Mathematical Modeling of Flowback

Water Treatment using Reverse Osmosis

and Nanofiltration Technologies

Pedro Rosa
Department of Chemical and Petroleum Engineering
University of Pittsburgh, Pittsburgh, PA 15261, USA

(April 27th , 2016)

 Outline
 Introduction & Background
 Objective

 Research Approach
 Reverse Osmosis (RO) Model
 Nanofiltration (NF) Model
 Sensitivity Analysis
 Comparison of Commercial RO and NF membranes
 Concluding Remarks

2
 Shale gas reserves in the world
 About 32% of the world’s total estimated natural gas reserves is in shale
formations

A. E. Outlook, "Energy Information Administration," Department of Energy, 2014. 3

 Recoverable shale gas and oil worldwide

 Technological advances in horizontal drilling and hydraulic fracturing

allowed the discovery of huge natural gas and oil recoverable reserves in
the US and worldwide.

A. E. Outlook, "Energy Information Administration," Department of Energy, 2014. 4

 Major US shale gas plays
New
Shale Basin Barnett Fayetteville Haynesville Marcellus Woodford Antrim
Albany
Area (sq. miles) 5,000 9,000 9,000 95,000 11,000 12,000 43,500
6,500 – 10,500 – 6,000 - 600 – 5000 -
Depth (ft) 1,000 – 7,000 4,000 – 8,500
8,500 13,500 11,000 2,200 2000
Thickness (ft) 100 – 600 20 - 200 200 - 300 50 - 200 120 - 220 70 - 120 50 - 100
Depth to base of
1,200 500 400 850 400 300 400
treatable water (ft)
Rock column between
5,300 – 10,100 – 5,600 – 300 – 100 –
pay and base of 500 – 6,500 2,125 - 7,650
7,300 13,100 10,600 1,900 1,600
treatable water (ft)
Total organic carbon
4.5 4 – 9.8 0.5 – 4 3 – 12 1 – 14 1 – 20 1 – 25
(%)
Total porosity (%) 4–5 2–8 8–9 10 3–9 9 10 – 14
Gas content (scf/ton) 300 – 350 60 – 220 100 – 330 60 – 100 200 – 300 40 – 100 40 – 80
Water production
0 0 0 0 - 5 – 500 5 – 500
(Barrels/day)
Well spacing (Acres) 60 – 160 80 – 160 40 – 560 40 - 160 640 40 – 160 80
Original Gas-in-Place
327 52 717 1,500 52 76 160
(tcf)
Reserves 44 42 251 363 – 500 11.4 20 19.2
Estimated production
338 530 625 – 1800 3,100 415 125 – 200 -
(mcf/day-well)

N. P. Cheremisinoff and A. Davletshin, Hydraulic fracturing operations: Handbook of environmental management practices: John Wiley
& Sons, 2015.
J. D. Arthur, B. K. Bohm, B. J. Coughlin, M. A. Layne, and D. Cornue, "Evaluating the environmental implications of hydraulic fracturing 5
in shale gas reservoirs," in SPE Americas E&P environmental and safety conference, 2009.
 Impact of shale gas on the US energy

 Exponential increase
of the shale gas plays
in the US since the
mid-2000.

 Advances in horizontal
drilling and hydraulic
fracturing have made
shale an attractive
natural gas source,
allowing the US to
ensure its energy
independence and
national security.

C. H. Arnaud, "Figuring out Fracking Wastewater," Chem. Eng. News, vol. 93, 2015.
6
 Hydraulic fracturing operation (Fracking)

C. H. Arnaud, "Figuring out Fracking Wastewater," Chem. Eng. News, vol. 93, 2015.
A. Granberg. (2008). What is Hydraulic Fracturing?
7
 Fracturing fluid
 The fracturing fluid consists mainly of water, multiple proprietary chemicals
and a proppant, such as sand, ceramic, or other solid particulates.

 In the fracking operation, huge volumes of water (2-5 million gal) and
chemicals (20,000-50,000 gal) are used per well.
Gelling Agent Scale Inhibitor
0.05% 0.04%
KCl pH Adjusting Agent
Friction Reducer 0.05% 0.011%
0.08%
Breaker
0.010%
Sand
8.95% Crosslinker
0.007%
Iron Control
0.005%
Corrosion Inhibitor
Other 0.002%
0.0045
Biocide
0.002%

Acid
Water 0.11%
90.60% Surfactant
0.08%
N. P. Cheremisinoff and A. Davletshin, Hydraulic fracturing operations: Handbook of environmental management practices:
John Wiley & Sons, 2015.
8
 Hydraulic fracturing water cycle

Water Availability
Water
Impact of Water Withdrawal on Water Quality
Acquisition
Impact of Other Users of Same Water

Release to Surface and Groundwater

Chemical
Chemical Transportation Incidents
Mixing
Chemical Handling Incidents

Accidental Release to Ground or Surface Water

Well
Fracturing/ Formation Fluid Migration into Aquifers
Design
Subsurface Formation Materials into Aquifers

Overflows and Releases to Surfaces and Groundwater

Flowback and
Leakage from On-Site Storage into Drinking Water
Produced Water
Improper Pit Construction, Maintenance and Closure
Surface/Subsurface Discharge into Surface and Groundwater
Wastewater
Incomplete Treatment of Wastewater and Solid Residuals
Treatment and
Incomplete Treatment of Unknown Constituents
Disposal
Wastewater Transportation Accidents

C. H. Arnaud, "Figuring out Fracking Wastewater," Chem. Eng. News, vol. 93, 2015. 9
 Composition of Marcellus shale flowback water

TDS
Sulfite
Sulfide total
Sulfate (SO₄⁻⁴)
Strontium total
Sodium (Na⁺)
Ra(226, 228)*
Phosphorus total
Oil and grease
Nitrite as N
Nitrate-Nitrite
Manganese total
Magnesium Total
Iron total
CaCO₃
Fluoride
Chloride (Cl⁻)
Calcium total
Bromides total
Barium total
Ammonia Nitrogen
0 0 1 10 100 1,000 10,000 100,000 1,000,000
* Unit: pCi/ml
Concentration (mg/L)

References [2], [19], [20], [21] and [22] in the Thesis.

10
 Composition of Marcellus shale flowback water
TDS
Sulfite
Sulfide total
Sulfate (SO₄⁻⁴)
Strontium total
Sodium (Na⁺)
Ra(226, 228)*
Phosphorus total
Oil and grease
Nitrite as N
Nitrate-Nitrite
Manganese total
Magnesium Total
Iron total
CaCO₃
Fluoride
Chloride (Cl⁻)
Calcium total
Bromides total
Barium total
Ammonia Nitrogen
0 0 1 10 100 1,000 10,000 100,000 1,000,000
* Unit: pCi/ml Concentration (mg/L)

References [2], [19], [20], [21] and [22] in the Thesis.

11
 Composition of Marcellus shale flowback water

TDS
Sulfite
Sulfide total
Sulfate (SO₄⁻⁴)
Strontium total
Sodium (Na⁺)
Ra(226, 228)*
Phosphorus total
Oil and grease
Nitrite as N
Nitrate-Nitrite
Manganese total
Magnesium Total
Iron total
CaCO₃
Fluoride
Chloride (Cl⁻)
Calcium total
Bromides total
Barium total
Ammonia Nitrogen

* Unit: pCi/ml 0 0 1 10 100 1,000 10,000 100,000 1,000,000

Concentration (mg/L)

References [2], [19], [20], [21] and [22] in the Thesis.

12
 Wastewater management in Pennsylvania

Road Spreading Centralized Waste

Storage Pending 0.0007%
Disposal or Reuse Treatment
0.31% 6.90%
Injection Disposal
Well
8.59%

Landfill
0.15%

Residual Waste
Reuse other than Processing/Transfer
road spreading Facility
66.26% 17.75%

O. Dawkins, "Pennsylvania Department of Environmental Protection," T. R. E. Center, Ed., ed, 2008. 13

 Wastewater management methods

 Chemical (ion exchange)

 Electrochemical (electrolysis)

 Thermal (vaporization)

 Physical (membrane filtration)

14
 Membrane filtration technologies
Microfiltration Ultrafiltration Nanofiltration Reverse Osmosis
Cut-off size > 100 nm 10 -100 nm 0.1- 1 nm < 0.1 nm
Filtered compound
- 103 -105 kg/kmol 200 – 103 kg/kmol < 103 kg/kmol
molecular weight
Transmembrane
0.02 -0.5 MPa 0.2 - 1 MPa 0.5 -3 MPa 2 -20 MPa
pressure
50 -1000 < 100 < 100 10 -35
Permeate flow
L/(m2 h) L/(m2 h) L/(m2 h) L/(m2 h)
Cross-flow speed 2 – 6 m/s 1 – 6 m/s 1 – 2 m/s < 2 m/s
Screening by Electrostatic Solubility and
Retention Screening by
membrane and repulsion and diffusion in the
mechanism membrane pores
gel layer screening membrane
Transport Hydrodynamic
Back diffusion Back diffusion Back diffusion
mechanism lift force
Tubular, Tubular, Tubular,
Tubular, hollow-fiber, hollow-fiber, hollow-fiber,
Unit modules
hollow-fiber spiral-wound, spiral-wound, spiral-wound,
plate and frame plate and frame plate and frame
Starch, sugar, Metal cations,
Protein, starch,
pesticides, acids, aqueous
Clay, bacteria, viruses, colloidal
herbicides, salts, sugar,
Materials retained viruses, silica, organics,
divalent anions, amino acids,
suspended solids dyes, fats, paint,
organics, BOD, monovalente salts,
suspended solids
COD, detergents BOD, COD
T. Hayes and D. Arthur, "Overview of emerging produced water treatment technologies," in 11th Annual International 15
Petroleum Environmental Conference, Albuquerque, NM, 2004.
 What is a membrane filtration?

Applied Pressure

Feed Retentate

Permeate

16
 How the membrane works?

https://www.youtube.com/watch?v=VmIlAySHhkQ 17
 Objective

 The main objective is to assess through mathematical modeling

the potential use and feasibility of deploying RO and NF
membrane technologies in the treatment of flowback water
produced during hydraulic fracturing operations.

 The following tasks are proposed to achieve this objective:

 Task 1: Develop mathematical models for RO and NF
membranes.
 Task 2: Conduct sensitivity analysis of the operating
variables.
 Task 3: Compare commercial RO and NF membranes used
in backflow water treatment.

18
 Research approach

 Solution Diffusion Model

 Assumptions:
1. The fluids on each side of the membrane are in equilibrium,
thus there is a continuous chemical potential gradient .

2. Pressure within the membrane is constant, and thus the

chemical potential gradient across the membrane can be
expressed only in terms of a concentration gradient.

3. The fluid and membrane are incompressible, and so the

pressure profile is uniform within the membrane.

19
 Solvent flux across the membrane

 Chemical potential, pressure and activity profiles across a membrane

Permeate
(Clean Water)

Membrane
On the membrane
(Permeate Side):
(Lp, ω, σo) In the Boundary Layer:
Flowback
pw, µAw, γAw
pp(m) , µAp(m), γAp(m) Water Bulk

Chemical
Potential, µA

In the Permeate: Feed Flow

pp , µAp, γAp Pressure , p

In the Bulk:
po, µAo, γAo

Feed Flow
Solvent (Water)
activity, γAcA

l Solution Diffusion Model Assumptions:

0 δ x

On the membrane (Bulk

Side):
pw(m) , µAw(m), γAw(m) 20
 Equations for solvent flux across the membrane

On the membrane
Membrane 𝝁𝑨𝒘 = 𝝁𝑨𝒘(𝒎)
(Permeate Side):
(Lp, ω, σo) In the Boundary Layer:
pw, µAw, γAw
pp(m) , µAp(m), γAp(m)
𝝁𝑨𝒑 = 𝝁𝑨𝒑(𝒎)
Chemical
Potential, µA

In the Permeate: 𝜇𝐴 = 𝜇𝐴𝑜 + 𝑅𝑇𝑙𝑛 𝛾𝐴 𝑐𝐴 + 𝜈𝐴 𝑝 − 𝑝𝐴𝑜

Pressure , p
pp , µAp, γAp
In the Bulk:
po, µAo, γAo
∴
Solvent (Water)
activity, γAcA 𝑐𝐴𝑤(𝑚) = 𝐾𝐴𝑤 𝑐𝐴𝑤
l 0 δ x
On the membrane (Bulk
Side):
pw(m) , µAw(m), γAw(m) −𝜈𝐴 𝑝𝑜 − 𝑝𝑝
𝑐𝐴𝑝 𝑚 = 𝐾𝐴𝑝 𝑐𝐴𝑝 ∙ 𝑒𝑥𝑝
𝑅𝑇

21
 Equations for solvent flux across the membrane
(cont.)

𝑫𝑨 𝒄𝑨𝒘(𝒎) − 𝒄𝑨𝒑(𝒎)
𝑱𝑨 =
On the membrane
Membrane 𝒍
(Permeate Side):
(Lp, ω, σo) In the Boundary Layer:
pw, µAw, γAw
pp(m) , µAp(m), γAp(m)
Chemical −𝝂𝑨 𝜟𝒑 − 𝜟𝝅
Potential, µA 𝑱𝑨 = 𝜿𝑨 𝒄𝑨𝒘 𝟏 − 𝒆𝒙𝒑
𝑹𝑻
In the Permeate:
Pressure , p
pp , µAp, γAp
In the Bulk: 𝑫𝑨 𝑲𝑨
po, µAo, γAo Water permeability: 𝜿𝑨 = 𝒍

Solvent (Water)
activity, γAcA

l 0 δ x 𝑱𝑩 = 𝜿𝑩 𝒄𝑩𝒘 − 𝒄𝑩𝒑
On the membrane (Bulk
Side):
pw(m) , µAw(m), γAw(m)

22
 Reverse osmosis model
 Single-Pass
Configuration:  Model Assumptions

1. ΔP across the membrane is negligible

Retentate

𝒅𝝅𝑨𝒘 𝒅𝝅𝑨𝒑
𝒅𝑱𝑨 = −𝜿′𝑨 𝒅𝒄𝑨𝒘 + 𝜿′𝑨 ( )𝒅𝒄𝑨𝒑
𝒅𝒄𝑨𝒘 𝒅𝒄𝑨𝒑

Permeate
𝒅𝑱𝑩 = 𝜿𝑩 𝒅𝒄𝑩𝒘 − 𝜿𝑩 𝒅𝒄𝑩𝒑

2. Concentration gradient in boundary

layer (Concentration Polarization)
Feed
𝒄𝑨𝒘 − 𝒄𝑨𝒑
𝑱𝑨 = 𝒌𝒎 𝒍𝒏
𝒄 − 𝒄𝑨𝒑

23
 Reverse osmosis model
 Single-Pass
Configuration:  Mass Balance across the membrane
 Dividing by the differential area (dA)
Retentate
𝒌𝒎 𝒅𝒄 𝒄𝑨𝒘 − 𝒄𝑨𝒑 𝒅𝒌𝒎
− 𝐥𝐧
𝒅𝒄𝑨𝒘 𝒄 − 𝒄𝑨𝒑 𝒅𝑨 𝒄 − 𝒄𝑨𝒑 𝒅𝑨
=
𝒅𝑨 𝒌𝒎 𝜽 𝒌 𝟏−𝜽 𝒅𝝅𝑨𝒘 𝒅𝝅𝑨𝒑
+ 𝒎 + 𝜿′𝑨 − 𝜿′𝑨 𝜽
𝒄 − 𝒄𝒑 (𝒄𝑨𝒘 −𝒄𝑨𝒑 ) 𝒅𝒄𝑨𝒘 𝒅𝒄𝑨𝒑

Permeate

𝒌𝒎 𝑱 𝒄𝑨𝒘 − 𝒄𝑨𝒑
𝟏 + 𝒏 𝒍𝒏
𝒅𝒄𝑩𝒘 𝑸 𝒄 − 𝒄𝑨𝒑
Feed =
𝒅𝑨 𝒌𝜽′ 𝒌 𝟏 − 𝜽′
+ 𝒎 + 𝜿′𝑨 𝒊𝑹𝑻 − 𝜿′𝑨 𝒊𝑹𝑻𝜽′
𝒄 − 𝒄𝑩𝒑 𝒄𝑩𝒘 − 𝒄𝑩𝒑

24
 Nanofiltration model

 Batch-Fed Configuration:  The main difference between NF and

RO models  in the overall solute
flux, besides the diffusion, NF has
the contribution of the Convenction
Flux

𝒄𝑩𝒂𝒗
𝑱𝑩 = 𝜿𝑩 𝒄𝑩𝒘 − 𝒄𝑩𝒑 + 𝟏 − 𝝈𝒐 𝑱𝑨
𝝊𝑨 × 𝟏𝟎𝟑

−𝝂𝑨 𝜟𝒑 − 𝝈𝒐 𝑹𝑻 𝒄𝑨𝒘 − 𝒄𝑨𝒑

𝑱𝑨 = 𝜿𝑨 𝒄𝑨𝒘 𝟏 − 𝒆𝒙𝒑
𝑹𝑻

25
 Nanofiltration model

 Batch-Fed Configuration:  Mass Balance across the membrane

𝒅𝒄
𝑽𝒐 = −𝑱𝑩 𝑨 + 𝑱𝑨 𝑨
𝒅𝒕

𝒅𝒄
= −(𝑱𝑨 𝑨 − 𝑱𝑩 𝑨)/𝑽𝟎
𝒅𝒕
𝜿𝑩 𝒄𝑩𝒘 − 𝒄𝑩𝒑
𝑱𝑩 = 𝑱𝑨
−𝝂𝑨 𝜟𝒑 − 𝜟𝝅
𝜿𝑨 𝒄𝑨𝒘 𝟏 − 𝒆𝒙𝒑 𝑹𝑻
𝒄𝑨𝒘 − 𝒄𝑨𝒑
𝑱𝑨 = 𝒌𝒎 𝒍𝒏
𝒄 − 𝒄𝑨𝒑
26
 Model parameters and operating conditions used
in the models (cont.)

Parameters Nomenclature Unit Min Max Average

Flowback flow rate – Inlet Flow rate Qo m3/s 5×10-4 5×10-3 2.75×10-3
Operating Pressure ΔP MPa 5.5 20 12.75
Temperature T K 275 370 322.5
Gas Constant R Pa.m3/K/mol - - 8314
Van’t Hoff Coefficient i - - - 1.0
Module diameter D m - - 0.2
Module length L m - - 1.0
Module surface area A m2 - - 41.0
Module permeate flow rate m3/s - - 3.15×10-4
Module packing density m2/m3 492 1247 869.5

27
 Sensitivity analysis results (Cl-) – RO

 Effect of Water Permeability (A)  Effect of Pressure Drop (P)

1.95 2

1.9 1.9 ΔP = 1.5 MPa

Solute Concentration (kmol/m3)

Solute Concentration (kmol / m3)

ΔP = 3.5 MPa
κA = 1.6 - 3.4 µm/s 1.8
1.85
0.4 increments
1.7 ΔP = 5.5 MPa
1.8
1.6
ΔP = 7 MPa
1.75
1.5
ΔP = 8 MPa
1.7
1.4
ΔP = 9 MPa

1.65 1.3
ΔP = 15 MPa
1.6 1.2
0 1 2 3 4 5 0 1 2 3 4 5
Area (m2) Area (m2)

28
 Sensitivity analysis results (Cl-) - RO

 Effect of Temperature (T)  Effect of Membrane Area (A)

1.95 2

1.9
1.9
Solute Concentration (kmol / m3)

Solute Concentration (kmol/m3)

A = 1 m²
1.85
1.8 A = 2 m²

1.8 A = 3 m²

1.7 A = 4 m²
1.75 A = 5 m²
T = 370 K
T = 350 K 1.6 A = 6 m²
1.7 T = 330 K A = 7 m²
T = 310 K 1.5 A = 8 m²
1.65 T = 298 K
A = 9 m²
T = 275 K 1.4 A = 10 m²
1.6
0 1 2 3 4 5 0 0.2 0.4 0.6 0.8 1
Area (m2) Dimensionless Length

29
 Sensitivity analysis results (Cl-) - RO

 Effect of Volumetric Flow Rate (Qo)

2
Qo = 10-3 m3/s
1.8 Qo = 4 10-4 m3/s
2 Qo = 3 10-4 m3/s
Qo = 10 m Qo = 2 10-4 m3/s
-3 3
1.6
1.8 Qo = 4 10-4 m3
Qo = 3 10-4 m3
-4 3
Qo = 2 10-4 Qo
m3 = 10 m /s
1.6
1.4
3)3
(kmol/m )

Qo = 10-4 m3
(kmol/m

1.4
1.2
Qo = 5 10-5 m3/s
1.2
Concentration

1 Qo = 5 10-5 m3
Concentration

1
0.8
0.8

0.6
0.6
Solute

0.4
0.4

0.2
0.2 Qo = 10-5 m3
Qo = 10-5 m3/s
0
00 1 2 3 4 5
0 1 2 (m2)
Area 3 4 5
Area (m2)
30
 Sensitivity analysis results (Cl-) - NF

 Effect of Water Permeability (A)  Effect of Solute Permeability (B)

0.5 0.5
κB
0.45 0.45
6.5 μm/s
5 μm/s
Solute Concentration (kmol / m3)

0.4 0.4

Solute Concentration (kmol / m3)

3.5 μm/s
κA = 5.5 - 8.5 µm/s
0.35 0.5 increments
0.35

0.3 0.3

0.25 0.25

0.2 0.2

0.15 0.15

0.1 0.1

0.05 0.05

0 0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600
Time (s) Time (s)

31
 Sensitivity analysis results (Cl-) - NF

 Effect of Pressure Drop (P)  Effect of Reflection coefficient

(o)
0.5 0.5

0.45 0.45
Solute Concentration (kmol / m3)

Solute Concentration (kmol / m3)

0.4 0.4

0.35 ΔP = 0.2 MPa

0.35

0.3 0.3

0.25 0.25

0.2 0.2

0.15 0.15
ΔP = 2 MPa
0.1 0.1

0.05 ΔP = 5 MPa 0.05

0 0
0 500 1000 1500 0 500 1000 1500
Time (s) Time (s)

32
 Sensitivity analysis results (Cl-) - NF

 Effect of Temperature (T)  Effect of Membrane Area (A)

0.5 0.55
0.45 0.5
T = 350 K

Solute Concentration (kmol / m3)

0.4 0.45
Solute Concentration (kmol / m3)

T = 298 K

0.35 T = 275 K 0.4

0.35
0.3
0.3
0.25
0.25
0.2
0.2
A = 0.2 - 3 m²
0.15
0.15 0.4 increments

0.1 0.1

0.05 0.05

0 0
0 100 200 300 400 500 600 0 1000 2000 3000
Time (s) Time (s)

33
 Comparison among commercial
membranes
 Reverse Osmosis

RO Membrane Selective Layer Material Water Permeability, kA (m/s)

XLE Polyamide 2.06×10-11
ESPA1 Polyamide 1.50×10-11
BW30 Polyamide 8.33×10-12
SWC4+ Polyamide 1.94×10-12

 Nanofiltration

NF Membrane Selective Layer Material Water Permeability, kA (m/s)

TFC-SR (Koch) Polyamide 5.47×10-11
NF-90 (Dow) Polypiperazine amide 1.00×10-11
NF-70 (Dow) Polypiperazine amide 7.22×10-12

33
 Properties of the solutes used in the comparison

Solute Permeability, Concentration in Flowback water Molar Mass

Solute Km (µm/s)
kA (µm/s) (mg/L) (kg/kmol)
Chloride (Cl-) Cl 11.16 4.1×10-3 98032.1 35.453
Sodium (Na+) Na 17.24 8.6 58534.6 22.99
Calcium total Ca 8.24 1.8×10-3 20518.9 40.078

 Cl-, Na+, Ca2+ account for 93% of the total flowback salt
ions concentration.

35
Comparison between RO and NF for Na+ removal

Reverse Osmosis Nanofiltration

90

80
Na+

70
Efficiency (%)

60

50

40

30

20

10
XLE ESPA1 BW30 SWC4+ TFC-SR NF-90

36
Comparison between RO and NF for Ca+2 removal

Reverse Osmosis Nanofiltration

90

80
Ca+2

70
Efficiency (%)

60

50

40

30

20

10
XLE ESPA1 BW30 SWC4+ TFC-SR NF-90 NF-70

37
Comparison between RO and NF for Cl- removal

90

80 Reverse Osmosis Cl-

Nanofiltration
70
Efficiency (%)

60

50

40

30

20

10
XLE ESPA1 BW30 SWC4+ TFC-SR NF-90 NF-70

38
 Concluding remarks

 Mathematical models for RO and NF processes were

developed to assess their performance in the treatment of
flowback water. The models were verified and implemented
in Matlab version R2015.

 For the RO, the pressure drop, inlet flow rate and membrane
area were the major parameters governing the process
performance.

 For NF the pressure drop, the effect of the reflection

coefficient and membrane area were the most important
parameters affecting the process performance.

39
 Concluding remarks (cont.)

 The models were also used to assess and compare the

performance of four different commercial RO and three NF
membranes.

 Actual filed data, such as inlet flowrate and flowback water

composition were used in the models.

 The models predictions showed that the RO membranes were

significantly superior to the NF membranes in the removal of Na+
and Ca2+.

 NF exhibited higher removal efficiencies for Cl- than that of the

reverse osmosis membranes.

40
41
 Introduction
 Water treatment technologies and their application to produced water
Suspended Ca & Mg Soluble Trace Desalination Silicate
Iron SAR
Treatment Method De-Oiling Solids Removal Organic Organic & Brine & Boron
Removal Adjustment
Removal Softening Removal Removal Volume Removal
API Separator
Deep Bed Filter
Hydrocyclone
Induced Gas
Flotation
Ultra-filtration
Sand filtration
Aeration &
Sedimentation
Precipitation
Softening
Ion Exchange
Biological
Treatment
Activated Carbon
Reverse Osmosis
Distillation
Freeze Thaw
Evaporation
Electrodialysis
Chemical Addition
42
 Solute permeability Calculation
• Empirical Model (Voros et al., 1996)

𝟏.𝟖𝟖
𝑿
𝜿𝑩 = 𝟎. 𝟑𝟗𝟓
𝟐. 𝟓𝟒 × 𝟏𝟎−𝟑

Where 𝜅𝐵 is the solute flux in 𝜇𝑚/𝑠 and 𝑋 is the molar fraction of the solute.

N. Voros, Z. Maroulis, and D. Marinos-Kouris, "Salt and water permeability in reverse

osmosis membranes," Desalination, vol. 104, pp. 141-154, 1996.
43
 Mass Transfer Coefficient Calculation

1) Diffusivity

2) Schmidt

3) Reynolds

4) Reynolds

5) Sherwood

6)
44
 Definition of Chemical Potential

• Energy Potential transferred in chemical reaction.

 Concentration Polarization
Permeate Boundary
Flowback
(Clean Water) Layer
Water Bulk
Cw, πw

Membrane (Lp, ω, σo)

Convection

Diffusion
Feed Flow

Cb, πb
Cp, πp

0 δ x

 There is a boundary layer near the membrane where the

concentration of the non-permeating fluid increases.
 There is a concentration gradient between the bulk and the
boundary layer.
 This reduces the water’s concentration and the boundary
layer which reduces the flux and membrane selectivity.