JPH11147713A - Production of raw material for rare earth-based abrasion material from waste of abrasion material - Google Patents
Production of raw material for rare earth-based abrasion material from waste of abrasion materialInfo
- Publication number
- JPH11147713A JPH11147713A JP32389897A JP32389897A JPH11147713A JP H11147713 A JPH11147713 A JP H11147713A JP 32389897 A JP32389897 A JP 32389897A JP 32389897 A JP32389897 A JP 32389897A JP H11147713 A JPH11147713 A JP H11147713A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- abrasive
- waste
- solid
- raw material
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 71
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 60
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002699 waste material Substances 0.000 title claims description 29
- 239000000463 material Substances 0.000 title abstract 9
- 238000005299 abrasion Methods 0.000 title abstract 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 10
- -1 rare earth metal carbonate Chemical class 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 20
- 239000003082 abrasive agent Substances 0.000 claims description 17
- 238000011282 treatment Methods 0.000 abstract description 8
- 238000005498 polishing Methods 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000002002 slurry Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
Landscapes
- Processing Of Solid Wastes (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】本発明はガラス表面等の研摩
に使用した希土類系廃研摩材から不純物を除去した後、
希土類の固形分を回収する希土類系研摩材原料の製造方
法に関する。The present invention relates to a method for removing impurities from a rare earth waste abrasive used for polishing a glass surface or the like.
The present invention relates to a method for producing a rare earth-based abrasive raw material for recovering rare earth solids.
【０００２】[0002]
【従来の技術】現在、ガラス基板や光学レンズ等の研摩
に年間４０００トンの希土類系研摩材が使用されてい
る。希土類系研摩材は８０重量％以上の希土類酸化物を
含み、そのうち４０〜９０重量％が酸化セリウムであ
る。2. Description of the Related Art At present, 4000 tons of rare earth abrasives are used annually for polishing glass substrates, optical lenses and the like. The rare earth-based abrasive contains at least 80% by weight of a rare earth oxide, of which 40 to 90% by weight is cerium oxide.
【０００３】希土類系研摩材は例えばアメリカで産出さ
れるバストネサイト等の希土類鉱物の鉱石から選鉱工程
で異種鉱物を除去した後、得られたバストネサイト精鉱
を原料として、粉砕、化学処理、濾過、乾燥、ばい焼、
粉砕、分級、添加剤混合の各工程を経て製造されている
（シーエムシー発行「レア・アースの最新応用技術」１
９８５年）。[0003] Rare earth-based abrasives are obtained by removing different kinds of minerals from a rare earth mineral ore such as bastnaesite produced in the United States in a beneficiation process and then pulverizing and chemically treating the obtained bastnaesite concentrate. , Filtration, drying, roasting,
Manufactured through each process of pulverization, classification, and mixing of additives (CMC “Latest application of rare earth” 1
985).
【０００４】このようにして製造された希土類系研摩材
はその優れた研摩特性のため、また研摩対象である液晶
ディスプレイ装置（ＬＣＤ）用ガラス基板やコンピュー
タ用ハードディスク記憶装置に使われるガラス基板の増
産のために年々需要が増加している。[0004] The rare-earth-based abrasives manufactured in this manner have excellent polishing properties and increase the production of glass substrates for liquid crystal display devices (LCDs) to be polished and hard disk storage devices for computers. The demand is increasing year by year.
【０００５】[0005]
【発明が解決しようとする課題】しかし、現在これらの
希土類系研摩材は使用後は産業廃棄物としてほぼ全量が
廃棄されている。増加する産業廃棄物が深刻な社会問題
となっている情勢の下、使用済みの希土類系研摩材のリ
サイクル使用に対する要望が高まりつつある。また、こ
れらの希土類系廃研摩材には乾量基準で４０重量％以上
の希土類元素が含まれておりこれらの資源の有効利用と
いう観点から、また輸入に依存している希土類資源の安
定確保という面からも希土類系廃研摩材の原料回収が必
要である。However, at present, almost all of these rare earth abrasives are discarded as industrial waste after use. Under the situation where the increasing industrial waste is becoming a serious social problem, there is an increasing demand for recycling of used rare earth abrasives. In addition, these rare earth waste abrasives contain 40% by weight or more of rare earth elements on a dry basis, and from the viewpoint of effective use of these resources, it is necessary to secure the stable use of rare earth resources that depend on imports. It is necessary to recover the raw materials of rare earth waste abrasive from the viewpoint of the surface.
【０００６】特許第２６０６１５６号には、使用済みの
研磨剤を精密濾過することにより粗大不純物を濃縮液側
に濃縮して除去し、その透過液を限外濾過により濃縮し
て、その濃縮液を回収することを特徴とする研磨剤粒子
の回収方法が提案されている。しかしながら上記方法が
対象とする研磨剤は粒径が数１０〜５００ｎｍと微細で
あり、本発明の対象である希土類系研摩材の粒径は０．
４〜３．０μｍであるため、上記方法は適用することが
できない。[0006] Japanese Patent No. 2606156 discloses that a used abrasive is finely filtered to concentrate and remove coarse impurities to the concentrated liquid side, and the permeated liquid is concentrated by ultrafiltration. There has been proposed a method for collecting abrasive particles, which is characterized by being collected. However, the abrasive targeted by the above method has a fine particle size of several tens to 500 nm, and the particle size of the rare-earth-based abrasive which is the object of the present invention is 0.1 mm.
Since the thickness is 4 to 3.0 μm, the above method cannot be applied.
【０００７】また特開平８−３５４３には、使用済みの
研磨材と研磨によって発生した不純物とが混在する研磨
廃棄物を原材料とし、前記研磨廃棄物から可溶性の不純
物を除去する化学処理工程と、前記研磨廃棄物を粉砕処
理して少なくとも規定値外の微粒子を除去する物理的処
理工程とからなる研磨材の製造方法が提案されている。
しかしながら上記方法が対象とする研磨材粒径は５〜２
０μｍであり、本発明が対象とする希土類系研摩材の粒
径は０．４〜３．０μｍであるため、上記方法は不適切
である。Japanese Patent Application Laid-Open No. 8-3543 discloses a chemical treatment step in which a polishing waste in which a used abrasive and impurities generated by polishing are mixed is used as a raw material, and a soluble impurity is removed from the polishing waste. There has been proposed a method for producing an abrasive, which comprises a physical treatment step of pulverizing the polishing waste to remove at least fine particles outside a specified value.
However, the abrasive particle size targeted by the above method is 5 to 2
0 μm, and the particle size of the rare earth-based abrasive targeted by the present invention is 0.4 to 3.0 μm, so the above method is inappropriate.
【０００８】本発明は上記に鑑みてなされたものであ
り、使用済みの希土類系研摩材から、簡単な設備を用い
経済的な工程で、希土類鉱石からの研摩材原料と同等品
質の希土類研摩材原料を製造する方法を提供することを
目的とする。[0008] The present invention has been made in view of the above, and a rare earth-based abrasive having the same quality as a raw material of an abrasive from a rare-earth ore can be produced from used rare-earth-based abrasives in an economical process using simple equipment. An object is to provide a method for producing a raw material.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
に本発明は、使用済みの希土類系廃研摩材からフッ化水
素酸を用いて可溶性の不純物を溶解除去する溶解工程、
及び溶解後固液分離を行う固液分離工程とからなること
を特徴とする、廃研摩材からの希土類系研摩材原料の製
造方法を提供する。To achieve the above object, the present invention provides a dissolving step of dissolving and removing soluble impurities from used rare earth waste abrasives using hydrofluoric acid.
And a solid-liquid separation step of performing solid-liquid separation after dissolution. A method for producing a rare earth-based abrasive raw material from waste abrasive is provided.
【００１０】また前記希土類系研摩材原料の製造方法に
おいて、前記固液分離工程により得られた固形分に酸化
希土又は炭酸希土を混合する成分調整工程を付加するこ
とを特徴とする。In the method for producing a rare earth-based abrasive material, a component adjusting step of mixing a rare earth oxide or a rare earth carbonate with the solid obtained in the solid-liquid separation step is added.
【００１１】さらに、前記使用済みの希土類系廃研摩材
は、乾量基準で希土類酸化物を４０重量％以上含むこと
が望ましい。４０重量％よりも低い場合は経済的に採算
性が悪いからである。Further, the used rare-earth waste abrasive preferably contains at least 40% by weight of a rare-earth oxide on a dry basis. If the amount is less than 40% by weight, economical profitability is poor.
【００１２】[0012]
【発明の実施の形態】本発明において、処理対象とする
「使用済みの希土類系廃研摩材」は希土類酸化物特に酸
化セリウムを主成分とする希土類系研摩材を、ガラス基
板表面研摩等に使用したものである。現在使われている
ガラス研摩用の希土類系研摩材は希土類酸化物を８０〜
９８重量％含んでいるが、その内酸化セリウムが最も多
く希土類酸化物の４０〜９０重量％を占めている。さら
にフッ素Ｆを５〜９重量％含んでいる。フッ素は元々バ
ストネサイト鉱石［（Ｃｅ，Ｌａ）(ＣＯ3)Ｆ］に含ま
れているが、ガラス研磨において物理研磨とともに重要
な、化学研磨の作用を持つため含有量を５〜９重量％に
調整している。希土類系研摩材の平均粒径としては０．
４〜３．０μmが好ましく使用されている。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the "used rare earth-based abrasive" to be treated is a rare earth-based abrasive mainly composed of a rare earth oxide, particularly cerium oxide, for polishing a glass substrate surface or the like. It was done. Currently used rare earth abrasives for glass polishing are rare earth oxides of 80 ~
Among them, cerium oxide accounts for 40 to 90% by weight of the rare earth oxide. Further, it contains 5 to 9% by weight of fluorine F. Fluorine is originally contained in bastnaesite ore [(Ce, La) (CO3) F], but has a chemical polishing effect which is important together with physical polishing in glass polishing. I am adjusting. The average particle size of the rare-earth-based abrasive is 0.
4-3.0 μm is preferably used.
【００１３】希土類系研摩材は、液晶ディスプレイ装置
やコンピュータのハードディスク記憶装置に使われるガ
ラス基板、レンズ等の光学ガラス、半導体ＩＣ用フォト
マスクのガラス基板、陰極線管（ＣＲＴ）用ガラス等の
研摩に使用されている。Rare earth abrasives are used for polishing glass substrates used for liquid crystal display devices and hard disk storage devices of computers, optical glasses such as lenses, glass substrates for photomasks for semiconductor ICs, and glass for cathode ray tubes (CRT). in use.
【００１４】希土類系廃研摩材スラリーを乾燥したも
の、あるいは希土類系廃研摩材スラリーを有機系または
無機系凝集剤で凝集させフィルタープレス等の脱水濾過
装置で固液分離した後の固形分（ケーキ）を乾燥したも
のの組成を調べると、研摩対象、研摩方法によっても差
は生じるが、ガラス成分、特にシリカ（ＳｉＯ2）が２
〜２０重量％含まれている。使用前の研摩材のシリカは
２重量％以下であるのでかなり増加している。[0014] Dried rare earth waste abrasive slurry, or solid content (cake) after agglomeration of rare earth waste abrasive slurry with an organic or inorganic coagulant and solid-liquid separation with a dehydration filtration device such as a filter press Inspection of the composition of the dried product shows that there is a difference depending on the object to be polished and the polishing method.
-20% by weight. The silica in the abrasive before use is less than 2% by weight, which has increased considerably.
【００１５】また、廃研摩材スラリーを凝集する際にポ
リ塩化アルミニウム（ＰＡＣ）を使用した場合はアルミ
ナ（Ａｌ2Ｏ3）も３〜２０重量％含まれている。When polyaluminum chloride (PAC) is used for coagulating the waste abrasive slurry, alumina (Al 2 O 3) is contained in an amount of 3 to 20% by weight.
【００１６】本発明においては、希土類系廃研摩材のス
ラリーまたは該スラリーを脱水濾過したケーキを、フッ
化水素酸を１０〜５５重量％含む水溶液の入った反応槽
中に入れ、０．５〜８時間室温で攪拌する。フッ化水素
酸の量はシリカ含有量に対するフッ化水素酸重量の割合
が必要量となるように決定する。すなわち、Ｓｉ／Ｆの
比を１／３〜１／８、好ましくは１／４〜１／６となる
ようにする。廃研摩材中にアルミナ成分が混入している
場合はさらにＡｌ／Ｆの比を１／２〜１／４としてフッ
化水素酸を増加する必要がある。In the present invention, the slurry of the rare-earth waste abrasive or the cake obtained by dewatering and filtering the slurry is placed in a reaction tank containing an aqueous solution containing 10 to 55% by weight of hydrofluoric acid, and then the slurry is placed in a reaction vessel. Stir at room temperature for 8 hours. The amount of hydrofluoric acid is determined such that the ratio of the weight of hydrofluoric acid to the content of silica is the required amount. That is, the ratio of Si / F is set to 1/3 to 1/8, preferably 1/4 to 1/6. When the alumina component is mixed in the waste abrasive, it is necessary to further increase the hydrofluoric acid by setting the Al / F ratio to 1/2 to 1/4.
【００１７】希土類系廃研摩材のスラリー濃度は１００
〜３００ｇ／ｌが望ましい。スラリー濃度を３００ｇ／
ｌ以上とすると粘度が上昇し作業性が低下する。スラリ
ー濃度が１００ｇ／ｌ以下では処理能力が小さくなる。The slurry concentration of the rare earth waste abrasive is 100
~ 300 g / l is desirable. Slurry concentration of 300g /
If it is 1 or more, the viscosity increases and the workability decreases. When the slurry concentration is 100 g / l or less, the processing capacity is reduced.
【００１８】前記溶解工程の後、反応槽中の懸濁液をフ
ィルタープレス等の脱水濾過装置で固液分離を行う。上
記の方法により廃研摩材中のシリカは大部分溶出し、残
留固形分（ケーキ）中のシリカ濃度は乾量基準で２重量
％以下とすることができる。Ｓｉ／Ｆの比が１／３より
も大きい（フッ化水素酸が少ない）場合はシリカ除去が
十分でなく、１／８より小さい場合は固液分離後のケー
キ中のフッ素が過剰となり好ましくない。希土類系廃研
摩材に乾量基準で３〜２０重量％のアルミナ成分を含む
場合も上記工程によりアルミナ成分が２重量％以下とな
る。After the dissolution step, the suspension in the reaction tank is subjected to solid-liquid separation by a dehydration filter such as a filter press. Most of the silica in the waste abrasive is eluted by the above method, and the silica concentration in the residual solid (cake) can be 2% by weight or less on a dry basis. When the ratio of Si / F is larger than 1/3 (the amount of hydrofluoric acid is small), the removal of silica is not sufficient, and when the ratio is smaller than 1/8, fluorine in the cake after solid-liquid separation becomes excessive, which is not preferable. . Even when the rare earth waste abrasive contains 3 to 20% by weight of alumina component on a dry basis, the alumina component is reduced to 2% by weight or less by the above process.
【００１９】前記溶解工程で不純物を除去する溶解液と
して、フッ化アンモニウムと硫酸の混合水溶液、又はフ
ッ化アンモニウムと硝酸の混合水溶液があるが、これら
を使用した場合は工場廃水中の窒素成分の規制強化のた
め廃水中の窒素成分除去が必要となる。そのために高価
な設備を必要とし、経済的でない。そこで、本発明は廃
水処理が容易なフッ化水素酸水溶液を使用することとし
た。As a dissolving solution for removing impurities in the dissolving step, there is a mixed aqueous solution of ammonium fluoride and sulfuric acid, or a mixed aqueous solution of ammonium fluoride and nitric acid. It is necessary to remove nitrogen components in wastewater to strengthen regulations. This requires expensive equipment and is not economical. Therefore, the present invention uses an aqueous solution of hydrofluoric acid that can easily treat wastewater.
【００２０】前記固液分離工程により得られたケーキに
は乾量基準で７５重量％以上の希土類酸化物が含まれて
いる。しかし研摩材原料としては乾量基準として８０重
量％以上の希土類酸化物が必要である。また前記ケーキ
に含まれるフッ素の量が規定範囲からはずれている場合
があるため、酸化希土または炭酸希土を添加して成分調
整を行う成分調整工程が必要な場合がある。酸化希土及
び炭酸希土は鉱石から製造される中間原料である。酸化
希土は各種希土類元素の混合酸化物であり、酸化セリウ
ムを５０〜９９．９重量％含むものである。また炭酸希
土は各種希土類元素の混合炭酸塩である。いずれも市販
されている。The cake obtained by the solid-liquid separation step contains 75% by weight or more of a rare earth oxide on a dry basis. However, as a raw material for abrasives, a rare earth oxide of 80% by weight or more on a dry basis is required. Further, since the amount of fluorine contained in the cake may be out of the specified range, a component adjusting step of adding rare earth oxide or rare earth carbonate to adjust the component may be necessary. Rare earth oxides and rare earth carbonates are intermediate raw materials produced from ores. The rare earth oxide is a mixed oxide of various rare earth elements, and contains 50 to 99.9% by weight of cerium oxide. Rare earth carbonate is a mixed carbonate of various rare earth elements. Both are commercially available.
【００２１】使用済みの希土類系廃研摩材をフッ化水素
酸による不純物溶解処理を行った後、固液分離を行い回
収した希土類系研摩材原料の組成（希土類酸化物及びフ
ッ素の含有量）が前記規定範囲に含まれている場合には
前記成分調整工程を経ずに、鉱石を原料とした研摩材製
造工程に投入する。前記固液分離により回収した希土類
系研摩材原料の組成が前記規定範囲に含まれていない場
合には、前記酸化希土または炭酸希土を加えて混合し、
成分調整を行う。混合する酸化希土または炭酸希土の比
率は回収した希土類系研摩材原料の組成や、目的とする
製品の用途、仕様等に応じて決定する。After the used rare-earth-based abrasive is subjected to an impurity dissolving treatment with hydrofluoric acid, the composition (the content of rare-earth oxide and fluorine) of the recovered rare-earth-based abrasive is determined by solid-liquid separation. If it falls within the above specified range, it is introduced into an abrasive production process using ore as a raw material without going through the above component adjustment process. When the composition of the rare earth-based abrasive raw material recovered by the solid-liquid separation is not included in the specified range, the rare earth oxide or the rare earth carbonate is added and mixed,
Perform component adjustment. The ratio of the rare earth oxide or rare earth carbonate to be mixed is determined according to the composition of the recovered rare earth-based abrasive raw material, the intended use of the product, and the specifications.
【００２２】希土類系廃研摩材中に粒径が３μｍ以上の
粗大粒子が含まれていない場合は成分調整工程は、鉱石
を原料とした研摩材製造工程の最初の工程である粉砕工
程の後に入れる。When the rare earth waste abrasive does not contain coarse particles having a particle size of 3 μm or more, the component adjusting step is performed after the pulverizing step which is the first step of the abrasive material manufacturing step using ore as a raw material. .
【００２３】希土類系廃研摩材中に粒径３μｍ以上の粗
大粒子が含まれている場合は、前記フッ化水素酸処理の
前に粉砕または篩い分けを行うか、あるいは鉱石を原料
とした研摩材製造工程の最初の工程である粉砕工程の前
に入れ、粉砕工程を通過させても良い。When the rare earth waste abrasive contains coarse particles having a particle size of 3 μm or more, the abrasive is crushed or sieved before the hydrofluoric acid treatment, or an abrasive made of ore is used as a raw material. It may be inserted before the pulverizing step, which is the first step in the manufacturing process, and may pass through the pulverizing step.
【００２４】前記成分調整工程において、異なる研摩対
象や異なる研摩条件で用いられ組成や粒径の異なる使用
済み希土類系廃研摩材を２種以上混合しても良い。In the component adjusting step, two or more kinds of used rare earth waste abrasives having different compositions and particle sizes used under different polishing targets and different polishing conditions may be mixed.
【００２５】尚、上記処理に供する廃研摩材は希土類酸
化物を乾量基準で４０重量％以上含むことが採算性の観
点より好ましい。It is preferred from the viewpoint of profitability that the waste abrasive to be subjected to the above treatment contains at least 40% by weight of a rare earth oxide on a dry basis.
【００２６】[0026]
【実施例】本発明を実施例により、さらに具体的に説明
する。 実施例１ 液晶ディスプレイ装置用ガラス基板を研磨した後の希土
類系廃研摩材スラリーを固液分離して得たケーキを用い
た。組成は乾量基準で希土類酸化物６８．０重量％、シ
リカ１４．０重量％、フッ素５．１重量％であった。８
０％フッ化水素酸を１３６ｋｇ、水を３．４４ｍ３を入
れた反応槽に上記廃研摩材を乾量基準で０．８ｔ入れて
合計４ｍ３とした。スラリー濃度は２００ｇ／ｌとなっ
た。上記反応槽を攪拌機で1時間攪拌した後上記懸濁液
をフィルタープレスにポンプで送り、固液分離を行っ
た。さらに０．８ｍ３の水でケーキ洗浄を行った。ここ
で得られたケーキ１．１３ｔを乾燥し、０．７９ｔとな
ったものを分析したところ、乾量基準で希土類酸化物は
７９．０重量％、シリカ１．４重量％、フッ素１１．５
重量％であった。希土類酸化物のうち、酸化セリウムは
５０．３重量％であった。EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 A cake obtained by solid-liquid separation of a rare earth waste abrasive slurry after polishing a glass substrate for a liquid crystal display device was used. The composition was 68.0% by weight of rare earth oxide, 14.0% by weight of silica, and 5.1% by weight of fluorine on a dry basis. 8
0.8 t of the above-mentioned waste abrasive was put into a reaction tank containing 136 kg of 0% hydrofluoric acid and 3.44 m3 of water on a dry basis to make a total of 4 m3. The slurry concentration became 200 g / l. After stirring the reaction tank for 1 hour with a stirrer, the suspension was pumped to a filter press to perform solid-liquid separation. Further, the cake was washed with 0.8 m3 of water. When 1.13 t of the cake obtained here was dried and 0.79 t was analyzed, 79.0 wt% of rare earth oxide, 1.4 wt% of silica and 11.5 wt of fluorine were used on a dry basis.
% By weight. Cerium oxide was 50.3% by weight of the rare earth oxide.
【００２７】分析方法は次の通りである。希土類酸化物
（ＴＲＥＯ、ＴｏｔａｌＲａｒｅＥａｒｔｈＯｘｉｄｅ
ｓ）の分析は、ＪＩＳＭ８４０４−１９７６に基づき行
った。シリカはアルカリ溶融処理の後ＩＣＰで定量分析
し、フッ素はアルカリ溶融の後イオンメータで定量分析
した。酸化セリウムの分析は蛍光Ｘ線分析装置で行っ
た。The analysis method is as follows. Rare earth oxides (TREO, TotalRareEarthOxide
The analysis of s) was performed based on JISM8404-1976. Silica was quantitatively analyzed by ICP after alkali melting treatment, and fluorine was quantitatively analyzed by ion meter after alkali melting. The analysis of cerium oxide was performed with a fluorescent X-ray analyzer.
【００２８】前記固液分離工程の後、得られた希土類系
研摩材原料に酸化希土を７：３の割合に加えて混合し、
成分調整を行った後希土類研摩材製造工程に投入した。
すなわち、粉砕、化学処理、濾過、乾燥、ばい焼、粉
砕、分級、添加剤混合の各工程で定法により処理し、製
品を前記の方法で分析した。その結果乾量基準で希土類
酸化物は８６．１重量%、シリカ１．０重量%、フッ素は
８．１重量%であった。希土類酸化物のうち酸化セリウ
ムは５１．４％であった。After the solid-liquid separation step, rare earth oxide is added to the obtained rare earth-based abrasive raw material in a ratio of 7: 3 and mixed.
After the components were adjusted, they were put into a rare earth abrasive production process.
That is, in each of the steps of pulverization, chemical treatment, filtration, drying, roasting, pulverization, classification, and additive mixing, treatment was carried out by a standard method, and the product was analyzed by the above-mentioned method. As a result, on a dry basis, the rare earth oxide was 86.1% by weight, silica was 1.0% by weight, and fluorine was 8.1% by weight. Cerium oxide was 51.4% of the rare earth oxides.
【００２９】前記製造方法により得られた希土類系回収
研摩材の粒径を空気透過法（ブレーン法）により測定し
た。その結果平均粒径は１．４μｍとなり、鉱石を原料
として製造した希土類系研摩材の粒径と同等であった。The particle size of the rare earth-based recovered abrasive obtained by the above production method was measured by an air permeation method (Brain method). As a result, the average particle size was 1.4 μm, which was equivalent to the particle size of the rare earth-based abrasive produced using ore as a raw material.
【００３０】前記製造方法により得られた希土類系回収
研摩材をオスカー式研摩機を用いて次の条件で「研摩
力」を評価した。研磨力とは、所定の条件で青板ガラス
板を１０分間研摩した後の削り取られたガラス厚み分
と、鉱石を原料として製造された、標準の研摩材製造工
程により得られた研摩材により削り取られたガラス厚み
分の比を１００倍した数値である。評価条件として、圧
力２００ｇ／ｃｍ2、回転数１２０ｒｐｍ、スラリー供
給量２ｌ／ｍｉｎ、スラリー濃度１００ｇ／ｌとした。
その結果得られた研摩力は９７であった。鉱石を原料と
して製造した希土類系研摩材とほぼ同様の研磨力とな
り、同等の品質が得られた。The "abrasive power" of the rare-earth-based recovered abrasive obtained by the above-described production method was evaluated using an Oscar-type grinder under the following conditions. Abrasive power is defined as the thickness of the glass that has been polished after polishing a soda lime glass plate under predetermined conditions for 10 minutes, and the abrasive obtained by a standard abrasive production process manufactured using ore as a raw material. It is a numerical value obtained by multiplying the ratio of the glass thickness by 100. Evaluation conditions were a pressure of 200 g / cm 2, a rotation speed of 120 rpm, a slurry supply rate of 2 l / min, and a slurry concentration of 100 g / l.
The resulting polishing force was 97. The polishing power was almost the same as that of a rare earth abrasive produced from ore, and the same quality was obtained.
【００３１】[0031]
【本発明の効果】以上のように、本発明によれば従来産
業廃棄物として廃棄されていた希土類系廃研摩材から不
純物を除去し、希土類系研摩材原料として繰り返し使用
することが可能となり、希土類資源の安定確保に貢献す
る。しかも既存の簡単な設備を使用し経済的な工程で希
土類鉱石からの研摩材原料と同等品質の研摩材原料を製
造できる。また使用薬品による公害を発生させることも
なく、廃棄物量を大幅に減少できるという効果がある。As described above, according to the present invention, it is possible to remove impurities from rare earth waste abrasives conventionally discarded as industrial waste and to reuse them as rare earth abrasive raw materials, Contribute to the stable securing of rare earth resources. In addition, it is possible to produce an abrasive raw material of the same quality as an abrasive raw material from a rare earth ore in an economical process using existing simple equipment. In addition, there is an effect that the amount of waste can be greatly reduced without causing pollution due to chemicals used.
Claims (3)
水素酸を用いて可溶性の不純物を溶解除去する溶解工
程、及び溶解後固液分離を行う固液分離工程からなるこ
とを特徴とする、廃研摩材からの希土類系研摩材原料の
製造方法。1. A dissolving step for dissolving and removing soluble impurities from used rare earth waste abrasive using hydrofluoric acid, and a solid-liquid separating step for performing solid-liquid separation after dissolving. , A method for producing rare earth-based abrasive raw materials from waste abrasives.
に酸化希土又は炭酸希土を混合する成分調整工程を付加
したことを特徴とする請求項１記載の希土類系研摩材原
料の製造方法。2. A process for producing a rare earth-based abrasive material according to claim 1, further comprising a component adjusting step of mixing a rare earth oxide or a rare earth carbonate with the solid content obtained in the solid-liquid separation step. Method.
基準で希土類酸化物を４０重量％以上含むことを特徴と
する請求項１記載の希土類系研摩材原料の製造方法。3. The method according to claim 1, wherein the used rare earth waste abrasive contains at least 40% by weight of a rare earth oxide on a dry basis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32389897A JP3560121B2 (en) | 1997-11-11 | 1997-11-11 | Method for producing rare earth-based abrasive raw materials from waste abrasive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32389897A JP3560121B2 (en) | 1997-11-11 | 1997-11-11 | Method for producing rare earth-based abrasive raw materials from waste abrasive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11147713A true JPH11147713A (en) | 1999-06-02 |
| JP3560121B2 JP3560121B2 (en) | 2004-09-02 |
Family
ID=18159851
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32389897A Expired - Fee Related JP3560121B2 (en) | 1997-11-11 | 1997-11-11 | Method for producing rare earth-based abrasive raw materials from waste abrasive |
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| Country | Link |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002096611A1 (en) * | 2001-05-29 | 2002-12-05 | Memc Electronic Materials, S.P.A. | Method for treating an exhausted glycol-based slurry |
| JP2005179147A (en) * | 2003-12-22 | 2005-07-07 | Matsushita Electric Works Ltd | Ceramic substrate for mounting photoelectric conversion element |
| WO2007105714A1 (en) * | 2006-03-13 | 2007-09-20 | Showa Denko K.K. | Method of recovering rare earth element from composition containing rare earth fluoride |
| JP2010222519A (en) * | 2009-03-25 | 2010-10-07 | Mitsui Mining & Smelting Co Ltd | Method for producing cerium-based abrasive and method for treating the same |
| JP2015536830A (en) * | 2012-09-17 | 2015-12-24 | エルジー・ケム・リミテッド | Recycling method of waste abrasive containing ceria |
| JP2017061710A (en) * | 2015-09-23 | 2017-03-30 | 三菱マテリアル株式会社 | Recovery method of rare earth element |
-
1997
- 1997-11-11 JP JP32389897A patent/JP3560121B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002096611A1 (en) * | 2001-05-29 | 2002-12-05 | Memc Electronic Materials, S.P.A. | Method for treating an exhausted glycol-based slurry |
| EP1561557A1 (en) * | 2001-05-29 | 2005-08-10 | MEMC Electronic Materials S.P.A. | Method for treating an exhausted glycol-based slurry |
| US7223344B2 (en) | 2001-05-29 | 2007-05-29 | Memc Electronic Materials, Spa | Method for treating an exhausted glycol-based slurry |
| JP2005179147A (en) * | 2003-12-22 | 2005-07-07 | Matsushita Electric Works Ltd | Ceramic substrate for mounting photoelectric conversion element |
| JP4654577B2 (en) * | 2003-12-22 | 2011-03-23 | パナソニック電工株式会社 | Ceramic substrate for mounting photoelectric conversion elements |
| WO2007105714A1 (en) * | 2006-03-13 | 2007-09-20 | Showa Denko K.K. | Method of recovering rare earth element from composition containing rare earth fluoride |
| JP2010222519A (en) * | 2009-03-25 | 2010-10-07 | Mitsui Mining & Smelting Co Ltd | Method for producing cerium-based abrasive and method for treating the same |
| JP2015536830A (en) * | 2012-09-17 | 2015-12-24 | エルジー・ケム・リミテッド | Recycling method of waste abrasive containing ceria |
| JP2017061710A (en) * | 2015-09-23 | 2017-03-30 | 三菱マテリアル株式会社 | Recovery method of rare earth element |
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