefore a low temperature range of 250 ° C. or lower (preferably 200 ° C. or higher). However, the organic halogen compound can be decomposed. In addition, since the carbon content in the catalyst is 0.1% by weight or less, the catalytic activity does not decrease, and organic halogen compounds such as dioxins and brominated dioxins may be re-synthesized by residual carbon. Absent. Further, according to the production method of the present invention, since the catalytic activity is exhibited without reduction using raw materials and auxiliaries that do not contain organic substances, the organic halogen decomposition with a carbon content of 0.1% by weight or less is performed. A catalyst can be produced.
Preferred embodiments of the present invention are shown below.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
(First embodiment: surface support)
The first and second embodiments relate to the production of the organic halogen decomposition catalyst according to claim 1. In the first embodiment, as shown in FIG. 1, a TiO 2 sol, which is an inorganic enhancer that does not contain an organic component, is added to an anatase-type TiO 2 powder that does not contain an organic component as a catalyst molding aid to obtain a predetermined shape. Mold. The anatase TiO 2 powder is used because the specific surface area is large and the contact area with the exhaust gas to be treated is widened, and the particle size is preferably about 1 to 100 μm. The amount of TiO 2 sol mixed is preferably about 5 to 15%. The forming shape is arbitrary, but may be, for example, a honeycomb shape or a granular shape.
[0017]
Next, a Pt and / or Pd salt or an amine compound of Pt and / or Pd is supported on the surface of the molded body. As the salt of Pt, for example, chloroplatinic acid or chloroplatinic acid hexahydrate can be used. As the salt of Pd, for example, palladium chloride or palladium nitrate can be used. As the amine compound of Pt, for example, dinitrodiamineplatinum (II), tetraamminedichloroplatinum, or ammonium chloroplatinate can be used. As the amine compound of Pd, for example, dinitrodiammine palladium (II), dichlorodiammine palladium, tetraammine palladium (II) dichloride can be used.
[0018]
Examples of the method of supporting the salt or amine compound on the surface of the molded body include, for example, a method of impregnating the molded body in a solution of the salt or amine compound and drying, or a predetermined amount on the surface of the molded body of unit volume. A method of allowing a salt or amine compound solution containing noble metal to flow down and drying can be employed.
[0019]
As described above, a Pt / Pd salt or a Pt / Pd amine compound is supported on the surface of the molded body and heated to about 300 ° C. in an oxidizing atmosphere such as in the air without performing conventional reduction. To do. As a result, an organic halogen decomposition catalyst having a carbon content of 0.1% by weight or less can be obtained. Moreover, since this organohalogen decomposition catalyst is used in an oxidizing atmosphere, it has been confirmed that it exerts sufficient power against CO and dioxins without performing reduction. As shown in the examples described later, if the carbon content in the catalyst exceeds 0.1% by weight, the possibility of re-synthesizing dioxins and the like is not preferable.
[0020]
(Second embodiment: pre-dope)
In the second embodiment, as shown in FIG. 2, the same anatase-type TiO 2 powder as described above and a salt of Pt and / or Pd or an amine compound of Pt and / or Pd are mixed in advance, Mold into a predetermined shape. In this case as well, it is preferable to add a TiO 2 sol, which is an inorganic enhancer that does not contain an organic component, as a catalyst forming aid to maintain the shape strength. Thereafter, the Pt / Pd activity is exhibited by heating in an oxidizing atmosphere. As a result, an organic halogen decomposition catalyst having a carbon content of 0.1% by weight or less can be obtained.
[0021]
(Third embodiment: surface support)
The third and fourth embodiments relate to the production of the organic halogen decomposition catalyst according to claim 2. In the third embodiment, as shown in FIG. 3, the surface of the ceramic substrate is first coated with the anatase TiO 2 powder. At this time, it is preferable to mix about 5 to 15% by weight of TiO 2 sol as a catalyst coating aid. Although the kind of ceramic base material is not specifically limited, For example, mullite and cordierite fired at 1000 ° C. or more can be used.
[0022]
Thereafter, the Pt and / or Pd salt or the amine compound of Pt and / or Pd is supported as in the first embodiment, and the activity is exhibited by heating in an oxidizing atmosphere. As a result, an organic halogen decomposition catalyst coated on the ceramic surface and having a carbon content in the catalyst of 0.1% by weight or less can be obtained.
[0023]
(Fourth embodiment: pre-dope)
In the fourth embodiment, as shown in FIG. 4, after anatase type TiO 2 powder and a salt of Pt and / or Pd or an amine compound of Pt and / or Pd are mixed in advance, the surface of the ceramic substrate is coated. Then, the activity is exhibited by heating in an oxidizing atmosphere. Also in this case, it is preferable to increase the coating strength by mixing about 5 to 15% by weight of TiO 2 sol. As a result, it is possible to obtain a pre-doped type organic halogen decomposition catalyst which is coated on the ceramic surface and has a carbon content in the catalyst of 0.1% by weight or less.
[0024]
The organohalogen decomposition catalyst of the present invention produced by the method of each of the above embodiments can exhibit activity even in a low temperature range of 250 ° C. or lower, and even when used for exhaust gas treatment of an incinerator, There is no need to heat. In addition, since the carbon content in the catalyst is 0.1% by weight or less, there is no possibility of re-synthesizing organic halogens such as dioxins. Further, since the reduction treatment is not performed, the organic substance for reduction becomes residual carbon and does not cover the surface of the catalyst, thereby preventing a decrease in catalyst activity.
[0025]
【Example】
Example 1
The Pt-based organohalogen decomposition catalyst produced by the method described in Embodiment 1 was filled in eight glass tubes connected in series, and the whole was maintained at 250 ° C. A test gas containing dioxins, which are typical organic halogen compounds as a relatively highly toxic compound, is allowed to flow into this flow path, although the amount is very small. The gas was sampled at three outlets at the same time, and the dioxins concentration was measured. The flow rate of SV was set to 4000 (h -1 ) in the middle of the catalyst and 2000 (h -1 ) at the outlet. For comparison, an experiment was performed under the same conditions using a Pt-based organic halogen decomposition catalyst produced by a conventional method. The carbon content in the catalyst was 0.055% by weight in the catalyst of the present invention, and 0.13% in the catalyst produced by the conventional method.
[0026]
As a result, when the Pt-based organohalogen decomposition catalyst produced by the conventional method was used, the dioxin concentration which was 1.86 (ngTEQ / m 3 N) at the inlet was 9.73 (ngTEQ / m 3 ) in the middle. N) and 13.54 (ngTEQ / m 3 N) at the outlet, and a tendency to increase by passing through an organic halogen decomposition catalyst was observed. This indicates that dioxins were re-synthesized with an organic halogen decomposition catalyst.
[0027]
In contrast, when using the Pt-based organic halogen decomposition catalyst of the present invention, the inlet at 2.24 (ngTEQ / m 3 N) in a dioxins concentration in the middle 1.24 (ngTEQ / m 3 N ) And 0.15 (ngTEQ / m 3 N) at the outlet, and it was confirmed that the dioxins were reliably decomposed by passing the organic halogen decomposition catalyst.
[0028]
(Example 2)
The experiment was conducted under the same conditions as in Example 1 except that the Pd-based organic halogen decomposition catalyst produced by the method described in Embodiment 2 was filled in eight glass tubes connected in series. As a result, when the Pd-based organohalogen decomposition catalyst produced by the conventional method was used, the dioxin concentration which was 0.93 (ngTEQ / m 3 N) at the inlet was 2.64 (ngTEQ / m 3 ) in the middle. N) and 2.48 (ngTEQ / m 3 N) at the outlet, and dioxins tended to be re-synthesized by passing through an organic halogen decomposition catalyst.
[0029]
In contrast, when the Pd-based organohalogen decomposition catalyst of the present invention was used, the dioxin concentration that was 1.19 (ngTEQ / m 3 N) at the inlet was 0.16 (ngTEQ / m 3 N) in the middle. ) And 0.07 (ngTEQ / m 3 N) at the outlet, and it was confirmed that the dioxins were reliably decomposed by passing the organic halogen decomposition catalyst.
[0030]
【The invention's effect】
As described above, according to the organic halogen decomposition catalyst and the production method thereof of the present invention, the organic halogen compound can be reliably decomposed even in a low temperature range of 250 ° C. or lower, and among the organic halogen compounds, A catalyst that does not have the risk of re-synthesizing dioxins can be obtained. This catalyst is suitable for treating dioxins in exhaust gas from an incinerator, but it goes without saying that it can be applied to other applications.
[Brief description of the drawings]
FIG. 1 is a block diagram showing a first embodiment.
FIG. 2 is a block diagram showing a second embodiment.
FIG. 3 is a block diagram showing a third embodiment.
FIG. 4 is a block diagram showing a fourth embodiment.
Claims (8)
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