Control of Specific Gaseous Pollutants

Dr.Vandana

ET ZC362: Environmental Pollution Control

BITS Pilani

Learning Objectives
Dry and wet techniques for desulphurization of flue gases

Control of NOx, CO, Hydrocarbons and pollutants from mobile sources

Summary of Lecture 7

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 : Involves the transfer of pollutant from gas phase to liquid phase across the interface . A two-resistance theory is used to explain this process, 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. Adsorption : Surface phenomenon by which gas or liquid molecules are captured & adhere to the surface of a solid. The molecules which are adsorbed on the surface is called adsorbate and the substance on which an adsorbate is adsorbed is called adsorbent. eg. molecular sieves, activated C etc. Two types: Physical adsorption and chemical adsorption

 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.

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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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.

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

Control of sp.gaseous pollutants

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. 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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Hydrodesulphurization of Coal:

Useful for removing both organic and inorganic forms of S. Solvent: Anthracene 1-2% H2 to avoid polymerization Temp: 450 0C Gasification of Coal
C + H2O CO + H2

S is converted to H2S and which is separated by either absorption or adsorption.

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 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.
The solvent is regenerated and H2S is converted to elemental S by Claus process.
1/3 H2S + 1/2 O2 1/2 SO2 + 2/3 H2S 1/3 SO2 + 1/3 H2O S + 2/3 H2O

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Adsorption of H2S

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

Sulphur reduction during combustion Dry limestone technique CaO + CO2 CaCO3

CaO + SO2 CaO + SO2 + 1/2 O2

CaSO3 CaSO4

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Treatment of flue gases 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

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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.
Alkalyzed Alumina Process
Na2O.Al2O3 + SO2 + 1/2 O2
Na2SO4 + Al2O3 + 4H2

Na2SO4 + Al2O3
Na2O.Al2O3 + H2S + 3H2O

Manganese oxide process (90% removal)

MnOx.yH2O + SO2 + 1/2 (2-x)O2 MnSO4 + y H2O

( N H ) S O + M n O y H 2 O M n S O + 2 N H + 2 H O + ( y 1 ) H O + 1 / 2 ( x 1 ) O 4 2 4 x 4 3 2 2 2

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Adsorption on activated carbon Attractive method for continuous removal of SO2 because of the high surface area and low cost of activated C. 1. The Reinluft Process Uses Cheap semicoke of peat, carbonized under vacuum at 6000C, as the adsorbent.

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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Adsorption of SO2 by Wet method

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 Hydrated lime can also be used in this process. 2Ca(OH)2 + 2 SO2 + O2

CaSO3 + CaSO4 + 2H2O

Various types of Scrubbers employed commercially : Spray towers, venturies, packed beds, and turbulent contact absorbers. The scrubbing systems can be designed for 80 95 % SO2 removal. Advantage: Relatively simple, low cost and the easy availability of limestone Disadvantage: Sludge disposal

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Magnesium Oxide Scrubbing

The flue gas is scrubbed with a slurry of MgO which absorbs SO2 and yields magnesium sulphite and sulphate.
MgO + SO2 MgSO3 + SO2 + H2O Mg(HSO3)2 + MgO MgSO3 + O2 heat MgSO3 Mg(HSO3)2 2 MgSO3 + H2O MgSO4

MgSO3
MgSO4 + C

MgO + SO2
MgO + SO2 + CO2

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Welman-Lord Process
Saturated sloution of Sodium sulphite absorb SO2 from flue gases; sulphite is converted to bisulphite.
Na2SO3 + SO2 + H2O 2 NaHSO3

Bisulphite decomposes into sodium sulphite around 1100C, releases conc.SO2 and steam.
2NaHSO3 Na2SO3 + SO2 + H2O

Degree of desulphurization : 90 %

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 SO2 oxidation leads to the formation of sodium sulphate which can not be regenerated and therefore it is purged from the system.
An equivalent amount of NaOH is addded to maintain the sodium balance.

Deg.of desulphurization 90 %

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Other flue Gas Scrubbing processes

1. Stone& Webster Ionics Process Reaction is based upon the reaction of caustic soda solution with SO2 to form sodium sulphite and bisulphite.
2 N aO H + C O N a2C O N a2S O N a2S O
3 3 3 2

N a2C O N a2S O
2

+ H 2O + CO
4 3 2

+ SO

+ 1 /2 O
2

N a2S O

+ SO

+ H 2O

2 N aH SO

NaHSO3/ Na2SO3 is treated with dil.H2SO4 to get sod.sulphate and Conc.SO2 gas.

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N a S O + H S O 2 3 2 4 2 N a H S O + H S O 3 2 4

N a S O + S O + H O 2 4 2 2 N a S O + 2 S O + H O 2 4 2 2

Electrolytic regeneration cell converts Na2SO4 into caustic soda and H2SO4. The overall reaction is The caustic soda is returned to the absorber and acid is used in the desorption tower. 2. The Atomics International molten salt process Unconventional scrubbing process which uses a mixture of lithium, sodium and potassium carbonates in a melt at about 4250C. SO2 and SO3 react with metal carbonates to yield corresponding sulphites and sulphates. .
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2 N a O H + H S O + H + 1 / 2 O N a S O + 3 H O 2 4 2 2 2 4 2

M2CO3 + SO2 M2CO3 + SO3

M2SO3 + CO2 M2SO4 + CO2 M- alkali metal ions

The mixture is regenerated in a two stage process. First stage, the sulphate and sulphite are reduced to sulphide by using producer gas ( CO + H2).
M2SO3 + 2CO + H2 M2SO4 + 2CO + 2H2 M2S + 2 CO2 + H2O M2S + 2CO2 + 2 H2O

The reduced melt is then reacted with steam and CO2 to produce H2S and M2CO3
M2S + H2O + CO2 M2CO3 + H2S
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Metal Smelting Operations - Sources of SO2 emissions The conc. of SO2 emissions from smelting is high enough to produce either H2SO4 or S. Liquid SO2 can be produced using the ASARCO process by absorbing SO2 in dimethylamine. Byproduct H2SO4 manufacture The manufacture of H2SO4 from smelting involves gas conditioning, drying, catalytic conversion, and absorption. The gas conditioning step removes impurities like As, Cl-, F-, fumes of metal sulphide or oxide, mercury etc. This is necessary to avoid rapid deactivation of the catalyst.

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 Gas coming out of the smelters has a temp. above 6000C and it is cooled to about 550C by injecting water and this prevents acid contamination and minimizes catalyst fouling. The gas is dried by using 93 % H2SO4 to absorb the moisture. The smelter gas is sent to a catalytic converter. The gas is passed through a four stage catalytic converter and SO2 is converted to SO3. (conventional single absorption contact plant) The gas is cooled and then absorbed in a circulating stream of 98% to 99% H2SO4. SO3 unites with the small excess of water in the acid to form more H2SO4.

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Double contact, double absorption (DCDA) method

This method provides higher plant efficiencies (99.5%) and SO2 emissions of below 500 ppm. The gases from the converter, after conversion of (90%) SO2 to SO3 passed at an intermediate stage to an absorber to remove the SO3. The gases are reheated and returned to the converter for further conversion. This then pass through additional catalyst, cooled and flow through a second absorber and then to the atmosphere.

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Absorption in Dimethylaniline- ASARCO Process

ASARCO- American Smelting& Refining Co. The waste gases containing SO2 are absorbed in dimethyaniline in the lower stages of an absorber. The desulphurized gas containing dimethylaniline is scrubbed with Na2CO3 solution and then with dil.H2SO4 to remove traces of SO2 and dimethylaniline. The SO2 rich liquor is fed to a steam distillation column which strips SO2 from the liquor and dimethylaniline is recycled. SO2 is dried with 98% H2SO4 in a drying tower, liquified and sent to storage for further processing. The tail gas leaving the stack after scrubbing contains around 500ppm SO2. This process is economical only for SO2 conc. Above 2%.

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Absorption in Ammonia
Aq.ammonia is used in the COMINCO (Consolidated mining and smelting Co.) process for reducing the SO2 conc. A 30% solution of aq.ammonia absorbs SO2 , producing ammonium bisulphite. SO2 is then stripped from this solution by adding 93% H2SO4 in a stripping column.

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Contact process is used to manufacture Oleum and Sulfuric acid. The methods involved in controlling SO2 emissions in this process.

Around 2000 PPM of SO2 is released through tail gases (limit: 500 PPM) DCDA (double contact and double absorption) process reduces the SO2 emissions. Here 90% of SO2 is converted to SO3. The gases are re-heated, passed through additional catalyst, cooled, flow through a second absorber and then to the atmosphere. Here microporous molecular sieves such as alumino-silicate zeolites are used as adsorbents. The sodium (Welman) and magnesium (Chemico) scrubbing systems have been used to reduce the SO2 emission to less than 300 PPM Ammonium scrubbing process is also used and here the ammonium sulphitebisulphite formed is reacted with nitric or orthophosphoric acid to produce the ammonium salt and SO2 is recovered for further processing.
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Petroleum Refining Sulphur is found in the combined form in crude oil; H2S and thiophenes are the most common S compounds , but it may also be present in the form of mercaptans and sulphides. Desulphurization is carried out , not only for the sake of pollution control but also for improving the product quality and minimizing corrosion problems in the processing plant. Removal of H2S and mercaptans can be carried out by washing the oil with aq.soda solution and complex S compounds have to be broken down catalytically . Hydrodesulphurization is the most common method in which H2 reacts with organic S compounds forming H2S which is collected and can be converted to S.

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Control of NOx emission

Two main sources of N2 which contribute to the formation of nitrogen oxides during combustion are atmospheric nitrogen and the other is the bound nitrogen in the fuel. NOx are formed in the combustion processes according to the reactions
1 / 2 N + 1 / 2 O 2 2 N O + 1 / 2 O 2 N O N O 2

The primary oxide is NO, which rapidly converts by reaction with O2 or ozone to NO2. NOx emissions from stationary sources can be reduced by 1. minimizing the residence time 2. minimizing temp. 3. minimizing the availability of O2 for reaction with N2.
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The methods for the removal of NOx can be grouped into two categories 1. Scrubbing - two ways a) Absorption by liquids b) Adsorption by solids 2. Catalytic decomposition and reduction : Involves decomposition of nitric oxide into N2 and O2 or reaction with another gas such as CO. Absorption by liquids The processes which have been proposed for controlling NOx emissions from power plants are 1. Treatment with lime slurry 2. Scrubbing with Magnesium hydroxide liquor 3. Absorption in H2SO4

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 All these processes are complex and require attainment of equimolar concentrations of NO and NO2 in the gas, since the absorption of the combined oxide N2O3 is most favourable. In Magnesium hydroxide scrubbing process, the oxides of nitrogen are absorbed by magnesium hydroxide liquor in an absorption tower. The resulting magnesium nitrate/nitrite solution is taken to a pressure reactor and nitrite is converted to nitrate. The byproduct NO is oxidized to NO2 and the liquid leaving the pressure reactor, consisting of Mg(NO3)2/ Mg(OH)2 is sent to a settling chamber. Here the nitrate is separated from the hydroxide which is recycled to the absorption tower. Part of the NO2 is sent to the absorber to maintain equimolar conc. Of NO and NO2 while the rest of NO2 is used for HNO3 production.

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Absorption of NOx by mag.hydroxide

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Other types of scrubbing techniques developed

1. Two stage absorption, first in water and then in NaOH, yielding nitrite and nitrate salts.

2. Absorption in various types of ammonical solutions such as ammonium bicarbonate and ammonium bisulphite : Ammonium bisulphite can be used as a scrubbing liquor when NOx react quickly at normal pressure and temp. to form ammonium sulphate which can be used a fertilizer. 3. Absorption with an aq.suspension of lime: Aq.suspension of calcium hydroxide as absorbing medium results in reduction of NOx levels to 200 ppm. The calcium nitrite can be converted to calcium nitrate by treating withH2SO4. During the oxidation of nitrite to nitrate, NO is evolved.
2H2SO4 + 3 Ca(NO2)2 2 CaSO4 + 4NO + Ca(NO3)2 + 2 H2O

The evolved NO is recycled to the HNO3 plant and calcium nitrate can be used as a fertilizer.

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Adsorption by solids
The commonly used adsorbents are activated C, silica gel, molecular sieves, ion exchange resins and metal oxides like manganese oxide and alkalised ferric oxides. These adsorbents shows some capacity for oxidising NO to NO2 and for adsorbing nitrogen dioxide. The main disadvantage of using molecular sieves as adsorbents is the simultaneous adsorption of water vapour in the tail gas which decreases the efficiency of the bed. The most suitable adsorbent is the one which can be regenerated and at the same time which does not react with water vapour or with CO2 and the most preferred adsorbent is ferrous salt.

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Catalytic Decomposition

The decomposition of NO ( both homogeneous and heterogeneous) is slow and therefore we can use variety of catalysts like Al2O3, Cr2O3, Fe2O3, ZrO3 and Co3O4 for the decomposition. At reasonable temp. no catalyst has been found with sufficient activity.
Catalytic Reduction Catalytic reduction is an attractive method for controlling nitrogen oxide emissions. Catalytic decolourizers are used to reduce NOx to NO, but NO reduction to N2 is limited. The decolourization product NO could be reduced to molecular N2 in the presence of reducing agents like H2, natural gas and CO or we can use the most effective catalysts like Pd and Pt (catalytic abatement process).

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 The noble metal catalysts used in HNO3 plants, for application to flue gas emission control, are expensive and subject to S poisoning in the case of coal and oil fired equipment and this led to the study of the reduction reaction over different types of commercial catalysts. There are two types of reduction process, selective and non-selective. The added reactant reduces NOx in selective reduction, and in non-selective reduction, the excessive oxygen must be consumed first and the former one is preferred because it minimizes the amount of reactant required. Selective reduction can be carried out with H2, CO or NH3 as the reactant gas.

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Typical reactions are 2 NO + 2 H2 2NO + 2CO N2 + 2H2O N2 + 2CO2

6NO + 4NH3

5N2 + 6H2O

In non-selective reduction, there are two types of reactions. First type involves the reaction of the fuel with oxygen and NO2, the latter being reduced to NO.
CH4 + 2O2 CH4 + 4NO2 CO2 + 2 H2O CO2 + 2H2O + 4 NO
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 The second reaction reduces the NO but the reduction does not take place until all the oxygen in the flue gas has been reacted with the fuel and reducing conditions have been achieved.
CH4 + 4NO CO2 + 2H2O + 2N2

CO control CO is an intermediate product of chemical reaction between fossil fuels and oxygen. There are two reasons for the formation of CO 1. 2. Because of insufficient quantity of O2. Due to poor turbulance of the fuel and air in the reaction chamber or due to dissociation of CO2 to CO in high temp zones.

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 The control of CO formation is not easy because the control strategies for CO and NOx are in conflict. The most practical method of reducing the CO emisions from stationary combustion sources is by proper design, installation, operation and maintenance of the combustion equipment. CO and H2 are widely used in the chemical industry for the manufacture of methanol,ammonia and various organic acids and aldehydes. The emissions from the chemical and petroleum industry are minor because of good design codes and careful operating practices.

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Control of Hydrocarbons Four techniques are there to control hydrocarbon emissions from stationary sources. 1. Incineration 2. Adsorption 3. Absorption 4. Condensation Adsorption: The polluted gas stream is passed through one or several adsorbers operated in parallel. Operating temp: between 30 and 600C Preferred adsorbent: granular activated C The adsorbed vapours are removed by passing steam through the system. The mixture of steam and hydrocarbons are liquefied in a mixture and cooled down to ambient temp. in a cooler.
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 The hydrocarbons are separated from the water and recovered for further use. The most effective way of removing hydrocarbons from a polluted stream is by contact with a liquid or a series of different liquids, in one or more absorption towers. If the hydrocarbons have sufficiently high solubility water is a suitable solvent . Condensation : - Direct Contact condenser (counter current flow) - Surface type condenser (shell and tube) In direct contact condensers, a stream of water or other cooling liquid is in contact with the vapour to be condensed. The polluted stream enters the condenser at the bottom and the cooling liquid is introduced at the top. The gaseous stream leaving the condenser at the top contains non condensable gases and the condensate is withdrawn from the bottom of the condenser.

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 Spray chambers, cyclone scrubbers and venturi scrubbers can be used as direct contact condenser.
Vertical type surface condenser

The polluted gas stream enters at the top and flows through the tube passes and the cold liquid enters at the bottom on the shell side and leaves at the top. The condensed liquid is separated from the non-condensable vapours at the bottom of the condenser.

Vertical condenser

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Biological Oxidation Biological oxidation is an important method in industry for hydrocarbon and odour control. In this method, microorganisms are employed to metabolize pollutants in gas streams. This process takes place at ambient temp., consume very little energy and produce no nitrogen oxides. The oxidation reactions are carried out in biofilters and the end products are CO2, H2O and microbial mass. If the conc. Of hydrocarbons is below 1.0 mg/m3 biofilters are most effective. Biofilter consists of a bed of packing material on which a microbial film is attached. Activated sludge from municipal waste water treatment plants are also used.

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 The polluted gas is introduced at the bottom of the filter and the pollutants diffuse into the biofilm and there they are metabolised by aerobic bacteria. Mobile Sources The principal pollutants emitted from mobile sources are CO, NOx and hydrocarbons. The major source of air pollution from automobiles is the exhaust pipe which accounts for about 70% of the pollution and crank case emissions about 20 % and evaporations from fuel tank and carburettor account for the remaining. Control methods applied to one pollutant influence the out put of other pollutants. Eg; The amount of CO formed during the combustion period is related to the ratio of air and fuel in the cylinder. If there is excess of fuel, then the products of combustion contain high level of CO and hydrocarbons and low levels of NOx.

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The control of pollutant emissions from automobiles is based on the following approaches:
1. Reduction of the amount of pollutants formed during combustion by suitable modification of the internal combustion engine. Development of exhaust system reactors that will complete the combustion process and change potential pollutants into more acceptable materials. Development of substitute fuels for petrol that will produce low levels of pollutants upon combustion. Replacement of internal combustion engine with low pollution producing engines.

2.
3. 4.

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 Exhaust system reactors , both thermal and catalytic can be used to reduce CO and hydrocarbon emissions. By changing the fuel either by mixing petrol with other substances or by substituting another fuel with petrol. Alternative fuels are there and the known petrol substitutes are methane or natural gas, hydrogen and methanol. Replacement of IC engines with other types of engines like steam, electric and gas turbine engines is a good solution to the emission control problem. The control of hydrocarbon emissions from automobiles is more complicated than control of CO emissions evaporation contribute to the pollution problem. The use of a canister filled with activated C to adsorb the hydrocarbon vapours can reduce the evaporation losses from fuel tank and carburettor. The adsorbed vapours are desorbed and returned to the carburettor and burned in the engine.

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The control of NOx emission from automobiles

1. Exhaust gas recirculation (EGR) In EGR, portion of the exhaust gas (inert), is continuously recirculated through the engine so that the burning air-fuel mixture is diluted. This decreases the O2 conc. In the burning mixture thereby lowering the combustion temperature. The exhaust gas is regulated by an EGR valve. 2. Catalytic reduction.

Dual catalyst system in which NO is reduced to N2 and hydrocarbons and CO are oxidized to CO2 and H2O simultaneously. The exhaust gases are passed over a reductive catalyst and here NO reacts with CO to form N2 and CO2.

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 Air is injected and the mixture is passed over an oxidative catalyst and the remaining hydrocarbons and CO are oxidised to CO2 and H2O. In reduction catalyst chamber, ammonia may form which will be converted to NO or N2O in the oxidising catalyst chamber.

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Briefly describe the two techniques used in Control of hydrocarbon emissions from stationary sources.
Incineration:

If the waste gas contains sufficient combustible material, then incineration may be the simplest route. Normally it is smokeless and odorless unless high molecular weight hydrocarbons are used. Most efficient in destroying diluted gas streams. Waste gas is preheated over an auxiliary fuel fired burner and passed into a combustion chamber where a temperature of 500-800 OC is maintained. Gas stream is kept at this temperature for a residence time of 0.3 to 0.7s to allow complete oxidation Gas stream is introduced in such geometry and at a velocity that promote turbulence and thorough mixing with a burning fuel. High operating cost of fuel is reduced by recovering the waste heat. It emits NOX, which can be reduced by adopting catalytic incineration.

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Adsorption:

Hydrocarbons (HC) are passed through one or several absorbers in parallel Operating temperature is kept between 30 -60OC. Adsorbent: granular activated carbon (particle diameter: 2-4 mm). Adsorbed vapors are removed by passing steam through the system. The mixture is liquefied in a condenser and cooled down to a ambient temperature. HC are separated from water and used again. Capital cost is high, but low maintenance .

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Write the name, source and control of air pollutants from automobiles?
Air Pollutants from automobiles: Principal Pollutants from automobiles: CO, NOx, HC Sources: Exhaust pipe, Crankcase emissions and Evaporations from fuel tank/ Carburettor. Exhaust emissions differs with the type of engine (petrol or diesel), because diesel engine works with compression ignition and petrol engine works with spark ignition. Control of Pollutant emission is possible by 1. Modification or replacement of internal combustion Engine 2. Developing the exhaust system 3. Developing the fuel alternatives

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