JP2009202084A - 排ガス処理触媒 - Google Patents
排ガス処理触媒 Download PDFInfo
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- JP2009202084A JP2009202084A JP2008045818A JP2008045818A JP2009202084A JP 2009202084 A JP2009202084 A JP 2009202084A JP 2008045818 A JP2008045818 A JP 2008045818A JP 2008045818 A JP2008045818 A JP 2008045818A JP 2009202084 A JP2009202084 A JP 2009202084A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 59
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 239000012320 chlorinating reagent Substances 0.000 abstract description 9
- 229910021478 group 5 element Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 12
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229940008718 metallic mercury Drugs 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
【解決手段】 アンモニアを還元剤として接触的に排ガス中の窒素酸化物を除去するとともに、ハロゲンを酸化剤として水銀を酸化する排ガス処理触媒において、TiO2を担体として、該担体上にV,W及びMoからなる群より選ばれる少なくとも1種類の酸化物を活性成分として担持し、かつ周期表第V族に属する元素を含む化合物から選ばれる少なくとも1種類を助触媒成分として担持することとした。
【選択図】 なし
Description
本発明に係る排ガス処理触媒は、さらに他の実施の形態で、上記助触媒成分がBiを含む化合物から成る。
例えば、Vの酸化物を活性成分とし、Pを含むヘテロポリ酸(モリブドリン酸)を助触媒成分とした場合、含有されるVの原子数:Moの原子数:Pの原子数=32:12:1〜10:12:1とすることが好適である。
また、例えば、Vの酸化物を活性成分とし、Biを含む化合物を助触媒成分とした場合、含有されるVの原子数:Moの原子数:Biの原子数=1:3:0.1〜1:10:1.5とすることが好適である。
上記の場合、担体100g当たり0.1〜2質量%の活性成分を担持することが好適である。
(1)例えば、担体成分及び活性成分を含む触媒ペーストをハニカム状に成型し、焼成する。
(2)助触媒成分をハニカムに含浸し、焼成する。
TiO2―V2O5系脱硝触媒(TiO2:V2O5=95.5:0.5(質量比))を以下のように調製した。
メタチタン酸スラリー(TiO2含量30質量%)3600gにNH3含量25%のアンモニア水を加えpHを6.5に調節し、2時間湿式で混練後乾燥し、さらに550℃で5時間焼成して、酸化チタン粉末を得た。この粉末にメタバナジン酸アンモンの水溶液をV2O5換算で0.5質量%、モリブデン酸アンモニウムの水溶液をMoO3換算で7質量%となるよう添加し、充分混合した後乾燥し450℃で4時間焼成して、酸化チタン[TiO2]―酸化バナジウム[V2O5]―酸化モリブデン[MoO3]からなる粉末(A)を得た。粉末(A)1000gにカルボキシメチルセルロース25g、ポリエチレンオキサイド12.5gをニーダーに入れ、適度の水を加えて30分混練し、30mm2のハニカム形状に押出し成型し、乾燥後500℃で5時間焼成した。さらに、硝酸ビスマスの水溶液を調整し、Bi2O3換算で1.5質量%となるようにハニカムに含浸し、500℃で3時間焼成して、Bi2O3(1.5)−MoO3(7)−V2O5/TiO2触媒を調製した。
以上のようにして調製したハニカム状の排ガス処理触媒1を4穴×7穴の500mm長さになるように図1に示すように3段に設置し、水銀酸化性能について試験を行った。
以下の表1に示すO2〜NOxの性状を持つサンプル排ガスを、同表1の条件で流し、排ガス処理触媒1の水銀酸化性能を試験した。なお、表中の記号の意味は、以下の通りである。
Ugs:空塔速度
AV:接ガス面積基準の処理ガス量
サンプル排ガスの抽出位置を図1中のS1〜S2とした。
TiO2―V2O5系脱硝触媒(TiO2:V2O5=95.5:0.5(質量比))を以下のように調製した。
メタチタン酸スラリー(TiO2含量30質量%)3600gにNH3含量25%のアンモニア水を加えpHを6.5に調節し、2時間湿式で混練後乾燥し、さらに550℃で5時間焼成して、酸化チタン粉末を得た。この粉末にメタバナジン酸アンモンの水溶液をV2O5換算で0.5質量%となる様添加し、充分混合した後乾燥し450℃で4時間焼成して、酸化チタン[TiO2]―酸化バナジウム[V2O5]からなる粉末(A)を得た。粉末(A)1000gにカルボキシメチルセルロース25g、ポリエチレンオキサイド12.5gをニーダーに入れ、適度の水を加えて30分混練し、30mm2のハニカム形状に押出し成型し、乾燥後500℃で5時間焼成した。さらに、リンモリブデン酸の水溶液を調整し、MoO3換算で7質量%となるようにハニカムに含浸し、500℃で3時間焼成して、P−MoO3(7)−V2O5(0.5)/TiO2触媒を調製した。
以上のようにして調製したハニカム状の排ガス処理触媒2を4穴×7穴の500mm長さになるように、実施例1の場合と同様に、図1に示すように3段に設置し、水銀酸化性能について試験を行った。
表1と同じO2〜NOxの性状を持つサンプル排ガスを、表3の条件で流し、排ガス処理触媒2の水銀酸化性能を試験した。
TiO2―V2O5系脱硝触媒(TiO2:V2O5=95.5:0.5(質量比))を以下のように調製した。
メタチタン酸スラリー(TiO2含量30質量%)3600gにNH3含量25%のアンモニア水を加えpHを6.5に調節し、2時間湿式で混練後乾燥し、さらに550℃で5時間焼成して、酸化チタン粉末を得た。この粉末にメタバナジン酸アンモンの水溶液をV2O5換算で0.5質量%、モリブデン酸アンモニウムの水溶液をMoO3換算で7質量%となる様添加し、充分混合した後乾燥し450℃で4時間焼成して、酸化チタン[TiO2]―酸化バナジウム[V2O5]―酸化モリブデン[MoO3]からなる粉末(A)を得た。粉末(A)1000gにカルボキシメチルセルロース25g、ポリエチレンオキサイド12.5gをニーダーに入れ、適度の水を加えて30分混練し、30mm2のハニカム形状に押出し成型し、乾燥後500℃で5時間焼成して、比較例のMoO3(7)−V2O5/TiO2触媒を調製した。
以上のようにして調製したハニカム状の比較用排ガス処理触媒を4穴×7穴の500mm長さになるように、実施例1の場合と同様に、図1に示すように3段に設置し、水銀酸化性能について試験を行った。
表1と同じO2〜NOxの性状を持つサンプル排ガスを流し、比較用排ガス処理触媒の水銀酸化性能を試験した。
本発明に係る排ガス処理触媒を用いる場合には、水銀を酸化するためのHCl、HBr噴霧装置やNH4Cl供給装置による新たな水銀酸化剤の添加は極微量でよい。そのため、腐食性の高いHClによる煙道腐食を減殺することができる。
また、石炭由来のHClが排ガス中に数十ppm含まれる場合は、HCl噴霧装置の設置は不要である。その場合、取扱い上注意要するHClの安全管理対策にかかる設備コストを大幅に低減できる。
したがって、本発明に係る排ガス処理触媒は、図2について説明した排ガス処理方法に用いることができる。
10 ボイラ
20 NH3供給箇所
21 HCl注入箇所
30 NH3タンク
40 水銀塩素化剤タンク
60 還元脱硝装置
70 エアヒータ
80 熱交換器
90 集塵器
100 脱硫装置
Claims (3)
- アンモニアを還元剤として接触的に排ガス中の窒素酸化物を除去するとともに、ハロゲンを酸化剤として水銀を酸化する排ガス処理触媒において、TiO2を担体として、該担体上にV,W及びMoからなる群より選ばれる少なくとも1種類の酸化物を活性成分として担持し、かつ周期表第V族に属する元素を含む化合物から選ばれる少なくとも1種類を助触媒成分として担持して成ることを特徴とする排ガス処理触媒。
- 上記助触媒成分がPを含む化合物から成ることを特徴とする請求項1の排ガス処理触媒。
- 上記助触媒成分がBiを含む化合物から成ることを特徴とする請求項1の排ガス処理触媒。
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RU2010106052/04A RU2429908C1 (ru) | 2008-02-27 | 2009-02-26 | Катализатор для обработки выхлопных газов |
CA2694632A CA2694632C (en) | 2008-02-27 | 2009-02-26 | Catalyst for treating exhaust gas |
KR1020107003692A KR101195633B1 (ko) | 2008-02-27 | 2009-02-26 | 배기가스 처리 촉매 |
PCT/JP2009/053573 WO2009107729A1 (ja) | 2008-02-27 | 2009-02-26 | 排ガス処理触媒 |
CN200980100196.9A CN102083529B (zh) | 2008-02-27 | 2009-02-26 | 废气处理催化剂 |
EP09714242.6A EP2248583B1 (en) | 2008-02-27 | 2009-02-26 | USE OF A CATALYST CONTAINING V2O5, MoO3 AND P ON TiO2-SUPPORT FOR EXHAUST GAS TREATMENT |
BRPI0903918-0A BRPI0903918A2 (pt) | 2008-02-27 | 2009-02-26 | Catalisador para tratar gás de exaustão |
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CN102218266A (zh) * | 2010-04-15 | 2011-10-19 | 中国科学院城市环境研究所 | 一种用于催化氧化燃煤烟气中单质汞的方法 |
JP2017500196A (ja) * | 2013-12-11 | 2017-01-05 | ゼァージァン ユニバーシティ | 硝石と水銀の共同コントロール用触媒とその製法 |
JP2020515384A (ja) * | 2017-03-31 | 2020-05-28 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | 排ガスを処理するための触媒、排気システム及び方法 |
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CN111760595A (zh) * | 2020-07-08 | 2020-10-13 | 河南城建学院 | 一种用于低温脱硝除Hg0的杂多酸/CeO2基催化剂及其制备方法和应用 |
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JP2020515384A (ja) * | 2017-03-31 | 2020-05-28 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | 排ガスを処理するための触媒、排気システム及び方法 |
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US20100210455A1 (en) | 2010-08-19 |
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