Term Report

Subject Separation Process-2

Topic Applications of Separation Adsorptions
Submitted to Sir Hidayatullah Mahar
Section B
Semester 7th
Submitted By
Name Roll No.
Arslan Ahmad 2k18-ChE-121
Usama Tariq 2k18-ChE-125
Usman Ashraf 2k18-ChE-136
Muhammad Awais Younas 2k18-ChE-140

Department of Chemical Engineering

NFC Institute of Engineering & Technology, Multan

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 Adsorption Separation Process
Introduction to Adsorption:
The use of solids for removing substances from either gaseous or liquid solutions has been
widely used since biblical times. This process, known as adsorption, involves nothing more
than the preferential partitioning of substances from the gaseous or liquid phase onto the surface
of a solid substrate.
From the early days of using bone char for decolorization of sugar solutions and other foods, to
the later implementation of activated carbon for removing nerve gases from the battlefield, to
today’s thousands of applications, the adsorption phenomenon has become a useful tool for
purification and separation.
Adsorption phenomena are operative in most natural physical, biological, and chemical systems,
and adsorption operations employing solids such as activated carbon and synthetic resins are
used widely in industrial applications and for purification of waters and wastewaters.

Physical adsorption is caused mainly by van der Waals forces and electrostatic forces between
adsorbate molecules and the atoms which compose the adsorbent surface. Thus adsorbents are
characterized first by surface properties such as surface area and polarity.

A large specific surface area is preferable for providing large adsorption capacity, but the
creation of a large internal surface area in a limited volume inevitably gives rise to large numbers
of small sized pores between adsorption surfaces.

Adsorption Separation of heavier isotopes in sub nanometer pores is given in figure:

The process of adsorption involves separation of a substance from one phase accompanied by its
accumulation or concentration at the surface of another.

The adsorbing phase is the adsorbent, and the material concentrated or adsorbed at the surface of
that phase is the adsorbate. Adsorption is thus different from absorption, a process in which
material transferred from one phase to another (e.g. liquid) interpenetrates the second phase to
form a “solution”. The term sorption is a general expression encompassing both processes.

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On the other hand, nonpolar adsorbents are generally “hydrophobic”. Carbonaceous adsorbents,
polymer adsorbents and silicalite are typical nonpolar adsorbents. These adsorbents have more
affinity with oil or hydrocarbons than water.

Adsorption Equilibrium:
Water pollution, such as heavy metals, dyes, organic, and inorganic pollutants, is a serious problem
for the human being with the rapid urbanization, industrialization, and technological innovations
in various disciplines. Many researchers have developed different methods and materials to
remove the contaminants.

Among them, high concentration of ammonium ions is the major pollutant and is harmful to animal
and human health and also attacks the water plumbing systems. The removal of Ammonical
nitrogen has attracted great attention in wastewater treatment.

For the water treatment, several methods such as chemical precipitation, biological processes, ion
exchange, and adsorption have been taken and applied to the removal of Ammonical nitrogen from
wastewater. Among these technologies, biological processes as one of the most widely used
technologies are effective for wastewater with low concentration ammonium ions but require
complicated configurations and process routing.

For example, Yusof et al reported that zeolite Y synthesized from rice husk ash waste was found
to have higher adsorption capacity than mordenite for ammonium removal, and the equilibrium
isotherm proved its monolayer adsorption. Mishra and Tiwari found that zeolite 13X originated
from Indian fly ash had a good sorption property for metal ions at acidic pH. However, the
collection and processing of these raw materials are the major engineering problems to be solved
in the case of commercializing those waste-originated zeolites.

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So, this work aims to realize the value of zeolite X/activated carbon composite synthesized from
solid waste on the removal of Ammonical nitrogen from aqueous solutions. The optimal values of
pH, temperature, and initial concentration were used for the batch experiments. In addition, the
kinetic and equilibrium behaviors of the composite were investigated and several adsorption
models such as Langmuir, Freundlich, and Redlich-Peterson were adopted to fit the adsorption
isotherm. The adsorption kinetic rates were calculated to evaluate the possible adsorption
mechanisms. The material has a significant potential in removing Ammonical nitrogen coexisting
with phenolic compounds from wastewater.

Adsorption Kinetics:
Dye, a constituent that is widely used in textile, paper, plastic, food, and cosmetic industries is an
easily recognized pollutant. Decolourizing of textile and manufacturing waste water is currently a
major problem for environmental managers. Dyes may significantly affect photosynthetic activity
in aquatic life due to the presence of aromatics, metals, chlorides, and so forth, in them. Many of
the dyes used in the industries are stable to light and oxidation, as well as resistant to aerobic
digestion. However, dyes usually have a synthetic origin and complex aromatic molecular
structure which makes them more stable so they are not biodegradable and photodegradable, it
brings some difficulties for the treatment of these pollutants. Congo red (CR) (1-
napthalenesulfonic acid, 3, 3′-(4, 4′-biphenylene bis (azo)) bis (4-amino-) disodium salt) is a
benzidine-based anionic disazo dye, this dye is known to metabolize to benzidine, a known human
carcinogen.

Physicochemical processes are generally used to treat dyes laden waste water. These processes
include flocculation, electro flotation, precipitation, electro kinetic coagulation, ion exchange,
membrane filtration, electrochemical destruction, irradiation, and ozonation. However, all these
processes are costly and cannot be used by small industries to treat wide range of dye waste water.
The adsorption process provides an attractive alternative for the treatment of contaminated waters,
especially if the sorbent is inexpensive and does not require an additional pretreatment step before
its application. Adsorption is known to be a better technique, which has great importance due to
the ease of operation and comparable low cost of application in decoloration process.

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 Adsorption kinetics for different initial concentration of dyes

Activated carbon is the most widely used adsorbent with great success due to its large surface area,
microporous structure, and high-adsorption capacity. However, its use is limited because of its
high cost. This has led to search for cheaper substitutes. Investigators have studied the feasibility
of using low-cost substances, such as waste apricot, coconut shell, dairy sludge, bamboo grass
treated with concentrated sulfuric acid, peat, orange peels, pea nut hulls, rice husk, ground nut
shells charcoal and bagasse, bamboo, jack fruit peels, pistachio nut shells, and date stone and palm
tree waste as adsorbents for the removal of dyes and heavy metals from waste water.

Mass Transfer of Adsorption Beds:

In the recent time, the increased industrial activities have escalated more environmental problems
such as the contamination of water sources due to the accumulation of various toxic pollutants
from the industrial wastewater. Phenol, one of the prominent pollutants in the wastewater, has been
designated as priority pollutant by the environmental regulations. Its permissible concentration
should be less than 0.1 mg/L before it is released into the aquatic environment.

Phenol is introduced into the aquatic environment from the wastewater released from various
industries such as pesticide, paper and pulp, resin, petrochemicals, fertilizers, and pharmaceutical
industries and petroleum refineries. It also causes harmful effects on the human health and aquatic
life. Therefore, there is a need to treat phenol from wastewater before it is released into the
environment.

In the previous work, the batch experiments were carried out to investigate adsorption isotherm,
adsorption kinetics, and adsorption thermodynamics. But the literature on the mass transfer studies

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on the adsorption of phenol from adsorbent is limited. Mass transfer studies are also required for
finding the rate-limiting step.

Mass transfer finds extensive applications in chemical engineering separation processes, where
material balance on components is performed. For separation processes, thermodynamics
determine the extent of separation, while mass transfer determines the rate at which the separation
will occur.

It is studied that adsorption on an adsorbent from the aqueous phase involves three steps:
(i) Transport of the solute from bulk solution to the film surrounding the adsorbent (film diffusion).
(ii) Internal diffusion of solute from the film to the pores of the adsorbent.
(iii) Adsorption of the adsorbate on the external surface of the adsorbent through binding of the
ions to the active sites.
The slowest of these steps will control the process or will be the rate-limiting step. It will also
determine the overall rate of the process. Therefore, the prediction of adsorption rate-limiting step
is an important aspect for the study and design of adsorption process.

Adsorbent Regeneration:

Adsorbent beds, sometimes referred to as process dryers or treaters, use an adsorption

mechanism to remove contaminants like water, hydrogen sulfide (H 2S), carbon dioxide (CO2),
and other polar molecules from process streams.

Drying/treating systems are very common in refineries and petrochemical manufacturing

facilities and have widespread applications. They are used to dry instrument air, remove sulfur
species and CO2 to meet product specifications, remove poisons from reactor feed streams, and
remove water and CO2 from cryogenic fractionation trains.

The beds contain an adsorptive desiccant, usually an activated alumina, a molecular sieve, or a
combination of the two.

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The choice of desiccant depends on the size and type of molecule to be removed, as well as the
final product specification. Activated aluminas have high loading capacities for more-polar
molecules, but they are not as selective as some of the molecular sieves.

A 3A molecular sieve, for instance, will adsorb water and ammonia, but will exclude H 2S and
CO2, which require at least a 4A molecular sieve. Activated aluminas, on the other hand, simply
adsorb molecules based on polarity, and the more-polar molecules will displace the less-polar
molecules.

The regeneration sequence consists of the following five steps:

1. Recover the process fluid.

2. Heat and purge the bed with a regeneration fluid to shift the equilibrium and remove the
contaminants.
3. Hold at the elevated temperature to ensure the bed is hot and contaminants are swept
from the bed.
4. Cool the bed to the process temperature with a contaminant-free stream.
5. Return the bed to standby service.

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Adsorbent Types:

1. Activated carbon

Activated carbon is a granular material produced mostly by roasting charcoal from coconut
shells or coal at 800 to 1000°C to “activate” it. Impurities are removed by acid washing.
Typically, it has pore sizes ranging from 500 to 1000nm and a surface area of about
1000m2/gram.

A much purer form of activated carbon is produced by pyrolysing polymer beads. Activated
carbon reduces free chlorine to chloride and carbon dioxide. It also breaks down chloramines by
a relatively slow catalytic reaction to produce ammonia, nitrogen and chloride. Organic
compounds are adsorbed in the pores of the carbon matrix.

The large surface area of the activated carbon enables significant quantities of organic material to
adsorb through ionic, polar and Van der Waals forces.

The very large surface area of activated carbons provides ideal growing areas for bacteria.
Adding a bactericide, such as silver, has been used to minimise this effect but the carbon
cartridges need to be changed regularly to keep bacterial build-up and shedding under control.
Its major use in pre-treatment is to remove free chlorine and chloramines before reverse osmosis
to prevent membrane damage due to oxidation. Activated carbon reacts very rapidly with free
chlorine in water to produce chlorides; a relatively small volume of carbon can be effective.

2. Zeolite molecular sieves

Molecular sieve adsorbents are crystalline aluminosilicates, known as zeolites. Their unique
structure allows the water of crystallization to be removed, leaving a porous crystalline structure.
These pores, or cages, have a high affinity to re-adsorb water or other polar molecules.

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Aided by strong ionic forces (electrostatic fields) due to the presence of cations such as sodium,
calcium and potassium, and by the enormous internal surface area of up to 1,000 m2/g,
molecular sieves will adsorb a considerable amount of water or other fluids.

If the fluid to be adsorbed is a polar compound, it can be adsorbed with high loading, even at
very low concentrations of the fluid. Molecular sieves will, therefore, remove gas or liquid
impurities to very low levels (ppm or less). Another feature of molecular sieve adsorbents is their
ability to separate gases or liquids by molecular size or polarity.

The pore, or cage, openings are the same size as many molecules, e.g., in the case of
hydrocarbon paraffins, straight-chained molecules can fit into the pores and be adsorbed, while
the branched-chain molecules cannot enter the pores and pass through the molecular sieve bed
unadsorbed.

Since its founding, Zeochem has been at the leading edge of synthetic molecular sieve
technology. We have developed an ultra-stable molecular sieve able to withstand thousands of
thermal regenerations with delayed decay and exceptional capacity retention.

Vendors are required to not only meet our stringent raw material specifications, but also to have
in place extensive quality systems geared toward the continuous improvement of their products
and processes. We demand that of ourselves and require it of our suppliers.

We continue to upgrade and expand our processes and manufacturing capabilities, including toll
manufacturing, regeneration of spent product and custom manufacturing. This continuous
improvement allows us to meet the challenges of the 21st century.

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3. Silica Gel and Alumina Adsorbents

Silica and alumina are both polar adsorbents so the more polar components in the mixture to be
separated are retained more strongly on the stationary phase and are therefore eluted from the
column last. Silica is recommended for most compounds, but as it is slightly acidic, it
preferentially retains basic compounds. Alumina is slightly basic, so will retain acidic
compounds more strongly.

It is good for separation of components that are weakly or moderately polar and the purification
of amines. Absorbent particle size affects how solvent flows through the column. Silica or
alumina are both available in a variety of sizes. The size is given by the mesh value which refers
to the number of holes in the mesh that is used to sieve the absorbent. Thus higher mesh values
such as "silica gel 230–400" have more holes per unit area and correspondingly smaller particles
than "silica gel 60".

Typically, 70–230 silica gel is used for gravity columns and 230–400 mesh for flash columns.
Alumina is available in types I, II, and III. This refers to the water content of the alumina, with I
having the least water and III the most. A lower water content means there are more polar sites in
the alumina free to bind organic compounds, and polar compounds will remain on the column
longer.

Alumina of activity II or III, 150 mesh, is most commonly employed. The techniques for packing
a column described below use silica as the stationary phase, but are equally suitable for use with
alumina.

4. Polymeric adsorbents

Polymeric adsorbents are spherical synthetic polymers with defined pore structure and high
surface area for efficient and selective removal of organic molecules, primarily in aqueous
applications. The surface area is inversely proportional to the pore diameter for a given pore
volume.

Figure of polymeric adsorbent material used for removal of phenolic derivatives from
wastewater is given as:

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5. Ion Exchangers

Strong Acid Resins:

The strongly acidic cation exchange resins are bead-like products which have a sulfonic acid
group in the cross-linked styrene frame. They can be used across the full pH range (0-14), and
are relatively stable to temperature, even withstanding high temperatures of 100-120℃.

They are used in a wide variety of fields including water purification, water softening, and
wastewater treatment, purification of pharmaceuticals and food, and catalysis. They are used in a
wide variety of fields including water purification, water softening, and wastewater treatment,
purification of pharmaceuticals and food, as well as catalysis. Used for Packed column or Batch
processing

Strong Base Resins:

An amino functional group is incorporated into the anion exchange resin enabling the exchange
of anions like the Cl- ion and the SO4-- ion. Strongly basic anion exchange resins and weakly
basic anion exchange resins can be defined according to the basic strength of the amino
functional group.

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The ion exchange resin that has a quaternary ammonium group is strongly alkaline and
dissociates just like NaOH and KOH. Therefore it is called a strongly basic anion exchange
resin. The strongly basic anion exchange resin is an anion exchange resin with quaternary
ammonium groups incorporated into the styrene frame. Two types with differing alkalinity
strengths are: Type I with a trimethyl ammonium group, and Type II with a dimethylethanol
ammonium group.
The strongly basic resin is used to produce high purity demineralized water, making use of the
capability to strongly adsorb anions.

Weak Acid Cation Resins:

Weak acid cation (WAC) exchange resins remove cations associated with alkalinity (temporary
hardness). Similar to SAC resins, WAC resins swap cations for hydrogen ions, resulting in
slightly greater acidity in the treated stream.

Their high affinity for divalent cations ions (Ca2+ and Mg2+) makes them a good choice for
applications demanding the removal of hardness ions associated with alkalinity. For high
temporary hardness applications, a WAC resin can be used ahead of a SAC resin in a two-step
IX process.

Additionally, WAC resins tend to have relatively high oxidation resistance and mechanical
durability, making them a good choice for streams containing oxidants such as hydrogen
peroxide and chlorine, among others.

Weak Base Anion Resins:

Weak base anion (WBA) exchange resins are the only major type of IX resins that do not have
exchangeable ions. These resins adsorb free mineral acidity (Cl and SO 4).

WBA resins have amine functional groups, and are typically regenerated with sodium hydroxide
(NaOH), ammonia (NH3), or sodium carbonate (Na2CO3).

In larger plants, WBA resin beds may be paired with SBA units for complete demineralization
applications, and WBA resins are also effective as total organic carbon (TOC) barriers ahead of
SBA beds.

WBA is also used for acid adsorption applications involving the removal of chloride, sulphate,
nitrate, and other anions associated with strong acids, though it is not effective for removal of
weak acids such as silica (SiO2) and carbon dioxide (CO2).

Equilibrium Constant:

The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical
equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed
at which its composition has no measurable tendency towards further change.

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For a given set of reaction conditions, the equilibrium constant is independent of the initial
analytical concentrations of the reactant and product species in the mixture. Thus, given the
initial composition of a system, known equilibrium constant values can be used to determine
the composition of the system at equilibrium.
However, reaction parameters like temperature, solvent, and ionic strength may all influence the
value of the equilibrium constant.
A knowledge of equilibrium constants is essential for the understanding of many chemical
systems, as well as biochemical processes such as oxygen transport by hemoglobin in blood
and acid–base homeostasis in the human body.
Stability constants, formation constants, binding constants, association constants and dissociation
constants are all types of equilibrium constants.

Separation Adsorption Processes and Industrial Applications:

Applications of adsorption of small drug particles at the surface of large excipients were
introduced, and different factors affecting adsorption process were discussed and summarized.
Several examples of adsorbing drugs to excipients to increase dissolution rate were exhibited in
this article.

Adsorption of small drug particles on the surface of large excipients has been widely used in the
pharmaceutical industry for various purposes, such as improving content uniformity of low-dose
drugs, enhancing the dissolution rate for poorly water-soluble drugs and enhancing some special
formulation designs. Achieving good content uniformity is a common challenge when
manufacturing solid dosage formulations. One of the frequently used approaches is adsorbing
small drug particles at the surface of large excipients by geometric mixing.

For poorly water-soluble drugs, adsorbing small drug particles at the surface of large excipients
can increase the dissolution rate by increasing drug surface area, and/or transforming drug from
crystalline form to the amorphous form. Surface adsorption has also been involved in other
pharmaceutical applications such as drug oxidation, granulation for oily medicines, and some
special formulation designs.

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 Representative Commercial Gas Phase Adsorption Separations

Gas Bulk Separations (b)

Separation (a) Adsorbent
Normal paraffins, isoparafins, aromatics Zeolite

N2/O2 Zeolite
O2/N2 Carbon molecular sieve
CO, CH4, CO2, N2, A, NH3/H2 Zeolite, activated carbon

Acetone/vent streams Activated carbon

C2H4/vent streams Activated carbon
H2O/ethanol Zeolite
Gas Purifications (c)
Separation (a) Adsorbent
H2O/olefin-containing cracked gas, natural Silica, alumina, zeolite
gas, air, synthesis gas, etc…

CO2/C2H4, natural gas, etc. Zeolite

Organics/vent streams Activated carbon, others

Sulfur compounds/natural gas, hydrogen, Zeolite
liquified petroleum gas (LPG), etc.

Solvents/air Activated carbon

Odors/air Activated carbon
NOx/N2 Zeolite
SO2/vent streams Zeolite
Hg/chlor-alkali cell gas effluent Zeolite

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References:

i. Separation Process Engineering Book by Phillip C. Wankat

ii. Separation Process Principles with Applications Using Process Simulators Book by D.
Keith Roper, Ernest J. Henley, and J. D Seader
iii. Separation Process Technology Book by George E. Keller and Jimmy L. Humphrey
iv. Industrial Separation Processes: Fundamentals Book by André B. de Haan and Hans
Bosch

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