Bioseparation Report - Final2
Bioseparation Report - Final2
Chemical
FACULTY OF CHEMISTRY
AND METALLURGY Engineering
Bioseparation
PROJECT SUBJECT
MEMBRANE SEPARATION
GROUP NO:
III
LIST OF FIGURES
Figure 1.1 A Simplified Schematic Diagram of a Membrane Separation Process ................ 2
Figure 1.2 Fundamentals of Membrane and Membrane Processes ....................................... 3
Figure 1.3 The ‘Sorting Demon’ Has Ensured That A Random Situation (A) Has Been
Transformed Into An Ordered One (B) .................................................................................. 4
Figure 1.4 History of the Development of Membrane Technology [6] ................................. 5
Figure 2.1 Pore Size Range in Microfiltration, Ultrafiltration and Reverse Osmosis ......... 10
Figure 2.2 Particle Sizes in Pressure Driven Membrane Processes ..................................... 10
Figure 2.3 Mechanism of Dialysis ....................................................................................... 11
Figure 2.4 Schematic flow-diagram for an Electrodialysis Stack ....................................... 12
Figure 2.5 Pervaporation Membranes [14] .......................................................................... 13
IV
LIST OF TABLES
Table 2.1 Kinds of Membrane Separation and Their Applications [9] .................................. 7
Table 2.2 Characteristics of Membrane Process .................................................................... 8
Table 2.3 Characteristics of Membrane Process .................................................................... 8
V
ABSTRACT
Membrane separation technology has become a cornerstone of modern industrial processes
due to its versatility, efficiency, and applicability across diverse fields. This report explores
the evolution, classification, mechanisms, and future prospects of membrane separation
systems. Beginning with a historical overview, it traces the development of membrane
technology and its growing significance in industries such as water purification,
biopharmaceuticals, and chemical processing.
The report also evaluates the advantages and disadvantages of membrane-based separation,
shedding light on its operational benefits and limitations. Looking to the future,
advancements in membrane materials, production techniques, and process design are
examined, emphasizing the potential of nanostructured materials and emerging fabrication
technologies like 3D printing to revolutionize the field. Finally, the integration of
membrane processes into a renewable-based industrial framework is discussed, showcasing
their importance in reducing energy consumption and improving sustainability.
1
1. INTRODUCTION TO MEMBRANE SEPARATION
In general, separation processes of fluid mixtures can be divided into two categories:
equilibrium separation and rate governed separation. Conventional separation processes
such as evaporation, distillation, extraction, adsorption and absorption, used on large scales
in industry, are based on equilibrium distribution. A first phase comprising a mixture to be
separated is brought into intimate contact with a second phase. After a certain time,
thermodynamic equilibrium is established between the two phases. This implies that both
phases show the same temperature and all components have the same chemical potential in
both phases. The analytical concentrations of a component in the two phases, however,
may differ, e.g. a component can be highly enriched in one phase and depleted in the other
one. If now the two phases are separated by an appropriate means, the enriched component
can be recovered usually by establishing a new equilibrium at a different temperature or
pressure. On the other hand, if separation is based on differences in transport rate through
some medium under the influence of a driving force resulting from a gradient in pressure,
concentration, temperature, or electrical field, it is termed as rate governed separation.
Membrane is one such medium, separating one phase from the other. Let us consider the
simplified diagram of a stirred cell membrane system shown in Figure 1.1. The membrane
is placed on a rigid and highly porous support plate hold between the two compartments.
The feed, composed of components A and B, enters into the upper chamber and flows over
the membrane. Part of the feed stream is transferred through the lower chamber. With a
perfect membrane, only component A will transfer through the membrane (permeate),
while component B will remain in the upper chamber (retentate). Either component (A or
B) may be the desired product [1].
2
Membrane technology is an emerging technology and has become increasingly important
in our life. A significant breakthrough for industrial applications of synthetic membranes
started in the 1960s, although the earliest recorded study of membrane phenomena can be
traced back to the middle of the eighteenth century [2]. With nearly 60 years of rapid
development, today, various membrane processes have found numerous industrial
applications, which cover water and dairy purification, sea and brackish water desalination,
wastewater reclamation, food and beverage production, gas and vapor separation, energy
conversion and storage, air pollution control and hazardous industrial waste treatment,
hemodialysis, proteins and microorganisms’ separation, etc. Our ability to restructure
production processes, protect the environment and public health, and develop new
technologies for sustainable growth has all been substantially improved by membrane
technology. With the development of new or improved membrane materials and
membranes with better mechanical, thermal, and chemical properties, or better
permeability and selectivity characteristics, as well as with lower capital and operating
costs, the range of applications for membrane technology is still growing.
The word “membrane” is derived from the Latin word “membrana” and was first used in
popular English media sometime before 1321. “Membrane” has different meanings in
different domains. In association with separation, concentration or purification processes, a
membrane can be essentially defined as a barrier to separate two phases and be able to
restrict the transport of various components in a selective manner, as shown schematically
in Fig. 1. A conventional filter also meets the definition of a membrane; however, the term
“filter” is usually limited to structures that separate particulate suspensions larger than 1–
10 mm [3].
3
1.1 History of Membrane Separation
Thought experiments have gained fame in physics due to Einstein. These thought
experiments are often used to lay the foundation for and simplify an idea. The basis of
membrane separation technology, which is the main subject of this report, is also based on
a thought experiment. Maxwell's demon is a thought experiment that appears to disprove
the second law of thermodynamics. It was proposed by the physicist James Clerk
Maxwell in 1867. [4] In his first letter, Maxwell referred to the entity as a "finite being" or
a "being who can play a game of skill with the molecules". Lord Kelvin would later call it
a "demon” [5]. In 1861, at about time that Graham reported his first dialysis experiments
using synthetic membranes, Maxwell created the ‘sorting demon’, a being whose faculties
are so sharpened that he can follow every molecule in its course and would be able to what
is at present impossible to us. In other words, the demon is able to discriminate between
molecules. Suppose that a vessel is divided into two parts A and B by a division in which
there is a small hole and that Maxwell’s demon sits at the hole which he can open and close
at will.
Figure 1.3 The ‘Sorting Demon’ Has Ensured That A Random Situation (A) Has Been Transformed
Into An Ordered One (B)
Part A is filled with a gas consisting of hot (H) and cold (C) molecules (i.e. H and C differ
in average speed) and the demon allows only the hot molecules (H) to pass. After he has
been doing this for a while, the hot (H) and cold (C) molecules will be separated
completely (Figure 1.b).
Hence, starting from a random situation, an ordered one is attained which is against the
second law of thermodynamics. This law states that a system tends to maximise its entropy,
i.e. when leftalone, the system tries to reach a situation of maximum disorder. Suppose
now we have a membrane that separates the two parts of the vessel, with part A being filled
4
with an isomeric mixture. Now, instead of employing a demon, we exert a driving force on
both isomers. The membrane may discriminate between the two types of molecules
because of differences in size, shape or chemical structure, and again separation will be
achieved, but only to a limited extent.
The separation of substances which mix spontaneously can be accomplished either via a
demon or some device which consumes energy supplied in the form of heat or mechanical
work. The basic principle of any separation process is that a certain amount of energy is
required to accomplish the separation. Hence, two substances A and B will mix
spontaneously when the free enthalpy of the product (the mixture) is smaller than the sum
of the free enthalpies of the pure substances. The minimum amount of energy (Wmin),
necessary to accomplish complete separation is at least equal to or larger than the free
enthalpy of mixing [6].
The concept of the ideal semipermeable membrane able to separate two species with the
theoretical minimum work has been used by thermodynamicists for more than 150 years,
but attempts to use membranes for practical separations did not begin until the 1900s,
when Bechhold devised a technique for preparing nitrocellulose membranes of graded pore
size.
Later workers, particularly Zsigmondy, Bachmann, Elford and Ferry, refined these
preparative techniques and membranes were used to separate a variety of laboratory
solutions by dialysis and microfiltration. By the 1930s, microporous membranes were
produced commercially on a small scale. The first ion exchange membranes were made at
about the same time; these were used by Teorell, Meyer and Seivers to develop their theory
5
of ion transport. This work led eventually to the development of electrodialysis. By the
1960s, therefore, the elements of modern membrane science had been developed, but
membranes were only used in laboratories and in a few small, specialized industrial
applications. There was no signiRcant membrane industry, and total sales for all
applications probably did not exceed US$10 million. Membrane processes suffered from
three problems that prohibited their widespread use: they were too slow, too expensive and
too unselective. Partial solutions to each of these problems have since been developed, and
sales of membranes and membrane separation equipment have grown several hundred-
fold. Currently, several tens of millions of square metres of membranes are produced each
year, and a membrane industry has been created. The problem of slow permeation rates
through membranes was largely overcome in the late 1960s and early 1970s by the
development of imperfectionfree ultrathin membranes. These membranes are anisotropic
structures and consist of a thin selective surface Rlm supported by a much thicker
microporous substrate to provide mechanical strength. Because the selective surface Rlm is
very thin, these membranes have high Suxes. The problem of packing a large membrane
area into a low-cost module has also been solved since the 1980s.
The earliest module designs were plate-andframe or tubular units similar to conventional
heat exchangers. These designs are still used in some processes, such as ultrafiltration, in
which the ability to clean fouling deposits from the membrane surface is important.
However, the cost of both designs is relatively high, and in most processes they have been
displaced by capillary, hollow-fine-fibre and spiralwound module designs [7].
6
Pressure driven membrane process:
Electrodialysis (ED)
Apart from the above processes, there are other membrane processes such as facilitated or
carrier mediated membrane transport, liquid membrane separation, pertraction, membrane
contactors, membrane reactors, membrane distillation, charge mosaic membranes, and
piezodialysis and hybrid processes in which membrane separation is combined with
conventional processes [8].
7
Table 2.2 Characteristics of Membrane Process
2.1. Microfiltration
8
up to 99% removal can be achieved by this technology. However, it is limited to virus
disinfection.
2.2. Ultrafiltration
Ultrafiltration works on same mechanism of size exclusion but the pores are smaller in this
process than microfiltration. It separates particles in the diameter range of 0.01- 0.1μm. In
addition to suspended solids, organic matter, pathogens, colloids and viruses can be
removed by this technology and biological oxygen demand; turbidity can be greatly
reduced up to 95%. These processes are frequently used as pre-treatment for the reverse
osmosis processes. Hydrodynamic conditions and physicochemical properties of
membrane materials are also responsible for the rejection achieved by these processes.
However some studies have reported that UF membranes do not completely block bacterial
permeation because of membrane deterioration due to biofouling. Ultrafiltration can also
remove the soluble and colloidal forms of nitrogen, phosphorus and organic carbon and 10-
85% rejection can be achieved depending on whether the contaminants are in soluble phase
or particulate. However this technology has limitation in removing dissolved solids.
2.3. Nanofiltration
Nanofiltration process works on high hydraulic pressure and used for separation of
dissolved chemicals such as salts. It is quite similar to reverse osmosis and separates the
same solutes as reverse osmosis, but its rejection efficiency is slight lower to reverse
osmosis. It is used as low energy demanding processes as compared to reverse osmosis for
some limited applications. These processes were introduced in the recent 2-3 decades for
purposely and selectively permeating some ionic solutes from feed to permeate.
Nanofiltration has higher water permeability and requires low pressure as compared to
reverse osmosis. Hence, it require less energy and in turn economical than reverse osmosis.
Solute rejection in this process involves different exclusion and transport mechanism than
low-pressure membrane processes. Solute exclusion is done on the basis of dielectric,
steric exclusion as well as adsorption to the membrane surface in some cases. Rejection
rate of nanofiltration is reported 20-80% for monovalent ions and above 95% for divalent
ions of the same charge. In the case of uncharged solutes, rejection depends on molecular
weight. Therefore, nanofiltration permeate sometimes contain molecules out of the size
range of membrane pore. In some new studies, some pre-treatment techniques like ozone
9
pre-treatment and non-thermal crystallization are also suggested for improving the
separation efficiency and reduction of membrane fouling.
In reverse osmosis process, high pressure is applied to pass the solvent through the
membrane and most solutes are removed, mostly dissolved solids. The applied pressure is
always higher than the osmotic pressure of feed to achieve desired separation by this
process. This process rejects mostly dissolved solids, organic molecules and viruses which
are major contaminants in the wastewater. Microfiltration/Ultrafiltration are used for pre-
treatment of feed before reverse osmosis to minimize the energy consumption as well as to
improve membrane performance. Reverse osmosis is commonly used in desalination of
water and it can reject up to 99.5-99.8% of sodium chloride salt. It provides complete
rejection of pathogens due to sub-nanometer scale of reverse osmosis membrane pores
[10].
Figure 2.1 Pore Size Range in Microfiltration, Ultrafiltration and Reverse Osmosis
10
2.5. Dialysis
Dialysis is the process of separating molecules in solution by the difference in their rates
of diffusion through a semipermeable membrane, such as dialysis tubing [11].
Dialysis is a common laboratory technique that operates on the same principle as medical
dialysis. In the context of life science research, the most common application of dialysis is
for the removal of unwanted small molecules such as salts, reducing agents, or dyes from
larger macromolecules such as proteins, DNA, or polysaccharides [12].Dialysis is also
commonly used for buffer exchange and drug binding studies.
2.6. Electrodialysis
11
Figure 2.4 Schematic flow-diagram for an Electrodialysis Stack
Depending on the type of membrane used, ions can be selected according to their valence.
Therefore this process can be used for fractionating ions of different valence. The main
application of electrodialysis is in demineralization in general and in the desalinization of
brackish water.
2.7. Pervaporation
12
Pervaporation is more expensive than other membrane processes due to the required supply
of heat to produce the evaporation. It is, therefore, used in the separation of components
from mixtures that are difficult to treat, such as azeotropic solutions and isomer mixtures,
for which conventional processes would be more costly [13].
13
3. MEMBRANE SEPARATION MECHANISM
14
Figure 3.2 Basic Type of Membrane Mechanisms Schematic Representation
There are many transport mechanisms involved in membrane separation depending on the
type of selective barrier [17]:
▪ Spiral-wound modules: An advanced form of plate and frame model in which two
membranes with their active side are placed facing each other separated by a feed
channel spacer and centrally connected to perforated permeate collection coil.
Central permeate collection tubes have membrane sheets wound around them; these
types of modules mostly used in reverse osmosis and nanofiltration [18].
16
Figure 3.4 Spiral Wound Reverse Osmosis (RO) Membrane Module
17
▪ Flat sheet modules: Flat sheet membranes are housed in plate-and-frame or
cassette devices, a gap of 0.5 to 2.0 mm between the membranes for feed flow. The
membranes are supported by plates and porous spacers on the permeate side.
Multiple membrane-and-plate units are stacked together to create a module or
cartridge [21].
Figure 3.6 Flat Sheet Membrane Module Designs with Electrophoresis Assistance
▪ Crossflow filtration systems: At the membrane surface, crossflow filters have the
ability to reduce the fouling buildup. The retentate stream can be easily
recirculated, making it possible to process large volumes of feed material. Scaling
up or down crossflow filtration is simple, as it just requires maintaining the
crossflow, either by keeping a constant flow rate per unit area or maintaining
constant pressure [22].
▪ Dead-end filtration systems: The simplest form of filtration is dead-end filtration
where the entire feed flow is pushed through the membrane, causing filtered
material to build up on the membrane’s surface. Since this buildup reduces
filtration capacity due to clogging, the process is batch-based and requires an
additional step to remove the accumulated material. Despite this, dead-end filtration
is highly effective for concentrating compounds [23].
18
Figure 3.7 Comparison Between Dead End and Cross Flow Filtration
3.2.3 Pumps
▪ High-pressure pumps: Used to provide the required pressure for processes such as
reverse osmosis, nanofiltration and high-pressure membranes.
▪ Peristaltic pumps: In the application of tangential flow filtration, the delivery
pump is required to provide pressure to drive the filtrate through the filter and
provide transmembrane pressure, so that the excess water molecules and other
small molecules (colorless and transparent) in the solution can pass through the
ultrafiltration membrane and be collected in a fixed container. It is required that the
delivery pump must have the characteristics of high precision, stable delivery and
low shear force [24].
19
3.2.4 Pressure vessels
Enclosed chambers designed to hold membrane modules under pressure, essential for
processes requiring high pressure.
Equipment for filtering and conditioning the feed stream before entering the membrane
module, which may include microfiltration systems, chemical dosing units, and
sedimentation tanks.
Equipment for cleaning and maintaining membrane to prevent fouling and extend
membrane life; often involves chemical cleaning solutions and backwashing systems.
Instruments for measuring parameters such as pressure, flow rate, temperature, and
concentration; often equipped with automated control systems for optimized operation.
Storage tanks for collecting permeate and retentate; essential for managing and analyzing
the separation output.
These types of equipment are essential in the effectiveness and efficiency of membrane
separation processes. They are widely used in various industries like water treatment, food
and beverage production, and biopharmaceutical manufacturing, helping to ensure smooth
and reliable operations in these fields.
20
4. DIVERSE APPLICATIONS OF MEMBRANE SEPARATION
TECHNOLOGY
Desalination technologies can be classified into three main types: membrane technology,
thermal technology, and chemical technology. Chemical technology is generally deemed
impractical for desalination, while thermal technology requires a significant amount of
thermal and electrical energy, resulting in high costs and substantial greenhouse gas
emissions. Consequently, membrane technology emerges as a viable and technically
feasible solution, being the most widely used method, with thermal technology being less
common. Over past few decades, cellulose based membranes and thin film composite
membranes have been successively employed in membrane desalination, showcasing
improved stability, water permeability, and molecular sieving performance [26].
Recently, considerable research has focused on membranes made from two dimensional
(2D) materials, introducing a novel approach to membrane desalination. Typically, two
distinct methods are used for desalination with 2D materials: leveraging the natural
nanochannels in stacked 2D layers and creating nanopores withing the membrane plane,
referred to as nanolaminate membranes and nanoporous membranes, respectively.
21
microfiltration. Despite the many advantages of these technologies, they face significant
challenges including high capital and operating costs [27].
Pressure driven membrane processes namely MF, UF, NF, and RO lead to effective
separation of components with a large range of particle sizes. Furthermore, membrane
processes are more economical in terms of energy consumption compared to traditional
techniques [28].
4.4 Biopharmaceuticals
Membrane separation technologies are widely applied in downstream processes for the
separation and purification of biopharmaceuticals through methods including
microfiltration, ultrafiltration, and diafiltration. The advanced technique of membrane
chromatography enables the efficient purification of monoclonal antibodies. Membrane
filtration techniques such as reverse osmosis and nanofiltration are being integrated with
bioreactors and advanced oxidation processes to recover wastewater produced by
pharmaceutical plants. Nanofiltration with organic solvent stable membranes can facilitate
solvent exchange and catalyst recovery during the synthesis of pharmaceutical compounds
22
and intermediates. Hollow fiber formed membranes are conveniently employed to facilitate
the crystallization of pharmaceutical compounds [29].
Membrane gas absorption (and stripping) process is a gas-liquid contacting operation. The
core in the membrane gas absorption process is a microporous hollow fiber membrane. The
gas stream is fed along one side of the membrane; at the same time, absorption liquid is
flowing at the other side of the membrane [30]. In the membrane absorption process, a
hydrophobic or hydrophilic hollow fiber contactor is used to separate a feed solution
containing a solute from the receiving gas phase. In the case of the stripping process, the
solute to transfer is contained in the gas phase.
4.6 Dialysis
23
5.ADVANTAGES AND DISADVATAGES OF SEPARATION WITH
MEMBRAN
5.1 Advantages
2. Energy Savings
▪ Membrane separation typically operates without phase change (e.g., no need for
boiling or condensation), which requires significantly less energy compared to
traditional methods like distillation or evaporation.
3. Environmentally Friendly
▪ Membrane processes often eliminate or significantly reduce the need for harmful
chemicals, making them cleaner and safer for the environment. This is particularly
beneficial in wastewater treatment and in industries aiming to reduce their
ecological footprint.
▪ Membrane systems are typically compact and modular, meaning they can fit into
smaller spaces and are easier to install, expand, or replace than traditional systems.
This makes them suitable for both small-scale and large-scale operations.
5. Continuous Operation
24
6. Scalability
▪ Membrane systems can be easily scaled up or down, making them versatile for
various production capacities and industries. The modular nature of these systems
means new units can be added or removed as needed.
▪ Since membrane systems often require less energy, minimal chemical additives,
and fewer moving parts, they tend to have lower operational and maintenance costs
over time compared to mechanical separation techniques.
9. Selective Separation
25
5.2 Disadvantages
1. Membrane Fouling
▪ One of the most common issues is fouling, where particles, organic matter, or
microorganisms accumulate on the membrane surface. This reduces permeability
and effectiveness, requiring frequent cleaning or replacement.
3. Limited Lifespan
4. Pressure Requirements
5. Selectivity Limitations
6. Concentration Polarization
▪ The buildup of retained particles near the membrane surface can create
concentration gradients, reducing the driving force for separation and lowering
process efficiency.
26
7. Sensitivity to Operating Conditions
8. Waste Generation
▪ While membranes reduce the use of chemicals, the cleaning processes (e.g.,
chemical backwashing) and the concentration of retained substances can create
waste streams that require proper disposal.
▪ Some membranes are not suitable for use with highly corrosive or abrasive
materials, which limits their applicability in industries dealing with such
environments.
27
6. THE FUTURE OF MEMBRANE PROCESSES
Polymers are the dominant material for industrial membrane processes, including porous
membranes used in microfiltration, ultrafiltration, and dialysis, and dense membranes used
in reverse osmosis, gas separation, and pervaporation. They provide cost-effective, scalable
solutions for creating thin separation layers using methods like phase inversion and
extrusion. While these materials exhibit limitations in temperature and chemical resistance,
advancements in nanostructured materials such as zeolites, carbon nanotubes, and
graphene have significantly surpassed the traditional permeability/selectivity trade-offs.
These materials exhibit high-temperature stability and chemical compatibility, enabling
innovative applications like high-temperature membrane reactors that integrate separation
and catalysis in a single unit [33].
Membrane module production faces challenges due to its reliance on toxic solvents and
complex fabrication techniques. Efforts to develop green solvents and bio-based materials
have made production more sustainable. Innovations like solvent-resistant polymers and
3D printing are revolutionizing the field. Though large-scale 3D-printed modules remain a
challenge, 3D printing has the potential to create intricate geometries, enabling more
efficient, customized designs that mimic biological structures for improved performance.
Process Systems Engineering (PSE) tools have optimized membrane design and operation
across numerous industrial applications. However, challenges remain in optimizing
complex multistage or hybrid systems. Emerging design paradigms are driving progress
toward more efficient and integrated solutions.
28
6.4 Membrane Processes in a New Industrial Environment
The transition from fossil fuels to renewable resources is reshaping industrial processes,
increasing the demand for energy-efficient separation technologies like membranes.
Membranes are particularly suited for biorefineries, which process heat-sensitive, aqueous
mixtures. Alternative driving forces, such as temperature gradients, electrical fields, and
light, are gaining attention for their potential in creating more sustainable and integrated
industrial systems.
29
7. CONCLUSION
Membrane separation technologies have emerged as a preferred solution in a wide range of
industries, from water purification and wastewater treatment to food processing and
biopharmaceuticals. These processes offer significant advantages, including sustainability,
high efficiency, and lower energy consumption compared to traditional separation methods.
However, despite their growing popularity, several challenges need to be addressed to
enable their broader adoption and optimization. The development of advanced membrane
materials with improved selectivity, permeability, and chemical stability is critical to
enhancing performance in diverse applications. Additionally, issues such as membrane
fouling and clogging, which can significantly reduce operational efficiency and increase
maintenance costs, must be resolved. Innovations in anti-fouling surface coatings, better
cleaning protocols, and enhanced module designs hold promise in mitigating these
limitations. By overcoming these technical barriers, membrane separation processes will
continue to evolve, unlocking their full potential for more sustainable industrial
applications, contributing to resource efficiency and environmental conservation.
30
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