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Internal Note 1969-38-I



December 1969

Atlantic Oceeanographic Laboratory

Bedford Institute

Dartmouth, N.S. Canada

This note does not represent the view of the Bedford Institute or
even necessarily the final view of the Author. It may not be
quoted or used as a basis for policy or decisions, excent as
specified by the Author. Circulation is the Author's responsibility.

Abstract (i)
Introduction 1

A critique of the Solvent Extraction Techniques used in

Sea Water Analysis for Trace Elements 2

Counter-Current Technique to Extract Trace Elements

from Sea Water at Sea 3

Trends in Extraction Column Design 5

Reported Construction Details of Pulsed Columns 5

Construction and Operation of the Proposed Laboratory

Pulsed Sieve-Plate Extraction Column '7

Extraction Column 7

Air Pulsing Unit 7

Operation of Extraction System 8


Appendix A

Appendix B

A pulsed sieve-plate extraction column is suggested for

processing large volumes of sea water, with a relatively small
volume of organic solvent carrying a chelating agent.
One inch diameter glass column is proposed as an experi-
mental apparatus to determine the feasibility of the above con-
cept. The column is designed so that both column length and
distance between sieve-plates can be altered. The sieve-plites
will be constructed from teflon, with performation of MB to
64 inch diameter and about 25% of the column cross-sectional
area available for the flow of fluid. The pulsing in the column
itself will be induced by an air pulser.

Apparent advantages of pulsed sieve-plate extraction

columns are discussed and compared with previously employed
extraction techniques. The construction of some reported col-
umns is outlined. The design and operation of such an apparatus
in extraction of chelated trace metals from sea water is discussed.


Quantitative analysis of trace elements in sea water is an important

aspect in marine chemistry and may contribute to an understanding of
ocean circulation and the productivity of the marine environment, as
well as provide information necessary to warrant action in instances
when the sea is being forced to receive industrial pollutants in con-
centrations that may prove toxic to its residents.

The low concentration of trace elements in sea water prohibits

the use of most modern instrumental techniques; preconcentration of the
trace elements in the sample is usually necessary before chemical
analysis for many of the trace elements is possible,and cases where the
sensitivity of the instrumental technique is adequate at the concen-
tration levels of trace elements in sea water, the determination is
subjected to interference by other constituents in the raw sample.
For example, although gamma-ray spectrometry is a powerful tool in trace
element analysis it is not directly applicable to a sample of sea water
because sodium (one of the major constituents in the sample) interferes
with the analysis and hence leads to erroneous results. In addition,
the presence of uranium complicates the interpretation of the spectra.
Such interfering elements must therefore be removed from the trace
element medium before meaningful analyses are possible. This may be
done by complexing the trace elements and then extracting these com-
plexes into an organic phase. This technique, (solvent extraction) in
addition permits the concentration of trace elements in the extract to
be increased greatly over those originally present in the sea water
sample. Solvent extraction has been very effective in many cases where
separation by classical methods such as fractional crystallization or
precipitation is difficult or impossible. The advantages of this pro-
cedure over classical ones include:

(a) high degree of selectivity in suitable circumstances

(b) ease and speed of operation

Mr1+-PnRIMR F i.-1-R- MR= Aqueous phase

lin it < interface
MRn HR Organic phase

FIGURE 1: Extraction of Metal Chelates

Selective removal of trace elements from sea water, by use of the

counter-current solvent extraction technique, with an organic phase
denser than water, appears very promising.2 A very high enrichment is

possible by this procedure and an enrichment of the order of 400,000

has been obtained by Brooks from a volume of approximately 8 liters of
sea water. By incorporating several chelating agents in the extraction
system which may then consist of more than one contacting apparatus,
it is possible to extract several elements at the same time. The
selectivity can be improved in solvent extraction through the control
of pH of the aqueous phase. Solvent extraction is therefore a powerful
technique for separating small amounts of the trace elements from large
volumes of sea water.

All but 20 of the 92 elements have been found in sea water; of

these, only 14 elements have concentrations larger than one part per
million11t Estimated concentration of some of these elements are listed
in Appendix A, along with the spectrographic detection limits. It is
apparent from these values that the trace elements present in sea water
should be extracted into a relatively small volume of organic phase
before any determination of trace elements is attempted.

The risk of contaminating the sample when working with trace

quantities of a substance is always a hazard. In solvent extraction
the risk is kept at a minimum. Only two reagents are required and both
can be purified to reduce the risk of serious contamination from the
reagents2. A counter-current extractor has a large surface in contact
with the liquids. The risk of contamination from this source is serious.
Coating- of much of the surface with teflon should reduce the risk of
contamination but no definite statement can be made regarding this aspect
of minimizing contamination.

The problem of determining trace elements has received considerable

attention, but to this day no reliable procedure is available to analyze
sea water for its trace elements. A different direction of attack is
therefore necessary.

A Critique of the Solvent Extraction Techniques used in Sea Water

Analysis for Trace Elements

The only attempts to preconcentrate trace elements in sea water

by solvent extraction have employed Craig-Post discontinuous counter-
current apparatus and the conventional separatory funnel.
Brooks used the Craig-Post extractor to concentrate a number of
trace elements. This apparatus consisted of 120 units and 20 hours
were required for each determination. Although laboratory installation
of such equipment is convenient particularly for automated operation,
it would be impractical to equip a ship laboratory with such a large and
complex apparatus, since its operation is extremely slow. Furthermore,

its operation may be hindered by the uncontrollable movement of the ship

and consequently undesirable transfers may take place.

Reduction of the volume of sea water sample by evaporation, and

applying the conventional separatory funnel technique, has been invest-
igated in this laboratorys. Besides being laborious, this procedure
is likely to yield results which are inconsistent or not representative
of natural sea water. Altering the ionic equilibria of the sample
before extraction may result in one sample undergoing changes that are
not consistent with another, depending on the concentrations of other
unknown species present in an average sample. To avoid such phenomena
from taking place, it is desirable to extract the trace elements with
the least amount of modification to the sample.

Since these methods are not suitable for onboard ship, or yield
unreliable results, a different method must be sought. As described in
the next section, a continuous counter-current extraction using a pulsed
sieve-plate extraction column would seem to provide a practical solution
to this problem.

Counter-Current Technique to Extract Trace Elements from Sea Water at Sea

Continuous counter-current extraction columns offer considerable

promise as extractors for installation onboard ship. These columns can
be secured in a rigid position and do not occupy much floor space.
They may, however, occupy considerable wall space if the extraction
system is to consist of several such columns.

Because of the relatively large volume of sea water that has to

be contacted, with an overall smaller volume of organic phase carrying
the chelating agent, a continuous counter-current column(s) is more
suitable than a discontinuous one. Efficient regenerating and recycling
the organic phase is possible in such an extractor. With continuous
counter-current operation, the aqueous-to-organic phase ratio in the
column can be kept at the minimum, thus giving better extraction effic-
iency, while the overall aqueous-to-organic phase is very much greater
than one.
As shown in Table I, mechanically agitated continuous counter-
current extractors are found to have higher extraction efficiencies
compared to other types of extractors. Scale-down models of such systems
should also perform efficiently.

For the shipboard extraction of trace elements from sea water,

mechanically agitated continuous counter-current extractors appear to
have the following advantages over other solvent extraction apparatus:

1. The rolling of ship can have no effect on extraction.

2. They can be operated from a direct sea water supply; hence,
large volume can be extracted without storage.
3. The space occupied by such a system will be less than a train
of Craig-Post tubes.
4. Many trace element extractions can be nerformed using a single
sire- of sea water by controlling the pH's at the inlets to the

Type Liquid - Plate or Spacing
Capacity Stage Between
of HTU* Efficiency Plates or
Combined Stages
ft3 ft2-hr ft % inches
Mixer-Settler - 75-100 -
Spray Column 50-250 10-20 - -
Packed Column 20-150 5-20 - -
Perforated Plate Column 10-200 1-20 6-24 30-70
Baffle Column 60105 4-6 5-10 4-6
Agitated Column** 50-100 1-2 80-100 12-24

* HUT E hei t of theoretical unit. To accomplish a set extraction

(say :4 /), a column with a smaller HTU requires shotter column height
than one with a laraer HTU.
** Pulsed sieve-plate extraction columns belong to this category.

Trends in Extraction Column Design

In recent years, the design of liquid/liquid multistage extraction

equipment has been based on the notion that one liquid phase must be
dispersed in the form of droplets in the other. Mass transfer rates in
liquid/liquid systems are affected by the rate of formation of the drop-
lets, the rate of passage of droplets through the continuous phase and
their rate of coalescence. "Recent work has shown that the rate of mass
transfer of solute during drop formation is large and that about 10%
of the extraction occurs in the formation period. However, the majority
of the extraction is accomplished during passage of the drops thrcuah
the continuous phase". The trend in column design is to produce oscil-
lating drops, because, in this type of drop the rate of mass transfer
is far greater than the rotating or stationary ones".

In keeping with the recent findings of mass transfer phenomena

in droplets, pulse sieve-plate extraction columns have received increas-
ing attention. Eastern European countries appear to be utilizing these
extractors in industrial plants". The U.S. atomic energy plants have
used the pulsed column very successfully for the reprocessing of irrad-
iated nuclear fuels18.

Reported Construction Details of Pulsed Columns

Details of the construction of some laboratory scale pulse extrac-

tion columns are listed in Table II. It is reported that close fitting
of the sieve-plates reduces the height of theoretical units (HTU). The
two methods of construction of a column have been used; shrinkina a
glass tube on a steel mandrel to achieve a bore within set tolerances and
then introducing a cartridge of sieve-plates; sandwiching metal plates
between short glass sections and holding the stack of these sections
in compression is the second method of construction.

The sieve-plates in a pulsed extractor usually have 1/8 inch

diameter perforations7 and about 20-25% of the cross-section area of
column is available for the flow of liquid. Smaller perforations have
been reported (Table II) but the area available for the flow of fluid
has been in the vicinity of 25% of the cross-sectional area of the




Column Plate % Column

Internal Bore Allowed Reference
Diameter For Flow of Number
(inch) Liquid

2 9 gauge, 304 1/8 23 9

tainless steel

3/4 gauge, 1/25 28 2

tainless steel

2 .tainless steel 3/50 23 10

2 tainless steel 3/25 23 10

- 7 -





Figure 2 is a block diagram illustrating the pulsed sieve-plate

extraction system. An air pulsing unit will be used to agitate the sea
water and the immiscible organic solution containing the chelating reagent.
The latter is considered as being less dense than sea water, for conven-
ience of discussion. The organic phase eventually rises to the top of the
column and is pumped to a stripping column where the trace element
chelates will undergo a second stage of concentration. The concentrate
will then proceed to the analytical instrumentation and the reclaimed
solvent will be charged with chelating agent if required and recycled
through the column. Sea water will be continuously entering at the top
of the extraction column, contacting the reagent as it passes through
the plates and exiting at the bottom of the column.

Extraction Column

A schematic diagram of the extraction column is given in Figure 3.

It will consist of about 30 glass sections of one inch internal diameter
and height one inch. 0-ring joints will be used to prevent leakage
beteween sections.

The sieve-plates will be constructed from teflon and sandwiched

between the glass sections of the column. About 25% of the cross-
sectional area will be available for the flow of liquid (perforation
diameter 98 to Y64, inch).

Air Pulsing Unit

As shown in Figure 4, this unit will consist of a compressed gas

supply, regulating valve, ballast tank and a cam operated three-way
valve. This valve will allow gas under pressure to be admitted to the
pulse leg and also the release of the built-up pressure for the down-
ward pulse. The frequency and amplitude of the oulses will be controlled
by the pressure in the ballast tank and the speed of the rotating cam.


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Operation of Extraction System

A vertical tower with perforated plates spaced evenly throughout

its height will make up the extraction section of the column. Both
ends of the column will be provided with sections to facilitate the
separation of the emulsion into distinct phases. These sections are of
a larger diameter than the extraction section (Figure 3).

The inlet for the more dense phase is located above the top plate
while that for the less dense phase is below the bottom plate. For a
system where the organic phase is more dense than sea water, its inlet
will be located above the top plate. This apparatus therefore has the
advantage of operating effectively when the density ratio of the aqueous-
to-organic phase is different from one.

Column pulsation is begun while the two liquid streams are being
introduced. Supposing the pulsing action is halted after the column
has attained steady state, then the two phases will settle down and the
column will have the appearance as illustrated in Figure 5. That is,
between two successive plates there will be two layers of liquid.
Immediately below the upper plate will be a region occupied by the less
dense phase and below this layer will be the more dense phase, occupying
a volume above the bottom plate. In the absence of pulsing action,
there will be no counter-current flow of liquid in the column.

Supposing the pulsing action is commenced on the quiescent sieve-

plate column. On the forward pulse the fluid body will be forced up-
wards and the less dense phase will be dispersed by the sieve-plate and
will rise through the more dense phase in droplets; which will coalesce
under the plate above. On the backward pulse the denser phase will be
subjected to the same action but only in reverse and will coalesce above
the plate below. Both actions are illustrated in Figure 6 and 7,
In addition to the kinetics of chelation of the metal ions and
the geometry of the column, the main factors affecting its performance
will be:

(a) Pulse amplitude

(b) Pulse frequency
(c) Through-put rates
(d) Phase flow ratio

Because the design of sieve-plate columns are still in the empir-

ical stage*, these factors will have to be determined experimentally.
The preliminary investigation with the apparatus will be to determine
its performance in extractino iron (Fe 111)3 from aqueous solution into

* See Appendix B.

- 12 -

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- 13 -

an organic phase: Benzene with a concentration near 0.2 molar of 2

Thenoyltrifluoroacetone (TTA). This particular system was chosen be-
cause TTA is a very versatile complexing agent and can be employed to
extract both transitional metals and rare earth ions. Data obtained
from this system should then provide sufficient information for the
design of an efficient system for the extraction of trace elements from
sea water.


1. Bell, C.F. and K.A.K. Lett. Modern Approach to Inorganic

Chemistry, Butterworth's 2nd edition (1966).
2. Brooks, R.R., Talanta, v.12, p.511 (1965).
3. De.A.K. and S.M. Khopkar, Anal Chim Acta, 22, p.223 (1960).
4. Jeffery, V.G., Chen. and Proc. Eng. 49, 11, p.111 (1968).
5. Kuwamoto, T. and I. Pagden, B.I.O. Internal Note 67-10-1 (1967).
6. McCabe, W.L. and J.C. Smith, Unit Operations of Chemical
Engineering McGraw-Hill, 2nd edition, p.723 (1967).
7. Perry, J.H., Chemical Engineers Handbook, McGraw-Hill, 4th edition.
8. Sege, G. and F.W. Woodfield, Chem. Eng. Prog. V.50, No.9, p.396
9. Schnel, G.A., A.L. Babb, Ind. and Eng. Chem. Process Design and
Development v.2, p.38, (1963).
10. Smoot, L.D. and A.L. Babb, Ind. and Eng. Chem. Fund, v.1, No.2,
p.93 (1962).
11. Vashist,.P.N. and R.B. Beckmann, Ind. and Eng. Chem. v.59, No.11,
p.71 (1967).
12. Watjen, J.W. and R.M. Hubbard, A.I.Ch.E. Journal; v.9, 5, p.614
13. Weech, M.E. and B.E. Knight, Ind. and Eng. Chem. Process Design
and Development, v.6, 4, p.480 (1967).
14. Weyl, P.K., Oceanography, Vol.II, John Wiley, 1st edition (1968).
- 15 -


Element Estimated Spectrographic

Concentration Detection Limit
in Sea Water (ppm)
Al 0.01 2

Sc 0.00004 2
Ti 0.001 10
V 0.002 5

Cr 0.00005 1
Mn 0.002 10

Fe 0.01 5

Co 0.0005 10
Ni 0.002 5
Cu 0.003 0.5

Zn 0.01 3

Ga 0.00003 3

Ge 0.00004 5

As 0.003 100
Rb 0.12 1

Sr 8 5

0.0003 10
Nb 0.00001 30

Mo 0.01 5'
Ag 0.0003 0.5
Cd 0.0001 10

In 0.02 1
- 16 -



TO: Mr. A. Coote

From: Rohan Pieries October 16, 1969


Object of the Meeting:

The purpose of our meeting was to solicit Dr. Chen's opinion as to

the usefulness of our proposed pulsed sieve-plate extraction column;
specifically to the processing of large volumes of sea water with
relatively small volumes of solvent. Two tynes of extractions can be

(a) Extraction of naturally occuring chelate systems.

(b) Extraction of chelated metal complexes, for separation and concen-
tration prior to analysis of trace metals.

We discussed the state of knowledge about the sieve-plate column

and Dr. Chen was of the opinion that sieve-plate columns were of sup-
erior contactino ability, to other known apparatus. Their efficiency
should be much greater than the Craig-Post discontinuous apparatus,
for example.

He was not familiar with the details of pulsed sieve-plate extrac-

tion columns but he suggested that through-put in such columns will be
determined largely by the hole size in plate and also the area of plate
available for free flow of fluid.
Dr. Chen mentioned that sieve-plate extraction systems should not
contain suspended particles because this might facilitate clogging,
hence resulting in a decreased efficiency in the column.

He thouaht that the extraction project that we proposed has

merit and that he would be interested in seeing how it developed.

He emphasized that the knowledge of theoretical design character-

istics of sieve-plate columns does not exist and therefore we should
have to proceed with column design on an empirical basis. This was as
we had suspected and that a column of arbitrary diameter and plate
characteristics should first be constructed and its efficiency measured.
Then the parameters determining efficiency, such as column diameter,
plate hole size percentage of free area for flow through plate, etc.,
can be examined and the efficiency optimized.

R. Pieties