Nuclear

Engineering
and Design
ELSEVIER Nuclear Engineering and Design 159 (1995) 209-212

Technical Engineering Note

Drying medium level liquid waste concentrates

S. K u n z e , K . G o m p p e r
Kernforschungszentrum Karlsruhe GmbH, lnstitut fiir Nukleare Entsorgungstechnik (INE), Pos([ach 3640,
D- 76021 Karlsruhe, Germany

Abstract

Experiments on drying simulated medium level liquid waste concentrates on the laboratory and technical scales
produced, under the selected conditions (40-80 °C, about 20-200 mbar), a dry salt cake (residual moisture less than
0.6%). Splashing of the drying product during the final phase of drying has been largely avoided by addition of small
amounts of sodium tetraborate. During the whole test (heating, drying, secondary drying, cooling) no exothermic
reactions took place.

I. Introduction impurities). Therefore, the thermal and chemical

In connection with decommissioning of the
Karlsruhe Reprocessing Plant (WAK) vacuum
drying in cast vessels was considered as an alterna-
tive to cementing for conditioning of the medium
level liquid waste concentrates (MLLWC) arising.
The advantage over cementing which is offered by
this method is the clearly smaller volume of the
waste forms (up to 15 times reduction, depending
On the M L L W C activity inventory). This means
savings in the costs of disposal.
Until now only borated waste solutions, decon-
tamination solutions, etc. from nuclear power
plants have been dried on a technical scale (Enge-
lage, 1985). However, experience accumulated in
these operations does not allow a direct statement
to be made on the drying behaviour of the
M L L W C because of the differences in chemical
composition (high nitrate concentration, organic
behaviour during vacuum drying of these wastes
had been investigated at the Institute of Nuclear
Waste Management Technology (INE) before the
drying technique was applied to MLLWC.
2. Experiments with 1 1 M L L W C
In more than 100 drying tests conducted on a
laboratory scale with simulated M L L W C also
containing organic substances the temperature
profile in the drying receptacle/dry product was
determined. In none of the operating phases
(heating, evaporation, drying, secondary heating,
cooling) were significant differences in tempera-
ture measured at the various points of measure-
ment in the dry product (Fig. 1). The organic
constituents investigated were substances occur-
ring as impurities in the MLLWC, e.g. citrate,

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210 S. Kunze, K. Gompper ,; Nuclear Engineering and Design 159 (1995) 209 212

OryTng
250 j ! i E ! i {
J C i t r o t e , !tartrate,! oxolate,! EDTA, T]BP, DBPi k e r o s i n e (Off-gas)

2 2 5 t w]ih--i 5-[g-y [-Na2~]~ O:7--;--::i-0--H 2 O- ~............. i.......... ] . . . . . . . . . .

C) ............ i ............ i ............... i ..... i ............ .............

o ~75-+............ i ............ :~............. ::............. :~..... i ...................

@ 15oJ ............. i ............ i ................... i ......................................

2
©
125 ~ Measuring points

i! :!
L
q) 100 ~
o_
E
0) 75i
Measuring point 5
50- A--A Measuring point 4
[] [] Measuring point 3
25 (3-49 Measuring point 2
ca. 200i m b a r i iJAWC 0`3 t I Mecsuring point 1
0 .... i .... i .... i .... i . . . . . . . . i ....
0 5000 10000 15000 20000 25000 50000 35000
Time / s

Secondery heating
2504 : ,, ; ; ; ;
Citrate, i:tartrate,Z: oxalate,:, EDTA, T~P, DBPi k e r o s i n ~ 5 (Off-gas)
225 ..... ............
~oo ~-wii-~--i-6-[g7i--~-~:~x6Y-;----6--~q~~........................... i ............
©
0 175 ............ i . . . . . . . . . . I i I1-

150 ........... " --i ............ 4............ i ...........

2 125 " ............ ::............ i ............ M gnn

" points
2
~_ 100 ....... ~............ i ............
r~

I-- Measuring point 5

50 ---" ............ Measuring point 4
Measuring point .3
25 ...... Measuring point 2
I Measuring poinf 1
0
0 5000 10000 15000 20000 25000 ,30000 .35000

Time / s
Fig. 1. Temperature plots from the dry product and off-gas in vacuum drying of simulated MLLWC (pH = 9) at 200 mbar.

E D T A , kerosine, at concentrations of a few 8 0 ° C at negative pressures of 2 0 m m water

grammes per litre. In order to simulate an acci- column and 200 m m water column) due to the
dent, a multiple o f the anticipated concentration organic constituents either during secondary
o f organic matter was used (second phase). In no heating of the dry product to 150 °C or in the
case has an influence been detected on the drying course of slow cooling down to room tempera-
behaviour during the drying phase (40 °C and ture.
 S. Kunze, K. Gompper / Nuclear Engineering and Design 159 (1995) 209 212 211

Table 1
Results of drying simulated M L L W C in 200 1 d r u m s

Mode of operation Course of experiment Duration Plate-outs in Dry product

of vapour pipes
experiment Residual Distribution of
(h) moisture compressive
(%) strength
Nmm 2

t First fill: 30 1 At temperatures of the 366 yes 0.25--8.3 << I 40

Refill: max. 601 recirculating air of 140 170 °C
200 m b a r vapour pipe clogged twice:
at temperatures of the
recirculating air < 130 °C
no plate-outs.
2 First fill: 80 1 At temperatures of the 390 no 0.31-0.56 < 1 34
Refill: max. 80 1 recirculating air < 130 °C
~ 200 m b a r no plate-outs.
3 First fill: 50 1 At temperatures of the 261 yes 0.10 1.00 < 1-34
Refill: max. 501 recirculating air between
~ 20 m b a r 150 and 170 °C
plate-outs in the vapour
pipes.
4 First fill: 160 1 Heavy splashing at 207 yes 0.24 4.52 << I 26
Refill: max. 1001 recirculating air
~ 20 m b a r temperatures up to 185 °C
plate-outs in the vapour
pipes extending to the ultra-
filter.

During the final phase of drying, when the
concentrated brine was transformed into a crystal
pulp and a dry salt blend, heavy splashing oc-
curred in the inactive experiments which might
lead to plate-outs in the off-gas pipework. By
addition of sodium tetraborate to the MLLWC
simulate solution to be dried (10gl 1) it was
possible to largely avoid splashing at drying tem-
peratures of 75 °C and above (Heller, 1975).
3. Technical-scale experiments
In 1992, vacuum drying was tested on a techni-
cal scale. A total of four drying experiments were
performed in cooperation with Gesellschaft fiir
Nuklearservice (GNS), Essen, in the PETRA-III
facility of the company installed at the Central
Decontamination Plants Department (HDB) of
the Karlsruhe Nuclear Research Centre (KfK).
Vacuum drying was performed in 2001 drums
at 20 and 200 mbar pressure and at the resulting
temperatures of the concentrates of 40 and 80 °C.
The 20 mbar level was chosen with reference to
experience gathered with NPP waste. The 200
mbar level followed from positive results obtained
in the laboratory-scale experiments. 7701 of
MLLWC simulate (set at pH 9) per drum were
dehydrated. In order to avoid splashing of the
product during the final phase of drying, 10 g 1-~
sodium tetraborate were added to the simulate
which in the laboratory-scale experiments proved
to be highly effective at concentrate temperatures
75 °C and above. The drums were heated by
recirculating air.
The results of the experiments are entered in
Table 1, Under the experimental conditions de-
scribed as modes 3 and 4 of operation in the
table, considerable plate-outs in the drum lids and
212 S. Kunze, K. Gompper / Nuclear Engineering and Design 159 (1995) 209-212
in the vapour pipes were found on account of
splashing of the drying product. The addition of
sodium tetraborate did not exert an effect on
account of the low temperature of 40 °C of the
concentrate at 20 mbar negative pressure. This
resulted in clogging of the pipework and hence in
the interruption of the process of drying. In con-
trast, in mode 1 of operation (200 mbar) the
heating power was excessively high. By reduction
of the temperature of recirculating heating to
130 °C or less it was possible to avoid any notice-
able plate-outs of splashed drying product (mode
2). The residual moisture and compressive
strength (Schmidt rebound hammer) were deter-
mined on drums with the shells removed and then
sawn apart. Here also, mode 2 produced the best
results (German Patent, 1993).
In none of the operating phases (heating, dry-
ing, secondary drying, cooling) were significant
temperature differences found at the various
points of measurement within the drums; so there
were no indications of any exothermic reactions
taking place. Neither did investigations based on
differential thermal analysis produce any indica-
tions in the range of temperatures below 200 °C.
The periods of drying were between 207 and
390 h. However, the PETRA-III facility used in
the experiments had not been optimised for dry-
ing waste solutions with a high salt content at
200 mbar and 80 °C. With the facility appropri-
ately conceived, remarkable shortening of the pe-
riod of drying can be anticipated.
References
H. Engelage, G. Gestermann and D. Rittscher, Kondition-
ierung von fliissigenradioaktivenAbf/illenin Zwischen-und
Endlagerbehfiltern durch Vakuumtrocknung, Atomkernen-
ergie, Kerntechnik 47 (1) (1985) 42-44.
German Patent DE 42 01 841 C1, June 24, 1993.
G. Heller, Boroxide, Borsfiuren, Borate, in K. Niedenzu and
K.-Ch. Buschbeck (eds.), Gmelin Handbuch der Organis-
chen Chemie, Erg/inzungswerk zur 8. Auflage, Band 28
Borverbindungen, Tell 7, Springer-Verlag, Berlin, 1975, pp.
126-132.