ADSORPTION

Adsorption is a process, similar to absorption, by which a substance in a gas or liquid becomes attached to a solid. The substance can be a pollutant, called an adsorbate, which is attracted to the surface of a special solid. Adsorption occurs naturally, but industrialists have perfected adsorption methods to clean up hazardous waste or purify drinking water. Natural or organic methods of adsorption take place all the time. For example, the ocean adsorbs carbon dioxide in the atmosphere, which effects climate and atmospheric temperature. Early humans observed that if they charred a piece of bone all the way through, they could put the bone in food mixtures, like sugar water, and it would collect polluting particles that weren't edible, thereby purifying the food. Particles colored in our visible spectrum, as well as those with strong odors, are easiest to adsorb. It's important to harness the power of adsorption in battling modern chemical hazards. Some solids are ideal for adsorption. They have a lot of surface area for their volume because they are pockmarked with micropores. Industrial and commercial uses for adsorption filters vary. For example, carbon makes cold drinking water taste better. A carbon filter can be heated to clean the surface of adsorbates and reused. Activated alumina removes harmful chemicals like fluoride and arsenic from liquids. Synthetic resins can clean up highly hazardous spills, such as nerve gas, in areas that might have high temperatures, like near explosives. Adsorption, the binding of molecules or particles to a surface, must be distinguished from absorption, the filling of pores in a solid. The binding to the surface is usually weak and reversible. Just about anything including the fluid that dissolves or suspends the material of interest is bound, but compounds with color and those that have taste or odor tend to bind strongly. Compounds that contain chromogenic groups (atomic arrangements that vibrate at frequencies in the visible spectrum) very often are strongly adsorbed on activated carbon. Decolorization can be wonderfully efficient by adsorption and with negligible loss of other materials. The most common industrial adsorbents are activated carbon, silica gel, and alumina, because they present enormous surface areas per unit weight. Activated carbon is produced by roasting organic material to decompose it to granules of carbon - coconut shell, wood, and bone are common sources. Silica gel is a matrix of hydrated silicon dioxide. Alumina is mined or precipitated aluminum oxide and hydroxide. Although activated carbon is a magnificent material for adsorption, its black color persists and adds a grey tinge if even trace amounts are left after treatment; however filter materials with fine pores remove carbon quite well. A surface already heavily contaminated by adsorbates is not likely to have much capacity for additional binding. Freshly prepared activated carbon has a clean surface. Charcoal made from roasting wood differs from activated carbon in that its surface is contaminated by other products, but further heating will drive off these compounds to produce a surface with high adsorptive

capacity. Although the carbon atoms and linked carbons are most important for adsorption, the mineral structure contributes to shape and to mechanical strength. Spent activated carbon is regenerated by roasting, but the thermal expansion and contraction eventually disintegrate the structure so some carbon is lost or oxidized. Temperature effects on adsorption are profound, and measurements are usually at a constant temperature. Graphs of the data are called isotherms. Most steps using adsorbents have little variation in temperature. Adsorbents [edit] Characteristics and general requirements

Activated carbon is used as an adsorbent Adsorbents are used usually in the form of spherical pellets, rods, moldings, or monoliths with hydrodynamic diameters between 0.5 and 10 mm. They must have high abrasion resistance, high thermal stability and small pore diameters, which results in higher exposed surface area and hence high surface capacity for adsorption. The adsorbents must also have a distinct pore structure which enables fast transport of the gaseous vapors. Most industrial adsorbents fall into one of three classes:

Oxygen-containing compounds Are typically hydrophilic and polar, including materials such as silica gel and zeolites. Carbon-based compounds Are typically hydrophobic and non-polar, including materials such as activated carbon and graphite. Polymer-based compounds - Are polar or non-polar functional groups in a porous polymer matrix.

[edit] Silica gel Silica gel is a chemically inert, nontoxic, polar and dimensionally stable (< 400 C) amorphous form of SiO2. It is prepared by the reaction between sodium silicate and sulfuric acid, which is followed by a series of after-treatment processes such as aging, pickling, etc. These after treatment methods results in various pore size distributions.

Silica is used for drying of process air (e.g. oxygen, natural gas) and adsorption of heavy (polar) hydrocarbons from natural gas. [edit] Zeolites Zeolites are natural or synthetic crystalline aluminosilicates which have a repeating pore network and release water at high temperature. Zeolites are polar in nature. They are manufactured by hydrothermal synthesis of sodium aluminosilicate or another silica source in an autoclave followed by ion exchange with certain cations (Na+, Li+, Ca2+, K+, NH4+). The channel diameter of zeolite cages usually ranges from 2 to 9 (200 to 900 pm). The ion exchange process is followed by drying of the crystals, which can be pelletized with a binder to form macroporous pellets. Zeolites are applied in drying of process air, CO2 removal from natural gas, CO removal from reforming gas, air separation, catalytic cracking, and catalytic synthesis and reforming. Non-polar (siliceous) zeolites are synthesized from aluminum-free silica sources or by dealumination of aluminum-containing zeolites. The dealumination process is done by treating the zeolite with steam at elevated temperatures, typically greater than 500 C (900 F). This high temperature heat treatment breaks the aluminum-oxygen bonds and the aluminum atom is expelled from the zeolite framework. [edit] Activated carbon Activated carbon is a highly porous, amorphous solid consisting of microcrystallites with a graphite lattice, usually prepared in small pellets or a powder. It is non-polar and cheap. One of its main drawbacks is that it is combustible.

Activated carbon nitrogen isotherm showing a marked microporous type I behavior Activated carbon can be manufactured from carbonaceous material, including coal (bituminous, subbituminous, and lignite), peat, wood, or nutshells (e.g., coconut). The manufacturing process consists of two phases, carbonization and activation. The carbonization process includes drying and then heating to separate by-products, including tars and other hydrocarbons, from the raw material, as well as to drive off any gases generated. The carbonization process is completed by heating the material at 400600 C in an oxygen-deficient atmosphere that cannot support combustion. The carbonized particles are "activated" by exposing them to an oxidizing agent, usually steam or carbon dioxide at high temperature. This agent burns off the pore blocking structures created during the carbonization phase and so, they develop a porous, three-dimensional graphite lattice structure. The size of the pores developed during activation is a function of the time that they spend in this stage. Longer exposure times result in larger pore sizes. The most popular aqueous phase carbons are bituminous based because of their hardness, abrasion resistance, pore size distribution, and low cost, but their effectiveness needs to be tested in each application to determine the optimal product. Activated carbon is used for adsorption of organic substances and non-polar adsorbates and it is also usually used for waste gas (and waste water) treatment. It is the most widely used adsorbent. Its usefulness derives mainly from its large micropore and mesopore volumes and the resulting high surface area.