Claims
- 1. A process for the recovery of gallium and rare earth values from mixtures of the oxides thereof, comprising:
- (i) acidulating and dissolving such admixtures in a chloride acidic medium;
- (ii) liquid/liquid extracting the solution which results with a water-insoluble organic extraction agent into an aqueous phase and an organic phase, whereby said gallium values are preferentially transferred from said aqueous phase into said organic phase; and
- (iii) recovering said gallium and said rare earth values from the respective phases comprising same.
- 2. The process as defined by claim 1, said acidic medium comprising at least one acid selected from the group consisting of hydrochloric acid and perchloric acid.
- 3. The process as defined by claim 2, said acidic medium being at a boil.
- 4. The process as defined by claim 3, said acidic medium being both pure and concentrated.
- 5. The process as defined by claim 2, said acidulating and dissolving being conducted under reflux in such stoichiometric excess of acid that the residual acidity of the acidic medium, upon completion of the acidulation dissolution, is greater than 2N.
- 6. The process as defined by claim 1 the starting material oxide admixture being particulate, and the particles thereof having diameter sizes of less than 400 microns.
- 7. The process as defined by claim 6, said diameter sizes ranging from 50 to 200 microns.
- 8. The process as defined by claim 1, said extractant being an anionic extractant selected from the group consisting of long-chain hydrocarbons comprising primary, secondary or tertiary amino functions, or quaternary ammonium, sulfonium or phosphonium salt functions.
- 9. The process as defined by claim 8, said anionic extractant being selected from the group consisting of:
- (i) primary amines of the formula: ##STR14## in which R is a hydrocarbon having from 18 to 24 carbon atoms; (ii) secondary amines of the formula: ##STR15## in which R.sub.1, R.sub.2 and R.sub.3 are hydrocarbons, the sum of the total carbon atoms of which is from 12 to 14;
- (iii) tertiary amines of the formula R.sub.3 N, in which R is a hydrocarbon having from 8 to 10 carbon atoms;
- (iv) quaternary ammonium salts of the formula:
- [R.sub.3 N--CH.sub.3 ].sup.+ X.sup.-
- in which R is a hydrocarbon having from 8 to 10 carbon atoms and X is a chloride, nitrate or sulfate anion; and
- (v) sulfonium salts of the general formula: ##STR16## in which R is a hydrocarbon having from 10 to 18 carbon atoms and X is a chloride or nitrate anion.
- 10. The process as defined by claim 1, said extractant being a solvating extractant selected from the group consisting of esters, ethers, sulfoxides, ketones, alcohols, neutral organophosphorus compounds and trialkylamine oxides.
- 11. The process as defined by claim 10, said solvating extractant being selected from the group consisting of:
- (i) esters of the general formula: ##STR17## in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (ii) ethers of the general formula R.sub.1 -O-R.sub.2, in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (iii) sulfoxides of the general formula: ##STR18## in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (iv) ketones of the general formula: ##STR19## in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (v) alcohols of the general formula ROH, in which R is a hydrocarbon radical having at least 4 carbon atoms;
- (vi) neutral organophosphorus compounds of the general formulae: ##STR20## in which R.sub.1 and R.sub.2 and R.sub.3 represent hydrocarbon radicals having at least 4 carbon atoms; and
- (vii) trialkylamine oxides of the general formula R.sub.3 NO, in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms.
- 12. The process as defined by claim 11 said solvating extractant being selected from the group consisting of ethyl acetate, butyl acetate, diethyl ether, isopropyl ether, di-n-butyl ether, di-n-pentylsulfoxide, di-n-octylsulfoxide, diphenylsulfoxide, diisopropyl ketone, methyl isobutyl ketone, mesityl oxide, cyclohexanol, n-hexan-1-ol, 2-ethylhexanol, n-heptanol, n-octanol, the stearyl and cetyl esters of phosphoric acid, tributyl phosphate, dibutyl butylphosphonate, 2-ethylhexyl bis-(2-ethylhexyl) phosphonate, butyl bis-(chloromethyl)phosphonate, tri-n-octylphosphine oxide, and trioctylamine oxide.
- 13. The process as defined by claim 1, the solution resulting upon acidulation/dissolution further comprising a nonextractable neutral salt, the anion of which corresponding to that of the acidic medium the cation thereof being selected from the group consisting of alkali and alkaline earth metal, and aluminum.
- 14. The process as defined by claim 1, said extractant being anionic or solvating and the acidic medium comprising chloride anion, further including the addition of hydrochloric acid to the solution resulting upon acidulation/dissolution.
- 15. The process as defined by claim 1, said organic phase further comprising a heavy alcoholic or heavy phenolic modifier.
- 16. The process as defined by claim 1, said organic extractant further comprising a diluent therefor.
- 17. The process as defined by claim 1, said extractant being an anionic or solvating extractant, and wherein the recovery (iii) from the organic phase comprises the liquid/liquid extraction thereof with an aqueous or weakly acidic aqueous solution, with either said gallium values or said rare earth values being transferred from said organic phase into the resulting second aqueous phase.
- 18. The process as defined by claim 17, said liquid llquid extraction being with a weakly acidic aqueous solution, the concentration of H.sup.+ ions therein being 0.1N or less.
- 19. The process as defined by claim 1, the starting material oxide mixture comprising waste fines from the production of garnets.
- 20. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula: ##EQU1## in which RE is at least one element selected from the group consisting of gadolinium, yttrium, samarium and neodymium, A is selected from the group consisting of aluminium and scandium, .alpha.=.+-.0.20, and 0.ltoreq.<1.
- 21. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula:
- (RE.sub.1).sub.3-x-y (RE.sub.2).sub.x M.sub.x Fe.sub.5-z Ga.sub.z Ge.sub.z O.sub.12
- in which 0<x <0.5, y.gtoreq.0, 0<z.ltoreq.1.5, RE.sub.1 is selected from the group consisting of samarium and europium in the trivalent state, and M is calcium.
- 22. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula:
- RE.sub.3-x M.sub.x Ga.sub.5-x A.sub.x O.sub.12
- in which 0.ltoreq.x<1, RE is at least one element selected from the group consisting of gadolinium, samarium and neodymium, M is selected from the group consisting of calcium, strontium and magnesium, and A is selected from the group consisting of tin and zirconium.
- 23. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxide of the formula:
- (RE).sub.3-x Bi.sub.x Fe.sub.5-y A.sub.y O.sub.12
- in which 0.2<x<2, 0<y<1.5, RE is at least one element selected from the group consisting of yttrium, neodymium, samarium and gadolinium, A=Ga.sub.1-.alpha. M.sub..alpha. with 0.ltoreq..alpha.<1, and M is selected from the group consisting of aluminum, indium and scandium.
- 24. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula:
- Y.sub.5 Al.sub.5-x Ga.sub.x O.sub.12 :Ce.sup.3+
- in which 0<x.ltoreq.5.
- 25. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula:
- (RE)MO.sub.3 :Nd.sup.3+
- in which RE is at least one element selected from the group consisting of yttrium, gadolinium, lutetium and lanthanum, and M=Al.sub.1-x Ga.sub.x with 0<x.ltoreq.1.
- 26. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula:
- MA.sub.2 O.sub.4 :Eu.sup.2+
- in which M is an element selected from the group consisting of magnesium, calcium, barium and strontium, and A=Ga.sub.x Al.sub.1-x with 0<x.ltoreq.1.
- 27. The process as defined by claim 1, the starting material oxide mixture comprising mixed oxides of the formula:
- MA.sub.12 O.sub.19 :Eu.sup.2+ or (RE)MA.sub.11 O.sub.19 :Tb.sup.3+
- in which M is an element selected from the group consisting of magnesium, calcium, strontium and barium, RE is at least one element selected from the group consisting of cerium in the trivalent state and gadolinium, and A=Al.sub.1-x GA.sub.x with 0<x.ltoreq.1.
- 28. The process of claim 1, wherein the starting material oxide mixture comprises waste fines from the production of gadolinium/gallium garnets.
- 29. The process of claim 1, wherein the rare earth values comprise gadolinium.
- 30. A process for the recovery of gallium and gadolinium values from a mixture comprising the oxides thereof, with the process comprising (i) acidulating and dissolving the mixture in an acidic medium by contacting the mixture with sufficient nitric acid such that the residual acidity is at least 2N, (ii) next liquid/liquid extracting the resulting solution with a quaternary ammonium organic anionic extractant into an aqueous phase and an organic phase, with the gadolinium values being extracted into the organic phase, and (iii) thence recovering said gallium and said gadolinium rare earth values from their respective phases, whereby the gadolinium values are recovered from the organic phase by contacting the organic phase with water or a weakly acid aqueous solution in which the concentration of H+ ions is less than or equal to 0.1N.
- 31. The process of claim 30, wherein the acidulating and dissolving are conducted under reflux.
- 32. The process of claim 30, wherein the anionic extractant is in nitrate form.
- 33. A process for the recovery of gallium and gadolinium values from a mixture comprising the oxides thereof, with the process comprising (i) acidulating and dissolving the mixture in an acidic medium by contacting the mixture with sufficient nitric acid such that the residual acidity is at least 2N, (ii) next liquid/liquid extracting the resulting solution with tributyl phosphate as an organic extractant into an aqueous phase and an organic phase, with the gadolinium values being extracted into the organic phase, and (iii) thence recovering said gallium and said gadolinium rare earth values from their respective phases, whereby the gadolinium values are recovered from the organic phase by contacting the organic phase with water or a weakly acid aqueous solution in which the concentration of H+ ions is less than or equal to 0.1N.
- 34. The process of claim 33, wherein the acidulating and dissolving are conducted under reflux.
- 35. A process for the recovery of gallium and gadolinium values from a mixture comprising the oxides thereof, with the process comprising (i) acidulating and dissolving the mixture in an acidic medium by contacting the mixture with sufficient hydrochloric acid such that the residual acidity is at least 2N, (ii) next liquid/liquid extracting the resulting solution with a quaternary ammonium organic extractant into an aqueous phase and an organic phase, with the gallium values being extracted into the organic phase, and (iii) thence recovering said gallium and said gadolinium rare earth values from their respective phases, whereby the gallium values are received from the organic phase by contacting the organic phase with water or a weakly acid aqueous solution in which the concentration of H+ ions is less than or equal to 0.1N.
- 36. Thc process of claim 35, wherein the acidulating and dissolving are conducted under reflux.
- 37. Tho process of claim 35, wherein the organic extractant is in chloride form.
- 38. A process for the recovery of gallium and gadolinium values from a mixture comprising the oxides thereof, with the process comprising (i) acidulating and dissolving the mixture in an acidic medium by contacting the mixture with sufficient hydrochloric acid such that the residual acidity is at least 2N, (ii) next liquid/liquid extracting the resulting solution with tributyl phosphate as the organic extractant into an aqueous phase and an organic phase, with the gallium values thereby being extracted into the organic phase, and (iii) thence recovering said gallium and said gadolinium rare earth values from their respective phases, whereby the gallium values are recovered from the organic phase by contacting the organic phase with water or a weakly acid aqueous solution in which the concentration of H+ ions is less than or equal to 0.1N.
- 39. The process of claim 38, wherein the acidulating and dissolving are conducted under reflux.
- 40. The process of claim 5, wherein the the extraction agent is an anionic extractant selected from the group consisting of long-chain hydrocarbons comprising primary, secondary or tertiary amine functions, or quaternary ammonium, sulfonium or phosphonium salt functions.
- 41. The process of claim 40, wherein the starting oxide mixture comprises the oxides of gallium and gadolinium.
- 42. The process of claim 5, wherein the extraction agent is a solvating extractant selected from the group consisting of esters, ethers, sulfoxides, ketones, alcohols, neutral organophosphorus compounds and trialkylamine oxides.
- 43. The process of claim 42, wherein the starting oxide mixture comprises the oxides of gallium and gadolinium.
- 44. The process of claim 5 wherein the extraction agent is a cationic extractant selected from the group consisting of organophosphorus acid, aliphatic acid, aromatic acid, halogen containing aliphatic, aromatic or cycloaliphatic acids, naphthenic acid, heavy acid fraction, sulfonic acid, versatic acid and beta-diketone.
- 45. The process of claim 44, wherein the starting oxide mixture comprises the oxides of gallium and gadolinium.
- 46. A process for the recovery of gallium and rare earth values from mixtures of the oxides thereof, comprising:
- (i) acidulating and dissolving such admixtures in a nitrate acidic medium;
- (ii) next liquid/liquid extracting the solution which results with a water-insoluble organic extraction agent into an aqueous phase and an organic phase, whereby said rare earth values are preferentially transferred from said aqueous phase to said organic phase; and
- (iii) recovering said gallium and said rare earth values from the respective phases comprising same.
- 47. The process of claim 46 wherein said nitrate acidic medium comprises nitric acid.
- 48. The process as defined by claim 47, said acidic medium being at a boil.
- 49. The process as defined by claim 4, said acidic medium being both pure and concentrated.
- 50. The process as defined by claim 47, said acidulating and dissolving being conducted under reflux in such stoichiometric excess of acid that the residual acidity of the acidic medium, upon completion of the acidulation dissolution, is greater than 2N.
- 51. The process as defined by claim 46, the starting material oxide admixture being particulate, and the particles thereof having diameter sizes of less than 400 microns.
- 52. The process as defined by claim 46, said extraction agent being an anionic extractant selected from the group consisting of long-chain hydrocarbons comprising primary, secondary or tertiary amino functions, or quaternary ammonium, sulfonium or phosphonium salt functions.
- 53. The process as defined by claim 52, said anionic extractant being selected from the group consisting of:
- (i) primary amines of the formula: ##STR21## in which R is a hydrocarbon having from 18 to 24 carbon atoms; (ii) secondary amines of the formula: ##STR22## in which R.sub.1, R.sub.2 and R.sub.3 are hydrocarbons, the sum of the total carbon atoms of which is from 12 to 14;
- (iii) tertiary amines of the formula R.sub.3 N, in which R is a hydrocarbon having from 8 to 10 carbon atoms;
- (iv) quaternary ammonium salts of the formula:
- [R.sub.3 N--CH.sub.3 ].sup.+ X.sup.-
- in which R is a hydrocarbon having from 8 to 10 carbon atoms and X is a chloride, nitrate or sulfate anion; and
- (v) sulfonium salts of the general formula: ##STR23## in which R is a hydrocarbon having from 10 to 18 carbon atoms and X is a chloride or nitrate anion.
- 54. The process as defined by claim 46, said extraction agent being a solvating extractant selected from the group consisting of esters, ethers, sulfoxides, ketones, alcohols, neutral organophosphorus compounds and trialkylamine oxides.
- 55. The process as defined by claim 54, said solvating extractant being selected from the group consisting of:
- (i) esters of the general formula: ##STR24## in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (ii) ethers of the general formula R.sub.1 --O--R.sub.2, in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (iii) sulfoxides of the general formula: ##STR25## in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (iv) ketones of the general formula: ##STR26## in which R.sub.1 and R.sub.2 are hydrocarbon radicals having at least 4 carbon atoms;
- (v) alcohols of the general formula ROH, in which R is a hydrocarbon radical having at least 4 carbon atoms;
- (vi) neutral organophosphorus compounds of the general formulae: ##STR27## in which R.sub.1 and R.sub.2 and R.sub.3 represent hydrocarbon radicals having at least 4 carbon atoms; and
- (vii) trialkylamine oxides of the general formula R.sub.3 NO, in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms.
- 56. The process as defined by claim 55 said solvating extractant being selected from the group consisting of ethyl acetate, butyl acetate, diethyl ether, isopropyl ether, di-n-butyl ether, di-n-pentylsulfoxide, di-n-octylsulfoxide, diphenylsulfoxide, diisopropyl ketone, methyl isobutyl ketone, mesityl oxide, cyclohexanol, n-hexan-1-ol, 2-ethylhexanol, n-heptanol, n-octanol, the stearyl and cetyl esters of phosphoric acid, tributyl phosphate, dibutyl butylphosphonate, 2-ethylhexyl bis-(2-ethylhexyl) phosphonate, butyl bis-(chloromethyl)phosphonate, tri-n-octylphosphine oxide, and trioctylamine oxide.
- 57. The process as defined by claim 53, wherein said anionic extractant is selected from the group consisting of the tertiary amines and the quaternary ammonium salts.
- 58. The process as defined by claim 55, wherein said solvating extractant is selected from the group consisting of organophosphorus compounds and the sulfoxides.
- 59. The process as defined by claim 46, the solution resulting upon acidulation/dissolution further comprising a nonextractable neutral salt, the anion of which corresponding to that of the acidic medium the cation thereof being selected from the group consisting of alkali and alkaline earth metal, and aluminum.
- 60. The process as defined by claim 46, said organic phase further comprising a heavy alcoholic or heavy phenolic modifier.
- 61. The process as defined by claim 46, said organic extractant further comprising a diluent therefor.
- 62. The process as defined by claim 46, said extraction agent being an anionic or solvating extractant, and wherein the recovery (iii) from the organic phase comprises the liquid/liquid extraction thereof with an aqueous or weakly acidic aqueous solution, with either said gallium values or said rare earth values being transferred from said organic phase into the resulting second aqueous phase.
- 63. The process as defined by claim 62, said liquid/liquid extraction being with a weakly acidic aqueous solution, the concentration of H.sup.+ ions therein being 0.1N or less.
- 64. The process as defined by claim 46, the starting material oxide mixture comprising waste fines from the production of garnets.
- 65. The process as defined by claim 46, the starting material oxide mixture comprising mixed oxides of the following formulae: ##EQU2## in which RE is at least one element selected from the group consisting of gadolinium, yttrium, samarium and neodymium, A is selected from the group consisting of aluminium and scandium, .alpha.=.+-.0.20, and 0.ltoreq.x<1;
- (RE.sub.1).sub.3-x-y (RE.sub.2).sub.x M.sub.x Fe.sub.5-z GA.sub.z Ge.sub.z O.sub.12 ( 2)
- in which 0<x<0.5, y.gtoreq.0, 0<z.ltoreq.1.5, RE.sub.1 is selected from the group consisting of samarium and europium in the trivalent state, and M is calcium;
- RE.sub.3-x M.sub.x Ga.sub.5-x A.sub.x O.sub.12 ( 3)
- in which 0.ltoreq.x<1, RE is at least one element selected from the group consisting of gadolinium, samarium and neodymium, M is selected from the group consisting of calcium, strontium and magnesium, and A is selected from the group consisting of tin and zirconium;
- (RE).sub.3-x Bi.sub.x Fe.sub.5-y A.sub.y O.sub.12 ( 4)
- in which 0.25<x<2, 0<y<1.5, RE is at least one element selected from the group consisting of yttrium, neodymium, samarium and gadolinium, A=Ga.sub.1-.alpha. M.sub..alpha. with 0.ltoreq..alpha.<1, and M is selected from the group consisting of aluminum, indium and scandium;
- Y.sub.5 Al.sub.5-x Ga.sub.x O.sub.12 :Ce.sup.3+ ( 5)
- in which 0<x.ltoreq.5;
- (RE)MO.sub.3 :Nd.sup.3+ ( 6)
- in which RE is at least one element selected from the group consisting of yttrium, gadolinium, lutetium and lanthanum, and M=Al.sub.1-x Ga.sub.x with 0<x.ltoreq.1;
- MA.sub.2 O.sub.4 :Eu.sup.2+ ( 7)
- in which M is an element selected from the group consisting of magnesium, calcium, barium and strontium, and A=Ga.sub.x Al.sub.1-x with 0<x.ltoreq.1; and
- MA.sub.12 O.sub.19 :Eu.sup.2+ or (RE)MA.sub.11 O.sub.19 :Tb.sup.3+( 8)
- in which M is an element selected from the group consisting of magnesium, calcium, strontium and barium, RE is at least one element selected from the group consisting of cerium in the trivalent state and gadolinium, and A=Al.sub.1-x GA.sub.x with 0<x.ltoreq.1.
- 66. The process of claim 46, wherein the starting material oxide mixture comprises waste fines from the production of gadolinium/gallium garnets.
- 67. The process of claim 46, wherein said extraction agent is a nitrate anionic extractant.
- 68. The process of claim 67, wherein said extraction agent is a quaternary ammonium salt anionic extractant.
- 69. The process of claim 46 wherein the rare earth values comprise gadolinium.
- 70. The process of claim 50, wherein the extraction agent is an anionic extractant selected from the group consisting of long-chain hydrocarbons comprising primary, secondary or tertiary amine functions, or quaternary ammonium, sulfonium or phosphonium salt functions.
- 71. The process of claim 70, wherein the starting oxide mixture comprises the oxides of gallium and gadolinium.
- 72. The process of claim 50, wherein the extraction agent is a solvating extractant selected from the group consisting of esters, ethers, sulfoxides, ketones, alcohols, neutral organophosphorus compounds and trialkylamine oxides.
- 73. The process of claim 72, wherein the starting oxide mixture comprises the oxides of gallium and gadolinium.
- 74. The process of claim 50, wherein the extraction agent is a cationic extractant selected from the group consisting of organophosphorus acid, aliphatic acid, aromatic acid, halogen containing aliphatic, aromatic or cycloaliphatic acids, naphthenic acid, heavy acid fraction, sulfonic acid, versatic acid and beta-diketone.
- 75. The process of claim 74, wherein the starting oxide mixture comprises the oxides of gallium and gadolinium.
- 76. The process as defined by claim 1, said extraction agent being a cationic extractant selected from the group consisting of organophosphorus acids; aliphatic or aromatic acids; halogen-containing aliphatic, aromatic, or cycloaliphatic acids; naphthene acids; heavy acid fractions; sulfonic acids; at least one acid having the general formula: ##STR28## in which R.sub.1 and R.sub.2 are substituted or unsubstituted hydrocarbon radicals; and B-diketones.
- 77. The process as defined by claim 76, said cationic extractant being selected from the group consisting of:
- (i) organophosphorus acids of the general formula: ##STR29## in which R.sub.1 and R.sub.2 represent aliphatic or aromatic hydrocarbon radicals which are such that the total number of carbon atoms in R.sub.1 and R.sub.2 is equal to at least 10;
- (ii) aliphatic acids in which the hydrocarbon radicals have from 3 to 20 carbon atoms;
- (iii) halogen-containing aliphatic, aromatic, or cycloaliphatic acids;
- (iv) naphthenic acids having the general formula: ##STR30## in which n>1; (v) heavy acid fractions selected from the group consisting of mixtures of C.sub.5 -C.sub.6, C.sub.7 -C.sub.9, C.sub.9 -C.sub.11, C.sub.10 -C.sub.16, C.sub.10 -C.sub.13, and C.sub.12 -C.sub.16 acids;
- (vi) di-nonylnaphthalene-sulfonic acid;
- (vii) ##STR31## (viii) at least one acid of the formula ##STR32## (a) and derived from the carboxylation of C.sub.9 olefins and in which R.sub.1 and R.sub.2 are hydrocarbon radicals in which the sum of the carbon atoms is equal to 7; or (b) derived by the oxo synthesis from C.sub.9 -C.sub.11 olefins and being a mixture of saturated tertiary monocarboxylic acids in which R.sub.1 and R.sub.2 hydrocarbon radicals in which the sum of the carbon atoms is equal to 6, 7, or 8; and
- (ix) acetylacetone.
- 78. The process as defined by claim 77 wherein said extraction agent is selected form the group consisting of: bis-(2-ethylhexyl)-phosphoric acid; bis-(2-ethylhexyl)-phosphonic acid; and butanoic, valeric, octoic, caproic, caprylic, capric, pelargonic, and lauric acids.
- 79. The process as defined by claim 46, said extraction agent being a cationic extractant selected from the group consisting of organophosphorus acids; aliphatic or aromatic acids; halogen-containing aliphatic, aromatic, or cycloaliphatic acids; naphthene acids; heavy acid fractions; sulfonic acids; at least one acid having the general formula: ##STR33## in which R.sub.1 and R.sub.2 are substituted or unsubstituted hydrocarbon radicals; and B-diketones.
- 80. The process as defined by claim 79, said cationic extractant being selected from the group consisting of:
- (i) organophosphorus acids of the general formula: ##STR34## in which R.sub.1 and R.sub.2 represent aliphatic or aromatic hydrocarbon radicals which are such that the total number of carbon atoms in R.sub.1 and R.sub.2 is equal to at least 10;
- (ii) aliphatic acids in which the hydrocarbon radicals have from 3 to 20 carbon atoms;
- (iii) halogen-containing aliphatic, aromatic, or cycloaliphatic acids;
- (iv) naphthenic acids having the general formula: ##STR35## in which n>1; (v) heavy acid fractions selected from the group consisting of mixtures of C.sub.5 -C.sub.6, C.sub.7 -C.sub.9, C.sub.9 -C.sub.11, C.sub.10 -C.sub.16, C.sub.10 -C.sub.13, and C.sub.12 -C.sub.16 acids;
- (vi) di-nonylnaphthalene-sulfonic acid;
- (vii) ##STR36## (viii) at least one acid of the formula ##STR37## (a) and derived from the carboxylation of C.sub.9 olefins and in which R.sub.1 and R.sub.2 are hydrocarbon radicals in which the sum of the carbon atoms is equal to 7; or (b) derived by the oxo synthesis from C.sub.9 -C.sub.11 olefins and being a mixture of saturated tertiary monocarboxylic acids in which R.sub.1 and R.sub.2 hydrocarbon radicals in which the sum of the carbon atoms is equal to 6, 7, or 8; and
- (ix) acetylacetone.
- 81. The process as defined by claim 80 wherein said extraction agent is selected form the group consisting of: bis-(2-ethylhexyl)-phosphoric acid; bis-(2-ethylhexyl)-phosphonic acid; and butanoic, valeric, octoic, caproic, caprylic, capric, pelargonic, and lauric acids.
Priority Claims (1)
Number |
Date |
Country |
Kind |
79 17212 |
Jul 1979 |
FRX |
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of application Ser. No. 670,061, filed Nov. 9, 1984, now abandoned, which is a continuation-in-part of Ser. No. 360,559, filed Mar. 22, 1982, now abandoned, which in turn is a continuation of Ser. No. 162,492, filed June 24, 1980, now abandoned.
US Referenced Citations (4)
Number |
Name |
Date |
Kind |
3575687 |
Drobnick et al. |
Apr 1971 |
|
3582263 |
Chiola et al. |
Jun 1971 |
|
4029733 |
Faugeras et al. |
Jun 1977 |
|
4041125 |
Alstad et al. |
Aug 1977 |
|
Foreign Referenced Citations (2)
Number |
Date |
Country |
45-25580 |
Aug 1970 |
JPX |
4042765 |
Nov 1974 |
JPX |
Non-Patent Literature Citations (1)
Entry |
Habashi, F. "Principles of Extractive Metallurgy", vol. 2, Gordon and Bresch, N.Y., 1970, pp. 347-370 and 385-388. |
Continuations (2)
|
Number |
Date |
Country |
Parent |
670061 |
Nov 1984 |
|
Parent |
162492 |
Jun 1980 |
|
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
360559 |
Mar 1982 |
|