-------
TABLE 4-61. FUEL GAS ANALYSIS - LOCATION 8
Component
Methane
Ethane
Propane
Iso-butane
N- butane
Pentanes
V.
Ethane
Propane
Nitrogen
Carbon dioxide
Hydrogen
Higher heating value
Concentration - Mole %
77.65
1.89
0.76
0.16
0.24
0.03
0.09
0.67
0.11
0.28
0.81
17.31
33.9. MJ/m3
' 910 Btu/CF
Analysis performed by mass spectrotnetry method.
215
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SECTION 5.0
RECOMMENDATIONS
The combustion modification and emission measurement tests conducted
in this program have provided a basis for recommendations for the purposes
of planning future research. These recommendations concern areas of investi-
gation that were outside of the scope of the current program, but are con-
sidered essential to the objective of reduced emissions from"industrial com-
bustion equipment. Most of the suggestions are logical extensions of the
completed work and are concerned with combustion modifications that require
more extensive hardware alterations than were possible in the existing
contract.
5.1 AREAS REQUIRING ADDITIONAL WORK
The survey of emissions data and literature (Appendix A) indicates
that the major industries with high emissions are petroleum refining, wood
products, cement, chemicals, and metals. Not all of these industries are
desirable candidates for additional combustion modification work since the
total emissions may be fragmented among many individual devices of different
design. This is particularly true in the chemicals industry. The most cost
effective approach is to concentrate on devices that make up a large segment
of their industry's emissions and are somewhat adaptable to combustion con-
trol. Consideration should be given to process heaters, wood/bark boilers,
cement kilns, and metals producing furnaces. The major emphasis should
also be on devices where existing technology is not totally adequate? i.e.,
where combustion modifications were of limited effectiveness in the current
program and where new approaches and technology development are required.
Process heaters were estimated to be highest in annual NO emissions
X
from the sources considered. Cement kilns are high in NO , SO , and parti-
3C X
culates although the latter two emissions are process or fuel related and
difficult to control with combustion modifications. Wood boilers are also
216
-------
high in NO emissions and there is reason to believe that current NO control
technology for boilers will be difficult to apply to these devices. The
metals producing industry has more fragmented emissions among several devices
such as furnaces, smelters, heat treat ovens, etc. However, soaking pits
and reheat furnaces are estimated to contribute a major portion of the NO
emissions from steel making operations.
The industrial combustion devices requiring the most attention
initially are process heaters. Their energy use is large and their emissions,
particularly NO , on an annual basis are significant. Most important, the
natural draft refinery heaters do not lend themselves readily to conventional
combustion modifications where significant emissions reduction can usually
be achieved by operational changes that modify the firing practice. Hard-
ware configuration and process constraints have prevented the successful
application of fuel-rich firing modes with burners out-of-service or over-
fire air ports. Low excess air firing has met with limited success and more
sophisticated methods such as flue gas recirculation were not possible since
units were not available with these provisions and hardware modifications
were outside of the scope of the current study. Natural draft units pose
specific contraints in terms of a'iir control mixing and draft requirements
that inhibit the application of low-NO modes.' However, based on American
and Japanese development efforts, significant emissions reductions may be
possible in many cases by relatively minor burner hardware modifications.
The success of these low NO and low excess air designs suggests
that significant NO reductions may also be possible on a retrofit basis
for existing units. Although process heaters are of primary concern,
similar conditions exist with kilns and furnaces where minor hardware
modifications may well be the most cost-effective approach to emissions
control through combustion modification.
217
-------
5.2 RECOMMENDED PROGRAM .OBJECTIVES
A Phase II effort is recommended to follow the current indus-
trial combustion devices program with these additional objectives:
1. Define and evaluate combustion modification concepts
requiring relatively minor hardware modifications to
control emissions on four major combustion device
categories.
2. , Examine the process constraints that may inhibit the
application of these concepts and select the approaches
showing the most promise.
3. Demonstrate the feasibility of the concept for retrofit
applications by conducting subscale reduced emissions
demonstration tests.
4. Establish the cost/benefit factors of candidate combus-
tion modification concepts from an emissions, fuel-effi-
ciency, and operations impact standpoint.
5. . Conduct full-scale combustion modification demonstration
tests in the field on units made available by cooperating
industries.
6. Evaluate emissions and operational performance data in
combination with cost/benefit analyses to recommend an
approach (or priority of approaches) for a given combus-
tion device.
7. Prepare a final engineering report that documents the
engineering development of the recommended combustion
concepts in a manner that will maximize technology
transfer to the relevant burner and process equipment
manufacturers.
5.3 PROPOSED PROGRAM SCOPE
The recommended Phase II program differs from the completed program
by involving hardware modifications that would require more time and funds
than are currently available. This is not a fundamental combustion or hard-
ware development program since a majority of the concepts to be examined will
fall in the category of retrofit burner modifications. The most complex task
proposed is that of instituting flue gas recirculation on a process heater
218
-------
which admittedly will require some extensive duct modifications. In most
cases, the modifications considered will concern optimization of existing
design parameters to minimize NO and can be implemented in most cases with
relatively minor equipment substitutions.
The first major element of the recommended program is the feasibility
demonstrations at the subscale level which could best be performed in coopera-
tion with a major burner manufacturer. The purpose for these demonstration
tests is two-fold. It provides a proving ground for a combustion modification
concept prior to its use on a full-scale field unit which is committed to a
process. It also allows the engineering personnel and -the burner manufacturer
to optimize the approach so that they can speak with confidence when approach-
ing industries to provide units for modification. The latter is the key
to the success of the program; commercial industry will be more receptive
to an emissions reduction concept if it has been proven on a full-scale
process. In the same manner, individual industries are more willing to
provide a production unit for demonstration of a combustion concept if it
has been developed previously on a smaller scale. For these reasons, the
subscale feasibility demonstrations are considered a major part of the program.
While 'they are taking place, it will also provide sufficient time to acquaint
potential host equipment owners with the objectives of the program and to
solicit their cooperation in providing volunteer units.
The second major element of the recommended program is the field
demonstration tests to confirm the effectiveness of the candidate NO control
x
concepts on full-scale operational units. The objective is not only to
demonstrate the feasibility of the concept on a specific unit design, but
also to show that the concept has a wide range of application by additional
tests on other basic combustion device configurations. The added experience
with more than one unit will provide a broader base of understanding and
emissions data concerning the modification and will also increase industry's
ability to adopt new emissions control technology.
219
-------
5.4 TECHNICAL APPROACH
Combustion nodification and emission measurement tests are essential
to the objective of reduced emissions from the four major categories of
combustion devices recommended for the Phase II program. Process heaters
were identified as one of the largest contributors and also as one with
design configurations that made it difficult to apply existing modified
firing practice methods that have proven attractive on industrial and utility
boilers. To illustrate the technical approach that should be followed in
Phase II, the process heater category was selected for a more detailed dis-
cussion of candidate combustion modification concepts. A final technical
scope of work should contain a similar attention to -concepts attractive for
kilns and furnaces. 'The primary intention is to indicate the type of
modified combustion concepts that could be considered, recognizing that
these ideas are preliminary in nature.
5.4.1 Background on Process Heater Combustion Modifications
The application of combustion modification methods to process heaters
for emissions reduction is more difficult than it is on industrial or utility
boilers because of several basic differences in design configurations. One
of the major limitations in combustion control on process heaters is the
fairly widespread use of natural draft designs. Total pressure drops through
the heater and across the burner are quite small O 125 Pa, 0.5" HO) and any
air flow adjustment or modification, that creates a positive pressure in the
top.of the heater could result in casing leaks and structural damage to the
unit. In addition, process heaters tend to have large numbers of burners
to achieve even heat distribution and therefore it is more difficult to
implement a burner's out-of-service low HO firing mode. The low velocity,
more laminar nature of the air flow tends to' inhibit mixing between the fuel-
rich in-service burners and the air-only burners, which also tends to produce
long flame zones and less even heat distribution. If the process heater
firebox is not high enough to permit complete fuel burnout prior to entering
the convective passes, an undesirable condition with flame impingement or
carryover may occur.
220
-------
The problems outlined above exist to a lesser extent on most moderate
to larger sized boilers where forced draft operation provides the opportunity
to control both the air and the fuel, and with more turbulence and mixing.
Boilers frequently have fewer burners (for the same unit heat rate) which
are easier to control and much larger changes in local air/fuel ratio and
flow rate can be made without influencing final steam, temperatures and unit
performance. In addition, most utility size boilers have very high furnace sec-
tions which provide an adequate combustion length to accommodate fuel-rich
combustion without flame carryover. For these reasons, some low NO firing
modes which are well suited for boiler applications are less adaptable to
process heaters.
The previous discussion has briefly identified some of the limitations
encountered in achieving significant emissions reductions in natural-draft
process heaters through minor operational combustion modifications in the
field. However, significant NO reductions may be possible through relatively
minor component modifications that would be attractive for implementation in
the field on a retrofit basis. The purpose of this discussion is to identify
these concepts and briefly examine their principle of operation and relative
attractiveness for field implementation.
5.4.2 Combustion Modification approaches
There are two general approaches that initially deserve consideration
in performing combustion modifications on process 'heaters. In natural draft
devices, the air flow, mixing, and flame shape are intimately interrelated;
air flow adjustments to alter burner stoichiometry have a negative
impact on the other parameters. Therefore, consideration should be given to
varying burner stoichiometry by adjusting the fuel and air flow parameters that
control the mixing. Another approach to limiting NO formation in the flame
X
zone is to control the local mixing and flame zone intensity by minor burner
design modifications to achieve more desirable temperature and stoichiometry
conditions.
221
-------
Low NO burner configurations for process heaters have recently been
X
developed in Japan and the United States for new units. The purpose of the
proposed combustion modification study is to examine methods that could be
implemented on existing process heaters and compare these methods with burner
replacement on a minimum cost retrofit basis. Several approaches recommended
for consideration are listed below:
1. Modified fuel injection
2. Controlled entrainment
3. Steam injection
4. Staged combustion
5. Flue gas recirculation
6. Modified atomization
7. Overfire air
8. Controlled heat withdrawal
5.5 SUPPORT AND DISCUSSION OF PROGRAM ELEMENTS
A four-phase combustion modification feasibility task is recommended
to examine the range of application and to resolve any possible difficulties
at a scale that is less expensive to modify. The initial phase of the
recommended task would concern further definition and evaluation of the con-
cepts with analytical examination of the requisite fluid mechanics, heat
• i
transfer, "etc. This would be followed by an examination of the process
constraints, the adaptability to a range of existing heater designs, and' any
unusual performance requirements. Assuming that the concept still remained
attractive, it would be tested on a single burner research test stand over
a range of operating parameters that would adequately define its emissions
performance and limitations. The support of the burner manufacturers and
process heater manufacturers would be a prerequisite for this effort. Prior
to the full scale tests, a fourth phase concerning cost/benefit calculations
of the combustion modifications from an emissions, efficiency, and operational
impact standpoint should be considered. With this background and support of
the equipment manufacturers, considerably less difficulty should be encountered
in acquiring a full-scale process heater for modification.
222
-------
The combustion modifications proposed (with the exception of Nos. 5,
7, and 8) are not major burner redesigns but rather are a refinement of
existing designs. If the development of a concept requires significant
research funding to achieve a significant emissions reduction, it will be
considered outside the scope of the present study and will be recommended
for individual research support. The primary objective of the study is to
identify process operational and design parameters that affect emissions and
efficiency and then establish the approximate range of desirable operation
for subsequent full scale demonstration tests.
223
-------
SECTION 6.0
REFERENCES*
1. Cato, G. A., et al., "Field Testing: Application of Combustion
Modifications to Control Pollutant Emissions from Industrial
Boilers - Phase I," EPA 650/2-74-078a, NTIS No. PB 238 920/AS,
October 1974.
2. Cato, G. A., et al., "Field Testing: Application of Combustion
Modifications to Control Pollutant Emissions from Industrial
Boilers - Phase II," EPA 600/2-76-086a, NTIS No. PB 253 500/AS,
April 1976.
3. Carter, W. A., et al., "Emissions Reduction On Two Industrial
Boilers With Combustion Modifications," EPA-600/7-78-099a, NTIS
No. PB 283 109, June 1978.
4. Hunter, S. C., et al., "Evaluation of Two Industrial Boilers With
Combustion Modifications for Reduced Pollutant Emissions,"
ASME Paper 77-WA/APC-l, December 1977.
5. Bartz, D. R., et al., "Control of Oxides of Nitrogen from Stationary
Sources in the South Coast 'Air Basin," Prepared for California Air
Resources Board, NTIS No. PB 237 688/7WP, September 1974.
6. Anon., "Energy Conservation Potential in the Cement Industry,"
Federal Energy Administration, FEA/D-75/400, June 1975.
7. Baumeister, T., ed., Mechanical Engineer's Handbook, McGraw-Hill
Book Co., Inc., 6th ed., 1958.
8. Anon., "Particulate Polycyclic Organic Matter," National Academy of
Sciences, 1972.
9. Jacko, R. B. and Neuendorf, D. W., "Trace Metal Particulate Emission
Test Results From a Number of Industrial and Municipal Point Sources,"
Journal of the Air Pollution Control Association, Vol. 27, No. 10,
Page 989, October 1977.
10. Cleland, J. G. and Kingsburg, G. L., "Multimedia Environmental Goals
for Environmental Assessment," Vol. I & II, EPA-600/7-77-136a and b,
November 1977.
*See additional references, Appendices A-G.
224
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SECTION 7.0
CONVERSION FACTORS
SI Units to Metric or English Units
To Obtain ppm
*These conversions depend on fuel composition.
The values given are for typical fuels.
Multiply*
Concentration
To Obtain
g/Mcal
6
10 Btu
BtU
lb/106 Btu
ft
in.
ft2
tv)
w 3
w ft
Ib
Fahrenheit
Fahrenheit
psig
psia
iwg (39.2 °F)
6
10 Btu/hr
GJ/hr
From
ng/J
GJ
gm cal
ng/J
m
cm
2
m
3
m
kg
Celsius
Kelvin
Pa
Pa
Pa
MW
MW
Multiply By
0.004186
0.948
-3
3.9685x10
0.00233
3.281
0.3937
10.764
35.314
2.205
t = 9/5 (t ) + 32
F c
t^ = 1.8t - 460
F K
—4
P . = (P } (1.450x10 J-14.7
psig pa
P . = (P } (1.450x10 )
f^O 1 is f"i:2
psia pa
P. = (P ) (4.014x10 )
iwg pa
3.413
3.60
at 3% O,, of
•e.
Natural Gas Fuel
CO
HC
NO or NO
X
SO. or SO
2 x
Oil Fuel
CO
HC
NO or NO
X
SO or SO
2 x
Coal Fuel
CO
HC
NO or NO
X
SO or SO
2 x
in ng/J by
3.23
5.65
1.96
1.41
2.93
5.13
1.78
1.28
2.69
4.69
1.64
1.18
-------
English and Metric Units to SI Units
10
Multiply*
To Obtain
ng/J
ng/J
GJ
m
cm
2
m
m
kg
Celsius
Kelvin
Pa
Pa
Pa
MW
MW
From
lb/106 Btu
g/Mcal
6
10 Btu
ft
in.
2
ft
ft3
Ib
Fahrenheit
Fahrenheit
psig
psia
iwg (39.2 °F)
6
10 Btu/hr
GJ/hr
,
Multiply By
430
239
1.055
0.3048
2.54
0.0929
0.02832
0.4536
tc = 5/9 (tp - 32)
t.. = 5/9 (t_ - 32) + 273
K. r
P = (P , + 14.7) (6.895x10 )
pa psig *
P = (P . ) (6. 895x10 )
pa psia
P = (P. ) (249.1)
pa iwg
0.293
0.278
*
To Obtain (
ng/J of in
Natural Gas Fuel
CO
HC
NO or NO (as NO )
SO,, or SO
2 x
Oil Fuel
CO
HC
NO or NO (as NO )
S0« or SO
2 x
Coal Fuel
CO
HC
NO or NO (as NO.)
x 2
SO. or SO
2 x
?oncentrat:
ppm i 3% (
0.310
0.177
0.510
0.709
0.341
0.195
0.561
0.780
0.372
0.213
0.611
0.850
*These conversions depend on fuel composition.
The values given are for typical fuels.
-------
APPENDIX A
EQUIPMENT SURVEY
227
-------
BLANK PAGE
228
-------
ABSTRACT
This appendix presents the results of a literature survey of
industrial combustion devices. The objective of this survey was to
recommend a set of devices for subsequent field testing wherein combus-
tion control techniques would be developed to reduce air pollutant
emissions and,- hopefully, simultaneously increase device operating
efficiency.
The survey was accomplished primarily through personal contacts
with device manufacturers and device users. Additional useful infor-
mation was obtained from the national associations representing
manufacturers and users.
This appendix presents the approach used in identifying the
set of combustion devices and, in essence, first-ranked industries in
terms of air pollutant emissions and energy usage and then identified
the significant combustion" devices within the high ranking industries.
The recommended combustion devices were then described in some detail
in order to assist in characterizing a representative unit(s). The
second task of the overall program involved physically locating these
units for the field testing activity.
229
-------
CONTENTS
Section ' Page
ABSTRACT , 229
FIGURES 231
TABLES 232
A-1-0 INTRODUCTION AND SUMMARY - 233
A-2.0 APPROACH 235
A-3.0 INDUSTRY EMISSION RANKING 238
A-4.0 ENERGY CONSIDERATIONS 241
A-5.0 COMPARISON BETWEEN EMISSION AND ENERGY RANKINGS 243
A-6.Q INDUSTRY RECOMMENDATIONS 243
A-7.0 COMPARISON WITH OTHER INDUSTRY RECOMMENDATIONS 244
A-8.Q COMBUSTION DEVICE RANKING 247
A-9.0 COMBUSTION DEVICE RECOMMENDATIONS FOR FIELD TEST 249
A-10-Q INDUSTRIAL COMBUSTION DEVICE CHARACTERISTICS 251
A-10.1 Quantity And Geographic Distribution of 251
Fuels Used
A-10.2 Cement Kilns 256
A-10.3 Glass Container Furnaces 266
A-10.4 Black Liquor Recovery Boilers 274
A-10.5 Wood Waste Boilers 281
A-10.6 Coke Ovens . 286
A-1Q.7 Blast Furnaces 291
A-10.8 Open Hearth Furnaces 296
A-10.9 Soaking-Pit, Reheating, And Heat-Treating Furnaces 302
A-10.10 Stationary Reciprocating Engines 309
A-10.11 Stationary Gas Turbines ' 322
A-10.12 Petroleum Refinery Process Heaters 333
A-11.0 POTENTIAL FUEL SAVINGS IN PULP, PAPER, AND PAPERBOARD 347
INDUSTRY
REFERENCES 23Q 349
-------
FIGURES
No. Page
A-10.2-1. Grate Type Preheater Kiln System (Portland 257
Cement Association)
A-lo.3-1. Regenerative Side-Port Glass Container Furnace 267
(Battelle Columbus Laboratories)
A-10.3-2. Burner Configurations For Glass Furnaces 268
(North American Mfg. Co.)
A-1Q.3-3. Regional Distribution of Glass Container 271
Manufacturers in the United States
A-1Q.4-1. Process Flow Diagram of a Typical Kraft Pulp 275
and Paper Mill (Babcock & Wilcox)
A-10.4-2. Black Liquor Recovery Boiler (Babcock & Wilcox) 276
A-1Q.5-1. Wood Waste Boiler (Babcock & Wilcox) 283
A-10.6-1. General Cut-Away of Coke Oven 288
A-10.7-1. Cross-Section of Typical Blast Furnace and Hot 293
Blast Stove (U.S. Steel Corp.)
A-10.8-1. Principal Parts of an Open-Hearth Furnace 297
(U.S. Steel Corp.) •
A-10.9-1. Soaking-Pit Furnaces (U.S. Steel Corp.) 304
A-10.10-1. Internal Combustion Engine With Integral Gas 314
Compressor (Cooper Energy Services)
A-10.11-1. 2.8 Mw Gas Turbine (Solar Div, International 326
Harvester)
A-10.11-2. Trends in Size of Turbines Sold For Gas 329
Compression Service
A-10.12-1. Total Emissions of Nitrogen Oxide for Refinery 344
Heaters and Boilers Operating on Refinery Gas
A-10.12-2. Emission Factor for Heaters and Boilers with 345
Refinery Gas Fuel
231
-------
TABLES
No. Page
A-l-1 Industries and Devices Recommended for Testing 234
A-2-1 National Associations And Other Organizations 237
Contacted
A-3-1 Industry NO Ranking 240
A-4-1 Purchased Energy For 1971 242
A-8-1 Combustion Device Emissions 248
A-9-1 Devices Recommended For Field Test And Number Of Tests 250
A-10.1-1 Fossil Fuels Purchased By Two-Digit SIC Industries (1971) 252
A-10.2-1 Trend In Average Cement Kiln Capacity 262
A-10,2-2 Cement Kiln Population By Capacity And Process 263
A-10.2-3 Cement Capacity And Kiln Distributions By State 264
A-10.3-1 Energy Utilization In Glass Container Industry 269
A-10.3-2 Characteristics Of Representative Glass Container Furnaces 272
A-10.4-1 Trends In Babcock And Wilcox Black Liquor Recovery Boilers 278
A-10.4-2 Distribution Of Numbers And Relative Capacities Of Kraft 279
Recovery Boilers By State
A-10.5-1 Distribution Of Bark Boilers And Relative Capacities By 284
State
A-10.6-1 Coke Oven Distribution By State ^ 289
A-10.7-1 Annual United States Pig Iron Production _ 292
A-10.7-2 Blast Furnace And Relative Capacity Distributions 294
By State
A- 10.8-1 Distributions Of Open Hearth Furnaces And Approximate 299
Capacity By State
A- 10.8-2 Open Hearth Furnace Air Pollution Emissions 301
A- 10.9-1 Distributions Of Soaking-Pits, Reheating, And Heat- 307
Treating Furnaces
A- 10.10-1 1C Engine Manufacturers _ 310
A- 10.10-2 Stationary 1C Engine Applications 317
A- 10.11-1 Major United States Gas Turbine Manufacturers 323
A- 10.11-2 Net Electrical Energy Produced By Gas Turbines 327
A- 10.11-3 Gas Turbines Installed In Electrical Generating 330
A- 10.11-4 NO Emissions From Gas Turbines 332
A
A- 10.12-1 Typical Refinery Fuel Gas Composition 337
A- 10.12-2 Geographic Distribution Of Petroleum Refineries In The 339
United States
A- 10.12-3 Distribution By Capacity Of Petroleum Refineries In The 340
United States
A-10.12-4 Fuel Use in Petroleum Refineries ' 342
232
-------
SECTION A-1.0
INTRODUCTION AMD SUiMMARY
A study was conducted to establish a set of significant industrial
combustion devices for subsequent field testing during this program. Major
inputs to the effort were a literature survey and personal contacts with
device manufacturers and users. Contacts were also made with national
associations representing the users.
The approach selected for the recommendation process involved con-
sideration of both air pollutant emissions and energy usage within major
industries and then searching these industries for the significant combustion
devices involved. As will be explained, this approach was deemed more direct
than first considering the devices emissions and energy usage and then
determining those industries which employed the devices.
The industries and significant combustion devices thus established
are shown in Table A-l-1.
Combustion devices of the "dryer" type were not recommended since
their air pollutant emissions, as found in the literature, were minor
compared to the above devices.
It is further noted that open hearth and heat-treating furnaces
•are common to both the steel foundry and iron and steel activities. This
commonality of usage will allow a carryover of testing results from one
industry to the other.
Data necessary to identify representative units in each of the
above categories were found to be very limited or nonexistent. As opposed
to conventional boilers that are fairly well defined as to type, size, etc.,
many industrial combustion devices are one-of-a-kind fabricated to specific
proprietary specifications. However, it was possible to define certain
characteristics as representative in the various categories to a degree
sufficient to select units suitable for testing.
233
-------
TABLE A-l-1. INDUSTRIES AND DEVICES RECOMMENDED FOR TESTING
Industry
Combustion Device
Petroleum refining
process heaters
Cement
kilns
Chemical manufacturing
charcoal retorts
ammonia reformers
Steel foundry
open hearth furnaces
heat-treating furnaces
Iron and steel*
coke ovens
blast furnaces
open hearth furnaces
soaking-pits
reheating furnaces
heat-treating furnaces
Wood pulp and pulpboard
Jkraft_process)
wood waste boilers
black lig;uor recovery boilers
Glass container
melting furnaces
reciprocating engines
gas turbines
*A11 these devices can be found in an integrated steel mill, i.e., at one
geographical location.
Not associated with a specific industry.
234
-------
SECTION A-2.0
APPROACH
The primary objective of the survey effort was the preparation
of a list of industrial combustion devices recommended for field testing.
The following steps were followed to secure this objective:
1. Identify those industries which are major sources of
air pollutant emissions.
2. Identify those industries which are major purchasers
of fossil fuel energy.
3. Rank those industries which are both major sources of
air pollutant emissions and purchasers of fossil fuel
energy.
4. Prepare a list of significant combustion devices involved
in the top ranked industries from step 3. These devices
will be those which are the major emission sources and
energy consumers within their respective industries.
Comprehensive listings of stationary combustion devices,
such as reported in Reference A-2-1, were employed as a
guide in establishing, at least on a generic basis, a
checklist of potentially significant devices.
5. Modify this list (step 4) by deleting those combustion
devices whose emissions are due to the material being
processed and not a result of the combustion process.
6. Again modify the step 4 list by including those devices
which by reason of an anticipated high level of
commonality offer a widespread usage of emission control
techniques obtained on a limited number of tests.
7. Prepare the final listing of devices recommended for
field testing.
This approach was adopted since air pollutant emissions contained
in the EPA NEDS listing (Ref.A-2-2) are grouped by industry and then by
device type within the industry. Furthermore, the energy usages
contained in Reference A-2-3 are structured by industry groupings only
and not by device type within the industry. Thus, it was impractical
to undertake an approach which concentrated at the device level and
then associated the devices with specific industrial applications.
235
-------
Simultaneously, contacts were made with national user's
associations, device manufacturers, and the users themselves in
order to obtain more specific information about those devices
recommended for field testing. (Table A-2-1 is a listing of those
organizations contacted.) Information requested from these sources
consisted of:
. Device and burner operational characteristics
. Number distribution vs. device rating and geographical
location
Current fuel usage and trends
Trends in equipment type, rating and age
Limitations in equipment use.
This, and other information, was required to establish the groundwork
for selecting representative units for field test. (The selection
process is performed during Task 2.) The selection of a truly
representative unit is of prime importance when the schedule permits
testing of only a single unit, i.e., the selection must be very
carefully made to allow the widest applicability of combustion control
techniques.
In this survey, conventional boilers burning only natural gas,
fuel oil, or coal were excluded since previous EPA programs have been
directed to those devices. However, boilers burning unusual fuels
such as black liquor, wood bark, carbon monoxide, or process gases
were considered.
236
-------
TABLE A-2-1. NATIONAL ASSOCIATIONS AND OTHER ORGANIZATIONS CONTACTED
Aluminum Association
International Lead Zinc Organization
American Paper Institute
Glass Container Manufacturing Institute
American Gas Association
Portland Cement Association
American Petroleum Institute
American Bureau of Metal Statistics
American Iron'and Steel Institute
Copper Development Association '
Institute of Gas Technology
Federal Energy Administration
Battelle Columbus Laboratories
Bureau of Mines - Office of Oil and Gas
Environmental Protection Agency
Toledo Engineering
St. Regis Paper
Institute of Paper Chemistry
Technical Association of the Pulp and Paper Industry
Major glass container manufacturer
National Council For Air And Stream Improvement (paper industry)
Combustion Engineering
Babcock and Wilcox
Koppers Co., Inc.
Kaiser Steel
Surface Combustion Div., Midland-Ross Corp.
MacMillan-Bloedel Ltd.
Society of Automotive Engineers
Engine Manufacturers Association
Aerotherm Div. Acurex
Southwest Research Institute
American Society of Mechanical Engineers •
Solar Div. International Harvester
McGraw-Hill Inc. (publishers of Electrical World)
Federal Power Commission
Petro-chem Development Co., Inc.
American Boiler Manufacturers Association
237
-------
SECTION A-3.0
INDUSTRY EMISSION RANKING
The industry ranking by yearly NO emission rates was accomplished
X
with the NEDS information (Ref. A-2-2). NO emissions are those produced
X
primarily by the combustion process (nitrogen fixation) and, therefore,
can be reduced by modifications in the combustion process. Reduced air pre-
heat, delayed combustion, off-stoichiometric operation, etc., can be employed
to reduce NO production in the flame. NO can also be formed from nitrogen
<**> X
organically bound in the fuel. This source of NO is more difficult to control.
SO production directly reflects the amount of sulfur present in the fuel and
cannot be controlled by combustion modifications. While it is true that the
combustion process can affect the production of incompletely reacted species
(hydrocarbons, HC, and carbon monoxide, CO) to some extent, the ranking system
focused on NO as the indicator. Each of the industry listings was evaluated
and retained if it involved a combustion device. Even then, some listings
were deleted if the majority of the NO emissions could be attributable to the
process or process material and not to the combustion device. For example,
the production of nitric acid involves a combustion device but the majority
of the NO emissions originate in the process material. In this instance the
NEDS information on nitric acid production was not included in the chemical
manufacturing industry total.
A problem arises if the NEDS format is strictly followed in that
such devices as wood boilers, reciprocating engines and gas turbines are
not associated with any specific industry grouping. Rather/ they are
contained under the general headings of External Combustion - Industrial
Boiler and Internal Combustion - Industrial, respectively. These devices are
noted to be large emitters, especially of NO , and they are included in the
X
combustion device ranking discussed in Section A-8. For the purposes of
ranking industrial emissions,'the NEDS listing for wood/bark boilers was
assigned to the wood pulp and pulpboard industry grouping.
238
-------
The results of this ranking are presented in Table A-3-1 and indicate,
Q
for example, that the petroleum refining industry ranks first with 9.69x10
kg/year (1,065,526 tons/year) of NO , about a factor of 10 higher than the
X
other categories. In addition, process heaters account for 91% of the
petroleum refining industry NO production.
X
Also of note from Table A-3-1 is that the NO emissions from the
x
petroleum refining, wood pulp and pulpboard, and cement industries amount
to over 95% of the total for the seven industries listed and that process
heaters, wood/bark boilers, and kilns are three important combustion devices
involved. The glass industry, although ranking last in NO emissions, is
.X
represented by a single type of combustion device. Thus, there exists a
strong potential for industry-wide application of emission reduction
techniques evaluated on a limited number of glass furnaces.
No attempt was made to critically assess the NEDS data summaries to
determine whether they truly represent total national emissions. Possible
data entry errors and the fact that the file may not include all sources
requires that the data be viewed with caution.
239
-------
TABLE A-3-1. INDUSTRY NO RANKING
x
Kg/Year (Tons/Year)
Rank
1
2
> 3
)
4
5
6
7
Industry
Petroleum Refining
Wood Pulp and Pulpboard
Cement
Chemical Mfg.
Steel foundry
Iron and Steel
Glass Container
NOX
969xl06
ISlxlO6
132xl06
27X106
19xl06
16xl06
• 5x1 O6
Emissions
(1,065,526)
(166,327)
(145,101)
(29,209)
(20,797)
(17,045)
(5,385)
Device (s)
Process Heater
Recovery Boiler
Wood/Bark Boiler
Kiln
Charcoal Retort
Ammonia Reformer
Heat-Treating Furnace
Open Hearth Furnace
Coke Oven
Steel Furnace (blast
and open hearth)
Furnace
Device Emission
% of Industry
Emissions
91
9
91
99
49
15
*
34
27
% 100
*The NEDS listing indicates that heat-treating furnaces anQ open hearth furnaces are large NO
sources. However, the listing contains a large "miscellaneous" entry and it is not possible
at this time to assign this entry to specific combustion devices.
x
-------
SECTION A-4.Q
ENERGY CONSIDERATIONS
In addition to emission rates, consideration was also given to energy
utilization on an industry basis. Information obtained by the Bureau of the
Census during 1971 and published in Reference A-2-3 was used in this assess-
ment. It is noted that these data apply only to industry groupings and not
to the device within the industry consuming the energy.
As presented, the data in Reference A-2-3 specifically addresses
quantities of fossil and electric energy purchased for heat and power by the
industry groupings and, therefore, does not necessarily imply an equivalence
to energy consumed. The difference between energy purchased and consumed
can be the result of such things as combustion of feedstock waste material.
The pulp and paper industry, in addition to purchasing energy, produces a
significant amount of its energy requirements from waste product boilers.
This energy source is not tabulated in Reference A-2-3 but is very important
when considering the industry's total energy requirements.
Petroleum refineries consume energy equivalent to approximately 8%
of the energy contained in the crude feedstock. This amounts to approxi-
mately 2911x10 joules/year* while the purchased energy quoted in Reference
A-2-3 for SIC 29 was 1600x10 joules/year for 1971. Thus, purchased energy
in a petroleum refinery amounts to 55.0% of the total consumed with the balance
being obtained principally from by-product refinery gas. Similarly, the
pulp, paper and paperboard industry for 1975 consumed 1950x10 joules/year
and purchased 1111x10 joules/year, or 57.1% (Ref. A-4-15. Black liquor
recovery boilers and wood-bark boilers are the main sources of the internally
generated energy in this industry.
* 1015 J = 0.948xl012 Btu
241
-------
In other industries, e.g., glass, there is essentially no
difference between energy consumed and energy purchased since there
are no waste or by-product combustion sources available to
supplement fossil fuel and electricity.
A major objective of this program is to achieve greater
efficiency in industrial combustion devices. This increased efficiency
can be equated to a decrease in purchased energy requirements since
those devices operating on waste or by-product sources will still be
using all of these sources available regardless of device efficiency
improvements. Thus, ranking of the industries was accomplished on
the basis of purchased energy, with the results presented in Table
A-4-1.
TABLE A-4-1. PURCHASED" ENERGY FOR 1971 (Ref. A-2-3)
Fossil Fuel and Electricity
Total of All Industries Surveyed = 13,860x10 J
Rank
1
2
3
4
5
6
7
8
9
Industry,
Industrial Chemicals
Blast Furnace and Basic Steel Products
Petroleum Refining
Paper and Allied Products
Cement, Hydraulic
Plastic Materials and Synthetics
Glass and Glassware, Pressed or Blown
Iron and Steel Foundries
Flat Glass
Total
SIC*
281
331
291
26
324
282
322
332
321
1015 J
2086
1604
1602
1388
484
477
222
167
62
8092
% of Total
15.1
11.6
11.6
10.0
3.5
3.4
1.6
1.2
0.5
58.4
*Standard Industrial Classification
242
-------
SECTION"A-5.0
COMPARISON BSTWEENEMISSION AND ENERGY RANKINGS
A comparison between Tables A-3-1 and A-4-1 indicates that, in general,
those industries which are large NO emission sources are also large consumers
of purchased energy. For example, the petroleum refining, wood pulp and pulp-
board, and cement industries which rank 1, 2, and 3 as NO emitters rank 3,
«rC
4, and 5 as energy purchasers. Thus, device efficiency improvement techniques
in these three industries could also have a significant impact on national
emission rates if both program objectives could be simultaneously satisfied.
SECTION A-6,0
INDUSTRY RECOMMENDATIONS
Based on an assessment of both NO emissions and energy usage,
•** ,
the following industries should be studied to determine the important combus-
tion devices involved;
Petroleum refining
Wood pulp and pulpboard
Cement
Steel foundry
Iron and steel
Chemical manufacturing
Glass container
The glass container industry is recommended on the basis of an
anticipated commonality between furnaces, i.e., this industry utilizes a
single major type of combustion device with the device consuming a large
majority (approximately 70%) of the entire glass container industry energy
requirement. Further, it is noted from Reference A-2-2 that glass container
industries (SIC 3221) purchased 50% of the total energy attributable to: flat
glass (SIC 3211); glass containers (SIC 3221); pressed and blown glass (SIC
3229); and products of purchased glass (SIC 3231). For these reasons the above
recommendations include only the glass container aspect of the glass industry.
243
-------
SECTION A-7.0
COMPARISON WITH OTHER INDUSTRY RECOMMENDATIONS
A previous study performed under contract for the EPA
(Ref. A-7-1) developed a list of industries based on the following
criteria;
Use large amounts of process heat directly from fossil
fuel combustion
Relatively large emitters of combustion-related air
pollutants
High potential for reducing energy consumption and air
pollutant emission.
Based on .these criteria the following industries were selected for
further analysis in that study:
Iron and steel (all energy-using processes)
Cement (primarily kiln operation)
Glass (melting, foreheater operation, annealing)
Aluminum (primary, melting, reheating, secondary production)
Petroleum refining.
The paper and paperboard manufacturing industry, although a
laxge consumer of energy, was not selected in the previous study because
95% of its energy is consumed in boilers for production of steam?
this operation is already highly efficient. Thus, it was concluded that
there is a low potential for reduction in energy consumption.
The present study does not concur in this observation for
two reasons:
This industry ranks second in NOx emissions, only
exceeded by petroleum refining. Thus, any NOjj
reduction would have significant national implications
even if the device efficiency could not be increased
by any amount.
244
-------
2. This industry ranks fourth in energy consumption,
of which 57.1% is purchased energy (the balance being
produced by liquor recovery and wood/bark boilers),
As shown in Section A-ll, a device efficiency improve-
ment from 80% to 81% will result in a 2.26% reduction
in purchased energy requirements which can be translated
into a yearly savings of 3.4x10 barrels of residual
oil—not an insignificant amount. This savings represents
approximately 5% of this industry's yearly purchase of
residual oil.
An examination of the NEDS listing (Ref. A-2-2) for both primary
and secondary aluminum operations indicates that combustion generated
emissions are minor compared to those contained in Table A-3-1. Indeed,
the values of NO were 2.11x10 kg/year (232 tons/year) which places
.X.
the aluminum industry (both primary and secondary operations) far
below the last ranked glass container industry in Table A-3-1,
On a purchased fossil fuel energy basis Reference A-2-3 indicates
that for .1971 primary aluminum (SIC 3334), aluminum rolling and drawing
(SIC 3352), aluminum castings (SIC 3361) and nonferrous forging (SIC 3392),
purchased a total of 260x10 J of fossil fuel. This places the aluminum
activities higher than glass container (SIC 3221 with 140x10 J) but
lower than cement (SIC 3241 with 450xlQ15 J).
In view of the low NO emissions,, moderate fossil fuel consumption,
jC
and multiple combustion device types, the aluminum industry was not
recommended for field testing.
The previous EPA study did not recommend the chemical manufacturing
industry because of the large number of processes and devices involved.
That is, although the industry as a whole is a large energy consumer the
per unit consumption is small.
245
-------
The present study, while not addressing a per device energy con-
sideration, identified two combustion devices within the chemical manufac-
turing industry which are large emission sources. One of these devices,
the ammonia reformer, is estimated to have a specific energy consumption
(energy/unit weight of product) that is greater than that required in the
cement industry.
The "Chemical Manufacturing" industry is too broad to be considered
as a single entity. However, this is no reason to ignore it since some
aspects of this industry (specific processes) are identifiable by energy
consumption and emissions.
The present study and that contained in the previous (Ref. A-7-1)
study agree on the remaining industries—iron and steel, cement, petroleum
refining and glass-^-as those industries that would benefit most from research
on emissions and energy consumption reductions.
246
-------
SECTION A-8.Q
COMBUSTION DEVICE RANKING
An examination of each industry yielded a set of important com-
bustion devices employed in that industry. These devices are ranked in
Table A-8-1 by NO emissions and emissions of other criteria pollutants
obtained from the NEDS listing are shown. In several instances this set
was composed of one member which accounted for nearly all the NO emissions
for the entire industry. In these instances there was no question as to
the type of device which would be selected for field testing.
In essence, the combustion device ranking involves identifying
major equipment items in those industries which have already been
ranked as high emission sources and energy users.
The process heater descriptor in the petroleum refining industry
is a general title for a family of devices which vary significantly in
configuration and operation depending on the type of process involved.
A more detailed examination of the process heater family was necessary
before specific unit types could be identified for field testing.
The steel furnace device is used in the iron and steel, and steel
foundry industries. There may exist some degree of commonality between the
two functions which will allow a more widespread use of emission reduction
techniques.
As previously discussed, the glass container furnaces should be
included in the field testing schedule even though this industry ranks low
on a NO emission basis.
x
An emission source, to be contained in the NEDS listing, must meet
certain requirements which consist of either the quantity of 'emissions (on
a weight per year basis) or be used within a specified industrial activity.
This latter requirement is rather extensive in length and should preclude
"overlooking" an important (high emission) industry. It then follows that
there is a low probability of also overlooking a high ranking combustion
device. However, there is no way of determining the degree to which all
existing industrial devices are actually entered in the NEDS data base system.
247
-------
TABLE A-8-1. COMBUSTION DEVICE EMISSIONS
kg/year (tons/year)
Device
Process heaters
Recip. engines - nat. gas
Wood boilers
Cement kilns
Gas turbines - natural gas
Steel foundry furnaces
Rccip. engines - diesel
Waste gas flares
Charcoal retorts
Recovery boilers
Iron and steel furnaces
Coke ovens (by-product)
Glass furnaces
Ammonia reformers
Plywood dryers
Cement dryers
No. of
Records*
2,818
1,549
1,259
411
144
349
35
213
110
219
414
375
244
55
510
229
NOV
8.8xl08 (9.7xl05)
2.2xl08 (2.4xl05)
1.4xl08 (l.SxlO5)
1.3xl08 <1.4xl05>
2.0xl07 <2.2xl04)
1.6xl07 (1.8xl04>
1.9X107 (2.1xl04)
1.4xl07 (l.SxlO4)
1.3xl07 <1.4xl04>
l.lxlO7 (l.ZxlO4)
6.1xl06 (6.7xl03)
5.3xl06 (5.8xl03)
4.9xl06 (5.4xl03)
3.9xl06 (4.3xl03)
l.SxlO6 (1.6xl03)
1.4xl06 (l.SxlO3}
. SOV
l.SxlO9 (1.7xl06)
7.0xl06 (7.7xl03)
2.2xl07 (2.4xl04)
6.8X108 (7.5xl05)
l.BxlO6 (2.0xl03)
S.lxlO6 (5.6xl03)
2.5xl06 (2.8xl03>
1.6xl08 (1.8xl05)
B.OxlO6 (8.8xl03)
7.5xl07 (8.2xl04)
l.OxlO8 (l.lxlO5)
l.SxlO8 (l.GxlO5)
2.1xl06 (2.3xl03)
5.5xl03 (6.0x10°)
3.4xl04 (3.7X101)
1.2xl07 (1.3xl04)
I!C
6.1xl07 (6.7xl04)
3.9xl07 (4.3xl04)
3.5xl07 (3.8xl04)
4.1xl04 (4.5X101)
l.SxlO6 (1.6xl03)
4.3xl05 (4.7xl02)
2.3xl06 (2.5xl03)
1.3xl07 (1.4xl04)
3.3X107 (3.6xl04)
3.8xl06 (4.2xl03)
4.3xl05 (4.7xl02)
8.3xl07 (9.1xl04)
1.7xl05 (1.9xl02)
l.lxlO8 (1.2xl05)
7.3xlO? (B.OxlO4)
0 (0)
CO
2.5xl07 (2.8xl04)
2.5xl07 (2.7xl04)
1.7xl08 (1.9xl05)
1.3xl05 (1.4xl02)
1.4xl06 (l.SxlO3}
6.3xl06 (6.9xl03)
4.1xl06 (4.5xl03)
l.BxlO6 (2.0xl03)
6.0xl07 (6.6xl04>
6.8xl08 (7.5xl05)
8.5xl09 (9.3xl06)
3.0xl07 (3.3xl04)
1.9xl04 (2-lxlO1)
6.9xl06 (7.6xl03)
4.4xlOS (4.8X102)
0 (0)
Parti culates
l.OxlO8 (l.lxlO5)
1.4xl06 (l.SxlO3)
2.4X108 (2.6xl05)
6.9xl08 (7.6xl05)
2.6xl05 (2.9xl02)
B.SxlO6 (9.4xl03)
1.4xl06 (l.SxlO3)
2.8xl05 (3.1xl02)
B.OxlO7 (B.BxlO4)
2.4X108 (2.6xl05)
4.4xl08 (4.8xl05)
8.2xl07 (9.0xl04)
1.3xl07 (1.4xl04)
l.BxlO5 (2.0X102)
1.9xl07 (2.1xl04)
1.4xl08 (l.SxlO5)
to
lt>
oo
•Interpreted as being the number of identifiable devices in the EPA National Emissions Data System
Includes open hearth and heat-treating furnace
-------
SECTION A-9.0
COMBUSTION DEVICE RECOMMENDATIONS FOR FIELD TEST
Selection of devices for testing involved first searching for industries
which were large emitters, especially of NO , and large consumers of energy.
Then, each industry was examined to determine the type(s) of combustion
device{s) representing a significant fraction of the industry's emission.
Other considerations, such as device commonality, also entered into the
recommendation process.
The program requires approximately 25 field tests and these were
allocated based on the relative NO emissions of the devices but with a
x
minimum of one test per device. This proportioning procedure resulted in
the number of tests for each device (Table A-9-1).
Table A-9-1 ranks devices by emissions and energy consumption. In
the actual selection, suitability for comb'ustion modifications must also be
considered.
249
-------
TABLE A-9-1. DEVICES RECOMMENDED FOR FIELD TEST AND NUMBER OF UNITS
Device No. of Units
Process heater, Petroleum 9
Reciprocating engine - natural gas fuel 2
Woodwaste boiler 2
Cement kiln 2
Gas turbine - natural gas fuel 1
Reciprocating engine - diesel fuel 1
Open hearth furnace, steel 1
Soaking pit/reheat furnace 1
Blast furnace 1
Charcoal retort 1
Recovery boiler 1
Coke oven 1
Glass furnace 1
Ammonia reformer 1
250
-------
SECTION A-1G.O
INDUSTRIAL COMBUSTION DEVICE CHARACTERISTICS
The following sections present characteristic information of
those combustion devices recommended for field testing. The discussions
will follow the format of:
1. Major manufacturers
2. Associations
3. Basic equipment and combustor design
4. Current fuel use, trends and properties
5. Trends in equipment type, age, size and use
6. Total number and geographic distribution
7. Limitations in equipment uses and fuels
8. Quantity and geographic distribution of fuels used
9. Air pollutant emissions.
The amount of information presented directly reflects the amount
of information obtained from national associations, equipment manufacturers,
and device users.
A-10.1 QUANTITY AND GEOGRAPHIC DISTRIBUTION OF FUELS USED
Reference A-2-3 presents the quantities of fossil fuels purchased
by the two-digit SIC industries in each of the 50 states for 1971. These
data were used to prepare Table A-10.1-1 which presents the fossil fuel
usage in the following important industries identified by the present
study:
Paper and allied products - SIC 26
Chemicals and allied products - SIC 28
Petroleum and coal products - SIC 29
Stone, clay, and glass products - SIC 32
Primary metal industries - SIC 33
Fabricated metal products - SIC 34
The fuels tabulated in Table A-10.1-1 are:
Distillate fuel oil
Residual fuel oil
Coal, coke and breeze
Natural gas
251
-------
TABLE A-1Q.1-1. FOSSIL FUEL PURCHASED BY TWO-DIGIT SIC INDUSTRIES (1971)
(gigajoules per year)
Alabama
JO*sk»
Arizona
Arkansas
California
Colorado
Cosiiec ti cut
Delaware
riorida
Georgia
Hawaii
Idatio
Illinois
Indiana
Iowa
KanSAS
Paper and
Allied
Products
SIC 2*
3.3S 4.26
2.47 3.97
-
-
3,3S 3.06
3.47
1.26 1.8S
1.35 2.S7
6.12 l.l4
2.25
-
-
8.16 3.57
l.S7
1.47 2.27
7.76 2.07
.
-
1.36 l.l6
l.l7 l.l7
6.6S 7.34
5.S6 2.4S
7,94 1.3S
4.2S 2.26
2.04 5.04
2.06
Chemicals and
Allied
Products
SIC 28
9.2S 7.25
i.77 3.67
: :
1.84
7.6s
1.83 2,8*
4.17
1.26 2.4S
S.57
4.93 3.8S
2.4S 2.1S
7.4S 1.07
4.14 9.85
.
3.76 S.26
l.O6 3.97
l.S6 2.06
2.96 1.57
-
1.4*
3.56
3.S6 3.26
2.27 3.47
7.5S 7.25
1.47 2.07
-
4.6S 3,5S
4.45 3.S7
Petroleum
and Coal
Products
SIC 29
6.74 4.24
2.6S
: :
-
l.l7
5.15 6.aS
l.S8
7.94 1.2S
2.3S
-
-
3.15 3.6S
3.3S
-
. _
-
5.95 1.8s
6.44 Z.O7
3.9S 1.37
9.4S
-
w —
Scone, Clay
and Glass
Products
SIC 32
1.66 2.94
6.46 2.37
-
4.44 3.35
6.46
S.55 4.56
1.27
2.4S 2.56
2.24 9.77
-
7.45 2.26
l.l6
.
5.96 l.l5
l.O7
1.76 l.l4
1.76 2.27
3.2S l.3S
- '
9.73 LI6
1.87 4.17
1.36 3.6S
1.67 2.97
-
l.l5 2.05
2.85 l.S7
Primary
Metal
Industries
SIC 33
7.73 4.7S
2.77 4.87
: :
S.7S 2.74
2.47
1.4* 4.64
6.8S
5.66 6.7S
3.7S 3.87
-
2.16 S.96
5.1S
1.35 1.4S
5.53 1.3S
2.34
1.46
3.15
4.4S
.
.
l.l7 7,96
S..37 l.l8
1.37 1-97
2.77 1.38
l.S5 1.74
S.2S
. _
Fabricated
Metal
Products
SIC 34
9. 14
1.4S 2.6S
.
I '7.65
8.75
2.6S 1.7S
1.S7
1.94
1.26
l.l6 2.2S
1.66
6.83 3.44
9.84
1.36
J.24 5.33
1.46
,
.
1.7S 1.26
1.95 2.17
5.6S 3.65
1.46 8.2S
1.35 4.64
1.98
3.34
1.26
I
I
State
SIC
Distillate
Coal, Coke
1
\
Residual
Natural Gas
9.1 * 9.1x10 equivalent gigajoules (GJ)
1 GJ
10* J « 0.948X106 Btu * 277 kW-hr
252
-------
TABLE A-10.1-1. Continued
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
J»ew Mexico
New York
H. Carolina
H. Dakota
Ohio
Oklahoma
Paper and
Allied
Products
SIC 26
3.34 6.94
6.86
2.06 5.36
6.47
4.86 5,2?
4.55
9.65 1.86
l.l7 2.36
5.56 l.l7
3.05 2.76
1.36 3.26
1.97 3.17
3.7S 2.76
4.46 2. I7
2.Q6 l.O6
2.87
: ;
.
_
_
4.3S 1.3?
a.7s
9, 86 1.67
2.96
-
1,27 1.97
8.06 4.96
8.35 2.97
1.97 ' 2.S6
-
1.66 2.45
3.9? l.l7
2.S3 l.l5
1.56
Chemicals and
Allied
Produces
SIC 28
S.85 3-D5
1.87 l.l7
3.04
2.S8
1.34 1.26
1.36 5.86
6. 86 6.66
2.36 4.8S
3.16
S.25 3.76
4.27 2.67
1.75 1.55
l.l6 7.65
1.35 2.75
2.77
l.l6 8.04
7.26 1.47
:
5.85
8.66
5.04 9.94
3.46
1.75 1.45
l.l5
3.37 2.27
7.86 1.77
-
6.S6 9.26'
2.57 9.86
S.86 5.9S
6.06 1.87
-
2.S6 2.16
6.S7 3.17
•1.76
Petroleum
and Coal
Products
SIC 29
_
6.36
2.38
-
-
-
-
; :
_
6.25 7.24
5. 16
4.96
: :
,
_
1.65 1.87
7.86
_
l.l6 1.6S
S.84 2.25
-
-
e.95 i.i6
9.7S " 2.67
l.l5
5.77
Stone f Clay ,
and Glass
Products
SIC 32
3.1S 4.85
3. I6 4.86
3.74
1.77
1.85 2.06
2.76 6.36
6. I6 6.46
2.46 3.26
l.l5
6.6S 7.35
3.77 1.47
6.35 1.76
l.l6 S.76
l.O5 7.44
l.l7
2.95 6.84
2.8? 2.77
9.a3
4.06
3.33
1.96 4,66
3.S5 3.34
7.96
2.55 3.45
2.2S
-
-
6.66 S.O6
8.06 1.37
l.l6 S.S6
7.54 9.26
-
2.06 l.O6
4.07 7.27
1.77
Pri.T^ry
Metal
Industries
SIC 33
4.15 3.9S
2.97 2. I7
_
2.64 7,64
l.l5
3.26 2.27
l.O6 1.37
1.86 1.86
l.l5 3.16
4.46 9.55
2.37 6,37
3.64 3.96
2.85 2.76
1.4S
6.25 1.65
2.26 l.O7
-
1.6S
l.l6
: :
2.25
3.46 9.S6
7.26 6.16
_
6.46 9.36
1.67 • 2.97
8.54 2.24
2. 16
_
1.57 4.96
1.78 1.78
l.O6 8.36
Fairicaced
Metal
Products
SIC 34
6.24
l.l6 4.36
3.34
3.75
— _
3.6S 1.45
2.4S
3.56 1.36
1.55 2.86
6.25 4.55
3.76 1.67
3.7S 8.44
2.24 2.36
2.53
5.55
3.34 1.34
4.56
-
2.34 4.34
9. 85
; ;
1.35 ' 4.54
l.l5
2.36 1.8S
5.16
-
1.56 1-86
2,2S 6.06
1.4S l.l4
1.36
-
4.25 1.85
7.26 2.3?
1.66
253
-------
TABLE A-10.1-1. Continued
Oregon
Rhode Island
3. Carolina
S. Dakota
Toanessee
Toxas
titan
Vemoiit
Virginia
Washington
H. Virginia
Wl*con»ln
Wyoming
0.3. Totals
Paper and
Allied
Products
SIC 26
l.O6 9.1*
2.07
6 7
2 fi7 2 I7
7.S4 1.56
2.25
1.47 1.27
2.16 7.4S
-
1.76 5.36
6.16 8.06
6.84 5.75
3.47
-
-
3.46 1.17
2.27 S.86
4.96 1.97
3.67
-
1.98 2.76
S.47 3.S7
-
l.l3 3.13
3.68 S.28
Chemicals and
Allied
Products
SIC 28
3.75 l.SS
1.26
, 06 . ,7
7 7
3.14 a.65
3.35
i.5S 1.78
2.97 1.4*
.
8.6S S.85
6.67 4.57
i.a3 6.4s
6. 18
2.8S 1.24
7.65
1.25
1.27 1.37
4.37 4.16
5.6S 6.85
8.5S l.l7
4.65 2.45
9.27 2.17
4.a5 2.2S
4.86 3. I6
-
9.17 1.38
5.18 1.6*
Petroleum
and Coal
Produces
SIC 29
5.34 2.7S
6.65
, ,6 7
s a6 2 o8
-
-
: :
9.04
1.7*
1.45 9.66
a.o8
3.i6
,
-
_
3.S4 8.24
6.3S l.i6
-
S.34
l.l7
2.07 7.17
9.96 1.49
Stone, Clay,
and Glass
Products
SIC 32
: :
6 .6
7 ,7
t.O5 3.15
2.0*
5.3S 8.9S
1.47
: :
4.4S 3.3S
l.l7 2.17
1.86 l.O5
8.77
f.O4 3.2S
1.46 4.86
3.2S 1.55
1.37 l.l7
-
1.35 l.O5
6.06 Z.77
4,65 -
2.26 2.8S
: :
6.87 5.67
2.88 7.78
Frimary
Metal
Industries
SIC 33
: :
1 77 3 47
, ,a a
7.35 7.9S
1.S*
5.15 2.9S
9.8S
: :
3.4S
1.7* l.l7
1.5* 7.25
4.17 l.O8
-
: :
7.3S
1.26 4.06
7.05 l.«6
5.S3 1.37
2.46 3.33
2.97 1.77
6.1S 8.6S
4.96 l.S?
„
9.a7 i-48
6.08 1.29
Fabricated
Metal
Products
SIC 34
.
, ,« , 06
II6 IS7
_
.
; ;.
1.4S 9.04
1.94 -3.86
1.44 -
1,37
.
_
7.14 2.44
l.i* 7.6S
2.84 1.6S
7.S5
1.1S i.S4
3.64 1.66
3.65 2.2S
7.iS 6.86
: :
i.a7 i.37
i.a7 1.7s
Stat«
sir
Distillate
Coal, Coke
Ratldual
Natural Gas
254
-------
The use of Table A-10.1-1 is illustrated by the following example:
In the state of Alabama, paper and allied products (SIC 26)
purchased the equivalent of:
Q
. 9.1 x 10 kw-hr of distillate fuel oil
• 1.2 x 10 kw-hr of residual fuel oil
9
6.6 x 10 kw-hr of coal, coke and breeze
• 1.1 x 10 kw-hr of natural gas
during 1971.
As presented in Reference A-2-3 these purchased fossil fuel usages
cover only the two-digit SIC activities. Thus, it was not possible to
extract similar information on, for example, the four-digit cement
activity (SIC 3241).
Table A-10.1-1 is intended to supply the bulk of the geographic
fuel usage data in one central location within the report instead of
breaking the information down when discussing specific industrial
combustion devices.
255
-------
A-10.2 CEMENT KILNS
Major Manufacturers
There are four major manufacturers of cement kilns:
Allis-Chalmers (Wisconsin)
Fuller (Pennsylvania)
Polysius (Georgia)
F. L. Schmidt (Pennsylvania)
These manufacturers can perform a "turn-key" operation; they will design
and construct an entire plant to the user's specifications. In some
instances an engineering firm will do the design work.
Associations
There are no known associations of cement kiln manufacturers. However,
the Portland Cement Association (Skokie, Illinois) represents the cement
manufacturers.
Basic Equipment and Combustor Design (Ref. A-10.2-1)
Cement kilns are typically of the rotary type and in dimension can be
up to 183 m (600 ft) long and 7.6 m (25 ft) in diameter constructed of a refrac-
tory lined metal shell. The axis of rotation is tipped so that the feed end is
higher than the discharge end. Typically a single burner is fitted at the
discharge end with the exhaust gases passing countercurrent to the material
motion.
Waste heat is extensively utilized, e.g.:
Secondary combustion air is preheated in the process of
cooling the clinker (kiln finished product)
Waste gas is used to preheat the incoming raw materials -
a substantial amount of calcining can be performed in this
manner
. Waste gas can also be used in a steam boiler.
Figure A-10.2-1 is a sketch of a. grate preheater kiln system.
256
-------
NJ
Ul
START-UP STACK
(OR BYPASS)
STACK
GRATEPREHEATER
POLLUTION CONTROL
HPRECIPITATOR.BAG HOUSE, ETC.)
BURNER
• GAS FLOW
MATERIAL FLOW
PRIMARY AIR
AND FUEL
GRATE-TYPE COOLER
SECONDARY AIR
SECONDARY CLINKER COOLING MAY OCCUR HERE
EXCESS COOLER AIR MAY BE VENTED TO ATMOSPHERE THROUGH POLLUTION CONTROL DEVICES
OR RECYCLED TO GRATE PREHEATER
Figure A-10.2-1. Grate type preheater kiln system (Portland Cement Association)
-------
Wet or dry processes are used to produce most of United States'
cement production with the wet process accepting raw feed material which
contains 20% or more water. The choice of a process for a cement kiln
is dictated by the water content of the raw materials available at the
plant location.
Shortly after entering the kiln, the feed material encounters a
chain system (a series of long strands, garlands, or curtains of steel
chains fastened to the kiln shell). The chains are alternately exposed
to hot exhaust gases and the feed slurry as the kiln rotates. This
action causes an increased heat transfer rate to the slurry and also
assists in conveying the material down the length of the kiln. A kiln
operating on the dry process may also contain a chain system for an
increased heat transfer rate. Kiln speed affects the heat transfer
rate.
As water evaporates, the material gradually is converted to
plastic modules, which the chains convey further. Slightly beyond
the end of the feed end chain system, the water is gone, and the
dry raw feed progresses through preheating, calcining, and burning
zones. The preheating zone raises the temperature from 373 to 1173 K
(212 to 1652 F) ; it also drives off combined water in the raw materials.
The calcining zone decarbonates the calcium and mangesium carbonates,
and the burning zone (at 1533 K [2300 F] to 1866 K [2900 F] material
temperature) causes the clinker-forming chemical reactions to occur.
The fresh clinker then travels through the cooling zone of the rotary
kiln and drops into a clinker cooler in which ambient air is forced
through the hot clinker. A substantial portion of this heated air
is then used for combustion of the fuel in the burning zone, while
the cool clinker is eventually removed from the cooler ready for
finish grinding or intermediate storage.
258
-------
Material preheaters are stationary devices located upstream
from the kiln feed entrance. The function of this device is to
initiate the calcining process using waste gas energy. The preheater
may consist of a series of from one to five cyclones within which
the powder feed is flowing countercurrent to the exhaust gas- The
highly turbulent motion is sufficient to induce 40-50% calcination
of the raw feed by the time it enters the rotary kiln. In another
preheater configuration the feed is first processed into pellets which
are placed on a traveling grate which conveys the pellets toward
the kiln inlet. At the same time, the kiln exhaust gases are passed
through the bed once, or more often twice, to dry, preheat, and
partially calcine the feed.
Burners for cement kilns are produced in a variety of configurations
primarily depending on the type of fuel being used. The burner is located
at the discharge end of the kiln on a non-rotating structure and may be
positioned above the kiln axis of rotation and directed toward the charge.
This positioning is necessary to avoid direct flame impingement on the
refractory lining.
For operation on natural gas the burner may consist of a single
pipe which introduces the fuel coaxially within the primary airstreairt.
The burner is designed to produce complete combustion within the minimum
distance ("short, hot flame"), or is adjustable to achieve a wide range
of flame shapes. The latter is a result of injecting a central core of
natural gas (which will yield a long, narrow flame) and another stream
through radial holes (provides a very short, bushy flame). By varying
the percentage of flow between these two streams, any desired resultant
flame shape is obtained.
For fuel oil, the mechanism is much the same. One controlled
oil .stream flows to oil tips that provide a very long, narrow flame; the
other oil stream flows to the tips that are wider in spray angle. A
typical adjustable oil burner will use six tips.
259
-------
Combination gas and oil adjustable kiln burners are designed so
that both gas and oil may be fired simultaneously. This permits
changeover from one fuel to the other without shutdown.
Burners are presently in service which permit the simultaneous
use of coke and either natural gas or fuel oil. These same burners
are capable of using any of these fuels alone or substituting pulverized
coal for the coke.
Development is proceeding on burners capable of using a coal-oil
slurry and a combination of refuse and natural gas.
Approximately 90% of the cement kilns in -the United States
are presently capable of using more than one fuel. (However, in
1975 only 77% of the kilns actually used more than one fuel type.)
The remaining kilns lack the storage or handling facilities (e.g.,
coal pulverizers, oil storage tanks) which would allow multiple
fuel usage, i.e., a facility problem rather than a kiln burner
inadequacy-
Current Fuel Use, Trends and Properties
Between 1960 and 1973, according to Reference A-10.2-1, there
was a gradual shifting away from the use of coal in the U.S. cement
industry. During the same time period there were increases by factors
of 3.3 and 1.3 in the use of petroleum products and natural gas,
respectively. However, in 1973 coal still supplied 39% of the
industry energy usage with petroleum products accounting for 15.6%
and natural gas for 45.4%. Energy utilization information recently
released for 1975 (Ref. A-10.2-2) indicates that the fuel usage trend
has reversed to the extent that coal now supplies 48% of the energy
requirements with petroleum products and natural gas accounting for
9.4% and 42.6%, respectively. Thus, between 1973 and 1975 the use of
coal has increased by 23% while the use of petroleum products and natural
gas has decreased by 40% and 6%, respectively, in supplying the energy
needs of the cement industry.
260
-------
Again between 1960 and 1973 kiln energy consumed per unit weight
of cement produced decreased by 12%; this decrease is partly attributable to
the proportionately greater use of the less energy intensive dry process.
Trends In Equipment Type, Age, Siza, and Use
Since 1965, according to Reference A-10.2-1, there has been a
small shifting toward the use of the less energy intensive dry process.
In 1975 (Ref. A-10.2-2) the dry process accounted for 42% of the industry
production, an increase from the 1965 level of 39.6%.
Table A-10.2-1, from information contained in Reference A-10.2-1,
shows the present kiln capacity broken down by year built. It is
concluded from these data that the newer kilns are being built in
larger capacities. Table A-10.2-2 is the present kiln population by
capacity and process with the size ranges between 46 x lo kg/year
and 320 x 10 kg/year containing the greatest number.
There are no data available giving the trend in kiln age;
however, the arithmetically average kiln was built in 1955, i.e.,
20-21 years old.
Total__jNumbe_r and Geographical Distribution
hs of December 31, 1975 there were 412 cement kilns in the
Q f~
United States producing 85.0 x 10 kg/year (93.5 x 10 short tons/year)
of cement. Reference A-10.2-3 details the distribution of the kilns by
company and geography, and Table A-10.2-3 herein lists the number of
kilns and total capacity (wet and dry) by state.
Limitations In Equipment Uses and Fuels
There are no limitations on the type of fuel used. Indeed,
as previously mentioned approximately 90% of the cement kilns are
capable of operating with more than one fuel type.
261
-------
TABLE A-10.2-1. TREND IN AVERAGE CEMENT KILN CAPACITY
Time Period Built
1975
1965 - 1974
1955 - 1964
1945 - 1954
1935 - 1944
Before 1935
No. Built
9
69
152
79
17
88
Average Kiln Clinker Capacity
10J kg/Year
370 000
367 000
219 000
136 000
155 000
96 000
(103 Short Tons/Year)
(407)
(404)
(241)
(149)
(170)
(106)
262
-------
TABLE A-10.2-2. CEMENT KILN POPULATION BY CAPACITY AND PROCESS
Capacity
10 b kg/YR
0 - 45.9
45.9 - 91.7
91.7 - 137.6
137.6 - 183.5
183.5 - 229.4
229.4 - 275.2
275.2 - 321.1
321.1 - 367.0
367.0 - 412.8
412.8 - 458.7
458.7 - 504.6
504.6 - 550.5
550.5 - 596.3
596.3 - 642.2
642.2 - 688.1
688.1 - 733.9
1055.1 - 1100.9
103 Tons/YR
0-50
50 - 100
100 - 150
150 - 200
200 - 250
250 - 300
300 - 350
350 - 400
400 - 450
450 - 500
500 - 550
550 - 600
600 - 650
650 - 700
700 - 750
750 - 800
1150 - 1200
Number by Process
Wet
2
27
48
38
36
27
15
6
3
6
3
3
0
1
3
3
1
222
Dry
14
44
20
23
32
15
11
5
6
4
4
8
2
0
0
1
0
189
263
-------
TABLE A-1Q.2-3. CSMENT CAPACITY AND KILN DISTRIBUTIONS BY STATE
State
Alabama
Arizona
Arkansas
California
Colorado
Florida
Georgia
Hawaii
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Michigan
Mississippi
Missouri
Montana
Nebraska
Nevada
New Mexico ~\
New York
North Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
South Carolina
South Dakota
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
6
Capacity, 10 kg/Year
2043
1564
1132
9404
1568
3407
1433
509
2535
3152
2395
2043
600
991
427
1645
5828
878
4352
600
959
364
382
5121
555
2627
1491
573
8752
2308
518
2172
8125
636
900
1487
820
401
172
No. Kilns
18
10
2
41
6
11
"5
3
8
13
17
14
1
6
1
7
22
4
12
2
6
2
2
18
2
12
6
5
63
7
3
13
48
6
4
7
3
1
1
264
-------
According to Reference A-10.2-1, most of the cement industry is
potentially an ideal consumer of higher-sulfur fuels, particularly
bituminous coal, a commodity which, for environmental reasons, is not
acceptable for power generating plants or other applications. Because
of the nature of the process, cement manufacturers can use higher-sulfur
fuels without the SO emission problems experienced by power plants,
X
and such use is in progress at some plants. During formation of cement
clinker, lime-rich materials are present throughout the kiln. These
f
reactive materials are capable of combining with sulfur oxides formed
by combustion of the fuel. In effect, the sulfur from the fuel becomes
part of the cement clinker rather than being emitted into the atmosphere,
Air Pollutant Emissions
The air pollution emissions from cement kilns, as contained in
the NEDS listing (Ref. A-2-2), were shown in Table A-8-1. Cement kilns
are ranked fourth in NO emissions. Particulate emissions are highest
of all the classes indicated. HC and CO emissions are relatively low
because of the long residence time in the kiln. SO emissions shown
A
are high in spite of the expected natural scrubbing. Some cement feed
materials may provide the scrubbing action.
265
-------
A-10.3 QIASS CONTAINER FUBNAC1S
Major Manufactures
There are two major manufacturers of glass container furnaces:
Toledo Engineering (Toledo, Ohio)
Anderson Construction (Pico Rivera, California) .
Each of these organizations will design and build the furnace to the
user's specifications or the user may do the design work. In either
event, the burners are furnished by another supplier (of which there
are 75) or will be built directly for the user by a local shop.
Associations
There are no known associations representing the furnace
manufacturers. However, the Glass .Packaging Institute (Washington, D.C.)
represents the users.
Basic Equipment and Cotnbustor Design
The furnaces are divided into two parts . The first part
melts the raw materials at high temperature and the second part refines
* *
the molten glass at a lower temperature. Two burners are fitted in the
end-port configuration (wherein the flame is directed the length of the
furnace) and multiple burners are used in the side-port arrangement
(the flame being directed across the width of the furnace), Natural
gas is the primary fuel with No. 2 oil or propane as a standby fuel. •
Regenerative air preheaters are employed and consist of refractory
brick checker work located at one end of an end port furnace and on
each side of a side-port furnace. Figure A-10.3-1 is a sketch of a
side-port glass container furnace showing these major components,
while Figure A-10.3-2 shows two types of burner configurations.
Electric boosting can be used to increase the production of a
furnace. Thus, the production of a fossil fueled furnace, which is
designed to meet a certain market demand, can be increased to meet an
increased market demand.
266
-------
RAW MATERIALS
1 (V/elqhingcndMn
REGENERATOR
trQ FEEDS?
FORMING
Figure A-10. 3-1. Regenerative side-port glass container furnace
(Battelle Columbus Laboratories).
267
-------
Standard inside-mixing burners for glass tanks.
Cooling water
" to burners "N.
Cracking and mixing burners for glass tanks.
Figure A-10.3-2. Burner configurations for glass furnaces
(North American Mfg. Co.).
268
-------
Natural gas fired annealing kilns are the next largest energy
consumers in the glass container industries and are used to stress
relieve the finished glass products.
Current Fuel Use, Trends and Properties
Table A-10.3-1, reproduced from Reference A-10.3-1, presents the
energy utilization, in the glass container industry for the years 1971,
1973, and 1974. During this time period the percentage use of natural
gas has decreased while that of both distillate and residual fuel oils
has increased; this reflects the limited supply of natural gas. The
total energy consumption has been estimated to have increased by 17.6%
for the 1971-1974 time period (Ref. A-10.3-1).
TABLE A-10.3-1. ENERGY UTILIZATION IN GLASS CONTAINER INDUSTRY (PERCENT)
Natural Gas
Electricity*
Distillate Fuel Oil
Residual Fuel Oil
Propane
1971
77.2
17.1
3.9
1.7
—
100.0
1973
70.5
17.4
' 7.8
3.8
0.5
100.0
1974
64.9
19.6
9.0
6.1
0.4
100.0
* Represents energy used to produce the electricity, i.e., a factor of
3.1 times larger than electricity actually consumed.
Trends In Equipment Type, Age, Size and Use
No trends in equipment type were found since each furnace is
designed and built to meet the needs of a particular manufacturer.
Extensive research has been, and is being, carried out to affect energy
conservation in the glass container industry. These areas include:
using exhaust gas to batch preheat the incoming load
pelletizing the incoming load to more effectively allow
preheating
269
-------
. proper burner positioning to eliminate flame impingement
use of oxygen enhancement to maintain flame temperature
while reducing fuel requirements
placing the burners at the bottom of the furnace under
the molten glass instead of having them above the molten
glass.
It is not apparent that any of these research activities have been widely
incorporated into the furnaces.
There is essentially little flexibility in glass container furnaces
since the choices in configuration are limited, e.g., end port vs. side port,
with/without electric boost, separately heated refining section or combustion
gas heating from melting section.
The. furnace is rebuilt periodically since the sidewall insulation
wears thin with time and the regenerators become plugged with material carried
over from the furnace. The time between rebuilds ("campaign") varies from 4
to 8 years with the shorter time period corresponding to furnaces which are
"pulled" harder (higher production rate). After a campaign the furnace could
be rebuilt so as to satisfy a new market damand for glass containers. Thus,
the average age of a furnace is 2-4 years old. . .
A leading glass container manufacturer has supplied representative
characteristics on their furnaces. These data are presented in Table A-10.3-2,
Total Number and Geographical Distribution
According to Reference A-10.3-2 there-are 334 continuous glass
container furnaces in the continental United States. Figure A-10.3-3 taken
from Reference A-10.3-1 shows the regional distribution of the 117 glass
container manufacturing plants.
No detailed information was found on furnace capacities, since these
data are closely held in this competitive industry.
270
-------
Figure A-10.3-3.Regional distribution of glass container manufacturers in the United States.
(Ref. 10.3-1)
-------
TABLE A-10.3-2.CHARACTERISTICS OF REPRESENTATIVE GLASS CONTAINER FURNACES
2 2
Melter Area, m (ft )
Production Rate, kg/day
(short tons/day)
Furnace Eating, m /kg/day
(ft2/short ton/day)
Energy Requirement, kJ/kg
(10° Btu/short ton)
Age, years
Glass Color
Melter Bridgewall Temperature ,
K (°F)
Waste Gas Temperature,
K (°F)
Number of Ports
Primary Fuel
Standby Fuel
Side-Port
83.7 (900)
141 000 (155)
0.00059 (5.8)
6012 (5.7)
4.6
Flint or green
1767 (2722)
783 (950)
10
Natural Gas
No. 2 Oil
End-Port
60.0 (645)
120 000 (132)
0.0005 (4.9)
5591 (5.3)
2.0
Flint or green
1783 (2750)
723 (842)
2
Natural Gas
No. 2 Oil
Limitations In Equipment Uses and_ Fuels
Present equipment limitations require that natural gas be used
in the refining section (if separately heated), forehearth, and
annealing ovens. Distillate oils can be substituted for natural gas
in the melting area of the furnace.
Greater use of distillate oils is possible but only with
equipment specifically designed for oil operation.
The use of electricity exclusively in the melter section is
possible once the charge has been brought to a molten state by a fossil
fuel source. However, the total energy requirements are greater for
electricity than fossil fuels if the energy required to produce the
electricity is considered.
272
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Most likely coal will not be directly used in the furnace since the
fly ash would adversely affect glass quality.
Air Pollutant Emissions
The yearly air pollution emissions from glass furnaces was shown in
Table A-8-1. The high level of particulate emissions is mostly due to entrain-
ment of glass batch particles by the exhaust gas stream. The NEDS information
(Ref. A-2-2) does not differentiate the emissions by the type of glass (flat,
container, pressed or blown) being produced.
273
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A-10.4 BLACK LIQUOR RECOVERY BOILERS
Major Manufacturers
There are two major manufacturers of black liquor recovery boilers
used in the sulfate (kraft) process for wood pulp:
Babcock and Wilcox (Wilmington, North Carolina)
Combustion Engineering (Chattanooga, Tennessee)
Associations
There are no known associations of black liquor recovery boiler
manufacturers. However, both of the above manufacturers are members of the
American Boiler Manufacturers Association. The Black Liquor Recovery Boiler
Advisory Committee serves the users in a safety advisory capacity.
The American Paper Institute (New York, NY), Technical Association
Of The Pulp and Paper Industry (Atlanta, Georgia) and the National Council
For Air And Stream Improvement (New York, NY) represent the pulp and paper
manufacturers.
Basic Equipment andCombustor Design (Ref. A-10.4-1)
These devices are used in" the recovery (refining) of the caustic
chemicals from the wood pulp digesters. The boilers require careful attention
to air distribution within the furnace to avoid excessive loss of the chemical
by oxidation. Figure A-10.4-1 is a flow diagram of the kraft process and
Figure A—10.4-2 is a cross-sectional view of a recovery boiler.
The black liquor, containing up to 60% by weight of organic material,
is sprayed onto the furnace walls by an oscillating nozzle where it is
dehydrated to form a char which drops to the furnace bottom. The organic
material is carried upward through the furnace where it is burned with air
from secondary and tertiary ports. Ash (inorganic material) from the char
bed is exposed to a reducing atmosphere to convert its sodium sulfate to
sodium sulfide which is then collected in the furnace bottom as a molten
smelt. The smelt is carefully kept from contact with a proportion of water
which would cause a violent reaction.
274
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LOS
BARKING DRUM
OIL 8URNER
KNOTTERS, R1FHJRS, i SCREENS
MULTIPLE-EFFECT EVAPORATORS
-3
DE^ASiNS
TANK
TOSiWER
CONOENSATE -
HEAVY-
SLACK-
LIQUOR
STORAGE,
Figure A-10.4-1. Process flow diagram of a typical kraft pulp and
paper mill {Babcock & Wilcox).
275
-------
ECONOMIZE*
FORC£n-on*Fr
PUMPS FAN RKMRCUlATINfi PUMPS
Figure A-10.4-2. Black liquor recovery boiler (Babcock s Wilcox)
276
-------
The use of supplemental fuels is limited to the boiler star~t and
warm-up cycle but may also be used for load sustaining.
Current Fuel Use, Trneds and Properties
Aside from boiler start and warm-up only black liquor fuel is used.
Therefore, there was no data on fuel use, trends and properties.
Trends In Equipment_Type, _Age_,..._S.iz_e_and_ Use
Information supplied by Babcock and Wilcox (Ref. A-10.4-2) was used to
determine trends in recovery boiler rating (size) between 1954 and 1975 for
units installed in the United States. These data are summarized in Table
A-10.4-1 with the number built and average BsW rating as a function of time.
(The non-dimensional B&W recovery boiler rating involves the: weight of solids
in the liquor per weight of pulp; heating value of the solids; daily pulp
output; and a constant. The trend in this rating factor, and not its magnitude,
is of interest for this discussion. A unit measure of the BsW rating corresponds
to 5-,714 kW-hr/day (19.5x10 Btu/day) gross heat input to the furnace.)
It is seen from Table A-10.4-1 that there has been a general increase
in the size (rating) of the recovery boilers. The "average" boiler was built
in 1964.
Total Number and Geographic Distribution
Information supplied by Babcock and Wilcox and Combustion
Engineering (Refs. A-10.4-2 and A-10.4-3) was used to determine the
geographical distribution of recovery boilers by state. Table A-10.4-2
presents the state-wide distribution of the 274 units reported by
both manufacturers. Also shown in Table A-10.4-2 is the distribution
of recovery boiler relative capacity which is directly proportional
to the furnace gross heat input. In essence, the relative capacity
data presented in Table A-10.4-2 is an indicator of the amount of wood
pulp processed by each state. The arithmetically average recovery
boiler has a gross furnace heat input of 2.80 x 10 kw-hr/day (9.56
x 109 Btu/day, 117 MW) .
277
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TABLE A-10.4-1. TRENDS IN BABCOCK AND WILCOX BLACK LIQOOR RECOVERS BOILERS
Year Built
1954
1955
1956
1957
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
No. Built
5
13
9
3
-
7
4
1
5
" 9
4
15
7
2
5
6
7
2
8
7
4
5
128
Aver. BSW Rating *
213.4
331.4
356.7
255.0
-
390.0
253.0
666.0
340.0
600.0
650.0
494.5
754.9
700.0
565.0
640.0
798.0
475.0
712.4
482.1
725.0
582.0
*This rating is diraensionless
(The non-dimensional B&W recovery boiler rating involves the; weight of
solids in the liquor per weight of pulp; heating value of the solids; daily
pulp output; and a constant. The trend in this rating factor, and not is
magnitude, is of interest for this discussion. A unit measure of the BSW
rating corresponds to 5,714 kW-hr/day <19.6xl06 Btu/day) gross heat input
to the furnace.)
278
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TABLE A-10.4-2.
DISTRIBUTIONS OF NUMBER AND RELATIVE CAPACITY
OF KRAFT RECOVERY BOILERS
State
Alabama
Arizona
Arkansas
California
Florida
Georgia
Idaho
Ken tucky
Louisiana
Maine
Maryland
Michigan
Minnesota
Mississippi
Montana
New Hampshire
New York
North Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
South Carolina
Tennessee
Texas
Virginia
Washington
Wisconsin
No.
26
2
14
6
19
30
4
3
24
13
2
5
4
9
4
2
2
18
2
1
17
4
7 '
3
14
13
19
7
274
Rel. Cap., %
9.76
0.60
5,47
1.55
8.01
10.99
0.80
1.00
10.03
4.01
1.16
1.17
1.03
4.24
1,55
0.51
0.48
6.56
0,37
1.12
5.43
0.61
3.51
0.99
5,67
4.39
7,44
1.57
279
-------
Limitations In Equipment Uses And Fuels
There are no known limitations in either equipment or fuel
used. However, operation of these devices, especially air distri-
bution, is quite important where chemical recovery efficiency and
safety are concerned.
Quantity And Geographic Distributions Of Fuel Used
There was no specific information found concerning this subject.
Aside from device start and warm-up there is no other requirement for
fossil fuels.
Air Pollutant Emissions
Total yearly emissions from recovery boilers are shown in
Table A-8-1. Ranked tenth in order of NO emissions, recovery boilers
are sixth in magnitude of SO emissions. The high sulfur content of
the black liquor is the source of SO as well as potential H S and
3C <£
other reduced sulfur compounds. Particulate emission levels are third
highest in the tabulation. CO emission levels are ranked second follow-
ing iron and steel furnaces.
280
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A-10.5 WOOD WASTE BOILERS
Major Manufacturers
The major manufacturers of wood waste (wood and bark) boilers
are:
Babcock and Wilcox (Wilmington, North Carolina)
Combustion Engineering (Chattanooga, Tennessee)
Foster Wheeler (Livingston, New Jersey)
Riley Stoker (Worcester, Massachusetts)
Associations
There is no known national association specifically for wood
waste' boiler manufacturers. However, all the above organizations are
members of the American Boiler Manufacturers Association.
Basic Equipment And Combustor Design (Refs. A-1Q.4-1 and A-1Q.5-1)
The material burned in these boilers consists of slabs, logs,
bark strips, sawdust and shavings originating in sawmills, plywood
facilities and pulp and paper mills. These materials will have a
highly variable moisture content reflecting the tree species, time of
if
year when cut, part of the tree, and its exposure to moisture during
transit and storage. In addition, salt content in the bark resulting
from transportation by sea creates other problems which must be
considered during boiler design. Due to seasonal variations in wood
waste supply, all boilers are equipped to bum a secondary fuel(s).
All material, except sawdust, is first reduced to chip size (hogged)
in-order to facilitate both charging into the furnace and subsequent
combustion.
Burning -of the wood waste occurs in three steps: drying' of the
material; distillation and combustion of the volatile matter; and,
combustion of the fixed carbon. Furnace designs for accomplishing
these steps include pile burning where the waste is deposited in a
pile on a grate ; combustion air enters from beneath the grate and
flows around the burning pile. This method of firing requires between
281
-------
30 and 40% excess air at the^boiler outlet. The wood waste may also
be burned in a furnace equipped with a traveling grate and a spreader
stoker similar to that used with coal. The smaller particles will dry
out and burn during flight with the balance of the burning occurring
on the grate.
Figure A-10.5-1 is a cross-sectional view of a wood waste boiler
designed to burn hogged wood with either oil, gas, or pulverized coal.
Current FuelUse, Trends and Properties
Information supplied by Babcock and Wilcox and Combustion
Engineering (Refs. A-10.4-2 and A-10.4-3) tabulates characteristics of wood
bark boilers installed by these firms. In each instance a supplementary
fuel (or fuels) was indicated and steam capacity on wood waste alone
ranged from 28-92% of the total steam capacity, with the supplemental
fuel(s) accounting for the balance. (The use of a supplemental fuel
can lead to the formation of an ash of lower melting temperature than
that of either ash taken separately and may become a problem.) In
several instances the furnace has been designed so that another
supplemental fuel, usually pulverized coal, can be used in the future.
The limited amount of information obtained precluded
establishing specific trends in fuel usage.
Total Number And Geographic Distribution
The total number of bark boilers reported in References A-10.4-2
and A-10.4-3 (107) was not sufficient to establish a definitive distribution
by state of these devices. Rather, the number reported for each state was
expressed as a percentage of all the units reported. This assumes that the
distributions of bark boilers installed by these manufacturers are representa-
tive of units installed by all manufacturers. These results are shown in
Table A-10.5-1.
282
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OUTl£T
CONTINUOUS
ASH REMOVAL
Figure A-10.5-1. Wood waste boiler (Babcock & Wilcox).
283
-------
TABLE A-10.5-1. DISTRIBUTIONS OF BASK BOILERS AND RELATIVE CAPACITIES
State
Alabama
Arkansas
California
Florida
Georgia
Idaho
Louisiana
Maine
Maryland
Michigan
Minnesota
Mississippi
North Carolina
Oklahoma
Oregon
South Carolina
Tennessee
Texas
Virginia
Washington
Wisconsin
Rel. No., %
14.0
3.7
1.9
9.4
8.4
0.9
3.7
5.6
0.9
0.9
0.9
3.7
3.7
0.9
7.5
1.9
1.9
7.5
1.9
14.0
6.5
Rel. Cap., %
11.9
4.5
1.9
7.3
11.9
0.7
6.5
8.0
0.1
0.5
0.8
6.7
1.8
1.7
4.9
1.0
1.2
10.5
1.8
7.8
8.8
Relative Capacity, %
Total sample number
Total steam rate
Boiler Steam Rate
All Boilers Steam Rate
107
= 12.16 x 10 kg steam/hr
x 100
284
-------
LimitationsIn Equipment UsesAnd Fuels {Refs. A-10.4-1 and A-10.5-1)
Wood waste boilers are limited by wood supply and wood moisture;
wood supply fluctuates with mill production. The net heating value of
the wood waste decreases as the moisture content increases and with
moisture contents above 65%, a large part of the energy in the wood is
required to evaporate the moisture, and little remains for steam genera-
tion. Burning of this wet waste becomes a means of disposal rather than
a source of energy.
Combustion temperatures resulting from burning dry waste may be
high enough for impurities to cause fluxing of furnace refractories
and fouling of heating surfaces. In addition, a furnace designed to
burn wet fuel will operate poorly with dry fuel, and a dry fuel furnace
may be unable to carry its normal load when supplied with wet fuel.
In soma cases, extremely dry fuel is sprayed with water so that its
moisture content is closer to design moisture.
Quantity And Geographic DistributionOf Fuels Used
No information was obtained for this subject in regard to either
wood waste or supplementary fossil fuels used. As noted in Reference
A-4-1, energy produced by hogged fuel and bark (at 50% moisture content
for each) amounted to 6.8% of the total energy consumption in the pulp,
paper and paperboard industry during the first six months of 1975.
Air Pollutant Emissions
The NEDS listing for air pollution emissions from wood and/or
bark boilers was shown in Table A-8-1. The boilers rank third in
magnitude of NO , CO, and particulates emissions but are sixth in terms
of HC and seventh in SO emissions.
x
285
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A-10.6 COKE OVENS
Major Manufacturers
The major manufacturers of coke ovens are:
Koppers Co. (Pittsburgh, Pennsylvania)
Wilputte Coke Oven Div., Salem Corp. (Morriston, New Jersey)
Qtto-McKee (Independence, Ohio)
Dravo-Still (Pittsburgh, Pennsylvania)
Kaiser-Didier (Oakland, California)
The last two named are recent entries into the field and as of December 1976
had not produced any ovens.
Each manufacturer will perform a turn-key operation in that
they will design, procure components, and construct the ovens as well
as the by-product plants which extract chemicals from the coke oven
gas.
Associations
There are no known coke oven manufacturer's trade associations.
Basic Equipment And Combustgr Design
Modern by-product coke ovens are tall, thin, long devices which
will heat metallurgical grade coal in the absence of air to produce
coke. The older beehive configurations are not common and will not
be discussed. The fuel for heating the coal is mostly coke oven gas,
i.e., the gaseous products of coal distillation, or blast furnace gas
with a small usage of both coke oven and blast furnace gas. All coke
oven gas is first routed through a by-product recovery plant and then
approximately 60% of the gas is used within the oven with the
balance routed to the steel mill. A grouping of coke ovens is termed
a battery and there may be anywhere from 5 to 106 ovens in a battery.
Typically, there is a minimum of 15 ovens in a battery. Reference
286
-------
A-10.6-1 presents details showing differences between the several types of
coke ovens. Basically, these differences involve the specific arrangement
of the hot gas flues within the ovens. Figure A-10.6-1, taken from Reference
A-10.6-1, is a cut-away view of a coke oven.
Current Fuel Use,TrendsAnd Properties
Approximately 85% of the devices use coke oven gas, 12% use
blast furnace gas, and 3% use a combination of these two fuels (Ref.
A-10.6-2). No other fuel types are used.
No information was obtained regarding trends in fuel usage.
Such trends might be approximately proportional to yearly coke
production.
Trends In Equipment Type,Age, Size And Use
The trend in equipment type has been to the by-product method;
as a result only one location in the United States uses the older beehive
method.
The life of a by-product oven battery .is from 20 to 30 years
(Ref. A-10.6-1) but no information was found on representative oven
age nor the trend in age.
There has been an upward trend in oven height and length, i.e.,
greater coke capacity per oven. The width of the oven is fairly well
fixed to allow for coking of the coal within approximately 17 hours,
i.e., if the width (minimum oven dimension) were increased the coking
time would also be increased. At the present state-of-the-art a
representative oven is 6.1 m (20 ft) high, 15.2 m (50 ft) long, and
0.5 m (18 in.) wide.
Total NumberAnd Geographical Distribution
As of 1974, according to Reference A-10.6-3, there were 11,694
coke ovens in the United States at 50 plant locations. The majority
of ovens (59%) were located in Pennsylvania, Indiana, and Ohio.
287
-------
Figure A-10.6-1. General cut-away of coke oven. i. Oven chamber.
2. Vertical combustion flues. 3. Horizontal flues.
4. Cross-over flues. 5. Regenerators. 6. Oven sole
flues. 7'. Gas and air connections to waste-gas flue.
8. Waste-gas flues. 9. Gas ducts for coke-oven gas.
10. Oven gas main. 11. Blast-furnace gas main.
12. Charging holes. (Koppers Company, Inc.)
288
-------
Additionally, 97.7% are the by-product type and the balance (2.3%)
are the beehive type. Table A-10.6-1 presents the coke oven distribution
by state.
TABLE A-10.6-1. COKE OVSN DISTRIBUTION BY STATE
• State
Alabama
California
Colorado
Illinois
Indiana
Maryland
Michigan
Minnesota
New York
Ohio
Pennsylvania*
Tennessee
Texas
Utah
West Virginia
No. of Ovens
691
315
216
424
1669
757
438
115
645
1665
3568
44
140
252
755
11,694
* State total includes 266 beehive ovens
Limitations InEquipment Uses And Fuels
A coke oven battery can use either coke oven or blast furnace
gas i_f it were originally designed to accommodate both fuels. A
substantial capital investment would be required to substitute blast
furnace gas for coke oven gas in that piping from the blast furnace
to the battery would be required. In addition, the marked differences
in heating value between the gases: coke oven gas 18.6 MG/m
(500 Btu/cf); blast furnace gas 3.3 - 3.7 MJ/m (90 - 100 Btu/cf)-
would probably require extensive revisions in the flue ductwork within
289
-------
•J
the oven since a greater volume of gas would be needed. In view of
the latter consideration it does not appear economically feasible to
substitute blast .furnace gas in those batteries which were not
originally designed for this fuel.
Quantity And Geographic Distribution Of Fuels Used
In a coke oven, the coal charge (feedstock) itself is the primary
source of fuel via the generated coke oven gas. According to Reference
A-10.6-4 for the year 1972, 77.9 x 10 kg (85,7 x 10 short tons) of coal
were used in the production of coke; 62.3x10 kg (68.5x10 short tons) of
10 3
coke, screening and breeze were produced. Also produced were 4.59 x 10 m
(1.62 xllO ft ) of coke oven gas. However, the amount of coke oven gas
used as fuel within the oven is less than this amount for two reasons:
1. The extraction of by-product chemicals
2. Routing of approximately 40% of the remaining gas to the
steel mill.
Thus, it is not possible at this time to determine the total
quantity and geographic distribution of fuels (coke oven and blast
furnace gas)' used in coke ovens.
Air Pollutant Emissions
The yearly air pollution emissions from by-product coke ovens
are contained in Table A-8-1. In this instance the "Number of Records"
obtained from the NEDS listing (Hef. A-2-2) is assumed to refer to the
number of coke oven batteries where each battery may contain a large
number of individual ovens. HC emissions are high (second) relative to
other devices tabulated. Emission levels of other pollutants listed are
much lower in the ranking order.
290
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A-10.7 BLAST FURNACES
Major Manufacturers
The major manufacturers of blast furnaces are:
Koppers Co., Inc. (Pittsburgh, Pennsylvania)
Arthur G. McKee (Cleveland, Ohio)
Dravo (Pittsburgh, Pennsylvania)
Each of these manufacturers will perform a complete operation
from design, to component procurement, and construction.
Associations
There are no known associations of blast furnace manufacturers.
The American Iron and Steel Association (AISI) represents the equipment
users.
BasicEquipment And Combustor Design (Ref. A-10.6-1)
A blast furnace is a device which produces essentially pure
metallic iron (pig iron) from iron containing materials. It is a
refractory lined, circular, conical structure with a hearth (lower) .
diameter ranging from 6.1 m to 9.2 m (20 - 30 ft) and total height
between 27.4 - 33.5 m (90 - 110 ft). The top end (smaller diameter)
of the furnace is fitted with a removable seal arrangement to allow
charging of materials which consist of:
. Iron-bearing material (ore, sinter, pellets, scale, slag, scrap)
. Fuel (coke)
.Flux (limestone and/or dolomite).
The hearth region is fitted with tuyeres for admitting preheated
(blast) air and, in most instances, a secondary fuel (gas, oil or
pulverized coal). The preheated blast air burns with part of the fuel
•(coke) to produce heat for the chemical reactions involved and for
melting the iron. The balance of the fuel and part of the gas produced
reduces (i.e., removes oxygen from) the metal. The blast furnace
exhaust gas, a low energy content gas, is cleaned and burned in the air
preheaters.
291
-------
Each furnace is furnished with from 3 to 8 (3 or 4 are typical)
hot blast stoves. These stoves are brick-lined regenerators whose
function is to preheat the blast air before entry into the furnace.
These devices are fueled with cleaned blast-furnace gas (with some
usage of coke oven gas) and contain brick checkerwork for countercurrent
air heating. For a 3 stove arrangement one is supplying heated air to
the blast furnace while the other two stoves are being heated by burning
blast-furnace gas. Figure A-10.7-1 is a general arrangement of a blast
furnace and hot blast stove.
Blast furnaces are rated in terms of their internal (stack)
volume while hot blast stoves are rated by their internal heat transfer
area.
Current Fuel. Use, Trends And Properties
Currently, coke is the main fuel used in the blast furnace proper.
Some oil, natural gas and pulverized coal are used as secondary fuels (the
coal is used at only one mill in the U.S.).
No information was found concerning fuel use trends as a result
of device efficiency improvements. Therefore, it was assumed that fuel
usage trends would follow the annual production of pig iron. Information
was obtained on pig iron production from the American Iron and Steel
Institute, and is presented in Table A-10.7-1, for the years 1966-1975.
These data reflect the general national economic climate in the
United States, i.e., pig iron production is high during periods of
relative prosperity and low during recessional phases.
TABLE A-10.7-1. ANNUAL UNITED STATES PIG IRON PRODUCTION
10 Metric Tons (103 Short Tons)
Year
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
Production
83,182
79,076
80,709
86,379
83,123
73,908
80,856
91,670
87,190
72,657
(91,500)
(86,984)
(88,780)
(95,017)
(91,435)
(81,299)
(88,942)
(100,837)
(95,909)
(79,923)
292
-------
A. Ore britlgts
'*- Ore transfer car
1". Ore storage yard
1'. Stockhousc
1M Ore and limestone bins
l>-2 Coke bin
I >-3 Scale car
Coke dust, recover}- chute
Krt'iiiht car
Skip and bell hoist
^kip bridge
Hlast fiirnucc
•M Itkttlvr valve
J-2 Cum uptake
J-3 KrrcivinK hopjn'r
J-4 Diniributor
J-S Small bell
J-6 Large bull
J-7 Stock line
J-S Stack
J-9 Bosh
J-10 Tuycros
J-ll Stag notch
J-12 Hearth
J-13 IJustle pi|H!
J-14 Iron notcli
K. Slag ladle
L. Cast house
1^-1 Iron' trough
L-2 Sbc f=ki«iiner
L-3 Iron runner
M.- IIot-n>»«taI ladle '
K. Fine ihtst mr
O. Dust catcher
P. Downconkr
ty. Hot blast lin« to furnaeo
11. Gas washer
Il-l Sludge liim to thickener
H-2 Spray washer
1^-3 Kluctrii-al preei|>i(aior
S. Gas otTtaki' to stove burner
T. Hot blast connection fnim stove
V. Stove
L'-l C'a» burner
U-2 ('ombiistiou ohiintlx'r
U-3 ChiM'kcr cluunter
\". Kxlmwt gas line to stack
\V. Cold biast line frum blmver
X. Surplus KII.S lino
Y. Stock—Ir«»n «ire, coke, limestone
Z. Jib Ixxim craiie
Figxire A-10.7-1.
Cross-section of typical blast furnace and hot blast
stove (U.S. Steel Corp.).
293
-------
Trends In Equipment Type, Age, Size And Use
No quantitative information was found concerning these aspects
of blast furnaces. In general, the furnace is rebuilt (refractories
changed) every five years and it is during these rebuilds that provision
is made for incorporating supplemental fuels.
New blast furnaces are being made larger ususally to replace
several smaller units. However, no specific information was obtained
regarding size as a function of time.
•Ratal Number and Geographic Distribution
Table A-10.7-2, prepared from data in Reference A-10.6-3, presents
the blast furnace number distribution by state. Of the total number
(189), 63.0% are concentrated in Pennsylvania, Ohio, and Indiana.
The blast furnace internal volume (stack volume) is the unit of
measure of capacity. Using data from Reference A-10.6-3 a tabulation was
made of stack volumes to arrive at a relative pig iron capacity (i.e., pig
iron capacity was taken as proportional to stack volume) by state. The
results are also shown in Table A-10.7-2. Pennsylvania, Ohio, and Indiana
account for 59.5% of the relative capacity.
TABLE A-10.7-2, BIAST FURNACE AND RELATIVE CAPACITY DISTRIBUTIONS BY-STATE
State
Alabama
California
Colorado
Illinois
Indiana
Kentucky
Maryland
Michigan
New York
Ohio
Pennsylvania
Texas
Utah
West Virginia
No. of Blast Furnaces
9
4
4
16
27
2
10
9
8
36
56
1
3
4
Rel. Cap., %
4.48
2.28
1.54
8.39
15.79
1.64
5.59
5.77
5.16
18.72
25.00
1.31
1.73
2.61
294
-------
Limitations In Equipment Uses And._F_uel3
The only fuel limitation noted was in secondary fuels. These can
be used only when the furnace was originally designed, or retrofitted, to
burn secondary fuels.
Quantity And Geographic Distribution Of Fuels Used
Table A-10.1-1 contains fossil fuels purchased by SIC 33, Primary
Metal Industries, by state. It is assumed that nearly all the coal and
coke entries for this industry are used in blast furnaces.
Air Pollutant Emissions
Air pollution emissions for the general heading of iron and steel
furnaces are shown in Table A-8-1. Emissions specific to blast furnaces
were not found. NO emissions are expected to be low based on limited data
X
(Ref. A-1Q.12-2) because of the low heat content of blast furnace gas.
295
-------
A-1Q.8 OPEN HEAHTH FUKNACES
Major Manufacturers
Open hearth furnaces are no longer being made for the Iron and Steel
Industry but the major manufacturer was Koppers Co., Inc. (Pittsburgh,
Pennsylvania).
Associations
No information was obtained on associations of open hearth
manufacturers.
Basic Equipment And Combustor Design (Ref. A-10.6-1)
The open hearth furnace consists of a refractory lined vessel
which is shallow compared to its length. A refractory lined arched
roof completes the basic reverberatory furnace structure. Regenerative
checkerwork is used for air preheating, and a wide variety of fuels are
used. Figure A-10.8-1 is a view of the principal parts of an open hearth
furnace.
A carefully controlled charging sequence is followed. First,
limestone (flux), scrap and iron ore is charged into the furnace and then
melted—mainly by radiation from the flame and roof. Then, molten pig
iron is charged and the heat is refined.and ready -for tapping in about
8-10 hours from the initial charging. (The shorter time period corresponds
to those furnaces equipped with roof mounted oxygen lances.)
A complex series of chemical reactions occurs within the molten
metal to remove the impurities by oxidation. The carbon content is also
carefully controlled. Oxygen is obtained partly from the iron ore and
partly from the furnace atmosphere. _ , '
At the correct time the furnace is tapped and deoxidizing agents
and alloying elements are added as the molten metal flows into the
ladle.
No specific details were obtained on burner characteristics.
296
-------
STAC
x
WPIK8
SPOUT
Fosetp AIR
INLET VALVE
On HU
SEHQVEO
KSEKMFME CHAHBtK
HTH ROOF AHD $!D£
9ALL
Figure A-10.8-1. Principal parts of an open-hearth furnace
(U.S. Steel Corp.).
297
-------
Open hearth furnaces are being gradually replaced by basic oxygen
furnaces (BOF) and electric arc furnaces. Between the years 1964 and 1974
production by the open hearth has dropped from 77.2% to 24.5% of total steel
output. During the same time period the use of BOF has increased from 11.8%
to 56.2% of the total steel production. However, the open hearth furnace
will probably survive for another 20 years before being completely replaced.
Additionally, BOF's are not combustion devices as no fuel source is required
directly in the BOF unit.
The capacity of open hearth furnaces is expressed by the amount of
charge loaded per heating cycle. Furnaces currently operating range from
45 Mg (50 tons) to 381 Mg (420 tons) per heat with the average size about
227 Mg (250 tons) per heat.
Current Fuel Use, Trends And Properties
Current practice is to use the following fuels, (usually in
combinations of two or more) (Ref. A-10.6-3):
. coke oven gas
. pitch
. tar
. oil (grade not specified)
. natural gas.
Only natural gas is definitely a purchased fuel while the others are normal
products of by-product coke ovens.
No information was obtained on the' relative proportions of
these fuels when used in combinations. Further, no specific information
was obtained on fuel usage trends; however, overall usage should approximate
the overall open hearth steel production previously quoted.
Trends In Equipment Type, Age, Size And Use
No information was obtained other than that no new units are being
constructed and existing units are being phased out.
298
-------
Total Number And Geographical Distribution
Table A-10.8-1, prepared from data contained in Reference A-10.6-3,
gives the distribution of the 189 open hearth furnaces by state. Open
hearth furnaces are rated on the amount of steel produced per cycle
(heat) since the furnace is a batch processor. (A heat may vary in duration
from 8 to 10 hours.) This rating factor was used to determine the approximate
open hearth steel production by state; the results are also shown in Table
A-10.8-1. Ohio, Pennsylvania, and Indiana comprise 71.4% of all the furnaces
and 70.4% of the approximate capacity.
TABLE A-10.8-1. DISTRIBUTIONS OF OPEN HEARTH FURNACES AND
APPROXIMATE CAPACITY BY STATE
State
Alabama
California
Illinois
Indiana
Maryland
New York
Ohio
Pennsy Ivania
Texas
Utah
No. of Furnaces
9
16
4
27
7
3
57
51
5
10
Approx. Cap. , %
3.66
5.82
2.19
16.20
6.45
1.25
27.72
26.50
2.74
7.46
LimitationsIn Equipment Uses And Fuels
In a steel mill which contains coke ovens, blast furnaces and
open -hearth furnaces, equipment fuel usage is established during the
initial mill design phase. Extensive hardware changes would be required
to substitute fuels in the devices, e.g., substituting coke oven gas for fuel
oil or natural gas necessitates long runs of large diameter ductwork and
burner changes. Thus, the economics of the situation would probably preclude
using fuels other than called for in the original design.
299
-------
Quantity And Geographic Distribution Of Fuels Used
It is assumed that the distribution of fuels used in open hearth
furnaces is proportional to the amount of coal and coke purchased by
SIC 33, Primary Metal Industries, as shown in Table A-10.1-1. The rationale
for this assumption is that in a steel mill with on-site by-product
coke ovens, the major source of fuel for the open hearth furnaces
would be coke oven gas and that the amount of this gas is proportional
to the amount of coal and coke purchased. (In this context, "purchasing"
nay amount to a "paper" transfer of a material within the same company
from one activity to another.5
Air Pollutant Emissions
Open hearth air pollution emissions are included in Table A-8-1 as
part of the "Iron and steel furnace" category. Table A-10.8-2 breaks them
out as a separate entry. Open hearth furnaces contribute 67% of the iron
and steel furnace category- emissions. These furnaces have very high
temperatures and long residence times that are conducive to NO formation.
Emissions also vary considerably over each cycle (Ref. A-1Q.12-2).
300
-------
TABLE A-10.8-2. OPEN HEARTH FURNACE AIR POLLUTION EMISSIONS
kg/Year (Short tons/Year)
With O2
Lance
Without O
Lance
Total
No. of
Records
66
75
141
NOX
6 3
2.5x10 (2.8x10 )
1.6xl06 (l.BxlO3)
4.1xl06 <4.6xl03)
sox
3.5xl07 (3.8xl04)
9.0xl05 (9.9xl02)
3.6xl07 {3.9xl04)
HC
2.7x10 (3x10°)
6. 8x10 4 (7.5X101)
7.1xl04 (7.8X101)
CD
0 (0)
l.lxlO7 (1.2xl04)
l.lxlO7 (1.2xl04)
Particulates
7 4
3.8x10 (4.2x10 )
4.9xlO? C5.4X104)
8. 7x10 ? (9.6xl04)
OJ
O
-------
A-10.9 SOAKING-PIT, REHEATING, AND HEAT-TREATING FURNACES
Major Manufacturers
Major manufacturers of soaking-pit and reheating furnaces are:
Surface Combustion Div., Midland-Ross Corp. (Toledo, Ohio)
Swindell-Dressier Div., Pullman Inc. (Pittsburgh, Pennsylvania)
Loftus Engr. Corp., Western Gear Corp. (Pittsburgh, Pennsylvania)
The major manufacturers of heat-treating furnaces are:
Surface Combustion
Swindell-Dressier
Associations
There are no known associations of manufacturers of these devices.
However, each of the above is a member of the American Iron and Steel
Engineers (Pittsburgh, Pennsylvania).
Basic Equipment And Combustor Design (Ref. A-10.6-1)
The primary functional objective of each of these devices is the
same — to raise the steel temperature to a specified range. In common
usage, a soaking-pit furnace is charged with steel ingot from the steel
mill and raises its temperature to a normal range between 1450 and 1617 K
(2150 - 2450°P) in preparation for the first rolling or forming operations.
A reheating furnace raises the temperature of the partially formed steel
"to the same temperature range for further hot-working.
Heat-treating .furnaces raise the finished steel product to a
temperature between 700 and 1144 K (800 - 1600°F) for the specific
purpose of controlling the mechanical properties of the final product.
Therefore, the operation of a heat-treating furnace is more critical than
that of a soaking-pit or reheating device insofar as the metal is concerned,
e.g., heating and cooling rates, as well as temperature levels, must be
carefully con-broiled. Additionally, the chemical composition within the
furnace must not adversely affect product surface quality.
302
-------
Soalcing-pit furnaces are usually batch type devices designed
to heat steel ingot prior to rolling or forming operations. Several
furnaces are usually grouped together so as to share the same ingot
handling equipment and interior walls. Each pit, in turn, is designed
to accommodate several ingots with the constraint being that the ingots
never cover more than 50% of the floor-plan area.
Burner design and placement, as well as exhaust port placement,
are chosen to promote strong internal circulation patterns of the
combustion gases to provide a uniform heating environment for the ingots.
This requirement has led to the development of a family of furnace geo-
metrical designs; each will generate these gas circulation patterns. For
example, one design ("vertically-fired") has the coabustor centrally
located and firing vertically into the furnace with the waste gases being
drawn off through the furnace outer walls. Another design has a series
of burners firing tangentially into a cylindrical furnace with the exhaust
port centrally located in the furnace floor. Figure A-10.9-1 shows two
types of soaking-pit furnaces—the one-way and vertically-fired configura-
tions.
Recuperators or regenerators are usually provided to preheat
the incoming combustion air. (Current practice is to provide recuperators
or regenerators on all furnaces. Such was not the case 20 years ago.)
Reheating furnaces are of both batch and continuous type and
are also designed to promote strong internal gas circulation. These
devices are used to reheat slabs, billets and blooms prior to further
hot-working operations. Burner placement in continuous reheating
furnaces vary from a single burner at the steel discharge end (firing
cpuntercurrent to the metal travel) to a series of up to five burner zones
located along the length of the furnace. fhe latter arrangement allows
the metal to undergo preheating, heating and soaking during its travel
through the furnace. Bais multi-zone furnace permits better control
of metal heating rates and the gradual temperature rise enables
charging all grades of cold steel without having to cool the furnace.
303
-------
BURNER-
WASTE 8AS
OUTLET PORT J*_
ONE END ONL1T
PLAN VIEW
BURNER «-1
(ONE END ONLY) """
WASTE 6*3 >*"*
OUTLET PORT^
•oil, (
ar%
•s,
1
t
jpr •
^S
\
I
t
S
\
\
\
1
—
*
'&?£'.&• :••: l^S^S-SvvSTft*
»*
\\
!i
J
'':y'r
ELEVATION
A. One-way fired
FIRING PORT
RECUPERATOR
ELEVATION
RECUPERATOR
E. Vertically-fired
Figure A-10.9-1. Soaking-pit furnaces (U.S. Steel Corp.)
304
-------
Heat-treating furnaces are either batch or continuous devices
and are further identified as being directly or indirectly heated.
They are usually well insulated and built tight to avoid the loss of
special atmosphere gas. Special attention is given to achieve a
uniform temperature distribution within the working volume. For annealing
operations the rate of temperature increase and decrease is very carefully
controlled. Quenching tanks are located in close proximity to the
furnace to minimize the time between discharge from the furnace to
immersion in the quenching tank.
Special atmosphere gases are used to minimize scaling caused
by attack of normal atmospheric gases. Continuous furnaces may also
include fire curtains at both the charging and discharging ends to
prevent atmospheric oxygen from entering the working volume.
There are many configurations of the batch and continuous
furnaces. An example of the former is the bell-type in which the steel
is loaded on a tracked carrier which is then moved into position under the
furnace body. The body is then lowered over the carrier and the heating
cycle commences. A single furnace body can be repositioned to service
several carriers.
A walking-beam furnace is an example of a continuous device and
,consists of a series of pivoted beams running the length of the furnace.
The steel is moved through the furnace as a set of beams are pivoted
causing the charge to move to the next set of beams, etc.
CurrentFuelUse, Trends And Properties (Ref. A-10.9-1)
Current fuel use includes fuel oil, natural gas, coke-oven and
cold blast furnace gas. Trends in fuel usage have been away from
natural gas to a combination of blast furnace and coke-oven gas, with
Hos. 2 and 6 fuel oils as alternates. Economic considerations preclude
furnace operation on blast furnace gas alone as this low energy fuel
would require extensive ductwork and burner modifications.
305
-------
Trends In Equipment Type, Age, Size And Use
According to Reference A-10.9-1, up until 3-4 years ago 30-40%
of their inquiries concerned nonregenerative (no air preheat) devices.
Since that time all requests have specified preheated air (either
recuperative or regenerative) in the interest of fuel economy.
Devices which had used natural gas exclusively have been
retrofitted with new burners to allow operation on other gaseous fuels,
e.g., coke-oven and blast furnace gas.
Ifeere has been no marked shift toward greater use of continuous
type furnaces mainly because these larger capacity devices are already
extensively used. However, within the continuous type device category,
newer installations have favored the walking-beam configuration to
achieve greater capacity. The capacity of a pusher type reheating
furnace is limited by the length of the pushing mechanism but such is
not the case for the walking-beam type.
No specific information was obtained on device age and size—
except that the trend is for larger capacity units.
Total NumberAnd Geographic Distribution
According to Reference A-10.6-3, there are 1435 soaking-pit
furnaces, 1264 reheating furnaces, and 3836 heat-treating furnaces
(for a grand total of 6535) distributed By state as shown in Table
A-10.9-1. Whenever possible devices using electricity as the heat
source were not included in the tabulation.
Limitations In Equipment Oses And Fuels
Limitations in this area pertain to fuels used. A device
which was originally designed to burn a specific fuel can not burn a
substitute fuel unless subsequent burner retrofit has been performed.
As previously discussed, there is no economic justification in using
low energy blast furnace gas by itself.
306
-------
TABLE A-10.9-1. DISTRIBUTIONS OF SOAKING-PITS» REHEATING,
AND HEAT-TREATING FURNACES
State •
Alabama
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Hawaii
Illinois
Indiana
Kentucky
Maryland
Michigan
Minnesota
Mississippi
Missouri
New Jersey
New York
North Carolina
Ohio
Oklahoma
Pennsylvania
Rhode 'Island
South Carolina
Tennessee
Texas
Utah
Virginia
Washing-ton
West Virginia
Wisconsin
Total
Soaking-Pits
29
-
-
32
59
4
5
-
8
-
73
212
60
85
49
-
-
12
2
135
-
204
_'
372
-
-
-
58
10
-
12
14
"""
1435
Reheating Furnaces
20
1
1
34
10
7
7
2
5
1
92
100
5
75
33
-
1
5
5
102
17
121
1
573
-
1
2
19
7
3
4
5
5
1264
Heat-Treating Furnaces
64
-
120
18
86
2
2
5
-
155
248
51
127
205
1
2
-
15
200
3
806
_
1529
9
-
1
39
1
-
29
90
28
3836
307
-------
Quantity And Geographic DistributionOf Fuels Used
A very approximate assessment of this subject is given by the
data in Table A-10.1-1 for SIC 33 - Primary Metal Industries and, to
a lesser degree, SIC 34 - Fabricated Metal Products. If it is assumed
that coke-oven gas consumption in heating furnaces is proportional
to coke consumption then Table A-10.1-1 provides at least the relative
amounts, on a geographic basis, of fuels used.
Aside from this approach there was no specific information
found at this time on.distributions of fuel used.
Air Pollutant Emissions
In this instance, the NEDS listing (Ref. A-2-2) for these devices
is completely inadequate. . A total of only 134 records (each record assumed
to be a separately identifiable device) was found for soaking-pit and
heat-treating furnaces in activity headings of: primary metals - steel
production (1 record); secondary metals - gray iron (16 records);
secondary metals - steel foundry (113 records); and, secondary
metals - malleable iron (4 records). As previously mentioned,
Reference A-10.6-3 listed a combined total of 6,535 soaking-pits,
reheating furnaces, and heat-treating furnaces.
In addition, Reference A-10.9-2 does not contain emissions
factors (weight of emission/unit measure of product) for any of
these combustion devices. Therefore, it is concluded that no- compre-
hensive air pollution emissions data are available for soaking-pits,
reheating furnaces, and heat-treating furnaces in the steel industry.
308
-------
A-10.10 STATIONARY RECIPROCATING ENGINES
Major Manufacturer's
The major manufacturers of internal combustion engines/ both
diesel and spark ignition, are shown in Table A-10.10-1 together with
information pertaining to engine characteristics. (These data were
secured from an unpublished source.)
Associations
The following associations represent engine manufacturers:
. Engine Manufacturers Association (Chicago, Illinois)
. American Trucking Association (Washington, D.C.)
. Diesel Engine Manufacturers Association (Cleveland, Ohio)
Basic Equipment And Combustor _Design
Diesel engine (compression ignited, CI) combustion is achieved
by injecting fuel into a cylindrical chamber containing eompressionally
heated air with combustion occurring spontaneously. Spark ignited (SI)
engines employ a high energy electrical spark to initiate combustion.
Usually these engines induct a premixed fuel-air mixture into the
cylinder (the mixing function being performed by the carburetor).
However, fuel injection into the cylinder containing compressed air
is also utilized. Gaseous fueled SI engines mix the fuel with air
at the intake valve.
Diesel engines of the dual-fuel type also operate on gaseous
fuels but require a small amount of liquid diesel fuel to initiate the
combustion process. Such engines are designed to operate with from
6 to 100 percent liquid fuel.
Both CI and SI engines are produced in two- and four-stroke
cycle arrangements. In the CI, a power stroke is generated for
every 360 deg of crankshaft rotation (corresponding to two strokes
of the piston) while the SI delivers a power stroke for every 720
deg of crankshaft rotation, i.e. one power stroke for every four
309
-------
TABLE A-10.10-1. 1C ENGINE MANUFACTURERS
Manufacturer
Large Bore Engines
Alco
Colt
Cooper-Bessemer
ElectroMotive Div (GM)
Enterprise
Dresser-Clark
Ingersoll-Rand
Worthingtorf*1
White Superior
Medium Bore Engines
All is- Chalmers
Case
Caterpillar
Cheverolet-Oldsmobile (GM)
Chrysler
Cooper-Penjax§
Cummins
Detroit Diesel
Ford
International Harvester
John Deere
Mi nneapol i s-Mol i ne
Murphy
Sterling
Stewart and Stevenson
Teledyne Continental
Waukesha*
White Engines (Hercules)
Bore,
inches
9
8-16
13 - 20
9
13 - 17
17 - 19
11 - 17
14 - 16
8-14
3-1/2 - 6
3-3/4 - 4-1/8
4-1/2 - 6-1/4
3-7/8 - 4-1/4
3-1/4 . 4-1/4
5-15
4-1/2 - 6-1/4
3-7/8 - 5-3/4
4-1/8 - 4-1/2
3,7/8 - 5-3/8
4 - 4-3/4
4-1/4 - 5-5/16
5-1/2 - 6-3/8
3 - 5-1/2
3.7/8 - 4-3/4
3-7/8
3-5/8 - 9-3/8
3-3/4 - 4-1/2
CID/cyl*
666
1037-3526
2155-6283
645
1200-4770
3860-5100
1350-.4993
2972-4021
510-3300
43-169
47-84
79-246
26-57
28-52
128-2827
63-192
53-149
26-67
39-136
55-89
71-133
142-207
16-166
53-149
28-4:1
38-586
35-80
Power
Range,
hpf
1000 - 4400
850 - 9400
900 - 13500
800 - 3600
1600 - 13500
1000 - 10000
1000 - 5500
2300 - 8600
400 - 2400
29 - 850
50-125
85 - 1000
50 - 2.15
43 - 175
15 - 300
120 - 1200
50 - 1100
38 - 200
16 - 325
44 - 180
90 - 180
110 - 520
16 - 152
30 - 1100
50 - 30
52 - 1550
34 - 130
Cylinder
Power,
hp/cyl
175 - 250
175 - 500
360 - 675
100 - 180
280 - 680
200 - 500
125 - 330
125 - 330
75 - 150
10 - 70
12 - 30
21 - 63
13 - 27
12 - 30
15 - 150
20 - 100
20 - 68
9-22
9-50
15-30
15 - 29
30 - 60
8-20
20 - 68
12 - 14
8 - 110
12 - 26
Speed
Range,
rpm
400-1200
500-900
250-600
900
400-600
300-330
300-550
300-500
900-1000
1200-2600
1200-2200
1200-2400
3600-4000
1200-4000
200-900
1200-2100
1800-2500
2500-4600
1800-3000
1500-2500
1800
1200-1800
1200-1800
1200-1800
2000-2400
1000-1800
2400-2800
£ Cubic inch displacement per cylinder
THorsepower is for rated conditions (continuous operation) 9 130°F intercooler water temoerature far
^large bore engines and 85°F inlet air temperature for medium bore engines.
JWorthington ceased producing engines during the writing of this report.
3'This manufacturer produces high power one- and two-cylinder engines.
#The manufacturer straddles the medium-large bore categories, however, the majority of engine production
is in the medium bore category.
Continued
310
-------
TABL1-A-10..10-1 continued
Manufacturer
Small Engines and Generator Sets
Kohler
Onan
Teledyne Wisconsin
Wills Industries
Wi tte
Very Small Engines
Briggs and Stratton
Chrysler
Clinton
Home lite
Jacobsen
Outboard Marine Corp.
(Lawn Boy)
McCulloch
Q&R
Tecumseh
Bore,
inches
_
3-1/4
2-3/4 - 4-1/8
4-1/4 - 5
2-3/8 - 3-9/16
2 - 2-1/4
2-1/2 - 2-3/8
1-7/16 - 2-3/4
2-1/8
2-3/8
1-3/8 - 2-1/4
1-1/8 - 1-17/32
2-3/8 - 3-1/2
CID/cyl*
Power
Ranoe,
hp'
3-3/4 - 28
8-30
3-1/2- - 80
11 - 28
9-27
2 - 16
3-1/4 - 8
4-7
2-4
3
<10
<20
1 - 2-1/4
2-1/2 - 16
Cylinder
Power,
hp/cyl
3-7
6-8
3-1/2 - 20
11 - 14
9-14
2-16
3-1/4 - 8
4-7
2-4
3
1 - 2-1/2
2-1/2 - 16
Speed
Range,
rpm
2000-2700
1800-3900
2400-3600
3000
800-1800
3100-4000
5500-7000
4600-5800
3600
,
6300-7200
2500-3600
Icubic inch displacement per cylinder
Horsepower is for rated conditions (continuous operation) I? 130°F intercooler water temperature for
large bore engines and 8S°F inlet air temperature for medium bore engines.
311
-------
piston strokes. The two-stroke arrangement offers the advantages of
a simpler mechanical design since it is possible to completely
eliminate the valves and valve drive train while also achieving twice
as many power strokes per unit of cylinder volume. However, these
advantages are achieved at the expense of fuel economy because a portion
of the incoming fuel charge may be swept across the cylinder and out the
exhaust port before complete combustion has been achieved.
The method of inducting air into the cylinder may also vary.
In the naturally aspirated design* the air is drawn into the cylinder
by piston pumping action. This is achieved by the slight negative
pressure produced in the cylinder of a four-stroke design as the piston
starts its downward motion during the intake stroke. In a two-stroke
engine, air is either inducted into the crankcase as the piston begins
its upward motion during the exhaust portion of the cycle or blown
into the cylinder. Thus, the amount of air inducted {and fuel also)
in a naturally aspirated engine is limited by geometry, valve timing,
and rotational speed.
In order to ease this limitation, engines are fitted with
turbochargers which are turbine driven air compressors operating from
engine exhaust energy. In this manner a greater mass of air can be
charged into the same cylinder volume and, therefore, can burn with
a greater mass of fuel. Thus, turbocharged engines can produce a
greater power output per unit cylinder volume. Estimates, reported
in Reference A-10.10-1, are that 55-60% of the diesels built today are
turbocharged and that this ratio will grow to 80% or more in years to
come.
Combustion chamber designs may include a precombustion volume into
which nearly all the fuel is injected and partially burned in a fuel
rich environment. The combustion is completed as these gases expand
into the main chamber and react with the balance of the air. These
divided chamber designs are incorporated into both CI and SI engine
312
-------
and nay reduce NO emissions via. a staged combustion technique. This
2fe
reduction is achieved, however, at an increase in fuel consumption
brought about partly by additional heat transfer losses through the
surface area represented by the precombustion chamber walls.
Figure A-10.10-1 shows an internal combustion engine—in this
instance a 2-stroke, spark ignited, natural gas fueled, turbocharged unit
with an integral gas compressor.
Current Fuel Use, Trends And Properties
Current fuels used in reciprocating 1C engines include:
distillate oil, residual oil and natural gas (dual fuel engines) for
CI engines; gasoline and natural gas for SI engines. Residual oil
with a sulfur content of 0.5 percent or less is considered to be
acceptable - higher sulfur concentrations are not recommended because
of possible excessive engine wear and acid compound contamination of
the lubricating oil.
No reference was found concerning the use of coal either directly
(pulverized or in a slurry) or indirectly {coal gasification) for these
e'ngine types.
Based on unpublished data it was determined that the total
energy produced by 1C engines amounts to;
. Diesel (distillate and residual oil) 71.6x10 J/yr
. Dual Fuel ' 22x10 J/yr
. Natural Gas 338xl015 J/yr
. Gasoline 48xlQ15 J/yr
Total 480xl015 J/yr
Natural gas accounts for 70.5% of the total energy produced by these
engines. mIndeed, the use of natural gas is even greater when duel fuel
engines are operating with a high percentage (90-95%) of natural gas on
an energy basis. For 90% natural gas usage in dual fuel engines, natural
gas supplies 74.6% of all the energy produced by reciprocating internal
combustion engines.
313
-------
Figure A-10.10-1. Internal combustion engine with integral gas compressor (Cooper Energy Services)
-------
Further, natural gas fueled engines used in the oil and gas produc-
tion and oil and gas industry categories account for 275x10 J/year or
81.2% of the energy produced by all natural gas fueled devices. This is
due to the close physical proximity of the fuel supply to the device, e.g.,
an engine driving a natural gas pipeline compressor will be a very short
distance from a fuel source (the pipeline).
Fuel use trends, while not quantitatively established, are anticipated
to result from shortages in both natural gas and low sulfur content fuel oils
(especially the former). Thus, in the future dual fuel diesel engines could
be operated with a higher percentage of fuel oil.
Trends In Equipment Type, Age, SizeAnd Ose
Reference A-10.10-2 indicates that there is no discernible
trend in 1C engines, especially those with outputs between 746 and
1864 kw (1,000 - 2,500 HP). There has been a tendency toward including
turbochargers on new engines and retrofitting turbochargers on older
naturally aspirated units in the interest of improved fuel economy.
There has also been some discussion by engine manufacturers to convert
natural gas fueled engines to utilize pj.1 fuels in the event that rising
natural gas prices'make it economically justifiable.
The matter of engine age, especially for large stationary units,
is difficult to establish since major components, e.g., cylinder head,
crankshaft, connecting rods, main and rod bearings, will last indefinitely
if the engine is properly operated. Minor overhauls are performed after
8,000 to 16,000 hours (0.9 to 1.8 years) and include new piston rings,
new or reground valves, and occasionally new or rebuilt pistons. After
20,000 to 80,000 hours (2.3 to 9.1 years) a major overhaul is performed
and may include new cylinder liners in addition to those items covered
by the minor overhaul.
Usually the old parts are either rebuilt to original specifica-
tions or replaced with identical new items. Occasionally the new parts
have been altered from original specifications, e.g., different piston
crown design, injector timing, etc., to reflect component improvement.
315
-------
This distinction is quite important since the former component replace-
ment approach probably will not require that the engine be subject to
emission regulations if it had not been previously necessary. The
latter approach, i.e., substitution of new design components, may require
that the engine be subject to emission regulations if these new
components result in greater emissions or emission of a new pollutant.
Total Number And Geographic Distribution
An unpublished study has produced the total number of
stationary internal combustion engines categorized primarily by fuel
type (diesel, dual fuel, natural gas and gasoline) and application.
For some applications the strict definition of "stationary" is not
clear but seems to include those engines which are used in a non-
propulsive mode and those propulsive units whose area and/or velocity
of movement is "small". For the latter category "small" would refer
to the subsequent spatial dispersion of air pollutant emissions as
being governed by atmospheric motion and not by the motion of the
source. This definition would then include, for example, gasoline
powered lawn mowers but would exclude diesel powered refrigeration
units used on long distance tractor-trailer rigs. Table A-10.10-2
herein is reproduced from the unpublished study.
No information was contained in the unpublished study or
found elsewhere as to the geographic distribution of the devices.
Limitations In Equipment Uses And Fuels
Large capacity stationary 1C engines are designed to operate
for long periods of time at rated power and, as a result, there is
little flexibility to change basic operational characteristics in an
effort to reduce air pollutant emissions. Such characteristics as
- spark or injection timing are not varied from the manufacturers
specifications. Indeed, such specifications were originally established
in older models as corresponding to maximum fuel efficiency. Obviously,
engines used in utility and industrial electric generation are not
permitted any variation in rotational speed.
316
-------
TABLE A-10.10-2. STATIONARY 1C ENGINE APPLICATIONS
Category
DIESEL
Oil & Gas Production
Off shore drilling
Land drilling
Oil ft Gas Transport
Electric Generation
General Industrial
i Agriculture
Municipal water
supply
Marine nonpropulsive
Construction, small
Miscellaneous, large§
Construction, large
Portable compressors^
Welders
Pumps
Generator sets(stand by)
<50 kw
50 kw - 400 kw
400 kw - 1000 kw
c
o
+J
u i"
"o *^
O VI
&, •«-
c
^
c
} soot
5flt
150t
200+
JL
5,000*
5,000
1,700
5,000
9,000
8,000
5,000
7,000
8,000
1,500
* .
c
o
«0 4-*
O. 3
Q-
675
3,050
500
400
2,100
15,000
50,000
~
50,000
90,000
80,000
25,000
70,000
160,000
30,000
i_
s
o
a, o-
oix:
(o
0)
<£
350
350
2000
2500
120
100
50
750
240
75
55
100
75
250
750
i_
o
u
ID
U-
•
to
=> >>
IO -C
C
KC
2000
2000
6000
2600
3000
3500
500
100
500
500
100
1000
500
250
100
I
c
o
•i 82
^i*
Jr t- i-
£|1
IB
3
C
c
Q. •!-
c
ID
3
C
C
) included
> In
) Diesel
* .
• H3 ,
o. 3
o
CL
1 included
f 1n
) Diesel
91,000
266,000
5,600
3,050
4,000
I 4,500
( 4,000
450
2,000
1,500
,_
s
o
a.
a> Q-
Q- *
(O
01
"*
100
15
200
350
750
2000
750
200
100
300
u
o
u
u.
•o
o
0.8
0.8
0.75
0.7
0.8
0.8
0.8
0.9
0.8
0.8
0.45
0.9
0.6
- *
£,
«3
I/I J-
r— W
i
bj in a.
r— »-H
It]
C
C
?,228
6,000
17,063
9,776
1,376
1,708
19,200
51 ,800
14,400
166.5
162
9
1,080
"O
m
o
c
K»
VI
C
o
X
X
X
X
X
X
X
X
X
TJ
X
Basis of estimate
HcGowin, Gas Facts'
FPC, Diesel & Gas
Power Costs
AGA Market Study
AGA Market Study
AGA Market Study
AGA Market Study
McGowin
Southwest Research
Institute^
Sou tlwe s t jtesearch
Instltute+T
FPC, Diesel & Gas
Power Costs
AGA Market Study
AGA Market Study
AGA Market Study
OJ
H
CO
Footnotes appear at end
-------
TABLE A-10.10-2 (continued). STATIONARY 1C ENGINE APPLICATIONS
\
Category
General Industrial
Industrial shaft
power
Plant air
Air conditioning
Commerlcal shaft
power
Municipal
water supply
waste treatment
GASOLINE
Agriculture
M1sc. machinery
Irrigation
General Industrial
Generator sets
>5 kw
Compressors
Welders
Miscellaneous
Construction
Small (<15 hp)
*•
a
o
*f i
u fc-
•§•£?
O fcfl
0.*-
c
r- 3
to
C
"*
20,000
5,000
35,000
1 7,000
18,000
5,000
5,000,.
12,600,0003
,
c
o
tt— ^
^°^ jl.
TO •£-
3 5
a =
o
a.
2,900
750
3,760
600
2,100
1,740
400,000
10,000
350,000
70,000
180,000
50,000
40,000
5 63,000,000
t-
lt
o
a.
a.
Oi Si
o>
tQ
t-
01
«s
200
100
80
2000
120
400
30
100
55
55
55
55
150
4.2
t-
o
<*->
^i
to
ii.
•a
to
o
0.75
0.5
0.4
0.6
0.75
0.45
0.5
0.75
0.5
0.5
0.5
0.5
0.5
0.5
&
to
!
l~~ I"
C.
C
ft
5000
4000
2000
1000
3000
4000
200
2000
400
400
400
400
500
50
1
c
o
U ***£
3 W) O
TO Olr-
C r—
L. a x
a. 1/1
1,11 "sir
s> - o.
-C
±i
c
c
•*
60
750
715
188
1100
1
^
o
0 *^
3 J2C
»•- ^ X
a. ^
?'•-"£•
flj *™" ^p-
c ,3 i
-C
,_, *•
U
c
c
2,175
150.4
240.6
720
567
1,566
1,200
1,500
7,150
1,500
6,615
•u
m
, o
i f
c
ta
c
o
o
X
X
X
X
X
X
•a
s
_J
01
t~^
1.
s»
X
X
X
• x
X
X
X
X
X
X
X
•u
01
OJ
o.
1/1
i *
c
c
o
X
X
X
X
X
X
X
XI
01
a>
a.
Qj
g^.
X)
1.
to
X
X
X
X
X
X
X
X
X
Basis of Estimate
AGA Market Study
AGA Market Study
AGA Market Study
AGA Market Study
AGA Market Study
AGA Market Study
Current Industrial
Reports, Indus-
try contacts
Current Industrial
Reports
See footnotes on following page.
-------
TABLE A-10.10-2 (continued). STATIONARY 1C ENGINE APPLICATIONS
Footnotes
* Annual production multiplied by life in years (based on estimated service life of 5000 hours for
diesel engines, 4000 hours for gasoline engines, or as noted) to complete population.
t Approximated, based on estimated population and annual usage.
* 7500-hr service life assumed.
§ Applications include pumps, snow blowers, aircraft turbine starters, etc.
# Excludes mobile refrigeration units.
** Population estimates come from the AGA market study. Annual production is not estimated for this
category since production has been changing rapidly, decreasing continuously since 1966 and,
therefore, an annual estimate of production could.be misleading.
tt includes transport, distribution, gathering, and storage.
tt Pull combines, balers, sprayers, dusters, etc.
§§ Estimated service life of 5 years.
-------
Aside from dual fuel engines there is a fairly definite
limitation in fuel usage. Diesel engines have some flexibility in
substituting a lower grade fuel oil especially if the engines include
a precombustion (divided) chamber (Ref. A-10.10-3). However, the use of
residual oil with a sulfur content greater than 0.5 percent is not
recommended.
Quantity And GeographicDistribution Of Fuels Used
No information was obtained on this subject.
AirPollutant Emissions
Air pollutant emissions for natural gas fuel reciprocating
engines, as found in Reference A-2-2 are shown in Table A-8-1. The
emissions for this fuel classification are much greater than for any
other fuel.
321
-------
A-10.11 STATIONARY GAS TOKBINES
Major United States Manufacturers
Table A-10.11-1, abstracted from Reference A-10.11-1, lists the
major U.S. manufacturers of stationary gas turbines along with their
applications and fuels used.
Associations
Gas turbine manufacturers are represented by the American Society
of Mechanical Engineers, Gas Turbine Division (New York, N.Y.).
Basic EquipmentAnd Combustor Design
A stationary gas turbine is composed of three basic components:
1. A compressor which produces high pressure air.
2. A combustion chamber within which fuel and air are burned.
3. A turbine which supplies energy to the compressor and
delivers useful shaft energy to the load.
There are several variations on each of these basic
components:
Compressor
The compressor may consist of a few (one or two) centrifugal
stages wherein -the air inlet is in the axial direction and the discharge
is in the radial direction (with respect to the axis of rotation).
Usually, this arrangement is employed on smaller capacity units. On
larger units the air flow is mainly in the axial direction with the
compressor consisting of a large number of stages (up to 17) with each
rotor stage separated by a set of stator blades (which redirect the
air flow for the following rotor stage).
Combustor
For smaller units there may be only a single combustion chamber
arranged in an annular manner around the axis of rotation. Larger units
will contain a series of individual combustor chambers (as many as 18)
322
-------
TABLE A-1Q.11-1. MAJOR UNITED STATES GAS TURBINE MANUFACTURERS
(Ref. A-10.11-1)
Manufacturer
Ai Research
AVCO Lycoming
Cooper-Bessemer
Curtiss-Wright
Delaval Turbine
Detroit Diesel Allison
Dresser Clark
General Electric
Ingersoll-Rand
Rohr Industries
Solar
Turbodyne
Turbo Power and Marine Systems
Westinghouse
Application*
G, SP
.1
SP
SP, G
CP
G, GC
SP
SP, G '
SP
PG
G, GC
G, SP
I
G, PG, PL
Fuelt
JP-4, JP-5, Jet A
NG, No. 2
NG, GT1, GT2
NG, GT1, GT2, No. 1, No. 2
NG, GT
NG, No. 1, No. 2
G, L (gaseous or liquid
available)
(Not specified)
NG, Diesel (grade not
specified)
No. 1, No. 2, JP-5, Jet A
NG, GT1, GT2
NG, BF, NO. 1-6, GT1-4.
NG, No, 1, No. 2
NG, GT1 - GT4
* CP s» Compressor drive
G = Generator drive
GC a Gas con^ressor drive
I «• Industrial
PG = Packaged power plant
PL = Peak load
SP * Shaft power
"f* BF = Blast-furnace gas
GT1 - GT4 = Gas turbine fuels per ASTM Spec. D-2880
Jet A = Aircraft kerosene
JP-4, JP-5 = USAF jet fuels or equivalent
NG = Natural gas
No. 1 - No. 6 - ASTM D-396 burner fuels or D-975 diesel fuels or
equivalent.
323
-------
with the chambers also arranged in an annular manner. In either situation
the combustor's functions are to inject and atomize the fuel (in the case
of liquid fuels3, mix the fuel vapor and air, initiate combustion,
stabilize the flame zone, and, by introducing additional air, reduce
the combustion gas temperature to a level consistent with the turbine's
capability. This last requirement will necessitate that the device
operate, on an overall basis, with a significant amount of excess air.
Turbine
The turbine may also be of the radial or axial flow design with
the former typically having one stage and the latter having anywhere from
1 to 6 stages. In addition, the multi-stage arrangement can have some of
the stages mounted on a shaft separate from the compressor shaft. In this
instance the "free" turbine stage(s) is delivering useful energy to the
load. This configuration allows the free turbine rotational speed to be
matched more closely with that required by the load. The compressor and
its turbine stage(s) can then rotate at a rate different from the free
turbine and the load.
: At present, there are three gas turbine cycles in use—
simple, regenerative and compound (Ref. A-10.11-2). In the simple
cycle the exhaust gas is discharged without any waste heat recovery.
This cycle will show a thermal efficiency on the order of 25' to 30%.
The regenerative cycle employs the turbine exhaust gas, at a temperature
of 756 to 867 K (900 to 1100°F), in a recuperative air preheater heat
exchanger. Typical thermal efficiency is from 35 to 37%. The combined
cycle is another manner in which waste heat is recovered from the
turbine exhaust. In this case, the exhaust gas is used to produce
steam in a steam boiler before being exhausted. The steam boiler
output may then be used to drive a steam turbine in which case the gas
turbine generates typically 60% of the total power produced with the
steam turbine producing 40%. In some cases, additional fuel is
burned with the oxygen rich turbine exhaust gas to produce higher
capacity/quality steam in the boiler. Thermal efficiency for the
compound cycle gas turbine is on the order of 40 to 42%.
324
-------
Figure A-10.11-1 shows a simple cycle gas turbine unit rated at
2.8 MW and intended for gas compression and shaft power applications.
Current Fuel Use,Trends And Properties
According to Reference A-10.11-1, and as shown in Table A-10.11-1,
current stationary gas turbine fuel use includes natural gas, residual and
distillate oils, and in one instance blast furnace gas. No use of coal is
noted because of possible particulate erosion of the turbine blades. Indeed,
Reference A-10.11-3, which is a listing of gas turbines on a worldwide basis,
does not contain a single listing of a gas turbine using coal as a fuel.
Dual fuel operation is not typical (Ref. A-10.11-4). This
manufacturer's gas turbines cannot operate simultaneously on gaseous
and liquid fuels—rather a change in the fuel supply system must be
made when switching from a gaseous to a liquid fuel and vice versa.
This fuel supply system change does not require any change in the
combustor.
Information obtained, from the Federal Power Commission (Kef. A-10.11-5)
listed net electrical energy produced by gas turbines for the years 1970-1975
by fuel type. (This is not to be confused with fuels consumed by gas turbines
in electrical generating activities.) The FFC data, shown in Table A-10.11-2,
does not differentiate between fuel oil types, e.g., distillate, residual,
etc.
These data are of prime interest in establishing trends in fuel
usage. As can be seen from Table A-10.11-2 the general trend since 1970
has been toward a greater utilization of fuel oil at the expense of natural
gas with the dip in 1973 probably due to the combined effects of the national
economic recession and oil embargo imposed by the producing nations.
Trends, In Equipment Type, Age, Size And Use
As noted in Table A-10.11-1 stationary gas turbines find a widespread
application in electrical generation and pipeline activities (oil pumping and
gas compression). According to Reference A-10.11-2 installed gas turbine
capacity in electrical generating in 1970 was 16,500 MW - approximately 5%
325
-------
Figure A-10.11-1. 2.8 Mw gas turbine (Solar Div. International Harvester)
326
-------
TABLE A-10.11-2. NET ELECTRICAL ENERGY PRODUCED BY GAS TOHBINES
CIO15 joules)
Year
1970
1971
1972
1973
1974
1975
Nat, Gas
28.3
37.7
39.0
47.4
45.3
30.0
Oil*
26.8
41.4
66.7
58.8
70.0
50.2
Total
55.1
79.1
106.0
106.0
115.0
80.2
Oil, % Of Total
48.7
52.3
63.1
55.4
60.7
62.6
*type not specified
327
-------
of the capacity from all sources. As of December 31, 1975 these figures
had increased to 43,526 MM and 8.6% (Ref. A-10.11-6). Thus, in 5 years,
gas turbine electrical generating capacity had increased by 164%. By 1980
planned additions will increase gas turbine capacity to 55,950 MW - an
increase in capacity of 239% between 1970 and 1980.
Current electrical utility plans still envisage the gas turbine
in a peaking role with a required life expectancy of 30 years. As a
result only 11 combined cycle units have been planned to be added in
an electrical generating application (Bef. A-1Q.11-7). (Peaking usage of a
combined cycle unit would require that the., steam boiler undergo several on-
off cycles per day. This intermittent operation of a steam boiler is not
desirable. In addition, the gas turbine portion of the unit can be brought
on-line much faster than the boiler, i.e., the steam boiler response time
is the controlling factor in the overall unit response time.)
As of 1971, according to Reference A-10.11-7, the largest gas
turbine electric generating station in the United States was the
Astoria, New York station of Consolidated Edison. This station had
13 units with a combined capacity of 744.5 MW.
• •
The largest single gas turbine produced in the United States
has a capacity of approximately 100 MW (Bef. A-10.11-7). It is a very
common practice for manufacturers to compound two or more separate
units together and sell them as a single unit with a nameplate capacity
equal to the sum of the individual, separate units. Thus, the 176.5
MW unit located at Consolidated Edison's plant in Astoria, New York,
is actually composed of 4 individual gas turbines packaged together.
Projections (Ref. A-1Q.11-2) indicate that a. 1,000 MW plant will
be available in the future and will probably be composed of 5 combined
cycle units each generating 200 MW.
Figure A-10.11-2, reproduced from Reference A-10.11-2, reports
the sales of gas turbines for gas compression service by power rating
for the years 1965 through 1970. Tliese figures indicate the increasing
328
-------
acquisition of units with ratings of 7457 kW (10,000 hp) and larger.
No further information was obtained on trends in gas compression
service, however, additional information is probably available.
IMS 1W6
Figure A-10.11-2. Trends in size of turbines sold for gas compression
service. (Ref. A-10.11-2)
Total NumberAndGeographic Distribution
As of January 1, 1974, according to Reference A-10.11-1, there
were 350 gas turbines in gas transmission line service in the United
States with a total power rating of 1,970 MW (2.64 x 10 hp). No
information was found on the geographic distribution of gas turbines
used in this service.
A survey conducted by the Federal Power Commission in 1975,
and'reported in Reference A-10.11-5, tabulated the state-wide distribution
of gas turbine electrical generating plants and installed capacity.
(The survey did not ask"for information broken down on a per device
basis.) The results of this survey are shown in Table A-10.11-3 and
indicate that there were gas turbines at 506 plants in the United States
with a combined capacity of 43,526.6 MW.
A similar survey conducted in 1971 {Kef. A-10.11-3) tabulated a
total of 761 gas turbines installed in electric generating service.
Only 15 units had any form of waste heat recovery, and only 4 of these
329
-------
TABLE A-10.11-3. GAS TURBINES INSTALLED IN ELECTRICAL GENERATING
State
Alabama
Arizona
California
Connecticut
Florida
Hawaii
Illinois
Iowa
Kentucky
Maine
Massachusetts
Minnesota
Missouri
Nebraska
N . Hampshire
N. Mexico
N. Carolina
Ohio
Oregon
S . Carolina
Tennessee
Vermont
Washington
Wisconsin-
No.
Plants
4
14
20
15
25
3
19
11
5
3
16
3,5.
15
8
4
3
11
25
3
21
3
5
3
15
Capacity,
MW
604.4
1,719.8
1,205.4
454.7
4,532.6
131.9
2,227.0
637,5
190.1
45.1
567.7
953.8
717.3
460.6
88.0
44.5
894.4
1,688.7
719.2
1,512.5
2,034.0
129.0
120.0
1,048.5
State
Alaska
Arkansas
Colorado
Delaware
Georgia
Idaho
Indiana
Kansas
Louisiana
Maryland*
Michigan
Mississippi
Montana
Nevada
N. Jersey
N. York
N. Dakota
Oklahoma
Pennsylvania
S . Dakota
Texas
Virginia
W. Virginia
Wyoming
No.
Plants
6
3
4
7
10
1
10
14
6
12
17
10
2
4
25
31
1
9
34
1
24
7
1
1
Capacity,
MW
281.6
308.1
200.0
156.7
1,255.2
50.0
466.2
756.1
90.8 •
1,419.3
993.4'
223.2
47.1
176.0
4,260.5
4,389.6
8.0
467.4
3,067.2
12.5
1,610.7
525.7
18.6
16.0
* Includes District of Columbia
330
-------
were a combined cycle device. The vast majority of the units (746 out
of 761} were simple open cycle gas turbines.
Limitations In Equipment Uses And Fuels
A definite limitation in gas turbine operation is the gas
temperature at the turbine inlet. Present turbine materials and blade
designs require that this temperature not exceed 1255 to 1310 K
(1800 - 1900°F). Material and blade design advances are expected to
raise this limit to 1590 K(2400°F), with the blades being cooled
by circulating air bled from the compressor.
The use of heavy residual oils is limited primarily by metals
content as related to turbine blade corrosion.
The direct use of coal, as opposed to gasified coal, is not
anticipated for use in a gas turbine. This is because of turbine
blade erosion due to the fly ash in the combustor exhaust gases.
Quantity And Geographic Distribution Of Fuels Osed
No specific information was obtained on this subject. However,
the relative amount of natural gas and fuel oil used can be approximated
•from proportioning the data in Table A-10.11-2 (for 1975} with that in
Table A-10.11-3 (also for 1975}, Thus, if it is assumed that fuel oil
supplied 62,57% of the energy throughout the United States, then this
value can be applied to the state-wide capacity distribution. The
balance of the fuel used would be natural gas.
»-
AirPollutant Emissions
Air pollutant emissions from natural gas fueled gas turbines
are shown in Table A-8-1. A more detailed examination of the NEDS listing
(Bef. A-2-2) indicates the NO emissions for gas turbines shown in
A
Table A-10.11-4.
331
-------
TABLE A-10.11-4. NO EMISSIONS FROM GAS TURBINES
X
Fuel
Distillate
Natural Gas
Residual
Jet Fuel
Process Gas
No. of Records
21
144
2
1
1
169
kg/Year
1 561 000
19 627 000
0
0
238 000
21 426 000
NO
Short Tons/Year
1,717
21,590
0
0
262
23,569
If the number of records does indeed correspond to the
number of gas turbines inventoried, then the NEDS listing is decidely
incomplete since there are at least 1111 units in gas compression
and electric generation. Even if the number of records corresponds to
the number of locations using gas turbines (with each location having
one or more units), the NEDS listing still appears incomplete. Reference
* *
A-10.11-5 tabulates 506 locations using gas turbines in the electric
generating service alone.
332
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A-1Q.12 PETROLEUM REFINERY PROCESS HEATERS
Major Manufacturers
No published information was found to be available. Contact with
refineries, API (American Petroleum Institute), and construction companies
provided the following list of major manufacturers:
Born, Inc. (Houston, Texas)
. C-E Lummus (Bloomfield, New Jersey)
. Foster Wheeler Energy Corporation (Io.vingston, New Jersey)
. Heat Research Corp. (New York, NY)
. Petro-ehem Development Co., Inc. (New York, NY)
» Selas Corp. of America (Dresner, PA)
The major burner manufacturers are:
John Zink Company (Tulsa, OK)
. National Airoil Burner Co. (Philadelphia, PA)
. Coen Company (Burlingame, CA)
Associations
The American Petroleum Institute is the major association. Activities
related to petroleum refinery heaters are concentrated in the API Manufacturers
and Contractors Subcommittee on Fired Heaters and in the API Committee on
Stationary Source Emissions.
Basic Equipment andCombustor Designs
The function of refinery process heaters is to'provide heat for three
basic functions:
1. temperature increase of liquid oil
2. vaporization
3. promoting chemical reactions.
All heating is indirect in that the flame does not directly contact the
material processed. Construction consists of an outer shell, refractory
lining, internal tubing to contain the heated process material, burner equip-
ment arranged for proper flame shape, and air inlet and exhaust ducting for
proper heat distribution and combustion. Heat is transferred by flame
333
-------
radiation and by convection. Furnaces are generally divided into two
sections: (1) a radiant section in which tubes are exposed to direct flame
radiation and (2) a convection section. The process oil being heated is
generally introduced in the cold end of the convection section and exits
after passing through the radiant section. Some heaters may not have a
convection section.
There are two major types of refinery heater construction:
1". Vertical tube cylindrical shell heaters
2. Horizontal tube box heaters.
Manufacturers indicate that construction is about equally divided between
these two types so that neither type is prevalent. Variations of these basic
types occur based on the specific needs for heat distribution within the
heater as discussed in Reference A-10.12-1. The proper division of heat
delivery by radiation and convection is the most critical design parameter.
Improper design or operation can cause tube overheating resulting in product
coking or tube failure. Product output temperature is the primary control
parameter.
The heater process function has a major influence on tile combustion
process. Processes can be ordered by the degree of process sensitivity to
combustion changes:
1. Heat medium heaters - heat oil or steam used as heat
source in other processes
2. Low temperature reboilers
3. Crude heating
4. Chemical reforming.
There are many other processes performed but the above are the
primary ones.
The process sensitivities are indicated by manufacturers to be more
important than heater design in influencing limitations on combustion modifi-
cations that could be performed for emissions reduction or efficiency improve-
ment.
334
-------
Combustor (burner) designs can be classified by the following
characteristics:
1. Draft
» natural
. balanced or forced
2. Burner orientation
. horizontal or side fired
. vertical-upward
„ vertical-downward
3. Atomization (liquid fuels)
« mechanical
. air
. steam
4. Air register type
. straight injection
. swirl promoting
5. Flame shape
The majority of refinery heaters have natural draft burners. Horizontal
tube box heaters tend to have many more burners than vertical cylindrical
heater types. Horizontal tube box heaters can be fired with burners in
-any orientation. Vertical tube cylindrical heaters normally have
burners located at the bottom firing vertically upward. Most natural
draft burners employ steam for liquid fuel akomization and tend to have
fairly simple straight injection air registers. Natural draft designs
generally do not have any windbox around the burners and air preheating
cannot be performed. Excess air required tends to be higher than for
forced draft burners.
Forced draft designs require a windbox to distribute the
pressurized air from a fan. These units are, therefore, more adaptable
to air preheat and to the use of flue gas reeirculation. Higher air
pressures also allow the use of swirl promoting air registers. This
improves the fuel-air mixing allowing operation at lower excess air
compared to natural draft types.
335
-------
Current.Fuel Use, Trends And Properties
About 50% of total refinery energy is provided by fuel gas
generated in "the various refinery processes. This gas varies widely
in composition, containing carbon monoxide, hydrogen, various light
hydrocarbons and inerts. Natural gas may be mixed in to reduce heat
content variation but heat content can still vary from 19 to 74 MJ/m
(500 to 2000 Btu/Cf). It is not possible to specify a typical refinery
gas since properties vary with time in every refinery. Refinery gas
composition at various levels of heat content is illustrated in
Table &-10.12-1 based on samples collected in refineries by KVB during
the study reported in Reference A-1Q.12-2. The variation in composition
can occur very quickly and this makes tests of these devices difficult
because stable operating conditions cannot be established. Some heaters
are operated at a constant air flow high enough to compensate for fuel
variations and therefore excess oxygen varies with fuel composition.
Other units may have excess air controls to adjust air as fuel composition
changes.
Refinery gas fuel is supplemented with oil or natural gas to
provide a total refinery, energy input to heaters equivalent to about
3 to 12% of the crude input energy content. Smaller refineries
require 3 to 5% and larger refineries require 5-12% heater heat input
based on crude heat content. Crude energy content is about 42 GJ/m
(6.3 million Btu per barrel). Heating a crude oil from 293 K to 543 K
(68°F to 700°F) requires a heat input of about 660 MJ/m3 (100,000
Btu/barrel) or about 1.5% of the crude heat content. This heating is
required for the initial crude distillation process and the crude heaters
required are generally the largest in the refinery. A large refinery
will have up to 6 separate crude heaters.
Details on refinery fuel use by device type are not published.
However, the general trend is to operate heaters on refinery gas and
steam boilers on oil or natural gas. Therefore, while overall only
50% of the refinery energy is provided by refinery gas, more than 50%
of heater fuel is refinery gas.
336
-------
TABLE A-10.12-1. TYPICAL REFINERY FUEL GAS COMPOSITION
Conponent
H hydrogen
N nitrogen
CO carbon dioxide
CH, methane
4
C?H ethylene
C H ethane
2 D
C_H propene
3 6
C H propane
i-C.H, .. i-butane
4 10
n-C,H,_ n-butane
4 10
CJH pentane
Heating value
MJ/m3
(Btu/CF)
Composition, mole fraction
1
0.644
0.010
0.245
— —
0.055
-—
0.034
0.004
0.002
0.006
25.66
(690)
2
0.535
0.027
0.278
0.008
0.071
-— —
0.078
0.002
0.001
"*"•""""
30.0
(807)
3
0.245
0.014
0.004
0.537
0.006
0.136
0.003
0.042
0.003
0.005
0.005
38.8
(1041)
4
0.393
0.014
0.001
0.240
0.039
0.111
0.030
0.087
0.037
0.039
0.010
45.7
(1227)
5
0.259
0.023
0.001
0.248
0.026
0.088
0.093
0.143
0.043
0.069
0.007
57.1
(1534)
6
0.155
0.018
0.307
0.039
0.087
0.106
0.120
0.030
0.123
0.015
64.2
(1724)
LO
Ut
-4
-------
Trends In Equipment Type, Age, Size And Use
Information on refinery heater type, age, size and use is not
published. The reported reason for this lack of data is the proprietary
and competitive nature of the industry.
Contact with manufacturers and refineries indicates that there
is a general trend toward increased use of air preheat and forced draft
burner designs. These trends are in the direction of improved efficiency
through reduced excess air and reduced stack temperatures.
Most older heaters are designed for gas firing only. Newer
designs are built for both gas and oil firing and many of the older
heaters are being converted to fire oil. No evidence was found for
any significant use of solid fuels.
. Increased requirements for low sulfur fuel oil as a replacement
for natural gas can be expected to cause a shift in refinery processes
away from gasoline processes such as cracking and reforming and toward
increased hydrogen desulfurization and demetallization.
Total Number And Geographic Distribution
No published data on petroleum refinery heaters is available.
The EPA NEDS file indicates about 2900 such heaters in the U.S. There
were 256 petroleum refineries tabulated in the 1976 annual refinery
survey (Ref. A-10.12-3). Table A-10.12-2 shows that most (32%) of these
refineries are located in Texas and California. Table A-10.12-3 shows
the distribution of refineries by crude capacity. The average refinery
size is about 8000 m /day (50,000 barrels/day). However, 52% of the
refineries are very small, less than 4800 m /SD (30,000 B/SD) and
account for only 10% of total capacity. These refineries would be
expected to have only a few heaters and subsequently low total emissions.
There are 60 refineries in the range of 4900-23900 m /SD (30,000-
150,000 B/SD) accounting for 36% of total capacity. The 26 largest
refineries account for 43% of total capacity. Excluding the small
refineries (under 4800 m /SD), the average refinery size is 17,610
m3/SD (111,000 B/SD).
338
-------
TABLE A-10.. 12-2.
GEOGRAPHIC DISTRIBUTION OF PETROLEUM REFINERIES
IN THE UNITED STATES
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Delaware
Florida
Georgia
Hawaii
Illinois
Indiana
Kansas -
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Missouri
Han tana
Nebraska
New Jersey
New Mexico
New York
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Number of
Refineries
3
4
1
4
35
3
1
1
2
2
11
7
11
3
19
2
6
3
5
1
7
1
4
7
2
3
7
12
1
11
1
46
7
1
7
3
1
11
256
Crude Ca
Barrels per
Stream Day
53,000
78,158
4,211
62,425
1,993,503
65,000
150,000
6,000
19,400
107,105
1,232,958
527,300
468,940
169,500
1,827,031
31,211
151,395
223,905
346,842
108,000
164,016
5,500
562,764
106,305
114,500
60,163
614,500
559,719
14,737
796,415
44,800
4,144,778
158,878
55,000
383,105
20,200
46,800
194,557
15,687,321
pacity
Cubic Meters
per Stream Day
8 425
12 425
669
9 924
316 908
10 300
23 845
954
3 084
17 027
196 000
83 825
74 548
26 945
290 444
4 962
24 067
35 594
55 138
17 169
26 074
874
89 463
16 900
18 200
9 564
97 637
88 979
2 343
126 606
7 122
- 658 897
25 257
8 743
60 902
3 211
7 440
30 929
2 493 821
339
-------
TABLE A-10.12-3. DISTRIBUTION BY CAPACITY OF
PETROLEUM 1EFIMERIES IN THE UNITED STATES
Hefinery Capacity
Range
1000 B/SD* m3/SD
0-10 0
11 - 20 1.7
21 - 30 3.3
31 - 40 4.9
41 - 50 6.5
51 - 100 8.1
101 - 150 16.1
151 - 200 24.0
201 - 300 32.1
301 - 460 47.8
- 1.6
- 3.2
- 4.8
- 6.4
- 8.0
- 16.0
- 23.9
- 32.0
- 47.7
- 73.1
Number of
Refineries
77
28
27
15
23
40
20
10
8
8
256
Percent of
Total Number
30
11
11
6
9
15
8
4
3
3
100
Percent of
Total Capacity
3
3
4
3
7
20
16
11
13
19
100
*B/SD - Barrels per stream day
340
-------
Data fathered fay KVB for inventory of NO from stationary
X
sources in the Los Angeles area (Ref. A-10.12-2) indicates that small
refineries have 4 to 10 heaters but larger ones can. have up to 60
heaters per refinery,and the average is about 26 heaters per refinery.
Using these averages together with total refinery count data by
capacity indicates that there are about 7000 refinery heaters in
the United States.
Every refinery has at least one crude heater. This is usually
the largest heater since all the refinery input is processed through
this unit as the initial step in the refining process.
Limitations inEquipment Uses and Fuels
Refinery process heaters are designed to perform a specific
refining process and therefore are not readily adapted to other uses.
The only changes that may occur relate to the processing of crudes of
differing source and properties.
Refinery heaters have been primarily fired with refinery gas but
distillate and residual oils are now being used in greater amounts. The
main fuel use limitation relates to the heat distribution to the
heater tubes. A change from a gas fuel to a heavy oil fuel would increase
the fraction of heat transferred by radiation. This could result in •
problems with internal tube coking or other overheating failures. Heaters
designed for oil firing require larger radiant fireboxes, larger tube
clearances and greater distances between the burners and tubes.
Convection sections on heaters designed for gas fuel have
high density finned tubes that are subject to plugging when oil is
used. Conversion to oil may require retubing with wider spaced fins.
Sootblowing equipment must also be installed.
Firing of liquid fuels that contain sulfur, vanadium and sodium
can present problems with heater tube corrosion in heaters designed
for gas fuel. This limits use to light distillate oils or requires
retubing with corrosion resistant tubes.
341
-------
Firing heaters on oil requires about 20% excess air while gas
fuel requires only 5-10% excess air. Therefore, natural draft heaters
may have a lower heat input capacity on oil because of draft limitations.
This can be resolved by conversion to forced'draft burners.
Quantity And Geographic Distribution Of FuelsUsed
Petroleum refineries generate many petroleum fractions that can
be used as fuels in process heaters:
. Liquified petroleum gas
. Refinery process off gases
. Naptha
. Light Distillate
. Atmospheric Residue
. Vacuum Residue
. Crude
. Tar
. Petroleum Coke
Information on the usage by refinery process heaters of each of the
above was not found. However, Reference A-10.12-4 indicates the process
heaters consume about 65% of refinery fuel input, with steam generation
consuming 25% and electricity generation consuming the remaining 10%.
Reference A-10.12-5 indicates the following distribution of fuel
use by type in petroleum refineries (Table A-10.12-4)t
TABLE A-10.12-4. FUEL USE IN PETROLEUM REFINERIES
Crude Oil
Distillate Oil
Residual Oil
Liquified "Petroleum Gas
Natural Gas
Refinery Gas
Petroleum Coke
Coal
% of Total
Fuel Use
0
1
11
1
31
40
16
0
Average Rate,
TJ/day
0
78
858
78
2418
3120
1248
0
Total 100 7800
342
-------
This data is based on a, survey of 56 refineries constituting 92.9
of U.S. refinery capacity for July 1 - December 31, 1975. While
process heaters consume about 65% of total fuel energy input most
of this is believed to be refinery gas but specific use of each
fuel type in process heaters alone is not available.
Geographic distribution of fuels consumed in petroleum
refineries is given in Table A-1Q.1-1. The consumption rates are
highest in Texas and California, the states with the largest number
of refineries.
Air Pollutant Emissions
There are only a few published sources of refinery heater .
emissions. The Los Angeles Air Pollution Control District conducted
a study in 1956 (Kef. A-10.12-6).
A study performed for the California Air Besources Board
(Pef. A-10.12-2) provides data on NO emissions as shown in Figure A-1Q.12-1
•JC
for operation on refinery gas. This data was further correlated by
heater characteristics as shown in Figure A-10.12-2. Conclusions from
this correlation are that natural draft heaters with no air preheat
have lowest NO emissions and emissions per unit heat input are not
a function of size. The use of forced draft or air preheat increased
NO and results in a siae sensitivity.
The high variation in NO emissions per unit heat input for the
-------
100. .
§
IB (N
•rj O
O
S3
10..
1- .
4 Horizontal
dk Horizontal
O Vertical
Q Vertical
O BA APCD Data
lOOl—"" •"•""• Best Fit to KVB Data
——— Best Pit to BA WCD Data
—-*'""*"• LA AtCD Natural Gas Curve
-—*-—— IA APCD Refinery Gas Curve
S5
9
10
_J_ J I I I I III
BURNER ORIENTATION
T I
Natural Draft
Balanced Draft:
Natural Draft
Balanced Draft
0
I I
,
.^r^faiy, f
10
MMH/h
100
t I i
10 GJ/h 10°
Heat Input to Device
1000
Figure A-10.12-1. Total emissions of nitrogen oxide for refinery heaters and boilers
operating on refinery gas.
-------
1000-T-
100- •
5
o
IS
£ I
1/1 w
.jfc i i " i • « | l i | i i l
:--rpr+3or 17
"j^t- Es = 0.268(Q/N>'17
iLii — ^?n9'
r\ __r— ju/3
'•"L*--* **
= 0,158(Q/N)'17
- +301
ts = 0,135
--30I
1 L
-
_
^Natural Draft, Horizontal Burners..
Kl^Flue Gas Recirculation
• (2) Extremely Hot Refractory -
n = Number of Burners
i i i l l 1 1 1 1 1 I f 1 |
||
0.1
10
100
MMB/h
0.1
10
GJ/h
Heat Release per Burner, Q/N
-t-
100
1000
Figure A-10.I2-2. Emission factor for heaters and boilers with refinery gas fuel
-------
H S per cubic meter but variations from 3.0 to 5600 mg H S/m are
** £
observed. Sulfur content is regulated to 50 grains H_S per .100 cubic
3
feet (1144 mg H S/m ) in that area. No data are available for other
areas of the U.S.
Table A-8-1 presents the estimated total emissions from
refinery heaters in the United States based on NEDS data. The NO
X,
emissions are significantly higher than for the other categories.
However, the presence of only 2818 data records in NEDS relative to
an estimated 7000 total heater count indicates that the NEDS emissions
data may be low.
346
-------
SECTION A-11.0
POTENTIAL FOEL SAVINGS IN FOLP, PAPER AND PAPERBQARD INDOSTIY
Reference A-ll-1 indicates that the estimated 1975 fossil fuel
energy utilization in this industry was:
Purchased:
+ Waste Recovery;
Consumed;
1006xl015 J
834xl015 J
1840X1015 J
(excluding steam and electricity)
(excluding steam and electricity)
Consider that the purchased and waste recovery fuels were combusted in
a "device" with an efficiency of 80%. The following situation would
develop:
Purchase
Waste
1006xl015 J . , SOSxlO15 J __
834xl015 J
n = 80%
667xl015 J
Total
Energy
Demand
1472x10 J
Now consider the situation if the "device" efficiency was increased
15
to 81%. The waste energy input of 834x10 J would still be used as it is
available "free" and purchased fuel would be reduced to meet the same total
energy demand.
Purchase
Waste
983xl015 J 796xl015 J
834xl015 J
n-a»
676xl015 J
Total
Energy
Demand
1472x10
347
-------
Therefore, the amount of purchased fossil fuel has decreased by 2.3%, or
a savings of 23x10 J. This can be translated into a yearly savings in
residual oil amounting to:
23x10 J m 0>s5xlo6 m3 regidual oil (3.46xl06 Barrels)
41.8x10 J/m
or approximately 5% of the industries yearly purchase of residual oil.
348
-------
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349
-------
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350
-------
A-10.11-4 Private communication between Paul Canty (Solar Div. International
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"Voluntary Industrial Energy Conservation, Progress Report 3,"
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A-10.12-6 Devorkin, H. and Steigerwald, B. J»» "Emissions of Air
Contaminants From Boilers and Process Heaters," Joint District,
Federal, and State Project for the Evaluation of Hefinery Emissions,
Report No. 7, June 1958, (Published by Los Angeles Air Pollution
Control District).
A-11-1 Anon., "U.S. Pulp, Paper And Paperboard Industry Estimated Fuel
And Energy Use (For) First Six Months - 1975," American Paper
Institute, Inc.
351
-------
BLANK PAGE
352
-------
APPENDIX B
GASEOUS AND P&RTICUIATE EMISSIONS TEST METHODS MID INSTRUMENTATION
B.1.0 SAMPLE COLLECTION AND ANALYSIS
The emission measurements were made with instrumentation carried
in a mobile laboratory trailer, A plan view of this laboratory trailer
is shown in Figure B-l. Exterior and interior views are shown in
Figure B-2. The gaseous species measurements, except sulfur trioxide,
are made with analyzers maintained in the mobile laboratory, while the
particulate, smoke spot and sulfur oxides measurements are conducted
with portable analyzers carried to the sanple port. The weighing and
titration operations which are part of the latter analyses are
conducted in or near the laboratory trailer, %ie trailer also includes
a work area which can be used for in-field laboratory analyses, meetings
and day-to-day review of the test plans and results.
, The emission measurement instrumentation used on the project
is summarized in Table B-l.
B.I.I Gas Sampling^ _andConditioning System
A flow schematic of the flue gas sampling and analyzing system
is shown in Figure B-3. This system is mounted on and behind the control
console. Cylinders of certified calibration gas are also located in
this area. The sampling system uses three pumps to continuously draw
flue gas from the boiler into the laboratory. A high capacity positive
displacement diaphragm pump is used to draw a high volume of flue gas into
the unheated portion of the system to provide adequate system response.
The pump pulls from a manifold connected to 24 unheated sample lines. Selec-
tor valves allow composites of up to 12 points to be sampled at one time.
The probes are connected to the sample manifold with 0.95 cm (3/8") nylon
line. Stainless steel quick-disconnect couplings are provided to
facilitate the connection between the sample lines and the instrumentation
laboratory. The sample from each line then passes through a glass
353
-------
in
Sulfur Oxid** Bonch
\
Hood
• iltctrlcal
Sa-pl. tin. com,.ctio
-------
000000:000000
Figure B-2. Exterior and interior
views of mobile air
pollution reduction
laboratory. This
laboratory has been
used in previous EPA-
sponsored field-test
programs.
355
-------
TABLE B-l.
SUMMARY Of EMISSION MEASUREMENT INSTRUMENTATION
Emission Parameter
Symbol Measurement Method
Equipment
Manufacturer
Nitric oxide NO
Oxides of nitrogen NO
x
Carbon monoxide CO
Carbon dioxide C0_
Oxygen O
Hydrocarbons HC
Sulfur dioxide SO
Sulfur dioxide SO,
Sulfur trioxide SO^
Total particulate
matter PM
Particulate size
distribution
Smoke spot
Opacity
Chemiluminescent
Chemiluminescent
Nondispersive infrared
Nondispersive infrared
Polarographic
Flame ionization
UV spectrotaetry
Absorption/titration
SPA Std. Method 5
Cascade impactor,
electro-balance
Field service type
smoke tester
EPA Std. Method 9
Thermo Electron
Thermo Electron
Beckman
Beckman
Teledyne
Beckman
Du Pont
She11-Emsryville
Absorption train
Joy Mfg. Co.
Anderson, Brink,
Cahn
356
-------
SAMPLE INLET TO LAB
DUMP MANIFOLD
PRESSURE GAGE
SAMPLE SELECTOR
VALVES
WATER DROPOUT FLASKS
SOLENOID DRAIN VALVES
REFRIGERATED .
CONDENSER
SOLENOID
DRAIN VALVES
FLOW CONTROL
VALVE AND
ROTAMETER
HI6H CAPACITY NASH PUMP
ISOLATION VALVE .
I g)
MANIFOLD BLEED VALVE
VACUUM DRAIN TANK
VACUUM PUMP
DRAIN VALVE
SAMPLE
PUMP
M
I fJL FILTER ELEMENT
-
-------
bubbler to remove water condensate. Drain valves are provided for
emptying the traps. A positive displacement diaphragm sample pump
draws a small portion of the unheated sample gas from the high volume
line, and transfers it through a refrigerated condenser to reduce the
dew point to 275 K (35 °F), a rotameter with flow cdntrol valve, the
sample pump, and a 1 micron filter, as it passes to instrumentation for
measurement of O , NO, CO, and CO . Flow to the individual analyzers
is measured and controlled with rotameters and flow control valves.
Excess sample is vented to the atmosphere.
Since heavy hydrocarbons may be condensible, and NO. and SO.
axe soluble in water, a heated sample line must be used to obtain
samples for the analysis of these components. For this reason
a separate, electrically-heated, sample line is used to bring the
sample into the laboratory for analysis. The line is 0.95 cm (3/8 inch)
stainless steel line, electrically traced and thermally insulated.
A heated metal bellows pump is used to provide sample to both the
hydrocarbon, NO , and SO analyzers.
X £
B.I.2 INSTRUMENTAL CONTINUOUS MEASUREMENTS
The laboratory trailer is equipped with analytical instruments
to continuously measure concentrations of NO, NO., CO, CO , O , SO , and
2. 2 2 *•
hydrocarbons. All of the continuous monitoring instruments and sample
handling system are mounted in the self-contained mobile laboratory. The
entire system requires only connection to on-site water, power, and
sampling lines to become fully operational. The instruments themselves
are shock mounted on a metal console panel. The sample flow control
measurement and selection, together with instrument calibration,are all
performed from the console face. Three-pen recorders provide a continuous
permanent record of the data taken. The sample gas is delivered to the
analyzers at the proper condition and flow rate through the sampling and
conditioning system described in the previous section. The following
sections below describe the analytical instrumentation.
358
-------
B.I.2.1 Nitric Oxide (NO) and Total Nitrogen Oxides (NO..)
^" —*••••™""^™^^^^"^^TC"™
Both the total nitrogen oxides (NO ) and nitric oxide (NO) concentra-
tions are measured from a sample gas obtained vising a heated sample line at
394 K (250 °F). In addition, the nitric oxide concentrations are measured
sequentially from samples obtained using the unheated sample line that is
connected to the same analyzer in the laboratory trailer. In the latter
case, water is first removed from, the sample gas by a drop-out bottle and
refrigeration unit. The analytical instrument used for these measurements
is the Thermo Electron Model 10A chemiluminescent gas analyzer.
For NO analyses, the sample gas is passed directly into the reaction
chamber where a surplus of ozone is maintained. The reaction between the
NO and the ozone produces light energy proportional to the NO concentra-
tion which is detected with a photomultiplier and converted to an electrical
signal. Air for the ozonator is drawn from ambient through an air dryer
and a 10-micron filter element. Flow control for the instrument is accom-
plished with a small bellows pump mounted on the vent of the instrument
downstream of a separator which insures that no water collects in the pump.
The chemiluminascent reaction with ozone is specific for NO. To
detect NO , a thermal converter has been designed to dissociate the NO to
NO by the bi-molecular reaction: 2 NO- ^ 2 NO + 0_. A Model 700 thermal
converter is used in conjunction with the chemiluminescent gas analyzer as
shown in Figure B-4. The converter is a coil of resistance-heated stainless
steel tubing drives the NO /NO ratio to its chemical equilibrium value at
the converter temperature and pressure. The unit is designed to operate at
923 K (1200 PF) and 1.3 kPa (10 torr). For these conditions and typical
stack gas O concentrations, the equilibrium NO concentration is 0.2% of the
total NO concentration. Therefore, when a gas sample containing NO is
X £,
passed through the converter, essentially all NO would be converted to NO.
The resulting total NO is then measured using the chemiluminescent analyzer
and the difference between the actual NO and the "total NO" would be the
sample NO_ concentration. The "total NO" is interpreted as NO .
359
-------
r
Capillary
.008"x 1-1/2
| ^ _/\_^2
.005" ,020"j
j Capillaries >
' Model 700 !
Heated
Sample
Line
Figure B-4. Schematic of NO /NO chemiluminescent analysis system.
360
-------
NO nay react upon contact with H_O (liquid phase) to form HNO,
(nitric acid). Under field test conditions, the exhaust gas may contain.
significant HO (depending upon the process and the ambient meteorological
conditions) and it is necessary to convert the NO_ to NO before the H_O
is allowed to condense in the sampling system. By using the heated" sample
line and the Thermo Electron Model 700 heated NO module, NO concentra-
ya. &
tions will effectively be measured. In reference to Figure B-4, the sample
is maintained above the HO dew point up to and through the 127 ym (0.005
in.) capillary in the heated module. Downstream of this capillary, the
flow network is maintained at 1.3 kPa (10 torr), where the partial pressure
of the HO in the sample is sufficiently low to prevent any condensation at
ambient temperature.
When using the heated system, NO, NO_, and NO are measured on a
wet basis. When not using the heated system, a condenser is placed up-
stream of the analyzer and NO is measured on a dry basis.
Specifications
Accuracy: 1% of full scale
Span stability: +_ 1% of full scale in 24 hours
Zero stability: +_ 1 ppm in 24 hours
Power requirements: 115 £ 10V, 60 Hz, 1000 watts
Responses 90% of full scale in 1 sec (NO mode);
0.7 sec (NO mode) X
Output: 4-20 ma
Sensitivity: 0.5 ppm
Linearity? +_ 1% of full scale
Vacuum detector operation
Range: 2.5, 10, 25, 100, 250, 1000, 2500, 10,000 ppm
full scale
B.I.2.2 Carbon Monoxide and Carbon Dioxide (CO andCO )
Carbon monoxide and carbon dioxide concentrations are measured using
Beckman Model 864 and 865 short pathJLength nondispersive infrared analyzers
(see Figure B-5). These instruments measure the differential in infrared
361
-------
Figure B-5. Schematic of NDIR analyzer.
362
-------
V
energy absorbed from energy beams passed through, a reference cell (con-
taining a gas selected to have minimal absorption of infrared energy in
the wavelength absorbed by the gas component of interest) and a sample
cell through which the sample gas flows continuously. The differential
absorption appears as a reading on a scale of 0% to 100% and is then related
to the concentration of the specie of interest by calibration curves supplied
with the instrument. A linearizer is supplied with each analyzer to provide
a linear output over the .range of interest. The operating ranges for the
CO analyzer are 0-100 and 0-2000 ppm, while the ranges for the CO_ analyzer
are 0-5% and 0-20%.
Specifications
Span stability: +_1% of full scale in 24 hours
Zero stability: +_ 1 ppm in 24 hours
Ambient temperature range: 273 to 322 K (32 °F to 120 °F)
Line voltage: 115 + 15V rms
Response: 90% of full scale in 0.5 or 2.5 sec
Linearity: Linearizer board installed for one range
Precision: +_ 1% of full scale
Output: 4-20 ma
B.I.2.3 Oxygen (0 )
A Teledyne Model 326A oxygen analyzer is used to automatically and
continuously measure the oxygen content-of the flue gas sample. The analy-
zer utilizes a micro-fuel cell which is specific for oxygen, has an absolute
zero, and produces a linear output from zero through 25% oxygen. The micro-
fuel cell is a sealed electrochemical transducer with no electrolyte to
change or electrodes to clean. Oxygen in the flue gas diffuses through
a Teflon membrane and is reduced on the surface of the cathode. A corres-
ponding oxidation occurs at the anode internally and an electric current
is produced that is proportional to the concentration of oxygen. This
current is measured and conditioned by the instrument's electronic circuitry
to give an output in percent 0_ by volume for operating ranges of 0% to 5%,
0% to 10%, and 0% to 25%.
363
-------
Spec ifications
Precision: +_ 1% of full scale
Response: 90% in less than 40 sec
Sensitivity: 1% of low range
Linearity: +_ 1% of full scale
Ambient temperature range: 273 K to 325 K (32 to 125 °F)
Fuel cell life expectancy: 40,000%+-hrs
Power requirement: 115 VAC, 50-60 Hz, 100 watts
Output: 4-20 ma
B.I.2.4 fotal Hydrocarbons (HC|
Hydrocarbon emissions are measured using a Backman Model 402
high-temperature hydrocarbon analyzer. The analyzer utilizes the flame
ionization method of detection which is a proven technique for a wide
range of concentrations (0.1 to 120,000 ppra). A flow schematic of the
analyzer is presented in Figure B-6. The sensor is a burner where a
regulated flow of sample gas passes through a flame sustained by regulated
flows of air and a premixed hydrogen/nitrogen fuel gas. Within the flame
the hydrocarbon components of the sample stream undergo a complex ionization
that produces electrons- and positive ions. Polarized electrodes collect
these ions, causing current to flow through electronic measuring circuitry.
Current flow is proportional to the rate at which carbon atoms enter the
burner.
The analysis occurs in a temperature controlled oven. The sample
is extracted from the stack with a stainless steel probe which has been
thermally treated and purged to eliminate any hydrocarbons existing in
the probe itself. An insulated, heat traced teflon line is used to
transfer the sample to the analyzer. The entire heated network is main-
tained at a temperature to prevent condensation of heavier hydrocarbons.
The flame ionization detector is calibrated with methane and the
total hydrocarbon concentration is reported as the methane equivalent.
FID's do not respond equally to all hydrocarbons but generally provide a
measure of the carbon - hydrogen bonds present in the molecule. The
FID does not detect pure carbon or hydrogen.
364
-------
TEMPERATURE-CONTSOLL60I 1 ] CO.H730LLEO OYeN
SAMPLE LINE I I
» IFU Tea!
• SAMPLE
CAPILLARY
5^ .SAMPLE H "==t~l
._ ^ BYPASS
U.I?LE' Oy O —
trPASS^n HS.J! I
I 8ECULATOR^^|gT.s
Figure B-6. Flow schematic of hydrocarbon analyzer (FID).
365
-------
Specifications
Full scale sensitivity; adjustable from 5 ppm CHL to 10% CH,
Ranges: Range multiplier switch has 8 positions: Xl, X5, XlO,
X50, X100, XSOO, X1000, and X5000. In addition, span
control provides continuously variable adjustment
within a dynamic range of 10:1
Response time: 90% full scale in 0.5 sec
Precision: +_ 1% of full scale
Electronic stability? +_ 1% of full scale per 24 hours with
ambient temperature change of less than
10 °P
Reproducibility: HK 1% of full scale for successive identical
samples
Analysis temperature: ambient
Ambient temperature: 273 K. to 317 K (32 °F to 110 °F)
Output: 4-20 ma
Air requirements: 250 to 400 cc/min of clean, hydrocarbon-free
air, supplied at 2.07 x 10^ to 1.38 x 10
n/vr (30 to 200 psig)
Fuel gas requirements: 75 to 80 cc/min of fuel consisting of
100% hydrogen supplied at 2.07 x 10^
to 1.38 x 106 n/m-2 (30 to 200 psig)
Electric power requirements: 120 V, 60 Hz
Automatic flame indication and fuel shut-off valve
B.I.2.5 Sulfur Dioxide (SO,,)
~™~^~—-----------^~r——~ . J I- ^""""
A Dupont Model 400 photometric analyzer is used for measuring S0_.
This analyzer measures the difference in absorption of two distinct wave-
lengths (ultraviolet) by the sample. The radiation from a selected light
source passes through the sample and then into the photometer unit where
the radiation is split by a semi-transparent mirror into two beams. One
beam is directed to a phototube through a filter which removes all wave-
lengths except the "measuring" wavelength, which is strongly absorbed by
the constituent in the sample. A second beam falls on a reference photo-
tube, after passing through an optical filter which transmits only the
366
-------
"reference" wavelength. The latter is absorbed only weakly, or not
at. all, by the constituent in the sample cell. The phototubes translate
these intensities to proportional electric currents in the amplifier.
In the amplifier, full correction is made for the logarithmic relation-
ships between the ratio of the intensities and concentration or thickness
(in accordance with Beer's Law). The output is therefore linearly pro-
portional, at all times, to the concentration and thickness of the sample.
The instrument has a lower detection limit of 2 ppro and full scale ranges
of 0-500 and 0-iOOO ppm.
Spec ifications
Noise: Less than 1/4%
Drift: Less than 1% full scale in 24 hours
Accuracy: (^ 1% of analyzer reading) + (+_ 1/4% of full scale range)
Sample cell: 304 stainless steel, quartz windows
Flow rate: 6 CFH
Light source: Either mercury vapor, tungsten, or "Osram"
discharge type lamps
Power rating: 500 watts maximum, 115 V, 60 Hz
Reproducibility: 1/4% of scale
Electronic response: 90% in 1 sec
Sample temperature: 378 K (220 °P)
Output: 4-20 ma d.c.
367
-------
B.I. 3 INTEGRATED AND SEMI-CONTINUOUS MEASUREMENTS
B-l-3.1 Oxides -of Sulfur (SO and SO ) •
The Absorption-Titration Method for the Determination of Oxides of
Sulfur in Stack Gases published by the Shell Development Company (62/69)
will be used for SO and SO measurements (see Figures B-7 and B-8). KVB
has utilized this procedure on a number of previous test programs.
The gas sample is withdrawn from the flue by a single probe made of
5mm ID Vycor glass tubing inserted approximately one-third to one-half way
into the duct. The inlet end of the probe has a section 50mm long by 15mm
OD to hold a quartz wool filter to prevent particulate matter from being
drawn into the sampling train. The entire probe is maintained above the dew
point of the flue gas during sampling (minimum temperature of 260aC). The
portion of the probe extending out of the stack is insulated to prevent it
from cooling to the point where SO, condenses as sulfuric acid. Provision is
made to heat the exposed probe if necessary to prevent condensation. Insulating
putty is used to provide a seal between the exposed end of the glass probe
and support tube. The glass probe terminates in a Vycor glass ball joint
to provide a gas tight connection to the absorber train.
The sample gas is passed through an absorption train consisting of
two lamp sulfur absorbers and a spray trap as. described by ASTM D1266, and
a secondary absorber as described by ASTM 01551. All joints are ground
glass or glass butt joints held together by vinyl tubing. All glass-vinyl
joints are made gas tight by using metal hose clamps. An ice bath is
provided for the first SO absorber to cool the incoming gas and prevent
excessive evaporation of the absorbing solutions. A trap with an ice
bath is inserted between the train and the sample pump to prevent any
liquid from reaching the pump or test meter. The sample is drawn with a.
total transfer diaphragm pump. A dry gas toest meter is used to measure
-4 3
the sample volume to 0.28 x 10 m (0.001 cubic feet).
368
-------
Flue Wall
Asbestos Plug
Ball Joint
End of Opening
15 mm 10
uf
n Insulation
S.S.
Support Tube
5 mm ID Yycor
Sample Probe
Keating
Tape
P.yrometer
and
Thermocouple
Figure B-7. SO /SO Sampling Probe Configiiration.
..Spray Trap
Oia! Thermometer
Presjuro Gauge
Volume Indicator
Vapor Trap
Diaphragm
Pump
Dry Tost Meter
Figure B=a. SO /so Absorption Train.
369
-------
The result of passing the sample through the absorber train is to
separate and then convert both SO and SO to H SO (sulfuric acid). The
first two absorbers contain 80% (by volume) 2-propanol (isopropyl alcohol)
in water. The S03 in the sample is absorbed into the solution and upon
contact with the solution, the SO is converted to H_SO. (sulfuric acid).
•5 ^4
Some of the sulfur trioxide is removed in the first absorber. The remain-
der passes through as sulfuric acid mist, is completely removed by the
secondary absorber mounted above the first. Most of the SO passes through
the first two absorbers and is oxidized to H SO by 3% hydrogen peroxide
with water in the third absorber. The isopropyl alcohol in the first two
absorbers prevents the S02 from oxidizing to SO . After the sample is
taken, the absorber train is purged with nitrogen. The nitrogen carries
any S02 which was dissolved in the first two absorbers over to the third
absorber. This procedure assures complete separation of SO and SO . The
O 4b
H2S04 that is produced is titrated in both cases with Pb (CIO ) (lead
4 *L
perchlorate) to a Sulfonazo III (3,6 bis (orthosulfophenylazo) 4, 5
dihydrozy 2, 7 (napthelene disulfonic acid) end point.
The concentration of the Pb (CIO ) titrant must be accurately
known. This concentration is determined by titrating it against a
standardized H2S04 solution to a Sulfonazo III indicator end point.
The H2SO4 solution is standardized by titrating it against a standard
NaOH (sodium hydroxide) solution to a phenophthalein end point. The
standard NaOH solution is obtained commercially.
SO^ and S03 concentrations are calculated using the following
equation:
SOx (ppm by volume) »
(A-B)
x (N) x
7
(F) x (460 +T)
«v
x (24)
370
-------
where s
A * ml of lead perchlorate solution used for titration of
the SO_ or SO, .samples
& J> '
B * ml used for blank
N * normality of lead perchlorate titrant
F » dilution factor
T = average temperature of dry test meter, degrees Fahrenheit
V » uncorrected volume of gas sample, cubic feet
P =» barometric pressure, inches of mercury
p =" average pressure in the dry test meter, inches of mercury
The SO is reported on a dry basis,
Xr
B.I.3.2 Particulate Matter Total Mass Concentration
Particulate matter is collected by filtration and wet impingement
in accordance with US-EPA Method No, 5. Nomograph techniques are utilized
to select the proper nozzle size and to set the isokinetic flow rates.
Gas samples for particulate sampling can be taken from the same
sample port as those for gas analysis and passed through the Joy Manufactur-
ing Company Portable Effluent Sampler. This system, which meets the EPA
design specifications for Test Method 5, Determination of Particulate
Emissions from Stationary Sources (Federal Re'gister, Volume 36, No. 27,
page 24888, December 24, 1971, and revisions thereof) is used to perform
both the initial velocity traverse and the particulate sample collection.
Dry particulates are collected in the heated case that may contain
a cyclone to separate particles larger than 5 pm and a 125 mm glass-fiber
filter to retain particles as small as 0.3 pm. Condensible particulates
are collected in four Greenburg-Smith iapingers immersed in a chilled
water bath.
371
-------
The sampling probe is positioned through an exhaust port and
attached to the sampling box. The probe consists of a sampling nozzle,
heated probe, gaseous probe, thermocouple, and pitot tube. The ball
joint from the heated probe connects to the cyclone and glass filter
holder assembly. These assemblies are positioned in the heated sampling
box which is maintained at 433 K (320 °F) above the predicted SO dew point,
in order to eliminate condensation. The sample then passes froa the heated
section to four Greenburg-Smith impingers immersed in an ice bath. Only
the second impinger has the original tip, the other three have had the
tip removed to decrease the pressure drop through them. The first and
second impingers are filled with 250 and ISO milliliters of distilled/
deionized water, respectively. The third impinger is left dry. The
fourth impinger is filled with approximately 200 grams of indicating
silica gel to remove entrained water. The use of silica gel assures that
a dry sample is delivered to the meter box. After sampling, the spent
silica gel is discarded and not used for any further analysis.
An umbilical cord connects the last impinger, the pitot tube, and
the heating elements to the meter box which is located in a convenient
place within 15 m of the sampling ports. The meter box contains a
vacuum pump, regulating valves, instantaneous and integrating flow meters,
pitot tube manometers, vacuum gauge, and electrical controls.
Particulate matter (solids and condensibles5 is collected in three
discrete portions by the sampling train: the probe and glassware upstream
of the filter; the filter; and the wet impingers. The probe and glass-
ware are brushed and rinsed with acetone; the matter is captured for
gravimetric analysis. The probe and glassware are then rinsed with
distilled water and the rinsings transferred to a second container for
analysis. The filter is desiccates and analyzed gravimetxically.
The combined impinger liquid is heated to drive off uncombined water
and the residue retained for analysis. The particulate matter analysis
is illustrated schematically in Figure B-9.
372
-------
PARTICULATE MATTER MASS DETERMINATION
sampling "1
train /
component r
partieulate 1
matter I
transfer \
procedure J
container ( ,
processing
analysis I
result (
.
Probe Cyclone Filter Impingers
>r ^ v
Brushing Acetone Distilled
Rinse Water
Rinse
V 6 ^
i T
(
i
Distilled
Water
Rinse
' 1
j e>
t \
t
Bake at 215°F to drive off uncombitied f^O and Acetone
v > r i
i \
,
Gravimetric to 0.1 milligrams
f V \
t \
i
mS &g tng mg
I^-.......--^ -t ___, - r
. V v *
, *>
•4
r
Samples stored for Compositional Analysis
Figure B-9. Processing and analyzing particulate matter.
373
-------
US EPA method 5 considers the particulate matter captured in
containers (1) and (3)j the filter, probe brushing, and probe acetone
rinse. Since EPA source standards are based on only solid particulates,
care is taken to differentiate between solid and the total (solid and
condensible) particulates. The water wash is performed because KVB's
test experience has shown that a significant amount of water soluble
material may sometimes be captured by the probe.
The dry sample volume is determined with a dry test meter at a
measured temperature and pressure and then converted to standard conditions.
The volume of condensed water in the impingers is measured in milliliters
and the corresponding volume of water vapor is then computed at standard
conditions. The dry sample volume and water vapor volume are then summed
to give the total sample volume. The dry sample volume is used in the
data reduction procedures.
A point of interest is the method chosen to calculate particulate
6
emissions in ng/J or lb/10 Btu from the experimental data. The particulate
sampling train, properly operated, yields particulate mass per unit flue
gas volume. Having measured g/m * -it is necessary to establish the flue
gas volume per unit heat input if emissions in ng/J are desired.
The original Method 5 involved determining a velocity traverse of the
stack, the cross sectional area, the flue flow rate, and fuel heating value.
A revised and more accurate method has been promulgated by the Environmental
Protection Agency that utilizes a fuel analysis (carbon content, hydrogen
content, high heating value, etc.) and the measured excess O. in the
exhaust to calculate the gas volume generated in liberating 1-055 GJ (a.
million Btu's). The velocity traverse approach generally results in a
20 to 30% higher value and is believed to be less accurate.
374
-------
B.I.3.3 Partj.cuJ.ate Size
Particulate matter size distribution is determined using a cascade
impaetor to collect the sample and a Cahn Model G-2 Electrobalance to weigh
the sample. When light fuels, i.e., No. 2 oil, are used and the flue gas
is relatively clean, a high volume type impactor, the Anderson 2000 Mark III,
is used. When the grain loading of the flue gas is heavy, as when coal is
burned, a low volume impactor, the Brink as shown in Figure B-10 is used.
To improve the accuracy of the weighing, lightweight substrate made
of aluminum foil or glass fiber are placed in or on each steel collection
stage. The particles are collected on these lightweight discs, and the
original steel collection stages are used only as a backing for these
substrata.
A common problem with impactors is that the particles do not adhere
to the stage surface, but strike it, rebound, and are re-entrained in the
flow through the slots down to the next stage. Re-entrainment has not proved
to be a problem with the cascade impactor measurements KVB currently is
making. The flue gas flow rate has been reduced from the nominal 46.7x10
m /s (2.8 liters per minute) to 33x10 m /s (2.0 LPM) or less. Visual
examination of the collection stages has found no evidence of scouring or
re-entrainment. One set of stages was further examined under an electron
microscope and there was no sign of a significant number of particulates
that were larger than the aerodynamic diameter cut point (D_n) of the
preceding stage. There was, however, a considerable amount of sponge-like
material that appeared to be an agglomeration of small particles.
If rebound proves to be a problem that cannot be solved by reducing
the throughput, the substrate is coated with an adhesive. Workers in the
field currently are using a solution of 5% polyethelene glycol 3000 in
benzene as the substrate coating substance. If a coating is used the
substrates are baked at 473 K (200 °C) for two hours or until the volatiles
have vaporized, and the weight ceases to change. At least one additional
substratum is processed as a blank.
375
-------
Dimension* of Cascade lm»
paclor Jets
13ilfl*f*BMSII* C*HI
Jet No.
1
2
J
4
$
Jet dinm.
• 0.249
0. 1775
0. 1374
o.c-ns
0.07J1
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jet alining*
0.747
O.SJJ
0.419
0.282
O.ZiO
* From collection cup turlao.
OLLECTION.
CUP
SPRING
JET SPINDLE
GASKET
-3 SLOTS
: The In-fin* impoctor has five >tog«. Particles In tho range of OJ to 3.0
micron* are collected by IUCCCSSIYS impingement
Collection cups are positioned so that
the distance from fh* jet decreases
os the jet diameter becomes smaller.
Annular flats around cup minimize
turbulence
Figure B-10. Design of a single stage from a Brink type cascade impactor.
375
-------
Back-up filters are used on all impactors to collect the
material that passes the last irapaction stage. Binderless, glass-
fiber filter material, such as high-purity Gelman Type A Glass Fiber-
Filter Webb are employed for this purpose. For the Brink brand of
impactor, 25 mm diameter circular filters are placed under the last
spring in the outlet stage of the impactor. The filter is protected
by a Teflon 0-ring and a second filter disc placed behind the actual
filter which acts as a support. The Andersen brand impactor uses
625 mm diameter filter discs placed above the final "F" stage.
For accurate weighing of collected material, a Cahn G-2
Electro-balance with a sensitivity of 0.05 micrograms is used. This
sensitivity is needed for the lower stages of the high loading impactors
where collection of 0.3 mg or less is not uncommon. KVB currently is
using this balance in the field and has found it to be insensitive to
vibration.
The flow through the impactor is measured to determine the
cut points of the individual stages. The flow is maintained by monitoring
the flow through the impactor assembly with the pressure gauges on the
EPA train control box. The pump on the control box is used to maintain
the flow. This technique is being used successfully in the field by
KVB, Inc. at present.
To ensure proper measurement by dry gas meter and to protect
the vacuum pumps from damage by water condensing from the flue gas,
the sample stream will be chilled arid the water dropped out by a
commercially available condenser of the type available for use with
the Western Precipitation, Inc. EPA Train.
If the stack pressure is less than the ambient pressure it is
possible for backflow to occur through the impactor when the pump is
turned off. This can cause the collected material to be blown off the
collection substrates and onto the underside of the jet plate above.
KVB avoids this problem by ensuring that no gas flow through the impactor
takes place, except when sampling, by using a check valve to close off
the impactor from the pump while removing the impactor froza the duct.
377
-------
The impactor is carefully loaded with the stage cups and the pre-
weighed stage substrates. The Andersen type impactor requires extra atten-
tion for the substrate stage and stage-to-stage alignments to ensure that
the jets of one stage are above the collection surface of the next stage,
After all stages are loaded and the cap and nozzle are added, the assembled
Brink is tightened with wrenches to make certain the high temperature
No. 116 asbestos gaskets are seated. Hand tightening suffices for the
Andersen impactor.
KVB has found that supplemental heating of the impactor is not
necessary to prevent the condensation of flue gas water inside the case.
If it is found with industrial combustion equipment that heating is
necessary to prevent water vapor from condensing in the impactor, heating
tape and the necessary insulation will be employed. A thermocouple
mounted in the sample gas flow immediately downstream of the impactor
outlet is used to monitor and control the impactor temperature. This
measurement also yields the temperature needed for calculating impactor
cut points.
The impactor will be preheated for at least 30 minutes before
sampling. The inlet nozzle will be pointed downstream of the flow field
during this heating phase to prevent the premature accumulation of
particulates in the impactor.
A predetermined flow rate will be established immediately and will
be maintained constant throughout the test. Attempts to modulate flow to
compensate for changes in the duct flow rate and to maintain isokinetic
sampling would destroy the utility of the data by changing the cut points
of the individual stages. Establishment of the correct flow rate quickly
is especially important for the short sampling times typical of coal fuels.
If a non-standard flow is necessary, the true cut points will be calculated
for the actual flue gas temperature and impactor pressure drop.
378
-------
KVB has found that the post-test procedure is very important in
obtaining accurate measurements. The crucial part is to make sure the
collected material stays where it originally impacted. After the test, the
impactor will be carefully removed from the duct without jarring, unscrewed,
from the probe, and allowed to cool. Proper disassembly is critical as
discussed below.
1. Brink Impactor: Careful disassembly of a Brink impactor is
necessary for obtaining good stage weights. If a precollector cyclone has
been used, all material from the nozzle to the outlet of the cyclone is
included with the cyclone catch. All of this material is brushed onto a
small 3 cm x 3 cm aluminum foil square and saved for weighing. Cleaning
the nozzle is also "important, especially if it is a small bore nozzle.
All material between the cyclone outlet and the second stage nozzle
will be included with material collected on the first collection substrate.
All adjacent walls will be brushed off, as well as around the underside
of the nozzle where a halo frequently occurs on the upper Brink stages.
All material between the second stage nozzle and third stage nozzle will
be included with that on the second collection substrate. This process
will be continued down to the last collection substrate. Finally, care will
be exercised in taking out the filter.
2, Andersen Impactor: The foil to hold the stage 1 substrate
will be laid out. Next the nozzle and entrance cone will be brushed
out and onto the foil. Then the material on stage 0 will be brushed
off. Next, any material on the top 0-ring and bottom of stage 0 will
be brushed onto the foil. The stage 1 filter substrate material will
then be placed on the foil and, finally, the top of the stage 1 plate
Q-ring and cross peice will be brushed off. Depending on how tightly
the impactor was assembled, some filter material may stick to the O-ring
edge contacting the substrate. This will be carefully brushed onto
the appropriate foil. This process will be continued through the lower
stages and the filter.
379
-------
All substrates, the backup filter, and the control blanks are
cooled to room temperature in a desiccator and weighed to £ 0.01 mg.
The weighing chamber of the balance also will be desiccated. Samples
and blanks are returned to the desiccator overnight and reweighed
until constant weight is established. The substrates are weighed soon
after the end of the test so that the data will be available for setting
up the following test.
Upon their arrival, the field test crew undertakes the combustion
modification testing, including total particulate measurement. While
this initial testing is being done an estimate of the grain loading
and particle size is made. The data used to select an isokinetic
nozzle for the EBA Train is also used to select a nozzle for the
impactor. In no case is an impactor nozzle of less than two millimeters
diameter to be used.
Measurements are made at a sufficient number of points across
the flue or smoke stack, as specified by 1PA Method 5, to make certain
that a representative sample of particulates is obtained. Whenever
possible, the impactor is oriented vertically so that the flow through
it is directed downward. This will minimize the tendency of the particulates
to fall off the'stages. When horizontal orientation is unavoidable, extra
care will be taken not to jar the impactor against the flue during removal
and cause particulates to fall from the stages,
When coal fuel is fired and sampling is done upstream of the dust
collector, the percentage (by weight) of material larger than ten micro-
meters is appreciable. In such cases a precutter cyclone, such as that
shown in Figure B-ll and currently used with the Brink impactor, is used
to prevent the upper impactor stages from overloading. A precutter cyclone
is used during the preliminary orientation run, and if the weight of material
obtained by the precutter is comparable to that on the first stage, the
precollector is used on subsequent runs.
The length of the sampling is dictated by grain loading and the
particulate size distribution. An estimate can be made from the following
typical data gathered during previous KVB test programs.
380
-------
.350-*.
-1.!
-\r /
\ /
\ /
—3 L—,.
.50 R
#4-40 Tap
Places
1-1/4 Circle
Inlet
2.695
3501
Assembled
Cyclone
©
7#7 Drill
/ .201 Tangent
/ To Bore
/ *
PRECUTTER CYCLONE
3 Slots
^•-Complete
• Stage
Single
Collection^
Cup
STAGE
Figure B-ll.
Detail of one stage and of precutter cyclone for cascade
iopactor.
381
-------
Sampling Duration
Fuel and/or Burner (min.)
No. 6 oil 120-240
Spreader stoker 59
No. 2 oil 300
The flow rate and nozzle size are closely coupled, and requirements
for isokinetic or near-isokinetic nozzle flow sometimes force a compromise
on nozzle selection. The general order of priorities used by investigators
to determine nozzle size in the field is (!) nozzle diameter (minimum only),
(2) last stage jet velocity, (3) isokinetic flow rate required, and (4)
nozzle diameter if greater than 2.0 mm.
The largest nozzle diameter should be used to minimize sampling errors
resulting from nozzle inlet geometry. Investigators have reported that when
very small nozzles have been used with the Brink impactor, there have been
some cases in which large amounts of material were retained in the nozzle or
the nozzle has been completely blocked. The smallest diameter nozzle KVB uses
is 2.0 mm. In some instances, a 90-degree elbow may be necessary due to port
location and gas flow direction, but_these situations will be avoided when
possible. Problems in cleaning elbows may occur as well as difficulties in
determining the size interval(s) from which the deposited material originated.
When these problems cannot be avoided, nozzle bends will be made as smooth as
possible and of sufficiently large radius to minimize the disturbance of the
flow.
For light oil fuel, 300 minutes was required to collect a measurable
sample. On the other hand, with coal, only 59 minutes was required. The long
test time for No. 2 oil was necessary because, a low-flow-rate Brink brand
impactor was used. To avoid long test time KVB used a high-flow-rate impactor
when the flue gas grain loading was low. However, in no case will the test
duration be less than 60 minutes in order to allow for short-term variations
in the operation of the combustion device.
382
-------
B.I.3.4 Smoke Spot
On combustion equipment where smoke numbers normally are taken,
such as oil-fired boilers, KVB, Inc. determines the smoke number using
test procedures according to ASTM Designation: D 2156-65. The smoke
number is determined at each combustion modification setting of the
unit. Examples are baseline, minimum excess air, low load, etc., and
whenever a particulate concentration is measured.
Smoke spots are obtained by pulling a fixed volume of flue gas
through a fixed area of a standard filter paper. The color (or shade) of
the spots that are produced are visually matched with a standard scale.
The result is a "Smoke Number" which is used to characterize the density
of smoke in the flue gas.
The sampling device is a hand pump similar to the one shown
in Figure B-12. It is a commercially available item that can pass 36,900
+_ 1650 cu cm of gas at 16°C and 1 atmosphere pressure through an enclosed
filter paper for each 6.S sq cm effective surface area of the filter
paper.
Sampling Tube
\ .
\
Filter Paper
F«sa 1
e
Plunger
Ss-Pf6-
ere.r • i»
Handle
Figure B-12. Field service type smoke tester.
KVB 6002-471
The smoke spot sampler is provided with a motor-driven
actuator to ensure a constant sampling rate independent of variations
in stroke rate that can occur when the sampler is operated manually.
383
-------
The required smoke scale consists of a series of ten spots numbered
consecutively from 0 to 9, and ranging in equal photometric steps from white
through neutral shades of gray to black. The spots are imprinted or other-
wise processed on white paper or plastic stock having an absolute surface
reflectance of between 82.5 and 87.5%, determined photometrically. The
smoke scale spot number is defined as the reduction (due to smoke) in the
amount of light reflected by a soiled spot on the filter divided by 10.
Thus the first spot, which is the color of the unimprinted scale,
will be No. 0. In this case there will be no reduction in reflected inci-
dent light directed on the spot. The last spot, however, is very dark,
reflecting only 10% of the incident light directed thereon. The reduction
in reflected incident light is 90%, and this spot is identified as No. 9.
Intermediate spot numbers are similarly established. Limits of permissible
reflectance variation of any smoke scale spot shall not exceed +_ 3% relative
reflectance.
The test filter paper is made from white filter paper stock
having absolute surface reflectance of 82.5 to 87.5%, as determined by
photometric measurement. . When making this reflectance measurement, the
filter paper will be backed by a white surface having absolute surface
reflectance of not less than 75%.
When clean air at standard conditions is drawn through clean filter
paper at a flow rate of 47.6 cu cm per sec per sq cm effective surface
area of the filter paper, the pressure drop across the filter paper will
fall between the limits of 1.7 and 8.5 kPa (1.3 and 6.4 cm of mercury).
The sampling procedure is specified in D 2156. A clean, dry, sampling
pump will be used. It will be warmed to room temperature to prevent condensa-
tion on the filter paper. When taking smoke measurements in the flue pipe,
the intake end of the sampling probe is placed at the center line of the flue.
When drawing the sample, the pressure in the flue gas stream and the sampler
is allowed to equalize after each stroke.
384
-------
The smoke density is reported on the Mobile Lab Data Sheet as Smoke
Spot Number on the standard' scale most closely corresponding to test spot.
Differences between two standard Smoke Spot Numbers will be interpolated to
the nearest half number. Smoke Spot Numbers higher than 9 will be reported
as "Greater than No. 9."
This procedure is deemed to be reproducible to within +_1/2 of a
Smoke Spot Number under normal conditions where no oily stain is deposited
on the disk.
KVB's field experience with industrial boilers has been that the
human factor involved in the interpretation of the smoke spot by an experi-
enced observer does not cause a significant lack of precision.
B.I.3.5 Opacity
Opacity readings are taken by a field crew member who is a certificated
graduate of a U.S. Environmental Protection Agency approved- "Smoke School".
Observations are made when particulate measurements are made. Additional
observations are made when necessary to gather the maximum amount of
information. The procedures set forth..in EPA Method 9, "Visual Determina-
tions of the Opacity of Emissions for Stationary Sources" are followed.
Observations are made and* recorded at 15 second intervals while
particulate concentration is being measured and at other times after the
unit has stabilized. Before beginning observations, the observer determines
that the feedstock or fuel is the same as that from which the sample was
taken for the fuel analysis.
Before beginning opacity observations, the observer makes arrangements
with the combustion unit operator to obtain the necessary process data for the
standard KVB Control Room Data Sheet. The control room data are recorded for
the entire period of observations, as is customarily done by KVB during an
emissions test. The process unit data that are obtained include:
385
-------
a. Production rates
1. maximum rated capacity
2. actual operating rate during test
b. Control device data
1. recent maintenance history
2. cleaning mechanism and cycle information -
The observer requests the appropriate plant personnel to
briefly review and comment on the opacity measurements and process
data and the observer will comment on:
a. the basis for choosing the observation periods used;
b. why it is believed the periods chosen constitute periods
of greatest opacity ?
c. why the observations span a time period sufficient to
characterize the opacity.
Consideration is given to postponing the EPA Method 5 particulate
tests during periods of cloudy or rainy weather because of the inability
of the observer to monitor the smoke. :*
386
-------
APPENDIX C
TRACE SPECIES AND ORGANICS
SAMPLING AND ANALYSIS PROCEDURES
Table of Contents
Page.
C-1.0 INTRODUCTION , 389
C-2.0 PREPARATION OF XAD-2 RESIN 392
C-3.0 PREPARATION FOR A SAMPLING RUN 395
C-4,0 SAMPLING PROCEDURES 402
C-5.Q TRAIN DISASSEMBLY AND SAMPLE RECOVERY 406
C-6.0 SUPPLEMENTARY REFERENCE MATERIAL . - 411*
C-7.0 SAMPLE PREPARATION AND ANALYSIS 417
Note: Units for values in this Appendix are.given in the actual English
or metric units as used or measured on field equipment. Alternate
English to metric, or metric to English conversions are not listed
to avoid confusion, as the Appendix is intended for direct field use.
A table of conversion factors is given in Section 7.0.
387
-------
BLANK PAGE
388
-------
C-l.Q INTRODUCTION
Sampling and analysis procedures for trace species and organics
emissions used in the current program were based on procedures developed
by the EPA Industrial Environmental Research Laboratory at Research
Triangle Park, NC. The IERL-RTP procedures are defined in a procedures
manual prepared for EPA by TRW Systems Group (Ref. C-l) that relates the
procedures in terms of a multi-media Level I stream prioritization
sampling and a Level II detailed assessment sampling. Although those
sampling procedures were adapted for the current program, this program
was not formulated in the specific Level I-Level II framework. Level I
sampling is intended to show the presence or absence and, within a fac-
tor of _+ 2 to 3, the emission rates of all inorganic elements, selected
inorganic anions and classes of organic compounds. The current program
objective is to obtain qualitative and quantitative data for a large
number of elements (approximately 60) by use of spark source mass spec-
trometry. This objective is similar to the Level I philosophy. A
second objective of the current program, more related'to the Level II
definition, is to more accurately quantify the emissions of the elements,
species, and organics as shown in Table C-l, and to relate the emissions
of these species, by mass balance, to the amounts input with fuel or
process materials. In addition to total quantities, information is
required on the relationship of particulate species emissions to parti-
culate size.
The referenced Level I procedures manual refers to several
multi-media sampling procedures. The current program is more narrowly
concentrated on exhaust emissions from the stacks of industrial com- *
bustion devices. Therefore Chapter III "Gaseous Streams Containing
Particulate Matter" of the referenced manual is that portion pertinent
to the current program.. That chapter discusses sampling with
a "Source Assessment Sampling System" CSASS3. The features of that
389
-------
TABLE C-l. TKACE SPECIES AND ORGANICS TO BE IDENTIFIED
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chlorine '
Chromium
Elements
Cobalt
Copper
Fluorine
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurium
fin
Titanium
Vanadium
Zinc
Species
Total sulfates
Total nitrates
Organics
Total polychlorinated biphenyls (PCS)
Total polycyclic organic matter (POM)
Specific POM compounds:
7, 12 - dimethyIbenz (a) anthracene
Dibenz (a,h) anthracene
Benzo (c) phenanthrene
3-Methylcholanthrene
Benzo (a) pyrene
Dibenzo (a«h) pyrene
Dibenzo (a,i) pyrene
Dibenzo (c»g) carbazole
sampling train axe presented in the referenced manual and will not be
repeated here. The remainder of this appendix presents the specifics
of the referenced procedures as adopted for the current program.
SASS sampling and analytical procedures are updated continuously. The
techniques used for this study were approved at the time, but may have
changed afterwards.
The SASS sampling train and saoples obtained are shown sche-
matically in Figure C-l.
390
-------
>10 \im 10-3 ym 3-1 pm
Probe Cy- Cy- Cy- XAD-2
and Nozzle clone clone clone Filter Absorber
Pre-Clean Liquids Post-Wash Liquids
Nitric Acid-LB il 50:50 Methanolj jj
BLANKS Distilled H20-LB #2 Methylene Chloride-LB «5 tt ffl
(I sample Isopropanol-LB J 3 50s50 IPA: Dist. Water-LB 16 M
each pec Methylene Chloride-LB *4 SB n SB |»2
test site) • • f~~ "~~" "~"~~ """"" """""* "~~* *~~ ~—+
HEATED OVEN fl. '
^ ^STffi ^ i U
TRAIN « 1_J L_J LJ | WxAD-2
j _j |l 1-
.
Irapingers
1234
Reagent Reagent Drier-
Si " #2 ite
LB «7 LB IS
^ |_^ — ^j I -.,-,. i r. .1 i=
J.JUL r'-'n 1LJL JLJLU.
^ "^ '^ ^
*— - «•
HQ 0.2 molar (NH4)SOa 75° «
* ^ u.u^ moiar Ag nO-
LIQUID
'SAMPLES
SOLID
SAMPLES
LB
SB
LS
SS
• 1
Condensate
LS|2 LS|3 LS«4
I Probe &
Nozzle
I Wash
10 I'm
Wash
3 pm
Wash
1 yrn
Wash
i
Filterl
Wash '
-||H
Absorber Cond. Liquid
Wash #1
LS«S
Liquid
«2
Liquid
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xobe
I Tappings
I SS tl
Cup .
SolidsJ
Cup
solids
Cup
solids
. .
iiter
SS
#2 - L SS #3 _ SS
§4
i
J
Liquid Blank
Solid Blank
Liquid Sample
Solid Sample
Discard
Driarrite
Possible Combined Blanks
Total Samples - Liquids
Solids
10
6
6
5
8
2
Figure C-l. SASS train schematic.
-------
C-2.0 PREPARATION OF XAD-2 RESIN
C-2.1 General Procedure
The XAD-2 resin to be used in the SASS train sorbent trap must
be cleaned prior to use. The resin as obtained from the supplier is
soaked with an aqueous salt solution. This salt solution plus residual
monomer and other trace organics must be removed before the resin can
be used for sampling trace organics.
Clean-up is normally achieved in a giant Soxhlet extractor. Any
other continuous extractor working on the same principle of circulating
.distilled solvent would be adequate.
The wet XAD-2 resin is charged into the extractor thimble and
extracted in sequence with refluxing solvent as follows:
1. Water, 20-24 hours
2. Methanol, 20-24 hours
3. Anhydrous ether, 8 hours (during day only)
4. Pentane, 20r-24 hours
Methanol is used primarily to remove the water from the resin. Ether
removes a substantial portion of the organics—overnight reflux is
acceptable if apparatus is secure to the hazards of ether. Pentane is
used as the final stage because it is the solvent used to extract the
resin after sample collection.
A commercial giant extractor has a dumping volume of 1500 ml and
thus about 2.5 1 of solvent is -required in a 3 1 flask.
After the final pentane extraction, the resin is transferred to
a clean flask and dried under vacuum aided by mild heat from a heat lamp.
Care should be taken (traps) to prevent backstrearning from vacuum systems.
C- 2.2 Soxhlet Cleaning of XAD-2
Follow the general procedure given above. However, the follow-
ing procedural details may be helpful to those not familiar with operating
the Soxhlet extractors. These recommendations and comments are based on
our recent experience in preparing XAD-2 for EPA SASS tests.
392
-------
1. Quality of solvents*
Water: Arrowhead distilled
Methanol: anhydrous methyl alcohol, Mallinckrodt, AR grade
Anhydrous ether: anhydrous (ethyl) ether, Mallinckrodt,
AR grade
Pentane: Mallinckrodt, spectr. AR grade
2. The use of paper (cellulose) thimbles was recommended
by ADL. With a soft lead pencil, mark on the outside
of the thimble the desired fill line which corresponds
to the entrance level of the syphon tube when the thimble
is inserted into the extractor. Handle the thimble with
plastic gloves,
3. Fill (i.e., "charge") the thimble with XAD-2 using a
stainless steel spoon. Intermittently moisten the XAD-2
with distilled water (from a plastic wash bottle) to
compact the XAD-2 in the thimble. Excess water will
flow through the walls of the thimble. In this manner,
add XAD-2 up to the pencil fill line.
4. Install the charged thimble in the extractor, place
approximately 300 ml of distilled water in the Soxhlet
flask and assemble the Soxhlet extractor. Room temperature
tap water is adequate for the condenser cooling.
'When inserting the charged thimble into the Soxhlet, make
a small indent at the bottom of the thimble to avoid
obstructing the inlet to the syphon tube.,
5. Bring the water to a boil and allow the extractor to
syphon several times (one hour of operation is adequate).
Discard the flask contents, refill with fresh distilled
water and continue the extraction. By discarding the
initial water, most of the salt originally contained in
the raw XAD-2 is removed from the system. This will prevent
salt carryover back into the XAD-2 and will "even out"
the boiling.
6. The methanol solvent should also be replaced in a similar
fashion. This assures complete removal of the water.
(Any water remaining during the ether extraction stage
will "plug" the XAD-2 pores thereby interferring with
the ether extraction.) Three hundred to four hundred
ml of methanol in the extraction flask is adequate for all-
night operation. Use room temperature tap water for the
condenser.
*Mention of trade names does not constitute approval by U.S. EPA.
393
-------
7, For the ether and pentane extraction, a circulating ice
bath should be used for condenser cooling to minimize vapor
loss through the top of the condenser. Three hundred to
four hundred ml of solvent is adequate for all-night pentane
operation. To avoid condensing water (from the air)
on the inside of the condenser during startup, operate
the Soxhlet for several minutes without condenser
cooling (until solvent vapors purge out the air) before
turning on the circulating water.
8. Use extreme caution when handling ether and pentane.
Both are -extremely volatile and highly flammable. Make
sure all heating mantles, electrical equipment, etc. are
off while containers are open.
9. The Soxhlet reflux rate can be judged by observing the
drip rate from the condenser onto the X&D-2. One to Two
drops per second is desirable. This is accomplished
by adjusting the power to the heating mantle. For this
condition, the water may be boiled vigorously but no*
boiling (bubbling) will be observed for the other three
solvents.
10. When changing over from one solvent to another, residual
solvent remaining in the thimble and extractor should be
removed to as high degree as practical(i.e., do not
desiccate or vacuum dry). One approach which works
quite well is to apply suction to the discharge end of the
Soxhlet syphon tube. The use of a plastic "filtering
pump" (an aspirator pump operated by tap water from the
faucet) has proved adequate,
11. While drying the X&D-2 in the vacuum desiccator, heat to
approximately 120°F using heating lamps. Do not use
vacuum grease on the desiccator. Protect the vacuum pump
from pentane vapors with a carbon trap. The XAD-2 may
be left in the paper thimbles while drying in the
desiccator. Use a filter (i.e., cotton in a flask)
between the carbon trap and the desiccator to prevent
backflow of carbon into the XAD-2 in the event of a.
rapid loss of desiccator vacuum.
394
-------
C-3.0 PREPARATION FOR A SAMPLING RON
C~ 3.1 Containers, Chemicals, and Laboratory Equipment
Table C-2 lists the samples to be recovered from the SASS train
and the recommended containers used for sample storage and shipping.
In some cases more than one container may be required. All containers
should be cleaned prior to use according to the procedure used for
cleaning the train as described in Section C-2.2.
Laboratory Equipment--
All sample recovery operations, sample weighing, and chemical
cleaning of train components and containers should be performed in a
clean area specially set aside for this work. In the field, this
"clean room" should consist of at least a clean enclosed work bench
or table top and every attempt should be made to observe the following
general recommendations:
1. Avoid drafts and areas with high foot traffic
2. Keep floors swept to minimize air borne dust
3. Use plastic table cloths
4. Inlet filters on air conditioners should be in place
5. Use common sense to avoid contaminating samples with
hair, fingerprints, perspiration, cigarette smoke or
ashes, etc.
6. Use plastic gloves or forceps when handling tared
containers; stainless steel tweezers when handling
filters
In addition to sample containers listed in Table C-2, the
following clean room accessories will be required:
SASS train tool kit
stainless steel tweezers (2)
stainless steel spatulas (2)
disposable plastic gloves
teflon or "guth" unitized wash bottles (3)
teflon policeman (optional)
110°C drying oven
weighing balance 160. gram capacity required
assorted powder and liquid funnels
assorted graduated cylinders, 250 ml to 1000 ml
1/2-gal mixing jugs (3)
395
-------
TABLE C-2. SAMPLE STORAGE/SHIPPING CONTAINERS
Train Component
Sample Type
Container Required*
Probe and nozzle
10u cyclone
3y cyclone
cyclone
Filter holder and
filter
XAD-2 Modules
(1) XAD-2 resin
(2) Condensate
(3) All surfaces
Intpinger #1
Impinger #2
Impinger §3
solid tappings
solvent wash
cup solids
solvent wash
cup solids
solvent wash
cup solids
solvent wash
solid tappings and
filter
solvent wash
solid adsorbent
contents of
condensate cup
solvent wash
contents
rinses
contents
rinses
contents
rinses
Tared 4 oz. LPE
500 ml amber glass (16 oz)
Add to probe and nozzle tappings,
Add to probe and nozzle wash.
Tared 4 oz. LPE
500 ml amber glass (16 oz)
Tared 4 oz. LPE
500 ml amber glass (16 oz)
Tared 150 mm glass petri dish
500 ml amber glass (16 oz)
500 ml amber glass (wide
mouth) (16 oz)
1 liter LPE
500 ml amber glass (16 oz)
1 liter LPE, with pressure
relief cap
500 ml amber glass (16 oz)
1 liter LPS
500 ml amber glass (16 oz)
1 liter LPE
500 ml amber glass (16 oz)
*All glass containers must have teflon cap liners.
"^"Linear polyethylene (same as "high density" or "type 3" polyethylene)
Additional sample bottles must be provided for all fuel, process
materials, and ashes to be collected. For train washes and liquids,
particularly the condensate, several bottles may be required.
396
-------
Quality of Chemicals—
An underlying concern in selecting chemicals for impinger solu-
tion and washes is to avoid introducing trace compounds similar to those
being analyzed. Although "blanks" of impinger solutions will be analyzed,
it is preferable to minimize chemical impurities when possible by using
highest quality chemicals rathern than adjust the final sample analyses
results. The following chemical grades were used:
Chemical
Quality
Impinger Solution:
distilled water
ammonium per (oxydi) sulf ate
0. IN silver nitrate (AgNO3)
30% hydrogen peroxide (H.O )
Train Precleaning:
distilled water
isopropyl alcohol
raethylene chloride (CH C123
Sample Recovery;
distilled water
methylene chloride (CH
methanol
isopropyl alcohol
[CH3CH(OH)CH3]
Commercial
distilled
AR
AR
Commercial
distilled
Spectr AR
Spectr AR
commercial
distilled
Spectr AR
Spectr AR
Spectr AR
If higher grade (lower impurity levels) of chemicals are available
they should be used.
397
-------
C-3.2 Cleaning the SASS Train
Newly purchased or previously unused train components and sample
containers should be washed with tap water and a plastic scouring pad.
All surfaces in the sampling train which come in contact with sample,
as well as all sample containers and impingers, should be prepassivated
by one-hour standing contact with a 50:50% volume solution of pure nitric
acid and distilled water. Remove any remaining traces of acid by rinsing
with tap water, then continue with the solvent cleaning procedure below.
Prior to sampling, all SASS train components and sample con-
tainers are cleaned in two or three successive stages (in the order
listed) using a different solvent in each stage:
All Except Impinger Sample Bottles Impinger Sample Bottles
1. distilled water 1. distilled water
2. isopropyl alcohol 2. isopropyl alcohol
3. methylene chloride (CH.Cl.)
The distilled water may be dispensed in plastic wash bottles; the iso-
propyl alcohol and^CH^Cl- should be dispensed using teflon or glass wash
•bottles. After each part is washed with CK^CI.-, it should be dried in
a filtered stream of dry air or nitrogen.
Any solid residues adhering to the internal surfaces should be
removed with tap water and a plastic scouring pad before preceding with
the solvent cleaning procedure.
After cleaning, assemble and cap off the cyclone assembly.
(All caps should be previously cleaned according to the above 3-solvent
procedure.) Cap off other sections of the train including the probe,
XAD-2 module, filter housing, impinger trains, and interconnecting
hoses.
398
-------
C-3.3 Impinger Solutions
Impinger
Reagent
Quantity
Purpose
fl
6M
#2
13
0.2M (NH4) S2
+ 0.02M AgN03
S_O_
2 2 B
0.2M
+ 0.02M AgNO.
Drierite (color
indicating)
750 ml Trap reducing gases such as
SO2 to prevent depletion of
oxidative capability of trace
element collecting impingers
2 and 3
750 ml Collection of volatile trace
elements by oxidative disso-
lution.
750 ml Collection of volatile trace
elements by oxidative disso-
lution .
750 g Prevent moisture from
reaching pumps
Suggested Formulas for Preparing Impinger Solutions—
Impinger #1 (6M H.,OJ
* * ' ' "" -"—
To prepare 750 ml of 6M H_O dilute 465 ml of standard
30% (by weight) H-CL with distilled water.
Iropingers #2 and #3 [0.2M (NH.) S,O0 4- 0.02M AgNO,]
-™ ............. ......... 4 2 *• cJ ' J
To prepare 1500 ml of solution combine:
1. 68.46 gm crystalline (NH ) SO
2. 300 ml 0.1 N AgNO solution
and dilute to 1500 ml using distilled water.
Additional solution should be prepared for at least 1 liter
of solution as a blank.
399
-------
Impinger t4 (color indicating Drierita)
Use 750 gm or approximately 750 cc of 8 mesh color indicating
Drierite (CaSO )
When installing the top on the impinger bottle, avoid forcing
Drierite "up into the center tube as this results in increased
pressure drop. Lay impinger on side while inserting top.
It may be necessary to replace the Drierite several times
during a SASS run. A marked decrease in Impinger #4 outlet
temperature (moisture absorption by Drierite produces heat)
may signal Drierite depletion if the Drierite color change
is difficult to detect.
The spent Drierite is not kept for analysis and can be dis-
carded or, preferably, rejuvenated for future use by heating
in a drying oven at 220°F to 250°F to blueness.
C-3.4 Filter Preparation
More than one filter will be required when particulate grain
loading is high (i.e., pulverized coal units, cement kilns, etc.).
Using stainless steel tweezers, place each filter in a clean, numbered
150 mm glass petri dish. Bake at 220°F for at least three hours in a
drying oven, then immediately transfer to a desiccator to cool.
Weigh the petri dish (plus f11tar). Weigh a second time,
preferably several hours later, to confirm the initial weighing. This
is the tare weight used to determine the mass particulata catch on the
filter.
The type of filter used is a Gelraan type A/E binderless glass
fiber.filter (142 mm diameter), purchased through Scientific Products,
C-3.5 SASS Train Assembly
Transport each separate train component to the sample port
area with all sealing caps in place. When removing caps for connection
of components, make certain no foreign matter enters the components.
If the ambient dust level is high, the train should be covered with
plastic drop cloths. Before installing the probe nozzle and with the
probe capped, turn on the vacuum pump and leak check the system. Leakage
rate should be held to 0.05 cfm at 20 "Hg pump suction. Avoid over-
tightening fittings and clamps.
400
-------
C-3.6 SASS Chemical "Blanks"
a. Blanks from impingers #2 and #3 should be prepared in the
field with the same distilled water used in preparing the
inpinger solution. To prepare a 1000 ml blank, mix the
following ingredients and dilute to 1000 ml with distilled
water:
1. 45.7gm crystalline (NH.). S20g
2. 200 ml 0.1 N A NO,
g 3
b. Blanks of impinger #1 can be prepared in the field
with the same HO and distilled water used for the
impinger solution.
c. Blanks of the wash solutions should be obtained in the
field (i.e., IPA, 50:50 meth, chlor. — methanol, H20).
d. At least one filter blank should be processed in the
same manner as sample filters; one blank per test
site.
e. At least one blank sample of the XAD-2 resin should be
preserved for each test site.
401
-------
C-4.0 SAMPLING PROCEDURES
The SASS train is basically a high volume Method 5 system modi-
fied to collect trace metal and organic compounds which would normally
pass through the standard Method 5 train. The major design differences
apparent in Figure C-l are the XAD-2 adsorbent module, multiple cyclone
assembly, and new impinger solutions. The SASS train is operated in
much the same fashion as a Method 5 train, but there are a number of
modifications as discussed below.
G-4.1 Sample Flowand Isokinetic Conditions
To preserve the cyclone "cut-off" points, the sampling flow
rate is adjusted to maintain approximately 4.0 awcfm (actual wet cubic feet
per minute) at the required 400°P cyclone oven temperature conditions.
Since isokinetic sampling is also still required, both these constraints
are satisfied to the highest degree possible by selecting the optimum
probe nozzle diameter.
* »
After stack velocities, temperatures, and oxygen levels are
established by the preliminary stack traverse, the nomogram, Section C-5,
may be used to select the proper nozzle diameter and "rough in" the
required sampling rate (but see STEP 5 below). However, if stack con-
ditions are encountered that are not covered by the.noroogram, the
following computational procedure may be used for each sampling location.
EQUATIONS:
d " 0.1192 /T /V CD
s s
Q = 281.4 (Vg)(d2)/Tg . (2a)
V . [Q (Ta)l/[281.4 (d2)] (2b)
Q (Tj/860) [1 - (%H20/100)] (3)
402
-------
d a nozzle diameter (inches)
T « stack temperature (°R)
s
V « stack velocity (ft/sec)
Q * sample flow rate at cyclones (awcfm)
O « sample flow rate at meter (adcfm)
T * meter temperature (°R)
m
%H 0 « sample moisture content (% by volume)
These equations are valid only when an oven (cyclone) temperature of
400°F is maintained and when the pressure of the stack and dry test
meter are roughly the same (i.e., +_ 1" Hg) .
STEP 1:
Select the nozzle size closest to the value computed from
Equation (1). Use this value in the following step:
Fractions of inch (nozzle diameter)
*s
vo
1
o
CO ^3* CO HI
v. X. N^ Vfc.
^H ^S. ^H ^*-
i-i r-i m r*
I 1 it
I II 1
Hi CM <*"! ^
* • * *
o o o o
"S..
^%
1
1
Ul
*
O
r«t CO X.
>^ "V. .-J
^, "S, ("1
en in r-»
i l i
i i
to r-
ci c>
•s^,
i
I
CO
O
Decimal Inches
STEP 2:
Compare the cyclone flow rate from Equation (2a) to the desired
rate of 4.0. If the values compare to within +_ 10%, proceed to next
step. Otherwise, calculate a stack velocity from Equation (2b) using
a value for Q which is within 10% of 4.0 [i.e., use 3.6 or 4.4,
whichever is closest to the value obtained from Equation (2a)]. This
calculated stack velocity should be within 10% of the actual stack
velocity. If not, stack conditions are very unusual and greater than
10% "tolerances" are necessary (i.e., deviations from isokinetic condi-
tions a/o deviations from 4.0 cfm conditions at the cyclone will be
necessary).
403
-------
STEP 3:
Calculate the meter flow rate from Equation (3) using the cyclone
flow determined in the previous step.
STEP 4:
Determine the approximate orifice AH corresponding to the flow
rate from the previous step. Use the nomogram plot of dH versus flow
rate determined experimentally for the particular control box and orifice.
This is based on the mid-size orifice of the three in the control box.
STEP 5:
The value of M determined in the previous step (or from the
nomograph) will be adequate to "rough in" the flow rate when the SASS
train is first turned on. However, as soon as possible, obtain more
accurate settings using the actual measured meter temperature and the
actual meter flow rate obtained from the meter readout and a stopwatch.
C-4.2 Organic Adsorber Module Operation
When the XAD-2 module is operated "cold" to condense moisture
from the sample, the following procedure may be used to transfer conden-
sate from the condensate cup at the base of the module to the' condensate
collection flask. This is necessary to avoid overfilling the condensate
cup which would result in condensate carryover into the irnpingers,
This transfer procedure can be accomplished without interrupt-
ing the sampling. The procedure should be performed frequently at the
start of a test until the actual condensate collection rate is established.
STEP 1:
Inspect the condensate collection flask and interconnecting tube
to confirm that all fittings are tight.
STEP 2:
Partially close off the large (1/2-inch) ball valve at the inlet
to the XAD-2 module until the vacuum gage on the pump increases by about
2 in. of mercury.
404
-------
STEP 3s
Open the condensate drain valve at the bottom of the module.
Since the collecting flask is initially at a higher pressure than
the inside of the nodule, air will flow from the flask into the
module (bubbling through the collected condensate) until pressures are
equalized.
STEP 4:
After a few seconds,to allow the equilibration of pressures,
open the 1/2-inch ball valve. This raises the pressure in the module
relative to the collection flask, forcing any condensate into the
bottle.
STEP 5:
_After all the condensate has been transferred, close the drain
valve.
C-4.3 Drierite
See Section C-2.3 for comments on Drierite depletion and
renewal (Impinger #4).
C-4.4 Filter Changes
When sampling coabustion effluents with high particulate loading,
plugging of the filter may occur before adequate sample volume is obtained.
In this event, it will be necessary to shut the train down and install a
new filter.
The rate of filter plugging is evident by the gradual increase
in sample punp vacuum required to maintain sample flow. To minimize
filter changes, the train may be operated with pump vacuums of 15 to
20 "Hg or until desired sample flow cannot be maintained.
405
-------
C-5.0 TRAIN DISASSEMBLY AND SAMPLE RECOVER*
1. After turning off train and withdrawing probe from stack, open
the cyclone oven to expedite cooling (turn oven cooling fan on)
2. Disconnect probe and cap off both probe ends and inlet to 10U
cyclone.
3. Disconnect the line joining the cyclone oven to the XAD-2
module at the exit side of the filter and cap off the filter
holder exit and the entrance to the joining line which was
disconnected from the filter holder exit point.
4. Disconnect the line joining the XAD-2 module to the irapinger
system at" the point where it exits the XAD-2 module. Cap off
the exit of the XM>-2 module and the entrance to the joining
line leading to the impinger system.
5. Disconnect the line exiting the Drierite impinger at the
point where it leaves the impinger and cap off the impinger
exit. Discard ice and water from the- impinger box to facili-
tate carrying.
6, Carry .the probe, cyclone-filter assembly, XAD-2 module (plus
joining line and condenaate collection flask) and irapinger
train (plus joining line) to the clean room for sample
recovery. Before entering the clean room, clean off all loose
particles from the exterior surfaces of the train components
using compressed air, brushes, etc.
7. Procedure for transferring samples from the various portions
of the SASS train into storage containers is outlined in the
flow diagrams on Figures C-2, C-3, and C-4.. Place copies of
these diagrams in an easily visible location in the clean room
for quick reference during the sample recovery and transfer
operations.
406
-------
o
Step 1: Hold, probe vertically
(nozzle end down) and tap vigor-
ously to clear loose solids from
fittings and drive them into
nozzle.
Step 2: Disconnect nozzle front
probe and tap loose solids into
tared nalgene container.
Step 3s Rinse adhered material
into amber glass container.
Figure C-2
SASS TRAIN SAMPLE RECOVERY —
PROBE, CYCLONES, FILTER, XAD-2 MODULE
Add to 10 M
cyclone solids
Add to probe rinse
Rinse into nozzle wash
container.
Add to 10 U
cyclona rinse
Step Is Reirove filter housing
from cyclone assembly, cap off
filter housing inlet and 1 |1
cyclone outlet, and set filter
housing aside.
Step 2s Briefly tap cyclone
assembly to clear solids from
fittings.
Step 3i Disconnect 10 U cyclone
from cyclone assembly and cap off
10 U cyclone outlet and 3 it
cyclone inlet. Vigorously tap
10 v cyclone to drive solids into
lower cup.
Remove cup, lift out
vanes with stainless
steel tweezers and
transfer cup contents
into nozzle tappings
container.
/Contoinaj
Step 4i Reconnect cyclone cup
assenbly (with vanes), remove
cyclone top and rinse top into
lower sections of cyclone.
Step St Rinse cyclone center
section into cup assembly.
Remove cup assembly, rinse
vanes into cup and transfer
cup contents into nozzle-
probe rinse container.
(Continued)
-------
o
00
Step li Briefly tap cyclone
assembly to clear solids from
3 ji - 1 u cyclone connecting
fitting.
Step 2i Disconnect 3 u cyclone
Crow 1 u and cap off 3 u cyclone
outlet and 1 M cyclone Inlet.
Vigorously tap 3 u cyclone to
drive solids into lower cup.
Remove cup assembly, lift
out vanes with stainless
steel tweezers and trans-
fer contents of cup into a
tared nalgene container.
Step 3t Reconnect cyclone cup
assembly, remove cyclone top
portion and rinse top portion
of cyclone into lower sections
of cyclone.
Figure C-2
(Continued)
SASS TRAIN SAMPLE RECOVERY-
PROBE, CY. CLONES,
FILTER, XAD-2 MODULE
Step 4i Rinse cyclone center
section into cup assentoly.
Step It Vigorously tap cyclone
to drive solids into lower cup.
Step 2s Disconnect upper portions
of cyclone and rinse them and the
ci^p into amber glass container.
Step It Open up filter housing,
remove filter using a stainless
steel tweezers and place filter
(particulate side down) in a
covered tared ISO mm glass petri
dish. Any appreciable solids
adhered onto the filter housing
may be tapped into the petri dish
(i.e. lift edge of the filter,
tap solids into bottom of petri dish
and then cover over with filter).
Remove cup assembly, rinse
vanes into cup and transfer
contents of cup into anfcer
glass container.
Disconnect cup and transfer
contents into a tared
nalgene container.
Step 2i Rinse both halves of
particulate housing (including
interconnect tubing attached)
into amber glass container.
NOTES I
1. Use SOiSO CHCl and CH-OH for
•11 rinses (use teflon wash
bottles or Guth unitized wash
bottles).
2. Handle all tared containers with
gloves.
3. Transfer of solids nay ba assisted
by the use of stainless steel
spatulas and powder funnels. Nylon
bristle brushes nay also be used
if necessary.
4. All nalgene containers must ba
high density polyethylene.
-------
SASS TRAIN SAMPLE RECOVERY — XAD-2 MODULE
STEP NO. 1, XAD-2
AND CONDENSATE REMOVAL
Release clamp 'joining XAD-2 cartridge
section to the upper gas conditioning
section.
Remove XAD-2 cartridge from cartridge
holder. Remove Cine mesh screen from
top of cartridge. E-ipty resin into
wide mouth glass amber jar.
Open condensate cup valve, raise con-
densate cup above the condensate
collection bottle and flow condensate
from the condensate cup into the
collection bottle through the Teflon
tube.
Unscrew Teflon tube from collection
bottle and cap off collection bottle.
The condensate is sent to the labora-
tory in this bottle.
I
Disconnect the Tnflon tube at the
condensate cup valve. Rinse Teflon
tube into amber glass bottle.
Install new collection bottle and
connect Teflon tube at the bottle.
Replace screen on canister, reinsert
canister into module. Join module
back together and replace clamp.
STEP NO. 2, XAD-2
MODULE RINSE
Close condensate cup drain valve.
Release upper clamp and lift out inner
well.
Rinse inner well surface into and along
condenser wall so that rinse runs down
through the module and into condensate
cup.
When inner well is clean, place to one
side.
Rinse braided entrance tube into module
interior. Rinse down the condenser wall
and allow solvent to flow down through the
system and collect in condensate cup.
Release central clamp and separate the
lower sections (XAD-2 and condensate
cup) from the upper section (condenser)
The entire upper section is now clean.
Rinse the now empty XAD-2 canister into
the condenaate cup. Remove canister and
place in a clean container. Rinse walls
of XAD-2 section into condensate cup.
Release lower clamp and remove XAD-2
section from condensate cup.
NOTE! USE 50:50 CH Cl; and CB.OH
FOR All. RINSES.
The condensate cup now contains all
rinses from the module. Drain into th«
amber glass bottle (via drain valve)
containing the Teflon tube rinse.
Figure C-3.
Rinse condensate collection flask and
Teflon connecting tubing into the above
amber glass bottle.
409
Assemble complete module and reconnect
Teflon tube at condensate cup valve.
-------
SASS TRAIN SAMPLE RECOVERY -- WINGERS
Step No. 1
Impinger No. 1
Impinger
Liquid
*Rinse From
Impinger Bottle
And Tubing
Rinse From
Connecting Line
Leading Prom XAD-2
Mod to First Impinger
Step No. 2
Impinger No. 2
Impinger
Liquid
* Rinse From
And Tubing
Nalgene
Container
Amber
Glass
Bottles*
Step No. 3
Impinger Ho. 3
Impinger
Liquid
* Rinse From
And Tubing
Nalgene
Container
Amber
Glass
Bottles*
•NOTEI ALL RINSES ARE
(1) XSOPROPYL ALCOHOL (FIRST)
(2) DISTILLED HATER (SECOND)
IPA AND HATER RINSES SHOULD
BE PLACED IN SEPARATE BOTTLES
Step. NO. 4
Impinger No, 4
Drier!to
Discard
Drierite
Figure C-4.
-------
C-6.0 SUPPLEMENTARY BEFERENCE MATERIAL
Physical Properties of SASS Chemicals, Figure c-5
Physical Properties of XAD-2, Table C-3
SASS Train Nomogram, Figure C-6
Miscellaneous Data, Table C-4
411
-------
PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS
No.
Name
Synonyms and Foratula
Mot
wt.
Color.
crystalline
form,
specific rotation
ind A^. (log ci
m.p.
•c
l».p,
*c
Density
«»
Solubility
w
al
cth
act
bz
other
solvents
Rcf.
Methane
,.! «4.93 |i»« <200
.32«» |l.4242"
lBI',13
Qpi 588
I»prapuol. Iiopropy I
slcohoL CH,CH(OH)CH»
60.11
I2.4"* 0.7»JJi» I.JT76"
BI>,I4I9
Orbmol. Mcihyl alcohol. 32.04
Wood alcohol. CH,OH
-93,»
S4.9«**« 0,79Mi« l,3288»
15"
50 * v chli BI*. 1147
PHYSICAL CONSTANTS OF INORGANIC COMPOUNDS
-.
M4
Ammonium
oiid«. 0#r-
Sy&onym* Had
Formula*
(NH*)»8iOi. ,, -,
HiOi
MoL
•«.
233.18
34.01
Cry»UJlin» lorn,
propvrtiec mad
index oft
ntmetioa
I.S02, 1.S8T
Uq 1.333. »l
1.30V. 1.313
eotlio: 1.4.U" . .
Dmuty or
1.982
1.000*
1.4422"
Mdtiag
point, *C
d 120
3.000
-0.41
Boiliog
poiot. *C
100.0OO
^
Cokt
S8.2*
illijr, IB ^i
Hot
oaf p«r 100 oo
Otbw toUenu
« «1
i al, «th: i p1. viol; • •">
•1ST nitno AcHOt...
10B.S7 col, rhomb, 1.7211.
1.744. 1.788
112
4444
122* iSSZ1" t «th
Figure C-5. Physical properties of SASS chemicals,
412
-------
TABLE C-3. XAD-2 RESIN
XAD-2 is available from:
Fluid Process Department
Rohn and Haas
Philadelphia, Pa.
A contact for questions is:
Mr. Charles Dickert
(215) 592-3000
The material is a styrene/divinylbenzene copolytaer and the material is
supplies wet with a salt solution.
Some relevant parameters are:
mesh range:
surface area:
avg. pore dia.:
specific density:
bulk density:
pore volume:
20-50
300-350 mz/
90A
1.02 g/cc
0.4 g/cc
0.85 cc/g
Costs were $96.50/cu. ft.
Property
Appearance
Solids
Porosity (ml.pore/ml.bead—dry basis)
Surface Area (m.a /g.— dry basis)
Effective Size (mm.)
Harmonic Mean Particle Size (mm.)
Average Pore Diameter (A— dry basis)
True Wet Density indistilled water (g./ml.)
Skeletal Density (g./ml.)
Bulk Density (lbs./ft.3)
(g./cc.)
Amberlite XAD-2
Hard, Spherical
opaque beads.
51 to 55
0.40 to 0.45
330
0.30 to 0.45
0.45 to 0.60
90
1.02
1.07
40 to 44
0.64 to 0.70
413 . - .
-------
-------
Figure C-6. (Continued) SASS operating nomogram.
-------
TABLE C-4. MISCELLANEOUS DATA
Cyclone cup capacities: 3U and 10u =370 cc; ly = 20 cc
XAD-2 canister volume = 402 cc
S—type pitot tube factor = 0.85 +. 0.02
Screen for XAD-2 canister:
316 stainless steel
80 mesh x 0.055 wire diameter
Purchase from:
Cambridge Wire Cloth Co.
3219 Glendale Blvd
Los Angeles, California
(213) 660-0600
Condensate container volume = 700 cc
XAD-2 module temperature = 68°F (20°C)
416
-------
C-7.0 SAMPLE PREPARATION AND ANALYSIS
Samples were analyzed by Calspan Corp., Buffalo, NY, by atomic
absorption, gas chromatography and wet chemistry. Spark source mass
spectrographic (SSMS) analyses were performed by Commercial Testing and
Engineering, Golden, COf as a subcontract to Calspan's work. Calspan and
CTE analyzed preselected samples that include base samples, blanks, and
duplicates. Additional samples were submitted to Battelle Memorial Institute,
Columbus, OH for analysis of POM by gas chromatograohy/mass spectrometry.
C-7.1 Sample Size
The sample size required for analysis is dependent on how much
sample can be obtained from the SASS train. Table C-5 lists the detec-
tion limit and sensitivity for all sample components to be analyzed.
For metal analysis, 200 ml of impinger liquids are necessary. For solid
samples, 4 to 5 grams are necessary. Analysis for chloride, fluoride,
sulfate, and nitrate requires up to 200 ml of liquid sample and 5 grams
of solid sample. PCS and POM analysis requires 10 to 50 grams of solids
and as much liquid as can be obtained (> 500 ml). Additional sample is
required for SSMS analysis.
The sample amounts given are desired amounts. Analysis can be
achieved on much smaller samples but with a sacrifice in detection
capability for desired components. The detection of individual compo-
nents, however, cannot be greater than the detection limits and sensi-
tivities given in the table. Detection limits may also be higher for certain
types of sample matrix.
C-7.2 Sample preparation
Analysis of SASS train samples involves pretreatment of the
samples after collection to place them in a form suitable for chemical
analysis. Atomic absorption requires that each sample be predissolved
or be in the liquid phase. The technique for solubilization of the
417
-------
TABLE OS. DETECTION LIMITS AND SENSITIVITY VALUES
Pollutant
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
PCS
POM
Sulfates
Nitrates
Detection Limit
Solids
(ug/g) *
10
0.10
1.5
0.25
0.10
0.15
1.0
1-5
0.5
1.0
2.5
0.5
0.01
1.0
0.1
10
5
15
10
0.25
5.0
5
0.1
50
50
5
Liquids
(yg/ml)
0.2
0.002
0.03
0.005
0.002
0.003
0.02
0.03
0.01
0.02
0.05
0.01
0.0002
0.02
0.002
0.2
0.1
0.3
0.2
0.005
1
0.1
0.002
0.1
1
0.1 •
Sensitivity
"Solids
(ug/g) *
25
0.5
20
1.25
1.25
4
5
10
5
5
25
2.5
0.05
7.5
0.1
50
200
100
40
1
250
12.5
0.50
100
250
10
Liquids
(lag/ml)
0.5
0.01
0.4
0.025
0.025
0.08
0.1
0.2
0.1
0.1
0.5
0.05
0.001
0.15
0.002
1
4
2
0.8
0.02
5
0.25
0.01
2
5
0.2
*Values given are for 1 gram of material dissolved in 50 ml of solution.
418
-------
metals is based on methods utilized by'the National Bureau of Standards
(Ref. C-2) for solubilizing both highly organic materials such as coal
and inorganic materials such as fly ash prior to sample analysis. The
outlined techniques allow for wet chemical ashing of material that
prevents loss of volatile elements like mercury, arsenic, and selenium.
The methods given use concentrated mineral, acids, and a strong oxidizing
acid, perchloric (HC1O,), to decompose organic materials.
One gram of highly organic material (coal, tar residue, fuel
oil, etc.) is transferred to a Teflon beaker. The sample is slowly
digested for several hours in 25 ml of NHO and cooled. A mixture of
5 ml of HP and 10 ml of HC1O. is added and the digestion is continued
at low heat. Extreme care is necessary, because excessive temperatures
can cause decomposition and explosion. Digestion is continued until
all carbonaceous material has been destroyed. The solution is then
transferred to a 50 ml volumetric flask and diluted to a calibrated
volume.
Low organic samples (fly ash, bottom ash, cement kiln dust,
etc.) are accurately weighed to one gram in a Teflon beaker. A mix-
ture of 5 ml of HNO and 5 ml of HF is added. The beaker is covered
and the sample digested for one hour. After complete cooling, 10 ml
of HC1O is added and the digestion is continued until all carbo-
naceous material has been destroyed. The cover is then removed and
the sample evaporated to dryness and baked until the solids turn brown
around the edges. A mixture of 2 ml of HC1 and 35 ml of distilled water
is added and the solution heated slightly until all solids dissolve.
The solution is then transferred to a 50 ml volumetric flask and diluted
to a calibrated volume.
Liquid samples from the SASS train are stabilized with 1 ml
of concentrated nitric acid to every 200 ml of impinger liquid. Whenever
possible,liquids are concentrated by boiling to one-half their received
volume to concentrate trace elements.
419
-------
. Both predissolved and concentrated liquids are analyzed
using atomic absorption spectroscopy using the most sensitive aspiration
techniques available. Analysis for both PCB and POM will involve extrac-
tion and concentration prior to analysis. The PCB and POM are coextracted
by liquid-liquid or liquid-solid extraction.
Solid samples (^ 50 grams) are extracted with benzene using
a Soxhlet extractor. The extract is concentrated using a Xuderna-
Danish evaporator to reduce the extract volume to 10 ml. Aliquots 2 to .
5 ul are injected directly into a gas chromatograph for PCB and
POM analysis after liquid-solid column separation and clean-up.
Both POM and PCB,after extraction with benzene,are isolated
as a class using adsorption chromatography by a technique called the
Rosen separation (Refs. C-3 and C-4). This technique entails adsorption
of the total sample on a silica gel column. The initial effluent from
the column when washed with pentane will contain an aliphatic hydrocarbon
fraction. The aromatic hydrocarbon fraction is eluted with benzene.
The benzene fraction which contains all POM and PCB is analyzed
using gas chromatography employing FID and EC detectors.
Detection and measurement of POM and PCB are accomplished by
using a gas chromatograph employing a flame ionization detector (FID)
and an electron capture (EC) detector equipped with Ni-63 source.
Confirmation is performed by comparing to POM standards and PCB standards
of known concentration and literature relative retention time data.
C- 7.3 Analysis Procedures
Analysis for chlorine, fluorine, nitrates, and sulfates all
involve wet chemical processing prior to actual measurement. Since all
chlorides, nitrates and most sulfates are water soluble, they can be
extracted from solid samples using a Soxhlet extractor. The extraction
scheme to be used has been effectively used by the Bay Area Air Pollution
Control District, San Francisco (Refs. C-5 and C-6).
420
-------
Fluorides, however, are not sufficiently soluble to allow for
effective aqueous extraction. Solid samples are fused with sodium
hydroxide to convert all fluorides to soluble sodium fluoride. The fused
melt is dissolved in 4 M HC1 and the resulting liquid analyzed as a
soluble fluoride.
Liquid samples analyzed for chlorine, fluorine, nitrates,
and sulfates are analyzed directly by techniques specific for each
anion-
Solubilized chloride is analyzed by adding dilute mercuric
nitrate solution to an acidified sample in the presence of mixed diphenyl-
carbozone-bromophenol blue indicator. The end point of the titration is
the formation of a blue-violet mercury, diphenylcarbozone complex (Ref.
C-7).
An alternative method involves direct measurement of chloride
with a specific ion electrode. Both methods are used and checked
to obtain the best sensitivity on the submitted samples.
Analysis for fluoride in liquid samples or solubilized fusion
products is performed by prior Bellack Distillation to remove
interfering substances. After distillation, the fluoride is deter-
mined potentiometrically using a selective ion fluoride electrode
(Ref. C-8) .
The analysis for nitrate is based upon the reaction of the nitrate
ion with brucine sulfate in a 13N H2SO. solution at 100°C. The color of
the resulting complex is measured at 410 nm (Ref. C-8).
Sulfate analysis is performed by converting sulfate ion to
barium sulfate suspension under controlled conditions. The resulting
turbidity is determined on a spectrophotometer and compared to a curve
prepared from standard sulfate solutions (Ref. C-8).
421
-------
Metal analyses are performed on liquid and solid samples
after pretreatment and solubilization of materials as outlined earlier.
A Perkin-Elmer Model 460 atomic absorption spectrometer with microcom-
puter electronics is used in conjunction with conventional aspira-
tion and time integration techniques. "Hie Model 460 is a relatively new,
highly sensitive instrument that allows accurate measurement of metal
concentrations. In addition, conventional hollow cathode source.lamps,
electrodeless discharge lamps (EDL), are available for lead, mercury,
arsenic, and selenium. These special lamps are more stable and provide
for more initial energy to allow accurate detection of difficult-to-
analyze elements.
Mercury is analyzed by the cold vapor technique developed
by Hatch and Ott (Ref. C-9). Arsenic and selenium are to be analyzed by
conversion of these elements with hydrogen to arsenic hydride and selenium
hydride vapor. Each of the vapor techniques allows for low-level detec-
tion and quantization for each of these elements.
A listing of the detection limits and sensitivity for each element
in liquid and solid samples is given in Table C-5 . In the table, detection
limit is defined as the concentration that produces a signal equivalent to
twice the magnitude of the background. Sensitivity is defined as the con-
centration in micrograms per milliliter of solution to produce a one
percent change in absorption or one percent change in the recording chart
readout.
The detection limits for solid samples are based on a
one gram sample dissolved or extracted into 50 ml volumes of analysis ,
solution. Each value given is conservative and is based on the possi-
bility of interference between components present. If the sample is
relatively "clean", i.e., no interfering or high background substances,
detection limits may be even lower.
422
-------
Polychlorinated biphenyls (PCB) and polycyclic organic materials
(POM) are analyzed using a Hewlett-Packard Model 5700 gas chroma-
tograph equipped with a flame ionization and an electron capture detector.
The electron capture detector contains a radioactive source, Ni-63, and
is highly sensitive to chlorinated and highly conjugated organic compounds,
The flame ionization detector is sensitive to all hydrocarbons. The gas
chromatographic column used in separation of components is four feet
long, packed with a substrate coated with 2.5% by weight of a liquid
crystal.
The analysis column used is the one suggested by Janini (Ref.
C-10) specifically for POM separations. Gas chromatographic column para-
meters are summarized below:
Column length: 4' x 1/8" OD
Column material: Stainless steel
Stationary phase: 2.5% BMBT*
Support: Chromosorb W HP, 100/120 mesh
Flow: 40 ml/rain helium
Temperature: 235°C, isothermal
*N, N-bis [p-methoxybenzylidene]- a, a1 - bi-p-toluidine
The gas chromatograph is operated in the isothermal temperature
mode. This is necessary due to the extreme temperature sensitivity•of
the electron .capture detector, any attempt to temperature program would
result in a gross baseline drift.
Alternate chroaatographic methodology and retention time data
has been obtained from an analytical method of Gouw, et al. (Kef. C-ll)
and Lao, et al. (Ref. C-12). Literature column retention time data is
available for all the desired POM listed in the request for proposal
with the exception of the dibenzo[c,g]carbazole.
423
-------
Four of the eight POM are commercially available and are used in
fixing retention times and in calibrating the instrument response factors for
the various components. The 7,12 dimethyIbenz[a]anthracene, benzo[a]pyrene,
dibenz[a,b]anthracene, and 3-aethylcolanthrene POM are obtained from the
Eastman Kodak Company in the pure form. The other POM listed are not avail-
able from any commercial source known, so literature relative retention time
data of the other POM is utilized to fulfill analyses requirements.
The quantitization of total POM is made by taking the total
area of all POM and reporting the response area as if it were 9-methylanthra-
cene (C.gH,,,, Mol. Wt. 192.26), If PCB is found to be present, the concen-
tration is subtracted from the total hydrocarbon response area. The standards
used in measuring PCB response and retention times are known (Aroclor)
standards. The eight individual POM specifically required for identification
are analyzed separately, and reported as such. The eight materials are also
included in the total POM reported values.
C-7.4 Quality _Contro1
Quality control is maintained by two principal modes. Through-
out this study a number of samples are analyzed in duplicate to
assure precision of results. More importantly, however, carefully prepared
analytical standards and blanks are utilized in preparing suitable calibration
curves, thereby assuring accurate measurement of data. To test the accuracy,
known additions are made to 'samples that can be obtained in large enough
quantity to test for quantitative recoveries.
424
-------
REFERENCES FOR APPENDIX C
C-l Hamersma, J. W., Reynolds, S. L., and Maddalone, R. F., "IERL-RTP
Procedures Manual: Level I Environmental Assessment," EPA
Report EPA-600/2-76-160a, OTIS No. PB 257 850, June 1976.
C-2 Private communication with Theodore C. Rains, U. S. Dept. of
Commerce, National Bureau of Standards, Washington, DC (1974).
C-3 Rosen, A. A., and Middleton, F. M., Anal. Chem. 27, 790 (1955).
C-4 Moore, G. E., Thomas, R. S., and Monkman, J. L., J. Chrontatogr.
26, 456 (1967).
C-5 Levaygi, D. A., et al., J. Air Pollution Association 2_6 (6) ,
554 (1976).
C-6 Sandberg, J. S., et al., J. Air Pollution Association 26 (6),
559 (19765.
C-7 ASTM Standards, Part 23, Water & Atmospheric Analysis, p. 273,
Method 512-67, Referee Method A (1973).
C-8 Methods of Chemical Analysis of Waters and Wastes, US EPA,
EPA-625/6-74-003 (1974).
C-9 Hatch, W. R., and Ott, W. L., "Determination of Sub~Microgram
Quantities of Mercury in Solution by a Flameless Atomic Absorp-
tion Technique," Atomic Absorption Newsletter 6_, 101 (1967) .
C-10 Janini, G. M., Hohnston, R., and Zrelinski, W., Anal. Chest. 47,
(1975).
C-ll Gouw, T. H., Whittemore, I. M., and Jentoft, R. E., "Capillary
Column Separation of Various Poly Cyclic Aromatic Materials,"
Anal. Chem. 42r, 1394 (1970) .
C-12 Lao, R. C., Thomas, H., Oja, H., and Dubois, L., "Application
of Gas Chromatograph-Mass Spectrometer Data Processor Combination
to the Analysis of the Polycyclic Hydrocarbon Content of Airborne
Pollutants," Anal. -Chem. 45, 908 (1973).
425
-------
BLANK PAGE
426
-------
APPENDIX D
EFFICIENCY MEASUREMENTS
D.I EFFICIENCY
Unit efficiencies for boilers are calculated and reported accord-
ing to the ASMS Power Test Codes. These codes present instructions for
two acceptable methods of determining thermal efficiency. One method is
the direct measurement of input and output and requires the accurate
measurement of the quantity and high-heating value of the fuel, heat
credits and the heat absorbed by the working fluids. The second
method involves the direct measurements of heat losses and is referred
to as the heat loss method. This method requires the determination
of losses, heat credits and ultimate analysis and high-heat value of
the fuel. Some of the major heat losses include losses due to heat
in dry flue gas, losses due to fuel moisture content, losses due to
combustible material in refuse and flue gas, and radiation losses.
Heat credits are defined as those amounts added to the process in
forms other than the chemical heat in the fuel "as fired". These
include quantities such as sensible heat in the fuel, heat in the
combustion air, and heat from power conversion in a pulverizer or fan.
The relationships between input, output, credits and losses for a
steam generator are illustrated in Figure D-l.
KVB's experience has shown the heat-loss efficiency determina-
tion method to be the most reliable when working with industrial
combustion devices. However, methods developed for boilers must be
modified for other types of industrial equipment. Accurate fuel input
measurements are rarely possible on industrial units due to the lack
427
-------
HEAT IN FUEL (H,) (CHEMICAL)
INPUT
BA MEAT IN ENTERING AIR
BZ MEAT IN ATOMIZING STEAM
^ » SENSIBLE MEAT IN FUEL
X PULVERIZER OR CRUSHER POWER
B X 80ILER CIRCULATING PUMP POWER
R
X PRIMARY AIR FAN POWER
B X R6C1RCULATING GAS FAN POWER
B«iA HEAT SUPPLIED BY MOISTURE
„ IN ENTERING AIR
m B- HEAT IN COOLING WATER
CREDITS (BT
BOUNDARY
c
c
•" HEAT IN PRIMARY STEAM
— MEAT IN DESUPERMEATER WATER AND CIRCULATING PUMP INJECTION WATER
+ MEAT IN F6EDWATER
— HEAT IN SLOWDOWN AND CIRCULATING PUMP LEAK.QFF WATER
•- HEAT IN STEAM FOR MISCELLANEOUS USES
•• MEAT IN REHEAT STEAM OUT
— MEAT IN OESUPERH6ATER WATER
«* MEAT IN REHEAT STEAM IN
LOSSES (L)
UNBURNEO CARSON IN REFUSE
HEAT IN DRY GAS
MOISTURE IN FUEL
MOISTURE FROM BURNING HYOROOEN
MOISTURE IN AIR
HEAT IN ATOMIZING STEAM
•co
CARSON MONOXIDE
"UH
UNBURN6Q
•"UHC UwauRNED MYQROCARBONS
RADIATION AND CONVECTION
RADIATION TO ASH PIT, SENSIBLE MEAT IN
SLAG S, LATENT HEAT OF FUSION OF SLAG
SENSIBLE MEAT IN FLUE OUST
MEAT IN PULVERIZER REJECTS
HEAT IN COOLING WATER
SOOT BLOWING
OUTPUT » INPUT - LOSSES
• DEFINITION: EFFICIENCY (PERCENT) = 17 r.) »
JttSMT » 100 « INgHT..- k * 100
INPUT Mj -f a
HEAT BALANCE: H, -h B = OUTPUT + L OR '17 (r.) s 1 - ~=-a
* L n,-f8j
x 100
Figure D-l. Heat balance of steam generator.
428
-------
of adequate instrumentation thus making the input-output method
undesirable. The accuracy of the efficiency based on the heat loss
method is determined primarily by the accuracy of the flue gas
temperature measurement immediately following the last heat removal
station, the stack gas excess O level, the fuel analysis, the
ambient temperature, and proper identification of the combustion
device external surfaces (for radiation losses). Determination of
the radiation and other associated losses may appear to be a rather
imposing calculation but in practice it can be accomplished by
utilizing standard efficiency calculation procedures. Inaccuracies
in determining efficiency occasionally occur even with the heat loss
method primarily because of out-of-calibration unit instrumentation
such as the stack gas exit temperature. However, this problem has
been resolved by KVB test engineers through the use of portable
instrumentation and separate temperature readings.
The abbreviated efficiency test procedure which considers
only the major losses and the chemical heat in the fuel as input will
be followed. Tables D-l and D-2 are the ASME Test Forms for Abbre-
viated Efficiency Tests on steam generators which exemplify the type
of forms to be used for recording the necessary data and performing
the required calculations.
These efficiency procedures have been* developed primarily for
steam generators and were used for steam generators tested in this
program. For other industrial combustion devices, there are no set
standards for efficiency computation. Methods for efficiency deter-
mination for those devices were developed separately after inspection
of the devices and based on discussions with the device operators, and
were based primarily on stack loss calculations.
429
-------
TABLE D-l
SUMMARY SHEET
A.SME TEST FORM
FOR ABBREVIATED EFFICIENCY
TEST
PTC 4.1-0(1964,
TEST NO BOILER NO.
DATE
OWNER OF PLANT LOCATION
TEST CONDUCTED BY OBJECTIVE OF TEST
DURATION
BOILER MAKE 1 TYPE RATED CAPACITY
STOKER TYPE S. SIZE
PULVERIZER, TYPE & SIZE • BURNER. TYPE
FUEL USED MINE COUNTY STATE
& SIZE
SIZE AS FIRED
PRESSURES i TEMPERATURES FUEL DATA
1
2
3
4
S
6
. 7
8
9
10
11
12
13
14
STEAM PRESSURE IN BOILER DRUM
STEAM PRESSURE AT S. H. OUTLET
STEAM PRESSURE AT R. H. INLET
STEAM PRESSURE AT R. H. OUTLET
STEAM TEMPERATURE AT 3. H. OUTLET
STEAM TEMPERATURE AT R H INLET
STEAM TEMPERATURE AT R.H. OUTLET
WATER TEMP. ENTERING (ECON HBOILERI
STEAM OUALITY1 MOISTURE OR P. P.M.
AIR TEMP. AROUND BOILER-(AMBIENT)
TEMP AIR FOR COMBUSTION
(Thi» it Reference Temperoture) t
TEMPERATURE-OP FUEL
GAS TEMP. LEA VINO (Boiler) (Econ.) (Air Htr.)
GAS TEMP. ENTERING AH (If condition! to be
corrected to guarantee)
PIIO
p«io
p«io
psio
F
F
F
F
F
F
F
F
F
UNIT QUANTITIES
15
16
17
18
19
20
21
22
23
24
25
ENTHALPY OF SAT. LIQUID (TOTAL HEAT)
ENTHALPY OF (SATURATED) (SUPERHEATED)
STM.
ENTHALPY OP SAT. FEED TO (BOILER)
(ECON.)
ENTHALPY OF REHEATED STEAM R.H. INLET
ENTHALPY OF REHEATED STEAM R. H.
OUTLET
HEAT ABS. LB OF STEAM (ITEM 16-ITEM 17)
HEAT ABS. LB R.H. STEAMdTEM 19-ITEM 18)
DRY REFUSE (ASH PIT » FLY ASH) PER LB
AS FIRED FUEL
Btu PER LB IN REFUSE (WEIGHTED AVERAGE)
CARBON BURNED PER LB AS FIRED FUEL
DRY CAS PER LB AS FIRED FUEL BURNED
Btu/lb
Btu/lb
Btu/lb
Btu/lb
Btu/lb
Btu'lb
Btu/lb
Ib/lb
Btu/lb
Ib/lb
Ib/lb
HOURLY QUANTITIES
26
27
28
29
30
31
ACTUAL WATER EVAPORATED
REHEAT STEAM FLOW
RATE OF FUEL FIRING (AS FIRED ~t)
TOTAL HEAT INPUT (Item 28 X Item 41)
1000
HEAT OUTPUT IN BLOw.DOWN WATER
H°JAU (Item 76.lte»20>.(lt... 27-11.". 21). Item 30
OUTPUT 1000
Ib/hr
Ib/Kr
Ib/hr
kB/hr
kB/hr
kB/hr
FLUE CAS ANAL. (BOILER) (ECON) (AIR HTR) OUTLET
32
33
34
35
36
CO,
0. .
CO
.N, (BY DIFFERENCE)
EXCESS AIR
•; VOL
•; VOL
r; VOL
-. VOL
•;
COAL AS FIRED
PROX. ANALYSIS
37
38
39
40
MOISTURE
VOL MATTER
FIXED CARBON
ASH
TOTAL
41
-12-
Btu per Ib AS FIRED
ASH SOFT TEMP.'
ASTM METHOD
S-
COAL OR OIL AS FIRED
ULTIMATE ANALYSIS
43
44
45
46
47
40
37
CARBON
HYDROGEN
OXYGEN
NITROGEN
SULPHUR
ASH
MOISTURE
TOTAL
COAL PULVERIZATION
48
49
50
64
GRINDABILITY
INDEX-
FINENESS ".THRU
50 M*
FINENESS % THRU
200 M*
51
52
53
44
41
OIL
FLASH
Sp. Grav
POINT F'
>tr De9. API-
VISCOSITY AT SSU'
BURNER SSF
TOTAL
% wt
Btu per
HYDROGEN
Ib
CAS
54
55
56
57
58
59
60
61
CO
CH4 METHANE
C,H, ACETYLENE
C,H, ETHYLENE
C,H, ETHANE
H,S
CO,
H, HYDROGEN
TOTAL
62
63
41
TOTAL
% wt
HYDROGEN
r. VOL
,
DENSITY 68 F
ATM. PRESS.
Btu PER CU FT
Btu PER LB
INPUT-OUTPUT ITEM 31
EFFICIENCY OF UNIT r.
100
ITEM 29
HEAT LOSS EFFICIENCY
65
66
67
68
69
70
71
72
HEAT LOSS DUE TO DRY GAS
HEAT LOSS DUE TO MOISTURE IN FUEL
HEAT LOSS DUE TO H,0 FROM COMB OFHj
HEAT LOSS DUE TO COMBUST. IN REFUSE
HEAT LOSS DUE TO RADIATION
UNMEASURED LOSSES
Btu/lb
A. F. FUEL
TOTAL
EFFICIENCY = (100 - Item 71)
r. of A. F
FUEL
"Not Required for Efficiency Testing
T For Poml of Meosurement See Par. 7.2.8.1. PTC 4.1-1964
430
-------
•CABLE D-2
CALCULATION SHEET
ASME TEST FORM
FOR ABBREVIATED EFFICIENCY TEST
PTC 4.1-b (1964)
Revised September, 1965
OWNER OF PLANT
30
24
25
34
4J
44
47
M
49
70
7J
72
I
HEAT OUTPUT IN BOILER SLOW-DOWN
1! impractical to weigh refuse, this
item eon be estimated as fallows
DRY REFUSE PER LB OF AS FIRED FUE
ITEM 43
CARBON BURNED
FUEL "°
TEST NO.
WATER 3L3 OF WATER BLOW.OQWN PER HR
* ASM IN AS FIRED COAL
100 - * COMB. IN REFUSE SAMPLE
~TEM22 ITEM 23 ~
X
14,500
DRY CAS PER LB 11CQ, * 80, * 7(N, » CO)
BURNED" "" «co, * cos ~ "
ITEM 33 ITEM 33 / ITEM 35
11 X * 8 X * 7V
3 x
CO
AIR t a 100 K --
' ' .24S2N, - (Oj _ C0_
2
/ITEM 32 ITEM 34 \
v * /
IT
BOILER NO. DATE
X
" ITEM IS ITEM 17"
1000
k3/hr
NOTE: IF FLUE OUST S ASH
PIT REFUSE DIFFER MATERIALLY
IN COMBUSTIBLE CONTENT, THEY
SHOULD BE ESTIMATED
SEPARATELY. SEE SECTION 7,
COMPUTATIONS.
BURNED PER LB AS.
ITEM 34 ]
* / X
FIRED FUEl
ITEM 24
. 3 ,,
' * « S1,
IT EM 47
*
_ 26? J
p,.-,, - 'T6M34
2
.2682 [ITEM 35) -(ITEM 33
ITEM 34 ,
2
HEAT LOSS EFFICIENCY
HEAT LOSS DUE LB DRY GAS ITEM 35 (ITEM13) ~- d«.»fm.rvoiton ** *>£*«» air »** Append** 9.2 - PTC 4.1-1964
* If (*»•*« or. nwt m««to/«d, wi* ABM A Siond.jrd Radiation Lo»» CSaft. F.q. 8, PTC 4.1*1964
** U«iMMi*furMl !***«* lifted irt PTC 4,t buf n»r t«b«lai*d abo
-------
BLANK PAGE
432
-------
APPENDIX E
D&TA RSCORDING FORMATS
E.I DOCUMENTATION OF RESULTS
£.1.1 Field Measurements
During testing, two sets of measurements are recorded: (1) control
room data which indicate the operating condition of the device and (2)
mobile laboratory data that were the readouts of the individual analyzers.
Figure E-l is a copy of a typical data sheet used to record the control
room data and Figure E-2 is the data sheet for the mobile laboratory data.
While the measurements are made, the console operator in the
laboratory fills in the mobile laboratory data sheet. Normally the
tests will be conducted with the combustion device control in the manual
mode in order to stabilize operating conditions and accelerate the test
program.
Concentrations of the following species are measured or calculated
and recorded:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Species name
Total Nitrogen Oxides
Nitric Oxide
Nitrogen Dioxide
Carbon Dioxide
Carbon Monoxide
Total Hydrocarbon
Sulfur Trioxide
Sulfur Dioxide
Oxygen
Solid ^articulates
Condensible Particulates
Particulate Size
Smoke Spot
Opacity
Symbol used
NOX
NO
N02
C°2
CO
HC
so3
so2
°2
Sid. Part.
Con. Part.
Part. Size
Smoke
Opac.
433
-------
The concentration of all gaseous species are measured and
displayed continuously by analyzers and strip chart recorders located
in the instrumentation trailer. The strip chart recorder tapes will
be retained for future reference. The sulfur oxides, smoke, and
particulates will be measured at the sampling port and the measurements
recorded in data sheets.
A number of data sheets have been developed for use in field
measurements of emissions. They are listed below together with their
purpose.
Figure
No.
Sheet Title
Purpose
E-3 SO Data Sheet
x
E-4 Sulfur Oxides
Calculations
E-5 Plume Opacity
Observation Record
E-6 Velocity Traverse
E-7 Method 5 Control
Console Readings
E-8 Particulate
Calculation.Sheet
E-9 Particulate Emission
Calculations
E-10 Brink Cascade Impactor
Data Sheet
E-ll Andersen Cascade
Impactor Data
2-12 Gaseous Fuel Analysis
E-13 Trace Species and
Organics Sampling Data
Record measurements taken
Change units, normalize to a standard
excess oxygen
Record plume opacity readings
Record temperature and velocity
profiles of flue
Record volumes, temperatures and
pressures of Method 5 unit
Calculate weight of solid particulate
catch
Calculate particulate emissions
Measured weights on stages of cascade
impactor
Measured weights on stages of
cascade impactor
Calculation of combustion parameters
from gas analysis
SASS train operational data
434
-------
Test No._
Unit No.
Date_
Fuel
Figure E-l
UNIT OPERATING DATA
Location
Test No._
Engr.
Capacity
Unit Type_
Burner Type
1. Test Number
2. Date
3 . Time
4. Load
5. Process Rate
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
435
Data Sheet 6002-1
-------
Figure E-2.
Test HO._
Unit No.
Cnit Type
Date
MOBILE LABORATORY DATA
Location
Test No._
Engx.
Fuel
Capacity
Burner Type_
1. Test No.
2. Date
3. Tine
4. Load
5. Process Rate
6. Flue Diam. or Size, ft
7. Probe Position
8. Oxygen (%)
9. NOx (hot) read/3% O? (ppm)*
10. NO (hot) read/3% 0^ (ppm)*
11, HO? (hot) read/3% 02 (ppa)*
12. SO (cold) read/3% 02 (ppm)*
13. Carbon Dioxide (%)
14. Carbon MonosdLda (ppm) uneor/cor
#
15. Hydrocarbon (ppm) uncor/cor
16. Sulfur Dioxide (pom) uncor/cor
17. Smoke Spot (Bacharach)
18. Atmos. Temp. (°P/°C)
19. Dew Point Temp. C*F/"C)
20. Afaaos. Pressure (in. Hg)
21. Relative Humidity (%)
22.
23.
24.
25.
26.
27.
28.
29.
3O.
*Correction to 3% O2 should not be performed if
the value is measured on a wet basis.
Data Sheet 6002-2
436
-------
Figure S-3.
Date
K V B. INC.
Test No.
SOX DATA SHEET
TEST NO.
UNIT NO.
FUSL
LOAD
b/hr
Location
Box No.
Time
Temp, in Gas Meter
Press, in Gas Meter
Meter Reading
Barom. Press,
Percent Oxygen
N2 Purge Time
Calculation:
(A - B) x N x F x (460 +• T) X 24
Vp)
Excess 0,
so
A » Ml of lead perchlorate used for sample =
B «• Ml of lead perchlorate used for bland «
N * Normality of lead perchlorate titrant =>
f » Dilution factor »
T ** Average temp, in gas meter «
V «» Volume of gas sample ft3 -
P - Barometric pressure *
p » Pressure in gas meter <*
Conc«ntration.,C, ppm ""
B - df 2090 1
EO.SJ-XOj I
where- *• J
fiBissioa ,2, g/Mcal *
Ib/MBtu "
so
C - pollutant concentration, g/dsos
P, •volwiw factor - dsqa/10 cal
from F«d. tog. 9/11/74 p 32BS6
60-14
r«v. 1/2/75
437
-------
Figure E-4.
Test
Date_
Sulfur Oxides Calculation
Nomenclature:
S*» % by weight of sulfur in fuel*
'HV=* Fuel Heating Value (BTU/lb)=
hi= (moles of species i)/lb fuel
h- « I of moles of dry flue gas/lb fuel
fg
Q= Fuel flow rate »
S02 2 * 1Cj4 Gl) ' -
S°2 (ib. foal in) - 2xl0*"2 (S)
S02 = 2 X 10(S4Q)
% carbon in fuel (value assumed)
% sulfur in fuel ( " " )
% hydrogen in fuel (" " )
% 02 in fuel ( " " )
% 02 in stack- gas .
*t"
V
% O2 fuel m
)2 32QQ
4.762 (Nc + Ng) -t- .9405 hg - 3.762 hQ fuel
1 - 4.762 T-jri- stack
SO2 (ppm) = jj— x,10 = (assumed)
S03 (ppm) - (0.1) S02 » (assumed)
43S
-------
Figure E-5.
PLUME OPACITY OBSERVATION RECORD
Test Run So.
LOCATION MO.
OHKSR
DATE
OBSERVER _
. BOILER NO.
"FUEL TYPE
CAPACITY
ktb/hz
BURNER TYPE
POINT OP EMISSION
POINT OP OBSERVATION
TEST
NO.
Time
am/pm
Type
p
Test
Load
Ki/hr
Opacity
%
WIND
Speed
»oh
Direct ,
Sky
Cond .
Sun
Posi-
tion
Coicaents
439
-------
Project:^
Date:
Figure E-6.
VELOCITY TRAVERSE
Test Description:
Location:_
Unit:
Test:
Fuel:
Stack Cross Section
Personnel:
Barometric Press, (in. Hg):
Absolute Static Press, in Stack (in. Kg):.
Pitot Tube Coefficient:
(P8>
V - 85.48 C
1/2
Time
Traverse Point
Port Depth
Velocity
Head
(in. H20)
AP
*
Gas Temp.
CF)
Gas Temp.
CR)
TS
Molecular
Wt.
«S
Velocity
(ft/sec)
vs
02
Cone.
(% Dry)
440
6002-13
-------
Figure E-7.
PLANT
LOCATION
OPERATOR"
DATE
METHOD S CONTROL CONSOLE READINGS
RUN NO.
SAMPLE BOX NOT
METER BOX NO. "
«ETER H ~~
- FACTOR"!
AMBIENT TEMPERATURE
BAROMETRIC PRESSURE "
ASSUMED MOISTURE, I "
HEATER BOX SETTING "
PROBE LENGTH, IN.
NOZ2LE DIAMETER, IN."
PROBE HEATER SETTING"
SCHEMATIC OP STACK CROSS SECTION
Traversa
Point
Number
TOTAL
WrRAOE
Sampling
Time
{ejMin.
Static
Pressure
«P
AVfi,
AVG.
Sample
Box
Pemprta-
ture
«P
AVG.
Temperature
of Gas
Leaving
Condenser on
Last Impinger
°P
-------
Figure E-8.
PASTICULATE CALCULATION SHEET
Test Crew
Test »o._
Box No.
Date
Location
Sample Probe Position
Test Description
Dry Gas Meter Vol. (
Final
Initial
Total
Beaker No.
Date
Weighed
Tare 1
Wt. 2
3
4
5
6
Aver
Bottle No.
Impinger
Content (Water)
Rinse (ml)
Date Weighed
or 250 Bake '
Final 1
Wt. 2SO 2
3
4
5
6
Avgf
Residue wt
Final 250-Tare
Date Weighed
or 650 Bake
Final 1
Wt. 650 2
3
4
5
6
Avg
Residue Wt
Final 650-Tare
ftj>
J
Probe
(Acetone)
Final
[nitial
a voi
Probe
(Water)
Impinger
1 2
Cyclone
(Acetone)
Water Vc
3
-
Flask
(Dry)
1 (ml)
S. Gel 1
Filter
Ho.
otal
Blank
No.
Comments:
Data Sheet 6002-3
442
-------
Test. No._
Obit So.
Figure E-9.
PAKTICUIATE EMISSION CALCULATIONS
Data Location
Fuel load
Test No,_
Engr.
Pitot Factor, Fs
Barometric Pressure, P,
bar-
Tot. Liquid Collected, V
ml Total Particulate, M
. Hg
m gm.
Velocity Head,
iwg Stack Temp., Ts_
*R stack Area, As
ft
Saiqale Volume, Vtn
ft'
Stack Press., Psg
jLwg Excess O_, X0_\.
Orifice Press. Diff., H_
Sample Time, 9
inin
1. Sample Gas Volume Vta _, - 0.0334 Vm(P.
std bar
iwg Stack Gas Sp. Gravity, Gs_
Hozzle Diameter, Dn
H/13.6)
Vw . . - 0.0474 V.
std 1
2. Water Vapor
3. Moisture Content Bwo - Eq. 2/CEq. 1 + Eq. 2}
4. Concentration a. C * 0.0154. Mn/Vm _,
Sto
b, C * 2.205 x 10~6 Mn/Vm
C. C - Eq. 4b x 16.018 x 10
std
3
5. Abs. Stack Press. Ps » P. x 13.6 + Psg
bar
6. Stack Gas Speed Vs « 174 Fs
407 1.00
Ps X Gs
7. Stack Gas Flow a. £»sw » Bq. 6 x As x ~^£ x 25_
Rate § 70*F Ts 4Q7
b. 2sd - Eq. 7a x (1. - Eq. 3)
8. Material Flow Ms - Eq. 7b x Eq. 4b x 60
2090/(20.9 - XO2%)
10.' Emission a. E » Eq. 4b x Fe x Eq. 9
9. XD factor
11. % Isokinetic
b. E - Eq. 4c x Fo x Eq. 9 x 1000
14077
B x Vs x Ps x Dn
Fe SC Feet/104 Btu
4
Fa SC Meters/10 joules
Oil
92.2
0.002475
Gas
87.4
0.002346
Coal
98.2
0. 002636
in.
n.d.
SCF
SCF
N.D.
graina/DSCF
Ib/DSCF
grams/OSCM
in. w abs.
ft/min
WSCF/min
DSCF/ndn
Ib/hr
N.D.
Ib/MMBtu
ng/joule
Data Sheet 6002-4
443
-------
Figure 5-10.
BRINK CASCADE IMPMIfOR DATA. SHEET
Test No.
tEST RUN HO.
IMPACTOR NO.
LOCATION
DATE
CYCLONE NO.
OPERATOR
SAMPLE POINT LOCATION
SUBSTRATE COATING
FUEL
TEST LOAD
IMPACTOR ORIENTATION
FLUE STATIC PRESSURE
NOZZLE OIA.
FLOW THRU IMPACTOR
.klb/hr
CFM
JLnH2O, VELOCITY_
am IMPACTOR PRESSURE DROP
END TIME
GAS METER END
CF
GAS METER START
GAS VOLUME
CF
START TIME
DURATION
CF
FLOW RATE
CFM
AMBIENT TEMPERATURE
PRESSURE
IN Hg. HUMIDITY
FLUE GAS MOLECULAR MT.
, TEMP.
*F, DENSITX
g/CC»VISCOSITY
POISE
Foil +• Saaple, g
Unused Foil, g
Sample, g
Correction
for Blank, g
Final Sample, g
• Stage Number
^
2
3
4
5
••
Stage
Blank
FILTER NO.
.Sample Blank
FILTER + SAMPLE,g
FILTER TARE, g
SAMPLE, g
CORRECTION FOR
BLANK, g
_PINAL SAMPLE,
FULL CONTAINER, f
EMPTY CONTAINER,
Of CLONE CATCB, g
444
-------
Figure E-ll.
ANDERSEN CASCADE IMFACTOR DATA
Test No. Location Owner
Impactor No. Nozzle Size Filter No.
Stack Temperature °F Impactor Flow Rate CFM
*>•
&
UT
Plate
1
2
3
4
5
6
7
8
Back Up
Filter
Tare (g)
Final (g)
Net (g)
i
%
j
Cum. %
BCD (y)
Data Sheet 6002-5
-------
Figure E-12.
GASEOOS FUEL ANALYSIS
TBSt No
Unit No.
Data
Fuel
Test So
Location
Engr
Fuel Sample No
Fuel Sample Point
Gas
CH4
C.H,,
C3H8
cffl
C It
G2Hi2
C3H6
48
cnHin
crtr®
22
Q6 6
N_
CO-
CO
H2
Methane
Ethane
Propane
Butane
Pentane
Ethylene
Propylene
Butylene
Pentylene
Acetylene
Benzene
Oxygen
Nitrogen
Carb-r Diox
Carb. Monox
Hydrogen
%
Volume
X
X
X
X
X
X
X
X
X
X
X
X
•
X
_ X
CF
CF
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
air
fuel
0955
1671
2387
3103
3819
1432
214S
2869
3580
1193
3580
Fuel Analysis by
Btu(HHV)
CF
9
17
25
fuel
.94
.51
.19
33.21
41
15
23
31
39
14
38
.11
.80
.33
.23
.16
.57
.48
CF C02
CF fuel
0.01
0.02
0.03
0>04
0.05
0.02
0.03
0.04
0.05
0.02
0.06
CF H^O
CF fuel
0.02
0.03
0.04
0.05
0.06
0.02
0.03
0.04
0.05
0.01
0.03
-0.0477
0.
0.
0239
0239
3
3
.15
.18
0.01
0.01
0.01
CF
CF
0.
0.
0.
0.
0.
0.
0,
0.
0.
0.
0,
-0.
0.
0.
0.
0.
Prod
fuel
1055
1821
2587
3353
4119
1532
2298
3063
3330
1343
3730
0377
01
01
0289
0289
Ib Fuel
CF fuel
0.000416
0.000786
0.001171
0.001548
0.001864
0.000726
0.001087
0.001449
0.001813
0.000682
0,002017
0.000828
0.000728
0.001145
0.000724
0.0000522
Total
Theoretical Air:
SCF air CF air
CF fuai ~ 10 / 'CF fuel
HSCF Prod
10s Btu
% Moisture
DSCF Prod
106 Btu
CF.JTOJL
CF fuel
6 Btu (HHV)
'
7
WSCF Prod (100 - %
1Q6 Btu' X 100
% C02, dry
CF fuel
x 100
L.SxlO
6
MM x {DSCF/106 Btu) ,
K1 "JV43Q
_6
Btu - (ppm @ 3* 02)/K
nf/J - (ppm « 3% 02>A'
SCF atr/lCT Bt« 9 70*F,
29.92 in. Bg.
Wet SCF Prod/106 Btu
Dry SCF/100 Btu
1C for
Stu
Data Sheet 6002-6 (Rev. 2)
446
-------
Figure E-13.
TRACE SPECIES AND ORGANIC SAMPLING DATA
Projects
Date:
Locations
Units
Testt
Fueli
Personnel: Barometric Press i
Absolute Static Press, in Stack (in. fig) i
Pi tot Tube Coefficients
(PS)
(in H20)
Orifice
&?
(in H2O)
Cum.
Meter
Volume
(ft3)
Pump
Suction
(in, Hg}
•
TEMPERATURE ( * F )
Stack
Probe
•
XAD-2
Iropinger
Out
Oven
Meter
In/Out
°2
Cone,
% dry
-------
BLANK PAGE
448
-------
APPENDIX F
TRACE SPECIES AND ORGANIC EMISSIONS DATA
location
Number
10
12
13
14
15
Device
Cement Kiln
Black Liquor
Recovery Boiler
Petroleum
Process Heater
Wood/Bark
Boiler
Steel Open.
Hearth Furnace
Diesel Engine
Contents
Fuel
Natural Gas
Black'Liquor
Refinery Gas
Wood and coal
No. 6 Fuel Oil
+ Natural Gas
No. 2 Diesel
Oil
Test Page
9-3 ESP inlet 452
9-4 ESP inlet 458
9-5 ESP outlet 461
9-6 ESP outlet 464
9 Overall average 470
10/2-10 ESP inlet • 471
10/2-12 ESP inlet 477
10/2-14 ESP outlet 480
10/2-16 ESP outlet 483
12/2-3 Stack 490
12/2-6 Stack 493
13-18 Dust Coll. Outlet 500
13-24 Dust Coll. Outlet 507
14-2 ESP inlet 510
15-10 Stack . 517
15-11 Stack ' 523
449
-------
BLANK PAGE
450
-------
TABLE F-l. GENERAL NOTES FOR TRACE SPECIES AND OBGANICS DATA TABULATIONS
1. All sample data are rounded to two significant digits and corrected for
blanks,
2. Single number indicates all sample concentrations were above detection
limits.
3. Single number preceded by "<" indicates all samples were less than
detection limits. Value shown is maximum undetected amount.
4. For two numbers separated by "<", the number on the left of < indicates
the detected amount, and the number on the right indicates the maximum
potential amount including amounts from samples with positive detection
and amounts based on the detection limit for samples that were reported
as below the detection limit.
5. < DL, concentration below detection limits
-B, sample value equals blank, net value assumed zero
< Bt sample value less than blank, net value assumed zero
MC, major component, exceeds maximum measurable quantity (about 1000 yg/g
for spark source mass spectrometry)
NES, not enough sample for adequate analysis
NR, not reported, results uncertain because of complex sample matrix
composition
6. Species for which either the emission rate or input (or both) were below
detection limits have mass balance values indicated as follows:
< DL, both emission and input below detection limit
- > value, input value is below detection limit or emission value is
above detection limit
< value, emission value is less than detection limit.
451
-------
TABLE F-2.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 9-3, CEMENT KILN
*»
Ul
Sunpl* Type
Supl* Huabar
Sa>ple Nelght/Vol.
Onlts
Antiaony
Arienlc
BariuB
Beryllitai
Cadmium
Calciun
ChrcMlua
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
TellorluB
Tin
Tltantua
Vanadtm
Zinc
Chloride
Fluorida
Nitritei
Sal fates
Total PCM
Total PCa
No»le, Probe,
10 )!• Cyclone
Solids
384
20.2657 9
V9/9
< 50
2.0
< 20
< 0.5
4.4
310,000
31
38
11
12,000
< 200
82
< 0.2
24
< 4
< 50
< 50
1,900
30
40
709
ISO
8.7
< 50
0.1
< 1
pg/ia1
< 350
14
< 140
< 3.5
30
2,100,000
210
260
76
83,000
< 1400
570
< 1.4
170
< 28
< 350
< 350
13,000
210
280
4,900
1,000
60
< 350
0.69
< 6.9
I \im Cyclone
Solids
386
23.5244 g
W/9
< 50
1.6
< 20
0.6
4,6
420.OOO
20
24
11
13,000
< 200
83
< 0.2
30
< 4
< 50
< 50
2,100
30
42
1,210
290
8.1
< 50
0.1
< 1
M9/B1
< 400
13
< 16O
4.8
37
3,4OO,OOO
160
192
88
100,000
< 1600
660
< 160
240
< 32
< 400
< 400
17,000
240
340
9,700
2,300
65
< 400
0.80
< 8.0
1 M* Cyclone
Solids
393
15.6894 9
U9/9
< 50
3.0
< 20
1.2
If?
250,000
31
30
13
18,000
< 200
70
< 0.2
30
< 4
< 50
< SO
2,700
. 55
40
2,810
256
13.0
< 50
0.1
< 1
I19/"1
< 270
16
< 110
6.4
25
1,300,000
170
160
69
96,000
< 1100
370
< 1.1
160
< 21
< 270
< 270
14,000
290
210
15,000
1,400
69
< 270
0.53
< 5.3
Pilter»
271
4.2785 g
(19/9
< 50
4.0
< 20
2:9 *
5.1
250,000
80
55
17
2.0OO
< 200
140
< 0.2
39
< 4
< SO
< 50
3,000
90
45
21,000
420
28
52,000
< I
< 1
ft/"3
< 73
S.8
< 29
> 4.2
7.4
360,000
120
, 80
25
32,000
< 290
200
'. < 2.9
57
< 5.8
< 73
< 73
4,400
130
65
31,000
610
41
76,000
< 1.5
< 1.5
Solid
Section
Mash
9-3 G
1381 nl
M9/»l
0
< 8
< B
< 0.005
p
560
< •
< 0.08
O.02
19
0.16
0.18
< 0.005
0.09
< 0.04
< 2
< 1
O.8S
< 0.1
0.01
11
3.8
< 0.2
< 6
0.010
< 0.001
V«/«J
0
0
0
< 2.4
o
260,000
0
38
9.4
8900
75
85
< 2.4
42
< 19
< 940
< 470
400
< 47
4.7
5,200
1,800
< 94
< 2,800
4.7
< 0.47
Sea nota* on Table F-l
-------
TABLE P-3.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 9-3, CEMENT KILN
Sample Type
Suple Dumber
San>le Weight /Vol.
Units
An tl »ony
JUraenic
Bariua
Beryl HUB
Ca
-------
TABLE F-4.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 9-3, CEMENT KILN
Sample Type
Sanple Number
Saaple Welght/Vol.
units
hat loony
Arsenic
Barium
Beryl Hun
CadinitBD
Calcitw
CbroaiuB
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Seieniun
TelluriuB
Tin
Titaniua
Vanadium
Zinc
Chlortcla
Fluoride
Nitrates
Sui fates
Total POM
Total PCB
emission
in tactic,
< 3 W*
393 t 275
19.96? 5
w/»3
< 340
22
< 130
11
12
14OOOOO
290
240
94
128
< 1400
570
< 4.0
220
< 27
< 340
< 140
1 8000
420
280
46OOO
2000
110
76000
O.S3 <0,68
< 6.8
fatal
Emission
Concen .
SASS
J. 937 BJ
Ma/a3
< 3700
48 < 92
< 1600
61 < 72
1« < 153
8800000
890
1500
1100
220000
83 < 14OOO
2300
S. 1 < 26
920
11 < 370
< 7800
1600 < 5800
51000
890 < 1600
950
170000
11000
1200 < 1300
82000 <890OO
85 < 180
< 85
Total Emission
lute
Kiln exit by
SASS
20.12 n3/s
M/B
< 75000
960 < 1800
< 32000
1200 < 1400
2900 < 3100
178 000000
18000
31000
22000
4500000
170O < 29OOOO
49000
103 < 510
18000
230 < 7500
< 160000
3200O < 1200OO
1000000
18000 < 32000
19000
3400000
210000 < 220000
25000 < 27000
1600000<1BOOOOO
1700 < 3600
< 1700
Kiln Feed Slurry
1016
26000 q/e
M9/9 .
< 25
1.7
< 15
0.1
1.7
240OOO
10
10
14
13000
< 100
50
< 0.1
10
< 4
< 25
< 25
1100
27
11
93.1
66.7
< I
41.7
0.5
< 1
iig/s
< 650000
440OOO
< 390000
7800
44000
6.2xl09
260000
260000
360000
140x10*
<2600OOO
1300000
< 2600
260000
< 100000
< 6SOOOO
< 650000
2.9X106
700000
2900OO
2400000
1700000
< 26000
1100000
13000
< 26000
Kiln Discharge Clinker
1017
10200 g/s
M9/9
< 50
1.7
< 20
1.4
S.4
450000
31
26
18
25000
< 200
140
< 0.2
23
< 4
< 50
< 50
2400
65
35
12.0
54.0
< 1.2
< 40
< 0.1
< 1
»•?/»
< 510000
17OOO
< 200000
14000
550OO
4.6xl09
320000
270000
180000
260xlQ6
< 2OOOOOO
1400000
< 2000
23OOOO
< 41000
< 510000
< 510000
24x10*
660000
360000
120000
560000
< 12000
< 4100OO
< 1000
< 10000
Kiln Emission
by Process Flows
Feed-Clinker
Mq/s
< OL
27000
< DL
0
Q
1.6x10*
0
0
180000
aoxio6
< DL
o
< OL
3OOOO
< DL
< PL.
< DL.
' 5000000
40000
0
230000O
iiooooo
< DL
O.69xl06
-------
TABLE P-5.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY
TEST 9-3, CEMENT KILN
ui
ui
Staple Type
Saaple Number
Sampla Welght/Vol.
Unit*
AntiBony
Arsenic
Barium
Beryl HIM
CadaiuB
CalcluM
Chromiua
Cobalt
Copper
Icon
Lead
Manganese
Harcury
Nickel
Salenlun
Tellurian
Tin
Titanium
Vanadium
Zinc
Chlorine
Fluorine
Combined
Solids
9-3 A
61,7780 q
U9/9
< 0.8
22
200
0.3
< 0.4
HC
36
6
10
HC
30
40
NR
10
1
< 0.2
0.7
930
40
30
900
560
pg/BJ
< 51
1400
13000
19
< 26
HC
2300
380
640
HC
190
2600
—
640
64
< 13
45
59000
2600
190
57000
36000
XAO-2 Resin
9-3 B
ISO g
MAr
< 0.5
< 2.1
3
< 0.5
< 0.9
24
< B
< 0.1
1.0
« B
< 2
0.5
HR
1.1
< 2
< 0.5
< 0.5
8.0
0.19
- B
« B
< B
M9/«J
< 26
< 110
150
< 26
< 46
1200
0
< 5.1
51
0
< 100
26
—
56
< 100
< 26
< 26
410
9.7
0
0
0
Combined
Liquids
9-3 C
4,692 Hi
(ig/Bl
0.020
< B
< B
< B
< 0.004
HC
0.060
0.0036
0.013
0.58
0.032
0.032
HR
0.042
< O.I
< 0.004
< B
< 0.095
0.0058
0.38
2.6
HC
M/»J
34
0
0
0
< 6.8
HC
100
6.5
21
990
54
54
—
72
< 170
< 6.8
O
< 160
9.9
650
4400
HC
Total
Emission
Concert .
SASS
2.937 m1
ug/»3
34 <111
1400<1510
13000
19 <45
< 79
1200 < MC
2400
390
710
99O OOOO
-------
TABLE F-6.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
: TEST 9-3, CEMENT KILN
l/l
Sample Type
Sample Number
Sample Helght/Vol.
Units
Aluminum
Biomuth
Boron
Bromine
Cerium
Cesium
Dysprosiun
Erbium
Europium
Gadolinium
Gallium
Germanium
Cold
Hafnium
Holmlum
Iodine
Iridiua
Lanthanum
Lithium
Lutetlum
Hagneaium
Molybdenum
Neodymium
Niobium
Osmium
Combined
Solids
9-3A
63.7780 g
W9/g
HC
0.5
6
20
28
35
1
0.5
0.5
0.9
a
0.5
< 0.2
1
0.7
22
< 0.2
25
13
0.2
HC
1
3
B
< 0.2
ug/m3
HC
32
380
1300
1800
2200
64
32
32
57
510
32
< 13
64
45
1400
< 13
1600
830
13
HC
64
190
510
< 13
XAD-2 Resin
9-3 B
150 g
pg/g
6.0
< o.s
2.0
< 7.0
< 0.5
1.0
< 0.5
< 0.5
< 0.5
< 0.5
<0.4.
< O.S
< 0.5
< 0.5.
< 0.5
< 3.5
< 0.5
< 0.5
0.8
< 0.5
56
< B
< 0.5
< 0.5
< 0.5
W9/m3
310
< 26
100
< 360
< 26
51
< 26
< 26
< 26
< 26
< 20
< 26
< 26
< 26
< 26
< 180
< 26
< 26
41
< 26
2900
0
< 26
< 26
< 26
Contained
Liquids
9-3 C
4692 ml
pg/ml
0.44
< 0.000
< B
0.028
0.016
0.0099
< 0.004
< 0.004
< 0.004
< 0.004
< B
< B
< 0.004
< 0.004
< O.O04
0.2
< 0.004
< 0.026
• B
< 0.004
< B
0.0022
0.02
< 0.004
< 0.004
M9/m3
750
< 14
0
48
26
17
< 6.B
< 6.8
< 6.8
< 6.8
0
0
< 6.B
< 6.8
< 6.8
330
< 6.8
44
0
< 6.8
0
3.7
34
< 6.8
< 6.8
Total
Emission
Concen.
SASS
2.937 m3
wg/.3
1100
-------
TABLE F-7.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 9-3f CEMENT KILN
Ul
S*i|?i* Type
Supl* Number
Sample Weight /Vol.
Units
Palladium
Platinua
Phosphorus
Potassium
Praseodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Silicon
silver
Sodium
Sulfur
Strontium
Tantalum
Thallium
Terbium
Thorium
Thulium
Tungsten
Uranium
Ytterbium
Yttxiiat
Zirconium
Combined
Solids
9-3 A
61,7780 g
uo/9
< 0.2
< 0.2
820
HC
1
< 0.2
< 0.2
140
< 0.2
2
5
HC
0.4
MC
HC
100
< 0.2
3
0.2
4
0.2
< 1
4
1
a
34
M9/«3
< 1J
^ 13
52000
HC
64
< 13
< 13
8900
< 13
130
320
MC
26
HC
HC
6400
< 13
190
13
260
13
< 64
260
64
510
2200
JtAD-2 Resin
9-3 B
150 g
pg/q
< 0.5
< 0.5
< B
550
< 0.5
< 0,5
< 0.5
0.3
< 0.5
< 0.5
0.4
360
< O.S
90
B
0.4
< 0.5
< 0.5
< 0.5
< O.S
< 0.5
< O.S
< 0.5
< 0.5
< 0.5
< B
pg/m
< 26
< 26
0
2SOOO
< 26
< 26
< 26
15
< 26
< 26
20
18000
< 26
4600
0
20
< 26
< 26
< 26
< 26
< 26
< 26
< 26
< 26
< 26
O
Combined
Liquids
9-3 C
4692 Hi
Mg/ml
< 0.004
< 0.004
0.016
HC
< 0.02
< O.004
< 0.004
0.095
< 0.004
< O.OO4
< O.005
< a
HC
HC
HC
< B
< 0.2
< 0.004
< 0.004
< 0,004
< 0.004
< O.OO4
< 0.004
< 0.004
< B
< B
w/«3
< 6.8
< 6.8
27
HC
< 14
< 6.8
< 6.8
160
< 6.8
< 6.8
< 8.4
0
HC
HC
HC
0
<340
< 6.8
< 6.8
< 6.8
< 6,8
< 6.8
< 6.8
< 6.8
0
O
Total
Emission
Cone en.
SASS
2.937B3
M9/»J
< 46
< 46
52000
28000 < HC
64 < 120
< 46
< 46
9100
< 46
130 < 160
340 < 350
18000< NC
26 < HC
46000 < HC
HC
64OO
< 380
190 < 220
< 46
260 < 290
13 < 46
< 97
260 < 29O
64 < 97
510 < 540
2200
Total
Emission
Rate
20,12n3/*
M9/«
< 920
< 920
1000000
560000 < HC
1 300 < 2SOO
< 920
< 920
1BOOOO
< 920
2600 < 3300
>800 < 7000
J60000 < NC
520 < HC
13000 < HC
HC
130000
< 7600
1800 <4500
< 920
5300 < 5900
260 < 290
< 1900
5100 <59OO
1300 < 1900
10000 < 11000
44000
See note on Table F-l
-------
TABLE F-8. TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 9-4,'CEMENT KILN
*>.
ui
00
Saaple Type
Sa*t>l* MtMfcer
Sapple Uelght/Vol.
Unit*
Aatlaony
ATMOic
Bariua
Berylliun
CadMiua
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
fluoride
Nitrate*
Sul fates
Total POH
Total PCB
Noizle, Probe,
10 in Cyclone
Solid*
394
17.6210 9
uq/g
< so
< 0.5
< 20
1.7
4.5
480000
21
36
14
10000
< 200
90
29
< 4
< 50
< 50
1900
40
40
990
140
6.6
50
HR
NR
lig/m3
< 300
< 3.0
< 120
10
27
2900000
110
220
85
61000
< 1200
S50
180
< 24
< 300
< 300
12000
240
240
6000
850
40
300
—
—
I \m Cyclone
Solid*
410
19.4157 q
ug/9
< SO
2.5
< 20
2.0
3.0
260000
18
31
12
10000
< 200
48
22
< 4
< 50
< 50
2000
50
35
1400
160
7.3
< 50
NR
NR
M9/»3
< 340
17
< 130
13
20
17OOOOO
120
210
80
67000
< 1300
320
ISO
< 27
< 340
< 340
13000
.340
230
9400
1100
49
< 340
—
—
1 \im Cyclone
Solid*
407
12.6696 g
M9/9
< SO
1.0
< 20
1.5
1.7
290OOO
32
34
14
17000
< 200
65
29
< 4
< SO
< 50
2600
70
41
3200
320
8.4
170
NR
NR
P9/m3
< 220
4.4
< 87
6.6
16
130OOOO
140
150
61
740OO
< 870
280
130
< 17
< 220
< 220
11000
310
180
14000
960
37
740
«
—
Filter*
274
4.4659 g
yg/g
< 50
1.0
• < 20
2.3
3.6
210000
42
34
17
22000
< 200
100
31 •
< 4
< 50
< 50
3000
80
42
24000
330
16
320OO
NR
NR
U9/m3
< 77
l.S
< 31
3.5
55
120000
65
52
26
34000
< 310
150
48
< 6.2
< 77
< 77
4600
120
65
37000
510
25
49000
—
~
Solid
Section
Wash
9-4 *
1625 ml
W/ml
0.1
- B
< B
< 0.005
0.005
299
< B
0.03
0.01
8.1
0.07
0.09
< 0.005
0.01
< 0.04
< 2
< 1
< 0.45
< 0.1
- B
1.1
0.48
< 0.2
6
NR
NR
pg/m3
56
0
0
< 2.8
2.8
170000
0
17
5.6
4500
39
50
< 2.8
5.6
< 22
< 1100
< 560
< 250
< 56
0
620
270
< 110
3400
—
—
See note* on Table F-l
-------
TABLE F-9.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 9-4, CEMENT KILN
Saiijpl« Typ«
£aj*>l« NUMiMt
Saic>U ttaight/Vol.
Unit*
kntlaonjf
Axaenic
BoriuB
Beryl liua
CadaiuH
Calciua
Chrc»iu»
Cobalt
Copjxar
Iron
Lead
MaagaoeB*
Mercury
Klckal
SelenitiM
Telluriua
Tin
Titanium
VaaaaiuB
Zinc
Chloride
riuocida
Nitrate*
Sulfat**
Total FON
Total PCB
XM>-2
Basin
299
148.1 g
Ui/y
'< 50
< 0.5
< 20
• •
< 0.5
< B
< 1
< 5
4
< B
< 190
< a
O.S
< 1.5
< 4
< 50
< 50
< 60
< 10
< •
< 4
31
< B
53
MR
NR ,
yg/»J
< 2600
< 26
< 1000
0
< 26
0
< 51
< 260
200
0
< 9700
0
26
< 77
< 200
< 2600
< 2600
< 3100
< 510
0
< 200
1600
0
2700
_.
'
Organic Hodul*
Rinse
221
307 ml
119/Bl
< B
< B
< B
< o.oos
" B
0.6
< B
< 0,02
- B
0.29
• B
0.020
< O.OOS
0,02
< 0.04
< 2 ,
< 1
< 0.45
< O.I
- B
1.1
< 0.4
< 0.2
6
NR
NR
V?/"1
0
0
0
< 0.53
0
64
0
< 2.1
0
31
0
2.1
< 0.53
2.1
< 4.2
< 210
< 110
< 48
< 11
0
120
< 42
< 21
640
-_
—
Condensate
9-4 B
1703 mi
(Jj/Bl
< 0.1
< 0.02
< 0.1
< 0.005
0.015
i.a
< 0.02
< 0.02
< 0.01
0.16
< 0.02
0.01O
< O.OOS
< 0.02
< 0.04
< 2
< I
< 0.5
< 0,1
0.05
0.42
0.34
0.26
< 6
NR
NR
yg/»J
< 59
< 12
< 59
< 2.9
8.8
1100
< 12
< 12
< 5.9
94
< 12
5.9
< 2.9
< 12
< 24
< 1200
< 590
< 290
< 59
29
250
200
ISO
<3500
--
—
Impinger Ho. 1
838
829 al
tig/Ml
< B
< B
< 0.09S
< 0.0049
< 0.0098
< B
< B
< 0.001
0.030
0.22
0.030
< 0.0007
< 0.0049
< 0.002
< 0.040
< 2.1
< 1.0
< 0.48
< 0.10
0.012
< 0.40
< 0.21
0.11
6.0
HH
MR
V?/"1
0
0
< 27
< 1.4
< 2.8
0
0
< 0.3
a. 6
62
8.6
< 0.2
< 1.4
< 0.7
< 11
< 590
< 290
< 140
< 29
3.5
< 110
< 59
Jl
1700 (SOjl
,.
—
I«pina«r Ho. 2
9-4 C
1214
U9/B1
0.12
< 0.012
< 0.0066
< O.OOS
O.O04
< B
< »
< B
< B
< B
< B
< B
< O.OOS
< B
< 0.040
< 2.0
< 0.99
< 0.099
< 0.099
< B
< B
< 0.20
..
r—
HK
NR
•1
ll«/»J
48
< 5.2
< 28
< 2.1
1.7
0
0
0
0
0
0
0
< 2.1
0
< 17
< 830
< 410
< 41
< 41
0
0
*B3
—
—
_
_.
iHDlnaar Ha. 3
Horn
iig/nl
"I/"1
Ul
&•• aotM on Tabl« F-l
-------
TABLE P-10.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 9-4, CEMENT KILN
Sample Type
Sanple Number
Simple Height/Vo
units
Antimony
Arsenic
Bar tun
Beryl HUB
Cadaiun
Calciuni
Chrooiun
Cobalt
Copper
Iron
bead
Han9aneso
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
Nitrates
Sulfates
Mission
in Partic.
< 3 |)«
407 * 274
U 17.1355
M9/*3
< 300
5.9
< 120
10
n
1600000
210
200
87
110000
< 1200
430
< 1.2
180
6.2 < 23
< 300
< 300
16000
430
250
51000
1500
62
50000
Total
Enission
Concen.
SASS
2.897 »3
yg/*3
100 < 3800
23 < 69
< 1600
34 < 45
B3 < 110
660000O
450 < S20
660 < 930
460
240000
48 < 13000
1400
29 < 38
520 < 620
< 350
< 7200
< 5600
41000<45000
1100 < 1700
760
66OOO
5200<5500
330 < 480
55000<62000
Total Emission
Rake
19.01 »J/s
V9/a
1900 < 72000
440 < 1300
< 30000
650 < 860
1600 < 2100
1.3X108
8600 < 9900
13000 < 1800O
9100
4600000
910 < 25000
27000
550 < 720
9900<12000
< 6700
< 140000
< 11 0000
780000 <860000
21000 < 32000
14000
1300000
99000 < 100000
6300 < 9100
1 000000 < 1200000
Kiln Feed
Slurry
1018
24000 g/3
\l
-------
TABLE F-ll.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 9-5, CEMENT KILN
Sa*l>l* fyp«
Saapl* Numbor
SaopU Woight/Vol.
Unit*
AntiiKMiy
Arsenic
Baritai
Barylliua
Cadniua
CalctiM
ChroKiua
Cobalt
Copper
Iron
Lead
Man9*n*aa
Mercury
Nickel
Seleniua
Tellurlun
Tin
Tit«niu» '
Vanadira
Zinc
Chlorld*
Fluoride
Nitrate*
Sulfates
Total POM
Total KB
Horzle, Probe,
ID (!• Cyclone
Solids
9-5 E
324 Bl
H9/9
< 0.1
< 0.003
< 0.5
< 0.005
< 0.01
110
0.10
< O.O2
< 0.02
4,3
< 0.1
0.1S
< 0.003
0.07
< 0.005
< 0.5
< 0.5
0.5
< 0.02
0.02
2.1
0.84
0.38
< a
NR
NR
Hf/*3
< 3.5
< 0.10
< 17
< 0.17
< O.S5
1800
3.5
< 0.69
< O.69
ISO
< 3.5
5.2
< 0.10
2.4
< 0.17
<17
<17
17
< 0.69
0.69
73
29
11
<28Q
—
"•*•
3 MB Cyclone
Mash
455
271 ml
\>q/*i
< B
< B
< 0.15
< 0,005
" B
370
0.15
0.04
- B
13
< 0.08
0.15
< O.008
0.13
< 0.005
< 0.5
< 0.5
2.4
0.2
< B
0.64
2.0
0.86
< B
HA
NR
yg/»3
0
0
< 10
< 0.14
0
11000
4.3
1.2
0
380
< 2.3
4.3
< 2,3
3.8
< 0.14
< 14
< 14
69
5.8
0
19
58
25
<230
—
««
1 |in Cyclone
Solids
9-5 F
HB "1
|ig/«
< 0.1
< 0.003
< 0.5
< 0.005
< 0.01
840
0.45
0.06
O.O6
42
< 0.1
0.42
< O.O03
0.30
< 0.005
< 0.5
< 0.5
7.3
0.2
0.17
1.1
2.6
1.9
18
NR
NR
M?/»3
< 1.6
< 0.047
< 7.9
< 0.079
< 0.16
13000
7.1
0.95
0.95
660
< 1.6
6.6
< 0.047
4.7
< 0.079
< 7.9
< 7.9
120
3.2
2.7
17
41
30
280
—
™~
Filt.re
275
0.1
M/9
< 500
25
< 40
a
20
440000
420
250
50
14000
< 2000
350
< 2.0
220
< 4
< soo
< 500
3500
< 100
MO
43000
__
7900
„
NR
NR
59 o
tt/»3
< 9.9
0.50
< 0,79
0.16
0.40
8700
8.3
5.0
0.99
280
< 4O
6.9
< 0.040
4.4
< 0.079
< 9.9
< 9.9
69
< 2.0
2|? - -
850
—
160
—
—
— *
riltor
Hash
365
i*
yq/«d
NES
NES
NES
< O.OOS
NES
3.0
NES
NES
NES
NES
< 0.1
NES
< 0.003
NES
NES
NES
NES
NES
NES
«
NES
NES
NES
NES
NR
NR
•I
Mq/»3
—
™
—
< O.OOB
4. a
—
—
._
< 0.16
—
< o.oos
„
—
WH
—
—
—
—
—
—
__
—
~~
Sea notes on Table F-l
-------
TABLE F-12.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 9-5, CEMENT KILN
Bampl» Typ*
Soapl* Muofecr
6AH>1« Meiqht/Vol.
Unit*
Xntioony
JkzMaic
BuiiM
Buryliiua
Cadmium
Calcltia
Chroniu.
Cobalt
Copper
Iron
Lud
N*ng*M**
Marcury
nickel
Selenium
TUluriu-
Sin
TltaniuB
Vanadiu*
Zinc
Chloride
fluoride
tiitr*t**
fiulfatei
total KM
Total PCfl
XAD-2
Ra.ln
300
158 g
JIS/9
< SO
< o.s
30
« B
1.0
23000
1
IS
4
170
< 190
2
< 0.2
6.5
< 4
< 50
< 50
110
< 10
l.S
17
2i
63
300
HB
MB
I*/.1
< 840
< 8.4
510
0
17
190000
51
250
67
2900
< 1200
14
< 3.4
110
< 67
< 840
< 840
1900
< 170
59
620
350
110
5100
—
—
Oceanic Hadul*
Rin««
323
176 Hi
U9/«l
< B
-------
TABLE F-13.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 9-5, CEMENT KILN
Sample Typ*
Sample
Number
Sample
Meight/Vol.
Units
Antinony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Nanganese
Mercury
Nickel
Selenium
Tellurium
tin
Titanium
Vanadium
Zinc
Chlorlda
Fluoride
Nitrates
Sul fates
Emission
In Partic.
< 3 UB
9-5 F +
275 » 365
W9/*3
< 12
0,SO«O.S5
< 8.7
0.16<1.7
0.40*0.56
22000
15
6.0
1.9
940
< 42
14
< 0.092
9.1
< 0.16
< 6.8
< 0.8
190
3.2 < 5.2
4.9
870
41
190
280
Total
Emission
Concen.
SASS
0.375 m3
W9/m3
110 < 990
O.5 < 23
530 < 620
O.16 <5.9
18 < 25
420000
150 < 160
300 < 310
76 < 78
4700
24 < 3300
120
< 9.1
160 < 170
< 110
< 29000
< 1900
2300 < 2600
11 < 290
98
12OOO<13OOO
480 < 690
2100
5800 < 7800
Total
Emission
Rate
21.1 »3/a
|ig/s
3300 < 21000
10 < 490
11000 < 13000
3,4 < 120
380 < 530
8900000
1200 < 3400
6300 < 65OO
1600
99000
510 < 70000
250OO
< 190
3400 < 3600
< 2300
< 610000
< 40000
4900O<55000
230 < 6100
2100
25000<270000
12000 < 15000
44000
120000<160OOO
Kiln Feed
Slurry
1021
24000 g/s
•f/9
< 3.5
1.6
< 15
1.3
1.0
77000
a
22
6
7700
< 150
SB
< 0.2
16
< 4
< 40
< 40
1300
20
20
79.6
40.6
4.01
28.6
l»9/s
<84000
38000
<360000
31000
24000
l.BKlO9
190000
53OOOO
140000
180x10
<3600000
1400000
< 4800
380000
< 96000
<960000
< 9 60000
31x10*
480000
460000
1900000
970000
96000
690000
Kiln Discharge
Clinker
1022
9200 cj/s
M9/9
<50
2.5
<20
1.0
5.4
520000
31
28
15
2300O
<200
110
< 0.2
24
< 4
< 50
< 50
2400
70
22
2.85
62.0
< 1.4
<45
n/a
<460000
21000
<180000
9200
50000
4.BX109
2900OO
260000
140000
aioxio6
<180000
1000000
< 1800
220000
< 37000
<460000
<460OOO
22x10*
640000
200000
2600O
570000
< 13000
<4 10000
electrostatic
Preclpitator
(ESP) Catch
1023
490 y/a
H9/9
<50
2.0
<20
1.8
4.3
280000
14
36
12
11000
<20O
80
< 0.2
24
< 4
< 50
< 50
2000
40
55
2100
163
8.22
< 45
\tg/a
<2SQOO
980
< 9800
860
2100
1.40xl06
6900
leooo
590O
5400000
< 98000
39000
< 98
12000
< 2000
< a 5000
< 25000
990000
2OOOO
27000
10000OO
80000
4000
<22OOO
Kiln
Qsisslan
by Process
Flows
Feed -
Clinker -
ESP
Vq/s
< DL
14OOO
< Dt
21000
0
0
0
250000
0
0
< DL
360000
< W.
150000
< ot,
< DL
< DL
8000000
0
250000
R7OOOO
320000
79000 < 92000
600OO<690000
Stack
Emission
Ratio
SASS
(Kiln
Emissions)
—
< DL
0.0007<0.035
< M.
0.0002<0.0057
< DL
< PL
< DL
0.025<0.026
< DL
< OL
< DL
O.O069
< DL
0.023<0.024
< DL
< DL
< DL
0. 0061 <0. 0069
< DL
0.0084
0.29 < O.31
0.038< 0.047
O.S6 > 0.48
2
Overall
Mass
Balance
(SASS »
Clinker »
ESP)
Feed
—
< DL
0.63<0.64
< OL
0.33
2.2
3.4
1.6
0.54
1.1
1,5
< OL
0.74
< DL
0.62
< DL
< DL
< DL
0.74
1.4
0.48
0.67<0.6B
0.68<0.69
0.50<0.64
0.170.6667
< DL
0,9959>O.B800
0.8418>0.7984
0.9402
0.6216*0.6106
0.7407<0.7347
0.7867
0.9820
< DL
0.9398
< OL
0.7792>0.7692
< DL
< OL
< OL
0.9528<0.9474
0. 9886 <0. 7663
0.9278
0.8000»0.7874
0.8696>O.B421
O.OB33
< DL
en
U)
See notes on Table F-l
-------
TABLE F-14.
THACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 9-6, CEMENT KILN
cr»
Sample Type
Sample Number
Sanpla Haight/Vol.
Unit*
Antimony
•nealc
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Hickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
nitrate* .
Sulfate*
Total MM
Total PC*
Ho trie. Probe,
10 urn Cyclon*
Solid*
409
0.0122 q
V9/9
<_ 0.8
20
120
0.5
S. 0.7
HC
66
3
15
HC
26
490
—
14
2
—
_< 0.9
HC
44
63
HC
HC
..
HC
M/«3
< 0,001
0.026
0,16
0.00065
£ 0.00091
—
0.086
0.0039
0.020
__
0.034
0.64
—
o.ois
O.OOJ6
—
< O.O013
—
0.057
0.082
—
—
—
—
3 urn Cyclone
Solid*
None
pq/g
WJ/m
*
1 UB Cyclone
Solids
408
0.5775 q
V9/9
< 26
0.65
< 65
< 0.7
< 1.3
260000
100
26.0
21.0
8800
< 13
100
< 0.02
65
< 0.5
< 65
< 65
3600
81
36
--
~
~
—
Mf/»J
< 1.6
0.040
< 4.0
< 0.043
< o.oao
16000
6.2
1,6
1.3
540
< 0.80
6,2
< 0,012
4.0
< 0.031
< 4.0
< 4.0
220
5.0
2.2
_.
..
..
—
Filtera
276
0.2042
M/4
< 500
10
< 20
16
16
440000
240
230
70
17000
< 2000
320
< 2
140
< 4
< 500
< 500
4000
10O
210
61000
_-
5850
—
|I?/»S
< 11
0.22
< 0.44
0.35
0.35
9600
5.2
5,0
1.5
370
< 44
7.0
< 0.044
3.0
< 0.087
< 11
< 11
87
2.2
5.0
1300
._
130
—
Solid
Section
Hash
Hone
in/ml
lia/m1
&•• not** on Tabl* F-l
-------
TABLE F-15.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 9-6, CEMENT KILN
Saapl* Typ«
Sa*f>l* Nuabar
Suepla Hatght/Vol.
Unit*
tatiaony
linwtlc
Bari.ua
Beryllium
Cadmiuia
Calcium
Chroiaiua
Cobalt
Capper
Iron
Lend
Nangan***
Mezcuxy
Mck«l
SulenluM
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
Nitrate*
Sulfetea
Total POM
Total PCS
XAD-2
Ma* la
295
161 g
V9/S
< 50
< O.S
<20
- B
< 0.5
30000
1
< J
1
23
* 190
< B
< 2
< 1.1
< 4
< 50
* SO
< 60
< 10
< B
19
30
41 '"
< 58
0.00091
MM
Wf/»J
< 860
< 8.6
< 340
0
< 8.6
520000
17
< 52
17
390
< 3300
0
< 34
< 26 .
< 69
< 860
< e60
< 100O
< 170
O
330
520
700
< 1000
0.016
NR
Organic Nodal*
Rin*e
475
417 »1
pa/ml
< B
< B
0.35
< 0.005
0.14
- B
B
< 0.02
0.04
0.3O
0.03
0.025
< O.OOS
0.02
< 0.04
< 2
< 1
' •
< 0.1
- •
3.6
< 0.4
1.0
< 6
0.000018
NR
HS/»*
0
0
16
< 0.22
6.2
0
0
< 0.89
1.8
11
1,1
1.1
< 0.22
0.89
< 1,8
< 89
< 44
0
< 4.4
0
160
< 1.8
44
<270
0.00081
NR
Compensate
9-6 K
2863 al
Uf/Bl
0.2
< 0.02
< 0,1
< 0.005
< 0.01
1.4
0.03
0.02
0.02
0.08
< 0.02
0.015
< 0.005
0.04
< 0.04
< 2
< 1
< 0.5
< 0.1
0.05
1.3
< 0.2
0.4.4
< 6
NR
NR
V9/»3
61
< 6.1
< 31
< 1.5
< 3.1
430
9.2
6.1
6.1
24
< 6.1
4.6
< l.S
12
< 12
< 610
< 110
< 150
< 31
15
400
< 61
130
<180O
NR
NR
iBPinqer No. 1
1027
3764 «a
M9/«>1
0.10
< 0.012
< 0.090
< O.OOS
< 0.010
1.4
0.021
0.014
0.020
0.14
0.029
0.017
< 0.005
0.035
< 0.040
< 2.0
< 1.0
< 0.48
< 0.10
0.048
0.043
< 0.020 •
0.64
< 6.1
I1R
NK
ny»s
42
< 4.7
< 36
< 2.0
< 3.8
550
8.5
5.8
8.0
55
12
6.9
< 2.0
14
< 16
< 800
< 410
< 190
< 41
19
170
< 80
260
<2500 (SO;)
NR
NR
laoinocr Ho. 2
9-6 L
2220 Hi
uq/aa
0.99
< 0.014
0.17
< 0.005
0.018
< B
0.17
0.12
0.18
< B
0.015
0.038
< 0.005
0.13
< O.040
< 1.4
< 0.99
< 0.24
< 0.099
O.014
68
< 0.20
—
—
HR
NR
|«p/»3
230
< 3.2
39
< 1.2
4.4
0
39
29
44
0
l.S
9.0
< 1.2
10
< 9.5
< 320
< 230
< 58
< 23
3.2
16000
< 47
—
._
HR
MR
Irclnaer No. 3
None
uq/Bl
M/»J
It
notes on Tabla F-l
-------
TABLE F-16.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 9-6, CEMENT KILN
Sample Type
Sample Number
Sample Height/Vol.
Units
Antimony
Arsenic
Barium
Beryl Hun
Cadni um
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Hanganese
Mercury
Hickel
Selenium
Tellurium,
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
Nitrates
Sulfates
Total POM
Total PCB
Emission
in Partic.
< 3 in»
408 + 276
0.7817 g
yg/»3
< 2.7
0.22
< 4.4
0.3S0.7059
< DL
0.9830>0.78S7
0.8879>0.7631
0.008264
0.8527
0.9167>0.8333
0.7097
0.9959
< DL
0.9787
< DL
0.8750<0.8305
< DL
< DL
< DL
0.9933>0.9643
0.9927>0.7829
0.9523
0.8219
0. 8900 <0. 8476
< DL
> 0.2796
—
See notes on Table F-l
-------
TABLE F-17.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY
TEST 9-6, CEMENT KILN
Saapl* Typ«
Sa*pl* Munber
S««>1* Maight/Vol.
Unit*
AntUuny
Arsenic
Mriun
Barylliua
CadmluM
Calciiui
Chroalun
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Saleniu*
TelluriuB
Tin
Titanium
Vanadiu*
Zinc
Chlorine
Fluorine
Combined
Solids
409 * 408 * 276
0.7939 g
V9/9
< 0.63
26
92
0.57
< 0.63
HC
120
8.6
9.9
HC
6.4
ISO
IW
53
2.4
< 0.33
1.2 < 1.3
150 < HC
99
29
HC
100 < MC
M9/»3
< 0.067
2.8
9.8
0.060
< 0.067
HC
13
0.91
1.1
MC
0.68
16
—
5.7
0.25
< 0.036
0.12 <0.14
16 < HC
10
3,0
HC
8.7 < HC
XAD-2 Re.in
9-6 B
161 9
lig/9
< 1
< B
1
< 0.5
< 0.5
ISO
< B
< 0.1
- B
5
< 2
< B
NR
< 8
< I
< 0.5
1
< 11
0.4
< B
8
< B '
|!9/«
< 17
0
17
< 9
< 9
3100
O
< 1,7
0
90
34
0
—
0
< 17
< 9
17
< 190
6.9
0
140
0
Combined
Liquids
9-6 C
8847 ml
Jlf/Bl
0.066
< B
0.044
< 0.0037
< 0.004
MC
0.029
0.0079
0.034
0.24
0.015
0.011
HB
0.49
< 0.1
< 0.004
< B
< 0.097
0.018
0.17
0.076
< B
WJ/m1
62
0
42
< 3.5
< 3.8
HC
27
7.5
32
220
14
10
—
46O
< 94
< 3.8
0
< 91
17
160
71
0
Total
Ei*i»cion
Concen.
SASS
9.375 m3
M
-------
TABLE F-18.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 9-6, CEMENT KILN
cr>
03
6a«I>la Type
Sa*v>l* Hurtwx
Ea«>le Helqht/Vol.
Unite
AlUBinun
•imuth
Baron
Bromine
Cerium
cesiuB
Dysprosium
Erblw
Europium
Gadolinium
GBlllum
Germanium
Gold
Hafnium
HolniuM
Iodine
IridiUB
Lanthanum •
Lithiun
Lutetian
Hagnesium
Molybdenum
IModyniium
Niobium
Osmium
Combined
Solids
409 •> 408 + 276
0.7939 g
M/i
HC
< 0.42
' 30
88
20
38
< 0.42
< 0.42
0.69
1.7
12
2.3
< 0.42
< 0.42
< 0.42
'22
< 0.42
20 -
20
< 0.42
HC
8.0
6.7
6.7
< 0.42
Jlg/»3
HC
< 0.036
2.5
7.4
lj?
3.2
< 0.016
< 0.036
0.059
0.14
1.0
0.19
< 0.036
< 0.036
< 0.036
1.8
< 0,036
1.7
1.7
< 0.036
HC
0.68
0.56
O.S7
< 0.036
XAO-2 Resin
9-6 B
161 g
vq/q
110
< 0.5
< 8
2
< 0.5
< 0.2
< 0.5
< 0.5
< O.S
< 0.5
< 0.4
< 0.5
< 0.5
< 0.5
< 0.5
< 0.7
< 0.5
< 0.5
- B
< 0.5
100
< B
< 0.5
< 0.5
< O.S
ll^/B3
1900
< 8.6
0
34
< §,6
< 3.4
< 8.6
< B.6
< B.6
< 8.6
< 6.9
< 8.6
< 8.6
< 8.6
< 8.6
< 12
< 8.6
< 8.6
0
< 8.6
1700
0
< 8.6
< 8.6
< 8.6
Combined
Liquids
9-6 C
884
MS/"1
0.17
< 0.004
< B
0.20
0.0065
0.0018
< D.004
< 0.004
< 0.004
< 0.004
< B
< B
< 0.004
< 0.004
< 0.004
0.40
< 0.004
< 0.027
0.0*021
< 0.004
< B
0.010
< 0.004
< 0.006
< 0.004
7 ill
W9/K3
160
< 3.8
0
190
6.2
1.7
< 3.8
< 1.8
< 3.8
< 3.8
0
0
< 3.8
< 3.8
< 3,8
180
< 3.8
< 26
2.0
< 3.8
a
9.5
< 3.8
< S.7
< 3.8
Total
Emission
Conceit.
s\ss
9. 175 »J
pg/«3
2100 < HC
< 12
2.5
230
7t» * 47
4.9 < 8.1
< 12
< 12
O.OS9 < 12
0.14 < 13
1.0 < 7.9
0.19 < 8.8
< 12
< 12
< 12
180 < 390
< 12
1.7 < 16
3.7
< 12
1700 < HC
10
0.56 < 13
0.57 < 15
< 12
fatal
Emission
Rate
21.7 m3/a
V9/*
45000
-------
TABLE F-19.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 9-6, CEMENT KILN
Supls ryp«
SUf>i* Number
Saapl* Weiqht/Vol.
Unit*
Palladium
Platinum
Phoaphoru*
PotABVium
Praseodymium
Rhenium
MiodiuB
Rubidium
RuttwnlUB
Samarium
Scandium
Silicon
Silvnr
Sodium
Sulfur
Strontium
Tantalum
Thallium
Terblun
Thorium
Thulium
Tungsten
Uranium
Xttarblum
Yttrium
Zirconium
Combined
Solids
409 + 408 » 276
0,7939 g
M9/S
< 0.43
< 0.42
ISO < MC
HC
5.2
< 0.42
< 0,42
240
< 0.42
3.5
6.4
HC
0.86
62 < HC
HC
ISO
< 0,42
0.031<0.6S
0.42
7.6 < 7,7
< 0.42
< 0.42
4.2
< 0.42
6.9
60
I*/.1
< 0.036
< 0.016
21 < HC
HC
0.44
< 0.036
< 0.036
20
< 0.036
0.29
0.54
HC
0.072
-------
TABLE F-20.
POM COMPOUNDS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY
LOCATION 9, CEMENT KILN
POM Component
Anthracene
Phenanthrene
Methyl Anthracenes
Fluoranthene
Pyrene
•Benzo (c)phenanthrene
Chrysene
Benz (a) anthracene
Methyl Chrysenes
*7,12-Dimethylbenz(a)
anthracene
Benzo Fluoranthenes
•BenzUJpyrene
Benz(e) pyrene
Perylene
• 3-M«thy Icholanthr ene
Indeno (1,2, 3-cd ) pyrene
Benzo (ghi)perylena
*D ibenzo (a , h ) anthracene
•Dibenzo (c, g) carbazole
•Olbenztai and ah) pyrene s
Total
Kiln Exit, Test 9-3
XAD-2 Resin
(296)
ng/g ntj/m
0.37
—
0.01
0.26
0.044
—
0.02
—
—
~
—
—
—
—
~
~
—
—
—
~—
0.71
19
~
0.51
13
2.2
~
1.1
—
—
—
—
__
—
—
—
_
__
~
—
—
36
Module Wash
(9-3H)
nq/ml ng/m
0.028
~
o.ooso
0.016
O.OOSO
—
—
—
—
—
0.012
0.012
~
—
—
_
—
~
—
—
0.084
7.8
—
2.2
4.5
2.2
—
—
—
—
—
3.4
3.4
—
_.
—
—
~
—
—
~ ™
24
ESP Exit, Test 9-6
XAD-2 Resin
(295) 3
ng/g ng/tn
0.35
0.02
0.15
0.27
0.11
—
0.013
0.0009
0.0011
~
0.0037
0.0022
0.002
0.0018
—
~
—
—
~
— *
0.91
6.0
0.35
2.5
4.6
1.8
~
0.23
0.016
0.019
—
0.063
0.038
0.035
0.031
„
—
—
—
—
•*—
16
Module Wash
(475)
ng/ml ng/m
0.0022
—
—
0.0013
0.015
—
—
—
—
—
—
—
—
_
—
—
—
—
~
~ ~
0.018
0.097
—
—
0.059
0.65
—
~
~
~
—
—
—
—
—
—
—
~
—
—
— '""
0.81
* Compounds required to ba identified for this contract
(1 ng • 10"9 g).
Note: Values in this table are expressed in nonograms (ng)
Values in other trace species and organi'cs tables in this report are
expressed in micrograms (pg), (1 pg - 10-6 g).
470
-------
TABLE F-21.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 10/2-10, BLACK LIQUOR RECOVERY BOILER
Ednple Type
Sample umber
Sample Haight/Vol.
Units
Antimony
Arsenic
BarlUB
Berylliua
Cattail ua
Calciu*
ChroKiu*
Cobalt
Copper
Iron
Land
Hanganeae
Mercury
Mickel
Selenium
Telluriua
Tin
Tltaniua
Vanadim
Zinc
Chloride
Fluoride
Nitrates
Sul fates
Total POM
Total PCB
Nozzle , Probe ,
10 Mm Cyclone
Solids
389
3.5376 g
W/f
< 20
< 1
70
0.2
14
200
27
6
3.6
210
16
75
< 0.5
19
< 1
« 100
< 50
IS
3
41
48000
75
< 1,5
710000
< 500
< 1000
Mg/»J
< 43
< 2
150
0.41
30
430
58
17
7.8
450
35
160
< i
41
< 2
< 220
< no
32
6
89
104000
160
< 7.6
1500000
< 1100
< 2100
3 M1* Cyclone
Solids
3ao
0.8531 9
vg/9
< 40
2
10
< 0.2
18
110
16
6
3.6
240
20
54
< 1.0
20
< 2
< 200
< 100
56
< 6
58
49000
(4600)
< 3.S
630000
NES
HES
M/»3
< 21
1.0
16
< O.I
• 9.4
57
19
1.1
1.9
130
10
28
< 5.2
10
< 1.0
< 10O
< 520
29
< 3.1
10
26000
2400
< 1.8
1300OO
NES
NES
1 im Cyclone
Solids
191
3.9293 9
l»9/9
< 20
5
40
< 0,1
10
29
8
8
2.0
110
18
31
< 0.5
17
< 1
< 100
< 50
< 15
< 3
56
47000
110
< 2.5
650000
< 200
< 500
M9/»3
< 48
12
96
< 0.24
24
70
19
19
4.8
260
43
74
< 1.2
41
< 2.4
< 240
< 120
< 36
< 7.2
130
1100OO
260
< 6.0
1600000
< 480
<1200
Filters
287 + 288
9.4446 9
\>1/9
< 2O
5
20
< 0.1
7
28
3.4
10
2.1
41
16
28
< 0.5
a
< 1
< 100
< 50
< 15
< 3
52
52000
130
< 2.5
75000O
210
< 200
M9/»J
< 120
29
120
< 0.58
40
160
20
58
12
240
91
160
< 2.9
46
< 5.8
< 580
< 290
< 87
< 17
300
100000
750
< 14
4300000
1200
< 12OO
Solid
Section
Hash
10/2-10 F
643 ml
(J9/al
« 0.5
< 0.02
< 0.1
< 0.003
0.01
1.1
0.14
< 0.02
0.01
1.3
< 0.1
a. 11
< 0.005
0.12
< 0.02
< 2
< 3
< 1
< 0.1
0.11
no
< 0.2
< 0.10
810
< o.oooi
< 0.001
U9/«J
< 200
< 7.9
< 39
< 1.2
3.9
510
55
< 7.9
12
510
< 39
43
< 2.0
47
< 7.9
< 790
<1200
< 390
< 19
51
41OOO
i
< 79
< 39
320000
* 0.1?
< 0.39
Se* note* on Table P-l
-------
TABLE F-22. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 10/2-10, BLACK LIQUOR RECOVERY BOILER
Sample Type
Sample Number
Sample Height/Vol.
Units
Antimony
Arsenic
Barium
BerylliuB
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
Hit rates
Sulfates
Total POM
Total PCB
XAO-2
Resin
292
164 g
pg/g
37
< 1
140
< 0.1
< 1
< B
1.7
< 1
< B
< B
< B
< B
< 0.5
< B
< 1
< 100
< 50
< 15
< 3
< B
< 13
96
< 1
< B
780
< 25
pg/m3
3700
< 100
14000
< 10
< 100
0
170
< 100
0
0
0
0
< 50
0
< 100
< 10000
< 5000
< 1500
< 300
0
< 1300
9600
< 100
0
78000
< 2500
Organic Module
Rinse
243
92 ml
pg/ml
< 0.5
< 0.02
NES
< 0.003
NES
NES
NES
UES
NES
NES
< 0.1
NES
< 0.005
NES
< 0.1
NES
NES
NES
NES
NES
< 2
< 2
1.7
.120
0.380
< 0.050
P9/»3
< 28
< 1.1
—
< 0.17
—
—
—
—
—
—
< 5.6
--
< 0.28
~
< 5.6
~
~
—
—
—
< 110
< 110
96
6700
21
< 2.8
Condensate
205
353 ml
pg/ml
< 0.5
< 0.020
< 0.1
< 0.003
< 0.01
1.3
0.08
< 0.02
< 0.01
4.3
< 0.1
1.2
< 0.05
0.32
< 0.03
< 2
< 3
< 1
< 0.1
< 0.05
50
< 0.2
< 0.1
680
< 0.001
< 0.005
ug/m3
< 110
< 4.3
< 22
< 6.5
< 2.2
280
17
< 4.3
< 2.2
930
< 22
260
< 11
69
< 6.5
< 430
< 650
< 220
< 22
< 11
11000
< 43
< 22
150000
< 0.22
< 1.1
Jmplnqer No. 1
10/2-10 G
1191 el
ug/ml
< 0.50
< 0.020
< 0.10
< 0.0030
< 0.010
0.21
0.077
0.025
0.013
0.60
< 0.10
0.38
< 0.0050
0.092
< 0.20
< 2.0
< 3.0
< 1.0
< 0.10
< B
< B
< 0.40
< B
76
< 0.00040
< O.O02O
pg/m3
< 370
< 15
< 73
< 2.2
< 7.3
150
56
18
9.2
430
< 73
280
3.7
67
150
<1500
<2200
< 730
< 73
0
0
< 290
0
56000
< 0.29
< 1.5
Impinoer No. 2
10/2-10 II
1301 ml
pg/ml
< B
< 0.020
< 0.10
< O.OO30
0.0085
0.71
0.20
0.073
0.043
1.2
< 0.059
0.12
< 0.0050
0.13
< 0.20
< 2.0
< 3.0
< 1.0
< 0.1
< B
210
< 0.10
—
—
< 0.00020
< O.O0050
wg/m3
0
< 16
< 79
< 2.4
6.7
570
160
58
34
980
< 47
98
< 4.0
100
<160
< 1600
< 2400
< 790
< 79
0
1 70000
79
—
—
0.16
0.40
Imnlnaer No. 3
304
983 ml
Mg/ml
< 8
< 0.020
< 0.10
< 0.030
0.024
8.6
0.29
0.54
0.040
2.1
< 0.046
0.078
< 0.0050
0.31
< 0.20
< 2.0
< 3.0
< 1.0
< 0.1
0.92
91
< 0.20
—
—
< 0.00020
< 0.00050
ug/m3
0
12
< 60
< 1.8
15
5200
180
320
24
1300
< 20
47
< 3.0
180
<120
< 1200
< 1800
< 600
< 60
550
54000
< 120
—
—
< 0.12
< 0.30
M
See notes on Table F~l
-------
TABLE P-23.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 10/2-10, BLACK LIQUOR RECOVERY BOILER
u>
Sample Type
Suipla Number
Saaple Weigbt/Vol.
Units
Antimony
Arsenic
BaritiB
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Horcury
Nickel
Selenium
Tellurium
Yin
Titaniua
Vanadium
Zinc
Chloride
Fluoride
Nitrates
Sulfatea
Total PCM
Total PCB
Enisilon
In. Partic.
< 3 pm
391,287,288
13.1739 q
W/m3
< 170
41
220
< 0. 82
M
230
39
77
17
500
140
230
< 4.1
87
< 8.2
< 820
< 410
< 120
< 24
430
310000
1000
< 20
5.9K10*
1200
< 1200
Total
Emission
Concert.
SftSS
1.636 *}
M9/*3
370O < 4600
42 < 200
15000
0.43 < 19
130 < 240
7300
750
560 < 610
100
5200
180 < 390
1200
< 80
540
< 560
< 11000
< 130OO
51 < 3900
6.7 < 610
' 12OO
790000
I 3000 <1 4000
200 < 290
7. 9*10*
790000
< 7300
Total
Emission
Rate
54.6 »3/s
M9/*
200000 <2SOO
2300 < 110O
820000
23 < 1000
1100 < 1300O
400000
41000
27000<3100O
5500
280000
3800 < 21000
66000
< 4400
29OOO
< 31000
<600000
<7 10000
3300<21000O
370 < 3300O
66000
4.3xl06
710000 <7600
U000<16000
430x10*
4.3xl06
< 400000
Fuel Input,
Black Liquor
297
15185 g/»
MA»
10 < 20
< 1
25
< 0.1
1.8
28
< 0.3
3.2
1.0
44
7
28
< 0.3
4
< 1
< 75
< 50
< 9
< 1
4
7300
0 46
NR
m
209
< 50
Jig/a
< 300000
< 15000
38OOOO
< 1520
27000
430000
< 4600
49000
150OO
670000
110000
43000O
< 4600
61000
< 15000
< l.lxlO6
< 760000
< 140000
< 150OO
61000
llOxlO6
7OOOOO
—
—
3.2xl06
< 760000
Smelt Output
1OOO
6536 9/8
V9/9
< 20
< 1
30
0.2
3
600
IB
11
4.3
110
3
96
< 0.5
10
< 1
< 100
< 50
25
4
7.3
15300
107
< 0.5
601OOO
< 5
< 10
MtA
< 1300OO
< 6500
20OOOO
1300
2OOOO
3.9X106
12000O
72OOO
2BOOO
720000
20000
630000
< 3300
65000
< 65OO
< 650000
< 330000
160000
26000
48000
lOQxlO
700000
< 3300
3.9xl09
< 33000
< 65000
Furnace
Emission
Liquor -
Snelt
W1/«
< 170000
< 8500
180000
220
7000
-3.5*106
- 120000
- 23000
- 13000
- 50000
90000
- 200OOO
< 1300
- 4000
8500
< 450000
< 430000
- 20000
- 11OOO
13000
10x10*
0
—
—
3,2X10*
< 700000
Furnace
Enuuion
Ratio
SASS
Liq-Snelt)
> 1.18
> 0.27
4.6
0.1
1.01
- 0.11
- 0.34
- 1.2
- 0.42
- 5.6
0.11
- 0.33
3.4
- 7.3
- 3.7
1.33
1.65
1.6S
- 0.03
5.1
0.43
—
—
—
1.36
< 0.6
Hail
Balance
(Snelt * SASS)
Liquor
1.1
0.6
2.7
O.9
1.0
10.0
>35.0
2.02
2.23
1.5
6.27
1.6
< 1.7
1.54
< 2.50
1.14
1.4
1.2
1.8
1.9
O.9S
2.0
—
—
1.36
< O.66
See notee on Table t-l
-------
TABLE P-24.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY
TEST 10/2-10, BLACK LIQUOR RECOVERY BOILER
*•
Sample Type
Sample Nunber
Sample Mnight/Vol.
Unit*
Antimony
Arsenic
Baritai
Beryllium
C*d*ium
Caieima
ChroBiua
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chlorine
Fluorine
Combined
Solids
10/2-10 A
17.7646 q
M9/9
< 0,8
2
a
< 0.8
< o.a
510
7
0.6
5
49
< O.B
20
NR
36
< 1
< o.a
< O.B
< 24
0.7
6
HC
130
M9/»3
< 8.7
22
07
< 8.7
< 8.7
5500
76
6.5
54
530
< 8.7
220
390
< 11
< 8.7
< 8.7
<260
7.6
65
MC
1400
XAD-2 Resin
10/2-10 B
164 g
w/g
< 2
< 2
9
< 2
< 2
HC
2
< 2
S
38
< 9
0.6
MR
7.3
< 2
< 2
< 2
2.3
0.8
S
2
12
yg/»3
< 200
< 200
900
< 200
< 200
HC
ZOO
< 200
500
3800
< 900
60
710
< 200
< 200
< 200
2300
BOO
500
200
1200
Combined
Liquids
1O/2-10 C
3299 ml
|ig/ml
0.0091
< B
0.048
< O.OO21
< O.OO3
HC
< B
0.1
< B
HC
0.056
0.0037
NR
0.16
0.04
- 0.003
' B
0.65
O.OO013
MC
< B
HC
pg/ni1
18
0
98
< 4.2
< 6.0
«C
0
200
< B
MC
110
760
330
81
< 6.0
0
1300
0.26
MC
0
MC
Total
Emission
Cancel).
SASS
1.636 •*
|lfl/«3
18 < 230
22 < 220
1100
< 210
< 210
5SOO < HC
280
210 <410
550
4300
-------
TABLE P-25.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 10/2-10, BLACK LIQUOR RECOVERY BOILER
-si
Ul
Sanpla Type
Sanple Number
Sample Weiqht/Vol.
Units
AluninuB
Bi smith
Boron
Brcmine
Ceriun
CenitiB
Dysprosiiu*
Erblun
EuropluB
GadaliniuB
CalliuH
G«maniUB
Gold
Hafnltw
ItoliUua
Iodine
Irldiua
Lanthamw
Lithium
Lutetiua
Magneslua
Molybdenum
N«odyuiu»
Hi obi tin
Osmium
Confined
Solids
10/2-10 *
17.7646 9
|«/9
10
< 0.8
9
31
< 0.8
< 0.8
< 0.8
< 0.8
< o.e
< 0.8,
< 0.7
< 0.8
< 0.8
< O.B
< O.B
9
< 0.8
< 0.8
85
< 0.8
330
< 0.8
< 0.8
< 0.6
< 0.8
H9/«J
110
< 8.7
98
340
< 8.7
< 8.7
< 8.7
< 8.7
< 8.7
< 8.7
< 7.6
< 8.7
< 8.7
< 8.7
< 8.7
98
< 8.7
< 8.7
920
< 8.7
3600
< 8.7
< 8.7
< 8.7
< 8.7
XAD-2 Resin
10/7-10 B
1G4 9
vg/9
9
< 2
< B
< 2
< 2
< 1
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
0.5
< 2
170
< B
< 2
< 2
< 2
U9/»J
900
< 200
O
< 200
< 200
< 100
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 2OO
< 200
SO
< 200
1700
0
< 200
< 2OO
< 200
Combined
Liquids
10/2-10 C
3299 ml
M9/»l
0.31
< O.003
< B
< B
< B
< O.O02S
< O.003
< 0.003
< 0.003
< 0.003
< B
< 0.003
< 0,003
< 0.003
< 0.003
< B
< O.O03
< B
0.0045
< O.003
0.51
< B
< O.MJ
< 0.003
< 0.003
w/»
620
< 6.0
0
0
o
< 5.1
< 6.0
< 6.0
* 6.0
< 6.0
0
< 6.0
< 6.0
< 6.0
< 6.0
0
< 6.0
0
9.0
< 6.0
1000
0
< 6.0
< 6.0
< 6.0
Total
Emission
Concen.
SASS
1.6)6
M9/»J
1600
< 210
98
340 < 540
< 210
< 110
< 210
< 210
< 210
< 210
< 210
< 210
< 210
< 210
< 210
98 < 300
< 210
< 210
980
< 210
6300
< 8.7
< 210
< 210
< 210
Total
Emission
Rate
54.6 in1/"
pa/s
87000
< 11000
5300
18OOO < 29000
< 11000
< 6000
< lloop
< 11OOO
< 11000
< 11000
< 11000
< 11000
< 11000
< 11000
< 11000
5400 < 16000
< 11000
< 11000
54000
< 11000
340000
< 5,00
< 11000
< 11000
< 11000
Sue note on Table f-l
-------
TABLE F-26.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 10/2-10, BLACK LIQUOR RECOVERY BOILER
*>•
-J
Sanple Type
Sample Number
Sample Height/Vol.
Units
Palladium
Platlnun
Phosphorus
Potassium
Praseodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Silicon
Silver
Sodium
Sulfur
Strontium
Tantalum
Thallium
Terbium
Thorium
Thullua
Tungsten
Uranium
Ytterbium
Yttrium
Zirconium
Combined
Solids
10/2-10 A
17.7646 g
pg/g
< 0.8
< O.B
120
HC
< 0.8
< 0.8
< 0.8
63
< 0.8
< 0.8
< 1
210
< 0.8
HC
HC
4
< 0.8
< 0.8
< O.B
< 0.8
< 0.8
< 0.8
< 0.8
< 0.8
< 0.8
1
pg/»3
< 8.7
< 8.7
1300
HC
< 8.7
< 8.7
< 8.7
680
< 8.7
< 8.7
< 11
2300
< 8.7
HC
HC
43
< 8.7 •
< 8.7
< 8.7
< 8.7
< 8.7
< 8.7
< 8.7
< 8.7
< 8.7
11
XAO-2 Resin
10/2-10 B
164 g
Mg/g
< 2
< 2
24
a
< 2
< 2
< 2
0.8
< 2
< 2
< 0.3
120
< 2
240
22
3
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< B
ug/n3
< 200
< 200
2400
BOO
< 200
< 200
< 200
80
< 200
< 200
< 30
12OOO
< 2OO
24000
2200
300
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 200
0
Combined
Liquids
10/2-10 C
3299 ml
Ug/nl .
< 0.003
< 0.003
< B
HC
< 0.003
< 0.003
< 0.003
< B
< 0.003
< 0.003
< 0.002
HC
HC
HC
MC
< B
< 0.003
< 0.003
< 0.003
< O.O03
< 0.003
< 0.003
< 0.003
< 0.003
< 0.003
< B
pg/«>3
< 6.0
< 6.0
0
HC
< 6.0
< 6.0
< 6.0
0
< 6.0
< 6.0
< 4.0
HC
HC
HC
HC
0
< 6.0
< 6.0
< 6.0
< 6.0
< 6.0
< 6.0
< 6.0
< 6.0
< 6.0
0
Total
Emission
Concen .
SASS
1.636
Mg/m3
< 210
< 210
• 3700
BOO < HC
< 210
< 210
< 210
760
< 210
< 210
< 45
14OOO < HC
HC
MOOO < HC
2200 < HC
340
< 210
< 210
< 210
< 210
< 210
< 210
< 210
< 210
< 210
11
Total
Emission
Rate
54.6 m3/s
ug/s
< 11000
< 11000
200000
140OO < HC
< 110OO
< 11000
< 11000
41000
< 11000
< 11000
< 2400
760000 < HC
HC
HC
.200OO
-------
TABLE F-27.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 10/2-12, BLACK LIQUOR RECOVERY BOILER
Sample Type
£**£>!• timber
S**pl* Weigh t/Vol.
Units
Antimony
Arsenic
aOXilW
Beiylliua
Ciulmi i«
OlCiUB
ChlTlBll !!•
Cab* It
Co«>«r
Iron
U»»d
MansaneM
Mrcuxy
Wckei
Selenium
TalluriuM
*ta
TiUuiiu«
Vanadium
Zinc
Chloride
riuorida
Nitrate*
Sulfate*
Total POM
Total PCS
NozclB, Probe,
10 W* Cyclone
Sol Ida
383
0.6481 q
V1/1
< 20
< 3
30
< 0.2
IS
200
58
12
4.0
370
25
74
< 1
38
< 2
< 200
< 100
10
< 6
52
31000
(4200)
< 8
64000
j»g/»J
< 9.7
< 0.97
15
< 0.097
7.3
97
28
5.8
1.9
180
12
36
< 0.49
19
< 0,97
< 97
< 49
15
< 2.9
25
15000
2000
< J.9
31000
3 IIM Cyclone
Solids
386
0.1911 q
pg/g
< 100
< 50
20
< 1
31
300
41
< 10
< 2
250
< 20
44
< 10
< 10
50
« 1000
< SOO
< 150
< 10
73
50000
780
< 60
690000
nq/x1
< 14
< 7.2
2.9
< 0.14
4.5
43
59
< 1.4
< 0.29
36
2.9
6.3
< 1.4
< 1.4
7.2
< 140
< 72
< 22
10
7200
110
< 8.6
99000
1 IN Cyclone
Solida
397
1.4589 1
(19/9
< 20
< I
20
< 0.1
10
16
IB
6
2.S
110
20
2,8
< 1
20
< 1
< 100
< 50
< 15
19
10000
< 1000
19
590000
V9/»3
< 22
< 1.1
22
< 0.11
11
39
20
6.6
2.7
140
22
3.1
< 1.1
22
< 110
< 55
< 16
41
31000
< 1100
21
650000
Filter*
285 •» 286
6.1269 Cf
pq/q
< 20
< 1
32
< 0.1
10
21
6.2
7
2.2
4.1
28
20
< 0.5
6
< 100
< 50
< 15
33
35000
40.0
28
670000
0.29
< 100
W"3
< 92
< 4.6
ISO
< 0.46
46
110
29
12
10
19
110
92
< 2.1
28
< 4.6
< 460
< 230
< 69
< 14
150
16000O
180
130
3100000
1.3
< 460
Solid
Section
Hash
10/2-12 I
95S mi
|Kf/al
< 0.5
< 0.020
< 0.1
< 0.001
0.02
l.S
0.27
0.07
0.04
1.1
< 0.1
0.066
< 0.005
0.10
< 0.2
< 2
< 1
< I
< O.I
O.O9
54
0.36
< 0,10
420
< 0.0002
< 0.0005
]Uj/*3
< 360
< 14
< 72
< 2.2
14
1100
190
50
29
790
< 72
47
< 1.6
72
<140
< 1400
< 2200
< 720
< 72
65
19000
2.58
< 72
300000
< 0.14
< 0.16
Bee notea on T*I>1* P~l
-------
TABLE F-28. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 10/2-12, BLACK LIQUOR RECOVERY BOILER
Simple Typ«
Sanple Nunber
Sample Heiqht/Vol.
Units
Antimony
Arsenic
Barium
Beryl HUM
Cadnlm
Colclua
ChcoatUM
Cobalt
Copper
Iron
Lead
Manganese
Harcury
Nickel
Selenlun
TeJlurlUB
Tin
Tltaniua
Vanadium
Zinc
Chloride
Fluoride
Nitrate*
Sul fates
Total POM
Total PCB
XAD-2
Resin
291
153 g
pa/a
< 20
< 1
10
< 0.1
< 1
< B
7.2
< i
< B
< B
< B
< B
< 0.5
< B
10
< 100
< 50
< 15
< 3
< B
97
32
< 1
< B
50
< 25
M9/«3
< 2300
< 120
1200
< 12
< 120
0
a 30
< 120
0
0
0
0
< 58
0
1200
< 1200
< 5800
< 1700
< 350
0
11000
1700
< 120
0
5800
c 29OO
Organic Module
Rinse
215
168 9
Vig/atl
< 1
< 0.02
< 0.05
< 0.005
< 0.01
0.66
0.36
< 0.02
< 0.01
4.2
< 0,02
0.40
< 0.005
0.40
< 0.02
< 3
< 1
< 0.5
< 0.1
0.11
9.9
1.1
0.40
40.0
WA>
< 130
< 2.5
< 6.3
< 0.6J
< 1.3
83
45
< 2.5
< 1.3
530
< 2.5
51
< 0.63
51
< 2.5
< 380
< 130
< 63
< 38
14
1300
140
51
6100
Condensate
206
246
M9/»l
< 0.5
< 0.020
< 0.1
< 0.003
0.04
1.6
0.11
0.04
< 0.01
4.4
< O.I
0.38
< 0.005
0.49
< 0.05
< 2
< 3.
< 1
< 0.1
0.15
12
0.54
0.58
340
< 0.001
< O.OOS
M9/»3
< 92
< 3.7
< 18
< 0.55
7.4
300
57
7.4
< 1.8
sto
< 18
70
< 0.92
91
< 9.2
< 370
< 550
< 180
< 18
28
2200
loo
110
63000
< 0.18
< 0.92
Impinger No. 1
314
9BS ml
llq/tol
< 0.50
< 0.020
< 0.10 .
< 0.0030
< 0.010
< B
o.oaa
< 0.017
< B
0.68
< o.io
0.035
< 0.0050
< 0.037
< 0.050
< 2.0
< 3.0
< 1,0
< 0.10
< B
< B
< 0.40
9.1
250
< 0.00020
< 0,00050
M9/»3
< 370
< 15
< 7.4
< 2.3
< 0.74
0
65
< 13
0
soo
< 7.4
26
< 3.7
< 27
< 37
< 1500
< 2300
< 74
< 7.4
0
o
< 293
6800
190000
< 0.15
< 0.37
Inpinqer Ho. ?
315
948 Ml
\i?/ml
< B
< 0.019
< 0.10
< 0.00)0
0.024
0. 097
0.29
O.036
0.030
2,1
< 0.042
0.068
< 0.0050
0.19
< 0.19
< 1.9
< 3.0
< 1.0
< 0,1
0.31
410
< 0,19
—
_-
< 0. 00040
< o.ooio
M9/»3
0
< 14
< 69
< 2.1
17
• 68
200
25
21
1400
< 29
47
< 3.5
140
<140
<1400
<2100
< 690
< 69
22O
290000
< 140
„
—
< 0.28
< 0.69
-J
09
See notes on Table F-l
-------
TABLE F-29.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 10/2-12, BLACK LIQUOR RECOVERY BOILER
Saapl* Type
Sample Nuinber
Sanple Weight/Vol.
Units
Antlnony
Mrc«nic
Barium
Beryl liu«
Cadniua
Calciua
chrcwiun
Cobalt
Capper
Iron
Lead
Han9&nese
Mercury
Nickel
Selenim
Tellurium
Tin
fitanivai
Vanadium
Zinc
Chloride
fluoride
Nitrates
Sul fates
Total fOH
Total PCB
Emission
In. Partlc.
< 3 M»
197,285,286
7. 5858
U9/»3
< 110
< 5.7
170
< 0.57
57
ISO
SO
18
13
160
150
95
< 3.4
50
< 5.7
< 570
< 780
< 85
< 17
190
190000
180 < 1100
150
3.8x10*
1.3
< 460
Total
emission
Concen.
SASS
1.130
M/«3
< 3400
< 200
1400 < 160C
< 23
1JO < 2SO
aooo
1700
160 < 290
71 < 75
S6OO
170 < 390
430
< 80
500 < 530
1100 < 1600
< 1900
< 16000
21 < 4900
< 620
560
4.1X106
6500 < B300
?100 < 7300
4.2xl06
5800
< 1100
Total
Emission
Rate
44.3 a3/"
Wfi>
< 150000
< 8900
62000 <710W
< 1000
5700 < 1100C
89000
75000
7100<1100(
3100 < 3100
250000
7500 < 170«
19000
< 3500
22000<23000
49000*71000
< B4000
< 710000
1000<220000
< 27000
25000
ISOxlO6
29OOOO<3700
31OOQQ<120D
186x10*
260000
<15OOOO
Fuel Input,
Black Liquor
1001
9964
-------
TABLE F-30. TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 10/2-714, BLACK LIQUOR RECOVERY BOILER, LOCATION 10
oo
o
Sample Type
Ejuople Nuvber
Sample Height /Vol.
Units
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Huiganese
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
fluoride
Nitrate*
Sul fates
Total POH
Total PCB
Nozzle, Probe,'
10 \im Cyclone
Solids
398
0.0669 g
ug/g
< 200
< 10
10
< 2
< 20
160
76
< 20
14
1100
< 80
44
< 10
< 20
200
< 200O
< 1000
400
< 60
120
65000
(29000)
< 350
5 70000
M9/»3
< 0.96
< 0.048
0.048
< 0.0096
< 0.096
0.77
0.36
< 0.096
0.067
5.3
< 0.3B
0.21
< 0.048
< 0.096
0.96
< 9.6
< 4.8
1.9
< 0.29
0.57
310
140
< 1.7
2700
3 MB Cyclone
Solids
NONE
ug/g
Mg/»3
1 un Cyclone
Solids
396
0.1125 q
Mg/g
< 200
< 10
20
< 1
< 10
140
BB
< 11
6.6
660
< 30
41
< 5
33
10
< 1000
< 500
300
< 33
87
130000
(46000)
< 800
720000
IJg/m3
< 1.6
< O.OBO
0.16
< O.OO80
< 0.080
1.1
0.71
< 0.089
0.053
5.3
< 0.24
0.33
< 0.040
0.27
0,080
< 8.0
< 4.0
2.4
< 0.27
0.70
1000
370
< 6.4
5800
Filters
279
0.3134 1
M9/9
< 20
< 1
130
0.36
5
37000
20
10
9.5
1100
25
36
< 0.5
11
40
< 100
< 50
140
4
37
88000
(3090)
< 90
590000
Mg/»3
< 0.45
< 0.022
2.9
0.0081
0.11
830
0.45
0.22
0.21
25
0.56
0.81
< 0.011
0.25
0.90
< 2.2
< 1.1
3.1
0.090
0.83
2000
69
< 2.0
13000
Solid
Section
Hash
10/2-14 J
914 B
U9/»l
< 0.5
< 0.02
< 0.1
< 0.003
< 0.01
1.0
0.08
0.05
0.03
0.42
< 0.1
o.oia
< O.OO5
< 0.05
< 0.001
< 2
< 3
< 1
< 0.1
0.05
30
< 0.2
< O.I
48
0.00037
<0.0005
1
pq/in3
< 33
< 1.3
< 6.5
< 0.20
< 0.65
65
5.2
3.3
2.0
27
< 6.5
1.2
< 0. 33 .
< 3.3
< 0.065
< 130
< 200
< 65
< 6.5
3.3
2000
< 13
< 6.5
3100
0.024
< 0.033
See notes on Table F-l
-------
TABLE F-31. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 10/2-14, BLACK LIQUOR RECOVERY BOILER, LOCATION 10
Sanpl* Type
Saaple Nusber
Sample Weight/Vol.
Units
Antiaotty
Arsenic
Bar tun
Barylliua
CadtBium
Calcium
ChroKiuB
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Telluriu*
tla
Titanium
VanadiuH
Zinc
Chloride
Fluoride
Nitrate*
Sul fates
Total fan
Total PCS
XJUJ-2
Resin
293
158.6 g
U9/9:
< 20
< 1
10
< 0,1
2
< «
3.2
< 1
< B
< B
< B
< B
< 0.5
< B
< 1
< 100
< 50
< IS
< 1
< B
< 20
77
< 1
< B
4900
< 25
w/»3
< 230
< 11
110
< 1.1
23
0
36
< 11
0
0
0
0
< 5.7
0
< 11
< 1100
< 570
< 170
< 34
0
< 230
B70
< 11
0
S6000
< 280
Organic Module
Rinse
225
215 Bl
(ig/nl
« 0.5
< 0.02
< O.I
< 0.003
0.01
1.9
0.26
< 0.02
0.02
2.1
< 0.1
0.085
< 0.005
0.19
< 0.1
< 2
< 3
< 1
< 0.1
0.48
14
0.56
1.1
6.0
0.61
< 0.005
ug/«3
< 7.7
< 0.31
< 1.5
< O.O46
0.031
29
4.0
< 0.31
0.31
32
< 1.5
1.3
< 0.077
2.9
< 1.5
<31
<46
<15
< 1.5
7.4
220
8.6
17
92
9.4 ,
< 0.077
Condensate
10/2-14 K
3348 nl
M/Bl
< 0,5
< 0,020
< 0.1
< 0.003
0.01
o.a
< 0.02
< 0.02
< 0.01
o.oa
< 0.1
0.020
< 0.005
< 0.05
< O.O2
< 2
< 3
< 1
< 0.1
0.02
< 2
< 0.2
< 0.10
60.0
< 0.0002
< O.OOO5
"9/n-
« 120
< 4.8
< 24
< 7.2
2.4
190
< 4.8
< 4.8
< 2.4
19
< 24
4.8
< 1.2
< 12
< 4.8
< 480
< 720
< 240
< 240
4.8
< 480
< 48
< 24
14000
< 0.048
< 0.0005
Inplnqer No. 1
10/2-14 L
2373 nl
pg/ml
< 0.51
< 0.020
< 0.10
< 0.0030
< 0.010
0.55
0.13
< 0.017
0.021
0.84
< 0.10
0.036
< 0.0051
< 0.040
< 0.020
< 2.0
< 3.0
< 1.0
< 0.1
0.037
< B
< 0.30
27
260
< 0.0020
< 0.00051
U9/»3
< 86
< 3.4
< 17
< 0.51
< 1.7
93
21
< 2.9
3.6
140
< 17
6.1
< 0.86
< 6.7
< 3.4
<340
<510
<170
< I?
6.2
0
< 51
4600
44000
< 0.34
< 0.086
Inpinqer Ho. 2
10/2-14 M
1891 ml
V9/»l
< 0.026
< 0.020
< 0.10
< 0.0030
0.0021
< B
0.24
0.022
0.0037
1.6
< 0.074
0.069
< O.O050
0.085
< 0.18
< 2.0
< 3.0
< 1.0
< O.I
< B
1100
0.26
—
—
0.012
< 0.0010
lig/m1
< 3.6
< 2.7
<14
< 0.41
0.29
0
33
2.9
0.50
220
< 10
9.3
< 0,68
11
< 24
« 270
< 410
e 140
< 14
0
140000
35
—
—
1.6
< 0.14
Ifopinoer Ho. 3
10/2-14 N
1827 nl
M9/«l
< 0.0055
< 0.020
< 0.099
< O.OOJO
0.032
< B
0.88
0.093
0.0038
6.0
< 0.071
0.14
< 0.0050
0.060
< 0.18
< 2.0
< 3.0
< 1.0
< 0.1
< B
660
0.42
—
—
O.O42
< 0.00010
1»9/1»3
< 0.72
< 2.6
<13
< 0.39
4.1
O
110
12
0.50
790
< 9.3
19
< 0.65
79
<24
<260
<390
<130
< 1,3
0
86000
55
—
—
5.5
< 0.013
See notes on Table f~l
-------
TABLE P-32.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 10/2-14, BLACK LIQUOR RECOVERY BOILER
*>
CD
Sample Typ«
S»of>la tlunber
Sample Weight/Vol.
Units
Antimony
Arsenic
BaxiuB
Berylliua
CadaiuB
Calcium
ChroBluB
Cobalt
Copper
Iron
Urad
Manganesa
Mercury
Hickcl
Selenlun
Telluiiua
Tin
Tifcttilu*
Vanadiim
Zinc
Chloride
fluoride
Nitrate*
Sul fates
Total PON
Total PCB
Emission
In. Partic,
< 3 ya
396 * 279
0.4259
M9/«3
2.1
0.10
3.1
1. 0081 <0. 016
0.11 < 0.19
830
1.2
0.22 < 0.31
0.26
30
0.56 < 0.80
1.0
< 0.051
0.52
0.98
< 10
< 5.1
5.5
0.090 <0.36
1.5
30OO
440
< 8.4
19000
Total
Rustier)
Cancan.
SASS
13.977 »3
V9/»3
< 490
< 15
120 < 190
9.008 < 1.4
30 < 33
1200
220
48 < 68
7.9 < 10
1400
2.1 < 69
51
< 9.3
93 < 120
1.9 < 72
<26QO
< 2900
7.5 < 950
0.09 < 110
2.4
160000
2400
4600
39000
56000
< 290
Total
Emis&ion
Rate
66.8 m3/a
V9/a
< 33000
< 1000
BOOO < 13000
0.5 < 220
2000 < 2200
80000
15000
3200 < 4500
520 < 670
93000
140 < 46OO
3400
< 620
6200 < 8000
130 < 4800
< 170000
< 190000
500 < 62000
6 < 7300
160
llxlO6
160000
30OOOO
2,6x10*
3.7x10*
< 19000
Fuel input.
Black Liquor
1009, 1010
14528 g/s
P9/I
< 20
< 1
26
< 0.1
1.2
49
< 0.7
2.6
1.6
24
6
30
< 0.5
2.0
< 2
< 150
< 50
< 11
< 2
a
6750
100
73
< 50
\tq/m
< 290000
< 14000
380000
< 1400
17000
710000
< 10000
38000
23000
350000
87000
440000
< 7300
29000
< 29000
< 2*1Q6
< 730000
< 160000
< 29000
120000
9.8x10*
1.4x10*
1M106
< 730000
Saelt Output
1007, 1008
5244 q/a
C9/9
< 20
< 1
35
0.2
3
aoo
17
13
4
115
7
98
< 0.5
10
< 1
< 100
< 50
< 15
3
11
29000
150
< 0.5
480000
< 10
< 50
MSA-
< 100000
< 5200
180000
10OO
16000
4.2.106
89000
68000
21000
600000
37000
510000
< 2600
52000
< 5200
< 520000
< 260000
< 79000
16000
58000
152X106
790000
2600
2.5x10*
< 5200O
< 260000
furnace
EaiBiion
Liquor - ,
Smelt
Ml/*
< 190000
* 9300
190OOO
< 400
1700
-3,5»106
- 79000
- 30000
2300
- asoooo
50000
- 78000
< 4600
- 23000
24000
< 1.6x10
< 460000
< 81000
< 13000
59000
- 54xl06
670000
IxlO6
< 460000
Furnace
!&i salon
Ratio
SASS
Uq-Snelt
< 0.18
< 0.11
0.04
0.0012
-------
TABLE F-33.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 10/2-16, BLACK LIQUOR RECOVERY BOILER
oa
Sample TYP«
Sample Muaber
Sample Maiqht/Vol.
Unit*
jbitiBony
Acsenic
Baritai
Beryllium
Cadaiu*
Calciun
ChroniuM
Cobalt
Copper
Iron
Lead
Hanganace
Mercury
Nickel
SeleniuB
Tclluriuo
Tin
TitajiiuM
Vanadium
Zinc
Chloride
Fluoride
Nitrates
Sulfatea
Total KIM
Total PCB
Nozzle, Probe,
10 pa Cyclone
Solid*
381
0.1016 9
HI/9
< 200
< 10
HES
< 2
HES
NES
HES
HES
HES
HES
< 100
NES
< 10
HES
200
HES
NES
HES
NES
HBS
69000
41400)
< 55
540000
M9/B1
< 1.5
< 0.076
—
< 0.01S
—
—
—
—
—
< 0.76
—
< 0.076
—
l.S
—
~
—
_-
—
52 0
11
< 0.42
4SOO
3 |IB Cyclone
Solids
HONE
M9/9
W"3
1 |m Cyclone
solids
382
0.0755 9
V9/9
'« 200
< 10
NES
< 1
HBS
HES
NBS
HES
HES
HES
< 50
HBS
< 5
HES
S
NES
NES
HES
HES
HES
68000
(1600)
< 90
SSOOOO
It?/"3
< 1.1
< 0.053
—
< 0.0051
—
:
—
—
„
< 0.27
—
< 0.027
_-
0.027
—
—
—
—
—
360
8.5
< 0.48
2900
Filters
330
0.2503 q
M9/9
< 20
< I
HES
< I
HES
HBS
NES
HBS
HES
HBS
25
HES
< 5
HES
20
HES
HBS
HES
HES
HES
48000
(2400)
< 270
51000
IKI/B1
< 0.35
< 0.018
~
< 0.018
—
:
..
_.
_.
0.44
—
< 0.088
—
0.35
—
__
..
_.
__
8SO
42
< 4.8
900
Solid
Section
Hash
10/2-16 A
840 pi
M/i"1
< O.S
< 0.02
HES
< 0.003
< 0.01
1.1
0.15
< 0.02
< 0.01
0.41
< 0.1
0.024
< 0.005
< 0.05
0.01
< 2
< 3
< 1
< O.I
0.06
23
0.58
< O.2O
86
0.0018
< 0.0001
w/«J
< 30
< 1.2
~
< o.ia
< O.S9
77
8.9
< 1.2
< 0.59
24
< 5.9
1.4
< 0.30
< J.O
0.59
<120
<180
< 59
< 5.9
3.5
1400
34
< 12
5100
0.11
< 0.0059
Sea notes on Table F-l
-------
TABLE P-34. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 10/2-16, BLACK LIQUOR RECOVERY BOILER
Sample Type
Sample Number
Sample Weiqht/Vol.
Units
Antinony
Arsenic
Bariua
Berylliiw
Cadniun
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Hanganeae
Mercury
Nickel
Selenium
Telluriua
Tin
Ticaniua
Vanadlun
Zinc
Chloride
Fluoride
Nitrates
Sul fates
Total POH
Total PCS
XftO-2
Resin
294
180 9
pg/g
< 50
< 0.1
12
0.4
1.0
< B
1.5
20
< a
100
5
- B
< 0,1
2.5
< s
< 100
< so
150
< 5
2.6
11
12
0.70
< B
380
< 10
Mg/"3
< 630
< 1.3
150
5.1
13
0
19
250
0
1300
63
0
< 6.3 •
32
< 63
< 1300
< 630
1900
< 63
33
140
150
8.9
0
4800
< 130
Organic Hodule
Rinse
267
198 ml
|ig/Bl
< 1
< 0.02
< 0.05
< 0.005
< 0.01
0.5
0.23
* 0.02
* 0.01
1.4
< 0.02
0.05
< 0,005
0.11
< 0.02
< 3
< 1
< 0.5
< 0.1
0.37
13
< 0,4
< 0.2
15
9,8
< 0,005
ug/»3
< 14
< 0,28
< 0.70
< 0.070
< 0.14
7.0
3.2
< 0.28
< 0.14
20
< 0.28
0.70
< 0.070
1.5
< O.28
< 42
< 14
< 7.0
< 1.4
5.2
ISO
< 5.6
< 2.B
210
140
< O.070
. __T
CoRdensate
10/2-16 r
4607 Hi
Ug/ml
< 0.5
< 0.020
--
< 0.003
< 0,01
0.9
0.05
< 0.02
< 0.01
0.04
< 0.1
0.035
< 0.005
< 0.05
< 0.01
< 2
< 3
< 1
< 0.1
0.13
4.3
< 0.2
< 0.20
100
0.00026
< O.OOOS
M9/"J
< 160
< 6,5
—
< 0.97
< 3.3
290
16
< 6.5
< 3.2
13
< 32
11
< 1.6
< 16
< 3.2
< 650
< 970
< 320
< 32
42
1400
< 65
< 65
32000
0.004
< 0.16
Imi>inger Ho. 1
10/2-16 G
1291 ml
lig/ml
< 0.50
< 0.020
—
< 0.0030
< o.oio
< B
0.25
< O.O16
0.015
0.19
< 0.10
0.021
< 0.0050
< 0.031
< O.OIO
< 2.0
< 3.0
< 1.0
< 0.10
< 8
< B
< 0.30
< B
51
O.O0053
< o.onoso
M9/»3
< 46
< 1.8
—
< 0.27
< 0.91
O
23
< 1.5
1.3
18
< 9.1
1.9
< 0.46
< 2.8
< 0.91
<180
<270
< 91
< 9.1
O
0
< 27
0
4600
0.048
< 0.046
Iwincfer No. 2
10/2-16 H
1849 *1
w/«l
< 0.011
< 0.020
—
< 0,0030
< 0.0016
0.13
0.30
0.04
0.015
1.6
< 0.092
0.076
< 0.0050
0.14
< 0.097
< 2.0
< 3.0
< 1.0
< O.I
< B
28
< 0.20
—
—
< 0.00040
<0. 000010
lig/i.1
< 1.4
< 2.G
-.
< 0.39
< 0.21
17
39
5.6
2.O
211
< 12
9.9
< 0.65
18
< 13
<260
<390
<130
< 1J .
0
3600
< 26
—
—
< 0.052
< 0.013
lw>in
-------
TABLE F-35.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 10/2-16, BLACK LIQUOR RECOVERY BOILER
CO
tn
Saaple Typ«
Saople Number
Sample Weight/Vol.
Units
Antinony
Arsenic
Bariua
Beryllium
CadaliM
Calciun
Chromium
Cobalt
Copper
Iron
Lead
Manganeae
Mercury
Nickel
Selanius
Tellurium
Tin
Titanium
Vanadiun
Zinc
Chloride
Fluoride
Nitrate*
Sul fates
Total POH
Total PCS
Bniasion
In. Fartic.
< 3 tim
382 » 280
0.1258 g
JJ9/B1
< 1.5
< 0.071
NES
< 0.023
NES
NES
NES
NES
NES
NES
0.44 < 0.71
HES
< 0.11
NES
0.062
NES
NES
NES
NES
NES
1200
51
< 5.3
3800
MR
MR
Total
Entssion
Concen .
SASS
14.213 »*
U9/P1
< 160
< 16
ISO
5.1 < 8.4
18 < 19
440
150
300 < 320
3.3 < 7
1700
63 < 130
32
< 10
69 < 91
1.9 < 110
< 2700
< 2800
1900 < 2600
< 130
B4
13000
330 < 46O
9.1 < 91
46000
5000
< 130
Total
Emission
Rate
60.7 »J/fc
ug/d
< 9700
< 970
91 OO
300 < 510
1100 <1200
27000
9100
1BOOO<19OOC
200 < 420
1OQOOO
3800 < 7900
1900
< 600
4200 < 5500
11O < 670O
< 1600OO
< 170000
11000CK160C
< 7900
5100
79000O
20000<280OO
550 < 5500
2.Bxl06
300000
< 7900
Fuel Input,
Black Liquor
1014
13263 g/s
U- 280000
< 16000
< 19000
- SOOxl 0*
220000
-_
—
< 170000
< 420000
furnace
Emission
Ratio
SASS
Liq-Smelt
< 0.04
< o.oa
0.03
- 0.3
0.11
- 0.04
<-17
- 0.8
O.O3
- 0.4
0.06
- O.04
< 0.06
- 3.8
- 0.01
< 0.1
< 0.16
>-0.4
< 0.5
> 0. 3
- 0.002
O.O9
..
—
i.a
< 0.02
Mass
Balance
(Swell » SASS)
Liquor
< 0.93
< O.15
0.29
2.0
0.3
2.7
> 2.5
2.2
0.7
2.9
0.)
l.l
0.22
1.4
1.8
< 0.3
< 0.3
> 3.0
< O.B
> 0.8 '
6.5
0.7 •
-.
—
1.5
< 0.37
See notes on Table
-------
TABLE F-36.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY
TEST 10/2-16, BLACK LIQUOR RECOVERY BOILER
00
Sample Type
Sample Number
Sample Height /Vol.
Units
Antinony
Arsenic
Barium
Berylliui
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
. Nickel
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chlorine
Fluorine
Solid Section Hash
10/2-16 A
540 ml
Mg/g
< O.OOB
< 0.004
0.04
< 0.008
< O.OOB
MC
0.39
O.OO7
0.02
0.41
0.05
0.097
NR
0.06
< 0.02
< o.ooa
< O.OOB
0.04
< 0.002
0.06
1.4
0.4
ug/m3
< 0.4B
< 0.24
2.4
< 0.48
< 0.48
MC
23
0.41
1.2
24
3.0
5.7
—
3.5
< 1.2
< 4.8
< 4.8
2.4
< 0.12
3.5
83
24
XAD-2 Resin
10/2-16 B
1BO g
pg/g
< 0.5
< 0.3
2
< 0.5
< 0.5
240
< B
0.1
1
s
< 2
- B
NR
1.3
< 0.5
< 0.5
< 1
1
0.1
< B
32
3
Mg/m
< 6.3
< 3.8
25
< 6.3
< 6.3
3000
0
1.3
13
63
< 25
0
—
16
< 6.3
< 6.3
< 13
13
1.3
6
410
38
Combined
Liquids
10/2-16 C
9313 ml
eg/ml
0.06B
< B
< B
< 0.0067
< 0.01
HC
0.27
0.0058
0.056
0.59
0.025
0.070
NR
0.079
0.4
< 0.007
0.18
< 0.14
0.018
0.48
0.82
MC
yg/m
44
0
0
< 4.4
< 6.6
MC
180
3.8
37
390
16
46
--
52
260
< 4.6
120
< 93
12
320
540
MC
Total
Emission
Concen .
SASS
14.213 n3
pg/m3
44 < 51
4.0
< 27
< 11
< 13
3000 < MC
20O
5.5
50
4 BO
19 < 44
52
NR
72
260 < 270
< 16
120 < 140
15 < 110
13
320
1000
62 < MC
Total
Emission
Rate
60.7 B3/s
Pg/s
2700 < 3100
< 240
1600
< 670
< 780
MC
12000
330
3OOO
29000
1100 < 2700
3100
—
4400
1600
< 970
7300
910 < 670C
790
19000
61000
MC
See notes on Table F-l
-------
TABLE F-37.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 10/2-16, BLACK LIQUOR RECOVERY BOILER
00
Sarple Type
Sample Nwber
Sample Welght/Vol.
Units
JUuMiniM
Bismuth
Boron
BroniiM
Cerium
Casio*
Dysproilu*
Erbtu.
Europium
Gadolinium
Gallium
German! IB
Gold
Hafnium
Holnium
lodin.
Iridlun
Lanthanum
Lithium
Lutetiun
Hagneaium
Molybdenua
NaodyBiiB
Niobium
OSDliun
Solid Section Hash
10/2-16 A
840 ml
lig/rnl
0,6
< O.O2
0.15
0.04
< 0.008
0.003
< 0.008
< 0.008
< o.ooa
< 0.008
< 0.007
< 0.005
< 0.008
< 0.008
< 0.008
< 0.01
< O.O08
< 0.008
0.015
< 0.008
2.7
0.07
< 0,008
< 0,008
< 0.008
M9/«3
3.5
< 1.2
0.89
2,4
< 0.48
0,18
* O.4S
< 0.48
< 0.48
< 0.48
< 0.41
< 0,30
< 0.48
< 0,48
< 0.48
< 0.59
< 0.48
< 0.48
0.89
< 0.48
160
4.1
< 0.48
< 0.48
< 0.48
HAD-: Resin
10/2-16 B
180 q
Pq/g
64
< 0.5
< B
< 2
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.4
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
O.i
< 0.5
37
< B
< 0.5
< 0.5
< 0.5
tig/"3
810
< 6.3
0
< 25
< 6.3
< 6.3
< 6.3
< 6.3
< 6.1
< 6.3
< S.I
< 6.3
< 6.3
< 6.3
< 6.3
< 6.3
< 6.3
< 6.3
1.3
< 6.3
470
0
<.6.3
< 6.3
< 6.3
Combined
Liquids
10/a-l6 C
9313
lig/»l
0.039
< 0.007
0.16
0.44
0.0061
0.0035
< 0.007
< 0.007
< 0.007
< 0.007
< a
< B
< 0.007
< 0.007
< 0.007
< B
< 0.007
0,035
0.037
< 0.007
1.4
0.019
< 0.007
0.03
< 0.007
pg/»3
26
< 4.6
100
29
4.0
2.3
< 4.6
< 4.6
< 4.6
< 4.6
0
0 •
< 4.6
< 4,6
< 4.6
0
< 4.6
23
24
< 4.6
910
12
< 4.6
20
< 4.6
Total
Emission
Concert .
SASS
4.113 a1
vg/**
840
< 12
100
31 < 56
4.0 < 11
2.5 < 8.8
< 11
< 11
< 11
< 11
< 5.5
< 6.6
< 11
< 11
< 11
< 6.9
< 11
23 < 30
26
< 11
1500
16
< 11
20 < 27
< 11
Total
Emission
Rate
60,7 **/a
Mg/s
51000
< 730
6000
1900
240 < 670
ISO < 530
< 670
< 670
< 670
< 670
< 330
< 4OO
< 670
< 670
< 670
< 420
< 670
1400
1600
< 670
91000
970
< 670
1200
< 670
Gee note on Table F-l
-------
TABLE F-38.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 10/2-16, BLACK LIQUOR RECOVERY BOILER
*>•
00
00
Sample Type
Sample Number
Sai*>la Height/Vol.
Units
Palladium
Platinum
PhaBphoruB
Potassium
Praseodymium
Bhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Silicon
Silver
Sodium
Sul far
Strontium
Tantalua
Thallium
Terbium
Thorium
Thulium
Tungsten
Uranium
Ytterbium
Yttrioa
Zirconium
Solid Section Hash
10/2-16 *
840 nl
W&*1
< 0.008
< 0.008
0.4
HC
< 0.008
< O.OOB
< 0.008
0.02
< 0.008
< o.ooa
< 0.01
1.8
< 0,01
MC
MC
0.0}
< 0.008
< 0.008
< 0.008
< 0.008
< 0.008
< 0.008
< 0,06
< 0.008
< O.OOB
0.03
P9/m3
< 0.48
« 0.4S
2.4
HC
< 0.48
< 0.48
< 0.48
1.2
« 0.4S
< 0.4B
< 0.59
110
< 0.59
HC
MC
1.8
< 0.48
< 0.48
< 0.48
< 0.48
< 0.48
< 0.4B
< 3.5
< O.4B
< 0.48
1.8
XAD-2 Rasin
10/2-16 B
180 g
pg/g
< 0.5
< 0.5
< B
< B
< 0.5
< 0.5
< O.S
0.2
< 0.5
< O.S
< 0.1
42
< 0.5
< B
14
0.4
< 0.5
< O.S
< 0.5
< 0.5
< 0.5
. < O.S
< O.S
< O.S
< 0.5
< B
M9/»3
< 6.3
< 6.3
0
0
< 6.3
< 6.3
< 6.3
2.S
< 6.3
< 6.3
< 1.3
530
< 6.3
0
180
5.1
< 6.3
< 6.3
< 6.3
< 6.1
< 6.1
< 6.3
< 6.3
< 6.3
< 6.3
0
Combined
Liquids
10/2-16 C
931
< 0.007
< 0.007
2.5
MC
0.01
< 0.007
< 0.007
< B
< 0.007
< 0.007
< 0.009
HC
HC
HC
HC
0,086
< 0.007
< 0.007
< 0.007
< 0.007
< O.OO7
< 0.007
< O.OO7
* O.OO7
< 0.0012
< B
ml
< 4.6
< 4.6
1600
MC
6.6
< 4.6
< 4.6
0
'< 4.6
< 4.6
< 5.9
HC
MC
HC
HC
56
< 4.6
< 4,6
< 4.6
< 4.6
< 4.6
< 4.6
< 4.6
< 4.6
< 0.77
0
Total
Emission
Cancen .
SASS
14, 2J} m3
M9/m3
< 11
< 11
1600
HC
616 < 13
< 11
< 11
3.7
< 11
< 11
7.8
640 < HC
HC
HC
180 < HC
63
< 11
< 11
< 11
< 11
< 11
< 11
< u
< 11
< 7.6
1.8
Total
Ftai a 3 ion
Rate
60.7 m /a
< 670
< 670
97000
HC
40O < 790
< 670
< 670
220
< 670
< 670
470
MC
HC
HC
MC
3800
< 670
< 670
< 670
« 670
< 670
< 670
< 670
< 670
See note on Table F-l
-------
TABLE F-39. POM COMPOUNDS BY GAS CHROMATOGRAPHY-MASS SPECTROM1TRY
LOCATION 10/2, BLACK LIQUOR RECOVERY BOILER
POM Component
Anthracene
Phenanthrene
Methyl Anthracenes
Fluoranthene
Pyrene
* Benzo ( c ) phenanthrene
Chrysene
Benz (a) anthracene
Methyl Chrysenes
*7 , 12-Dimethy Ibenz (a)
anthracene
Benzo Fluorantiienes
«Benz(a)pyren*
Benz (a }pyrene
Perylene
*3-Methyleholantlirene
Zndeno (1,2, 3~cd } pyrene
Benzo (ghi } pery lene
•Dibenzo (a ,h) anthracene
•Dibenzo (c , g ) car bazo 1«
*Dibenz(ai and ahjpyrenes
Total
Furnace Outlet, 10/2-10
XAD-2 Resin
293 3
ng/g ng/m
81
—
0.93
7.7
2.5
~
0.42
—
~-
-—
0.11
0.06
—
—
—
—
—
— ,
--
— —
93
8100
_
93
770
250
~
42
—
—
™
11 •
6
•—
__
—
_ .
—
~
—
^~
9300
Modul
2
ng/tnl
.0.057
—
—
0.2
0.15
—
1.6
0.06
—
—
0.95
0.22
0.23
—
—
—
~
~
-.
~~
3.4
e Wash
43 3
ng/B
3.2
—
—
11
a. 4
—
88
3.4
—
«•".
53
, 12
13
_
—
—
—
—
._
— «•
193
ESS Outlet, 10/2-16
XAD-2
29
n«r/g
130
_
6.6
19
11
0.08
3.8
—
0.08
»_
3
1.6
—
—
—
0.42
0.14
0.15
_
—
170
Resin
4 ,3
ng/»
14000
—
730
2100
1200
S.8
420
—
8.8
~—
330
180
—
—
—
46
15
17
__
••—
19000
Module Wash
267 3
ng/ml ng/m
40
—
—
17
0.14
0.026
3.6
0.47
0.044
*—
2.0
0.33
0.34
0.084
—
0.036
0.14
—
~
•—
68.6
550
—
—
240
2
0.36
51
6.6
0.61
~—
28
4.6
4.8
1.2
—
1.2
2.0
— ,
__
«
960
Compounds required to be identified for this contract
Not*:
(1 ng - lo"9 gj.
Values in this table are expressed in nonogramit (ng),
Values in other trace species and organics tables in this report are
expressed in micrograns (Ug), (1 wg « 10~6 g).
489
-------
TABLE F-40.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 12/2-3, PETROLEUM PROCESS HEATER
*»
10
o
Sanola Type
Sample number
Sanfle Melfht/VBl.
Unit*
Antimony
Arssaie
Barium
Beryllium
Cadmium
Calcium
ChxoniuB
cobalt
Copper
Iron
Load
Manganese
Mercury
Nickel
Selenium
Tellurium
Via
Titanium
Vanadium
Zinc
Chloride
Fluoride
Nitrate*
Sill fates
Total MM
Total PCS
Nozcls, Probe,
10 M* Cyclona
Solid*
Nona
W/9
M/.1
3 lim Cyclon*
Solids
Nona
M/9
M9/«J
1 IIM Cyclone
Solids
None
W/f
ug/«3
Filters
277
•<. 0,1 a
M9/9
KE3
MBS
NES
NES
(1ES
NES
N8S
NES
HES
BBS
HES
NES
< 0.2
Nes
fffi?
NES
NES
NES
NES
NES
S20
NES
< 200
780000
KES
NES
m/m3
__
—
—
—
—
—
•*—
—
—
0
—
— •
—
—
~
3.8 .
~
<1.S
5700
—
~~
Solid
Section
Hash
12/2-J A
691 111
iw/ia
< 0.5
< 0.01
< o.os
< 0.005
< 0-ft*
< B
0.17
O.C8
O.OB
16-1
< 0.01
1.2
< 0.005
l.S
< n-M
< 5
< 1
< I
< 0.1
0.45
1.0
0.40
O.OB
24.0
NR
HR
IIB/B*
< 30'
< O.5
< 3
< 0.3
< n.i;
0
S.6
4
4
BIO
< 1.5
160
< 0.3
76
< O.S
< 300
< 50
< 50
< 5
7.6
SO
2O
4
120O
—
•»•»
See notes on Table F-l
-------
TABLE F-41. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 12/2-3, PETROLEUM PROCESS HEATER
Saopla Type
Sample HiMijar
Supla Heifht/Vol.
Unit*
Anttaony
Axsanic
BarlM
BerylliiHi
Cadnlua
Calciu*
Chroniua
Cobalt
Coppar
Iron
Lead
Kangaae**
Maccury
Hickel
SelaniuB
TalluriuB
Tin
Titanium
Vanadiw
Zinc
Chloride
rtuoeida
nitrate*
Suliataa
Total PON
Total PC*
XAP-2
Resin
298
1S8 q
l»fl/f
< SO
< 3
< 2.5
< 0.5
6400
< •
7.0
< 25
2.0
I/O
< B
" B
< 0.5
< 1.0
< 5
< 35
< 250
50
< S
4.5
2.6
16.1
< B
220
< 1
< 1
V9/m*
< 600
< 30
< 29
< 6
74000
0
80
< 290
20
}Q
0
0
< 6
< 10
< 58
< 290
<29OO
600
< 60
52
30
41?
0
2500
< 12
< 12
Organic Hodulc
Rinse
12/2-3 B
IP "^
{jig/ia
< 0.5
< 0.010
< 0.05
< 0.05
< 0.0\
0.10
0.15
< 0.05
0.02
?-*
< 0.01
0.11
< 0.005
0.15
< o,B|
< 5
< 1
< 1
< 0.1
0.072
1.0
0.32
- B
18.0
< 0.01
< 0.001
M«/»J
< 20
< 0.5
< 2
< 2
< 0.5
5
6.8
< 2
90
loo
< 1
14
< 0.2
6.8
< 0.5
< 200
< 40
< 40
< 4
3.2
40
14
0
812
< 0.5
< 0.05
4
Condena*t«
12/2-3 C
5326
Vq/ml
< 0.23
< 0.0058
< 0.051
< 0.0043
< 0.007}
< B
0.039
< 0.048
< 0.0071
fKI^I
< B
0.043
< 0.051
< 0.069
< n 0043
< 5.1
< 1.0
< 1.0
< 0.10
0.032
18
0.54
< B
1400 (scy
HR
tt|
ml
Mf/»3
< 88
< 2.3
< 2.0
< 1.7
< 2ift
0
IS
< 19
< 2.8
2?ft
0
17
< 20
< 27
< 1.7
<2000
< 39O
« 390
< 39
12
6800
210
0
19000 (SO )
—
Inplnqnr No, 1
Combined with
C^ft^an
l>9/Bl
If^TI*
Wm*
Inpinqor No. 2
Coifclnad with
Condansate
fM/al
•
Mf/»*
l^oinoef Ho. 3
CoHbiiwd with
Condenaate
|I4/«1
w/*1
VD
Sa* notai on Tabla F-l
-------
TABLE F-42.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 12/2-3, PETROLEUM PROCESS HEATER
Sa*ple Type
S**f>l» MuBbac
Saople Height/Vol.
Unit*
Antimony
Armenia
Bariuai
Beryllium
(^Advim
Caleiua
Chromium
Cobalt
Copper
Iron
Lead
Hangane»
Harcury
Nickel
Selenium
TellmciuB
fin
Titanium
Vanadium
Zinc
Chloride
Fluoride
Nitrate*
Suit a tea
Total POM
Total VCB
Emission
in fartie.
< 3 V*
NES
(ig/*3.
-_
—
—
—
_.
—
—
_.
._
—
—
_.
0
—
__
—
—
~
—
—
3.8
—
—
5700
._
Totsl
i^ftission
Conceit.
1J.67 »3
pa/a1
< 700
< 40
< 40
< 10
74000
S
110
4 < 300
120
1210
< J
190
< 30
83 < 120
< 60
< 2000
< 3400
600 < 1100
< 110
75
£900
660
S.5
10000
< 13
< 12
Total
Ealaaian
Rat*
2.9 •*/«
MS/»
< 2000
< 120
< 120
< 30
210000
IS
320
12 < 900
350
3500
< 9
550
< 90
!40 < 350
< 170
< 8100
< 9900
1700 <3200
< 120
220
20000
1900
16
30000
< 38
< 35
See notei on Table P-l
-------
TABLE F-43.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 12/2-6, PETROLEUM PROCESS HEATER
*»
VO
ui
]
Sample fyp*
Sa^l* HiatMC
Saunpl* Heifht/Vol.
Units
Jmtioany
kJTianic
Buiua)
Beryllium
CwlBiuii
Calciuii
Chro*ii»
Cobalt
Cof*«r
Iron
Lead
MuguiBM
Marcury
Mickal
SeleniuB
Teiluriua
Tin
Titanian
Vsnadiui
zinc
Chloride
fluoride
Mltrataa
Sulf»t«a
Total POM
totml PCB
Nossla, Proba,
U |« Cyclona
Solids
Nona
V9/9
W/»*
J (• Cyclon*
Solids
Hone
Ug/9
yg/»J
.
1 \tm Cyclona
Solid*
Hone
pq/g
-i/-J
filteta
278
f.l
tig/9
NES
HBS
HES
NES
HES
NES
KES
HES
HES
HES
HES
NES
< 0.2
HES
HES
NES
MES
HES
HES
NES
4800
NES
360
910000
NES
KES
019 3
|l<|/»3
_-
__
..
—
—
.,
.,
_.
—
--
-_
< 0.001
—
,_
_
.-
—
,-
—
44
• —
3.3
8200
..
-.
Solid
Section
Hash
12/2-6 0
7§J ml
ua/Bl
< o.s
< 0.01
< 0.05
< 0.005
0.01
< B
0.21
< 0.05
0.02
7.9
< 0.03
2.1
< o.oos
0.8S
< 0.01
< 5
< 1
< 1
< 0.1
0.04
- B
< 0.2
0.10
13
HR
MR
Ha/*1
< JO
< 0.7
< 3
< O.J
0.7
0
14
< 3
1
530
< 2
140
< O.J
58
< 0.7
<300
< 70
< 70
< 7
3
0
< 10
6.8
880
—
—
Sa* ootei on Tabla F-l
-------
TABLE F-44. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 12/2-6, PETROLEUM PROCESS HEATER
Saople Typo
Sample Number
SajsjJlo Haight/Vol.
Units
Antlaony
Arsenic
Bariua
Berylliu*
Cadaiua '
Calciu«
ChroaiuB
Cobalt
Copper
Iron
Mad
Manganese
Harcury
Nickel
Seleniua
Tellurium
Tin
Titaniua
Vanadiua
Zinc
Chloride
Fluoride
Nitrate*
Sul fates
Total PON
Total PCB
XAD-3
Da tin
534
160 g
ui/1
< 50
< 3
10
< 0.5
0.5
30000
6.5
< 25
3.0
110
2.0
12
< 0.5
6.0
< 5
< as
< 2SO
190
< 5
10
< 2.6
51
< B
230
< 1
< 1
wg/»3
< 710
< 43
140
< 7
7
280000
93
< 360
28
1600
28
170
< 7
as
< 70
< 360
<36QO
2700
< 70
140
< 37
750
0
3300
< 14
< 14
Organic Module
Rinse
12/2-6 E
682 ml
M AL!
< 0.5
< 0.01
< o.os
< 0.005
< 0.01
0.1
0.19
< 0.05
< 0.01
1.2
< 0.03
0.17
< 0.005
0.15
< 0.01
< 5
< 1
< 1
< 0.1
0.01
< B
< 0.2
< •
10.0
0.01
< 0.001
H?'»3
< 30
< 0.6
< 3
< 0.3
< 0.6
6
12
< 3
< 0.6
73
< 2
10
< 0.3
9.1
< 0.6
< 300
< 60
< 60
< 6
0.6
0
< 12
0
610
0.6
< 0.06
Condon sate
12/2-6 r
4788 ill
pq/ml
'< 0.19
< 0.0054
< 0.050
< 0.0042
< 0.0069
< B
0.12
< 0.047
< 0.0069
0.63
< B
0.031
< 0.0050
0.066
< 0.0038
< 5.0
< 1.0
< 1.0
< 0.069
0.0033
< B
0.25
< B
9400 |S02)
MR
HR
HV«3
< BO
< 2.3
< 2.1
< 1.8
< 2.9
0
50
< 20
< 2.9
270
0
13
< 2.1
28
< 1.6
<2100
< 430
< 430
< 29
1.4
0
110
0
110000(S02)
—
Inplnger No. 1
Combined with
Condensate
pg/nl
lil
W9/«3
Inainqer Jia. 3
Combined with
Condensate
uq/nl
U9/»3
IO
See note* on Table r-1
-------
TABLE F-45,
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 12/2-6, PETROLEUM PROCESS HEATER
IO
Ul
Saapl* TyP*
fiMpl* Nuaber
SaapU Waiqht/Vol.
Unite
fcntinony
Jkricaio
Bariu*
Berylliu»
C£dftiikiM
Calciua
ChromiUB
Cobalt
Ooptw*
Icon
taad
McngaiMM
Mercury
Nickel
Seleniua
Y«llurii*
Tin
TituiiiiB
Vanadium
Zinc
Chloride
Fluoride
Nitmtaa
Suldttt*
Tot«l POM
Tot»l PCS
EmiMdion
la Pirtlo.
< 3 Wi
NES
m/»*
M
•
< 0.001
44
3.3
8200
Tot* I
million
Concur! .
11.34 »3
U«/»*
< 850
< 47
140 < ISO
< 10
7.7 < 11
280000
170
< 190
29 < 33
2500
28 < 32
330
< 10
180
< 73
< 3100
< 4200
2700 < 3300
112
ISO
44 < 81
860 < 880
10,1
13000
0,6 < 15
< 15
Total
million
Rate
3.03 «3/«
in/»
< 2600
< 140
420 < 450
< 28
23 < 33
850000
S20
< 1200
88 < 100
7600
as < 97
1000
< 29
550
< 22
< 9400
<13000
3200 < 10000
340
450
130 < 250
2600 < 2700
31
39000
1.8 < 45
< 45
SB* nota> on Table F-l
-------
TABLE F-46.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY
TEST 12/2-6, PETROLEUM PROCESS HEATER
*»
10
Saapl* Typa
Sample NuBber
Sanpla Helght/Vol.
Units
Antimony
Ars*nic
&»riui»
Beryl 11 via
Odntuii
Calclua
ChroniuB
Cobalt
Copper
Iron
Lead
Hanganet*
Mercury
Nickel
Selenium
Tellurium
Tin
Tittnlu*
Vanadiua
Zinc
Chlorine
Fluorine
Combined
Solid*
278
0,1019 9
pg/g
0. J
2
35
< 0.01
0.3
NC
12
o.e
14
190
6
8
NR
8
< 0.2
< 0.3
4
12
1
35
ISO
350
M/«3
0.0027
O.O1B
0.32
< 9-lxlo"5
0.0027
MC
0.11
O.OO73
0.13
1.7
O.OS4
O.073
--
0.073
< 0.0018
< 0.0027
0.0036
0.11
0.0091
0.32
1.3
3.2
XAD-2 Resin
534
160 g
ug/g
< 0.4
< 0.2
10
< O.4
< 0.6
BO
2.5
< 0.1
3
19
< 2
0,5
NR
2
< 5.5
< 0.55
< 0.75
4
0.2
5.5
3.4
11
. m/**
< 5.7
< 2.8
140
< 5.7
< 8.5
1100
36
< 14
43
270
28
7.1
—
28
< 78
< 7.8
< 11
57
2.8
78
48
160 •
Combined
Liquids
12/2-6 C
5470 ml
I<9/»1
< B
< B
0.00091
< 0.0013
< O.OO60
< 1.2
< B
0.0027
0.37
< B
< O.0024
< B
NR
0.037
< B
< 0.004O
< B
0.031
< B
0.18
« B
< B
lig/B
0
0
0.44
< 0.62
< 2.9
< 600
0
1.3
ISO
0
< 1.2
0
-•
18
0
< 2.0
0
15
O
87
0
0
Total
Emiision
Conceit.
SASS
11.24 n3
M9/IB1
0.002 7
-------
TABLE F-47.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 12/2-6, PETROLEUM PROCESS HEATER
SufilB Type
Sajqpl* Hmbsc
Sanpl* Naight/Vol.
Units
MuidnuB
BiMBlth
Boron "
BromliM
Cariua
Ceaiua
Dyiproalua
ErbiuB
EuropiuM
GadoliniuB
Gal HUB
Germanium
Gold
HafniuB
Holmiua
lodlna
Irldlu»
LanthanUB
Lithlua
LutBtiim
Magnesium
ttolybdenun
Neodyniiai
Hioblun
Osnitw
Coabined
Solids
278
0,1019 g
119/9
MC
< 0. 1
iso
0-7
0.5
0.1
< O.I
< 0.1
< 0.1
0.1
0.5
< 0.1
< O.I
0.1
< O.I
0.2
< 0.1
1
O.I
< 0,1
HC
0.5
0.1
< O.I
< 0.1
Ug/»*
MC
< 0.00091
1.3
0.006]
0.0045
0.00091
< 0.00091
< 0.00091
< 0.00091
0.00091
0.0045
< 0.00091
< 0.00091
0.0027
< 0.00091
0.001B
< 0.00091
0.0091
0.00091
< 0.00091
HC
0.0045
0.00091
< 0.00091
< 0.00091
XAD-2 Resin
S34
160 g
Vq/g
2.0
< 0.4
2.5
< 0.9
< 0.45
< 0.25
< 0.4
< 0.4
< 0.4
< 0.4
< 0.3
< 0.4
< 0.4 ,
< 0.4
< 0.4
0.65
< 0.4
< 0.65
0.10
< 0.4
12
7.0
< 0.4
< 0.4
< 0.4
w/«3
0.18
< 0.036
0.22
< O.080
< 0.040
< 0.022
< 0.036
< 0.036
< 0.036
< O.O36
< 0.027
< 0.036
< 0.036
< 0.036
< O.O36
O.OS8
< 0.036
< 0.058
0.0089
< 0.036
1.1
0.62
< 0.036-
< 0.036
< O.OJ6
Conbinad
Liquids
12/6 C
5470 nl
pg/Bl
0.018
< 0.0069
< B
< B
* B
< B
< 0.0040
< 0.0040
< 0.0040
< 0.004O
< B
< B
< 0.0040
< 0.0040
< 0.0040
0.0027
< 0.0040
0.0033
O.OO069
< 0.0040
< B
• B
< 0.0040
< 0.0040
< 0.0040
yg/»J
8.7
< 3.4
0
o
0
0
< 2.0
< 2.0
< 2.0
< 2,0
0
0
< 2.0
< 2.0
< 2.0
1.3
2.0
1.6
0.14
< 2.0
0
0
< 2.0
< 2.0
< 2.0
Total
Emission
Concen.
SASS
11.24 »3
M?/*1
a. 9 < HC
< 3.4
1.5
).0063<0£8G
).0045.0091<0,023
< 2.0
< 2.0
< 2.0
>.0091<2.0
I.O045.0082<6.2
< 6.2
4.1
6.1
4.8 < 5.1
1.1
< 6.2
3.3 < HC
1.0
).0028<6.2
< 6.2
< 6.2
Sea note on Table F->
-------
TABLE P-48.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 12/2-6, PETROLEUM PROCESS HEATER
*>
10
03
Sample Type
Sample Number
Sample Halqhl/Vol.
Unit*
Palladium
Platinum
Phosphorus
Potassium
Praseodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Silicon
Silver
Sodium
Sulfur
Strontium
Tantalum
Thallium •
Terbium
Thorium
Thulium
Tungsten
Uranium
Ytterbium
Yttrium
Zirconium
Combined
Solids
278
0,1019 Q
M9/S
< 0,1
< 0.1
23
>500
< O.I
< O.I
< 0,1
'3
< O.I
0.2
< 0.1
HC
42
HC
HC
3
< 0,1
0.2
< 0.1
0.8
< 0.1
< 0,3
0.6
< 0.1
0.6
10
V*/*3
4.5
<0. 00091
-------
TABLE F-49.
POM COMPOUNDS BY GAS CHROMATOGRAHPY-MASS SPECTROMETRY
LOCATION 12/2, PROCESS HEATER
POM Component
Anthracene
XAD-2 Resin
534
na/a na/w
0.50 7.1
Module Hash
12/2-6E 3
nej/ml na/m
0.018 1.1
Phenanthrena
Methyl Anthracenes
Fluoranthene
Byr*n«
*Benzo-(c) phenanthrane
Chrysane
Benz (a)anthracene
Methyl Chrys«n«a
•7,12-0iinethylbenz (a!
anthracene
Benzo Fluoranthenes
*B«nz Ca!pyrene
B«nz {•) pyrene
Perylane
* 3-Me thyleholanthrone
Intone (1,2,3-cd) pyr ane
B«azo(9hi)peryl«aa
*Di!»nso (a,h)anthrac«»«
•Dibenzo(c,g)carbazola
*Dibenz(ai and ah)pyrones
0.11
0.07
0.04
0.0007
1.6
0.93
0.54
0.01
0.007
0.002
0.44
0.11
Total
0.71
10.1
0.027
1.66
* Compounds required to be identified for this contract
Note: Values in this table are expressed in nonograms (ng), (1 ng -10 g),
Values in other trace species and organics tables in this report are
expressed in aicrograiB* (ug) , (1 yg - 10-6 g;.
499
-------
TABLE F-50.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 13-18, WOOD-BARK BOILER
Sanple Typa
Sample Number
Sample Height/Vol.
Unit*
Antlnony
Arsenic
Barium
Berylllua
Cadaiun
Calclun
Chronlun
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenlun
Tellurlua
Tin
Titan! un
Vanadlun
Zinc
Chloride
Fluoride
Nitrates
Sul fates
Total POM
Total PCB
Nozzle, Probe,
10 |ia Cyclone
Solids
392
0.2803
V9/9
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
0.6
NES
NES
NES
NES
NES
NES
NES
NES
2500
NES
NES
NES
NES
ug/»3
—
~
—
—
—
—
—
~
„
—
--
—
0.01S
—
—
—
—
~
—
—
62
—
—
—
— —
3 (in Cyclone
Solids
737
0.2647 g
Pg/9
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
0.5
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
119/»3
—
—
—
—
—
—
—
—
—
—
—
—
0.012
—
—
—
—
—
—
— '
—
—
—
—
"**"
1 tin Cyclone
Solids
740
1.1314 g
M9/9
NES
1700
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
0.4
NES
NES
NES
NES
NES
NES
NES
130
NES
< 5
80000
90
< 1
W9/B3
—
170
—
—
—
—
~
—
--
--
--
~
0.040
—
—
—
—
—
—
13
—
0.50
8000
0.91
< 0.1
Filters
282
1.2379 g
P9/9
NES
1800
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
0.4
NES
NES
NES
NES
NES
NES
NES
NES
840
NES
NES
49
< 1
Ug/«3
~
180
—
—
—
—
—
—
~
--
—
0.040
—
—
—
—
—
—
—
84
—
--
S.4
< 0.11
Solid
Section
Wash
13-18 H
1334 ml
(Jg/nl
< 0.5
0.04
< 0.05
< 0.005
< 0,01
200
0.05
< 0.05
0.06
6.9
0.21
1.6
< 0.005
0.15
< 0.01
< 5
< 1
< 1
< 0.1
0.60
2.1
< 0.2
0.86
55
2.5
< 0.01
U9/-3
< 59
4.7
< 5.9
< 0.59
< 1.2
24000
5.9
< 5.9
7.1
820
25
<190
< 0.59
18
< 1.2
< 590
< 120
< 120
< 12
71
250
< 24
100
6500
300
< 1.2
tn
O
O
See notes on Table F-l
-------
TABLE P-51.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 13-18, WOOD-BARK BOILER
Sample Type
Saiqple Nuaber
SupU Ueight/Vol.
Unit*
Antiaooy
Ar sonic
Barium
Berylliua
Cadaiua
Calcium
Chromiua
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurian
Tin
Titaniusi
V«U1*diUB
Zinc
Chloride
Fluoride
Nitrates
Sulf«tes
Total K>H
Total PCB
SkB-2
Resin
530
134 9
U4/9
< 50
< 1
2.5
< 0,5
< 0.5
< B
2.5
< 2.5
1.5
< B
< B
< B
< 0.4
< B
< 5
< 25
< 250
< B
< 5
< B
11
46
0.2
520
3.2
< 1
U9/»J
< 620
< 37
31
< 6.2
< 6.2
0
31
< 110
19
0
0
0
< 4.9
0
< 62
< 310
< 3100
0
•< 62
0
140
570
2.5
6400
40
< 12
Organic Modulo
Ulnae
13-18 M
349 ml
vg/ml
< 0.5
0.10
< 0.05
< 0,005
< 0.01
0.31
1.10
< 0.05
0.02
11.0
< B
0.57
< O.OOS
2.2
< 0.01
< 5
< 1
< 1
< 0,1
0.088
15
4.1
0.44
32
0.23
< 0.01
W"*
< 16
3.1
< 1.6
< 0.16
< 0.31
1O
34
< 1.6
0.62
340
0
18
< 0.16
68
< 0.31
< 160
< 31
< 31
< 3.1
2.7
470
130
14
looo
7.1
< 0.31
Condensftte
13-18 0
3641 al
pg/«l
< 0.060
< 0.0012
< 0.0060
< 0.00060
< 0.0012
0.038
< 0.0060
< 0.0060
< 0.0012
< 0.0060
< 0.0036
< 0.0012
< 0.00060
< O.O060
< 0.0012
< 0.60
< 0.12
< 0.12
< O.012
< 0.00060
< 0.047
0.096
0.008
< 0.16(30,;
HR
NB
U9/"3
< 20
< 0.18.
< 2.0
< 0.2
< 0. 18
12
< 2.0
< 2.0
< 0.38
< 2.0
< 1.2
< 0.38
< 0.2
< 2.0
< 0.38
< 200
< 18
< 38
< 1.8
< 0.2
< 15
11
2.4
< 51(SO2)
—
lapinqer No. X
Combined with
Condensate
\iq/*l
H?'"3
Iwplnqer No. 2
Coofcined with
Condensat*
vg/ml
l»g/«3
fnpinae? Mf}t ^
Combined with
Candeasate
V9/ml
Uf/n1
m
o
See notes on Table F-l
-------
TABLE F-52.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 13-18, WOOD-BARK BOILER
Simple Type
Sanple Number
Sample Height/Vol.
IMits
Antiaoay
Arsenic
Barium
Beryl liua
Cadmium
CalciuB
Chrooliua
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Seleniua
Telluriua
Tin
Tltaniun
Vanadiun
Zinc
Chloride
Fluoride
Hi traces
Sulfatea
Total KM
Total KB
Emission
in Par tic.
< 3 fin
740 4- 282
2.3693_1
M/»3- -,-
NES
150
IKS
NES
NES
NBS
NES
HliS
NES
HES
NES
NES
o.oao
IBS
NES
HES
NES
UBS
HES
HES
NES
920
NES
HES
6.3
< 0.2
Total
Enisaioo
Concert.
SASS
11.25 B3
uW
140 < 840
170 < 420
11 < 55
< 8.6
1.9 «9.8
24000
270
< 55
59
2600
9.8 < 28
2SO
O.il «52
260
< 67
< 2700
< 3600
470
< 110
110
1200
3700
190
22000
350
< 14
Total
Emission
Rate
10.8 a3 /a
M/s
1500 < 9100
4000 < 4SOO
135 < 590
< 93
21 < 110
260000
2900
< 590
640
28000
110 < 300
2700 '
1.5 < 560
. 2800
< 720
< 29000
< 39000
5100
< 1200
1200
13000
29000
2100
240000
3800
< 150
.Coal Fuel Input
1038
1100 g/a
|J9/f
< 50
< 3
S
2
< 0.5
140
10
< 25
5.5
6200
10
14
< 0.5
S.O
< 5
< 25
< 250
700
15.0
12
< 13
67
11
1800
¥<${"
< ssooo
< 1300
5500
2200
< 550
150000
11000
< 28000
6100
680OOOO
11000
1500(1
< 550
5500
< 5500
< 28000
< 280000
770000
17000
13000
< 14000
74000
12000
20000OO
Wood Fuel Input
1032
640 9/a
"9/9
< 50
< 3
5
< 0.5
0.5
5000
3.5
< 25
3
650
< 5
125
< 0.5
< 1
< 5
< 25
< 250
240
5
18
405
31
15
132
M/s
< 32000
< 1900
3200
< 320
320
3200000
2200
< 16000
1900
420000
< 3200
80000
< 320
< 64O
< 3200
< 16000
< 160000
150000
3200
12000
260000
20000
9600
84000
Boiler Ash Output
1013
379/8
H9/9
< 50
< 1
165
4.3
4,S
275
86
< 25
40
345000
17
as
< 0.5
SO
< 5
< 25
< 250
14000
115
18.5
< 11
160
< 5
675
(ig/B
< 1900
110
6100
160
^70
10000
1200
< 930
1500
1300000
610
1200
< 19
1900
< 190
< 930
< 9300
520000
5000
680
< 480
5900
< 190
25000
Duet Collector
Ash Output
1034
69,/g
M9/«
< 50
60
100
5.5
4.3
35000
71
< 25
64
45000
S3
700
< 0.5
48
6.5
< 25
< 250
5200
120
185
255
133
< 5
25500
IK^H
< 3500
4140
21000
380
300
2400000
4900
< 17OO
4400
3100000
6400
48000
< 15
1300
450
< 1700
< 17000
160000
8300
13000
18000
9200
< 350
1800000
Mass
Balance
(SASS +
Output)
Input
—
< DL
> 1.6
3.20
0.25 <0.29
l.S
0.81
0.85
< DL
O.82
0.62
0.65
0.57
< DL
l.S > 1.3
> 0.52
< DL
< pi.
0.96
0.65< 0.71
O.61
0.12
0.47
0.09S<0.12
0.97
Emission
Ratio
SASS
(Input -
Output)
—
< DL
> 4.4
-0.018
< 0.06
-0.14«p.05
0.29
0.59
< DL
0.10
0.01
0.03
0.06
3.1
< DL
< DL
< DL
0.13
< 0.9
0.11
0.05
0.37
0.09B
0.77
Ul
o
to
See notes on Table F-l
-------
TABLE P-53.
TRACE SPECIES EMISSIONS BY' SPARK SOURCE MASS SPECTROMETRY
TEST 13-18, WOOD-BARK BOILER
in
o
Ul
samel* vyp*
Supln KUBkMC
Sample Meight/Vol.
Unite
Antincmy
•runic
Bsriia
MtyllitB
CtdBiuB
CalciuB
CtirCMllUB
Cobalt
Cofffar
icon
Lend
Manganese
Mercury
Hick*!
Selenlua
TallurilB
fin
fitaniua
Vanadiua
Zinc
Chlorine
Fluorine
Confrinad
Solids
13-18 X, B t C
2.9141 9
wg/g
110
79O < HC
26 < HC
1.7
12
MC
160 < MC
28
87 < HC
MC
17 < HC
MC
NR
420
58
11
110
11 < MC
51 < MC
MC
240 < MC
38 < MC
vg/»a
28
200 < MC
0.67 < 1C
0.44 < MC
8.1
HC
40 < MC
7.1
2J < MC
MC
4.S < MC
MC
—
110
IS
8.6 < 8.7
28
2.7 < MC
11 < MC
HC
62 < MC
10 < MC
UD-2 Resin
13-18 D
119 g
W/9
< 0.2
< 8
- B
< 0.2
< 0.4
< B
< B
< 0.1
1
- B
< 0.9
- B
NR
1.1
< 0.2
< 0.2
< 0.2
< B
0.092
< B
< B '
< B
M,/.1
< 2.S
0
0
< 2.5
< 4.9
O-
O
< 1.2
12
0
< 11
0
—
14
< 2.5
< 2.5
< 2.5
O
1.1
0
0
0
Combined
Liquids
11-18 E
1990 ml
Jig/sa
< 0.004
< 0.0025
0.051
< 0,004
< 0.007
< B
0.90
0.020
< B
1.5
0.01
0.059
NR
0.40
< 0.015
< 0.004
< 0.004
0.0012
< B
< B
< B
< B
M/"1
< 1.4
< 0.87
18
< 1-4
< 2.S
O
320
7.1
0
540
11
21
—
140
< 5.3
< 1.4
< 1.4
1.1
0
0
0
o
total
Emission
Conce® .
11.25 »3
w«3
28 < 12
200 < MC
19 < MC
1.44 < MC
8.1 < 16
MC
360 < MC
14 < 16
15 < MC
540 < MC
16 < MC
21 < MC
NR
260
15 < 21
8.6 < 11
38 < 32
1.8 < MC
14 < MC
MC
62 < MC
10 < MC
Tot»l
Emission
Rate
10.8 nVs
W"
300 < 41
2200 < MC
200 < HC
4.8 < MC
90 < 170
MC
3900 < MC
160 < 170
380 < MC
5900 < MC
170 < MC
210 < MC
~
2900
160 < 250
93 < 140
100 < 140
41 < MC
ISO < MC
MC
670 < MC
110 < MC
Sea note* on Table F-l
-------
TABLE F-54,
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 13-18, WOOD-BARK BOILER
en
o
Sample Type
Sample Nunber
Sample Helght/Vol.
Units
Aluminum
Bl*KlUi
Boron
Bronlne
CerluB »
Cesiu*
Oyapraaiun
ErbluB
Europiun
Gadolinium
Gallium
Gamsniu*
Cold
HafniuB
HOlKluB
I odln.
Iridlu*
Lanthanum
Uthiu*
!*ute tiuja
MagnesiuM
Molybdenun
Neodyniua
NiobluB
OsBiiun
Cort>ined
Solids
13-18 A, B, I O
2,9143
M9/9
HC
8.4
580 < HC
46
ISO
19
3.6
1.7
t.7
2.7
74 < HC
5.4 < MC
< 0.10
1.7
i.a
11
< 0.10
46
36
0.21 < 0.22
HC
120 .
16
40
< o.ie
M/»3
HC
2.2
150 < MC
12
39
4.8
0.94
0.44
0.44
0.70
1.9 < HC
1.4 < HC
< 0.026
0.44
0.49
2.9
< 0.026
12
9.3
0.054
-------
TABLE F-55.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 13-18, WOOD-BARK BOILER
ui
o
i/i
Sanplg Typ*
S«I>1. Hu>b»
San>l* Weiqht/Vol.
Units
Palladiuw
Flatinua
Phosphorus
Potaasiun
Praaeodyalua
Rhenium
UradiuB
Rubidium
Ruthtniua
SanariiiBj
Scandium
Silicon
Silvar
Sodium
Sulfur
StrontiUB
Tantaliat
Thalliua
Terbium
Thorium
Thuliua
Tungsten
Uranium
ytterbium
Yttriua
Zircon! urn
Combined
Solids
13-18 A, B, i C
2.9143 9
U9/9
3.4
< 0.26
HC
HC
5.9
< 0.10
< 0.18
56
< 0.10
9.0
17
MC
14
MC
MC
0.48
< 0.56
41
0.89 <0.90
14
0. 35 < 0. 36
10
12
1.8
36
260
J>«/»3
0.89
< 0.068
HC
HC
1.5
< 0.026
< 0.04?
IS
< 0.026
2,3
4.3
HC
3.5
HC
HC
0.12
< 0.15
11
0.23
3.6 < 3.7
0.09
2.6
3.1
0.47
9.4
67
XAD-2 Resin
13-18 D
139 g
yg/g
< 0.2
< 0.2
< B
9
< 0.2
< 0.2
< 0.2
< B
< 0.2
< 0.2
< 0.1
< B
0.7
48
- B
1.7
< 0.2
< 0.2
< O.2
< o.a
< 0.2
< 0,2
< 0.2
< 0.2
0.2
" B
|ig/»J
< 2.5
< 2.5
0
110
< 2.5
< 2.5
< 2.5
0
< 2.5
< 2.5
< 1.2
0
8.6
590
0
3.7
< 2.5
< 2.5
< 2.5
< 2.5
< 2.5
< 2.S
< 2.5
< 2,5
Z.S
0
Combined
Liquids
13-18 E
3990 nl
m/mi.
< 0.004
< 0.004
< B
1.5 < HC
< 0.004
< 0.004
< 0.004
O.0023
< 0.004
< 0.004
< 0.002
< B
MC
HC
MC
< B
< 0.004
< 0.004
< 0.004
< O.O04
< 0.004
< 0.004
< 0.004
< 0.004
< 0.004
< B
M9/B1
< 1.4
< 1.4
0
550 < HC
< 1.4
< 1.4
< 1.4
0.83
< 1.4
< 1.4
0.71
0
HC
HC
HC
0
< 1.4
< 1,4
< 1.4
< 1.4
< 1.4
< 1.4
< 1.4
< 1.4
< 1.4
0
Tot»l
Emission
Concen .
11.25 •'
««/»*
0.89 < 4.8
< 4.0
HC
660 < HC
1.5 < 5.4
< 3.9
< 3.9
16
< J.9
2.3 < 6.2
5.0 < 5.1
HC
12 < MC
590 < MC
HC
3.8
< 4.1
11 < 15
0.23 < 4.1
3.6 < 7.6
O.O9 < 4.0
2.6 < 6.5
3.1 < 7.0
0.47 < 4.4
12 < 13
6?
Tot*l
EMi salon
Data
10.8 J»3/s
Mg/«
9.6 < 52
< 43
HC
7100 < HC
16 < 58
< 42
< 43
170
<• 42
25 < 67
54 < 55
HC
130' < HC
6400 < HC
HC
41
< 44
120 < 160
2.5 < 45
39 < 82
0.97 < 43
28 < 70
33 < 76
< 47
130 < 144
720
ee note cm Tabl* F-l
-------
TABLE F-56.
POM COMPOUNDS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY
LOCATION 13, WOOD-BARK BOILER
POM Component
Anthracane
Phenanthrene
Methyl Anthracenes
Fluoranthene
Pyrene
•Benzo (c ) phenanthrene
Chrysene
Benz (a) anthracene
Methyl Chrysenes
•7 , 12-Dimethylbenz (a )
anthracene
Benzo Fluoranthenes
»Benz(a)pyrene
Benz(e)pyr«ne
Perylene
*3-Methylcholanthrene
Indeno (1,2, 3-cd ) pyrene
Benzo (ghi)perylene
•Dibenzo (a, h) anthracene
•Dibenzo (c , g) carbazole
*Dibenz(ai and ahlpyrenes
Total
Stack Exit, Test 13-18
Cyclone Wash
605,606,607,333
nq/ml nq/m
0.0045
~
--
0.0009
~
—
0.0022
—
—
—
._
—
—
—
--
— '
~
—
—
—
0.0077
0.54
—
—
0.11
—
—
0.26
—
—
—
~
—
—
—
_
—
—
~
—
— -
0.91
XA0-2 Resin
530
nq/q nq/m
0.12
0.018
0.019
0.43
0.013
—
0.0026
—
—
—
0.0046
0.0031
0.0034
~
—
—
~
—
—
—
0.22
1.4
0.22
0.23
0.53
0.15
—
0.032
—
—
—
O.OS6
0.039
0.042
~
—
—
—
—
—
— .
2.7
Module Wash
264,331 3
nq/ml nq/m
0.019
—
~
0.0075
—
—
0.03
—
—
—
--
— •
—
~
—
—
~
—
—
—
0.057
0.60
~
~
0.23
—
—
0.93
—
—
—
--
—
--
—
—
—
__
~
-—
1.8
» Compounds required to be identified for this contract
Note: Values in this table are expressed in nonograms (ng), (1 ng -10 g),
Values in other trace species and organics tables in this report are
expressed in micrograms (ug), (1 ug " 10-6 g).
506
-------
TABLE F-57.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 13-24, WOOD-BARK BOILER
tn
O
-4
Saatpla TflMi
S««j>l* Maaber
Saapla Ihlgttt/Vbl.
Units
Anticony
AiMnic
B*rlua
Beryllium
C*fl*frM»w
C*lcii»
GirOBiUtt
Cobalt
Copper
Iron
Lead
Mongan*!*
Mercury
Nickel
SaleniuB
Talluriua
Tin
Tit»niu» >
V»n«diiiB
Zinc
Chlorida
Fluoride
Nitrate*
Sulfataa
total KM
total PCS
Hoxcle, Probe,
10 M" Cyclon*
Solid!
739
0.4806 1
uq/q
< 140
140
430
7
16
100000
140
< 70
l*»
33000
370
3900
1.4
110
17
< 70
< 700
4600
130
1300
N£S
920
KES
MBS
HES
KES
W»3
< 6.0
6.0
19
0.31
0.69
4300
6.0
< 1.0
6.9
1400
16
170
0.060
4.7
0.73
< 3.0
< 30
200
S.6
56
—
40
—
—
"
1 \m Cyclone
Solid*
731
0.3S27 q
W/9
< 170
300
430
7
13
57000
100
< 80
160
31000
350
4000
< 1.5
66
33
< 80
< 800
S700
120
1400
NKS
1300
HES
NGS
H?/"J
< 5.4
9.5
13
0.22
0.41
16OO
3.2
< 2.5
5.1
980
11
130
< 0.047
2.1
1.0
< 2.5
< 25.
180
3.8
44
—
41
—
~ "*
1 \m CycloiM
Solid!
735
1.2542 9
wq/g
< 170
260
420
7
18
65000
100
< 80
180
29000
330
5000
< 1.5
62
20
< 80
< 800
48OO
130
1500
130
1100
< 5
140000
l'9/»>
< 19
29
47
0.79
2.0
7300
11
< 9.0
20
3100
37
560
< 0.17
7.0
2.2
< 9.0
< 90
540
IS
170
15
120
< 0.56
16000
Filter*
284
* 1.2 g
W/9
< 100
120
460
11
76
£7000
170
< 50
4BO
21000
13000
3400
1.0
110 •
20
< 50
< 500
4400
210
7600
HES
1200
HES
NES
pg/«J
11
13
49
1.4
8.2
7200
18
5.4
52
2300
UOO
370
0.11
12
2.1
5.4
S4
470
23
820
—
110
~
—
Solid
Section
Wash
1847 ml
pq/Kl
< 0.5
< 0.01
< 0.05
< 0.005
0.01
100
0.05
< 0.05
0.09
5.9
0.08
2.0
< O.OOS
0.10
< 0.01
< 5
< 1
< 1
< O.I
0.47
2.1
< 0.20
1.1
45
0.010
< 0.005
IW/*1
< 83
< 1.7
< 8.1
< 0.83
1.7
17000
8.3
< 8.3
15
980
13
330
< 0.83
17
< 1.7
< 810
< 170
< 170
< 17
78
ISO
< 13
180
7400
1.7
< 0.83
So* notes oa Tabl* F-l
-------
TABLE F-58.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 13-24, WOOD-BARK BOILER
Saspla Type
Staple Muaber
Sample Weight/Veil.
Unit*
Juttlaony
Arsenic
Bariw
BerylliiiB
Cadniun
CalciUB
Ctammlum
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Tellurium
Tin
Titanium
Vanadiun
Zinc
Chloride
Fluoride
Nitrates
Sul fates
Total POM
Total PCB
Retin
531
167 q
W/g
< 50
< 3 •
< 3
< 0.5
< 0,5
< B
2,5
< as
1.0
< B
5
< B
< 0.5
< B
< S
< 25
< 250
15
< 5
< B
26
96
3.0
22
U9/«3
< 750
< 45
< 45
< 7.5
< 7.5
0
37
< 370
15
O
75
0
< 7.5
0
< 75
< 370
< 3700
22O
< 75
0
390
540
45
330
Organic Module
Rinse
609
298 ml
jigy«i
< 0.5
< 0.01
< 0.05
< O.O05
< 0.01
< 0.05
0.46
< 0.05
0.02
9.6
< B
0.28
< O.005
1.4
< 0.01
< &
< 1
< 1
< 0.1
0,038
11
3.3
0.22
5.0
0.23
< 0.010
W9/*3
< 13
< 0.27
< 1.3
< 0.13
< 0.27
< 1.3
12
< 1.3
0.53
260
0
7.5
< 0.13
37
< 0.27
< 130
< 27
< 27
< 2.7
1.0
290
88
5.9
130
6.1
< 0.27
Condensate
13-24 B
4048 nl
M9/»l
0.35
< 0,0099
< 0.049
< 0.0049
0.016
0.15
0.47
< 0.049
0.11
3.0
< 0.030
0.096
< 0.0049
0.42
< 0.0099
< 4.9
< 0.99
690
< 0.099
0.069
< B
5.4
0.46
17000
(so2)
M9/»3
130
< 3.6
< 18
< 1.8
5.9
56
170
< 18
40
1100
« 11
35
< 1.8
150
< 3.6
< 1800
< 360
250000
< 36
25
0
2000
79
3000000 (SO2
lapingar No, \
Combined with
Condensate
M/ml
M9/»J
iBPififff He}. 2,
Combined with
ConUa
yg/«d
naate
U9/«3
fppllMBf NtJ. 3
Combined with
Oopd?
lig/ml
sate
w/»3
Ul
o
03
See notam on Table F-l
-------
TABLE F-59.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 13-24, WOOD-BARK BOILER
Sample Tyva
Saapla Hunter
San^la Weight/Vol.
units
Antiaony
Arsenic
Barium
BerylliuM
Cadaiua
Calcium
CtuomiuB
Cobalt
Copper
Iron
Lead
ManganeiM
Mercury
Hiekal
Selenlua
Tellurian
Tin
TiUmiun
VaoaditiB
Zinc
Chloride
Fluoride
Nitrate*
Sulfate*
Total POM
Total PCB
EBi*sion
IB Partic.
< 3 (in
755 + 284
•»-2.5
wgy«3
11 < 10
42
96
2.2
2'8
15000
29
5.4 <14
72
5400
1400
930
O.U<0.28
19
4.3
5.4 < i4
54 < 140
1000
38
990
IS
25O
< 0.56
16000
total
£*ission
Conctm.
SASS
11.17 •'
w/»3
130 <980
58 < 110
130 < 200
2.7<11.4
19 < 26
23000
270
< 420
ISO
9800
1600
1500
O.17 < 11
210
6.2 < 87
< 1100
< 4500
250000
46 < 18O
1200
1100
1000
110
24000
7.9
< 1.1
Total
Kainsion
Rate
11. 0 «3/a
VJ 1.2
0.76
0.72
1.0
1.4
0.78
< DL
1.4
0.17
1.9
o.aa
< 01.
1.7
0.14
< PI.
< M.
1.4
1.1
1.1
0.78>O.S7
0.51
0.14 < IS
0.47
EBiaftlon
Ratio
SASS
(Input -
Output)
_„
< W,
< Ot
0.52
0.071
1. 1 < 1.5
0.63
0.49
< DL
5.7
0.013
3.6
O.61
< Dfc
-1.7 > -2.8
O.O24
< DL
< 01,
la
-0.51 <0.26
1.2
0.57 > 0.14
0.45
0.13
0.10
Ul
See notea on Table F-l
-------
TABLE P-60.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 14-2, STEEL OPEN HEARTH FURNACE
U1
H
O
Sample Tvnp«
Sanple Nuaber
Saaple W«ight/Vol.
Unit*
Antimony
krceaio
Barium
Beryllium
CadatiuB
Calcium
ChroeUum
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Seleniui*
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
Nitrates
Sulfste*
Total POM
Total PCB
Nozzle, Probe,
10 V* Cyclone
Solids
556
8.8596 g
Jig/fl
< 50
75
20
< 0.5
130
30000
320
< 25
940
240OOO
9500
2200
< 0.5
130
< 5
50
< 25O
500
60
6SOOO
400
560
11.0
19000
70.5
< 1
M/"1
< 37
56
15
< 0.17
96
22000
240
< 19
700
180000 .
7000
1600
< 0.37
96
< 3.7
37
< 190
370
44
48000
300
420
a. 2
14000
52
< 0.7
) |IB Cyclone
solid*
574
2.0105 9
lw/9
< 100
70
30
< 0.5
280
49000
ISO
< 50
1500
340000
22000
2700
< 0.6
ISO
< 10
250
< 500
1000
50
160000
1800
600
16
23000
NES
NES
pg/»3
< 17
12
5.0
< 8.4
47
82OO
64
< 840
250
57000
3700
450
< 1.0
25
< 1.7
42
< 84
170
840
27000
300
100
2.7
3900
—
1 IJH Cyclone
Solids
568
7.0748 g
\ig/g
< ISO
80
20
< 0.5
280
18000
330
< 25
1500
270000
12000
2100
< 0.5
130
< 5
ISO
< 500
500
SO
1 30000
iaoo
290
190
29000
104
< 1
H3/"J
< 89
47
12
< 2.9
170
11000
200
< 15
890
160000
7100
1200
< O.I
77
< 3.0
220
< 100
300
10
77000
1100
170
110
17000
62
< 0.6
Filter.
14 J
4.8611 g
V9/9
< 150
75
16
< 1.5
550
27000
310
< 25
1700
270000
620OO
2300
< 0.7
110
< 16
730
< 800
830
66
120000
2.6
250
eso
19000
NES
HES
W/"3
< 61
31
6.5
< 0.61
220
11000
130
< 10
690 '
110000
25000
940
< 0.28
• SI
< 6.5
300
< 330
340
27
49000
1.1
100
350
7700
—
"
Solid
Section
Hash
14 K
1683 ml
ug/nl
< 0.5
0.025
< 0.05
< 0.005
0,11
1.6
0.21
< 0.05
0.52
120
9.1
1.2
< 0.005
o.io
< 0.01
< 5
< I
< 1
< 0.1
20
2.7
< B
3.9
5.0
Nf)
NR
|iq/«3
< 70
3.5
< 7.0
< 0.7
15
230
30
< 7.0
.73
17000
1300
170
< O.7
14
< 1.4
< 700
< 140
< 140
< 14
2800
380
0
550
700
—
"
Sea notes on Table P-l
-------
TABLE F-61. TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 14-2, STEEL OPEN HEARTH FURNACE
Sample Type
sample Hurt**
SajopU Nelghfc/Val.
Unit*
JUttiacwy
Jknmic
BarlUB
Burylliu*
Cadaiua
CalciuH
GtoomiM*
Cobalt
Copper
Iron
Manganese
Mercury
nickel
Seleniun
TellurltiB
Tin
TitaniuB
Vanadiu*
Zinc
Chloride
fluoride
Nitrates
Sulfata*
•total PON
Total PCB
X*D-2
Statin
532
14? 4
ua/a
< 50
< 3
< 2.5
< 0.5
< O.S
- B
- B
< 25
- B
IS
< 5
• B
< O.S
1.5
5
< 25
< 250
15
< 5
O.S
• B
~
36
100
9.5
0.194
fa/"1
< 620
< 17
< 31
< 6.2
< 6.2
0
0
< 310
0
180
< 62
0
< 6.2
IB
62
< 310
< 3100
180
< 62
6.2
0
—
440
1200
120
2.4
Organic Nodule
Rinoe
616
430 ml
Ha/»i
< 0.5
< 0.01
< 0.05
< O.OO5
0.046
< 0.005
5.3
0.15
0.05
41
< 0.03
0.43
< 0.005
7.0
< 0.01
< 5
< 1
< 1
< 0.1
0.04S
29
20
0.84
3.0
0.021
< 0.01
||9/*J
< 18
< 0.36
< 1.8
< o.ia
1.7
< 0.18
190
5.4
1.8
1500
< 1.1
15*
< 0.18
25O
< 0.36
< ieo
< 36
< 36
< 3.6
1.6
1000
720
30
110
0,97
< O.36
Ccmdensate
14 L
4293 ml
HW*"1
0.33
< 0.01
< 0.049
< 0.0049
0.028
0.96
4.4
0.14
0.054
28
< B
0.1?
< 0.0049
4.4
< 0.01
< 4.9
< 1.0
< 1.0
< 0.1
0.1
< B
37
1,0
400 (SO.)
NR
NR
l«/«3
120
< 3.6
< 18
< 1.8
10
340
1600
50
19
10000
0
61
< 1.8
1600
< 3.6
< 180O
< 360
< 360
< 36
37
0
13000
370
140000 (S02)
—~
Xmpinqer No. 1
Combined with
Condertsate
Vf/"1
Hi'"3
Imiininr No. 2
Conbiiwd with
Coculenaate
M3/»l
w/»J
IMlnMr
Coafcined with
Conrteii
|»S/Bl
sate
Mi/"*
U)
See note* on Table f-1
-------
TABLE F-62.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCES
TEST 14-2, STEEL OPEN HEARTH FURNACE
ui
Sa«^>l« Type
Sample Number
Su#la Waiqht/Vol.
Units
Antimony
Arsenic
Bariuii
BerylliuB
Cadmium
CaiciUB
ChroniuB
Cobalt
Copper
Iron
lead
Manganese
Mercury
Nickel
SaleniuB
Tellurium
Tin
Tltaniun
Vanadiua
Zinc
Chloride
Fluoride
Nitrates
Sul fates
Total POH
Total PCB
Emission
in Partic.
< 3 (in
568 + 14 J
11.93S9 9
M/»3
< ISO
78
19
< 3.5
390
22000
330
< 25
1600
270000
32000
2100
< 3.3
130
< 9.5
520
< 610
640
57
130000
1100
270
460
25000
62
< 0.6
Total
S^sission
Concen .
SASS
11.95 B3
Jig/n
120 < 1000
150 < 190
38 < 92
0.37 < 10
S70 < 580
53000
2400
120 < 430
2700
530000
44000
3000
< 10
2100
62 < 81
590 < 3500
< 4400
1300 < 1900
110 < 230
200000
3100
15000
1600
45000
230
2.4 < 4.1
Total
Emission
lute
SASS
48.3 n3/*
W"s
5800 < 48000
7200 < 9200
1800 < 4400
16 < 4bO
28000
2.6K106
120000
5800 < 2 1000
130000
26x10*
Z.lmlO6
140000
< 4BO
lOOOOO
3000 < 3900
28000 < 170000
< 210000
63000 < 92000
5300 < 11000
9.7x10
I 50000
720000
77000
2.2x10*
11000
< 17
No. 6 Fuel Oil
1031
402 9/8
M9/9
< 25
< 2
< 5
< 0.3
< 0.3
31
< 5
< 10
< 3
39
< 3
1.0
< 0.1
10
< 1
< 25
< 25
< 250
33
3
< 17.1
38.0
NR
NR
NR
NR
M9/S
< 10000
< soo
< aooo
< 120
< 120
12000
< 2000
< 4000
< 1200
16000
< 1200
400
< 40
4000
< 400
< 10000
< 10000
< 100000
13000
1200
< 6900
15000
"•*
--
—
Mass Balance
SASS
Fuel
—
> 0.58
> 9.0
> 0.91
> 0.15
> 230
220
> 58
> 1.4
> 110
1600
>1800
350
< OL
25
> 7.4
> 2.8
< Dt
> 0.62
0.41 < 0.85
8000
> 22
47
I
—
—
Sea notes on Table F-l
-------
TABLE F-63.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPEGTROM1TRY
TEST 14-2, STEEL OPEN HEARTH FURNACE
SupiB Type
Sajnplo Number
Sample Haiqht/Vol.
Units
kntiwHty
JUmenlc
Bariim
Beryllium
CadniitioB
Calcium
ChrOBiliBI
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Seleniua
Tellurlu*
Tin
Titanium
Vanadiun
Zinc
Chlorine
Fluorine
Co«Un«d
Solids
14 A
22,8060 9
W«
23
98
MC
0.8
3
HC
540
36
320
MC
210
HC
m
110
36
< 0.7
24
HC
220
MC
•440
160 ,
U9/*3
44
190
HC
1.5
5.1
HC
1000
69
610
HC
400
HC
,.
210
69
< 1.3
46
HC
420
MC
840
310
XAD-2 Resin
14 B
14? q
Fi/9
< 0,3
< 0,3
2.5
< O.J
< 0.15
94
6
< 0.1
1
39
< 1
0.35
NM
1
0.45
< 0.5
0.4 < 0.55
7.6
0.05 < 0.1
0.5
< B
2
ug/«J
< 3.7
< 3.7
31
< J.7
< 4.3
1200
74
1.2
12
400
< 12
4.3
—
12
5.5
6.2
4,9 < 6. S
93
0.62 < 1.2
6.2
0
25
Combined
Liquids
14 C
4713 Hi
Pf/Bl
< 0.003
< 0,002
< B
< 0.001
< O.OO6
MC
9.0
< 0,003
< B
HC
< 0.006
0.17
NR
6.0
< 0.01
< 0.001
< Q.003
- B
< B
< B
< B
< B
U9/»J
< 1.2
< 0.79
0
< 0.39
< 2.4
HC
3500
< 1.2
0
HC
< 2.4
68
—
2400
< 3.9
< 1.2
< 1.2
0
0
0
< B
0
Total
Emission
Concen.
SASS
11.95 in1
M 21
460
4.4 < HC
> 0.72
> 1.8
4.2 < HC
1000
340 > 110
75
2,0 < HC
95
25 < MC
—
38
> 12
> 3.O
> 25
11 < MC
3.0
0.37 < MC
29
2.8
Best
Balance
M C SS
M or SS
Eniaaiun
M or SS
Input
0.58 < 4,8
360
5.3 < MC
> 0.72
> 1.8
185
5SO
340 > 1,4
75
1.5 < JfpO
95
7-3 < 1000
< OL
23
> 7,5
> 2.8
> 2S
11 < 160
0.80
8000
29
1.1
un
M
U)
Sea notes on Tabla F-l
-------
TABLE P-64.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 14-2, STEEL OPEN HEARTH FURNACE
Sample Type
Sample Number
Sample Weight /Vol.
Units
Aluminum!
Bi south
Boron
Bromine
Cerium
Cesium
Dysprosium
Erbium
Europium
Gadolinium
Gallium
Gemaniun
Cold
Itafnlun
Hoi mi urn
Iodine
Iridiu*
Ejmthanua
Lithium
LutetluB
Magnesium
Molybdenum
NeodymiuB
Niobium
Osmium
Combined
Solids
14 «
22.8060 g
OT/«
HC
2
HC
45
91
4
5
2
2
3
78
66
< 0.1
0.5
3
6
< 0.1
49
33
0.3
HC
53
26
27
< 0.1
W9/»3
«C
3.8
HC
B6
170
7.6
9,5
3.8
3.8
5.7
150
130
< 0.19
0,95
5.7
11
< 0,19
94
63
0.57
MC
100
50
52
< 0.19
XAD-2 Resin
14 B
147 9
U9/4
60
< 0.3
< B
< B
0.15 < 0.3
< 0.1
< 0.3
< 0.3
< 0.3
< 0.3
0.25
< 0.25
< 0.3
< 0.3
< 0.3
0.2 < 0.35
< 0.3
< 0.45
0.1 < 0.15
< 0.3
8
< B
< 0.3
< 0.3
< 0.3
H9/»3
740
3.7
0
0
1.8 < 3.7
< 1.2
< 3.7
< 3.7
< 3.7
< 3.7
3.1
< 3.1
< 3.7
< 3.7
< 3.7
2.5 < 4.3
< 3.7
5.5
1.2 < l.B
< 3.7
98
0
< 3.7
< 3.7
< 3.7
Combined
Liquids
14 C
4713 nl
|K?/»1
< B
< 0.003
< B
0.073
< 0.0017
< 0.003
< 0.003
< 0.003
< 0.003
< 0.003
< O.OO3
< 0.003
< O.003
< 0.003
< 0.003
0.00083
< 0.003
3OO < 650O
< 250
46 < 280
280 < 510
>70 < 740
< 250
4800
3100
?ao < 510
1700 < HC
14000
!400 < 2700
!500 < 2700
< 250
Input
No. 6 Fuel Oil
1031
402 q/a
Ma/a
2.4
< 0.25
3
0.45< O.S5
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
< 0.15
< 0.25
< 0.25
< 0.25
< 0. 25
< 0.25
< 0.25
< 0.25
0.3
< 0.25
7
6.5
< 0.25
< 0.25
< 0.25
yg/s
96O
< 100
12OO
ISO < 220
< 100
< 100
< 10O
< 100
< 10O
< 100
60
< 100
< 1OO
< 100
< 100
< 100
< 100
< 100
120
< 100
2800
2600
< 100
< 100
< 10O
SSHS
Has*
Balance
Entl salon
Input
37 < HC
> 3.6
HC
31 < 25
> 83
> 3.7
> 4.6
> 1.8
> 1.8
> 2.8
> 120
> 63
< DL
> 0.46
> 2.8
> 6.7
< DL
> 48
26
> 28
1.7 < HC
5.4
> 24
> 25
< DL
Ul
See note on Table F-l
-------
TABLE F-65.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 14-2, STEEL OPEN HEARTH FURNACE
Saaple Type
Eaople Nuad>er
Saaple Height/Wei.
Unit!
Palladium
Platlnun
Phosphorus
Potass I UK
Praseodymium
RheniuB
Rbodiya
Rubidlun
Buthenlua
SaaarillB
Scandium
Silicon
Sliver
Sodiua
Sal fur
Strontium
Tantalum
Thallium
Terbium
Thorium
Thulium
Tungsten
Uranium
Ytterbium
Tttriim
Zirconium
Combined
Solids
14 A
22.8060 g
Mf/sf
< 0, 1
< 0,1
MC
MC
12
< O.I
< O.I
200
< 0,1
6
IS
'MC
s
MC
HC
760
< O.B
28
1
22
0.4
7
17
2
39
100 .
Ilf/m1
< 0.19
< 0.19
HC
HC
23
< 0.19
< 0.19
380
< 0.19
11
29
HC
9.5
HC
MC
1500
< 1.5
53
1.9
42
7.6
13
32
3.8
74
190
XAD-2 Reaiit
14 B
147 9
tig/f
< 0. 3
< 0,3
17
220
0.15< 0.3
< 0.3
< 0.3
< B
• < 0.3
< 0.3
. B
400
7
7.5
B
0.7
< 0.3
< 0,3
< 0.3
< 0.3
< 0.3
< 0.3
< 0.3
< 0.3
0,15 < 0.1
- B
«/.»
< 3.7
< 3.7
210
2 BOO
1.8 < 3.7
< 3.7
< 3.7
0
< 3.7
< 3.7
0
4900
86
920
98
8.6
< 3.7
< 1.7
< 1.7
< 3.7
< 3.7
< 3.7
< 3.7
< 3.7
1.8 < 3.7
0
Combined
Liquids
14 C
4713 *l
|ig/«l
< 0.003
< 0.003
HC
HC
< 0.003
< 0.003
* O.003
< 0.0029
< 0.003
< 0.003
< 0.001
MC
HC
MC
MC
< B
< 0.003
< 0.001
< 0.003
< 0.003
< 0.003
< 0.003
< O.OO3
< 0.003
< 0.003
< B
Pfl/m1
< 1.2
< 1.2
MC
MC
< 1.2
< 1.2
< 1.2
< 1.1
< 1.2
< 1.2
< 0.19
MC
MC
MC
HC
0
< 1.2
< 1.2
« 1.2
< 1.2
< 1.2
< 1.2
< 1.2
< 1.2
< 1.2
0
Total
End 88 ion
Conceri.
SASS
11.95 n1
|>g/B
< 5.1
< 5.1
210 < «C
2800 < HC
25 < 28
< 5.1
< 5.1
380
< 5.1
11 < IS
29
4900 < MC
96 < HC
920 < MC
98 < MC
1500
< 6.4
53 < 58
1.9 < 5.1
42 < 47
7.6 < 13
13 < 18
32 < 37
3.8 < 8.7
76 < 79
190
Total
Etal»ion
Rate
48.3 n3/«
yg/B
< 250
< 250
10000 < MC
140000 < MC
1200 < 1300
< 250
< 250
18000
< 250
530 < 720
1400
240000< MC
4600 < MC
44000 < HC
4700 < MC
72000<73000
< 310
2600 < 2800
92 < 250
2000 < 2 300
370 < 60O
630 < 860
1500 < 1800
180 < 420
3700 < 3800
9200
Input
No. 6 Fuel Oil
1031
402 g/s
V9/9
< 0.25
< 0.25
5.5
IB
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
0,15 < 0.2
59
0.1 < 0.25
33
160 < MC
0.35
< 0.25
'< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
< 0.25
1.5
U9/«
< 100
< 100
2200
7200
< 100
< 100
< 100
< 100
< 100
< 100
60 < 80
24000
40 < 100
13000
64000< MC
141
< 100
< 1OO
< 100
< 100
< 100
< 100
< 100
< 100
< 100
6OO
SSMS
Ma*l
Balance
Bmi avion
Input
< DL
< OL
4.5 < MC
19 < HC
> 12
< OI>
< DL
> 180
< DL
> 5.3
23 > 17
10 < MC
114
3.3 < MC
0.07
510 < 520
< DL
> 26
> 0.92
20
> 3.7
> 6.3
> 15
> 1.8
> 37
15
in
l_i
Ul
See note on fable P~l
-------
TABLE F-66.
POM COMPOUNDS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY
LOCATION 14, OPEN HEARTH STEEL FURNACE
POM Component
Anthracene
Phenanthrene
Methyl Anthracenes
Fluoran thane
Eyrena
•Benzo (c) phenanthrene
Chrysene
Benz (a) anthracene
Methyl Chrysenes
*7,12-0iaiethylbenz (a)
anthracene
Benzo Fluoranthenes
*Benz (a) pyrene
&enz (a)pyrene
Perylene
* 3~Methy lehalanthrana
' Indenod, 2, 3-cd) pyrene
Senzo (gra)peryler.e
•Dibenzo (a,h) anthracene
•Difaenzo (c , g) carbazole
•Dihenzfai and ah)pyrenas
Total
Stack Exit Test 14-2
XAD-2 Resin
532
ng/g ng/»
0.38
0.022
0.098
0.20
0.047
—
0.020
—
—
—
0.0071
~
—
— "
—
— •
— •
~
~
~
0.73
4.7
0.27
1.2
2.5
0.58
—
0.25
__
—
_
0.087
__
_
—
—
, —
—
— .
~
~
9.6
Module Wash
616
ng/mX ng/et
0.0094
—
—
0.0023
—
—
—
—
__
__
-_
__
—
__
__
—
—
—
™
—
0.012
0.43
—
—
0.12
—
—
—
._
_-
—
—
—
—
._
—
—
—
__
—
—
0.60
» Coa^iounds r*quir*d to be identified for this contract
Note:
(1 ng - 10~9 g).
Values in this table are expressed in nonograms (ng}
Values in other trace species and organics tables in this report are
expressed in microgratas tug), (1 ug - 10~6 g).
516
-------
TABLE F-67.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 15-10, DIESEL ENGINE
Ul
H
-J
Saiiple Typ«
Ba*pl* Number
Sajupla Helght/Vol.
Unite
JUitlnony
Arsenic
Barium
Berylllua
Cadmium
Calciua
Ctiromlua
Cobalt
Copper
Iron
Lead
Manganese
Hercury
Nickel
Seleniua
Tellurium
Tin
Titaniua
Vsnadiun
Zinc
Chloride
Fluoride
Nitrates
6ul fates
Total PON
Total PCS
NoxzlH, Probe,
10 |M Cyclone
Solids
563
0.0032 q
ug/g
NES
NES
HES
NES
NES
NES
NES
NES
NES
HES
NES
(res
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
NES
M9/«3
3 |la Cyclone
Solids
None
ng/9
M9/"3
1 w« Cyclone
Solids
None
M9/9
H9/»3
r liter* "
541
0.233S q
yg/g
< 200
< a.o
< 80
< 4.0
< 4,0
68000
64
12
20
1300
< 40
40
< O.16
20
16
< 200
< 400
< 1200
< 80
670
NES
< 5
NES
NES
NES
NES
M9/»3
< 2-7
< O.li
< 1.1
< 0.053
< 0.05J
0.90
0.8S
0.41
0.27
17
< 0.53
O.S3
< 0.0021
0.27
O.21
< 2.7
< 5.3
< 16
< 1.1
8.9
—
< 0.067
—
—
—
--
Solid
Section
Hash
15-10 A
1407 ml
w/«a
< 0.5
< o.oos
< 0.1
< 0.005
< 0,005
0.04
0.03
< 0.2
< 0.02
a. IB
< 0.05
0.12
< 0.005
0.47
< fl.niq
< 0.3
< 1
< 1
< 0.1
0.15
1.6
< 0.1
0.12
- B
HR
NR
M9/«3
< 40
< 0.4
< 8.0
< 0.4
< O.4
3.2
2.4
< 16
< 1.6
3O
< 4.0
9.6
< 0.4
38
< n.B
< 24
< 80
< 80
< 8.0
\2
130
< 8.0
9.6
0
See notes on Table F-l
-------
TABLE F-68.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 15-10, DIESEL ENGINE
Sample Type
Supple Nuaber
Sjuaple Woight/Vol.
Units
Antimony
Xrsenic
Bariua
Berylliua
Cddmiua
Calciua
Chromium
Cobalt
Copper
Iron
Lead
H*ng*n«»e
Heccury
Nickel
Seleniuit
Tolluriu.
Tin
Tituiiua
Vanadium
Zinc
Chloride
Fluoride
Nitrate*
Sulfateg
Total POM
Total PCB
XAD-2
Reain
1041
ISO g
W/1
< 23
0.1
< B
0.46
< B
< B
< B
< B
< B
5
< 2.1
0.3
< 0.02
2.3
1.9
< 21
< 46
< 140
< 9.3
2.4
S3
< B
55
90
< 0.1
< 1
W/-3
< 200
O.SS
0
3.9
O
0
0
0
0
43
* 20
2.6
< 0.17
20
16
< 200
< 390
<1200
< 79
20
450
0
470
770
< 0.9
< 9
Organic Module
RillbB
899
398 Ml
yg/ni
< 0.5
0.02
< 0.1
< 0.005
0.03
0.08
2.0
< 0,2
0.10
3.2
< 0.05
0.09
< O.OOS
0.51
0.05
< 0.3
< 1
< 1
< 0.1
0.13
0.54
0.21
0.06
19
HiS
NES
w»3
< 11
0.45
< 2.3
< O.U
0.6B
i.a
45
< 4.5
2.3
73
< 1.1
2.0
< O.U
12
1.1
< 6.8
< 23
< 23
< 2.3
2.9
12
4,8
1.4
430
~
Condensate
15-10 B
3877 nl
P9/»l
< 0.49
0.010
< 0.10
< 0.0049
0.013
0.41
0.39 .
< 0.20
0.034
1.5
< 0.031
0.064
< O.0049
0.23
0.020
< 0.31
< 1.0
< 1.0
< o.io
0.13
3.1
0.28
< B
1300 (S02)
NR
NR
ug/»3
< 110
2.2
< 22
< 1.1
2.9
91
85
< 44
7.4
340
< 6.8
14
< 1.1
51
4.4
< 68
< 220
< 220
< 22
30
680
63
0
290000 (SO 1
—
Xnpinqer No. 1
Combined with
Condensate '
n/*1
yg/o3
•
Implnqer Mo, 2
Combined with
Conde
pg/«l
nsate
W9/«3
imlnaer
Combined with
Cot^densate
V9/0.
yg/»3
Ul
l_l
CD
Sea notes on Table f-l
-------
TABLE P-69.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCE
TEST 15-10, DIESEL ENGINE
ui
H
10
iatiple Typa
Saaple Number
Sickle Waight/Vol.
Units
AntiBonjf
JU«enic
Barium
B*rylliu«
Cadaiun
Calciua
CturoBiuB
Cobalt
Copper
Iron
Lent
H*n9*ne*a
Mercury
nickel
SeleniuM
Talluriua
Tin
Titaniim
VaAadiua
Zinc
Ch lor Ida
fluoride
HitHtec
Sulfate*
Total SOU
Total KB
BaifiBion
In Par tic.
< 3 Ji»
541
0.2335 q
M9/»3
< 2.7
< 0,11
< 1.1
< O.OS3
< 0.053
0.90
0.85
0.43
0.27
17
< 0.53
0.53
< 0.0021
0.27
0.21
< 2.7
< 5.'3
< 16
< 1.1
8.9
—
< 0.06?
~
~
NES
HES
Total
Emission
Concen.
SASS
17.55 a3
M9/«3
< 360
4.1
< 34
3.9 < 5.6
3.6 < 4.1
1000
140
0.43 < 68
9.7 < 11
510
< 32
30
< 1.8
120
22 < 23
« 300
< 740
< 1500
< 110
74
1100
68 < 74
480
1200
< 0.9
< 9
Total
Emission
Rat a
SASS
0.575 «3/B
lig/s
< 210
2.4
< 20
2.2 < 3.2
2.1 < 2.4
560
ai
0.25 < 39
5.6 < 6.3
290
< 18
17
< 1.0
69
13
< 170
< 430
< 660
< 63
43
630
39 < 43
280
690
< 0.5
< 5
foal Input
Ho. 2 Diesel oil
1042
26,4 B/«
M9/9
< 25
< 2
30
< 0.3
< 0.3
30
< 5
< 10
< 3
< 5
< 5
1.0
< 0.1
< 1.0
< 1.0
< 25
< 25
< 250
< 5
10
< 10
12.5
1.95
44.3
MR
NR
lig/a
< 660
< 51
790
< 7.9
< 7,f
790
< 130
< 260
< 79
< 130
< 130
26
< 2.6
< 2.6
< 2.6
< 660
< 660
< 6600
< 130
260
< 260
330
52
1200
_-
—
Haas
Balance
Emission
Input
< DL
> 0.05
> 0.03
> 0.28
> O.26
0.73
> 0.62
< DL
> 0.071
> 2.2
< DJ.
0.65
< DL
> 2.7
> 0.5
< DL
< Ob
< DL
< m.
0.17
> 2.4
0.12 < 0.11
5.4
0.38
..
—
See not** on Tabl* F-l
-------
TABLE F-70.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY
. TEST 15-10, DIESEL ENGINE
Staple Type
Simple Number
Sample Height/Veil.
Units
Antimony
Arsenic
Bari.ua
Beryllium
Cadmium
Calciua
Chronium
Cobalt
Copper
Iron
I*ad
Manganese
Mercury
Nickel
Selenium
Tellurium
fin
Titanium
Vanadium
Zinc
Chlorine
Fluorine
Corel)! ned
Solids
15-10 E £ A'
0.2335
ng/g
240
190
3BOO
< 120
1 < 120
HC
looo
200
1600
30000
44OO
230
NR
390O
4SO
< 120
13 < 130
760
1800
1800 < HC
ISO
nc
w/»3
3.2
2.5
50
< 1.6
0.057 <1,6
MC
14
2.7
2.2
400
59
3.1
—
52
6.4
< 1.6
1.4 < 1.8
10
24
24 < HC
•2.4
HC
XAD-2 Resin
15-10 F
150 9
W/9
< 0.1
< 0.1
< B
< 0.1
< 0.1
< B
< B
< 0.1
< 0.1
" B
< 0.5
< 0.1
HR
< B
< 0.1
< 0.1
< 0.1
< B
« B
< B
* B
1
M9/B3
< 0.85
< 0.85
0
< 0.85
< 0.85
0
0
< 0.85
O
0
< 4.3
< 0.85
—
0
< 0.85
< 0.85
< 0.85
0
0
0
0
8.5
Combined
Liquids
15-10 G
4275 mi
tig/Hi
0.009
0.026
< B
< O.O01
0.0053
MC
< B
O.068
< B
6.1
0.19
0.021
NR
< B
< o.ol
< O.OO3
< O.OOB
0.18 •
0.011
0.0056
< 8
< B
M/»3
2.2
6.5
0
< 0.24
1.3
HC
O
17
0
1500
46
5.1
—
0
< 2.4
< 0.73
< 1.9
44
2.7
1.4
0
0
Total
Emission
Concen .
SASS
17.55 mJ
V9/*3
5.4 < 6.3
9.0 < 9.9
SO
< 2.7
1.4 < 3.8
HC
14
20 < 21
2.2
1900
110
8.2 < 9.1
NR
52
6.4 < 9.7
.< 3.2
1.4 < 4.6
54
27
25 < HC
2.4
a. 5 < HC
Total
Emission
Rate
0.575 «J/«
(jg/s
3.1 < 3.6
5.2 < 5.7
29
< 1.5
7.8 < 2.2
HC
8.1
11 < 12
1.3 {
1100
6O
4.7 < 5.2
—
30
3.7 < 5.5
< 1.8
0.81 < 2.6
31
15
. 15 < HC
1.4
4,9 < HC
Input
No. 2 Diesel Oil
15-10 H (1042)
26.4 g/s
M9/g
0.009
O.OOB
O.07
< 0.004
< 0.008
1
0.01
0.002
0.08
0.1
0.06
0.005
NR
0.02
< 0.01
< 0.004
< O.O04
O.05
0.003
0.4
0.3
0.4
M9/S
0.24
O.2i
1.8
< 0.11
< O.21
26
0.26
0.053
2.1
2.6
1.6
0.13
—
5.3
< 0.26
< 0.11
< 0.11
1.3
O.O79
11
7.9
11
SSMS
Mass
Balance
Emission
Input
1J < 15
25 < 27
16
< DL
> 3.7
HC
30
210 < 220
O.6O
410
33 < 40
36 < 39
—
57
14 < 21
< DL
> 7.6
24
190
1.4 < HC
0.17
O.46 < HC
Best
Balance
AA t SS
M or SS
Ealaslon
Input
11 < 15
11
16
> 20
> 0.99
0.73
31
4.7 < 740
0.62
110
< 11
6.5
< DL
5.7
> 0.50
< DL
> 7.4
24
190
1.4 < HC
0.18
0.44
Ul
la
O
See notes on Table F-l
-------
TABLE F-71.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 15-10, DIESEL ENGINE
sample TYP«
Sample Dumber
Sample Neight/Vol.
Units
Aluminum
Bi smith
Boron
Stamina
Cerium
Cesium
Dysprosium
erbium
Europium
Gadolinium
Gallium
German 1 IK
Gold
Hafnium
Holmium
lodin*
Iridium
Lanthanum
Lithium
Lutetiua
Magnesium
Molybdenum
Neodymium
Niobium
OsBiu*
Combined
Solids
15-10 E £ ft'
0.2335
U9/4
> 2300
0.4 < 120
1100
65
240
180
< 1ZO
< 120
< 120
< 120
1 < 61
< 120
< 120
< 120
< 120
190
< 120
420
0.5 < 6.5
< 120
2SOOO
3000
0.3 < 120
0.3 < 120
< 120
M/s>J
> 31
9.0053 < 1.6
14
0.87
3.2
2.4
< 1.6
< 1.6
< 1.6
< 1.6
J.013 <0.82
< 1.6
< 1.6
< 1,6
< 1.6
2.6
< 1.6
5.6
XAD-2 Resin
15-10 r
150 g
|ig/q
- B
< O.I
< a
< B
< O.I
< O.I
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
< O.I
< O.I
< O.I
< 0.1
0.2
< 0.1
< 0.1
>.0067 3.7
< O.O03
< B
< B
0.0061
O.O025
< 0.003
< 0.003
0.004
< 0.003
0.004
< 0.002
< 0.003
* 0.003
< 0.003
< B
< 0.003
0.034
< B
< 0.001
HC
< B
0.1
0.004
< 0.003
M9/*3
> 900
< 0.73
0
0
1.5
0.62
< 0.73
< 0.73
0.97
< 0.73
0.97
< 0.49
< O.73
< 0.73
< 0.73
0
< 0.73
S. 4
0
< 0.73
HC
0
2.4
0.97
< 0.73
Total
Emission
Concen.
SASS
17.55 a3
M9/«3
> 930
0.0053< iJt
14
0.87
4.7 < 5.6
3.0 < 3.9
< 3.2
< 3.2
3.97 < 3.4
< 3.2
3.98 < 2.6
< 2.9
< 3.2
< 3.2
< 3.2
4.3
< 3.2
14 < 15
3.86 <0.94
< 3.2
380 < MC
40
2.4 < 4.9
).97 < 11
< 3.2
Total
EBlssion
Rate
0.575 •*,*
M9/«
< 540
3.0O30<0.9I
8.1
0,50
2.7 < 3.2
1.7 < 2.2
< 1.8
< 1.8
5.6 < Z.O
< 1.8
O.57 < 1.5
< 1.7
< i.a
< 1.8
< 1,8
2.5
< i.a
8.1 < 8.5
>.49<0.54
< 1.8
220 < HC
23
1.4 < 2.8
).S6 < 6.4
< i.a
Input
Ho. 2 Diesel Oil
15-10 H (1042)
26.4 q/a
ya/9
0.06
< O.OO4
0.02
0.02
0.01
< O.O02
< 0.004
< 0.004
< 0.004
< 0.004
O.OO3
< O.O04
< 0.006
< 0.004
< 0.004
0.009
< 0.004
0.01
< O.OOl
< 0.004
0.2
0.1
< 0.004
< 0.004
< O.004
M/s
1.6
< O.ll
0.53
0.53
0.26
< 0.053
< O.ll
< 0.11
< 0.11
< 0.11
0.079
< 0.11
< 0.16
< 0.11
< 0.11
0.24
< 0.11
0.26
< O.O26
< 0.11
5.3
2.6
< 0.11
< 0.11
< O.ll
SSHS
Ha»
Balance
Emission
Input
> 340
> 0,029
15
0.95
10 < 12 .
> 33
< m.
< BE.
> 5.1
< Dl>
7.1 < 19
< Dt
< Ot
< DI.
< DL ,
10
< DL
30 < 32
> 19
< OL
41 < MC
8.7
> 13
> 5.J
< DL
Ul
K>
Sea note on Table f~l
-------
TABLE F-72.
TRACE SPECIES EMISSIONS BY SPARK SOURCE MASS SPECTROMETRY (Continued)
TEST 15-10, DIESEL ENGINE
Saople Type
Sample Number
Eanple Helght/Vol.
Units
Palladium
Platinum
Phospnorua
Potassium
Praseodymium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Silicon
Silver
Sodium
Sulfur
Strontium
Tantalum
Thai HUB
Terbium
Thorium
Thuliua
Tungsten
Uranium
Ytterbium
yttrium
Zirconium
Combined
Solids
15-10 E f. A'
0.2335
UO/9
< 120
< 120
HC
27000 < HC
120
< 120
< 120
43
< 120
< 120
< 60
14000 320
25
< B
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
< 0,1
< 0.1
< 0.1
< 0.1
- B
ug/«3
< 0.85
< o.as
51
0
< 0.85
< 0.85
< 0.85
< 0.85
< 0.85
< 0.85
< O.BS
0
0.85
> 2700
210
0
< 0.85
< 0.85
< 0.85
< 0.85
< 0.85
< 0.85
< 0,85
< 0.85
< 0.85
0
Combined
Liquids
15-10 G
4275 ml
(ig/ml
< 0.003
< 0.003
HC
< B
O.O06
< 0.003
< 0.003
< B
< 0.003
< 0.01
< 0.004
< B
HC
HC
HC
0.12
< 0.003
< 0.003
< 0.003
< 0,003
< 0.003
< B
0,036
< O.OO3
0.003
< B
J
< 0.73
< 0.73
MC
0
1.5
< 0.73
< 0.73
0
< 0.73
< 2,4-
< 0.97
0
MC
MC
HC
30
< 0.73
< 0.73
< 0.73
< 7,1
< 0.73
0
8.9
< 0.73
0,73
0
Total
End as ion
Concen.
SASS
17.55 n3
M9/»J
< 3.2
< 3.2
51 < MC
360 < HC
3.1 < 4.0
< 3.2
f 3.2
0.57 < 1,4
< 3.2
< 4.9
< 2,6
190 < HC
240 < MC
2700 < MC
220 < MC
100
< 3.2
< 3.2
< 3.2
0.027 <24
< 3.2
0.080 <2,6
9,1 < 26
< 3.2
0.74 < 3.2
6.7
Total
Emission
Rate
O.575 »3/fc
|ig/«
< 1.8
< 1.8
29 < HC
210 < HC
1.8 < 2.3
< 1.8
< 1.8
0.33 <0.82
< 1.8
< 2.8
< 1.5
110 < MC
140 < HC
•160O 17
< DL
< DL
12 < 31
< DL
< DL
< OL
10 < HC
260 < HC
150 < HC
4.8 < MC
220
< DL
< DL
< DL
0.012 < 11
< DL
0.44 < 14
313 < 9.3
•c DL
4.0
2.1
Ul
See note on Table P-l
-------
TABLE F-73.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS SOLIDS SECTION COLLECTION
TEST 15-11, DIESEL ENGINE
en
to
to
Santple Type
Sup la Humber
Sanple Hoight/Vol.
Unit*
Antinony
Arsenic
Bariuai
Beryl HUB
CadMiuB
Caiciu*
ChfOMlUB
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nickel
Seleniua
Tellurium
Tin
Titanium
Vanadiu*
Zinc
Chloride
Fluoride
Nitrate*
Sul fates
Total POH
Total PCS
Nozzle, Probe,
10 Ma Cyclone
Sol Ida
NONE
pg/g
Mi/"3
3 M» Cyclone
Solids
HONE
J»9/9
il9/»3
1 M« Cyclone
Solids
NONE
w/9
M/»J
niters
542
0.23
M9/g
< 100
< 16
< 280
< 2
< 2
< 60000
25
17
14
< 1000
< 10
< 34
< 0.08
< 10
< 4
< 100
< 200
< 600
< 40
2700
NGS
NES
NES
NES
NES
NES
f4 0-
u,/-3
< 1.3
< 0.2
< J.7
< 0.026
< 0.026
< 790
0.33
0.22
0.45
< 11
< 0.13
< 0.45
< 0.0011
< 0.13
< 0.053
< 1.3
< 2.6
< 7.9
< 0.53
35
__
—
__
—
—
*"""
Solid
Section
Wash
15-11 »
141
ug/*i
< O.S
< 0.005
< O.I
< O.O05
< 0.005
0.75
O.O1
< 0.2
< O.O2
O.14
< 0.05
0.03
< 0.005
0.11
< 0.01
< a. j
< I
< 1
< 0.1
0.18
0.54
« 0.1
« B
2.0
NR
HR
p El
M9/1B
< 39
< 0.39
< 7.9
< 0.39
< 0,3?
59
0.79
< 16
< 1.6
11
< 1.9
2.4
< O. 39
8.7
< 0.79
< 24
< 79
< 79
< 7.9
14
42
< 7.9
0
160
„
"
Sea notes on Table f-i
-------
TABLE F-74.
TRACE SPECIES AND ORGANIC EMISSIONS, SASS ORGANIC
AND LIQUIDS SECTION COLLECTION
TEST 15-11, DIESEL ENGINE
Simple Typo
Sample MuBber
Suple Weight Aol-
Unltt
Antinony
lursenic
BariuM
Beryllium
Cadaiua
CalciuB
ChraaiuB
Cobalt
Copper
' Iron
Lead
Hanganeae
Mercury
Hickel
Seleniuai
Tellurium
Tin
Titanium
Vanadiua
Zinc
Chloride
Fluoride
Nitrates
SuU*te*
Total POM
Total KB
XAD-2
Rosin
1044
1S4 g
M/9
< 23
S.5
100
< 0.46
< B
< B
< B
0.7
2.1
< B
—
• B
< 0.02
< 2.3
< 0.91
< 21
< 46
< 140
< 9.1
< B
< 11
< B
1.5
< 50
< 0.1
< 1
M9/«3
< 200
4?
860
< 3.9
0
0
0
6.0
18
0
—
0
< 0.17
< 20
< 7.8
< 200
< 390
<1200
< 78
0
< 94
0
13
< 430
< 0.9
< 9.0
Organic Module
Rinsa
941
402 ml
(jg/ml
< 0.5
0.01
< 0.1
< 0.005
0.03
0.10
0.82
< 0.2
0.04
1.5
< 0.05
0.04
< 0.005
0.25
0.04
< 0.3
< J
< 1
< 0.1
• B
0.54
< 0.1
0.02
5.2
< 0.001
< 0.001
H3/»3
< 11
0.22
< 2.2
< 0.11
0.67
2.2
18
< 4.5
0.89
34
< 1.1
0.89
< 0.11
5.6
0.69
< 6.7
< 22
< 22
< 2.2
0
.12
< 2.2
0.45
120
< O.O2
< 0.02
Condeusdtu
15-11 B
4062 ml
pg/ml
< 0.49
< 0.0049
< 0.10
< 0,0049
0.0064
0.39
0.12
< 0,20
< 0.013
0.42
< 0.032
0.015
0.0049
0.010
O.O2
< 0.30
< 1.0
< 1.0
< O.I
0.14
S4
0.21
< B
1300 (SO2)
NH
HK
, , w/p3
< 110
< 1,1
< 23
< 1.1
1.9,
89
27
< 45
< 2.8
94
< 7.2
3.4
1.1
21
4.5
< 67
< 230
< 230
< 23
32
12000 *
47
0
290000 (SO)
-"*
Xiapinger Ho. 1
Combined with
Condensate
]ig/Bl
wa/s1
IiJpinqer Ho. 2
Combined with
CondenBate
- W
-------
TABLE F-75.
TRACE SPECIES AND ORGANICS EMISSIONS, PROCESS SAMPLES AND MASS BALANCE
TEST 15-11, DIESEL ENGINE
(Jl
to
U1
Saapl* Type
Sacple Hunber
Sample Halght/Vol.
Units
Antiaony
Xrsenic
BarilM
BerylliiM
Cadmium
Calcium
Ctirojuua
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Kicks!
Selenium
Tellurium
Tin
Titanium
Vanadium
Zinc
Chloride
Fluoride
nitrates
Sulfstae
Total KM
To tan PCB
EniMlon
in Par tic.
< 3 MB
542
0.2364
H9/«3
< 1.3
< 0.2
< 3.7
< 0.026
< 0.026
< 790
0.31
0.22
0.45
< 13
< 0.13
< O.4S
< 0.0011
< 0.13
< 0.053
< 1.3
< 2.6
< 7.9
< 0.53
35
NES
NES
NBS
NES
NES
NES
Total
Emission
Concen.
SASS
18.00 a3
yg/m3
< 360
47 < 49
830 < 890
< 5.6
2.6 < 3
160 < 780
46
6.1 < 72
19 < 24
140 < ISO
< 12
6.7 < 7.2
< 1.8
3.7 < 56
5.4 < 14
< 290
< 720
<1500
< 110
89
12000
47 < 56
13
280 < 710
< 0.92
< 9.0
Total
Emission
Rate
0.582 m3/s
U^a
< 210
27 < 29
480 < 520
< 3.3
1.5 < 1.7
93 < 450
27
3.6 < 42
11 < 14
si < a?
< 7.0
3.9 < 4.2
0.51
> 3.7
< M.
> 0.19
0.12
> 0.21
< DL
> 0.14
> 0.62
< DL
0.49
< M*
> O.O8S
> 0.12
< DL
< DL
< DL
< Ol
1 > 4
> 29
O.O75
0.036
0.12
..
--
See note* on Tabla F-l
-------
TABLE F-76.
POM COMPOUNDS BY GAS CHRQMATOGRAPHY-MASS SPECTROMETRY
LOCATION 15, DIESEL ENGINE
Stack Exit
XAD-2 Resin
1041
Module Wash
941
POM Component
nq/g
ngr/m
ng/ml
ng/n
Anthracene
Phenanthrene
Methyl Anthracenes
Fluoranthene
Pyrene
•flenzo (c)phenantftrana
Chrysene
Benz ta) anthracene
Methyl Chrysenes
•7 , 12-Dimethylbenz (a)
anthracene
Benzo Fluoranthene s
*Benz(a)pyrene
Benz(e)pyrane
Perylene
* 3-Methy Icholanthrene
Indeno {1,2, 3-cd } py ren«
Benzo (fhi)perylene
•Dibenzo (a,h) anthracene '
•Dibenzo (e, g) carbazole
•Oibenz{ai and alsSpyrenes
Total
17
0.11
14
0.16
—
O.OQ27
0.0079
0.0003
0.0018
—
0.0035
0.0028
0.0027
—
—
—
—
—
—
—
32
148
0.93
122
1.4
—
0.023
0.068
0.0068
0.015
—
0.030
0.024
0.023
—
—
_
_
~
—
—
273
0.0028
—
—
0.0017
—
—
0.011
—
—
—
0.0040
--
'
—
—
. —
—
—
--
—
0.02
0.062
—
—
0.039
—
__
0.24
--
—
—
0.094
—
—
—
_
—
—
>_
_«
— -
0.44
• Compounds required to be identified for this contract
Note; Values in this table are expressed in nonograms
-------
APPENDIX G
SASS TRAIN EVALUATION TEST
527
-------
BLANK PAGE
528
-------
SECTION G-1,0
INTRODUCTION
The Aerothem prototype S&SS train was delivered to KVB for evaluation.
tests conducted on a boiler in the K7B laboratory burning West Virginia
Pittsburgh No. 8 coal. The purpose of these tests was to determine the
ability of the train to collect all of the trace elements and organics
required for the current program. By weighing and analysis of the coal and
all solid ashes and comparison with train catch, the ability of the train to
establish mass balances on the desired elements could be established. In
addition to evaluation of the chemical performance of the train, mechanical
performance and suitability for field testing was evaluated and recommenda-
tions made for improved operation.
529
-------
SECTION G-2.0
SOURCE ASSESSMENT SAMPLING SYSTEM__TEST_
An evaluation test of the Source Assessment Sampling System (SASS)
was conducted on July 21, 1976.
The test was conducted on a KVB laboratory boiler firing Pittsburgh
No. 8 coal. The SASS train and pulverized coal were obtained from Aerotherm.
The train was completely disassembled and cleaned according' to IERL-RTP SASS
procedures (Report EPA 600/2-76-160a, June 1976).
XAD-2 organic absorbent was obtained from Arthur D. Little and loaded
into two canisters obtained from TRW. The canisters each held 150 g of XAD-2.
A broken weld on the 1 urn cyclone had to be rewelded by KVB.
Also many of the fittings on the train had been previously overtightened
and caused difficulty during assembly 'and filter changes during the
test. Most of-the mechanical problems occurred with the cyclone
assembly. The remainder of the train functioned satisfactorily.
Samples were taken in a 0.28 m (11 inch) diameter stack above the
boiler. A velocity traverse indicated uniform flow to within +; 10%
of the average velocity of 12 rn/s (40 ft/sec), A 15.87 mm
(5/8 inch) probe nozzle was used. The sampling rate was set for 4
actual CFM (.1133 am3/min) at 478 °K (400 °F) to obtain the cali-
brated cut points on the 3 cyclones. Nominal cut points (DSQ)
are 12, 3 and 1 urn at this flow. EPA-PMB* (Bill Kuykendahl) had
indicated that the cyclones were to be redesigned for 4 SCFM (.1133
sm /min) so that 30 m3 could be collected in the 4.4 hour sampling
period. However, as the train had not been run at the higher flow
rate/ nor had the cyclones been calibrated at that flow, it was de-
cided to operate at the original design rate for a period of 7.5 hours,
to collect 30 m3 (1060 ft3).
*EPA - Process Measurements Branch
530
-------
The sampling run required 11.75 hours elapsed time for 7.53
hours of actual sampling. Dryerite was changed 5 times and the filter
was changed twice (1-2 hour required per change). Filter change
required removal of the complete eyelone-filter assembly because of
"frozen" fittings. During the second change, one filter holder fitting
galled and silastic sealent was required to seal the fitting.
The objective established for train operation was to maintain
a 4 ACFM (.1133 am /min) sample rate at the cyclones within £ 10% and
to maintain isokinetic sampling within HK 10%. The sampling rate
varied from 3.62 to 4.58 ACFM (.102-. 130 am /min) and the percentage
of isokinetic flow varied froa 82% during initial start-up to a high
of 106%. For the majority of the sampling time, the sampling rate
was within +_ 5% of isokinetic conditions. The sample probe was
traversed to 3 points in the stack. The total sample collected was
33.4 m (1180 ft ) registered on the dry gas meter or 30.0 sm
(1060 SCF).
A total of 1558 kg'(3427 Ib) of coal was burned in 16.7 hours
of boiler firing. Following the test, ashes cleaned from the boiler
were:
kg_ Ib %
Furnace tube 51.4 113 42.64
Firetubes 25.9 57 21.51
Stack surfaces 1.4 3 1.13
Baghouse 41.8 92 34.72
120.5 265
Data from Aerotherm indicate ash content by 2 analyses of 7.53 and 7.84%.
Ash yield for the amount of coal burned should by 117-122 kg (258-268 Ib)
Collected ash was within this range.
531
-------
A total of 1125 kg (2475 Ib) of coal was burned during the
11.75 hour period from the start of sampling until sampling was
terminated. For the 7.53 hr of actual sampling train on time the coal
burned is estimated to be 721 kg {1586 Ib). At an ash content of
7.5-7.8% and 35% of the ash transmitted out of the boiler to the
baghouse, the expected particulates isokinetic catch in the train is
61.3-63.8 g. This is based on a duct to nozzle area ratio of 310/1.
The actual catch was:
grams
Probe solids .0939
10 urn cyclone 38.5477
3 urn cyclone 23.7844
' 1 um cyclone 11.2979
Filters (3) 3.3463
77.0702
This catch is 20% greater than expected on the basis of coal burned.
The collected solid particulate concentration was 2.6 g/DSCM (1.12 gr/DSCF)
or 950 ng/J (2.23 lb/10 Btu). The operating results are summarized in
Table G-l.
Samples from the train and boiler ashes were recovered according
to IEKL-TRP procedures with assistance by a TRW representative.
Samples were split into two equal parts with the exception of
probe, cyclone and filter washes. The two sample batches and blanks
were delivered to TRW, Redondo Beach, CA, and to Calspan, Buffalo,
New York for analysis.
Conclusions from the test are:
1. The train functioned properly throughout the test with respect to
sample acquisition capability.
2. Mechanical problems with the cyclone assembly are attributed to the
type of connecting fittings used. The Swagelok fittings are not
well suited for repeated use since deformation of mating surfaces
(rendering separation difficult) is not easily avoided when a leak-free
532
-------
TABLE G-l. KOT BOILER TEST RESULT SUMMARY
Total
Boiler
Operation
Period
SASS
Train
Sampling
Period
Operating time, min
Boiler firing rate,
GJ/h UO6 Btu/h)
Coal burned, kg (Ib5
Ash collected, kg (Ito)
Furnace tube
Firetubes
Stack surface
Baghouse
Total
1002
2.98 (2.8)
1558 (34273
51.4 (113)
25.9 (57)
1.4 (3)
41.8 (92)
120.5 (265)
452
3.05 (2.9)
721 (1586)
23.6 (52)
11.8 (26)
.5 (1)
19.5 (43)
55.4 (122)
Stack conditions (average)
Velocity m/s (ft/s), oiam * 0.28 m
Flow rate sm /min (SCFM), wet
Gas temperature,
Excess oxygen, %
Moisture, %
Total gas Volume,
K (°
dry
m3
(ft3)
12.7
21.5
629
5.9
5.0
9232
(41.7)
(760)
(673)
(326,028)
(ft ) , dry
m^ (ft ) , dry
SASS train conditions
Actual cyclone flow rate
am3/s (ACFM) , wet
Total meter volume, m^
Total standard volume, m
Oven temperature, K (°F)
XAD-2 module temperature, K (6F)
Isokinetic rate, %
Particulate collected, g
Particulate loading, g/DSCM (gr/DSCF)
• Emission factor, ng/J (Ib/MMBtu) ,
.1133 (4.0) +. 10%
33.4 (1180)
30.0 (1060)
478+2 (400+5)
328+_2 (130+_S)
100,6
77.07
2.6 (1.12)
957 (2.2.3)
533
-------
joint is desired. The threaded parts also have a tendency to
gall at elevated temperatures when no lubricants are used.
Various possible lubricants will be investigated and Aerotherm
plans modifications to improve the assembly and sealing,
3. Ice consumption was excessive, 122 kg (270 Ib) were used.
Insulating the ice bath from surrounding air may help to
maximize its cooling effectiveness.
4. No condensation-occurred in the XAD-2 module operated at
328 K (130 °P). This temperature is above the due point
for coal fuel and IEKL-PMB is considering a reduced temperature.
The XAD-2 module satisfactorily maintained the adsorbent
. temperature within 3 °K (5 °F) of the desired temperature.
5. Boiler ash recovered was close to 100% of expected ash.
SASS train particulate catch was 20% higher than expected.
These results should provide a good basis for mass' balance
of the trace elements.
6. Pluggage of the sampling filter necessitated renewal of the
filter element two times during the test. Particulate grain _ ' '
loadings were similar to those encountered upstream of particulate
removal devices at conventional pulverized coal fired
boilers. To minimize downtime for filter changes, a large filter
design should be pursued to allow a 4 to 5 hour run period per filter,
As a result of the relatively successful test, fabrication of a
new train for KVB field was performed. All modifications possible for
improved operation were incorporated. Cyclone design flow remained at
0.113 am /rain (4 ACFM).
Costs for SASS train support and spare equipment were significantly
higher than expected. One important factor is the XAD-2. Original costs
were estimated on the basis of Tenax and with the assumption that Tenax
could be recycled. Both XAD-2 and Tenax can be recycled if analysis is
only done for organics. However, post-use cleaning only provides for
organic removal. Inorganics may build up to unacceptable background levels
and prevent reuse.
534
-------
SECTION G-3.0
SASS TESTS ON KVB BOILER, ASH ANALYSES
Sauries of the coal and ashes collected in the SASS at KVB were sub-
mitted to Aecu-Labs (A-L) and Commercial Testing and Engineering (CTE) for
standard analysis. The results for the coal are presented in Table G-2.
Sample analyses provided to KVB by Aerotherm are also included. These analyses
were for the coal prior to shipment to KVB, Two analyses were performed by
A-L and CTE on a "total composite" sample of all coal burned during the entire
KVB boiler run. Also, two analyses were run for a composite sample collected
for the coal only during the period of time when the SASS train was actually
collecting samples. The composite samples were compiled by extracting equal
amounts of coal from 26 sample containers accumulated during the entire boiler
operating period.
Except for moisture content, the three analyses performed by CTE are
quite consistent indicating little variation in coal properties. The varia-
tion between laboratories on a given sample appears to be greater than the
variation between samples,
A primary purpose in obtaining these analyses was to determine ash
content for comparison with total ash collected in the boiler. The average
of as received ash analysis for all three samples is 7.66% compared with 7.63%
for the total composite sample and 7.68% for the SASS train run composite
sample. Analyses were also performed on the collected boiler ashes. Table
G-3 indicates the amount of each ash type recovered, carbon content, moisture
and amount recovered on a carbon-free, dry basis. Carbon content in the
firetube ash was the highest (26%). The total amount of carbon in all ash
samples is about 12 kg (26 Ib3. A total of 1554 kb (3427 Ib) of coal was
burned. At 76% carbon in the coal (1181 kg) the carbon combustion efficiency
was 98.98%, indicating that the boiler was properly operating. At the average
ash content for the coal (7.63%), a total of 119 kg (262 Ib) should have been
recovered. Table G-3 indicates 108.1 kg (238 Ib) of carbon and moisture-free
ash were actually recovered, or 91% of the expected value.
535
-------
TABLE G-2.
PITTSBURGH #8 COAL ANALYSES
Sample Number
Proximate (% weight)
Moisture
Volatile
Fixed carbon
Ash
Sulfur
J/g
m (Btu/lb>
Ul
cr>
Ultimate {% weight)
Moisture
Carbon ' •
Hydrogen
Nitrogen
Sulfur
Chlorine
Ash
Oxygen (diff)
From Aerotherm
PTL
AR
1.19
37.00
53.97
7.84
2.56
31814
13678
-
-
-
-
-
-
_
""
Dry
-
37.45
54.62
7.93
2.59
32197
13843
-
77.23
5.15
1.23
2.59
-
7.93
5.87
CTE
AR
1.92
36.73
53.82
7.53
2.58
31972
13746
1.92
76.33
5.07
1.17
2.58
0.02
7.53
5.38
Dry
-
37.45
54.87
7.68
2.63
32597
14015 •
-
77.82
5.17
1.19
2.63
0.02
7.68
5.49
Total Test Composite Sample
' CTE
AR
1.66
37,65
53.17
7.52
2.67
31902
13716
1.66
76.15
5.11
1.37
2;67
0.03
7.52
5.49
BSL
-
38.29
54.06
7.65
2.72
32442
13948
4
_
77.44
5.20
1.39
2.72
0.03
7.65
5.57
Accu-Labs
AR
0.96
36.80
54.52
7.73
2.75
32058
13783
0.96
75.92
5.09
1.32
2.75
-
7.73
6.23
SEX.
-
37.15
55.05
7.80
2.78
32369
13917
-
76.65
5.14
1,33
2.78
-
7.80
6.29
Composite Sample During SASS Run
CTE
AR
1.50
37.89
53.15
7.46
2.69
31827
13684
1.5
76.28
5.19
1.39
2.69
0.04
7.46
5.45
Dry
-
38.47
53.96
7.57
2.73
32311
13892
-
77.44
5.27
1.41
2.73
0.04
7.57
5.54
Accu-Labs
AR .
0.89
37.08
54.14
7.89
2.81
31841
13690
76.05
5.10
1.30
2.81
_
7.89
5.96
Dry
_
37.41
54.63
7.96
2.84
32128
13813
76.73
5.14
1.32
2.84
-
7.96
6.02
-------
TABLE G-3. ANALYSES OF BOILER ASHES
Sample
Furnace slag chunks
Furnace slag powder
Fire tube ash
Lower stack ash
Horz. duct ash
Baghouse ash
Totals
Amount
Recovered
kg(lb) Sample
(%) No. Lab* AR Dry % Moisture
27.2(60) None CTE
(22.6%) 199/200 A-L 0.18 0.18 0403
24.0(53) 175 CTE 2.91 2.92 0.37
'(19.9%) 174 A-L 2.68 2.69 0.22
25.8(57) 177 CTE 26.60 27.22 2.29
(21.4%) 176 A-L 26.20 26.60 1.47
1.4(3) All used for T.E. analysis
(1.1%)
.5(1} All used for T.E. analysis
(.4%)
41.8(92) 173 CTE 9.62 9.68 0.63
(34.6%) 172 A-L 9.87 9.92 0.48
120.7(266)
Amount
Collected
Carbon Free
and Dry
kg(lb)
27.2(59.9)
23.3(51.3)
23.3(51.5)
18.4(40.5)
18.7(41.2)
1.2(2.7) est.
.4(.9) est.
37.5(82.6)
37.4(82.5)
108.1(238.3)
CTE - Commercial Testing & Engineering, Chicago, IL
A-L - Accu-Labs, Denver, CO
-------
SECTION G-4.0
KVB _BOILER SASS TEST SAMPLED ANALYSIS, INORGANICS
Table G-4 presents results for the major elements barium, calcium, and
titanium. There was a substantial difference in concentration of barium
between the two coal samples (58 \ig/g in the composite sample of total coal
burned versus 81 yg/g in the coal sample collected only during the SASS run).
For calcium, the SASS run coal sample was 40% higher than the total sample.
Titanium was within 3% for both coal samples.
The total coal sample and SASS run coal sample were composite samples
obtained from 26 separate coal samples collected during the run. The majority
of the elements appeared to be consistent between the two samples. Elements
that showed a fairly large difference include: antimony, arsenic, barium,
cadmium, and fluoride. The mercury content in both samples was < 0.03 yg/g.
Calspan had the SASS run coal sample analyzed by CTE using a .gold amalgamation-
AA method and a value of 0.03 yg/g was obtained, exactly equal to the Calspan
AA detection limit.
Boiler ash collection appeared very good. Total ash barium content was
93% of the total"coal sample barium content but only 66% of the SASS run coal
sample content. Comparison of the boiler ash samples with the total coal
sample rather than the SASS run coal is more appropriate since the ash was
generated by the total amount of coal burned. For calcium, the ash content
was 138% of total coal calcium and 108% of the SASS run coal content. For
titanium, the ash content was 95% of the total coal content and 92% of the
SASS run coal sample.
SASS train collections of barium, calcium and titanium were also very
good. The majority of these three elements was collected in the solids portion
of the train. The specific concentrations (yg/g) in the cyclone solids are
comparable to the specific concentrations in the boiler baghouse ash. Total
stack emissions of the three major elements were estimated by three methods:
538
-------
TABLE G-4. KVB BOILER SASS TRAIN TEST MASS BALANCE OF MAJOR ELEMENTS
Barium
Quantity During Relative
Saaml« Train Run Aaount
Fuel
153
154
^^*
Total Coal
SASS Run Coal
719.3 kg
719.3 kg
58
81
ug/g
ug/g
Total
41,7 g
58.3 g
Calciun
Relative
Aseunt
1100
1400
Ug/g
ug/g
Total
791
1007
g
g
Titaniua
Relative
Ajaount
840 ug/g
870 Ug/9
Total
604 g
626 g
Boiler As has
190
167
169
171
179
165
Slag Chunks
Slag Powder
Firatube
Stack
Duct
Baghous*
Total Ash
» of Total/SASS Coal
Train Saoples
Comb. P,N,C,? Washes
182
184
186
188
151
139
108
109
110
112
10 U> Solids
3 UB Solids
1 u« Solids
Filters
XA02 Resin
XAD2 Hast)
Inping. »1(1!
Imping. il<2)
Imping. *2
Inping. *3
Total Train Catch
U9/«>3
% as Vapor
12.6 kg
11.1 kg
12.0 kg
.6 kg
.2 kg
19.5 kg
56.0 kg
365 ml
38.5758 g
23.7092 g
11.3035 g
3.3463 g
151.4 g
274 ml
937 al
• 9SO ml
1295 ml
SS8 al
>1000
720
630
310
330
530
.64
900
600
420
480
4
.13
.10
,076
,044
.080
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/mi
ug/g
ug/g
ug/g
ug/g
wg/g
IIQ/O
\tf3/W&!
yct/Bili
wg/ml
ug/al
12.6*g
7.99 g
7.56 g
.19 g
.07 g
10.34 g
3S.75*g
93/66
234 ug
34718 Ug
14225 Ug
4747 Ug
1606 ug
606 ug
36 yg
94 ug
75 ug
57 ug
45 ug
56443 Ug
1880
1.6
3000
17000
5600
8200
3500
23000
ug/g
ug/g
ug/g
wg/g
ug/g
Ug/g
378
189
67
5
1
449
1089
g
g
g
g
g
g
g
9700 ug/g
9400 Ug/g
8200 ug/g
8200 ug/g
1600 ug/g
12500 ug/g
138/108
14.6
2100
ug/ml
ug/g
24000 ug/g
17000 ug/g
2600O ug/g
98 wg/g
.a
ug/»a
5.3
8J.O
569
192
87
IS
.2
•9
•g
•9
•g
»9
ag
ng
<.Q2 ug/ml 0
.04
.12
.08
ug/ml
ug/ml
ug/«i
.4
.2
.04
1679
55929
0.9
tnq
n*j
3.5 ug/*l
ilooo ug/g
13500 ug/g
14000 ug/g
9200 ug/g
<50 ug/g
122 g
104 g
98 g
5 g
.3 g
244 g
573 g
95/92
1.3 ag
424 mg
320 Big
158 Bg
31 ag
0
<2 yg/ml 0
<2 ug/»l 0
<2 uf/a
<2 U9/"
1 0
1 0
rog <2 ug/al 0
-0
934 ag
31112
0
Total Stack Enu.ssi.an:
Area Ratio - 309 (Duct/Hozzla)
VoluM Ratio - 308 0232/30 »3)
Solids Ratio - 2S3 (19500/77 g)
% Mass Balance A,V, S Ratio -
* Has* Balance A,v, S Ratio -
Total Coal
SASS Coal
17.44 g
17.38 g
14.28 g
liO/109/102
79/79/73
519
517
424
g
g
g
147/146/135
1
xs/u.
4/1C
)6
289 g
283 g
236 g
102/101/94
99/ 98 /90
539
-------
1. Area Ratio - Duct Area/SASS Nozzle Area = 309
2. Volume Ratio = Total Stack Volume/SASS Sample Volume = 308
3. Solids Ratio = Baghouse Ash Weight/SASS Solids Weight =253
These ratios are based on:
Duct Area at Sample Point = 0.0613 m
2
SASS Nozzle Area = 0.000198 m
Total Stack Volume = 9232 SCM , dry
SASS Sample Volume = 30.02 SCM, dry
Baghouse Ash Weight = 19,500 g
SASS Solids Weight = 76.9 g
Mass balances based on each ratio and for the two coal samples are shown in
the table. The balance was made by subtracting baghouse ash content from
total ash content, adding the stack emission obtained by train collection
and dividing by the coal content. The various balance values vary from 73
to 146%. The mass balance on titanium was from 90 to 105%. These are con-
sidered to be excellent results and /indicate that the basic sample collection
procedure was properly conducted.
Table G-5 presents preliminary results for four of the more volatile
elements. Sach element is discussed below.
Arsenic
The total arsenic collected in the boiler ashes is 94% of the total
coal arsenic (141% of SASS run coal content). This suggests that the arsenic
did not behave as a volatile element. The baghouse ash contained 38% of the
arsenic collected in the ashes and the baghouse total ash was 35% of the total
boiler ash. Arsenic content of the total coal sample was 1.5 yg/g or 19.7
Ug/g if considered to be present only in the coal ash at an ash content of
7.63%. Boiler ash concentrations varied from 12 to 26 Ug/g of arsenic (see
Appendix A) or an average of 18.1 Pg/g. It would appear that all arsenic
remained in the boiler ash. Essentially all of the arsenic collected in the
SASS train was present in the solids section, consistent with the above. How-
ever, the train solids concentrations were higher (40-100 Pg/g) than in the
ashes and the resultant total mass balance varied from 176 to 303%. Arsenic
collected by the train, converted to total emission by the 3 ratios, exceeds
the total coal arsenic content.
540
-------
TABLE G-5. KVB BOILER SASS TRAIN TEST MASS BALANCE OF VOLATILE TRACE ELEMENTS
Quantity During
Saagle
Fuel
IS 3 Total Coal
154 SASS Run Coal
Boiler Ashes
180 Slag Chunks
167 Slag Powder
169 firstuba
171 Stack
179 Duct
165 Saghousa
Total Ash
% of Total/SASS Coal
Train Saa^les
Con*. P,N,C,F Hashes
132 10 U a Solids
134 3 "a Solids
186 1 UB Solids
188 Filters
1S1 XAD2 Resin
139 XA02 Huh
108 Imping. »1 (1)
109 Imping, fl (21
110 Imping. 12
112 lisping. *3
Total Train Catch
.ug/m3
% as vapor
Total Stack Emiiiions
Area Ratio " 309
Volume Ratio - 308
Solids Ratio - 253
* Mass Balance, A,v,S Ratio - Total Coal
* Mass Balance, A,v,s Ratio - SASS Coal
train Run
719.3 kg
719.3 kf
12.6 kg
11.1 kg
12.0 kg
.6 k»
.2 kf
19.5 kg
56.0 kg
365 ml
38.5758 g
23.7092 g
11.3035 f
3.3463 f
151.4 f
274 ml
937 ml
980 ml
1295 ml
558 ml
Arsenic
1079 tug
719 Bf
151 ag
144 Bf
312 ag
IS ag
3 Bf
390 mg
1015 mg
94/141
22 Uf
1544 Ug
2371 Ug
348 Uf
251 Ug
<1S1 Uf
<11 Uf
<4 ug
«4 Ug
-------
Antimony
Only 0.1 to 0.2% of the antimony was retained in the boiler ashes.
This suggests that almost all antimony was vaporized and train collection
would be expected to occur in the impinger sections. Such was not the case.
Sixty percent of the antimony was collected' in the train solids section.
Total antimony mass balance was 79 to 97% based on the SASS coal sample, in-
dicating excellent collection of antimony. The high unexpected fraction found
in the solid section may indicate that as the sample is cooled from 625 K
(665°F) stack temperature to 478 K (400°F) cyclone temperature, condensation
of antimony may occur. However, if that were the case, the antimony would
be enriched on the small particles and that did not occur as indicated below:
Antimony
yg/g mg
10 ym solids 150 5786
3 ym solids 200 4740
1 jam solids 180 2034
Filter 90 301
There was no significant increase in antimony concentration for smaller particle
size.
Selenium
Selenium concentrations were below detection limits for both coal
samples and all SASS train samples. All boiler ash samples were above de-
tection limits. No conclusions can therefore be drawn regarding selenium
collection.
Mercury
Coal mercury content was relatively low (0.03 pg/g3 compared with
typical coal concentrations (about 0.15 pg/g). Only 18% of the mercury was
retained in the boiler ashes. Some mercury was collected in the 10 micron
cyclone and on the filter but 77% was collected in the XAD2 wash and impingers.
The total mass balance was about 60% with the largest amount collected in
Impinger No. 2. If all train samples for which mercury was below detection,
were taken at the detection limit values, total mercury collected would still
be only 89% of coal mercury.
542
-------
Blank Values
Comparison of test results for blanks and samples for the XAD2 resin
and the filter indicates that blank trace element contents were in several
instances higher than in the samples.
Conclusions
Based on major trace element mass balances, the KVB SA.SS test appears
to have been a satisfactory test run. For volatile elements of main interest,
arsenic was collected in excess of the expected amount, antimony collection
was excellent on a mass balance basis, selenium was not present in sufficient
quantities to evaluate collection, and only about 60% of the mercury was
recovered by the train.
543
-------
SECTION G-5.0
KVB BOILER TEST PARTICLE SIZE ANALYSIS
The SASS train cyclones were designed for nominal cut sizes of 10,
3, and 1 microns. A particle sizing analysis was obtained by KVB from Calspan
Corporation. The sizing was performed by a Coulter Counter xi?hich optically
analyzes particles suspended in a liquid. The result is a volume-based
diameter while the actual desired result should be based on aerodynamic
diameter. Sizing was done for the 1, 3, and 10 micron cyclone particulate
collected. Sizing of the filter collection was requested but no results were
obtained since the Coulter technique is valid only for particles over 1 micron.
Figures G-l, G-2, and G-3 present the results for the 10, 3, and 1
micron cyclone respectively. The 50% cut point for the 10 micron cyclone
(Fig. G-l) was 10.7 microns and 54% of the particulate was over 10 microns.
Since the basic design is based on a 50% collection at 10 microns, this is
an extremely accurate result. Ninety percent of the particulate was between
3.7 and 23 microns.
For the 3 micron cyclone, particles theoretically should be from
3 to 10 microns. Results of Figure G-2 show 73% of the particulate -between
3 and 10 microns. The 50% cut point was 6.7 microns and 90% of the particles
were between 2.8 and 17 microns.
For the 1 micron cyclone, particles should theoretically be between
1 and 3 microns. The results for the 1 micron cyclone are shown in.Figure
G-3. The 50% cut point was 2.7 microns and 63% was between 1 and 3 mircons.
Ninety percent was between 1.3 and 5.7 microns.
These results were obtained at a cost less than $100. They appear to
substantiate the design sizing of the cyclones. However, the design is based
on an aerodynamic diameter while the Coulter Counter provides a volume based
diameter independent of particulate density.
544
-------
Figure G-l.
CCHM.TII ttiCtlCNKI WC.
®< COULTER COUNTER* Model UTA PARTICLE SIZE ANALYSIS ,"„";, *'»»
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-------
Figure G-2.
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@- COULTER COUNTER* Model T*TA PARTICLE SIZE ANALYSIS ,"„,?,- *.»».
* • Kt*i.l*N, »*.*. 1J6SB
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Calspan
QPIlAlOB
iguiruiMr
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KVB #184, 3-10 ym cyclone, KVB Boiler Test
D50 = 6*^ ^m (volume) 73* between 3-10 ym
40% between 2.7-17 ym
-^- £• (#•)'•*-—'" £•
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-------
Figure G-3.
„ couuii iiiciiOMo INC
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* HULIAN, FLA. MH
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D,. = 2.7 pm (volume) 63% between 1-3 ym
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MICRON DIAMETER, Log Scale
-------
SECTION G-6.0
ORGANICS
Analysis of polycyclic organic matter (POM) and polychlorinated
biphenyls (PCB) in samples collected during the initial SASS train test on
the KVB boiler was performed. The results are presented in Table G-6.
Total POM in the coal burned during the sampling time was 94 grains. The
total ash content was 272 mg of total POM of which the majority, 264 mg,
was in the firetube ash and 3.5 mg in the baghouse ash.
Total POM collected in the SASS train was 6.6 mg. Of this, 83% or
5.5 mg was collected in the XAD-2 module wash and 15% or 1.0 mg was collected
in the XAD-2 resin. The remainder was present in the 1 ym cyclone solids
(0.097 mg} and in the 3 ym cyclone solids (0.018 mg). Based on 30 m of
stack gas collected by the train, the total POM emission was 220 yg/m or,
on a heat input basis, 0.081 ng/J. Total POM in samples from nozzle, probe,
cyclone, and filter washes, the filter itself, and from the irnpingers were
all below the detectable limit. The potential total undetected amount is
1.1 mg of total POM.
The gas chromatograms for POM did not show any distinct peaks that
could be attributed to any of the eight specific POM compounds required to
be identified. Compound separation was substantial based on a review of
Calspan calibration runs. However there are evidently so many compounds
present in the samples where total POM amount is high that identification
of specific POM by GC analysis alone is not adequate. As a result of this
test, samples with high POM content were subjected on a selected basis to
analysis by GC/MS for compound identification.
Calspan results for total PCB content of all samples were below the
limit of detectability in all samples.
548
-------
TABLE G-6. POM AND PCB EMISSIONS PROM KVB BOILER TEST OF SASS TRAIN
Sample
No.
153
154
180
167
169
171
179
165
Comb.
182
184
186
188
151
139
108,109
110
112
Sample Type
FUEL
Total Coal
SASS Coal
BOILER ASHES
Slag Chunks
SUg Powder
Firetube Ash
Stack Ash
Duct Ash
Baghouse Ash
Total Ash
TRAIN SAMPLES
* Solid Section Washes
10 pra Solids
3 pm Solids
1 um Solids
Filter
** XAD-2 Resin
* Org. Module Wash
* Impinger ttl
* Impinger tt2
* Impinger #3
Total Train Catch
Quantity During
Train Run
71i,3 kg
719.3 kg
12.6 kg
11.1 kg
12.0 kg
0.6 kg
0.2 kg
19.5 kg
56.0 kg
365 ml
38.5758 g
23.7092 g
11.3035 g
3.3463 g
151.4 g
274 ml
1917 ail
1295 ml
558 ml
Total POM
Concentration
229 yg/g
130 pg/g
< 0.2 \ig/g
0.17 pg/g
22.0 pg/g
4.2 pg/g
< 0.2 yg/g
0.18 yg/g
< 1 pg/ml
< 0.2 pg/g
0.74 pg/g
8.6 pg/g
< i pg/g
6.7 pg/g
20,0 yg/ml
< 0.2 pg/ml
< 0.2 pg/ml
< 0.2 pg/ml
Amount
165 g
94 g
1.9 mg
264.0 Dig
2.5 mg
3.5 mg
271.9 mg
—
18 yg
97 pg
1014 pg
5480 pg
6600 yg
Total PCB
Concentration
< 10 pg/g
< 10 pg/g
< 10 yg/g
< 10 pg/g
< 10 yg/g
< 10 pg/g
< 10 yg/g
< 10 yg/g
< 10 pg/ml
< 10 yg/g
< 10 pg/g
< 10 yg/g
< 10 pg/g
< 10 pg/g
< 1 yg/ml
< 1 pg/ml
< 1 yg/ml
< 1 yg/ml
N.D.
Stack Concentration
% as Vapor
Total Stack Emission by Volume Ratio of 327
220 yg/m
98
2158 mg
*Blank values for all liquids: POM < 0.2 yg/ml, PCB < 1 pg/ml.
••Blank values for XAD-2 reains POM < 0.2 Pf/g, PCB < 10 yg/g.
N.D.
-------
TECHNICAL REPORT DATA
(Please read Instrucrions on the reverse before completing)
1. REPORT NO, 2.
EPA-600/7-79-G15a
4. TITLE AND SUBTITLE
Application of Combustion Modifications to Industrial
Combustion Equipment
7. AUTHOfUSJ
S.C. Hunter, W, A. Carter, M.W. McElroy,
S.S. Cherry, and H. J.Buening
9. PERFORMING QROANIZATiCN NAME AND ADDRESS
KVB, Inc.
17332 Irvine Boulevard
Tustin, California 92680
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESSION- NO.
5, REPORT DATE
January 1979
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
KVB 6002-743
10. PROGRAM ELEMENT NO.
E HE 62 4 A
11. CONTRACT/GRANT NO.
68-02-2144
13, TYPE OF REPORT AND PERIOD
Final; 1/76 - 5/77
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES T£RL-RTP project officer is Robert E. Hall, Mail Drop 65
541-2477.
COVERED
, 919/
16, ABSTRACT
The report gives results of a field test program to evaluate the effect of
minor combustion modifications on pollutant emissions from a variety of industrial
combustion equipment types."Tested were 22 units , Including refinery process hea-
ters; clay and cement kilns; steel and aluminum furnaces; boilers burning black li-
quor, wood bark, and CO gas; internal combustion engines; and gas-turbine combinet
cycles. Process variables, fuel types, excess air reduction, burner adjustments,
and staged combustion were evaluated primarily for their effect on NOx emissions.
Emissions of NOx, SOx, CO, and HC were measured on all units. Emissions of
particulate mass and size, trace species, and organics were measured on selected
units. Baseline (as-found) NOx emissions from the test units varied from 35 to 1320
ng/J (52 to 2250 ppm corrected to 3% O2, dry basis). With combustion modifications
NOx emissions from some units were reduced by up to 69%; however, for certain
kinds of equipment, NOx reductions were low or-insignificant. The main conclusion
was that combustion modifications can be applied to many devices without process
disruption; however, process limitations on certain types of equipment restrict the
degree of NOx reduction that can be achieved.
17.
a.
Air Pollution
Combustion
Boilers
Furnaces
Nitrogen Oxides
Fossil Fuels
Particle Size
18. DISTRIBUTION STATE
Unlimited
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Chemical Analysis
Inorganic Compound
Organic Compound
Gas Turbine Engine
Reciprocating En-
gine
Industrial Process
WENT
b.lDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Stationary Sources
Combustion Modification
Particulate
Excess Air
Staged Combustion
19. SECURITY CLASS (This Report/
Unclassified
20. SECURITY CLASS (This page)
Unclassified
c. COSATI Field/Group
13B 07D
2 IB
ISA 07C
2 IE
07B
2 ID 21G
14B 13H
21. NO. OF PAGES
560
22. PRICE
EPA Form 2220-1 (9-73}
550
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