JP2002018291A - Metal oxide catalyst and method for manufacturing the same - Google Patents
Metal oxide catalyst and method for manufacturing the sameInfo
- Publication number
- JP2002018291A JP2002018291A JP2000202894A JP2000202894A JP2002018291A JP 2002018291 A JP2002018291 A JP 2002018291A JP 2000202894 A JP2000202894 A JP 2000202894A JP 2000202894 A JP2000202894 A JP 2000202894A JP 2002018291 A JP2002018291 A JP 2002018291A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- weight
- catalyst
- tio
- parts
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 88
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 109
- 239000000126 substance Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 90
- 239000000654 additive Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 38
- 230000000996 additive effect Effects 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 229910000510 noble metal Inorganic materials 0.000 claims description 29
- 229920001451 polypropylene glycol Polymers 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 239000007795 chemical reaction product Substances 0.000 abstract description 6
- 230000035515 penetration Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 150000004703 alkoxides Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000376 reactant Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229960002429 proline Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- -1 M n Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 229930182821 L-proline Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 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
- 229960003646 lysine Drugs 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】 本発明は、金属酸化物系触
媒及び金属酸化物系触媒の製造方法に関する。より詳し
くは、反応物質の活性部位への迅速な浸入及び反応生成
物の活性部位からの迅速な脱離と、活性部位での高い触
媒活性を同時に達成して、極めて高い触媒効果を発揮す
ることができ、特に、ダイオキシン分解反応又は水素製
造反応に有用な金属酸化物系触媒及び金属酸化物系触媒
の製造方法に関する。TECHNICAL FIELD The present invention relates to a metal oxide catalyst and a method for producing a metal oxide catalyst. More specifically, a very high catalytic effect is achieved by simultaneously achieving rapid penetration of a reactant into an active site and rapid desorption of a reaction product from an active site, and high catalytic activity in the active site. In particular, the present invention relates to a metal oxide catalyst useful for a dioxin decomposition reaction or a hydrogen production reaction, and a method for producing a metal oxide catalyst.
【０００２】[0002]
【従来の技術】 近年、酸化チタン等の金属酸化物系触
媒が、光触媒等として広く用いられている。また、環境
保全の意識の高まりにともない、このような金属酸化物
系触媒をダイオキシン分解反応又は水素製造反応へ利用
することが検討されている。2. Description of the Related Art In recent years, metal oxide catalysts such as titanium oxide have been widely used as photocatalysts and the like. In addition, with increasing awareness of environmental conservation, utilization of such a metal oxide-based catalyst for a dioxin decomposition reaction or a hydrogen production reaction is being studied.
【０００３】 従来、金属酸化物系触媒の製造方法とし
ては、チタンと白金等の貴金属を含む添加物を成膜して
加熱を行うことにより、非常に微細な貴金属をＴｉＯ2
粒子に分散させて触媒を製造する方法が開示されている
（特開平１０−１１４５２１号公報）。この製造方法
は、金属酸化物系触媒の活性を高める白金等の貴金属を
ＴｉＯ2粒子に分散させて触媒を製造することにより高
活性の金属酸化物系触媒を製造するものである。Conventionally, as a method for producing a metal oxide-based catalyst, an additive containing a noble metal such as titanium and platinum is formed into a film and heated to convert a very fine noble metal into TiO 2.
A method for producing a catalyst by dispersing it in particles has been disclosed (JP-A-10-114521). In this production method, a noble metal such as platinum which enhances the activity of the metal oxide catalyst is dispersed in TiO 2 particles to produce a catalyst, thereby producing a highly active metal oxide catalyst.
【０００４】 しかし、この製造方法では、触媒中に形
成される孔径を制御していないため、孔径が小さいとこ
ろでは反応物質が迅速に活性部位まで浸入できず、孔径
が大きいところでは活性部位で高い触媒活性を得ること
ができなかった。However, in this production method, since the pore size formed in the catalyst is not controlled, the reactant cannot quickly penetrate to the active site where the pore size is small, and is high in the active site where the pore size is large. No catalytic activity could be obtained.
【０００５】 これに対して、金属アルコキシドとアル
コールアミン等から調製したゾル液にポリエチレングリ
コール、又はポリエチレンオキサイドを添加した後、加
熱する製造方法が提案されている（特開平１０−２５９
０７４号公報）。この製造方法では、高分子化合物であ
るポリエチレングリコール、又はポリエチレンオキサイ
ドをその分子量及び濃度を制御することにより、触媒に
形成される細孔の孔径及び細孔容積率を一定範囲で制御
することができるものである。On the other hand, there has been proposed a production method in which polyethylene glycol or polyethylene oxide is added to a sol solution prepared from a metal alkoxide and an alcoholamine, and then heated (JP-A-10-259).
No. 074). In this production method, by controlling the molecular weight and concentration of polyethylene glycol or polyethylene oxide, which is a polymer compound, the pore diameter and pore volume ratio of pores formed in the catalyst can be controlled within a certain range. Things.
【０００６】[0006]
【発明が解決しようとする課題】 しかしながら、この
製造方法では反応物質を迅速に活性部位まで浸入させ、
その後反応生成物を迅速に活性部位から脱離させるため
に好適な孔径の細孔を適切な細孔容積率で有すること
と、活性部位での高い触媒活性を獲得するために好適な
孔径の細孔を適切な細孔容積率で有することとを同時に
達成することができないため、必ずしも十分な触媒効果
を有するものではなかった。However, in this production method, the reactants are quickly penetrated to the active site,
Thereafter, having a pore with a suitable pore size at an appropriate pore volume ratio for quickly desorbing the reaction product from the active site, and a pore having a suitable pore size for obtaining high catalytic activity at the active site. It is not always possible to achieve a sufficient catalytic effect because it is not possible to simultaneously achieve pores with an appropriate pore volume ratio.
【０００７】 本発明は、上述の問題に鑑みなされたも
のであり、反応物質の活性部位への迅速な浸入及び反応
生成物の活性部位からの迅速な脱離と、活性部位での高
い触媒活性を同時に達成して、極めて高い触媒効果を発
揮することができ、特に、ダイオキシン分解反応又は水
素製造反応に有用な金属酸化物系触媒及び金属酸化物系
触媒の製造方法を提供することを目的とする。[0007] The present invention has been made in view of the above-mentioned problems, and has a problem in that a rapid intrusion of a reactant into an active site, a rapid desorption of a reaction product from an active site, and a high catalytic activity in the active site are performed. Simultaneously to achieve a very high catalytic effect, particularly to provide a metal oxide catalyst useful for dioxin decomposition reaction or hydrogen production reaction and a method for producing a metal oxide catalyst. I do.
【０００８】[0008]
【課題を解決するための手段】 本発明者は、上述の課
題を解決するべく鋭意研究した結果、特定の粒径のゾル
物質と、特定の分子量の高分子物質とを特定の割合で混
合してこの混合物を特定温度で加熱するにより、上記目
的を達成するために好適な異なる孔径及び細孔容積率を
有する二種の細孔を形成できることを知見し、本発明を
完成させた。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a sol material having a specific particle size and a polymer material having a specific molecular weight are mixed at a specific ratio. The present inventors have found that by heating a leverage mixture at a specific temperature, two types of pores having different pore diameters and pore volume ratios suitable for achieving the above object can be formed, and the present invention has been completed.
【０００９】 本発明によれば、孔径３〜３０ｎｍの第
一の細孔を０．０１〜０．６０ｃｍ3／ｃｍ3（細孔容積
／触媒の見掛け容積）の細孔容積率で有するとともに、
孔径５０〜５００ｎｍの第二の細孔を０．０１〜０．６
０ｃｍ3／ｃｍ3（細孔容積／触媒の見掛け容積）の細孔
容積率で有することを特徴とする金属酸化物系触媒が提
供される。本発明の金属酸化物系触媒においては、金属
酸化物中に貴金属を分散してなるものが好ましい。ま
た、金属酸化物系触媒が、ハニカム形状を有してなるも
の、又はハニカム形状の支持体上に金属酸化物が担持さ
れてなるものが好ましい。本発明の製造方法は、好適に
はダイオキシン分解反応又は水素製造反応に用いられ
る。According to the present invention, the first pores having a pore diameter of 3 to 30 nm have a pore volume ratio of 0.01 to 0.60 cm 3 / cm 3 (pore volume / apparent volume of the catalyst), and
A second pore having a pore diameter of 50 to 500 nm is set to 0.01 to 0.6.
A metal oxide catalyst having a pore volume ratio of 0 cm 3 / cm 3 (pore volume / apparent volume of catalyst) is provided. In the metal oxide-based catalyst of the present invention, a catalyst obtained by dispersing a noble metal in a metal oxide is preferable. Further, it is preferable that the metal oxide-based catalyst has a honeycomb shape, or that the metal oxide is supported on a honeycomb-shaped support. The production method of the present invention is suitably used for a dioxin decomposition reaction or a hydrogen production reaction.
【００１０】 一方、本発明によれば、粒径３〜５０ｎ
ｍの金属酸化物粒子を含有するゾル物質５〜５０重量部
（金属酸化物換算重量）と、分子量２００〜２００万の
高分子物質５〜５０重量部とを混合し、当該混合物を３
００〜７００℃で加熱することを特徴とする金属酸化物
系触媒の製造方法が提供される。本発明の製造方法にお
いては、金属酸化物粒子が、ＴｉＯ2粒子であることが
好ましい。また、高分子物質は、ポリプロピレングリコ
ールであることが好ましい。また、ゾル物質と高分子物
質の混合物に、貴金属と貴金属以外の金属とを含有する
添加物をさらに所定量添加することが好ましい。この添
加物の添加量は、混合物１０〜１００重量部に対して、
５０〜９５重量部（金属酸化物換算重量）であることが
好ましく、添加物に含有される貴金属は、白金であるこ
とが好ましい。添加物は、チタン（Ｔｉ）と白金（Ｐ
ｔ）とを分子内に有する化合物を含むものであることが
より好ましい。On the other hand, according to the present invention, the particle size is 3 to 50 n.
5 to 50 parts by weight (weight in terms of metal oxide) of a sol substance containing metal oxide particles of m and 5 to 50 parts by weight of a polymer substance having a molecular weight of 2 to 2,000,000.
A method for producing a metal oxide-based catalyst characterized by heating at 00 to 700 ° C is provided. In the production method of the present invention, the metal oxide particles are preferably TiO 2 particles. Further, the polymer substance is preferably polypropylene glycol. Further, it is preferable to further add a predetermined amount of an additive containing a noble metal and a metal other than the noble metal to the mixture of the sol substance and the polymer substance. The amount of the additive is 10 to 100 parts by weight of the mixture.
The amount is preferably 50 to 95 parts by weight (weight in terms of metal oxide), and the noble metal contained in the additive is preferably platinum. The additives are titanium (Ti) and platinum (P
It is more preferable to include a compound having (t) in the molecule.
【００１１】[0011]
【発明の実施の形態】 以下、本発明の実施の形態を、
具体的に説明する。本発明の金属酸化物系触媒は、孔径
３〜３０ｎｍの第一の細孔を０．０１〜０．６０ｃｍ3
／ｃｍ3（細孔容積／触媒の見掛け容積）の細孔容積率
で有するとともに、孔径５０〜５００ｎｍの第二の細孔
を０．０１〜０．６０ｃｍ3／ｃｍ3（細孔容積／触媒の
見掛け容積）の細孔容積率で有するものである。また、
本発明の金属酸化物系触媒の製造方法は、粒径３〜５０
ｎｍの金属酸化物粒子を含有するゾル物質５〜５０重量
部（金属酸化物換算重量）と、分子量２００〜２００万
の高分子物質５〜５０重量部とを混合し、当該混合物を
３００〜７００℃で加熱するものである。以下、それぞ
れについて具体的に説明する。Hereinafter, embodiments of the present invention will be described.
This will be specifically described. The metal oxide-based catalyst of the present invention has a first pore having a pore diameter of 3 to 30 nm of 0.01 to 0.60 cm 3.
/ Cm 3 and having pore volume rate (apparent volume of pore volume / catalyst), 0.01~0.60cm 3 / cm 3 the second pores having a pore diameter of 50 to 500 nm (pore volume / catalyst (Apparent volume). Also,
The method for producing a metal oxide-based catalyst of the present invention has a particle diameter of 3 to 50.
5 to 50 parts by weight (weight in terms of metal oxide) of a sol material containing metal oxide particles having a diameter of 200 nm and 5 to 50 parts by weight of a polymer material having a molecular weight of 2 to 2,000,000 are mixed. Heat at ℃. Hereinafter, each of them will be specifically described.
【００１２】１．金属酸化物系触媒 前述したとおり本発明の金属酸化物系触媒は、異なる特
定孔径の第一の細孔及び第二の細孔をそれぞれ特定の細
孔容積率で有するものである。1. Metal Oxide Catalyst As described above, the metal oxide catalyst of the present invention has first pores and second pores having different specific pore sizes at specific pore volume ratios.
【００１３】 第一の細孔の孔径は、３〜３０ｎｍ、好
ましくは１０〜２５ｎｍである。第一の細孔の孔径がこ
の範囲外であると、活性部位で高い触媒活性を得ること
がきなくなる。ここで、細孔の孔径は、ポロシメータに
より求めたものである。[0013] The pore size of the first pore is 3 to 30 nm, preferably 10 to 25 nm. If the pore diameter of the first pores is out of this range, it becomes impossible to obtain high catalytic activity at the active site. Here, the pore diameter of the pore is determined by a porosimeter.
【００１４】 第一の細孔の細孔容積率は、０．０１〜
０．６０ｃｍ3／ｃｍ3（細孔容積／触媒の見掛け容
積）、好ましくは０．１０〜０．４０ｃｍ3／ｃｍ3（細
孔容積／触媒の見掛け容積）である。第一の細孔の細孔
容積率が、０．０１ｃｍ3／ｃｍ3（細孔容積／触媒の見
掛け容積）未満であると触媒効果が不十分となり、０．
６０ｃｍ3／ｃｍ3（細孔容積／触媒の見掛け容積）を超
えると触媒の機械的強度が低下し、実用上において問題
となる。[0014] The pore volume ratio of the first pores is 0.01 to
0.60 cm 3 / cm 3 (apparent volume of pore volume / catalyst), preferably 0.10~0.40cm 3 / cm 3 (apparent volume of pore volume / catalyst). When the pore volume ratio of the first pores is less than 0.01 cm 3 / cm 3 (pore volume / apparent volume of the catalyst), the catalytic effect becomes insufficient, and the pore volume ratio becomes lower.
If it exceeds 60 cm 3 / cm 3 (pore volume / apparent volume of the catalyst), the mechanical strength of the catalyst decreases, which is problematic in practical use.
【００１５】 本発明の第二の細孔の孔径は、５０〜５
００ｎｍ、好ましくは、１００〜３００ｎｍである。孔
径が５０ｎｍ未満であると、反応物質の活性部位への浸
入及び反応生成物の活性部位からの脱離が妨げられ結局
触媒効果が不十分となり、５００ｎｍを超えると反応物
質が活性部位でほとんど滞留しくなるためやはり触媒効
果が不十分となり、また、機械的強度が低下して実用上
において問題となる。なお、第二の細孔の孔径は、第一
の細孔の孔径と同様にして求めたものである。The pore size of the second pore of the present invention is 50 to 5
00 nm, preferably 100 to 300 nm. If the pore size is less than 50 nm, the intrusion of the reactant into the active site and the desorption of the reaction product from the active site are prevented, resulting in insufficient catalytic effect. If the pore size exceeds 500 nm, the reactant almost stays in the active site. As a result, the catalytic effect becomes insufficient, and the mechanical strength is reduced, which is problematic in practical use. The pore size of the second pore is determined in the same manner as the pore size of the first pore.
【００１６】 第二の細孔の細孔容積率は、０．０１〜
０．６０ｃｍ3／ｃｍ3（細孔容積／触媒の見掛け容
積）、好ましくは０．２０〜０．５０ｃｍ3／ｃｍ3（細
孔容積／触媒の見掛け容積）である。第二の細孔の細孔
容積率が、０．０１ｃｍ3／ｃｍ3（細孔容積／触媒の見
掛け容積）未満であると触媒効果が不十分となり、０．
６０ｃｍ3／ｃｍ3（細孔容積／触媒の見掛け容積）を超
えると機械的強度が低下し、実用上において問題とな
る。[0016] The pore volume ratio of the second pores is 0.01 to
0.60 cm 3 / cm 3 (apparent volume of pore volume / catalyst), preferably 0.20~0.50cm 3 / cm 3 (apparent volume of pore volume / catalyst). If the pore volume ratio of the second pores is less than 0.01 cm 3 / cm 3 (pore volume / apparent volume of the catalyst), the catalytic effect becomes insufficient, and 0.
If it exceeds 60 cm 3 / cm 3 (pore volume / apparent volume of the catalyst), the mechanical strength decreases, which is problematic in practical use.
【００１７】 本発明においては、金属酸化物系触媒の
形状について特に制限はないが、反応物質との接触面積
を増大させるため、ハニカム形状とするのが好ましい。
また、金属酸化物系触媒をハニカム形状とするのが困難
な場合はハニカム形状の支持体上に金属酸化物を担持さ
せてもよい。In the present invention, the shape of the metal oxide-based catalyst is not particularly limited. However, in order to increase a contact area with a reactant, the catalyst is preferably formed in a honeycomb shape.
When it is difficult to make the metal oxide catalyst into a honeycomb shape, the metal oxide may be supported on a honeycomb-shaped support.
【００１８】 なお、本発明の金属酸化物系触媒は、ダ
イオキシン分解反応又は水素製造反応の極めて好適な触
媒として用いることができる。また、本発明の金属酸化
物系触媒は、以下で述べる製造方法で得ることができ
る。The metal oxide catalyst of the present invention can be used as a very suitable catalyst for a dioxin decomposition reaction or a hydrogen production reaction. Further, the metal oxide-based catalyst of the present invention can be obtained by the production method described below.
【００１９】２．金属酸化物系触媒製造方法 前述したように本発明の金属酸化物系触媒製造方法は、
特定のゾル物質と特定の高分子物質とを所定割合で混合
し、得られた混合物を特定温度で加熱するものである。2. Metal oxide catalyst production method As described above, the metal oxide catalyst production method of the present invention,
A specific sol substance and a specific polymer substance are mixed at a predetermined ratio, and the resulting mixture is heated at a specific temperature.
【００２０】 本発明に用いられるゾル物質は、３〜５
０ｎｍ、好ましくは５〜３０ｎｍの粒径の金属酸化物粒
子を含有するものである。金属酸化物粒子の粒径がこの
範囲外であると、活性部位で高活性を得るために好適な
孔径を有する第一の細孔を形成することができなくなる
ため、触媒効果が低下する。The sol substance used in the present invention is 3 to 5
It contains metal oxide particles having a particle size of 0 nm, preferably 5 to 30 nm. If the particle size of the metal oxide particles is out of this range, it is not possible to form first pores having a pore size suitable for obtaining high activity at the active site, so that the catalytic effect is reduced.
【００２１】 ゾル物質に含有する金属酸化物粒子とし
ては、例えば、Ａｌ、Ｂ、Ｂａ、Ｃａ、Ｃｄ、Ｃｅ、Ｃ
ｏ、Ｃｒ、Ｆｅ、Ｇｅ、Ｈｆ、Ｉｎ、Ｌｉ、Ｍｇ、Ｍ
ｎ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐｂ、Ｒｕ、Ｓｉ、Ｓｎ、Ｓ
ｒ、Ｔａ、Ｔｉ、Ｖ、Ｗ、Ｙ、Ｚｒからなる群から選ば
れる少なくとも１種を含む金属酸化物粒子等を挙げるこ
とができる。中でも、触媒活性及び触媒寿命の点からＴ
ｉＯ2粒子が好ましい。The metal oxide particles contained in the sol material include, for example, Al, B, Ba, Ca, Cd, Ce, C
o, Cr, Fe, Ge, Hf, In, Li, Mg, M
n, Mo, Nb, Ni, Pb, Ru, Si, Sn, S
Metal oxide particles containing at least one selected from the group consisting of r, Ta, Ti, V, W, Y, and Zr can be used. Among them, from the viewpoint of catalyst activity and catalyst life, T
iO 2 particles are preferred.
【００２２】 本発明に用いられるゾル物質は、例え
ば、所定の粒径にした金属酸化物粒子を分散媒としての
溶媒に懸濁して製造することができる。この際、溶媒と
しては、例えば、水、アルコール類等を挙げることがで
き、必要に応じて分散促進剤として界面活性剤を添加し
てもよい。The sol substance used in the present invention can be produced, for example, by suspending metal oxide particles having a predetermined particle size in a solvent as a dispersion medium. At this time, examples of the solvent include water, alcohols, and the like. If necessary, a surfactant may be added as a dispersion accelerator.
【００２３】 本発明に用いられるゾル物質は、この他
に、例えば、アルコールと金属塩又は金属と反応させて
得られる金属アルコキシド；金属アルコキシドの一部を
アセチルアセトナート基等の置換基で置換した金属アル
コキシド誘導体；金属アルコキシドに溶解した金属塩等
を加水分解して調製することができる。The sol substance used in the present invention may be, for example, a metal alkoxide obtained by reacting an alcohol with a metal salt or a metal; a part of the metal alkoxide is substituted with a substituent such as an acetylacetonate group. Metal alkoxide derivative; can be prepared by hydrolyzing a metal salt or the like dissolved in a metal alkoxide.
【００２４】 金属アルコキシドとしては、例えば、Ａ
ｌ、Ｂ、Ｂａ、Ｃａ、Ｃｄ、Ｃｅ、Ｃｏ、Ｃｒ、Ｆｅ、
Ｇｅ、Ｈｆ、Ｉｎ、Ｌｉ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎ
ｉ、Ｐｂ、Ｒｕ、Ｓｉ、Ｓｎ、Ｓｒ、Ｔａ、Ｔｉ、Ｖ、
Ｗ、Ｙ、Ｚｒからなる群から選ばれる少なくとも１種を
含む金属アルコキシド等を挙げることができる。これら
金属アルコキシドは、１種単独で又は２種以上を組合わ
せて用いることができる。As the metal alkoxide, for example, A
1, B, Ba, Ca, Cd, Ce, Co, Cr, Fe,
Ge, Hf, In, Li, Mg, Mn, Mo, Nb, N
i, Pb, Ru, Si, Sn, Sr, Ta, Ti, V,
Metal alkoxides containing at least one selected from the group consisting of W, Y and Zr can be mentioned. These metal alkoxides can be used alone or in combination of two or more.
【００２５】 また、金属塩としては、例えば、Ａｌ、
Ｂ、Ｂａ、Ｃａ、Ｃｄ、Ｃｅ、Ｃｏ、Ｃｒ、Ｆｅ、Ｇ
ｅ、Ｈｆ、Ｉｎ、Ｌｉ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎ
ｉ、Ｐｂ、Ｒｕ、Ｓｉ、Ｓｎ、Ｓｒ、Ｔａ、Ｔｉ、Ｖ、
Ｗ、Ｙ、Ｚｒからなる群から選ばれる少なくとも１種の
酢酸塩、蓚酸塩、２−エチルヘキサン酸塩、ステアリン
酸塩、乳酸塩、アセチル酢酸塩等を挙げることができ
る。これら金属塩は、１種単独で又は２種以上を組合わ
せて用いることができる。As the metal salt, for example, Al,
B, Ba, Ca, Cd, Ce, Co, Cr, Fe, G
e, Hf, In, Li, Mg, Mn, Mo, Nb, N
i, Pb, Ru, Si, Sn, Sr, Ta, Ti, V,
Examples include at least one kind of acetate, oxalate, 2-ethylhexanoate, stearate, lactate, acetyl acetate, and the like selected from the group consisting of W, Y, and Zr. These metal salts can be used alone or in combination of two or more.
【００２６】 これら金属アルコキシド等を加水分解し
てゾル物質を調製する際には、モノエタノールアミン、
ジエタノールアミン、トリエタノールアミン、Ｎ−メチ
ルジエタノールアミン、Ｎ−エチルジエタノールアミ
ン、Ｎ−ジメチルジアミノエタノール、ジイソプロパノ
ールアミン等のアルコールアミン類を添加することが好
ましい。これにより均一で透明なゾル物質が得られ、耐
久性に優れる触媒とすることができる。When preparing a sol substance by hydrolyzing these metal alkoxides and the like, monoethanolamine,
It is preferable to add alcohol amines such as diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-dimethyldiaminoethanol, and diisopropanolamine. As a result, a uniform and transparent sol substance is obtained, and a catalyst having excellent durability can be obtained.
【００２７】 なお、本発明においては、ゾル物質中の
金属酸化物の濃度について特に限定はないが、１０〜３
０重量％が好ましく、１５〜２５重量％がより好まし
い。In the present invention, the concentration of the metal oxide in the sol substance is not particularly limited.
0% by weight is preferable, and 15 to 25% by weight is more preferable.
【００２８】 本発明に用いられる高分子物質は、２０
０〜２００万、好ましくは、１０００〜１００万の分子
量を有するものである。分子量が、２００未満であると
反応物質を活性部位へ迅速に浸入させるのに好適な孔径
を有する第二の細孔を形成することができないため、結
局触媒効果が低下する。一方、２００万を超えると反応
物質を活性部位で一定時間滞留させるのに好適な孔径を
有する第二の細孔を形成することができないため、結局
触媒効果が低下する。ここで、高分子物質の分子量は、
ゲルクロマトグラフィー法（ＧＰＣ法）により求めたも
のである。The polymer substance used in the present invention is 20
It has a molecular weight of from 0 to 2,000,000, preferably from 1,000 to 1,000,000. If the molecular weight is less than 200, the second pore having a pore diameter suitable for allowing the reactant to rapidly penetrate into the active site cannot be formed, so that the catalytic effect eventually decreases. On the other hand, if it exceeds 2,000,000, it is impossible to form a second pore having a pore diameter suitable for retaining the reactant in the active site for a certain period of time, so that the catalytic effect is eventually reduced. Here, the molecular weight of the polymer substance is
It was determined by a gel chromatography method (GPC method).
【００２９】 本発明に用いられる高分子物質として
は、例えば、ポリエチレングリコール、ポリプロピレン
グリコール、ポリエチレンオキサイド、ポリプロピレン
オキサイド等が好ましい。中でも、形成される第二の細
孔を好適な孔径及び細孔容積率とすることができる点か
らポリプロピレングリコールが特に好ましい。これら高
分子物質は、例えば、触媒添加加熱法により製造するこ
とができる。As the polymer substance used in the present invention, for example, polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide and the like are preferable. Among them, polypropylene glycol is particularly preferred in that the formed second pores can have a suitable pore diameter and pore volume ratio. These polymer substances can be produced, for example, by a catalyst addition heating method.
【００３０】 本発明の金属酸化物系触媒製造方法では
前述したゾル物質５〜５０重量部（金属酸化物換算重
量）に、前述した高分子物質を５〜５０重量部、より好
ましくは前述したゾル物質７〜３０重量部（金属酸化物
換算重量）に、前述した高分子物質を１０〜３０重量部
混合する。ゾル物質の割合が、５重量部（金属酸化物換
算重量）未満であると第一の細孔の細孔容積率が小さく
なって触媒活性が低下し、５０重量部（金属酸化物換算
重量）を超えると第二の細孔形成が不十分なって触媒活
性が低下する。また、高分子物質の割合が、５重量部未
満であると第二の細孔形成が不十分なって触媒活性が低
下し、５０重量部を超えると第一の細孔の細孔容積率が
小さくなって触媒活性が低下する。In the method for producing a metal oxide-based catalyst of the present invention, 5 to 50 parts by weight of the above-mentioned sol substance (weight in terms of metal oxide) and 5 to 50 parts by weight of the above-mentioned polymer substance, more preferably the above-mentioned sol 10 to 30 parts by weight of the above-described polymer substance is mixed with 7 to 30 parts by weight (weight in terms of metal oxide) of the substance. When the proportion of the sol substance is less than 5 parts by weight (weight in terms of metal oxide), the pore volume ratio of the first pores becomes small and the catalytic activity decreases, and 50 parts by weight (weight in terms of metal oxide). If it exceeds 300, the formation of the second pores will be insufficient and the catalytic activity will decrease. When the proportion of the polymer substance is less than 5 parts by weight, the formation of the second pores is insufficient and the catalytic activity is reduced. It becomes smaller and the catalytic activity decreases.
【００３１】 本発明の製造方法では、金属酸化物系触
媒の活性をさらに高める点から前述したゾル物質と高分
子物質の混合物に、さらに貴金属と貴金属以外の金属と
を含有する添加物を添加することが好ましい。なお、こ
の添加物は、触媒とするための加熱により貴金属と金属
酸化物、又は貴金属酸化物と金属酸化物に変化する。In the production method of the present invention, an additive containing a noble metal and a metal other than a noble metal is further added to the above-mentioned mixture of the sol substance and the polymer substance in order to further enhance the activity of the metal oxide-based catalyst. Is preferred. The additive changes into a noble metal and a metal oxide or a noble metal oxide and a metal oxide by heating to be used as a catalyst.
【００３２】 貴金属としては、例えば、金、白金、
銀、パラジウム、ロジウム、オスミウム、イリジウム、
ルテニウム等を挙げることができる。中でも金属酸化物
系触媒の活性を高める効果が大きな点で白金が好まし
い。これら貴金属は、１種単独で又は２種以上を組合わ
せて用いることができる。As the noble metal, for example, gold, platinum,
Silver, palladium, rhodium, osmium, iridium,
Ruthenium and the like can be mentioned. Among them, platinum is preferable because the effect of increasing the activity of the metal oxide catalyst is large. These noble metals can be used alone or in combination of two or more.
【００３３】 貴金属以外の金属としては、例えば、Ａ
ｌ、Ｂ、Ｂａ、Ｃａ、Ｃｄ、Ｃｅ、Ｃｏ、Ｃｒ、Ｆｅ、
Ｇｅ、Ｈｆ、Ｉｎ、Ｌｉ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎ
ｉ、Ｐｂ、Ｒｕ、Ｓｉ、Ｓｎ、Ｓｒ、Ｔａ、Ｔｉ、Ｖ、
Ｗ、Ｙ、Ｚｒからなる群から選ばれる少なくとも１種を
含むものを挙げることができる。これら金属酸化物は、
１種単独で又は２種以上を組合わせて用いることができ
る。Examples of the metal other than the noble metal include A
1, B, Ba, Ca, Cd, Ce, Co, Cr, Fe,
Ge, Hf, In, Li, Mg, Mn, Mo, Nb, N
i, Pb, Ru, Si, Sn, Sr, Ta, Ti, V,
Examples include those containing at least one selected from the group consisting of W, Y, and Zr. These metal oxides
One type may be used alone, or two or more types may be used in combination.
【００３４】 貴金属と貴金属以外の金属とを含有する
添加物としては、例えば、貴金属を貴金属以外の金属中
に分散してなるもの、貴金属と貴金属以外の金属とを１
分子内に含む化合物等を挙げることができる。中でも、
金属酸化物系触媒の活性を高める作用が大きい点でチタ
ン（Ｔｉ）と白金（Ｐｔ）とを１分子内に含む化合物が
好ましい。Examples of the additive containing a noble metal and a metal other than the noble metal include, for example, one obtained by dispersing a noble metal in a metal other than the noble metal, or one containing noble metal and a metal other than the noble metal.
Compounds contained in the molecule can be exemplified. Among them,
A compound containing titanium (Ti) and platinum (Pt) in one molecule is preferable because the effect of increasing the activity of the metal oxide catalyst is great.
【００３５】 この化合物は、例えば、チタンのアルコ
キシド又はアルコキシドの一部をアセチルアセトナート
基で置換したアルコキシド誘導体と、白金の塩化物と
を、アミノ酸を介して結合させることにより調製するこ
とができる。アミノ酸としては、メタノール、エタノー
ル等の溶媒に対する溶解性が高い点から、リシン、プロ
リン等を用いることが好ましい。また、調製の際には、
チタン（Ｔｉ）９５．０〜９９.９重量％に対して、白
金（Ｐｔ）を０．１〜５重量％含有するように調製する
ことが好ましい。白金（Ｐｔ）が、０．１重量％未満で
は、金属酸化物系触媒の活性を高める効果が不十分とな
り、５重量％を超えると金属酸化物系触媒の活性を高め
る効果が飽和状態になり、徒にコストの上昇を招くこと
になる。This compound can be prepared, for example, by bonding an alkoxide of titanium or an alkoxide derivative in which a part of the alkoxide is substituted with an acetylacetonate group, to a chloride of platinum via an amino acid. As the amino acid, lysine, proline and the like are preferably used because of their high solubility in solvents such as methanol and ethanol. Also, during preparation,
It is preferable to prepare platinum (Pt) so as to contain 0.1 to 5% by weight with respect to 95.0 to 99.9% by weight of titanium (Ti). When platinum (Pt) is less than 0.1% by weight, the effect of increasing the activity of the metal oxide catalyst is insufficient, and when it exceeds 5% by weight, the effect of increasing the activity of the metal oxide catalyst becomes saturated. However, the cost increases.
【００３６】 また、この添加物の濃度は、例えばリシ
ン、プロリンを用いた場合には約０．０５〜１ｍｏｌ／
ｌとするのが好ましい。さらには、この添加物のｐＨ
は、前述したゾル物質のｐＨとの差が３以下であること
が好ましい。The concentration of the additive is, for example, about 0.05 to 1 mol / mol when lysine or proline is used.
It is preferably 1. Furthermore, the pH of this additive
It is preferable that the difference from the above-mentioned pH of the sol substance is 3 or less.
【００３７】 本発明においては、前述したゾル物質と
高分子物質との混合物１０〜１００重量部に対して、貴
金属と貴金属以外の金属とを含有する添加物を５０〜９
５重量部（金属酸化物換算重量）添加することが好まし
い。In the present invention, an additive containing a noble metal and a metal other than a noble metal is added to 50 to 9 parts by weight of 10 to 100 parts by weight of the mixture of the sol substance and the polymer substance described above.
It is preferable to add 5 parts by weight (weight in terms of metal oxide).
【００３８】 添加物の添加量が５０重量部（金属酸化
物換算重量）未満では、貴金属による金属酸化物触媒の
増感効果が十分に得られず、触媒効果が不十分となって
しまうことがあり、９５重量部（金属酸化物換算重量）
を超えると第一の細孔の形成が十分でなく触媒効果が不
十分になることがある。If the amount of the additive is less than 50 parts by weight (weight in terms of metal oxide), the sensitizing effect of the noble metal on the metal oxide catalyst may not be sufficiently obtained, and the catalytic effect may be insufficient. Available, 95 parts by weight (weight in terms of metal oxide)
If it exceeds 300, the formation of the first pores may not be sufficient and the catalytic effect may be insufficient.
【００３９】 本発明の製造方法では、上述のようにし
て得られた混合物を３００〜７００℃、好ましくは、４
００〜５００℃で加熱する。３００℃未満では、形成さ
れる第一の細孔及び第二の細孔の孔径が所望の孔径より
大きくなり、触媒効果が低下してしまう。一方、７００
℃を超えると第一の細孔及び第二の細孔が形成できない
か形成できても所望の孔径より小さくなり、触媒効果が
低下してしまう。In the production method of the present invention, the mixture obtained as described above is treated at 300 to 700 ° C., preferably at 4 ° C.
Heat at 00-500 ° C. If the temperature is lower than 300 ° C., the pore diameters of the formed first and second pores are larger than desired pore diameters, and the catalytic effect is reduced. On the other hand, 700
If the temperature exceeds ℃, the first pores and the second pores cannot be formed, or even if they can be formed, the pore diameter becomes smaller than a desired pore diameter, and the catalytic effect is reduced.
【００４０】 加熱時間は、加熱温度に応じて適宜決定
することができるが、通常は、数分から数時間程度行う
ことが好ましい。また、加熱雰囲気としては、貴金属を
含有する添加物を添加する場合には、貴金属の粒成長を
抑制するため水素等の還元ガスを用いて還元ガス雰囲気
とするのが好ましい。The heating time can be appropriately determined according to the heating temperature, but is usually preferably from several minutes to several hours. In addition, when an additive containing a noble metal is added, the heating atmosphere is preferably a reducing gas atmosphere using a reducing gas such as hydrogen to suppress grain growth of the noble metal.
【００４１】[0041]
【実施例】 以下、本発明を実施例により具体的に説明
するが、本発明はこれら実施例によって何等限定される
ものではない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
【００４２】（実施例１）ジイソプロポキシビスチタン
の７５％イソプロパノール溶液８７０ｇと、アミノ酸で
あるＬ−プロリン９．６ｇと、塩化白金酸８．０ｇとを
１リットルの７５℃メタノール中で反応させ、その後水
を添加してチタン（Ｔｉ）と白金（Ｐｔ）を分子内に含
む添加物溶液を調製した。なお、この添加物溶液中には
固形成分中ＴｉＯ2９８重量％、白金２重量％含んでい
る。次に、粒径３ｎｍのＴｉＯ2粒子を含有するＴｉＯ2
ゾル５重量部（ＴｉＯ2換算重量）と、分子量２０００
のポリプロピレングリコール５０重量部とを混合し、こ
の混合物５５重量部に対して、予め調製した添加物溶液
を９５重量部（ＴｉＯ2換算重量）添加した。次いで添
加物を添加後の混合液を室温で乾燥し、その後大気雰囲
気下、４５０℃、１時間加熱しＴｉＯ2系触媒を製造し
た。Example 1 870 g of a 75% isopropanol solution of diisopropoxybistitanium, 9.6 g of L-proline as an amino acid, and 8.0 g of chloroplatinic acid were reacted in 1 liter of methanol at 75 ° C. Then, water was added to prepare an additive solution containing titanium (Ti) and platinum (Pt) in the molecule. The additive solution contains 98% by weight of TiO 2 and 2 % by weight of platinum in the solid component. Then, TiO 2 containing TiO 2 particles having a particle size of 3nm
5 parts by weight of sol (weight in terms of TiO 2 ) and molecular weight of 2000
Was mixed with 50 parts by weight of polypropylene glycol, and 95 parts by weight of a previously prepared additive solution (weight in terms of TiO 2 ) was added to 55 parts by weight of this mixture. Next, the mixed solution after the addition of the additive was dried at room temperature, and then heated at 450 ° C. for 1 hour in an air atmosphere to produce a TiO 2 -based catalyst.
【００４３】（実施例２）実施例１において、ＴｉＯ2
ゾル３０重量部（ＴｉＯ2換算重量）と、ポリプロピレ
ングリコール５０重量部とを混合し、この混合物８０重
量部に対して、添加物溶液を７０重量部（ＴｉＯ2換算
重量）添加したこと以外は実施例１と同様にしてＴｉＯ
2系触媒を得た。(Example 2) In Example 1, TiO 2
The procedure was performed except that 30 parts by weight of sol (weight in terms of TiO 2 ) and 50 parts by weight of polypropylene glycol were mixed, and 70 parts by weight of the additive solution (weight in terms of TiO 2 ) was added to 80 parts by weight of this mixture. TiO as in Example 1
A 2- system catalyst was obtained.
【００４４】（実施例３）実施例１において、ＴｉＯ2
ゾル５０重量部（ＴｉＯ2換算重量）と、ポリプロピレ
ングリコール５０重量部とを混合し、この混合物１００
重量部に対して、添加物溶液を５０重量部（ＴｉＯ2換
算重量）添加したこと以外は実施例１と同様にしてＴｉ
Ｏ2系触媒を得た。(Example 3) In Example 1, TiO 2
A mixture of 50 parts by weight of sol (weight in terms of TiO 2 ) and 50 parts by weight of polypropylene glycol is mixed.
In the same manner as in Example 1, except that 50 parts by weight (weight in terms of TiO 2 ) of the additive solution was added to the parts by weight.
An O 2 -based catalyst was obtained.
【００４５】（実施例４）実施例１において、粒径１０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル５重量部（ＴｉＯ2換算重量）に対してポリプ
ロピレングリコールを５重量部混合したこと、及び添加
物溶液を添加した後の混合物を加熱する温度を３００℃
としたこと以外は実施例１と同様にしてＴｉＯ2系触媒
を得た。(Example 4)
for the use of TiO 2 sol containing nm of TiO 2, T
5 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) was mixed with 5 parts by weight of polypropylene glycol, and the temperature of heating the mixture after adding the additive solution was set to 300 ° C.
A TiO 2 -based catalyst was obtained in the same manner as in Example 1, except that
【００４６】（実施例５）実施例１において、粒径１０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル３０重量部（ＴｉＯ2換算重量）と、ポリプロ
ピレングリコール５重量部とを混合し、この混合物３５
重量部に対して、添加物溶液を７０重量部（ＴｉＯ2換
算重量）添加したこと、及び混合物を加熱する温度を３
００℃としたこと以外は実施例１と同様にしてＴｉＯ2
系触媒を得た。(Example 5)
for the use of TiO 2 sol containing nm of TiO 2, T
A mixture of 30 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 5 parts by weight of polypropylene glycol was mixed.
70 parts by weight of the additive solution (weight in terms of TiO 2 ) was added to the parts by weight, and the temperature at which the mixture was heated was 3%.
TiO 2 in the same manner as in Example 1 except that the temperature was set to 00 ° C.
A system catalyst was obtained.
【００４７】（実施例６）実施例１において、粒径１０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル５０重量部（ＴｉＯ2換算重量）と、ポリプロ
ピレングリコール５重量部とを混合し、この混合物５５
重量部に対して、添加物溶液を５０重量部（ＴｉＯ2換
算重量）添加したこと、及び混合物を加熱する温度を３
００℃としたこと以外は実施例１と同様にしてＴｉＯ2
系触媒を得た。(Example 6)
for the use of TiO 2 sol containing nm of TiO 2, T
A mixture of 50 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 5 parts by weight of polypropylene glycol was mixed.
50 parts by weight of the additive solution (weight in terms of TiO 2 ) was added to the parts by weight, and the temperature at which the mixture was heated was 3%.
TiO 2 in the same manner as in Example 1 except that the temperature was set to 00 ° C.
A system catalyst was obtained.
【００４８】（実施例７）実施例１において、粒径５０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル５重量部（ＴｉＯ2換算重量）と、ポリプロピ
レングリコール３０重量部とを混合し、この混合物３５
重量部に対して、添加物溶液を９５重量部（ＴｉＯ2換
算重量）添加したこと、及び混合物を加熱する温度を７
００℃としたこと以外は実施例１と同様にしてＴｉＯ2
系触媒を得た。(Example 7)
for the use of TiO 2 sol containing nm of TiO 2, T
5 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 30 parts by weight of polypropylene glycol are mixed, and this mixture 35
95 parts by weight of the additive solution (weight in terms of TiO 2 ) was added to the parts by weight, and the temperature at which the mixture was heated was 7%.
TiO 2 in the same manner as in Example 1 except that the temperature was set to 00 ° C.
A system catalyst was obtained.
【００４９】（実施例８）実施例１において、粒径５０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル３０重量部（ＴｉＯ2換算重量）と、ポリプロ
ピレングリコール３０重量部とを混合し、この混合物６
０重量部に対して、添加物溶液を７０重量部（ＴｉＯ2
換算重量）添加したこと、及び混合物を加熱する温度を
７００℃としたこと以外は実施例１と同様にしてＴｉＯ
2系触媒を得た。(Embodiment 8)
for the use of TiO 2 sol containing nm of TiO 2, T
30 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 30 parts by weight of polypropylene glycol are mixed, and this mixture 6
70 parts by weight of the additive solution (TiO 2
TiO 2 in the same manner as in Example 1 except that the mixture was added and the temperature at which the mixture was heated was 700 ° C.
A 2- system catalyst was obtained.
【００５０】（実施例９）実施例１において、粒径５０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル５０重量部（ＴｉＯ2換算重量）と、ポリプロ
ピレングリコール３０重量部とを混合し、この混合物８
０重量部に対して、添加物溶液を５０重量部（ＴｉＯ2
換算重量）添加したこと、及び混合物を加熱する温度を
７００℃としたこと以外は実施例１と同様にしてＴｉＯ
2系触媒を得た。(Example 9)
for the use of TiO 2 sol containing nm of TiO 2, T
50 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 30 parts by weight of polypropylene glycol were mixed.
50 parts by weight of the additive solution (TiO 2
TiO 2 in the same manner as in Example 1 except that the mixture was added and the temperature at which the mixture was heated was 700 ° C.
A 2- system catalyst was obtained.
【００５１】（実施例１０）実施例１においてＴｉＯ2
ゾル５０重量部（ＴｉＯ2換算重量）に対してポリプロ
ピレングリコールを５０重量部混合したこと、及びチタ
ン（Ｔｉ）と白金（Ｐｔ）を分子内に含む添加物の溶液
を添加しなかったこと以外は実施例１と同様にしてＴｉ
Ｏ2系触媒を得た。(Example 10) In Example 1, TiO 2
Except that 50 parts by weight of propylene (50 parts by weight in terms of TiO 2 ) were mixed with 50 parts by weight of sol and that a solution of an additive containing titanium (Ti) and platinum (Pt) in the molecule was not added. Ti as in Example 1
An O 2 -based catalyst was obtained.
【００５２】（実施例１１）実施例１において、ＴｉＯ
2ゾル５０重量部（ＴｉＯ2換算重量）と、ポリプロピレ
ングリコール５０重量部とを混合し、この混合物１００
重量部に対して、添加物の溶液を５０重量部（ＴｉＯ2
換算重量）添加したこと、及び混合物を加熱する温度を
３００℃としたこと以外は実施例１と同様にしてＴｉＯ
2系触媒を得た。(Embodiment 11)
2 50 parts by weight of sol (weight in terms of TiO 2 ) and 50 parts by weight of polypropylene glycol are mixed, and this mixture 100
50 parts by weight of the additive solution (TiO 2
TiO 2 in the same manner as in Example 1 except that the mixture was added and the temperature at which the mixture was heated was 300 ° C.
A 2- system catalyst was obtained.
【００５３】（実施例１２）実施例１において、ＴｉＯ
2ゾル５０重量部（ＴｉＯ2換算重量）と、ポリプロピレ
ングリコール５０重量部とを混合し、この混合物１００
重量部に対して、添加物の溶液を５０重量部（ＴｉＯ2
換算重量）添加したこと、及び混合物を加熱する温度を
７００℃としたこと以外は実施例１と同様にしてＴｉＯ
2系触媒を得た。(Example 12) In Example 1, TiO
2 50 parts by weight of sol (weight in terms of TiO 2 ) and 50 parts by weight of polypropylene glycol are mixed, and this mixture 100
50 parts by weight of the additive solution (TiO 2
TiO 2 in the same manner as in Example 1 except that the mixture was added and the temperature at which the mixture was heated was 700 ° C.
A 2- system catalyst was obtained.
【００５４】（比較例１）実施例１において、ＴｉＯ2
ゾル３重量部（ＴｉＯ2換算重量）と、ポリプロピレン
グリコール５０重量部とを混合し、この混合物５３重量
部に対して、添加物の溶液を９７重量部（ＴｉＯ2換算
重量）添加したこと、及び混合物を加熱する温度を２５
０℃としたこと以外は実施例１と同様にしてＴｉＯ2系
触媒を得た。Comparative Example 1 In Example 1, TiO 2
3 parts by weight of sol (weight in terms of TiO 2 ) and 50 parts by weight of polypropylene glycol were mixed, and 97 parts by weight of an additive solution (weight in terms of TiO 2 ) was added to 53 parts by weight of this mixture; The temperature at which the mixture is heated to 25
A TiO 2 -based catalyst was obtained in the same manner as in Example 1 except that the temperature was set to 0 ° C.
【００５５】（比較例２）実施例１において、ＴｉＯ2
ゾル３重量部（ＴｉＯ2換算重量）と、ポリプロピレン
グリコール５０重量部とを混合し、この混合物５３重量
部に対して、添加物の溶液を９７重量部（ＴｉＯ2換算
重量）添加したこと、及び混合物を加熱する温度を７５
０℃としたこと以外は実施例１と同様にしてＴｉＯ2系
触媒を得た。Comparative Example 2 In Example 1, TiO 2
3 parts by weight of sol (weight in terms of TiO 2 ) and 50 parts by weight of polypropylene glycol were mixed, and 97 parts by weight of an additive solution (weight in terms of TiO 2 ) was added to 53 parts by weight of this mixture; The temperature at which the mixture is heated to 75
A TiO 2 -based catalyst was obtained in the same manner as in Example 1 except that the temperature was set to 0 ° C.
【００５６】（比較例３）実施例１において、粒径５０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル７５重量部（ＴｉＯ2換算重量）と、ポリプロ
ピレングリコール６０重量部とを混合し、この混合物１
３５重量部に対して、添加物の溶液を２５重量部（Ｔｉ
Ｏ2換算重量）添加したこと、及び混合物を加熱する温
度を２５０℃としたこと以外は実施例１と同様にしてＴ
ｉＯ2系触媒を得た。(Comparative Example 3)
for the use of TiO 2 sol containing nm of TiO 2, T
75 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 60 parts by weight of polypropylene glycol were mixed.
25 parts by weight of the additive solution (Ti
O 2 equivalent weight), and the temperature of the mixture was heated to 250 ° C.
It was obtained iO 2-based catalyst.
【００５７】（比較例４）実施例１において、粒径５０
ｎｍのＴｉＯ2を含有するＴｉＯ2ゾルを用いたこと、Ｔ
ｉＯ2ゾル７５重量部（ＴｉＯ2換算重量）と、ポリプロ
ピレングリコール６０重量部とを混合し、この混合物１
３５重量部に対して、添加物の溶液を２５重量部（Ｔｉ
Ｏ2換算重量）添加したこと、及び混合物を加熱する温
度を７５０℃としたこと以外は実施例１と同様にしてＴ
ｉＯ2系触媒を得た。(Comparative Example 4)
for the use of TiO 2 sol containing nm of TiO 2, T
75 parts by weight of TiO 2 sol (weight in terms of TiO 2 ) and 60 parts by weight of polypropylene glycol were mixed.
25 parts by weight of the additive solution (Ti
O 2 in terms of weight) that was added, and the temperature for heating the mixture, except that the 750 ° C. in the same manner as in Example 1 T
It was obtained iO 2-based catalyst.
【００５８】（比較例５）実施例１において、分子量１
５０のポリプロピレングリコールを用いたこと以外は実
施例１と同様にしてＴｉＯ2系触媒を得た。Comparative Example 5 In Example 1, the molecular weight was 1
A TiO 2 -based catalyst was obtained in the same manner as in Example 1, except that 50 polypropylene glycols were used.
【００５９】（比較例６）実施例１において、分子量３
×１０6のポリプロピレングリコールを用いたこと以外
は実施例１と同様にしてＴｉＯ2系触媒を得た。Comparative Example 6 In Example 1, the molecular weight was 3
A TiO 2 -based catalyst was obtained in the same manner as in Example 1 except that × 10 6 of polypropylene glycol was used.
【００６０】（比較例７）実施例１において、粒径１０
０ｎｍのＴｉＯ2粒子を含有するＴｉＯ2ゾルを用いたこ
と以外は実施例１と同様にしてＴｉＯ2系触媒を得た。(Comparative Example 7)
A TiO 2 -based catalyst was obtained in the same manner as in Example 1 except that a TiO 2 sol containing 0 nm TiO 2 particles was used.
【００６１】（比較例８）実施例１において、ポリプロ
ピレングリコールに代え、ポリエチレングリコールを用
いたこと、添加物の溶液を添加した後の混合物を加熱す
る温度を７５０℃としたこと以外は実施例１と同様にし
てＴｉＯ2系触媒を得た。Comparative Example 8 Example 1 was repeated except that polyethylene glycol was used in place of polypropylene glycol, and that the temperature at which the mixture after adding the additive solution was heated was 750 ° C. In the same manner as in the above, a TiO 2 -based catalyst was obtained.
【００６２】（比較例９）実施例１において、ポリプロ
ピレングリコールを混合しなかったこと以外は実施例１
と同様にしてＴｉＯ2系触媒を得た。Comparative Example 9 Example 1 was repeated except that no polypropylene glycol was used.
A TiO 2 -based catalyst was obtained in the same manner as described above.
【００６３】（評価方法及び評価）実施例１〜１２及び
比較例１〜９で得られたＴｉＯ2系触媒を以下の方法で
測定、評価した。(Evaluation Method and Evaluation) The TiO 2 -based catalysts obtained in Examples 1 to 12 and Comparative Examples 1 to 9 were measured and evaluated by the following methods.
【００６４】１．評価方法 （１）孔径、細孔細孔容積率 実施例１〜１２及び比較例１〜９で得られたＴｉＯ2系
触媒をポロシメーターを用いて測定した。1. Evaluation method (1) Pore diameter, pore pore volume ratio The TiO 2 catalysts obtained in Examples 1 to 12 and Comparative Examples 1 to 9 were measured using a porosimeter.
【００６５】（２）ｏ−クロロトルエン（ダイオキシン
の模擬物質）分解率 実施例１〜１２及び比較例１〜９のＴｉＯ2系触媒の製
造途中で得られる添加物を添加後の混合液を、外径３０
×３０×長さ１００ｍｍ、ハニカムセルピッチ６ｍｍか
らなるコージェライト製ハニカム状支持体にディップコ
ートし乾燥後、実施例１〜１２及び比較例１〜９のＴｉ
Ｏ2系触媒の製造方法と同一の条件で加熱しＴｉＯ2系触
媒を製造した。得られたＴｉＯ2系触媒の存在下、２０
０℃の温度で、ｏ−クロロトルエンを５００ｐｐｍ含む
ガスを流して、反応室出口のｏ−クロロトルエン濃度と
反応室入口のｏ−クロロトルエン濃度より分解率を測定
した。(2) Decomposition rate of o-chlorotoluene (simulated substance of dioxin) The mixture obtained after adding the additives obtained during the production of the TiO 2 -based catalysts of Examples 1 to 12 and Comparative Examples 1 to 9 was Outer diameter 30
Dip-coating on a cordierite honeycomb-shaped support consisting of × 30 × length 100 mm and a honeycomb cell pitch of 6 mm, followed by drying, followed by Ti of Examples 1 to 12 and Comparative Examples 1 to 9
The TiO 2 -based catalyst was manufactured by heating under the same conditions as in the method for manufacturing the O 2 -based catalyst. In the presence of the obtained TiO 2 -based catalyst, 20
A gas containing 500 ppm of o-chlorotoluene was flowed at a temperature of 0 ° C., and the decomposition rate was measured from the o-chlorotoluene concentration at the reaction chamber outlet and the o-chlorotoluene concentration at the reaction chamber inlet.
【００６６】２．評価 本発明の製造方法で得られたＴｉＯ2系触媒では８０％
以上の高い分解率を示したが、比較例の製造方法で得ら
れたＴｉＯ2系触媒では、８０％以下の低い分解率を示
した。孔径、細孔細孔容積率及びｏ−クロロトルエン分
解率の評価結果は触媒製造条件とともに表１に示す。2. Evaluation In the TiO 2 -based catalyst obtained by the production method of the present invention, 80%
Although the above high decomposition rate was exhibited, the TiO 2 -based catalyst obtained by the production method of the comparative example exhibited a low decomposition rate of 80% or less. Table 1 shows the evaluation results of the pore diameter, the pore pore volume ratio, and the o-chlorotoluene decomposition rate together with the catalyst production conditions.
【００６７】[0067]
【表１】 [Table 1]
【００６８】[0068]
【発明の効果】 以上説明した通り、本発明の金属酸化
物系触媒の製造方法及び金属酸化物系触媒では、反応物
質の活性部位への迅速な浸入及び反応生成物の活性部位
からの迅速な脱離と、活性部位での高い触媒活性を同時
に達成して、極めて高い触媒効果を発揮することがで
き、特に、ダイオキシン分解反応又は水素製造反応に有
用な金属酸化物系触媒及び金属酸化物系触媒の製造方法
を提供することができる。As described above, according to the method for producing a metal oxide-based catalyst and the metal oxide-based catalyst of the present invention, rapid infiltration of a reactant into an active site and rapid reaction product from an active site can be achieved. Desorption and high catalytic activity at the active site can be achieved at the same time, and extremely high catalytic effect can be exhibited. Particularly, metal oxide catalysts and metal oxide catalysts useful for dioxin decomposition reaction or hydrogen production reaction A method for producing a catalyst can be provided.
フロントページの続き (72)発明者 戸田 久敬 愛知県豊橋市大脇町字大脇ノ谷139−１ (72)発明者 浜島 誠治 愛知県豊明市栄町村前51 (72)発明者 安井 広陵 愛知県春日井市八田町八丁目４番地の９ (72)発明者 磯貝 佳孝 愛知県碧南市羽根町三丁目57番地 Ｆターム(参考） 4D048 AA11 AB03 BA07X BA30X BB02 4G069 AA03 AA08 AA09 AA12 BA04B BA13B BA27B BB08B BC75B CA02 CA10 CA19 DA06 EC06X EC07X EC14X EC15X EC16X EC17X FB15 FB23 FB36Continuing on the front page (72) Inventor Hisataka Toda 139-1 Owakinotani, Owaki-cho, Toyohashi-shi, Aichi Prefecture (72) Inventor Seiji Hamajima 51, Sakaecho-mura, Toyoake-shi, Aichi Prefecture (72) Inventor Hiroyo Yasui Hachi, Kasugai-shi, Aichi Prefecture 9-72, Tamachi 8-chome (72) Inventor Yoshitaka Isogai 3-57, Hane-cho, Hekinan-shi, Aichi F-term (reference) EC07X EC14X EC15X EC16X EC17X FB15 FB23 FB36
Claims (13)
１〜０．６０ｃｍ3／ｃｍ3（細孔容積／触媒の見掛け容
積）の細孔容積率で有するとともに、孔径５０〜５００
ｎｍの第二の細孔を０．０１〜０．６０ｃｍ3／ｃｍ
3（細孔容積／触媒の見掛け容積）の細孔容積率で有す
ることを特徴とする金属酸化物系触媒。1. The method according to claim 1, wherein the first pore having a pore size of 3 to 30 nm is 0.0
It has a pore volume ratio of 1 to 0.60 cm 3 / cm 3 (pore volume / apparent volume of catalyst) and a pore diameter of 50 to 500.
nm of the second pore is 0.01 to 0.60 cm 3 / cm
A metal oxide catalyst having a pore volume ratio of 3 (pore volume / apparent volume of catalyst).
金属を分散してなる請求項１に記載の金属酸化物系触
媒。2. The metal oxide catalyst according to claim 1, wherein the metal oxide catalyst comprises a noble metal dispersed in a metal oxide.
してなる請求項１又は２に記載の金属酸化物系触媒。3. The metal oxide-based catalyst according to claim 1, wherein the metal oxide-based catalyst has a honeycomb shape.
持体上に金属酸化物が担持されてなる請求項１又は２に
記載の金属酸化物系触媒。4. The metal oxide catalyst according to claim 1, wherein the metal oxide catalyst is formed by supporting a metal oxide on a honeycomb-shaped support.
項１〜４のいずれか１項に記載の金属酸化物系触媒。5. The metal oxide catalyst according to claim 1, which is used for a dioxin decomposition reaction.
のいずれか１項に記載の金属酸化物系触媒。6. The method according to claim 1, which is used for a hydrogen production reaction.
The metal oxide-based catalyst according to any one of the above.
有するゾル物質５〜５０重量部（金属酸化物換算重量）
と、分子量２００〜２００万の高分子物質５〜５０重量
部とを混合し、当該混合物を３００〜７００℃で加熱す
ることを特徴とする金属酸化物系触媒の製造方法。7. 5 to 50 parts by weight (weight in terms of metal oxide) of a sol material containing metal oxide particles having a particle size of 3 to 50 nm.
And 5 to 50 parts by weight of a high molecular substance having a molecular weight of 2 to 2,000,000, and heating the mixture at 300 to 700 ° C.
ある請求項７に記載の金属酸化物系触媒の製造方法。8. The method according to claim 7, wherein the metal oxide particles are TiO 2 particles.
コールである請求項７又は８に記載の金属酸化物系触媒
の製造方法。9. The method for producing a metal oxide-based catalyst according to claim 7, wherein the polymer substance is polypropylene glycol.
金属とを含有する添加物をさらに所定量添加した請求項
７〜９のいずれか１項に記載の金属酸化物系触媒の製造
方法。10. The method for producing a metal oxide-based catalyst according to claim 7, wherein an additive containing a noble metal and a metal other than the noble metal is further added to the mixture in a predetermined amount.
０〜１００重量部に対して、５０〜９５重量部（金属酸
化物換算重量）である請求項１０に記載の金属酸化物系
触媒の製造方法。11. The method according to claim 1, wherein the amount of the additive is 1%.
The method for producing a metal oxide catalyst according to claim 10, wherein the amount is 50 to 95 parts by weight (weight in terms of metal oxide) based on 0 to 100 parts by weight.
金である請求項１０又は１１に記載の金属酸化物系触媒
の製造方法。12. The method for producing a metal oxide-based catalyst according to claim 10, wherein the noble metal contained in the additive is platinum.
（Ｐｔ）とを分子内に有する化合物を含むものである請
求項１０〜１２のいずれか１項に記載の金属酸化物系触
媒の製造方法。13. The method for producing a metal oxide catalyst according to claim 10, wherein the additive contains a compound having titanium (Ti) and platinum (Pt) in a molecule. .
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002001117A (en) * | 2000-04-20 | 2002-01-08 | Ngk Insulators Ltd | Method for manufacturing catalyst for decomposition of organic halogen compound and method for manufacturing filter for decomposition of organic halogen compound |
| JP2007107723A (en) * | 2006-12-18 | 2007-04-26 | Honda Motor Co Ltd | Disk brake |
| JP2009125705A (en) * | 2007-11-27 | 2009-06-11 | Ishifuku Metal Ind Co Ltd | Manufacturing method of titanium oxide carrier carrying platinum group metal or alloy of platinum group metal and other metal |
| JP4834274B2 (en) * | 2000-05-15 | 2011-12-14 | メタウォーター株式会社 | Adsorbent having organic halogen compound decomposition function and method for producing the same |
-
2000
- 2000-07-04 JP JP2000202894A patent/JP2002018291A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002001117A (en) * | 2000-04-20 | 2002-01-08 | Ngk Insulators Ltd | Method for manufacturing catalyst for decomposition of organic halogen compound and method for manufacturing filter for decomposition of organic halogen compound |
| JP4508459B2 (en) * | 2000-04-20 | 2010-07-21 | メタウォーター株式会社 | Method for producing organohalogen compound decomposition catalyst and method for producing organohalogen compound decomposition filter |
| JP4834274B2 (en) * | 2000-05-15 | 2011-12-14 | メタウォーター株式会社 | Adsorbent having organic halogen compound decomposition function and method for producing the same |
| JP2007107723A (en) * | 2006-12-18 | 2007-04-26 | Honda Motor Co Ltd | Disk brake |
| JP2009125705A (en) * | 2007-11-27 | 2009-06-11 | Ishifuku Metal Ind Co Ltd | Manufacturing method of titanium oxide carrier carrying platinum group metal or alloy of platinum group metal and other metal |
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