JP2013132624A5 - - Google Patents
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- JP2013132624A5 JP2013132624A5 JP2011286115A JP2011286115A JP2013132624A5 JP 2013132624 A5 JP2013132624 A5 JP 2013132624A5 JP 2011286115 A JP2011286115 A JP 2011286115A JP 2011286115 A JP2011286115 A JP 2011286115A JP 2013132624 A5 JP2013132624 A5 JP 2013132624A5
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- titanium
- granular powder
- honeycomb
- exhaust gas
- tungsten
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- 239000000843 powder Substances 0.000 claims description 279
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 225
- 239000010936 titanium Substances 0.000 claims description 211
- 229910052719 titanium Inorganic materials 0.000 claims description 211
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 127
- 239000003054 catalyst Substances 0.000 claims description 92
- 239000007789 gas Substances 0.000 claims description 90
- 239000002131 composite material Substances 0.000 claims description 67
- 239000000654 additive Substances 0.000 claims description 56
- 230000000996 additive effect Effects 0.000 claims description 56
- 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 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000004408 titanium dioxide Substances 0.000 claims description 39
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 33
- 229910052721 tungsten Inorganic materials 0.000 claims description 32
- 239000010937 tungsten Substances 0.000 claims description 32
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 31
- 229910052750 molybdenum Inorganic materials 0.000 claims description 31
- 239000011733 molybdenum Substances 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 23
- 238000002441 X-ray diffraction Methods 0.000 claims description 22
- 150000001805 chlorine compounds Chemical class 0.000 claims description 18
- 150000003464 sulfur compounds Chemical class 0.000 claims description 18
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 17
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 7
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 238000004898 kneading Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011236 particulate material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 23
- 229910010413 TiO 2 Inorganic materials 0.000 description 21
- 150000003608 titanium Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 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 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Description
第３の発明は、タングステン及びモリブデンの少なくとも一方と、チタンとを含む金属元素の複合酸化物（Ｘ）と、（i）タングステン含有窒素化合物、（ii）タングステン含有硫黄化合物、（iii）タングステン含有塩素化合物、（iv）モリブデン含有窒素化合物、（v）モリブデン含有硫黄化合物、及び（vi）モリブデン含有塩素化合物から選ばれた添加剤（Ｙ）とを、以下に示す割合で混合する工程を含むハニカム状排ガス処理触媒製造用のチタン含有粒状粉末の製造方法であって、
（１）前記添加剤（Ｙ）として、（i）タングステン含有窒素化合物または（iv）モリブデン含有窒素化合物を使用する場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる窒素原子のモル数をＢで表したとき、そのモル比（Ｂ／Ａ）が、８．７０×１０−４〜２．７８×１０−１の範囲となる割合で前記複合酸化物と該添加剤とを混合する工程からなり、
（２）前記添加剤（Ｙ）として、（ii）タングステン含有硫黄化合物または（v）モリブデン含有硫黄化合物を使用する場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる硫黄原子のモル数をＣで表したとき、そのモル比（Ｃ／Ａ）が、６．９６×１０−３〜５．５５×１０−１の範囲となる割合で前記複合酸化物と該添加剤とを混合する工程からなり、また
（３）前記添加剤（Ｙ）として、（iii）タングステン含有塩素化合物または（vi）モリブデン含有塩素化合物を使用する場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる塩素原子のモル数をＤで表したとき、そのモル比（Ｄ／Ａ）が、６．９６×１０−３〜６．９４×１０−１の範囲となる割合で前記複合酸化物と該添加剤とを混合する工程からなる
ことを特徴とするハニカム状排ガス処理触媒製造用のチタン含有粒状粉末の製造方法である。
さらに、前記第３の発明は、以下の要件を備えていることが好ましい。
（ａ）前記チタン含有粒状粉末が、前記金属元素の複合酸化物（Ｘ）と、（i）タングステン含有窒素化合物、（ii）タングステン含有硫黄化合物、（iii）タングステン含有塩素化合物、（iv）モリブデン含有窒素化合物、（v）モリブデン含有硫黄化合物、及び（vi）モリブデン含有塩素化合物から選ばれた少なくとも１種の添加剤（Ｙ）とを混合して得られたものであること。
The third invention is a composite oxide (X) of a metal element containing at least one of tungsten and molybdenum and titanium, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, and (iii) tungsten-containing Honeycomb including a step of mixing a chlorine compound, (iv) a molybdenum-containing nitrogen compound, (v) a molybdenum-containing sulfur compound, and (vi) an additive (Y) selected from the molybdenum-containing chlorine compound at a ratio shown below A method for producing titanium-containing granular powder for producing a flue gas treatment catalyst,
(1) When (i) tungsten-containing nitrogen compound or (iv) molybdenum-containing nitrogen compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium-containing granular powder is represented by A. In addition, when the number of moles of nitrogen atoms contained in the titanium-containing granular powder is represented by B, the molar ratio (B / A) is from 8.70 × 10 −4 to 2.78 × 10 −1 . Comprising the step of mixing the composite oxide and the additive in a proportion that falls within a range,
(2) When (ii) tungsten-containing sulfur compound or (v) molybdenum-containing sulfur compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium-containing granular powder is A. When the number of moles of sulfur atoms contained in the titanium-containing granular powder is expressed by C, the molar ratio (C / A) is 6.96 × 10 −3 to 5.55 × 10 −1 . And (3) using a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound as the additive (Y). When the number of moles of titanium atoms contained in the titanium-containing granular powder is represented by A and the number of moles of chlorine atoms contained in the titanium-containing granular powder is represented by D, the molar ratio ( D / A) is 6 96 × 10 -3 ~6.94 × 10 percentage in the composite oxide in the range of -1 and honeycomb exhaust gas treatment catalyst of titanium-containing particulate for production characterized by comprising the step of mixing the additive It is a manufacturing method of powder.
Furthermore, it is preferable that the third invention has the following requirements.
(A) The titanium-containing granular powder comprises the composite oxide (X) of the metal element, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, and (iv) molybdenum. It is obtained by mixing at least one additive (Y) selected from a nitrogen-containing compound, (v) a molybdenum-containing sulfur compound, and (vi) a molybdenum-containing chlorine compound.
［ハニカム状排ガス処理触媒］
本発明に係るハニカム状排ガス処理触媒は、上述のハニカム構造体からなる排ガス処理触媒であって、前記チタン含有粒状粉末を全重量の６０質量％以上、好ましくは７０〜９９．９質量％の範囲で含有していることが望ましい。該チタン含有粒状粉末の含有割合が６０質量％より少ない場合には、所望の脱硝活性が得られないことがある。また、上述のように、本発明のチタン含有粒状粉末を６０質量％以上含有していれば、例えば本発明でいう複合酸化物と添加剤とを含まない本発明の技術的範囲外の粒状粉末（例えば、二酸化チタン粉末など）を４０質量％未満含有していてもよい。
前記ハニカム状排ガス処理触媒には、窒素酸化物を除去するための活性成分がさらに含まれる。前記活性成分としては、例えば、バナジウム（Ｖ）、タングステン（Ｗ）、モリブデン（Ｍｏ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、パラジウム（Ｐｄ）、イットリウム（Ｙ）、セリウム（Ｃｅ）、ネオジウム（Ｎｄ）、インジウム（Ｉｎ）、イリジウム（Ｉｒ）などの金属成分が挙げられる。
上述の活性成分のうち、特にバナジウム酸化物（Ｖ２Ｏ５）は、比較的安価であり且つ窒素酸化物の除去率が高いため、好適に使用される。また、窒素酸化物を除去するための排ガス処理触媒に使用される活性成分の含有量は、金属酸化物として全触媒重量の０．１〜３０質量％の範囲にあることが好ましい。
このように、前記複合酸化物を含むチタン含有粒状粉末を少なくとも６０質量％以上含有するようにして成形されたハニカム状排ガス処理触媒は、前記活性成分を含むハニカム構造体の焼成時における二酸化チタンの結晶化進行が抑制されるばかりでなく、これを用いて排ガス処理を行った場合、高い窒素酸化物の除去率を達成することができる。
[Honeycomb exhaust gas treatment catalyst]
A honeycomb-shaped exhaust gas treatment catalyst according to the present invention is an exhaust gas treatment catalyst comprising the above-described honeycomb structure, and the titanium-containing granular powder is 60% by mass or more, preferably in the range of 70 to 99.9% by mass. It is desirable to contain. When the content ratio of the titanium-containing granular powder is less than 60% by mass, desired denitration activity may not be obtained. In addition, as described above, if the titanium-containing granular powder of the present invention is contained in an amount of 60% by mass or more, for example, the granular powder outside the technical scope of the present invention does not include the complex oxide and additive referred to in the present invention. (For example, titanium dioxide powder etc.) may be contained in less than 40% by mass.
The honeycomb-shaped exhaust gas treatment catalyst further includes an active component for removing nitrogen oxides. Examples of the active component include vanadium (V), tungsten (W), molybdenum (Mo), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), silver ( Examples thereof include metal components such as Ag), gold (Au), palladium (Pd), yttrium (Y), cerium (Ce), neodymium (Nd), indium (In), and iridium (Ir).
Of the above-mentioned active ingredients, vanadium oxide (V 2 O 5 ) is particularly suitable because it is relatively inexpensive and has a high nitrogen oxide removal rate. Moreover, it is preferable that content of the active component used for the exhaust gas treatment catalyst for removing a nitrogen oxide exists in the range of 0.1-30 mass% of the total catalyst weight as a metal oxide.
Thus, the honeycomb-shaped exhaust gas treatment catalyst formed so as to contain at least 60% by mass of the titanium-containing granular powder containing the composite oxide is a titanium dioxide at the time of firing the honeycomb structure containing the active component. Not only is the progress of crystallization suppressed, but when exhaust gas treatment is performed using this, a high nitrogen oxide removal rate can be achieved.
一般に、活性物質としての酸化バナジウムまたはその前駆物質を添加、或いはこれらの懸濁水溶液で含浸した酸化チタン担体（例えば、ハニカム構造体）を焼成すると、バナジウムの存在により二酸化チタンの結晶化が進行することが知られている。そこで、本発明の排ガス処理触媒を製造するに際しては、酸化バナジウムまたはその前駆物質（これらの懸濁水溶液を含む）を添加しない状態で焼成して得られたチタン含有粒状粉末を用いている。このことから、チタン含有粒状粉末の焼成段階から上記のバナジウム源を添加することは好ましくなく、このバナジウム源を含ませた触媒前駆体（ハニカム構造体）を得た段階で焼成することが好ましい。また、このようにバナジウム源を添加した触媒前駆体を焼成しても、本発明のチタン含有粒状粉末を用いて調製された触媒前駆体であるならば、上記の理由により二酸化チタンの結晶化の進行度合いを十分に抑えることができる。
このようにして得られたハニカム状排ガス処理触媒（ハニカム構造体）の形状は、特に限定されるものではないが、正方四角柱や長方四角柱などからなっており、ハニカム孔の貫通方向の一端側から見た平面には、図１に示すような四角形のハニカム孔が複数個（例えば、４〜２５００個）が穿たれている。ただし、このハニカム孔は、四角形ではなく蜂の巣形状などを有するものであってもよい。また前記ハニカム構造体の外形寸法は、（i）前記ハニカム孔の貫通方向の一端から平面の長さ（以下、「平面の一辺の長さ」という場合がある。）が約３０〜３００ｍｍ、好ましくは約５０〜２００ｍｍ（ii）ハニカム孔の貫通方向の長さ（以下、「貫通方向の長さ」という場合がある。）が約１００〜３０００ｍｍ、好ましくは約３００〜１５００ｍｍ、（iii）ハニカム孔（四角形）を形成する開口部の一辺の長さ（以下、「目開き」という場合がある。）が約１〜１５ｍｍ、好ましくは約２〜１０ｍｍ、（iv）ハニカム孔の間に形成される隔壁の厚さ（以下、「隔壁の厚さ」という場合がある。）が約０．１〜２ｍｍ、好ましくは約０．１〜１．５ｍｍ、（ｖ）ハニカム構造体の開口率が６０〜８５％、好ましくは７０〜８５％の範囲にあることが望ましい。このように四角柱の形状を有するハニカム構造体の外形寸法が前記寸法の範囲を外れる場合には、その成形が困難になったり、ハニカム構造体の強度が弱くなったり、或いは単位体積当たりの脱硝活性や有機ハロゲン化合物の分解活性等が低くなったりする場合がある。
In general, when vanadium oxide as an active substance or a precursor thereof is added or a titanium oxide support (for example, a honeycomb structure) impregnated with an aqueous suspension thereof is fired, crystallization of titanium dioxide proceeds due to the presence of vanadium. It is known. Therefore, when producing the exhaust gas treatment catalyst of the present invention, a titanium-containing granular powder obtained by firing without adding vanadium oxide or a precursor thereof (including an aqueous suspension thereof) is used. For this reason, it is not preferable to add the vanadium source from the firing stage of the titanium-containing granular powder, and it is preferable to fire the catalyst precursor (honeycomb structure) containing the vanadium source. Further, even if the catalyst precursor added with the vanadium source is calcined as described above, if the catalyst precursor is prepared using the titanium-containing granular powder of the present invention, the crystallization of titanium dioxide is performed for the above-mentioned reason. The degree of progress can be sufficiently suppressed.
The shape of the honeycomb-shaped exhaust gas treatment catalyst (honeycomb structure) obtained in this way is not particularly limited, but is composed of a square quadrangular prism, a rectangular quadrangular prism, etc. In the plane viewed from one end side, a plurality of (for example, 4 to 2500) rectangular honeycomb holes as shown in FIG. 1 are formed. However, the honeycomb holes may have a honeycomb shape instead of a square shape. In addition, the external dimensions of the honeycomb structure are as follows: ( i ) the length of the plane from one end in the penetration direction of the honeycomb holes (hereinafter sometimes referred to as “the length of one side of the plane”) is about 30 to 300 mm. Is about 50 to 200 mm (ii) the length in the penetration direction of the honeycomb holes (hereinafter sometimes referred to as “the length in the penetration direction”) is about 100 to 3000 mm, preferably about 300 to 1500 mm, (iii) the honeycomb holes The length of one side of the opening that forms (square) (hereinafter sometimes referred to as “aperture”) is about 1 to 15 mm, preferably about 2 to 10 mm, and (iv) is formed between the honeycomb holes. The partition wall thickness (hereinafter sometimes referred to as “partition wall thickness”) is about 0.1 to 2 mm, preferably about 0.1 to 1.5 mm, and (v) the honeycomb structure has an aperture ratio of 60 to 60 mm. 85%, preferably in the range of 70-85% It is desirable to be. Thus, when the outer dimensions of the honeycomb structure having a quadrangular prism shape are out of the above range, it becomes difficult to form the honeycomb structure, the strength of the honeycomb structure becomes weak, or denitration per unit volume. In some cases, the activity and the activity of decomposing organic halogen compounds may be lowered.
［実施例１］
＜チタン含有粒状粉末（ａ）及びハニカム状排ガス処理触媒（Ａ）＞
(1) チタン含有粒状粉末（ａ）
硫酸法による二酸化チタンの製造工程より得られる硫酸チタン溶液を熱加水分解してメタチタン酸スラリーを得た。予め１５重量％アンモニア水１５ｋｇを入れておいた還流器付攪拌槽にメタチタン酸スラリーを二酸化チタン換算で２３．８ｋｇ加えて、さらにパラタングステン酸アンモニウムを１．１３ｋｇ加えた後、９５℃で１時間に亘り十分な攪拌を行いつつ加熱熟成した。加熱熟成後のスラリーを冷却して攪拌槽から取り出し、その固形分を濾過、脱水して、洗浄ケーキを得た。該洗浄ケーキを１１０℃の温度で２０時間乾燥した後、これを５５０℃の温度で５時間焼成した。これにより、添加された原料などに含まれる窒素原子は、アンモニアとして系外に放出された。次に、この焼成物を予めボールミルで粉砕して、全体の９９．９質量％以上が４５μｍ以下の粒子径をもつ、チタンおよびタングステンの金属元素を含む複合酸化物の粒状粉体（ａ’）を得た。
次いで、この複合酸化物の粒状粉体（ａ’）に、添加剤としてのパラタングステン酸アンモニウムを０．２８２ｋｇ加え、ブレンダーで均一になるように混合してチタン含有粒状粉末（ａ）を調製した。このように調製されたチタン含有粒状粉末をボールミルを用いて解砕し、その全量の９９．９質量％以上が４５μｍ以下の粒子径をもつチタン含有粒状粉末（ａ）を得た。
次に、このようにして得られたチタン含有粒状粉末（ａ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２９７および０．９０であり、その比（Ｂ／Ａ）は３．０３×１０−３であった。
また、前記チタン含有粒状粉末（ａ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、しかも該アナターゼ型結晶の（１０１）面のピーク強度をＰ1とし、また二酸化チタンの基準粉末（石原産業株式会社製 ＭＣ−９０）におけるアナターゼ型結晶の（１０１）面のピーク強度をＰ0で表したとき、そのピーク強度の比（Ｐ1／Ｐ0）が０．９７であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９３ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ａ）
次に、このようにして得られたチタン含有粒状粉末（ａ）２３．６ｋｇに、メタバナジン酸アンモニウム０．１７４ｋｇをモノエタノールアミン０．２５０ｋｇに溶解した溶液を加え、次いでアンモニア水と水を加えて、この混合スラリーのｐＨを６以上とした。さらに、補強材であるグラスファイバー（以下、「ＧＦ」という場合がある。）１．２５ｋｇとポリエチレンオキサイド０．５００ｋｇとを該混合スラリーに加えてニーダーにて加熱、捏和して押出成形に適した捏和物を調製した。次いで、該捏和物を真空押出成形機で押出成形して、外径寸法が、平面の一辺の長さ７５ｍｍ、貫通方向の長さ約５００ｍｍ、目開き（四角形の貫通孔径）６．７ｍｍ、隔壁の厚さ０．７５ｍｍ、開口率８０％、のハニカム構造体を得た。このようにして得られたハニカム構造体を６０℃で２４時間乾燥後、６００℃で３時間焼成して、該ハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比がそれぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であるハニカム状排ガス処理触媒（Ａ）を調製した。
[Example 1]
<Titanium-containing granular powder (a) and honeycomb-shaped exhaust gas treatment catalyst (A)>
(1) Titanium-containing granular powder (a)
The titanium sulfate solution obtained from the manufacturing process of titanium dioxide by the sulfuric acid method was hydrolyzed to obtain a metatitanic acid slurry. After adding 23.8 kg of metatitanic acid slurry in terms of titanium dioxide and adding 1.13 kg of ammonium paratungstate to a stirring tank equipped with a reflux vessel in which 15 kg of 15% by weight aqueous ammonia has been added in advance, 1 hour at 95 ° C. The mixture was aged by heating with sufficient stirring. The slurry after heat aging was cooled and taken out from the stirring vessel, and the solid content was filtered and dehydrated to obtain a washed cake. The washed cake was dried at a temperature of 110 ° C. for 20 hours and then calcined at a temperature of 550 ° C. for 5 hours. Thereby, the nitrogen atom contained in the added raw material etc. was discharge | released out of the system as ammonia. Next, the fired product is previously pulverized by a ball mill, and a composite oxide granular powder (a ′) containing a metal element of titanium and tungsten having a particle diameter of 45 μm or less of 99.9% by mass of the whole. Got.
Next, 0.282 kg of ammonium paratungstate as an additive was added to the granular powder (a ′) of the composite oxide, and mixed so as to be uniform with a blender to prepare a titanium-containing granular powder (a). . The titanium-containing granular powder thus prepared was pulverized using a ball mill to obtain a titanium-containing granular powder (a) in which 99.9% by mass or more of the total amount had a particle diameter of 45 μm or less.
Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (a) thus obtained by the atomic weight is obtained. Furthermore, the value B obtained by dividing the mass of the nitrogen atom which is an element constituting the additive (ammonium paratungstate) by the atomic weight was determined. As a result, the values A and B were 297 and 0.90, respectively, and the ratio (B / A) was 3.03 × 10 −3 .
Further, when the titanium-containing granular powder (a) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the anatase type crystal of the peak intensity of (101) plane and P 1, and when representing the peak intensity of (101) plane of anatase-type crystal in the reference powder (Ishihara Sangyo Kaisha Ltd. MC-90) of titanium dioxide P 0, the The ratio of peak intensity (P 1 / P 0 ) was 0.97. Furthermore, it was 93 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (A)
Next, a solution obtained by dissolving 0.174 kg of ammonium metavanadate in 0.250 kg of monoethanolamine was added to 23.6 kg of the titanium-containing granular powder (a) thus obtained, and then ammonia water and water were added. The pH of this mixed slurry was 6 or more. Furthermore, 1.25 kg of glass fiber (hereinafter sometimes referred to as “GF”) as a reinforcing material and 0.500 kg of polyethylene oxide are added to the mixed slurry, heated and kneaded with a kneader, and suitable for extrusion molding. A koji product was prepared. Subsequently, the kneaded product is extruded using a vacuum extruder, and the outer diameter is 75 mm on one side of the plane, the length in the penetrating direction is about 500 mm, the aperture (square through-hole diameter) is 6.7 mm, A honeycomb structure having a partition wall thickness of 0.75 mm and an aperture ratio of 80% was obtained. The honeycomb structure thus obtained was dried at 60 ° C. for 24 hours and then fired at 600 ° C. for 3 hours, so that the weight composition ratios of the metal elements contained in the honeycomb structure based on oxides were TiO 2 respectively. A honeycomb-shaped exhaust gas treatment catalyst (A) having a ratio of 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5.00 was prepared.
［実施例２］
＜チタン含有粒状粉末（ｂ）及びハニカム状排ガス処理触媒（Ｂ）＞
(1) チタン含有粒状粉末（ｂ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）を調製する際にパラタングステン酸アンモニウムの添加量を０．８４５ｋｇに変えたこと以外は、実施例１と同様の方法にて調製して複合酸化物の粒状粉体（ｂ’）を得た。
また、この複合酸化物の粒状粉体（ｂ’）に、添加剤として加えたパラタングステン酸アンモニウムの量を０．５６４ｋｇに変えた以外は、実施例１と同様の方法にてチタン含有粒状粉末（ｂ）を調製した。
次に、このようにして得られたチタン含有粒状粉末（ｂ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２９７および１．８０であり、その比（Ｂ／Ａ）は６．０５×１０−３であった。
また、前記チタン含有粒状粉末（ｂ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９５であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９４ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｂ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｂ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｂ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 2]
<Titanium-containing granular powder (b) and honeycomb-shaped exhaust gas treatment catalyst (B)>
(1) Titanium-containing granular powder (b)
In the same manner as in Example 1, except that the amount of ammonium paratungstate added was changed to 0.845 kg when preparing the composite oxide granular powder (a ′) obtained in Example 1. Thus, a composite oxide granular powder (b ′) was obtained.
Further, a titanium-containing granular powder was produced in the same manner as in Example 1, except that the amount of ammonium paratungstate added as an additive to the granular powder (b ′) of this composite oxide was changed to 0.564 kg. (B) was prepared.
Next, the value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (b) thus obtained by the atomic weight is obtained. Furthermore, the value B obtained by dividing the mass of the nitrogen atom which is an element constituting the additive (ammonium paratungstate) by the atomic weight was determined. As a result, the values A and B were 297 and 1.80, respectively, and the ratio (B / A) was 6.05 × 10 −3 .
Further, when the titanium-containing granular powder (b) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95. Furthermore, it was 94 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (B)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (b) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (B) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例３］
＜チタン含有粒状粉末（ｃ）及びハニカム状排ガス処理触媒（Ｃ）＞
(1) チタン含有粒状粉末（ｃ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）を調製する際にパラタングステン酸アンモニウムの添加量を０．２８１ｋｇに変えたこと以外は、実施例１と同様の方法にて調製して複合酸化物の粒状粉体（ｃ’）を得た。
また、この複合酸化物の粒状粉体（ｃ’）に添加剤として加えたパラタングステン酸アンモニウムの量を１．１３ｋｇに変えたこと以外は、実施例１と同様の方法にてチタン含有粒状粉末（ｃ）を調製した。
次に、このようにして得られたチタン含有粒状粉末（ｃ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２９７および３．６０であり、その比（Ｂ／Ａ）は１．２１×１０−２であった。
また、前記チタン含有粒状粉末（ｃ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９６であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９３ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｃ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｃ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｃ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 3]
<Titanium-containing granular powder (c) and honeycomb-shaped exhaust gas treatment catalyst (C)>
(1) Titanium-containing granular powder (c)
In the same manner as in Example 1, except that the amount of ammonium paratungstate added was changed to 0.281 kg when preparing the composite oxide granular powder (a ′) obtained in Example 1. Thus, a composite oxide granular powder (c ′) was obtained.
Further, the titanium-containing granular powder was prepared in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the granular powder (c ′) of this composite oxide was changed to 1.13 kg. (C) was prepared.
Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (c) thus obtained by the atomic weight is obtained. Furthermore, the value B obtained by dividing the mass of the nitrogen atom which is an element constituting the additive (ammonium paratungstate) by the atomic weight was determined. As a result, the values A and B were 297 and 3.60, respectively, and the ratio (B / A) was 1.21 × 10 −2 .
Further, when the titanium-containing granular powder (c) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.96. Furthermore, it was 93 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (C)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (c) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (C) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例４］
＜チタン含有粒状粉末（ｄ）及びハニカム状排ガス処理触媒（Ｄ）＞
(1) チタン含有粒状粉末（ｄ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）を調製する際にメタチタン酸スラリーを二酸化チタン換算で２２．５ｋｇとパラタングステン酸アンモニウムの添加量を１．４１ｋｇに変えたこと以外は、実施例１と同様の方法にて調製して複合酸化物の粒状粉体（ｄ’）を得た。
また、この複合酸化物の粒状粉体（ｄ’）に添加剤として加えたパラタングステン酸アンモニウムの量を１．４１ｋｇに変えた以外は、実施例１と同様の方法にてチタン含有粒状粉末（ｄ）を調製した。
次に、このようにして得られたチタン含有粒状粉末（ｄ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２８２および４．４９であり、その比（Ｂ／Ａ）は１．６０×１０−２であった。
また、前記チタン含有粒状粉末（ｄ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９１であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、８８ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｄ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｄ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｄ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８５．１／９．４５／０．５０／５．００であった。
[Example 4]
<Titanium-containing granular powder (d) and honeycomb-shaped exhaust gas treatment catalyst (D)>
(1) Titanium-containing granular powder (d)
When preparing the composite oxide granular powder (a ′) obtained in Example 1, the metatitanic acid slurry was changed to 22.5 kg in terms of titanium dioxide and the addition amount of ammonium paratungstate was changed to 1.41 kg. Except for the above, a composite oxide granular powder (d ′) was obtained in the same manner as in Example 1.
Further, a titanium-containing granular powder (in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the granular powder (d ′) of this composite oxide was changed to 1.41 kg. d) was prepared.
Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (d) thus obtained by the atomic weight is obtained. Furthermore, the value B obtained by dividing the mass of the nitrogen atom which is an element constituting the additive (ammonium paratungstate) by the atomic weight was determined. As a result, the values A and B were 282 and 4.49, respectively, and the ratio (B / A) was 1.60 × 10 −2 .
Further, when the titanium-containing granular powder (d) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.91. Furthermore, it was 88 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (D)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (d) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (D) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=85.1/9.45/0.50/5, respectively. 0.00.
［実施例５］
＜チタン含有粒状粉末（ｅ）及びハニカム状排ガス処理触媒（Ｅ）＞
(1) チタン含有粒状粉末（ｅ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）を調製する際にメタチタン酸スラリーを二酸化チタン換算で２０．０ｋｇとパラタングステン酸アンモニウムの添加量を２．８１ｋｇに変えたこと以外は、実施例１と同様の方法にて調製して複合酸化物の粒状粉体（ｅ’）を得た。
また、この複合酸化物の粒状粉体（ｅ’）に添加剤として加えたパラタングステン酸アンモニウムの量を２．８１ｋｇに変えたこと以外は、実施例１と同様の方法にてチタン含有粒状粉末（ｅ）を調製した。
次に、このようにして得られたチタン含有粒状粉末（ｅ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２５０および８．９９であり、その比（Ｂ／Ａ）は３．５９×１０−２であった。
また、前記チタン含有粒状粉末（ｅ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．８３であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、７６ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｅ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｅ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｅ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝７５．６／１８．９／０．５０／５．００であった。
[Example 5]
<Titanium-containing granular powder (e) and honeycomb-shaped exhaust gas treatment catalyst (E)>
(1) Titanium-containing granular powder (e)
When preparing the granular powder (a ′) of the composite oxide obtained in Example 1, the metatitanic acid slurry was changed to 20.0 kg in terms of titanium dioxide and the addition amount of ammonium paratungstate was changed to 2.81 kg. Except for the above, a composite oxide granular powder (e ′) was obtained by the same method as in Example 1.
Further, a titanium-containing granular powder was produced in the same manner as in Example 1 except that the amount of ammonium paratungstate added as an additive to the granular powder (e ′) of this composite oxide was changed to 2.81 kg. (E) was prepared.
Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (e) thus obtained by the atomic weight is obtained. Furthermore, the value B obtained by dividing the mass of the nitrogen atom which is an element constituting the additive (ammonium paratungstate) by the atomic weight was determined. As a result, the values A and B were 250 and 8.99, respectively, and the ratio (B / A) was 3.59 × 10 −2 .
Further, when the titanium-containing granular powder (e) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.83. Furthermore, it was 76 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (E)
Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (e) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (E) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=75.6/18.9/0.50/5, respectively. 0.00.
［実施例６］
＜チタン含有粒状粉末（ｆ）及びハニカム状排ガス処理触媒（Ｆ）＞
(1) チタン含有粒状粉末（ｆ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）に加えた添加剤を二硫化タングステン（添加量０．２６７ｋｇ）に変えたこと以外は、実施例１と同様の方法でチタン含有粒状粉末（ｆ）を得た。
次に、このようにして得られたチタン含有粒状粉末（ｆ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（二硫化タングステン）を構成する元素である硫黄原子の質量をその原子量で除して得られる値Ｃを求めた。その結果、前記の値ＡおよびＣは、それぞれ２９７および２．１６であり、その比（Ｃ／Ａ）は７．２６×１０−３であった。
また、前記チタン含有粒状粉末（ｆ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９５であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９４ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｆ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｆ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｆ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 6]
<Titanium-containing granular powder (f) and honeycomb-shaped exhaust gas treatment catalyst (F)>
(1) Titanium-containing granular powder (f)
Titanium was prepared in the same manner as in Example 1, except that the additive added to the composite oxide granular powder (a ′) obtained in Example 1 was changed to tungsten disulfide (added amount: 0.267 kg). The contained granular powder (f) was obtained.
Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (f) thus obtained by the atomic weight is obtained. Further, a value C obtained by dividing the mass of sulfur atoms , which are elements constituting the additive (tungsten disulfide), by the atomic weight was determined. As a result, the values A and C were 297 and 2.16, respectively, and the ratio (C / A) was 7.26 × 10 −3 .
Further, when the titanium-containing granular powder (f) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95. Furthermore, it was 94 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (F)
Next, a honeycomb-shaped exhaust gas comprising a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (f) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (F) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例７］
＜チタン含有粒状粉末（ｇ）及びハニカム状排ガス処理触媒（Ｇ）＞
(1) チタン含有粒状粉末（ｇ）
実施例２で得られた複合酸化物の粒状粉体（ｂ’）に加えた添加剤を二硫化タングステン（添加量０．５３５ｋｇ）に変えたこと以外は、実施例１と同様の方法でチタン含有粒状粉末（ｇ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｇ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（二硫化タングステン）を構成する元素である硫黄原子の質量をその原子量で除して得られる値Ｃを求めた。その結果、前記の値ＡおよびＣは、それぞれ２９７および４．３１であり、その比（Ｃ／Ａ）は１．４５×１０−２であった。
また、前記チタン含有粒状粉末（ｇ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９５であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９４ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｇ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｇ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｇ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 7]
<Titanium-containing granular powder (g) and honeycomb-shaped exhaust gas treatment catalyst (G)>
(1) Titanium-containing granular powder (g)
Titanium was obtained in the same manner as in Example 1 except that the additive added to the granular powder (b ′) of the composite oxide obtained in Example 2 was changed to tungsten disulfide (addition amount: 0.535 kg). The contained granular powder (g) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (g) thus obtained by the atomic weight is obtained. Further, a value C obtained by dividing the mass of sulfur atoms , which are elements constituting the additive (tungsten disulfide), by the atomic weight was determined. As a result, the values A and C were 297 and 4.31, respectively, and the ratio (C / A) was 1.45 × 10 −2 .
Further, when the titanium-containing granular powder (g) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95. Furthermore, it was 94 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (G)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (g) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (G) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例８］
＜チタン含有粒状粉末（ｈ）及びハニカム状排ガス処理触媒（Ｈ）＞
(1) チタン含有粒状粉末（ｈ）
実施例３で得られた複合酸化物の粒状粉体（ｃ’）に加えた添加剤を二硫化タングステン（添加量１．０７ｋｇ）に変えたこと以外は、実施例１と同様の方法でチタン含有粒状粉末（ｈ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｈ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（二硫化タングステン）を構成する元素である硫黄原子の質量をその原子量で除して得られる値Ｃを求めた。その結果、前記の値ＡおよびＣは、それぞれ２９７および８．６３であり、その比（Ｃ／Ａ）は２．９０×１０−２であった。
また、前記チタン含有粒状粉末（ｈ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９７であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９４ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｈ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｈ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｈ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 8]
<Titanium-containing granular powder (h) and honeycomb-shaped exhaust gas treatment catalyst (H)>
(1) Titanium-containing granular powder (h)
Titanium was prepared in the same manner as in Example 1, except that the additive added to the composite oxide granular powder (c ′) obtained in Example 3 was changed to tungsten disulfide (added amount: 1.07 kg). The contained granular powder (h) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (h) thus obtained by the atomic weight is obtained. Further, a value C obtained by dividing the mass of sulfur atoms , which are elements constituting the additive (tungsten disulfide), by the atomic weight was determined. As a result, the values A and C were 297 and 8.63, respectively, and the ratio (C / A) was 2.90 × 10 −2 .
Further, when the titanium-containing granular powder (h) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.97. Furthermore, it was 94 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (H)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (h) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (H) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例９］
＜チタン含有粒状粉末（ｉ）及びハニカム状排ガス処理触媒（Ｉ）＞
(1) チタン含有粒状粉末（ｉ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）に加えた添加剤を六塩化タングステン（添加量０．４３ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｉ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｉ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（六塩化タングステン）を構成する元素である塩素原子の質量をその原子量で除して得られる値Ｄを求めた。その結果、前記の値ＡおよびＤは、それぞれ２９７および６．４７であり、その比（Ｄ／Ａ）は２．１８×１０−２であった。
また、前記チタン含有粒状粉末（ｉ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９７であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９１ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｉ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｉ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｉ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 9]
<Titanium-containing granular powder (i) and honeycomb-shaped exhaust gas treatment catalyst (I)>
(1) Titanium-containing granular powder (i)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (a ′) of the composite oxide obtained in Example 1 was changed to tungsten hexachloride (addition amount 0.43 kg). A granular powder (i) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (i) thus obtained by the atomic weight is obtained. It was determined more value D obtained by dividing the mass of the element a is chlorine atom constituting the additive (tungsten hexachloride) in its atomic weight. As a result, the values A and D were 297 and 6.47, respectively, and the ratio (D / A) was 2.18 × 10 −2 .
Further, when the titanium-containing granular powder (i) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.97. Furthermore, it was 91 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (I)
Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (i) was used instead of the titanium-containing granular powder (a) described in Example 1. Treated catalyst (I) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例１０］
＜チタン含有粒状粉末（ｊ）及びハニカム状排ガス処理触媒（Ｊ）＞
(1) チタン含有粒状粉末（ｊ）
実施例２で得られた複合酸化物の粒状粉体（ｂ’）に加えた添加剤を六塩化タングステン（添加量０．８６ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｊ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｊ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（六塩化タングステン）を構成する元素である塩素原子の質量をその原子量で除して得られる値Ｄを求めた。その結果、前記の値ＡおよびＤは、それぞれ２９７および１２．９であり、その比（Ｄ／Ａ）は４．３５×１０−２であった。
また、前記チタン含有粒状粉末（ｊ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９６であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９２ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｊ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｊ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｊ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 10]
<Titanium-containing granular powder (j) and honeycomb-shaped exhaust gas treatment catalyst (J)>
(1) Titanium-containing granular powder (j)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (b ′) of the composite oxide obtained in Example 2 was changed to tungsten hexachloride (addition amount 0.86 kg). A granular powder (j) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (j) thus obtained by the atomic weight is obtained. It was determined more value D obtained by dividing the mass of the element a is chlorine atom constituting the additive (tungsten hexachloride) in its atomic weight. As a result, the values A and D were 297 and 12.9, respectively, and the ratio (D / A) was 4.35 × 10 −2 .
Further, when the titanium-containing granular powder (j) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.96. Furthermore, it was 92 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (J)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (j) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (J) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例１１］
＜チタン含有粒状粉末（ｋ）及びハニカム状排ガス処理触媒（Ｋ）＞
(1) チタン含有粒状粉末（ｋ）
実施例３で得られた複合酸化物の粒状粉体（ｃ’）に加えた添加剤を六塩化タングステン（添加量１．７１ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｋ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｋ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（六塩化タングステン）を構成する元素である塩素原子の質量をその原子量で除して得られる値Ｄを求めた。その結果、前記の値ＡおよびＤは、それぞれ２９７および２５．９であり、その比（Ｄ／Ａ）は８．７１×１０−２であった。
また、前記チタン含有粒状粉末（ｋ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９５であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９４ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｋ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｋ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｋ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 11]
<Titanium-containing granular powder (k) and honeycomb-shaped exhaust gas treatment catalyst (K)>
(1) Titanium-containing granular powder (k)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (c ′) of the composite oxide obtained in Example 3 was changed to tungsten hexachloride (addition amount 1.71 kg). A granular powder (k) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (k) thus obtained by the atomic weight is obtained. It was determined more value D obtained by dividing the mass of the element a is chlorine atom constituting the additive (tungsten hexachloride) in its atomic weight. As a result, the values A and D were 297 and 25.9, respectively, and the ratio (D / A) was 8.71 × 10 −2 .
Further, when the titanium-containing granular powder (k) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.95. Furthermore, it was 94 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (K)
Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (k) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (K) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［実施例１２］
＜チタン含有粒状粉末（ｌ）及びハニカム状排ガス処理触媒（Ｌ）＞
(1) チタン含有粒状粉末（ｌ）
実施例２で得られた複合酸化物の粒状粉体（ｂ’）に加えた添加剤をモリブデン酸アンモニウム（添加量０．６１３ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｌ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｌ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（モリブデン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２９７および２．９８であり、その比（Ｂ／Ａ）は１．００×１０−２であった。
また、前記チタン含有粒状粉末（ｌ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９８であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９３ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｌ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｌ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｌ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／ＭｏＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／２．８４／１．８９／０．５００／５．００であった。
[Example 12]
<Titanium-containing granular powder (l) and honeycomb-shaped exhaust gas treatment catalyst (L)>
(1) Titanium-containing granular powder (l)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (b ′) of the composite oxide obtained in Example 2 was changed to ammonium molybdate (addition amount 0.613 kg). A granular powder (l) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (l) thus obtained by the atomic weight is obtained. Further, a value B obtained by dividing the mass of nitrogen atoms , which are elements constituting the additive (ammonium molybdate), by the atomic weight was determined. As a result, the values A and B were 297 and 2.98, respectively, and the ratio (B / A) was 1.00 × 10 −2 .
Further, when the titanium-containing granular powder (l) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.98. Furthermore, it was 93 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (L)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (l) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (L) was prepared. The weight composition ratio represents a metal element contained in the honeycomb structure on an oxide basis, respectively TiO 2 / WO 3 / MoO 3 / V 2 O 5 /GF=89.8/2.84/1. It was 89 / 0.500 / 5.00.
［実施例１３］
＜チタン含有粒状粉末（ｍ）及びハニカム状排ガス処理触媒（Ｍ）＞
(1) チタン含有粒状粉末（ｍ）
実施例２で得られた複合酸化物の粒状粉体（ｂ’）に加えた添加剤を二硫化モリブデン（添加量０．５６２ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｍ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｍ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（二硫化モリブデン）を構成する元素である硫黄原子の質量をその原子量で除して得られる値Ｃを求めた。その結果、前記の値ＡおよびＣは、それぞれ２９７および６．９５であり、その比（Ｃ／Ａ）は２．３４×１０−２であった。
また、前記チタン含有粒状粉末（ｍ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９７であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９２ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｍ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｍ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｍ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／ＭｏＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／２．８４／１．８９／０．５００／５．００であった。
[Example 13]
<Titanium-containing granular powder (m) and honeycomb-shaped exhaust gas treatment catalyst (M)>
(1) Titanium-containing granular powder (m)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (b ′) of the composite oxide obtained in Example 2 was changed to molybdenum disulfide (added amount: 0.562 kg). A granular powder (m) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (m) thus obtained by the atomic weight is obtained. Further, a value C obtained by dividing the mass of sulfur atoms , which are elements constituting the additive (molybdenum disulfide), by the atomic weight was determined. As a result, the values A and C were 297 and 6.95, respectively, and the ratio (C / A) was 2.34 × 10 −2 .
Further, when the titanium-containing granular powder (m) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.97. Furthermore, it was 92 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (M)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (m) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (M) was prepared. The weight composition ratio represents a metal element contained in the honeycomb structure on an oxide basis, respectively TiO 2 / WO 3 / MoO 3 / V 2 O 5 /GF=89.8/2.84/1. It was 89 / 0.500 / 5.00.
［実施例１４］
＜チタン含有粒状粉末（ｎ）及びハニカム状排ガス処理触媒（Ｎ）＞
(1) チタン含有粒状粉末（ｎ）
実施例２で得られた複合酸化物の粒状粉体（ｂ’）に加えた添加剤を五塩化モリブデン（添加量０．９５１ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｎ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｎ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（五塩化モリブデン）を構成する元素である塩素原子の質量をその原子量で除して得られる値Ｄを求めた。その結果、前記の値ＡおよびＤは、それぞれ２９７および１７．４であり、その比（Ｄ／Ａ）は５．８４×１０−２であった。
また、前記チタン含有粒状粉末（ｎ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９８であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、９２ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｎ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｎ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｎ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／ＭｏＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／２．８４／１．８９／０．５００／５．００であった。
[Example 14]
<Titanium-containing granular powder (n) and honeycomb-shaped exhaust gas treatment catalyst (N)>
(1) Titanium-containing granular powder (n)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (b ′) of the composite oxide obtained in Example 2 was changed to molybdenum pentachloride (added amount: 0.951 kg). A granular powder (n) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (n) thus obtained by the atomic weight is obtained. It was determined more value D obtained by dividing the mass of the element a is chlorine atom constituting the additive (pentachloride molybdenum) at its atomic weight. As a result, the values A and D were 297 and 17.4, respectively, and the ratio (D / A) was 5.84 × 10 −2 .
Further, when the titanium-containing granular powder (n) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.98. Furthermore, it was 92 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (N)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (n) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (N) was prepared. The weight composition ratio represents a metal element contained in the honeycomb structure on an oxide basis, respectively TiO 2 / WO 3 / MoO 3 / V 2 O 5 /GF=89.8/2.84/1. It was 89 / 0.500 / 5.00.
［実施例１５］
＜チタン含有粒状粉末（ｏ）及びハニカム状排ガス処理触媒（Ｏ）＞
(1) チタン含有粒状粉末（ｏ）
実施例４で得られた複合酸化物の粒状粉体（ｄ’）に加えた添加剤をモリブデン酸アンモニウム（添加量１．５３ｋｇ）に変えた以外は、実施例１と同様の方法でチタン含有粒状粉末（ｏ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｏ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（モリブデン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２８２および７．４５であり、その比（Ｂ／Ａ）は２．６４×１０−２であった。
また、前記チタン含有粒状粉末（ｏ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９０であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、８５ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｏ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｏ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｏ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／ＭｏＯ３／Ｖ２Ｏ５／ＧＦ＝８５．１／４．７３／４．７３／０．５００／５．００であった。
[Example 15]
<Titanium-containing granular powder (o) and honeycomb-shaped exhaust gas treatment catalyst (O)>
(1) Titanium-containing granular powder (o)
Titanium-containing in the same manner as in Example 1 except that the additive added to the granular powder (d ′) of the composite oxide obtained in Example 4 was changed to ammonium molybdate (addition amount 1.53 kg). A granular powder (o) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (o) thus obtained by the atomic weight is obtained. Further, a value B obtained by dividing the mass of nitrogen atoms , which are elements constituting the additive (ammonium molybdate), by the atomic weight was determined. As a result, the values A and B were 282 and 7.45, respectively, and the ratio (B / A) was 2.64 × 10 −2 .
Further, when the titanium-containing granular powder (o) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.90. Furthermore, it was 85 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (O)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (o) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (O) was prepared. The weight composition ratio represents a metal element contained in the honeycomb structure on an oxide basis, respectively TiO 2 / WO 3 / MoO 3 / V 2 O 5 /GF=85.1/4.73/4. It was 73 / 0.500 / 5.00.
［実施例１６］
＜チタン含有粒状粉末（ｐ）及びハニカム状排ガス処理触媒（Ｐ）＞
(1) チタン含有粒状粉末（ｐ）
実施例５で得られた複合酸化物の粒状粉体（ｅ’）に加えた添加剤をモリブデン酸アンモニウム（添加量３．０７ｋｇ）に変えた点以外は、実施例１と同様の方法でチタン含有粒状粉末（ｐ）を得た。次に、このようにして得られたチタン含有粒状粉末（ｐ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（モリブデン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２５０および１４．９であり、その比（Ｂ／Ａ）は５．９５×１０−２であった。
また、前記チタン含有粒状粉末（ｐ）を上記に示すＸ線回折により測定したところ、該チタン含有粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．８３であった。さらに、前記チタン含有粒状粉末の比表面積を上記の方法により測定したところ、７８ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｐ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｐ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｐ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／ＭｏＯ３／Ｖ２Ｏ５／ＧＦ＝７５．６／９．４５／９．４５／０．５００／５．００であった。
［比較例１］
＜複合酸化物の粒状粉体（ｑ）及びハニカム状排ガス処理触媒（Ｑ）＞
(1) 複合酸化物の粒状粉体（ｑ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）を調製する際にメタチタン酸スラリーを二酸化チタン換算で２３．６ｋｇとパラタングステン酸アンモニウムの添加量を１．４１ｋｇに変えたこと以外は、実施例１の複合酸化物の粒状粉体（ａ’）と同様の方法にて調製して複合酸化物の粒状粉体（ｑ）を得た。
また、前記複合酸化物の粒状粉体（ｑ）を上記に示すＸ線回折により測定したところ、該複合酸化物の粒状粉体中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９７であった。さらに、前記複合酸化物の粒状粉体の比表面積を上記の方法により測定したところ、９２ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｑ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、この複合酸化物の粒状粉体（ｑ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｑ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Example 16]
<Titanium-containing granular powder (p) and honeycomb-shaped exhaust gas treatment catalyst (P)>
(1) Titanium-containing granular powder (p)
Titanium was prepared in the same manner as in Example 1 except that the additive added to the granular powder (e ′) of the composite oxide obtained in Example 5 was changed to ammonium molybdate (amount added: 3.07 kg). The contained granular powder (p) was obtained. Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (p) thus obtained by the atomic weight is obtained. Further, a value B obtained by dividing the mass of nitrogen atoms , which are elements constituting the additive (ammonium molybdate), by the atomic weight was determined. As a result, the values A and B were 250 and 14.9, respectively, and the ratio (B / A) was 5.95 × 10 −2 .
Further, when the titanium-containing granular powder (p) was measured by the X-ray diffraction shown above, the titanium oxide contained in the titanium-containing granular powder had an anatase type crystal structure, and the ratio of the peak intensities (P 1 / P 0 ) was 0.83. Furthermore, it was 78 m < 2 > / g when the specific surface area of the said titanium containing granular powder was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (P)
Next, a honeycomb-shaped exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (p) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (P) was prepared. The weight composition ratio represents a metal element contained in the honeycomb structure on an oxide basis, respectively TiO 2 / WO 3 / MoO 3 / V 2 O 5 /GF=75.6/9.45/9. It was 45 / 0.500 / 5.00.
[Comparative Example 1]
<Particulate oxide powder (q) and honeycomb-shaped exhaust gas treatment catalyst (Q)>
(1) Granular powder of complex oxide (q)
In preparing the composite oxide granular powder (a ′) obtained in Example 1, the metatitanic acid slurry was changed to 23.6 kg in terms of titanium dioxide and the addition amount of ammonium paratungstate was changed to 1.41 kg. Except for the above, a composite oxide granular powder (q) was prepared in the same manner as in the composite oxide granular powder (a ′) of Example 1.
Further, when the granular powder (q) of the composite oxide was measured by the X-ray diffraction shown above, the titanium oxide contained in the granular powder of the composite oxide had an anatase type crystal structure. The peak intensity ratio (P 1 / P 0 ) was 0.97. Furthermore, it was 92 m < 2 > / g when the specific surface area of the granular powder of the said complex oxide was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (Q)
Next, a honeycomb structure was formed in the same manner as in Example 1 except that this composite oxide granular powder (q) was used instead of the titanium-containing granular powder (a) described in Example 1. A honeycomb-shaped exhaust gas treatment catalyst (Q) was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［比較例２］
＜二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）及びハニカム状排ガス処理触媒（Ｒ）＞
(1) 二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）
メタチタン酸スラリー（二酸化チタン換算で２５．０ｋｇ）にパラタングステン酸アンモニウムを添加しない以外は、実施例１の（ａ’）と同様の方法にて二酸化チタンの粒状粉体（ｒ’）を調製した。次いで、この二酸化チタンの粒状粉体（ｒ’）に、パラタングステン酸アンモニウムを１．４１ｋｇ加え、ブレンダーで均一になるように混合して二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）を調製した。このように調製された二酸化チタンとパラタングステン酸アンモニウムの粒状粉体をボールミルを用いて解砕し、その全量の９９．９質量％以上が４５μｍ以下の粒子径をもつ二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）を得た。
次に、このようにして得られた二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２９７および４．４９であり、その比（Ｂ／Ａ）は１．５１×１０−２であった。
また、前記二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）を上記に示すＸ線回折により測定したところ、該二酸化チタンとパラタングステン酸アンモニウムの粒状粉体中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９７であった。さらに、前記二酸化チタンとパラタングステン酸アンモニウムの粒状粉体の比表面積を上記の方法により測定したところ、９５ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｒ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｒ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８９．８／４．７３／０．５０／５．００であった。
[Comparative Example 2]
<Titanium dioxide and ammonium paratungstate granular powder (r) and honeycomb-shaped exhaust gas treatment catalyst (R)>
(1) Granular powder of titanium dioxide and ammonium paratungstate (r)
A granular powder (r ′) of titanium dioxide was prepared in the same manner as in (a ′) of Example 1 except that ammonium paratungstate was not added to the metatitanic acid slurry (25.0 kg in terms of titanium dioxide). . Next, 1.41 kg of ammonium paratungstate is added to the granular powder (r ′) of titanium dioxide, and mixed uniformly with a blender to obtain granular powder (r) of titanium dioxide and ammonium paratungstate. Prepared. The granular powder of titanium dioxide and ammonium paratungstate prepared in this manner is crushed using a ball mill, and 99.9% by mass or more of the total amount of titanium dioxide and ammonium paratungstate have a particle size of 45 μm or less. Granular powder (r) was obtained.
Next, the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the granular powder (r) of titanium dioxide and ammonium paratungstate thus obtained is divided by the atomic weight. The value A obtained was obtained, and the value B obtained by dividing the mass of the nitrogen atom that is an element constituting the additive (ammonium paratungstate) by the atomic weight was obtained. As a result, the values A and B were 297 and 4.49, respectively, and the ratio (B / A) was 1.51 × 10 −2 .
Further, when the granular powder (r) of titanium dioxide and ammonium paratungstate was measured by the X-ray diffraction shown above, the titanium oxide contained in the granular powder of titanium dioxide and ammonium paratungstate was anatase type. The peak intensity ratio (P 1 / P 0 ) was 0.97. Furthermore, it was 95 m < 2 > / g when the specific surface area of the granular powder of the said titanium dioxide and ammonium paratungstate was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (R)
Next, in place of the titanium-containing granular powder (a) described in Example 1, this honeycomb and ammonium paratungstate granular powder (r) was used in the same manner as in Example 1 to obtain a honeycomb structure. A honeycomb-shaped exhaust gas treatment catalyst (R) comprising a body was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=89.8/4.73/0.50/5, respectively. 0.00.
［比較例４］
＜二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｔ）及びハニカム状排ガス処理触媒（Ｔ）＞
(1) 二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｔ）
比較例２の二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）２２．５ｋｇにパラタングステン酸アンモニウム（２．８１ｋｇ）を混合する以外は、比較例２と同様の方法により、チタンとパラタングステン酸アンモニウムの粒状粉体（ｔ）を得た。
次に、このようにして得られたチタンとパラタングステン酸アンモニウムの粒状粉体（ｔ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２８２および８．９９であり、その比（Ｂ／Ａ）は３．１９×１０−２であった。
また、前記二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｔ）を上記に示すＸ線回折により測定したところ、該二酸化チタンとパラタングステン酸アンモニウムの粒状粉体中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．９２であった。さらに、前記二酸化チタンとパラタングステン酸アンモニウムの粒状粉体の比表面積を上記の方法により測定したところ、８５ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｔ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、この二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｔ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｔ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝８５．１／９．４５／０．５０／５．００であった。
[Comparative Example 4]
<Titanium dioxide and ammonium paratungstate granular powder (t) and honeycomb-shaped exhaust gas treatment catalyst (T)>
(1) Granular powder of titanium dioxide and ammonium paratungstate (t)
Titanium and paratungsten were produced in the same manner as in Comparative Example 2 except that 22.5 kg of granular powder (r) of titanium dioxide and ammonium paratungstate of Comparative Example 2 was mixed with ammonium paratungstate (2.81 kg). A granular powder (t) of ammonium acid was obtained.
Next, the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the granular powder (t) of titanium and ammonium paratungstate thus obtained is divided by the atomic weight. The obtained value A was determined, and further the value B obtained by dividing the mass of nitrogen atoms , which are the elements constituting the additive (ammonium paratungstate), by the atomic weight was determined. As a result, the values A and B were 282 and 8.99, respectively, and the ratio (B / A) was 3.19 × 10 −2 .
Further, when the granular powder (t) of titanium dioxide and ammonium paratungstate was measured by the X-ray diffraction shown above, the titanium oxide contained in the granular powder of titanium dioxide and ammonium paratungstate was anatase type. The peak intensity ratio (P 1 / P 0 ) was 0.92. Furthermore, it was 85 m < 2 > / g when the specific surface area of the granular powder of the said titanium dioxide and ammonium paratungstate was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (T)
Next, in the same manner as in Example 1, except that this titanium dioxide and ammonium paratungstate granular powder (t) was used instead of the titanium-containing granular powder (a) described in Example 1, the honeycomb was obtained. A honeycomb-shaped exhaust gas treatment catalyst (T) comprising a structure was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=85.1/9.45/0.50/5, respectively. 0.00.
［比較例６］
＜二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｖ）及びハニカム状排ガス処理触媒（Ｖ）＞
(1) 二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｖ）
比較例２の二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｒ）２０．０ｋｇにパラタングステン酸アンモニウム（５．６３ｋｇ）を混合する以外は、比較例２と同様の方法により、二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｖ）を得た。
次に、このようにして得られた二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｖ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（パラタングステン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ２５０および１８．０であり、その比（Ｂ／Ａ）は７．１８×１０−２であった。
また、前記二酸化チタンとパラタングステン酸アンモニウムの粒状粉体（ｖ）を上記に示すＸ線回折により測定したところ、該二酸化チタンとパラタングステン酸アンモニウムの粒状粉体中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．８０であった。さらに、前記二酸化チタンとパラタングステン酸アンモニウムの粒状粉体の比表面積を上記の方法により測定したところ、７５ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｖ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタンとパラタングステン酸アンモニウムの粒状粉体（ｖ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｖ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／Ｖ２Ｏ５／ＧＦ＝７５．６／１８．９／０．５０／５．００であった。
[Comparative Example 6]
<Titanium dioxide and ammonium paratungstate granular powder (v) and honeycomb-shaped exhaust gas treatment catalyst (V)>
(1) Granular powder of titanium dioxide and ammonium paratungstate (v)
Except for mixing ammonium paratungstate (5.63 kg) with 20.0 kg of granular powder (r) of titanium dioxide and ammonium paratungstate of Comparative Example 2, titanium dioxide and para A granular powder (v) of ammonium tungstate was obtained.
Next, the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the granular powder (v) of titanium dioxide and ammonium paratungstate thus obtained is divided by the atomic weight. The value A obtained was obtained, and the value B obtained by dividing the mass of the nitrogen atom that is an element constituting the additive (ammonium paratungstate) by the atomic weight was obtained. As a result, the values A and B were 250 and 18.0, respectively, and the ratio (B / A) was 7.18 × 10 −2 .
Further, when the granular powder (v) of titanium dioxide and ammonium paratungstate was measured by the X-ray diffraction shown above, the titanium oxide contained in the granular powder of titanium dioxide and ammonium paratungstate was anatase type. The peak intensity ratio (P 1 / P 0 ) was 0.80. Furthermore, it was 75 m < 2 > / g when the specific surface area of the granular powder of the said titanium dioxide and ammonium paratungstate was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (V)
Subsequently, in place of the titanium-containing granular powder (a) described in Example 1, this honeycomb and ammonium paratungstate granular powder (v) was used in the same manner as in Example 1 to obtain a honeycomb structure. A honeycomb-shaped exhaust gas treatment catalyst (V) comprising a body was prepared. The weight composition ratios of the metal elements contained in this honeycomb structure on the basis of oxides were TiO 2 / WO 3 / V 2 O 5 /GF=75.6/18.9/0.50/5, respectively. 0.00.
［比較例１０］
＜チタン含有粒状粉末（ｚ）及びハニカム状排ガス処理触媒（Ｚ）＞
(1) チタン含有粒状粉末（ｚ）
実施例１で得られた複合酸化物の粒状粉体（ａ’）を調製する際にメタチタン酸スラリーを二酸化チタン換算で１５．０ｋｇとパラタングステン酸アンモニウムの添加量を０．８４５ｋｇに変えたこと以外は、実施例１と同様の方法にて調製して複合酸化物の粒状粉体（ｚ’）を得た。
また、この複合酸化物の粒状粉体（ｚ’）に加える添加剤をモリブデン酸アンモニウム１１．３ｋｇに変えた以外は、実施例１と同様の方法にてチタン含有粒状粉末（ｚ）を調製した。
次に、このようにして得られたチタン含有粒状粉末（ｚ）中に含まれる、前記複合酸化物を構成する金属元素であるチタン原子の質量をその原子量で除して得られる値Ａを求め、さらに前記添加剤（モリブデン酸アンモニウム）を構成する元素である窒素原子の質量をその原子量で除して得られる値Ｂを求めた。その結果、前記の値ＡおよびＢは、それぞれ１８８および５５．１であり、その比（Ｂ／Ａ）は２．９３×１０−１であった。
また、前記複合酸化物の粒状粉末（ｚ）を上記に示すＸ線回折により測定したところ、該複合酸化物の粒状粉末中に含まれる酸化チタンがアナターゼ型の結晶構造を有しており、前記ピーク強度の比（Ｐ1／Ｐ0）が０．７５であった。さらに、前記複合酸化物の粒状粉末の比表面積を上記の方法により測定したところ、７０ｍ２／ｇであった。
(2) ハニカム状排ガス処理触媒（Ｚ）
次いで、実施例１に記載のチタン含有粒状粉末（ａ）の代わりに、このチタン含有粒状粉末（ｚ）を用いた以外は、実施例１と同様の方法により、ハニカム構造体からなるハニカム状排ガス処理触媒（Ｚ）を調製した。なお、このハニカム構造体に含まれる金属元素を酸化物基準で表した重量組成比は、それぞれＴｉＯ２／ＷＯ３／ＭｏＯ３／Ｖ２Ｏ５／ＧＦ＝５６．７／２．８４／３５．０／０．５００／５．００であった。
[Comparative Example 10]
<Titanium-containing granular powder (z) and honeycomb-shaped exhaust gas treatment catalyst (Z)>
(1) Titanium-containing granular powder (z)
In preparing the composite oxide granular powder (a ′) obtained in Example 1, the metatitanic acid slurry was changed to 15.0 kg in terms of titanium dioxide and the addition amount of ammonium paratungstate was changed to 0.845 kg. Except for the above, a composite oxide granular powder (z ′) was obtained in the same manner as in Example 1.
A titanium-containing granular powder (z) was prepared in the same manner as in Example 1, except that the additive added to the composite oxide granular powder (z ′) was changed to 11.3 kg of ammonium molybdate. .
Next, a value A obtained by dividing the mass of titanium atoms, which are metal elements constituting the composite oxide, contained in the titanium-containing granular powder (z) thus obtained by the atomic weight is obtained. Further, a value B obtained by dividing the mass of nitrogen atoms , which are elements constituting the additive (ammonium molybdate), by the atomic weight was determined. As a result, the values A and B were 188 and 55.1, respectively, and the ratio (B / A) was 2.93 × 10 −1 .
Further, when the composite oxide granular powder (z) was measured by the X-ray diffraction shown above, the titanium oxide contained in the composite oxide granular powder had an anatase type crystal structure, The peak intensity ratio (P 1 / P 0 ) was 0.75. Furthermore, it was 70 m < 2 > / g when the specific surface area of the granular powder of the said complex oxide was measured by said method.
(2) Honeycomb exhaust gas treatment catalyst (Z)
Next, a honeycomb-like exhaust gas composed of a honeycomb structure was produced in the same manner as in Example 1 except that this titanium-containing granular powder (z) was used instead of the titanium-containing granular powder (a) described in Example 1. A treated catalyst (Z) was prepared. The weight composition ratio represents a metal element contained in the honeycomb structure on an oxide basis, respectively TiO 2 / WO 3 / MoO 3 / V 2 O 5 /GF=56.7/2.84/35. It was 0 / 0.500 / 5.00.
チタン含有粒状粉末、複合酸化物及びチタン粉末とパラタングステン酸アンモニウムの混合物（以下、これらをまとめて「チタン含有粒状粉末等」ともいう。）（ａ）〜（ｚ）についての前記Ａ〜Ｄの値を（表１）に示し、チタン含有粒状粉末等（ａ）〜（ｚ）についての比表面積（ＳＡ）、アナターゼ型結晶の（１０１）面のピーク強度の比（Ｐ1／Ｐ0）、ハニカム状排ガス処理触媒（Ａ）〜（Ｚ）の比表面積（ＳＡ）、細孔容積（ＰＶ）、成型性試験の結果、脱硝率、摩耗率、耐熱性（試験前後のアナターゼ型結晶の（１０１）面のピーク強度の比（Ｐ1’／Ｐ1）を（表２）に示す。
Titanium-containing granular powder, composite oxide and mixture of titanium powder and ammonium paratungstate (hereinafter collectively referred to as “titanium-containing granular powder etc.”) A to D of (A) to (z) above The values are shown in (Table 1), the specific surface area (SA) for the titanium-containing granular powders etc. (a) to (z), the ratio of the peak intensity of the (101) plane of the anatase type crystal (P 1 / P 0 ), As a result of the specific surface area (SA), pore volume (PV), moldability test of honeycomb-shaped exhaust gas treatment catalyst (A) to (Z), denitration rate, wear rate, heat resistance ((101 The ratio (P 1 ′ / P 1 ) of the peak intensity of the) plane is shown in Table 2.
Claims (12)
（１）前記添加剤（Ｙ）として、（i）タングステン含有窒素化合物または（iv）モリブデン含有窒素化合物を含む場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる窒素原子のモル数をＢで表したとき、そのモル比（Ｂ／Ａ）が、８．７０×１０−４〜２．７８×１０−１の範囲にあり、
（２）前記添加剤（Ｙ）として、（ii）タングステン含有硫黄化合物または（v）モリブデン含有硫黄化合物を含む場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる硫黄原子のモル数をＣで表したとき、そのモル比（Ｃ／Ａ）が、６．９６×１０−３〜５．５５×１０−１の範囲にあり、また
（３）前記添加剤（Ｙ）として、（iii）タングステン含有塩素化合物または（vi）モリブデン含有塩素化合物を含む場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる塩素原子のモル数をＤで表したとき、そのモル比（Ｄ／Ａ）が、６．９６×１０−３〜６．９４×１０−１の範囲にある
ことを特徴とするハニカム状排ガス処理触媒製造用のチタン含有粒状粉末。 A composite oxide (X) of a metal element containing at least one of tungsten and molybdenum and titanium, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, (iv) A titanium-containing granular powder for producing a honeycomb-shaped exhaust gas treatment catalyst, comprising a molybdenum-containing nitrogen compound, (v) a molybdenum-containing sulfur compound, and (vi) an additive (Y) selected from molybdenum-containing chlorine compounds. And
(1) When the additive (Y) includes (i) a tungsten-containing nitrogen compound or (iv) a molybdenum-containing nitrogen compound, A represents the number of moles of titanium atoms contained in the titanium-containing granular powder. Further, when the number of moles of nitrogen atoms contained in the titanium-containing granular powder is represented by B, the molar ratio (B / A) is in the range of 8.70 × 10 −4 to 2.78 × 10 −1 . And
(2) When the additive (Y) contains (ii) a tungsten-containing sulfur compound or (v) a molybdenum-containing sulfur compound, A represents the number of moles of titanium atoms contained in the titanium-containing granular powder. Furthermore, when the number of moles of sulfur atoms contained in the titanium-containing granular powder is represented by C, the molar ratio (C / A) is in the range of 6.96 × 10 −3 to 5.55 × 10 −1 . And (3) when the additive (Y) includes (iii) a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound, the number of moles of titanium atoms contained in the titanium-containing granular powder. Is represented by A, and when the number of moles of chlorine atoms contained in the titanium-containing granular powder is represented by D, the molar ratio (D / A) is 6.96 × 10 −3 to 6.94 × 10 6. and wherein in the range of -1 Honeycomb exhaust gas treatment catalyst containing titanium granular powder for manufacturing that.
かつ、前記チタン含有粒状粉末の比表面積が４０〜３００ｍ２／ｇの範囲にあることを特徴とする請求項１に記載のハニカム状排ガス処理触媒製造用のチタン含有粒状粉末。 When the titanium-containing granular powder is measured by X-ray diffraction, the titanium oxide contained in the titanium-containing granular powder has an anatase type crystal structure, and the peak intensity of the (101) plane of the anatase type crystal Is P 1, and the peak intensity of the (101) plane of the anatase type crystal in the standard powder of titanium dioxide (MC-90 manufactured by Ishihara Sangyo Co., Ltd.) is represented by P 0 , the ratio of the peak intensity (P 1 / P 0 ) is in the range of 0.30 to 1.3,
And the specific surface area of the said titanium containing granular powder exists in the range of 40-300 m < 2 > / g, The titanium containing granular powder for honeycomb-shaped exhaust gas treatment catalyst manufacture of Claim 1 characterized by the above-mentioned.
（１）前記添加剤（Ｙ）として、（i）タングステン含有窒素化合物または（iv）モリブデン含有窒素化合物を使用する場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる窒素原子のモル数をＢで表したとき、そのモル比（Ｂ／Ａ）が、８．７０×１０−４〜２．７８×１０−１の範囲となる割合で前記複合酸化物と該添加剤とを混合する工程からなり、
（２）前記添加剤（Ｙ）として、（ii）タングステン含有硫黄化合物または（v）モリブデン含有硫黄化合物を使用する場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる硫黄原子のモル数をＣで表したとき、そのモル比（Ｃ／Ａ）が、６．９６×１０−３〜５．５５×１０−１の範囲となる割合で前記複合酸化物と該添加剤とを混合する工程からなり、また
（３）前記添加剤（Ｙ）として、（iii）タングステン含有塩素化合物または（vi）モリブデン含有塩素化合物を使用する場合には、前記チタン含有粒状粉末中に含まれるチタン原子のモル数をＡで表し、さらに該チタン含有粒状粉末中に含まれる塩素原子のモル数をＤで表したとき、そのモル比（Ｄ／Ａ）が、６．９６×１０−３〜６．９４×１０−１の範囲となる割合で前記複合酸化物と該添加剤とを混合する工程からなる
ことを特徴とするハニカム状排ガス処理触媒製造用のチタン含有粒状粉末の製造方法。 A composite oxide (X) of a metal element containing at least one of tungsten and molybdenum and titanium, (i) a tungsten-containing nitrogen compound, (ii) a tungsten-containing sulfur compound, (iii) a tungsten-containing chlorine compound, (iv) For producing a honeycomb-shaped exhaust gas treatment catalyst comprising a step of mixing an additive (Y) selected from a molybdenum-containing nitrogen compound, (v) a molybdenum-containing sulfur compound, and (vi) a molybdenum-containing chlorine compound at the following ratios: A method for producing a titanium-containing granular powder of
(1) When (i) tungsten-containing nitrogen compound or (iv) molybdenum-containing nitrogen compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium-containing granular powder is represented by A. In addition, when the number of moles of nitrogen atoms contained in the titanium-containing granular powder is represented by B, the molar ratio (B / A) is from 8.70 × 10 −4 to 2.78 × 10 −1 . Comprising the step of mixing the composite oxide and the additive in a proportion that falls within a range,
(2) When (ii) tungsten-containing sulfur compound or (v) molybdenum-containing sulfur compound is used as the additive (Y), the number of moles of titanium atoms contained in the titanium-containing granular powder is A. When the number of moles of sulfur atoms contained in the titanium-containing granular powder is expressed by C, the molar ratio (C / A) is 6.96 × 10 −3 to 5.55 × 10 −1 . And (3) using a tungsten-containing chlorine compound or (vi) a molybdenum-containing chlorine compound as the additive (Y). When the number of moles of titanium atoms contained in the titanium-containing granular powder is represented by A and the number of moles of chlorine atoms contained in the titanium-containing granular powder is represented by D, the molar ratio ( D / A) is 6 96 × 10 -3 ~6.94 × 10 percentage in the composite oxide in the range of -1 and honeycomb exhaust gas treatment catalyst of titanium-containing particulate for production characterized by comprising the step of mixing the additive Powder manufacturing method.
（２）前記スラリー液に構造補強材を加えて混練し、前記成分を含む混和物を得る工程、
（３）前記混和物を押出形成してハニカム構造体を得る工程、および
（４）前記ハニカム構造体を乾燥させた後、さらに４００〜７００℃の温度条件下で焼成する工程を少なくとも含むことを特徴とするハニカム状排ガス処理触媒の製造方法。 (1) Water and vanadium oxide or a precursor thereof are mixed with the titanium-containing granular powder for manufacturing the honeycomb-shaped exhaust gas treatment catalyst manufactured by the manufacturing method according to claims 10 to 11, and these components are included. Obtaining a slurry liquid,
(2) adding a structural reinforcing material to the slurry and kneading to obtain a mixture containing the components;
(3) Extruding the admixture to obtain a honeycomb structure, and (4) After drying the honeycomb structure, further comprising firing at 400 to 700 ° C. A method for producing a honeycomb-shaped exhaust gas treatment catalyst.
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| KR1020147017326A KR101667863B1 (en) | 2011-12-27 | 2012-12-27 | Titanium-containing granular powder and method for production thereof, and exhaust gas treatment catalyst using same and method for production thereof |
| CN201280064415.4A CN104023840B (en) | 2011-12-27 | 2012-12-27 | Titaniferous nodular powder, the catalyst for treating waste gas using it and these manufacture method |
| PCT/JP2012/008353 WO2013099253A1 (en) | 2011-12-27 | 2012-12-27 | Titanium-containing granular powder and method for production thereof, and exhaust gas treatment catalyst using same and method for production thereof |
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| JP6441140B2 (en) * | 2014-03-28 | 2018-12-19 | 日揮触媒化成株式会社 | Method for producing titanium oxide fine powder using spent catalyst and method for producing exhaust gas treatment catalyst using the powder |
| JP6671163B2 (en) * | 2015-01-09 | 2020-03-25 | 日揮触媒化成株式会社 | Exhaust gas treatment honeycomb catalyst and method for producing the same |
| CN105214482A (en) * | 2015-11-14 | 2016-01-06 | 华玉叶 | A kind of domestic briquet stove flue gas purifying method |
| JP6555340B2 (en) * | 2016-02-24 | 2019-08-07 | 三菱ケミカル株式会社 | Multi-hole extrusion die, method for producing metal compound extrusion, method for producing catalyst extrusion for producing unsaturated aldehyde and / or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and / or unsaturated carboxylic acid |
| CN111229291B (en) * | 2020-03-24 | 2021-02-09 | 苏州道一至诚纳米材料技术有限公司 | Composite non-noble metal denitration catalyst and preparation method thereof |
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| JPS5624031A (en) * | 1979-08-03 | 1981-03-07 | Babcock Hitachi Kk | Removal of nitrogen oxide in exhaust gas |
| JPS5935028A (en) * | 1982-08-19 | 1984-02-25 | Mitsubishi Heavy Ind Ltd | Preparation of calcined titanium oxide and catalyst |
| DE3740289A1 (en) * | 1987-11-27 | 1989-06-08 | Degussa | CATALYST FOR THE SELECTIVE REDUCTION OF NITROGEN OXIDES WITH AMMONIA |
| JP3321423B2 (en) | 1991-11-27 | 2002-09-03 | バブコック日立株式会社 | Exhaust gas purification method |
| JPH0947637A (en) | 1995-08-03 | 1997-02-18 | Babcock Hitachi Kk | Exhaust gas denitration catalyst, preparation process for catalyst and exhaust gas denitraction process by catalyst |
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