Gas adsorption processes

The rate of adsorption of a molecular species depends on the nature of the adsorption process. Gas molecules may be held on a surface by the weak van der Waal attractive forces which exist between all molecules or by stronger chemical types of bonds (chemisorption) which depend on the... 

R. Krishna, A unified approach to the modeling of intraparticle diffusion in adsorption processes, Gas Sep. Purif. 7(2) 9l (1993). 

Activated carbon is a very important industrial adsorbent because it exhibits a well developed porosity (micro, meso and macroporosity) and this is coupled with a great thermal and chemical stability, a relatively large hydrophobicity (thus favouring the adsorption of non-polar substances in the presence of humidity), low production cost, etc. Additionally, the surface of activated carbon can be functionalised with different heteroatoms (but mainly oxygen), thus modifying the chemical nature. A large and accessible surface area is a necessary but not sufficient condition for the preparation of activated carbons to be used in industrial adsorption processes (gas and liquid phase purification, separation, environmental control, etc.), since the last few years has shown that the chemical composition of the carbons surface plays a very important role in the process. 

Satterfield, C. N., Mass Transfer in Heterogeneous Catalysis, MIT Press, Cambridge, MA, (1970), p. 157. For a more detailed discussion of diffusion in porous media, see Krishna, R., A unified approach to the modeling of intraparticle diffusion in adsorption processes. Gas Separat. Purificat. 7 (2), 91-104 (1993). 

The BET treatment is based on a kinetic model of the adsorption process put forward more than sixty years ago by Langmuir, in which the surface of the solid was regarded as an array of adsorption sites. A state of dynamic equilibrium was postulated in which the rate at which molecules arriving from the gas phrase and condensing on to bare sites is equal to the rate at which molecules evaporate from occupied sites. 

R. T. Yang, Gas Separation bj Adsorption Processes, Butterworths, Stoneham, Mass., 1987. 

Compounds having low vapor pressures at room temperature are treated in water-cooled or air-cooled condensers, but more volatile materials often requite two-stage condensation, usually water cooling followed by refrigeration. Minimising noncondensable gases reduces the need to cool to extremely low dew points. Partial condensation may suffice if the carrier gas can be recycled to the process. Condensation can be especially helpful for primary recovery before another method such as adsorption or gas incineration. Both surface condensers, often of the finned coil type, and direct-contact condensers are used. Direct-contact condensers usually atomize a cooled, recirculated, low vapor pressure Hquid such as water into the gas. The recycle hquid is often cooled in an external exchanger. 

Adsorption. Adsorption processes have been used to recover hydrocarbons that are heavier than ethane from natural gas. Although the adsorption process has appHcations for the recovery of pentane and heavier hydrocarbons from lean gas, the percentage recovery of LPG components in these plants usually is low compared to the normal recovery of LPG in modem turboexpander or oil-absorption plants. 

Less propane and butanes are produced compared to natural gas Hquids by the adsorption process than are obtained normally for the same gas by the oil-absorption process. Because adsorption efficiency increases with a decrease in temperature, the adsorption cycle should operate at the lowest temperature that is economically feasible. 

Solid-Bed Dehydration. Sihca gel, bauxite, activated alurnina, or molecular sieves can be used for removing dissolved water to meet propane specifications. The soHd-bed dehydrators are used in a cycHc adsorption process. After an adsorption cycle has completed, the bed is heated with a purge gas or a vaporized Hquid-product stream for regeneration. If the latter is used, the Hquid product is condensed, separated from the free water, and returned to the process. After the beds are regenerated, they are cooled and returned to the adsorption cycle. 

If objective is to recover adsorbed components (free of water vapor), inlet gas stream should be dried before molecular sieve adsorption process occurs (water adsorption on mol sieves is particularly strong because of polarity of surface). 

Adsorption Processes. The processes based on adsorption of hydrogen sulfide onto a fixed bed of soHd material are among the oldest types of gas treating appHcations (4). Two common sorbent materials for low concentration gas streams are iron oxide and zinc oxide. 

Process Stream Separations. Differences in adsorptivity between gases provides a means for separating components in industrial process gas streams. Activated carbon in fixed beds has been used to separate aromatic compounds from lighter vapors in petroleum refining process streams (105) and to recover gasoline components from natural and manufactured gas (106,107). 

Pressure Swing Adsorption. A number of processes based on Pressure Swing Adsorption (PSA) technology have been used in the production of carbon dioxide. In one version of the PSA process, CO2 is separated from CH using a multibed adsorption process (41). In this process both CH4 and CO2 are produced. The process requires the use of five adsorber vessels. Processes of this type can be used for producing CO2 from natural gas weUs, landfiU gas, or from oil weUs undergoing CO2 flooding for enhanced oil recovery (see Adsorption, gas separation). 

Adsorption Processes. More recendy, pressure swing adsorption (PSA) processes utilizing a high selectivity copper adsorbent have been utilized to effectively separate carbon monoxide from blast furnace gas and coke oven gas (97—101). 

Experience in air separation plant operations and other ciyogenic processing plants has shown that local freeze-out of impurities such as carbon dioxide can occur at concentrations well below the solubihty limit. For this reason, the carbon dioxide content of the feed gas sub-jec t to the minimum operating temperature is usually kept below 50 ppm. The amine process and the molecular sieve adsorption process are the most widely used methods for carbon dioxide removal. The amine process involves adsorption of the impurity by a lean aqueous organic amine solution. With sufficient amine recirculation rate, the carbon dioxide in the treated gas can be reduced to less than 25 ppm. Oxygen is removed by a catalytic reaction with hydrogen to form water. 

Material balances, often an energy balance, and occasionally a momentum balance are needed to describe an adsorption process. These are written in various forms depending on the specific application and desire for simplicity or rigor. Reasonably general material balances for various processes are given below. An energy balance is developed for a fixea bed for gas-phase application and simphfied for liquid-phase application. Momentum balances for pressure drop in packed beds are given in Sec. 6. 

When a gas comes in contact with a solid surface, under suitable conditions of temperature and pressure, the concentration of the gas (the adsorbate) is always found to be greater near the surface (the adsorbent) than in the bulk of the gas phase. This process is known as adsorption. In all solids, the surface atoms are influenced by unbalanced attractive forces normal to the surface plane adsorption of gas molecules at the interface partially restores the balance of forces. Adsorption is spontaneous and is accompanied by a decrease in the free energy of the system. In the gas phase the adsorbate has three degrees of freedom in the adsorbed phase it has only two. This decrease in entropy means that the adsorption process is always exothermic. Adsorption may be either physical or chemical in nature. In the former, the process is dominated by molecular interaction forces, e.g., van der Waals and dispersion forces. The formation of the physically adsorbed layer is analogous to the condensation of a vapor into a liquid in fret, the heat of adsorption for this process is similar to that of liquefoction. 

Activated carbon is an amorphous solid with a large internal surface area/pore strucmre that adsorbs molecules from both the liquid and gas phase [11]. It has been manufactured from a number of raw materials mcluding wood, coconut shell, and coal [11,12]. Specific processes have been developed to produce activated carbon in powdered, granular, and specially shaped (pellet) forms. The key to development of activated carbon products has been the selection of the manufacturing process, raw material, and an understanding of the basic adsorption process to tailor the product to a specific adsorption application. 

Adsorbents, and activated carbon in particular, are typically characterized by a highly porous structure. Adsorbents with the highest adsorption capacity for gasoline or fuel vapors have a large pore volume associated with pore diameters on the order of 50 Angstroms or less. When adsorption occurs in these pores, the process is comparable to condensation in which the pores become filled with hquid adsorbate. Fig. 5 depicts the adsorption process, including transfer of adsorbate molecules through the bulk gas phase to the surface of the solid, and diffusion onto internal surfaces of the adsorbent and into the pores. 

Activated carbon in particular is very versatile as a filter media because it not only can physically separate out suspended solids, but it can adsorb materials. The adsorption process occurs at solid-solid, gas-solid, gas-liquid, liquid-liquid, or... 

Yang, R. T. (1987). "Gas Separation by Adsorption Processes. Butterworth, Boston. 

Adsorption processes use a solid material (adsorbent) possessing a large surface area and the ability to selectively adsorb a gas or a liquid on its surface. Examples of adsorbents are silica (Si02), anhydrous alumina (AI2O3), and molecular sieves (crystalline silica/alumina). Adsorption processes may be used to remove acid gases from natural gas and gas streams. For example, molecular sieves are used to dehydrate natural gas and to reduce its acid gases. 

Adsorption of n-paraffms (C10-C14) from a kerosine or a gas oil fraction can be achieved in a liquid or a vapor phase adsorption process. 

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