JP2012106333A - Method for recovering cerium oxide polishing agent and recovered product containing cerium oxide polishing agent - Google Patents
Method for recovering cerium oxide polishing agent and recovered product containing cerium oxide polishing agent Download PDFInfo
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- JP2012106333A JP2012106333A JP2011228617A JP2011228617A JP2012106333A JP 2012106333 A JP2012106333 A JP 2012106333A JP 2011228617 A JP2011228617 A JP 2011228617A JP 2011228617 A JP2011228617 A JP 2011228617A JP 2012106333 A JP2012106333 A JP 2012106333A
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- cerium oxide
- abrasive
- polishing agent
- waste
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 113
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000005498 polishing Methods 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 claims abstract description 54
- 238000011084 recovery Methods 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 33
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011260 aqueous acid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003082 abrasive agent Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract 3
- 239000007788 liquid Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 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 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-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
- 239000003973 paint Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010922 glass waste Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
- B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
Abstract
Description
本発明は、酸化セリウム系研磨剤の回収方法、及び該酸化セリウム系研磨剤の回収方法により得られる酸化セリウム系研磨剤を含有する回収物に関する。 The present invention relates to a method for recovering a cerium oxide-based abrasive and a recovered material containing a cerium oxide-based abrasive obtained by the method for recovering the cerium oxide-based abrasive.
コンピューター、液晶ディスプレー、携帯電話などの普及により、ガラスディスク、水晶ウエーハ、液晶パネルなどガラス材料の使用量が増大している。これらガラス材料の表面は、鏡面に研磨される。研磨には、酸化セリウム成分が主たる効果を有するが、原料鉱石に、酸化セリウムと同時に含有される酸化ランタン、酸化ネオジム、酸化プラセオジムなどを含んだ粉体が酸化セリウム系研磨剤として使用されている。酸化セリウム系研磨剤は、スラリー化して使用されるが、使用しているうちに研磨剤の劣化、及び研磨されたガラス屑のスラリーへの混入により、所望の研磨速度が維持できなくなるとともに、研磨面の傷の原因となる。一定時間使用した酸化セリウム系研磨剤は、ガラス屑とともにそのほとんどが産業廃棄物として処理されているのが現状である。 With the spread of computers, liquid crystal displays, mobile phones, etc., the use of glass materials such as glass disks, crystal wafers, and liquid crystal panels is increasing. The surface of these glass materials is polished to a mirror surface. For polishing, the cerium oxide component has the main effect, but powders containing lanthanum oxide, neodymium oxide, praseodymium oxide, etc. contained in the raw ore at the same time as cerium oxide are used as cerium oxide abrasives. . The cerium oxide-based abrasive is used in the form of a slurry, but the desired polishing rate cannot be maintained due to deterioration of the abrasive during use and the mixing of the polished glass debris into the slurry. Causes scratches on the surface. At present, most of the cerium oxide abrasive used for a certain period of time is treated as industrial waste along with glass waste.
酸化セリウム系研磨剤に含有されるセリウム、ランタン、ネオジム、プラセオジムなどは、希土類金属であり、埋蔵量が少ない上に、産出場所が偏在している。例えば、これら希土類金属は、日本国内では産出しないため、日本はこれら希土類金属の入手を輸入に頼っている。
そのため、使用済みの酸化セリウム系研磨剤の回収と再利用が望まれている。
Cerium, lanthanum, neodymium, praseodymium, and the like contained in the cerium oxide-based abrasive are rare earth metals and have a small amount of reserves and are unevenly distributed. For example, since these rare earth metals are not produced in Japan, Japan relies on imports to obtain these rare earth metals.
Therefore, it is desired to recover and reuse the used cerium oxide abrasive.
使用済みの酸化セリウム系研磨剤の回収方法としては、例えば、ケーキ状の使用済み研磨剤粒子を水で再分散したスラリーとする工程、該再分散スラリーを酸で処理する工程、得られた酸処理スラリーを固液分離する工程、得られたケーキを乾燥し、解砕する工程からなるセリウム系研磨剤の回収方法が提案されている（特許文献１）。
しかし、この提案の技術は、工程が多く回収効率が悪いという問題がある。
As a method for recovering the used cerium oxide-based abrasive, for example, a step of making cake-like used abrasive particles re-dispersed with water, a step of treating the re-dispersed slurry with an acid, and the obtained acid A method for recovering a cerium-based abrasive comprising a step of solid-liquid separation of a treated slurry and a step of drying and crushing the obtained cake has been proposed (Patent Document 1).
However, this proposed technique has a problem that there are many steps and the recovery efficiency is poor.
また、酸化セリウム系研磨剤を研磨に使用して生じた研磨剤廃棄物を原料とし、前記研磨剤廃棄物とアルカリ水溶液とを混合して可溶性の不純物を溶解した後、この不純物が溶解した水溶液と固形分を分離し、次いでこの分離した固形分を篩分けして、微細な研磨剤を回収する研磨剤の回収方法が提案されている（特許文献２）。
しかし、この提案の技術は、研磨剤廃棄物をアルカリ水溶液と混合した際に、酸化セリウム系研磨剤の凝集物が十分にほぐれず、酸化セリウム系研磨剤の回収効率が悪いという問題がある。
In addition, an abrasive waste produced by using a cerium oxide-based abrasive for polishing is used as a raw material, the abrasive waste and an alkaline aqueous solution are mixed to dissolve soluble impurities, and then an aqueous solution in which the impurities are dissolved. A polishing agent recovery method has been proposed in which a solid content is separated, and then the separated solid content is sieved to recover a fine abrasive (Patent Document 2).
However, this proposed technique has a problem that when the abrasive waste is mixed with an alkaline aqueous solution, aggregates of the cerium oxide abrasive are not sufficiently loosened, and the recovery efficiency of the cerium oxide abrasive is poor.
また、酸化セリウム系研磨剤と、該酸化セリウム系研磨剤の粒子径よりも小さな小径異物と、前記酸化セリウム系研磨剤の粒子径よりも大きな大径異物とが凝集し凝集物として存在している酸化セリウム系研磨剤スラリー廃液から酸化セリウム系研磨剤を回収する回収方法であって、前記酸化セリウム系研磨剤スラリー廃液の機械的な分散処理を行う分散工程と、前記分散処理された分散液を濾過処理して前記分散液から前記大径異物を除去する濾過工程と、前記濾過処理された濾過液をサイクロンによって分級処理し、該濾過液中の前記酸化セリウム系研磨剤と前記小径異物とを分級する分級工程とを備えた酸化セリウム系研磨剤スラリー廃液からの研磨剤回収方法が提案されている（特許文献３）。
しかし、この提案の技術は、研磨剤スラリー廃液を用いる研磨剤回収方法であり、ケーキ状の研磨剤廃棄物への適用は想定されていない。また、研磨剤スラリー廃液は、水が多く酸化セリウム系研磨剤の含有濃度が低いため、機械的な分散処理等において処理効率が低いという問題がある。
Further, the cerium oxide-based abrasive, the small foreign matter smaller than the particle size of the cerium oxide-based abrasive, and the large foreign matter larger than the particle size of the cerium oxide-based abrasive are aggregated and exist as aggregates. A recovery method for recovering a cerium oxide abrasive slurry from a cerium oxide abrasive slurry waste liquid, a dispersion step for performing a mechanical dispersion treatment of the cerium oxide abrasive slurry waste liquid, and the dispersion treated dispersion liquid A filtration step of removing the large-diameter foreign matter from the dispersion by filtering, and classifying the filtered filtrate with a cyclone, and the cerium oxide-based abrasive and the small-diameter foreign matter in the filtrate There has been proposed a method of recovering an abrasive from a cerium oxide-based abrasive slurry waste solution, which includes a classification step for classifying the particles (Patent Document 3).
However, this proposed technique is an abrasive recovery method using an abrasive slurry waste liquid, and is not expected to be applied to cake-like abrasive waste. Further, the abrasive slurry waste liquid has a problem that the processing efficiency is low in mechanical dispersion processing and the like because it contains a lot of water and the content concentration of the cerium oxide abrasive is low.
したがって、簡易な工程であり、更に酸化セリウム系研磨剤の回収効率、特に酸化セリウム系研磨剤に含有される希土類酸化物の回収効率が優れる酸化セリウム系研磨剤の回収方法、及び該回収方法により得られる酸化セリウム系研磨剤を含有する回収物の提供が求められているのが現状である。 Therefore, the recovery process of the cerium oxide abrasive is excellent in the recovery efficiency of the cerium oxide abrasive, particularly the rare earth oxide contained in the cerium oxide abrasive, and the recovery method. At present, it is required to provide a recovered material containing the obtained cerium oxide-based abrasive.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、簡易な工程であり、更に酸化セリウム系研磨剤の回収効率、特に酸化セリウム系研磨剤に含有される希土類酸化物の回収効率が優れる酸化セリウム系研磨剤の回収方法、及び該回収方法により得られる酸化セリウム系研磨剤を含有する回収物を提供することを目的とする。 An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is a simple process, and further, the recovery efficiency of the cerium oxide abrasive, particularly the recovery method of the cerium oxide abrasive that is excellent in the recovery efficiency of the rare earth oxide contained in the cerium oxide abrasive, and An object is to provide a recovered material containing a cerium oxide-based abrasive obtained by the recovery method.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 酸化セリウム系研磨剤及びガラス研磨屑を含有するケーキ状の研磨剤廃棄物を、酸水溶液及びアルカリ水溶液のいずれかと混合し、解砕機により解砕する解砕工程を少なくとも含むことを特徴とする酸化セリウム系研磨剤の回収方法である。
＜２＞ 解砕機が、メディア型ミル、ラインミキサー、及びロールミルのいずれかである前記＜１＞に記載の酸化セリウム系研磨剤の回収方法である。
＜３＞ 酸水溶液が、塩酸、硫酸、硝酸、及びシュウ酸の少なくともいずれかを用いた酸水溶液である前記＜１＞から＜２＞のいずれかに記載の酸化セリウム系研磨剤の回収方法である。
＜４＞ 解砕工程の後に、酸化セリウム系研磨剤とガラス研磨屑とを分離する分離工程を含む前記＜１＞から＜３＞のいずれかに記載の酸化セリウム系研磨剤の回収方法である。
＜５＞ 前記＜１＞から＜４＞のいずれかに記載の酸化セリウム系研磨剤の回収方法により得られることを特徴とする酸化セリウム系研磨剤を含有する回収物である。
＜６＞ 全希土類酸化物の含有量が、９０質量％以上である前記＜５＞に記載の酸化セリウム系研磨剤を含有する回収物である。
＜７＞ 全希土類酸化物における酸化セリウムの含有量が、７０質量％以上である前記＜５＞から＜６＞のいずれかに記載の酸化セリウム系研磨剤を含有する回収物である。
＜８＞ 乾燥粉体、含水ケーキ、及びスラリーのいずれかである前記＜５＞から＜７＞のいずれかに記載の酸化セリウム系研磨剤を含有する回収物である。
Means for solving the problems are as follows. That is,
<1> It includes at least a crushing step of mixing a cake-like abrasive waste containing a cerium oxide-based abrasive and glass polishing scraps with either an aqueous acid solution or an aqueous alkaline solution and crushing with a crusher. This is a method for recovering a cerium oxide abrasive.
<2> The method for recovering a cerium oxide abrasive according to <1>, wherein the crusher is any one of a media mill, a line mixer, and a roll mill.
<3> The method for recovering a cerium oxide-based abrasive according to any one of <1> to <2>, wherein the acid aqueous solution is an acid aqueous solution using at least one of hydrochloric acid, sulfuric acid, nitric acid, and oxalic acid. is there.
<4> The method for recovering a cerium oxide abrasive according to any one of <1> to <3>, further including a separation step of separating the cerium oxide abrasive and the glass polishing waste after the crushing step. .
<5> A recovered material containing a cerium oxide abrasive, which is obtained by the method for recovering a cerium oxide abrasive according to any one of <1> to <4>.
<6> The recovered material containing the cerium oxide-based abrasive according to <5>, wherein the total rare earth oxide content is 90% by mass or more.
<7> A recovered material containing the cerium oxide-based abrasive according to any one of <5> to <6>, wherein the content of cerium oxide in all rare earth oxides is 70% by mass or more.
<8> A recovered material containing the cerium oxide-based abrasive according to any one of <5> to <7>, which is any one of a dry powder, a water-containing cake, and a slurry.
本発明によると、従来における前記諸問題を解決することができ、簡易な工程であり、更に酸化セリウム系研磨剤の回収効率、特に酸化セリウム系研磨剤に含有される希土類酸化物の回収効率が優れる酸化セリウム系研磨剤の回収方法、及び該回収方法により得られる酸化セリウム系研磨剤を含有する回収物を提供することができる。 According to the present invention, the conventional problems can be solved, the process is simple, and the recovery efficiency of the cerium oxide-based abrasive, particularly the recovery efficiency of the rare earth oxide contained in the cerium oxide-based abrasive is high. An excellent method for recovering a cerium oxide-based abrasive, and a recovered product containing a cerium oxide-based abrasive obtained by the recovery method can be provided.
（酸化セリウム系研磨剤の回収方法、及び酸化セリウム系研磨剤を含有する回収物）
本発明の酸化セリウム系研磨剤の回収方法は、解砕工程を少なくとも含み、更に必要に応じて、分離工程などのその他の工程を含む。
本発明の酸化セリウム系研磨剤を含有する回収物は、本発明の前記酸化セリウム系研磨剤の回収方法により得られる。
(Recovery method of cerium oxide-based abrasive and recovered material containing cerium oxide-based abrasive)
The method for recovering a cerium oxide-based abrasive of the present invention includes at least a crushing step, and further includes other steps such as a separation step as necessary.
The recovered material containing the cerium oxide-based abrasive of the present invention is obtained by the method for recovering a cerium oxide-based abrasive of the present invention.
＜解砕工程＞
前記解砕工程としては、酸化セリウム系研磨剤及びガラス研磨屑を含有するケーキ状の研磨剤廃棄物を、酸水溶液及びアルカリ水溶液のいずれかと混合し、解砕機により解砕する工程であれば、特に制限はなく、目的に応じて適宜選択することができる。
前記解砕とは、前記研磨剤廃棄物中の前記酸化セリウム系研磨剤の凝集状態を解きほぐすことを意味する。
前記研磨剤廃棄物中の前記酸化セリウム系研磨剤は凝集剤などにより凝集状態にあるため、前記解砕工程において前記研磨剤廃棄物を解砕しつつ酸又はアルカリにより処理することで、前記酸化セリウム系研磨剤と前記ガラス研磨剤などの他の成分とを分離し、前記酸化セリウム系研磨剤の回収が容易になる。
また、前記解砕工程においては、解砕機に前記研磨剤廃棄物を投入する際に、ケーキ状の状態で投入でき、スラリー状にする必要がないため、工程の短縮が可能であり、かつ解砕工程において使用する水の量を低減できるため、解砕工程における処理効率が高くなる。
<Crushing process>
As the crushing step, a cake-like abrasive waste containing a cerium oxide-based abrasive and glass polishing waste is mixed with either an acid aqueous solution or an alkali aqueous solution, and if it is a step of crushing with a crusher, There is no restriction | limiting in particular, According to the objective, it can select suitably.
The crushing means unraveling the aggregation state of the cerium oxide-based abrasive in the abrasive waste.
Since the cerium oxide-based abrasive in the abrasive waste is in an agglomerated state due to an aggregating agent or the like, the oxidizing waste can be treated with an acid or an alkali while being crushed in the crushing step. The cerium-based abrasive and other components such as the glass abrasive are separated, and the cerium oxide-based abrasive can be easily recovered.
Further, in the crushing step, when the abrasive waste is put into the crusher, it can be put in a cake state and does not need to be in a slurry state, so that the process can be shortened and Since the amount of water used in the crushing process can be reduced, the treatment efficiency in the crushing process is increased.
−研磨剤廃棄物−
前記研磨剤廃棄物は、酸化セリウム系研磨剤と、ガラス研磨屑とを少なくとも含有し、更に必要に応じて、凝集剤などのその他の成分を含有する。
前記研磨剤廃棄物は、ケーキ状である。
ケーキ状の前記研磨剤廃棄物は、例えば、使用済みの酸化セリウム系研磨剤とガラス研磨屑とが混在した混合物スラリーに凝集剤を添加して酸化セリウム系研磨剤を凝集させた後に、固液分離手段などにより水分を減少又は除去して湿ケーキ状（脱水ケーキ状）又はそれを乾燥することにより得られる。前記研磨剤廃棄物の水分量は、通常、３０質量％〜６０質量％程度である。
ここで、「ケーキ」とは、固形分が水分を含有した状態でろ過装置による圧搾などで固まり状になったもののことをいい、「スラリー」とは、固形分が水などの液中に分散され、液状または泥状になったもののことをいう。
-Abrasive waste-
The abrasive waste contains at least a cerium oxide abrasive and glass polishing waste, and further contains other components such as an aggregating agent as necessary.
The abrasive waste is in the form of a cake.
For example, the cake-like abrasive waste is obtained by adding a flocculant to a mixture slurry in which used cerium oxide abrasive and glass polishing scraps are mixed to agglomerate the cerium oxide abrasive. It is obtained by reducing or removing moisture by a separating means or the like and drying it in the form of a wet cake (dehydrated cake). The water content of the abrasive waste is usually about 30% to 60% by mass.
Here, “cake” means that the solid content is in a solid state containing water, and is solidified by squeezing with a filtration device, etc., and “slurry” is dispersed in a liquid such as water. Means liquid or mud.
前記研磨剤廃棄物の状態（大きさ）としては、特に制限はなく、解砕機に供給可能な大きさ（一般的には数ｃｍ程度以下）になっていればよい。 There is no restriction | limiting in particular as a state (size) of the said abrasive waste, What is necessary is just to become the magnitude | size (generally about several cm or less) which can be supplied to a crusher.
−−酸化セリウム系研磨剤−−
前記酸化セリウム系研磨剤の材質、形状、大きさ、構造としては、特に制限はなく、目的に応じて適宜選択することができる。
--Cerium oxide abrasive--
There is no restriction | limiting in particular as a material, a shape, a magnitude | size, and a structure of the said cerium oxide type abrasive | polishing agent, According to the objective, it can select suitably.
前記酸化セリウム系研磨剤の材質としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、酸化セリウムを少なくとも含有し、更に必要に応じて酸化ランタン、酸化プラセオジムなどを含有する酸化セリウム系研磨剤が挙げられる。
前記酸化セリウム系研磨剤の平均粒子径としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、０．５μｍ〜１０μｍが挙げられる。ここで、平均粒子径は、例えば、レーザー回折式粒度分布測定装置（一例として、島津製作所製、ＳＡＬＤ２０００Ａ）により測定することができる。
The material of the cerium oxide-based abrasive is not particularly limited and may be appropriately selected depending on the purpose. For example, it contains at least cerium oxide, and further contains lanthanum oxide, praseodymium oxide, and the like as necessary. A cerium oxide type abrasive | polishing agent is mentioned.
There is no restriction | limiting in particular as an average particle diameter of the said cerium oxide type abrasive | polishing agent, According to the objective, it can select suitably, For example, 0.5 micrometer-10 micrometers are mentioned. Here, the average particle diameter can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus (for example, SALD2000A manufactured by Shimadzu Corporation).
前記酸化セリウム系研磨剤に含有されるセリウム、ランタン、プラセオジムなどの希土類元素（レアアース）は、貴重な資源であり、回収による再利用が望まれている元素である。 Rare earth elements (rare earth) such as cerium, lanthanum, and praseodymium contained in the cerium oxide-based abrasive are precious resources and are elements that are desired to be reused by recovery.
−−ガラス研磨屑−−
前記ガラス研磨屑は、前記酸化セリウム系研磨剤を用いて、ガラスディスク、水晶ウエーハ、液晶パネルなどのガラス材料を研磨した際に発生する研磨屑である。
前記酸化セリウム系研磨剤を用いた前記ガラス材料の研磨は、通常の研磨剤（例えば酸化アルミニウム）を用いた研磨のように、物理的又は機械的に被研磨物を削るようなものではなく、前記酸化セリウム系研磨剤が前記ガラス材料と接触したとき、珪素成分が化学的に反応を起こし、原子レベルの大きさで剥ぎ取られ、酸化セリウムに付着することによって行われると考えられている。そのため、前記ガラス研磨屑の大きさは、前記酸化セリウム系研磨剤よりも非常に小さい。そして、前記研磨剤廃棄物において前記ガラス研磨屑は、主に前記酸化セリウム系研磨剤に付着している。
--- Glass polishing waste--
The glass polishing waste is polishing waste generated when a glass material such as a glass disk, a quartz wafer, or a liquid crystal panel is polished using the cerium oxide abrasive.
The polishing of the glass material using the cerium oxide-based abrasive is not physically or mechanically scraping the object to be polished, such as polishing using an ordinary abrasive (for example, aluminum oxide), It is considered that when the cerium oxide abrasive comes into contact with the glass material, the silicon component chemically reacts, is peeled off at the atomic level, and adheres to cerium oxide. Therefore, the size of the glass polishing waste is much smaller than that of the cerium oxide-based abrasive. And in the said abrasive | polishing agent waste, the said glass grinding | polishing waste has mainly adhered to the said cerium oxide type abrasive | polishing agent.
−−凝集剤−−
前記研磨剤廃棄物は、前記のとおり、ケーキ状とする際に、凝集剤を使用することが一般的である。
前記凝集剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、塩化鉄、塩化アルミニウム、硫酸アルミニウム、高分子凝集剤などが挙げられる。
--Flocculant--
As described above, when the abrasive waste is made into a cake, a flocculant is generally used.
There is no restriction | limiting in particular as said flocculant, According to the objective, it can select suitably, For example, iron chloride, aluminum chloride, aluminum sulfate, a polymer flocculant, etc. are mentioned.
−酸水溶液及びアルカリ水溶液−
−−酸水溶液−−
前記酸水溶液としては、特に制限はなく、目的に応じて適宜選択することができるが、塩酸、硫酸、硝酸、及びシュウ酸の少なくともいずれかを用いた酸水溶液であることが好ましい。
前記酸水溶液と前記研磨剤廃棄物とを混合した際の混合物のｐＨとしては、特に制限はなく、目的に応じて適宜選択することができるが、ｐＨ５以下が好ましく、ｐＨ１〜ｐＨ３がより好ましい。前記ｐＨが、１未満であると、有用成分の溶解が過剰に進み、回収率が低下することがあり、３を超えると、処理に時間を要し効率が低下したり、さらに処理時間が長くなることでメディアによる粉砕が進み、回収物の粒度分布が微粒側にシフトし、研磨剤として再利用した際の研磨効率が悪化することがある。前記ｐＨが、前記より好ましい範囲であると、回収率と時間的な処理効率の両立という観点から有利である。
-Aqueous acid solution and alkaline solution-
--Aqueous acid solution--
There is no restriction | limiting in particular as said acid aqueous solution, Although it can select suitably according to the objective, It is preferable that it is an acid aqueous solution using at least any one of hydrochloric acid, a sulfuric acid, nitric acid, and an oxalic acid.
There is no restriction | limiting in particular as pH of the mixture at the time of mixing the said acid aqueous solution and the said abrasive | polishing agent waste, Although it can select suitably according to the objective, pH 5 or less is preferable and pH1-pH3 are more preferable. When the pH is less than 1, dissolution of useful components proceeds excessively, and the recovery rate may decrease. When the pH exceeds 3, the treatment takes time and the efficiency decreases, and the treatment time further increases. As a result, the pulverization by the media proceeds, and the particle size distribution of the recovered material may shift to the fine particle side, and the polishing efficiency when reused as an abrasive may be deteriorated. When the pH is in the more preferable range, it is advantageous from the viewpoint of achieving both recovery and temporal treatment efficiency.
−−アルカリ水溶液−−
前記アルカリ水溶液としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水酸化ナトリウム水溶液などが挙げられる。
前記水酸化ナトリウム水溶液などの前記アルカリ水溶液で前記研磨剤廃棄物中の不要成分である酸化ケイ素（ＳｉＯ２）などを溶解させることにより、有用成分である酸化セリウム等の希土類酸化物を回収することができる。
--- Alkaline aqueous solution--
There is no restriction | limiting in particular as said alkaline aqueous solution, According to the objective, it can select suitably, For example, sodium hydroxide aqueous solution etc. are mentioned.
Recovery of rare earth oxides such as cerium oxide which is a useful component by dissolving silicon oxide (SiO 2 ) which is an unnecessary component in the abrasive waste with the alkaline aqueous solution such as the sodium hydroxide aqueous solution. Can do.
前記酸水溶液及び前記アルカリ水溶液の少なくともいずれかと、前記研磨剤廃棄物との混合割合としては、特に制限はなく、目的に応じて適宜選択することができるが、前記酸水溶液及び前記アルカリ水溶液の少なくともいずれか（Ａ）と前記研磨剤廃棄物（Ｂ）との質量比（Ａ：Ｂ）で、１００：３０〜１００：２が好ましく、１００：１０〜１００：５がより好ましい。前記質量比において、前記酸水溶液及び前記アルカリ水溶液の少なくともいずれかが、好ましい範囲未満であると、ケーキ状の前記研磨剤廃棄物の解砕が困難になる、又は解砕に時間が掛かることがあり、好ましい範囲を超えると、前記酸水溶液及び前記アルカリ水溶液の少なくともいずれかと、前記研磨剤廃棄物との混合物における水の量が多くなり、解砕の際の処理効率が低くなることがある。前記混合割合が、前記より好ましい範囲であると、解砕の際の処理効率が高い点で有利である。 The mixing ratio of at least one of the acid aqueous solution and the alkali aqueous solution and the abrasive waste is not particularly limited and may be appropriately selected depending on the purpose. The mass ratio (A: B) between any (A) and the abrasive waste (B) is preferably 100: 30 to 100: 2, and more preferably 100: 10 to 100: 5. In the mass ratio, if at least one of the acid aqueous solution and the alkali aqueous solution is less than the preferred range, it may be difficult to crush the cake-like abrasive waste, or it may take time to crush. If it exceeds the preferable range, the amount of water in the mixture of at least one of the acid aqueous solution and the alkali aqueous solution and the abrasive waste increases, and the treatment efficiency at the time of crushing may be lowered. When the mixing ratio is in the more preferable range, it is advantageous in that the treatment efficiency at the time of crushing is high.
酸及びアルカリは、前記ガラス研磨屑や前記凝集剤などの酸及びアルカリに可溶な不純物を溶解し、前記解砕工程において、前記酸化セリウム系研磨剤と、前記ガラス研磨屑や前記凝集剤などの他の成分との分離を容易にする。 The acid and alkali dissolve acid- and alkali-soluble impurities such as the glass polishing waste and the flocculant, and in the crushing step, the cerium oxide-based abrasive, the glass polishing waste and the flocculant, etc. Facilitates separation from other components.
−解砕−
前記解砕は、解砕機により行うことができる。
−−解砕機−−
前記解砕機としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メディア型ミル、ロールミル、強撹拌型の撹拌機、ラインミキサーなどが挙げられる。
-Disintegration-
The crushing can be performed by a crusher.
--- Crusher--
There is no restriction | limiting in particular as said crusher, According to the objective, it can select suitably, For example, a media type mill, a roll mill, a strong stirring type stirrer, a line mixer etc. are mentioned.
前記メディア型ミルとしては、容器内にボール又はビーズ（以下、メディアと称することがある）を入れ、固体や液体と共に攪拌する装置であれば、特に制限はなく、目的に応じて適宜選択することができる。
前記メディア型ミルとしては、例えば、密閉容器を機械的に振盪しメディアを強力に攪拌するペイントシェイカー、密閉容器を機械的に回転させメディアを攪拌するボールミル、蓋付き容器内に攪拌子（回転軸に多数の棒を取り付けた攪拌子や回転軸に多段の円盤を取り付けた攪拌子等、機器メーカーにより様々な形状を有する）を入れて回転させ、メディアを強力に攪拌するアトライターやサンドミル、密閉容器内に多数の円盤（アジテーターディスクと称される）が取り付けられた回転軸を有し、これを回転させ、メディアを強力に攪拌するビーズミルなどが挙げられる。
前記メディア型ミルの装置の呼称は製造メーカーによって異なる場合も多々あるが、何れの装置においても、固体や液体と一緒に攪拌されるメディア同士の衝突力により、強力に解砕できることが特徴である。これらの装置は、無機物の粉砕、分散、混合等や、塗料顔料の練肉、分散等に広く用いられているものが使用できる。
前記メディアの材質としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ソーダガラス、アルミナ、ジルコニア、テフロン（登録商標）などが挙げられる。
前記メディアの大きさとしては、特に制限はなく、目的に応じて適宜選択することができるが、直径が、５ｍｍ〜３０ｍｍが好ましく、１０ｍｍ〜２０ｍｍがより好ましい。
The media type mill is not particularly limited as long as it is a device in which balls or beads (hereinafter sometimes referred to as media) are placed in a container and stirred together with a solid or liquid, and is appropriately selected according to the purpose. Can do.
Examples of the media type mill include, for example, a paint shaker that mechanically shakes a sealed container to stir the medium strongly, a ball mill that mechanically rotates the sealed container to stir the medium, and a stirrer (rotating shaft) in the lidded container. (A variety of shapes, such as a stirrer with a large number of rods attached to it, or a stirrer with a multi-stage disk attached to the rotating shaft, etc.) A bead mill that has a rotating shaft with a large number of disks (referred to as agitator disks) mounted in a container, and rotates the medium to vigorously stir the media can be used.
The name of the device of the media type mill is often different depending on the manufacturer, but in any device, it is characterized in that it can be crushed strongly by the collision force between the media stirred together with the solid or liquid. . As these apparatuses, those widely used for pulverizing, dispersing, mixing and the like of inorganic substances, and for grinding and dispersing paint pigments can be used.
There is no restriction | limiting in particular as a material of the said media, According to the objective, it can select suitably, For example, soda glass, an alumina, a zirconia, Teflon (trademark) etc. are mentioned.
There is no restriction | limiting in particular as a magnitude | size of the said medium, Although it can select suitably according to the objective, A diameter is 5-30 mm, and 10-20 mm is more preferable.
前記ロールミルとしては、例えば、２本ロールミル、３本ロールミルなどが挙げられる。これらの中でも、解砕能力の点から３本ロールミルが好ましい。３本ロールミルの運転条件としては、特に制限はなく、目的に応じて適宜選択することができるが、前ロール回転数５０ｒｐｍ〜２００ｒｐｍ、前ロール：中ロール：後ロールの各回転比が１．０：１．５：５．０〜１．０：３．０：８．０であることが好ましい。 Examples of the roll mill include a two-roll mill and a three-roll mill. Among these, a three-roll mill is preferable from the viewpoint of crushing ability. The operating conditions of the three-roll mill are not particularly limited and may be appropriately selected depending on the purpose. The rotation ratio of the front roll: 50 rpm to 200 rpm, front roll: middle roll: rear roll is 1.0. : It is preferable that it is 1.5: 5.0-1.0: 3.0: 8.0.
前記解砕機の運転時間、即ち前記解砕の時間としては、特に制限はなく、目的に応じて適宜選択することができる。例えば、前記研磨剤廃棄物中の凝集剤含有量が多い、又は含水率が低いなどの理由によりケーキの強度が高いときには、解砕の時間を長くすることで、解砕の効果を高めることができる。前記研磨剤廃棄物の成分組成や、ケーキの性状によって解砕の適正条件は変化するが、前記解砕の時間が短い場合には、充分な解砕が行われないことで、凝集状態を保った固形物の内部に酸処理の効果が及ばず、目的とする再生品（回収物）の組成や粒度が得られないことがあり、前記解砕の時間が長い場合には、解砕後の一次粒子の粉砕が過剰に進行し、再生品（回収物）の粒度が研磨剤などのリサイクル用途の目的とそぐわないことがある。 There is no restriction | limiting in particular as operation time of the said crusher, ie, the time of the said crushing, According to the objective, it can select suitably. For example, when the strength of the cake is high due to a high flocculant content in the abrasive waste or a low moisture content, the effect of crushing can be enhanced by lengthening the crushing time. it can. Although the appropriate conditions for crushing vary depending on the composition of the abrasive waste and the properties of the cake, when the crushing time is short, sufficient crushing is not performed, and the agglomerated state is maintained. The effect of acid treatment does not reach the inside of the solid matter, and the composition and particle size of the intended recycled product (recovered product) may not be obtained. The pulverization of primary particles proceeds excessively, and the particle size of the recycled product (collected material) may not be suitable for the purpose of recycling such as abrasives.
前記解砕工程により得られる解砕物の平均粒子径としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、０．５μｍ〜１０μｍが挙げられる。ここで、平均粒子径は、例えば、レーザー回折式粒度分布測定装置（一例として、島津製作所製、ＳＡＬＤ２０００Ａ）により測定することができる。 There is no restriction | limiting in particular as an average particle diameter of the crushed material obtained by the said crushing process, According to the objective, it can select suitably, For example, 0.5 micrometer-10 micrometers are mentioned. Here, the average particle diameter can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus (for example, SALD2000A manufactured by Shimadzu Corporation).
＜分離工程＞
前記分離工程は、前記酸化セリウム系研磨剤と前記ガラス研磨屑とを分離する工程であり、前記解砕工程の後に行われる。
前記分離工程としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、分級処理、固液分離処理などが挙げられる。
<Separation process>
The separation step is a step of separating the cerium oxide-based abrasive and the glass polishing waste, and is performed after the crushing step.
There is no restriction | limiting in particular as said separation process, According to the objective, it can select suitably, For example, a classification process, a solid-liquid separation process, etc. are mentioned.
−分級処理−
前記分級処理は、例えば、分級機により行うことができる。
前記分級機としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、風力分級機、慣性式分級機、篩式分級機などが挙げられる。前記分級機の一例としては、例えば、微粉を除去する能力の観点から、ケーシング内に鉛直方向に配置された駆動軸を中心軸とする分級ロータと、該分級ロータと同一の駆動軸を中心軸とし、該分級ロータの外周の分級ゾーンに該分級ロータの外周とは間隔を空けて配置された不動の螺旋状案内羽根とを有する分級機が挙げられる。かかる構造を有する分級機の具体例としては、特開平１１−２１６４２５号公報の図２、特開２００４−７８０６３号公報の図６に図示された分級機や、ホソカワミクロン社製の「ＴＳＰ」シリーズ等の市販品などが挙げられる。
前記酸化セリウム系研磨剤と比較して前記ガラス研磨屑は小さいため、前記分級処理により前記酸化セリウム系研磨剤と前記ガラス研磨屑を効率よく分離することができる。
-Classification process-
The classification process can be performed by, for example, a classifier.
There is no restriction | limiting in particular as said classifier, According to the objective, it can select suitably, For example, an air classifier, an inertia classifier, a sieve classifier etc. are mentioned. As an example of the classifier, for example, from the viewpoint of the ability to remove fine powder, a classifying rotor having a driving shaft arranged in a vertical direction in a casing as a central axis, and a driving shaft identical to the classifying rotor as a central axis And a classifier having a stationary spiral guide blade disposed in the classification zone on the outer periphery of the classification rotor and spaced from the outer periphery of the classification rotor. Specific examples of the classifier having such a structure include the classifier shown in FIG. 2 of JP-A-11-216425, FIG. 6 of JP-A-2004-78063, the “TSP” series manufactured by Hosokawa Micron, and the like. Of commercial products.
Since the glass polishing waste is smaller than the cerium oxide abrasive, the classification treatment can efficiently separate the cerium oxide abrasive and the glass abrasive waste.
−固液分離処理−
前記固液分離処理は、前記解砕工程により解砕された前記酸化セリウム系研磨剤と前記ガラス研磨屑を含む液分とを分離する工程である。
前記固液分離処理は、例えば、吸引濾過、加圧濾過、沈降分離、遠心分離、水洗などにより行うことができる。
前記固液分離処理では、前記酸化セリウム系研磨剤と前記ガラス研磨屑との大きさの違いを利用し、前記酸化セリウム系研磨剤を含む固体と、前記ガラス研磨屑を含む液分とを分離することができる。
-Solid-liquid separation process-
The said solid-liquid separation process is a process of isolate | separating the said cerium oxide type abrasive | polishing agent crushed by the said crushing process, and the liquid component containing the said glass grinding | polishing waste.
The solid-liquid separation treatment can be performed by, for example, suction filtration, pressure filtration, sedimentation separation, centrifugation, washing with water, and the like.
In the solid-liquid separation process, the solid containing the cerium oxide abrasive and the liquid containing the glass abrasive waste are separated using the difference in size between the cerium oxide abrasive and the glass abrasive waste. can do.
前記酸化セリウム系研磨剤を含有する回収物における全希土類酸化物（ＴＲＥＯ）の含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましい。前記含有量が、９０質量％未満であると、前記回収物を研磨剤として再利用した際に、研磨剤としての性能に影響を及ぼすこと、又は不純物成分による研磨への影響があることがある。
ここで、前記全希土類酸化物（ＴＲＥＯ）とは、酸化セリウム、酸化ランタン、及び酸化プラセオジムを意味し、前記全希土類酸化物（ＴＲＥＯ）の含有量とは、酸化セリウム、酸化ランタン、及び酸化プラセオジムの合計含有量を意味する。
The total rare earth oxide (TREO) content in the recovered material containing the cerium oxide-based abrasive is not particularly limited and may be appropriately selected depending on the intended purpose, but is 90% by mass or more. Preferably, it is 95 mass% or more. When the content is less than 90% by mass, when the recovered material is reused as an abrasive, the performance as an abrasive may be affected, or polishing by an impurity component may be affected. .
Here, the total rare earth oxide (TREO) means cerium oxide, lanthanum oxide, and praseodymium oxide, and the total rare earth oxide (TREO) content means cerium oxide, lanthanum oxide, and praseodymium oxide. The total content of
前記回収物の前記全希土類酸化物における酸化セリウムの含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、７０質量％以上であることが、研磨剤における有効成分としての酸化セリウムの含有量が高く、再生された材料としての機能に優れる点で好ましい。 There is no restriction | limiting in particular as content of the cerium oxide in the said all rare earth oxides of the said collection | recovery, Although it can select suitably according to the objective, It is 70 mass% or more as an active ingredient in an abrasive | polishing agent. The cerium oxide content is high, and this is preferable because of its excellent function as a regenerated material.
前記酸化セリウム系研磨剤を含有する回収物の性状としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、乾燥粉体、含水ケーキ、スラリーなどが挙げられる。酸化セリウム系研磨剤を使用する工程や企業において、乾燥粉体であることが都合がよければ、前記回収方法において、脱水・乾燥を行い乾燥粉体として前記回収物を得て、前記回収物を乾燥粉体として供給することも可能であるし、研磨工程で用いられるように水に分散された状態が都合がよければ、適切なパルプ濃度のスラリー状態で前記回収物を得ることで、脱水・乾燥工程の実施を省略でき低コストで前記回収物を得ることできる。 There is no restriction | limiting in particular as a property of the collection | recovery containing the said cerium oxide type abrasive | polishing agent, According to the objective, it can select suitably, For example, a dry powder, a water-containing cake, a slurry, etc. are mentioned. In a process or company that uses a cerium oxide abrasive, if it is convenient that the powder is a dry powder, in the recovery method, dehydration and drying are performed to obtain the recovered product as a dry powder. It can be supplied as a dry powder, and if it is convenient to be dispersed in water as used in the polishing process, the recovered material is obtained in a slurry state with an appropriate pulp concentration. Implementation of the drying step can be omitted, and the recovered product can be obtained at low cost.
前記回収物として得られた希土類酸化物は、研磨剤として再利用が可能である。再利用の方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記回収物をそのまま研磨剤として使用すること、及び前記回収物を新品の研磨剤に混合して使用することが挙げられる。前記回収物を新品の研磨剤に混合して使用する際には、前記回収物により研磨剤の粒度分布を調整することができる。
前記回収物として得られた希土類酸化物は、希土類酸化物の工業的原料として、また希土類酸化物を含むより工業的な付加価値の高い材料、例えば化学反応触媒の原料としても活用可能である。例えば、前記回収物として得られた希土類酸化物は、組成調製のためのプロセスを付加することで、工業的に付加価値の高い石油の流動接触分解（ＦＣＣ：Ｆｌｕｉｄ Ｃａｔａｌｙｓｔ Ｃｒａｃｋｉｎｇ）プロセスで用いられるＦＣＣ触媒（流動床接触分解触媒）などの原料としても利用可能である。
The rare earth oxide obtained as the recovered material can be reused as an abrasive. The recycling method is not particularly limited and can be appropriately selected according to the purpose. For example, the recovered material is used as an abrasive as it is, and the recovered material is mixed with a new abrasive. Use. When the recovered material is mixed with a new abrasive and used, the particle size distribution of the abrasive can be adjusted by the recovered material.
The rare earth oxide obtained as the recovered product can be used as an industrial raw material for rare earth oxides and as a more industrial value-added material containing rare earth oxides, for example, a raw material for chemical reaction catalysts. For example, the rare earth oxide obtained as the recovered product is added with a process for preparing a composition, thereby being used in an FCC (Fluid Catalytic Cracking) process of industrially high added value petroleum. It can also be used as a raw material for a catalyst (fluidized bed catalytic cracking catalyst).
以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
（実施例１）
表１に示す組成を有する酸化セリウム系研磨剤を含有するケーキ状の研磨剤廃棄物（水分量４９質量％）６０ｇを磁製ポット（ボールミル、アズワン社製、容量２，０００ｍＬ）に入れた。続いて、該磁製ポットへ、１Ｎ−塩酸１．０Ｌ、及び直径１０ｍｍのジルコニアボール５，０９６ｇ（磁製ポットの容量の８０体積％に相当）を入れた。
この磁製ポットを回転数５０ｒｐｍで２時間回転させ、解砕工程を行った。
解砕工程後の磁製ポット内の内容物（ジルコニアビーズは除く）のｐＨは１．２、固形分の平均粒子径は０．８μｍであった。
解砕工程後の磁製ポット内の内容物からジルコニアビーズを取り除いた後、その内容物をろ紙（ＡＤＶＡＮＴＥＣ社製、４Ａタイプ）を用いてろ過し、続いてろ紙上の固形物を２Ｌの水を用いて水洗した後、１０５℃で２時間乾燥して、固形の回収物を得た。
得られた回収物について、蛍光Ｘ線分析装置（株式会社リガク製、ＺＳＸ ＰｒｉｍｕｓＩＩ）を用いて組成分析を行った。また、回収物の質量を測定して、回収率を求めた。結果を表１に示す。
Example 1
60 g of cake-like abrasive waste (water content: 49% by mass) containing a cerium oxide abrasive having the composition shown in Table 1 was placed in a magnetic pot (ball mill, manufactured by AS ONE, capacity 2,000 mL). Subsequently, 1.0 L of 1N hydrochloric acid and 5,096 g of zirconia balls having a diameter of 10 mm (corresponding to 80% by volume of the capacity of the porcelain pot) were put into the porcelain pot.
The porcelain pot was rotated at a rotation speed of 50 rpm for 2 hours to perform a crushing process.
The pH of the contents (excluding zirconia beads) in the porcelain pot after the crushing step was 1.2, and the average particle size of the solid content was 0.8 μm.
After removing the zirconia beads from the contents in the porcelain pot after the crushing step, the contents are filtered using a filter paper (ADVANTEC 4A type), and then the solid matter on the filter paper is 2 L of water. After washing with water, it was dried at 105 ° C. for 2 hours to obtain a solid recovered product.
The collected material was subjected to composition analysis using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, ZSX Primus II). Further, the mass of the recovered material was measured to determine the recovery rate. The results are shown in Table 1.
（比較例１）
実施例１に用いた酸化セリウム系研磨剤を含有するケーキ状の研磨剤廃棄物と同じ研磨剤廃棄物６０ｇを２Ｌガラスビーカーに入れた。続いて、該ガラスビーカーへ、１Ｎ−塩酸１．０Ｌを入れた。
このガラスビーカーの内容物をケミスターラー（アズワン社製、高速撹拌機ＳＴ−２００）により回転数３００ｒｐｍで、１時間撹拌した。
撹拌後、篩目の目開きが５ｍｍの篩を通し、篩を通過したスラリーについて、ろ紙（ＡＤＶＡＮＴＥＣ社製、４Ａタイプ）を用いてろ過し、続いてろ紙上の固形物を２Ｌの水を用いて水洗した後、１０５℃で２時間乾燥して、固形の回収物を得た。
得られた回収物について、蛍光Ｘ線分析装置（株式会社リガク製、ＺＳＸ ＰｒｉｍｕｓＩＩ）を用いて組成分析を行った。また、回収物の質量を測定して、回収率を求めた。結果を表１に示す。
なお、篩上に残ったのは、凝集がほぐれていない研磨剤廃棄物の固形物であった。この固形物は、凝集がほぐれておらず、固形物内部の酸処理が十分ではないため、回収物としては不適であるため、回収物の質量、分析値などの評価には含めなかった。
(Comparative Example 1)
60 g of the same abrasive waste as the cake-like abrasive waste containing the cerium oxide abrasive used in Example 1 was placed in a 2 L glass beaker. Subsequently, 1.0 L of 1N hydrochloric acid was added to the glass beaker.
The contents of the glass beaker were stirred for 1 hour at a rotational speed of 300 rpm by a Chemistrar (manufactured by AS ONE, high-speed stirrer ST-200).
After stirring, the slurry having a mesh opening of 5 mm is passed through the sieve, and the slurry that has passed through the sieve is filtered using a filter paper (ADVANTEC 4A type), and then the solid matter on the filter paper is used with 2 L of water. After washing with water, it was dried at 105 ° C. for 2 hours to obtain a solid recovered product.
The collected material was subjected to composition analysis using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, ZSX Primus II). Further, the mass of the recovered material was measured to determine the recovery rate. The results are shown in Table 1.
In addition, what remained on the sieve was a solid material of abrasive waste that was not loosened. This solid was not included in the evaluation of mass, analytical value, etc. of the recovered product because it was unaggregated and was not suitable as a recovered product because the acid treatment inside the solid was not sufficient.
表１に示すとおり、実施例１においては、ＴＲＥＯ（全希土類酸化物）の回収率が８１．２質量％であり非常に高かった。一方、比較例１においては、固形物回収率が低い上に、ＴＲＥＯ（全希土類酸化物）の回収率が５１．０質量％と低かった。
また、実施例１においては、回収物中のＴＲＥＯ（全希土類酸化物）の含有率が９４．５質量％であり非常に高かった。これは、回収物中のセリウム系研磨剤の純度が高い、すなわち不純物が少ないことを示す。
また、実施例１で得られた回収物の平均粒子径は０．８μｍであった。ハードディスクの研磨に使用される研磨剤の平均粒子径は、一般的に、０．７μｍ〜１．０μｍ程度であることから、本発明の回収方法により得られた回収物は、そのままでも再利用可能であると考えられる。
As shown in Table 1, in Example 1, the recovery rate of TREO (total rare earth oxide) was 81.2% by mass, which was very high. On the other hand, in Comparative Example 1, the solids recovery rate was low, and the TREO (total rare earth oxide) recovery rate was as low as 51.0% by mass.
In Example 1, the content of TREO (total rare earth oxide) in the recovered material was 94.5% by mass, which was very high. This indicates that the purity of the cerium-based abrasive in the recovered material is high, that is, there are few impurities.
Moreover, the average particle diameter of the recovered material obtained in Example 1 was 0.8 μm. Since the average particle size of the abrasive used for polishing the hard disk is generally about 0.7 μm to 1.0 μm, the recovered material obtained by the recovery method of the present invention can be reused as it is. It is thought that.
本発明の酸化セリウム系研磨剤の回収方法は、簡易な工程であり、更に酸化セリウム系研磨剤の回収効率、特に酸化セリウム系研磨剤に含有される希土類酸化物の回収効率が優れることから、研磨剤廃棄物からの酸化セリウム系研磨剤の回収に好適に用いることができる。 The method for recovering the cerium oxide-based abrasive of the present invention is a simple process, and furthermore, the recovery efficiency of the cerium oxide-based abrasive, particularly the recovery efficiency of the rare earth oxide contained in the cerium oxide-based abrasive is excellent. It can be suitably used for recovering a cerium oxide-based abrasive from abrasive waste.
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