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OAR Box 1828 

Prepped by Ollie Stewart 

Document Number: 

293) IV-A-3 

Docket Number: 

A-83-27 

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Third Interim Report: Continuous Sulfur Dioxide 

Monitoring at Steam Generators 

Vol urns I: Summary of Results 

March 1979 

TED STATES ENVIRONMENTAL PROTECTION AGENCY 

Office of Air and Waste Management 

Office of Air Quality Planning and Standards 

Emission Measurement Branch 

Research Triangle Park. North Carolina 
P.3 

EMB ReDort Mo. 77SPP23C 

March 15, 1979 

AIR POLLUTION EMISSION TEST 

Third Interim Report 

Continuous Sulfur Dioxide Monitorinq at 

Steam Generators 

Volume I - Summary of Results 

W. E. Kelly and P. R. Westlin 

Emission Measurement Branch 

C. B. Sedman 

Industrial Studies Branch 

United States Environmental Protection Agency 

Office of Air Ouality Planning and Standards 

Emission Standards and Engineering Division 

Research Trianale Park, North Carolina 27711 
P.4 

TABLE OF CONTENTS 

List of Fiqures 

List of Tables 

Summary of Results 

Sections 

Page No. 

i 

ii 

1 

I. INTRODUCTION AND DESCRIPTION OF TEST SITES 2 

A. Introduction 2 

B. Description of Test Sites 3 

1. Shawnee 1OA and 10B FGD Prototypes, Tennessee Valley Authority, 

Paducah, Kentucky 3 

2. Lawrence Unit No. 4, Kansas Power and Light Company, 

Lawrence, Kansas 3 

II. DATA GATHERING AND REDUCTION 7 

A. Data Gathering Systems 7 

1. Shawnee 10A and 10B FGD Prototypes, Tennessee Valley Authority, 

Paducah, Kentucky 7 

2. Lawrence Unit No. 4, Kansas Power and Li ant Company, 

Lawrence, Kansas 9 

8. Data Reduction Procedures 11 

III. OATA ANALYSIS 15 

A. Data Calculation Assumptions 15 

B. Data Availability 15 

C. Statistical Analyses 17 

IV. RECOMMENDATIONS AND CONCLUSIONS 24 
LIST OF FIGURES 

P.5 

Figure 

I-l 

1-2 

I I-l 

11-2 

III-l 

III-2 

111-3 

III-4 

III-5 

III-6 

Shawnee 10A and lOB Scrubber Gas Flow 

Lawrence No. 4 Scrubber Gas Flow 

Instrument System Schematic, Shawnee 10A and 10B 

Instrument System Schematic, Lawrence No. 4 

Probability vs. Log Inlet SO- i - Shawnee Venturi 

Probability vs. Loo Outlet SOp - Shawnee Venturi 

Probability Log Percent SOp Emitted - Shawnee Venturi 

Probability vs. Log Inlet SO-. - Lawrence No. 4 

Probability vs. Log Outlet SOp - Lawrence No. 4 

Probability vs. Log Percent SOp Emitted - Lawrence No. 4 

Page No. 

4 

5 

8 

10 

18 

19 

20 

21 

22 

23 
P.6 

LIST OF TABLES 

Table Page 

II-1 Analyzer Soecifications for Lawrence No. 4 ll 

III-l Categorization of Oata 15 

n 
P.7 

TABLE OF CONTENTS 

List of Figures 

List of Tables 

Summary of Results 

Sections 

I. INTRODUCTION AND DESCRIPTION OF TEST SITES 

A. Introduction 

B. Description of Test Sites 

Page No. 

i 

ii 

1 

2 

2 

3 

1. Shawnee 10A and 10B FGD Prototypes, Tennessee Valley Authority, 

Paducah, Kentucky 3 

2. Lawrence Unit No. 4, Kansas Power and Light Company, 

Lawrence, Kansas 3 

II. DATA GATHERING AND REDUCTION 7 

A. Data Gathering Systems 7 

1. Shawnee 1OA and 10B FGD Prototypes, Tennessee Valley Authority, 

Paducah, Kentucky 7 

2. Lawrence Unit No. 4, Kansas Power and Lioht Company, 

Lawrence, Kansas 9 

8. Data Reduction Procedures 11 

III. DATA ANALYSIS 15 

A. Data Calculation Assumptions 15 

B. Data Availability 15 

C. Statistical Analyses 17 

IV. RECOMMENDATIONS AND CONCLUSIONS 24 
LIST OF FIGURES 

P.8 

Figure 

• 1 

[-2 

[-1 

[-2 

:i-i 

:i-2 

:i-3 

:i-4 

1-5 

:n-6 

Shawnee lOA and lOB Scrubber Gas Flow 

Lawrence No. 4 Scrubber Gas Flow 

Instrument System Schematic, Shawnee 10A and 10B 

Instrument System Schematic, Lawrence No. 4 

Probability vs. Loq Inlet SO- i - Shawnee Venturi 

Probability vs. Loo Outlet S0-

Probability Log Percent SO- 'Emitted 

- Shawnee Venturi 

Shawnee Venturi 

Probability vs. Log Inlet SO- - Lawrence No. 4 

Probability vs. Log Outlet SO- - Lawrence No. 4 

Probability vs. Log Percent SO- Emitted - Lawrence No. 4 

Page No. 

4 

5 

8 

10 

18 

19 

20 

21 

22 

23 
P.9 

LIST OF TABLES 

Table Page 

II-l Analyzer Soecifications for Lawrence No. 4 n 

III-l Categorization of Oata 16 

ii 
P.10 

SUMMARY OF RESULTS 

SO- monitoring at the Shawnee FGD test facility and Lawrence No. 4 

steam generator of Kansas Power and Light Company was performed by EPA with 

emphasis upon obtaining 30 continuous days of SO- data, using monitors certified 

according to procedures in the October 6, 1975, Federal Register. 

At the Shawnee site, a venturi scrubber using limestone with adipic acid 

additive was monitored for 49 continuous days with the existing on-site 

SOp monitoring system. Due to some monitoring problems, 31 days data were 

obtained (63 percent reliability) which showed average SO- emissions of 

0.22 lb/10 Btu and SOp emission reduction of 96.1 percent. 

EPA used a mobile sampling van to obtain SO- data from the Lawrence No. 4 

FGD unit, a venturi scrubber with limestone applied to combustion of 

low-sulfur coal. For the 22 days of continuous scrubber operation (with two 

periods of interruption due to sampling pump failures), the SO- monitors were 

86 percent reliable, measuring average SO- emissions of 0.03 lb/10 Btu and 

96.6 Dercent SO- removal for 22 days. The relative variability in outlet 

emissions from both sources was significantly higher than for previous tests, 

due to the low absolute values of the data. 
P.11 

I INTRODUCTION AND DESCRIPTION OF TEST SITES 

A. Introduction 

This report summarizes the results of the latest EPA efforts to monitor 

SOp emissions and SOp removal efficiencies from coal-fired utility steam 

generators using flue gas desulfurization (FGD) systems. Previous reports 

77SPP23A and B described activities at seven FGD sites on boilers firing 

high (3-5 percent) sulfur coals using lime/limestone scrubbers. In the 

systems described below, results are presented for SO- monitoring at a 

low-sulfur coal-fired boiler using a limestone FGD system and a high-sulfur 

coal boiler using adipic acid injection into a limestone FGD system. All 

instrumentation and orocedures followed have been previously discussed in 

the earlier reports. A noteworthy exception herein was the mobile van equipped 

with fluorescence analyzers for sulfur dioxide and polarographic/paramegnetic 

analyzers for oxygen at the Lawrence test site, described in Section II A of 

this report. 

At both installations, SO- and Op concentrations were measured upstream 

and downstream of the FGD system using continuous instrumental monitors. Copies 

of boiler operation logs and FGD system operation logs were obtained to 

document process operating conditions during the monitoring periods. 

As in all cases, the instruments used to generate data have been subjected 

to the appropriate test procedures (Federal Register, Vol. 40:194, 

October 6, 1975) to assure accuracy of all data reported herein. 
P.12 

B. Description of Test Sites 

1. Shawnee FGD Prototypes, Tennessee Valley Authority 

The Shawnee Power Station, operated by the Tennessee Valley Authority 

(TVA), is a coal-fired steam generation station having 10 turbines, each 

served by a boiler and stack. A portion of the exhaust gases from one of 

these stacks is directed for use with three pilot plant scale wet scrubbers 

systems - a venturi with a spray tower after absorber, a turbulent contact 

absorber (TCA), and a marble bed absorber. Testing was performed on the 

venturi/spray tower using limestone enhanced with adipic acid and the TCA using 

lime only. This report describes the test and results for the venturi/spray 

adipic acid enhanced limestone system. 

The venturi system was manufactured by Chemical Construction Company 

in the late 1960's and contains an adjustable throat which permits control 

and variation of pressure drop. No design performance data are available. 

Figure I-l is the process flow diagram for the Shawnee venturi system. 

For this test, limestone and adipic ad d were added to the scrubber effluent 

hold tank with adipic acid concentrations maintained at 1500 parts per 

million volume during the entire test period. 

2. Lawrence Unit No. 4, Kansas Power and Light Company 

The Lawrence No. 4 steam generating unit is rated at 125 megawatt 

electrical output and burns low-sulfur Wyoming coal with an average heating 

value of 10,000 Btu/hr, sulfur content of 0.5 percent and ash content of 

9.8 percent. The FGD system consists of two 50 percent capacity scrubber 

modules of a Combustion Engineering - Bed Scrubber/Spray Tower two-stage 

system as shown in Figure 1-2. Pulverized limestone slurry contacts the 
1 FUEL OIL >-»f"REHEATER 

|FLUE GAS^O-®- , 

VENTURI 

SCRUBBER 

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SAMPLE POINTS 

OGAS COMPOSITION 

®PARTICULATE COMPOSITION & LOAOING 

©SLURRY OR SOLIDS COMPOSITION 

VACUUM 

FILTER 

— GAS STREAM 

— LIQUOR STREAM 

Figure I-l 

Tennessee Valley Authority, Shawnee No. IU Prototype Unit: 

General Process Diagram. 

STACK 

0 

DISCHARGE 

SETTLING I'O.'II) 
FLUE GAS 

> >> > >)) ) 

SPRAY TOWER 

• EFFLUENT LINE 

Figure 1-2 Kansas Power and Light, Lawrence No. 4 Operational FGD System: 

Simplified Flow Diagram. 

• •;:»= --••! ! <i iA.-K'i.Wvri'; 
P.15 

flue gas in both the rod scrubbers and spray tower. Overall SO- removal 

is designed for a minumum 73 percent. A detailed description of this system 

may be found in EPA 600/7-78-058b pp. 255-276, "Proceedings of the Symposium 

on Flue Gas Desulfurization, November 1977. 
P.16 

II DATA GATHERING AND REDUCTION 

A. Data Gathering Systems 

1. Shawnee FGD Prototypes, Tennessee Valley Authority, Paducah, Kentucky 

A schematic diagram of the monitoring system used at each monitoring 

location at Shawnee is shown in Figure III-l. The sulfur dioxide (SOp) 

instrument at each location is a DuPont 460 analyzer. The oxygen (0-) analyzer 

is a Thermox model WDG 3 instrument. The ranges of the scrubber inlet SOp 

analyzers are set at 0-4000 ppm SOp and the ranges of the two scrubber outlet 

SOp analyzers are 0-1000 ppm. The ranges of 0- analyzer are all set at 

0-10 percent 0-. The SO- and 0- probes tips are located at the stack centers 

with the 0- rpobe approximately one stack diameter upstream of the SOp probe 

at each location. The analyzers operating on approximately 8-minute cycles 

during which stack gas concentration measurements are made continuously except 

for an automatic 1-minute backflush period. Concentration measurements are 

recorded continuously on four strip chart recorders located in the scrubber 

control room. 

The moisture content correction for the SOp gas measurements was determined 

from the temperature measurement in the sample gas stream immediately following 

the knock-out trap in the analyzer case. This gas was assumed saturated at 

this temperature. The moisture content correction for the 0- gas measurements 

was the stack moisture content as the 0- analyzers measured a wet gas stream. 

Mention of a specific company or product name does not constitute endorsement 

by the Environmental Protection Agency. 
OO 

S02 Probe 

tzz> 

02 Probe 

-<-

Heated Teflon line 

- ^ 

Calibration gas 

valve 

0? Recorder S( uu 

P Recon'er 

DuPont analyzer 

-r -=rKnock-out 

trap 

Figure 11— 1 Instrument System Schematic, Shawnee Power Station 
P.18 

2. Lawrence Unit No. 4, Kansas Power and Light Company, Lawrence, Kansas 

The monitoring system used at Lawrence No. 4 consisted of an extraction/ 

conditioning module and a mobile laboratory which housed the analyzers. Thermo 

Electron Model 40 pulsed fluorescence analyzers were utilized to monitor sulfur 

dioxide at both the inlet and outlet of the south scrubber. A Beckman Model 742 

polarographic analyzer was used to monitor the inlet oxygen concentration while 

a MSA paramagnetic analyzer was utilized to monitor outlet concentration of 

oxygen. 

Figure I1-2 contains a schematic diagram of the sample extraction/ 

conditioning module. Briefly, the system consists of a heated orobe with a 

3/4 inch nozzle oriented away from the gas flow, a heated filter box/pump 

box assembly, a refrigeration cooler and finally a distribution panel to 

readily enable the sampling of calibration or samole streams. All connecting 

lines from the probe to the refrigeration cooler consisted of 1/2 inch 

O.D. Teflon tubing was used. A 0-15 psi back pressure regulator was placed at 

the end of the exhaust vent line to cause a fraction of the gas from the source 

to be transported through the analyzers. 

Data acquisition was accomplished using an Accurex Auto Data Nine data 

acquisition system with a 24-channel Esterline Angus multipoint recorder as 

a backup in dase of Auto Data Nine failure. 

The extraction system was operated at a constant flow rate of approximately 

1.5 ft/min with a constant back pressure of 5 osi. All heat traced lines 

and heated boxes were operated at temperatures ranaing from 130°C to 200°C. 

3 Sample flows to the oxygen analyzers were maintained at 1.6 ft /hr while 
SuMnllug fore 

'==== = ==J9_ 

si«i> riuw 

Figure 11-2 Schematic of Monitoring System of Lawrence No. 4 
P.20 

those for the SO- analyzers were not visually maintained as the analyzers 

contained individual sampling pumps which controlled the analyzer sample demand, 

All analyzers were calibrated daily at approximately 0900 with a zero, 

midscale and 90 Dercent of full-scale range standards.- Data was collected 

instantaneously at five minute intervals by the Auto Data Nine. . These data 

printouts also contained secondary parameters such as line temperatures, 

cooler temperatures, etc. 

Prior to the initiation of monitoring, a profile was conducted at both 

the inlet and outlet to the scrubber in order to ensure a homogeneous gas 

stream. At the completion of this exercise, the probes were oriented as close 

to the center of the duct as possible. 

The invidivual analyzers were operated on the ranges shown in Table 1 and 

calibrated with the type of standard listed. 

TABLE II-l ANALYZER SPECIFICATIONS 

Analyzer Location Range Calibration Standard 

S02/air 

S02/air 

02/N2 

02/N2 

The types of data that were collected for reduction purposes were: 

inlet S02 strip chart (2 Inlets) 

inlet 02 strip chart (2 inlets) 

outlet S02 strip chart (2 outlets) 

outlet 02 strip chart (2 outlets) 

TECO Model 40 

TEC0 Model 40 

Beckman Model 742 

MSA Paramagnetic. 

Analyzer 

B. Data Reduction 

Inlet 

Outlet 

Inlet 

Outlet 

Procedures 

0-1000 ppm 

0-100 ppm 

0-10% 

0-1055 

11 
P.21 

scrubber logs (including boiler load and coal feed rate) 

instrument logs 

instrument calibration data sheets 

manual test results 

The data were first logged in as received and then were reviewed for 

possible data gaps. The charts were then transcribed to a tabular format 

using a strip chart data digitizer. The tabular data were then processed 

through a manual keypunch operation so that appropriate scale factors, moisture 

values, process data, and descriptive comments could be included prior to data 

listing. The punched cards were then processed by computer to obtain a data 

listing and calculated results for each 15 minute data point. The data listings 

were reviewed by the EPA contractor for keypunch or other transcription errors. 

The scrubber and instrument logs were reviewed so that periods of boiler outage, 

scrubber outage, bypass, startup or shutdown could be properly identified and 

coded so that these data would not be included in the calculation of averages 

and summaries. 

After data editing was completed, average summaries were prepared. 

Averages based on the 15-minute data were prepared for consecutive 1-hour, 

3-hour, 8-hour, and 24-hour intervals. In order to calculate an average 

result for a single interval, it was specified that at least 75 percent of 

the 15-minute data points be available for that interval. For example, an 

8-hour average could only be calculated when 24 of the possible 32 15-minute 

data points were available. When less than 75 percent of the data were 

available for an interval, an average was not calculated and blanks were 

entered in the summary printouts. 

After each 30 days of average interval data, a statistical summary 

was prepared to determine the following parameters for the average. 

12 
P.22 

mean 

average deviation 

minimum 

percent standard deviation 

standard deviation 

maximum 

range 

These parameters were calculated assuming the data were normally distributed. 

The calculation procedures used to convert the analyzer outputs for 

sulfur dioxide and oxygen concentrations to mass emission factors are given 

in 40 CFR 60 Subpart D. This procedure is known as the F-factor approach and 

is outlined below: 

F . CFK v 20.9 L

 " T^M"

 x 20.9-0-

Where E = 

C = 

F = 

K •• 

°2 = 

M = 

Emission factor - lb/million Btu 

S 02 concentration - ppmv, wet basis 

Stoichiometric conversion factor, 9820 dscf/million Btu for 

subbituminous coal 

,-7 Conversion factor, 1.659 x 10 Ib/dscf per ppmv 

Oxygen concentration, percent by volume as measured 

Moisture fraction as measured (for dried samples, M»0) 

The sulfur dioxide and oxygen concentration results were obtained by multiplying 

the strip chart readings as a percent of scale by the appropriate calibration 

factor. 

13 
P.23 

The emission factor was calculated for each FGD system inlet and outlet test 

point. The sulfur dioxide removal efficiency for a module is calculated by: 

Efficiency =

 Ein ^ out x 100 percent 

When more than one inlet and/or outlet test point was monitored, the total system 

emission factors and sulfur dioxide removal efficiencies were calculated by a 

weighted average procedure. The equation for this calculation for total system 

efficiency is given by: 

EFF total = EFFA (F"A) + EFFg(Fg) 

Where, 

EFFtQ .j = total system efficiency 

EFF. » efficiency of module or module set A 

F. = fraction of gas flow through module or module set A 

EFF- » efficiency of module or module set B 

FB = fraction of gas flow through module or module set B 

14 
III. DATA ANALYSIS 

A. Data Calculation Assumptions 

In previous SOp monitoring reports, several assumptions were made due to 

direct oxygen or moisture readings being unavailable, which led to a maximum 

error level due to the assumptions of 3 percent in emissions and 0.5 percent 

in percent removal efficiency. 

For the data to be described, no assumptions were made. 

B. Data Availability 

Table III-l shows the data gathering breakdown for the two sites. The 

total days sampling time was ascertained, then the boiler and scrubber down time 

was subtracted to yield the net days availabile for scrubber perfonnance data. 

Data for each one-hour period was compiled and 24-hour periods characterized 

as full data periods, i.e., when the boiler/scrubber system was operable 

18 hours or more and 18 hours or more of monitor data was obtained within a 

calendar day. 

As shown in Table III-l the percentage data availability ranged from 

63.3 percent total days at Shawnee to 84.6 percent at Lawrence No. 4 for 

overall efficiency, where both inlet and outlet data were available. 

Comparison of performance at the Shawnee site to design is not possible 

since the design S02 removal for adipic acid injection is not known due to 

the limited operating experience. What is significant is that the limestone/ 

adipic acid venturi system achieved 96.1 oercent S02 removal on identical flue 

gas to that which the lime-TCA FGD system previously reported an 88.6 percent 

SOp removal. 

15 
TABLE III- l CATEGORIZATION OF DATA 

Total Days 

Boiler Down 

Scrubber Down 

cr> 

Net 

Full Data Days 

% Data Available 

Shawnee Venturi FGD 

49 

0 

0 

49 

31 

63.3 

Lawrence FGD 

37 

0 

11 

26 

22 

84.6 
Comparison of the Lawrence performance to design SOp removal is 

interesting in that the 73 percent design figure was easily exceeded by the 

96.6 percent figure demonstrated during the 22 days testing. This is because 

a slight overdesign of a low sulfur FGD system may show significant additional 

SOp removal when compared to similar overdesign of a high sulfur FGD 

application. Another way of stating this is that removal of an extra 50 ppm 

is very significant when there is only 60 ppm remaining, as compared to 

when 600 ppm remain. This ease of scrubbing low sulfur coals was discussed 

in EPA 600/7-78-030 b, March 1978, by Bechtel Corporation. 

C. Statistical Analyses 

Figures III-l, JII-2, and III-3 graphically illustrate FGD performance at 

the Shawnee venturi site using limestone with adipic acid additive. Figure III-l 

shows inlet S02 loadings average 5.6 percent lb/10 Btu with a geometric 

dispersion (GD) of 1.070. Figure III-2 shows outlet S02 emissions averaging 

0.22 lb/10 Btu with a GD of 1.518. Percent S02 emitted averaged 3.9 percent 

(96.1 percent S02 removal) for the 31 day period with a GD of 1.427. 

Figures II1-4 through II1-6 show the performance of the Lawrence venturispray FGD using limestone slurry. Figure III-4 shows average inlet S02 

loadings of 1.02 lb/10 Btu, while Figure III-5 shows average outlet SOp 

emissions of 0.03 lb/10 Btu. Geometric dispersions are 1.122 and 2.342 for 

inlet and outlet respectively. In Figure III-6 the percent S02 emitted is 

shown to be 3.4 (96.6 percent S02 removal) with a GO of 1.885. 

The high geometric dispersions occur for both systems on the outlet and 

percent emissions due to the extrememly low emission levels; the magnitude of 

variance [e.g., x (g-1) and x/(g-l)] is smaller than for previous results from 

FGD monitoring studies. 

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P.33 

IV. RECOMMENDATIONS AND CONCLUSIONS 

1. The two systems monitored in this report illustrate very low emissions 

achievable with FGD systems on low sulfur coal with conventional limestone 

scrubbing and on high sulfur coal with conventional limestone scrubbing 

assisted by low concentrations (1500 ppm) of adipic acid. 

2. The relative ease of SO2 removal from low sulfur coal flue gas is shown 

by the Lawrence data, where 96.6 percent SO2 is removed. 

3. The benefits of adipic acid injection are shown by comparison of the 

system examined here compared to conventional lime scrubbing, where adipic acid 

enhancement of limestone showed 96.1 percent S02 removal compared to 88.6 percent measured o.n a parallel system with lime scrubbing only. 

24