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Third Interim Report: Continuous Sulfur Dioxide
Monitoring at Steam Generators
Volume I: Summary of Results
V \
?v:*S:^i-.^'?• ***+' *
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March 1979
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Emission Measurement Branch
Research Triangle Park. Norllt Carolina

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EMB ReDort No. 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 Quality Planning and Standards
Emission Standards and Engineering Division
Research Trianale Park, North Carolina 27711

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TABLE OF CONTENTS
Page No.
List of Fiqures	i
List of Tables	ii
Surriary of Results	1
Sections
I.	INTRODUCTION AND DESCRIPTION OF TEST SITES	2
A.	Introduction	2
B.	Description of Test Sites	3
1.	Shawnee 1 OA 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 Gatherinq Systems	7
1.	Shawnee 10A and 1 OB FGD Prototypes,	Tennessee Valley Authority,
Paducah, Kentucky	7
2.	Lawrence Unit No. 4, Kansas Power and Liaht Company,
Lawrence, Kansas	9
B.	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

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LIST OF FIGURES
Figure	Page No.
1-1	Shawnee 1 OA and 1 OB Scrubber Gas Flow	4
I-2	Lawrence No. 4 Scrubber Gas Flow	5
II-1	Instrument System Schematic, Shawnee 1 OA and 10B	8
II-2	Instrument System Schematic, Lawrence No. 4	10
III-l	Probability vs. Loq Inlet SOg i - Shawnee Ventun	18
II1-2	Probability vs. Loa Outlet SO^ - Shawnee Venturi	19
II1-3	Probability Loq Percent SOg "Emitted - Shawnee Venturi	20
II1-4	Probability vs. Log Inlet SO^ - Lawrence No. 4	21
II1-5	Probability vs. Log Outlet SO2 - Lawrence No. 4	22
111-6	Probability vs. Log Percent SO2 Emitted - Lawrence No. 4	23
i

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LIST OF TABLES
Table	Page
II-1	Analyzer SDecifications for Lawrence No. 4	11
III-1	Categorization of Data	16
ii

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TABLE OF CONTENTS
Page No.
List of Fiqures	i
List of Tables	ii
Summary of Results	1
Sections
I.	INTRODUCTION AND DESCRIPTION OF TEST SITES	2
A.	Introduction	2
B.	Description of Test Sites	3
1.	Shawnee 1 OA and 1 OB FGD Prototypes, Tennessee Valley Authority,
Paducah, Kentucky	3
2.	Lawrence Unit No. 4, Kansas Power and Lioht Company,
Lawrence, Kansas	3
II.	DATA GATHERING AND REDUCTION	7
A. Data Gatherinq Systems	7
1.	Shawnee 1 OA and 10B FGD	Prototypes, Tennessee Valley Authority,
Paducah, Kentucky	7
2.	Lawrence Unit No. 4, Kansas Power and Lioht Comoany,
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

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LIST OF FIGURES
Figure	Page No.
1-1	Shawnee 1 OA and 1 OB Scrubber Sas Flow	4
I-2	Lawrence No. 4 Scrubber Gas Flow	5
II-1	Instrument System Schematic, Shawnee 10A and 1 OB	8
II-2	Instrument System Schematic, Lawrence No. 4	10
III-1	Probability vs. Loq Inlet S02 i - Shawnee Venturi	18
II1-2	Probability vs. Loa nutlet SOg - Shawnee Venturi	19
II1-3	Probability Loq Percent SOg "Emitted - Shawnee Venturi	20
II1-4	Probability vs. Log Inlet SO^ - Lawrence No. 4	21
II1-5	Probability vs. Log Outlet S02 - Lawrence No. 4	22
II1-6	Probability vs. Log Percent S02 Emitted - Lawrence No. 4	23
i

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LIST OF TABLES
Table	Page
II-l	Analyzer Specifications for Lawrence No. 4	11
III-1	Categorization of Data	16
ii

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SUMMARY OF RESULTS
SO2 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 S02 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
S02 monitoring system. Due to some monitoring problems, 31 days data were
obtained (63 percent reliability) which showed average S0£ emissions of
0.22 lb/10® Btu and SO2 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 S02 monitors were
86 percent reliable, measurinq average SO2 emissions of 0.03 lb/10® Btu and
96.6 Dercent SO2 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.
1

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I INTRODUCTION AND DESCRIPTION OF TEST SITES
A. Introduction
This report summarizes the results of the latest EPA efforts to monitor
SO2 emissions and SOg 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 Dercent) sulfur coals using lime/limestone scrubbers. In the
systems described below, results are presented for SOg 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 Drocedures 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, SOg and O2 concentrations were measured upstream
and downstream of the FGD system using continuous instrumental monitors. Copies
of boiler operation loqs 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.
2

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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. Mo desiqn performance data are available.
Figure 1-1 is the process flow diagram for the Shawnee venturi system.
For this test, limestone and adipic acid 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
3

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| AIR
| FUEL OIL >-
REHEATER
Ifiue GAS>-Q-®-,
FAN
VENTURI
SCRUBBER
r	+-—O—-^"j 7fT.
I
——
®sss»
SPRAY
TOWER
1 LIME >-

SCRUBBER
EFFLUENT
NOLO
TANK
SAMPLE POINTS
CLAP. F ER
BLEED
PROCESS!
WATER
HOLD TANK
VACUUM
FILTER
|~o——
OGAS COMPOSITION
®PARTICULATE COMPOSITION & LOADING
® SLURRY OR SOLIDS COMPOSITION
GAS STREAM
LIQUOR STREAM
Figure 1-1
Tennessee Valley Authority, Shawnee Ho. 1U Prototype Unit;
General Process Diagram.
STACK
0
DISCHARGE
St III IIIG 1'IKII)

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STACK
FAN
o
FLUE GAS
SPRAY TOWER
ROD SCRUBBER
oo
*• EFFLUENT LINE
Figure 1-2 Kansas Power and Light, Lawrence No. 4 Operational FGO System:
Simplified Flow Diagram.

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flue gas in both the rod scrubbers and spray tower. Overall SO2 removal
is designed for a minumum 73 percent. A detailed description of this system
may be found in EPA 600/7-78-058b dp. 255-276, "Proceedings of the Symposium
on Flue Gas Desulfurization, November 1977.
6

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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 II1-1. The sulfur dioxide (S02)
instrument at each location 1s a DuPont 460 analyzer J The oxygen (O2) analyzer
is a Thermox model WDG 3 instrument. The ranges of the scrubber inlet SO2
analyzers are set at 0-4000 Dpm SOg and the ranges of the two scrubber outlet
SO2 analyzers are 0-1000 ppm. The ranges of O2 analyzer are all set at
0-10 percent 02- The S02 and 02 probes tips are located at the stack centers
with the 02 rpobe apDroximately one stack diameter upstream of the SO2 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 fcur strip chart recorders located in the scrubber
control room.
The moisture content correction for the SO2 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 02 gas measurements
was the stack moisture content as the 02 analyzers measured a wet gas stream.
Mention of a specific company or product name does not constitute endorsement
by the Environmental Protection Agency.
7

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Heated Teflon line
S0o Probe
Calibration gas
valve
0o Probe
DuPont analyzer
Analyzer
Knock-out
trap
<-
Recorder
S(L Recorder
Figure 11-1 Instrument System Schematic, Shawnee Power Station

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2. Lawrence Unit No. 4, Kansas Power and Liqht 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 probe 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 sample 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.
Oata acquisition was accomplished using an Accurex Auto Data Nine data
acquisition system with a 24-channel Ester!ine 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 os1. All heat traced lines
and heated boxes were operated at temperatures ranaing from 130°C to 200°C.
Sample flows to the oxygen analyzers were maintained at '1.6 ft^/hr while
9

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•<•1 ereute NuiIim)
SM|>lli»g fori
Rvhiunc* pulliod
Sampling Fort
O
llatt Tl«c«
SMfit LlM
Hofell* Laboratory
Powtr mi4
Control Llucc
D4I• Ac^ulslllvo
8]T«I«b
SO.
Icaicr Control#
•imI Switching
SO
*w.
i Hulerlui
Tutsi* ¥•!*•»
Figure 11-2 Schematic of Monitoring System of Lawrence No. 4

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those for the S02 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
TECO Model 40	Inlet	0-1000 ppm	S02/air
TEC0 Model 40	Outlet 0-100 ppm	S02/air
Beckman Model 742	Inlet	0-10S	02/N2
MSA Paramagnetic.
Analyzer	Outlet 0-10%	02/N2
B. Data Reduction Procedures
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)
11

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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

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mean	standard deviation
average deviation	maximum
minimum	range
percent standard deviation
These parameters were calculated assuming the data were normally distributed.
The calculation procedures used to convert the analyzer outputs for
sulfur dioxide and oxyaen concentrations to mass emission factors are given
1n 40 CFR 60 Subpart D. This Drocedure is known as the F-factor approach and
is outlined below:
r _ CFK .. 20.9
E _ T3T x 20.9-O2	
T^T
Where E = Emission factor - lb/million Btu
C = SOg concentration - ppmv, wet basis
F = Stoichiometric conversion factor, 9820 dscf/million Btu for
subbituminous coal
K =¦ Conversion factor, 1.659 x 10"^ lb/dscf Der ppmv
02 s Oxygen concentration, percent by volume as measured
M = 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

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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 3	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 (Fa) + EFFB(Fg)
Where,
EFFtotai a total system efficiency
EFFa	= efficiency of module or module set A
FA	= fraction of gas flow through module or module set A
EFFg	» efficiency of module or module set B
Fg	3 fraction of gas flow through module or module set B
14

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III. DATA ANALYSIS
A.	Data Calculation Assumptions
In previous SO2 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 samplinq time was ascertained, then the boiler and scrubber down time
was subtracted to yield the net days availabile for scrubber performance 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 SO2 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 percent SO2 removal on identical flue
gas to that which the lime-TCA FGD system previously reported an 88.6 percent
SOj removal.
15

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TABLE III-l CATEGORIZATION OF DATA
Shawnee Venturl FGD	Lawrence FGD
Total Oays	49	37
Boiler Down	0	0
Scrubber Down	0	11
Net	49	26
Full Oata Days	31	22
% Data Available	63.3	84.6

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Comparison of the Lawrence performance to design S02 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
SO2 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 111-1, J11-2, and 111-3 graphically illustrate FGD performance at
the Shawnee venturi site using limestone with adlpic acid additive. Figure III-l
shows inlet SOg loadings average 5.6 percent lb/10® Btu with a geometric
dispersion (GD) of 1.070. Figure II1-2 shows outlet S02 emissions averaging
0.22 lb/10® Btu with a GD of 1.518. Percent SOg emitted averaged 3.9 percent
(96.1 percent SOg removal) for the 31 day period with a GD of 1.427.
Figures II1-4 through II1-6 show the performance of the Lawrence venturi-
spray FGD using limestone slurry. Figure II1-4 shows average inlet SOg
loadings of 1.02 lb/10® Btu, while Figure II1-5 shows average outlet S0£
emissions of 0.03 lb/106 Btu. Geometric dispersions are 1.122 and 2.342 for
inlet and outlet respectively. In Figure II1-6 the percent SOg emitted is
shown to be 3.4 (96.6 percent SOg removal) with a GD of 1.885.
The hiqh 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.
17

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10
9
8
6
5
99 99 99.9 99 8	99 98 95 90	80 /0 00 SO
Figure 111-1 Shawnee Venturi-Llmestone/Adlplc
Acid - 31 Days Inlet SO^
40
30
20
10
05
0 2 0 1 OO'j 0 01
10
•>
8
/
6
5
5 ,0'
9
ci" 8
7
*->
2 6
5.(
5.68
I'«¦ i 'i:
g = V6.28 = 1.070
5TTZ
0 01 0 05 0 1 0 2
05
10
20
30
40 SO 60
70
80
90
95
98 99
99 8 99 9
99 99

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99 99
99.9 99 8
I 0 5 0? 0 1 0.05 0 01
/O 60 SO 40 30
Figure 111-2 Shawnee Venturl-Liniestone/Adipic Acid
31 Days Outlet SOp Emissions
= 1.518
0 01 0 05 0 1 0.2 0 5
99.8 99.9
99 99

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() 40
JO
20
10
05
(I Z 0 I 0 01)
001
Figure 111-3 Shawnee Venturi-Llmestone/AdlpIc Acid
31 Oays Percent SO^ Emitted.
m
X
9
3.9
3^§T68"
2.3
= 1.427
( i

0 01 0 00 0 1 0 2
05
10
20
30
40 50 60
70
80
90
95
98
99
99 8 99.9
99 99

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46 8040
lv t KtllMtl HlbSLRCi)
99 98 96 90
99 9 99 8
70 60 bO 40
Oi 0 1 IMI'j OOI
Figure II1-4 Lawrence
22 Days Inlet SO?
3/T21
1.122

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KllllMl M lyjl(IM) mm* »h
46 8040
0 5
99 9 99.8
Figure 111-5 Lawrence - 22 Days
Outlet SO-, Emissions
9b
90
70 60 SO <10
30
20
80
IO
001
10
0.032
2/^71
2.342
0133
rj
to
o
\J * 1
to
4-»
QJ
r—
*->
3
o
0.001
80
90
30 40 60 60 70
95
98 99
0 01 0 0b 0 1 0 2 0.5 I
20
99 8 99 9
99 99
2
5
10
i

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Ab »U4U
9999 99 9 99.8	99 98 95
Figure II1-6 Lawrence - 22 Days
Percent SOy Emitted

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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 S0£ is removed.
3.	The benefits of adipic acid injection are shown by comparison of the
system examined here compared to conventional Hme scrubbing, where adipic acid
enhancement of limestone showed 96.1 percent SO2 removal compared to 88.6 per-
cent measured on a parallel system with lime scrubbing only.
24

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