Organo-phosphorus Solvent Patents (Class 423/10)
  • Patent number: 6623710
    Abstract: A spent fuel reprocessing method including the steps of partitioning U and Pu(III) in a solvent by solvent extraction and subsequently polishing the solvent in a neptunium rejection operation for removing Np therefrom. The solvent obtained from the neptunium rejection operation (the polished solvent or NpA solvent product) is then recycled to a U/Pu partitioning operation. The method enables a reduction in solvent feed and solvent effluent volumes.
    Type: Grant
    Filed: September 29, 2000
    Date of Patent: September 23, 2003
    Assignee: British Nuclear Fuels PLC
    Inventors: Emmanuel Gaubert, Gavin Paul Towler, Andrew Lindsay Wallwork
  • Publication number: 20030012715
    Abstract: A multicolumn selectivity inversion generator has been developed in which bismuth-213 is selectively extracted from an HCl solution of the actinium-225 parent (and its radiogenic descendents) by a primary separation column containing a separation medium containing a neutral oxygenated organophosphorus extractant. After rinsing with dilute HCl, the bismuth-213 is stripped with a buffered NaCl solution. The stripped solution is passed through a cation-exchange resin guard column that retains the actinium-225 and radium-225 contaminants while the bismuth-213 elutes. This generator method minimizes the unpredictable effects of radiation damage to the support material and permits the reliable production of bismuth-213 of high chemical and radionuclidic purity.
    Type: Application
    Filed: May 31, 2002
    Publication date: January 16, 2003
    Inventors: Andrew H. Bond, E. Philip Horwitz
  • Patent number: 6504077
    Abstract: A method of decontaminating a radioactively contaminated oxide on a surface. The radioactively contaminated oxide is contacted with a diphosphonic acid solution for a time sufficient to dissolve the oxide and subsequently produce a precipitate containing most of the radioactive values. Thereafter, the diphosphonic solution is separated from the precipitate. HEDPA is the preferred diphosphonic acid and oxidizing and reducing agents are used to initiate precipitation. SFS is the preferred reducing agent.
    Type: Grant
    Filed: October 10, 2000
    Date of Patent: January 7, 2003
    Assignee: The University of Chicago
    Inventors: Ankur Purohit, Michael D. Kaminski, Luis Nunez
  • Patent number: 6468445
    Abstract: The present invention relates to solvents, and methods, for selectively extracting and recovering radionuclides, especially cesium and strontium, rare earths and actinides from liquid radioactive wastes. More specifically, the invention relates to extracting agent solvent compositions comprising complex organoboron compounds, substituted polyethylene glycols, and neutral organophosphorus compounds in a diluent. The preferred solvent comprises a chlorinated cobalt dicarbollide, diphenyl-dibutylmethylenecarbamoylphosphine oxide, PEG-400, and a diluent of phenylpolyfluoroalkyl sulfone. The invention also provides a method of using the invention extracting agents to recover cesium, strontium, rare earths and actinides from liquid radioactive waste.
    Type: Grant
    Filed: April 27, 2001
    Date of Patent: October 22, 2002
    Assignee: The United States of America as represented by the United States Department of Energy
    Inventors: Valeriy Nicholiavich Romanovskiy, Igor V. Smirnov, Vasiliy A. Babain, Terry A. Todd, Ken N. Brewer
  • Patent number: 6436358
    Abstract: A method and apparatus for removing metal contaminants from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents may be added to precipitate the metal oxide and/or the metal as either metal oxide, metal hydroxide, or as a salt. The precipitated materials are filtered, dried and packaged for disposal as waste or can be immobilized as ceramic pellets. More than about 90% of the metals and mineral residues (ashes) present are removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be spray-dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 1.0 ppm of contaminants.
    Type: Grant
    Filed: May 21, 1999
    Date of Patent: August 20, 2002
    Assignee: The Regents of the University of California
    Inventors: Peter C. Hsu, Erica H. Von Holtz, David L. Hipple, Leslie J. Summers, William A. Brummond, Martyn G. Adamson
  • Patent number: 6379634
    Abstract: A method of dissolving in an ionic liquid a metal in an initial oxidation state below its maximum oxidation state, characterized in that the ionic liquid reacts with the metal and oxidizes it to a higher oxidation state. The initial metal may be in the form of a compound thereof and may be irradiated nuclear fuel comprising UO2 and/or PuO2 as well as fission products. The ionic liquid typically is nitrate-based, for example a pyridinium or substituted imidazolium nitrate, and contains a Bronstead or Franklin acid to increase the oxidizing power of the nitrate. Suitable acids are HNO3, H2SO4 and [NO+]. Imidazolium nitrates and certain pyridinium nitrates form one aspect of the invention.
    Type: Grant
    Filed: July 2, 1999
    Date of Patent: April 30, 2002
    Assignee: British Nuclear Fuels Plc
    Inventors: Mark Fields, Graham Victor Hutson, Kenneth Richard Seddon, Charles Mackintosh Gordon
  • Patent number: 6312653
    Abstract: The invention involves a process for separating actinides and lanthanides by liquid-liquid extraction by means of calixarenes. These calixarenes have the formula: with R1 and R2 being alkyl groups or o-nitrophenoxy alkyl groups and R3 and R4 being aryl groups, and they are used in an organic liquid phase containing an organic diluent. The diluent and the calixarene concentration of the organic phase are chosen so as to ensure an enrichment of the organic phase with the actinide(s) and/or lanthanide(s) to be separated from an aqueous acid or saline solution.
    Type: Grant
    Filed: April 27, 2000
    Date of Patent: November 6, 2001
    Assignee: Commissariat A l'Energie Atomique
    Inventors: Laetitia Delmau, Nicole Simon, Jean-François Dozol, Bernard Tournois, Christine Roussin-Bouchard, Serge Eymard, Volker Böhmer, Cordula Grüttner, Alexander Shivanyuk, Christian Musigmann
  • Patent number: 6312654
    Abstract: The invention relates to a method of separating trivalent actinides from at least one trivalent lanthanide and/or yttrium, whereby the trivalent actinides are extracted from an aqueous solution containing a H+ concentration of 0.01 to 2 moles/liter by using as extractant an (aryl)dithiophosphinic acid of the Formula R1R2PS (SH), in which R1 is phenyl or naphthyl, R2 is phenyl or naphthyl, or R1 and R2 are each phenyl or naphthyl substituted by methyl, ethyl, propyl, isopropyl, cyano, nitro, or halogen, with addition of an extraction synergist selected from the group consisting of trioctylphosphate, tris-(2-propylpentyl)-phosphate, and tris-(2-ethylhexyl)-phosphate. The use of the synergist in the extraction allows for a more selective extraction.
    Type: Grant
    Filed: March 16, 2000
    Date of Patent: November 6, 2001
    Assignee: Forschungszentrum Julich GmbH
    Inventors: Giuseppe Modolo, Reinhard Odoj
  • Patent number: 6306355
    Abstract: The invention involves the separation of actinides and lanthanides by membrane transport by means of a calixarene. To this end, a first aqueous solution containing at least one metal from the group of actinides and lanthanides to be separated is placed in the compartment 3 and a second aqueous re-extraction solution such as a 10−2 mol/L solution of HNO3 is placed in the compartment 5. The membrane 6 is a microporous membrane of which the pores are filled with a liquid organic phase (calixarene and diluent) chosen in order to favour membrane transport of the metal(s) to be separated from compartment 3 to compartment 5.
    Type: Grant
    Filed: April 19, 2000
    Date of Patent: October 23, 2001
    Assignee: Commissariat a l'Energie Atomique
    Inventors: Laetitia Delmau, Nicole Simon, Jean-François Dozol, Bernard Tournois, Christine Roussin-Bouchard, Volker Böhmer, Ralf A. Jakobi, Oliver Mogck, Abdi Tunayar
  • Patent number: 6303090
    Abstract: A process for converting UF6 to a solid uranium compound such as UO2 and CaF. The UF6 vapor form is contacted with an aqueous solution of NH4OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH4OH and NH4F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH4OH and NH4F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH)2 to precipitate CaF2 leaving dilute NH4OH.
    Type: Grant
    Filed: May 17, 2000
    Date of Patent: October 16, 2001
    Assignee: The United States of America as represented by the United States Department of Energy
    Inventors: Alan B. Rothman, Donald G. Graczyk, Alice M. Essling, E. Philip Horwitz
  • Patent number: 6258333
    Abstract: The present invention relates to solvents, and methods, for selectively extracting and recovering radionuclides, especially cesium and strontium, rare earths and actinides from liquid radioactive wastes. More specifically, the invention relates to extracting agent solvent compositions comprising complex organoboron compounds, substituted polyethylene glycols, and neutral organophosphorus compounds in a diluent. The preferred solvent comprises a chlorinated cobalt dicarbollide, diphenyl-dibutylmethylenecarbamoylphosphine oxide, PEG-400, and a diluent of phenylpolyfluoroalkyl sulfone. The invention also provides a method of using the invention extracting agents to recover cesium, strontium, rare earths and actinides from liquid radioactive waste.
    Type: Grant
    Filed: October 7, 1999
    Date of Patent: July 10, 2001
    Assignee: The United States of America as represented by the United States Department of Energy
    Inventors: Valeriy Nicholiavich Romanovskiy, Igor V. Smirnov, Vasiliy A. Babain, Terry A. Todd, Ken N. Brewer
  • Patent number: 6137027
    Abstract: Disclosed herein are a solid waste treatment agent comprising phosphorous acid or a derivative thereof and/or hypophosphorous acid or a derivative thereof, or phosphorous acid or a derivative thereof and/or hypophosphorous acid or a derivative thereof, and an aluminum compound and/or a titanium compound, and a method of treating solid waste, which comprises adding the solid waste treatment agent to solid waste containing harmful metals and/or organic chlorinated compounds such as dioxins and PCB to make the solid waste harmless.
    Type: Grant
    Filed: February 10, 1999
    Date of Patent: October 24, 2000
    Assignee: Miyoshi Yushi Kabushiki Kaisha
    Inventors: Masatake Kawashima, Takashi Ogawa, Kazuhiro Terada, Hiroyuki Okayama, Katsushi Sugiyama, Kazuo Hosoda, Masafumi Moriya
  • Patent number: 6093375
    Abstract: A spent fuel reprocessing method includes at least the formation of an aqueous solution and at least one solvent extraction step. Formohydroxarmic acid is used to reduce any Np(VI) to Np(V) and/or to form a complex with Np(IV). As a result, substantially all the neptunium present is retained in the aqueous phase during solvent extraction.
    Type: Grant
    Filed: August 7, 1998
    Date of Patent: July 25, 2000
    Assignee: British Nuclear Fuels PLC
    Inventors: Robin John Taylor, Iain Stewart Denniss, Andrew Lindsay Wallwork
  • Patent number: 5966584
    Abstract: Trivalent actinides can be separated from trivalent lanthanides in aqueous solutions at H.sup.+ concentrations of 2 mol/l to 0.001 mol/liter by extraction with bis(aryl)dithiophosphinic acid and a synergist such as TBP, TOPO and TBPO in an organic solvent. A high separation efficiency results. The method is applicable to high-level liquid waste from reactors and nuclear-material processing plants.
    Type: Grant
    Filed: September 17, 1997
    Date of Patent: October 12, 1999
    Assignee: Forschungszentrum Julich GmbH
    Inventors: Giuseppe Modolo, Reinhard Odoj
  • Patent number: 5866087
    Abstract: The invention relates to novel calixarenes of formula: ##STR1## in which m is equal to 0 or 1, n is an integer from 2 to 8, with 4.ltoreq.n(m+1).ltoreq.8,R.sup.1 and R.sup.2, which can be the same or different, are alkyl or O-nitrophenoxyalkyl groups andR.sup.3 and R.sup.4, which can be the same or different, are alkyl or aryl groups.The calixarenes can be used for extracting actinides and lanthanides from aqueous solutions from spent fuel reprocessing.
    Type: Grant
    Filed: October 14, 1997
    Date of Patent: February 2, 1999
    Assignee: Commissariat a l'Energie Atomique
    Inventors: Jean-Fran.cedilla.ois Dozol, Helene Rouquette, Volker Bohmer, Cordula Gruttner, Ralf A. Jakobi, Dagmar Kraft, Walter Vogt
  • Patent number: 5758255
    Abstract: A method of reducing the entrainment of aqueous mineral acid solutions in organic extractants used in the solvent extraction of metals from the aqueous fluid is disclosed. The method comprises adding an effective, entrainment prevention amount of a water soluble cationic polymer having a molecular weight of from about 10,000 to about 500,000 to a metal rich aqueous mineral acid solution, immediately prior to, or during mixing with a metal poor organic extractant, and then recovering a metal poor aqueous mineral acid phase, and a metal rich organic extractant phase having a reduced level of entrainment of the aqueous mineral acid solution. In a preferred embodiment the metal is copper, and the polymer is poly(diallyldimethylammonium) chloride.
    Type: Grant
    Filed: August 19, 1996
    Date of Patent: May 26, 1998
    Assignee: Nalco Chemical Company
    Inventors: E. Michael Kerr, Kenneth M. Smith, II
  • Patent number: 5708958
    Abstract: A method is provided for separating trivalent actinides and rare earth elements in the TRUEX method using a CMPO-TBP mixed solvent. The method of separating trivalent actinides and rare earth elements comprises a trivalent actinide/rare earth extraction step wherein trivalent actinides and rare earth elements are extracted by a solvent from highly acid waste generated by reprocessing of spent nuclear fuel, a nitric acid removal step wherein the nitric acid concentration of the solvent used to extract the trivalent actinides and rare earth elements is reduced, and a separation step wherein the trivalent actinides and rare earth elements contained in the solvent of low nitric acid concentration, are separated from each other.
    Type: Grant
    Filed: August 12, 1996
    Date of Patent: January 13, 1998
    Assignee: Doryokuro Kakunenryo Kaihatsu Jigyodan
    Inventors: Yoshikazu Koma, Masayuki Watanabe, Shinichi Nemoto
  • Patent number: 5702676
    Abstract: This invention provides an improved process of preparing UO.sub.2 powder from poor quality, partially oxidized powder containing organic and inorganic impurities. The process is illustrated in the flow chart of FIG. 1 which includes the steps of (a) oxidizing a uranium-containing scrap also containing inorganic and cationic organic impurities; (b) solubilizing, typically with nitric acid, the uranium contained in the oxidized scrap to produce uranyl nitrate; (c) solvent extracting the solubilized product of step (b) to remove cation impurities to provide a purified uranyl nitrate solution; (d) precipitating the purified uranyl nitrate with ammonia to form ammonium diuranate powder; and (e) calcining and passivating the ammonium diuranate powder to produce UO.sub.2 powder; and optionally (f) forming the UO.sub.2 powder of step (e) into pellets and sintering the formed pellets to produce sintered UO.sub.2 pellets.
    Type: Grant
    Filed: June 20, 1996
    Date of Patent: December 30, 1997
    Assignee: General Electric Company
    Inventors: Richard I. Larson, Stephen E. Selby, Michael P. Enger
  • Patent number: 5682593
    Abstract: Use of diethyl dodecylphosphonate (DEDP) for the extraction of acids and metal salts from aqueous solutions.
    Type: Grant
    Filed: October 19, 1995
    Date of Patent: October 28, 1997
    Assignee: Bayer Aktiengesellschaft
    Inventors: Christoph Holzner, Hans-Dieter Block, Hans-Heinrich Moretto
  • Patent number: 5678242
    Abstract: Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.
    Type: Grant
    Filed: July 7, 1994
    Date of Patent: October 14, 1997
    Assignee: Arch Development Corporation
    Inventors: Earl Philip Horwitz, Ralph Carl Gatrone, Kenneth LaVerne Nash
  • Patent number: 5625862
    Abstract: A method for simultaneously partitioning a metal oxide and silica from a material containing silica and the metal oxide, using a biphasic aqueous medium having immiscible salt and polymer phases.
    Type: Grant
    Filed: May 1, 1995
    Date of Patent: April 29, 1997
    Assignee: ARCH Development Corporation
    Inventors: David J. Chaiko, R. Mensah-Biney
  • Patent number: 5587142
    Abstract: A method of dissolving metal oxides using a mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: December 24, 1996
    Assignee: Arch Development Corporation
    Inventors: Earl P. Horwitz, Renato Chiarizia
  • Patent number: 5585043
    Abstract: In a method of coextracting neptunium and plutonium, a nitric acid solution containing a mixture of neptunium and plutonium is oxidized by irradiation of ultraviolet light. As a result, different valences of neptunium are adjusted all into the valence 6, which can remain in water, and in the meantime, valences of plutonium are adjusted into the valence 4 or 6, which can be extracted in the organic phase. It is therefore possible to coextract neptunium and plutonium without difficulty. The coextracted neptunium and plutonium can be used in forming mixed fuel by blending at least a portion of at least one of neptunium and plutonium which neptunium and plutonium have been formed by separating a nitric acid solution containing neptunium and plutonium by exposing the solution and a reducing agent to ultraviolet radiation to adjust the valences, and extracting the solution using an organic phase to extract plutonium from the solution into the organic phase.
    Type: Grant
    Filed: September 12, 1994
    Date of Patent: December 17, 1996
    Assignee: Doryokuro Kakunenryo Kaihatsu Jigyodan
    Inventors: Yukio Wada, Kyoichi Morimoto, Takayuki Goibuchi, Hiroshi Tomiyasu
  • Patent number: 5500192
    Abstract: In a method of separating neptunium and plutonium, a nitric acid solution containing a mixture of neptunium and plutonium is oxidized by irradiation of ultraviolet light in the presence of a reducing agent. As a result, different valences of neptunium are adjusted all into the valence 5, which can remain in water, and in the meantime, valences of plutonium are adjusted into the valence 4 or 6, which can be extracted in the organic phase. It is therefore possible to separate neptunium and plutonium from each other without difficulty.
    Type: Grant
    Filed: September 12, 1994
    Date of Patent: March 19, 1996
    Assignee: Doryokuro Kakunenryo Kaihatsu Jigyodan
    Inventors: Yukio Wada, Kyoichi Morimoto, Takayuki Goibuchi, Hiroshi Tomiyasu
  • Patent number: 5468456
    Abstract: A process for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents.
    Type: Grant
    Filed: February 4, 1994
    Date of Patent: November 21, 1995
    Assignee: The University of Chicago
    Inventors: Luis Nunez, George F. Vandergrift
  • Patent number: 5463177
    Abstract: The extraction process includes supplying solvent under gas pressure for introduction of the solvent adjacent the bottom of a vessel containing the sample. The vessel lies in a water bath and ultrasonic energy is applied to the bath and hence to the sample to facilitate interaction between the solvent and the sample. Because the solvent is immiscible in the sample and of lesser density, the solvent and solubilized material rise to the top of the vessel. An extraction tube under vacuum pressure continuously removes the solvent with the solubilized material.
    Type: Grant
    Filed: August 23, 1994
    Date of Patent: October 31, 1995
    Assignee: General Electric Company
    Inventor: John K. Youngs
  • Patent number: 5443731
    Abstract: A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.
    Type: Grant
    Filed: July 21, 1994
    Date of Patent: August 22, 1995
    Assignee: The United States of America as represented by the United States Department of Energy
    Inventors: Bruce A. Moyer, Richard A. Sachleben, Peter V. Bonnesen
  • Patent number: 5437847
    Abstract: A method of recovering volatile ruthenium, which is separated and formed by constant potential electrolysis from high-level radioactive liquid waste discharged from the reprocessing step of spent nuclear fuel by purex process, in the form of stable solid. The method comprises electrolyzing at a constant potential a high-level radioactive liquid waste from which palladium has substantially been removed in advance, thereby vaporizing ruthenium, bringing the vaporized ruthenium into contact with an aqueous solution of formic acid to precipitate ruthenium oxide, and separating the precipitate from the aqueous solution of formic acid.
    Type: Grant
    Filed: December 7, 1994
    Date of Patent: August 1, 1995
    Assignee: Doryokuro Kakunenryo Kaihatsu Jigyodan
    Inventors: Masayuki Yoneya, Kazuhiro Kawamura, Shin-ichiro Torata, Takeshi Takahashi
  • Patent number: 5409678
    Abstract: An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.
    Type: Grant
    Filed: March 11, 1993
    Date of Patent: April 25, 1995
    Assignee: The United States of America as represented by the Department of Energy
    Inventors: Barbara F. Smith, Gordon D. Jarvinen, Dale D. Ensor
  • Patent number: 5332531
    Abstract: Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.
    Type: Grant
    Filed: June 10, 1992
    Date of Patent: July 26, 1994
    Assignee: Arch Development Corporation
    Inventors: Earl P. Horwitz, Ralph C. Gatrone, Kenneth L. Nash
  • Patent number: 5276251
    Abstract: A process for treating organic phosphates, comprising(a) mixing a waste organic solvent mainly composed of an organic phosphate with an additive mainly composed of at least one of metal salts of aliphatic carboxylic acids represented by formula:(C.sub.n H.sub.2n+1 COO).sub.m MwhereinM is K, Ca or Al, andm is a positive integer of 1, 2 or 3,(b) heating the resulting mixture, and(c) optionally burning the mixture to form stable solid containing phosphor content. The metal salts of aliphatic carboxylic acid are preferably metal salts of acetic acid such as potassium acetate, calcium acetate and aluminum acetate. Typical organic phosphate solvent is tributyl phosphate or a mixed solution of tributyl phosphate and benzene.
    Type: Grant
    Filed: March 2, 1993
    Date of Patent: January 4, 1994
    Assignee: Mitsubishi Nuclear Fuel Co.
    Inventors: Yoshinobu Kamei, Wataru Shirato
  • Patent number: 5246901
    Abstract: This invention provides novel compositions comprising aryl phosphonic or phosphinic acids substituted with more than one sulfo radical. These novel compounds may be reacted with tetravalent metal ions to provide polymers having an inorganic backbone, which polymers are useful as acid catalysts.
    Type: Grant
    Filed: May 23, 1988
    Date of Patent: September 21, 1993
    Assignee: Catalytica, Inc.
    Inventor: William A. Sanderson
  • Patent number: 5188736
    Abstract: A new chemical separation process was developed in this invention using 2-methoxyethanol or methyl collosolve (MCS) and ethylene glycol (EG) as separation agents, to separate the valuable extractants such as di(2-ethylhexyl) phosphoric acid(D2EHPA), tri n-octyl-phosphine oxide (TOPO) from spent solvent and to recover the extractants. The process comprises separation and recovery sections. In the separation section the extractants were removed by the polar solution from spent solvent based on the difference of miscibilities. In the recovery section, the polar solution loaded with extractants was distillated under vacuum to remove MCS as a distillate and water was added to the bottom product to facilitate the separation of the extractants. By using this novel process, 99% of D2EHPA and 70% of TOPO in the spent solvent were separated and 98% of D2EHPA was recovered. MCS and EG can be regenerated and reused in the process.
    Type: Grant
    Filed: August 27, 1991
    Date of Patent: February 23, 1993
    Assignee: Institute of Nuclear Energy Research
    Inventors: Ben-Li Pen, Dah-Ping Wang, Ying-Chu Hoh, Kuo-Hao Tsao
  • Patent number: 5169609
    Abstract: The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal.
    Type: Grant
    Filed: June 19, 1991
    Date of Patent: December 8, 1992
    Assignee: The United States of America as represented by the United States Department of Energy
    Inventors: E. Philip Horwitz, Mark L. Dietz
  • Patent number: 5156824
    Abstract: New diphosphonic derivatives are capable of extracting the uranium in phosphoric acid with a P205 content ranging from 10 to 50 per unit.The new diphosphonic derivatives have the following formula: ##STR1## wherein R is selected from the group consisting of hydrogen and alkyl radicals having 1 to 15 carbon atoms and having at most 2 branchings in the alkyl radical, and A is a mono- or di- substituted methylene radical wherein the substituents are selected from the group consisting of an alkyl group having at most two branchings, hydroxyl, an amino group, and hydrogen, wherein the total number of carbon atoms in the R and A groups is from 15 to 50 carbon atoms, with the proviso that when A is substituted by hydroxy or amino. A has 15 to 25 carbon atoms, and wherein A is linked to a water insoluble crosslinked ion exchange resin skeleton.
    Type: Grant
    Filed: June 13, 1989
    Date of Patent: October 20, 1992
    Assignee: Compagnie Francaise de Mokta
    Inventors: Pierre Blanquet, Francois Ricalens
  • Patent number: 5156722
    Abstract: Two alternate, mutually exclusive, methods of removing radio contaminants from metal are taught based respectively on electrowinning or electrorefining of the base metal. The alternative using electrorefining controls the anolyte oxidation potential to selectively reduce the technetium in the metallic feedstock solution from Tc(VII) to Tc(IV) forcing it to report to the anodic slimes preventing it from reporting to the cathodic metal product. This method eliminates the need for peripheral decontamination processes such as solvent extraction and/or ion exchange to remove the technetium prior to nickel electrorefining. The other alternative method combines solvent extraction with electrowinning. By oxidizing technetium to the heptavalent state and by using mixtures of tri-n-octyalphosphine oxide and di-2-ethyl phosphoric acid in aliphatic hydrocarbon carriers to extract the radio contaminants prior to electrowinning, the background metal may be recovered for beneficial reuse.
    Type: Grant
    Filed: July 25, 1991
    Date of Patent: October 20, 1992
    Assignee: Westinghouse Electric Corp.
    Inventors: Thomas S. Snyder, William R. Gass, Samuel A. Worcester, Laura J. Ayers
  • Patent number: 5057289
    Abstract: A process for the separation of uranium and plutonium as well as fission ducts including technetium from a nitric acid feed solution (fuel solution) in which said solution is treated with an extraction agent in an organic solvent to charge said agent with U, Pu and fission products including technetium by the counterflow process. The charged extraction agent containing U, Pu and fission products including technetrium is treated with a washing solution and subsequently with a reducing agent for the separation of the uranium from the plutonium and from fission products including technetium not previously washed out. To improve the separation of uranium and obtain a cleaner uranium end product, the treatment of the organic solvent containing said charged agent with reducing agent is effected in one or more stages by the crossflow process instead of by the counterflow process.
    Type: Grant
    Filed: March 9, 1989
    Date of Patent: October 15, 1991
    Assignee: Deutsche Gesellschaft fur Wideraufarbeitung von Kernbrennstoffen mbH
    Inventors: Wolfgang Issel, Werner Knoch, Hartmut Ramm
  • Patent number: 5017344
    Abstract: A process for separating iron +3 from uranium +6 is an organic solution of a neutral phosphine oxide and an acid organophosphorus compound. The uranium-containing organic solution is contacted with aqueous oxalic acid or an aqueous mixture of phosphoric acid and sulfuric acid so that most of the uranium remains in the organic solution and most of the iron passes into the aqueous acid.
    Type: Grant
    Filed: July 11, 1989
    Date of Patent: May 21, 1991
    Assignee: Compagnie Generale des Matieres Nucleaires (Cogema)
    Inventors: Andre Textoris, Georges Lyaudet, Andre Bathelier
  • Patent number: 5000927
    Abstract: The "Purex" solvent extraction and separation process for recovering uranium from scrap material or spent fuel containing gadolinia is modified by treating uranium containing scrap or spent fuel with nitric acid to convert uranium oxide to soluble uranyl nitrate in an aqueous medium, separating the uranyl nitrate from the aqueous media with an organic medium containing tri-butyl phosphate, and then releasing the separated uranium from the organic medium with water. The improvement comprises monitoring the density of the organic medium and controlling the feed rate of the uranium in the aqueous medium in response to the density measurements.
    Type: Grant
    Filed: March 31, 1989
    Date of Patent: March 19, 1991
    Assignee: General Electric Company
    Inventors: Steven J. Babb, William R. Becker
  • Patent number: 4983300
    Abstract: The invention relates to a process for the reextraction in aqueous solution of the plutonium present in an organic solvent, more particularly usable for uranium-plutonium separation.According to this process the organic solvent is contacted with an acid aqueous solution of uranous salt, e.g. uranous nitrate, and hydroxylamine salt, e.g. hydroxylamine nitrate. Under these conditions, the uranous nitrate acts as a reducing agent for plutonium at valency (III and the hydroxylamine nitrate, which is also a plutonium reducing, agent, stabilizes Pu(III) and U(IV) in aqueous phase.Performances comparable to those of the U(IV)-hydrazone nitrate system are obtained without forming prejudicial hydrazine nitrate decomposition products. (FIG. 2).
    Type: Grant
    Filed: December 16, 1988
    Date of Patent: January 8, 1991
    Assignee: Commissariat a l'Energie Atomique
    Inventors: Michel Germain, Bruno Gillet, Jean-Yves Pasquiou
  • Patent number: 4981616
    Abstract: In a method for recovering plutonium and uranium from spent nuclear fuel by solvent extraction having solvent consisting of tri-n-butyl phosphate, dibutyl phosphate and n-dodecane, the improvement comprises separating the n-dodecane from the phosphate by freeze-drying and separating the phosphate from each other and residual impurities by fractional distillation.
    Type: Grant
    Filed: August 29, 1989
    Date of Patent: January 1, 1991
    Assignee: Doryokuro Kakunenryo Kaihatsu Jigyodan
    Inventors: Katsuyuki Ohtsuka, Isao Kondoh, Toru Suzuki
  • Patent number: 4950425
    Abstract: Alkyl phosphates, undiluted or dissolved in hydrophobic solvents can be destroyed in situ by reaction with hydrogen peroxide in the presence of certain transition metal catalyst systems. The invention catalyst system comprises a chromium compound, which dissolves in the aqueous phase, typically an alkali metal chromate, which is employed in conjunction with introduction of an alkali, preferably sodium hydroxide, or in the presence of an alkali buffer to keep the pH of the aqueous phase within a window spanning mildly acidic to mildly alkaline pH during the course of progressive introduction of the hydrogen peroxide, which often lasts from 3 to 10 hours, thereby enabling the oxidation of the alkyl phosphate to continue. The reaction is preferably carried out at a temperature of at least 60.degree. C., and particularly at about 65.degree. to 75.degree. C., or at about the boiling point of the aqueous phase.
    Type: Grant
    Filed: May 11, 1989
    Date of Patent: August 21, 1990
    Assignee: Interox Chemicals Limited
    Inventors: Kenneth T. Rowbottom, John N. R. Wilkinson, Terence M. Conboy, Graham V. Hutson
  • Patent number: 4943318
    Abstract: Thorium is removed from raffinate effluent by pre-washing with odorless kerosene to remove organic contaminants, followed by solvent extraction counter-currently with tri-n-octylphosphine oxide in odorless kerosene. The loaded solvent from the solvent extraction is back-washed with K.sub.2 CO.sub.3 solution at about 60.degree. C., and subsequent lime addition precipitates Th(OH).sub.4.
    Type: Grant
    Filed: December 27, 1989
    Date of Patent: July 24, 1990
    Assignee: British Nuclear Fuels PLC
    Inventor: Alan Rushton
  • Patent number: 4941998
    Abstract: The invention is directed to a method of washing a solvent in the reprocessing of irradiated nuclear fuel. The solvent is washed with an aqueous solution in a mixer-settler having at least one stage which includes a mixing chamber and a settling chamber. The pH of the dispersion in the mixing chamber is measured and an amount of washing solution is added which influences the pH toward the desired operational value. An apparatus for carrying out the method is also disclosed.
    Type: Grant
    Filed: May 18, 1988
    Date of Patent: July 17, 1990
    Assignee: Deutsche Gesellschaft fur Wiederaufarbeitung von Kernbrennstoffen mbH
    Inventors: Klaus Eiben, Heinz Evers
  • Patent number: 4922012
    Abstract: Novel organic tertiary phosphine oxides for example, bidentate organophosphorus actinide extractants, such as the carbamoylmethylphosphine oxides (CMPO's) are disclosed, such compounds can be prepared (e.g., in 85% or better yield and purity) by a process involving phase transfer catalysis, under conditions where degradive hydrolysis of the products or reactants is substantially avoided. For example, tertiary carbamoylmethylphosphine oxides which are useful as extractants for transplutonium elements are disclosed and can be prepared by reaction of the corresponding secondary phosphine oxides with 2-substituted acetamides (wherever the substituent is a good leaving group, e.g., chlorine) in a two-phase system containing a high concentration of an aqueous base (preferably sodium hydroxide) and a suitable phase transfer catalyst, e.g., tetralkylammonium chlorides.
    Type: Grant
    Filed: January 12, 1984
    Date of Patent: May 1, 1990
    Assignee: Occidental Chemical Corporation
    Inventor: Kenneth M. Kem
  • Patent number: 4891163
    Abstract: High-purity uranium can be effectively recovered from gadolinium-containing nuclear fuel scraps by dissolving the scraps in a mineral acid, extracting uranium from the resulting solution with a solvent, washing the organic phase with water or a dilute mineral acid, and counter-extraction with water or a dilute mineral acid. This invention also provides an efficient method of recovering high-purity gadolinium from the acidic washings coming from the above washing step and containing small amounts of radioactive elements (uranium, thorium and others) by adding an alkali, removing the precipitate thus formed, lowering the pH of filtrate to 2 or less, and adding an oxalic acid source to precipitate gadolinium oxalate.
    Type: Grant
    Filed: October 1, 1986
    Date of Patent: January 2, 1990
    Assignee: Sumitomo Metal Mining Company Limited
    Inventors: Cyuzaburo Tanaka, Teruyoshi Yazama, Yoshiki Miyajima, Masaharu Kashiwa, Hiroshi Sugai
  • Patent number: 4871478
    Abstract: A process for the extraction of uranium and plutonium from spent nuclear fuels or breeder reactor materials. The spent nuclear fuels or breeder reactor materials are dissolved in nitric acid to provide an aqueous acid solution containing uranium, plutonium, neptunium, other transuranium elements, fission products, corrosion products, activation products and other contamination products. This aqueous acid solution is fed, as an aqueous phase, at a controllable flow rate into a liquid-liquid extraction apparatus also having an organic solvant phase flowing at a controllable rate. The organic phase contains an extraction agent. The temperature of solutions in the extraction apparatus and/or the concentration of the aqueous acid solution before the said aqueous acid solution is fed into the extraction apparatus, is adjusted to satisfy the following inequality: ##EQU1## where T.sub.E =the temperature of the solutions in the extractor (.degree.C.);U.sub.f =the uranium concentration of the feed solution (g/l);Pu.
    Type: Grant
    Filed: November 9, 1987
    Date of Patent: October 3, 1989
    Assignee: Kernforschungszentrum Karlsruhe GmbH
    Inventors: Georg Petrich, Helmut Schmieder
  • Patent number: 4867951
    Abstract: An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).
    Type: Grant
    Filed: March 31, 1988
    Date of Patent: September 19, 1989
    Assignee: The United States of America as represented by the United States Department of Energy
    Inventors: Barbara F. Smith, Gordon D. Jarvinen, Robert R. Ryan
  • Patent number: 4836956
    Abstract: Polyvalent cations (e.g., U(IV), Fe(III) can be extracted from aqueous solution using novel organophosphorus compounds of the formulas: ##STR1## wherein R.sup.1 and R.sup.2 are the same or different and are selected from alkyl, alkoxyl, alkylaryl and alkylaryloxyl groups having from 1 to 18 carbon atoms or hydroxyl;R.sup.3 is independently selected from substituted and unsubstituted alkyl and alkylaryl groups having 1 to about 18 carbon atoms or hydrogen;R.sup.4 is independently selected from alkyl and alkylaryl groups having 1 to about 18 carbon atoms; provided that the sum of the carbon atoms of the R.sup.1, R.sup.2, R.sup.3 and R.sup.4 groups is at least 15; andR.sup.5 is independently selected from substituted and unsubstituted alkyl and alkylaryl groups having 1 to about 18 carbon atoms or a polymeric group; provided that the sum of the carbon atoms of the R.sup.1, R.sup.2 and R.sup.5 groups is at least 16.
    Type: Grant
    Filed: July 24, 1987
    Date of Patent: June 6, 1989
    Assignee: Occidental Chemical Corporation
    Inventor: Kenneth M. Kem
  • Patent number: 4834787
    Abstract: A process providing solubilization of phosphate rock by contacting the rock with sulfurous acid in the presence of an oxidizing agent selected from the group consisting of hydrogen peroxide and ozone. Use of sulfurous acid in combination with a substoichiometric amount of hydrogen peroxide significantly enhances the solubilization of phosphate rock.
    Type: Grant
    Filed: April 3, 1987
    Date of Patent: May 30, 1989
    Assignee: Dolores R. Pircon
    Inventors: Jerome S. Ratliff, Ladislav J. Pircon