AU609462B2 - Proton ionizable macrocyclic compositions and selective competitive separation of desired metal ions from mixtures thereof with other ions - Google Patents

Description

f tu*I i n I I~~I5~J.r1 VA 'I 1 fl'.~h~I STA/5856T

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4 i l i: ild' I 9462 S F Ref: 48818 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class 4 1 8 4, Complete Specification Lodged: Accepted: Published: Priority: Related Art: amendments made under Section 40 nd correct for printing I E

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#4 Name and Address of Applicant: Brigham Young University Provo Utah 84602UNITED STATES OF AMERICA Address for Service: Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Proton lonizable Macrocyclic Compositions and Selective Competitive Separation of Desired Metal Ions from Mixtures thereof with other Ions The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3

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i: 51-- i r: c~

ABSTRACT

The invention has composition of matter and process aspects. The composition of matter aspect relates to compounds selected from the class consisting of

X

H

N- N

)"NS

0 H 0. 0 OOnR where X 0 or S; n integers from 0 to 3, inclusive; R CxH2x+l JO,, x integers from 6 to 18 0 0 0 00 where n integers from 0 to 3, inclusivt R CxH2x+l x integers from 6 to 18 O- O where n integers from 1 to 4 inclusive R CxH2x+l x integers from 6 to 18 -1- 11 0 where X 0 or S; n integers from 0 to 3, inclusive;

R

1 H or Blocker;

R

2

CH

2

OCH

2

CH=CH

2

CH

2 0(CH 2 3 Si(R3) 2 C1,

CH

2

O(CH

2 3 Si(R4) 20- SILICA GEL;

N-N

0 0 where n integers from 0 to 3, inclusive;

R

1 H or Blocker; 2 R CH 2

OCH

2

CH=CH

2 CH20(CH 2 Si(R 3 )2 Cl,

C;

2 0(CH2) 3 Si(R 4 )20- SILICA GEL;

R

3

CH

3 or Cl;

R

4

CH

3 or 0- SILICA GEL 0

N

0- -0 0 0 o-

R

2 /n where n integers from 1-4, inclusive;

R

l H or Blocker; 2 R CH 2

OCH

2

CH=CH

2

CH

2 0(CH 2 3 Si(R 3 2

C,

CH

2 0(CH 2 3 Si(R 4 2 0- SILICA GEL;

R

3

CH

3 or Cl;

R

4

CH

3 or 0- SILICA GEL 0a 00 00 0 0 0 00 10' 00 00 0 0 0 o 0 ~000 0040

R

3

CH

3 or Cl;

R

4

CH

3 or 0- SILICA GEL 0 The process aspect involves the use of these compounds to complex with and separate a desired selected ion from a multiple ion solution, breaking the complex to free the desired ion and recovering the freed desired ion. This process can be carried out in these ways: as *go. ligands in a liquid membrane phase for selectively and competitively S' separating desired metal ions from mixtures with other ions in a separate source phase and transporting these ions to a separate receiving phase, with both of which the liquid membrane phase is in interfacial contact long enough to effect substantial removal of the desired ions from the source o phase and transporting them to the receiving phase from which they are S recovered, as covalently bonded to silica gel supported in a column through which the multiple ion solution is first flowed, followed by receiving liquid, and (C) 1A as ligand in an organic liquid filling pores or apertures in the wall of a hollow f iber in a bunidle of hollow fibers on opposite sides of which flow the multiple ion solution and the receiving liquid.

PROTON IONIZABLE MACROCYCLIC COMPOUNDS AND SELECTIVE COMPETITIVE SEPARATION OF DESIRABLE METAL IONS FROM MIXTURES THEEOF WITH OTHER IONS

INTRODUCTION

The present invention comprises a composition of matter and a process of using it. The composition of matter comprises certain proton-ionizable macrocyclic compounds. The process comprises separating a selected ion from a plurality of other ions in a multiple ion solution by bringing the multiple ion solution into contact with a compound of the invention in a number of different embodiments, each embodiment being capable .of carrying out the unifying principle involving separating a desired ion from a multiple ion solution, a mixture thereof with other ions under selective, competitive conditions. Specific embodiments disclosed herein 4 include carrying out the process by bringing the multiple ion solution into U 0 contact with a compound of the invention as a ligand .in a liquid membrane for selective, competitive transport of desired metal ions complexed with said ligand from a separate source phase containing the mixture of ions to a separate receiving phase, where the separation means may be only the liquid membrane, as in an emulsion, or both a physical barrier and the liquid membrane as in an apparatus having a receiving vessel with an open-ended tube located in it with the liquid membrane phase immersing the lower end of the tube which contains one of the other phases and is surrounded by the other phase, as an addition compound to silica gel in a separation column through which the mixture is first flowed to complex the desired ion with said compound followed by the flow through the column of a receiving liquid to break the complex, dissolve the desired ions and carry them out of the column, and as a ligand in a liquid phase located in pores or apertures in the wall of each hollow filament in a bundle of filaments through which one of the other two phases. flows while the other phase flows over the outsides of them. In each embodiment, the desired transported metal ions are recovered. from the receiving phase by well known procedures.

More particularly, embodiment of the process comprises the selective, competitive tzanspoit of desired metsal ions from a source phase containing a mixtuDre thereof with othe r ions by establishing a separate *sovi'ce phase containing the mixture of ions to be separated, a separate receiving phase, and a liquid membrane phase containing at least one such compound, a macrocyclic inner cavity proton-ionizable pyridone ligand, in a liquid membrane solvent phase interfacing with said source and receiving phases, maintaining the interfacial. contact for a period of time long enough to transport a substantial part of the desired meta]l ions from ,the source phase to the receiving phase. This embodiment of the process. may *.be referred to as selective transport of metal ions from a separate source phase to a separate receiving phase by a proton-metal ion coupled mechanism through a liquid membi-ane phase -using macrocyclic ligands which have an ionizable proton. Embodiment of the process comprises forming a chemical covalent bond between a silica gel and at least one *of the compounds, placing the resulting bonded silica gel in a tall column, causing the mixture of ions to flow through the column where the desired ions comp lex with the bonded silica gel which separates them from the rest of the mixture which flows out of the column, then flowing a receiving liquid through the column to break the complex, dissolve and carry out of the column the desired ions. Embodiment involves filling the apertures in the wall of 2 I. II each filament of a bundle of hollow filaments with a liquid containing the macrocyclic compound of the invention, flowing one of the two other phases through the filaments and the other phase over them while the macrocyclic compounds in the apertures transport the desired ions from the source phase to the receiving phase. In each embodiment the desired metal ions are recovered from the receiving phase by well known procedures.

BACKGROUND OF THE INVENTION The fact is known that cyclic proton-ionizable pyridone polyethers, other cyclic polyethes. and macrocyclic ligands are characterized by their size-related selectivity in binding cations, as noted by J. D. Lamb, R. M.

Izatt, J. J. Christensen, D. J. Eatough, in COORDINATION CHEMISTRY OF MACROCYCLIC COMPOUNDS, edited by G. A. Melson, PLENUM, pages 145 217 S(1979). A few macrocyclic compounds having a replaceable proton on a side 4 4 chain have been disclosed for selective competitive alkali metal interactions such as in an article entitled HIGH LITHIUM SELECTIVITY IN COMPETITIVE ALKALI-METAL SOLVENT EXTRACTION BY LIPOPHILIC CROWN CARBOXYLIC ACIDS by Richard A. Bartch, Bronislaw P. Czech, Sang Ihn Kang, Louis E.

Stewart, Wladyslaw Walkowiak, Witold A. Charewicz, Gwi Suk Heo and Byungki Son, J. Am. Chem. Soc., 1985, 107, 4997 4998. However, no proton-ionizable macrocycles of the type disclosed in the invention have been previously reported. Articles such ais those entitled ION-CHROMATOGRAPHIC SEPARATION OF SILICA GRAFTED WITH BENZO-18-CROWN-6 CROWN ETHER by M. Lauth and Ph.

Germain, J. Liquid Chromatogr., 1985, 8, 2403 2415, and ION CHROMATOGRAPHY ON POLY (CROWN ETHER-MODIFIED) SILICA POSSESSING HIGH AFFINITY FOR SODIUM by M. Nakajima, K. Kumura, E. Hayata, and T. Shono, J. Liquid Chromatogr., 1984, 7, 2115 2125, have disclosed the bonding of crown ethers to silica, gels but they and all other known bonded silicas contain a benzene group or other elecron withdrawing groups which reduce the ability of the macrocycle to bond with cations and other solutes and also involve secondary reactions of the silica gel with solutes, the interaction of the OH sites with metal cations. Prior researchers in this field confined their research to chromatographic applications and disclosed no concept of industrial separation applications where high purity products aro required. No prior disclosure has been found of the attachment of proton-ionizable crown compounds to silica gel.

According to a first embodiment of the present invention there is provided a process of separating a selected ion from a plurality of other ions in a multiple ion solution characterized by bringing the multiple ion solution into contact with a compound selected from the class consisting of I t tc 0 H O 0 0 0 o.^ ^^nR N- N 0 0 where n integers from 0 to 3, inclusive R CxH2x+I x integers from 6 to 18 0 0-P-O where n integers from 1 to 4 inclusive R CxH2x+l x integers from 6 to 18 where X 0 or S; n integers from 0 to 3, inclusive; R CH 2x+l x integers from 6 to 18 under conditions which cause said compound to complex with the selected ion and remove it from said multiple ion solution, separating said multiple ion solution from which said selected ion has been removed from said complex, and breaking said complex to free and recover said selected ion in a receiving liquid.

4 _i i 4 0 0 According to a second embodiment of the present invention there is provided the process of separating desired metal cations from liquid mixtures thereof with other cations characterized by: A. establishing a separate basic source phase of the cations to be separated, a separate receiving phase and a membrane liquid phase containing a water-insoluble macrocyclic proton-ionizable ligand in a water-insoluble solvent interfacing with the source phase and the receiving phase; B. maintaining this interfacial contact for a period of time long enough to transport a substantial part of the desired metal cations from the source phase to the receiving phase; and C. recovering the metal cations from said receiving phase, said ligand being selected from the class consisting of

X

I I

N

0 0 where X 0 or S; n integers from 0 to 3, inclusive; R

CH

2 x+ 1 x integers from 6 to 18 N- N

N

0 0 o where n integers from 0 to 3, inclusive R CxH 2 x+ 1 x integers from 6 to 18 t 4 9 0

O

(0 0n O' n dhere n integers from 1 to 4 inclusive R CxH2x+1 x integers from 6 to 18 441 According to a third embodiment of the present invention there is provided the process of covalently bonding on silica gel a macrocycle from the classes consisting of: 4A -I I.

L r ;G 3 O R 1

O

0 R 0 0 where X 0 or S; n integers from 0 to 3, inclusive; 1 R H or Blocker;

R

2 CH20CH 2

CH=CH

2 N- N

N

O O0 where n integers from 0 to 1, inclusive; R H or Blocker;

R

2

CH

2

OCH

2

CH=CH

2 CHO2(CH 2 3 Si(R 3 2 C1,

R

3

CH

3 or C1 0

R

2 O- O where n integers from 1-4 inclusive;

R

1 H or Blocker;

R

2

CH

2

OCH

2

CH=CH

2 i 41 4 4 with HSi(CH 3 2 C1 in the presence of a platinum catalyst to convert R 2 to CH 2 0(CH 2 3 Si(CH 3 2 C1 and heating silica gel with said compound to effect said covalent bond.

According to a fourth embodiment of the present invention there is provided compounds characterized by the structural formulae selected from the class consisting of: 4 4 4 4 4 1 4 4 444' «I 44 4 4 4 4 tI I L 4 4 4 44 4 t 1 4 4 O H 0 0 0 kO~ik

N

N

0 0 L R 0 0- P-O 0 0 On Qo o]- 4B _r_ where X 0 or S; n integers from 0 to 3, inclusive; R CxH2x+l; x integers from 6 to 18 where n integers from 0 to 3, inclusive; R CxH2x+l; x integers from 6 to 18 where n integers from 1 to 4, inclusive; R CxH2x+l; x integers from 6 to 18 According to a fifth embodiment of the present invention there is provided compounds selected from the group consisting of: X R1 Nai N-N 1 0 0111-

P

O R O a.

O O? nR 2 'i0 where X 0 or S; n integers from 0 to 3, inclusive;

R

1 H or Blocker;

R

2

CH

2

OCH

2

CH=CH

2

CH

2 0(CH 2 3 Si(R3) 2 C1 2 )3Si(R4) 2- SILICA GEL;

R

3

CH

3 or C1;

R

4

CH

3 or 0- SILICA GEL where n integers from 0 to 3, inclusive;

R

1 H or Blocker; 2 R CH 2 0CH 2

CH=CH

2

CH

2 0(CH 2 3 Si(R3)2C1,

CH

2 0(CH 2 3 Si(R4)20- SILICA GEL;

R

3

CH

3 or C1;

R

4

CH

3 or 0- SILICA GEL where n integers from 1 to 4, inclusive;

R

1 H or Blocker; 2 R CH 2 0CH 2

CH=CH

2 CH20(CH 2 )3S(R3 2C1, CH20(CH 2 )3Si(R4 SILICA GEL;

R

3

CH

3 or C1;

R

4

CH

3 or 0- SILICA GEL SUMMARY OF THE INVENTION The compounds of the present invention are characterized by a replacable or ionizable proton forming part of a macrocyclic compound having a lipophilic group attached to the molecule. It has been discovered that these compounds are particularly useful as ligands in a liquid membrane for selectively transporting desired metal ions from a source 4C L WE~~ 4 v nn w nr tt,~ _zccuphase to a receiving phase, as addition compounds to silica gel chains for selectively complexing with desired metal ions as a source phase flows over them through a column followed by a receiving phase which breaks the complex and washes the desired metal ions out of the column, and as transport agents in apertures in the wall of each filament in a bundle of filaments through which one of the two phases flows while the other flows over the outsides of them. These compounds are very effective and selective as transporters or carriers of desired metal cations and (2) as complexing receivers of said metal cations. They are characterized in embodiment of the invention by a high degree of transport selectivity for desired metal cations (according to the pH of both source and receiving i 4D x 2x+1 1 x int egers from integers from x integers from 6 to 18 6 to 18 6 to 18 ./2 'm U q v i -II I I 1 phases and macrocyclic cavity size) over various other metal cations, a low solubility in water, which minimizes macrocycle loss to adjacent aqueous phases, and the formation of neuti~al cation complexes through the loss of a, proton so.that the anion does not need to accompany the cation through the membrane. This latter property makes it possible to couple the transport of cations to the reverse flux of protons through the membrane. They are chaiacterized in embodiment of the invention utilizing the compounds of the invention as addition compounds to silica gel chains in a column by high selectivity for and removal of desired metal ions from the source phase containing a mixture of metal ions as it flows over them in a column. They ai-e characterized in embodiment of the invention by a high degree of selectivity for removing the desired metal ions fi~om the source phase and rapid transport of them through the short length of the ligand solution in the apertures of the walls of the filaments into the ieceiving phase. In all embodiments, the recovery of the desired metal ions from the receiving phase S is easily accomplished by well known procedures.

ERIEF DESCRIPTION OF THE DRAWINGS The invention will be described and illustrated by reference to the drawings in which: Fig. 1 is a diagramatic representation in vertical section of one form of apparatus which is suitable for use in embodiment of the process of the invention; Figs. 2 and 3 represent the molecular structures of two specific compounds of the invention, viz., octyl-substituted 4-pyridono-18-crown-6 and octyl-substituted 4-pyridono-15-crown 5, respectively, which are preferred embodiments of macrocyclic compounds used in the prc'ess of the invention; Fig. 4 represents two isomers a and b of one family of proton-ionizable macrocyclic compounds of the invention in which n is an integer from 0 through 4, inclusive, X is chosen from. the group consisting of oxygen and sulfur and y is an integer from 6 through 18, inclusive. In solution, the 4-hydroxypyridine structure of Fig. 4a is in equilibrium with the pyridone structure of Fig. 4b; Fig. 5 represents another family of proton-ionizable compounds of the invention having a hydrogen phosphate group in the macrocyclic molecule; S' Fig. 6 represents the plot of cation flux from a source phase at pH S values from 7 to 14 into a receiving phase of water at pH 6 or nitric acid S' at pH 1.5 using the compound shown in Fig. 2 as the ligand in the membrane phase; Figs. 7, 8 and 9 represent the reactions involved in bonding a proton ionizable macrocycle to silica gel; Q41 Fig. 10 represents schematically a suitable column for holding the a a silica gel-proton ionizable addition compound through which a solution of metal ions can be flowed to complex selectively with a desired ion in accordance with embodiment of the invention; Fig. 11 represents a suitable apparatus for carrying out embodiment (C) of the invention; Fig. 12 is a fragmentary perspective view of a short length of a filament on a much larger scale to show apertures in the wall thereof; and Fig 13 represents another family of proton-ionizable compounds having a triazolo subcyclic ring system as part of the macroccycle.

DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION Preparation Of The Compounds The compdunds of the invention may be prepared by any suitable method.

One method of preparing the compound of Fig. 3, for oxample, is to react the octyl-substituted triethylene glycol ditosylate and 4-(tetrahydro- 2-pyranoxy)-2,6-pyridinedimethanol followed by acid hydrolysis as follows: 0

OTHP

n o-t1 base acid TsO O O OTs 0 0 N 0 HO OH n-octyl i A method for producing the compound of Fig. 2 comprises reacting the ditosylate derivative of 4-THP blocked pyridinedimethanol and octyl substituted tetraethylene glycol as follows:

C

1 0 C OTHP OTHP n-octyl )base H o Na H C 4-HO 0 0 OH 2)acd 0) q N TsC1 .O HO OH TsO OTs n-octyl SBR/TGK/0077F 7 'Wo r The synthesis of 4-pyridone compounds of the invention, which is not part of the present invention, is described in greater detail in an article entitled PROTON-IONIZABLE CROHN ETHERS. 3. SYNTHESIS AND STRUCTURAL STUDIES OF MACROCYCLIC POLYETHER LIGANDS CONTAINING A 4-PYRIDONE SUBCYCLIC UNIT by Jerald S. Bradshaw, Yohji Nakatsuji, Peter Huszthy, Bruce E. Wilson, N. Kent Dalley and Reed M. Izatt, J. Heterocyclic Chem., Vol. 23, pages 353-360 (1986), which is incorporated herein by reference.

The synthesis of the thiopyridone crown compounds of the invention (Fig. 4 in which X is sulphur) comprises treating the pyridone crowns in which X is oxygen with a good thionation reagent, P2S5 and 2,4bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's Reagent, see Aldrich reagent number 22, 743-9).

The synthesis of the hydrogen phosphate containing compounds shown in Fig. 5 comprises reacting the appropriate oligoethylene glycol with t phosphorus oxychloride followed by treating the crude chloride with water in dioxane as follows:

R

HO -0 0 OH HO O O O OH

II

CHCI

2 0 0 /n 0

I!

0-P-0 water

OH

0 R in which n is an integer from 0 to 3, inclusive, and R is C6- 18 H13-37' SBR/TGK/0077F The synthesis of the triazolo compounds shown in Pig. 13 comprises reacting the appropriate oligoethylene glycol with 1-N-THP-blocked-triazolefollowed by 1) base and 2) dilute acid to remove the blocking group.as follows:

/THP

N--N

Cl Cl

R

HO O O O OH 1) base 2) H

H

N--N

AN

0 0 S*g in which THP represents the tetrahydropyranyl block group, n an integer from 0 to 3, inclusive, and R Cg 18 H 3 37 o0~o C.co The formation of a crown compound covalently bonded to silica gel is OO'oOe illustrated in Figs. 7, 8 and 9 of the drawing which comprises reacting a crown compound having a side chain -CH 2 -0-CH 2

-CH=CH

2 with HSi(CH 3 2 -Cl in Q 4 the presence of a platinum catalyst to convert the side chain into

(CH

2 3 -Si(CH) 2 -Cl and heating this compound with silica gel to produce a crown compound linked to a silica gel by a s.de chain -CH2-O-(CH2)- Si(CH 3 2 -0-silica gel. The silicon atom in Fig 7 and 8 can have three attached chlorine atoms rather than two methyl groups and one chlorine. The compounds of Figs. 4 and 5, and other species within the scope of Fig. 13, in addition to the one species illustrated in Fig. 7, can be used to form covalently bonded silica gel-crown compounds.

Metal Ion Recovery Process The metal ion recovery process of the invention relates to the selective recovery of desired metal ions from mixtures thereof with other :i metal ions using the compounds of the invention as defined above. Effective methods of recovery and/or separation of metal ions, particularly lithium, sodium and potassium, from one another in waste solutions, deposits and industrial solutions and silver recovery from waste solutions, from emulsions on photographic and X-ray film, represent a real need in modern technology. The present invention accomplishes this separation effectively and efficiently by the use of compounds in the families represented by Figs.

4 and 5, and more particularly by the compounds represented by Figs. 2, 3, 7 and 13.

Embodiment A 0° Separation by use of a ligand-containing liquid membrane procedure of o° c the invention involves the transport of metal ions from a separate source phase to a separate receiving phase through the liquid membrane which o el oooo interfaces with the two separate phases, as an emulsion or in an

C

0 apparatus such as illustrated in Fig. 1 of the drawing which is described in detail hereinafter.

o The cyclic compound of Fig. 2 exhibits the property of selectively complexing with K under basic conditions at a source phase of pH 12 and higher and a receiving aqueous phase, H4), at pH 7 and HNOo at pH ooego 1.5. The greater transport occurred with acid at pH 1.5 than with water S at pH 7 as the receiving phase.

The cyclic compound of Fig. 3 exhibits the property of selectively complexing with Li+ under basic conditions at a source phase of pH of 12 and higher and a receiving aqueous phase of water at pH=7 or HNO at Better transport of Li was noted with a receiving phase of HO0 at pH=7.

This result apparently is due in part to the complexation of Li by OH- to form LiOH (aq) in the receiving phase. The other alkali metal ions do not form similar MOH(aq) complexes.

A suitable apparatus in which the embodiment of the process of the invention can be carried out is shown in Fig. 1 in which 10 represents an outer container having an open top and a bottom wall closing the bottom, 12 is an open-ended inner container of smaller cross sectional area than the cross sectional area of 10 located within container 10 with its open bottom end spaced above the bottom wall of the outer container, 14 is a layer of liquid membrane containing the ligand which is deep enough to cover the open bottom end of the inner container 12, 16 is the source phase, viz., a body of aqueous solution of the metal ions to be separated located in the inner Scontainer 12 above the liquid membrane, and 18 is an aqueous receiving phase o located in the outer container 10 outside the container 12 above the level 4 of the liquid membrane. A stirring means, a magnetic stirrer 20, may be included, if desired. In this apparatus the source phase 16 is separated from the receiving phase 18 by the liquid membrane 14 and by a physical barrier, the inner container 12, and the membrane phase. The containers may be made of any suitable material such as metal, glass, plastic and the like.

Embodiment of the process of the invention is not dependent upon the use of this apparatus, however, because the process can be carried out in any apparatus which provides means for holding a separate aqueous 'phase containing the metal ions to be separated, a separate aqueous receiving phase and a membrane phase which separates and interfaces with the other two phases. For example, the phases may be in any kind of container as an emulsion of the two separate aqueous phases as dispersed droplets in a continuous organic liquid phase containing the ligand. In such 11 *I I I .11 1 apparatus the source phase is separated from the receiving phase only by the liquid membrane phase.

In embodiment of the process of the invention, the desired metal ions are selectively removed from the source phase 16 of the aqueous solution containing them by the deprotonated ligand in phase 14 across the interface between 14 and 16 and are delivered from the ligand to the aqueous receiving phase 18 across the interface between phases 16 and 18.

The deprotonated hydrogen from the ligand forms water with the hydroxide from the source phase in the liquid membrane phase, causing the liquid membrane phase to become cloudy. Hydrogen from the receiving phase then protonates the ligand, being driven back across interfaces 16 and 18 through the liquid membrane phase, where the process repeats itself, causing a secondary driving force.

The separate aqueous phase containing the metal ions to be separated may be prepared in any suitable manner from any starting material having metal values which it is desired to recover in whole or in part.

The membrane phase containing the ligand in a suitable hydrophobic organic solvent may be prepared in any suitable manner from liquids known o in the art to be useful for this purpose, any of those mentioned in .Q J.D. Lamb, J3.. Christensen, J.L. Oscarson, B.L. Nielsen, B.W. Assay and o R.M. Izatt, J. Am. Chem. Soc., 102, pages 6820 6824 (1980) which is °oo incorporated herein by reference. Typically the solvent Is a ,polychlorinated hydrocarbon.

The receiving phase may be distilled water, deionized water, nitric acid solution in water having a suitable pH, 1 7, and the like.

The three liquid phases, after preparation, are placed in the apparatus in which the process is to be carried out.

I

a 3 0-0 04, t 0 0 00 0 0-o~ O 3 00 O 00o 12 In the apparatus without a rysical barrier separating the source and receiving phases, the source phase and the reoeiving phase are emlsifed as separate droplets in a continuous liquid membrane phase in any suitable container.

In using the apparatus of Fig. 1, the membrane phase is first introduced into the container 10 until it covers the lower end of tube 12, as illustrated in Fig. 1, the receiving phase is introduced into the container 10 outside the tube 12, and the source phase is introduced into the tube 12 both floating on the membrane phase and separated by the tube 12. 7he transport of the metal ions from the source phase to the receiving phase then takes place through the membrane phase by means of the selective ligand over a long enough period of time for substantially ccmplete removal of the desired metal ions fran the source phase and their delivery to the receiving phase.

Working exaMles of Embodiment A 4 4 4 Three liquid membranes are prepared of each of the two ligands represented by Figs. 2 and 3, referred to scmetimes hereafter as the ccPuds in Figs. 2 and 3, respectively, by dissolving enough of each ligand in an organic liquid membrane solvent of methylene chloride to form a 1.0 mM solution.

Using the apparatus illustrated in Fig. 1, into each of these 4-dram vials serving as outer containers 10 is poured 3.0 ml of each solution, which is enough to cover the lower end of inner glass tube 12. Atop this organic liquid are placed in the space in container 10 outside the tube 12, ml of distilled, deionized water, and in the tube 12, 0.8 ml of a source phase containing the ions to be separated. After 24 hours the receiving phase is sampled by extracting 3 ml and analyzed for cation concentration by atomic absorption spectrometry. Three runs are made of each ligand and the results 13 ~fr- P%~i 1.

averaged. The standard deviation among the values in each run is less than The results are given in TABLES I, 3I, III and IV.

Table I gives the non-competitive fluxes of alkali metal ions from an aqueous source phase of various pH values across a liquid membrane phase containing the compound in Fig. 2 into either of two different receiving phases, either water at pH 7 or nitric acid at pH Table II gives the competitive fluxes of alkali metal ions fraom an aqueous source phase at pH 14 across a liquid membrane phase containing the c01pound of Fig. 2 into either of two different receiving phases. For each cation mixture the ratio of metal ion fluxes is also given.

Table III gives the non-competitive fluxes of alkali metal ions fraom aqueous source phases of various pH values across a liquid membrane phase containing the ccmpound of Fig. 3 into receiving phases of either water at pH 7or nitric acid at pH F Table IV gives the competitive fluxes of alkali metal ions fraom an ,o aqueous source phase at pH 14 across a liquid menibrane phase containing the compound of Fig. 3 into either of two different receiving phases. For each cation mixture the ratio of metal ion fluxes is also given.

Fluxes are equal to JM(moles/s-m 2 x 10- 8 in which JM is the flux, s is 2 seconds and m is meters.

TABLE I Single M+ fluxesa in a bulk H 2 0-CH 2 Cl 2

-H

2 0 liquid membraneb system(Figure 1) using the Compound of Figure 2 as carrier.

Receiving Source Phase pH f',Phase pH 11 12 13 13.5 14 Li+ 7 72 56 N 7 6 9 47 503 6 8 60 633 KY 7 6 32 375 920 805 3 21 325 871 1631 Rb+ 7 <1 4 298 892 2032 0 1 187 880 1601 Cs+ 7 1 2 48 326 566 <1 <1 55 327 779 b Phase compositions: Source: 1.0 M in each metal cation using appropriate amounts of MN0 3 and MOH to achieve the initial source phase pH1. Membrane: 1 mM of the Compound of Figure 2 in CH 2 C1 2 Receiving: initial pH of 7 (H120) or 1.5 (HNO 3 as indicated.

'I

I I I ta Ia 111111 I I II.TABLE II Comxpetitive M+ fluxesa in a bulk H 2 0-CH 2 01 2

-H

2 0 liquid membraneb system (Figure 1) using the Compound of Figure 2 as carrier Metal 1(1+ Ions 2 Aqueous Receiving Phase pH- 7 Flux Ratio PH 1. Flux Ratio 1217 17 1229 263 909 332 1021 163 71.5 4.7 2.7 6.3 1263 6 2469 375 1458 601 1715 225 21.0.5 6.6 2.4 7.6 q, I S

I

*0*S 4* 4 I 4 4 4 1 4 bPhase compositions. Source: initial pH of 14, 0.5M in each metal hydroxide. Membrane: 1 mM of the Compound of Figure 2 in CH 2 C1 2 Receiving: initial pH of 7 (H 2 0) or 1.5 (HNO 3 as indicated.

-w U TABLE III Single MH fluxesa in a bulk H 2 0-CH 2 C1 2

-H

2 0 liquid membraneb system using the Compound of Figure 3 as carrier.

Receiving Source Phase pH M+ Phase pH 11 12 13 13.5 14 Li+ Na+

KY

'Rb+ It f I Cs t 1 I I I I 7 7 7 7 7 2313 785 74 209 113 111 86 83 47 174 4254 929 309 641 421 461 124 135 133 246 aJM-(mol*si m-2)10" bphase compositions: Source: 1.0 M in each metal cation using appropriate amounts of MN0 3 and MOH to achieve the initial source phase pH. Membrane: 1 mM of the Compound of Figure 3 in CH 2 C1 2 Receiving: initial pH of 7 or 1.5 (HNO 3 as indicated.

44 4 4 4 4 4 4 4 I Ii 44 44 4 4 4 4 4 ~4494 4444'.

4 4 TABLE IV Competitive Mt fluxesa in a bulk H 2 0-CH 2 C1 2

-H

2 0 liquid membraneb system (Figure 1) using the Compound of Figure 3 as carrier.

Metal i{l+ Ions M 2 Aqueous Receiving Phase p11-7 PH1-1.5 FlxRatio Flux Ratio Li 449 2.0 1443 2.3 Na 228 630 Li, 474 2.6 1074 K 184 237 Li 753 2.1 545 2.4 Rb 353 232 Li 507 2.9 892 2.8 Cs 172 317 Na193 1.1 519 2.1 K 181 245 Na 612 0.8 339 4.3 Rb 767 79 Na 857 1.0 302 2.1 Cs 833 147 K 223 0.7 310 0.8 Rb 335 384 K 138 0.6 178 0.8 Cs 215 219 Rb 268 1.1 237 0.9 Cs 242 256 aJM bPhase compositions. Source: initial pH of 14, 0.5 M. in each metal hydroxide. Membrane: I mH of the Compound of Figure 3 in CH 2 C1 2 Receiving: initial pH of 7 (H 2 0) or 1.5 (HNQ 3 as indicated.

TABLE II demonstrates selective transport of Kt over other alkali metal cations with the solution of the compound in Fig. 2 at high pH with both H0 and HN0, pH 1.5 as receiving phases. TABLE IV demonstrates selectivity for Li+ and, to a lesser degree, Na+ over other alkali cations with the compound of Fig. 3 at high pH with both H20, pH 7, and HN03, pH =1.5 as receiving phases.

While the invention does not depend on the reason or hypothesis for the difference in selectivity, it may be noted that the two ligands vary in the size of their central cavities. The alkali metal, ions decrease in size as follows: Cs+ 1.70 A; Rb 1.48 A; K 1.36 A; Na 1.01 A; Li 0.67 A. It may well be that the selectivity is a function of a complexing Srelation between cavity size and cation size.

t t The competitive flux data in TABLE II demonstrate that K+ is transported selectively by the larger-cavity pyridone ligand of Fig. 2.

Reducing the cavity size to that of the. compound of Fig. 3 results in selective transport of Na+ and Li+ over the remaining .ations, as seen in Table IV. In this latter case, Li is transported selectively over Na+ by 2.3 fold. A further improvement in-Li selectivity over Na is to be expected with a still smaller cavity pyridone macrocycle of Fig. 4 when n 0- It is likely that M selectivity is related to the relative hydration energies of the cations studied, since partial or complete dehydration of the cation occurs in the complexation process.

Experiments were carried out using the compound of Pig. 2 to measure the rate of K transport under conditions of varying source phase pH values, which demonstrates the exchange of a proton for the cation at the source phase interface, but H 0 (H from the ligand and OH- from the source phase) may be pulled into the liquid membrane phase. This is evidenced by the degree of cloudiness (which coincides with the degree of transport) in the liquid membrane phase.

Mixtures of MNO- 3 and MOH were used as the source phase. The relative amounts of the two solutes were adjusted to maintain the total M+ concentration at 1.00 M in each case. The transport rates are small below pH 12 but rise rapidly at pH values above 12, as seen in Fig. 6. This result confirms the fact that a proton is removed from the ligand in the complexation process and that for appreciable transport to take place, the source phase must be quite basic (pH>12).

Tests of transport of various metal ions at various beginning pH values of the receiving phase were carried out in the manner described previously using various macrocyclic compounds of-the invention with results compiled 4 in Tables V through IX as follows: Table V, Transport of lithium metal ions by the compound of Fig. 3.

Table VI, Transport of silver metal ions by the compound of Fig. 4 in which x 0 and n 1.

Table VII; Non-competitive fluxes of alkali metal ions by the sulfur analog (X S, n 2, y 8) of the compound of Fig. 4 from an aqueous source phase at various pH values across a liquid membrane phase into two different receiving phases, either water at pH 7 or nitric acid at ph Table VIII, Competitive fluxes of alkali metal ions from an aqueous source phase at pH 14 across the liquid membrane phase containing the compound of Fig4 (X S, n 2, y 8) into a nitric acid receiving phase.

Cblumn a gives the mixture of ions in the source phase. Column b gives the SBR/TGK/0077F ratio of al~kali mietal. fluxes in a receiving phase of nitric acid of pH1 Table DC, Non-competitive fluxes of alkali metal ions from an aqueous source phase of various pH1 values across a liquid membrane phase containing the compound of Fig. 5 into two different receiving phases, either water at pH 7 or nitric acid at pH 1 TABLE X gives data on separations of silver from lead effected in apparatus of~ the type illustrated in Fig. 1 using proton-ionizable triazolo crown ethers.

4 ii 44 II 4 4 4 4 4 .4 0G9 400* *0444 S SBR/TGK/0077F -8- TABLE V Flws of Lithium Metal Ions in Liquid membrane Systemsc(Figure 1) using the Compound of Figure 3 aBeginning pH 7.00 4.20 3.13 2.03 1.44 aEnding pH >12.33 >12.27 >12.38 11.97 1.58 bFlues 4254 3798 4785 3224 929 aReceiving phase pH and source phase pH(lithium hydroxide) >13.3 bFluxes (mol-s-. -m2) x 108 cMembrane system- 1 mM of the compound of Figure 3 in CH 2 C12 00 o 0 00 00 0 0 0 o00 TABLE

VI

000 0 Fluxes of Silver Metal Ions in -Liquid Membrane 0 "Systemsc(Figure 1) using the Compound of Figure 4* o 09 Saeginnng pH 6.80 4.08 3.13 2.03 1.42 SwaBeginning pH S aEnding pH 4.49 3.93 3.05 2.05 1.41 b 607 520 663 451 289 06V bFluxes *a vaReceiving phase pH and source phase pH(silver nitrate) 6.9 bFluxes (mols-1.m-2) x 108 cMembrane system- 1 mM of the compound of Figure 4* in CH 2 C12 *X O, Y 8 and n 1.

22 V V TABLE VII Single M+ fluxesa in a bulk H 2 0-CH 2 Cl 2

-H

2 0 liquid membraneb system(Figure 1) using the Compound of Figure 4* as carrier.

Receiving Source Phase pH K Phase pH 11 12 13 13.5 14 Li+ 7 22 51 56 84 266 1 12 18 39 153 Nat 7 84 116 118 124 54 26 46 151 563 172 K+7 844 604 713 568 122 168 473 712 935 733 Rb+ 7 299 366 363 298 66 44 158 420 578 328 Cs+ 7 136 173 222 133 67 1.5 43 61 211 239 243 C C CII I

CIII

1114~f C I I bPhase compositions: Source: 1.0 M in each metal cation using appropriate amounts 1 MR of

(H

2 0) or *x S, of MN0 3 and MOH to achieve the3 initial source phase pH. Membrane: the Compound of Figure 4* in CH 2 C1 2 Receiving: initial pH of 7 1.5 (11N0 3 as indicated.

Y 8 and n 2.

TABLE VIII Competitive e+ fluxesa in a bulk H 2 0-CH 2 Cl 2

-H

2 0 liquid membraneb systeni(Figure 1) using the Compound of Figure 4a* as carrier.

a b a ba b Li <1Li 14. K 225 Rb 277 CS 275 K 248 K 31R 196 Rb 84 CS 27 CS 46 a system b ratio of metal ion fluxes, receiving phase pH 1. 5 and source phase pH1 14 X S, Y 8, n 2.

rtft 1444 44,444 I 4 a

I

i TABLE IX Single M fluxes a in a bulk H 2 0-CH 2 Cl 2

-H

2 0 liquid membraneb system(Figure 1) using the Compound of Figure 5 as carrier.

Receiving Source Phase pH M Phase pH 11 12 13 13.5 14 Li

K+

.Rb+ S Cs C 4 t F t i 7 7 7 7 7 11 27 76 218 49 187 57 202 51 1910 11 35 49 246 52 621 70 338 50 169 18 34 53 305 55 745 54 851 84 238 29 26 43 191 52 1099 53 661 36 621 aJM-(mol-s-l.m-2)108 bphase compositions: Source: 1.0 M in each metal cation using appropriate amounts of MN0 3 and MOH to achieve the initial source phase pH. Membrane: 1 mM of the Compound of Figure 5 in CH 2 C1 2 Receiving: initial pH of 7 or 1.5 (HN0 3 as indicated.

-ifr_ TABLE X Single Ag+ and Pb 2 -I and Competitive Ag+ vs Pb 2 Crown Ether' Receivin, Fluxc ((mo1. s- .u2) 1 a Phase pH 0 Ag+ Pb 2 Ag+ vs Pb 2 4- (single) (single) Octyl-triazolo-15C5 7 55 293 56 1 452 -2 Oetyl-triazolo-18C6 7 328 876 420 87 1019 61 1303 73 0 Dicyclohexano, riazoo -l18C6 7 276 401 720 7 0 01.5 1927 246 1549 8 .~Dibenzotriazolo-18C6 7 30 2 47 <1 001.5 253 <1 288 <1 0 0a a1 niH of compound analogs in C11 2 C1 2 r0 0 Obp 11 7 H120; pH 1.5 HN0 3 c oThe source phase was 1.0K in each of the cations present

I

An analog of the compound in Fig. 3 (described above as highly selective for lithium at source phase pH=14) is the compound in Pig. 4a (X 0, n 1, y 8) which shows a high transport for silver at source phase pH 6.9 and at receiving phase pH =1.5 (HNO 3 Transport more than doubled with the receiving phase at pB=7 (H20) as seen in Table VI.

In the transport of silver ions the compound in Fig. 4a (X 0, n 1, y 8) shows the proton shifted to the oxygen atom on top, with the pyridone ring bonding structure modified to the 4-hydroxy pyridine structure so thatan anion must accompany the metal across the system. Lower transport of Ag+ with acid receiving phase is due to the anion N03 in the receiving phase inhibiting transport of Ag NO 3 across the interface.

Silver transport by the compound in Fig. 4a (X 0, n 1, y 8) in an 4 emulsion liquid membrane parallels transport in the bulk liquid membrane. An emulsion liquid membraia. is similar to a bulk liquid membrane, except that the membrane separates the aqueous source phase and receiving phase by surrounding the receiving phase as ian emulsified droplet. In the emulsions studied, the source phase contained 0.001 M A&IO0, the membrane was a 0.02 M macrocycle solution in toluene, sorbitan monooleate was used as the surfactant v/v) and the receiving phase contained either M2 0 3 (0.1 M) or HNO 3 (pH After 30 minutes, 98% of the Ag was transported when 3 was present in the receiving phase compared to 12% transport when HNO was present in the receiving phase. The difference in the amounts of transport is due to a transport mechanism where N0 3 is co-transported across the membrane by the macrocycle as seen in the bulk liquid membrane experiments.

The sulfur analog of the compound in Fig. 4 (see Fig. 4b: X S, n 2, y 8) appears to have a decrease in transport at source phase pH=14 (Table VII) but is still selective for IK over other alkali metals in competitive systems (Table VIII). This sulfur analog allows selective transport at lower pH source phase ranges.

Phosphorous proton-ionizable compounds have also shown high transport iates (Table IX) with results similar to those shown in Table VII.

TABLE X gives data on separations of silver from lead effected in apparatus of the type illustrated in Fig. 1 using proton-ionizable triazolo crown ethers. In all cases, silver is transported selectively over Pb 2 r Using a pH 7 or lower source phase, all other cations tested (alkali and alkaline earth cations, Fe 3 Ca 2 Ni 2 and Zn 2 showed little or no transport. Greater transport of Ag with an acidic receiving phase indicates that the transport of Ag+ by these triazolo macrocycles proceeds by a proton-ionizable mechanism.

0 0 4 o a An emulsion liquid membrane consisting of 0.9 ml of 0.03 M t bis(octyl)triazolo-18-crown-6 in phenylhexane as the membrane, 9 ml of 0.001 .t M AgNO 3 and 0.001 M PbNO3) 2 as the source phase and 0.9 ml of an HN0 3 receiving phase (pH 1.5) transferred 70% of the Ag and only 1% of the I' Pb 2 initially present in the source phase in 30 minutes.

A solvent extraction system of 4 ml of 0.03 M bis(octyl)triazolo-18crown-6 in phenylhexane and 4 ml of 0.001 M AgNO 3 in water extracted Ag into the phenylhexane phase quantitatively by a proton-ionizshle mechanism.

Triazolo-type macrocycles are selective for Ag over all other cations tested.

28 i _i.

Embodiment B In this embodiment of the invention, a column is packed over a support of glass wool with a macrocycle covalently bonded to silica gel as illustrated in Fig. 10 in which the column is designated generally by reference number 30 and comprises a wall 32 of any suitable material, e.g., glass, tapering at the bottom 34 to a closure member comprising a plug 36 having a petcock 38 rotatable therein by means of a handle 46. Plug 36 has a liquid passage 42 capable of communicating with the column and the atmosphere when the petcock is open. Petcock 38 has a passageway through itwhich in one position aligns with passage 42 to permit discharge of liquid from the column through a nozzle 48 into any suitable container (not shown) and in other positions prevents such discharge. A support layer of glass Swool is placed in column 30 above the outlet 42, as shown, which adequately supports a layer of the silica gel-crown compound complex placed above it without interfering with the flow of liquid through the gel-crown layer.

A suitable method of preparing the complex of silica gel with a crown compound is illustrated in Figs. 7, 8 and 9. The crown compound of Pig. 7 in which n may be 0 3 is reacted in the presence of a platinum catalyst with HSi(CH-3) 2 Clto yield the compound of Fig. 8 which is then reacted by heat with silica gel to yield the crown-bonded silica gel of Fig. 9. A sufficient quantity thereof is then placed in the column 30 on top of the glass wool support to yield a layer deep enough to complex the crown compound with substantially all of the desired cation contained in the multi-cation liquid flowed through the column.

The selective complexing properties of these compounds are retained while the stability of packed silica gel columns is maintained.

29 Furthermore, these separations correlate directly to the equilibrium constants for solute-macrocycle interaction in solution, as shown in the following working examples.

The process of Embodiment B can be carried out with other crown compounds from the other families disclosed by using a compound selected from these classes in the process represented by Figs. 7, 8 and 9, respectively, instead of the compound shown in each of these Figs.

t t( e t3 ,i;i r Working examples of Embodiment B A silica gel-containing crown-ether pendant groups was synthesized by passing a mixture of 1.0 gram of dimethylchlorosilane (freshly distilled) and 2.1 grams of benzene through an activated charcoal column having a diameter of 1 centimeter and a length of 45 centimeters to remove any trace impurities. 2.0 grams of the crown alkene were heated to 850 C in a milliliter round bottom flask fitted with a reflux condenser and purged with argon gas for an hour. 7 ae catalyst H 2 PtCl was added as 15 microliter of a 0.4% solution (98 THF, 1 EtOH, 1 H 2 PtC16). The reaction proceeded for hours. This mixture was then added to 25.0 grams of silica gel (60 200 mesh, dried at 3500 C for 4 hours and at 2500 C for 6 hours) suspended in CC14. The mixture was stirred and heated at reflux for an additional 24 hours. The silica gel was then collected by filtration and washed 5 times l !with CH2C12 (25 ml portions) and three times with Me0H (25 ml portions). The final product was dried and the washings were checked to determine the yield. Based on the residue, the yield for the process was 99%.

One column containing unbonded silica gel was prepared to examine whether any separations observed were due to interactions of solutes with silica gel rather than the macrocycle. A second column was prepared by packing it with silica gel bonded to 18-crown-6. The height and diameter of both cylindrical columns were 150 centimeters and 19 centimeters, respectively. The exact same procedure was followed with each column. All tests were done in triplicate and the standard deviation in the tests was always less than 5% of the mean.

In each test a solute-containing water solution was passed through the columns until the concentrations leaving the columns were equivalent to the 31

L:

g^.rn m w m a mrn concentrations entering them so that the columns would be at equilibrium with the solute-containing solution. The columns were then washed with sufficient water to remove any solutes from the column which were not bound to the column. The use of 200 ml of water was found to be sufficient for the solute concentrations used. An eluent solution was then flowed through the columns until no solutes could be detected in the solution emerging from the columns. The following solute-containing water solutions were used: (A) Sr(N0 3 (Fisher) vs. Mg(N0 3 )2 with both nitrates present at 0.1 0.01 and S0.001 M; Sr(N0 3 )2 vs. Ca(N0O)'2 (Baker Adamson) with both nitrates present at 0.1 and 0.001 M; 0.5 M Ca(N0 3 vs. 0.001 M Sr(N 4 0.1 M Sr(NO 3 vs. either 0.1 M, 0.01 M or 0.001 M Ba(Nq: (Baker); 2 and 0.9 M Mg(NO) vs. 0.1 M Ca(NOV vs. 0.001 M Sr(N0 3 The alkaline earth cations used interact with 18-crown-6 in water and are easily eluted from the column with acetate or citrate. A 1.0 M citrate buffer preparied from 1.0 M citric acid (Fisher) and 2.5 M LiOH (Pierce) was used as the eluent solution except when Ba was one of the cations present.

Since the solubility of barium citrate is low, a 1.0 M acetic acid (J.T.Baker) and 0.5 M LiOH buffer was used as the eluent when Ba 2 was present. Citrate is the preferred eluent because the equilibrium constants for citrate-alkaline earth cation interactions are greater than the corresponding constants for acetate. Since the equilibrium constants for the interactions of both citrate and acetate with various alkaline earth cations are similar, the eluent will have little effect on the separations performed. All solutions collected from the columns were analyzed for the appropriate alkaline earth cation concentrations by atomic absorption spectrophotometry (Perkin Elmer Model 603).

32 -i r- Results of working examples of Embodiment B Bonded silica has OH sites which may also intei .ct with alkaline earth cations and since this interaction, if it occurs, would affect the separation selectivity, the selectivity of pure silica gel for alkaline earth cations is given in TABLE XI in the column headed "Blank Column Selectivity." An alternative, method for determining the selectivity of the macrocycle may be used vhere the interaction properties of the two cations with the OH groups are the same but one cation preferentially interacts with the macrocycle. This is done by placing the less interactive cation in It 4 1 9 excess of the other cation so that nearly all of the OH sites will interact S' only with the less macrocycle-interactive cation and any change in selectivity observed will then be due to the interactive properties of the 'Eao *Ia ,macrocycle. In TABLE XI the selectivity of 18-crown-6-covalently-bondedsilica gel for alkaline earth cations is given. An example of using the aoaa oo data in TABLE XI to determine macrocycle -3electivity for one cation over another is provided by the Ba+/Sr 2 system. When Sr 2 is present in excess of Ba 2 (bottom two entries) the Ba 2 +/Sr 2 selectivity is increased approximately ten-fold in comparing the data for the Blank and Macrocycle columns. This ten-fold selectivity is consistent with the equilibrium constants for macrocycle-cation interaction reported in tle literature.

33 TABLE XI Earth Cations using Separation of Alkaline an 18-crown-6 Bonded Silica Gel Selectivity Ratio Sr2/Mg 2 Sr 2 +/H4g 2 Sr 2 +/Ca 2 Sr 2 +/ca 2 Sr 2 +/Cg 2 Sr 2

+/C

2 Sr 2 +/Mg 2 Ba 2 +/Sr 2 Ba 2 +/sr 2 Ba 2 +/Sr 2 Cation Concentrations 0.1 M Sr 2 0.1 H Hg 2 0.01 M Sr 2 0.01 M Hg 2 0.001 H Sr 2 0.001 H Hg 2 0.1 H Sr 2 0.1 M Ca 2 0.01 M Sr 2 0.01 H Ca 2 0.001 H~ Sr 2 0.5 M Ca 2 C0.001 H Sr 2 0.1 M Ca 2 0.9 M Hg 2 0.1 M Ba 2 0.1 M Sr 2 0.01 M Ba 2 0.1 M Sr 2 0.001 H Ba 2 0.1 M Sr 2 Macrocycle Column Selectivity 17.0 17.0 23.5 23.6 3.3 2.6 0.154 0.54 0.54 1.0 2.8 0.5 0.105 Blank Column SelectivigX 1.34 0.88 1.14 0.99 0.74 0.0025, 0.00813 0. 00685 1.2 1.3 0.056 0.011 4 4 Embodiment C Referring now to Figs. 11 and 12, reference number 50 designates a casing having an internal header 52 secured near one end so as to leave an open chamber 55 and a like internal header 54 secured near the other end so as to leave an open chamber 57. In and. between headers 52 and 54 in a chamber 61 individual hollow fibres 56 are mounted as shown. Casing 50 has an inlet opening 58 into chamber 57 communicating with a supply line 60 for a multi-cation liquid. This liquid enters each filament and flows through it into chamber 55 at the other end of casing 50 from which it flows out through opening 62 into exhaust line 64. The chamber 61 in casing 50 between headers 52 and 54 in which the bundle of filaments 56 is located has an inlet opening 66 communicating with a liquid supply line 68 and an outlet opening 70 communicating with a line 72.

Fig. 12 shows the structure of a portion of an individual hollow fiber 56 in which the cylindrical wall is provided with a large number of tiny pores or apertures 78. Each aperture is filled with a ligand-containing Sorganic solvent of the type described in Embodiment A by filling chamber 61 .with its liquid phase, flowing the organic liquid-ligand phase through inlet 58 followed by the other liquid phase to be flowed through the apparatus which flushes out the organic liquid except from the pores or apertures 78.

The very short distance between the two phases through the organic-.igand liquid which occupies the pores or apertures of the hollow fiber gives a very short path of transport for the cations by the ligand from the multication liquid on one side of the wall of the hollow fiber to the receiving liquid on the other side of it.

In use, the liquid containing the cations to be separated is usually flowed thiough the hollow interior of the fibers 56 and receiving liquid through chamber 61 but this is not essential and may be reversed, if desired. In any event the flow of .the multi-cation liquid and the receiving liquid on opposite sides of the wall of hollow fiber .56 gives good contact of the macrocyclic crown compounds situated in each aperture 78 with both liquids which are separted by the very short distance of the wall thickness of the hollow fibers, making the length of transport of the selected desired cation very short and the efficiency of the transport very high.

I Examples from our work using hollow fiber liquid membranes containing a particular macrocycle to make separations include separating e from other alkali cations and Sr 2 from other alkaline earth cations. A phenylhexane solution containing a hydrophobic analog of dicyclohexano-18-crown-6 was used as the membrane. Specifically, when all cations were present in the S source phase as NO0 salts at 0.1 M the macrocycle was present at 0.05 M in the membrane and the receiving phase was water, K was transported over Na+ by a factor of 60 and Sr 2 was transported over Ba 2 by a factor of 2. The macrocycles described in the invention can be used similarly in a hollow fiber system.

Although the invention has been described and illustrated by reference to certain specific proton-ionizable compounds and processes of using them, analogs of these macrocycles are within the scope of the compounds and processes of the invention.

36 :il

Claims (23)

1. A process of separating a selected ion from a plurality of other ions in a multiple ion solution characterized by bringirg the multiple ion solution into contact with a compound selected from the class consisting of X 0, 0 00 0 00a 0 o 00 O t 0 0 ola o 0 0 O H O 0 0 where X 0 or S; n integers from 0 to 3, inclusive; P CxH2x+l x integers from 6 to 18 H N- N I-S 0 0 0 0 where n integers from 0 to 3, inclusive R CxH2x+l x integers fror 6 to 18 0 0- P- O H I 0 0 where n integers from 1 to 4 inclusive R CxH2x+l x integers from 6 to 18 under conditions which cause said compound to complex with the selected ion and remove it from said multiple ion solution, separating said multiple ion 5 solution from which said selected ion has been removed from said complex, and breaking said complex to free and recover said selected ion in a receiving liquid.

2. The process as set forth in claim 1 further characterized by the multiple ion solution being brought into contact with said compound by flowing it through and out of a column packed with silica gel which has said compound covalently bonded to it, such flow first effecting the complexing of the selected ion with said compound and second the separation of the solution therefrom, breaking the complex by flowing a receiving liquid 37 STA/1227y through said column to take said selected ion into solution therein and form a recovery solution, and recovering said selected ion from said recovery solution.

3. .'he process as set forth in claim 1 further characterized by the solution being brought into contact with said compound as a ligand in solution in a membrane liquid which is in separate contact with said multiple ion solution and said receiving liquid, the contact of the ligand with the multiple ion solution causing said compound to complex with the selected ion and transport it through the membrane liquid into contact with said receiving liquid which breaks the complex and frees the selected ion off( to be taken into solution in the receiving liquid, and recovering the selected ion from the receiving liquid.

4. The process as set forth in claim 3 further characterized by a physical barrier separating said multiple ion solution, said membrane liquid 0a o and said receiving liquid. o.i° 5. The process as set forth in claim 3 further characterized by said multiple ion solution and said receiving liquid being separately emulsified in said membrane liquid.

6. The process as set forth in claim 3 further characterized by said multiple ion solution and said receiving liquid being on opposite sides of the wall of a hollow fiber having apertures therein with said membrane liquid in said apertures.

7. The process as set forth in claim 1 further characterized by flow of said multiple ion solution and said receiving liquid on opposite sides of the wall of a hollow fiber having apertures therein containing the macrocycle compound as a ligand in an organic liquid. gL- l II. i i

8. The process of separating desired metal cations from liquid mixtures thereof with other cations characterized by: A. establishing a separate basic source phase of the cations to be separated, a separate receiving phase and a membrane liquid phase containing a water-insoluble macrocyclic proton-ionizable ligand in a water-insoluble solvent interfacing with the source phase and the receiving phase; B. maintaining this interfacial contact for a period of time long enough to transport a substantial part of the desired metal cations from the source phase to the receiving phase; and C. recovering the metal cations from said receiving phase, said ligand being selected from the class consisting of o ~tr rr r ri r a r o D N- N r N o o O C 0 O o 0 On nR 0 O-P-O 0 0 'i where X 0 or S; S n integers from 0 to 3, inclusive; R CxH2x+ x integers from 6 to 18 where n integers from 0 to 3, inclusive R CxH2x+l x integers from 6 to 18 where n integers from 1 to 4,inclusive R= CxH2x+l x integers from 6 to 18 39 STA/1227y

9. The process as set forth in claim 8 further characterized by the water-insoluble solvent being a polychlorinated hydrocarbon. The process as set forth in claim 8 further characerized by the source phase being separated from the receiving phase by both the membrane liquid phase and a physical barrier.

11. The process as set forth in claim 8 further characterized by the source phase being separated from the receiving phase by the membrane liquid phase only.

12. The process as set forth in claim 8 further characterized by the ligand being selected from the family represented by this structural formula: O 11-1 4 IN 0 H 0 0 0 OxH2x+l

13. The process as set forth in claim 12 further characterized by n being 0 of 1 and x being 8. il;

14. The process as set forth in claim 8 further characterized by the ligand being selected from the family represented by this structural formula: S N O H 0 0 0 O CxH 2 x+ The process as set forth in claim 14 further characterized by n being 0 or 1 and x being 8.

16. The process as set forth in claim 8 further characterized by the macrocycle being selected from the family represented by the structural formula: H /H N- N N 0 0 o O O CxH2x+ 1

17. The process as set forth in claim 8 further characterized by the ligand being selected from the family represented by this structural formula: 0 O I r P S O l CxH2x+1

18. The process as set forth in claim 17 further characterized by n being 2 and R being CH 17 I t I t

19. The process of covalently bonding on silica gel a macrocycle from the classes consisting of: o R' where X =0 or S; n integers from 0 to 3, inclusive; R= H or Blocker; R 2 CH 2 OCH 2 CH=CH 2 N-N N (0 0) 0 0 J 11 0 1n' where n integers from 0 to 1, inclusive; R H or Blocker; R CH 2 OCHCH=CH 2 9 CH 2 0(CH 2 3 Si (R 3 2 C1, R 3 CH 3 or Cl 0* Be 0- 0 2 O R. where n integers from 1-4 inclusive; R= H or Blocker; R2= CH 2 0CH 2 CH=CH 2 00 0 4.~4.0 4.0 4. 0 4.4 0 4.4 4. 43 4.~ 4.4 t~ 4. 4.44.4 *00002 4. 4. with HSi(CH 3 2 C1 in the presence of a platinum catalyst to convert R to CH 2 0(CH 2 3 Si(CH 3 2 C1 and heating silica gel with said compound to effect said covalent bond. Compounds characterized by the structural formulae selected from the class consisting of: 44 t4. (0 C0 HO) N- O 0 O 0 0 O-P-0 0 0 Yn U 0 -43 STA/l 227y where X 0 or S; n integers from 0 to 3, inclusive; R CxH2x+l; x integers from 6 to 18 where n inteoers from 0 to 3, inclusive; R CxH2x+1; x integers from 6 to 18 where n integers from 1 to 4, inclusive; R C x H2x+l' x integers from 6 to 18

21. The compound A as set forth in claim 20 characterized by X being 0 or S.

22. 0, 1, 2 or

23. 0, 1, 2 or

24. 1, 2, 3 or The compound A as set forth 3 and R being C 8 H 17 The compound B as set forth 3 and R being C 8 H 17 The compound C as set forth 4 and R being C 8 H 17 Compounds selected from the X in claim 20 characterized by n being in claim 20 characterized by n being in claim 20 characterized by n being group consisting of: 0 R' 0 O 0' where X 0 or S; n integers from 0 to 3, inclusive; R 1 H or Blocker; R 2 CH 2 OCH 2 CH=CH 2 2 3 Si(R3) 2 C1, 2 3 Si(R4)20- SILICA GEL; R 3 CH 3 or C1; R 4 CH 3 or 0- SILICA GEL N- N 0 0 L O where n integers from 0 to 3, inclusive; R 1 H or Blocker; 2 R CH 2 0CH 2 CH=CH 2 CH 2 O(CH 2 3 Si(R 3 2 C1, CH 2 0(CH 2 3 Si(R4)20- SILICA GEL; R 3 CH 3 or Cl; R 4 CH 3 or 0- SILICA GEL where n integers from 1 to 4, inclusive; R 1 H or Blocker; 2 R CH 2 0CH 2 CH=CH 2 CH 2 0(CH 2 3 Si(R 3 2 C1, CH 2 O(CH 2 3 i(R 4 2 0- SILICA GEL; R 3 CH 3 or C1; R 4 CH 3 or 0- SILICA GEL 44 ^227y 1 >tt0 l As r n .r i

26. A process of separating a selected ion from a plurality of other ions in a multiple ion solution, substantially as hereinbefore described with reference to any one of Figs 1, 10, 11 or 12 or any one of The Working Examples of Embodiments A, B or C or any one of Tables I to XI.

27. Compounds according to claim 20 substantially as hereinbefore described with reference to any one of Figs 2, 3, 4, 5 or 13.

28. Compounds according to claim 25 substantially as hereinbefore described with reference to any one of Figs. 7 to 9. DATED this TWENTY-SECOND day of JANUARY 1991 Brigham Young University SPatent Attorneys for the Applicant SPRUSON FERGUSON o4 a a109 0 4 i 4