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US 5,666,642 AGranted
Extraction of cesium and strontium ions from nuclear waste
AssigneeCoremetals Research, Inc.
InventorsM. Frederick Hawthorne, Gary B. Dunks
Life of this patent
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Abstract
Methods and agents for extracting cesium and strontium ions from aqueous solutions, including aqueous fission product waste solutions, are disclosed using substituted metal dicarbollide ions containing one or more chemical groups that increase solubility of the substituted metal dicarbollide ion in non-nitrated, non-chlorinated solvents, or using metal dicarbollide ion-substituted silicones.
Claims42
A substituted dicarbollide comprising a compound selected from the group consisting of:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1).sub.2.sup.- ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si--O--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d -[Si(R"')(R')--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3 ;
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a Z).sub.2 ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.6 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and g are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.6 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, --Si(R').sub.2 (C.sub.6 H.sub.5) or R"', k is 1 to 10, and R', R", R"', b, c and d are as defined above;
- and
- R.sub.2 is selected from the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
28 more elements
The conjugate acid of a substituted dicarbollide;
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1).sub.2 ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si-O{[Si (R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.4 -[SiR"') (R')--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a Z).sub.2.sup.- ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and q are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5) or R"', k is 1 to 10, and R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
28 more elements
An extraction agent comprising an organosiloxane having at least one metal dicarbollide ion moiety bound thereto.
A method for selectively extracting cesium ions from an aqueous phase, comprising:
- forming an aqueous-nonaqueous liquid combination by contacting a pregnant aqueous phase containing cesium ions with a first nonaqueous phase comprising at least one extraction agent, wherein the extraction agent is a substituted dicarbollide;
- and
- separating the liquid combination into a stripped aqueous phase and a pregnant nonaqueous phase, wherein the pregnant nonaqueous phase contains cesium ions extracted from the pregnant aqueous phase;
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1)2.sup.- ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si-O{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d -[SiR"')(R')--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a Z).sub.2 ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and g are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--]d}.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5) or R"', k is 1 to 10, and R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
31 more elements
A method for selectively extracting strontium ions from a substantially cesium-free aqueous solution, comprising:
- adding a polyethylene glycol pr p-nonylphenyl-nonaethylene glycol to a pregnant aqueous phase containing strontium ions;
- forming an aqueous-nonaqueous liquid combination by contacting the pregnant aqueous phase with a first nonaqueous phase comprising at least one extraction agent, wherein the extraction agent is a substituted dicarbollide;
- and
- separating the liquid combination into a stripped aqueous phase and a pregnant nonaqueous phase, wherein the pregnant nonaqueous phase contains strontium ions extracted from the pregnant aqueous phase;
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1).sub.2.sup.- ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si-O{[Si(R').sub.2 --O--].sub.d -[SiR"'--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a Z).sub.2 ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where i is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and q are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5) or R"', k is 1 to 10, and R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
32 more elements
A method for selectively extracting cesium and strontium ions from an aqueous solution, comprising:
- forming an aqueous-nonaqueous liquid combination by contacting the pregnant aqueous phase containing cesium and strontium ions with a first nonaqueous phase comprising at least one extraction agent, wherein the extraction agent is a substituted dicarbollide;
- and
- separating the liquid combination into a stripped aqueous phase and a pregnant nonaqueous phase, wherein the pregnant nonaqueous phase contains cesium ions extracted from the pregnant aqueous phase;
- modifying the stripped aqueous phase by adding a polyethylene glycol or p-nonylphenylnonaethylene glycol;
- forming a second aqueous-nonagueous liquid combination by contacting the modified, stripped aqueous phase with a fresh nonaqueous phase comprising at least one extraction agent, wherein the extraction agent is a substituted dicarbollide;
- separating the second liquid combination into a stripped aqueous phase and a second pregnant nonaqueous phase, wherein the second pregnant nonaqueous phase, wherein the second pregnant nonaqueous phase contains strontium ions;
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1)2;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si-O{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d -[SiR"') (R')--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-1 R.sub.a Z).sub.2 ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and q are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5) or R"', k is 1 to 10, and R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
34 more elements
A method for extracting cesium ions from an aqueous solution, comprising contacting the cesium ions with at least on extraction agent comprising a substituted dicarbollide;
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1)2.sup.- ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:.
- (R').sub.3 Si-0{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d -[SiR"') (R')--O--].sub.e [Si(R').sub.2 --O--].sub.f [SiR'R"'--O--].sub.g [Si(R').sub.2--O--].sub.h }.sub.j Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a Z).sub.2.sup.- ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and g are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5 H) or R"', k is 1 to 10, and R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
28 more elements
A method for extracting strontium ions from an aqueous solution, comprising contacting the strontium ions, in the presence of polyethylene glycol or p-nonylphenylnonaethylene glycol, with at least one extraction agent comprising a substituted dicarbollide;
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1)2.sup.- ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si-O{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d -[SiR"') (R')--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"'is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.z Z).sub.2 ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to S, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and g are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to S, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m- fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5) or R"', k is 1 to 10, and
- R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
29 more elements
A semipermeable membrane, comprising a silicone elastomer or microporous polymer film wherein the elastomer of film comprises at least one substituted dicarbollide:
- wherein the substituted dicarbollide comprises:
- a) a metal dicarbollide ion of the formula:
- M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a+1)2.sup.- ;
- or
- b) a metal dicarbollide ion-substituted organosiloxane of the formula:
- (R').sub.3 Si-O{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d -[SiR"') (R')--O--].sub.e -[Si(R').sub.2 --O--].sub.f [SiR'R"--O--].sub.g [Si(R').sub.2 --O--].sub.h }.sub.i Si(R').sub.3
- wherein M is a transition metal capable of forming a trivalent oxidation state;
- R' is methyl or trifluoromethyl;
- R" is phenyl or fluoro- substituted phenyl;
- R"' is a metal dicarbollide ion moiety of the formula:
- --W--[M(B.sub.9 C.sub.2 H.sub.10-a R.sub.a Z).sub.2.sup.- ]
- where W is oxygen or alkylene having from 2 to about 10 carbon atoms, and each Z is independently selected from hydrogen, alkyl having from about 1 to about 10 carbon atoms;
- fluoro- substituted alky1 having from 1 to about 10 carbon atoms;
- phenyl or substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl;
- a is 0 to 3;
- b, d, f, and h are 0 to 10;
- c and g are 0 or 1;
- and e and i are 1 to 10;
- and each R is independently selected from R.sub.1 or R.sub.2, where
- R.sub.1 is alkyl having from about 7 to about 10 carbon atoms;
- fluoro- substituted alkyl having from 2 to about 10 carbon atoms;
- substituted phenyl of the formula:
- --C.sub.5 H.sub.5-j Y.sub.j
- where j is 1 to 5, and Y is fluorine, phenyl or fluoro- substituted phenyl, with the proviso that R.sub.1 cannot be 1-m-fluorophenyl or 1-p-fluorophenyl;
- or R.sub.1 is an organosiloxane of the formula:
- --W--{[Si(R').sub.2 --O--].sub.b [SiR'R"--O--].sub.c [Si(R').sub.2 --O--].sub.d }.sub.k E
- where E is --Si(R').sub.3, Si(R').sub.2 (C.sub.2 H.sub.5) or R"', k is 1 to 10, and R', R", R"', b, c and d are defined as above;
- and R.sub.2 is selected form the group consisting of chlorine, bromine, methyl and trifluoromethyl;
- provided that at least one R must be R.sub.1.
28 more elements
Dependencies are inferred from the claim text.