JP4729914B2 - Fine iron oxide powder and method for producing the same - Google Patents
Fine iron oxide powder and method for producing the same Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 119
- 239000000843 powder Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002245 particle Substances 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000011164 primary particle Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000011325 microbead Substances 0.000 claims description 10
- -1 iron ions Chemical class 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 description 53
- 239000003054 catalyst Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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Description
本発明は、触媒などに用いられる微細な酸化鉄粉末とその製造方法に関する。 The present invention relates to a fine iron oxide powder used for a catalyst or the like and a method for producing the same.
安定な酸化鉄としては、黒色の Fe3O4と赤茶色の Fe2O3が知られ、粉末状態として磁性体原料、顔料、研磨材、触媒などの用途に広く用いられている。しかし酸化鉄粒子は、単独では凝集して粗大粒子になりやすく、触媒として用いた場合には表面積の低下によって活性が低下するという不具合があった。 As stable iron oxide, black Fe 3 O 4 and red-brown Fe 2 O 3 are known, and they are widely used in powdered materials, pigments, abrasives, catalysts and the like. However, iron oxide particles tend to agglomerate into coarse particles by themselves, and when used as a catalyst, there is a problem that the activity decreases due to a decrease in surface area.
この問題を解決するために、例えば特開平06−116504号公報には、面積平均径が 0.1〜 1.0μｍの酸化鉄粒子粉末にAl、Zrなどの酸化物を付着させてなる酸化鉄粒子粉末が提案されている。しかし酸化鉄粒子の表面がAl、Zrなどの酸化物で覆われるために、酸化鉄としての表面効果が低下するため、触媒として用いる場合には実用的でない。 In order to solve this problem, for example, Japanese Patent Laid-Open No. 06-116504 discloses an iron oxide particle powder obtained by attaching an oxide such as Al or Zr to an iron oxide particle powder having an area average diameter of 0.1 to 1.0 μm. Proposed. However, since the surface of the iron oxide particles is covered with an oxide such as Al or Zr, the surface effect as iron oxide is reduced, so that it is not practical when used as a catalyst.
また酸化鉄に比べて凝集しにくい他の酸化物を担体とし、その担体に酸化鉄を担持して用いることも行われている。例えば特開平11−123330号公報には、アルミナ、ジルコニアなどの酸化物担体にIr、Pt、Rh、Pd、Ag、Co、Cu、Ni、Fe、Mg及びランタニド元素からなる群より選択される少なくとも一種の元素を0.01〜10重量％担持させた排ガス浄化触媒が開示されている。担持されたFeは、使用中に酸化されて酸化鉄となると考えられる。 In addition, other oxides that are less likely to aggregate than iron oxide are used as a carrier, and iron oxide is supported on the carrier and used. For example, in JP-A-11-123330, at least selected from the group consisting of Ir, Pt, Rh, Pd, Ag, Co, Cu, Ni, Fe, Mg and a lanthanide element on an oxide carrier such as alumina and zirconia. An exhaust gas purification catalyst carrying 0.01 to 10% by weight of a kind of element is disclosed. The supported Fe is considered to be oxidized to iron oxide during use.
ところが酸化物担体に酸化鉄を担持した場合には、高温雰囲気下では担持されている酸化鉄どうしが粒成長して粗大化し、活性が低下するのが免れない。例えば上記公報に記載された触媒では、図２に示すように、Fe２は酸化物担体の一次粒子１が凝集してなる二次粒子の表面に担持されている。二次粒子は表面積が比較的小さいため、所定量の酸化鉄を担持した場合には酸化鉄粒子どうしの距離が近くなって粒成長しやすくなる。 However, when iron oxide is supported on an oxide carrier, it is inevitable that the supported iron oxide grows and coarsens in a high temperature atmosphere and the activity decreases. For example, in the catalyst described in the above publication, as shown in FIG. 2, Fe2 is supported on the surface of secondary particles formed by agglomerating primary particles 1 of an oxide carrier. Since the secondary particles have a relatively small surface area, when a predetermined amount of iron oxide is supported, the distance between the iron oxide particles becomes close to each other and grain growth is facilitated.
また特開平09−262473号公報には、アルミナ、チタニアなどの母材に、粒径10〜1000Åの Fe2O3と、粒径10〜1000ÅのPtとを担持してなる光触媒が記載されている。この光触媒によれば、可視領域の光を照射すると粒径10〜1000Åの微粒子状の Fe2O3によって水が分解され水素が発生する。Ptは水素発生反応の助触媒として働く。 Japanese Patent Application Laid-Open No. 09-262473 describes a photocatalyst formed by supporting Fe 2 O 3 having a particle size of 10 to 1000 と and Pt having a particle size of 10 to 1000 に on a base material such as alumina or titania. Yes. According to this photocatalyst, when irradiated with light in the visible region, water is decomposed by finely divided Fe 2 O 3 having a particle diameter of 10 to 1000 mm to generate hydrogen. Pt acts as a promoter for the hydrogen generation reaction.
しかし母材上に Fe2O3を粒径10〜1000Åの微粒子として担持するには、上記公報には鉄をターゲットとするスパッタリングによって行う旨の記載があり、一般的な担持方法に比べて装置が大がかりとなるとともに工数が多大となるため、高価な触媒となってしまう。
本発明は、上記事情に鑑みてなされたものであり、酸化鉄粒子を微細な状態で長期間保持することを解決すべき課題とする。また本発明のもう一つの目的は、そのような微細酸化鉄粉末を安価に製造することにある。 This invention is made | formed in view of the said situation, and makes it the subject which should be solved to hold | maintain an iron oxide particle in a fine state for a long period of time. Another object of the present invention is to produce such fine iron oxide powder at low cost.
上記課題を解決する本発明の微細酸化鉄粉末の特徴は、セリア及びジルコニアの少なくとも一方を含み平均粒径が１〜 100nmの一次粒子レベルまで微細化された担体酸化物粒子と、担体酸化物粒子に２〜30重量％の範囲で担持された酸化鉄と、からなることにある。 A feature of the fine iron oxide powder of the present invention that solves the above problems is that carrier oxide particles containing at least one of ceria and zirconia and having an average particle size of 1 to 100 nm and being refined to a primary particle level, and carrier oxide particles And iron oxide supported in the range of 2 to 30% by weight .
そして本発明の微細酸化鉄粉末の製造方法の特徴は、本発明の微細酸化鉄粉末を製造する方法であって、マイクロビーズを用いセリア及びジルコニアの少なくとも一方を含む担体酸化物を平均粒径が１〜 100nmの一次粒子レベルまで粉砕して微細な担体酸化物粒子を調製する分散工程と、担体酸化物粒子に鉄イオンを担持した後に焼成し担体酸化物粒子に２〜30重量％の範囲で酸化鉄を担持する担持工程と、を行うことにある。 A feature of the method for producing fine iron oxide powder of the present invention is a method for producing the fine iron oxide powder of the present invention, wherein the carrier oxide containing at least one of ceria and zirconia is used in the average particle diameter using microbeads. A dispersion step of preparing fine carrier oxide particles by pulverizing to a primary particle level of 1 to 100 nm, and firing after supporting iron ions on the carrier oxide particles in a range of 2 to 30% by weight in the carrier oxide particles And a supporting step for supporting iron oxide.
分散工程は湿式で行うことが望ましい。またマイクロビーズは、担体酸化物に含まれる少なくとも一種の金属の酸化物からなることが好ましい。さらに、分散工程は液体中で行うことで微細な担体酸化物粒子が分散した分散液を調製し、担持工程は分散液中に鉄イオンを溶解し蒸発乾固した後に、又はpH調整により沈殿物を生成した後に、焼成することが望ましい。 It is desirable to carry out the dispersion process in a wet manner. The microbead is preferably made of an oxide of at least one metal contained in the carrier oxide. Furthermore, the dispersion step is performed in a liquid to prepare a dispersion in which fine carrier oxide particles are dispersed. In the supporting step, the iron ions are dissolved in the dispersion and evaporated to dryness, or the precipitate is adjusted by adjusting the pH. It is desirable to bake after producing.
本発明の微細酸化物粉末によれば、一次粒子レベルまで微細化された担体酸化物粒子は凝集状態が緩和された粒子であり高分散状態を形成できるので、それに担持された酸化鉄も高分散となり粒成長が抑制される。また担持されている酸化鉄が拡散障壁となるために、担体酸化物粒子どうしの凝集も抑制される。したがって担体酸化物粒子に酸化鉄が担持された粒子が集合してなる本発明の微細酸化物粉末は、粗大化が抑制され微細な状態を長期間維持することができる。 According to the fine oxide powder of the present invention, the carrier oxide particles refined to the primary particle level are particles whose aggregation state is relaxed and can form a highly dispersed state, so that the iron oxide supported thereon is also highly dispersed. Grain growth is suppressed. Further, since the supported iron oxide serves as a diffusion barrier, aggregation of the carrier oxide particles is suppressed. Therefore, the fine oxide powder of the present invention in which iron oxide-supported particles are aggregated on carrier oxide particles can suppress coarsening and maintain a fine state for a long period of time.
そして本発明の製造方法によれば、マイクロビーズを用いて担体酸化物粒子を一次粒子レベルまで粉砕し、それに酸化鉄を担持するだけであるので、スパッタリングなどを用いる必要なく安価に、かつ安定して微細酸化物粉末を製造することができる。 According to the production method of the present invention, the carrier oxide particles are pulverized to the primary particle level using microbeads, and only iron oxide is supported thereon, so that it is inexpensive and stable without the need to use sputtering or the like. Thus, a fine oxide powder can be produced.
本発明の微細酸化物粉末では、一次粒子レベルまで微細化された担体酸化物粒子に酸化鉄が担持されている。この状態は、図１に示すように、担体酸化物粒子の微細な一次粒子１それぞれの表面に酸化鉄２が略層状に担持された状態である。
In the fine oxide powder of the present invention, iron oxide is supported on carrier oxide particles refined to the primary particle level. In this state, as shown in FIG. 1,
一方、通常状態の担体酸化物は、図２に示すように、一次粒子１が凝集してなる二次粒子の状態で存在している。したがって、それに酸化鉄を担持すると、酸化鉄２は二次粒子の表面に略層状に担持される。ここで図１と図２の一次粒子１の量を同量とし、酸化鉄２の担持量を同量とした場合、担体酸化物の表面積は一次粒子１が分散状態にある図１の方が大きいので、酸化鉄２の担持密度は図１の方が低くなる。したがって図１の本発明の場合には、担持されている酸化鉄どうしの距離が大きく、酸化鉄どうしの粒成長が抑制される。
On the other hand, the carrier oxide in the normal state exists in the state of secondary particles formed by agglomeration of the primary particles 1 as shown in FIG. Therefore, when iron oxide is supported on the
さらに担持されている酸化鉄２が拡散障壁となるために、一次粒子１どうしの凝集も抑制される。したがって本発明の微細酸化物粉末は、粗大化が抑制され微細な状態を長期間維持することができる。
Further, since the supported
担体酸化物としては、鉄との相互作用に優れているという意味から、セリア及びジルコニアの少なくとも一方を含むことが好ましい。 The carrier oxide preferably contains at least one of ceria and zirconia from the viewpoint of excellent interaction with iron .
酸化鉄としては、 Fe3O4及び Fe2O3のどちらも用いることができるが、触媒として用いる場合には Fe2O3が好ましい。この酸化鉄の担持量は、２〜30重量％の範囲とすることが好ましい。担持量が２重量％未満であると酸化鉄としての機能の発現が困難となり、30重量％を超えて担持すると酸化鉄どうしが粗大化しやすく微細な状態を維持することが困難となる。 As the iron oxide, both Fe 3 O 4 and Fe 2 O 3 can be used, but Fe 2 O 3 is preferable when used as a catalyst. The amount of iron oxide supported is preferably in the range of 2 to 30% by weight. If the loading amount is less than 2% by weight, it will be difficult to exhibit the function as iron oxide. If the loading amount exceeds 30% by weight, the iron oxides are likely to be coarsened and it is difficult to maintain a fine state.
担体酸化物を一次粒子レベルまで微細化するには、レーザー粉砕などを用いることもできるが、直径が30〜 100μｍ程度のマイクロビーズを用いるのが簡便であり安価である。また一次粒子レベルまで微細化された担体酸化物を安定して保持し、再凝集を抑制するためには、乾式粉砕より湿式粉砕を用いることが望ましいし、現時点では乾式粉砕は困難である。 Laser pulverization or the like can be used to refine the carrier oxide to the primary particle level, but it is simple and inexpensive to use microbeads having a diameter of about 30 to 100 μm. In order to stably hold the carrier oxide refined to the primary particle level and suppress reaggregation, it is desirable to use wet pulverization rather than dry pulverization, and at present, dry pulverization is difficult.
マイクロビーズを用いる場合、不純物の混入を避けるために、担体酸化物に含まれる少なくとも一種の金属の酸化物からなるマイクロビーズを用いることが望ましい。ジルコニアは粉砕媒体として好適であるので、ジルコニア製のマイクロビーズを用いる場合には、担体酸化物として少なくともジルコニアを用いることが望ましい。なお同様の理由から、粉砕容器も担体酸化物に含まれる少なくとも一種の金属の酸化物からなるものを用いることが望ましい。 When microbeads are used, it is desirable to use microbeads made of an oxide of at least one metal contained in the carrier oxide in order to avoid contamination with impurities. Since zirconia is suitable as a grinding medium, when using zirconia microbeads, it is desirable to use at least zirconia as a carrier oxide. For the same reason, it is desirable to use a pulverization container made of at least one metal oxide contained in the carrier oxide.
一次粒子レベルまで微細化された担体酸化物粒子に酸化鉄を担持するには、先ず鉄イオンを担持した後に焼成して酸化鉄とする。最初から酸化鉄として担持するためには、酸化鉄を微細な担体酸化物粒子以上に微細とする必要があり、粗大化しやすい酸化鉄をそのような微粒子状態とすることは困難であるからである。 In order to support iron oxide on carrier oxide particles refined to the primary particle level, iron ions are first supported and then baked to obtain iron oxide. This is because it is necessary to make iron oxide finer than fine carrier oxide particles in order to carry it as iron oxide from the beginning, and it is difficult to make iron oxide that tends to coarsen into such fine particle state .
鉄イオンを担持するには、硝酸鉄など水溶性の鉄塩の水溶液を担体酸化物粒子に接触させて吸着担持する方法、水溶性の鉄塩の水溶液を担体酸化物粉末に含浸させた後に焼成して吸水担持する方法などがある。 In order to support iron ions, a method of adsorbing and supporting an aqueous solution of a water-soluble iron salt such as iron nitrate on the carrier oxide particles, and impregnating the carrier oxide powder with an aqueous solution of a water-soluble iron salt and firing. Then, there is a method of carrying water absorption.
本発明の製造方法では、分散工程は液体中で行うことで微細な担体酸化物粒子が分散した分散液を調製し、担持工程は分散液中に鉄イオンを溶解し蒸発乾固した後に、又はアンモニア水などでpH調整することで沈殿を生成した後に、焼成することが特に望ましい。この方法によれば、微細な担体酸化物粒子を常に水で保護された状態として酸化鉄を担持できるので、酸化鉄の担持までに担体酸化物粒子どうしが凝集するのを抑制でき、きわめて微細な微細酸化鉄粉末を製造することができる。また分散工程と担持工程を連続的に行うことができるので、生産性が向上する。 In the production method of the present invention, the dispersion step is performed in a liquid to prepare a dispersion in which fine carrier oxide particles are dispersed, and the supporting step is performed after dissolving iron ions in the dispersion and evaporating to dryness, or It is particularly desirable to calcine after producing a precipitate by adjusting the pH with aqueous ammonia or the like. According to this method, iron oxide can be supported in a state where the fine carrier oxide particles are always protected with water, so that the aggregation of the carrier oxide particles before the iron oxide is supported can be suppressed. Fine iron oxide powder can be produced. Further, since the dispersing step and the supporting step can be performed continuously, productivity is improved.
以下、実施例及び比較例により本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
（実施例１）
CeO2−ZrO2複合酸化物粉末（モル比Ce：Zr＝１：１、平均粒子径 320nm、80重量％以上の粒子が粒径 380nmで比表面積が65m2／ｇ）を0.25Ｌのジルコニア製容器に80ｇ投入し、さらにジルコニア製マイクロビーズ（直径50μｍ） 400ｇと、イオン交換水 700ｇを投入し、6000 rpmにて90分間分散し、最後に酢酸を添加してpHを３とした。これにより平均粒子径が22nm、80重量％以上の粒子が粒径43nm、比表面積が62m2／ｇであるCeO2−ZrO2複合酸化物粉末のゾル液が得られた。
(Example 1)
CeO 2 —ZrO 2 composite oxide powder (molar ratio Ce: Zr = 1: 1, average particle size 320 nm, particles of 80% by weight or more having a particle size of 380 nm and a specific surface area of 65 m 2 / g) made of 0.25 L of zirconia 80 g was charged into the container, 400 g of zirconia microbeads (diameter 50 μm) and 700 g of ion-exchanged water were added, dispersed for 90 minutes at 6000 rpm, and finally acetic acid was added to adjust the pH to 3. As a result, a sol solution of CeO 2 —ZrO 2 composite oxide powder having an average particle size of 22 nm, particles having a particle size of 43 nm and a specific surface area of 62 m 2 / g was obtained.
得られたゾル液に所定濃度の硝酸鉄水溶液の所定量を混合し、蒸発乾固後 300℃で３時間焼成して、各CeO2−ZrO2複合酸化物粒子に Fe2O3を担持した。 Fe2O3の担持量は 7.4重量％である。この触媒粉末を圧粉成形した後粉砕し、 0.5〜１mmに整粒してペレット触媒を調製した。 A predetermined amount of an aqueous iron nitrate solution having a predetermined concentration was mixed with the obtained sol solution, evaporated to dryness, and calcined at 300 ° C. for 3 hours to carry Fe 2 O 3 on each CeO 2 —ZrO 2 composite oxide particle. . The supported amount of Fe 2 O 3 is 7.4% by weight. This catalyst powder was compacted and then pulverized and sized to 0.5 to 1 mm to prepare a pellet catalyst.
（比較例１）
実施例１と同様のCeO2−ZrO2複合酸化物粉末（モル比Ce：Zr＝１：１、平均粒子径 320nm、80重量％以上の粒子が粒径 380nmで比表面積が65m2／ｇ）に所定濃度の硝酸鉄水溶液の所定量を含浸させ、実施例１と同様に Fe2O3を担持し、ペレット触媒を調製した。
(Comparative Example 1)
CeO 2 —ZrO 2 composite oxide powder as in Example 1 (molar ratio Ce: Zr = 1: 1, average particle size 320 nm, particles of 80 wt% or more having a particle size of 380 nm and a specific surface area of 65 m 2 / g) Was impregnated with a predetermined amount of an aqueous iron nitrate solution having a predetermined concentration, and Fe 2 O 3 was supported in the same manner as in Example 1 to prepare a pellet catalyst.
＜試験・評価＞
各ペレット触媒を評価装置にそれぞれ 1.5ｇ充填し、H2が５％過剰のリッチガスとO2が５％過剰のリーンガスを５分間ずつ交互に流しながら 800℃で５時間保持する耐久試験を行った。耐久試験後の各ペレット触媒について、表１に示すモデルガスを流しながら、 100℃〜 500℃まで12℃／分で昇温させ、その時のC3H6浄化率を連続的に測定した。そしてC3H6を50％浄化できる温度を求め、結果を表２に示す。
<Test and evaluation>
An endurance test was performed in which 1.5 g of each pellet catalyst was filled in the evaluation apparatus, and the gas was held at 800 ° C. for 5 hours while alternately flowing a rich gas containing 5% excess of H 2 and a lean gas containing 5% excess of O 2 for 5 minutes each. . With respect to each pellet catalyst after the durability test, the temperature was raised from 100 ° C. to 500 ° C. at 12 ° C./min while flowing the model gas shown in Table 1, and the C 3 H 6 purification rate at that time was continuously measured. The temperature at which C 3 H 6 can be purified by 50% was determined, and the results are shown in Table 2.
表２より、実施例１のペレット触媒は比較例１に比べてC3H6浄化活性が高いことがわかり、これは実施例１の触媒における酸化鉄の表面積が比較例１の触媒より高いことに起因していると考えられる。すなわち一次粒子レベルの微細なCeO2−ZrO2複合酸化物粒子に酸化鉄を担持することで、浄化活性が大幅に向上していることが明らかであり、実施例１の触媒は各粒子どうしの分散性が維持されていることが明らかである。 From Table 2, it can be seen that the pellet catalyst of Example 1 has a higher C 3 H 6 purification activity than that of Comparative Example 1, which indicates that the surface area of iron oxide in the catalyst of Example 1 is higher than that of the catalyst of Comparative Example 1. It is thought to be caused by That is, it is clear that the purification activity is greatly improved by supporting iron oxide on fine CeO 2 —ZrO 2 composite oxide particles at the primary particle level. It is clear that the dispersibility is maintained.
本発明の微細酸化鉄粉末は、自動車の排ガス浄化用触媒の他、分散安定性に優れているので、塗料や化粧品などの顔料、微細研磨材などにも有用である。 Since the fine iron oxide powder of the present invention is excellent in dispersion stability in addition to a catalyst for exhaust gas purification of automobiles, it is useful for pigments such as paints and cosmetics, fine abrasives, and the like.
１：一次粒子 ２：酸化鉄 1: Primary particles 2: Iron oxide
Claims (5)
マイクロビーズを用いセリア及びジルコニアの少なくとも一方を含む担体酸化物を平均粒径が１〜 100nmの一次粒子レベルまで粉砕して微細な担体酸化物粒子を調製する分散工程と、
該担体酸化物粒子に鉄イオンを担持した後に焼成し該担体酸化物粒子に２〜30重量％の範囲で酸化鉄を担持する担持工程と、を行うことを特徴とする微細酸化鉄粉末の製造方法。 A method for producing the fine iron oxide powder according to claim 1,
A dispersion step of preparing fine carrier oxide particles by pulverizing a carrier oxide containing at least one of ceria and zirconia to a primary particle level of 1 to 100 nm using microbeads;
And a supporting step of supporting iron oxide in the range of 2 to 30% by weight after supporting iron ions on the carrier oxide particles and firing. Method.
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