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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 doesnt get affected. This method has advantage over other alternative methods, as it is simple, cost effective, and doesnt 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

104 | Ladola et al. : Recovery of locked-up Uranium in slag disc by co-melting in Magnesio-Thermic Reduction

schedule for the initiation and completion of reaction. The initiation of reaction is generally called firing of the charge. Firing is observed by temperature rise in temperature recorder. 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. The reaction is exothermic and final temperature of the product mass i.e. U and MgF2 goes up to around 1600-1700oC. At this temperature, both U and MgF2 are in molten state. U settles down at bottom due to large density difference with MgF2. This separation is very important for effective yield. 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. This interface is removed by cutting before subsequent refining and fuel fabrication. This cut interface, which contains metal droplets that could not coalesce with parent metal, some amount of parent metal and a substantial volume of MgF2, is called 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. Different methods can be planned for recovery of this locked up uranium. These methods are described in Table 1 with their merits and demerits. However, a brief mention about them here will be useful. Dissolution of slag disc in nitric acid is associated with the problem of huge NOx generation. Slag discs have to be cut into small pieces to enable their effective dissolution with controlled addition. Moreover, considerable amount of harmful fluoride goes in nitric acid stream. Fluoride makes complex with uranyl ions that adversely affect impurity

Fig. 1 : Schematic diagram of MTR reactor with slag disc.

Table 1
Different methods of U recovery from slag disc Method Dissolution of slag disc in nitric acid. 1. Advantage Recovery of uranium with desired purity. 1. 2. 3. Disadvantage Huge amount of NOx generation. 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. Additional setup is required. Recovered U has to pass through all step of uranium metal production from dissolution. Additional step, process setup and energy are required.

4. 5. 1.

Direct melting of slag disc for slagmetal separation.

1. 2. 1.

Good amount of slag discs can be melted together in single batch. If slag disc contains some impurity, then it can be treated as separate batch. No additional process setup, step or energy is required.

Co-melting with MTR charge.

1.

If slag disc contains impurity, it can build-up in product metal ingot and overall recovery will be reduced. Limitation on weight of slag disc that can be co- melted per batch.

2.

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

Ladola et al. : 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. Sr No Slag disc Wt. (kg) Separation Ingot Wt. (kg) Position of disc from top H, 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. 2 : Enthalpy of reactant (UF 4 and Mg) at different temperature.

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

4.0 5.0 6.3 6.8 8.3 6.3 5.9 11.4 8.2 7.0 8.3 9.1 4.2 3.8 2.0+3.5 11.8 11.4 7.6 9.7 4.1 6.7 13.7 7.0 8.6 8.9 7.3 7.4 8.8 16.2 16.1 245.4 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

199.5 198.5 200.0 206.0 201.5 191 208 212.5 203.5 188.0 169.0 210.0 207.0 202.0 200.0 205.0 207.0 203.0 192.0 200.0 205.0 192.0 198.5 206.0 197.5 191.5 207.0 189.0 205.0 217 Average. Wt ~200 kg

removal in the subsequent Solvent Extraction (SX) for purification and refining. It corrodes the stainless steel reaction tanks also1, which necessitate frequent maintenance. This demands additional operating system for accommodating fluoride in the process stream and use of exotic material of construction for better corrosion resistance. 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. This method also requires additional costintensive setup. Third method is Co-melting of slag disc with MTR charge by utilizing the heat generated during exothermic MTR reaction. This method has the advantage over other alternative methods as it is simple, cost effective, and doesnt demand additional process step, setup and energy. It has the limitation on the maximum weight of slag disc/discs that can be melted in a single batch.

2. CALCULATION FOR DETERMINING THE MAXIMUM WEIGHT OF SLAG DISC THAT CAN BE CO-MELTED WITH MTR CHARGE
For simplification, basic assumptions are made a. b. c. No heat loss through out the process. Average reaction temperature is 450oC. No heat is utilized for post reduction increase in temperature beyond melting point of MgF2 (1263oC).

When the MTR reaction is initiated at 25oC, reaction heat is not sufficient to melt reaction products (U & MgF 2 ) completely and an additional heat of 6.8kcal/per gm mole must be supplied to effect their complete melting 2 . Preheating is done to supply this additional heat. As temperature changes, enthalpy of reactants (UF4 and Mg) changes as shown in Fig. 2. Generally, firing occurs after 630 oC of set temperature, measured at outer wall of the reaction vessel. Temperature is not uniform through out the charge.

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

106 | Ladola et al. : Recovery of locked-up Uranium in slag disc by co-melting in Magnesio-Thermic Reduction

2.1 Heat balance Average temperature of reactants can be assumed as Enthalpy of charge mixture (UF4 + 2Mg) at 450oC is 17.2kcal/ gm-mole of uranium as shown in Fig. 2. Therefore, extra heat available for co-melting of slag disc is 10.4 kcal/ gm mole of uranium. Basis of this calculation is for production of 1 kmole of uranium. Melting points of U and MgF 2 are 1133 o C and 1263 oC respectively. However, immediately after the reaction, both will be at the molten state at a temperature beyond their respective melting points. However, 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. Now, Heat required for melting MgF2 [i.e. converting MgF2 (s) at RT (298K) to MgF2 (l) at its melting point (1536K)] is estimated to be 37.08 kcal/gm mole 2 and that of U [i.e. converting U (s) at RT (298K) to U (l) at 1536K, the MP of MgF2] is 16.35 kcal/gm mole 2. Considering all available extra heat is fully utilized for comelting, amount of MgF2 (slag) and U that can be co-melted is 0.28 kmole (10.4 / 37.08) and 0.636 kmole (10.4 / 16.35) respectively. Assuming that 0.84 kmole of Uranium ingot is produced in one batch, maximum feasible value for MgF2 (slag) and U that can be co-melted can be given as 14.34 kg (0.84 X 0.28 X 61) and 127.15 kg (0.84 X 0.636 X 238) respectively. Considering general composition of slag disc to be 20% of MgF2 and 80% of U, maximum weight of the slag disc that can be co-melted as per calculation is estimated to be 49 kg. But, for all practical purposes, initial assumptions for basic calculation do not hold true fully and needs actual experimentation for process standardization 450oC.

4. RESULTS AND DISCUSSION


30 experiments have been conducted and the results are tabulated in Table 2. Average weight of an ingot produced through MTR route is around 192kg with a recovery of 96%. But, it has been observed that average weight of ingot where slag discs were co-melted was more and was around 200 kg. This increase in ingot weight is a definite indication of recovery of uranium from the slag disc. Through these experiments, around 180kg of locked-up U could be recovered. Around 245 kg of slag disc with 80% uranium value were co-melted in 30 MTR batches. Results obtained for determining optimum position/location of the disc also appear to be satisfactory for all the position of slag disc. There are good to excellent slag separation observed in all the experiments. No adverse effects have been observed during these experiments except experiment no. 11, where weight of ingot reduced to 169 kg. Some times, lower yield has been obtained during normal MTR operation too and so, this can be considered a stray case. 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. Though there was chance of contamination due to long term storage of the discs in an uncontrolled atmosphere, practically that didnt affect the purity of the finished product. Maximum weight of single slag disc that was co-melted with MTR charge is 16.2 kg. Average recovery of metal from slag disc is calculated to be 92%.

5. CONCLUSIONS
This locked up uranium can be recovered by different methods as described in Table 1 with their merits and demerits. Experiments were conducted for co-melting in MTR operation by utilizing the heat generated during exothermic MTR reaction. Experiments have shown that 16 kg of slag disc can be co-melted with MTR charge. Findings of these experiments are encouraging. It has been observed that purity of the finished product doesnt get affected while recovering U from slag discs by co-melting with MTR operation. Satisfactory results have been obtained for all the positions of slag disc. Co-melting method appears to have huge potential as an alternative for recovery of U from old stock. It is also very simple, cost effective, and doesnt demand additional process step, setup and energy.

3. EXPERIMENTS
Slag discs were weighed, numbered and co-melted with regular MTR production batches. 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. Slag discs were put vertically in charge and their positions were measured and recorded from the top as shown in Fig. 1. Positions of slag discs were varied to understand the effect of positioning. In this series of experiments, slag disc weighing up to 16kg has been co-melted. Each ingot was weighed and observed for slag separation. Excellent slag separation was found with minimum thickness or minimum weight slag disc.

REFERENCES
1. 2. Harrington C D and Ruehle A E (ed.) Uranium Production Technology. D. Van Nostrand co. Inc. (1959). Bendict M, Pigford T H and Levi H W, Nuclear Chemical Engineering, McGraw Hill Co. 2nd Edition (1981).

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

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