OPTIMIZATION OF FORWARD OSMOSIS

PROCESS FOR WATER DESALINATION

Abstract
MS thesis report contains the introduction, Mathematical model, motivation for project,
methodology for the optimization and achievements so far

Zia Ur Rehman
Zia8t.zk@gmail.com
What is forward osmosis?

Forward osmosis is the process of spontaneous water diffusion across a semi-

permeable forward osmosis membrane in response to a difference in solute
concentrations (i.e. osmotic pressures) on either side of the semi-permeable
membrane. In essence, the diffusion of water can be explained by the second law of
thermodynamics, which implies that systems always spontaneously evolve towards a
state of thermodynamic equilibrium where the system’s entropy (or amount of
disorder) is maximized. And from an entropy point of view, maximum disorder – in a
system consisting of two aqueous solutions with different solute concentrations
separated by a semi-permeable membrane – is achieved when enough water has
diffused from the low concentration side to the high concentration side to eliminate the
difference in solute concentration.

Forward osmosis is a natural process, which takes place all

around us on an everyday basis. Forward osmosis enables plants to transport water
from their root systems to their leaves and it provides the primary means of
transporting water in and out of cells across most organisms in Nature.

How does a forward osmosis membrane work?

Generally speaking, membranes for water treatment applications are thin, porous, and
permeable materials, which can be used as selective barriers between aqueous
solutions. In most applications, water treatment membranes are used to remove
unwanted substances (e.g. suspended solids, bacteria, solutes, etc.) from aqueous
solutions. In simpler terms, contaminated water enters on one side of the membrane
and – depending on the membrane’s selectivity properties – less contaminated water
exits on the other side of the membrane. Selectivity properties are commonly achieved
by adjusting the pore size of the membrane material to prevent contaminants of
interest to pass through the membrane.

Forward osmosis membranes are typically designed to be more or less exclusively

selective towards water molecules, which enables them to separate water from all
other contaminants. In forward osmosis membrane processes, the driving force for
water separation is quantified by the osmotic pressure difference between solutions on
either side of the forward osmosis membrane: higher osmotic pressure difference →
higher rate of water diffusion. In ideal solutions with low solute concentration the
osmotic pressure difference (ΔΠ) can be approximated by the Morse equation:

Δ∏ = iRTΔM

 i is The Van’t Hoff factor, which reflects the dissociation multiple of the solute
species in question. For a dilute solution of sodium chloride, the Van’t Hoff
factor is equal to 2 because 1 mole of NaCl dissociates into 2 moles of solutes
in aqueous solution.
 R is the gas constant in L*atm*K-1*M-1
 T is the temperature of the solution in Kelvin [K]
 M is the molarity of the solution in Molar [M]

It is important to note, that osmotic pressure is a colligative property of solutions,

meaning that it depends exclusively on the number ratio of solute particles to solvent
molecules in a solution, and NOT on the type of chemical species present. Hence a 1M
NaCl solution with a Van’t Hoff factor of 2 will exert the same osmotic pressure as a 2M
sugar solution with a Van’t Hoff factor of 1.
COPYRIGHT FORWARDOSMOSISTECH

How do forward osmosis membranes differ from reverse osmosis

membranes?

Both forward osmosis membranes and reverse osmosis membranes are designed to be
almost exclusively selective to water molecules – the difference lies in the means by
which water molecules are driven through the membrane. To better understand how
the mode of water transport across a membrane influences its physical design and
resulting mechanical properties we start with the equation relating water flux ( across
a membrane to the driving force at work:

Jw = A(ΔP-ΔΠ)

 A is the “pure water permeability coefficient” – an intrinsic membrane

property
 ΔP is the difference in hydraulic pressure across the membrane
 ΔΠ is the difference in osmotic pressure across the membrane

As mentioned earlier, forward osmosis process are driven by osmotic pressure

differences and the direction of water diffusion is from low concentration (the feed
side) to high concentration (the draw side). In most cases, there is no hydraulic
pressure difference at work in forward osmosis processes (ΔP = 0). Reverse osmosis
processes, on the other hand, are driven by hydraulic pressure differences and the
direction of water diffusion is from high concentration to low concentration (i.e. against
the osmotic pressure). In other words, in reverse osmosis applications, the hydraulic
pressure applied must be larger than the osmotic pressure of the solution to be treated
in order for water to diffuse through the reverse osmosis membrane.

So the main difference between forward osmosis membranes and reverse osmosis
membranes is that reverse osmosis membrane require energy-intensive hydraulic
pressures to operate whereas forward osmosis membranes require only osmotic
pressures. Well – you may ask – if forward osmosis membranes do not require energy-
intensive hydraulic pressures, why aren’t all water membrane processes based on
forward osmosis processes? The short answer to this question is that forward osmosis
systems do not directly produce decontaminated water as is the case for reverse
osmosis systems. In forward osmosis processes, the decontaminated water ends up in
the high concentration draw solution and – if needed as an end product – must be
subsequently separated from the draw solutes.

The difference in driving force between reverse osmosis and forward osmosis
processes is reflected in the physical design and mechanical properties of reverse
osmosis and forward osmosis membranes as illustrated below. Reverse osmosis
membranes must be mechanically stable to cope with prolonged exposure to hydraulic
pressure while forward osmosis membranes must be as thin as possible to allow for
rapid diffusion of water and solutes in the bulk membrane material:
Mathematical Model

Modelling FO membranes was first discussed by Lee et al. which was updated by Loeb
et al. and resulted in the following relationship of the water flux through the membrane

𝑩 + 𝑨 𝝅𝑫,𝒃
𝑱𝒘 = 𝑲𝒎 𝑰𝒏 ( )
𝑩 + 𝑱𝒘 + 𝑨 𝝅𝑭,𝒎

Where

𝑨,B=water and salt permeability respectively

𝑫
𝝅𝑫,𝒃 , 𝝅𝑭,𝒎 =Draw solution and feed osmotic pressures And 𝑲𝒎 = 𝑺

Where D is the solute diffusion coefficient and S is the support layer structural
parameter of the FO membrane.
Mass transfer coefficient for the solute on both sides is

𝟏 𝑫𝜺𝒆𝒇𝒇
=
𝑲 𝝉𝒍

And resistance to solute diffusion is the reciprocal of the mass transfer coefficient given
by Lee et al. as follows.

𝝉𝒍
𝑲=
𝑫𝜺𝒆𝒇𝒇

Where 𝝉=tortuosity of the support layer of the membrane.

l=support layer thickness

D=diffusion coefficient

𝜺=effective support layer porosity.

The structural parameter was expressed by McCutcheon et al. as follows:

𝝉𝒍
𝑆 = 𝐾𝐷 =
𝜺𝒆𝒇𝒇

Until recent studies FO utilized polyamide based thin film composite RO :(TFC) RO
membranes or commercially available asymmetric cellulose triacetate (CTA)
membranes. But the problem arose with (TFC) RO was that being gold standard in RO
for high water permeability & selectivity and chemical and physical stability it poses
high resistance to the water flow at low pressure due nonporous structure having
structural parameter greater than 10,000.

On contrary CTA membranes were more successful than the TFC membranes in FO in
spite of having low permeability and selectivity.
But recent research led to the dramatic decrease of the structural parameter of TFC
membranes by its formation with phase inversion-formed support which specifically
decrease the structural parameter.

Based on recent developments in reduction of Structural parameter of TFC membranes

A.Tiraferi et al. led to the expression of water flux through the membrane as follows:

𝜋𝐷 exp (−𝐽𝑤 𝑆)− 𝜋𝐹 exp (𝐽𝑤 )

𝐷 𝐾𝑓
𝐽𝑤 = 𝐴
𝐵 𝐽𝑤 𝐽 𝑆
1+ − exp ((− 𝑤 ))]
{ 𝐽𝑤 [𝑒𝑥𝑝 (𝐾𝑓 ) 𝐷 }

What determines forward osmosis membrane performance?

Before going into details about forward osmosis membrane performance, it is useful to
note that most forward osmosis membranes are of the asymmetric composite type –
meaning that they consist of a nanometer thin rejection layer (typically 100-200nm in
thickness) fused with a micrometer sized underlying support layer (typically 100-
200μm in thickness), which provides mechanical support and overall strength to the
membrane material.

It turns out that forward osmosis membrane performance is governed by the physical
properties of both the rejection layer and the underlying support layer:

The A-value of a forward osmosis membrane – the higher the better

The membrane A-value value (also known as the pure water permeability coefficient)
is a property of the membrane’s active layer and it determines the water flux
performance at a given osmotic pressure difference across the active layer of the
membrane. FO membrane developers seek to increase the membrane A-value to
improve the water flux across the membrane during FO operation.

The B-value of a forward osmosis membrane – the lower the better

The membrane B-value (also known as the salt permeability coefficient) is a property
of the membrane’s active layer and it determines the reverse diffusion of a given draw
solute at a given concentration difference of the solute across the active layer of the
membrane. FO membrane developers seek to reduce the membrane B-value to limit
the amount of draw solute being lost into the feed stream during FO operation.

The S-value of a forward osmosis membrane – the lower the better

The membrane S-value (also known as the structural parameter) is a measure of the
resistance of the membrane’s support layer towards solute diffusion . FO membrane
developers seek to reduce the membrane S-value because the smaller the S value, the
easier it is for solutes to diffuse inside the porous support layer, and the higher the
water flux performance.

Which geometrical form-factors are available for forward osmosis

membranes?

Forward osmosis membranes fall into three general geometrical categories, namely:

1. flat-sheet forward osmosis membranes, which are assembled into plate &
frame (stacked) or spiral wound modules
2. hollow fibre forward osmosis membranes, which are assembled into hollow
fibre modules
3. tubular forward osmosis membranes, which are assembled into tubular
modules

Motivation:

Pakistan is facing the crucial crises of water due to the rapid growth of population,
urbanization, and industrialization. The water scarcity not only affects the country's
economy but also endangers the human health. Few decades ago, Pakistan was among
the world's richest fresh water countries but now, Pakistan is among those countries
that are facing the severe shortage of clean water. Furthermore, it is expected to rise
in future if prudent policies are not made and implemented at the earliest. Thus, it is
very important to explore the new and cheap water treatment technologies.

To date, a variety of membrane processes have been developed for clean water
production. Among them, reverse osmosis (RO) is the most common and widely
applied process but it still demands high energy and reveals the limitation of severe
membrane fouling, and low feed recovery. Forward Osmosis (FO) has recently been
explored as an alternate of RO process for clean water production. In contrast to RO, it
is based on the osmotic pressure difference across a semipermeable membrane and
thereby requires no/low hydraulic pressure. Thus, FO process has the advantages of
high water recovery, low fouling propensity, high energy efficiency and consequently
the low cost than the IRO. To date, although both modeling and experimental research
work has been done on FO but still there is a lot to contribute towards this end. It is
due to the fact that FO is still facing the critical challenges of concentration
polarization, optimum draw solution, membrane fouling, reverse solute diffusion, and
consequently there is a need to optimize the membrane structural
parameters. So, this current project would be focused on the modeling/experimental
study of the different membrane morphologies/materials to achieve the best possible
performance in FO membrane process.

Methodology:

Optimization required for FO membrane process will result in the best water flux and
selectivity at reduced structural parameters. Manipulations can be made for the
optimization in

1. Use of different types of draw solutions

2. Use of DS recovery techniques e.g. NF/RO/MD
3. Use of different membrane materials e.g. CTA/TFC-FO/PA
4. Use of different feed concentrations i-e salinity etc.
5. Use of different structures of membranes based of structural parameters.
6. Use of Energy recovery options if NF/RO is used
Optimization can be achieved by the use of process simulation software Aspen Plus.
Methodology consists of the creation of membrane module in Aspen Custom Modeler
by writing code for the calculation of required parameters. To interface it with Aspen
Plus, Aspen Custom Modeler file .acmf will be converted in MSI type file in Visual
studio. Then it will be transported to the Aspen Plus and plant level run will be made
and manipulations will be done to see the effects.

Achievement So Far.

1. Understanding of flow sheeting and results compilation in Aspen Plus.

2. Understanding of development of process module in ACM.
3. Developed FO Membrane module for the calculation of Water flux.