A New Way to Mine: Efficient Uranium Seawater Extraction

Optimizing Copolymer Ratios and Polymer Recycling Methods

Chemistry and Materials Science

Simon Munyan
Abstract
A New Way to Mine: Efficient Uranium Seawater Extraction
Optimizing Copolymer Ratios and Polymer Recycling Methods
Chemistry and Materials Science
Finding a source of renewable and sustainable energy is the greatest challenge humanity
currently faces. Nuclear energy stands to bridge the gap as we transition from fossil fuels to
renewable energy sources. One challenge of using nuclear power is a sustainable fuel source.
Uranium mining has significant negative environmental impact and is limited to specific
geographic areas. The oceans, however, contain an estimated 4.5 billion tons of dissolved
uranium (1). Current methods including polymers, resins, and hydrogel adsorbents have been
developed and tested to collect uranium from the seawater (2). Optimization of reactants and the
method of removing the uranium from adsorbents will help make them economically viable.
I began by fitting a trendline to experimental data of uranium adsorbed per mass of
adsorbent against the ratio of the two primary reactants for a specific, amidoxime based
adsorbent (2). I used calculus to differentiate this trendline and found the absolute maximum. I
repeated this procedure for molar ratios of adsorbed uranium to vanadium ions against reactant
ratios. Using the two maximums as bounds, I found the optimal range of reactant ratios. A
function was modeled to predict the mass of recovered uranium based on the mass adsorbed,
relative capacity, and fractional uranium stripping (3). This function was applied to data from
three methods of uranium stripping (elution), and graphed. Trendlines were fit for each method
and the maximums were located.
The initial range of reactant ratios was between 3.793 and 4.214 (mol/mol). The
maximum recovered mass of uranium was predicted to be 8.626 grams of uranium at a reactant
ratio of 3.82 mol/mol. This was achieved by elution with hydroxylammonium acetate in acetic
acid (3).
Introduction
Energy production is the greatest challenge humanity currently faces. Fossil fuel burning,
which has made great strides in efficiency in cleanliness, simply is not a renewable or sustainable
source of energy. On the other hand, renewable energy sources such as solar, wind, and
hydroelectric, lack efficiency to take on the burden of our energy demand, even if their future
potential is great. Nuclear fission power lies somewhere in the middle, with a large energy output
and minimal emissions. Nuclear power stands to be an intermediary between power resources, as
we transition from fossil fuels to renewables. One of the significant challenges facing nuclear
energy is its non-renewable fuel source: uranium. Current uranium mining methods are
problematic, including issues such as runoff contamination in surface water and groundwater as
well as mine waste contamination. High-quality uranium ore is also geographically specific,
which disadvantages some regions where such deposits are sparse. Recent research
developments have indicated that the oceans could be our next source of uranium. It is estimated
that there is about 4.5 billion tons of uranium dissolved in seawater (2). Furthermore, since
uranium is in solubility equilibrium, the uranium extracted from the ocean is replaced by new
uranium in the earth’s crust, according to Le Chatelier's principle. A technology that could
passively extract uranium from seawater and recover it would move nuclear energy a step
towards being renewable. Current research at Oak Ridge National Laboratory has produced a
few specialized polymeric adsorbents which have shown potential in adsorbing uranium out of
seawater and recovering it through an elution process.

There are numerous challenges and requirements that face such a technology. Some
include:
● Very low concentration of uranium in seawater (3.3 ppb; 1.4 E-8 mol/L) (1)
● Uranyl (UO​2​), the common form of uranium, is tightly bound to carbonate (CO​3​) in a
uranyl tricarbonate metal complex in seawater, where the carbonate groups surround a
uranyl ion (3-5)
● Seawater contains many other undesirable ions in far greater concentrations (1)
● Must not harm aquatic life
● Must operate at the pH of seawater (~8) (1)
● Must be economical; cost of seawater extraction must be the same or less than
conventional uranium mining

During my investigation, I focused largely on developing an economical solution, which

encompasses most of the other listed issues, as well as improving reusability of the extraction
technology and reducing competition with other, undesirable ions.
My research pertains to the AI series adsorbents which were developed by ORNL as one
solution to uranium seawater extraction. My goal is to find the optimal ratio of reactants involved
in producing AI adsorbents, namely acrylonitrile (AN) and vinylphosphonic acid (VPA), as well
as method of elution (the means by which the uranium is recovered from the adsorbent) that
would return the greatest ratio of recovered uranium per mass of adsorbent.
In short, the optimal ratio of acrylonitrile to vinylphosphonic acid will return the highest
ratio of recovered uranium to adsorbent, taking into account the effects of ion competition and
elution methods on adsorbent capacity.

Materials and Methods

To better understand this project as a whole, it is important to mention the details in the
formation and structure of AI adsorbents. Researchers at Oak Ridge National Laboratory
developed these characteristic adsorbents through the use of radiation induced graft
polymerization (2). Hollow, gear-shaped polyethylene fibers were exposed to an electron beam
in order to create free radicals (6). The fibers were then submerged in solutions of varying
acrylonitrile and vinyl phosphonic acid molar ratios (2). Nitrile and phosphonate groups readily
grafted onto the polymer fibers (3). Following polymerization, the fibers were then exposed to 5
wt % hydroxylamine, which converted the grafted nitrile groups to amidoxime groups (2). The
fibers were lastly conditioned with 0.44 M KOH, which aids in the transport of uranyl ions
through the fibers (2). The data I worked with largely comes from testing of the adsorbent fibers
in flow-through columns with seawater taken from Sequim Bay at the PNNL Marine Sciences
Laboratory (3). These tests were 56 day cycles in which the adsorbent fibers extracted uranium
from the seawater (2).
I began by graphing the various ratios of AN/VPA and their associated adsorption per
mass of adsorbent. This data was obtained from experiments done by ORNL. After graphing the
data, I fit a sixth degree polynomial trendline. While the end behavior is obviously extreme, the
trend fits most of the interior data points well, as evidenced by an r-squared value of 0.998. I
then used calculus to differentiate the trend curve and find extrema. The absolute maximum
towards the center of the data distribution, excluding the extreme peak to the right, was my point
of interest. I found it to occur at a AN/VPA ratio of 3.793 with a predicted adsorption of 3.381
g-U/Kg-ads. This value predicts the maximum amount of adsorption, but not the true value of the
amount of recoverable uranium. However, it gives a baseline of where that true value should lie
near.
 Another key factor that contributes to the true recoverable amount of uranium is the ratio
of vanadium to uranium adsorbed. Vanadium ions, which are present in seawater at about 1.9
ppb, are highly competitive with uranium ions (2). In the flow-through column testing done by
ORNL, the concentration of adsorbed vanadium was about five times that of uranium (2). The
vanadium binds so strongly that it can not be removed without damaging the amidoxime fibers
(3). Such damage reduces the capacity of the fibers, as does leaving the vanadium to remain on
the fibers. This must be taken into consideration when attempting to predict the amount of
recoverable uranium over a multi-cycle lifetime of the fibers.
Using data from ORNL’s simulated, 56 day sea trial, I graphed the ratios of uranium to
vanadium for the varying ratios of AN/VPA (7). I then fit a quadratic trend curve to the data in
order to interpolate values and find the maximum ratio. The maximum was located at an
AN/VPA ratio of 4.214 which corresponded to a predicted U/V ratio of 0.05083. This reveals
that the optimal AN/VPA ratio lies between 3.793 and 4.214.
 The last step was to combine both factors, uranium uptake and uranium to vanadium
ratios, into one function which could then be optimized. This took the form of recoverable
uranium per kilogram of adsorbent, which in itself is a function of adsorption capacity. This is
significant because the function takes into account the amount of uranium that will be recovered
over multiple cycles. This function can be expressed by:

where ​R​ is the recovered grams of uranium per kilogram of adsorbent, ​n​ is the cycle number, ​a​ is
the grams of uranium adsorbed per kilogram of adsorbent, ​f​ is a constant value of 0.8, which
represents the fractional value of uranium removed,​ c​n​ is the capacity of the adsorbent in a given
cycle, and​ c​ is a constant of 3.0 mg U/g-adsorbent, which is the relative capacity without
competition from vanadium. It is important to note that this function predicts the recoverable
uranium after three cycles of adsorption and elution. There has been no extensive investigation
into the lifetime of these adsorbents, but data is available for up to three cycles.

Results
The function​ R(a)​ was graphed against a, the ratio of AN/VPA, for three different elution
methods. Elution is the process by which the uranium is stripped from the adsorbent fiber and
collected. The method used can affect the lifetime capacity and performance of these fibers. The
function ​R(a)​ was applied for each elution method in order to compare the total uranium
recovered over three cycles. This resulted in three scatter plots, each with its own trendline. I
used a sixth degree polynomial trend to obtain the closest fit in the interior points. Using the
same method as before, I found the local maximums for each each and their associated AN/VPA
ratios.
Conclusion
The red trendline shows that the elution method involving hydroxylammonium acetate in
acetic acid as a solvent performed best (3). The absolute maximum, ignoring the extreme peak to
the right, is 8.26 g-U/Kg-ads, which occurs at 3.82. Thus, the optimal ratio of AN/VPA is
predicted to be 3.82 mol/mol. I predict this will, over a lifespan of three cycles, recover 8.626
grams of uranium per kilogram of adsorbent.
Perhaps the greatest surprise was the results that the 0.5 M hydrochloric acid performed
better than acetic acid over three cycles. Past studies have shown that hydrochloric acid has a
damaging effect on the adsorption capacity of the fiber (4). They have also shown that both
acetic acid and hydroxyl ammonium acetate in acetic acid have little to no impact on the
longevity of the adsorbents (8). However, at least in the short lifespan of three cycles,
hydrochloric acid outpaces the acetic acid in its ability to strip vanadium more aggressively.

Discussion
There are certainly difficulties with the mathematical approach I used. Firstly, the data
obtained by ORNL that I manipulated and interpreted does not fit well into a trend. This is
largely due to few data points, and significant distance between each point. In order to fit the
central points which I was most interested in, I had to use high-degree polynomials which
became extremely high in error towards the ends of the scatter plot. This increasing error should
be expected as one extrapolates further from data points, however, it certainly questions the
accuracy of the model.
Another challenge was the lack of data for the three elution methods I compared. To find
the percent adsorption capacity over multiple cycles, I had to use relative values from data that
was obtained for only one of the elution methods. The ​f( cnc )​ term in the function handles this, as
it takes a ratio of the capacity of the adsorbent from one elution method to the capacity of the
adsorbent from the hydroxylammonium acetate in acetic acid. This is done because I only have
the data for the fractional value of uranium removed for the hydroxylammonium acetate in acetic
acid method, which is ​f​, or 0.8. Multiplying this fraction by the capacity of an elution method
without absolute data relative to the hydroxylammonium acetate in acetic acid method gives a
good estimation. Fortunately, since I am only looking for extreme rather than absolute values, a
relative scale works well.
For further research, AF Series adsorbents could be investigated, where the copolymer
acid is itaconic acid rather than vinyl phosphonic acid (9). In the future, it may be valuable to
compare adsorbents and fibers prepared via methods other than radiation-induced graft
polymerization. One of these, atom-transfer radical polymerization, may allow for a lower
manufacturing cost and finer tuning of the reactant ratios (10). This method utilizes a multiple
acrylonitrile branches connected in a permeable network (11).
References

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