UNIT 3
Advance Treatment Methods
UNIT 3
TERTIARY/ADVANCED WASTEWATER TREATMENT:
Ultrafiltration, Filtration, Adsorption on Activated Carbon, Ion Exchange,
Reverse Osmosis.
BIOLOGICAL NUTRIENT REMOVAL:
Introduction, Biological nitrogen removal-, Nitrification–denitrification.
Physicochemical process for nitrogen removal - Air stripping
Filtration
Parameter Microfiltration (MF) Ultrafiltration (UF) Nanofiltration (NF) Reverse Osmosis (RO)
< 0.001 µm (dense,
Pore size range ≈ 0.05–10 µm ≈ 0.001–0.1 µm ≈ 0.001–0.01 µm
non porous like)
Very low; retains small
MWCO (approx.) Not usually defined by MWCO 1–800 kDa 80–800 Da
ions/molecules
20–80 bar (high; up to 80+
Typical pressure 1–5 bar (low) 2–10 bar (moderate) 10–20 bar (moderate–high)
for seawater)
Viruses, some organics, Almost all dissolved salts,
Bacteria, suspended solids, Bacteria, viruses, colloids,
Particles removed cysts, some protozoa proteins, larger organics
divalent ions (Ca²⁺, Mg²⁺), ions, small organics,
some organics bacteria
Partial removal (especially
Dissolved salts Very little (no desalting) +1
Little (mainly large
multivalent ions; 50–90%
High desalination (90–99+
removed solutes) % salt rejection) +1
salt rejection)
Water quality Turbidity & bacteria removal; High clarity water, Softened water, reduced Very low TDS, near pure
outcome not for desalination microorganism removal hardness & organics water
Pre treatment for RO, Softening, organic Desalination (seawater/
Pre treatment, clarifiers, basic
Main applications drinking water filters drinking water plants, removal, low energy brackish), ultrapure water
dairy/food processing +1 desalination (brackish) for labs/industry
Energy
Low Low–moderate Moderate High
requirement
‑
‑
‑
‑
‑
‑
‑
‑
‑
Ultrafiltration
• Ultrafiltration is a pressure-driven membrane separation process in which water and low
molecular weight substances permeate through the membrane while the particles, colloid and
macromolecules are retained.
• The primary removal mechanism is size exclusion, although the electrical charge and the
surface chemistry of the particle or membrane may affect the efficiency.
• UF has evolved since the 1960s as a consequence of the development of asymmetric RO
membranes.
• However, unlike RO, which mainly deals with desalination and similar operations, UF has a
broader range of applications.
Ultrafiltration
• Ultrafiltration pore ratings ranges from approximately 1000–500,000 Da, thereby making UF
more permeable than nanofiltration (200–1000 Da).
• Since only high molecular weight species are removed by ultrafiltration, the osmotic pressure
difference across the membrane surface is negligible.
• Therefore, in ultrafiltration low applied pressure is sufficient to achieve high flux rates.
• UF can be used to accomplish one or more of the following:
❖ Concentration of solutes by removal of solvent
❖ Purification of solvent by removal of solute
❖ Fractionation of solute
❖ Analysis of complex solutions for specific solutes
Ultrafiltration
Ultrafiltration
• In conventional ultrafiltration configurations, the process solution is pressurised, typically
between 10–70 psi, while in contact with a supported semi-permeable membrane.
• Solutes smaller than the molecular weight cut off emerges as ultrafiltrate, and retained
molecules are concentrated on the pressurised side of membrane.
• Pressure sources such as compressed gas (nitrogen) and pump systems are commonly used.
The figure below depicts basic system of ultrafiltration:
Ultrafiltration
• UF is used to separate solutes of size ranging from 5 kDa to 500 kDa.
• To achieve the above, a pore size of 1 to 20 nm is needed.
• The demarcation between UF and other processes such as RO and MF, is often not very
distinct.
• UF has been successfully used to concentrate macromolecules, however its use to fractionate
macromolecules has gained a lot of attention in the past few years.
• The view that UF is a completely size-exclusion-based process is only true as a first
approximation.
• Factors such as solute–solute interaction, solute–membrane interaction and mode of solute
transport such as either diffusive or convective, also plays a role.
Ultrafiltration
• The first commercial use of UF was for the concentration of proteins.
• UF based separation and purification is attractive because of (1) high throughput of product,
(2) low process cost and (3) ease of scale-up.
• The major areas of applications are:
❖ Fractionation of macromolecules ❖ Removal of solvents from solutions of
macromolecules ❖ Diafiltration: removal of salts and other low molecular weight
compounds ❖ Removal of cells and cell debris from fermentation broth ❖ Virus removal
from therapeutic products ❖ Harvesting of biomass ❖ Membrane reactors and
bioreactors❖ Effluent treatment (domestic as well as industrial)
Ultrafiltration
• To carry out the UF process efficiently, the UF membrane must have the following
features:
❖High hydraulic permeability to solvent•
❖Sharp ‘retention cut-off’
❖Good mechanical durability
❖Good chemical as well as thermal stability
❖Excellent manufacturing reproducibility• Ease of manufacture
Ultrafiltration
• UF membranes differ from MF membranes in terms of their morphology.
• MF membranes are usually symmetric whereas UF membranes are anisotropic.
• They have a ‘skin layer’ fused on the top of a microporous layer.
• This skin layer gives the selectivity to the UF membrane whereas the microporous layer
provides mechanical support.
• The thickness of skin layer ranges from 0.2 to 10 micron
depending on the material and application.
Advantages
❖The process can be carried out at ambient temperature, thus avoiding thermal as well as
oxidative degradation of product. However, in such cases solute diffusion coefficient is
temperature dependent.
❖Ultrafiltration permits the removal of water up to 90% at ambient temperature.
❖Since, there is no phase change, breaking of emulsions, collapse of gels and mechanical
damage do not occur.
❖No solvent or other precipitating agents are required for the concentrating process.v. No
generation of wastewater.
❖Keeps essential minerals in water.
❖Can be installed quickly and easily.
Basic Features
❖Driving force: Pressure gradient (1–10) bar
❖Transport mechanism: Pore flow
❖Separation principles: Sieving (or size exclusion)
❖Size of retained species: 10–100 Å
❖Type of membrane: Asymmetric, porous, composite
❖Membrane material: Polysulfone, polyethersulfone, polyvinylidene fluoride,
polyacrylonitrile, polyimide, aliphatic polyamides, cellulosic, ceramic
❖Pore size: 1–100 nm
❖Flux: 50–1000 L/m²·h
❖Energy consumption: 10–150 W/m³
Membrane Characterstics
The important characteristics of membrane material are:
• Porosity, morphology, surface properties, mechanical strength, chemical resistance.
• Polymeric materials such as polysulfone, polyethersulfone, polyvinylidene fluoride,
polyacrylonitrile, polyimide, etc. have been successfully used as ultrafiltration
membrane.
• These membranes usually have two layers:
❖ Thin (0.1 – 0.5 µm) semipermeable membrane made of cellulose ester, and
❖ Substructure support material
• Most of today’s UF membranes are prepared by variations of the Loeb–Sourirajan
process.
Membrane Characterstics
The important characteristics of membrane material are:
• Porosity, morphology, surface properties, mechanical strength, chemical resistance.
• Polymeric materials such as polysulfone, polyethersulfone, polyvinylidene fluoride,
polyacrylonitrile, polyimide, etc. have been successfully used as ultrafiltration
membrane.
• These membranes usually have two layers:
❖ Thin (0.1 – 0.5 µm) semipermeable membrane made of cellulose ester, and
❖ Substructure support material
• Most of today’s UF membranes are prepared by variations of the Loeb–Sourirajan
process.
Membrane Characterstics
• One of the oldest and most widely used separation techniques.
• Primarily used for water purification.
• First adopted for seawater desalination (1950).
• Initially slow and limited to laboratory applications.
• Significant advancements due to:
❖ Research and technological development
❖ Improvements in polymer science
❖ Development of efficient membranes
• Currently used worldwide for:
❖ Industrial purposes
❖ Residential water purification
❖ Commercial applications
❖ Scientific use
Reverse Osmosis Process
• A semi-permeable membrane is used in the process.
• Large solute molecules cannot pass through the membrane.
• Solute remains on the pressurized side.
• Pure solvent passes through the membrane.
• Solute concentration increases on one side.
• The other side becomes more dilute.
• Liquid levels may change slightly during the process.
• Reverse osmosis occurs when:
❖ Solvent moves against the concentration gradient
❖ Flow is from higher concentration to lower concentration
Reverse Osmosis Process
• Osmotic pressure is the minimum pressure required to stop solvent flow through a
semipermeable membrane.
• When pressure applied on the solution side is greater than osmotic pressure:
❖ Solvent moves through the membrane
❖ Flow occurs from high solute concentration → low solute concentration
• This reverse movement of solvent is called reverse osmosis
• Key condition: Applied pressure must be higher than osmotic pressure
• Osmotic pressure is a colligative property and depends on the concentration of the solution.
• Widely used in water purification systems and its an essential step in many modern water
purifiers
Reverse Osmosis Process
• Osmotic pressure is the minimum pressure required to stop solvent flow through a
semipermeable membrane.
• When pressure applied on the solution side is greater than osmotic pressure:
❖ Solvent moves through the membrane
❖ Flow occurs from high solute concentration → low solute concentration
• This reverse movement of solvent is called reverse osmosis
• Key condition: Applied pressure must be higher than osmotic pressure
• Osmotic pressure is a colligative property and depends on the concentration of the solution.
• Widely used in water purification systems and its an essential step in many modern water
purifiers
Reverse Osmosis Process
Reverse Osmosis Benefits
Some of the benefits of reverse osmosis are discussed below.
• This process can be used to effectively remove many types of dissolved and suspended
chemical particles as well as biological entities (like bacteria) from the water.
• This technique has a wide application in treating liquid wastes or discharges.
• It is used in purifying water to prevent diseases.
• It helps in desalinating seawater.
• It is beneficial in the medical field.
Reverse Osmosis Advantages
Reverse Osmosis has several advantages, including the following:
❖Bacteria, viruses and pyrogen materials are rejected by the intact membrane. In this
respect, RO water approaches distilled water in quality.
❖Available units are relatively compact and require little space. They are well suited to
home dialysis.
❖In average use, the membrane has a life of a little more than one to two years before
replacement is necessary.
❖Periodic complete sterilization of the RO system with formalin or other sterilant is
practical
Reverse Osmosis Disadvantages
The disadvantages of RO systems include the following;
❖Cellulose acetate membranes have limited pH tolerance. They degrade at
temperatures greater than 35°C. They are vulnerable to bacteria. They eventually
hydrolyze.
❖Polyamide membranes are intolerant of temperatures greater than 35°C. They have
poor tolerance for free chlorine.
❖Thin-film composites are intolerant of chlorine.
❖High flux polysulfones require softening or deionization of feed water to function
properly.
Reverse Osmosis Performance
Water flux through membrane
Jw is the water flux (volume of water per unit membrane area per unit time, e.g., L/
m²·h)
ΔP is the net applied pressure difference across the membrane (feed side pressure
minus permeate side pressure)
Δπ is the difference in osmotic pressure between feed and permeate sides,
A is the membrane water permeability coefficient (a property of the RO membrane).
‑
‑
Reverse Osmosis Performance
Salt flux through membrane
where:
Js is salt flux (salt mass per area per time),
B is the salt permeability coefficient,
Cf is the average salt concentration on the feed side,
Cp is the salt concentration in the permeate.
Reverse Osmosis Performance
Salt rejection and salt passage
Salt rejection (SR, %):
Cp and Cf can be TDS or specific ion concentrations
Salt Passage (SP, %):
Reverse Osmosis Performance
Permeate flow, recovery, and feed/concentrate relations
System recovery (R, %)
Concentrate (brine) flow rate:
Approximate concentrate salt concentration (when feed splitting is small):
where
Cc is concentrate concentration and R is recovery (in decimal).
Reverse Osmosis Performance
Osmotic pressure (for seawater / brackish water)
For dilute aqueous salt solutions, a common approximation is:
where
i is the van’t Hoff factor (≈ 2 for NaCl),
R is the gas constant,
T is temperature in K,
C is molar concentration
Reverse Osmosis – Numerical
A small brackish water RO unit treats feed water with total dissolved solids (TDS) of
2500 mg/L. The system produces permeate at 15 m³/h, while the feed flow rate is 20 m³/
h and the permeate TDS is 120 mg/L.
Calculate:
The recovery rate (%) of the RO system.
The salt rejection (%) of the membrane.
The concentrate flow rate (m³/h).
Comment on whether this system is operating efficiently (use typical industrial ranges).
‑
Reverse Osmosis – Numerical
Reverse Osmosis – Numerical
4. Efficiency / performance comment
Recovery: 75% is within the typical industrial range (50–85%), so the system is
efficiently converting feed into usable water.
•Rejection: 95.2% salt rejection is good for a brackish water RO system; industrially
RO units often target ≥95–99% rejection.
‑
Osmosis and Diffusion
Electrodialysis
• In contrast to the reverse osmosis process, electrodialysis employs the removal of the solute from the solution
rather than the removal of the solvent.
• In this process, use is made of selective permeable membranes and an electrical potential difference to extract
ions from solution.
• Two types of membranes (anionic and cationic) are arranged alternatively to form many compartments between
the electrodes placed at the two ends.
• When voltage is applied across the cell containing mineralized water, the anions migrate to the positive
electrode and the cations migrate to the negative electrode.
• This causes solution in alternate compartments to become more concentrated while that in the remaining
becomes more dilute.
• The electric power requirement is proportional to the number of ions removed from the water.
Electrodialysis
Key Advantages
• High water recovery (often 85–95%), which is valuable where water scarcity or wastewater reuse is
important.
• Low energy consumption because separation occurs without phase change and does not require high
pressure pumps.
• Operates at low pressure, so membrane fouling and scaling are reduced and aggressive chemical
cleaning is less necessary.
• High selectivity for ionic species, allowing removal or concentration of salts, acids/bases, nutrients,
or heavy metals while leaving non ionized components largely unaffected.
• Can achieve high water quality and is suitable for brackish water desalination, wastewater reuse, and
resource recovery with relatively simple operation and long membrane lifetime
‑
Key Limitations
• High initial investment for membranes, stacks, and power supply; membrane cost also
limits large scale installation.
• Ineffective for non ionic species, so organics, colloids, silica, and suspended solids are not
removed and require separate treatment steps.
• Membrane fouling and scaling from hardness, organic matter, silica, and biofilm reduce
efficiency and need pretreatment and cleaning.
• Less suitable or less economical for very high salinity feeds (like seawater) and for
achieving extremely low final salt concentrations, where energy efficiency declines.
• Operation requires careful control of current density, flow distribution, and polarity to avoid
water splitting and performance loss.
‑
‑
‑
Applications
• Brackish water desalination at low–moderate salinity (typically <3 g/L TDS), where its energy use is
comparable to or better than RO and water recovery is high.
• Selective removal of specific ions such as hardness (Ca²⁺, Mg²⁺), heavy metals, or targeted
contaminants from industrial or brackish streams, often with tailored membranes.
• Nutrient recovery from concentrated wastewaters (e.g., anaerobic digester centrate) to produce
ammonium- and potassium-rich fertiliser solutions.
• Recovery and concentration of valuable acids, bases, and organic acids from fermentation broths or
industrial effluents, where ED can simultaneously purify water and concentrate the product.
• Coupling with renewable energy (e.g., photovoltaic-powered ED) for decentralized treatment of
brackish groundwater in remote or off grid regions.
‑
Ion Exchange Method
What Is Ion Exchange?
Ion exchange is a chemical process to remove unwanted dissolved ions in
water and wastewater. To remove the ions, they are exchanged with ions that
have a similar charge.
Ion Exchange Method
There are two groups of ions:
• Positively charged ions (cations)
• Negatively charged ions (anions)
When positive ions are exchanged during water treatment, the cations that come into contact with the
ion exchange resin are exchanged with other positively charged ions available (usually sodium) on the
resin surface.
During anion exchange, negatively charged ions are exchanged with other negative ions on the resin
surface, these ions are usually chloride ions.
Anion exchange is important as the ions can remove contaminants such as nitrate, arsenic, sulfate, and
fluoride.
Types of Ion Exchange Resins
• Ion exchange resins are either synthetically or industrially produced. Resins are
microporous beads made from polyacrylate and polystyrene. They consist of tiny,
microporous beads that range from 0.3 to 1.3 millimeters.
• When water is passed through the beads, ions inside the resin interact with ions
present in the water. This is how contaminants are captured in the water.
• There are four basic categories of industrial water treatment resins:
• Strong Acid Cation (SAC) Resins
• Strong Base Anion (SBA) Resins
• Weak Acid Cation (WAC) Resins
• Weak Base Anion (WBA) Resins
Types of Ion Exchange Resins
SAC resins neutralize strong bases and convert the salts into corresponding acids. They can
remove all cations, replacing them with hydrogen ions. SAC resins are used over all pH
ranges. (Ex: sulfonated polystyrene–divinylbenzene (PS-DVB) resins)
SBA resins neutralize strong acids and convert the salts into corresponding bases. These are
common in water softening and demineralization processes. (Ammoimium group)
WAC and WBA resins both neutralize strong bases and acids. They are used in partial and
complete demineralization processes and dealkalization systems.
WAC resins remove cations to produce carbonic acid; however, they cannot remove all the
cations in most water supplies. Their high regeneration efficiency (reducing waste) compared
to SAC resins, is what makes them popular. (Carboxylic group)
WBA resins remove acids such as sulfuric, nitric, and hydrochloric acid (Amine group)
Water Softening
• Sodium zeolite softening is the most commonly used ion
exchange water treatment, as zeolites have excellent ion
exchange and absorption rates
• During zeolite softening, water that contains calcium and
magnesium ions (scale-forming ions), passes through a
SAC resin containing sodium. In the resin, the scale-
forming ions in the water are exchanged with the sodium.
• This is why the process is called softening, as the water
becomes hardness-free.
• Water treated with sodium zeolite softening can be used for low to medium-
pressure boiler feedwater, reverse osmosis systems, commercial applications, and
some chemical applications.
Water Deionization
• Water deionization utilizes synthetic resins to remove unwanted dissolved solids from the water via ion
attraction and exchange. The resin contains positively charged hydrogen or hydroxide ions, which causes
the resin to release their ions for exchange.
• The two types of deionizers are mixed-bed deionizers and separate-bed deionizers. Mixed-bed deionizers
use both cation and anion resins in a single vessel, which produces very high water quality. Separate-bed
deionizers contain separate vessels containing cation and anion resins. Separate-bed deionizers have an
economical advantage over mixed-bed deionizers.
Water Demineralization
• While water softening is most commonly used, it
is an insufficient ion exchange method for high-
pressure boiler feedwaters and streams,
particularly ones used to manufacture electrical
equipment.
• Water demineralization removes all inorganic salts in
the ion exchange process.
• During demineralization, a SAC resin (hydrogen form)
converts dissolved salts into their corresponding acids. The
SBA resin (hydroxide form) removes the acids.
• Water demineralisation produces water quality similar to freshwater distillation processes, but
at a much lower cost.
Dealkalization
• When water treatment processes need to remove the water hardness, and reduce alkalinity, but not
remove other solids, dealkalization is used.
• A dealkalizer is similar to a water
softener in removing unwanted
ions from the water, but instead
of removing the calcium and
magnesium ions, the dealkalizer
removes the carbonate ions and
exchanges them for chloride ions.
Advantages
The primary advantages of ion exchange process in water include:
• Rapid results
• Very effective in removing inorganic ions from water
• They can be used for short and long-term applications
• They are quickly installed
• Requires little maintenance
• Possibility to regenerate resin that’s used
• The initial investment is relatively inexpensive
Dis-advantages
There are also a few disadvantages to take into account.
These include the following:
• They cannot effectively remove bacteria from water
• Long-term costs are expensive
• When ion exchange beds are regenerated, salt water is dumped into the
environment
Dis-advantages
There are also a few disadvantages to take into account.
These include the following:
• They cannot effectively remove bacteria from water
• Long-term costs are expensive
• When ion exchange beds are regenerated, salt water is dumped into the
environment
Adsorption
Activated Carbon