EPA-R2-73-272
June 1973
Environmental Protection Technology Series
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EPA-R2-73-272
LIMITED
OIL GASIFICATION
EXPERIMENT
by
Harold P. Sorensen
International Materials Corporation
Northwest Industrial Park
Second Avenue
Burlington, Massachusetts 01803
Contract No. 68-02-0296
Program Element No. 1A2013
EPA Project Officer: William J. Rhodes
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
June 1973
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This report has been reviewed by the Environmental Protection Agency and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Agency, nor does
mention of trade names or commercial products constitute endorsement
or recommendation for use.
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TABLE OF CONTENTS
Page
OBJECT 1
SUMMARY 1
RESULTS 2
CONCLUSIONS 2
RECOMMENDATIONS 3
DISCUSSION 4
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Object
This Limited Oil Gasification Program is an experimental
investigation of the International Materials' SEGAS™ system process-
ing No. 2 and No. 4 fuel oils and No. 6 high sulfur residual fuel oil.
The experiment was designed to evaluate the feasibility of gasifying a
range of fuel oils and to evaluate the product gas for use as a non-
pollutant fuel gas.
Summary
Tests were run to evaluate the capability of the SEGAS oil gas-
ification process on No. 2 and No. 4 fuel oil and on No. 6 high sulfur
residual oil. Existing hardware, which was designed to fit within the
envelope constraints of an automotive application and to operate on un-
leaded automotive gasoline, was used as the test reformer. Hardware
modifications were kept to the minimum consistent with the program's
objectives.
The reformers consist of three finned tubes connected in series
and mounted in the hot gas outlet of a burner. A boiler-superheater com-
bination, mounted over the reformer and located in the same hot gas
stream, supplied the steam to the reformer for the petrochemical process
within the reformer.
The calibration and endurance programs were completed with
qualified success on No. 2 fuel and were essentially completed success-
fully on No. 4 fuel oil. In the former case, the endurance test produced
a carbon buildup that is thought to have been caused by operating off the
test point because of inadequate control of the process rather than be-
cause the test point had not been properly established in the calibration run,
The calibration program on No. 6 high sulfur residual oil was not
completed by the end of the contract's period of performance. A problem
had been experienced in injecting the oil into the reformer in such a way
as to prevent its coking at the entrance. Several combinations of fuel
nozzles, steam injection techniques, reformer packing, and steam and
reformer temperature variations were investigated; and significant progress
was made as evidenced by decreased rate of coke buildup. However, satis-
factory operating conditions for the endurance test were not established.
Samples of the product gas were taken at specific times through-
out the endurance test programs. Some of these samples were analyzed
-1-
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-2-
by a gas chromatograph at International Materials and the remainder were
sent to an outside laboratory for an independent analysis.
Results
1. The SEGAS™ process did not adequately reform No. 2 fuel
oil on this program. This was evidenced by an erratic reformer pressure
drop during the endurance test, condensable deposits in the output plumb-
ing from the reformer and a carbon deficient analysis of the process based
on a chemical analysis of the fuel and a chromatographic analysis of the
output gas.
2. The test on No. 4 fuel oil was essentially successful in that
the six hour endurance run produced no buildup in reformer pressure drop
and subsequent inspection showed no evidence of carbon accumulation in
the reformer or any significant amount of condensables in the output plumb-
ing. However, the mass balance performed on the basis of the chemical
analysis of the fuel and the chromatographic analysis of the output gas
shows a small carbon deficiency.
3. The calibration test on No. 6 high sulfur residual was not
completed in that conditions were not achieved that produced a non-
deficient process analysis or that showed no accumulation of carbon in
the reformer or of condensables in the output plumbing. However, excellent
progress was made toward achieving stable operation of the system in that
runs of over one-half hour had been made before the reformer pressure drop
became excessive.
Conclusions
1. The increasing reformer pressure drop during the endurance
run on No. 2 fuel oil suggests carbon accumulation in the reformer. This
is because the rate of decomposition of the hydrocarbon fuel is greater than
the rate of gasifying. These rates can be brought into balance by changing
the rates of heat transfer into the process gas and/or by lowering the
pressure at which the reaction takes place. The condensable hydrocarbons
in the output plumbing and the failure to achieve a mass balance on the
process show that the process had not been carried to completion. This
can be corrected by increasing the time at which the reacting constituents
are at temperature which can be accomplished by increasing the length of
the reaction tubes and/or modifying process pressure. Therefore, it is felt
that with additional effort the prospects of meeting the program objectives
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-3-
with No. 2 fuel oil are very good.
2. The lack of carbon buildup in the reformer on the No. 4 fuel
oil endurance test indicates that the process was being conducted in a
state of equilibrium. The slight mass unbalance and the small amount
of oily deposit in the product gas plumbing suggests that the process
was not quite going to completion, in that there were condensable hydro-
carbons in the product gas. This can be corrected by slightly increasing
the time at which the process constituents are at the reacting tempera-
ture, which requires that the length of the reformer be increased and/or
that process pressure be increased. Thus, only a slight increase in
reformer length may be required to meet the program objectives with
No. 4 fuel oil.
3. The increasing reformer pressure drop experienced on the No. 6
high sulfur residual oil calibration test indicates that the run was not
made at equilibrium conditions. For successful operation these conditions
will have to be established and the determination of reformer length to
carry the process to completion will have to be made.
Recommendations
1. The decomposing and reforming reaction characteristics of
hydrocarbon fuels suggest that the program objectives can be met by
operating the reformer at different temperature and pressure conditions
than were used and by increasing the length of the reformer. It is recom-
mended that the investigation be continued in this direction and, when
satisfactory operating conditions are established, the endurance test
should be rerun.
2. The program on No. 4 fuel oil was essentially completed
successfully. The only objective not completely met was that the process
was not quite carried to completion as was shown by a mass balance
analysis and which was verified by a light oily deposit in the product gas
plumbing. This suggests that the length of the reformer and/or process
pressure should be increased. It is recommended that the calibration test
be run using a longer reformer and, when satisfactory operating conditions
are established, the endurance run should be repeated.
3. The progress experienced in establishing acceptable operating
conditions with No. 6 high sulfur residual oil suggests that the prospects
are good for meeting the program objectives. Therefore, it is suggested
that the calibration program be continued and, when satisfactory operating
conditions are established, a six hour endurance run should be made.
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-4-
Discussion
1. SEGAS™ Process
The SEGAS process is a high temperature petrochemical reaction
in which a liquid hydrocarbon is thermally decomposed and, in the presence
of high temperature steam, is reformed into a synthesis gas product, the
composition of which depends somewhat on the conditions at which the
process is operated. The criteria of acceptable performance is that the
reformer should run in stable equilibrium indefinitely and that the process
should be carried to completion, i.e. no condensable hydrocarbons in
the output product.
The cracking process is pressure and temperature dependent, the
rate increasing with an increase in either of these parameters. This
process takes place throughout the reformer as the fuel decomposes
progressively from higher hydrocarbon compounds to carbon with the
addition of heat.
The reforming process is temperature and pressure dependent, the
rate increasing rapidly with increasing temperature and, consistent with
the LeChatelier-Braun principle, decreasing somewhat with increasing
pressure. This process takes place in the presence of an oxidizer, high
temperature steam, which is injected into the reformer with the fuel. Thus,
with the rate of cracking increasing with temperature and pressure and
the rate of reforming increasing with temperature and decreasing with
pressure, the regime of satisfactory reformer operation is bounded by a
complex temperature-pressure relationship.
In addition to the chemical reaction considerations, there is the
thermal transfer consideration. The SEGAS process may be described as
one that operates at high temperature and requires a substantial heat input.
Because of the high temperature, most of the heat transfer is by radiation.
Radiant heat transfer is time related and so the heat transfer to the re-
acting constituents is increased with the length of residence time in the
radiating environment. Since residence time increases with process
pressure, radiant heat transfer also increases with process pressure. This,
then, makes it desirable to operate the process at the maximum pressure
consistent with the tolerance of the petrochemical reaction. Because process
completion is residence time dependent, the use of existing small reformers
was damaging to this program in that these reformers were not large enough
to provide the residence time needed to completely gasify the No. 2 and
No. 4 fuel oils and the No. 6 high sulfur resid oil run on this program.
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-5-
2. Test Procedure
The reformer was set up for the No. 2 fuel oil test on No. 1 test
facility at International Materials and was pressure checked preparatory
to operation. The test stand instrumentation consisted of: pressure
sensors, temperature sensors, flow sensors, pressure regulators, and
flow regulators — all of which were checked out and calibrated prior to
the test. With the test facility in order, the first phase of the test program,
the calibration run, was started. This was an exploratory program in
which acceptable conditions were established for the endurance run with
the reformer operating at an acceptable steam-fuel ratio of 4 to 6:1.
With the operating conditions established in the calibration run,
the endurance test was started. The reformer was brought to the established
conditions and data points were recorded at about 15 minute intervals.
The data read were: time of reading, fuel and air flow to the main burner,
fuel flow to the reheat burner, oil flow and water flow to the reformer,
temperature of the steam into the reformer, of the reformer tube, of the
gas out of the reformer, and pressures of the steam at the mixing chamber,
of the fuel at the nozzle and of the product gas at the reformer outlet.
The same calibration and operating procedures as used for No. 2
fuel oil were used for No. 4 fuel oil. The calibration test was in process
on No. 6 high sulfur residual oil when the contract's period of performance
ended.
3. Test Hardware
The reformers that were used on this program were designed to
provide the fuel demands and to fit within the envelope constraints of an
automotive application and to operate on unleaded automotive gasoline.
A sketch of the reformer is shown in Figure 1. The feedstock is sprayed
through a fuel injection nozzle into the mixing chamber at the input end
of the reformer where it mixes with high temperature steam prior to pass-
ing through the reformer and being decomposed and reformed. The reformer
consists of three high temperature alloy tubes connected in series by
short crossover pipes. Thus, as the reforming process proceeds, the
fuel and steam pass through all three tubes. The reforming process is
endothermic and so heat must be supplied continuously. This is provided
by an external burner in which gas and air are mixed and burned and which
is located under the reformer tubes. The products of combustion pass
around the reformer tubes which are finned to encourage convective heat
transfer in addition to the radiant heat transfer that would normally occur.
After the products of combustion have heated the reformer tubes, additional
burner gas is supplied to a reheat burner to raise the temperature to that
required by the boiler superheater which produces steam for the reformer.
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The products of combustion then pass through snd release energy to the
steam superheater. From the superheater the products of combustion
pass through the air preheater, releasing heat energy to and raising the
temperature of the air being supplied to the burner. The products of
combustion are then exhausted to the atmosphere. The calibration
procedure was to bring the reformer to operating temperature with steam
flowing and then to turn the fuel oil on. The oil flow, steam flow and
temperature and output gas temperature were then adjusted to operate the
reformer at the maximum temperature where it would be in stable equilib-
rium. Complete readings and'gas samples were taken. This procedure
was run on No. 2 and No. 4 fuel oils and was being run on No. 6 high
sulfur residual oil when the contract's period of performance ended.
The reformer tubes are filled with non-catalytic packing material
which receives radiant energy from the tube walls and provides heat
transfer surface for the reaction. This material also promotes turbulent
flow and aids in mixing the reacting constituents. After the gas is
processed through the reformer, it passes out through a condenser where
the residual water is separated out. The reformed or product gas then
passes through a back pressure regulating valve which serves to control
the pressure at which the process is operating. The product gas then
passes through a flare tube where it is burned or from which test samples
are drawn.
4. Test Facility
It was initially intended that the Limited Oil Gasification
Experiment would be run on a time sharing basis with other programs in
an existing facility. With this arrangement it soon became apparent that
schedule conflicts would cause excessive delays in the program. There-
fore, a separate test facility was built on International Materials funds
for the Limited Oil Gasification Experiment and has been used exclusively
for this work. In addition, a portion of this program was run in the facility
originally intended. Schematic drawings of the two test facilities are
shown in Figures No. 2 and 3.
These facilities are similar in that they contain systems for
controlling and measuring: the flow of oil to the reformer, of water to
the steam generator, of fuel and air to the reformer burner, and of measur-
ing temperatures and pressures: of the steam into the reformer, of the gas
out of the reformer and of the temperature of the reformer tube. The primary
difference between the facilities is in the manner in which fuel flow is
measured. In the original test facility the fuel flow was measured by means
of rotameter flow sensors which indicate flow visually by the position of a
-------
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ball in the flowing fluid stream. The fuel supply was from a tank charged
with regulated air pressure to supply the flow producing force. On leav-
ing the tank, the fuel passes through the rotameter flow sensor and then
to the flow control system which consists of a micrometer adjustable
valve across which the pressure drop is controlled by a throttling regulator
valve. Thus, the flow through the system is a function of the opening of
the adjustable valve and is unaffected by variations in upstream or down-
stream pressures in the system.
Because the new test facility was intended to be used for the
Limited Oil Gasification Experiment in which opaque No. 4 fuel oil and
No. 6 high sulfur residual oil would be run, a visual flow sensing system
such as a rotameter was not acceptable. It was decided to use, as the
flow sensor, a calibrated positive displacement pump driven by a variable
speed electric motor and equipped with a speed counter. The pump was
calibrated over the range of flows and backpressures that were anticipated
for the test program by flowing the output into a graduated flask for a
specific period of time. The runs were repeated and it was found that
consistent calibrations were obtained and that, within the limits of observa-
tion accuracy and over the range that was to be used on the test program,
the system was insensitive to backpressure. The calibration curve is
shown as Figure 4.
The gas supply to the reformer main and reheat burners was from a
regulated constant pressure source and was measured with a rotameter.
The calibration curves are shown as Figures 5 and 6. The flow was con-
trolled by means of a throttling micrometer valve. The flow of air to the
burner was supplied by a turbo blower and was determined by measuring
the pressure drop across an orifice of known size. The calibration curve
is shown as Figure 7. Control was by adjusting the position of a waste
gate located between the blower and the sensing orifice. Thus, if the
pressure drop across the orifice was too large, indicating excessive flow
to the burner, the waste gate opening could be increased to bypass a
portion of the blower output to the atmosphere. In the converse case,
the waste gate opening would be decreased to reduce the wastage and in-
crease the flow to the burner.
The temperature of the steam leaving the steam generator and enter-
ing the reformer was measured by means of sheathed chromel-alumel thermo-
couples projecting, at right angles, into the flow stream paths. The reformer
tube temperature was measured using an intrinsic platinum-platinum 10%
rhodium thermocouple and the product gas temperature was measured by a
sheathed thermocouple inserted into the product gas outlet of the reformer.
The reformer output flow was passed through a cooling coil to
-------
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-15-
condense the excess water and condensable hydrocarbons. The liquids
were then collected in a reservoir and were periodically tapped off for
visual inspection. The product gas was passed through a regulator valve
which served to hold the process pressure at the selected value by modulat-
ing the flow orifice area. The flow rate was measured downstream of the
regulator valve by passing the gas through a fixed orifice of known area
and determining the gas temperature and pressure drop. From these data
the flow was computed. Downstream of the regulator the gas passed
through a flare tube to the atmosphere where it was burned. The flare tube
was equipped with a "T" to which flasks were attached for drawing off gas
samples for analysis.
5. Test Results
The graphic log of the endurance tests on No. 2 fuel oil and the
product gas sample analysis are shown by Figures 8 and 9. The data sheets
are shown by Figures 10, 11 and 12. The graphic log shows the reformer
tube temperature, steam to mixing chamber temperature, the output gas
temperature, the mixing chamber pressure, and the backpressure.
Inspection of the graphic log shows excursions in reformer tube
temperature from 2070° F to 2160° F. It can be noted that there is a
corresponding variation in the temperature of the steam to the mixing
chamber. These temperature excursions are large enough to have an up-
setting effect on the process and, because they occur together, indicate
inadequate control of the reformer burner temperature. This is because
the superheater, which supplies the steam to the mixing chamber, is heated
by the same gas stream, supplied by the main burner, that heats the
reformer tubes. The curve of temperature of the steam to the mixing chamber
shows a dramatic drop after 5 1/2 hours of endurance operation. Subsequent
to the test, the thermocouple was checked and inspected and was found to
be malfunctioning. It is assumed that the failure occurred after 5 1/2 hours.
The output gas curves show a drop of 100° F at the 4 1/4 hour point. There
is no other data to corroborate this drop; and because of this, and because
it is exactly 100° F below where it is expected to be, it is felt that it is
a reading error.
The reformer pressure drop can be obtained by subtracting the back
pressure from the mixing chamber pressure. Comparing the curves of these
pressures it can be seen that this pressure drop is erratic and the variations
increase toward the end of the test run. An increase in pressure drop
across the reformer indicates partial blocking with deposited but unreformed
carbon. An erratic pressure drop indicates a variation in the rates of carbon
deposition and reformation. These variations in reformer pressure drop can
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I TO H 132
7 X 10 INCHES »
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PRODUCT
GAS SAMPLE ANALYSIS
CORRECTED TO BE FREE OF AIR & H2O & NORMALIZED
No. 2 Fuel Oil C7 3 H12 lg
Sample No.
12-12-72-1
*12-12-72-2A
*12-12-72-3
12-12-72-4B
*12-12-72-5C
12-12-72-6C
*12-12-72-7D
H2
%
61.8
68.5
64.6
62.5
67.2
64.6
65.1
CH4
%
5.0
4.0
6.3
5.9
4.7
4.5
5.6
CO
%
26.0
20.1
23.7
26.0
20.7
22.5
22.3
C02
%
7.9
7.4
5.4
5.6
7.4
8.1
6.9
C2H4
%
0
0.02
0.02
0.02
0.02
0.34
0.02
% Carbon
Deficiency
- 1.77
+ 36.6
+ 30.9
+ 15.7
+33.3
+ 16.4
+ 27.7
H.H.V.
Btu/cu ft
329.2
322.7
344.0
340.7
326.8
327.2
334.6
12-12-72-8 62.9 5.4 24.8 6.8 0.01 +13.2 333.6
*Analysis by an outside testing laboratory
FIG. 9
-------
Run No.:
TEST OBJECTIVE:
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be seen to generally correlate with high reformer tube and steam to the
mixing chamber temperatures, which are known to be critical to the rates
of the decomposing and reforming reactions. Therefore, it is felt that
better control of the burner temperature would have significantly improved
the test results. The graphic log also includes notations of when gas
samples were taken for chromatograph analysis. The unmarked analyses
were performed on the gas chromatograph at International Materials and
those indicated by an asterisk were performed by an independent outside
laboratory. A copy of the laboratory report is attached, Fig. 13. This
report shows the carbon monoxide concentration to be lower and the methane
concentration to be higher than was shown by the analyses at International
Materials. The descrepancy was found to be caused by these values being
interchanged in the outside laboratory report. This is explained in their
letter, Figure 14.
To evaluate the completeness of the process, a mass balance was
performed using the chemical analysis of the fuel and the chromatograph
analysis of the output reformed gas. The criterion developed to express
the degree of completeness was percentage of carbon deficiency. This
can be expressed:
i % Carbon Deficiency = Input Carbon - Output Carbon X 100
Input Carbon
An analysis showing zero carbon deficiency is for the reaction going to
completion and an analysis showing some carbon deficiency indicates
condensable hydrocarbons in the output product and therefore showing
that the reaction has not proceeded to completion. The greater the carbon
deficiency the less complete the reaction.
The graphic log for the No. 4 Fuel Oil Endurance Test is presented
in Fig. 15. These curves show the reformer tube temperature, steam to
mixing chamber temperature and output gas temperature to be maintained
at close limits and a negligible variation in reformer pressure drop to exist
throughout the test run. The test was interrupted after about 4 hours to
replenish the gas supply system for the reformer burner. The shutdown
period was approximately 45 minutes, during which the backpressure valve
was disassembled and inspected. A light oily film was found on the parts,
was wiped off and the unit was reassembled. The test proceeded to
completion without incident. A tabulation of the output gas analysis from
the No. 4 Fuel Oil Endurance Test is given on Fig. No. 16. As in the
case with the tabulation of the No. 2 Fuel Oil Endurance Test, the samples
indicated by asterisks were analyzed by an outside independent testing
laboratory and the remainder were analyzed using a gas chromatograph at
International Materials. These analyses also can be shown to be slightly
-------
-22-
NEW ENGLAND ANALYTICAL & TESTING LABORATORY
2 SHADY OAK LANE
NATICK, MASS. 01760
(area 617) 873-8469
Jecember 15, 1972
REPORT OF ANALYSIS
?or: international Materials Corp.
Northwest industiial park P.S.R. 23066
Second Avenue
Burlington, Mass. 01303
.-.tt: Mr. ril. Able
problem: TO analyze four gas samples for the following components;
H2, 02, N2| CO, CH4, CO2 , C2 , H4, ana C2H6.
Instrument: Gas Chromatograph with Thermal conductivity jetector.
Results:
Component sample Numbers
Hydrogen 69.523 62.524 647537 6677T4"
Oxygen 0.036 0.036 0.140 0.039
Nitrogen 0.150 0.163 0.613 0.175
Carbon Monoxide 4.095 6.066 4.516 5.746
Methane 20.410 22.945 19.955 22.330
Carbon Dioxide 7.479 5.220 7.135 7.097
Sthylene All samples had less than 0.02%
Ethane None observed in any sample.
rill samples were run in duplicate.
&2spectfully submitted,
Lawrence C. O'Brien
LCO'Breo
FIG. 13
-------
-23-
NEW ENGLAND ANALYTICAL & TESTING LABORATORY
2 SHADY OAK LANE
NATICK, MASS. 01760
(area 617) 873-8469
January 8, 1973
Mr. Jim Able
International Materials Corp.
Northwest Inudstrial park
Second Avenue
Burlington, Mass. 01303
jear Jim,
New England Analytical & Testing Laboratory has been analy-
zing 3as R-euctor samples for international Materials since .-ipril
of 1972, with satisfactory results.
Recently, N.E.a.T Lab. has analyzed two sets of four samples
each, reported on December 15, 1972, and January 5, 1973. These
results reported to international Material each contained an error
as follows:
December 15, 1972 Report. The figures calculated for the
^ethane, and carbon Monoxide concentrations were interposed, i.e.,
the CO figures were reported for the CH4, and vice versa. The fig-
ures should have read;
Component SAMPLE NUMBERS
Methane #2 A 3B 5C 7D
4709T 67H66 475*16 57746
Carbon Monox-
ide 20.410 22.945 19.955 22.330
These changes were verbally corrected with Chuck paltz on jec-
ember 17, 1972.
January 15, 1973 Report. This report contained an abnormally
high concentration of carbon jioxiae. The source of the error was
found to be a new instrument that was put into service on Jan. 3, 1973.
The resistors of the attentuat.or in the #3, and #16 position were iden-
tical, instead of being 50^ different. so, the figures reported were
twice the concentration of what was actually present. The following
figures are the real concentrations which should have been reported;
Component sample Numbers
#2 #3 #5"" #7
Carbon Dioxide 6.512" 6TTTO 5.830 7.975
yours very truly,
Lawrence C. O'Brien
LCO'B;eo
FIG. 14
-------
.. . J TC :H ._ 13
7 X 10 INCHES «»OI III U.S.A.
KEUFFEL. « ES8ER CO.
-------
PRODUCT
GAS SAMPLE ANALYSIS
CORRECTED TO BE FREE OF AIR & H2O & NORMALIZED
No.
Sample No.
12-28-72-1
*12-28-72-2
*12-28-72-3
12-28-72-4
12-28-72-5
*12-28-72-6
*12-28-72-7
12-28-72-8
"2
62.4
61.6
61.7
60.8
60.3
61.9
60.0
60.4
CH4
6.1
7.1
7.0
7.2
7.1
7.0
8.0
8.1
CO
23.6
24.1
23.6
25.8
27.3
24.2
23.4
25.5
co2
7.9
7.2
7.6
6.0
5.0
6.8
8.6
5.3
C2/H4
0.02
0.08
0.07
0.25
0.25
0.08
0.034
0.51
C2H6
0
0
0
0
0.04
0
0
0.15
% Carbon
Deficiency
+ 9.8
+ 12.9
+ 12.8
+ 12.2
+ 10.8
+ 16.0
+ 4.9
+ 18.4
H.H.V.
Btu/cu ft
334.6
344.1
342.5
351.1
353.9
345.3
345.6
364.9
*Analysis by an outside testing laboratory
FIG. 16
-------
-26-
carbon deficient indicating that the reformer was not quite long enough to
completely decompose and reform the No. 4 fuel oil. Copies of the test
data sheets are included, Figs. No. 17, 18, 19 and 20. The report from
the independent laboratory is shown, Fig. 21. This report shows the
carbon monoxide concentration to be higher than was shown by the
analyses at International Materials. The discrepancy was determined to
have been caused by an incorrectly assembled attenuator in a new piece
of test equipment being used for this work. This is explained in a letter
from the vendor, Fig. 14. Laboratory analyses of the fuels used on this
test and of the content of the ash are shown in Figs. 22 and 23.
The test program on No. 6 high sulfur residual oil was in the
calibration phase when it was halted. Progress had been made toward
establishing satisfactory endurance conditions but completely acceptable
conditions had not yet been achieved.
Early in the calibration program it was found that No. 6 oil behaved
differently in a reformer from No. 2 and No. 4 oil. There were both
mechanical problems in that No. 6 oil was much harder to spray and process
problems in that No. 6 oil had different kinetics on decomposing and reform-
ing than No. 2 and No. 4 fuel oils.
The problem in spraying the fuel was in the availability of equip-
ment to spray No. 6 high sulfur oil at the rates required by this program.
There was an abundance of equipment available for spraying No. 6 oil in
fine enough droplet sizes for the requirement of this program. However,
the available equipment was designed for large power plant boiler applica-
tions and the minimum flow capability was much more than the maximum
flow capability of the reformers used on this test. Some steam injection
nozzles were investigated but their minimum steam flow requirement at
the fuel flow that the reformer could handle resulted in an unacceptable
steam-carbon ratio for the test.
Work was done at International Materials to find ways to use the
process steam to break the fuel stream into acceptably small droplets to
establish a reformer packing density that would control the rate of decompos-
ing the oil within acceptable limits and to find ways to inject the superheated
steam to achieve the desired high rate of reforming. However, at the time
that the test was halted, the kinetics of processing No. 6 high sulfur
residual oil were not well enough understood or controlled to permit a run
of over about 1/2 hour before the reformer pressure drop became excessive.
This required that the fuel be shut off and the reformer be cleaned out by
purging with high temperature steam. There are many reformer operating
conditions and combinations of conditions that remain to be explored and
it is felt that a regime will be found where the decomposing and reforming
-------
Run No.:
-27-
REFORMER DATA SHEET
Date: lZ-Z8'7Z
TEST OBJECTIVE:
FUEL
UEL lL
Ol
Sheet No. / OF
OtL
TIME ON: IZ!O6
TIME OFF:
NOZZLE: 6O°CoAj£r 6ouo - /.SGPtf- Moo. TUBE PACKING:
TPMC
FLOWS: Air M^fj^^^
Air Ref. # 2
Air Ref. # 3
* /*/^ w^
v&V£>£Vv09DA4S
H2 ReP. * 1 Rehear ^/<5^
H2 Ref. # 2
H2 Ref. # 3
Main Water Gt/tf,^
Auxiliary Water
Oil CC/H,*/
TEMPS: Ref. Tube #1
«y£T Ref. Tube #2
Ref. Tube # 3
Steam to Mix. Chamber
Output Ref. # 1
Auxiliary Steam
Output Reformer ^ 2
Output Reformer # 3
Pressures: Oil Nozzle
/°5/ Mixing Chamber
£A0 To IpuP^oiatnx
UutpuT Ker.
//^P ^"5 f^9StMK
(JUTpUl Ket . i
F<*ea,jESacygffbaB6.
input net. a
Cathedral Ref. # 3
Output Ref. # 3
Back Pressure
/^'^
ZO
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3O
0
1200
800
6>oo
Vj \
«?l
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f.Z
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1670
ffoO
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5
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&
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IO
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I/*L
(U
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IZ:30
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36
6
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mo
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£
18
10
//r
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/c/c/
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io
12:36
ZO
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6
1980
1730
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59
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ZO
1.3
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36
6
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1730
/&30
0
Si
61
5~4
^~
vjO
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(O
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to
I.I
¥6-
36
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to
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36
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60
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sy
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36
6
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I5VO\
ll
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60
GV
^T^7
\j /
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/<-/t-/
to
3~*/-
FIG 17
-------
Run No.:
TEST OBJECTIVE:
-28-
REFORMER DATA SHEET
Fi/tTL. OlL.
Date:
Sheet No.
FUEL:
NOZZLE: 6O*
TIME ON: TIME OFF:
PACKING:
TM€
A /* /*/ M4CWE5 OF HtO
FLOWS: Air Ref.n^gJt,
Air Ref. * 2
Air Ref. # 3
H2 Ref, * Pfifg™1*
,, n . a 6CKj£&*BtAA
H2 Ref. # 1 Reheat ffc£
H2 Re?f. # 2
H2 Ref. # 3
Mdn Water C.C/H,u
Auxiliary Water
Oil
to
I.Z
#r
J6
£
&>*r
/7^o
/5%?
60
SV
S7
too
10
W
/:tt
1.0
I.Z
ftf
36
6
teif
1700
/57 CiJ
P__i
'
60
SV
^7
/^^7
10
5V
2/50
Z.0
/.2
US'
36
^
20^3
/753-
3:30
Z.O
I.Z
W
36
6
ZPVO
/690
I5OO
N
\
«r^
^
60
5"^
5~7
/OO
10
5V
3:^
z,o
I.Z
US'
36
6
2&to
1690
iszo
V
R
d
60
5~T
v5-?
/O^>
10
53-
FIG. 18
-------
Run No.:
-29-
REFORMER DATA SHEET
Date:
O/L
TEST OBJECTIVE: # ty f=i/£L
FUEL: #if- FuEl. OlL. TIME ON: TIME OFF:
NOZZLE: (>O*Coi(Je3ouO-{S~(3PH'Woo. TUBE PACKING:
Sheet No. v3
FIG. 19
-------
Run No.:
-30-
REFORMER DATA SHEET
Date:
- 72
TEST OBJECTIVE:
Sheet No.
FUEL:
TIME ON:
TIME OFF:
7:01
NOZZLE: 6O*&>4/E- $OUQ- I.S~GPH~MoO. TUBE PACKING:
TIW€
FLOWS: Air' Ref. ]$-*ffi*,ffJ$£
Air Ref. .* 2
Air Ref. * 3
2 ?l * - • ^^Ti** fi^
H2 Ref. * 1 Reheat Fic£
H2 Re*. # 2
H2 Ref. * 3
Mcrfn Water CC/rf,*j
Auxiliary Water
Oil CC/HnJ
TEMPS: Ref. Tube #1
^5f/^fpMa?n ex.
^
HjOTPltfti f~^moo
36
6
2PSO
1690
/s/o
v ^
s f
^ o
y fr,
»
•
/
.
50
f*
5o
/ OO
to
5D
FIG. 20
-------
-31-
NEW ENGLAND ANALYTICAL & TESTING LABORATORY
2 SHADY OAK LANE
NATICK, MASS. 01760
(area 617) 873-8469
January 5, 1972
REPORT OF ANALYSIS
?or: international Materials Corp.
Northwest industrial park P.O.tt Mr. sorensen*3
Second avenue Letter
Burlington, Mass. 01303
Att- Mr. Harold p. sorensen
Engineering Mgr.
problem; TO analyze four gas samples labeled #122372-2, 3, 6 & 7,
for the following components; Hydrogen, Oxygen, Nitrogen, car-
bon monoxide, Methane, carbon Dioxide, Ethylene, sthane, and
CarjDOnyl sulfide, and Hydrogen Sulfide.
instrument: Gas Chromatograph with Thermal conductivity Detector,
and Linear Temperature programmer.
Results:
Sample numbers
Component
Hyarogen
Oxygen
Nitrogen
Methane
Car. Monoxide
Car. Dioxide
Ethylene
Ethane
Hy. Sulfide
#2 #3
"557365 BTT752
0.029 0.202
0.129 0.341
6.347 6.206
21.633 20.976
13.024 13.421
0.073 0.060
None Resolved
None detected by
53T322
0.231
1.273
6.037
20.366
11.660
0.070
response or odor.
#7
557? 74
0.145
0.587
7.419
21.749
15.950
0.032
Car.sulfide** 2-4ppm. 2-4ppm. 4-6ppm. 8-10ppm.
** Identity estimated by retention time plots, and odor.(NO standards
with samples.)
Remarks: All samples run in duplicate. Results called into Mr.
Sorensen the morning of January 2, 1973.
submitted,
,^ /*
Lawrence c. O'Brien
LCO'Breo
FIG. 21
-------
-32-
FUEL SAMPLE ANALYSIS
Conducted by
WALBAR LABORATORIES
Sample
No. 2 Fuel Oil No. 4 Fuel Oil No. 6 Residual Oil
c
H2
S
N
BTU/lb.
Specific Gravity
Viscosity
87.58
12.16
00.00
00.054
19,464
.85571
33.9° API
86.94
12.23
00.40
00.126
19,317
.89190
27.2° API
85.83
11.29
2.05
0.416
18,570
.95805
16.2° API
FIG. 22
-------
-33-
r-.iylcon, Inc. P.O. Box 86
Wide spectrum analytical & Boston, Mass. 02122 January 23, 1973
consulting services Tel. 617 287-0200
CLIENT; International Materials Co.
Northwest Industrial Park
Second Avenue
Burlington, Massachusetts 01803
Attention: Mr. Sorensen
CASE NO. 1417
PURPOSE OF TEST: Chemical analysis of two (2) samples of
fuel oil
SAMPLE IDENTIFICATION; Sample marked: #4, #6
METHOD OF TEST; Ash Content: A.S.T.M D482
Ash Composition: Emission Spectroscopy
RESULTS;
£4 £6
Ash % By Weight 0.07 0.09
Composition Of Ash;
Silicon D 3E
Vanadium 3E D
Nickel E 3E
Tin 3F F
Iron F F
Sodium F E
Lead F F
Zinc F F
Aluminum 3G 3F
Calcium 3G 3F
Copper 3G] 3G
Chromium 3G 3G
Magnesium 3G F
Barium G G
Titanium G 3G
FIG. 23
-------
-34-
January 23, 1973
International Materials Co.
Case No. 1417
- 2 -
Composition Of Ash; (Continued)
Silver
Manganese
Molybdenum
Strontium
II
3G
3H
£6
3G
3H
G
3H
KEY; A - Greater Than 10%
B = 1 - 10%
C = .1 - 1.0%
D = .01 - .1%
H *•
COMMENT:
E = .001 - .01%
F = .0001 - .001%
G = Less Than .0001%
3B = Three Times Letter Value
Silica and vanadium were the major ingredients in the #4 oil.
Vanadium, nickel and silicon were the major ingredients in the
#6 oil.
Respectfully submitted,
ANYLCON, INC.
Robert A. Sullivan
Presdient
RAS:pr
-------
-35-
kinetics will be compatible and stable reformer operation will be possible
with the reaction going to completion.
6. Variations in the Test Results
The differences in the normalized air and water free gas sample
analyses tabulated in Figures 9 and 16 can be attributed to actual differences
in the gas samples and to variations in the gas analysis and data redaction
techniques. The differences in the gas samples are due primarily to the
difference in temperature at which the process was being run at the time
that the samples were taken.
The graphic log for the No. 2 fuel oil test, Figure No. 8, shows
significant differences between the steam temperatures and between the
reformer tube temperatures when the various gas samples were taken. Be-
cause reactions taking place in the process are strongly temperature
dependent, the product gas composition is also strongly temperature depen-
dent. Thus, the differences in the process temperature at the time that
the samples were taken can be expected to produce a significant difference
in composition of the gas samples. The process temperature control was
closer on the No. 4 fuel oil run than it was on the No. 2 fuel oil run as can
be seen by comparing the graphic logs for the two tests, Figures Nos. 8
and 15. Comparing the gas analysis tabulations for these tests, Figures 9
and 16, shows a much smaller difference in gas composition on the No. 4 fuel
oil run than on the No. 2 fuel oil run. The smaller difference is attributed
to better process temperature control.
In addition to the difference in gas composition, there are differences
in the gas analysis due to differences in operating the gas chromatograph
and in interpreting the results. Gas chromatography compares the type and
concentration of constituents in a sample gas to the concentration of the
same constituents in a calibration gas. The output is a series of peaks
on a strip chart. To minimize the chance of error due to nonlinearity in the
equipment, the calibration gas sample is made up to be as near to the
expected concentration as is possible. Because the calibration gas sample
is the reference for the analysis, it is necessary that its constituents be
accurately known. The calibration gas is made by injecting into a container
each constituent at a fixed temperature and at a pressure that is a function
of its desired partial pressure in the mixture. Thus, the limitations of
pressure instrumentation dictates that the percentage error in each constituent
in the calibration gas is an inverse function of the proportion of that con-
stituent in the whole. Therefore, a larger error can be expected in the
minor constituents than in the major constituents in the calibration. This
error, which will appear in the analysis of unknown samples, can be expected
-------
-36-
to vary linearly from as much as + 2.5% for constituents that are 10% of the
whole to + 0.4% for constituents that are 60% of the whole.
Another variation in gas chromatograph analysis is in the method
by which the gas samples are injected into the chromatograph. The chro-
matograph at International Materials has an automatic gas sampling valve
through which samples of a fixed volume are injected. Because the process
is automatic, there is no change for error due to differences in operator
technique. The temperature of the gas samples being injected is held to
+ 1° F and, because the reference is absolute zero, this will be responsible
for an error of less than + .25% in the output. The samples are injected
into the chromatograph at atmospheric pressure. Because calibration
samples are run daily, the error due to pressure differences will be that
caused by the daily variation in barometric pressure, which seldom is as
much as one inch of mercury. Because the reference is absolute pressure,
the error from this source will generally be less than one part in 30 or about
+ 3%. The temperature and pressure effects will act on all of the constituents
proportionally. Thus, a change in atmospheric pressure or sample tempera-
ture between calibrating the chromatograph and running the test will cause
the total of the test analysis to deviate from 100%, but each of the con-
stituents will be the correct proportion of the whole. Therefore, normalizing
the result will eliminate the variations due to changes in atmospheric
pressure and sample temperature.
The third source of error is that associated with reducing the data
from the strip chart. The output of the chromatograph appears as a series
of peaks on a strip chart recording. The position of the peak with respect
to the time at which the sample was injected into the chromatograph reveals
the constituent and the area under the peak determines the amount of the
constituent. In practice, to avoid tedious procedures for determining the
areas under the peaks, the amount of the constituent is approximated by
using the height of the peak as an indication of the area under the peak. This
"peak height determination" method is a recognized and widely used technique
in gas chromatography and has been shown to give a one sigma error distribu-
tion of + 4%.
As an overall check on the procedure at International Materials, a
gas sample was carefully made up by a competent external supplier and
was treated as an unknown. The result of this test is shown in the following
table:
-------
-37-
International Materials
Constituent Analysis Actual
H2 55.379 54.9
O2 .997 1.0
N2 3.918 3.8
CH4 10.004 9.8
CO 19.258 20.1
CO2 6.082 6.2
C2H4 2.015 2.1
C2H6 2.189 2.2
The procedure used by the independent outside laboratory was
similar to that used at International Materials except that the manual
syringe method of injecting gas samples into the chromatograph was
employed and their chromatograph was not calibrated on a daily basis.
The syringe method of injecting gas samples is a recognized
technique and can be done with a high degree of accuracy by a skilled
operator. The operators at the independent outside laboratory have the skill
required for accurate work using syringe injection. Thus, it is felt that this
procedure did not have a significant effect on the accuracy of their results.
In spite of the fact that the outside laboratory did not calibrate their equip-
ment daily, they did analyze a test sample gas every day to verify that
their equipment was functioning properly. This is felt to be a reasonable
check. Thus, their lack of daily calibration is not expected to have a
significant effect on their results.
The following conversion table and plot, Figures 24 and 25, will
be helpful in converting from the English units used on this program to the
metric system.
-------
-38-
CONVERSIONS
English Metric
Cubic Feet X 28.32 = Liters
Pounds X453.6= Grams
o
Pounds per square inch X 7.031 X 10 = Kilograms per square meter
Inches X 2.540 = Centimeters
Fig. 24
-------
-£
i TO -I 132
7 X IO INCHES KADI III U.I.I.
KCUFFEL A E88ER CO,
[HI
i
CO
to
I
OS:
I
-------
-40-
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-R2-73-272
3. Recipient's Accession No.
4. Title and Subtitle
Li mi t ed Oi 1 Gasification Experiment
5. Report Date
June 1973
6.
I. Autrior(s)
Harold P. Sorensen
&• Performing Organization Rept.
No.
9. Performing Organization Name and Address
International Materials Corporation
Northwest Industrial Park, Second Avenue
Burlington, Massachusetts 01803
10. Project/Task/Work Unit No.
11. Contract /Grant No.
68-02-0296
12. Sponsoring Organization Name and Address
EPA, Office of Research and Monitoring
NERC/RTP, Control Systems Laboratory
Research Triangle Park, North Carolina 27711
13. Type of Report & Period
Covered
Final
14.
IS. Supplementary Notes
sracts The rep0rt documents tne results of a limited oil gasification program
to experimentally investigate the feasibility of using International Materials
Corporation's Segas system for processing No. 2 and 4 fuel oils and No. 6 high-
sulfur residual oil. Existing hardware, originally designed to operate on gasoline
for automotive applications, was modified for these tests. The process consists of a
high-temperature petrochemical reaction in which a liquid hydrocarbon is thermally
decomposed and then reformed to a synthesis gas in the presence of high-temperature
steam. Although all tests were not completed by the end of the contract, sufficient
progress was made and sufficient results obtained to indicate that the process is
capable of stable sustained operation.
17. Key Words and Document Analysis. 17o. Descriptors
Air Pollution
*Gasification
Sulfur
Oils
Residual Oils
Fuel Oil
Pyrolysis
Petrochemistry
17b. Identifiers/Open-Ended Terms
Air Pollution Control
*Segas process
Fuel Gas
Reformer
Reformed Gas
'"up 2ID, 7C, 13B
18. Availability Statement
Unlimited
19..Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
40
22. Price
FORM NTIS-3S (R6V. 3-721
USCOMM-DC M932-P72
------- |