WO1998002594A1 - Selective separation of dissolved metal species with substituted 1,3,5 triazine extractants - Google Patents
Selective separation of dissolved metal species with substituted 1,3,5 triazine extractants Download PDFInfo
- Publication number
- WO1998002594A1 WO1998002594A1 PCT/GB1996/001700 GB9601700W WO9802594A1 WO 1998002594 A1 WO1998002594 A1 WO 1998002594A1 GB 9601700 W GB9601700 W GB 9601700W WO 9802594 A1 WO9802594 A1 WO 9802594A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- triazine
- metal species
- compound
- heterocyclic
- organic phase
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0295—Obtaining thorium, uranium, or other actinides obtaining other actinides except plutonium
-
- 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
Definitions
- the present invention relates to certain 1,3,5- triazines having heterocyclic substituents at the 2,4 and 6-positions, some of which are novel compounds.
- the heterocyclic groups may be nitrogen-containing heterocycles such as pyridyl or quinolyl.
- the heterocyclic substituents are selected to give the species hydrophobic character. This may be effected by the presence of hydrophobic substituents (e.g. alkyl groups) on the heterocyclic rings.
- the invention also relates to the synthesis of the triazines and their uses as solvent extraction reagents for the separation of metal-containing species.
- metal-containing complexes formed by the interaction of the above triazines with the metal- containing complexes may have different chemical and/or physical properties from the original metal-containing species, and these properties may be exploited.
- a metal species in aqueous solution or suspension may be extracted by reaction with one of the above triazines, followed by solvent extraction to take the species formed into a different, typically organic, phase.
- selectivity of the combination of the metal-containing species with the above triazines followed by solvent extraction can give an improved process for selectively removing a particular metal or class of metals e.g. separation of actinides (An), from lanthanides ( n ) .
- separation of trivalent americium [Am(III)] from trivalent europium [Eu(III)] by the above reagents is embodied in this invention.
- TPTZ 5-triazine
- the present invention is primarily concerned with the incorporation of substituents in triazines so as to improve their hydrophobic and selectivity properties.
- the invention provides a 1,3,5 triazine having a heterocyclic substituent at each of the 2,4 and 6 positions (the three substituents being the same or different). At least 1 or 2 and preferably all of the heterocyclic substituents are selected to give the triazine external hydrophobic character ( facilitating extraction into an organic phase) while providing .( together with the triazine nitrogen atoms) a polar interior.
- a generally polar heterocycle such as pyridine may have one or more hydrophobic substituents e.g. alkyl groups.
- the invention is also concerned with compounds such as 2,4,6- tripyridyl-1,3, 5-triazines wherein one or more of the pyridine rings bears at least one hydrophobic substituent.
- a pyridine-containing compound of this invention may have the general formula depicted in Figure 1 wherein the groups R, and R 2 and R 3 are the same or different and may alternatively or additionally be located in the 2, 3 or 5 positions of the pyridine rings.
- the groups may be alkyl, aryl, substituted aryl, alkoxy or heterocyclic. (Some, but not all, may be hydrogen.)
- substituents are heterocycles, then these may in turn have ( non-heterocyclic ) substituents of the types specified for R : , R 2 and R 3 .
- a molecule tends to present a highly hydrophobic exterior, with an interior containing polar nitrogen atoms which may be suitably disposed for bonding directly through coordination, or indirectly through ion-pair formation, to metal ions.
- Embodiments of this invention can.be used for extraction systems to produce compounds and wastes, the organic components of which are completely incineratable.
- the organic component usually comprises compounds containing C,H, N and oxygen but other elements such as S and P are not specifically excluded.
- the invention provides methods for preparing compounds according to the first aspect.
- a method may employ a step of trimerising a cyano-substituted heterocycle to generate a triazine ring with three heterocyclic substituents.
- a method may employ a step of introducing hydrophobic substituents into the heterocyclic rings of a tri-(2,4,6- heterocyclic)-l,2,5-triazine, e.g. by free-radical alkylation.
- the invention provides a method for extracting a metal species from a mixture comprising adding a compound according to the first aspect to the mixture so that it forms a complex with the desired metal species; partitioning the system between organic and inorganic phases; and recovering the metal species from the organic phase .
- Fig. 1 shows the formula of one class of compound embodying the invention
- Fig. 2 shows a synthetic scheme for converting 4-t- butylpyridine to the 2-cyano-der ⁇ vat ⁇ ve
- Fig. 3 is a scheme showing the trimerisation- cyclization of 2-cyano-4-t-butylpyr ⁇ d ⁇ ne.
- Figs. 4 and 5 are graphs showing the effects of nitric acid concentration and extractant concentration on distribution coefficients.
- the triazines may be prepared from the cyclisation of the corresponding cyano compound.
- E.g. 2,4, 6-tri-(4-t-butyl)-l,3,4-tr ⁇ azme ( TtBPTZ ) may be synthesised by cyclisation of the 2-cyano-4- tertbutylpyridine compound.
- TtBPTZ 6-tri-(4-t-butyl)-l,3,4-tr ⁇ azme
- one stage in the preparation may be to prepare the corresponding alkyl cyano compound by alkylation of 2-cyanopyridine.
- the substituted pyridine may be cyanidised through the N- oxide, as shown in Fig. 2.
- M * for (4) has m/z equal to 161.
- Trimerisation of 2-cvano-4-tert-butylpyrid ⁇ ne (4) to TtBPTZ A possible mechanism for the trimerisation/cyclisation of 2-cyano-4-terr-butylpyridine (4) is shown in Figure 3.
- the trimerisation of (4) was carried out in a methanolic solution at 65 °C with a pressure of about 10 kbar for 6 days. Yields ranged from 5-60% depending on the presence of a suitable ammonium salt with an active hydrogen atom. This increased the rate of formation of TtBPTZ.
- High pressure cyclisation of (4) to TtPTZ proceeded via the addition of methanol to form a pyridyliminoester (5).
- di erised to (6) di erised to (6).
- the dimer (6) then added on a further molecule of the ester ( 5 ) to form TtBPTZ.
- TtBPTZ Thin layer chromatography using hexane/diethyl ether (1:1) revealed that four different components were present in the reaction mixture after trimerisation.
- a flash chromatography column with silica gel as stationary phase was set up to separate the components. The first fraction was isolated by running 100% hexane; the second with hexane/diethyl ether (1:1); the third with 100% diethyl ether and finally the last fraction, of TtBPTZ, with methanol.
- TtPBTZ was characterised by mass spectrometry; m.pt., FT-IR spectroscopy, elemental analysis and 400 Mhz NMR.
- the FT-IR spectrum did not have any bands attributable to free CN groups. Found: C, 74.11;: H, 7.80; N, 17.24; C 30 H, 3 N 5 requires C, 74.96; H, 7.55; N 17.48%).
- the 400MHz NMR in deuterochloroform showed ring protons at 2(3H,d):7.58 ppm; 3(3H,d):8.S3 ppprn; 5 . ( 3H,d) : 8.86 ppm; a-the butyl hydrogens- ( 27H, s ): 1.46 ppm.
- Alkylation of TPTZ Substituents can also be introduced into the heterocyclic rings after formation of the triazine structure.
- the pyridine rings of TPTZ can be alkylated by free radical alkylation.
- Alkyl radicals e.g. .C-(CH 3 ) 3 or . C 5 H U
- Each experiment used a 2- phase system containing trace amounts of Am ⁇ : ⁇ and Eu Ii: , at room temperature.
- the aqueous phase contained nitric acid in varying amounts.
- the organic phase contained ⁇ - bromocapric acid (1 molar) and varying amounts of TPTZ or TtBPTZ, in TPH (a mixture of branches hydrocarbons, average C 12 ) .
- the results are presented in Table 1 and in Figs 4 and 5.
- Figure 5 shows the variation of distribution coefficient ( D ) with the concentration of TP TZ or TtBPTZ , for systems using 0.05 molar nitric acid as the aqueous phase.
- the separation of Am ( III ) and EU ( III ) is much b etter at low concentrations of
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9425776A GB2296917B (en) | 1994-12-21 | 1994-12-21 | Separation of actinides from lanthanides using 1,3,5-triazine derivatives |
PCT/GB1996/001700 WO1998002594A1 (en) | 1994-12-21 | 1996-07-16 | Selective separation of dissolved metal species with substituted 1,3,5 triazine extractants |
JP50570098A JP3901736B2 (en) | 1996-07-16 | 1996-07-16 | Selective separation of dissolved metal species using substituted 1,3,5 triazine extractants |
EP96924093A EP0850322B1 (en) | 1996-07-16 | 1996-07-16 | Selective separation of dissolved metal species with substituted 1,3,5 triazine extractants |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9425776A GB2296917B (en) | 1994-12-21 | 1994-12-21 | Separation of actinides from lanthanides using 1,3,5-triazine derivatives |
PCT/GB1996/001700 WO1998002594A1 (en) | 1994-12-21 | 1996-07-16 | Selective separation of dissolved metal species with substituted 1,3,5 triazine extractants |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998002594A1 true WO1998002594A1 (en) | 1998-01-22 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1996/001700 WO1998002594A1 (en) | 1994-12-21 | 1996-07-16 | Selective separation of dissolved metal species with substituted 1,3,5 triazine extractants |
Country Status (2)
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GB (1) | GB2296917B (en) |
WO (1) | WO1998002594A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2296917B (en) * | 1994-12-21 | 1998-08-26 | Univ Reading | Separation of actinides from lanthanides using 1,3,5-triazine derivatives |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0070226A1 (en) * | 1981-07-09 | 1983-01-19 | COMMISSARIAT A L'ENERGIE ATOMIQUE Etablissement de Caractère Scientifique Technique et Industriel | Process for separating trivalent actinides from trivalent lanthanides in an acidic aqueous solution |
FR2607021A1 (en) * | 1986-11-21 | 1988-05-27 | Commissariat Energie Atomique | Process for selective extraction of transition metals from acidic solutions using polydentate nitrogenous ligand systems and cation exchangers |
US5510091A (en) * | 1993-01-05 | 1996-04-23 | Japan Atomic Energy Research Institute | Method of separating transplutonium elements from lanthanides in acidic solutions by solvent extraction |
GB2296917A (en) * | 1994-12-21 | 1996-07-17 | Univ Reading | 1,3,5-Triazines useful for extracting metal species |
-
1994
- 1994-12-21 GB GB9425776A patent/GB2296917B/en not_active Expired - Fee Related
-
1996
- 1996-07-16 WO PCT/GB1996/001700 patent/WO1998002594A1/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0070226A1 (en) * | 1981-07-09 | 1983-01-19 | COMMISSARIAT A L'ENERGIE ATOMIQUE Etablissement de Caractère Scientifique Technique et Industriel | Process for separating trivalent actinides from trivalent lanthanides in an acidic aqueous solution |
FR2607021A1 (en) * | 1986-11-21 | 1988-05-27 | Commissariat Energie Atomique | Process for selective extraction of transition metals from acidic solutions using polydentate nitrogenous ligand systems and cation exchangers |
US5510091A (en) * | 1993-01-05 | 1996-04-23 | Japan Atomic Energy Research Institute | Method of separating transplutonium elements from lanthanides in acidic solutions by solvent extraction |
GB2296917A (en) * | 1994-12-21 | 1996-07-17 | Univ Reading | 1,3,5-Triazines useful for extracting metal species |
Non-Patent Citations (4)
Title |
---|
CHEMICAL ABSTRACTS, vol. 53, no. 18, 25 September 1959, Columbus, Ohio, US; abstract no. 17146g, XP002027360 * |
CHEMICAL ABSTRACTS, vol. 65, no. 8, 10 October 1966, Columbus, Ohio, US; abstract no. 12205g, XP002027361 * |
F.H. CASE AND E. KOFT: "The synthesis of certain substituted 1,3,5-triazines containing the ferroin group", J. AM. CHEM. SOC., vol. 81, 1959, pages 905 - 906 * |
FRANCIS H. CASE: "preparation of triazines related to 6-cyano-2,2'-bipyridine", J. ORG. CHEM., vol. 31, no. 7, 1966, pages 2398 - 2400 * |
Also Published As
Publication number | Publication date |
---|---|
GB2296917A (en) | 1996-07-17 |
GB9425776D0 (en) | 1995-02-22 |
GB2296917B (en) | 1998-08-26 |
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