JPH09132406A - Fine particles of phosphate of rare earth element and their production - Google Patents

Fine particles of phosphate of rare earth element and their production

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Publication number
JPH09132406A
JPH09132406A JP7288296A JP28829695A JPH09132406A JP H09132406 A JPH09132406 A JP H09132406A JP 7288296 A JP7288296 A JP 7288296A JP 28829695 A JP28829695 A JP 28829695A JP H09132406 A JPH09132406 A JP H09132406A
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rare earth
particles
washed
treated
aq
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Inventor
Hisashi Tamai
Hajime Yasuda
源 安田
久司 玉井
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Mitsubishi Heavy Ind Ltd
三菱重工業株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide fine particles of phosphate of a rare earth element having a large specific surface area and suitable for use as a catalyst, ceramic stock, etc. by suspending fine org. polymer particles carrying Pd in an aq. soln. contg. a salt of the rare earth element and a phosphite and carrying out treatment at a specified temp. and firing. SOLUTION: Styrene-acrylic acid copolymer of about 0.5μm diameter in an amount of 10g is, for example, treated with 200ml 0.1N aq. NaOH soln., washed, treated with 0.2N aq. SnCl2 soln. for 1hr, separated by filtration and washed to obtain particles. These particles are treated with 200ml aq. PdCl2 soln. having 0.01mol/l concn. for 3hr and they are well washed to obtain fine org. polymer particles carrying Pd. A slurry ocntg. 7.5g/l of the polymer particles, 0.125mol/l NaN2 PO2 and 0.125mol/l Pr(NO3 )3 is prepd. and held at 90 deg.C for 3hr under stirring. The resultant particles are separated by filtration, washed and fired at 900 deg.C in air to obtain the objective hollow fine particles of PrPO4 uniform in particle size.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】本発明は、比表面積の大きな微粒子状の希土類リン酸塩及びその製造方法に関し、例えば触媒及びセラミックス原料等に用いて好適なものを提供する。 The present invention relates to relates to a large particulate rare earth phosphate and its manufacturing method of the specific surface area, to provide a suitably used for, for example, the catalyst and ceramics raw materials.

【0002】 [0002]

【従来の技術及び発明が解決しようとする課題】希土類のリン酸塩は耐熱性のある安定な化合物であるが、従来のものはその比表面積が窒素(N 2 )のBET吸着法による値が高々5m 2 /g程度であり、例えば触媒としての適用を考えると、少なくとも上記値として20m 2 Phosphates of the rare earth BACKGROUND OF INVENTION Problems to be Solved] is a stable compound having heat resistance, but conventional ones values according to BET adsorption method of a specific surface area of nitrogen (N 2) at most 5 m 2 / g approximately, for example, considering the application as a catalyst, as at least the value 20 m 2 /
g程度以上のものが要求されているので、性能の面から十分な物性を備えているものではない。 Since more than about g is required, it does not have sufficient properties in terms of performance.

【0003】本発明は、従来合成することが困難であった高比表面積を有する微粒子状希土類リン酸塩及びその製造方法を提供することを目的とする。 [0003] The present invention aims to provide a particulate rare earth phosphate and its manufacturing method having a high specific surface area is difficult to conventionally synthesized.

【0004】 [0004]

【課題を解決するための手段】前記目的を達成する本発明の希土類リン酸塩微粒子の構成は、Pdを担持した有機高分子微粒子を、希土類塩及び次亜リン酸塩水溶液に懸濁させて30〜90℃で処理し、焼成してなることを特徴とする。 Means for Solving the Problems The configuration of the rare earth phosphate particles of the present invention to achieve the object, the organic polymer microparticles carrying Pd, was suspended in a rare earth salt and hypophosphite aqueous solution It was treated with 30 to 90 ° C., and characterized by being fired.

【0005】上記希土類リン酸塩微粒子において、有機金属微粒子が直径0.1μm〜1.0μmで金属イオンに交換可能または金属錯体形成能を有することを特徴とする。 [0005] In the rare earth phosphate particles, organic fine metal particles and having a replaceable or a metal complex forming ability with a metal ion in diameter 0.1Myuemu~1.0Myuemu.

【0006】また、一方の微粒子状希土類リン酸塩の製造方法は、Pdを担持した有機高分子微粒子を、希土類塩及び次亜リン酸塩水溶液に懸濁させ、30〜90℃で処理し、その後空気中で焼成して希土類リン酸塩微粒子を得ることを特徴とする。 [0006] In the method of manufacturing one particulate rare earth phosphate salt, an organic polymer microparticles carrying Pd, suspended in a rare earth salt and hypophosphite aqueous solution is treated with 30 to 90 ° C., thereafter calcined in air, characterized in that to obtain a rare earth phosphate particles.

【0007】以下、本発明の内容を説明する。 [0007] In the following, describing the contents of the present invention.

【0008】本発明の希土類リン酸塩微粒子は、Pdを担持した有機高分子微粒子を、希土類塩及び次亜リン酸塩水溶液に懸濁させて30〜90℃で処理し、焼成してなるものである。 [0008] rare earth phosphate particles of the present invention, the organic polymer microparticles carrying Pd, which was suspended in a rare earth salt and hypophosphite aqueous solution was treated with 30 to 90 ° C., made by firing it is.

【0009】この希土類リン酸塩微粒子の製造は以下の工程により合成することができる。 The preparation of the rare earth phosphate particles can be synthesized by the following steps. (第1工程)金属イオン交換能あるいは金属錯体形成能を有する有機高分子微粒子にパラジウム(Pd)を担持させる。 (First step) is supported on organic polymer microparticles palladium (Pd) with a metal ion exchange capacity or a metal complex-forming ability. (第2工程)Pdを担持した有機高分子微粒子を希土類と次亜リン酸塩水溶液に懸濁させ、30〜90℃に保持する。 The organic polymer particles carrying the (second step) Pd suspended in rare earth and hypophosphite aqueous solution, kept at 30 to 90 ° C.. (第3工程)上記第2工程の懸濁液を濾過し、水洗した後、空気中で焼成する。 A suspension of (third step) the second step is filtered, washed with water and calcined in air.

【0010】ここで、本発明で上記第1工程の有機高分子微粒子としては、少なくとも1つの官能基を有するα,β−不飽和単量体(以下、「単量体A」という)の単独重合体、共重合体および単量体Aと1つの官能基も有しないα,β−不飽和単量体(以下、「単量体B」という)との共重合体微粒子である。 [0010] As the organic polymer fine particles of the first step in the present invention, alpha having at least one functional group, beta-unsaturated monomer (hereinafter, referred to as "monomer A") alone polymers, copolymers and monomer a and one functional group having no alpha, beta-unsaturated monomer (hereinafter, referred to as "monomer B") is a copolymer particles with. 上記単量体Aとしては、例えば、アクリル酸,メタクリル酸,スチレンスルホン酸,ビニルスルホン酸,2−アクリルアミド−2− As the monomer A, for example, acrylic acid, methacrylic acid, styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2
メチルプロパンスルホン酸,マレイン酸,フマル酸,イタコン酸およびそれらの塩;アクリルニトリル,メタクリルニトリル,アクリルアミド,メタアクリルアミド, Methylpropane sulfonic acid, maleic acid, fumaric acid, itaconic acid and salts thereof; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide,
アクリロイルモルホリン,ジメチルアミノエチルメタクリート,ジメチルアミノエチルアクリレート,アミノエチルメタクリレート,ビニルピロリドン,ビニルピリジン,ビニルイミダゾールなどが挙げられるが、本発明はこれらに限定されるものではない。 Acryloyl morpholine, dimethylaminoethyl methacrylate cleat, dimethylaminoethyl acrylate, aminoethyl methacrylate, vinyl pyrrolidone, vinyl pyridine, and vinyl imidazole, the present invention is not limited thereto. 上記単量体Bとしては、例えば、スチレン,酢酸ビニル,プロピオン酸ビニル,アクリル酸メチル,アクリル酸エチル,アクリル酸ブチル,アクリル酸オクチル,アクリル酸ドデシルなどのアクリル酸エステル類;メタクリル酸メチル,メタクリル酸エチル,メタクリル酸ブチル,ルメタクリル酸オクチル,メタクリル酸ドデシルなどのメタクリル酸エステルなどがが挙げられるが、本発明はこれらに限定されるものではない。 As the monomer B, for example, styrene, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, acrylic esters, such as dodecyl acrylate; methyl methacrylate, ethyl, butyl methacrylate, Le octyl methacrylate, but methacrylic acid esters such as dodecyl methacrylate and the like, but the present invention is not limited thereto.

【0011】また、用いる有機高分子微粒子の大きさは、直径0.1〜1.0μmの範囲のものが好ましい。 [0011] The size of the organic polymer fine particles to be used is preferably in the range of diameter 0.1 to 1.0 [mu] m.

【0012】有機高分子微粒子にパラジウム(Pd)を担持させる方法としては、先ずSnCl 2水溶液で処理した後、PdCl 2水溶液で処理する方法、或いは先にPdCl 2水溶液で処理後、NaBH 4等の還元剤で処理する方法を適用することができるが、本発明はこれに限定されるものではない。 [0012] The palladium (Pd) in an organic polymer fine particles as the method for supporting the first was treated with SnCl 2 solution, a method of treatment with PdCl 2 solution, or earlier after treatment with PdCl 2 solution, such as NaBH 4 Although it is possible to apply a method of treatment with a reducing agent, the present invention is not limited thereto.

【0013】上記第2の工程で使用する希土類塩としては、硝酸塩又は塩化物のいづれを用いてもよい。 [0013] As the rare earth salt used in the second step, it may be used Izure of nitrates or chlorides.

【0014】本発明の希土類リン酸塩の製造においては、Pdを担持した有機高分子微粒子のPdの触媒作用によって、次亜リン酸イオンをリン酸イオンに酸化し、 [0014] In the production of the rare earth phosphate of the present invention, by the catalytic action of Pd in ​​the organic polymer fine particles carrying Pd, oxidizing the hypophosphite ion to phosphate ion,
作成したリン酸イオンを希土類金属イオンが反応し薄膜状態に有機高分子微粒子上に析出する。 Phosphate ions of rare earth metal ions created is deposited on the organic polymer fine particles in the reaction a thin film state. このことがその後の焼成工程を経た後、高比表面積の希土類リン酸塩の生成に寄与するものと思われる。 Thereafter it is passed through the subsequent baking step, it is believed to contribute to the generation of a rare earth phosphate having a high specific surface area.

【0015】 [0015]

【発明の実施の形態】以下本発明を実施する実施の形態を説明するが、本発明はこれに限定されるものではない。 Describing PREFERRED EMBODIMENTS Embodiment of carrying out the invention below, but the present invention is not limited thereto.

【0016】本実施の形態では、Pd超微粒子を表面に担持した高分子微粒子を調整し、Pdの触媒作用を利用して希土類リン酸塩を焼成することにより、希土類リン酸塩の中空微粒子を得ることができる。 [0016] In this embodiment, by adjusting the polymer microparticles carrying Pd ultra-fine particles on the surface, by firing a rare earth phosphate by utilizing the catalytic action of Pd, the hollow fine particles of the rare earth phosphate it is possible to obtain. 例えば希土類硝酸塩としてPr(NO 33を用いて得られた高分子微粒子をTEM像を観察すると、高分子微粒子表面での結晶の成長による均一なコア−シェルタイプの複合化が認められた。 For example, the polymer fine particles obtained by using Pr (NO 3) 3 as the rare earth nitrate to observe a TEM image, uniform core due to the growth of crystals in the polymer particles surface - composite shell type was observed. X線分析の結果、ラプドフェノンタイプの希土類リン酸塩の微結晶の生成が確認された。 Results of X-ray analysis, the product Lapu de acetophenone type microcrystalline rare earth phosphates was confirmed.

【0017】得られた複合微粒子を900℃で焼成したところ、monaziteタイプの微結晶からなる粒子サイズの均一なPrPO 4中空微粒子を生成した。 [0017] When the obtained composite particles were calcined at 900 ° C., to produce a uniform PrPO 4 hollow fine particle size comprising a microcrystalline monazite type.

【0018】 [0018]

【実施例】以下、本発明の効果を示す実施例について詳細に説明する。 EXAMPLES Hereinafter, described in detail for Example showing the effect of the present invention.

【0019】(実施例1)直径が0.5μmのスチレン/アクリル酸共重合体10gを0.1Nの水酸化ナトリウム水溶液200mlで処置した後、水洗し、0.2N [0019] After treatment with (Example 1) having a diameter of 0.5μm styrene / acrylic acid copolymer 10g of 0.1N aqueous sodium hydroxide 200 ml, washed with water, 0.2 N
SnCl 2水溶液で1時間処理した後、濾過し水洗した。 After 1 hour at SnCl 2 solution, it was filtered and washed with water. 得られた粒子を0.01mol/lのPdCl 2水溶液200mlで3時間処理した後、よく水洗をした。 The obtained particles were treated for 3 hours with PdCl 2 solution 200ml of 0.01 mol / l, were well washed with water.
この得られたPdを担持した有機高分子粒子を7.5g The organic polymer particles carrying the resulting Pd 7.5 g
/l、及びNaH 2 PO 2 0.125mol/l、Pr / L, and NaH 2 PO 2 0.125mol / l, Pr
(NO 33 0.125mol/lの濃度のスラリー水溶液とし、攪拌しながら90℃で3時間保持した。 (NO 3) 3 was slurried aqueous solution having a concentration of 0.125 mol / l, and held for 3 hours with stirring 90 ° C.. その後、濾過し水洗し、 空気中900℃で焼成し、粒子サイズの均一なPrPO 4の中空微粒子を得た。 Then, filtered and washed with water, then calcined at 900 ° C. in air, to obtain a hollow fine particles of uniform PrPO 4 of particle size. この得られた生成物をS−1とする。 The resultant product was named as S-1.

【0020】(実施例2〜14)上記実施例1において、Pr(NO 33の代わりに、他の希土類の硝酸塩として、Ce(NO 33 ,Nd(NO 33 ,Sm [0020] (Example 2 to 14) above in Example 1, in place of Pr (NO 3) 3, as nitrate of another rare earth, Ce (NO 3) 3, Nd (NO 3) 3, Sm
(NO 33 ,La(NO 33 ,Eu(NO 33 (NO 3) 3, La ( NO 3) 3, Eu (NO 3) 3,
Gd(NO 33 ,Tb(NO 33 ,Dy(NO 3 Gd (NO 3) 3, Tb (NO 3) 3, Dy (NO 3)
3 ,Ho(NO 33 ,Er(NO 33 ,Tm(NO 3, Ho (NO 3) 3 , Er (NO 3) 3, Tm (NO
33 ,Yb(NO 33及びLu(NO 33を各々用い、実施例1と同様に操作して生成物を得た。 3) 3, Yb (NO 3 ) 3 and Lu (NO 3) 3 with respectively, to give the product in the same manner as in Example 1. この得られた生成物を各々S−2〜S−14とする。 The resulting product, respectively a S-2~S-14.

【0021】(実施例16〜28)上記実施例1において、Pr(NO 33の代わりに、他の希土類の塩化物として、PrCl 3 ,CeCl 3 ,NdCl 3 ,SmC [0021] (Example 16 to 28) above in Example 1, in place of Pr (NO 3) 3, as chlorides other rare earth, PrCl 3, CeCl 3, NdCl 3, SmC
3 ,LaCl 3 ,EuCl 3 ,GdCl 3 ,TbCl l 3, LaCl 3, EuCl 3 , GdCl 3, TbCl
3 ,DyCl 3 ,HoCl 3 ,ErCl 3 ,TmC 3, DyCl 3, HoCl 3, ErCl 3, TmC
3 ,YbCl 3及びLuCl 3を各々用い、実施例1 Each reference to l 3, YbCl 3 and LuCl 3, Example 1
と同様に操作して生成物を得た。 To give the product using the same method as. この得られた生成物を各々C−1〜C−14とする。 The resulting product, respectively a C-1~C-14.

【0022】(比較例1)0.25mol/lPr(N [0022] (Comparative Example 1) 0.25mol / lPr (N
33水溶液と0.125mol/lのNa 3 PO 4 O 3) 3 aqueous solution and 0.125mol / l Na 3 PO 4
水溶液を等量混合し、生成する沈澱を濾過水洗し、その後空気中で900℃で焼成してPrPO 4の粉末を得た。 The aqueous solution was mixed in equal amounts and the resulting precipitate was filtered washed with water to obtain a powder of PrPO 4 was calcined at 900 ° C. Thereafter the air. この得られた生成物をR−1とする。 The resulting product with R-1.

【0023】(比較例2〜14)上記比較例1において、Pr(NO 33の代わりに、Ce(NO 33 [0023] (Comparative Example 2 to 14) Comparative Example 1, in place of Pr (NO 3) 3, Ce (NO 3) 3,
Nd(NO 33 ,Sm(NO 33 ,La(NO 3 Nd (NO 3) 3, Sm (NO 3) 3, La (NO 3)
3 ,Eu(NO 33 ,Gd(NO 33 ,Tb(NO 3, Eu (NO 3) 3 , Gd (NO 3) 3, Tb (NO
33 ,Dy(NO 33 ,Ho(NO 33 ,Er 3) 3, Dy (NO 3 ) 3, Ho (NO 3) 3, Er
(NO 33 ,Tm(NO 33 ,Yb(NO 33及びLu(NO 33を各々用い、実施例1と同様に操作して生成物を得た。 (NO 3) 3, Tm ( NO 3) 3, Yb (NO 3) 3 and Lu (NO 3) 3 with respectively, to give the product in the same manner as in Example 1. この得られた生成物を各々R−2〜 Each R-. 2 to the resulting product
R−14とする。 And R-14.

【0024】上記実施例1〜28の生成物S−1〜S− [0024] The product of Example 1~28 S-1~S-
14及びC−1〜C−14,並びに比較例1〜14の生成物R−1〜R−14について、窒素(N 2 )の吸着によるBET比表面積を測定した。 14 and C-1 through C-14, as well as the product R-1 to R-14 in Comparative Examples 1-14, the BET specific surface area was measured by adsorption of nitrogen (N 2). この結果を、下記「表1」及び「表2」に示す。 The results are shown in the following "Table 1" and "Table 2".

【0025】 [0025]

【表1】 [Table 1]

【0026】 [0026]

【表2】 [Table 2]

【0027】上記「表1」及び「表2」の結果より明らかなように、本実施例の生成物S−1〜15及びC−1 [0027] The "Table 1" and as is clear from "Table 2" in the result, the product of this example S-1 to 15 and C-1
〜15は、比較例1〜15の生成物R−1〜15に較べて、はるかに大きな比表面積を有しており、従来にはない物性を備えたものであった。 15 is compared to the product R-15 in Comparative Examples 1 to 15 has a much larger specific surface area, was equipped with conventionally no physical properties.

【0028】以上の結果より、本実施例により得られた微粒子の比表面積は、いずれも25m 2 /g以上のものとなっており、触媒及び吸着材として用いる最低必要とされる比表面積である20m 2 /gの条件をすべて上回っている。 [0028] From the above results, the specific surface area of fine particles obtained by the present embodiment are both has a 25 m 2 / g or more of, is minimum The required specific surface area is used as catalyst and adsorbents It is greater than all of the conditions of 20m 2 / g. これに対して従来例による微粒子は5m 2 Microparticles by conventional contrast 5 m 2 /
g以下であり、触媒及び吸着材として用いることができない。 g or less, can not be used as catalysts and adsorbents.

【0029】 [0029]

【発明の効果】以上、実施の形態及び実施例と共に述べたように、本発明によれば、比表面積の大きな微粒子状の希土類リン酸塩を得ることができ、例えば触媒及びセラミックス原料等に用いて好適なものとなる。 Effect of the Invention] Thus, as described in conjunction with the embodiments and examples, according to the present invention, it is possible to obtain a large particulate rare earth phosphate of the specific surface area, using for example catalysts and ceramics raw materials becomes suitable Te.

【0030】また、希土類塩としての塩化物を用いた場合には、硝酸塩に較べて原料コストが安価であり、触媒及び吸着材の製造コストの更なる低減を図ることができる。 Further, in the case of using the chlorides as the rare earth salt, raw material cost compared to nitrate it is inexpensive, it is possible to further reduce the manufacturing cost of the catalyst and adsorbent.

Claims (3)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 Pdを担持した有機高分子微粒子を、希土類塩及び次亜リン酸塩水溶液に懸濁させて30〜90 The method according to claim 1 the organic polymer fine particles carrying Pd, was suspended in a rare earth salt and hypophosphite aqueous 30-90
    ℃で処理し、焼成してなることを特徴とする希土類リン酸塩微粒子。 It was treated with ° C., rare earth phosphate particles which characterized by being fired.
  2. 【請求項2】 請求項1記載の希土類リン酸塩微粒子において、 有機高分子粒子が直径0.1μm〜1.0μmで金属イオンに交換可能または金属錯体形成能を有することを特徴とする希土類リン酸塩微粒子。 2. A rare earth phosphate particles of claim 1, wherein the rare earth organic polymer particles and having a replaceable or a metal complex forming ability with a metal ion in diameter 0.1μm~1.0μm phosphorus salt particles.
  3. 【請求項3】 Pdを担持した有機高分子微粒子を、希土類塩及び次亜リン酸塩水溶液に懸濁させ、30〜90 The wherein organic polymer fine particles carrying Pd, suspended in a rare earth salt and hypophosphite aqueous solution, 30 to 90
    ℃で処理し、その後空気中で焼成して希土類リン酸塩微粒子を得ることを特徴とする希土類リン酸塩微粒子の製造方法。 It was treated with ° C., the production method of the subsequent rare earth phosphate particles by firing in air, characterized in that to obtain a rare earth phosphate particles.
JP7288296A 1995-11-07 1995-11-07 Fine particles of phosphate of rare earth element and their production Granted JPH09132406A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002535225A (en) * 1999-01-26 2002-10-22 バイタ・ライセンシング・インコーポレーテツド Inorganic molding matrix and its preparation and use
WO2014069127A1 (en) * 2012-10-31 2014-05-08 三井金属鉱業株式会社 Optical material, method for manufacturing same and aqueous dispersion
US9220595B2 (en) 2004-06-23 2015-12-29 Orthovita, Inc. Shapeable bone graft substitute and instruments for delivery thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002535225A (en) * 1999-01-26 2002-10-22 バイタ・ライセンシング・インコーポレーテツド Inorganic molding matrix and its preparation and use
US9220595B2 (en) 2004-06-23 2015-12-29 Orthovita, Inc. Shapeable bone graft substitute and instruments for delivery thereof
US9789225B2 (en) 2004-06-23 2017-10-17 Orthovita, Inc. Shapeable bone graft substitute and instruments for delivery thereof
WO2014069127A1 (en) * 2012-10-31 2014-05-08 三井金属鉱業株式会社 Optical material, method for manufacturing same and aqueous dispersion
JP2014089373A (en) * 2012-10-31 2014-05-15 Mitsui Mining & Smelting Co Ltd Optical material and production method of the same, and aqueous dispersion liquid

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