O
EPA REPORT NUMBER 72-PC-ll
AIR
EMISS
CHAMPION INTERNATIONAL
Pasadena, Texas
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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SOURCE TEST REPORT
EPA No.: 72-PC-ll.
Particulate and Gaseous
Emissions From
A Kraft Pulp Hill
U. S. PLYWOOD - CHAMPION PAPERS
Pasadena, Texas
EPA Contract No.: 68-02-0232
Task No.: 7
Environmental Engineering, Inc.
2324 Southwest 34th Street
Gainesville, Florida 32601
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TABLE OF CONTENTS
Page Number(s)
I. INTRODUCTION 1
II. SUMMARY AND DISCUSSION OF RESULTS 2-6
TABLE 1 - TRS Daily Averages 4
TABLE 2 - Participate and Sulfur Dioxide Emissions 5
TABLE 3 - Carbon Dioxide, Oxygen, and Carbon
Monoxide Concentrations 6
TABLE 4 - Nitrogen Oxide Concentrations No. 6
Recovery Furnace Outlet 6
III. PROCESS DESCRIPTION AND OPERATION 7-16
Figure 1 - Flow Diagram of Recovery Furnace and
Black Liquor Oxidation System .... 8
TABLE 5 - Summary of the Recovery Furnace
Process Data 13
TABLE 6 - Sodium Sulfide Concentrations in Black
Liquor Fed to the Direct Contact
Evaporator 14
TABLE 7 - Summary of Process Data for the Black
Liquor Oxidation System 15
TABLE 8 - Summary of Process Data for the
Electrostatic Precipitator 16
IV. LOCATION OF SAMPLING POINTS 17-18
Figure 3 - Top View of Particulate Sampling Ports 18
V. SAMPLING AND ANALYTICAL PROCEDURES 19-32
Figure 4 - GC Gas Sampling System 21
Figure 5 - Barton Sampling System 23
Figure 6 - Particulate and S0? Train 26
Figure 7 - C02> 02> and CO Sampling System ... 30
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I.. INTRODUCTION
In accordance with Section 111 of the Clean Air Act as amended
of 1970, the Environmental Protection Agency is charged with the
establishment of performance standards for new stationary sources
which may contribute significantly to air pollution. These standards
are based upon the best air pollution control technology that has been
demonstrated.
This report presents the results of an extensive source testing
program conducted at Champion Paper Company, Pasadena, Texas, June 3-9,
1972, to obtain data for a partial basis in consideration of new source
performance standards in the kraft pulping industry.
Stack emissions were measured from the chemical recovery boiler
for particulate, sulfur dioxide, reduced sulfur compounds, oxides of
nitrogen, carbon dioxide, carbon monoxide, and oxygen. Emissions from
the first and second stages (individually vented) of the black liquor
oxidation system were also measured for sulfur dioxide and reduced
sulfur. The recovery boiler utilizes a cascade direct contact evaporator
and strong black liquor oxidation and exit gases are controlled with an
electrostatic precipitator.
Reduced sulfur compounds were measured by flame photometric gas
chromatography and coulometric titration. Carbon monoxide and carbon
dioxide were measured with infrared analyzers and oxygen was monitored
with a paramagnetic oxygen analyzer. All other stack emissions were
measured with .EPA reference methods.
1
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II. SUMMARY AND DISCUSSION OF RESULTS
Table 1 summarizes results of gaseous sulfur determinations
utilizing both flame photometric and coulometric detection systems.
All summary results are reported in terms of TRS as hLS. TRS is
defined as hydrogen sulfide plus methyl mercaptan plus dimethyl
sulfide plus dimethyl disulfide; all compounds are reported as hydrogen
sulfide. It should also be noted that dimethyl disulfide (RSSR) con-
centrations, determined with the chromatographic system, are assumed
to yield twice those concentrations when considered as hydrogen sulfide.
Complete gaseous sulfur data is contained in Appendix A.
Results from the particulate emission tests on the recovery
furnace are shown in Table 2. Emission rates were calculated on the
basis of the moisture content determined from a separate moisture test
instead of the condensed moisture in the impingers. The reason for
this is that the evaporation rate of the isopropanol in the impingers
was found to be excessive based upon previous tests.
The third and fourth impingers, which contained 3% hydrogen peroxide,
were analyzed for sulfur dioxide by using barium perchlorate titrations.
The data are also included in Table 2.
Complete particulate and sulfur dioxide data are contained in
Appendix B.
Daily mean concentrations for oxygen, carbon dioxide, and carbon
monoxide are presented in Table 3. The results are reported on a dry
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gas basis. Complete results of the gas concentrations at 15-minute
intervals are included in Appendix C.
The results from the nitrogen oxide emission testing are summarized
in Table 4. Complete NO data are included in Appendix B.
A
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Table 1
TRS DAILY AVERAGES
(Coulometric and Flame Photometric Detection)
U. S. PLYWOOD - CHAMPION PAPERS
Pasadena, Texas
Date
6-3-72
6-4-72
6-5-72
6-6-72
6-7-72
6-8-72
6-9-72
Source
PPT Outlet
PPT Outlet
PPT Outlet
PPT Outlet
PPT Outlet
PPT Outlet
1st Stage BLO (5)
2nd Stage BLO
Flame Photometric Detection
ppm (1)
2.02 (2)
1.41 (3)
1.40
1.54
0.77
1.58
38.90
23.25
Ibs/hr
1.54
1.06
1.06
1.16
0.58
1.20
1.21
0.62
Ibs/ADTP
Coulometric Detection
ppm
4.1
2.9
2.7
2.5
2.9
3.1
48.8
6.8
Ibs/hr
3.13
2.19
2.04
1.88
2.19
2.35
1.52
0.18
Ibs/ADTP
.
(1) Parts per million by volume - Dry Gas Basis
(2) H2S only
(3) RSR & RSSR
(4) }^S & RSH
(5) BLO - Black Liquor Oxidation
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• TABLE 2
PARTICULATE AND SULFUR DIOXIDE EMISSIONS
Date
Time Began
Time End
Barometric Pressure, In. Hg Absolute
Meter Orifice Pressure Drop, In.'H20
3
Vol. Dry Gas @ Meter Conditions, ft
Average Gas Meter Temperature, °F.
Vol. Dry Gas @ S.T.P.*, ft
Stack Gas Moisture, %,Volume
% C02
% 02
% CO
% N2
Average Stack Gas Temperature, °F.
Stack Pressure, In. Hg Absolute
Stack Gas Velocity @ Stack Cone!. ., fpm
Stack Gas Flow Rate @ S.T.P.", scfm
Net Time of Test, min.
Percent Isokinetic
Particulate Concentrations, grains/scf
Front half and Filter
Total
Particulate Emissions, Ibs/hr
Front half nnd Filter
Total
Particulate Emissions, Ibs/ton
Front half and Filter
1
S02 Emissions, Ibs/hr
Run #1
6/3/72
12:45
18:23
30
0.14
42.431
86
41.312
25.5
10.4
10.7
0
78.9
314.2
30.07
4633
141512
180
113.4
0.085
0.184
103.32
223.04
4.13
8.92
14.77
Run 12
6/5/72
9:25
13:05
30
0.14
42.530
87
41.333
25.3
10.7
11.4
0
77.9
304.2
30.07
4683.6
145321
200
99.4
0.096 •
0.199
110.07
248.18
4.40
9.93
63.82
Run #3
6/6/72
9:52
13:32
30
0.09
45.294
89
43.853
21.9
11.8
10.1
0
78.1
302.6
30.07
4554.1
148042
200
103.5
0.092
0.197
116.51
250.03
4.66
10.00
Neg.
i
Based upon 600 tons ADP/day
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Table 3
Carbon Dioxide, Oxygen, and Carbon Monoxide Concentrations
Date
6/3/72
6/4/72
6/5/72
6/6/72
6/7/72
6/8/72
Daily Averages
CO
(ppm) •
153
93
84
95
102
51
co2 %
10.4
8.2
10.7
11.8
12.9
11.1
o2 %
10.7
11.4
11.4
10.1
10.1
9.9
Table 4
Nitrogen Oxide Concentrations No. 6 Recovery Furnace Outlet
Date
6/3/72
6/5/72
6/6/72
Time
1605
1830
1400
1630
1700
1440
1535
1600
NOX, ppm
19.3
19.8
19.8
24.2
17.9
20.2
34.3
34.5
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III. PROCESS DESCRIPTION AND OPERATION
The Champion International Plant at Pasadena, Texas is a complete
mill, producing 600 tons of fine paper and newsprint per day from its
own bleached kraft pulp and groundwood. The EPA test program at
this mill was limited to two facilities; the black liquor oxidation
system, and the recovery furnace system. These systems are a small but
important part of the plant complex, and are part of the process for
recovering spent cooking chemicals from the kraft pulping operation.
Diagrams of both systems are shown in Figure 1.
Process Description
A. General
The mill produces kraft pulp by cooking wood chips in white liquor,
a water solution of sodium hydroxide and sodium sulfide. The spent
cooking solution, called black liquor, is treated to regenerate cooking
solution. During regeneration, the black liquor is concentrated in
evaporators and then burned in a recovery furnace. At the furnace bottom,
inorganic chemicals are recovered as a sodium carbonate-sodium sulfide
smelt. The molten smelt is tapped off and dissolved in water. The
resulting mixture, called green liquor, is drawn from the dissolving
tank and treated with lime to complete the regeneration of cooking
solution.
Heat released in the recovery furnace from combustion of the black
liquor is used to generate process steam and to complete the evaporation
of additional black liquor. The recovery furnace, sometimes called a
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Contact
Evaporator
iquor
Atnosphore
black liquor
let Sta-;-:
Oxidation
lc-ctrostot
'reel pita tor
black —
liquor
(oxidized)
Atmosphere
2nd Starjc
Oxidation
air
Stack
Figure 1 . Flov/ Oiagrar: of ".ocovary Furnace and Black Liquor .Oxidation
systo,.i.
8
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recovery boiler, employs water walls and boiler tubes to absorb part
of the available heat. Combustion gases leave the furnace at about
700°F and go to a direct contact evaporator; black liquor, fed counter-
currently to this unit, contacts the hot gases directly and is evaporated
to a solids content of about 60 percent. The concentrated liquor is
sprayed into the furnace; combustion gases leaving the direct contact
evaporator are cleaned in an electrostatic precipitator and then vented
to the atmosphere through a tall stack.
Chemical reactions between the combustion gases and black liquor
in the direct contact evaporator can generate hydrogen sulfide. To
inhibit these reactions the black liquor is first sparged with air in
a two stage oxidation system. Oxidation converts sulfide in the liquor
to thiosulfate and effectively reduces subsequent hydrogen sulfide
formation.
B. Recovery Furnace System
The test unit was installed in 1958 and designated the #6 recovery
furnace. This furnace was designed by Babcock and Nil cox for a heat
input of 575 million BTU per hour, equivalent to a pulp production rate
of 650 tons per day. Associated with this furnace is a cascade direct
contact evaporator.
A portion of the product steam is used to blow soot from the boiler
tubes. Tubes are cleaned continuously, one section at a time.
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C. Oxidation System
The oxidation system was designed by Champion to oxidize strong
black liquor by sparging with air in two sequential stages. The first
stage was installed in 1951 and the second stage in 1967." In each stage,
air is blown through the black liquor and vented through a cyclone to the
atmosphere. Number 2 heating oil is pumped to the second stage at about
15 gallons per hour to inhibit foaming, and each stage has a foam breaker.
Black liquor from the cyclones and foam breakers are recycled. The
oxidation system serves two recovery furnaces with a total equivalent
pulp production of 900 tons per day.
D. Electrostatic Preci pita tor
The precipitator was designed for a collection efficiency of 98 percent
and installed by the Koppers Company in 1958. Inlet gas is divided into
three parallel chambers, and each chamber has three fields. The inlet
fields of chambers 1 and 2 are coupled electrically; the center fields
of chambers 2 and 3 are also coupled. Accordingly, the precipitator has
seven separately controlled sections.
Rappers operate every 2 1/2 minutes; during each cycle the inlet
sections rap for 5 seconds, followed by the center sections for 10
seconds, and the outlet sections for 15 seconds. Salt cake drops to
the hoppers and is recycled to the recovery furnace by circulating
black liquor.
Process Operation
During testing, records were kept of process variables for the
recovery furnace, electrostatic precipitator, and the black liquor
10
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oxidation system. Wherever process monitors were available, operating
conditions that affect emission rates were recorded. The raw process data
sheets and a key explaining the entries are included in the Appendix D.
A. Recovery Furnace
The process records, as well as statements by the operators, indicate
that during the tests the recovery furnace was operated normally. The
observed ranges of major operating, variables are given in Table 5; where
information is available from the company, the design and normal values
are also shown. As seen from the table, black liquor feed rate, solids
content, and steam temperature, pressure, and production rate, were all
within a few percent of normal; reduction ratio was greater than 95 per-
cent, as proper. (Reduction ratio, determined from green liquor samples,
is the concentration of sodium sulfide divided by the sum of sodium
sulfide and sodium carbonate concentrations.) These records show that
the furnace received a normal charge and performed its major functions
(production of smelt and steam) in a normal way during the tests.
Many operating parameters (such as distribution of furnace combustion
air, manner of spraying feed liquor, etc.) affect furnace emissions. Those
that could be monitored were recorded. There is no indication from the
records or from operators' statements that unusual practices were followed.
The sodium sulfide concentration in black liquor fed to the direct
contact evaporator is a process variable of special interest, because of
its strong influence on the generation of hydrogen sulfide. Sulfide levels
are determined routinely by the Company and were made available for the
11
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test period. As shown in Table 6, sulfide levels were frequently unde-
tectable; the highest levels (June 5 and 6) caused no measurable increases
in hydrogen sulfide emissions.
B. Black Liquor Oxidation System
A limited amount of process data was obtained June 9 during tests on
the oxidation system. Readings of the available process monitors were
recorded on data sheets included in the appendix. These data are sum-
marized in Table 7.
As far as known from the process data and statements by the operators,
the oxidation system was operated normally during the test.
C. Electrostatic Precipitator
Precipitator operation was monitored during all the furnace tests.
Primary current, secondary current, and secondary voltage in each of the
seven control sections were recorded hourly. The raw data sheets are
included in the appendix. These data are summarized in Table 8; information
supplied by Champion International on design and normal operating conditions
is included where available.
During most of the particulate sampling the precipitator was operated
normally. The major exception occurred in the first run; during the last
hour of sampling, the primary current in one control section dropped
from about 78 to 46 amperes. (Particulate emissions, however, were
lowest for this run.) The second run was postponed a day until the
precipitator was repaired. When the faulty section was cleaned out
and several damaged collector plates were welded into place, normal
current was restored.
12
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Table 5. SUMMARY OF THE RECOVERY FURNACE PROCESS DATA
Operating Condition
Black Liquor Feed Rate
Black Liquor Solids
Content
(r)
Steam Production v;
Steam Temperature
Steam Pressure
Reduction Ratio'6'
Units
GPM
Wt. %
103 Ib/hr
°F
psig
x
Design^3
200(b)
67
299
750
375
During Item No.
\ Test on Data
' Normal 6/3-8/72 Sheets
208 214-223
65 64.2-66.5
225^ 200 - 255
700 670 - 750
330 321 - 357
95.7 - 97.1
10
14
1
4
5
^'Information supplied by Champion. International.
* 'Calculated by Champion International from design heat input using
current operating parameters.
(c)
v 'Net production, not including steam used for soot blowing in the
recovery furnace.
* 'Original design did not contemplate current rate of saturated steam
usage for soot blowing.
13
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Table 6. SODIUM SULFIDE CONCENTRATIONS IN BLACK LIQUOR FED
TO THE DIRECT CONTACT EVAPORATOR
Date
1972
3 -
4
4
5
5
6
6
i
i
7
3
9
Time
24 hour
1330
0700
1430
0730
1500
0745
1530
0645
0710
1315
0640
Sodim Sulfide^
gra^s/litcr
0.0
0.117
0.0
0.390
0.0
0.2£5
0.156
0,195
0.0
0.0
0.0
(a)
Determined by Champion International by potentiometric titration.
14
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Table 7. SUMMARY OF PROCESS DATA FOR THE BLACK LIQUOR OXIDATION SYSTEM
Stage 1
Operating Condition
Black Liquor Feed Rate
Air Feed Rate
Air Feed Pump Pressure
Units
GP;i
SCR!
psig
Design
535
6000
G
Morr.ial
542
During Test
(6/9/72)
350 - 500
not Measured
G 1/4 - G 1/2
Statie 2
1 \ "t \~
Air
Our inn last
Operating Condition
rr~~ j ^-4--,
t '*. v; o • \Lt vv-
Feed P-j.np Pressure
Units
CCF,I
PS13
Ocsiqn
3000
C
formal
(J/S/72)
nr\ t1 n,'i;i c : i r ••»."•
6 3/4
NOTE: Stage 2 liquor feed rate is not measured; it is slightly less than
stage 1 because of evaporative water losses in stage 1.
15
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Table 8. SUMMARY OF PROCESS DATA FOR THE ELECTROSTATIC PRECIPITATOR
Operating Condition
Gas Volume
Gas Temperature
Inlet Loading
Outlet Loading
Efficiency
Primary Current
Primary Voltage
Secondary Voltage
Secondary Current
Units
103 ACFM
°F
gr/SDCF
gr/SDCF
amps
volts
103 volts
Design
281
325-350
2.5-6.0
0.05^
98
90
440
65
Normal
265
325
4.0
97.5
85-95
45-60
During Test
6/3,5,6/72
273-281
303-314
0. 085-0. 096^
46 - 96(c)
310 - 400
325 - 490
(a)
(b)
(c)
Texas Air Control Board method; similar to EPA Method 5.
EPA Method 5; front half only.
Primary current in one control section was low for about 30 minutes;
minimum current at all other times during particulate testing was 70 amps.
16
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IV. LOCATION OF SAMPLING POINTS
The outlet stack from the electrostatic precipitator on the No. 6
recovery furnace was sampled at the rectangular duct entering tnto the
vertical stack, as shown in Figures 2 and 3.
The traverse points sampled in each of the four ports are as
follows:
Distance From
Sample Point No. Inside Hall, In.
1 5 3/4
2 17 1/4
3 28 3/4
4 40 1/4
5 51 3/4
6 63 1/4
7 74 3/4
8 86 1/4
9 97 3/4
10 109 1/4
NOTE: The traverse points were utilized for determination of particulates,
gas volumes, moisture and other necessary stack gas parameters.
The gaseous constituents were extracted from the source gas stream
based upon the assumption that the gases were homogeneously mixed.
Therefore, gaseous sulfurs, nitrogen oxides, carbon dioxide, oxygen
and carbon monoxide were sampled from relatively fixed points in
the gas handling system.
17
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Electrostatic
Precipitator
3-Ducts
Manifold
Four Participate
Sampling Ports
Gas Sampling
Ports
V
Stack
SIDE VIEW OF MO. 6 RECOVERY
FURNACE GAS OUTLET
Figure 2
6 I. 21" | 30" I 22" |S"
^^iro1 &~*y- f'~<^ ^-4'? •"••
6 6 (!) 6
Flow .
TOP VIEW OF PARTICULATE
SAMPLING PORTS
.Figure 3
18
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V. SAMPLING AND ANALYTICAL PROCEDURES
Chromatographic Sampling System
Figure 4 illustrates the ;ystem which v/as emoloyed in conveying
the gases from the source to the sensing equipment. The stainless steel
probe and Teflon sampling line were maintained at temperatures exceeding
the dew point of the source gases. The sampling line consisted of an
insu.lated, electrically heated 1/4-inch Teflon tube. The sample gases
were transmitted to the heated dilution box where they were split into
two separate streams. One stream was conveyed to the vacuum source and
wasted to minimize lag time in the sampling line. The remainder of the
flow was diluted with nitrogen by an amount sufficient to lower the dew
point of the gases below ambient temperature. A portion of this diluted
sample was injected into the chromatograph through the Gas/Liquid
Chromatograph (GLC) sampling valve. The remainder of the diluted gas
was wasted through the vacuum source.
Chromatographic Analysis
Gaseous sulfur concentrations were determined with a Tracer
Model 250 Gas/Liquid Chromatograph. This unit is equipped with a flame
photometric detector which is specifically for sulfur compounds. Two
analytical columns were utilized in the separation and analysis of the
gaseous sulfur compounds. One was a 36-foot by 1/8-inch OD Teflon
column packed with polyphenyl ether liquid phase on a solid support of
grannular Teflon with stripper column. The second column, constructed
of identical materials, v/as 8 feet long. Both columns were operated at
50°C.
19
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The 36-foot column was utilized for analyzing hydrogen sulfide,
sulfur dioxide, and methyl mercaptan while the 8-foot column facilitated
the analysis of dimethyl sulfide and dimethyl disulfide.
The chromatograph was calibrated for hydrogen sulfide, sulfur
dioxide, methyl mercaptan, dimethyl sulfide, and dimethyl disulfide,
using the spinning syringe technique.
20
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Stack
. XGlass
J\\ 7 Wool
Dilution
Nitrogen
Heated Sample
ne 4"Teflon
(_.J /.
GC GAS SAMPLING SYSTEM
Figure 4
~(5?) Carrier Gas
(N2)
Gas
Chromatograph
GC
Sampling Valve
Vacuum Pump
,M: Rotameter
><) : Metering Valve
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'•-• '.Couloinetric DatectoK.(Barton Titrator)
•;.'."'••'• Figure 5' illustrates the system which was employed in conveying
.",'• *'• "*•
/ ;..;;-
'•'•'.- the gases from the source to the Barton Titrator. The stainless steel
. probe and Teflon sampling line were maintained at temperatures exceeding
the dew point of the stack gases. The sampling line was the same as
the sampling line used with the GLC. The sample gases were transmitted
to the Barton Titrator by a vacuum source.
Barton Titrator
Total reduced sulfur (TRS) concentrations were analyzed using
a Barton Titrator, Model 400. Furnace gases were scrubbed through a
3% solution of potassium acid phthalate (KHP) which removes sulfur dioxide
and a large fraction of water vapor from the sample gases. The sample
gas was then introduced to a coulometric titration cell which utilizes
hydrobromic acid (HBr) as an electrolyte. The electrolytic cell
generates bromine from the HBr electrolyte which reacts with the
sulfur compounds entering the titration cell. The quantity of current
required to generate the excess bromine, to consume the sulfur compound,
is proportional to the gaseous sulfur concentrations introduced. The
current required to operate the titration cell is sensed and trans-
mitted to a recorder where a continuous readout is accomplished. The
recorded output is converted to TRS concentrations, as H?S from cali-
bration data generated with the "spinning syringe" technique.
22
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Glass Wool
Heated
Sample Line
1/4" Teflon
so2
Scrubbers
Data
Recorder
Barton
Titrator
BARTON SAMPLING SYSTEM
Figure 5
Flow
Meter
A
X"—>> Micro
f\'' jMetering
Vjyvalve
v
Vacuum Pump
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Sampling Procedure for Participate Emissions
Prior to performing the actual participate emission tests, certain
preliminary stack parameters had to be determined for the stack gases.
This preliminary data included the average stack gas temperature,
velocity head, moisture content, stack dimensions, and number of
sampling points.
The stack gas temperature was determined by using bimetallic ther- •
mometers and a pyrometer.
The approximate stack gas moisture content selected for setting
the nomograph was based upon previous tests made on the same boiler. The
final moisture content used in calculating the stack emissions from the
recovery furnace was based upon the amount of condensate collected in the
impingers and the silica gel from a separate moisture test.
The sampling points selected and tiie respective stack gas velocities
were determined by using Methods No. 1 and 2 of the Federal Register (Vol.
36, No. 247, December 23, 1971). Velocity head measurements were made by
using a calibrated S-type pi tot tube with an inclined manometer.
The sampling train configuration used during the tests consisted
of the following: a stainless steel nozzle; a heated glass-lined probe;
a heated glass-fiber filter; two Greenburg-Smith impingers with tips,
each containing 100 ml of 80% isopropanol; two Greenburg-Smith impingers
without tips, each containing 100 ml of 3% hydrogen peroxide; one
Greenburg-Smith impinger without a tip, containing about 200 grams
of silica gel; a flexible sample line; an air-tight vacuum pump; a
24
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dry-test meter; and finally a calibrated orifice with an inclined
manometer (see Figure 6). Velocity head measurements were conducted
simultaneously with the sampling at each point so that each point
could be sampled isokinetically.
The impinger portion fo the sampling train was feed down to
collect the condensables, and to determine the actual stack gas
moisture.
25
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3.
4.
5.
r,
10.
11.
12.
13.
14.
15.
16.
17.
18.
T ^
i .> •
20.
20
Stainless steel nozzle
Glass-lined probe (heated)
Heated box (250°F)
Glass-fiber filter and holder
Ice bath
Impingcr with Tip, 100 ml of 80% Isopropanol
Impinger vn'th Tip, 100 ml of 80% Isopropanol
Impinger without Tip,.100 ml of 3%
Impinger without Tip, 100 ml
n-c •?'•' u n
0 i o/j r>oUo
Inpinger' with 200 grams
of Silica Gel
Thermometer
Flexible sample line
Vacuum gauge
Coarse valve
Fine valve
Vacuum pump
Drg-test meter
Calibrated orifice
Inclined manometer
S-typs pi tot .tube
13
I n.
14
FIGURE 6 '
PARTICIPATE AND S02 TRAIN
-------
Samp 1 e Recovery and Ana 1 ys e s of Pa r 11 c u 1 ate s
Sample recovery from the particulate train was accomplished
by. separating train components into the following containers:
Container No. 1 - The previously weighed glass-fiber filter
was placed into this container, then sealed and labeled.
Container. No. 2 - All portions of the train from the nozzle
through the front half of the filter holder were rinsed with
acetone and the contents placed into a glass container, then
sealed and labeled.
. Container llo. 3 - The volume of liquid from the first and
second impingers was measured and the contents placed into
a glass container. Also, all sample-exposed surfaces between
the filter and third impinger were rinsed with 80;i isopro-
panol and placed into this Container, then sealed and labeled.
Container No. 4 - The volume of liquid from the third and
fourth impingers was measured and the contents placed into
separate glass containers. All glassware between the second
and fifth impingers was then rinsed with deionized, dis-
tilled water and then added to each respective container.
The liquid samples were then sealed and labeled. Only one
sample container was used for both impingers used in the
smelt dissolving tank sampling.
Container No. 5 - The previously weighed silica gel was re-
moved from the fifth impinger and placed into the original
polyethylene jar and sealed.
27
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:•..
The samples recovered were analyzed as follows:
Container No.. 1 - The filter and all loose material in the
sealed petri dish were transferred to a tare glass weighing
dish, desiccated, and dried to'a constant weight.
Container No. 2 - The acetone washings were transferred to a
tared beaker and evaporated to dryness at ambient temperature
and pressure. It was desiccated and dried to a constant weight.
Container No. 3 - The contents were transferred to a tared
beaker, and then evaporated at 212°F. The residue was desic-
cated and dried to a constant weight.
Container No. 4 - The liquid contents were shaken, and then
a 25 ml aliquot of each container was pipetted into separate
250 ml Erlennieyer flasks. One hundred ml of isopropanol,
plus two to four drops of thorin indicator was added to each
sample. The samples were titrated with barium perch!orate
to a pink end point. Another duplicate sample and blank was
titrated in the same manner as the first sample. Samples
were analyzed at the plant site.
Container No,. 5 - The spent silica gel was weighed at the site
and recorded.
The filter from Container No. 1, and the beakers from Containers
No. 2 and 3 for each run were sent to the EPA project officer after the
initial analysis for additional analyses.
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Sampling System for Oxygen, Carbon Dioxide, and Carbon Monoxide
Figure 7 is a schematic.'-diagram of the sampling system.
Source gases were drawn continuously through a glass-lined probe and
polyethylene tubing to a moisture trap consisting of silica gel im-
pingers immersed in an ice bath. Valves on the pressure side of the
vacuum pump controlled the flow"of sample gas to the detectors. A
bleed valve was provided to maintain adequate purging of the sample
line. Gases to the oxygen and carbon monoxide detectors were passed
through an ascarite bed to remove carbon dioxide which potentially
interferes with the HDIR determination of carbon monoxide. Sample to
the carbon dioxide detector v/as diluted with nitrogen to accommodate
the range requirements of the detector.
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From Stack
Ice Bath
Silica
Gel
Midget Impinger
w/Silica Ge"T
To COp System
~1
f Ascarite
Impinger
Vent~«—£>;
A
CO
Cal
Gas
Vent
-MX
A
co2
Cal
Gas
Bleed V
T
Vacuum Pump
To CO. On ,$_ystem
CO
NDIR
°2
Paramagnetic
Analv?er
Flowmeter
Dilution System
NDIR
C02, 02, and CO SAMPLING SYSTEM
Figure 7
Flow
—[Xh>
V.ent
Cal
Gas
-(X}>-Vent
Dilution
Nitrogen
30
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A Beckrcan model F-3 paramagnetic oxyg.cn analyzer capable of
measuring 0 - 25f= oxygen was used for. CL detection. Beckman NDIR
models 315-B and 315-A, respectively, were used in determining carbon
dioxide and carbon monoxide concentrations. The instrument configura-
tions were 0 - 5% CO,, and 0 - lOOOppm CO. All instruments were supplied
with a lov/, medium and high range which were calibrated separately. The
detectors were switched on and allowed to run continuously 24 hours per
day for the entire sampling interval.
Calibration
All calibration gases were supplied and analyzed by Matheson
Gas Products, Inc., Morrow, Georgia, and La Porte, Texas. The calibra-
tion procedure was conducted prior to sampling each morning and was re-
peated at the end of each day. Nitrogen was introduced into each
instrument and the zero control was adjusted to obtain a steady "zero
trace" on the recorder. Appropriate standards were then passed into
the instruments at less than 100 cc/minute. The gain controls for each
range were adjusted to provide maximum deflection and accuracy.
Daily Operation
Each morning after calibrating the instruments, charging the
traps, and checking the probe, the system was assembled as shown in
Figure >7. The dilution to the carbon dioxide detector was regulated
to provide an accurate deflection range at a total flow rate less than
100 cc/minute. Flows for sample gas and dilution nitrogen were measured
with a bubble tube. The recorder traces were observed and the ranges
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were adjusted throughout the sampling interval as required. Occasionally
sampling was interrupted to obtain odor samples, charge traps, or to
check the system.
Sampling Procedure for jiitrogen Oxides
Nitrogen oxide concentrations of the recovery furnace outlet gases
were determined by using the EPA Method 7, which is described in the
Federal Register (Volume 36, No. 247, December 23, 1971).
Essentially, the method consisted of collecting a grab sample of
the gas in an evacuated 2-liter flask containing a dilute sulfuric acid-
hydrogen peroxide absorbing solution. The sample remained in the flask
at least 16 hours, and was then placed in a glass storage bottle. Sodium
hydroxide (IN) was then added to the sample until alkaline. The samples
were taken back to the laboratory in Gainesville, Florida, and measured
colorimetrically using the phenoldisulfonic acid procedure.
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