United States
Environmental Protection
Agency
Environmental Sciences Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-78-126
July 1978
Research and Development
Analytical System
for Measuring
Malodorous
Compounds from
Kraft Mills
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are.
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4 Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8 "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion .ServJce,'. Springfield, Virginia 22161.
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EPA-600/2-78-126
July 1978
ANALYTICAL SYSTEM FOR MEASURING MALODOROUS
COMPOUNDS FROM KRAFT MILLS
by
James D. Mulik, Robert K. Stevens, and Ralph E. Baumgardner
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
-------
DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
ii
-------
ABSTRACT
Automated chromatographs equipped with flame photometric detectors were
developed for the qualitative and quantitative analysis of low- and high-
molecular-weight sulfur compounds in kraft mill effluents. One chromatograph
equipped with a Teflon column packed with Teflon and coated with polyphenyl
ether measured the following low-molecular-weight sulfur compounds: hydrogen
sulfide (H S), sulfur dioxide (SO ), methyl mercaptan (CH SH), ethyl mercaptan
(C2H5SH), dimethyl sulfide ((CH ) S) , and propyl mercaptan (C H SH). A second
chromatograph equipped with a Teflon column packed with Teflon and coated with
Triton X-305 measured the higher-molecular-weight sulfur compounds: butyl
mercaptan (C^H^SU), dimethyl disulfide ((CH ) S ), and dibutyl sulfide ( (C H ) S)
Kraft mill effluents containing sulfur species ranging in concentrations
from 5 ppb to percent levels were analyzed using a 6-stage dynamic dilution
system.
Sulfur emission data were collected from two kraft mills, one employing
strong black liquor oxidation and the other weak black liquor oxidation. Part
of the study was dedicated to determining the relationship between the total
gaseous sulfur and the individual sulfur compounds observed chromatographi-
cally. In most cases, more than 90 percent of the sulfur emitted from the
kraft mills studied was accounted for by chromatographically identified
compounds.
This report covers a period from 1969 to 1971 and work was completed as of
December 1972. For further information contact Robert K. Stevens, Environmental
Sciences Research Laboratory, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina 27711.
iii
-------
SECTION 1
INTRODUCTION
The growth of the kraft pulping industry has created a definite need for
more quantitative data on gaseous emissions from kraft paper mills. Previous
studies by Brink, Thomas, and Feuerstein (1) and Adams and Koppe (2) indicate
the complexity of identifying and measuring the pollutants generated by kraft
mill activities. Highly sophisticated and complicated analytical techniques
are necessary to quantitatively characterize these emissions. Vital to the
analytical systems used, is a detector that specifically senses sulfur, as the
characteristic, unpleasant, decayed-vegetable odor related to kraft mill
activities is produced by sulfur compounds. Adams and Koppe (2) and Brink
et al. (1) used the microcoulometric detector designed to measure sulfur
constituents specifically as they are eluted from a gas chromatographic col-
umn. Most gas chromatographic systems, however, have proven unreliable be-
cause many sulfur compounds (H_S, SO , and CH SH) are so reactive that they
fail to pass quantitatively through conventional gas chromatographic columns.
Koppe and Adams (3) reported gross losses of these compounds at concentrations
below 10 ppm. Walther and Amberg (4) described a process-chromatograph using
thermal conductivity and flame ionization detectors consecutively for sulfur
analysis. A thermal conductivity detector was required for fixed gases such
as H S and SO which have no flame ionization response. By amplifying the
thermal conductivity detector signal, Walther and Amberg were able to detect
concentrations of H S as low as 2 ppm. The flame ionization detector is
approximately a thousand times as sensitive as the thermal conductivity de-
tector and responds to all organic compounds.
-------
Stevens, Mulik, Krost, and O'Keeffe (5) reported on the first automated
gas chromatographic flame photometric analysis of sub-ppm levels of sulfur
compounds in the ambient air. This technology led to the development of
methodology for analyzing sulfur compounds in kraft mill effluents.
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SECTION 2
EXPERIMENTAL
The flame photometric detector for the analysis of sulfur compounds, as
described by the Draegers (6) in 1962, was used by Crider (7) in 1967 for
monitoring SO in animal exposure chambers. The flame photometric detector of
Brody and Chaney (8), shown in Figure 1, was used by Stevens et al. (5) for
the sub-ppm analysis of sulfur compounds in the ambient air. The flame
photometric detector measures sulfur compounds by detecting the chemilumines-
cent emission from the excited S molecules formed whenever sulfur compounds
are burned in a hydrogen-rich air flame. A narrow-band-pass interference
filter between the flame and the photomultiplier tube isolates a particular
band of the S emission at 394 mp. The interference filter virtually elimin-
ates interferences from sulfur-deficient constituents. Because only the
chemiluminescent emission above the flame is viewed, the background flame
noise is reduced.
The gas chromatographic flame photometric system shown in Figure 2 was
developed to measure low-molecular-weight sulfur compounds in kraft mill ef-
fluents. The analyzer consists of a Varian 122 gas chromatographic oven
(Varian Associates, Walnut Creek, California), a flame photometric detector
(Meloy Laboratories, Alexandria, Virginia), a power supply and electrometer
(Tracor, Austin, Texas), and a modified 10-part sliding plate valve (Beckman
Instrument Company, Fullerton, California) equipped with a 10-cc Teflon sample
loop, stripper column, and analytical column. The function of the stripper
column is to vent heavier sulfur compounds by backflushing, thereby prevent-
ing them from reaching the analytical column. The analytical column is 36-
foot by 0.085-inch I.D. Teflon tubing packed with 30/60 mesh Teflon and coated
with 10 grams of polyphenyl ether and 500 mg of orthophosphoric acid. The 2-
foot by 0.085-inch I.D. stripper column is packed with the same material as
3
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HEATED EXHAUST
H2
INLET
COLUMN
EFFLUENT INLET
INTERFERENCE
FILTER
PHOTOMULTIPLIER
TUBE
|Z HEATER
AIR INLET
Figure 1. Cross-sectional view of flame photometric detector.
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FLAME
PHOTOMETRIC
DETECTOR
CARRIER IN N2
HEATED
EXHAUST
NEEDLE
VALVES
SOLENOID
VALVES
15 MINUTE
INDUSTRIAL
CAM TIMER
SAMPLE IN
iiiiiiiiiiiiiiiiiiiiriiiiiiiiiin
STRIPPER
COLUMN
* 10 PORT
ESAMPLING
= VALVE
SAMPLE
VACUUM
DEENERGISED
POSITION
ANALYTICAL COLUMN
Figure 2. Automated gas chromatographic-FPD sulfur gas analyzer equipped with a pre-colnmn,
backflusing modifications, and a 36-foot by 0.085-inch Teflon column packed with
Teflon and coated with no.1 yphenyl ether.
-------
the analytical column. Two solenoids and an industrial cam timer automati-
cally actuate the valve at 10-minute intervals. The timing sequence to ac-
tuate the valve for sample injection, foreflushing, and backflushing is as
follows:
1. Valve is energized for 1 minute.
a. Sample is injected into stripper column and analytical column.
2. Valve is de-energized for 9 minutes.
a. Stripper column backflushes heavy sulfur compounds to vent
while the analytical column continues to be foreflushed.
b. Sample loop is refilled.
Th'j 10-part valve was modified to minimize the sample-to-metal contact
that can cause severe losses at levels below 10 ppm. The fittings on the
valve connecting the 1/16-inch pipe to the 1/8-inch tube were drilled out so
that the Teflon lines would go through the fitting and into the body of the
valve up to the Teflon slider, thus making the valve essentially all Teflon.
The column exit was also fitted into the base of the detector to further
minimize sample-to-metal interaction.
A chromatogram of a sub-ppm mixture of sulfur compounds which was ob-
tained using permeation tubes as a source of sulfur compounds is shown in
Figure 3. Hydrogen sulfide, sulfur dioxide, methyl mercaptan, ethyl mercap-
tan, dimethyl sulfide, and propyl mercaptan were resolved in 10 minutes on the
36-foot by 0.085-inch I.D. polyphenyl ether Teflon column. Chromatographic
conditions were as follows:
• Nitrogen carrier gas flow of 100 cc/minute.
• Detector temperature of 105°C.
• Exhaust temperature of 110°C.
• Column temperature of 50°C.
• Flame conditions: hydrogen flow of 80 cc/minute; oxygen flow of 20
cc/minute.
-------
4 KlO'9a
•» • —
0.24 ppm
S02
2x109,
0.17 ppm 0 18 pprr
CH3SCH3 C2H5SH
2x10 -9 a
0 ?4 ppni
C3H7SH
10
MINUTES
Figure 3. Chromatogram of a mixture of hydrogen sulfide, sulfur dioxide, methyl
mercaptan, dimethyl sulfide, ethyl mercaptan, and propyl mercaptan.
-------
The analytical system developed for the heavier sulfur compou >cls is shown
in Figure 4. A Teflon 6-port gas sampling valve (Chromatronix, Inc., 2743
Eighth Street, Berkeley, California), equipped with a 10-cc Teflon sample
loop, was used since backflushing was not necessary. The analytical column is
10-foot by 0.085-inch I.D. Teflon tubing packed with 30/60 mesh Teflon coated
with 10 percent Triton X-305. The lighter sulfur compounds emerge rapidly
from this column as one peak, followed by heavy sulfur compounds that elute
separately.
A chromatogram of a sub-ppm mixture of high-molecular-weight sulfur
compounds is shown in Figure 5. Butyl mercaptan, dimethyl disulfide, dipropyl
sulfide, and dibutyl sulfide were resolved in 10 minutes on the 10-foot by
0.085-inch I.D. Triton X-305 column. Chromatographic conditions were as
follows:
• Nitrogen carrier gas flow of 100 cc/minute.
• Detector temperature of 105°C.
• Exhaust temperature of 110°C.
• Column temperature of 70°C.
• Flame conditions: hydrogen flow of 80 cc/minute; oxygen flow of 20
cc/minute.
Teflon permeation tubes gravimetrically calibrated according to the
procedure of O'Keeffe and Ortman (9) were used as primary standards. The
permeation tube assembly is shown in the upper right of Figure 4. The instru-
ments were calibrated by injecting aliquots of an air stream flowing over the
tubes into the chromatographic column. The concentration of the sulfur com-
pound is inversely proportional to the air flow over the permeation tube.
When kraft mill stack effluents are sampled directly, special sampling
techniques are required to reduce losses due to the high moisture content and
the wide concentration range of the sulfur compounds present (ppb to percent
levels). Grimly, Smith, and Martin (10) designed and constructed a dynamic
8
-------
GAS
II SAMPLING
U) VALVE
PERMEATION TUBE
ASSEMBLY
HEATED EXHAUST
FILTER
D.C. POWER
SUPPLY
CHARCOAL
FILTER
PHOTOMULTIPLIER
TUBE
ELECTROMETER
AIR
SOURCE
Figure 4. Automated gas chromatographic-FPD sulfur gas analyzer equipped with a 6-port gas
sampling and a 10-foot by 0.085-inch Teflon column packed with Teflon coated with
Triton X-305. Also shown is the permeation tube sample dilution system.
-------
4x10-* a
0.22 ppm
CH3SSCH3
2x10-8 a
0.21 ppm
(C3H7)2S
2 x 10'8 a
0.18 ppm
Figure 5. Chromatogram of a mixture of propyl mercaptan butyl mercaptan,
dimethyl disulfide, dipropyl disulfide, and dibutyl sulfide.
-------
dilution system to bring the effluent samples into the inherently limited
dynamic range of the flame photometric detectors. The dynamic dilution system
is capable of diluting effluent samples from a 10-to-l dilution to a 10 -to-1
dilution.
To determine if the chromatographic peaks represent the total volatile
sulfur introduced into the chromatographs, a Meloy total sulfur analyzer
continuously monitored the diluted sample.
11
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SECTION 3
RESULTS AND DISCUSSION
SAMPLING
The chromatographs, sample dilution system and total sulfur flame
photometric detector were installed in a mobile laboratory, which was moved
first to a kraft mill employing the strong black liquor oxidation process and
then to a plant using the weak black liquor oxidation process.
Figure 6 is a diagram of a typical chemical pulping operation. The weak
black liquor oxidation plant investigated for this study differed slightly
from the typical plant in that the lime kiln had a separate stack vent. In
the strong black liquor oxidation pulping operation, the emission from the
lime kiln was vented through a scrubber and into the recovery stack. The
letters in Figure 6 designate the points where samples were extracted for
analysis. Samples from each emission point were pulled to the dilution ap-
paratus through a 250- by 1/4-inch heated Teflon line. The sampling line was
maintained at about 180°C to prevent sample condensation. The probe was fixed
into position in the emission-source gas stream and sampled at a flow rate of
50 liters per minute. Multiple measurements were made over a 3- to 4-hour
period at each sampling point to determine the extent of the variation in
concentration of the individual sulfur compounds with time. Wide variations
in concentrations of the major constituents were not observed in this study;
the data contained in Tables 1 through 4 can be considered typical.
12
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BLACK LIQUOR
OXIDATION
Cr. ' IQUOR
OXIDATluN
ELECTROSTATIC
PRECIPITATOR F2
DIRECT CONTACT
EVAPORATOR
MULTIPLE EFFECT
EVAPORATOR
\
Fl-
RECOVERY FURNACE
i
h
SCRUBBER
Jl
LIME KILN
DEMISTER
CAUSTICIZER
SMELT
TANK
riqure 6. Diagram of a typical chemical pulping operation. Letters
designate points where samples were extracted for analysis.
-------
TABLE 1. STRONG BLACK LIQUOR OXIDATION
Sample point
Black liquor
oxidation vent
Knotter vent
Brown- stock
washer vent
Brown-stock
seal— frank v^nt-
Figure _
^ . „, Concentration, ppm
tion scfm H S SO CH3SH CH3SCH3 CH3CH2CH2CH2SH CH3SSCH3 Compound X
A 6,000 9.0 1.27 18.75 7.35 - 0.35 0.22a
B n.d.b tr° tr tr 3.22 - 3.30 tr
C 37,800 tr .29 tr 2.34 - .75 tr
D 1,970 268 tr 18.30 305 - 48 1.87
Inlet to direct-
contact evaporator 1
n.d.
tr
244.0
.21
*-*uu-t.cu L.VJ ti.i-i.ei-i.
contact evaporator 2
Precipitator inlet G
Precipitator outlet
Smelt-tank vent H
Non-condensables
to lime kiln
Lime kiln
scrubber inlet 1
Lime kiln
scrubber outlet 2
n.d. tr 164.70 - - -22
72,000 - 164.70 - - -
G2 31,000 - 146.40 - - - .12
20,000 2.08 tr -
10 291.2 - 5,720.0 6,240.0 - 572.0 tr
14,000 30.0 tr - - -
17,000 103.7 32.94 - - -
Calculated as dibutyl disulfide
Not determined
Trace
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TABLE 2. WEAK BLACK LIQUOR OXIDATION
Sample point
Figure
designa- Flow
tion scfm
H2S
SO,,
Concentration, ppm
CH SH
CH 3CH CH CH CH CH2SH
CH SSCH Compound X
tn
Black liquor
oxidation vent
Washer head vent
Multiple effect
evaporator inlet
Multiple effect
evaporator outlet
Direct contact
evaporator inlet
Direct contact
evaporator outlet
Precipitator
inlet
Precipitaor
outlet
Smelt tank
after demister
Non-condensables
to lime kiln
Lime kiln
scrubber inlet
Lime kiln
scrubber outlet
A
C
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
15,000
n.d.
n.d.
18,000
tr
2.27
14,400
tr
0.28
1.20
100,000 1.28
143,000 1.52
4.0
16.25
70.50
1.20
tr
tr
tr
tr
1.20
3.38
13,500
9,500
1.20
0.448
0.96
1.20
19,800
tr
0.80
3.90
4,500
0. 384
tr
0. 384
14,400
tr
.28
tr
tr
tr
tr
tr
10.40
2.4
1,980
950
tr
tr
0.136
7,200
Not determined
o
Trace
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TABLE 3. WEAK BLACK LIQUOR OXIDATION KRAFT MILL
Sample point
Figure
designation
Total sulfur concentration, ppm
Gas
chromatography
Flame
photometric
detector
Black liquor
oxidation vent
Washer head vent
Multiple-effects
evaporator inlet
Multiple-effects
evaporator outlet
Direct-contact
evaporator inlet
Direct-contact
evaporator outlet
Precipitator
inlet
Precipitator
outlet
Smelt tank
after demister
Non-condensables
to lime kiln
Lime kiln
scrubber inlet
Lime kiln
scrubber outlet
12.4
12.3
29,880
14,950
1.50
2.80
1.7
2.5
7.7
41,400
16.3
70.5
17.0
12.4
17,100
15,250
1.80
1.80
1.1
1.3
7.2
39,600
16.3
70.5
16
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TABLE 4. STRONG BLACK LIQUOR OXIDATION KRAFT MILL
Sample point
Figure
designation
Total sulfur concentration, ppm
Gas
chromatography
Flame
photometric
detector
Black liquor
oxidation vent
Knotter vent B
Brown-stock
washer vent
Brown-stock
seal-tank vent
Inlet to direct-
contact evaporator 1
Outlet to direct-
contact evaporator 2
Precipitator
inlet 1
Precipitator
outlet :
Smelt-tank vent H
Non-condensables
to lime kiln
Lime kiln
scrubber inlet ]
Lime kiln
scrubber outlet '<.
37.0
11.0
3.40
643.0
244.0
165.0
165.0
146.0
2.10
73.0
11.0
4.20
624.0
195.0
153.0
134.0
171.0
2.60
30.0
137.0
23.0
110.0
17
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ANALYTICAL RESULTS
The principal emissions from the kraft mills employing the weak black
liquor oxidation process were hydrogen sulfide and methyl mercaptan. Trace
amounts, (that is, concentrations less than 5 ppb), of the following compounds
were also present: sulfur dioxide, dimethyl sulfide, butyl mercaptan, dimethyl
sulfide and an unknown sulfur compound. This unknown compound, (for this
text termed compound X), was the last to elute from the Triton X-305 column
and had a retention time of 17 minutes. Dibutyl disulfide (boiling point
226°C) had a retention time of 16 minutes on this column; therefore, the un-
known compound probably has a boiling point greater than 226°C, or it is an
extremely polar compound.
As noted in Tables 1 and 2, there was no chromatographic evidence of the
presence of a wide variety of sulfur compounds. In fact, the chromatograms
were so uncomplicated that, at least for these plants, hydrogen sulfide and
methyl mercaptan can be considered the only significant emissions. The un-
complicated nature of these emissions is important, as the correlation of
malodor with sulfur in the ambient air of this kraft mill cannot be totally
determined by a simple sulfide test, especially since the ratio of sulfide to
methyl mercaptan from the main recovery stack is roughly 1 to 1. Tables 2 and
3 list: (a) the sum of the sulfur emissions obtained by gas chromatography
from each sampling point; and, (b) the values obtained with the total-sulfur
flame photometric detector analyzer. With the exception of the measurements
made at the inlet to the multiple-effect evaporator, the gas chromatographic
and total-sulfur measurements were in close agreement. This indicates that
sulfur compounds identified chromatographically represent the majority of the
emissions. The discrepancy in the values obtained from the multiple-effects
evaporator may have been the result of sampling problems caused by the high
concentration of particles, water vapor, and organics.
The identified emissions from the strong black liquor oxidation process
are shown in Table 4. Sulfur dioxide and hydrogen sulfide represent the major
18
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pollutants emitted from this plant. Again, the chromatographic data were
relatively uncomplicated although measurable quantities of dimethyl sulfide
and dimethyl disulfide were emitted to the atmosphere from several vents.
DISPERSION CALCULATIONS
A measurement not made during these studies was the determination of the
concentrations of sulfur compounds downwind of the kraft mills. Although
these determinations were not made, estimates of the impact of emissions from
the recovery furnace stack and lime kiln stack can be made using Turner's
dispersion estimates (11). On the basis of Turner's calculations for a night-
time inversion, (wind speed 3 meters per second), the concentrations of the
sulfur dioxide, hydrogen sulfide and methyl mercaptan from the weak black
liquor oxidation and strong black liquor oxidation kraft mills were determined
and are listed in Table 5. Based on these estimates, the concentration of the
sulfur gases in the ambient air 6000 meters from the source, indicates that
the malodor impact of these gases would be negligible.
The total malodor impact of a kraft mill on the surrounding community can
only be determined, however, by chromatographic measurements of the sulfur
gases downwind of the plant. These determinations are necessary because a
typical kraft mill is comprised of many separate point sources, some emitting
only two or three sulfur compounds while others emit a variety of inorganic
and organic sulfur species.
19
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TABLE 5. ESTIMATE OF ATMOSPHERIC DISPERSIONS OF
SULFUR GAS FROM KRAFT MILLS
Strong black liquor oxidation
Source concentration, ppm Estimate of abmient concentration, ppm
Emission
source
so.
SO,
Recovery
furnace
stack
146
0.004
Lime kiln
103
33
0.001
0.001
Weak black liquor oxidation
Source concentration, ppm Estimate of ambient concentration, ppm
Emission
source
CH SH
CH SH
Recovery
furnace
stack
1.52
0.96
0.001
0.001
Lime kiln
70.50
0.017
20
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REFERENCES
1. Brink, D.L., J.F. Thomas, and R. Feuerstein. Malodorous Products from
the Combustion of Kraft Black Liquor. Tappi, 50(6):276-285, 1967.
2. Adams, D.F., and R.K. Koppe. Direct GLC Coulometric Analysis of Kraft
Mill Gases. J. Air Pollu. Control Asso., 17 (1):161-165, 1967.
3. Koppe, R.K., and D.F. Adams. Evaluation of Gas Chromatographic Columns
for Analysis of Subparts per Million Concentrations of Gaseous Sulfur
Compounds. Environ. Sci. Technol., 1:479-481, 1967.
4. Walther, J.E., and H.R. Amberg. Mobile Laboratory for Source-Sampling
Kraft Mill Emissions. Tappi, 51(11):126A-129A, 1968.
5. Stevens, R.K., J.D. Mulik and A.E. O'Keeffe. Gas Chromatography of
Reactive Sulfur Gases in Air at the Parts per Billion Level. Anal.
Chem., 43(6):827-831, 1971.
6. Draeger, B., and H. Draeger. West German Patent 1-33918. Patent Date
July 1962.
7. Crider, W.L. An Automatic Flame Emission Instrument for Selectively
Monitoring SO in Animal Exposure Chambers. In: Proceedings of the
12th Annual Analysis Instrumentation Symposium, 1966. pp. 67-73.
8. Brodey, S.S., and J.E. Chaney. Flame Photometric Detector. The
Application of a Specific Detector for Phosphorus and for Sulfur Com-
pounds Sensitive to Subnanogram Quantities. J. Gas Chromatogr.,
4(2):42-46, 1966.
21
-------
9. O'Keeffe, A.E., and G.C. Ortman. Primary Standards for Trace Gas
Analysis. Anal. Chem. , 38 (6) -.160-763, 1966.
10. Grimley, K.W., Jr., W.S. Smith and R.M. Martin. The Use of a Dynamic
Dilution System in the Conditioning of Stack Gases for Automated
Analysis by a Mobile Sampling Van. Presented at 63rd APCA Meeting,
St. Louis, Missouri, June 1970.
11. Turner, D.B. Workbook of Atmospheric Dispersions Estimates.
Public Health Service, Publication No. 99-AP-26, Revised 1969.
12. Lindvall, T. On Sensory Evaluation of Odorous Air Pollutant Intensities,
Nordisk Hygienisk Tidschrift, Supplementum 2. Karolinska Institutet,
National Institute of Public Health, No. 5-104-01, Stockholm, Sweden,
1970.
22
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1. REPORT NO.
EPA-600/2-78-126
3. RECIPIENT'S ACCESSION NO.
4. TITLE ANDSUBTITLE
ANALYTICAL SYSTEM FOR MEASURING
MALODOROUS COMPOUNDS FROM KRAFT MILLS
5. REPORT DATE
July 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
J. D. Mulik, R. K. Stevens and
R. E. Baumgardner
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Environmental Sciences Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
10. PROGRAM ELEMENT NO.
1AD712
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Final
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Automated chromatographs equipped with flame photometric detectors were
developed for the qualitative and quantitative analysis of low- and high-
molecular-weight sulfur compounds in kraft mill effluents. One chromatograph
equipped with a Teflon column packed with Teflon and coated with polyphenyl
ether measured the following low-molecular-weight sulfur compounds: hydrogen
sulfide (H2S), sulfur dioxide (S0?), methyl mercaptan (CH^SH), ethyl mercaptan
(C2HrSH), aimethyl sulfide ( (CrL)?S), and propyl mercaptan (C-H?SH). A second
chromatograph equipped with a Teflon column packed with Teflon and coated with
Triton X-305 measured the higher-molecular-weight sulfur compounds: butyl
mercaptan (C.HgSH), dimethyl disulfide ( (CH-)?S2), and dibutyl sulfide ( (C.Hq)~S)
Kraft mill effluents containing sulfur Species ranging in concentrations
from 5 ppb to percent levels were analyzed using a 6-stage dynamic dilution
system.
Sulfur emission data were collected from two kraft mills, one employing
strong black liquor oxidation and the other weak black liquor oxidation. Part
of the study was dedicated to determining the relationship between the total
gaseous sulfur and the individual sulfur compounds observed chromatographi-
cally. In most cases, more than 90 percent of the sulfur emitted from the
kraft mills studied was accounted for by chromatograDhicallv identified compounds.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
* Air pollution
* Sulfur inorganic compounds
* Sulfur organic compounds
* Sulfate pulping
* Chemical analysis
* Chromatography
b.IDENTIFIERS/OPEN ENDED TERMS
COSATI 1'ield/Group
13B
07B
07C
13H
07 D
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19 SECURITY CLASS (This Report!
UNCLASSIFIED
21. NO. OF PAGES
27
20. SECURITY CLASS iThi
UNCLASSTFTFD
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION .s OBSOLETE
23
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