JP6232223B2 - 排ガス浄化方法 - Google Patents
排ガス浄化方法 Download PDFInfo
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- JP6232223B2 JP6232223B2 JP2013154752A JP2013154752A JP6232223B2 JP 6232223 B2 JP6232223 B2 JP 6232223B2 JP 2013154752 A JP2013154752 A JP 2013154752A JP 2013154752 A JP2013154752 A JP 2013154752A JP 6232223 B2 JP6232223 B2 JP 6232223B2
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- exhaust gas
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- 238000000034 method Methods 0.000 title claims description 48
- 238000000746 purification Methods 0.000 title claims description 34
- 239000007789 gas Substances 0.000 claims description 181
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 85
- 239000003054 catalyst Substances 0.000 claims description 65
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 55
- 238000002485 combustion reaction Methods 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000004868 gas analysis Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013056 hazardous product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- F01N3/18—Exhaust 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
- F01N3/20—Exhaust 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
- F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
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Description
図1に示す構成の脱硝試験装置を使用して排ガスの脱硝試験を行った。脱硝試験の手順は、次のとおりである。
ZSM−5(MFI)型ゼオライト(HSZ−830NHA、東ソー株式会社製)、およびイオン交換水、シリカゾル〔シリカドール(登録商標)、日本化学工業株式会社製〕を、重量比100:100:46で混合し、スラリーを得た。
得られた平板状基材を、温度80℃に加熱した30重量%の硝酸コバルト溶液5Lに6時間以上浸漬し、イオン交換により、ZSM−5(MFI)型ゼオライトにコバルトを担持させた脱硝触媒を作製した。
上記で得られた脱硝触媒について、図1にフロー図を示す脱硝試験装置を使用して排ガスについての脱硝触媒性能試験を行った。
ここで、表1における「Balance」は、ガス組成がトータルで100%になるように添加されるものを表し、NO、エタノール、水分以外のガス組成が空気(表中ではAirと表示)によって占められていることを示している。また、「面積速度」は下記の数式(I)より算出した。
面積速度=ガス流量/触媒幾何面積 …(I)
反応管(1)から出て、ライン(18)から取り出された処理済みガスのガス分析は、NOx計を用いて反応管(1)の出口NOx濃度を測定した。NOx計での測定値から、下記の数式(II)によって触媒のNOx除去性能である脱硝率を算出した。
得られた脱硝触媒性能の評価試験の結果を、下記の表2に示した。
上記実施例1の場合と同様にして、本発明の排ガス浄化方法に対応する脱硝触媒性能評価試験を、上記表1に示す試験条件とほぼ同様の条件で実施するが、上記実施例1の場合と異なる点は、実施例2〜8では、処理すべき原排ガスに、追加用水槽(21)からの定量送液ポンプ(22)の汲み上げ量を調整して、ライン(20)によってさらに水蒸気を添加し、水分調整排ガス中の水蒸気濃度が、原排ガス既存含有水蒸気および添加水蒸気の合計で4.9容量%(実施例2)、8.6容量%(実施例3)、10.1容量%(実施例4)、11.0容量%(実施例5)、14.0容量%(実施例6)、19.1容量%(実施例7)、および21.2容量%(実施例8)と、順次増加させた水分調整排ガスを、脱硝触媒層を具備する反応管(1)にそれぞれ供給した点にある。
参考のために、上記実施例1の場合と同様にして、触媒性能評価試験を実施するが、上記実施例1の場合と異なる点は、反応管(1)に導入する試験用の原排ガスを、ライン(4)からの空気、およびライン(5)からのNO/N2ガスを混合することにより調製し、原水槽(11)の定量送液ポンプ(12)および追加用水槽(21)の定量送液ポンプ(22)の作動をいずれも停止させて、水蒸気濃度0容量%の原排ガスを、脱硝触媒層を具備する反応管(1)に導入した点にある。そして、反応管(1)から出た処理済みガスのガス分析を、上記実施例1の場合と同様に行い、得られた脱硝触媒性能の評価試験の結果を、下記の表2にあわせて示した。
上記実施例1の場合と同様にして、本発明の排ガス浄化方法に対応する脱硝触媒性能評価試験を、上記表1に示す試験条件とほぼ同様の条件で実施するが、上記実施例1の場合と異なる点は、上記実施例1では、原排ガス中への水蒸気の添加を、燃焼排ガス中に液体状または気体状の水を導入して行ったのに対し、実施例9では、原排ガス中への水蒸気の添加を、燃焼排ガス中にエタノール水溶液を導入して行った点にある。そのために、図3にフロー図を示す脱硝試験装置を使用して排ガスについての脱硝触媒性能試験を行った。
2:排ガス供給ライン
3:処理済みガス排出ライン
4:空気供給ライン
5:NO/N2ガス供給ライン
6:バルブ
7:バルブ
8:原排ガス供給ライン
9:蒸発器
10:水分供給ライン
11:原水槽
12:定量送液ポンプ
13:エタノール供給ライン
14:エタノール貯留槽
15:空気供給ライン
16:バルブ
17:処理済みガス排出ライン
18:処理済みガス一部取出しライン
20:追加用水供給ライン
21:追加用水槽
22:定量送液ポンプ
24:エタノール水溶液貯留槽
25:定量送液ポンプ
26:エタノール水溶液供給ライン
Claims (6)
- 還元剤としてアルコールを添加した燃焼排ガスを脱硝触媒に接触させることにより、排ガス中の窒素酸化物を除去する排ガスの浄化方法において、
該脱硝触媒は、ZSM−5(MFI)型ゼオライトにコバルトを担持させた脱硝触媒であり、
処理すべき原排ガスにさらに水蒸気を添加して、排ガス中の水蒸気濃度を増加させた水分調整排ガスを、該脱硝触媒層に導入することを特徴とする、排ガス浄化方法。 - 水分調整排ガス中の水蒸気濃度が、原排ガス既存含有水蒸気および添加水蒸気の合計で22.0容量%以下であることを特徴とする、請求項1に記載の排ガス浄化方法。
- 原排ガス中への水蒸気の添加を、燃焼排ガス中に液体状または気体状の水を導入して行うことを特徴とする、請求項1または2に記載の排ガス浄化方法。
- 原排ガス中への水蒸気の添加を、燃焼排ガス中にアルコール水溶液を導入して行うことを特徴とする、請求項1または2に記載の排ガス浄化方法。
- アルコールがエタノールであり、原排ガス中に導入するエタノール水溶液の濃度が5.0容量%以下であることを特徴とする、請求項4に記載の排ガス浄化方法。
- 排ガスが、船舶用ディーゼルエンジンからの燃焼排ガスであることを特徴とする、請求項1〜5のうちのいずれか一項に記載の排ガス浄化方法。
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