Desalination 312 (2013) 67–74

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Desalination
journal homepage: www.elsevier.com/locate/desal

Pilot demonstration of the NH3/CO2 forward osmosis desalination process on high

salinity brines
Robert L. McGinnis ⁎, 1, Nathan T. Hancock ⁎⁎, Marek S. Nowosielski-Slepowron, Gary D. McGurgan 2
Oasys Water, Inc. 21 Drydock Ave. 7th Floor, Boston, MA 02210, USA

H I G H L I G H T S

► Frac flowback from the Marcellus shale was treated in a NH3/CO2 FO pilot system.
► Average feed TDS was 73,000 ± 4200 mg/L, and hardness was 17,000 ± 3000 mg/L as CaCO3.
► Product water concentration was 300 ± 115 mg/L TDS.
► Energy use was 57% less than that estimated for an open cycle evaporator.
► Commercial system energy use is projected to be 42% less than MVC evaporators.

a r t i c l e i n f o a b s t r a c t

Article history: An NH3/CO2 forward osmosis (FO) membrane brine concentrator (MBC) pilot was tested in the desalination of frac
Received 25 October 2012 flowback and produced waters from natural gas extraction operations in the Marcellus shale region. The average
Received in revised form 22 November 2012 concentration of these waters was 73,000±4200 mg/L total dissolved solids (TDS), with an average hardness of
Accepted 27 November 2012
17,000±3000 mg/L as CaCO3. Pretreatment included chemical softening, media filtration, activated carbon, and
Available online 20 December 2012
cartridge filtration. Average pilot performance characteristics were: system recovery of 64±2.2%, nominal water
Keywords:
flux of 2.6±0.12 L/m2-h, concentrated brine concentration of 180,000±19,000 mg/L TDS, and product water
Forward osmosis with 300±115 mg/L TDS. The thermal energy required by the FO MBC pilot, when operated within the efficient
FO flow specification of the draw solution recycling system, averaged 275±12 kWhth/m3 of product water, approx-
Ammonia carbon dioxide forward osmosis imately 57% less thermal energy input than that estimated for a conventional evaporator operated in a comparable
NH3/CO2 single stage, non-mechanical vapor compression (MVC) configuration. In an MVC configuration, which uses elec-
Desalination trical rather than thermal energy, modeling indicates that the FO MBC process will require 42% less electrical en-
Brine concentrator ergy than a conventional forced circulation MVC evaporator.
Hydraulic fracturing
© 2012 Elsevier B.V. All rights reserved.
Shale gas
Produced water
Brine

1. Introduction
Relying on hydraulic fracturing to stimulate production of oil and nat-
ural gas from shale formations leads to a tremendous demand on fresh
water resources. Approximately 13,000 m3 of water is required per well
during the development and stimulation phase [1]. Subsequently, the
stimulation of the well results in the production of large volumes of
high salinity is frac-flowback and co-produced water (the mixture of
both streams referred to subsequently as “produced water”). Global
⁎ Corresponding author. Tel.: +339-203-7445
** Corresponding author. Tel.: +617-599-8253
E-mail addresses: robertlmcginnis@gmail.com (R.L. McGinnis),
nhancock@oasyswater.com (N.T. Hancock).
1
Current affiliation: Copia Research, 195 Binney Street, #1402, Cambridge, MA
02142, USA.
2
Current affiliation: GE Water and Power, 5951 Clearwater Drive, Minnetonka,
MN 55343, USA.
oil and gas produced water volumes now total more than 11 billion m 3
of water per year, and often contain chemicals used in the oil and gas
recovery process [2]. These chemicals, along with the salinity of the pro-
duced water stream, cause concern about the impacts of hydraulic frac-
turing activities on water resources in the environment [2]. Methods of
managing these produced water streams include disposal through
wastewater treatment facilities into fresh water streams, spreading on
roads for dust suppression, deep well injection, reuse with dilution in
hydraulic fracturing operations [3], and desalination [4]. Desalination
may be required for beneficial use of the produced water or to enable
surface discharge [4,5]. As the concentration of these streams is typical-
ly between 70,000 and 250,000 mg/L total dissolved solids (TDS), only
evaporative desalination technologies are typically capable of treating
these streams to the lower salinity levels required for surface discharge.
Commercially available evaporation technologies include mechanical
vapor compression (“MVC”, sometimes also referred to as mechanical
vapor recompression, or “MVR”) evaporators, as well as open cycle

0011-9164/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2012.11.032
68 R.L. McGinnis et al. / Desalination 312 (2013) 67–74
evaporation techniques that evaporate water to the air rather than pro-
ducing a fresh water stream [1]. An additional proposed evaporation
technique, that is not yet commercially available, is membrane distilla-
tion. This process is expected to have similar performance characteristics
to evaporative techniques that produce a fresh water stream, while
reducing the capital cost of such treatment. No pilot data from treatment
of oil and gas waters using membrane distillation is yet available, with
respect to either capital and operating costs, or energy use [6]. Commer-
cially available evaporative desalination technologies, however, are
perceived as having prohibitive cost and complexity by the oil and
gas industry, delaying or preventing their use.
One proposed method for reducing the cost of desalination is the use
of an osmotically driven membrane process known as forward osmosis
(FO). In this process, a solution consisting of specially selected solutes
(often called the “draw solution”) is used to provide a solution with a
lower chemical potential energy of water than the feed stream to be
treated. A semi-permeable membrane is used to employ this difference
in potential energy (manifested by an osmotic pressure gradient) to
spontaneously dewater the feed stream by means of water permeation
through the semi-permeable membrane, into the draw solution, which
becomes dilute. A secondary process is then used to re-concentrate the
draw solution, producing water with substantially less TDS compared to
the feed. The energy or fuel resource requirements of the secondary pro-
cess may be less than those of conventional alternatives such as reverse
osmosis (RO) or evaporation, and fouling and scaling phenomena in the
FO membrane system may be substantially reduced [7,8]. In this study,
an FO membrane brine concentrator (MBC), based on an NH3/CO2 draw
solution [9] (a mixture of thermolytic ionic solutes that disassociate into
gases when a solution containing them is heated), was tested in the desa-
lination of produced water from natural gas production in the Marcellus
shale. The primary objective of this study is to experimentally investigate
the pilot scale performance of an NH3/CO2 FO desalination process. A sec-
ondary objective is to determine if the FO MBC process tested in this study
is a viable option to treat oil and gas produced water.
Previous studies established the necessary characteristics of mem-
branes for an NH3/CO2 FO process [10], an estimate of the energy re-
quired for the separation and re-concentration of the NH3/CO2 draw
solution based on modeling along with several methods for thermal in-
tegration [11], and the potential benefits of the use of the process [12].
In this paper, we report experimental findings from the testing of a
fully integrated, steady state NH3/CO2 FO process. For this study, a con-
tainerized pilot comprising the FO membrane system, draw solution
recycling system, heating and cooling subsystems (consisting of a boiler
delivering system heat, and an evaporative cooling tower providing
system cooling), instruments, and automated controls (Oasys Water,
Inc.), was delivered to the field pilot location in Southern Massachusetts
for testing. A conventional skid-mounted pretreatment system (Oasys
Water, Inc.), designed for the pilot trial, was also delivered to this site.
The feedwater treated by the pilot system was produced water
from shale gas production in the Marcellus shale region of Southern
Pennsylvania. This water was sent by trucks, without selection or prior
treatment, to the pilot site in Southern Massachusetts. The water was
understood to be a blend of several sources, and to change in origin
and composition daily. Pilot testing was conducted over a period of
four months, with the longest continuous testing periods consisting of
approximately 100-hour intervals each.
2. Materials and methods
2.1. Pilot design
The FO MBC pilot system design was based on an FO membrane
array of spiral wound membrane elements, 0.1 m (4 in.) in diameter
and 1 m (40 in.) long, in a 2 × 1 configuration of membrane pressure
vessels containing 6 elements each. The elements contained approxi-
mately 3.3 m2 installed membrane area each, for a total installed area
of approximately 59.4 m2. The spiral wound elements were modified
to accommodate two cross-flow streams, in a manner described in pre-
vious publications [7]. The elements employ mesh feed channel spacers
commonly used in reverse osmosis (RO) elements to induce turbulent
flow. The membrane contained within the elements is a polyamide FO
thin film composite, (Oasys Water, Inc., Boston, MA), the fabrication
and characteristics of which were previously described [13]. The FO
membrane mass transfer parameters (water permeability (A), NaCl
salt permeability (B), and structural parameter (S) measured by a stan-
dardized method [14]) for the membrane employed in the spiral wound
elements are summarized in Table 1.
Pretreated Marcellus shale produced water (referred to subsequent-
ly as “feed brine” in reference to pilot streams) was directed to the feed
channel contacting the active layer side of the membrane. The pilot feed
flow rate was designed to be variable between 5.5 and 22.1 m 3/day
(34.3 and 137.1 bbl/day). The draw solution was directed along the
support layer side of the membrane in a counter-current flow path,
with a flow rate typically between 50 and 100% that of the feed brine
flow rate. The pressures of both the feed brine and concentrated draw
solution streams were dictated solely by the pressure drop characteris-
tics of the membrane solution channels, resulting in typically less than
40 psi drop for each stream throughout the membrane array. Residence
volumes of the feed and draw solutions within the pilot were typically
less than 2 m3 each. The draw solution concentration was maintained
at between 5.5 and 6.0 M, on a carbon molarity basis, by controlling the
energy supplied to the distillation columns, resulting in the appropriate
amount of vapor transfer to the column condenser. The ratio of ammonia
to carbon dioxide of the draw solution was approximately 2.4:1.
The FO MBC pilot process is shown schematically in Fig. 1A. Water
permeated the membrane from the feedwater to the draw solution, con-
centrating the feedwater, and diluting the draw solution. The diluted
draw solution was directed to a distillation column for thermal stripping
of its draw solutes. The reject from the membrane system, (referred to
subsequently as “concentrated brine”) was directed to a separate distilla-
tion column (referred to as the “brine stripper”), stripping it of any draw
solutes introduced by reverse salt flux [15,16] in the membrane array.
Both columns were operated at atmospheric pressure, with no energy re-
covery system (no MVC or heat pump). The vaporized draw solutes from
both columns were directed by means of flexible pipes to condensers
(heat exchangers), also at atmospheric pressure, cooled by a closed loop
of cooling water circulating between the condensers and an evaporative
cooling tower. This cooling caused the vapor streams to condense and
these streams were combined to form the re-concentrated draw solution,
which was continuously reused within the process. No energy input was
required for the condensation of the draw solute vapors, other than the
power used by the fan of the cooling tower, which is included in the elec-
trical power use measured for the pilot process.
The product water from the dilute draw solution column was direct-
ed to a conventional RO system for a “second pass” reduction in product
TDS, to ensure that the system met the 500 mg/L product water TDS
specification. This was necessary due to the high average TDS of the
brine on the feed side of the FO MBC membrane array (approximately
140,000 ppm). Even with FO membranes using polyamide chemistries
achieving 99.5% in standardized testing (membranes used in the pilot
achieved 98% in such tests), reduction to 500 ppm in a single pass is
not possible. The RO system was run at high pressure (approximately
Table 1
Summary of polyamide TFC FO membrane mass transfer parameters for the membrane
employed in this study.
Parameter Value Units
Pure water permeability (A) 1.13 × 10−11 ± 1.13 × 10−13 m/s-Pa
Solute (NaCl) permeability (B) 1.76 × 10−7 ± 2.18 × 10−8 m/s
Structural parameter (S) 266 ± 45.5 μm
 R.L. McGinnis et al. / Desalination 312 (2013) 67–74 69

Fig. 1. (A) Block flow diagram of the MBC. Darkening color gradation indicates concentration of a stream while a lightening color gradient indicates dilution. Flows from the dis-
tillation column and brine stripper to the condenser are gas flows. (B) Photographs of the exterior and interior of the FO MBC pilot system.

800 psi) to maximize system recovery. Concentrate reject from the RO
system was directed to the feed brine stream entering the pilot mem-
brane system. The energy used by the RO system is included in the elec-
trical energy use reported here for the pilot system. Photographs of the
pilot system are shown in Fig. 1B.
2.2. Pretreatment
Pretreatment of raw feed brine was conducted using conventional
methods. Raw feed brine was chemically oxidized with NaOCl, floccu-
lated with FeCl3 and softened using NaOH to adjust its pH and Na2CO3
70 R.L. McGinnis et al. / Desalination 312 (2013) 67–74
to increase its alkalinity. Solids from the slurry formed by this process
were removed by the use of a filter press. Softened water was further
treated by manganese greensand media filtration (continuously
regenerated by the addition of KMnO4); activated carbon adsorption,
to reduce the concentration of organic compounds in the feed brine
directed to the FO MBC process; and cartridge filtration. A scale inhib-
itor (Vitec™ 7000) was added to the feed stream after pretreatment,
to ensure no scaling events occurred (Applied Membranes, Inc., Vista,
CA).
2.3. Chemical analysis
Draw solution carbon molarity and ammonia to carbon dioxide
molar ratio were determined by the titration of a weak base with a
strong monoprotic acid (HCl). Draw solution samples were diluted by
a factor of 200 with doubly deionized water (D4631, Thermo Scientific
with RO pretreatment) prior to analysis. Sample volume used for each
dilution was gravimetrically validated based on sample density
(GD-503-NTEP, Sartorius). A 0.1 M HCl acid solution was created from
37% stock ACS grade HCl (Thermo Scientific) and utilized for all draw
solution titrations. Titrant concentration was validated by titration
with a known molarity of NaOH (Fisher Chemical) created by the disso-
lution of a known weight of ACS grade NaOH pellets into doubly deion-
ized water. Weak base titration of the draw solution occurs through two
chemical equilibrium stages:
NH4 COONH2 þ ðNH4 Þ2 CO3 þ H2 O þ 2HCl↔2NH4 HCO3 þ 2NH4 Cl ð1Þ
NH4 HCO3 þ HCl↔NH4 Cl þ CO2 ðgÞ þ H2 O: ð2Þ
An automatic titrator (HI-902c, Hanna Instruments) was used to de-
termine the moles of titrant required to achieve these two equivalence
points along the titration curve. The number of moles of titrant con-
sumed to achieve the second equivalence point indicates the moles of ni-
trogen in solution. The moles of titrant required to transition between
the first and second equivalence points are equivalent to the number of
moles of carbon.
TDS was measured according to standard method 2540C. Measure-
ment of primary anions (bromide, chloride, fluoride, nitrate, phosphate,
and sulfate) and cations (ammonium, calcium, magnesium, potassium,
and sodium) was performed with ion chromatography (simultaneous
injection tandem ICS-1100, Thermo Scientific). Anions were analyzed
according to standard method 4110A. Cations were analyzed according
to ASTM method D6919-09. Phenolphthalein and total alkalinity were
measured by digital titration with a colorimetric method (method
8203, Hach Company) and used to calculate carbonate and bicarbonate
concentrations for ion charge balance analysis. Sample aliquots were
drawn from the FO MBC feed, FO membrane concentrate, final concen-
trate, and MBC product at regular intervals. A total of 54 aliquots were
drawn from each stream during the pilot study.
Measurements of gross alpha and beta particle emitters were made
according to standard method 7110B. TOC was analyzed according to
standard method 5310B. VOCs were analyzed according to method
SW846 8260C. A total of 76 VOCs were test for each sample, and 17 ali-
quots for VOC and TOC analysis were drawn from each stream during
the pilot study. Of these, only acetone was detected in the feed brine.
Trace inorganic constituents were measured according to method
SW846 6010C except for mercury, which was measured according to
EPA 245.1/7470A. Data for individual water samples was discarded if
the ion charge balance exceeded a percentage difference greater than
7% or if TDS and estimated TDS based on the summation of individual
ions exceeded a percentage difference of 7%.
2.4. Calculation of FO membrane system water flux and recovery, and energy
consumption, of pilot FO MBC
Membrane system water flux was calculated by the net increase in
draw solution flow rate through the FO membrane array measured by
electronic flow transmitters (3-2551, George Fischer), divided by the
total installed surface area of FO membrane in the array: Jw = (QDS,
Out − QDS, in) / A, where DS is draw solution, and A is membrane area.
While this describes the overall system water flux, the flux calculated
by this method does not consider inefficiencies in area utilization
known to occur within modified spiral wound membrane elements
of the type used in the FO MBC pilot. Portions of the installed area
may not contribute equally to water flux, due to superficial velocity
distributions that can lead to stagnant regions within the element
[17]. For this reason, the reported flux should not be assumed to in-
dicate the actual water flux at any specific location in the membrane
array, but should be interpreted as a measure of overall system per-
formance. Water recovery is the ratio between the flow rate of prod-
uct water and the feed brine being fed to the FO MBC: Recovery =
Qp / Qf .
Energy consumption of the diluted draw solution distillation col-
umn was measured by correlating the pressure (673-8, Dwyer In-
struments) of the heating steam supplied to the reboiler (heat
exchanger with heating steam on one side, and column bottom prod-
uct circulating between the column sump and reboiler on the other)
with the thermal energy transferred to the column as steam rising
through the column internals. To establish this calibration, the col-
umn was run with low salinity (municipal tap) water in the column
sump and heating steam supplied to the reboiler. This caused a por-
tion of the water in the column sump to be vaporized, in proportion to
the heat supplied to the reboiler at each steam supply pressure. This
steam rose through the column to the condenser (a second heat exchang-
er, with column steam on one side, and circulating cooling water on the
other). The steam was condensed completely, collected, and measured
on a balance (RC30LS, Ohaus) during a set time interval to determine
the condensate mass flow rate m _ =(Δmass/Δtime). The condensate
mass flow rate was multiplied by the specific enthalpy of the vaporization
of water (2256.4 kJ/kg) at 100 °C and 1 atm. By this method, a correlation
between column heat flow and measured heating steam supply pressure
was established.
During normal pilot testing, heating steam supply pressure to the di-
lute draw solution distillation column was measured continuously and
averaged over the testing interval for each steady state pilot testing con-
dition. The linear fit of the steam supply pressure data was employed to
calculate the energy consumption under that condition, using the steam
supply pressure/heat flow calibration. The average observed column en-
ergy use during the operation interval was divided by the mass flow
rate of product water over that interval to obtain the specific energy con-
sumption of the dilute draw solution distillation column per m3 of water
produced.
The brine stripper introduced heat for separation of draw solutes
from the concentrated brine stream by direct steam injection through a
side port orifice. Brine stripper heat consumption was calculated based
on steam feed pressure to the brine stripper through the 0.25-inch diam-
eter orifice, using linear interpolation from an orifice flow chart. The spe-
cific energy consumption of the brine stripper was calculated as brine
stripper energy use per m3 of pilot product water. This brine stripper
specific energy use was added to the dilute draw solution distillation col-
umn specific energy use to give overall pilot system specific thermal en-
ergy use for the low salinity water product.
Using these methods, determination of specific energy consumption
for the pilot system was furthermore conducted under flow conditions
matching specifications for the diluted draw solution distillation col-
umn used in the pilot system. The diameter of the column was matched
to a diluted draw solution flow rate of 17.3 m 3/day, corresponding to a
system feedwater rate of approximately 21.8 m3/day. Significant
 R.L. McGinnis et al. / Desalination 312 (2013) 67–74 71

deviations from this flow rate were expected to cause corresponding
changes to the liquid loading rate of the column packing, a condition
known to cause significant deviations from efficient column perfor-
mance, due to dewetting phenomena and maldistribution of liquid
flows [18]. Therefore, even though the column was designed to operate
within a system feed flow rate range of 5.5 to 22.1 m 3/day (to allow for
a wide range of testing conditions for the FO membrane system), only
flows above approximately 16.3 m 3/day allowed for accurate measure-
ment of specific energy use.
The electrical power demand of the supporting systems for the pilot,
including circulation pumps and the cooling tower fan, was based on
measured flow rates and hydraulic pressure increases, the
motor-to-pump efficiency, and the variable frequency drive (VFD) effi-
Q ⋅ΔP
ciency for each pump according to P ¼ η , where P is power, Q is
motor ⋅ηVFD
the flow rate, ΔP is the hydraulic pressure increase performed by the
pump, and η is the efficiency of the motor and VFD, respectively.
Power draw for the RO post treatment process was calculated by mea-
suring the amperage draw of the pump operating with a 460 V,
pffiffiffi
3-phase line according to the equation Power ¼ 3⋅V⋅I⋅PF, where V is
the voltage, I is the current draw of the motor, and PF is the power factor
of the variable frequency drive. The power demand of each pump was
converted to specific energy consumption per kg of product water by as-
suming 24-hour continuous operation and dividing by the known prod-
uct mass flow rate.
2.5. Calculating theoretical minimum energy consumption of single stage
process and estimated energy consumption of MVC mode of operation of
the FO MBC
It is useful to compare the theoretical energy demand of (i) a conven-
tional evaporation process (solvent changes phase to achieve separation),
and (ii) the process investigated here, a membrane brine concentrator
using forward osmosis with thermally separable solutes (solutes change
phase to achieve separation). The two cases are shown diagrammatically
in Fig. 2A and B with calculated enthalpies for each stream. In the first
case (i), one may calculate the enthalpy required to evaporate 1 kg of
pure water (stream 2) from 1.6 kg of water with 120,000 mg of NaCl
(stream 1), concentrating this stream by 62.5% to 120,000 mg of NaCl
in 0.6 kg of water (~200,000 mg/L at 20 °C) (stream 3). In the second
case (ii) a perfectly selective membrane is presumed to have contacted
the 75,000 mg/L stream with a 6.0 M (as carbon) and 12.0 M (as nitro-
gen) draw solution. Water spontaneously diffuses through the selective

A (i)

B (ii)

Fig. 2. Mass and enthalpy balance diagrams based on thermophysical modeling. (A) Case (i), production of 1 kg of pure water through evaporation of the solvent (water) from a
saline source. (B) Case (ii), production of 1 kg of water through evaporation of the solute (shown here as molar flows of C and N, which are equivalent to molar flows of CO2 and NH3
in stream (5)) from a draw solution diluted by permeate from an FO membrane process.
72 R.L. McGinnis et al. / Desalination 312 (2013) 67–74
membrane barrier and concentrates the feed to 200,000 mg/L, simulta-
neously diluting the draw solution to 1 kg of water with 2.5 M as carbon
and 5.0 M as nitrogen (stream 4). The enthalpy required to fully vaporize
the draw solutes (stream 5) (assuming infinite equilibrium stages) and
produce 1 kg of pure water (stream 6) may then be calculated. A com-
mercial thermophysical modeling software package (OLI Stream Analyz-
er, OLI Systems Inc.) was employed to calculate the enthalpies of the
various streams. The change in enthalpy for each process is calculated
by the sum of the enthalpy for each stream flowing out of the pro-
cess minus the enthalpy of the stream flowing into the process. For
case (i) shown in Fig. 2A the enthalpy change is 633 W-h and is com-
posed of the specific enthalpy used to produce 1 kg of water vapor that
will be condensed to form 1 kg of purified water; for case (ii) shown in
Fig. 2B the enthalpy change is 102 W-h and is composed of the specific
enthalpy to produce 2.5 moles of carbon dioxide and 5 moles of ammonia
as gases, leaving behind 1 kg of purified water. These calculations demon-
strate that for a concentrated saline feed, under ideal conditions, it re-
quires approximately six times more energy, per kg of purified water
produced, to purify the stream by evaporation of water rather than by
evaporation of ammonia and carbon dioxide gases from an FO draw solu-
tion. Real engineered FO systems, although unlikely to fully achieve these
theoretical energy requirements, do in practice derive their energy effi-
ciency advantage over solvent evaporation methods from this fundamen-
tal difference in required energy input.
Energy consumption of the FO MBC process using MVC latent heat re-
covery was modeled with chemical process modeling software (Aspen
Plus 7.2, Aspen Technology, Inc.), employing the enh3co electrolyte
model. An example process flow diagram (PFD) from the modeling pro-
cess is shown in Fig. 3. The basis for the model was a system with an
input of 636 m3/day (4000 bbl/day or bpd) feed brine that would operate
in the same manner as the pilot system, but with a compressor to recover
latent heat from the solute gas stream. The design basis is for a diluted
draw solution distillation column consisting of 12 theoretical stages, pro-
ducing a product with b 500 mg/L TDS and b 1 mg/L NH3; a concentrated
brine draw solute recovery column consisting of 10 theoretical stages,
producing a concentrated brine with >200,000 mg/L TDS and b5 mg/L
NH3; an FO membrane with polyamide chemistry that achieves 99.8%
salt rejection in standard seawater RO tests; and a compressor driven
by an internal combustion engine configured for partial capture of
21
Pump
Compressor
Feed
6
1 Feed-product
heat exchanger
2 3 4 12
Pressure Pre-heater
reducer
5 13
Column
Fig. 3. Aspen Plus PFD for the dilute draw solution distillation column subsystem, showing the use of a compressor for recovery of latent heat from the draw solution solute vapor
stream. Membrane system and brine stripping column are not shown.
exhaust heat. Electrical energy required for circulation pumps, lights, con-
trols, and post-treatment RO is provided by a separate mobile generator.
3. Results and discussion
3.1. System operation
The initial testing of the NH3/CO2 FO MBC pilot system consisted of the
exploration of a wide range of system operating conditions to establish
the optimal conditions for economical and efficient steady state perfor-
mance. This period of testing occupied the first 10 weeks of the 16-
week trial. Following this period, the system was operated for 5 weeks
in both 24 h/day (4–5 days/week), and daily start up and shut down
modes of operation, during which further exploration of changes in oper-
ating conditions were less frequent, and covered smaller spans of the pos-
sible operating envelope. Experimental data on average feed and product
water quality shown is from this 5-week testing period, as well as from
the final week of testing. In the final week of the trial, the system was op-
erated without modification of operating conditions to allow measure-
ment of a longer period of steady state performance. The experimental
data presented in Fig. 4 shows water flux and recovery measured during
this 100-hour period. The feed rate during the final 100-hour period was
set to 5.5 m3/day. The average water flux was 2.6±0.12 L/m2-h (LMH).
The average water recovery of the system was 64±2.2%, producing a
concentrated brine concentration averaging 180,000±19,000 mg/L
TDS. During this 100-hour period, no makeup draw solution or draw solu-
tion solutes were added to the draw solution, which maintained a volume
of approximately 200 L throughout the testing period. The carbon molarity
of the draw solution was 6.0±0.16 mol C/L and the nitrogen to carbon
molar ratio was 2.4±0.04 for the duration of this 100-hour period.
By way of comparison, evaporative brine concentrators used in similar
applications typically treat water of between 70,000 and 80,000 mg/L,
concentrating it to between 200,000 and 230,000 mg/L, a similar degree
of concentration (and therefore rate of recovery) to that observed for
the FO MBC [1]. RO systems typically have water flux rates higher than
those observed here, for feed streams of salinities of up to approximately
50,000 mg/L, but are unable to treat waters of the concentrations treated
in this study.
22 Concentrated product
18 To fan cooler
10
17 19 Condenser
11
Engine exhaust Product
heat exchanger water
16
14 15
Flash drum Pump
9
8
7
Pump
20
 R.L. McGinnis et al. / Desalination 312 (2013) 67–74 73

5 80% The average ammonium/ammonia concentration of the concentrat-

ed brine was 121± 43.7 mg-NH4/L. The average alkalinity of the con-
70%
centrated brine was 9340±3360 mg-CaCO3/L. It is apparent from the
4
Water Flux,L/m2 -hr

60% measured water recovery, and water quality shown in Table 2, that

Water Recovery
the ammonium/ammonia and alkalinity found in the concentrated
3 50% brine is indigenous to the feed brine, rather than to reverse salt flux of
draw solution solutes.
40%
2 30% 3.3. System energy use

20% Measurement of specific energy of the pilot system was made during
1 a period of operation in which the feed rate to the pilot exceeded the min-
Water Recovery 10% imum rate necessary for efficient liquid loading in the distillation col-
Water Flux
0 0% umns. The specific thermal energy consumption of the distillation
0 20 40 60 80 100 column and brine stripper combined was 275±12 kWhth/m3 of water
Time,hr produced. The pilot system was measured to use an additional approxi-
mate 8.5 kWhe/m3 of electrical energy, for all primary and supporting
Fig. 4. System water recovery and flux plotted over the final 100-hour steady state testing processes, including circulation pumps, membrane system, distillation
period. columns, condenser, cooling tower, control systems, and post-treatment
RO, but not including pretreatment.
The pilot feed rate during this testing period was 21.8 m 3/day.
This feed rate resulted in a higher nominal system water flux (5.8±
0.66 LMH) and lower recovery (50%) than that measured during the
3.2. Water quality lower feed flow rate (5.5 m 3/day) data collection period discussed else-
where in this paper. From the perspective of the specific energy of the
The water quality data collected during the final 6-week pilot testing solute recycling system, however, the primary meaningful difference
period indicated that the product water met the water quality standards was in the diluted draw solution concentration. In the 5.5 m 3/day test
for surface discharge in the state of Pennsylvania (25 Pa. Code § period, the concentration of the diluted draw solution sent to the distil-
95.10(b)(3))(b500 mg/L TDS, b 250 mg/L chlorides, b 10 mg/L barium, lation column averaged 2.9 ±0.13 mol C/L. In the 21.8 m3/day trial
b10 mg/L strontium). Water characteristics for the pretreated feed used for specific energy measurement, the concentration averaged
brine and final product water are shown in Table 2. The average TDS 2.1 ± 0.02 mol C/L. Aspen modeling indicates that, based on this differ-
of the pretreated feed brine was 73,000 ±4,200 mg/L. The average ence in diluted draw solution concentration, the energy use in the lower
TDS of the product water was 300± 115 mg/L. High rejection of all feed rate, higher recovery case discussed elsewhere in the paper would
measured chemical species was observed. be approximately 16% higher than that measured in the higher feed
rate, lower recovery case used for the determination of specific energy
for the pilot.
For comparison to evaporative desalination methods, producing 1 kg
of water product by evaporating water from a 73,000 mg/L NaCl solution
Table 2 to a recovery of 50% (identical to the recovery of the FO MBC pilot during
Average concentrations of the chemical species measured in the pretreated feed brine specific energy testing), in a similarly configured evaporative brine con-
fed to the pilot system and the product water produced, shown with standard devia- centrator (open cycle, single stage, no energy recovery), is estimated to
tions, during the final 6-week testing period. All measurements are in mg/L, except
require an energy input of approximately 633 kWhth/m3 of thermal
those for radionuclides, which are in pCi/L, and pH. BDL stands for below detection
limit, and means the analyte concentration could not be measured because it was energy. This is 2.3 times the energy measured in the FO MBC pilot (275
below the detection limit of the instrument or method used. kWhthm3), measured in the FO MBC pilot. Desalination systems relying
on water evaporation also require additional electrical energy to power
Category Constituent Pretreated Product Solute
feed brine water rejection
circulation pumps and other auxiliary components in the range between
1 and 8 kWhe/m3 [19,20], which is similar to the range to the electrical
Cations and Aluminum 0.327 ± 0.098 BDL, b0.05 ≥78.2%
metals Ammonium 57.2 ± 28.8 0.564 ± 0.764 99.0 ± 1.43%
energy use measured in the FO MBC pilot system.
Barium 1.93 ± 1.05 BDL, b0.025 ≥97.2%
Boron 7.64 ± 2.05 BDL, b0.5 ≥91.1% 3.4. Projections of commercial system energy use
Calcium 104 ± 115 0.073 ± 0.156 99.9 ± 2.40%
Iron BDL, b0.15 BDL, b0.15 N/A
In both technology approaches to brine concentration – evaporation
Magnesium 5.54 ± 24.9 0.12 ± 0.24 97.8 ± 4.81%
Manganese BDL, b0.02 BDL, b0.02 N/A of solvent (water in conventional evaporators), or thermal vaporization
Nickel BDL, b0.05 BDL, b0.05 N/A of thermolytic solutes (NH3 and CO2 in the FO MBC) – there are several
Potassium 270 ± 200 1.61 ± 0.827 99.4 ± 0.896% methods to optimize latent heat recovery [11,20]. One method is MVC,
Silicon 7.06 ± 2.58 BDL, b0.5 ≥88.8% which is commonly used in evaporation desalination systems. In this
Sodium 28,400 ± 2390 91.8 ± 38.0 99.7 ± 0.421%
method, the vapor produced in the evaporative process is compressed,
Strontium 3.97 ± 2.07 BDL, b0.5 ≥73.4%
Anions Bicarbonate 1500 ± 2610 104 ± 45.9 93.1 ± 1.67% allowing it to transfer its latent heat to induce vaporization of a portion
Bromide 229 ± 33.1 0.669 ± 0.351 99.7 ± 0.543% of the feed brine, greatly reducing total energy input to the system
Carbonate 3090 ± 644 59.5 ± 69.6 98.1 ± 1.17% [21]. MVC based forced circulation evaporative desalination systems
Chloride 41,400 ± 3.340 81.4 ± 46.6 99.8 ± 0.577%
used to treat oil and gas produced water have been shown to
Sulfate 22.7 ± 19.6 0.047 ± 0.022 99.8 ± 0.980%
Radionuclides Gross Alpha 14.6 ± 8.73 1.48 ± 1.49 89.9 ± 1.05% require between 28 and 39 kWhe/m3 (4.5–6.2 kWhe/bbl) of feed [22],
Miscellaneous Acetone 0.298 ± 0.128 BDL, b0.025 ≥85.3% for a range of feed TDS between 45,000 and 80,000 mg/L [23]. For a
TOC 59.0 ± 9.14 BDL, b1.0 ≥98.0% feed TDS of 70,000–80,000 mg/L, this is approximately 37 kWhe/m3
pH 10.7 ± 0.800 10.7 ± 0.199 N/A (5.8 kWhe/bbl). In comparison, process modeling shows that when
TDS 73,000 ± 4200 300 ± 115 99.6 ± 0.386%
the FO MBC process is operated in an MVC configuration, where
74 R.L. McGinnis et al. / Desalination 312 (2013) 67–74
draw solute gases are compressed to allow for the reuse of their la-
tent heat in a manner similar to that of MVC evaporators, it will re-
quire a total energy input of 21 kWhe/m 3 (3.38 kWhe/bbl) of feed,
resulting in a 42% reduction in total energy use compared to a forced
circulation MVC evaporator.
3.5. Concluding remarks
The NH3/CO2 FO desalination process was experimentally investigat-
ed at the pilot scale. In the desalination of high salinity (>70,000 ppm
TDS) produced waters from shale gas exploration, it was found to achieve
feedwater recoveries similar to those of evaporative brine concentration
technologies (>60%). The product water generated in the process was
found to meet surface water discharge quality criteria (b500 mg/L TDS,
b250 mg/L chlorides, b10 mg/L barium, b10 mg/L strontium) for the
State of Pennsylvania, the state where the high salinity produced waters
originated. Retention of draw solution solutes within the system was ex-
cellent, with stable draw solution concentrations and no supplementa-
tion of draw solutes necessary in over 100 h of continuous operation.
The measured energy use of the pilot was 275 kWhth/m3 of product
water, 57% less thermal energy input than that estimated for a conven-
tional evaporator operated in a comparable single stage, non mechani-
cal vapor compression (MVC) configuration, with similar electrical
energy inputs (approximately 8 kWhe/m 3). In an MVC configuration,
the projected energy use of the FO MBC system is 21 kWhe/m3, 42%
less energy than is typically required by a conventional forced circula-
tion MVC evaporator in the same application.
RO, while using significantly less specific energy when desalinating
lower salinity feeds (approx. 2.5 kWhe/m3, for example when treating
SW at approximately 35,000 ppm TDS), is not capable of treating wa-
ters of the high TDS concentrations examined in this study. While the
NH3/CO2 FO desalination process is projected to use less energy than
that found here for the desalination of lower salinity feeds [11], it is like-
ly that heat recovery methods of the type investigated in this study will
not be sufficient to reduce its energy consumption to lower levels than
those typical of RO. Investigations of the cogeneration of water and
power, using rejected heat from power generation to drive the FO pro-
cess, may be necessary to determine if cost or energy efficiency advan-
tages may be found for NH3/CO2 FO for the treatment of lower salinity
feeds.
Acknowledgment
We thank the pilot team members at Oasys for their invaluable contri-
bution to the construction and operation of the pilot system. Funding for
this research was provided by Oasys Water, Inc.
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