JPH09276659A - Catalyst for removal of nitrogen oxide contained in exhaust gas by reduction and manufacture of catalyst - Google Patents
Catalyst for removal of nitrogen oxide contained in exhaust gas by reduction and manufacture of catalystInfo
- Publication number
- JPH09276659A JPH09276659A JP8096548A JP9654896A JPH09276659A JP H09276659 A JPH09276659 A JP H09276659A JP 8096548 A JP8096548 A JP 8096548A JP 9654896 A JP9654896 A JP 9654896A JP H09276659 A JPH09276659 A JP H09276659A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- weight
- parts
- molded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000007789 gas Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 230000009467 reduction Effects 0.000 title abstract description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 42
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 abstract description 23
- 238000000465 moulding Methods 0.000 abstract description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 238000002485 combustion reaction Methods 0.000 description 16
- 238000005299 abrasion Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008859 change Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 8
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000004323 axial length Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- LYSTYSFIGYAXTG-UHFFFAOYSA-L barium(2+);hydrogen phosphate Chemical compound [Ba+2].OP([O-])([O-])=O LYSTYSFIGYAXTG-UHFFFAOYSA-L 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- RPUZVWKKWXPKIP-UHFFFAOYSA-H dialuminum;hydrogen phosphate Chemical compound [Al+3].[Al+3].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O RPUZVWKKWXPKIP-UHFFFAOYSA-H 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- XGFPOHQJFNFBKA-UHFFFAOYSA-B tetraaluminum;phosphonato phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O XGFPOHQJFNFBKA-UHFFFAOYSA-B 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、排ガスに含まれる
窒素酸化物を還元剤を用いて還元除去するための触媒と
方法とに関し、更に、そのような触媒の製造方法に関す
る。特に、本発明は、排ガスに含まれる窒素酸化物を還
元剤を用いて還元除去するための触媒であって、排ガス
に含まれるダストによる摩耗に対する抵抗を有する触媒
と、排ガスに含まれる窒素酸化物を還元剤を用いて還元
除去するに際して、そのような触媒を用いる方法とに関
し、更に、そのような触媒の製造方法に関する。TECHNICAL FIELD The present invention relates to a catalyst and a method for reducing and removing nitrogen oxides contained in exhaust gas by using a reducing agent, and further to a method for producing such a catalyst. In particular, the present invention is a catalyst for reducing and removing nitrogen oxides contained in exhaust gas using a reducing agent, the catalyst having resistance to abrasion due to dust contained in the exhaust gas, and nitrogen oxides contained in the exhaust gas. The present invention relates to a method of using such a catalyst for reducing and removing methane using a reducing agent, and further relates to a method of producing such a catalyst.
【０００２】[0002]
【従来の技術】排ガスに含まれる窒素酸化物を触媒の存
在下にアンモニア等の還元剤と接触させて、還元除去す
る、即ち、脱硝するための触媒と方法は、既に種々のも
のが知られている。このような触媒のなかでも、触媒反
応器において、排ガスの流れ方向に貫通孔を有する固定
床を構成する成形触媒、例えば、所謂ハニカム触媒は、
一般に、ガス流れによる圧力損失が少ないので、他の固
定床触媒を充填した触媒反応器に比較して、排ガスの線
速度を大きくすることができ、更に、排ガスがダストを
含むときには、そのダストによって、上記貫通孔が目詰
まりを起こすことが少ないので、効率よく所要のガス接
触反応を行わせることができる利点を有し、従って、ハ
ニカム触媒は、従来、例えば、ボイラ等から発生する窒
素酸化物を含む燃焼排ガスの脱硝反応のために広く用い
られている。2. Description of the Related Art Various catalysts and methods have already been known for removing nitrogen oxides contained in exhaust gas by contacting them with a reducing agent such as ammonia in the presence of a catalyst, that is, for removing NOx. ing. Among such catalysts, in the catalytic reactor, a shaped catalyst forming a fixed bed having through holes in the flow direction of exhaust gas, for example, a so-called honeycomb catalyst,
Generally, since the pressure loss due to the gas flow is small, the linear velocity of the exhaust gas can be increased as compared with other catalytic reactors packed with other fixed bed catalysts. Since the through holes are less likely to be clogged, there is an advantage that the required gas contact reaction can be efficiently performed. Therefore, the honeycomb catalyst is conventionally used, for example, a nitrogen oxide generated from a boiler or the like. It is widely used for the denitrification reaction of combustion exhaust gas containing.
【０００３】しかしながら、このようなハニカム触媒を
用いる排ガスの処理においても、排ガスが摩耗性を有す
るダストを含むときには、このダストによってハニカム
触媒が摩耗し、その結果、ハニカム触媒が徐々に減耗
し、最終的には形状を失なって、使用に耐えなくなる場
合さえある。However, even in the treatment of exhaust gas using such a honeycomb catalyst, when the exhaust gas contains dust having abradability, the honeycomb catalyst is abraded by the dust, and as a result, the honeycomb catalyst is gradually depleted and finally In some cases, it loses its shape and becomes unusable.
【０００４】そこで、従来、例えば、特公昭５７−１４
２１１号公報、特公昭５７−２６８２０号公報、特公昭
５７−２６８２０号公報や、米国特許第 4,294,806号等
に記載されているように、排ガスの入口と出口とを備え
た触媒反応器に充填して用いる成形触媒であって、上記
入口からその触媒反応器に導入される排ガスの流れ方向
に少なくとも１つの貫通孔を有する成形触媒において、
排ガスの入口を含む成形触媒の先端部分を焼結したり、
或いはガラス物質で被覆し、強化して、耐摩耗性とする
ことが知られている。このような先端部分を強化した成
形触媒によれば、排ガスが摩耗性を有するダストを含む
場合であっても、成形触媒の先端部分をダストによる摩
耗から防止することができる。Therefore, conventionally, for example, Japanese Patent Publication No. 57-14.
No. 211, JP-B-57-26820, JP-B-57-26820, US Pat. No. 4,294,806, etc., the catalyst reactor provided with an exhaust gas inlet and an outlet is filled. A molded catalyst used as a molded catalyst having at least one through hole in a flow direction of an exhaust gas introduced into the catalytic reactor from the inlet,
Sinter the tip of the molded catalyst including the exhaust gas inlet,
Alternatively, it is known to coat and strengthen glass materials to make them wear resistant. According to the shaped catalyst having the reinforced tip portion, the tip portion of the shaped catalyst can be prevented from being worn by the dust even when the exhaust gas contains dust having abradability.
【０００５】しかし、代表的には、石炭焚きボイラから
の燃焼排ガスのように、摩耗性を有するダストを多量に
含む燃焼排ガスの脱硝処理においては、触媒反応器の断
面における排ガスの流れの不均一が起こりやすく、この
ことに起因して、触媒反応器内において、ダスト濃度の
不均一やダストの粒度分布の偏り等が生じることにな
り、かくして、上述したように、先端部分を強化した成
形触媒を用いる場合であっても、成形触媒がその他の箇
所において、局部的に摩耗することとなる。[0005] However, typically, in the denitration treatment of a combustion exhaust gas containing a large amount of dust having abradability such as a combustion exhaust gas from a coal-fired boiler, the flow of the exhaust gas in the cross section of the catalytic reactor is not uniform. Is likely to occur, and due to this, in the catalytic reactor, non-uniformity of the dust concentration and uneven distribution of the particle size distribution of dust occur, and thus, as described above, the molded catalyst with the tip portion reinforced. Even in the case of using, the shaped catalyst is locally worn at other places.
【０００６】そこで、成形触媒のガス入口を含む端面か
ら貫通孔の方向に長い距離にわたる先端部分を強化すれ
ば、その分、成形触媒を耐摩耗性とすることができる
が、反面、このように強化処理した触媒壁の面積が大き
くなればなるほど、得られる成形触媒は、初期の触媒活
性が低いものになる。Therefore, by strengthening the tip portion over a long distance in the direction of the through hole from the end surface including the gas inlet of the shaped catalyst, the shaped catalyst can be made wear-resistant by that amount, but on the other hand, The larger the area of the strengthened catalyst walls, the lower the initial catalytic activity of the resulting shaped catalyst.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、排ガスに含
まれる窒素酸化物を触媒の存在下に還元剤を用いて還元
除去するための従来の触媒及び方法における上述したよ
うな問題を解決するためになされたものであって、耐摩
耗性と強度にすぐれ、排ガスに含まれる窒素酸化物を長
期間にわたって安定して還元除去することができる触媒
と方法とを提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in conventional catalysts and methods for reducing and removing nitrogen oxides contained in exhaust gas by using a reducing agent in the presence of a catalyst. It is an object of the present invention to provide a catalyst and a method which are excellent in wear resistance and strength and can stably reduce and remove nitrogen oxides contained in exhaust gas over a long period of time.
【０００８】特に、本発明は、触媒活性を損なうことな
く、排ガス中に含まれる摩耗性を有するダストによる摩
耗に対する強度を付与した触媒と、更に、排ガスに含ま
れる窒素酸化物を還元剤を用いてそのような触媒の存在
下に長期間にわたって安定して還元除去することができ
る方法を提供することを目的とする。更に、本発明は、
上述したような触媒の製造方法を提供することを目的と
する。[0008] In particular, the present invention uses a catalyst that imparts strength to abrasion by dust having abradability contained in exhaust gas without impairing catalytic activity, and further uses nitrogen oxide contained in the exhaust gas as a reducing agent. It is an object of the present invention to provide a method capable of performing stable reduction and removal over a long period of time in the presence of such a catalyst. Further, the present invention provides
It is an object of the present invention to provide a method for producing the above catalyst.
【０００９】[0009]
【課題を解決するための手段】本発明による排ガスに含
まれる窒素酸化物を還元除去するための成形触媒は、
(a) 酸化チタン又は酸化チタン−シリカ複合酸化物１０
０重量部に対して、(b) 三酸化タングステン５〜２０重
量部と、(c) 五酸化バナジウム０〜2.０重量部とを含む
多孔質成形体に硫酸マグネシウム水溶液を含浸させ、加
熱焼成して、硫酸マグネシウムを0.５〜5.５重量部の範
囲で上記多孔質成形体に担持させてなることを特徴とす
る。A molded catalyst for reducing and removing nitrogen oxides contained in exhaust gas according to the present invention comprises:
(a) Titanium oxide or titanium oxide-silica composite oxide 10
0 parts by weight of (b) 5 to 20 parts by weight of tungsten trioxide and (c) 0 to 2.0 parts by weight of vanadium pentoxide are impregnated with an aqueous magnesium sulfate solution and heated and baked. Then, magnesium sulfate is supported on the porous molded body in a range of 0.5 to 5.5 parts by weight.
【００１０】[0010]
【発明の実施の形態】本発明において、窒素酸化物と
は、例えば、一酸化窒素、三酸化二窒素、二酸化窒素等
をいうものとする。本発明において、成形体は、主成分
が酸化チタンか、又は酸化チタン−シリカ複合酸化物か
らなり、従成分として、三酸化タングステンを含み、必
要に応じて、五酸化バナジウムを含む多孔質体であっ
て、このような多孔質成形体に硫酸マグネシウム水溶液
を含浸させ、加熱焼成して、硫酸マグネシウムを担持さ
せたものが本発明による成形触媒である。本発明におい
ては、上記成形体を形成する上記成分を触媒成分とい
う。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the nitrogen oxides mean, for example, nitric oxide, dinitrogen trioxide, nitrogen dioxide and the like. In the present invention, the molded body is a porous body containing titanium oxide as a main component or titanium oxide-silica composite oxide, containing tungsten trioxide as a subordinate component, and, if necessary, vanadium pentoxide. Therefore, the molded catalyst according to the present invention is obtained by impregnating such a porous molded body with an aqueous magnesium sulfate solution, heating and firing it to support magnesium sulfate. In the present invention, the above-mentioned components forming the above-mentioned molded body are called catalyst components.
【００１１】本発明による特に好ましい成形触媒は、排
ガスの入口と出口とを備えた触媒反応器に充填して用い
る成形触媒であって、上記入口から上記触媒反応器に導
入される排ガスの流れ方向に少なくとも１つの貫通孔を
有し、通常、多数の貫通孔を有する所謂ハニカム触媒と
呼ばれるものである。A particularly preferred shaped catalyst according to the present invention is a shaped catalyst which is used by filling it in a catalytic reactor having an exhaust gas inlet and an outlet, and the flow direction of the exhaust gas introduced into the catalytic reactor through the inlet. It is a so-called honeycomb catalyst that has at least one through-hole in each of the above, and usually has many through-holes.
【００１２】本発明において、上記多孔質成形体を形成
する触媒成分のうち、酸化チタンの原料としては、予め
調製された酸化チタンのほか、チタン酸、水酸化チタ
ン、硫酸チタン等のチタン化合物が用いられる。また、
成形体の主成分が酸化チタン−シリカ複合酸化物からな
るとき、そのような複合酸化物は、例えば、硫酸チタン
等のチタン塩の水溶液にシリカゾルを加え、得られた混
合物にアンモニア等のアルカリを加えて、沈殿物を生じ
させ、次いで、このようにして得られた沈殿物を洗浄
し、乾燥させた後、１５０〜８５０℃で焼成することに
よって得ることができる。また、酸化チタンについて
は、その製造方法は何ら限定されるものではないが、例
えば、硫酸法による酸化チタンの製造工程から得られる
硫酸チタンをアンモニアで中和し、これを乾燥し、焼成
して得られる二酸化チタンが好ましく用いられる。In the present invention, among the catalyst components forming the above-mentioned porous molded body, as raw materials for titanium oxide, titanium oxide prepared in advance and titanium compounds such as titanic acid, titanium hydroxide and titanium sulfate can be used. Used. Also,
When the main component of the molded body is composed of titanium oxide-silica composite oxide, such a composite oxide is obtained by adding silica sol to an aqueous solution of titanium salt such as titanium sulfate and adding an alkali such as ammonia to the resulting mixture. In addition, it can be obtained by forming a precipitate, and then washing the precipitate thus obtained, drying it, and calcining it at 150 to 850 ° C. Further, the production method of titanium oxide is not limited at all, but for example, titanium sulfate obtained from the production process of titanium oxide by the sulfuric acid method is neutralized with ammonia, dried and calcined. The titanium dioxide obtained is preferably used.
【００１３】三酸化タングステンの原料としては、それ
自体のほか、パラタングステン酸アンモニウム、メタタ
ングステン酸アンモニウム等が好ましく用いられる。ま
た、五酸化バナジウムの原料としては、それ自体のほ
か、メタバナジン酸アンモニウム等が好ましく用いられ
る。このような触媒成分からなる多孔質成形体は、従
来、知られている通常の方法によって調製することがで
きる。例えば、触媒成分のそれぞれの酸化物を混合し、
焼成する方法、触媒成分のそれぞれ水溶性塩の混合物か
らそれぞれの酸化物を共沈させ、これらを焼成する方法
等によればよい。As the raw material of tungsten trioxide, ammonium paratungstate, ammonium metatungstate, etc. are preferably used in addition to itself. As the raw material for vanadium pentoxide, ammonium metavanadate and the like are preferably used in addition to itself. A porous molded article containing such a catalyst component can be prepared by a conventionally known ordinary method. For example, mixing each oxide of the catalyst component,
A method of calcination, a method of coprecipitating each oxide from a mixture of water-soluble salts of catalyst components, and calcining these may be used.
【００１４】具体例を挙げれば、例えば、硫酸チタンに
アンモニアのようなアルカリを加えて、沈澱させ、乾燥
させ、焼成し、これにメタタングステン酸アンモニウム
水溶液や、必要に応じて、メタバナジン酸アンモニウム
水溶液を混合し、成形し、乾燥し、焼成することによっ
て、触媒成分からなる成形体を得ることができる。この
ような方法によれば、既によく知られているように、圧
力２０００kg／cm2 、水銀圧入法による測定にて、通
常、0.１〜0.５ｍＬ／ｇ、好ましくは、0.２〜0.４ｍＬ
／ｇ程度の細孔容積を有する多孔質の成形体を得ること
ができる。To give a specific example, for example, an alkali such as ammonia is added to titanium sulfate to cause precipitation, drying and firing, and then an ammonium metatungstate aqueous solution and, if necessary, an ammonium metavanadate aqueous solution are added. By mixing, molding, drying, and firing, a molded body composed of the catalyst component can be obtained. According to such a method, as is well known, the pressure is 2000 kg / cm 2 , and the measurement is usually 0.1 to 0.5 mL / g, preferably 0.2 to 0.2, as measured by the mercury penetration method. 0.4 mL
It is possible to obtain a porous molded body having a pore volume of about / g.
【００１５】本発明によれば、触媒成分からなる多孔質
成形体は、例えば、粒状物、環状物、筒状物、ハニカム
構造体等であるが、このような多孔質成形体を製造する
に際して、必要に応じて、粘土等の鉱物物質、シリカゾ
ル等の無機バインダーやポリビニルアルコール等の有機
バインダー等の種々の成形助剤、ガラス繊維やセラミッ
ク繊維等の種々の補強材等の充填材を用いてもよい。According to the present invention, the porous molded body made of the catalyst component is, for example, a granular material, a ring-shaped material, a cylindrical material, a honeycomb structure, or the like. , If necessary, various fillers such as mineral substances such as clay, inorganic binders such as silica sol and organic binders such as polyvinyl alcohol, and various reinforcing materials such as glass fiber and ceramic fiber. Good.
【００１６】本発明による成形触媒においては、多孔質
成形体は、酸化チタン又は酸化チタン−シリカ複合酸化
物１００重量部に対して、三酸化タングステン５〜２０
重量部と、五酸化バナジウム０〜2.０重量部、即ち、必
要に応じて、五酸化バナジウム2.０重量部以下とを含
み、このような多孔質成形体に後述するようにして、0.
５〜5.５重量部の範囲で硫酸マグネシウムを担持させる
ことによって、耐摩耗性と強度にすぐれ、排ガスに含ま
れる窒素酸化物を長期間にわたって安定して還元除去す
ることができる成形触媒を得ることができる。In the molded catalyst according to the present invention, the porous molded body contains 5 to 20 parts by weight of tungsten trioxide based on 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide.
Parts by weight, and vanadium pentoxide 0 to 2.0 parts by weight, that is, vanadium pentoxide 2.0 parts by weight or less, if necessary. .
By supporting magnesium sulfate in the range of 5 to 5.5 parts by weight, it is possible to obtain a molded catalyst having excellent wear resistance and strength and capable of stably reducing and removing nitrogen oxides contained in exhaust gas over a long period of time. be able to.
【００１７】本発明において、触媒成分として五酸化バ
ナジウムを用いることによって、低温域での触媒活性を
高めることができる。他方、五酸化バナジウムは、二酸
化イオウの三酸化イオウへの酸化能が高いほか、反応温
度が高温であるときは、還元剤であるアンモニアを酸化
したり、或いはチタンの結晶成長を促進して、熱劣化を
加速する。従って、イオウ酸化物を高濃度に含む排ガス
を処理する場合には、五酸化バナジウムは、触媒成分と
して用いないか、又は用いても、低温域での触媒活性の
向上とのバランスを考慮して、少量の配合にとどめるの
が好ましい。特に、反応温度が４００℃以上である場合
や、排ガスがイオウ酸化物を高濃度に含む場合には、通
常、触媒には、五酸化バナジウムを担持させないのが好
ましい。しかし、反応温度が４００℃未満である場合に
は、触媒活性を高めるために、通常、酸化チタン又は酸
化チタン−シリカ複合酸化物１００重量部に対して、0.
１重量部以上を担持させるのが好ましい。In the present invention, by using vanadium pentoxide as the catalyst component, the catalytic activity in the low temperature range can be enhanced. On the other hand, vanadium pentoxide has a high ability to oxidize sulfur dioxide to sulfur trioxide, and when the reaction temperature is high, oxidizes ammonia as a reducing agent or promotes titanium crystal growth, Accelerates thermal degradation. Therefore, when treating an exhaust gas containing a high concentration of sulfur oxide, vanadium pentoxide is not used as a catalyst component, or even if it is used, considering the balance with the improvement of the catalyst activity in the low temperature range. However, it is preferable to keep only a small amount. In particular, when the reaction temperature is 400 ° C. or higher, or when the exhaust gas contains a high concentration of sulfur oxide, it is usually preferable not to support vanadium pentoxide on the catalyst. However, in the case where the reaction temperature is lower than 400 ° C., in order to enhance the catalytic activity, it is usually 0.100 with respect to 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide.
It is preferable to support 1 part by weight or more.
【００１８】本発明による成形触媒は、このようにして
多孔質成形体を調製した後、この成形体に硫酸マグネシ
ウム水溶液を含浸させ、乾燥させた後、加熱焼成して、
酸化チタン又は酸化チタン−シリカ複合酸化物１００重
量部に対して、硫酸マグネシウムを0.５〜5.５重量部の
範囲で担持させることによって得ることができる。ここ
に、本発明において、硫酸マグネシウムの担持量は、よ
り好ましくは、酸化チタン又は酸化チタン−シリカ複合
酸化物１００重量部に対して、1.０〜5.０重量部の範囲
である。上記硫酸マグネシウムとしては、例えば、硫酸
マグネシウム７水塩が好ましく用いられる。In the molded catalyst according to the present invention, after the porous molded body is prepared in this manner, the molded body is impregnated with an aqueous magnesium sulfate solution, dried, and then heated and calcined,
It can be obtained by supporting magnesium sulfate in an amount of 0.5 to 5.5 parts by weight with respect to 100 parts by weight of titanium oxide or a titanium oxide-silica composite oxide. Here, in the present invention, the supported amount of magnesium sulfate is more preferably in the range of 1.0 to 5.0 parts by weight with respect to 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide. As the magnesium sulfate, for example, magnesium sulfate heptahydrate is preferably used.
【００１９】例えば、成形体を硫酸マグネシウム水溶液
に浸漬した後、通風乾燥し、この後、１００〜１２０℃
の温度で加熱乾燥させ、次いで、空気中、３００〜５０
０℃程度の温度で加熱焼成して、成形体に硫酸マグネシ
ウムを担持させることができる。このようにして、本発
明によれば、成形体の全体にわたって、実質的に均一に
硫酸マグネシウムを担持させることができる。ここに、
硫酸マグネシウムは、水和物又は無水物として、成形体
中に担持されている。For example, the molded body is dipped in an aqueous solution of magnesium sulfate, dried by ventilation, and then 100 to 120 ° C.
And dried in air at 300-50.
By heating and firing at a temperature of about 0 ° C., magnesium sulfate can be supported on the molded body. In this way, according to the present invention, magnesium sulfate can be supported substantially uniformly over the entire molded body. here,
Magnesium sulfate is supported in the molded body as a hydrate or anhydrate.
【００２０】しかし、本発明によれば、必要に応じて、
成形体の先端部分のみに硫酸マグネシウム水溶液を含浸
させ、通風乾燥し、この後、１００〜１２０℃の温度で
加熱乾燥させ、次いで、空気中、３００〜５００℃程度
の温度で加熱焼成して、成形体の先端部分のみに硫酸マ
グネシウムを担持させてもよい。この場合においても、
硫酸マグネシウムの担持量は、その先端部分において、
酸化チタン又は酸化チタン−シリカ複合酸化物１００重
量部に対して、0.５〜5.０重量部の範囲であり、好まし
くは、1.０〜5.０重量部の範囲である。However, according to the invention, if desired,
Only the tip portion of the molded body is impregnated with the magnesium sulfate aqueous solution, air-dried, and then heated and dried at a temperature of 100 to 120 ° C., and then heated and baked in air at a temperature of about 300 to 500 ° C. Magnesium sulfate may be supported only on the tip portion of the molded body. Even in this case,
The amount of magnesium sulfate loaded is
It is in the range of 0.5 to 5.0 parts by weight, and preferably in the range of 1.0 to 5.0 parts by weight, based on 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide.
【００２１】本発明による成形触媒は、このように、触
媒成分からなる多孔質成形体に硫酸マグネシウムを担持
させることによって、触媒活性を損なうことなく、排ガ
ス中の摩耗性のダストによる摩耗に対する強度を有する
成形触媒を得ることができる。成形触媒における硫酸マ
グネシウムの担持量が酸化チタン又は酸化チタン−シリ
カ複合酸化物１００重量部に対して、5.５重量部を越え
るときは、得られる触媒の活性を低下させ、反対に、0.
５重量部よりも少ないときは、ダストによる摩耗に対す
る強度を付与することができない。The shaped catalyst according to the present invention thus supports magnesium sulfate on a porous shaped body composed of a catalyst component, and thereby has a strength against abrasion due to abradable dust in exhaust gas without impairing catalytic activity. A shaped catalyst having can be obtained. When the supported amount of magnesium sulfate in the shaped catalyst exceeds 5.5 parts by weight with respect to 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide, the activity of the obtained catalyst is lowered, and conversely, it is 0.
When the amount is less than 5 parts by weight, strength against abrasion due to dust cannot be imparted.
【００２２】本発明によれば、予め触媒成分からなる成
形体を調製し、これに硫酸マグネシウム水溶液を含浸さ
せ、加熱焼成して、成形触媒とするので、硫酸マグネシ
ウムは多孔質成形体の細孔において、特に、酸化物の粒
子が相互に接触する接点の近傍に局在して、酸化物の粒
子を相互に接着させるので、成形触媒の重量に対して、
少量のみを担持させることによって、目的とするダスト
に対する強度を得ることができる。更に、本発明によれ
ば、成形触媒の所要の部分のみに硫酸マグネシウムを担
持させることができる利点もある。更に、本発明によれ
ば、硫酸マグネシウム水溶液を多孔質成形体に含浸させ
た後、加熱焼成する過程で、硫酸マグネシウム水和物が
その結晶水を失なって、結晶の寸法が変化しても、成形
体が予め調製されているので、強度を強化しても、低下
させることはない。According to the present invention, a molded body composed of a catalyst component is prepared in advance, and this is impregnated with an aqueous magnesium sulfate solution and heated and baked to obtain a molded catalyst. In particular, since the oxide particles are localized in the vicinity of the contact point where they contact each other and adhere the oxide particles to each other,
By supporting only a small amount, the desired strength against dust can be obtained. Further, according to the present invention, there is an advantage that magnesium sulfate can be supported only on a required portion of the shaped catalyst. Furthermore, according to the present invention, even after the magnesium sulfate hydrate loses its crystal water in the process of impregnating the porous molded body with the magnesium sulfate aqueous solution and then heating and firing, the size of the crystal changes. Since the molded body is prepared in advance, the strength is not reduced even if it is strengthened.
【００２３】これに対して、成形触媒に硫酸マグネシウ
ムを担持させるために、他の方法、例えば、触媒成分と
共に硫酸マグネシウムを湿式混練して、成形触媒を得る
方法によれば、硫酸マグネシウムは、酸化物の粒子の表
面に均一に分布し、従って、触媒成分に対して多量を用
いながら、目的とする強度を得ることが困難であり、更
に、余りに多量を用いれば、所要の強度を得ることがで
きても、初期活性の低いものとなる。また、成形体を加
熱焼成する過程で、硫酸マグネシウム水和物がその結晶
水を失なって、結晶の寸法が変化した際に、成形体自体
の強度を低下させるおそれもある。On the other hand, in order to support magnesium sulfate on the shaped catalyst, according to another method, for example, a method of wet kneading magnesium sulfate with a catalyst component to obtain a shaped catalyst, magnesium sulfate is oxidized. Since it is evenly distributed on the surface of the particles of the product, it is difficult to obtain the desired strength while using a large amount for the catalyst component. Furthermore, if too much is used, the required strength can be obtained. Even if it is possible, the initial activity will be low. Further, in the process of heating and firing the compact, the magnesium sulfate hydrate loses its water of crystallization, and when the size of the crystal changes, the strength of the compact itself may be reduced.
【００２４】本発明による成形触媒は、好ましくは、排
ガスの入口と出口とを備えた触媒反応器に充填して用い
られるものであって、上記入口から上記触媒反応器に導
入される排ガスの流れ方向に少なくとも１つの貫通孔を
有する構造体であり、特に、好ましくは、多数の貫通孔
を有する所謂ハニカム触媒である。従って、本発明によ
れば、成形触媒を上述したような触媒反応器に充填し、
これに排ガスを還元剤であるアンモニアと共にその入口
から導入し、出口から排出するようにして、成形触媒の
有するガス流れ方向の貫通孔を通過させ、その間に、排
ガスを成形触媒に接触させて、窒素酸化物を窒素と水と
に変換して、排ガスから除去する。The shaped catalyst according to the present invention is preferably used by being filled in a catalytic reactor having an exhaust gas inlet and an outlet, and the flow of the exhaust gas introduced into the catalytic reactor from the inlet. It is a structure having at least one through hole in the direction, and particularly preferably a so-called honeycomb catalyst having a large number of through holes. Therefore, according to the present invention, a shaped catalyst is loaded into a catalytic reactor as described above,
Exhaust gas is introduced into this together with ammonia as a reducing agent from its inlet, and is discharged from the outlet so as to pass through a through hole in the gas flow direction of the shaped catalyst, while the exhaust gas is brought into contact with the shaped catalyst, The nitrogen oxides are converted to nitrogen and water and removed from the exhaust gas.
【００２５】本発明によれば、前述したように、ダスト
を含む燃焼排ガスを脱硝処理する場合に、特に、成形触
媒の先端部分のダストによる摩耗を防止するために、成
形触媒を触媒反応器に充填した場合の前面のガス入口を
含む先端部分を耐摩耗性としてもよい。また、必要に応
じて、成形触媒を触媒反応器に充填した場合の後面のガ
ス出口を含む後端部分を耐摩耗性としてもよい。このよ
うに、成形触媒の先端部分を耐摩耗性とするには、例え
ば、既に、特公昭５７−１４２１１号公報、特公昭５７
−２６８２０号公報、特公昭６１−１７５４８号公報、
米国特許第 4,294,806号に記載されているように、幾つ
かの方法によることができる。According to the present invention, as described above, when the combustion exhaust gas containing dust is subjected to the denitration treatment, in particular, in order to prevent wear of the tip portion of the shaped catalyst due to dust, the shaped catalyst is placed in the catalytic reactor. The tip portion including the gas inlet on the front surface when filled may be made wear resistant. Further, if necessary, the rear end portion including the gas outlet on the rear surface when the molded catalyst is filled in the catalytic reactor may be made wear-resistant. As described above, in order to make the tip portion of the molded catalyst wear resistant, for example, Japanese Patent Publication No. 57-14211 and Japanese Examined Patent Publication No.
-26820, Japanese Patent Publication No. 61-17548,
Several methods can be used, as described in US Pat. No. 4,294,806.
【００２６】第１の方法として、成形触媒の先端部分に
重リン酸塩又は縮合リン酸塩の水溶液を含浸させた後、
加熱して、硬化物を形成させることによって、強化する
ことができる。重リン酸塩としては、例えば、第一リン
酸水素カルシウム、第一リン酸水素バリウム、第一リン
酸水素アルミニウム等を挙げることができる。また、縮
合リン酸塩としては、例えば、メタリン酸塩やポリリン
酸塩等を挙げることができる。As a first method, after impregnating the tip portion of the shaped catalyst with an aqueous solution of a heavy phosphate or a condensed phosphate,
It can be strengthened by heating to form a cured product. Examples of the heavy phosphate include calcium hydrogen phosphate, barium hydrogen phosphate, aluminum hydrogen phosphate and the like. Examples of condensed phosphates include metaphosphates and polyphosphates.
【００２７】具体的には、このような重リン酸塩又は縮
合リン酸塩の水溶液に、必要に応じて、マグネシアクリ
ンカー等のような骨材、粘土、リン酸ナトリウム、ケイ
酸アルカリ等を加え、水溶液又はスラリーとし、これに
成形触媒の先端部分を浸漬し、先端部分に付着させ、加
熱焼成すればよい。この加熱温度は、通常、２００〜１
０００℃の範囲であり、通常、４００〜５００℃程度で
ある。例えば、重リン酸アルミニウムの水溶液を成形触
媒の先端部分に塗布し、通常、４００〜５００℃程度の
温度に加熱すれば、硬化物の被膜が形成されて、成形触
媒の先端部分を強化することができる。Specifically, if necessary, an aggregate such as magnesia clinker, clay, sodium phosphate, alkali silicate or the like is added to an aqueous solution of such a heavy phosphate or condensed phosphate. The solution may be made into an aqueous solution or slurry, and the tip portion of the shaped catalyst may be dipped in the solution, adhered to the tip portion, and baked by heating. This heating temperature is usually 200 to 1
The temperature is in the range of 000 ° C, and is usually about 400 to 500 ° C. For example, when an aqueous solution of aluminum diphosphate is applied to the tip portion of the shaped catalyst and heated to a temperature of about 400 to 500 ° C., a film of a cured product is formed to strengthen the tip portion of the shaped catalyst. You can
【００２８】第２の方法として、成形触媒の先端部分を
ガラス物質で被覆することによって、強化することがで
きる。ガラス物質としては、例えば、水ガラス、チタニ
アゾル、シリカゾル、アルミナゾル、ケイ酸リチウム、
ホウ酸鉛、酸化ホウ素、ホウ砂、種々の釉、例えば、ホ
ウ酸鉛系釉、硬質磁器系釉等を挙げることができる。具
体的には、ガラス物質や釉を溶融させ、この融液中に成
形触媒の先端部分を浸漬するか、或いは上記融液を成形
触媒の先端部分に塗布し、冷却して、ガラス物質や釉で
被覆することによって、強化することができる。As a second method, the tip portion of the shaped catalyst can be strengthened by coating it with a glass material. As the glass substance, for example, water glass, titania sol, silica sol, alumina sol, lithium silicate,
Examples thereof include lead borate, boron oxide, borax, and various glazes such as lead borate-based glaze and hard porcelain-based glaze. Specifically, the glass substance or glaze is melted and the tip portion of the shaped catalyst is immersed in this melt, or the melt is applied to the tip portion of the shaped catalyst and cooled to cool the glass substance or glaze. It can be strengthened by coating with.
【００２９】第３の方法として、例えば、成形触媒の先
端部分を焼結してもよい。また、成形触媒の先端部分を
成形触媒の先端部分の端面と同じ形状の貫通孔を有する
金属製や磁器製の保護板で被覆してもよい。本発明によ
れば、還元剤の存在下に、窒素酸化物を含む排ガスを上
述したような成形触媒に接触させることによって、排ガ
スに含まれる窒素酸化物を還元除去することができる。
ここに、還元剤としては、アンモニア、尿素等が用いら
れるが、特に、実用的には、アンモニアが好ましく用い
られる。還元剤は、排ガスに含まれる窒素酸化物と完全
に反応するに必要な化学量論の0.１〜1.５倍程度、好ま
しくは、0.１〜1.２倍程度用いられる。As a third method, for example, the tip portion of the shaped catalyst may be sintered. Further, the tip portion of the shaped catalyst may be covered with a protective plate made of metal or porcelain having a through hole having the same shape as the end surface of the tip portion of the shaped catalyst. According to the present invention, the nitrogen oxide contained in the exhaust gas can be reduced and removed by bringing the exhaust gas containing the nitrogen oxide into contact with the shaped catalyst as described above in the presence of the reducing agent.
Here, as the reducing agent, ammonia, urea and the like are used, but particularly practically, ammonia is preferably used. The reducing agent is used in an amount of about 0.1 to 1.5 times, preferably about 0.1 to 1.2 times the stoichiometric amount required to completely react with the nitrogen oxides contained in the exhaust gas.
【００３０】排ガスにこのように還元剤を混合し、これ
を、通常、１５０〜５００℃、好ましくは、３００〜４
５０℃の温度で空間速度（ＮＴＰ換算空塔基準）２００
０〜５００００ｈｒ-1、好ましくは、２０００〜１００
００ｈｒ-1の範囲にて触媒に接触させることによって、
排ガス中の窒素酸化物を効率よく還元分解することがで
きる。The exhaust gas is mixed with the reducing agent in this manner, and this is usually added at 150 to 500 ° C., preferably 300 to 4
Space velocity at a temperature of 50 ° C. (NTP conversion empty tower standard) 200
0-50000 hr -1 , preferably 2000-100
By contacting the catalyst in the range of 00 hr -1 ,
The nitrogen oxides in the exhaust gas can be efficiently reduced and decomposed.
【００３１】本発明による成形触媒は、排ガスがダスト
を含む場合であっても、実質的に摩耗することがなく、
従って、例えば、石炭焚きボイラからの燃焼排ガス等の
摩耗性を有するダストを含む排ガス中の窒素酸化物を接
触還元除去するために好適に適用することができる。し
かし、本発明による成形触媒の用途は、これに限定され
るものではない。The formed catalyst according to the present invention does not substantially wear even if the exhaust gas contains dust,
Therefore, for example, it can be suitably applied for catalytic reduction removal of nitrogen oxides in exhaust gas containing abrasive dust such as combustion exhaust gas from a coal-fired boiler. However, the use of the shaped catalyst according to the present invention is not limited to this.
【００３２】[0032]
【発明の効果】以上のように、本発明によれば、触媒成
分からなる多孔質成形体に硫酸マグネシウム水溶液を含
浸させ、加熱焼成して、硫酸マグネシウムを所定量担持
させるので、触媒活性を損なうことなく、成形触媒にダ
ストによる摩耗に対する強度を与えることができ、成形
触媒は実質的に摩耗することがない。従って、本発明に
よる成形触媒を用いれば、長期間にわたって安定して効
率よく、排ガスの脱硝処理を行なうことができる。Industrial Applicability As described above, according to the present invention, a porous molded body composed of a catalyst component is impregnated with an aqueous magnesium sulfate solution and heated and baked to carry a predetermined amount of magnesium sulfate, thereby impairing the catalytic activity. Without increasing the strength of the molded catalyst against abrasion due to dust, the molded catalyst does not substantially wear. Therefore, by using the shaped catalyst according to the present invention, it is possible to perform denitration treatment of exhaust gas stably and efficiently for a long period of time.
【００３３】また、例えば、触媒反応器に多数の成形触
媒を充填して、排ガスの脱硝処理を行なうような場合、
触媒反応器における排ガスの流れの不均一により生じる
ダスト濃度の不均一やダストの粒度分布の偏り等によっ
て、成形触媒に局部的な摩耗が生じると予想される位置
に、本発明による成形触媒を用いることによって、長時
間にわたって安定して窒素酸化物の接触還元除去するこ
とができる。更に、本発明によれば、成形触媒の一部に
のみ、選択的に、所要の強度を与えることができるの
で、特に、摩耗の生じやすい箇所に硫酸マグネシウムを
担持させて、そのような摩耗から触媒を保護することも
できる。In addition, for example, when a catalyst reactor is filled with a large number of shaped catalysts to denitrate exhaust gas,
The molded catalyst according to the present invention is used at a position where local wear of the molded catalyst is expected to occur due to non-uniformity of dust concentration caused by non-uniformity of exhaust gas flow in the catalytic reactor and deviation of particle size distribution of dust. As a result, the nitrogen oxide can be stably removed by catalytic reduction over a long period of time. Furthermore, according to the present invention, the required strength can be selectively imparted only to a part of the formed catalyst, so that magnesium sulfate is supported particularly on a portion where abrasion is likely to occur, and such a abrasion can be prevented. The catalyst can also be protected.
【００３４】[0034]
【実施例】以下に、実施例を挙げて本発明を説明する
が、本発明はこれら実施例により何ら限定されるもので
はない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００３５】実施例１ 硫酸法による酸化チタン製造工程から得られるメタチタ
ン酸を中和した後、濾過、水洗して、ケーキ状のメタチ
タン酸を得た。このメタチタン酸（二酸化チタン換算に
て８２０ｋｇ）に６7.５％硝酸８ｋｇを加え、メタチタ
ン酸を部分的に解膠した後、得られたゾル液を蒸発乾固
し、更に、５００℃で３時間焼成した。この後、冷却
し、微粉砕し、その粒度を調整して、二酸化チタン粉末
を得た。Example 1 Metatitanic acid obtained from the step of producing titanium oxide by the sulfuric acid method was neutralized, then filtered and washed with water to obtain cake-shaped metatitanic acid. 8 kg of 67.5% nitric acid was added to this metatitanic acid (820 kg in terms of titanium dioxide) to partially deflocculate the metatitanic acid, and the resulting sol solution was evaporated to dryness, and further at 500 ° C. for 3 hours. Baked. Then, the mixture was cooled, pulverized, and its particle size was adjusted to obtain a titanium dioxide powder.
【００３６】モノエタノールアミン水溶液に五酸化バナ
ジウム5.２ｋｇとパラタングステン酸アンモニウム１１
２ｋｇを溶解した水溶液３００Ｌ、ポリビニルアルコー
ル５０ｋｇ及び炭化ケイ素繊維（繊維径１１μｍ、繊維
長さ３ｍｍ、日本カーボン（株）製）１００ｋｇを上記
二酸化チタン粉末８００ｋｇに水約１００Ｌと共に加
え、ニーダーにてこれらを混練した。5.2 kg of vanadium pentoxide and ammonium paratungstate 11 in an aqueous monoethanolamine solution
300 L of an aqueous solution in which 2 kg was dissolved, 50 kg of polyvinyl alcohol, and 100 kg of silicon carbide fiber (fiber diameter: 11 μm, fiber length: 3 mm, manufactured by Nippon Carbon Co., Ltd.) were added to 800 kg of the above titanium dioxide powder together with about 100 L of water, and these were kneaded. Kneaded
【００３７】次いで、この混練物をハニカム押出ノズル
を備えたスクリュー付き真空押出機によってハニカム成
形体に押出成形した。このハニカム成形体を十分に時間
をかけて自然乾燥させた後、１００℃で５時間通風乾燥
した。この後、軸方向の両端を切り揃え、電気炉内にて
５００℃で５時間焼成して、外径１５０ｍｍ×１５０ｍ
ｍ、軸方向長さ８００ｍｍ、セルピッチ7.４ｍｍ、内壁
厚さ1.１５ｍｍのハニカム成形体Ｉを得た。Next, this kneaded product was extruded into a honeycomb formed body by a vacuum extruder with a screw equipped with a honeycomb extrusion nozzle. The honeycomb formed body was naturally dried for a sufficient time, and then air-dried at 100 ° C. for 5 hours. After that, both ends in the axial direction are cut and aligned, and baked in an electric furnace at 500 ° C. for 5 hours to give an outer diameter of 150 mm × 150 m.
m, an axial length of 800 mm, a cell pitch of 7.4 mm, and an inner wall thickness of 1.15 mm were obtained.
【００３８】別に、硫酸マグネシウム７水塩の結晶６２
ｋｇを溶解した水溶液２４０Ｌに上記成形体を１５分間
浸漬した後、引き上げた。次いで、触媒に通風して、過
剰に付着している上記水溶液を吹き払い、１１０℃で３
時間乾燥した後、４００℃で３時間焼成して、酸化チタ
ン１００重量部に対して、三酸化タングステン１2.４３
重量部、五酸化バナジウム0.６５重量部及び硫酸マグネ
シウム4.５５重量部を担持させてなる成形触媒（ハニカ
ム触媒）Ａを得た。Separately, magnesium sulfate heptahydrate crystals 62
The molded body was immersed in 240 L of an aqueous solution in which kg was dissolved for 15 minutes and then pulled up. Then, the catalyst is ventilated to blow off the above-mentioned excessively adhered aqueous solution, and the mixture is kept at 110 ° C. for 3 hours.
After drying for 3 hours, calcination is performed at 400 ° C for 3 hours.
A molded catalyst (honeycomb catalyst) A was prepared by supporting 1 part by weight, 0.65 part by weight of vanadium pentoxide and 4.55 part by weight of magnesium sulfate.
【００３９】実施例２ 硫酸マグネシウム７水塩の結晶１7.７ｋｇを溶解した水
溶液２４０Ｌに上記実施例１で得たハニカム成形体Ｉを
１５分間浸漬した後、引き上げた。次いで、触媒に通風
して、過剰に付着している上記溶液を吹き払い、１１０
℃で３時間乾燥した後、４００℃で３時間焼成して、酸
化チタン１００重量部に対して、三酸化タングステン１
2.４２重量部、五酸化バナジウム0.６５重量部及び硫酸
マグネシウム1.２７重量部を担持させてなる成形触媒
（ハニカム触媒）Ｂを得た。Example 2 The honeycomb formed article I obtained in Example 1 was immersed in 240 L of an aqueous solution in which 17.7 kg of magnesium sulfate heptahydrate crystals were dissolved, and then it was pulled up. Then, the catalyst is ventilated to blow off the excessively adhered solution,
After drying at ℃ for 3 hours, calcination at 400 ℃ for 3 hours, 1 part tungsten trioxide to 100 parts by weight titanium oxide.
A molded catalyst (honeycomb catalyst) B supporting 2.42 parts by weight, 0.65 parts by weight of vanadium pentoxide and 1.27 parts by weight of magnesium sulfate was obtained.
【００４０】実施例３ 硫酸法による酸化チタン製造工程から得られるメタチタ
ン酸を中和した後、濾過、水洗して、ケーキ状のメタチ
タン酸を得た。このメタチタン酸（二酸化チタン換算に
て８２０ｋｇ）に６7.５％硝酸８ｋｇを加え、メタチタ
ン酸を部分的に解膠した後、このゾル液を蒸発乾固し、
更に、５００℃で３時間焼成した。この後、冷却し、微
粉砕して、粒度を調整して、二酸化チタン粉末を得た。Example 3 Metatitanic acid obtained from the process for producing titanium oxide by the sulfuric acid method was neutralized, then filtered and washed with water to obtain a cake-shaped metatitanic acid. 8 kg of 67.5% nitric acid was added to this metatitanic acid (820 kg in terms of titanium dioxide) to partially peptize the metatitanic acid, and then the sol liquid was evaporated to dryness,
Furthermore, it baked at 500 degreeC for 3 hours. Then, it was cooled and pulverized to adjust the particle size to obtain a titanium dioxide powder.
【００４１】モノエタノールアミン水溶液にパラタング
ステン酸アンモニウム１１２ｋｇを溶解した水溶液３０
０Ｌ、ポリビニルアルコール５０ｋｇ及び炭化ケイ素繊
維（繊維径１１μｍ、繊維長さ３ｍｍ、日本カーボン
（株）製）１００ｋｇを上記二酸化チタン粉末８００ｋ
ｇに水約１００Ｌと共に加え、ニーダーに共に加え、こ
れらを混練した。An aqueous solution 30 in which 112 kg of ammonium paratungstate is dissolved in an aqueous monoethanolamine solution
0 L, polyvinyl alcohol 50 kg, and silicon carbide fiber (fiber diameter 11 μm, fiber length 3 mm, manufactured by Nippon Carbon Co., Ltd.) 100 kg are used as the titanium dioxide powder 800 k.
About 100 L of water was added to g, and the kneader was added together, and these were kneaded.
【００４２】次いで、この混練物をハニカム押出ノズル
を備えたスクリュー付き真空押出機によってハニカム成
形体に押出成形した。このハニカム成形体を十分に時間
をかけて自然乾燥させた後、１００℃で５時間通風乾燥
した。この後、軸方向の両端を切り揃え、電気炉内にて
５００℃で５時間焼成して、外径１５０ｍｍ×１５０ｍ
ｍ、軸方向長さ８００ｍｍ、セルピッチ7.４ｍｍ、内壁
厚さ1.１５ｍｍのハニカム成形体Ｊを得た。Next, this kneaded product was extruded into a honeycomb formed body by a vacuum extruder with a screw equipped with a honeycomb extrusion nozzle. The honeycomb formed body was naturally dried for a sufficient time, and then air-dried at 100 ° C. for 5 hours. After that, both ends in the axial direction are cut and aligned, and baked in an electric furnace at 500 ° C. for 5 hours to give an outer diameter of 150 mm × 150 m.
m, an axial length of 800 mm, a cell pitch of 7.4 mm, and an inner wall thickness of 1.15 mm were obtained.
【００４３】別に、硫酸マグネシウム７水塩の結晶６1.
７ｋｇと五酸化バナジウム4.３ｋｇとを含むシュウ酸水
溶液２４０Ｌに上記ハニカム成形体Ｊを１５分間浸漬し
た後、引き上げた。次いで、触媒に通風して、過剰に付
着している上記溶液を吹き払い、１１０℃で５時間乾燥
した後、４００℃で３時間焼成して、酸化チタン１００
重量部に対して、三酸化タングステン１2.４３重量部、
五酸化バナジウム0.６５重量部及び硫酸マグネシウム4.
５５重量部を担持させてなる成形触媒（ハニカム触媒）
Ｃを得た。Separately, crystals of magnesium sulfate heptahydrate 61.
The honeycomb formed body J was immersed in 240 L of an aqueous oxalic acid solution containing 7 kg and 4.3 kg of vanadium pentoxide for 15 minutes and then pulled up. Then, the catalyst is ventilated to blow off the excessively adhered solution, dried at 110 ° C. for 5 hours, and then calcined at 400 ° C. for 3 hours to obtain titanium oxide 100.
12.43 parts by weight of tungsten trioxide with respect to parts by weight,
0.65 parts by weight of vanadium pentoxide and magnesium sulfate 4.
Molded catalyst supporting 55 parts by weight (honeycomb catalyst)
C was obtained.
【００４４】実施例４ 硫酸法による酸化チタン製造工程より得られる硫酸チタ
ン溶液（二酸化チタン換算にて１００ｇ／Ｌ濃度）７０
００Ｌとシリカゾル溶液（ＳｉＯ2 換算で２０重量％濃
度、日産化学（株）製）６１８ｋｇを十分混合した後、
アンモンニア水にて中和し、濾過、水洗して、ケーキを
得た。このケーキを乾燥し、５００℃で３時間焼成した
後、冷却し、微粉砕して、粒度を調整したチタン−シリ
カ複合酸化物を得た。Example 4 Titanium sulfate solution (100 g / L concentration in terms of titanium dioxide) obtained from the production process of titanium oxide by the sulfuric acid method 70
After thoroughly mixing 00 L and 618 kg of a silica sol solution (concentration of 20% by weight in terms of SiO 2 , manufactured by Nissan Kagaku Co., Ltd.),
It was neutralized with Ammonia water, filtered, and washed with water to obtain a cake. The cake was dried, calcined at 500 ° C. for 3 hours, cooled, and finely pulverized to obtain a titanium-silica composite oxide having a controlled particle size.
【００４５】モノエタノールアミン水溶液に五酸化バナ
ジウム5.２ｋｇとパラタングステン酸アンモニウム１１
２ｋｇを溶解した水溶液３００Ｌ、ポリビニルアルコー
ル５０ｋｇ及び炭化ケイ素繊維（繊維径１１μｍ、繊維
長さ３ｍｍ、日本カーボン（株）製）１００ｋｇを上記
複合酸化物粉末８００ｋｇに水約１００Ｌと共に加え、
ニーダーにてこれらを混練した。In an aqueous solution of monoethanolamine, 5.2 kg of vanadium pentoxide and ammonium paratungstate 11
300 L of an aqueous solution in which 2 kg was dissolved, 50 kg of polyvinyl alcohol and 100 kg of silicon carbide fiber (fiber diameter 11 μm, fiber length 3 mm, manufactured by Nippon Carbon Co., Ltd.) were added to 800 kg of the above complex oxide powder together with about 100 L of water,
These were kneaded with a kneader.
【００４６】次いで、この混練物をハニカム押出ノズル
を備えたスクリュー付き真空押出機によってハニカム成
形体に成形した。このハニカム成形体を十分に時間をか
けて自然乾燥させた後、１００℃で５時間通風乾燥し
た。この後、軸方向の両端を切り揃え、電気炉内にて５
００℃で５時間焼成して、外径１５０ｍｍ×１５０ｍ
ｍ、軸方向長さ８００ｍｍのセルピッチ7.４ｍｍ、内壁
厚さ1.１５ｍｍのハニカム成形体を得た。Next, this kneaded material was molded into a honeycomb molded body by a vacuum extruder with a screw equipped with a honeycomb extrusion nozzle. The honeycomb formed body was naturally dried for a sufficient time, and then air-dried at 100 ° C. for 5 hours. Then, both ends in the axial direction are cut and aligned, and 5
Baking at 00 ℃ for 5 hours, outer diameter 150mm × 150m
m, an axial length of 800 mm, a cell pitch of 7.4 mm, and an inner wall thickness of 1.15 mm were obtained.
【００４７】別に、硫酸マグネシウム７水塩の結晶５9.
４ｋｇを溶解した水溶液２４０Ｌに上記成形体を１５分
間浸漬した後、引き上げた。次いで、ハニカム成形体に
通風して、過剰に付着している上記水溶液を吹き払い、
１１０℃で３時間乾燥した後、４００℃で３時間焼成し
て、酸化チタン−シリカ複合酸化物１００重量部に対し
て、三酸化タングステン１2.４３重量部、五酸化バナジ
ウム0.６５重量部及び硫酸マグネシウム4.５５重量部を
担持させてなる成形触媒（ハニカム触媒）Ｄを得た。Separately, crystals of magnesium sulfate heptahydrate 59.
The molded body was immersed in 240 L of an aqueous solution in which 4 kg was dissolved for 15 minutes and then pulled up. Then, the honeycomb formed body is ventilated to blow off the excessively adhered aqueous solution,
After drying at 110 ° C. for 3 hours, it is baked at 400 ° C. for 3 hours to give 100 parts by weight of titanium oxide-silica composite oxide, 12.43 parts by weight of tungsten trioxide, 0.65 parts by weight of vanadium pentoxide, and A molded catalyst (honeycomb catalyst) D supporting 4.55 parts by weight of magnesium sulfate was obtained.
【００４８】実施例５ 硫酸マグネシウム７水塩の結晶６1.５ｋｇを溶解した水
溶液２４０Ｌに実施例３で得た成形体Ｊを１５分間浸漬
した後、引き上げた。次いで、ハニカム成形体に通風し
て、過剰に付着している上記水溶液を吹き払い、１１０
℃で５時間乾燥した後、４００℃で３時間焼成して、酸
化チタン１００重量部に対して、三酸化タングステン１
2.４３重量部及び硫酸マグネシウム4.５５重量部を担持
させてなる成形触媒（ハニカム触媒）Ｊ１を得た。Example 5 The molded body J obtained in Example 3 was immersed in 240 L of an aqueous solution in which 61.5 kg of magnesium sulfate heptahydrate crystals was dissolved for 15 minutes and then pulled up. Then, the honeycomb formed body is ventilated to blow off the excessively adhered aqueous solution.
After drying at ℃ for 5 hours, calcination at 400 ℃ for 3 hours, 1 part tungsten trioxide to 100 parts by weight titanium oxide.
A molded catalyst (honeycomb catalyst) J1 supporting 2.43 parts by weight and 4.55 parts by weight of magnesium sulfate was obtained.
【００４９】実施例６ 第一リン酸アルミニウム水溶液（多木化学（株）製、Ｐ
2 Ｏ5 として３３重量％、Ａｌ2 Ｏ3 として8.５重量％
含有し、ｐＨは1.４）を水にて２倍に希釈した。次い
で、実施例１で得た成形触媒Ａを、そのガス入口を含む
先端部分を軸方向に端面から５ｃｍの距離にわたって約
５分間浸漬した後、引き上げた。次いで、成形触媒に通
風して、過剰に付着している上記水溶液を吹き払い、１
１０℃で３時間乾燥した後、４００℃で３時間加熱し
て、成形触媒の先端部分を耐摩耗性とした成形触媒Ａ１
を得た。Example 6 Aqueous aluminum monophosphate solution (manufactured by Taki Chemical Co., Ltd., P
33% by weight as 2 O 5 , 8.5% by weight as Al 2 O 3
Containing, pH 1.4) was diluted 2-fold with water. Next, the molded catalyst A obtained in Example 1 was immersed in the tip portion including the gas inlet in the axial direction over a distance of 5 cm from the end surface for about 5 minutes, and then pulled up. Then, the molded catalyst is ventilated to blow off the excessively adhered aqueous solution,
After being dried at 10 ° C. for 3 hours, it is heated at 400 ° C. for 3 hours so that the tip portion of the molded catalyst has abrasion resistance.
I got
【００５０】実施例７ 実施例６において、成形触媒Ａに代えて、実施例で得た
成形触媒Ｃを用いた以外は、実施例６と同様にして、そ
のガス入口を含む先端部分を軸方向に端面から５ｃｍの
距離にわたって約５分間浸漬した後、引き上げ、次い
で、成形触媒に通風して、過剰に付着している上記水溶
液を吹き払い、１１０℃で３時間乾燥した後、４００℃
で３時間加熱して、成形触媒の先端部分を耐摩耗性とし
た成形触媒Ｃ１を得た。Example 7 In the same manner as in Example 6, except that the molded catalyst C obtained in Example was used in place of the molded catalyst A in Example 6, the tip portion including the gas inlet was axially moved. After being soaked for about 5 minutes from the end surface for about 5 minutes, then pulled up, and then blown over the formed catalyst to blow off the excessively adhered aqueous solution, and dried at 110 ° C. for 3 hours, and then 400 ° C.
By heating for 3 hours, a molded catalyst C1 having abrasion resistance at the tip of the molded catalyst was obtained.
【００５１】実施例８ 実施例１、２、３、４及び５にて得た触媒Ａ、Ｂ、Ｃ、
Ｄ及びＪ１をそれぞれ、断面４５ｍｍ×４５ｍｍ、長さ
１００ｍｍに裁断し、これを触媒反応に充填した。摩耗
材としてケイ砂（平均粒子径４０μｍ）を濃度７０ｇ／
ｍ3 にて含むガスを大気圧下、２０℃で成形触媒断面当
り、４０ｍ／秒の流速にて３０分間、成形触媒に通過さ
せて、その間の成形触媒の摩耗量から、摩耗強度を求め
た。試験結果を表１に示す。摩耗強度は、 〔（Ｗ0 −Ｗ）／Ｗ0 〕×１００（％） で与えられる。ここに、Ｗ0 は摩耗試験前の成形触媒の
重量、Ｗは摩耗試験後の成形触媒の重量であり、摩耗試
験前後の成形触媒の重量は、それぞれ１１０℃で５時間
加熱乾燥させた後、測定した重量である。Example 8 Catalysts A, B, C obtained in Examples 1, 2, 3, 4 and 5
Each of D and J1 was cut into a cross section of 45 mm × 45 mm and a length of 100 mm, and this was filled in the catalytic reaction. Concentration of silica sand (average particle size 40 μm) as abrasion material 70 g /
The gas containing m 3 was passed through the molded catalyst at a flow rate of 40 m / sec for 30 minutes per cross-section of the molded catalyst at 20 ° C. under atmospheric pressure, and the wear strength was obtained from the amount of wear of the molded catalyst during that time. . Table 1 shows the test results. The wear strength is given by [(W 0 −W) / W 0 ] × 100 (%). Here, W 0 is the weight of the formed catalyst before the abrasion test, W is the weight of the formed catalyst after the abrasion test, and the weight of the formed catalyst before and after the abrasion test is respectively after heating and drying at 110 ° C. for 5 hours, It is the measured weight.
【００５２】実施例９ 実施例１、２、３及び４で得た触媒Ａ、Ｂ、Ｃ及びＤを
触媒反応器に充填して、石炭を燃料とする燃焼排ガスの
流通下、８０００時間にわたって、脱硝処理を行なっ
た。上記燃焼排ガスの性状及び脱硝処理条件は次のとお
りである。脱硝処理前後の触媒活性を表１に示す。 （燃焼排ガスの性状） ダスト濃度：１５ｇ／Ｎｍ3 硫黄酸化物濃度：１６４０ｐｐｍ 窒素酸化物濃度：３２０ｐｐｍ 酸素濃度：4.２容量％ （脱硝処理条件） 排ガス温度：３４０℃ ガス流速：2.５５Ｎｍ／秒 空間速度（ＳＶ）：４５４０ｈｒ-1 アンモニア／窒素酸化物モル比：1.０Example 9 The catalysts A, B, C and D obtained in Examples 1, 2, 3 and 4 were charged in a catalytic reactor, and 8000 hours were passed under the flow of coal-burned combustion exhaust gas. A denitration process was performed. The properties of the combustion exhaust gas and the denitration treatment conditions are as follows. Table 1 shows the catalytic activity before and after the denitration treatment. (Properties of combustion exhaust gas) Dust concentration: 15 g / Nm 3 Sulfur oxide concentration: 1640 ppm Nitrogen oxide concentration: 320 ppm Oxygen concentration: 4.2% by volume (Denitration treatment condition) Exhaust gas temperature: 340 ° C. Gas flow rate: 2.55 Nm / Second space velocity (SV): 4540 hr -1 Ammonia / nitrogen oxide molar ratio: 1.0
【００５３】更に、上述したようにして、燃焼排ガスの
脱硝処理を行なった成形触媒の先端部分の内壁（貫通孔
壁）厚さの変化と成形触媒のガス流れ方向の全長の１／
２の位置における内壁厚さの変化を調べた。その結果を
表１に示す。成形触媒の先端部分の内壁（貫通孔壁）厚
さの変化は括弧内に示す。Further, as described above, the change in the thickness of the inner wall (through-hole wall) of the front end portion of the molded catalyst subjected to the denitration treatment of the combustion exhaust gas and 1 / l of the total length of the molded catalyst in the gas flow direction.
The change in the inner wall thickness at position 2 was investigated. Table 1 shows the results. The change in the thickness of the inner wall (through hole wall) at the tip of the shaped catalyst is shown in parentheses.
【００５４】実施例１０ 実施例５で得た触媒Ｊ１を触媒反応器に充填して、石炭
を燃料とする燃焼排ガスの流通下、８０００時間にわた
って、脱硝処理を行なった。上記燃焼排ガスの性状及び
脱硝処理条件は次のとおりである。脱硝処理前後の触媒
活性を表１に示す。 （燃焼排ガスの性状） ダスト濃度：２２ｇ／Ｎｍ3 硫黄酸化物濃度：８９０ｐｐｍ 窒素酸化物濃度：２６０ｐｐｍ 酸素濃度：4.０容量％ （脱硝処理条件） 排ガス温度：４５０℃ ガス流速：2.１１Ｎｍ／秒 空間速度（ＳＶ）：３５６０ｈｒ-1 アンモニア／窒素酸化物モル比：1.０Example 10 The catalyst J1 obtained in Example 5 was filled in a catalytic reactor and subjected to denitration treatment for 8000 hours under the flow of combustion exhaust gas using coal as a fuel. The properties of the combustion exhaust gas and the denitration treatment conditions are as follows. Table 1 shows the catalytic activity before and after the denitration treatment. (Properties of combustion exhaust gas) Dust concentration: 22 g / Nm 3 Sulfur oxide concentration: 890 ppm Nitrogen oxide concentration: 260 ppm Oxygen concentration: 4.0% by volume (Denitration treatment condition) Exhaust gas temperature: 450 ° C. Gas flow rate: 2.11 Nm / Second space velocity (SV): 3560 hr −1 Ammonia / nitrogen oxide molar ratio: 1.0
【００５５】更に、上述したようにして、燃焼排ガスの
脱硝処理を行なった成形触媒の先端部分の内壁（貫通孔
壁）厚さの変化と成形触媒のガス流れ方向の全長の１／
２の位置における内壁厚さの変化を調べた。その結果を
表１に示す。成形触媒の先端部分の内壁（貫通孔壁）厚
さの変化は括弧内に示す。Further, as described above, the change in the thickness of the inner wall (through-hole wall) of the tip portion of the shaped catalyst after denitration of the combustion exhaust gas and 1 / l of the total length of the shaped catalyst in the gas flow direction.
The change in the inner wall thickness at position 2 was investigated. Table 1 shows the results. The change in the thickness of the inner wall (through hole wall) at the tip of the shaped catalyst is shown in parentheses.
【００５６】実施例１１実施例６及び７で得られた触媒
Ａ１及びＣ１をそれぞれ触媒反応器において成形触媒に
局部的な摩耗が生じる位置に充填した以外は、実施例９
と同じ条件下に、石炭を燃焼とする燃焼排ガスの流通
下、８０００時間にわたって、脱硝処理を行なって、成
形触媒の先端部分の内壁（貫通孔壁）厚さの変化と成形
触媒のガス流れ方向の全長の１／２の位置における内壁
厚さの変化を調べた。結果を表２に示す。成形触媒の先
端部分の内壁（貫通孔壁）厚さの変化は括弧内に示す。Example 11 Example 9 was repeated except that the catalysts A1 and C1 obtained in Examples 6 and 7 were charged in the catalytic reactor at the positions where the molded catalyst was locally worn.
Under the same conditions as above, under the flow of combustion exhaust gas that burns coal, denitration treatment was performed for 8000 hours to change the thickness of the inner wall (through hole wall) of the tip portion of the formed catalyst and the gas flow direction of the formed catalyst. The change in the thickness of the inner wall was examined at a position of 1/2 of the total length. Table 2 shows the results. The change in the thickness of the inner wall (through hole wall) at the tip of the shaped catalyst is shown in parentheses.
【００５７】比較例１ 実施例１による成形体Ｉの調製を比較例１とする。即
ち、成形体Ｉは、酸化チタン１００重量部に対して、三
酸化タングステン１2.４３重量部と五酸化バナジウム0.
６５重量部とからなる。Comparative Example 1 The preparation of the molded article I according to Example 1 is referred to as Comparative Example 1. That is, the molded product I was obtained by adding 12.43 parts by weight of tungsten trioxide and 0.1% of vanadium pentoxide to 100 parts by weight of titanium oxide.
65 parts by weight.
【００５８】比較例２ 硫酸マグネシウム７水塩の結晶3.４ｋｇを溶解した水溶
液２４０Ｌに上記成形体Ｉを１５分間浸漬した後、引き
上げた。次いで、成形体に通風して、過剰に付着してい
る上記溶液を吹き払い、１１０℃で３時間乾燥した後、
４００℃で３時間焼成して、酸化チタン１００重量部に
対して、三酸化タングステン１2.４２重量部、五酸化バ
ナジウム0.６５重量部及び硫酸マグネシウム0.２５重量
部を担持してなる成形触媒Ｅを得た。Comparative Example 2 The above molded article I was immersed in 240 L of an aqueous solution in which 3.4 kg of magnesium sulfate heptahydrate crystals were dissolved for 15 minutes and then pulled up. Then, the molded body is ventilated to blow off the excessively adhered solution and dried at 110 ° C. for 3 hours.
Molded catalyst prepared by calcining at 400 ° C. for 3 hours and supporting 100 parts by weight of titanium oxide, 12.42 parts by weight of tungsten trioxide, 0.65 part by weight of vanadium pentoxide and 0.25 part by weight of magnesium sulfate. I got E.
【００５９】比較例３ 硫酸マグネシウム７水塩の結晶８９ｋｇを溶解した水溶
液２４０Ｌに前記成形体Ｉを１５分間浸漬した後、引き
上げた。次いで、触媒に通風して、過剰に付着している
上記溶液を吹き払い、１１０℃で３時間乾燥した後、４
００℃で３時間焼成して、酸化チタン１００重量部に対
して、三酸化タングステン１2.４２重量部、五酸化バナ
ジウム0.６５重量部及び硫酸マグネシウム6.６重量部を
担持してなる成形触媒Ｆを得た。Comparative Example 3 The molding I was immersed in 240 L of an aqueous solution in which 89 kg of magnesium sulfate heptahydrate crystals were dissolved for 15 minutes and then pulled up. Then, the catalyst is ventilated to blow off the excessively adhered solution and dried at 110 ° C. for 3 hours, and then 4
Molded catalyst prepared by calcining at 00 ° C for 3 hours and supporting 100 parts by weight of titanium oxide, 12.42 parts by weight of tungsten trioxide, 0.65 parts by weight of vanadium pentoxide and 6.6 parts by weight of magnesium sulfate. I got F.
【００６０】比較例４ 実施例８において、触媒として、比較例１で得られた成
形体Ｉ、比較例２及び３で得られた成形触媒Ｅ及びＦを
それぞれ用いた以外は、実施例８と同じ条件下に、成形
体又は成形触媒の摩耗試験を行なった。結果を表１に示
す。Comparative Example 4 As in Example 8, except that the molded article I obtained in Comparative Example 1 and the molded catalysts E and F obtained in Comparative Examples 2 and 3 were used as the catalysts in Example 8, respectively. Under the same conditions, the wear test of the molded body or molded catalyst was performed. The results are shown in Table 1.
【００６１】比較例５ 実施例９において、触媒として、比較例１で得られた成
形体Ｉ、比較例２及び３で得られた成形触媒Ｅ及びＦを
それぞれ用いた以外は、実施例９と同じ条件下に、燃焼
排ガスの脱硝試験を行なって、触媒の触媒活性を試験し
た。結果を表１に示す。更に、上述したようにして、燃
焼排ガスの脱硝処理を行なった成形触媒の先端部分の内
壁（貫通孔壁）の壁厚さの変化と成形触媒のガス流れ方
向の全長の１／２の位置における内壁の壁厚さの変化を
調べた。その結果を表１に示す。成形触媒の先端部分の
内壁（貫通孔壁）厚さの変化は括弧内に示す。Comparative Example 5 As in Example 9, except that the molded article I obtained in Comparative Example 1 and the molded catalysts E and F obtained in Comparative Examples 2 and 3 were used as the catalysts, respectively. Under the same conditions, a flue gas denitration test was performed to test the catalytic activity of the catalyst. The results are shown in Table 1. Further, as described above, the change in the wall thickness of the inner wall (through-hole wall) of the tip portion of the molded catalyst that has been subjected to the denitration treatment of the combustion exhaust gas and the position of 1/2 of the total length of the molded catalyst in the gas flow direction. The change in the wall thickness of the inner wall was investigated. Table 1 shows the results. The change in the thickness of the inner wall (through hole wall) at the tip of the shaped catalyst is shown in parentheses.
【００６２】比較例６ 実施例１１において、触媒Ａ１及びＣ１に代えて、比較
例１得られた成形体Ｉ、比較例２及び３で得られた成形
触媒Ｅ及びＦをそれぞれ用いた以外は、実施例１１と同
じ条件下に、触媒反応器において成形触媒に局部的な摩
耗が生じる位置に充填した以外は、実施例９と同じ条件
下に、石炭を燃焼とする燃焼排ガスの流通下、８０００
時間にわたって、脱硝処理を行なった。試験結果を表２
に示す。成形触媒の先端部分の内壁（貫通孔壁）厚さの
変化は括弧内に示す。Comparative Example 6 In Example 11, the catalysts A1 and C1 were replaced by the molded article I obtained in Comparative Example 1 and the molded catalysts E and F obtained in Comparative Examples 2 and 3, respectively. Under the same conditions as in Example 11, under the same conditions as in Example 9, except that the molded catalyst was charged in a position where localized wear was generated in the catalytic reactor, under the flow of combustion exhaust gas in which coal was burned, 8000
A denitration treatment was performed over time. Table 2 shows test results
Shown in The change in the thickness of the inner wall (through hole wall) at the tip of the shaped catalyst is shown in parentheses.
【００６３】[0063]
【表１】 [Table 1]
【００６４】[0064]
【表２】 [Table 2]
【００６５】本発明によれば、所定の触媒成分からなる
成形体に硫酸マグネシウム水溶液を含浸させ、加熱焼成
して、硫酸マグネシウムを所定の範囲で担持させること
によって、触媒活性を損なうことなく、ダストによる摩
耗に対する強度を成形触媒に付与することができ、かく
して、排ガスを長期間にわたって、脱硝処理を行なって
も、触媒活性の低下は少なく、また、成形触媒の内壁厚
さの摩耗も殆ど生じていない。According to the present invention, a molded body made of a predetermined catalyst component is impregnated with an aqueous solution of magnesium sulfate and heated and baked to support magnesium sulfate in a predetermined range, so that the catalyst activity is not impaired and dust is produced. It is possible to impart strength to the formed catalyst to abrasion, and thus even if exhaust gas is subjected to denitration treatment for a long period of time, there is little deterioration in catalyst activity, and abrasion of the inner wall thickness of the formed catalyst is almost generated. Absent.
【００６６】これに対して、比較例１、２及び４によれ
ば、触媒活性は、長期間にわたる脱硝処理においても、
低下は少ないが、しかし、ハニカム触媒の内壁厚さが著
しく摩耗しており、長期間の使用には耐えない。更に、
比較例３及び４によれば、ハニカム触媒の内壁厚さの摩
耗は生じていないが、触媒の初期触媒活性が低く、ま
た、触媒活性の低下も大きく、同様に、長期間の使用に
耐えない。On the other hand, according to Comparative Examples 1, 2 and 4, the catalytic activity was high even in the denitration treatment for a long period of time.
Although the decrease is small, however, the thickness of the inner wall of the honeycomb catalyst is significantly worn, and it cannot withstand long-term use. Furthermore,
According to Comparative Examples 3 and 4, although the inner wall thickness of the honeycomb catalyst is not abraded, the initial catalyst activity of the catalyst is low, and the catalyst activity is greatly reduced, and similarly, it cannot withstand long-term use. .
───────────────────────────────────────────────────── フロントページの続き (72)発明者 出本 昌則 長崎県長崎市飽の浦町１番１号 三菱重工 業株式会社長崎造船所内 (72)発明者 飯田 耕三 広島県広島市西区観音新町４丁目６番22号 三菱重工業株式会社広島研究所内 (72)発明者 力丸 浩昭 大阪府堺市戎島町５丁１番地 堺化学工業 株式会社内 (72)発明者 馬場 敏勝 大阪府泉大津市臨海町１丁目18番地 堺化 学工業株式会社内 (72)発明者 吉川 嘉之 大阪府泉大津市臨海町１丁目18番地 堺化 学工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masanori Demoto 1-1, Atsunoura-machi, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Shipyard (72) Inventor, Kozo Iida 4-chome, Kannon-shinmachi, Nishi-ku, Hiroshima-shi, Hiroshima No. 22 Mitsubishi Heavy Industries, Ltd. Hiroshima Research Institute (72) Inventor Hiroaki Rikimaru 5-1, Ebishima-cho, Sakai City, Osaka Prefecture Sakai Chemical Industry Co., Ltd. (72) Inventor, Toshikatsu Baba 1-1-18, Rinkai-cho, Izumiotsu-shi, Osaka Prefecture Sakai Kagaku Kogyo Co., Ltd. (72) Inventor Yoshiyuki Yoshikawa 1-18 Rinkai-cho, Izumiotsu City, Osaka Prefecture Sakai Kagaku Kogyo Co., Ltd.
Claims (7)
合酸化物１００重量部に対して、 (b) 三酸化タングステン５〜２０重量部と、 (c) 五酸化バナジウム０〜2.０重量部とを含む多孔質成
形体に硫酸マグネシウム水溶液を含浸させ、加熱焼成し
て、硫酸マグネシウムを0.５〜5.５重量部の範囲で上記
多孔質成形体に担持させてなることを特徴とする排ガス
に含まれる窒素酸化物を還元除去するための成形触媒。Claims: 1. To (a) 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide, (b) 5 to 20 parts by weight of tungsten trioxide and (c) 0 to 2.0 parts by weight of vanadium pentoxide. Characterized in that it is impregnated with a magnesium sulfate aqueous solution into a porous molded body including a part and is heated and baked to support magnesium sulfate in the range of 0.5 to 5.5 parts by weight on the porous molded body. Molded catalyst for reducing and removing nitrogen oxides contained in exhaust gas.
るために、排ガスの入口と出口とを備えた触媒反応器に
充填して用いる成形触媒であって、上記入口から上記触
媒反応器に導入される排ガスの流れ方向に少なくとも１
つの貫通孔を有する請求項１に記載の成形触媒。2. A molded catalyst which is used by filling a catalytic reactor provided with an inlet and an outlet of exhaust gas for reducing and removing nitrogen oxides contained in the exhaust gas, wherein the catalyst is supplied from the inlet to the catalytic reactor. At least 1 in the flow direction of the introduced exhaust gas
The molded catalyst according to claim 1, which has one through hole.
耐摩耗性にした請求項２に記載の成形触媒。3. The molded catalyst according to claim 2, wherein the tip portion of the molded catalyst including the exhaust gas inlet is made wear resistant.
を請求項１、２又は３のいずれかに記載の成形触媒に接
触させる排ガスに含まれる窒素酸化物を還元除去する方
法。4. A method for reducing and removing nitrogen oxides contained in an exhaust gas, which comprises contacting the exhaust gas containing nitrogen oxides with the molded catalyst according to claim 1, 2 or 3 in the presence of a reducing agent.
合酸化物１００重量部に対して、 (b) 三酸化タングステン５〜２０重量部と、 (c) 五酸化バナジウム０〜2.０重量部とを含む多孔質成
形体に硫酸マグネシウム水溶液を含浸させ、加熱焼成し
て、硫酸マグネシウムを0.５〜5.５重量部の範囲で上記
多孔質成形体に担持させることを特徴とする排ガスに含
まれる窒素酸化物を還元除去するための成形触媒の製造
方法。5. (a) 5 to 20 parts by weight of tungsten trioxide and (c) 0 to 2.0 parts by weight of vanadium pentoxide with respect to 100 parts by weight of titanium oxide or titanium oxide-silica composite oxide. An exhaust gas characterized by impregnating an aqueous magnesium sulfate solution into a porous molded body containing a part and heat-calcined to support magnesium sulfate in the range of 0.5 to 5.5 parts by weight on the porous molded body. A method for producing a molded catalyst for reducing and removing nitrogen oxides contained in.
るために、排ガスの入口と出口とを備えた触媒反応器に
充填して用いる成形触媒の製造方法であって、上記入口
から上記触媒反応器に導入される排ガスの流れ方向に少
なくとも１つの貫通孔を有する請求項５に記載の成形触
媒の製造方法。6. A method for producing a shaped catalyst, which is used by filling a catalytic reactor provided with an inlet and an outlet of exhaust gas to reduce and remove nitrogen oxides contained in the exhaust gas, the catalyst being supplied from the inlet to the catalyst. The method for producing a molded catalyst according to claim 5, wherein at least one through hole is provided in the flow direction of the exhaust gas introduced into the reactor.
耐摩耗性にする請求項６に記載の成形触媒の製造方法。7. The method for producing a molded catalyst according to claim 6, wherein the front end portion of the molded catalyst including the exhaust gas inlet is made wear-resistant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9654896A JP3595622B2 (en) | 1996-04-18 | 1996-04-18 | Catalyst and method for reducing and removing nitrogen oxides contained in exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9654896A JP3595622B2 (en) | 1996-04-18 | 1996-04-18 | Catalyst and method for reducing and removing nitrogen oxides contained in exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09276659A true JPH09276659A (en) | 1997-10-28 |
| JP3595622B2 JP3595622B2 (en) | 2004-12-02 |
Family
ID=14168151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9654896A Expired - Lifetime JP3595622B2 (en) | 1996-04-18 | 1996-04-18 | Catalyst and method for reducing and removing nitrogen oxides contained in exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3595622B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001096154A (en) * | 1999-09-29 | 2001-04-10 | Yamada Sangyo Kk | Vanadium oxide/titania hybrid photocatalyst and its manufacturing method |
| KR100515907B1 (en) * | 2002-06-27 | 2005-09-20 | 재단법인 한국환경기술진흥원 | Catalyst for removing dioxin and/or nitrogen oxide, and preparation method thereof |
| JP2006231332A (en) * | 2000-01-20 | 2006-09-07 | Nippon Shokubai Co Ltd | Abrasion resistant catalyst molded body |
-
1996
- 1996-04-18 JP JP9654896A patent/JP3595622B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001096154A (en) * | 1999-09-29 | 2001-04-10 | Yamada Sangyo Kk | Vanadium oxide/titania hybrid photocatalyst and its manufacturing method |
| JP2006231332A (en) * | 2000-01-20 | 2006-09-07 | Nippon Shokubai Co Ltd | Abrasion resistant catalyst molded body |
| KR100515907B1 (en) * | 2002-06-27 | 2005-09-20 | 재단법인 한국환경기술진흥원 | Catalyst for removing dioxin and/or nitrogen oxide, and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3595622B2 (en) | 2004-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU602270B2 (en) | Catalyst for the selective reduction of nitrogen oxides with amnonia | |
| US4294806A (en) | Method for preventing the wear of a monolithic catalyst by dusts | |
| US5212140A (en) | Catalyst for decomposing ozone | |
| RU2058814C1 (en) | Catalyst for selective nitrogen oxides reduction with ammonia and a method of its preparing | |
| KR100781726B1 (en) | Method for manufacturing de-nox scr coating catalyst using porous ceramic substrate | |
| RU2393014C2 (en) | Crust catalyst specifically designed for oxidising methanol to formaldehyde and method of preparing said catalyst | |
| JPH02194839A (en) | Silver catalyst for producing ethylene oxide and production thereof | |
| JPH08196B2 (en) | Catalyst for reducing nitrogen oxide content in flue gas | |
| JP2008512234A (en) | Catalyst support substrate coated with a washcoat comprising fibrous material | |
| JPH11507007A (en) | Catalyst carrier | |
| KR20090080268A (en) | Fabrication Method of Zeolite Honeycomb type Catalyst for Reducing Nitrogen Oxide | |
| KR100739409B1 (en) | Silicon carbide-based catalytic body and process for producing the same | |
| KR101362606B1 (en) | NOx REMOVAL CATALYST FOR HIGH-TEMPERATURE FLUE GAS, MANUFACTURING METHOD THEREOF, AND NOx REMOVAL METHOD FOR HIGH-TEMPERATURE FLUE GAS | |
| JPH0242536B2 (en) | ||
| RU1837957C (en) | Catalyst for treatment of sulfur-containing gases | |
| JPS63185448A (en) | Catalyst and method for removing nitrogen oxide in exhaust gas | |
| CN114011400A (en) | Preparation method of acid system waste incineration SCR denitration catalyst and prepared denitration catalyst | |
| JPS63274455A (en) | Plate-shaped catalyst for removing nitrogen oxide from exhaust gas and its production | |
| JPH09276659A (en) | Catalyst for removal of nitrogen oxide contained in exhaust gas by reduction and manufacture of catalyst | |
| KR101187758B1 (en) | METHOD FOR MANUFACTURING DE-NOx SCR CATALYST USING CALCIUM SULFATE HEMIHYDRATE | |
| JPH0480742B2 (en) | ||
| JP6157916B2 (en) | NOx removal catalyst and method for producing the same | |
| JPS603859B2 (en) | catalyst molded product | |
| JP3496964B2 (en) | Catalyst for ammonia reduction of nitrogen oxides in exhaust gas and method for producing the same | |
| JPH09220468A (en) | Catalyst for removal of nox in exhaust gas, its production and method for removing nox in exhaust gas using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040206 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040217 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040416 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040518 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040716 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040824 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040906 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070910 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080910 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090910 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090910 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100910 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100910 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110910 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120910 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130910 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |