United States Office of Air Quality EMB Report No. 81-PMR-1
Environmental Protection Planning and Standards March 1982
Agency Research Triangle Park NC 27711
&EPA Polymers and Resins
Organic Compound
Emissions from Incineration
Emission Test Report
ARCO Chemical Company
LaPorte Plant
Deer Park, Texas
Volume I: Summary of Results
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DCN #82-222-018-07-06
POLYMERS AND RESINS
VOLATILE ORGANIC COMPOUND
EMISSIONS FROM INCINERATION
EMISSION TEST REPORT
ARCO CHEMICAL COMPANY
LAPORTE PLANT
DEER PARK, TEXAS
VOLUME 1: SUMMARY OF RESULTS
FINAL REPORT
EPA Contract No. 68-02-3542
Work Assignment 07
ESED 78/24
Prepared for:
Winton Kelly
U.S. Environmental Protection Agency
- ESED/EMB (MD-13)
Research Triangle Park, North Carolina 27711
Prepared by:
K.W. Lee, C.J. Thielen,
D.L. Lewis, J.L. Randall, J.R. Boettcher and
Program Manager - J.W. Kamas
Radian Corporation
8501 Mo-Pac Boulevard
Austin, Texas 78759
31 March 1982
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TABLE OF CONTENTS
Section Page
LIST OF TABLES vi
LIST OF FIGURES ix
ACKNOWLEDGMENT x
GLOSSARY OF ACRONYMS xi
1.0 INTRODUCTION 1
2.0 SUMMARY OF RESULTS 4
2.1 Destruction Efficiencies 4
2.2 Process and Gas Phase Data o
2.3 Composition of Atactic Waste and NOx Levels 12
3.0 PROCESS AND INCINERATOR DESCRIPTIONS 16
3.1 Process Description 16
3.2 Incinerator Description 17
4.0 SAMPLING METHODOLOGY 23
4.1 Description of Sampling Points 23
4.1.1 Incinerator Inlet 23
4.1.2 Waste Heat Boiler Outlet 25
4.1.3 Scrubber Stack Outlet 25
4.2 Volatile Organic Carbon Sampling Methods 25
4.2.1 EPA Method 25 25
4.2.2 Proposed EPA Method 18 26
4.2.3 Byron Method 30
4.3 NDx Sampling at Waste Heat Boiler Stack 31
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TABLE OF CONTENTS (Continued)
Section Page
4.4 Scrubber Stack Volumetric Flow Rate 33
4.5 Flue Gas Molecular Weight and Flue Gas Moisture 33
4.6 Atactic Waste Sampling 35
4.7 Waste Gas Stream 37
4.8 Natural Gas 37
4.9 Miscellaneous Readings 37
5.0 ANALYTICAL METHODOLOGY 39
5.1 Gas Analysis 39
5.1.1 Proposed Method 18 for Hydrocarbons ........ 39
5.1.2 Byron Total Hydrocarbon Analyzer 41
5.1.3 Volatile Organic Compounds (VOC's) - EPA Method 25 . 42
5.1.4 Hydrocarbon Speciation 42
5.1.5 Fixed Gases 43
5.1.6 NOx 44
5.1.7 BGI Filters 44
5.2 Aqueous Condensate Analysis . 45
5.2.1 Total Organic Carbon (TOG) 45
5.2.2 Inorganic Species 46
5.3 Atactic Waste Analysis 47
5.3.1 Ultimate, Proximate, Btu Content .... 47
5.3.2 Moisture 47
iii
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TABLE OF CONTENTS (Continued)
Section Page
6.0 QUALITY ASSURANCE 48
6.1 Summary of Audit Results and Conclusions 48
6.2 Systems Audit - Approach and Conclusions 51
6.3 Performance Audit 53
6.3.1 Methods for Quantitation of Accuracy and Precision. . 54
6.3.2 Quantitation of Data Quality 60
7.0 RESULTS 82
7.1 Gas Phase Data 82
7.1.1 Volatile Organic Carbon (VOC) Measurement 87
7.1.2 Hydrocarbon Speciation Results 90
7.1.3 Fixed Gases 93
7.1.4 BGI Filters 93
7.2 Total Organic Carbon (TOG) Analyses of Aqueous Condensate . 95
7.3 Atactic Waste Analysis 95
7.4 Calculations 95
7.4.1 Calculation of Destruction Efficiencies 95
7.4.2 Calculation of Excess Oxygen 103
7.5 Miscellaneous Analyses 103
7.5.1 Inorganic Species 104
7.5.2 NOx 104
iv
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TABLE OF CONTENTS (Continued)
Section Page
REFERENCES 113
APPENDIX A
APPENDIX B
APPENDIX C
APPENDIX D
APPENDIX E
APPENDIX F
APPENDIX G
v
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LIST OF TABLES
Table Page
1-1 TEST MATRIX FOR INCINERATOR VARIABLES 2
2-1 INCINERATOR DESTRUCTION EFFICIENCIES FOR EACH SET OF CONDITIONS. . 5
2-2 INCINERATOR DESTRUCTION EFFICIENCIES (CALCULATIONS BASED ON
WASTE GAS ONLY) 7
2-3 INCINERATOR DESTRUCTION EFFICIENCIES (METHOD 18 ANALYSIS OF
GASEOUS HYDROCARBONS AND IMPINGER TOG) 9
2-4 INCINERATOR DATA SUMMARY - AVERAGE VALUES FOR EACH SET
OF INCINERATOR CONDITIONS 10
2-5 PERCENT CARBON, Btu/LB AND PERCENT MOISTURE IN ATACTIC WASTE ... 14
2-6 NOx RESULTS FOR SELECTED INCINERATOR CONDITIONS 15
3-1 TYPICAL INCINERATOR PARAMETERS BASED ON DATA FROM AUGUST, 1981
(PROVIDED BY ARCO CHEMICAL COMPANY FROM PROCESS DATA) 21
5-1 METHODS USED TO DETERMINE THE INORGANIC SPECIES 46
6-1 SUMMARY OF ESTIMATED VERSUS MEASURED DATA QUALITY 50
6-2 AUDIT STANDARDS 54
6-3 SUMMARY OF PRECISION OF HYDROCARBON DETERMINATIONS 61
6-4 SUMMARY OF PERFORMANCE AUDIT RESULTS FOR METHOD 18 ON-SITE
HYDROCARBON DETERMINATIONS 63
6-5 PERFORMANCE AUDIT RESULTS FOR OFF-SITE METHOD 18
HYDROCARBON SPECIATION 65
6-6 SUMMARY OF PRECISION FOR OFF-SITE METHOD 18 HYDROCARBON SPECIATION 66
6-7 SUMMARY OF EPA METHOD 25 PERFORMANCE AUDIT RESULTS 67
6-8 SUMMARY OF PERFORMANCE AUDIT RESULTS FOR BYRON METHOD ANALYSES . . 68
6-9 SUMMARY OF PRECISION OF TOC ANALYSES 70
VI
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LIST OF TABLES (Continued)
Table Page
6-10 SUMMARY OF PERFORMANCE AUDIT DATA FOR TOG ANALYSES 71
6-11 SUMMARY OF ANALYTICAL PRECISION OF PROXIMATE AND
ULTIMATE ANALYSES 72
6-12 SUMMARY OF PERFORMANCE AUDIT RESULTS FOR PROXIMATE AND
ULTIMATE ANALYSES 73
6-13 SUMMARY OF ANALYTICAL REPLICABILITY OF WATER DETERMINATION. ... 74
6-14 SUMMARY OF PERFORMANCE AUDIT RESULTS FOR KARL-FISCHER
MOISTURE DETERMINATIONS 75
6-15 SUMMARY OF PERFORMANCE AUDIT RESULTS FOR FIXED GAS ANALYSES ... 77
6-16 SUMMARY OF PRECISION FOR FIXED GAS DETERMINATIONS 78
6-17 SUMMARY OF PRECISION FOR NOX ANALYSES 80
6-18 SUMMARY OF NOX AUDIT SAMPLE ANALYSES 81
7-1 INCINERATOR DATA SUMMARY FOR EACH SAMPLING RUN 83
7-2 INCINERATOR DATA SUMMARY - AVERAGE VALUES FOR EACH SET
OF INCINERATOR CONDITIONS 88
7-3 HYDROCARBON SPECIATION OF BOILER OUTLET SAMPLES 91
7-4 PERCENT EXCESS OXYGEN FOR EACH SET OF OPERATING CONDITIONS. ... 94
7-5 RESULTS OF ORGANIC ANALYSIS OF BGI FILTERS 94
7-6 TOC LEVELS IN IMPINGER CATCHES 96
7-7 IMPINGER CATCHES TOC VS. TOTAL SAMPLE TOC 97
7-8 PERCENT CARBON, Btu/LB AND PERCENT MOISTURE IN ATACTIC WASTE
FOR EACH SET OF OPERATING CONDITIONS 98
7-9 AVERAGE Btu/LB, PERCENT CARBON AND PERCENT MOISTURE IN
ATACTIC WASTE FOR EACH DAY OF SAMPLING 99
VII
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LIST OF TABLES (Continued)
Table Page
7-10 RESULTS OF PROXIMATE, ULTIMATE, Btu CONTENT AND MOISTURE
ANALYSES FOR ATACTIC WASTE 100
7-11 PROCESS FLOW RATES DURING EACH SET OF OPERATING CONDITIONS. . . . 110
7-12 ARCO INCINERATOR IMPINGER CATCHES - INORGANIC ANALYSIS OF
BOILER OUTLET SAMPLE Ill
7-13 NOX RESULTS FOR SELECTED INCINERATOR CONDITIONS 112
viii
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LIST OF FIGURES
Figure Page
3-1 Schematic of Incinerator Showing Inlet and Outlet Streams 18
3-2 Incinerator System with Dimensions 20
4-1 Incinerator System with Sampling Point
Locations 24
4-2 Method 25 Sample Acquisition Apparatus 27
4-3 EPA Proposed Method 18 Sampling Apparatus 28
4-4 Schematic Diagram of Byron Sample Acquisition Apparatus 32
4-5 EPA Method 7 - NOx Sampling Train 34
4-6 Atactic Waste Sampling Bomb 36
ix
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ACKNOWLEDGMENT
The authors wish to express their appreciation to the many indivi-
duals who contributed to this project. Special expression of gratitude for
their beneficial contributions to the work described in this report go to:
Winton Kelly (United States Environmental Protection
Agency - ESED/EMB - Research Triangle Park, North
Carolina)
J.W. Parker, A.H. Bitzer and J. Requena (ARCO Chemical
Company, LaPorte Plant, Deer Park, Texas)
H. Shukla and A. Limpiti (EEA, Research Triangle Park,
North Carolina)
W. Draiskar, F. Meadows and D.T. Robinson (Pollution
Control Science, Inc., Miamisburg, Ohio)
C.N. Dominick, D.S. Lewis, R.D. Cox, S. Dennis and
C.B. Chapman (Radian Corporation, Austin, Texas).
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GLOSSARY OF ACRONYMS
ACFM - Actual Cubic Feet Per Minute
AW - Atactic Waste
BO - Boiler Outlet
AP - Pressure differential across pitot,
used to measure gas velocity
EPA - Environmental Protection Agency
FID - Flame lonization Dectector
GC - Gas Chromatograph(y)
GRAV - Gravimetric Residue After Evaporation
HC - Hydrocarbons
NG - Natural Gas
NMHC - Nonmethane Hydrocarbons
NOx - Oxides of Nitrogen
SCFM - Standard Cubic Feet Per Minute
SO - Scrubber Outlet
TCO - Total Chromatographable Organics
THC - Total Hydrocarbons
TNMHC - Total Nonmethane Hydrocarbons
VOC - Volatile Organic Carbon
WG - Waste Gas
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1.0 INTRODUCTION
This report presents the results of measurements of VOC (Volatile
Organic Carbon) destruction efficiencies in ARCO Chemical Company's Monument
II Plant incinerator (Deer Park, Texas) as a function of:
1) operating temperature, and
2) feed stocks, including waste gas and atactic
(unsymmetrical) polymeric waste.
The measurements were performed by Radian Corporation from October 21 through
October 29, 1981. This work was funded and administered by the Emission
Measurement Branch of the U.S. Environmental Protection Agency. The purpose
of these tests was to develop data to be used in support of New Source
Performance Standards (NSPS) for the Polymers and Resins industry. The ARCO
facility provided data on a relatively new and efficient incinerator. A
secondary purpose of this project was to compare results of different analy-
tical methods applicable to the measurement of VOC emissions.
The test matrix in the order performed is shown in Table 1-1.
Eight conditions were tested. No high temperature test was performed for
waste gas and natural gas because the incinerator could not maintain 2000°F
using this gas mixture as fuel. The methods used to measure VOC emissions
included:
• EPA Method 25,
• Proposed EPA Method 18 (both on-site and off-site analyses
performed), and
• Byron Instruments Model 90 sample collection system and
Model 401 Hydrocarbon Analyzer sampling system and
instrument combination.
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TABLE 1-1. TEST MATRIX FOR INCINERATOR VARIABLES
TEMPERATURE
FUEL MIXTURES 1600°F 1800°F 2000°F
Natural Gas +
Waste Gas +
Atactic Waste 4*
Natural Gas +
Waste Gas 87**
Natural Gas +
Atactic Waste
* Listed in order performed.
** Incinerator could not maintain 2000°F using this fuel mixture.
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The following sections present a summary of results, process and
incinerator description, sampling and analytical methodologies, quality
assurance/quality control and detailed results of all analyses. The appen-
dices include a full listing of analytical and process data along with a
complete evaluation of the Byron method for measuring VOC emissions.
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2.0
SUMMARY OF RESULTS
This section summarizes the results given in detail in Section 7.
The ultimate goal of this project was to determine the destruction efficien-
cies in the incinerator.
The volatile organic carbon (VOC) measurements were made by three
independent methods under specified incinerator temperatures and fuel mixes.
These measurements are compared in this section for the eight different
conditions achieved by the incinerator.
2.1
Destruction Efficiencies
Destruction efficiencies (DE's) are based on calculated or measured
values of the carbon contents of the waste stream inlets and the volatile
organic carbon (VOC) content of the incinerator flue gas. The equation used
to compute the percent destruction efficiencies of the waste streams is as
follows:
% Destruction Efficiency = 100 -
grams of VOC in Stack Gas
grams Organic Carbon in Atactic Waste +
grams of Organic Carbon in Waste Gas
X 100
where grams of VOC in the stack gas were measured by the four analytical
methods and the amounts of carbon have been normalized by a set time interval
(e.g., g/sec.). This computation does not represent overall combustion
efficiency of the unit since the supplemental fuel (natural gas) is not
included in the denominator
Table 2-1 contains the measured destruction efficiencies (DE's)
based on analytical method and incinerator conditions. The values which
have greater than signs (>) indicate that no volatile organic carbon (VOC)
was measured and the detection level was used to calculate the DE's. Each
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TABLE 2-1. INCINERATOR DESTRUCTION EFFICIENCIES
FOR EACH SET OF CONDITIONS
% Destruction Efficiencyt
Conditions
AW/NG/WG
0 2,000°F
AW/NG/WG
0 1,800°F
AW/NG/WG
0 1,600°F
NG/WG
0 1,800°F
NG/WG
@ 1,600°F
AW/NG
0 2,000°F
AW/NG
@ 1,800°F
AW/NG
@ 1,600°F
GC
• HC
>99.99777±. 00008
>99.9979±.0004
>99. 99721 ±.00009
99.8+.1
>99.76±.07
99. 99674±. 00007
>99.990±.004
>99. 9975+. 0001
film!
Byron
THC
99.994±.002
99.996±.001
99. 9961 ±.0003
99.9+.1
99.8±.10
99.9941±.0001
99. 983+. 007
99.994±.002
ated for Each Method-
Byron
NMHC
99. 99 7±. 002
99.998±.001
99.9957±.0002
99.6±.4
99.88±.04
99. 99796±. 00005
99.983±.007
99.995±.003 *
Method**
25
99. 844 ±.006
99.8±.4
99.6±.2
76±20
66+10
96. 32+. 08
98±3
99+1
Speciated
Hydrocarbons
99.88±.04
99.9979±.0001
* Difficulties with analysis - Based on most probable value
** Data not believed to represent true values.
, „ „ . . . ..,,. . inn r grams of organic carbon (gC) in Stack Gas
t % Destruction Eff1C1ency - 100 - [ grams of carbon (gC) in Atactic Waste + grams of carbon (gC) in Waste Gas
-------
sampling and analytical method combine to define VOC levels in the incinera-
tor outlet. However, careful inspection of the DE's indicate that nearly
all VOC numbers under each condition overlap when measured by the proposed
EPA Method 18, the Byron 401 in the total hydrocarbon (THC) mode, the Byron
401 in the non-methane hydrocarbon (NMHC) mode and the off-site, detailed
hydrocarbon speciation method. The absolute values for the DE's by EPA
Method 25 are consistently lower and of poorer quality. The poorer quality
is indicated by the overall larger standard deviations; this is further dis-
cussed in the Quality Assurance/Quality Control Section (Section 6.0). The
VOC values by EPA Method 25 and any data resulting from their use are ques-
tioned as to representing true values. The Byron 401 NMHC mode had a similar
problem but this was rectified on-site (see Appendix D for details).
When the waste gase was the only waste to the incinerator, the DE's
appear to be lower. The waste gas carbon flow rate (~1.8g/sec, see Table
7-10) was very low compared to the natural gas (~110g/sec) which was used as
a supplemental fuel with the waste gas. VOC measured under these conditions
was compared to a very small number (waste gas carbon flow rate) to obtain
the DE. If any VOC was measured, the DE for the waste gas appeared to be
somewhat lower than other waste stream combinations while it may instead be
due to the natural gas contribution to the VOC. Natural gas alone was not
one of the conditions tested.
There is interest in the waste gas DE's when waste gas was used
as a minor fuel component with atactic waste as the major component. When
this test condition existed, natural gas was also used as a minor fuel com-
ponent. The DE's calculated for the waste gas only using this three-component
fuel mixture are given in Table 2-2. Again, because of low carbon contribu-
tions from the waste gas (—1% of the total fuel mixture) very low VOC values
still could result in somewhat lower waste gas DE's. If Method 25 results
are ignored, the DE's based on the waste gas only are still above 99.5%.
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TABLE 2-2. INCINERATOR DESTRUCTION EFFICIENCIES*
(CALCULATIONS BASED ON WASTE GAS ONLY)
% DESTRUCTION EFFICIENCY
AW/NG/WG
1600°F-
AW/NG/WG
1800°F-
AW/NG/WG
2000°F-
BYRON
GCIIC THC
>99.81±.12 99.74±.17
>99.750±.009 99.581.15
>99. 831.02 99.54±.13
BYRON
NMHC
99.71±.18
99.73±.13
99.79±.13
METHOD**
25
73±20
22±50
89±1
* v n t.... ~rn. ,. inn r &C in stack Sas as VOC ,
gc in waste gas
** Not believed to be true values.
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Moisture was a problem during sampling of the incinerator outlet
gases (at the Waste Heat Boiler); therefore, a series of two small, dry
impingers were used to condense the moisture before entering any of the three
sampling systems. Only a few drops of aqueous condensate were collected
during each run. This amount was rinsed out with distilled water (25 ml)
and sent back to Radian's Austin laboratory for total organic carbon (TOC)
analysis. Even though the blank for the distilled water was relatively high
(~-3 ppm) , some samples were above this blank. If this organic material is
defined as VOC then it must be added to the VOC measured by the methods for
gas phase VOC. The results of these additions are listed in Table 2-3. In
one set of incinerator conditions, this addition increased the amount of
VOC as much as fifty times the level seen in the gas phase. However, the
relative error in the TOC measurements is large in most instances and the
percent DE values for gaseous hydrocarbons alone and gaseous hydrocarbons
with the impinger catches overlap within the calculated standard deviations.
2.2 Process and Gas Phase Data
Table 2-4 summarizes the important process and gas phase data for
each of the eight incinerator conditions. The table includes results of
gas analyses on samples taken from the Boiler Outlet (BO), waste gas (WG)
and natural gas (NG) sampling points.
The first, readily apparent, observation is that the proposed
EPA Method 18 (on-site and off-site) results and the two types of measure-
ments made by the Byron Method are similar in values. The averages and
standard deviations overlap in most cases. The EPA Method 25 values for VOC
from the Boiler Outlet are 100 to 1000 times greater than the other methods.
This difference suggests that the Method 25 data may not represent true
values and that the method may have an inherent problem when applied to
combustion processes.
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TABLE 2-3. INCINERATOR DESTRUCTION EFFICIENCIES
(METHOD 18 ANALYSIS OF GASEOUS
HYDROCARBONS AND IMPINGER TOC)
CONDITIONS
AW/NG/WG
@ 2000 °P
AW/NG/WG
@ 1800 °F-
AW/NG/WG
@ 1600 °F
NG/WG
@ 1800 °F-
NG/WG
@ 1600 °F-
AW/NG
@ 2000°F
AW/NG
@ 1800°F-
AW/NG
@ 1600°F
% D.E.
GASEOUS
HYDROCARBONS
>99.99777±. 00008
>99.9979±.0004
>99.99721±. 00009
99.81.1
>99.76±.07
99. 99674±. 00007
. 99.990±.004
>99. 9975±. 0001
% D.E.
IMPINGER
TOC
99.90±.02
99.995±.005
NA
99.4±.6
99.3±.7
99.9911.008
99.781.02
99.9971.008
% D.E.
GASEOUS HC AND
IMPINGER TOC
>99.901.02
>99. 9931. 005
>99. 997211. 00009
99.21.7
>99.11.7
99.9881.008
99.781.02
>99. 9951. 008
NA = Not applicable - No impinger TOC found
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TABLE 2-4. INCINERATOR DATA SUMMARY - AVERAGE VALUES FOR EACH SET OF INCINERATOR CONDITIONS
Oate
Sample Location (')
Process Data Fuel
Condition 0)
Incinerator Temp. (°F)
N2 Flow (xlOOO SCFH)
Natural fias Flow (x3500
SCFH)
Fixed Gases
Method Iff
CO 9%
CO*
N2%
02X
Volumetric Flow
SO Temp. (°F)
Bar. Pressure ("Hg)
AP ("H20)
Velocity (fps)
ACFM
SCFH (dry)
* Moisture
Hydrocarbons
Method 18
BO (ppm - C2-Cg)
WG (vol.* - C2-C6)
NG (vol.* - CH4)
(vol.% - C2-Cfi)
Ryron 401 ppmv-C)
THC (w/ascarlte)
THC (wo/ascar1te)
NHHC (w/ascar1te)
HMHC (wo/ascarlte)
CO (w/ascar1te)
CO (wo/ascarlte)
Method 25
Spec la ted IIC
tl) AW - Atactlc Waste, NG
10/22
RO
AW/NG
1800
6.3+0.1
2.6^0
5.32+0.14
0+0
8T.35+0.30
14.28+0.20
126+6
30.T+0.0
0.31+0.00
33+0
39200+420
30500+710
13.5+J.l
4.98+2.0
R.5+3.5
98
R.5+3.5
123
57*3
315
1,230+1390
* Natural Gas, WG *
10/26
RO
AH/NG
1600
4.8+J1.6
3.3^0.1
4.73+0.13
0+0
8T.70+0.18
15. 0370.18
127+0
30.5+0.0
0.165+0.007
24.5+0.7
28450+640
22050+490
14.+0"
<1 .0
2.2jfl.l
2.1+1.2(2)
<0.5
440090
0.84
Waste Gas, RO - Haste
10/26*
RO
AH/NG
2000
5.2
7.5
6.75
0
83.0
12.05
133
30.5
0.15
23
27,300
20,400
16
1.6
2.9
2.1
1.0
2.1 iZ)
2.0
0.7
1806
(Continued)
Heat Boiler Outlet
10/27
RO
AW/NG/WG
1600
6.25^0.07
4.25^0.35
4.62+0.04
0+0
82.5+0.2
14.91+0.04
128
30.5
0.15
23
27,200
21 ,000
14
<1 .0
1.4+0.1
1 .55+^0.07
6+0
143+56
10/27 10/27
WG RO
AW/NG/WG AW/NG/WG
1600 1800
6.25+.0.07 6.2+0.0
4.25^0.35 5.75+0.07
0+0 6.18+0.78
0+0 0+0
9T.83+1.03 81.75+0.57
1.54+J.21 13.45+0.07
132+1.4
30.5"+0.0
0.15+0.00
23+0~
27,300+0
20,550+210
15.5+0.7
<1 .0
10+6.3
1 .7+_0.6
1.1+.0.5
2.7+,0.8
93.8^201
10/27
WG
AW/NG/WG
1800
6.2+0.0
5.75+0-.07
0+0
0+0
95".38+0.46
2.08+J.01
7.57+^0.27
I'' Difficulties with analysis, value given represents probable concentration.
*S1ngle determination. Therefore, no error Units.
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TABLE 2-4. (CONTINUED)
Date
Sample Location v ')
Process Oata
Fuel Condition (')
Incinerator Tenp. (°F)
N2 Flow (xlOOO SCFH)
Natural Gas Flow (x3500 SCRI)
Fixed Gases
Method 18
COo*
coy,
fl %
o?%
Volumetric Flow
SO Temp. (°F)
Bar. Pressure ("Hq)
AP ("H2Q)
Velocity (fps)
ACFM
SCFM (dry)
% Moisture
Hydrocarbons
Method 18
RO (ppm - Cj-Cg)
WG (vol.% - C2-C6)
NG (vol.* - CH4
(vol.* - Cy-fg)
Ryron 401 (pnnv-C)
10/28
RO
AH/NG/WG
2000
6.05+0.07
7. 65*0.07
6.46+0.09
0+0
83.55+0.14
11.78+0.18
135.5+0.7
30.5+0.0
0.14+0.00
22+0
26^400+0
19,350+210
17.510.7
<1 .0
10/28
WG
MI/NG/Wfi
2000
6.1+0.0
7.63+0.07
0+0
0+0
91.8+0.7
2.2H0.01
10.8211 .33
10/28 !0/?fl
RO MR
NR/WR MR/WG
1800 1800
6.1+0.0 6.1+0.6
>10 >10
4.76+0.00 0+0
0+0 0+0
87.3+0.1 95". 18+0.53
13.410.1 0.90VT.12
,
135.5+2.1
30.5+Tl.O
0.125+0.007
21.5+0.7
24 ,950+640
18.400+850
17+1.4"
<1 .0
9.3611.90
10/29
no
NR/WR
1600
4.0+0.0
9.310.0
4.53+0.61
0+0
8?.8+0.8
14.6310.18
133.5+0.7
30.5+ff.O
0.125+0.007
21.5+0.7
24900+710
18.600+570
1610 ~
<1 .0
10/29
WG
Nfi/WG
1600
4.0+0.0
9.310.0
0+0
0+0
91.4+0.1
0.3H0.34
10. 8313. 40
10/26,29
MR
AW/NR
1800+200
4.810.7
7.4+1 .9
1.11+0.54
0+0
0+0
0+0
76.2+0.7
9.4615.11
THC Cw/ascarlte)
THC (wo/ascarlte)
NMIir (w/ascarlte)
NMIIC (wo/ascar1te)
CO (w/ascarlte)
CO (wo/ascarlte)
Method 25
NMIIC /
Specia ted HC
1.3+0.8
1.6J7.2
69.6+0.2
i.un.e
0.7+0.5
2.3j+2.3
129+89
tilAW - Atactle Waste, NG = Natural Gas, WG • Waste Has, RO = Waste Meat >ofler nutlet
'?' nifflcultles with analysis, value given represents prohable concentration.
*S1ngle rteternlnatlon. Therefore, no error Unit.
0.9+0.4
1. 2510.02
143118
0.49+.07
-------
During 10/21 and the first test during 10/22, the VOC content of
the Boiler Outlet was much higher than during the rest of the project. This
resulted from a process control malfunction of the meter which indicated
the ratio between combustion air and quench air. There was not enough com-
bustion air and too much quench air. Many compounds were seen during the
on-site hydrocarbon analyses during this upset period. Furthermore, it
was observed that the flame color in the incinerator was a dark orange during
this period while the flame was a bright yellow during proper operation.
Table 2-4 also presents average values obtained for fixed gas
analyses during the various burn conditions. The overall average value for
excess oxygen in the boiler outlet was 172%, but as shown below, as the in-
cinerator temperature was increased, the excess oxygen decreased.
Incinerator Temperature Average Excess Oa (%)
2000°P 117
1800°F 168
1600°F 212
This occurance was as expected and demonstrates that with a relatively con-
stant air flow into the incinerator, more oxygen is consumed at higher tempe-
ratures (higher fuel rates). Fixed gas analyses of the boiler outlet accounted
for approximately 100% of the gases in all tests.
2.3 Composition of Atactic Waste and NOx Levels
This section contains details on the composition of atactic waste
and NOx levels at the scrubber stack measured during the incinerator tests.
These test results are contained in Section 7 of this document.
Atactic waste is the waste resulting from incomplete polymeriza-
tion. The waste stream also contains spent solvents and catalyst from the
12
-------
process. The composition and heat value of these wastes are important para-
meters when considering the feasibility of incineration. The atactic waste
was therefore, subjected to ultimate/proximate, Btu/lb and mositure analyses.
Table 2-5 presents the average results relative to temperature and fuel con-
ditions. The percentage of carbon in the atactic waste and its heat value
(Btu/lb) showed little fluctuation during the testing period. These data
show a substantial amount of carbon present in the atactic waste and, con-
sequently, a relatively high heating value associated with it. The low
moisture content of the waste also contributes to its high net heat value.
Complete results of these analyses are contained in Appendix C.
The results of the NO measured at the stack are given in Table 2-6.
X
The highest level of NO was reached when the incinerator was tested at 2000°F
using AW/NG/WG as the fuel feed. All other NO values are the same within two
X
sigma (the 95% confidence interval).
13
-------
TABLE 2-5. PERCENT CARBON, Btu/LB AND PERCENT MOISTURE IN ATACTIC WASTE
FOR EACH SET OF OPERATING CONDITIONS
AW
X
X
X
X
X
X
Fuel Conditions
NG UG
X
X
X
X X
X X
X X
OVERALL AVERAGE
Temperature
1800
1600
2000
1600
1800
2000
Percent Carbon
76.67 ± 0.79
75.81 i 0.35
75.84 ± 0.19*
75.56 1 0.09
75.63 ± 0.19
75.95 ± 0.35
75.96 1 0.56
Btu/lb
18848 ± 043
18437 ± 057
18503 ± 003.
18338 ± 086
18570 ± 042
18656 t 036
18576 i 190
Percent Moisture
—
0.05 i 0
5* 0.095 t 0.007*
0.12**
0.19 t 0.028*
0.30**
0.13 ± 0.096
*0ne sample, Two determinations
**0ne determination
-------
TABLE 2-6. NOX RESULTS FOR SELECTED INCINERATOR CONDITIONS
INCINERATOR NOX*
CONDITIONS yg/Nm3 (ppm)
AW/NG
@ 1800°F 6.08E4±4.17E3 (22.33±1.53)
AW/NG
@ 1600°F 6.92E4H.13E4 (25.40±4.16)
AW/NG/WG
@ 1600°F 6.60E4±6.05E3 (24.25±2.22)
AW/NG/WG
@ 2000°F 1.05E5±S.31E3 (38.6±3.05)
NG/WG
@ 1600°F 5.50E4±4.03E3 (20.20±1.48)
*Average includes results from duplicate analyses of identical samples
on the same day and repeated analysis of samples on different days.
15
-------
3.0 PROCESS AND INCINERATION DESCRIPTIONS
The incinerator for this study is located at the ARCO Chemical
Company Plant in Deer Park, Texas. To provide a basis for comparison of
the operation and efficiency of this incinerator with others as may be required
by New Source Performance Standards (NSPS), a brief description of the process
and a detailed description of the incinerator follows. The incinerator des-
cription includes operational and physical details.
3.1 Process Description
The incinerator and associated waste heat boiler are integral
parts of the ARCO Plant. The plant produces "raw" polypropylene which
is shipped out for final processing into finished products. The facility
actually includes two plants - Monument Plants I and II. The older,
Monument I Plant has four polypropylene process trains while Monument II has
two process trains. The two plants discharge their wastes to the incinera-
tor system where they are burned. The wastes in the plants occur from:
• processing chemicals and dilution solvents for the catalyst,
• spent catalyst,
• waste polymeric material (atactic waste), and
• nitrogen swept propylene from the final stages of the
process.
The feed rates of these wastes to the incinerator vary according to which
trains are running and what start-ups are occurring in the two plants. Feed
rate variations were observed during the two weeks of the incinerator test.
16
-------
The waste heat boiler associated with the incinerator provides
a major portion of the process steam needed by the two polymer plants.
Natural gas is used as an auxiliary fuel to fire the incinerator. If neces-
sary, fuel oil can also be used. Under full production conditions, the
atactic waste provides approximately 50% of the energy needed to produce
the steam and the natural gas is reduced to a minimum.
3.2 Incinerator Description
The incinerator and associated equipment were designed by John
Zink, Incorporated. The system (Model Number SO-083047) was put into opera-
tion on August 16, 1978. The incinerator's two main purposes are to destroy
organic waste from the polymer processes (primary) and to provide heat to
generate steam (secondary).
Figure 3-1 contains a flow diagram of the incinerator and associated
equipment. The organic wastes from the Monument I and II Plants are sent
to the atactic storage tank. The purge gases are sent directly to the in-
cinerator as shown. To prevent the atactic waste from solidifying in the
storage tank and lines, the waste is continuously recirculated (through
heat traced lines) to and from the incinerator. A valve in the line between
the incinerator and recirculation line regulates the flow of waste into the
incinerator. Air and natural gas are also shown in Figure 3-1 entering the
incinerator. Each inlet stream has its own nozzle inside the incinerator.
The natural gas is used to start up the incinerator, to maintain
a preset temperature and to act as a pilot. Combustion air is fed into the
incinerator at the burner nozzles located approximately 4 feet beyond the
incinerator entrance. The combustion air flow rate is regulated manually.
The quench air enters the incinerator within 3 feet of the burner nozzles.
It is used to maintain a constant temperature and provide excess combustion
air. The quench air flow rate is automatically controlled by incinerator
temperature.
17
-------
Steam to
Plants
Wastes from
Monument I Plant
Atactic Reclrculation
System
Condensate System
Wastes from
Monument II Plant
Steam
Purge Column Waste Gases
Air
Stack
Natural Gas
Scrubber
FIGURE 3-1. SCHEMATIC OF INCINERATOR SHOWING
INLET AND OUTLET STREAMS
-------
During normal operation with all waste streams entering the in-
cinerator, the natural gas is cut back and the atactic waste becomes the
major fuel source. The energy poor purge gas, containing about 95%
nitrogen, must always be sent to the incinerator for destruction of the
volatile organic carbon (VOC) content since there is no storage facility in
the system. During incinerator upset, this stream is sent to a flare.
As the hot gases exit the incinerator, they enter the waste heat
boiler where much of the thermal energy is used to produce steam as illus-
trated in Figure 3-1. The gases then enter a venturi scrubber and are
sent to the final caustic cleaning process at the base of the stack.
Figure 3-2 gives the physical dimensions of the system and illustrates
the downstream components associated with the incinerator. The sampling point
at the top of the waste heat boiler was used to obtain all gaseous samples
for VOC analyses after incineration. However, this point could not be
used to obtain flowrate measurements due to obstructions in the waste heat
boiler. The volumetric flowrate, therefore, was determined on the stack
where the Environmental Protection Agency stack sampling criteria were met.
ARCO Chemical Company provided data to illustrate normal
operating parameters for the incinerator. These are listed in Table 3-1
and represent the average of the parameters for the month of August, 1981.
The following are considered design parameters:
• 7.45 MM Btu/hr,
• air supply ^ 33,900 SCFM
• firebox temperature = 1800°F (2200°F maximum),
• firebox residence time =1.5 seconds, and
• pressure = 78" H20 .
19
-------
N)
O
Waste Cas
Combustion Air
Natural Gas
Sampling
Point
\
».
t
Sampling
Point
Quench
Air
1
Waste
Heat
Volumetric
Flow
Sampling —
Outlet Sampling Point
Boiler
Thermal Incinerator
f „ Inlui
At alt ic Sampling
Waste lolllt
.Point
*
I
Gas -500°F
r r
— ITU
\ 1
/ '
Id
/
Separate
Vent/Sta
5' O.D.
12' O.D.
— •« Platform
\
Venturl Scrubber / \
6'5 1/2" x A'6" / \
j \
o Mist fad— ^
A "JK A
1
Figure 3-2. Incinerator System with Dimensions
-------
TABLE 3-1. TYPICAL INCINERATOR PARAMETERS BASED ON DATA FROM AUGUST, 1981
(PROVIDED BY ARCO CHEMICAL COMPANY FROM PROCESS DATA)
Parameter
Temperature:
Pressure:
Steam Rate:
Average
Range
Average
Range
Maximum
Average
Monument I Plant
-Waste Llquld-
60-68°C(140-155°F)
960-1, 030kPa
-------
TABLE 3-1. (CONTINUED)
N3
Parameter
Temperature :
Pressure :
Average
Range
Average
Atactic Waste
-Incinerator Inlet-
66-68°C(150-155°F)
413kPa(60psig)
Air to Incinerator
-Combustion and Quench-
41°C(105°F)
Natural Gas*
-Incinerator Inlet-
29°C(85°F)
"• r
Steam Production
-From Waste Heat Boiler-
193°C(380°F)
l,240kPa(180psig)
Waste Heat
Boiler Outlet
-VOC Sampling Point-
211°C(412°F)
Range
Maximum
Steam Rate: Average
Maximum
Air Flow: Average
Maximum
Nitrogen Flow: Range
Organic Solids: Average
Organic Liquids: Average
Organic Gases: Average
Range
* 1/6 Fuel oil can he substituted for natural gas.
** During test period, tliis pressure was —10" HaO.
34-69kPa(5-10psig)
8.5-18kPa(34-71"H20)**
3,250g/sec(25,800Lb/hr)
6,680g/sec(53.000Lb/lir)
11.34m3/sec(24,000scfm)
16.02mJ/sec(3A,OOOscfm)
0.079-0.llSm'/sec
(10,000-15,OOOscfh)
(Cut back during
Atactlc Waste
incineration)
-------
4.0 SAMPLING METHODOLOGY
This section describes the sampling procedures and sampling
locations used to determine the VOC destruction efficiency of ARCO Chemical
Company's Monument II incinerator. Typically, referenced methods were used
in this program. In situations where a non-referenced method or modifi-
cations of referenced methods were used, documentation of the specific
technique(s) is presented. Schematic diagrams of each sampling system are
also included in this section.
4.1 Description of Sampling Points
To characterize the VOC destruction efficiency across the
thermal incinerator, liquid, solid, and gas phase sampling was performed.
Figure 4-1 is a schematic of the incinerator process with the five sampling
locations indicated. These locations were:
• Incinerator Inlet
1. Waste gas stream,
2. Natural gas stream,
3. Atactic waste stream,
• Waste Heat Boiler Outlet, and
• Scrubber Stack Outlet.
4.1.1 Incinerator Inlet
The incinerator inlet consists of the following three individual
process streams;
• Waste gas,
23
-------
N3
Haste Cas-
Combustion Air•
Natural Gas •
Quench
Air
Waste
Heat
Boiler
\ /
*
1
Gas -500° F
r r
— trr
\ /
_ Vent
Water Manifold
Thermal Incinerator
12' O.D. x 50' L
Separator
Vent/Stack
— •< Platform
Venturl Scrubber
/I
\
Water— -»
6" Mist Pad— «-
JL A A
Atactlc
Waste
Figure 4-1. Incinerator System with Sampling Point Locations
-------
• Natural gas, and
• Atactic waste streams.
Figure 4-1 shows that the three sampling points are located just before the
three streams enter the incinerator.
. 4.1.2 Waste Heat Boiler Outlet
Figure 4-1 also shows the location of the sampling point for the
incinerator waste heat boiler. A half inch stainless steel tube exiting
the waste heat boiler was heat traced and maintained at a temperature of
•*-250°F. Samples were collected simultaneously by the Byron 90, Method 25,
and proposed Method 18 procedures. The temperature of the flue gas exiting
the waste heat boiler ranged from 420°F to 450°F and gas pressure ranged
from 8 to 12 inches of water.
4.1.3 Scrubber Stack Outlet
Due to the physical constraints of the process ducting, volumetric
flow rate determinations for the flue gas exiting the incinerator were not
made at the exit of the waste heat boiler. Flow rate determinations were
instead performed at the incinerator's scrubber stack outlet where sampling
points meeting EPA criteria are located. These sampling points, two four
inch ports positioned at 90 degrees to each other, provided access to the
flue gas.
4. 2 Volatile Organic Carbon S_acpling Methods
4.2.1 EPA Method 25
EPA Method 25 (1) provided a means for determining total gaseous
25
-------
nonmethane organic emissions as carbon. It is applicable to measuring
volatile organic carbon (VOC) as total gaseous nonmethane organics (TGNMO).
Organic particulates, if present, interfere with the analysis and were con-
sequently removed with a filter.
All Method 25 sampling was subcontracted to Pollution Control
Science, Inc., and was performed using personnel and equipment supplied by
the subcontractor.
The sampling system used for Method 25 consisted of a mini-impinger
moisture knockout, a condensate trap, a flow control system, and a sample
tank. This is depicted in Figure 4-2. Initially, the entire probe, trap,
and tank system were leak-tested to ensure sample integrity. Sampling
was accomplished by evacuating the tank, inserting the probe in the waste
heat boiler port, adjusting the flow to maintain a constant flow into the
tank, and monitoring the time until constant flow could no longer be main-
tained or until sufficient sample had been collected. A post-sampling leak
test was then performed. Lighter VOC components were separated into the
gas phase in the tank and the heavier components were condensed in the trap
along with water vapor if it had not been removed upstream. A more complete
description of this method is found in Appendix E.
4.2.2 Proposed EPA Method 18
The following section discusses the procedures which were used to
collect samples of organics following the proposed EPA Method 18 (2). It
also includes a discussion of method validation. Samples were collected
using a modification of EPA Method 110 (3) for benzene which is also in-
cluded in the proposed EPA Method 18. This modification was necessary due
to the high moisture content of the incinerator gases and the positive pres-
sure of the emissions.
Figure 4-3 illustrates the sampling train used to collect samples
26
-------
BYRON 90
PORT
WASTE
HEAT
BOILER
—A-
ho
5L METHOD18
"VM PORT
PROBE
pi QUICK
OCONNECT
TEFLON
LINE
IMPINGERS
IN ICE BATH
CONDENSATE
TRAP
EVACUATED
SAMPLE
TANK
Figure 4-2. Method 25 Sample Acquisition Apparatus
-------
GLASS FIBER
FILTER HEAT
TRACED-250°F
TEFLON
SAMPLE
LINE
1/2" LINE
FROM WASTE
HEAT BOILER '
STACK
MALE
QUICK
CONNECT
S3
oo
LEAK PROOF
30 GAL. PLASTIC
DRUM
Figure 4-3. EPA Proposed Method 18 Sampling Apparatus
-------
from the Waste Heat Boiler stack. There are three differences between this
system and the one proposed in Method 18. These are:
• a glass fiber filter for particulate removal,
• a metering valve to regulate flow due to pressure from
the stack, and
• a set of two modified impingers in an ice bath to condense
out moisture.
To ensure that a representative, integrated sample was collected
using the modified Method 18 shown in Figure 4-3, three validation tests for
sample flow rate and sample volume into the Tedlar bag were performed. These
tests were performed by inserting a rotameter and dry gas meter into the
sampling system at points both before and after the Tedlar collection bag.
Sample flow rates and sample volumes into the Tedlar bag were compared to the
flow rates and volumes of air displaced from the collection bag's leak-proof
container. For all three tests both flow rates and total volumes agreed
within ±5%. Also, three comparisons for total volume collected in the
Tedlar bags were made. This was done by totally evacuating three bags and
monitoring the evacuated volume with a dry gas meter. These volumes were
compared to the gas volumes obtained for each bag when the bags were filled
according to sampling procedures. The agreement was within ±3%.
Gas samples of the waste gas stream were also obtained using the
Method 18 sampling procedure. Samples were obtained from the waste gas
stream without a pump since the stream was under sufficient positive pre-
sure for passive collection. Also, the filter was omitted at this location
since particulates were not present.
29
-------
4.2.3 Byron Method
Byron Instruments produces a Model 401 analyzer which, when used
in conjunction with their Model 90 sample collector and Model 75 converter,
is capable of performing analyses similar to EPA Method 25. Sampling with
the Byron Method is outlined below. The analytical technique is discussed
in Section 5.
The principle underlying this method is the same as EPA Method
25. However, rather than using a modified standard GC, the Byron Method
uses a process analyzer. This instrument speciates Cz from higher hydro-
carbons, but gives a single value for all nonmethane hydrocarbons. After
separation, all carbonaceous material is combusted to CC>2 which is then convertec
to CHij before being measured by an FID. Thus, the variable response of the
FID to different types of organics is eliminated in the Byron 401 as it is
in EPA Method 25.
The Byron 90 sampling system has the following components:
* fiberglass filter plug,
* 1/4" stainless steel probe,
* mini-impinger moisture knockout,
• Teflon sample lines,
* trap for heavy organics,
* pump, and
• mass flowmeter and Tedlar collection bag.
30
-------
A schematic diagram of this sampling train is depicted in Figure 4-4.
Prior to sampling, the filter, probe,, moisture knockout, trap,
pump, and bag system were leak tested. During sampling the probe was in-
stalled and the sample was allowed to flow through the Model 90 system.
Due to sufficient gas pressure the pump was not needed. A one-hour inte-
grated sample was collected at a constant flow rate between 100-120 cc/min.
At the end of the sampling hour, the 10-liter Tedlar bag contained CH^, CO,
COa, water vapor, and other light organics not removed by the heavy organic
trap. Due to blank problems encountered with the heavy organics trap, it
was eliminated during most of the testing. These problems are discussed
further in Appendix D.
When the heavy organics trap was used, the trapped organics were
recovered through the use of a modified Byron 75 conversion unit. The or-
ganic trap was attached to the unit and a small volume of zero air was
blown through to remove entrained C02. A volume of carrier gas equivalent
to the original sample volume was then passed through- the trap while the
trap was heated to a dull red. The remobilized organics were directed over
a catalyst and converted to COa before being collected in another 10-liter
bag. Flow into the bag was measured using a digital mass flowmeter. Thus,
at the end of this phase of the analysis, the sample had been split into
two 10-liter Tedlar bags, each containing the same volume of gas. The ori-
ginal gas contained non-trapped VOC, C02, CO, and any water vapor from the
sample. The second bag contained the COa obtained from oxidizing all of
the trapped organics.
4.3 NOX Sampling at Waste Heat Boiler Stack
The oxides of nitrogen (NOx) content of the flue gas was'deter-
mined using the methodology specified in EPA Method 7 (1). Based on this
method, triplicate grab samples of the flue gas were collected in evacuated
31
-------
PROBE
TEFLON
LINE
WASTE
HEAT
BOILER
to
)
-V
MASS
FLOWMETER
'" P
-------
flasks that contained a dilute sulfuric acid-hydrogen peroxide solution.
An illustration of the NOX sampling train is presented in Figure 4-5.
4.4 Scrubber Stack Volumetric Flow Rate
The total gas flow rate was determined two or three times daily
using procedures described in EPA Method 2 (1). Based on this method, the
volumetric gas flow rate was determined by measuring the cross-sectional area
of the stack and the average velocity of the flue gas. The area of the stack
was determined by direct measurements.
The average gas velocity was calculated from the average gas velo-
city pressure (measured by the pressure differential across the pitot - AP),
the average flue gas temperature, the absolute static pressures, and the wet
molecular weight determined from EPA Method 3 (1) and 4 (1) (Section 4.5).
Pressure and temperature profile data was obtained by traversing both dia-
gonals of the stack. The number of sampling points required to statisti-
cally measure the average gas velocity was determined using the procedures
outlined in EPA Method 1. The number of sampling points and their distance
from the duct wall is a function of the proximity of the sampling location
to its nearest upstream and downstream flow disturbance.
AP and temperature profile data were measured at each of the
sampling points using an S-type pitot and K-type thermocouple. A Magnahelic
gauge of the proper range was used to measure the pressure drop (AP) across
the S-type pitot. A barometer was used to obtain the barometric pressure
at least twice daily. The static gas pressure at the scrubber outlet was
measured by disconnecting one side of the S-type pitot and then rotating the
pitot so that it was perpendicular to the gas flow. A Magnahelic gauge
attached to the S-type pitot measured the static pressure within the duct.
4.5 Flue Gas Molecular Weight and Flue Gas Moisture
The dry and the wet molecular weight of the flue gas were
33
-------
LO
HEATED PIIQUE
FILTER
P) EVACUATED EVACUATE (7) EVACUATE
FLASK VALVE
FLASK
FLASK SHIELD
SQUEEZEOULD
PUMP VALVE
SAMPLE (-1 1 SAMPLE Ml SAMPLE
PUMP
THERMOMETER -J
Figure 4-5. EPA Method 7 - NOX Sampling Train
-------
calculated using data from the fixed gas analyses of the Method 18 samples
and from the scrubber stack moisture determinations. The method for calcu-
lating flue gas molecular weight is described in EPA Method 3. The
moisture content of the scrubber stack gas was obtained from a psychometric
chart once the moisture was determined to be at the saturated level.
4.6 Atactic Waste Sampling
The atactic waste is a combination of gaseous and semisolid wastes
from the polypropylene process. There are two plants at the facility which
produce this waste. The atactic (unsymmetrical polymeric) waste is piped
from these two plants through heat-traced lines to a heated surge tank
where the pressure is reduced to about 60 psig by venting excess gases to
a flare. The atactic waste is then pumped to the incinerator in a con-
tinuous, heated loop to prevent solidification. A portion of the waste
enters the incinerator while the rest recirculates to the surge tank. No
process flow measuring devices are present in any part of the atactic waste
system.
Samples of the atactic waste were obtained from an on/off valve
in the heated loop just before the incinerator. The valve had two feet
of flexible stainless steel pipe (1") onto which the sampling vessels were
attached. Since samples of the gas as well as the semisolid were required,
a special apparatus was prepared for this purpose as illustrated schematically
in Figure 4-6. After connecting the sampling vessel to the flexible stain-
less steel tube, the atactic waste feedline was purged through the sample
purge valve shown in Figure 4-6. After 4 to 6 seconds the purge valve was
closed and the on/off valve to the sampling device was opened slowly to
allow approximately 200 to 500 grams of sample to be collected. The neces-
sary collection time was determined by trial and error. Both valves were
then closed and the sample purge valve opened to relieve line pressure in
the one-inch tube.
35
-------
CO
MA" FITTING
METERING
VALVE
5um FILTER
ON/OFF
VALVE
1 1
l_l
1
u
1
ON/OFF
SAMPLE
PURGE
VALVE
ATACTIC
WASTE
1" NPT
FITTING
70/>rM34
(ALL STAINLESS STEEL)
Figure 4-6. Atactic Waste Sampling Bomb
-------
The sampling device was then brought to the mobile laboratory and
weighed. To determine if dissolved gases were present in the atactic waste,
any off-gases were vented through the metering valve into a clean Tedlar bag.
Visual observation of the bags following gas collection and reweighing of
the sampling device after venting indicated little if any gas being vented.
An attempt to collect the vent gas sample immediately following collection
of the atactic waste sample resulted in a large amount of the atactic solid/
liquid phase being vented into the Tedlar bag.
4.7 Waste Gas Stream
The sampling procedure used for the waste gas stream was again a
modification of EPA Method 110. This methodology was described in Section
4.2.2 and the proposed sampling train is illustrated in Figure 4-3. Due
to the high moisture content of this stream, the impinger-condenser system
was used. Since particulates were not a problem in this stream, the in-
line glass fiber filter was not used. A sampling pump was not necessary
since the line pressure (2 psig) was sufficient to collect an integrated
sample. Metering valves and a rotameter were used to control the sampling
flow rate.
4.8 Natural Gas
Since the composition of ARCO's natural gas feed stream proved to
be constant, only grab samples were collected for analysis. The grab samples
were passively collected in 70 liter Tedlar bags since line pressures of
approximately 3 psig allowed sample acquisition without a pump.
4.9 Miscellaneous Readings
In addition to the streams described above, other streams were
monitored to determine inlet loadings and outlet emission rates. During
37
-------
testing periods process information was collected for:
• Nitrogen flow rate*
• Steam production rate,
• Propylene usage rate*
• Polypropylene production rate,
• Natural gas flows,
• Atactic surge tank levels, and
• Incinerator temperature.
A complete list of process information is given in Appendix B.
38
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5.0 ANALYTICAL METHODOLOGY
5.1 Gas Analysis
During the testing phase of this program three different methods
were used for the collection and analysis of hydrocarbons. These were:
1) Proposed EPA Method 18,
2) Byron Method, and
3) Method 25.
In addition to hydrocarbon data, the proposed Method 18 samples
were also analyzed for fixed gases and speciated for hydrocarbons.
5.1.1 Proposed Method 18 for Hydrocarbons
Light hydrocarbons (Cj-Cg) and heavy hydrocarbons (C7+) were
determined on-site under the following conditions:
Instrument: Antek Model 460 GC-FID
Column: 1.8 m x 3.2 mm O.D. stainless steel; Porapak Q
80/100 mesh
Carrier: Nitrogen at 40 mL/min
Oven Program: 40°C for 2 min; 10°C/min to 160°C;
160°C for 12 min
Backflush: 20 min
Integrator: Hewlett-Packard 3390A
39
-------
Gas samples were introduced into the instrument through 100 uL,
1 mL or 5 mL sample loops which had been flushed 100-fold with sample. After
the Ci-C6 components had eluted, the column was backf lushed to obtain the
C7+ compounds. Chromatograms were integrated using a Hewlett-Packard 3390A
integrator. All eluted peaks were then quantitated against certified pro-
pane standards.
To ensure data quality, daily calibrations of the instrument were
performed. A one point calibration with certified propane standard was used
for quantification and a Ci-Cy normal hydrocarbon mixture was used daily to
update retention times. Once the instrument was calibrated, a quality control
(QC) standard was analyzed. The values for the QC standard were always well
within the acceptance criteria of ±20% of the average value for the standard
(See Section 6.0).
The following discussion illustrates the conversion of peak areas
to carbon mass per volume. First, the response factor (RF) for ppmv-C was
calculated from the daily calibration as follows :
Peak Area from Propane Standard
Certified ppmv-propane x 3 Carbon atoms/propane molecule
= Area/ppmv-C
When a sample was analyzed the peak areas of interest were summed (e.g.,
TO Cs). The resulting area was then divided by the RF:
_,„ ,. _ = Area(s) of Species of Interest
ppmv-C/Species of Interest - •' . , -r
RF (Area/ppmv-C)
40
-------
Finally, to convert ppmv-C to carbon mass per unit volume (using pounds per
standard cubic foot as an example) the following equation was used:
PPmv~c (Species of Interest) 12 g/mole
10 6 ppmv/Unit Volume x 454 g/lb
0.8493 ft3 /mole*
ifi
IDS 6
* at 68°F and 29.92" Hg
where SCF is defined as standard cubic feet at 68°F and 29.92" Hg.
To obtain mass per unit time (e.g., Ibs C/hr) , the flow rate (e.g., SCF/hr)
of the stream at 68°F and 29.92" Hg was multiplied by mass per unit volume
(Ibs C/SCF).
Mass Flow (Ibs/hr) = Flowrate (SCF/hr) x Mass per Unit Volume (Ibs C/SCF)
5.1.2 Byron Total Hydrocarbon Analyzer
During the on-site testing the Byron Model 401 Total Hydrocarbon
Analyzer was operated in its "full cycle" mode, producing data for total
hydrocarbons, non-methane hydrocarbons, carbon dioxide, methane and carbon
monoxide. Analysis of the gas sample was accomplished by first separating
the carbonaceous compounds in a series of chromatographic columns. These
hydrocarbons were then passed separately through a catalytic oxidizer where
they were oxidized to CC>2 then through a catalytic reducer where they were
reduced to methane. A flame ionization detector (FID) measured the re-
sulting methane. An initial instrument calibration was run using a series
of three standards of varying concentrations. A daily standard was run to
determine the daily response factor of each compound and to ensure that the
instrument response had not drifted more than 10% from the 3-point calibra-
tion. Appendix D contains more infomation concerning this analytical method.
41
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5.1.3 Volatile Organic Compounds (VOC's) - EPA Method 25
Each Method 25 sampling run yielded 2 sample fractions which
were analyzed separately for VOC's.
• The chilled condensate trap contained organics which were
oxidized to COa and quantitatively collected in an evacuated
vessel. An aliquot of the COa was then reduced to CHi* and
quantitated using an FID.
• The sample tank was also analyzed for volatile organics.
An aliquot from the tank was inj ected into a gas chroma-
tographic column to achieve separation of the non-methane
organics from CO, COa and CHi*. These compounds were then
oxidized to COa, reduced to CHi* and determined by FID.
The results from both sample fractions were then totalled to yield the
total gaseous .nonmethane organics (TGNMO) present in the sample. Appendix
E contains a detailed description of Method 25 as performed by Pollution
Control Sciences, Incorporated.
5.1.4 Hydrocarbon Speciation
Samples of the boiler outlet gas were sent back to Radian and analyzed
for low level hydrocarbon species. This was accomplished under the follow-
ing conditions :
Instrument: Varian Model 3700 GC-dual FID
Column 1: 6 m x 1.6 mm O.D. stainless steel micropacked;
n-octane on Porasil C, 100/120 mesh (used for
Cz-Cs analysis)
Carrier 1: Nitrogen at 7 mL/min
42
-------
Column 2: 60m x 0.32mm I.D. fused silica capillary;
SE-30 (used for C5-Ci0 analysis)
Carrier 2: Helium at 2 mL/min
FID Make-up: Nitrogen at 30 mL/min
Oven Program: -50°C for 2 min; 6°C/min to 80°C;
80°C for 20 min
Integrator: Varian Vista 401 chromatographic data system
To attain the desired detection levels, immediately prior to
analysis, gas samples were concentrated in 2 cryogenic traps. The samples
were then desorbed onto the head of each chromatographic column and analyzed
according to the above conditions. All peaks were quantitated against
propane standards (for Ca-Cs) or hexane standards (for CS-CIQ). A detailed
description of this chromatographic system which was interfaced with a
computerized data center is given in Appendix F.
5.1.5 Fixed Gases
The on-site fixed gas analyses were performed under the following
conditions:
Instrument: Fisher Gas Partitioner Model 1200 GC-TCD
Column 1: 2m x 3.1mm; Porapak PQ
Column 2: 3.4m x 4.8mm; Molecular Sieve 13X
Carrier: Helium at 30 mL/min
43
-------
Oven Temp: 50 C
Bridge Current: 275 mA
The instrument was calibrated using 3 sets of certified standards at varying
concentrations. Additional standards were also run daily to ensure that
the instrument calibration had not drifted. Peaks were recorded on a chart
recorder and quantitated against standards using peak height measurements.
5.1.6 NO
x
Samples obtained from the Method 7 NO runs were analyzed according
X
to the EPA methods contained in Reference 1. In this procedure, the nitrogen
oxides (except nitrous oxide) are collected and oxidized to nitrate in a
sulfuric acid-hydrogen peroxide absorbing solution. Following the pH adjust-
ment using ammonium hydroxide, all samples were filtered to remove the
resulting solids. The yellow compound which results from the reaction of
nitrate and phenoldisulfonic acid is measured colorimetrically at 400 nm and
quantitated against a calibration curve as NO .
X
5.1.7 BGI Filters
The BGI filters used to remove entrained particulate were prepared
for analysis by soxhlet extracting the filters for 24 hours with methylene
chloride, then concentrating the methylene chloride extract to 2 mL. The
extracts were analyzed for total chromatographable organics (TCO) and the
gravimetric residue after evaporation (GRAY) (Ref. 4). These analyses provide
a quantitation of the amount of extractable organic material in the sample.
The TCO method quantitates organics in the 100°-300°C boiling range and the
GRAV value represents organics with a boiling point greater than 300°C.
Extracts were analyzed for TCO under the following conditions:
Instrument: Tracer Model 560 GC-FID
44
-------
Column: 3.05m x 2mm, I.D. glass; 10% OV-101 on
100/120 Supelcoport
Oven Program: 50°C for 5 min; 20°C/min to 250°C;
250°C for 15 min
Carrier: Nitrogen at 40 mL/min
Injector Temp: 200°C
Detector Temp: 300°C
Chromatograms were quantitated against a Cs, Ci2, Ci6 n-paraffin standard
using a Hewlett Packard 3380A integrator.
GRAY analyses were performed by evaporating 1 mL of each extract
at room temperature and weighing to a constant weight (±0.1mg) on a Mettler
H35AR four place balance.
5.2 Aqueous Condensate Analysis
Aqueous condensate samples collected from the proposed Method 18
impingers were analyzed for total organic carbon content (TOC). Selected
samples of this condensate were characterized for various inorganic species
instead of TOC.
5.2.1 Total Organic Carbon (TOC)
Total organic carbon was determined according to EPA Method
415.1 using a Beckman Model 915A Total Organic Carbon Analyzer. Carbonace-
ous material in the samples was converted to C02 by catalytic combustion.
The C02 formed was measured by a nondispersive infrared detector. Prior
to analysis, inorganic carbon (HCO^, CO^) was removed by acidification and
sparging with nitrogen.
45
-------
5.2.2
Inorganic Species
Table 5-1 below gives the methods used to determine the
inorganic species. In each case the referenced procedures are indentical
except where modifications are noted.
TABLE 5-1. METHODS USED TO DETERMINE THE INORGANIC SPECIES
TOC
PH
TSS
po;3
so;2
ACIDITY
ALKALINITY
cr
F~
NO! t
N(h
1 EPA, Methods
EPA1
415.1
150.1
160.1
365.2
375.4
305.1
310.1
325.3
(340.2)**
"
354.1
for Chemical
STANDARD
METHODS 2
505
402
209D
(424F
424C-III
Digestion)
426C
(402)*
403
407B
(4138)**
418B
419
Analysis of Water
ASTM3
D2579-74
D1293-65
01888-67
D515-72, Method A
D516-68, Method B
01067-70, Method 8*
01067-70, Method B
0512-67, Method A
(D1179-72, Method B)**
-
Dl 254-67
and Wastes, EPA-600 4-79-020
U.S. EPA, Cincinnati, Ohio, March 1979.
2 Standard Methods for Examination of Water and Wastewater, 15th Edition,
APHA, AWWA, and WPCF, 1981.
3 Annual Book of ASTM Standards, Water, 1977, American Society for Testing
and Materials, Philadelphia, PA, 1977.
* plus H202 digestion
** Ion selective electrode using standards addition instead of a calibration
curve.
f Chromatropic acid
46
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5.3 Atactic Waste Analysis
5.3.1 Ultimate, Proximate, Btu Content
The ultimate, proximate and Btu content of the atactic waste
were determined according to the following ASTM methods:
Analysis ASTM Method Number
Ultimate D3176-74
Proximate D3172-73
Btu content D3286-77
5.3.2 Moisture
The weight percent moisture in the atactic waste was obtained
by Karl Fischer titration, following ASTM Method D-1744.
47
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6.0 QUALITY ASSURANCE
The work performed during this program incorporated a comprehensive
quality assurance/quality control (QA/QC) program as an integral part of the
overall sampling and analytical effort. The major objective of the QA/QC
program was to provide data of known quality with respect to:
• completeness,
• accuracy,
• precision,
• representativeness, and
• comparability.
The quality assurance function was organized to provide independent
review and assessment of project activities and ability to achieve the stated
data quality objectives. The QA coordinator for the project had the responsi-
bility of evaluating the adequacy and effectiveness of the QC system and
providing assurance that it was, in fact, responsive to the specific needs
of the program.
While the system of QA activities was necessarily independent of
the technical effort per se, the QC system was an integral part of the daily
technical effort. It was designed to provide an overall system for generating
data of a specified quality. This section provides an assessment of the QC
program and a summary of resulting data quality, as determined by the QA audit.
6.1 Summary of Audit Results and Conclusions
As part of the quality assurance program for this project, a per-
formance and systems audit was performed during the period 27 and 28 October
1981. Audit activities, results, and conclusions are presented below.
48
-------
Table 6-1 is a summary of measured values for precision and
accuracy of the various parameters as compared to the estimated values which
were presented in the Quality Assurance Project Plan prepared for this program.
Overall, the results are considered to be quite adequate to meet the program
objectives in terms of data reliability. The values for measured accuracy,
which are presented in Table 6-1, represent the mean value for percent
accuracy with the 95 percent confidence interval for this value indicated.
The values for precision represent the mean value for replicability of sample
analyses. Other types of precision, which were measured (e.g., repeatability
of samples, replicability of control sample analyses, etc.) are discussed and
documented later in this section.
The data presented in Table 6-1, as well as the more detailed
summaries presented in tables throughout this section, should be considered
in terms of the data quality implications which are indicated. Looking at
Table 6-1, it is seen that in most cases the measured accuracy (mean) falls
well within the confidence interval defined by the precision value. An
exception to this is seen for the determination of percent moisture in the
atactic waste. Referring to Table 6-1, the largest (poorest) precision
value measured is 14.9 percent, representing one standard deviation. If
random error is considered to be the sole source of inaccuracy, then all
measurements should be accurate within ±29.8 percent of the mean (±2 standard)
deviations) more than 95 percent of the time. Since the measured accuracies
for both audit samples were far outside these bounds, systematic error is
indicated as the source of bias. Since the moisture content of the audit
samples is of the same approximate magnitude as that of the samples, the
audit data should realistically reflect the quality of the sample data.
Judging from the low concentrations indicated, these data indicate that the
moisture contents considered were at or below the detection limit of the
method. The data for the Method 25 determinations likewise tend to indicate
that some inherent procedural problem is responsible for the poor precision
and accuracy observed.
49
-------
TABLE 6-1. SUMMARY OF ESTIMATED VERSUS MEASURED DATA QUALITY
Ul
o
Parameter
Hydrocarbon Determinations
Method 18 (on-site)
£ Cz-Cg (ppm level)
£ C2-C6 (% level)
Method 18 (off-site)
Method 25
Byron Method
TI1C
NMHC
CO
Condensate TOC
Atactic Waste Characterization
Proximate
Ultimate
Btu
Moisture (Karl-Fischer)
Velocity & Volumetric Flowrate
Fixed Gas Analyses
CO 2
N2
02
NO Determinations
Accuracy
Estimated Measured1
± 152 0.21 ± 2. 712
-5.68 t 14. 6Z
± 10% 81.4 ± 1382
± 10%
-2.9 ± 162
-4.2 1 9.92
12. 4Z
± 202 1.11 ± 7.92
t 10% See Table
± 102 See Table
± 10t -2.70X
± 20X -92.1 ± 33. OX
± HZ ± HX1*
± 25Z
-2.4 ± 8.9Z
3.0 ± 11. 4Z
8.8 t 82. 61
± 20Z 8.97 ± 29.061
Precision
Estimated Measured2
10Z
16.97Z
1.20%
1.04Z
10Z 22.34Z/2.32Z 3
10Z
18. 4Z
23. 2Z
5.42Z
10Z 3.8Z
10Z
10Z
10% 0.16Z
10Z 11. 2Z
202 202 *
102
0.67Z
0.302
1.58Z
102 8.132
*Mean value plus 95% confidence Interval.
•^Pooled relative standard deviation for replicabllity of sample analyses.
3Tank/Trap repllcabllity.
''Based on systems audit results.
-------
For both the Method 18 and Byron data, a disparity between
precision (replicability) for sample analyses and that for audit sample
analyses is generally apparent. This is likely due to the general inclina-
tion for variability to increase with decreasing analyte concentration. In
most cases, the samples had hydrocarbon concentrations very near the detec-
tion limits of the methods. At this analyte level, however, the ultimate
impact of this variability on overall data quality, i.e., calculated destruc-
tion efficiency of the incinerator, is relatively insignificant. These
examples illustrate the importance of considering data quality measurements
in context and using them as a tool to define the limitations of the data.
From this standpoint, both the performance audit results and the systems
audit conclusions indicate that the overall data quality is adequate to meet
the program objectives.
6.2 Systems Audit - Approach and Conclusions
A systems "audit is an on-site qualitative review of various aspects
of a total sampling and/or analytical system to assess its overall effective-
ness. The systems audit results represent a subjective evaluation of a set
of interactive systems with respect to strengths, weaknesses, and potential
problem areas. The audit was designed to evaluate the following:
• adherence to accepted procedures in performing reference
method source sampling;
• adequacy of internal quality control procedures;
• equipment and facilities;
• qualification and training of personnel;
• calibration procedures and documentation;
51
-------
• sample handling, custody, and storage; and
• data recording, review and handling.
The systems audit checklists, which are presented in Appendix G,
delineate the specific aspects of the sampling/analytical system which are
deemed to be especially important in obtaining quality data. The activities
which were observed during the audit included:
• hydrocarbon determination (EPA Method 25, EPA Method 18
and the Byron Method),
• NO determination (EPA Method 7),
x
• velocity and volumetric gas flow rate determination
(EPA Methods 1 and 2),
• gas phase molecular weight determination (gas parti-
tioner), and
• collection of atactic waste samples.
As indicated on the audit checklists, careful compliance with
accepted sampling procedures was observed for all sampling activities. The
sampling crew exhibited an obvious familiarity with the equipment and methods
used. Internal QC checks such as pre- and post-test leak checks, check of
sampling train configuration, etc., were carefully followed. The facilities
and procedures used in sample handling and storage were judged to be quite
adequate. All data records were well organized and utilized preformatted
data sheets in most instances. All equipment calibration data were complete
and similarly well organized. This data is presented in Appendix G. Overall,
the systems audit indicated an efficient, well orchestrated sampling effort
which was judged to be adequate for achieving data quality commensurate with
the program requirements.
52
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6.3 Performance Audit
A performance audit is a quantitative assessment of the data quality
of a sampling and/or analytical system. Both field and laboratory (analytical)
operations were addressed in the performance audit for this program. Audit
activities included:
• field check of the laboratory balances (Mettler PC 4400
and OHAUS 1119);
• checks of field calculations;
• analyses of audit gases (both on-site and off-site);
• analyses of NO EPA audit materials;
• blind analysis of a commercial coal standard with the
atactic waste samples for proximate, ultimate and Btu
analyses;
• analyses of potassium acid phthalate audit standards
for TOC determination; and
• analyses of water in xylene audit standards for
moisture determination using the Karl-Fischer
method.
Table 6-2 lists the audit standards which were used for the perfor-
mance audits.
53
-------
TABLE 6-2. AUDIT STANDARDS
Parameter „ Aud",
Material
Hydrocarbon Gas Mixture
EPA Method 25
EPA Method 18 Gas Mixture
TOC Aqueous
Potassium
Acid phthalate
Byron Method Gas Mixture
N0x
Proximate, Coal Standard
Ultimate and
BTD
H20 Determination- Water in
Karl-Fischer Method Dry Xylene
Audit
ID
AAL 6956 l
BAL 339
BAL 317
AAL 6480 *
BAL 318
BAL 339
BAL 317
AAL 6956
AAL 772
A 9541
A 5401
RAD-1
RAD-2
AAL 6480
BAL 318
AAL 772
BAL 317
SSC-1
SSC-3
SSC-7
SSC-8
SSC-9
AR 776
RAD-1
RAD-2
Concentration
CO - 56.2 ppm
CH» - 52.1 ppm
C02 - 1.88Z
C3H, - 9.97Z
Propylene/N2 - 9163 ppm
Propane/N2 - 296.0 ppm
CO - 493 ppm
CH» - 493 ppm
C02 - 9.97Z
CjHa - 197 ppm
Propane/N2 - 19.7 ppm
(see above)
(see above)
(see above)
CO - 0.952Z
CH» - 1.03Z
C02 - 12. OZ
02 - 17. 2Z
C02 - 46. OZ
CHi, - 39. 9Z
N2 - 9.96Z
02 - 4.04Z
C2H6 - 29. 9Z
C3H8 - 9.99Z
N2 - 60. 1Z
1426 ppm C
60.5 ppm C
(see above)
(see above)
(see above)
(see above)
697.3 mg/DSCM2
298.7 mg/DSCM*
896.5 mg/DSCM2
149.4 mg/DSCM2
498.0 mg/DSCM2
11.01Z Ash
52.45Z Volatile Matter
36.54Z Fixed Carbon
14512 BTU
1.29Z Sulfur
76.75Z Carbon
6.89Z Hydrogen
1.30Z Nitrogen
0.07Z Chlorine
11.01Z Ash
1.14Z weight H20
0.57Z weight H20
Audit Material Source
Scott Environmental Technology
"
"
"
US EPA
US EPA
Scott Environmental Technology
"
ii
"
US EPA
"
"
Scott Environmental Technology
"
"
"
"
Scott Environmental Technology
n
"
"
Scientific Gas Products
"
11
Radian
"
Scott Environmental Technology
US EPA
-Scott Environmental Technology
US EPA
US EPA
n
n
"
it
Alpha Resources, Inc.
"
"
it
"
"
n
it
it
11
Radian
II
1Balance Gas HC Free Air
2Dry Standard Cubic Meters
54
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6.3.1 Methods for Quantitation of Accuracy and Precision
Performance audit results presented in the following tables are
expressed in terms of relative accuracy. The relative accuracy for each
parameter is calculated as:
%A . 0^1 x 100
where ,
% A = relative accuracy, percent
M = measured value
T = true value of reference standard
100 = factor for conversion to percentage basis.
The overall estimate of accuracy based upon more than one audit
sample for a given analytical parameter represents the mean of the values
for percent accuracy for the set of audit samples. If the associated confi-
dence interval indicates an accuracy range which includes 0 percent, then
bias cannot be confirmed based on the available data. If 0 percent is not
within the indicated accuracy range, then bias, either low (-) or high (+)
is indicated. The + value associated with the mean %A represents the
95 percent confidence interval based upon the variability of the individual
%A values. The 95 percent confidence interval is calculated using a two-
tailed t-test where range for %A (±) equals
wher e ,
SD = standard deviation of measured %A values based
on two or more audit samples
55
-------
n - number of measured values for %A (i.e., number of
audit samples)
t = t-statistic from table of t-values for Student's t-test.
When fewer than four audit standards were analyzed, the 95 percent
confidence interval for the overall accuracy of the measurement becomes quite
large due to the uncertainty associated with relatively few data points. This
influence is seen by referring to the table of t-values below for the 95 per-
cent confidence level using a two-tailed test.
n
2
3
4
5
6
7
8
df
1
2
3
4
5
6
7
t
12.7
4.30
3.18
2.78
2.57
2.45
2.36
n = number of measurements
df = degrees of freedom, n-1
Based on various internal QC procedures incorporated into the
sampling and analytical protocol, several different aspects of sampling and/or
analytical precision may be estimated from the data. One measure of analytical
precision is replicability. Data used for calculating analytical replicability
included results of:
• replicate analyses of process samples,
• replicate analyses of audit materials, and
• replicate analyses of control standards.
56
-------
In each case, the mean (X) and standard deviation (SD) of the values associ-
ated with a group of replicates were calculated for a given method. The
overall replicability of the method, the pooled relative standard deviation
(PRSD), was then calculated using the following equation:
n
PRSD =
n
I DF.
1=1
where,
X. = RSD of data set i,
DF. = degrees of freedom for data set i (k.-l).
n = total number of data sets,
k. = number of data points in set i,
i = data set 1,2,3 ... n
In instances when only two determinations were performed, i.e.,
duplicate analyses, the standard deviation was estimated from the relative
range (percent difference) of the measurements according to the procedure
outlined in Appendix C of EPA publication 600/9-76-005 (8). The RSD is
calculated as:
RSD = J5r
where,
%D = J*1. *?L x 100
X2)/2
57
-------
and,
Xi = measurement No. 1
X2 = measurement No. 2
A second measure of analytical precision is repeatability. This
is a measure of the day-to-day variability associated with an analytical
system. Generally, repeatability is estimated from repeat analyses of con-
trol standards. Repeatability is expressed as relative standard deviation,
where,
— x 100 = RSD
Appendix G contains control charts for the hydrocarbon (Method 18 and Byron
Method) and fixed gas control samples analyses which graphically illustrate
repeatability.
The concept of repeatability may be expanded to include both
sampling and analytical repeatability. Sampling repeatability for this
program is a measure of the variability associated with data for a given
parameter (hydrocarbon and fixed gas concentrations) obtained from analyses
of samples taken under the same process conditions (e.g., incinerator tempera-
ture, fuel) but at different times. This is actually a measure of total
variability arising from three sources:
• analytical variability,
• sampling variability, and
• process operating variability.
The value for "sample repeatability" should generally be greater
(i.e., the precision is poorer) than that for either analytical replicability
or analytical repeatability since these are components of sample repeatability.
58
-------
Another type of precision, which was measured for the NCL. data, is
A
sample replicability. Here the relative standard deviation of the values
for triplicate samples was calculated. This is similar to the concept of
sample repeatability, but does not include the temporal variability of the
process as one of the contributing components. Since all three samples of
a given group were obtained at virtually the same time, only the inherent
variability of the sampling method and the analytical system contribute to
sample replicability. As for the analytical replicability, the RSD for each
set of triplicate samples was calculated, then the pooled RSD (PRSD) was
taken to represent the overall precision.
The final type of precision considered was reproducibility. This
is a measure of method to method (or interlaboratory) variability for a given
parameter. Reproducibility is reported only for the detailed hydrocarbon
speciation analyses and is calculated using data for the audit sample analyses
on the capillary column vs. the micropacked column.
The following is a brief list of general procedures used in evalua-
ting the QA and QC data:
• mean values of replicate analyses were used in calculating
the RSD for repeatability;
• mean values of replicate analyses were used in calculating
relative accuracy for each parameter;
• suspect data were tested as outliers using the Dixon
criteria and rejected at the 95 percent confidence level;
outliers identified were not included in precision and
accuracy estimates;
• values reported as "less than detection limit" were not
included in precision and accuracy estimates;
59
-------
• estimates of overall sample replicability, overall
analytical replicability and overall sample repeatability
represent the pooled relative standard deviation (PRDS); and
• the 95 percent confidence interval for the accuracy
estimates were calculated from individual measurements
of percent A, where the mean value for analysis of a
given audit standard was used to calculate one value for
percent A. When only one audit sample was analyzed,
no confidence interval could be calculated.
6.3.2 Quantitation of Data Quality
The basis for the quantitation of data quality, in terms of pre-
cision and accuracy, for each measurement parameter are briefly discussed
below and results are summarized in the accompanying tables.
Hydrocarbon Determinations
Hydrocarbon concentrations of the waste gas, boiler outlet gas,
and natural gas were determined by three different sampling/analytical methods
including proposed EPA Method 18, EPA Method 25 and the Byron Method. The
data quality for these methods is summarized below.
Gas samples collected using the Method 18 integrated bag sample
technique were analyzed both on- and off-site. Two Antek 460 gas chromato-
graphs with FID detectors were used for the on-site analyses. One instrument
was calibrated for carbon concentrations in the ppm range while the other was
calibrated in the percent range. Appropriate level standard gas mixtures
were used as control samples. Likewise, several different audit gas
mixtures, in both ranges, were used to conduct the performance audits of this
method. Precision and accuracy data for the Method 18 determinations are
presented in Tables 6-3 and 6-4. The indicated poorer precision for
60
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TABLE 6-3. SUMMARY OF PRECISION OF HYDROCARBON DETERMINATIONS
Samples
Control (QC) Standards
Method/Parameter Repeatability of Replicabillty of Repeatability of
Analyses Analyses Analyses
X n2 PRSD3 X n2 PRSD3 X
Method 18 (GC A)
CH4 — — — — — — 14.7 ppmC
C2 — — — — — — 28.2 ppmC
C3 — — — — — — 47.1 ppmC
C,, — — — — — — 53.0 ppmC
C6 — — — — — — 81.1 ppmC
Overall ( £ C2-C6) 2.0 ppmC 4 100. 5Z 2.7 ppmC 3 16.97Z 55.4 ppmC
Method 18 (GC B)
CHH — — — 9.5Z C 3 1.93 38.6 Z C
C2 — -- -- — — — 10.1 % C
C3 — — — — — — 6.3 X C
Clt — — — — — — 4.1 2 C
C5 — — — — — —, 4.7 X C
C6 — -- — — — — 1.3 X C
Overall (2C2-C6) 9.7Z C 5 . 26.08Z 9.9Z C 6 1.20 5.3 Z C
n1
7
7
7
7
7
5
4
4
4
4
4
4
5
RSD
4.92%
4.68%
8.77X
4.74Z
9.69X
7.83Z5
7.58X
6.66Z
6.49Z
4.25%
7.38%
9.37Z
6.83Z 5
Repltcablllty of
Analyses
X
16.0 ppmC
29.4 ppmC
50.7 ppmC
55.4 ppmC
90.7 ppmC
58.6 ppmC
37.2 Z C
9.8 Z C
6.1 Z C
4.0'Z C
4.7 Z C
1.3 Z C
5.2 Z C
n2
1
1
1
1
1
5
3
3
3
3
3
3
15
PRSD3
10.99Z
6.27X
4.89*
2.60%
3.62Z
4.09%
3.68X
3. 94%
4.09Z
7.71Z
15.4%
21. 1Z
10.44Z
Audit Samples
Replicabillty of
Analyses
Range"1 n2 PRSD
48-44 ppm 3 1.41%
— —
29-893 ppm 6 0.77X
29-893 ppm 6 0.77%
0.96-37.4% 2 3.28%
59.7% 1 1.54%
31.6% 1 1.12%
— —
— —
31.6-59.7% 2 1.33%
'Number of sets of repeat samples or standards.
2Nuraber of sets of replicate samples or standards.
3Pooled relative standard deviation for all sets of replicates or repeats.
''Range of concentrations of audit gas mixtures for each component.
5Pooled RSD for C2-C6.
(Continued)
-------
TABLE 6-3 (Continued).
M
Met hod /Parameter
Byron Method
THC
Samples Control (QC) Standards Audit Samples
Repeatability of Repllcablllty of Repeatability of Repllcablllty of Repllcablllty of
Analyses Analyses Analyses Analyses Analyses
X n1 PRSD3 X n2 PRSD3 X n1 RSD X 0.2 PRSD3 Range1* n2 PRSD3
1.7 ppmC 6 40.42Z 1.7 ppmC 13 18.42 648 ppmC 3 1.44 Z 648 ppmC 3 0.58Z 28.7 ppmC- 5 0.492
NM11C
Overall
Method 25
Light 11C (Tank)
Heavy HC (Trap)
Total HC
1.0 ppmC 5 38.89* 1.0 ppmC 11 23. 2Z 621 pproC 3 4.00 Z
1.8 ppmC 2 44.46Z 2.7 ppmC 8 5.42Z 528 ppmC
1.4 ppmC 13 40. 2Z 1.7 ppmC 32 18. 2Z 599 ppmC
27.0 ppmC 4 39.74% 29.8 ppmC
303 ppmC 7 76.55* 418 ppmC
319 ppmC 7 74.89Z
12
17
22.34Z
2.86Z
3 0.808Z
9 2.1Z
1.17Z C
621 ppmC 3 1.21Z 26.1-836 5 1.44Z
ppmC
528 ppmC 3 0.80Z 1.07Z C 1 1.43Z
599 ppmC 9 0.86Z 26 ppmC- 11 1.10Z
1.17Z C
208 ppmC 5 5.44Z
94 ppmC 2 3.75Z
'Number of seta of repeat samples or standards.
2Number of sets of replicate samples or standards.
3Pooled relative standard deviation for all sets of replicates or repeats.
''Range of concentrations of audit gas mixtures for each component.
5Pooled RSD for C2-Cg.
-------
TABLE 6-4. SUMMARY OF PERFORMANCE AUDIT RESULTS FOR METHOD 18 ON-SITE HYDROCARBON DETERMINATIONS
U)
Sample Identification
ARCO-060 (Cyl 0AAL-6480)
ARCO-061 (Cyl fBAL-318)
ARCO-065 (Cyl JBAL-339)
ARCO-069 (Cyl *BAL-317)
ARCO-074 (Cyl JAAL-6956)
ARCO-096 (Cyl 0AAL 6956)
ARCO-12A (Cyl 0A-9451)
ARCO-13A (Cyl 0A-5401)
C, C2 C3
GC ID Measured Conc. Measured Conc. Measured Conc. . ,
Actual JA Actual „, Actual
Mean' RSD* Conc-' Mean' RSD2 Conc-J Mean' RSD* Conc''
A 440 ppm" 1.13Z 493 -10.75 572 ppm" 0.12Z 591 ppm - 3.2
A 59.6 ppm 0.59Z 59.1 ppm 0.84
A 28.8 ppm 0.98% 28.9 ppm - 0.35
A 892 ppm"1 1.82Z 888 ppm 0.45
A 47.5 ppm 1.191 52.1 ppm - 8.83 57.8 ppm 0.73Z 59.4 ppm - 2.69
A 47.8 ppm 1.92Z 52.1 ppm - 8.25 58.2 ppm 0.36Z 59.4 ppm - 2.02
B 37.41 3.03Z 39.98Z - 6.45
B _ 59. 6Z 1.54Z 59.8 Z - 0.33 31. 6Z 1.12% 29.97 Z 5.44
Mean ZA - - 8.57 ± 2.82 < Mean ZA - - 0.33 Mean %A - - 0.21 ± 2.71
'Mean value of duplicate analyses, ppmv-C (CC A) or Z C, v/v (GC B).
2Relative standard deviation of duplicate analyses, Z.
^Certified concentration of audit gases, ppmv-C or Z C, v/v.
''Measured value was outside Instrument calibration and working ranges.
-------
replicability of sample analyses, as compared to replicability for control
samples or audit samples, is most likely a function of the low hydrocarbon
concentrations encountered.
Four gas samples obtained at the boiler outlet of the incinerator
were shipped in sample canisters to Radian's Austin laboratory for detailed
gas chromatographic speciation. The analyses were performed on a Varian 3700
gas chromatograph. Two audit samples were introduced into similar canisters
and shipped for analysis along with the actual samples. The audit results
for these samples is presented in Table 6-5. Precision data for the off-site
GC analyses is presented in Table 6-6.
The EPA Method 25 determinations of the total gaseous non-methane
organic emissions from the flue gas were performed by Pollution Control
Science, Inc. (PCS). A total of 19 samples were collected at the waste heat
boiler outlet and analyzed off-site. Five audit samples were provided to PCS
by Radian's quality assurance personnel. Of these five samples, one pair of
samples was taken from each of two different audit gas mixtures. For each
pair, one sample was collected using the sample train configuration used for
actual samples, with the water knockout in place. The other sample of the
pair was collected with the water knockout omitted. The fifth sample repre-
sents a third mixture collected using the moisture knockout. Based on the
measured accuracies for these analyses, data pertaining to errors associated
with use of the moisture knockout are inconclusive, as shown in Table 6-7.
Precision data for the method are summarized in Table 6-3.
The third method for VOC determinations used was the Byron Method.
The results of these analyses generally agreed with those obtained by
Method 18. Measured values for precision and accuracy are also generally
comparable, as indicated in Tables 6-3 and 6-8.
For all three of the above methods, the performance audit consisted
of submitting certified standard gas mixtures for analysis along with actual
64
-------
TABLE 6-5. PERFORMANCE AUDIT RESULTS FOR OFF-SITE METHOD 18 HYDROCARBON SPECIATION
Ln
Sample
Identification
ARCO 104
(Cyl #BAL 339)
ARCO 105
(Cyl #AAL 6956)
, .1 PA"DTTT AT*V POT TTMM . . .
LiAr ILLAKl L.ULUWIN
Measured
X1 n2 RSD3 Actual
25. 48" 3 2.16 28.9
51. 465 3 1.09 59.4
Mean % A =
%A
-11.8
-13.4
=====
-12.6±10
.. .. . MTPnr^T) A nwnTi prM TT>-TM ..... ...
MJ.liUUlALiK.UilJ LiULUMN
Measured • •
X1 n2 RSD3 Actual %A
27.70k 3 0.26 28.9 -4.2
63. 395 3 0.67 59.4 6.7
==
.2% Mean % A = 1.25±69.0!
of replicate analyses, ppmv-C.
2Number of replicates.
3Relative standard deviation of replicates, percent.
kQualitatively identified as propylene.
Qualitatively identified as propane.
-------
TABLE 6-6. SUMMARY OF PRECISION1 FOR OFF-SITE METHOD 18 HYDROCARBON SPECIATION
Column/Sample ID
Capillary Column
ARCO 104 (Cyl //BAL 339)
ARCO 105 (Cyl //AAL 6956)
Micropacked Column
ARCO 104 (Cyl //BAL 339)
ARCO 105 (Cyl //AAL 6956)
REPLICABILITY OF ANALYSES
(ppmv-C) n RSD
25.48 3 2.16%
51.46 3 1.09%
PRSD = 1.58%
27.70 3 0.26%
63.39 3 0.67%
PRSD = 0.46%
REPRODUCIBILITY2 OF ANALYSES
(ppmv-C) n RSD
26.59 2 5.90%
57.42 2 14.69%
PRSD = 10.30%
Based on analyses of audit samples only.
2Results for capillary column versus micropacked column.
-------
TABLE 6-7. SUMMARY OF EPA METHOD 25 PERFORMANCE AUDIT RESULTS
Measured Concentration (ppm-C)
Sample Identification Tank Trap
Mean1 RSD2 Mean1 RSD2
ARCO-1095 (Cyl 0AAL-6956) 75.2 5.4Z 151 1.66Z 217
ARCO-1106 (Cyl IALL-6956) 88.2 4.5X < 15 88.2
ARCO-1136 (Cyl JBAL-339) 28.7 7.6X 37.2 5.8U 57.2
ARCO-1145 (Cyl 0BAL-339) 30.4 7.2X < 15 30.4
ARCO-1216 (Cyl JBAL-317) - 815 2.5Z < 15 815
•
Actual
Concentration1* I A
59.4 265 X
59.4 48.52
28.89 98.0%
28.89 3.6Z
888 - 8.2Z
81.4 ± 138
'Mean concentration of replicate analyses.
2Relatlve standard deviation for replicate analyses.
3Total reported concentration, ppmv-C, total non-methane hydrocarbon.
''Certified concentration of audit gas, ppmv-C, total non-methane hydrocarbon.
^Molsure knockout omitted from sample train for audit gas sample.
6Audlt sample Introduced through complete sampling train with moisture knockout as used for sample collection.
-------
TABLE 6-8. SUMMARY OF PERFORMANCE AUDIT RESULTS FOR BYRON METHOD ANALYSES
Sample Identification
THC
Measured Cone. Actual
Cone.
Mean1
RSD2
ZA
NHHC
Measured Cone.
Mean*
RSD*
Actual
Cone.
CO
Measured Cone.
Mean1
RSD2
Actual
Cone.
ZA
ARCO-060 (Cyl 0AAL-6480)
ARCO-061 (Cyl JBAI.-318)
ARCO-062 (Cyl *BAL-772)
ARCO-069 (Cyl 0BAL-317)
ARCO-065 (Cyl 0BAU-339)
1130 0.62
49.7 0.18
1.17Z 0.18
748 0.47
28.7 0.66
1084
1 59.1
1 1.03%
888
28.89
4.2
-15.9
13.6
-15.8
- 0.7
619 2.70
55.5 0.49
70.0 1.17
836 0.75
26.1 0.78
591
59.1
_3 _
888
28.89
4.7
- 6.1
—
- 5.9
- 9.7
1.07Z 1.43Z
0.952
12.4
Mean ZA - - 2.9 ± 16.0
Mean ZA - - 4.2 ± 9.9
Mean ZA - 12.4
CO
Mean value of replicate analyses, ppmv-C except as noted.
^Relative standard deviation of replicate analyses.
Mlydrocarbon residue - not quantified.
-------
samples. Three of these audit gas mixtures were obtained from the Quality
Assurance Management Staff of the U.S. Environmental Protection Agency (EPA).
The audit samples for the Byron method and the on-site Method 18 determina-
tions were introduced into clean Tedlar bags by the auditor and given to the
scientists performing the analyses as blind samples. Samples for off-site
analysis were introduced into collection vessels identical to those for
actual samples. Precision estimates for the methods are based upon results
of replicate analyses of samples, control standards, and audit samples,
repeat samples obtained under similar process conditions, and repeat analyses
of control standards.
Samples of aqueous condensate collected in the moisture knockouts
were submitted for TOG analysis to determine the contribution of emissions
if this is defined as VOC. The data quality of these analyses are summarized
in Tables 6-9 and 6-10. Aqueous solutions of potassium acid phthalate were
prepared by personnel not associated with the sample analyses. Different
batches, at different concentrations, were used as control standards and
audit samples.
Atactic Waste Characterization
In order to assess the atactic waste, in terms of characteristics
related to its use as a fuel, 17 samples were submitted for proximate, ul-
timate, and Btu analysis. Eight samples were also submitted for moisture
determinations by the Karl-Fisher titration method. Commercial Testing and
Engineering Company (CT&E) was subcontracted to perform these analyses.
Three blind duplicates were submitted for the proximate, ultimate, and Btu
analyses, and two were submitted for moisture determination. A certified
coal sample was used as the audit sample for the former, while two samples
of water in dry xylene were used for the latter. Precision and accuracy
data for the ultimate/proximate analyses are summarized in Table 6-11 and
6-12. These data for the moisture determinations are presented in Tables
6-13 and 6-14. Considering the accuracy data for the moisture determinations,
69
-------
TABLE 6-9. SUMMARY OF PRECISION OF TOC ANALYSES
Replicability of Repeatability of
Sample Analyses QC Sample Analyses
Sample ID X1
ARCO 084 47
ARCO 057 0
ARCO 123 775
ARCO 002-80 835
TOC Control
Overall
n2 RSD3 X1 n2 RSD3
2 6.0
2 0.0
2 8.2
2 0.8
32 3 4.8
PRSD =3.8
!Mean of replicate analyses, ppm-C
2Number of replicates.
3Relative standard deviation of replicate analyses, percent.
^Pooled RSD for all samples.
70
-------
TABLE 6-10. SUMMARY OF PERFOEMANCE AUDIT DATA FOR TOC ANALYSES
Sample ID
Audit #1
Audit #1
Audit #2
Audit #2
Audit #2
Measured
Cone.
1346
1385
605
624
671
Actual
Cone.
1426
1426
605
605
605
Overall %
%AJ
-5.61
-2.88
0.00
3.14
10.91
A = 1.1117.92%
1Based on single daily determinations of the two
audit standard solutions.
71
-------
TABLE 6-11. SUMMARY OF ANALYTICAL PRECISION OF PROXIMATE AND ULTIMATE ANALYSES
Parameter
Proximate
Z Moisture
Z Ash
Z Volatile
Z Fixed Carbon
Btu/lb
Z Sulfur
Ultimate
Z Carbon
Z Hydrogen
Z Nitrogen
% Chlorine
Z Sulfur
Z Ash
Sample
X '
0.10
0.72
99.28
0.0
18320
0.22
75.91
12.92
0.14
0.56
0.22
0.72
No.
n2
2
2
2
2
2
2
2
2
2
2
2
2
055
USD3
7.4
0.98
0.01
0.0
0.02
47.1
0.26
0.16
10.1
3.75
47.1
0.98
Sample
X '
0.19
0.72
99.28
0.0
18635
0.24
75.90
12.92
0.15
0.54
0.24
0.72
No.
n2
2
2
2
2
2
2
2
2
2
2
2
2
077
RSD3
14.9
2.93
0.02
0.0
0.12
51.2
0.21
0.66
0.0
16.9
51.2
2.93
X >
0.55
0,45
0.0
18540
0.28
75.59
13.01
0.19
0.56
0.28
0.55
Sample No.
n2
2
2
2
2
2
2
2
2
2
2
2
079
RSD3
33.4
0.18
0.0
0.33
7.71
0.24 .
0.87
14.9
6.37
7.71
33.4
Analytical R
•PSRD (I)1*
11.2
12.4
0.07
0.0
0.16
35.3
0.24
0.56
8.30
9.01
35.3
12.4
epllcabillty
n
3
3
3
3
3
3
3
3
3
3
3
3
'Mean value for replicate analyses.
^Number of replicates.
^Relative standard deviation of replicates.
''Pooled relative standard deviation.
-------
TABLE 6-12. SUMMARY OF PERFORMANCE AUDIT RESULTS FOR
PROXIMATE AND ULTIMATE ANALYSES
PARAMETER
Proximate
% Moisture
% Ash
% Volatile
% Fixed Carbon
Btu/lb.
% Sulfur
Ultimate
% Carbon
% Hydrogen
% Nitrogen
% Chlorine
% Sulfur
% Ash
MEASURED*
0.40
9.52
52.69
37.79
14120
1.39
78.86
5.86
1.25
0.13
1.39
9.52
ACTUAL*
11.01
52.45
36.54
14512
1.29
76.75
6.89
1.30
0.07
1.29
11.01
RELATIVE
ACCURACY
-13.5
0.46
3.42
-2.70
7.75
-3.77
-14.9
-3.85
85.7
7.75
-13.5
*A11 values except moisture on a dry basis; measured values based on a
single determination.
73
-------
TABLE 6-13. SUMMARY OF ANALYTICAL REPLICABILITY OF WATER DETERMINATION
Replicability of Sample Analyses
Sample ID P n2 RSD3
#055-A/B
//077-A/B
0.10% 2
0.19% 2
PRSD =
7.4
14.9
11.2
JMean value of replicate analyses.
2Number of replicates.
3Relative standard deviation of mean, percent.
74
-------
TABLE 6-14. SUMMARY OF PERFORMANCE AUDIT RESULTS FOR
KARL-FISCHER MOISTURE DETERMINATIONS
Sample ID
RAD-1
RAD-2
Measured*
(% Weight)
0.06
0.06
Actual
(% Weight)
1.14
0.57
Relative
Accuracy
-94.7
-89.5
Mean % A = -92.1+33.0
*Measured value represents mean of replicate analyses.
75
-------
it appears that both the samples and the audit standards had water concentra-
tions at or below the detection limit of the method, resulting in the rather
poor analytical accuracy.
Velocity and Volumetric Flowrate
The U.S. EPA has conducted extensive collaborative testing to define
the achievable accuracy and precision of the Reference Method test procedures
for source sampling. Independent evaluation and measurement of precision
and accuracy of procedures such as the determination of velocity and volu-
metric flowrate relies upon the results of these tests and systems audit
results, i.e., subjective appraisal of the techniques used. The systems audit
results are augmented by performance audits of component parts of the pro-
cedure when direct measure of data quality is possible. Results of the
on-site fixed gas analyses were used to calculate gas molecular weight
(modified Method 3) which, in turn, is used in calculating velocity and
volumetric flowrate. As for the hydrocarbon analyses, standard gas mixtures
were submitted for analysis to facilitate a performance audit of this
procedure. Results are summarized in Table 6-15. Precision data for the
fixed gas analyses is presented in Table 6-16. Based upon these data and
the systems audit results, the velocity and volumetric flowrate determinations
should be within the precision and accuracy ranges estimated for the methods.
NO Determinations
Five sets of triplicate NO samples were collected during the field
sampling effort. Analyses of these samples were performed at Radian's Austin
laboratory. When the samples were analyzed initially, three samples were
split and analyzed as duplicates. The precision (analytical replicability)
of these analyses was not as good as that typically associated with this
method. The accuracy of the analyses, as measured by results for EPA N0x
audit materials (two samples) also indicated the possibility of problems,
although no bias was indicated since the measured N0x concentrations were
76
-------
Sample
Identification
TABLE 6-15. SUMMARY OF PERFORMANCE AUDIT RESULTS FOR FIXED GAS ANALYSES
CH,, C02 CO 02
Measured Actual ZA Measured Actual ZA Measured Actual ZA Measured Actual ZA Measured Actual ZA
Cone.1 Cone.2 Cone.1 Cone.2 Cone.1 Cone.2 Cone.1 Cone.2 Cone.1 Conc.z
ARCO-060 N/A3 9.66 9.97 - 3.1 21.8 18.9 15.311 71.8 70.31* 2.1
(Cyl JAAL-6480)
ARCO-062 1.04 1.03 0.97 11.8 12.0 - 1.7 1.16 0.952 21.8 17.6 17.2 2.3 72.7 68.81* 3.9
(Cyl 0AAL-772)
Mean ZA - 0.97 Mean ZA - 2.4 ± 8.9 Mean ZA - 21.8 Mean ZA - 8.8 t 82.6 Mean ZA - 3.0 1 11.4
Mean value for duplicate analyses, percent by volume.
^Certified concentration of audit gas, percent by volume, except as noted.
^Not analyzed.
^Calculated concentration baaed on balance gas used, air or nitrogen.
-------
TABLE 6-16. SUMMARY OF PRECISION FOR FIXED GAS DETERMINATIONS
Parameter
Samples
Control (QC) Standards
Repeatability of
Analyses
X n> PRSD3
Replicabillty of
Analyses
J. n2 PRSD3
Repeatability of
Analyses
7 n1 RSD
Replicabillty of
Analyses
Audit Samples
Replicabillty of
Analyses
>2 PRSD3 Range1* n2 PRSD'
CO 2
02
CO
CHi,
5.2X 8 6.27X
87.7X 12 0.57X
9.IX 13 50.96Z
5.2Z 17 0.67Z
86.4* 19 0.30Z
11.4Z 21 1.58Z
19.61
65.21
15.2Z
1.1Z
l.OZ
8 0.84Z
8 4.96Z
8 1.18Z
8 4.69Z
8 6.06Z
19.5Z
62.91
15.1Z
1.15Z
i.03Z
0.67Z
0.3BZ
0.43Z
1.50Z
3.13X
10.72 2 0.75Z
72. 2Z 2 0.462
19.7X 2 0.77X
00
Number of sets of repeat samples or standards.
2Number of sets of replicate samples or standards.
^Pooled relative standard deviation for all sets of replicates or epeats.
^Range of concentrations of audit gas mixtures for each component
-------
within the range predicted by the measured precision. To check the initial
analyses, approximately one-half of the samples were reanalyzed on two sub-
sequent days. The results for these repeat analyses were ultimately
invalidated based on the results for the audit samples analyzed concurrently.
These repeat data are not included in the summaries of precision and accuracy.
A second set of repeat analyses were performed approximately two months after
the original analyses by a different analyst using different equipment and
reagents. These results compared favorably with the original values for the
seven samples which were repeated. Table 6-17 summarizes the precision data
for the NO determinations with respect to replicability and repeatability.
The results of the audit sample analyses are summarized in Table 6-18. Results
for the two samples which led to the invalidation of the first set of repeat
analyses are included in this table but are not considered to be indicative
of the accuracy for the reported results.
Field Check of Laboratory Balances
The accuracy of the laboratory balances, a Mettler PC 4400 and an
OHAUS Model 1119, was checked using a set of NBS traceable Class S weights.
Replicate weighings were made on weights ranging from 1.0 gram to 100 grams.
On the Mettler PC 4400 balance, differences between balance reading and actual
weight were observed for the 50 g and 100 g weights. The difference with the
50 g weight was 0.02 g or 0.04 percent; the difference with the 100 g weight
was 0.01 or 0.01 percent. The OHAUS Model 1119 balance had the greatest
difference using the 10.0 g weight. This difference was 0.02 or -2.0 percent.
79
-------
TABLE 6-17. SUMMARY OF PRECISION FOR N0x ANALYSES
oo
o
Replicabllity of Samples' Replicabllity of Analyses Repeatability of Analyses
Sample X2 n3 RSD Sample X~2 ns RSD Sample X1 n2 RSD
018 63.92 2" 6.7 064-2 64.14 2 13.8 018-1 59.42
037 76.09 3 14.4 125-1 59.64 2 2.14 037-2 . 43.24
064 68.31 3 5.8 PRSD - 8.0 037-3 76.00
097 112.4 3 4.2 097-1 107.9
125 57.89 3 4.0 097-2 102.7
PRSD - 8.1 125-3 55.3
064-3 66.72
2
2
2
2
2
2
2
PRSD -
2.4
15.2
13.3
11.2
6.3
13.1
11.2
10.4
Replicabllity of Analyses
Sample X1 n2 'RSD
Audit 17 1140 2 21.7
Audit 18 147.9 2 7.03
Audit 11 688.5 2 1.95
PRSD - 10.2
'Triplicate samples taken simultaneously.
2X " mean value of n measurements, mg/DSCM
3n ™ number of measurements.
''One of three measurements rejected as outlier at 95Z confidence level.
-------
TABLE 6-18. SUMMARY OF N0x AUDIT SAMPLE ANALYSES
Audit Sample Measured
Identification
7
8
9
3
1
Mean1
1140.3
147.9
824.0
179.8
688
RSD2
21.7
7.03
5.33
14.4
2.0
AC Lua. j.
896.5
149.4
498.0
298.7
697.3
/oA
27.2
1.02
65. 53
-39. 83
- 1.3
Overall 8.97^±29.06
1Mean value of duplicate analyses, mg/DSCM.
2Relative standard deviation of duplicate analyses.
3Results of samples analyzed along with these audit samples
were invalidated. These values are not included in estimated
overall accuracy.
4Mean value for audit samples #7, #8, and #1.
81
-------
7.0 RESULTS
This section discusses the detailed results which include the
following major topics:
• composition of gases,
• organics in condensate catches,
• composition of atactic waste,
• calculations, and
• miscellaneous results such as NOx data and inorganic
species in the gas from the incinerator
The results of all analyses which impact the destruction efficiencies are
presented first, then the calculations for the destruction efficiencies are
presented.
7.1 Gas Phase Data
The following subsections include discussions of various gas phase
analytical results. Instead of presenting separate tables for each type
of analysis, Table 7-1 is presented here so that all data can be viewed to-
gether. This table includes:
• sample identification numbers so that the raw data in the
appendices can be matched to the data presented in the table,
e process data summary which can also be found in the appendices
where all values are recorded,
82
-------
TABLE 7-1. INCINERATOR DATA SUMMARY FOR EACH SAMPLING RUN
oo
UJ
Date 10/21" 10/21"
Sample 10:
Method 18 004 002
Volumetric MOM 019 019
Byron 401 005 009
Method 25 - 006
line (Test Stirt) 1100 1310
Simple Location (') 60 BO
Process Data , .
fuel Condition d) AW/NG AW/NG
Incinerator Temp. CF) 1600 1800
N2 Flow (xlOOO SCFH) 6.2 6.2
Natural Gas Flow (<3SOO
SCFII) 2.6 2.6
Fined Gases
Method 25
C02J 5. 27*. 06 4.95*. 05
COI 00"
N2X 69(2) 69(2)
02I 13.54t..l6 I3.45«..08
Volumetric Flou
time 1513 1513
SO Temp (°F) 132 132
Bar. Pressure ("Kg) 30.5 30.5
AP ("H20) .32 .32
Velocity (fps) 34 34
ACFM 40.200 40,200
SCFM (dry) 30.100 30.100
t Moisture (3) 16 16
Hydrocarbons
Method 1ST
BO (ppm - C2-C6) 269.4 649.3
UG (vol.1 - C2-C6)
KG (vol.1 - CH<)
(vol.1 - C2-C6)
Byron 401 (ppmv-C)
tllC (w/»scarlte) 41*. 8
ICH (wo/ascarlte) 169.1.65 6I.6_.17
I.1..02
<0.5'
881
10/26
033
_
042
040
1145
BO
AU/NG
1600
4.2
3.2
4. 58*. 03
0
81. 4. .71
15.2T.14
1.6
3. 4.. 48
~
3.4«>
<0.5-
125
0.84
10/26
044
041
045
046
I35S
BO
AW/NG
1600
5.2
3.2
4.81*0
0 ~
81. 55*. 21
I4.85T.07
1325
127
30.5
.16
24
28.000
21,700
14
(1.0
1.9^.03
l.9(<)
<0.5«
314
10/26
049
047
051
053
1626
Bo
AU/NG
2000
5.2
7.5
6. 75*. 09
0 ~
83.04.28
12.05>.07
1640
133
30.5
.15
23
27,300
20.400
16
1.6
2.91.07
2.17.31
LOT
2.|H)
2.0
.7
1806
!2 - Data not valid since concentration was outside range of calibration standard
3 - Determined from psychonetric chart.
4 - Difficulties with analysis. Value given represents probable
concentration
(5) - Data not believed to represent true values
-------
TABLE 7-1. (CONTINUED)
00
•P-
te
Vie 10:
let hod IS
'olumetrlc Flow
lyron 401
let hod 25
ne (Test Start)
nple Location H)
ocess Oata
uel Condition (')
nclnerator Temp (*F)
N2 Flow («IOOO 5CFH)
Natural Gas Flow (<3500
SrFM)
ted Gases
1T.LAJ TJI
letnoci in
EOT*
CO*
ly%
umetrlc Flow
tme
SO Temp. CF)
Bar. Pressure ("Hq)
IP ("H20)
Velocity (fpi)
HCFM
SCFN (dry)
I Holsutre I3)
drocarbons
let Rod 18
10 (ppm - C2-C6)
UG vol.» - C2-C6)
UK (vol.* - CRi)
(vol. 1 - C2-C6)
ron 401 (ppnw-C)
Tflir[w7ascarlt(!J
HIIIIC (w/ascarlte)
(HI 1C (wo/ascarlte)
CO (u/ascarlte)
thod 25(5)
wiiic
10/27
054
-
058
059
1020
80
AU/NG/UG
1600
6.3
- 4.0
4.64
0
82. 3*. 64
I5.0TO
I.I3*.»
I.3J.23
1.5*. 25
6*_0
103
10/27
057
071
068
066
1304
BO
AU/NG/UG
1600
6.2
4.5
4. 59*. 08
0
82.6
14. 95* .07
1425
128
30.5
.15
23
27,200
21,000
14
<1.0
1.5*. 11
1.6*. 22
6^.05
182
10/27
038
052
-
1026
UG
AU/HG/UG
1600
6.3
4.0
0
0
94.1*. 57
0.68*. II
1035
I2fl
30.5
'.14
22
26.300
20,300
14
14.4
10/27
063
-
.
-
1302
UG
AU/NG/UG
1600
6.2
4.5
0
0
95. 55*. 07
2.39 ~
5.53*^.07
(Continued)
10/27
067
073
072
076
1520
80
AU/NG/UG
1800
6.2
s.n
5. 62*. 01
0 ~
83. IS*. 21
I3.4_*5
1530
131
30.5
.15
23
27,300
20,700
15
-------
TABLE 7-1. (CONTINUED)
oo
Ui
ate
ample ID;
Method 18
Volumetric Flow
Byron 401
Method 25
Ime (Test Start)
ample Location '"
rocess Data , ,
Fuel Condition 0)
Incinerator Temp. (*F)
N> Flow (xlOOO SCFH)
Natural Gas Flow (i3500
(SCFH)
Ixed Cases
Method IB
CQ«(
COf
Njl
"ft
olumetrtc Flow
Time
SO Temp. (*F)
Bar. Pressure (*Hg)
AP ("HjO)
Velocity (fps)
ACFM
SCFM (dry)
X Moisture (})
ydrocarbons
Method 18
BO (ppm - Cj-Cs)
WG vol.. - C2-C6)
NG (vol.. - CH4)
(vol.1 - C2-C6)
yrpn 401 (ppmv-C)
THC (w/ascarlte)
TIC (wo/ascarlte)
NHIIC (w/ascarlte)
NMllC (wo/ascarlte)
CO (w/ascarlte)
CO (wo/ascarlte)
lethod 25 *5'
OTIC
•For two determinations
"•Shakedown run data presented for
10/28 in/2fl
084 090
087 095
086 094
088 093
0927 1126
BO BO
AM/Nfl/WG AW/NG/UG
2000 2000
6.1 6.0
7.7 7.6
6. 52*. 06 6. 39*. Oil
0 ~ 0 ""
83. 65*. 21 83.45*. 07
1l.65j.07 ll.Sjff
1000 1135
116 135
30.5 10.5
.14 .14
22 22
26,400 26,400
19,200 19,500
18 17
1.61 IO
4.76*0
0
81.4*. 14
11.13)
1511
114
30.5
.13
22
25,400
19,000
16
<1 .0
0.7«.30
0.3*. 12
0.7<:.01
66.8
10/28 10/28 10/28
101 098 108
107
106
111
1643 1419 1640
CO WG WG
NG/UG NG/UG NG/UG
1800 1800 1800
6.1 6.1 6.1
MO MO MO
4.76 0 0
000
83.2 94.80*0 95.55*. 92
I3.S 1.69*9 .10».Bl
1720
117
30.5
.12
21
24.500
17,800
IB
<1.0
8. 02*. 10 10.70t.28
1.5*. 36
1.0*.24
3. 9*. 12
192
. 80 • Waste Heat Boiler Outlet
of calibration
standard
probable concentration
[5) - Data not believed to represent true values
-------
TABLE 7-1. (CONTINUED)
oo
ON
Pate
Sample 10:
Method la
Volumetric Flow
Ryron 401
Method 25
Time (Test Start)
Sample location 1"
Process Oata
Fuel Condition (')
Nj Flow (xlOOO SCFH)
Natural Gas Flow (x3500 SCFH)
Fixed Gases
Hethod~Tir
CO?
02*
Volumetric Flow
TfiS
SO Temp. |'F)
Bar. Pressure ("HgJ
AP ("HpO)
Velocity (fps)
ACFH
SCFH (dry)
I Moisture I1'
Hydrocarbons
Method 18
M"(ppm - Cj-C6)
UG (vol.1 - C -C6)
NG (vol.1 - CH4)
(vol.1 - C2-C6)
Byron 401 (ppmv-C)
~7BC™[w7ascar1te)
TIC (wo/ascarlte)
NM1IC (w/ascarlte)
M1MC (wo/ascarlte)
CO (w/ascarlte)
CO (wo/ascarlte)
Method 25 '5>
NHHC
Speclated HC-TIIHHC (ppmv-C)
10/29
112
116
115
122
0858
BO
NG/UG
1600
4.0
9.3
4. 10*. 02
0
83. 3*. 14
14.75^.07
0915
134
30.5
.12
21
24.400
18.200
16
<1.0-
0.6*.05
0.5*. 22
1.3*. 02
0.491.07
10/29 10/29 10/29 10/26 10/26 10/29
117 120 123 050 056 126
118 - - ...
119 - -
27 - - ...
1100 0656 MOO 1506 1648 1027
BO UG UG NG NG NG
IK/UG NG/UG NG/UG NG/AW NC/AU NG/UG
1600 IfiOO 1600 1600 2000 1600
4.0 4.0 4.0 5.2 5.2 4.0
9.3 9.3 9.3 5.5 7.4 9.3
4.96 00 .80 .80*.02 1.74
0 00 0 0 ~ 0
82.2 95.3 95.5 000
14.5 0.07 0.55 000
1120
133
30.5
.13
22
25.400
19,000
16
13.25t.07 8.44
75.9*1.3 75.6*1.7 77*1.4
6.39*.23 6.63«.13 15.35«.03
1.H.I5
0.47».ll
l.2*.23 '
"'For two determ1n»tions
"Shakedown run data presented for conpleteness only
(1) - AU • At«ctlc Haste. NT. • Natural fes. UC, * Ua.te fcs, QO • Waste Heat Roller Outlet
(?) - Data not valid stnce concentration was outside range of calibration standard
(3) - Determined from psychonetrlc chart.
(4) - Difficult lei with analysis. Value given represents probable concentration
(5) - Data not believed to represent true values
-------
• volumetric flow data for each run,
• fixed gas results from the proposed EPA 18 samples, and
• hydrocarbon results from the Byron, Proposed EPA 18 and
EPA 25 methods along with the totals from the off-site
hydrocarbon speciation analyses.
A summary of average values under each test condition is given in Table 7-2.
7.1.1 Volatile Organic Carbon (VOC) Measurements
Three independent sampling and five different analytical tech-
niques were used to measure the VOC remaining after incineration. These
procedures which have been discussed earlier included:
• EPA Method 25,
• proposed EPA Method 18 including on-site and detailed
off-site analyses, and
• Byron Instruments Method which included a direct total
hydrocarbon (THC) analysis along with the oxidative/reductive
steps to obtain NMHC.
The results of these analyses are shown in Table 7-1 under the heading of
Hydrocarbons. All of these results are for the Waste Heat Boiler Outlet
(BO) unless otherwise noted under Method 18.
The first, readily apparent, observation is that the proposed
Method 18 (on-site and off-site) results and the two types of measurements
made by the Byron Method gave similar values. The average and standard
deviations overlap in most cases.
87
-------
TABLE 7-2. INCINERATOR DATA SUMMARY - AVERAGE VALUES FOR EACH SET OF INCINERATOR CONDITIONS
00
CO
Date
Sample Location (' '
Process Data Fuel
Condition u)
Incinerator Temp. (°F)
N2 Flow (xlOOO SCFH)
Natural Gas Flow (x3500
SCFH)
Fixed Gases
Method 18
coi
Nj*
ii£ia
02%
Volumetric Flow
SO Temp. (°F)
Bar. Pressure ("Hg)
AP ("H20)
Velocity (fps)
ACFH
SCFH (dry)
X Moisture
Hydrocarbons
Method 18
RO (ppm - Co-Cc)
WG (vol.* - C2-C6)
NG (vol.* - CH4)
(vol.* - C2-Cfi)
Byron 401 ppmv-C)
THC (w/ascarlte)
THC (wn/ascar1te)
NMHC (w/ascar1te)
NHHC (wo/ascar1te)
CO (w/ascar1te)
CO (wo/ascarlte)
Method 25
NHHC
Speciated MIC
0) AW - Atactlc Waste, HG =
10/22
RO
AW/NG
1800
6.310.1
2.610
5.32+0.14
0+0
8T.35+0.30
14. 2810. 20
126+6
30.T+0.0
0.31+0.00
33+0
39500+420
30500+710
13.51?.!
4.9812.0
B.S+3.5
98 ~
«.5+3.5
123
57+3
315
1,23011390
Natural Gas, WG * Waste Gas,
10/26
RO
AH/NG
1600
4.810.6
3.310.1
4.73+0.13
0+0
8T.70+0.18
15. 0310.18
127+0
30.5+0.0
0.165"+0.007
24.5+0.7
28450+640
22050+490
14.10
<1 .0
2.211.1
2.111.2(2)
<0.5
440+390
0.84
, BO = Haste
10/26*
RO
AH/NG
2000
5.2
7.5
6.75
0
83.0
12.05
133
30.5
0.15
23
27,300
20.400
16
1.6
2.9
2.1
1 .0
2.1 >')
2.0
0.7
1806
(Continued)
Heat Boiler Outlet
10/27
RO
AM/NG/WG
1600
6.2510.07
4.2510.35
4.62+0.04
0+0
82.5+0.2
14. 9810.04
128
30.5
0.15
23
27,200
21 ,000
14
<1 .0
1 .4+0.1
1.5510.07
6+0
143156
10/27 10/27
WG RO
AH/NG/WG AW/NG/WG
1600 1800
6.2510.07 6.210.0
4.2510.35 5.7510.07
0+0 6.18+0.78
0+0 0+0
9T.83+1.03 81.75+0.57
1.54lT.21 13. 4510. 07
132+1.4
30.5+0.0
0.15+0.00
23+0
27,300+0
20,550+210
15.510.7
<1 .0
1016.3
1.7+0.6
1.110.5
2.7+0.8
93.81201
10/27
WG
AW/NG/HG
1800
6.210.0
5.7510-.07
0+0
0+0
95". 38+0. 46
2.081T.01
7.5710.27
'') Difficulties with analysis, value given represents probable concentration.
*S1ngle determination. Therefore, no error limits.
-------
TABLE 7-2. (CONTINUED)
00
vo
Pate
Sample Location (<>
Process Data
Fuel Condition (')
Incinerator Temp. f°F)
N2 Flow (xlOOO SCFH)
Natural Ras Flow (x3500 SCFH)
Fixed Rases
Method 18
f Oo%
CTO
"2*
Volumetric Flow
SO Temp. (°F)
Bar. Pressure ("Hq)
AP ("H20)
Velocity (fps)
ACFM
SCFM (dry)
% Moisture
Hydrocarbons
Method T8~
R~^ (ppm - Co-Cf:)
WG (vol.* - C2-C6)
NR (vol.% - CH4
(vol.% - C2-C6)
Ryron 401 (ppnv-C)
THC (w/ascarlte)
TIIC (wo/ascar1te)
NMHC (w/ascar1te)
NMHC (wo/ascarlte)
CO (w/ascarlte)
CO (wo/ascar1te)
Method 25
NMHC
Spec 1 a ted HC
10/28
RO
All/Nfi/WR
2000
6.05+0.07
7.65+.0.07
6.46+0.09
n+n
83.55+n.l4
n.7Bin.ia
135.5+0.7
30.5+0.0
0.14+0.00
22+0
26 ,400+0
19,350+210
17.510.7
<1 .0
2.810.7
1.310.8
1.612.2
69.610.2
10/28 10/28 in/28
Hfi RO UR
AII/NR/WR Nfi/WR NR/WR
2nnn 1800 laoo
6.1+0.0 6.1+0.0 6.1+0.6
7.6"5+0.07 >10 >10
0+0 4.76+0.00 0+C
o+o o+o n+n
91.8+0.7 81.3+0.1 9?. 18+0. 53
2.2U0.01 13.410.1 0.90lT.12
135.5+2.1
30.5+fT.O
0.125+0.007
21.5+0.7
24,950+640
18.400+850
1711.4
O .0
10. 8211.33 9.3611.90
1.H0.6
0.710.5
2.312.3
1 29189
10/29
RO
NR/WR
1600
4.0+0.0
9.310.0
4.53+0.61
0+0
81.8+0.8
14. 6310. 18
133.5+0.7
30.5+T5.0
0.125+0.007
21 .5+IT.7
24900+710
18,600+570
1610
<1 .0
0.910.4
0.4910.02
1.2510.02
143118
0.49+.07
10/29 10/26,29
VIG NG
NG/VK AW/NR
1600 1800+200
4.0+0.0 4.8+0.7
9.310.0 7.411.9
0+0 1.11+0.54
0+0 0+0
95.4+0.1 0+0
0.3110.34 OlO
10.83+3.40
76.2+0.7
9.46+5.11
AW - Atactlc Waste, NR - Natural Ras, WG • Waste Ras, RO = Waste Heat Roller nutlet
'?' nifflcult1es with analysis, value given represents probable concentration.
*S1ngle determination. Therefore, no error Unit.
-------
The Method 25 values for VOC from the Boiler Outlet are 100 to
1000 times greater than the other methods. This difference suggests that
the Method 25 data do not represent true values and there is an inherent
problem with the method when applied to combustion processes. A problem
which may be similar occurred with the Byron Instruments method. During
the separations, the C02 would bleed into the peak areas of the hydrocarbons
because of its high value (-5%). Ascarite was used to scrub the samples
of COa before they were analyzed by the Byron 401. This problem and solu-
tion are discussed in much more detail in Appendix D.
A second observation of the data is also readily seen. During
10/21 and the first test during 10/22, the VOC content of the Boiler Outlet
was much higher than during the rest of the project. This resulted from a
process control malfunction of the meter which indicated the ratio between
combustion air and quench air. There was not enough combustion air and too
much quench air. ARCO personnel worked over the weekend of 10/23 and 10/24
to rectify this problem. Many compounds were seen during the on-site hydro- '
carbon analyses during this upset period. Furthermore, it was observed that
the flame color in the incinerator was a dark orange during this period while
the flame was a bright yellow during proper operation.
Lastly, during the analyses by the proposed Method 18 and Byron
401, there was no methane observed. This indicates that what little VOC's
were measured are potentially reactive organics in ozone formation. At-
tempted identifications of these low level species are contained in the
next section.
7.1.2 Hydrocarbon Speciation Results
Three samples including a duplicate sample for hydrocarbon specia-
tion were obtained from the proposed Method 18 samples. The results of these
analyses are listed in Table 7-3.
90
-------
TABLE 7-3. HYDROCARBON SPECIATION OF BOILER
OUTLET SAMPLES (ppbv-C)
COMPOUND
Ethane
Propane
Propylene
Propyne
Unknown #29
Isobutane
Isobutene
Butane
1-Pentene
2-Me thy 1- 1- But ene
Pentane
2-Methyl-2-Butene
cis-2-Pentene
Neohexane
Isobutyr aldehyde
3-Me thy lp ent ane
Methylcyclohexane
Hexane
Benzene
Toluene
Octane
Unknown #2
Unknown #44
m-Xylene
Unknown #106
Styrene
o-Xylene
AW/NG, 1600 °F
10/26, 1145
B.O.
25.3
42.7
-
26.6
54.3
26.6
29.8
-
21.6
18.3
15.8
57.2
-
-
-
17.0
13.5
-
-
136.1
25.1
-
33.4
44.8
-
15.1
16.8
NG/WG, 1600°F
10/29, 0858
B.O.
_
-
20.4
-
16.0
10.5
26.6
9.2
-
21.7
18.9
-
33.1
-
15.1
-
-
221.7
19.0
45.4
8.2
6.2
6.4
15.2
-
6.2
-
NG/WG, 1600°F
10/29, 0858
B.O.
26.5
-
28.4
8.0
21.9
-
10.8
9.2
7.9
-
13.1
-
52.4
28.3
-
-
-
-
-
29.0
10.3
-
12.7
20.6
6.3
7.5
8.3
91
-------
TABLE 7-3. (Continued)
AW/NG, 1600 F
10/26/, 1145
B.O.
NG/WG, 1600 F
10/29, 0858
B.O.
NG/WG, 1600 F
10/29, 0858
B.O.
Nonane
a-Pinene
p-E thy 1 toluene
Unknown #19
3-Pinene
1, 2, 4-Trimethylbenzene
1— Decene
p— Isopropyltoluene
Unknown #52
Decane
Undecane
Ethylbenzene
TOTAL (TNMHC)
% IDENTIFIED
40.9
16.7
14.1
-
27.6
18.4
45.0
14.0
13.0
-
28.8
-
838.5
88.0%
15.4
6.2
5.8
-
6.8
6.7
-
-
-
21.6
11.4
-
537.7
95.0%
18.9
8.2
6.6
10.4
5.5
6.6
-
16.9
-
25.8
11.7
5.5
437.3
88.3%
92
-------
The total non-methane hydrocarbons are about what was observed
during the on-site analyses by the Byron 401 and gas chromatographic method
(EPA Method 18). Furthermore, the totals indicate that the higher concentra-
tions of hydrocarbons were found when the atactic waste was being incinerated.
Many of the compounds are of questionable identification due to their low
levels and blank interferences. However, fourteen of the same compounds
occurred in all three samples.
7.1.3 Fixed Gases
Table 7-2 presents average values obtained for fixed gas analysis
during the various burn conditions. From these analyses, the percent excess
oxygen for each condition was calculated. These results are given in
Table 7-4. Example calculations are discussed in Section 7.4.2. The overall
average excess 02 is 172%. As the temperature of the incinerator was
increased, the excess oxygen decreased. This occurrence was as expected and
demonstrates that with a relatively constant air flow into the incinerator,
more oxygen is consumed at higher temperatures (higher fuel rates). The
different fuel mixtures generally do not appear to affect the excess oxygen.
Fixed gas analyses of the boiler outlet accounted for approximately
100% of the gases in all tests.
7.1.4 BGI Filters
Table 7-5 presents the results of the organic analysis of three
of the BGI particulate filters. This table shows that all of the volatile
organics (as TCO) are all less than the blank, and the organics which were
measured are considered to be those with a boiling point greater than 300°C
(GRAV). Because of the high molecular weight of the compounds found, they
have been considered to be non-volatile and hence are not included in any
of the calculations for destruction efficiencies.
93
-------
TABLE 7-4. PERCENT EXCESS OXYGEN FOR EACH
SET OF OPERATING CONDITIONS
Incinerator Conditions
% Excess Oxygen Average Excess 02
AW/NG @ 1600°F
NG/WG @ 1600°F
AQ/NG/WG @ 1600°F
AW/NG @ 1800°F
NG/WG @ 1800°F
AQ/NG/WG @ 1800°F
AW/NG @ 2000°F
Aw/NG/WG @ 2000°F
OVERALL AVERAGE
223%
198%
215%
193%
153%
157%
120%
113%
212%
168%
117%
172%
TABLE 7-5. RESULTS OF ORGANIC ANALYSIS OF BGI FILTERS
Conditions
AW/NG
1800°F
AW/NG
1600°F
AW/NG/WG
2000°F
Blank
TCO
Less than Blank
Less than Blank
Less than Blank
66 total yg
GRAV
0
1800 total ye
44,400 yg/Nm*
600 total yg
24,100 yg/Nm3
400 total yg
Total Extractable
Organics
Less than Blank
1800 total yg
44,400 yg/Nm3
600 total yg
24,100 yg/Nm3
94
-------
7.2 Total Organic Carbon (TOG) Analyses of Aqueous Condensate
TOG analyses were performed on the aqueous condensate to determine
the amount of volatile carbon which was not collected in the bag/drum sampling
apparatus. Table 7-6 shows the amount of TOG which was collected for each
run. Table 7-7 relates these concentrations to the total volatile carbon
determined from bag sampling and impingers. Impinger samples from the boiler
outlet generally contained at least 65 percent of the total volatile carbon.
The waste gases, however, exhibited a much lower carryover into the impingers.
The average concentration of waste gas hydrocarbons in the bag was ~5,400,000
pg/m3 while the impinger TOG content was around 100,000 yg/m3. Because of
this large difference, the percent of total carbon due to the impinger catch
was very small. Typically, it was less than 2 percent of the total.
7.3 Atactic Waste Analysis
The atactic waste was subjected to ultimate/proximate, heat content
and moisture analyses. Table 7-8 presents selected results relative to tem-
perature and fuel conditions. The percentage of carbon in the atactic waste
and its heat content (Btu/lb) showed little fluctuation during the testing
period. These data show a substantial amount of carbon present in the atactic
waste and, consequently, a relatively high heating value associated with it.
The low moisture content of the waste also contributes to its high net heat
value. Table 7-9 also shows little difference in these parameters for each
day of sampling (~2% for the greatest difference). Complete results of
these analyses are contained in Appendix C. A summary of these data is
presented in Table 7-10.
7.4 Calculations
7.4.1 Calculation of Destruction Efficiencies
This section explains the parameters required and shows example
calculations for the determination of incinerator destruction efficiencies
based on four sets of hydrocarbon data. The calculations presented (for
95
-------
TABLE 7-6. TOG LEVELS IN IMPINGER CATCHES*
SAMPLE #
002
015 or Oil**
021
024
027
033
038
044
049
054
057
067
078
084
090
091
098
100
103
108
112
117
120
123
TOC
20,8001184
1,925+70.7
350±70.7
225+70.7
-------
TABLE 7-7. IMPINGER CATCH TOC VS. TOTAL SAMPLE TOG
Operating Conditions
and
Sampling Point
Impinger Catch
TOC yg/m3
Total VOC
(Impinger and Bag)
Ug/m3
Impinger % of
Total VOC
AW/NG-BO
1800°F
AW/NG-BO
1600°F
AW/NG-BO
2000°F
AW/NG/WG-BO
1600°F
AW/NG/WG-WG
1600°F
AW/NG/WG-BO
1800°F
AW/NG/WG-BO
2000°F
AW/NG/WG-WG
2000"F
NG/WG-BO
1800°F
NG/WG-WG
1800°F
NG/WG-BO
1600°F
NG/WG-WG
1600°F
1.96E412.9E3
2.29E3±2.16E3
66.2
72.6
1.73
>69.1
>98.0
1.50
>77.5
2.04
>73.9
1.05
*Average of two determinations, one determination was
-------
OO
TABLE 7-8. PERCENT CARBON, BTU/LB AND PERCENT MOISTURE IN ATACTIC WASTE FOR
EACH SET OF OPERATING CONDITIONS
Fuel Conditions
AW NG WG
X X
X X
X X
XX X
XX X
XX X
OVERALL AVERAGE
Temperature
1800
1600
2000
1600
1800
2000
Percent Carbon
76.
75.
75.
75.
75.
75.
75.
67
81
84
56
63
95
96
± 0.
± 0.
± 0.
± 0.
± 0.
± 0.
± 0.
79
35
19*
09
19
35
56
Btu/lb Percent Moisture
(Gross)
18848 ±
18437 ±
18503 ±
18338 ±
18570 ±
18656 ±
18576 ±
043
057 0.05 ± 0
003.5* 0.095 ± 0.007*
086 0.12**
042 0.19 ± 0.028*
036 0.30**
190 0.13 ± 0.096
*0ne sample, Two determinations
**0ne determination
-------
TABLE 7-9. AVERAGE BTU/LB, PERCENT CARBON AND PERCENT MOISTURE
IN ATACTIC WASTE FOR EACH DAY OF SAMPLING
Dates 10/22/81
Average Btu/lb. 18848±043
(Gross)
Average % Carbon 76.67±0.79
Average % Moisture
(Karl Fisher Method)
10/26/81
18454±057
75.82±0.29
0.065±0.03
10/27/81
18453±145
75.59±0.13
0.155±0.05
10/28/81
18656±036
75.95±0.30
0.30**
**0ne determination.
VO
-------
TABLE 7-10.
RESULTS OF PROXIMATE, ULTIMATE, Btu CONTENT
AND MOISTURE ANALYSES FOR ATACTIC WASTE
o
o
Sample Description
020*
(10/26;0926)
Proximate Analysis'
% Moisture
% Ash
% Volatile
% Fixed Carbon
Ultimate Analysis*
% Moisture
X Carbon
% Hydrogen
X Nitrogen
% Chlorine
1 Sulfur
% Ash
% Oxygen
(by difference)
Btu/lb (Gross)
% Moisture (Ut. X)
X
0.59
99.41
0.00
X
75.89
13.01
0.28
0.34
0.59
0.35
9.54
18391
AW/NG
1600°F
032 055* 013
(10/26;0914) (10/26;1645). (10/22;0916)
0.05
0.77
99.18
0.00
0.05
75.40
12.89
0.09
0.58
0.14
0.61
10.24
18419
0.05
0.10 t 0.007 X
0.73 i 0.007 0.56
99.18 ± 0.0 99.44
0.0 0.00
0.10 i 0.007 X
75.84 t 0.19 77.58
12.91 t 0.02 12.86
0.14 ± 0.01 0.20
0.57 ± 0.02 0.31
0.23 i 0.11 0.15
0.73 t 0.007 0.56
9.52 ± 0.06 8.34
18503 i 3.5 18824
0.10 ± 0.007
AW/NG
1800-F
0)4 031
(10/22;1310) (10/22;1616)
X 0.05
0.53 0.62
99.47 99.33
0.00 0.00
X 0.05
76.81 76.25
12.95 12.80
0.17 0.13
0.56 0.26
0.53 0.36
0.34 0.62
9.27 9.53
18898 18822
0.05
AW/NG
2000 °F
048
(10/26;1645)
X
0.49
99.51
0.00
X
76.11
12.69
0.19
0.17
0.49
0.22
10.13
18501
'
* Samples recorded 1n log Improperly
t All results on "as received" basis.
-------
TABLE 7-10. (CONTINUED)
AW/NG/UG
1600°F
Proximate Analysis
1! Moisture
% Ash
X Volatile
X Fixed Carbon
039
(10/27;1027)
0.12
0.68
99.20
0.00
070
(10/27;1330)
X
0.81
99.19
0.0
Sample Description
AW/NG/UG AW/NG/WG
1800°F 2000° F
077 079 043
(10/27;1540) (10/27;1735) (10/28;1004)
0.19 t 0.03 X X
0.73 ± 0.02 0.55 t 0.18 0.72
99.09 ± 0.007 99.45 ± 0.18 99.28
0.0 0.0 0.00
092 .
(10/28ill58)
0.30
0.83
98.87
0.00
Ultimate Analysis'
% Moisture 0.12
% Carbon 75.49
% Hydrogen 12.98
% Nitrogen 0.41
% Chlorine 0.60
% Sulfur 0.24
% Ash 0.68
% Oxygen 9.48
;(by difference)
Btu/lb 18399
* Moisture (Wt. X) 0.12
NO
X
75.62
12.71
0.21
0.35
0.81
0.28
10.02
18277
0.
75.
12.
0.
0.
0.
0.
9.
19
76
90
15
55
24
73
50
±
±
±
±
±
±
±
±
0
0
0
0
0
0
0
0
.03
.13
.08
.0
.09
.12
.02
.01
75
13
0
0
0
0
9
.49
.01
.19
.56
.28
.55
.94
X
±
t
t
t
±
±
±
0.
0.
0.
0.
0.
0.
0.
04
11
03
04
02
18
04
18600 ± 17
0.19 ± 0.028
18540 t 62
X
75.70
12.98
0.20
0.54
0.27
0.75
9.56
18630
0.30
76.19
13.18
0.24
0.61
0.32
0.83
8.33
18681
0.30
* Samples recorded In log Improperly.
t All results on "as received" basis.
-------
AW/NG/WG at 2000°F) are representative of the calculations used to generate
Table 2-1 in Section 2.1. All data used in these calculations are taken
from Tables 7-2 and 7-6.
First the carbon mass flow rates for inlet and outlet streams must
be determined. The flow rates for waste gas and natural gas inlet streams and
the stack gas outlet stream were calculated directly. The carbon flow into the
incinerator was calculated for waste gas and natural gas. The carbon mass flow
rate in the waste gas, the waste gas flow rate and the pounds of carbon per
standard cubic foot in the waste gas were calculated as shown in Equations
A and B. Then the pounds of carbon per hour attributable to the waste gas
was calculated (Equation C). Although the total organic carbon (TOG) deter-
mined in the aqueous condensate impinger catches generally contributed a
negligible amount to the total carbon, it was included for completeness.
These calculations are shown in Equations D and E. The impinger contribution
was then added to the amount of carbon determined in C to give the total
carbon flow rate of the waste gas (Equation F). These same calculations
were applied to the natural gas, except there was no impinger contribution
and the flow rate was taken from process data (Equations G, H and I).
The carbon flow rate out of the incinerator was calculated from
the stack gas emissions. This was determined again following the procedures
as for waste gas with the impinger contribution (Equations J, K and L) using
CC>2 as the major carbon-containing species. The stack gas flow rate was
measured on-site.
Since the flow rate of the atactic waste could not be measured
directly, the carbon flow rate was estimated-from the carbon flow rates of
the waste gas, nautral gas and stack gas (Equation M). Using the results
of the ultimate analysis of the atactic waste, the flow rate of the atactic
waste itself was also estimated (Equation N).
102
-------
With this information, destruction efficiencies were then calculated.
Paragraph 0 shows the hydrocarbon determinations taken from Table 7-2 for each
method, represented as percent carbon. Equations P and Q show the equations
for calculation of destruction efficiencies and Sections 1 through 4 carry
these calculations through for each method of hydrocarbon determination.
For operating conditions where the atactic waste was not used to
fuel the incinerator, a carbon balance around the incinerator was attempted.
These data are shown in Table 7-11.
7.4.2 Calculation of Excess Oxygen
The percent excess oxygen was calculated in order to determine the
amount of oxygen remaining after stoichiometric combustion of the waste
products. This section discussed the calculations required to determine
excess oxygen. All data used in the calculations were taken from Table 7-2.
To calculate the excess oxygen, the 02 flow into the incinerator
must first be determined. This was done indirectly since no empirical
measurements were available. The N£ flow due to combustion air first calcu-
lated from the total stack flow and the % flow from the waste gas (R).
This value was used to then obtain total air flow in (S) and from that 02
flow into the incinerator (T). Oxygen flow out of the incinerator must
then be calculated. This was easily accomplished as shown in U. From
these parameters, the oxygen consumed in combustion (V) and the percent
of excess oxygen (W) were calculated.
7.5 Miscellaneous Analyses
Other analyses which were done were not required for the determina-
tion of destruction efficiencies. These analyses discussed below, were
accomplished to gain better insight into the composition of the stack gas.
103
-------
7.5.1 Inorganic Species
Table 7-12 presents results from the analyses of the aqueous con-
densate in the impinger catches from a boiler outlet sample. These data
characterize this condensate as relatively acidic, and give an indication
of what acid gases (pH=3.1) may be present in the gas stream. The NaOH
impinger contains primarily dissolved C02- If this represents about 4.5%
CC>2 as determined from fixed gas analysis, all other species determined
are <0.05% by volume.
7.5.2 N0x
Table 7-13 summarizes the results of the N0x data obtained for
each set of incineration conditions. The highest value of N0x occurred
for the fuel mixture of waste gas, natural gas and atactic waste at 2000°F.
Within two standard deviations (95% confidence interval) all other conditions
have the same NO levels.
X
104
-------
EXAMPLE CALCULATIONS
AW/NG/WG @ 2000°F
INLET STREAMS
A WastP Gas flnw rat? fWGFR^ - Nitrogen Flow Rate in (NFRI) x inn
A. Waste bas flow rate (WbFRJ Waste Gas % N (WGN) X 10°
- 610° ± ° X TOO = 6503 ± 48 SCFH
93.8 ± 0.7
WGN = 93.8% ± 0.7%
NFRI = 6100 ± 0 SCFH
_ Waste Gas % C (WGQ/100 y 12 g/mole
b. LBb L/bLh in Wb 0.8493 ft3/moleX 454 g/Tb
= 10.821.33/100 _ __ _ ±
0.8493 A 454 ~
WGN - 10.82% ± 1.33%
C. LBS C in WG/HR = WGFR X LBS C/SCF in WG
= (6503 ± 48) (0.00337 ± 4E-4) = 21.9 ± 2.6
D. LBS C/SCF in impinger = TOC
= 8.81E5 ± 1.73E3
= 5.69E-5 ± 1.12E-7 LBS C/SCF
E. Impinger Contribution = (LBS C/SCF) (6503 ± 48 SCFH)
(5.69E-5 ± 1.12E-7 LBS C/SCF) (6503 ± 48 SCFH) =^0.37 ± 0.0028
105
-------
F. Total LBS C/HR = IBS C/HR in WG + Impinger Contribution (IBS C/HR)
= (21.9 ± 2.6) + (0.37 ± 0.0028) = 22.3 ± 2.6
6. LBS C/SCF in Natural Gas (NG) = Natural Gas % C (NGQ/100 X 12 g/mole
.8493 ftVmole454 g/lb
NGC =76.2 ± .7 % C from CH,»
+ 9.46 ± 5.11 % C from C2 - C6
85.66 ± 5.16 % C Total
H. LBS C/SCF NG = 85.66 ± 5.16 /TOO X J2_ = .0267 ± .0016
.8493 454
I. LBS C NG/HR = Natural Gas Flow Rate (NGFR) X LBS C/SCF NG
= (26,800 ± 245. SCFH)(.0267 ± .0016 LBS C/SCF) = 716 ± 43
OUTLET STREAM
J. LBS C Stack Gas (SG) = Stack Gas Total Carbon (SGTQ/100 X 12 g/mole
.8493 ft'mole454 g/lb
= 6.46 ± .09/100 X 1_2_ = 2.01 E-3 ± 2.8 E-5 LBS C/SCF
.8493 454
SGTC = 6.46% ± .09%
LBS C/SCF Impinger = 1.56E-6 ± 2.57E-7 (calculated same way as for WG)
K. TOTAL LBS C = LBS C in SG + LBS C in .Impinger
= (2.01E-3 ± 2.8E-5) + (1.56E-6 ± 2.57E-7)
= 2.011E-3 ± 2.8E-5
106
-------
L. LBS CSG = Stack Gas Flow Rate (SGFR) X Total LBS C/SCF SG
HR~
= (116100 ± 12600 SCFH) (2.01E-3 ± 2.8E-5) = 2334 ± 41 LBS C/HR
SGFR = 19,350 SCFM X 60 MIN
HR
= 1161000 SCFH
M. LBS C ATACTIC WASTE
LBS C ATACTIC WASTE = LBS C<-r - [LBS ;C.,r:+ LBS C,.rl
LI rv od I \_tn 11*3 tin ~ nCi 1
nr\ I nr\ HK 1
L -*
= (2334 ± 41) - [(716 ± 43) + (22.3 ± 2.6)]
= 2334 ± 41 - (738 ± 43) = 1596 ± 59 LBS C/HR
N. LBS ATACTIC WASTE
= 1596 ± 59 LBS C in Atactic Waste
.7596 ± .0056 % C in Atactic Waste (from ultimate analyses)
= 2101 79 LBS Atactic Waste/HR
DESTRUCTION EFFICIENCIES
0. GCHC <1.0ppm-C =<1.0E-4%
Byron-THC 2.8 ± 0.7 ppm-C = 2.8E-4 ± 0.7E-4X
Byron-NMHC 1.3 ± 0.8 ppm-C = 1.3E-4 ± 0.8E-4%
Method 25 = 69.6 ± 0.2 ppm-C = 6.96E-3 ± 0.2E-4%
P. % Destruction Eff = 100 -
P Ibs SGVOC/HR y , nn"l
[ibs CAW/HR+ Ibs CWG/HR IUUJ
Q. LBS Stack Gas Volatile Organic Carbon (SGVOC)/HR =
SGFR X SGVOC X 12 g/mole
100 454 g/lb
.8493 ftVmole
107
-------
1.) by GCHC LBS SGVOC =
= < .0361
(116100 ± 12600 SCFH) X <1.0E-4 /TOO X J2.
.8493 454
Destruction Eff = 100 -
< .0361
(1596 ± 59) + (22.3 ± 2.6)
X 100
= 100 -
< .0361
1618 ± 59
X 100
= 100 - ( 2.23E-3 ± 8.13E-5)
= > 99.99777 ± .00008
2.) by BYRON-THC
LBS S6linr = (1161000 ± 12600 SCFH)(2.8E-4 ± .7E-4) Y 12 = .1012 ± .0253
VUL 100 454
.8493
% Destruction Eff = 100 - .1012 ± .0253
1618 ± 5T~
= 100 - (6.25E-3 ± 1.58E-3) = 99.994% ± .002%
3.) by BYRON-NMHC
LBS S6unr = (1161000 ± 12600 SCFH)(1.3E-4 ± 0.8E-4) /TOO X 12
VUL .8493 454
.0470 ± .0290
Destruction Eff = 100 - -0470 ± .0290
1nnl
1UUJ
[_ 1618 ± 59
= 100 - (2.91E-3 ± 1.80E-3) = 99.997% ± .002%
108
-------
4.) by METHOD 25
IBS SG./nr = (1161000 ± 12600 SCFH)(6.96E-3 ± 0.2E-4)/100 X 12_ = 2.52 ± .028
VUL .8493 454
% Destruction Eff = 100 -f2.52 ± .028 Y lnnl = 100 - (1 .56E-3 ± 9.6E-5 X 100)
[1618 ± 59 * IUUJ
= 100 - (.156 ± .0059) = 99.84% ± .01%
CALCULATION OF EXCESS OXYGEN
R. N2 Flow in Stack Gas = (volumetric flow (SCFM) x% N2,n" S'G" - (N2 Flow (SCFH)
IUU /60 min/hr
= (19350 SCFM x .8355) - (6050 SCFH/60 min/hr) = 16070 SCFH
<: fl-iv Fin,, -: <^-x^ - 16070 SCFM N2
b. Air MOW in btacK - >7808 (Fraction of N2 in Air) = 20580 SCFM
T. 02 Flow into Stack = 20580 SCFM Air x .209 (Fraction of 02 in Air) = 4300 SCFM
U. 02 Out of Stack = Volumetric Flow (SCFM) x % °2 S'G>
= (19350 SCFM x .1178) = 2280 SCFM
V. 02 Use = 02 in - 02 out = 4300 SCFM - 2280 SCFM = 202 SCFM
u Fvr0« n - Q2 out lnn _ 2280 SCFM ,nn _ ,,.„
W. Excess 02 - Oz use x 100 - 2020 SCFM x 100 - 113/o
109
-------
TABLE 7-11. PROCESS FLOW RATES DURING EACH SET
OF OPERATING CONDITIONS
Conditions
AW/NG/WG
0 2,000°F
AW/NG/WG
0 1 ,800°F
AW/NG/WG
(? 1,600°F
NG/WG
@ 1 ,800°F
NG/WG
0 1,600°F
AW/NG
0 2,000°F
AW/NG
@ 1,800°F
AW/NG
@ 1,600°F
^Difficulties
Ibs/hr X
g C Natural
Gas /sec
(Ibs/hr)
90.3±5.4
(716±43)
67.7±4.2
(537±33)
50±5.1
(397±40.4)
>118
(>935)
11 6+6.6
(869+52.1)
88±5.3
(701 ±42)
30.6±1.8
(243±14.6)
39±2.6
(308±20.7)
with analysis
g C Waste
Gas/sec
(Ibs/hr)
2.77±.33
(22±2.6)
1.93±.069
(15.3±.55)
2.6±1.6
(20.8±12.9)
2.3±.54
(18.7±4.3)
1.8±.55
(14.5±4.4)
- •
-
-
g C Atactic
Waste/ sec
(Ibs/hr)
20U7.4
(1596±59)
229±38.1
(1815±302)
175±5.7
(1384±45.2)
-
-
236±5.3
(1869±42)
352±13.6
(2795±108)
206±9.1
(1637±72)
- Based on most probable
1 hr Y 1 min „
60 min * 60 sec
qC in waste qas + gC
g Atactic
Waste/ sec
(Ibs/hr)
265±10.0
(2101±79)
301 ±50. 2
(2389±398)
230±7.7
(1822±61)
-
-
310±7.3
(2460±58)
464±18.3
(3680±145)
272±12
(2155±96)
value
g C Stack
Percent Gas/sec
Closure t (Ibs/hr)
294±5.2
(2334±41)
299±37.8
(2367±300)
227±2.0
(1802±15.6)
206±9.5
58% (1634±75)
198±27
56.2±8.4 (1573±217)
324
(2570)
383±13.6
(3038±107)
245±8.7
(1945±69)
Production
Rate of Steam
(xlOOO Ibs/hr)
31
27.5
21.5
25
20.5
33
<35*
23.5
^ = Slf
in Natural gas ,QQ
gC in stack gas
110
-------
TABLE 7-12.
ARCO INCINERATOR IMPINGER CATCHES - INORGANIC ANALYSIS
OF BOILER OUTLET SAMPLE*
Parameter
pH
Acidity (as CaCOj) mg/L
Alkalinity (as CaC03) mg/L
HCOs mg/L
COa2 mg/L
Cl~ mg/L
F~ mg/L
NOa (as N) mg/L
Total P04 (as P) mg/L
SO;2 mg/L
Impinger 11
(Dry)
3.1
12800
-
-
< 1
490
0.12
12.2
0.75
340
Impinger #2
(100 mL IN NaOH)
9.1
-
49490
33950
15540
100
0.12
8.4
0.52
66
Blank
(IN NaOH)
12.6
-
56110
< 1
1150
157
0.05
< 0.1
0.03
4
*Sampling Period: 10/28, 1800 hrs. to 10/29, 0800 hrs.
Fuel: Natural Gas and Waste Gas
Incinerator Temperature: ~ 1700°F
N2 Flow: ~ 5000 scfh
Natural Gas Flow: - 34000 scfh/Comb. Air P: ~ 3.2" H20
111
-------
TABLE 7-13. NOX RESULTS FOR SELECTED INCINERATOR CONDITIONS
INCINERATOR NOX*
CONDITIONS ug/Nm3 (ppm)
AW/NG
@ 1800°F 6.03E4±4.17E3 (22.33±1.53)
AW/NG
@ 1600°F 6.92E4±1.13E4 (25.40±4.16)
AW/NG/WG
@ 1600°F 6.60E4±6.05E3 (24.25±2.22)
AW/NG/WG
<§ 2000°F 1.05E5±S.31E3 (38.6±3.05)
NG/WG
@ 1600°F 5.50E4+4.03E3 (20.20±1.48)
*Average includes results from duplicate analyses of identical samples
on the same day and repeated analysis of samples on different days.
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REFERENCES
1. Reference Methods. Appendix A to 40 CFR 60. Environmental Reporter.
Bureau of National Affairs, Washington, D.D., December 5, 1980.
2. EPA Proposed Method 18, Draft. Personal communication with William
Grimley, U.S. EPA, September 9, 1981.
3. Test Methods. Appendix B to 40 CFR 61. Federal Register Vol. 45, No.
77, Friday, April 18, 1980.
4. D.E. Lentzen, D.E. Waggoner, E.D. Estes,,and W.F. Gutknecht, IERL-RTP
Procedures Manual; Level 1 Environmental Assessment (Second Edition),
NTIS No. Pb-293-795 Research Triangle Institute, Research Triangle Park,
NC, Octber 1978.
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