RE ENGINEERING THE PROCESS IN PLANT SCALE PRODUCTION OF AMMONIUM URANATE USING VAPOUR AMMONIA AS A PRECIPITATION REAGENT

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Key Words : Vapour Ammonia, Equilibrium Precipitation, Ammonium Uranate

ABSTRACT
Uranium Oxide Plant (UOP) in Nuclear Fuel Complex produces reactor grade Uranium Dioxide Powder. The process of precipitating Uranyl Nitrate Pure Solution (UNPS) is an important step where soluble uranium is converted into solid form and all critical powder characteristics are shaped. Authors have successfully replaced the aqueous ammonia with gaseous ammonia as a reagent, to achieve equilibrium precipitation in shorter duration, with increased throughput and improved performance parameters. Paper discusses about the effect of modified process parameters on the nature of ammonium uranate. INTRODUCTION: There are two types of industrial manufacturing processes for the preparation of nuclear grade UO2 powder. They are dry and wet processes. In the wet process, a chemical reaction can be initiated with uranyl nitrate solution and it is well known that ammonium uranate[AU] (1) and ammonium uranyl carbonate [AUC] (2) are precipitated as intermediates. Particularly that AUC process which has been developed in 1960s by Nukem, Germany has distinct advantage. The AUC derived UO2 powder (2-4) has particles of spheroid or prismatic type which provide the flowable characteristics, important for the die filling aspect during compaction step. This type of powder, therefore, not required to have pre treatment and can be directly lead to final pressing. It also found easy to control powder surface area which plays an important role in obtaining high sintered density, by controlling micro pores within the particles. Typical UO2 ex AUC powder has bimodal pore distribution (4), and an average particle diameter of 10

microns (3). The work by NIKUSI (2,4,5) has the advantage of low temperature oxidative sintering, which is definitely beneficial for the fuel manufacture from the economic point of view. These advantages are due to high crystalline of the AUC precipitates and soluble impurities are easily filtered and washed. Another difference between AUC and AU is that AUC has a defined formulae and structure so that its production is very reproducible and the shape of crystal is conserved when transformed to UO2. The industrial AUC powders possess defined characteristics of form and particle size distribution determined by the production process (6). Large porosity is produced during the transformation from AUC to UO2. This porosity accounts for the porosity of the green pellet and controls the initial condition of the behavior of the material during sintering and consequently the final density of the pellet. Therefore many companies in Germany, Sweden, Korea, Argentina and so on have commercialized the AUC process. However the process of AUC precipitation suffers from high loss of uranium in filtrate[7] which would further require ion exchange process to recover the uranium from the filtrate. Among UO2 ex-AUC, powders of high surface area can be considered as hard from a point of view of compaction behaviour, because of the micropores existing with in particles. These micropores can accommodate the pressure during compaction of the powder, which decrease the compressibility of the powder bed. During sintering, however, in UO2 ex-AUC having high surface area, the micro pores in individual particles formed during the conversion process can enhance the densification of the compacted body [8]. Ammonium Uranates produced through aqueous ammonia as a reagent is found to give an excellent property of agglomeration which would retain upto the sinterable stage and would give excellent sintered densities. Higher surface areas, uniform porosity distribution, are easy to compress and give high sintered densities [9]. The precipitates of AU at higher pH found to give smaller agglomerates resulting in higher densities and uniform microstructure [10]. The precipitates of AU produced under equilibrium conditions proved to contain uniform microstructure and better flowability in comparison to continuous precipitation or single stage precipitation, which would result in poor flowability and non-uniform microstructure. The morphology and powder properties of AU precipitates and derived UO2 powders are however remarkably different from AUC precipitates and the UO2 powders produced from AUC. Contrary to the AUC precipitates of prismatic and discrete crystals, AU tends to form agglomerates of irregular shaped particles. The UO2 powders form AU generally inherits the shape of the original AU powders [7]. The UO2 powders from AU form a fluffy mass with poor flowability with an apparent density of 1.2 g/cc and a tap density of 1.3 g/cc, while the UO2 powders from AUC possess good flowability with an apparent density in the range of 1.3 to 2.0 g/cc and a tap density in the range of 1.4 to 2.2 g/cc. Thus the pelletising of UO 2 powders from AU require repeated filling of UO2 powders in to the die cavity with intermittent pressings in order to obtain the same L/D ratios as obtained by the UO2 powders from AUC. That is how, preslugging and granulation is necessary for the UO2 powders from AU. UO2 powders from AU also show complete growth of grains with clearer grain boundaries from AU source as compared to the UO2 powders from AUC. This is due to the duplex grain structure of AU powder produced under equilibrium conditions at higher pH values [7]. The particle of powder derived from AUC process is an aggregate with

many micropores but the powder derived from AU process is a soft agglomerate. The powder compacts often produced from AUC process are inhomogeneous because of the undeformed and deformed particles. The typical property of undeformed particle, the aggregate with many micropores, is preserved well, but the bonding between crystals is mostly broken in that deformed particle. The powder compacts from the AU process are homogeneous, and the bonding does not exist differently from an aggregate. The deformed particle exhibits the broken aggregate, which appear similar to the morphology of the powder compact from the AU process. From a morphological point of view, the densification and grain growth in the deformed particles are different from those in the undeformed particles similar to AU process [11]. The large grains are considered to be one of the desirable properties, because a Nuclear Fuel with large grains show low fission gas release during irradiation [12]. So, it is desirable to enlarge the grains of Uranium di oxide as explained above from AU source material. DISCUSSION: The present study is aimed at in achieving UO2 compacts with good density and uniform microstructure with enlarged grains. For this, the retention of agglomerate structure like AU and flowability of aggregates like in AUC are required to achieve above qualities. The fluffy nature of UO2 compacts produced from AU could be tackled by changing the reagent in the gaseous form to result in better flowability. As it would produce an anhygroscopic precipitate which would retain the similar nature in subsequent steps. The study is targeted in exploiting the non-aqueous solvent nature of vapour ammonia, which has low melting point, boiling point, density, viscosity, di-electric constant and electrical conductivity. The dissociation constant Kb is 1.774 x 105 at 25oC and increases slightly with increasing temperature. At pH 9.25, half of ammonia will be unionized (NH 3) and half will be ionised (NH4+). At pH 8.25 and 7.25, 90 and 99% of the ammonia will be ionised respectively. Therefore, at most environmentally significant pHs ammonia will be largely ionised; The fraction of unionized ammonia will become increasingly more important at pH above 7. As a result many physical and chemical properties are function of pH. For example, the solubility of ammonia in water will increase with decrease in pH. The volatility of ammonia increases with increase in pH. Therefore, it volatises freely from solution at high pH values. Ammonium salts such as ammonium nitrate is strongly dissociate and highly soluble (389.6 g/ 100g)[13] and these changes in pH will not normally result in the formation of ammonium precipitates. This is the reason why we can get consistent composition of ammonium uranates at different pH values using unionized ammonia vis--vis ionised ammonia in solutions. Because of its very low density and weak bonds, ammonia as a precipitating agent forms NH4+ with the hydrogen from hydrated molecules surrounding uranyl ions. The nascent ammonium molecule readily forms the salt with high electronegative anion NO 3- and where as ammonium hydroxide is weak base because of its poor dissociation constant and dissociated ammonium hydroxide participate in the reaction. Thus ammonium ion in ammonium hydroxide are very inactive due to the strong bond which leads to low rate of reaction and requires higher temperature to maintain low solubility product. Where as ionised ammonia ions (NH3-) are completely in dissociated form and readily diffuses due to its polar covalent bonds and ionic character. Ammonium ion is a tetragonal in structure with

greater stability with covalent bonds. The polarisability of large size cation like uranium is poor. Due to which uranyl ions combine with hydroxide to form uranyl hydroxides which subsequently forms UO2. 2H2O. The effect of temperature and concentration of Uranium in mother liquor is studied by LC Watson et.al. The findings are in unanimity of theoretical reductions agreeing that the precipitation temperature has a least effect sinterable density of powders precipitated with vapor ammonia, compared to linear effect of temperature of precipitation on sinterable density of powders precipitated with aqueous ammonia. Thus ammonia as precipitant, the sinterable density is independent of precipitation temperature. The same is confirmed during the trials conducted at room temperature by obtaining the similar settling rates and the equilibrium curve in comparison with the precipitation carried at higher temperatures. Unlike the studies by LC Watson et.al., the equilibrium conditions under which the precipitation is carried would further nullify the effect of temperature. It is observed that the rate of evolution of heat is much higher with vapour ammonia in comparison with aqueous ammonia, hence shows precision in increase in temperature. The rise in temperature from 30 oC to 47oC observed due to high solubility of vapour ammonia at low temperatures. And thus also helps in maintaining low solubility product and avoiding super saturation resulting in the similar precipitate. It is observed that vapour ammonia as reagent, the majority of ammonium precipitate is type-I AU with loosely held molecules of hydrates in octahedral structure due to the lower symmetry. The lower symmetry is due to the hydrogen bond interaction between inter layer H2O groups and oxygen atoms of the structural sheet. This is due to presence of 12 oxygen atoms in interlayer unbonded to any cation (14). The product of hydrolysis reaction was predicted in the form of UO2 (UO3)n OH+ or UO2[(OH)2UO2]4 ++ [15-17]. It is reported that ammonium ion reacts with UO2[(OH)2UO2]4 ++ to form AU. Under equilibrium condition when ammonia added slowly the precipitate composition was [(NH4)2O]3[UO3H2O]20.13H2O, which reacted further to form [(NH4)2O]5[UO3H2O]20.7H2O, under non-equilibrium conditions, with faster addition of ammonia resulted in precipitate of the composition [(NH4)2O]2.5[UO3H2O]20.14H2O, which further formed [(NH4)2O]5[UO3H2O]20. 7H2O. As the mole ratio of ammonium hydroxide to uranyl nitrate increase beyond 1.6 to 1.0 it formed poly-uranates, as pH increased rapidly. With vapour ammonia it is found the formation of precipitate type-I AU remained unaltered irrespective of change in mole ratio of ammonia to Uranyl nitrate. Thus the composition obtained through vapour ammonia is more stoichiometric and complete resulting in the uniform precipitate. The equilibrium conditions under aqueous ammonia as a reagent, produced precipitate which is easily filterable and to certain extent reproducible when carried over a period of 20 to 24 hours. The better quality precipitate took only 8 to 10 hours for carrying equilibrium precipitation using vapour ammonia. This is due to high polarisability of vapour ammonia which helps in maintaining low solubility allowing the particles to grow uniformly and rapidly and thus keeping nucleation to minimum at higher pH values. The settling rate indirectly a parameter of measuring the relationship between the particle shape and size depending on stokes law has shown maximum tolerance levels in the range of 60-65cc in 5 min per 500 ml with vapour ammonia over a wide periods of precipitation ranging from 6 hours to 20 hours. Where as the settling rate is very

sensitive and has shown less tolerance with aqueous ammonia precipitation over a range of 60 to 100 cc in 5 min per 500 ml ever for same duration of precipitation time of 20-24 hours. Any further fluctuation in precipitation time only resulted in abnormal variance of settling rates. This is due to the composition of ammonium uranate in which uranyl ion surrounded by loosely held hydrated molecules in case of type I AU produced by vapour ammonia route. The precipitate with aqueous ammonia has more of non-stoichiometric composition which is varying with respect to time and rate of addition of ammonia. As the precipitate shown the presence of uranyl and hydrated molecules without any ammonia molecules in the matrix the product found to be free flowable and anhygroscopic in nature when compared to the matrix of AU which held ammonium molecules when precipitated with aqueous ammonia. The better flowability of the precipitate can also be attributed due to the high diffusivity of unionised ammonia resulting in heterogeneous gas liquid based reaction unlike weak mobility of ammonium ion in ammonium hydroxide in a homogeneous reaction of liquid to liquid based reaction. Hence the flowability of AU is comparable with AUC which is confirmed by the flowability test carried using halls flow meter (8mm dia). The same test failed with AU produced from aqueous ammonia route. For the powders having high flowability the angle of repose is the indirect measurement to know the cavity of die filling without repeated fillings. The powder from vapour ammonia route have shown less angle of repose by about 5o when compared to the powders from aqueous ammonia route. The same characteristics are carried forward to the subsequent steps assessing the effect on sinterable density. The SEM pictures of AU (fig-1) produced from vapour ammonia has shown the agglomerate structure with less needle type and with more uniform porosity distribution similar to the observation conducted on AUC. The agglomerate of AU from vapour ammonia remained almost same as that of aqueous ammonia, unlike the flake type structure of type-I AUC produced. This is advantage from the point of better sinterability, which would require low temperatures. The composition of AU from vapour route confirms the presence of UO3.2H2O a type-I AU and also presence of U3(NH3)2 O9.4H2O a type-IV AU and UO3. NH3. H2O, a component of diuranate, by XRD studies. The type-I needle type monoclinic structure is predominant compound in comparision to numerous compounds of uranate from aqueous ammonia route. The composition variations in AU at different pH values through vapour ammonia route are to be further investigated though the variation of composition between 7 to 9 pH is not much, unlike the polyuranates formation from aqueous ammonia route for the same range of pH. It also may be possible to produce different types of AU by altering final pH through vapour ammonia through precise control over the hydrolysis reaction. The particles produced are larger in size and smooth or soft surface indicating monoclinic symmetry like AUC significantly different from AU produced from aqueous ammonia. TG curves of AUC have shown type-IV looses its weight at above 375oC, converting to UO3, where as type-I and II have significant weight loss starting from 175oC and completed at 225oC [18]. The ammonium uranate produced from vapour ammonia is found to behave as type-I AUC loosing all its loosely bound water molecules in the same

temperature range unlike the AU produced from aqueous ammonia route at higher pH values which behaved much like type-III and type-IV AUC. At effective temperatures below 275oC entire conversion of AU to -UO3 has taken place confirming stoichiometric nature of AU produced with vapour ammonia. The monoclinic structure of AU remains through UO3, after the decomposition, which would occur at 273oC [19]. The UO2 produced [fig-II] through -U3O8 calcination route between 675-700 oC does not show much difference in terms agglomeration and shows more of spherical in nature.This could be due to the nature of particle being course. The -UO3 thus produced has a distinct advantage of getting converted directly in to UO2 powder inview of its layered monoclinic structure and forming an intermediate compound of -U2O5 with layered hexagonal structure similar to -U3O8 which also undergoes the distortion from orthorhombic to hexagonal with monoclinic distortion before getting it reduced to fluorite structure with cubic crystal lattice of UO2. The intermediate packing sequence of ABAC between the ABC fluorite sequence in UO2 to the AAA sequence in -U3O8 [20]. -UO3 with similar packing arrangement the Uranium layers are destorted from hexagonal symmetry with an angle beta of 99.03 o rather than required 120o [21]. The reported crystallographic data indicate a sharp transition point between the two structures at the composition U2O5 with no reported fluorite type oxides higher than U2O5 and no layer type oxide lower than U2O5 the exposure of -U3O8 and -UO3 in reducing atmosphere at temperatures of 823 and 923o K has been shown to bring about reduction to UO2 [20]. This eliminates the process of conversion of AU to U3O8 before producing the final product of UO2 . The mother liquor at the end of the precipitation at pH 8 and above with vapour ammonia as a reagent found to contain the Uranium less than 3.2 mg/l which does not require a step of ion exchange to recover Uranium, as in the case of AUC production. This is due to trigonal pyramid shape of ammonia molecule with low symmetry as predicted by VSEPR theory, which gives the molecule an overall dipole moment and makes it polar so that the nitrogen atom in the molecule which has lone electron pair makes ammonia acts as a base. Due to this the ammonia molecules readily undergoes nitrogen inversion at room temperature i.e. the nitrogen atom passes through the plane of symmetry of the three hydrogen atoms; A useful anology is an umbrella turning itself out in a strong wind. The energy barrier to this inversion is 24.7 KJ/mole in ammonia. Which means in aqueous solution it takes proton from water to produce hydroxide anion and an ammonium cation which has regular tetrahedron. The degree to which ammonia forms the ammonium ion depends on the pH of the solution at physiological ~ 7 pH about 99% of the ammonia molecules are protonated[22].

9 PRECIPITATION CURVE OF VAPOUR AMMONIA 8

5 pH 4 3 2 1 0
0h rs 0h rs rs hr s 0h rs rs 0h rs hr s 0h rs 18 .3 0h rs rs 12 .3 0h 15 .3 0h 9. 30 h 13 .3 0 17 .3 0 10 .3 11 .3 14 .3 16 .3 8. 3 30 h 19 . rs

Morphology of ADU Powder Produced by NH4OH Route

TIME

CONCLUSION: The successful study which has been adopted in the plant scale has given good results keeping all the benefits of AUC, AU and negating the limitations of both the processes by using vapour ammonia as a reagent without using any carrier gas or inert gas, under equilibrium conditions. The process eliminates the steps such as preparation and handling of aqueous ammonia, reduced the cycle time of the batch to 50% and increase in batch size by 10%,which means increase in throughput by more than two folds. It also improved the filterability and the load factor of the drier resulting in stochiometric UO3 which paved the way for direct reduction eliminating the step of producing U3O8 as an intermediate compound. It lead to the conservation of energy, water, steam and manhours.

SEM picture of AU powder produced by aqueous ammonia

SEM picture of AU powder produced by vapor ammonia FIGURE-1

SEM picture of UO2 powder produced by aqueous ammonia

SEM picture of UO2 powder produced by vapour ammonia FIGURE-II

Morphology of UO2 Powder Produced Vapor Route

8 by Ammonia

ACKNOWLEDGEMENTS: The authors are thankful to Shri.G.V.S.Hemanth Rao,Dy.Chief Executive-Fuels and Shri.R.N.Jayaraj, Chief Executive-NFC, staff members of Uranium Oxide Plant for their co-operation for conducting these trials, Quality control and Characterisation laboratories for their analyses inputs. REFERENCES: 1. 2. 3. 4. 5. 6. PA Haas, Nuclear technology, 81 (1988) 393. E. Brandau, H Assmann and W. Doerr, Trans. Am. Nucl. Soc. , 31 (1979) 148. V. Mathieu, Trans. Am. Nucl. Soc. 28 (1978) 327 H Assmann and M Becker, Trans. Am. Nucl. Soc. (1979) 147 H. Assmann, W Doerr and M. Peehs, J. Nucl. Mate. (1986)1. E. Brandau and W. Doerr, in Proc. Meeting Europ. Nucl. Soc., Hamburg, Germany, May 6-11, 1979, page: 149. 7. Yi Ming Pan, J. Nucl. Mat. 99 (1981) 141-144. 8. Y.W. Lee and M.S. Yang, J. Nucl. Mat 178 (1991) 226 9. E.H.P. Cordfunke, J. Inorg. Nucl. Chem. 24, (1962), 303. 10. J. Janov, J. Nucl. Mat. 44 (1972) 174. 11. K.W. Song, J. Nucl. Mat. 200 (1993) 41-49. 12. J.A. Turnbull, J. Nucl. Mat. 50 (1974) 62. 13. R.C. Weast et.al (1988) Handbook of chemistry, 14. Rodney C Ewing, Can. Min. Vol. 34, (1996) 1071-1088. 15. Ball MC, J. Inorg. Nucl. Chem. 36 (1974) 1527-1529. 16. A Deptula, Nukleoniaka 7, (1962) 265-274 17. RC Hoyt, PhD thesis, Iowa state University, 1978, USA. 18. E H Kim et.al, J. Nucl. Mat. 209 (1994) 303, 304. 19. L Halldahl and M Nygren, J. Nucl. Mat. 138 (1986) 99 20. G.C. Allen, J. Nucl. Mat. 223 (1995) 234 21. P.C. Debets, Acta Crystallog. 21 (1966) 589. 22. C.E. Cleeton & N.H.Williams (1934) Online version; archive. URL last accessed May 8, 2006.

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