JP4488831B2 - Method for producing rare earth oxide sol or hydroxide sol - Google Patents
Method for producing rare earth oxide sol or hydroxide sol Download PDFInfo
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- JP4488831B2 JP4488831B2 JP2004230059A JP2004230059A JP4488831B2 JP 4488831 B2 JP4488831 B2 JP 4488831B2 JP 2004230059 A JP2004230059 A JP 2004230059A JP 2004230059 A JP2004230059 A JP 2004230059A JP 4488831 B2 JP4488831 B2 JP 4488831B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 62
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 229910052775 Thulium Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052727 yttrium Inorganic materials 0.000 claims description 14
- 229910052691 Erbium Inorganic materials 0.000 claims description 13
- 229910052765 Lutetium Inorganic materials 0.000 claims description 13
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- 229910052779 Neodymium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052689 Holmium Inorganic materials 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 24
- 239000000460 chlorine Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 238000000108 ultra-filtration Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- -1 rare earth compounds Chemical class 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 230000008719 thickening Effects 0.000 description 9
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 7
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical group 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、一価の無機酸根が少なく、且つゾルとしての安定性に優れた希土類元素の酸化物ゾルまたは水酸化物ゾルの製造方法に関する。
The present invention relates to a method for producing an oxide sol or hydroxide sol of a rare earth element having a small amount of monovalent inorganic acid radicals and excellent stability as a sol.
希土類元素（Ｓc、Ｙ、Ｌa、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）は特異な物理・化学的性質を有することから、ＩＴ関連や地球環境保全、エネルギー分野などの次世代を担う新規な材料として研究が盛んに行われている。工業的な応用製品としては、希土類元素化合物を用いた蛍光体が有名であり、このほかにも誘電体材料の特性調整剤として、あるいはセラミクスの焼結助剤として、また希土類元素の酸化物の屈折率が例えばＹ２Ｏ３＝１．８７、Ｌａ２Ｏ３＝１．９５、ＣｅＯ２＝２．２０と高いことから、高屈折率材料としての応用例が知られている。
これらの用途に用いられる希土類元素の水酸化物や酸化物は、近年の電子セラミクス関連製品の微小化、高性能化の要求から微粒子化されたものが求められており、特に数百ナノメーター以下の、いわゆるナノ粒子が必要とされている。
Since rare earth elements (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) have unique physical and chemical properties, Research is actively conducted as a new material for the next generation in IT-related, global environmental conservation, and energy fields. As industrially applied products, phosphors using rare earth compounds are well-known, and in addition to these, they are used as dielectric material property modifiers, ceramic sintering aids, and rare earth element oxides. Since the refractive index is high, for example, Y 2 O 3 = 1.87, La 2 O 3 = 1.95, and CeO 2 = 2.20, an application example as a high refractive index material is known.
Rare earth element hydroxides and oxides used in these applications are required to be finely divided due to recent demands for miniaturization and high performance of electronic ceramics-related products, especially several hundred nanometers or less. There is a need for so-called nanoparticles.
このような要求のもと、これまで希土類水酸化物ゾルの製造に関しては種々報告されている。例えば、希土類元素の塩水溶液と過剰量のアンモニアとの反応により、水酸化物ゲルを形成させた後、生成したアンモニウム塩を除去することにより希土類水酸化物のゾルを製造する方法が提案されている（例えば、特許文献１参照）。この方法は、希土類元素の塩水溶液の中和、生成ゲルの洗浄、熱処理という単純な工程でゾルが得られるという利点を有し、経済的にも大量生産に適した方法である。しかしながら、この製造法によって得られるゾルは、原料に塩化物や硝酸塩等の無機酸塩を使用しているため、通常の中和工程だけでは原料に由来する塩素や硝酸イオン等の一価の無機酸根がゾル中に残留する。特に、元素番号の大きい重希土類元素（Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）は塩基性が強く、一価の無機酸根を強く吸着する性質が強いため、例えば重希土類元素の塩化物を出発原料とする場合には、塩素イオンの相当量の残存を避けることができない。 Under such demands, various reports have been reported regarding the production of rare earth hydroxide sols. For example, a method of producing a rare earth hydroxide sol by forming a hydroxide gel by a reaction between an aqueous salt solution of a rare earth element and an excess amount of ammonia and then removing the produced ammonium salt has been proposed. (For example, refer to Patent Document 1). This method has an advantage that a sol can be obtained by simple steps of neutralization of a salt solution of rare earth elements, washing of a generated gel, and heat treatment, and is economically suitable for mass production. However, since the sol obtained by this production method uses inorganic acid salts such as chlorides and nitrates as raw materials, monovalent inorganic substances such as chlorine and nitrate ions derived from the raw materials can be obtained only by a normal neutralization step. Acid radicals remain in the sol. In particular, heavy rare earth elements having a large element number (Ho, Er, Tm, Yb, Lu) are strong in basicity and strongly adsorb monovalent inorganic acid radicals. In this case, a considerable amount of chlorine ions cannot be avoided.
従って、特許文献１に示すような従来法によって得られるゾルは、通常希土類元素の酸化物に対するモル比で０．１以上、重希土類では０．５以上の一価の無機酸根を含んでいるのが一般的である。例えば、希土類元素酸化物Ｍ２Ｏ３の平均的分子量を３６２とし、１０質量%の酸化物を含む塩酸型のゾルを想定した場合には、ゾル中に含まれる塩酸量は約１０００ｐｐｍとなる。これは希土類の元素の種類によって多少異なるが、これ以上の無機酸根の存在はいずれも望ましくなく、無機酸根量は出来るだけ少なくすることが望まれている。 Therefore, the sol obtained by the conventional method as shown in Patent Document 1 usually contains a monovalent inorganic acid group having a molar ratio of rare earth element to oxide of 0.1 or more and heavy rare earth of 0.5 or more. Is common. For example, assuming an average molecular weight of the rare earth element oxide M 2 O 3 of 362 and a hydrochloric acid type sol containing 10% by mass of oxide, the amount of hydrochloric acid contained in the sol is about 1000 ppm. This slightly differs depending on the kind of rare earth element, but any inorganic acid radicals beyond this level are undesirable, and it is desired to reduce the amount of inorganic acid radicals as much as possible.
前述の通り、希土類元素の多くは、セラミックス材料や触媒用途にも利用されており、これら材料の焼結時に発生する塩素イオン由来の酸性ガスは炉体または環境に悪影響を及ぼす可能性があるだけでなく、製品の性能そのものを悪化させる原因ともなっている。そこで、特許文献１ではこれらの問題を解決するため、過剰量のアルカリ剤であるアンモニアを投与して脱酸根を行っているが、過剰量の添加であるために生産効率は著しく悪いものであり、その結果、製造されたゾルは高価なものとなる。また酸根の除去効率向上のため中和・洗浄時の温度を高くすると、生成するゾルの粒子が大きくなり、所望する粒子径の小さなゾルを得ることができない欠点があった。 As mentioned above, most rare earth elements are also used for ceramic materials and catalyst applications, and the acidic gas derived from chlorine ions generated during sintering of these materials can only have an adverse effect on the furnace body or the environment. Not only that, it also causes the product performance itself to deteriorate. Therefore, in Patent Document 1, in order to solve these problems, deoxidation radicals are performed by administering an excessive amount of ammonia, which is an alkaline agent, but the production efficiency is extremely poor due to the excessive amount of addition. As a result, the produced sol becomes expensive. Further, if the temperature during neutralization / washing is increased to improve the removal efficiency of acid radicals, the sol particles produced increase in size, and there is a drawback that a desired sol with a small particle diameter cannot be obtained.
ところで、希土類元素の酸化物または水酸化物は塩基性化合物であるため、ゾルを構成する粒子を分散安定化させるためには陰イオン性物質を表面に吸着させる必要がある。それゆえに、特許文献１に於いては塩素イオンが分散安定化剤として作用しているため、これを単純に除去すると粒子が小さいゾルは得られるものの安定性に乏しいものとなり、沈殿、固化するという問題がある。 By the way, since the rare earth element oxide or hydroxide is a basic compound, it is necessary to adsorb an anionic substance on the surface in order to disperse and stabilize the particles constituting the sol. Therefore, in Patent Document 1, since chloride ions act as a dispersion stabilizer, if this is simply removed, a sol with small particles can be obtained, but the stability will be poor, and it will precipitate and solidify. There's a problem.
一方、塩素イオン等の一価の無機酸根を含有せず、酢酸で分散安定化した稀土類元素の酸化物ゾルが提案されている（例えば、特許文献２参照）。
この酢酸は無機の酸根の様な腐食性はなく、比較的利用しやすいものの、熱処理時にその臭気が問題になる場合があり、その結果用途は著しく限定されていた。また、上記従来技術によって得られる希土類元素のゾルはいずれも酸性領域のみで安定なもので、中性からアルカリ領域では不安定であり、塩基性物質を加えるとゲル化するという欠点を有していた。
On the other hand, a rare earth element oxide sol that does not contain monovalent inorganic acid radicals such as chloride ions and is stabilized by dispersion with acetic acid has been proposed (for example, see Patent Document 2).
Although this acetic acid is not corrosive like an inorganic acid radical and is relatively easy to use, its odor sometimes becomes a problem during heat treatment, and as a result, its use has been remarkably limited. In addition, the sols of rare earth elements obtained by the above-mentioned prior art are all stable only in the acidic region, unstable in the neutral to alkaline region, and have the disadvantage of gelling when a basic substance is added. It was.
希土類元素の酸化物の一種である酸化セリウムについて、本出願人は有機酸で解膠したセリウムゾルに関する技術を開示したが、この技術については、本発明で云う希土類元素の全てに適用できるものではなく、また酸根に関しては何ら詳細な説明を行なっていない(例えば、特許文献３及び特許文献４参照)。
前述のような背景技術から、希土類元素の酸化物または水酸化物のゾルを工業的に利用するためには、腐食性や臭気の問題が無く、且つ、酸性からアルカリ性の広い範囲で長期にわたって安定なものが強く要望されている。
Regarding cerium oxide, which is a kind of rare earth element oxide, the present applicant has disclosed a technique relating to cerium sol peptized with an organic acid, but this technique is not applicable to all rare earth elements in the present invention. In addition, no detailed explanation is given regarding acid radicals (see, for example, Patent Document 3 and Patent Document 4).
From the background art described above, in order to industrially use rare earth oxide or hydroxide sol, there is no problem of corrosiveness and odor, and it is stable over a wide range from acidic to alkaline. There is a strong demand for something.
本発明は、前述のように各種機能性材料に使用できる希土類元素酸化物を提供する希土類元素の酸化物ゾルまたは水酸化物ゾルの製造方法に関する。本発明は、有害なガスを発生する塩素イオン、硝酸イオン等の一価の無機酸根を実質的に含まないか或いは極めて少なく、しかも酢酸のような刺激臭を有しない、長期にわたって安定性の高い希土類元素の酸化物ゾルまたは水酸化物ゾルの製造方法を提供することを目的とする。
The present invention relates to a method for producing a rare earth oxide sol or hydroxide sol that provides a rare earth oxide that can be used in various functional materials as described above. The present invention has substantially no or very few monovalent inorganic acid radicals such as chlorine ions and nitrate ions that generate harmful gases, and has no irritating odor such as acetic acid, and has high stability over a long period of time. It is an object of the present invention to provide a method for producing a rare earth oxide sol or hydroxide sol.
本発明は、一価の無機酸根で安定化されていたため、その用途が限定されていた希土類元素の酸化物ゾルまたは水酸化物ゾルの改良に係り、特定範囲のメジアン径を有する希土類元素の酸化物ゾルまたは水酸化物ゾルに、ヒドロキシカルボン酸を用いて分散安定化させることにより、一価の無機酸根を実質的に含有せず、極めて安定で広範な用途に適合しうる希土類元素の酸化物ゾルまたは水酸化物ゾルが得られることを見出し、係る知見に基づき本発明を完成したものである。 Since the present invention is stabilized by monovalent inorganic acid radicals, the present invention relates to the improvement of rare earth element oxide sols or hydroxide sols whose use has been limited, and oxidation of rare earth elements having a median diameter in a specific range. Oxides of rare earth elements that do not contain any monovalent inorganic acid radicals and are extremely stable and suitable for a wide range of applications, by dispersing and stabilizing the product sol or hydroxide sol using hydroxycarboxylic acid The present inventors have found that a sol or hydroxide sol can be obtained, and have completed the present invention based on such knowledge.
即ち、本発明は、メジアン径が１０〜３００ｎｍであり、ヒドロキシカルボン酸を希土類元素Ｍ（但し、Ｍは、Ｓｃ、Ｙ、Ｌa、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＬｕから選ばれた希土類元素を示す）に対し、ヒドロキシカルボン酸／Ｍ２Ｏ３（モル比）として０．０５〜０．５の範囲で含有する希土類元素の酸化物ゾルまたは水酸化物ゾルの製造方法に関する。
That is, in the present invention, the median diameter is 10 to 300 nm, and hydroxycarboxylic acid is a rare earth element M (where M is Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Oxidation of rare earth elements contained in the range of 0.05 to 0.5 as hydroxycarboxylic acid / M 2 O 3 (molar ratio) with respect to rare earth elements selected from Ho, Er, Tm, Yb and Lu) The present invention relates to a method for producing a product sol or a hydroxide sol.
本発明で得られる希土類元素の酸化物ゾルまたは水酸化物ゾル中には、一価の無機酸根を実質的に含有せず、或いは含有しても極めて少量であることから、セラミックス材料等の焼結時に発生する不要なガスの生成もなく、炉体あるいは環境に対する悪影響のないゾルである。
また、ゾルとして頗る安定なゾルが得られるため、希土類元素を用いる製品の性能向上に極めて有効である。
The rare earth element oxide sol or hydroxide sol obtained in the present invention contains substantially no monovalent inorganic acid radical or contains a very small amount. It is a sol that does not generate unnecessary gas generated during congealing and does not adversely affect the furnace body or the environment.
Further, since a stable sol that can be obtained as a sol can be obtained, it is extremely effective in improving the performance of products using rare earth elements.
以下本発明のゾルについて詳細に説明する。
本発明のゾルは、ゾルを構成する粒子のメジアン径が１０〜３００ｎｍであることが第一の特徴であり、更にヒドロキシカルボン酸を希土類元素Ｍ（但し、Ｍは、Ｓｃ、Ｙ、Ｌa、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＬｕから選ばれた希土類元素を示す）に対し、ヒドロキシカルボン酸／Ｍ２Ｏ３（モル比）として０．０５〜０．５の範囲で含有していることが特徴である。
Hereinafter, the sol of the present invention will be described in detail.
The first feature of the sol of the present invention is that the median diameter of the particles constituting the sol is 10 to 300 nm. Further, the hydroxycarboxylic acid is a rare earth element M (where M is Sc, Y, La, Ce). , Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu represents a rare earth element) and 0 as hydroxycarboxylic acid / M 2 O 3 (molar ratio) It is characterized by containing in the range of 0.05 to 0.5.
このメジアン径が１０ｎｍ以下の粒子径の小さなゾルは、機能性物質を構成する希土類元素の酸化物原料としては好ましいものではあるが、きわめて増粘し易く、長期安定性に問題がある。そこで、このような微細な粒子を安定化させるには分散安定化剤の量が非常に多く必要となり、効果に対する経済性が損なわれるという欠点がある。
一方、メジアン径が３００ｎｍ以上の大きな粒子のゾルでは、粒子が安定分散せず重力によって沈殿を生じるため好ましくない。
従って、更に好ましくはメジアン径は１５〜１５０ｎｍの範囲であることが推奨される。尚、本発明で云うメジアン径とは、動的光散乱法によって測定したゾル分散状態下でのゾル粒子の平均直径をいう。
Although a sol having a median diameter of 10 nm or less and having a small particle diameter is preferable as an oxide raw material for a rare earth element constituting a functional substance, it is very easy to thicken and has a problem in long-term stability. Therefore, in order to stabilize such fine particles, a very large amount of the dispersion stabilizer is required, and there is a drawback that the economic efficiency is impaired.
On the other hand, a sol of large particles having a median diameter of 300 nm or more is not preferable because the particles do not stably disperse and precipitate due to gravity.
Therefore, it is more preferable that the median diameter is in the range of 15 to 150 nm. The median diameter in the present invention refers to the average diameter of sol particles under a sol dispersion state measured by a dynamic light scattering method.
ゾルの分散安定化剤としては、ヒドロキシカルボン酸またはその塩類が最も適しており、これによって希土類元素の酸化物ゾルまたは水酸化物のゾルを長期にわたり安定に分散させることができる。
ヒドロキシカルボン酸の含有量については、ゾルが安定である範囲内で少ない方が好ましいが、実質的にはヒドロキシカルボン酸／Ｍ２Ｏ３（モル比）で０．０５〜０．５の範囲が望ましい。より好ましくはヒドロキシカルボン酸／Ｍ２Ｏ３（モル比）で０．１〜０．４５の範囲である。上記範囲を逸脱した場合は、ゾルが不安定になり、増粘、ゲル化するという問題を生じる。
As the sol dispersion stabilizer, hydroxycarboxylic acid or a salt thereof is most suitable, whereby the rare earth oxide sol or hydroxide sol can be stably dispersed over a long period of time.
The hydroxycarboxylic acid content is preferably as small as possible within the range in which the sol is stable, but the hydroxycarboxylic acid / M 2 O 3 (molar ratio) is substantially in the range of 0.05 to 0.5. desirable. More preferably in the range of 0.1 to 0.45 with a hydroxy carboxylic acid / M 2 O 3 (molar ratio). When deviating from the above range, the sol becomes unstable, causing the problem of thickening and gelling.
本発明のゾルに含有されるヒドロキシカルボン酸は、水酸基とカルボキシル基を分子内に有する化合物であれば特段限定されず、希土類元素の酸化物粒子または水酸化物粒子を分散安定化することができる。本発明の希土類元素の酸化物ゾルまたは水酸化物ゾルのように、非常に微細な粒子を液中で安定化させるためには、キレート性能に富んだものが好ましく、例えばクエン酸、リンゴ酸、酒石酸など、カルボキシル基を２以上有するものの使用が好ましく、最も好ましくはカルボキシル基を３つ有するクエン酸が推奨される。
カルボキシル基の数が多いものほど希土類元素の酸化物または水酸化物の微粒子を安定化させる効果が高く、しかも一価の無機酸根の含有量を低減させることができる。上記ヒドロキシカルボン酸は最終的に酸の状態でもアミンやアンモニアと反応した塩の形でゾル中に含有されていてもよい。
The hydroxycarboxylic acid contained in the sol of the present invention is not particularly limited as long as it is a compound having a hydroxyl group and a carboxyl group in the molecule, and can disperse and stabilize rare earth element oxide particles or hydroxide particles. . In order to stabilize very fine particles in the liquid, like the rare earth oxide sol or hydroxide sol of the present invention, those having a high chelating ability are preferable, such as citric acid, malic acid, Preference is given to using tartaric acid or the like having two or more carboxyl groups, most preferably citric acid having three carboxyl groups.
The larger the number of carboxyl groups, the higher the effect of stabilizing the rare earth element oxide or hydroxide fine particles, and the content of monovalent inorganic acid radicals can be reduced. The hydroxycarboxylic acid may be finally contained in the sol in the form of a salt reacted with amine or ammonia even in the acid state.
本発明のメジアン径が１０〜３００ｎｍを有するゾルの製造法については、特許文献１に記載しているような従来法に示されるように、希土類元素の塩化物をアルカリで中和することによって得た沈降性のゲルを、洗浄、熱処理してゾル化して製造することができ、無機酸根を含むものの、元素の種類に応じて経済的で再現性よくゾルを得ることができる。また、特許文献２に示すような方法により、酢酸を含むゾルを得ることによっても上記範囲の粒子を有するゾルが得られる。
本発明のゾルは、これらのゾルの分散剤をヒドロキシカルボン酸で置換することにより最も簡単に製造することができる。
The method for producing a sol having a median diameter of 10 to 300 nm according to the present invention is obtained by neutralizing a rare earth element chloride with an alkali as shown in the conventional method described in Patent Document 1. The precipitated gel can be produced by washing and heat treatment to form a sol. Although it contains an inorganic acid radical, the sol can be obtained economically and reproducibly depending on the type of element. A sol having particles in the above range can also be obtained by obtaining a sol containing acetic acid by a method as shown in Patent Document 2.
The sol of the present invention can be most easily produced by replacing the dispersant of these sols with hydroxycarboxylic acid.
以下に、従来法による無機酸根を含むゾルの製法についてより詳細に説明し、更に一価の無機酸根の除去とヒドロキシカルボン酸による安定化法について詳述する。
本発明によるゾル構成元素は、希土類元素として、Ｓｃ、Ｙ、Ｌa、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＬｕから選ばれた希土類元素であり、本発明のゾル製造に用いる希土類元素の水酸化物ゲルは公知方法によって得られるゲルを使用することができる。
例えば、水溶性の希土類元素の塩とアルカリ剤を反応させた後、副生する塩を洗浄除去して得られるゲルを使用することができる。
水溶性の希土類元素の塩としては、希土類元素の塩化物、硝酸塩等が例示でき、これらは市販の材料から入手することができるが、希土類元素の酸化物を塩酸、硝酸等の無機酸に溶解させて得ることもできる。
また使用するアルカリ剤としては、アンモニア、水酸化ナトリウム等をはじめ、有機アミン類や水酸化カリウム、水酸化リチウム等も使用することができる。上述のごとくして得られる希土類元素のゲルは、含有する酸根により自然にゾル化する場合も有るが、必要に応じて熱処理等により解膠してゾルとすることができる。
このとき含有する一価の酸根は、希土類元素のうち、Ｓｃ、Ｙ、Ｌa、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、ＴｂおよびＤｙに関しては、一価の酸根／Ｍ２Ｏ３（モル比）＝０．０４〜０．６の範囲で含有するものが、所望するメジアン径で安定であり、希土類元素のうち、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＬｕに関しては、一価の酸根を一価の酸根／Ｍ２Ｏ３（モル比）＝０．３〜１．５の範囲で含有するものが安定である。
一価の酸根が、上記所定範囲内にないときは、別途無機酸をゲルに所定量となるように添加すればよい。
いずれの場合も、一価の酸根が下限を下廻ると解膠が充分でなくなり、透明で安定なゾルを得ることができない。一方、上限を超えると酸に対する溶解度が大きくなり、収率が低下する。
Below, the manufacturing method of the sol containing the inorganic acid radical by the conventional method is demonstrated in detail, Furthermore, the removal method of a monovalent | monohydric inorganic acid radical and the stabilization method by hydroxycarboxylic acid are explained in full detail.
The sol constituent elements according to the present invention are rare earth elements selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu as rare earth elements. In addition, the rare earth element hydroxide gel used in the sol production of the present invention may be a gel obtained by a known method.
For example, it is possible to use a gel obtained by reacting a salt of a water-soluble rare earth element with an alkali agent and then washing and removing the by-product salt.
Examples of water-soluble rare earth element salts include rare earth element chlorides and nitrates, which can be obtained from commercially available materials, but rare earth element oxides are dissolved in inorganic acids such as hydrochloric acid and nitric acid. It can also be obtained.
Moreover, as an alkaline agent to be used, ammonia, sodium hydroxide, etc., organic amines, potassium hydroxide, lithium hydroxide, etc. can be used. The rare earth element gel obtained as described above may be naturally solated by the acid radicals contained therein, but if necessary, it can be peptized by heat treatment or the like to form a sol.
The monovalent acid radicals contained at this time are Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy among the rare earth elements, and are monovalent acid radicals / M 2 O 3 (moles). Ratio) = 0.04 to 0.6 is stable in the desired median diameter. Among rare earth elements, Ho, Er, Tm, Yb and Lu are monovalent acid radicals. it is stable those containing in a range of valence of acid radical / M 2 O 3 (molar ratio) = 0.3 to 1.5.
When the monovalent acid radical is not within the predetermined range, an inorganic acid may be separately added to the gel so as to have a predetermined amount.
In either case, when the monovalent acid radical is below the lower limit, peptization is not sufficient, and a transparent and stable sol cannot be obtained. On the other hand, when the upper limit is exceeded, the acid solubility increases and the yield decreases.
解膠時の希土類元素の水酸化物ゾルの濃度に関しては、特段限定されないが、Ｍ２Ｏ３として大略１〜１０質量％の範囲が好ましい。
熱処理条件に関しては、通常の１００℃までの加熱処理だけでなく、１００℃以上の水熱処理を用いることもできる。本発明のゾルの種類、用途に応じてこの加熱条件を設定し、メジアン径１０〜３００ｎｍで安定な希土類元素の酸化物ゾルまたは水酸化物ゾルを製造することができる。
The concentration of the rare earth element hydroxide sol at the time of peptization is not particularly limited, but is preferably in the range of about 1 to 10% by mass as M 2 O 3 .
Regarding heat treatment conditions, not only normal heat treatment up to 100 ° C. but also hydrothermal treatment at 100 ° C. or higher can be used. This heating condition is set according to the kind and use of the sol of the present invention, and a stable rare earth oxide sol or hydroxide sol having a median diameter of 10 to 300 nm can be produced.
次いで得られたゾルに、所定量のヒドロキシカルボン酸を添加し、アルカリ剤によりｐＨを９〜１２に調整した後、限外濾過する工程に供する。
本発明で使用するヒドロキシカルボン酸の添加量は、希土類元素の酸化物１モルに対し０．３〜０．７モルの範囲が好ましい。この範囲以下では、残存している酸根を後述する操作によって充分除去することができず、本発明の一価の無機酸根含有量の極めて少ないゾルが得られないため好ましくない。
一方、添加量がこの範囲以上になるとアルカリ剤の添加時にゾルが溶解し、限外濾過による洗浄中に濾過漏れを生じる可能性があり、その場合には収率が極端に低下し好ましくない。その態様に関しては、固体、水溶液いずれの状態で投入してもよいが、最終的にゾル中に全てのヒドロキシカルボン酸が溶解していることが必要である。
Next, a predetermined amount of hydroxycarboxylic acid is added to the obtained sol, and the pH is adjusted to 9 to 12 with an alkali agent, followed by ultrafiltration.
The amount of the hydroxycarboxylic acid used in the present invention is preferably in the range of 0.3 to 0.7 mol with respect to 1 mol of the rare earth element oxide. Below this range, the remaining acid radicals cannot be sufficiently removed by the operation described later, and a sol with an extremely low monovalent inorganic acid radical content of the present invention cannot be obtained.
On the other hand, if the amount added exceeds this range, the sol dissolves when the alkaline agent is added, and filtration leakage may occur during washing by ultrafiltration. In this case, the yield is extremely lowered, which is not preferable. With regard to the embodiment, it may be charged in either a solid state or an aqueous solution, but it is necessary that all hydroxycarboxylic acids are finally dissolved in the sol.
例えば、撹拌下にある解膠したゾルに１〜１０質量%のヒドロキシカルボン酸水溶液をゆっくり添加すれば、安定に添加することができる。ヒドロキシカルボン酸の添加によってゾルは一時的に濁るか、または増粘する場合があるが、後段の工程でのアルカリ剤の添加によって溶液は再びゾルの外観を呈するようになる。添加時の増粘が著しい場合は原料ゾルの濃度を低下させれば良い。一価の無機酸根は、ヒドロキシカルボン酸の存在下でのアルカリ剤の添加によって、ヒドロキシカルボン酸と置換して遊離し、続いて行われる限外濾過による洗浄により系外に取り除かれる。 For example, if a 1-10 mass% hydroxycarboxylic acid aqueous solution is slowly added to the peptized sol under stirring, it can be added stably. Although the sol may become temporarily turbid or thickened by the addition of hydroxycarboxylic acid, the solution again becomes sol-like by the addition of the alkaline agent in the subsequent step. If the thickening at the time of addition is significant, the concentration of the raw material sol may be lowered. Monovalent inorganic acid radicals are liberated by replacement with hydroxycarboxylic acid by the addition of an alkaline agent in the presence of hydroxycarboxylic acid, and then removed out of the system by washing by subsequent ultrafiltration.
本発明で使用するアルカリ剤の種類としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、アンモニア、アミン類などを用いることができるが、経済性、作業性の点から水酸化ナトリウムおよびアンモニア水が好ましい。アルカリ剤添加時の濃度に関しては特段制限はないが、アルカリ剤の添加量に関しては、ゾルのｐＨが９〜１２となる様に添加すれば良い。このｐＨ範囲を逸脱すると一価の無機酸根を充分除去することができない。
ところでオキシカルボン酸、アルカリ剤の添加時の温度に関しては、１０〜９０℃の範囲内であれば特段制限はなく、温度によって性能が大きく異なることはないが、本発明で重要な点は、ヒドロキシカルボン酸の添加の後にアルカリ剤を添加することであり、この添加順序を逆にすると安定なゾルを得ることはできない。
ヒドロキシカルボン酸およびアルカリ剤を添加した後のゾルは、限外濾過による洗浄を行い濾液の電気伝導度が５Ｓ／ｍ以下となるまで洗浄することが好ましい。
この洗浄が不十分な場合は、一価の酸根やヒドロキシカルボン酸の残存量が多くなり、ゾルの安定性が低下するため好ましくない。
また、洗浄後に限外濾過または加熱により濃縮することもでき、Ｍ２Ｏ３濃度として５〜５０質量%のゾルを得ることができる。
As the kind of alkaline agent used in the present invention, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, amines and the like can be used. From the viewpoint of economy and workability, sodium hydroxide and aqueous ammonia are used. Is preferred. There is no particular restriction on the concentration when the alkali agent is added, but the amount of the alkali agent added may be added so that the sol has a pH of 9-12. When deviating from this pH range, monovalent inorganic acid radicals cannot be sufficiently removed.
By the way, the temperature at the time of addition of the oxycarboxylic acid and the alkali agent is not particularly limited as long as it is within the range of 10 to 90 ° C., and the performance does not vary greatly depending on the temperature. An alkaline agent is added after the addition of the carboxylic acid. If the order of addition is reversed, a stable sol cannot be obtained.
The sol after the addition of the hydroxycarboxylic acid and the alkaline agent is preferably washed by ultrafiltration until the electrical conductivity of the filtrate is 5 S / m or less.
Insufficient washing is not preferable because the residual amount of monovalent acid radicals and hydroxycarboxylic acid increases, and the stability of the sol decreases.
It is also possible to concentrate by ultrafiltration or heating after washing, it is possible to obtain a 5 to 50 wt% of sol as M 2 O 3 concentration.
この様にして得られる希土類元素の水酸化物ゾルは、ゾル中に残存していた一価の無機酸根が除去され、希土類元素のうち、Ｓｃ、Ｙ、Ｌa、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙに関しては、希土類元素の酸化物１モルに対する一価の酸根は０．０５以下となる。
また、希土類元素のうち、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕに関しては、希土類酸化物１モルに対する一価の酸根は０．１以下となる。希土類元素の水酸化物ゾルは、実質的にヒドロキシカルボン酸で分散安定化されたゾルとなる。希土類元素の水酸化物ゾル中のオキシカルボン酸量に関しては、希土類元素の酸化物のモル数に対して０．０５〜０．５の範囲内となる。本発明の希土類元素の水酸化物ゾルのｐＨに関しては、その製造条件によって異なるが、概ね６〜１０の範囲内にあり、必要に応じてヒドロキシカルボン酸塩あるいはアンモニア、アミン類を添加することで所望のｐＨに調整することができ、その状態で長期にわたり安定となる。
In the rare earth element hydroxide sol thus obtained, the monovalent inorganic acid radicals remaining in the sol are removed, and among the rare earth elements, Sc, Y, La, Ce, Pr, Nd, Sm, Regarding Eu, Gd, Tb, and Dy, the monovalent acid radical with respect to 1 mol of the rare earth element oxide is 0.05 or less.
Of the rare earth elements, Ho, Er, Tm, Yb, and Lu have a monovalent acid radical of 0.1 or less with respect to 1 mol of the rare earth oxide. The rare earth element hydroxide sol is substantially a dispersion-stabilized sol with hydroxycarboxylic acid. The amount of oxycarboxylic acid in the rare earth element hydroxide sol is in the range of 0.05 to 0.5 with respect to the number of moles of the rare earth element oxide. The pH of the rare earth element hydroxide sol of the present invention varies depending on the production conditions, but is generally in the range of 6 to 10, and by adding a hydroxycarboxylate, ammonia, or amines as necessary. It can be adjusted to a desired pH and is stable for a long time in that state.
以下に、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。尚、実施例において％は、特に断らない限り全て質量％を示す。
また、実施例中の限外濾過装置は、限外濾過膜として「ラボモジュール」型式ＳＬＰ−１０５３（旭化成(株)製）を用いた。更に、保存安定性の試験は、試料を５０ｃｃ容サンプル瓶に入れて封入し、３５℃の恒温槽で行なった。
本発明の希土類元素の酸化物ゾルまたは水酸化物ゾルの物性は、以下の方法で測定した。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In Examples, “%” means “% by mass” unless otherwise specified.
Moreover, the ultrafiltration apparatus in an Example used "lab module" model SLP-1053 (made by Asahi Kasei Co., Ltd.) as an ultrafiltration membrane. Furthermore, the storage stability test was performed by placing the sample in a 50 cc sample bottle and sealing it in a thermostatic chamber at 35 ° C.
The physical properties of the rare earth oxide sol or hydroxide sol of the present invention were measured by the following methods.
（１）メジアン径の測定
メジアン径は、動的光散乱色粒度分布測定装置LB-500（堀場製作所(株)製）を用いて測定した。
(1) Measurement of median diameter The median diameter was measured using a dynamic light scattering color particle size distribution analyzer LB-500 (manufactured by Horiba, Ltd.).
（２）ヘイズ率の測定
ヘイズ率は、色差計COH-300A（日本電色工業(株)製）を用いて測定した。測定条件としては、試料を光路長１ｃｍのガラスセルに入れて測定した。
(2) Measurement of haze ratio The haze ratio was measured using a color difference meter COH-300A (manufactured by Nippon Denshoku Industries Co., Ltd.). As measurement conditions, the sample was placed in a glass cell having an optical path length of 1 cm and measured.
（３）電気伝導度の測定
電気伝導度は、電気伝導度計CM-14P（TOA ELECTRON Ltd．製）を用いて測定した。
(3) Measurement of electric conductivity The electric conductivity was measured using an electric conductivity meter CM-14P (manufactured by TOA ELECTRON Ltd.).
１％アンモニア水溶液１８７８gに酸化ツリウム（３Ｎ、日本イットリウム(株)製）５０ｇを塩酸に溶解させた０．５％溶液１００００ｇを撹拌下で添加し、ツリウムゲルを生成させた。これを限外濾過装置を用いてゲル中の塩化アンモニウムを除去し、塩素根がＣｌ／Ｔｍ２Ｏ３（モル比）として０．７を含有するＴｍ２Ｏ３濃度２％のツリウムゲル溶液を得た。
次いで、これをオートクレーブに入れ、１１０℃で３時間水熱処理を行ない、Ｔｍ２Ｏ３濃度２％のツリウムゾルを得た。次いでこのゾルにＴｍ２Ｏ３１モルに対して０．５モルの１０％クエン酸溶液を添加し、更に３％アンモニア水を用いてｐＨ９．５に調整した後、限外濾過装置を用いて濾液の電気伝導度が５Ｓ/ｍ以下になるまで濾過・濃縮を行い、Ｔｍ２Ｏ３として１０％のツリウムゾルを得た。
得られた１０％のツリウムゾルは、メジアン径１２４ｎｍ、Ｃｌ／Ｔｍ２Ｏ３（モル比）＝０．０６、クエン酸／Ｔｍ２Ｏ３（モル比）＝０．４、ヘイズ率２４．９％、電気伝導度２．１Ｓ／ｍ、ｐＨ６．９であった。また１ヶ月間でのゾルの保存安定性は増粘や沈殿物の発生もなく良好であった。更に、この溶液に２８％アンモニア水を添加しゾルのｐＨを１０に調整し、３ヶ月後の保存安定性の試験を行なった結果、安定状態を維持していた。
To 1878 g of a 1% aqueous ammonia solution, 10000 g of a 0.5% solution prepared by dissolving 50 g of thulium oxide (3N, manufactured by Nippon Yttrium Co., Ltd.) in hydrochloric acid was added with stirring to produce a thulium gel. This was used to remove ammonium chloride in the gel using an ultrafiltration device, and a thulium gel solution with a Tm 2 O 3 concentration of 2% containing 0.7 as Cl / Tm 2 O 3 (molar ratio) of chlorine roots was obtained. It was.
Next, this was put in an autoclave and hydrothermally treated at 110 ° C. for 3 hours to obtain a thulium sol having a Tm 2 O 3 concentration of 2%. Next, 0.5 mol of 10% citric acid solution was added to this sol with respect to 1 mol of Tm 2 O 3, and the pH was adjusted to 9.5 using 3% aqueous ammonia, and then an ultrafiltration device was used. Filtration and concentration were performed until the electrical conductivity of the filtrate was 5 S / m or less, and 10% thulium sol was obtained as Tm 2 O 3 .
The obtained 10% thulium sol had a median diameter of 124 nm, Cl / Tm 2 O 3 (molar ratio) = 0.06, citric acid / Tm 2 O 3 (molar ratio) = 0.4, and a haze ratio of 24.9%. The electrical conductivity was 2.1 S / m and the pH was 6.9. Also, the storage stability of the sol within one month was good without thickening or generation of precipitates. Further, 28% ammonia water was added to this solution to adjust the pH of the sol to 10 and a storage stability test was conducted after 3 months. As a result, the stable state was maintained.
比較例として特公平７−６１，８６４号公報に従い、２Ｎ酢酸溶液１Ｌと酸化ツリウム（３Ｎ、日本イットリウム(株)製）２９０ｇを混合し、機械的に撹拌して分散させた。さらに、７０℃で３時間３０分間加熱を行い、得られた溶液を遠心分離機により３５０ｒｐｍで２０分間遠心分離を行った。次いで、上澄みを５Ｃ濾紙で濾過し、希釈調整してＴｍ２Ｏ３として１０％のツリウムゾルを得た。得られた酢酸で安定化されたツリウムゾルは、電気伝導度３３．５Ｓ／ｍ、ｐＨ７．２であった。また、１ヶ月間での保存安定性は、増粘後、沈殿を生成した。更に、この溶液に２８％アンモニア水を添加し、ゾルのｐＨを１０に調整したところ、直ちにゲル化した。 As a comparative example, according to Japanese Patent Publication No. 7-61,864, 1 L of 2N acetic acid solution and 290 g of thulium oxide (3N, manufactured by Nippon Yttrium Co., Ltd.) were mixed and dispersed by mechanical stirring. Furthermore, heating was performed at 70 ° C. for 3 hours and 30 minutes, and the obtained solution was centrifuged at 350 rpm for 20 minutes using a centrifuge. Next, the supernatant was filtered with 5C filter paper and diluted to obtain 10% thulium sol as Tm 2 O 3 . The obtained thulium sol stabilized with acetic acid had an electric conductivity of 33.5 S / m and a pH of 7.2. Moreover, the storage stability within one month produced a precipitate after thickening. Furthermore, when 28% ammonia water was added to this solution and the pH of the sol was adjusted to 10, gelation occurred immediately.
１％水酸化ナトリウム水溶液５５８５gに酸化ランタン（３Ｎ、稀産金属(株)製）５０ｇを塩酸に溶解させた０．５％溶液１００００ｇを撹拌下で添加し、ランタンゲルを生成させた。これを限外濾過装置を用いてランタンゲル溶液中の塩化ナトリウムを除去し、塩素根がＣｌ／Ｌａ２Ｏ３（モル比）として０．０８含有するＬａ２Ｏ３濃度５％のランタンゲル溶液を得た。
次いで、これをオートクレーブに入れ、９０℃で５時間水熱処理を行ない、Ｌａ２Ｏ３濃度５％のランタンゾルを得た。次に、このゾルにＬａ２Ｏ３１モルに対して０．５モルの１０％クエン酸溶液を添加し、更に３％アンモニア水を用いてゾルｐＨ９．５に調整した後、限外濾過装置を用いて濾液の電気伝導度が５Ｓ/ｍ以下になるまで濾過・濃縮を行い、Ｌａ２Ｏ３として１０％のランタンゾルを得た。
得られた１０％のランタンゾルは、メジアン径３９．４ｎｍ、Ｃｌ／Ｌａ２Ｏ３(モル比）＝０．０１、クエン酸／Ｌａ２Ｏ３(モル比）＝０．２、ヘイズ率１２．３％、電気伝導度１．２Ｓ／ｍ、ｐＨ８．０であった。また、１ヶ月間でのゾルの保存安定性は、増粘や沈殿物の発生もなく良好であった。
To 5585 g of a 1% sodium hydroxide aqueous solution, 10000 g of a 0.5% solution obtained by dissolving 50 g of lanthanum oxide (3N, manufactured by Rare Metal Co., Ltd.) in hydrochloric acid was added with stirring to produce a lanthanum gel. This was used to remove sodium chloride in the lanthanum gel solution using an ultrafiltration device, and the lanthanum gel solution containing 5% La 2 O 3 in which the chlorine root contained 0.08 as Cl / La 2 O 3 (molar ratio). Got.
Next, this was put in an autoclave and hydrothermally treated at 90 ° C. for 5 hours to obtain a lanthanum sol having a La 2 O 3 concentration of 5%. Next, after adding 0.5 mol of 10% citric acid solution to 1 mol of La 2 O 3 and adjusting the sol to sol pH 9.5 using 3% ammonia water, an ultrafiltration device was added. The solution was filtered and concentrated until the electric conductivity of the filtrate was 5 S / m or less, to obtain 10% lanthanum sol as La 2 O 3 .
The obtained 10% lanthanum sol had a median diameter of 39.4 nm, Cl / La 2 O 3 (molar ratio) = 0.01, citric acid / La 2 O 3 (molar ratio) = 0.2, and a haze ratio of 12 The electrical conductivity was 1.2 S / m, and the pH was 8.0. Also, the storage stability of the sol within one month was good without thickening and generation of precipitates.
１％水酸化ナトリウム水溶液５４０９gに酸化ネオジウム（３Ｎ、稀産金属(株)製）５０ｇを塩酸に溶解させた０．５％溶液１００００ｇを撹拌下で添加し、ネオジウムゲルを生成させた。これを限外濾過装置を用いてゲル中の塩化アンモニウムを除去し、塩素根がＣｌ／Ｎｄ２Ｏ３（モル比）として０．０７を含有するＮｄ２Ｏ３濃度５％のネオジウムゲル溶液を得た。
次いで、これをオートクレーブに入れ、１００℃で３時間水熱処理を行ない、Ｎｄ２Ｏ３濃度５％のネオジウムゾルを得た。次にこのゾルにＮｄ２Ｏ３１モルに対して０．５モルの１０％リンゴ酸溶液を添加し、更に３％アンモニア水を用いてゾルｐＨ１０に調整した後、限外濾過装置を用いて濾液の電気伝導度が５Ｓ/ｍ以下になるまで濾過・濃縮を行い、Ｎｄ２Ｏ３として１０％のネオジウムゾルを得た。
得られた１０％のネオジウムゾルは、メジアン径１６．７ｎｍ、Ｃｌ／Ｎｄ２Ｏ３（モル比）＝０．０２、リンゴ酸／Ｎｄ２Ｏ３（モル比）＝０．１、ヘイズ率２１．１％、電気伝導度１．８Ｓ／ｍ、ｐＨ８．４であった。また、１ヶ月間でのゾルの保存安定性は、増粘や沈殿物の発生もなく良好であった。
To 5409 g of a 1% sodium hydroxide aqueous solution, 10000 g of a 0.5% solution in which 50 g of neodymium oxide (3N, manufactured by Rare Metal Co., Ltd.) was dissolved in hydrochloric acid was added with stirring to produce a neodymium gel. Using an ultrafiltration device, the ammonium chloride in the gel was removed, and a Nd 2 O 3 concentration 5% neodymium gel solution containing 0.07 as the chlorine root Cl / Nd 2 O 3 (molar ratio) was prepared. Obtained.
Next, this was put in an autoclave and hydrothermally treated at 100 ° C. for 3 hours to obtain a neodymium sol having an Nd 2 O 3 concentration of 5%. Next, 0.5 mol of 10% malic acid solution is added to this sol with respect to 1 mol of Nd 2 O 3, and the sol pH is adjusted to 10 using 3% ammonia water, and then using an ultrafiltration device. Filtration and concentration were performed until the electrical conductivity of the filtrate was 5 S / m or less, and a 10% neodymium sol was obtained as Nd 2 O 3 .
The obtained 10% neodymium sol had a median diameter of 16.7 nm, Cl / Nd 2 O 3 (molar ratio) = 0.02, malic acid / Nd 2 O 3 (molar ratio) = 0.1, haze ratio 21 The electrical conductivity was 1.8 S / m and the pH was 8.4. Also, the storage stability of the sol within one month was good without thickening and generation of precipitates.
１％アンモニア水溶液１８２３gに酸化イッテルビウム（３Ｎ、信越化学(株)製）５０ｇを塩酸に溶解させた０．５％溶液１００００ｇを撹拌下で添加し、イッテルビウムゲルを生成させた。これを限外濾過装置を用いてゲル中の塩化アンモニウムを除去し、塩素根がＣｌ／Ｙｂ２Ｏ３（モル比）として０．６含むＹｂ２Ｏ３濃度５％のイッテルビウムゲル溶液を得た。
次いで、これをオートクレーブに入れ、１１０℃で３時間水熱処理を行ない、Ｙｂ２Ｏ３濃度５％のイッテルビウムゾルを得た。次にこのゾルにＹｂ２Ｏ３１モルに対して０．５モルの１０％クエン酸溶液を添加し、更に３％アンモニア水を用いてゾルｐＨ９．５にした後、限外濾過装置を用いて濾液の電気伝導度が５Ｓ/ｍ以下になるまで濾過・濃縮を行い、Ｙｂ２Ｏ３として１０％のイッテルビウムゾルを得た。
得られた１０％のイッテルビウムゾルは、メジアン径１３９ｎｍ、Ｃｌ／Ｙｂ２Ｏ３（モル比）＝０．０３、クエン酸／Ｙｂ２Ｏ３（モル比）＝０．４、ヘイズ率３５．２％、電気伝導度１．５Ｓ／ｍ、ｐＨ７．０であった。
また、１ヶ月間でのゾルの保存安定性は、増粘や沈殿物の発生もなく良好であった。
To 1823 g of a 1% aqueous ammonia solution, 10000 g of a 0.5% solution in which 50 g of ytterbium oxide (3N, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in hydrochloric acid was added with stirring to produce an ytterbium gel. This was used to remove ammonium chloride in the gel using an ultrafiltration device to obtain an ytterbium gel solution having a chlorine root of 0.6 as Cl / Yb 2 O 3 (molar ratio) and having a Yb 2 O 3 concentration of 5%. .
This was then placed in an autoclave and hydrothermally treated at 110 ° C. for 3 hours to obtain a ytterbium sol having a Yb 2 O 3 concentration of 5%. Next, after adding 0.5 mol of 10% citric acid solution to 1 mol of Yb 2 O 3 to this sol, and further adjusting the sol pH to 9.5 using 3% ammonia water, an ultrafiltration device was used. Then, filtration and concentration were performed until the electric conductivity of the filtrate became 5 S / m or less, and 10% ytterbium sol was obtained as Yb 2 O 3 .
The obtained 10% ytterbium sol had a median diameter of 139 nm, Cl / Yb 2 O 3 (molar ratio) = 0.03, citric acid / Yb 2 O 3 (molar ratio) = 0.4, and a haze ratio of 35.2. %, Electric conductivity 1.5 S / m, pH 7.0.
Also, the storage stability of the sol within one month was good without thickening and generation of precipitates.
１％アンモニア水溶液２０８２gに酸化ルテチウム（３Ｎ、信越化学(株)製）５０ｇを塩酸に溶解させた０．５％溶液１００００ｇを撹拌下で添加し、ルテチウムゲルを生成させた。これを限外濾過装置を用いてゲル中の塩化アンモニウムを除去し、塩素根がＣｌ／Ｌｕ２Ｏ３（モル比）として１．１含有するＬｕ２Ｏ３濃度２％のルテチウムゲル溶液を得た。
次いで、これをオートクレーブに入れ、１１０℃で３時間水熱処理を行ない、Ｌｕ２Ｏ３濃度２％のルテチウムゾルを得た。次にこのゾルにＬｕ２Ｏ３１モルに対して０．５モルの１０％リンゴ酸溶液を添加し、更に３％アンモニア水を用いてゾルｐＨ１０に調整した後、限外濾過装置を用いて濾液の電気伝導度が５Ｓ/ｍ以下になるまで濾過・濃縮を行い、Ｌｕ２Ｏ３として１０％のルテチウムゾルを得た。
得られた１０％のルテチウムゾルは、メジアン径１１１ｎｍ、Ｃｌ／Ｌｕ２Ｏ３（モル比）＝０．０７、リンゴ酸／Ｌｕ２Ｏ３（モル比）＝０．４、ヘイズ率５４．０％、電気伝導度１．６Ｓ／ｍ、ｐＨ６．５であった。
また、１ヶ月間でのゾルの保存安定性は、増粘や沈殿物の発生もなく良好であった。
To 2082 g of 1% aqueous ammonia solution, 10000 g of a 0.5% solution in which 50 g of lutetium oxide (3N, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in hydrochloric acid was added with stirring to produce a lutetium gel. This was used to remove ammonium chloride in the gel using an ultrafiltration device to obtain a lutetium gel solution containing 2% of Lu 2 O 3 concentration containing 1.1 as Cl / Lu 2 O 3 (molar ratio) of chlorine radicals. It was.
Next, this was put in an autoclave and hydrothermally treated at 110 ° C. for 3 hours to obtain a lutetium sol having a Lu 2 O 3 concentration of 2%. Next, 0.5 mol of 10% malic acid solution is added to this sol with respect to 1 mol of Lu 2 O 3, and the sol pH is adjusted to 10 using 3% ammonia water, and then using an ultrafiltration device. Filtration and concentration were performed until the electrical conductivity of the filtrate was 5 S / m or less, and 10% lutetium sol was obtained as Lu 2 O 3 .
The obtained 10% lutetium sol had a median diameter of 111 nm, Cl / Lu 2 O 3 (molar ratio) = 0.07, malic acid / Lu 2 O 3 (molar ratio) = 0.4, and a haze ratio of 54.0. %, Electric conductivity 1.6 S / m, pH 6.5.
Also, the storage stability of the sol within one month was good without thickening and generation of precipitates.
１％アンモニア水溶液１８７８gに酸化エルビウム（３Ｎ、信越化学(株)製）５０ｇを塩酸に溶解させた０．５％溶液１００００ｇを撹拌下で添加し、エルビウムゲルを生成させた。これを限外濾過装置を用いて塩化アンモニウムを除去し、塩素根がＣｌ／Ｅｒ２Ｏ３（モル比）として０．６含有するＥｒ２Ｏ３濃度２％のエルビウムゲル溶液を得た。
次いで、これをオートクレーブに入れ、９０℃で８時間水熱処理を行ない、Ｅｒ２Ｏ３濃度２％のエルビウムゾルを得た。次にこのゾルにＥｒ２Ｏ３１モルに対して０．５モルの１０％酒石酸水溶液を添加し、更に３％アンモニア水を用いてゾルｐＨ１０にした後、限外濾過装置を用いて濾液の電気伝導度が５Ｓ/ｍ以下になるまで濾過・濃縮を行い、Ｅｒ２Ｏ３として１０％のエルビウムゾルを得た。
得られた１０％のエルビウムゾルは、メジアン径１３５ｎｍ、Ｃｌ／Ｅｒ２Ｏ３（モル比）＝０．０７、酒石酸／Ｅｒ２Ｏ３（モル比）＝０．４、ヘイズ率２６．６％、電気伝導度３．５Ｓ／ｍ、ｐＨ７．９であった。
また１ヶ月間でのゾルの保存安定性は、増粘や沈殿物の発生もなく良好であった。
An erbium gel was produced by adding 10000 g of a 0.5% solution prepared by dissolving 50 g of erbium oxide (3N, manufactured by Shin-Etsu Chemical Co., Ltd.) in hydrochloric acid to 1878 g of a 1% aqueous ammonia solution. From this, ammonium chloride was removed using an ultrafiltration device to obtain an Er 2 O 3 concentration 2% erbium gel solution containing 0.6 as Cl / Er 2 O 3 (molar ratio) of chlorine roots.
Next, this was put in an autoclave and hydrothermally treated at 90 ° C. for 8 hours to obtain an erbium sol having an Er 2 O 3 concentration of 2%. Next, 0.5 mol of 10% tartaric acid aqueous solution was added to 1 mol of Er 2 O 3 to this sol, and the sol pH was adjusted to 10 using 3% aqueous ammonia, and the filtrate was filtered using an ultrafiltration device. Filtration and concentration were performed until the electric conductivity became 5 S / m or less, and 10% erbium sol was obtained as Er 2 O 3 .
The obtained 10% erbium sol had a median diameter of 135 nm, Cl / Er 2 O 3 (molar ratio) = 0.07, tartaric acid / Er 2 O 3 (molar ratio) = 0.4, and a haze ratio of 26.6%. The electrical conductivity was 3.5 S / m and the pH was 7.9.
Also, the storage stability of the sol within one month was good without thickening and generation of precipitates.
実施例２と同様にして、希土類元素種 Ｙ、Ｃｅ、Ｐｒ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ及びＨｏについて各々Ｙ２Ｏ３（４Ｎ、阿南化成(株)製）、Ｃｅ２（ＣＯ３）３（３Ｎ、新日本金属工業(株)製）、Ｐｒ６Ｏ１１（３Ｎ、日本イットリウム(株)製）、Ｓｍ２Ｏ３（３Ｎ、信越化学工業(株)製）、Ｅｕ２Ｏ３（３Ｎ、信越化学工業(株)製）、Ｇｄ２Ｏ３（３Ｎ、日本イットリウム(株)製）、Ｄｙ２Ｏ３（３Ｎ、日本イットリウム(株)製）及びＨｏ２Ｏ３（３Ｎ、日本イットリウム(株)製）を用いてゾルを製造した。
これらのゾルについて各種物性を測定した。その結果を表１に示した。
In the same manner as in Example 2, for rare earth element species Y, Ce, Pr, Sm, Eu, Gd, Dy, and Ho, Y 2 O 3 (4N, manufactured by Anan Kasei Co., Ltd.), Ce 2 (CO 3 ) 3 (3N, manufactured by Shin Nippon Metal Industry Co., Ltd.), Pr 6 O 11 (3N, manufactured by Nippon Yttrium Co., Ltd.), Sm 2 O 3 (3N, manufactured by Shin-Etsu Chemical Co., Ltd.), Eu 2 O 3 (3N , Shin-Etsu Chemical Co., Ltd.), Gd 2 O 3 (3N, manufactured by Nippon Yttrium Co., Ltd.), Dy 2 O 3 (3N, manufactured by Nippon Yttrium Co., Ltd.) and Ho 2 O 3 (3N, Japanese Yttrium ( A sol was produced using a
Various physical properties of these sols were measured. The results are shown in Table 1.
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| JP2008513053A (en) * | 2004-09-14 | 2008-05-01 | オプトクリツト・アー・ベー | Superparamagnetic gadolinium oxide nanoscale particles and compositions comprising such particles |
| JP4646055B2 (en) * | 2004-10-20 | 2011-03-09 | 多木化学株式会社 | Tantalum oxide sol and method for producing the same |
| JP4731220B2 (en) * | 2005-06-01 | 2011-07-20 | 第一稀元素化学工業株式会社 | Method for producing ceria sol |
| JP4836532B2 (en) * | 2005-08-26 | 2011-12-14 | 第一稀元素化学工業株式会社 | Method for producing neodymium oxide sol |
| JP5674083B2 (en) * | 2009-09-02 | 2015-02-25 | 多木化学株式会社 | Iron oxyhydroxide sol and method for producing the same |
| JP5562162B2 (en) * | 2009-10-29 | 2014-07-30 | 三井金属鉱業株式会社 | Aqueous dispersion containing oxide of lanthanoid element |
| JP5570011B2 (en) * | 2010-05-31 | 2014-08-13 | 国立大学法人岐阜大学 | Method for producing yttrium oxide precursor aqueous sol and yttrium oxide precursor aqueous sol |
| JP6696711B2 (en) * | 2015-12-28 | 2020-05-20 | 多木化学株式会社 | Nickel sol |
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| JPH03232721A (en) * | 1989-12-15 | 1991-10-16 | Rhone Poulenc Chim | Preparation of colloidal dispersing element of cerium iv compound in aqueous medium and dispersing element thus obtained |
| JPH0431307A (en) * | 1990-05-28 | 1992-02-03 | Teika Corp | Production of fine-grain metal oxide |
| JPH07284651A (en) * | 1994-02-18 | 1995-10-31 | Rhone Poulenc Chim | Organosol of quadrivalent metal oxide and use thereof as additive for hydrocarbon compound |
| JP2003034526A (en) * | 2001-07-18 | 2003-02-07 | Kinya Adachi | Method for manufacturing nanoparticles of rare earth metal oxide |
| JP2003529516A (en) * | 1999-11-23 | 2003-10-07 | ロディア テレ ラレ | Aqueous colloidal dispersion based on at least a lanthanide compound and a complex forming compound, a method for producing the same and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03232721A (en) * | 1989-12-15 | 1991-10-16 | Rhone Poulenc Chim | Preparation of colloidal dispersing element of cerium iv compound in aqueous medium and dispersing element thus obtained |
| JPH0431307A (en) * | 1990-05-28 | 1992-02-03 | Teika Corp | Production of fine-grain metal oxide |
| JPH07284651A (en) * | 1994-02-18 | 1995-10-31 | Rhone Poulenc Chim | Organosol of quadrivalent metal oxide and use thereof as additive for hydrocarbon compound |
| JP2003529516A (en) * | 1999-11-23 | 2003-10-07 | ロディア テレ ラレ | Aqueous colloidal dispersion based on at least a lanthanide compound and a complex forming compound, a method for producing the same and use thereof |
| JP2003034526A (en) * | 2001-07-18 | 2003-02-07 | Kinya Adachi | Method for manufacturing nanoparticles of rare earth metal oxide |
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