JP6236647B2 - Alumina particles - Google Patents
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- JP6236647B2 JP6236647B2 JP2014035736A JP2014035736A JP6236647B2 JP 6236647 B2 JP6236647 B2 JP 6236647B2 JP 2014035736 A JP2014035736 A JP 2014035736A JP 2014035736 A JP2014035736 A JP 2014035736A JP 6236647 B2 JP6236647 B2 JP 6236647B2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 85
- 239000002245 particle Substances 0.000 title claims description 79
- 239000011148 porous material Substances 0.000 claims description 141
- 239000003054 catalyst Substances 0.000 claims description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 3
- 239000003595 mist Substances 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 14
- 239000000446 fuel Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000000017 hydrogel Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 230000010718 Oxidation Activity Effects 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 Platinum group metals Chemical class 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- RAFNAMHEPCFDRC-UHFFFAOYSA-N [W].[Mo].[Co].[Ni] Chemical compound [W].[Mo].[Co].[Ni] RAFNAMHEPCFDRC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Description
本発明は、新規な細孔構造を有するアルミナ粒子に関するものであり、より詳細には、触媒担体として、特に排ガス浄化用触媒の担体として好適に使用されるアルミナ粒子に関する。 The present invention relates to an alumina particle having a novel pore structure, and more particularly to an alumina particle suitably used as a catalyst carrier, particularly as a carrier for an exhaust gas purification catalyst.
白金、パラジウム、ロジウムに代表される白金族金属は、排ガス浄化用触媒活性成分としての機能を有しており、このような白金族金属を多孔質担体に担持させたものは、例えば自動車の排ガス中に含まれる炭化水素（ＨＣ）、一酸化炭素（ＣＯ）、窒素酸化物（ＮＯｘ）を浄化するための触媒として使用されている（特許文献１参照）。 Platinum group metals typified by platinum, palladium, and rhodium have a function as a catalytic active component for exhaust gas purification, and those in which such a platinum group metal is supported on a porous carrier are, for example, automobile exhaust gases. It is used as a catalyst for purifying hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) contained therein (see Patent Document 1).
ところで、上記のような白金族金属は貴金属であり、非常に高価であるため、その触媒機能が効率よく発揮されるように多孔質担体（触媒担体）に保持しなければならない。従って、触媒担体として好適に使用される多孔質担体についても種々の提案がなされている。 By the way, the platinum group metal as described above is a noble metal and is very expensive. Therefore, the platinum group metal must be held on a porous carrier (catalyst carrier) so that its catalytic function is efficiently exhibited. Accordingly, various proposals have been made for porous carriers that are suitably used as catalyst carriers.
例えば、特許文献１には、アルミナ、セリア、ジルコニア、チタニア、シリカ、ゼオライト及びメソポーラスシリカからなる群より選択された少なくとも１種を、上記白金族金属を担持させる触媒担体として用いることが提案されている。
また、特許文献２には、規則的周期構造を有する均一なメソ孔を備え且つ一定割合でＳｉ−Ｏ−Ｚｒ結合を有するメソポーラスシリカを触媒担体として用いることが提案されている。
さらに、特許文献３には、細孔直径が１０〜１００ｎｍの範囲にあるミクロポア、及び細孔直径が３００〜９００ｎｍの範囲にあるマクロポアを有している細孔構造を有している触媒担体として用いるアルミナが開示されており、さらには、ミクロポア及びマクロポアに加え、細孔直径が６０００〜９０００ｎｍの範囲にある超マクロポアを有するアルミナも開示されている。
For example, Patent Document 1 proposes that at least one selected from the group consisting of alumina, ceria, zirconia, titania, silica, zeolite, and mesoporous silica is used as a catalyst carrier for supporting the platinum group metal. Yes.
Patent Document 2 proposes to use mesoporous silica having uniform mesopores having a regular periodic structure and having Si—O—Zr bonds at a certain ratio as a catalyst carrier.
Further, Patent Document 3 discloses a catalyst carrier having a pore structure having a micropore having a pore diameter in the range of 10 to 100 nm and a macropore having a pore diameter in the range of 300 to 900 nm. Alumina to be used is disclosed, and furthermore, in addition to micropores and macropores, alumina having a super macropore having a pore diameter in the range of 6000 to 9000 nm is also disclosed.
上述した各種の触媒担体は、これに白金などの触媒活性成分を担持させたとき、何れも、ある程度の触媒能（ＨＣ、ＣＯ、ＮＯｘ等に対する浄化作用）を示すとともに、中でもアルミナ粒子を主体とするものは安価であるという利点を有している。一方、本発明者等の研究によると、通常、浄化すべきガスがミスト状で供給されたとき、ガス状で供給された場合に比して、その触媒能が低下するという問題があり、特に自動車の排ガスなどは、揮発性の低い燃料成分（炭化水素）がミスト状になって排出されることがあるため、これに対する改善が必要であるというのが本発明者等の見解である。 Each of the various catalyst supports described above exhibits a certain degree of catalytic ability (purifying action against HC, CO, NOx, etc.) when a catalytically active component such as platinum is supported thereon, and mainly contains alumina particles. What has to do has the advantage of being inexpensive. On the other hand, according to the studies by the present inventors, there is a problem that the catalytic ability is usually lowered when the gas to be purified is supplied in the mist state as compared with the case where the gas is supplied in the gaseous state. Since the exhaust gas of automobiles or the like has a low volatile fuel component (hydrocarbon) which may be discharged in the form of a mist, it is the view of the present inventors that improvement is necessary.
従って、本発明の目的は、触媒担体として好適に使用され、特に白金などの触媒活性成分を担持した時、処理物質がミスト状で供給された場合においての活性低下を有効に回避することが可能なアルミナ粒子を提供することにある。 Accordingly, the object of the present invention is to be suitably used as a catalyst carrier, and in particular, when a catalytically active component such as platinum is supported, it is possible to effectively avoid a decrease in activity when the processing substance is supplied in a mist form. It is to provide an alumina particle.
本発明によれば、細孔直径が４〜５０ｎｍのメソ孔の細孔容積Ｖ１が０．０５〜０．８０ｃｍ３／ｇの範囲にあり、細孔直径が５０〜８０００ｎｍのマクロ孔の細孔容積Ｖ２が０．０５〜０．５０ｃｍ３／ｇの範囲にあり、且つ、細孔直径が４〜８０００ｎｍの細孔のトータル細孔容積Ｖｔが０．１０〜１．３０ｃｍ３／ｇの範囲にある多元細孔構造を有し、非押出物であり、排ガス浄化用触媒を担持する担体として使用されることを特徴とするアルミナ粒子が提供される。 According to the present invention, the pore volume V 1 of the mesopores having a pore diameter of 4 to 50 nm is in the range of 0.05 to 0.80 cm 3 / g, and the macropores having a pore diameter of 50 to 8000 nm are fine. There pore volume V 2 is in the range of 0.05~0.50cm 3 / g, and the pore diameter is the total pore volume V t of the pores of 4~8000nm 0.10~1.30cm 3 / g have a range near Ru multi original pore structure of a non-extrudates, alumina particles, characterized in that it is used as a carrier for carrying an exhaust gas purifying catalyst is provided.
本発明のアルミナ粒子においては、
（１）前記マクロ孔の細孔容積Ｖ２とメソ孔の細孔容積Ｖ１との容積比（Ｖ２／Ｖ１）が０．１０〜０．８０の範囲にあること、
（２）１００×Ｓｉ／（Ｓｉ＋Ａｌ）で表されるＳｉ量が１．０〜１０．０モル％となる量でシリカが分散されていること、
（３）シリカを含まないこと、
（４）前記メソ孔の細孔容積Ｖ １ が０．３３〜０．４４ｃｍ ３ ／ｇの範囲にあり、前記マクロ孔の細孔容積Ｖ ２ が０．０５〜０．１４ｃｍ ３ ／ｇの範囲にあり、且つ、前記トータル細孔容積Ｖ ｔ が０．３９〜０．５４ｃｍ ３ ／ｇの範囲にあること、
が好ましい。
In the alumina particles of the present invention,
(1) The volume ratio (V 2 / V 1 ) between the pore volume V 2 of the macropores and the pore volume V 1 of the mesopores is in the range of 0.10 to 0.80,
(2) Silica is dispersed in an amount such that the amount of Si represented by 100 × Si / (Si + Al) is 1.0 to 10.0 mol%,
(3) not containing silica ,
(4) The pore volume V 1 of the mesopores is in the range of 0.33~0.44cm 3 / g, the range pore volume V 2 of the macropores of 0.05~0.14cm 3 / g And the total pore volume V t is in the range of 0.39 to 0.54 cm 3 / g,
Is preferred.
本発明によれば、また、上記アルミナ粒子に白金族金属を担持してなる排ガス浄化用触媒が提供される。 According to the present invention, there is also provided an exhaust gas purifying catalyst comprising a platinum group metal supported on the alumina particles.
尚、本明細書において、メソ孔及びマクロ孔との表現は、細孔直径の相対的な大きさを考慮して、細孔直径が４〜５０ｎｍの大きさの細孔（メソ孔）及び細孔直径が５０〜８０００ｎｍの大きさの細孔（マクロ孔）を示すものとして、説明の便宜上用いたものであり、当業者の間で一定の大きさの細孔を示すものとして一義的に使用されている表現ではない。例えば、特許文献３には、「マクロ孔」なる表現が記載されているが、その細孔直径の範囲は、本明細書で規定するマクロ孔の範囲とは異なっている。 In this specification, the expression “mesopore” and “macropore” refers to pores (mesopores) and fine pores having a pore diameter of 4 to 50 nm in consideration of the relative size of the pore diameter. It is used for convenience of explanation as indicating pores (macropores) having a pore diameter of 50 to 8000 nm, and is uniquely used to indicate pores of a certain size among those skilled in the art. It is not an expression that has been made. For example, Patent Document 3 describes the expression “macropore”, but the pore diameter range is different from the macropore range defined in this specification.
本発明のアルミナ粒子は、細孔直径が４〜８０００ｎｍの細孔のトータル細孔容積Ｖｔが０．１０〜１．３０ｃｍ３／ｇの範囲にあるという細孔構造を有しているが、特に重要な特徴は、細孔直径が４〜５０ｎｍのメソ孔の細孔容積Ｖ１が０．０５〜０．８０ｃｍ３／ｇの範囲あり、細孔直径が５０〜８０００ｎｍのマクロ孔の細孔容積Ｖ２が０．０５〜０．５０ｃｍ３／ｇの範囲にあるという多元細孔構造を有している点にある。
即ち、本発明のアルミナ粒子は、上記のような多元細孔構造を有していることに関連して、これに触媒活性成分を担持させたとき、触媒反応に供する処理物質がミスト状で供給された場合においても、触媒性能を低下させることなく、安定に反応を促進させることが可能となる。例えば、後述する実施例２及び比較例２に示されているように、上記多元構造を有する本発明のアルミナ粒子（実施例２）に白金を担持させ、これに軽油のミストを供給して燃焼させたとき、その５０％が分解する燃焼温度Ｔ５０は２８０℃であるが、上記のようなマクロ孔の細孔容積が小さいアルミナ粒子（比較例２）に白金を担持して同様の試験を行うと、燃焼温度Ｔ５０は約３１５℃となっており、触媒性能が低下していることが判る。
このような本発明のアルミナ粒子を担体として使用することにより、触媒反応に供する処理物質がミスト状で供給されたときの触媒性能の低下を有効に回避することができる。
The alumina particles of the present invention have a pore structure in which the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm is in the range of 0.10 to 1.30 cm 3 / g. The important features are that the pore volume V 1 of mesopores having a pore diameter of 4 to 50 nm is in the range of 0.05 to 0.80 cm 3 / g, and the pore volume of macropores having a pore diameter of 50 to 8000 nm. The V 2 has a multi-pore structure in which it is in the range of 0.05 to 0.50 cm 3 / g.
That is, the alumina particles of the present invention have a multi-pore structure as described above, and when a catalytically active component is supported on the alumina particles, the treatment substance used for the catalytic reaction is supplied in a mist form. Even in such a case, the reaction can be stably promoted without deteriorating the catalyst performance. For example, as shown in Example 2 and Comparative Example 2, which will be described later, platinum is supported on the alumina particles (Example 2) of the present invention having the above-mentioned multi-component structure, and light oil mist is supplied to this and burned. The combustion temperature T50 at which 50% is decomposed is 280 ° C., but platinum is supported on the alumina particles (Comparative Example 2) having a small pore volume as described above, and the same test is performed. The combustion temperature T50 is about 315 ° C., and it can be seen that the catalyst performance is reduced.
By using such alumina particles of the present invention as a carrier, it is possible to effectively avoid a decrease in catalyst performance when a treatment substance to be subjected to a catalytic reaction is supplied in a mist form.
本発明において、上記のような多元細孔構造を有するアルミナ粒子を担体として使用することにより触媒性能の低下を有効に回避できるという事実は、多くの実験により現象として見出されたものであり、その理由は明確に解明されるには至っていないが、本発明者等は次のように推定している。 In the present invention, the fact that a decrease in catalyst performance can be effectively avoided by using alumina particles having a multi-pore structure as described above as a support has been found as a phenomenon by many experiments, The reason for this has not been clearly elucidated, but the present inventors presume as follows.
即ち、本発明のアルミナ粒子におけるメソ孔は、触媒活性成分を安定に保持する空間として機能するものと考えられる一方で、マクロ孔は、触媒反応に供する処理物質を、触媒活性成分が担持されている領域に安定に導入するための導入空間として機能するものと思われる。
この点について詳述すると、上記のようなメソ孔が一定量存在することにより、触媒活性成分を担持させて触媒能を発揮させることが可能となるのであるが、このようなメソ孔のみでは、触媒反応に供する処理物質がミスト状で供給されたとき、その触媒能が十分に発揮されないことは、前述した比較例の実験結果が物語っている。このような触媒能の低下は、おそらく、ミスト（例えば燃料の熱分解物）により担体外表面における細孔の目詰まりが生じ、この結果、触媒活性成分と触媒反応に供する処理物質との接触が阻害され、触媒能の低下が生じてしまう。しかるに、本発明にしたがい、上記のような大きなマクロ孔を一定量存在せしめると、ミストによる細孔の目詰まりが有効に抑制され、結果として、触媒と触媒反応に供する処理物質との接触活性成分が阻害されず、安定して触媒能が発揮されるものと信じられる。
That is, the mesopores in the alumina particles of the present invention are considered to function as a space for stably holding the catalytically active component, while the macropores are treated substances for the catalytic reaction, and the catalytically active component is supported. It seems to function as an introduction space for stable introduction into a certain area.
When this point is described in detail, the presence of a certain amount of mesopores as described above makes it possible to support the catalytically active component and exert its catalytic ability, but only with such mesopores, The experimental results of the comparative examples described above indicate that the catalytic ability is not sufficiently exerted when the treatment substance used for the catalytic reaction is supplied in the form of a mist. Such a decrease in catalytic ability is probably caused by clogging of pores on the outer surface of the carrier due to mist (for example, thermal decomposition product of fuel), and as a result, contact between the catalytically active component and the treatment substance to be subjected to the catalytic reaction is reduced. Inhibited, resulting in a decrease in catalytic ability. However, according to the present invention, when a certain amount of large macropores as described above are present, clogging of the pores due to mist is effectively suppressed, and as a result, a catalytically active component between the catalyst and the treatment substance used for the catalytic reaction. It is believed that the catalytic ability is exhibited stably without being inhibited.
＜アルミナ粒子＞
本発明のアルミナ粒子は、後述する多元細孔構造を有するものであれば、その結晶構造は特に制限されず、γ、θ、δ、η、κ等の結晶構造を有するものであってよいが、特に安定した多元細孔構造を容易に形成できるという点で、γ−アルミナが好適である。
<Alumina particles>
The alumina particles of the present invention are not particularly limited as long as they have a multi-pore structure described later, and may have a crystal structure such as γ, θ, δ, η, and κ. In particular, γ-alumina is preferable in that a stable multi-pore structure can be easily formed.
また、このアルミナ粒子は、細孔直径がさらに、細孔直径が４〜５０ｎｍの大きさであるメソ孔と、細孔直径が５０〜８０００ｎｍの大きさのマクロ孔とを有する多元細孔構造を有するものであり、このために、細孔直径が４〜８０００ｎｍの細孔のトータル細孔容積Ｖｔが０．１０〜１．３０ｃｍ３／ｇ、特に０．１５〜０．９０ｃｍ３／ｇの範囲にある。即ち、このトータル容積Ｖｔが小さすぎると、上記のようなメソ孔及びマクロ孔を一定の量で形成することが困難となってしまう。特に全細孔を占めるマクロ孔の割合が小さくなってしまい、処理物質がミスト状で供給されたときの触媒性能の低下を回避することできなくなってしまう。また、トータル容積Ｖｔが過度に大きいと、このアルミナ粒子の耐熱性や粒子強度が低くなってしまい、触媒活性成分を担持する担体としての性能が損なわれ、粒子の熱収縮や崩壊等により多元細孔構造を安定に保持することができず、触媒性能を安定して発揮させることが困難となってしまう。 The alumina particles have a multi-pore structure having mesopores having a pore diameter of 4 to 50 nm and macropores having a pore diameter of 50 to 8000 nm. For this reason, the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm is in the range of 0.10 to 1.30 cm 3 / g, particularly 0.15 to 0.90 cm 3 / g. It is in. That is, if the total volume Vt is too small, it becomes difficult to form mesopores and macropores as described above in a certain amount. In particular, the proportion of macropores occupying all the pores becomes small, and it becomes impossible to avoid a decrease in catalyst performance when the processing substance is supplied in the form of mist. Further, if the total volume Vt is excessively large, the heat resistance and particle strength of the alumina particles are lowered, and the performance as a carrier for supporting the catalytically active component is impaired. The pore structure cannot be stably maintained, and it becomes difficult to stably exhibit the catalyst performance.
さらに、本発明においては、細孔直径が４〜８０００ｎｍの細孔のトータル細孔容積Ｖｔが上記範囲内であることを条件として、細孔直径が４〜５０ｎｍのメソ孔の細孔容積Ｖ１が０．０５〜０．８０ｃｍ３／ｇ、特に０．１０〜０．６０ｃｍ３／ｇの範囲にあり、細孔直径が５０〜８０００ｎｍのマクロ孔の細孔容積Ｖ２が０．０５〜０．５０ｃｍ３／ｇ、特に０．０５〜０．３０ｃｍ３／ｇの範囲にあることが必要である。
即ち、メソ孔の細孔容積Ｖ１が上記範囲よりも小さいと、十分な量の触媒活性成分を担持させることが困難となり、触媒性能自体が不満足なものとなってしまい、マクロ孔の細孔容積Ｖ２が上記範囲よりも小さいと、処理物質がミスト状で供給されたときの触媒性能の低下を回避することできなくなってしまう。さらに、メソ孔の細孔容積Ｖ１或いはマクロ孔の細孔容積Ｖ２が上記範囲よりも大きいと、メソ孔の細孔容積Ｖ１及びマクロ孔の細孔容積Ｖ２の何れか一方が上記範囲よりも小さくなってしまい、結果として、処理物質がミスト状で供給されたときの触媒性能（以下、ミスト触媒性能と略すことがある）の低下が困難となるか、或いは触媒性能自体の低下を生じてしまう。
Furthermore, in the present invention, on the condition that the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm is within the above range, the pore volume V 1 of mesopores having a pore diameter of 4 to 50 nm. Is in the range of 0.05 to 0.80 cm 3 / g, particularly 0.10 to 0.60 cm 3 / g, and the pore volume V 2 of the macropores having a pore diameter of 50 to 8000 nm is 0.05 to 0. .50cm 3 / g, it is necessary to particularly in the range of 0.05~0.30cm 3 / g.
That is, if the pore volume V 1 of the mesopores is smaller than the above range, it becomes difficult to carry a sufficient amount of the catalytically active component, and the catalyst performance itself becomes unsatisfactory, and the pores of the macropores when the volume V 2 is smaller than the above range, the processing material can no longer be able to avoid a decrease in catalytic performance when fed with mist. Further, when the pore volume V 1 of the mesopores or the pore volume V 2 of the macropores is larger than the above range, either the pore volume V 1 of the mesopores or the pore volume V 2 of the macropores is the above. As a result, it becomes difficult to lower the catalyst performance (hereinafter, sometimes abbreviated as mist catalyst performance) when the processing substance is supplied in a mist form, or the catalyst performance itself is lowered. Will occur.
このような多元細孔構造を有する本発明のアルミナ粒子は、マクロ孔の細孔容積Ｖ２とメソ孔の細孔容積Ｖ１との容積比（Ｖ２／Ｖ１）が０．１０〜０．８０、特に０．２０〜０．６０の範囲に調整されていることが好ましい。即ち、このアルミナ粒子に触媒活性成分を担持させたときの触媒性能を高めるにはメソ孔の細孔容積（Ｖ１）を大きくすればよく、一方、ミスト触媒性能の点では、マクロ孔の細孔容積（Ｖ２）を大きくすればよいが、トータルの細孔容積（Ｖｔ）が制限されるため、一方の細孔容積を大きくすると、他方の細孔容積が低下してしまう。従って、優れた触媒性能とミスト触媒性能とをバランスよく確保するという点で、細孔容積比（Ｖ２／Ｖ１）を上記範囲内に調整することが好ましい。 The alumina particles of the present invention having such a multi-element pore structure have a volume ratio (V 2 / V 1 ) of the pore volume V 2 of macropores to the pore volume V 1 of mesopores of 0.10 to 0. .80, and particularly preferably in the range of 0.20 to 0.60. That is, in order to enhance the catalyst performance when the catalytic active component is supported on the alumina particles, the mesopore volume (V 1 ) should be increased. Although the pore volume (V 2 ) may be increased, the total pore volume (Vt) is limited. Therefore, if one of the pore volumes is increased, the other pore volume is decreased. Therefore, it is preferable to adjust the pore volume ratio (V 2 / V 1 ) within the above range in terms of ensuring a good balance between excellent catalyst performance and mist catalyst performance.
尚、本発明において、上述した各種の細孔容積Ｖｔ、Ｖ１及びＶ２は、水銀圧入法によって測定することができる。 In the present invention, the various pore volumes Vt, V 1 and V 2 described above can be measured by mercury porosimetry.
また、上述した多元細孔構造を有する本発明のアルミナ粒子は、細孔容積Ｖｔ、Ｖ１及びＶ２が前述した範囲にあることに関連して、高い比表面積を有しており、例えばＢＥＴ比表面積が、１００〜４００ｍ２／ｇの範囲にある。 In addition, the alumina particles of the present invention having the above-described multi-pore structure have a high specific surface area in connection with the pore volumes Vt, V 1 and V 2 being in the above-described ranges, for example, BET The specific surface area is in the range of 100 to 400 m 2 / g.
さらに、本発明のアルミナ粒子は、微量の微細なシリカが分散されていることが好ましく、例えば、１００×Ｓｉ／（Ｓｉ＋Ａｌ）で表されるＳｉ量が１．０〜１０．０モル％、特に１．５〜８．０ｍｏｌ％となる量でシリカが分散されていることが好ましい。
即ち、このような微量のシリカが分散されたアルミナ粒子は、白金などの触媒活性成分を担持させて排ガス浄化用触媒として使用するときの触媒活性の耐熱耐久性が極めて高い。即ち、多元細孔構造を有するアルミナ粒子は、高温（例えば７００℃以上）に曝されたとき、細孔の収縮を生じるが、微量のシリカが分散されているときには、細孔の熱収縮が有効に抑制され、この結果、細孔内に触媒活性成分が安定に保持され、高温での熱処理によっても触媒活性が損なわれず、安定に維持することができる。
Furthermore, the alumina particles of the present invention preferably have a minute amount of fine silica dispersed therein. For example, the amount of Si represented by 100 × Si / (Si + Al) is 1.0 to 10.0 mol%, particularly Silica is preferably dispersed in an amount of 1.5 to 8.0 mol%.
That is, alumina particles in which a small amount of silica is dispersed have extremely high heat resistance and durability of catalytic activity when used as an exhaust gas purifying catalyst by supporting a catalytically active component such as platinum. That is, alumina particles having a multi-element pore structure cause pore shrinkage when exposed to high temperatures (eg, 700 ° C. or higher), but when a small amount of silica is dispersed, thermal shrinkage of the pores is effective. As a result, the catalytically active component is stably held in the pores, and the catalytic activity is not impaired even by heat treatment at a high temperature and can be stably maintained.
尚、Ｓｉ含有量（ｍｏｌ％）が上記範囲よりも大きい場合には、分散されているシリカ量が多く、この結果、細孔内への触媒活性成分の担持に支障を来たし、触媒活性そのものが低下してしまう。また、Ｓｉ含有量（ｍｏｌ％）が上記範囲よりも小さいときには、分散されているシリカ量が少ないため、アルミナ細孔の熱収縮を十分に抑制することができず、触媒活性の耐熱耐久性を高めることが困難となる。 When the Si content (mol%) is larger than the above range, the amount of dispersed silica is large, resulting in hindering the support of the catalytically active component in the pores, and the catalytic activity itself is It will decline. Also, when the Si content (mol%) is smaller than the above range, the amount of silica dispersed is small, so the heat shrinkage of the alumina pores cannot be sufficiently suppressed, and the heat resistance and durability of the catalytic activity is reduced. It becomes difficult to increase.
＜アルミナ粒子の製造＞
本発明のアルミナ粒子は、硫酸アルミニウム等のアルミニウム塩の水溶液を原料とし、この原料液とアルカリとを混合してゲル化、水洗、乾燥及び焼成することにより製造されるが、ゲル化を細孔調整剤の存在下で行うことが必要である。
<Manufacture of alumina particles>
The alumina particles of the present invention are produced by using an aqueous solution of an aluminum salt such as aluminum sulfate as a raw material, mixing the raw material liquid and an alkali, and gelling, washing with water, drying and firing. It is necessary to carry out in the presence of a modifier.
アルミニウム塩水溶液と混合するアルカリとしては、苛性ソーダ、苛性カリ、水酸化アンモニウム等が使用され、該アルカリは、原料液との混合液のｐＨがアルカリ性の範囲となる量で使用される。 As the alkali to be mixed with the aluminum salt aqueous solution, caustic soda, caustic potash, ammonium hydroxide or the like is used, and the alkali is used in such an amount that the pH of the mixed liquid with the raw material liquid is in the alkaline range.
また、細孔調整剤としては、有機樹脂粒子が使用される。即ち、このような有機樹脂粒子の存在下でゲル化が行われ、有機樹脂粒子を包含するようにアルミナのヒドロゲルが生成し、さらに、その後の焼成で有機樹脂粒子が分解して除去されるため、前述した多元細孔構造を有するアルミナ粒子を得ることができる。
従って、このような有機樹脂粒子は、焼成過程において、ある程度の高温に昇温されるまで粒子の形態を維持しているものであることが必要であり、このために、耐アルカリ性が高く、融点乃至軟化点が比較的高いもの（例えば１００℃以上）が使用される。例えば、ポリメチルメタクリレート（ＰＭＭＡ）やポリスチレンの樹脂粒子を好適に使用することができ、これらの樹脂は、共重合により改質され、架橋構造の導入により耐熱性や耐アルカリが高められていてもよい。また、東洋紡（株）等により市販されている架橋ポリ（メタ）アクリル酸ナトリウムや架橋ポリ（メタ）アクリル酸カリウムなどの粒子を使用することもできる。
Further, organic resin particles are used as the pore adjusting agent. That is, since gelation is performed in the presence of such organic resin particles, an alumina hydrogel is formed so as to include the organic resin particles, and further, the organic resin particles are decomposed and removed by subsequent firing. The alumina particles having the above-mentioned multi-pore structure can be obtained.
Therefore, it is necessary that such organic resin particles maintain the form of the particles until the temperature is raised to a certain high temperature in the firing process. For this reason, the alkali resin has a high alkali resistance and a melting point. Or a thing with a comparatively high softening point (for example, 100 degreeC or more) is used. For example, resin particles such as polymethyl methacrylate (PMMA) and polystyrene can be suitably used. These resins are modified by copolymerization, and heat resistance and alkali resistance are improved by introducing a crosslinked structure. Good. In addition, particles such as cross-linked sodium poly (meth) acrylate and potassium poly (meth) acrylate marketed by Toyobo Co., Ltd. can be used.
このような有機樹脂粒子は、特にマクロ孔の形成に寄与するものであり、微細であることが好ましく、例えばレーザ回折散乱法で測定した体積基準の平均粒径（Ｄ５０）が０．１〜１０μｍの範囲である微細粒子であることが好適である。即ち、この粒子径が過度に大きいと、該有機樹脂粒子をゲル中に均一に分散させることが困難となるばかりか、該粒子を包含した状態でのゲル化も困難となり、細孔調整を効果的に行うことができなくなるおそれがある。さらに、粒径が過度に小さい場合には、取り扱いが困難であるばかりか、凝集等を生じ易く、細孔調整も困難となるおそれがある。 Such organic resin particles particularly contribute to the formation of macropores, and are preferably fine. For example, the volume-based average particle diameter (D 50 ) measured by a laser diffraction scattering method is 0.1 to 0.1. The fine particles are preferably in the range of 10 μm. That is, if the particle size is excessively large, it becomes difficult not only to uniformly disperse the organic resin particles in the gel, but also gelation in a state including the particles becomes difficult, and pore adjustment is effective. There is a risk that it will not be possible to perform it automatically. Furthermore, when the particle size is excessively small, not only handling is difficult, but agglomeration or the like is likely to occur, and pore adjustment may be difficult.
本発明においては、上記の有機樹脂粒子の使用量が多いほど、トータルの細孔容積Ｖｔを占めるマクロ孔の細孔容積（Ｖ２）の割合が多くなる。従って、前述した多元細孔構造のアルミナ粒子を得るためには、かかる有機樹脂粒子は、硫酸アルミニウム水溶液に含まれる酸化物換算でのＡｌ量（Ａｌ２Ｏ３）１００質量部当り５〜４０質量部の量で使用するのがよい。 In the present invention, the larger the amount of the organic resin particles used, the greater the proportion of macropore pore volume (V 2 ) occupying the total pore volume Vt. Therefore, in order to obtain alumina particles of the above-mentioned multi-pore structure, such organic resin particles, Al quantity (Al 2 O 3) 5~40 weight per 100 parts by weight as oxides contained in an aqueous solution of aluminum sulfate It is better to use in parts quantity.
前述した硫酸アルミニウム等のアルミニウム塩の水溶液（原料液）とアルカリを混合してのゲル化は、該原料液及び有機樹脂粒子を４５．０〜８０．０℃の温度に加熱したアルカリ溶液に混合し（混合液のｐＨは、先に述べた通りアルカリ性）、ゲル形成後、水洗を行い、これにより、アルミナヒドロゲルが得られる。 The above-mentioned gelation by mixing an aqueous solution (raw material solution) of an aluminum salt such as aluminum sulfate and an alkali is performed by mixing the raw material solution and organic resin particles into an alkaline solution heated to a temperature of 45.0 to 80.0 ° C. (The pH of the mixed solution is alkaline as described above), and after gel formation, washing with water is performed, whereby an alumina hydrogel is obtained.
上記で得られたアルミナヒドロゲルを乾燥し、水分を除去して有機樹脂粒子を内包したキセロゲルを得、これを焼成することにより、目的とする多元細孔構造を有するアルミナ粒子が得られる。即ち、焼成により、キセロゲル中に含まれる有機樹脂粒子が分解して除去され、所定の大きさのメソ孔と共にマクロ孔を有するアルミナ粒子が得られるわけである。
焼成温度は、６００〜９００℃程度である。この温度がα−アルミナ化するような高温だと、細孔収縮が大きく、触媒活性成分の担持に不適当となるおそれがある。また、温度が低すぎると、有機樹脂粒子が分解除去出来ないおそれがある。
The alumina hydrogel obtained above is dried, moisture is removed to obtain a xerogel encapsulating organic resin particles, and this is fired to obtain alumina particles having a target multi-pore structure. That is, by firing, the organic resin particles contained in the xerogel are decomposed and removed, and alumina particles having macropores together with mesopores of a predetermined size are obtained.
The firing temperature is about 600 to 900 ° C. If this temperature is high enough to form α-alumina, the pore shrinkage is large, which may be inappropriate for supporting the catalytically active component. If the temperature is too low, the organic resin particles may not be decomposed and removed.
また、上述した方法により製造されたアルミナ粒子では、耐熱性が低く、例えば６００℃以上の高温雰囲気下に保持された場合、熱収縮により細孔が収縮してしまい、触媒性能の低下が生じることがある。このような不都合を防止するために、原料液をアルカリ液に混合してのゲル化に際して、酸性シリカゾルを共存させることが好ましい。
即ち、酸性シリカゾルの共存下で前述したヒドロゲルの生成を行い、さらに乾燥及び焼成を行うことにより、副生したシリカの微粒子がアルミナ粒子中に分散され、このシリカ微粒子が、アルミナ粒子が高温に保持されたときの細孔収縮を有効に抑制し、安定した多元細孔構造を維持し、この結果として細孔収縮による性能低下を有効に回避することができる。
In addition, the alumina particles produced by the above-described method have low heat resistance. For example, when held in a high temperature atmosphere of 600 ° C. or higher, the pores shrink due to thermal shrinkage, resulting in a decrease in catalyst performance. There is. In order to prevent such inconvenience, acidic silica sol is preferably allowed to coexist during gelation by mixing the raw material liquid with an alkali liquid.
That is, the above-described hydrogel is produced in the presence of acidic silica sol, and further dried and calcined to disperse by-produced silica fine particles in alumina particles, and these silica fine particles are kept at a high temperature. As a result, it is possible to effectively suppress pore shrinkage and maintain a stable multi-pore structure. As a result, it is possible to effectively avoid performance degradation due to pore shrinkage.
このような酸性シリカゾルは、原料液中のＡｌに対するＳｉ量、即ち、１００×Ｓｉ／（Ｓｉ＋Ａｌ）のｍｏｌ比が１．０〜１０．０ｍｏｌ％、特に１．５〜８．０ｍｏｌ％の範囲内となるような量で使用される。上記範囲よりも多量のＳｉの使用は、得られるアルミナ粒子の多元細孔構造を変動させるおそれがあり、その使用量が少量の場合には、高温時の細孔の収縮を抑制する効果が不十分となる。 Such an acidic silica sol has a Si amount relative to Al in the raw material liquid, that is, a molar ratio of 100 × Si / (Si + Al) is in the range of 1.0 to 10.0 mol%, particularly 1.5 to 8.0 mol%. Is used in such an amount. Use of a larger amount of Si than the above range may change the multi-pore structure of the resulting alumina particles, and if the amount used is small, the effect of suppressing pore shrinkage at high temperatures is ineffective. It will be enough.
尚、酸性シリカゾルの共存下でゲル化を行って目的とするアルミナ粒子を製造する場合、乾燥及び焼成の何れかを水分の存在下で行うことが好ましい。即ち、理論的に解明されているわけではないが、熱履歴に際しては水分を介在させることにより、焼成時におけるシリカ粒子の熱収縮が抑制され、シリカ粒子の存在による細孔の変動が抑制されるものと思われる。 In addition, when gelatinizing in the presence of acidic silica sol and producing the target alumina particle, it is preferable to perform either drying or baking in the presence of moisture. That is, although not theoretically clarified, the thermal contraction of silica particles during firing is suppressed by interposing moisture in the thermal history, and fluctuations in pores due to the presence of silica particles are suppressed. It seems to be.
水分存在下での乾燥は、所謂スチーム乾燥により行うことができる。例えば６０℃以上、特に１００〜２００℃の蒸気を吹き付けることや乾燥機内の排気を抑えヒドロゲルからの水分を長時間滞留させながら乾燥を行うのがよい。
また、水分存在下での焼成は、スチーム焼成により行うことができる。このスチーム焼成は、キセロゲル自体から発生する水分を長時間滞留させながら焼成することができる容器で所定の焼成温度に加熱することにより行われる。
Drying in the presence of moisture can be performed by so-called steam drying. For example, it is preferable to perform drying while spraying steam at 60 ° C. or higher, particularly 100 to 200 ° C. or suppressing exhaust in the dryer and retaining moisture from the hydrogel for a long time.
Further, firing in the presence of moisture can be performed by steam firing. This steam firing is performed by heating to a predetermined firing temperature in a container that can be fired while retaining moisture generated from the xerogel itself for a long time.
酸性シリカゾルを用いる場合においては、乾燥及び焼成の何れかを、上記のような水分存在下で行うことが望ましいが、最も好ましくはスチーム乾燥とスチーム焼成との両方を行うのがよい。即ち、このような手段を採用することにより、より有効に粒子（特にシリカ粒子）の収縮が抑制され、シリカ粒子の導入による細孔の変動をより確実に回避することができる。 When an acidic silica sol is used, it is desirable to perform either drying or firing in the presence of moisture as described above, but it is most preferable to perform both steam drying and steam firing. That is, by adopting such means, the shrinkage of particles (particularly silica particles) can be more effectively suppressed, and fluctuations in pores due to the introduction of silica particles can be avoided more reliably.
このようにして得られたシリカ分散アルミナは多孔質であり、内部に微量の微細シリカ粒子が均一に分散した構造を有しており、これにより、高温での熱処理による細孔の収縮が抑制され、さらにはＳｉ含有量の増大に伴う焼成時の細孔の変動も有効に抑制され、触媒担体として優れた特性を示すことになる。 The silica-dispersed alumina thus obtained is porous and has a structure in which a minute amount of fine silica particles are uniformly dispersed therein, thereby suppressing pore shrinkage due to heat treatment at high temperature. In addition, fluctuations in the pores during firing accompanying an increase in the Si content are effectively suppressed, and excellent characteristics as a catalyst carrier are exhibited.
＜触媒＞
上記のような特性を有するアルミナ粒子は、極めて安価であり、例えば押出成形、造粒成形等の公知の方法によって、円筒状、粒状、錠剤等の種々の形態に成形し、これに白金などの触媒活性成分を担持させて触媒としての使用に好適に適用される。
特にミスト状態に処理物質が供給されたときの触媒活性の低下が有効に回避されているため、白金族金属を担持させた自動車排ガス浄化用触媒として極めて好適であり、排ガス中のＨＣ、ＣＯ、ＮＯｘを浄化することができる。
さらに、微量のシリカが分散されている本発明のアルミナ粒子では、その耐熱耐久性も優れており、エージング等により高温に保持されたものであっても、細孔収縮が有効に抑制されているため、優れた触媒性能を発揮することができる。
<Catalyst>
Alumina particles having the above characteristics are extremely inexpensive, and are formed into various forms such as cylindrical, granular, and tablet by known methods such as extrusion molding and granulation molding, and platinum or the like is formed thereon. The catalyst active component is supported and applied suitably for use as a catalyst.
In particular, since a decrease in catalytic activity when a processing substance is supplied in a mist state is effectively avoided, it is extremely suitable as a catalyst for purifying automobile exhaust gas carrying a platinum group metal, and HC, CO, NOx can be purified.
Furthermore, the alumina particles of the present invention in which a small amount of silica is dispersed have excellent heat resistance and durability, and even when held at a high temperature by aging or the like, pore shrinkage is effectively suppressed. Therefore, excellent catalyst performance can be exhibited.
排ガス浄化用触媒として使用される白金族金属としては、白金、パラジウム、ロジウム、イリジウム、ルテニウムが代表的であるが、何れも極めて高価な貴金属である。このため、本発明の安価なアルミナ粒子を担体として用いた排ガス用触媒は、エージングなどの高温処理によっても触媒活性の低下が有効に回避され、長期間にわたって触媒性能を維持させることができるため、大幅なコストダウンに適している。
また、上述したアルミナ粒子は、特に高価な白金族触媒以外にも、水素化精製触媒、水素化脱硫触媒、水素化脱窒素触媒等の触媒としての機能を有する他の金属、例えば、銅、バナジウム、マンガン、クロム、モリブデン、タングステン、鉄、コバルト、ニッケル、オスミウム、モリブデン−コバルト、モリブデン−ニッケル、タングステン−ニッケル、モリブデン−コバルト−ニッケル、タングステン−コバルト−ニッケルまたはモリブデン−タングステン−コバルト−ニッケル等を担持させる担体として使用することもでき、各種の触媒として使用することもできる。
Typical platinum group metals used as exhaust gas purifying catalysts are platinum, palladium, rhodium, iridium and ruthenium, all of which are extremely expensive noble metals. For this reason, the exhaust gas catalyst using the inexpensive alumina particles of the present invention as a carrier can effectively avoid a decrease in catalytic activity even by high temperature treatment such as aging, and can maintain the catalyst performance over a long period of time. Suitable for significant cost reduction.
In addition, the above-described alumina particles may be used in addition to expensive platinum group catalysts, as well as other metals having a function as catalysts such as hydrorefining catalysts, hydrodesulfurization catalysts, hydrodenitrogenation catalysts, such as copper and vanadium. Manganese, chromium, molybdenum, tungsten, iron, cobalt, nickel, osmium, molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel, tungsten-cobalt-nickel or molybdenum-tungsten-cobalt-nickel, etc. It can also be used as a carrier to be supported, and can also be used as various catalysts.
触媒活性成分の担持方法としては、上述したアルミナ粒子の成形体（担体）を触媒活性成分の可溶性塩の溶液に浸漬し、該金属成分を担体中に導入する含浸法、或いはアルミナ粒子の製造の際、金属成分を同時に沈殿させる共沈法等、公知の方法を採用することができるが、操作上容易であり、触媒特性の安定化維持に好都合な含浸法によることが好ましい。例えば、このアルミナ粒子の担体を、常温または常温以上で含浸溶液に浸漬して所望成分が十分担体中に含浸する条件下で保持するのがよい。含浸溶液の量および温度は、所望量の触媒活性成分が担持されるように適宜調整することができる。また、触媒活性成分の所望担持量により含浸溶液に浸漬する担体の量を決定することができる。 As a method for supporting the catalytically active component, an impregnation method in which the above-mentioned molded article (support) of alumina particles is immersed in a solution of a soluble salt of the catalytically active component and the metal component is introduced into the support, or an alumina particle is produced. At this time, a known method such as a coprecipitation method for simultaneously precipitating the metal components can be employed, but it is preferable to use an impregnation method that is easy in operation and convenient for maintaining the stabilization of the catalyst characteristics. For example, the support of alumina particles may be immersed in an impregnation solution at room temperature or above and kept under conditions where the desired component is sufficiently impregnated in the support. The amount and temperature of the impregnation solution can be appropriately adjusted so that a desired amount of the catalytically active component is supported. Further, the amount of the carrier immersed in the impregnation solution can be determined according to the desired loading amount of the catalytically active component.
尚、二種以上の触媒活性成分を担持するには、二種以上の触媒活性成分をあらかじめ混合し、その混合溶液から同時に含浸する一液含浸法を採用することができるし、また、二種以上の活性成分の溶液を別々に調製し、逐次含浸していく二液含浸法を採用することもできる。 In order to carry two or more types of catalytically active components, a one-component impregnation method in which two or more types of catalytically active components are mixed in advance and simultaneously impregnated from the mixed solution can be adopted. It is also possible to employ a two-component impregnation method in which the above active ingredient solutions are separately prepared and impregnated sequentially.
本発明を、次の実験例により詳細に説明する。
尚、以下の実験に用いた各種の測定方法は次の通りである。
The present invention will be described in detail by the following experimental examples.
Various measurement methods used in the following experiments are as follows.
（１）化学分析；
Ｓｉ、Ａｌの測定はＪＩＳ．Ｍ．８８５３に準拠して測定した。
(1) Chemical analysis;
Si and Al are measured according to JIS. M.M. Measured according to 8853.
（２）比表面積；
Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＴｒｉＳｔａｒＩＩ ３０２０を用いて窒素吸着法にて測定を行った。比表面積は比圧が０．０５から０．２０の吸着側窒素吸着等温線からＢＥＴ法で解析した。
(2) specific surface area;
Measurement was performed by a nitrogen adsorption method using TriStarII 3020 manufactured by Micromeritics. The specific surface area was analyzed by the BET method from the adsorption side nitrogen adsorption isotherm having a specific pressure of 0.05 to 0.20.
（３）細孔容積、細孔分布、マクロ細孔径ピークトップ；
Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡｕｔｏＰｏｒｅ IV ９５００を用いて水銀圧入法にて測定を行った。細孔直径が４〜５０ｎｍのメソ孔の細孔容積Ｖ１は５０００〜６００００ｐｓｉａの圧入量より、細孔直径が５０〜８０００ｎｍのマクロ孔の細孔容積Ｖ２は２７．５〜５０００ｐｓｉａの圧入量より、細孔直径４〜８０００ｎｍの細孔のトータル細孔容積Ｖｔは２７．５〜６００００ｐｓｉａの圧入量より求めた。細孔分布は差分細孔容積で表現し、細孔直径が５０〜８０００ｎｍの範囲で最大差分細孔容積値を示した細孔直径をマクロ細孔径ピークトップとした。
(3) pore volume, pore distribution, macropore diameter peak top;
Measurement was performed by mercury porosimetry using an AutoPore IV 9500 manufactured by Micromeritics. The pore volume V 1 of mesopores having a pore diameter of 4 to 50 nm is an indentation amount of 5000 to 60000 psia, and the pore volume V 2 of macropores having a pore diameter of 50 to 8000 nm is an indentation amount of 27.5 to 5000 psia. Thus, the total pore volume Vt of pores having a pore diameter of 4 to 8000 nm was determined from the press-fit amount of 27.5 to 60000 psia. The pore distribution was expressed as a differential pore volume, and the pore diameter showing the maximum differential pore volume value in the range of the pore diameter of 50 to 8000 nm was defined as the macropore diameter peak top.
（４）触媒調製；
アルミナに対して０．９ｗｔ％Ｐｔ＋０．１ｗｔ％Ｐｄとなるように白金およびパラジウムのジニトロジアンミン硝酸溶液を含浸担持し、水素中４００℃で還元後、空気中５００℃１時間で処理し、これを空気中７５０℃５０時間でエージング処理を行ったものを触媒性能評価用試料とした。
(4) catalyst preparation;
It is impregnated with platinum and palladium dinitrodiammine nitric acid solution to 0.9 wt% Pt + 0.1 wt% Pd with respect to alumina, reduced at 400 ° C in hydrogen, treated in air at 500 ° C for 1 hour, A sample subjected to aging treatment at 750 ° C. for 50 hours in air was used as a sample for evaluating catalyst performance.
（５）ＨＣ、ＮＯ酸化活性評価；
常圧固定床流通反応法により行った。試料４０ｍｇに模擬排ガスとしてのＮＯ２００ｐｐｍ＋Ｃ１０Ｈ２２(デカン)１８０ｐｐｍ＋Ｃ１１Ｈ１０(α−メチルナフタレン)１８ｐｐｍ＋１０％Ｈ２Ｏ＋５％Ｏ２（Ｎ２希釈）を４００ｍＬ・ｍｉｎ−１流通させ、５００℃から階段状に降温し、ＨＣが５０％転化する温度、及び３５０℃におけるＮＯからＮＯ２への転化率を求めた。
(5) HC, NO oxidation activity evaluation;
It was carried out by a normal pressure fixed bed flow reaction method. A sample exhaust gas of NO200 ppm + C 10 H 22 (decane) 180 ppm + C 11 H 10 (α-methylnaphthalene) 18 ppm + 10% H 2 O + 5% O 2 (N 2 diluted) as a simulated exhaust gas was passed through 400 mL · min −1 and stepped from 500 ° C. The temperature at which the HC was converted to 50% and the conversion rate from NO to NO 2 at 350 ° C. were determined.
（６）燃料ミスト酸化活性評価；
図１に示す固定床流通型反応装置により行った。内径１０ｍｍの石英リアクター中央部に０．１ｇの粒状触媒を設置した。触媒層に燃料ミストが直接到達するように石英ウールは下部底面のみ設置し、リアクター内壁での燃料の結露を防ぐため電気炉から上部の部分はアルミ箔で覆い保温した。熱電対（Ｋ型）は触媒下部石英ウールの中央部分に挿入し反応温度を連続モニターした。燃料としての軽油（ＪＩＳ２号）は加圧し液体マスフローコントローラ（ジーエルサイエンス製、試験は２μＬ・ｍｉｎ−１で燃料供給した）により流量制御後、ＩＣＰ用二流体噴霧ノズル(藤原製作所製)に導入した。噴霧用気体としての空気０．１Ｌ・ｍｉｎ−１を同時に導入することで燃料ミストを直接反応管に添加した。さらに噴霧部の周囲から空気０．９L・ｍｉｎ−１を添加、希釈した。これにより、燃料５０００ｐｐｍＣ＋５％Ｏ２（Ｎ２希釈）を触媒層に１L・ｍｉｎ−１流し、５００℃から連続降温（３℃・ｍｉｎ−１）した。常に同じ試験条件にするために、ノズル先端からヒータおよび触媒層上部までの距離を各々４０ｍｍ、９０ｍｍに保持した。反応管の後段には０℃に冷やしたガラスウール入りのＵ字管を設け、未反応の燃料ミストを捕捉、分離した後、さらに後段にある分析装置にガス成分を導入した。ガス分析はＮＤＩＲ−ＣＯｘ計（島津、ＣＧＴ７０００）を用い、ＣＯおよびＣＯ２濃度をモニターした。触媒活性は、ＣＯ２への完全酸化率が１０、５０、９０%となる温度（Ｔ１０、Ｔ５０、Ｔ９０）で比較した。なお、表１の値はＴ５０である。
(6) Evaluation of fuel mist oxidation activity;
This was carried out by a fixed bed flow type reactor shown in FIG. 0.1 g of granular catalyst was installed in the center of a quartz reactor having an inner diameter of 10 mm. Quartz wool was installed only at the bottom of the bottom so that the fuel mist could reach the catalyst layer directly, and the upper part from the electric furnace was covered with aluminum foil to keep it warm in order to prevent fuel condensation on the inner wall of the reactor. A thermocouple (K type) was inserted into the central part of the catalyst lower quartz wool, and the reaction temperature was continuously monitored. Light oil (JIS No. 2) as fuel was pressurized and flow rate controlled by a liquid mass flow controller (manufactured by GL Science, supplied with 2 μL · min −1 for fuel), and then introduced into a two-fluid spray nozzle for ICP (manufactured by Fujiwara Seisakusho). . The fuel mist was added directly to the reaction tube by simultaneously introducing 0.1 L · min −1 of air as the atomizing gas. Furthermore, air 0.9L * min < -1 > was added and diluted from the circumference | surroundings of the spraying part. As a result, a fuel of 5000 ppmC + 5% O 2 (N 2 dilution) was flowed through the catalyst layer at 1 L · min −1 , and the temperature was continuously decreased from 500 ° C. (3 ° C. · min −1 ). In order to always maintain the same test conditions, the distance from the nozzle tip to the heater and the upper part of the catalyst layer was kept at 40 mm and 90 mm, respectively. A U-shaped tube containing glass wool cooled to 0 ° C. was provided at the rear stage of the reaction tube. After capturing and separating unreacted fuel mist, the gas component was further introduced into the analyzer at the rear stage. Gas analysis NDIR-COx meter (Shimadzu, CGT7000) was used to monitor the CO and CO 2 concentration. The catalytic activity was compared at temperatures (T10, T50, T90) at which the complete oxidation rate to CO 2 was 10, 50, 90%. The value in Table 1 is T50.
＜実施例１＞
アルミナ源の原料として硫酸アルミニウム（Ａｌ２Ｏ３ １１．３％、ＳＯ３ １４．５％、ＳＧ １．２５）を使用した。硫酸アルミニウム３００ｇに対し、細孔調整剤として平均粒子径３．０μｍのアクリル粒子を１０．２ｇ添加し攪拌混合したものを、水６００ｍＬと４９％苛性ソーダ７３．２ｇを混ぜ６０℃に加熱した容器に注加し、６０℃に加温したイオン交換水で、洗浄液が１０μＳ／ｃｍ以下になるまで洗浄して有機樹脂粒子添加アルミナヒドロゲルを得た。このゲルを３００ｍＬビーカーに入れてアルミ箔で上部を覆うことで水熱雰囲気とし、１５０℃で２４時間乾燥しキセロゲルを得た。得られたキセロゲルを１５５ｍＬの坩堝に入れ蓋をして水熱雰囲気とし、７５０℃で２時間焼成してマクロ孔付与アルミナを得た。得られたマクロ孔付与アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Example 1>
Aluminum sulfate (Al 2 O 3 11.3%, SO 3 14.5%, SG 1.25) was used as a raw material for the alumina source. To 300 g of aluminum sulfate, 10.2 g of acrylic particles having an average particle size of 3.0 μm as a pore adjusting agent was added and stirred and mixed in a container heated to 60 ° C. by mixing 600 mL of water and 73.2 g of 49% sodium hydroxide. It was poured and washed with ion-exchanged water heated to 60 ° C. until the washing liquid became 10 μS / cm or less to obtain an organic resin particle-added alumina hydrogel. This gel was put into a 300 mL beaker and the upper part was covered with aluminum foil to make a hydrothermal atmosphere and dried at 150 ° C. for 24 hours to obtain a xerogel. The obtained xerogel was put in a 155 mL crucible, covered with a hydrothermal atmosphere, and calcined at 750 ° C. for 2 hours to obtain macropore-added alumina. The obtained macropore-added alumina was measured for physical properties and evaluated for catalyst performance. The results are shown in Table 1.
＜比較例１＞
細孔調整剤を添加せず乾燥、焼成を水熱雰囲気にしなかったこと以外は実施例１と同様の操作を行いアルミナを得た。得られたアルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Comparative Example 1>
Alumina was obtained in the same manner as in Example 1 except that the pore modifier was not added and drying and firing were not performed in a hydrothermal atmosphere. The obtained alumina was measured for physical properties and evaluated for catalyst performance, and the results are shown in Table 1.
＜実施例２＞
ケイ酸ソーダ（ＳｉＯ２ ２２．５％、Ｎａ２Ｏ ７．２％、ＳＧ １．３０）と４５％濃度の硫酸を両者が瞬時接触を可能な装置を用いて供給し、この溶液に等倍の水を加えて調整した酸性シリカゾルを、硫酸アルミニウム３００ｇに対して３０ｇ添加した以外は実施例１と同様の操作を行いマクロ孔付与シリカ分散アルミナを得た。得られたマクロ孔付与シリカ分散アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Example 2>
Sodium silicate (SiO 2 22.5%, Na 2 O 7.2%, SG 1.30) and 45% sulfuric acid were supplied using an apparatus capable of instantaneous contact with both, and this solution was supplied at the same magnification. Except that 30 g of acidic silica sol prepared by adding water was added to 300 g of aluminum sulfate, the same operation as in Example 1 was carried out to obtain macropore-added silica-dispersed alumina. The obtained macropore-added silica-dispersed alumina was measured for physical properties and evaluated for catalyst performance, and the results are shown in Table 1.
＜比較例２＞
細孔調整剤を添加しなかったこと以外は実施例２と同様の操作でシリカ分散アルミナを得た。得られたシリカ分散アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Comparative example 2>
A silica-dispersed alumina was obtained in the same manner as in Example 2 except that the pore modifier was not added. The obtained silica-dispersed alumina was measured for physical properties and evaluated for catalyst performance, and the results are shown in Table 1.
＜実施例３＞
硫酸アルミニウム３００ｇに対し、細孔調整剤を５．１ｇ添加したこと以外は実施例１と同様の操作を行いマクロ孔付与アルミナを得た。得られたマクロ孔付与アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Example 3>
Except that 5.1 g of a pore adjusting agent was added to 300 g of aluminum sulfate, the same operation as in Example 1 was performed to obtain macropore-added alumina. The obtained macropore-added alumina was measured for physical properties and evaluated for catalyst performance. The results are shown in Table 1.
＜比較例３＞
硫酸アルミニウム３００ｇに対し、細孔調整剤を１．４ｇ添加したこと以外は実施例１と同様の操作を行い、アルミナを得た。得られたアルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Comparative Example 3>
The same operation as in Example 1 was carried out except that 1.4 g of a pore regulator was added to 300 g of aluminum sulfate to obtain alumina. The obtained alumina was measured for physical properties and evaluated for catalyst performance, and the results are shown in Table 1.
＜比較例４＞
硫酸アルミニウム３００ｇに対し、細孔調整剤を１７．０ｇ添加したこと以外は実施例１と同様の操作を行い、アクリル粒子添加アルミナヒドロゲルを調製したが、ゲルの浮力が高かったため、洗浄工程でゲルが流出し回収することが出来なかった。
<Comparative Example 4>
An acrylic particle-added alumina hydrogel was prepared in the same manner as in Example 1 except that 17.0 g of a pore adjuster was added to 300 g of aluminum sulfate. However, since the gel had high buoyancy, the gel was washed in the washing step. Spilled out and could not be recovered.
＜実施例４＞
細孔調整剤として平均粒子径０．５μｍのアクリル粒子を６．４ｇ添加したこと以外は実施例１と同様の操作を行い、マクロ孔付与アルミナを得た。得られたマクロ孔付与アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Example 4>
Except that 6.4 g of acrylic particles having an average particle size of 0.5 μm was added as a pore modifier, the same operation as in Example 1 was performed to obtain macropore-added alumina. The obtained macropore-added alumina was measured for physical properties and evaluated for catalyst performance. The results are shown in Table 1.
＜実施例５＞
細孔調整剤として平均粒子径１．５μｍのアクリル粒子を１０．２ｇ添加したこと以外は実施例１と同様の操作を行い、マクロ孔付与アルミナを得た。得られたマクロ孔付与アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Example 5>
Except that 10.2 g of acrylic particles having an average particle size of 1.5 μm was added as a pore modifier, the same operation as in Example 1 was performed to obtain macropore-added alumina. The obtained macropore-added alumina was measured for physical properties and evaluated for catalyst performance. The results are shown in Table 1.
＜実施例６＞
細孔調整剤として平均粒子径３．５μｍのスチレン粒子を１０．２ｇ添加したこと以外は実施例１と同様の操作を行い、マクロ孔付与アルミナを得た。得られたマクロ孔付与アルミナについて物性測定と触媒性能の評価を行い、結果を表１に記した。
<Example 6>
Except that 10.2 g of styrene particles having an average particle size of 3.5 μm was added as a pore modifier, the same operation as in Example 1 was performed to obtain macropore-added alumina. The obtained macropore-added alumina was measured for physical properties and evaluated for catalyst performance. The results are shown in Table 1.
表１のマクロ孔容積（Ｖ２）、Ｖ２／Ｖ１容積比より、本発明のマクロ孔付与アルミナ（実施例１〜６）はアルミナ源に細孔調整剤を入れて合成し、焼成することによりマクロ孔が付与されていることがわかる。さらに、マクロ孔直径ピークトップよりサイズの異なる細孔調整剤種を用いることによってマクロ孔サイズを調整可能であることがわかる。また、燃料ミスト酸化活性より、マクロ孔付与アルミナ（実施例１〜２）は比較例１〜２に比べてより低温で酸化活性を示すことから、ミストによる細孔の目詰まりが有効に抑制されていることがわかる。 From the macropore volume (V 2 ) and the V 2 / V 1 volume ratio in Table 1, the macropore-added alumina of the present invention (Examples 1 to 6) is synthesized by putting a pore regulator in an alumina source and calcined. This shows that the macropores are provided. Furthermore, it can be seen that the macropore size can be adjusted by using a different type of pore adjuster than the macropore diameter peak top. In addition, since the pores with macropores (Examples 1 and 2) exhibit oxidation activity at a lower temperature than Comparative Examples 1 and 2 due to the fuel mist oxidation activity, clogging of pores due to mist is effectively suppressed. You can see that
Claims (6)
非押出物であり、
排ガス浄化用触媒を担持する担体として使用されることを特徴とするアルミナ粒子。 The pore volume V 1 of mesopores having a pore diameter of 4 to 50 nm is in the range of 0.05 to 0.80 cm 3 / g, and the pore volume V 2 of macropores having a pore diameter of 50 to 8000 nm is 0. .05~0.50cm 3 / g in the range of, and, the pore diameter is the total pore volume V t of the pores of 4~8000nm multi area by the near of 0.10~1.30cm 3 / g possess the original pore structure,
Non-extruded,
An alumina particle characterized by being used as a carrier for supporting an exhaust gas purification catalyst .
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