[en] A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated β-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated β-diketone and a trialkyl phosphate, or a fluorinated β-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated β-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process

[en] A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated β-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated β-diketone and a trialkyl phosphate, or a fluorinated β-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated β-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs

[en] Upon extracting separation of metal elements from nitric acid solution in which spent fuels are dissolved, gaseous inorganic materials which can not be used ordinarily as an extraction medium are maintained in a supercritical state to improve solubilization of materials to be used as an extraction medium. In the extracting method, a supercritical fluid of gaseous inorganic materials such as CO₂, CO, ammonium, sulfur hexafluoride or nitrogen is used as an extractor, to provide an extraction rate for rare earth elements higher than that in an existent extraction method using an organic medium as an extraction medium. In addition, the generation amount of radioactive wastes caused by the medium can be remarkably reduced. (T.M.)

[en] The feasibility of using supercritical carbon dioxide as a substitute extraction solvent in nuclear reprocessing was tested by the extraction of lanthanide ions from acidic solution. Lanthanides were extracted from 6 M HNO₃-3 M LiNO₃ solutions using tributyl phosphate- (TBP-) modified CO₂. Synergistic effects were also investigated using a combination of thenoyltrifluoroacetone (TTA) and TBP-modified CO₂ as the extractant. It was found that near-quantitative extraction of Sm³⁺, Eu³⁺, Gd³⁺, and Dy³⁺ was achieved while the extraction efficiencies for La³⁺, Ce³⁺, Yb³⁺, and Lu³⁺ were much lower. The light lanthanides extracted as Ln(NO₃)₃·3TBP and the heavy lanthanides extracted as Ln(NO₃)₃·2TBP when TBP-modified CO₂ was used as the extractant, while Ln(TTA)₃· 3TBP and Ln(TTA)₃·2TBP adducts were extracted when TTA was added to TBP-modified CO₂. 17 refs., 1 fig., 3 tabs

[en] Direct extraction of metal ions by supercritical carbon dioxide is highly inefficient because of the charge neutralization requirement and the weak solute-solvent interactions. One suggested approach of extracting metal ions by supercritical carbon dioxide is to convert the charged species into metal chelates using a chelating agent in the fluid phase. This paper describes a method of extracting lanthanide and uranyl ions from a solid material by supercritical carbon dioxide containing a fluorinated beta-diketone, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione(FOD). Potential applications of this SFE method for separating the f-block elements from environmental samples are discussed. 13 refs., 2 tabs

[en] The removal of toxic organics, metals, and radioisotopes from solids or liquids is a major concern in the treatment of industrial and nuclear wastes. For this reason, developing methods for selective separation of toxic metals and radioactive materials from solutions of complex matrix is an important problem in environmental research. Recent developments indicate supercritical fluids are good solvents for organic compounds. Many gases become supercritical fluids under moderate temperatures and pressures. For example, the critical temperature and pressure of carbon dioxide are 31 degrees C and 73 atm, respectively. The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties of supercritical fluid extraction (SFE). Since CO₂ offers the additional benefits of stability and non-toxicity, the SFE technique avoids generation of organic liquid waste and exposure of personnel to toxic solvents. While direct extraction of metal ions by supercritical fluids is highly inefficient, these ions when complexed with organic ligands become quite soluble in supercritical fluids. Specific ligands can be used to achieve selective extraction of metal ions in this process. After SFE, the fluid phase can be depressurized for precipitation of the metal chelates and recycled. The ligand can also be regenerated for repeated use. The success of this selective chelation-supercritical fluid extraction (SC-SFE) process depends on a number of factors including the efficiencies of the selective chelating agents, solubilities of metal chelates in supercritical fluids, rate of extraction, ease of regeneration of the ligands, etc. In this report, the authors present recent results on the studies of the solubilities of metal chelates in supercritical CO₂, experimental ions from aqueous solution, and the development of selective chelating agents (ionizable crown ethers) for the extraction of lanthanides and actinides