ARC '16

Energy and Environment Pillar

http://dx.doi.org/10.5339/qfarc.2016.EEPP1948

Application of Osmotic Concentration for Volume Reduction of Produced/Process

Water from Gas-Field Operations
Samer Adham1, Ana Santos1, Joel Minier-Matar1, Altaf Hussain1, Arnold Janson1, Rong Wang2, Anthony G. Fane2

ConocoPhillips - Global Water Sustainability Center, QA

1

Singapore Membrane Technology Centre, Nanyang Technological University, SG

2

Email: samer.adham@conocophillips.com

In order to ensure long-term sustainability of the reservoir, the gas industry in Qatar is faced with the challenge of
reducing the volume of produced and process water (PPW) sent to disposal wells by 50% [1-3]. Recently, Qatargas
initiated a project to recycle process water and thus, reduce disposal volumes using commercial advanced water
treatment technologies [4]. One emerging technology, “osmotic concentration” (OC) has been identified that offers
a low-energy alternative to conventional thermal or membrane volume reduction methods. Osmotic concentration
is a membrane filtration process that mimics first step in a forward osmosis (FO) system. It requires a high salinity
draw solution (DS) which passes on one side of a semi-permeable FO membrane while the feed passes on the other
side. Water from the feed is drawn through the membrane, via natural osmosis, reducing the feed volume and
increasing the volume of the draw solution. This paper summarizes the results of bench-scale volume reduction
tests with PPW collected from Qatar’s North Field operations as the feed and either seawater or the concentrated
brine from thermal desalination plants as the draw solution. While in conventional forward osmosis, the draw
solution is regenerated, in OC, there is no regeneration of the draw solution. The diluted seawater or brine would
be simply discharged to the Arabian Gulf. For future projects/developments, the authors have proposed OC for PPW
volume reduction, which can be a cost-efficient alternative to achieve 50% reduction in disposal volumes (Figure 1).
This approach is particularly applicable in Qatar due to close proximity of desalination plants and gas processing
facilities. In all membrane processes, the driving force for permeation is pressure. The mechanism by which the
pressure is created differentiates various membrane processes: Reverse osmosis: static pressure generated by a
pump Membrane distillation: vapor pressure differential due to a difference in temperature Osmotic concentration:
osmotic pressure differential due to a difference in salinity. In these examples, the driving force or transmembrane
pressure (TMP) can be measured in units of kPa or bar. In reverse osmosis, the TMP ranges from 15 to 60 bar
depending on the salinity of the feed. In osmotic concentration, a comparable TMP of 15 to 60 bar is generated

Cite this article as: Adham S, Santos A, Minier-Matar J, Hussain A, Janson A, Wang R, Fane AG. (2016). Application
of Osmotic Concentration for Volume Reduction of Produced/Process Water from Gas-Field Operations. Qatar
Foundation Annual Research Conference Proceedings 2016: EEPP1948 http://dx.doi.org/10.5339/qfarc.2016.
EEPP1948.

This abstract is available through QScience.com

simply by high salinity the draw solution, i.e. without any static pressure being required
and hence the low energy requirements for OC processes. In addition to significantly
lower operating energy requirements [5], an OC process offers the following advantages
over reverse osmosis (RO): Lower capital cost because pressure-rated vessels and high
pressure pumps are not required [6]; There is strong evidence that FO membranes are less
prone to irreversible fouling than RO membranes and foulants can be removed by simple
flushing with clean water with no addition of chemicals [7,8]; The water discharged to the
Arabian Gulf is of lower salinity and that provides an environmental benefit. The primary
disadvantages of OC are that there is no water recovery after the separation process
and there is limited experience from full-scale water treatment installations. The main
objective of this study was to investigate the feasibility of OC to concentrate PPW from gas
operations by 50% using brine from thermal desalination plants as draw solution. The PPW
was a combination of gas field produced water extracted from an offshore reservoir and
process water from onshore operations. The blending ratio between produced and process
water was approximately 1:5. The PPW underwent deoiling, H2S removal and cartridge
filtration (2 mm). The detailed composition of PPW and brine from thermal desalination
plant are shown in Table 1. During this study, experiments were conducted to evaluate OC
performance in treating PPW in the following areas: membrane configuration membrane
fouling effect of pretreatment process optimization long-term stability/performance. In
all tests, the active layer faced the feed solution (AL-FS mode) since this configuration
provides better control of feed-side fouling. Membrane configuration During this project,
two membrane configurations were evaluated: Flat sheet (FS) membranes, commercially
available [9]Hollow fiber (HF) membranes, Singapore Membrane Technology Centre [10,
11]. The membrane surface areas were 0.014 and 0.0106 m2 for the FS and HF modules,
respectively. Experiments were conducted using two feed solutions: DI water and PPW.
Results showed that the HF membranes had improved performance from both the water
flux and reverse solute flux (RSF) perspectives. The HF membrane flux was ≈35 to 45%
higher for both DI water and PPW (Figure 2). With PPW as feed at 25 °C, the RSF was
measured for both membranes and the results showed that HF membranes exhibited ≤3
mmol/m2 h RSF for Na+ and Cl– while FS membranes showed a RSF of ≈20 mmol/m2h for
both ions. RSF is highly sensitive to operating temperature. Because HF membranes showed
superior performance and there are also commercial advantages (higher packing density,
lower fabrication cost), experiments focused on evaluating HF performance in treating PPW.

Membrane fouling
To assess if membrane fouling occurred, a benchmark test with DI water as feed solution
and 1M NaCl as draw solution at 25 °C was conducted before and after each fouling test.
A decline in the benchmark flux after treating PPW would indicate that membrane fouling
had occurred. The fouling tests were conducted on two feed streams: synthetic PPW
(mimicking only the inorganic content of PPW) and real PPW. During the experiments,
the initial volume of PPW was reduced by 50% and the draw solution (DS) was 1M NaCl.
The DS concentration, for both benchmark and fouling tests, was maintained constant
throughout the experiments by adding concentrated NaCl solution based on conductivity
measurements. While the results for synthetic PPW showed that no fouling had occurred,
the results showed that PPW could cause fouling on the membrane surface since the
benchmark flux decreased from 17.5 to 15 L/m2 h (Figure 3). The fouling was attributed to
the organics present in the PPW since no flux decline was observed on the when synthetic
PPW was used as feed. These results highlighted the need for effective pretreatment to
remove organics.

Effect of pretreatment
To determine if pretreatment could remove the organics responsible for fouling, a number
of methods were screened and ultimately powdered activated carbon (PAC) was selected
for pretreatment of the PPW. PAC is widely used for organics removal and previously
evaluated for similar applications [12]. Lab results showed that at a dosage of 500 mg/L PAC,
the TOC from the PPW was reduced from 132 to 45 mg/L. The PAC dosage was considered
very high for a full-scale application and further pretreatment optimization is needed before
field implementation. OC performance experiments showed no decline in benchmark flux
when the volume of pretreated PPW was reduced by 50% indicating that pretreatment is
essential for the successful implementation OC to reduce PPW disposal volumes. Results
also showed that the HF membranes have good rejection for organics. For both the treated
and untreated PPW, the TOC in the draw solution after OC treatment was below the 1 mg/L
detection limit indicating that the membrane rejection of the organics was >99%.

Process optimization: Box-Behnken design

The main operating parameters for this application were optimized using a Box-Behnken
design (BBD) [13, 14]. BBD is a response surface methodology that explores the effect of
different input variables (temperature, draw solution concentration and feed crossflow
velocity) on the output response (flux). This statistical tool takes into consideration the
combined effects and interdependence of the input variables and significantly reduces
the number of tests required as compared to the conventional factorial experimental
design. The following parameters and test values were used during the BBD experiments:
Temperature: 25, 35 and 45 °C Draw solution concentrations: 40, 55 and 70 g/L NaCl Feed
crossflow velocity: 40, 60, 80 cm/s. Results showed that the temperature has the greatest
impact on the flux, since it influences the water viscosity. DS concentration directly affects
the osmotic pressure, influencing the flux. The feed crossflow velocity did not affect the
process performance over the range tested. These results are consistent with authors’
expectations and general published results. Based on the BBD analysis, the optimized
process conditions were: 45°C temperature, 70 g/L draw solution concentration and 80
cm/s feed crossflow velocity. Figure 4 shows the comparison of the OC performance, to
achieve 50% feed volume reduction, at benchmark (25 °C, 70 cm/s, 58.5 g/L NaCl) and
optimized (45 °C, 80 cm/s, 70 g/L NaCl) conditions.

Long-term performance and water quality

The elimination of the water recovery step in osmotic concentration makes it an energy
efficient process [5]. To confirm if the brine from thermal desalination plants is a suitable
DS for the treatment of PPW, a long-term experiment was performed simulating full-scale
operation. In earlier experiments, the concentration of the DS was maintained constant,
by adding concentrated DS. Since this is not feasible in full-scale applications, a process
stability experiment was carried out without controlling the DS’s concentration, allowing
it to dilute with time as water permeates through the FO membrane. The experiment was
conducted using pretreated PPW as feed and brine from thermal desalination plant as DS.
The solution temperature was 45 °C since this is the expected temperature of the brine
discharged from the desalination plant. The feed and draw solutions crossflow velocities
were 80 and 40 cm/s respectively. The test was conducted for 80 hours. The PPW initial
volume was 42 L and it was reduced in volume by 50% while the volume of the draw
solution, initially 21 L, was increased to 42 L, reducing its salinity by 50%. A relatively
stable performance was observed throughout the experiment with a 30% decrease in flux
(from 28 to 20 L/m2 h) due to the decrease of the effective osmotic pressure and to the
influence of the internal concentration polarization (ICP). After a sharp initial decline in
osmotic pressure differential, the decline in flux almost tracked the decline in the osmotic
pressure differential (Figure 5). DI water fluxes during benchmark tests conducted before
and after the experiment remained constant at 19.4 L/m2 h indicating that negligible
fouling occurred. To evaluate the ability of HF membranes to reject specific contaminants,
various water quality analyses were performed. Results showed that HF membranes have
high rejection capabilities. The ions with the highest solute fluxes values were sodium and
chloride with a RSF of 120 and 91 mmol/(m2 h) respectively at 45 °C (Table 2). Although
a small amount of nitrogen passed through the membrane from the PPW to the draw
solution, at the levels found (5.8 mg/L), it was below the discharge limits set by the State
of Qatar and the European commission (10 mg/L) [15]. The results also showed that the
organic carbon present in the PPW was rejected by the membrane and retained in the
PPW. A slightly increase in the TOC concentration in the DS was observed and it could
be attributed to uncertainties in the analysis since the results were at the low end of the
measurement accuracy. Finally, preliminary cost estimates and energy calculations showed
that OC is economically feasible to reduce PPW injection volumes from gas fields in an
environmentally sustainable manner. The research team is currently evaluating different
pilot testing opportunities to further demonstrate the cost-effectiveness of this technology
under relevant field conditions.