COURSE MODULE ON STATIONARY SOURCE SAMPLING AND ANALYTICAL METHODS FOR GASEOUS POLLUTANTS

FOR INDUSTRIAL POLLUTION PREVENTION AND CONTROL (IPPC) DR. AMBEDKAR INSTITUTE OF PRODUCTIVITY MADRAS

PREPARED BY

V.S.S.Bhaskara Murty
Director (Environment) Dr Ambedkar Institute of Productivity National Productivity Council, Chennai

1995

1.0 INTRODUCTION

Many industrial processes, such as Smelters, Fertiliser plants fossil fuel combustions etc. emits gaseous air pollutant. The gas sampling method constitutes the collection of representative gas sample from the parent gas stream in a suitable absorbing media and analysing the grab samples by wet chemical analysis. The representative gas samples are collected through the sampling port from any point across the cross section of the duct since the gas composition is uniform. However proportional sampling techniques have to be implemented if the source is unsteady and vary with time. Most frequently measured gas components viz. sulfur dioxide (SO2), sulfur trioxide (SO3), acid mist, Nitrogen Oxides NOx) are described below. 2.0 SULFUR DIOXIDE AND SULFUR TRIOXIDE CPCB has prescribed emission standards for SO2 and SO3 for different industrial operations as given in the Annexure-1. For sulfuric acid manufacture these two gas components are analysed combinedly interms of SO2 and in addition acid mist concentration is another important parameter. The emission load of SO2 has importance in calculating the minimum stack height requirements of industrial operations. 2.1 PRINCIPLE AND APPLICABILITY The basic problem is to detect SO2 in the presence of SO3 and H2SO4. Therefore the latter components first must be removed from the sample. The sulfur dioxide is then absorbed in a hydrogen peroxide solution and eventually is determined quantitatively by titration with barium perchlorate or barium chloride. Thorin is used as a color indicator for this titration.

2.2

INTERFERENCES

Metal sulfates, phosphates, sulfuric acid mist, and cations which complex with the thorin indicator or coprecipitate with barium, interfere but can be eliminated by proper use of a filter. 2.3 SAMPLING TRAIN

The sampling train is similar to that of particulate sampling as shown in Fig-1 except for the dust collecting thimble holder which is replaced by a set of midget impingers for the absorption of the gaseous components. 2.3.1 Sampling probe: A short sampling probe Pyrex or quartz is used to prevent condensation prior to sample collection. Quartz of Pyrex glass wool is placed in the entry of the probe to prevent particulate matter from entering the scrubbers. Alternatively a midget bubbler stuffed with glass wool is placed at the end of the sampling probe along with the gas absorption equipment. The particulate matter contains sulfates and also other impurities which may precipitate with barium or complex with the thorin indicator. Acid mist is also removed at this point. 2.3.2 Absorption equipment: The sample collector consists of three midget impingers (Fig-2) placed in an ice bath. The first midget impinger contains 100 ml of 80% isopropyl alcohol solution. This removes the SO3 and any carry over H2SO4 from the filter. Some glass wool is placed at the top of the midget bubbler to act as a filter and thus preventing any H2SO4 mist from carrying over into the following midget impingers. The gas stream becomes saturated with the isopropyl alcohol vapor, which inhibits the oxidation of SO2 to SO3 because the alcohol is more readily oxidized.

The SO2 is removed in the next two midget impingers, which contain 100 ml each of hydrogen peroxide solutions. SO2 is absorbed in the impingers and converted to form H2SO4.

2.3.3 Flow metering: Finally the gases are passed through silica gel drying column to protect the Dry Gas Meter which follow it. To achieve the optimum absorption efficiency, the sampling flow rate has to be set at a minimum constant flow rate of 2 lpm with the help of rota meter and the needle valve. 2.3.4 Vacuum pump: Since the sampling flow rates are very low the pressure drop across the sampling train is around 10 to 15 mmHg and hence a small capacity vacuum pump is enough for such purpose.

2.4

GLASSWARE & REAGENTS

The following reagents and glass ware have to be kept ready in the laboratory for analysis of the field samples. 2.4.1 Glassware: - Glass wash bottle to hold the deionized water - Polyethylene storage bottles for storing impinger samples prior to analysis. - Transfer pipettes: 5 ml and 10 ml sizes with 0.1 ml divisions and 25 ml size with 0.2 ml divisions - Volumetric flasks : 50 ml, 100 ml and 1000 ml - Burettes : 5 ml and 50 ml - Erlenmeyer flask : 125 ml - Dropping bottle for indicator solution.

2.4.2

Reagents:

2.4.3 deionized distilled water 2.4.4 Hydrogen peroxide,(3% solution): Prepare by diluting 100 ml of 30% hydrogen peroxide to 1 liter with deionized water. Caution: the 30% H2O2 is a strong skin irritant which is not noticeable until a few minutes after the injury occurs. This solution must be prepared daily. 2.4.5 Isopropyl alcohol,(80% solution): Prepare by mixing 80 ml of isopropyl alcohol with 20 ml of deionized water. This solution is stable. 2.4.6 Thorin indicator: [1-(0-arsonophenylazo) -2-naphthol-3, 6-disulfonic acid, disodium salt (or equivalent)]. Prepare by dissolving 0.2 grams in 100 ml of deionized distilled water. It should be stored in a polyethylene container since it tends to deteriorate if stored in glass. 2.4.7 Barium perchlorate (0.01N): Prepare by dissolving 1.95 grams of barium perchlorate, Ba(ClO4)2 3H2O in 200 ml of deionized water. Then dilute to 1 liter using isopropyl alcohol. Alternatively, dissolve 1.22 grams of barium chloride, BaC12.2H2O, in 200 ml deionized water and then dilute to 1 liter with the isopropyl alcohol. The normality of this solution should be standardized with standard sulfuric acid. 2.4.8 Sulfuric acid standard (0.01N): Purchase or standardize to + or - 0.0002 N against 0.01 NaOH which has previously been standardized against primary standard grade potassium acid phthalate.

2.5

SAMPLING PROCEDURE

This method determines only the concentration in the gas stream. The volumetric flow rate of the stack must be determined according to EPA methods 1 and 2. The same sampling port which is used for the velocity monitoring can be used for the gaseous

sampling. Eventhough the gas composition is uniform across the cross section of the duct, it is advised to collect the sample at the centroid of the duct or not closer than 200mm to the duct wall.

The sampling train is assemble as shown in the Fig-1 and leak tested by plugging the probe inlet and pulling 300mmHg vacuum. Observing the dry gas meter, the leakage rate should not exceed 1% of the desired sampling rate. If the leakage is severe, each joint of the train should be inspected and the leak test performed again. A thin film of silicone grease often helps to make the joints leak tight. The impingers are filled with the reagents as given in 5.2. The initial reading of the DGM is recorded and a sampling flow rate of 2 lpm is maintained at the rotameter. In case of unsteady source conditions, " proportionate sampling" is implemented by introducing the Pitot tube in to the duct along with the sampling probe and the sampling flow rate varies with the variations in the velocity of the gas stream. Gas samples are collected for a minimum period of 20 to 30 minutes and the final DGM reading, meter temperature and pressure are recorded. At the end of the sampling disconnect the sampling probe from impingers and flush the impingers with about 10 litres of atmospheric air by turning on the vacuum pump. It is necessary to transfer the entrapped SO2 in the first impinger and absorbed in the following impingers. Transfer the contents of the impingers into the polythene bottles and continue sampling for next set of samples. A minimum of two samples have to be collected to get consistent and representative data.

2.6 ANALYTICAL PROCEDURES 2.6.1 Sulfur Trioxide (SO3): Transfer the sample from the first impinger to a 100ml volumetric flask and make up to the mark with distilled, deionized water. SO3 is absorbed by water and forms H2SO4. Pipette a 10 ml aliquot to a 125-ml Erlenmeyer flask and add 40 ml of isopropanol and 2 to 4 drops of the Thorin indicator solution. The solution will then have a yellow-orange color. The sulfuric acid is titrated against standardized barium usually as the perchlorate or chloride. Thorin is used, which acts to complex, and excess barium is added, thus giving a color indicator. Titrate to a pink end point with the 0.01 N barium perchlorate and record results. During the titration the barium is consumed by the sulfate and forms, in the presence of isopropyl alcohol, a gelatinous type of precipitate which equilibrates rapidly. At the first presence of any excess barium, a pink barium-thorin complex forms indicating that all of the sulfate has been consumed. The determination of the end point by the color change may take some practice on the part of the analyst; it is less vivid than some other calorimetric indicators but nonetheless proves to be quite adequate. The standard laboratory procedure of using a blank of deionized water should be used for all sets of samples, allowing any systematic error due to the reagents or procedures to be accounted for. 2.6.2 Sulfur Dioxide (SO2): Transfer the samples from the two midget impingers in to two 100ml volumetric flasks separately and make up to the mark with distilled water. The SO2 has been oxidized to SO3 with H2O2 and hydrolyzed to form sulfuric acid in the impingers. Follow the same analytical procedure as given in 2.6.1 for the samples in both the impingers separately to check the absorption efficiency and to ensure that there is no escape of SO2 along with the gas.

2.7

DATA ANALYSIS

2.7.1 Volume of the gas sampled: The difference of the initial and final readings of DGM gives the gas volume sampled at meter temperature (Tm) and Pressure (Pm) conditions. This can be further converted to normal conditions as

Qn Where

Qm

Tn x Pm --------Tm x Pn

. . .

(1)

Qn .. Qm .. Tn Tm Pn Pm

Volume of gas sample under normal condition, NM3 Volume of gas sample under meter conditions, M3

.. The absolute gas temperature at normal conditions,298 oK .. The absolute dry gas meter temperature, oK .. The absolute pressure at normal conditions, 760 mmHg .. The absolute pressure at the gas meter, mmHg

2.7.2

SO3 concentration:

The concentration of SO3 in the gases is determined using the following expression:

(A-B) x V x N x 40 CSO3, mg/NM3 = ----------------------v x Qn

. . . (2)

Where A .. Volume of the Ba(ClO4)2 consumed by the sample aliquot,ml B .. Volume of the Ba(ClO4)2 consumed by the blank,ml v .. Volume of the aliquot,ml V .. Volume of the absorbing solution,ml N .. Normality of Ba(ClO4)2 48 .. Equivalent weight of SO3, gm/gm mole 2.7.3 SO2 concentration:

The concentration of SO2 in the gases is determined using the same expression for SO3 by replacing the equivalent weight with 36 gm/gm mole. The average concentration of SO2 is estimated by considering the arithmetic average of both the impinger readings. 2.8.0 SUMMARY

Laboratory analysis is completely wet chemical and several hazardous solutions are used. For example extreme care must be used when working with the 30% hydrogen peroxide solution. This strong oxidant is a harsh skin irritant, the effect of which is unnoticed until about 5 minutes after exposure.

3.0

ACID MIST CONCENTRATION

Acid mist from sulfuric acid plant emissions is sampled by isokinetic sampling techniques using a glass fibre thimble since the acid mist also persists in different droplet sizes. The sampling train similar to particulate matter concentration measurements is employed for acid mist sampling as shown in Fig-3.

For analysis the thimble is thoroughly washed with distilled water and the resultant solution is titrated against Ba(ClO4)2 as given in 2.6.1. The concentration of acid mist is calculated by using the same (2) for SO3 estimation by replacing the equivalent weight by 49 gm/gm mole.

4.0

NITROGEN OXIDES (NOx)

Nitrogen oxides mainly consisting nitrogen dioxide (NO2) and nitrous oxide (NO) forms by the combustion reactions. Combustion temperatures up to about 600oC NO2 formation is maximum. Normally in industrial operations where the combustion temperatures are about 1000oC, Nitrogen Oxides comprise of about 90-95% of NO and remaining NO2. CPCB has prescribed standard procedure for sampling and analysis of NOx based on the method EPA-7. However CPCB has not yet prescribed any standards for the NOx emissions. However NOx is a dominant pollutant in atmospheric reactions and formation of secondary pollutants. 4.1 PRINCIPLE AND APPLICABILITY

The sample is removed by a grab sampling technique. It is captured in a 1-litre grab pipette or a 1-litre evacuated flask which contains an absorbing solution of hydrogen peroxide and sulfuric acid which converts the NOx (except N2O) in the captured gas to HNO3 in solution. The amount of nitrate in solution is determined by the phenoldisulfonic acid method. The amount of nitrate (NOx) is then determined by calorimetric comparison to standard solutions of potassium nitrate.

4.2

INTERFERENCES

Phenoldisulfonic acid (PDS) forms a strong color complex with NOx and no interferences are reported. 4.3.0 SAMPLING TRAIN of NOx samples by wool is packed in from entering the through the grab 2 lpm by a needle

The sampling train for collection and analysis grab pipette is shown in Fig-4. Quartz or Pyrex the glass probe to prevent particulate matter flask. A vacuum pump draws the gas sample pipette. The sampling flow rate is adjusted at

valve so that there is excessive vacuum build up in the grab pipette. The method EPA-7 suggest evacuated flask method as shown in Fig-5. The stopcocks and the T-bore insure the proper sequence for evacuating, purging and sampling. A high capacity vacuum pump pulls the vacuum in the flask up to a maximum of 70 mmHg (absolute). The evacuated flask as a part of the sampling train is connected to the source and with the help of the T-bore the sample is drawn in to the flask. The accuracy of measurement depends on the maximum vacuum created in the sample flasks. If the vacuum pump has no enough capacity to draw the vacuum it is suggested to use the grab pipette method which can produce the results with acceptable range of error.

4.4.0 4.4.1

GLASSWARE, EQUIPMENT AND REAGENTS Glassware - Beakers or casseroles, 250 ml - Volumetric pipettes, 1, 2 and 10 ml - Transfer pipette, 10 ml with 0.1 ml divisions - Volumetric flasks : 100 ml for each sample; 1000 ml for standard - Graduated cylinder, 100 ml with 1.0 ml divisions

4.4.2

Equipment - Steam bath - Spectrophotometer, measurement at 420 nm - Analytical balance, measure to 0.1 mg.

4.4.3

Reagents - Concentrated H2SO4 - 3% H2O2

- Distilled water - 1 N NaOH solutions (add 40 g NaOH in distilled water and dilute to one liter)

- Red litmus paper - Phenoldisulfonic acid (PDS) - Potassium nitrate

4.5.0 4.5.1

SAMPLING PROCEDURES Laboratory procedure

The volume of the flask/grab pipette must be determined. This is done by filling the flask/grab pipette with water and then measuring the volume of water with a graduated cylinder. Record the volume on each flask/grab pipette. The absorbing solution is prepared by adding 2.8 ml of concentrated H2SO4 to 1 liter of distilled water. To this mixed solution, add 6 ml of 3% hydrogen peroxide. Fresh solution should be prepared weekly and protected from heat or sunlight. 4.5.2 Field procedure

This method determines only the concentration in the gas stream. The volumetric flow rate of the stack must be determined according to EPA methods 1 and 2. Three repetitions are required per test and two grab samples are required per source. These two samples should be taken over a two-hour interval, if the process characteristics are not known. If the process is known to be steady, then the time can be shortened. Clean justification of this modification should be included in the final report.

4.5.2.1 Grab pipette: Connect the grab pipette (Fig-4) to the sampling probe and the vacuum pump through the rotameter and needle valve. Set the sampling flow rate at 2 lpm. Insert the sampling probe into the duct, open both the stop cocks of the pipette and allow purging for about 5 minutes with the process gas. Close the stop cocks at the out let of the pipette first and the second one immediately so that there is no evacuation of the gas from the pipette or the gas collection is under vacuum. 4.5.2.2 Sampling in evacuated flask: Pipette 25 ml of absorbing solution into a sample flask. Insert the flask valve stopper into the flask with the valve in the "purge" position. Assemble the sampling train as shown in Fig-5 and place the probe at the sampling point. Turn the flask valve and the pump valve to their "evacuate" positions. Evacuate the flask to at least 70mmHg absolute pressure. Turn the pump valve to its "vent" position and turn off the pump. Check the manometer for any fluctuation in the mercury level. If there is a visible change over the span of one minute, check for leaks. Record the initial volume, temperature, and barometric pressure. Turn the flask valve to its "purge" position, and then do the same with the pump valve. Purge the probe and the vacuum tube using the squeeze bulb. If condensation occurs in the probe and flask valve area, heat the probe and purge until the condensation disappears. Then turn the pump valve to its "vent" position. Turn the flask valve to its "sample" position and allow sample to enter the flask for about 15 seconds. After collecting the sample, turn the flask valve to its "purge" position and disconnect the flask from the sampling train. Shake the flask for 5 minutes. 4.6.0 Analytical procedure 4.6.1 Recovery: This method specifies a minimum sample absorption time of 16 hours. Margolis and Driscolls theoretically predicted a 97% recovery would require 28.7 hrs. Hence the absorption process is the slowest step in the NOx procedure. The samples may be returned to the laboratory in the

flask/pipette and kept in a cool and dark place for a minimum period of 24 hrs. 4.6.2 Analysis: After the absorption period shake the contents of the flask/pipette for 2 minutes. The contents of the flask are then transferred to 100 ml china dish. The flask/pipette is rinsed with two small portions of distilled water (10 ml). An accompanying blank of absorbing solution, along with an equal amount of rinse, is also processed. Then 1.0 N NaOH is added to the absorbing solutions until they are alkaline to litmus paper.

Evaporate the solution to dryness on a steam bath and then cool. Add 2 ml phenoldisulfonic acid solution to the dried residue and dissolve all the residue thoroughly using a glass rod. Make sure the solution contacts all the residue. Add 1 ml distilled water and 4 drops of concentrated sulfuric acid. Heat the solution on a steam bath for 3 minutes with occasional stirring if any undissolved matter presents. Cool, add 20 ml distilled water, mix well by stirring, and add concentrated ammonium hydroxide drop wise with constant stirring until alkaline to litmus paper. Transfer the solution to a 100 ml volumetric flask and wash the beaker three times with 4 to 5 ml portions of distilled water. Dilute to the mark and mix thoroughly. If the sample contains solids, transfer a portion of the solution to a clean, dry centrifuge tube, and centrifuge, or filter a portion of the solution. Measure the absorbance/extintion of each sample in a spectro photometer at 420 nm using the blank solution as a zero. Read the amount of NO2 value "m" correspond to the absorbance/extintion value from the standard calibration grab drawn following the procedure given in 4.6.3. Dilute the sample and the blank with a suitable amount of distilled water if absorbance falls outside the range of calibration. 4.6.3 Calibration

The standard solution is prepared by dissolving 0.5495 g of KNO3 in distilled water and diluting to 1 liter. The working solution is prepared by diluting a 10-ml portion of the standard solution to 100 ml; 1 ml of this solution then is equivalent to 25 ug of NO2. The calibration curve is prepared by adding 0.0 to 16.0 ml of standard solution to a series of china dishes. To each dish add 25 ml of absorbing solution and follow the same analytical procedure given in 4.6.2. A calibration graph (Fig-6) is then drawn in micro grams of NO2 per sample versus absorbance/extintion at 420 nm.

4.7.0 4.7.1

DATA ANALYSIS Sample gas volume in evacuated flask

The sample volume at normal conditions is calculated by the following expression. a) For Evacuated flask _ _ | | | Pf Pi | Tn |----- - ---- | x -| Tf Ti | Pn |_ _|

Vn

= (Vf-Va) x

b) For Grab pipette

Vn

Ps x Tn (Vf-Va) x --------Pn x Ta

Where

Vn Vf Va Pf Pi Ps Ta Tf Ti

.. Dry sample volume at normal conditions, ml .. Volume of flask and valve, ml .. Volume of absorbing solution, 25 ml .. Final absolute pressure of flask, mmHg .. Initial absolute pressure of flask, mmHg .. Absolute stack pressure, mmHg .. Absolute ambient temperature, oK .. Final absolute temperature of flask, oK .. Initial absolute temperature in flask, oK

The calibration curve is used in conjunction with the following expression to determine stack gas concentration.

m x 1000 CNOx,mg/NM3 = ---------Vn Where CNOx .. Concentration of NOx as NO2 (dry basis), mg/NM3

m .. Micro gram of NO2 from the calibration graph

4.8 SUMMARY The NOx field test can be conducted easily by one person. In fact this field test can be run at the same time as other pollutant tests. Thus if a team of 2 or 3 people is conducting an isokinetic particulate matter test, the NOx samples can be run concurrently.

The NOx laboratory procedure is lengthy, requires a number of steps and analysis must be performed by a qualified chemist or laboratory technician. Errors may arise due to improper procedures and deterioration of reagents. The velocity traverse must be run concurrently with this NOx test. Also the pertinent process information for the sampling period is essential. Remember, the NOx concentration data may only be part of what is needed to determine compliance. Regulations are sometimes stated on the basis of pounds per million BTU's input or pounds per ton of process weight.

5.0 OTHER GASEOUS COMPONENTS The sampling and analytical procedures for other frequently encountered gases like Ammonia, Urea (dust), Fluorides are given in Annexures 6 to 8.

ANNEXURE -

DIFFERENT INDUSTRIAL EMISSION STANDARDS FOR GASEOUS POLLUTANTS - PRESCRIBED BY CPCB -----------------------------------1. SULFURIC ACID MANUFACTURE ---------------------------------------------------------------Process Sulphur dioxide Acid mist emission emission ----------------------------------------------------------------Single conversion Single absorption Double conversion Double absorption 10 Kg/tonne of concentrated (100%) acid produced 4 Kg/tonne of 50 mg/Nm3 50 mg/Nm3

concentrated (100%) acid produced. ---------------------------------------------------------------2.0 NITRIC ACID --------------------------------------------------------------Standard for oxides of nitrogen, NOx 3Kg of Nox per tonne of weak acid (before concentration) produced. --------------------------------------------------------------3.0 OIL REFINERIES: ----------------------------------------------------------------Process Emission Limit ----------------------------------------------------------------Standard for sulphur dioxide Distillation (Atmospheric Plus Vacuum) Catalytic Cracker Sulphur Recovery Unit 0.25 Kg/Te of feed* 2.5 Kg/Te of feed

120 Kg/Te of Sulphur in the feed --------------------------------------------------------* Feed indicates the feed for that part of the process under

consideration only.

4.0 COKE OVEN ----------------------------------------------------------------Standard for Carbon monoxide 3.0 kg/T of coke produced

-----------------------------------------------------------------

5.0 POWER GENERATION BOILERS --------------------------------------------------------------------------------------------------------------------------------Boiler size Stack height ----------------------------------------------------------------Standard for Sulphur dioxide control (through stack height) Less than 200 MW 200 MW to less than 500 MW 500 MW and more H = 14 (Q) 0.3 220 meters 275 meters

----------------------------------------------------------------Q = Sulphur Dioxide emission in kg/hr H = Stack height in meters 6.0 STACK HEIGHT FOR COAL FIRED BOILERS --------------------------------------------------------Capacity of Steam generation Stack height

--------------------------------------------------------1. Less than 2 tons/hour (or 2.6 MT/day of coal used) Two and a half times the neighboring building height of 9.0 m whichever is more 12.0 m

2.

More than 2 tons/hr to 5 tons/ hour (or 2.6 MT/day to 6.5 MT/day of coal used)

3.

More than 5 tons/hr to 10 tons/ 15.0 m hour (or 6.5 MT/day to 13 MT/ day of coal used)

4.

More than 10 tons/hr to 15 tons 18.0 m /hour(or 13 MT/day to 19.5 MT/day of coal used)

----------------------------------------------------------------Contd ....

--------------------------------------------------------Capacity of Steam generation Stack height

--------------------------------------------------------5. More than 15 tons/hr or 20 tons 21.0 m /hour (or 19.5 MT day to 26.0 MT/day of coal used) More than 20 tons/hr to 25 tons/hour (or 26 MT/day of coal used) More than 25 tons/hr to 30 tons/hour (or 32.5 MT day 39 MT/day of coal used) More than 30 tons/hour (or than 39 MT/day of coal used) 24.0 m

6.

7.

27.0 m

8.

30.0 m or using the formula H=14) where H=minimum stack height required in metres. Q is sulfur dioxide emissions in kg/hr, whichever is more)

--------------------------------------------------------

ANNEXURE - 2

MODEL PROBLEM FOR SULFUR DIOXIDE AND SULFUR TRIOXIDE ANALYSIS AND ESTIMATION -----------------------------------------------------------1.0 A Fertiliser plant has a 100 TPD sulfuric acid plant producing concentrated sulfuric acid (98%) through DCDA process. Source emission monitoring was conducted at the stack located at the end of the second absorption column. The flow rate of the gases was measured to be 12,500 NM3/hr at 52oC following the EPA standards methods 1 to 4. 1.1 Sulfur trioxide and sulfur dioxide samples were collected and analysed by EPA standard method 6. The data collected are as follows: Volume of the gas sample DGM temperature Vacuum at DGM Volume of the absorption media for SO3 estimation Volume of the absorption media for SO2 estimation collected = 50 lit = 35oC = 14 mmHg = 98 ml = 192 ml

Volume of the aliquot for both SO2 & SO3 analysis = 20 ml Ba(ClO4)2 consumption by SO2 aliquot Ba(ClO4)2 consumption by SO3 aliquot Ba(ClO4)2 consumption by blank Ba(ClO4)2 normality Atmospheric pressure = 9.8 ml = 3.5 ml = 1.2 ml = 0.00987N = 740 mmHg

Calculate the concentrations of SO2 and SO3 in the emissions and also check whether the emissions comply with emission regulations.

1.2 The acid mist sample in the emissions was also collected following the method EPA-8 and the collected data are as follows: Volume of the gas sample collected across the duct through isokinetic sampling = 345 lit DGM temperature Average vacuum recorded in the DGM Volume of the sample after thible wash Volume of the aliquot for analysis Ba(ClO4)2 consumption by the aliquot Ba(ClO4)2 consumption by blank Ba(ClO4)2 normality = 35oC = 18 mmHg = 250 ml = 50 ml = 4.6ml = 1.2 ml = 0.00987N

Calculate the concentrations of acid mist in the emissions and also check whether the emissions comply with emission regulations.

2.0 2.1

SOLUTIONS: Estimation of SO3 Volume of the gas sample collected Under normal conditions, Qn = 50 lit

Qn

0.05 x 726 x 298 = ----------------760 x 308

0.046 NM3

Concentration of sulfur trioxide is calculated by (A-B) x V x N x 40 CSO3, mg/NM3 = --------------------v x Qn

. . . (2)

Where A .. Volume of the Ba(ClO4)2 consumed by the sample aliquot,ml B .. Volume of the Ba(ClO4)2 consumed by the blank,ml v .. Volume of the aliquot,ml V .. Volume of the absorbing solution,ml N .. Normality of Ba(ClO4)2 48 .. Equivalent weight of SO3, gm/gm mole

(3.5-1.2) x 98 x 0.00987 x 40 CSO3, mg/NM3 = -------------------------------20 x 0.046 = 96.7 or 29.6 ppm

SO3 emission load = SO3 conc. x emission flow rate = 96.7 mg/NM3 x 12,500 NM3/hr = 1.21 kg/Hr H2SO4 manufacture = 100 TPD (98%) = 98 TPD (100%) = 4.08 T/Hr 1.21 SO3 emission factor = ---- = 0.3 kg/T of 100% acid 4.08

2.2 Estimation of SO2

Concentration of sulfur dioxide is calculated by

(A-B) x V x N x 32 CSO2, mg/NM3 = --------------------v x Qn

. . . (2)

Where A .. Volume of the Ba(ClO4)2 consumed by the sample aliquot,ml B .. Volume of the Ba(ClO4)2 consumed by the blank,ml v .. Volume of the aliquot,ml V .. Volume of the absorbing solution,ml N .. Normality of Ba(ClO4)2 32 .. Equivalent weight of SO2, gm/gm mole

(9.8-1.2) x 192 x 0.00987 x 32 CSO2, mg/NM3 = -------------------------------20 x 0.046 = 567 or 434 ppm

SO2 emission load = SO2 conc. x emission flow rate = 567 mg/NM3 x 12,500 NM3/hr = 7.09 kg/Hr 7.09 SO2 emission factor = ---- = 1.74 kg/T of 100% acid 4.08 SO2 emissions are satisfying the CPCB standards of 4kg of SO2 per T of 100% sulfuric acid produced.

2.3

Estimation of Acid mist

Volume of the gas sample collected Under normal conditions, Qn

= 345 lit

Qn

0.345 x 722 x 298 = ----------------- = 760 x 308

0.317 NM3

Concentration of sulfuric acid mist is calculated by

(A-B) x V x N x 48 C H2SO4 mist, mg/NM3 = --------------------v x Qn

Where A .. Volume of the Ba(ClO4)2 consumed by the sample aliquot,ml B .. Volume of the Ba(ClO4)2 consumed by the blank,ml v .. Volume of the aliquot,ml V .. Volume of the absorbing solution,ml N .. Normality of Ba(ClO4)2 48 .. Equivalent weight of H2SO4, gm/gm mole

(4.6-1.2) x 250 x 0.00987 x 48 CSO2, mg/NM3 = -------------------------------50 x 0.317 = 25.4

ANNEXURE - 3

MODEL PROBLEM FOR NITROGEN OXIDES ANALYSIS AND ESTIMATION -----------------------------------------------------------A) PROBLEM A source sampling test was conducted on a 200 KVA diesel generator set. The flue gas analysis reveals 13% - CO2, 1.0% - CO and 5% - O2. Flue gas temperature measured to be 370oC. The samples for nitrogen oxide analysis were collected in an evacuated flask. The collected samples were analysed by Phenol Disulfonic Acid method following the standard EPA - 7 method. The analysis data are as follows Volume of the evacuated flask,ml Absolute flask pressure before sampling,mmHg Absolute stack pressure,mmHg Atmospheric pressure,mmHg Ambient temperature,oC Volume of the absorbing solution,ml Dilution ratio Extintion reading Corresponding NO2 value from calibration graph, ug NO2 quantity considering dilution, ug : 960 : 70 : 735 : 740 : 35 : 25 : 1:2 : 0.348 : 350 : 700

Calculate the concentration of NOx in the DG set exhaust gases in mg/NM3. B) SOLUTION Concentration of the NOx using evacuated flask method and with the given data can be calculated by using the following equation

Vn

= (Vf-Va) x

_ _ | | | Pf Pi | Tn |----- - ---- | x -| Tf Ti | Pn |_ _|

m x 1000 CNOx,mg/NM3 = ---------Vn

Where Vn Vf Va Pf Pi Ps Ta Tf Ti .. Dry sample volume at normal conditions, ml .. Volume of flask and valve, ml .. Volume of absorbing solution, ml .. Final absolute pressure of flask, mmHg .. Initial absolute pressure of flask, mmHg .. Absolute stack pressure, mmHg .. Absolute ambient temperature, oK .. Final absolute temperature of flask, oK .. Initial absolute temperature in flask, oK mg/NM3

CNOx .. Concentration of NOx as NO2 (dry basis),

m .. Micro gram of NO2 from the calibration graph _ _ | | | 735 70 | 298 = (960-25) x |----- - -----| x --| 308 308 | 760 |_ _| = 792

Vn

700 x 1000 CNOx,mg/NM3 = ---------Vn = 884

----------------------------------------------------------------S No. C O N T E N T S Page No.

----------------------------------------------------------------1.0 2.0 3.0 4.0 5.0 Introduction . . . . . . . . . . . . . . . 1 1 10 12 21

Sulfur Dioxide and sulfur trioxide (EPA - 6) Acid mist concentration (EPA - 8) Nitrogen oxides estimation(EPA -7) Other gases

. . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

ANNEXURES 1 2 2A 3 3A 4 5 6 7 8 Emission standards for gaseous pollutants CPCB . . . . Model problem and calculation for analysis of SO2 & SO3 . . . . Computerised data sheets for SO2 analysis . . . Model problem and calculation for analysis of NOx . . . . Computerised data sheets for NOx analysis . . . Sampling and analysis of ammonia emissions. . . Sampling and analysis of Urea emissions . . .

22 25 30 31 33 34 41 46 51 58

Sampling and analysis of Fluoride emissions . . Sampling and analysis of H2S and CS2 References . . . . .

. . . . . . . . . . . . . . .

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* * * ANNEXURE - 7 SAMPLING AND ANALYSIS HYDROGEN SULFIDE AND CARBON DISULFIDE ___________________________________________________________ 1.0 PRINCIPLE:

The gas containing hydrogen sulfide and carbon disulfide is initially passed through cadmium chloride solution. Hydrogen sulfide reacts with cadmium chloride and precipitated as cadmium sulfide which is quantitatively estimated by iodometric titration. Subsequently the gas containing only carbon disulfide is passed through potassium hydroxide solution where CS2 froms potassium xanthate which is estimated quantitatively by iodometric tritration.

2.0 2.1

SAMPLING EQUIPMENT AND THE CHEMICALS: EQUIPMENT FOR SAMPLE COLLECTION:

Sampling probe: Sampling probe made of corrosion resistant material like quartz or stainless steel Quartz wool filter: About 10mm - 15 mm dia and 150 mm long heated quartz wool filter Five Glass impingers: Mid-jet impingers of 250 ml capacity Ice bath: Leak proof ice bath to accomodate five impingers Suction pump:

To facilitate 60 lit/hr flow rate. Gas volume meter: Suitable for 60 lit/hr flow rate.

Thermometer: To measure the gas temperature at the Gas volume meter. Barometer: To measure the atmospheric pressure at the sampling site. 2.2 GLASS WARE FOR ANALYSIS:

Burette: 25ml capacity with 0.05 ml minimum graduations - 2 Nos Erlenmeyer Flask: 300 ml capacity, Wide mouth with ground stopper joint.- 6 Nos

2.3

CHEMICALS:

All chemicals should be of Analytical grade should be used.

Cadmium chloride solution: 25g of cadmium chloride is dissolved with 900 ml of double distilled water in 1.0 lit volumetric flask. Add 20 ml of 0.5N NaoH and make it upto 1.0 lit. Iodine solution: 0.1N and 0.01N Iodine solutions Sodium thiosulfate solution: 0.1N Sodium thiosulfate solution.

Acetic acid: 100 ml of acetic acid is diluted to 1000 ml with double distilled water in a volumetric flask.

Starch solution: distilled water.

1.0g of starch dissolved in 100ml of double

Potassium Hydroxide: 5 gm of KOH dissolved in 2-3 ml of distilled water, cooled in ice bath and make it to 100 ml with absolute alcohol/methy alcohol. Phenolpthaline indicator:

3.0

SAMPLING TRAIN

The sampling train is similar to that of EPA -5 for particulate sampling except for the dust collecting thimble holder which is replaced by a set of midget impingers for the absorption of the gaseous components as given in Fig - A. 3.1 Sampling probe: A short sampling probe Pyrex or quartz is used to prevent condensation prior to sample collection. Quartz of Pyrex glass wool is placed in the entry of the probe to prevent particulate matter/water droplets from entering the impingers. Alternatively an additional midget bubbler stuffed with glass wool is placed at the end of the sampling probe along with the gas absorption equipment. 3.2 Absorption equipment: The sample collector consists of four midget impingers placed in an ice bath. The first two midget impingers contain 100 ml of calcium chloride solution. This removes the H2S. To ensure efficient absorption a second impinger with 100 CaCl2 is placed. Two impingers with 100 ml each of alcoholic potassium hydroxide are placed in series to absorb carbon disulfide. A fifth impinger in series is preferred to trap the liquid droplets. It is essential to keep the the implinger set in ice/chilled water bath to prevent the escape of CS2 while sampling. 3.3 Flow metering: Finally the gases are passed through silica gel drying column to protect the Dry Gas Meter which follow it.

To achieve the optimum absorption efficiency, the sampling flow rate has to be set at a minimum constant flow rate of 2 lpm with the help of rota meter and the needle valve. 3.4 Vacuum pump: Since the sampling flow rates are very low the pressure drop across the sampling train is around 10 to 15 mmHg and hence a small capacity vacuum pump is enough for such purpose.

4.0 4.1

SAMPLING AND ANALYTICAL PROCEDURE: SAMPLING:

The first two impingers are filled with 100ml each of cadmium chloride solution. The following two impingers are filled with 100 ml each of potassium hydroxide. The fifth imger is kept empty to trap any carry over moisture droplets. Gas sample is drawn through the probe and the quartz filter and bubbled through the impingers. A sampling flow rate of 1.0 lpm is maintained. If the sample time is limited then the flow rate has to be increased accordingly. Generally the sample volumes of 30 to 50 lit are being collected to get the repersentative data. However it should be ensured that the absorption is completed in the first impinger itself and the quantity of gas component in the second impinger is negligible.

Cadmium chloride is white turbid solution and when it reacts with H2S it becomes yellow precipitate. The strength of the color depends on the amount of cadmium sulfide forms and care should be taken that the sampling should be stopped before the solution the second impinger turns pale yellow. The reaction of CS2 with KOH can also be observed by changing its color to pale yellow with high concentrations. care should be

taken that the second following impinger should not change its color.

4.2

ANALYSIS: Hydrogen Sulfide, H2S:

4.2.1

The solution from the impingers are transfered independently in to two iodometric flasks. Add 20 to 50ml of 0.1N iodine depending on the quantity of CdS in the solution. Add 25 ml of 10% acetic acid, close the stoppers and keep the flasks in dark for about 10 to 15 mts. Titrate the solution with standardised 0.1N Na2S2O3 till pale yellow and add two drops of stacrch to get dark blue color. Continue the titration till it becomes colorless. Repeat the titration for blank starting with cadmium chloride solution and following the same analytical procedure parallely. Record both the sample and blank readings. 4.2.2 Carbon Disulfide:

Transfer the contents in two 250ml Erlenmeyer flask and cool the sample in chilled water for 10 to 15 mts. Neutralise the solution with 10% acetic acid using phenolpthaline as indicator. Add starch and titrate with 0.01N iodine solution till the buff color end point appears. Repeat the procedure with blank.

5.0

CALCULATIONS:

5.1

HYDROGEN SULFIDE (H2S) Concentration of H2S in the gas sampled is calculated by the

following equation (Yo - Y) x 1.702 ----------------Vn

C H2S

Qn

Qm x Pm x Tn -------------Pn x Tm

Where C H2S Yo Y Qn Qm Pn, Tn .. .. .. .. .. .. Concentration of H2S in the sample gas, mg/NM3 Consumption of 0.1N sodium thiosufate by the blank Consumption of 0.1N sodium thiosufate by the sample Sample gas volume at normal conditions,NM3 (25oC,760mmHg) Sample gas volume, M3 Pressure and temperature under normal condition (25oC,760mmHg) mg of H2S per ml

1.702 5.2

..

CARBON DISULFIDE (CS2)

Concentration of CS2 in the gas sampled is calculated by the following equation (P - Po) x 0.38 ----------------Qn Qm x Pm x Tn -------------Pn x Tm

C CS2

Qn

Where C CS2 Po P .. .. .. Concentration of H2S in the sample gas, mg/NM3 Consumption of 0.1N Iodine by the blank Consumption of 0.1N Iodine by the sample

Qn Qm Pn, Tn

.. .. ..

Sample gas volume at normal conditions,NM3 (25oC,760mmHg) Sample gas volume, M3 Pressure and temperature under normal condition (25oC,760mmHg) mg of CS2 per ml

0.38

..

6.0

RANGE OF APPLICABILITY: Minimum quantity .. 0.05 mg

Minimum concentration .. 1.0 mg/Nm3 ( 50 L sample volume) Standard deviation .. 0.5 mg/NM3 at 25 mg/NM3

ANNEXURE - 9 REFERENCES 1. Air Pollution - Vol - III, 3rd edition, A.C.Stern, Academic Press, New York 2. Emission regulations - Part-III, Comprehensive Industry Document Series, COUINDS/20/1984-85 - CPCB, New Delhi 3. EPA-Code of Federal Regulations, Title-40: Standards of Performance for new Stationary Sources - reference methods 4. Industrial source sampling, D.L. Brenchley et.al, Ann arbor Publishers, Inc., Michigan 5. Hand book of air pollution analysis, II edition Roy.M.Harison et.al., University Press, Cambridge.

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