Trans. Indian Inst. Met. Vol. 61, Nos. 2-3, April-June 2008, pp.

103-106

TP 2189

Recovery Of Locked-up Uranium In Slag Disc By Co-melting In Magnesio-Thermic Reduction
Y.S Ladola, S. Chowdhury, S. Sharma and S.B. Roy
Uranium Extraction Division, Bhabha Atomic Research Centre, Trombay, Mumbai - 400 085, India E-mail : ladola@gmail.com (Received 5 December 2007 ; in revised form 7 February 2008)

ABSTRACT
Magnesio-thermic Reduction (MTR) of Uranium tetra Fluoride (UF4) is one of the main industrial methods for producing commercial pure uranium metal in massive form. Nuclear grade natural Uranium (U) metal ingots are produced regularly in UED, BARC following MTR route for fuelling research reactors in BARC. This is a bomb type reaction and is represented by UF4 + 2Mg = U + 2MgF2('Ho298 = – 83.5 Kcal/gm mole) MTR reaction mechanism is a complex one. A large number of side reactions as well as parallel reactions also occur during the conversion of UF4 to U. This reaction is exothermic and final temperature of the molten product mass i.e. U and MgF2 goes up to around 1600-1700oC. U settles down at bottom due to large density difference with slag. Good separation is very important for the better yield. Interface of U metal and slag is rich in U content because freshly reduced U metal droplets, which do not get chance to coalesce with the bulk of the metal due to the formation of firm crust at the interface of metal and slag end up getting accumulated at the interface. This interface is removed before subsequent vacuum induction melting and fuel fabrication. This cut interface, which contains entrained metal that could not coalesce with parent metal, some amount of parent metal and quite a good amount of MgF2, is called the ‘slag disc’. It is desirable to recover U locked-up in these slag discs as the recovery of U will not only augment current U inventory but also will reduce the burden of radioactive material storage. To recover this U, experiments were conducted using co-melting in MTR operation along with charge by utilizing the heat generated during exothermic MTR reaction. Experiments have been also conducted to find the optimum weight of the slag disc and its location inside the reactor along with charge to maximize the U recovery. Results obtained are encouraging, as it has been observed that purity of finished product doesn’t get affected. This method has advantage over other alternative methods, as it is simple, cost effective, and doesn’t demand additional process step, setup and energy.

Small excess of magnesium is required to achieve maximum yield. This thermite type reduction is carried out in a closed reaction vessel, popularly known as MTR reactor, lined with magnesium fluoride powder. MTR reactors are made of boiler quality steel. Use of MgF2, a reaction by-product, as lining material completely eliminates the chance of foreign element contamination. This lining of MgF2 not only prevents direct contact of the molten metal and slag with the reaction vessel but also acts as an insulating material immediately after firing and holds the hot molten mass for longer period, thereby facilitating adequate metal-slag separation. This is a batch process and stoichiometric quantity of UF4 and Mg chips are blended and charged inside the lined reactor. Once the charging is over, the surface is covered with fine MgF2 powder and sealed by fixing a lid. This sealed reactor is then heated inside an electric furnace at a predefined heating schedule for the reduction to take place. The initiation of reaction is called ‘Firing”.

1. INTRODUCTION
Uranium (U) metal can be produced in a number of ways. Reduction of Uranium tetra fluoride (UF4) by magnesium (Mg) or calcium (Ca) has been used for large-scale production of nuclear grade Uranium. When UF 4 is reduced under specific conditions, a solid regulus of material is formed under cover of slag. For obtaining massive uranium, the products of the reaction, the uranium and slag should be sufficiently fluid and remain so, long enough for the dispersed particles of freshly produced uranium to come together, coalesce and merge to the primary interface. The heat of reaction should be enough to melt uranium and slag to a condition of sufficient fluidity and compensate heat

losses. We are using Magnesiothermic Reduction (MTR) of UF4 in UED, BARC for production of nuclear grade uranium metal ingot. Magnesio-thermic Reduction reaction is carried out in boiler quality reaction vessel popularly called MTR reactor. The reactor is lined with refractory material i.e. magnesium fluoride (MgF2) to protect vessel from melting due to the heat of reaction and prevent contamination of the U metal with the material of the reaction vessel. The blended UF4 and Mg charge is packed in lined reactor. Top of the charge is capped with MgF2 powder to protect lid. The lid is then bolted to the reactor. This sealed reactor is loaded into the furnace for preheating. Preheating is done following predefine heating

then it can be treated as separate batch. Recovered U has to pass through all step of uranium metal production from dissolution. Additional setup is required. Nos. 2-3. The initiation of reaction is generally called firing of the charge. Firing is observed by temperature rise in temperature recorder. 1. both U and MgF2 are in molten state. April-June 2008 . U and MgF2 goes up to around 1600-1700oC. 2. 1. Met. It is desirable to recover U locked-up in these slag discs as the recovery of U will not only augment current U inventory but also will reduce the burden of radioactive material storage. This separation is very important for effective yield. step or energy is required. However. If slag disc contains impurity. it can build-up in product metal ingot and overall recovery will be reduced. process setup and energy are required. U settles down at bottom due to large density difference with MgF2. Co-melting with MTR charge. The reaction is exothermic and final temperature of the product mass i. Slag discs have to be cut into small pieces to enable their effective dissolution with controlled addition. is called ‘slag disc’. 1. MTR reaction mechanism is a complex one.e. 2. If slag disc contains some impurity. 1.104 | Ladola et al. a brief mention about them here will be useful. 61. Indian Inst.melted per batch. The interface of U metal and slag is rich in U content due to the presence of the freshly reduced metal droplets that could not coalesce with the bulk of the metal due to the formation of firm crust at the interface of metal and slag. Table 1 Different methods of U recovery from slag disc Method Dissolution of slag disc in nitric acid. 5. This interface is removed by cutting before subsequent refining and fuel fabrication. No additional process setup. Different methods can be planned for recovery of this locked up uranium. 2. some amount of parent metal and a substantial volume of MgF2. Disadvantage Huge amount of NOx generation. which contains metal droplets that could not coalesce with parent metal. Additional step. These methods are described in Table 1 with their merits and demerits. Vol. considerable amount of harmful fluoride goes in nitric acid stream. 3. 1. 1. Good amount of slag discs can be melted together in single batch. Moreover. Size reduction of slag disc is required Considerable amount of fluoride goes in nitric acid that creates problem in subsequent refining step and creates corrosion problem. This cut interface. Limitation on weight of slag disc that can be co. 4. Trans. Advantage Recovery of uranium with desired purity. Direct melting of slag disc for slag–metal separation.. : Recovery of locked-up Uranium in slag disc by co-melting in Magnesio-Thermic Reduction schedule for the initiation and completion of reaction. Fluoride makes complex with uranyl ions that adversely affect impurity Fig. Dissolution of slag disc in nitric acid is associated with the problem of huge NOx generation. A large number of side reactions as well as parallel reactions also occur during the conversion of UF4 to U. At this temperature. 1 : Schematic diagram of MTR reactor with slag disc.

This demands additional operating system for accommodating fluoride in the process stream and use of exotic material of construction for better corrosion resistance.0 205. 2. This method has the advantage over other alternative methods as it is simple. firing occurs after 630 oC of set temperature. When the MTR reaction is initiated at 25oC. Indian Inst.1 4. (kg) Position of disc from top H. It has the limitation on the maximum weight of slag disc/discs that can be melted in a single batch.5 207.0 189.0 200.0 8. measured at outer wall of the reaction vessel.8 8.0 6. cost effective.4 8.0 192. Nos.9 11. 61. setup and energy.4 8.5 191 208 212. basic assumptions are made a.5 191. As temperature changes. Trans.5 203.0 5. Third method is Co-melting of slag disc with MTR charge by utilizing the heat generated during exothermic MTR reaction.0 210.5 206.9 7. Sr No Slag disc Wt.8 11.0 205.0 200.0 201. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 4.5 200.2 16. (kg) Separation Ingot Wt..0 8. It corrodes the stainless steel reaction tanks also1.8kcal/per gm mole must be supplied to effect their complete melting 2 .3 6.3 9.8 2.0 207. reaction heat is not sufficient to melt reaction products (U & MgF 2 ) completely and an additional heat of 6.4 kg Good Excellent Excellent Good Good Excellent Good Good Excellent Good Good Excellent Good Excellent Excellent Excellent Excellent Excellent Excellent Good Good Excellent Excellent Excellent Very good Good Good Excellent Very good Very good 199. Vol.2 7. and doesn’t demand additional process step. 2.5 198.6 9.0 192.2 3. : Recovery of locked-up Uranium in slag disc by co-melting in Magnesio-Thermic Reduction | 105 Table 2 Results of slag discs co-melted in MTR batches. 2 : Enthalpy of reactant (UF 4 and Mg) at different temperature.8 16. c. which necessitate frequent maintenance. cm 71 64 64 64 64 56 64 38 38 46 46 46 56 46 51 51 51 56 64 43 53 51 51 48 51 58 51 43 43 64 Fig.7 4.Ladola et al.0 217 Average. Generally.0 206.0 198. b. 2-3.0+3.1 245. Second method of uranium recovery is direct melting of slag discs in high temperature system. This method looks more attractive as more number of slag discs can be melted in single batch.5 11.5 188. CALCULATION FOR DETERMINING THE MAXIMUM WEIGHT OF SLAG DISC THAT CAN BE CO-MELTED WITH MTR CHARGE For simplification. This method also requires additional costintensive setup.0 203.7 7.0 202.4 7. April-June 2008 . enthalpy of reactants (UF4 and Mg) changes as shown in Fig. Wt ~200 kg removal in the subsequent Solvent Extraction (SX) for purification and refining.0 207.0 205.0 169.1 6.7 13. Average reaction temperature is 450oC. Preheating is done to supply this additional heat. No heat loss through out the process.6 8.3 7.0 197. Met.3 5. Temperature is not uniform through out the charge.3 6. No heat is utilized for post reduction increase in temperature beyond melting point of MgF2 (1263oC).

Harrington C D and Ruehle A E (ed. McGraw Hill Co. But.2 kg. Heat required for melting MgF2 [i. one of the basic assumptions is that no heat is utilized for post reduction increase in temperature beyond melting point of MgF 2 (1263oC) and the extra heat available is completely used for slag disc melting and subsequent recovery of uranium. April-June 2008 . maximum feasible value for MgF2 (slag) and U that can be co-melted can be given as 14.e. Positions of slag discs were varied to understand the effect of positioning. Basis of this calculation is for production of 1 kmole of uranium. Considering all available extra heat is fully utilized for comelting.34 kg (0. lower yield has been obtained during normal MTR operation too and so. Nuclear Chemical Engineering. 2-3. Average weight of an ingot produced through MTR route is around 192kg with a recovery of 96%. 3. However.08 kcal/gm mole 2 and that of U [i.15 kg (0.636 kmole (10. REFERENCES 1. Maximum weight of single slag disc that was co-melted with MTR charge is 16.4 kcal/ gm mole of uranium.84 kmole of Uranium ingot is produced in one batch. (1959).35 kcal/gm mole 2. Though there was chance of contamination due to long term storage of the discs in an uncontrolled atmosphere. Satisfactory results have been obtained for all the positions of slag disc.28 kmole (10. Indian Inst. 11. There are good to excellent slag separation observed in all the experiments. maximum weight of the slag disc that can be co-melted as per calculation is estimated to be 49 kg. Co-melting method appears to have huge potential as an alternative for recovery of U from old stock. 4. amount of MgF2 (slag) and U that can be co-melted is 0. Excellent slag separation was found with minimum thickness or minimum weight slag disc. Melting points of U and MgF 2 are 1133 o C and 1263 oC respectively. Average recovery of metal from slag disc is calculated to be 92%. both will be at the molten state at a temperature beyond their respective melting points. Van Nostrand co. Experiments were conducted for co-melting in MTR operation by utilizing the heat generated during exothermic MTR reaction. This increase in ingot weight is a definite indication of recovery of uranium from the slag disc. But. Results obtained for determining optimum position/location of the disc also appear to be satisfactory for all the position of slag disc. around 180kg of locked-up U could be recovered. 2. it has been observed that average weight of ingot where slag discs were co-melted was more and was around 200 kg. and doesn’t demand additional process step.106 | Ladola et al. cost effective. where weight of ingot reduced to 169 kg. 2. 2nd Edition (1981). Met. It has been observed that purity of the finished product doesn’t get affected while recovering U from slag discs by co-melting with MTR operation. CONCLUSIONS This locked up uranium can be recovered by different methods as described in Table 1 with their merits and demerits.35) respectively. 5. Pigford T H and Levi H W. Trans.2kcal/ gm-mole of uranium as shown in Fig. converting U (s) at RT (298K) to U (l) at 1536K. D. Assuming that 0. RESULTS AND DISCUSSION 30 experiments have been conducted and the results are tabulated in Table 2. No adverse effects have been observed during these experiments except experiment no.) Uranium Production Technology.4 / 16. Therefore. Nos. Some times.. numbered and co-melted with regular MTR production batches. this can be considered a stray case. Through these experiments. One disc per MTR batch has been co-melted except experiment number 15 where two small slag discs were co-melted in a single MTR batch. initial assumptions for basic calculation do not hold true fully and needs actual experimentation for process standardization 450oC. In this series of experiments.28 X 61) and 127. Now. However. slag disc weighing up to 16kg has been co-melted. 1. Each ingot was weighed and observed for slag separation. Slag discs were put vertically in charge and their positions were measured and recorded from the top as shown in Fig.636 X 238) respectively. converting MgF2 (s) at RT (298K) to MgF2 (l) at its melting point (1536K)] is estimated to be 37. Analysis shows that there is no impurity build-up due to slag disc co-melting with MTR charge and all the ingots are pure and qualified for fuel fabrication.1 Heat balance Average temperature of reactants can be assumed as Enthalpy of charge mixture (UF4 + 2Mg) at 450oC is 17. Experiments have shown that 16 kg of slag disc can be co-melted with MTR charge.84 X 0. Considering general composition of slag disc to be 20% of MgF2 and 80% of U. practically that didn’t affect the purity of the finished product. Inc. Findings of these experiments are encouraging.84 X 0. Vol. immediately after the reaction.e.08) and 0. Around 245 kg of slag disc with 80% uranium value were co-melted in 30 MTR batches. for all practical purposes.4 / 37. Bendict M. : Recovery of locked-up Uranium in slag disc by co-melting in Magnesio-Thermic Reduction 2. 61. It is also very simple. extra heat available for co-melting of slag disc is 10. the MP of MgF2] is 16. EXPERIMENTS Slag discs were weighed. setup and energy.