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Overview
INTRODUCTION
Contamination caused by improper
disposal of radioactive waste1 is of great
concern to industrialized countries.
Many nuclear testing sites and training
grounds are polluted by high levels of
radionuclides. There are two major categories of radioactive waste: high level
and low level. High-level waste (both
solids and liquids) result from spent fuel
generated from commercial and defense
R&D reactors, isotope production reactors, fuel reprocessing, fuel fabrication,
and weapon production activities. Lowlevel waste (solids and liquids) are generated from reactor operation, fuel cycle,
reprocessing, defense R&D and testing,
institutions, industry, uranium mining
and milling, and extraction activities.
6.00
2.00
0.00
2.00
4.00
6.00
8.00
0.00
LV = BV
Inc
Bac reasi
teri ng
al A
dhe
LV < BV
Bacterial
Adhesion
20.00
on
ng esi
asi dh
cre l A
De cteria
Ba
BV = Constant
40.00
60.00
SV (ergs/cm2)
80.00
PYRO- AND
HYDROMETALLURGICAL
PROCESSING
Bio-Redemediation
Bio-remediation of radionuclides is a
technique for cleaning uranium-contaminated soils. In this context, Reddy and
coworkers4 proposed a theoretical approach to predict a selective bacterial
attachment on surfaces of uranium-contaminated soil. A thermodynamic model5
was developed to calculate the Gibbs
energy of adhesion for several bacteriamineral systems. The kinds of bacteria
that could be used in uranium-leaching
processes were evaluated by using the
Gibbs energies of adhesion and the proposed limiting conditions for adhesion.
Their results indicated, for systems containing higher LV liquids or SV solids
(where is surface tension, S is solid, L is
liquid, and V is vapor), bacterial adhesion is strongly favored for uraniumcontaminated soils having negatively
charged surfaces. Thiobacillus ferroxidans
has been recommended as a suitable
microorganism for the uranium-contaminated soil. The change in Gibbs energy of bacterial adhesion per-unit surface area is given as:
Gadh = BS BL SL
sio
Gadh (ergs/cm2)
LV < BV
No Bacterial Adhesion
4.00
Large quantities of these radioactive substances contaminate the soil and ground
water, especially at U.S. Department of
Energy facilities.2 For example, the concentration of uranium in contaminated
soil and tailings of mine waste3 was 0.012
and 0.0020.11 percent respectively. Due
to stringent environmental regulations,
methods for disposing of radioactive
waste are being thoroughly investigated
and several processes for containing the
radioactive waste have been attempted.
(1)
100
Bacteria
80
Uranium Extraction (%)
60
40
20
0
0
Sterile
100
200
300
Time (hour)
400
500
(2)
where, is the fraction of uranium extracted in time (t), and R is the rate
constant containing the specific rate-constant per-unit-mass per-unit-time. In a
study of the effect of the particle size of
uranium-contaminated soil on the rate
21
U% Absorbed
80.0
60.0
40.0
20.0
Chabazite
Clinoptilolite
Erionite
Mordenite
0.0
1.0 2.0 3.0 4.0 5.0 6.0 7.0
pH
22
0.058
0.016
902.0 1.3
ZSM5
97.48
0.071
0.068
0.012
902.5 1.3
ZSM11
94.09
0.247
0.076
0.024
902.5 1.4
SSZ24
97.56
0.011
0.234
0.013
0.005
903.5 1.3
Hexagonal faujasite 86.75
3.542
2.152
0.229
0.239
0.032
900.2 1.3
Cubic faujasite
95.73
0.119
0.013
0.005
0.001
897.1 1.2
faujasite were measured by high-temperature solution calorimetry. The results obtained in those studies are given
in Table I. These zeolites have enthalpies
of 897.1903.5 kJ/mol and are only 714
kJ/mol less stable than quartz32 (910.7
1.0 kJ/mol), and only 0.56.5 kJ/mol less
stable than silica glass. Amorphous silica
derived from gels is higher in activation
enthalpy than fused glass (010 kJ/mol).
Since zeolites and amorphous silica occupy an overlapping range of energies33 ,
their enthalpies are not a strong function
of molar volume or related parameters
such as framework density or pore size.
Adsorption Kinetics
Considerable interest has been shown
toward the adsorption of heavy metal
cations, such as uranium, by zeolites.3440
Zeolites, which are able to adsorb as
much as their own weight of aqueous
and organic liquids, are a family of complex aluminosilicates having a three-dimensional network structure with
unique structural and chemical characteristics.41 Zeolites are also crystalline
and have pores interconnected by large
and small channels. The structural openings in zeolites are occupied by alkali,
alkaline earth cations, and loosely held
water molecules. The cations are exchangeable and the exchange is very
similar to crystalline SYNROC.42
Zeolites have excellent ion-exchange,
selective-adsorption, and catalytic properties.43 Grant et al.44 developed a system
to treat a variety of low-level, liquid,
radioactive waste streams generated
100 m
Figure 4. Scanning-electron micrograph of
uranium-adsorbed chabazite at pH2 and
298 K.
100 m
Figure 5. Scanning-electron micrograph of
uranium adsorbed chabazite at pH6 and 298
K.
Table II. Reaction Rates for Uranium Adsorption on Natural Zeolites at pH 2 and 298 K
Rate of Reaction (min.1)
Chabazite
Clinoptilolite
Erionite
Mordenite
1.7
0.5
0.5
0.3
0.9
0.3
0.23
0.27
0.29
0.14
0.11
0.12
0.096
0.044
0.035
0.038
Time
(min.)
10
30
100
316
from a nuclear-fuel processing plant using a non-regenerative-zeolite ion-exchange process. The minimum fluidizing velocity was calculated using the
equation developed by Ergun.45 The required fluidization velocity increased
with the voidage of the bed until it was
equal to the terminal velocity of the particles as the voidage approached one.
Once the terminal velocity of a particle
was exceeded, the particle would be entrained and carried from the bed. Relationships were developed between laboratory and full-scale systems.
Reddy et al.34,46 studied the adsorption
of uranium from aqueous solutions on
various natural zeolites (i.e., chabazite,
clinoptilolite, erionite, and mordenite).
Their results showed that uranium species are strongly adsorbed on zeolites
between pH 69 and that the adsorption
strongly depended on the pH of the
solution and the type of zeolite. The
reaction rates of uranium adsorption on
different zeolites at pH 2 and temperature 298 K are given in Table II. The
values of reaction rates are higher for
chabazite in comparison with other zeolites. From these studies, it can be concluded that, of all the zeolites tested,
chabazite has the maximum adsorption
capacity for uranium. This observation
could be related to the Si/Al ratio. If all
the factors are kept equal, a lower Si/Al
ratio means a higher zeolite capacity. In
a study on the removal of heavy metals
and other cations from wastewater,
Zamzow et al.47 observed maximum recoveries of lead with chabazite, suggesting that higher Si/Al ratios have higher
zeolite capacities. Bulk density must be
considered when selecting a zeolite since
the capacities are measured per unit
weight. Among the four zeolites studied, chabazite has the least bulk density
(most porous).34
Reddy et al.34,46 also studied the temperature dependence of uranium adsorption on chabazite and mordenite. The
results showed an activation-enthalpy
value of 3.6 kJ/mol in the temperature
range 293313 K. These results indicate
that the reaction is more favorable at
slightly high temperatures (Table III).
The uranium adsorptions on various
zeolites as a function of solution pH
were investigated in nitric-acid solutions
and at 298 K. The experimental results
(Figure 3) show that the amount of zeolite adsorption increases as the pH of the
solution increases. Scanning-electron
micrographs of two chabazite samples
23
Uranium Wastes
Pyrometallurgy/
Electrometallurgy
Precipitation
Adsorption on
Zeolites
Solution to
Recycle
Solids to
Discard
Salt Cake
U-ppt. Solids
U-with Zeolites
Hydrometallurgy
Solids to
Discard
Concentrated
Cake
Recovery of U
Storage/Disposal
Market
Figure 6. A pyro- and hydrometallurgical conceptual flow sheet for the disposal/recovery of
uranium from waste containing radionuclides.
16. S.Y. Lee and R.W. Tank, Applied Clay Science, 1 (1985), pp.
145162.
17. D.W. Oscarson and S.C.H. Cheung, Atomic Energy Can
Ltd. Rep. (1983), p. 37.
18. F. Bucher and M. Muller-Vonmoos, Applied Clay Science,
4 (1989), pp. 157177.
19. R.E. Grim, Clay Minerology (New York: McGraw-Hill,
1975).
20. R.N. Yong and B.P. Warkentin, Soil Properties and Behavior
(New York: Elsevier Scientific Publishing Co., 1975).
21. J.K. Mitchell, Fundamentals of Soil Behavior (New York:
John Wiley and Sons, 1975).
22. R. Soundararajan, Journal of Hazardous Materials, 24 (1990),
pp. 199212.
23. J.A.C. Marples, Glass Technology, 29 (6) (1988), pp. 230
247.
24. S.D. Moegling, Proc. Specialty Conference on Environmental
Engineering (New York: ASCE, 1989), pp. 15459.
25. P.A. Tempest, Nuclear Technology, 52 (1981), pp. 415425.
26. M.E. Morgenstein and D.L. Shettel, Jr., Proc. of the 4th
Annual Intl. Conf., American Nuclear Society and American
Society of Civil Engineers (Reston, VA: ASCE,1993), pp. 1728
1734.
27. A.E. Ring Wood, Safety Disposal of High-Level Nuclear
Reactor Waste: A New Strategy (Canberra, Australia: Australian National University Press, 1978).
28. H.D. Megaw, Proc. Phys. Soc., 85 (133) (1946).
29. R.G. Reddy and K.N. Hebbar, Proc. Symp. on New
Remediation Technology in the Changing Environmental Arena,
ed. B.J. Scheiner et al. (Littleton, CO: SME, 1995), pp. 171175.
30. I. Petrovic et al., Chem. Mater., 5 (1993), pp. 18051813.
31. A. Navrotsky, MRS Bulletin, 22 (5) (1997), pp. 3541.
32. CODATA Task Group, J. Chem. Thermodyn., 8 (1976), p.
603.
33. J.Y. Ying, J.B. Benziger, and A. Navrotsky, J. Am. Ceram.
Soc., 76 (1993), p. 1465.
34. M.K. Mohan and R.G. Reddy, Global Symposium on Recycling, Waste Treatment and Clean Technology, vol. I., ed. I.
Gaballah, J. Hager, and R. Solozabal (Warrendale, PA: TMS
1999), pp. 857868.
35. F.C.V. Renaud, J. Chem. Soc. Faraday Trans., 86 (24) (1990),
pp. 40954099.
36. R.T. Pabalan et al., Mat. Res. Soc. Symp. Proc., 294 (1993),
pp. 777782.
37. M.T. Olguin and M. Solache, Separation Science and Technology, 29 (16) (1984), pp. 21612178.
38. H. Mimura and K. Akiba, J. of Nuclear Science and Technology, 30 (5) (1993), pp. 436443.
39. H. Mimura, K. Akiba, and K. Kawamura, J. of Nuclear
Science and Technology, 31 (5) (1994), pp. 46369.
40. S. Forberg, T. Westermark, and L. Falth, Proc. of 3rd Int.
Symp. on the Scientific Basis for Nuclear Waste Management
(New York: Plenum Press, 1980), pp. 227234.
41. D.E.W. Vaughan, Properties of Natural Zeolites: Occurrence,
Properties, Use, ed. L.B. Sand and F.A. Mumption (New York:
Pergamon Press, 1978), pp. 353355.
42. R.A. Munson, Properties of Natural Zeolities, U.S. Bur. of
Mines Rept. of Invest. 7744 (1973), pp. 13.
43. J.V. Smith, Zeolite Chemistry and Catalysis, Monogr. 171,
ed. J.A. Rabo (New York: Am. Chem. Soc., 1976).
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and Ion Exchange: Fundamentals and Applications, 84 (264)
(New York: AIChE, 1988), pp. 1322.
45. S. Ergun, Chem. Eng. Prog., 48 (89) (1952).
46. R.G. Reddy and Z. Cai, Light Metals 1996, ed. W.R. Hale
(Warrendale, PA: TMS, 1996), pp. 11731180.
47. M.J. Zamzow et al., Separation Science and Technology, 25
(13-15) (1990), pp. 15551569.
48. M. Saleem and M. Afzal, Separation Science and Technology,
27 (2) (1992), pp. 239253.
49. U. Cetin and R.K. Mehta, Pre-print (Paper presented at
the SME Annual Meeting, Orlando, Florida, March 1998).
50. P.E. Eberly, Jr., Zeolite Chemistry and Catalysis, ed. J.A.
Rabo, ACS Monogr. 171 (Washington D.C.: ACS, 1976), p.
392.
51. D.M. Ruthven, Diffusion in Zeolites: A Review of Recent
Progress, in the Properties and Applications of Zeolites, ed. R.P.
Townsend (London: Chem. Soc., 1980), p. 44.
52. M.K. Mohan and R.G. Reddy, Recent Res. Devel. Metallurg.
& Materials Sci., 3 (1999), pp. 4969.
R.G. Reddy is the ACIPCO Chair Professor at the University of Alabama, Tuscaloosa.
For more information, contact R.G. Reddy, The
University of Alabama, A-129 Bevill, Tuscaloosa,
Alabama 35487-0202; phone: (205) 348-4246;
fax: (205) 348-2164; e-mail: rreddy@coe.
eng.ua.edu.
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JOM January 2001