EPA-600/2-76-096
April 1976
Environmental Protection Technology Series
;CTION m
STACK SAMPLING SYSTEMS FOR
EMISSIONS IN FLUE GASES
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are.
1. Environmental Health EffectsTiesearch
2 Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This docBnfent is available to the public through the National Technical Informa-
tion Service. Springfield. Virginia 22161.
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COLLECTION EFFICIENCIES OF STACK SAMPLING SYSTEMS FOR
VANADIUM EMISSIONS IN FLUE GASES
by
H. L. Goldstein and C. W. Siegmund
Exxon Research and Engineering Company
Products Research Division
P. 0. Box 51
Linden, New Jersey 07036
Contract No. 68-02-1748
Project Officer
James L. Cheney
Stationary Source Emission Measurement Branch
Environmental Science Research Laboratory
Research Triangle Park, North Carolina 27711
U. S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL SCIENCE RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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- ii -
DISCLAIMER
This report has been reviewed by the Environmental Science
Research Laboratory, U. S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U. S. Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
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CONTENTS
LIST OF FIGURES
LIST OF TABLES vii
ACKNOWLEDGEMENTS ix
1. INTRODUCTION 1
2. SUMMARY 4
3. CONCLUSIONS 9
4. RECOMMENDATIONS 10
5. BACKGROUND 11
5.1 Vanadium in the Environment 11
5.1.1 Ambient Air Measurements 11
5.1.2 Toxicity of Vanadium Compounds 13
5.1.3 Natural Occurrence of Vanadium in Fuels 14
5.2 Nature of Vanadium in Emissions 16
5.2.1 Mechanism of Particulate Formation 16
6. EXPERIMENTAL PROGRAM 21
6.1 Research Plan 21
6.2 Combustion Test Facility 23
6.2.1 50 hp Cleaver Brooks Package Boiler 23
6.3 Program Design 27
6.4 Boiler Tube Deposits 32
6.5 Stack Sampling Systems 33
6.5.1 Method 5 EPA 33
6.5.2 ER&E Collection System 35
6.6 Particulate Sampling 37
6.7 Particulate Isolation Method - General Procedure 46
6.8 Determination of Vanadium in Particulate 46
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7. RESULTS AND DISCUSSIONS ...................................... 52
7.1 Basis for Comparing Vanadium Recovery ................... 52
7.2 Vanadium Material Balance Around the
Cleaver Brooks Boiler ................................... 52
7.2.1 Total Vanadium Recovery Using
All-Venezuelan Resids ............................ 52
7.2.2 Erratic Vanadium Recovery
Using Light Arab Residuum ........................ 56
7.2.3 Statistical Analysis to Compare
Vanadium Recovery ................................ 59
7.2.4 Vanadium-Bearing Particulate Inventory ........... 61
7.2.5 Size Distribution of Vanadium-Bearing
Particulates ..................................... 67
7 . 3 Sampling System Collection Efficiency ................... 70
7 . 4 Vanadium Input - Fuel Analysis .......................... 71
7.5 Vanadium Recovery in the Boiler ......................... 75
7.5.1 Preliminary Tests - Evaluation of
Boiler Pass Tube Inserts ......................... 75
7.5.2 Factorial Program Results - Vanadium
Recovery at High Firing Rate ..................... 79
7.5.3 Vanadium Recovery Made at Low Firing Rate ........ 81
7.5.4 Further Consideration of
Total Vanadium Recovery .......................... 83
7.6 Recovery of Vanadium in the Stack - Summation ........... 86
7.7 The Problem of Sulfate Formation
in Water Impingers ...................................... 90
7.7.1 Sulfuric Acid Formation .......................... 90
7.7.2 The Nature of Artificial Particulate ............. 91
7.8 Determination of Oxidation State
of Vanadium Particulate in Flue Gas ..................... 94
8 . REFERENCES [[[ 96
APPENDIX 1 STATE OF THE ART REVIEW
VANADIUM ANALYSIS AND PARTICULATE
SAMPLING METHODOLGY 98
APPENDIX 2 LABORATORY ISOLATION OF PARTICULATE
COLLECTED FROM STACK SAMPLING TRAINS 116
APPENDIX 3 THE DETERMINATION OF VANADIUM IN PARTICULATES 122
APPENDIX 4 OPERATIONAL DATA FROM FACTORIAL PROGRAM 133
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No.
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LIST OF FIGURES
Page
5.1 >10 MICRON PARTICULATE EMISSIONS
(CENOSPHERES) 18
5.2 INTERMEDIATE SIZE RANGE (1-10 MICRONS)
PARTICULATE ..... 19
5.3 THE EFFECTS OF TEMPERATURE AND OXYGEN AVAILABILITY
ON EQUILIBRIUM COMPOSITION FOR THE REACTION
2V 0 j—7+ 4VOo + 02 20
2. j ~"
5.4 VAPOUR PRESSURES OF FUEL OIL ASH CONSTITUENTS 20
6-l THE FOUR PASS CONSTRUCTION OF A TYPICAL C-B BOILER 24
6.2 50 HP CLEAVER BROOKS BOILER 25
6.3' ARRANGEMENT OF FLUE GAS MONITORING SYSTEMS 26
6.4 LONGER RESIDENCE TIME FAVORS
BURNOUT OF CENOSPHERES 29
6.5 FOUR PASSES OF CLEAVER BROOKS BOILER 34
6.6 EPA METHOD 5 SAMPLING TRAIN 35
6. 7 ER&E STACK SAMPLING TRAIN 36
6.8 OVERALL VIEW OF BOILER, STACK SAMPLING SYSTEMS
AND CONTROL MODULES 38
6-9 ARRANGEMENT FOR SIMULTANEOUS OPERATION OF EPA AND ERE STACK
SAMPLING TRAINS. (POSITION 1) EPA TRAIN LOCATED
ON LEFT HAND SIDE 39
6.10 CLOSE-UP VIEW OF PORT HOLE CONFIGURATION FOR
SIMULTANEOUS SAMPLING 40
6.11 OVEN ASSEMBLY OF ER&E SYSTEM SHOWING ANDERSEN CASCADE
IMPACTOR, IMPINGER SYSTEM AND MAKEUP AIR LINE. GLASS
TUBE UPSTREAM OF IMP ACTOR IS CONNECTED TO PROBE 41
6.12 VOLATILES KNOCKOUT SYSTEM CONNECTED TO ER&E TRAIN
FEATURES A DRY ICE ACETONE COOLED CONDENSER 42
7.1 TOTAL VANADIUM RECOVERED IN BOILER AND STACK -
SHORT RESIDENCE CASE 54
7.2 TOTAL VANADIUM RECOVERED IN BOILER AND STACK -
LONG RESIDENCE CASE 55
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LIST OF FIGURES (CONT'd.)
No.
7.3
7.4
7.5
TOTAL VANADIUM RECOVERED - LIGHT ARAB FUEL
VANADIUM RECOVERY IN BOILER -
SHORT RESIDENCE CASE
VANADIUM RECOVERY IN BOILER -
LONG RESIDENCE CASE
Page
58
80
82
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LIST OF TABLES
No. Page
5.1 CONCENTRATIONS OF V IN AMBIENT AIR 12
5.2 CHARACTERISTICS OF MIDDLE EAST AND
VENEZUELAN CRUDES AND FUEL OILS 14
5.3 CONCENTRATIONS OF VANADIUM IN DOMESTIC COALS 15
6.1 RESIDUAL FUEL OILS USED IN V COLLECTION
EFFICIENCY STUDY 27
6.2 HEAVY FUEL OIL INSPECTIONS 28
6.3 EXPERIMENTAL PROGRAM DESIGN 31
6.4 HEAT EXCHANGE SURFACE IN THE CLEAVER BROOKS 32
6.5 INFLUENCE OF COMBUSTION CONDITIONS ON
BOILER AND STACK TEMPERATURE 33
6.6 STACK VELOCITY PROFILE FROM BOILER 43
6.7 LOW LEVEL SOURCE PROFILE 44
6.8 MASS CONCENTRATION PROFILE IN STACK
IS UNIFORM 45
6-9 EFFECT OF ASHING METHOD ON VANADIUM
ANALYSIS BY ATOMIC ABSORPTION 48
6.10 COMPARISON OF INSTRUMENTAL METHODS
OF VANADIUM ANALYSIS 49
6.11 ELEMENTAL ANALYSIS BY EMISSION SPECTROSCOPY 51
7.1 AVERAGE PARTICIPATE AND VANADIUM INVENTORY
FOR LIGHT ARAB FUEL 60
7.2 ANALYSIS OF VARIANCE - TOTAL VANADIUM
RECOVERY IN BOILER AND STACK 62
7.3 TOTAL VANADIUM RECOVERY AS AFFECTED BY STACK
SAMPLING SYSTEM AND COMBUSTION CHAMBER RESIDENCE TIME 63
7.4 AVERAGE PARTICULATE AND VANADIUM INVENTORY
HIGH ASH ALL VENEZUELAN FUEL OIL (F!> 64
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LIST OF TABLES (Cont'd.)
No. Page
7.5 PARTICULATE COMPOSITION INFLUENCED BY SIZE 65
7. 6 DISTRIBUTION OF V205 IN PARTICULATE ASH 66
7.7 AVERAGE PARTICULATE AND VANADIUM INVENTORY
INTERMEDIATE ASH ALL VENEZUELAN, FUEL OIL (F2) 68
7-8 RELATIVE SIZE DISTRIBUTION OF STACK PARTICULATE 69
7.9 SAMPLING SYSTEM COLLECTION EFFICIENCY 72
7.10 DRUM TO DRUM VARIATION OF VANADIUM ANALYSIS 73
7.11 VARIATION OF SAMPLES WITHIN A DRUM OF
ALL-VEN FUEL OIL 74
7.12 VARIATION OF PARTICULATE DISTRIBUTION
IN BOILER (PRELIMINARY TESTS) 76
7.13 VARIATION OF VANADIUM DISTRIBUTION IN BOILER -
PRELIMINARY TESTS 78
7.14 PARTIAL ELEMENTAL COMPOSITION OF BOILER SOLIDS 78
7.15 PARTICULATE AND VANADIUM INVENTORY IN BOILER 84
(SHORT COMBUSTION CHAMBER RESIDENT TIME -
2 LB./MIN. F. R. )
7.16 PARTICULATE AND VANADIUM INVENTORY IN BOILER
(LONG COMBUSTION CHAMBER RESIDENCE TIME -
0.5 LBS./MIN. F. R. ) 85
7.17 VANADIUM RECOVERY IN THE BOILER 87
7.18 RECOVERY OF VANADIUM IN STACK SAMPLING SYSTEMS 88
7.19 COMPARISON OF PARTICULATE SULFATE/
SULFURIC ACID INVENTORY 92
7.20 ARTIFICIAL PARTICULATE FORMATION IN
WATER IMPINGERS OF METHOD 5 93
7.21 COMPOSITION OF SOLIDS FROM METHOD 5
WATER IMPINGERS 95
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ACKNOWLEDGEMENTS
The authors wish to express their appreciation to Messrs. J. Singleton
and J. DeHoff for performing the laboratory work described in this
report.
We also wish to acknowledge the efforts of the personnel of the
Analytical Division who were responsible for developing the analytical
methodology and carrying out the vanadium analysis,particularly
Drs. R. A. Hofstader, P. R. Gaines and M. C. Grandolfo.
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1. INTRODUCTION
Studies of vanadium concentration in ambient air have
shown a strong link between residual fuel oil combustion and high
vanadium levels. There is also growing evidence which suggests that
the major part of the vanadium emissions from stationary combustion
sources are concentrated in the fine sized particles (1»2). As there
are no direct reading instruments for measuring vanadium in stack
gases, emission factors for this element must be based on conventional
particulate sampling methods, i.e. collecting dust or fumes on filters,
electrostatic precipitators and/or impingers. These methods have
in common several potential drawbacks:
(1) the possibility that fine particles may not be collected
very effectively and therefore pass through the sampling
device.
(2) the possibility that volatile vanadium compounds will be
lost from the sample by continuously drawing flue gas over
the particulate.
The study performed for this contract was to compare experimentally
the effectiveness of the U. S. Environmental Protection Agency's (EPA)
standard Method 5 particulate sampling train and a stack sampling
system developed by Exxon Research and Engineering Company (ER&E)
for collecting vanadium emissions in flue gas from heavy fuel oil
combustion. The ER&E system overcomes some of the major shortcomings
traditionally associated with stack samplers more commonly used. It
permits the determination of size distribution of the particulate down
to about Q.4 ym and it collects finer particulate in several impingers
containing a liquid medium which can operate at stack temperatures. -This
avoids any possibility that S02 will oxidize to sulfate in the impingers
which would create false particulates.
To assess collection efficiency of the two sampling trains
in a real environment under realistic but closely controllable
conditions, an actual boiler was used. The unit consisted of a completely
instrumented 50 hp, four pass package boiler manufactured by Cleaver
Brooks. For particulate sampling, a platform mounted above the boiler
allowed access to two 3" ports which had been drilled at right angles
to each other in the 12" diameter boiler stack. Using this arrangement,
both sampling trains were operated simultaneously during the tests.
The package boiler burns heavy fuel oil under combustion
conditions typical of those in a field installation. The gases moving
through the system are cooled in a realistic manner so particulate burn-out
and condensation from the vapor phase is realistic. Thus, this boiler is
the best equipment of reasonable size for generating particulate
approximating those which will be encountered in the field. A large boiler
would be too cumbersome in terms of fuel requirements and operating
difficulties to carry out such a study under closely controlled conditions.
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In order to establish the effectiveness of the collection
systems, i.e. their ability to inventory all the vanadium particulate
entering the stack, a vanadium material balance was carried out
around the boiler. In essence by knowing the vanadium content of
the fuel which is burned and determining the amount of vanadium deposited
in the boiler, it is possible to establish quantitatively how much of
the vanadium particulate is carried into the stack with the flue gas.
Since the Cleaver Brooks is a four pass boiler, that is, the combustion
products pass the length of the boiler four times before entering the
stack, vanadium deposits in each of the passes must be carefully inventoried.
Ideally, the firetube, which constitutes pass 1, and the 32 heat
exchanger tubes making up the 3 other passes would be completely cleaned
out and the amount of vanadium collected would be measured after each
run. However, cleaning all the tubes after each run would be extremely
time consuming and tedious. To avoid this and at the same time provide
a high degree of accuracy, two methods for measuring the amount of
vanadium deposition in the boiler were originally proposed. The first
involved isokinetically sampling the combustion gases at the end of
the firetube. The second involved collecting fallout in stainless steel
liners placed in selected heat exchanger tubes in the passes. This
latter was selected by the EPA as the most practicable technique.
The amount of vanadium entering the boiler during a given run
was determined by knowing the vanadium content of the fuel and the fuel
firing rate. This was compared with the vanadium output from a run
consisting of: the amount measured in the flue gas leaving the boiler
using the sampling systems mentioned previously plus, the amount of
vanadium collected in the boiler tubes and passages. In order to
measure the latter without going through a long and tedious boiler
clean-out after each run, tube liners were used. These were stainless
steel inserts which were machined to fit snugly inside certain of the
32 heat exchanger tubes in the four passes. At the end of each run,
these liners were removed and the particulates in them were weighed
and analyzed for vanadium. The vanadium collected in each insert
was considered to be typical of the amount collected in the other tubes
in the same pass.
The difference between the vanadium entering the boiler with
the fuel, that accounted for in boiler deposits and that collected
in the sampling systems gave a measure of the inefficiency of the sampling
system and/or inaccuracies in the other measurements involved.
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In order to determine how accurate the sampling systems
would be over a range of vanadium particulate levels in the flue gas
and particle size distributions, runs were made on several fuel oils
over a range of operating conditions. The fuels were chosen on the
basis that they were typical of those in use now and in the future in
the U. S. and that their vanadium contents would span the range which
would normally be encountered in U. S. fuel oils.
The primary variable used to adjust combustion conditions
was residence time in the combustion zone. Previous (company sponsored)
studies by Exxon Research and Engineering Company'-^ had shown that
increasing residence time decreased total particulate level by
burning out carbonaceous particles and shifted size distribution
towards smaller particles as the large ones burned out. It was
felt that if size distribution had a significant influence on the
effectiveness of the sampling systems, it would be primarily because
of their inability to collect very small particles quantitatively.
The basic information being sought in this study was (1) what
percent of the fuel vanadium was accounted for by the collection systems
after correcting for boiler deposits, (2) whether there was a significant
difference between the effectiveness of the two systems, and (3) how
much the effectiveness changed as vanadium content and size distribution
was varied.
Ultimately, four variables were involved in this investiga-
tion viz., sampling system, fuel oil, combustion chamber residence time
and sample location in the stack. The latter was selected to rule out
the possibility that particulate maldistribution in the flue gas would
produce a bias in the results. The two sample systems were tested si-
multaneously in each run using sample ports located 90° apart. A sys-
tematic maldistribution might have caused one or the other port to give
higher vanadium recovery. A factorial design of the type 2x2x2x3
was used to study the responses of the variables and also provide a frame-
work for analysis and interpretations of the results.
While the factorial program constituted our major effort, some
limited experiments were conducted to determine the oxidation state of
vanadium particles collected on the filter of the Method 5 sampling train.
The methodology consisted of exposing several vanadium oxides to hot flue
gas from combustion of a conventional high sulfur fuel oil and then check-
ing for possible changes in the oxidation state.
Prior to the start of the factorial program, a literature survey
to assess methods of sampling and analyses of vanadium emissions from
combustion sources was made. Sources which were searched included the
American Petroleum Institute, Literature and Patents files from 1964 through
1975, NTIS (Government Reports) 1964 through current, and Chemical Abstracts
1970-1975. A bibliography covering this state-of-the-art review is pre-
sented in the first Appendix.
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2. SUMMARY
Exxon Research and Engineering Company (ER&E) has conducted
an experimental study to measure the efficiency of a standard EPA
Method 5 stack sampling train to collect vanadium emissions in flue
gas and compare it with an ER&E developed stack sampling system.
The ER&E system employs an Andersen Cascade Impactor and several
high velocity impingers filled with silicone oil. The impactor gives
size distribution down to approximately 0.4 microns, finer material
is collected in the impingers which now can operate at stack
temperature and, therefore do not produce false sulfate type particulate.
The stack solids are not soluble in silicone oil so separation of this
material is easily accomplished. In these tests the entire sampling
system was maintained at 400°F. The full EPA Method 5 sampling train
consisting of a probe, a cyclone, a fiber glass filter (MSA-1106BH)
and two water impingers were also employed. Sampling was accomplished
using the published EPA methodology (4) with the exception that the probe,
cyclone and filter were heated uniformly to 400°F rather than the
prescribed 225-250°F.
The ability of these sampling systems to collect vanadium
emissions was measured in a series of runs on particulates generated
by combustion of typical residual fuel oils in a 50 hp four pass
package boiler modified to simulate boilers of a variety of sizes.
This latter was accomplished by changing combustion chamber residence
time. Experimentally, this was carried out by varying the fuel oil
firing rate and/or adding an additional section of refractory to
the existing combustion chamber. With these procedures residence time
could be changed almost 7 fold from roughly 50 msec to 350 msec. In
comparison the combustion zone of a large utility boiler may provide a
residence time of more than 1 second.
Variables in this study were selected on the basis that they
might affect the amount and size distribution of vanadium in the
flue gas. Two levels of combustion chamber residence time and three
residual fuel oil compositions, which would normally be encountered
in the U. S., were chosen. Included were two all-Venezuelan resids
with vanadium contents of 359 ppm and 149 ppm respectively and a light
Arab resid with a vanadium content of 39 ppm.
An important part of the experimental procedure was the
simultaneous operation of both particulate sampling trains during each
run. This served to eliminate sampling bias attributable to fluctuations
in boiler operation. To accomplish simultaneous sample withdrawal, two
sampling ports located 90 degrees apart in the stack were used. As
a further precaution, to safeguard against possible maldistribution of
particulate in the stack, the sampling trains were systematically
rotated between sampling port locations. Thus half of the test program
was carried out with a sampling train at one port and the other half
with the sampling train at the second port. The selection of sampling
port location was accomplished using a restricted randomization.
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Ultimately, four variables were involved in this study:
sampling system, fuel oil, combustion chamber residence time and
sample port location in the stack. To evaluate these factors and provide
a framework for statistical analysis, a factorial experimental design
of the type 2x2x2x3 was employed. A total of 36 experiments were
made consisting of 12 base case runs each with two levels of replications.
The key to evaluating sampling system collection efficiency
was a vanadium balance in the boiler. B7 knowing the vanadium
content of the fuel which is burned and by determining the amount of
vanadium that deposits in the boiler, it is possible to establish
how much vanadium enters the stack. The amount not accounted for in
the sampling train represents a combination of collection inefficiency
and/or experimental error in measurement and other inaccuracies.
Vanadium analysis of the boiler and stack solids was accomplished using
Atomic Absorption Spectroscopy.
The amount of vanadium deposited within the boiler was
determined by using removable stainless steel liners in one of the
heat exchanger tubes in each pass of the boiler. At the end of each
run, the tubes were removed and the deposits in each were collected
and analyzed for vanadium. Total deposits were estimated by assuming
that the vanadium deposited in a liner was equal to the vanadium deposited
in each of the other tubes in the same pass. Fire-tube deposits were
measured by cleaning the fire-tube after each run. Any vanadium
not accounted for in the boiler was assumed to have entered the stack
with the flue gas.
The flue gas in the stack was sampled isokinetically using
either Method 5 or ER&E systems. Particulate samples from the probe,
cyclone, filter and impingers of the EPA system were measured separately
and analyzed for vanadium. Particulate samples from the ER&E system
were combined into size fractions: >10 microns, 1 to 10 microns and
<1 micron. Each fraction was analyzed for vanadium.
For each run the material balance obtained with the EPA
Method 5 system was compared with that obtained with the ER&E system.
In addition, the material balances between runs were compared to
determine the influences of fuel type and vanadium content, combustion
residence time and sampling position within the stack. These comparisons
were made using analysis of variance.
It was determined that vanadium recovery was dependent on
only two variables, combustion chamber residence time and sampling
system; fuel type, i.e. amount of vanadium in the fuel, and sampling
position in the stack were not statistically significant.
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Results obtained with the light Arab fuel oil were very
erratic and indicated a high degree of experimental error. This
was attributed to the very low V content in the fuel and consequently
in the particulate. Vanadium recovery with either sampling train
averaged in excess of 100% and ranged between 70% and 174% of the fuel
V input. Tests made with this particular fuel could not be used
to measure collection system efficiency. In contrast, results
obtained using the two all-Ven (Venezuelan) fuels were very consistent
and therefore served as the basis for the evaluation.
At short combustion chamber residence time (high fuel
firing rate), particulate distribution was predominantly in the
coarse size range, total vanadium recovery (boiler plus stack) was
highest using the EPA Method 5 system and averaged 88.6 wt. % of the
fuel V input. Based on-the number and potential inaccuracies of the
measurements used to make the overall vanadium material balance (i.e.
vanadium deposition in the boiler headers is not accounted for) this
value represents nearly quantitative recovery. In contrast, total
V recovery using the ER&E system was lower by 7.7% and averaged
81.8 wt. %. This difference was statistically significant (90 percent
confidence limit) but still within acceptable limits.
At the short residence time, recovery of vanadium in
the fire-tube and boiler passes averaged 29.3 wt. % of the fuel V input
or about 34% of the total recovered.
In tests made at long residence time (low fuel firing rate),
which by comparison is about 1/3 less than found in a large utility
boiler, the particulate distribution was shifted to the submicron size
range. This resulted in a significant decrease in total vanadium
recovery (boiler plus stack sampling systems) averaging about 21%. This
gross change in vanadium recovery, however, is not fully ascribed to
collection inefficiency. Part, if not all of the problem, may be
caused by the failure to inventory completely the vanadium which
deposits in the boiler. At the firing rate used in these tests, the
volumetric flow rate of the combustion product gas stream is very low
and may produce some maldistribution as it goes through the boiler
passes. Since our estimate of the quantity of vanadium sampled in
the stack is predicated on the amount recovered in the boiler, it is
evident that an error here would distort the recovery value in the
stack. Vanadium recovery in the boiler for this case amounted to 22.7
wt. % of the fuel V input, which represents a decrease of 23% compared
to the previous tests made at short residence time. On this basis
total vanadium recovery using Method 5 averaged 73.9 wt. % versus
62.3 wt. % obtained with the ER&E system.
The difference in recovery between the two sampling systems
is real and significant at long residence times. This indicates that
V collection efficiency in the ER&E sampling system is lower and is
primarily due to the inability of the silicone oil impingers to retain
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very fine vanadium particles. In contrast, the fiber glass filter
used in the Method 5 system has a lower particle size cut-off limit
i.e., it retains more of the very fine vanadium particles than do
the silicone oil impingers.
The inefficiency of the high velocity impingers to collect
the very fine submicron particles was general and not confined to
the particular collection medium. In Method 5 several water filled
impingers were used as back-up for the filter. Essentially none
of the vanadium was found in these impingers even at long residence
time where the data suggests that fine vanadium particles were passing
through the filter.
Total particulate emissions which were also measured with
each sampling system were in reasonable agreement. This was taken
as a further indication that only fine highly concentrated vanadium-
bearing particulate were being lost through the silicone oil impingers.
At short residence time, the two stack sampling trains had total
particulate inventories less than 1% apart. At long residence time
stack loading was significantly reduced and total particulate
inventories differed by about 13%. The higher inventory was obtained
with Method 5 and was consistent with the higher vanadium assay.
A variable and highly erratic amount of solids isolated
from the chilled water impingers of the Method 5 train were not
included in the total particulate inventory. These solids were composed
predominantly of ammonium sulfate and ammonium bisulfate and were
therefore regarded as artificial particulate, i.e. an artifact of the
chilled water impinger system only. The origin of ammonia in the flue
gas is not known.
Vanadium collection efficiency of the sampling systems as
defined in this study is the ratio of the amount of V collected in the
respective stack sampling train to the amount of V in the fuel minus
the amount deposited in the boiler/ Vs \ . This presupposes
( V]7-FB J
\^ S
that all losses of vanadium occur from the stack sampling system. Since
there is a finite possibility that some of these losses are due
to inaccuracies in the boiler measurement, the calculated collection
efficiency may be taken as representing only a minimum value. In
addition, because of the lower base used in these calculations, collection
efficiency is always lower than the corresponding vanadium recovery.
At short combustion chamber residence time, typical of a
small boiler, the EPA Method 5 stack sampling train had a minimum
vanadium collection efficiency of 83.9%. The ER&E train operated
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at the same condition had a collection efficiency of 74.3%. At
long combustion chamber residence time, typical of a large boiler,
where V emissions are mostly in the submicron size range, collection
efficiency of the EPA Method 5 system apparently decreased. Collection
efficiency amounted to 66.2% compared to 51.1% obtained with the
ER&E system.
Several experiments were also conducted to determine
the oxidation state of vanadium emissions collected on the Method 5
fiber glass filter. Using selected vanadium oxides and exposing them
to flue gas at elevated temperature, it was found that some
vanadium (V) was partially reduced to vanadium (IV). Although this
is by no means definitive, the results do suggest the possibility
that both V ** and V" emissions may be present in the flue gas.
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3. CONCLUSIONS
On the basis of this completed factorial study to evaluate
and compare collection efficiency of Method 5 and ER&E type stack
sampling systems, the following conclusions can be made:
1. Both EPA Method 5 and ER&E sampling systems show good
vanadium recovery at short residence time.
2. Recovery in both sampling systems decreases at long residence
time but the decrease was significantly greater in the ER&E
system.
3. The EPA Method 5 sampling system generally produced a better
vanadium material balance because it collected more of the
fine vanadium particles.
4. The Method 5 system collects no fine vanadium particles in
the water impingers.
5. The fiber glass filter used in Method 5 has a lower fine particle
cut-off size limit than the high velocity Greenberg-Smith type
impingers containing the silicone oil or water.
6. The low vanadium content of the light Arab fuel oil made it difficult
to obtain a reliable vanadium material balance around the
boiler.
7. Total particulate inventories measured by ER&E and Method 5
(front half) sampling trains at 400°F are similar and within
experimental error.
8. The back half of the EPA system (water impingers) collects a
highly variable quantity of artificial particulate matter.
9. Oxidation states of vanadium emissions in the flue gas may
include V1"^ as well as
-------
- 10 -
4. RECOMMENDATION FOR FURTHER TESTING
The vanadium material balance measured with the Method 5
train at short residence time probably represents nearly quantitative
recovery. The main inaccuracy appears to be associated with the
boiler inventory. For example, the amount of particulate fallout
occurring at the headers at either end of the boiler is not known.
This represents about 10% of the surface area of the boiler and
therefore could contribute to the error noted in these measurements.
At long combustion chamber residence time, there is some
uncertainty as to how accurate vanadium collection is. The probability
that at the low firing rate the combustion gas stream is maldistributed
in the boiler passes must rank high. To obtain a better vanadium
material balance, i.e., to determine where the losses are, additional
efforts may be directed either to improving the collection in the
stack or in the boiler. Since the stack sampling train results
suggest that very fine vanadium particles are being lost, the chances
of collecting them with existing equipment is slight. Therefore
primary emphasis in any further testing should be initially placed
on improving the vanadium material balance in the boiler.
Vanadium collection in the boiler may be accomplished in
several additional tests by two techniques. The first consists of
making a complete collection and inventory of all material which
deposits in the boiler after a run. While this will be tedious and
quite time consuming, it does provide the highest reliability and
accuracy. The second employs isokinetic sampling of the fire-tube.
While this requires less time to accomplish it, it may also be less
accurate particularly if the combustion gases in the fire-tube are
maldistributed. Both of these techniques, however, can provide a
better and potentially more accurate measure of vanadium particle
fallout in the boiler than the single tube insert which was used.
-------
- 11 -
5. BACKGROUND
5.1 Vanadium in the Environment
5.1.1 Ambient Air Measurements
A number of ambient air particulate sampling studies have determined
the concentration of specific elements in the collected particulate samples.
These surveys have shown, among other things, that the suspended particulate
from certain urban areas have significantly higher concentrations of vanadium
(V) than corresponding samples from rural areas, or for that matter from
certain other urban areas. ( 5,6,7,8) The highest concentrations, either as
fraction of total particulate or yg/m^ in ambient air, have been found in
cities along the East Coast of the U.S. Measurements in New York City during
the 1950's showed annual averages in the range of 2.5 yg/m^ . (9) Data gathered
in 1967 showed that a number of sampling locations in the New York-New Jersey-
Connecticut area averaged about 0.5 yg/m on an annual basis• (8) Other East
Coast sampling locations averaged 0.1-0.2 vig/m3.This is shown in Table 5.1.
By wav of contrast urban areas in the south and midwest averaged
.01 to .05 Mg/m of V in ambient air.This level was only a little higher
than the V concentrations in rural areas of the same portions of the U.S.
Information of this type on ambient concentration of V particulates
has led a number of investigators to the conclusion that the primary source
of vanadium in ambient air is fuel oil combustion. Most of the fuel oil
used in the United States is burned in the major metropolitan areas along
the East Coast, where the highest ambient V concentrations were found.
During the period in which much of the data was obtained the fuel oil used
was almost exclusively of Venezuelan origin which meant that it had rela-
tively high V content — about 200-400 ppm by weight — compared with fuel
oils from U.S. or Middle East fuels which usually contain well under 100
ppm V. About 1970 fuel sulfur regulations went into effect along the East
Coast, forcing a drastic change in fuel oil composition. A comparison of
National Air Sampling Network data on ambient V concentration in 1967 and
1970 for Philadelphia and Washington, D.C. indicates a reduction in level
which is consistent with the lower V content of the low S fuel oil, about
196/8) 19?0 (10)
Philadelphia .264 .14
Washington, D.C. .165 .09
50-100 ppm, rather than 200-400 ppm. Many investigators have noted the
seasonal variation of ambient V in the areas of high concentration.(9,11} jt ^
highest during the winter months when large quantities of fuel oil are burned
for space heating.
The relatively low ambient concentrations of V in midwestern urban
areas, indicate that coal combustion is probably not a significant source
of V particulates. These areas are as highly industrialized as those on
the East Coast, but they use coal as the major fuel. Although many coals
contain a certain amount of vanadium, its concentration is low compared with
total ash content. Evidently most of the V is retained with the other ash
-------
- 12 -
TABLE 5.1
CONCENTRATIONS OF V IN AMBIENT AIR
YEAR
1967
1970
New York, N. Y.
Bayonne, N. J.
Philadelphia, Pa.
New Haven, Conn.
Washington, D. C.
Chicago, 111.
E. St. Louis, 111.
Hammond, Ind.
Montgomery, Ala.
St. Louis, Mo.
Pittsburgh, Pa.
Akron, Ohio
Phoenix, Ariz.
Denver, Cola.
Dubuque, Iowa
Monroe State Forest, Ind.
Rio Arriba County, N.M.
Annual
Avg.
905
445
264
49
165
Ug/m3
Max.
1.4
.99
.43
.74
.23
4th Quarter Annual Avg
.06
.006
.034
.0033
.0116
.016
.0063
.0037
.0034
.0062
.0013
.0014
.10
.007
.054
.0033
.025
.034
.013
.0042
.0034
.0062
.0017
.0014
.12
.09
.07
.03
.14
.09
.06
-------
- 13 -
constituents in the electrostatic precipitators or other particulate collec-
tion devices on coal fired combustors.
In areas where low ambient concentrations of V have been found,
soil is considered to be the most likely source. On the basis of V/A1
ratio Marten et al^-^) concluded that soil dust was responsible for a
major portion of the V found in large particles in the San Francisco Bay
area. They also concluded that fuel oil combustion sources were responsible
for V in smaller particles,
-------
- 14 -
Animal exposures to concentrations of 8,000 to 18,000 yg/m of
^0 for 2 hours daily for a period of 9 to 12 months resulted in acute and
nronic poisoning.' '
These studies and episodes were all related to airborne concentra-
tions which were order of magnitudes higher than those encountered in ambient
air. There is no clear cut evidence that exposure to airborne particulate
vanadium compounds at the concentrations normally encountered in ambient air
has any acute toxic effects. However, exposures to concentrations of 20 to
900 Pg/rn^ have been related to reduced cholesterol concentrations.
(13)
In a statistical study, Hickey et al found a moderate correla-
tion between ambient vanadium concentration and "diseases of the heart" in
25 communities in the U.S. They also found high correlations with bronchitis,
pneumonia and lung cancer. However, there was no way of establishing a cause
and effect relationship in these studies.
The National Academy of Science has recently completed a study of the
health effects of ambient concentrations of V particulates. They concluded
that there is no health hazard at the concentrations normally encountered in
ambient air. There may be a health hazard associated with high localized
concentrations which might be encountered in industries which form or use
vanadium compounds, i.e. manufacture of high alloy steel or the suppliers
of the vanadium for this use.
5.1.3 Natural Occurrence of Vanadium in Fuels
Vanadium is one of the most common inorganic ash constituents of
crude petroleum. Its concentration varies widely according to crude source.
North African crudes from Libya and Nigeria are generally very low in V
content about 1 to 5 ppm. Middle East crudes tend to be intermediate —
25 to 50 ppm and Venezuelan crudes tend to be high — 100 to 500 ppm V.
Table 5.2 shows the concentration of V in typical Middle East and Venezuelan
crudes and fuel oils which have been used in U.S. fuel oils.
TABLE 5.2
Characteristics of Middle East and
Venezuelan Crudes and Fuel Oils(14)
Lt. Arabian
Fuel
Crude Oil
Kuwait
Fuel
Crude Oil
Tia Juana Med Libyan
Fuel
Crude Oil
Fuel
Crude Oil
Gravity, °API
Sulfur, Wt.%
Pour Point, °F
Viscosity, SSU @ 100°F
Viscosity, SSF @ 122°F
Vanadium, ppm
Nickel, ppm
34.7
1.7
-55
44
-
13
4
15.
3.
+55
-
175
37
11
5
0
31.4
2.5
-20
56
-
31
7
15.5
5.0
+55
-
175
61
14
26.
1.
-40
116
-
156
20
5
5
16.
2.
+20
-
170
350
31
3
0
39.
0.
+40
40.
-
3
-
2
2
5
22.2
0.4
+105
-
65
10
-
-------
- 15 -
The vanadium in these crudes is in the form of organo-metallic
compounds which are thought to include many porphorins or porphorin like
compounds. A small part of the vanadium is in the form of volatile
compounds in the vacuum gas oil boiling range, but by far the most is
non-volatile and is associated with the asphaltene fraction. A number of
studies have been carried out at Exxon Research and elsewhere in an
to characterize this fraction and the organo-metallics it contains. (15,16,17)
However, because of its extreme complexity very little separation has been
achieved.
Basically, however, the vanadium containing compounds are known
to be non-volatile, which means that essentially all of the vanadium in
the crude remains in the residual fraction which is normally the basic
component of heavy fuel oil. Furthermore, it is primarily associated with
the asphaltenes in that residuum. These materials are the most resistant
to cracking and volatilization during the combustion process. They form
the carbonaceous residue of the spray droplets during the fuel oil com-
bustion process after the volatiles have burned off. These residues,
called cenospheres, contain essentially all of the vanadium from the fuel.
As the cenospheres burn out in the combustion zone, the vanadium is oxi-
dized, primarily to V 0 which forms the ash residue.(18)
Vanadium concentration in U.S. coal is normally in the range of
15-50 ppm. It is usually in the form of organo-metallic compounds similar
to those found in crude oil. The relatively low total V content in con-
junction with the high ash content (olO%) of these coals makes vanadium
a minor constituent of the total ash. As indicated in Table 5.3, V amounts
to .01-.05% of the ash from coal combustion. As such most of it is removed
from the flue gas in the electrostatic precipitators or other ash collection
devices. Emission of V particulate from coal firing is only a minor source
of atmospheric V as indicated by the low ambient concentrations in indus-
trialized sections of the Midwest where coal is the primary fuel.
TABLE 5.3 (FROM REFERENCE 8)
Concentrations of Vanadium in Domestic Coals
Vanadium in Ash Vanadium in Coal
Coal Source % ppm
Northern Great Plains .001 - .058 16
Eastern Interior Region — 35
Appalachian Region — 21
Texas, Colorado, N.Dakota, S.Dakota 0.01 - 0.1
West Virginia 0.018 - 0.039
Pennsylvania (Anthracite) 0.01 - 0.02
Buck Mountain Bed . 0.11 176
Diamond Bed 0.09 92
-------
- .16 -
5.2 Nature of Vanadium in Emissions
5.2.1 Mechanism of Particulate Formation
Fuel oil is sprayed into the combustion zone of a boiler in the
form of 100 - 300 Vtai droplets which are mixed with combustion air as they
enter the flame. Single droplet studies have given a good picture of what
happens to the droplets in the combustion zone. As the droplet heats up,
the volatile materials boil off, especially those in the outer layer and
burn in the vapor phase. This leaves a shell of non-volatile solid material
around the surface of the droplet. As the droplet temperature increases,
volatile material from the interior of the droplet vaporizes and ruptures
the outer shell, leaving holes in it and forming a solid layer further in.
This process is repeated until all of the volatile material has vaporized
and as much of the non-volatile material as will crack into volatile hydro-
carbons has done so. This leaves a solid, carbonaceous residue roughly the
size of the original droplet but containing a high percentage of void volume.
This residue is called a cenosphere. Most of the material in the cenosphere
is the asphaltene fraction of the fuel oil. We have found that the asphaltene
content of a fuel oil is a very accurate predictor of the amount of cenosphere
which will be formed during combustion, and of the total weight of stack solids
which will be emitted at a given set of combustion conditions. Figure 5.. 1
shows electron microscope pictures of cenospheres which are >10ym and Figure
5.2 shows partially burned out material in the 1-lOym.
Since essentially all of the vanadium in the fuel is contained in
the asphaltenes, it will also remain in the cenospheres. When the ceno-
spheres form, most of the vanadium is still in the form of organo-metallic,
porphoryn-like compounds. As the cenospheres burn out, the vanadium is
converted into the oxide form. No studies are available to tell what
oxide is present in the partially burned out cenospheres, but after complete
burn out, V-0,. is formed at combustion conditions. Almost all of the ceno-
spheres do burn out before they leave the combustion zone. The asphaltene
content of a typical high S (2.2%s) Venezuelan fuel oil is 10-12%, whereas
total particulate emissions from a well run boiler are less than 0.1-0.2
wt.% on fuel.
When the carbonaceous portion of the cenosphere burns out, the V
in the ash residue tends to form V_0,-. Figure 5.3, which is from reference
19, shows the equilibrium between V20, and Vo^V Increasing 0- content favors
the formation of V 0 but increasing temperature favors V«0 formation. At
normal combustion conditions significant V 0_ formation is savored. Under
combustion zone conditions, V 0 has a significant vapor pressure, as shown
in Figure 5.4, also from reference 19. It is high enough so that all of
the V present even in the highest ash fuel oil can be vaporized. As the
combustion gases move through the heat exchanger sections of the boiler,
they are cooled and the vapor pressure of V 0 drops. Particulate V 0
forms. The bulk of it is in the very small size range because of the rapid
cooling rate. When the gases leave the boiler at 5-600°F or less, the
vapor pressure of V 0,. is low enough so that only a negligible amount is
in the vapor phase, vanadyl chloride VC1, which boils at 300°F has a vapor
pressure, and would be in the vapor phase in the flue gas. However, no
one has reported any formation of VC1, in the combustion of fuel oil.
-------
- 17 -
Thus vanadium particulates in the flue gases leaving a boiler
are distributed over the entire range of sizes. The cenospheres which
are 10-50ym in diameter contain vanadium in the carbonaceous matrix;
partially burned out cenospheres in the l-10ym range contain a higher
percentage of V; and submicron particles of V?0,. are formed by condensation
from the vapor phase.
-------
FIGURE 5.1
>10 MICRON PARTICULATE EMISSIONS
(CENOSPHERES)
10 Microns
00
-------
- 19 -
FIGURE 5.2
INTERMEDIATE SIZE RANGE (1-10 MICRONS) PARTICULATE
1.0 Microns
-------
50
o
630
en
0*20
O
<
>-,
en
o
-10
^•/". . ^ — ~Z_ i —*-<-__Excess a\r
/ — ~^£- ~- ~~ ^sf IV.Excess a\r
"' *? ^"^ '
./__ __ [—,x-5V. Excess a\r
woo
OV.V204
80
20
60
AO
40
60
20
60
OV.V205
100V. V204
Fig. 5.3 . The cffi-cls uf toinpcr.tturc and oxygen availability on equilibrium
fur ilii; reaction 2V2O. -,- -VVOj + Oj
700 800 900 1.000 1.100 1.300 1.500
Temperature. °C
J . 4> Vapour pressures of fuel oil ash constituents
N)
O
-------
- 21 -
6. EXPERIMENTAL PROGRAM
6.1 Research Plan
This section discusses combustion facilities, the design of the
experimental program, test methodology, analytical procedures used for
evaluating vanadium collection efficiency of the EPA Method 5 and ER&E
stack sampling trains. The general approach taken in this investigation
consisted of three phases:
1. State-of-the-Art-Review: An initial literature review was
made to assess stack sampling and analytical methodology for collecting
and analyzing vanadium-containing particulate (both gaseous and solids)
from fossil fuel combustion sources. The survey indicated that Atomic
Absorption Spectroscopy followed by Arc Emission Spectroscopy are the two
most precise and widely used techniques to analyze for vanadium-containing
particulate (both gaseous and solids) from fossil fuel combustion sources.
Collection of particulates in flue gas has been carried out with an ever-
increasing number of devices. However, there is nothing in the literature
to indicate that the standard fiber glass filter employed in the Method 5
sampling train is less efficient than other collectors. For particulate
sizing, the Cascade Impactor, in spite of its many "stated problems",
still remains the method employed by most investigators.
2. Develop Test Program: A factorial experimental program was
developed and approved by the EPA. This program, conducted in our combus-
tion facility,was designed to permit evaluation of vanadium particulate
collection efficiency for a standard EPA Method 5 stack sampling train and
an ER&E developed sampling system. It employs a factorial design to mea-
sure the interactions between several variables which were chosen because
they might affect the amount of vanadium in the flue gas and the size
distribution of the vanadium emissions. These variables were combustion
chamber residence time and fuel composition (ash and asphaltene content).
Two levels of residence time and three typical heavy fuel oil compositions
were selected for evaluation. In addition, two sampling locations,
90° apart in the stack, were included as variables in the study
to eliminate any bias attributable to particulate maldistribution in
the flue gases. To evaluate these factors, 36 experiments were
planned - 12 base runs, each with two levels of replications. An important
aspect of the test procedure was the simultaneous operation of both sampling
trains in each test. This feature not only served to double the data base,
but it also eliminated sample bias attributable to run to run fluctuations
in boiler performance. This influenced our decision to use restricted
randomization for selecting the sequence of experiments.
The key to evaluating sampling system collection efficiency was
a vanadium balance around the boiler. By knowing the vanadium content
of the fuel which is burned and determining the amount of vanadium that
deposits in the boiler, it is possible to establish how much vanadium
enters the stack. The amount not accounted for in the sampling train
-------
- 22 -
represents the combination of collection inefficiency and/or experimental
error in measurement and other inaccuracies.
To accomplish a vanadium material balance in the boiler, two
methods were originally proposed. The method actually used in the study
consisted of inserting a removable, thin wall, stainless steel liner
into one heat exchanger tube in each boiler pass. At the end of a test,
the inserts were removed, their contents were inventoried and assayed for
vanadium. Assuming that the combustion gases were not maldistributed,
the amount of vanadium found in one insert times the number of heat ex-
changer tubes in that particular pass equalled the amount of vanadium
deposited. This method has two potential causes of inaccuracy. The
first is the supposition that combustion gases flow equally through all
the heat exchanger tubes. The other shortcoming results from not being
able to inventory the two water backed face plates in which the heat
exchanger tubes are set. These plates account for about 10% of the
total surface area of the passes.
In order to overcome these problems, a second method was pro-
posed involving isokinetic sampling of the combustion gases at the end
of the firetube. The advantage of sampling there is that the combustion
gases have not as yet gone through any heat exchanger tubes or return
sections, which tend to collect particulates. Thus a material balance
would obviously be facilitated.
The disadvantages of sampling in the firetube are that the
gases are still very hot and that there may be greater maldistribution
of particulates than in other sections. At the point where the sample
would be taken, gas temperature is 1100-1600°F depending upon combustion
conditions. The gas sample would have to be quenched rapidly from fire-
tube temperature to 400°F in the collection system. Since some of the
ash components might still be vaporized at firetube temperature, this
quenching would cause them to precipitate in a different form than they
might have in a heat exchanger. Thus size distribution might be affected.
Particulate maldistribution may come about from inhomogeneities
in the flame and the swirl imparted to the combustion gases by the burner.
This problem simply means that greater care would have to be taken in tra-
versing to get a good sample of the overall particulate loading.
In view of budget limitations it was decied only one method
should be used. Since the tube inserts appeared the most practicable
means of measuring vanadium deposits in the boiler, they were chosen.
During the initial phase of the program several preliminary experiments
were conducted to debug this technique. Samples from these runs were also
used to establish the analytical methodology for determining vanadium
content of the particulate.
3. Conduct Test Program: Paired tests were conducted in the package
boiler during each week of operation. Experimental pairings were based on
alternating combustion chamber residence time. This technique was employed
as a means of minimizing the effects of possible long term fluctuations in
boiler performance. Of the 36 tests constituting the factorial program
only one (Run 61) had to be terminated and the results eliminated because
-------
- 23 -
of problems traced to boiler operation. The entire test program required
5 months to complete. Additionally several experiments were made to
determine changes in oxidation state of vanadium compounds retained on a
filter when subjected to the stack gas environment.
6.2 Combustion Test Facility
6.2.1 50 hp Cleaver Brooks Package Boiler
All combustion experiments were carried out in a 50 h.p package
boiler having a nominal firing rate of 2 Ibs/min. (15.0 gph) of residual
fuel oil. This boiler is a horizontal firetube type; by means of appro-
priate baffles and heat exchanger tubes, the combustion gases are forced
to pass the length of the boiler four times before being emitted into the
stack. A cut-a-way view of a typical C-B boiler showing the four pass
construction is illustrated in Figure 6.1. In these tests, firing rates
of 2 Ibs/min. and 0.5 Ibs/min. were used. This difference represents a
four-fold change in combustion chamber residence time; the reciprocal of
firing rate Cp^) is roughly proportional to residence time. To amplify
even more the effect of residence time, in those runs using the low firing
rate an added second refractory chamber was butted to the existing com-
bustion chamber. This increased the overall combustion volume by about
66>% and residence time by an additional 1.6 times. When not required, the
added refractory was removed from the boiler. Firing rate and fuel con-
sumption were accurately metered in each test by periodically monitoring
the loss in weight of the oil supply drum. Atomization of the residual
fuel oil was accomplished by maintaining a constant volume of air at low
pressure (10 psi) on the burner gun. In all tests the fuel oil viscosity
at the atomizing nozzle was maintained at 30 centistokes by heating the
fuel to a predetermined temperature with an electrical heater.
Secondary air for combustion was furnished by a centrifugal
blower mounted in the boiler head. The air was forced through a diffuser
plate to thoroughly mix with the atomized oil before combustion. The
amount of the secondary air was controlled by means of a damper which was
regulated to keep oxygen concentration in the flue gas, normally at 2%
(VLO% excess air).
For monitoring boiler performance, the concentration of CO,
C02 and Q£ in the flue gas was continuously measured using Beckman instru-
ments. Both carbon monoxide and carbon dioxide were measured using non-
dispersive infrared analysis while oxygen was determined polarographically.
Figure 6.2 is a front view photograph of the Cleaver Brooks boiler
illustrating the oil supply drum monitoring arrangement and air control
damper/burner housing. Figure 6.3 shows the instrument bank (foreground)
for monitoring composition of flue gas. Controls for the stack sampling
systems are positioned alongside the boiler.
To insure operational stability, the package boiler was allowed
to warm up for a minimum of one hour before the start of a run which would
normally last from 1-2 hours. During the test, minor adjustment of the
secondary air to maintain flue gas oxygen concentration at 2% was
normally the only control required to hold conditions constant. The oil
firing rate was set immediately upon start up of the boiler. Temperature
of the combustion gases at passes 1, 2 and 3 as well as in the stack were
recorded continuously. Other ancillary measurements included pressures in
-------
THE FOUR PASS CONSTRUCTION OF A TYPICAL C-B BOILER
Pass 3
Pass 4
Pass 2
to
I
FIGURE 6.1
This cutaway view shows the gases are constrained to flow through the four passes in the order indicated. The
combustion air enters the burner through an Adjustable Damper. The blower forces air through the diffusor and
into the combustion chamber, this constitutes Pass (No. 1). Baffling allows gases to pass to the front of the
boiler only through Pass (No. 2). A plate constrains gases to travel to the rear of the boiler through Pass (No.
From the rear head,gases are forced through Pass (No. 4) to the stack.
3).
-------
-25-
FIGURE 6.2 - 50 HP CLEAVER BROOKS BOILER
FRONT VIEW OF BOILER SHOWING OIL SUPPLY MONITORING SYSTEM, AIR DAMPER
CONTROL AND BURNER HOUSING.
-------
- 26 -
FIGURE 6.3 - ARRANGEMENT OF FLUE GAS MONITORING SYSTEMS
FOREGROUND: INSTRUMENTS INCLUDE CO, C02, 02 AND NOX MONITORS. CONTROL
EQUIPMENT FOR PARTICULATE SAMPLING TRAINS IS POSITIONED NEAR BOILER.
-------
-27-
the windbox and end of first pass, and back pressure on the oil line and
atomizing air line.
6.3 Program Design
The object of our experimental program was to measure and compare
the effectiveness of the standard EPA type stack sampling system and the
Exxon Research developed system for collecting vanadium emissions from com-
bustion of appropriate residual fuel oil. A standard EPA type train was
used which consisted of an 18 inch glass lined probe, a cyclone, a glass
fiber filter (125 mm, Type MSA-1106BH) and two chilled water impingers.
With the exception of the latter all components were heated to 400°F.
The ER&E system comprises an 18 inch glass lined probe, an 8-stage
Andersen Cascade Impactor and two silicone oil-containing impingers, all
heated to a temperature of 400°F. As back-up to this system, a dry ice-
acetone finger trap at -100°F was used in the line after the last impinger
to condense any volatile vanadium compounds.
The reliability of the two systems, i.e., the ability to collect
all of the vanadium-bearing materials entering the stack sampling system
was determined on the basis of a vanadium balance made around the boiler.
Inventorying the particulate fallout in the four boiler passes was accom-
plished with removable, thin wall, stainless steel liners inserted in
one of the heat exchanger tubes in each pass. At the end of a test the
inserts were removed, their contents were collected and weighed by the
same means used for isolating sample probe solids. Analysis for vanadium
in the particulate was made using atomic absorption spectroscopy.
It was expected that particle size distribution of the vanadium
particulate would have a major bearing both on the amount of material that
deposits in the boiler tubes and on the collection efficiency of the stack
sampling systems. Since the concentration and chemistry of vanadium in
the fuel during combustion could influence this distribution, residual fuel
oils encompassing a range of ash contents and asphaltenes (hexane insolu-
ble material) were employed. Selected resids included a high and an inter-
mediate sulfur fuel oil produced from Venezuelan (Tia Juna Medium) crude
and a high sulfur Light Arab fuel oil. All fuels are typical of those
currently being used in the United States. Key inspections are presented
in Tablt 6.1. Complete analyses are shown in Table 6.2.
TABLE 6.1
Residual Fuel Oils Used in V Collection Efficiency Study
Asphaltene Content
Fuel Designations Sulfur Vanadium Nickel Ash (Hexane Insolubles)
& Type Wt. % wppm wppm wt.% Wt. %
F , Hi. S (Venezuelan)
F2, Med. S
F-, Hi. S. (Light Arab)
2.8 39 10 0.01
2.2
1.0
359
149
63
26
0.09
0.05
12
5
-------
TABLE 6.2
Inspection
% Ash
B S & W
BTU///
% Carbon
% Hydrogen
% Sulfur
Con Carbon
Flash Point, °F
API Gravity, 60°F
% Hexane Insolubles
% Nitrogen
Pour Point
Sed. by Hot Filtration
Vis. SSU @ 100
Total Oxygen %
Metals, ppm
V (Range)
Na
Ni
Fe
Heavy
Low Ash
Light Arab
Test Fuel F0
0.01
0.06
18,708
85.22
11.04
2.84
7.18
220
16.4
3.74
0.21
+40
0.02
1444
0.20
37-42
Trace
10
10
Fuel Oil Inspections
High Ash
Venezuelan
Test Fuel Fn
0.09
0.16
18,540
84.73
11.23
2.20
12.70
178
14.7
11.79
0.48
+20
0.20
4694
0.42
335-383
24
63
9
Intermediate Ash
Venezuelan
Test Fuel F0
0.04
0.80
18,976
86.63
12.24
0.96
5.63
216
20.7
4.98
0.28
-10
0.20
500
0.40
138-158
10
26
6
to
00
-------
- 29 _
Of the two Venezuelar fuel oils it may be noted that ash and
asphaltene contents are roughly proportional to their sulfur content.
This results from the desulfurization process used. Since ash and
asphaltene in the Venezuelan residua cause intolerable catalyst deac-
tivation in the desulfurization process, the residuum is vacuum dis-
tilled before it is hydrotreated. Only the overhead cuts from the
vacuum tower, which are free of ash and asphaltenes, are desulfurized.
A portion of the high sulfur vacuum bottoms is blended back into the
desulfurized vacuum gas oil to make the final low S fuel oil. The
amount which can be added is limited by the fuel oil S target. A 1%
sulfur fuel oil contains only about half as much vacuum resid as the
high sulfur (2%) fuel oil. Since all of the ash and asphaltenes are
contained in the vacuum resid the concentrations of these components
are proportional to the sulfur content. Thus a 1% S resid would have
about half that of a 2% S fuel oil.
Residence time in the combustion zone is a major variable
affecting particle size distribution and distribution of vanadium among
the particle size range. Residence time is also one of the primary
differences between different sized boilers. Previous studies at Exxon
Research have measured the change in particulate distribution as a
function of residence time. This effect is illustrated in Figure 6.4.
As residence time in the combustion zone increases, more of the large
carbonaceous particles are consumed, shifting size distribution toward
submicron particles. These are generally the most difficult to collect
in a sampling system. A major change in size distribution resulted
from cutting firing rate in half with an extra combustion chamber. Total
particulates decreased by about half to 0.11 wt.% and almost all the
cenosphere and intermediate size particles were consumed. Inorganics
and refractory carbon material comprised the remaining particulate.
FIGURE 6.4
LONGER RESIDENCE TIME FAVORS
BURNOUT OF CENOSPHERES
200
BASE
1 LB/MIN
1 CHAMBER
0.5 LB/MIN
2 CHAMBERS
0.5 LB/MIN
3 CHAMBERS
-------
- 30 -
In the experimental program, two levels of residence time were
studied. For the base level (H) tests were run at a firing rate of
2 Ibs/min. (15 gal/hr.) using tne normal combustion chamber configura-
tion. At this combustion condition the calculated volumetric flow rate
was on the order of 450 cu. ft./min., which gave a residence time of
roughly 50 msec in the combustion chamber. In this case large particu-
late dominated the size distribution. For the second level ('T-f ) , firing
rate was decreased to 0.5 Ibs/min. (3.5 gal/hr.) and an additional
refractory chamber was added. These changes produced about', a 7-fold
increase in residence time to 350 msec. More importantly, at this
combustion condition carbonaceous material burned off and the particle
size distribution was shifted toward the submicron range.
As both residence time and fuel composition are main variables
which may influence vanadium collection efficiency a factorially designed
experimental program was employed. The program plan is outlined in
Table 6.3. There were 12 different experiments each replicated three
times for a total of 36 runs. As previously indicated both EPA and ER&E
sampling trains were operated simultaneously in each experiment. This
was possible by using two ports located at right angles to each other
in the boiler stack. To prevent the possibility of sample bias, since
it was not feasible to make a standard traverse in each port for every
run, the sampling train positions were rotated as indicated in
the table. On the basis of finding no statistical difference between
results from the two positions, the experimental design allows the
pooling of these data. In essence, this would double the number of
replications and degrees of freedom in defining the experimental error.
Selection of the order in which the experiments were run
was based on a restricted randomization. With truly randomized tests,
there is a finite probability that a block of experiments involving
a particular residence time (jTo or'TiO will be grouped toward either
end of the program. Any long term change in boiler performance would
influence residence time and seriously prejudice the results. Since
we were interested in comparing collection efficiency of the sampling
systems for vanadium particulate emitted in different size ranges,
a restricted test approach was used. Accordingly, paired tests, a
test at one residence time followed by the same test but at the
other residence time were used. Since only two tests a week could be
run, this grouping was most efficient.
To analyze for vanadium in the collected particulate, Atomic
Absorption spectroscopy was used. This method combines both high precision
with rapid sample throughput. The latter means that many samples can
be run in a short time period. This was an important feature since over
the life of this study approximately 475 samples were analyzed.
-------
TABLE 6.3
Experimental Program Design
Residence Time
TO = 50 msec.
Standard - Normal
Combustion Chamber,
15 Gnls/hr. firing rate
Residence Time
T j = 350 msec.
*vr fold increase with
double chamber and
3.75 Gals/hr. firing rate
Stack Sampling Probe Location
(1) EPA p->
EPA Vs. ER&E 1
Residual Fuel Type
Hi S Ven.
Run No.
55
57
68
54
56
67
F2
Med S Ven .
Run No.
48
69
75
49
70
76
F3
Light Arab
Run No .
47
61*
78
46
60
77
Stack Sampling Probe Location
(2) 1 +4 EPA
ER&E Vs. EP/I 1
Residual Fuel Type
Hi S Ven..
Run No .
52
71
79
53
72
80
(finish)
F2
Med S Ven .
Run No.
45
63
74
44 (start
62
73
F3
Light Arab
Run No.
50
58
65
51
59
66
Cycle 1
Cycle 2
Cycle 3
Cycle 1
Cycle 2
Cycle 3
• Experimental order based on restricted randomization of pairs.
• Total experiments = 36
• Time frame = 5- months
Notes on Experiments
*Run No. 61 was terminated after boiler upset. No data obtained in this run.
-------
- 32 -
6.4 Boiler Tube Inserts
Each of the passes in the Cleaver Brooks boiler consisted of
cooled heat exchanger tubes, 121 inches long by 2-1/4 inches internal
diameter. There are fourteen of these tubes in pass 2, ten in pass 3
and eight in pass 4 providing a total of 192 ft. of heat exchanger
surface area. Pass 1 is significantly different from the others.
It consists of a refractory lined combustion chamber 30 inches long x
12 inches diameter expanding into a water backed firetube, 19 inches in
diameter.' As summarized in Table 6.4, the firetube (pass 1) accounts for
roughly 15% of the total heat exchanger surface area. Pass 2 has
the greatest surface area, accounting for 33%. Pass 3 accounts
for 24%, while pass 4 makes up 19% of the area. There are water
backed face plates at either end of the boiler which could not be
inventoried for vanadium particulate. These account for 9% of the
surface area.
TABLE 6.4
Heat Exchange Surface in the Cleaver Brooks
Pass
1
2
3
4
Ends
No. of Tubes
(firetube)
14
10
8
Total Surface Area, Ft.'
37.6
84.0
60.0
48.0
22.0
% of Total
15
33
24
19
9
251.6
100
Particulates are thought to deposit within the heat exchanger
section by two mechanisms. Large particles drop out by impaction on
the walls of the tube or in the headers where gases reverse direction
between passes. It was not possible to collect and inventory particulates
from the headers after each run so this is a potential source of error.
The other collection mechanism is thermal or molecular
diffusion of fine particles to the walls of the tubes. The temperature
gradient between flue gas and water backed metal surface served as a
driving force for diffusion. Since metal surface was essentially
constant,this varied from pass to pass and between runs. Table 6.5
shows temperature levels measured in each pass at high and low firing
rates. By the end of the second pass, temperature has dropped to
within a few hundred degrees of stack temperature, especially at low
firing rate. Thus driving force for thermal diffusion is highest
in the first two passes.
-------
- 33 -
TABLE 6.5
Influence of Combustion Conditions on Boiler and Stack Temperatures
Fuel Firing Rate, Ibs./min.
Temperature °F 0.5 2.0
End Pass 1 1060 1625
End Pass 2 380 705
End Pass 3 283 500
End Pass 4 225 360
Stack 220 355
Removable thin wall stainless steel liners were used to
measure particulate and vanadium fallout in the passes. These were
machined from 304 seamless 2-1/4 inch OD x .065 wall OD pipe. These
liners were inserted during a run into one tube in each pass and then
removed and their contents inventoried at the end of each run. Since
it was not possible to sample the firetube by this method, a manual
cleaning method was used, (sweeping out the firetube). In Figure 6.5,
photographs A and B show the back end of the Cleaver Brooks boiler
with removable liners inserted in the various passes. The pictures
show two tubes per pass, but in most runs only one per pass was used.
The 14 second pass tubes are around the firetube in the bottom half of
the boiler. The chalk line drawn across the boiler facing separates
the 10 tubes in the third pass from the 8 tubes in the fourth pass.
Combustion gas enters the third pass at the front end of the boiler.
Since this area is not easily accessible, a locking collar was welded
into three of the tubes to prevent channeling of the gas stream between
liner and tube. Channeling was prevented at the back end of the boiler
by a collar welded on the liners. The collar fits tight against the
tube and face plate providing a seal. Photographs C and D show the
firetube .refractory lined combustion chamber and a front view where
the burner housing has been exposed.
6.5 Stack Sampling Systems
6.5.1 EPA Method 5
The EPA Method 5 stack sampling system used in this study was
a commercially available Joy Emission Parameter Analyzer. This unit
consisted of an 18 inch glass lined probe, a cyclone, a 125 mm glass
fiber filter (filter type MSA-1106BH) and two water impingers. The
configuration is shown schematically in Figure 6.6. With the exception
of the impingers, the entire sampling train was maintained at 400°F
in every run. This insured that stack gases entering the sampling system
were well above the acid dew point. Therefore sulfuric acid could not
condense on the collected particulate or the walls of the equipment.
-------
- 34 -
FIGURE 6.5 - FOUR PASSES OF CLEAVER BROOKS BOILER
it
A. THIN WALL STAINLESS STEEL REMOVABLE LINERS
FITTED INTO SELECTED HEAT EXCHANGER TUBES
IN PASSES 2, 3 AND 4. (BACK END VIEW) -
COLLAR ON END OF LINER PREVENTS CHANNEL-
ING OF THE COMBUSTION PRODUCT GAS STREAM.
B. BACK TO FRONT VIEW OF BOILER ILLUSTRAT-
ING CENTRAL FIRETUBE AND HEAT EXCHANGER
TUBES. REMOVABLE LINERS UAVE BEEN IN-
SERTED INTO HEAT EXCHANGER TUBES. CHALK
MARK OUT LINE INDICATES TUBES IN PASS
3 AND 4.
>v
-*.
J C* J '•
C. CENTRAL FIRETUBE LOOKING TOWARD BURNER
GUN. AREA OF REFRACTORY LINING IS THE
COMBUSTION CHAMBER.
D. FRONT VIEW OF BOILER WITH BURNER HOUSING
AND ACCESS DOOR REMOVED. SHELF SEPARATES
PASS 4 FROM PASS 3.
-------
- 35 -
FIGURE 6.6
EPA Method 5 Sampling Train
PROBE
REVERSE-TYPE
PITOT TUBE
HEATED AREA
FILTER HOLDER
THERMOMETER
VELOCITY
PRESSURE
GAUGE
CHECK VALVE
VACUUM LINE
ORIFICE
GAUGE
COARSE VALVE
DRY TEST METER
AIR-TIGHT
PUMP
6.5.2 ER&E Collection System
Because of the problems with existing stack sampling trains
and to meet the Company's program needs, ER&E developed a system several
years ago with more analytical capability than "<.od 5. This system
permitted segregation of particulate into several size fractions;
it eliminated the formation of "artificial type particulate" and it
allowed collection of relatively large samples which could be quantitatively
recovered for analysis. Rather than spend considerable time and effort
in hardware development, the best available components were selected
and built into a sampling system. Thus the stack sampling train illustrated
in Figure 6.7 evolved.
The heart of the system is an Andersen eight stage Cascade
Impactor and several Greenberg-Smith, high velocity impingers filled
with silicone oil. These are all mounted in an oven maintained at 400°F.
The high temperature impingers make it possible to obtain a true inventory
of "real particulate" with no sulfuric acid formation or hydrocarbon
condensation. Both can and do occur in cold water impingers to a
different degree than they do in stack plumes. Since particulate loading
is reported on a mass basis, a more accurate inventory is possible with
the ER&E system
-------
FIGURE 6.7
ER&E STACK SAMPLING TRAIN
DRY AIR METERING SYSTEM
OPTIONAL BACK-UP SYSTEM
Ji Jl
s* ~ ~~^y f ~ ~~~SJ '
O tf !
(MICRO L—I
MANOMETER)
CERAMIC LINED OVEN AT 400°F
ICE WATER
TRAP
ORIFICE
BY-PASS
VALVE MAIN
VALVE
DRY ICE
CONDENSER
VAC.
GAUGE
( JL- LEAKPROOF
V J VACUUM PUMP
V—"\
-------
- 37 -
In most of the experiments, a sampling rate of about 0.90
SCFM was used with this system. With the isokinetic sampling
requirement, however, when that amount of flue gas could not be withdrawn,
dry filtered makeup air was provided to the unit upstream of the cascade
impactor. With this provision, it was possible to still sample
isokinetically while maintaining a fixed flow rate through the impactor
and impingers. The makeup air was heated to 400°F and supplied at
atmospheric pressure. To alleviate the problem of wall loss and particle
bounce in the cascade impactor, it was found necessary to have leak-proof
operation and during sampling maintain a constant volumetric flow rate
through the system.
Particle distribution was divided into three (mass) size
ranges: >10 urn, 1-10 Mm and 1 ym. The amount in each of these ranges
was determined mathematically by plotting on logarithmic probability
paper the aerodynamic particle diameter versus cumulative weight percent
of the collected particulate. Aerodynamic diameter was determined
based on a computer, solution of the Ranz-Wong equation^ ' for the
individual stages of the Andersen Impactor. The 50% cut-off points
(050) calculated for the stages were generally in agreement with the
manufacturer's values. At the conditions employed, stage 0 had a
cut-off of approximately 10 urn while stage 5 had a cut-off of roughly
1 ym. On this basis, all material isolated from stages 6 and 7 plus
the impingers made up the submicron particulate fraction.
As further illustrated in Figure 6.7, the ER&E system uses a
dry ice-acetone cold trap at -100°F to insure knock-out of any
volatile compounds. The two impingers outside the oven section, one
empty and the other containing chilled water, remove silicone oil or
other materials entrained by the flue gas. The probe was designed
to obtain even heating over its entire length. To minimize particle
deposition the probe length was kept to a minimum, about 18 inches.
Figures 6.8- 6.12 are photographs of the EPA and ER&E sampling
trains and major components making up the ER&E system. Figure 6.9 and 6.10
illustrate the arrangement used for sampling simultaneously with the
two trains at the ports located 90° apart in the stack. This arrangement
was designated in the factorial program as location 1. Location 2 was
obtained by rotating the position of the'sampling trains.
6.6 Particulate Sampling
Sampling of flue gas from combustion of heavy fuel oil in
the Cleaver Brooks Boiler was carried out in a 12 inch circular stack.
A single sample point located midway on the radius was employed for
sampling particulate. This procedure was experimentally justified
by our previous findings of uniform gas flow and particulate dispersion
across the stack. Velocity profiles across the stack were determined
with a standard 6-point pitot tube traverse (in the north-south
direction). The traverse points were located at the center of each of
-------
- 38 -
FIGURE 6.8 - OVERALL VIEW OF BOILER, STACK SAMPLING SYSTEMS
AND CONTROL MODULES.
-------
- 39 -
FIGURE 6.9 - ARRANGEMENT FOR SIMULTANEOUS OPERATION OF EPA AND ERE STACK
SAMPLING TRAINS. (POSITION 1) EPA TRAIN LOCATED ON LEFT HAND SIDE.
-------
-40-
FIGURE 6.10 - CLOSE-UP VIEW OF PORT HOLE CONFIGURATION FOR SIMULTANEOUS SAMPLING.
-------
-41-
•
FIGURE 6.11 - OVEN ASSEMBLY OF ER&E SYSTEM SHOWING ANDERSEN CASCADE IMPACTOR,
IMPINGER SYSTEM AND MAKEUP AIR LINE.GLASS TUBE UPSTREAM OF IMPACTOR
IS CONNECTED TO PROBE.
-------
- 42 -
FIGURE 6.12 - VOLATILES KNOCKOUT SYSTEM CONNECTED TO ER&E TRAIN FEATURES A
DRY ICE ACETONE COOLED CONDENSER.
-------
-43-
six equal area zones. Representative results are illustrated in
Table 6.6. Normally test conditions (firing rate and excess combustion
air) are such that gas velocities on the order of a few feet/second
are obtained. Hence calculated, flue gas velocity based on combustion
conditions, is used for setting the isokinetic sampling rate. The
agreement between calculated and measured values is quite good.
The data in Table 6.6 also show the uniform flow behavior of the flue
gas in the stack.
TABLE 6.6
Stack Velocity Profile from Boiler
(Fuel, firing rate, 1.1 Ibs./min. 10% excess air)
Traverse
Point
Number
1
2
3
4
5
6
Midpoint
(N/S)
Distance
into Flue
Inches
0.5
1.8
3.5
8.
10,
11.5
6.0
Pitot Tube
AP
Inches H?0
0.011
0.011
0.010
0.010
0.011
0.011
0.010
Stack Temp.
°R
680
700
740
752
750
748
743
Stack Velocity, ft./min.
Measured Calculated
401
407
399
402
421
420
400
368
379
401
407
406
405
402
A second port drilled into the stack at the same height
but 90° removed (east-west direction) permits simultaneous withdrawal
of particulate. Characteristic velocity profiles were developed for
both sampling planes and are tabulated in Table 6.7. The data indicate
a balanced flow across the stack. At the midpoint location,measured
velocities were within 10% of each other and of the calculated velocity.
Pitot tube readings (AP) were measured with an inclined Dwyer micro-
manometer.
-------
- 44 -
TABLE 6.7
Low Level Source Profile
(Fuel firing rate ^0.65 Ibs/min)
Traverse
Point
Number
N/S
1
2
3
4
5
6
Distance
Into Flue
Inches
0.5
1.8
3.5
8.5
10.2
11.5
Pitot Tube
AP
Inches, H20
0.004
0.005
0.004
0.005
0.005
0.008
Stack Temp.
°R
706
712
712
736
736
742
Midpoint 6.0
E/W
1
2
3
4
5
6
0.5
1.8
3.5
8.5
10.2
11.5
Midpoint 6.0
0.005
0.005
0.005
0.005
0.006
0.005
0.008
0.005
Stack Velocity, ft/min.
Measured Calculated
738
730
728
732
734
738
744
734
249
279
250
284
284
360
298
283
282
283
310
283
361
283
265
267
267
276
276
278
277
274
273
275
275
277
279
275
In order to insure that the particulate mass flow rate was
uniform from point to point within the cross section of the stack a
similar type 6-point traverse was also made. The results are summarized
in Table 6.8 and compared with the particulate catch obtained by simply
sampling only at the midpoint in the stack. Both tests were conducted
with marine bunker fuel. On average the mass concentration of particulates
determined by the two procedures differed by only a negligible amount,
about 1%. Comparing size distribution, however, only the mass concentration
of submicron particulates was in agreement. The intermediate and large
size fractions obtained by traversing the stack were almost the reverse
of the distribution from single point sampling. Normally an 18 inch
long sample probe is used to withdraw the flue gas. To accomplish the
traverse, however, a 5 foot probe was employed. With the latter length
-------
-45-
there was considerable deposition of solids on the wall of probe.
Although both large and intermediate size particles were probably
present, the probe sample (by convention) was considered to be
large particulate. This would, of course, bias the results in the
direction observed in the table. Any decrease in the amount of
solids attributed to the >10 ym fraction would produce an equivalent
weight increase in the 1-10 ym fraction and, overall, would place the
total particulate distribution in better agreement with the single
point sample.
TABLE 6.8
Mass Concentration Profile in Stack is Uniform
Particulate Spectrum I II
mg/SCM 6-Point Traverse Single Point Sample
(5 ft. probe) (18 in. probe)
>10 microns 76.07 46.18
1-10 microns 50.72 92.37
<1 micron 126.78 118.03
- Total Mass 253.57 256.58
%A — 1.2
- Wt. % on Fuel 0.32 0.32
Since both the total mass concentration of solids, and
gas velocity, in the stack were steady (no variation with time) and
uniform (no variation from point to point within the cross section)
only one measurement is required for accurate results ' '. While this
measurement may be taken from anywhere within the cross section, a
midpoint sample station has been utilized. It should be noted that
even with an unsteady but uniform source condition, measurements are
needed at only one location. In the later case, however, the measurements
must be taken over an entire cycle, or over as long a time period
as possible, for noncyclic operation. Although the Cleaver Brooks
operation is indeed noncyclic a sampling time of up to three hours
was used in the program.
-------
6. 7 Particulate Isolation Method - General Procedure
Recovery of particulate from the stainless steel liners
inserted into the heat exchanger tubes of the boiler was accomplished
using the same procedure employed for collecting the sampling probe
solids. A water/organic solvent wash was normally all that was required
to remove the solids quantitatively. In several experiments, an
acid rinse of the tubes was employed as a back-up wash. Subsequent
analysis for vanadium in the acid showed only trace quantities.
Particulate from the firetube and the three other passes were kept
segregated and analyzed for vanadium content separately. Prior to
analysis each sample was dried under vacuum for a minimum of A hours,
at a temperature between 250 and 300°F. Analysis of all particulate
samples was carried out by Atomic Absorption Spectroscopy. The
detailed procedure is presented in Appendix 3.
Isolation of the solids in both sampling trains were
accomplished using the following general scheme:
Particulate matter from the various parts of the sampling
train were isolated separately in order to determine net particulate
weight. This was accomplished with water and organic solvent washings.
Solvents were removed by evaporation and all particulate material was
dried under vacuum at 300°F prior to weighing. The isolated solids
were combined into three fractions for chemical analysis (normally
only vanadium) and characterization. In the ER&E train these consisted
of probe material and stage 0 of the impactor; stages 1-5 of the
impactor; stages 6,7 and the impingers. For the EPA Method 5 train
they consisted of probe and cyclone; filter, and impingers.
The detailed procedures used for isolation and characterization
of the particulate are presented in Appendix 2.
6.8 Determination of Vanadium in Particulate
Atomic Absorption was the primary instrumental method used
to determine vanadium content of the particulate in this study. It
has high precision and it is fast. However it does require that the
vanadium be in solution. To accomplish this, two procedures were
initially evaluated.
In the first method, a series of particulate samples held
in porcelain crucibles were ashed at 1450°F overnight. (This is
a modification of the standard method of test for ash from petroleum
product; ASTMD-482). While there was some concern that at this
temperature V^s would volatilize, there has been no evidence to support
this. On the contrary Foster et al'22)f in a study of phase equilibrium.
-------
- 47 -
relationships in the system Na20-SC>3-V205 found that a crucible
containing V2C*5 showed absolutely no weight loss in six hours
at ^1600°F. An identical test showed that a mixture of 20% Na2SC>4 -
80% V2C>5 lost no weight during 27 hours of exposure at 1600°F. It
was further demonstrated by Milan ^ ) that in vacuo ^^65 begins
to dissociate into V2C>4 and 02 at temperatures only slightly above
its melting point of 1274°F. For example, at 1382°F the oxygen
partial pressure in the gas phase corresponded to a melt containing
0.56% V20s while at 1832°F the melt contained 2.75% V204- It was
also noted that the dissociation was reversible provided that the
composition of the melt or condensed phase remained constant.
While V205 may not volatilize during the high temperature
ashing, it does melt and fuse on the interior surfaces of the crucible.
The melt also exhibits a tendency to creep up the side walls increasing
the possibility for direct material loss. Dissolving the fused
vanadium is extremely difficult and time consuming and there is no
real assurance that all of the metal will go into solution. To avoid
these complications, a second treatment labeled "liquid fire" was
also evaluated. In brief, this method employs a digestion of the
particulate sample using a mixture of concentrated acids, HN03, HC104
and I^SO^. In Table 6.9 vanadium analyses run by Atomic Absorption
are compared for the two different ashing procedures. Samples of
boiler deposits were obtained from several preliminary experiments
(runs 33 and 34) made to check the reproducibility of the heat
exchanger tube inserts. The deposits from the four passes in run 34
were ashed using both methods. In run 33 only the samples from passes
3 and 4 were tested in this manner, the other two were run using
only the liquid fire method.
The results indicate a significantly lower vanadium content
from the high temperature ashing procedure. Of the 6 samples run using
both methods, only one showed agreement (9.3% vs. 9.2%), two other
samples were about 10% apart. Where similar samples were subjected
to, high temperature ashing, the results also showed considerable
variation in vanadium content. For the liquid fire treatment, samples
from the two test series generally were in good agreement. As noted
previously, high temperature ashing caused the V205 to fuse on the
crucible wall making complete removal extremely difficult. Any loss
of material in this manner would, of course, lower the vanadium analysis.
-------
- 48 -
TABLE 6.9
Effect of Ashing Method on Vanadium Analysis by Atomic Absorption
Wt. % Vanadium in Sample
Sample Identification Ashing at High Temp.* Liquid Fire
Run 34
Firetube Deposit 4.7 7.8
Pass 2 Deposit 9.3 9.2
Pass 3 Deposit 2.3 6.2
Pass 4 Deposit 3.7 4.7
Run 33
Firetube Deposit - 7.5
Pass 2 Deposit - 8.2
Pass 3 Deposit 3.9 4.3
Pass 4 Deposit 4.3 4.8
*Ashed at 1450°F overnight.
Arc Emission Spectroscopy was also evaluated as an
alternate means of instrumental analysis. The major advantage of
this method is the ability to obtain multi-element analysis on the
same sample. The primary disadvantage is that a much larger
sample is required than with Atomic Absorption. In this study, the
firetube deposit from a third experiment, run 40, was used. Since
there appeared to be pieces of refractory from the combustion chamber
contaminating the sample a simple sieving separation was employed.
To provide a homogenous sample, only material passing through a
-200 mesh standard sieve £v75vtn) was used. This amounted to
roughly 95% of the total. Ten separate samples were analyzed using
the spectrometric procedure. Ten other samples of the sieved material
were analyzed using liquid fire/Atomic Absorption. A comparison of
the results are presented in Table 6.10. The two methods showed good
agreement and both had satisfactory precision.
-------
- 49 -
TABLE 6.10
Comparison of Instrumental Methods of Vanadium Analysis
Emission Spectroscopy
6.8
6.8
6.9
6.7
6.4
6.8
6.8
6.5
6.6
6.9
x 6.7
Atomic Absorption
6.6
6.7
6.6
6.8
6.8
6.5
7.1
6.1
7.0
6.9
6.7
s =
(x-x)2 = 0.73
s = 0.17
= 0.27
= + 2.5%
= + 4.0%
-------
- 50 -
In Table 6.11 the complete multi-elemental analysis
obtained using Emission Spectroscopy has been summarized. The
first determination was made on the fire chamber sample before
sieving. The ash level is significantly higher, which may be
attributed to refractory material rich in silica and probably
some rust particles. After sieving, the ash determinations were
quite uniform. The ratio of Ni to V in the sample is on the same
order as in the residual fuel oil; Na content, however, is slightly
higher.
To complete the analytical procedure, a method was
developed that permitted quantitative extraction of vanadium from
the particulate collected on a standard EPA-type, fiber glass
filter mat. The fiber glass filter was supplied by Western
Precipitation as a part of their stack sampler (Emission Parameter
Analyzer) and was stated to be equivalent to MSA-1106BH. In
practice, the glass filter (125 mm) after being cut into strips
was extracted with a heated solution of 5% nitric acid for about
one hour. The solution was filtered to remove carbonaceous residue
and then analyzed by Atomic Absorption. The vanadium content is
obtained by relating the measured absorbance of the solution to the
absorbance of standard solutions. To insure that the filter itself
did not contain appreciable vanadium several blanks were run. The
results were all negative. In this respect, the filter may be
similar to the spectro grade type A glass fiber filter distributed
by Gelman Instrument Company. Based on a product description
bulletin, for the typical 8" x 10" filter sheet V content is <10 Mg.
Carbonaceous particulate remaining from the extraction
process was similarly analyzed for vanadium. The solids were
first digested using liquid fire and then analyzed by Atomic Absorption.
Vanadium content proved to be negligible, amounting to <0.2% of the
total vanadium associated with the filter particulate.
-------
- 51 -
TABLE 6.11
Elemental Analysis by Emission Spectroscopy
(Run 35, Fire Chamber)
Determination Ash*%
1 35.2
After sieving
thru 200 mesh
2 31.4
3 " " 30.9
4 " " 31.2
5 " " 30.7
6 " " 31.0
7 " " 30.9
8 " 31.1
9 " " 31.3
10 " " 30.9
11 " " 31.0
Fe %
8.5
8.3
8.2
8.3
7.8
7.7
8.2
8.3
8.2
8.1
8.6
Si %
0.4
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
Ni %
0.9
1.1
1.1
1.0
1.0
1.0
1.1
1.1
1.0
1.0
1.1
Na %
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
V %
6.9
6.8
6.8
6.9
6.7
6.4
6.8
6.8
6.5
6.6
6.9
*Ashed at 1450°F
-------
- 52 -
7. RESULTS AND DISCUSSIONS
7.1 Basis for Comparing Vanadium Recovery
This section discusses the results of the factorial test
program to measure vanadium particulate collection efficiency of the
EPA Method 5 sampling train and compare it with the ER&E developed
system. The operating data for the 32 tests constituting this program
are presented in Appendix A Tables 1-10. Complete particulate and
vanadium inventories are presented in Appendix 5 Tables 1-12. This
section also discusses the several experiments run to determine changes
in oxidation state of selected vanadium compounds exposed for several
hours to flue gas at elevated temperatures.
The strategy for establishing vanadium collection efficiency
was based on making a vanadium material balance around the boiler.
The elements of this balance involved establishing the amount of vanadium
entering the boiler from the fuel and then comparing it with the amount
of vanadium collected in the solids deposited in the boiler passes
plus the amount collected in the respective stack sampling train. The
amount of vanadium entering the boiler was easily determined knowing
the fuel firing rate and vanadium analysis of the oil. The amount
deposited in the boiler was based on collection of all deposits from
the tube inserts as discussed in section 6.4. The amount sampled in
the stack, however, represents only a small portion of the total
vanadium being carried in the flue gas leaving the boiler and is
normally expressed in terms of concentration, i.e. mg/SCM, flue gas.
To relate this fraction to the total volume of flue gas produced during
combustion in these experiments, a stoichiometric calculation was
made based on the elemental analysis of the fuel and the excess
combustion air. Since the three test fuels which were used had fairly
similar C/H ratios, the amount of combustion gas produced per pound
of fuel fell within a narrow range; 195-200 SCFDB/lb. fuel at 110% of
stoichiometric air. Using this relationship, it is possible to convert
particulate concentration expressed as mg/SCM into weight percent on
fuel burned, and hence into part per million (ppm), on a fuel basis.
This latter nomenclature is used throughout this report to express
vanadium content in particulates. The concentration of particulate
in flue gas has also been corrected to a standard basis of 3% 02 at 1
atmosphere pressure and 77°F. In addition all gas volumes are reported
on a dry basis (i.e. SCMDB).
7.2 Vanadium Material Balance Around
the Cleaver Brooks Boiler
7.2.1 Total Vanadium Recovery Using All-Venezuelan Resids
This section compares the overall vanadium balance around
the Cleaver Brooks boiler which then provides the basis for comparing
the collection efficiency of the stack sampling systems. The results
-------
- 53 -
are illustrated graphically in Figures 7.1 - 7.3. Vanadium recovery,
which is defined as the amount of vanadium recovered in the boiler
plus the amount of vanadium recovered in the respective stack sampling
systems as a percent of the vanadium input from the fuel, is represented
in bar chart form as a function of fuel type and combustion conditions.
At high firing rate (short combustion chamber residence time,/|o), total
vanadium recovery from the all-Ven (Venezuelan) fuels (F^ and F2) ranged
between 58 wt. % and 104 wt. %. The combined average, however, based
on the 24 runs made with both sampling systems in this block of the
study amounted to 85.3 wt. % + 3.7 (95 percent confidence limit).
This recovery is excellent and probably represents the best that may
be obtained in our system. For example, consider that the vanadium
inventory in the boiler made no allowance for possible V fallout at
the two headers. Additionally vanadium recovery was based on the analysis
of vanadium in a minimum of ten separate particulate samples and
that each of these measurements had an associated precision of + 4.5%.
Comparing the two stack sampling system invididually, it is readily
apparent that Method 5 recovered on average more vanadium, 88.6 wt. %
than the ER&E system, 81.8 wt. %.
At this combustion condition, the amount of vanadium collected
in the boiler was fairly consistent averaging 29.3 wt. %. This
represents about one-third of the total vanadium recovered. The stack
sampling systems had combined recovery of 56.0 wt. %.
At the low firing rate (residence time was increased by a
factor of almost 7), vanadium inventoried in the boiler passes plus the
stack sampling systems was significantly lower. Total vanadium recovered
amounted to 68.1 wt. % + 3.7 (95 percent confidence limit). This
represents a decline of 20% relative to the low firing rate runs
(long residence time). This may be observed in Figure 7.2. Vanadium
recovered in the boiler averaged 22.7 wt. % versus 29.3 wt. % in the
previous series of runs. The reason for the reduction in the amount
of vanadium fallout in the boiler passes is not understood. It may be
speculated that the low volumetric flow rate of the combustion gases at
reduced firing results in a maldistribution of the combustion
products as they go through the passes. Since only one insert
wa= used per pass to collect the vanadium-bearing particulate, any mal-
distribution would easily upset the inventory. These points will be amplified
at greater length in section 7.5, where vanadium recovery in the boiler
is considered in detail. The main point to be noted here, however, is
that a decrease in V recovery in the boiler affects the material balance
and has a disproportionate effect on sample system collection efficiency
because of the difference in bases used for the comparisons.
-------
FIGURE 7.1
TOTAL VANADIUM RECOVERED IN BOILER AND STACK-SHORT RESIDENCE CASE
_l
LU
Z>
LL
•z.
o
^ 100
i—
£
o
!/) 80
Q
"Z.
<
o:
LU
5 ^O
O
CO
LU
CC
^ 40
^^
o
o
LU
CE
^
13
< 20
•^.
<
**
FUEL Fj ALL-VEN. V = 359 FUEL F? ALL-VEN. V = 149
V ppm 230 201 249 180 254 182 EPA 80 96 102 81 106 59
in
Stack 205 190 211 185 232 150 ERE 80 78 77 78 70 70
EPA ERE EPA ERE
X" 89.1 WT.% 83.4
~ s
—
-
—
-
—
—
_
X
^^^m
^
l-l
C3
Q_
CO
n
11.4
—
_^
*-•
z
_J
Q_
CO
LU
rv
CO
LU
CO
CO
^
o.
LU
_J
O
CO
I^B^
10.3
^^^
—
r— 1
—
^•M
^T
1— (
|—
z:
Ou
CO
d.
LU
•zr
»— «
|—
tD
Q_
CO
LU
or
LU
CO
LU
CO
CO
Q_
or
LU
_J
1— 1
0
CO
^^^m
^•^^H
88.2 WT. % 80.3
14.8
—
^•^H
^^^
7.0
~—
^^^
-
—
-
—
_
—
-
i
Ul
1
55 57 68 52 71 79 48 69 75 45 63 74
Sampling Location 12 12
-------
FIGURE 7.2
TOTAL VANADIUM RECOVERED IN BOILER AND STACK-LONG RESIDENCE CASE
1
UJ
ID
O
=5 100
-
o
00 80
0
UJ
1
§ 60
Q
UJ
Cd
UJ
o 40
o
1 1 1
on
:>
^
a
i 20
>
/•>
FUEL FT ALL-VEN. V = 359 FUEL F2 ALL-VEN V = 149
V ppm 189 181 163 188 180* 173 EPA 79 71 84 69 80 88
in
Stack 158 170 116 139 175 126 ERE 43 63 62 49 57 69
EPA ERE EPA ERE
I = 71.2 WT. % 62.4 X" = 76.6 WT. % 62.3
sx = 4.8 9.7 sv = 6.6 6.7
A A
_^
-
—
—
—
™
^^^m
l—t
t—
(T
1
Q.
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eC
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UJ
-
1— 1
CtT
1—
o
z
a.
CO
UJ
of
CC. CO
Ul UJ
_l CO
•— ' CO
o <:
CO CL.
—
—
fm^m
^—^m
—
^^^
__
-^
«
Z
1— 1
Q_
*t
Ul
S
a:
^
_j
a.
CO
Ul
Ul
a: co
Ul Ul
_l CO
•— " CO
o ^c
CQ Q-
^^^B
—
_
"
-
—
™
URun: 5A 56 67 53 72 80 49 70 76 44 62 73
V « v / - j \ ( 1
Sampling Location
-------
- 56 -
The stack sampling system accounted for most of the decrease
(^60%) in vanadium recovery. The combined average for both EPA and ER&E
trains amounted to 45.4 wt. % representing a decline of 19% relative
to recovery at the high firing rate Clo) runs. The ER&E train showed
the lowest recovery of vanadium averaging 39.5 wt. %, exclusive of
the boiler inventory. In contrast, the EPA system averaged 51.2 wt. %.
The difference between the two systems, roughly 25%, represents a
measure of collection inefficiency - the inability to collect fine
particles of vanadium. It is evident that the silicone oil-impingers
of the ER&E system do not collect all the fine vanadium-bearing
particles which pass the last stage of the Andersen Cascade Impactor.
The latter has a size cut-off (d5g) of roughly 0.4 microns. These
fine particles also appear to pass through the dry ice-acetone cooled condenser.
The inefficiency of the Greenberg-Smith type impingers
to collect fines is not attributable to use of only our liquid medium
but appears to be general since the same problem was encountered
with the water impingers used in Method 5. Fine V particles which
are capable of passing through the fiber glass filter (MSA-1106BH)
also pass cleanly through the impingers. This was particularly
apparent at long residence time where at most only a few ppm of
vanadium were ever isolated from the impingers even though up to 20%
more vanadium fines (by weight) appeared to have passed through the
filter. Relative to the combination of Cascade Impactor/impingers,
the filter has a lower particle size cut-off thus it collects more of
the vanadium-bearing submicron particulate.
7.2.2 Erratic Vanadium Recovery
Using Light Arab Residuum
The runs made with the light Arab fuel oil at both high
and low firing rates were characterized by extreme fluctuations in
vanadium recovery and generally poor reproducibility. As illustrated
in Figure 7.3 with the exception of a few run^ most of the inventories
were over 100%. At the high firing rate CT^) recovery in the boiler
ranged from 36 wt. % to 67 wt. % and over the five runs averaged 51.3
wt. %. This was significantly higher than the inventory obtained
with either of the all-Yen fuel oils. Recovery of vanadium in the
stack, based on the combined sampling systems, averaged 71.5 wt. %.
Taken together, the total of boiler and stack inventories equaled
122.8 wt. % + 18.8 (95 percent confidence limit). The confidence limits
are directly proportional to the spread of the data and therefore
serve as a measure of experimental error. The lack of run to run
reproducibility is indicated by the large limits placed around the
average + 18.8%.
-------
- 57 -
At the reduced firing rate ( I i) recovery in the boiler
was somewhat more uniform but still substantially lower than that at
the higher firing rate. Directionally, these results confirm the
difference noted in boiler inventory with the two all-Ven fuels
fired at the respective combustion conditions. The V inventory
from the various passes in the boiler averaged 32.3 wt. % and the stack
sampling systems averaged 73.2 wt. %. Total recovery therefore
equaled 105.5 + 28.4% (95 percent confidence limit). The large
experimental uncertainty is associated in this case with the stack
sampling systems, particularly the inventory made in Run 51 where
recovery amounted to 174% (ER&E system) versus 87.1% (Method 5).
Since results obtained in the tests with light Arab fuel
were so erratic, it served no useful purpose to carry them through
a statistical analysis. Therefore, this test series was not included
in the overall analysis of variance (ANOVA).
The very low vanadium content in the particulate is
probably the main cause for the large fluctuations observed in these
runs. Since V inventory in these tests was based on the sum of the
individual V analyses of a large number of different samples,
handling and/or analytical errors were probably compounded. For
example, tests conducted at high firing rates (short residence time),
showed the largest absolute variation in the amount of V collected.
Solids deposited in the boiler varied by as much as 12 ppm (on fuel)
or roughly 30% of total V input from the fuel. In the stack, the
range was about 15 ppm. At this combustion condition, a large amount
of carbonaceous particulate was emitted; the boiler and stack solids
totaled 361 mg/SCM, equivalent to 0.46 wt. % on fuel. Included in
this total was the fuel ash which accounted for about 0.01 wt. % or
roughly 2% of the particulate weight. Since the carbonaceous particles
each contain some ash, the concentration of vanadium in the particulate
was low (i.e. the V content in the solids averaged about 1.0 wt. %).
At long residence time, 79% of the carbonaceous solids
were consumed. This resulted in a particulate inventory of 77 mg/SCM;
equivalent to 0.10 wt. % on fuel. The concentration of ash in the
particulate was increased to 10%. The average vanadium content in the
solids amounted to 7.8 wt. % compared to 1.0 wt. % at the short
residence time. While the vanadium content was higher, the weight of
solids collected was quite low. This latter proved to be a limiting
factor, affecting sensitivity of the analtytical method. These data
are summarized in Table 7.1.
Comparing the stack particulate inventory made with the
entire ER&E system but only the front half of the Method 5, there
was excllent agreement. The largest difference between the two sampling
trains occurred at the high firing rate (short residence) and amounted
to 16 mg/SCM or about 7% on total weight. At the low firing rate
-------
FIGURE 7.3
TOTAL VANADIUM RECOVERED-LIGHT ARAB FUEL
u_
z
o
o
100-
80-
o
CQ
Qi
UJ
>
O
o
UJ
O
60-
40-
20 -
0
—
Run:
ocatior
^^^m
»— 1
1— 1
Q.
s:
D-
UJ
<~0
n
• — i
•K
i
z
1 — 1
a.
to
UJ
a:
UJ
to
UJ
to
to
Q.
UJ
_l
t— «
0
CO
IT)
CO
CO
I— 1
*
CVJ
1 — 1
*
—
10
f— 1
I-H
*
F
uel V input = 39 ppm
SHORT RESIDENCE//
^^^m
47 78 50 58 65
i 1
\ /
V
2
LONG RESIDENCE/
EPA SAMPLING TRAIN |
| ERE SAMPLING TRAIN |
UJ
to
2
C£
UJ
»— i
O
CQ
^H^M
J
1
—
»—)
-K
•^^
^^^H
r
r
i
0
if
sx
~N^/
1
sr
sx
•M^HI
EPA ERE
111.3 134.4
26.6 23.7
94.0 116.9
11.0 34.9"
60 77 51 59 66
1
\ /
2
:
—
Ul
00
-------
- 59 -
(long residence) where particulate emissions were lower, a relative
difference of about 4% (1 mg/SCM) was obtained.
The back half or impinger part of the Method 5 train was
also found to contain solids. However, it was determined that this
material, consisting mostly of sulfate, was an artifact of the chilled
water impingers. In runs made with the two all-Ven fuels, the same
type solids ,in varying amounts were also isolated from the water
impingers. Since these solids were not real particulate emitted
during combustion of fuel oil, they were not counted in the total
inventory. A more detailed discussion of the nature of these
artificial particulates is presented in section 7.7.
7.2.3 Statistical Analysis to Compare
Vanadium Recovery
An analysis of variance (ANOVA) was made to compare
the influence of stack sampling system (S) fuel oil (F), combustion
chamber residence time (T), and port location in stack (L), on
total vanadium recovery. The ANOVA which is presented in Table 7.2
indicates that fuel type and sample port location are not statistically
significant and therefore do not affect vanadium recovery. The main
effects, as indicated by the F ratio in excess of the critical table
value P(F >5.57) = 0.05 at fy-^, $32 (degrees of freedom) are residence
time and sampling system. Since there were no significant interactions,
vanadium recovery may simply be represented as a,function of these
two variables. The effect of residence time ( T) is to reduce vanadium
recovery by 20% and this appears to be independent of the tested
levels of the other variables (none of the interactions T-F, T-S,
T'F-S, T-L, T-S-L, T-F-S-L are large). The effect of sampling
system(S) is to reduce vanadium recovery by 11% (81.3 wt. % to 72.1 wt. %)
and this also appears to be independent of the tested levels of the
other variables (none of the interactions TtS, F«S, T-F-S, S-L,
T-S-L, F-L-S, T-F-S-L are large). Residence time, with one degree of
freedom, accounted for 42.6% of the total experimental variation
(sum of squares/total error). Residence time ('T ) and sampling system (S)
combined,with two degrees of freedom, accounted for more than half
of the variation, 54.8%. Pure experimental error (residual effect)
estimated with 32 degrees of freedom amounted to 35.1% of the total
variation. The remainder was associated with the interaction effects
which were very minor, amounting to 10.1% of the total calculated
experimental variation.
Pooling the two nonsignificant variables, fuel and port
location, a two way analysis of variance was made to obtain a better
estimate of experimental precision. The new variance with 44 degrees
of freedom was 83.31 whereas the previous variance had 32 degrees of
-------
TABLE 7.1
Particulate Distribution
• Boiler Solids
• Stack Particulate
- ER&E Train
l-10ym
-------
- 61 -
freedom and was equal to 90.61. The twelve additional degrees of
freedom permitted by folding over the factorial design gave about
an 8% improvement in estimating the experimental precision.
The relative variance (percent of the total experimental
variance of 83.31) associated with vanadium recovery in the boiler
passes amounted to 23%, while the variance associated with vanadium
recovery in the stack (both sampling systems) accounted for 59%. The
remainder, 18%, was the unexplained variance and represented the
sum of all unaccountable experimental errors, i.e. errors attributed
to sampling, handling and V analysis. It may be noted that the stack
measurement part of the experiment had the lowest precision. However,
this represents the totality of all treatments, a large part of this
was probably associated with the decrease in ER&E system collection
efficiency particularly at the low firing rate (/Tl).
The highest vanadium recovery was obtained using the
EPA Method 5 train at short combustion residence time. Total recovery
as summarized in Table 7.3 averaged 88.6 wt. % + 5.2 (95 percent
confidence limit). This value which was based on an overall vanadium
material balance conducted around the boiler probably represents close
to quantitative recovery of V considering the number of measurements
that were involved and the potential inaccuracies. In comparison
vanadium recovery based on the ER&E stack sampling system was lower
by 7.7% and averaged 81.8 wt. % + 5.2 (95 percent confidence limit).
The difference in averaged recovery between the two sampling systems
was not found to be significant at the 95 percent level using
"Student's t-test". However, when tested at the 90 percent level the
difference was significant. Overall, the two sampling trains gave
acceptable vanadium recovery.
At long combustion chamber residence time, vanadium recovery
measured by either stack sampling system was significantly lower, however,
the decrease obtained in the ER&E system was much greater. Based on
Method 5, total V recovery went from 88.6 wt. % to 73.9 wt. % + 5.2
(95 percent confidence limit) representing a relative decrease of 16.6%
Based on the ER&E system, recovery was decreased by 24%, to a level of
52.3 wt. %. Comparing the two sampling systems the change in vanadium
recovery amounted to 16%.
7.2.4 Vanadium-Bearing Particulate Inventory
Although the amount of vanadium collected by the
sampling systems was different, the total amount of particulate
collected was similar and well within experimental error. For the
high ash (V = 359 ppm) all-Ven fuel oil (Fj). presented in Table 7.4
at short residence time, total particulate emissions inventoried in the
ER&E stack sampling system amounted to 305 mg/SCM equivalent to 0.39 wt. %
on fuel oil. The Method 5 train collected 301 mg/SCM equivalent to
0.38 wt. % on fuel oil. The vanadium content in the total particulate
-------
TABLE 7.2
LEVELS OF FACTORS
ANALYSIS OF VARIANCE - TOTAL VANADIUM
RECOVERY IN BOILER AND STACK
F f'p- 2 ri><:
, £PA 5££ t *^?"
U ,«.«.«• ^ ^
D / 1, 7 .T^
^^ f.J"«e. (
•J-5~J
S.S1
S"-$7
- g-j
'
£'57
5.60334
6.45336 * / sy 1 -r -.
1.84081 CJPVC.' ^^''•L "r£-&'OP*%£ /!*/'
0 18749 i *- y
90'61 - s' AM ^Jtl^ly
-------
- 63 -
TABLE 7.3
TOTAL VANADIUM RECOVERY AS AFFECTED BY STACK SAMPLING SYSTEM
AND COMBUSTION CHAMBER RESIDENCE TIME
EPA Method 5
ER&E Train
t Test
/
/
N
88.6 wt. %
(Short \J (83.4 - 93.8 wt.
Residence/1
V
Time
/
P (.95)
81.8 wt. %
(76.6 - 87.0 wt. H
P (-95)
t calcd. =1.54
0 = 44
At 95%,Critical Table
Value =1.96
Difference not significant
At 90% difference is
significant
73.9 wt. %
(68.7 - 79.1 wt.
P (-95)
62.3 wt. %
(57.1 - 67.5 wt. %)
P (-95)
t calcd = 4.41
0 = 44
At 95%,Critical Table
Value = 1.96
Difference is significant
NOTE:
Experiment variance; = s = 83.31
Standard error = s = f-3»~. = 2.63
X I - \S
95 percent confidence interval = t (.025,44)= 1.96 x 2.63 + X
Probability -5.2 <_ X <_ + 5.2 = 0.95
-------
TABLE 7.4
Particulate Distribution
• Boiler Solids
• Stack Particulate
- ERE Train
>10um
1-1OMm
Total
- EPA Train
Probe and Cyclone
Filter
Water Impingers
Total
AVERAGE PARTICULATE AND VANADIUM INVENTORY
.HIGH ASH ALL VENEZUELAN FUEL OIL (Fi)
Short Residence Time
Particulate
mg/SCM
222
104
145
56
305
184
117
(301)
8
309
Vanadium
Analysis
wt. %
3.68
1.81
5.36
10.09
2.43
10.67
Vanadium
Content
ppm (on fuel)
104
24
99
72
195
57
159
(216)
Trace
216
Long Residence Time
Particulate
mg/SCM
61
3
12
48
63
7
65
(72)
5
77
Vanadium
Analysis
wt. %
9.91
5.23
15.04
19.95
3.36
21.26
Vanadium
Content
ppm (on fuel)
77
2
23
122
147
3
176
(179)
Trace
179
NOTES;
(1) All data corrected to 3% 0 .
(2) Results from individual runs summarized in Tables 1-4 , Appendix 5.
-------
- 65 -
collected by the ER&E train averaged 5.02 wt. % compared to 5.63
wt. % in Method 5. On an absolute basis, this difference amounted
to 21 ppm V and was mainly associated with the filter catch. Typically the
smallest sized particulate have the highest vanadium contents. In this
case, however, the particulate on the filter had a higher V concentration than
particulate isolated in the submicron size range, 10.67 wt. % versus
10.09 wt. % V. While this may appear paradoxical, the situation could
arise if the filter collected finer submicron particles than the
impingers, i.e., the filter had a much lower size range cut-off. If
it is assumed that the missing 21 ppm of vanadium (as V205> passed
through the ER&E system, then the difference in particulate inventory
necessary to account for it would amount to about 3 mg/SCM. Even
if the V content in the missing particulate was 10.09 wt. %, the
difference would amount to only about 17 mg/SCM or about 7% on the
total inventory. This magnitude is well within the expected experimental
variation and would not be detected.
Some insight into the nature of particulate emissions was
obtained in previous company sponsored studies. Table 7.5 shows the
C, N and ash composition of the particulate in the different size
ranges.
TABLE 7.5
PARTICULATE COMPOSITION INFLUENCED BY SIZE
(High Sulfur Fuel Oil)
Particulate Analysis, wt. %
Fraction
>10 micron
1-10 micron
<1 micron
The largest particles, mostly cenospheres, have a high
carbon content, 79.4%, and a relatively low ash content, about 10%. The
intermediate size range has a slightly lower carbon content and a somewhat
higher ash content, about 18%. The submicron particles have a relatively
low carbon content, only 30.1% and a much higher ash content, about 57%.
Carbon
79.4
70.7
30.1
Nitrogen
1.8
1.2
0.3
Inorganic Ash
10.1
18.1
57.1
-------
- 66 -
Analysis of the ash residue from the three size ranges,
Table 7.6 indicated that a large part of each was vanadium. Expressed
relative to fuel oil the vanadium oxide in the particulate ranged
from as little 24 ppm in the very large particles to 137 ppm in the
smallest particles.
TABLE 7.6
DISTRIBUTION OF V20s IN PARTICULATE ASH
V2°5
Na00
Wt. % in Ash Fraction
1-10 <]
41.6
1.7
63.7
1.8
58.2
3.4
Wt. % on Fuel in Size Range
1-10 <1
.0024
.0002
0.0110
.0003
.0137
.0008
At long residence time, the total difference in particulate
inventory between the two sampling systems amounted to about 14%, which
on an absolute basis was only 9 mg/SCM. The ER&E system collected
63 mg/SCM of particulate,(0.08 wt. % on fuel)versus 72 mg/SCM (0.09
wt. % on fuel)for Method 5. The net effect of increased residence time
is that most of the carbonaceous residues burn-out, so that the total
weight of particulate is substantially reduced. Additionally, the
size distribution of these particles is shifted toward the submicron
range. Ash material, mainly vanadium oxide, which would normally have
been distributed among the carbonaceous particulate is probably
vaporized into the combustion gas stream, then recondenses in the cooler
part of the boiler as submicron particles. As may be noted in Table 7.4,
about 83% of the vanadium particles collected by the ER&E sampling system
were in the submicron size range compared to 37% at short residence time.
This shift in size distribution is also borne out by the Method 5 train.
Vanadium collected on the glass filter (<5 micron) amounted to 74% at
short residence time compared to 98% at long residence time. The
concentration of vanadium in the fineparticulate was also substantially
higher than in the previous runs at/YQ. Submicron particulate
collected in the silicone oil impingers had a vanadium content of
20 wt. % and those collected on the fiber glass filter had a V content
of 21.3 wt. % versus roughly 10.5 wt. %. Since the concentration of
-------
-67-
V in the particulate is high, the loss of only a small amount of these
fine particles may have a critical effect on the overall V recovery.
For example, the difference between sampling system particulate inventory
amounted to 9 mg/SCM or on a relative basis about 14%. If the
vanadium content in this amount of particulate was roughly 27 wt. %,
which is not much higher than the concentration actually assayed, it
would account for the 34 ppm difference obtained in vanadium inventory.
On the other hand in the Method 5 sampling system, if the fines which
passed through the filter were V205, an increase in total particulate
inventory of about 10% would be sufficient to bring vanadium recovery
up to 90%.
In tests made with the intermediate ash, all-Ven fuel oil
(F2> summarized in Table 7.7, total particulate collected by Method 5
(front half only) and ER&E stack sampling trains also showed good
agreement. Directionally the results were very similar to those
obtained with fuel F^. At short residence time particulate inventories
were identical, 127 mg/SCM versus 128 mg/SCM, equivalent to 0.16 wt. %
on fuel oil. However, the average vanadium content was higher in the
solid collected by Method 5, 4.64 wt. % versus 5.34 wt. %. This
difference on an absolute basis amounted to 12 ppm V or roughly 15%
of the total inventoried in the stack. Again, it may be concluded
that the loss of vanadium from the ER&E train was associated with
the passage of a relatively small amount of fine, vanadium-bearing
particulate out the impingers. This situation also occurred in the
runs made at long residence time. However, in this case, it was
further aggravated by the shift in size distribution to nearly all
submicron particles and the higher vanadium content in these fines.
The EPA system collected about 13% more particulate, which on an
absolute basis amounted to 5 mg/SCM. The vanadium content in the
particulate was also higher averaging 14.93 wt. % versus 12.43 wt. %.
7.2.5 Size Distribution of
Vanadium-Bearing Particulates
The size distribution of the vanadium-bearing particulate
which deposited in the boiler was also influenced by combustion
conditions. At short residence time, the vanadium content in these
deposits averaged 3.9 wt. %. Based on a similar concentration in the
stack, 3.3 wt. %, the particulate were predominantly in the 1-10 micron
size range. At long residence time, the boiler deposits averaged
7.6 wt. %, indicating a mix of submicron and 1-10 micron particles.
The size distribution of particulate in the stack as
previously noted was significantly altered by combustion conditions.
The results which have been determined with the ER&E sampling train are
summarized in Table 7.8. At short residence time, irrespective of
fuels, approximately 29% of the total particulate weight was emitted
as cenospheres (>10 microns) while 76% of the particulate was emitted
in the size range >1 micron. Submicron particulate amounted to 24% of
the emissions. At the increased residence time, combustion of the
-------
TABLE 7.7
Particulate Distribution
• Boiler Solids
• Stack Particulate
- ERE Train
>10ym
1-lOym
Total
- EPA Train
Probe and Cyclone
Filter
Water Impingers-
Total
AVERAGE PARTICULATE AND VANADIUM INVENTORY
INTERMEDIATE ASH ALL VENEZUELAN, FUEL OIL (F2)
Short
Particulate
Mg/SCM
89
30
57
40
127
51
73
(128)
13
141
Residence
Vanadium
Analysis
wt. %
3.88
1.57
3.30
8.83
2.00
7.96
Time
Vanadium
Content
ppm (on fuel)
44
6
24
45
75
13
74
(87)
Trace
87
Long
Particulate
Mg/SCM
37
4
7
25
36
5
36
(41)
10
51
Residence
Vanadium
Analysis
wt. %
7.64
1.96
5.61
16.01
1.57
16.79
Time
Vanadium
Content
ppm (on fuel)
36
1
5 i
51 ON
57
i
1
77
(78)
Trace
78
NOTES;
(1) All data corrected to 3% 0-.
(2) Results from individual runs summarized in Tables 5-8, Appendix 5.
-------
- 69 -
TABLE 7.8
RELATIVE SIZE DISTRIBUTION OF STACK PARTICULATE
NOTE: Based on Data From ER&E Sampling System
Size Distribution
>10Mm
l-10ym
10ym
1-lOym
100%
Fuel
~ Intermediate Ash, All-Ven
24
45
31
8
32
60
11
19
70
2
9
89
100%
100%
100%
Fuel FT - Low Ash, Light Arab
>10ym
1-lOum
28
49
23
100%
13
28
59
100%
11
18
71
100%
3
3
94
100%
-------
- 70 -
carbonaceous residues was facilitated and resulted in a pronounced
shift in particle size distribution to the submicron range. At
this condition, roughly 72% of the total particulate were emitted
as submicrons compared to 24% in the previous run. The amount of
cenospheres was decreased by almost 70% and now accounted for
only 9% of the total weight. As cenosphere and cenosphere derived-
residue burn out the volatile ash material present in these particles,
particularly vanadium, is liberated into the gas stream to condense
in the cooler part of the boiler as fine particles. Only 2% of
the vanadium remained associated with these large particles compared
to 11% at the short residence time. Approximately 12% of the vanadium
was in >1 micron particles while 88% was in the submicron particles.
From the preceding it may be concluded that at the long residence
time, sampling system collection efficiency is influenced by the
presence of a large amount of submicron particles.
7.3 Sampling System Collection Efficiency
Vanadium collection efficiency as used in this report
is the ratio of the amount of vanadium collected in the stack
sampling train divided by the amount of vanadium in the fuel mjLnus
the amount of vanadium that deposited in the boiler
Thus, it is apparent that for a particular level of vanadium recovery,
the calculated collection efficiency will be lower because of the
different basis used. Collection efficiency will be equal to 100%
only if all of the vanadium introduced into the boiler from the
fuel is recovered. Any vanadium which is not accounted for in the
deposits from the passes is assumed to enter the stack. If the
amount of vanadium inventoried by the stack sampling is insufficient
to close the balance then the difference is attributed to the
inefficiency of the collection system for collecting V fines. In this
study, the highest vanadium recovery averaged 88.6 wt. % using the
Method 5 train at short residence time. However, this probably
represents the best material balance obtainable with the resources
employed; primarily the boiler tube inserts. Consequently, there is
little direct data to indicate where the loss of vanadium, in this
particular case 11.4% of the input, has occurred. Assigning it
entirely to the sampling system as has been done in Table 7.9, the
resulting vanadium collection efficiency of 83.9% represents the
minimum value for Method 5. If the entire loss of vanadium occurred
in the boiler passes then collection efficiency of Method 5 would
naturally amount to 100% and the other values could be scaled up
accordingly. The change in collection efficiency from 83.9% with
Method 5 to 74.3% with the ER&E train is a real effect. This
difference is attributed to the inability of the hot silicone oil
impingers to collect all of the very fine vanadium particles.
-------
- 71 -
At long combustion chamber residence time, the collection
efficiency of Method 5 decreased from 83.9% to 66.2%, roughly
a change of 21%. However of this total, more than half, 14%, was
related to a lower vanadium inventory in the boiler passes. If the
same amount of vanadium had been deposited in the passes at both
residence times,sampling system collection efficiency would be
equal to 72.4%. The collection efficiency of the ER&E system relative
to Method 5 decreased by an additional 23% to a level of 51.1%. At
short residence time, the relative loss in efficiency was only 11%.
The steeper decline in ER&E stack train performance at long residence
time is associated with the emissions of significantly smaller
vanadium particles which pass unchecked through the hot oil impingers.
In contrast, the fiber glass filter used in Method 5 retains more of
these fine particles. Vanadium fines which do pass through the filter
are not collected in the water impingers again indicating the inefficiency
of this type of system to collect submicrons.
To sum up, the fiber glass filter used in Method 5 train
has a significantly lower particle size cut-off than the high velocity
type Greenberg Smith impingers. With this type of filter, Method 5
collection efficiency for vanadium particles in combustion-produced
flue gas will amount to, at the very least, 66-84%. Large boilers
which normally have bigger combustion chambers and therefore longer
combustion chamber residence time will tend toward the lower
vanadium collection efficiency.
7.4 Vanadium Input - Fuel Analysis
The first element of the material balance involved establishing
the vanadium content of the three fuel oils. Although each fuel
was drawn from a bulk lot, they were segregated and stored in 55 gallon
drums. Each test was run with a new drum of fuel oil. Thus over the
course of the program 36 drums of oil were sampled and analyzed for
vanadium content prior to use. As illustrated in Table 7.10 the all-Ven,
high ash fuel designated F-^ had a vanadium content averaging 359 ppm
+ 8.4 (95 percent confidence limit) which expressed as V^Oij accounted
for about 70% of the fuel ash. Nickel podium and iron were the other
components in the ash. The intermediate ash all-Ven fuel oil, F2, had
a vanadium content averaging 149 ppm + 4.2 (95 percent confidence limit).
Expressed as V205, it accounted for about 66% of the ash weight. The
light Arab low ash fuel designated F3 had an average vanadium content
of 39 ppm + 2.0 (95 percent confidence limit) accounting for about 70%
of the ash, on the basis of V20^. Relative analytical precision was
about the same, roughly 4% for the vanadium analysis in the three fuels.
-------
- 72 -
TABLE 7.9
SAMPLING SYSTEM COLLECTION EFFICIENCY
EPA Method 5
ER&E
Short Residence
Time,
83.9%
74.3%
Long Residence
Time
66.2%
51.1%
As the precision of these analyses represented drum to
drum variation only, fuel samples were drawn periodically from one
drum and analyzed. This procedure served to test the hypothesis
that the drum samples came from the same population and therefore
the average value was representative of the vanadium content in the
test fuel lot. The mean, as shown in Table 7.11, for the 11 vanadium
determinations was 351 ppm with a standard deviation of 23 ppm or
on a relative basis, 6.5%. Thus from a statistical standpoint the
value of 359 ppm representing the average of all drums adequately
describes the vanadium content of test fuel F]_. By inference, the
same holds true for fuels F2 and F3. The vanadium content of the
fuel oil multiplied by the fuel consumption gives the vanadium input.
-------
- 73 -
TABLE 7.10
Drum to Drum Variation of Vanadium Analysis
Mean = x
s
Std. dev. = x
Std. Error =
-------
- 74 -
TABLE 7.11
Variation of Samples Within A Drum of All-Ven Fuel Oil
Date: 8/21 9/23 10/24 11/27 12/31 1/30 1/2/20 2/28 3/28 4/30 5/30
V,ppm: 330 300 330 373 350 358 365 353 360 380 360
*11 = 350'8 PPm
sx = 22.84
*% = 6.9
Relative std. dev. =6.5%
-------
- 75 -
7.5 Vanadium Recovery in the Boiler
7.5.1 Preliminary Tests - Evaluation of Boiler
Pass Tube Insers
Several preliminary runs were made to determine how well
the heat exchanger tube inserts worked and if replication of particulate
inventory was possible. Two removable tube inserts were randomly
placed in each of the three heat exchanger passes. Tests were then
made using firing rates of 1 Ib./min. and 2 Ibs./min. at 10% excess
combustion air. Results are presented in Table 7.12 and indicate that
the inserts provide a reliable measure of particulate fallout in the
boiler. To facilitate comparisons, the weight of particulate was
divided by the calculated combustion gas volume CVL95 SCFDB/lb. fuel)
then multiplied by the total number of tubes in the pass to give
mg/SCMDB (corrected to 3% 02). Runs 33 and 34 may be directly
compared since a similar firing rate, 1 Ib./min. was used.
The difference between tube inventories in the same pass
ranged from less than 1% to as much as 13%. However, for all tests
the average was 5%. Run to run variation of fallout averaged about 9%.
This somewhat higher difference was most likely associated with some
facet of boiler operation (i.e. slightly different firing rates, stability,
etc.) rather than handling errors. The major variation in particulate
fallout between runs occurred in pass 2. This pass had the most
surface area and therefore was prone to fluctuations or changes in
boiler operation. For example, comparing Run 33 with Run 35, the fuel
firing rate was increased from 1 to 2 Ibs./min. The largest change
in particulate was in pass 2 where the amount of fallout tripled in
weight.
In Run 35, the effect on particulate fallout on changing
combustion chamber residence time may be noted. As a result of
increasing the fuel firing rate and therefore decreasing residence
time, the amount of solids deposited in the passes was doubled. Since
burnout of a carbonaceous particle in the combustion zone of a boiler
is believed to take place by diffusion of oxygen to the particles'
surface - a fairly slow process, shortening residence time increases
the probability that the particle will escape unburned.
-------
TABLE 7.12
VARIATION OF PARTICULATE DISTRIBUTION IN BOILERfpRELIMINARY TESTJ
Pass
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Run 33
Total Particulate/Pass
mg/SCM*
A B
29.2
18.0
11.7
99.0
40.1
31.4
18.1
12.9
102.5
Run 34
Total Particulate/Pass
mg/SCM*
A B
35.2
21.0
12.0
110.5
Run 35
Total Particulate/Pass
mg/SCM*
A B
42 .3
36.9 106.3
Sample Contaminated 36.9
12.1 __1±1
226.7
82.2
105.0
32.3
1.4
220.9
Fuel Consumption; Lb.
- Inserts in Place
- Total Run
Firing Rate, Lbs./Min.
194.50
320.50
1
198.25
305.75
1
373.50
556.25
2
*Corrected to 3% 0,
-------
- 77 -
Residence time also had considerable influence on the
concentration and distribution of vanadium in the boiler solids.
For a particular combustion condition, as shown in Table 7.13, there
was little variation between runs in vanadium content of particulate
from the same pass. On average the difference amounted to less than
5%. This is on the same order as the analytical precision for the
Atomic Absorption method. Since somewhat more variation between
runs was found in the absolute weight of particulate, the amount of
vanadium collected also varied. In these preliminary trials the
difference in the total amount of V inventory between runs was on
the order of 20%. Considering the relatively small amount of solids
collected, this difference is about as good as can be expected.
Increased combustion chamber residence time serves to
promote burnout of cenospheres. Given sufficient residence time,
all of the carbonaceous matter in the particle would be consumed
and only ash (vanadium particles) would be emitted into the combustion
product gas stream. With short residence time, i.e., high firing
rate, most of the ash is retained in the cenosphere. Thus the
deposits in the boiler, depending upon combustion conditions should
have distinct vanadium contents. In runs 35 and 36, the solids
isolated in the boiler averaged 3.54 and 3.31 wt. % V, respectively.
Almost all the vanadium fallout,99%,was in the first three passes.
In Runs 33 and 34, fallout in the first three passes accounted for 90%
of the total deposits but 78% was in the first two passes alone.
The vanadium content in these solids averaged 7.07 and 7.64 wt. %
respectively or about double the previous runs. These results are
summarized in Table 7.13.
Some idea of the nature of the deposits in the various boiler
passes were obtained from their elemental analysis. In Table 7.14
C, H, N and S analysis of deposits from Run 33 are presented.
The solids from pass 1 and 2 which had the highest vanadium
content roughly 8% (ash) also had the lowest carbon content, averaging
about 53%. In passes 3 and 4 when vanadium content averaged about 4.5
wt. % (lower ash) carbon content was considerably higher and amounted
to 74%. While a sulfur analysis is presented, most of the sulfur
is believed to be associated with the ash as sulfate. Sulfuric acid
would not be a factor since the high temperature in the passes
would preclude its formation. Sulfur content appears highest in
the solids containing the least amount of carbon, therefore, the
most ash.
-------
- 78 _
TABLE 7.13
VARIATION OF VANADIUM DISTRIBUTION IN BOILER - PRELIMINARY TESTS
(ALL-VEN HIGH ASH RESID FUEL)
FUEL FIRING RATE 1 Ib./MIN
Run 33 Run 34
Particulate Inventory Particulate Inventory
Boiler Deposits mg/SCM Wt.%V ppm V mg/SCM Wt.% V ppm V
Pass 1 (firetube) 40 7.5 38 42 7.8 42
Pass 2 38 8.2 32 36 9.2 42
Pass 3 18 4.3 11 21 6.2 17
Pass 4 12 4.8 9 12 4.7 7_
Total 100 90 111 108
t FUEL FIRING RATE 2 LBS./MIN.
Boiler Deposits
Run 35 Run 36
Pass 1 (firetube) 82 3.0 31 75 2.7 26
Pass 2 106 4.0 54 93 3.8 45
Pass 3 35 3.3 15 27 3.1 11
Pass 4 1 6.6 1 2 5.9 1
Total 224 101 197 83
TABLE 7.14
PARTIAL ELEMENTAL COMPOSITION OF BOILER SOLIDS
(FUEL FIRING RATE 1 LB./MIN. - RUN 33)
Elemental Composition
Boiler Deposits C H N S
Pass 1 (firetube) 47.1 0.8 0.9 10.2
Pass 2 58.8 0.8 1.0 8.0
Pass 3 76.8 0.7 1.2 5.9
Pass 4 72.2 0.8 1.0 7.0
-------
- 79 -
7.5.2 Factorial Program Results - Vanadium Recovery
at High Firing Rate
Once it was established that the tube inserts provide
a reasonably consistent measure of vanadium particulate fallout in
the boiler, the factorial experimental program was conducted. In
each run, total vanadium was determined in the boiler solids and
in each stack sampling system. In Figures 7.4 - 7.5 bar
charts graphically illustrate vanadium recovery in the four passes
(V recovered in boiler solids as a percent of V input from fuel)
as a function of fuel type and combustion chamber residence time.
Figure 7.4 summarizes the tests conducted at short residence time
(r\ o)> i-e. 2 Ibs./min. fuel firing rate. It shows that there was
no difference in percent recovery of vanadium between the high and
intermediate ash all-Yen fuels. The absolute amount in the deposits,
however, differed considerably because of the difference in the
amount of V in the fuel oils. Over the twelve tests, recovery in
the boiler tubes averaged 29.3 wt. %. Run to run fluctuations were
minimal, amounting to less than 30 ppm. In contrast, vanadium
recovery in the five runs made with the low ash, light Arab fuel oil
averaged 51.3 wt. % of the V in the fuel and showed considerable
variation between runs. This increase in variability was further
indicated by the large standard deviation. In this case standard
statistical techniques, i.e., F-Ratio and Bartlett's chi square tests
were used to compare variability of the three groups of runs. It was
established that the variances associated with the means from the
all-Ven fuel oils were from the same population distribution but were
different from the variance obtained in the light Arab runs.
A primary cause for 'the lack of repeatability in tests
conducted with light Arab fuel oil was the low concentration of
vanadium in the boiler solids. The V content as shown in Table 5.15
ranged from as little as a few tenths of one percent up to 2.5 wt. %
but averaged about 1.0 wt. %. On the other hand, the V content of
solids from the high ash all-Ven ranged from 2 wt. % to 10 wt. %,
averaging 3.7 wt. %. Those from the intermediate ash all-Ven fuel
varied from 2.0 wt. % to 5.5 wt. %, averaging 3.9 wt. %.
There was more particulate deposition in the boiler passes
with light Arab fuel oil even though it was lower in asphaltenes
(hexane insolubles) than the all-Ven fuel ^2- Tne all-Ven fuel F^,
had the highest asphaltene content and produced the most solid emissions.
The propensity of heavy oil to form carbonaceous solids is directly
-------
CO
UJ
CO
CO
cc.
o
CO
o:
LU
>
o
o
LU
Cf.
FIGURE 7.4
VANADIUM RECOVERY IN BOILER - SHORT RESIDENCE CASE
y 60
50
40
30
20
10
-
FUEL Fi ALL-VEN.
HIGH ASH, V = 359
Epm V 108 91 107 105 120 94
FUEL F2 ALL-VEN.
MED. ASH, V = 149
43 57 51 32 40 43
F
L
20
Mean = X" = 29.0 WT. % I = 29.7 WT. %
Std. Dev. = s = 2.9 s = 5.9
X X
—
—
MMH
P4
P3
P2
^^mm
PI
m^mm
^^mt
••^^
^^^m
_^_
««
^M^M
^•i^
^^^M
^—
^^^
P4
P3
P2
•^M
PI
^^•i
^•^H
^^M
^••M
—
•^•H
^•^^
^i^^
^^^m
P4
P3
P2
PI
rer
)W /
7F
^^^M
F3 LT. ARAB
SH, V = 39
14
•^IMM
•^^^
23
^^^^
^^^^
17
-
X" = 51.3'
s = 12.1
X
^^^M
•^^H
:
—
—
00
o
Run: 55 57 68 52 71 79
48 69 75 45 63 74
47 78 50 58 65
-------
- 81 -
related to its asphaltene content. However, this relationship
may be modified by the type and molecular weight range of these
complex multi-ring structures. The light Arab fuel oil is believed
to contain highly aromatic molecules which may form very refractory
carbonaceous solids in the combustion chamber. The higher output
of carbonaceous solids containing low ash (V) dilutes even further
the concentration of vanadium in the particles.
7.5.3 Vanadium Recovery Made at Low Firing Rate
At long residence time.burnout cf carbonaceous material
was promoted, as illustrated in Figure 7.5. Therefore, particle
size was shifted toward the submicron and the relative ash content in the
particles was increased. The increase of V concentration in the
solids produced from the light Arab fuel improved run to run
repeatability. There was no statistical difference in precision
between the three groups of runs. Considering overall V recovery
for the five runs on light Arab fuel, the average was 32.3 wt. % of the
fuel V. This was considerably higher than the recoveries made with
fuel F-^, which averaged 21.4 wt. % or fuel F£ which averaged 24.0
wt. %. Combining the latter two, the overall average for all-Ven
fuels was 22.7 wt. %, or about 40% less than for the light Arab.
The concentration of vanadium in the boiler deposits
from the long residence time runs were considerably higher than
obtained at short residence time. The average V content of deposits
in the boiler burning the high ash all-Ven fuel (F^) was about
9.9 wt. %. Roughly 80% of the total vanadium fallout was obtained
in the first two passes while close to 95% of the total was in the
first three passes. This latter value also coincided with total
particulate inventory in the first three passes. At short residence
time, the distribution was quite similar , 93% of the V in the boiler
was recovered in the first three passes and about 95% of the particulate
was obtained there.
Combustion of the intermediate ash all-Ven fuel oil
resulted in deposits having an average V content of 7.6 wt. %. In
this case about 90% of the V was accounted for in the first three
passes along with 87 wt. % of the particulate fallout. At short
residence time the distributions were similar, 90 wt. % and 89 wt. %
respectively.
The light Arab fuel oil produced boiler solids which had
an average V content of 2.0 wt. %. The V and total particulate distributions
with this fuel were somewhat more erratic and showed less correspondence.
In the first three passes approximately 87% of the V and 83% of the
particulate were collected while at short residence time 93% of the V
and 89% of the particulate were collected. These data are summarized in
-------
FIGURE 7.5
VANADIUM RECOVERY IN BOILER - LONG RESIDENCE CASE
60
LJ
o
^ 50
i—
CO
LJ
CO
< 40
n
Qi
LJ
1
_J
0
CD
z 30
a
1 i 1
LLJ
on
LJ
>
8 20
LJ
Q-
— i
Q
1 "
n
FUEL Fi ALL-VEN.
HIGH ASH, V = 359
_ppm V 78 79 82 65 100
—
-
Mean = I = 21.4 WT. %
~Std.Dev. s = 4.1
X
-
^^ ^^
-
_
_
—
-
—
_P4
P3
^••M
P2
"PI
^^•^
^IBM
•^^H
•^^
"^
MMM
^i^MI
57
M^M
^^^
^^H
FUEL F2 ALL-VEN. FUEL F3 LT. ARAB
MED. ASH, V = 149 LOW ASH, V = 39
35 27 40 44 32 37 13 14 13 13 10 -
^™
-
X" = 24.0 WT. % X" = 32.3 WT. %
s = 4.0 sx = 3'9
X
^_^^
P4
^—
P3
MM
P2
^•^
PI
^^
—
—
^^f^
—
^^™
•^
^^B
^~~
^^^^
^^•1
^^^
^••M
^"^
^"™
— I
•^^H
P4
^^^
P3
P2
^^^m
PI
^•^^
HI^B^
"
•^M
^^•^
^^
^^^
^ ••
__
-
-
—
•
00
1
Run: 54 56 67 53 72 80
49 70 76 44 62 73
60 77 51 59 66
-------
- 83 -
Table 7.16. While the concentration of V in the particulate obviously
increases the amount of particulate actually collected is so very low
that handling and work up constitute the major source of errors. This
is further indicated in Run 65 where duplicate samples were analyzed
for V. The largest difference between analyses was about 22%, however,
the V content of the samples were quite low amounting to 0.61 wt. %
and 0.75 wt. %. On the total amount of V recovered, i.e. 17 ppm the
difference in analysis was only 1 ppm or about a 6% relative error.
7.5.4 Further Consideration of
Total Vanadium Kecovery
Regarding overall vanadium recovery at the long residence
time, the fact that it was lower than at short residence time is
somewhat surprising. Considering the temperature differential existing
between the flue gas and heat exchanger tube surfaces and the
overall length of these tubes (equivalent to a probe 40 feet long)
it was thought that thermal diffusion would cause deposition of a
large amount of fine particles. As previously noted in section 7.2.5
at long residence time upwards of 80% of the vanadium-bearing
particulate were in the submicron size range. Since these particles
had the highest V content, total recovery from the passes should have
been equal to or exceeded recovery obtained at short residence time.
Temperature differentials are highest between the flue gas and
tube surfaces in passes 1 and 2. Therefore thermal forces would be
maximized. Consistent with this mechanism at long residence
time, particulate with the highest V content were deposited in the
first two passes. In passes 3 and 4 the V contents of the solids
were lower and more in line with the concentration found in the
particulate deposited at short residence time. There was no apparent
V concentration gradient in the particulate deposited in the passes
at the latter combustion condition.
To determine if there was any interaction between fuels
and vanadium recovery, a computer analysis of variance (ANOVA)
procedure was employed. However, only the runs using the all-Ven
fuels FI and F2 were compared. Results from the light Arab fuel
experiments were so different that these tests could not be considered
as having come from the same population as the others. In Table 7.17
the analysis of variance is reproduced. Based on an F ratio test,
the only significant variable affecting vanadium recovery in the
boiler was residence time; fuel type had no effect.
-------
TABLE 7.15
PARTICULATE AND VANADIUM INVENTORY IN BOILER
(LONG COMBUSTION CHAMBER RESIDENCE TIME - 0.5 LBS./MIN. F.R.)
f FUEL FI, ALL-VEN, HIGH ASH (V
Total
= 359 PPM
Run 54
Vanadium
Particulate Analysis
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
mg/SCM
12
29
11
7
59
• FUEL F?, ALL-VEN, MEDIUM ASH,
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
• FUEL FT, LIGHT ARAB,
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
13
9
18
10
50
LOW ASH
12
19
12
6
49
W Wt.%
10.70
12.26
7.80
7.00
(V = 149 PPM)
Run 49
5.33
9.41
4.60
3.00
(V = 39 PPM)
Run 60
2.70
1.91
1.07
2.62
Vanadium
Content
ppm
(on fuel)
16
45
11
6
78
9
11
11
4
35
4
5
2
2
13
Run 56
Total
Part. V
mg/
SCM
13
24
8
6
51
14
10
4
3
31
3
24
12
7
46
Anal.
Wt.%
10.12
14.34
10.93
8.93
Run 70
2.53
11.97
8.73
7.90
Run 77
5.60
2.17
1.88
3.29
V
Con-
tent
ppm
17
43
12
7
79
4
16
4
3
27
2
7
3
2
14
Run 67
Total
Part. V
mg/
SCM
19
27
14
4
64
7
12
7
3
29
10
22
8
8
48
Anal.
Wt.%
11.92
12.00
4.91
6.96
Run 76
11.67
13.08
6.78
6.32
Run 51
0.73
3.48
0.98
1.05
V
Con-
tent
Ppm
28
42
8
4
82
11
20
6
3
40
1
10
1
1
13
Run 53
Total
Part. V
mg/
SCM
16
31
10
8
65
19
7
18
6
50
5
18
13
11
47
Anal.
Wt.%
7.82
9.15
6.51
5.62
Run 44
4.90
9.71
8.40
6.87
Run 59
4.06
2.54
1.34
1.29
V
Con-
tent
ppm
15
36
8
6
65
12
8
19
5
44
3
6
2
2
13
Run 72
Total
Part. V
mg/
SCM
23
26
11
5
65
8
13
6
3
30
13
20
15
11
59
Anal.
Wt.%
10.29
15.58
9.62
9.60
Run 62
6.88
11.51
5.49
4.64
Run 66
1.82
1.82
0.78
0.85
V
Con-
tent
ppm
30
51
13
6
100
7
19
4
2
32
3
5
1
1
10
Run 80
Total
Part. V
mg/
SCM
20
25
12
8
65
8
11
7
4
30
Anal.
Wt.%
4.72
9.90
5.53
4.70
Run 73
8.65
11.71
8.24
9.40
V
Con-
tent
ppm
12
32
8
5
57
9
17
7
4
37
NOTES:
All weights corrected to
V
-------
TABLE 7.16
PARTICULATE AND VANADIUM INVENTORY IN BOILER
(SHORT COMBUSTION CHAMBER RESIDENCE TIME - 2 LB./MIN. F.R.)
• FUEL Fi, ALL-VEN, HIGH ASH (V = 359 PPM)
Total
Run 55
Vanadium
PartiQulate Analysis
Particulate Distribution m
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
• FUEL F2, ALL-VEN, MEDIUM
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
• FUEL F3, LIGHT ARAB, LOW
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
B/SCM1-1^
35
81
38
8
162
ASH (V =
23
31
15
9
78
ASH (V =
28
83
37
11
159
Wt.%
5.31
5.19
4.82
7.10
149 PPM)
Run 48
3.85
5.30
3.59
3.19
39 PPM)
Run 47
0.76
1.38
0.29
0.68
Vanadium
Content
ppm
(on fuel)
24
54
23
7
108
11
21
7
4
43
3
15
1
1
20
Run 57
Total
Part. V
mg/
SCM
61
148
47
11
267
23
35
21
10
89
36
71
39
16
162
Anal.
Wt.%
3.34
2.12
3.17
4.44
Run 69
5.45
5.60
4.66
2.86
Run 78
1.67
1.22
1.02
1.10
V
Con-
tent
ppm
26
40
19
6
91
16
25
12
4
59
8
11
5
2
26
Run 68
Total
Part. V
mg/
SCM
60
69
27
7
163
28
45
24
10
107
36
77
35
13
161
Anal.
Wt.%
4.29
5.15
6.32
7.38
Run 75
3.22
4.48
3.50
3.29
'Run 50
1.02
0.58
0.53
0.69
V
Con-
tent
ppm
33
45
22
7
107
11
26
10
4
51
6
6
2
1
14
Run 52
Total
Part. V
mg/
SCM
79
117
52
19
267
19
31
17
11
78
22
71
39
17
149
Anal.
wt.%
2.40
3.58
2.99
3.33
Run 45
2.07
4.21
2.86
2.67
Run 58
2.55
1.07
0.75
1.22
V
Con-
tent
ppm
24
53
20
8
105
5
17
6
4
32
Run 71
Total
Part. V
mg/
SCM
45
102
35
8
190
20
44
23
9
96
Anal
Wt.%
4.39
4.93
4.67
10.06
Run 63
3.68
3.47
2.94
3.64
V
Con-
tent
ppm
25
64
21
10
120
9
19
8
4
40
Run 79
Total
Part. V
mg/
SCM
78
145
46
13
282
21
35
20
11
87
Anal.
Wt.%
1.86
2.11
4.50
5.42
Run 74
4.43
3.90
3.43
2.91
V
Con-
tent
ppm
19
39
27
9
94
12
18
9
4
43
Run 65(2)
7
10
4
2
23
22
60
35
20
137
1.59-1
1.07-1
0.61-0
0.35-0
.69 5
.00 8
.75 3
.42 1
17
00
01
NOTES:
(1)
(2)
All weights corrected to 3% 0~-
Separate sample submitted under blind designation.
-------
- 86 -
Vanadium recovery for the 24 runs averaged 26.0 wt. %
+ 2.04 (95 percent confidence limit) of the fuel V input. The
particular fuel employed did not affect vanadium recovery. Combining
both residence times using fuel FI, recovery averaged 25.2 wt. %
versus 26.8 wt. % obtained with fuel F2. On this basis, the six
runs made with each fuel at the particular residence time were
pooled to provide the respective total averages. Thus at short
residence time, vanadium recovery averaged 29.3 wt. % + 2.04
(95 percent confidence limit) versus 22.7 wt. % + 2.04 (95 percent
confidence limit) at long residence time. This difference of
roughly 23% is statistically significant effect at the 95
percent confidence level.
The variance associated with the boiler inventory
amounted to 18.97 out of the total experimental variance of 83.31
determined for the entire program. Therefore, 23% of the total
variance could be explained by the variation in V recovery
determined in the passes.
7.6 Recovery of Vanadium in the Stack - Summation
In each test, both stack sampling systems were operated
simultaneously to prevent sample bias. For the same reason, they
were alternated between the two sample ports 90 degrees apart.
The four variables, i.e. sampling system, residence time, fuel and
sample port location, were tested for their effect on vanadium
recovery using the analysis of variance procedure (ANOVA). Since
runs made with the light Arab fuel, as previously noted, gave V
recoveries in many cases well over 100 percent, these tests were
eliminated from the ANOVA.
The results of the analysis of variance indicated there
were only two primary effects: residence time (T) which produced
a change in V recovery of 10.5 units or roughly 20% and sampling
systems which produced a change in recovery of about 9.3 units or
18%.
Since sample port (the flue gases were not maldistributed
in the stack) and fuel type did not have an effect on vanadium
recovery, tests with these variables were pooled. A two way analysis
of variance using only residence time and sampling system variables
was run to obtain a better estimate of experimental precision. This
served as the basis for Table 7.18 which compares average vanadium
recovery in the two sampling systems as a function of combustion
chamber residence time. Under conditions of short residence time,
-------
TABLE 7.17
VANADIUM RECOVERY IN THE BOILER
ANALYSIS OF VARIANCE
S3JRCE
COLUMNS
R3dS X COLUMNS
ERROR
TOTAL
3RAND viEAM
ERROR STD DEV
ss
0.2660004E 03
0.1650041E 02
0.5510421E 01
0.37936H3E 03
0.6673795E 03
0.26020B3E 02 r 3(t,.D
01 -
ROW MEAMS
0.2269166E 02
0.293<»999E 02
COL MEANS
0.2519166E 02
0.268^.999E 02
._ ^
^j. ' I,
p
/, 7
DF
1
I
1
20
23
*/t>
0.2660004E 03 O.U02333E 02
0.16500^1E 02 0.8698887E 00
0.5510421E 01 0.-2905051E 00
0.1896841E 02 •=.
T, \ ^
t
-------
- 88 -
both sampling trains gave acceptable vanadium recovery. The Method 5
train, however, had a higher collection efficiency inventorying
about 11-1/2% more vanadium than the ER&E system. When residence
time was increased, both sampling systems suffered a loss in collection
efficiency but the ER&E system declined the most. While the EPA
train went from 59.3 wt. % down to 51.2 wt. %, a decrease of nearly
15%, the ER&E system decreased by 25%, going from 52.5 wt. % to 39.5
wt. %. At this lower level, vanadium recovery in the Method 5 train
was almost 23% greater than in the ER&E system. It can be concluded
from the preceding that the glass filter used in the Method 5 system
is more efficient than the silicone oil-containing Greenberg-Smith
impingers in collecting fine vanadium-bearing particles. It is these
submicron particles which apparently pass through the last stage of
the Andersen Cascade Impactor, which has a cut-off of 0.4 ym and then
out the impingers and dry-ice acetone cooled condenser. The inability
of the impingers to trap the very fine vanadium particulate was also
evident in the EPA system. In most of the tests no more than a trace
of vanadium <0.5 ppm was isolated from the chilled water impingers.
In only one of the 36 runs did the amount of vanadium exceed 1 ppm
and that resulted from combustion of light Arab fuel oil where about
3 ppm was found.
Regarding the Method 5 train, since there was an apparent
decrease in V recovery from 59.3 wt. % to 51.2 wt. %, it was expected
that downstream of the fiber glas filter a small amount of vanadium
would be detected. As noted, however, there was no difference in
the V content of the water impingers at either residence time. The
silica gel trap backing the impingers, which is employed to dry the
flue gas prior to metering, was also checked for the presence of
vanadium. In Runs 72, 76 and 80 the silica gel, approximately 200
grams, was extracted with water and analyzed for V by Atomic Absorption.
In all three cases, the vanadium content of the silica gel traps
amounted to no more than a few ppm out of the more than 20 ppm that
was missing. The uncertainty in analysis was largely due to the
dilute state of the sample and subsequent high noise to signal ratio.
While this amount of vanadium does not materially alter the total material
balances in the three runs, it does suggest that some fine particles
may be passing through the sampling system unimpeded. A check of the
ER&E system was similarly attempted by submitting the contents of the
oiler..attached to the vacuum pump for V analysis. The results were
inconclusive since here too only a few ppm V were found.
To sum up, if vanadium is passing through the sampling system
as the results imply, the particles are in an extremely fine size
range probably <0.1ym, and are uncollectable using standard techniques,
i.e. filter, impingers and impaction devices.
-------
- 89 -
TABLE 7.18
RECOVERY OF VANADIUM IN STACK SAMPLING SYSTEMS
(Basis: No statistical difference between fuel
and F2 or stack sampling location)
(ft
EPA Method 5 Train
59.3 wt. %
vanadium recovery
(55.3 - 63.3)
51.2 wt. %
(47.2 - 55.2)
ER&E Train
52.5 wt.
(48.5 - 56.5)
39.5 wt. %
(35.5 - 43.5)
* Test
= 2.02
\= 22
/%025,44)':rom Table
zl.96
= 4.99
^=22
Xl0.025,44)From Table
= 1.96
NOTE:
Experimental variance = 49.56
Std. error = .M!k=12 = 2.03
95 percent confidence interval
Probability -4.0 <_ X <_ + 4.0
44^ =
= 0.95
x 2"03 X
-------
- 90 -
7.7 The Problem of Sulfate Formation
in Water Impingers
7.7.1 Sulfuric Acid Formation
The sulfur trioxide (803) content of flue gas from
combustion of a typical high sulfur fuel oil burned in the Cleaver
Brooks is about 20 ppm. There is sufficient water vapor present
to convert this entire amount to sulfuric acid. If this occurred
the acid, on condensing, would produce about 80 mg/SCM. Provided
the stack temperature and gas stream are maintained above the acid
dew point (280°F) condensation will not occur. Sulfur dioxide can
also be converted to acid. While this reaction was thought to be
slow unless a catalyst was employed, recent data published by Battelle^ '
indicates that a significant part of the S02 in the flue gas will
dissolve in the Method 5 water impingers and may oxidize over a
period of several hours. The rate of oxidation is proportional to
the amount of dissolved oxygen in the water. With a high sulfur fuel
oil, each water impinger can dissolve as much as 20 mg S02/100 ml
H20. Therefore, the oxidation of only a small amount of this will
produce a measurable quantity of acid particulate. Since the potential
to form significant amounts of 1^504 is so high, it is not surprising
that the water impingers used in the Method 5 system have been a
source of varying quantities of particulate.
To overcome this problem in our Company sponsored studies,
we switched from using water in the impingers to a liquid which
could be heated to temperatures >350°F and in which S02 is insoluble.
A number of experiments were run to evaluate the concept of a hot
liquid impinger system as a means of overcoming the sulfate problem.
Several cross comparisons were made with water impingers.
The initial evaluation was made with a sampling train
consisting of a heated probe, Andersen Cascade Impactor and high
velocity chilled water impingers. Under normal base load combustion
conditions in the Cleaver Brook using a high sulfur fuel oil,
approximately 25-30% of the particulate passed through the system and
was collected in the cold water impingers. In this case about 45 mg/SCM.
Approximately 90% of this material was water soluble. Analyses indicated
almost an equal split between S04= tied up with metals such as V, Ni,
Na, Fe and as free sulfuric acid. The acid was determined by potentio-
metric titration of the H+, the sulfate by gravimetric precipitation
with BaCl2- On a mass basis sulfuric acid accounted for roughly 15 mg/
SCM of the total impinger particulate.
-------
- 91 -
With the sampling system consisting of a probe, Andersen
Cascade Impactor and silicone oil in place of water impingers,
particulate passing into the latter accounted for 25 wt. % of the total
inventory, nearly 30 mg/SCM. Most noteworthy was the absence of sulfuric
acid. Total sulfate tied up with metals in this case amounted to 16%
of the impinger solids whereas in the former case, with the water
impingers the amount was nearly 25% of the catch. In another modification
of this experiment, a glass fiber filter was placed after the Andersen
Cascade Impactor and the particulate catch in the silicone oil impingers
system was measured. A small amount of particulate did pass through
the filter, ^4 wt. % of the total inventory, about 5 mg/SCM. Analysis
indicated the particulate contained a small amount of sulfate but
no free sulfuric acid. The weight of filter catch plus impinger
material equaled 35 mg/SCM compared to the previous case of 30 mg/SCM
where particulate not retained by the Andersen Impactor passed directly
into the impinger system. While the weight of these particulate catches
were nearly the same, the sulfate content was quite dissimilar. With
the filter present in the system, sulfate comprised almost half (50%)
of the solids weight compared to less than a quarter (20%) without the
filter. This difference may be an indication that there was interaction
between particulate retained on the filter and flue gas.
A final experiment used the Andersen Impactor, fiber glass
filter and water impingers. Particulate catch from the Andersen
and filter were the same as in the previous case. However, the impinger
catch was much higher amounting to 20 mg/SCM compared to 5 mg/SCM with
silicone oil. Based on a potentiometric titration of the H"1" about
12 mg of this total was free sulfuric acid. Other type sulfate accounted
for 2 mg. These data are summarized in Table 7.191
7.7.2 The Nature of Artificial Particulate
In the factorial study, a highly variable and unpredictable
quantity of artificial particulate was isolated in each run from the
chilled water impingers of the Method 5 train. These solids which
consisted predominantly of ammonia and sulfate were recovered in
amounts ranging from 2 to 44 mg/SCM. Attempts to correlate the formation
of this material with any of the obvious variables including fuel oil
sulfur content were not successful. As shown in Table 7.20 when either
the light Arab (2.8 wt. % S) or intermediate ash all-Ven (1 % S) fuels
were burned, a similar quantity of solids, approximately 13 mg/SCM,
was isolated from the impingers. When the high ash 2.2% S fuel oil
was burned, a considerably lower inventory was obtained averaging 8 ppm.
Combustion chamber residence time had only a slight effect on the
amount of particulate.
-------
- H2S°4
TABLE 7.19
COMPARISON OF PARTICULATE SULFATE/SULFURIC ACID INVENTORY
Filter, mg/SCM
- Sulfate
Cascade Impactor
Cascade Impactor Plus Filter
Water Impingers Silicone Oil Impingers Water Impingers Silicone Oil Impingers
16
16
- Total Particulate
30
30
Impingers, mg/SCM
- Sulfate
10
15
5
None
2
12
0.5
None
- Total Particulate
45
30
20
-------
- 93 -
TABLE 7.20
ARTIFICIAL PARTICULATE FORMATION
IN WATER IMPINGERS OF METHOD 5
Combustion Conditions
Short Residence Time Long Residence Time
*uel Type Impinger Solids. mg/SCM Impinger Solids. mg/SCM
2.2% Sulfur, High Ash
(All-Ven(Fl) 8 5
1.0% Sulfur, Intermed.
Ash All-Ven (F£) 13 10
2.8% Sulfur, Low Ash, Lt
Arab (F3)
The composition of the solids isolated from the water
impingers was determined for a number of runs, and is shown in
Table 7.21. These solids, which were totally water soluble, contained
very little ash (at 1450°F), generally less than 5 wt. %. Vanadium,
which would be one of the major metallic constituents of the ash was
present but in an exceedingly low concentration, ranging from 0.5
wt. % to 1.5 wt. % (expressed as X^O^). Carbon content of the solids
was generally under 10.00 wt. %. This taken together with the low
ash content tends to rule out the possibility that the material
represents "real" particulate.
The major constituents of the solids are ammonia and
sulfate. The latter is present in concentrations of up to 70%. In
some of the preliminary runs, these artificial particulate were
analyzed by X-RAY spectroscopy and found to consist of a mixture
of ammonium sulfate and ammonium bisulfate exclusively. In the runs
where both ammonia and sulfate analysis have been reported,the ratios
also suggest a mixture of the two compounds. In several cases, the
solids were dissolved in water and a standard acid-base titration was
made to determine the hydrogen ion concentration. This has been converted
-------
to the equivalent amount of sulfuric acid and is reported as such
in the table. The amounts generally range from 0.2 to .5 wt. %. Since
the solids were dried under vacuum at 300°F for up to 8 hours, it
is possible that a significant amount of free acid was removed
prior to the analysis. Therefore, too much emphasis should not be
placed on these titrations.
Ammonium sulfate is stable at temperatures up to 400°F.
Since this material was not found in the hot silicone oil impingers
but was only recovered from the water impingers of Method 5, it can
be regarded as an artifact of that system. This artificial particulate
would not be emitted from a boiler during combustion. Therefore,
its inclusion in a particulate inventory is not corrected and will
result in an erroneously high stack loading.
The presence of NH in the flue gas in these runs is
puzzling and has not been resolved.
7.8 Determination of Oxidation State
of Vanadium Particulate in Flue Gas
A short series of experiments were run to determine the
change in oxidation state of vanadium exposed to flue gas. Milligram
samples of three vanadium oxides: V203 (III), ^2°^ (V) were placed
separately on a fiber glass filter, heated to 375°F and each exposed
for 2 hours to flue gases produced by firing the high sulfur all-Ven
heavy fuel oil with 10% excess air. Only the V205 gave any indication
of reaction, changing color from mustard yellow to green. After
exposure each of the samples was transferred under a nitrogen blanket
into a flask and dissolved in sulfuric acid. A colorimetric determination
run on the sulfuric acid solutions of the oxides indicated that
approximately one third of the pentavalent vanadium (V) was reduced
to tetravalent V (IV). While these experiments are by no means
definitive, they do"~indicate that some of the vanadium in the particulate
may be emitted in V 4 state. In a previous Company sponsored study,
color changes were noted for particulate which had been collected
on a hot fiber glass filter used to back up the Andersen Cascade
Impactor. In that work the filter was normally taken apart in the
laboratory and the particulate were, therefore, exposed to air. The
fines which were usually green in color at 375°F became black or grey
on cooling to ambient temperature. Subsequent reheating would not
produce the reverse color change.
+4
Since the normal vanadyl type compounds formed by V
are not volatile at stack temperatures, the presence of V™ would not
explain the loss of vanadium from the sampling systems.
-------
TABLE 7.21
Run No.
52
53
54
55
56
57
67
68
71
48
49
62
63
69
46
47
50
59
60
Fuel
High Ash
it ii
it n
tt n
All-Ven
it n
it n
it
it
n
n
n
n
n
n
Interned. Ash-All-Ven
n
it
n
n
it
ii
it
tt
it
Low Ash-Lt . Arab
n
n
.on of Solids from
Solids
Isolated, mg/SCM
14
9
6
8
4
8
4
10
6
4
12
4
5
11
20
6
37
11
23
Method 5 Water
V C
0.31
-
0.66
None 5 .
0.56
0.26
0.25
0.14
0.10
None 12 .
0.40 10.
Trace
0.20
0.83
None 2 .
1.3 4.
None 1.
Trace
0.38
Impingers
H N
_ —
-
- -
01 2.29 8.81
-
-
- -
- -
0.47*
29 3.65 8.65
98 3.43 8.29
0.22*
0.26*
_ _
83 5.28 16.24
51 3.60 8.35
21 4.18 11.86
0.3*
0.2'-
NH^
_
-
-
-
-
-
-
1.73
Trace
—
9.08
Trace
-
9.3
18.82
2.87
13.96
-
Trace
69.76
23.0
51.31
26.10
40.02
50.25
32.01
46.17
60.62
*Reported as H SO,
-------
- 96 -
8. REFERENCES
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-------
- 98 -
APPENDIX 1
STATE OF THE ART REVIEW
VANADIUM ANALYSIS AND PARTICIPATE SAMPLING METHODOLOGY
-------
- 99 -
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Compounds, Litton Systems, Inc. Bethesda, Md. Environmental
Systems Div., PB-188 093, p. 105 (September 1969).
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190. Thompson, R.J., Morgan, G.B., Purdue, L.J. (Div. Air Qual. Emiss. Data,
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Atomic Absorption, Anal. Instrum. 7, 9-17 (1969).
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of Air Pollution, Chem. Weekbl. 65(30) 7-8 (1969).
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Monitoring of Particle Size and Concentration of Aerosols By A
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193. Flesch, J.P., (Natl. Center for Air Pollut. Control) Calibration
Studies of a New Sub-Micron Aerosol Size Classifier, 153rd
ACS Nat. Mtg. (Miami Beach 4/9-14/67) J. Colloid Interface Sci.,
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194. Brandon, J.H., Can A Fuel Treatment Program Control Stack
Emissions, Combustion Vol. 41, No. 4, p20-24, Air Pollution;
Fuel Oils (October 1969).
195. Lees, B., (Brit. Petrol. Co. Ltd.) Chemistry of Deposits in Oil -
Fired Boilers, J. Inst. Fuel 42 #344:356-57 (September 1969).
196. Liu, B.T.G., Marple, V.A., Yazdani, H., Comparative Size
Measurements of Monodisperse Liquid Aerosols by Electrical
and Optical Methods, Univ. Environ. Sci. Technol. 3, #4:381-86,
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Air Pollut. Control Admin. Publ. //AP-51, p.551 (January 1969).
198. Bando, S., Tsuyoshi (Japan At. Energy Res. Inst. Oarai, Japan)
Determination of Vanadium in Deposit and Airborne By Neutron
Activation Analysis, Kagaku 18(12), 1447-82 (1969).
199. Householder, M.K. (Youngstown State Univ., Ohio) Goldschmidt, V.W.,
Impaction of Spherical Particles on Cylindrical Collectors,
J. Colloid Interface Sci. Vol. 31, No. 4 p. 464-78 (December 1969).
200. Battigelll (Univ. N.C. Sch. Med.) Particulates: Air Quality
Criteria Based on Health Effects, API, Air Qual. Monogr. //69-2
p. 15 (February 1969).
201. Byers, R.L. (Pa. State Univ.), Particulate Collection Equipment
and Characteristics — 2. West Scrubbers and Electrostatic
Precipitators, Lehigh Valley Air Conser. Council Joint
"Eng. Aspects Air Pollut. Contr." Conf. (Bethlehem 5/22/69)
Proc. p. 29.
202. Perman, J., Perman, E., Spectrographic Determination of Metal
Traces in the Atmosphere, Bol, Geol. Minero 1969, 80(5), 476-84.
203. Himi, Y. Mori, 0., Studies on Sampling Points for Measurement
of Dust Concentration in Horizontal Straight Flue, J. Chem.
Soc. Japan, Vol. 72, No. 11, p.2347-51 (November 1969).
204. Halstead, W.D., (Chem. Div., Cent. Elec. Res. Lab., Leatherhead, Eng.)
Thermodynamics of Fuel Oil Ash Constituents in Combustion Systems,
J. Inst. Fuel, 42 (346), p.419-24 (1969).
205. Yen, T.F., Boutcher, L.J. et al. (Carnegie-Mellon Univ.) Vanadium
Complexes and Porphyrins in Asphaltenes, J. Inst. Petrol. 55,
#542:87-99 (March 1969).
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206. Hoffman, G.L., Duce, R.A. (Univ. Hawaii), Zoller, W.H. (Mass. Inst.
Technol.) Vanadium, Copper, and Aluminum in the Lower Atmosphere
Between California and Hawaii, Environ. Sci. Technol. 3, //11:1207-10,
(November 1969).
207. Air Quality Data from the National Air Surveillance Networks and
Contributing Seate and Local Networks 1966 Edition
National Air Pollution Control Administration, Durham, N.C.,
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208. Rama, S., Paggi, A. (Univ. Siena) An Apparatus for Collecting
Smoke and Other Particulate Samples on Microscope Slides in
(Subsequent) Particle-Size Determinations, Riv. Combust. 23,
//6:325-28 (June 1968).
209. Keane, J.R., Fisher, E.M.R. (Health Phys. Med. Div. at Energy Res.
Establ., Harwell, Eng.) Analysis of Trace Elements in Airborne
Particulates By Neutron Activation and X-Ray Spectrometry,
Atmos. Environ. 2(6), p.603-14 (1968).
210. Andreatch, A.J., Innes, W.B., Characterization of Petroleum Waste
Products By Selective Combustion Thermal Effects, 155th ACS
Natl. Mtg. (San Francisco 3/31-4/5/68) ACS Div. Petrol Chem. Inc.
Preprints Vol. 13, No. 2, Motor Fuels; Air Pollution
211. Wiele, H., Kasten, G. , Combustion and Determination of Compounds
Containing Inorganic Sulfur, Inorganic Fluorine, and Organic
Phosphorus, Arsenic, Vanadium and Lead by the Wickbold Method
Under Application of a Metal Burner, Fresenius'Z. Anal. Chem.
235(4), p.335-41 (1968).
212. Osamu, T., (Div. Hyg., Inst. Sci. Labor, Tokyo, Japan),
Determination of Toxic Substances in Air Inorganic Compounds,
Rep. Inst. Sci. Labour, No. 69, p.10-22 (1968).
213. Volodarskii, I. Kb.., Grekhov, I.T., Panin, V.I., Shmuk, E.I.,
Shpirt, M. Ya. (USSR), Distribution of Some Rare and Nonferrous
Metals During Combustion of Coals, Khim. Tverd. Topi (2), p.103-6
(1968).
214. Lundgren, D.A. (Univ. Calif., Statewide Air Pollut. Res. Center)
The Effects of Various Fluoride Sources Citrus Growth and Fruit
Production, Univ. Calif. Statewide Air Pollut. Res. Center
Univ. Calif Riverside Extension "Air Pollut. Calif.: Past,
Present & Future Conf. "Air Pollut: Causes & Effects Symp.
(Riverside, Calif. 9/26/68) p.15-23.
215. Shiraiwa, T., Matsuno, F., Identification of Vanadium-Attack
Products, Sumitomo Kinzoku 20 //2 (1968) (Abstr) Ccrros. Abstr.
7, //5:328, (September 1968).
216. Jerman, L., Jettmar, V. , Polarographic Determination of Vanadium
in Air of Work Areas (Hyg-Stat. Bezirksnat Ausschusses, Prague, Czech),
Z. Gesamte Hyg. Ihre Grenzgeb 1968 14(1), 12-14.
217. Bergmann, J.G., Ehrhardt, C.H. et al. (Am. Oil Co.) Trace Analysis
of Metals By Ion Exchange Concentration and X-Ray Fluorescence (XRF)
153rd ACS Natl. Mtg. (Miami Beach 4/9-14/67) Abstr., Papers:
Abstr. No. B14.
218. Bergmann, J.G., Ehrhardt, C.H. et al (Am. Oil Co.) Determination
of Sub-PPM Nickel and Vanadium in Petroleum by Ion Exchange
Concentration and X-Ray Fluorescence, 153rd ACS Mtg. (Miami Beach
April 1967), Anal. Chem. 39 //11:1258-61 (September 1967).
219. Laamanen, A. (Tyoterveyslaitos, Helsinki), Air Pollution in Helsinki,
Kern. Teollisuus, 23(7), p.619-25 (1966).
220. Guest, R.J., Ingles, J.C. (Extraction Met. Div. Mines Branch, Dept.
Mines Tech. Surv., Ottawa) Analytical Procedures for a Vanadium
Recovery Process, Can. Dept. Mines Tech. Surv., Mines Branch Tech.
Bull. TB 79, p.62 (1966).
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221. Rich, T.A., (General Electric, Res. & Development Center, Schenectady,
New York), Apparatus and Method for Measuring the Size of Aerosols,
J. de Recherches Atmospheriques, p.79-86, (1966).
222. Kuz'micheva, M.N., Determination of Vanadium in the Air of Working
Areas and in Biological Media, Vop. Gig. Tr. Prof. Patol, 369-79
(1966).
223. Kuzmicheva, M.N. (F.F. Erisman Inst. Hyg., Moscow) Determination
of Vanadium in the Atmosphere, Gigiena & Sanit .31(2), 53-4 (1966)
224. Wehrberger, F., Problems in Oil-Fired Boilers of Industrial Power
Plants, Mitt. Ver. Grosskesselbesitzer #98:349-57 (October 1965);
(Abstr.) Combustion 37 #12:47 (June 1966).
225. Suboch, W.P. (Brit. Am. Oil Co. Ltd.) Vanadium Analyzer Useful Tool,
Oil Gas J. 64 #9:116-17,119 (2/28/66).
226. Kuz'micheva, M.N. (F.F. Eoisman Sci. Res. Inst. Hyg. Moscow)
Method for Detecting Vanadium in the Air, Gigiena & Sanit. 30(5),
71-2(1965).
227. Bird, R.J., Small, N.J.H. (Shell Res. Ltd.) The Combustion of
Heavy Fuel Oil: Some Observations on Carbonaceous Droplet Residues
and on the Ash from the Gas Stream, J. Inst. Petrol., 51 #494:71-77
(February 1965).
228. Bol'shakov, G.F., An Investigation of Ash Composition in Hydrocarbon
Fuels, Khim. i Teknol. Toplivi Massel 9 #10:48-52 (October 1964).
229. Bender, R.J., How Low for Low Excess Air, Power 108 #3:63-65 (March 1964);
(Abstr.) Corrosion Abstr. 3, #5:367 (September 1964).
230. Guinn, V.P., Wagner, C.D. (Shell Develop. Co., Calif.) Instrumental
Neutron Activation Analysis, Anal. Chem. 32, 317-23 (1960).
231. Hansen, J., Hodgkins, C.R. , Wet Ash Spectrochemical Method for
Determination of Trace Metals in Petroleum Fractions, Exxon Research
and Engineering Company, Linden, Analytical Chemistry, Vol. 30,
No. 3, pages 368-372, March 1958.
232. Hirt, R.C., Doughman, W.R. and Gisclard, J.B. (American Cyanaraid,
Stamford, Conn.) Application of X-Ray Emission Spectrography to
Airborne Dusts in Industrial Hygiene Studies, Anal. Chem. 28, 1649-51
(1956).
233. Allen, N.P., Kubaschewski, 0., Goldbeck, von, 0., (Nat. Physical Lab,
Teddington, Middlesex, Eng.) The Free Energy Diagram of the Vanadium
Oxygen System , J. of the Electrochemical Soc., p. 417-423
(November 1951).
234. Milan, E.F., The Dissociation Pressure of Vanadium Pentoxide, Vol. 33,
p. 498-508 (1929).
235. Ammonium Sulphate and Vanadium Recovery from Flue Dust Obtained
During Heavy or Crude Oil Combustion, Azuma Kako Co., Ltd. JA-7141211-R.
Analysis of Waters Containing Vanadium - By Complex, JA-4850559-Q
Collecting Metal Oxide Particles from Furnace Waste Gas - For
Addition to Heavy Oil to Reduce Pollution on Combustion, Showa Denko KK
JA-7J29283-R.
236. Zegel, W.C. (Doylestown, Pa., assignor to Scott Research Lab., Pa.)
Method and Equipment for Catalytic Analysis of Gases, Filed June 3, 1969
Ser. No. 830,012 - U.S. 3,687,631.
237. Pollard, A.J. (Rosecroft Park, Md. assignor to the United States of America
as represented by the Secretary of the Navy), Method for Removing
Vanadium Deposits from the Fire Side of Heat Transfer Surfaces.,
#3,369,934
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- 115 -
238. Whigham, W, (Ville de'Anlon, Quebec, Canada), Production of
Vanadium Values from Crude Oil, #3,416,882.
239.. Richardson, H.L., (Pittsburgh, Pa., assignor to Chemical Construction
Corporation, New York) Removal of Solids from Flue Gas, #3,568,403.
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APPENDIX 2
LABORATORY ISOLATION OF PARTICIPATES
COLLECTED FROM STACK SAMPLING TRAINS
-------
APPENDIX 2
Laboratory Isolation of Particulates
Collected from Stack Sampling Trains
MATERIALS
4 800 ml beakers
2 1,000 ml beaker
1 2,000 ml beaker
8 30 ml porcelain crucibles previously marked with run no.
and appropriate designations .
crucibles placed in furnace @ 1400°F for several hours.
1 Metier 5 decimal place balance Model H20T
1 Blackstone ultra-sonic cleaner
1 Millipore stainless steel 47 mm pressure filter holder
REAGENTS
Hexane
Isopropyl Alcohol
Dist. H20
Chloroform
FIRE CHAMBER
The solids accumulated in the fire chamber are swept into
a teflon container then sieved through a 100 mesh screen to remove
extraneous particles such as pieces of fire brick.
The two fractions, <100 and >100 are transferred to tared
bottles and put into the vacuum oven to dry at 275°F for four hours » The
weight is recorded and the sampler submitted for chemical analysis.
BOILER TUBE INSERTS
After completion of the warm up period, the boiler was shut down
and the rear door opened. A single stainless steel tube was inserted
into a randomly selected boiler tube in each of the three passes of the
Cleaver Brooks Boiler. The rear door was closed and the boiler restarted.
As soon as run conditions were achieved, stack sampling began. Weights
of fuel at restart and at start of stack sampling and at completion
of run were recorded.
The boiler tube inserts were removed and labelled as to their
location in the passes.
The tubes were cleaned in the following manner; the tube insert
was mounted vertically to platform with clamps and a labelled 1000 ml
beaker placed under it. The tube was washed alternately with dist. H20
and isopropyl alcohol. A plunger consisting of a rubber disc conforming
to the inner diameter of the tube and mounted on a long stainless steel
rod was passed up and down the length of the tube several times in order
to remove any material that might adhere to the sides of the tube.
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Following this the tube was again rinsed with dist. H20 and isopropyl
alcohol. The beaker was removed and put on steam bath and evaporated to a
manageable volume. This was transferred to a tared and labelled
crucible. Then evaporated to dryness. The solids were placed in a
vacuum oven at 275°F to dry. After weighing,samples from each of
the three batches of solids were submitted for vanadium analysis.
In several tests, the final wash of the tubes was accomplished using
about 500 ml of 0.5 NH Cl. The solution was submitted directly for
V analysis.
PROBE
Cap off both ends of probe and rinse off all material that
was collected on outside of the probe during run. Remove cap from
nozzle tip and wash inside of nozzle and probe with dist. 1^0. When
probe is full place caped end into ultra-sonic bath for approx. 30 sec.
Pour into 250 ml beaker. Repeat using isopropyl alcohol. Remove cap
and rinse probe from capped and directly into beaker with dis. H20 and
isopropyl alcohol.
Glass connector, probe to Andersen: Repeat same procedure
used in washing probe. Rinse into 250 ml beaker containing probe
wash. Place on steam bath to evaporate.
CYCLONE
Solids are recovered from cyclone using probe isolation
procedure. Solids are dried under vacuum at 300°F.
ANDERSEN CASCADE IMPACTOR
8 separate stages with a corresponding stainless steel
plate are washed in same manner. (The head of the Andersen is washed
along with the "0" stage and plate). Carefully remove stage, wash rim
and face with dist. H20 and isopropyl alcohol into beaker. Reverse
stage and repeat procedure. If any material appears to remain, use
rubber policeman to remove. Remove stage and using forceps place
corresponding plate into the washings, cover with water glass. Place
beaker with washings and plate into ultra-sonic bath for approx. 30
sec. or until all solids are off plate. Remove plate from washings.
Rinse both sides into beaker with dist. water and isopropyl alcohol.
Place beaker on steam bath to evaporate.
After the last plate has been removed the base of the
Andersen neck, and connector leading to the impingers will remain.
They are rinsed with dist. H20 and isopropyl alcohol into a 1,000
ml beaker marked "impinger water wash". Cover beaker and keep it
aside to be used again later on in work-up.
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GLASS CONNECTORS
Remove stop-cock grease. Fill connector with hexane.
Cap both ends and place in ultra-sonic bath for 1 minute. Pour into
2,000 ml beaker with impinger washings. Repeat again, then rinse
connectors until all traces of silicone oil are removed. Allow to
dry.
FILTRATION OF SILICONE OIL
Stir oil and hexane washings in 2,000 ml beaker to be
filtered. Weigh 1 millipore teflon .20 mu filter paper and place in
pressure filter and lock. Add approx. 300 ml of impinger wash from
beaker to sample container. Lock. Use approx. 60 psi pressure
to filter. All of sample should filter in 3 hours. At end of
filtration rinse sample container with 3 x 100 ml increments of
hexane and pressure these through filter. When filtration is complete
remove filter paper and dry in vacuum oven at 300°F for four hours.
Remove filter paper, place in desicator to cool. Weigh when filter
paper is at room temperature.
WATER WASH OF IMPINGERS
(This is done while impingers are filtering) check dry
impingers for any traces of silicone oil. If there are traces of
silicone oil, wash with hexane again adding washings to impinger sample,
when there is no further trace of oil present, the dry impingers are
washed with distilled water and isopropyl alcohol in the same manner
as with the hexane wash. Should any trace of material remain after the
water isopropyl alcohol wash an additional wash using chloroform should
be used. All washings should be added to previously obtained "impinger
water wash" beaker and placed on steam bath to evaporate.
WATER IMPINGERS
After removal from sampling train removal all traces of
stop-cock grease from impingers. Place each impinger in ultra-sonic
bath for approximately five minutes, empty contents into a 2,000 ml
beaker labelled "impinger H20 wash". Each impinger is washed by the
same method; thoroughly rinse all inner surfaces of impinger, neck and
arm into impinger with 100-150 ml of water. Place in ultra-sonic
bath for two cr three minutes. Empty into 2,000 ml "impinger wash"
beaker. Repeat same procedure using isopropyl alcohol. Pour wash
into beaker. If any material remains, an additional wash using
chloroform is used. Evaporate contents of "impinger wash" to dryness
on steam bath. Transfer material from beaker to tared 30 ml crucible
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- 120 -
using water, isopropyl alcohol as a rinse. Evaporate crucible to
dryness. Place in vacuum oven at 300°F for four hours. Cool in
dessicator to room temperature. Weigh and record weight on particulate
emissions data sheet. Submit dry sample in screw neck vials for
typical analysis.
PROBE, PLATES, IMPINGER WATER WASH SAMPLES
Weigh 30 ml crucibles and record tare weights. Transfer
samples on steam bath to appropriate crucibles rinsing with water and
isopropyl alcohol. Evaporate to dryness. Place in vacuum oven at
300°F. Remove crucibles, place in dessicator, weigh when crucibles
are at room temperature. Record weights of all fractions on particulate
emissions data sheet.
SILICONS OIL IMPINGERS
Open all impingers and wipe off stop-cock grease from ground
glass joints. Place on steam bath. This will help make silicone oil
less viscous and easier to handle (this can be done prior to work-up
of Andersen so silicone oil will be reasonably fluid for work-up).
Pour contents of all impingers into 2,000 ml beaker, rinsing with
hexane. Pour approx. 250 ml hexane into each impinger. Place impinger
into ultra-sonic bath for approx. 2 mins. while impinger is in ultra-
sonic bath, use squeeze bottle and wash inside of impinger neck and
arm into the impinger. Pour hexane into 2,000 ml beaker. Wash
impinger bottle and neck thoroughly with hexane until no trace of
silicone oil is present. Repeat with each impinger. Allow impingers
to dry.
COMBINATION OF FRACTIONS
After all weights are recorded, samples are combined into
three fractions: probe and "0"; plates 1 thru 5; plates 6,7 and impinger,
and submitted for vanadium analysis by Atomic Absorption Spectroscopy.
The filters, one from the filtration of the silicone oil in the ER&E
train, and the fiber glass filter from the Method 5 train, after drying
under vacuum at 300°F for four hours are also submitted for vanadium
analysis.
ASH PROCEDURE
Using three weighing boats that have been previously heated
in a furnace at 1450°F overnight and cooled to room temperature in a
dessicator. Obtain tare weights on boats. Place approximately 10 mg.
sample of material from each of the three fractions (dried at 500°F
overnight) into the boats. Weigh and record. Place boats in furnace
overnight at 1000°F. Following morning remove boats, place in dessicator
to cool to room temperature. Weigh and record sample loss. Calculate
ash.
-------
COMPARISON OF TIME REQUIREMENTS
FOR WORK UP OF SAMPLING SYSTEMS
Probe
Cyclone
Filter
Impinger
(+ Connectors)
Leak Check
Totals
EPA SYSTEM
Prep. Work Up*
5 10
5 10
15 15
10 45
5
40 mins. 80 mins.
ER&E
Probe + 0
Andersen 1-5
Andersen 6,7
Impingers (filtering)
(+ Connectors)
Traps
Leak Check
Totals
SYSTEM
Prep. Work Up*
5 15
45
5
15
15 210
15 20
5 - i
45 mins. 305 mins. M
i
Total Work Up + Prep. = 2 hours
Total Work Up + Prep. 5 Hrs. 50 mins.
*Exclusive of drying isolated solids.
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APPENDIX 3
THE DETERMINATION OF VANADIUM IN PARTICULATES
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- 123 -
APPENDIX 3
The Determination of Vanadium in Particulates
ABSORPTION SPECTROSCOPY
Atomic absorption spectroscopy is a single element technique
requiring at least 3 cm^ of sample solution per determination. Due to
the small sample sizes encountered in this project only the vanadium
determination was evaluated.
Sample Preparation
The solid particulate samples were dried before weighing. The
dried sample was then digested with a mixture of perchloric, nitric, and
sulfuric acids. This acid digestion was found to be quicker than dry
ashing and is not as subject to error through loss when working with
small samples.
The teflon and silica filter particulate samples were extracted
with 5% HN03 acid. It was found that at least 99% of the vanadium is
removed by this technique. Aqueous samples were analyzed directly.
Accuracy
The accuracy of an atomic absorption analysis is dependent
upon the accuracy of the calibration standards, as well as physical
and chemical interferences. Reagent grade VOS04 , ^'205 and Fisher
1000 p.p.m. standards were used. Calibration standards prepared from
each of these sources agreed quite well.
Several chemical species have been reported to chemically
interfere with the vanadium determination. Sachaleu, Robinson, and
West^1' have reported using the addition of A1C13 to overcome these
interferences. This technique was therefore used for all vanadium
determinations associated with this project.
The accuracy of vanadium by optical emission has been well
established and was therefore used to check the atomic absorption
results. Good agreement was obtained as can be seen from an inspection
of Table I.
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TABLE 1
COMPARISON OF VANADIUM ANALYSIS BY ATOMIC ABSORPTION
AND OPTICAL EMISSION SPECTROSCOPY
wt% V
Sample A. A. 0. E. S,
1 3.7 3.8
2 3.3 3.8
3 4.1 3.6
4 2.3 2.2
5 3.6 3.7
6 2.6 2.4
7 5.0 4.9
8 8.4 8.4
Sensitivity
The sensitivity of the vanadium determination is such that a
minimum of 50 yg of vanadium is required per analysis. This means that
a 2 mg particulate sample containing less than 2.5 wt70 V could not be
determined by this technique.
'S. L. Sachaleu. J. W. Robinson, and P. W. West, Anal. Chim. Acta.,
37 (1967) 12.
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- 125 -
Precision
A day to day precision study was conducted using a large sample
which had been sieved, dried, and thoroughly mixed. Aliquots of this
sample were put through the entire procedure and the resulting sample
solutions were saved. Each day a new sample solution was prepared and
analyzed with previous preparations. The columns of data in Table II
are the repetitive results for each sample preparation and were used to
calculate the day-to-day precision of the measurement step. The top
diagonal of data in Table II are the first results obtained for each
new sample preparation and were used to calculate the day-to-day precision
for the entire procedure. An average relative standard deviation (la)
of 2.8% was calculated for the measurement step as compared to 4.3% for
the entire procedure. These results show that the sample preparation
can be carried out as precisely as the measurement.
PROCEDURE-ATOMIC ABSORPTION
Apparatus
A P&E Model 403 atomic absorption spectrometer, equipped with
a vanadium hollow cathode lamp and a strip chart recorder were used in
this study.
Instrumental Parameters
The following parameters apply to the P&E Model 403 unit.
Wavelength - 319.2 nm; UV setting
Lamp Current - 14 mA
Slit 4 (Spectral Band Pass - 0.2 nm)
Fuel - Acetylene
Oxidant - Nitrous oxide
Flame Stoichiometry - Reducing; red cone
1 - 1 1/2 cm in height
REAGENTS (A.A.)
3
Standard Vanadium Solution 1000 Mg/cm
Available from Fisher Scientific Company.
Digestion Acid Mixture
To 150 cm of cone. HN03 add 50 cm3 of 72% HCIO^ and 180 cm3 of
cone ^SO,/;. After stirring and cooling, the solution is made up to 400 c
with cone. HN03.
-------
TABLE II
,^Date Prepared
Date Analyze'3""*--^^
1/21
1/22
1/24
1/30
1/31
2/11
2/13
2/21
2/24
2/25
1/21
6.58
6.36
6.22
6.46
6.67
6.76
6.31
6.62
6.64
1/22
6.28
6.28
6.28
6.64
6.82
6.37
6.64
6.73
VANADIUM
1/24
6.48
6.71
6.78
6.78
6.56
6.56
6.59
PRECISION
1/30
6.56
6.36
6.92
6.92
6.50
6.74
6.83
STUDY
1/31 2/11 2/13 2/21 2/24 2/25
6.39
6.86 6.26
6.76 6.62 7.07
6.66 6.15 7.16 6.86
6.80 6.50 7.25 6.95 6.84
6.77 6.50 7.09 6.07 7.02 6.94
-------
- 127 -
3
Aluminum Solution 3000 ug/cm
3
- Weigh 6.00 g of aluminum metal into a 400 cm beaker. Add
40 cm of aqua regia and a few milligrams of a mercury salt. Transfer
to a 2-litre volumetric flask after dissolution is complete and dilute
to volume with deionized water.
Nitric Acid Solution 5% (v/v)
Add 50 cm-^ of concentrated nitric acid to a 1-litre Volumetric
flask and dilute to volume with deionized water.
Calibration
(1) Add 0, 1, 5, 10, and 15 cm of the 1000 ug/cm stock vana-
dium solution to each of 5-100 cm^ volumetric flasks.
3
(2) Add to each of these flasks 1 cm of the acid digestion
mixture and 10 cm^ of the aluminum solution. Then dilute up to volume
with deionized water and mix well. This makes 0, 10, 50, 100, and 150 ug/cm
vanadium standards, respectively.
2 (3) Aspirate each of the standards into the flame using the
0 Mg/cm solution as the blank.
T (4) Prepare a calibration curve plotted as absorbance versus
Mg/cm vanadium.
Sample Analysis
The samples associated with this project consisted of three
types: free particulate, particulate on filter paper (teflon or silica),
and aqueous extract solutions.
A. Free Particulates
(1) Dry the sample for at least 1 hour at 110°C and allow to
cool in a desiccator containing anhydrous magnesium perchlorate or
calcium chloride as the desiccant.
(2) Weigh between 2 and 100 milligrams of sample, depending
upon availability, into a 30 ml Kjeldahl digestion flask.
(3) Place the flask onto a Kjeldahl digestion rack equipped
with a glass hood and bubbler system.
(4) Add 2 cm of the acid digestion mixture and heat slowly
until the brown fumes disappear and the solution is clear.
(5) Bring the mixture to fumes of perchloric acid and continue
to heat for 15 minutes.
-------
- 128 -
(6) Cool, add 5 cm of water, and bring to a boil.
(7) Transfer the digestate quantitatively to a 10 cm volu-
metric flask after cooling.
(8) Add 1 cm of the aluminum solution and dilute to volume
with deionized water.
(9) Measure the absorbance of the sample solution and determine
the corresponding ug/cm3 of vanadium from the calibration curve. If the
absorbance is higher than the highest calibration standard, dilute to
within the working range making certain that the final solution contains
300 yg/cm3 of Al+3.
(10) Calculate the wt. % vanadium using the following equation:
> (cm of final solution) (c
sample weight (milligrams)
„. ,. (ug/cm vanadium) (cm of final solution) (dilution factor) x 10
wt. 7, vanadium = -JJ=a
B. Filter Samples
(1) Cut the entire filter into small pieces being careful not
to lose sample and place into a 400 cm3 beaker.
3
(2) Add 50 cm of 5% nitric acid to the beaker.
(3) Place a watch glass over the beaker and boil for 30 minutes.
^ (A) Cool and filter through //I Whatman filter paper into a
100 cm volumetric flask.
(5) Add 10 cm of the aluminum solution and dilute to volume
with deionized water.
(6) The remainder of the sample preparation is described in
steps 9 and 10 of Part A. (Free Particulates).
C. Aqueous Solutions
3 3
(1) Accurately transfer 9 cm of the sample into a 10 cm
volumetric flask.
(2) Dilute to volume with the aluminum solution and mix well.
(3) The remainder of the sample preparation is described in
steps 9 and 10 of Part A. (Free Particulates).
-------
- 129 -
EMISSION SPECTROSCOPY
Emission spectroscopy is a multi-element analysis technique yielding
a relative precision of at least 10%. Our existing capability at the
onset of this project allowed the simultaneous determination of Ni,
Fe, V, Si and Na in relatively large samples. Due to the small
sample sizes to be encountered, work was done to extend the lower
working limit without affecting the accuracy or precision of the
method. Only solid particulate samples were studied although this
technique could be extended to filter and aqueous samples.
Sample Preparation
The particulate samples were dry ashed in porcelain
crucibles. The formation of a friable ash was accomplished through
the addition of glycerin to the sample before ashing.
Calibration Standards
Standards consisted of the oxides of Ni, Fe, V, and Si,
and NaCl. Each element was introduced into the standard to cover
the low, high, and intermediate points of the range of interest. The
2.750 gm total for each standard consisted of the metal oxides,
sodium chloride, and lithium tetraborate. A straight line curve was
obtained for each element indicating that the amount of matrix does
not produce variation in the calibration curves over the range studied.
Five standards were fired to calibrate the instrument and prepare the
standard curves. Scale deflection units (Y-axis) were plotted versus
mgs of each element (X-axis).
The emission spectroscopy procedure is calibrated to cover the
range of 0.5 to 5 mg V, 0.05 to 0.5 mg Ni, 1.00 to 25 mg Si, 1.00 to 25
mg Na, and 1.00 to 25 mg Fe.
PROCEDURE - EMISSION SPECTROSCOPY
Apparatus
Direct reading ARL Quantometer. Excitation source is a
voltage spark of the ARL multisource unit, Model #4700.
ARL power driven hydraulic press with a 12.7 mm die (1/2").
-------
- 130 -
Instrumental Parameters
5 sec prespark
50 sec exposure controlled by integration of a constant
amount of energy from the internal standard.
Set in 10-100 scale deflection units.
Wavelengths of analytical emission lines are:
o
A
Li 4972.0 (reference line)
V 3184.0
Ni 3414.8
Si 2881.6
Na 5896.0
Fe 3020.6
Reagents
(1) Certified Spectranalyzed Glycerin.
(2) 1,128407 - 4-9's pure - Spex Industries.
(3) SP-1 grade graphite - Spex Industries.
(4) Graphite rod with a flat tip - 6.35 x 50.8 mm - high purity
Spex Industries.
Procedure
(1) Weigh a minimum of 10 mg into a porcelain crucible and
add 1 cm of glycerin.
(2) Ash the sample at 540°C for one hour.
(3) Weigh the ash.
(4) Transfer the ash to a graphite crucible.
(5) Cover the ash with 1126407 so that the total weight of ash
plus 1,126407 equals 2.750 g. (Example: If ash weight is 2.0 mg add
2.748 g Li2B407) •
(6) Fuse at 980°C for 10 minutes.
-------
- 131-
(7) Grind the glass-like bead obtained from the fusion in
a tungsten carbide mill.
(8) Sieve the ground material through a 200 mesh cloth.
(9) Blend one part of sample with two parts of SP-1
pelletizing graphite.
(10) Press a portion ( ^ 1 g) into a 12.7 mm briquette with
the press set at 40,000 psi.
(11) Place the briquette in a brass holder. The counter
electrode is a 6.35 x 50.8 ram graphite rod.
(12) Set in and fire the standards and then fire the samples
on the Quantometer.
(13) Read and record scale deflection units for each element.
Determine the mgs of the element from the appropriate curve.
-------
SUMMARY OF
ATOMIC ABSORPTION SPECTROSCOPY
Lam:
•M
-:ama ccrirair.ing
sample
j ^
H I
Monc:'.-..'orr>ator
-_^— -^ " '
'^^^-^ 1
Detecto: &
recorder
s
Wavelength. X
Hollow cathode lamp emits
line spectrum of element to
be determined
Resultant spccVfwim after
ibcorption by sample
A
U)
NJ
Photodctcctor sees only the
resonance line, diminished
by sample absorption
-------
- 133 -
APPENDIX 4
OPERATIONAL DATA FROM FACTORIAL PROGRAM
-------
APPENDIX 4
EXPERIMENTAL
Experiment No.
Fuel Type
Residence Time
Stack Position
Vanadium Analysis in Fuel, ppm
Operational Data
Flue Gas Oxygen, %
Nozzle Temperature, °F
Stack Temperature, °F
Fuel Consumption, Lbs.
• Firetube
• Heat Exchanger Inserts
• Particulate Sampling
Bacharach Smoke Tape No.
Boiler Deposits, grams
Firetube
Pass 2 (1 tube of 14)
Pass 3 (1 tube of 10)
Pass 4 (1 tube of 8)
Corrected Distribution, mg/SCM (Combustion Gas)
Firetube
Pass 2 (all tubes)
Pass 3 (all tubes)
Pass 4 (all tubes)
Total
Vanadium Analysis, Wt. %
Firetube
Pass 2
Pass 3
Pass 4
Vanadium Distribution In Boiler Solids, ppm (on fuel)
Firetube
Pass 2
Pass 3
Pass; 4
Total
Vanadium Recovery
Average V Content in Solids, wt. %
TABLE 1
DATA SUMMARY FOR
44
F2
TT
2
145
2.0
147
213
194
111
104
2.5
21.76
0.32
1.19
0.51
19
7
18
6
50
4.90
9.71
8.40
6.87
12
8
19
5
44
6.9
BOILER
45
£2
To
2
150
2.0
150
318
450
264
237
5.5
51.61
3.49
2.66
2.20
19
31
17
11
78
2.07
4.21
2.86
2.67
5
17
6
4
32
3.2
OPERATION
46
,13
Ti
i
40
2.0
186
220
245
172
162
1.5
19.30
1.56
0.77
0.80
14
22
8
7
51
2.91
8.81
3.81
3.64
5
25
4
3
37
5.7
47
Ti
1
37
2.0
187
328
579
452
362
6
94.75
15.36
9.67
3.42
28
83
37
11
159
0.76
1.38
0.29
0.68
3
15
1
20
1.0
48
¥.
i
138
2.0
150
318
403
262
237
5.5
56.15
3.42
2.40
1.72
23
31
15
_9
78
85
30
59
3.19
11
21
7
_4
43
4.3
49
T?
1
140
2.0
140
215
99
99
74
2.5
7.76
0.38
1.08
0.71
13
9
18
IP.
50
5.33
9.41
4.60
3.00
9
11
11
4
35
5.3
-------
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
ERE Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Volume SCFDB
• Gross Particulate Weights, mg
Probe & 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
Total
• Vanadium Analysis, Wt. %
Probe & 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
• Particulate Distribution, Wt. %
>10u
EPA Sampling Train, Operating Data
• Isokinetic Sampling Rate , %
• Sample Volume, SCFDB
• Gross Particulate Weights, mg
Probe
Cyclone
Filter
Impingers
Total
• Vanadium Analysis, Wt. %
Probe & Cyclone
Filter
Impingers
*Based on Cumulative Distribution.
EXPERIMENTAL
44
F2
145
T'
2
93
43.23
11.79
11.99
5.13
24.37
53.28
1.53
2.60
15.99
23
25
52
98
56.60
17.56
2.50
59.56
50.78
130.40
2.15
14.61
None Detected
APPENDIX 4
TABLE 2
DATA SUMMARY FOR
45
F2
X¥o
2
99
78.91
55.51
141.67
18.30
75.31
290.79
1.26
2.76
10.70
21
47
32
98
78.91
14.05
54.28
221.82
103.89
394.04
1.30
6.31
None Detected
STACK SAMPLING
A6
F3
40,
Ti
1
95
.65.49
4.82
15.39
10.95
13.33
44.49
1.56
1.36
2.28
12
35
53
1.06
83.70
7.11
3.70
52.17
50.05
113.03
0.74
7.86
1.30
SYSTEMS
4?
F3
iV
1
93
112.99
218.38
385.48
22.09
126.85
752.80
Trace
0.11
1.16
6.84
31
49
20
92
121.26
119.88
209.39
459.41
20.45
809.13
0.14
1.24
None Detected
48
F2
To?
i
93
83.52
49.05
136.44
11.60
62.40
259.49
1.63
3.44
10.80
13.95
24
47
29
95
81.34
23.31
38.59
190.13
9.71
261.74
1.37
7.73
None Detected
96
39.83
8.90
11.03
4.89
21.85
46.67
0.21
92
56
15.26
21
24
55
1.05
43.26
5.10
1.63
50.32
15.25_
72.30
Trace
15.70
0.40
-------
APPENDIX It
Experiment No.
Fuel Type
Vanadium Analysis, ppra
Residence Time
Stack Position
Operational Data
Flue Gas Oxygen, %
Nozzle Temperature,°F
Stack Temperature, °F
Fu2l Consumption, Lbs.
o Fire tube
o Heat Exchanger Inserts
o Particulate Sampling
Bacharach Smoke Tape No.
Boiler Deposits, grams
Firetube
Pass 2
Pass 3
Pass 4
(1 tube of 14)
(1 tube of 10)
(1 tube of 8)
Total
(Combustion Gas)
Corrected Distribution, mg/SCM
Firetube
Pass 2 (all tubes)
Pass 3 (all tubes)
Pass 4 (all tubes)
Total
Vanadium Analysis, wt. %
Firetube
Pass 2
Pass 3
Pass 4
Vanadium Distribution in Boiler Solids, ppm (on fuel)
Firetube
Pass 2
Pass 3
Pass 4
Total
Vandadium Recovery
Average V Content in Solids, wt. %
TABLE
DATA SUMMARY
50
F3
39
T°
2
2
185
325
469
264
241
6
102.54
8.41
5.33
2.54
118.82
36
77
35
13
161
1.02
0.58
0.53
0.69
5
6
2
1
14
3
FOR BOILER OPEM
51
F3
40
Tl
2
2
178
216
233
154
141
2
13.65
1.40
0.73
0.93
16.71
10
22
8
8
48
0.73
3.48
0.93
1.05
1
10
1
1
13
52
Fl
350
To
2
2
215
316
240
129
90
6
108.83
6.21
3.86
1.74
120.64
79
117
52
19
267
2.40
3.58
2.99
3.33
24
53
20
8
105
53
0.7
2.1
3.1
368
Ti
2
2
205
214
122
70
48
2
10.87
0.88
0.40
0.41
12.56
15
31
10
8
64
7.82
9.15
6.51
5.62
15
36
8
6
65
8.0
54
Fl
350
Ti
1
2
201
218
173
80
65
2
11.70
0.94
0.50
0.41
13.55
12
28
11
7
58
10.70
12.26
7.80
7.00
16
45
11
6
78
55
Fl
358
(To
1
2
205
346
556
301
114
5
111.94
10.15
6.50
1.70
130.29
35
81
38
8
162
5.31
5.19
4.82
7.10
24
54
23
7
108
56
Fl
^
1
2
198
217
203
90
67
2
14.90
0.87
0.43
0.41
16.61
13
24
8
6
51
10.12
14.34
10.93
8.93
17
43
12
7
79
57
.FI
363
1
2
200
341
427
214
118
5
148.93
13.04
5.84
1.75
169.56
61
148
47
11
267
3.34
2.12
3.17
4.44
26
40
19
6
91
10.6
5.2
12.2
2.7
-------
APPENDIX 4
ppm
Experiment No.
Fuel Type
Vanadium Analysis,
Residence Time
Stack Position
ERE Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Volume, SCFDB
• Gross Particulate Weight, mg
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6, 7
Impingers
Total
• Vanadium Analysis, Wt. %
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
• Particulate Distribution*
52
53
55
56
57
Wt. %
1-10 X.
EPA Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Volume, SCFDB
• Gross Particulate Weight, mg
Probe
Cyclone
Filter
Impingers
Total
• Vanadium Analysis, Wt. %
Probe + Cyclone
Filter
Impingers
92
75
114.5
282.9
1 .0
173.1
98
61
2.8
7.6
19.2
23.5
94
26
71.6
142.7
26.0
43.1
96
55
6.1
17.6
16.2
61.4
95
74
4.9
18.4
22.4
80.0
98
41
93.8
113.5
9.5
40.2
93
78
11.4
21.0
24.9
88.6
92
41
112.5
207.4
13.3
43.0
283.4
101.3
125.7
257.0
145.9
352.6
02
99
0.31
135.7
5.40
25.06
None
171.1
8.33
22.86
0.66
381.4
3.78
15.63
None
186.1
5.21
21.95
0.56
376.2
0.44
0.46
1.18
3.28
23
57
20
93
86
30.3
58.4
229.0
93.2
2.50
2.73
2.50
17.76
6
18
76
105
75
3.3
1.7
42.4
16.6
1.10
4.18
3.82
8.25
27
51
22
96
34
57.9
66.7
213.6
14.4
4.17
13.11
18.38
19.09
6
22
72
96
62
3.9
7.4
107.0
17.4
7.00
18.86
25.74
21.77
4
17
79
95
79
4.2
3.3
150.5
13.1
2.43
8.90
16.80
13.12
35
46
19
105
44
45.1
112.9
112.6
10.8
3.88
22.97
18.52
23.71
7
17
76
94
84
9.5
7.3
158.5
10.8
1.66
4.62
14.29
9.31
32
54
14
105
48
43.2
260.3
128.7
9.3
i
OJ
-J
1
441.5
2.29
11.96
0.26
*Based on Cumulative Distribution.
-------
APPENDIX 4
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
Operational Data
Flue Gas Oxygen, %
Nozzle Temperature, °F
Stack Temperature, °F
Fuel Consumption, Lbs.
• Firetube
e Heat Exchanger Inserts
• Particulate Sampling
Bacharach Smoke Tape No.
Boiler Deposits, grams
Firetube
Pass 2 (1 tube of 14)
Pass 3 (1 tube of 10)
Pass 4 (1 tube of 8)
Total
Corrected Distribution, mg/SCM
Firetube
Pass 2 (all tubes)
Pass 3 (all tubes)
Pass 4 (all tubes)
Total
Vanadium Analysis, wt. %
Firetube
Pass 2
Pass 3
Pass 4
Vanadium Distribution in Boiler Solids, ppm (on fuel)
Firetube
Pass 2
Pass 3
Pass 4
Total
Vanadium Recovery
Average V Content in Solids, wt. %
(Combustion Gas)
TABLE 5
EXPERIMENTAL DATA SUMMARY
58
F3
51
2
2
188
357
518
264
184
6
66.05
7.71
5.96
3.16
82.88
22
71
39
17
149
2.55
1.07
0.75
1.22
7
10
4
2
23
FOR BOILERS
59
F3
42
Of
2
2
186
234
267
109
55
2
8.00
0.82
0.84
0.88
10.54
5
18
13
11
47
4.06
2.54
1.34
1.29
3
6
2
2
13
60
F3
38
1
2
178
218
159
75
62
2
10.52
0.57
0.50
0.33
11.92
12
19
12
6
49
2.70
1.91
1.07
2.62
4
5
2
2
13
62
F2
158
1.2
2.1
2.1
2
145
222
213
108
48/82
2
10.47
0.59
0.37
0.26
11.59
8
13
6
3
30
6.88
11.51
5.49
4.64
7
19
4
_2
32
8.3
63
F2
2
145
341
687
325
178
6
81.94
6.09
4.39
2.20
94.62
20
44
23
9
96
3.68
3.47
2.94
3.64
9
19
8
_2
40
3.3
65
F3
40
2
186
346
667
324
120/160
6
83.94
8.01
6.54
4.57
103.06
22
60
35
20
137
1.59/1.69
1.07/1.00
0.61/0.75
0.35/0.42
5
8
3
_2
17
1.0
-------
APPENDIX 4
TABLE 6
EXPERIMENTAL DATA SUMMARY FOR STACK SAMPLING SYSTEMS
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
ERE Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Volume, SCFDB
• Gross Particulate Weight, mg
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
Total
• Vanadium Analysis, We. %
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
• Particulate Distribution* , Wt. %
>10y
1-lOu
-------
APPENDIX 4
TABLE 7
EXPERIMENTAL DATA SUMMARY FOR BOILERS
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
Operational Data
Flue Gas Oxygen, %
Nozzle Temperature, °F
Stack Temperature, °F
Fuel Consumption, Lbs.
• Firetube
• Heat Exchanger Inserts
• Particulate Sampling
Bacharach Smoke Tape No.
Boiler Deposits, grams
66
67
68
69
70
71
72
Firetube
Pass 2 (1
tube of 14)
Pass 3
Pass 4
(1 tube of 10)
(1 tube of 8)
Total
(Combustion Gas)
Corrected Distribution, mg/SCM
Firetube
Pass 2 (all tubes)
Pass 3 (all tubes)
Pass 4 (all tubes)
Total
Vanadium Analysis, wt. %
Firetube
Pass 2
Pass 3
Pass 4
Vanadium Distribution in Boiler Solids, ppm (on fuel)
Firetube
Pass 2
Pass 3
Pass 4
Total
Vanadium Recovery
Average V Content in Solids, wt. %
5
/Ti
2
2
183
219
202
91
69
2
14.79
0.81
0.81
0.74
17.15
13
20
15
11
59
1.82
1.82
0.78
0.85
3
5
1
1
10
343
/IT
1
2
199
217
216
97
53
2
22.85
1.09
0.75
0.29
24.98
19
27
14
4
64
11.92
12.00
4.91
6.96
28
42
8
4
82
363
at
i
2
205
354
296
296
152
6
100.94
8.36
4.54
1.58
115.42
60
69
27
7
163
4.29
5.15
6.32
7.38
33
45
22
7
107
F2
/ft
1
2
150
446
627
296
153
6
84.00
4.49
3.69
2.14
94.32
23
36
21
10
90
5.45
7.34
4.66
2.86
16
33
12
4
65
!§£>
(h
1
2
151
218
222
66
56
2
18.36
0.29
0.14
0.14
18.93
14
10
4
3
31
2.53
11.97
8.73
7.90
4
16
4
3
27
Fl
383,
2
2
197
413
820
314
179
6
212.04
13.12
6.30
1.71
233.17
45
102
35
8
190
4.39
4.93
4.67
10.06
25
64
21
10
120
Fl
335;
nr
2
2
195
220
197
102
91
2
26.13
1.08
0.62
0.38
28.21
23
26
11
5
65
10.29
15.58
9.62
9.60
30
51
13
6
100
1.3
10.1
5.2
5.8
6.9
5.0
12.2
o
i
-------
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
ERE Sampling Train, Operating Data
mg
• Isokinetic Sampling Rate, %
• Sample Volume, SCFDB
• Gross Particulate Weight,
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
Total
• Vanadium Analysis, Wt . %
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
• Particulate Distribution
Wt . %
1-lOp
EPA Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Voluem SCFDB
• Gross Particulate Weight, mg
Probe
Cyclone
Filter
Impingers
Total
• Vanadium Analysis, Wt . %
Probe + Cyclone
Filter
Impingers
APPENDIX 4
TABLE 8
EXPERIMENTAL DATA SUMMARY
0
2
1
0
66
F3
38
-------
APPENDIX 4
TABLE 9
EXPERIMENTAL DATA SUMMARY FOR BOILERS
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
Operational Data
Flue Gas Oxygen, %
Nozzle Temperature, °F
Stack Temperature, °F
Fuel Consumption, Lbs.
• Firetube
• Heat Exchanger Inserts
• Particulate Sampling
Bacharach Smoke Tape No.
Boiler Deposits, grams
Firetube
Pass 2 (1 tube of 14)
Pass 3 (1 tube of 10)
Pass 4 (1 tube of 8)
Total
Corrected Distribution, mg/SCM (Combustion Gas)
Firetube
Pass 2 (all tubes)
Pass 3 (all tubes)
Pass 4 (all tubes)
Total
Vanadium Analysis, wt. %
Firetube
Pass 2
Pass 3
Pass 4
Vanadium Distribution in Boiler Solids, ppm (on fuel)
Firetube
Pass 2
Pass 3
Pass 4
Vanadium Recovery Total
Average V Content in Solids, wt. %
73
F2
150
T*
2
2
150
238
199
88
66
2
9.06
0.42
0.35
0.25
10.08
8
11
7
4
30
8.65
11.71
8.24
9.40
9
17
7
4
37
9.8
74
F2
«*
2
2
150
455
662
358
252
6
83.55
5.36
4.32
2.99
96.22
21
35
20
11
87
4.43
3.90
3.43
2.91
12
18
9
4
43
3.8
75
F2
150
'/*
1
2
150
410
378
207
117
6
63.22
4.02
2.91
1.50
71.65
28
45
24
10
107
3.22
4.48
3.50
3.29
11
26
10
4
51
3.7
76
F2
145
rfi~
1
2
150
225
209
91
78
2
9.08
0.47
0.35
0.23
10.13
7
12
7
3
29
11.67
13.08
6.78
6.32
11
20
6
3
40
10.7
77
F3
38
T
2
185
219
174
98
89
2
2.70
0.98
0.66
0.46
4.80
3
24
12
7
46
5.60
2.17
1.88
3.29
2
7
3
2
14
2.4
78
F3
38
.-TO
2
185
391
482
196
119
6
100.85
5.72
4.37
2.30
113.24
36
71
39
16
162
1.67
1.22
1.02
1.10
8
11
5
2
26
1.2
79
&
sfr-
2
2
200
384
463
191
115
6
207.56
11.40
5.00
1.78
225.74
78
145
46
13
282
1.86
2.11
4.50
5.42
19
39
27
9
94
2.6
80
s,
2
202
219
198
84
63
2
22.85
0.86
0.57
0.47
24.75
20
25
12
8
65
4.72
9.90
5.53
4.70
12
32
8
5
57
6.9
-------
APPENDIX 4
Experiment No.
Fuel Type
Vanadium Analysis, ppm
Residence Time
Stack Position
ER&E Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Volume, SCFDB
• Gross Particulate Weight (uncorrected) ,Mg
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
Total
o Vanadium Analysis, wt. %
Probe + 0 Stage
Andersen Stages 1-5
Andersen Stages 6,7
Impingers
• Particulate Distribution* wt. %
EPA Sampling Train, Operating Data
• Isokinetic Sampling Rate, %
• Sample Volume, SCFDB
• Gross Particulate Weight (uncorrected) , rag
Probe
Cyclone
Filter
Impingers
Total
Vanadium Analysis, wt. %
Probe + Cyclone
Filter
Impingers
TABLE
EXPERIMENTAL
73
F2
150,
f\\
2
95
79
5.0
9.3
9.7
58.7
82.7
3.27
12.70
17.38
16.29
6
14
80
96
90
7.0
3.1
82.5
4.3
96.9
3.47
21.71
1.18
10
DATA SUMMARY
74
F2
150
/TO
2
92
83
57.6
142.9
25.3
87.4
313.2
1.99
3.05
8.29
6.66
18
46
36
97
86
29.0
49.9
156.0
20.7
255.6
1.86
6.60
0.09
75
F2
150
MO
1
97
42
45.6
82.5
10.9
39.9
178.9
1.89
3.59
5.56
8.44
29
42
29
98
42
22.6
64.8
91.5
5.0
183.9
2.11
9.18
0.83
76
F2
145
1
96
101
4.0
13.8
7.7
67.0
92.5
2.41
8.23
10.50
18.70
5
14
81
98
104
3.3
13.9
100.0
12.8
130.0
2.96
19.60
2.50
77
Fi
38^
1
94
112
8.7
25.1
6.1
44.8
84.7
1.76
2.76
6.46
13.96
12
27
61
102
122
5.2
15.5
95.4
5.5
121.6
1.88
7.10
0.49
78
F3
99
42
72.9
126.6
12.8
66.9
279.2
0.63
0.80
1.56
2.21
26
45
29
101
43
43.6
96.8
130.1
5.1
275.6
0.59
15.22
1.41
79
Fl
365
2
95
42
165.1
218.8
18.4
52.7
455.0
1.27
3.20
7.55
9.20
40
44
16
100
44
66.2
271.6
156.1
7.3
501.2
1.35
9.18
0.28
80
FI
373 .
''2
93
78
8.2
30.4
17.8
87.4
143.8
3.16
8.99
14.63
20.11
6
18
76
100
83
8.2
29.9
161.6
6.6
206.3
1.79
20.57
0.64
*Based on Cumulative Distribution.
-------
- 144 -
APPENDIX 5
PARTICULATE INVENTORY AND VANADIUM BALANCE
(All data corrected to 3% 0- in flue gas)
-------
TABLE 1
Particulate Inventory and Vanadium Balance From
Combustion of High Ash Venezuelan Resid
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Stack Particulate
• ER&E Train
Total
1-lOp
EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
Total
Total
Particulates
mg/SCM
35
81
38
8
162
75
97
39
211
123
86
(209)
8
217
(Short
Run 55
Vanadium
Analysis
Wt. %
5.31
5.19
4.82
7.10
2.43
8.90
14.53
3.78
15.63
-
Combustion Chamber Residence
Vanadium
Content
ppm(on Fuel)
24
54
23
7
108
23
110
72
205
59
171
-
230
Total
Particulates
mg/SCM
61
148
47
11
267
99
167
43
309
215
91
(306)
7
313
Time)
Run 57
Vanadium
Analysis
Wt. %
3.34
2.12
3.17
4.44
1.66
4.62
12.87
2.29
1.96
0.26
Vanadium
Content
ppm(on Fuel)
26
40
19
6
91
21
98
71
190
63
138
Trace
201
Run 52
Total Vanadium
Particulates Analysis
mg/SCM Wt. %
97
183
79
359
128
214
(
14
356
(342)
1.10
4.18
7.37
1.02
5.99
0.31
Vanadium
Content
ppm(on Fuel)
79
117
52
19
267
2.40
3.58
2,99
3.33
24
53
20
8
105
14
97
74
185
17
163
Trace
180
-------
TABLE 2
Particulate Inventory and Vanadium Balance From
Combustion of High Ash Venezuelan ResId
(Short Combustion Chamber Residence Time)
Run 68
Run 71
Run 79
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Stack Particulate
• ER&E Train
Total
l-10y
Total
Total
Particulate
ma/SCM
60
69
27
7_
163
55
115
60
230
Vanadium
Analysis
Wt. %
it.29
5.15
6.32
7.38
2.59
7.83
10.24
Vanadium
Content
ppm(on fuel)
33
45
22
7
107
18
115
78
211
Total
Particulate
mg/SCM
45
102
35
8
190
152
152
58
362
Vanadium
Analysis
Wt. %
4.39
4.93
4.67
10.06
2.16
5.54
11.08
Vanadium Total Vanadium Vanadium
Content Particulate Analysis Content
ppm(on fuel) mg/SCM Wt.% ppm (on fuel)
25
64
21
10
120
42
108
82
232
144
158
58
360
1.86
2.11
4.50
5,42
1.27
3.20
8.52
19
39
27
_9
94
23
64
63
150
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
102
101
10
213
(203)
4.50
14.85
0.14
58
191
Trace
249
280
92
6_
378
(372)
2.87
13.00
<0.10
102
152
Trace
254
256
118
380
(374)
1.35
9.18
0.38
44
138
Trace
182
-------
TABLE 3
Particulate Inventory and Vanadium Balance From
Combustion of High Ash Venezuelan Resld
(Long Combustion Chamber Residence Time)
Run 54
Run 56
Run 53
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Stack Particulate
• ER&E Train
Total
Total Vanadium
Particulates Analysis
mg/SCM Wt. %
Vanadium
Content
ppm(on Fuel)
12
29
11
7
59
10.70
12.26
7.80
7.00
16
45
11
6
78
Total
Particulates
mg/SCM
13
24
8
_6
51
Vanadium
Analysis
Wt. %
10.12
14.34
10.93
8.93
Vanadium
Content
ppm(on Fuel)
17
43
12
J_
79
Total Vanadium
Particulates Analysis
mg/SCM Wt. %
Vanadium
Content
ppm(on Fuel)
16
31
10
8
65
7.82
9.15
6.51
5.62
15
36
8
6
65
>10p
l-10u
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
2
10
45.
57
Total
3
64.
(
I2.
89
(67)
7.00
18.86
23.35
8.33
22.86
0.66
2
23
133
158
3
186
Trace
189
4
11
47
62
(70)
_4
74
3.88
22.97
22.83
5.21
21.95
0.56
2
31
137
170
4
177
Trace
181
4
14
44^
62
6
58
(
_9
73
(64)
4.17
13.11
20.16
5.40
25.06
2
23
114
139
4
184
188
-------
Partlculate Inventory and Vanadium Balance From
Combustion of High Ash Venezuelan Resid
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Stack Particulate
• ER&E Train
Total
1-10M
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
Total
(Long Combustion Chamber Residence Time)
Total
Particulate
mg/SCM
19
27
14
4
64
3
11
54
68
7
70
(77)
4
81
Run 67
Vanadium
Analysis
Wt. %
11.92
12.00
4.91
6.96
1.51
12.29
14.38
5.00
17.74
0.25
Vanadium
Content
ppm(on fuel)
28
42
8
4
82
1
17
98
116
4
159
Trace
163
Total
Particulate
mg/SCM
23
26
11
5
65
3
15
46
64
5
67*
72 (37)
4
76
Run 72
Vanadium
Analysis
Wt. %
10.29
15.58
9.62
9.60
6.51
18.46
23.33
5.71
24.65
0.63
Vanad ium
Content
ppm(on fuel)
30
51
13
6
100
3
35
137
175
3
100
Trace
103
Total
Partlculate
mg/SCM
20
25
12
8
65
4
11
47
62
15
^ (80)
3
83
Run 80
Vanadium
Analysis
Wt. %
4.72
9.90
5.53
4,70
3.16
8.99
18.53
1.79
20.57
0.64
Vanad ium
Content
ppm (on fuel)
12
32
8
5
57
t-
*•
i
2
13
111
126
3
170
Trace
173
"Average of Runs 53 and 80.
-------
TABLE 5
Particulate Inventory and Vanadium Balance From
Combustion of Intermediate Ash Venezuelan Resid
Particulate Distribution .
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Stack Particulate
• ER&E Train
>10y
l-10y
Total
EPA Train
Probe & Cyclone
Filter
Water Impingers
(Short Residence Time Case)
Run
Total
Particulate
mg/SCM
19
31
17
11
78
26
58
40
124
29
95
(124)
44
168
45, Fuel F2
Vanadium
Analysis
Wt. %
2.07
4.21
2.86
2.67
1.26
2.76
10.70
1.30
6.31
Trace
Vanadium
Content
ppm(on fuel)
5
17
6
4
32
4
20
54
78
5
76
-
81
Run 48, Fuel
Total
Part.
mg/SCM
23
31
15
9
78
26
51
31
108
24
77
(101)
4
105
V
Anal.
Wt. %
3.85
5.30
3.59
3.19
1.63
3.44
13.42
1.37
7.73
F2
V Cont.
ppm
(On fuel)
11
21
7
4
43
5
22
53
80
4
76
Total
Part.
mg/SCM
20
44
23
9
96
34
51
46
131
88
62
Run 63
V
Anal.
Wt. %
3.68
3.47
2.94
3.64
1.33
3.44
7.18
2.70
9.66
V Cont.
ppm
(on fuel)
9
19
8
4
40
6
22
42
70
30
76
(150)
Trace
-
80
5
155
0.20
Trace
106
vo
I
-------
TABLE 6
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Particulate Inventory and Vanadium Balance From
Combustion of Intermediate Ash Containing Venezuelan Resid
(Short Residence Time Case)
Run 69 Run 74
Total
Particulate
mg/SCM
Vanadium
Analysis
Wt. %
Vanadium
Content
ppm(on fuel)
Total
Part.
mg/SCM
V
Anal.
Wt. %
V Cont.
ppm
(on fuel)
Run 75
Total
Part.
mg/SCM
V
Anal.
Wt. %
V Cont.
ppm
(on fuel)
23
36
21
12
90
5.45
7.34
4.66
2.86
16
33
12
_4
65
21
35
20
11
87
4.43
3.90
3.43
2.91
12
18
9
4
43
28
45
24
10
107
3.22
4.48
3.50
3.29
11
26
10
4
51
Stack Particulate
• ER&E Train
>10y
l-10y
Total
29
65
39
133
2.05
3.90
7.6
8
32
38
78
23
58
45
126
1.99
3.05
7.15
6
23
41
70
41
59
41
141
1.89
3.59
7.65
10
27
40
77
Ul
o
t EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
69
71
11
151
(140)
1.80
8.72
0.83
16
79
_
96
31 1.86
62 6.60
(93)
8
101
0.09
7
52
Trace
59
69 2.11
72_ 9.18
(141)
0.83
18
84
102
-------
TABLE 7
Particulate Inventory and Vanadium Balance From
Combustion of Intermediate Ash Venezueland Resid
(Long Residence Time Case)
Run 44, Fuel F,.
Run 49, Fuel F
Run 62
Particulate
Distribution
Total
Particulate
mg/SCM
Vanadium
Analysis
Wt. %
Vanadium
Content
ppm(on fuel)
Total
Part.
mg/SCM
V
Anal.
Wt. %
V Cont.
ppm
(on
fuel)
Total
Part.
mg/SCM
V
Anal.
Wt. %
V Cont.
ppm
(on fuel)
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Stack Particulate
19
7
18
_6
50
4.90
9.71
8.40
6.87
12
8
19
_5
44
13
9
18
10
50
Na
Na
Na
3.00
Est.(44)
8
13
6
3
30
6.88
11.51
5.49
4.64
7
19
4
2
32
• ER&E Train
>10y
l-10y
Total
9
10
II
41
1.53
2.60
15.99
2
3
44.
49
8
10
22
40
0.21
2.92
14.10
Trace
4
39
43
3
5
26
34
1.34
2.13
16.61
1
1
55
57
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
12
_36
_30
78
(48)
2.15
14.61
3
66
69
5
li
12.
56
15.70
(44)
79
79
5 Flask Broke -
_35_ 17.90 80
(40)
4 <0.1 Trace
44 80
-------
TABLE 8
Particulate Inventory and Vanadium Balance From
Combustion of Intermediate Ash Venezuelan Resid
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Stack Particulate
t ER&E Train
Total
(Long Residence
Run 70
Total
Particulate
mg/SCM
Vanadium
Analysis
Wt. %
Vanadium
Content
ppm(on fuel)
Time Case)
Run 73
Total
Part.
mg/SCM
V
Anal.
Wt. %
V Cont.
ppm
(on fuel)
Total
Part.
mg/SCM
Run 76
V
Anal.
Wt. %
V Cont.
ppm
(on fuel)
1-10
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
14
10
4
3
31
2.53
11.97
8.73
7.90
4
16
4
3
27
3
4
2£
36
2
_42
J3
52
(44)
5.00
10.00
14.9
2.50
13.11
0.25
2
6
55
63
1
70
Trace
71
8
11
7
4
30
8.65
11.71
8.24
9.40
9
17
7
4
37
7
12
7
3
29
11.67
13.08
6.78
6.32
11
20
6
3
40
2
5
28
35
3.27
12.70
16.82
1
8
60
69
2
4
25
31
2.41
8.23
17.58
1
5
56
62
i
M
Ln
1
4 3.47 2
31 21.71 86
(35)
_2 1.18
-------
TABLE 9
Particulate Inventory and Vanadium Balance
From Combustion of Low Ash Light Arab Resid
(Short Residence Time Case)
Particulate Distribution
Run 47
Total
Particulate
mg/SCM
Vanadium
Analysis
Wt. %
Vanadium
Content
ppm (on fuel)
Run 50
V Cont.
pprt
(on fuel)
Total
Part.
mg/SCM
Run 58
V
Anal.
Wt. %
Cont.
.ppm
(on fuel)
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Stack Particulate
• ER&E Train
Total
l-10y
EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
28
83
37
11
159
69
109
45
223
90
128
224
(218)
0.76
1.38
0.29
0.68
Trace
0.11
6.84
0.14
1.24
3
15
1
1
20
2
34_
36
2
20
22
36
77
35
13
161
1.02
0.58
0.53
0.69
5
6
2
1
14
22
71
39
17
149
2.55
1.07
0.75
1.22
7
10
4
2
23
50
123
43
216
0.44
0.46
2.90
3
7
16
26
59
101
38
198
0.59
0.83
5.23
4
11
25
40
35
90
37
162
0.36
0.92
(125)
2
11
13
140
79
225
0.69
1.52
0.65
Ul
OJ
12
15
Trace
27
-------
TABLE 1,0
Particulate Inventory and Vanadium Balance
From Combustion of Low Ash Light Arab Resid
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Stack Particulate
• ER&E Train
>10y
l-10y
Total
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
(Short Residence Time Case)
Total
Particulate
mg/SCM
22
60
35
20
137
48
98
54
200
115
93
(208)
13
221
Run 65
Vanadium
Analysis
Wt. %
(1)
Duplicate
1.59 - 1.69
1.07 - 1.00
0.61 - 0.75
0.35 - 0.42
0.67 - 0.61
0.77 - 0.71
2.3
0.67 - 0.57
1.53
0.25 - 0.47
Vanadium
Content
ppm (on fuel)
Average
5
8
3
1
17
4
9
16
29
9
18
Trace
27
Total
Particulate
mg/SCM
36
71
39
16
162
58
100
64
222
109
101
(210)
4
214
Run 78
Vanadium
Analysis
Wt. %
1.67
1.22
1.02
1.10
0.63
0.80
2.08
0.59
15.22
1.41
Vanad ium
Content
ppm (on fuel)
8
11
5
2
26
i
i
4
10
17
31
8
20
<1
28
(1)
Separate samples submitted under blind designation.
-------
TABLE 11
Particulate Inventory and Vanadium Balance
From Combustion of Low Ash Light Arab Resid
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass 2
Pass 3
Pass 4
Total
Stack Particulate
• ER&E Train
>10y
1-10M
Total
EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
(Long Residence
Total
Particulate
mg/SCM
14
22
8
7
51
3
8
12
23
4
21
(25)
20
45
Run 46
Vanadium
Analysis
Wt. %
2.94
8.81
3.81
3.64
1.56
1.36
2.28
Trace
7.86
1.30
Vanadium
Content
ppm(on fuel)
5
25
4
3
37
<1
1
4
5
_
21
3
34
Time Case)
Total
Part.
mg/SCM
5
18
13
11
47
6
4
Run 59
V
Anal.
Wt. %
4.06
2.54
1.34
1.29
2.21
3.04
23 10.67
33
6
22
(28)
11
39
3.54
9.14
Run 60
V Cont.
ppm
(on fuel)
3
6
2
2
13
2
1
31
34
3
25
Total
Part.
mg/SCM
12
19
12
6
49
2
4
19
25
4
29
V
Anal.
Wt. %
2.70
1.91
1.07
2.62
1.95
3.40
9.35
2.35
6.00
V Cont.
ppm
(on fuel)
4
5
2
2
13
< 1
2
23
25
1
22
(33)
0.76
1
29
23
56
0.10
Trace
23
Ul
Ul
-------
TABLE 12
Partlculate Inventory and Vanadium Balance
From Combustion of Low Ash Light Arab Resid
Particulate Distribution
Boiler Solids
Pass 1 (firetube)
Pass. 2
Pass 3
Pass 4
Total
Stack Particulate
• ER&E Train
l-10y
Total
• EPA Train
Probe & Cyclone
Filter
Water Impingers
Total
Total
Particulate
mg/SCM
13
20
15
11
59
3
4
23
30
3
26
(29)
3
32
(Long
Run 66
Vanadium
Analysis
Wt. %
1.82
1.82
0.78
0.85
0.43
2.81
7.6
1.82
6.27
0.13
Residence Time Case)
-
Vanadium
Content
ppm (on fuel)
3
5
1
1
10
<1
1
.22
23
1
21
Trace
22
Total
Particulate
mg/SCM
3
24
12
7
46
3
7
16
26
6
26
(32)
2
34
Run 77
Vanadium
Analysis
Wt. %
5.60
2.17
1.88
3.29
1.76
2.76
12.26
1.88
7.10
0.49
Vanadium
Content
ppm (on fuel)
2
7
3
2
14
1
2
25
28
1
24
Trace
25
Ln
I
-------
- 157 -
APPENDIX 6
CONVERSION FACTORS
ENGLISH TO METRIC UNITS
To Convert From To Multiply By
OF »c (»F _32) 5/9
"H20 mm Hg 1.8682
ft3 m3 0.02832
Ibs/min Kg/min 0.45359
Inches mm 25.4
Btu/lbs Kcal/Kg 0.555
Feet Meters 0.30480
-------
- 158 -
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
l. REPORT NO.
EPA 600/2-76-096
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
COLLECTION EFFICIENCIES OF STACK SAMPLING SYSTEMS FOR
VANADIUM EMISSIONS IN FLUE GASES
5. REPORT DATE
April, 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
H. Lawrence Goldstein and C. W. Siegmund
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Exxon Research and Engineering Company
Products Research Division
P. 0. Box 51
Linden, N. J. 07036
10. PROGRAM ELEMENT NO.
1AA010
11. CONTRACT/GRANT NO.
68-02-1748
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final 7/74 - 6/75
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
SUMMARY - An experimental program has been conducted to measure and compare the effi-
ciency of two stack sampling systems to collect vanadium-bearing particulate emissions
in flue gas. One sampling system was EPA's Method 5, the other was developed by
Exxon Research and Engineering Company for specialized in-house studies.
To evaluate collection efficiency, an extensive factorial study was carried out in
a 50 hp four-pass firetube boiler burning typical residual fuel oils. In each test the
sampling systems were operated simultaneously in the stack to collect the vanadium-
bearing particulate emissions. Three residual fuel oils were tested: two Venezuelan
(359 and 149 ppm V) and one Arabian (39 ppm V). A vanadium balance was established
for each experiment by inventorying both the particulate emissions and the particulate
remaining in the boiler. Test variables, in addition to the sampling systems and fuel
oils, also included two combustion residence times and two sampling probe locations.
The results of the study show that vanadium collection efficiency depends on two
variables: combustion residence time and sampling system. For both systems efficiency
decreases as combustion residence time increases, which results in a particulate size
distribution shift to the submicron range. Where particulate emissions are in the
coarse size range, collection efficiency in both sampling systems is almost quantita-
tive. The oxidation states of vanadium in fuel oil emissions are briefly discussed.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Particles
*Vanadium
*Residual Oil
Flue gases
*Collecting methods
*Efficiency
Chemical analysis
13B
07B
21D
21B
14B
07D
18. DISTRIBUTION STATEMENT
Released to Public
19. SECURITY CLASS (This Report)
21. NO. OF PAGES
167
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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INSTRUCTIONS
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17. KEY WORDS AND DOCUMENT ANALYSIS
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