Separation and Purification Technology 237 (2020) 116466

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Separation and Purification Technology

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Separation performance of desanding and deoiling hydrocyclones treating T

three-phase feeds: Effect of oil-particle aggregates
Andrii V. Gorobets, Volodymyr V. Tarabara
⁎

Department of Civil and Environmental Engineering, Michigan State University, East Lansing, MI 48824, USA

ARTICLE INFO ABSTRACT

Keywords: The study presents preliminary results on the separation of a three-phase (oil, particulate SiO2, water) feed by
Hydrocyclone desanding and deoiling hydrocyclones. Optical microscopy confirms formation of oil particle aggregates (OPAs)
Oil particle aggregate of a range of morphologies. Presence of OPAs does not affect the efficiency of oil separation but lowers the
Separation efficiency efficiency of separation of solids. In both hydrocyclones, OPAs preferentially partition into the overflow stream
Deoiling
so that oil and SiO2 can be viewed as the “lead” and the “follower” phases, respectively. A model is developed to
Desanding
calculate the fraction of the “follower” phase incorporated in aggregates. Applied to data from the desander, the
model shows that ~30% to 40% of SiO2 is captured in oil/SiO2 aggregates and that the fraction does not depend
on the split ratio. In contrast, during deoiling, the fraction of SiO2 locked up in oil/SiO2 aggregates does not
exceed 10% and is lower at lower split ratios; these observations can be attributed to aggregate break-up in a
higher shear flow in the deoiler.

1. Introduction
Oil and gas extraction processes generate large volumes of waste-
water that is typically a multiphase dispersion (e.g. oil/gas/water, oil/
solids/water) that needs to be treated prior to disposal or water reuse.
This waste stream, known as produced water, is a complex mixture of
organic and inorganic compounds in both dissolved and suspended
phases [1]. Dissolved species may include oil, production chemicals,
dissolved minerals and gases. Suspended materials may include both oil
and solids. The latter is a broad category that comprises formation sand,
silt and clays; precipitated solids; corrosion and scale products; and
proppants [2,3]. The concentration of total suspended solids is gen-
erally site-specific and in the case of oilfield-originating produced water
can vary from one oilfield platform to another [3,4]. Unless removed,
solids in produced water can increase the costs of oil production. For
example, common scales and biofilms can clog flow lines and form oily
sludge. Three phase mixtures can also result from accidental oil spills
where oil, sediment, and oil-sediment aggregates are all present in the
water column. Indeed, aggregates of oil and suspended particulate
matter have been the subject of increasing research scrutiny [5–12]
spurred in large part by catastrophic events such as the 1989 Exxon
Valdez and 2010 Kalamazoo River oil spills [8–10,13]. When the solid
constituents are inorganic, such aggregates have been described as oil-
mineral aggregates [5] or, in the case of solids of biological origin,
“marine oil snow” [14]. A more general term "oil-particle aggregates"
(OPA) has also been used [8–10,12].
Separation of a three-phase feed (oil, solids, water), can be chal-
lenging and often involves more than one unit process. Commonly used
technologies include gravity separators (e.g. skim tanks with plate
coaleascers, API separators), dissolved air flotation, coalescence in
granular media, and hydrocyclones. Hydrocyclones [15,16] are used for
solid-liquid, liquid-liquid and three-phase separations and are em-
ployed to treat produced water [17] as well as other multiphase
streams. Example applications include separation of multiphase mix-
tures in paper processing [18], removal of suspended catalyst from oil
[19], separation of particles from flu gas in a desulfurization system
[20], soil washing [21], and coke powder removal from quench oil
[22]. While the flow within hydrocyclones is complex [23], they are
simple to operate, robust units with no moving parts, inexpensive to
install and maintain and configurable as compact, low-footprint devices
[24]. Three-product cyclones have been used to separate complex feeds
into three effluent streams [25]. A modification of a conventional hy-
drocyclone, three-product hydrocyclones have either the overflow
outlet or the underflow outlet split. For instance, a double-underflow
three-product hydrocyclone was used to separate middle-size particles
and coarse particles into two underflow outlets [26]. In another ex-
ample, a hydrocyclone with two concentric vortex finders in the over-
flow was employed to classify low grade platinum ore containing high

⁎
Corresponding author.
E-mail address: tarabara@msu.edu (V.V. Tarabara).

https://doi.org/10.1016/j.seppur.2019.116466
Received 5 August 2019; Received in revised form 13 December 2019; Accepted 20 December 2019
Available online 23 December 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
A.V. Gorobets and V.V. Tarabara Separation and Purification Technology 237 (2020) 116466

Nomenclature Qin flow rate of the inflow

Qover flow rate of the overflow
List of symbols Qunder flow rate of the underflow
x fraction of SiO2 captured in oil/SiO2 aggregates
Cinagg concentration of SiO2 captured in oil/SiO2 aggregates in agg
reduced separation efficiency for SiO2 captured in oil/SiO2
the inflow aggregates in tests with three-phase (oil/SiO2/water) feed
agg
Cunder concentration of SiO2 captured in oil/SiO2 aggregates in free
reduced separation efficiency for oil-free SiO2 in tests with
the underflow three-phase (oil/SiO2/water) feed
Cinfree concentration of oil-free SiO2 in the inflow free + agg
reduced separation efficiency for SiO2 (including both oil-
free
Cover concentration of oil-free SiO2 in the overflow free SiO2 and SiO2 captured in oil/SiO2 aggregates) in tests
CinSiO2 concentration of SiO2 in the inflow with three-phase (oil/SiO2/water) feed
SiO2
Cover concentration of SiO2 in the overflow oil
reduced separation efficiency for oil in tests with two-
Cinoil concentration of oil in the inflow phase (oil/water) feed
oil
Cunder concentration of oil in the underflow SiO2
reduced separation efficiency for SiO2 in tests with two-
F flow ratio phase (SiO2/water) feed
S split ratio

Fig. 1. Design of the (a) single-inlet solid-liquid separation hydrocyclone (SLHC) and (b) dual-inlet liquid–liquid separation hydrocyclone (LLHC) as well as c) the
flow loop used to test the performance of both SLHC and LLHC. Table S1 (see SM) gives size ratios for LLHC. SLHC and LLHC are drawn to 1:2 scale. The units of
length are millimeters. Components of the flow loop are: feed tank (1); pump (2); hydrocyclone inlet (3), overflow (4) and underflow (5) outlets; pressure gauges (6);
and control valves (7).

2
A.V. Gorobets and V.V. Tarabara
density chromite and low density silica carrying platinum group metals;
by capturing silica in a separated overflow stream, the recovery of
platinum was improved [27].
While the knowledge base on OPAs is quickly growing, most of
research is done in the context of formation, fate and transport of OPAs
in natural waters. To our knowledge there has been no prior work on
the separation of OPAs for wastewater treatment or oil spill mitigation.
The present study addresses this knowledge gap. Two specific objec-
tives were 1) to assess the separation performance of conventional
hydrocyclones treating a three-phase oil/solids/water feed and 2) to
evaluate the impact of OPAs on the separation efficiency. Given that
hydrocyclonic separation relies on the density differential between
phases, aggregation of positively and negatively buoyant particles may
have a significant effect on separation. Laboratory-scale experiments
were performed using a solid-liquid hydrocyclone (SLHC, “desander”)
and a liquid-liquid hydrocyclone (LLHC, “deoiler”) challenged with
model feeds that included both three-phase (mineral oil, particulate
SiO2, water) and two-phase (oil/water, SiO2/water) dispersions.
2. Materials and methods
2.1. Reagents
Mineral oil ( oil = 0.86 g/cm3; Rite Aid pharmacy) and anti-
microbial treated silica (SiO2) sand ( SiO2 = 2.65 g/cm3, particle
size < 40 µm; U.S. Silica) were used to prepare model feeds for se-
paration tests. Ultrapure water (~17 MΩ·cm) was provided by
Barnstead E-pure water purification system. Tetrachloroethylene
(99.8%; J.T. Baker) and diluted (x5) hydrochloric acid (EMD
Chemicals) were used for oil extraction from emulsions during oil
concentration measurements. Oil-Red-O dye was purchased from
Sigma-Aldrich and used as received.
2.2. Two phase (oil/water, SiO2/water) and three phase (oil/SiO2/water)
feeds
Emulsions were prepared by adding 21 mL of mineral oil to 2 L of
ultrapure water and stirring the resulting mixture for 18 h using a di-
gital mixer (model RW 20, IKA Werke) at 1000 rpm. The emulsion was
diluted to 1000 mg(oil)/L with 16 L of DI water and mixed for an ad-
ditional 25 min, after which droplet size distribution and oil con-
centration in the emulsion were measured. SiO2 suspensions of
1000 mg(SiO2)/L were prepared by adding 18 g of SiO2 particles to 18 L
of ultrapure water and mixing the suspension for 30 min. The three-
phase feed was prepared by adding SiO2 to the oil-water emulsion
(prepared as described above) and mixing during 30 min. In hydro-
cyclone separation tests, the initial concentration of oil and SiO2 par-
ticles in the inflow was determined to be 969 ± 374 mg(oil)/L and
1158 ± 210 mg(SiO2)/L, respectively, based on the measured con-
centrations in the overflow and underflow streams. This approach
based on the mass balance had to be used because direct measurements
in the inflow (i.e. in the feed tank) gave highly variable results possibly
due to incomplete mixing or accumulation of SiO2 particles and oil in
the pump. No surfactants were added to any of the feeds.
The concentration of suspended solids in natural water bodies can
be highly variable and depends on factors such as salinity, streamflow,
mixing conditions, runoff, etc. For example, the Kalamazoo River has a
relatively low suspended sediment concentration of less than 100 mg/L
[8]. Similarly, concentration of oil during a spill varies with time,
proximity to the spill location, mixing conditions, and other factors. The
concentration employed in the present work (~970 mg(oil)/L) was si-
milar to that (~790 mg(oil)/L) used by Waterman and Garcia in their
study on oil-particle interactions in freshwater environment where
conditions of the diluted bitumen spill into the Kalamazoo River were
simulated [28].
3
Separation and Purification Technology 237 (2020) 116466
2.3. Solid-liquid and liquid-liquid hydrocyclones
The single-inlet SLHC (Fig. 1a) and dual-inlet LLHC (Fig. 1b) were
manufactured by ChemIndustrial Systems, Inc. (CSI, Cedarburg, WI). The
single-inlet modular design of SLHC afforded a number of different geo-
metries, four of which (Figure S3) were evaluated in preliminary se-
paration tests. The geometry of LLHC was that of the Young hydrocyclone
[29] (Table S1). Each hydrocyclone had an underflow valve, which was
used to control the backpressure and regulate the flow ratio (see Fig. 1)
2.4. Design of the hydrocyclones separation system
Fig. 1c shows the flow loop constructed to test the separation per-
formance of SLHC and LLHC. A progressive cavity pump 2 (Moyno. 332,
Fluid Process Equipment, Inc) supplied the feed from the 18.9 L (5
gallon) feed tank 1 to the hydrocyclone inlet 3. After entering the hy-
drocyclone tangentially though the inlet, the feed formed a vortex
within the device and separated into the overflow and the underflow
streams that exited the device through the corresponding outlets 4 and
5. Pressure gauges 6 were installed at the inlet and at each outlet. The
flow ratio was regulated by control valves 7. Both overflow and un-
derflow streams were cycled back to the feed tank 1.
2.5. Measuring concentrations of oil and particulate SiO2
Concentration of SiO2 in two phase (SiO2/water) dispersions was
measured using the gravimetrical method. Samples from inlet, over-
and underflow (100 mL each) were filtered through glass fiber mem-
branes GA-55 (Sterlitech) and the sediments were dried in an oven at
120 °C and weighed on an analytical balance (AE 240, Mettler).
Oil concentration was determined based on infrared adsorption
measurements. Oil/water or oil/SiO2/water samples were diluted 10
times with DI water, acidified to below pH 2 with HCl, and the oil was
extracted by tetrachloroethylene. Then, 10 mL of the diluted sample
were mixed with 10 mL of tetrachloroethylene and the mixture was kept
on a shaker for 30 min. The IR absorption measurements were performed
using a TOG/TPH analyzer (Infracal CVH Wilks Enterprise, Inc).
2.6. Size distribution measurements and confocal microscopy
The size distribution of SiO2 particles and oil droplets was measured
using laser diffraction analysis (Mastersizer 2000, Malvern). Refractive
indices of 1.54 and 1.46 were used for SiO2 and mineral oil, respec-
tively [30,31]. Both silica and mineral oil were assumed to be non-
absorbing (i.e. imaginary part of the refractive index is zero). Samples
were taken in locations immediately downstream of the overflow and
underflow outlets and from the feed tank.
Brightfield transmitted light images were collected using a Zeiss
Pascal confocal laser scanning microscope equipped with a dry objec-
tive with magnifications in the 10x to 40x range. Oil-Red-O dye was
excited using a 543 nm He-Ne gas laser and fluorescence emission was
collected using a 560 nm long pass emission filter.
2.7. Determining separation efficiency
The SLHC (often referred to as a “desanding” hydrocyclone) is de-
signed to preferentially direct solids into the underflow and separate
the feed into a relatively solids-free overflow (“product” stream) and a
high solid fraction underflow (“concentrate” or “waste” stream).
Accordingly, the reduced separation efficiency for SiO2 is defined as
SiO2
Cover
SiO2
=1
CinSiO2 (1)
where and
SiO2
Cover are concentrations of SiO2 in the overflow and
CinSiO2
inflow, respectively. The ideal separation corresponds to no SiO2 in the
A.V. Gorobets and V.V. Tarabara Separation and Purification Technology 237 (2020) 116466

overflow ( sand = 1). By contrast, LLHC (often referred to as a
“deoiling” hydrocyclone) is designed to preferentially direct oil into the
overflow and separate the feed into a relatively oil-free underflow
(“product” stream) and a high oil content overflow (“concentrate” or
“waste” stream). Accordingly, the reduced separation efficiency for oil
is defined as
challenged with three-phase feeds where both oil and SiO2 were present
in the inflow. For consistency, we applied Eq. (1) to describe removal of
SiO2 and Eq. (2) to describe removal of oil regardless of the hydro-
cyclone type (SLHC or LLHC).
The separation efficiency is known to be a function of the split ratio,
S , or its complementary metric, flow ratio, F = 1 S ):

oil Qover
Cunder S=
oil =1 Qin (3)
Cinoil (2)
Qover Q Qover Q
where Cunder
oil
and Cinoil are concentrations of oil in the underflow and F=1 = in = under
Qin Qin Qin (4)
inflow, respectively. The ideal separation corresponds to no oil in the
underflow ( oil = 1). In the present study, both SLHC and LLHC were where Qin , Qunder and Qover are flow rates in the inflow, underflow and

Fig. 2. Volume-based (a, c) and number-based (b, d) size distributions of SiO2 particles (a, b) and oil droplets (c, d) in the inflow and two outflow streams of SLHC (a,
b) treating SiO2-water mixture (with the split ratio of 10%) and LLHC (c, d) treating oil-water mixture (with the split ratio of 9.7%). Lines are added to guide the eye.

4
A.V. Gorobets and V.V. Tarabara
overflow streams, respectively. Thus, we tested both SLHC and LLHC in
experiments where the hydrocyclones were operated under a range of
different split ratios. Spilt ratio, S , and flow ratio, F , are commonly
used as metrics of the fraction of the inflow that is directed to the
“waste” (or “concentrate”) stream, which is overflow for a deoiler and
underflow for a desander; thus, S is commonly used in conjunction with
deoiling and F – in conjunction with desanding.
3. Results and discussion
The fate of oil/SiO2 aggregates in a hydrocyclone flow should de-
pend on their effective density relative to that of the continuous phase.
The aggregate density is determined by the densities of constituent
phases, which are known ( oil = 0.86 g/cm3, sand = 2.65 g/cm3) as
Fig. 3. Representative confocal microscopy images of oil-particle aggregates in the three-phase suspension. The oil phase contains Oil-Red-O dye and appears in red.
Images of oil droplets and SiO2 particles in non-aggregated systems are given in SM.
5
Separation and Purification Technology 237 (2020) 116466
well as by two apriority unknown characteristics: aggregate size and the
relative fractions of oil and SiO2 within aggregates. Thus, we first
present results on particle and droplet size measurements with two-
phase feeds as well as confocal microscopy images of oil/SiO2 ag-
gregates. Subsequently, we present data on the efficiency of hydro-
cyclonic separation in tests with two-phase (oil/water, SiO2/water) and
three-phase (oil/SiO2/water) feeds. The final section describes the
calculation of the relative fractions of oil and SiO2 in the oil/SiO2 ag-
gregates and the implications of the findings for practical separations.
3.1. Oil, SiO2 and oil/SiO2 aggregates: Size distribution and morphology
Fig. 2a and 2b show size distribution of SiO2 particles in the feed of
the desanding hydrocyclone (i.e. SLHC). The volume-based distribution
A.V. Gorobets and V.V. Tarabara
data indicate that ~6.5% of the SiO2 volume is in particles (or, possibly,
aggregates) larger than 40 µm, which is the cut-off size according to the
vendor. Based on the Wentworth scale of particle sizes [32], the solid
phase is categorized as mostly silt (defined as particles in the 3.9 µm to
63 µm range) but also includes very fine sand (63 µm to 125 µm). The
mean particle size (d 0.5 ) in the inlet, overflow and underflow streams is
13.5 µm, 9.9 µm and 21.4 µm, respectively. A comparison of number-
based data (Fig. 2b) for the inlet (feed) and the underflow streams
points to a roughly bimodal number-based distribution of particle sizes
with submicron particles forming one (much more populous: 81.6% by
number in the feed) fraction and particles mostly in the 2 µm to 20 µm
range forming another fraction. The latter fraction, which is minor by
number (6.1%) but not by volume (64.2%) in the feed, is comprised of
particles that the hydrocyclone separates into the underflow.
Fig. 2c and 2d show size distribution of oil droplets in the feed of the
deoiling hydrocyclone (i.e. LLHC). The mean particle size (d 0.5) in the
inlet, overflow and underflow streams is 16.0 µm, 9.5 µm and 19.8 µm,
respectively. A comparison of volume-based distributions for the feed,
underflow and overflow streams shows that most smaller droplets es-
caped into the underflow while larger droplets, as expected, were
predominantly directed into the overflow. For example, droplets
smaller than 5 µm correspond to 15.9%, 7.5% and 28.1% of all the oil in
the feed, overflow, and underflow streams, respectively. Yet the cor-
responding numbers for droplets larger than 20 µm are 38.8%, 49.6%,
and 17.6%. Although the size distributions for the feed suspensions of
SiO2 (Fig. 2a; inflow) and oil (Fig. 2c; inflow) are similar, the separation
of the larger particles was more effective for SiO2; this result was ex-
pected based on the higher density differential with respect to the
continuous phase (~1.65 g/cm3 for SiO2, ~0.14 g/cm3 for oil. Because
of possible coalescence and break up, the oil droplet distribution can
change depending on the shear conditions in the process stream. Thus,
droplet size distributions presented here are specific to the conditions of
this study (e.g. flow rate, flow ratio, type of hydrocyclone, type of oil).
Particle size distributions are consistent with results of settling ki-
netics measurements wherein oil in the underflow (Fig. S1a) and SiO2
in the underflow (Fig. S1b) settle the fastest. For the three-phase feeds,
the overall settling kinetics could be predicted based on settling kinetics
of constituent phases; there was no apparent synergistic enhancement
Fig. 4. Reduced separation efficiency of SiO2 particles ( SiO2 = 1 Cover
SiO2
/ CinSiO2 ) and oil ( oil = 1 Cunder
or oil/water) and three-phase (oil/SiO2/water) feeds. The efficiencies are plotted as functions of the flow ratio (F = Qunder / Qin ) for the SLHC and of the split ratio
(S = Qover / Qin ) for LLHC. Lines are added to guide the eye. SLHC and LLHC were operated at the inlet flow rate Qin of 20 L/min and 15 L/min, respectively.
6
Separation and Purification Technology 237 (2020) 116466
or delay in sedimentation due to formation of the oil/SiO2 aggregates
(Fig. S1b). The settling time required for a 50% decrease in turbidity
was ~1 h. The size distribution of solids (very fine silt to very fine sand)
was generally consistent with what can be expected during an oil spill
in a freshwater environment. For example, during the Kalamazoo River
spill, suspended particle sizes were mainly in the silt-size range [8]. The
size distribution of oil droplets depends on the mixing conditions and
properties of both the oil and the continuous phase [33]. The oil dis-
persions employed in this work had relatively small droplet sizes cor-
responding to higher mixing energy inputs and lower surface tensions.
Figure S6 shows cumulative volume fractions (a commonly used format
when reporting particle and droplet sizing data) for SiO2 and mineral
oil in the mixture fed to the hydrocyclones.
Particle size distributions obtained by laser diffractometry are sen-
sitive to the values of the real and the imaginary components of the
refractive index [34,35]. In this study, the imaginary components are
assumed to be zero for both silica and mineral oil (see Section 2.6).
Thus, particle size data should be viewed as estimates and not quanti-
tatively reliable predictions. For oil-particle aggregates, the refractive
index was not known because of their complex (and likely variable)
makeup. Thus, particle size distribution in the three-phase mixture (oil/
SiO2/water) could not be obtained by laser diffractometry. Instead, we
employed confocal microscopy imaging of the suspensions (Fig. 3). Oil-
particle aggregates presented 4 distinct morphologies: droplets with a
submonolayer coating by clay-sized particles (Fig. 3a, Fig. 3e), silt
coated by a thin layer of oil (Fig. 3b, Fig. 3f), agglomerates of similar
sized droplets and silt (Fig. 3c), and silt particles enveloped in larger oil
droplets (Fig. 3d). By comparison, Hayter et al, considered three types
of OPAs in their modeling of OPA transport in surface waters: Type 1
(large droplet with silt coating), Type 2 (silt aggregates with smaller oil
droplets) and Type 3 (large silt aggregate with small oil droplets) [36];
the latter two types may be grouped together and described as oil
droplets “trapped within or adhering to large particles” [37].
3.2. Separation in the solid-liquid hydrocyclone (desander) and the liquid-
liquid hydrocyclone (deoiler)
In a study of hydrocyclones with different cone combinations to
oil
/ Cinoil ) in a) SLHC and b) LLHC treating two phase (SiO2/water
A.V. Gorobets and V.V. Tarabara Separation and Purification Technology 237 (2020) 116466

remove solids in a flue gas desulphurization system, Yang et al. showed SiO2 aggregates in the inflow.
that cone angle change had significant effect on the separation effi- Reduced separation efficiency for the oil-free SiO2 particles can be
ciency and sharpness along with several other important parameters written in the following form (analogous to Eq. (1)):
such as energy consumption [20]. With no prior studies on the se- free free
Cover Cover
paration of OPAs by hydrocyclones, no a priori guidance on the optimal free =1 =1
hydrocyclone geometry was available; thus, the present study included Cinfree (1 x ) CinSiO2 (6)
preliminary testing of four different SLHC geometries with different where is the concentration of oil-free SiO2 particles in the over-
free
Cover
combinations of cone angles and lengths (Fig. S3) to identify an optimal flow. We assume that in tests with the three-phase feed (oil/SiO2/
geometry. The design shown in Fig. 1a was selected as giving the water), the separation efficiency of oil-free SiO2 particles is same as that
highest SiO2 separation efficiency for 0.50 < S < 0.95 (Fig. S4). in the tests with the SiO2/water feed (empty squares in Fig. 4) and the
Young geometry for LLHC is one of the more common designs that gives separation efficiency of SiO2 particle-free oil is same as that in the tests
a near-optimal performance. The LLHC geometry was not optimized in with the oil/water feed (empty circles in Fig. 4). Further, based on the
the present work; this decision reflected the assumption that SLHC experimental funding that oil is not affected by the presence of SiO2
should be the primary separation method for removing OPAs. LLHC (see Section 3.2), we assume that oil/SiO2 aggregates are separated by
performance in the absence of adequate pretreatment is still of interest, the hydrocyclone as if they were SiO2 particle-free oil droplets. The
so one LLHC geometry (that of a Young hydrocyclone) was evaluated. separation efficiency of SiO2 captured in oil/SiO2 aggregates, agg , is
The separation data (Fig. 4) revealed three salient trends: then equal to oil :
agg = oil (7)
1) Separation efficiencies for both SiO2 and oil increased with an in-
crease in flow ratio (in SLHC) and split ratio (in LLHC). The trend and can be can be determined using the relationship analogous to Eq.
reflects the trade-off between the degree of treatment (i.e. the extent (2):
of deoiling or desanding) and the product stream flow rate. The agg agg
Cunder Cunder
trend was less pronounced for oil in SLHC; this was expected as the agg =1 =1
desanding hydrocyclone is not optimal for removing oil. In contrast, Cinagg xCinSiO2 (8)
LLHC showed a relatively high efficiency in separating SiO2, even where is the concentration of SiO2 locked up in oil/SiO2 ag-
agg
Cunder
though the Young design is optimized for liquid-liquid separations. gregates in the underflow. We note that agg was not directly measured
2) The separation efficiencies for both SiO2 and oil are relatively low. in our experiments with three-phase feeds. Instead, we measured the
This can be explained by the large volume fraction of the dispersed overall separation efficiency for SiO2 (i.e. all SiO2, including both oil-
phase incorporated in small particles or droplets. For example, free SiO2 and SiO2 captured in oil/SiO2 aggregates), free + agg :
~31 vol% of oil is in droplets smaller than 10 µm - the approximate
free agg free agg
size cut-off, below which liquid-liquid hydrocyclones become in- free + agg Cover + Cover Cover Cover
=1 =1
effective [38]. Although the density differential is significantly CinSiO2 CinSiO2 CinSiO2 (9)
higher for SiO2, the solids had a very small particle size (Fig. 2). In The separation efficiency free + agg is denoted as filled squares in
addition, SLHC was an experimental model that was subjected to Fig. 4.
only limited optimization (Fig. S3). The second term on the right-hand side of Eq. (9) can be expressed
3) A difference in the separation of SiO2 and oil by the hydrocyclones is using Eq. (6):
that the presence of SiO2 particles does not have a statistically sig-
free
nificant effect on oil , while the presence of oil decreases sand , Cover free )(1
=(1 x)
especially so at lower recoveries (i. e. at higher values of F in SLHC SiO2
Cin (10)
and S in LLHC).
As shown in SM, the third term on the right-hand side of Eq. (9) is
given by
In light of the microscopy-based evidence of the formation of oil-
particle aggregates, the trends in separation efficiencies indicate that in agg
Cover x (1 oil ) x (1 S)
=
both SLHC and LLHC, oil-particle aggregates behave as oil droplets and CinSiO2 S (11)
preferentially partition into the overflow stream. When a portion of
SiO2 particles is carried with oil into the overflow, the separation effi- Plugging Eq. (10) and Eq. (11) into Eq. (9) gives the following ex-
ciency of SiO2 should be lowered. Indeed, such a decrease was observed pression for the fraction of SiO2 that is captured in oil/SiO2 aggregates
experimentally (filled squares versus empty squares in Fig. 4). free free + agg
x=
Of the two suspended phases that make up the aggregates, one phase 1
[1 (1 oil )(1 S )] (1 free )
(12)
can be considered a “lead” phase while another one - a “follower” phase.
S

The distinction is drawn based on the separation behavior of the ag-
gregates: in the degree that aggregates preferentially separate as one of
the phases, that phase is the “lead” and the other one is the “follower”. In
the present case, oil is the “lead” while particulate SiO2 is the “follower”.
3.3. Fraction of SiO2 captured in oil/SiO2 aggregates: Model and model
predictions
Assuming that x is the fraction of SiO2 that is captured in oil/SiO2
aggregates, the overall concentration of SiO2 in the three-phase inflow,
CinSiO2 , can be expressed as
Applied to results obtained with SLHC, Eq. (12) predicts that the
fraction x of SiO2 captured in oil/SiO2 aggregates is 35.1%, 31.0%,
40.9%, and 32.3% for flow ratios of 30.0%, 17.0%, 9.0%, and 6.0%,
respectively. Applied to results obtained with LLHC, Eq. (12) predicts
that the fraction x of SiO2 captured in oil/SiO2 aggregates is 10.0%,
4.1%, 1.1%, and < 0.1% for split ratios of 17%, 9.5%, 4.5%, and 3.2%,
respectively. The dependence of x on the flow distribution for LLHC can
be explained by the higher shear in LLHC that can possibly break up the
aggregates. The decrease of x with a decrease in the split ratio points to
the higher aggregate break-up in the underflow, which is the higher
flow rate stream for low split ratios.

CinSiO2 = Cinfree + Cinagg (5) 3.4. Implications and future work

where Cinfree = (1 x ) CinSiO2 is the concentration of oil-free SiO2 in the Compared with oil-free sand and sand-free oil, three-phase mixtures
inflow, and Cinagg = xCinSiO2 is the concentration of SiO2 captured in oil/ with oil/sand aggregates are more difficult to separate by

7
A.V. Gorobets and V.V. Tarabara
sedimentation and flotation because of a smaller density difference
between the aggregates and the continuous phase. Featuring very high
centripetal accelerations (g-force typically in the 500 g to 5000 g range
[39]) hydrocyclones have a unique advantage over the traditional
gravity-based technologies in treating such challenging feeds. In addi-
tion, hydrocyclones have a much smaller footprint and a higher
throughput than gravity separators. For example, the SLHC tested in the
present work achieves ~50% removal of both SiO2 particles and oil at
the inflow rate of 20 L/min. Given the device volume of ~184 cm3, this
translates into the hydraulic residence time of ~0.5 s. By contrast, the
roughly same level of separation of 50% (based on turbidity reduction;
Fig. S1c) by gravity requires settling times 3 to 4 orders of magnitude
higher (~1 h). Furthermore, hydrocyclones have an additional ad-
vantage over gravity settlers in that a high shear within hydrocyclones
may break up OPAs and thereby improve separation performance.
The present study is preliminary with its scope limited to a simple
model feed and two hydrocyclone configurations. Future work should
explore a broader set of operational conditions and consider practically
relevant feeds with oil and solid phases of a range of properties.
Different sizes, densities and concentrations of particles should trans-
late into different aggregation kinetics, different morphologies, sizes
and densities of OPAs and, by extension, different separation behaviors.
Surfactants, drag reducers, and other dissolved components commonly
present in the continuous phase can affect stability of droplets and
OPAs. Understanding of physicochemical properties of OPAs and their
hydrodynamic interactions within the swirling flow of a hydrocyclone
can provide guidance on how to better design and operate hydro-
cyclones to separate such three-phase mixtures.
4. Conclusions
The study presents preliminary results on the separation of a three-
phase (oil, particulate SiO2, water) feed by a solid–liquid separation
hydrocyclone (SLHC) and a liquid–liquid separation hydrocyclone
(LLHC). The feed is challenging because of the small particle sizes of the
dispersed phase (d 0.5 of 13.5 µm and 16.0 µm for SiO2 and oil, respec-
tively) and because of the presence of oil/SiO2 aggregates with a lower
density differential with respect to water, than oil-free SiO2 and SiO2-
free oil. To our knowledge, this study is the first to explore separation of
oil-particle aggregates by conventional hydrocyclones.
A set of separation tests spanning a range of split ratios showed that
the presence of OPAs does not affect the efficiency of oil separation but
lowers the efficiency of separation of solids, especially at lower re-
coveries. The trends indicate that in both SLHC and LLHC the oil/SiO2
aggregates behave as oil droplets and preferentially partition into the
overflow stream. We operationally define oil and silica as the “lead” and
the “follower” phases, respectively wherein the separation behavior of
two-phase aggregates is that of the “lead” phase. Based on the above
findings, a model is developed to calculate the fraction of the “follower”
phase incorporated in aggregates. Applied to SLHC data, the model
shows that ~30% to 40% of SiO2 is captured in oil/SiO2 aggregates and
that the fraction does not depend on the split ratio. In LLHC, however, oil
and SiO2 appear to exist mostly as separate phases. During deoiling by
LLHC, the fraction of SiO2 locked up in oil/SiO2 aggregates does not
exceed 10% and the fraction is lower for lower split ratios; these ob-
servations can be attributed to aggregate break-up in a higher shear flow
in LLHC. While the scope of the study is limited to a simple model feed
and two hydrocyclone configurations, the results and the proposed
methodology can help frame future work on the design of treatment
processes for separating complex dispersions with oil-particle aggregates.
CRediT authorship contribution statement
Andrii V. Gorobets: Conceptualization, Methodology, Validation,
Formal analysis, Investigation, Resources, Data curation, Writing -
original draft, Writing - review & editing, Visualization.
8
Separation and Purification Technology 237 (2020) 116466
Volodymyr V. Tarabara: Conceptualization, Methodology,
Validation, Formal analysis, Writing - review & editing, Visualization,
Supervision, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This material is based upon work supported in part by the U.S
Environmental Protection Agency award no. RC-83518301, the U.S.
National Science Foundation (award no. IIA-1243433), and MSU
Foundation (Strategic Partnership Grant no. 71-1624).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.seppur.2019.116466.
References
[1] E.T. Igunnu, G.Z. Chen, Produced water treatment technologies, Int. J. Low-Carbon
Technol. 9 (2012) 157–177.
[2] T. Liden, I.C. Santos, Z.L.S. Hildenbrand, K. A., Treatment modalities for the reuse
of produced waste from oil and gas development, Sci. Total Environ., 643 (2018)
107–118.
[3] A. Fakhru’l-Razi, A. Pendashteh, L.C. Abdullah, D.R.A. Biak, S.S. Madaeni, Z.Z.
Abidin, Review of technologies for oil and gas produced water treatment, J. Hazard.
Mater., 170 (2009) 530–551.
[4] M. Bagheri, R. Roshandel, J. Shayegan, Optimal selection of an integrated produced
water treatment system in the upstream of oil industry, Proc. Saf. Environ. 117
(2018) 67–81.
[5] K. Lee, Oil-particle interactions in aquatic environments: Influence on the transport,
fate, effect and remediation of oil spills, Spill Sci. Technol. Bull. 8 (2002) 3–8.
[6] U. Bandara, P. Yapa, H. Xi, Fate and transport of oil in sediment laden marine
waters, J. Hydro-Environ. Res. 5 (2011) 145–156.
[7] Y. Gong, X. Zhao, Z. Cai, S. O’Reilly, X. Hao, D. Zhao, A review of oil, dispersed oil
and sediment interactions in the aquatic environment: Influence on the fate,
transport and remediation of oil spills, Mar. Pollut. Bull. 79 (2014) 16–33.
[8] F. Fitzpatrick, M.C. Boufadel, R. Johnson, K. Lee, T.P. Graan, A.C. Bejarano, Z. Zhu,
D. Waterman, D.M. Capone, E. Hayter, S.K. Hamilton, T. Dekker, M.H. Garcia,
J.S. Hassan, Oil-particle interactions and submergence from crude oil spills in
marine and freshwater environments, Review of the science and future science
needs (Open-File Report 2015–1076), (2015).
[9] L. Zhao, M.C. Boufadel, X. Geng, K. Lee, T. King, B. Robinson, F. Fitzpatrick, A-
DROP: A predictive model for the formation of oil particle aggregates (OPAs), Mar.
Pollut. Bull. 106 (2016) 245–259.
[10] L. Zhao, M.C. Boufadel, J. Katz, G. Haspel, K. Lee, T. King, B. Robinson, A new
mechanism of sediment attachment to oil in turbulent flows: Projectile particles,
Environ. Sci. Technol. 51 (2017) 11020–11028.
[11] S.A. Gustitus, T.B. Clement, Formation, fate, and impacts of microscopic and
macroscopic oil-sediment residues in nearshore marine environments: A critical
review, Rev. Geophys. 55 (2017) 1130–1157.
[12] Z. Zhu, D. Waterman, M. Garcia, Modeling the transport of oil-particle aggregates
resulting from an oil spill in a freshwater environment, Environ. Fluid Mech. 18
(2018) 1–10.
[13] L. Jones, M.H. Garcia, Development of a rapid response riverine oil-particle ag-
gregate formation, transport, and fate model, J. Environ. Eng. 144 (2018)
04018125.
[14] K.L. Daly, U. Passow, J. Chanton, D. Hollande, Assessing the impacts of oil-asso-
ciated marine snow formation and sedimentation during and after the Deepwater
Horizon oil spill, Anthropocene 13 (2016) 18–33.
[15] D. Bradley, The Hydrocyclone, Pergamon Press, Oxford, 1965.
[16] L. Svarovsky, Hydrocyclones, Holt, Rinehart and Winston, London, 1984.
[17] J.M. Walsh, Produced-water-treating systems: Comparison of North Sea and deep-
water Gulf of Mexico, Oil and Gas Facilities 4 (2015) 73–86.
[18] S. Bednarski, Three-product hydrocyclone for simultaneous separation of solids
both heavier and lighter than liquid medium, Hydrocyclones, Springer, 1992, pp.
397–404.
[19] Z.-S. Bai, H.-L. Wang, S.-T. Tu, Removal of catalyst particles from oil slurry by
hydrocyclone, Separ. Sci. Technol. 44 (2009) 2067–2077.
[20] Q. Yang, H.-L. Wang, Y. Liu, Z.-M. Li, Solid/liquid separation performance of hy-
drocyclones with different cone combinations, Separ. Purif. Technol. 74 (2010)
271–279.
[21] M.J. Mann, Full-scale and pilot-scale soil washing, J. Hazard. Mater. 66 (1999)
A.V. Gorobets and V.V. Tarabara
119–136.
[22] L. Ma, Q. Yang, Y. Huang, P. Qian, J.G. Wang, Pilot test on the removal of coke
powder from quench oil using a hydrocyclone, Chem. Eng. Technol. 36 (2013)
696–702.
[23] M. Motin, V.V. Tarabara, C.A. Petty, A. Benard, Hydrodynamics within flooded
hydrocyclones during excursion in the feed rate: Understanding of turndown ratio,
Separ. Purif. Technol. 185 (2017) 41–53.
[24] Q. Yang, Z.M. Li, W.J. Lv, H.L. Wang, On the laboratory and field studies of re-
moving fine particles suspended in wastewater using mini-hydrocyclone, Separ.
Purif. Technol. 110 (2013) 93–100.
[25] Y. Liu, Q. Cheng, B. Zhang, F. Tian, Three-phase hydrocyclone separator–a review,
Chem. Eng. Res. Des. 100 (2015) 554–560.
[26] M.M. Ahmed, G.A. Ibrahim, M.G. Farghaly, Performance of a three-product hy-
drocyclone, Int. J. Miner. Process. 91 (2009) 34–40.
[27] A. Mainza, M. Powell, B. Knopjes, Differential classification of dense material in a
three-product cyclone, Miner. Eng. 17 (2004) 573–579.
[28] D. Waterman, G.M. H., Laboratory Tests of Oil-Particle Interactions in a Freshwater
Riverine Environment with Cold Lake Blend Weathered Bitumen. Technical Report,
Ven Te Chow Hydrosystems Laboratory, University of Illinois at Urbana-
Champaign, 2014.
[29] G.A.B. Young, W.D. Wakley, D.L. Taggart, S.L. Andrews, J.R. Worrel, Oil-water
separation using hydrocyclones: an experimental search for optimum dimensions,
Petrol. Sci. Eng. 11 (1994) 37–50.
[30] J. Raaf, A. Bazarko, G. Garvey, E. Hawker, R. Johnson, G. Mills, A. Pla-Dalmau, R.
Tayloe, Mineral oil tests for the MiniBooNE detector, 2001 IEEE Nuclear Science
Separation and Purification Technology 237 (2020) 116466
Symposium Conference Record (Cat. No. 01CH37310), IEEE, 2001, pp. 564–568.
[31] NIST, Standard Reference Material 1922. Liquid Refractive Index - Mineral Oil,
Gaithersburg, MD, 2009.
[32] C.K. Wentworth, A scale of grade and class terms for clastic sediments, J. Geol. 30
(1922) 377–392.
[33] L. Zhao, J. Torlapati, M.C. Boufadel, T. King, B. Robinson, K. Lee, VDROP: A
comprehensive model for droplet formation of oils and gases in liquids -
Incorporation of the interfacial tension and droplet viscosity, Chem. Eng. J. 253
(2014) 93–106.
[34] A.F. Rawle, Best practice in laser diffraction - a robustness study of the optical
properties of silica, Procedia Eng. 102 (2015) 182–189.
[35] C.M. Keck, R.H. Muller, Size analysis of submicron particles by laser diffractometry
- 90% of the published measurements are false, Int. J. Pharm. 355 (2008) 150–163.
[36] E. Hayter, R. McCulloch, T. Redder, M. Boufadel, R. Johnson, F. Fitzpatrick,
Modeling the transport of oil particle aggregates and mixed sediment in surface
waters (ERDC Technical Report), U.S. Army Corps of Engineers, Vicksburg, MS,
2015.
[37] National Academies of Sciences, Engineering, and Medicine. Spills of Diluted
Bitumen from Pipelines: A Comparative Study of Environmental Fate, Effects, and
Response, Washington, DC: The National Academies Press, 2016.
[38] T. Frankiewicz, Understanding the fundamentals of water treatment. The dirty
dozen-12 common causes of poor water quality, Produced Water Seminar, Houton,
TX, 2001.
[39] A. Davailles, E. Climent, F. Bourgeois, Fundamental understanding of swirling flow
pattern in hydrocyclones, Separ. Purif. Technol. 92 (2012) 152–160.