Lecture 7

Air Pollution Control Methods and Equipment (Control of Gaseous Pollutants)

Dr.Vandana

ET ZC362: Environmental Pollution Control

BITS Pilani

Learning Objectives Control of Gaseous Emissions

Control of Gaseous Emissions

There are two classes of tech. by which gaseous pollutants may be removed from an effluent gas 1.Sorption of pollutant Absorption Adsorption 2. Chemical alteration of the pollutant combustion catalytic treatment

Absorption by liquids
This tech. is widely used for controlling/ removing the gaseous pollutants from an effluent gas It involves the transfer of pollutant from gas phase to liquid phase across the interface . A two-resistance theory is used to explain this process. According to this theory, the interface offers no resistance to mass transfer and the mass transfer rate between the two phases is controlled by the rates of diffusion through the phases on each side of the interface.

 For dilute solutions, the equilibrium relation between pA and cA can be expressed in terms of Henrys law.

Henrys Law : Definition At a constant temp, the amount of gas that dissolves in a liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid. Mathematically we can express Henrys as pA = KcA Where K is the Henrys constant, p is partial pressure and c is concentration. Or pA = K1xA, x is mole fraction. K depends on nature of solute, solvent and temperature. Smaller value of K1 represents higher solubility.

Selection of solvents

Effectiveness of absorption process highly depends on Gas solubility in the solvent Solvent vapor pressure (low VP is favorable) Corrosiveness of solvent (non corrosive is favorable) Solvent regeneration (easy to regenerate) Cost of solvent (low cost) Operating temperature (low temp.) Viscosity of solvent(low viscosity) Chemical stability

Adsorption by Solids

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Two types of adsorption 1. Physical adsorption ( Physisorption)

The attractive forces holding the molecules at the surface is physical. The gaseous material condenses upon the surface of the solid, accompanied by an evolution of heat. The adsorbed material can be removed by reducing the pressure or by increasing the temperature and so it is reversible. 2. Chemical adsorption ( Chemisorption) Result of a chemical interaction between the solid and the adsorbed material. The molecules are held to the solid surface by chemical bonds.

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 Adsorption techniques are widely used in the field of odour control and also used for collecting valuable organic substances that can not be picked by scrubbing. The rate of adsorption depends on the concentration of the material around the adsorbent, the surface area of the adsorbent, the pore volume of the adsorbent, and properties like temperature, molecular polarity and the chemical nature of the adsorbent surface. Commonly used adsorbents in air pollution control are activated C, activated alumina, silica gel and molecular sieves.

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Adsorbents and their uses

Adsorbent Activated Carbon Uses Removal of odours and trace of impurities from gases, purification of Industrial gases and hydrocarbons, solvent recovery. Dehydration of gases and liquids. Dehydration and purification of gases Selective adsorption of CO2, NH3, C2H2, H2S and SO2.

Activated Alumina Silica Gel Molecular sieves

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Adsorption Steps
Diffusion of the pollutant from the bulk gas phase to the external surface of the solid ( similar to the diffusion of the gas to the gasliquid interface in absorption.) Diffusion of the gas molecules into the pores of the solid.

Actual adsorption on the active sites in the pores.

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Removal of Pollutants by Adsorption

Removal of pollutants by adsorption can be carried out in a batchwise or continuous manner of operation. Eg; Fixed bed absorber.

Some time before sending the waste gas to the adsorber , it is filtered to prevent bed contamination by soot, resin droplets & large particulates. Molecular sieves are normally used for the removal of gaseous pollutants.
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The adsorber is normally regenerated when the break-through point is reached. The removal of pollutants from the adsorbent and thereby renewing it for further use is called regeneration.

Regeneration is often enabled by using parallel beds, one of which removes pollutant while the other is being regenerated.

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Combustion/ Thermal Oxidation

Thermal oxidation ( flaring/ incineration ) is the process of oxidizing combustible materials in presence of air at a high temperature for sufficient time to complete combustion to CO2 and water vap. For complete combustion, the O2 must come into intimate contact with the combustible material through adequate turbulence at sufficiently high temperature and have a sufficiently long residence time. Time, temp; and turbulence have important roles in combustion and they are often called the three Ts of combustion. Normal ranges: Temp: 375 825 oC, residence time: 0.2 0.5 sec, gas velocity: 4.5 7.5 m/s.

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Three methods of combustion 1. Direct combustion ( Flaring) 2. Thermal incineration (Flame combustion) 3. Catalytic Oxidation

1. Flaring Highly combustible streams with high heating values can be eliminated by flaring. This method is not good, if the gas streams contain excessive amounts of inorganic pollutants ( like S, F, Cl2etc). The gas streams have to be pretreated before flaring. Unsaturated hydrocarbons ( aromatics, olefins etc) produce smoke and we can use some designs in such a way that it allows them to burn smokelessly.
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Steam Injection type Flare

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Thermal Incineration

Preheating of the gas stream is required, if the combustible gases are diluted with inert gases. Thermal incineration is the most flexible technique for destroying diluted gas streams.

The waste gas is preheated and passed into a combustion chamber where a temp.of 500-8000C is maintained.

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Catalytic Oxidation
Catalytic oxidizers or catalytic incinerators, operate similarly to thermal oxidizers. The primary difference is that the gas, after passing through the flame area, passes through a catalyst bed.
The temp. requirement is much lower than the thermal ignition. Waste gas is typically heated by auxiliary burners to 320 4300C before entering the catalyst bed. The max. design temp of the catalyst exhaust is 540 6750C. Generally catalysts are oxides of precious metals such as Pt & Pd. The potential poisons of the catalyst are S, Si, P, As. To maintain catalyst activity and to achieve complete combustion 1% excess O2 is allowed
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Catalytic combustion unit

This technique is recommended for gases that are free of particulate matter and certainly free of metallic substances which could poison the catalyst. To achieve complete combustion and to maintain the catalyst in an active state, about 1% excess O2 is required.

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Chapter 6

Control of Specific Gaseous Pollutants

Learning Objectives

Application of air pollution control equipment and strategies for the control of major gaseous pollutant emissions.

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Introduction
The sulphur oxides, the oxides of N2, CO2 and hydrocarbons are the important gaseous air pollutants because of their known harmful effects and their presence in the atmosphere.

Control of SO2 Emission

The main source of SO2 emissions are the fossil fuel burning .

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 Most convenient method of solving SO2 problem is to disperse SO2 containing waste gas from stacks at sufficient height, but due to more stringent HSE policy, sometimes this method is not acceptable
Three basic procedures for controlling SO2 emissions from stationary combustion sources: 1. The extraction of sulphur from fuels 2. Sulphur reduction within the combustion chamber 3. Treatment of flue gases.

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1. Extraction of S from fuels

S in coal is present in both inorganic and organic forms. All inorganic S exists in the coal as FeS2, i.e; in the form of pyrites and marcasites and organic S in the form of cystin, thiols, sulphides and some cyclic compounds. Washing can reduce the pyritic S content by 30 % and the organic S can be removed only by chemical processing.

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Hydrodesulphurization of Coal

This process can remove both the inorganic as well as organic forms of Sulphur.

In this process, finely ground coal is slurried with anthracene oil ( a small amount of H2 is added to avoid repolymerization and the slurry is heated at a high temperature in order to dissolve the coal.
The ash residue containing pyritic S and other minerals is eliminated by pressure filtration.

The filtrate is sent to a flash evaporator ( light fractions is removed) and subsequent operation in a distillation unit recovers the solvent.

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2. Gasification of coal
Partial oxidation of coal in the presence of O2 and steam to yield CO and H2. C + H2O CO + H2

O2 added to burn some coal to attain reaction temperature. S is converted to H2S and which is separated by either absorption or adsorption. For absorption, Na2CO3 or ethanolamine is used to scrub the gases, followed by the regeneration of the reagent with the production of elemental S. The absorption of H2S takes place in a 15 20 % aq. solution of the amine and a temperature of 30-400C and the reaction is shown below.
R N H + H S R N H H S 2 2 3

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 Then the solvent is regenerated and H2S is converted to elemental S by Claus process.
1 / 3 H S + 1 / 2 O 2 2 1 / 2 S O + 2 / 3 H S 2 2 1 / 3 S O + 1 / H O 2 3 2 S + 2 / 3 H O 2

The S is condensed and sent to a S storage tank.

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Claus Process

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 The absorption process are simple but require cooling of the gas that involves considerable heat losses. Dry methods can be carried out at high temperatures and one such processes involves the adsorption of H2S on ferric oxide in a fluidized bed at 4000C.

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Adsorption of H2S
For adsorption
Adsorbent : FeO in fluidized bed Temp: 4000C FeO is regenerated by roasting it in air at 8000C Generated SO2 used in H2SO4 plant

Iron oxide is often used for H2S removal. It can remove H2S by forming insoluble iron sulfides. The chemical reactions involved in this process are Fe2O3 + 3H2S Fe2S3 + 3H2O Fe2S3 + 3/2O2 Fe2O3 +3S Iron oxide is often used in a form called iron sponge for adsorption processes. Iron sponge is iron oxide-impregnated wood chips. Iron oxides of the forms Fe2O3 and Fe3O4 are present in iron sponge. It can be regenerated after it is saturated, but it has been found that the activity is reduced by about one-third after each regeneration cycle . Iron sponge has removal rates as high as 2,500 mg H2S/g Fe2O3.
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 The most effective method for the removal of S from the fuel oil is the hydrodesulphurization. Treats fuel oil with H2 over a catalyst at temp. of 300- 500oC and pressures of 40- 150 atm. H2 reacts with S compounds forming H2S which is collected and used for production of S. The catalyst used is Co-Mb based.

Drawback Cost of desulphurization is high.

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Fuel Oil Gasification Involves catalytic steam cracking where the hydrocarbon reacts with steam over Ni catalyst at temp. of 700- 10000C and at atmospheric pressure to form CO, CH4 and H2. The S in the fuel is converted into H2S which is then separated by one of the known processes, e.g., ethanolamine. H2S is finally converted to S in a Claus system plant.

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Sulphur reduction during combustion

Dry limestone technique Limestone is used in the combustion chamber and it is calcinated to CaO by the heat of combustion. This reacts with SO2 in the flue gas to form sulphites and sulphates.
C aC O 3 C aO + S O 2 C a O + S O 2 + 1 /2 O 2 C aO + C O 2 C aS O 3 C aS O 4

The solid reaction products, unreacted materials and fly ash are removed by either dry collectors or by wet scrubbing.

Disadvantages:

S reduction is 50 % only. CaSO4 is unstable at high temperature. Limestone does not react completely with SO2
Fluidized bed combustion process

Limestone and crushed coal together form the fluidized bed and air is used as the fluidizing medium. Operating temp: 700- 1000 0C Degree of desulphurization is 90 %, more than twice as high as that in the dry limestone tech. Drawback
Requires novel design of boilers and additional installations for the preparation of limestone, collection of solid particles carried off from the fluidized bed and regeneration of CaSO4.

Control of Sulphur dioxde Emission Treatment of flue gases

The process may be dry or wet, wet process are more effective but costly Dry process are a) adsorption of SO2 by metal oxide to form sulphites or sulphates & then regeneration of oxide & recovery of S b) adsorption on activated C and then followed by regeneration & conversion of SO2 to H2SO4 Wet process are a) Lime Limestone scrubbing b) Magnesium oxide scrubbing c) WelmanLord process

Adsorption of SO2 by metal oxides

Aluminium sodium oxide ( alkalized alumina) and manganese oxide are the widely used adsorbents, but oxides of Co and Cu are also active. Metal oxides on support exhibit an enhanced reactivity compared with that of bulk oxides. Na (or K), Sr, Cr, and Cu impregnated oxides supported on alumina are rated as superior catalysts.

Alkalyzed Alumina Process

The dust free flu gas is fed to a reactor wherein the adsorbent, a porous form of sodium aluminate (Na2O.Al2O3) , adsorbs SO2 at a temp. of 3150C. During this process, the SO2 and O2 in the flue gas react with the adsorbent.
N a O . A l O + S O + / O N a S O + A l O 2 2 3 2 1 2 2 2 4 2 3

The spent material is in contact with a reducing gas ( H2) in a regenerator at about 6800C to produce H2S.
N a O . A l O 3 + H S + 3 H O N a S O + A l O + 4 H 2 2 2 2 2 4 2 3 2

The sodium aluminate pellets are recycled and the H2S gas is sent to a Claus unit for S production

Drawback

Major problem is related to maintenance of the granular strength of the sorbent. Exposure of the sorbent to continued sorption-regeneration cycle results is uneconomically high attrition rates.

Manganese oxide process (90% removal)

The powdered adsorbent is fed into an entrainment reactor and in that, the activated MnO reacts with SO2 to produce MnSO4.
MnOx.yH2O + SO2 + 1/2 (2-x)O2 MnSO4 + y H2O

Where x is in bet. 1.5 & 1.8 and y is in bet. 0.1 &1.

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 The regeneration of the spent sorbent is carried out by reacting the MnSO4 with air and NH3 to produce ammonium sulphate.

MnOx is filtered out and & filtrate is passed through crystallizer to separate out ammonium sulphate which is used for fertilizer.

Other dry removal systems 1) Cat-Ox process produces sulphuric acid 2) Shell copper oxide process produces elemental sulphur. Cat-Ox process Fly ash is removed from the flue gas by a high temperture electrostatic precipitator, SO2 is catalytically oxidized to SO3 and recovered as sulphuric acid. The catalyst is Cat-ox A ( from Monsanto company). Shell copper oxide process- The copper oxide is impregnated onto an inert base (alumina). SO2 reacts with copper oxide at about 4000C to form copper sulphate. SO2 +1/2 O2 + CuO CuSO4

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 CuSO4 is reduced in a hydrogen rich gas CuSO4 + 2H2 Cu + SO2 + 2 H2O The concentrated SO2 is then sent to Claus sulphur recovery unit. Attractive method for continuous removal of SO2 because of the high surface area and low cost of activated C.

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The Reinluft Process Uses Cheap semicoke of peat, carbonized under vacuum at 6000C, as the adsorbent

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Draw back Instability of C in the presence of flue gas O2 which leads to C combustion. Attrition of C and corrosion. Recirculation of very large amounts of C and cost of heat and heat reducing agent is high.

BF process
Developed an improved tech. which use harder, less combustible activated C and the processes is called BF process. This uses a specially developed activated C having high resistivity against ignition and high SO2 adsorption capacity. The adsorbent can be regenerated either thermally or by washing with water. .

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Westvaco Process This process utilizes fluidized beds of high efficiency activated C and uses H2S to reduce H2SO4 to sulphur. Flue gas is contacted with activated C in the adsorber unit where the C acts as a catalyst in the oxidation of SO2 to SO3. O2, H2O SO3 H2SO4

The spent C is fed to a S generator and it is contacted with H2S to form S.

H2SO4 + 3 H2S 4S + 4 H2O

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 A fraction of the sulphur is recovered by vaporization by hot inert gases in a sulphur stripper and is recondensed as a molten product. The remaining S reacts with hydrogen in a hydrogen sulphide generator to form H2S. The regenerated C is recycled to the adsorber.

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