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LEGAL NOTICE
This report was prepared as an account of
Government sponsored work. Neither the
United States, nor the Commission, nor any.
person acting on behalf of the Commission:
A. Makes any warranty or representa-
tion, expressed or implied, with respect to
| the accuracy, completeness, or usefulness
of the information contained in this report,
or that the use of any information, appa-
ratus, method, or process disclosed in this
report may not infringe privately owned
rights; or
B. Assumes any liabilities with respect
to the use of, or for damages resulting from
the use of any information, apparatus,
| method, or process disclosed in this report.
As used in the above, "person acting on
behalf of the Comraission" includes any em-
ployee or contractor of the Commission, or
employee of such contractor, to the extent
that such employee or contractor of the
Commission, or employee of such contractor
prepares, disseminates, or provides access
to, any information pursuant to his employ-
ment or contract with the Commission, or
his employment with such contractor.
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SEP 16 1965
ORNL. P.152:2
CONF-650919-3
- ALKYLBENZENE SULFONATE (ABS) CONTROL FOR
THE FOAM SEPARATION PROCESS*
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W. R. Laing and E. C. Lynn
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Oak Ridge National Laboratory
Oak Ridge, Tennessee
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*
RELEASED FOR ANNOUNCEZENT
IN NUCLEAR SCIENCE ABSTRACT'S
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*Research sponsored by the U. S. Atomic Energy Commission under co
atract
with the Union Carbide Corporation
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.. In nuclear fuel reprocessing the spent fuel elements
are dissolved, the unused uranium 18 recovered, and the
- radioactive fission products are concentrated. A byproduct
of these operations is thousands of gallons of slightly ·
radicactive process waste water. It is not practical to :::::
concentrate or store these large volumes of water, 80 . .
processes have been developed to remove radioactive com-
ponents. Some of the methods which have been used are
caustic-carbonate scavenge, ion exchange, and dilution.
In a search for better decontamination methods, ...
workers at Radiation Applications, Inc., found that strontium ·
was concentrated by alkylbenzene sulfonate foam (4). Alkyl-
benzene sulfonate or ABS is' the general name for the surface
active agents used in synthetic detergents. A specific
alkylbenzene sulfonate, which will be mentioned later, is
dodecylbenzene sulfonate or DBS. This discovery lead to
the development of the Foam Separation Process by Radiation
Applications, Inc., and Oak Ridge National Laboratory (2). :
:.: In this process (Fig. 1) the waste water is mixed with
grundite clay, and 2-9 ppm of iron is added. The pH is
adjusted to 11.3 with NaOH and Na,coz. The precipitate and
particulate matter are removed in a suspended bed sludge
column. Dodecylbenzene sulfonate is added to give a con- .
centration of 60-100 ppm. The water then flows to a counter-
current foam column where air is bubbled through the column
to generate foam. The foam is removed and broken with a
basket centrifuge. The DBS level of the foam concentrate 18
: 2000 ppm. The column effluent 18 10-30 ppm.
Fig. 1
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ORNL DWG. 64-7834
FOAM CONDENSATE
LOW-LEVEL-WASTE FEED
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GRUNDI TE CLAY ::
(-250 mesh fired
at 600°C for 20 min.).
FOAM
ALMOST CLEAR
EFFLUENT
und
wommen
Fe 3+
-9 ppm
Toporomom
cresce
FOAMING AGENT
DBS*, 60 ppm
SLUDGE BED
pH = 11.3:
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.::::,
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OR
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REMOVAL OF SLUDGE
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PRECIPITANT:
NaOH, 5 x 10-3 M
Na2CO3; 5 x 10-3 M
DECONTAMINATED
PRODUCT
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::.......
...
*DBS = Dodecylbenzene sulfonate
figuretat
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Fig. 2
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The effectiveness of the removal of fission product
radionuclides is shown in figure 2. Decontamination factor
is defined as the concentration of radioisotope in the feed
stream divided by the concentration in the column effluent.
The principal element to be removed from the waste water is
Sr, and its decontamination factor is 3500.
A pilot plant was built to demonstrate the effective. ..
ness of this process. It operated successfully from June,
1964 through December, 1964.
The Technicon AutoAnalyzer was used to provide process
control for the DBS concentration during the operation of
the pilot plant. The procedure used for this analysis 18
called the Methylene Blue Method (3) and consists of the
following steps:
1. React DBS with methylene blue.
2. Extract the DBS-methylene blue complex into chloro-
form.
3. Scrub the chloroform extract with wash solution. .
4. Measure the absorbancy of the chloroform phase at :
625 mu.
This method, when done by hand, requires considerable
time because the extraction of the DBS-methylene blue complex
into chloroform is not complete in a single extraction. It ..
requires three extractions with fresh chloroform, and this
is followed by a wash of the organic phasei .
The flow diagram for the AutoAnalyzer, method is shown
in figure 3.. Sample (1-8 ppm DBS) is picked up by the
sempler, mixed with methylene blue and then with chloroform. : ;
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Fig. 3
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ORNL-LR-Dwg 64-8531
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: DECONTAMINATION OF
SPIKED ORNL LOW-LEVEL WASTE BY
FOAM SEPARATION PROCESS
FEED: 0.005M EACH NOOH; Na2CO3; GRUNDITE CLAY 1/2 lb/1000 gal..
- VARIABLE
Ca...
85 Sr
2
OVERALL
100
3500
220
DECONTAMINATION FACTORS
SLUDGE COLUMN FOAM COLUMN
50
16
21
0.85
2.3
0.85
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3.8
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137CS
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TIOMNIC
ICON
AutoAnalyzer
METHOD ALKYLBENZENE SULFONATE (ABS)
Reference
Concentration Range det. Le
Type Sample Foam Separation Process
Dato_July 14, 1965
Signaturo.
Affiliation ORN
methodology
+
:::
:
•.
Upper
al
: Tube Size
(inches)
SAMPU
Rate: 40 per hour
0.056 sample
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extraction
column
0.056 air
,
10.065 methylene blue
*
*
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TOTOJOTTOTO
0.081 chloroform *****
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33.
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10.081 chloroform
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0.110 Plowcell
, WASTE
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B i modified :
PROPORTIONING
PUMP
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All tubing is Acidflex
*
RECORDER:
COLORIMETER
15 mm Tubular Ilc
650 my Filters
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figure 3
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• It then goes to the extraction column where the DBS-methylene
blue complex 18 extracted into the organic phase. Following
the extraction column 18 a phase separator where the aqueous
and a portion of the organic is sent to waste. The re- :
mainder of the organic is pumped through the flow cell, and
the absorbancy is measured.
This flow diagram is slightly different from the
standard AutoAnalyzer ABS flow diagram (1). The scrub .
of the chloroform phase has been eliminated. With the higher
ABS concentrations in the Foam Separation Process, it 18
not necessary to use the scrub section.
The sampler is operated at 40 samples per hour with
water in every other cup. The rate by hand using the recom- :
mendod procedure is fouü per hour. All reagents are the
same as in the standard AutoAnalyzer flow diagram.
The equipment has operated satisfactorily except for
a tendency for the nipples to slip out of the acidflex
pump tubes that are in contact with chloroform. This
problem was solved by wiring the nipples in place.
· A calibration curve using 3, 5, and 8 ppm DBS is shown
'in figure 4. Absorbancy paper is used on the recorder, and
a p.lot of DBS concentration vs. absorbancy should give a
straight line. The slope of this line will be the calibra- .
: tion factor in ppm DBS/ abs. unit. The absorbancy of a ...
sample multiplied by this factor will give ppm DBS.
Control of the pH of the sample dilution is necessary
with this flow diagram. The optimm pH range 18 8-10.
Below pH 7 there is a loss in sensitivity and broadening of
the recorder peaks. If phenolphthalein is added to the
: sample dilution and it is ad justed to light pink with acid
or base, the pH will be in the correct range.
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Fig. 4
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imeinen train de baie...'.
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8 ppm
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ABSORBANCY
figured...
DBS STANDARDS
CDC
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ORNL - DWG. 65-7521

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A comparison of some synthetic DBS solutions by the Auto-
Analyzer and by hand are shown below:
Comparison of Synthetic DBS Solutions
Actual DBS
Conc. ppm
Solution No.
Found by
AA
Found by.
: Hand
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20
21
80
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19
80
..... 2050
79
2000:
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1950
"
During the operation of the pilot plant we analyzed
about 2000 samples. The speed and accuracy. were satisfactory.
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References
1. Anon., Technicon AutoAnalyzer Methodology, Alkylbenzene
Sulfonates, Technicon Controls, Inc., Chauncey, New
York, 1963.
2. Davis, 'W., Jr., Kibbey, A. H., and Schonfeld, E., .
"Laboratory Demonstration of the Two Step Process for
Decontaminating Low Radioactivity Process Waste Water
by Scavenging - Precipitation and Foam Separation,"
ORNL-3811, in press.
Farber, L., Editor, Standard Methods for the Examination .
of Water and Waste Water, lith ed., Albany, N. Y., Boyd.
Printing Co., 1960, p. 246.
4. Schonfeld, E., Sanford, R., Mazzella, G., Ghosh, D.,
and Mook, S., "The Removal of Strontium and Cesium .
From Nuclear Waste Solutions by Foam Separation," :
· 140-9577, July, 1960.
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3. . Thennam
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DATE FILMED
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