JP2002302668A - Method for producing cerium abrasive - Google Patents
Method for producing cerium abrasiveInfo
- Publication number
- JP2002302668A JP2002302668A JP2001401151A JP2001401151A JP2002302668A JP 2002302668 A JP2002302668 A JP 2002302668A JP 2001401151 A JP2001401151 A JP 2001401151A JP 2001401151 A JP2001401151 A JP 2001401151A JP 2002302668 A JP2002302668 A JP 2002302668A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- cerium
- abrasive
- lanthanum
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polishing Bodies And Polishing Tools (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は酸化セリウムを主成
分とするセリウム研摩材の新規な製造方法に関する。[0001] The present invention relates to a novel method for producing a cerium abrasive containing cerium oxide as a main component.
【０００２】[0002]
【従来の技術】セリウム研摩材はテレビブラウン管のパ
ネル（前面ガラス）、液晶表示素子用ガラス、各種光学
用ガラス及び板ガラス等の研摩に広く用いられている。
セリウム研摩材にはＣｅＯ2 （酸化セリウム）の含有率
によって高セリウム研摩材と、低セリウム研摩材とに分
けられ、酸化セリウムの含有率が高ければ研摩力も大き
くなるがコストも高くなる。低セリウム研摩材は酸化セ
リウムの含有率が５０％前後乃至それ以下で、残りはＬ
ａ2Ｏ3（酸化ランタン）、Ｎｄ2 Ｏ3 （酸化ネオジウ
ム）、Ｐｒ6 Ｏ11（酸化プラセオジム）等の軽希土類の
酸化物からなる混合希土酸化物研摩材である。本発明は
低セリウム研摩材の製造方法に適する。2. Description of the Related Art Cerium abrasives are widely used for polishing panels (front glass) of television cathode-ray tubes, glass for liquid crystal display elements, various optical glasses and sheet glass.
Cerium abrasives are classified into high cerium abrasives and low cerium abrasives depending on the content of CeO 2 (cerium oxide). The higher the content of cerium oxide, the greater the polishing power but the higher the cost. The low cerium abrasive has a cerium oxide content of around 50% or less, and the rest is L
a 2 O 3 (lanthanum oxide), Nd 2 O 3 (neodymium oxide) is Pr 6 O 11 made of an oxide of the light rare earths (praseodymium oxide) or the like mixed rare earth oxide abrasive. The present invention is suitable for a method for producing a low cerium abrasive.
【０００３】セリウム研摩材の原料としては、モナザイ
ト精鉱、バステナサイト精鉱及びバステナサイト精鉱か
ら得られたセリウムコンセントレ−ト等が用いられてい
る。モナザイト鉱は資源的に豊富に存在しているが、ト
リウムやウラニウム等の放射性元素を比較的多く含んで
いることから、ウランやトリウムの原料として用いられ
ることが多く、それを目的として高次な処理体系が確立
されている。従ってこれからセリウム研摩材の原料を得
るとコスト的に高くなる。従って、比較的安価な低セリ
ウム研摩材の原料としては主としてバステナサイト精鉱
が用いられている。As raw materials for cerium abrasives, monazite concentrate, bastenasite concentrate, cerium concentrate obtained from bastenasite concentrate, and the like are used. Monazite ore is abundant in resources, but because it contains a relatively large amount of radioactive elements such as thorium and uranium, it is often used as a raw material for uranium and thorium. A processing system has been established. Therefore, if the raw material of the cerium abrasive is obtained from this, the cost becomes high. Accordingly, bastenasite concentrate is mainly used as a raw material for relatively inexpensive low cerium abrasives.
【０００４】バステナサイトはフッ化炭酸希土（Ｒ（Ｃ
Ｏ3 ）Ｆ）で、原鉱石は鉱脈型鉱床として存在し、例え
ば１２％のバステナサイト鉱石を含有し、磁選や浮選に
よる選鉱により方解石、重晶石、ケイ石等を除いて精鉱
とされる。その代表的なマウンテンパス鉱山のバステナ
サイト精鉱の組成を酸化物換算重量で示すと、例えばＣ
ｅＯ2 ：３５％、Ｌａ2 Ｏ3 ：２４％、Ｎｄ2 Ｏ3 ：８
％、Ｐｒ6 Ｏ11：３％、他の希土類酸化物：０．７％、
全希土類酸化物：６８〜７３％、強熱減量：２０％であ
り、非希土類元素は同様に酸化物換算で１８％（Ｓｒ
Ｏ：１％、ＣａＯ：１．８％、ＢａＯ：２．７％、Ｆ：
６％、ＳｉＯ2 ：２．５％、Ｐ2 Ｏ5 ：１．２％、Ｆｅ
2 Ｏ3 ：０．６％、ＳＯ4 ：２．２％）含有されてい
る。放射性物質のトリウム、ウラニウムも含まれている
が、上限は法的基準値をＴｈＯ2 換算した値０．１３５
％以下に規制されている。Bastenasite is a rare earth fluoride (R (C
In O 3 ) F), the ore is present as a vein-type ore deposit, containing, for example, 12% of bastenasite ore, and concentrates except for calcite, barite, silica, etc. by ore separation by magnetic separation or flotation. It is said. When the composition of the bastenasite concentrate of a typical mountain path mine is expressed in terms of oxide equivalent weight, for example, C
eO 2 : 35%, La 2 O 3 : 24%, Nd 2 O 3 : 8
%, Pr 6 O 11 : 3%, other rare earth oxides: 0.7%,
Total rare earth oxide: 68-73%, loss on ignition: 20%, and non-rare earth elements are similarly 18% (Sr
O: 1%, CaO: 1.8%, BaO: 2.7%, F:
6%, SiO 2: 2.5% , P 2 O 5: 1.2%, Fe
2 O 3 : 0.6%, SO 4 : 2.2%). Thorium and uranium as radioactive materials are also included, but the upper limit is 0.135, which is the legal standard value converted to ThO 2.
% Or less.
【０００５】バステナサイト精鉱からのセリウム研摩材
の製造方法は、例えば精鉱のセリウムやフッ素含量につ
いて必要に応じて成分調整し、他の添加剤を加えたりし
た後、粉砕、粒度調整が行われ、予備乾燥される。次い
でロ−タリ−キルン又はシャトルキルン中で６００℃〜
１０００℃で焼成され、粉砕、分級、再度の粒度調整が
行われて製品であるセリウム研摩材とされている。A method for producing a cerium abrasive from bastenasite concentrate involves, for example, adjusting the cerium and fluorine contents of the concentrate as necessary, adding other additives, and then pulverizing and adjusting the particle size. Done and pre-dried. Then in a rotary kiln or shuttle kiln at 600 ° C.
It is fired at 1000 ° C., pulverized, classified, and subjected to particle size adjustment again to obtain a cerium abrasive as a product.
【０００６】[0006]
【発明が解決しようとする課題】我国では低セリウム研
摩材原料としては、品質が安定しており、大量に安定的
に供給されることから、主としてマウンテンパス鉱山か
ら産出精鉱されたバステナサイトが利用されてきている
が、しかし研摩材の組成は、この原鉱石の産出地と当該
鉱石の精鉱法及び製造プラント能力によって大半が決定
されるので、必ずしも希望通りの満足すべきセリウム研
摩材が得られるとは言えなかった。In Japan, as a low cerium abrasive raw material, since its quality is stable and it is supplied stably in a large amount, the bastenasite mainly produced from a mountain path mine is concentrated. However, since the composition of the abrasive is largely determined by the source of the ore and the concentrate method and production plant capacity of the ore, a satisfactory cerium abrasive is not necessarily desired. Could not be obtained.
【０００７】例えば、原料であるバステナサイトにはト
リウムやウラン等の放射性物質が含まれており、近年環
境問題が重要視されるに従い、法定基準値内とはいえセ
リウム研摩材中の放射性物質の含量を、可能な限り少な
くすることが望まれている。For example, the raw material bastenasite contains radioactive substances such as thorium and uranium. In recent years, as environmental issues have become more important, the radioactive substances contained in cerium abrasives have fallen within legal standards. Is desired to be as low as possible.
【０００８】また原料中のアルカリ金属及びアルカリ土
類金属元素の含有量が多いと、焼成時にシンタリングの
原因となり、酸化希土の均一な焼成がしにくい。焼きす
ぎると結晶化度が上がり被研摩物にキズを生じやすくな
り、焼きが甘いと研削力が低下してしまう。この為焼成
温度の制御に十分な注意が必要で、大量の製品を常に均
一に製造していくための品質管理が大変である。If the content of the alkali metal and alkaline earth metal elements in the raw material is large, it causes sintering during firing, and it is difficult to uniformly fire the rare earth oxide. Too much baking increases the degree of crystallinity and easily causes scratches on the material to be polished. For this reason, it is necessary to pay sufficient attention to the control of the firing temperature, and it is very difficult to control the quality in order to always produce a large number of products uniformly.
【０００９】さらに、原料中には塩基性の強いランタン
が炭酸ランタンとして含まれており、焼成により酸化ラ
ンタンとして研摩材に含まれることになる。塩基性の強
い酸化ランタンの存在は、研摩時に研摩パッドの目詰ま
りを生じ、研摩面の研摩材水性スラリ−循環によるリフ
レッシュに悪影響を与える。殊に低セリウム研摩材では
ランタン含量が比較的高いので問題となりやすい。この
問題はバステナサイト精鉱中に含まれるフッ素によりフ
ッ化ランタンになることにより緩和されるが、フッ素含
量はバステナサイト精鉱の組成に依存し、十分緩和され
るとは限らない。そこでフッ化希土類を別途添加するこ
とも行われているが、これによっても完全とは言えなか
った。Further, lanthanum carbonate having a strong basic property is contained in the raw material, and will be contained in the abrasive as lanthanum oxide by firing. The presence of strongly basic lanthanum oxide causes clogging of the polishing pad during polishing and adversely affects the refresh of the polished surface due to the aqueous slurry circulation. In particular, low cerium abrasives tend to be problematic due to the relatively high lanthanum content. This problem is mitigated by the conversion of lanthanum fluoride by fluorine contained in the bastenasite concentrate, but the fluorine content depends on the composition of the bastenasite concentrate and is not always reduced sufficiently. Therefore, a rare earth fluoride is separately added, but this is not complete.
【００１０】また低セリウム研摩材の場合は特にフッ素
含量は研削力に関係し、フッ素含量は研削力が高く耐久
性のあるセリウム研摩材にするのに重要な要素である。
即ちフッ化希土類が含まれていると、ガラス表面で機械
的な摩擦研摩の他に、一種の水和侵食層が形成され、ケ
イフッ化物を生成して研摩を促進すると言われている。
よって、セリウムの含有量が少ないセリウム研摩材では
フッ素含量の調整は重要である。In the case of a low cerium abrasive, particularly, the fluorine content is related to the grinding power, and the fluorine content is an important factor for obtaining a cerium abrasive having high grinding power and durability.
In other words, it is said that when a rare earth fluoride is contained, in addition to mechanical friction polishing on the glass surface, a kind of hydrated erosion layer is formed to generate silicon fluoride and promote polishing.
Therefore, in a cerium abrasive having a low cerium content, the adjustment of the fluorine content is important.
【００１１】従って、アルカリ金属、アルカリ土類金属
及び放射性物質の含量が低減され、ランタンの影響及び
研削力の点からフッ素含量を自由にコントロ−ルできる
セリウム研摩材の製造方法が望まれていた。Therefore, there has been a demand for a method for producing a cerium abrasive in which the contents of alkali metals, alkaline earth metals and radioactive materials are reduced and the fluorine content can be freely controlled in view of the influence of lanthanum and the grinding power. .
【００１２】[0012]
【課題を解決するための手段】本発明者等は鋭意研究し
た結果、上述した課題を解決したセリウム研摩材の製造
方法に到達した。すなわち本発明では、セリウム及びラ
ンタンを含む軽希土類、アルカリ金属、アルカリ土類金
属並びに放射性物質を含む希土精鉱を粉砕し、アルカリ
金属、アルカリ土類金属及び放射性物質等の希土類以外
の成分を化学的に極力分離除去して、これらの含量が低
減されたセリウムを主成分とする軽希土類原料とした
後、フッ酸により部分フッ素化し、その後、焼成するよ
うにした。Means for Solving the Problems As a result of intensive studies, the present inventors have arrived at a method for producing a cerium abrasive which has solved the above-mentioned problems. That is, in the present invention, light rare earths containing cerium and lanthanum, alkali metals, alkaline earth metals and rare earth concentrates containing radioactive materials are pulverized, and components other than rare earths such as alkali metals, alkaline earth metals and radioactive materials are pulverized. After chemically separating and removing as much as possible to obtain a light rare earth raw material containing cerium as a main component, the content of which is reduced, partially fluorinated with hydrofluoric acid, and then fired.
【００１３】セリウム及びランタンを含む軽希土類、ア
ルカリ金属、アルカリ土類金属並びに放射性物質を含む
希土精鉱としては、バステナサイト精鉱以外の希土精
鉱、例えば複雑鉱精鉱等を使用することができるが、バ
ステナサイト精鉱を用いてもよい。コスト的には中国白
雲鉱希土複雑鉱精鉱が好ましい。As rare earth concentrates containing cerium and lanthanum, alkali metals, alkaline earth metals and radioactive materials, rare earth concentrates other than bastenasite concentrates, such as complex ore concentrates, are used. Alternatively, bastenasite concentrate may be used. From the viewpoint of cost, a rare earth complex concentrate of Chinese white cloud ore is preferable.
【００１４】アルカリ金属、アルカリ土類金属及び放射
性物質の化学的な分離除去には、濃硫酸処理による希土
類の可溶化と熱水による抽出と不溶解成分の分離、複塩
形成による結晶化分離、中和、塩酸処理とＰＨ制御によ
る鉄分、放射性物質の除去、ネオジウム等の有効成分の
溶媒抽出分離及び塩化物のアルカリ処理による炭酸塩化
の一連の工程を含む従来公知の鉱物の化学的処理方法の
採用が好ましい。精鉱中のフッ素は初期の硫酸焙焼で全
て除去されてしまう。Chemical separation and removal of alkali metals, alkaline earth metals and radioactive substances include solubilization of rare earths by treatment with concentrated sulfuric acid, extraction with hot water and separation of insoluble components, crystallization separation by formation of double salts, Conventionally known methods of chemical treatment of minerals include a series of steps of neutralization, removal of iron and radioactive substances by hydrochloric acid treatment and PH control, solvent extraction separation of active ingredients such as neodymium, and carbonation by alkali treatment of chloride. Adoption is preferred. Fluorine in the concentrate is completely removed by the initial sulfuric acid roasting.
【００１５】アルカリ金属、アルカリ土類金属及び放射
性物質を化学的に分離除去して得られた軽希土類原料を
フッ酸によりフッ素化すると、反応させるフッ酸量によ
り軽希土類原料中の希土類は一様にフッ素化される。反
応させるフッ酸量としては、軽希土類原料中に含まれて
いるランタンがフッ化ランタンとなって中和される量を
最低とし、また焼成中にこのフッ化希土類が焼結を起こ
さない量を最高とする。なお最終製品であるセリウム研
摩材中のフッ素含量は３〜９重量％が好ましく、高研削
性を求める場合には５〜７重量％がよい。従って、これ
に応じてフッ酸量が選択される。When a light rare earth material obtained by chemically separating and removing an alkali metal, an alkaline earth metal and a radioactive substance is fluorinated with hydrofluoric acid, the rare earth in the light rare earth material is uniform depending on the amount of hydrofluoric acid to be reacted. Is fluorinated. The amount of hydrofluoric acid to be reacted should be such that the amount of lanthanum contained in the light rare earth material to be neutralized as lanthanum fluoride is minimized, and that the rare earth fluoride does not cause sintering during firing. To be the highest. The fluorine content in the cerium abrasive as the final product is preferably 3 to 9% by weight, and when high grinding property is required, 5 to 7% by weight is preferred. Therefore, the amount of hydrofluoric acid is selected accordingly.
【００１６】なお、本発明では、必ずしも希土精鉱を出
発物質とする必要はなく、アルカリ金属、アルカリ土類
金属及び放射性物質が化学的に分離除去されてその含量
が低減されたセリウムを主成分とされた軽希土類原料
を、出発物質としてもよい。In the present invention, it is not always necessary to use rare earth concentrate as a starting material, and cerium whose content is reduced by chemically separating and removing alkali metals, alkaline earth metals and radioactive materials is mainly used. The light rare earth material used as a component may be used as a starting material.
【００１７】また、アルカリ金属、アルカリ土類金属及
び放射性物質が分離除去されてそれらの含量が低減され
たセリウムを主成分とする軽希土類原料の組成として
は、好ましくは酸化物換算３５重量％以上の軽希土類を
含有し、セリウムが全希土類酸化物に対して５０重量％
以上であり、またアルカリ金属酸化物が０．５重量％以
下、アルカリ金属及びアルカリ土類金属酸化物の合計が
１．５重量％以下であり、酸化トリウム及び酸化ウラニ
ウムの合計が０．０５重量％以下であるのがよい。The composition of the light rare earth raw material containing cerium as a main component from which alkali metal, alkaline earth metal and radioactive material are separated and reduced to reduce their contents is preferably 35% by weight or more in terms of oxide. Cerium is 50% by weight based on the total rare earth oxide
0.5% by weight or less of alkali metal oxide, 1.5% by weight or less of alkali metal and alkaline earth metal oxide in total, and 0.05% by weight of thorium oxide and uranium oxide in total. %.
【００１８】なお、フッ酸による部分フッ素化の代わり
に、セリウムを主成分とするフッ化希土類を添加するよ
うにすることもできる。フッ化希土類の添加により、製
品中の酸化ランタン比率を低下させることができ、さら
に焼成時に酸化ランタンは酸化セリウム及びフッ素と反
応しＣｅＬａ2 Ｏ3 Ｆのようにマトリックスを形成して
研摩に好影響を与える。少なくとも研摩具に悪影響を与
えないようにするためには、製品中の酸化ランタン含有
量を極力低減することがよい。また最終製品中のフッ素
含量が３〜９重量％になるようにするのが好ましい。Instead of the partial fluorination with hydrofluoric acid, a rare earth fluoride containing cerium as a main component may be added. By adding rare earth fluoride, the ratio of lanthanum oxide in the product can be reduced, and during sintering, lanthanum oxide reacts with cerium oxide and fluorine to form a matrix like CeLa 2 O 3 F, which has a favorable effect on polishing. give. In order not to adversely affect the polishing tool at least, the content of lanthanum oxide in the product should be reduced as much as possible. It is preferable that the fluorine content in the final product is 3 to 9% by weight.
【００１９】[0019]
【発明の実施の形態】中国白雲鉱希土複雑鉱精鉱（酸化
希土換算含量３０％）を粉砕し、硫酸焙焼処理して希土
硫酸塩粉とする。その際、ＨＦ、ＣＯ2 、ＳＯ3 等は揮
散する。希土硫酸塩粉を水で抽出して、ＢａＳＯ4 、Ｃ
ａＳＯ4 、ＳｉＯ2 などの不溶性残渣を分離する。硫酸
希土溶液に食塩を加え、塩化ナトリウムの複塩として結
晶析出させ、その後水酸化ナトリウムで水酸化希土ケ−
キとする。これを塩酸と反応させ塩素化するがＰＨを調
整して酸性度を制御して、Ｔｈ、Ｆｅなどの難溶性の水
酸化物及び不溶性のシリカ分を分離除去する。BEST MODE FOR CARRYING OUT THE INVENTION Rare earth complex ore concentrate of Chinese white cloudite (rare oxide equivalent content: 30%) is ground and sulfuric acid roasted to obtain rare earth sulfate powder. At that time, HF, CO 2 , SO 3 and the like volatilize. Rare earth sulfate powder is extracted with water, and BaSO 4 , C
Separate insoluble residues such as aSO 4 and SiO 2 . Salt is added to the rare earth sulfate solution to precipitate crystals as a double salt of sodium chloride.
G This is reacted with hydrochloric acid and chlorinated, but the pH is adjusted to control the acidity to separate and remove hardly soluble hydroxides such as Th and Fe and insoluble silica.
【００２０】塩化希土溶液から塩化ネオジウムを溶媒抽
出し、残余の塩化セリウムを主成分とする希土塩化物
を、重炭酸アンモニウムで処理して軽炭酸希土類原料を
得る。水酸化希土類も研摩材原料として考えられるが、
炭酸希土類が取扱いが容易である。軽炭酸希土類原料の
組成を酸化物換算重量％で一例を示すと、ＣｅＯ2 ：２
３．０％、Ｌａ2 Ｏ3 ：１０．０％、Ｎｄ2 Ｏ3 ：２．
０％、Ｐｒ6 Ｏ11：４．８％、他の希土類：０．３％、
全希土類：４０．１％、強熱減量：５８．３５％、非希
土組成物：１．５５％（Ｎａ2 Ｏ：０．１０％、ＳｒＯ
＋ＣａＯ＋ＢａＯ：０．５５％、Ｃｌ：０．４０％、Ｆ
ｅ2 Ｏ3 ：０．１０％、ＳＯ4 ：０．３５％）である。
なお、酸化トリウム換算の放射性物質量はベクレルレベ
ルでほとんどカウントしない。Neodymium chloride is solvent-extracted from the rare earth chloride solution, and the remaining rare earth chloride mainly composed of cerium chloride is treated with ammonium bicarbonate to obtain a rare earth light carbonate raw material. Rare earth hydroxides can also be considered as a raw material for abrasives,
Rare earth carbonate is easy to handle. An example of the composition of the rare earth carbon dioxide raw material in terms of weight% in terms of oxide is CeO 2 : 2.
3.0%, La 2 O 3 : 10.0%, Nd 2 O 3 : 2.
0%, Pr 6 O 11 : 4.8%, other rare earths: 0.3%,
All rare earth: 40.1%, loss on ignition: 58.35%, the non-rare earth composition: 1.55% (Na 2 O: 0.10%, SrO
+ CaO + BaO: 0.55%, Cl: 0.40%, F
e 2 O 3: 0.10%, SO 4: 0.35%).
The amount of radioactive material in terms of thorium oxide is hardly counted at the becquerel level.
【００２１】軽炭酸希土類原料では、放射性物質が実質
的に除去され、焼成時のシンタリングの原因となるアル
カリ性強塩基物質である酸化ナトリウム、酸化カルシウ
ム、酸化バリウム、酸化ストロンチウム等のアルカリ金
属及びアルカリ土類金属酸化物が除かれている。In the rare earth carbon dioxide raw material, radioactive substances are substantially removed, and alkali metals such as sodium oxide, calcium oxide, barium oxide, and strontium oxide, which are alkaline strong base substances that cause sintering during firing, are used. Earth metal oxides have been removed.
【００２２】次に軽炭酸希土類原料を粉砕し、スラリ−
状態下にフッ酸水溶液を撹拌下に滴下する。このように
炭酸希土類をフッ酸水溶液で処理すると、希土類は一様
にフッ素化され、ランタンをはじめ塩基性物質は中和さ
れる。反応させるフッ酸量としては、最終製品であるセ
リウム研摩材中のフッ素含量が３〜９重量％になるよう
にされる。Next, the rare earth carbonaceous material is pulverized, and a slurry is prepared.
Under this condition, a hydrofluoric acid aqueous solution is added dropwise with stirring. When the rare earth carbonate is treated with the hydrofluoric acid aqueous solution, the rare earth is uniformly fluorinated, and the basic substances including lanthanum are neutralized. The amount of hydrofluoric acid to be reacted is such that the fluorine content in the final product, cerium abrasive, is 3 to 9% by weight.
【００２３】次に部分フッ素化されたものを焼成する。
焼成により主成分のセリウムは４価の酸化セリウムとな
る。焼成温度は、目的とする研摩対象物によって結晶化
度を制御するので一様でなく、また製品粒度によっても
異なるが、６００℃〜１０００℃の間が好ましい。高研
削性を得るためには高い温度での焼成が望ましく、一
方、柔らかいガラス材が対象の場合や、研摩後のガラス
表面の面精度を重視する場合には、比較的低い温度での
焼成が望ましい。焼成後、粉砕し、それぞれの目的に応
じて分級し製品であるセリウム研摩材とする。Next, the partially fluorinated product is fired.
The main component cerium becomes tetravalent cerium oxide by firing. The firing temperature is not uniform since the degree of crystallinity is controlled depending on the target object to be polished, and varies depending on the particle size of the product. Firing at a high temperature is desirable in order to obtain high grindability.On the other hand, when soft glass material is the target or when the surface accuracy of the glass surface after polishing is important, firing at a relatively low temperature is desirable. desirable. After firing, the product is pulverized and classified according to each purpose to obtain a cerium abrasive as a product.
【００２４】[0024]
【実施例】以下に、アルカリ金属、アルカリ土類金属及
び放射性物質が化学的に分離除去されてその含量が低減
されたセリウムを主成分とする軽炭酸希土類原料を出発
物質として、セリウム研摩材を製造した実施例を示す。EXAMPLE A cerium abrasive was used as a starting material, starting from a cerium-based rare earth dicarbonate raw material having a reduced content of alkali metals, alkaline earth metals and radioactive substances by chemical separation and removal. The manufactured example is shown.
【００２５】炭酸希土類中の酸化物換算全希土（ＴＲＥ
Ｏ）含量４１％、ＴＲＥＯ中の酸化セリウム含量が６０
％である軽炭酸希土類原料１８００ｇに水道水１２００
ｍｌを加え、湿式ボ−ルミルで数時間粉砕し、平均粒度
１〜４ミクロンの粉体にした。これを容器内に入れ、水
を加えてスラリ−状にし、撹拌しながら５５％フッ酸９
１ｍｌを徐々に滴下し、滴下終了後さらに約１時間撹拌
して反応させることにより、部分フッ素化されたスラリ
−とした。Oxidized total rare earth (TRE) in rare earth carbonate
O) Content 41%, Cerium oxide content in TREO is 60
1800 g of rare earth carbonic acid raw material
Then, the mixture was pulverized with a wet ball mill for several hours to obtain a powder having an average particle size of 1 to 4 μm. This was put in a container, water was added to make a slurry, and 55% hydrofluoric acid 9 was added while stirring.
1 ml was gradually added dropwise, and after the completion of the addition, the mixture was stirred and reacted for about 1 hour to obtain a partially fluorinated slurry.
【００２６】スラリ−は濾過、予備乾燥後、乾式粉砕器
でさらに粉砕し、電気炉中で６００℃〜１０００℃で、
５〜１０時間焼成した。放冷後、粉砕、分級して平均粒
度が１．４〜２．４ミクロンのセリウム研摩材を得た
（これをサンプル１とする）。The slurry is filtered, pre-dried, and further pulverized in a dry pulverizer at 600 to 1000 ° C. in an electric furnace.
It baked for 5 to 10 hours. After being allowed to cool, it was pulverized and classified to obtain a cerium abrasive having an average particle size of 1.4 to 2.4 microns (this is referred to as Sample 1).
【００２７】同様にＴＲＥＯ含量４１％、酸化セリウム
含量が５０％の軽炭酸希土類原料を用いてサンプル１と
同様に処理してセリウム研摩材を得た（これをサンプル
２とする）。Similarly, a cerium abrasive was obtained by treating in the same manner as Sample 1 using a rare earth light carbonate raw material having a TREO content of 41% and a cerium oxide content of 50% (this is referred to as Sample 2).
【００２８】さらに、ＴＲＥＯ含量４６％、ＴＲＥＯ中
の酸化セリウム含量が５０％の軽炭酸希土類原料１８０
０ｇに、フッ化希土２７０ｇ、水道水１４００ｍｌを加
え、湿式ボ−ルミルで数時間粉砕し平均粒度１〜４ミク
ロンの粉体にし、サンプル１及び２と同様に焼成、粉
砕、分級処理をしてセリウム研摩材を得た（これをサン
プル３とする）。Further, a rare earth light carbonaceous material 180 having a TREO content of 46% and a cerium oxide content of 50% in TREO was used.
To 0 g, 270 g of rare earth fluoride and 1400 ml of tap water were added and pulverized with a wet ball mill for several hours to obtain a powder having an average particle size of 1 to 4 μm. Thus, a cerium abrasive was obtained (this is referred to as Sample 3).
【００２９】マウンテンパス鉱山のバステナサイト精鉱
から製造された市販のセリウム研摩材を比較例としてサ
ンプル１〜３の研削力試験を行った。試験方法は削材
（青板）を１回４５分間研摩し、青板の重量減を測定す
る。１日８回、４日間同様な操作を繰り返した。比較例
の場合の重量減を１００として各サンプルの重量減を相
対値で表１に示した。なお研摩機として５Ｂラッピング
マシンを使用し、削材として直径５０ｍｍの青板を使
用、研摩圧は９２ｇ／ｃｍ2 、スラリ−濃度は２０重量
％、定盤回転数は４０ｒｐｍとした。Samples 1 to 3 were subjected to a grinding force test using a commercially available cerium abrasive produced from the bastenasite concentrate of the Mountain Pass mine as a comparative example. In the test method, the cut material (blue plate) is polished once for 45 minutes, and the weight loss of the blue plate is measured. The same operation was repeated eight times a day for four days. Table 1 shows the weight loss of each sample as a relative value, with the weight loss in the comparative example as 100. A 5B lapping machine was used as a polishing machine, a blue plate having a diameter of 50 mm was used as a cutting material, the polishing pressure was 92 g / cm 2 , the slurry concentration was 20% by weight, and the rotation speed of the platen was 40 rpm.
【００３０】[0030]
【表１】 [Table 1]
【００３１】この結果から、本発明のセリウム研摩材は
いずれも比較例と比較して優れた研削力を有しているこ
とがわかる。また研摩品位については比較例と同等の表
面特性を保持していた。From these results, it can be seen that all of the cerium abrasives of the present invention have superior grinding power as compared with the comparative examples. In addition, the surface quality equivalent to that of the comparative example was maintained for the polishing quality.
【００３２】[0032]
【発明の効果】本発明では希土精鉱を化学的に処理して
軽希土類原料としてから、又は化学的に処理されて得ら
れた軽希土類原料を出発物質として使用して、同一プロ
セス内でフッ酸と反応させて部分フッ素化するので、フ
ッ素化の程度を自由に制御でき、最終製品中のフッ素含
量の制御も容易である。According to the present invention, a rare earth concentrate is chemically treated as a light rare earth raw material, or a light rare earth raw material obtained by chemical treatment is used as a starting material, and is used in the same process. Since it is partially fluorinated by reacting with hydrofluoric acid, the degree of fluorination can be freely controlled, and the control of the fluorine content in the final product is easy.
【００３３】同一工程内でのフッ酸による部分フッ素化
プロセスであることから、焼成に際してより均質なＣｅ
Ｌａ2 Ｏ3 Ｆマトリックス形成を得ることができ、耐久
性のある研摩材にすることができる。Since the process is a partial fluorination process using hydrofluoric acid in the same process, a more uniform Ce
La 2 O 3 F matrix formation can be obtained, and a durable abrasive can be obtained.
【００３４】またフッ酸による部分フッ素化の代わり
に、軽希土類原料にセリウムを主成分とする軽フッ化希
土類を添加して焼成する方法によっても、同様に研削力
のある研摩材とすることができる。低セリウム研摩材に
おいては、酸化ランタンによる悪影響をＣｅＬａ2 Ｏ3
Ｆを生成させる方向で解決できる。Also, instead of the partial fluorination with hydrofluoric acid, a method of adding a light fluoride rare earth element containing cerium as a main component to a light rare earth material and firing the same can produce an abrasive having a similar grinding power. it can. In low cerium abrasives, the adverse effects of lanthanum oxide are reduced by CeLa 2 O 3.
The problem can be solved in the direction of generating F.
【００３５】本発明方法により製造されたセリウム研摩
材は、放射性物質が極めて低いレベルに制御されている
ので、作業者に対する影響や環境問題に、より配慮した
製品といえる。The cerium abrasive produced by the method of the present invention has a radioactive substance controlled to an extremely low level, and can be said to be a product that is more conscious of the effects on workers and environmental issues.
【００３６】またアルカリ金属及びアルカリ土類金属の
含有量が低減されているので、高温焼成時のシンタリン
グの問題が生じにくく、管理し易い温度条件幅で焼成で
き、均一な製品を得ることができる。Further, since the contents of the alkali metal and the alkaline earth metal are reduced, the problem of sintering at the time of high-temperature firing is less likely to occur, the firing can be performed at a temperature condition range which can be easily controlled, and a uniform product can be obtained. it can.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 角田 毅弘 神奈川県茅ケ崎市茅ケ崎３丁目２番10号セ イミケミカル株式会社内 Ｆターム(参考） 3C063 BB01 CC01 4G076 AA02 AA05 AB21 BA38 BD02 CA02 DA30 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takehiro Tsunoda 3-2-1-10 Chigasaki, Chigasaki-shi, Kanagawa F-term in Imi Chemical Co., Ltd. (reference) 3C063 BB01 CC01 4G076 AA02 AA05 AB21 BA38 BD02 CA02 DA30
Claims (3)
ルカリ金属、アルカリ土類金属並びに放射性物質を含む
希土精鉱を粉砕し、アルカリ金属、アルカリ土類金属及
び放射性物質を化学的に分離除去してこれらの含量を低
減し、フッ素を含まずセリウムを主成分とする軽希土類
原料を作製し、該軽希土類原料にセリウムを主成分とす
るフッ化希土類を添加した後６００℃〜１０００℃で焼
成するセリウム研摩材の製造方法であって、得られるセ
リウム研摩材のフッ素含量が、前記軽希土類原料中のラ
ンタンがフッ化ランタンとなる量から、焼成中に前記フ
ッ化希土類が焼結を起こさない量までの範囲となるよう
に前記フッ化希土類の添加量を調整することを特徴とす
る酸化セリウムを主成分とするセリウム研摩材の製造方
法。A rare earth concentrate containing cerium and lanthanum, an alkali metal, an alkaline earth metal, and a rare earth concentrate containing a radioactive material are pulverized to chemically separate and remove the alkali metal, the alkaline earth metal and the radioactive material. To produce a light rare earth material mainly containing cerium without fluorine and adding a rare earth fluoride mainly containing cerium to the light rare earth material, followed by firing at 600 ° C. to 1000 ° C. A method for producing a cerium abrasive, wherein the fluorine content of the obtained cerium abrasive is such that the lanthanum in the light rare earth raw material becomes lanthanum fluoride, and the rare earth fluoride does not cause sintering during firing. A method for producing a cerium abrasive containing cerium oxide as a main component, wherein the amount of the rare earth fluoride added is adjusted so as to fall within the range up to the amount.
ルカリ金属、アルカリ土類金属並びに放射性物質を含む
希土精鉱を粉砕し、アルカリ金属、アルカリ土類金属及
び放射性物質を化学的に分離除去してこれらの含量を低
減し、フッ素を含まずセリウムを主成分とする軽希土類
原料を作製し、該軽希土類原料にセリウムを主成分とす
るフッ化希土類を添加した後６００℃〜１０００℃で焼
成するセリウム研摩材の製造方法であって、得られるセ
リウム研摩材のフッ素含量が３〜９重量％となるように
前記フッ化希土類の添加量を調整することを特徴とする
酸化セリウムを主成分とするセリウム研摩材の製造方
法。2. A method for pulverizing a rare earth concentrate containing cerium and lanthanum, an alkali metal, an alkaline earth metal, and a rare earth concentrate containing a radioactive substance to chemically separate and remove the alkali metal, the alkaline earth metal and the radioactive substance. To produce a light rare earth material mainly containing cerium without fluorine and adding a rare earth fluoride mainly containing cerium to the light rare earth material, followed by firing at 600 ° C. to 1000 ° C. A method for producing a cerium abrasive, comprising adjusting the amount of the rare earth fluoride to be adjusted so that the fluorine content of the obtained cerium abrasive is 3 to 9% by weight. Method for producing cerium abrasives.
である請求項１又は２に記載のセリウム研摩材の製造方
法。3. The method for producing a cerium abrasive according to claim 1, wherein the rare earth concentrate is a rare-earth complex concentrate of Chinese white cloudite.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006107116A1 (en) * | 2005-04-04 | 2006-10-12 | Showa Denko K.K. | Cerium oxide abrasives, process for production of the same, and use thereof |
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| WO2006107116A1 (en) * | 2005-04-04 | 2006-10-12 | Showa Denko K.K. | Cerium oxide abrasives, process for production of the same, and use thereof |
| US7722692B2 (en) | 2005-04-04 | 2010-05-25 | Show A Denko K.K. | Cerium oxide-based abrasive, and production method and use thereof |
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