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

Authors:
  • University of British Columbia
Lithium Recovery from Oil and Gas Produced
Water: A Need for a Growing Energy Industry
Demand 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
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 CO2adsorbents 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 dicult 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 signicant 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 elds both in the
U.S. and globally. Various technologies that enable recovery of
Li from oil elds have been tested in order to provide the large
markets with Li from more diverse and often geographically
closer sources. Although there is a plethora of reports on oil
eld brines, less has been published on the use of wastewater
from oil elds as a Li resource. This Viewpoint evaluates the
potential for Li resource recovery from oil eld wastewater.
Figure 2 shows that certain oil eld brines around the world
contain high concentrations of Li. For example, Smackover
brines in the U.S. have a maximum of over 500 mg/L of Li,
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
elds has lower concentration but nevertheless has potential as
a Li resource because there is no need to build new wells and
because oil producers can benet from the revenue stream
generated by Li recovery from the wastewater, which would
otherwise be a nancial burden. Estimates of the Li resource
range for some U.S. oil and gas elds 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
Received: April 10, 2019
Accepted: May 3, 2019
Published: June 5, 2019
Figure 1. Li recovery technology platform.
Figure 2. Li concentration in water from unconventional oil and
gas (UOG) elds in the U.S.
4
and some oil eld brines.
5
Figure 3. Estimated resource range in metric tonnes of Li metal
equivalent in wastewater from unconventional oil and gas
formation in the U.S. The estimated values were calculated from
a median of Li concentration in UOG produced water from some
formation (44 mg/L, calculated from 155 data points) and the
volume of wastewater from each oil and gas formation (long-term
produced water rates in gallons per day), both of which are
reported in an EPA report.
4
The calculation assumes 100% Li
recovery and a formation lifespan of 30 years.
Viewpoint
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wastewater volume and its Li concentration are also unstable
and constantly changing.
Figure 3 shows that wastewater from oil and gas production
can contain from several dozen to several hundred tonnes of
Li. The total amount of Li potentially available for recovery
from these oil and gas production wastewaters can be
comparable to that of some small Li deposits with several
thousand tonnes of Li, such as in the Outovesi pegmatite
deposits in Finland (2000 metric tonnes Li metal equivalent).
6
To be sure, general Li oil eld deposits usually contain much
more Li: Fox Creek and Valleyview in Canada have 362 000
and 385 000 metric tonnes of Li metal equivalent, respectively,
while the Smackover Formation in the U.S. has 750 000 metric
tonnes of Li metal equivalent.
6
The exploitation of Li from oil
and gas elds will enable U.S. markets to obtain Li
domestically and avoid the potential for monopoly pricing by
the South American concerns. In terms of capital cost, Li
producers can make use of existing oil and gas wells and
thereby reduce their expenses for Li recovery. For example,
based on a technoeconomic study on the Smackover
Formation in the U.S., Daitch reported that because wells
did not need to be drilled the cost for Li recovery could be
reduced signicantly.
7
In addition, oil and gas producers could
increase prots by selling Li obtained from their wastewater.
Therefore, the exploitation of oil and gas production
wastewater with its high potential as a Li resource should be
evaluated carefully, particularly in locations that frequently
import Li from other regions. This presents a potential benet
for oil and gas producers as well as the end users of Li.
For the past several decades, a combination of solar
evaporation and carbonation has been utilized to produce
pure Li compounds. Solar ponds can, however, be applied only
to brine that has a relatively high concentration of Li, roughly
more than 500 mg/L. Evaporation also takes approximately 1
year to concentrate the Li suciently to ensure eective
precipitation of Li carbonate upon the addition of soda ash.
Recently, other, more rapid processes to recover lower
concentrations of Li, starting at around 100 mg/L, a common
concentration in oil eld brines, have been considered, as
summarized in Table 1. This section reviews such technologies
and discusses their applicability to oil and gas wastewater by
considering some practical examples.
Table 1. Technologies for Li Extraction from Brine
ACS Energy Letters Viewpoint
DOI: 10.1021/acsenergylett.9b00779
ACS Energy Lett. 2019, 4, 14711474
1472
Phosphate precipitation is a newly developed technology to
replace the carbonation step in the solar evaporation process.
While this method requires extra processing steps to convert Li
phosphate into the desired Li carbonate or hydroxide,
8
it has
succeeded in shortening the time needed for the solar
evaporation step because Li phosphate, with solubility of
0.39 g/L, can be precipitated at ambient temperature at much
lower concentrations than Li carbonate, whose solubility is
13.3 g/L. POSCO currently has projects to recover Li from
brine or battery recycling with this method.
9,10
However, it is
doubtful that phosphate precipitation can be applied to oil eld
wastewater because it still partially requires solar evaporation,
which can concentrate Li only from highly concentrated brine
(e.g., more than 500 mg/L) within reasonable time, as a
preconcentration step.
Adsorbents such as ion exchange resins are typically used in
packed columns for practical operations. Although it is a
conventional method for recovery of metal ions from solution,
Li is much more dicult to adsorb selectivley than other metal
ions, e.g., copper. The reason is that in brine much higher
concentrations of sodium, potassium, calcium, and magnesium
ions are present, sometimes 100-fold greater than the Li molar
concentration, and these ions have better anity for strong
acidic cation exchange resins. Because of the unfavorable
solution conditions for eective recovery by conventional ion
exchange resins, Dow Chemical in the U.S. developed
aluminum-loaded resins that can take up Li selectively from
brine,
1113
although challenges remain due to low selectivities.
There have been some reports in which Li is extracted into
solvent-impregnated resins. Nishihama et al., for example, used
1-phenyl-1,3-tetradecanedione (C11phβDK)/tri-n-octylphos-
phine oxide (TOPO)-impregnated resins to separate Li from
sodium and potassium ions.
26
These solvent-impregnated
resins are one of the most promising ways to recover Li
because of their high selectivity, but the gradual elution of
solvent from the resin, which makes the resin more dicult to
reuse, remains problematic especially in oil and gas wastewater,
which can contain some organic components.
Other adsorbents that can be packed in columns are certain
metal oxides/hydroxides, which show good capacity for Li
adsorption. While they have higher selectivity for Li than ion
exchange resins, it does take longer to complete extraction than
with conventional ion exchange resins because Li needs to
intercalate into the layers of the metal oxides/hydroxides.
Aluminum-based adsorbents are typically LiCl/Al(OH)3
compounds, which are very similar to the aluminum-loaded
resin. Because the aluminum-loaded resin has adsorption sites
only on the surface of the resin and the aluminum-based
adsorbent has adsorption sites along its whole surface, the
latter generally has a higher capacity. Some companiesFMC,
Simbol, and Eramethave their own patents for aluminum
adsorbents.
1419
A manganese-based adsorbent with high
selectivity for Li was rst reported by Ooi et al.,
2729
raising
interest among many researchers. Papers published after the
rstreportindicatethattheadsorptionmechanismis
essentially the same as that with aluminum adsorbents. The
manganese-based adsorbent is now being tested with the
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
reported by Chitrakar et al.,
30
and Neometals used a similar
kind of titanium-based absorbent to successfully extract Li
directly from brine.
21
The three adsorbents are granulated for
practical operation in columns, and they are currently being
studied in terms of an optimal binder formulation and
granulation method. Despite the potential for the eective
recovery of Li by the three adsorbents, there are few practical
operations; only a small number of pilot tests have been carried
out. Given the clear potential for Li recovery from oil and gas
wastewater, it is desirable to keep moving forward to improve
these adsorbents.
Solvent extraction is another promising method.
22
This
technology also shows higher selectivity for Li over other
monovalent ions such as sodium and potassium ions. On the
other hand, divalent ions, such as magnesium and calcium,
should be removed, and Li should be preconcentrated prior to
the solvent extraction step to maintain the eciency of the
process. Tenova has its own process to extract Li by solvent
extraction and electrolysis,
22,23
however, for produced water
from oil elds because the Li concentration needs to be
elevated to a certain degree, the divalent ions need to be
removed before solvent extraction, and organic impurities can
have a signicant negative impact on the eciency of solvent
extraction.
Finally, membrane technology is expected to play an
important role for Li extraction. Somrani et al. studied
nanoltration and low-pressure reverse osmosis for Li-ion
separation from brine.
31
Although temperature and pressure
control are required, the membrane process can be applied to
low concentrations of Li, such as those found in oil and gas
wastewater. Furthermore, while fouling can be a very large
concern, as discussed in other membrane applications,
membrane processes can be applied to a variety of brines or
wastewaters when conditions are properly determined and
controlled. In fact, MGX has reported success in Li extraction
from oil eld produced wastewater using membranes.
24,25
In conclusion, various technologies can replace conventional
solar evaporation to meet the Li demand by accelerating
concentration processes and adapting systems to lower Li
concentration. When it comes to Li extraction from oil and gas
wastewater, this Viewpoint shows that the three reported metal
oxide adsorbents and membrane technologies are the most
promising. Despite this potential, few practical systems are
operational. Greater eciency is required, which can be
attained both by improving the discussed methods and by
developing novel methods in order to recover Li from
solutions with a range of dierent characteristics and
conditions.
Amit Kumar*
,,
Hiroki Fukuda
§
T. Alan Hatton*
,
John H. Lienhard, V*
,
Department of Mechanical Engineering, Massachusetts
Institute of Technology, 77 Massachusetts Avenue,
Cambridge, Massachusetts 02139-4307, United States
Department of Chemical Engineering, Massachusetts
Institute of Technology, 77 Massachusetts Avenue,
Cambridge, Massachusetts 02139-4307, United States
§
Department of Materials Engineering, University of British
Columbia, Vancouver, British Columbia, Canada V6T 1Z4
AUTHOR INFORMATION
Corresponding Authors
*E-mail: amitkum@mit.edu.
*E-mail: lienhard@mit.edu.
ACS Energy Letters Viewpoint
DOI: 10.1021/acsenergylett.9b00779
ACS Energy Lett. 2019, 4, 14711474
1473
*E-mail: tahatton@mit.edu.
ORCID
Amit Kumar: 0000-0001-7807-3427
T. Alan Hatton: 0000-0002-4558-245X
John H. Lienhard, V: 0000-0002-2901-0638
Notes
Views expressed in this Viewpoint are those of the authors and
not necessarily the views of the ACS.
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
A.K. was partly supported by a grant through the MIT Energy
Initiative.
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ACS Energy Letters Viewpoint
DOI: 10.1021/acsenergylett.9b00779
ACS Energy Lett. 2019, 4, 14711474
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By 2050, the global Earth population will reach 10 billion, leading to increased water, food, and energy needs. Availability of water in sufficient quantities and appropriate quality is a prerequisite for human societies and natural ecosystems. In many parts of the world, excessive water consumption and pollution by human activities put enormous pressure on this availability as well as on food and energy security, environmental quality, economic development, and social well-being. Water, food/materials, and energy are strongly interlinked, and the choices made in one area often have consequences on the others. This is commonly referred to as the “water-food-energy” nexus. These interconnections intensify as the demand for resources increases with population growth and changing consumption patterns, and Humanity continues using a linear economy model of ‘take-make-dispose’. The nexus makes it difficult for governments, public and private organisations, and the public, to set and follow a clear path towards a sustainable economy i.e “meeting the needs of the present without compromising the ability of future generations to meet their own needs”. Humanity best chance at mitigating climate change, and shortage of resources is to harness the value of water as much as possible, as shown below in a nutshell. This paper reviews the latest publications about the water-food-energy nexus and climate change, putting numbers into perspective, attempting to explain why water circularity is part of the key factors to accelerate the transition from a linear economy to a circular economy, and to meet the UN Sustainable Development Goals, and how circularity can be implemented in the water sector.
Chapter
Produced water is the water found in the same formations as oil and gas and is a by‐product of hydrocarbon production operations that is brought to the surface along with oil and gas from onshore and offshore wells. Reuse and recycling of produced water is possible through a range of current separation processes to reduce the organic (mostly oil) and inorganic (mostly salt) components to levels acceptable for the intended usage. This chapter aims to review the current technologies and present new directions for produced water treatment with a focus on sustainability, energy efficiency, and produced water reuse. Sustainable produced water management involves a holistic approach to environmental management that takes into consideration the direct, indirect, and cumulative impacts across the project life cycle. This includes the coordinated development and management of water to maximize the resultant economic and social welfare in an equitable manner without compromising the sustainability of vital ecosystems.
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The details of the ion exchange properties of layered H2TiO3, derived from the layered Li2TiO3 precursor upon treatment with HCl solution, with lithium ions in the salt lake brine (collected from Salar de Uyuni, Bolivia) are reported. The lithium adsorption rate is slow, requiring 1 d to attain equilibrium at room temperature. The adsorption of lithium ions by H2TiO3 follows the Langmuir model with an adsorptive capacity of 32.6 mg g(-1) (4.7 mmol g(-1)) at pH 6.5 from the brine containing NaHCO3 (NaHCO3 added to control the pH). The total amount of sodium, potassium, magnesium and calcium adsorbed from the brine was <0.30 mmol g(-1). The H2TiO3 was found capable of efficiently adsorbing lithium ions from the brine containing competitive cations such as sodium, potassium, magnesium and calcium in extremely large excess. The results indicate that the selectivity order Li(+) ≫ Na(+), K(+), Mg(2+), Ca(2+) originates from a size effect. The H2TiO3 can be regenerated and reused for lithium exchange in the brine with an exchange capacity very similar to the original H2TiO3.
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Magnesium-doped lithium manganese oxides LimMgxMnIIIyMnIVzO4 (0 < x ¯ 0.5) with cubic spinel structure were synthesized by a coprecipitation method followed by calcination at 450 °C in air. Protonated samples were obtained after treatment with HCl solution. Chemical stability is very important for lithium uptake in industry. We used 0.5M HCl for desorption of lithium, then dissolution of Mn decreased from 5.8 wt% for a sample without Mg to 1.0 wt% for a Mg-doped sample (Mg/Mn = 0.33). Raw brine was collected from the Salars de Uyuni, Bolivia. The effects of magnesium-doping on lithium adsorptive properties of the protonated samples in NaHCO3 containing brine were studied by a batch method. The results showed that lithium adsorptive capacity and chemical stability of the protonated samples increased with increase in Mg/Mn ratio. The regeneration of the sample with Mg/Mn = 0.33 up to 10 cycles showed good performance with lithium adsorptive capacity of 23-25 mg/g at pH 6.6, and the dissolution of manganese ca. 0.25 wt% Mn.
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The aim of the present work is to study the separation of lithium from salt lake brines by NF and LPRO. NF90 membrane compared to the XLE a LPRO membrane appeared more efficient for Li+ extraction due to its higher hydraulic permeability to pure water and 0.1 M NaCl solution, its lower critical pressure (Pc = 0), its higher selectivity between monovalent ions (40%) obtained at low operating transmembrane pressure (below 15 bar) and its lower average roughness (105 ± 10 nm) decreasing the propensity to be fouled. NF90 exhibited 100% rejection of magnesium in the first step separation from brine diluted ten times as 15% for Li+, with a final separation of 85% between Mg2 +/Li+. The permeability to the diluted brine is 0.7 L.h− 1.m− 2.bar− 1 usable to size full scale experiments, but the fouling mechanism has to be discovered in the future work. In a second step we have not succeeded to separate totally Li+ and Na+ in the permeate obtained before (15% of separation only between Li+ and Na+). To solve this problem, we did dialysis. We obtained a total separation between Li+ and Na+ with a diffusion flux (4.42 10− 7 mol.s− 1.m− 2 at 20 °C) for NaCl 0.1 M 5 times higher for NF90 vs XLE.
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Ensuring the supply of strategic metals is crucial for the growth of industrialised countries. One of these strategic metals is lithium, which is used in a variety of high tech product and everyday objects. In this study the lithium market is analysed including areas of application, drivers of demand as well as lithium price development. A demand forecast up to 2020 is given in four different scenarios, including the increasing demand in electric mobility, forced by political driven influences. To meet the growing demand of lithium huge lithium projects are planned or under construction. The projects are summarised with a completion up to 2020 and a capacity of more than 20,000 t lithium carbonate equivalents (LCE).
Chapter
Spent lithium-ion (Li-ion) batteries are considered to be a secondary source of valuable metals, such as cobalt, nickel, aluminum, copper manganese, etc. Recently, the recovery of lithium has been considered to be needed not only to increase the material recovery rate of the existing process, but also to use the spent lithium-ion batteries (LiBs) as a source of the metal, of which almost one-third of the production is applied in the battery industry. In this chapter research activities and current recycling technologies for LiBs are described. The characterization of the waste shows that spent LiBs are heterogeneous waste not only because of the different materials used for battery construction, but also because of the differences in the active material composition. Discharging processes, followed by mechanical pretreatment and separation are necessary parts of the spent batteries treatment, especially when hydrometallurgy is implemented for metal recovery. This chapter describes current efforts in recycling using hydrometallurgical treatment applying inorganic and organic acids for leaching, as well as bioleaching methods. Processes of metal recovery using solvent extraction and precipitation are also described. Thermal pretreatments are introduced as an example for removing organic compounds and carbon in order to improve the metal recovery. Current industrial processes that apply mechanical treatment, pyrometallurgy, hydrometallurgy, or combined processes for LiBs recycling are described as well.
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This book is concerned with two major industrial minerals: Lithium and Calcium Chloride. The geology of their deposits is first reviewed, along with discussions of most of the major deposits and theories of their origin. The commercial mining and processing plants are next described, followed by a review of the rather extensive literature on other proposed processing methods. The more important uses for lithium and calcium chloride are next covered, along with their environmental considerations. This is followed by a brief review of the production statistics for each industry, and some of their compounds phase data and physical properties. • Describes the chemistry, chemical engineering, geology and mineral processing aspects of lithium and calcium chloride • Collects in one source the most important information concerning these two industrial minerals • Presents new concepts and more comprehensive theories on their origin.
Book
Lithium Process Chemistry: Resources, Extraction, Batteries and Recycling presents, for the first time, the most recent developments and state-of-the-art of lithium production, lithium-ion batteries, and their recycling. The book provides fundamental and theoretical knowledge on hydrometallurgy and electrochemistry in lithium-ion batteries, including terminology related to these two fields. It is of particular interest to electrochemists who usually have no knowledge in hydrometallurgy and hydrometallurgists not familiar with electrochemistry applied to Li-ion batteries. It is also useful for both teachers and students, presenting an overview on Li production, Li-ion battery technologies, and lithium battery recycling processes that is accompanied by numerous graphical presentations of different battery systems and their electrochemical performances. The book represents the first time that hydrometallurgy and electrochemistry on lithium-ion batteries are assembled in one unique source.
Article
Lithium is a highly interesting metal, in part due to the increasing interest in lithium-ion batteries. Several recent studies have used different methods to estimate whether the lithium production can meet an increasing demand, especially from the transport sector, where lithium-ion batteries are the most likely technology for electric cars. The reserve and resource estimates of lithium vary greatly between different studies and the question whether the annual production rates of lithium can meet a growing demand is seldom adequately explained. This study presents a review and compilation of recent estimates of quantities of lithium available for exploitation and discusses the uncertainty and differences between these estimates. Also, mathematical curve fitting models are used to estimate possible future annual production rates. This estimation of possible production rates are compared to a potential increased demand of lithium if the International Energy Agency's Blue Map Scenarios are fulfilled regarding electrification of the car fleet. We find that the availability of lithium could in fact be a problem for fulfilling this scenario if lithium-ion batteries are to be used. This indicates that other battery technologies might have to be implemented for enabling an electrification of road transports.
Article
Selective recovery of lithium from seawater was conducted by using two successive processes of ion exchange methods. The preliminary concentration process of lithium from seawater, using the benchmark-scale chromatographic operation with a granulated λ-MnO2 adsorbent, showed the recovery efficiency of lithium at ca. 33%. The purification of lithium from concentrated liquor from the benchmark plant was then conducted with a novel separation process which was developed by a combination of ion exchange methods using cation exchange resin and solvent impregnated resin. The purification process of lithium consists of the removal of divalent metal ions in the liquor with strongly acidic cation exchange resin; the removal of Na and K with the β-diketone/TOPO impregnated resin; and lastly the recovery of Li as precipitates of Li2CO3 using (NH4)2CO3 saturated solution. The yield of recovered Li2CO3 with the present recovery process was 56% with more than 99.9% purity.