Crown ether uranyl halide complexes

Claim 2

A complex of: (A) a uranyl halide; and (B) a crown ether selected from the group consisting of dicyclohexano-18-crown-6 and crown ethers wherein the cyclic ring consists of 4 to 10-O-J-units wherein J for a particular compound is (a) --CHR--CHR-- or (b) --CHR--CR 2 --CHR--, wherein each R is independently selected from the group consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, or wherein at least one J is (b) and the remaining J's are (a).

Claim 3

A complex according to claim 1 wherein the crown ether is one in which the cyclic ring contains no more than 24 atoms and in which the R's if alkyl have no more than two carbon atoms.

Claim 4

A complex according to claim 2 wherein the uranyl halide is hydrated.

Claim 5

A complex according to claim 2 having the formula UO.sub.2 Cl.sub.2.(18-crown-6).3H.sub.2 O.

Claim 6

A complex according to claim 2 having the formula UO.sub.2 Cl.sub.2.(15-crown-5).3H.sub.2 O.

Claim 7

A complex according to claim 2 having the formula UO.sub.2 Cl.sub.2.(12-crown-4).2H.sub.2 O.

Claim 8

A complex according to claim 2 having the formula (UO.sub.2 Cl.sub.2).sub.2.(18-crown-6).

Claim 9

A complex according to claim 2 having the formula (UO.sub.2 Cl.sub.2).sub.2.(15-crown-5).sub.3.2HCl.

Claim 10

A uranyl halide complex according to claim 2 having the formula UO.sub.2 Cl.sub.2.(12-crown-4).

Claim 11

A uranyl halide complex according to claim 2 having the formula (UO.sub.2 Cl.sub.2).sub.2.(dicyclohexano-18-crown-6).

Claim 14

A method according to claim 11 wherein the crown ether is one in which the cyclic ring contains no more than 24 atoms and in which each R if alkyl has no more than two carbon atoms.

Claim 15

A method according to claim 12 wherein said admixing is conducted at a temperature in the range of about 20° to about 40° C.

Claim 16

A method according to claim 13 wherein said uranyl halide is selected from the group consisting of uranyl chloride, uranyl bromide, and uranyl iodide.

Claim 17

A method according to claim 14 wherein the uranyl halide has water associated therewith.

Claim 18

A method according to claim 15 wherein said crown ether is selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, and dicyclohexano-18-crown-6.

Claim 19

A method according to claim 16 wherein said uranyl halide and said crown ether are admixed in glacial acetic acid containing no more than 1 weight percent water.

Claim 20

A method according to claim 17 wherein the molar ratio of uranyl halide to crown ether is in the range of about 0.1:1 to about 10:1.

Claim 21

A method according to claim 18 wherein the weight ratio of glacial acetic acid to the combined weight of uranyl halide and crown ether is in the range of about 3:1 to about 20:1.

Claim 22

A method according to claim 19 wherein said uranyl halide is uranyl chloride trihydrate.

Claim 23

A method according to claim 20 wherein a solution of uranyl chloride trihydrate in glacial acetic acid is added to a solution of said crown ether in glacial acetic acid and said combined solutions are stirred until said uranyl chloride crown ether complex is formed.

Claim 24

A method according to claim 13 wherein said uranyl halide is anhydrous and said uranyl halide and said crown ether are admixed in an anhydrous liquid.

Claim 25

A method according to claim 22 wherein said anhydrous uranyl halide is selected from the group consisting of uranyl chloride, uranyl bromide, and uranyl iodide.

Claim 26

A method according to claim 23 wherein said uranyl halide and said crown ether are admixed in anhydrous acetic acid.

Claim 27

A method according to claim 24 wherein said crown ether is selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, and dicyclohexano-18-crown-6.

Claim 28

A method according to claim 25 wherein the molar ratio of said uranyl halide to said crown is in the range of about 0.1:1 to about 10:1.

Claim 29

A method according to claim 26 wherein said anhydrous acetic acid is a mixture of glacial acid and acetic anhydride.

Claim 30

A method according to claim 27 wherein said anhydrous acetic acid is a mixture of glacial acetic acid and about 5 to about 10 weight percent of acetic anhydride.

Claim 31

A method according to claim 28 wherein said uranyl halide is anhydrous uranyl chloride.

Claim 32

A method according to claim 11 wherein said uranyl halide is anhydrous and said uranyl halide and said crown ether are admixed in an anhydrous liquid.

Claim 33

A process for the selective separation of at least one uranyl halide from one or more nickel halides and/or copper halides comprising dissolving said at least one halide in a solvent in which a uranyl halide.-18-crown-6 complex is stable and admixing 18-crown-6 therewith under conditions such that a uranyl halide.18-crown-6 complex is formed, wherein said 18-crown-6 is in an amount no greater than the amount needed to complex all of the uranyl halide in the solution, and recovering the uranyl halide.-18-crown-6 complex that is formed.

Claim 34

A process for the selective separation of at least one uranyl halide from one or more nickel halides and/or copper halides comprising dissolving said at least one halide in a solvent in which a uranyl halide.-18-crown-6 complex is stable and admixing 18-crown-6 therewith under conditions such that a uranyl halide.18-crown-6 complex is formed, wherein said 18-crown-6 is in an amount no greater than the amount needed to complex all of the uranyl halide in the solution, and recovering the uranyl halide.-18-crown-6 complex that is formed.

Claim 35

A process according to claim 31 wherein the moles of 18-crown-6 employed are no greater than the number of moles of uranyl halide in the solution.

Claim 36

A process according to claim 31 wherein said at least one uranyl halide is dissolved in methanol and diethyl ether is added to precipitate the uranyl halide.18-crown-6 complex after said complex is formed.

Claim 37

A process for obtaining uranium oxide from an aqueous solution of uranyl halide comprising: extracting uranyl halide from said aqueous solution with an organic solvent which will permit the formation of recoverable uranyl halide crown ether complex; forming at least one uranyl halide crown ether complex by admixing with the organic solution of uranyl halide a suitable amount of at least one crown ether selected from the group consisting of dicyclohexyl-18-crown-6 and crown ethers wherein the cyclic ring consists of 4 to 10-O-J-units wherein J for a particular compound is ##STR4## wherein each R is indpendently selected from the group consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, or wherein at least one J is (b) and the remaining J'are (a); contacting said uranyl halide crown ether complex with water, carboxylate ion, and light under conditions sufficient to produce uranium oxide hydrate; and recovering said uranium oxide hydrate.

Claim 38

A process for obtaining uranium oxide from an aqueous solution of uranyl halide comprising: extracting uranyl halide from said aqueous solution with an organic solvent which will permit the formation of recoverable uranyl halide crown ether complex; forming at least one uranyl halide crown ether complex by admixing with the organic solution of uranyl halide a suitable amount of at least one crown ether selected from the group consisting of dicyclohexyl-18-crown-6 and crown ethers wherein the cyclic ring consists of 4 to 10-O-J-units wherein J for a particular compound is ##STR4## wherein each R is indpendently selected from the group consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms, or wherein at least one J is (b) and the remaining J'are (a); contacting said uranyl halide crown ether complex with water, carboxylate ion, and light under conditions sufficient to produce uranium oxide hydrate; and recovering said uranium oxide hydrate.

Claim 39

A process according to claim 34 wherein said crown ether is selected from the crown containing no more than 24 atoms in the cyclic ring and in which each R if alkyl has no more than two carbon atoms.

Claim 40

A process according to claim 35 wherein said at least one crown ether is selected from the group consisting of dicyclohexano-18-crown-6, 12-crown-4, 15-crown-5, 18-crown-6, and 24-crown-8.

Claim 41

A process according to claim 36 wherein the water is employed in such an amount that the uranium in said uranyl halide amounts to about 0.005 to about 10 weight percent of the weight of the water.

Claim 42

A method according to claim 37 wherein about 1 to about 10 moles of carboxylate ion is employed per mole of uranyl halide.

Claim 43

A method according to claim 38 wherein said uranyl halide crown ether complex is converted to uranium at a temperature in the range of about 20° C. to about 40° C.

Claim 44

A method according to claim 29 wherein the sole crown ether complex employed is 18-crown-6.

Claim 45

A method according to claim 16 wherein said uranyl halide and said crown ether are admixed in diethyl ether.

Claim 46

A method according to claim 41 wherein said crown ether is 15-crown-5.

Claim 47

A method according to claim 42 wherein said uranyl halide is uranyl chloride trihydrate.

Claim 48

A method according to claim 13 wherein said uranyl halide is uranyl chloride.

Claim 49

A method according to claim 11 wherein said uranyl halide is anhydrous and said uranyl halide and said crown ether are admixed in an anhydrous liquid.