JP4639673B2 - 複合酸化物の製造方法 - Google Patents
複合酸化物の製造方法 Download PDFInfo
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- JP4639673B2 JP4639673B2 JP2004206528A JP2004206528A JP4639673B2 JP 4639673 B2 JP4639673 B2 JP 4639673B2 JP 2004206528 A JP2004206528 A JP 2004206528A JP 2004206528 A JP2004206528 A JP 2004206528A JP 4639673 B2 JP4639673 B2 JP 4639673B2
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- 239000002131 composite material Substances 0.000 title claims description 43
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- 239000008346 aqueous phase Substances 0.000 claims description 55
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- 229910021645 metal ion Inorganic materials 0.000 claims description 32
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [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
- 238000002485 combustion reaction Methods 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
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- 150000002902 organometallic compounds Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- AZJLMWQBMKNUKB-UHFFFAOYSA-N [Zr].[La] Chemical compound [Zr].[La] AZJLMWQBMKNUKB-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 230000012447 hatching Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
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- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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Images
Description
内容積5リットルのビーカーにシクロヘキサン3.0リットル、ポリオキシエチレン(n=5)ノニルフェニルエーテル224gを入れ、硝酸セリウム6.65gと蒸留水120mLよりなる水溶液を加え撹拌した。室温下でマグネチックスターラーを用い撹拌して逆ミセル(油中水滴型マイクロエマルション、水滴実測直径30nm)を作成した。これとは別に、ジルコニウムブトキシド0.27モルをシクロヘキサン0.8リットルに溶解させたジルコニウムアルコキシド溶液を作成し、これを上記マイクロエマルションに加えた。この際の水(水相)に対するシクロヘキサン(有機相)の体積比(O/W)は18である。また、逆ミセル内の水相における陽イオン(水素イオンを除く)濃度は、3.5mol/Lであり、また逆ミセル内の水相における全金属イオン濃度は、2.5mol/Lである。室温下においてこの混合物をよく撹拌すると、ただちにビーカー内が白黄色に曇り、コロイド粒子(二次粒子、粒径20nm程度)が生成した。
マイクロエマルションにおける硝酸セリウムの濃度、およびジルコニウムアルコキシド溶液中のジルコニウムの濃度を、上記の実施例1とは異ならせた以外は、実施例1と同様にしてセリアジルコニア複合酸化物を生成した。すなわち、シクロヘキサン3.0リットル、ポリオキシエチレン(n=5)ノニルフェニルエーテル224g、硝酸セリウム0.8g、蒸留水120mLを混合してマイクロエマルション(油中水滴型マイクロエマルション、水滴実測直径30nm)を作成した。また、ジルコニウムブトキシド0.033モルをシクロヘキサン0.8リットルに溶解させたジルコニウムアルコキシド溶液を作成した。これらの溶液を混合して得られた溶液の水相に対する有機相の体積比(O/W)は18であり、また、逆ミセル内の水相における陽イオン(水素イオンを除く)濃度は、3.5mol/Lとし、また逆ミセル内の水相における全金属イオン濃度は、0.61mol/Lである。なお、複合酸化物の収量は、0.24kg/容器100Lであった。
実施例1および実施例2で得られた多孔質複合酸化物について、600℃×2時間の焼成後の細孔容積を、液体窒素温度下、窒素吸着により測定した。その結果を図4に示す。図4に示す結果から明らかなように、実施例1および実施例2のいずれの多孔質複合酸化物における細孔分布はシャープなものとなったが、細孔容積がピークとなる細孔直径は、実施例1のものは10nm程度となり、これに対して実施例2のものとは7nm程度となった。すなわち、二次粒子が生成・成長する逆ミセル内の水相における全金属イオンの量(濃度)を多くすれば、細孔容積がピークとなる細孔直径が大きくなり、これとは反対に逆ミセル内の水相における全金属イオンの量(濃度)を少なくすれば、細孔容積がピークとなる細孔直径が小さくなることが認められ、逆ミセル内の水相における全金属イオンの量(濃度)によって細孔分布を制御できることが確認された。また、細孔分布がシャープなものとなることから知られるように、細孔径の制御を正確におこなえることが認められた。
Claims (3)
- 2種以上の金属元素を含む複合酸化物の一次粒子の凝集体である二次粒子を更に凝集させ、その二次粒子同士の凝集体を焼成する多孔構造の複合酸化物の製造方法において、
加水分解することにより水酸化物もしくは酸化物を生成する第1の金属元素の化合物を有機溶媒に溶解した溶液と、有機溶媒中に界面活性剤が形成する逆ミセルの内部の水相に第2以降の金属元素のイオンを含むマイクロエマルションとを混合し、
この逆ミセルの界面において第1の金属元素の化合物を加水分解させるとともに第2以降の金属元素を取り込ませ、
重縮合させて複合酸化物の前駆体の一次粒子を形成し、
この一次粒子を含む系において一次粒子を凝集させて二次粒子を形成し、
さらにこの二次粒子を凝集させることを含み、
この加水分解時に上記逆ミセル内の水相における水素イオンを除く陽イオンの濃度を2mol/L以上として電気的反発力によって逆ミセル同士の融合もしくは合一を抑制するとともに、その陽イオンの一部である金属イオンの濃度によって前記複合酸化物における細孔径を制御することを特徴とする複合酸化物の製造方法。 - 前記加水分解時における前記逆ミセルの径が20nm以上であることを特徴とする請求項1に記載の複合酸化物の製造方法。
- 前記加水分解時における油相と水相との体積比を40以下とすることを特徴とする請求項1または2に記載の複合酸化物の製造方法。
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JPH04265150A (ja) * | 1991-02-19 | 1992-09-21 | Mitsubishi Materials Corp | セラミック中空球の製造方法 |
JPH054817A (ja) * | 1991-06-26 | 1993-01-14 | Murata Mfg Co Ltd | ペロブスカイト型複合酸化物粉末の製造方法 |
JPH11267502A (ja) * | 1998-03-23 | 1999-10-05 | Jisedai Haigas Shokubai Kenkyusho:Kk | 排ガス浄化触媒およびその製造方法 |
JP3466856B2 (ja) * | 1997-02-05 | 2003-11-17 | トヨタ自動車株式会社 | 排ガス浄化触媒およびその製造方法 |
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JPH04265150A (ja) * | 1991-02-19 | 1992-09-21 | Mitsubishi Materials Corp | セラミック中空球の製造方法 |
JPH054817A (ja) * | 1991-06-26 | 1993-01-14 | Murata Mfg Co Ltd | ペロブスカイト型複合酸化物粉末の製造方法 |
JP3466856B2 (ja) * | 1997-02-05 | 2003-11-17 | トヨタ自動車株式会社 | 排ガス浄化触媒およびその製造方法 |
JPH11267502A (ja) * | 1998-03-23 | 1999-10-05 | Jisedai Haigas Shokubai Kenkyusho:Kk | 排ガス浄化触媒およびその製造方法 |
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