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L- 23 .ASSIFIED
Subject Category: CIIlEMISTRY
UNITED STATES ATOMIC ENERGY COMMISSION
NOTES ON THE EFFECT OF MAGNESIUM
December 7, 1954
Upton, New York
Technical Information Service, Oak Ridge, Tennessee
Work performed under Contract No. AT-30-2-Gen-16.
Date Declassified: November 16, 1955.
This report has been reproduced directly from the best
Issuance of this document does not constitute authority
for declassification of classified material of the same or
similar content arid title by the same authors.
Printed in USA, Price 15 cents. Available from the
Office of Technical Services, Department of Commerce, Wash-
ington 25, D. C.
This report was prepared asa scientific account of Govern-
ment-sponsored work. Neither the United States, nor the Com-
mission, nor any person acting on behalf of the Commission
makes any warranty or representation, express or implied, with
respect to the accuracy, completeness, or usefulness of the in-
formation contained in this report, or that the use of any infor-
mation, apparatus, method, or process disclosed in this report
maynot infringe privatelyowned rights. The Commission assumes
no liability with respect to the use of,or from damages resulting
from the use of, any information, apparatus, method, or process
disclosed in this report.
NOTES ON THE EFFECT OF MAGNESIUM ON PROCESSING
By J. Weisman
'his spo reports the results of a number of experiments involving
magnesium. Although only preliminary results have been obtained, it is
felt that they should be placed on record.
T Effect of Macnesium on the Solubility of Uranium in aismuth
The effect of magnesium on uranium solubility at 5000C was investigated.
Initial runs were made as follows: Approximately 10 grams of purified bismuth,
1 gm of uranium plus the required amount of magnesium were placed above a
coarse pyrex frit. The bismuth was melted under high vacuum, equilibrated
at 5000C, and then filtered by application of helium pressure.
This procedure was not satisfactory because the magnesium reacted with
glass. To prevent this, a graphite cup was inserted in the tube above the
frit. To prevent bypassing of gas in filtration the glass was shrunk around
the graphite. Holes which were small enough to retain the bismuth until gas
pressure was applied, were drilled in the bottom of the cup. The molten
metal was thus in contact with glass only for the few seconds required
Tsaing the pranhite sleeves the data shown in fig. 1 were obtained. It
is seen that magnesium has a small but nopreciable effect on uranium solubility.
More data should be obtained, particularly at low magnesium concentrations.
IT Peduction of "ranium and Thorium Compounds by Magnesium
The presence of large quantities of uranium oxide in Loop C, despite
the addition of magnesium, indicates that at 5000C magnesium does not reduce
rT02. Th02 also appears stable with respect to magnesium.
In one experiment Th and TT were oxidized into the salt phase by adding
LiOH to the salt. This salt was then contacted with bismuth containing
4900 ppm Mg. Although there were 930 ppm of U and 430 pTn of Th in the
salt, no more than 10 ptu of U and Th were detected in the metal.
In contrast to this, the chlorides of IT and Th are reduceable. The
results of two runs are given below. With 54 pnm of Mg in the metal, only
a slight reduction is obtained. However, with 450 ppm of Mg, good reduction
is obtained. Furthermore, the reduction of uranium proceeded to a far
greater extent than that of thorium. In this run a separation factor of
about 22 was obtained. It may be possible to base a blanket processing
scheme on the selective reduction of uranium ani thorium chlorides.
uin Vo, Procedure n sm:th "alt LiCl)
787 Th and U present in salt as oxides 40 ppn U 930 ppm U
or hydroxides. Salt then contacted 10 ppm Th 410 pnp Th
with bismuth containing magnesium. 1900 ppn Mg
907 Th and U added to salt as chlorides. 1,60 ppm Th 2,250 plm Th
Salt then contacted with Bi con- 1,600 ppn U 1P7 ppm U
training Mg. 450 ppn Mg
920 60 ppm nY 230 pmp U
47 ppm Th 280 ppm Th
5t pmn Mg
III The Peluction of ware Earth Chlorides
If the molten salt is thrown away after it is used for fission product
extraction, its cost may be a considerable item. A cheap method of recovery
and reuse of the salt would thus appear desirable.
Previous experiments have shown that the rare earths may be extracted
from the salt into molten bismuth by adding Mg to the metal. Since, in
this case the bismuth acts only as an inert carrier, it should be possible
to substitute lead for it. This will, of course, result in a considerable
saving as the price of lead is less than 1/10 that of bismuth.
Preliminary experiments have been carried out by J. Speirs using
mixtures of lead and bismuth. Cerium was first transferred into the salt
by contacting the salt with molten Bi containing Ce metal. The salt was
then removed and contacted with a molten Pb Bi alloy containing Mg. The
results obtained are as follows
PPM Ce in PPM Ce in Mg added to
Run No. Metal Salt metal initially
9?2 67.7 141 500 ppm
Mg analysis of
983 64.7 171 1000 ppm metal after
984 62.7 147 1000 pum contact not
much less than
The results obtained indicate that cerium can be transferred to lead.
They of course do not establish the capacity of the lead for fiseion products
since the runs were carried out at low reductant concentrations. The capacity
should be quite large since it is not necessary to retain the fission products
in solution. If a large excess of reductant is used, the fission products
should be extracted from the salt after their solubility in the metal is ex-
ceeded. The limiting concentration would probably be set by heat removal
Further experiments should be run using much larger excesses of the re-
ducing agent. Both calcium and magnesium should be tried.
IV Use of Variable Oxidation Potential in Fuel Processing Scheme
Several chemical processing loops are now being planned by the Fuel ,
Processing Group. In order to intelligently develop pumps, instrumentation
and other components it is necessary to have some idea of the size of
equipment which might eventually be used in an IMFP. A preliminary flow
sheet has therefore been drawn up.
The flow sheet proposed in fig. 2, has used as a design basis those
parameters developed by 0. E. Dwyer in PNL D-2q20. The flow sheet differs
from that shown in D-2820 in that a closed salt cycle is used. It was
also assumed that it was desirable to operate all columns continuously.
This limits the minimum flow rate of any stream to about 1/20 of a gpn,
(smallest flow in D-2320 was 1/5 gal/hr). The use of larger flows
necessitated the addition of another uranium stripping column in order
to avoid excessive T losses.
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