-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development. U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/7-84-074a
July 1984
ENVIRONMENTAL ASSESSMENT OF A
CRUDE-OIL HEATER USING STAGED AIR
LANCES FOR NOX REDUCTION
Volume I
Technical Results
By
R. DeRosier
Acurex Corporation
Energy & Environmental Division
555 Clyde Avenue
P.O. Box 7555
Mountain View, California 94039
EPA Contract 68-02-3188
EPA Project Officer: Robert E. Hall
Industrial Environmental Research Laboratory
Research Triangle Park. North Carolina 27711
for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ACKNOWLEDGMENTS
This test was performed in cooperation with TOSCO Corporation at their
refinery located in Bakersfield, California. Appreciation is gratefully
extended to J. Caufield, C. Mulkey, J. McCaskill, and D. Walker of TOSCO
Corporation for their help and cooperation in arranging and conducting this
test. Recognition is extended to R. Tidona, A. Frohoff, and J. Pionessa of
KVB, Inc. for operating the continuous monitors and staged air lances.
Special recognition and thanks are extended to the Acurex field test crew of
M. Chips, J. Holm, J. Sniffen, and J. Steiner, under the supervision of
B. DaRos.
-------
TABLE OF CONTENTS
Section Page
1 INTRODUCTION 1-1
2 SOURCE DESCRIPTION AND OPERATION . 2-1
3 EMISSION RESULTS 3-1
3.1 CRITERIA AND OTHER GAS PHASE SPECIES EMISSION
RESULTS 3-1
3.2 TRACE ELEMENT EMISSION RESULTS 3-8
3.3 ORGANIC EMISSION RESULTS 3-16
3.3.1 GI-CS Hydrocarbon, TCO, and Gravimetric Analyses . . . 3-17
3.3.2 IR Spectra of Total Extracts 3-20
3.3.3 Low Resolution Mass Spectrometry (LtfMS) of Total
Extracts 3-20
3.3.4 Gas Chromatography/Mass Spectrometry Analysis of XAD-2
Extracts 3-24
3.4 RADIONUCLIDE EMISSION RESULTS 3-27
4 ENVIRONMENTAL ASSESSMENT 4-1
4.1 EMISSIONS ASSESSMENT 4-1
4.2 BIOASSAY ANALYSIS 4-2
4.3 CONCLUSIONS 4-2
APPENDIX A ~ TEST EQUIPMENT AND PROCEDURES A-l
APPENDIX B — TRACE ELEMENT CONCENTRATIONS AND MASS
BALANCES B-l
111
-------
LIST OF ILLUSTRATIONS
Figure Page
2-1 Schematic of the Crude-Oil Heater Tested 2-2
2-2 Flow Schematic of Staged Combustion Air System for a Natural
Draft Process Heater 2-5
3-1 Refinery Crude Heater Sampling Locations 3-3
IV
-------
LIST OF TABLES
Table page
1-1 Completed Tests During the Current Program .......... 1-4
2-1 Heater Operating Conditions ................. 2-3
3-1 Flue Gas Measurements .................... 3-2
3-2 Gaseous Emissions ...................... 3-4
3-3 Fuel Analyses ........................ 3-6
3-4 Sulfur Balance ...... . ................ 3-7
3-5 Flue Gas Trace Element Emissions ..... .- .......... 3-9
3-6 Relative Trace Element Concentrations Between the Baseline and
Low-N0x Tests ........................ 3-11
3-7 Baseline Test Trace Element Mass Balance ........... 3-12
3-8 Low NOX Test Trace Element Mass Balance ........... 3-14
3-9 Summary of Total Organic Emissions .............. 3-18
3-10 XAD-2 Extract TCO Results .................. 3-19
3-11 Summary of IR Analyses of SASS Sample Total Extracts ..... 3-21
3-12 Summary of LRMS Analyses of XAD-2 Extracts .......... 3-22
3-13 Compound Classes and Characteristic Fragment Ions Sought by
Direct- Insert ion Probe LRMS ......... . ........ 3-23
3-14 Compounds Sought in the GC/MS Analysis and Their Detection
Limits . ........................... 3-25
3-15 Results of the GC/MS Analyses ................ 3-26
3-16 Particulate Radioactivity .................. 3-27
4-1 Flue Gas Species Emitted at Levels Exceeding 0.1 of an
Occupational Exposure Limit ................. 4-3
4-2 Bioassay Results .............. . ........ 4~3
-------
SECTION 1
INTRODUCTION
This report describes and presents results of environmental assessment
tests performed for the Industrial Environmental Research Laboratory/Research
Triangle Park (IERL/RTP) of the Environmental Protection Agency (EPA) under
the Combustion Modification Environmental Assessment (CMEA) program, EPA
Contract No. 68-02-3188. The CMEA started in 1976 with a 3-year study (NOX
EA), EPA Contract No. 68-02-2160, having the following four objectives:
• Determine multimedia environmental effects from stationary
combustion sources and combustion modification technology
• Develop and document control application guidelines to minimize
these effects
• Identify stationary source and combustion modification R&D
priorities
• Disseminate program results to intended users
During the first year of the NOX EA, data and methodologies for the
environmental assessment were compiled. Furthermore, priorities for the
schedule and level of effort for the various source/fuel/control combinations
were identified. This effort revealed major data gaps, particularly for
noncriteria pollutants (organic emissions and trace elements) for virtually
all combinations of stationary combustion sources and combustion modification
techniques. Consequently, seven environmental field test programs were
1-1
-------
undertaken to fill these data gaps. The results of these tests are documented
In seven individual reports (references 1-1 through 1-7) and in the final
NOX EA report summarizing the entire 3-year effort (reference 1-8).
The current CMEA program has as its major objective the continuation
of multimedia environmental field tests initiated in the original NOX EA
program. These tests, using standardized Level 1 sampling and analytical
procedures (reference 1-9) are aimed at filling the remaining data gaps and
addressing the following priority needs:
Advanced NOX controls
Alternate fuels
Secondary sources
EPA program data needs
— Residential oil combustion
~ Wood firing in residential, commercial, and industrial sources
— High interest emissions determination (organics, radionucl ides,
candidate hazardous air pollutant species, etc.)
Nonsteady-state operations
Advanced forms of combustion modifications have been developed in
recent years as a means of reducing NOX emissions without adverse
consequences, such as capacity loss caused by derating the unit. Staged
combustion using air injection lances is one form of combustion modification
that is relatively easy to retrofit to industrial-sized combustion equipment
since it requires only minor hardware modification.
A refinery crude oil heater, using staged combustion by means of air
injection lances (reference 1-10), was selected for environmental tests under
the CMEA program. The objective of the tests was to quantify air emissions
from the heater operating in its normal state and compare these with emissions
1-2
-------
from the heater in the low-NOx configuration while using the air lances. The
data presented in this report quantify stack emissions and identify pollutants
of concern using results from standard sampling and analytical procedures.
Table 1-1 lists all tests performed to date in the CMEA effort and
outlines the source, fuel, combustion modifications, and level of sampling and
analysis in each case. Results of these test programs are discussed in
separate reports available through EPA.
1-3
-------
Table 1-1. Completed Tests During the Current Program
Source
Description
Test Points
Unit Operation
Sampling Protocol
Test Collaborator
Spark ignited natural
gas-fired reciprocating
internal combustion
engine
Large bore, 6-cylinder,
opposed piston, 186 kW
(250 Bhp)/cyl. 900 rpm,
Model 38TDS8-1/8
Baseline (pre-NSPS)
Increased air-fuel
ratio aimed at
meeting proposed
NSPS of 700 ppm
corrected to IS
percent 02 and
standard atmospheric
conditions
Engine exhaust:
— SASS
— Method 5
-- Gas sample (Cj - Cg HC)
-- Continuous NO, NOX, CO,
C02, 02, CH4, TUHC
Fuel
Lube oil
Fairbanks Morse
Division of Colt
Industries
Compression ignition
diesel-fired
reciprocating internal
combustion engine
Large bore, 6-cyUnder
opposed piston, 261-kU
(350 Bhp)/cyl, 900-rpm,
Model 38TDD8-1/8
Baseline (pre-NSPS)
Fuel injection retard
aimed at meeting pro-
posed NSPS of 600 ppm
corrected to IS per-
cent 0? and standard
atmospheric conditions
Engine exhaust:
-- SASS
— Method 8
-- Method 5
— Gas saipple (Cj - Cf, HC)
— Continuous NO, NOX, CO,
COZ, 02. CH4, TUHC
Fuel
Lube oil
Fairbanks Morse
Division of Colt
Industries
Low-N0x residential
condensing heating
system furnished by
Karl sons Blueburner
Systems Ltd. of Canada
Residential hot water
heater equipped with
M.A.N. low-NOx burner,
0.55 ml/s (0.5 gal/hr)
firing capacity, con-
densing flue gas
Low-N0x burner design
by M.A.N.
Furnace exhaust:
-- SASS
-- Method 8
— Method 5
-- Gas sample (Cj - Cg HC)
-- Continuous NO, NO,, CO,
C02, 02, CH4, TUHC
Fuel
Waste water
New test
Rocketdyne/EPA
1ow-NOx residential
forced warm air furnace
Residential warm air
furnace with modified
high pressure burner and
firebox. 0.83 ml/s
(0.7S gal/hr) firing
capaci ty
Low-N0x burner design
and Integrated furnace
system
Furnace exhaust:
- SASS
— Method 8
— Controlled condensation
— Method 5
-- Gas sample (Cj - Cg HC)
— Continuous NO. NOX, CO.
C02, 02, CH4. TUHC
Fuel
New test
-------
Table 1-1. Continued
Source
Pulverized coal-fired
utility boiler,
ConesviUe station
Nova Scotia Technical
College industrial
boiler
Adelphi University
industrial boiler
Pittsburgh Energy
Technology Center (PETC)
Industrial boiler
Description
400-MU tangent 1 ally
fired; new NSPS
design aimed at
meeting 301 ng/J
NOX limit
1.14 kg/s steam
(9,000 Ib/hr) ftretube
fired with a mixture
of coal-oll-water (COW)
1.89 kg/s steam
(15,000 Ib/hr)
hot water
fire tube fired with a
mixture of coal-oll-
water (COM)
3.03 kg/s steam
(24.000 Ib/hr) watertube
fired with a mixture of
coal-oil (COM)
Test Points
Unit Operation
ESP inlet and outlet,
one test
- Baseline (COW)
-- Controlled SO?
emissions wttn
limestone injection
-- Baseline (COW)
-- Controlled S02
emissions with
Na2COj injection
-- Baseline test only
with COM
Sampling Protocol
ESP inlet and outlet:
— SASS
— Method 5
— Controlled condensation
-- Gas sample (Ct - C6 HC)
-- Continuous NO, NOX, CO,
C02. 02
Coal
Bottom ash
ESP ash
Boiler outlet:
-- SASS
— Method 5
— Method 6
— Controlled condensation
-- Gas sample (Cj - C6 HC)
-- Continuous 02, C02,
CO. NO
Fuel
Boiler outlet:
-- SASS-
-- Method 5
-- Method 8
-- Controlled condensation
-- Gas Sample (q - C6 HC)
-- Continuous 02, C02, NO,
CO
Fuel
Uoiler outlet:
-- SASS
-- Method 6
-- Controlled condensation
-- Continuous 02> C02, NO.
TUIIC, CO
-- N^O ijrdb sainplu
Fuel
Test Collaborator
Exxon Research and
Engineering (ER&E)
conducting cor-
rosion tests
Envirocon per-
formed part icu late
and sulfur
emission tests
Adelphi University
PETC and lienural
Electric (ill)
-------
Table 1-1. Continued
Source
Description
Test Points
Unit Operation
Sampling Protocol
Test Collaborator
TOSCO Refinery vertical
crude oil heater
2.54 Ml /day
(16,000 bbl/day) natural
draft process heater
burning oil/refinery gas
Baseline
Staged combustion
using air Injection
lances
Heater outlet:
-- SASS
-- Method 5
-- Controlled condensation
— Gas sample (C( - C6 ItC)
-- Continuous 0?. NO, CO,
CO?, HC
— N?0, grab sample
Fuel otl
Refinery gas
KVB coordinating
the staged com-
bustion operation
and continuous
emission monitoring
Mohawk-Getty Oil
industrial boiler
8.21 kg/s steam
(65.000 Ib/hr)
watertube burning
mixture of refinery gas
and residual oil
Baseline
Ammonia injection
using the noncatalytic
Thermal DeNOx
process
Economizer outlet:
— SASS
-- Method 5, 17
-- Controlled condensation
•- Gas Sample (Ci - C6 HC)
— Ammonia emissions
— N?0 grab sample
-- Continuous 02, NO,
CO, C02
Fuels (refinery gas and
residual oil)
New test
Industrial boiler
2.52 kg/s steam
(20,000 Ib/hr) watentube
burning woodwaste
Basel1ne (dry wood)
Green wood
Boiler outlet:
-- SASS
-- Method 5
-- Controlled condensation
-- Gas sample (Cj - C6 HC)
— Continuous 02. NO, CO
Fuel
Flyash
North Carolina
Department of
Natural Resources,
EPA 1ERL-RTP
Industrial boiler
3.16 kg/s steam
(29,000 Ib/hr)
firetube with refractory
firebox burning woodwaste
-- Baseline (dry wood)
Outlet of cyclone participate
collector:
-- SASS
-- Method 5
-- Controlled condensation
-- Gas sample (Ct - Ce HC)
-- Continuous 02, NOX, CO
Fuel
Bottom ash
North Carolina
Department of
Natural Resources,
EPA 1ERL-RTP
-------
Table 1-1. Continued
Source
Description
Test Points
Unit Operation
Sampling Protocol
Test Collaborator
Enhanced oil recovery
steam generator
15 MW (SO million Btu/hr)
steam generator burning
crude oil equipped with
MHI low-NOx burner
-- Performance mapping
— Low NOX operation
Steamer outlet:
— SASS
-- Method 5
— Method 8
— Gas sample (Cj - C6 IIC)
Continuous Oy, NOX, CO,
CO?
NoO grab sample
Fuel
Getty Oil Company,
CE-Natco
Pittsburgh Energy
Technology Center
(PETC) Industrial
boiler
3.03 kg/s steam
(24,000 Ib/hr) watertube
fired with a mixture of
coal-water (CUM)
Baseline test only
with CUM
Boiler outlet:
-- SASS
— Method 5
— Method 8
-- Gas sample (Cj - C6 HC)
Continuous ,0?. NOX. CO,
COp, TUIIC
NoO grab sample
Fuel
Bottom ash
Collector hopper ash
PETC and General
Electric
-------
Table 1-1. Concluded
Source
Internal combustion
engine — nonselective
NOX catalyst
Industrial boiler
Industrial boiler
Description
BIB HP Waukesha engine
equipped with OuPont USER
catalyst
180 kg/hr steam
(400 Ib/hr) stoker fired
with a mixture of coal
and waste plastic
7.6 kg/s steam
(60,000 Ib/hr) watertube
retrofit for CHM firing
Test Points
Unit Operation
— Baseline
— Baseline (coal)
— Coal and plastic
— Baseline (CUM)
Sampling Protocol
Catalyst inlet and outlet
-- SASS
-- NH3
-- HCN
— Grab sample NgO
-- Continuous 0?, CO?, NOX
TUHC fuel
Boiler outlet
~ SASS
— VOST
— Method 5/8
-- HC1
— Continuous 02. NOX, CO,
CO?, 1UHC
— N?0 grab sample
Fuel
Flyash
Bottom ash
Cyclone ash
Boiler outlet
-- SASS
-- VOST
— Method 5/8
— Grab sample (Ci-Cg HC)
— Grab sample ^0
— Continuous NOX. CO, CO?,
02. TUHC, S02
Fuel
Test Callaborator
Southern California
Gas
Vermont Agency of
Environmental
Conservation
EPRI, E. 1. OuPont
I
CO
-------
REFERENCES FOR SECTION 1
1-1. Larkin, R., and E. B. Higginbotham, "Combustion Modification Controls
for Stationary Gas Turbines: Volume II. Utility Unit Field Test,"
EPA-600/7-81-122b, NTIS PB 82-226473, July 1981.
1-2. Higginbotham, E. B., "Combustion Modification Controls for Residential
and Commercial Heating Systems: Volume II. Oil-fired Residential
Furnace Field Test," EPA-600/7-81-123b, NTIS PB 82-2311756, July 1981.
1-3. Higginbotham, E. B., and P. M. Goldberg, "Combustion Modification NOX
Controls for Utility Boilers: Volume I. Tangential Coal-fired Unit
Field Test," EPA-600/7-81-124a, NTIS PB 82-227265, July 1981.
1-4. Sawyer, J. W., and E. B. Higginbotham, "Combustion Modification NOX
Controls for Utility Boilers: Volume II. Pulverized-Coal Wall-fired
Unit Field Test," EPA-600/7-81-124b, NTIS PB 62-227273, July 1981.
1-5. Sawyer, J. W., and E. B. Higginbotham, "Combustion Modification NOX
Controls for Utility Boilers: Volume III. Residual-Oil Wall-Fired
Unit Field Test," EPA-600/7-81-124c, NTIS PB 82-227281, July 1981.
1-6. Goldberg, P. M,, and E. B. Higginbotham, "Industrial Boiler Combustion
Modification NOX Controls: Volume II. Stoker Coal-Fired Boiler Field
Test — Site A,ft EPA-600/7-81-126b, NTIS PB 82-231085, July 1981.
1-7. Lips, H. I., and E. B. Higginbotham, "Industrial Boiler Combustion
Modification NOX Control: Volume III. Stoker Coal-Fired Boiler Field
Test — Site B,fl EPA-600/7-81-126c, NTIS PB 82-231093, July 1981.
1-8. Waterland, L. R., et al., "Environmental Assessment of Stationary
Source NOX Control Technologies — Final Report," EPA-600/7-82-034,
NTIS PB 82-249350, May 1982.
1-9. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition},'1 EPA-600/7-78-201,
NTIS PB 293795, October 1978.
1-10. Tidona, R. J., et al., "Refinery Process Heater NOX Reductions Using
Staged Combustion Air Lances," EPA-600/7-83-022, NTIS PB 83-193946,
March 1983.
1-9
-------
SECTION 2
SOURCE DESCRIPTION AND OPERATION
The tests were performed on a natural draft, crude-oil process heater
located at the TOSCO oil refinery in Bakersfield, California. The heater has
a rated maximum firing rate of 16 MW (55 million Btu/hr) heat input. The
heater is fired by six John Zink D8A-22 natural draft burners, which are
combination oil/gas burners with a turndown ratio of 3:1. Testing was
performed with the unit firing approximately a 64/36 (heat input basis)
refinery gas/oil mixture. All six burners were firing reabsorber gas from the
plant. However only four were cofiring oil during the tests due to plugged
oil guns in the other two burners which could not be cleaned in time for the
tests. This unit normally fires exclusively reabsorber gas during the summer
(when tests were performed) since it is in plentiful supply as a result of
normal refinery operations at this time of year.
Figure 2-1 is a schematic diagram of the process heater. The sampling
ports were located approximately 6 stack diameters from the damper which is
not enough to establish a uniform velocity profile. This is supported by
preliminary traverse data which indicated that the flow was predominately on
one side of the stack (reference 2-1). Table 2-1 summarizes the boiler
operating data for both tests. As noted, the heater was firing about
64 percent reabsorber gas and 36 percent oil (by heat input for both tests).
The fuel flowrates remained essentially constant throughout the tests. There
2-1
-------
Cl
o =
o E
-CM
•Stack 4 ft, 6 in.
outside diameter
(1.4m)
c
LO
c
CM =
Lft _
o ^
" CM
4->
•*- 1
CO f
u
ra;
Convection
section
'Jot 'to Scale
Radiant section
16 ft, 9.5 in.
outside diameter
(5.1m)
15 ft, 9.5 in.
inside diameter
(4.8m)
Air plenum and
sound suppression
box
Figure 2-1. Schematic of the Crude-Oil Heater Tested
2-2
-------
Table 2-1. Heater Operating Conditions
Process rate, 1/s (bbl/day)
Reabsorber gas
Flowrate m3/min (scfm)
Heat input MW (million Btu/hr)
Fuel oil
Flowrate kg/mi n (Ib/min)
Heat input MW (million Btu/hr)_
Temperatures, °C (°F)
Crude in
Crude out (east)
Crude out (west)
Tube 13, pass A
Tube 13, pass B
Tube 15, pass A
Tube 15, pass B
Tube 20, pass A
Tube 20, pass B
Tube 25, pass A
Tube 25, pass B
Pressures, kPa, (psig)
Crude in (east)
Crude in (west)
Crude out
Burner - oil3
Burner - steam3
Burner - gasb
Gas pressure to heater
Excess air (percent)0
Baseline
21.5 (11,640)
7.1 (251)
8.35 (28.5)
6.59 (14.5)
4.77 (16.3)
c
196 (384)
338 (641)
336 (637)
403 (758)
407 (764)
391 (735)
373 (704)
397 (746)
411 (772)
411 (771)
416 (780)
960 (140)
896 (130)
227 (33)
324 (47)
537 (78)
30 (4.4)
234 (34)
22
Low NOX
21.5 (11,640)
7.1 (251)
8.13 (27.7)
6.55 (14.4)
4.75 (16.2)
196 (384)
339 (642)
339 (642)
405 (761)
395 (743)
387 (728)
373 (704)
395 (743)
395 (743)
406 (762)
408 (766)
960 (140)
896 (130)
234 (34)
324 (47)
537 (78)
30 (4.3)
241 (35)
17
3Average of four burners using oil
^Average of all six burners
Calculated from fuel analyses and flue gas
measurements
2-3
-------
were no significant changes in the operating conditions of the heater which
would affect the crude oil flowing through it.
The-low NOX test used a system of air injection lances to effect staged
combustion for NOX control. Figure 2-2 presents a schematic of the system
which consists of a fan to supply air to the lances, a manifold and associated
tubing, and 24 (4 per burner) variable-height lances (reference 2-2). The
lances consist of vertical tubes of 316 stainless steel, having a 3.18-cm
(1.25-in.) outer diameter with a 45° elbow near the end. The elbow provides
better mixing across the flame. Although the air lances are capable of
delivering half of the stoichiometric combustion air, they delivered 44
percent during the test. The rest of the combustion air is delivered through
secondary air registers located at the base of the heater. Air flow through
the heater is controlled by the stack damper located above the convection
section.
2-4
-------
r\j
i
en
Heater
L_ J
Staged air system
Flexible tubing
Butterfly valve
See detail A and B
r3-in. PVC VIO-in. x 8-in.
I ball valve \reducer
X
8-in. cap
7
''a-'
-™- outlet
8-in. x 4-in. saddle fFVC) td> connect 8-in. PVC to 4-in. x 3-in. bushing
90° PVC
,
-in. PVC-T
3-in. PVC-1
1.75-in. ID
flexible tube
3-in. x 1.25-in.
reducer
Pi tot tube
3-in. ball valve
Detail A
Side view
typical
)=O=(
-3-in. x 1.25-in.
reducer
3-in. PVC
8-in. PVC
Detail B
Top view
typical
Figure 2-2.
Flow Schematic of Staged Combustion Air System
for a Natural Draft Process Heater
cv
i
X
-------
REFERENCES FOR SECTION 2
2-1. R. DeRosier and B. OaRos, "Environmental Assessment of a Crude-Oil
Heater Using Staged Air Lances for NOX Reduction," Vol II: Data
Supplement, Acurex Technical Report, TR-82-94/EE, November 1983.
2-2. Tidona, R. 0., et al, "Refinery Process Heater NOX Reductions Using
Staged Combustion Air Lances," EPA-600/7-83-022, NTIS PB 83-193946,
March 1983.
2-6
-------
SECTION 3
EMISSION RESULTS
The objective of this test program was to measure flue gas emissions
from a crude-oil heater in an "as-found" (baseline) configuration and using
staged combustion for NOX control via air injection lances. Table 3-1
summarizes the flue gas emissions measurements made' by Acurex and the test
collaborator KVB, Inc. Figure 3-1 shows the sampling locations. Succeeding
discussion of the measurement results has been arranged by pollutant grouping.
Criteria and other gas phase emissions are discussed in section 3.1, inorganic
trace elements in section 3.2, organic species in section 3.3, and
radionuclides in section 3.4. Section 4 presents an environmental assessment
of the emissions and the results of biological testing of the organic sample
extracts.
3.1 CRITERIA AND OTHER GAS PHASE SPECIES EMISSION RESULTS
Table 3-2 summarizes gaseous and particulate emissions measured during
both the baseline and staged combustion tests. Continuous monitors (described
in appendix A) were used to measure Og, CO?, CO, NOX, and S02 emissions. The
only significant changes in these measurements between the two tests were
decreases in 03 and NOX. Emissions of other species remained relatively
unchanged. The average Og level in the low-NOx test was 3.3 percent compared
to a baseline level of 4.0 percent. The NOX reduction for this test was 31
percent, a decrease to 118 ppm from a baseline level of 172 ppm (at 3 percent
°2» dry)' In previous tests, KVB has achieved 64 percent NOX reductions
3-1
-------
Table 3-1. Flue Gas Measurements
Pollutant
Measurement Technique3
NOX, 02, C02, CO, S02
Particulate matter
S02/S03
C1"C6 hydrocarbons
Volatile and condensable
organic species, trace
elements
Continuous monitors^
EPA Method 5
Controlled condensation
Gas chromatography
Source Assessment Sampling System (SASS)
Measurement and analysis techniques are discussed in detail in appendix A
Performed by KVB
3-2
-------
ULU
UJU
Method 5
SASS
C,-Cg grab samples
N90 grab samples
'
Controlled
condensation
,
Heated sampling
line to continuous
monitors
02, C02', CO, S02, NO,
Oil and readsorber gas
JFuel samples
Figure 3-1. Refinery Crude Heater Sampling Locations (Sketch not to Scale)
3-3
-------
Table 3-2. Gaseous Emissions
As Measured
0?, percent (dry)
C02, percent (dry)
CO, ppm (dry)
NOX, ppm (dry)
SO?, ppm
Continuous monitor (wet)
Controlled condensation (dry)
S03
Controlled condensation, ppm (dry)
Water, percent
N20, ppm (wet)
Vapor phase organics (Ci-C$) ng/dscm
Sennvolati le organics (TCO), rag/rtscm
Nonvolatile organics (Gravimetric),
mg/dscm
Corrected
CO
NOX (as N02)
N?0
Continuous monitor
Controlled condensation
S03
Controlled condensation
Paniculate ~ Method 5
Solid
Condensable
inarticulate -- SASS
Vapor phase organics (Ci-Cs)
rcu
Gravimetric
Baseline
Range
3.3 to 4.3
10.5 to 13.6
0 to 10
152 to 174
120 to 170
a
—
•-
~
.-
—
—
ppmb
4.0
172
59
190
103
2.5
mg/dscm
31.1
9.4
8.7
16.3
0.4
0.4
ng/J
1.19
83
27
128
69
2.1
8.35
2.52
2.34
4.4
0.11
0.11
Average
4.0
12.1
3.8
162
151
97
2.4
15.9
47.1
16.3
0.4
0.4b
lb/106 Btu
0.0028
0.19
0.064
0.30
0.16
0.0049
0.019
0.0059
0.0054
0.010
0.00019
0.00026
Low NOX
Range
3.1 to 4.2
11.3 to 12.4
0 to 10
108 to 125
125 to 170
—
—
--
—
—
~
—
PP."
3.5
118
33
180
117
1.8
pig/dscm
20.0
3.2
8.1
2.8
0.09
0.5
ng/J
- 0.99
56
15
118
77
1.5
5.0
0.80
2.0
0.72
0.022
0.13
Average
3.3
11.7
3.4
116
148
115
1.8
16.5
27.15
2.8
0.08
0.5
lh/106 Btu
0.0023
0.13
0.0315
0.27
0.18
0.0035
0.012
0.0019
0.0046
0.0017
0.000023
0.00030
Extractive sample
bAt 3 percent Og, flry
3-4
-------
although these were with 100 percent refinery gas firing (references 3-1
and 3-2).
Since the nitrogen content of the oil was the same for the two tests
(0.83 percent measured for the baseline and 0.85 percent measured for the low
NOX as shown in table 3-3), the reduction in NOX can be essentially attributed
to the staging provided by the air lances. Similar to the NOX trend, ^0
emissions decreased from 59 to 33 ppm (at 3 percent 02, dry) from the baseline
to low-NOx tests. CO levels dropped slightly, from 4.0 to 3.5 ppm (at
3 percent 02, dry).
Sulfur species emissions were measured by continuous monitors (S02), a
controlled condensation train (S02 and $03), and SASS (particulate sulfur).
As shown in table 3-2, S02 emissions, as measured by continuous monitors
decreased from 190 ppm (at 3 percent 02, dry) in the baseline test to 180 ppm
(at 3 percent Og, dry) in the low-NOx test. The controlled condensation train
measurements showed an increase from 103 ppm to 117 ppm (both at 3 percent 02,
dry) between the baseline and low-NOx tests. However, the relative magnitude
of change for each method is small enough that a conclusion that S02 emissions
were unchanged is warranted. The fact that the sulfur content of the fuel oil
was measured to be 0.94 percent for the baseline and 0.90 percent for the
low-NOx test, supports this conclusion. S03 emissions, as measured by the
controlled condensation train, decreased from 2.5 ppm to 1.8 ppm (at 3 percent
°2» dnO although, again, the magnitude of this change is insignificant.
Particulate sulfur emissions for both tests were reported as greater than
0.56 yg/dscm because the sulfur concentration in the SASS filter catch
exceeded the upper measurement limit of the spark source mass spectrometry
(SSMS) analysis methodology. Based on the above information, table 3-4
presents a sulfur mass balance for the two tests. In both tests,
3-5
-------
Table 3-3. Fuel Analyses
Fuel gas (percent by volume)
Hydrogen
Nitrogen
Carbon monoxide
Methane
Ethane
Ethyl ene
Propane
Propylene
Isobutane
n-butane
Total butenes
Isopentane
n-pentane
CQ plus
Heating value, MJ/m3
(Btu/ft3)
Oil (percent by weight)
Carbon
Hydrogen
Oxygen (by difference)
Nitrogen
Sulfur
Heating value, MJ/kg
(Btu/lb)
Baseline
8.7
1.1
0.4
22.7
16.7
3.8
29.2
3.3
11.1
1.7
0.5
0.2
0.1
0.5
70.56
1,892
87.37
10.47
0.39
0.83
0.94
43.44
18,720
Low NOX
9,3
0.8
0.5
24.5
16.5
4.0
28.5
3.6
9.5
1.3
0.7
0.2
0.1
0.5
68.71
1,842.6
86.66
10.98
0.61
0.85
0.90
43.54
18,760
3-6
-------
Table 3-4. Sulfur Balance (g/s as Sulfur)
Fuel
Flue gas
S02a
S03b
Parti cul ate
Totals
Balance
(out/In)
Baseline
In
1.03
1.03
Out
0.84
0.01
>2 x 10-6
0.85
82 percent
Low NOX
In
0.98
t
0.98
Out
0.77
0.01
>2 x 10-6
0.78
80 percent
aFrom continuous monitor
controlled condensation
3-7
-------
approximately 80 percent of the sulfur is accounted for. The imbalance is
probably attributable to inaccuracies in estimation of the fuel flowrates,
rather than the particulate sulfur measurements (the balance increases to only
93 percent in the baseline test if it is assumed that all the solid
particulate collected in the Method 5 train were sulfur, an unlikely
possibility).
Because of the small amount of particulate expected from burning oil
and gas, no particulate size fractionation was done in the SASS train.
However, particulate emissions, as measured by both SASS and Method 5, showed
a decrease for the low-NOx test. SASS particulate dropped from 8.7 to
8.1 mg/dscm (at 3 percent 03), while the solid particulate measured by
Method 5 dropped from 31.1 to 20.0 mg/dscm (at 3 percent 03} and condensable
particulate decreased from 9.4 to 3.2 mg/dscm (at 3 percent 02). The
significant discrepancy between the SASS and the Method 5 results is most
likely due to the proximity of the sampling location to a flow disturbance.
For this reason the multipoint Method 5 result is more reliable than the
single-point SASS result.
3.2 TRACE ELEMENT EMISSION RESULTS
The SASS train samples from the heater outlet were analyzed for
73 trace elements using Spark Source Mass Spectrometry (SSMS) and Atomic
Absorption Spectroscopy (AAS). Once the trace element concentrations were
determined by laboratory analysis, trace element flowrates for the flue gas
vapor and condensed phases could be computed. Appendix B presents trace
element concentrations in the SASS components and in the gas stream as well as
flowrates on a mass per time and mass per heat input basis.
Table 3-5 summarizes the trace element concentrations which exceeded
the lower detectability limits in either test. The elements calcium,
3-8
-------
Table 3-5. Flue Gas Trace Element Emissions^
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Cerium
Ces i urn
Chlorine
Chromium
Cobalt
Copper
Dysprosium
Erbium
Europium
Fluorine
Gadolinium
Gallium
Germanium
Gold
Hafnium
Hoi mi urn
Iodine
Iridium
Iron
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
Emissions
Basel ine
(ug/dscm)
__b
<0.97
<0.97
6.6
<0.004
>1.8
6.6
0.0004
—
__
0.18
100
4.2
0.039
7.4
180
0.18
__
__
__
0.27
28
--
0.0093
0.038
0.89
1.3
<0.71
0.015
Low NOX
(ug/dscm)
80
<0.96
<0.96
15
<0.0004
--
22
0.47
380
1.2
<0.47
66
28
0.079
52
0.47
0.0016
0.00040
__
__
0.94
190
2.7
1.2
0.0060
9.4
11
<0.32
3.0
Element
Neodymium
Nickel
Niobium
Osmium
Palladium
Phosphorus t
Platinum
Potassium
Praseodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Terbium
Thallium
Thorium
Thul ium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
Emissions
Baseline
{ug/dscm)
>30
0.35
0.012
...
110
--
0.18
__
<0.71
750
0.0036
>910
14
>880
0.0004
—
<0.0004
5.3
—
0.81
—
12
0.94
Low NOX
(ug/dscm)
29
2.7
33
--
1,100
--
<2.5
<0.13
0.0016
770
6.8
>690
2.3
>1,600
<0.54
0.0012
0.0004
5.4
0.0012
1.7
0.27
f\C
95
8.5
aBlanks indicate concentration below the detection limit of the sampling and
analysis protocol
^Measured concentration less than concentration in blank
3-9
-------
chlorine, fluorine, iron, potassium, silicon, sodium, and sulfur were detected
at concentrations exceeding 0.1 mg/dscm in at least one of the tests. Of
these eight elements, two (sodium and sulfur) could not be quantified because
the concentration in the sample exceeded the upper quantification limit of the
SSMS technique.
Table 3-6 summarizes the changes in trace element concentrations
measured in each test. This information identifies those trace elements whose
concentration differed by more than a factor of three (the accuracy of Level 1
analysis) between the two tests. Of the 48 trace elements detected at greater
than the limit of the analysis method, emission levels of nine were within a
factor of three between the two tests, six were higher in the baseline test,
25 were higher in the low-NOx test, and the changes in eight were
indeterminate. Roughly half of the trace element concentrations which
differed by more than a factor of three between the two tests, differed by a
factor of 10 or more (four out of six of those higher in the baseline and
12 out of 25 of those higher in the low-NOx).
Table 3-7 presents the trace element mass balance for the baseline
test, based upon the SSMS analysis of the fuel oil and the SASS components.
From the table, it is apparent that for only three elements do the inlet and
outlet balance within a factor of three, which is the limit of Level 1
accuracy. The oil analysis results are probably high for chromium, nickel,
and iron, due to potential contamination from the Parr bomb ashing of the oil
for SSMS analysis. However, the mass balance does indicate six elements which
were detected in the fuel but not in the outlet, and 15 elements which were
detected at the outlet, but not in the fuel.
Table 3-8 presents the trace element mass balance for the low-NOx test.
For this test, only two elements are detected in the fuel but not the exhaust,
3-10
-------
Table 3-6. Relative Trace Element Concentrations Between the Baseline and
Low-N0x Tests
Unable to
Determine
Cs
Ni
Rb
Se
Na
S
Te
Sn
Higher in Baseline
By a Factor of >3a
Be*
B*
F*
Ga*
Li
Sr
Within Factor
of 3 Between
Tests5
Sb
As
Cl
Co
Hg
Mo
Si
Ti
V
Higher in Low NOX
By a Factor of >3a
Al
Ba
Br
Cd*
Ca*
Ce*
Cr
Cu
Ge*
I
Fe
La*
Pb*
Mg*
Mn
Nb
P*
K*
Sc*
Ag*
Th
U*
Y
Zn
Zr
aAn asterisk indicates where the concentration differed by a factor
of greater than 10
^Changes in concentration within a factor of 3 indicated that the
concentrations are equal within the accuracy of the analysis
3-11
-------
Table 3-7. Baseline Test Trace Element Mass Balance
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Bromine
Cadmium
Calcium
Cesium
Chlorine
Chromium
Cobalt
Copper
Fluorine
Gallium
Germanium
Iodine
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Niobium
Phosphorus
Platinum
Potassium
Rubidium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tellurium
Thorium
Tin
Titanium
Oil
(wg/s)
1,600
220
11
55
3,300
220
66
<11
770
22
33
11
1,400
22
98
1,100
77
Na
880
990
220
8,700
<11
4,900
<11
11
>35,000
<44
660
Heater Outlet
(wg/s)
0.1
<3.4
<3.4
23
<0.014
>630
2.3
0.0014
0.62 to 2.3
360
15
0.14
26
620
0.63
0.94
99
0.33
0.13
3.1
4.5
<2.5
0.054
>110
1.2
0.043
400
0.62 to 2.3
• <2.5
2,650
0.013
>3,200
50
>3,100
0.0014
<0.0014
19
Mass Balance
(Out/In)
0.000062
*b
*
0..10
*
>5.7
0.43
*
0
*
1.6
0.22
>0.012
0.034
28
0.019
*
0.86
0.070
0.015
0.0014
0.0028
0.058
*
*
>0.12
*
0.000043
0
0.045
*
0
*
0.54
*
>290
4.6
*
*
0
*
0.028
j*Not determined
°Unable to determine
3-12
-------
Table 3-7. Concluded
Element
Uranium
Vanadium
Yttrium
Zinc
Zirconium
Oil
(ug/s)
<55
220
22
980
88
Heater Outlet
(ng/s)
2.8
43
3.3
Mass Balance
(Out/In)
0
0.013
0
0.044
0.038
3-13
-------
Table 3-8. Low NOX Test Trace Element Mass Balance3
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Bromine
Cadmium
Calcium
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Fluorine
Gallium
Germanium
Iodine
Iron
Lanthanum
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Niobium
Phosphorus
P 1 at i num
Potassium
Rubidium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Oil
(u9/s)
1,420
190
110
1,750
550
110
<22
660
44
11
2,800
98
220
1,310
55
Nb
870
550
1,200
7,210
1,750
660
56
3,600
Heater Outlet
(ug/s)
260
<3.2
<3.1
49
<0.0013
68 to 77
1.5
-1,260
4.0
<1.5
2,200
91
0.26
170
1.5
0.0053
0.0013
3.1
630
8.9
4.1
0.02
31
37
<1.05
9.8
96
8.9
110
3,630
<8.2
<0.44
0.0053 to 8.9
2,550
22
>2,300
7.6
>5,300
Mass Balance
(Out/In)
0.19
*c
*
0.45
*
0
*
*
0.72
*
*
4.0
0.83
0.012
0.26
0.035
0.00048
*
*
0.22
*
0.041
0.000091
0.0023
0.68
*
*
0.11
*
0.20
0
0.50
*
*
*
1.5
*
>3.5
0.14
>1.5
aBlanks indicate elements below the detection limit;
trace elements not listed were not detected in either
the inlet or outlet
bNot analyzed
cUnable to determine
3-14
-------
Table 3-8. Concluded
Element
Tellurium
Thorium
Tin
Titanium
Uranium
Vanadium
Yttrium
Zinc
Zirconium
Oil
(yg/s)
<98
1,100
<88
87
330
Heater Outlet
(yg/s)
<1.8
0.0040
0.0013
18
0.0040
5.5
0.89
310
28
Mass Balance
(Out/In)
*
0.000040
*
0.016
0.000045
0.063
*
0.95
*
3-15
-------
while 19 are detected in the exhaust but not the fuel. However, eight trace
elements (Ba, Zn, Mn, Cr, Ca, K, Cl and Si) balanced within a factor of three.
The same potential contamination problem with iron, nickel, and chromium in
the oil sample still exists, so those results should be treated with
suspicion.
For both sets of data, some of the concentrations were indeterminate
because the sample and blank concentrations were both reported as larger than
the upper quantisation limit of the SSMS methodology.
3.3 ORGANIC EMISSION RESULTS
Organic analyses were performed on selected SASS samples according to
EPA Level 1 protocol (reference 3-3), as outlined in appendix A. Volatile
organic species having boiling points nominally in the CI~CQ range of -106° to
32°C (-160° to 90°F) were determined by onsite gas chromatographic analyses of
grab samples. SASS samples were extracted with methylene chloride in a
soxhlet apparatus. Semi volatile organic matter with boiling points nominally
in the Cy-Cjs range of 32° to 300°C (90° to 572°F) were determined in the
laboratory by total chromatographable organic (TCO) analysis of the organic
module sorbent (XAO-2) and condensate sample extracts. Nonvolatile organic
species having boiling points nominally in the greater than Cj/ range of
>300°C (>572°F) were measured by gravimetric analysis of SASS sample extracts
including filter catches.
Infrared spectrometry (IR) was also performed on the gravimetric
residue filter catch and organic module sorbent extracts to identify organic
functional groups present. If certain TCO and gravimetric criteria were met,
further analysis by low resolution mass spectrometry (LRMS) was performed. In
addition, specific polynuclear aromatic and selected other organic species
3-16
-------
were identified by gas chromatography/mass spectrometry (GC/MS) analysis of
total sample extracts. A discussion of the analytical results follows.
3.3.1 C]-_C_g Hydrocarbon, TCP, and Gravimetric Analyses
As indicated in table 3-9, vapor-phase hydrocarbon (C^-Cs) emissions
decreased from 16.3 mg/dscm under baseline conditions to 2.8 mg/dscm under
low-NOx conditions. In the baseline test, they were somewhat evenly divided
among the €3, €3, and €4 boiling point ranges while the low-NOx test produced
only nominal C2 hydrocarbons. Total organic emissions in both tests were
dominated by the Cj-Cs fraction; these accounted for 95 percent in the
baseline and 73 percent in the low-NOx test.
Table 3-9 also summarizes organic emission results from the TCO and
gravimetric analyses. The TCO results have been compromised somewhat in these
tests due to the use of XAD-2 resin which had been inadvertantly contaminated
by acetone between resin preparation and eventual use. Thus, several acetone
solvent contaminants and acetone dimerization products, all of low-molecular
weight and in the TCO boiling point range, were introduced into the resin.
This resulted in a high TCO blank for the XAD-2 resin for both tests.
Table 3-10 shows the sample extract and field blank TCO values from both
tests, and indicates the high, contaminated blank.
In an attempt to correct for the high blank, GC/MS analyses of the
extracts were performed to identify and quantitate specific contaminant
species in both the blank and sample extracts. Subtracting the amount of
these contaminant species found in both sample and blank extracts from the TCO
levels of each, allowed defining a corrected TCO value for both samples and
the blank. These corrected levels are also shown in table 3-10. TCO values
listed in table 3-9 reflect these corrected values. It should be noted that
3-17
-------
Table 3-9. Summary of Total Organic Emissions
Organic Emissions
Volatile organic gases analyzed in
the field by gas chromatography:
n
P
C5
C6
Total Cj-Cg
Volatile organic material analyzed
by TCO:
XAD-2
Organic module condensate
Total Cj-C-[Q
Nonvolatile organic material
analyzed by gravimetric procedure:
Filter
XAD-2
Organic module condensate
Total Ci6+
Total organics
Baseline
(mg/dscm)
0
3.6
4.8
6.4
1.5
0
16.3
0.36
<0.001
0.36
<0.2
0.4
0.4
17.1
Low NOX
(mg/dscm)
0
2.8
0
0
0
0
2.8
0.06
0.02
0.08
<0.3
0.3
0.2
0.5
3.4
3-18
-------
Table 3-10. XAD-2 Extract TCO Results
Baseline TCO
(n>g)
Low-N0x TCO
(mg)
Uncorrected
Sample extract
Blank
Sampl e
Corrected
Sample extract
Blank
Sample
39
30
11
0.5
10.5
25
30
<5
2.3
0.5
1.8
3-19
-------
all contamination consisted of TCO boiling range compounds so gravimetric
results should be unaffected.
The data shown in table 3-9 suggest that emissions of C;+ organics are
unchanged with firing mode. Again, these data are compromised to some degree
because of the resin contamination. However, given the GC/MS corrective
procedure employed, the data are defensible.
In order to evaluate the overall reliability of the organic extraction
and analysis procedure, a sample of clean (and uncontaminated) XAD-2 was
spiked with 1.0 mg of TCO material. Extraction, concentration, and TCO
analysis of this spiked sample gave 0.74 mg implying a 74 percent recovery
by the procedure.
No liquid chromatography (LC) fractionation of extracts was performed
for these tests, since the TCO + gravimetric organic content of no extract
sample exceeded the LC fractionation criterion of 15 mg.
3.3.2 IR Spectra of Total Extracts
IR spectrometry was used to identify organic functional groups present
in SASS samples. Table 3-11 summarizes the results of these analyses for the
filter, XAD-2, and the organic module condensate extracts for both tests.
Only the XAD-2 extract from the baseline test showed measurable absorbances.
These were characteristic of aliphatic hydrocarbons.
3.3.3 Low Resolution Mass Spectrometry (LRMS) of Total Extracts
Table 3-12 presents the results of direct-insertion probe LRMS of the
total XAD extracts from both tests. Table 3-13 lists the compound classes and
fragment ions used to identify compound categories present. In the baseline
test, ethers, heterocyclic sulfur compounds, and carboxylic acids are major
components indicated, while halogenated aliphatics, aromatic hydrocarbons,
nitriles, alcohols, and heterocyclic nitrogen compounds are minor categories
3-20
-------
Table 3-11. Summary of IR Analyses of SASS Sample Total Extracts
Baseline
SASS Component
Filter
XAD-2
OMC
Frequency
(cm-1)
—
2,920
2,840
—
Assignment
No Peaks
CH Alkane
CH Alkane
No Peaks
Low NOX
SASS Component
Filter
XAD-2
OMC
Frequency
—
—
--
Assignment
No Peaks
No Peaks
No Peaks
3-21
-------
Table 3-12. Summary of LRMS Analyses of XAD-2 Extracts
Species Category
Baseline: TCO + Grav = 0.76 mg/dscm
Ethers
Carboxylic acids
Heterocyclic sulfur
compounds
Alkyl ha 1 Ides
Alcohols
Nitriles
Aromatic hydrocarbons
Heterocyllc nitrogen
compounds
Total
Low NOX: TCO + Grav =0.35 mg/dscm
Alyphatic hydrocarbons
Amines
Carboxylic acids
Aromatic hydrocarbons
Total
Intensity
100
100
100
10
10
10
10
10
350
100
100
10
10
220
Estimated Flue
Gas Concentration
(mg/dscm)
0.22
0.22
0.22
0.02
0.02
0.02
0.02
0.02
0.76
0.16
0.16
0.02
0.02
0.36
3-22
-------
Table 3-13. Compound Classes and Characteristic Fragment Ions Sought by
Direct-Insertion Probe LRMS
Compound Class
Fragment Ions (m/e")
Polycyclic aromatic hydrocarbons
Aliphatic hydrocarbons
Halogenated aliphatics
Aromatic hydrocarbons
Ethers
Alcohols
Phenols
Nitriles
Phthalate esters
Amines
Ketones
N-Heterocyclics
Mercaptans, sulfides
Benzothiophenes
Carboxylic acids
Amides
178, 202, 216, 228, 252, 276
57, 71
79, 81, 93, 95, 107, 109, 49, 63
50, 51, 77, 78, 79, 91
•45, 59, 73
45, 59, 61,' 73, 75
51, 77, 94
54, 68, 82
61, 59, 71, 87
44, 58
51, 71
117, 167, 129, 179
47, 61, 75
57, 58, 59, 69, 70, 85, 97, 111, 125
60, 73, 149
58, 72, 86, 100
3-23
-------
indicated. In the 1ow-NOx test, aliphatic hydrocarbons and amines are
indicated as major components while aromatic hydrocarbons and carboxylic acids
are indicated as minor components. The estimated emission level for each
compound category detected, shown in table 3-12, was calculated by
proportioning the total €7+ organic emission levels shown in table 3-9 among
the intensities noted in table 3-12.
3.3.4 Gas Chromatography/Mass Spectrometry Analysis of XAD-2 Extracts
GC/MS analyses of the organic module extracts from the SASS train were
performed to detect and quantify specific polycyclic organic materials (POM)
and selected other organic compounds. The POM and other compounds sought in
the analysis are listed in table 3-14 along with their detection limits in the
GC/MS analyses. The results of the GC/MS analyses are summarized in
table 3-15. Duplicate analyses of the low-NOx XAD-2 extract were performed to
assess the precision of the analyses. Table 3-15 shows that these agreed
quite well. The average of these two analysis runs are used in the following
comparison between baseline and low-NOx emissions.
Eleven specific compounds were identified in concentrations ranging
from <0.04 to 1.4 ug/dscm. In general, emissions of these species were lower
in the low-NOx test than the baseline. The general decrease in these
semivolatile organic priority pollutant species emissions from a total of
4.1 ug/dscm to 1.9 ug/dscm is consistent with the decrease in total organic
emissions noted previously.
Analysis of XAD-2 resin spiked with naphthalene, phenanthrene, and
pyrene yielded recoveries of 33 percent, 38 percent, and <1 percent,
respectively. This suggests that the uncertainty in the data presented in
table 3-14 is approximately a factor of three, at least for the more volatile
species analyzed for.
3-24
-------
Table 3-14.
Compounds Sought in the GC/MS Analysis and Their Detection Limits
(ng/yl Injected)
Acid Compounds
2,4,6-trichlorophenol
p-chloro-m-cresol
2-chTorophenol
2,4-di chlorophenol
2,4-dimethylphenol
5 2-nitrophenol
5 4-nitrophenol
5 2,4-dinitrophenol
5 4,6-dinitro-o-cresol
5 pentachlorophenol
phenol
5
20
20
20
5
1
Base Neutral Compounds
1,2,4-trichlorobenzene 1
1,2-dichlorobenzene 1
1,2-diphenylhydrazine 1
(as azobenzene)
1,3-dichlorobenzene 1
1,4-dichlorobenzene 1
2,4-dinitrotoluene 1
2,6-dinitrotoluene 1
2-chloronaphthalene 1
3,3'-dichlorobenzidine 5
3-methyl cholanthrene 40
4-bromophenyl phenyl ether 1
4-chlorophenyl phenyl ether 1
7,12-dimethyl benz(a)anthracene 40
N-nitrosodi-n-propylamine 5
N-nltrosodimethylamine NA
N-nitrosodiphenylami ne 1
acenaphthene 1
acenaphthylene 1
anthracene 1
benzo(ghi)perylene 5
benzidine 20
benzo(b)fluoranthene 1
benzo(k)fluoranthene 1
benzo(a)anthracene 1
benzo(a)pyrene 1
benzo(c)phenanthrene 40
bis{2-chloroethoxy)methane 1
bis(2-chloroethyl)ether 1
bis(2-chloroisopropyl)ether 1
bis(2-ethylhexy!)phthalate 1
butyl benzyl phthalate 1
chrysene 1
di-n-butyl phthalate 1
di-n-octyl phthalate 1
dibenzo(a,h)anthracene 5
dibenzo(c,g)carbazole 40
diethyl phthalate 1
dimethyl phthalate 1
fluoranthene 1
fluorene 1
hexachlorobenzene 1
hexachlorobutadiene 1
hexachlorocyclopentadiene 1
hexachloroethane 1
indeno(l,2,3-cd}pyrene 5
isophorone 1
naphthalene 1
nitrobenzene 1
perylene 40
phenanthrene 1
pyrene 1
3-25
-------
Table 3-15. Results of the GC/MS Analyses
Species
Phenol
Naphthalene
1,3-dichlorobenzene
1,4-dlchlorobenzene
1 ,2-dichl orobenzene
Nitrobenzene
2-n1trophenol
Diphenylamine
1,2-diphenylhydrazlne
(as azobenzene)
Phenanthrene
2,6-dinitrotoluene
Other polynuclears
Baseline
(ug/dscm)
1.0
<0.04
0_.08
0.04
0.1
0.2
<0.2
0.1
1.4
1.2
<0.04
<0.04
Low NOX
(yg/dscm)
Run 1
0.20
0.40
<0.04
0.04
<0.04
0.04
0.43
0.08
<0.04
0.10
0.10
<0.04
Run 2
0.55
0.78
<0.04
O.Q8
<0.04
0.08
0.39
0.08
0.04
0.20
<0.04
<0.04
Average
0.4
0.6
<0.04
0.06
<0.04
0.06
0.41
0.08
0.04
0.15
0.07
<0.04
3-26
-------
3.4 RADIONUCLIDE EMISSION RESULTS
Portions of the SASS filters were analyzed for alpha, beta, and gamma
activity. In both cases, the filter activities were less than or equal to the
activity of the blank, as shown in table 3-16. Thus, there are no significant
participate radionuclide emissions from this source.
Table 3-16. Particulate Radioactivity
Basel ine
Low NOX
Blank
'Activity pCi/filter*
(*
Gross Al pha
1 18
15 ± 12
1 19
Gross Beta
60.6 + 7.8
75.0 ^ 11.3
99.6 +_ 13.5
Gross Gamma
5 143
£ 143
< 142
aThe + values are the 2 sigma Poisson standard deviation of the
counfing error.
3-27
-------
REFERENCES FOR SECTION 3
3-1. Tidona, R. J., et al., "Refinery Process Heater NOX Reductions Using
Staged Combustion Air Lances," EPA-600/7-83-022, NTIS PB 83-193946,
March 1983.
3-2. Hunter, S. C., W. A. Carter, and R. J. Tidona, "Control of NOX
Emissions from Petroleum Process Heaters Using Staged Air Lances,"
presented at the West Coast Section meeting of the Air Pollution
Control Association, Palm Springs, CA, October 1981.
3-3. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level I
Environmental Assessment (Second Edition)," EPA-600/7-78-201, NTIS
PB 293795, October 1978.
3-28
-------
SECTION 4
ENVIRONMENTAL ASSESSMENT
This section discusses the potential environmental significance of the
refinery heater testing including bioassay testing. As a means to rank
f
species discharged for possible further consideration, flue gas stream species
concentrations are compared to occupational exposure guidelines. Bioassay
analyses were conducted as a more direct measure of the potential health
effects of the effluent streams. Both of these analyses are aimed at
identifying potential problem areas and providing the basis for ranking
pollutant species and discharge streams for further consideration.
4.1 EMISSIONS ASSESSMENT
To obtain a measure of the potential significance of the pollutant
levels in the flue gas analyzed in this test program, flue gas concentrations
were compared to an available set of health-effects-related indicies. The
indices used for comparison were occupational exposure guidelines,
specifically the time-weighted-average Threshold Limit Values (TLV's) defined
by the American Conference of Governmental Industrial Hygienists (ACGIH)
(reference 4-1).
The comparisons of the flue gas stream species concentrations to these
indices should only be performed to rank species emission levels for further
testing and analyses. Table 4-1 lists those pollutant species emitted at
levels greater than 10 percent of their occupational exposure guidelines.
4-1
-------
4.2 BIOASSAY RESULTS
Bioassay tests were performed on the organic sorbent (XAD-2) extracts.
The bioassay tests performed were health effects tests only (reference 4-2).
These were:
• Ames assay, based on the property of Salmonella typhimurium mutants
to revert due to exposure to various classes of mutagens
• Cytotoxicity assay (CHO) with mammalian cells in culture to measure
cellular metabolic impairment and death resulting from exposure to
soluble toxicants
A detailed description of the biological analyses performed- is presented in
Volume II (Data Supplement) of this report.
Table 4-2 summarizes the results from the Ames and CHO assays. The
XAD-2 extract showed moderate toxicity and moderate to high mutagenicity.
4.3 CONCLUSIONS
The use of staged air lances resulted in a decrease in NOX emissions,
with no significant adverse impacts. Particulate and organic emissions
exhibited slight decreases while trace element emissions exhibited an apparent
increase which may be only partially attributable to increases in the trace
element concentrations in the fuel. Bioassay results of XAD-2 extracts
indicated that the extracts were of moderate toxicity for both tests although
the mutagenicity of the extracts increased from moderate for the baseline test
to high for the low-NOx test.
4-2
-------
Table 4-1. Flue Gas Species Emitted at Levels Exceeding 0.1 of an
Occupational Exposure Limit
Species
S02
NCL (as N02)
Silver, Ag
Potassium, Kb
Sodium, Nab
Phosphorus, P
Nickel, Ni
Copper, Cu
Iron, Fe
Calcium, Cab
Flue Gas Concentration (yg/dscm)
Baseline
480,000
200,000
0.0036
110
>910
0.012
>3.0
7.4
28
<0.004
Low NOX
470,000
140,000
6.8
1,100
>690
33
29
52 '
190
380b
Occupational Exposure
Guideline (ug/m^)a
5,000
6,000
10
2,000
2,000
100
100
200
1,000
2,000
threshold Limit Value {reference 4-1)
bTrue value probably higher; at least one component of the SASS train showed a
sample and blank concentration higher than the upper quantification limit
Table 4-2. Bioassay Results
Test
XAO-2 extract:
Baseline
Low NOX
Bioassay
Amesa
M
H
CHOb
M
M
aM - Moderate mutagenicity, H - High mutagenicity
bM - Moderate toxicity
4-3
-------
REFERENCES FOR SECTION 4
4-1. "Threshold Limit Values for Chemical Substances and Physical Agents in
the Work Environment with Intended Changes for 1982," American
Conference of Governmental Industrial Hygienists, Cincinnati, Ohio,
1982.
4-2. Brusick, D. J., and R. R. Young, "IERL-RTP Procedures Manual: Level 1
Environmental Assessment, Biological Tests," EPA-600/8-81-024, NTIS
PB 228766, October 1981.
4.4
-------
APPENDIX A
TEST EQUIPMENT AND PROCEDURES
A.I CONTINUOUS MONITORING SYSTEM
KVB, Inc. provided continuous" vapor phase species emissions monitoring
f
for this test program using a rack-mounted monitor and recorders located in a
mobile emission laboratory. A flow schematic of this flue gas sampling and
analyzing system is shown in figure A-l. The sampling system uses one of
three double-headed positive-displacement diaphragm pumps to continuously draw
flue gas from the stack into the laboratory. The sample pumps pull from up to
six unheated sample lines. Selector valves allow composites of up to six
points to be sampled at one time. The probes are connected to the sample
pumps with 0.95-cm (3/8-in.) or 0.64-cm (1/4-in.) nylon line. The
positive-displacement diaphragm sample pumps provide unheated sample gas to
the refrigerated condenser (to reduce the dew point to 1.7°C (35°F)), to a
rotameter with flow control valve, and to the 02, NOX, CO, and COg
instrumentation. Flow to the individual analyzers is measured and controlled
with rotameters and flow control valves. Excess sample is vented to the
atmosphere.
To obtain a representative sample for the analysis of N02, S02, and
hydrocarbons, the sample must be kept above its dew point, since both water
and heavy hydrocarbons may be condensable, and S02 and N02 are quite soluble
in water. For this reason, a separate electrically heated sample line is used
A-l
-------
ro
Heated Lin*
Mao I fold
Vacuum
Hot
fianpl* Dry Ba»pl«l Lln««
Lina (Typical 6«t-Up Si* Lln«a|.
Banpl*
Puap*
U)
CondaitMr
Not/Cold
Switch
Rafriteration CondeniBr
a*pla Praaiura
. A
^ )Span li iSpan
CO
CO,
Figure A-l. Flue Gas Sampling and Analyzing System (Reference A-l)
-------
to bring the sample into the laboratory for analysis. The sample line is
0.95-cm (3/8-in.) Teflon line, electrically traced and thermally insulated
to maintain a sample temperature of up to 204°C (400°F). A heated diaphragm
pump provides hot sample gas to the hydrocarbon, S02 and NOX analyzers and
cold, dried gas to the other continuous analyzers via the condenser previously
described.
The laboratory trailer is equipped with the analytical instruments
shown in table A-l to continuously measure concentrations of NO, N02, CO, C02,
03, S02, and hydrocarbons. All of the continuous monitoring instruments and
t
sample handling system are mounted in the self-contained mobile laboratory.
The instruments themselves are shock mounted on a metal console panel.
Due to the failure of the electronic datalogger just prior to the start
of these tests, the gaseous emission measurements were determined by manually
interpreting the stripchart recordings and recording 15-min averages.
A-2. PARTICULATE TESTS
Particulate mass emission tests were performed each day in accordance
with EPA Methods 1 through 5. The sampling train used is illustrated in
figure A-2. Both solid particulate matter collected in the filter ahead of
Table A-l. Emission Measurement Instrumentation
Species
Carbon monoxide
Oxygen
Carbon dioxide
Nitrogen oxides
Sulfur dioxide
Measurement Method
IR spectrometer
Polarographic
IR spectrometer
Chemi 1 unri nescent
UV spectrometer
Manufacturer
Beckman Instruments
Tel edyne
Beckman Instruments
Thermo Electron Co.
DuPont Instruments
Model
No.
865
326A
864
10A
400
A-3
-------
•Smith-Greenberq impinger
Stack temperature T.C.
Probe temperature T.C.
>\\\\\\\\\\\v\
"S" type
pi tot tube
Pi tot AP
magnehelic
pressure gages
AH orifice plate
Orifice AH
magnehelic gage
Modified Smith-Greenberg
impingers
meter ^00ml (each) Empty ALice bath
Fine adjustment
by pass valve
Silica gel
•dessicant
Dry test meter
Figure A-2. Particulate Sampling Train
Vacuum
Gauge
'Coarse
adjustment
valve
Air tight
vacuum
pump
Vacuum
line
-------
the impinger section and condensable particulate collected in the impingers
were measured, as indicated in figure A-3.
A.3 SULFUR EMISSIONS
Sulfur emissions (SO? and $03) were measured using the controlled
condensation system illustrated in figure A-4. This sampling system, designed
primarily to measure vapor phase concentrations of $63 as HjSO^ consists of a
heated Vycor probe, a condenser (condensation coil), impingers, a pump, and a
dry gas test meter- By using the condenser, the gas is cooled to the dew
point where 503 condenses as HgSO^ S02 interference is prevented by
t
maintaining the temperature of the gas above the water dew point. Sulfur
dioxide is collected in a 3 percent hydrogen peroxide solution. Both SOg and
503 (as H2$04) are measured by titration with a 0.02 N NaOH solution using
barium thorin as the indicator. A more detailed discussion of the sampling
and analytical techniques for the controlled condensation system is given in
reference A-2.
A.4 TRACE ELEMENTS AND ORGANIC EMISSIONS
Emissions of inorganic trace elements and organic compounds were
sampled with a Source Assessment Sampling System (SASS). The SASS train was
designed and built for EPA's Industrial Environmental Research Laboratory,
Research Triangle Park, for Level 1 environmental assessment (reference A-3).
It collects large quantities of gaseous and solid samples required for
subsequent analyses of inorganic and organic emissions as well as particle
size measurements.
The SASS system, illustrated in figure A-5, is generally similar to the
system utilized for total particulate mass emission tests, with the exception
of:
A-5
-------
FILTER
DESICCATE AND
WEIGH TO
CONSTANT WEIGHT
PROBE. NOZZLE
AND FILTER WASH
EVAPORATE AT
ROOM TEMPERATURE
AND PRESSURE
EVAPORATE AT
ROOM TEMPERATURE
AND PRESSURE
MEASURE VOLUME
TO -1 ml
DESICCATE AND
WEIGH TO
CONSTANT WEIGHT
EXTRACT WITH
3 i 25 ml
ETHYL ETHER
EXTRACT WITH
3 I 25 ml
ETHYL ETHER
EXTRACT WITH
3 > 25 ml
CHLOROFORM
FILTER THROUOH
i? mm TYPE A
GLASS FILTER
EVAPORATE AT
ROOM TEMPERATURE
AND PRESSURE
DESICCATE AND
WEIGH TO
CONSTANT WEIGHT
EVAPORATE ON
STEAM BATH
AND WEIGH TO
CONSTANT WEIGHT
FILTER THROUOH
A 4T mm TYPE A
GLASS FILTER
ROOM TEMPERATURE
CONSTANT WEIGHT
NOTES.
11 ALL WEIGHTS ARE TO NEAREST OOlQ
2) DESICCATE ALL SAMPLES FOR 24 HOURS PRIOR TO WEIGHING
Figure A-3. Sample Analysis Scheme for Particulate Sampling Train
A-6
-------
-1/b" quartz nozzle
316 stainless steel union
-High temperature
heating mantle
Goksoyr/Ross
condenser
Quartz filter holder
Probe T.C
5/8" quartz probe
Heavy wal I
1/4" 1.0.
Latex tubing
Submersible water
circulation pump
I Stainless
condenser heat
Coarse adjustment
valve
Orifice AP
magnehelfc gauge
Dry test nieter
Air tight vacuum pump
_Sm!th-Greenberg
implnyer (100 nt Jt (1,0
[nipty modified Smlth-
Impninei
~Slli(d <|t>l (il'SUdllt tl cl|)
Control nioiJule
Figure A-4. Controlled Condensation System
-------
iluatcd oven -
CO
Stainless
steel
sample
nozzle
Stack
velocity
Magnehelic
gauges
!/<"' fi
11 if
I -.(> lotion
ball voIvu
Organic module
Stainless steel
probe assembly
Gas temperature T.C.
1/2" Teflon line
Oven
Sorbent cartridge
Heater controller
W'Tefbnli
Condcnsate
_lcol lector vessejl
Imp/cooler trace
element collector
Coarse adjustment
Fine adjustment
valve
Orifice 6H
Magnehelic
gauge
Vacuum pumps
I
1(10 ft3/min each)
Inipinger
T.C.
Ice bath
600 grams
Silica gel
desiccant
500 ml
0.2 M AgNOi
0.2 M (NH4)2 S208
SOO ml
30% H202
Heavy wal 1
vacuum line
Figure A-5. Schematic of SASS Train
-------
o Particulate cyclones (not used in these tests) heated in the oven
with the filter to 230°C (450°F)
• The addition of a gas cooler and organic sampling module
* The addition of necessary vacuum pumps
Schematics outlining the sampling and analytical procedures used with
the SASS equipment are presented in figures A-6 and A-7.
Inorganic analyses of solid and liquid samples from the SASS train were
performed with spark source mass spectroscopy (SSMS) for most of the trace
elements. Atomic absorption spectrffscopy (AAS) was used for analyses of
<•
mercury (Hg), antimony (Sb) and arsenic (As).
Quantitative information on total organic emissions was obtained by gas
chromatography for total chromatographable organics (TCO) and by gravimetry
(6RAV) of methylene chloride extracts of solid samples and samples collected
in the sorbent module (XAO-2) and condensate trap. Infrared spectroscopy (IR)
and GC/MS were used for identification of organic functional groups and
polycyclic organic matter (POM) and other organic species in solid and liquid
extract SASS samples. Liquid chromatography of extract samples was not
performed in this test program because the samples contained less than 15 mg
of total organics. Direct insertion probe low resolution mass spectroscopy
(LRMS) of the XAD-2 resin extracts was performed to identify and semiquantify
organic categories present in extract samples. Figure A-8 illustrates the
organic analysis methodology used.
Passivation of the SASS train with 15 percent by volume HN03 solution
was performed prior to equipment preparation and sampling to produce
biologically inert surfaces. Detailed descriptions of equipment preparation,
sampling procedures, and sample recovery are discussed in reference A-3 and
will not be repeated here.
A-9
-------
SAMPLE
SORSENT CARTRIDGE —
AaulOUSCONDENSATE
FIRST IMP1NGER
SECOND ANO THIRD
IMOIMRCOC rnupiwcn
« 0 a x *
1 SI g 2 2 S
5 «a s £ * 2
1 IIs- i > i i a
£ *o> x «OT *S
2 000 S OH" J H
*Sv» ^/ *
>— «C SPLIT
f^ ^ • •
•^ ^ - -^
^ -i ^X ' • • •
._ *
SPtlT X A A
S GRAMS * *
COMBINE
^ AQUEOUS PORTION
\ ORGANIC EXTRACT * • • N
u
3 1
a i
z <
•i
• •
TOTALS
5 2 5
8 1
* If r*amr«d. umoi* ifiould tit Mt •••<• »oc biological irulyin it th« point.
Thit u»o • r«qu,r«d to d««in« th« ton) "»» of o»rtieul»t«
-------
Figure A-7. Exhaust Gas Analysis Protocol
-------
Organic Extract
or
Neat Organic Liquid
1
I
TCO
Analysis
Concentrate
Extract
1
GC/MS Analysis,
POM, and other
organic species
1
I
I
LRMS
Infrared
Analysis
-------
A.5 Cx-C6 HYDROCARBON SAMPLING AND ANALYSIS
Samples of flue gas for Cj-Cg hydrocarbon analysis were collected using
a grab sampling procedure. Flue gas was extracted from the stack at an
average velocity point that corresponded with the average velocity point
selected for SASS sampling. Samples for hydrocarbon analysis were collected
using the apparatus diagramed in figure A-9. The equipment consisted of a
nonheated 0.63 cm (0.25-in.) (o.d.), stainless-steel probe fitted with an
0.7 urn-sintered, stainless-steel filter attached to the probe inlet. The
outlet of the sampling probe was directly attached to the inlet of a Thomas,
i
Teflon-lined, diaphragm vacuum pump. A 500-cm3, stainless-steel, heated
sampling cylinder placed on the outlet of the pump was used to collect this
sample under pressure.
Sampling cylinder construction consisted of specially wrapping each
assembly with a 1.8m (6-ft), heavily insulated, 576-watt, heat tape powered by
a percentage voltage controller. A type K (Alumel/Chrome!) thermocouple
implanted on the metal surface of the sampling cylinder was used to monitor
the cylinder temperature during operation. To ensure even and efficient
heating of the sample cylinder each unit was covered with approximately
1.9-cm (0.75-in.) of ceramic fiber insulation. Figure A-10 presents a
schematic of the sampling cylinder construction details.
Prior to flue gas sampling, the sampling cylinders were preconditioned
by heating each unit to approximately 150°C (300°F) and purging with zero air
(grade 0.1) for 10 min. To extract a flue gas sample the assembled apparatus
was positioned and allowed to preheat to the desired sampling temperature of
120° to 150°C (250° to 300°F). Once up to temperature the diaphragm pump was
started and the sampling cylinder was alternately pressurized and vented with
flue gas to purge the system. Usually 8 to 10 purge cycles were performed with
A-13
-------
sintered stainless-steel filter
l/4-1n. stainless-steel
probe
Teflon diaphragm pump
Pressure gauge
Inlet valve
500-cm stainless-steel
sample cylinder
I
t—•
-p.
• •iAlllllllllllBlllI
Cleramic insulation
and heat tape
Outlet
valve
Thermocouple
Figure A-9.
Hydrocarbon Sampling System
-------
01
Ceramic fiber insulation
Heat tape
Stainless-steel sample valve
Stainless-steel
sample valve
Figure A-10. Schematic of Sampling Cylinder Construction
-------
the last one being retained for analysis. Final pressure in the sampling
cylinder was typically 207 to 345 kPa (30 to 50 psia).
Sample analysis was conducted onsite using a Varian, Model 3700, gas
chromatograph. This unit is equipped with a flame ionization detector (FID)
automatic injection loop, and automatic linear temperature programming.
Table A-2 details the instrument specifications. The gas chromatograph output
was recorded using a Hewlett-Packard Model 3390A reporting integrator.
All samples and calibration standards were analyzed using repeated
injections via the automatic 2-cm3 heated sampling loop. Separation of CI-GS
hydrocarbon components was done on a 1.8m x 0.32 cm x 0.63 cm
(6 ft x 1/8 in. x 1/4 in.) (o.d.) silanized stainless-steel column packed with
60/80 mesh Poropak Q (Super 0) using an isothermal program at 120°C. Table
A-3 presents a summary of the GC operating condition used for the field
analysis.
A summary of Cj-Cg hydrocarbon analysis conducted on selected samples,
sample blanks, and calibration standards may be found in volume II of this
report. Calibration standards consisting of a mixture of C^-Cg parafinic
hydrocarbons (15 ppm each) in nitrogen were analyzed at the beginning and end
of each sample day. Blank samples of zero air were also analyzed in order to
quantify any sample apparatus equipment interference.
A.6 NeO EMISSIONS
The stack gas grab samples were extracted into stainless steel
cylinders for laboratory analysis for ^0. For analysis each sample cylinder
was externally heated to 120°C (250°F), then a 1-ml sample was withdrawn with
a gas-tight syringe for injection into a gas chromatograph. The analytical
equipment consisted of a Varian 3700 gas chromatograph equippped with a 63Ni
electron capture detector and a 3.65-m (12-ft) stainless-steel column packed
A-16
-------
with Poropak Super Q, 80/100 mesh. The injector temperature was kept at
the detector at 350°C, and the column temperature at 33°C. Elution time for
was approximately 5 min, with a flowrate of 20 ml/min of nitrogen.
A-17
-------
Table A-2. Gas Chromatograph Specifications
Van an Model 3700 Gas Chromatograph
Sensitivity
Zero range
Noise (inputs capped)
Time constant
Gas required
1 x 10-12 A/mV at attenuation 1 and
range 10-12 A/mV
-lO"1! to 10"9 A (reversible with
internal switch)
5 x 10-15 A; 0.5 uV peak to peak
220 ms on all ranges (approximate Is
response to 99 percent of peak)
Carrier gas (helium), combustion air,
fuel gas (hydrogen)
Table A-3. Summary of GC Operating Conditions
Injector temperature
Column temperature
Detector temperature
Temperature program
Carrier gas
Fuel gas
Combustion air
120°C
120°C
250°C
Isothermal (120°C.)
Helium (grade 5.0)
Hydrogen (grade 5) 276 kPa
.(40 psi)
Zero air (grade 0.1) 414 kPa
(60 psi)
A-18
-------
REFERENCES FOR APPENDIX A
A-l. Tidona, R. J., "NOX Emissions Assessment: Gaseous Emissions From a
Refinery Process Heater in Baseline and Low NOX Configurations," KVB,
Inc., Irvine, CA, KVB11 47800-1284, prepared for Acurex Corporation,
July 1981.
A-2. Maddalone, R. and N. Gainer, "Process Measurement Procedures:
Emissions," EPA-600/7-79-156, NTIS PB 80-115959, July 1979.
A-3. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201,
NTIS PB 293795, October 1978.
A-l 9
-------
APPENDIX B
TRACE ELEMENT CONCENTRATIONS AND MASS BALANCES
Symbols appearing in the tables:
DSCM Dry standard cubic meter at 1 atm and 20°C
MCS Microgram
PPM Part per million by weight
SEC Second
ng/J Nanogram per Joule
< Less than
> Greater than
N Element not analyzed
U Unable to determine
Trace elements having concentrations less than the detectable limit
or having a blank value greater than the sample value were given an
arbitrary concentration of zero. Values in the form A < x < B were
determined by letting elements reported as less than some concentration be
represented by a concentration of zero for the low value and the reported
concentration as the high value.
B-l
-------
Detectability limits for the various samples were the following:
• Filter — <0.1 yg/g
t XAD-2 — <0.1 ug/g
• Impinger and organic
module concentrate — <0.001
t Fuel Oil — <0.1 pg/g
Baseline Low NOX
FUEL IN
Gas
m3/s
MW
Oil
9/s
MW
EXHAUST GAS OUT
DSCM collected by SASS 27.568 27.702
DSCM/s 3.519 3.288
Molecular weight dry 30.01 30.01
Moisture, percent 15.9 16.5
02, percent dry 4.0 3.3
Standard conditions: 20°C (68°F) and 1 atm. One molecular weight of
an ideal gas occupies 24.04£ at standard conditions;
0.118
8.32
109
4.74
OJ18
8.10
109
4.75
B-2
-------
CO
to
PPM
- - ELEMENT - -
URANIUM
THORIUM
LEAD
MERCURY
G41LD
PLATINUM
' HAFNIUM
PRASEODYMIUM
CtR IUM
LANTHANUM . .
BARIUM
" CESIU"
IODINE
TELLURIUM
' ' ANIlfOTY
TIN
' CADMIUM,
SILVER
NULVBOENUN
' NIOBIUM
mCGNIUH
1 YTTRIUM
STRONTIUM
" RUBIDIUM
" SELENIUM
GERMANIUM
GALLIUM
• 21 NC - -
COPPER
NICKEL - - -
CUBALT
1 RON
MANGANESE ...
CHROMIUM
VANADIUM
IITANIUM
SCANDIUM
CALCIUM ....
POTASSIUM
CHLORINE
SULFUR
PNUSPHURUS
- SILICCN
BASELINE
PPM
- FUEL OIL ----- -
<.SOOEtOO
.200EtOO
N.O EtOO
.0 EtOO
.200Et01
.0 EtOO
.0 EtOO
.2CO£t01
,0 ftoa
. lOOEtQO
.0 EtOO
.. -o f tijn .
.0 EtOO
.0 EtOO
.0 EtOO
.0 ft 00
.BOO EtOO
.?c«Ftoa
.lOOEtOO
.0 EtOO
-Ifln Ft no
.0 EtOO
.0 ftuo
.0 EtOO
.300EtOO
... . .ICUEtOl
.700EtOI
<.uo£tuu
,130Et02
-.TCOEtOO-
.tOOEtOO
.6COEt01
i.lOOEtOO
.300E»02
.«OOEt02
.200£tOL
.ICUEtQI
FILTER ..
.O EtOO
.It ftnn
.6I3E-OI
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.I33£to0
.0 EtOfl
.267E-02
.267E-02
N.O EtOO
<.267E-02
.767F-0?
.240E-OI
.lOIEtflO
.0 EtOO
.a Etoo
.0 EtOO
.0 EtOO
.53.3E-OI
<.267F-02
N.O Etoa
.0 EtOO
.1076-01
.S33E-OI
IteoEtoi
,0 EtOO
.9606-01
.0 EtOO
.0 EtOO
_ U.O EtOO
U.O EtOO
U.O EtOO
>.373EtOI
.eooE-oi
J.O FtQO
._ - HAD- 2 ...
.0 EtOO
.a Etna
.0 EtOO
«.l06EtQO
.0 FtOO
.0 EtOO
. 0 EtOO
.0 EtOO
.0 EtOO
. lOOEtol
«.100EtOO
.0 E »00
.0 EtOO
N.O EtOO
.0 EtOO
.0 etoo
.0 EtOO
.0 EtOO
.0 EtOU
.200EtOO
.0 EtOO
. 300£»0l
<. lOOEtOO
.UOEtOl
.0 EtOO
N.O EtOO
.0 EtOO
.0 EtOO
. ZOUEtOl
.lOOEtOI
.0 EtOO
. 300£tOl
. lUOEtOO
.TOOEtOO
.0 EtOO
.0 EtOO
.0 EtUO
,0 EtOO
.240Et02
.300£tOl
.tOOEtOI
.0 EtOO
. ".OOEtOI
1ST IMPINGE*
.0 EtOO
.a Etoo
.0 EtOO
<.800E-03
.0 Etoa
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.210E-OI
.200E-02
.3006-02
.0 EtOO
N.O EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.400E-02
.0 EtOO
.0 EtOO
.100E-02
.200E-02
.0 EtOO
<.800E-02
N.O EtOO
.0 EtQO
.200E-02
.300E-01
.300E-01
.820E-OI
.0 E too
.ISOEtOO
,9006-02
.IOOE-OI
.0 EtOO
.tOOE-OI
.0 EtOO
.0 EtOO
.0 EtOO
.lOOEtol
>.970EtOl
.0 EtOO
.830£tOI
2ND t 3RD INPINGENS
N.O EtOO
N.O EtOO
N.O EtOO
<.900E-03
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
<.130£-01
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
1
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtQO
N.O EtOO
<.130E-OI
N.O EtOO
N.O (»00
N.O E»00
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
N.O EtOO
:':
•:|
;•
»
•
;•
"
fi
tj
-1
'•4
•1
\
-------
PPN
. ELEMENT
ALUMINUM
MAGNESIUM
SUOIUH
FLUORINE
BORON
BEHVLLIUN
.LITHIUM _
IOSCQ
BASELINE
PPM
FUEL OIL
,UOE»02
<.IOOE»00
.«0t»00
.0 E»00
_,900E»00__
FILTER
U.O E«00
U.O E*00
u.o e»oo
.0 E«00
>.10»E»02.
<.267E-Ol
__.253E«00_
.0 E»00
.0_ E»0«_
"".BOOEtOl
.0 E»00
.0_ E»00
.0 E»00
.0 E«00
1ST IMPINGED
.0 E»00
.I OOE-OI
>.9BO£»01
.200E»01
.200E-02
.0 E»00
.0 E»00
2ND C JRO IMPINCEKS
N.O E»00
N.O E»00
N.o""e»o6
N.O E«00
N.O E»00
N.O
N.O
E«OO
E»00
CO
-Jr'
I.'
-------
CD
I
O1
i
,1
-
;
i-
t—
»
f
.
•
-
-
-
\
HASS/htAl INCUl
tLEHENT
UK AN IUX
IHGMluH
LEAO
MEKCUMt
COLO
PLAIIKUM
HAFNIUM..
PHASEOOVMIUM
CEHIUH
LANTHANUM
BARIUM
iESIUH
IODINE
TELLUMIUH
ANTlMONtf
TIN
CA.UM1UN
SILVER
MOLYBDENUM
NIOBIUM
2IRCONIUM
tHKIUM
SIMON HUM
RunluiuM
UMOHINE
SELENIUM
1RSCMC
GERMANIUM
GALLIUM
1INC
COCPCH
NICKEL
CdUALT
IKIIN
MANlJANCSt
CHHUMIUH
VANAUIUM
T1IANIUM
SCAN01UM
CALCIUM
PUIA^IUM
PllCift.t KUi
Sill 11.1
Rut
dASt
Nu/J
fill EH
.0 £«UO
.0 EtOO
.249E-05
.0 EtOO
.0 EtOO
.0 EtOO
.U EtOu
.0 EtOO
.0 EtOO
.0 EtfiO
.I04E-06
.IOBE-06
N fU, f»00
< . 10KE-U6
.1 Ollt- 06
.9T6E-06
!u E»UO
.0 EtOO
.0 EtOO
.0 EfOO
.0 EtOO
< .IOBE-06
N .U EtOC
.0 tfOO
> .IO/t-02
.i05E~04
.0 EtOO
'.nit-Oi
.0 EtOO
.0 EtUO
U .U EtUO
U .U E»JO
ii .O F*oo
"} • 1 *J 2 t! — 0 J
• J2*jl— Oi
j-
LINE
XAO-2
.'o EtOO
.0 EtOO
< . 134E-03
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.O EtOO
.0 EtOO
.12TE-02
< .I2JE-03
.0 EtOO
.O EtOO
N .0 £tOO
.0 EtOO
,0 EtOO
.0 EtOO
.0 EtUO
.0 EtOO
.2S3E-03
.a Etoo
< Il2TE-0)
. 17IE-02
.0 EtOO
N .0 EtOO
.0 EtOO
.0 EtOO
.253E-02
.I2IE-02
.0 EtOO
.3BOE-02
.127E-03
.887E-03
.J EtJO
.0 EtOO
.0 EtOO
.304E-OI
. JHOt-02
.iOIE-02
.0 EtOO
.SO/E-U2
1ST IMPINbER 2ND t 3RD IMPINCEKS
.0 EtOO
.a EtOO
.O EtQO
< .190E-04
.0 EtOO
.U EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.0 E*00
.V99E-O3
.J13E-0*
.0 6*00
N .0 EtOO
.O EtOO
.0 EtOO
*0 EtOO
.0 EtOO
.0 EtOO
*415E-04
.0 EtOO
< .I90E-0)
N .0 E»00
.0 EtOO
IlDE'03
.7UE-03
.19SE-02
.0 EtOO
,3»l£-02
.2I4E-01
.23BE-OJ
.0 EtOO
.14JE-02
.0 EtOO
.U EtOO
.21UE-OI
> .23(EtOO
.0 EtOO
,|97EtOO
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
H
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
.0
.0
EtOO
EtOO
.0 E*00
.tBlE-04
.0 e»uo
.0
.0
.0
.0
t°
.0
.0
.5
.0
• 24
.0
.0
.0
.0
.0
.0
.0
• 0
.0
.0
EtOO
EtOO
1*60
EtOO
EtOO
EtOO
EtOO
E*OO
EtOO
IE-OS
EtOO
EtOO
EtOO
EtOO
E*00
EtOO
EtOO
l»UU
EtOO ,
EtOO
.0 EtOO
.26IE-03
.0
.0
.0
.0
.0
.U
.0
r°
.0
.0
.0
.0
.0
.0
.11
.0
.0
.0
ttoo
EtOO ~
E»00
EtOO
EtOO
t»oo
EtOO
£»00
Etop
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
Etflfl
EtOO
EtOO
HEAHH OUTLEI
.0 EtOO
.0 EtUi)
.249E-OS
< .190E-03
.0 EtOO
.0 EtOO
.0 EtOO
.0 E»00
.0 EtOO
.0 EtOO
. IIJE-02
.I08E-06
< .261E-03
< .IOBE-06
.IOBE-06
*4I2E-OS
.951E-0*
.2S3E-03
.0 E»00
479('04 .B09E-02
!rS6E-02
.14IE-03
.1136-02
.21IE-03
.I43E-02
.0 EtOO
.0 EtOO
.304E-OI
.2>bE-OI
> .21«EtOO
.12 IE -05
.202£tOO
,
J
1
3
:
3
'•
H
1
:
:
i
i
-------
I' SLu
INI'UI
SUDlilH
FLUORINE
BEimUUH
\ II 1th
u *o t *uo
U . J E«UC
U .0 £»OC
.•) £»00
.103E-OS
1AJ-2
.o ttao
.0 E>00
~
.0 t«00
.a E.DO
.a E»UD
.0 Eiao
I SI INCINUER
2ND C 3HD IHHINCEftS
.It E»OU
.2JBE-1I3
"
N .0 E»OU
K .0 E*OO
N ?B E»06
N .0 E»00
N .0 E»00
Ht»ltk DUIlt!
.O E»UO
.0 E«00
N .0 E»00
N .0 E»00
.0 e»oo
_.23«E-(»3
Ul&E-OI
> .481E-03
< .IOBE-05
.I03E-0*
00
I
t ;
i.
-------
07
I
t
',
«
'
•
'
-
•
-
[
-
t
MASS / HLAl INHJ1
ELEHCNf
URANIUM
IhOKIU!
LEAD
MERCUNV
COLO
PLAIINUN
HAfMUM
PRASEODYMIUM
CERIUM
LANIHANUM
BARIUM
CESIUM
IODINE
TELLURIUM
ANIIMONV
UN
CAUMIUM
SILVE*
MULVBUENUM
NIOtilUM
MKLGMUH
VIIMIUN
STHONIIUM
RUBIUIUM
6DUMINE
SELENIUM
ARSENIC
CEKHANIUM
GALLIUM
IINC
CUPPEk
NILKEL
CUUAL t
IKON
MANGANESE
CHNUMIUM
VANADIUM
Tl IANIUM
SCANDIUM
CALLIUM
PlUiSIUM
ttlLCHIKE
SULfUH
. H.SC"
BASELINE
Nfi/J
tUtL OIL
< .HSE-01
< *9I^E~U2
•^S^E^O?
N .0 t»00
.0 EtOO
,*59E-Ol
.u EtOu
.0 EtOO
.U EtOO
.0 EtOO
.0 E tOO
•230E-02
.0 EtdO
•U EtUQ
.0 £tOO
.0 EtuO
.0 £'00
.0 EtOO
.0 • £»00
*is«E-02
.23UE-02
.0 EtOO .
.115E-01
.0 EtOO
.O EtOO
.0 EtOO
.6BSE-02
.20TEtOO
.IblE'OO
< .23UE-02
.29VttOO
.IfrU-OI
.I3HE-UI
.I3actoo
.*s.t-ti
• 2U IE tOV
• 1 U Jfc * 0 1
HtAIER OUILEI
.0 EtOO
.U EtOO
< !l90E-03
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtOO
.0 E»UO
.0 EtOO
.II7E-02
.714E-0*
. 108E-04
< .26IE-01
< . loaE-ot
.ioaE-06
*«!2E-Oi
.2S3E-03
.0 EtOlI
. 3B2E-02
»rSE-0««<.I74E-01
.178E-02
< .19UE-03
< -26IE-03
.0 EtOO • • ""* ~" ' - '
.180E-04
.329E-02 '
.IVHE-02
. > .H09E-02
.10&E-04 ' '
.7S66-02
.I13E-02
.2UE-03
.H.3E-OJ
.0 EtOO
.0 {too
".276E-UI
>1.2J4Et06" '" — "
.325E-05
.202EtoO
-------
00
I
00
HA!>! / I'lAl
BASELINE
hli/J
HEMtR OOILEI
ALUHlNiJN
HAliNlSIUH
SODIUM
fLUCRINt
.2UE»00
.0 E»00
.2JBC-01
SENmlUH
LllhlUM
.0 E»OU < .10dE-OS
-ZJIE-OI . ltUE-0*
"I
-------
00
I
•o
CUNCEN1 RATION
ELEMENT - -•
URANIUM
IHOfllUN
LEAD
MERCURY
GOLT • ••
PLATINUM
HAFNIUM
PRASEODYMIUM
CERIUM
1 - LAMHANUM •
BARIUM
' cbsiun
IODINE
TELLURIUM
ANTIMONY
TIN
C40PIIM
SILViR
MOLV8UENUM
NIOBIUM
ZIRCONIUM
" »»TP,IMP
SIHONTIUM
RUBIDIUM
1 BROMINE
" SELENIUM
ARSENIC
GERMANIUM
CALL IUM
I INC
COPPER
.- NICKEL
COBALT
IRUN
. - MANGANESE.. -
CHROMIUM
VANADIUM
IIIANIUM
SCAhOIUH
- .. . CALCIUM __.
POTASSIUM
- - . CHLUHINE . _ .
SULFUR
PHCSPMOttUS
ilLICUN
BASELINE
MCG/OSCM
— MLI6R
.0 E»00
.0 E«00
.92DE-02
< .686E-01
.0 £«00 .
.0 E«00
0 E'OO
.0 E«00
.0 E»00
. 0 E*OQ
.202E-01
.0 E'OO
.*u*e-a3
.*04E-01
N .0 f»OQ
< .400E-03
,40*F-a*
.363E-02
.ISJE-CI
•0 S'QO
.0 E«0fl
,n f.nn
.0 E*00
.0 E»00
.80TE-1?
< .404E-03
H .0 f.nn
.0 E»00
.161E-02
- _ ..UttEfOO
.80rE*02
> .tDOEtQl
.3SZE-OI
.rzrEtoo
..0 E»00 .
.USE-01
ifKHiEtOO
.0 E»00
.0 E*00
u. .a E»OD _ .
U .0 E»00
U .0 E>00
> .565E»00
.1216-01
U .U E>00
- KAO-2
.0 E*00
.0 E<00
.0 E»00
< .500E<00
.0 f «00
.0 E»00
.O f«no
.0 £»00
.0 E»00
,0 f»00
.»71E»01
< ,^riF»on
.0 E»00
.0 E»00
H .0 F'On
.0 E»00
.a ttaa
.0 E»00
.0 E»00
,0 F»<"»
.9S3E»00
.0 E»OQ
.I*1E«02
< ,*HE»00
.KfrOE»ot
.0 E»00
N -p F»(lfl
.0 E»00
.0 E»00
.q«lE>ol
.*T1E»OI
, ia<)f»02
.0 E»00
,MIE»02
.«11E*00
.330E«Ol
.a E»00
.0 E»uO
.0 E»00
. .0 . £»00
.II3E>OI
.14IE»OJ _
.184E»02
.0 E«00
.i9Od ,
.a E*OO
.0 E»00
. titEtoa
.0 E«00
.0 E»00
.885E-OI
.I?7E»00
.a E»oo
< . ToaE»oo
H .a E«oo
.0 E»00
.177E»00
.265E»01
.26»E»01
.726E»01
.0 E»DO
.I33E»02
.r«6E»00
.8eSE«00
.0 E»OO
.oie»oi
.0 E»00
.0 EtOO_._
.0 E*00
,R85F,»02
> .856EI03
.0 E «00
• 73*F,»OJ
.2ND &_ 3RD IHPJNGERS
N .0 E»00
N .0 H-Ofl
N . 0 E »OO
< .672E-OL
N .0 f»on
N .0 E«00
H .0 e»oo _
N .0 E»00
N .0 E»00
N - O f»OQ
N .0 E»00
N .0 F»00
N .0 E»00
N .0 E»00
< .4I|F.»0I?
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
H .0 E»00
N .0 E«OO
H .0 £»00
N .0 E»00
N .0 E*00
N .0 E«00
< .<>71E»00
N .0 E»00 -
N .0 E«00
N .0 E»00
N .0 E»00
N .0 E*00
N .0 E«00
N .0 E»00
N .0 £»00
N .0 E«OO
N 3P £«OQ
N .0 E»00
N .0 E»00
N_.0 ?»00
N .0 E»00
N ,Q E»00
N .0 E«00
N .0 E»00
N .0 E»00
HEATER OUT LEI
.0 E»00
.0 E»00
.•J24E-02
< . 706E»00
.0 6»00
.0 E»00
.0 E»00
.0 E»00
.0 E«09
.a E»OO
,6»<>E»01
.lTTfi»00OI
< .7086 »00
< .971E»oa
.0 E»00
,179E»00
.123E»02
.7386*01
> .301E»02
.392E-01
,281E«02
,I27E>01
.420E»01
. 8Q6E»00
.»S1E»01
.0 E»00
«0 E*00
.1I)E»03
.10JE»0>
> .8786*01
.I2IE-OI
,7S3E>0)
~^— —^^— v\
:
^
•;
'.
H
"~
•;
;;
t"
H
.. . t-
•
-------
CONCENTRATION
EL EH EN I
ALUPIMJN
NAbNESIUH
SODIUM
FLUORINE
BORON
BERYLLIUM
.LITHIUM.
.IOSCO ...
BASELINE
HCto/OSCN
ML IE"
U .0 E»00
. U_.0_E»00
U .0 E»00
.0 E«00
> »UIE»OI ... .
KAD-2
.0 E»00
.0_.l»00_
.3TTE»02
.0 E»00
.0 E»00 .
.0 E»00
. I ST. IMPINGE*
.0 E»00
__ .885E«00_
> . 86TE»03
_2MO t WO IftPINGERS HEATER OUTLET
..... ..?B3E=OI
,im»oo
.0 E«00
.0 _ E«00_
N .0 E»00
_N _.0 E»00_
N" .'0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
H .0 E»00
.O E»00
.ITIE*03
< .404E-02
.383E-01
oa
i
-------
1
I
)
t
I
»
»
»
:;
•
MASS/TIME
ELEMENT - -
URANIUM
• THUKIUM •
LEAD
NEHCURY
GOLD
PLAT INUH
HAFNIUM
PRASEODYMIUM
CEXIUM
LANTHANUM
BARIUM
CESIUM
100 IKE
TELLURIUM
-ANTIMONY -
TIN
CA01IUH
SILVER
MOLYBDENUM
NIOBIUM
ZIRCONIUM
YTTRIUM
SIRONTIUM
RUBIDIUM
ttf>r)p|NF
SELENIUM
ARSENIC
GERMANIUM
CALL IUM
- I INC
CCPPER
NICKFI
COOALT
IRON
MN'.CkfSF
CHROMIUM
HANAOIUM
TITANIUM
SCANDIUM
-CALCIUM
POTASSIUM
CHLORINE
SUlfUH
PHOSPHORUS
. SILICON
TGSCO
BASELINE
HCG/SEC
-- --FILTER - - -
.0 E»00
.0 E»00
.32TE-01
< .2«2E»00
.0 E»QO
.0 E»00
>O EfOO
.0 E*00
.0 E»UO
.0 f>
.TlOE-01
,0 F»nn
.142E-02
.1*26-02
N ..0 E*00
< .U2E-02
,l*?F-<»
.IZBE-Ot
.9MJE-01
ifl €«0fr
.0 E»00
-i> r.nn
.0 E*00
•0 E»00
,? rltlF»Q2
.138E»00
.256EKM
.n F»OO
.SUE-QI
.2H4EIDI
.0 E»00
.0 E«00
U__.0_£*OQ
U .0 E»00
U ..0 E»00
> .litftai
.426E-OI
U .0 E»00
HkO-i .
.0 E»00
.0 f*00
.0 E»UO
< .1T«E»OI
-.0 -E»00
.a E«OO
•o E'oa
.U E»00
.0 E»00
,0 F")<>
.166E*02
<-.*166E»QI
.0 E*00
.0 E»00
_N .0 E»0a
.0 E*00
.n rtaa
.0 E»00
.0 E»00
•0 F»00
,J32E»Ol
.a Ftiia
.498E»02
< .I66E»01
. ?l?fKl?
.0 E»00
_M .0 _E*PO
.0 E«00
.0 E»00
.J32F»Q2
.I66E»02
,fcfc^f.»02
.0 E«UO
.49BE«02
,I66E»01
.UtE»02
.a f«oo
.0 E»00
.0 EtOO
.1) EtOO
.39«E«03
.498E>02
.66*E»02
.0 E»00
.6t<,£tU2
. -1ST IMPINCER - 2ND t-JRD.^MPINGERS
.0 6*00
-a Ftoa
.O €»00
< .2*9E»00
-n Ftao
.0 E»00
,(t Ftaa
.0 6*00
.0 E«00
.a f«nn
.«5*E»01
.fc?JE»00
.<»3*E»00
.0 E»00
N .a f»ao
.0 E»OO
.0 e»no
.0 C»oo
.0 E»00
.12«F»DI
.0 E»00
.0 F»0fl
.311E»00
.623E»00
.0 E»00
< .2*9E»01
N .0 E»00
.0 6*00
.623F»00
.93«E«01
.93«E«OI
.255E*02
.0 EtUO
.*5rE*02
.280E»U1
.JllE.Ol
.0 E»00
.187E»02
.0 E»00
.0 E*00
.0 E»00
.3HE»03
> .302E«04
.0 FtOO
.259E»04
N .0 E*00
N .0 E+00
N .0 E»00
< .23TE»00
M .a F»nn
N .0 E»00
N .a ftoa
N .0 E»00
N .0 E*00
N .a E»OO
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
< .3f2E»Ol
N .0 e»oo
N .0 E»00 ^_
N .0 E*00
N .0 E»00
N .0 EH10
N .0 E»00
N .O 6*00
N .0 EKJO
N .0 E»00
N .0 E»00
N .0 E»00
< . 3*2E»01
N .0 e»00 .
N .0 E>00
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E*00
N .0 E»00
N .0 EK)0
N ,0 EtOO
N .0 E»00
N .0 E»00
N .0 Ei-00
N .0 E»00
N .0 E«00
N .0 E»00
N .0 E»00
N .0 E»00
.. HEATER OUTLET
.0 E»00
.0 E«00
.32TE-01
< ,2*9E»01
.a E»00
.0 E»00
.a e»oo
.0 E*00
.0 E»00
.O EtOO
.2326*02
,ft23£»00 .I06E»03
.138E»00
.99[£»02
.446E*OI
.M6E*02
.26*E»01
.18TE»02
.0 E»00
.0 E*00
. 3 .309E»0*
.426E-01
.265E«0»
i
;•
;•
;;
»
i]
»
•j
»
.4
*i
3
::i
^
^
••
H
. ... .
-------
MASS/TIME
ELEHENT
ICSCC. .
BASELINE
MCli/SEC
FILTER
HACNESIUM
SOOIUH
FLUURINE
BORON
U .0 E»00
U .0 E»00
U 40 E»00
.0 E»00
> .566E«OI
< .M2C-OI
X»0-2
.0 E»UO
.0 E*00
.I33E»01
.0 E»00
.0 E»00
,0_E»OQ_
SI INPINGER
.0 f»00
.3IIEXH
> ,10«E»(H
.622E»03
,62JE»00
.0 E»00
.0 E»00
IHO t 9
N
N
N
N
N
N
N
no
.0
.0
.0
.0
.0
.0
.0
IMPINGEHS HEAIFP OUHET '.
6*00 .0 E»OO '
£•00 .MIE»01 ',
E»00 > .119E»04
E*00 .622C>03
E»00 > .63IE»OI !
E»00 < .142E-01
E»00 .U5E«00
CD
I
ro
-------
CO
I
MASS/ TIME
f L EMENT
URANIUM
THORIUM
LEAD
MERCURY
COLO -- -
PLATINUM
— HAFNIUM
PRASEODYMIUM
CER 1UH
• LANTHANUM -
BARIUM
1 CESIUM
100 INE
1 tELLURIUM
ANTIMONY ..
UN
CADMIUM
" SILVER
" MOLYBDENUM
' NIOBIUM
* ZIRCONIUM
YTTRIUM
STRONTIUM
RUOIDIUM
" BROMINE
SELENIUM
AKSEN1C
CERMANIUM
GALLIUM
ZINC
COPPER
Nir.m
COBALT
IKON
- MANGANESE- --
CHHOMIUM
- VANADIUM
TITANIUM
SCANDIUM
CALCIUM
POTASSIUM
CHLCRINE _ ._.
SULFUR
PHOSPHORUS
S1LILUN
BASELINE
MCG/SEC
- FULL OIL .
< .5<.TE»02
-- - < .438E*02
.2I9E>02
N .0 E»00
-.0 E»00
.2I9E>03
,i) E«0o
.0 E<00
.0 E»00
- - - - .0 E»00
.219E«03
.0 f»f>i)
.109E»OZ
.0 E«00
.0 ftnn
.0 E»00
,0 Eton
.0 E'OO
.0 E»00
.0 f-no
.8TSE»02
,?|9f.n?
HE A I Eft OUTLET. _ .... - -.__.. . __ . .
.0 E«00
.0 F»OQ
.I2TE-OI
< .249E»Ul
.0 F»i.'Q
.0 E»00
tO E*yf
.0 E»00
.0 E»UO
-O f»00
.232E«02
ifkn>
.0 E»00
,n ftca
.0 E«00
.1ZBE»02
- .9flSEKn ...
.f«6E»OJ
_.«7*£»ni
< ,IOVE»02
.I42E»04
.T66E»02
.6»6E«02
,?|«f «ftl
.6SiE»01
< .I04E»OZ
. - . .328E»0»
.8»5E»04,
-- -21SE»03
> .]«OE»0)
.9aSE»OI
.'••JiE'O'i
< .2*9E»OI
< .34?F»O1
.0 t»oa
.629CIOO
.«32E«Q2
.2tOE»02
/ . JQtE»Jl
.13SE>00
.99IE»02
.44&E»ul
.I«8£t02
.284ttOI
.l8fE»U2
.0 E«00
.0 E»00
. »SUt»U3
.361E»03 . _. . .
> .309E»O«
.*i6E-«l
.26»£»0*
-------
TIME
ELENENI
M.L.MIMJM
MAGriESIUH
SCOIUH
fLUCRINE
BOHON
BERYLLIUM
LITHIUM
FUEL OK
IOSCO . .
BASELINE
HC&/SLC
.109E*02
.2l9E»02
.109E»02
.0 E»00
HEATER OUILET
.0 E»00
.31IE»Ol
> .J19EK)*
> .63IE»OI
< . U2E-OI
,13SE»00
CO
-------
ca
i
1
•
•
—
BASELINE
NCS/SK „• !
HEATER MA," BALANCE
IN < FUEL OIL OUT > HEATER
ELEMENT TOTAL IN
URANIUM X<.5*TE»02
THORIUM X<.*J«E*02
LEAO - .2i9E*02 - - -
MEKCURY
GULD
PLATINUM .2196*03
HAFNIUM
PRASEODYMIUM
CERIUM
LANTHANUM
BARIUM .2196*03
CESIUM
IODINE tl09f*n'
TELLURIUM
ANTIMONY
YIN
CADMIUM
ilLYEP
MOL VBOENUM
NIOBIUM
I1RCONIUN .8T5E*02
YTTRIUM .219£*02
STRONTIUM ,iQ9Ctft)
RUBIDIUM
BROMINE .54TE«02
SELENIUM
ARSENIC
GERMANIUM
GALLIUM .328E«02
IINC .9856*03
COPPER .ffcbf»03
NICKEL .8J5E*OJ
COBALT ... ... XC.1U9E>Q2.
IRON .1^26*04
MANGANESE . 766E*02
CHROMIUM .*16E»02
VANADIUM .2196*0)
TITANIUM .656E*0)
SCANDIUM X<.IO«Ei02
CALCIUM .3286*04
POTASSIUM .8J5E»(K
CHLORINE .2116*03
SULFUH .15CE*OS 2
X{ •2^*J£#01
XC «3^?£*0l
.629E*00
.2606*02
.I06E*03
^
*
* 1
.3T9E-OI
.0 E *00
*
*
*
.1926-01
.4386-01
.JJ9E-01
.I21E*00
-------
IN I FUEL OIL
ELEMENT
ALUMINUM'
MAUNESIUN
SODIUM
FLUORINE
60 RON
BERYLLIUM
LITHIUM
._. ICSCO _
BASELINE
MtWSIC
HEATER MASS (UlANCE . .
OUT I HtMCR EXHAUST CAS
.219E»02
.10«E»02
TOTAL IN
X<.IOVE»02
\
TOTAL OUT
MASS BALANCEIOUT/INI
,3HE»OI
.314E*04
-------
I
t—>
--4
t
PPM
ELEMENT
URANIUM
• • THQKIUH
LEAO
MERCURf
-- GOLD
PLATINUM
11 _™ , HAFNIUM
PRASEODYMIUM
CCft IUM
" LANTHANUM
BARIUM
" CESIUM
IODINE
TELLURIUM
1 ANT 1 HUN V
TIM
CAOHIUH
SILVER
MOLYBDENUM
NIOBIUM
ZIRCONIUM
YTTRIUM
STRONTIUM
RUBIDIUM
1 BR(jMINE
SELENIUM
M AKSENIC
GERMANIUM
GALLIUM
I INC
COPPER
M — — NICKEL--
COBALT
IKIIN
MANGANESE -
CHRUHIUM
VANA01UH .
IUANIUH
SCANDIUM
CALCIUM
POIASSIUM
CHLORINE
SULFUR
PHOSPHORUS
SILICON
- TCSCO--
LUN NO *
PI'M
FUEL OIL
<.eou£»oo
<.900E*00 -
.40uc+oo
N.O EtOO
.O- E*00 - •- -
. IIOE+U2
,0 £+QO
.0 E+00
.0 E»00
iO E+00
.100E»OI
.,) ftQQ
.0 E+00
.0 E+00
,o e*-oo
.0 E+OO
,0 E"N>
.9 E*00
.0 E»00
.0 E^'»n
.0 E»00
.0 f»nn
,500E»00
.0 E»00
-0 ftnn
.0 6»00
_4 f.n.i
.0 6»l)0
.IOOE»00
. JCOF'CI
.6006^01
,H(tqF>n|
<.20ltE»00
.2tOE»OZ
. «,r,.>
.ICOE*01
.AQQC»UQ
.10(tE»OZ
.0 £»00
.I60£»0i
.»«0€»Q2
.5COt«01
.11UE*02
.40aE«Ql
..16I)E»02
-- FILTER - - -
.7S2E-02
.'J2E-02 --r -,-
•133E*UO
<.2$IE»UO
>l) E»00
.0 E»00
. ..0 -EiOO
.0 E»00
.u E»OO
.0 e»oo
.•iOIE»00
.0 s»oo
.0 E»00
<.251E-02
M.O f*nn
.2S1E-02
, 7SiF-nj
.2*8E»00
,22U»00
.0 F»nn
.U E»UO
^OJE-02
.0 E»00
.0 E«00
.>«iF-al
.IOOE-01
M-Q E»0fl
.2SIE-02
. 100E-01
.(lottOl
.20IFtOO
T?>-«F»n7
.4V«E*00
.T02E>01
... .201EtUO
.491E»00
„ .SQIE»01
.0 E»00
.0 E»00
Utti E*00
U.O £»00
U.O E*0a
>.»IE>01
.1266 tOO
u.u t«oa
KAD-2
.0 E'OO
-l> F»pfl
<.430E-01
. - .a ttoo
.0 £«00
.U F«QO
.0 6*00
.0 £»00
^0 p»no
.200E»OI
<. inoFKin
.200E»00
.0 E»00
N.a F.nn
.0 E»00
.iuoe»oo
.0 £»00
. e>aQE»oo
.0 ftoa
. IOOE1-01
. . , .0 E»00
.U EfOO
<. IOOE»00
.4tOt:»OI
.a E»OO
N.O £>00
.0 E»UO
.0 E»00
.O £>OO
.hOO£»Ul
.a E»oo
.1) E«00
. 2i»OC»02
. 1UOE»00
.<,TOE»Ol
. IOOE«00
.U E»00
.0 E«00
, 790E>02.
.23«E>0)
. 1<,OE»U2
. 7UJE»02
. IUOE«OL
.I65E«03
1SI-JHPINOER 2HO
.0 E»OO
.0 E»00
<«700£-.9SOE
-------
PPM
ELEMENT
ALUMINUM
MAGNESIUM
SODIUM
FLUORINE
. BORON
BERYLLIUM
.LUHIUH
TOSCO
LCM NOX
PPH
fUEL OIL. . _ FILTER.
. I30E»02 O.O E«00
,120E»U2 U.O E»00
,600E»Ol U.O E»00
.400E>00 .0 E»00
. ..|OOE»UI .0. E«00
.0 E»00 <.25IE-02
. 170E»02
... __ ... *. ,.*
0 . E»00
.1ST IHPINGER
.0 E»00
,a_ E»OO
U.O E»00
.0 E»00
.0 E»00
.0 E»00
.0 E»00
.0 e»oo
.0 E»00
2ND & 3RD 1 WINGERS
N.O E*00
N.O__E«00_
"N.d E»oo
N.O £»00
N.O E«00
.0 E«00
N.O E»00
OD
I—»
00
-------
CO
I
t
.
»~~
'•
»
*
I
\
':
c
•
•
"
•
1
MASS/nLAI INCul
ELlMtNI
UHAI4IUH
IllflRllJM
LEAD
MEHCUHY
com
PLAIIMJH
HAt-NIUM
PHASECOTMIUM
CERIUH
LANTHANUM
BAHIUM
CESIUM
IODINE
TELLUMUH
ANIIMuNt
UN
CADMIUM
SILVER
MULVUOtNUM
NIOUIUH
MHCONIUM
SI DON HUN
RUBIDIUM
BROMINE
SELEMUM
AUSCNIC
GERMANIUM
CALL IUM
/INC
COPPER
NICKEL
CCUALT
IKON
MANGANESE
CMHCHIuM
VANACIUH
MIAMiM
SlAftUliJM
CAU.IUH
PUIASSIUM
SULfUH
ciiCiChr.Mus
S|iK<<"*
K..C.':
Llx MIX
Nb/J
MITtK XAO-2
.J026-U
• ^ 34E— OS
< • ! UL E™04
.0 E»UO
.0 E«00
.0 E*OU
.0 EtOO
.0 E*UO
.0 E»00
.161 £-04
.0 £»OU
.0 t»00
< .10U-06
N .0 EtUO
.101E-06
.101E-06
.wee-os
.B87E-U5
.0 EtflO
.0 £»00
.2Q2E-OD
.0 EtOO
.0 E*00
.101E-OS
.4036-04
N .0 E»00
.lOU-Ot
,B07E-Oi
.US/E-01
I282E-03
.U07E-US
.20IE-0)
.0 E»00
.0 t»l)0
U .0 E«00
U .0 E'OO
U .0 b»UU
> .UIE-UJ
.1 3U-U4
U .0 E«DJ
.0 t»00
.0 E>00
.0 E»00
< .5066-04
.0 E»00
.0 E«00
.0 E*00
.0 E*00
.0 E»00
.Z36E-Q2
< .IIBE-U3
.234E-J3
.0 £*00
N .0 E»00
.0 £*UO
.H8E-03
.0' E»00
.7QJE-03
.0 £*00
.UBE-02
.0 E'OO
.6 £»oo
< .118E-03
.S18E-02
.0 E*oO
N .0 E»UO
.0 £»00
.0 E«00
.0 E»00
. 707E-02
.0 E*00
.0 E»DO
!uat-03
IllBE-03
.U C>00
.0 E«go
.V30E-OI
.277E»UO
.IbSE-Ol
.U24E-02
1ST IMCINGER 2NU C IRQ IMPINCERS HEATED OUTLET
.0 E»00
.0 E>00
< Iz37E-05
.0 £«00
.0 E>00
.0 E>00
.0 £«00
.305E-OJ
.67*6-03
.(36E-02
.0 E«00
,0 E'Od
< .136E-03
N .0 E«JO
.0 E»00
.0 E»00
!6T8E-03
.678E-04
.576E-01 —
< .506E-03
< .&7SE-03
< .67BE-03
N .0 E»00
.0 E«00
.0 E«00
.23TE-01
.610E-02
.0 E*OO
tzne-02
.136E-02
. 136E-02
< .339E-04
.339E-02
U .U £ »00
.0 E«00
> .322E*00
.0 E*00
.0 EtOO
N
N
<
N
N
N
N
N
N
N
PT
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
M
N
N
.0
.0
• 1 1
.0
.0
.0
lo
.0
.0
.0
£•00
£•00
~"E»oo"~
>ȣ-04
E«JO
£•00
E»00
EtOO
EtOO
£•00
£•00
EtOO
.0 E*00
.0 E«00
.240E-OJ
.0
.0
;o
• 0
.0
.0
.0
.0
,0
*o
£•00
EtOO
"EWO
EtOO
e*oo
£•00
EtOO
EtOO
EtOO
.0 EtOO
. 240E-01
• 0
.0
T°
.0
.0
• U
.0
.0
.0
.0
• 0
.0
.0
.0
.0
• 0
.0
.0
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
£•00
EtOO
.3026-00
.302E-Ofc '.
.3i5r-o3 !
< .SOIE-04
.0 EtOO
.0 EtOO
.0 EtOO
.0 EtQO
.305E-OJ
.67BE-03
'.3I3E-02 1
< .II8E-03 U
• 21tE-OJ .J
< .I36E-03
< .240E-03
.IUIE'06
.U8E-03 :
.IIOb-U^ .j
I«T8E-0) '1
' .Z13E-02
.6eOE-04 I
< .626E-03
.*l»E'0»<»<.58fcE-02
.»03E-06 .*0*k*00
.826E-02
-------
MAS WML II
U UN I NUN
HACHtblU'1
SOOIUH
FLUOKIKk
UQKCK
QEMVI.LIUH
IIIHIUH
L I H M X
hu/J
IWIN6ER
2NU t 3HO IMP1KCERS
HEAIIR null El
.0 t«uo
.00
.0 E»00
.0 E«00
.0 E»00
.20UE-UI
.IUE-01
.0 e*oo
< .IOIC-O6
.ISIE-OS
DO
I
-------
CD
I
r\>
<
•
*
V
K
"-
"
-
f
I"1
MAii/htAI INI'Ul
ELLMEHI
UKAhlUM
IHCKIUM
LEAU
HEMCUHV
bOLC
PLAT INUH
HAHllYM
PkASEbOVMIUH
CERIUM
LANIhANUH
BARIUM
IODINE
lELlUhlUN
UN
CADMIUM
HULveilENUN
NIOBIUM
mCCNIUM
STNONTIUM
KUUIDIUN
wdGKiNt
itLCNIUN
AK>LNIC
CCHMANIUN
UAILIUM
ZINC
CUCCtK
NILKEI.
CllttAll
IHI.N
CMKCMIUH
SCANUIUX
PIIIAiihlH
H'l HH Iril
SlRHIK
LfM Mil
KU/J
< .IB3E-OI
< .2U(,E-Ol
.206E-01
N .a £«oo
.U 6*00
.O E>OU
.0 EtOO
.0 E»00
.0 €*OI)
.J E*UO
.0 EtOO
.0 E«UO
.a e*uo
.0 £2 f f E * UO
.I64C-U1
) »^ 0^ E 9 ulJ
• tj2t* E~ o^
» I *i 'i E * 0 1)
-------
MA^/HCAI IMKUf
H .t'
If.< N.IK
NO/ J
UU
ME4UR OUILEI
.2UOE-OI
.23l>e-02
-
"SOU I DM
fLUCHlNE
BORON
.•Jl7t-U2
.U8E-OJ
.0 £»UO
BEH1TLIIUH
LMHIUM
.0 E«UO
< .10U-06
.ISIE-05
DO
I
ro
-il
-------
ro
i
ro
1
-
•
»
»
•
-
•
CONCENTRATION
CLEMENT
URANIUM
- THORIUM . . --
LEAD
MERCURY
GOLD
PIATIMIH
-HAFNIUM
PRASEODYMIUM
CERIUM
LANTHANUM - -
BARIUM
CESIUM
IODINE
TELLURIUM
- ANTIMONY - _
TIN
e AM* HIM
SILVER
MOLVaOEMIN
NIOBIUM . .
IIRCCNIUM
VTT'IUH
STNONtlUN
RUBIDIUM
BROMINE
SELENIUM
ARSENIC
GERMANIUM
GALLIUM
11NC - --
COPPER
NICKEL - -
CCbALI
IRON
. MANGANESE
CHROMIUM
- VANADIUM .
IIIANIUM
SCANDIUM
(AlCIUM
POTASSIUM
-CHLORINE
SULCUR
PHOSPHORUS
SILICON -
TCSCO
LCu MIX
MCd/OSCM
- FILTER
.1216-02
. .- -12IE-02
.2116-01
< ,*02E-Ol
-. --- -.0 E»00 -
.0 E»00
• 0 E")n
.0 E»00
.0 E«00
.0 e*oo
.643E-OI
,0 f»OQ
.0 6»00
< .4026-03
_^_ M To Ft DO
.<-02E-03
.tn;e.oi
.J98E-01
.3S4L--01
.0- E»00
.0 E»00
.flO?F-m
.0 E»OO
.0 E«00
.402E-02 -
.I»IE-02
N ..0, E»00. . .
.402E-03
. 161E-02
- .111E»QO . ..
.32IE-OI
. .JSaEtOl
.791E-OI
U12E»01
.321E-01
.159E»00
,H Off tan
.0 E*00
.0 E»00
U .0 E»00
. U ..Q E»QO
> .»62E»00
.5226-01
U .a £»00
. . XAD-2 . .
.0 E»00
. .0 £>oa
.0 £»00
< .202£»00
-_ .0 E»OU .
.0 E»00
.0 F'OQ
.0 e«oo
.0 E»00
.0 F<00
.936E»Ol
it_.469E*00
.938E»00
.0 E»00
H .0 E»00
.0 E»00
.4&9E*00
.0 t»00
.2«2E»01
.a f»na
.469E»OI
tO ?»"0
.0 E«00
< .469E»00
.206E»02
.0 E*00
. H. .0 E«00
.0 E*00
.0 EKJO
. .0 £»00 ._
.282E>02
.0 F»00
.0 E*00
.l)6E«Ot
.....469E«00._.
.221E»02
.4&4E«UO
.0 E»00
.0 E»OO
•3?IE*03
. IIOE»0«
.65?E»02
.32«E*01
.12BE»02
. / ?«E»03
. .. 1ST .IMP1NCER ..
.0 E»00
.0 E.OO
.12IE>OI
< .945E-02
. ._ .0. E«00 .
.0 E»00
.0 E»aa
.0 E»00
.121E«OI
.27l>E»O|
.S40E»OI
.a F«OO
.0 E»00
< ,S40E»OO
N .0 E>00
.0 E»00
.0 E»00
.675E»OI
.135E«00
-270E»OI
. 37BE»Ol
,2TOE»00
.22<)E»01
< .202E»Ol
< .ttottal
< ,2/OE»01
N .0 E»OO
.0 E»00
.0 E»00
.9<>SE»02
.2*3E»02
.256E»D2
.0 E»l)0
.553E»02
.108E»02
.*40E»01
.40SE»00
.s«OE»ai
< .I15E»OU
« 135£*02
U .0 E »00
.(1 E»UO
> .I2«E»0*
.0 EtOO
.0 E»QO
2ND t 3RO MPINGERS
N .0 E»00
.0 e»oo
N .0 E»00
< .6T6E-OI
... N_.0...£»00.
N .0 E»OO
.a E»ao
N .0 E»00
N .0 E»00
N ,0 E»00
N .0 E»OQ
N .0 E»00
N .0 E»00
N .0 E»00
< .9STE»OO
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
N . 0 E »00
N .0 E»00
N .0 E»00
N .0 E»00
N .0 t«00
N .0 E»00
< .«57E»00
N .0 E»00
N .0 EH)0
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
N .0 E»00
N_.0 E*00
N .0 E»00
N .0 E«00
N .0 E»00
N .0 E«00
N «0 E *00
N .0 E»OO
N .0 E »00
N .O EiOO
N .0 E»00
N .0 E»00
HEATER OUTLFT
.1216-02
.I2IE-02
.I24E»OI
< .319E»00
.0 E*00
.0 E»00
.0 E»00
.0 E»00
.121E»OI
.2TOE»OI
.l*«E«02
< .469E*00
.938E»00
< .5*OE»00
< -957£»00
.402E-03
.*70E«00
.«T9E»Ol
.299E»01
.2TOE»OI
.8«7E»01
.271E»00
.229f»OI
< .249E«OI
.206C»0203
. H3f»02
.276E»02
. 16«E»01
.S40E»OI
< .I35E»00
f 3B4E*03
. IIOEXH
.65>E>02
> ,1«IE»0*
.329F»02
,7?4E»03
•
•
;;
"•
"
'••
1^'
'•
4
:i
••i
i
j
*
_
"i
-------
CCWCENIMTJUN
ELEMENT
*LUNINUN
MAGNESIUM
SUOIUM
fLUOfllNE
BORON
BERULlUN
.LITHIUM
ICSCQ _ -.
ICM HO*
NCfl/OSCM
f IlIER
U .0 E»00
U_..0_ E»00 ..
U .0 €»00
.0 E«00
. .0 £»00 ..
< .4Q2E-OI
.6<»OE»OJ
.«6«E»00
,0 E»00
.0 e»oo
tO__.i«OP_
1ST INPJNGEM
.0 E»00
_.0_E»00
.0 E»00
.0 E>00
.0 _ E«00
2ND C MO IHPINGERS
.0 E*00
.0 £»00 _
.0 E+00
.0 E*00
.0 E»00
HEAIER OUTLET.
.T98E»OZ
_ .<>38E»OI
.0 (E»00
.0 E»00
< .402E-0)
.603E-02
CD
I
ro
-------
CD
I
ro
ui
MASS/TIME
ELEMENT
' URANIUM
' THORIUM
LEAD
MEHCURY
' 6010
PLATINUM
HAFNIUM-
PRASEODYMIUM
CERIUM
LAMHANUN
BARIUM
CESIUM
IODINE
TELLURIUM
-ANTIMONY
TIN
CADMIUM
SILVER
MOLYBDENUM
NIOBIUM.
ZIRCONIUM
H YTTRIUM
STRONTIUM
RUBIDIUM
' — . BKONlflE-
SELENIUH
H . AMSFNIC
GERMANIUM
GALLIUM
' - - 1 INC
COPPER
NICKEL
CCIALT
IRON
1 MANCANESE
CHROMIUM
' VANADIUM
TIIANIUM
SCANCIUM
' CALCIUM
POTASSIUM
' CHLORINE - -
SULtUK
PHOSPHORUS
- SILICON
ICSCO
LCM MOX
MCG/SEC
-FILTER
.396E-02
.70UE-01
< .!32EtQO
- .0 EtOO - . -
.0 EtOO
.0 FtOO
.0 EtOO
.0 EtOO
.0 Ftnn
.2ll£tOO
.0 ftnn
.0 E too
< .132E-02
u -n Ftnn
.132E-02
.131EJOO
.U6Etou
.0 -£tUQ _
.0 EtOO
.0 EtOO
.0 EtOO
.I28E-02
N .v F ton
.132E-02
.S26E-02
.106EtOO
.260E»00
.3TOEtOt
.IQ6EtOO _
.523EtoO
.0 EtOO
.0 EtOO
U .0 FtOO
U .0 EtOO
U- .0 EtOO
> .I8i£»01
.172f»00
U .0 EtUO
XAO-2- - .. -
.0 EtOO
.0 . -Etoo _
< .663EtOO
.0 EtOO .
.0 EtOO
.0 EtOO
.0 E»00
-u Ftnn
• 30VE t 02
C ft j %^E tell
.309E»01
.0 EtOO
N- .0.. EtOO
.0 EtOO
.0 EtOO
.926E»Ol
,0 Etoo
.0 EtOO
.0 EtOO
M .0 F.CIQ
.0 EtOO
.0 EtOO
-Q F»no
.«26Et02
. .n F»nn
.0 EtOO
x 4 7(+03
• | *J4p • Ol
.72*Et02
.0 EtOO
.0 EtOO
.363Et04
.I08[>03
_ ISt IHP1NGER -
.O EtOO
< .3IIE-01
.0 ftnn
.0 E»00
.0 EtOO
. 178E»02
.0 FtOO
.0 EtOO
C * I f 9 £ *0i
N r ^ E*00
.0 EtOO
.0 EtOO
,222E»02
.a««f»ni
.I2<,E«02
.888£tOO
< .666f.t01
< .B88EtOl
< .6B«EtOI
M .0 EtOO
.0 EtOO
.0 EtOO
.UlEtOl
.»»•»£ to?
«0 EtOO
• 1 8£E 1 03
t ^55£t 02
.IT8Et02
.IllEtol
. ir«£«02
U .0 EtOO
,0 EtOO
to EtOO
_. .0 EtOO
1
2ND t JRD.IHPINGERS. JIEAIfR OUTLET. .'
ti .0 EtOO
.0 Eton
N .0 6*00
< .222£tQO
.N .0 EtOO
N .0 EtOO
.0 EtOO
N .0 EtOO
N .0 EtOO
N .0 Ftoo
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 Etoo
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 Etoo
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
< .UlEtOl
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
N *0 EtOil
M .0 EtOO
N .0 EtOO
M .0 Etoo
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
N_.9_£tfl«
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
N .0 EtOO
. 396F-02
t 396E~O?
*407£tQ|
< .lOSEtOI
.0 FtOO
.0 EtOO
.0 EtOO
.0 EtOO
.8«8EtQl
.309EtQl
< .ITSEtQI
. I32F-02
,223E»02
.888E+01
.890EtOO
< ,820Ftol
.6T9Et0203
.«08£t02
r«SlEtol
.I78E»02
• 126Ft04
. 361E«0»
,IOHE>03
'
»
'•
•
;•
••
;;
«
',
;;
;;
•i
-
f
-------
CO
I
• IQSffl
• HASS/TINE IOW NOK
, MCG/SEC
, ELEHENT FILTER HADrZ. „ 1ST |MPINGER.
ALUMINUM U .0 E»00 .Z6ZE»OI .0 E*00
• NACftmUH U .0 e»00 .HWEtOZ .0 E»00
SODIUM U .0 E»00 > .22IE»0* U .0 E»00
FLUODINE •<» 6»00 .15*E»01 .0 E*00
mfW .0 E»00 .0 E»00 ... . ,0 E*00
BER»LLIUH < .I3ZE-OZ .0 E»00 .0 E*00
, HTHf'M .I9BE-01 .0 E»00 .0 6*00
•
'
'
H
K
-
•
;
•
*
ZNO C 3RD 1MPINGERS HEATER OUTLET
N .0 E»00 .Z6ZE»0)
N .0 £»00 . J09E»OZ
N .0 £»00 > .22TE«A«
H .0 E*00 .IS4E*01
N .0 E*00 .0 E»00
.0 E»00 < .I3ZE-OZ
N .0 E»00 .19«E-01
1
..... .
$
M
'!
'•
;•
»
"
•
;•
•'
;;
'
M
^
j
-------
CO
I
ro
MASS/TIME
URANIUM
LEAD
NERCUKV
PLA11NUM
HAF NIUH
PRASEODYMIUM
CERIUM
" LAN1HANUM
BARIUM
CESIUM
IODINE
tELLURIUM
^HUIOIT
III
CAQHIUi*
SILVER
MOLYBDENUM
NIOBIUM
" ZIRCONIUM
* YfTRIUM
StRONtlUM
" RUBIOIUM
BROMINE
SELENIUM
ARSENIC
GEHMANIUM
CALLIUM
JINC
COPPER
NICKEL
CUBALI
IRON
M4NCHNE5E
CNROKIUM
VANADIUM
IIIANIUM
SCANUIUM
CALCIUM . . _
POTASSIUM
CHLORINE
SULtUR
PHOSPHORUS
- - SILICON -
LCH NOX
MCG/SEC
F UE I OIL
< .a?«E»U2
-™ - < .983E»02
.99JE»02
N .0 €«00
*0 6*00
.1ZOE»0*
.0 f»0n
,(i E»00
.0 E»00
.1) t»nn
.I09E»03
,n f>nn
.0 E»00
.0 E»OQ
.n ftnn
.0 E»00
.0 F*nn
.0 F+00
.0 E»00
.0 • f »on
.0 E»00
.n onn
,5**E»02
.0 E»00
,0 f*fli)
.0 E»00 .
.4 F»nn
.0 E*00
.104E*02
.•>?DF.ni
.655E»Q3
.«7^f «ni
< .ZIUE*02
,2««.C«0*
, •SiifrFtn}
.101E«03
T«jn:».13
.lfl»E*0«
.0 E»00
,n*{H)»i
.r;iE»04
• 5*fr£ »^l j
.}60E<04
.J«6E>03
.lfiE»04
Mfkf^-R CII'IE'
. JS6E-02
-lQt.F-02
.nF>no
.755E»Ol
< ,820E»OI
i>T«E»02 .53UE»0«.
,I08E»03
.253E.O* ._.
«
1 >•
•c
;:
;;
'•'•
•i
.. .. j
!
t;
-------
NASS/TIKE
ELEHEN1
ALUMINUM
_NAC«ESIUH .
SODIUM
ftUORINE
BORON
BEftULIUM
.UTKJUM
. .. ILSCO
LCM NOX
MCG/SEC
Hit I OIL . .HEATER. OUTLET
.262E»0)
.0
,718E»03_
.0 E»00
< .132E-02
,|98E-Ol_
03
I
ro
oo
-------
CB
I
ro
UD
«
•
"
•
INI FUEL OIL
ELEMENT
URANIUM
THORIUM
-LEAD
MEHCURT
GOLD
PLATINUM
HAFNIUM
PRASEODYMIUM
CERIUM
LANTHANUM
BARIUM
CESIUM
IODINE
TELLURIUM
ANTIMONY
TIN
CADMIUM
SHVtH
MOLYBDENUM
NicaiuM
ZIRCONIUM
YTTRIUM
STRONTIUM
RUBIDIUM
BROMINE
SELENIUM
ARSENIC
GERMANIUM. ..
GALLIUM
I INC
COPPER
NICKEL
CCBAH ....
IKON
MANGANESE
CHROMIUM
VANAUIUM
IIIAMUM
SCANDIUM
CALCIUM
POIASStUM
CHLCHINE
SULFUR
PHCSPHOMUS
SILKUN
TC5CO
LCM NUX
MCG/SEC
HEA1ER MASS BALANCE ....
OOI 1 HEATER EXHAUST GAS
TOTAL IN TOTAL OUT
X<.BT4E»02 . 3<16E-02
X<.VB3E»02 .396E-02
..983C»02 -- .*OIE»Ol ..
U20E»0*
'.8«8E»01
.109E»03 .*88E«02
X<.I54E»01
X<.I78E»01
X<.3lSE»Ol
.132E-02
.982E»OI
,88HE»Ot
.274E*02
.a«OE«00
x<.a20E»oi
.\\2t-Ql
.|C9E*02 .S2BE-02
.328E*03 ,3IIE«03
.655E»03 .IT3E«03
,8?*E»03 .96IE»U2
X<.2la£»02 . „ ,260E»OQ
.2e^E»0*> ,633E»03
,5'i6C»02 . 1»2E»Q2
.I09E«03 .90aE»OZ
.B)'iE>02 ,551E»01
.1?»E»04 ,I26E»0»
• 72|E^04 • 36 3F *O^V
«S46f|tQ) «2l^i£*^03
.360[»0«, . S30E«0* 0«
MASS BALANCE IOUT/ INI
::SI:S «
•
.0 E*00
*
"•
*
*
•
• 1
. 138£*00
*
!9JUE»00
.263E«00
.I10E>00
.I19E-01
-------
INI FUEL Oil
EL EM EN!
'ALUMINUM~
HAGNESIU*
SUDIUH _ .
FLUORINE
BOSON
_ . TOSCO . . _ ........—
LCH NUX
HCi/SfC
HEATEK MASS BALANCE
UUI I HE A ftH EXHAUS1 GAS
TOTAL IN TOTAL OUT
MASS BALANCE (OUT/ IN I
.}09E*02
.Z35E-01
.6S5€»OJ...._
__
.3SJE-01
.0 E»00
BEHVLLIUM
LITHIUM
X<.I3ZE-02
.210E»03
.198E-01
.90TE-04
CO
O
-------
TECHNICAL REPORT DATA
(Please read /nunictwns on the reverse before t ample ting)
1. REPORT NO.
EPA-600/7-84-074a
2,
3 RECIPIENT S ACCESSION NO.
4. TITLE AND SUBTITLE
Environmental Assessment of a Crude-Oil Heater
Using Staged Air Lances for NO Reduction; Volume
I. Technical Results
5. REPORT DATE
July 1984
6. PERFORMING ORGANIZATION CODE
7, AUTHOfl(S)
8. PERFORMING ORGANIZATION REPORT NO
R. DeRosier
TR-82-94/EE
9. PERFORMING ORGANIZATION NAME AND ADDRESS
A cur ex Corporation
P.O. Box 7555
Mountain View, California 94039
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO
68-02-3188
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 6/81 - 11/83
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES iERL-RTP project officer is Robert E. Hall, Mail Drop 65; 919 /
541-2477. Volume II is a Data Supplement.
16. ABSTRACT
This volume of the report gives emission results from field tests of a
crude-oil process heater burning a combination of oil and refinery gas. The heater
had been modified by adding a system for injecting secondary air to reduce NOx
emissions. One test was conducted with the staged air system (low NOx), and the
other, without (baseline). Tests included continuous monitoring of flue gas emissions
and source assessment sampling system (SASS) sampling of the flue gas with subse-
quent laboratory analysis of the samples utilizing gas chromatography (GC), infra-
red spectrometry (IR), gas chromatography/mass spectroscopy (GC/MS), and low
resolution mass spectrometry (SSMS) for trace metals. Flue gas concentrations of
NOx were reduced 30 percent (from 83 to 56 ng/J) with the staged air system. Total
organic emissions dropped from 17.1 to 3.4 mg/dscm from the baseline to the low-
NOx test (due primarily to a reduction in the C sub 1 to C sub 6 boiling point range
compounds which constituted most of the organic emissions). GC/MS analysis iden-
tified 11 semivolatile priority pollutant compounds in both tests, most of them pre-
sent in higher concentrations during the baseline test. LRMS analysis suggested the
presence of eight compound categories in the organic emissions during the baseline
test and four in the low-NOx test.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
C. COSATI I ICId/CfOUp
Pollution
Nitrogen Oxides
Crude Oil
Gases
Heating Equipment
Lances
Flue Gases
Assessments
Pollution Control
Stationary Sources
Staged Combustion
Refinery Gas
Air Lances
Environmental Assess-
ment
13 B
07B
UH, 08G
07D
13A
131
21B
14B
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
102
2O. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
B-31
------- |