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US4371505A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for the recovery of uranium contained in an impure phosphoric acid

Assignee: Rhone Poulenc Industries SA
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Filing: 1980-02-28
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Granted: 1983-02-01
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Expires: 2000-02-28
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Abstract

Abstract The invention concerns a process for the recovery of the uranium contained in an impure phosphoric acid. The impure acid is treated with an organic phase capable of extracting U (VI), and the resultant organic phase is then re-extracted with an aqueous solution containing complexing acid and an oxidizing-reducing agent in the reduced state, said oxidizing-reducing agent being capable of reducing U +6 to U +4 in said aqueous solution. The resultant aqueous phase is then subjected to electrochemical oxidation, followed by extraction with a second organic phase from which the uranium is recovered, the depleted aqueous solution being recycled to the re-extraction after electrochemical reduction, with the process comprising two organic phase cycles and a cycle of a complexing aqueous solution. The process is of particular interest when applied to the recovery and concentration of uranium contained in a wet process phosphoric acid.

Inventors

  • 👤 Jean-Marc Pautrot

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-02 23:40
CPC Classifications
C; C22; C22B; C22B60/00; C22B60/02; C22B60/0204; C22B60/0217; C22B60/0252; C22B60/026; C25; C25B; C25B1/00; C25B1/01; Y; Y02; Y02P; Y02P10/00; Y02P10/20

Claims Analysis

Total Claims: 37
Claim 1
Independent Claim 482 words
In a continuous process for the recovery of uranium (VI) contained in an impure phosphoric acid comprising: (a) a first cycle comprising (i) extracting an impure phosphoric acid with an organic phase which extracts uranium (VI) without extracting substantial amounts of uranium (IV), followed by separating the phases; (ii) extracting the resultant organic phase charged with uranium (VI) with an aqueous solution containing an oxidizing-reducing agent in the reduced state, said oxidizing-reducing agent being a reducing agent for uranium (VI) to uranium (IV) in said aqueous solution and comprising iron (II) ions, said aqueous solution being a solution of phosphoric acid and the phosphoric acid concentration of said aqueous solution being between about 18% and about 70% by weight of P 2 O 5 , followed by separating the phases; (iii) recycling the resultant organic phase depleted of uranium to the extracting of the impure phosphoric acid; and (iv) treating the resultant aqueous solution charged with uranium (IV), to oxidize the uranium (IV) to uranium (VI) and to convert the oxidizing-reducing agent to its oxidized state; and (b) a second cycle comprising (i) extracting the oxidized aqueous solution resulting from the first cycle with an organic phase which extracts uranium (VI), followed by separating the phases; (ii) washing the resultant organic phase charged with uranium (VI) with a phosphoric acid solution free of iron, the concentration of the phosphoric acid in the washing solution being close to that of the aqueous extracting solution employed in step (ii) of the first cycle, followed by separating the resultant purified organic phase, treating said purified organic phase with an aqueous solution containing carbonate and ammonium ions to precipitate the uranium in said solution in the form of ammonium uranyl tricarbonate, separating the depleted organic phase from the aqueous suspension and recovering the uranium from said aqueous suspension in the form of ammonium uranyl tricarbonate; and (iii) regenerating and then recycling the resultant organic phase depleted of uranium to the second cycle extracting step; the improvement comprising: (i) carrying out step (iv) of the first cycle by treating the aqueous solution charged with uranium (IV) resulting from the extracting step (ii) of the first cycle in its entirety in the anodic compartment of an electrolytic cell under direct current voltage; (ii) carrying out step (i) of the second cycle by treating the oxidized aqueous phase issuing from and anodic compartment with the organic extracting phase of the second cycle; (iii) treating the resultant aqueous phase depleted of uranium in its entirety in the cathodic compartment of said electrolytic separation cell under direct current voltage, to afford an aqueous phase containing the oxidizing-reducing agent in the reduced state; and (iv) recycling the resultant aqueous phase to the back extracting step of the first cycle; whereby the aqueous solution is circulated in a closed loop between the first and second cycles, in the form of a third cycle.
Claim 2
Dependent Claim 482 words
In a continuous process for the recovery of uranium (VI) contained in an impure phosphoric acid comprising: (a) a first cycle comprising (i) extracting an impure phosphoric acid with an organic phase which extracts uranium (VI) without extracting substantial amounts of uranium (IV), followed by separating the phases; (ii) extracting the resultant organic phase charged with uranium (VI) with an aqueous solution containing an oxidizing-reducing agent in the reduced state, said oxidizing-reducing agent being a reducing agent for uranium (VI) to uranium (IV) in said aqueous solution and comprising iron (II) ions, said aqueous solution being a solution of phosphoric acid and the phosphoric acid concentration of said aqueous solution being between about 18% and about 70% by weight of P 2 O 5 , followed by separating the phases; (iii) recycling the resultant organic phase depleted of uranium to the extracting of the impure phosphoric acid; and (iv) treating the resultant aqueous solution charged with uranium (IV), to oxidize the uranium (IV) to uranium (VI) and to convert the oxidizing-reducing agent to its oxidized state; and (b) a second cycle comprising (i) extracting the oxidized aqueous solution resulting from the first cycle with an organic phase which extracts uranium (VI), followed by separating the phases; (ii) washing the resultant organic phase charged with uranium (VI) with a phosphoric acid solution free of iron, the concentration of the phosphoric acid in the washing solution being close to that of the aqueous extracting solution employed in step (ii) of the first cycle, followed by separating the resultant purified organic phase, treating said purified organic phase with an aqueous solution containing carbonate and ammonium ions to precipitate the uranium in said solution in the form of ammonium uranyl tricarbonate, separating the depleted organic phase from the aqueous suspension and recovering the uranium from said aqueous suspension in the form of ammonium uranyl tricarbonate; and (iii) regenerating and then recycling the resultant organic phase depleted of uranium to the second cycle extracting step; the improvement comprising: (i) carrying out step (iv) of the first cycle by treating the aqueous solution charged with uranium (IV) resulting from the extracting step (ii) of the first cycle in its entirety in the anodic compartment of an electrolytic cell under direct current voltage; (ii) carrying out step (i) of the second cycle by treating the oxidized aqueous phase issuing from and anodic compartment with the organic extracting phase of the second cycle; (iii) treating the resultant aqueous phase depleted of uranium in its entirety in the cathodic compartment of said electrolytic separation cell under direct current voltage, to afford an aqueous phase containing the oxidizing-reducing agent in the reduced state; and (iv) recycling the resultant aqueous phase to the back extracting step of the first cycle; whereby the aqueous solution is circulated in a closed loop between the first and second cycles, in the form of a third cycle.
Claim 3
Dependent Claim 47 words
The process of claim 1 wherein, in the third cycle, the oxidized aqueous phase is treated with a small quantity of oxidizing agent to complete the oxidation of U(IV) to U(VI) prior to treating said oxidized aqueous phase with the organic extracting phase of the second cycle.
Claim 4
Dependent Claim 28 words
The process of claim 1 wherein the concentration in phosphoric acid of the impure acid is between 20% and 60% by weight of P 2 O 5 .
Claim 5
Dependent Claim 21 words
The process of claim 1 or 3 wherein the uranium content of the impure acid is between 30 and 300 mg/1.
Claim 6
Dependent Claim 20 words
The process of claim 1 wherein the organic phase of the first cycle contains a cationic extractant for uranium (VI).
Claim 7
Dependent Claim 38 words
The process of claim 5 wherein the cationic extractant is at least one member selected from the group consisting of monoalkylphosphoric, dialkylphosphoric, alkylphenylphosphoric, alkylphosphinic, alkylphosphonic and alkylpyrophosphoric acids, wherein the alkyl groups contain 4 to 10 carbon atoms.
Claim 8
Dependent Claim 12 words
The process of claim 5 wherein the cationic extractant is di(2-ethylhexyl)phosphoric acid.
Claim 9
Dependent Claim 15 words
The process of claim 6 wherein said organic phase further contains a synergistic extraction agent.
Claim 10
Dependent Claim 15 words
The process of claim 7 wherein said organic phase further contains a synergistic extraction agent.
Claim 11
Dependent Claim 13 words
The process of claim 9 wherein the synergistic extraction agent is thioctylphosphine oxide.
Claim 12
Dependent Claim 33 words
The process of claim 1 wherein said organic phase of the first cycle contains an extractant of an anionic character selected from the group consisting of secondary and tertiary amines insoluble in water.
Claim 13
Dependent Claim 32 words
The process of claim 1 wherein said organic phase of the first cycle contains an extractant of a neutral character immiscible with water, selected from the group consisting of the trialkyl phosphates.
Claim 14
Dependent Claim 39 words
The process of claim 1 wherein said organic phase of the first cycle further contains an organic diluent inert with respect to the extractants selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and petroleum ethers.
Claim 15
Dependent Claim 35 words
The process of claim 10 wherein said organic phase further contains an organic diluent inert with respect to the extractants selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and petroleum ethers.
Claim 16
Dependent Claim 11 words
The process of claim 13 wherein the organic diluent is kerosene.
Claim 17
Dependent Claim 11 words
The process of claim 14 wherein the organic diluent is kerosene.
Claim 18
Dependent Claim 37 words
The process of claim 14 wherein the concentration in the organic diluent of di-(2-ethylhexyl)phosphoric acid is between about 0.1 and about 2 molar and the concentration of trioctylphosphine oxide is between about 0.01 and about 2 molar.
Claim 19
Dependent Claim 11 words
The process of claim 17 wherein the organic diluent is kerosene.
Claim 20
Dependent Claim 25 words
The process of claim 1 wherein the uranium concentration in said organic phase of the first cycle is between 20 and 3000 mg per liter.
Claim 21
Dependent Claim 25 words
The process of claim 19 wherein the uranium concentration in said organic phase of the first cycle is between 50 and 500 mg per liter.
Claim 22
Dependent Claim 25 words
The process of claim 1 wherein the percent by weight of P 2 O 5 in the aqueous extracting solution is greater than about 28%.
Claim 23
Dependent Claim 39 words
The process of claim 1 wherein iron (II) ions are present in the aqueous extracting solution employed in step (ii) of the first cycle in an amount between 0.5 and 100 g per liter of said aqueous extracting solution.
Claim 24
Dependent Claim 21 words
The process of claim 1 wherein the process is carried out at a temperature between about 20° and about 80° C.
Claim 25
Dependent Claim 12 words
The process of claim 23 wherein the temperature is about 50° C.
Claim 26
Dependent Claim 35 words
The process of claim 1 wherein the ratio of the flow rate of the organic extracting phase of the first cycle to the flow rate of the aqueous extracting solution is between 20 and 60.
Claim 27
Dependent Claim 12 words
The process of claim 2 wherein the oxidizing agent is hydrogen peroxide.
Claim 28
Dependent Claim 13 words
The process of claim 2 wherein the oxidizing agent is air or oxygen.
Claim 29
Dependent Claim 12 words
The process of claim 27 wherein the oxidizing agent is under pressure.
Claim 30
Dependent Claim 25 words
The process of claim 1 wherein the organic extracting phase of the second cycle is of the same nature as that of the first cycle.
Claim 31
Dependent Claim 25 words
The process of claim 16 wherein the organic extracting phase of the second cycle is of the same nature as that of the first cycle.
Claim 32
Dependent Claim 38 words
The process of claim 1 wherein the ratio of the flow rate of the aqueous solution of the third cycle to the flow rate of the organic extracting phase of the second cycle is between 0.2 and 3.
Claim 33
Dependent Claim 38 words
The process of claim 30 wherein the ratio of the flow rate of the aqueous solution of the third cycle to the flow rate of the organic extracting phase of the second cycle is between 0.2 and 3.
Claim 34
Dependent Claim 51 words
The process of claim 1 wherein the amount of iron extracted in the second extracting step of the first cycle by the aqueous solution of the third cycle is equal to the amount extracted from the aqueous solution of the third cycle by the organic extractive phase of the second cycle.
Claim 35
Dependent Claim 27 words
The process of claim 1 wherein the ammonium uranyl tricarbonate is separated from the aqueous suspension and the resultant aqueous solution is recycled to the precipitation stage.
Claim 36
Dependent Claim 26 words
The process of claim 34 wherein the carbonate and ammonium ion content of the aqueous solution is adjusted prior to its recycling to the precipitation phase.
Claim 37
Dependent Claim 17 words
The process of claim 1 wherein the impure phosphoric acid is a raw wet process phosphoric acid.

References Cited (Backward Citations)

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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1986-01-31 1986-08-02 1987-02-01 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1990-01-31 1990-08-02 1991-02-01 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1994-01-31 1994-08-02 1995-02-01 $7700.00 Window Closed / Lapsed

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