JP5574527B2 - Method for producing cerium oxide fine particles - Google Patents
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- JP5574527B2 JP5574527B2 JP2009295561A JP2009295561A JP5574527B2 JP 5574527 B2 JP5574527 B2 JP 5574527B2 JP 2009295561 A JP2009295561 A JP 2009295561A JP 2009295561 A JP2009295561 A JP 2009295561A JP 5574527 B2 JP5574527 B2 JP 5574527B2
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims description 61
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims description 61
- 239000010419 fine particle Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000002244 precipitate Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910017464 nitrogen compound Inorganic materials 0.000 description 7
- 150000002830 nitrogen compounds Chemical class 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229940044927 ceric oxide Drugs 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PQBKXYUMEMUVIH-UHFFFAOYSA-H cerium(3+);trisulfate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PQBKXYUMEMUVIH-UHFFFAOYSA-H 0.000 description 2
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical class [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、酸化セリウム微粒子の製造方法に関し、より詳しくは、窒素系化合物を含有する廃液なしに酸化セリウム微粒子を製造する方法に関する。 The present invention relates to a method for producing cerium oxide fine particles, and more particularly to a method for producing cerium oxide fine particles without a waste liquid containing a nitrogen-based compound.
酸化セリウム微粒子は、従来から、触媒担体、研磨材又はガラス添加剤として使用されている。例えば、磁気記録媒体用基板、半導体ウエハ、光学レンズ、プリズム、ミラー等の製造において、ガラス、カーボン、およびセラミックス等の材料の表面を研磨する研磨材として、酸化セリウム微粒子が使用されている。 Cerium oxide fine particles are conventionally used as a catalyst carrier, an abrasive or a glass additive. For example, in the manufacture of substrates for magnetic recording media, semiconductor wafers, optical lenses, prisms, mirrors, etc., cerium oxide fine particles are used as an abrasive for polishing the surface of materials such as glass, carbon, and ceramics.
酸化セリウム微粒子の製造方法は種々検討がなされており、例えば、特許文献１には、セリウム（ＩＶ）の塩の水溶液を酸性媒体中で加水分解し、得られた沈殿をろ過し、洗浄し、所望によりそれを乾燥し、続いて３００〜６００℃で焼成することにより酸化第二セリウムを製造する方法が開示されている。前記特許文献１の方法により、測定温度３５０〜４５０℃において少なくとも８５±５ｍ２／ｇ以上の比表面積を有する酸化第二セリウムを得ることができる。 Various methods for producing cerium oxide fine particles have been studied. For example, in Patent Document 1, an aqueous solution of a cerium (IV) salt is hydrolyzed in an acidic medium, and the resulting precipitate is filtered, washed, A method for producing ceric oxide is disclosed by optionally drying it and subsequently calcining at 300-600 ° C. By the method of Patent Document 1, ceric oxide having a specific surface area of at least 85 ± 5 m 2 / g at a measurement temperature of 350 to 450 ° C. can be obtained.
また、特許文献２には、セリウム塩水溶液と硫酸イオン含有水溶液を反応させることにより塩基性硫酸第二セリウム塩を沈澱させ、得られた沈澱をろ過し、洗浄し、所望により乾燥し、続いて３００〜５００℃で焼成することにより酸化第二セリウムを製造する方法が開示されている。前記特許文献２の方法により、測定温度３５０〜５００℃において８５±５ｍ２／ｇ以上の比表面積を有する酸化第二セリウムを得ることができる。 Patent Document 2 discloses that a basic cerium sulfate salt is precipitated by reacting a cerium salt aqueous solution with a sulfate ion-containing aqueous solution, and the resulting precipitate is filtered, washed, and optionally dried. A method for producing ceric oxide by firing at 300-500 ° C is disclosed. By the method of Patent Document 2, ceric oxide having a specific surface area of 85 ± 5 m 2 / g or more at a measurement temperature of 350 to 500 ° C. can be obtained.
そして、特許文献３には、上記のような微細な酸化第二セリウムを製造するための中間生成物及びその製造方法が開示されている。その中間生成物は一般式Ｃｅ（ＯＨ）ｘ（ＮＯ３）ｙ・ｐＣｅＯ２・ｎＨ２Ｏ（式中、ｘはｘ＝４−ｙとなるような数であり、ｙは０．３５〜１．５であり、ｐは０以上２．０以下であり、ｎは０以上約２０以下である。）で表されるセリウム（ＩＶ）化合物であり、その製造方法は、セリウム（ＩＶ）塩水溶液を酸性媒体で加水分解し、得られた沈殿物を分離し、場合によって熱処理することからなる。その中間生成物はＸ線回折ではＣｅＯ２と同じ形を示すが、燃焼損失が２０％ある。また、その中間生成物は焼成後に比表面積の大きい酸化セリウムが生成する。 And patent document 3 is disclosing the intermediate product for manufacturing the above fine ceric oxides, and its manufacturing method. The intermediate product is a general formula Ce (OH) x (NO 3 ) y · pCeO 2 · nH 2 O (wherein x is a number such that x = 4-y, and y is 0.35 to 1). 0.5, p is 0 or more and 2.0 or less, and n is 0 or more and about 20 or less.), And its production method is a cerium (IV) salt aqueous solution. Is hydrolyzed with an acidic medium, and the resulting precipitate is separated and optionally heat treated. The intermediate product shows the same shape as CeO 2 in X-ray diffraction, but has a combustion loss of 20%. Further, the intermediate product produces cerium oxide having a large specific surface area after firing.
特許文献４には、粒径を揃えるために、硫酸セリウム水溶液とアンモニア水溶液とを、アンモニアの当量数がセリウムの当量数以上であり、反応媒体のｐＨが６より大であるように連続的に同時混合し、得られた沈殿物を濾取し、乾燥し、６００〜１２００℃で焼成し、得られた酸化物をジェットミル粉砕する諸工程からなる製造方法が提案されている。 In Patent Document 4, in order to make the particle sizes uniform, an aqueous cerium sulfate solution and an aqueous ammonia solution are continuously added so that the equivalent number of ammonia is equal to or greater than the equivalent number of cerium and the pH of the reaction medium is greater than 6. There has been proposed a production method comprising the steps of simultaneously mixing, collecting the resulting precipitate by filtration, drying, firing at 600 to 1200 ° C., and jet milling the resulting oxide.
さらに、特許文献５には、硝酸第一セリウムの水溶液と塩基とを、ｐＨが５〜１０となる量比で攪拌混合し、続いて７０〜１００℃に急速加熱し、その温度で熟成することを特徴とする粒径が１０〜８０ｎｍの酸化セリウム単結晶からなる酸化セリウム超微粒子の製造方法が開示されている。 Furthermore, in Patent Document 5, an aqueous solution of cerium nitrate and a base are stirred and mixed at a quantitative ratio that results in a pH of 5 to 10, followed by rapid heating to 70 to 100 ° C. and aging at that temperature. A method for producing ultrafine cerium oxide particles comprising a cerium oxide single crystal having a particle size of 10 to 80 nm is disclosed.
従来の酸化セリウム微粒子の製造方法では、その製造工程において、窒素含有溶媒を用いて処理を行うため、窒素系化合物を含有した廃液がでる可能性がある。窒素系化合物は水質汚濁防止法による規制物質であり、環境へ影響を与えるものであるため、窒素系化合物を除去する処理が必要である。
そこで、本発明は、廃液中に窒素系化合物を含有することのない、酸化セリウム微粒子を製造する方法を提供することを目的とする。
In the conventional method for producing cerium oxide fine particles, since the treatment is performed using a nitrogen-containing solvent in the production process, there is a possibility that a waste liquid containing a nitrogen-based compound may be produced. Nitrogen compounds are substances regulated by the Water Pollution Control Law and affect the environment, and therefore treatment for removing nitrogen compounds is necessary.
Then, an object of this invention is to provide the method of manufacturing cerium oxide microparticles | fine-particles which do not contain a nitrogen compound in a waste liquid.
本発明者らは、上記の課題を解決すべく鋭意検討した結果、特定のセリウム塩を特定の塩基性化合物とその酸化セリウム換算に対するモル比が特定の範囲となるように混合することで廃液中に窒素系化合物を排出することなく酸化セリウム微粒子を製造できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have mixed a specific cerium salt with a specific basic compound and its molar ratio with respect to cerium oxide conversion into a specific range in the waste liquid. The inventors have found that cerium oxide fine particles can be produced without discharging nitrogen-based compounds, and have completed the present invention.
すなわち、本発明の課題は下記（１）〜（３）の手段により達成される。
（１）（I）硫酸セリウム水溶液又は塩化セリウム水溶液を５０〜９８℃に加温し、次いでアルカリ金属の水酸化物を、酸化セリウム（ＣｅＯ２）換算のモル数に対するアルカリ金属の水酸化物のモル数の割合が１〜１０となる範囲で混合し、５０〜９８℃で３時間以上加温・熟成した後、冷却して、沈殿物を得る工程、（II）工程（I）で得られた沈殿物を乾燥し、結晶子径５〜５０ｎｍの酸化セリウム微粒子を得る工程、を有することを特徴とする酸化セリウム微粒子の製造方法。
（２）前記工程（I）が、前記得られた沈殿物を洗浄する工程を含むことを特徴とする上記（１）に記載の酸化セリウム微粒子の製造方法。
（３）前記アルカリ金属の水酸化物が、水酸化ナトリウム、水酸化カリウム、水酸化リチウムから選ばれる１種又は２種以上であることを特徴とする上記（１）または（２）に記載の酸化セリウム微粒子の製造方法。
That is, the object of the present invention is achieved by the following means (1) to (3).
(1) (I) was warmed cerium sulfate aqueous solution or cerium chloride solution to 50 to 98 ° C., then the hydroxide of alkali metal, hydroxide of alkali metal to cerium oxide (CeO 2) the number of moles of converted Mixing in the range where the molar ratio is 1 to 10, heating and aging at 50 to 98 ° C. for 3 hours or more , then cooling to obtain a precipitate, (II) obtained in step (I) And a step of drying the resulting precipitate to obtain fine cerium oxide particles having a crystallite diameter of 5 to 50 nm.
(2) The method for producing cerium oxide fine particles according to (1), wherein the step (I) includes a step of washing the obtained precipitate.
(3) The alkali metal hydroxide is one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide, as described in (1) or (2) above A method for producing fine cerium oxide particles.
本発明に係る酸化セリウム微粒子の製造方法により、酸化セリウムの単結晶を得ることができる。また、この製造方法によれば、製造工程で生じる廃液に窒素化合物を含むことがなく、窒素化合物の除去処理を必要としない。 A cerium oxide single crystal can be obtained by the method for producing cerium oxide fine particles according to the present invention. In addition, according to this manufacturing method, the waste liquid generated in the manufacturing process does not contain a nitrogen compound, and no nitrogen compound removal treatment is required.
以下、本発明の酸化セリウム微粒子の製造方法について詳細に説明する。
本発明の酸化セリウム微粒子の製造方法は、（I）硫酸セリウム水溶液又は塩化セリウム水溶液とアルカリ金属の水酸化物とを、酸化セリウム（ＣｅＯ２）換算のモル数に対するアルカリ金属の水酸化物のモル数の割合が１〜１０となる範囲で混合し、５０〜９８℃に加温・熟成した後、冷却して、沈殿物を得る工程、（II）工程（I）で得られた沈殿物を乾燥し、結晶子径５〜５０ｎｍの酸化セリウム微粒子を得る工程、を有している。
Hereafter, the manufacturing method of the cerium oxide microparticles | fine-particles of this invention is demonstrated in detail.
The method for producing fine cerium oxide particles according to the present invention comprises: (I) an aqueous solution of cerium sulfate or cerium chloride and an alkali metal hydroxide, the molar amount of alkali metal hydroxide relative to the number of moles in terms of cerium oxide (CeO 2 ). Mixing in the range where the number ratio is 1 to 10, heating and aging to 50 to 98 ° C., then cooling to obtain a precipitate, (II) the precipitate obtained in step (I) Drying to obtain fine cerium oxide particles having a crystallite diameter of 5 to 50 nm.
＜工程（I）＞
本発明にかかる酸化セリウム微粒子の製造方法では、出発原料として、硫酸セリウム又は塩化セリウムを用いる。これは、排液中に窒素系化合物を流出させないためである。硫酸セリウム又は塩化セリウムを用いることで、窒素化合物の除去処理を必要としない。
<Process (I)>
In the method for producing cerium oxide fine particles according to the present invention, cerium sulfate or cerium chloride is used as a starting material. This is to prevent the nitrogen compound from flowing out into the drainage. By using cerium sulfate or cerium chloride, no nitrogen compound removal treatment is required.
硫酸セリウムと塩化セリウムは水系溶媒に溶解して、硫酸セリウム水溶液、塩化セリウム水溶液として使用する。水系溶媒としては、例えば、イオン交換水、蒸留水、精製水、等が挙げられる。
硫酸セリウム水溶液又は塩化セリウム水溶液の濃度としては、水溶液中、酸化セリウムが０．０５〜１ｍｏｌ／Ｌとなるように調整すればよく、０．１〜０．５ｍｏｌ／Ｌがより好ましく、０．１〜０．３ｍｏｌ／Ｌが特に好ましい。水溶液中の酸化セリウムの濃度が０．１ｍｏｌ／Ｌ以上であれば、収率よく生産できるため好ましく、１ｍｏｌ／Ｌ以下であれば、シャープな粒度分布となるため好ましい。
Cerium sulfate and cerium chloride are dissolved in an aqueous solvent and used as a cerium sulfate aqueous solution and a cerium chloride aqueous solution. Examples of the aqueous solvent include ion exchange water, distilled water, purified water, and the like.
The concentration of the cerium sulfate aqueous solution or the cerium chloride aqueous solution may be adjusted so that the cerium oxide in the aqueous solution is 0.05 to 1 mol / L, more preferably 0.1 to 0.5 mol / L, -0.3 mol / L is particularly preferred. If the concentration of cerium oxide in the aqueous solution is 0.1 mol / L or more, it can be produced with good yield, and if it is 1 mol / L or less, a sharp particle size distribution is preferable.
アルカリ金属の水酸化物としては、水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）又は水酸化リチウム（ＬｉＯＨ）などが好適に使用される。このうち、特に水酸化ナトリウムの使用が推奨される。アルカリ金属の水酸化物は、１種を単独で又は２種以上を混合して用いることができる。尚、コストの観点から、水酸化ナトリウムを用いることが好ましい。 As the alkali metal hydroxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH) or the like is preferably used. Of these, the use of sodium hydroxide is particularly recommended. The alkali metal hydroxide can be used alone or in combination of two or more. In addition, it is preferable to use sodium hydroxide from a viewpoint of cost.
アルカリ金属の水酸化物は、硫酸セリウム水溶液又は塩化セリウム水溶液との溶解性を高めるため、あらかじめ水系溶媒に溶解して用いることが好ましい。
アルカリ金属の水酸化物の水溶液の濃度としては、水溶液中、アルカリ金属の水酸化物が０．０５〜１ｍｏｌ／Ｌとなるように調整すればよく、０．１〜０．５ｍｏｌ／Ｌがより好ましく、０．１〜０．３ｍｏｌ／Ｌが特に好ましい。水溶液中の塩基性酸化物の濃度が０．１ｍｏｌ／Ｌ以上であれば、収率よく生産できるため好ましく、１ｍｏｌ／Ｌ以下であれば、シャープな粒度分布となるため好ましい。
The alkali metal hydroxide is preferably used by dissolving it in an aqueous solvent in advance in order to enhance the solubility with an aqueous cerium sulfate solution or an aqueous cerium chloride solution.
The concentration of the alkali metal hydroxide aqueous solution may be adjusted so that the alkali metal hydroxide is 0.05 to 1 mol / L in the aqueous solution, and more preferably 0.1 to 0.5 mol / L. 0.1 to 0.3 mol / L is particularly preferable. If the concentration of the basic oxide in the aqueous solution is 0.1 mol / L or more, it can be produced with good yield, and if it is 1 mol / L or less, a sharp particle size distribution is obtained.
前記硫酸セリウム水溶液又は塩化セリウム水溶液とアルカリ金属の水酸化物は、酸化セリウム（ＣｅＯ２）換算のモル数に対するアルカリ金属又の水酸化物のモル数の割合が１〜１０となる範囲で混合することが好ましく、１〜５がより好ましく、１〜１．５が特に好ましい。酸化セリウム（ＣｅＯ２）換算のモル数に対してアルカリ金属の水酸化物のモル数が１以上であると、高収率となり好ましく、アルカリ金属の水酸化物のモル数が１０以下であると、後工程での洗浄回数が軽減できるため好ましい。 The cerium sulfate aqueous solution or cerium chloride aqueous solution and the alkali metal hydroxide are mixed so that the ratio of the number of moles of the alkali metal or hydroxide to the number of moles in terms of cerium oxide (CeO 2 ) is 1 to 10. 1 to 5 is more preferable, and 1 to 1.5 is particularly preferable. When the number of moles of the alkali metal hydroxide is 1 or more with respect to the number of moles in terms of cerium oxide (CeO 2 ), a high yield is preferable, and the number of moles of the alkali metal hydroxide is 10 or less. It is preferable because the number of washings in the subsequent process can be reduced.
尚、硫酸セリウム水溶液又は塩化セリウム水溶液とアルカリ金属の水酸化物との混合液は、ｐＨ値がｐＨ３〜１０となるようにすることが好ましく、ｐＨ４〜７がより好ましく、ｐＨ４〜６が特に好ましい。ｐＨ値がｐＨ３以上であると、結晶度が高くなるため好ましく、ｐＨ１０以下であると、後工程での洗浄回数が軽減となるため好ましい。
上記ｐＨの範囲となるように、適宜、ｐＨコントローラー等を用いて調整すればよい。
The cerium sulfate aqueous solution or the mixed solution of the cerium chloride aqueous solution and the alkali metal hydroxide preferably has a pH value of pH 3 to 10, more preferably pH 4 to 7, and particularly preferably pH 4 to 6. . A pH value of pH 3 or higher is preferred because the crystallinity increases, and a pH value of 10 or lower is preferred because the number of washings in the subsequent process is reduced.
What is necessary is just to adjust suitably using a pH controller etc. so that it may become the range of the said pH.
前記硫酸セリウム水溶液又は塩化セリウム水溶液と前記アルカリ金属の水酸化物の水溶液とを混合し、加温して熟成させる。
硫酸セリウム水溶液又は塩化セリウム水溶液とアルカリ金属の水酸化物の水溶液の混合液を加温する温度としては、前記混合液が沸騰しない温度であれば特に限定されないが、５０〜９８℃程度が好ましく、７０〜９３℃がより好ましく、９０〜９３℃が特に好ましい。加温する温度が５０℃以上であると、結晶度が高くなるため好ましい。
混合液の熟成方法としては、特に限定されないが、液温を前記温度範囲に維持した状態で、攪拌下で、所定時間熟成させる方法、ポンプにより循環させる方法等が挙げられる。
混合液の熟成時間としては、特に限定されないが、３〜２４時間程度であり、３〜１２時間が好ましく、４〜８時間がより好ましく、５〜６時間が特に好ましい。熟成時間が３時間以上であると、高収率となるため好ましく、２４時間以下であると、結晶度が高く好ましい。
The cerium sulfate aqueous solution or cerium chloride aqueous solution and the alkali metal hydroxide aqueous solution are mixed, heated and aged.
The temperature at which the mixed solution of the cerium sulfate aqueous solution or the cerium chloride aqueous solution and the alkali metal hydroxide aqueous solution is heated is not particularly limited as long as the mixed solution does not boil, but is preferably about 50 to 98 ° C. 70-93 degreeC is more preferable, and 90-93 degreeC is especially preferable. A heating temperature of 50 ° C. or higher is preferable because the crystallinity increases.
The aging method of the mixed solution is not particularly limited, and examples thereof include a method of aging for a predetermined time with stirring while maintaining the liquid temperature in the above temperature range, and a method of circulating with a pump.
The aging time of the mixed solution is not particularly limited, but is about 3 to 24 hours, preferably 3 to 12 hours, more preferably 4 to 8 hours, and particularly preferably 5 to 6 hours. A ripening time of 3 hours or longer is preferable because of high yield, and a ripening time of 24 hours or shorter is preferable because of high crystallinity.
尚、本発明において、硫酸セリウム水溶液又は塩化セリウム水溶液を５０〜９８℃に加温しておき、その後にアルカリ金属の水酸化物の水溶液を添加してもよい。 In the present invention, an aqueous cerium sulfate solution or an aqueous cerium chloride solution may be heated to 50 to 98 ° C., and then an aqueous solution of an alkali metal hydroxide may be added.
前記加温・熟成の後、混合液を冷却して沈殿物を得る。
混合液は、６０℃以下、好ましくは５０℃以下、特に好ましくは３０℃以下に冷却し、６時間以上、好ましくは８時間以上、特に好ましくは１２時間以上静置することで、混合液中の酸化セリウム微粒子が沈殿し、沈殿物が得られる。当該沈殿物は白色沈殿であり、酸化セリウム微粒子が含有されている。
また、シャープレス等を用いて遠心分離により沈殿物を回収してもよい。
After the heating and aging, the mixed solution is cooled to obtain a precipitate.
The mixed solution is cooled to 60 ° C. or less, preferably 50 ° C. or less, particularly preferably 30 ° C. or less, and is allowed to stand for 6 hours or more, preferably 8 hours or more, particularly preferably 12 hours or more. Cerium oxide fine particles are precipitated, and a precipitate is obtained. The precipitate is a white precipitate and contains cerium oxide fine particles.
Further, the precipitate may be collected by centrifugation using a sharp press or the like.
＜工程（II）＞
次に、前記工程（I）で得られた酸化セリウム微粒子を含む沈殿物を乾燥する。すなわち、上澄みを除去し、沈殿物を回収し、乾燥して、粉末状の酸化セリウム微粒子を得る。
沈殿物の乾燥方法としては特に制限はないが、例えば、沈殿物を容器に入れて加熱、乾燥させる方法、スプレードライヤーで乾燥させる方法、真空乾燥機で乾燥させる等が挙げられる。
乾燥温度としては、８０〜２００℃が好ましく、８０〜１５０℃がより好ましく、８０〜１２０℃が特に好ましい。乾燥温度が８０℃以上であると乾燥温度が低いため、生産効率が上がり、また１５０℃以下であると一部粒子間の脱水結合による粒子の結合が防止できるため好ましい。
乾燥時間としては、８〜２４時間が好ましく、８〜１６時間がより好ましく、８〜１２時間が特に好ましい。乾燥時間が８時間以上であると乾燥が充分終了する。
次に、前記工程（I）で得られた酸化セリウム微粒子を含む沈殿物をイオン交換水で希釈し、ＮａＯＨ、ＫＯＨ等でｐＨをアルカリ性に調整した後に酸化セリウム微粒子を分散させる。
分散方法としては特に制限はないが、例えば、サンドミル分散機、超音波分散機等が挙げられる。
酸化セリウム微粒子の濃度としては、５％〜２０％が好ましく、７〜２０％がより好ましく、７〜１５％が特に好ましい。濃度が５％以上であると各種用途に用いる場合に利便性があり、２０％以下であると粒子の安定性を維持できるため好ましい。
ｐＨが８以上であると酸化セリウムの表面−ＯＨ基の解離が充分であり、分散に必要な表面チャージが得られる。ｐＨが１１以下であると過剰なイオンの含有を防止でき、分散性を維持することができる。
<Process (II)>
Next, the precipitate containing the cerium oxide fine particles obtained in the step (I) is dried. That is, the supernatant is removed, and the precipitate is collected and dried to obtain powdered cerium oxide fine particles.
Although there is no restriction | limiting in particular as a drying method of a deposit, For example, the method of putting a deposit in a container and heating and drying, the method of drying with a spray dryer, drying with a vacuum dryer etc. are mentioned.
As drying temperature, 80-200 degreeC is preferable, 80-150 degreeC is more preferable, and 80-120 degreeC is especially preferable. When the drying temperature is 80 ° C. or higher, the drying temperature is low, so that the production efficiency is improved.
The drying time is preferably 8 to 24 hours, more preferably 8 to 16 hours, and particularly preferably 8 to 12 hours. If the drying time is 8 hours or more, the drying is sufficiently completed.
Next, the precipitate containing the cerium oxide fine particles obtained in the step (I) is diluted with ion-exchanged water, and the pH is adjusted to alkaline with NaOH, KOH or the like, and then the cerium oxide fine particles are dispersed.
Although there is no restriction | limiting in particular as a dispersion method, For example, a sand mill disperser, an ultrasonic disperser, etc. are mentioned.
The concentration of the cerium oxide fine particles is preferably 5% to 20%, more preferably 7 to 20%, and particularly preferably 7 to 15%. A concentration of 5% or more is convenient for use in various applications, and a concentration of 20% or less is preferable because the stability of the particles can be maintained.
When the pH is 8 or more, the surface-OH group of cerium oxide is sufficiently dissociated, and a surface charge necessary for dispersion can be obtained. When the pH is 11 or less, excessive ions can be prevented from being contained and the dispersibility can be maintained.
本発明の製造方法により得られる酸化セリウム微粒子は、平均結晶子径が５〜５０ｎｍの酸化セリウム微粒子であり、その平均粒子径は５〜５０ｎｍの範囲となる。尚、得られた酸化セリウム微粒子を超音波、サンドミル等の再分散処理を行うことで、所望の粒子径を有する酸化セリウム微粒子を得ることができる。 The cerium oxide fine particles obtained by the production method of the present invention are cerium oxide fine particles having an average crystallite diameter of 5 to 50 nm, and the average particle diameter is in the range of 5 to 50 nm. The obtained cerium oxide fine particles are subjected to redispersion treatment such as ultrasonic wave and sand mill, whereby cerium oxide fine particles having a desired particle diameter can be obtained.
本発明において、前記工程（I）で得られた沈殿物を洗浄する工程を行ってもよい。
沈殿物を洗浄する方法としては、遠心分離機によるデカンテーション法又は限外濾過膜法等を挙げることができる。洗浄工程を１回乃至は複数回行うことで不純物が除去され、より純度の高い酸化セリウム微粒子を得ることができる。
In the present invention, a step of washing the precipitate obtained in the step (I) may be performed.
Examples of the method for washing the precipitate include a decantation method using a centrifuge or an ultrafiltration membrane method. Impurities are removed by performing the washing step once or a plurality of times, and cerium oxide fine particles with higher purity can be obtained.
以下、実施例及び比較例を示して本発明をより詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited to these Examples.
実施例および比較例において採用した測定方法と分析方法は次の通りである。
［結晶子径測定］
酸化セリウム微粒子の結晶子径は、Ｘ線回折装置（商品名：ＲＩＮＴ１４００，理学電気株式会社製）を用いて、Ｘ線回折法により、２θ＝２５．３°のピークの半値幅を測定し、Debye-Schrrerの式により計算によって求めた。
The measurement methods and analysis methods employed in the examples and comparative examples are as follows.
[Measurement of crystallite size]
The crystallite diameter of the cerium oxide fine particles was measured by measuring the half width of the peak at 2θ = 25.3 ° by an X-ray diffraction method using an X-ray diffractometer (trade name: RINT1400, manufactured by Rigaku Denki Co., Ltd.) It was calculated by the Debye-Schrrer equation.
［ｐＨ測定］
試料５０ｍｌを入れたセルを、２５℃の温度に保たれた恒温槽中で、ｐＨ４、７および９の標準液で校正が完了したｐＨメータ（商品名：Ｆ−２２，株式会社堀場製作所製）のガラス電極を挿入して測定した。
[PH measurement]
A pH meter (trade name: F-22, manufactured by Horiba, Ltd.) in which a cell containing 50 ml of the sample was calibrated with standard solutions of pH 4, 7, and 9 in a thermostatic chamber maintained at a temperature of 25 ° C. The glass electrode was inserted and measured.
（実施例１）
硫酸セリウム（III）八水和物１０．４ｇ及び蒸留水４８９．７ｇを５Ｌ容器に入れて攪拌（２００ｒｐｍ）し、溶解した。
引き続き攪拌しながら温度を９３℃に昇温し、１．０％水酸化ナトリウム水溶液３４８ｇの全量を一度に加え、攪拌しながら温度９３℃で６時間維持した。
次に３０℃以下に冷却したところ、白色沈殿が得られた。この溶液のｐＨは１０．０であった。
この溶液を遠心分離装置を用いて、１４０００ｒｐｍで１０分間処理した後、上澄み液を除去した。白色沈殿に蒸留水８００ｇを加え、更に遠心分離装置で、１４０００ｒｐｍで１０分間処理した。この操作を合計３回行って、沈殿物を洗浄した。
得られた沈殿物を透過型電子顕微鏡（ＴＥＭ 倍率２５万倍）で観察した。その結果を図１に示す。図１により、平均粒子径１３ｎｍの単分散粒子であることがわかる。
そして、８０℃の乾燥機で１２時間乾燥させることにより白色粉末５．２ｇを得た。この白色粉末をＸ線回折した結果、酸化セリウムであった。半値幅から求めた結晶子径は１３．４ｎｍである。結果を表１および図２に示す。
ＴＥＭ写真およびＸ線回析から求めた結晶子径より、単結晶の粒子が得られたことがわかる。
Example 1
10.4 g of cerium (III) sulfate octahydrate and 489.7 g of distilled water were placed in a 5 L container and stirred (200 rpm) to dissolve.
Subsequently, the temperature was raised to 93 ° C. while stirring, and 348 g of a 1.0% aqueous sodium hydroxide solution was added all at once, and the temperature was maintained at 93 ° C. for 6 hours with stirring.
Next, when it cooled to 30 degrees C or less, white precipitate was obtained. The pH of this solution was 10.0.
This solution was treated at 14000 rpm for 10 minutes using a centrifugal separator, and then the supernatant was removed. Distilled water (800 g) was added to the white precipitate, and further treated with a centrifugal separator at 14000 rpm for 10 minutes. This operation was performed three times in total to wash the precipitate.
The obtained precipitate was observed with a transmission electron microscope (TEM magnification: 250,000 times). The result is shown in FIG. FIG. 1 shows that the particles are monodisperse particles having an average particle diameter of 13 nm.
And it dried by 80 degreeC dryer for 12 hours, and obtained white powder 5.2g. As a result of X-ray diffraction of this white powder, it was cerium oxide. The crystallite diameter determined from the half width is 13.4 nm. The results are shown in Table 1 and FIG.
It can be seen from the TEM photograph and the crystallite diameter determined from X-ray diffraction that single crystal particles were obtained.
（実施例２）
硫酸セリウム（III）八水和物１０．４ｇ及び蒸留水４８９．６ｇを５Ｌ容器に入れて攪拌（２００ｒｐｍ）し、溶解した。
引き続き攪拌しながら温度を９３℃に昇温し、１．０％水酸化ナトリウム水溶液２８０ｇの全量を一度に加え、攪拌しながら温度９３℃で６時間維持した。
次に３０℃以下に冷却したところ、白色沈殿が得られた。この溶液のｐＨは５．０だった。
この溶液を遠心分離装置を用いて、１４０００ｒｐｍで１０分間処理した後、上澄み液を除去し、蒸留水８００ｇを加え、更に遠心分離装置で、１４０００ｒｐｍで１０分間処理した。この操作を合計３回行って、沈殿物を洗浄した。
得られた沈殿物を透過型電子顕微鏡（ＴＥＭ 倍率２５万倍）で観察した。その結果を図３に示す。図３により、平均粒子径１６ｎｍの単分散粒子であることがわかる。
そして、８０℃の乾燥機で１２時間乾燥させることにより白色粉末４．５ｇを得た。この白色粉末をＸ線回折した結果、酸化セリウムであった。半値幅から求めた結晶子径は１６．５ｎｍである。結果を表１および図４に示す。
ＴＥＭ写真およびＸ線回析から求めた結晶子径より、単結晶の粒子が得られたことがわかる。
(Example 2)
10.4 g of cerium (III) sulfate octahydrate and 489.6 g of distilled water were placed in a 5 L container and stirred (200 rpm) to dissolve.
The temperature was raised to 93 ° C. while stirring, and 280 g of a 1.0% aqueous sodium hydroxide solution was added all at once, and the temperature was maintained at 93 ° C. for 6 hours with stirring.
Next, when it cooled to 30 degrees C or less, white precipitate was obtained. The pH of this solution was 5.0.
This solution was treated with a centrifugal separator at 14000 rpm for 10 minutes, then the supernatant was removed, 800 g of distilled water was added, and further treated with a centrifugal separator at 14000 rpm for 10 minutes. This operation was performed three times in total to wash the precipitate.
The obtained precipitate was observed with a transmission electron microscope (TEM magnification: 250,000 times). The result is shown in FIG. FIG. 3 shows that the particles are monodisperse particles having an average particle diameter of 16 nm.
And 4.5 g of white powder was obtained by making it dry with an 80 degreeC dryer for 12 hours. As a result of X-ray diffraction of this white powder, it was cerium oxide. The crystallite diameter determined from the half width is 16.5 nm. The results are shown in Table 1 and FIG.
It can be seen from the TEM photograph and the crystallite diameter determined from X-ray diffraction that single crystal particles were obtained.
（実施例３）
塩化セリウム（III）七水和物１０．８ｇ及び蒸留水４８９．２ｇを５Ｌ容器に入れて攪拌（２００ｒｐｍ）し、溶解した。
引き続き攪拌しながら温度を９３℃に昇温し、１．０％水酸化ナトリウム水溶液３５９ｇの全量を一度に加え、攪拌しながら温度９３℃で６時間維持した。
次に３０℃以下に冷却したところ、白色沈殿が得られた。この溶液のｐＨは１１．０だった。
この溶液を遠心分離装置を用いて、１４０００ｒｐｍで１０分間処理した後、上澄み液を除去し、蒸留水８００ｇを加え、更に遠心分離装置で、１４０００ｒｐｍで１０分間処理した。この操作を合計３回行って、沈殿物を洗浄した。
得られた沈殿物を透過型電子顕微鏡（ＴＥＭ 倍率１０万倍）で観察した。その結果を図５に示す。図５により、一次粒径８〜１５ｎｍ程度の粒子がつながって、長さ１００〜３００ｎｍ程度、太さ３０〜５０ｎｍ程度の鎖状粒子が形成されているのがわかる。そして、８０℃の乾燥機で１２時間乾燥させることにより白色粉末５．４ｇを得た。この白色粉末をＸ線回折した結果、酸化セリウムであった。半値幅から求めた結晶子径は９．６ｎｍであった。結果を表１および図６に示す。
ＴＥＭ写真およびＸ線回析から求めた結晶子径より、多結晶の粒子が得られたことがわかる。
(Example 3)
10.8 g of cerium (III) chloride heptahydrate and 489.2 g of distilled water were placed in a 5 L container and stirred (200 rpm) to dissolve.
Subsequently, the temperature was raised to 93 ° C. while stirring, and 359 g of a 1.0% aqueous sodium hydroxide solution was added all at once, and the temperature was maintained at 93 ° C. for 6 hours with stirring.
Next, when it cooled to 30 degrees C or less, white precipitate was obtained. The pH of this solution was 11.0.
This solution was treated with a centrifugal separator at 14000 rpm for 10 minutes, then the supernatant was removed, 800 g of distilled water was added, and further treated with a centrifugal separator at 14000 rpm for 10 minutes. This operation was performed three times in total to wash the precipitate.
The obtained precipitate was observed with a transmission electron microscope (TEM magnification: 100,000 times). The result is shown in FIG. FIG. 5 shows that particles having a primary particle size of about 8 to 15 nm are connected to form chain particles having a length of about 100 to 300 nm and a thickness of about 30 to 50 nm. And 5.4g of white powder was obtained by making it dry with a 80 degreeC dryer for 12 hours. As a result of X-ray diffraction of this white powder, it was cerium oxide. The crystallite diameter determined from the half width was 9.6 nm. The results are shown in Table 1 and FIG.
It can be seen that polycrystalline particles were obtained from the crystallite diameter determined from the TEM photograph and X-ray diffraction.
（実施例４）
塩化セリウム（III）七水和物１０．８ｇ及び蒸留水４８９．２ｇを５Ｌ容器に入れて攪拌（２００ｒｐｍ）し、溶解した。
引き続き攪拌しながら温度を９３℃に昇温し、１．０％水酸化ナトリウム水溶液２８０ｇの全量を一度に加え、攪拌しながら温度９３℃で６時間維持した。
次に３０℃以下に冷却したところ、白色沈殿が得られた。この溶液のｐＨは３．１だった。
この溶液を遠心分離装置を用いて、１４０００ｒｐｍで１０分間処理した後、上澄み液を除去し、蒸留水８００ｇを加え、更に遠心分離装置で、１４０００ｒｐｍで１０分間処理した。この操作を合計３回行って、沈殿物を洗浄した。
得られた沈殿物を透過型電子顕微鏡（ＴＥＭ 倍率２５万倍）で観察した。その結果を図７に示す。図７により、平均粒子径２０ｎｍの単分散粒子であることがわかる。
そして、１２０℃の乾燥機で１２時間乾燥させることにより白色粉末３．５ｇを得た。この白色粉末をＸ線回折した結果、酸化セリウムであった。半値幅から求めた結晶子径は１９．７ｎｍである。結果を表１および図８に示す。
ＴＥＭ写真およびＸ線回析から求めた結晶子径より、単結晶の粒子が得られたことがわかる。
(Example 4)
10.8 g of cerium (III) chloride heptahydrate and 489.2 g of distilled water were placed in a 5 L container and stirred (200 rpm) to dissolve.
The temperature was raised to 93 ° C. while stirring, and 280 g of a 1.0% aqueous sodium hydroxide solution was added all at once, and the temperature was maintained at 93 ° C. for 6 hours with stirring.
Next, when it cooled to 30 degrees C or less, white precipitate was obtained. The pH of this solution was 3.1.
This solution was treated with a centrifugal separator at 14000 rpm for 10 minutes, then the supernatant was removed, 800 g of distilled water was added, and further treated with a centrifugal separator at 14000 rpm for 10 minutes. This operation was performed three times in total to wash the precipitate.
The obtained precipitate was observed with a transmission electron microscope (TEM magnification: 250,000 times). The result is shown in FIG. FIG. 7 shows that the particles are monodisperse particles having an average particle diameter of 20 nm.
And it dried with 120 degreeC dryer for 12 hours, and obtained 3.5 g of white powder. As a result of X-ray diffraction of this white powder, it was cerium oxide. The crystallite diameter determined from the half width is 19.7 nm. The results are shown in Table 1 and FIG.
It can be seen from the TEM photograph and the crystallite diameter determined from X-ray diffraction that single crystal particles were obtained.
本発明の製造方法によれば、廃液中に窒素系化合物を含有することがないため、除去処理を行う必要がなく、従って、排水処理コストの低減に有用である。また、得られた酸化セリウム微粒子は、半導体基板、配線基板などの半導体ウエハ、ガラス製ハードディスク、アルミナ製ハードディスク用の研磨砥粒などに利用できる。さらに、紫外線吸収剤、ガスセンサー、固体酸化物燃料電池用の電極材料、さらにゼオライト表面に酸化セリウム微粒子を吸着させることにより、自動車用ＮＯｘ浄化触媒として利用できる。 According to the production method of the present invention, since the nitrogen-based compound is not contained in the waste liquid, it is not necessary to perform the removal treatment, and therefore it is useful for reducing the wastewater treatment cost. The obtained cerium oxide fine particles can be used for polishing wafers for semiconductor wafers such as semiconductor substrates and wiring boards, glass hard disks, and alumina hard disks. Furthermore, it can be used as a NOx purification catalyst for automobiles by adsorbing cerium oxide fine particles on the surface of zeolite by ultraviolet absorbers, gas sensors, electrode materials for solid oxide fuel cells, and zeolite.
Claims (3)
（II）工程（I）で得られた沈殿物を乾燥し、結晶子径５〜５０ｎｍの酸化セリウム微粒子を得る工程、
を有することを特徴とする酸化セリウム微粒子の製造方法。 Warmed (I) sulfate aqueous solution of cerium or cerium chloride solution to 50 to 98 ° C., then the hydroxide of alkali metal, cerium oxide (CeO 2) of the alkali metal to the moles of converted moles of hydroxide A step of mixing within a range of 1 to 10 and heating and aging at 50 to 98 ° C. for 3 hours or more , followed by cooling to obtain a precipitate;
(II) drying the precipitate obtained in step (I) to obtain fine cerium oxide particles having a crystallite diameter of 5 to 50 nm,
A process for producing cerium oxide fine particles, comprising:
１に記載の酸化セリウム微粒子の製造方法。 The method for producing fine cerium oxide particles according to claim 1, wherein the step (I) includes a step of washing the obtained precipitate.
から選ばれる１種又は２種以上であることを特徴とする請求項１または請求項２に記載の
酸化セリウム微粒子の製造方法。 3. The cerium oxide fine particle according to claim 1, wherein the alkali metal hydroxide is one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide. 4. Production method.
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