SEPA
United States
Environmental Protection
Agency
Research and
Development
EPA-600'7-84-073a
July 1984
ENVIRONMENTAL ASSESSMENT OF
A RECIPROCATING ENGINE
RETROFITTED WITH NONSELECTIVE
CATALYTIC REDUCTION
Volume I. Technical Results
Prepared for
Office of Air Quality Planning and Standards
Prepared by
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
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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.
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EPA-600/7-84-073a
July 1984
ENVIRONMENTAL ASSESSMENT OF A
RECIPROCATING ENGINE RETROFITTED
WITH NONSELECTIVE CATALYTIC
REDUCTION
Volume !
Technical Results
by
C. Castaldini and L R. Waterland
Acurex Corporation
Energy & Environmental Division
555 Clyde Avenue
P.O. Box 7555
Mountain View, California 94039
Contract No. 68-02-3188
EPA Project Officer:
R.E. Hall
Combustion Research Branch
Energy Assessment and Control Division
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
Prepared for:
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, DC 20460
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ABSTRACT
The two-volume report describes results obtained from testing a rich-
burn reciprocating internal combustion engine retrofitted with a nonselective
catalytic reduction system (NSCR) for NOX reduction. A comprehensive test
program was performed to characterize catalyst inlet and outlet organic and
inorganic emissions at optimum catalyst NOX reduction performance, follow-
ed by a 15-day exhaust emission monitoring program to measure the catalyst
performance under typical engine operating conditions. Over the 1-day com-
prehensive test period, the NOX reduction performance of the catalyst ranged
between 54 and 81 percent, with an average of 70 percent. NOX emissions
averaged 1700 ppm at the catalyst inlet and 550 at the catalyst outlet. Catalyst
inlet CO and TUHC concentrations averaged 14, 600 ppm and 115 ppm, respec-
tively. These inlet combustible concentrations were the result of engine oper-
ation at an air/fuel ratio near or slightly below the stoichiometry required for
efficient NOX reduction. Catalyst outlet CO and TUHC levels were reduced to
13, 200 ppm and 125 ppm, respectively. Total organic emissions were also re-
duced by the catalyst from 15. 5 to 2.1 mg/dscm. Ammonia and cyanide levels
increased by factors of 15 and 450, respectively, across the catalyst. Over
the 15-day monitoring period, NOX reduction performance was mostly in the
0 to 40 percent range. Only occasionally did NO reduction exceed SO percent.
^t
During these periods of better performance, CO and TUHC emissions at the
inlet were as high as 1 percent and 0.1 percent, respectively.
11
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CONTENTS
Figures ............................ iv
Tables ............................ v
Acknowledgments ........................ vi
1. Introduction ...................... 1-1
2. Source Description and Operation ............ 2-1
3. Emission Results .................... 3-1
3.1 Sampling Protocol ............... 3-1
3.2 Criteria Pollutant and Other Vapor
Species Emissions ............... 3-3
3.3 Trace Element Emissions ............ 3-13
3.4 Organic Species Emissions ........... 3-13
3.5 Extender! Continuous Emissions Monitoring . . . 3-2-1
4. Environmental Assessment ................ 4-1
4.1 Emissions Assessment ............. 4-1
4.2 Bioassay Results ............... 4-2
b. Test Quality Assurance and Quality Control ....... 5-1
b.l NUX Certification Results ........... 5-1
5.2 Duplicate Analyses .............. 5-3
Appendices
A. Sampling and Analysis Methods
B. Trace Element Concentrations
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FIGURES
Nunber Page
3-1 Sampling sites and analysis test matrix 3-1
3-2 Test activity schedule 3-4
3-3 Exhaust gas Oj during comprehensive tests 3-6
3-4 Exhaust gas C02 during comprehensive tests 3-7
3-5 Exhaust gas NOX emissions during comprehensive tests . . . 3-9
3-6 Catalyst NOX reduction efficiency during
comprehensive tests 3-10
3-7 Exhaust gas hydrocarbon emissions during
comprehensive tests 3-12
3-3 Exhaust Qฃ for the 15-day continuous monitoring
period 3-26
3-9 Exhaust C02 for the 15-day continuous monitoring
period 3-27
3-10 CO emissions for the 15-day continuous monitoring
period 3-23
3-11 TUHC emissions for the 15-day continuous monitoring
period 3-29
3-12 MOX emissions for the 15-day continuous monitoring
period 3-30
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TABLES
Number Pace
1-1 Completed Tests During the Current Program ....... 1-4
2-1 Engine Model Specifications ............... 2-1
2-2 Engine Operation .................... 2-4
3-1 Criteria and Other Gas Species Emissions
Comprehensive Tests .................. 3-5
3-2 N20 and NOX Emissions .................. 3-14
r
3-3 Inorganic Trace Element Emission Rates ......... 3-1^
3-4 Compounds Sought in the HC/MS and Their
Detection Limits ................... 3-20
3-b Total Organic and Semivolatile Organic
Priority Pollutant Emissions, ^g/dscm ......... 3-21
3-6 IR Spectra Summary ................... 3-23
3-7 TCO and GRAV Results for the LC Fractions of the Catalyst
Inlet XAU-2 Extract .................. 3-23
3-d Summary of IR Spectra for LC Fractions of the
Catalyst Inlet XAD-2 Extract ............. 3-25
4-1 Exhaust Gas Components Emitted at Levels Exceeding
ID Percent of Their Occupational Exposure Guideline . . 4-3
4-2 Bioassay Results .................... d-a
3-1 Method 7 Certification Results: June 8 ......... 5-2
3-2 Method 7 Certification Results: June 20 ........ 5-4
3-3 Duplicate SSMS Analyses of Catalyst Outlet SASS
Impinger 1 Sample, mg/1 ................ 5-5
5-4 Results of Duplicate Organic Analyses of SASS Samples . . 5-*
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ACKNOWLEDGMENTS
This test was performed in cooperation with Southern California Gas
Company (SoCal). Appreciation is greatly extended to G. Gardetta and W.
Matlock of SoCal. Special recognition and thanks are extended to the Acurex
field test crew of Bruce DaRos, Regan Best, Pete Kaufmann, Greg Nicoll, and
Sherman Smith under the supervision of Howard Mason, the project leader at
the site.
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SECTION 1
INTRODUCTION
This report describes and presents results for a set of environmental
assessment tests performed for the Industrial Environmental Research
Laboratory/Research Triangle Park (IERL/RTP) of 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 the NOX Control
Technology Environmental Assessment (NOX EA, EPA Contract No. 68-02-2160),
having the following objectives:
o Identify potential multimedia environmental effects of stationary
combustion sources and combustion modification technology
Develop and document control application guidelines to minimize
these effects
o 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 developing emission data 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
1-1
-------
sources and combustion modification techniques. Consequently, a series of
seven environmental field test programs was 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 NOX EA final report summarizing the
entire 3-year effort (Reference 1-8).
The current CMEA program has, as major objectives, the continuation of
multimedia environmental field tests initiated in the original NOX EA
program. These new tests, using standardized sampling and analytical
procedures (Reference 1-9) are aimed at filling remaining data gaps and
addressing the following priority needs:
9 Advanced NOX controls
o Alternate fuels
9 Secondary sources
o EPA program data needs
-- Residential oil combustion
-- Wood firing in residential, commercial, and industrial sources
-- High interest emissions determination (e.g., listed and
candidate hazardous air-pollutant species)
o Nonsteady-state operations
In California, the South Coast Air Quality Management District (SCAQMD;
continues to be in nonattainment of both federal and state NC>2 standards.
Reciprocating internal combustion engines (ICE's) in this district are
estimated to contribute 14 percent of the NOX (about 59 Mg/'day (65 tons/day))
from all stationary sources and 5.1 percent of the total NOX emissions in the
basin (References 1-10 and 1-11). Furthermore, since acid precipitation in
noncoal-burning regions such as the SCAQMD is being increasingly attributed
1-2
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to NOX emissions fron sources with low stacks, reciprocating ICE's are he^g
viewed as possibly contributing to the acid rain problem.
In 1979, the California Air Resources Board (CARB) proposed a control
strategy for ICE's that called for retrofit of these sources with
nonselective and selective gas treatment catalysts (NSCR and SCR,
respectively). In keeping with this CARB strategy, the SCAOMD passed
rule 1110 calling for demonstration tests of NSCR and SCR technologies fnr
engine NOX control. Southern California Gas Company (SoCal ) has conducteo
several performance tests to evaluate NSCR and SCR catalysts for their
applicability in reducing NOX from SoCal operated ICE's. In addition to th?
t
problem of sustained NOX reduction performance, several environment*1
concerns associated with this technology have been documented
(Reference 1-12). In the case of NSCR, for example, the formation of ammonia
and cyanide gases by the catalyst has been highlighted. For SCR,
breakthrough ammonia and NgO formation are also concerns.
In response to these concerns, a rich-burn reciprocating ICE operated
by SoCal and retrofitted with a commercially available NSCR system was
selected for testing under the CMEA program. The objective of the tests was
to quantify multimedia emissions (including organics, inorganics, as well as,
ammonia and cyanides) at the inlet and outlet of the NSCR catalytic reactor.
In addition to these tests, NOX reduction performance of the NSCR was
monitored continuously over 15 days-under typical operating conditions.
Table 1-1 lists all the tests performed in the CMEA program, outlining
the source tested, fuel used, combustion modifications implemented and the
level of sampling and analysis performed in each case. Results of these test
programs are discussed in separate reports.
1-3
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TABLE L-l. COMPLETED TESTS DURING THE CURRENT PROGRAM
Source
Description
Test points
unit operation
Sampl Ing protocol
Test col lahorator
Spark-Ignited natural -
gas-fueled reciprocating
Internal coiiihustlon
engine
Large-bore, 6-cyl1nder,
opposed piston, 186 kW
(250 l)hp)/cyl . 900 rpm.
Model 38TDS8-1/8
Baseline (pre-NSPS)
Increased air-fuel
ratio aimed at
meeting proposed
NSPS of 700 ppm
corrected to 15
percent 0? and
standard atmospheric
condi tlons
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 Col t
Industries
Compression-Ignltlon
dlesel-fueled
reciprocating Internal
combustion engine
Large-bore, 6-cyl Inder
opposed piston, 261 -kW
(350 Bhp)/cyl, 900-rpm,
Model 38TD08-1/8
Baseline
Fuel Injection retard
aimed at meeting pro-
posed NSPS of 600 ppm
corrected to 15 per-
cent 0? and standard
atmospheric conditions
Engine exhaust:
- SASS
-- Method 8
-- Method 5
-- Gas sample (C
-- Continuous NO,
C02, 02, CH4.
Fuel
Lube oil
Fairbanks Morse
Division of Colt
Industries
Cs HC)
NOX , CO,
TUHC
Low-N0x residential
condensing heating
system furnished by
Karl sons niueburner
Systems Ltd. of Canada
Residential hot water
heater equipped with
H.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-Cs HC)
-- Continuous NO, NOX, CO,
C02. 02, CH4, TUHC
Fuel
Waste water
New test
Rocketdyne/EPA
low-NOx residential
forced warm air furnace
Residential warm air
furnace with modified
high pressure burner and
firebox , 0.83 ml/s
(0.75 gal/hr) firing
capacity
Low-M0x burner design
and Integrated furnace
system
Furnace exhaust:
SASS
Method 8
Controlled condensation
Method 5
Gas sample (Cj-Cg HC)
-- Continuous NO, NO., CO,
New test
Fuel
C02. 02, CH4. TUHC
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TABLF 1-1. (continued)
Source
Pulverized coal - fi red
utility boiler,
Conesvllle station
Description
Test points
unit operation
Sain pi Ing protocol
Test col 1 aborator
i
en
400-MW tangential ly
fired; new NSPS
design aimed at
meeting 301 ng/J
NO. limit
ESP inlet and outlet,
one test
ESP inlet and outlet:
SASS
Method 5
Controlled condensation
Gas sample (C[-C6 HC)
-- Continuous NO, NOX, CO.
C02, 02
Coal
Bottom ash
ESP ash
Exxon Research and
Engineering (ER4E)
conducting cor-
rosion tests
Nova Scotia Technical
College Industrial
boiler
1.14 kg/s steam
(9,000 Ib/hr) firetube
fired with a mixture
of coal-oil-water (COW)
Baseline (COW)
-- Controlled SOo
emissions with
limestone Injection
Boiler outlet:
SASS
Method 5
Method 8
Envlrocon per-
formed partlculate
and sul fur
emission tests
-- Controlled condensation
-- Gas sample (Ct-Cfi HC)
-- Continuous 02, C02,
Fuel
CO, NOX
Adelphi University
industrial boiler
1.89 kg/s steam
(15,000 Ib/hr)
hot water
firetube fired wi th a
mixture of coal-o1l-
water (COW)
Baseline (COW)
Controlled SO?
emissions with
N32C03 injection
Boiler outlet:
SASS
Method 5
Method 8
-- Controlled condensation
"-- Gas Sample (C\-C(, HC)
-- Continuous 02, C02. NOX,
CO
Fuel
Adelphi University
Pittsburgh Energy
Technology Center (PETC)
Industrial boiler
3.03 kg/s steam
(24,000 Ib/hr) water tube
fired with a mixture of
coal-oil (COM)
Basel Ine test only
with COM
Boiler outlet:
-- SASS
-- Method 5
-- Controlled condensation
-- Continuous 0ฃ, CO?, NOX,
TUHC, CO
-- N;>0 grab sample
Fuel
PETC and General
Electric (GE)
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TABLE 1-1. (continued)
Source Description
Test points
unl t operation
Sampling protocol
Test collaborator
TOSCO Refinery vertical
crude oil heater
2.54 Ml/day
(16,000 bhl/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 (Cj-Cs HC)
-- Continuous 03, NOX, CO,
C02. HC
-- N?0, grab sample
Fuel oil
Refinery gas
KVB coordinated
the staged com-
bustion operation
and continuous
emission monitoring
Mohawk-Getty Oil
Industrial boiler
CTl
8.21 kg/s steam
(65,000 Ib/hr)
watertube burning
mixture of refinery gas
and residual oil
BaselIne
Ammonia Injection
using the noncatalytlc
thermal deNOx
process
Economizer outlet:
-- SASS
-- Method 5, 17
-- Controlled condensation
-- Gas Sample (Ci-C6 HC)
-- Ammonia emissions
-- N20 grab sample
-- Continuous 0^, NOX,
CO. C02
Fuels (refinery gas and
residual oil)
Mohawk-Getty Oil
Industrial boiler
2.52 kg/s steam
(20,000 Ib/hr) watertube
burning woodwaste
BaselIne (dry wood)
Green wood
Boiler outlet:
-- SASS
-- Method 5
-- Controlled condensation
-- Gas sample (Ci-C6 HC)
-- Continuous 02, NOX, CO
Fuel
Flyash
North Carolina
Department of
Natural Resources,
EPA 1ERL-RTP
Industrial boiler
3.16 kg/s steam
(29,000 Ib/hr)
flretube with refractory
firebox burning woodwaste
-- Baseline (dry wood)
Outlet of cyclone partlculate
col lector:
SASS
Method 5
Controlled condensation
-- Gas sample (CpCc HC)
-- Continuous 02, NOX, CO
Fuel
Bottom ash
North Carolina
Department of
Natural Resources,
EPA IERL-RTP
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TABLF 1-1. (continued)
Source
Enhanced oil recovery
steam generator
Description
15-MW (50 million Btu/hr)
steam generator burning
crude oil equipped with
Mill low-NOx burner
Test points
unit operation
-- Performance mapping
-- Low NOX operation
Sampl Ing protocol
Steamer outlet
SASS
Method 5
Method 8
Gas sample (Cj-Cg HC)
-- Continuous 0;>, NOX, CO,
CO?
N^O grab sample
Fuel
Test col laborator
Getty 0)1 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 slurry (CWS)
-- Basel Ine test only
with CWS
Boiler outlet
-- SASS
Method 5
Method 8
-- Gas sample (Cj-Cg HC)
-- Continuous 02, NOX, CO,
C02, FUHC
-- N^O grab sample
Fuel
Bottom ash
Collector hopper ash
PETC
Internal combustion
engine -- nonselectlve
NOX catalyst
(610 kW (818-hp) Waukesha
engine equipped with
OuPont NSCR catalyst
Low-N0x with catalyst
15-day emissions
monitoring
Catalyst Inlet and outlet
-- SASS
-- NII3
MCN
Grab sample
Southern CalIfornla
Gas Company
Industrial boiler 180 kg/hr steam -- Baseline (coal)
(400 Ih/hr) stoker-fired -- Coal anrl plastic
with a mixture of coal waste
and plastic waste
-- Continuous Op, C02, NOX
TUHC
Fuel
Boiler outlet Vermont Agency of
-- SASS Environmental
-- VOST Conservation
-- Method 5/8
-- HC1
-- Continuous 02, NOK , CO,
C0?. TUHC
-- H;>0 grab sapnple
Fuel
Bottom ash
Cyclone ash
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TABLE 1-1. (concluded)
Source
Description
Test points
unit operation
Santpl ing protocol
Test collaborator
Industrial boiler
7.6 kg/s steam
{60,000 Ib/hr watertube
retrofit for coal water
slurry firing
-- Baseline (CHS)
Boiler outlet
SASS
VOST
Method 5/8
Grab sample (C^Cg HC)
-- Grab sample (N20)
-- Continuous NOX, CO, 0)3,
EPRI, OuPont
Fuel
02, TUHC, S02
Enhanced oil recovery
steam generator
15-MW (50 million Btu/hr)
steam generator burning
crude oil, equipped with
the EPA/:ER IOW-NOX
burner
Low NOX
30-day emissions
monitoring
Steamer outlet
SASS
- VOST
Method 5/8
Controller condensation
Chevron U.S.A.,
EERC
oo
-- Anderson monitors
-- Grab sample (CpCg HC)
-- Grab sample (N20)
-- Continuous NOX, CO, C02,
Fuel
02, S02
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REFERENCES FOR SECTION 1
1-1. Larkin, R. and E. B. Higginhothan, "Combustion Modification Controls
for Stationary Gas Turbines: Volume II. Utility Unit Fiel^ Test,"
EPA-60U/7-81-122b, NTIS PBS2-226473, July 1981.
1-2. Higginbothan, E. B., "Combustion Modification Controls for Residentiป1
and Commercial Heating Systems: Volume II. Oil-fired Residential
Furnace Field Test," EPA-6no/7-81-123b, NTIS PB82-231175, July 19ป1.
1-3. Higginbothan, E. 3. and P. M. Goldberg, "Combustion Modification NDX
Controls for Utility Boilers: Volume I. Tangential Coal-fired iini".
Field Test," EPA-600/7-81-124a, NTIS PB82-227265, July 1981.
1-4. Sawyer, J. W. and E. B. Higginbotham, "Combustion Modification N^x
Controls for Utility Boilers: Volume II. Pulverized-coal Wall-fire^
Unit Field Test," EPA-600/7-81-124b, NTIS PR82-227273, July 1981.
l-t>. Sawyer, J. W. and E. 3. Hi ggi nbotham, "Combustion Modification NOX
Controls for Utility Boilers: Volume III. Residual-oi1 Uall-f
Unit Field Test," EPA-600/7-81-124c, NTIS PRR2-227281, July 1981.
1-6. Goldberg, P. M. and E. B. Hi ggi nbothan, "Industrial Boiler Comh.js
Modification NOX Controls: Volume II. Stoker Coal-fired Boiler
Test - Site A/ EPA-600/7-81-126b, NTIS PB82-231085, July 1981.
1-7. Lips, H. I. and E. B. Higginhothan, "Industrial Boiler Combustion
Modification NOX Controls: Volume III. Stoker Coal-fired Boiler
Field Test Site B," EPA-600/7-81/126c, NTIS PR82-231D93,
July 1981.
1-y. Waterland, L. R., et al., "Environmental Assessment of Stationary
Source NOX Control Technologies Final Report," EPA-fiOO/7-82-D34,
NTIS PB82-24935U, May 1982.
1-y. Lentzen, D. E., et al., "IERL-R"TP Procedures Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201, NTIS
PB29379b, October 1978.
1-1U. Bartz, L)., et al., "Control of Oxides of Nitrogen from Stationary
Sources in the Sixth Coast Air Basin," KVB, Inc., Irvine, California,
September 1974.
1-11. "Draft Air Quality Management Plan," South Coast Air Quality
Management District, El Monte, California, October 1978.
1-9
-------
1-12. Khakhiz, S., "Engineering Report -- DuPont Non-Selective System at
Honor Rancho," Southern California Gas Company Engineering Job
'1-82-35, April 1983.
1-10
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SECTION 2
SOURCE DESCRIPTION AND OPERATION
The tests were performed on a four-stroke, naturally aspirated WauKesha
electric generator engine equipped with a PR-5 DuPont NSCR catalyst. This
engine is located at the SoCal Honor Rancho underground storage field near
Valencia, California. Table 2-1 summarizes the engine model specifications.
The PR-5 DuPont catalyst, installed in November 1982 and having an initial
operating life (per vendor information) of about 4,000 hr, is a
platinum-rhodium-based formulation with an upper operating temperature limit
of 788ฐC (1,450ฐF). The catalyst, located downstream of the engine silencer,
was designed to reduce NOX emissions by 90 percent or greater, and thereby
meet SCAQMD rule 1110 of 0.28 yg/J (heat output), as N02 (0.75 g/Bhp-hr) .
Reducing gases, H2, TUHC, and CO, in the exhaust gas react with NOX in the
presence of this noble metal catalyst to reduce both NO and N02. The NSCR
chemical reaction process has been suggested to be as follows
(Reference 2-1):
1. CH4 - 4N02 C02 + 4NO + 2H2ฐ
2. CH4 + 202 C02 + 2H20
3. CH4 + 4NO C02 + 2N2 + 2H20
4. 2CO + 2NO 2C02 + N2
5. 2H2 + 2ND 2H20 + N2
The NSCR process then requires fuel-rich engine operation or the
addition of reducing agents in the flue gas upstream of the catalyst. To
2-1
-------
TABLE 2-1. ENGINE MODEL SPECIFICATIONS9
Manufacturer
Model
Strokes
Air charging
Number of cylinders
Bore
Stroke
Qisplacement/cyl
Compression ratio
BMEP
Bhp/cyl @ rpm
Generator output (electrical)
BSFC
Lubricating oil consumption
Waukesha
L7042 GU
4
Naturally aspirated
V-12
0.238 m (9.375 in.)
0.216 m (8.50 in.)
9.62 1 (587 in.3)
10:1
703 kPa (102 psi)
50.7 kW (68 Bhp) @ 900 rpm
610 kW
10,200 kJ/kWh (7,200 Btu/Bhp-hr)
70 1/kWh (1.37 gal/Bhp-hr)
aEngine operating performance is based on continuous operation,
ambient conditions of 99.2 kPa (29.38 in. Hg) and 29ฐC (85ฐF)
and a natural gas fuel (lower heating value) of 33.5 MJ/m3
(900 Btu/ft3).
2-2
-------
provide for an adequate concentration of reducing agents in rhe e
the engine often has to be operated with an air-to-fuel ratio (A/F) richer
than that necessary for minimum fuel consumption. SoCal expedient0 wit"i the
test engine has shown that A/F in the range of 17.2 to 17.4 is required tn
reduce NOX emissions by 90 percent or more (Reference 2-2). Since the engin^
is not equipped with an automatic A/F controller, several manual adjustments
are required to maintain this narrow range of A/F, especially during engine
load changes. During normal operation, fluctuating demands are imposed on
the engine generator and thus engine horsepower. This in turn causes changes
in A/F and NOX concentrations in the exhaust gas, often resulting in
decreased catalyst performance.
During the CMEA tests, exhaust emissions (NDX, 02, CO, C02, and TMHP.>
were measured on a continuous basis for a period of 15 days during norma"1
engine operating conditions (fluctuating loads and A/F). In adHi"ion, a
comprehensive emission test program was performed over a 1-day period during
which engine load and A/F were tightly controlled for catalyst. NOX reduction
of greater than 80 percent. Table 2-2 summarizes the engine operation and
annient atmospheric conditions during this 1-day comprehensive testing
peri od.
As noted, the comprehensive test program was performed at approximately
78 percent of rated load. Engine horsepower was most conveniently measured
by the generator output, which corresponds to 1.45 tines the generator
Kilowatts. Engine load oscillated ahout 60 hp (10 percent^ over the test
period with probable effects on A/F. Specific fuel consumption mpas'irpd
12,3.1)1) kJ/kWh (8,660 Btu/Bhp-hr) based on the lower heating value of the *iei
gas. This fuel consumption was well above the engine manufacture^
2-3
-------
TABLE 2-2. ENGINE OPERATION
Parameter
Range
Average
Ambient
Dry bulb temperature, ฐC (ฐF)
Wet bulb temperature, ฐC (ฐF)
Relative humidity, percent
Barometric pressure, kPa (in. Hg)
Engine Operation
Generator output, kW
Engine load, kWt (Bhp)a
Fuel flow, m3/h (scfh)
Heat input, MW (million Btu/hr)b
Specific fuel consumption, KJ/kWh
(Btu/Bhp-hr)b
Air manifold pressure
1, kPa (in. Hg vac)
o R, kPa (in. Hg vac)
Speed , rpm
Catalyst inlet temperature, ฐC (ฐF)
Catalyst output temperature, ฐC (ฐF)
Gas Analysis, Percent Volume0
02
N2
C02
CH4
C?Hc
C3H8
iso-C4H10
n-C4H10
iso-C5H12
n-C5H12
C6+
HHV. MJ/m3 (3tu/ft3)d
LHV, MJ/rn3 (Btu/ft3)d
26 to 29 (79 to 85)
20 to 22 (68 to 71)
--
--
415 to 455
448 to 492 (601 to 660)
--
--
--
14 to 16 (4.1 to 4.5)
14 to 16 (4.1 to 4.8)
900 to 910
533 to 536 (991 to 997)
534 to 561
(994 to 1,042)
--
--
--
--
--
--
--
--
29 (84)
22 (71)
52
96.4 (28.55)
425
459 (616)
156 (5,509)
1.56 (5.33)
12,300 (3,660)
15 (4.4)
15 (4.5)
905
535 (995)
552 (1,025)
0.073
1.119
0.890
90.119
6.294
1.247
0.094
0.106
0.029
0,029
0.003
39.9 (1,072)
36.0 (968)
aHorsepower not a measured value calculated from generator output times
1.45
&Based on lower heating value
cBased on data supplied by SoCal
dCalculated heating value
2-4
-------
specifications. Exhaust gas temperature across the catalyst increased abo.
17ฐC (30ฐF) on the average reflecting the exothermic oxidation reaction
promoted by the catalyst.
2-5
-------
REFERENCES FOR SECTION 2
2-1. Chehaske, J. T., "NOX Flue Gas Treatment," presented at the Seminar
2-2,
on Emissions and Air Quality At Natural
San Antonio, Texas, November 12, 1980.
Gas Pipeline Installations,
Khakbiz, S., "Engineering Report OuPont Non-Selective System At
Honor Rancho," Southern California Gas Company Engineering Job
M-82-35, April 8, 1983.
2-6
-------
SECTION 3
EMISSION RESULTS
The objectives of this test program were: (1) to measure engine exhaust
emissions during a 15-day test period to evaluate the continuous performance
of the catalyst, utilizing continuous NOX and other gas emission analyzers,
and (2) to perform comprehensive tests over a 1-day period to measure the
effect of the catalyst on inorganic and organic emissions including the
possible formation of nitrogen compounds, such as NH3 and HCN. Emission
measurements were performed in cooperation with SoCal, owner and operator of
the test facility, whose field crew and equipment included an enission
monitoring laboratory with operating staff.
3.1 SAMPLING PROTOCOL
Figure 3-1 illustrates a schematic of the test site highlighting the
sampling locations, sampling and analytical test matrix, and the test team
performing the sampling and evaluation. As indicated, continuous monitoring
of flue gas was performed both upstream and downstream of the catalytic
reactor utilizing both heated and unheated sample lines. The sampling and
gas conditioning system for this test program included continuous monitors
for 02, COj, CO, NO, NOX, and TUHC. The continuous monitors were operated
throughout a 15-day test period while engine load fluctuated according to
generator demand. Certification of the NOX analyzer readings was performed
twice during this 15-day test period using standard EPA Method 7 protocol.
3-1
-------
Stack
Lube oi1
pump
Sample Location Type of Sample
Grab sample -- Fuel
A Natural
gas to
engine
B -- Catalyst
inlet
C Catalyst
outlet
D -- Lube oil
pump
Analyses3
Gas chromatography for
composition; heating value,
specific gravity
Extractive Sample 03, CC>2, CO, TUHC, NO, NOX,
Continuous Monitors
Sampling train
SASS
Samp!ing train
Modified Method 6
Sampling train
Modified Method 6
Grab samp! e Gas
bomb
Grab sample --
Method 7 flasks
Particulate by gravimetry,
inorganics by SSMS and
semi- and nonvolatile
organics by EPA Method 625
MH3 by selective ion
HCN by selective ion
N20 by GC/ECD
MOy
Same as location B except no Method 7 taken
Grab sample Lube Inorganics
oil
Measurement and analysis techniques used are discussed in detail in
Appendix A.
Figure 3-1. Campling sites and analysis test matrix.
3-2
Test
Number
SoCal
Acurex
Acurex
Acurex
Acurex
Acurex
Acurex
Acurex
-------
The source assessment sampling system (SASS) , the NH3, and the HCN,
sampling trains were operated during 1 day of tests at both the inlet and
outlet of the catalytic converter. Simultaneous inlet and outlet samples
were performed to measure any change in the organic and inorganic composition
of the exhaust gas across the catalyst. These measurements were performed
while engine load was maintained constant and A/F was adjusted for effective
NOX reduction by the catalyst.
Figure 3-2 illustrates the actual test activity schedule. The following
sections summarize the emission results. Sections 3.2 through 3.4 present
emission results obtained during the comprehensive tests that took place on
June 7, 1983. Section 3.5 summarizes results of continuous emission
measurements and EPA Method 7 certification tests performed over the 15-day
test period. Details of the sampling and analysis procedures used are
discussed in Appendix A.
3.2 CRITERIA POLLUTANT AND OTHER VAPOR SPECIES EMISSIONS
Table 3-1 summarizes gaseous and particulate emissions measured during
the 1-day comprehensive tests performed at the beginning of the 15-day
continuous monitoring period. Exhaust 03 was essentially undetected
(reported as 0.1 percent dry). This indicates that the air-fuel mixture was
near or below stoichiometn'c conditions, about 17.2 A/F weight basis.
Figures 3-3 and 3-4 show the vernation in exhaust gas 02 and C02
concentrations over the comprehensive test day (June 7, 1983). As indicated
in the 02 chart (Figure 3-3), prior to the start of the tests exhaust 02 was
reading approximately 0.8 percent. At about 9:00 a.m. the A/F was adjusted
for richer burning conditions with exhaust 02 dropping essentially to zero.
3-3
-------
June 1983
Test activity 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Continuous monitors A
(inlet/outlet)
Comprehensive tests
(inlet/outlet)
SASS
NH3
HCN
N20
Method 7 certification
tests (inlet)
A
A
A
A
A
A
Figure 3-2. Test activity schedule
-------
TABLE 3-1. CRITERIA AND OTHER GAS SPECIES EMISSIONS COMPREHENSIVE TESTS
Pollutant3
Catalyst Inlet
Catalyst Outlet
As measured by
continuous gas
analyzers, range
(average)
03, percent dry
CO?, percent dry
CO, ppn dry*5
NOX, ppn dry
TUHC, ppn dry
as CH4
- (0.1)
9.8 to 10.5 (10.2)
13,750 to 15,500 (14,600]
1,650 to 1,850 (1,700)
140 to 370 (215)
-- (0.1)
9.8 to 10.6 (10.2)
12,000 to 14,000 (13.20U1
300 to 800 (550)
80 to 200 (125)
Corrected average
gaseous emissions:
CO
N0xf
TUHC9
NH3
Total cyanide0
Solid particjlate
mass emissions:
-- SASS solid
pprrr-
ng/Jd g/Bhp-hre
ppmc
ng/Jd g/3hp-hr8
4,270
486
61
8.9
0.005
1,210
770
34
5.2
0.005
12.2
7.79
0.33
0.05
5.1 x 10-5
3,860
157
36
140
2.3
1,030
250
20
82
2.2
10.4
2.53
0.20
0.82
0.022
0.309 0.003
0.303
0.003
aAppendix i\ discusses continuous monitor analyses used, sample gas
conditioning system, particulate sampling equipment, and other sampling
trains and procedures.
^CO emission data provided by SoCal .
Corrected to 15 percent 02, dry.
^On heat input basis, lower heating value.
eShaft output basis.
fAs NO2
9As CH4
hAs HCN
3-5
-------
INLET 02 _ i
I A OUTLET 02
in !
'-'
I- J"1
Z I
LLJ j
o: mj n
u : a n
o_ n n n n
OJ
-------
(\J
0_
z00
111
u
a:
LiJ
Q.
(\J
a
u
(D
(M
D-h
0
~r
8
I
12
16
a nn
G INLET CO2
A OUTLET C02
20
TIME (JUNE 7>
Figure 3-4. Exhaust gas CO? during comprehensive tests,
3-7
-------
This condition was maintained until approximately 5:00 p.m. when all emission
measurements were concluded.
CO emissions exceeded 3,000 ppm as measured by the low range CO analyzer
in the Acurex van (the high range CO analyzer was inoperative on the
comprehensive test day). This is above the quantisation limit of the
analyzer. However, SoCal instrumentation provided data on CO during the test
period. These emissions showed CO in excess of 1 percent at both inlet and
outlet concentration. Only a 10 percent CO reduction by the catalyst was
recorded by SoCal.
NOX emissions at the catalyst inlet ranged from about 1,650 to 1,850 ppm
as measured (at zero percent 03) outlet emissions showed a greater variation,
from 300 to 800 ppm. Figure 3-5 shows the variation in NOX emissions over
the test period. Inlet NOX emissions corrected to 15 percent 02 were about
800 ppm prior to the start of the comprehensive tests. Following engine
adjustment for richer burning condition, inlet concentration decreased to
about 530 ppm at the start of the tests with an apparent further decrease to
470 ppn at the end of the tests. At the conclusion of the tests, the engine
load and A/F changed, resulting in an increase in NOX back to about 800 ppn
(15 percent 02). Catalyst outlet NOX emissions were monitored during the
8-hr comprehensive test period. These data show an initial concentration of
about 90 ppm (at 15 percent 02) followed by a gradual increase to 230 ppm at
the end of the tests.
The resulting NOX reduction efficiency of the catalyst during this time
period is illustrated in Figure 3-6. Catalyst performance ranged from a
maximum of 81 percent NOX reduction at the start of the tests to 54 percent
at the end of the tests. This reduced efficiency may have been caused by a
3-8
-------
o
o
D
^ o_; n Q
i\! 8~b
ID D
z
Q. o
D
n
u
n
D INLET NOX
A OUTLET NOX
n
X
9
ฐ
A
i
4
1
8
1
12
1
16
TIME CJUNE
1
20
24
Figure 3-5. Exhaust gas NOX enissions during conprehensi ve tests,
3-9
-------
K* 9
(J
UJฎ
ii
U
H-l
I, O
t"
UJ
h-
U
Q (M
UJ
ฃ
gฐ
D
n
n
n
I
S
1
12
I
16
TIME CJUNE 7>
20
24
Figure 3-6. Catalyst NOX reduction efficiency during comprehensive tests.
3-10
-------
small perturbations in A/F. As indicated earlier, the exhaust Q? of near
zero percent indicates combustion at or below stoichiometric conditions.
Small perturbations in A/F in this range would not be detected from
monitoring fy levels which were already near zero. Neither the NOX reduction
efficiency nor the outlet NOX concentrations measured during this test would
meet the SCAQMD rule 1110 efficiency of 90 percent or an emission rate of
0.28 ug/J heat output.
Total unburned hydrocarbon ranged from 140 to 370 ppm as measured
(215 ppm average) at the inlet. These emissions were reduced on passage
through the catalyst to a range of 80 to 200 ppm (125 ppm average) at the
outlet. This corresponds to an average hydrocarbon emission reduction of
42 percent. Figure 3-7 shows the variation in TUHC emissions over the test
day. The increase in TUHC at about 8:00 a.m. corresponds to the adjustment
in engine A/F toward rich burning condition.
Ammonia emissions were measured with an extractive sampling train, once
at the inlet location and twice at the outlet location. The inlet
concentration was 31 ppm at stack conditions (0.05g/Bhp-hr). Outlet NH3
emissions ranged from 440 to 530 ppm (0.66 to 0.80g/Bhp-hr) with an average
of 483 ppm (0.82g/Bhp-hr) . This corresponds to a 15-fold increase in NH3
emissions across the catalyst. Total cyanide emissions althougn lower than
NH3 emissions at both locations also, showed a significant increase from about
0.02 ppm as measured at the inlet (0.051 mg/Bhp-hr) to 8.2 ppm (22 mg/Bhp-hr)
at the outlet, a 400-fold increase.
Solid particulate emissions measured by the SASS train at both locations
showed essentially no change from the inlet to outlet location.
3-11
-------
a
t\j-
a
*a
ID OD
h-
< a.
(0
a_
o_
D_
y
_i_
D
D
A
INLET TUHC
OUTLET TUHC
D
D
D
D
A
A
i
8
I
12
D
A
1
16
20
24
TIME CJUNE
Figure 3-7. Exhaust gas hydrocarbon emissions during comprehensive tests.
3-12
-------
N20 emissions were measured by gas chromatography with electron capture
detection of exhaust gas samples taken at the inlet and outlet of the catalyst.
Table 3-2 summarizes these results. Information on 03, NO, NOX, and N02 (by
difference) are also indicated. These emissions were recorded by continuous
analyzers during the grab sampling of the gas for N20 analyses. As indicated,
no NOX reduction was taking place during the time the N20 samples were taken.
The concentration of N02 varied from about 6 to 8 percent of the total NOX.
measured in duplicate tests at both inlet and outlet locations ranged from 64 to
about 180 ppm at the inlet and 17 to 56 ppm at the outlet. All concentrations
are corrected to 3 percent 02- These ^0 concentrations represent about 2 to 7
percent of the total inlet NOX and 0.6 to 2 percent of the total outlet NOX.
Previous I^O data collected in the CMEA program has shown that ^0 from
uncontrolled external combustion sources has ranged between 15 to 20 percent of
the total NOX (Reference 3-2). Although the concentration of ^0 varied for
these two tests, the percent reduction by the catalyst remained fairly constant
at 70 percent ^0 reduction by the catalyst. Conversely apparent N02 reduction
by the catalyst was 15 to 20 percent.
3.3 TRACE ELEMENT EMISSIONS
Inorganic trace element concentrations were measured in the exhaust gas
samples collected at the inlet and outlet of the catalytic reactor.
Laboratory analyses included spark source mass spectroscopy (SSMS) for
70 elements and atomic absorption spectroscopy (AAS) for mercury, antimony,
and arsenic. AAS was also used to confirm SSMS results on selected organics
whose concentration exceeded the upper quantisation limit of the SSMS
analyses. Once concentrations in the samples were determined by these
analyses, trace element concentrations in both flue gas streams could be
3-13
-------
TABLE 3-2. N20 AND NOX EMISSIONS3
^^^=5
02.
NOX
NO,
N02
N20
N20
Component
percent dry
, ppm dry
ppm dry at 3 percent 02
ppm dry
ppm dry at 3 percent 02
b, ppm dry
ppm dry at 3 percent 02
, test 1, ppm dry
ppm dry at 3 percent 02
test 2, ppm dry
ppm dry at 3 percent 02
Upstream of
catalyst
2.8
2,700
2,670
2,500
2,470
200
198
181
179
65
64
Downstream of
catalyst
2.0
2,840
2,690
2,660
2,520
180
171
56
53
18
17
Emissions are measured the day after the comprehensive tests are
completed.
bBy difference, NOX to NO.
3-14
-------
computed. These concentrations are summarized in Appendix 3. Table 3-3
summarizes the emission rate of inorganic elements at the catalyst inlet anr"
outlet locations. Only those elements detected at greater than blank levels
in at least one sample are noted in the table. The emissions are reporter in
micrograms per second (ng/s). The mass balance is expressed by the ratio of
emission rate to input rate from the lube oil. The consumption of luhe oil
was assumed to be 0.093 nl/s (1.37 gal/Bhp-hr) based on the engine
manufacturer specifications.
Sulfur emissions were the highest of all elements ranging fron 89 to
280 mg/s (240 to 740 ng/dscm). These emissions translate to a sulfur
concentration in the natural gas fuel of about 0.01 to 0.04 percent,
corresponding to a typical h^S concentration. The sulfur concentration in
the lube oil accounted for an insignificant fraction of these emissions.
Sodium emissions were second highest after sulfur. Again, the lube oil did
not contribute to these emissions. It is possible that sodium salts may have
been present in the gas fuel along with sulfur. It is also likely that
suspended salts (NaCl and other sodium compounds) may have been present in
the intake air-
Other trace elements whose emission rate exceeded 10 ug/s (26 ug/dscm}
at either inlet or outlet location were barium, calcium, chromium, copper,
fluorine, iron, magnesium, manganese, nickel, potassium, silicon, silver,
tungsten, and zinc. In nearly all 'cases, the catalyst outlet emissions were
higher than the inlet emissions, often by as much as one order of magnitjde.
This was especially the case for metals such as copper, iron, magnesium,
manganese, nickel, and zinc. In general, the lube oil trace element input
rates were insufficient to account for either catalyst inlet or- outlet
3-15
-------
TABLE 3-3. INORGANIC TRACE ELEMENT EMISSION RATES
Emissions (ug/s)
Mass balance
(exhaust gas/lube oil)
Element
Al uminum
Antimony
Arsenic
Barium
Beryl 1 ium
Bi smuth
Bromine
Cadmium
Calcium
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Fluorine
Gallium
Germanium
Hafnium
Iodine
Iron
Lanthanum
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel
Inlet
6.5
0.0025
0.064
19
<0. 0000064
0.0010
0.015
0.00047
180
3.1
0.00015
>1.5
0.26
5.7
5.9
>0.83
0.20
0.00060
0.0030
0.32
15
31
0.056
0.29
10
0.4
0.070
3.1
0.00049
0.31
Outlet
2.4
0.11
0.25
23
<0.041
0.043
0.88
58
0.20
1.6
>1.4
290
2.3
>420
>120
1.9
0.00086
0.0043
0.024
150
<0.20
0.15
0.19
57
12
0:037
0.99
0.0047
250
Catalyst
inlet/lube
15
NAa
MA
0.23
NA
0.061
MA
NA
6.2
NA
NA
>1.7
15
340
70
>1.9
NA
NA
NA
19
36
NA
3.3
11
30
4.7
13
37
NA
1.8
Catalyst
Outlet/lube
5.6
NA
NA
0.28
NA
0.25
NA
NA
2.0
NA
NA
1.7
>17,000
>140
5,000
>290
NA
NA
NA
1.4
350
NA
9.1
7.3
170
140
6.9
12
NA
1,500
aNA ~ Not applicable lube oil concentration was zero
3-16
-------
TABLE 3-3. (concluded)
Emissions (yg/s)
Mass balance
(exhaust gas/lube oil)
El ement
Niobium
Palladium
Phosphorus
Potassium
Praseodymium
Rhodium
Rubidium
Ruthenium
Scandium
Selenium
Sil icon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tell urium
Thorium
Tin
Titanium
Tungsten
Uranium
Vanadium
Yttrium
Zinc
Zirconium
Inlet
1.5
0.0010
2.0
68
0.00013
0.012
__
<0.00015
_-
0.0090
220
0.59
59,000
1.0
89,000
0.00016
0.0045
0.031
51
0.0032
0.030
0.0016
9.5
Out! et
0.17
0.0057
11
130
0.000094
0.0043
0.41
<0. 00043
0.21
0.55
500
79
60,000
2.0
280,000
4.1
0.12
0.0072
0.013
4.1
2.6
0.0016
0.40
0.044
170
1.1
Catalyst
inlet/lube
NA
NA
0.038
40
NA
NA
NA
NA
0
0.053
88
NA
23,000
12
250
NA
NA
NA
NA
0
NA
NA
1.8
NA
0,43
0
Catalyst
Outlet/lube
NA
NA
0.21
77
NA
NA
NA
NA
>25
3.2
200
NA
23,000
1 A
24
780
MA
NA
NA
NA
>240
NA
NA
24
it A
NA
7T
.7
26
aNA Not applicable ~ lube oil concentration was zero
3-17
-------
emission rates. This suggests that metallic element emissions originated
fron internal parts of the engine, the muffler and/or the catalytic reactor.
However, some contamination of the samples by means of sampling trains may
also have been possible. This is probable in the case of silver results
because silver nitrate is used in one of the SASS impingers as an absorbing
solution.
Overall, it is quite evident that the exhaust gas trace element content
increased across the catalyst. Platinum and rhodium, the two noble metals of
the catalyst, generally were present at low levels. In fact, platinum was
not detected in the exhaust gas at either location. This result was in part
due to blank concentration exceeding sample concentration. Rhodium emissions
were in the range of 4.3 to 12 ng/s. However, there was no detected increase
across the catalyst.
3.4 ORGANIC SPECIES EMISSIONS
Organic analyses were performed on the exhaust gas samples collected at
the catalyst inlet and outlet locations. SASS samples were analyzed for
semivolatile and nonvolatile organics according to the EPA Level 1 protocol
(Reference 3-1) as outlined in Appendix A. Semivolatile organic compounds
with boiling points in the nominal Cj to C\ฃ range of 100ฐ to 300ฐC (210ฐ to
570ฐF) were determined in the laboratory by total chromatographable organic
(TCO) analysis of the combined organic module sorbent (XAD-2) and condensate
extracts. Nonvolatile organic species having boiling points in the nominal
Ci6+ range of >300ฐC (570ฐF) were measured by gravimetric (GRAV) analysis of
SASS sample extracts.
Infrared spectrometry (IR) was performed on the GRAV residue of SASS
train extracts to identify organic functional groups possibly present. Gas
3-18
-------
chromatography/mass spectrometry (GC/MS) analyses of the XAD-2 extracts were
also performed to identify specific polynuclear aromatic hydrocarbons '?AH)
and other organic components (the semivolatile organic priority pollutants).
The components sought in the GC/MS analysis and their respective detection
limits are listed in Table 3-4. In addition, liquid chromatography (LC)
separation of selected sample extracts, with TCO and GRAV, and the analyses
of the fractions eluted from the column, were performed.
3.4.1 TCO, GRAV, GC/MS and IR Analyses of Total Sample Extracts
Table 3-5 summarizes organic emission results based on TCO, GRAV and
GC/MS analyses. The concentration of organics at the catalyst inlet location
is significantly higher than that at the outlet location. This is evidenced
by both TCO and GRAV results as well as by the concentration of the priority
pollutants noted. The high levels of organics at the catalyst inlet reflect
the near stoichiometric A/F setting prevalent during these tests. The
reduction in organic emissions across the catalyst parallels the decrease in
CO and hydrocarbon emissions noted in the preceding section.
Total organics in the range of >C^ (boiling points greater than 100ฐC)
were about 15 mg/dscm at the catalyst inlet location. The corresponding
concentration at the catalyst outlet was about 2.0 mg/dscm.
Priority pollutants at the catalyst inlet whose concentration exceeded
10 ug/dscm were acenapthene, acenaphthylene, fluorene, and phenanthrene. All
these compounds showed concentrations below or near the method detection
limit (0.4 yg/dscm) at the outlet location indicating oxidation by the
catalyst.
Interestingly, the PAH compounds most abundant in the catalyst inlet
exhaust were those containing three or more fused rings. Naphthalene, the
3-19
-------
TABLE 3-4. COMPOUNDS SOUGHT IN THE GC/MS AND THEIR DETECTION LIMITS
(ng/yl INJECTED)
Acid Compounds
2,4,6-trichlorophenol
p-chloro-m-cresol
2-chlorophenol
2,4-dichlorophenol
2,4-dimethyl phenol
5 2-nitrophenol
5 4-m'trophenol
5 2,4-dinitrophenol
5 4,6-dinitro-o-cresol
5 pentachlorophenol
phenol
Base Neutral Compounds
1,2,4-trichl orobenzene 1
1,2-dichlorobenzene 1
1,2-diphenylhydrazine 1
(as azobenzene)
1,3-dichlorobenzene 1
1,4-dichl orobenzene 1
2,4-dinitrotoluene 1
2,6-dinitrotoluene 1
2-chloronaphthalene 1
3,3'-dichlorobenzidine 5
3-nethyl 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-nitrosodimethylamine NA
N-m'trosodi phenyl amine 1
acenaphthene 1
acenaththylene 1
anthracene 1
benzo(ghi)perylene 5
benzidine 20
benzo(b)fl uoranthene 1
benzo(k)fl uoranthene 1
benzo(a)anthracene 1
benzo(a)pyrene 1
benzo(c)phenanthrene
bis(2-chl oroethoxy)methane
bi s(2-chloroethyl)ether
bis(2-ch1oroisopropy1)ether
bi s(2-ethyl hexyl)phthal ate
butyl benzyl phthalate
chrysene
di-n-butyl phthalate
di-n-octyl phthal ate
dibenzo(a,h)anthracene
dibenzo(c,g)carbazol el oteher
diethyl phthalate
dimethyl phthalate
fl uoranthene
fluorene
hexachlorobenzene
hexachlorobutadiene
hexachlorocyclopentadiene
hexachloroethane
indeno(l,2,3-cd)pyrene
isophorone
naphthalene
nitrobenzene
perylene
phenanthrene
pyrene
5
20
20
20
5
1
40
1
1
1
1
1
1
1
1
5
40
1
1
1
1
1
1
1
1
5
1
1
1
40
1
1
3-20
-------
TABLE 3-5. TOTAL ORGANIC AND SEMIVOLATILE ORGANIC
PRIORITY POLLUTANT EMISSIONS, ug/dscn
Catalyst inlet
Catalyst outlet
Organic Category:
C7 to Ci6 (TCO)
Ci6+ (GRAV)
Total , > C;
8,000^
7,400
15,400
1,800
300
2,100
Senivolatile Priority
Pollutants
Run 1 Run 2 Average
Acenapthene
Acenaphthylene
Benz(a)anthracene
Benzofluoranthenes
Bis(2-chloroethyl )ether
Bis(2-ethylhexyl )phthalateb
Butyl benzyl phthalateb
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Phenol
Pyrene
16.5
62.3
5.1
1.9
2.1
54.9
0.7
1.9
0.5
17.9
<0.4
40.3
<0.4
2.2
<0.4
1.2
<0.4
<0.4
<0.4
1.0
<0.4
<0.4
<0.4
<0.4
26.8
1.2
1.6
<0.4
<0.4
1.2
<0.4
<0.4
<0.4
1.3
<0.4
<0.4
<0.4
<0.4
30.2
1.5
2.1
<0.4
<0.4
1.2
<0.4
<0.4
<0.4
1.2
<0.4
<0.4
<0.4
<0,4
28.5
1.4
1.8
<0.4
aThis number is based on the average of results of duplicate analyses which
showed 270 ng and 170 mg TCO, respectively.
"Level corresponds tn that comnonly found in laboratory blanks.
3-21
-------
two-fused-ring PAH very commonly found in combustion system exhaust gas, was
absent in the catalyst inlet gas, as was phenol. At the catalyst outlet,
however, levels of the higher order PAH's were much lower, but naphthalene
and phenol levels were increased. Evidently, the higher order PAH's were
being oxidized, though not completely, with naphthalene and phenol as
incomplete oxidation products.
Table 3-6 summarizes results of the IR spectroscopy analyses of the
XAD-2 plus organic module condensate extracts. As noted in the table, the
catalyst outlet sorhent nodule extract and the sorbent blank extract had weak
IR spectra (no peaks). The spectrum for the catalyst inlet sorbent extract
(which had higher total organic content) suggests the presence of aliphatic
hydrocarbons and oxygenates such as alcohols, carboxylic acids, aldehydes,
and ketones.
3.4.2 Column Chrgjiaj^g_rajjhy_ _S_ep_a_ratii_o_n__a_n_d_ I_R__Sp_ec_t_ra^ of__LC__Fra_c_t_i_qns_
The XAD-2 and organic module sample extracts for the catalyst inlet
sample were separated by polar character via LC fractionation on silica gel.
GRAV and TCO content were then obtained for each LC fraction. Results of
these analyses are summarized in Table 3-7. The data show a relatively even
distribution of organics in each fraction, although the concentration in
fraction 2 was the lowest at 0.16 mg/dscm. The highest was in LC6 with 1.9
mg/dscm. Fraction 6 normally contains oxygenated organics such as alcohols,
phenols, esters, ketones, and amines. Fraction 3, the second highest in
concentration generally contains aromatic hydrocarbons. Fractions 1 and 4,
both at about 1 mg/dscm, generally contain aliphatic hydrocarbons and less
polar oxygenated hydrocarbons such as ethers, respectively.
3-22
-------
TABLE 3-6. IR SPECTRA SUMMARY
Sample
XAD-2 + OMC extract,
catalyst inlet
Number
(cm-1)
3571-2944
2907
1673
1538
1439
1266
Intensity3
M
S
S
M
M
M
Assignment
0-H stretch
CH alkyl
C=0 stretch
Unassigned
CH2 alkyl
C-0 stretch
XAD-2 + OMC extract,
catalyst outlet
XAD-2 blank extract
No peaks
No peaks
aS = Strong
M Moderate
TABLE 3-7. TCO AND GRAV RESULTS FOR THE LC FRACTIONS OF THE CATALYST
INLET XAD-2 EXTRACT*
Total
Total
Fraction
LCI
LC2
LC3
LC4
LC5
LC6
LC7
TCO
mg/dscm
<0.033
0.033
0.51
0.073
<0.018
<0.0i8
<0.018
GRAV
mg/dscm
0.99
0.13
1.2
0.92
0.55
1.9
0.51
mg/dscm
0.99
0.16
1.7
0.99
0.55
' 1.9
0.51
ng/J heat input
0.23
0.037
0.39
0.23
0.13
0.44
0.12
mg/Bhp-hr
2.3
0.37
3.9
2.3
1.3
4.3
1.2
0.62
6.2
6.8
1.6
15.7
aResults are based on the total organics recovered in each fraction
corrected to total organics in the original sample.
3-23
-------
IR spectra were obtained on the GRAV residue of each LC fraction.
Table 3-8 summarizes these IR spectra results. Absorhances consistent with
the presence only of aliphatic hydrocarbons were in the LCI spectrum. The
spectra of LC3 and 4 suggest the possible presence of aldehydes, ftfeher
oxygenated hydrocarbons such as carboxylic acids, alcohols, and ketones are
suggested by the spectra of LC6 and 7. Comparing Table 3-5 to Table 3-7
shows that all absorbances in the spectrum of the total sample extract are
accounted for in the fraction spectra. In fact the LC fraction spectra are
none defined.
3.b EXTENDED CONTINUOUS EMISSIONS MONITORING
Continuous monitoring for exhaust gas 02, C02, CO, NOX and TUHC was
performed for a 15-day period from June 6 to June 21, 1983. With the
exception of June 7, the engine was operated under normal conditions with no
restrictions imposed on load or A/F; recall that the engine had no automatic
A/F controller. Figures 3-8 through 3-12 illustrate emission data over this
period. The emission data in these figures represent hourly averages of data
taKen on 5- to Ib-minute intervals.
Although this method of presenting the test data represents a more
manageable task, it also tends to "smooth out" some of the peaks in emissions
that occurred during abrupt changes in engine operation. Nevertheless, the
data do highlight some important characteristics of NSCR performance during
unconstrained engine operation.
Exhaust 02 data, summarized in Figure 3-8, show the near stoichiometric
A/F of the comprehensive tests performed during June 7. Following these
tests, the A/F was increased resulting in exhaust 02 of shout 2 percent at
the catalyst inlet for most of the 15-day test period. Occasionally, the 02
3-24
-------
TABLE 3-8. SUMMARY OF IR SPECTRA FOR LC FRACTIONS OF THE CATALYST INLET
XAD-2 EXTRACT9
Fraction
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Frequency
(cm-1)
2945
No Peaks
2940
1715
2930
1700
1555
2930
3360
3065
2935
1710
1605
1555
1540
1380
1278
740
3540
2940
1710
Intensity13
S
S
S
M
S
M
S
M
W
S
S
w
M
W
w
w
w
S
w
w
Possible
assignment
C-H Alkyl
C-H Alkyl
C=0
C-H Alkyl
C=0
Not assigned
C-H Alkyl
0-H Stretch
C-H Alkyl
C-H AUyl
C=0 Stretch
C-C Alkenyl
Not assigned
CH2
CH3
C-0
C-H Alkyl
0-H Stretch
C-H Alkyl
C=0 Stretch
Possible compound
categories present0
Aliphatic Hydrocarbons
--
Hydrocarbons, aldehydes
Hydrocarbons, aldehydes
Hydrocarbons
Hydrocarbons (Alkyl and
alkenyl), carboxylic acids,
alcohols, ketones
Hydrocarbons, carboxylic
acids, alcohols
aSpectra for the XAD-2 blank LC fractions had no peak.
bS = Strong, M Moderate, W Weak
cPossible compound categories present consistent with spectra and LC
fraction.
3-25
-------
ID-
m-
(\J
O en-I
t\i-
D
n
A
INLET 02
OUTLET C2
11 13 15
JUNE 1983
17
19
21
Figure 3-8. Exhaust 02 for the .15-day continuous monitoring period
3-26
-------
in.
o
u
Q_
01-
03-
D INLET CO2
A OUTLET CO2
D ซ&" <D
a
A
i i i
11 13 15
JUNE 1983
i
17
1
19
21
Figure 3-9. Exhaust C02 for the 15-day continuous monitoring period.
3-27
-------
D INLET CO
A OUTLET CO
JUNE 1983
Figure 3-10. CO emissions for the 15-day continuous monitoring period.
3-28
-------
o
o.
<\J
O
O
O
D INLET TUHC
A OUTLET TUHC
11 13 15
JUNE 1983
\
17
19
21
Figure 3-11. TUHC emissions for the 15-day continuous monitoring period.
3-29
-------
INLET NOX
OUTLET NOX
9
11 13 15
JUNE 1983
Figure 3-12. NOX emissions for the 15-day continuous monitoring period.
3-30
-------
the catalyst inlet for most of the 15-day test period. Occasionally, the 02
climbed as high as 3 and 4 percent but remained at this level for less than a
day. The difference between outlet 02 and inlet 02 shown in the data for the
period following June 13 is considered suspect since it is unlikely that the
02 would increase across the catalytic reactor.
Figure 3-9 illustrates the C02 emission trends. During the
comprehensive tests and periods immediately preceding and following these
tests exhaust C02 ranged from about 10 to 11 percent on a dry basis. Since
stoichiometric C02 for the natural gas burned during these tests is 12
percent the CO emissions were probably in the'range of 1 to 2 percent. The
increase in inlet C02 to 13 and 14 percent after June 10 is considered
suspect. In contrast, outlet C02 concentration was usually in the range of
10 to 12 percent. This may be more indicative of actual combustion
conditions. This range of 10 to 12 percent C02 corresponds to 3.5 and zero
percent 02, respectively, with complete combustion.
Figure 3-1Q illustrates the CO emission trends. Generally CO emissions
were 700 ppm, corrected to 15 percent 02, or lower for most of the test
period. Although simultaneous inlet/outlet data were often not available.
CO at the catalyst outlet was always lower than at the catalyst inlet.
Spikes of CO up to 5,000 ppm (corrected to 15 percent 02) at either the
inlet or outlet location can be seen. These are indicative of richer burning
conditions. These spikes were often accompanied by improved NOX reduction
performance by the catalyst. A trend toward lower CO emissions in the latter
part of the 15-day test period is also apparent. This is in agreement with
the increased 02 levels measured.
3-31
-------
TUHC emissions, illustrated in Figure 3-11, show a substantial increase
following the comprehensive tests on June 7. The highest emissions, up to
800 ppm at 15 percent 03) were registered just prior to June 13. CO
emissions were also highest during this period. Following this peak, TUHC
emission decreased, in parallel with CO emissions as noted above. Outlet
TUHC generally was 100 ppm lower than inlet TUHC.
Figure 3-12 illustrates catalytic inlet and outlet NOX emissions over
the monitoring period. The effective catalyst NOX reduction during the
comprehensive tests of June 7 is clearly evident. Also evident is the
reduced catalyst performance throughout most of the remaining test period.
One clear exception is the test data taken late in the day of June 17 and
into the following morning. During this period outlet NOX was reduced to
below 50 ppm (15 percent Og). This increased catalyst NOX reduction
performance occurred during richer engine operation, as suggested by the high
measured CO emissions.
REFERENCES FOR SECTION 3
3-1. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition," EPA-600/7-78-201, MTIS
PB293795, October 1978.
3-2. Waterland, L. R., et al., "Environmental Assessment of Industrial
Boilers Firing Coal-Liquid Mixtures and Wood," in Proceedings of the
1982 Joint Symposium of Stationary Combustion NOX Control, Volume 2.
EPRI CS-3182, July 1983.
3-32
-------
SECTION 4
ENVIRONMENTAL ASSESSMENT
This section discusses the potential environmental significance of the
engine tested, including results of the bioassay testing of samples collected
during the tests. As a means of ranking species dischargpH for possible
further consideration, exhaust gas discharge stream species concentrations
are compared to occupational exposure guidelines. Bioassay analyses were
conducted as a more direct measure of the potential health and ecological
effects of the emission stream. Both these analyses are aimed at identifying
problem areas and providing the basis for ranking of 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 exhaust gas analyzed in this test program, exhaust
concentrations were compared to an available set of health-effects-related
indices. The indices used for comparison were occupational exposure
guidelines. Two sources of such guidelines were used: the
time-weighted-average Threshold LimitfValues (TLV's) defined by the American
Conference of Governmental Industrial Hygienists (ACGIH) (Reference 4-1)
8-hr time-weighted-average exposure limits established by the Occupational
Safety and Health Administration (OSHA) (Reference 4-2).
4-1
-------
The comparisons of discharge stream species concentrations to these
indices should be used only for ranking species emission levels for further
testing and analyses. Table 4-1 lists those pollutant species emitted in the
catalyst inlet and outlet exhaust gas streams at levels greater than
10 percent of their occupational exposure guideline.
4.2 BIOASSAY RESULTS
Health effects bioassay tests were performed on the organic sorbent
(XAD-2) extract collected by the SASS train at the catalyst inlet and outlet
locations. A detailed description of the biological analyses performed is
presented in Volume II (Data Supplement) of this report. The bioassay tests
performed (Reference 4-3) 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
The results of these assays are summarized in Table 4-2. The data
suggest that the XAD-2 extracts from both locations were of high mutagenicity
and high to moderate toxicity. These are typical bioassay responses for
combustion source XAD-2 extract.
4-2
-------
TABLE 4-1. EXHAUST GAS COMPONENTS EMITTED AT LEVELS EXCEEDING 10 PERCENT
OF THEIR OCCUPATIONAL EXPOSURE GUIDELINE
Emission concentration, mg/dscm
Pollutant
Carbon monoxide, CO
Nitrogen oxide, NOX
Ammonia, NH3
Nitrous oxides, N20b
Cyanide, HCN
Sodium, Na
Barium, Ba
Calcium, Ca
Chromium, Cr
Copper, Cu
Iron, Fe
Nickel, Ni
Phosphorus, P
Potassium, K
Silicon, Si
Silver, Ag
Zinc, Zn
Catalyst inlet
5,350
3,410
23
270
0.022
150
0.049
0.45
0.0007
0.015
0.039
0.0008
0.005
0.17
0.57
0.0015
0.024
Catalyst outlet
4,840
1,180
320
170
10
160
0.064
0.16
>0.78
>1.2
0.41
0.69
0.030
0.36
1.4
0.22
0.46
Occupational
exposure
guidel ine
(ng/n3)
55
6.0
18
C
5.0
2.0^
0.5
2.0
0.05
O.lOe
1.0
0.10
0.10
2.0
-------
TABLE 4-2. BIOASSAY RESULTS
Assay
Sample Amesa CHOb
Catalyst inlet XAD-2 extract H H/M
Catalyst outlet XAD-2 extract H M
aMutagenicity assay.
bToxicity assay.
H high; M moderate; H/M = high to moderate.
REFERENCES FOR SECTION 4
4-1. "Threshold Limit Values for Chemical Substances and Physical Agents in
the Work Environment with Intended Changes for 1983-84," American
Conference of Governmental Industrial Hygienists, Cincinnati, Ohio,
1983.
4-2. OSHA Safety and Health Standards, 29 CFR 1910, Subpart Z.
4-3. Brusick, D. J., and R. R. Young, "IERL-RTP Procedures Manual: Level 1
Environmental Assessment, Biological Tests," EPA 600/8-81-024, NTIS
PB81-228766, October 1981.
4-4
-------
SECTION 5
TEST QUALITY ASSURANCE AND QUALITY CONTROL
Quality assurance (QA) activities implemented for this test included:
Certification of the NOX continuous monitoring analyzer using
standard EPA Method 7 protocol for accuracy determination of NOX
readings.
Duplicate SSMS, TCO and GC/MS analyses of SASS samples for
determination of analytical precision.
The following paragraphs discuss the results of these QA activities.
5.1 NOX CERTIFICATION RESULTS
EPA Method 7 test protocols were used twice during the 15-day continuous
monitoring period to certify the accuracy of the NOX analyzers. Table 5-1
shows that, for the first certification test conducted on June 8, the NOX
monitor readings were consistently 550 to 650 ppm higher than corresponding
Method 7 results. The associated relative accuracy of the instrument as
determined by this test was 29 percent. This compares to an allowable
relative accuracy of 20 percent in performance specification 2 (40 CFR,
Part 60, Appendix B). However, the 'Method 7 results for this first test may
be suspect. Insufficient 02 may have been present in the engine exhaust
tested to completely oxidize all the NO to N02 as required by the method.
Method 7 procedures caution that if the gas being sampled contains
insufficient 02 for the conversion of NO to N02, then 02 should be introduced
5-1
-------
TABLE 5-1. METHOD 7 CERTIFICATION RESULTS: JUNE 8
Test
No.
1
2
3
4
5
6
7
8
9
NOX Reference Method Samples (ppm)
Sample 1
1,760
2,770
2,040
2,110
2,500
2,470
2,070
2,250
2,260
Sample 2
1,960
1,880
2,110
2,450
2,330
1,940
2,100
1,870
2,210
Sample 3
2,580
2,170
2,130
2,400
2,020
2,380
2,090
2,190
2,000
Sample
Average
2,100
2,270
2,090
2,320
2,280
2,260
2,090
2,100
2,160
Average
Analyzer
Reading
Catalyst
Inlet
(ppm)
2,650
2,660
2,750
2,790
2,820
2,800
2,770
2,750
2,800
Difference
(ppm)
550
390
660
470
540
540
680
650
640
Mean reference method 2,190
test value
Mean of differences 570
95 percent confidence interval = 70 ppm
Mean of differences
Relative accuracy
+ 95 percent confidence interval ,nrt
Mean reference method value " *"w
= 29 percent3
aPoor relative accuracy (-20 percent allowed) due to Insufficient
O in gas sample to efficiently oxidize NO to
5-2
-------
into the sampling flasks. However, the method procedures offer no guide as
to what constitutes insufficient 03. For this first certification test,
exhaust 02 was about 2.7 percent; NOX analyzer readings were 2,700 to 2,800
ppm. During the test it was decided that sufficient Qฃ was available.
However the discrepancy between the Method 7 results and the analyzer
readings suggest this may not have been the case. For the second
certification test performed on June 20, 02 (air) was added to the Method 7
sampling flasks. Exhaust 02 for this test was about 1.9 percent; NOX
analyzer readings were 2,900 to 3,000 ppm. Table 5-2 shows that, for this
second certification test, Method 7 results and analyzer readings were in
much closer agreement. The calculated relative accuracy of the analyzer
during this test was 9.2 percent, well within the performance specification.
5.2 DUPLICATE ANALYSES
Blind duplicates were submitted for analysis of trace elements by SSMS.
Precision of the analysis was then determined based on the relative standard
deviation of the replicate samples. Table 5-3 summarizes the results of
these SSMS duplicate analyses.
The average relative standard deviation for all the trace elements was
53 percent within the acceptable range of -50 to 100 percent or a factor of 2
in analytical precision.
Results of duplicate analyses for organic samples are summarized in
Table 5-4. The average relative standard deviation for these duplicate
analyses was 21 percent, well within the project precision goal for these
measurements.
5-3
-------
TABLE 5-2. METHOD 7 CERTIFICATION RESULTS: JUNE 20
Test
No.
1
2
3
4
5
6
7
8
9
NOX Reference Method Samples (ppm)
Samp! e 1
2,770
2,680
2,830
2,870
2,590
2,460
2,750
2,990
2,710
Sample 2
2,670
2,610
2,780
2,820
2,740
2,660
2,890
2,880
2,760
Sample 3
2,940
2,860
2,860
2,800
3,000
2,830
2,990
3,000
2,770
Sample
Average
2,790
2,720
2,820
2,830
2,780
2,650
2,880
2,960
2,750
Average
Analyzer
Reading
Catalyst
Inlet
(ppm)
2,970
3,020
2,900
3,070
2,960
2,950
2,870
2,840
2,880
Difference
(ppm)
180
300
80
240
180
300
(10)
(120)
130
Mean reference method 2,800
test value
Mean of differences 140
95 percent confidence interval = 110 ppm
Mean of differences
Relative accuracy
+ 95 percent confidence interval .--
' Mean reference method value * AWU
= 8.9 percent3
Air was cycled to the flasks to ensure sufficient oxidant for
NO to N02 conversion resulting in relative accuracy within Method
7 performance specification
5-4
-------
TABLE 5-3. DUPLICATE SSMS ANALYSES OF CATALYST OUTLET SASS IMPINGER 1
SAMPLE, mg/1
Element
Silver
Chlorine
Fluorine
Sodium
Sul fur
Selenium
Mercury
Lead
Tungsten
Lanthanum
Barium
Tell eri urn
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Bromine
Arsenic
Gal 1 i urn
Zinc
Copper
Nickel
Cobal t
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Phosphorus
Silicon
Aluminum
Magnesium
Boron
Beryl 1 i urn
Lithium
Sam pi e
819379
1.75
<3
7.18
1,440
9,000
<0.002
7J.0003
0.02
0.01
0.005
0.09
0.003
0.02
0.002
0.003
0.002
0.009
0.04
0.001
0.08
10
>10
0.3
0.01
0.5
0.1
0.2
0.004
0.4
0.01
2
6
0.3
1
0.2
2
0.002
0.001
0.007
Sampl e
819394
2.12
<3
T.44
1,480
4,800
0.003
0.0004
0.02
0.007
0.006
0.06 '
<0.001
0.1
0.007
0.009
0.001
0.05
0.05
0.001
0.03
5
>10
0.2
0.01
0.3
0.07
0.07
0.005
0.2
0.002
2
0.8
0.2
. 2
0.07
0.1
0.001
0.001
0.002
Relative
standard deviation
(percent)
13.5
0
1.6
1.9
43
28
20
25
13
28
71
94
79
71
47
98
16
0
64
47
0
/\O
28
0
35
25
68
9
47
94
0
108
28
47
68
128
47
79
Average standard deviation
53
5-5
-------
TABLE 5-4. RESULTS OF DUPLICATE ORGANIC ANALYSES OF SASS SAMPLES
Sample No. Relative
369 370 standard deviation
Analyses Total mg Total yg (percent)
TCO 270,170
GC/MS:
Phenol 42, 55
Naphthalene 710, 800
Acenaphthylene 31, 32
Phenanthrene 31, 41
Bis(2-ethyl hexyl )-phthalate 26, 35
38
19
8.4
2.2
20
21
Average standard deviation 21
5-6
-------
APPENDIX A
SAMPLING AND ANALYSIS METHODS
Emissions test equipment was provided by Acurex Corporation. Onsite
equipment included a continuous monitoring system for emissions measurements
of gaseous criteria pollutants; the SASS train for particulate mass, selected
inorganics, and semi volatile and nonvolatile prganics; two separate sampling
trains for NH3 and HCN measurement; gas grab sampling equipment for
determining NgO emissions by laboratory gas chromatography, and for
validation of NOX measurements with EPA Method 7. The following sections
summarize the sampling and analysis equipment and methods used in the field
and laboratory.
A.I CONTINUOUS MONITORING SYSTEM
Acurex provided a continuous monitoring system modified to allow online
simultaneous NOX sampling capability at inlet and outlet of the catalytic
reactor. Figure A-l illustrates a simplified schematic of the gas
conditioning and monitoring system. The monitoring capability included 02,
C02, CO (high and low concentrations), NO, NOX, NOX + NHs, and TUHC. A
refrigeration gas conditioning system was used primarily at the inlet
location and provided NO emissions. The heated sample line system was used
primarily at the outlet location and provided data on NO and total NOX.
Table A-l lists the instrumentation constituting the continuous monitoring
and flue gas extractive sampling system. A datalogger was used .in addition
to strip charts to record data continuously.
A-l
-------
,- 5-urn
-j I S.S. filter
Flow
Catalytic converter
, Flow
Ambient air (or NO*, NH3
cal ibration gas)
I I I ' I I I I l I l i l i l i l l l l l H-MKj | I I I I I I I I I I I I I I I I I I I I I I
Pressure
rti 1111 i 11 l 11 [ 111 11 1111 111 111 H h gauge
Refrigeration I
Condensate
TUHC
CO
(high)
CO
(low)
ppm
Calibration gases
CO,
Figure A-l. Schematic of gas conditioning and continuous monitoring system.
A-2
-------
Table A-l. CONTINUOUS MONITORING EQUIPMENT IN THE MOBILE LABORATORY
Instrument
N0a
NOX
TUHC
CO
C02
02
Sample gas
conditioner
Data Logger
Strip chart
recorder
Principle of
operation
Chemil uminescence
Flame ionization
detection
Nondispersive
infrared (NDIR)
Nondispersive
infrared (NDIR)
Fuel eel 1
Refrigerant
dry-condenser
Electronic
Dual pen analog
Instrument
Manufacturer model Range
Thermo Electron 10 AR 0-100 ppm
0-500 ppm
0-1,000 ppm
0-5,000 ppm
Beckman 400 0-10 ppm
0-100 ppm
0- 1,000 ppm
ANARAD - 500R 0-1,000 ppm
ANARAD AR500 0-20 percent
Teledyne 0-5 precent
0-25 percent
Hankinson E-46-SS 10 scfm
Acurex Audodata 9 99 channels
Linear 400 1-10 mV
1-100 mV
0-1 V
0-10 V
aTwo analyzers used for simultaneous inlet and outlet sampling
A-3
-------
A.2 TRACE ELEMENTS AND ORGANIC EMISSIONS
Emissions of inorganic trace elements and organic compounds were sampled
using the source assessment sampling system (SASS). Designed for Level 1
environmental assessment (Reference A-l), the SASS collects large quantities
of gas and solid samples required for subsequent analyses of inorganic and
organic emissions.
The SASS, illustrated in Figure A-2, is generally similar to the system
utilized for total particulate mass emission tests (a high volume Method 5
train) with the exception of:
The addition of a gas cooler and organic sampling module
The addition of necessary vacuum pumps to allow a sampling rate of
2 1/s (4 cfm)
Particulate cyclones shown in Figure A-2 were not used for these tests
because of low particulate loading in the flue gas.
Schematics outlining the standard sampling and analytical procedures
using the SASS equipment are presented in Figures A-3 and A-4. The following
paragraphs briefly describe analytical procedures used in measuring trace
elements and organic emissions.
Inorganic analyses of samples from the SASS train were performed by
spark source mass spectroscopy (SSMS) for most of the trace elements. Atomic
absorption spectrometry (AAS) was used for analyses of volatile mercury (Hg),
antimony (Sb), and arsenic (As). Confirmatory analyses for selected metals
were performed using flame atomic absorption spectrophotometry. Phosphorus
was determined col orimetric ally and sulfur was determined turbidimetrically
in samples needing confirmatory analyses.
A-4
-------
Mealed oven
filter
i
01
Stack T.C.
1/2" Teflorl
1 ine
Isolation
ball valve
Stainless
steel
sample
nozzle
Organic module
Gas temperature T.C.
1/2" Teflon line
Stack
velocity
AP magnehelic
gauges
Stainless steel
probe assembly
Oven
Sorbent cartridge
Heater controller
Imp/cooler trace jf
element collector -S\
Uas meter T.C.
Coarse adjustment
All orifice plate
Orifice All
magnehelic
gauge
Dry lust motor
Impinger
T.C.
Ice bath
GOO grams
.s II lea gel
deslcant
500 ml
0.2 M AgNOj
0.2 M (Nll4)2
500 ml
30X H202
Fine adjustment
valve
Vacuum pumps Heavy wall-
(10 ft3/min each) V4cuum llne
Note: T.C. = Thermocouple
Figure A-2. Source assessment sampling train schematic
-------
SAMPLE
3p CYCLONE
i, rYCLOMF
rii rro , ,
SQR8ENT CARTRIDGE
AQUEOUS CONDENSATE
FIRST IMPINGER
So I 1
d* !_rง " S
s* Jv B ฐ
a 5 a 5 5
* "-a m s 9
o _ u* ฃ e y
< * Z S j -J <
s o < . z'lieM
S ป-0> x < 0 = C 5
x ue= o =06 < S
yj GOD M OH.J a.ta
\* >^ SPLIT
W 99
__.^._,. ^ ^
~\^ SPLIT
COMBINE ^^ 0 ^
______ __^ ^ *
>- - < . -A < < -
SPLIT \
5 GRAMS w w
COMBINE
- AQUEOUS PORTION
N^ ORGANIC EXTRACT N.
/
u>
^
<
^
o
5
1
u)
<
SECOND AND THIRD
IMPINGHRS COMBINED
TOTALS 1 1524525
* If rซquir
-------
Figure A-4. Flue gas sample analysis protocol.
-------
Quantitative information on total organic emissions was obtained by gas
chromatography/flame ionization detector for total chromatographable organics
(TCO) and by gravimetry (GRAV) of sample extracts. Infrared spectroscopy
(IR) and gas chromatography/mass spectroscopy (GC/MS) were used for
identification of organic functional groups and for determining polycyclic
organic matter (POM) and other organic species concentrations (the
semivolatile organic priority pollutants) in extract samples. Figure A-5
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-l and
will not be repeated here.
A.3 NH3 AND HCN SAMPLING AND ANALYSES
NH3 and HCN were measured at the inlet and outlet locations of the
catalytic converter utilizing two separate sampling trains. Both trains were
similar to an EPA Method 6 train except that impinger solutions for NH3
absorption were acid based (HC1) and for HCN were caustic based (NaOH).
Concentrations of NH3 and HCN in solutions were determined in the laboratory
using approved wet chemical methods (Reference A-2).
A.4 N20 SAMPLING AND ANALYSES
The stack gas grab samples were extracted into stainless steel
cylinders for laboratory analysis for N20 using a sampling train illustrated
in Figure A-6. For analysis each sample cylinder was externally heated to
12DฐC (250ฐF), then a 1-ml sample was withdrawn with a gas-tight syringe for
injection into the gas chromatograph (GC) equipped with an electron capture
A-8
-------
Organic Extract
or
Neat Organic Liquid
<
r
TCO
Analysis
Concentrate
Extract
T T t
GC/MS Analysis,
POM, and other
organic species
LRMS
Infrared
Analysis
r t
Repeat TCO
Gravimetric Analysis
if necessary
Figure A-5. Organic analysis methodology.
A-9
-------
Teflon diaphragm pump
Pressure gauge
0.7 urn sintered stainless-steel filter
1/4-ln. stainless-steel
probe
500-cm stainless-steel
sample cylinder
I
ป-
o
(:eram1c Insulation -'
and heat tape
Proportional
voltage
controller
Outlet
valve
Thermocouple
Figure A-6. ^Q sampling system.
-------
detector (ECD). The GC column used was a 10 ft x 1/8 in. stainless steel
column packed with 80/100 mesh chromosorb 101. The flow of nitrogen was
20 ml/min with the column kept at 45ฐC. Elution time for ^0 was
approximately 5 min.
A.5 NOX SAMPLING AND ANALYSES
Certification of the continuous NOX monitor was performed using the
standard EPA Method 7 equipment and protocols.
A-ll
-------
REFERENCES FOR APPENDIX A
A-l. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201,
NTIS PB293795, October 1978.
A-2. "Methods for Chemical Analysis of Water and Wastes," EPA-600/4-79-020,
NTIS PB 297 686, March 1979.
A-l 2
-------
APPENDIX B
TRACE ELEMENT CONCENTRATIONS
The following tables present sample trace element analysis results and
trace element discharge stream concentrations. The tables labeled "ppm"
represent element analysis results (pg/g or yg/ml) for each sample analyzed.
The composition of lube oil and all catalyst inlet and outlet SASS train
samples (filter, XAD-2, first impinger, and second and third impinger) are
noted.
The tables labeled "concentration" give the calculated flue gas
concentration (ug/dscm) of each element corresponding to each SASS train
catalyst sample, and the SASS train sum (labeled "catalyst inlet" and "stack
outlet," respectively).
Symbols appearing in the tables are:
dscm Dry standard cubic meter at 1 atm and 20ฐC
MCG Microgram
ppm parts per million by weight
< Less than
> Greater than
ป
N Element not analyzed
Trace element concentrations less than the detectable limit or having a blank
value greater than the sample value were given an arbitrary concentration of
zero.
B-l
-------
Detectability limits for the various SASS and liquid samples were the
following:
Filter <0.1 ug/g
XAD-2 <0.1 yg/g
Impinger and organic module concentrate <0.1 pg/ml
Lube oil <0.1 ug/ml
The data inputs to a computer code for calculation of trace element flowrates
were the following:
Inlet Location
~ Gas volume sampled by SASS = 27.3 dscm
-- Calculated exhaust gas flowrate = 0.362 dscm/s
Weight of final filter = 1.0264g
-- Filter tare weight 0.9897g
Weight of XAD-2 = 130g
-- SASS inpinger 1 final volume 1,725 ml
Organic condensate final volume = 1,900 ml
-- SASS impinger 2 and 3 final volume 1,735 ml
Outlet Location
Gas volume sampled by SASS = 26.5 dscm
-- Calculated exhaust gas flowrate 0.366 dscm/s
-- Weight of final filter = 1.0326g
-- Filter tare weight 1= 0.9950g
Weight of XAD-2 130g
-- SASS impinger 1 final volume = 1,425 ml
-- Organic condensate final volume = 1,515 ml
-- SASS impinger 2 and 3 final volume 2,600 ml
B-2
-------
Engine Parameters
-- Total heat input rate = 1.73 MW
-- Lube oil consumption rate - 0.093 ml/s
B-3
-------
PPM LUBE OIL
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
PPM
LUBE OIL ELEMENT
. 500E+01 STRONTIUM
. 000E+00 SULFUR
. 000E+00 TANTALUM
.970E+03 TELLURIUM
.000E+00 THORIUM
. 200E+60 TIN
. 100E+00 TITANIUM
,000E-f-00 TUNGSTEN
. 000E+00 URANIUM
. 334E+03 VANADIUM
.000E+00 YTTRIUM
.000E+00 ZINC
.100E+02 ZIRCONIUM
<.200E+00
<.200E+00
.100E+01
.500E+01
.000E+00
.000E+00
. 000E+06
. 200E-I-00
.500E+01
.000E+00
. 200E+00
. 300E+00
.400E+01
. 100E+01
.620E-01
. 100E+01
.000E-1-00
.200E+01
.000E-ป-00
.000E+00
.620E+03
.200E-H02
.000E+00
.000E+00
.000E+00
.080E+00
.000E+00
<. 100E+90
.200E+01
.300E+02
PPM
LUBE OIL
.100E+02
.420E+04
. 000E-t-00
. 000E400
.000E-t-00
.000E400
<.200E-t-00
. 000E+00
. 000E+00
. 200E+00
.000E+00
.260E+03
.500E+00
.300E+02
B-4
-------
HONOR RANCHO ENGINE
PPM INLET NAT. GAS BASELINE
PPM
ELEMENT FILTER XAO
ALUMINUM .438E+03 .000E+00
ANTIMONY .171E+00 .000E+00
ARSENIC .433E+01 .000E+00
BARIUM . 130E+04 .000E+00
BERYLLIUM <.434E-03 .000E+00
BISMUTH .700E-01 .000E+00
BORON U.000E+00 .000E+00
BROMINE .104E+01 .000E+00
CADMIUM .317E-01 .000E+00
CALCIUM .177E+04 .890E-1-02
CERIUM .235E+00 . 160E+01
CESIUM .100E-01 .000E+00
CHLORINE >.100E-i-03 000E+00
CHROMIUM . 176E+02 .090E+00
COBALT .213E+02 .290E+01
COPPER .562E+01 .200E+01
FLUORINE >.560E+02 .000E+00
GALLIUM .617E-I-00 .100E+00
GERMANIUM .404E-01 .000E+00
HAFNIUM .200E+00 .000E+00
IODINE .113E+00 .000E+00
IRON .104E+04 .000E+00
LANTHANUM .426E+00 .250E+01
LEAD .381E+01 .000E+00
LITHIUM .000E+00 .100E+00
MAGNESIUM .264E+03 .000E+00
MANGANESE .233E-t-01 .000E-I-00
MERCURY .982E-0I .180E-01
MOLYBDENUM .207E+02 .150E+01
NEOOYVIUM .330E-01 .000E+00
NICKEL .210E-I-02 .000E+00
NIOBIUM .330E+00 .000E+80
PALLADIUM .700E-01 000E+00
PHOSPHORUS .134E+03 000E+00
POTASSIUM .000E+00 .310E+02
PRASEODYMIUM .868E-02 .000E+00
RHODIUM .800E-I-00 .000E+00
RUBIDIUM .322E-01 .000E+00
RUTHENIUM <.100E-01 .000E+00
SAMARIUM .000E+00 .000E+00
SCANDIUM .000E+00 .000E-I-00
SELENIUM .613E+00 .0Q0E+00
SILICON .323E+04 .100E+02
SILVER .394E+01 .000E-I-00
SODIUM .281E+01 .100E+02
IMPINGER 1
. 000E+00
.000E+00
.000E+00
.000E-t-00
.000E+00
. 000E-I-00
. 000E+00
.000E+00
.000E+00
. 200E-02
.000E-I-00
.000E-t-00
.000E+00
.000E+00
.400E-01
.000E+00
.000E+00
. 000E+00
.000E+80
. 600E-02
. 000E+00
.600E-02
.000E+00
.200E-02
. 1 20E+00
.700E-02
.000E+00
. 000E+00
. 000E+00
.000E+00
.300E-01
.000E+00
.000E+00
. 200E+00
. 000E-t-09
.000E+00
.000E-(-00
.000E+00
.000E+00
.000E4-00
.000E+00
.300E+01
. 100E-01
.113E+04
IMPINCER 2+3
. 000E-1-00
.000E+00
. 000E-I-00
.000E-1-00
.000E+03
.000E-t-0S
.000E-K00
.000E-1-00
.000E+00
.000E-t-00
.000E+00
.000E-I-00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E-t-08
.000E+00
.000E+00
.100E+01
.000E-t-00
.000E+00
. 000E+80
. 000E4-00
. 140E-02
.000E+00
. 000E-I-00
. 000E-I-00
. 000E-I-00
.000E+00
.000E+00
.000E+00
.000E+06
.000E+00
. 000E+00
.000E-I-00
.000E+00
. 000E-1-00
.000E+00
.000E+00
.000E+00
.000E+00
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
.542E402
.126E+93
.000E+00
.109E-01
.304E400
.304E+00
U.000E400
.900E+01
.214E+00
.204E+01
.109E+00
.290E+03
.000E+00
.100E-I-00
. 100E-I-02
.000E+00
.000E+00
.000E+00
.000E+B0
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E-I-00
.100E-02
. 170E+04
.000E+00
.000E+00
.000E+00
<.100E-02
.000E+00
.980E+00
.000E+00
.000E-K00
.000E+00
.100E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E-I-00
.000E+00
. 000E+00
.000E+00
.000E+00
.000E+00
B-5
-------
PPM OUTLET
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
PPM
FILTER XAD
.508E402 .000E400
.371E+00 .000E400
.173E402 .000E400
.159E404 .000E-I-00
<.331E-03 .000E400
.300E400 .000E400
U.000E400 .000E400
.403E401 .000E-(-00
.000E400 .000E400
. 116E404 .000E400
.123E401 .100E-I-00
<.100E-01 .000E400
X100E403 .000E400
.301E402 .157E403
.290E+02 .900E400
.396E402 .300E401
>.555E402 .150E+02
.613E+00 .000E400
.603E-01 .000E-I-00
.300E400 .000E400
. 171E+01 .000E400
.221E403 .750E402
.000E+00 .000E400
.108E402 .000E400
.426E+00 .100E+00
.116E-t-03 .100E+02
.632E+01 .4B0E+01
.113E+00 .160E-01
.671E+01 .500E+00
.332E+00 .000E+00
.240E+02 .135E+03
.323E+00 .000E+00
400E+00 .000E+00
.143E+03 .500E-I-01
.000E+00 .110E+02
.662E-02 .000E+00
.300E-I-90 .000E-1-00
.517E-61 .000E+00
<.300E-61 .000E+00
.000E+00 .000E+00
.510E+90
.710E+00
.126E+04
. 194E+01
.000E+00
.000E+00
.300E+00
.270E+03
.900E+00
.100E+02
IMPINGER 1
.400E-01
<.500E-02
.aeae+00
.200E-01
<.100E-02
.000E+00
.000E+00
.200E-01
.000E+00
.100E+01
.000E+00
.400E-01
<.270E401
.100E+00
.700E-02
>.998E-t-01
.231E+01
.460E-01
.000E+00
.000E-t-00
. 000E-t-00
. 300E+00
<.500E-02
. 000E+00
.000E+00
.920E+00
.770E-01
.150E-03
.000E+00
.000E-I-00
. 193E+00
400E-62
. 000E-H00
.000E+00
.270E+01
.000E+00
.000E+00
. 100E-01
. 000E+00
. 000E+00
. 500E-02
.000E+00
. 000E+00
.194E-H31
. 14SE4-04
IMPINGER 2+3
.000E+00
. 000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E400
.000E+00
.000E+00
.000E400
.000E+00
.000E+00
.009E+09
.000E+00
. 000E-I-00
. 000E-1-00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E400
.000E+00
. 000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E-I-00
.000E400
.000E+00
.000E400
.000E+00
. 000E400
. 000E+00
.000E400
.000E400
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
.482E402
.214E403
.130E400
.662E-03
.503E400
.903E+00
U.090E400
.700E401
.113E+00
.303E+01
.207E400
.327E+03
.298E+00
.100E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.200E400
.000E+00
.300E401
.600E400
.280E-01
. 680E404
. 100E400
. 300E-02
.000E400
.000E400
.100E400
.600E-01
.000E400
.000E400
.100E-02
.390E401
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
. 000E400
.000E400
.000E400
.000E400
.000E400
.000E400
B-6
-------
tfl
CONCENTRATION
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
HONOR RANCHO ENGINE
NAT. CAS BASELINE
MCG/OSCM
CATALYST INLET FILTER
XAD
.165E402
.644E-02
.163E400
.490E402
.163E-04
.263E-02
.000E400
.392E-01
.119E-02
448E403
.789E401
.376E-03
.000E400
.661E400
.146E402
.151E402
.090E-1-00
.499E400
.152E-02
.752E-02
.803E400
.392E402
.763E402
. 143E400
.742E400
.259E402
. 102E401
.178E400
.792E401
.124E-02
.788E400
400E+01
.263E-02
.504E401
.174E403
.326E-03
'.301E-01
. 121E-02
.376E-0J
.000E400
.165E402
.644E-02
.163E400
490E402
.I63E-04
.263E-02
.000E400
392E-01
.1I9E-02
.666E+02
.882E-02
.376E-03
.376E+01
.661E+00
.801E400
.211E+00
.211E401
.232E-01
.152E-02
.752E-02
-425E-02
.392E+02
.160E-01
.143E+00
.000E400
.994E401
.876E-01
.369E-02
.779E+00
. 124E-02
.788E+00
. 124E-0I
.263E-02
.504E401
.000E+00
.326E-03
.301E-01
. 121E-02
..376E-03
.000E400
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.381E403
.762E401
.000E+00
.000E+00
.000E+00
. 138E+02
.952E4ซ1
.000E400
. 476E+00
.000E+00
.000E400
.000E+00
.000E+00
.119E+02
.000E+00
.476E+00
. 000E+00
.000E400
.857E-01
.714E+01
.000E400
.000E+00
.000E400
.000E+00
.000E+00
.148E+03
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
IMPINGER 1
.000E+00
.000E+00
.000E+00
.000E+00
. 000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.266E+00
.000E-I-00
.000E+00
.000E+00
.000E400
.532E401
. 000E400
.000E400
.000E400
. 798E400
.000E400
.798E400
.000E400
.266E400
.160E402
.932E400
.000E400
.000E400
.000E400
.000E400
.399E401
.000E400
.000E400
.266E402
.000E400
.000E400
.000E400
.000E400
.C00E400
IMPINGER 243
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.636E402
.000E400
.000E400
.000E400
.000E400
.890E-01
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
(continued)
-------
HONOR RANCHO ENGINE
CONCENTRATION NAT. GAS BASELINE
MCG/DSCM
ELEMENT CATALYST INLET FILTER
XAD
IMPINGER 1
IMPINGER 2+3
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
.000E+00
.230E-01
.566E+03
.148E+01
.150E406
. 000E-f 00
.230E-01
.122E+03
. 148E+00
.106E+00
. 000E+00
.000E+00
.476E+02
.000E+00
476E+02
.000E400
.000E+00
.399E+03
.133E+01
.150E+06
.000E-i-0e
.000E-I-00
.000E400
.000E+00
.000E+00
a
i
00
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
.265E4-01
.226E*06
.000E+00
.409E-03
, .114E-01
-------
ta
CO
CONCENTRATION
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RURIDIUM
RUTHENIUM
SAMARIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
MCG/DSCM
CATALYST OUTLET FILTER
XAD
.645E401
.000E400
.783E403
.633E401
.000E400
.000E400
.516E401
.235E-02
. 117E-01
.666E-01
.410E403
.558E400
.421E409
.507E400
.156E403
.324E402
.996E-01
.271E401
.129E-01
.685E403
4S9E400
.156E-01
.301E402
.356E403
.258E-03
. 117E-01
.112E+01
. 117E-02
.000E400
.198E401
.145E-0I
.675E400
.618E402
.129E-04
.117E-0I
.000E400
.157E400
.000E409
.453E402
.478E-0I
.390E-03
.390E40I
. 117E40I
.113EH0I
.154E40I
.216E40I
.239E-0I
.235E-02
. 117E-0I
.666E-01
.861E40I
.000E400
.421E400
.166E-0I
.453E40I
.246E400
.440E-02
.26IE400
.129E-01
.933E400
.126E-01
.156E-0I
.556E401
.000E400
.258E-03
. 117E-01
.20IE-02
C .H7E-02
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.491E400
.000E400
.000E400
.770E403
.442E401
.392E402
.736E+02
.000E400
.000E400
.000E400
.000E400
.368E403
.000E400
.000E400
.491E400
.491E402
.235E402
.785E-0I
.245E401
.000E400
.662E403
.000E400
.000E400
.245E402
.540E402
.000E4-00
.000E400
.008E400
.000E400
.000E400
IMPINGER 1
.447E401
< .558E400
.000E400
.223E401
< .II2E400
.000E400
.000E400
.223E401
.000E400
.112E403
.000E400
.447E401
< .302E403
.1I2E402
.782E400
> .111E404
.25BE403
.514E401
.000E400
.000E400
.000E400
.335E402
< .558E400
.000E400
.0eeE400
.103E403
.860E401
.166E-01
.000E400
.000E400
.216E402
.447E400
.000E400
.000E400
.302E403
.000E400
.000E400
.1I2E401
.000E400
.006E400
IMPINGER 243
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.900E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
(continued)
-------
HONOR RANCHO ENGINE
CONCENTRATION NAT. GAS BASELINE
MCG/DSCM
ELEMENT CATALYST OUTLET FILTER
XAO
IMPINGER 1
IMPINGER 243
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
.578E+00
.I50E+01
.137E+04
.217E+03
.163E+06
.199E-01
.277E-01
.491E+02
.757E-01
.000E+00
.000E+00
.I47E+01
.I32E+04
.000E+00
.491E+02
.558E+00
. 000E+00
.000E+00
.217E+03
.163E+06
. 080E+00
.000E+00
.000E+00
. 060E-1-00
. ee0E-l-00
w
*
o
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
.549E+Q1
.760E+06
. 112E+02
.335E+00
.196E-01
.352E-01
.112E+02
.697E+01
.440E-02
.110E+01
.120E+00
.463E403
.295E+01
.188E401
.832E+01
.390E-02
.258E-04
.196E-01
.352E-01
.000E+00
.273E+00
.440E-02
.118E+00
.805E-02
.127E+02
.116E-01
.491E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E400
.000E+00
.000E+00
.000E+06
.98IE+00
.000E+00
.147E+02
.294E401
.313E+01
.760E-1-06
. 112E+02
.335E+00
.000E+00
.000E+00
. 112E+02
.67CE+01
.000E+00
.000E+00
.112E+00
.436E+03
.000E+00
.000E+00
.000E+00
.008E+00
.000E+00
.000E+00
.000E+00
.000E-f00
.000E+00
.000E+00
.000E+00
.000E+00
.000E4-00
.000E+00
-------
w
I
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
NG/J
CATALYST INLET FILTER
XAO
.377E-02
.147E-05
.373E-04
. 112E-01
.374E-08
.603E-06
.000E400
.898E-05
.273E-06
.102E400
.181E-02
.861E-07
. 000E400
.151E-03
.334E-02
.345E-02
.000E400
. 114E-03
.348E-06
.172E-05
.184E-03
.896E-02
.175E-01
.328E-04
.170E-03
.593E-02
.233E-03
.408E-04
.181E-02
.284E-06
.180E-03
.917E-03
.603E-06
. 115E-02
.399E-01
.747E-07
.689E-05
.277E-06
.861E-07
.000E+00
.377E-02
.147E-C5
.373E-04
.112E-0I
.374E-08
.603E-06
.000E400
.898E-05
.273E-06
.152E-01
.202E-05
.861E-07
.861E-03
. 151E-03
.183E-03
.484E-04
.482E-03
.531E-05
.348E-06
.172E-05
.973E-06
.896E-02
.367E-05
.328E-04
.000E400
.228E-02
.201E-04
.845E-0S
.178E-03
.284E-06
.180E-03
.284E-05
.603E-06
.I15E-02
.000E400
.747E-07
.689E-05
.277E-06
.861E-07
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
. 000E400
.872E-ei
.174E-02
.000E400
.000E400
. 000E400
.316E-02
.218E-02
.000E400
.109E-03
.000E400
.000E400
.000E+00
.000E400
.273E-02
.000E400
.109E-03
.000E+00
.000E400
.196E-04
.164E-02
.000E400
. 000 E-f 00
.000E400
.000E400
.000E400
.338E-01
.000E400
. 000E400
.000E400
.000E400
.000E400
IMPINGER 1
.000E+00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.C00E400
.609E-04
.000E400
.000E400
.000E400
.000E400
. 122E-02
.000E400
.000E400
.000E400
.000E400
.183E-03
.000E400
. 183E-03
.000E400
.609E-04
.366E-02
.213E-03
.000E400
.000E400
.000E400
.000E400
.9ME-03
.000E400
.000E400
.609E-02
.000E400
.000E400
.000E400
.000E400
.000E400
IMPINGER 243
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.B00E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E+00
.000E400
. 145E-01
.000E400
.000E+00
.000E400
.000E400
.204E-04
.000E400
.000E400
.000E400
.000E+00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.OOOE400
(continued)
-------
w
I
H-ซ
CO
MASS/HEAT INPUT
ELEMENT
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
HONOR
NAT.
NG/J
ALYST INLET
.0008:460
.523E-05
.130E400
.339E-03
.344E402
.606E-03
.518E402
.000E400
.935E-07
.262E-05
-------
td
ii
CO
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
NG/J
CATALYST OUTLET FILTER
.138E-02
.000E400
.167E400
.135E-02
.000E400
.000E400
.110E-02
.502E-06
.250E-05
.142E-04
.876E-01
.119E-03
.900E-04
.108E-03
.334E-01
.692E-02
.213E-94
.580E-03
.277E-05
. 146E400
.982E-04
.333E-05
.643E-02
.760E-01
.551E-07
.250E-05
.239E-03
: .250E-06
.000E400
.423E-03
.309E-05
. 144E-03
.132E-01
.276E-08
.250E-05
.000E400
.336E-04
.000E400
.969E-02
. 102E-04
.833E-07
.833E-03
.250E-03
.242E-03
.330E-03
.462E-03
.511E-05
.502E-06
.250E-05
.142E-04
. 184E-02
.000E400
.900E-04
.355E-05
.969E-03
.527E-04
.94IE-06
.559E-04
.277E-05
.199E-03
.269E-05
.333E-05
.119E-02
.000E400
.551E-07
.250E-05
.430E-06
: .250E-06
.000E400
XAD
.000E400
.000E+00
.000E400
.000E400
.000E+00
.000E400
.000E+09
.000E400
.000E400
.000E400
.105E-03
.000E400
.000E400
.165E400
.944E-03
.839E-02
.157E-01
.000E400
.000E400
.000E+00
.000E+00
.786E-01
.000E400
.000E400
.105E-03
.105E-01
.503E-02
. 168E-04
.524E-03
.000E400
.142E400
.000E4C0
.000E400
.524E-02
.115E-01
.000E400
.000E400
.000E400
.000E400
.000E400
IMPINGER 1
.955E-03
< .119E-03
.000E400
.478E-03
< .239E-04
.000E400
.000E400
.478E-03
.000E400
.239E-8I
.000E400
.955E-03
C .645E-01
.239E-02
.167E-03
> .238E400
.552E-01
.110E-02
.000E400
.000E400
.000E400
".716E-02
< .119E-03
.000E400
.000E400
.220E-01
.1B4E-02
.358E-05
.000E400
.000E400
.461E-02
.955E-04
.000E400
.000E400
.645E-01
.000E400
.000E400
.239E-03
.000E400
.000E400
IMPINGER 243
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.090E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
(continued)
-------
MASS/HEAT INPUT
ELEMENT
HONOR RANCHO ENGINE
NAT. GAS BASELINE
NG/J
CATALYST OUTLET FILTER
XAD
IMPINGER 1
IMP1NGER 2+3
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
.124E-03
.320E-03
.294E400
.463E-01
.348E402
.425E-05
.59IE-05
.105E-01
.162E-04
.000E400
.000E400
.315E-03
.283E400
.000E400
.105E-B1
.119E-03
.000E400
.000E400
.463E-01
.348E402
.000E400
.000E400
.000E400
.000E+00
.000E+00
W
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTVRIUM
ZINC
ZIRCONIUM
.117E-02
.162E+03
.239E-02
.716E-04
.419E-05
.752E-05
.239E-02
.149E-02
.941E-06
.235E-03
.256E-04
.990E-01
.632E-03
.401E-03
.178E-02
.833E-06
.551E-08
.419E-05
.752E-05
.000E400
.583E-04
.941E-06
.253E-04
. 172E-05
.272E-02
.248E-05
. 105E-03
.000E400
.000E400
.000E+00
. 000E400
.000E400
. 600E400
.000E+00
. 000E400
.210E-03
. 000E400
.315E-02
.629E-03
.669E-03
. 162E403
.239E-02
.716E-04
.000E400
.000E400
.239E-02
.143E-02
.000E+00
.000E400
.239E-04
.931E-01
.000E400
.e00E400
.000E400
.800E400
. 800E400
. 000E400
. 000E400
.000E400
.000E400
.000E400
. 000E400
. 000E4C0
. 800E400
-------
MASS FLOW
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
LUBE OIL
.424E+00
.000E+00
.000E+00
.824E+02
.000E+90
.170E-01
.849E-02
.000E+00
.000E+00
.284E+02
.000E+00
.000E+00
.849E+00
< .170E-01
< .170E-01
.849E-01
.424E+00
.000E+00
.000E+00
.000E+00
.170E-01
424E+00
.000E+00
.170E-01
.255E-01
.340E+00
.849E-01
.526E-02
.849E-01
.000E-(-e0
.170E+00
.000E-I-00
.000E+00
.526E+02
.170E+01
.000E+00
.000E+00
.000E+00
.000E+00
.000E-1-00
< .849E-02
. 170E+00
.255E-I-01
.000E+00
.255E+01
.849E+00
.357E+03
.000E+00
.000E+00
.000E+00
.000E+00
< .170E-01
.000E-H30
.000E+00
.170E-01
.000E+00
.221E+02
.424E-01
HONOR RANCHO ENGINE
NAT. GAS BASELINE
MCG/SEC
CATALYST INLET
.645E401
.252E-02
.6J8E-01
. 192E+02
< .640E-05
.103E-02
.000E+00
.154E-01
. 468E-0.3
.175E-I-03
.309E-t-01
. 147E-03
> .147E+01
.259E+00
.573E+01
.590E+01
> .825E-t-08
.196E+00
.596E-03
.295E-02
.315E+00
.153E-t-02
.299E-1-02
.561E-01
.291E+00
. 102E+02
.400E+00
.699E-01
.311E-1-01
.487E-03
.309E+00
.157E+01
.103E-02
.197E+01
.683E+02
. 128E-03
.118E-01
.474E-03
< .147E-03
.000E+00
.000E-(-00
.903E-02
.223E+03
.580E+00
.589E+05
.104E+01
.887E-M35
.000E+00
.160E-03
.449E-02
.449E-02 .143E+01
. 286E+03
.232E+01
> .423E+03
> . 122E+03
. 189E+01
.860E-03
.428E-02
.244E-01
. 1 50E+03
< .204E+00
. 1 54E+00
.186E+00
. 119E-H32
.365E-01
. 993E+00
. 474E-02
. 1 68E+00
. 570E-02
.110E+02
.130E+03
.944E-04
. 428E-02
.410E+00
< .428E-03
.000E+00
.212E-I-00
.549E-I-00
. 503E+03
.793E+02
.597E+05
.201E-(-01
.278E+06
.409E+01
.123E-I-00
.718E-02
.129E-01
.255E+01
.161E-02
. 402E+00
.438E-01
.169E+03
.108E-I-01
B-15
-------
DO
i
i-j
05
MASS FLOW
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
MCG/SEC
CATALYST INLET XAD
.645E401
.252E-02
.638E-01
.192E402
< .640E-05
.103E-02
.000E400
.154E-01
.468E-03
.I75E403
.309E401
.I47E-03
> .000E400
.259E400
.573E-f01
.590E401
> .000E+00
.196E400
.596E-03
.295E-02
.315E400
.153E402
.299E402
.561E-01
.291E400
.102E402
.400E400
.699E-01
.311E401
.487E-03
.309E400
.157E40J
.103E-02
.197E401
.683E402
.128E-03
.118E-01
.474E-03
< .147E-03
.000E400
.000E400
.000E-I-00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E+00
.149E403
.299E401
.000E+00
.000E+00
.000E+00
.541E+01
.373E+01
.000E+00
.187E+00
.000E+00
.000E+00
.000E+00
.000E+00
.467E+01
.000E+00
.187E+00
.000E+00
.000E400
.336E-01
.2B0E-4-01
.000E+00
.000E+00
.000E+00
.000E400
.000E400
.579E402
.000E400
.000E400
.000E400
.000E400
.000E400
XAD
.000E400
.000E400
.000E400
.006E400
.000E400
.000E400
.000E400
.000E400
.000E400
.149E+03
.299E401
.000E400
.000C400
.000E400
.541E401
.373E401
.000E400
.187E400
.000E400
.000E+00
.000E+00
.000E400
.467E401
.000E400
.187E400
.000E400
.000E+00
.336E-01
.280E401
.000E400
.000E400
.000E400
.000E400
.000E400
.579E+02
.000E400
.000E400
.000E400
.000E400
.000E400
IMPINGER 1
.600E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
. 104E400
.000E400
.000E400
.000E400
.209E401
.000E400
.000E400
.000E400
. 000E+00
.313E400
. 000E400
.313E400
. 000E400
. I04E400
.626E401
.365E400
.000E+00
.000E400
.000E400
. 000E4-00
. 156E401
.000E400
. 000E400
. 104E402
. 000E400
.000E400
.000E400
.000E400
.000E400
IMPINGER 2+3
.000E400
.000ฃ400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E408
.000E400
.000E400
.000E+00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.600E400
.000E400
.249E+02
.000E400
.000E400
.000E400
.000E400
.349E-0I
.000E400
.000E400
.000E400
.000E400
.000E+00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
(continued)
-------
MASS TLOW
ELEMENT
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
MCG/SEC
CATALYST INLET XAO
.000E400
.903E-02
.223E+03
.S80E+00
.589E+05
.000E+00
.000E+00
. 187E+02
.000E+00
. 187E+02
XAD
.000E+00
.000E+00
.187E+02
.000E+00
. 187E+02
IMPINGER 1
.000E+00
.156E+03
.522E+00
.589E+85
IMPINGER
.000E+00
. 000E+00
. 000E+80
. 000E+00
. 000E400
td
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
.104E+01
.887E+05
.000E+00
.160E-03
.449E-02
-------
td
I1
oo
MASS FLOW
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
MCG/SEC
CATALYST OUTLET FILTER
XAD
.236E401
.000E-ป00
.286E403
.232E401
.> .000E400
> .000E400
.189E401
.860E-03
42BE-02
.244E-01
.150E403
< .204E400
.154E400
.186E400
.572E402
.119E402
.365E-0I
.993E400
.474E-02
.251E403
.168E400
.570E-02
. 110E402
. 130E403
.944E-04
.428E-02
.410E400
< .428E-03
.000E400
.725E400
.529E-02
.247E400
.226E402
.472E-05
.428E-02
.000E400
.575E-01
.000E400
166E402
.175E-0I
.143E-03
.143E401
. 429E400
.414E400
.565E400
.792E400
.B75E-02
.860E-03
,428e-02
.244E-01
.315E401
.000E400
.154E400
.608E-02
. 166E401
.902E-01
. 161E-02
.957E-01
.474E-02
.342E400
.46)E-02
.570E-02
.204E401
.000E400
.944E-04
.428E-02
.737E-03
.428E-03
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.180E400
.000E400
.000E400
.282E403
.162E401
. 144E402
.269E402
.000E400
.000E400
.000E400
.000E400
.135E403
.000E400
.000E400
.1B0E400
.180E402
.862E401
.287E-01
.898E400
.000E400
.242E403
.000E400
.000E400
.898E401
.198E402
.000E400
.000E400
.000E+00
.000E400
.000E400
IMPINGER 1
.164E401
< .204E400
.000E400
.8I8E400
< .409E-0I
.000E400
.000E400
.818E400
.000E400
.409E402
.000E400
.164E40I
< .110E403
.409E401
.286E400
> .408E403
.944E402
. I88E401
.000E400
.000E400
.000E400
.123E402
< .204E400
.000E400
.000E400
.376E402
.315E401
.613E-02
.000E400
.000E400
.789E401
.I64E400
.000E400
.000E400
.110E403
.000E400
.000E400
.409E400
.000E400
.000E400
IMPINGER 243
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E+00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E+00
.000E400
. 000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E+00
.000E400
.000C400
.000E400
.000E400
.000E400
(continued)
-------
HONOR RANCHO ENGINE
MASS FLOW NAT. GAS BASELINE
MCG/SEC
ELEMENT CATALYST OUTLET FILTER
XAD
IMPINGER 1
IMPINGER 2+3
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
.212E400
.549E400
.503E403
.793E402
.597E405
.727E-02
.101E-01
.180E402
.277E-01
.000E400
.008E400
.539E400
.485E403
.000E400
.180E402
.204E400
.000E400
.000E400
.793E402
.596E405
.090E400
. 090E-l-e0
.000E+00
.000E+C0
.000E+00
W
I
t'
CO
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
.201E+01
.278E4-06
.409E+01
.123E+00
.718E-02
. 129E-01
.409E+01
.255E+01
. 16IE-02
402E+00
.438E-01
. 169E403
.108E+01
.687E400
.305E+01
.143E-02
.944E-05
.718E-02
.129E-01
.000E+00
.998E-01
.161E-02
433E-01
.295E-02
.466E401
.425E-02
. 180E+00
.000E+00
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.000E+00
.359E+00
.000E+00
.539E401
.108E+01
.1ME401
.278E+06
.409E401
.123E400
.000E400
.000E+00
.409E+01
.245E401
.000E4C0
.000E+00
.409E-01
.159E+03
.000E+00
.000E+00
.000E+00
.000E+08
.000E+00
.000E+00
.000E400
.000E+00
.000E+00
.0e0E+ee
.000E+00
.000E400
.000E+00
.000E400
-------
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
OUTPUT=CATALYST INLET
ENGINE MASS BALANCE
INPUT = LUBE OIL (MAIN FUEL = NATURAL GAS, NOT ANALYZED FOR TRACE ELEMENTS)
TOTAL IN TOTAL OUT MASS BALANCE (OUT/IN)
.424E+00
.8241+92
.170E-01
.849E-02
.284E402
.B49E+00
X<.170E-01
X<.170E-01
.849E-01
.424E+00
.170E-01
.424E+00
.170E-01
.255E-01
.340E+00
.849E-01
.526E-02
.849E-01
.170E+00
.526E+02
.170E+01
X<.849E-02
.645E+01
.252E-02
.638E-01
.192E+02
X<.640E-05
.103E-02
.154E-01
.468E-03
.175E+03
.309E+01
.147E-03
.147E+01
-------
HONOR RANCHO ENGINE
NAT. GAS BASELINE
OUTPUT=CA!AI_rST OUTLET
INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THORIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
ENGINE + CATALYST
LUBE OIL (MAIN FUEL = NATURAL GAS. NOT ANALYZED FOR TRACE ELEMENTS)
TOTAL IN TOTAL OUT MASS BALANCE (OUT/IN)
.424E+00
.824E+02
.170E-01
.849E-02
. 284E-I-02
.849E+00
X<.170E-01
X<.170E-01
.849E-01
424E+00
. 170E-01
.424E+00
.170E-01
.255E-01
.340E+00
.849E-01
.526E-02
.849E-01
, 170E-I-00
.526E+02
. 170E+01
X<.849E-02
. 170E+00
.255E+01
.255E+01
.849E+00
.357E+03
X<.170E-01
. 170E-01
.221E+02
.424E-01
.236E+01
.529E-02
.154E+00
.186E+00
.572E+02
.119E+02
.365E-01
.993E+00
.474E-02
.251E+03
.168E+00
.570E-02
.110E+02
.130E+03
.944E-04
.428E-02
.410E+00
X<.204E+00
.556E+01
.284E+00
.252E+00
.000E+00
.203E+01
.168E+01
-------
INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
HAFNIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PALLADIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RHODIUM
RUBIDIUM
RUTHENIUM
SAMARIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
HONOR RANCHO ENGINE
NAT. GAS BASELINE
CATALYST
CATALYST INLET OUTPUT - CATALYST OUTLET
TOTAL IN TOTAL OUT
.645E-t-ei
.252E-02
.638E-01
.192E+02
X<.640E-05
.193E-02
.154E-01
.468E-03
.175E+03
.309E+01
.147E-03
.147E+01
-------
TECHNICAL REPORT DATA
(Please read liiLLructioiis on the reverse before completing)
. REPORT NO.
EPA-600/7-84-073a/b
3. RECIPIENTS ACCESSION'NO.
4. TITLE AND SUBTITLE
Environmental Assessment of a Reciprocating Engine
Retrofitted with Nonselective Catalytic Reduction;
Vol. I. Technical Results; Vol. II. Data Supplement
5. REPORT DATE
July 1984
6. PERFORMING ORGANIZATION CODE
7733
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
C. Castaldini and L. R. Water land
TR-84-153/EE
9. PERFORMING ORGANIZATION NAME AND ADDRESS
A cur ex Corporation
Environmental and Energy Division
P. O. Box 7555
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; 6/83 - 5/84
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES JJERL-RTP project officer is Robert E. Hall, Mail Drop 65; 919/
541-2477.
16. ABSTRACT
two-volume report describes results from testing a rich-burn recipro-
cating internal combustion engine retrofitted with a nonselective catalytic reduction
system for NOx reduction. A comprehensive test program was performed to charac-
terize catalyst inlet and outlet organic and inorganic emissions at optimum catalyst
NOx reduction performance, followed by a 15-day exhaust emission monitoring pro-
gram to measure the catalyst performance under typical engine operating conditions.
Over the 1-day comprehensive test period, the NOx reduction performance of the
catalyst ranged between 54 and 81%, averaging 70%. NOx emissions averaged 1700
ppm at the catalyst inlet and 550 ppm at the catalyst outlet. Catalyst inlet CO and
total unburned hydrocarbon (TTJHC) concentrations averaged 14, 600 and 115 ppm,
respectively. These inlet combustible concentrations were the result of engine oper-
ation at an air/fuel ratio near or slightly below the stoichiometry required for effi-
cient NOx reduction. Catalyst outlet CO and TTJHC levels were reduced to 13, 200 and
125 ppm, respectively. Total organic emissions were also reduced by the catalyst
from 15. 5 to 2. 1 mg/dscm. Ammonia and cyanide levels increased by factors of 15 and
450, respectively, across the catalyst. Over the 15- day monitoring period, NOx re-
duction performance was mostly in the 0 to 40% range. _
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI l-'ietd/Group
Pollution
Internal Combustion Engines
Reciprocating Engines
Catalysis
Assessments
Pollution Control
Stationary Sources
Environmental Assess-
ment
Nonselective Catalytic
Reduction (NCR)
13B
21K
21G
07D
14B
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
99
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Perm 2220-1 (9-73)
B-23
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