A New Way to Mine: Efficient Uranium Seawater Extraction
Optimizing Copolymer Ratios and Polymer Recycling Methods
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 run-off 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 (3). 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.
Challenges
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 (UO2), the common form of uranium, is tightly bound to carbonate (CO3) in a uranyl
tricarbonate metal complex in seawater (1,2)
● 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.
Hypothesis
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 (3). Hollow,
gear-shaped polyethylene fibers were exposed to an electron beam in order to create free radicals.
The fibers were then submerged in solutions of varying acrylonitrile and vinylphosphonic acid
molar ratios (3). Nitrile and phosphonate groups readily grafted onto the polymer fibers. Following
polymerization, the fibers were then exposed to 5 wt % hydroxylamine, which converted the
grafted nitrile groups to amidoxime groups (3). The fibers were lastly conditioned with 0.44 M
KOH, which aids in the transport of uranyl ions through the fibers (3). 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. These tests were 56 day cycles in which
the adsorbent fibers extracted uranium from the seawater (3).
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
Pictured above is the process by which the amidoxime
predicts the maximum amount of adsorption, but not the true
fibers are produced. This process is detailed under
“Materials and Methods” Credit goes to the authors (5). 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 (3). In the flow-through column testing done by ORNL,
the concentration of adsorbed vanadium was about five times that of uranium (3). The vanadium
binds so strongly that it can not be removed without damaging the amidoxime fibers. 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. 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, cn 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 (4). 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 hydroxylammonium acetate in acetic
acid have little to no impact on the longevity of the adsorbents (4). 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/Critique
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(cn/c) term in
my 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.
References
[1] Alexandratos, Spiro D., and Stephen Kung. "Preface to the Special Issue: Uranium in Seawater." Industrial & Engineering Chemistry
Research 55.15 (2016): 4101-102. Print.
[2] Saito, Kyoichi, and Terukatsu Miyauchi. "Chemical Forms of Uranium in Artificial Seawater." Journal of Nuclear Science and
Technology 19.2 (1982): 145-50. Print.
[3] Das, S., Y. Oyola, R. T. Mayes, C. J. Janke, L.-J. Kuo, G. Gill, J. R. Wood, and S. Dai. "Extracting Uranium from Seawater: Promising AI
Series Adsorbents." Industrial & Engineering Chemistry Research 55.15 (2016): 4103-109. Print.
[4] Berton, Paula, Steven P. Kelley, and Robin D. Rogers. "Stripping Uranium from Seawater-Loaded Sorbents with the Ionic Liquid
Hydroxylammonium Acetate in Acetic Acid for Efficient Reuse." Industrial & Engineering Chemistry Research 55.15 (2016): 4321-327.
Print.
[5] Oyola, Yatsandra, and Sheng Dai. "High Surface-area Amidoxime-based Polymer Fibers Co-grafted with Various Acid Monomers
Yielding Increased Adsorption Capacity for the Extraction of Uranium from Seawater." Dalton Trans. 45.21 (2016): 8824-834. Print.