Variation of Core temperature with Heating schedules in MTR Operation

Ladola Y S, S Chowdhury, Vivek Sharma, S B Roy Uranium Extraction Division, BARC, Mumbai-400094 email-id: ladola@gmail.com

Abstract:
Magnesio-thermic Reduction (MTR) of Uranium tetra Fluoride (UF4) is one of the important industrial methods for producing nuclear 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. MTR is a batch type operation and batch size has been scaled up over the years from 80 kg to 500kg in phases. 500kg process has been recently designed and established at UED, BARC. This is a bomb type reaction and is represented by UF4 + 2Mg = U + 2MgF2 (ΔH0298 = – 83.5 Kcal/gm mole) [1]

Small excess of magnesium is required to improve yield. This thermite type reduction is carried out in a closed reaction vessel, 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 reduces the chance of foreign element contamination. 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. For conducting the reduction reaction, stoichiometric

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quantity of UF4 and Mg chips are blended and charged inside the lined reactor. Once the charging is over, the top surface of charge is covered with fine MgF2 powder and the reactor is 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”. MTR reaction mechanism is a complex one. A large number of side reactions as well as parallel reactions 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 1600-17000C. U settles down at bottom due to large density difference with slag. When the MTR reaction is initiated at 25 0C, reaction heat is not sufficient to melt reaction products (U & MgF2) completely and an additional heat of 6.8 kcal/per gm mole must be supplied to effect their complete melting [2]. Preheating is done to supply additional heat. Heat balance calculation shows that the charge should attain a minimum temperature of 200oC before firing to have molten U and MgF2. Even this is not sufficient for adequate metal-slag separation. Better metal-slag separation requires low viscous molten product mass (U and MgF2) and that can be assured by higher temperature of reaction product. High temperature can be obtained by higher heat input to charge before firing. Higher core temperature ensures higher heat input. But, there is a limit to heat input to reactant charge. Temperature of charge can not be increased endlessly before firing as surplus heat may lead to a violent explosive reaction. Considering these two contradicting demands, understanding of variation of core temperature with preheating is very important for safe and efficient production of uranium metal. In this paper we have studied response pattern of core temperature with different heating schedule in 500kg MTR Batch. Key words: Magnesiothermic reduction, heat transfer, core temperature and heating schedule.

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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 metal ingots. When UF4 is reduced under specific conditions, a solid regulus of material is formed under cover of slag. The initiation of reaction is generally called firing of the charge. Firing is confirmed by sensing sudden rise in charge temperature which is recorded by thermocouple inserted inside the top capping of the charge. This temperature is called “Core Temperature”. For obtaining massive uranium, the products of the reaction, the uranium and the 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 obtain such condition even after compensating heat losses to the containers and its surroundings. Magnesiothermic Reduction (MTR) of UF4 is being practiced in UED, BARC for production of nuclear grade uranium metal ingot and it has been observed that to obtain above mentioned condition an optimized preheating schedule is essential.

2. Reaction features:
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. These reactions are 1) UF4 + 2Mg 2) Mg+2UF4 3) Mg + UO2F2 4) 2Mg + UO2 U + 2MgF2 MgF2 + 2 UF3 UO2 + MgF2 2MgO +U (ΔH0298 = – 83.5 Kcal/gm mole) [1]

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5) Mg + UO3 6) 2Mg + U3O8 7) 2Mg + O2 8) 3Mg + N2 9) Mg + H2O 10) Mg + 2HF 11) 2UF4 + O2 12) 9UO2F2 13)2UF4 + 2H2O + O2 14) UO2F2 + H2O 15) UF4 + 2H2O 16) N2+3H2

MgO + UO2 2MgO + 3UO2 2MgO 2Mg3N2 MgO + H2 MgF2 + H2 UF6 +UO2F2 3UF6 + 2U3O8 +O2 2UO2F2 + 2HF 2U3O8 + 12HF+ O2 UO2+ 4HF NH3

The reaction between uranium tetraflouride and Magnesium is less exothermic than to be adequate by itself to realize the fusion of the products. When the MTR reaction is initiated at 25
0

C, reaction heat is not sufficient to melt reaction products (U & MgF2) completely and heat

balance calculation shows an additional heat of 6.8 kcal/per gm mole must be supplied to effect their complete melting [2]. However, the necessary temperature for fusion and separation is being attended by adding heat to the charge before the reaction initiation. Once the reaction is initiated, it proceeds to completion spontaneously yielding massive amount of metal. 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 yield improvement. Due to high

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density difference between charge and product material, after cooling a cavity is formed above product mass.

3. Materials and methods: Magnesio-thermic Reduction reaction is carried out in boiler quality reaction vessel 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 the lined reactor. Top of the charge is capped with MgF2 powder to protect lid. The lid is then bolted to the reactor and the sealed reactor is loaded in the furnace for preheating. Preheating is done by following predefined heating schedule for the initiation and completion of the reaction. Temperature is measured at different position of reactor using thermocouples as shown in Figure 1. Zone temperature is controlled by PLC controller as per heating schedule. All zone

temperatures and core temperature are continuously recorded till completion of firing. MTR batch size has been scaled up over the year from 80 kg ‘U’ to 500 kg ‘U’. Furnace has been changed from bogie type to pit furnace for better utilization of heat input. Based on previous experience, different heating schedules as shown in Figure 2(a)-2(d) were selected for preheating of the 500 kg MTR Batches. Core temperature is continuously observed for firing indication. Firing is indicated by sudden rise of ‘Core temperature’ as core temperature suddenly increases due to heat of reaction.

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4. Results and discussions: With increase in preheating temperature, enthalpy of reactants (UF4 and Mg) changes as shown in Figure 3 [2]. Therefore preheating is done to supply additional heat to effect complete charge melting and it has been calculated that whole charge should attain a minimum temperature of 200oC before firing to have molten U and MgF2. However, this is also not sufficient for adequate metal-slag separation. Better metal-slag separation occurs in low viscous molten mass (U and MgF2), which can be assured by higher temperature of reaction products. For attaining this higher temperature higher heat input to charge before firing is necessary. But, there is a limit to heat input to reactant charge before firing as excess heat may lead to violent reaction which may cause explosion [3]. Considering these two contradicting demands, understanding of variation of core temperature with preheating schedule is very important for safe and efficient production of uranium metal. Since this is a bomb type reaction and triggering can occur anywhere in the charge, exact measurement of firing temperature is not possible. Moreover, though sufficient soaking time is provided, temperature distribution in the charge is not uniform [4]. Firing occurs when any single point of charge reaches at firing temperature and this sets limit on heating rate as higher rate of heating increases temperature of some portion of charge at firing temperature level before adequate heating of full charge and leads to premature firing. Low rate of heating take more time to complete any batch and lead to lower rate of production. Optimum rate of heating is very important which is ensured by following optimum heating schedule. It has been observed that increase of core temperature during preheating is an indicator of rate of heat input. Therefore study of response pattern of core temperature is very important in optimizing the heating schedules. During present study, response of core temperature with time for different heating schedules has been observed and is shown in Figure 2(a)-2(d). It has been observed that

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heating schedule 1, 2 and 3 have similar core temperature pattern. Temperature pattern of heating schedule 4 is initially similar to other heating schedules but it becomes sluggish at the end. Recovery of different batches with different hating schedule is tabulated in Table 1. Very good recovery has been obtained in all heating schedules. However both excellent and poor recoveries have been observed for heating schedule 3 and 2. From available limited data it can be observed from profile of core temperature that heating schedule 4 have optimum rate of heating and consistent recovery. 5. Conclusion: Heating schedule is important for control of rate of heating and overall heat input. As expected, during preheating variation of core temperature for a particular heating schedule shows similar pattern with a difference in absolute value within a range of ± 50 oC. This may be due to variation of properties of reactants and linning material. Heating schedule 2 and 3; both have one premature firing with firing temperature 265 oC and 273 oC. Therefore it can be concluded that for higher recovery ignition point core temperature must be above 300 oC and preferably above 340 oC. From the limited no. of available data it appears that heating schedule 4 have optimum rate of heating and heat input. However, to establish its effectiveness more trials are needed.

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6. Reference: 1. C D Harrington and A E Ruehle (ed.) Uranium Production Technology. D. Van Nostrand co. Inc. (1959) 2. Y S Ladola, S Chowdhury, S Sharma and S B Roy “Recovery of locked up Uranium in Slag disc by co-melting in MTR”, Trans. IIM, vol. 61, April-June 2008, pp 103-106. 3. A K Mohanty “Physico-chemical aspects of metallothermic reduction” proceedings of the symposium on ‘Metallothermic processes in metal and alloy extraction’, December 1983, pp 21-41 4. S Soni, S Manna, V Iswaran, S B Roy and P Munshi “Modeling of unsteady state heat transfer in externally heated Magnesiothermic Reduction Reactor” in press, November 2008, IAEA, Austria.

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Table 1: MTR batch details MTR Batch No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Equipment: Furnace, Reactor, Lid 301, G1, G1 301, G1, G1 301, G1, G1 301, G3, G3 302, G7, G7 302, G8, G8 302, G7, G7 302, G8, G8 302, G7, G7 302, G8, G8 302, G7, G7 302, G8, G7 302, G8, G8 302, G8, G8 Heating Schedule, total heating Time (hr), Energy consumption (kW-hr) H1 34.00 895 H1 31.00 865 H1 27.00 920 H1 29.55 985 H2 36.15 1245 H2 24.30 990 H2 24.40 895 H2 17.25 755 H3 28.50 801 H2 22.10 778 H3 15.50 775 H2 17.05 670 H4 28.35 905 H4 29.40 925 Recovery Core Temperature at time of firing

% 88.67 89.11 91.90 90.10 89.54 92.23 90.14 81.55 94.34 94.34 62.76 71.68 90.59 90.37

348 351 381 377 458 395 345 315 348 371 265 273 366 395

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TC

TT

TM

TB

Figure 1 Schematic diagram of MTR reactor 1.Red colour: reactor body and lid 2.Black clour: graphite crucible 3. Green colour: UF4 and Mg charge 4. Gray colour: MgF2 linning and capping) 5. TC: core temperature thermocouple 6. TT: top zone thermocouple 7. TM: middle zone thermocouple 8. TB is bottom zone thermocouple.

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700 600 500 400
Temperature (oC)

Heating Schedule 1

300 200 100 0 0 5 10 15 20
Time (hr)

1 2 3 4

25

30

35

40

Figure 2a: Response of Core temperature for heating Schedule 1

700 600 500 400
Temperature (oC)

Heating Schedule 2

300 200 100 0 0 5 10 15
Time (hr)

5 6 7 8 10 12

20

25

30

35

40

Figure 2b: Response of Core temperature for heating Schedule 2

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700 600 500
Temperature (oC)

Heating Schedule 3

400 300 200 100 0 0 5 10 15
Time (hr)
9 11

20

25

30

35

40

Figure 2c: Response of Core temperature for heating Schedule 3

700 600 500
Temperature (oC)

Heating Schedule 4

400 300 200 100 0 0 5 10 15 20
Time (hr)
13 15

25

30

35

40

Figure 2d: Response of Core temperature for heating Schedule 4 12

20

Enthalpy of material, Kcal/gm mole

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UF4 + 2Mg UF4

10

5

Mg
0

Temperature, 0 C Figure 3: Enthalpy of reactant (UF4 and Mg) at different temperature.

0

100

200

300

400

500

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