CD
o
EPA PROJECT REPORT NUMBER 75-LIM-8
R
EMISS
FEB 181975
•Jm
WOODVILLE LIME AND CHEMICAL COMPANY
Woodvilie, Ohio
UNITED 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
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PARTICULATE, SULFUR DIOXIDE, AND NITROGEN OXIDES
EMISSION MEASUREMENTS FROM LIME KILNS
EMB Projects Report No.
75-LIM-8
Plant Tested
Hoodville Lime and Chemical Company
Woodville, Ohio
August 6, 7, and 8, 1974
Prepared for
Environmental Protection Agency
Office of Air Quality Planning and Standards
Emission Measurement Branch
Research Triangle Park
North Carolina 27711
by
W. R. Feairheller
D. L. Harris
MONSANTO RESEARCH CORPORATION
DAYTON LABORATORY
1515 Nicholas Road
Dayton, Ohio 45^07
Report Reviewed by Clyde E. Riley
.Contract No. 68-02-1404, Task No. 2
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TABLE OP CONTENTS
Page
I. INTRODUCTION . 1
II. SUMMARY OF RESULTS 3
III. PROCESS DESCRIPTION 11
IV. LOCATION OF SAMPLING POINTS Hi
V. PROCESS OPERATION AND TEST CONDITIONS 19
VI. SAMPLING AND ANALYTICAL PROCEDURES 23
ill
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LIST OF ILLUSTRATIONS
Page
1 Stack Port Locations 15
2 . Test Site No. 1 Kiln Precipitator Outlet 17
3 Particulate Test Traverse Cross Section 18
^ Integrated Gas Sampling Train 25
5 Particulate Sample Train 26
6 Nitrogen Oxide Sampling Equipment . 30
7 S02/S03 Sampling Train 32
LIST OF TABLES
Page
1 .Summary of Particulate Results (English 4
Units)
2 Summary of Particulate Results (Metric Units) 5
3 Summary of NOX Results 6
4 Summary of S02 Results 7
5 Visible Emissions Summary 9
6 Total Sulfur Content of Silo Feed, Fuel Oil, 10
Product and ESP Dust
7 Summary of Operating Variables 22
IV
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SECTION I
INTRODUCTION
Under the Clean Air Act of 1970, the Environmental Protection
Agency is given the responsibility of establishing performance
standards for new installations or modifications to existing
installations in stationary source categories. As a contractor,
Monsanto Research Corporation (MRC), under the Environmental
Protection Agency's "Field Sampling of Atmospheric Emissions"
Program, was asked to provide emission-data from the Woodville
Lime and Chemical Company of Woodville, Ohio.
The field test work was directed by Clyde E. Riley, Field
Testing Section, Emission Measurement Branch. The sampling
was performed by Monsanto Research Corporation with Darrell L.
Harris as Team Leader.
This report tabulates the data collected at the No. 1 lime kiln
of the Woodville Lime Company during the sampling program of
August 6, 7, and 8, 197^. This kiln is equipped with a Buell
electrostatic precipitator to control particulate emissions.
The feed for the kiln is a dolomitic stone, quarried at the
site, and sized at one inch to two and one-fourth inches. Feed
rate is approximately 700 tons per day and product rate is
approximately 350 tons per day. The kiln is. fired with a
mixture of natural gas and a number 6 fuel oil, and no pre-
heater .is used. The product is cooled in a Neims cooler before
storage and no crushing is performed.
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Sampling was performed at the outlet of the electrostatic pre-
cipitator. The outlet was measured for particulate concentra-
tions according to procedures described in the Federal Register1
Method 5, "Determination of Particulate Emissions from Stationary
Sources." Method'1, "Sample and Velocity Traverses for Station-
ary Sources"; Method 2, "Determination of Stack Gas Velocity
and Volumetric Flow Rate (Type S Pitot Tube)".; and Method 3,
"Gas Analysis for .Carbon Dioxide, Excess Air and Dry Molecular
Weight" are other procedures that were required for the Method 5
tests. Other tests that were performed were a combination of
Method 8 and Method 6, "Determination of Sulfur Dioxide Emissions
from Stationary Sources"; Method 7, "Determination of Nitrogen
Oxide Emissions from Stationary Sources"; and Method 9, "Visual
Determination of the Opacity of Emissions from Stationary
Sources." All of the above methods are described in the
Federal Register.2
No modifications were necessary to prepare the kiln stack for
sampling. Sampling performed previously by another contractor
required an extension of the stack and the erection of scaffold-
ing for placement of the sampling devices. These modifications
were unchanged for this program (see EMB report 74-LIM-3A).
The following sections of this report include: (1) summary
of results, (2) description of the process, (3) location of
sampling points and traverse data, (4) process operating condi-
tions, and (5) sampling and analytical procedures. Appendices
include all field data from this sampling project. Process
production rates are not included in this report but will be
available in a future publication.
'Federal Register, Vol. 36, No. 159, August 17, 1971.
2Federal Register, Vol. 36, No. 2^7, December 23, 1971.
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SECTION II
SUMMARY OP RESULTS
Data on particulate emissions from the lime kiln are summarized
in Tables 1 and 2. Emissions of filterable particulate, as
measured by the probe and filter catch, averaged 7-^3 pounds
per hour (Ib/hr) at a concentration of 0.0303 grains per dry
standard cubic foot (grains/dscf). Total particulate emissions
averaged 12.2 pounds per hour at a concentration of 0.0500
grains/dscf. Emissions from the first test (P-l) were obviously
much higher than the other two runs. While the reason for
this difference is not apparent, it can probably be attributed
to variations in process operations and to problems encountered
with control equipment operating parameters, described in
Section IV, "Process Operation." In addition, it should be
pointed out that this increase in emissions is concurrent with
the visible emission data.
Data on the oxides of nitrogen emissions are summarized in
Table 3- These data show an average N02 concentration of
279 ppm by volume and an hourly emission rate of 55.-5 pounds
per hour.
Data on sulfur dioxide emissions are summarized in Table 4.
These data show an average S02 concentration of 15-3 ppm by
volume and an hourly emission rate of 4.21 pounds per hour.
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Table 1
SUMMARY OP PARTICULATE RESULTS
(English Units)
Run Number
Date
Method Type
3.
Volume of gas sampled-dscf
Percent moisture by volume
Average stack temperature-0? .
Stack volumetric flow rate-dscfm
Stack volumetric flow rate-acfm
Percent isokinetic
Duration of run-minutes
Particulates-probe, cyclone and filter catch
• mg d
grains/dscf
Ib/hr
Particulates-total catch
mg d
grains/dscf
Ib/hr
Percent impinger catch
p-1
8-6-7^
EPA-5
105.92
9.61
611
28986
65320
98.7
192
422.9
0.0615
15.3
667.8
0.0971
24.1
36.7
P-2
8-7-74
EPA-5
128.16
11.05
661
27704
66488
104.5
• 192
119-1
0.0143
3.40
253-3
0.0304
. 7.23
53-0
P-3
8-r8-74
EPA-5
119.80
10.81
655
27559
65754
97.4
192
117-3
0.0152
3.59 •
173-5
0.0225
5.31
32.4
averag
117.96
10.49
642
28083
65854
100.2
192
219.8
0.0303
7-43
364.9
0.0500
12.21
40.7
Dry standard cubic feet § 70°P, 29.92 in. Hg
'Dry standard cubic feet per minute § 70°F, 29.92 in. Hg
'Actual cubic feed per minute-stack conditions
Grains per dry standard cubic feet
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Table 2
SUMMARY OP PARTICULATE RESULTS
(Metric Units)
Run Number P-l P-2 P-3 Average
Date 8-6-71* 8-7-74 8-8-74
Method Type EPA-5 EPA-5• EPA-5
Volume of gas sampled-Nm3 a 3-000 3-630 3-364 3-331
Percent moisture by volume . 9-61 11.05 10.8l~ 10.49
Average stack temperature-°C 322 349 346 339
Stack volumetric flow rate-Nm3/sec 13-68 13-08 • 13-01 ' 13-26
Stack volumetric flow rate-acfm3/sec 30.83 31-38 31-04 31.08
Percent isokinetic 98.7 104.5 97-4 100.2
Duration of run-minutes 192 192 192 192
Particulates-probe, cyclone and filter catch
mg 422.9 119-1 117-3 219.8
mg/Nm3 140.9 32.81 34.87 69-53
Kg/hr • 6.934 1.543 1.630 3-369
Particulates-total catch
mg 667-8 253-3 173-5 364.9
mg/Nm3 222.6 69-78 51.58 114.7
Kg/hr . 10.95 3.281 2.412 5-548
Percent impinger catch 36.7 53-0 -32.4 40.7
aNormal cubic meters at 21.1°C, 760 mm Hg
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Table 3
SUMMARY OF NO,
RESULTS
Date Run #
/
8-6-74 N-1A
8-6-74 N-1B
8-6-74- N-1C
8-6-74 N-1D
N-l Average
8-7-74 N-2A
8-7-74 N-2B
8-7-74 N-2C
8-7-74 N-2D
N-2 Average
8-8-74 N-3A
8-8-74 . N-3B
8-8-74 N-3C
8-8-74 N-3D
N-3 Average
N-l, N-2, and
N-3 Average
Time
1540
1630
1820
1920
—
1200
1240
1415
1510
—
1045
1130
1230
1335
—
a
ppm
174
226
202
200
201
341
355
436
320
363
.253
276
292
276
274
279
X "
Ib/DSCF
x 10~5
2.06
2.68
.2.39
2.37
2.38
4.04
4.21
5.16
3-78
4.28
2.99 •
3-27
3.45
3-27
3.24
3.30
grams/Nm3
0.330
0.430
0.383
0.380
0.382
0.648
0.675
0.827
0.606
0.686
0.479
0.524
0.553
0.524
0.519 •
0.529
lb/hrb
35.8
46.6
41.6
41.2
41.3
67.2
70.0
85.8
62.8
71.4
49.4
54.1
57.0
54.1
53-7
55.5
Kg/hr1
16.3
21.2
18.9
18.7
18.8
30.5
31.8
39.0
28.5
32.4
•22.4
24.6
25-9
24.6
.24.4
25.2
b
^Parts per million, by volume
Based on volumetric flow rate from corresponding Method 5
run (DSCPM)
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Table 4
SUMMARY OF S02 RESULTS
Run # S-l S-2 S-3 Average
Date 8-6-74 8-7-74 8-8-74 .
Volume of gas sampled (dscf) 146.8 96.14 73-84 105-59
(Nm3) 4.157 2.723 2.091 2.980
Run Time (min) 187 180 164 177
SC>2 Concentration
(ppm, by volume) 6.08 26.6 13.1 15-3
(Ib/dscf x 10-6) 1.01 4.38 2.17 2.52
(mg/Nm3) 16.1 70.2 . 3/1.8 40.4
S02 Emission Ratea
(Ib/hr) 1.70 , 7.35 3-59 4.21
(Kg/hr) . 0.772 3.34 1.63 1.91
o
Based on velocity taken from corresponding Method 5 run
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Visual emissions measurements were recorded from the No. 1
kiln stack plume independently by two MRC personnel during
each particulate test. Data for these opacity measurements
are summarized in Table 5. The average opacity for all tests
was less than five (5) percent. Periods of high emissions,
however, did occur during certain sequential minute intervals
for the first test, during which opacity levels exceeded the
5 percent normal range. .This normal range value of 5 percent
opacity or less was considered typical of the Woodville control
device as well as other well-controlled lime-producing opera-
tions.
Samples of the limestone feed material in the storage silo,
the kiln product, fuel oil, and the dust recovered by the
electrostatic precipitator (ESP) were collected near the
beginning and end of each of the sampling runs. A composite
was prepared of the feed material and fuel oil on which analy-
sis for the total sulfur content was performed along with the
individual samples of product and ESP dust. These results
are presented in Table 6.
Additional detailed results of the test program are presented
in Section V, "Sampling and Analytical Procedures."
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Table 5
VISIBLE EMISSIONS SUMMARY
.Run No.
Date
Interval of observations
Start
End
Duration of observation
(min)b
Total no. of readings0
No. of readings unobservable
No. of readings % 0% 'opacity
5%
10%
Percent readings unobserv-
able
Percent readings @ 0% opacity
5%
10%
p-1
8-6-7^
Obs. 1 Obs. 2
1525
1925
197
788
0
.555
221
12
0
70.43
28.05
1.52
1525
1925
213
852
0
182
641
29
0
21.36
75.23
3.41 '
P-2
8-7-74
Obs. 1 Obs. 2
1143
1522
193
773
0
682
89
2
0
88.23
11.51
0.26
1143
1522
194
776
7
558
208
3
0.90
71.91
26.80
0.39
P-3
8-8-74
Obs. 1 Obs. 2
1026
1357
194
776 •
0
748
26
2
0
96.39-
3.35
0.26
1026
1357
197
788
1
717
68
2
0.13
90.99
8.63
0.25
24-hour clock start and end times . •>
Excluding the time that readings were not recorded for period of observation
'Readings recorded at 15-second intervals unless otherwise noted
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Table 6
TOTAL SULFUR CONTENT OF SILO FEED, FUEL OIL,
PRODUCT AND ESP DUST
Date
8-6-74
Sample No.
S-74-001-788
791
792
793
795
796
Material
Silo Feed
Fuel Oila
Kiln Product
Kiln Product
ESP Dust
ESP Dust
'% Sulfur Found
0.028, 0.028
1.52
0.081, 0.099
0.098', 0.108
0.572, 0.707
0.527, 0.650
Avg
% Sulfur
0.028
1.52
0.097
0.614
8-7-711 S-74-011-836 Silo Feed
839 Fuel Oila
840 Kiln Product
841 Kiln Product
843 ESP Dust
84-4 ESP Dust
0.034, 0.036 0.035
1.36 1.36
0.40, 0.30 0.23
0.11, 0.11
0.76, 0.87 .0.77
0.70, 0.74
8-8-74
S-74-001-873
876
.877
878
880
881
Silo Feed
Fuel Oila
Kiln Product
Kiln Product
ESP Dust.
ESP Dust
0.053, 0.048 0.051
1.37 1.37
0.071, 0.077 0.11
0.149, 0.148
0.733, 0.672 0.71
0.688, 0.732
a
The fuel oil samples were also analyzed for the Btu content with
the following results:
S-74-001-791
S-74-001-839
S-74-001-876
18236 Btu/lb
18343 Btu/lb
18404 Btu/lb
10
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SECTION III
• PROCESS DESCRIPTION
Limestone consisting primarily of calcium carbonate or. .combi-
nations of calcium and magnesium carbonate with varying amounts
of impurities is quarried at the Woodville Plant. The lime-
stone is calcined or burned to form lime, commonly divided
into two basic products—quicklime and hydrated lime. Calci-
nation expels carbon dioxide from the raw limestone, leaving
calcium oxide (quicklime). With the addition of water, calcium
hydroxide (hydrated lime)-is formed.
The basic processes in production are: (1) quarrying the
limestone raw material, (2) preparing the limestone for kilns
by crushing and sizing, (3) calcining the limestone, and
(4) optionally processing the quicklime further by additional
crushing and sizing followed by hydration. The majority of
lime is produced in rotary kilns which can be.fired by coal,
oil, or gas. Rotary kilns have the advantage of producing
high production per manhour and a more uniform product. They
do, however, require higher capital investment and unit fuel
costs than most vertical kilns.
The Woodville Lime and Chemical plant has two rotary kilns
each equipped with a Buell electrostatic precipitator. The
kilns are almost identical. The feed for both is a dolomitic
stone, quarried on the site and fed in sizes ranging from
1 inch to 2-1/4 inches at a rate of about 700 tons per day.
11
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There is no preheater. Normally the kiln is fueled with a
mixture of 95 percent Number 6 fuel oil and 5 percent natural
gas. Both kilns have two heat transfer sections, each 20
feet long. The product, about 350 tons per day, is cooled in
a Neims cooler before storage. There is no product crushing,
but undersize material is separated and returned to 'the kiln.
The majority of the product is used in the steel industry,
mostly in basic oxygen furnaces. None of the product is
hydrated.
The electrostatic precipitator on kiln Number 1 was put in
operation in July 1971. In this kiln the main process fan is
located before the ESP, with a cyclone before the fan to reduce
fan blade erosion. The precipitator on kiln Number 2 was put
in operation in December 1973- The main process fan is after
the ESP, and there is no cyclone.
In both systems the inlet gas to the precipitators is cooled
to-about 600°P with a combination of water injection and/or
tempering air. Each precipitator has 28,800 square feet of
collecting surface area, which includes one cell and two
fields. Design gas velocity is 1.5 feet per second and treat-
ment time is 10.0 seconds. The plant manager reported that
an earlier emission test showed exit loadings of less, than
0.005 grains per dry standard cubic foot.
At present the dust collected from the precipitators is dis-
posed of in the quarry. It is expected that in the future
'the dust will be granulated and used as a .component of dry
mix fertilizers that are blended in another part of the
complex.
12
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At the time of the initial plant inspection (February 8,
197*0 > the precipitators were working satisfactorily and had
been very well maintained. The plant is representative of
modern design. Raw materials and products are typical of
those in the industry.
13
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SECTION IV
LOCATION OF SAMPLING POINTS
Figure 1 shows the sampling ports used in the Number 1 lime
kiln exit stack. The sampling ports were located in a 63.5-
inch inside diameter vertical stack, 4 feet (0.75 diameter)
from the stack exit, and 12 feet (2.26 diameters) from the
nearest upstream disturbance. In order to meet the sampling
requirements of Methods 1 and .5 of the Federal Register,
Vol. 36, No. 2^7, it was necessary to use an existing stack
extension that had been left on the ESP exhaust outlet from
a preceding test program. Forty-eight traverse points (2*1
along each of two perpendicular diameters) w.ere used as
described in the Federal Register, Method 1. The stack was
found to be slightly elliptical at this location, measuring
62-3/4 inches on the east-west diameter and 63-1/2 inches on
the north-south diameter. The larger diameter was used for
calculation of the stack area.
Test Methods 1, 2, 3, 5 and 7 were performed at the set of
90° ports on the -stack 146 inches from the outlet of the ESP
and 48 inches from the atmospheric outlet of the stack.
Additional sampling points in the existing stack at a lower
site were used for some of the gas sampling. Modified Method
6 tests were conducted at the west port located 53 inches
from the ESP outlet and l4l inches from the stack outlet.
Sampling was done at a single point on the west port traverse
at a probe insertion depth of 33 inches. -
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3 PORTS
90° APART
Figure 1. Stack port locations
15
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Figure 2 shows a top view of the -stack and the scaffolding
location. Figure 3 is a cross-sectional view of the outlet
which shows the location of the ^8 traverse points.
16
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TOP VIEW
45" _
\s
EDGE OF ROOF
-45'
SCAFFOLDING
\
Figure 2. Test site No. 1 kiln precipitator outlet
17
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WEST PORT
SOUTH PORT
48 POINT TRAVERSE
63.5" ID
Figure 3. Particulate test traverse cross section
18
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SECTION V
PROCESS OPERATION AND TEST CONDITIONS
Prom previous plant visits and discussions with plant per-
sonnel, it was found that the two electrostatic precipitators
operate under normal conditions with essentially no visible
emissions. Plant 'operations appeared to be normal for the
Number 1 kiln and electrostatic precipitator on the morning
of August 6, 197*1, with visible emission opacity readings in
the range of 0 to 5 percent.
However, several problems developed during the first day of
testing. At 8:10 a.m. the plant manager informed the Project
Officer that a fan shutdown was scheduled on the Number 1
kiln. The fan is located on the inlet to the ESP and has to
be cleaned of adhering dust material on a routine basis.
The shut-down was scheduled for 8:30 a.m..and lasted for only
ten minutes.
The first series of tests was started at. 3:25 p.m. A probe
tip exchange was necessary .at 4:15 p.m. due to subisokinetic
sampling conditions caused by a low orifice pressure calibra-
tion factor. As testing progressed, the opacity readers
reported an increasing number of 5 percent readings, with
occasional "puffs" as high as 10 percent. Observations of
the.plume were difficult because of the cloudy overcast sky
background as well as the excessive fugitive dust emissions
created by trucks loading and unloading ESP dust and quarry
19
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rock in the vicinity of either the ESP unit or the observ-
ers .
The oil feed rate to the kiln had to be substantially increased
at 2:30 p.m. to maintain the desired kiln temperature. This
condition was caused by another kiln starting up which reduced
the natural gas pressure on the main feed line. The test was
completed at 7:00 p.m.
Near the end of the test, the ESP inlet temperature increased
to 710°P at which time (6:00 p.m.), it was noticed that the
stack opacity was clearing up. Mr. Judd, the plant chemist,
was asked if they could maintain the inlet temperature between
700°F and 710°F for the second test, which would start the
following morning.
Upon arrival at the plant the following morning, the stack
opacity was observed to be at 0 percent. The process
operator stated that the ESP inlet temperature had not
dropped below 700°F for the last 16 hours.
The second test was started on August 7 at 11:^4 a.m. The
majority of visible emissions were recorded to be 0 percent
opacity with minor periods of 5 percent opacity through this
test sequence. During the test, no sampling or process problems
i
were encountered. The test was completed at 3:22 p.m.
The third test was conducted during the following morning
(August 8, 197*0 starting at 10:27 a.m. The stack plume was
reading at.0 percent opacity and the process was operating
at a normal production rate. The visible emission readers
reported that they were observing a lower percentage of 5
percent readings compared with the second test. Short, puffs
20
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of 5 percent were the only readings observed during this
testing sequence.
The kiln feed rate was calculated by multiplying a conversion
factor times the'total indicated tonnage recorded from the
control room stone totalizer meter. These data are not
available at this time but will be supplied in a future
publication. Operating variables for the three test runs are
summarized in Table 7- Additional detailed information per-
taining' to the process operation during the testing periods
is presented in Appendix F.
The Woodville Lime and Chemical plant is very representative
of modern design' and operation, and has a typical raw material
and product. During the entire test program conducted between
August 6, 197^5 and August 8, 197^, the process and electro-
static precipitator were operating at a normal production
rate for which the facility was designed. It is therefore
recommended that the results of the emission tests conducted
at this installation be used in the development of standards
of performance for the lime producing industry.
21
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Table 7
SUMMARY OF OPERATING VARIABLES
Date 8-6-7*1 8-7-7*1 8-8-7*1
Particulate test no. P-l P-2 P-3
Stone feed rate (ton/hr)a - - -.
Oil rate (gal/hr) 29*1 311 316
Firing zone temp (°F) 26*19 2662 2600
Mid-kiln temp'(°F) 1352 1373 1360
Kiln feed end temp (°F) 1025 . 1031 1023
Before ESP temp (°F) .702 711 712
Stack; temp (°F) 663 673 669
ELECTROSTATIC PRECIPITATOR DATA
"A" Field
Primary current (amps) 7*J 68 69
Primary voltage (volts) 251 257 256
.Precipitator current (amps) . *(5 .39 • **0
"B" Field
Primary current (amps) 72 70 . 70
Primary voltage (volts) 238 2*18 2*15
Precipitator current (amps) . *l*t .*)*( .44
Obtained by multiplying indicated meter tonnage by a con-
version factor
•22
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SECTION VI
SAMPLING AND ANALYTICAL PROCEDURES
The outlet gases of the Electrostatic precipitator at the
Woodville Lime and Chemical Company lime kiln were sampled
for particulate emissions, sulfur dioxide, and. nitrogen
oxides concentrations. Runs of the particulate series were
identified by a number prefixed by "P" followed by the number
of'the series. SOa and NO run numbers were preceded with
X
an "S" or "N", respectively.
Sampling- procedures were designated by EPA. Analyses of
collected samples were performed by Monsanto. Appendix J
presents detailed sampling and analytical procedures.
Velocity and Gas Temperature,
Gas velocities were measured with a .calibrated type S pitot
tube and inclined draft gage. Velocities were' measured at
each sampling point across the stack diameter to determine an
average- value according to procedures described in the
Federal Register1, Method 2. Temperatures were measured with
the use of a thermocouple.
federal Register, Vol. 36, No. 2^7, December 23, 1971.
23
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Molecular Weight
A 4-hour integrated sample of the stack gases was collected
during each particulate test by pumping the gas into a Tedlar
plastic bag at the rate of approximately 0.-005 cfm. The
sampling train was assembled as shown in Figure 4. This bag
sample was then analyzed with an Orsat analyzer for C02, Oz,
and CO as described in the Federal Register, Method 3.
Particulates
Concentrations of particulate matter in stack gases were
measured by Method 5 as described in the Federal Register.1
A rigid train consisting of a heated glass-lined probe, a
3-inch diameter glass-fiber filter, and a series of Greenburg-
Smith impingers was used for particulate sampling, as shown in
.Figure 5-
Sampling was conducted under isokinetic conditions by moni-
toring stack-gas velocity with a pitot tube and adjusting
the sampling rate accordingly.
The three particulate runs were performed on three successive
days. All runs used two 24-point traverses, for a total-of
48 points, and each point was sampled 4 min for a total run
time of 192 min. On the first run (P-l), a .374 inch nozzle
was used to start the run. At the eleventh point of the first
traverse, it became obvious that the flow rate would not be
sufficient to maintain an isokinetic rate with the .374 inch
nozzle throughout the run. Preparation was made for a nozzle
change. Between the 13th and 14th points (52 min into the
federal Register, Vol. 36, No. 159, August 17, 1971.
24
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PROBE
AIR-COOLED
CONDENSER
RATE
METER
RIGID
CONTAINER
Figure *J. Integrated gas sampling train
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CTN
THERMOMETER
HEATED
GLASS
PROBE
ICE
I BATH
LI ' OlLlV.nULL-'l
Jj_0_0_mJL_ OF_WATER |
CALIBRATED ORIFICE
UMBILICAL
CORO
MANOMETER i
Figure 5. Particulate sample train
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run) the sampling was stopped, and a 0.2^4 inch nozzle was
installed for the remainder of the run.'
This nozzle change, caused no problem in the calculation of
particulate grain loading; however, calculation of the isokine-
tic percentage was more difficult.. Calculation was accomplished
by treating the two parts of the run as separate runs and
taking a weighted average t.o determine the final percentage
by the following method:
Io =
Pi + P2
where:
Io = overall isokinetic percentage
Ii = isokinetic percentage with first nozzle
la = isokinetic percentage with 2nd nozzle
P! = number of first nozzle points
P2 = number of second nozzle points
During Run P-l, at approximately 150 minutes into the run,
the AH reading dropped below its set point and the vacuum
increased indicating a plug in the system.- It became impossi-.
ble to control the flow rate at a sufficiently high level,
so the run was stopped. An inspection of the equipment
revealed no noticable plug, but it was suspected that the
umbilical -tubing had become kinked. The run was're-started,
and no additional flow stoppage occurred.
Samples from the Method 5 sampling trains were recovered as
outlined in the August 17, 1971, Federal Register. After removal
of the filter, all sample exposed surfaces were washed with
distilled water or reagent grade acetone as specified. All
sample bottles for liquid samples were obtained from Wheaton
27
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Scientific, Catalogue No. 219630. Each of these bottles,
except those used-for collecting S02 samples, was acid-
soaked with 1:1 HNOs for one day, rinsed with distilled
water, and soaked with distilled water for one day.
The particulate sample was recovered by rinsing the nozzle,
probe, cyclone by-pass, and front half of the filter holder
twice with acetone into a glass container. The inside walls
of the probe were brushed while rinsing. The back half of the
filter holder, impingers, and connecting tubes were rinsed
twice with distilled water and the washings placed in a glass •
container with the impinger contents. These components were
then double-rinsed with acetone into another glass container.
The filter was placed in a separate container. Blank samples
of water and acetone were also taken.
Analytical procedures for the Method. 5 samples follow the
Federal Register guidelines, with one exception. Container
Number 3 as indicated in the method contains water from the
impingers and washing of the glassware of the train. The
solution was extracted with chloroform and ether, and then
the extracted portion was dried to constant weight, as speci-
fied. In addition, the water remaining after extraction was
evaporated to dryness at 212°F to constant weight. Both
weights were included in the total mass of particulate.
Sample weights from the Method 5 samplers were reported as
"front half" (probe washings and filter collection weights)
and "total" (front half plus water, chloroform-ether extract
and impinger acetone washing weights). Sample residues were
sent to EPA for trace metal analysis.
28
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NO
Nitrogen oxides were collected in evacuated 2-liter flasks
containing 25 ml'of.a dilute sulfuric acid/hydrogen peroxide
absorbing solution. The sampling and analytical procedure
was described in Method 7 of the,Federal Register.1 The
sampling train was assembled as shown in Figure 6. Pour
nitrogen oxide samples were collected at equal intervals during
each of the particulate runs. Each sample was collected using
a 2-foot glass-lined probe at the upper port locations. Each
flask was evacuated and pressure tested for one minute, and
the initial flask temperature, pressure, and barometric pressure
recorded. The sampling probe was inserted into the stack
and heated, and th'e sample flask connected. The 3-way stopcock
was turned to the "purge" position and stack gas drawn through
the system with a rubber squeeze bulb to check for condensa-
tion in the probe line. The 3-way stopcock was then turned
to the sample position for 1.5 to 30 seconds. The flask valve
was then closed and disconnected from the probe. The contents
were shaken for at least 5 minutes.
i
The flasks were allowed to set for at least 16 hours. They
were then shaken for at least 2 minutes, the final pressure,
temperature,, and barometric pressure were taken, and the sample
was transferred to a storage bottle.
The samples were analyzed using the Phenoldisulfonic acid,
photometric analysis described in the above mentioned Federal
Register.1 Table 3 gives the calculated amounts of nitrogen
oxides given as N02 in both parts per million and mass per unit
^Federal Register, Vol. 36, No. 2^7, December 23, 1971.
29
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EVACUATION SYSTEM
0 purge
(R evacuate
i ^r
(D sample
°>
0
vacuum gauge
valve
3-way stopcock
flask
pump
foam encasement
SAMPLING
/
heated Pyrex probe
*>
glasswool
fillor
squeeze bulb
Figure 6. Nitrogen oxide sampling equipment
30
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volume. Mass per unit time figures were calculated using the
volumetric flow rate from the corresponding Method 5 run pitot
traverse.
S02
Sulfur dioxide sampling procedures followed those described
in Method 6. However, due to the low expected concentrations,
the Method 8 sampling train shown in Figure 7 was used. The
first impinger contained 150 ml of 80 percent isopropanol;
the second and third impingers contained 100 ml each of 3
percent hydrogen peroxide/water solution. The SOa determina-
tion runs were performed simultaneously with each Method 5
run on the three days and are of the same general duration.
The first run (S-l) was conducted using a flow rate of
approximately 1 acfm and the second and third runs (S-2 and
S-3) using a rate of approximately 0.5 acfm at meter condi-
tions. On the last run (S-3), at the 164th minute,'the dial
shaft of the dry gas meter broke, and the run was stopped and
considered to be complete at this point. For all three runs,
the solution in the first impinger was replaced with fresh
solution during port switching. Also during these shut downs,
the silica gel was changed, if necessary. After sampling,
ambient air was passed through the train for 10 to 15 minutes.
The isopropanol solution was discarded, and the peroxide
solution rinsed into a glass container. Samples collected
from the sulfur dioxide modified Method 6 runs were analyzed
by the barium perchlorate titration using thorin indicator
as outlined in the December 23, 19713 Federal Register.
Table 4 gives the summary of results of the S02 testing. The
SOa emission rates are based on the velocity determined during
the Method 5 run of the same sampling period.
31
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SS NOZZLE
HEATED GLASS PROBE
STACK WALL
OJ
rv>
.__TO PUMP
AND METER
1. G-S Impinger- - 100 ml 80% isopropanol
2. Modified G-S Impinger - 100 ml 3% H202
3. G-S Impinger - 100 ml 3% H202
4. Modified G-S Impinger - 200 g Silica Gel.
5. Filter Holder w/Glass Fiber Filter
Figure 7. S02/S03 sampling train
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Visible Emissions
Visible emissions were determined according to procedures
presented in Method 9- Two observers were employed to record
simultaneous visible emission data during the particulate
testing. The observers started recording readings just prior
to the start.of the Method 5 run and ended just after the
Method 5 run stopped. Readings were also discontinued during
shut-down periods for port changing, etc.
Readings were difficult to determine at times due to trucks
loading and unloading ESP dust and quarry rock in the vicinity
of either the ESP unit or the observer, and the light-colored
plume against an overcast and partly .cloudy sky caused poor
distinction. In addition, during the first run certain ESP
rappers set up a visible emission condition, "puffs," that read
approximately 5 to 10 percent opacity for about 2 to 3 seconds
every rapping cycle. Readings were taken and recorded every
15 seconds. The summary of these readings is presented in
Table 5-
Total Sulfur Analysis
Samples of the limestone feed material in the storage silo,
the kiln product, the fuel oil, and the dust collected by the
electrostatic precipitator (ESP) were collected near the be-
ginning and end of each sampling run. A composite was prepared
of the feed material and fuel oil on which analysis of the total
sulfur content was performed along with the individual samples
of product and ESP dust. The sulfur content of the fuel oil
was analyzed by the Parr bomb calorimeter method.
33
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A major problem was encountered in the analysis of the sulfur
content of the limestone (silo feed), kiln rr'^uct, am] ESP
dust. It was suggested by EPA that the materials be analyzed
by the Parr bomb method (ASTM D271-46). The materials would
not ignite using the standard method, and benzoic acid was
added as a combustible material as suggested in the alternate
method. The procedure is basically a gravimetric technique
in which the sulfur is' converted to sulfate and precipitated
as BaSCU, a white material. However, the precipitate was
brown, indicating the formation of Fe(OH)3 which coprecipitated
and thus lead to apparently high sulfur values. An alternate
procedure specific Tor limestone and lime analysis (ASTM C-25-7P)
was. suggested to EPA. This Na2Cp3 fusion method was used to
obtain the sulfur content of the lime and limestone sample?.
Fuel oil samples were analyzed for -sulfur content by using
Standard Method of Test for Sulfur in petroleum Products by
the Bomb Method, D129-64. The complete sulfur results for
these samples can be found in Table 6.
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