JP5679158B2 - 希土類金属の溶媒抽出用有機相の製造方法 - Google Patents
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 66
- 239000012074 organic phase Substances 0.000 title claims description 55
- 238000000638 solvent extraction Methods 0.000 title claims description 42
- 150000002910 rare earth metals Chemical class 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 29
- 230000008569 process Effects 0.000 title claims description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 42
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 38
- 238000000605 extraction Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000007810 chemical reaction solvent Substances 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 125000005265 dialkylamine group Chemical group 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
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- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 6
- WBZVQGYKIVWFGQ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)acetic acid Chemical compound NC(=O)COCC(O)=O WBZVQGYKIVWFGQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 claims description 3
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 3
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- KOHUSHSNNOEPFN-UHFFFAOYSA-N 2-[2-(dioctylamino)-2-oxoethoxy]acetic acid Chemical compound CCCCCCCCN(C(=O)COCC(O)=O)CCCCCCCC KOHUSHSNNOEPFN-UHFFFAOYSA-N 0.000 description 9
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- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 5
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- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VJLDTOPHCSPHKF-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)-2-octyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)(OCC(N)=O)CCCCCCCC VJLDTOPHCSPHKF-UHFFFAOYSA-N 0.000 description 1
- QXCAQVWXGYSKIZ-UHFFFAOYSA-N 2-(2-amino-2-oxoethoxy)-4-ethyl-2-(2-ethylhexyl)octanoic acid Chemical compound C(C)C(CC(C(=O)O)(OCC(=O)N)CC(CCCC)CC)CCCC QXCAQVWXGYSKIZ-UHFFFAOYSA-N 0.000 description 1
- SIPNYJMPXHJGBH-UHFFFAOYSA-N 2-[2-[bis(2-ethylhexyl)amino]-2-oxoethoxy]acetamide Chemical compound C(COCC(=O)N)(=O)N(CC(CCCC)CC)CC(CCCC)CC SIPNYJMPXHJGBH-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
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- MGFUUKQPXCYIJZ-UHFFFAOYSA-N C(CCCCCCC)C(C(=O)N)(OCC(=O)O)CCCCCCCC Chemical compound C(CCCCCCC)C(C(=O)N)(OCC(=O)O)CCCCCCCC MGFUUKQPXCYIJZ-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- RGZVRADFLSQOLD-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl) hydrogen phosphate Chemical compound CC(C)(C)CC(C)COP(O)(=O)OCC(C)CC(C)(C)C RGZVRADFLSQOLD-UHFFFAOYSA-N 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- HCIQUGMKXQZZMG-UHFFFAOYSA-N ethyl hexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCC HCIQUGMKXQZZMG-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
-
- 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
- Y02W30/50—Reuse, recycling or recovery technologies
Description
請求項1:
下記一般式(1)
で表されるジアルキルジグリコールアミド酸を抽出剤成分とする希土類金属抽出剤を含む希土類金属の溶媒抽出用有機相を製造する方法であって、
ジグリコール酸Xmolを、無水酢酸及び無水トリフルオロ酢酸から選ばれるエステル化剤Ymol中、モル比Y/Xを2.5以上とし、反応温度70℃以上で、反応時間1時間以上で反応させ、その後、減圧濃縮することで、未反応物及び反応残分を除去して反応中間生成物を得、
更に、前記反応中間生成物に、反応溶媒として、トルエン、キシレン、ヘキサン、イソドデカン、ケロシン及び炭素数5〜8の直鎖のアルコールから選ばれる有機溶媒を加え、前記反応中間生成物とジアルキルアミンZmolとを、モル比Z/Xを0.9以上として反応させ、反応溶媒を除去することなく、そのままで又は前記有機溶媒を更に加えて、前記有機相とすることを特徴とする希土類金属の溶媒抽出用有機相の製造方法。
請求項2:
前記有機溶媒が、ヘキサン及びケロシンから選ばれることを特徴とする請求項1記載の希土類金属の溶媒抽出用有機相の製造方法。
請求項3:
ジグリコール酸とエステル化剤との反応において、モル比Y/Xが、2.5≦Y/X≦6.5の範囲であることを特徴とする請求項1又は2記載の希土類金属の溶媒抽出用有機相の製造方法。
請求項4:
前記ジグリコール酸とエステル化剤との反応中間生成物と、ジアルキルアミンとの反応において、モル比Z/Xが、0.9≦Z/X≦1.2の範囲であることを特徴とする請求項1乃至3のいずれか1項記載の希土類金属の溶媒抽出用有機相の製造方法。
請求項5:
反応溶媒を、反応後に生成したジアルキルジグリコールアミド酸濃度COが0.1mol/L≦CO≦1.5mol/Lとなる量使用して反応させることを特徴とする請求項1乃至4のいずれか1項記載の希土類金属の溶媒抽出用有機相の製造方法。
請求項6:
前記減圧濃縮において、無水ジグリコール酸の純度が90%以上であり、かつ未反応のジグリコール酸及びエステル化剤を含むように未反応物及び反応残分を除去して反応中間生成物を得ることを特徴とする請求項1乃至5のいずれか1項記載の希土類金属の溶媒抽出用有機相の製造方法。
ジグリコール酸54g(0.40mol)、無水酢酸240g(2.35mol)の混合溶液を2時間加熱還流し、その後、過剰の無水酢酸及び反応で生成した酢酸を減圧除去した。得られた濃縮物(反応中間生成物)にトルエン300gを加え、次いで、ジオクチルアミン96g(0.40mol)を滴下し、室温で2時間攪拌することで、反応生成物のトルエン溶液を得た(実施例1)。
ジグリコール酸56g(0.42mol)、無水酢酸240g(2.35mol)の混合溶液を4時間加熱還流し、その後、過剰の無水酢酸及び反応で生成した酢酸を減圧除去した。得られた濃縮物(反応中間生成物)にヘキサン300gを加え、次いで、ジ(2−エチルヘキシル)アミン101g(0.42mol)を滴下し、室温で2時間攪拌することで、反応生成物のヘキサン溶液を得た(実施例2)。
ジグリコール酸67g(0.5mol)、無水酢酸255g(2.50mol)の混合溶液を、下記表3で示される条件にて加熱還流し、その後、過剰の無水酢酸及び反応で生成した酢酸を減圧除去した。得られた濃縮物(反応中間生成物)にトルエン200gを加え、次いで、ジ(2−エチルヘキシル)アミン121g(0.5mol)を滴下し、室温で2時間攪拌することで、反応生成物のトルエン溶液を得た。
下記表4中、Xで示される量のジグリコール酸と、下記表4中、Yで示される量の無水酢酸の混合溶液を4時間加熱還流し、その後、過剰の無水酢酸及び反応で生成した酢酸を減圧除去した。得られた濃縮物(反応中間生成物)にトルエン400gを加え、次いで、下記表4中、Zで示される量のジオクチルアミンを滴下し、室温で2時間攪拌することで、反応生成物のトルエン溶液を得た。用いたジグリコール酸の量(Xmol)と、エステル化剤である無水酢酸の量(Ymol)との比であるY/X、及びジグリコール酸の量(Xmol)とジオクチルアミンの量(Zmol)との比であるZ/Xは、表4に示すとおりである。
ジグリコール酸60g(0.45mol)、無水酢酸230g(2.25mol)の混合溶液を4時間加熱還流し、その後、過剰の無水酢酸及び反応で生成した酢酸を減圧除去した。得られた濃縮物(反応中間生成物)にケロシンAmLを加え、次いで、ジ(2−エチルヘキシル)アミン109g(0.45mol)を滴下し、室温で2時間攪拌することで、反応生成物のケロシン溶液を得た。反応溶媒であるケロシン量Aは、表5に示す通りである。
Claims (6)
- 下記一般式(1)
で表されるジアルキルジグリコールアミド酸を抽出剤成分とする希土類金属抽出剤を含む希土類金属の溶媒抽出用有機相を製造する方法であって、
ジグリコール酸Xmolを、無水酢酸及び無水トリフルオロ酢酸から選ばれるエステル化剤Ymol中、モル比Y/Xを2.5以上とし、反応温度70℃以上で、反応時間1時間以上で反応させ、その後、減圧濃縮することで、未反応物及び反応残分を除去して反応中間生成物を得、
更に、前記反応中間生成物に、反応溶媒として、トルエン、キシレン、ヘキサン、イソドデカン、ケロシン及び炭素数5〜8の直鎖のアルコールから選ばれる有機溶媒を加え、前記反応中間生成物とジアルキルアミンZmolとを、モル比Z/Xを0.9以上として反応させ、反応溶媒を除去することなく、そのままで又は前記有機溶媒を更に加えて、前記有機相とすることを特徴とする希土類金属の溶媒抽出用有機相の製造方法。 - 前記有機溶媒が、ヘキサン及びケロシンから選ばれることを特徴とする請求項1記載の希土類金属の溶媒抽出用有機相の製造方法。
- ジグリコール酸とエステル化剤との反応において、モル比Y/Xが、2.5≦Y/X≦6.5の範囲であることを特徴とする請求項1又は2記載の希土類金属の溶媒抽出用有機相の製造方法。
- 前記ジグリコール酸とエステル化剤との反応中間生成物と、ジアルキルアミンとの反応において、モル比Z/Xが、0.9≦Z/X≦1.2の範囲であることを特徴とする請求項1乃至3のいずれか1項記載の希土類金属の溶媒抽出用有機相の製造方法。
- 反応溶媒を、反応後に生成したジアルキルジグリコールアミド酸濃度COが0.1mol/L≦CO≦1.5mol/Lとなる量使用して反応させることを特徴とする請求項1乃至4のいずれか1項記載の希土類金属の溶媒抽出用有機相の製造方法。
- 前記減圧濃縮において、無水ジグリコール酸の純度が90%以上であり、かつ未反応のジグリコール酸及びエステル化剤を含むように未反応物及び反応残分を除去して反応中間生成物を得ることを特徴とする請求項1乃至5のいずれか1項記載の希土類金属の溶媒抽出用有機相の製造方法。
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