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Lithium Recovery from Oil and Gas Produced Water: A Need for a Growing
Energy Industry

Article in ACS Energy Letters · June 2019

DOI: 10.1021/acsenergylett.9b00779

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Cite This: ACS Energy Lett. 2019, 4, 1471−1474 http://pubs.acs.org/journal/aelccp

Lithium Recovery from Oil and Gas Produced

Water: A Need for a Growing Energy Industry
D emand for lithium (Li) is expected to continue to rise
sharply with the growing worldwide deployment of
electric vehicles, and prices are projected to continue
to rise. Li can be sustainably recovered from oil and gas
produced water by utilizing Li recovery technologies such as
adsorbents, membrane-based processes, and electrolysis-based
systems (Figure 1). Li is a valuable metal, broadly known for
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Figure 2. Li concentration in water from unconventional oil and

gas (UOG) fields in the U.S.4 and some oil field brines.5

generated by Li recovery from the wastewater, which would

otherwise be a financial burden. Estimates of the Li resource
range for some U.S. oil and gas fields are given in Figure 3. It
should be noted that these estimated values are not precise,
not only because some data are lacking but also because

Figure 1. Li recovery technology platform.

its current application in the energy-storage sector, in Li-ion

batteries, and for its potential use in thermonuclear fusion; Li is
also used in CO2 adsorbents in aircrafts and submarines, glass
production, medical products, and materials such as plastic and
grease. In fact, the value of Li has increased sharply in recent
times due to high demand and low supply of this alkali metal,
and the future of Li price is now difficult to predict because
both supply and demand for Li is currently unstable.1
While most of Li used for Li batteries is currently produced
in the Li triangle of Argentina, Bolivia, and Chile in South
America,2,3 the large markets with significant demands for Li
are in North America, Europe, and Asia. Thus, with resource-
security in mind, increasing attention has been given to
recovery of Li from produced water at oil fields both in the
U.S. and globally. Various technologies that enable recovery of
Li from oil fields have been tested in order to provide the large
markets with Li from more diverse and often geographically Figure 3. Estimated resource range in metric tonnes of Li metal
closer sources. Although there is a plethora of reports on oil equivalent in wastewater from unconventional oil and gas
field brines, less has been published on the use of wastewater formation in the U.S. The estimated values were calculated from
from oil fields as a Li resource. This Viewpoint evaluates the a median of Li concentration in UOG produced water from some
potential for Li resource recovery from oil field wastewater. formation (44 mg/L, calculated from 155 data points) and the
Figure 2 shows that certain oil field brines around the world volume of wastewater from each oil and gas formation (long-term
contain high concentrations of Li. For example, Smackover produced water rates in gallons per day), both of which are
brines in the U.S. have a maximum of over 500 mg/L of Li, reported in an EPA report.4 The calculation assumes 100% Li
recovery and a formation lifespan of 30 years.
and some projects are moving forward to test its suitability as a
Li resource.6,7 On the other hand, wastewater from oil and gas
fields has lower concentration but nevertheless has potential as Received: April 10, 2019
a Li resource because there is no need to build new wells and Accepted: May 3, 2019
because oil producers can benefit from the revenue stream Published: June 5, 2019

© 2019 American Chemical Society 1471 DOI: 10.1021/acsenergylett.9b00779

ACS Energy Lett. 2019, 4, 1471−1474
ACS Energy Letters Viewpoint

Table 1. Technologies for Li Extraction from Brine

wastewater volume and its Li concentration are also unstable did not need to be drilled the cost for Li recovery could be
and constantly changing. reduced significantly.7 In addition, oil and gas producers could
Figure 3 shows that wastewater from oil and gas production increase profits by selling Li obtained from their wastewater.
can contain from several dozen to several hundred tonnes of Therefore, the exploitation of oil and gas production
Li. The total amount of Li potentially available for recovery wastewater with its high potential as a Li resource should be
from these oil and gas production wastewaters can be evaluated carefully, particularly in locations that frequently
comparable to that of some small Li deposits with several import Li from other regions. This presents a potential benefit
thousand tonnes of Li, such as in the Outovesi pegmatite for oil and gas producers as well as the end users of Li.
deposits in Finland (2000 metric tonnes Li metal equivalent).6 For the past several decades, a combination of solar
To be sure, general Li oil field deposits usually contain much evaporation and carbonation has been utilized to produce
more Li: Fox Creek and Valleyview in Canada have 362 000 pure Li compounds. Solar ponds can, however, be applied only
and 385 000 metric tonnes of Li metal equivalent, respectively, to brine that has a relatively high concentration of Li, roughly
while the Smackover Formation in the U.S. has 750 000 metric more than 500 mg/L. Evaporation also takes approximately 1
tonnes of Li metal equivalent.6 The exploitation of Li from oil year to concentrate the Li sufficiently to ensure effective
and gas fields will enable U.S. markets to obtain Li precipitation of Li carbonate upon the addition of soda ash.
domestically and avoid the potential for monopoly pricing by Recently, other, more rapid processes to recover lower
the South American concerns. In terms of capital cost, Li concentrations of Li, starting at around 100 mg/L, a common
producers can make use of existing oil and gas wells and concentration in oil field brines, have been considered, as
thereby reduce their expenses for Li recovery. For example, summarized in Table 1. This section reviews such technologies
based on a technoeconomic study on the Smackover and discusses their applicability to oil and gas wastewater by
Formation in the U.S., Daitch reported that because wells considering some practical examples.
1472 DOI: 10.1021/acsenergylett.9b00779
ACS Energy Lett. 2019, 4, 1471−1474
ACS Energy Letters Viewpoint

Phosphate precipitation is a newly developed technology to practical operation in columns, and they are currently being
replace the carbonation step in the solar evaporation process. studied in terms of an optimal binder formulation and
While this method requires extra processing steps to convert Li granulation method. Despite the potential for the effective
phosphate into the desired Li carbonate or hydroxide,8 it has recovery of Li by the three adsorbents, there are few practical
succeeded in shortening the time needed for the solar operations; only a small number of pilot tests have been carried
evaporation step because Li phosphate, with solubility of out. Given the clear potential for Li recovery from oil and gas
0.39 g/L, can be precipitated at ambient temperature at much wastewater, it is desirable to keep moving forward to improve
lower concentrations than Li carbonate, whose solubility is these adsorbents.
13.3 g/L. POSCO currently has projects to recover Li from Solvent extraction is another promising method.22 This
brine or battery recycling with this method.9,10 However, it is technology also shows higher selectivity for Li over other
doubtful that phosphate precipitation can be applied to oil field monovalent ions such as sodium and potassium ions. On the
wastewater because it still partially requires solar evaporation, other hand, divalent ions, such as magnesium and calcium,
which can concentrate Li only from highly concentrated brine should be removed, and Li should be preconcentrated prior to
(e.g., more than 500 mg/L) within reasonable time, as a the solvent extraction step to maintain the efficiency of the
preconcentration step. process. Tenova has its own process to extract Li by solvent
Adsorbents such as ion exchange resins are typically used in extraction and electrolysis,22,23 however, for produced water
packed columns for practical operations. Although it is a from oil fields because the Li concentration needs to be
conventional method for recovery of metal ions from solution, elevated to a certain degree, the divalent ions need to be
Li is much more difficult to adsorb selectivley than other metal removed before solvent extraction, and organic impurities can
ions, e.g., copper. The reason is that in brine much higher have a significant negative impact on the efficiency of solvent
concentrations of sodium, potassium, calcium, and magnesium extraction.
ions are present, sometimes 100-fold greater than the Li molar Finally, membrane technology is expected to play an
concentration, and these ions have better affinity for strong important role for Li extraction. Somrani et al. studied
acidic cation exchange resins. Because of the unfavorable nanofiltration and low-pressure reverse osmosis for Li-ion
solution conditions for effective recovery by conventional ion separation from brine.31 Although temperature and pressure
exchange resins, Dow Chemical in the U.S. developed control are required, the membrane process can be applied to
aluminum-loaded resins that can take up Li selectively from low concentrations of Li, such as those found in oil and gas
brine,11−13although challenges remain due to low selectivities. wastewater. Furthermore, while fouling can be a very large
There have been some reports in which Li is extracted into concern, as discussed in other membrane applications,
solvent-impregnated resins. Nishihama et al., for example, used membrane processes can be applied to a variety of brines or
1-phenyl-1,3-tetradecanedione (C11phβDK)/tri-n-octylphos- wastewaters when conditions are properly determined and
phine oxide (TOPO)-impregnated resins to separate Li from controlled. In fact, MGX has reported success in Li extraction
sodium and potassium ions.26 These solvent-impregnated from oil field produced wastewater using membranes.24,25
resins are one of the most promising ways to recover Li In conclusion, various technologies can replace conventional
because of their high selectivity, but the gradual elution of solar evaporation to meet the Li demand by accelerating
solvent from the resin, which makes the resin more difficult to concentration processes and adapting systems to lower Li
reuse, remains problematic especially in oil and gas wastewater, concentration. When it comes to Li extraction from oil and gas
which can contain some organic components. wastewater, this Viewpoint shows that the three reported metal
Other adsorbents that can be packed in columns are certain oxide adsorbents and membrane technologies are the most
metal oxides/hydroxides, which show good capacity for Li promising. Despite this potential, few practical systems are
adsorption. While they have higher selectivity for Li than ion operational. Greater efficiency is required, which can be
exchange resins, it does take longer to complete extraction than attained both by improving the discussed methods and by
with conventional ion exchange resins because Li needs to developing novel methods in order to recover Li from
intercalate into the layers of the metal oxides/hydroxides. solutions with a range of different characteristics and
Aluminum-based adsorbents are typically LiCl/Al(OH)3 conditions.
compounds, which are very similar to the aluminum-loaded Amit Kumar*,†,‡
resin. Because the aluminum-loaded resin has adsorption sites Hiroki Fukuda§
only on the surface of the resin and the aluminum-based T. Alan Hatton*,‡
adsorbent has adsorption sites along its whole surface, the John H. Lienhard, V*,†
latter generally has a higher capacity. Some companiesFMC, †
Department of Mechanical Engineering, Massachusetts
Simbol, and Eramethave their own patents for aluminum Institute of Technology, 77 Massachusetts Avenue,
adsorbents.14−19 A manganese-based adsorbent with high Cambridge, Massachusetts 02139-4307, United States
selectivity for Li was first reported by Ooi et al.,27−29 raising ‡
Department of Chemical Engineering, Massachusetts
interest among many researchers. Papers published after the
Institute of Technology, 77 Massachusetts Avenue,
first report indicate that the adsorption mechanism is
Cambridge, Massachusetts 02139-4307, United States
essentially the same as that with aluminum adsorbents. The §
manganese-based adsorbent is now being tested with the Department of Materials Engineering, University of British
Columbia, Vancouver, British Columbia, Canada V6T 1Z4

■
Uyuni salt lake solutions in Bolivia by Japan Oil, Gas and
Metals National Corporation (JOGMEC).20 A titanium-based
adsorbent with comparable capacity for Li recovery has been AUTHOR INFORMATION
reported by Chitrakar et al.,30 and Neometals used a similar Corresponding Authors
kind of titanium-based absorbent to successfully extract Li *E-mail: amitkum@mit.edu.
directly from brine.21 The three adsorbents are granulated for *E-mail: lienhard@mit.edu.
1473 DOI: 10.1021/acsenergylett.9b00779
ACS Energy Lett. 2019, 4, 1471−1474
 ACS Energy Letters Viewpoint

*E-mail: tahatton@mit.edu. (20) Chitrakar, R.; Makita, Y.; Ooi, K.; Sonoda, A. Magnesium-
Doped Manganese Oxide with Lithium Ion-Sieve Property: Lithium
ORCID
Adsorption from Salt Lake Brine. Bull. Chem. Soc. Jpn. 2013, 86 (7),
Amit Kumar: 0000-0001-7807-3427 850−855.
T. Alan Hatton: 0000-0002-4558-245X (21) Neometals. Successful ‘Proof of Concept’ testing of Direct Lithium
John H. Lienhard, V: 0000-0002-2901-0638 and Potassium Extraction from Brines. https://www.neometals.com.au/
reports/749-DX01062017.pdf (accessed Nov 29, 2018).
Notes (22) Cohen, L.; McCallum, T.; Tinkler, O.; Szolga, W.
Views expressed in this Viewpoint are those of the authors and Technological Advances, Challenges and Opportunities in Solvent
not necessarily the views of the ACS. Extraction from Energy Storage Applications. Extraction 2018
The authors declare no competing financial interest. Preceedings; 2018; pp 2033−2045.

■
(23) Tenova. Lithium Processing. https://www.tenova.com/product/
ACKNOWLEDGMENTS lithium-processing/ (accessed Nov 29, 2018).
(24) Bogner, S. Successful Independent Verification of the MGX
A.K. was partly supported by a grant through the MIT Energy Lithium Extraction Technology. https://www.rockstone-research.com/
Initiative. images/PDF/MGX20en.pdf (accessed Nov 29, 2018).

■
(25) McEachern, P. Lithium Recovery from Oilfield Produced Water
REFERENCES Brine & Wastewater Treatment. https://rockstone-research.com/
images/pdfs/MGX_TechnicalReportRapidLithiumExtractionProcess.
(1) Martin, G.; Rentsch, L.; Höck, M.; Bertau, M. Lithium Market pdf (accessed Nov 29, 2018).
Research − Global Supply, Future Demand and Price Development. (26) Nishihama, S.; Onishi, K.; Yoshizuka, K. Selective Recovery
Energy Storage Mater. 2017, 6, 171−179. Process of Lithium from Seawater Using Integrated Ion Exchange
(2) United States Geological Survey. Mineral Commodity Summaries Methods. Solvent Extr. Ion Exch. 2011, 29 (3), 421−431.
2018; 2018. (27) Ooi, K.; Miyai, Y.; Katoh, S. Recovery of Lithium from
(3) Vikström, H.; Davidsson, S.; Höök, M. Lithium Availability and Seawater by Manganese Oxide Adsorbent. Sep. Sci. Technol. 1986, 21
Future Production Outlooks. Appl. Energy 2013, 110, 252−266. (8), 755−766.
(4) United States Environmental Protection Agency. Technical (28) Miyai, Y.; Ooi, K.; Kato, S. Adsorbent for Lithium and a
Development Document for the Effluent Limitations Guidelines and Method for the Preparation Thereof. Patent US4665049A, 1987.
Standards for the Oil and Gas Extraction Point Source Category; 2016. (29) Chitrakar, R.; Kanoh, H.; Miyai, Y.; Ooi, K. Recovery of
(5) Garrett, D. E. Handbook of Lithium and Natural Calcium Lithium from Seawater Using Manganese Oxide Adsorbent
Chloride; Academic Press: Cambridge, 2004. DOI: 10.1016/B978-0- (H1.6Mn1.6O4) Derived from Li1.6Mn1.6O4. Ind. Eng. Chem. Res.
12-276152-2.X5035-X. 2001, 40 (9), 2054−2058.
(6) Chagnes, A.; Swiatowska, J. Lithium Process Chemistry: Resources, (30) Chitrakar, R.; Makita, Y.; Ooi, K.; Sonoda, A. Lithium Recovery
Extraction, Batteries, and Recycling; Elsevier: Amsterdam, The from Salt Lake Brine by H2TiO3. Dalt. Trans. 2014, 43 (23), 8933−
Netherlands, 2015. DOI: 10.1016/B978-0-12-801417-2.00007-4. 8939.
(7) Daitch, P. J. Lithium Extraction from Oilfield Brine. Master’s (31) Somrani, A.; Hamzaoui, A. H.; Pontie, M. Study on Lithium
Thesis, The University of Texas at Austin, 2018. Separation from Salt Lake Brines by Nanofiltration (NF) and Low
(8) Chon, U.; Lee, I. C.; Kim, K. Y.; Han, G.-C.; Song, C. H.; Jung, Pressure Reverse Osmosis (LPRO). Desalination 2013, 317, 184−192.
S. R. Method for Manufacturing Lithium Hydroxide and Method Using
Same for Manufacturing Lithium Carbonate. Patent US9598291B2,
2017.
(9) POSCO. POSCO Begins Lithium Production First Time in Korea.
http://www.posco.com/homepage/docs/eng5/jsp/prcenter/news/
s91c1010025v.jsp?idx=2701&onPage=1 (accessed Nov 29, 2018).
(10) Jamasmie, C. POSCO to Buy Lithium Mining Rights in Argentina
from Galaxy. http://www.mining.com/posco-buy-lithium-mining-
rights-argentina-galaxy/ (accessed Nov 29, 2018).
(11) Lee, J. M.; Bauman, W. C. Recovery of Lithium from Brines.
Patent US4159311A, 1979.
(12) Lee, J. M.; Bauman, W. C. Recovery of Lithium from Brines.
Patent US4347327A, 1982.
(13) Burda, J. L., I. Method of Making Crystalline 2-Layer Lithium
Aluminates in Ion Exchange Resins. Patent US4461714A, 1984.
(14) Bauman, W. C.; Burda, J. L., I Recovery of Lithium Values from
Brines. Patent US5389349A, 1995.
(15) Bauman, W. C.; Burda, J. L., I. Recovery of Lithium Values
from Brines. Patent US5599516A, 1997.
(16) Bauman, W. C.; Burda, J. L., I. Composition for the Recovery of
Lithium Values from Brine and Process of Making/Using Said
Composition. Patent US6280693B1, 2001.
(17) Harrison, S.; Sharma, C. V. K.; Viani, B. E.; Peykova, D.
Lithium Extraction Composition and Method of Preparation Thereof.
Patent US8637428B1, 2014.
(18) Burda, J. L., I; Stewart, R. F.; Viani, B. E.; Harrison, S.; Vogdes,
C. E.; Lahlouh, J. G. S. Sorbent for Lithium Extraction. Patent
US8753594B1, 2014.
(19) Boualleg, M.; Lafon, O.; Burdet, F. A. P.; Soulairol, R. C. J. R.
Method of Preparing an Adsorbent Material Shaped in the Absence of
Binder and Method of Extracting Lithium from Saline Solutions
Using Said Material. Patent US20160317998B1, 2016.

1474 DOI: 10.1021/acsenergylett.9b00779

ACS Energy Lett. 2019, 4, 1471−1474

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