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Methods of Activation of different Adsorbent Materials

By Miss Kousar Parveen Daudani

Title of course.

Advanced Surface Chemistry


Course No.868 Course coordinator. Prof. Dr. Ghulam Zohra Memon

ADSORBATE AND ADSORBENT

The substance which is adsorbed on the


surface is called ADSORBATE

The substance on which adsorption takes place


is called ADSORBENT

Adsorption

Absorption

Adsorption is ideally suited key tool for purification Applications as well as difficult separations. Different adsorbent materials are used in the application of surface chemistry.

Adsorbents are processed by different methods of activation

CLASSIFICATION OF ADSORBENTS ON THE BASIS OF POLARITY.


There are three classes of Adsorbents 1.Oxygen-containing compounds Zeolites)

Hydrophilic and polar (e.g.: silica gel and Hydrophobic and non-polar (e.g.: activated
carbon and graphite ) 2.Carbon-based compounds

Polar or non-polar functional groups , porous


polymer matrix

3.Polymer-based compounds

ACTIVATION OF ADSORBENTS
ACTIVATION is a physical or chemical process by
which adsorbent with following characteristics are produced. rods and mouldings have high abrasion resistance, high thermal stability and small pore diameters which result in large surface capacity for adsorption.

ADSORBENT are in the form of spherical pellets ,


ADSORBENT

ADSORBENT have a distinct pore structure

enabling fast transport of the gaseous vapours.

TYPES OF ACTIVATION METHODS

There are two types of common activation methods

Physical activation and Chemical activation

of adsorbents.

Physical activation is carried out by heat treatment


hydrothermal treatment or decrease in particle size.

Chemical activation is carried out by treatment with


various types of chemicals where by surface area as well as necessary functional groups are increased in given adsorbent.

Important Commercial Adsorbents

Activated Carbon Silica Gel Activated Alumina Zeolites

Different Physical Forms Of Activated Carbon

Activated Carbon

ACTIVATED CARBON

HOW CARBON IS ACTIVATED


Activated carbons are produced by carbonization Treatment with oxidizing agents (steam , carbon
petroleum coke and many others employing slow substrate heating in the absence of air , this removes volatiles . Then chemical or physical activation follows dioxide or oxygen) at elevated temperature or with chemical act vents completes the activation.

The commonly used raw materials are wood, peat

o in Oxidizing step the gases can be used are (air ,


water vapour and CO2 ) because intrinsic surface reaction rate is much slower than the pore diffusion rate

o During backing the raw materials are oxidised and


carbonised, the process is highly exothermic and the temperature is strictly controlled .

o The creation of active surface is done during the


activation step . temperature between 800-1,000C are required to accelerate endothermic reaction b/w the raw material and water vapour and CO2

o Oxygen reacts with carbon several hundred


thousand times faster then CO2 or water vapour.

REACTIONS

H2O + C 2H2O + C CO2 + C CO

---- CO + H2 ---- CO2 + 2H2 ----- 2CO

H= + 117 KJ H= + 75 KJ H= + 159 KJ H= - 285 KJ

+ O2 ---- CO2

H2

+ O2 ----- H2O

H= - 238 KJ

UNIQUE PROPERTIES OF ACTIVATED CARBON


The unique surface property of activated carbon, in contrast to the other major sorbents, is that its surface is non-polar or only slightly polar. This unique property gives activated carbon the following advantages: It is the only commercial sorbent used to perform separation and purification processes moisture removal, is needed in air purification. For the same reason, it is also widely used as a sorbent for processes treating aqueous solutions.

Because of its large, accessible internal surface (and large pore volume), it adsorbs more non-polar and weakly polar organic molecules than other sorbents do. The heat of adsorption, or bond strength, is generally lower on activated carbon than on other sorbents. This is because only nonspecific, van der Waals forces are available as the main forces for adsorption.

ACTIVATED CARBON

MANUFACTURE OF ACTIVATED CARBON FROM COAL

INCREASE IN MAGNIFICATION AFTER ACTIVATION PROCESS

TABLE OF SOME CHEMICAL ACTIVANTS OF CARBON


Feedstock Almond shell, olive stone ,and peach stones Activant condition Heating in CO2 at 606C Conc.H2SO4 H2O2/H2O,N2 H3PO4/H2SO4 H3PO4 KOH/H2O H2SO4 KOH/NaOH Fe(NO3)3/CO2 H3PO4 Parts by weight H2SO4 for 24 at 150C 450C , 1h 730C , 6h 450 C 700-850 C , 4h 10% (v/v),350 C 930 C 850 C,1h;825 C ,6h Chemical activation with H3PO4 /physical with CO2
at 400-800C

Coconut shell
Fertilizer slurry Palm tree cobs Coconut shell Petroleum coke Raffination earth Algerian coal Pine saw dust Almond and peach shells

COCONUT SHELL

Feedstock Bituminous coal Coal Petroleum coke Lignite Peanut hulls Fly ash

Actvant ZnCl2 KOH


Na2MoO4/NaWO4/NH4VO3 /(NH4)2MoO4/FeCl3/Fe(NO3)3

Condition N2/400-700C
Phosgene or chlorine gas at 180C Dehydration at 400C , Activation in 500-900C Inert atmosphere /600-800C
150C,sodium bicarbonate Forth flotation, hydrophobic char was separated from hydrophilic ash with the help of methyl isobutyl ketone Fast pyrolysis at 500C with inert nitrogen

H2SO4

Oat hulls Solvent extracted olive pulp and olive stones

Steam

K2CO3

under vacuum and atmos: pressure 60C/min;800C; activation under N2 at 10C/min


Carbonized with H2SO4 and activated at 600C,1h

Coconut shell and coconut shell fibers

SILICA GEL OPEN

SILICA GEL

SILICA GEL

It is most widely used desiccant because Silica gel is being applied in an


of its large capacity for water .(~40% by weight) and ease in regeneration ~150C

Silica gel sorbents are meso porous that


is with pores mostly larger than 20A.

increasing number of application in chromatography.

SILICA GEL PREPARATION AND ACTIVATION


It can be formed by two routes 1. Polymerization of silicic acid 2. Aggregation of particles of colloidal silica Commercially it is prepared by mixing sodium silicate solution with a mineral acid H2SO4 , or HCl, white jelly like SiO2 is formed known as silicic acid, Hydrosol, or silica gel Na2SiO3+2HCl+nH2O > 2NaCl+SiO2.nH2O+H2O

ACTIVATION AND SURFACE CHEMISTRY OF SILICAS: THE SILANOL GROUPS


The surface chemistry of silicas is dominated by the surface hydroxyl groups, or silanols (Si-O-H). The silanol groups participate in adsorption There are three basic types of surface silanol groups Another type, vicinal hydroxyls, applies to free hydroxyls that are adjacent to each other on the surface.

BASIC TYPES OF SILANOL (HYDROXYL) GROUPS ON SILICAS


THREE

Many techniques have been used to identify and quantify the different silanol groups. IR spectroscopy of the adsorbed water and hydroxyls the most useful absorption band is the OH stretching frequency. In addition to the surface OH groups, there also exist internal OH groups in the silica structure.

ACTIVATION METHODS OF SILICAS

ACTIVATED ALUMINA

ACTIVATED ALUMINA AS SPECIAL SORBENTS


It is an important desiccant. Activated alumina is a versatile sorbent that can be tailored for many special applications.

APPLICATION S OF ACTIVATED ALUMINA

ZEOLITE STRUCTURE PROPERTY RELATIONSHIP

ZEOLITES AND MOLECULAR SIEVES

Zeolites are crystalline alumino silicates of alkali or


They have general chemical composition Mx/n
alkaline earth elements .
[(AlO2)(SiO2)y].H2O

The primary structural units of zeolites are the They are potentially strong sorbents due to
tetrahedra of silicon and aluminum giving three dimensional frame work. presence of cavities, channels and cage like frame work.

APPLICATIOS OF ZEOLITES

SYNTHESIS AND ACTIVATION OF ZEOLITES


At least 40 different types of zeolites are naturally

occuring. Many more zeolite-like, crystalline molecular sieves have been successfully synthesized by using amine additives as templating agents Many alkali metal hydroxides and raw materials containing silica and alumina can be used in lowtemperature synthesis. The steps involve the Na2OAl2O3-SiO2-H2O system. Zeolites do not need any extra activation treatment in view of their special structures.

Polymeric resins and their derivatives have A broad range of synthetic non-ionic polymers The polymeric resins and carbonaceous These are ease in regeneration The sorbent sorbets interactions are
are available for use a sorbents , ionexchanger and chromatographic column packings. been used commercially for adsorption and ion exchange.

polymers are significantly more hydrophobic than activated carbon.

stronger on the carbonized resins are suited for achieving high particles or ultra purification.

OPEN CARBON NANO TUBES

CARBON NANOTUBES
These are not commercially used
However they each have interesting and unique adsorption properties and are subjects of active research . Carbon Nanotubes in particular hold tremendous potential for applications because of their unique electrical conductivities , high strength and high stiffness. A single-wall nano-tubes (SWNT) is a seamless cylinder wrapped by a graphite sheet. Carbon Nanotubes have high cylindrical pores are adsorbate molecule interacts with the carbon atoms on the surrounding walls. Carbon nanotubes can adsorb molecules much more strongly than activated carbon.

ADSORPTION PROPERTIES OF CARBON NANOTUBES


Carbon nanotubes have cylindrical pores. An adsorbate molecule interacts with the carbon atoms on the surrounding walls The resulting potential in the cylindrical pore can be substantially higher than that in a slit-shaped pore with the same dimension. In addition, carbon nanotubes are highly graphitic (much more so than activated carbon). The surface of the nanotubes is highly aromatic and contains a high density of electrons The most unexpected and potentially most important adsorption property of carbon nanotubes is hydrogen storage. While controversy remains, intensive research efforts on this subject are on-going worldwide.