JP6591919B2 - Method for manufacturing honeycomb-type denitration catalyst - Google Patents
Method for manufacturing honeycomb-type denitration catalyst Download PDFInfo
- Publication number
- JP6591919B2 JP6591919B2 JP2016057488A JP2016057488A JP6591919B2 JP 6591919 B2 JP6591919 B2 JP 6591919B2 JP 2016057488 A JP2016057488 A JP 2016057488A JP 2016057488 A JP2016057488 A JP 2016057488A JP 6591919 B2 JP6591919 B2 JP 6591919B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oxide
- kneading
- mass
- titanium
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 198
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 title description 32
- 238000004898 kneading Methods 0.000 claims description 102
- 239000012784 inorganic fiber Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000002131 composite material Substances 0.000 claims description 50
- 239000002243 precursor Substances 0.000 claims description 36
- 150000003464 sulfur compounds Chemical class 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 125000004434 sulfur atom Chemical group 0.000 claims description 15
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 13
- 239000004480 active ingredient Substances 0.000 claims description 10
- MYHPJINPUDBKHX-UHFFFAOYSA-N [Si].[W].[Ti] Chemical compound [Si].[W].[Ti] MYHPJINPUDBKHX-UHFFFAOYSA-N 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 67
- 239000007789 gas Substances 0.000 description 32
- 239000007788 liquid Substances 0.000 description 31
- 229910010413 TiO 2 Inorganic materials 0.000 description 23
- 229910004298 SiO 2 Inorganic materials 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 239000011491 glass wool Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 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 9
- 238000000465 moulding Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000000265 homogenisation Methods 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 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
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Description
本発明は、ハニカム型脱硝触媒（窒素酸化物除去用触媒）の製造方法に関する。本発明に係るハニカム型脱硝触媒（窒素酸化物除去用触媒）は、例えば、重油焚きボイラや石炭焚きボイラ、ガス焚きボイラ、ガスタービン、ガスエンジン、ディーゼルエンジン、火力発電所、ごみ焼却炉および各種工業プロセスから排出される排ガス中に含まれる窒素酸化物（ＮＯｘ）を除去するのに用いられる。 The present invention relates to a method for producing a honeycomb-type denitration catalyst (a catalyst for removing nitrogen oxides). The honeycomb type denitration catalyst (nitrogen oxide removal catalyst) according to the present invention includes, for example, a heavy oil fired boiler, a coal fired boiler, a gas fired boiler, a gas turbine, a gas engine, a diesel engine, a thermal power plant, a waste incinerator, and various types Used to remove nitrogen oxides (NOx) contained in exhaust gas discharged from industrial processes.
一般に、重油焚きボイラや石炭焚きボイラ、ガス焚きボイラ、ガスタービン、ガスエンジン、ディーゼルエンジン、火力発電所、ごみ焼却炉および各種工業プロセスから排出される排ガス中には、窒素酸化物（ＮＯｘ）が含まれている。そして、この排ガス中の窒素酸化物を除去する目的で現在実用化されている窒素酸化物の除去方法としては、アンモニアまたは尿素などの還元剤を用いて排ガス中の窒素酸化物を触媒上で接触還元して窒素および水に分解する選択的触媒還元法（ＳＣＲ法）が一般的である。近年、酸性雨に代表されるように窒素酸化物による環境汚染が世界的に深刻化するに伴い、高性能な触媒が求められている。 Generally, nitrogen oxides (NOx) are present in exhaust gas discharged from heavy oil fired boilers, coal fired boilers, gas fired boilers, gas turbines, gas engines, diesel engines, thermal power plants, waste incinerators, and various industrial processes. include. As a method for removing nitrogen oxides currently in practical use for the purpose of removing nitrogen oxides in the exhaust gas, the nitrogen oxides in the exhaust gas are contacted on the catalyst using a reducing agent such as ammonia or urea. A selective catalytic reduction method (SCR method) which reduces to nitrogen and water is common. In recent years, as environmental pollution caused by nitrogen oxides has become serious worldwide, as represented by acid rain, a high-performance catalyst has been demanded.
一方、上記排ガス中には硫黄酸化物（ＳＯｘ）等の酸性ガスも含まれていることから、当該排ガスの処理に用いられる触媒にはＮＯｘ除去性能に加えて耐ＳＯｘ性を有していることが必要であり、この観点からはチタニア系触媒が有望とされている。 On the other hand, since the exhaust gas contains an acid gas such as sulfur oxide (SOx), the catalyst used for the treatment of the exhaust gas has SOx resistance in addition to NOx removal performance. From this point of view, a titania-based catalyst is considered promising.
ここで、チタニア系の脱硝触媒をハニカム型触媒の形態とすることで、触媒の表面積および細孔容積を大きくし、低温、高空間速度でも高性能を示す高活性な脱硝触媒とすることが行われている。しかしながら、ハニカム型触媒は強度が小さく、特にガスとの接触面が摩耗に弱いという欠点がある。また、例えば石炭焚きボイラに使用される場合、その排ガスには石炭燃焼灰等がダスト（煤塵）として数百ｍｇ／ｍ３〜数十ｇ／ｍ３含まれることも少なくない。このように多量のダストを含む排ガスをハニカム型触媒の形態のチタニア系脱硝触媒を用いて処理すると、ガスとの接触面がダストにより摩耗し、排ガス処理効率が低下したり、粉塵が排ガスとともに系外に排出されて二次公害を引き起こしたり、後流層の触媒層が閉塞したりするなどの問題を引き起こす可能性がある。 Here, by making the titania-based denitration catalyst into the form of a honeycomb-type catalyst, the surface area and pore volume of the catalyst are increased, and a highly active denitration catalyst exhibiting high performance even at low temperature and high space velocity is performed. It has been broken. However, the honeycomb type catalyst has a disadvantage that its strength is small, and particularly the contact surface with the gas is weak against abrasion. For example, when used in a coal fired boiler, the exhaust gas often contains several hundred mg / m 3 to several tens g / m 3 of coal combustion ash and the like as dust. When exhaust gas containing a large amount of dust is treated with a titania-based denitration catalyst in the form of a honeycomb-type catalyst, the contact surface with the gas is worn by dust, and the exhaust gas treatment efficiency is reduced, or dust is combined with exhaust gas. There is a possibility of causing problems such as secondary pollution caused by being discharged to the outside and clogging of the catalyst layer in the wake layer.
従来、脱硝触媒の耐摩耗性を向上させることを目的として、酸化チタン（ＴｉＯ２）と、バナジウム（Ｖ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、鉄（Ｆｅ）のうちの一種以上の元素の化合物（活性成分）とを含有する脱硝触媒において、酸化チタンに上記活性成分を加熱混練して担持したものの乾燥または仮焼粉末からなる第一成分と、含水酸化チタン粉末からなる第二成分との混練物成形体を乾燥・焼成することにより脱硝触媒を得る技術が提案されている（特許文献１を参照）。 Conventionally, for the purpose of improving the wear resistance of a denitration catalyst, one or more elements of titanium oxide (TiO 2 ) and vanadium (V), molybdenum (Mo), tungsten (W), and iron (Fe) are used. A first component comprising a dried or calcined powder and a second component comprising a hydrous titanium oxide powder, wherein the active component is supported by heating and kneading on titanium oxide. There has been proposed a technique for obtaining a denitration catalyst by drying and firing the kneaded product (see Patent Document 1).
また、酸化チタンまたは酸化チタン−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により脱硝触媒を得る技術も提案されている（特許文献２を参照）。 A magnesium sulfate aqueous solution is formed on a porous molded body containing 5 to 20 parts by weight of tungsten trioxide and 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. In addition, a technique for obtaining a denitration catalyst by impregnating and heating and firing magnesium sulfate in the range of 0.5 to 5.5 parts by weight on the porous molded body has been proposed (see Patent Document 2). ).
本発明者らが検討を行ったところ、特許文献１〜２に開示されている脱硝触媒では、ハニカム型触媒としての耐摩耗性が依然として十分ではないことが判明した。一方、耐摩耗性を向上させようとすると、場合によっては脱硝性能が低下してしまうというトレードオフが存在することも判明した。 As a result of investigations by the present inventors, it has been found that the denitration catalyst disclosed in Patent Documents 1 and 2 still does not have sufficient wear resistance as a honeycomb catalyst. On the other hand, it has also been found that there is a trade-off that if the wear resistance is improved, the denitration performance is lowered in some cases.
そこで本発明は、ハニカム型脱硝触媒において、脱硝性能の低下を最小限に抑制しつつ、耐摩耗性を向上させうる手段を提供することを目的とする。 Accordingly, an object of the present invention is to provide means for improving the wear resistance of a honeycomb type denitration catalyst while minimizing a decrease in the denitration performance.
本発明者らは、上記課題を解決すべく鋭意検討を行った。その結果、所定の酸化物と、所定の活性成分と、無機繊維と、水と、を含む触媒ペースト前駆体を混練して得られた触媒ペーストをハニカム状に成型し、焼成してハニカム型脱硝触媒を製造する際に、前記酸化物として、硫黄化合物の含有量が所定の範囲内の値に制御された硫黄原子換算で１．５〜３．５質量％であるものを用い、得られる触媒における前記無機繊維の含有量を１４〜２０質量％とし、かつ、前記混練を２段階以上で行い、前記無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加することで上記課題が解決されうることを見出し、本発明を完成させるに至った。 The present inventors have intensively studied to solve the above problems. As a result, a catalyst paste obtained by kneading a catalyst paste precursor containing a predetermined oxide, a predetermined active component, inorganic fibers, and water is formed into a honeycomb shape and fired to form a honeycomb-type denitration catalyst. When producing a catalyst, a catalyst obtained by using, as the oxide, 1.5 to 3.5% by mass in terms of sulfur atom in which the content of the sulfur compound is controlled to a value within a predetermined range. The content of the inorganic fiber in is 14 to 20% by mass, the kneading is performed in two or more stages, and the inorganic fiber is added in two or more stages so as to correspond to the kneading in two or more stages. Thus, the inventors have found that the above problems can be solved, and completed the present invention.
すなわち、本発明の一形態によれば、チタン酸化物、チタン−ケイ素の混合酸化物および／または複合酸化物、チタン−タングステンの混合酸化物および／または複合酸化物、並びにチタン−ケイ素−タングステンの混合酸化物および／または複合酸化物からなる群から選択される酸化物と、バナジウム、タングステンおよびモリブデンからなる群から選択される少なくとも１種の活性成分と、無機繊維と、水と、を含む触媒ペースト前駆体を混練して触媒ペーストを得ること、および、前記触媒ペーストをハニカム状に成型し、焼成することを含む、ハニカム型脱硝触媒の製造方法が提供される。そして、当該製造方法においては、前記酸化物に含まれる硫黄化合物の含有量が、硫黄原子換算で１．５〜３．５質量％であり、得られる触媒における前記無機繊維の含有量が、１４〜２０質量％であり、前記混練を２段階以上で行い、前記無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加する点に特徴がある。 That is, according to one aspect of the present invention, titanium oxide, titanium-silicon mixed oxide and / or composite oxide, titanium-tungsten mixed oxide and / or composite oxide, and titanium-silicon-tungsten A catalyst comprising an oxide selected from the group consisting of mixed oxides and / or composite oxides, at least one active ingredient selected from the group consisting of vanadium, tungsten and molybdenum, inorganic fibers, and water. There is provided a method for producing a honeycomb-type denitration catalyst, comprising kneading a paste precursor to obtain a catalyst paste, and molding and firing the catalyst paste into a honeycomb shape. And in the said manufacturing method, content of the sulfur compound contained in the said oxide is 1.5-3.5 mass% in conversion of a sulfur atom, and content of the said inorganic fiber in the catalyst obtained is 14 ˜20% by mass, characterized in that the kneading is performed in two or more stages, and the inorganic fibers are added in two or more stages so as to correspond to the kneading in two or more stages.
本発明によれば、脱硝性能の低下を最小限に抑制しつつ、耐摩耗性が向上したハニカム型脱硝触媒が提供されうる。 ADVANTAGE OF THE INVENTION According to this invention, the honeycomb type denitration catalyst which improved abrasion resistance can be provided, suppressing the fall of denitration performance to the minimum.
以下、図面を参照しながら、本発明を実施するための具体的な形態について詳細に説明するが、本発明の技術的範囲は特許請求の範囲の記載に基づいて定められるべきであり、下記の形態のみには限定されない。 Hereinafter, specific embodiments for carrying out the present invention will be described in detail with reference to the drawings. The technical scope of the present invention should be determined based on the description of the claims, and It is not limited only to the form.
本発明の一形態によれば、チタン酸化物、チタン−ケイ素の混合酸化物および／または複合酸化物、チタン−タングステンの混合酸化物および／または複合酸化物、並びにチタン−ケイ素−タングステンの混合酸化物および／または複合酸化物からなる群から選択される酸化物と、バナジウム、タングステンおよびモリブデンからなる群から選択される少なくとも１種の活性成分と、無機繊維と、水と、を含む触媒ペースト前駆体を混練して触媒ペーストを得ること（以下、「工程（１）」とも称する）、および、前記触媒ペーストをハニカム状に成型し、焼成すること（以下、「工程（２）」とも称する）を含む、ハニカム型脱硝触媒の製造方法であって、前記酸化物に含まれる硫黄化合物の含有量が、硫黄原子換算で１．５〜３．５質量％であり、得られる触媒における前記無機繊維の含有量が、１４〜２０質量％であり、前記混練を２段階以上で行い、前記無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加することを特徴とする、ハニカム型脱硝触媒の製造方法が提供される。 According to one aspect of the present invention, titanium oxide, titanium-silicon mixed oxide and / or composite oxide, titanium-tungsten mixed oxide and / or composite oxide, and titanium-silicon-tungsten mixed oxidation Catalyst paste precursor comprising: an oxide selected from the group consisting of oxides and / or composite oxides; at least one active ingredient selected from the group consisting of vanadium, tungsten and molybdenum; inorganic fibers; and water. The body is kneaded to obtain a catalyst paste (hereinafter also referred to as “step (1)”), and the catalyst paste is formed into a honeycomb and fired (hereinafter also referred to as “step (2)”). A method for producing a honeycomb-type denitration catalyst, wherein the content of the sulfur compound contained in the oxide is 1.5 to 3.5 mass in terms of sulfur atom The content of the inorganic fiber in the obtained catalyst is 14 to 20% by mass, the kneading is performed in two or more stages, and the inorganic fiber is mixed in two or more stages so as to correspond to two or more stages of kneading. A method for producing a honeycomb-type denitration catalyst, characterized by being added in portions, is provided.
［工程（１）］
工程（１）は、所定の原料を含む触媒ペースト前駆体を得た後、これを混練して触媒ペーストを得る工程である。
[Step (1)]
Step (1) is a step of obtaining a catalyst paste by kneading this after obtaining a catalyst paste precursor containing a predetermined raw material.
（触媒ペースト前駆体）
触媒ペースト前駆体は、所定の酸化物、所定の活性成分、無機繊維、および水を必須に含み、必要に応じて、バインダなどの添加剤をさらに含んでもよい。
(Catalyst paste precursor)
The catalyst paste precursor essentially includes a predetermined oxide, a predetermined active component, inorganic fibers, and water, and may further include an additive such as a binder as necessary.
・酸化物
触媒ペースト前駆体に含まれる所定の酸化物は、以下のものからなる群から選択される酸化物である：
チタン酸化物（ＴｉＯ２）；
チタン−ケイ素の混合酸化物（ＴｉＯ２とＳｉＯ２との混合物）；
チタン−ケイ素の複合酸化物（ＴｉＯ２−ＳｉＯ２複合酸化物（「ＴＳ複合酸化物」とも称する））；
チタン−タングステンの複合酸化物（ＴｉＯ２−ＷＯ３複合酸化物（「ＴＷ複合酸化物」とも称する））；
チタン−タングステンの混合酸化物（ＴｉＯ２とＷＯ３との混合物）；
チタン−ケイ素−タングステンの複合酸化物（ＴｉＯ２−ＳｉＯ２−ＷＯ３複合酸化物（「ＴＳＷ複合酸化物」とも称する））；
チタン−ケイ素−タングステンの混合酸化物（ＴｉＯ２とＳｉＯ２とＷＯ３との混合物、ＴＳ複合酸化物またはＴＳＷ複合酸化物とＷＯ３との混合物、ＴＷ複合酸化物またはＴＳＷ複合酸化物とＳｉＯ２との混合物、ＴＳ複合酸化物とＴＷ複合酸化物（さらに必要に応じてＳｉＯ２および／またはＷＯ３）との混合物、）。
Oxide The predetermined oxide contained in the catalyst paste precursor is an oxide selected from the group consisting of:
Titanium oxide (TiO 2 );
Titanium-silicon mixed oxide (a mixture of TiO 2 and SiO 2 );
Titanium-silicon composite oxide (TiO 2 —SiO 2 composite oxide (also referred to as “TS composite oxide”));
Titanium-tungsten composite oxide (TiO 2 —WO 3 composite oxide (also referred to as “TW composite oxide”));
Titanium-tungsten mixed oxide (mixture of TiO 2 and WO 3 );
Titanium-silicon-tungsten composite oxide (TiO 2 —SiO 2 —WO 3 composite oxide (also referred to as “TSW composite oxide”));
Titanium-silicon-tungsten mixed oxide (a mixture of TiO 2 , SiO 2 and WO 3 , a TS composite oxide or a mixture of a TSW composite oxide and WO 3 , a TW composite oxide or a TSW composite oxide and SiO 2 A mixture of TS composite oxide and TW composite oxide (and a mixture of SiO 2 and / or WO 3 if necessary)).
本形態に係る脱硝触媒およびその製造方法において、上記所定の酸化物は、ケイ素の酸化物（ＳｉＯ２）を含むものであることが、脱硝性能および耐摩耗性の両立の観点からはより好ましい。すなわち、上記所定の酸化物は、チタン−ケイ素の混合酸化物および／または複合酸化物、並びにチタン−ケイ素−タングステンの混合酸化物および／または複合酸化物からなる群から選択されることが好ましい。 In the denitration catalyst and the production method thereof according to this embodiment, it is more preferable that the predetermined oxide contains silicon oxide (SiO 2 ) from the viewpoint of achieving both denitration performance and wear resistance. That is, the predetermined oxide is preferably selected from the group consisting of a titanium-silicon mixed oxide and / or composite oxide and a titanium-silicon-tungsten mixed oxide and / or composite oxide.
なお、上記所定の酸化物はチタン酸化物（ＴｉＯ２）を必須成分として含むものであるが、上記所定の酸化物がチタン酸化物（ＴｉＯ２）以外の成分をも含む場合、上記所定の酸化物におけるチタン酸化物（ＴｉＯ２）の含有割合は、酸化物換算で好ましくは７０〜９９．９質量％であり、より好ましくは８０〜９９．５質量％である。 The predetermined oxide includes titanium oxide (TiO 2 ) as an essential component. However, when the predetermined oxide includes components other than titanium oxide (TiO 2 ), The content of titanium oxide (TiO 2 ) is preferably 70 to 99.9% by mass in terms of oxide, and more preferably 80 to 99.5% by mass.
本形態に係る脱硝触媒およびその製造方法では、触媒ペースト前駆体（および触媒ペースト）に含まれる上記所定の酸化物が、所定量の硫黄化合物を含有する点に特徴がある。すなわち、本形態に係る脱硝触媒およびその製造方法において、上記所定の酸化物における硫黄化合物の含有量は、硫黄原子換算で１．５〜３．５質量％であることが必須であり、好ましくは２．０〜３．５質量％である。上記所定の酸化物における硫黄化合物の含有量が１．５質量％未満であると、触媒の脱硝性能および耐摩耗性が悪化してしまうという問題がある。一方、上記硫黄化合物の含有量が３．５質量％を超えると、触媒製造時の焼成工程段階で硫黄化合物が大気に多量に放出するため、高価な後処理装置の設置が必要となる場合がある。ここで、上記所定の酸化物に含まれる硫黄化合物の具体的な形態について特に制限はなく、当該硫黄原子は、例えば、硫酸チタン、硫化タングステン、硫酸アンモニウム等といった硫黄化合物の形態で上記酸化物中に存在しうる。なお、上記所定の酸化物における硫黄化合物の含有量の値としては、後述する実施例の欄に記載の手法を用いて得られた値を採用するものとする。 The denitration catalyst and the manufacturing method thereof according to this embodiment are characterized in that the predetermined oxide contained in the catalyst paste precursor (and the catalyst paste) contains a predetermined amount of a sulfur compound. That is, in the denitration catalyst according to the present embodiment and the manufacturing method thereof, the content of the sulfur compound in the predetermined oxide is essential to be 1.5 to 3.5% by mass in terms of sulfur atom, preferably It is 2.0-3.5 mass%. There exists a problem that the denitration performance and abrasion resistance of a catalyst will deteriorate that content of the sulfur compound in the said predetermined oxide is less than 1.5 mass%. On the other hand, if the content of the sulfur compound exceeds 3.5% by mass, a large amount of sulfur compound is released into the atmosphere at the stage of the calcination process at the time of producing the catalyst, so that it may be necessary to install an expensive aftertreatment device. is there. Here, the specific form of the sulfur compound contained in the predetermined oxide is not particularly limited, and the sulfur atom is contained in the oxide in the form of a sulfur compound such as titanium sulfate, tungsten sulfide, ammonium sulfate, or the like. Can exist. In addition, as a value of the content of the sulfur compound in the predetermined oxide, a value obtained by using the method described in the column of Examples described later is adopted.
上記所定の酸化物の平均粒子径は、好ましくは０．５〜５０μｍであり、より好ましくは１〜５０μｍであり、さらに好ましくは１〜４０μｍである。当該酸化物の平均粒子径が０．５〜５０μｍであれば、触媒が持つ細孔容積の細孔径０．１〜１０μｍの範囲のマクロ細孔を形成しやすくなって脱硝活性を向上できる。また、上記の酸化物および活性成分の原料である塩類等を混合する際に添加する水分量を適正な範囲に制御することができ、媒強度および摩耗強度を向上できるという利点がある。なお、当該酸化物の平均粒子径の値は、粒子径分布測定装置という装置を用い、レーザー回折散乱法という方法によって測定された値を採用するものとする。また、当該酸化物のＢＥＴ比表面積は、好ましくは７０〜２５０ｍ２／ｇであり、より好ましくは８０〜２００ｍ２であり、さらに好ましくは９０〜１８０ｍ２／ｇである。当該酸化物のＢＥＴ比表面積が７０〜２５０ｍ２／ｇであれば、酸化物および活性成分の原料である塩類等を混合する際に添加する水分量を適正な範囲に制御することができ、触媒強度および摩耗強度を向上できるという利点がある。 The average particle diameter of the predetermined oxide is preferably 0.5 to 50 μm, more preferably 1 to 50 μm, and further preferably 1 to 40 μm. When the average particle diameter of the oxide is 0.5 to 50 μm, it is easy to form macropores in the pore diameter range of 0.1 to 10 μm of the pore volume of the catalyst, and the denitration activity can be improved. Further, there is an advantage that the amount of water added when mixing the above-mentioned oxides and salts as raw materials of the active ingredient can be controlled within an appropriate range, and the medium strength and wear strength can be improved. In addition, the value measured by the method called laser diffraction scattering method shall be employ | adopted for the value of the average particle diameter of the said oxide using the apparatus called a particle diameter distribution measuring apparatus. The BET specific surface area of the oxide is preferably 70 to 250 m 2 / g, more preferably 80 to 200 m 2 , and still more preferably 90 to 180 m 2 / g. When the oxide has a BET specific surface area of 70 to 250 m 2 / g, the amount of water added when the oxide and salts as raw materials of the active ingredient are mixed can be controlled within an appropriate range, and the catalyst There is an advantage that strength and wear strength can be improved.
上記所定の酸化物としては、市販品を購入したものを用いてもよいし、自ら調製したものを用いてもよい。上記所定酸化物のなかでも複合酸化物を自ら調製する方法としては、例えば、共沈法が挙げられる（後述する実施例８〜９を参照）。共沈法によって複合酸化物を得る方法自体は従来公知であり、公知の知見が適宜参照されうる。共沈法によって調製された複合酸化物は比表面積が高いなどの優れた特性を有しており、触媒性能も高くなることから、より好適に用いられる。この際、チタンの原料としては、塩化チタン、硫酸チタン、四塩化チタン、硫酸チタニル、テトライソプロピルチタネートが挙げられ、ケイ素の原料としては、シリカゾル、水ガラス、四塩化ケイ素が挙げられ、タングステンの原料としては、三酸化タングステン、タングステン酸、メタタングステン酸アンモニウム、パラタングステン酸アンモニウムが挙げられる。 As the predetermined oxide, a commercially available product may be used, or a product prepared by itself may be used. Among the predetermined oxides, a method for preparing a composite oxide by itself includes, for example, a coprecipitation method (see Examples 8 to 9 described later). The method itself for obtaining a complex oxide by the coprecipitation method is conventionally known, and known knowledge can be referred to as appropriate. The composite oxide prepared by the coprecipitation method has excellent characteristics such as a high specific surface area, and the catalyst performance is also improved, so that it is more preferably used. At this time, titanium raw materials include titanium chloride, titanium sulfate, titanium tetrachloride, titanyl sulfate, and tetraisopropyl titanate, and silicon raw materials include silica sol, water glass, and silicon tetrachloride, and tungsten raw materials. Examples thereof include tungsten trioxide, tungstic acid, ammonium metatungstate, and ammonium paratungstate.
・活性成分
本形態に係る脱硝触媒およびその製造方法において、触媒ペースト前駆体は、活性成分を含む。この活性成分は、バナジウム、タングステンおよびモリブデンからなる群から選択される少なくとも１種を必須に含有する。これらの活性成分は通常、当該成分を含む化合物またはその溶液（例えば、水溶液）の形態で供給されて、触媒ペースト前駆体中に導入される。上記活性成分の原料（化合物）としては、例えば、バナジウム原料として五酸化バナジウム、メタバナジン酸アンモニウム、硫酸バナジル、シュウ酸バナジル；タングステン原料として上記と同様の三酸化タングステン、タングステン酸、メタタングステン酸アンモニウム、パラタングステン酸アンモニウム；モリブデン原料として三酸化モリブデン、モリブデン酸、パラモリブデン酸アンモニウムが挙げられる。
-Active component In the denitration catalyst and its manufacturing method which concern on this form, a catalyst paste precursor contains an active component. This active ingredient essentially contains at least one selected from the group consisting of vanadium, tungsten and molybdenum. These active components are usually supplied in the form of a compound containing the component or a solution thereof (for example, an aqueous solution) and introduced into the catalyst paste precursor. As the raw material (compound) of the active ingredient, for example, vanadium pentoxide, ammonium metavanadate, vanadyl sulfate, vanadyl oxalate as a vanadium raw material; tungsten trioxide, tungstic acid, ammonium metatungstate similar to the above as a tungsten raw material Ammonium paratungstate; examples of molybdenum raw materials include molybdenum trioxide, molybdic acid, and ammonium paramolybdate.
なお、上述した活性成分以外の活性成分が含まれてもよく、例えば、ケイ素、アルミニウム、ジルコニウムなどが含まれてもよい。また、これらの原料としては、ケイ素原料として上記と同様のシリカゾル、水ガラス、四塩化ケイ素；アルミニウム原料としてアルミナ、ベーマイト、硝酸アルミニウム、シュウ酸アルミニウム、硫酸アルミニウム；ジルコニウム原料として酸化ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、オキシ塩化ジルコニウムが挙げられる。 Note that active ingredients other than the active ingredients described above may be included, and for example, silicon, aluminum, zirconium, and the like may be included. In addition, as these raw materials, the same silica sol, water glass, and silicon tetrachloride as above as silicon raw materials; alumina, boehmite, aluminum nitrate, aluminum oxalate, aluminum sulfate as aluminum raw materials; zirconium oxide, zirconium nitrate, as zirconium raw materials, Examples include zirconium sulfate and zirconium oxychloride.
・無機繊維
本形態に係る脱硝触媒およびその製造方法において、触媒ペースト前駆体は、無機繊維を含む。この無機繊維は、得られる触媒の強度を向上させるための強化用部材として添加されるものである。この目的で用いられる無機繊維の具体的な形態について特に制限はないが、無機繊維としては、例えば、グラスウール等のガラス繊維、ロックウール、セラミック繊維、炭素繊維などが用いられうる。繊維長さは３〜１０ｍｍ、繊維径は３〜１５μｍの範囲のものが好ましい。
-Inorganic fiber In the denitration catalyst which concerns on this form, and its manufacturing method, a catalyst paste precursor contains an inorganic fiber. This inorganic fiber is added as a reinforcing member for improving the strength of the obtained catalyst. Although there is no restriction | limiting in particular about the specific form of the inorganic fiber used for this purpose, For example, glass fiber, such as glass wool, rock wool, ceramic fiber, carbon fiber, etc. can be used as inorganic fiber. The fiber length is preferably 3 to 10 mm, and the fiber diameter is preferably 3 to 15 μm.
本形態に係る脱硝触媒およびその製造方法では、得られる触媒における無機繊維の含有量にも特徴がある。すなわち、本形態に係る脱硝触媒およびその製造方法において、得られる脱硝触媒における無機繊維の含有量は、１４〜２０質量％であることが必須であり、好ましくは１６〜２０質量％である。得られる脱硝触媒における無機繊維の含有量が１４質量％未満であると、触媒の耐摩耗性が悪化してしまうという問題がある。一方、上記無機繊維の含有量が２０質量％を超えると、触媒の脱硝性能が悪化してしまうという問題がある。 The denitration catalyst and the production method thereof according to this embodiment are also characterized by the content of inorganic fibers in the obtained catalyst. That is, in the denitration catalyst and the production method thereof according to the present embodiment, the content of inorganic fibers in the obtained denitration catalyst is essential to be 14 to 20% by mass, and preferably 16 to 20% by mass. There exists a problem that the abrasion resistance of a catalyst will deteriorate that content of the inorganic fiber in the denitration catalyst obtained is less than 14 mass%. On the other hand, when the content of the inorganic fiber exceeds 20% by mass, there is a problem that the denitration performance of the catalyst is deteriorated.
・水
本形態に係る脱硝触媒およびその製造方法において、触媒ペースト前駆体は、水を含む。この水は、上述した活性成分を触媒ペースト前駆体に導入する際の溶液の溶媒として導入される場合のほか、水のみの形態で別途添加されることにより導入される場合がある。
-Water In the denitration catalyst and the method for producing the same according to the present embodiment, the catalyst paste precursor contains water. In addition to the case where the water is introduced as a solvent of the solution when the active ingredient described above is introduced into the catalyst paste precursor, this water may be introduced by being added separately in the form of water alone.
本形態に係る脱硝触媒およびその製造方法において、触媒ペースト前駆体に含まれる水の含有量は、上述した所定の酸化物の質量当たり好ましくは４５０〜７００ｇ／ｋｇであり、より好ましくは５００〜６５０ｇ／ｋｇである。この水の量が上述の範囲内の値であれば、脱硝性能と耐摩耗性とが十分に両立されうる。 In the denitration catalyst and the production method thereof according to this embodiment, the content of water contained in the catalyst paste precursor is preferably 450 to 700 g / kg, more preferably 500 to 650 g per mass of the predetermined oxide described above. / Kg. If the amount of water is a value within the above range, the denitration performance and the wear resistance can be sufficiently achieved.
・添加剤
触媒ペースト前駆体は、必要に応じて、上述した成分以外の添加剤を含みうる。かような添加剤としては、例えば、グラスウール等の無機繊維からなる強化用部材や、シリカゾル、澱粉、ポリビニルアルコール、メトロース（セルロース系増粘剤、信越化学工業株式会社の商品名やカルボキシルセルロース等）等からなる成型助剤（バインダ）が挙げられる。これらの添加剤の種類および添加剤の添加量について特に制限はなく、本発明の作用効果を損ねない範囲で、従来公知の知見を参照しつつ適宜決定されうる。
-Additive The catalyst paste precursor may contain additives other than the above-described components as necessary. Examples of such additives include reinforcing members made of inorganic fibers such as glass wool, silica sol, starch, polyvinyl alcohol, and metrose (cellulose thickener, trade name of Shin-Etsu Chemical Co., Ltd., carboxyl cellulose, etc.) And the like. There is no restriction | limiting in particular about the kind of these additives, and the addition amount of an additive, In the range which does not impair the effect of this invention, it can determine suitably, referring a conventionally well-known knowledge.
（混練工程）
工程（１）は、上記で得られた触媒ペースト前駆体を混練する工程（混練工程）を含む。触媒ペースト前駆体は、混練工程を経ることで粘度が調整されて組成も均一化されて触媒ペーストとなり、後述の工程（２）において使用される。
(Kneading process)
Step (1) includes a step of kneading the catalyst paste precursor obtained above (kneading step). The viscosity of the catalyst paste precursor is adjusted through the kneading step, the composition is made uniform, and becomes a catalyst paste, which is used in step (2) described later.
混練工程の詳細について特に制限はなく、触媒ペースト前駆体の粘度、硬度を後述する成型に適した値に制御することができ、かつ、組成物の組成を均一化することが可能な手段であれば、従来公知の任意の手段が採用されうる。例えば、双軸式ニーダー、コンティニュアスニーダー、双腕型ニーダー、連続スクリュー式ニーダー、加圧型ニーダー、多羽根式ニーダー、混合機（パグミキサー、リボンミキサー）などが用いられる。 There are no particular restrictions on the details of the kneading step, and any means that can control the viscosity and hardness of the catalyst paste precursor to values suitable for molding, which will be described later, and can make the composition uniform. For example, any conventionally known means can be employed. For example, a twin-screw kneader, a continuous kneader, a double-arm kneader, a continuous screw kneader, a pressure kneader, a multi-blade kneader, a mixer (pug mixer, ribbon mixer) or the like is used.
本発明に係る脱硝触媒の製造方法において、混練工程は、２段階以上の多段階（例えば、２段階）で行われる。ここで、「混練工程が多段階で行われる」とは、条件の異なる混練、混合操作を続けて行うことを意味する。この際、「異なる条件」としては、混練工程の際の混練強度、温度、装置の種類、装置の回転速度、装置内圧力、処理量、時間の１つまたは２つ以上が挙げられるが、特に好ましいのは、異なる装置を用いて多段階（好ましくは２段階）の混練、混合操作を行うことである。例えば２段階での混練処理を例に挙げると、１段階目の混練工程に用いる第１の混練装置としては、比較的混練強度の大きい、いわゆる混練機が好ましい。混練機としては、例えば、加圧型ニーダー、双軸式ニーダー、コンティニュアスニーダー、連続スクリュー式ニーダーのうち１機種を用いることが好ましい。また、２段階目の混練工程に用いる第２の混練装置としては、比較的混練強度の小さい、いわゆる混合機が好ましい。混合機としては、パグミキサー、リボンミキサー、双腕型ニーダー、多羽根式ニーダーのうち１機種を用いることが好ましい。混練機と混合機を併用する好ましい実施形態について説明したが、混練機と混合機とを併用することが好ましく、上述したように混練機を先に用い、混合機をその後の工程で用いることがより好ましい。言い換えれば、混練工程の途中で混練強度を弱めるように変化させることが好ましく、混練機→混合機のように装置の種類を変更することによってかような混練強度の変化を達成することがより好ましい。このような構成とすることで、触媒ペースト前駆体の粘度、硬度を成型に適した値に制御し、組成物の組成を均一化することが確実に行われうるという利点がある。これは、混練強度が大きいと混練対象物をしっかりと強く練ることができ、目的とする練物の粘度、硬度を得ることができる。一方で、この工程でしっかりと強く練ると、添加した無機繊維が破壊される結果、もとの繊維長さを維持することができない可能性もある。このため、混練強度のより大きい混練の後、混練強度のより小さい混練の前に無機繊維を添加する工程を含むことがより好ましい。これにより、触媒の摩耗強度をよりいっそう向上させることができる。 In the method for producing a denitration catalyst according to the present invention, the kneading step is performed in two or more stages (for example, two stages). Here, “the kneading step is performed in multiple stages” means that kneading and mixing operations under different conditions are continuously performed. In this case, “different conditions” include one or two or more of kneading strength, temperature, type of apparatus, apparatus rotation speed, apparatus internal pressure, throughput, and time during the kneading process. Preference is given to performing kneading and mixing operations in multiple stages (preferably two stages) using different apparatuses. For example, taking a two-stage kneading process as an example, the first kneading apparatus used in the first-stage kneading process is preferably a so-called kneader having a relatively high kneading strength. As the kneader, for example, one of a pressure type kneader, a twin-axis kneader, a continuous kneader, and a continuous screw kneader is preferably used. Further, as the second kneading apparatus used in the second stage kneading step, a so-called mixer having relatively low kneading strength is preferable. As the mixer, it is preferable to use one of a pug mixer, a ribbon mixer, a double-arm kneader, and a multi-blade kneader. Although a preferred embodiment in which a kneader and a mixer are used together has been described, it is preferable to use a kneader and a mixer together, as described above, using the kneader first, and using the mixer in the subsequent steps. More preferred. In other words, it is preferable to change so as to weaken the kneading strength in the middle of the kneading step, and it is more preferable to achieve such a change in kneading strength by changing the type of the apparatus such as a kneader → mixer. . By adopting such a configuration, there is an advantage that the viscosity and hardness of the catalyst paste precursor can be controlled to values suitable for molding and the composition can be made uniform. If the kneading strength is high, the object to be kneaded can be kneaded firmly and strongly, and the desired viscosity and hardness of the kneaded material can be obtained. On the other hand, if kneaded firmly and strongly in this step, the added inorganic fiber may be destroyed, so that the original fiber length may not be maintained. For this reason, it is more preferable to include a step of adding inorganic fibers after kneading with higher kneading strength and before kneading with lower kneading strength. Thereby, the abrasion strength of the catalyst can be further improved.
そして、本形態に係る脱硝触媒およびその製造方法における混練工程での上記詳細をさらに説明する。本発明では、上述した無機繊維の添加形態に最大の特徴がある。すなわち、上述したように混練工程では混練を２段階以上で行うが、この際、無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加する点に特徴を有しているのである。ここで、「無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加する」とは、２段階以上の混練（上記で定義したように条件の異なる２つ以上の混練操作をつづけて行うこと）の各混練操作の開始前に、混練の段階の数と同じ数に分割しておいた所望の量の無機繊維を触媒ペーストの混合物中に添加することを意味する。例えば、混練を２段階で行うのであれば、得られる触媒に含まれる所望の量の無機繊維を２つに分割しておき、分割された無機繊維を２段階の各混練操作の開始前にそれぞれ触媒ペーストの混合物中に添加すればよい。なお、最初の混練操作の時点で添加されている無機繊維は、最初の混練操作の開始前に触媒ペーストの混合物中に含まれていれば、その添加のタイミングについて特に制限はない。また、無機繊維を分割する際には、均一な組成の触媒ペーストを得るという観点からは、等分に近いように分割するほど好ましいが、厳密に等分に分ける必要はなく、ｎ段階の混練操作に対応するように無機繊維をｎ個に分割する場合の好ましい実施形態として、例えば、添加する無機繊維の全量を１００質量％としたときに、分割後のそれぞれの無機繊維の質量が１００／ｎ±１０（％）の範囲に含まれていることが好ましく、１００／ｎ±５（％）の範囲に含まれていることがより好ましい。また、上述したように、得られる脱硝触媒における無機繊維の含有量は１４〜２０質量％であることが必須であるが、他の好ましい実施形態においては、混練を２段階で行い、無機繊維を２段階の混練に対応するように２段階に分割して添加し、この際、それぞれの混練段階における前記無機繊維の添加量を、得られる触媒の質量の８〜１０質量％とする。かような構成とすることで、特に脱硝性能および耐摩耗性に優れた脱硝触媒が提供されうる。 And the said detail in the kneading | mixing process in the denitration catalyst which concerns on this form, and its manufacturing method is further demonstrated. In this invention, there exists the biggest characteristic in the addition form of the inorganic fiber mentioned above. That is, as described above, in the kneading step, kneading is performed in two or more stages. At this time, the inorganic fiber is added in two or more stages so as to correspond to two or more stages of kneading. It is. Here, “adding inorganic fibers in two or more stages so as to correspond to two or more stages of kneading” means two or more stages of kneading (two or more kneading under different conditions as defined above) This means that before the start of each kneading operation, a desired amount of inorganic fibers divided into the same number of kneading stages is added to the catalyst paste mixture. For example, if kneading is performed in two stages, a desired amount of inorganic fibers contained in the obtained catalyst is divided into two, and the divided inorganic fibers are respectively separated before the start of each kneading operation in two stages. What is necessary is just to add in the mixture of a catalyst paste. In addition, if the inorganic fiber added at the time of the first kneading operation is contained in the mixture of the catalyst paste before the start of the first kneading operation, the timing of the addition is not particularly limited. Further, when dividing the inorganic fibers, from the viewpoint of obtaining a catalyst paste having a uniform composition, it is preferable to divide the fibers so that they are close to equal parts. As a preferred embodiment when dividing the inorganic fiber into n so as to correspond to the operation, for example, when the total amount of the inorganic fiber to be added is 100% by mass, the mass of each inorganic fiber after the division is 100 / It is preferably included in the range of n ± 10 (%), and more preferably in the range of 100 / n ± 5 (%). In addition, as described above, it is essential that the content of the inorganic fiber in the obtained denitration catalyst is 14 to 20% by mass. In another preferred embodiment, kneading is performed in two stages, and the inorganic fiber It is added in two stages so as to correspond to the two-stage kneading. At this time, the amount of the inorganic fiber added in each kneading stage is 8 to 10% by mass of the mass of the obtained catalyst. By adopting such a configuration, it is possible to provide a denitration catalyst that is particularly excellent in denitration performance and wear resistance.
上述した混練工程を経て、工程（１）では触媒ペーストが得られるが、この触媒ペーストの硬度（土壌硬度計にて測定）は、好ましくは２０ｍｍ以上であり、より好ましくは２２ｍｍ以上である。この触媒ペーストの支持力強度は、好ましくは６．３ｋｇ／ｃｍ２以上、より好ましくは８．５ｋｇ／ｃｍ２以上である。 Through the kneading step described above, a catalyst paste is obtained in step (1). The hardness of the catalyst paste (measured with a soil hardness meter) is preferably 20 mm or more, and more preferably 22 mm or more. The support strength of the catalyst paste is preferably 6.3 kg / cm 2 or more, more preferably 8.5 kg / cm 2 or more.
［工程（２）］
工程（２）は、工程（１）において得られた触媒ペーストをハニカム状に成型し、焼成する工程である。これにより、ハニカム型脱硝触媒が得られる。
[Step (2)]
Step (2) is a step in which the catalyst paste obtained in step (1) is formed into a honeycomb and fired. Thereby, a honeycomb type denitration catalyst is obtained.
成型工程の詳細についても特に制限はなく、従来公知の任意の手段が採用されうる。例えば、押出し成形機を用いてハニカム状に成型すればよい。 The details of the molding process are not particularly limited, and any conventionally known means can be employed. For example, it may be formed into a honeycomb shape using an extrusion molding machine.
得られた成型体については、その後、５０〜１２０℃程度の温度でよく乾燥する。次いで、３００〜７５０℃程度、好ましくは４００〜６５０℃、より好ましくは４９０〜５２０℃の温度で、１〜１０時間、好ましくは３〜１０時間焼成する。これにより、ハニカム状脱硝触媒を得ることができる。 The resulting molded body is then well dried at a temperature of about 50 to 120 ° C. Next, baking is performed at a temperature of about 300 to 750 ° C., preferably 400 to 650 ° C., more preferably 490 to 520 ° C. for 1 to 10 hours, preferably 3 to 10 hours. Thereby, a honeycomb-shaped denitration catalyst can be obtained.
得られた脱硝触媒の特性について特に制限はないが、触媒の比表面積については、８０ｍ２／ｇ以上の範囲が好ましく、８０〜２５０ｍ２／ｇの範囲がより好ましい。触媒の比表面積が８０ｍ２／ｇ以上程度あれば、十分な脱硝性能を得ることができる。 No particular limitation on the characteristics of the denitration catalyst obtained, but for the specific surface area of the catalyst, 80 m 2 / g or more ranges are preferred, and more preferably in the range of 80~250m 2 / g. If the specific surface area of the catalyst is about 80 m 2 / g or more, sufficient denitration performance can be obtained.
また、触媒の細孔容積については、全細孔容積が０．２５〜０．５ｍＬ／ｇの範囲にあるのがよく、より好ましくは０．３〜０．５ｍＬ／ｇがよい。触媒の細孔容積が０．２５ｍＬ／ｇ以上であれば十分な脱硝性能が得られ、０．５ｍＬ／ｇ以下であれば触媒の機械的強度も十分なものとなり、耐磨耗性も十分に確保されうる。 The pore volume of the catalyst is such that the total pore volume is in the range of 0.25 to 0.5 mL / g, more preferably 0.3 to 0.5 mL / g. If the pore volume of the catalyst is 0.25 mL / g or more, sufficient denitration performance is obtained, and if it is 0.5 mL / g or less, the mechanical strength of the catalyst is sufficient and the wear resistance is also sufficient. Can be secured.
本形態に係る脱硝触媒は、各種排ガスの処理に用いられる。排ガスの組成については特に制限はないが、重油焚きボイラや石炭焚きボイラ、ガスタービン、ガスエンジン、ディーゼルエンジン、火力発電所、産業廃棄物や都市廃棄物を処理する焼却施設および各種工業プロセスから排出される窒素酸化物（ＮＯｘ）の分解活性に優れるため、これら窒素酸化物を含む排ガスの処理に好適に用いられる。 The denitration catalyst according to this embodiment is used for treating various exhaust gases. There are no particular restrictions on the composition of the exhaust gas, but it is emitted from heavy oil fired boilers, coal fired boilers, gas turbines, gas engines, diesel engines, thermal power plants, incineration facilities that process industrial and municipal wastes, and various industrial processes. Therefore, it is suitably used for the treatment of exhaust gas containing these nitrogen oxides.
本形態に係る脱硝触媒を用いて窒素酸化物の除去を行うには、本形態に係る触媒をアンモニアや尿素などの還元剤の存在下、排ガスと接触させることで、排ガス中の窒素酸化物を還元除去することができる。アンモニア量は、窒素酸化物を窒素と水に分解できる当量に対して０．３〜１．５倍、好ましくは０．５〜１．２倍である。アンモニア量が窒素酸化物を窒素と水に分解できる当量に対して０．３倍以上であれば窒素酸化物の処理効率を十分に確保することができ、１．５倍以下であれば未反応のアンモニアの残存量の増大に伴う環境への悪影響を防止することができる。ここで、窒素酸化物を窒素と水に分解できる当量について、対象物質がＮＯの場合は、ＮＯ １モルに対してアンモニアは１モルであり、対象物質がＮＯ２の場合は、ＮＯ２ １モルに対してアンモニアは１．３３〜２モルである。なお、尿素をも用いる場合は、尿素はアンモニアの２倍モルとして作用するのでアンモニア量の半分のモル量となる。 In order to remove nitrogen oxides using the denitration catalyst according to this embodiment, the catalyst according to this embodiment is brought into contact with exhaust gas in the presence of a reducing agent such as ammonia or urea, so that nitrogen oxide in the exhaust gas is removed. It can be reduced and removed. The amount of ammonia is 0.3 to 1.5 times, preferably 0.5 to 1.2 times the equivalent amount capable of decomposing nitrogen oxides into nitrogen and water. If the amount of ammonia is 0.3 times or more than the equivalent amount capable of decomposing nitrogen oxides into nitrogen and water, the treatment efficiency of nitrogen oxides can be sufficiently secured, and if it is 1.5 times or less, unreacted It is possible to prevent adverse effects on the environment due to an increase in the residual amount of ammonia. Here, regarding the equivalent amount capable of decomposing nitrogen oxides into nitrogen and water, when the target substance is NO, ammonia is 1 mole with respect to 1 mole of NO, and when the target substance is NO 2 , 1 mole of NO 2 In contrast, ammonia is 1.33 to 2 mol. When urea is also used, urea acts as a double mole of ammonia, so that the mole amount is half of the ammonia amount.
本形態に係る脱硝触媒を用いて窒素酸化物の除去を行う際の条件について特に制限はなく、この種の反応に一般的に用いられている条件で実施することができる。具体的には、排ガスの種類、性状、要求される除去率などを考慮して適宜決定すればよい。 There is no particular limitation on the conditions for removing nitrogen oxides using the denitration catalyst according to the present embodiment, and the conditions can be implemented under conditions generally used for this type of reaction. Specifically, it may be determined as appropriate in consideration of the type and properties of the exhaust gas and the required removal rate.
なお、触媒入口ガス温度は１００〜６００℃の範囲であることが好ましく、より好ましくは１５０〜５００℃、さらに好ましくは２００〜４５０℃がよい。また、その際の空間速度は１００〜２０００００ｈｒ−１（ＳＴＰ）が好ましく、１０００〜１０００００ｈｒ−１（ＳＴＰ）がより好ましく、さらに好ましくは２０００〜５００００ｈｒ−１（ＳＴＰ）がよい。なお、排ガス中の窒素酸化物の濃度は、５〜５０００ｐｐｍ、好ましくは１０〜２０００ｐｐｍである。 The catalyst inlet gas temperature is preferably in the range of 100 to 600 ° C, more preferably 150 to 500 ° C, and even more preferably 200 to 450 ° C. Also, the space velocity at that time 100~200000hr -1 (STP) are preferable, 1000~100000hr -1 (STP), more preferably, more preferably 2000~50000hr -1 (STP) is good. In addition, the density | concentration of the nitrogen oxide in waste gas is 5-5000 ppm, Preferably it is 10-2000 ppm.
以下、実施例を用いて本発明の実施形態をより詳細に説明するが、本発明の技術的範囲は下記の実施例に限定して解釈されるべきではない。なお、実施例８の製造方法に対応したフロー図を図１に示す。 Hereinafter, although embodiment of this invention is described in detail using an Example, the technical scope of this invention should not be limited and limited to the following Example. In addition, the flowchart corresponding to the manufacturing method of Example 8 is shown in FIG.
＜ハニカム型触媒の製造＞
（実施例１）
所定の酸化物としてＴＳ混合酸化物を用いて、以下の手法によりハニカム型脱硝触媒を得た。
<Manufacture of honeycomb type catalyst>
Example 1
A honeycomb type denitration catalyst was obtained by the following method using TS mixed oxide as the predetermined oxide.
具体的には、まず、２Ｌの水にパラタングステン酸アンモニウム２．２３ｋｇおよびモノエタノールアミン０．９６ｋｇを混合して溶解させ、均一溶液（ａ液）を調製した。また、４Ｌの水にメタバナジン酸アンモニウム０．３４ｋｇおよびシュウ酸０．４６ｋｇを混合して溶解させ、均一溶液（ｂ液）を調製した。 Specifically, first, 2.23 kg of ammonium paratungstate and 0.96 kg of monoethanolamine were mixed and dissolved in 2 L of water to prepare a uniform solution (liquid a). Further, 0.34 kg of ammonium metavanadate and 0.46 kg of oxalic acid were mixed and dissolved in 4 L of water to prepare a uniform solution (liquid b).
一方、所定の酸化物であるＴＳ混合酸化物（硫黄化合物を硫黄原子換算で３．５質量％含むチタン−ケイ素混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２＝８８：１２（質量比）］；平均粒子径３μｍ）２０．０ｋｇを計量した。計量したＴＳ混合酸化物を混練機に投入し、この上からａ液およびｂ液を投入し、成形助剤を追加水とともに加え、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））を加えて混合して触媒ペースト前駆体を得た。この触媒ペースト前駆体を混練機内で適度な硬さになるまで混練した（第１混練工程）。その後、第１混練工程で得られた混練物を混合機へ移し、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール）を加えて、混練機よりも小さい混練強度で混練することにより、成分の均一化を促進させた（第２混練工程）。 On the other hand, TS mixed oxide which is a predetermined oxide (powder of titanium-silicon mixed oxide containing 3.5 mass% of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 = 88: 12 (mass Ratio)]; average particle size 3 μm) 20.0 kg was weighed. The weighed TS mixed oxide is put into a kneader, and the liquid a and liquid b are added from above, and the molding aid is added together with additional water, and further 8% by mass with respect to 100% by mass of the obtained catalyst. An amount of inorganic fiber (glass wool; Owens, GW (830A)) was added and mixed to obtain a catalyst paste precursor. This catalyst paste precursor was kneaded in a kneader until the hardness became appropriate (first kneading step). Thereafter, the kneaded product obtained in the first kneading step is transferred to a mixer, and an inorganic fiber (glass wool) is added in an amount of 8% by mass with respect to 100% by mass of the obtained catalyst, which is smaller than the kneader. By kneading with kneading strength, homogenization of the components was promoted (second kneading step).
第２混練工程で得られた混練物を、押出し成形機を用いて８０ｍｍ角の格子状（ハニカム状）に成型した。次いで、得られた成型体を乾燥した後、４９０℃にて５時間焼成して、ハニカム型脱硝触媒を得た。得られた触媒中のＶ２Ｏ５およびＷＯ３の含有量は、それぞれ１．０質量％および７．５質量％であった。また、得られたハニカム型脱硝触媒の貫通孔の相当直径は６ｍｍ、セル肉厚は１．０ｍｍ、比表面積は１１０ｍ２／ｇであった。なお、触媒ペースト前駆体における水の含有量（ａ液に用いた水、ｂ液に用いた水および混練時に追加した追加水の合計量）は、ＴＳ混合酸化物の質量当たり５４０ｇ／ｋｇとした。 The kneaded product obtained in the second kneading step was molded into an 80 mm square lattice (honeycomb) using an extruder. Subsequently, the obtained molded body was dried and then fired at 490 ° C. for 5 hours to obtain a honeycomb type denitration catalyst. The contents of V 2 O 5 and WO 3 in the obtained catalyst were 1.0% by mass and 7.5% by mass, respectively. Moreover, the equivalent diameter of the through-hole of the obtained honeycomb type denitration catalyst was 6 mm, the cell thickness was 1.0 mm, and the specific surface area was 110 m 2 / g. The water content in the catalyst paste precursor (the total amount of water used in the liquid a, the water used in the liquid b, and the additional water added during kneading) was 540 g / kg per mass of the TS mixed oxide. .
（実施例２）
ＴＳ混合酸化物として、硫黄化合物を硫黄原子換算で３．０質量％含むチタン−ケイ素混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２＝８８：１２（質量比）］（平均粒子径３μｍ）を用いたこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１０８ｍ２／ｇであった。
(Example 2)
As TS mixed oxide, powder of titanium-silicon mixed oxide containing 3.0% by mass of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 = 88: 12 (mass ratio)] (average particle diameter A honeycomb type denitration catalyst was obtained in the same manner as in Example 1 except that 3 μm) was used. The specific surface area of the obtained honeycomb type denitration catalyst was 108 m 2 / g.
（実施例３）
ＴＳ混合酸化物として、硫黄化合物を硫黄原子換算で２．０質量％含むチタン−ケイ素混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２＝８８：１２（質量比）］（平均粒子径３μｍ）を用いたこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１０８ｍ２／ｇであった。
(Example 3)
As TS mixed oxide, powder of titanium-silicon mixed oxide containing 2.0% by mass of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 = 88: 12 (mass ratio)] (average particle diameter A honeycomb type denitration catalyst was obtained in the same manner as in Example 1 except that 3 μm) was used. The specific surface area of the obtained honeycomb type denitration catalyst was 108 m 2 / g.
（実施例４）
ＴＳ混合酸化物として、硫黄化合物を硫黄原子換算で１．５質量％含むチタン−ケイ素混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２＝８８：１２（質量比）］（平均粒子径３μｍ）を用いたこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１０６ｍ２／ｇであった。
Example 4
As TS mixed oxide, powder of titanium-silicon mixed oxide containing 1.5% by mass of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 = 88: 12 (mass ratio)] (average particle diameter A honeycomb type denitration catalyst was obtained in the same manner as in Example 1 except that 3 μm) was used. The specific surface area of the obtained honeycomb type denitration catalyst was 106 m 2 / g.
（実施例５）
無機繊維（グラスウール）の添加量を実施例１から変更して、以下の手法によりハニカム型脱硝触媒を得た。
(Example 5)
The amount of inorganic fiber (glass wool) added was changed from that in Example 1, and a honeycomb type denitration catalyst was obtained by the following method.
具体的には、まず、２Ｌの水にパラタングステン酸アンモニウム２．３６ｋｇおよびモノエタノールアミン１．０１ｋｇを混合して溶解させ、均一溶液（ａ液）を調製した。また、４Ｌの水にメタバナジン酸アンモニウム０．３６ｋｇおよびシュウ酸０．４９ｋｇを混合して溶解させ、均一溶液（ｂ液）を調製した。 Specifically, first, 2.36 kg of ammonium paratungstate and 1.01 kg of monoethanolamine were mixed and dissolved in 2 L of water to prepare a uniform solution (liquid a). Moreover, 0.36 kg of ammonium metavanadate and 0.49 kg of oxalic acid were mixed and dissolved in 4 L of water to prepare a uniform solution (liquid b).
一方、所定の酸化物であるＴＳ混合酸化物（硫黄化合物を硫黄原子換算で３．５質量％含むチタン−ケイ素混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２＝８８：１２（質量比）］；平均粒子径３μｍ）２０．０ｋｇを計量した。計量したＴＳ混合酸化物を混練機に投入し、この上からａ液およびｂ液を投入し、成形助剤を追加水とともに加え、さらに得られる触媒の質量１００質量％に対して１０質量％の量の無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））を加えて混合して触媒ペースト前駆体を得た。この触媒ペースト前駆体を混練機内で適度な硬さになるまで混練した（第１混練工程）。その後、第１混練工程で得られた混練物を混合機へ移し、さらに得られる触媒の質量１００質量％に対して１０質量％の量の無機繊維（グラスウール）を加えて、混練機よりも小さい混練強度で混練することにより、成分の均一化を促進させた（第２混練工程）。 On the other hand, TS mixed oxide which is a predetermined oxide (powder of titanium-silicon mixed oxide containing 3.5 mass% of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 = 88: 12 (mass Ratio)]; average particle size 3 μm) 20.0 kg was weighed. The weighed TS mixed oxide is put into a kneader, the liquid a and liquid b are added from above, and the molding aid is added together with additional water, and further 10% by mass with respect to 100% by mass of the resulting catalyst. An amount of inorganic fiber (glass wool; Owens, GW (830A)) was added and mixed to obtain a catalyst paste precursor. This catalyst paste precursor was kneaded in a kneader until the hardness became appropriate (first kneading step). Thereafter, the kneaded product obtained in the first kneading step is transferred to a mixer, and further 10% by mass of inorganic fiber (glass wool) is added to the mass of the obtained catalyst of 100% by mass, which is smaller than the kneader. By kneading with kneading strength, homogenization of the components was promoted (second kneading step).
第２混練工程で得られた混練物を、押出し成形機を用いて８０ｍｍ角の格子状（ハニカム状）に成型した。次いで、得られた成型体を乾燥した後、４９０℃にて５時間焼成して、ハニカム型脱硝触媒を得た。得られた触媒中のＶ２Ｏ５およびＷＯ３の含有量は、それぞれ１．０質量％および７．５質量％であった。また、得られたハニカム型脱硝触媒の貫通孔の相当直径は６ｍｍ、セル肉厚は１．０ｍｍ、比表面積は１２５ｍ２／ｇであった。なお、触媒ペースト前駆体における水の含有量（ａ液に用いた水、ｂ液に用いた水および混練時に追加した追加水の合計量）は、ＴＳ混合酸化物の質量当たり５４０ｇ／ｋｇとした。 The kneaded product obtained in the second kneading step was molded into an 80 mm square lattice (honeycomb) using an extruder. Subsequently, the obtained molded body was dried and then fired at 490 ° C. for 5 hours to obtain a honeycomb type denitration catalyst. The contents of V 2 O 5 and WO 3 in the obtained catalyst were 1.0% by mass and 7.5% by mass, respectively. In addition, the equivalent diameter of the through hole of the obtained honeycomb type denitration catalyst was 6 mm, the cell thickness was 1.0 mm, and the specific surface area was 125 m 2 / g. The water content in the catalyst paste precursor (the total amount of water used in the liquid a, the water used in the liquid b, and the additional water added during kneading) was 540 g / kg per mass of the TS mixed oxide. .
（実施例６）
所定の酸化物としてＴＳＷ混合酸化物を用いて、以下の手法によりハニカム型脱硝触媒を得た。
(Example 6)
Using a TSW mixed oxide as the predetermined oxide, a honeycomb type denitration catalyst was obtained by the following method.
具体的には、まず、２Ｌの水にパラタングステン酸アンモニウム１．７５ｋｇおよびモノエタノールアミン０．７５ｋｇを混合して溶解させ、均一溶液（ａ液）を調製した。また、４Ｌの水にメタバナジン酸アンモニウム０．３３ｋｇおよびシュウ酸０．４５ｋｇを混合して溶解させ、均一溶液（ｂ液）を調製した。 Specifically, first, 1.75 kg of ammonium paratungstate and 0.75 kg of monoethanolamine were mixed and dissolved in 2 L of water to prepare a uniform solution (liquid a). Further, 0.33 kg of ammonium metavanadate and 0.45 kg of oxalic acid were mixed and dissolved in 4 L of water to prepare a uniform solution (liquid b).
一方、所定の酸化物であるＴＳＷ混合酸化物（硫黄化合物を硫黄原子換算で３．０質量％含むチタン−ケイ素−タングステン混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２：ＷＯ３＝９５：３：２（質量比）；平均粒子径３μｍ）２０．０ｋｇを計量した。計量したＴＳＷ混合酸化物を混練機に投入し、この上からａ液およびｂ液を投入し、成形助剤を追加水とともに加え、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））を加えて混合して触媒ペースト前駆体を得た。この触媒ペースト前駆体を混練機内で適度な硬さになるまで混練した（第１混練工程）。その後、第１混練工程で得られた混練物を混合機へ移し、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール）を加えて、混練機よりも小さい混練強度で混練することにより、成分の均一化を促進させた（第２混練工程）。 On the other hand, TSW mixed oxide which is a predetermined oxide (powder of titanium-silicon-tungsten mixed oxide containing 3.0% by mass of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 : WO 3 = 95: 3: 2 (mass ratio); average particle diameter 3 μm) 20.0 kg was weighed. The weighed TSW mixed oxide is put into a kneader, the liquid a and liquid b are added from above, the molding aid is added together with additional water, and further 8% by mass with respect to 100% by mass of the resulting catalyst. An amount of inorganic fiber (glass wool; Owens, GW (830A)) was added and mixed to obtain a catalyst paste precursor. This catalyst paste precursor was kneaded in a kneader until the hardness became appropriate (first kneading step). Thereafter, the kneaded product obtained in the first kneading step is transferred to a mixer, and an inorganic fiber (glass wool) is added in an amount of 8% by mass with respect to 100% by mass of the obtained catalyst, which is smaller than the kneader. By kneading with kneading strength, homogenization of the components was promoted (second kneading step).
第２混練工程で得られた混練物を、押出し成形機を用いて８０ｍｍ角の格子状（ハニカム状）に成型した。次いで、得られた成型体を乾燥した後、４９０℃にて５時間焼成して、ハニカム型脱硝触媒を得た。得られた触媒中のＶ２Ｏ５およびＷＯ３の含有量は、それぞれ１．０質量％および７．５質量％であった。また、得られたハニカム型脱硝触媒の貫通孔の相当直径は６ｍｍ、セル肉厚は１．０ｍｍ、比表面積は１１０ｍ２／ｇであった。なお、触媒ペースト前駆体における水の含有量（ａ液に用いた水、ｂ液に用いた水および混練時に追加した追加水の合計量）は、ＴＳ混合酸化物の質量当たり５４０ｇ／ｋｇとした。 The kneaded product obtained in the second kneading step was molded into an 80 mm square lattice (honeycomb) using an extruder. Subsequently, the obtained molded body was dried and then fired at 490 ° C. for 5 hours to obtain a honeycomb type denitration catalyst. The contents of V 2 O 5 and WO 3 in the obtained catalyst were 1.0% by mass and 7.5% by mass, respectively. Moreover, the equivalent diameter of the through-hole of the obtained honeycomb type denitration catalyst was 6 mm, the cell thickness was 1.0 mm, and the specific surface area was 110 m 2 / g. The water content in the catalyst paste precursor (the total amount of water used in the liquid a, the water used in the liquid b, and the additional water added during kneading) was 540 g / kg per mass of the TS mixed oxide. .
（実施例７）
以下の手法により、所定の酸化物であるＴＳ複合酸化物を得た後、これを用いてハニカム型脱硝触媒を得た。
(Example 7)
After obtaining a TS composite oxide as a predetermined oxide by the following method, a honeycomb type denitration catalyst was obtained using this.
［酸化物（ＴＳ複合酸化物）の調製］
具体的には、まず、所定の酸化物であるＴＳ複合酸化物（ＴｉＯ２−ＳｉＯ２の複合酸化物の粉体）を、以下に述べる方法で調製した。
[Preparation of oxide (TS composite oxide)]
Specifically, first, a TS composite oxide (TiO 2 —SiO 2 composite oxide powder) as a predetermined oxide was prepared by the method described below.
水１０００Ｌにアンモニア水（ＮＨ３＿２５％）７１５Ｌを添加し、これに３０質量％のシリカゾル溶液４４ｋｇを加えた。得られた水溶液に、硫酸チタニルの硫酸水溶液（ＴｉＯＳＯ４［ＴｉＯ２換算］２５０ｇ／Ｌ、Ｈ２ＳＯ４＿１１００ｇ／Ｌ）４０１Ｌを水８００Ｌに添加して希釈したチタン含有硫酸水溶液を撹拌下で徐々に滴下して、共沈ゲルを生成させた。さらに、そのまま４０時間放置して静置した。このようにして得られたＴｉＯ２−ＳｉＯ２ゲルを濾過し、水洗した後、乾燥し、次いで５５０℃にて５時間、空気雰囲気下で焼成して、ＴＳ複合酸化物（ＴｉＯ２−ＳｉＯ２の複合酸化物の粉体）を得た。得られたＴＳ複合酸化物の組成は、酸化物としての質量比でＴｉＯ２：ＳｉＯ２＝８８：１２であった。なお、上記ＴＳ複合酸化物に含まれる硫黄化合物の量は、硫黄原子換算で３．０質量％であった。また、当該ＴＳ複合酸化物の平均粒子径は２０μｍであった。 To 1000 L of water, 715 L of aqueous ammonia (NH 3 —25%) was added, and 44 kg of a 30% by mass silica sol solution was added thereto. To the obtained aqueous solution, a sulfuric acid aqueous solution of titanyl sulfate (TiOSO 4 [in terms of TiO 2 ] 250 g / L, H 2 SO 4 _ 1100 g / L) 401 L was added to 800 L of water, and a titanium-containing sulfuric acid aqueous solution diluted was gradually added with stirring. To form a coprecipitated gel. Furthermore, it was left to stand for 40 hours as it was. The TiO 2 —SiO 2 gel thus obtained was filtered, washed with water, dried, and then fired at 550 ° C. for 5 hours in an air atmosphere to produce a TS composite oxide (TiO 2 —SiO 2). A composite oxide powder). The composition of the obtained TS composite oxide was TiO 2 : SiO 2 = 88: 12 in terms of mass ratio as an oxide. In addition, the quantity of the sulfur compound contained in the said TS complex oxide was 3.0 mass% in conversion of the sulfur atom. The average particle size of the TS composite oxide was 20 μm.
［ハニカム型触媒の製造］
２Ｌの水にパラタングステン酸アンモニウム２．２３ｋｇおよびモノエタノールアミン０．９６ｋｇを混合して溶解させ、均一溶液（ａ液）を調製した。また、４Ｌの水にメタバナジン酸アンモニウム０．３４ｋｇおよびシュウ酸０．４６ｋｇを混合して溶解させ、均一溶液（ｂ液）を調製した。
[Manufacture of honeycomb type catalyst]
In 2 L of water, 2.23 kg of ammonium paratungstate and 0.96 kg of monoethanolamine were mixed and dissolved to prepare a uniform solution (liquid a). Further, 0.34 kg of ammonium metavanadate and 0.46 kg of oxalic acid were mixed and dissolved in 4 L of water to prepare a uniform solution (liquid b).
一方、上記で調製した所定の酸化物であるＴＳ複合酸化物（平均粒子径２０μｍ）を２０．０ｋｇ計量した。計量したＴＳ複合酸化物を混練機に投入し、この上からａ液およびｂ液を投入し、成形助剤を追加水とともに加え、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））を加えて混合して触媒ペースト前駆体を得た。この触媒ペースト前駆体を混練機内で適度な硬さになるまで混練した（第１混練工程）。その後、第１混練工程で得られた混練物を混合機へ移し、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール）を加えて、混練機よりも小さい混練強度で混練することにより、成分の均一化を促進させた（第２混練工程）。 On the other hand, 20.0 kg of TS complex oxide (average particle diameter 20 μm), which is the predetermined oxide prepared above, was weighed. The weighed TS composite oxide is put into a kneader, the liquid a and liquid b are added from above, and the molding aid is added together with additional water, and further 8% by mass with respect to 100% by mass of the resulting catalyst. An amount of inorganic fiber (glass wool; Owens, GW (830A)) was added and mixed to obtain a catalyst paste precursor. This catalyst paste precursor was kneaded in a kneader until the hardness became appropriate (first kneading step). Thereafter, the kneaded product obtained in the first kneading step is transferred to a mixer, and an inorganic fiber (glass wool) is added in an amount of 8% by mass with respect to 100% by mass of the obtained catalyst, which is smaller than the kneader. By kneading with kneading strength, homogenization of the components was promoted (second kneading step).
第２混練工程で得られた混練物を、押出し成形機を用いて８０ｍｍ角の格子状（ハニカム状）に成型した。次いで、得られた成型体を乾燥した後、４９０℃にて５時間焼成して、ハニカム型脱硝触媒を得た。得られた触媒中のＶ２Ｏ５およびＷＯ３の含有量は、それぞれ１．０質量％および７．５質量％であった。また、得られたハニカム型脱硝触媒の貫通孔の相当直径は６ｍｍ、セル肉厚は１．０ｍｍ、比表面積は１２５ｍ２／ｇであった。なお、触媒ペースト前駆体における水の含有量（ａ液に用いた水、ｂ液に用いた水および混練時に追加した追加水の合計量）は、ＴＳ複合酸化物の質量当たり５４０ｇ／ｋｇとした。 The kneaded product obtained in the second kneading step was molded into an 80 mm square lattice (honeycomb) using an extruder. Subsequently, the obtained molded body was dried and then fired at 490 ° C. for 5 hours to obtain a honeycomb type denitration catalyst. The contents of V 2 O 5 and WO 3 in the obtained catalyst were 1.0% by mass and 7.5% by mass, respectively. In addition, the equivalent diameter of the through hole of the obtained honeycomb type denitration catalyst was 6 mm, the cell thickness was 1.0 mm, and the specific surface area was 125 m 2 / g. The water content in the catalyst paste precursor (the total amount of water used in the liquid a, the water used in the liquid b, and the additional water added during kneading) was 540 g / kg per mass of the TS composite oxide. .
（実施例８）
以下の手法により、所定の酸化物であるＴＳＷ複合酸化物を得た後、これを用いてハニカム型脱硝触媒を得た。
(Example 8)
After obtaining a TSW composite oxide as a predetermined oxide by the following method, a honeycomb type denitration catalyst was obtained using this.
［酸化物（ＴＳＷ複合酸化物）の調製］
具体的には、まず、所定の酸化物であるＴＳＷ複合酸化物（ＴｉＯ２−ＳｉＯ２−ＷＯ３の複合酸化物の粉体）を、以下に述べる方法で調製した。
[Preparation of oxide (TSW composite oxide)]
Specifically, first, a TSW composite oxide (a powder of composite oxide of TiO 2 —SiO 2 —WO 3 ), which is a predetermined oxide, was prepared by the method described below.
水１０００Ｌにアンモニア水（ＮＨ３＿２５％）７１５Ｌを添加し、これに３０質量％のシリカゾル溶液１９ｋｇを加えた。そこへ、別途調製した、水５Ｌにモノエタノールアミン（ＭＥＡ）を１ｋｇ加え、その上からパラタングステン酸アンモニウムを２．６ｋｇ混合し、約６０℃まで加温して、パラタングステン酸アンモニウムを溶解した液を加えた。得られた水溶液に、硫酸チタニルの硫酸水溶液（ＴｉＯＳＯ４［ＴｉＯ２換算］２５０ｇ／Ｌ、Ｈ２ＳＯ４＿１１００ｇ／Ｌ）４２１Ｌを水８００Ｌに添加して希釈したチタン含有硫酸水溶液を撹拌下で徐々に滴下して、共沈ゲルを生成させた。さらに、そのまま４０時間放置して静置した。このようにして得られたＴｉＯ２−ＳｉＯ２−ＷＯ３ゲルを濾過し、水洗した後、乾燥し、次いで５５０℃にて５時間、空気雰囲気下で焼成して、所定の酸化物（ＴｉＯ２−ＳｉＯ２−ＷＯ３の複合酸化物の粉体）を得た。得られた所定の酸化物の組成は、酸化物としての質量比でＴｉＯ２：ＳｉＯ２：ＷＯ３＝９５：３：２であった。なお、上記ＴＳＷ複合酸化物に含まれる硫黄化合物の量は、硫黄原子換算で３．５質量％であった。また、所定の酸化物の平均粒子径は２５μｍであった。 715 L of aqueous ammonia (NH 3 —25%) was added to 1000 L of water, and 19 kg of a 30% by mass silica sol solution was added thereto. Then, 1 kg of monoethanolamine (MEA) was added to 5 L of water separately prepared, 2.6 kg of ammonium paratungstate was mixed from above, and heated to about 60 ° C. to dissolve the ammonium paratungstate. The liquid was added. A titanium-containing sulfuric acid aqueous solution obtained by adding 421 L of sulfuric acid aqueous solution of titanyl sulfate (TiOSO 4 [TiO 2 equivalent] 250 g / L, H 2 SO 4 _1100 g / L) to 800 L of water was gradually added with stirring to the obtained aqueous solution. To form a coprecipitated gel. Furthermore, it was left to stand for 40 hours as it was. The TiO 2 —SiO 2 —WO 3 gel thus obtained is filtered, washed with water, dried, and then fired at 550 ° C. for 5 hours in an air atmosphere to obtain a predetermined oxide (TiO 2 to obtain a powder) of the composite oxide -SiO 2 -WO 3. The composition of the obtained predetermined oxide was TiO 2 : SiO 2 : WO 3 = 95: 3: 2 in terms of mass ratio as an oxide. The amount of the sulfur compound contained in the TSW composite oxide was 3.5% by mass in terms of sulfur atom. The average particle diameter of the predetermined oxide was 25 μm.
［ハニカム型触媒の製造］
２Ｌの水にパラタングステン酸アンモニウム１．７５ｋｇおよびモノエタノールアミン０．７５ｋｇを混合して溶解させ、均一溶液（ａ液）を調製した。また、４Ｌの水にメタバナジン酸アンモニウム０．３３ｋｇおよびシュウ酸０．４５ｋｇを混合して溶解させ、均一溶液（ｂ液）を調製した。
[Manufacture of honeycomb type catalyst]
To 2 L of water, 1.75 kg of ammonium paratungstate and 0.75 kg of monoethanolamine were mixed and dissolved to prepare a uniform solution (liquid a). Further, 0.33 kg of ammonium metavanadate and 0.45 kg of oxalic acid were mixed and dissolved in 4 L of water to prepare a uniform solution (liquid b).
一方、上記で調製した所定の酸化物であるＴＳＷ複合酸化物（平均粒子径２５μｍ）を２０．０ｋｇ計量した。計量したＴＳＷ複合酸化物を混練機に投入し、この上からａ液およびｂ液を投入し、成形助剤を追加水とともに加え、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））を加えて混合して触媒ペースト前駆体を得た。この触媒ペースト前駆体を混練機内で適度な硬さになるまで混練した（第１混練工程）。その後、第１混練工程で得られた混練物を混合機へ移し、さらに得られる触媒の質量１００質量％に対して８質量％の量の無機繊維（グラスウール）を加えて、混練機よりも小さい混練強度で混練することにより、成分の均一化を促進させた（第２混練工程）。 On the other hand, 20.0 kg of the TSW composite oxide (average particle size 25 μm) which is the predetermined oxide prepared above was weighed. The weighed TSW composite oxide is put into a kneader, and the liquid a and liquid b are added from above, and the molding aid is added together with additional water, and further 8% by mass with respect to 100% by mass of the resulting catalyst. An amount of inorganic fiber (glass wool; Owens, GW (830A)) was added and mixed to obtain a catalyst paste precursor. This catalyst paste precursor was kneaded in a kneader until the hardness became appropriate (first kneading step). Thereafter, the kneaded product obtained in the first kneading step is transferred to a mixer, and an inorganic fiber (glass wool) is added in an amount of 8% by mass with respect to 100% by mass of the obtained catalyst, which is smaller than the kneader. By kneading with kneading strength, homogenization of the components was promoted (second kneading step).
第２混練工程で得られた混練物を、押出し成形機を用いて８０ｍｍ角の格子状（ハニカム状）に成型した。次いで、得られた成型体を乾燥した後、４９０℃にて５時間焼成して、ハニカム型脱硝触媒を得た。得られた触媒中のＶ２Ｏ５およびＷＯ３の含有量は、それぞれ１．０質量％および７．５質量％であった。また、得られたハニカム型脱硝触媒の貫通孔の相当直径は６ｍｍ、セル肉厚は１．０ｍｍ、比表面積は１１５ｍ２／ｇであった。なお、触媒ペースト前駆体における水の含有量（ａ液に用いた水、ｂ液に用いた水および混練時に追加した追加水の合計量）は、ＴＳＷ複合酸化物の質量当たり５４０ｇ／ｋｇとした。 The kneaded product obtained in the second kneading step was molded into an 80 mm square lattice (honeycomb) using an extruder. Subsequently, the obtained molded body was dried and then fired at 490 ° C. for 5 hours to obtain a honeycomb type denitration catalyst. The contents of V 2 O 5 and WO 3 in the obtained catalyst were 1.0% by mass and 7.5% by mass, respectively. In addition, the equivalent diameter of the through hole of the obtained honeycomb type denitration catalyst was 6 mm, the cell thickness was 1.0 mm, and the specific surface area was 115 m 2 / g. The water content in the catalyst paste precursor (the total amount of water used for the liquid a, the water used for the liquid b and the additional water added during the kneading) was 540 g / kg per mass of the TSW composite oxide. .
（比較例１）
ＴＳ混合酸化物として、硫黄化合物を硫黄原子換算で１．０質量％含むチタン−ケイ素混合酸化物の粉体［混合比がＴｉＯ２：ＳｉＯ２＝８８：１２（質量比）］（平均粒子径３μｍ）を用いたこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１０６ｍ２／ｇであった。
(Comparative Example 1)
As TS mixed oxide, powder of titanium-silicon mixed oxide containing 1.0% by mass of sulfur compound in terms of sulfur atom [mixing ratio is TiO 2 : SiO 2 = 88: 12 (mass ratio)] (average particle diameter A honeycomb type denitration catalyst was obtained in the same manner as in Example 1 except that 3 μm) was used. The specific surface area of the obtained honeycomb type denitration catalyst was 106 m 2 / g.
（比較例２）
無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））の添加量を、得られる触媒の質量１００質量％に対して１２質量％とし、第１混練工程前および第２混練工程前の添加量をそれぞれ６質量％としたこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１１０ｍ２／ｇであった。
(Comparative Example 2)
The addition amount of inorganic fibers (glass wool; GW (830A), manufactured by Owens) is 12% by mass with respect to 100% by mass of the obtained catalyst, and the addition amount before the first kneading step and before the second kneading step. A honeycomb type denitration catalyst was obtained by the same method as in Example 1 except that the content of each was 6 mass%. The specific surface area of the obtained honeycomb type denitration catalyst was 110 m 2 / g.
（比較例３）
無機繊維（グラスウール；オーウェンス社製、ＧＷ（８３０Ａ））の添加量を、得られる触媒の質量１００質量％に対して２５質量％とし、第１混練工程前および第２混練工程前の添加量をそれぞれ１３質量％および１２質量としたこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１３０ｍ２／ｇであった。
(Comparative Example 3)
The addition amount of inorganic fibers (glass wool; GW (830A), manufactured by Owens) is 25% by mass with respect to 100% by mass of the obtained catalyst, and the addition amount before the first kneading step and before the second kneading step. A honeycomb type denitration catalyst was obtained by the same method as in Example 1 except that the content was 13% by mass and 12% by mass, respectively. The specific surface area of the obtained honeycomb type denitration catalyst was 130 m 2 / g.
（比較例４）
第１混練工程前に無機繊維の全量（得られる触媒の質量１００質量％に対して１６質量％）を添加し、第２混練工程前には無機繊維を添加しなかったこと以外は、上述した実施例１と同様の手法により、ハニカム型脱硝触媒を得た。なお、得られたハニカム型脱硝触媒の比表面積は１１２ｍ２／ｇであった。
(Comparative Example 4)
The total amount of inorganic fibers (16% by mass with respect to 100% by mass of the obtained catalyst) was added before the first kneading step, and the inorganic fibers were not added before the second kneading step. A honeycomb type denitration catalyst was obtained in the same manner as in Example 1. The specific surface area of the obtained honeycomb-type denitration catalyst was 112 m 2 / g.
［ハニカム型脱硝触媒の評価］
上記の実施例および比較例で得られたハニカム型脱硝触媒を用いて、下記の条件で触媒の耐摩耗性（摩耗率）および脱硝性能（脱硝率）を評価した。結果を下記の表２に示す。なお、表２には、レーザー回折散乱法という手法により測定した酸化物の平均粒子径の値、および、水銀圧入法により測定したハニカム型脱硝触媒の細孔容積の値についても併せて記載する。
[Evaluation of honeycomb type denitration catalyst]
Using the honeycomb-type denitration catalysts obtained in the above Examples and Comparative Examples, the wear resistance (wear rate) and the denitration performance (denitration rate) of the catalyst were evaluated under the following conditions. The results are shown in Table 2 below. Table 2 also shows the value of the average particle diameter of the oxide measured by the laser diffraction scattering method and the value of the pore volume of the honeycomb type denitration catalyst measured by the mercury intrusion method.
（耐摩耗性の評価（摩耗率の測定））
ハニカム型脱硝触媒を９セル×９セル×１００ｍｍ長さのサイズに切り出し、摩耗率測定用サンプルとした。このサンプルの貫通孔内に３８ｇ／ｍ３の濃度の硅砂を含む空気を１６ｍ／ｓ（触媒断面あたり）のガス流量で常温にて２時間導入することにより強制摩耗試験を行い、下記式に従って摩耗率を算出した。なお、摩耗率の値が小さいほど、耐摩耗性に優れることを意味する。
(Evaluation of wear resistance (measurement of wear rate))
A honeycomb-type denitration catalyst was cut into a size of 9 cells × 9 cells × 100 mm in length and used as a sample for wear rate measurement. A forced wear test was conducted by introducing air containing 38 g / m 3 of dredged sand into the through hole of this sample at a normal gas flow rate of 16 m / s (per catalyst cross section) for 2 hours. The rate was calculated. In addition, it means that it is excellent in abrasion resistance, so that the value of an abrasion rate is small.
摩耗率（％）＝（［テスト前触媒質量−テスト後触媒質量）／テスト前触媒質量］×１００
（脱硝率の測定）
ハニカム型脱硝触媒を３セル×３セル×３０６ｍｍ長さのサイズに切り出し、ステンレス製の反応管に充填した。この反応管に、下記の表１の組成を有する合成ガスを導入した。そして、反応管入口ガスおよび出口ガスのＮＯｘ濃度を化学光学式ＮＯｘ計により測定し、下記式に従って脱硝率を算出した。なお、脱硝率の値が大きいほど、脱硝性能に優れることを意味する。
Abrasion rate (%) = ([catalyst mass before test−catalyst mass after test) / catalyst mass before test] × 100
(Denitration rate measurement)
The honeycomb type denitration catalyst was cut into a size of 3 cells × 3 cells × 306 mm and filled into a stainless steel reaction tube. A synthesis gas having the composition shown in Table 1 below was introduced into the reaction tube. And the NOx density | concentration of reaction tube inlet gas and outlet gas was measured with the chemical optical NOx meter, and the denitration rate was computed according to the following formula. In addition, it means that it is excellent in denitration performance, so that the value of denitration rate is large.
脱硝率（％）＝［（入口ＮＯｘ濃度−出口ＮＯｘ濃度）／入口ＮＯｘ濃度］×１００ Denitration rate (%) = [(inlet NOx concentration−outlet NOx concentration) / inlet NOx concentration] × 100
表２に示す結果から、酸化物中の硫黄含有量が少な過ぎる比較例１や、無機繊維の添加量が少な過ぎる比較例２、無機繊維を分割して添加していない比較例４では、脱硝性能は優れるものの、十分な耐摩耗性を得ることができていない。一方、無機繊維の添加量が多過ぎる比較例３では、耐摩耗性は優れるものの、十分な脱硝性能を得ることができていない。 From the results shown in Table 2, in Comparative Example 1 in which the sulfur content in the oxide is too small, in Comparative Example 2 in which the amount of inorganic fibers added is too small, and in Comparative Example 4 in which the inorganic fibers are not dividedly added, denitration is performed. Although the performance is excellent, sufficient wear resistance cannot be obtained. On the other hand, in Comparative Example 3 in which the amount of inorganic fiber added is too large, the wear resistance is excellent, but sufficient denitration performance cannot be obtained.
これに対し、所定の酸化物と無機繊維とを含む触媒ペースト前駆体を混練してからハニカム状に成型して脱硝触媒を製造する際に、上記酸化物として所定量の硫黄化合物を含むものを用い、かつ、得られる触媒に含まれる無機繊維の添加量所定の範囲内の値に制御するとともに混練工程を２段階以上行い、上記無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加することで、脱硝性能の低下を最小限に抑えつつ、耐摩耗性に優れるハニカム型脱硝触媒を得ることができることがわかる。 On the other hand, when a catalyst paste precursor containing a predetermined oxide and inorganic fibers is kneaded and then formed into a honeycomb shape to produce a denitration catalyst, the oxide contains a predetermined amount of a sulfur compound as the oxide. And the addition amount of the inorganic fiber contained in the obtained catalyst is controlled to a value within a predetermined range and the kneading process is performed in two or more stages, and the inorganic fiber is mixed in two or more stages so as to correspond to the kneading in two or more stages. It can be seen that a honeycomb type denitration catalyst having excellent wear resistance can be obtained while adding a decrease in the denitration performance while minimizing a decrease in the denitration performance.
Claims (5)
前記触媒ペーストをハニカム状に成型し、焼成することを含む、ハニカム型脱硝触媒の製造方法であって、
前記酸化物に含まれる硫黄化合物の含有量が、硫黄原子換算で１．５〜３．５質量％であり、
得られる触媒における前記無機繊維の含有量が、１４〜２０質量％であり、
前記混練を２段階以上で行い、前記無機繊維を２段階以上の混練に対応するように２段階以上に分割して添加することを特徴とする、ハニカム型脱硝触媒の製造方法。 Titanium oxide, mixed oxide and / or composite oxide of titanium-silicon, mixed oxide and / or composite oxide of titanium-tungsten, and mixed oxide and / or composite oxide of titanium-silicon-tungsten A catalyst paste is obtained by kneading a catalyst paste precursor containing an oxide selected from the group, at least one active ingredient selected from the group consisting of vanadium, tungsten and molybdenum, inorganic fibers, and water. And
A method for producing a honeycomb-type denitration catalyst, comprising forming the catalyst paste into a honeycomb shape and firing the catalyst paste,
The content of the sulfur compound contained in the oxide is 1.5 to 3.5% by mass in terms of sulfur atom,
Content of the said inorganic fiber in the catalyst obtained is 14-20 mass%,
A method for producing a honeycomb type denitration catalyst, wherein the kneading is performed in two or more stages, and the inorganic fibers are added in two or more stages so as to correspond to two or more stages of kneading.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016057488A JP6591919B2 (en) | 2016-03-22 | 2016-03-22 | Method for manufacturing honeycomb-type denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016057488A JP6591919B2 (en) | 2016-03-22 | 2016-03-22 | Method for manufacturing honeycomb-type denitration catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017170308A JP2017170308A (en) | 2017-09-28 |
| JP6591919B2 true JP6591919B2 (en) | 2019-10-16 |
Family
ID=59969868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016057488A Active JP6591919B2 (en) | 2016-03-22 | 2016-03-22 | Method for manufacturing honeycomb-type denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6591919B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295865B (en) * | 2018-03-02 | 2024-03-22 | 河北工业大学 | Integral honeycomb low-temperature SCR denitration catalyst and preparation method thereof |
| CN111167489B (en) * | 2020-02-14 | 2022-10-04 | 江苏龙净科杰环保技术有限公司 | Honeycomb anti-poison low-temperature SCR denitration catalyst and preparation method thereof |
| CN113262777A (en) * | 2021-06-03 | 2021-08-17 | 江苏龙净科杰环保技术有限公司 | Cement denitration catalyst with large aperture and high mechanical strength and preparation method thereof |
| CN113457667A (en) * | 2021-07-16 | 2021-10-01 | 国家电投集团远达环保催化剂有限公司 | Denitration and dust removal integrated catalyst and preparation method thereof |
-
2016
- 2016-03-22 JP JP2016057488A patent/JP6591919B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017170308A (en) | 2017-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6591919B2 (en) | Method for manufacturing honeycomb-type denitration catalyst | |
| KR100370460B1 (en) | DeNOx CATALYST FOR REDUCING THE NOx CONCENTRATION IN A STREAM OF FLUID, AND METHOD OF MANUFACTURING THE CATALYST | |
| JP2008119651A (en) | Catalyst for nitrogen oxide removal, and exhaust gas treating method | |
| JP2008516757A (en) | Nitrogen oxide removal catalyst of metal oxide supported on highly active titania | |
| JP2013091045A (en) | Exhaust gas treating method | |
| JP2730987B2 (en) | Catalyst for removing nitrogen oxides and method for removing nitrogen oxides using the catalyst | |
| JP4538198B2 (en) | Titanium dioxide powder for honeycomb exhaust gas treatment catalyst and honeycomb exhaust gas treatment catalyst using the titanium dioxide powder | |
| JP2015142917A (en) | Titanium-containing powder, exhaust gas treatment catalyst, and method of producing titanium-containing powder | |
| JP4098703B2 (en) | Nitrogen oxide removing catalyst and nitrogen oxide removing method | |
| CN103301831A (en) | Catalyst for removing nitrogen oxide in emission exhaust and preparation method thereof | |
| JP2015182067A (en) | Catalyst and method for treating marine exhaust gas | |
| JP2008024565A (en) | Modified titanium oxide particle and its manufacturing method and exhaust gas treating catalyst using the same | |
| JP2020515384A (en) | Catalyst, exhaust system and method for treating exhaust gas | |
| JP6132498B2 (en) | Titanium / silicon / tungsten oxide, denitration catalyst using the same, method for preparing the oxide, and denitration method | |
| JP6663761B2 (en) | Method for producing honeycomb type denitration catalyst | |
| JP5215990B2 (en) | Exhaust gas treatment catalyst and exhaust gas treatment method | |
| JP2006150352A (en) | Catalyst and method for exhaust gas treatment | |
| JP3337634B2 (en) | Denitration catalyst, its preparation method, and denitration method | |
| JP2012206058A (en) | Denitration catalyst and denitrification method | |
| JP3749078B2 (en) | NOx removal catalyst and NOx removal method | |
| JP6261260B2 (en) | Ship exhaust gas treatment catalyst and exhaust gas treatment method | |
| JP6906420B2 (en) | Manufacturing method of inorganic composite oxide and exhaust gas treatment method using this | |
| JPH08229412A (en) | Catalyst and method for removing nitrogen oxide | |
| JP2013071071A (en) | Method for treating exhaust gas | |
| JP2004290753A (en) | Heat-resistant denitrification catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190826 |
|
| 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: 20190903 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190919 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6591919 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |