JP6478113B2 - Recovery method of rare earth elements - Google Patents
Recovery method of rare earth elements Download PDFInfo
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- JP6478113B2 JP6478113B2 JP2015186174A JP2015186174A JP6478113B2 JP 6478113 B2 JP6478113 B2 JP 6478113B2 JP 2015186174 A JP2015186174 A JP 2015186174A JP 2015186174 A JP2015186174 A JP 2015186174A JP 6478113 B2 JP6478113 B2 JP 6478113B2
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 130
- 238000000034 method Methods 0.000 title claims description 41
- 238000011084 recovery Methods 0.000 title claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 101
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 33
- 239000002893 slag Substances 0.000 claims description 33
- 239000003513 alkali Substances 0.000 claims description 28
- 229910017082 Fe-Si Inorganic materials 0.000 claims description 27
- 229910017133 Fe—Si Inorganic materials 0.000 claims description 27
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 239000004071 soot Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 238000010309 melting process Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 150000002910 rare earth metals Chemical class 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002386 leaching Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010703 silicon Substances 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052692 Dysprosium Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RCYIWFITYHZCIW-UHFFFAOYSA-N 4-methoxybut-1-yne Chemical compound COCCC#C RCYIWFITYHZCIW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
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Classifications
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、希土類磁石スクラップなどから効率よく希土類元素を回収する方法に関し、より詳しくは、希土類磁石スクラップの溶融処理によって生じるアルカリシリケートから効率よく希土類元素を回収する方法に関する。 The present invention relates to a method for efficiently recovering rare earth elements from rare earth magnet scraps and the like, and more particularly to a method for efficiently recovering rare earth elements from alkali silicate generated by melting processing of rare earth magnet scraps.
希土類元素は先端技術分野の有用な物質であるが、産出が限られていることから、廃棄物から回収して再利用することが求められている。例えば、永久磁石の一種である希土類磁石には希土類元素が多く含まれており、希土類磁石のスクラップから希土類元素が回収されている。希土類磁石を備えたモータから希土類元素を回収するには、磁石類は主に回転部に取り付けられているので、モータから取り外した回転部を加熱して磁石を消磁した後に磁石を取り外して破砕し、この破砕物から希土類元素を回収している。 Rare earth elements are useful materials in the advanced technology field, but their production is limited, so that they are required to be recovered from waste and reused. For example, rare earth magnets, which are a kind of permanent magnet, contain a large amount of rare earth elements, and rare earth elements are recovered from scraps of rare earth magnets. In order to recover rare earth elements from motors equipped with rare earth magnets, magnets are mainly attached to the rotating part, so the rotating part removed from the motor is heated to demagnetize the magnet, and then the magnet is removed and crushed. The rare earth elements are recovered from the crushed material.
希土類磁石のスクラップから希土類元素を回収する方法として、以下の方法が知られている。
（イ）希土類磁石のスクラップ等を塩酸に溶解して不溶残渣を分離した後に、酸化剤および蓚酸溶液を加え、ｐＨを調整して希土類元素を蓚酸塩として沈殿させて回収する方法（特開平01−183415号公報）
（ロ）希土類元素と鉄族元素を含む処理対象物を酸化性雰囲気中で加熱して含有金属元素を酸化物にした後、塩酸溶液を加えてｐＨ２.０未満にして加熱し、希土類元素を溶出させ、希土類元素と共に溶出した鉄族元素を沈殿させた後、固液分離して希土類元素を含む液分を回収し、この濾液に沈殿剤を加えて希土類元素を沈殿させて回収する方法（特開2012−237053号公報：特許第5741323号公報）。
（ハ）希土類元素含有物質をＢ２Ｏ３の共存下で加熱溶融し、Ｂ２Ｏ３相と、希土類元素の富化相を形成し、溶融状態の各相を分液して希土類富化相を分離し、希土類富化相から希土類を溶出させ、この希土類溶液のｐＨを調整して希土類元素塩を析出させて回収する方法（特開2013−199698号公報）。
The following methods are known as methods for recovering rare earth elements from scraps of rare earth magnets.
(A) A method in which scraps of rare earth magnets and the like are dissolved in hydrochloric acid to separate insoluble residues, and then an oxidizing agent and an oxalic acid solution are added to adjust the pH to precipitate and collect the rare earth elements as oxalates (Japanese Patent Laid-Open No. 01). -183415)
(B) A processing object containing a rare earth element and an iron group element is heated in an oxidizing atmosphere to convert the contained metal element into an oxide, and then heated to a pH of less than 2.0 by adding a hydrochloric acid solution. Elution and precipitation of the iron group element eluted together with the rare earth element, followed by solid-liquid separation to recover the liquid containing the rare earth element, and then adding a precipitant to the filtrate to precipitate and collect the rare earth element ( JP 2012-237053 A: Patent No. 5743323).
(C) heating and melting in the presence of a rare earth element-containing substance B 2 O 3, and B 2 O 3 phase was formed enrichment phase of the rare earth elements, rare earth enriched were separated phases in the molten state A method in which phases are separated, rare earth is eluted from the rare earth-enriched phase, and the pH of the rare earth solution is adjusted to precipitate and collect a rare earth element salt (Japanese Patent Laid-Open No. 2013-199698).
しかし、上記(イ)の方法は酸溶解時に水素ガスが発生するので危険であり、さらにスクラップのほぼ全量を溶解するために多量の酸を使用する問題がある。また、上記(ロ)の方法は希土類元素と鉄の分離が面倒であり、加熱処理を繰り返す手間がかかる。さらに、上記(ハ)の方法はホウ酸を含む廃液が大量に生じるため水処理コストが増す問題がある。 However, the method (b) is dangerous because hydrogen gas is generated when the acid is dissolved, and there is a problem that a large amount of acid is used to dissolve almost the entire amount of scrap. In the method (b), separation of rare earth elements and iron is troublesome, and it takes time and effort to repeat the heat treatment. Furthermore, the method (c) has a problem that the cost of water treatment increases because a large amount of waste liquid containing boric acid is generated.
本発明の方法は、従来の希土類回収方法の問題を解消したものであり、希土類元素を安全に回収することができ、酸の使用量が少なく、希土類元素と鉄の分離性が良く、廃液処理の負担が少ない希土類元素回収方法を提供する。 The method of the present invention solves the problems of conventional rare earth recovery methods, can recover rare earth elements safely, uses less acid, has good separability between rare earth elements and iron, and waste liquid treatment To provide a method for recovering rare earth elements.
本発明は上記課題を解決した以下の希土類元素の回収方法に関する。
〔１〕アルカリ金属酸化物とシリカの混合物であって希土類元素を含有するアルカリシリケートをアルカリ浸出してシリカを溶出させ、固液分離したアルカリ浸出滓を酸溶解して希土類元素と残留シリカを溶出させ、この酸溶解液にアルカリを添加してシリカを析出させると共に希土類元素を液分に残し、固液分離した液分から希土類元素を回収することを特徴とする希土類元素の回収方法。
〔２〕希土類元素を含有するアルカリシリケートが、希土類元素含有廃棄物にＦｅ−Ｓｉ合金とアルカリ金属源およびシリカを加えて不活性ガス性雰囲気下で溶融するＦｅ−Ｓｉ溶融処理において生じたスラグである上記[１]に記載する希土類元素の回収方法。
〔３〕希土類元素を含有するアルカリシリケートをアルカリ水溶液に加え、水酸基濃度０.５モル/Ｌ以上の強アルカリ性下で、１５０℃以上に加熱して該アルカリシリケートに含まれるシリカを溶出させ、これを固液分離してアルカリ浸出滓を回収する上記[１]または上記[２]に記載する希土類元素の回収方法。
〔４〕アルカリ浸出滓をｐＨ２以下の強酸性下で酸溶解してアルカリ浸出滓に含まれる希土類元素および残留シリカを溶出させる上記[１]〜上記[３]の何れかに記載する希土類元素の回収方法。
〔５〕希土類元素および溶出シリカを含む酸溶解液にアルカリを添加してｐＨ４〜６に調整し、５０℃以上に加熱してシリカを析出させ、これを固液分離してシリカ滓を除去し、希土類元素を含む液分を回収する上記[１]〜上記[４]の何れかに記載する希土類元素の回収方法。
〔６〕希土類元素を含む回収液に、酸を添加してｐＨ１〜２に調整した後に、抽出溶媒を添加して希土類元素を抽出し回収する上記[１]〜上記[５]の何れかに記載する希土類元素の回収方法。
The present invention relates to the following rare earth element recovery methods that have solved the above problems.
[1] Alkali silicate containing rare earth elements, which is a mixture of alkali metal oxides and silica, is alkali-leached to elute silica, and the solid-liquid separated alkali leachate is acid-dissolved to elute rare earth elements and residual silica. A method of recovering a rare earth element, wherein an alkali is added to the acid solution to precipitate silica and the rare earth element is left in the liquid, and the rare earth element is recovered from the solid-liquid separated liquid.
[2] The slag generated in the Fe-Si melting process in which an alkali silicate containing a rare earth element is melted in an inert gas atmosphere by adding an Fe-Si alloy, an alkali metal source and silica to the rare earth element-containing waste. A method for recovering a rare earth element according to [1] above.
[3] An alkali silicate containing a rare earth element is added to an alkaline aqueous solution and heated to 150 ° C. or higher under strong alkalinity with a hydroxyl group concentration of 0.5 mol / L or more to elute the silica contained in the alkali silicate, The method for recovering a rare earth element according to the above [1] or [2], wherein the alkali leachate is recovered by solid-liquid separation.
[4] The rare earth element according to any one of the above [1] to [3], wherein the alkaline leaching soot is dissolved in a strong acid having a pH of 2 or less to elute the rare earth element and residual silica contained in the alkaline leaching soot. Collection method.
[5] Add an alkali to an acid solution containing rare earth elements and eluted silica to adjust to pH 4-6, and heat to 50 ° C. or higher to precipitate silica, which is solid-liquid separated to remove silica soot. The method for recovering a rare earth element according to any one of [1] to [4] above, wherein a liquid component containing the rare earth element is recovered.
[6] The solution according to any one of [1] to [5] above, wherein an acid is added to a recovery liquid containing a rare earth element to adjust the pH to 1-2, and then an extraction solvent is added to extract and recover the rare earth element. A method for recovering rare earth elements as described.
〔具体的な説明〕
以下、本発明の希土類元素回収方法を具体的に説明する。本発明に係る回収方法の処理工程図を図１に示す。
本発明の回収方法は、アルカリ金属酸化物とシリカの混合物であって希土類元素を含有するアルカリシリケートをアルカリ浸出してシリカを溶出させ、固液分離したアルカリ浸出滓を酸溶解して希土類元素と残留シリカを溶出させ、この酸溶解液にアルカリを添加してシリカを析出させると共に希土類元素を液分に残し、固液分離した液分から希土類元素を回収することを特徴とする希土類元素の回収方法である。
[Specific description]
Hereinafter, the rare earth element recovery method of the present invention will be described in detail. FIG. 1 shows a process chart of the recovery method according to the present invention.
The recovery method of the present invention is a mixture of an alkali metal oxide and silica, and alkaline silicate containing a rare earth element is alkali leached to elute the silica. A method for recovering a rare earth element, comprising eluting residual silica, precipitating silica by adding an alkali to the acid solution, leaving the rare earth element in the liquid, and recovering the rare earth element from the solid-liquid separated liquid It is.
本発明の回収方法は、アルカリ金属酸化物とシリカの混合物であって希土類元素を含有するアルカリシリケートを処理する。このアルカリシリケートは、希土類元素含有廃棄物にＦｅ−Ｓｉ合金とアルカリ金属源およびシリカを加えて不活性ガス性雰囲気下で溶融するＦｅ−Ｓｉ溶融処理において生じたスラグを用いることができる。 The recovery method of the present invention treats an alkali silicate containing a rare earth element, which is a mixture of an alkali metal oxide and silica. As the alkali silicate, slag generated in an Fe-Si melting process in which an Fe-Si alloy, an alkali metal source, and silica are added to a rare earth element-containing waste and melted in an inert gas atmosphere can be used.
〔溶融処理工程〕
希土類磁石のスクラップなどの希土類元素含有廃棄物に、Ｆｅ−Ｓｉ合金、炭酸ナトリウム（Na２CO３）などのアルカリ金属源、およびシリカを加えて、不活性ガス性雰囲気下で、１２５０℃〜１５５０℃に加熱してこれらを熔融すると、希土類磁石スクラップに含まれる鉄は酸化されずにＳｉと反応してＦｅ−Ｓｉ溶融合金に取り込まれ、Ｆｅ含有量が増加したＦｅ−Ｓｉ溶融合金が形成される。
[Melting process]
Add an alkali metal source such as Fe-Si alloy, sodium carbonate (Na 2 CO 3 ), and silica to a rare earth element-containing waste such as rare earth magnet scrap, and in an inert gas atmosphere, 1250 ° C. to 1550 ° C. When these are melted by heating to ° C., the iron contained in the rare earth magnet scrap reacts with Si without being oxidized and is taken into the Fe—Si molten alloy to form an Fe—Si molten alloy with an increased Fe content. The
一方、炭酸ナトリウム（Na２CO３）などのアルカリ金属源は添加したシリカと反応してアルカリシリケート溶融スラグ（Na２O−SiO２スラグ等）を形成する。また、希土類磁石スクラップに含まれる希土類元素も酸化されて希土類元素酸化物を形成し、上記アルカリシリケート溶融スラグに取り込まれる。 On the other hand, an alkali metal source such as sodium carbonate (Na 2 CO 3 ) reacts with the added silica to form an alkali silicate molten slag (Na 2 O—SiO 2 slag, etc.). In addition, rare earth elements contained in the rare earth magnet scrap are also oxidized to form rare earth element oxides, which are taken into the alkali silicate molten slag.
アルカリ金属酸化物および希土類元素酸化物が形成される酸素分圧は、酸化鉄が形成される酸素分圧より十分に低いので、不活性ガス雰囲気下でも、アルカリ金属および希土類元素が酸化される酸素分圧が保たれていれば、アルカリ金属酸化物および希土類元素酸化物が形成され、これらはアルカリシリケートスラグに取り込まれる。一方、鉄は酸化されずにＳｉと反応してＦｅ−Ｓｉ合金に取り込まれる。通常の不活性ガス雰囲気下では、鉄は酸化されずにＳｉと反応してＦｅ−Ｓｉ合金を形成し、アルカリ金属および希土類元素は酸化されてアルカリシリケートスラグに取り込まれる。このＦｅ−Ｓｉ溶融処理によって、希土類磁石スクラップ等に含まれている希土類元素と鉄はおのおのスラグと合金に分離することができる。 Since the oxygen partial pressure at which alkali metal oxides and rare earth element oxides are formed is sufficiently lower than the oxygen partial pressure at which iron oxide is formed, oxygen in which alkali metals and rare earth elements are oxidized even in an inert gas atmosphere If the partial pressure is maintained, alkali metal oxides and rare earth element oxides are formed, and these are taken into the alkali silicate slag. On the other hand, iron reacts with Si without being oxidized and is taken into the Fe—Si alloy. Under a normal inert gas atmosphere, iron is not oxidized but reacts with Si to form an Fe—Si alloy, and the alkali metal and rare earth element are oxidized and taken into the alkali silicate slag. By this Fe-Si melting treatment, the rare earth element and iron contained in the rare earth magnet scrap or the like can be separated into slag and alloy, respectively.
上記Ｆｅ−Ｓｉ溶融処理において生じるＦｅ−Ｓｉ溶融合金は、アルカリシリケートスラグより重いので、Ｆｅ−Ｓｉ溶融合金とアルカリシリケートスラグの二層に分離し、これらは何れも熔融物であるので、各々を容易に抜き出して分離回収することができる。また、ここで回収したＦｅ−Ｓｉ合金の一部を再び溶融工程に戻して利用することができる。 Since the Fe-Si molten alloy generated in the Fe-Si melting process is heavier than the alkali silicate slag, it is separated into two layers of an Fe-Si molten alloy and an alkali silicate slag, both of which are melts. It can be easily extracted and separated and recovered. In addition, a part of the Fe—Si alloy recovered here can be returned to the melting step for use.
上記溶融処理工程において用いるＦｅ−Ｓｉ合金は、鉄粉と粗粉砕したシリコン粉の混合物を、不活性ガス雰囲気下で、加熱溶融することによって得ることができる。例えば、鉄粉７５wt％と粗粉砕したシリコン２５wt％の混合物を黒鉛ルツボに装入し、アルゴン雰囲気下で、１４００℃程度に１時間加熱して溶融させた後に、冷却してＦｅ−Ｓｉ合金を得ることができる。 The Fe—Si alloy used in the melting treatment step can be obtained by heating and melting a mixture of iron powder and coarsely pulverized silicon powder in an inert gas atmosphere. For example, a mixture of 75 wt% iron powder and 25 wt% coarsely pulverized silicon is placed in a graphite crucible, heated to about 1400 ° C. for 1 hour in an argon atmosphere and melted, and then cooled to obtain an Fe—Si alloy. Can be obtained.
上記溶融工程において用いる炭酸ナトリウム（Na２CO３）などのアルカリ金属源とシリカは、Na２O−SiO２スラグの状態で用いることができる。このNa２O−SiO２スラグは、Na２CO３粉とSiO２粉を混合して大気中で１１００℃程度に加熱溶融して得ることができる。Na２CO３とSiO２をNa２O−SiO２スラグの状態で用いることによって、希土類元素の吸収が容易になり、かつＦｅ−Ｓｉ溶融合金と分離しやすくなる。 The alkali metal source such as sodium carbonate (Na 2 CO 3 ) and silica used in the melting step can be used in the state of Na 2 O—SiO 2 slag. This Na 2 O—SiO 2 slag can be obtained by mixing Na 2 CO 3 powder and SiO 2 powder and heating and melting to about 1100 ° C. in the atmosphere. By using Na 2 CO 3 and SiO 2 in the state of Na 2 O—SiO 2 slag, it becomes easy to absorb rare earth elements and easily separate from the Fe—Si molten alloy.
〔アルカリ浸出工程〕
希土類元素を含有するアルカリシリケートをアルカリ浸出してシリカを溶出させる。例えば、希土類元素を含有するアルカリシリケートをアルカリ水溶液に加え、水酸基濃度０.５モル/Ｌ以上の強アルカリ性に調整し、オートクレーブ内で１５０℃以上に加熱し、数時間撹拌し混合すると、上記アルカリシリケートに含まれるシリカが溶出する。アルカリシリケートに含まれるシリカの概ね７割程度が溶出するので、これを固液分離して溶出したＳｉを含む液分（Ｓｉ浸出液）を系外に除去して浸出残渣を回収する。
[Alkaline leaching process]
Silica is eluted by alkali leaching of an alkali silicate containing a rare earth element. For example, an alkali silicate containing a rare earth element is added to an alkaline aqueous solution, adjusted to a strong alkalinity with a hydroxyl group concentration of 0.5 mol / L or higher, heated to 150 ° C. or higher in an autoclave, stirred for several hours, and mixed. Silica contained in the silicate is eluted. Since about 70% of the silica contained in the alkali silicate is eluted, this is solid-liquid separated to remove the Si-containing solution (Si leaching solution) out of the system and recover the leaching residue.
アルカリシリケートに含まれる希土類元素はアルカリ浸出せずに大部分が浸出残渣に含まれる。また、熔融工程で分離回収したスラグは非晶質であるが、このアルカリ浸出によってスラグに含まれる希土類元素は結晶性の水酸化物や、ナトリウムやシリカとの複合酸化物に変化する。 Most of the rare earth elements contained in the alkali silicate are contained in the leaching residue without alkali leaching. The slag separated and recovered in the melting step is amorphous, but the rare earth element contained in the slag is changed into a crystalline hydroxide or a composite oxide with sodium or silica by this alkali leaching.
アルカリシリケートをアルカリ浸出せずに酸と混合しても、液分に溶解する希土類元素はアルカリシリケートに含まれる量の約３割程度である。溶融処理工程と酸溶解工程との間にアルカリ浸出工程を加えることによって、酸溶解工程において希土類元素の約９割以上を浸出させることができる。希土類元素がアルカリ浸出工程において結晶性の水酸化物や、ナトリウムやシリカとの複合酸化物に変化するためと考えられる。 Even if the alkali silicate is mixed with an acid without leaching with alkali, the rare earth element dissolved in the liquid is about 30% of the amount contained in the alkali silicate. By adding an alkali leaching step between the melt treatment step and the acid dissolution step, about 90% or more of the rare earth element can be leached in the acid dissolution step. This is probably because the rare earth element is changed to a crystalline hydroxide or a composite oxide with sodium or silica in the alkali leaching process.
〔酸溶解工程〕
上記アルカリ浸出滓を酸溶解して、アルカリ浸出滓に含まれている希土類元素および残留シリカを溶出させる。例えば、アルカリ浸出滓を水に混合し、これに塩酸を添加してｐＨ２以下の強酸性下にすると、アルカリ浸出滓に含まれる希土類元素および残留シリカが溶出する。
[Acid dissolution step]
The alkali leached soot is acid-dissolved to elute rare earth elements and residual silica contained in the alkali leached soot. For example, when alkaline leaching soot is mixed with water and hydrochloric acid is added thereto to bring it to a strong acidity of pH 2 or lower, rare earth elements and residual silica contained in the alkaline leaching soot are eluted.
〔シリカ析出工程〕
希土類元素および溶出シリカを含む酸溶解液にアルカリを添加し、ｐＨ４〜６に調整してシリカを析出させる。例えば、上記酸溶解液に水酸化ナトリウム溶液を添加してｐＨ４〜５に調整し、液温５０℃以上に加温しながら数時間撹拌し混合すると、シリカが析出する。これを固液分離してシリカ滓を除去し、希土類元素を含む液分を回収する。回収した液分には、希土類磁石スクラップに含まれていた希土類元素の約９０％前後が含まれている。
[Silica precipitation step]
An alkali is added to an acid solution containing a rare earth element and eluted silica, and the pH is adjusted to 4 to 6 to precipitate silica. For example, when a sodium hydroxide solution is added to the acid solution to adjust to pH 4 to 5, and the mixture is stirred for several hours while being heated to a liquid temperature of 50 ° C. or higher, silica is precipitated. This is subjected to solid-liquid separation to remove silica soot, and a liquid component containing rare earth elements is recovered. The recovered liquid contains about 90% of the rare earth elements contained in the rare earth magnet scrap.
〔溶媒抽出工程〕
シリカ滓を除去した液分から溶媒抽出によって希土類元素を回収することができる。例えば、シリカ滓を除去した液分に塩酸を加えてｐＨ１〜２に調整した後に、抽出溶媒（商品名ＰＣ−８８Ａ等）を添加して希土類元素を抽出することができる。
[Solvent extraction step]
Rare earth elements can be recovered from the liquid from which the silica soot has been removed by solvent extraction. For example, after adding hydrochloric acid to the liquid from which the silica soot has been removed to adjust the pH to 1-2, an extraction solvent (trade name PC-88A or the like) can be added to extract the rare earth element.
本発明の回収方法によれば、希土類磁石スクラップなどの希土類含有廃棄物から、純度９９.９％以上の希土類元素を、９０％以上の収率で回収することができる。
本発明の回収方法は、希土類磁石スクラップなどを酸溶解する方法ではないため、酸の使用量が少なく、またＢ２Ｏ３の共存下で加熱溶融する方法ではないのでホウ酸が発生せず、廃液処理の負担が少ない。
本発明の回収方法は、希土類磁石スクラップなどに含まれる鉄はＦｅ−Ｓｉ合金に取り込ませ、希土類元素はアルカリシリケートスラグに取り込ませるので、希土類元素と鉄の分離性が良く、鉄などの不純物が少ない高純度の希土類元素を収率良く回収することができる。
According to the recovery method of the present invention, a rare earth element having a purity of 99.9% or more can be recovered from a rare earth-containing waste such as a rare earth magnet scrap in a yield of 90% or more.
Since the recovery method of the present invention is not a method of dissolving rare earth magnet scraps or the like with acid, boric acid is not generated because the amount of acid used is small, and it is not a method of heating and melting in the presence of B 2 O 3 , Less burden of waste liquid treatment.
In the recovery method of the present invention, the iron contained in the rare earth magnet scrap or the like is incorporated into the Fe-Si alloy, and the rare earth element is incorporated into the alkali silicate slag, so that the separation of the rare earth element and iron is good, and impurities such as iron are present. A small amount of high-purity rare earth elements can be recovered with good yield.
〔実施例１〕
下記(イ)〜(ト)の工程に従って希土類元素を回収した。処理工程を図１に示す。結果を表１に示す。
(イ)Fe-Si合金調製
鉄粉と粗粉砕したシリコンを、Fe75wt％、Si25wt％の割合に混合した後、黒鉛ルツボに装入し、電気炉内、アルゴン雰囲気下で、１４００℃にて１時間保持した。その後、試料を急冷しＦｅ−Ｓｉ合金を回収した。
(ロ)Na ２ O−SiO ２ スラグ調製
Na２CO３とSiO２の混合物（Na２O：28wt％、SiO２：59wt％）を白金るつぼに装入し、電気炉を用い、大気中で１１００℃にて加熱溶融してNa２O−SiO２スラグを調製した。１時間後に試料を取り出し、ルツボ内の溶融スラグを鉄板上に注ぎ回収した。
(ハ)希土類磁石の溶融処理
希土類磁石[Ａ]５ｇを粉砕し、上記(イ)で調製したFe−Si合金１２ｇと、上記(ロ)で調製したNa２O−SiO２スラグ７.５ｇと、上記希土類磁石粉砕物とを混合して黒鉛ルツボに装入し、これを電気炉に入れ、アルゴンガスを３００mL/minの流量で炉内導入しながら１３００℃で５時間保持した。処理後、ルツボを電気炉から取り出して水急冷し、スラグ[Ｂ]１０ｇとFe−Si合金[Ｃ]１５.５ｇを回収した。上記希土類磁石破砕物の鉄および希土類元素の含有量を表１に示す。回収したスラグ[Ｂ]およびFe−Si合金[Ｃ]のシリコンおよび希土類元素(Nd、Dy)の含有量、移行率を表１に示す。上記スラグのＸＲＤ分析チャートを図２に示す。
(ニ)スラグのアルカリ浸出
上記溶融処理で回収したスラグ１０ｇを粉砕して水酸化ナトリウム水溶液５０mL（NaOH濃度１１０g/L)と混合し、オートクレーブに入れて加熱し、１５０℃で６時間混合した。処理後に放冷し濾過して、４３mLのＳｉ浸出液[Ｄ]と７.５ｇのアルカリ浸出滓[Ｅ]を回収した。該アルカリ浸出滓[Ｅ]のシリコンおよび希土類元素(Nd、Dy)の含有量、移行率を表１に示す。表１に示すように、スラグ[Ｂ]に含まれていた希土類元素の９９wt％以上はアルカリ浸出滓[Ｅ]に回収された。該アルカリ浸出滓[Ｅ]のＸＲＤ分析チャートを図３に示す。上記スラグ[Ｂ]とアルカリ浸出滓[Ｅ]のＸＲＤ分析チャートを比較すると、非晶質であったスラグは、アルカリ浸出によって希土類元素が結晶性のよい水酸化物に変質していることが分かる。例えば、ネオジムを含む非晶質のアルカリシリケートが結晶性の水酸化ネオジム〔Nd(OH)３〕や〔NaNd９(SiO４)６O２〕に変質している。
(ホ)希土類元素の酸溶解
アルカリ浸出滓[Ｅ]７.５ｇを１００mLの水に混合し、塩酸を添加してｐＨ２に調整し、２時間混合してアルカリ浸出滓[Ｅ]に含まれるシリカおよび希土類元素を溶出させた。
(ヘ)シリカ析出
上記(ホ)の酸溶解液に水酸化ナトリウム液を添加しｐＨ５に調整し、液温を６０℃に加熱しながら３時間混合してシリカを析出させた。放冷後に固液分離してシリカ滓[Ｆ]２ｇと濾液[Ｇ]９４mLを回収した。該シリカ[Ｆ]滓に含まれるシリコンおよび希土類元素(Nd、Dy)の含有量、移行率を表１に示す。回収した濾液[Ｇ]に含まれるシリコンおよび希土類元素の含有量、移行率を表１に示す。
(ト)溶媒抽出
上記(ヘ)の濾液に塩酸を加えてｐＨ２に調整し、溶媒（商品名PC-88A）を添加して希土類元素を溶媒に抽出した。純度９９.９％のＮｄおよびＤｙを回収した。
[Example 1]
Rare earth elements were recovered according to the following steps (a) to (g). The processing steps are shown in FIG. The results are shown in Table 1.
(A) Preparation of Fe-Si alloy Iron powder and coarsely pulverized silicon were mixed at a ratio of Fe 75 wt% and Si 25 wt%, and then charged into a graphite crucible, and 1400 in an electric furnace under an argon atmosphere. Hold at 1 ° C. for 1 hour. Thereafter, the sample was rapidly cooled to recover the Fe—Si alloy.
(B) Preparation of Na 2 O—SiO 2 slag
Na 2 CO 3 and mixtures of SiO 2 (Na 2 O: 28wt %, SiO 2: 59wt%) was charged into a platinum crucible, using an electric furnace, and heated and melted at 1100 ° C. in air Na 2 O It was prepared -SiO 2 slag. One hour later, the sample was taken out, and the molten slag in the crucible was poured onto an iron plate and recovered.
(C) the melt processing <br/> rare earth magnet [A] 5 g of the rare-earth magnet was crushed, the a Fe-Si alloy 12g prepared in (b), the (b) Na 2 O-SiO 2 slag prepared in 7.5 g and the pulverized rare earth magnet were mixed and charged into a graphite crucible. The graphite crucible was charged into an electric furnace and maintained at 1300 ° C. for 5 hours while introducing argon gas into the furnace at a flow rate of 300 mL / min. . After the treatment, the crucible was taken out of the electric furnace and rapidly cooled with water to recover 10 g of slag [B] and 15.5 g of Fe—Si alloy [C]. Table 1 shows the contents of iron and rare earth elements in the crushed rare earth magnet. Table 1 shows the contents of silicon and rare earth elements (Nd, Dy) and the migration rate in the recovered slag [B] and Fe—Si alloy [C]. An XRD analysis chart of the slag is shown in FIG.
(D) Alkali leaching of slag 10 g of slag recovered by the above melting treatment is pulverized and mixed with 50 mL of an aqueous sodium hydroxide solution (NaOH concentration 110 g / L), heated in an autoclave and heated at 150 ° C for 6 hours. Mixed for hours. After the treatment, it was allowed to cool and filtered to recover 43 mL of Si leachate [D] and 7.5 g of alkaline leachate [E]. Table 1 shows the contents of silicon and rare earth elements (Nd, Dy) and the migration rate of the alkaline leachate [E]. As shown in Table 1, 99 wt% or more of the rare earth element contained in the slag [B] was recovered in the alkali leach [E]. FIG. 3 shows an XRD analysis chart of the alkali leached soot [E]. Comparing the XRD analysis charts of the slag [B] and the alkali leached soot [E], it can be seen that the amorphous slag has been transformed into a hydroxide with good crystallinity due to alkali leaching. . For example, amorphous alkali silicate containing neodymium has been altered to crystalline neodymium hydroxide [Nd (OH) 3 ] or [NaNd 9 (SiO 4 ) 6 O 2 ].
(E) Acid dissolution of rare earth element 7.5 g of alkaline leachate [E] is mixed with 100 mL of water, adjusted to pH 2 by adding hydrochloric acid, mixed for 2 hours and mixed with alkaline leachate [E]. The silica and rare earth elements contained in were eluted.
(F) Silica precipitation A sodium hydroxide solution was added to the acid solution of (e) above to adjust the pH to 5, and the mixture was mixed for 3 hours while heating the solution temperature to 60C to precipitate silica. After cooling, solid-liquid separation was performed to recover 2 g of silica gel [F] and 94 mL of filtrate [G]. Table 1 shows the contents and migration rates of silicon and rare earth elements (Nd, Dy) contained in the silica [F] soot. Table 1 shows the contents and migration rates of silicon and rare earth elements contained in the collected filtrate [G].
(G) Solvent extraction Hydrochloric acid was added to the filtrate of (f) above to adjust the pH to 2, and a solvent (trade name PC-88A) was added to extract rare earth elements in the solvent. Nd and Dy with a purity of 99.9% were recovered.
〔実施例２〕
実施例１で回収したFe−Si合金（Fe：81wt％、Si：19wt％）１１ｇとシリコン塊０.８ｇを用い、実施例１で用いた希土類磁石粉砕物[Ａ２]５ｇと、実施例１のNa２O−SiO２スラグ７.５ｇとの混合物を電気炉で１３００℃に加熱して溶融させ、電気炉から取り出して水急冷し、スラグ[Ｂ２]１０ｇとFe−Si合金[Ｃ２]１５.５ｇを回収した。このスラグ[Ｂ２]１０ｇを粉砕して水酸化ナトリウム水溶液５０mL（NaOH濃度110g/L)と混合し、オートクレーブに入れて加熱し、１５０℃で６時間混合した。処理後に放冷し濾過して、４４mLのＳｉ浸出液[Ｄ２]と７.３ｇのアルカリ浸出滓[Ｅ２]を回収した。このアルカリ浸出滓[Ｅ２]７.３ｇを１００mLの水に混合し、塩酸を添加してｐＨ２に調整し、２時間混合してアルカリ浸出滓[Ｅ２]に含まれるシリカおよび希土類元素を溶出させた。この酸溶解液に水酸化ナトリウム液を添加しｐＨ５に調整し、液温を６０℃に加熱しながら３時間混合してシリカを析出させた。放冷後に固液分離してシリカ滓[Ｆ２]２.０ｇと濾液[Ｇ２]９８mLを回収した。この濾液に塩酸を加えてｐＨ２に調整し、溶媒（商品名PC-88A）を添加して希土類元素を溶媒に抽出し、純度９９.９％のＮｄおよびＤｙを回収した。この結果を表２に示した。
[Example 2]
Using 11 g of the Fe—Si alloy (Fe: 81 wt%, Si: 19 wt%) and 0.8 g of silicon lump recovered in Example 1, 5 g of the pulverized rare earth magnet [A2] used in Example 1, and Example 1 A mixture of 7.5 g of Na 2 O—SiO 2 slag was heated to 1300 ° C. in an electric furnace to be melted, taken out of the electric furnace and quenched with water, 10 g of slag [B2] and Fe—Si alloy [C2] 15 .5g was recovered. 10 g of this slag [B2] was pulverized, mixed with 50 mL of an aqueous sodium hydroxide solution (NaOH concentration 110 g / L), heated in an autoclave, and mixed at 150 ° C. for 6 hours. After the treatment, it was allowed to cool and filtered to recover 44 mL of Si leachate [D2] and 7.3 g of alkaline leachate [E2]. 7.3 g of this alkaline leachate [E2] was mixed with 100 mL of water, hydrochloric acid was added to adjust the pH to 2, and the mixture was mixed for 2 hours to elute the silica and rare earth elements contained in the alkaline leachate [E2]. . Sodium hydroxide solution was added to this acid solution to adjust to pH 5, and the mixture was mixed for 3 hours while heating the solution temperature to 60 ° C. to precipitate silica. After cooling, solid-liquid separation was performed to recover 2.0 g of silica gel [F2] and 98 mL of filtrate [G2]. Hydrochloric acid was added to the filtrate to adjust the pH to 2, and a solvent (trade name PC-88A) was added to extract rare earth elements into the solvent to recover Nd and Dy having a purity of 99.9%. The results are shown in Table 2.
Claims (6)
The rare earth element according to any one of claims 1 to 5, wherein an acid is added to the recovery liquid containing the rare earth element to adjust to pH 1-2, and then an extraction solvent is added to extract and collect the rare earth element. Collection method.
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