AUSTRALIA Patents Act COMPLETE SPECIFICATION (ORIGINAL) Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: Rohm and Haas Company Actual Inventor(s): Areski Rezkallah Address for Service and Correspondence: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: METHOD FOR THE RECOVERY OF URANIUM FROM PREGNANT LIQUOR SOLUTIONS Our Ref : 948453 POF Code: 83886/83886 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6006q Docket 71418 Method for the Recovery of Uranium from Pregnant Liquor Solutions The present invention is directed to a new more environmentally friendly method for the recovery of uranium from acid leach pregnant liquor solutions that comprise high levels of 5 chloride by using an amino phosphonic functionalized resin. Numerous minerals are present in subsurface earth formations in very small quantities which make their recovery extremely difficult. However, in most instances, these minerals are also extremely valuable, thereby justifying efforts to recover the same. An example of one such mineral is uranium. However, numerous other valuable minerals, such as copper, nickel, 10 molybdenum, rhenium, silver, selenium, vanadium, thorium, gold, rare earth metals, etc., are also present in small quantities in some subsurface formations, alone and quite often associated with uranium. Consequently, the recovery of such minerals is fraught with essentially the same problems as the recovery of uranium and, in general, the same techniques for recovering uranium can also be utilized to recover such other mineral values, whether associated with uranium or 15 occurring alone. Therefore, a discussion of the recovery of uranium will be appropriate for all such minerals. Uranium occurs in a wide variety of subterranean strata such as granites and granitic deposits, pegmatites and pegmatite dikes and veins, and sedimentary strata such as sandstones, unconsolidated sands, limestones, etc. However, very few subterranean deposits have a high 20 concentration of uranium. For example, most uranium-containing deposits contain from about 0.01 to I weight percent uranium, expressed as U 3 0 8 as is conventional practice in the art. Few ores contain more than about 1 percent uranium and deposits containing below about 0.1 percent uranium are considered so poor as to be currently uneconomical to recover unless other mineral values, such as vanadium, gold and the like, can be simultaneously recovered. 25 There are several known techniques for extracting uranium values from uranium containing materials. One common technique is roasting of the ore, usually in the presence of a combustion supporting gas, such as air or oxygen, and recovering the uranium from the resultant ash. However, the present invention is directed to the extraction of uranium values by the utilization of aqueous leaching solutions. There are two common leaching techniques (or 30 lixiviation techniques) for recovering uranium values, which depend primarily upon the accessibility and size of the subterranean deposit. To the extent that the deposit containing the 1A Docket 71418 uranium is accessible by conventional mining means and is of sufficient size to economically justify conventional mining, the ore is mined, ground to increase the contact area between the uranium values in the ore and the leach solution, usually less than about 14 mesh but in some cases, such as limestones, to nominally less than 325 mesh, and contacted with an aqueous leach 5 solution for a time sufficient to obtain maximum extraction of the uranium values. On the other hand, where the uranium-containing deposit is inaccessible or is too small to justify conventional mining, the aqueous leach solution is injected into the subsurface formation through at least one injection well penetrating the deposit, maintained in contact with the uranium-containing deposit for a time sufficient to extract the uranium values and the leach solution containing the uranium, 10 usually referred to as a "pregnant" leach solution (PLS), is produced through at least one production well penetrating the deposit. It is this latter in-situ leaching of subsurface formations to which the present invention is directed. The most common aqueous leach solutions are either aqueous acidic solutions, such as sulfuric acid solutions, or aqueous alkaline solutions, such as sodium carbonate and/or 15 bicarbonate. Aqueous acidic solutions are normally quite effective in the extraction of uranium values. However, aqueous acidic solutions generally cannot be utilized to extract uranium values from ore or in-situ from deposits containing high concentrations of acid-consuming gangue, such as limestone. While some uranium in its hexavalent state is present in ores and subterranean 20 deposits, the vast majority of the uranium is present in its valence states lower than the hexavalent state. For example, uranium minerals are generally present in the form of uraninite, a natural oxide of uranium in a variety of forms such as UO 2, UO 3, UO.U 20 3 and mixed U 3 0 8 (UO 2 .2UO 3 ), the most prevalent variety of which is pitchblende containing about 55 to 75 percent of uranium as UO 2 and up to about 30 percent uranium as UO 3 . Other forms in which 25 uranium minerals are found include coffinite, carnotite, a hydrated vanadate of uranium and potassium having the formula K 2 (UO 2 ) 2 (VO 4 ) 2 .3H 2 0, and uranites which are mineral phosphates of uranium with copper or calcium, for example, uranite lime having the general formula CaO.2UO 3 .P 2 0 s .8H 2 0. Consequently, in order to extract uranium values from subsurface formations with aqueous acidic leach solutions, it is necessary to oxidize the lower 30 valence states of uranium to the soluble, hexavalent state. 2 Docket 71418 Combinations of acids and oxidants which have been suggested by the prior art include nitric acid, hydrochloric acid or sulfuric acid, particularly sulfuric acid, in combination with air, oxygen, sodium chlorate, potassium permanganate, hydrogen peroxide and magnesium perchlorate and dioxide, as oxidants. However, the present invention is directed to the use of 5 sulfuric acid leach solutions containing appropriate oxidants and other additives, such as catalysts. There are two commonly used methods for the recovery of uranium from pregnant leach solution (PLS). One technique, solvent extraction, employs the use of a non aqueous solvent to selectively extract uranium from the PLS. 10 The second method involves ion exchange technology. Strong and weak base anion exchange resins are commonly used. This ion exchange method has become the more preferred method of uranium recovery in various regions of the world because of its environmental benefits as well as its safety benefits. Flammable toxic solvents need not be used for the present method as compared to the solvent extraction method where harmful chemicals are employed. 15 Additionally it has been discovered that in environments where there is a relatively high concentration of sulfate, i.e. greater than 25g/L, based on the composition of the PLS fouling of the ion exchange resin occurs. This fouling results in a decreased loading capacity of the resin. US 4599221 uses an amino phosphonic functionalized resin to recover uranium from phosphoric acid; however a need exists for a method to recover uranium from acid leach in high sulfate 20 environments. Recovery of uranium from phosphoric acid is a different process from the acid leach process because there are competing ions, such as sulfate, in an acid leach solution that can foul any recovery media. The phosphoric acid process does not have such. Additionally, the levels of uranium in a phosphoric acid process are relatively low, i.e. less than 300ppm. In acid leach, the loading capacity of uranium must be much greater as the levels of uranium in acid 25 leach liquors can be present in up to 2000 mg/L (or ppm) It is known that for the same concentration of uranium in the PLS, the operating capacity is much greater in acid leach liquor than in phosphoric acid liquor. Therefore one of skill in the art would not typically apply the same techniques from the recovery of metals from phosphoric acid to acid leach. The present invention solves these problems of the art by proving an amino phosphonic 30 functionalized resin type useful for the recovery of uranium that does not foul in sulfate environments of greater than 25g/L. 3 Docket 71418 The present invention provides a method for the recovery of uranium from a pregnant liquor solution comprising: i) providing an amino phosphonic functionalized resin; ii) providing a pregnant liquor solution comprising sulfate and uranium; 5 iii) passing the pregnant liquor solution over the amino phosphonic functionalized resin to separate the uranium from the pregnant liquor solution; and iv) eluting the uranium wherein the sulfate is present in an amount from 25 to 280 g/L. As used herein the term amino phosphonic functionalized resin is meant to include either 10 an amino phosphonic resin or an amino hydrophosphonic functionalized resins. In the present invention the resin is a styrene polymer resin having active amino phosphonic functional groups linked to the polymer matrix. The term "styrene polymer" indicates a copolymer polymerized from a vinyl monomer or mixture of vinyl monomers containing styrene monomer and/or at least one crosslinker, wherein the combined weight of 15 styrene and cross linkers is at least 50 weight percent of the total monomer weight. The level of cross linking ranges from 4 to 10%. All percentages herein are weight percentages. A crosslinker is a monomer containing at least two polymerizable carbon-carbon double bonds, including, e.g., divinylaromatic compounds, di- and tri-(meth)acrylate compounds anddivinyl ether compounds. Preferably, the crosslinker(s) is a divinylaromatic crosslinker, e.g., 20 divinylbenzene. The structure of the polymer can be either gel or macroporous (macroreticular). The term "gel" or "gellular" resin applies to a resin which was synthesized from a very low porosity (0 to 0.1 cm 3 /g), small average pore size (0 to 17 A) and low B.E.T. surface area (0 to 10 m 2 /g) copolymer. The term "macroreticular" (or MR) resin is applied to a resin which is synthesized 25 from a high mesoporous copolymer with higher surface area than the gel resins. The total porosity of the MR resins is between 0.1 and 0.7 cm 3 /g, average pore size between l7and 500 A and B.E.T. surface area between 10 and 200 m 2 /g. The resin is in appropriate ionic form, preferably acid or acidic form. The resin of the present invention may be in sodium form. The resin is used to treat an acid leach pregnant liquor solution (PLS). The PLS of the 30 present invention comprises uranium and sulfate. Uranium is primarily present in the form of
U
3 0 8 ; although other commonly known forms and isotopes of uranium may be present. As used 4 Docket 71418 herein, the term uranium refers to all forms and isotopes of uranium. Uranium is present in the PLS in an amount from 25 to 2000 mg/L, preferably from 50 to 1500mg/L, and further preferably from 60 to 1000 mg/L. Sulfate ion and sulfate complexes together as "sulfate" is present in the PLS in an amount from 25 to 280 g/L and preferably form 35 to 220g/L and 5 further preferably from 40 to 180 g/L. The PLS of the present invention may optionally contain a variety of other components. Such components include but are not limited to: iron, sulfuric acid, sodium, calcium, potassium, chloride, copper, phosphorus, and aluminum. The pH of the PLS is acidic and ranges from 0 to 4, preferably 0 to 3, more preferably 0 to 2, most preferably 0 to 1.8, . Furthermore, the PLS may be obtained from any method commonly known to those of 10 skill in the art including but not limited to in situ leach, heap, leach, resin in pulp, and in situ recovery. Uranium is separated from the PLS by passing the PLS over the amino phosphonic functionalized resin. Techniques commonly used in the art to separate the uranium from the PLS may be applied. Such techniques include but are not limited to fixed bed, co-current or 15 countercurrent fluidized bed, resin in pulp (RIP). The process may be batch or continuous. Typically the flow rate within the column or packed bed system is from 0.5 to 50BV/h. The amino phosphonic functionalized resin retains the uranium from the PLS and the uranium is then recovered by elution. Methods of elution used by those of ordinary skill in the art are used herein. Preferably, the uranium loaded resin may be treated with a solution of ammonia or 20 ammonia hydroxide. Afterwards, the resin is eluted with a solution of sodium carbonate. The uranium is then recovered from solution by known separations techniques, such as for example precipitation. It is beneficially found that the at least 10% of the uranium found in the original PLS may be recovered. Within the pH range of 0 to 4 of the PLS, uranium recovery levels of up to 25% may be achieved, preferably up to 10%. The uranium may be recovered at levels ranging 25 from 5-25%, preferably 10-25%, and more preferably 15-25%. In addition to ion exchange technology, solvent extraction technology may also be employed to recover uranium from PLS comprising high levels of sulphate. Traditionally, solvent extraction employs solvents with a tertiary amine functional group. In the present invention, affixing an amino phosphonic group or an amino hydrophosphonic group to a solvent 30 molecule may be advantageously employed in lieu of tertiary amine functional groups. Conventional methods of solvent extraction may be utilized herein. 5 Docket 71418 Examples Laboratory equipment used Jacketed glass column (height 30cm, 0 2-3cm, fitted with sintered glass of porosity 1). Peristaltic pump with flexible tubings. 10, 100 graduated cylinder. 25 mL plastic flasks for samples collections. 5 Stopwatch. Appropriate equipment for Uranium analysis (Le: ICP). Standard laboratory glassware Resin used AMBERSEPTM 940U, is a registered trademark of Rohm and Haas Company, a wholly owned subsidiary of The Dow Chemical Company. The resin is in sodium form having a polystyrenic matrix, crosslinked with divinyl benzene and containing aminophosphonic functional groups. 10 Note The resin was converted in its appropriate ionic form (i.e: acidic form) before carrying out the experiments. Examples Solution 15 Solution 1: A solution containing 500 mg/L of uranium (expressed as U), 25g/L of sulfate, Og/L of chloride 2g/L of iron (as Fe 3 ) was left in contact with a sample of AMBERSEPTM 940U for 8 hours. Solution 2: A solution containing 500 mg/L of uranium (expressed as U), 195g/L of sulfate, 20g/L of chloride 2g/L of iron (as Fe 3 ) was left in contact with a sample of AMBERSEP TM 940U for 8 hours. Solution 3: A solution containing 500 mg/L of uranium (expressed as U), 278g/L of sulfate, Og/L of 20 chloride 2g/L of iron (as Fe 3 ) was left in contact with a sample of AMBERSEPTM 940U at 2.5 BV/h. 6 Docket 71418 Experiments All experiments were carried out at 25*C. 500 milliliters of solution was left in contact with a 10 milliliters sample of AMBERSEPTM 940U. The ratio of I part resin to 50 parts of solution was kept constant in order to avoid any external perturbation. The pH of the solutions was adjusted at different 5 values (i.e: 0, 1, 1.8, 2.5, 3) in order to determine the impact on the loading capacity. After shaking for 8 hours, the analysis of the uranium residual in the supernatant was measured and the resin loading determined. Results pH 0 1 1.8 2.5 3 Solution 1 41.0 37.4 29.0 34.8 38.0 M CL Solution 2 36.2 24.2 19.4 23.0 27.8 0 Solution 3 24.8 21.9 16.7 16.2 21.1 10 10 The uranium loading increases when the pH decreases. The operating capacity equates 36.2 g/LR (expressed as U) when the pH is equal to 0 for a solution containing 195g/L. The results prove that the resin AMBERSEPTM 940U exhibits very good performance of uranium recovery under very high concentration of sulfate. 15 It is remarkable that the lower the pH the better the operating capacity. Such characteristic offers the possibility to use sample of AMBERSEPTM 940U to recover uranium when the concentration of sulfate is very high. The resin performance (i.e: operating capacity) can be improved by lowering the pH. 7 Docket 71418 Elution The loaded resin (obtained from experiment with the Solution 2 at pH 0) was treated with 2 bed volumes of a solution of ammonia hydroxide at a concentration of 1 mol/L (IN). Afterwards, the resin was eluted with a solution of sodium carbonate at a concentration of 1 N. 5 The totality of uranium loaded was eluted within 7 bed volumes of sodium carbonate solution. 8