Electrically Dewatering Microalgae
Electrically Dewatering Microalgae
Electrically Dewatering Microalgae
Edward F. Kelley
KELTEK, LLC
PO Box 866
Niwot, CO 80544, USA
ABSTRACT
Microalgae are being developed as a source of fuels and/or chemicals. A processing challenge is
dewatering the algae. Electrical approaches to dewatering include exploiting electrophoresis or
electroflocculation. The reported experiments show that electrophoresis does occur but is
complicated by the effects of the fluid motion. It appears that the coupling of the algal cell and
the fluid can be sufficiently strong such that fluid motion effects can influence or dominate
behavior. Electroflocculation appears to be a robust process. It does, however, inherently leave
electrically induced trace metal flocculants in the dewatered algae.
Index Terms — Algae, dewatering, electroflocculation, electrophoresis
development.
1 INTRODUCTION An obvious approach for consideration, as algae normally
MICROALGAE is an environmentally friendly, renewable carry a negative charge, is electrophoresis. In a water solution,
energy source [1]. The term “algae” is broad and may be however, both electrophoresis and electroflocculation can
divided into macroalgae, commonly known as seaweed, and occur under the same set of circumstances. The research
microalgae. Depending on their species, their sizes can range reported here was stimulated by the simple observation that if
from a few micrometers to a few hundred micrometers. The a tray of algae in its growth medium was exposed to an
species used in this study are microalgae. Cultivation of electric field by placing metallic electrodes on two sides of the
microalgae, a rapidly growing single-celled micro-organism, tray and energizing them with a dc voltage, algae
has also been suggested as a way to address the environmental concentrations would occur at both electrodes
issues of carbon dioxide (CO2) greenhouse gas sequestration, (electrophoresis) and at the bottom of the tray
generating renewable fuels, and wastewater remediation [2, 3, (electroflocculation).
4]. Alternative energy research is generally viewed as This research focused on assessment of the factors
important considering the continuing and increasing per-capita influencing electrophoresis and electroflocculation of algae in
global energy consumption, and the reported diminishing its growth medium. These two processes tend to be linked
fossil fuel reserves [5, 6]. The current popularity of algae as a because, if metal electrodes are in contact with the algae and
biomass energy crop may be a result of the ability of algae to water, both processes can occur.
grow in water of a wide range of quality including brackish
The microalgae selected for this work was Chlorella sp.
waters, waste water, and salt water. In addition, algal growth
Appropriate test cells were designed for these studies,
concurrently sequesters carbon dioxide.
including a flow-through test cell with aluminum electrodes.
The high oil content of alga species such as
Nannochloropsis sp., with a reported 29% oil, makes algae an
attractive biofuel crop [7]. Microalgae cultured as a
2 ELECTROPHORESIS
suspension, grown in optimized bioreactors has been reported Electrophoresis is the field-induced motion of a particle
at densities as high as 1% (volume/volume basis) [8], which is with respect to the fluid. Algae have a net negative charge that
10 to 100 times natural growth densities. helps keep them separated [11]. Growth media is water based
Because of the high water-to-algae ratio, energy efficient and contains required chemicals, predominantly monovalent
dewatering is a challenge in the commercialization of biofuels sodium (Na+) and potassium (K+) ions, which may make up at
from algae. For algae growth to be cost-effective, the algae least some of the counterions in electrophoresis. Because the
must be concentrated and the water returned to the growth algae are charged, the force resulting from an electric field
facility. Microalgae is typically removed from large volumes could, in principle, move the algae toward an anode, thus
of water more easily by flocculation and sedimentation than increasing concentration.
by filtration [9, 10], but both approaches are under active There are obvious complexities [12] to the simple
2
observation that an electric field should result in a force on the can be observed. The voltage pulse has a 5 ms width and the
algal cell. These include: average electric field was 1.5 kV/cm. The exposure time for
• Microalgae experience drag forces, so it is difficult to each of the two frames shown is 10 µs.
decouple algal motion from fluid motion. The photograph at the end of the pulse shows algal
• The medium surrounding the algae cells is movement under conditions where effects from the
predominantly water with uncontrolled concentrations electrohydrodynamic phenomena and injections from the
of neutral and ionized material, with the field acting on electrodes are both minimal. In this case, the suspension of
both the algae and the medium. algae moves preferentially but not exclusively toward the
anode, becoming significantly less dense. This effect is likely
• Electrode effects include the injection of metal ions due to the fact that the media also contains positive ions that
into the medium. are attracted to the cathode, initiating fluid flow in that
• Electrohydrodynamic phenomena can be induced and direction. Locally, the fluid flow is sufficient to overcome the
produce complex flow patterns depending on coupling force imposed by the electric field on the algal cell.
of the charge carriers to the fluid and the influence of Higher electric fields were used to highlight the effects of
the test chamber on fluid motion. injection from the electrodes and electrodynamic effects. This
From a process engineering perspective, there is another experiment was performed under the same conditions as
fundamental constraint that must be acknowledged. To Figure 2, with the exception of using a higher voltage (field of
minimize processing cost, the dewatering is ideally done in a 3 kV/cm). The results are seen in Figure 3. The five frames
flow process rather than a batch process. Thus, in the simplest (10 µs exposure, 200 µs between frames) illustrate the process
embodiment of concentration by electrophoresis, the algae in sequential order, during application of the electrical pulse.
would be entrained in a fluid flow approximately orthogonal The first frame shows that the algae are initially attracted to
to the field. This introduces another source of flow. both electrodes (likely due to a combination of electrophoresis
To gain insight into the processes that occur, a high speed and hydrodynamic drag effects as seen in Figure 2).
camera was used to photograph the movement of the algae as Subsequently, emission from the cathode causes fluid motion
a voltage step was applied to a set of parallel electrodes. The which induces significant optical distortion [13, 14]. As the
experimental set up is shown in Figure 1. A light emitting electrical current flow continues, the anode turbulence
diode (LED, Luxeon Rebel, cool white, 140 lm) was used to becomes more severe. If the observation were continued, the
illuminate a test cell in which algae samples were introduced turbulence would fill the entire inter-electrode gap mixing the
by syringe injection. The LED is fan-cooled and has an suspension.
aperture of about 1 mm. The first lens, near the LED, is a 30
mm focal-length coated Achromat. The camera has a 512 x
512 CMOS detector. The test cell is cylindrical with a 19 mm
diameter and a 9.5 mm length along the optical axis. In the test
cell, a voltage pulse with a rise time less than a nanosecond
and duration of several milliseconds was applied to a
suspension of the algae in its growth medium.
Figure 1. Schematic of the optical system from the illuminating laser to the
high speed camera. The algae were introduced into the test cell using the
syringe. An electric field was generated in the test cell by applying a step
voltage to parallel electrodes.
The apparatus illustrated in Figure 1 produced the images Figure 2. Microscopic images of algal movement prior to and following an
shown in Figure 2. applied electric field. The large dark structures in each frame are electrodes
energized so that the anode is on the right as indicated. The stream of small
Figure 2 shows two photographs of algae suspended in black dots is the microalgae flowing in its medium between the electrodes.
growth medium inside the test cell. Prior to the electrical The primary effect of the pulsed electric field is to broaden the algae stream,
pulse, the algae stream is approximately centered between the with preferential broadening toward the anode. This is expected as the algae
carry a negative charge.
electrodes and orthogonal to the direction in which the electric
field will be applied. The dark objects on either side of each This phenomenon likely results from the electrical current
picture are electrodes, with the anode on the right edge of each flow being primarily influenced by ions in the medium and/or
picture. Following the application of the voltage pulse the fluid motion, and only to a lesser extent by the algal cells. If
algae dispersion and migration toward the positive electrode that is a correct assumption, the resistivity of the slurry is
3
expected to increase with increasing algal density. This An algae-water suspension is pumped into the cell through
hypothesis implies that even though there is a current due to the hole on the right side of the chamber in Figure 5. The
algae transport, IA, there is also a current due to ion flow mixture flows between the two electrodes and exits through
through the water surrounding the algae, Iion. The hypothesis is one of two separated chambers. If the electric field moves the
simply that Iion >> IA. A separate experiment was performed to algae preferentially toward either electrode, a corresponding
assess this hypothesis. change in the concentration of algae between the two exiting
streams would result.
Although some algal localization to the cathode was
observed in the high-speed photomicrograph data, such a
separation was not observed on the macroscopic scale. The
data indicate only a slight separation under direct current (DC,
50 V), consistent with the observations in Figure 2, but no
significant separation in this apparatus. The fluid flow appears
to dominate over electric field in the determination of algae
motion.
3 ELECTROFLOCCULATION
Electroflocculation was reported as early as 1903 in the
Figure 4. Conductivity of a slurry of the algae in its growth medium at
patent literature and has found extensive use in the petroleum
different algae concentrations versus applied voltage. Cell density has a industry to break emulsions and remove oils [15, 16, 17]. In
significant influence on electrical conductivity of the mixture, as expected. traditional flocculation processes, polyvalent metal ions such
An electrical test cell was constructed to validate the as iron (Fe+3) or aluminum (Al+3) are added to water as salts to
microscopic results on a macroscopic level. The test cell is cause the flocculation. The algal growth media contains trace
shown in Figure 5. It consists of a machined polypropylene quantities of divalent calcium (Ca+2), and magnesium (Mg+2)
block with a central channel and fluid inlet and outlet holes. ions, as well as polyvalent iron (Fe+3) ions. Electroflocculation
Aluminum electrodes lined the central channel. Provisions differs from traditional flocculation in that sacrificial
were made at the outlet end of the test cell for two liquid polyvalent metal electrodes generate metal ions in water,
streams to exit in a volume ratio of 2:1 to evaluate additional replacing the external addition of a salt. Because the sacrificial
water removal due to cell electrophoresis. A regulated dc electrode is consumed, an inexpensive material is
power supply was set to the desired voltage and connected to recommended [15].
the electrodes. Microalgae do not naturally flocculate or coagulate due to,
4
at least in part, their net negative charge. Algal growth medial material was then measured to determine the clearance rate.
also typically contains only trace quantities of the divalent and The data presented are the averages of at least six samples and
polyvalent cations required. The accepted mechanism by the error bars represent one standard deviation of the sample
which flocculation occurs is that electrochemical reactions at mean. Statistical analysis was performed by one way
the electrodes create positive, polyvalent ions [15]. These ANOVA. Figure 7 shows the settling of the algae as a function
positive ions attract the negatively charged algal cells. The of time after exposure.
algal cells and polyvalent ions create a growing network of a This analysis showed that dewatering effectiveness
charged neutral system. The networks can extend to other increased with increasing current over the range tested.
neutral systems and continue to grow into larger assemblies of Specifically, 1.0 A – 2.0 A caused a significant (p<0.01)
flocculated algae. increase in algae (Chlorella sp.) clearance within one minute
Faraday’s law of electrolysis says that the mass of metallic of electroflocculation, and highly significant clearance
ions emitted by the anode is proportional to the change (p<0.001,) at five minutes, compared to non-flocculated
transported through the circuit. In these tests, the algae-water controls. At these currents, >95% of the pure Chlorella culture
mixture flowed between the electrodes while a constant was dewatered in 10 minutes.
current was applied perpendicular to the flow. Since each In practical situations, however, it has typically been very
element of the liquid was exposed for the same amount of expensive to maintain a monoculture. So, the process was also
time, the current is expected to be approximately proportional evaluated with a mixture of cynobacteria and Chlorella.
to the change. Cyanobacteria is a common species that grows in combination
Test Setup with microalgae in many areas of the world.
The electroflocculation tests were conducted in the same With a mixture of cynobacteria and Chlorella, the clearance
test cell that was used for the electrophoresis testing, Figure 5. (settling) rate at a given current was slower, with less settling,
The test cell was, however, modified as indicated in Figure 6. and more current was required to maximize settling.
Specifically, the two exit ports were connected together so that Microscopic observation revealed that the cyanobacteria were
all of the mixture that was exposed to the electric field was fragmented following electrophoresis, and thus more likely to
collected in a single flask. The concentration of algae in the remain in solution.
efluent was determined by an optical measurement. The Dewatering of the mixed cynobacteria and Chlorella
optical effect was not subtle, i.e., settling was visually obvious cultures reached a maximum of 75% at a current of 2.0 A.
with, but not without, exposure to the current and electric Currents of 1.0 A, 1.5 A, and 2.0 A improved dewatering of
field. The optical measurement was used to provide mixed cultures significantly (p<0.05, p<0.01, and p<0.001,
quantitative information of the rate of settling. As the algae respectively). By comparison, for Chlorella monocultures, 1.0
flocked and settled to the bottom of the vial, the algal solution A was sufficient to clear algae; 80% and 100% within five and
became less dense. Density readings were taken periodically 20 minutes, respectively. While this process appeared to
over a 60-minute period. Data are reported as the rate of algae separate the Chlorella from the cyanobacteria, no quantitative
clearance from the incubating solution. measurements were performed to determine separation
efficiency.
were performed, with algae at densities of 0.2 g/L and 0.6 g/L. concentrated algae. Since this trace metal can reduce the value
The algal density was measured by two methods: 1) dry of the products produced, dewatering methods that do not
weight of the biomass, and 2) cell counts based on leave trace metals would generally be preferred.
measurements using a hemocytometer. Hemocytometer Thus, both processes occur in systems containing
calculations were based on counts of 10 random fields. Figure microalgae in their growth medium. Both appear to require
8 illustrates density making an observable difference. further development if they are ever to be viable candidates
This difference is presumably due to the fact that the for cost effective dewatering of microalgae at a commercial
flocked algal cells have a greater likelihood of continuing to scale.
flocculate into larger ionic networks at the higher density. It is
also interesting to note that the algae were 50% dewatered by ACKNOWLEDGMENT
one minute at 5 ml/s for lower density (0.2g/L) Chlorella sp.
cultures, but that the higher density culture was slower to M.E.F. thanks Dr. Jerry Brand and Dr. Martin Poenie of the
clear. University of Texas, and Adelheid Kuehnle of Kuehnle
AgroSystems for critical discussion regarding algal growth
and handling. This work was supported in part by OpenAlgae.
APPENDIX
Organism and growth conditions. The microalgae Chlorella
sp., (Strain KAS01110803) were obtained from Kuehnle
AgroSystems, Inc., (Honolulu, Hawaii, USA). The algae
suspension cultures were grown in six-liter Erlenmeyer flasks
with continuous aeration at an airflow rate of 250 ml min-1.
The flasks were arranged on a rack illuminated with daylight
fluorescent lamps at a light intensity of 120 µmol photons m-2
s-1. The cultures were maintained with a circadian light: dark
cycle of 12:12 h at 25° C. The microalgae Chlorella sp. were
grown as non-axenic cultures on F2 media [18], modified by
replacing the sodium nitrate (nitrogen source) with urea
(equimolar on a nitrogen basis).
Chlorophyll a (Chl a) Spectrophotometric Measurement.
The Chl a spectrophotometric measurements were performed
at the chlorophyll Soret band (430nm), using a Bausch &
Lomb Spec20 spectrophotometer (10 nm bandwidth) [19].
Measuring the Chl a absorbance at 430 nm in the Soret band,
as compared to the Q-band (630-700 nm), results in a
calculated 3.4-fold sensitivity improvement and is also
thought to eliminate the interference from accessory pigments,
observed at wavelengths above 460 nm, specifically in the Q-
Figure 8. Settling vs. time for different flow rates and a current of 1.0 A. The
band [20].
upper chart shows results with an algal density of 0.2 gm/l and the lower a
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process options and economics,” Biotechnology Advances, Vol. 20, No. the Center for Electromechanics at the University of Texas
7-8, pp. 491-515, January 2003. at Austin since 2002 and is currently pursuing his Ph.D. in
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Conf. Properties and Applications of Dielectric Materials, Tokyo, Japan, University in 1977. He started in a post-doctoral position at
pp. 264-266, July 1991. NIST in high-voltage impulse measurements using the
[14] M. Haidara and P. Atten, “Role of EHD motion in the electrical electro-optical Kerr effect. He continued at NIST as a staff
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Filtration & Separation, Vol. 32, No. 2, pp. 153-156, February 1995. Optical Delay designed for photographing random events before they happen
[14] I.F. Saur, S. Rubachs, J.S. Forde, G. Kjaerheim, and U. Syversen, but after they occur. After going to Idaho to get a taste of private consultation
“Electroflocculation: Removal of oil, heavy metals and organic and university teaching, he returned to NIST in 1992 to work in the Flat Panel
compounds from oil-in-water emulsions,” Filtration & Separation, Vol Display Laboratory of the Display Metrology Project to assist industry in
33, No. 4, pp. 295-303, 1996. developing measurement standards to quantify display quality. He has served
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[18] C. C. Trees, D. K. Clark, R. R. Bidigare, M. E. Ondrusek, and J. L. Austin. He has over 27 years of experience working in
Mueller, “Accessory pigments versus chlorophyll a concentrations research and development, including: principle investigator
within the euphotic zone: a ubiquitous relationship,” Limnology and for high power and energy prototype and thermal analysis,
Oceanography, Vol. 45, No. 5, pp. 1130-1143, 2000. and materials and process engineering. He has more than 70
technical publications.
BIOGRAPHIES Mr. Werst currently is the Program Manager for the Algae Oil Extraction
Program and is responsible for the scale up of the electromagnetic lysing
Robert V. Pearsall received his B.S. in Mechanical process and end-to-end oil processing commercialization efforts. Previously,
Engineering in 2004 from the University of Texas at Austin he was the Program Manager for CEM’s roll of developing the power supply
and is now a Research Engineer there at the Center for for the US Navy’s Electromagnetic Aircraft Launch System. Other recent
Electromechanics. He has extensive experience in prototype programs include development of high density motors and generators using
design and manufacturing and has contributed to a variety of HTS trapped field magnets and development of magnetic gearboxes for wind
research projects during, participating in concept generation, turbine applications.
prototype development, design, analysis, testing, project
planning, internal documentation, and external publications. Robert E. Hebner, Ph.D., (S’70-M’71-SM’83-F’93) is
Since May 2008, Mr. Pearsall has been a key team member in the Algae Oil Director of the Center for Electromechanics at the University
Extraction Program centered on advanced biofuels and renewable energy. He of Texas at Austin. The Center develops technology,
became the Secondary Lead Mechanical Engineer and currently serves as a primarily novel motors, generators, and suspension
Project Team Leader for the program. components, and teams with companies to get the technology
into the market.
Rhykka L. Connelly received her B.S. and Ph.D. in Cell
Biology in 2000 and 2006, respectively, from Northern Previously, Dr. Hebner was the acting Director of the U.S.
Illionois University in DeKalb, Illinois. She joined the National Institute of Standards and Technology (NIST). In addition, he has
University of Texas in Austin (UT) Center for directed NIST’s Electronic and Electrical Engineering Laboratory, a
Electromechanics in February 2009. UT is conducting a laboratory with a staff of more than 250. He also worked at the Defense
multidisciplinary research and development program directed Advanced Research Projects Agency where he developed programs to
toward cost-effective extraction of renewable algal oil and improve semiconductor manufacturing.
other industrially relevant biomolecules. Dr. Connelly has directed the Throughout his career, Dr. Hebner has been active in having authored or
activities in the biochemical processing laboratory, including detailed analysis coauthored more than one hundred technical papers and reports. He has
of UT and customer algae, training of technical staff, and development of extensive experience in international technology programs. This work
projects and intellectual properties pertaining to the algae program. included the modernization of the measurement systems needed to support
global trade and the assessment of the effectiveness of government technology
programs in stimulating domestic economies.