JP2010214239A - Catalyst for removing nitrogen oxide, method of producing the same, and method of removing nitrogen oxide using the same - Google Patents
Catalyst for removing nitrogen oxide, method of producing the same, and method of removing nitrogen oxide using the same Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 15
- 239000007789 gas Substances 0.000 claims abstract description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 230000009970 fire resistant effect Effects 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 230000001603 reducing effect Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、窒素酸化物除去用触媒、その製造法およびその触媒を用いた窒素酸化物除去方法に関するものである。 The present invention relates to a nitrogen oxide removing catalyst, a production method thereof, and a nitrogen oxide removing method using the catalyst.
窒素酸化物および酸素を含むガスにおいて、窒素酸化物を還元し窒素にするための技術が多く提案されている。排煙脱硝処理にあっては、当該ガスにアンモニア、尿素を添加し、バナジウム系触媒により窒素に還元する技術が提案されている。このような触媒は比較的低温であれば問題は無いが９００℃近くの温度に曝されたとき触媒が焼結し比表面積が低下し触媒活性が低下することがある（引用文献１）。また４００℃以下で低温かつ定常のガスに対して触媒用担体としてセラミック担体を用いることがある（引用文献２）。当該担体は耐熱性があるが、熱導電率が低く急激な温度の変化のあるガスに対して有効な活性を生じさせることには不向きである。 Many techniques for reducing nitrogen oxides to nitrogen in a gas containing nitrogen oxides and oxygen have been proposed. In flue gas denitration treatment, a technique has been proposed in which ammonia and urea are added to the gas and reduced to nitrogen by a vanadium catalyst. Such a catalyst has no problem as long as it is at a relatively low temperature, but when exposed to a temperature close to 900 ° C., the catalyst may sinter, the specific surface area may decrease, and the catalytic activity may decrease (Cited Document 1). In addition, a ceramic carrier may be used as a catalyst carrier for a low temperature and steady gas at 400 ° C. or lower (Cited document 2). Although the carrier has heat resistance, it is not suitable for producing an effective activity against a gas having a low thermal conductivity and a rapid temperature change.
更に、窒素酸化物、酸素および水素を含むガスにおける窒素酸化物の処理、特に水素、アンモニアを燃料とする内燃機関から生じるガスの処理技術の開示はないことが多く（特開平５−３３２１５２号、特表２００１−５１２４１２号）、開示があったとしても還元触媒を用いて処理することの記載はあるが、ガスが高温かつ濃度が変動する条件下に使用できる具体的な触媒について提案はなく、如何なる触媒組成、形状が適用できるのか不明である（特許文献３）。 Further, there is often no disclosure of a technique for treating nitrogen oxides in a gas containing nitrogen oxides, oxygen, and hydrogen, particularly treatment of gases generated from an internal combustion engine fueled with hydrogen and ammonia (Japanese Patent Laid-Open No. 5-332152, Even if there is a disclosure, there is a description of treatment using a reduction catalyst, but there is no proposal for a specific catalyst that can be used under conditions where the gas is at a high temperature and the concentration varies, It is unclear what catalyst composition and shape can be applied (Patent Document 3).
本発明は、先行技術において具体的に開示のない触媒およびその形状を提案するものである。更に窒素酸化物を含むガスの処理の分野において処理用のガスが有する特性、即ちガス温度の変動が激しく、空間速度が速い条件下で用いる触媒を提供することにある。 The present invention proposes a catalyst and its shape not specifically disclosed in the prior art. Another object of the present invention is to provide a catalyst used in the field of treatment of a gas containing nitrogen oxides, that is, a characteristic of a gas for treatment, that is, a gas temperature fluctuates greatly and a space velocity is high.
本発明者らは、上記課題を解決するために鋭意検討した結果、下記手段を見出し、発明を完成した。本発明は下記の通り特定されるものである。 As a result of intensive studies to solve the above problems, the present inventors have found the following means and completed the invention. The present invention is specified as follows.
本発明の第一発明は、平均粒子径０．０１μｍ〜５μｍ窒素酸化物浄化用触媒成分の粒子を、１平方インチ当たり２００〜６００個の貫通孔を有するハニカムまたはコルゲートの耐火性三次元構造体に被覆したものであることを特徴とする窒素酸化物除去用触媒である。本発明の第二発明は、上記触媒の製造法であり、第三発明は上記触媒を用いたガス中の窒素酸化物の除去方法である。 The first invention of the present invention is a honeycomb or corrugated fire-resistant three-dimensional structure having 200 to 600 through-holes per square inch of particles of an average particle diameter of 0.01 μm to 5 μm nitrogen oxide purification catalyst component A catalyst for removing nitrogen oxides, characterized in that it is coated on the surface. The second invention of the present invention is a method for producing the above catalyst, and the third invention is a method for removing nitrogen oxides in a gas using the above catalyst.
本発明は、窒素酸化物を含むガスであって、ガス温度の変動が激しく、空間速度が速い条件下でも、十分に窒素酸化物を除去できる触媒を提供することにある。 An object of the present invention is to provide a catalyst containing nitrogen oxides, which can sufficiently remove nitrogen oxides even under conditions where the gas temperature varies greatly and the space velocity is high.
本発明の第一発明は、窒素酸化物、酸素および水素を含むガスであって当該ガス中の酸素濃度が０〜１０容量％である当該ガスにアンモニアまたは尿素を導入し、窒素酸化物を浄化する触媒であって、当該触媒が平均粒子径０．０１μｍ〜５μｍ触媒成分の粒子を、１平方インチ当たり２００〜６００個の貫通孔を有するハニカムまたはコルゲートの耐火性三次元構造体に被覆したものであることを特徴とする窒素酸化物除去用触媒である。 The first invention of the present invention purifies nitrogen oxides by introducing ammonia or urea into the gas containing nitrogen oxides, oxygen and hydrogen and having an oxygen concentration of 0 to 10% by volume. A catalyst having a mean particle size of 0.01 μm to 5 μm coated with particles of a catalyst component on a honeycomb or corrugated fire-resistant three-dimensional structure having 200 to 600 through-holes per square inch This is a catalyst for removing nitrogen oxides.
当該触媒成分が耐火性三次元構造体１リットル当たり、１０ｇ〜５００ｇ被覆されてなることが好ましい。当該触媒成分が、モリブデン、バナジウム、タングステン、ニッケル、コバルト、鉄、パラジウム、ロジウム、ルテニウム、白金およびイリジウムからなる群から選ばれる少なくとも一種の触媒活性成分と、耐火性無機酸化物とを含むことが好ましい。 The catalyst component is preferably coated with 10 to 500 g per liter of the refractory three-dimensional structure. The catalyst component includes at least one catalytically active component selected from the group consisting of molybdenum, vanadium, tungsten, nickel, cobalt, iron, palladium, rhodium, ruthenium, platinum and iridium, and a refractory inorganic oxide. preferable.
第二発明は、当該触媒が、当該触媒成分の粉体を酸性水性媒体中で湿式粉砕により、平均粒子径０．０１μｍ〜５μｍの触媒成分を含むスラリーとし、当該スラリーを当該耐火性三次元構造体に被覆して得られることを特徴とする上記窒素酸化物除去用触媒の製造法である。 In the second invention, the catalyst is a slurry containing a catalyst component having an average particle size of 0.01 μm to 5 μm by wet pulverization of the catalyst component powder in an acidic aqueous medium, and the slurry is the fire-resistant three-dimensional structure. A method for producing the above-mentioned catalyst for removing nitrogen oxides, which is obtained by coating the body.
第三発明は、上記触媒を用いて窒素酸化物、酸素および水素を含むガスであって当該ガス中の酸素濃度が０〜１０容量％である当該ガスにアンモニアまたは尿素を導入し、窒素酸化物を浄化することを特徴とする窒素酸化物浄除去方法である。 A third invention introduces ammonia or urea into a gas containing nitrogen oxides, oxygen and hydrogen, wherein the oxygen concentration in the gas is 0 to 10% by volume using the catalyst, This is a method for purifying and removing nitrogen oxides.
本発明が対象とするガスは窒素酸化物、酸素および水素を含むガスであって当該ガス中の酸素濃度が０〜１０容量％であり、好ましくは０〜７容量％である。また、当該ガスがアンモニアを改質し水素へ転換されたガスを用いた内燃機関の排ガスであってもよい。当該内燃機関は、特許文献３記載の内燃機関等である。 The gas targeted by the present invention is a gas containing nitrogen oxides, oxygen and hydrogen, and the oxygen concentration in the gas is 0 to 10% by volume, preferably 0 to 7% by volume. Further, the gas may be exhaust gas of an internal combustion engine using a gas obtained by reforming ammonia and converting it to hydrogen. The internal combustion engine is an internal combustion engine described in Patent Document 3.
当該水素濃度が０〜１容量％であり、好ましくは０〜０．５容量％である。 The hydrogen concentration is 0 to 1% by volume, preferably 0 to 0.5% by volume.
当該窒素酸化物濃度は１０ｐｐｍ〜５容量％であり、好ましくは５０ｐｐｍ〜２容量％である。窒素酸化物とは、Ｎ２Ｏ、ＮＯ、ＮＯ２の何れであっても良い。 The nitrogen oxide concentration is 10 ppm to 5% by volume, preferably 50 ppm to 2% by volume. Nitrogen oxide may be any of N 2 O, NO, and NO 2 .
窒素酸化物の処理とは窒素酸化物を窒素に還元することをいう。排ガス中に当該窒素酸化物を窒素に還元するに足る還元物質、例えば水素が存在するときは問題なく窒素酸化物を処理することができるが、還元物質が少ないときは当該ガス中に還元物質を導入し窒素酸化物を還元することもできる。還元物質は通常還元作用のあるものであれは何れのものであっても良いが、好ましくは水素、アンモニア、尿素である。当該ガス中に導入する還元物質の量は、窒素酸化物を化学量論的に窒素にする量であるが、窒素酸化物の種類、窒素酸化物の還元速度を考慮すると、アンモニア量は窒素酸化物１モルに対して０．８〜１．５モル、好ましくは１．０〜１．２モルである。なお、尿素を用いるときはアンモニアの１／２モルである。 Nitrogen oxide treatment refers to reducing nitrogen oxides to nitrogen. When there is a reducing substance sufficient to reduce the nitrogen oxide to nitrogen in the exhaust gas, for example, hydrogen, the nitrogen oxide can be treated without problems, but when there is little reducing substance, the reducing substance is added to the gas. Nitrogen oxide can also be reduced by introduction. The reducing substance may be any substance that usually has a reducing action, but is preferably hydrogen, ammonia, or urea. The amount of reducing substance introduced into the gas is an amount that makes nitrogen oxide stoichiometrically nitrogen. However, in consideration of the type of nitrogen oxide and the reduction rate of nitrogen oxide, the amount of ammonia is reduced by nitrogen oxidation. It is 0.8-1.5 mol with respect to 1 mol of things, Preferably it is 1.0-1.2 mol. In addition, when using urea, it is 1/2 mol of ammonia.
反応温度は、１００℃〜６５０℃、好ましくは２００℃〜６００℃である。 The reaction temperature is 100 ° C to 650 ° C, preferably 200 ° C to 600 ° C.
当該ガス量は、空間速度（ＳＶ）で１，０００〜１，０００，０００ｈｒ−１であり、好ましくは５，０００〜１００，０００ｈｒ−１である。 The gas quantity is 1,000～1,000,000Hr -1 at a space velocity (SV), preferably 5,000~100,000hr -1.
本発明にかかる耐火性三次元構造体は１平方インチ当たり２００〜６００個の貫通孔を有するハニカムまたはコルゲートである。当該貫通孔をガスが通過する際、当該孔壁に被覆された触媒により当該ガス中の窒素酸化物が窒素に還元されるものである。当該耐火性三次元構造体の貫通孔は好ましくは１平方インチ当たり２００〜６００個、更に好ましくは３００〜４００個である。材質はコージェライトなどのセラミック製、金属製のものを用いることができる。また、セラミック製のハニカムを用いるとき当該孔壁の厚さは壁厚が０．００１インチのハニカム〜０．００４インチ、好ましくは０．００１５〜０．００３インチである。 The fire-resistant three-dimensional structure according to the present invention is a honeycomb or corrugate having 200 to 600 through holes per square inch. When the gas passes through the through-hole, the nitrogen oxide in the gas is reduced to nitrogen by the catalyst coated on the hole wall. The number of through holes of the fireproof three-dimensional structure is preferably 200 to 600, more preferably 300 to 400 per square inch. The material may be ceramic or metal such as cordierite. Further, when a ceramic honeycomb is used, the thickness of the hole wall is from a honeycomb having a wall thickness of 0.001 inch to 0.004 inch, preferably 0.0015 to 0.003 inch.
本発明に係る触媒は平均粒子径０．０１μｍ〜５μｍ、好ましくは平均粒子径が０．０２〜３μｍである。当該平均粒子の測定方法は通常粒子の粒子径を測定する装置であれば良く、例えば後方散乱光検出方式超微粒子粒度分布測定装置、レーザー回折・散乱式粒子径分布測定装置等を使用することができる。 The catalyst according to the present invention has an average particle size of 0.01 to 5 μm, preferably an average particle size of 0.02 to 3 μm. The average particle measurement method may be any device that measures the particle size of normal particles. For example, a backscattered light detection type ultrafine particle size distribution measurement device, a laser diffraction / scattering type particle size distribution measurement device, or the like may be used. it can.
触媒活性成分は、窒素酸化物を処理するものであれば何れのものであっても良い。好ましくは、モリブデン、バナジウム、タングステン、ニッケル、コバルト、鉄、パラジウム、ロジウム、ルテニウム、白金、イリジウムであり、好ましくはモリブデン、バナジウム、タングステン、白金、パラジウムである。パラジウム、ロジウム、ルテニウム、白金およびイリジウムを金属系触媒活性成分、モリブデン、バナジウム、タングステン、ニッケル、コバルトおよび鉄を金属酸化物系触媒活性成分と称する。 The catalytically active component may be any as long as it can treat nitrogen oxides. Preferred are molybdenum, vanadium, tungsten, nickel, cobalt, iron, palladium, rhodium, ruthenium, platinum and iridium, preferably molybdenum, vanadium, tungsten, platinum and palladium. Palladium, rhodium, ruthenium, platinum and iridium are referred to as metal catalyst active components, and molybdenum, vanadium, tungsten, nickel, cobalt, and iron are referred to as metal oxide catalyst active components.
当該触媒活性成分は、金属、酸化物、炭酸塩であっても良いが、好ましくは当該ガス中で安定な状態を保つものが良く、金属又は酸化物である。 The catalytically active component may be a metal, an oxide, or a carbonate, but is preferably a metal or an oxide that maintains a stable state in the gas.
当該触媒活性成分は単独でも使用することができるが、耐火性無機酸化物に担持しまたは混合し用いることができる。当該耐火性無機酸化物としては、耐火性を有し、比表面積が５０〜２００ｍ２／ｇ（ＢＥＴ表面積）のものを用いることができ、例えばアルミナ、シリカ、ジルコニア、チタニア、シリカ−アルミナ、アルミナ−ジルコニア、ゼオライトなどを用いることができる。当該ガス中に硫黄分が含まれるときは、チタン酸化物を用いるのが好ましく、チタン酸化物とは、チタン酸化物、チタンと珪素、ジルコニウム、アルミニウムの少なくとも一種を用いることができる。特に金属系触媒活性成分は当該耐火性無機酸化物に担持して使用することが好ましい。また、金属系触媒活性成分は金属酸化物系活性成分に担持することもできる。 The catalytically active component can be used alone, but can be supported on or mixed with a refractory inorganic oxide. As the refractory inorganic oxide, those having fire resistance and a specific surface area of 50 to 200 m 2 / g (BET surface area) can be used. For example, alumina, silica, zirconia, titania, silica-alumina, alumina -Zirconia, zeolite, etc. can be used. When the gas contains a sulfur component, it is preferable to use titanium oxide. As the titanium oxide, at least one of titanium oxide, titanium and silicon, zirconium, and aluminum can be used. In particular, the metal catalyst active component is preferably used by being supported on the refractory inorganic oxide. Further, the metal catalyst active component can be supported on the metal oxide active component.
当該金属系触媒活性成分は、耐火性三次元構造体１リットル当たり０．０５ｇ〜５０ｇ、好ましくは０．１〜１５ｇ使用することができる。当該金属酸化物系触媒活性成分酸化物として、耐火性三次元構造体１リットル当たり１０ｇ〜５００ｇ、好ましくは３０ｇ〜３００ｇ使用することができる。 The metal-based catalytically active component can be used in an amount of 0.05 to 50 g, preferably 0.1 to 15 g, per liter of the refractory three-dimensional structure. As the metal oxide-based catalytically active component oxide, 10 g to 500 g, preferably 30 g to 300 g can be used per liter of the refractory three-dimensional structure.
当該触媒の平均粒子径は、０．０１μｍ〜５μｍ、好ましくは０．０２〜２μｍである。当該平均粒子径の触媒粒子は触媒粉体をボールミル、ビーズミル等通常湿式粉砕用の粉砕機を用いて得ることができる。 The average particle diameter of the catalyst is 0.01 μm to 5 μm, preferably 0.02 to 2 μm. The catalyst particles having the average particle diameter can be obtained by using a normal wet pulverizer such as a ball mill or a bead mill.
また、当該平均粒子径の測定方法は、Ｘ線粒度分布測定器などを用いて測定することができる。 Moreover, the measuring method of the said average particle diameter can be measured using a X-ray particle size distribution measuring device etc.
以下に本発明に係る触媒の調製法を示すが本発明の趣旨に反しない限り、下記の調製法に限定されるものではない。
（１）触媒活性成分を酸性水性媒体に添加し、湿式粉砕機に投入し粉砕することでスラリーを得た後、当該スラリーに耐火性三次元構造体を浸し、余剰のスラリーを除いた後、乾燥、焼成することで触媒を得る方法。
（２）耐火性無機酸化物を酸性水性媒体に添加し、湿式粉砕機に投入し粉砕することでスラリーを得た後、上記（１）で得られた触媒を浸し、余剰のスラリーを除いた後、乾燥、焼成することで触媒を得る方法。
（３）触媒活性成分と耐火性無機酸化物とを酸性水性媒体に添加し、湿式粉砕機に投入し粉砕することで、スラリーを得る。得られたスラリーに耐火性三次元構造体を浸し、余剰のスラリーを除いた後、乾燥、焼成することで触媒を得る方法。
（４）耐火性無機酸化物を酸性水性媒体に添加し、湿式粉砕機に投入し粉砕することでスラリーを得た後、当該スラリーに耐火性三次元構造体を浸し、余剰のスラリーを除いた後、乾燥、焼成した後、触媒活性成分を含む水性媒体に浸し、余剰の液を除き、乾燥、焼成することで触媒を得る方法。また、触媒活性成分を耐火性無機酸化物に担持した後、酸性媒体に添加し、湿式粉砕機に投入し粉砕することで、スラリーを得る。得られたスラリーに耐火性三次元構造体を浸し、余剰のスラリーを除いた後、乾燥、焼成することで触媒を得る方法をとることもできる。
Although the preparation method of the catalyst based on this invention is shown below, unless it is contrary to the meaning of this invention, it is not limited to the following preparation method.
(1) After adding a catalytically active component to an acidic aqueous medium, obtaining a slurry by putting it in a wet pulverizer and pulverizing it, immersing the refractory three-dimensional structure in the slurry and removing excess slurry, A method of obtaining a catalyst by drying and firing.
(2) After adding a refractory inorganic oxide to an acidic aqueous medium and putting it in a wet pulverizer to obtain a slurry, the catalyst obtained in (1) above was immersed to remove excess slurry. Thereafter, the catalyst is obtained by drying and firing.
(3) A slurry is obtained by adding a catalytically active component and a refractory inorganic oxide to an acidic aqueous medium, putting the mixture into a wet pulverizer, and pulverizing. A method of obtaining a catalyst by immersing a fire-resistant three-dimensional structure in the obtained slurry, removing excess slurry, and drying and firing.
(4) After adding a refractory inorganic oxide to an acidic aqueous medium and putting it into a wet pulverizer to obtain a slurry, the slurry was immersed in the refractory three-dimensional structure to remove excess slurry. Then, after drying and calcination, the catalyst is obtained by immersing in an aqueous medium containing a catalytically active component, removing excess liquid, and drying and calcination. Moreover, after carrying | supporting a catalyst active component on a refractory inorganic oxide, it adds to an acidic medium, throws into a wet crusher, and grind | pulverizes to obtain a slurry. A method of obtaining a catalyst by immersing the fire-resistant three-dimensional structure in the obtained slurry, removing excess slurry, and drying and firing can also be used.
以下に実施例と比較例を用いて詳細に発明を説明するが、下記実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail using Examples and Comparative Examples, but is not limited to the following Examples.
（実施例１）
蓚酸バナジルを水に溶解し、これを酸化チタンと混合し、乾燥、焼成する。焼成した後の粉体を、湿式粉砕機で粉砕しスラリーを得る。耐火性三次元構造体として、貫通孔数が１平方インチ当たり４００個、壁厚が０．００３インチのハニカムを、当該スラリーに浸し余剰のスラリーを吹き払い、乾燥、焼成し触媒を得る。当該触媒を水素エンジンの排ガス排出口に設置する。一方、当該触媒と当該排出口との間にアンモニア導入口を設け排ガスと混合し、当該排ガス中の窒素酸化物を窒素に還元する。
Example 1
Vanadyl oxalate is dissolved in water, mixed with titanium oxide, dried and fired. The powder after firing is pulverized with a wet pulverizer to obtain a slurry. As a fire-resistant three-dimensional structure, a honeycomb having 400 through-holes per square inch and a wall thickness of 0.003 inches is immersed in the slurry, and the excess slurry is blown off, dried and fired to obtain a catalyst. The catalyst is installed at the exhaust port of the hydrogen engine. On the other hand, an ammonia introduction port is provided between the catalyst and the discharge port and mixed with exhaust gas, and nitrogen oxides in the exhaust gas are reduced to nitrogen.
（実施例２）
実施例１において、当該ハニカムを、コルゲート型の耐火性三次元構造体を用いた以外は実施例１と同じ手順により窒素酸化物の還元処理を行うことができる。
(Example 2)
In Example 1, the honeycomb can be subjected to nitrogen oxide reduction treatment by the same procedure as in Example 1 except that a corrugated fire-resistant three-dimensional structure is used.
本発明は、窒素酸化物、酸素および水素を含むガス中における窒素酸化物の窒素への還元処理に関する分野に用いることができる。 The present invention can be used in the field related to the reduction treatment of nitrogen oxides to nitrogen in a gas containing nitrogen oxides, oxygen and hydrogen.
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