JP2002326036A - Method of producing catalyst made of inorganic fiber and catalyst made of inorganic fiber obtained by the method - Google Patents
Method of producing catalyst made of inorganic fiber and catalyst made of inorganic fiber obtained by the methodInfo
- Publication number
- JP2002326036A JP2002326036A JP2001171768A JP2001171768A JP2002326036A JP 2002326036 A JP2002326036 A JP 2002326036A JP 2001171768 A JP2001171768 A JP 2001171768A JP 2001171768 A JP2001171768 A JP 2001171768A JP 2002326036 A JP2002326036 A JP 2002326036A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic fiber
- fiber
- catalyst
- inorganic
- acid salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000010304 firing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- -1 organic acid salt Chemical class 0.000 claims description 72
- 239000000835 fiber Substances 0.000 claims description 61
- 239000004480 active ingredient Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 23
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000243 solution Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 239000013618 particulate matter Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101100325793 Arabidopsis thaliana BCA2 gene Proteins 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ディーゼルエンジ
ンから排出される排ガス中に含まれる粒子状物質〔Ｓｏ
ｏｔ（すす）（固体炭素微粒子、固体炭化水素微粒
子）、ＳＯＦ（有機溶剤可溶の炭化水素微粒子）〕を燃
焼除去するための触媒；触媒燃焼用触媒；ＮＯｘ、未燃
ガス等の排ガス浄化触媒等として有用な触媒およびその
製造方法に関する。[0001] The present invention relates to a particulate matter [So] contained in exhaust gas discharged from a diesel engine.
Catalyst for burning and removing ot (soot) (solid carbon fine particles, solid hydrocarbon fine particles), SOF (organic solvent-soluble hydrocarbon fine particles); catalytic combustion catalyst; purification of exhaust gas such as NO x and unburned gas The present invention relates to a catalyst useful as a catalyst and the like and a method for producing the same.
【０００２】より詳しくは、ディーゼルエンジンから排
出される排ガス中の粒子状物質をＤＰＦ（ディーゼルパ
ティキュレートフィルタ／排ガス浄化装置）で捕集し大
気中に放出されるのを防止する際、本発明により得られ
た触媒を用いていれば、その触媒作用により捕集した粒
子状物質をより低温で燃焼除去することができるような
触媒およびその製造方法に関する。More specifically, when particulate matter in exhaust gas discharged from a diesel engine is collected by a DPF (diesel particulate filter / exhaust gas purifier) and prevented from being released to the atmosphere, the present invention provides The present invention relates to a catalyst capable of burning and removing particulate matter collected by the catalytic action at a lower temperature if the obtained catalyst is used, and a method for producing the same.
【０００３】[0003]
【従来の技術】無機繊維からなるフィルタは、ハニカム
状のフィルタに比べて反応表面積が大きく、衝撃に強い
という点で優れており、無機繊維フィルタに触媒を担持
させて、ディーゼルエンジン排ガス中のＮＯｘを還元浄
化する技術等が検討されている。2. Description of the Related Art A filter made of inorganic fibers is superior in that it has a larger reaction surface area and is more resistant to impacts than a honeycomb filter. Techniques for reducing and purifying x have been studied.
【０００４】この際に重要となるのが触媒活性成分を無
機繊維フィルタへいかに均一に担持させるかという担持
技術であり、これまで、無機繊維フィルタが、炭化珪素
繊維等のように疎水性で平滑な表面であると、従来のス
プレーコート法やウォッシュコート法では触媒活性成分
をはじいてしまい、無機繊維フィルタの積層内部まで均
一に担持させかつ触媒活性を十分生かせることができな
かった。What is important in this case is how to uniformly support the catalytically active component on the inorganic fiber filter. Until now, the inorganic fiber filter has been made of a hydrophobic and smooth material such as silicon carbide fiber. If the surface is too rough, the conventional spray coating method or wash coating method repels the catalytically active component, making it impossible to uniformly support the inside of the laminated inorganic fiber filter and to make full use of the catalytic activity.
【０００５】そのため、無機繊維自体を改質する方法が
開発されており、特開２０００−２８８３５２号公報に
は、微細孔を有する無機繊維構造体に触媒を担持した繊
維状の触媒体を利用してガス改質触媒装置に利用するこ
とが記載されているが、多孔性材料を使用して改質する
手間が必要であり、一般的な方法ではなかった。また、
この方法では、金属アルコキシドを使用して触媒を無機
繊維構造体に担持させているが、大量のアルコールを使
用したり、水と反応しやすく高度な担持技術を必要とす
るという問題があった。Therefore, a method of modifying the inorganic fiber itself has been developed. Japanese Patent Application Laid-Open No. 2000-288352 discloses a method in which a fibrous catalyst in which a catalyst is carried on an inorganic fiber structure having fine pores is used. However, this method is not a general method because it requires a time and effort for reforming using a porous material. Also,
In this method, the catalyst is supported on the inorganic fiber structure using a metal alkoxide. However, there is a problem that a large amount of alcohol is used, and the catalyst easily reacts with water and requires an advanced supporting technique.
【０００６】また、特開平５−５８７３４号公報におい
ては、炭化珪素表面を水蒸気処理で改質することによ
り、炭化珪素表面をＳｉＯ２に転化してアルミナ、白金
等の触媒成分の水溶性物質の担持を容易にするような工
夫が記載されているが、水蒸気処理という特殊な処理を
要するため市販の炭化珪素繊維では触媒担体として適用
できないという問題があった。In Japanese Patent Application Laid-Open No. 5-58734, the surface of silicon carbide is converted into SiO 2 by modifying the surface of silicon carbide by steam treatment to convert the water-soluble substance of a catalyst component such as alumina and platinum. Although a device that facilitates the carrying is described, there is a problem that a special treatment such as steam treatment is required, so that commercially available silicon carbide fibers cannot be used as a catalyst carrier.
【０００７】一方、特開昭６１−２７１０３４号公報で
は、シリカ−アルミナ繊維に界面活性剤を使用して、白
金、パラジウムを均一に担持させ、触媒バーナーとして
利用することが記載されているが、疎水性の炭化珪素繊
維に担持した記載はなく、また白金族元素のみを適用し
た例であり一般的でなく、更に硝酸塩、塩酸塩等を使用
するものであり、乾燥・焼成工程において腐食性ガスを
生じるという問題や硝酸痕等の残存物が触媒活性に悪影
響を及ぼす可能性があった。On the other hand, Japanese Patent Application Laid-Open No. 61-271,034 describes that platinum and palladium are uniformly supported on a silica-alumina fiber by using a surfactant to be used as a catalyst burner. There is no description supported on hydrophobic silicon carbide fibers, and it is an example in which only a platinum group element is applied, which is not common, and further uses nitrate, hydrochloride, etc. There is a possibility that a problem such as generation of a catalyst or a residue such as traces of nitric acid may adversely affect the catalytic activity.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、炭化
珪素繊維等からなる無機繊維構造体に特別の表面処理を
しなくとも、容易に無機繊維構造体の表面および内部に
まで均一に触媒活性成分を担持させて、触媒製造時に腐
食性ガスを発生させない若しくはほとんど発生させず、
触媒活性を十分発揮する触媒を製造できる、無機繊維製
触媒の製造方法および該方法によって得られる無機繊維
製触媒を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst which can easily and uniformly cover the surface and inside of an inorganic fiber structure without special surface treatment of the inorganic fiber structure made of silicon carbide fiber or the like. By supporting the active ingredient, no or almost no corrosive gas is generated during catalyst production,
An object of the present invention is to provide a method for producing a catalyst made of inorganic fiber, which can produce a catalyst exhibiting sufficient catalytic activity, and a catalyst made of inorganic fiber obtained by the method.
【０００９】[0009]
【課題を解決するための手段】即ち、本発明は、（Ａ）
活性成分元素を有する有機酸塩と（Ｂ）界面活性剤、と
を含む活性成分水溶液に、（Ｃ）無機繊維構造体を浸漬
した後、前記構造体を乾燥、焼成することを特徴とする
無機繊維製触媒の製造方法を提供するものである。That is, the present invention provides (A)
(C) immersing an inorganic fiber structure in an aqueous solution of an active component containing an organic acid salt having an active component element and (B) a surfactant, followed by drying and firing the structure. A method for producing a fiber catalyst is provided.
【００１０】また、本発明は、（Ａ）活性成分元素を有
する有機酸塩と（Ｄ）水溶性有機溶剤、とを含む活性成
分水溶液に、（Ｃ）無機繊維構造体を浸漬した後、前記
構造体を乾燥、焼成することを特徴とする無機繊維製触
媒の製造方法を提供するものである。[0010] The present invention also provides a method for immersing (C) an inorganic fiber structure in an aqueous solution of an active ingredient containing (A) an organic acid salt having an active ingredient element and (D) a water-soluble organic solvent. An object of the present invention is to provide a method for producing an inorganic fiber catalyst, which comprises drying and firing a structure.
【００１１】前記無機繊維構造体は、炭化珪素繊維、耐
熱性金属繊維、チタン酸カリウム繊維、チラノ繊維、ア
ルミナ繊維、シリカ繊維、シリカ・アルミナ繊維、ジル
コニア繊維、チタニア繊維、炭化珪素被覆炭素繊維およ
びガラス繊維からなる群から選ばれる少なくとも１種の
材質でできていてもよい。The inorganic fiber structure includes silicon carbide fiber, heat-resistant metal fiber, potassium titanate fiber, tyrano fiber, alumina fiber, silica fiber, silica / alumina fiber, zirconia fiber, titania fiber, silicon carbide-coated carbon fiber, It may be made of at least one material selected from the group consisting of glass fibers.
【００１２】有機酸塩は、酢酸塩、シュウ酸塩、ギ酸
塩、グリコール酸塩およびクエン酸塩からなる群から選
ばれる少なくとも１種であってもよい。[0012] The organic acid salt may be at least one selected from the group consisting of acetate, oxalate, formate, glycolate and citrate.
【００１３】前記水溶液が更に、（Ｅ）活性成分元素を
有する、無機酸塩および／または錯体塩を含んでおり、
前記無機酸塩が、硝酸塩、リン酸塩、硫酸塩、炭酸塩、
塩酸塩および金属酸塩からなる群から選ばれる少なくと
も１種であり、前記錯体塩がアンミン錯体塩であっても
よい。The aqueous solution further contains (E) an inorganic acid salt and / or complex salt having an active ingredient element,
The inorganic acid salt is nitrate, phosphate, sulfate, carbonate,
It is at least one selected from the group consisting of hydrochloride and metal salt, and the complex salt may be an ammine complex salt.
【００１４】前記有機酸塩の活性成分元素は、アルカリ
金属元素、第ＶＩＩＩ族元素、ランタニド元素およびチ
タン族元素からなる群から選ばれる少なくとも１種の元
素であってもよい。The active ingredient element of the organic acid salt may be at least one element selected from the group consisting of an alkali metal element, a group VIII element, a lanthanide element and a titanium group element.
【００１５】界面活性剤の量は、活性成分水溶液全量基
準で２０ｖｏｌｐｐｍ以上１ｖｏｌ％以下であってもよ
い。水溶性有機溶剤の量は、活性成分水溶液全量基準で
３０〜７０質量％であってもよい。The amount of the surfactant may be 20 vol ppm or more and 1 vol% or less based on the total amount of the aqueous active ingredient solution. The amount of the water-soluble organic solvent may be 30 to 70% by mass based on the total amount of the aqueous active ingredient solution.
【００１６】さらに本発明は、本発明の製造方法で製造
される無機繊維製触媒であり、無機繊維構造体表面に、
銅、金、銀、カリウム、セシウムおよびルビジウムから
なる群から選ばれる１種以上の元素を含む活性金属ある
いは活性金属化合物が形成されている無機繊維製触媒を
提供するものである。Further, the present invention relates to an inorganic fiber catalyst produced by the production method of the present invention.
An object of the present invention is to provide an inorganic fiber catalyst in which an active metal or an active metal compound containing at least one element selected from the group consisting of copper, gold, silver, potassium, cesium and rubidium is formed.
【００１７】前記活性金属あるいは活性金属化合物は、
更にセリウム、チタンおよびランタンからなる群から選
ばれる１種以上の元素を含んでいてもよい。The active metal or active metal compound is
Further, it may contain one or more elements selected from the group consisting of cerium, titanium and lanthanum.
【００１８】[0018]
【発明の実施の形態】（Ａ）成分として本発明において
用いることのできる有機酸塩としては、活性成分元素を
有する有機酸塩であれば特に限定されないが、酢酸塩、
シュウ酸塩、ギ酸塩、グリコール酸塩およびクエン酸塩
からなる群から選ばれる少なくとも１種を使用すること
ができる。BEST MODE FOR CARRYING OUT THE INVENTION The organic acid salt that can be used in the present invention as the component (A) is not particularly limited as long as it is an organic acid salt having an active ingredient element.
At least one selected from the group consisting of oxalate, formate, glycolate and citrate can be used.
【００１９】活性成分元素としては、例えばアルカリ金
属元素、第ＶＩＩＩ族元素、ランタニド元素およびチタ
ン族元素からなる群から選ばれる少なくとも１種の元素
である。水溶性の有機酸塩が好ましい。The active component element is, for example, at least one element selected from the group consisting of alkali metal elements, Group VIII elements, lanthanide elements, and titanium group elements. Water-soluble organic acid salts are preferred.
【００２０】本発明で用いる有機酸塩のアルカリ金属元
素は、Ｎａ、ＫおよびＣｓからなる群から選ばれる少な
くとも１つのアルカリ金属元素であってもよい。本発明
で用いる有機酸塩の第ＶＩＩＩ族元素としては、Ｆｅ、
ＣｏおよびＮｉからなる群から選ばれる少なくとも１つ
の元素を使用することができる。本発明で用いる有機酸
塩のランタニド元素としては、Ｃｅ、Ｌａ、Ｐｒ、Ｎｄ
およびＳｍからなる群から選ばれる少なくとも１つの元
素を使用することができる。本発明で用いる有機酸塩の
チタン族元素としてはＴｉが挙げられる。The alkali metal element of the organic acid salt used in the present invention may be at least one alkali metal element selected from the group consisting of Na, K and Cs. As the Group VIII element of the organic acid salt used in the present invention, Fe,
At least one element selected from the group consisting of Co and Ni can be used. The lanthanide element of the organic acid salt used in the present invention includes Ce, La, Pr, Nd
And at least one element selected from the group consisting of Sm. Ti is mentioned as a titanium group element of the organic acid salt used in the present invention.
【００２１】これら元素の組み合わせについては特に限
定されず、その用途により、アルカリ金属元素、第ＶＩ
ＩＩ族元素、ランタニド元素およびチタン族元素を適宜
組み合わせて使用することができる。例えば、ＤＰＦ用
には、Ｋ、Ｃｓから選ばれる１つ以上の元素が触媒に含
まれていれば良く、更に必要に応じてＣｅ、Ｔｉ、Ｌａ
から選ばれる１つ以上の元素を含ませることができる。
更に具体的にはＫ、Ｃｓのうちから選ばれる１つ以上の
元素とＬａの組み合わせが好ましい。The combination of these elements is not particularly limited, and depending on the use, an alkali metal element, VI
Group II elements, lanthanide elements, and titanium group elements can be used in appropriate combinations. For example, for DPF, one or more elements selected from K and Cs may be contained in the catalyst, and if necessary, Ce, Ti, La
And at least one element selected from the group consisting of:
More specifically, a combination of one or more elements selected from K and Cs with La is preferable.
【００２２】有機酸塩を使用することの有利な効果は幾
つかあるが、例えば有機酸塩は焼成処理によって腐食性
ガスを発生しないので、製造環境を良好に保つことがで
きる。また無機繊維構造体に活性金属や活性金属化合物
を担持できる程度に、有機酸塩は十分に水に溶解するこ
とができる。有機酸塩の方が無機酸塩よりも溶解度の大
きいものもあり、触媒担持量を多くすることができる場
合がある。Although the use of the organic acid salt has several advantageous effects, for example, the organic acid salt does not generate corrosive gas by the calcination treatment, so that the production environment can be kept good. The organic acid salt can be sufficiently dissolved in water to such an extent that the active metal or the active metal compound can be supported on the inorganic fiber structure. Some organic acid salts have higher solubility than inorganic acid salts, and in some cases, the amount of supported catalyst can be increased.
【００２３】有機酸塩を使用する本発明の触媒活性成分
担持方法は、疎水性の無機繊維構造体にも活性成分を均
一に担持させることができるが、有機酸塩と界面活性剤
とを組み合わせて使用することで、更に均一に無機繊維
構造体に触媒活性成分を担持させることができる。In the method for supporting a catalytically active component of the present invention using an organic acid salt, the active component can be uniformly supported on a hydrophobic inorganic fiber structure. By using this, the catalytically active component can be more uniformly supported on the inorganic fiber structure.
【００２４】一方、有機酸塩ではなく無機酸塩を使用し
た場合には、焼成時に腐食性ガスを発生することがあ
り、その処理に問題があり、また酸の痕が残留すること
により触媒活性低下を招いたり、無機繊維構造体の強度
低下が現れる可能性が有る。On the other hand, when an inorganic acid salt is used instead of an organic acid salt, a corrosive gas may be generated at the time of calcination, and there is a problem in the treatment. It may cause a decrease or a decrease in the strength of the inorganic fiber structure.
【００２５】さらに、金属アルコキシドを用いた方法と
比べても、本発明の方法は水分を遮断する必要もなく、
大量のアルコールを使用する必要もないという利点を有
する。Further, compared with the method using a metal alkoxide, the method of the present invention does not need to block moisture,
It has the advantage that it is not necessary to use a large amount of alcohol.
【００２６】有機酸塩の使用量は、目的とする担持量に
応じて適宜設定できる。ただし、有機酸塩の種類によっ
て水に溶ける量に上限があるので、その場合に担持量を
増やしたいならば、繰り返し、無機繊維構造体を、溶液
に浸漬、乾燥、焼成すればよい。The amount of the organic acid salt to be used can be appropriately set according to the intended amount of the carrier. However, there is an upper limit to the amount of water soluble in water depending on the type of organic acid salt. In this case, if it is desired to increase the supported amount, the inorganic fiber structure may be repeatedly immersed in the solution, dried, and fired.
【００２７】（Ａ）成分の活性金属成分を複数組み合わ
せるときの各成分量については特に限定されるものでは
なく、用途に応じて適宜設定することができる。例え
ば、ディーゼル排ガスに含まれる粒子状物質のＳＯＦ割
合、Ｓｏｏｔ割合、あるいはそれら成分自体の性質は、
エンジンの型式・使用条件などにより大きく変化し、さ
らには燃料の諸性状（セタン価、芳香族分割合、添加剤
の種類など）によっても変化する。したがって、実際に
排出される粒子状物質の性質は、車両等の実走行で変化
していくものと考えられ、その変化が大きい場合に、よ
り良好に触媒を作用させることができるようにするため
に、適宜、触媒中の各成分の混合比は変更できる。The amount of each component when a plurality of active metal components (A) are combined is not particularly limited, and can be appropriately set according to the application. For example, the SOF ratio and the Soot ratio of the particulate matter contained in the diesel exhaust gas, or the properties of these components themselves,
It varies greatly depending on the engine type and operating conditions, and also varies depending on the properties of the fuel (cetane number, aromatic content, type of additive, etc.). Therefore, it is considered that the properties of the particulate matter actually discharged change in actual running of a vehicle or the like, and when the change is large, the catalyst can be made to act better. In addition, the mixing ratio of each component in the catalyst can be appropriately changed.
【００２８】（Ｂ）成分の界面活性剤としてはカチオン
性界面活性剤、アニオン性界面活性剤、両性界面活性
剤、非イオン性界面活性剤などいかなる物でも使用でき
る。例えばカチオン性界面活性剤としてアルキルアミン
塩、第４級アンモニウム塩等があり、アニオン性界面活
性剤として脂肪酸塩、硫酸エステル塩、リン酸エステル
塩、アルキルベンゼンスルホン酸塩等があり、両性界面
活性剤ではアルキルベタイン系、アミノカルボン酸類、
イミダゾリン等があり、非イオン性界面活性剤としては
ポリオキシエチレンアルキルエーテル、ポリオキシエチ
レンアルキルアリルエーテル、多価アルコールの脂肪酸
エステル、ポリオキシアルキレンエステル、ポリグリセ
リン等があり、これらをそれぞれ単独あるいは任意の組
み合わせで用いることができる。As the surfactant of the component (B), any surfactant such as a cationic surfactant, an anionic surfactant, an amphoteric surfactant and a nonionic surfactant can be used. For example, cationic surfactants include alkylamine salts, quaternary ammonium salts, etc., and anionic surfactants include fatty acid salts, sulfate esters, phosphate ester salts, alkylbenzene sulfonates, etc., and amphoteric surfactants. Alkyl betaines, aminocarboxylic acids,
There are imidazoline and the like, and the nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, fatty acid ester of polyhydric alcohol, polyoxyalkylene ester, polyglycerin, etc. Can be used in combination.
【００２９】界面活性剤を使用すると、無機繊維のぬれ
性が改善でき、疎水性無機繊維構造体に対しても、担持
を行う際に水溶液を利用できることがある。この効果は
水溶性有機溶剤を混合しても得ることが出来る。ただし
無機繊維構造体の材質、形状によっては、同等の効果を
得るために、有機酸塩を含む活性成分水溶液に、水溶液
全量基準で３０％以上の有機溶剤を混合する必要があ
る。実施するスケールが大きい場合、大量の有機溶媒が
必要となることや、場合によっては排煙処理、残溶液の
処理工程が必要となる場合がある。When a surfactant is used, the wettability of the inorganic fibers can be improved, and an aqueous solution can be used when carrying the hydrophobic inorganic fiber structure. This effect can be obtained even by mixing a water-soluble organic solvent. However, depending on the material and shape of the inorganic fiber structure, it is necessary to mix an organic solvent containing an organic acid salt with an organic solvent in an amount of 30% or more based on the total amount of the aqueous solution in order to obtain the same effect. When the scale to be performed is large, a large amount of an organic solvent may be required, and in some cases, a step of exhausting smoke and a step of treating a residual solution may be required.
【００３０】また、界面活性剤は上記の効果だけでな
く、触媒活性成分を無機繊維構造体へ均一に担持させる
ことができるという効果がある。活性成分水溶液に分散
しにくい元素やその割合が同一条件でも、界面活性剤の
添加割合を一定範囲にすることにより、均一な分散担持
が可能となる。Further, the surfactant has the effect that not only the above effects but also the catalytically active component can be uniformly supported on the inorganic fiber structure. Even when the elements and their proportions that are difficult to disperse in the aqueous active ingredient solution are the same, the dispersion can be uniformly dispersed and supported by keeping the addition ratio of the surfactant within a certain range.
【００３１】（Ｂ）成分は、金属、ハロゲン等の、焼成
後に残留する成分等があるときは、触媒活性や無機繊維
構造体の寿命に影響を及ぼすことがあるのでこれらの影
響を考慮して処方を決定することが好ましい。The component (B) may affect the catalytic activity and the life of the inorganic fiber structure when there are components such as metals and halogens remaining after firing. It is preferred to determine the formula.
【００３２】非イオン性界面活性剤は、焼成後に、金属
等の残留する物質を有していないので好ましく用いるこ
とができる。前記非イオン性界面活性剤としてはポリオ
キシエチレン−ポリオキシプロピレン−ポリオキシエチ
レングリコール（プルロック型）、テトロニック型含窒
素非イオン界面活性剤、ポリオキシエチレングリコー
ル、ポリオキシエチレングリコールアルキルエーテル、
ポリオキシエチレンアルキルエステル、ポリオキシエチ
レンアルキルアリルエーテル、ポリオキシエチレンアル
キルアミン、ポリオキシエチレンアルキルアマイド、ポ
リオキシエチレンソルビタン等の脂肪酸エステルが使用
できる。The nonionic surfactant can be preferably used because it has no residual substances such as metals after firing. Examples of the nonionic surfactant include polyoxyethylene-polyoxypropylene-polyoxyethylene glycol (Pullock type), tetronic type nitrogen-containing nonionic surfactant, polyoxyethylene glycol, polyoxyethylene glycol alkyl ether,
Fatty acid esters such as polyoxyethylene alkyl ester, polyoxyethylene alkyl allyl ether, polyoxyethylene alkylamine, polyoxyethylene alkyl amide, and polyoxyethylene sorbitan can be used.
【００３３】（Ｂ）成分の使用量は特に限定されない
が、活性成分水溶液全量基準で２０ｖｏｌｐｐｍ〜１ｖ
ｏｌ％である。The amount of the component (B) is not particularly limited, but may be 20 vol ppm to 1 v based on the total amount of the aqueous active ingredient solution.
ol%.
【００３４】（Ｃ）成分の無機繊維構造体は触媒の担体
として用いるものであり、その形態は特に限定されず、
無機繊維自体あるいは無機繊維を焼結したものであって
もよく、さらに無機繊維に加工を施して、フェルト、マ
ット、織物、編み物、フィルタ、粉砕物等様々な形態に
して用いてもよい。The inorganic fiber structure of the component (C) is used as a catalyst carrier, and its form is not particularly limited.
The inorganic fiber itself or a sintered inorganic fiber may be used, and the inorganic fiber may be further processed and used in various forms such as a felt, a mat, a woven fabric, a knitted fabric, a filter, and a crushed product.
【００３５】無機繊維構造体の材質は、触媒の担体とし
て使用できるものであれば問題はないが、例えば炭化珪
素繊維、耐熱性金属繊維、チタン酸カリウム繊維、チラ
ノ繊維、アルミナ繊維、シリカ繊維、シリカ・アルミナ
繊維、ジルコニア繊維、チタニア繊維、炭化珪素被覆炭
素繊維、ガラス繊維等からなる群から選ばれる少なくと
も１種の材質からなるものでも、本発明の製法によっ
て、表面を改質しなくとも触媒活性成分を担持できる。There is no problem with the material of the inorganic fiber structure as long as it can be used as a carrier for the catalyst. For example, silicon carbide fiber, heat-resistant metal fiber, potassium titanate fiber, tyrano fiber, alumina fiber, silica fiber, Even if it is made of at least one material selected from the group consisting of silica / alumina fiber, zirconia fiber, titania fiber, silicon carbide coated carbon fiber, glass fiber, etc., the catalyst can be produced without modifying the surface by the production method of the present invention. It can carry active ingredients.
【００３６】特に表面が平滑で触媒活性成分を担持困難
であった繊維、炭化珪素繊維、耐熱性金属繊維、チタン
酸カリウム繊維、チラノ繊維などは、活性金属を含む水
溶液との濡れ性がよくないため、従来の製法では繊維が
多層に積層した構造体内部にまで触媒活性成分を担持す
ることは困難であったが、本発明による触媒の製造方法
（担持方法）はそれを可能にし、このような濡れ性がよ
くない繊維に触媒活性成分を均一に担持させることに関
して特に有効である。In particular, fibers having a smooth surface and having difficulty carrying a catalytically active component, silicon carbide fibers, heat-resistant metal fibers, potassium titanate fibers, and tyrano fibers have poor wettability with an aqueous solution containing an active metal. For this reason, it was difficult to support the catalytically active component even in the inside of the structure in which the fibers were stacked in multiple layers by the conventional manufacturing method. However, the method for manufacturing the catalyst (supporting method) according to the present invention enables this. This is particularly effective for uniformly supporting the catalytically active component on fibers having poor wettability.
【００３７】無機繊維構造体を使用することにより、閉
塞による機能低下を防ぐことができる。例えばＤＰＦと
して本発明の触媒を用いる場合、排ガスをフィルタに通
過させることにより、フィルタが粒子状物質を捕集する
が、無機繊維構造体を使用することにより、フィルタ閉
塞を抑制することができる。また、無機繊維構造体を用
いることで粒子状物質をフィルタの厚み方向に均一に分
散させて捕集できるので、フィルタ再生時にフィルタが
局部的に高温となることを防ぐことができる。また無機
繊維構造体は自由度が高いため、これを備えた触媒は熱
衝撃および圧衝撃にも柔軟に対応できる。By using the inorganic fiber structure, it is possible to prevent functional deterioration due to blockage. For example, when the catalyst of the present invention is used as the DPF, the filter captures the particulate matter by passing the exhaust gas through the filter. However, by using the inorganic fiber structure, the filter clogging can be suppressed. In addition, since the particulate matter can be uniformly dispersed and collected in the thickness direction of the filter by using the inorganic fiber structure, it is possible to prevent the filter from being locally heated during filter regeneration. Further, since the inorganic fiber structure has a high degree of freedom, a catalyst provided with the inorganic fiber structure can flexibly cope with thermal shock and pressure shock.
【００３８】ＤＰＦに使用されるフィルタとしてウォー
ルスルー型のハニカムが知られているが、無機繊維構造
体が有する上記の好ましい機能に比べて、このハニカム
の機能は不都合であり、さらにこのハニカムに触媒活性
成分を担持して用いた場合でも、触媒担持層を粒子状物
質が覆う形になり、フィルタ再生時の酸素拡散が充分に
行われず、再生が十分行われないことがあり問題があ
る。Although a wall-through type honeycomb is known as a filter used in the DPF, the function of the honeycomb is inconvenient as compared with the above-mentioned preferable functions of the inorganic fiber structure. Even when the active component is supported and used, there is a problem that the catalyst-supporting layer is covered with the particulate matter, oxygen is not sufficiently diffused at the time of filter regeneration, and regeneration is not sufficiently performed.
【００３９】本発明は（Ｂ）成分の界面活性剤に代えて
（Ｄ）成分の水溶性有機溶剤、好ましくは水溶性極性有
機溶剤を使用することができる。この場合、使用する水
溶性極性有機溶剤は水と相溶性があればよく、通常水１
リットルに対して２０ｇ以上溶けるものが好ましく、低
級アルコール類、ケトン類、グリコール類、セロソルブ
類、環状エーテル類等いずれでも良い。これらの中で例
えば、エタノール、イソプロパノールは入手しやすく、
イソプロパノールは活性成分水溶液全量基準で最大４０
質量％を混合するだけで済むことができる。In the present invention, a water-soluble organic solvent as the component (D), preferably a water-soluble polar organic solvent, can be used in place of the surfactant as the component (B). In this case, the water-soluble polar organic solvent used only needs to be compatible with water.
It is preferably soluble in 20 g or more per liter, and may be any of lower alcohols, ketones, glycols, cellosolves, cyclic ethers and the like. Among them, for example, ethanol and isopropanol are easily available,
Isopropanol is up to 40 based on the total amount of the aqueous active ingredient solution.
It is only necessary to mix the mass%.
【００４０】（Ｄ）成分の使用量は、活性成分水溶液全
量基準で３０〜７０質量％である。（Ｂ）成分の界面活
性剤と（Ｄ）成分の水溶性有機溶剤を併用してもよい。
この場合、（Ｂ）成分：（Ｄ）成分の比率は適宜設定す
ることができる。The use amount of the component (D) is 30 to 70% by mass based on the total amount of the aqueous solution of the active ingredient. The surfactant (B) and the water-soluble organic solvent (D) may be used in combination.
In this case, the ratio of the component (B) to the component (D) can be set as appropriate.
【００４１】本発明では、有機酸塩に加えて更に（Ｅ）
活性成分元素を有する、無機酸塩および／または錯体塩
を用いてもよく、該無機酸塩としては、硝酸塩、リン酸
塩、硫酸塩、炭酸塩、塩酸塩および金属酸塩から選ばれ
る少なくとも１種を使用することもできる。その他、錯
体塩としてはアンミン錯体塩等を使用することができ
る。In the present invention, in addition to the organic acid salt, (E)
An inorganic acid salt and / or complex salt having an active ingredient element may be used, and the inorganic acid salt is at least one selected from nitrate, phosphate, sulfate, carbonate, hydrochloride and metal salt. Seeds can also be used. In addition, an ammine complex salt or the like can be used as the complex salt.
【００４２】活性成分水溶液を調製する際に、有機酸塩
を使用することが好ましいが、入手しやすさおよび低コ
ストであるという理由で、触媒活性、フィルタに悪影響
を及ぼさない範囲で、前記無機酸塩および／または錯体
塩を併せて使用することができる。例えば銅成分につい
て、硝酸銅を用いることができる。In preparing the aqueous solution of the active ingredient, it is preferable to use an organic acid salt. However, because of availability and low cost, the organic acid salt is used within a range that does not adversely affect the catalytic activity and the filter. Acid salts and / or complex salts can be used in combination. For example, for the copper component, copper nitrate can be used.
【００４３】無機酸塩および錯体塩の活性成分元素とし
ては、Ｒｂ、Ｐｔ、Ｐｄ、Ｉｒ、Ｒｕ、Ｒｈ、Ｏｓ、Ｃ
ｕ、Ａｇ、Ａｕ、Ｚｒ、Ｈｆ、Ｔｈ、ＰｍおよびＥｕか
らなる群から選ばれる少なくとも１種が挙げられる。The active components of the inorganic acid salts and complex salts include Rb, Pt, Pd, Ir, Ru, Rh, Os, C
At least one selected from the group consisting of u, Ag, Au, Zr, Hf, Th, Pm, and Eu.
【００４４】有機酸塩に、活性成分元素を有する、無機
酸塩および／または錯体塩を組み合わせることにより、
溶解性等の問題で、有機酸塩のみでは製造できない化合
物をも製造することができる。By combining an organic acid salt with an inorganic acid salt and / or complex salt having an active ingredient element,
Due to problems such as solubility, a compound that cannot be produced only with an organic acid salt can be produced.
【００４５】上記効果を考えて、これら無機酸塩および
／または錯体塩の使用量を適宜設定することができる
が、有機酸塩に対する、無機酸塩および／または錯体塩
のモルベース割合、すなわち（無機酸塩および／または
錯体塩のモル数）／（有機酸塩のモル数）×１００＝１
〜８０モル％に設定できる。In consideration of the above effects, the amount of the inorganic acid salt and / or complex salt used can be appropriately set. The molar ratio of the inorganic acid salt and / or complex salt to the organic acid salt, that is, (inorganic salt) Number of moles of acid salt and / or complex salt) / (number of moles of organic acid salt) × 100 = 1
It can be set to ８０80 mol%.
【００４６】（Ｅ）成分を使用する場合、（Ａ）成分と
（Ｅ）成分の各成分は通常、それぞれ水等に溶解させて
活性成分水溶液とし、この水溶液に無機繊維構造体を浸
漬し、この構造体を取り出して乾燥して水等の溶媒を除
去した後に、空気中で通常、８００℃以下、好ましくは
４００〜６００℃、通常、２〜１０時間焼成することに
より、（Ａ）、（Ｅ）両活性成分が担持した本発明の無
機繊維製触媒を得ることができる。When the component (E) is used, each of the components (A) and (E) is usually dissolved in water or the like to form an aqueous solution of the active component, and the inorganic fiber structure is immersed in the aqueous solution. This structure is taken out and dried to remove a solvent such as water, and then calcined in the air usually at 800 ° C. or lower, preferably 400 to 600 ° C., usually for 2 to 10 hours to obtain (A), (A) E) The inorganic fiber catalyst of the present invention carrying both active components can be obtained.
【００４７】このようにして得られた無機繊維製触媒
は、その表面に銅、金、銀、カリウム、セシウムおよび
ルビジウムからなる群から選ばれる１種以上の元素を含
む活性金属あるいは活性金属化合物が形成されている。
活性金属あるいは活性金属化合物は、更にセリウム、チ
タンおよびランタンからなる群から選ばれる１種以上の
元素を含んでいてもよい。The inorganic fiber catalyst thus obtained has an active metal or an active metal compound containing at least one element selected from the group consisting of copper, gold, silver, potassium, cesium and rubidium on its surface. Is formed.
The active metal or active metal compound may further contain one or more elements selected from the group consisting of cerium, titanium and lanthanum.
【００４８】本発明においては、（Ａ）、（Ｅ）各成分
をそれぞれ別個に無機繊維構造体に担持させてもよい。
例えば（Ａ）成分の各成分を水等に溶解させて、これに
界面活性剤および／または水溶性有機溶剤を加えて活性
成分水溶液となし、この水溶液に無機繊維構造体を浸漬
した後に、この構造体を取り出して乾燥、焼成し、次に
（Ｅ）成分、界面活性剤および／または水溶性有機溶剤
を含む活性成分水溶液に、焼成した前記構造体を浸漬し
た後、同様に乾燥、焼成することで無機繊維製触媒を製
造してもよい。In the present invention, each of the components (A) and (E) may be separately supported on the inorganic fiber structure.
For example, each component of the component (A) is dissolved in water or the like, and a surfactant and / or a water-soluble organic solvent is added thereto to form an aqueous solution of the active component. After immersing the inorganic fiber structure in this aqueous solution, The structure is taken out, dried and fired, and then the fired structure is immersed in an active ingredient aqueous solution containing the component (E), a surfactant and / or a water-soluble organic solvent, and then dried and fired similarly. Thus, a catalyst made of inorganic fibers may be produced.
【００４９】上記のようにこれら（Ａ）、（Ｅ）成分を
含む活性成分水溶液の組成や、無機繊維構造体への担持
順序は任意とすることができる。As described above, the composition of the aqueous active ingredient solution containing these components (A) and (E) and the order of loading on the inorganic fiber structure can be determined arbitrarily.
【００５０】１度に（Ａ）、（Ｅ）両活性成分を担持し
たほうが、各活性成分がそれぞれ多成分で構成されてい
る場合、各金属成分を均一に担持できるので好ましい。
また別個に担持する場合、水溶性である有機酸塩のアル
カリ金属元素を最後に担持すれば、意図的にアルカリ金
属元素を触媒表面に多く分布させることが出来る。It is preferable to carry both the active components (A) and (E) at one time, since each active component can be carried uniformly when each active component is composed of multiple components.
When separately supported, if the alkali metal element of the water-soluble organic acid salt is supported last, a large amount of the alkali metal element can be intentionally distributed on the catalyst surface.
【００５１】フィルタへの触媒活性成分担持量は用途や
要求性能により適宜選択することができるが、通常、５
ｇ／Ｌ〜１００ｇ／Ｌであり、平面状フィルタであれば
５〜２０ｍｇ／ｃｍ２である。The amount of the catalytically active component carried on the filter can be appropriately selected depending on the application and required performance.
g / L to 100 g / L, and 5 to 20 mg / cm 2 for a planar filter.
【００５２】溶液中の各成分濃度は、各成分が溶解する
範囲において任意に設定できるが、焼成後の活性成分担
持割合が５〜２０ｍｇ／ｃｍ２となることがより好まし
い。この場合に考慮すべきことは、無機繊維構造体の吸
水割合（ｇ／ｃｍ２）、溶解成分の焼成後の質量減少で
ある。The concentration of each component in the solution can be arbitrarily set within a range in which each component dissolves. However, it is more preferable that the active component carrying ratio after firing is 5 to 20 mg / cm 2 . In this case, what should be considered are the water absorption ratio (g / cm 2 ) of the inorganic fiber structure and the mass reduction of the dissolved component after firing.
【００５３】例えば、吸水割合０．５ｇ／ｃｍ２のフィ
ルタ１００ｃｍ２に、酸化セリウムを１０ｍｇ／ｃｍ２
担持する際に、酢酸セリウム水溶液を用いた場合、Ｃｅ
（ＣＨ３ＣＯ２）３・Ｈ２Ｏの分子量は３３５．２７で
あるが、焼成後、ＣｅＯ２に変化し、その分子量は１７
２．１２であり、４８．７％の質量減少が見込まれる。
よってこの場合、１００ｃｍ２×０．５ｇ／ｃｍ２＝５
０ｇの水に、１００ｃｍ２×１０ｍｇ／ｃｍ２×０．０
０１ｇ／ｍｇ÷（１−０．４８７）＝１．９５ｇの酢酸
セリウムを溶解した水溶液を使用する。[0053] For example, the filter 100 cm 2 water absorption rate 0.5 g / cm 2, the cerium oxide 10 mg / cm 2
When an aqueous cerium acetate solution is used for loading, Ce
Although the molecular weight of (CH 3 CO 2 ) 3 .H 2 O is 335.27, it changes to CeO 2 after firing, and the molecular weight is 17
2.12 and a 48.7% weight loss is expected.
Therefore, in this case, 100 cm 2 × 0.5 g / cm 2 = 5
100 cm 2 × 10 mg / cm 2 × 0.0 in 0 g of water
01 g / mg０１ (1-0.487) = 1.95 g of an aqueous solution in which cerium acetate is dissolved is used.
【００５４】活性成分水溶液の温度は特に制限されない
が、２０〜４０℃に設定できる。ただし、この範囲での
各成分の溶解度が低く、水温を上げることで溶解度を向
上できる場合には、上記範囲以上に温度を上昇させても
よい。Although the temperature of the aqueous solution of the active ingredient is not particularly limited, it can be set at 20 to 40 ° C. However, when the solubility of each component in this range is low and the solubility can be improved by increasing the water temperature, the temperature may be raised to a temperature higher than the above range.
【００５５】活性成分の担持量は繰り返し浸漬、乾燥、
焼成を行うことでは増やすこともできる。The loading amount of the active ingredient was repeatedly immersed, dried,
By performing firing, it can be increased.
【００５６】また本発明の担持方法は、触媒活性成分を
スラリー状にして担持するスラリーコート法；スラリー
状の触媒活性成分を繊維構造体に吹きかけそして乾燥し
て担持するスプレーコート法等他の如何なる担持方法と
も組み合わせることができる。The supporting method of the present invention may be any other method such as a slurry coating method in which the catalytically active component is supported in a slurry form; a spray coating method in which the slurry-like catalytically active component is sprayed on the fiber structure, dried and supported. It can be combined with a supporting method.
【００５７】[0057]
【実施例】以下に実施例を示し、本発明を具体的に説明
する。ただし、本発明はこれら実施例に限定されるもの
ではないことはいうまでもない。実施例１ （金属繊維フィルタへの触媒活性成分水溶液担
持） 純水５０ｍｌに酢酸セリウム５．０ｇを溶解した後、非
イオン性界面活性剤（ポリオキシエチレンラウリルエー
テル、商品名：エマルゲン１０９Ｐ）（花王（株）製）
２００ｐｐｍをこれらに添加して、触媒活性成分水溶液
を調製した。The present invention will be specifically described below with reference to examples. However, it goes without saying that the present invention is not limited to these examples. Example 1 (Supporting aqueous solution of catalytically active component on metal fiber filter) After dissolving 5.0 g of cerium acetate in 50 ml of pure water, a nonionic surfactant (polyoxyethylene lauryl ether, trade name: Emulgen 109P) (Kao) (Made by Corporation)
A 200 ppm aqueous solution of the catalytically active component was prepared by adding 200 ppm to these.
【００５８】次に繊維径５０μｍ、目付重量１４００ｇ
／ｍ２の金属繊維フィルタ（商品名：リバーライト）
（川崎製鉄（株）製、Ａｌ／Ｆｅ／Ｃｒ＝５／２０／７
５％）を１０００℃で５時間処理（表面にＡｌ２Ｏ３膜
生成）し、このように処理した金属繊維フィルタを直径
１インチ（２．５４ｃｍ）の円盤状に切り抜き、前記の
ように調製した水溶液に充分に浸積した。金属繊維フィ
ルタを引き揚げた後、このフィルタを１２０℃で２ｈ乾
燥し、次にこのフィルタを６００℃で５時間焼成して、
触媒活性成分担持フィルタ（無機繊維製触媒）を得た。
担持割合は１０ｍｇ／ｃｍ２であった。Next, the fiber diameter is 50 μm and the basis weight is 1400 g.
/ M 2 of metal fiber filter (trade name: River Light)
(Kawasaki Steel Corporation, Al / Fe / Cr = 5/20/7
5%) at 1000 ° C. for 5 hours (formation of an Al 2 O 3 film on the surface), cut out the metal fiber filter thus treated into a disk having a diameter of 1 inch (2.54 cm), and prepared as described above. Immersed in the aqueous solution. After withdrawing the metal fiber filter, the filter is dried at 120 ° C. for 2 hours, and then the filter is baked at 600 ° C. for 5 hours.
A catalyst active component-carrying filter (catalyst made of inorganic fiber) was obtained.
The loading ratio was 10 mg / cm 2 .
【００５９】実施例２（有機酸塩＋無機酸塩＋炭化珪素
繊維＋界面活性剤の例） 純水５０ｍｌに酢酸セリウム２．３ｇ、硝酸銅２．７ｇ
を溶解した後、非イオン性界面活性剤（ポリオキシエチ
レンラウリルエーテル、商品名：エマルゲン１０９Ｐ）
（花王（株）製）２００ｐｐｍをこれらに添加して、触
媒活性成分水溶液を調製した。 Example 2 ( Example of organic acid salt + inorganic acid salt + silicon carbide fiber + surfactant) 2.3 g of cerium acetate and 2.7 g of copper nitrate in 50 ml of pure water
After dissolving, a nonionic surfactant (polyoxyethylene lauryl ether, trade name: Emulgen 109P)
200 ppm (manufactured by Kao Corporation) was added thereto to prepare an aqueous solution of the catalytically active component.
【００６０】次に繊維径１４μｍ、目付重量２３０ｇ／
ｍ２のＳｉＣ繊維フィルタを直径１インチの円盤状に切
り抜き、前記のように調製した水溶液に充分に浸積し
た。ＳｉＣ繊維フィルタを引き揚げた後、このフィルタ
を１２０℃で２ｈ乾燥し、次にこのフィルタを６００℃
で５時間焼成して、触媒活性成分担持フィルタを得た。
担持割合は１０ｍｇ／ｃｍ２であった。Next, the fiber diameter was 14 μm and the basis weight was 230 g /
Crop SiC fiber filter m 2 in a one-inch diameter disk-shaped and sufficiently immersed in an aqueous solution prepared as described above. After withdrawing the SiC fiber filter, the filter was dried at 120 ° C. for 2 hours, and then the filter was dried at 600 ° C.
For 5 hours to obtain a filter carrying a catalytically active component.
The loading ratio was 10 mg / cm 2 .
【００６１】このようにして得た触媒活性成分担持フィ
ルタの内部層を取り出し、この内部層を電子顕微鏡（日
本電子社製走査型電子顕微鏡、加速電圧１５ｋｅＶ）で
観察した。得られた電子顕微鏡写真（倍率４５００倍）
コピーを図２に示す。図２中、白色箇所が触媒活性成分
である。このように無機繊維構造体内部にまで均一に触
媒活性成分が担持していることを確認できた。The inner layer of the filter carrying the catalytically active component thus obtained was taken out, and the inner layer was observed with an electron microscope (scanning electron microscope manufactured by JEOL Ltd., acceleration voltage: 15 keV). Obtained electron micrograph (magnification: 4500 times)
The copy is shown in FIG. In FIG. 2, the white area is the catalytically active component. As described above, it was confirmed that the catalytically active component was uniformly supported inside the inorganic fiber structure.
【００６２】実施例３（有機酸塩＋無機酸塩＋炭化珪素
繊維＋界面活性剤の例） 純水５０ｍｌに酢酸セリウム２．８ｇ、硝酸銅３．３ｇ
を溶解した後、イソプロパノール２０ｍｌをこれらに混
合して、触媒活性成分水溶液を調製した。次に繊維径１
４μｍ、目付重量２３０ｇ／ｍ２のＳｉＣ繊維フィルタ
を直径１インチの円盤状に切り抜き、前記のように調製
した水溶液に充分に浸積した。ＳｉＣ繊維フィルタを引
き揚げた後、このフィルタを１２０℃で２ｈ乾燥し、次
にこのフィルタを６００℃で５時間焼成して、触媒活性
成分担持フィルタを得た。担持割合は１０ｍｇ／ｃｍ２
であった。 Example 3 ( Example of organic acid salt + inorganic acid salt + silicon carbide fiber + surfactant) 2.8 g of cerium acetate and 3.3 g of copper nitrate in 50 ml of pure water
After dissolving, 20 ml of isopropanol was mixed with these to prepare an aqueous solution of a catalytically active component. Next, fiber diameter 1
A 4 μm SiC fiber filter having a basis weight of 230 g / m 2 was cut into a disk having a diameter of 1 inch and sufficiently immersed in the aqueous solution prepared as described above. After withdrawing the SiC fiber filter, the filter was dried at 120 ° C. for 2 hours, and then fired at 600 ° C. for 5 hours to obtain a filter carrying a catalytically active component. The loading ratio is 10 mg / cm 2
Met.
【００６３】実施例４（有機酸塩＋炭化珪素繊維＋界面
活性剤の例） 純水５０ｍｌに酢酸セリウム７．０ｇを溶解した後、イ
ソプロパノール２０ｍｌをこれらに混合して、触媒活性
成分水溶液を調製した。 Example 4 ( Example of Organic Acid Salt + Silicon Carbide Fiber + Surfactant) After dissolving 7.0 g of cerium acetate in 50 ml of pure water, 20 ml of isopropanol was mixed therewith to prepare an aqueous solution of a catalytically active component. did.
【００６４】次に繊維径１４μｍ、目付重量２３０ｇ／
ｍ２のＳｉＣ繊維フィルタを直径１インチの円盤状に切
り抜き、前記のように調製した水溶液に充分に浸積し
た。ＳｉＣ繊維フィルタを引き揚げた後、このフィルタ
を１２０℃で２ｈ乾燥し、次にこのフィルタを６００℃
で５時間焼成して、触媒活性成分担持フィルタを得た。
担持割合は１０ｍｇ／ｃｍ２であった。Next, the fiber diameter was 14 μm and the basis weight was 230 g /
Crop SiC fiber filter m 2 in a one-inch diameter disk-shaped and sufficiently immersed in an aqueous solution prepared as described above. After withdrawing the SiC fiber filter, the filter was dried at 120 ° C. for 2 hours, and then the filter was dried at 600 ° C.
For 5 hours to obtain a filter carrying a catalytically active component.
The loading ratio was 10 mg / cm 2 .
【００６５】比較例１（無触媒による粒子状物質（Ｐ
Ｍ）燃焼） 繊維径１４μｍ、目付重量２３０ｇ／ｍ２ののＳｉＣ繊
維フィルタを直径１インチの円盤状に切り抜いたものを
用意した。 Comparative Example 1 (Particulate matter (P
M) Combustion) A SiC fiber filter having a fiber diameter of 14 μm and a basis weight of 230 g / m 2 was cut into a disk shape having a diameter of 1 inch.
【００６６】（触媒の活性評価）実施例２で得られた触
媒活性成分担持フィルタについて、以下のように活性評
価を行なった。発電機ディーゼルエンジンにＪＩＳ２号
軽油を満たし、触媒活性成分担持フィルタに一定条件で
ディーゼル排ガスを流通させることによって、一定量
（２．５ｍｇ／ｃｍ２）の粒子状物質を捕集した。(Evaluation of Activity of Catalyst) The activity of the filter carrying the catalytically active component obtained in Example 2 was evaluated as follows. A generator diesel engine was filled with JIS No. 2 light oil, and a fixed amount (2.5 mg / cm 2 ) of particulate matter was collected by flowing diesel exhaust gas under a certain condition through a catalyst active component-carrying filter.
【００６７】その後、このようにして得た粒子状物質捕
集済触媒活性成分担持フィルタを、遠赤外線反応装置
〔真空理工社製、商品名：ＲＨＬ−Ｅ４５Ｐ（１４４
Ｖ、４．８ｋＷ）〕にセットした。１０％Ｏ２／Ｎ２流
通下、２０℃／分で昇温し、粒子状物質を燃焼させた際
のＣＯ２発生推移を調べた。Thereafter, the particulate matter-collected catalytically active component-carrying filter obtained as described above was used in a far-infrared ray reactor [trade name: RHL-E45P (144, manufactured by Vacuum Riko Co., Ltd.)
V, 4.8 kW)]. The temperature was raised at a rate of 20 ° C./min under a flow of 10% O 2 / N 2 , and the transition of CO 2 generation when the particulate matter was burned was examined.
【００６８】実施例２で得られたＣｅＣｕ触媒の性能
は、図１に示すように、ＣＯ２発生ピーク温度が５００
℃、５５０℃であり、比較例１で用意した無触媒金属繊
維フィルタ（ＣＯ２発生ピーク温度：６５０℃）に比べ
て、捕集した粒子状物質を低温で燃焼除去させることが
でき、燃焼活性に優れていることが確認できた。[0068] Performance of CeCu catalyst obtained in Example 2, as shown in FIG. 1, CO 2 generation peak temperature 500
C., 550 ° C., compared with the non-catalytic metal fiber filter (CO 2 generation peak temperature: 650 ° C.) prepared in Comparative Example 1, the collected particulate matter can be burned and removed at a low temperature, and the combustion activity It was confirmed that it was excellent.
【００６９】[0069]
【発明の効果】活性金属の有機酸塩水溶液に、界面活性
剤を添加することで、無機繊維構造体で構成される触媒
担体に対して、触媒活性成分を表面はもちろん内部にま
で均一に担持させることができる。According to the present invention, by adding a surfactant to an aqueous solution of an organic acid salt of an active metal, a catalytically active component is uniformly supported not only on the surface but also on the inside of a catalyst carrier composed of an inorganic fiber structure. Can be done.
【００７０】また、構造体の表面および内部にまで均一
に触媒活性成分が担持されており、かつ有機酸塩を含む
溶液を焼成することにより触媒活性成分を得ているた
め、硝酸痕等の残存成分がなく燃焼活性等に優れた触媒
を製造することができる。Further, the catalytically active component is uniformly supported on the surface and inside of the structure, and the catalytically active component is obtained by baking the solution containing the organic acid salt. A catalyst having no components and excellent in combustion activity and the like can be produced.
【００７１】併用する界面活性剤の中でも特に非イオン
性界面活性剤を使用するとその効果は顕著である。The effect is remarkable when a nonionic surfactant is used among the surfactants used in combination.
【図１】 無機繊維製触媒による粒子状物質燃焼性能を
示す図である。FIG. 1 is a diagram showing the particulate matter combustion performance of an inorganic fiber catalyst.
【図２】 無機繊維構造体内部の電子顕微鏡写真コピー
である。FIG. 2 is an electron micrograph copy of the inside of the inorganic fiber structure.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｄ 53/94 Ｂ０１Ｊ 23/10 Ａ Ｂ０１Ｊ 23/10 23/76 Ａ 23/76 37/02 １０１Ｚ 37/02 １０１ Ｆ０１Ｎ 3/02 ３０１Ａ Ｆ０１Ｎ 3/02 ３０１ ３２１Ａ ３２１ Ｂ０１Ｄ 53/36 １０４Ｂ Ｆターム(参考） 3G090 AA01 AA03 BA01 4D019 AA01 BA02 BA04 BA05 BB01 BC07 4D048 AA06 AA14 AA18 AB01 BA03Y BA06X BA07Y BA08Y BA10X BA14Y BA18Y BA19X BA30Y BA31Y BA32Y BA33Y BA35X BA39X BA41Y BA42Y BA45X BB08 4G069 AA03 AA08 BA01A BA02A BA03A BA04A BA05A BA14A BA17 BA18 BA21C BA26C BB02A BB02B BB04A BB04B BB06A BB08C BB10C BB12C BB14C BB15A BB15B BB16C BC01A BC01C BC03A BC05A BC31A BC31B BC32A BC33A BC41A BC41C BC42A BC43A BC43B BC44A BC44C BC49A BC49C BC50A BC65A BC69A BC69C BC70A BC70C BC71A BC71C BC72A BC72C BC73A BC73C BC74A BC74C BC75A BC75C BD05A BD05B BD12C BE08C BE44C CA02 CA03 CA07 CA13 CA15 CA18 EA09 FA02 FB05 FB16 FB30 FC08Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) B01D 53/94 B01J 23/10 A B01J 23/10 23/76 A 23/76 37/02 101Z 37/02 101 F01N 3 / 02 301A F01N 3/02 301 321A 321 B01D 53/36 104B F term (reference) 3G090 AA01 AA03 BA01 4D019 AA01 BA02 BA04 BA05 BB01 BC07 4D048 AA06 AA14 AA18 AB01 BA03Y BA06X BA07Y BA10Y BA10X BA18Y BA10X BA41Y BA42Y BA45X BB08 4G069 AA03 AA08 BA01A BA02A BA03A BA04A BA05A BA14A BA17 BA18 BA21C BA26C BB02A BB02B BB04A BB04B BB06A BB08C BB10C BB12C BB14C BB15A BB15B BB16C BC01A BC01C BC03A BC05A BC31A BC31B BC32A BC33A BC41A BC41C BC42A BC43A BC43B BC44A BC44C BC49A BC49C BC50A BC65A BC69A BC69C BC70A BC70C BC71A BC71C BC72A BC72C BC73A BC73C BC74A BC74C BC75A BC75C BD05A BD05B BD12C BE08C BE44C CA02 CA03 CA07 CA13 CA15 CA18 EA09 FA02 FB05 FB16 FB30 FC08
Claims (10)
（Ｂ）界面活性剤、とを含む活性成分水溶液に、（Ｃ）
無機繊維構造体を浸漬した後、前記構造体を乾燥、焼成
することを特徴とする無機繊維製触媒の製造方法。1. An active ingredient aqueous solution containing (A) an organic acid salt having an active ingredient element and (B) a surfactant,
A method for producing an inorganic fiber catalyst, characterized by drying and firing the structure after immersing the inorganic fiber structure.
（Ｄ）水溶性有機溶剤、とを含む活性成分水溶液に、
（Ｃ）無機繊維構造体を浸漬した後、前記構造体を乾
燥、焼成することを特徴とする無機繊維製触媒の製造方
法。2. An active ingredient aqueous solution containing (A) an organic acid salt having an active ingredient element and (D) a water-soluble organic solvent,
(C) A method for producing a catalyst made of inorganic fibers, wherein the structure is dried and fired after immersing the inorganic fiber structure.
耐熱性金属繊維、チタン酸カリウム繊維、チラノ繊維、
アルミナ繊維、シリカ繊維、シリカ・アルミナ繊維、ジ
ルコニア繊維、チタニア繊維、炭化珪素被覆炭素繊維お
よびガラス繊維からなる群から選ばれる少なくとも１種
の材質からなることを特徴とする、請求項１または２に
記載の無機繊維製触媒の製造方法。3. The method according to claim 1, wherein the inorganic fiber structure comprises silicon carbide fibers,
Heat-resistant metal fiber, potassium titanate fiber, tyrano fiber,
The material according to claim 1 or 2, wherein the material is at least one material selected from the group consisting of alumina fiber, silica fiber, silica / alumina fiber, zirconia fiber, titania fiber, silicon carbide-coated carbon fiber, and glass fiber. A method for producing the inorganic fiber catalyst described in the above.
塩、グリコール酸塩およびクエン酸塩からなる群から選
ばれる少なくとも１種であることを特徴とする、請求項
１〜３のいずれか１つに記載の無機繊維製触媒の製造方
法。4. The method according to claim 1, wherein the organic acid salt is at least one selected from the group consisting of acetate, oxalate, formate, glycolate and citrate. A method for producing an inorganic fiber catalyst according to any one of the above.
を有する、無機酸塩および／または錯体塩を含んでお
り、前記無機酸塩が、硝酸塩、リン酸塩、硫酸塩、炭酸
塩、塩酸塩および金属酸塩からなる群から選ばれる少な
くとも１種であり、前記錯体塩がアンミン錯体塩である
ことを特徴とする、請求項１〜４のいずれか１つに記載
の無機繊維製触媒の製造方法。5. The aqueous solution further comprises (E) an inorganic acid salt and / or a complex salt having an active ingredient element, wherein the inorganic acid salt is a nitrate, a phosphate, a sulfate, a carbonate, The inorganic fiber catalyst according to any one of claims 1 to 4, wherein the complex salt is at least one selected from the group consisting of a hydrochloride and a metal salt, and the complex salt is an ammine complex salt. Manufacturing method.
リ金属元素、第ＶＩＩＩ族元素、ランタニド元素および
チタン族元素からなる群から選ばれる少なくとも１種の
元素であることを特徴とする、請求項１〜５のいずれか
１つに記載の無機繊維製触媒の製造方法。6. The active ingredient element of the organic acid salt is at least one element selected from the group consisting of an alkali metal element, a group VIII element, a lanthanide element and a titanium group element. Item 6. The method for producing an inorganic fiber catalyst according to any one of Items 1 to 5.
基準で２０ｖｏｌｐｐｍ以上１ｖｏｌ％以下であること
を特徴とする、請求項１または請求項３〜６のいずれか
１つに記載の無機繊維製触媒の製造方法。7. The inorganic fiber according to claim 1, wherein the amount of the surfactant is 20 vol ppm or more and 1 vol% or less based on the total amount of the active ingredient aqueous solution. Method for producing catalyst.
全量基準で３０〜７０質量％であることを特徴とする請
求項２〜６のいずれか１つに記載の無機繊維製触媒の製
造方法。8. The method for producing an inorganic fiber catalyst according to claim 2, wherein the amount of the water-soluble organic solvent is 30 to 70% by mass based on the total amount of the aqueous solution of the active ingredient. Method.
法で製造された無機繊維製触媒であり、無機繊維構造体
表面に、銅、金、銀、カリウム、セシウムおよびルビジ
ウムからなる群から選ばれる１種以上の元素を含む活性
金属あるいは活性金属化合物が形成されている無機繊維
製触媒。9. An inorganic fiber catalyst produced by the method according to any one of claims 1 to 8, wherein the surface of the inorganic fiber structure comprises copper, gold, silver, potassium, cesium, and rubidium. An inorganic fiber catalyst on which an active metal or an active metal compound containing at least one element selected from the group is formed.
が、更にセリウム、チタンおよびランタンからなる群か
ら選ばれる１種以上の元素を含むことを特徴とする請求
項９に記載の無機繊維製触媒。10. The inorganic fiber catalyst according to claim 9, wherein the active metal or the active metal compound further contains at least one element selected from the group consisting of cerium, titanium and lanthanum.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001171768A JP2002326036A (en) | 2001-05-02 | 2001-05-02 | Method of producing catalyst made of inorganic fiber and catalyst made of inorganic fiber obtained by the method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001171768A JP2002326036A (en) | 2001-05-02 | 2001-05-02 | Method of producing catalyst made of inorganic fiber and catalyst made of inorganic fiber obtained by the method |
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|---|---|
| JP2002326036A true JP2002326036A (en) | 2002-11-12 |
Family
ID=19013486
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005270714A (en) * | 2004-03-23 | 2005-10-06 | Matsushita Electric Ind Co Ltd | Exhaust gas cleaning material and its manufacturing method |
| JP2007512211A (en) * | 2003-04-28 | 2007-05-17 | ナノシス・インク． | Super lyophobic surface, its preparation and use |
| EP2025397A1 (en) | 2007-08-09 | 2009-02-18 | Nissan Motor Company Limited | Inorganic fiber catalyst, production method thereof and catalyst structure |
| US10682637B2 (en) | 2014-11-20 | 2020-06-16 | Kao Corporation | Method for producing catalyst fibrous structure |
| CN113694931A (en) * | 2021-08-30 | 2021-11-26 | 一汽解放汽车有限公司 | Composite catalyst, catalyst suspension, preparation method and application thereof |
| SE2250571A1 (en) * | 2022-05-12 | 2023-11-13 | Scandcycle Ab | Process and active catalyst for the glykolysis of polyethylene terephthalate (pet) |
-
2001
- 2001-05-02 JP JP2001171768A patent/JP2002326036A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007512211A (en) * | 2003-04-28 | 2007-05-17 | ナノシス・インク． | Super lyophobic surface, its preparation and use |
| JP2005270714A (en) * | 2004-03-23 | 2005-10-06 | Matsushita Electric Ind Co Ltd | Exhaust gas cleaning material and its manufacturing method |
| EP2025397A1 (en) | 2007-08-09 | 2009-02-18 | Nissan Motor Company Limited | Inorganic fiber catalyst, production method thereof and catalyst structure |
| JP2009061443A (en) * | 2007-08-09 | 2009-03-26 | Nissan Motor Co Ltd | Inorganic fiber catalyst, production method thereof and catalyst structure |
| US7910514B2 (en) | 2007-08-09 | 2011-03-22 | Nissan Motor Co., Ltd. | Inorganic fiber catalyst, production method thereof and catalyst structure |
| US10682637B2 (en) | 2014-11-20 | 2020-06-16 | Kao Corporation | Method for producing catalyst fibrous structure |
| CN113694931A (en) * | 2021-08-30 | 2021-11-26 | 一汽解放汽车有限公司 | Composite catalyst, catalyst suspension, preparation method and application thereof |
| CN113694931B (en) * | 2021-08-30 | 2023-11-07 | 一汽解放汽车有限公司 | Composite catalyst, catalyst suspension, preparation method and application thereof |
| SE2250571A1 (en) * | 2022-05-12 | 2023-11-13 | Scandcycle Ab | Process and active catalyst for the glykolysis of polyethylene terephthalate (pet) |
| WO2023217897A1 (en) * | 2022-05-12 | 2023-11-16 | Scandcycle Ab | Process and active catalyst for the glykolysis of polyethylene terephthalate (pet) |
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