Projeet No. 76-CBK-5
CD
o
PHILLIPS PETROLEUM COMPANY
Toledo Phil black Plant
(> :
Toledo, Ohio
June 1976
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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EMISSION TEST REPORT
EMB Project No 76CBK5
Phillips Petroleum Company
Toledo Philblack Plant
Toledo, Ohio
Environmental Protection Agency
Office of Air Quality Planning and Standards
i
Research Triangle Park, North Carolina 27711
June 1976
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TABLE OF CONTENTS
SECTION TITLE PAGE NO.
I. Introduction 1
II. Summary of Results 2
III. Process Description and Operation 5
\
IV. Sample Locations 8
V. Sampling and Analytical Procedures 11
APPENDIX
A. Sample Calculations
B. Field Data
C. Test Log
D. Project Participants
LIST OF TABLES
Title Page No.
Table II-l: Summary of Results 3
Table III-l: Line 1 Operating Parameters 7
LIST OF FIGURES
Title
Figure IV-1: Sample Location, No. 1 Boiler 9
Figure IV-2: Sample Location, No. 1 Combustion Furnace 10
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I. INTRODUCTION
Under the Clean Air Act of 1970 as amended,-the Environmental
Protection Agency is charged with the establishment of standards of
performance for new or modified stationary sources which may contribute
significantly to air pollution. A performance standard is based on
the best emission reduction systems which have been shown to be
technically and economically feasible.\
In order to set realistic performance standards, accurate data
on pollutant emission is usually gathered from the stationary source
category under consideration.
The Toledo Phil back Plant of Phillips Petroleum Company at
Toledo, Ohio is equipped with process off-gas combustion devices and
was selected for an emission testing program. Testing was performed
by Emission Measurement Branch personnel on December 10, 1975.
Lists were performed after the No. 1 off-gas boiler and after
the Number 1 drier combustion furnace. Samples were collected to
determine carbon monoxide concentrations, carbon dioxide content, and
oxygen levels in each of the two exhaust streams.
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II. SUMMARY OF RESULTS
A total of six samples were collected at this facility; three at
each test location. Each test was of 1-hour duration. Analysis of
the samples was performed approximately 3 hours after collection. The
sampling locations and sampling and analytical procedures are described
in sections 4 and 5 respectively.
The results of testing are presented in Table I. The carbon
monoxide concentrations found in the No. 1 CO-boiler flue gases averaged
124 ppm by volume on a dry basis. The carbon dioxide and oxygen con-
tents are also given in Table I.
The carbon monoxide concentration in the No. 1 Drier Combustion
Furnace off-gases was less than detectable on the lowest instrument
range available, which was 0-500 ppm. It is estimated that the minimum
concentration detectable is 10 ppm. Therefore, the results are reported
as "not detectable" or "less than 10 ppm by volume, dry basis. Carbon
dioxide and oxygen contents are also reported in Table I for this unit.
It can be observed that there was a definite change in the carbon
dioxide and oxygen concentrations in the exhaust gases from both units
during run number 3, as compared to the results obtained in runs 1 and 2.
Since the samples with the same numbers were collected essentially
simultaneously at each source, the change in fixed gases during run 3
suggests that there may have been a change affecting the process off-gas
(fuel) quality. However, there was no appreciable change in the carbon
monoxide concentration in the Boiler flue gas.
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Table II-l. SUMMARY OF TEST RESULTS
Boiler No. 1
Combustion Furnace No. 1
Run No.
bate
Time
ppmv CO, dry basis
% C02 by NDIR
% C0£ by gas chromatography
% 02 by GC
B-l
12/10
1410-
1510
128
12.0
11.1
5.4
B-2
12/10
1518-
1619
123
12.0
11.4
5.2
B-3
12/10
1623-
1723
120
11.4
10.7
10.5
AVG
124
D-l
12/10
1415-
1515
ND
11.7
10.6
7.3
D-2
12/10
1515-
1615
ND
10.0
-11.5
8.1
D-3
12/10
1615-
1715
ND
8.1
9.8
10.1
AVG
ND
ND = <10 ppm
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Process parair.Aers as recorded during the testing are presented
in Section 3. There were no known process or control unit malfunctions
that would have had an effect on the emissions during testing.
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III. PROCESS DESCRIPTION AND OPERATION
°*.
The fundamental steps in carbon black manufacturing by the furnace
process are as follows:
A. Production of the black from feedstock.
B. Separation of the black from the gas stream.
C. Final conversion of the black to a marketable product.
In the furnace process, carbon black is produced by burning heavy
aromatic oil with a limited supply of combustion air. The feed oil is
preheated and injected into a reactor that has been heated by a natural
gas or oil. The flue gases and entrained carbon from the reactor (furnace)
are cooled by water quench and heat exchange against the reactor feed.
This stream is then sent to bag filters for carbon black recovery. The
recovered carbon black is transported to a finishing area by screw or
pneumatic conveyors. In the finishing area the black is passed through a
pulverizer to break up lumps. This produces a 5 to 12 Ib/cu. ft. bulk
density. In order to obtain a marketable material that can be transported,
the carbon black is converted into pellets or beads with a 20 to 35 Ibs/cu.
ft. bulk density. This pelletizing is done with water in a paddle or pin
type mixer. The resulting wet product is sent to driers. The dried product
is then screened and sent to storage.
The Phillips Petroleum Company, Toledo, Ohio plant was source tested
April 9-12, 1973, by an EPA contractor (Test report number 73-CBK-T).
Although the basic plant has remained as it was at that time, many changes
have been made to decrease the natural gas usage of the plant. The plant
is becoming as fuel efficient as possible, and is converting its operations
from natural gas to oil.
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The Toledo Philblack plant has two independent process lines. The
off-gases are combusted in two parallel CO-boilers and two indirect
combustor driers. If the total heat available in the off-gas stream were
used for these purposes, more steam would be generated than could be used
in the plant. Although the plant has an incinerator for combusting any
excess off-gas, it is no longer in operation.
The equipment tested was the No. 1 COrboiler and the No. 1 indirect
combustor dryer furnace. The boiler was a standard Babcock and Wilcox
small-tube, twin drum, water-tube boiler, with water cooled combustion
chamber. The boiler is designed to produce 45,000 Ib/hour of 400 psig,
650°F steam.
The operating parameters of the Lime 1 boiler and dryer combustion
furnace were monitored during testing and are shown in Table 4-1. According
to the operator the plant was running normally throughout testing.
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Table -.1-1. LINE 1 OPERATING PARAMETERS
Run No.
Date
Steam Flow (Ib/hr)
Steam Temp. (°F)
Boiler Press, (psig)
Header Press, (psig)
Outlet Gas Temp. (°F)
1
12-10-75
33,000
674
385
391
589
2
12-10-75
32,700
677
377
391
590
3
12-10-75
32,800
675
379
391
592
Average
32,800
675
381
391
590
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IV. SAMPLE LOCATIONS
"i>
The sampling location at the No. 1 CO Boiler is shown in
Figure IV - 1. The samples were extracted from ports in the boiler
exit breeching prior to the stack to atmosphere. The sampling
location at the No. 1 Combustion Furnace is shown in Figure IV - 2.
This sample was withdrawn through a sample tap normally used for the
plant carbon monoxide measurement system, but was disconnected for
sampling access. The tap is located in the combustion furnace flue
prior to the drier inlet manifold.
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. I
S/1HPL6
, A/0.
10
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V. SAMPLING AND ANALYTICAL PROCEDURES
Sampling was conducted according to the integrated bag procedure
given in Method 10 (FR v. 39 n. 47 March 8, 1974). The sample was
withdrawn from the respective port or sample tap through stainless
steel and/or teflon tubing. The sample was passed through a drying
tube containing Drierite*, through a leakless diaphram pump and rota-
meter, and finally into flexible tedlar bag. After the 1-hour sampling
period was complete, the bag was sealed and stored for transport to
the analysis location.
Analysis was performed approximately 3 hours after sample collection.
Carbon monoxide was determined according to Method 10 using a Beckman
Model 315A NDIR. Carbon dioxide was determined using a Beckman Model 315A
NDIR and also by a Fisher Model 29 Gas Partitioner. This unit is a gas
chromatograph equipped with a molecular sieve column for component separa-
tion and a thermal conductivity detector. Oxygen was also determined
using the Gas Partitioner.
*trade name
n
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APPENDIX A
SAMPLE CALCULATIONS
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SAMPLE CALCULATIONS
1. A calibration is prepared by passing zero gas and span gas
through the analyzer and adjusting the response to that
given by the manufacturer's supplied calibration curve.
2. To determine the CO concentration on a dry, C00 free basis,
the response of the instrument for a sample is compared to the
calibration curve and the corresponding concentration is found
3. To convert to an actual gas basis.
CCO STACK = CCONDIR ^ " FCO^
where
CCQ CTAQK = Carb°i'! monoxide concentration in stack, ppmv, dry \
= Carbon monoxide concentration measured by NDIR,
= Volume Fraction COp in stack
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APPENDIX B
FIELD DATA
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131
DRY MOLECULAR HEIGHT DETERMINATION
PLANT.
DATE.
?£
COMMENTS:
SAMPLING TIME (24-hr CLOCKS £ ' 1° ~3V/O P/T\
SAMPLING LOCATION />?// irtf
SAMPLE TYPE (BAG, INTEGRATED, CONTINUOUS).
ANALYTICAL METHOD
AMBIENT TEMPERATURE.
OPERATOR T^A V/5
\, RUN
GAS ^\^
C02
0 2 (NET IS ACTUAL 02
READING MINUS ACTUAL
C02 READING)
CO(NET IS ACTUAL CO
READING MINUS ACTUAL
02 READING)
N2 (NET IS 100 MINUS
ACTUAL CO READING)
1
ACTUAL
READING
674
r7a
2/./«₯
IV
NET
XR
33
2
ACTUAL
READING
NET
3
ACTUAL
READING
NET
AVERAGE
NET
VOLUME -
MULTIPLIER
44/ioo
i
i
32/100
'" J
Z8/ioo
28/ioo
TOTAL
MOLECULAR WEIGHT OF
STACK GAS (DRY BASIS)
f,ld, Ib/lb-rnole
ll.it, l/lW
Gt~. 1
5.kl "
ms PP#
EPA (Dur) 230
4/72
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DRY MOLECULAR WEIGHT DETERMINATION
PLANT Thl/LL/9.5 /?fl Mbit
DATE
, O/4
/o
COMMENTS:
SAMPLING TIME (24-hr CLOCK)
SAMPLING LOCATION
3 I / f ~ 4~ '//
t?>O I L £31
SAii'.PLE TYPE (BAG, INTEGRATED, CONTINUOUS).
ANALYTICAL METHOD
AMBIENT TEMPERATURE.
OPERATOR
^^^ RUN
GAS ^\
C02
02 (NET IS ACTUAL 02
READING MINUS ACTUAL
C02 READING)
CO(NET IS ACTUAL CO
READING MINUS ACTUAL
02 READING)
^2 (NET IS 100 MINUS
ACTUAL CO READING)
1
ACTUAL
READING
#u
rnGf
/- '"Jtl,^
6-P
32.5
j/?
NET
$3
ZR
2
ACTUAL
READING
NET
3
ACTUAL
READING
NET
AVERAGE
NET
VOLUME
MULTIPLIER
4Vioo
I '
32/100
I
28/ioo
28/100
TOTAL
MOLECULAR WEIGHT OF
STACK GAS (DRY BASIS)
IYid, Ib/lb-mole
1 1,^7A ll,o%
\ j./-?
W %"
IUO '?//
EPA (Out) 230
4 m
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DRY MOLECULAR WEIGHT DETERMINATION
PLANT
DATE.
COMMENTS:
SAMPLING TIME (24-hr CLOCK)
SAMPLING LOCATION
S~)U r/ <~
SAMPLE TYPE (BAG, INTEGRATED, CONTINUOUS).
ANALYTICAL METHOD
AMBIENT TEMPERATURE.
OPERATOR
\. RUN
GAS ^\
C02
02 (NET IS ACTUAL 02
READING MINUS ACTUAL
C02 READING)
CO(NET IS ACTUAL CO
READING MINUS ACTUAL
02 READING)
^2 (NET IS 100 MINUS
ACTUAL CO READING)
1
ACTUAL
READING
7
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DRY MOLECULAR WEIGHT DETERMINATION
PLANT
DATE
9K;\\n
COMMENTS:
1 ?/ i,;l -7 T
SAMPLING TIME (24-hr CLOCK).
SAMPLING LOCATION __jiij_
SAMPLE TYPE (BAG, INTEGRATED, CONTINUOUS).
ANALYTICAL METHOD *''-^M (<
AMBIENT TEMPERATURE
OPERATOR
3 a
^^^^ RUi^
GAS ^^^^
C02
Q£ (NET IS ACTUAL 02 "
READING MINUS ACTUAL
C02 READING)
CO(NET IS ACTUAL CO
READING MINUS ACTUAL
02 READING)
N 2 (NET IS 100 WIN US
ACTUAL CO READING)
1
ACTUAL
READING
si.i^
CP
L o- Jxw
c-r
o
i(\
NET
72
TR
2
ACTUAL
READING
NET
3
ACTUAL
READING
NET
AVERAGE
NET
VOLUME
MULTIPLIER
44/ioo
1
32/100
_ I
28/100
28/ioo
MOLECULAR WEIGHT OF
STACK GAS (DRY BASIS)
Md, Ib/lb-mole
11,71
to, C ?<
XR
7.3 7.
o .
IK
TOTAL
EPA (Dur) 230
4/72 ..
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£-2-
DRY MOLECULAR WEIGHT DETERMINATION
\T- ion s"
PLANT_
DATE
SAMPLING TIME (24-hr CLOCK).
SAMPLING LOCATION Jj- 1
SAV.PLE TYPE (BAG, INTEGRATED, CONTINUOUS).
ANALYTICAL METHOD ^ ° "v
AMBIENT TEMPERATURE_
OPERATOR Kt\VM
COMMENTS:
\. RUN
GAS ^\
C02
02 (NET IS ACTUAL 02
READING MINUS ACTUAL
C02 READING)
CO(NET IS ACTUAL CO
READING MINUS ACTUAL
02 READING)
1^2 (NET IS 100 MINUS
ACTUAL CO READING)
1
ACTUAL
READING
§^m
£ P
^20
'
C-P
O
if\
NET
fTC
J-f\
2
ACTUAL
READING
NET
3
ACTUAL
READING
NET
AVERAGE
NET
VOLUME
MULTIPLIER
44/100
1" "
32/iOO
_ _i
28/ioo
Jfl
a/m
MOLECULAR WEIGHT OF
STACK GAS (DRY BASIS)
iil^, Ib/lb-tnole
//,$% (Or7
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DRY MOLECULAR WEIGHT DETERMINATION
PLANT.
DATE_
COMMENTS:
\
SAMPLING TIME (24-hr CLOCK).
SAMPLING LOCATION j+ I
AC'S- 171
er
SAMPLE TYPE (BAG, INTEGRATED, CONTINUOUS).
ANALYTICAL METHOD K.'Oll1.
AMBIENT TEMPERATURE_
OPERATOR \4" IIH
\^ RUN
GAS ^^"\
C02
O£(NET is ACTUAL o2
READING MINUS ACTUAL
C02 READING)
CO(NET IS ACTUAL CO
READING MINUS ACTUAL
02 READING)
N 2 (NET IS -100 MINUS
ACTUAL CO READING)
1
ACTUAL
READING
C-P
LjO.O
0
In
NET
(c-V
I/?
2
ACTUAL
READING
NET
3
ACTUAL
READING
NET
AVERAGE
NET
VOLUME
MULTIPLIER
44/ioo
1 ~"
32/100
I
28/100
28/100
TOTAL
MOLECULAR WEIGHT OF
STACK GAS (DRY BASIS)
Md, Ib/ib-mole
' G-P i Ift
10,1%
0
it
EPA (Dur) 230
4.^72
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park, N.C. 27711
SUBJECT: Analysis of Cylinder Samples DATE: NOV. 21, 1975
FROML Berne I. Bennett, QAB/EMSL/RT/^/jfj/^
TO: Mr. Thomas J. Logan, ESED, M.D. #19
We have analyzed your three cylinders and find the CO concentration
to be as follows:
\
Cylinder CO concentration, ppm
111 78 216
LL170 531
LL181 537
cc: T. A. Clark
J. B. Clements
EPA Form 1320-6 (Kay. 6-72)
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. . \r ;<->) p i > '~0
- ' '>.
P 0.
S.O.
315 A
20525
'1 t *» /*
j u u I1 o
D.S.P.IL
Cincinj-jali, Ohio
Carbon Dioxide
200U34 ,.,.-.,
l\'iiro[;'on c ^i.-
Sec Manual c,,',;
0-20'/o by volume
210 3 A
A Lniospheric
A {.ir.osi'l'ieri c
PERCENT C02 IN N2 BY. VOLUME
-------
v /c < i" ~r* i "tin
.H. '3*H A'.D :C'H '. %' "CS'L^.VFiV tZ.r':~.f
-------
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5TH. 1CTK AND2Cfrii:SF PEOGSESSIVEIY ACCCN'TED
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APPENDIX C
TEST LOG
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TEST LOG
December 10, 1975
1100: arrive plant and begin setup.
1410 - 1510: Test B-l, Boiler exhaust
1415 - 1515: Test D-l, Furnace exhaust
1518 - 1618: Test B-2
1515 - 1615: Test D-2
1623 - 1723: Test B-3
1615 - 1715: Test D-3
1900 - 2030: Instrument Calibration and Sample Analyses,
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APPENDIX D \
PROJECT PARTICIPANTS
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PROJECTS PARTICIPANTS
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
TEAM LEADER: WINTON KELLY
JOHN DAVIS
RAYMOND MOBLEY
PROCESS ENGINEER: K. C. HUSTVEDT
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