SPA 6CO/2~'C.I"017
February 1?G1
CATALYTIC INCINERATION OF LOW
CONCENTRATION ORGANIC VAPORS
by
Norman A. Martin
Engelhard/Systems
Engelhard Minerals and Chemicals Corporation
2655 U.S. Route #22, Union, New Jersey 07083
EPA Contract 68-02-3133
EPA Project Officer: ..Bruce Tichenor
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
Prepared for
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
-------
-------
IERL-RTP-1135
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-600/2-81-017
2.
3. REC
4. TITLE AND SUBTITLE
Catalytic Incineration of Low Concentration
Organic Vapors
5. REPORT DATE
FEBRUARY 1981 ISSUING DATE.
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
Norman A. Martin
8. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
Engelhard Minerals and Chemicals Corporation
2655 U.S. Route 22
Union, New Jersey 07083
10. PROGRAM ELEMENT NO.
1AB604
11. CONTRACT/GRANT NO.
68-02-3133
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 10/78-3/80
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES
919/541-2547.
project officer is Bruce A. Tichenor, Mail Drop 62,
The report gives results of a demonstration of the catalytic abatement of
low concentration hydrocarbon vapors on both a pilot- and full-scale system. The
tests were conducted on industrial exhausts containing CO and volatile hydrocarbons.
An economic comparison was made between thermal and catalytic abatement sys-
tems, utilizing this data. The pilot-scale data was obtained over a 5-month period
from a plastic printing plant where the major solvents were ethanol, n-propyl ace-
tate, and heptane. The full-scale data was obtained over a 9-month period from a
Formox (Reichold Chemical Co.) formaldehyde plant exhaust containing CO, di-
methyl ether, methanol, and formaldehyde. The pilot- and full-scale units were
able to convert 97-99% of the pollutants to CO2 and water.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Pollution
Incinerators
Hydrocarbons
Vapors
Catalysis
Plastics Processing
Formaldehyde
Pollution Control
Stationary Sources
Organic Vapors
Thermal Systems
Plastics Printing
13B
07C
07D
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
78
i
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
REPRODUCED BV
NATIONAL TECHNICAL
INFORMATION SERVICE
US. DEPARTMENT OF COMMERCE
' • SPRINGFIELD, VA 22161
-------
DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, Research Triangle Park, N.C., 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 Agencys nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
ii
-------
ABSTRACT
Catalytic abatement of low concentration hydrocarbon vapors has been
demonstrated. This report presents the results of the demonstration con-
ducted on both a pilot and full-scale system. The tests were conducted on
industrial exhausts which contained carbon monoxide as well as volatile
hydrocarbons. Utilizing this data an economic comparison was made between
thermal and catalytic abatement systems.
The pilot data was obtained in a plastic printing plant in which the
major solvents were ethanol, n-propyl acetate, and heptane. Test data was
obtained for a five month period.
The full-scale data was obtained from the exhaust of a Formox* formal-
dehyde plant. The exhaust contained carbon monoxide, dimethyl ether, meth-
anol, and formaldehyde. Test data was gathered over a nine month period.
The pilot and full-scale units were able to convert 97%-99% of the pol-
lutants to carbon dioxide and water. ' .••
This report was submitted in. fulfillment of Contract No. 68-02-3133 by,
the Systems Department of the Engelhard Industries Division of Engelhard
Minerals & Chemicals Corporation under the sponsorship of the U.S. Environ-
mental Protection Agency. . This report covers the period October 1, 1978 to
March 31, 1980, and was completed November 15, 1980.
*Trademark of Reichhold Chemical Company
iii
-------
TABLE OF CONTENTS
Abstract , ill
Figures vi
Tables vii
Acknowledgements viii
1. Introduction 1
2. Conclusions 3
a. Pilot Unit 3
b. Full-Scale Unit 3
3. Pilot Catalytic Unit 4
a. Process Search 4
b. Process Selection 4
c. Process Description 5
d. Pilot Test Unit Description 5
e. Pilot Test Program 10
f. Analytical Techniques 11
g. Results and Discussion 12
4. Full-Scale Catalytic Unit 23
a. Installation 23
b. Process Description 23
c. Full-Scale Unit Description 26
d. Test Program 28
e. Analytical Techniques 28
f. Results and Discussions 28
iv
-------
TABLE OF CONTENTS
5. Economic Comparison . 32
a. Purchase Cost ' 33
b. Annual Cost 33
References • ^0
Appendices
A. Pilot Unit Tests - Complete Data 41
B. Full-Scale Unit Test - Complete Data 48
C. Analytical Methods - Pilot Unit 54
D. Analytical Methods - Full Scale 57
-------
FIGURES
Number Page
1 Flow Schematic - Printing Press Catalytic Pilot Unit 6
2 Flow Schematic Pilot Test Unit 7
3 Catalytic Reactor. . . . 9
4 Effects of Time and Space Velocity on Conversion Efficiency of
Total Hydrocarbons at 370°C „ 16
5 Effects of Time and Space Velocity on Conversion Efficiency of
Total Hydrocarbons at 315°C 17
6 Effects of Time and Space Velocity on Conversion Efficiency of
Total Hydrocarbons at 260°C 18
7 Effects of Time, Temperature and Space Velocity on the Conversion
Efficiency of n-propyl Acetate 20
8 Effects of Time, Temperature and Space Velocity on the Conversion
Efficiency of Heptane 21
9 Flow Schematic - Formaldehyde Plant - Catalytic Abatement System 24
10 Full Scale Catalytic System. 25
11 Flow Sheet - Plastic Printing Plant Catalytic Abatement System . 36
12 Flow Sheet - Plastic Printing Plant - Thermal Incinerator. ... 37
13 Flow Sheet - Formaldehyde Plant Catalytic Abatement System ... 38
14 Flow Sheet - Formaldehyde Plant Thermal Incinerator 39
vi
-------
TABLES
Number . . Pagt
1 Pilot Test Data Summary, Preliminary 13
2 Pilot T-est Data Summary, Months One and Two 14
3 Pilot Test Data Summary, Months Three and Five 15
4 Full-Scale Test Data Summary 30
5 Capital and Annual Costs 34
6 Cost Comparison Factors 35
vxi
-------
ACKNOWLEDGMENTS
The cooperation of the Georgia Pacific Corporation and
their personnel; Mr. Robert O'Conner, Plant Manager and Mr.
Robert Dunne, Plant Manager, is gratefully acknowledged. We
also wish t'o express appreciation to Mr. David Tonini, Tech-
nical Director, La Monte Division, Georgia Pacific and Mr.
Kenneth Dunder, Senior Development Chemist, Georgia Pacific,
for their cooperation, active support, and sustained interest
in the project.
viil.
-------
SECTION 1
INTRODUCTION
A study of catalytic incineration of low concentration organic vapors
has been conducted. The scope of the study included both pilot-scale and
full-scale demonstration testing of catalytic abatement systems. In addition
to the assessment of the catalytic systems' abilities to reduce organic emis-
sions, an economic comparison was made between catalytic and thermal air
pollution abatement systems.
Catalysis is the process of changing the velocity of a chemical reac-
tion by the presence of a substance (catalyst) that remains apparently
chemically unaffected throughout the reaction. •
The catalyst used in this report is a precious metal formula evenly
distributed over a high surface area aluminum oxide support material. The
support material comes in two forms, pellet and honeycomb. High catalyst
surface area is a major contributing factor in^catalyst activity in that it
assists.in exposing a.maximum.number of active catalytic sites to the flowing
gas. Many catalyst formulas using platimun, palladium or other precious
metals are used in combination with surface preparation to give the proper-
ties necessary for each application. Selection of a catalyst formulation
and operating temperature depends on many interrelating factors. These
include the organic materials to be removed, the outlet concentration to be
achieved, the operating temperature, and the catalyst life which in itself is
dependent on temperature, solid particles concentration in the gas and ele-
ments such as sulfur, which reduce catalyst life.
Pelletized catalyst makes for easy loading and unloading and is less
expensive compared to honeycomb catalyst. It is used in pressurized chemical
processes. Honeycomb catalyst with its fixed .direct flow-through passages
has a much lower pressure drop resulting in a smaller reactor vessel and
lower power consumption by the gas moving device. Honeycomb catalyst is used
-------
in the catalytic abatement systems.
Organic vapors as well as carbon monoxide can be removed effectively
from many kinds of off-gas streams by oxidation in catalytic reactors. When
the off-gases containing these pollutants are heated to suitable temperatures
at a given space velocity, the combustible components react with oxygen from
the air to form harmless carbon dioxide and water vapor. The term space
velocity is defined as the volume of gas flowing through the catalyst per
hour, divided by the volume occupied by the catalyst. Space velocity
replaces the term contact time used in thermal incinerators. As a frame of
2
reference, contact times in thermal units are usually 0.3 to 0.5 seconds.
A space velocity of 50,000 hr. is equivalent to a contact time of 0.072
seconds.
In a thermal incinerator, pollutants are oxidized directly in the resi-
dence chamber at high temperature— typically above 1300°F. Because of the
high fuel consumption required to maintain these temperatures in a thermal
incineratorj the alternative of catalytic reaction is often preferable.
In a catalytic reactor, the catalyst induces oxidation at lower tem-
peratures, typically at 600° - 800°F.
Lower operating temperatures mean lower fuel consumption. Lower equip-
ment costs from smaller reactors and heat exchangers help balance the addi-
tional cost of catalyst making the overall equipment cost comparable to
thermal systems.
In some cases, the heat generated by the chemical reaction within the
catalytic reactor permits self-sustained operation: depending on concentra-
tion and other factors, a well-designed catalytic abatement system equipped
with a heat recuperator may be self-sufficient after initial lightoff. Lower
operating temperatures also have the advantage of preventing NOx formation.
The study was divided into four phases. Phase I was the process sel-
ection.
Phase II was the preparation and installation of a pilot demonstration
unit on a plastic printing plant.
Phase III was a full-scale demonstration of a catalytic air pollution
abatement system installed on a Formox* type formaldehyde plant.
Phase IV is this final report in which the data are presented and
analyzed.
-------
SECTION 2
CONCLUSIONS
PILOT TEST UNIT
The catalytic abatement of low level hydrocarbons from slip stream of
a plastic printing press exhaust have resulted in low level emissions in that
stream,
—1
1. The catalytic abater at a space velocity of 50,000/hr and an
exhaust temperature of 315°C would reduce total hydrocarbons from
the plastic printing plant 95% or more for a period of three years.
2. Increased conversion efficiency may be obtained by increasing tem-
perature or reducing space velocity.
3. Increased catalyst life may be obtained by increasing temperature.
4. Conversion efficiency varies for the different components of
the 'exhaust. . ;
FULL-SCALE. UNIT ;•: .• /' •••-;: . '•'..'-.._'.'."''.". .'.. .; ',-,".::. . , •
The catalytic abatement system has been operating on the exhaust of a
Formox* formaldehyde plant for a period of one year.
1. The removal efficiency of the catalytic abatement system has
remained in the range of 97.9% to 98.5%. There is no trend in the
data points which would predict a maximum catalyst life. A mini-
mum of three to five years is indicated.
2. The catalytic abatement system was not receiving any appreciable
( 1 ppm) NOx nor was any NOx produced by the system.
-------
SECTION 3
PILOT CATALYTIC UNIT
PROCESS SEARCH
As a preliminary, a search of the literature was conducted in order to
identify the major industrial sources of pollution which would lend them-
selves to reduction by catalytic incineration. The search produced the fol-
lowing major categories which were deemed most appropriate for an E.P.A.
study.
1. Polymers and resins
2. Basic chemical manufacture
3. Chemical products manufacture
4. Evaporative loss sources
While the literature search was being conducted, Engelhard's inquiry files
for the last three years Were searched to find prospective test sites. A
list of 68 possible test sites were identified.
PROCESS SELECTION
The list of test sites was screened to eliminate undesirable sites.
Off-gas with catalyst poisons such as sulfur and heavy metals, or high solid
loading, sites no longer interested or available, and systems not falling
within the categories selected were eliminated. A final list of eight test
sites was chosen. The companies were contacted and the program was outlined.
Preliminary interest in the program was followed by visits to several test
sites. Negotiations with several companies were conducted before a site was
chosen.
The selection of the test site chosen was concluded on the basis of a
desirable catalytic application, the interest of the company granting permis-
sion, and the facilities offered for the test program. The site chosen was
-------
at a plastic film printing plant. The off-gas was a mixture of volatile sol-
vents in air.
PROCESS DESCRIPTION
The test was conducted on the exhaust stream of a plastic film printing
press manufactured by the Pape.r Converting Machine Company. It is a 6-
station, 60 inches wide central impression cylinder flexographic printing
press. The press contains dryers which evaporate volatile organic solvents
from the plastic film after printing. (Figure 1)
3 -1
The total exhaust stream from the dryers is 4.72 m s . Maximum
exhaust gas temperature is 85°C. Drying is accomplished with two high veloc-
ity hot air impingement type dryers. Heat for the dryers is provided by two
natural gas fired burners. The drying system consists of two sections: a
between color dryer and main tunnel dryer. The between color dryer section
partially dries each ink layer prior to the next printing station and the
main tunnel dryer completes the drying sequence.
The product film is used for paper tissue packaging. The product is a
reverse printed polyethylene film. Each design employs 5 to 6 colors requir-
ing one printing station for each color.
The inks employed are solvent based polyamid printing inks which are
approximately 78% by weight volatile at the proper printing viscosity. The
major volatile components of the inks are ethanol, n-propyl and 2-propyl
alcohol, heptane9 and n-propyl and 2-propyl acetate. Ethanol is the major
solvent component but the percentage of all components varies widely with
different colors as does the amount of additional solvent added to the origi-
nal inks to bring them to the proper printing viscosity.
PILOT TEST UNIT DESCRIPTION
The pilot test unit consists of a blower, electric heater, catalytic
reactor and temperature, flow, and pressure instrumentation. . A flow sche-
matic of the unit is shown in Figure 2.
The blower draws a sample of exhaust gas from the exhaust system shown
in Figure 1. Exhaust under pressure from the blower is metered through the
system with a manual valve and flowmeter. An electric heater maintains the
-------
BALANCING DAMPER
STACh*1
EXHU5T
BLOWER,
HOT AIR HEATER-
/ \
y
PRINTED
FILM
PRINTINGS
MACHINE
(SIMPLIFIED)
NEW
. PLASTIC
FILM
I6T PRINTING ROLL
1ND PRINTING- ROLL
SAMPLE LINE
EXHAUST
PILOT
TEST
UNIT
Figure 1. Flow Schematic - Printing Press/Catalytic Pilot Unit.
-------
LE&END
F1 FLOW INDICATOR
TIP OVERTEMP. SHUT OFF
TIC TEMP CONTROLLER
PI PRESS. INDICATOR
DPI DIFFERENTIAL PRESS INDICATOR
FV CONTROL VALVE
FROM
STAGh
DAMPE-R /
INLET
ELECTRIC HEATER
OUTLET
SAMPLE
POINr
{XI
Figure 2. Flow Schematic Pilot Test Unit
-------
exhaust at the proper temperature entering the catalyst bed. A damper on the
exhaust of the catalyst bed produces a positive head throughout the system
preventing leaks into the system at the sample points. The sample points are
located before and after the catalyst bed. As the unit was built with
i i.
English units, all descriptions in this section will be in English units to
avoid confusion.
Blower
The blower is a Rotron Simplex Spiral Blower which employs the regen-
erative principle for moving air with a capacity of 55 SCFM at 365" ELO. It
is a Model No. SL2P2.
Flowmeter
The Teledyne Hastings Linear Mass Flowmeter is an in-line device oper-
ating on the thermal principle which depends on the mass flow of gas and its
heat capacity to change the temperature along a heated conduit. The tempera-
ture change is measured at zero flow by thermocouples.
The device is calibrated for a range of 1 to 10 SCFM of air. The scale
is linear. Each graduation is 0.2 SCFM. It is Model FM-42.
Electric Preheater
The electric preheater is a General Electric Calrod Circulation heater.
The unit is a 4.5 KW, JG series heater with type 321 stainless steel ele-
ments. Watt density is 11 watts per square inch.
The heater elements are controlled by West Series 800 temperature con-
trollers TIC-1 (inlet thermocouple) or TIC-3 (outlet thermocouple) via Variac
No. 1. TIC-3 was selected to control thereby maintaining a fixed outlet
temperature or bed temperature for all the experiments. This eliminated the
fluctuations of outlet temperature caused by changes in hydrocarbon content
which in turn varied the temperature rise.
Catalytic Reactor
The reactor is shown in Figure 3. The reactor contains Engelhard's
proprietary catalyst. The catalyst is a precious metal formula on a unitary
ceramic substrate. The Pilot Test Unit contains two catalyst elementss each
1% inches in diameter by 3 inches deep. The total volume of the bed is
0.006 cubic feet.
-------
-THERMOCOUPLE
HEAT RADIATION SHIELD
^THERMAL INSULATION
ELECTRIC. HEATER
THERMO COUPLE
CATALYST
Figure 3. Catalytic Reactor
-------
In order to properly measure the inlet and outlet temperature of the
reactor, two thermocouples are furnished. The inlet thermocouple is wired
to TIC-l, The tip of the inlet thermocouple is approximately 2 to 3 inches
upstream of the bed. The outlet is less than one inch from the catalyst bed.
The catalyst shell temperature is controlled by a temperature controller
TIC-2 which controls heater elements mounted on the shell. This heater pre-
vents heat losses from the small catalyst bed.
Thermocouples located in the air gap between the shells are wired to
TIC-2 and TIP-2. While TIC-2 controls the heater elements via Variac No. 2,
TIP-2 prevents the reactor shell from overheating. If a runaway reaction
should occur in which the shell overheats, the unit will automatically shut
down.
The reactor outlet is exhausted to the room. A damper is located on
the exhaust line to control the back pressure.
PILOT TEST PROGRAM
The test program was conducted over a period of six months beginning
in July and concluded in December, 1979. A total of five tests were con-
ducted during the six-month period. The tests were all performed at three
temperatures and three space velocities. A target for conversion efficiency
of 95% for a three-year period was'chosen. These numbers were chosen arbi-
trarily from past experience but proper selection of the data would make it
possible to alter these numbers to meet a specific application.
During the initial testing periods, the inlet and outlet were sampled
to determine the content of n-propyl acetate, ethanol and n-propyl alcohol.
After testing, a comparison was made of the actual temperature rise to the
calculated temperature rise. It was found that the calculated rise from the
measured hydrocarbon contact was less than actual temperature rise. This
indicated additional unmeasured hydrocarbon was probably present and addi-
tional testing was necessary. As a result, it was decided to also monitor
total organic carbon and heptane in the exhaust. Heptane monitoring began
on the September 25 test. Total hydrocarbon monitoring began on October 30.
The tests were conducted on the exhaust stream of the printing press.
The printing press is used to print on polyethylene sheets and paper; however,
10
-------
the pilot test was conducted only while the machine was printing on the poly-
ethylene sheets as the paper printing had no organic solvents in the ink.
During a typical 8 hour production day, the press occasionally shut down
causing the temperature rise across the reactor to fall rapidly to zero.
When the machine resumed printing, no test data was taken until the tempera-
tures had stabilized s.o that results would be comparable with previous data.
This practice was followed for test purposes only. Since the test unit was
kept in operation during the down times, the reactor was immediately operable
when the press resumed production. The testing was conducted at three outlet
temperatures,- which are 260°C, 315°C and 370°C. At each of these tempera-
tures, data was taken at three space velocities for a total of nine data
points per test. Since the velocity through the catalyst bed was extremely
fast compared to the time of analysis in a gas chromatograph, it was neces-
sary to sample the inlet and outlet simultaneously with chromatographs. This
insured inlet and outlet samples of the same original composition. The
sampling procedure was conducted as follows: the sample pumps were turned on
to continuously withdraw the samples from the exhaust and insure a fresh sam-
ple to the instruments. When the gases had circulated for at least one min-
ute, the samples were injected. At this point, readings were recorded from
the pilot test unit for temperature.,, pressure and flow rate. A minimum of
three samples were-taken at each of the nine data points. -The concentrations
which are shown on the data sheets are the averages.of the three chromato- ,
graphic readings. For example, at a space velocity of 30,000 hr. and a
temperature of 260°C, three samples were drawn to each chromatograph. For
each constituent, the results were averaged to show one data point for the
inlet and one data point for the outlet at each temperature and space veloc-
ity.
ANALYTICAL TECHNIQUES
For all tests, two chromatographs were employed, one dedicated to the
reactor inlet and one to the reactor outlet. Chromatographs were either
Carle 9700 or Varian 1200. The chromatographs were equipped with flame
ionization detectors. Both analyzers were calibrated with prepared standards
of ethanol, propanol, propyl acetate and heptane (when required). The
11
-------
detected results were recorded on a two-pen strip chart recorder. Concentra-
tions were then calculated.
All analysis work was conducted by Environmental Consulting and Testing
Services. The analysis was performed under the supervision of J. E.
Dennison, Ph.D. Details of the analytical procedures are given in Appendix
C.
RESULTS AND DISCUSSION
The catalytic unit operated continuously except when the plant was
printing paper. Normal operation was approximately 80% on plastic with the
plant running 24 hours per day, 5 to 6 days a week. The test unit was not
shut down over the weekend but ran on whatever residual material was in the
press as it did during additional down periods for changeover of printing
designs or press breakdowns. During these times the exhaust was essentially
room air. On this basis, discounting downtimes, the actual time of abate-
ment of the solvents was approximately 400 hours per month. Test data for
the pilot test is contained in Appendix A.
A summary of the data is given in Tables 1, 2, and 3. The total
removal percentage calculation is as follows:
Inlet Concentration Outlet Concentration
Ethanol 374 0.98
N-Propanol 194 0.41
N-Propyl Acetate 11.2 0.25
Total 579.2 1.64
- 1 fid
- Li°± x 100% = 99.7%
579.2
(Refer to Table A-l Measurement No. 1 for data and Table 1 Measurement No. 1
for result.)
Three plots (Figures 4,5 & 6) show the percent conversion of hydrocarbons versus
months of operation. The percent conversion is based on the total of the
individual components, heptane being absent from the first two points. The
three plots are for 260°C, 315°CS and 370°C exhaust temperatures. The three
curves on each plot are at the three space velocities: 30,000/hr ,
50,000/hr~ , and 70,000/hr . The omission of heptane which was not
12
-------
TABLE 1. . Pilot Test Data Summary, Preliminary
Test
Date
Time
Measurement No.
Flow Rate (m3/h)
Space Velocity x 1000
Catalyst Inlet Temp.( C)
Catalyst Outlet Temp. ( C)
Catalyst Press. Drop (Pa)
Removal %
Ethanol
N-Propanol
N-'Propyl Acetate
Total
Preliminary Testing
/17
0929
1
8.3
49
371
402
622
99.7
99.8
97.8
99.7
7/17
1001
2
11,9
70
371
406
846
99.6
99.8
97.8
99.6
7/17
1030
3
15.3
90.
371
407
1120
99.6
99.4
93.1
99.4
7/17
1305
4
14.6
86
316
360
996
99.6
99.1
94. 6
99.3
7/17
1400
5
11.9
70
316
362
871
99.6
99.2
97.1
99.4
7/17
1430
6
8.5
50
316
362
572
99.6
99.6
97.2
99.5
7/17
1500
7
5.1
30
313
360
373
99.8
99.9
99.4
99.8
7/17
1643
8
5.1
30
260
316
249
99.6
99.8
97.5
99.6
7/18
1320
'9
11.9
70
266
316
747
98.6
98.7
99.4
98.6
7/18
1352
10
8.5
50
291
313
498
99.0
99.3
92.2
99.0
7/18
1515
1.1
5. 1
30
277
311
249
99.8
99.9
97.7
99.8
7/19
1021
12
5. 1
30
338
354
249
99.8
99.8
94.4
99.7
7/19
1200
13
8.5
50
346
371
498
99.4
99.6
97.7
99.4
7/19
1115
14
12.2
72
340
368
747
98.9
99.1
90.8
98.9
-------
TABLE 2. Pilot Test Data Summary, Months One and Two
Test
Date
Time
Measurement No.
Flow Rate (m /h)
Space Velocity x 1000
Catalyst Inlet Temp( C)
Catalyst Outlet Temp(°C)
Removal %
Ethanol
N— Propanol
N-Propyl Acetate
Heptane
Total
One Month
8/15
1221
1
11.9
70
327
365
747
98.8
99.0
95.1
_
98.7
8/15
1301
2
8.5
50
327
368
622
99.2
99.4
97.8
_
99.2
8/15
1346
3
5.1
30
333
368
373
99. 7
99.8
99.8
_
99. 7
8/15
1542
4
11.9
70
230
260
622
99.4
98.0
58.6
_
97.0
8/15
1614
5
8.5
50
232
260
373
99.4
99. 1
68.3
_
98.2
8/15
1642
6
5.1
30
227
260
249
99.8
99.7
82.0
_
99.1
8/16
1112
7
11.9
70
285
316
747
98.4
96.5
91.7
_
97.4
8/16
1138
8
8.5
50
288
316
498
98.8
97.8
94.5
_
98.3
8/16
1303
9
5. 1
30
282
316
249
99.8
99.6
99.2
_
99.7
Two Month
9/17
1420
1
12.1
71
337
371
747
99.4
99.7
96.5
96.9
9?. 5
9/17
1445
2
8.5
50
335
371
809
99.5
99.9
99.0
97.3
99.6
9/17
1545
3
5.1
30
326
371
373
99.9
99.9
99.6
97.6
99.9
9/18
0925
4
11.7
69
285
316
747
98.2
97.9
93.5
88.1
97.8
9/18
0957
5
8.5
50
288
316
498
98.9
98.8
95.8
84.0
98.9
9/18
1005
6
4.9
29
285
313
249
99.3
99.4
99.1
98.0
99.3
9/18
1208
7
11.7
69
232
260
96.9
97.0
54.8
34,7
95.1
9/18
1253
8
8.5
50
229
263
i 373
98. 1
97. 2_
59.8
sa.o
95.9
9/18
13S7
9
5.1
30 ._
241
257
249
99.7.
99.8
93,3
92.7
99.4
-------
Table 3,
Pilot Test Data Summary, Months Three & Five
Test
Date '.
Time
leasurement
Flow Rate (m^/h)
Space Velocity x 1000
Catalyst Inlet Temp.( C)
Catalyst Outlet Temp ( C)
Catalyst Press. Drop(Pa)
Removal %
E t hanol
N-Propanol
N-Propyl Acetate
jeptane
Total
Total Oreanics**
Three Month
0/10
* .
1
11.9
70
337
371
647
98.3
99.9
96.2
98.8
97.7
0/10
*
2
8.5
50
337
371
498
99. 1
99.9
99.6
_
99.5
98.0
0/10
*
3
5.1
30
327
362
299
99.8
99.9
99.7
_
99. 9
98.0
0/11
. *
4
11.9
70
279
316
647
97.2
96.3
86.5
83 . 3
96.2
94.3
0/11
*
5
8.5
50
285
316
498
98.0
97.3
93.0
63. 8
97. 3
95.0
0/11
*
6
5.1
30
271
316
249
99.7
99.8
98.5
97.7
99.6
95.2
0/11
*
7
11.9
70
238
266
622
95.7
95.0
52.9
57.7
93.0
82.6
0/11
*
8
8.5
50
230
260
373
97.6
97.2
51.0
62.0
95V9
85.8
0/11
*
9
5.1
30
232
260
249
99.7
99.7
61.5
78.0
98.9
87.5
Five Month
2/11
1458
1
11.9
70
330
371
560
98.7
98.6
96.2
_
98.5
2/11
1615
2
8.5
50
330
371
436
99.5
99.5
99.8
_
99.5
2/12
1019
3
5.1
30
319
365
249
99.8
99.8
99.8
99.0
99.8
2/12
1117
4
11.9
70
260
321
498
97.8
97.3
85.0
85. 3
96.9
2/12
1230
5
8.5
50
260
319
373
98.9
98.8
93.1
91.9
98.5
2/12
1318
6
5.1
30
252
319
249
99.7
99.8
99.0
98. 3
99.7
2/12
1453
7
11.9
70
221
260
436
96.0
95.5
44.2
24,1
90.7
2/12
1515
8
8.5
50
224
265
324
97.5
97.5
59.6
50,4
94.0
2/1.2
1540
9
5. 1
30
221
760
199
99.6
99.8
78.0
77.0
97.9
*Average of three or more tests.
**As analyzed. See data section.
-------
% CONVERSION
100
98
94-
92
90
SPACE VELOCITY
30,000
0 50,000
X 70,000
0
345
MONTHS OF OPERATIONS
-------
7
lo
CONVERSION
100
96
92
90
X
X
SPACE VELOCITY
A 30,000
© 50,000
X 70,000
0
345
MONTHS OF OPERATION
(D
Figure 5. Effects of Time and Space Velocity on Conversion Efficiency of Total Hydrocarbons at 315°C
-------
oo
01
10
CONVERSION
100
SPACE VELOCITY
A 30,000
© 50,000
X 70,000
0
3 ----- 4- 5
MONTHS OF OPERATION
Figure 6. Effects of Time and Space Velocity on Conversion Efficiency of Total Hydrocarbons at 260°C
-------
originally in the analysis has little effect on the overall conversion'effi-
ciency as it is only 2% or 3% of the total organic content.
If a conversion efficiency of 95% over a three year period were to be
chosen as the basis of a full-scale design the curves plotted in Figures 4,
5, and 6 would help to determine the minimum space velocity and temperature.
It is evident from Figure 6 that at 260°C none of the data would provide a
95% conversion for three years. Even at a space velocity of 30,000/hr the
slope of the line is approximately -0.275% per month which amounts to a 10%
reduction in conversion efficiency. The slope was determined as
slope = % conversion month 5 - % conversion month 1
4 months
In Figure 4 there is no slope to the curves for space velocities at
30,000/hr~ and 50,000/hr" at 370°C. This means the catalyst at these con- .
ditions has an indeterminate life beyond anything predictable. At a space
velocity of 70,000/hr and 370°C the slope of the curve is approximately
-0.06% per month which amounts in 3 years to a 2% reduction in conversion '•>
efficiency from an initial efficiency of 99%. This easily meets the criteria.
At a temperature of 315°C, Figure 5, the slope of the 305000/hr~ space
velocity curve is indeterminate predicting it would again meet the criteria.
At 50,000/hr space velocity the slope is approximately -0.1% per month
after the first three months. Adding the slope to the value at the end of
three months gives an approximate conversion percentage of 94.5% at the end
of 3 years. At 70,000/hr space velocity the conversion would be much less
than 95%.
Additional individual component plots were drawn (Figures 7 & 8) of
n-propyl acetate and heptane which are more difficult to oxidize. This was
done to accentuate the differences in percent conversion of organics at vary-
ing temperatures and space velocities. Figure 7 is a plot similar to Fig-
ures 4, 5, and 6, but is for n-propyl acetate only. Being more difficult to
oxidize than the two alcohols, the trend of the curve is easier to identify.
Fortunately, the data are quite regular and provide smooth curves. Repeat-
ing this procedure for heptane component (Figure 8), was not as satisfactory,
but the general position of points is similar to the n-propyl acetate.
These two components combined make up less than 10% of the total pollutants
19
-------
SPACE VELOCITY
106
80
7Q
I 1 | 1 1 1 ' 1 1 1 T 1
Jl 54501 £34501 2345
Figure 7. Effects of Time, Temperature, and Space Velocity on Conversion Efficiency of n-Proply Acetate
-------
70 CONVERSION/
00
90
80
70
foO
50
40
30
20
10
r>
-A A
-
^ -y-ito r- ^
-*S o / 1 -
-1**! ... OI«O U ^
,. j . -.,
SPACE VELOGiTf
A 30,000
© 50,000
A X 70,000
A A
0
© X
0
-------
and, therefore, do not affect the overall conversion to a large degree.
It should be noted that the initial eight data points are not shown in
any of the data plots. These points were taken on start-up to determine the
operating parameters. In addition, the temperature parameter at 260°C was
not determined to be necessary until after the first month's testing was com-
plete.
An additional test was conducted at the end of the fourth month. This
was an analysis for total hydrocarbons using hexane as the standard. Results
on the basis of conversion efficiency closely paralleled the values obtained
from using the total of independent components, but at somewhat lower effi-
ciencies. A review of the chromatographic recordings when testing for the
individual components did not reveal any substantial curves to indicate a
quantity of unknown compounds which might explain the lower conversion
efficiencies.
22
-------
SECTION 4
FULL SCALE CATALYTIC UNIT
INSTALLATION
The full-scale unit is an Engelhard Deoxo Catalytic Pollution Abatement
System, Model PAS-4, installed on a formaldehyde plant using the Formox* pro-
cess under license from Reichhold Chemicals, Inc. (Figure 9). The process
makes formaldehyde 'by passing preheated air and recycled process gas mixed
with methanol through a Formox* catalyst. The reaction without balancing
the equation is
CH OH + 0, + inerts *- HCHO + CELOCH + CO + inerts
-J • 4* -J J
methanol oxygen formal- dimethyl carbon
dehyde ether monoxide
Recycling takes place with sufficient air addition to keep the inlet oxygen
level at about 10%. It is, therefore, necessary to withdraw approximately
,25% of the exhaust gas to remove the inerts, i.e. nitrogen, dimethyl ether
and carbon monoxide.
The catalyst is contained in a multiple tube converter where a con-
trolled reaction takes place. Formaldehyde is absorbed in multiplate columns
which produce an essentially methane1-free product.
PROCESS DESCRIPTION
The catalytic incinerator (Figure 10) is used to reduce hydrocarbon
emissions being exhausted in the off-gas from a Formox* formaldehyde plant.
The gas stream, under saturated conditions, exits the plant at a rate of
4500-6000 m /h entering the catalytic incinerator at 32-43°C. The entering
gas passes through a gas-to-gas recuperative heat exhanger to raise the tem-
perature to 232°C minimum. The gas then proceeds through a gas-fired pre-
heater which is used to start the system or add heat if the incoming exhaust
23
-------
5TAGh
J L
AIK FEED
[XK
GLEAN EXHAUST
1-0
-p-
METHANOL
FE.ED
RECYCLE
HX3—i
PLAN!
EXHAU5T
FORMALDFHYDE PLANT CATALYTIC ABATEMENT SYSTEM
Figure 9. Flow Schematic Formaldehyde Plant/Catalytic Abatement System
-------
Burner
Catalyst Bed
Heat Exchanger
Bypass Valve
Stack
Bypass Duct
Warm Gas Duct
Mixing Section
Figure 10. Full Scale Catalytic System
-------
is low in heat content. It then passes through a mixing section to assure
even distribution of the heat before entering the catalyst bed. After com-
bustion, the temperature rises to 427-621°C, depending on hydrocarbon load-
ing, the hot exhaust gas passes through the heat exchanger to the exhaust
stack. A bypass of the inlet gas around, the heat exchanger permits regula-
tion of the incoming gas stream temperature.
The exhaust stream inlet has the following composition**:
Carbon Monoxide 3000-8000 ppm
Methanol 100-900 ppm
Dimethyl Ether 2500-4500 ppm
Formaldehyde 50-500 ppm
Nitrogen 90-92%
Oxygen 6-7%
FULL SCALE UNIT DESCRIPTION
The Engelhard Deoxo Catalytic Pollution Abatement System, Model PAS-4
(Figure 10) includes a catalytic reactor, heat exchanger, burner system,
mixing section, and instrumentation for proper operation.
Exhaust enters the system below the heat exchanger and proceeds through
the heat exchanger or bypasses it before going to the mixing section where
additional heat may be added; After mixing thoroughly to assure a uniform
reaction, it passes through the catalyst bed exiting into the heat exchanger
and up the stack.
Catalytic Reactor
The reactor contains Engelhard's proprietary precious metal formula on
a honeycomb ceramic substrate. The substrate is in block form and is layered
between stainless steel wire supported by a stainless open grating.
Heat Exchanger
The inlet gas is preheated by passing vertically inside the tubes of
the heat exchanger. A bellows seal on the tube side prevents leakage of
untreated exhaust gas to the clean exhaust side. The hot clean exhaust from
the catalyst bed passes horizontally through the heat exchanger to preheat
**0n a dry basis. Actual gas is saturated at 25°-38°C.
26
-------
the incoming untreated exhaust. The heat exchanger is constructed of Type
304 stainless steel tubes and a carbon steel shell which is internally insu-
lated.
Burner System
The burner system consists of a blower to furnish combustion air, a gas
train, a modulating air valve, a burner, an ultraviolet flame sensor, and a
supervisory panel to control the burner 'system. The burner system is a com-
plete package designed to meet the insurance requirements for burner safety
i.e., flow switches, purge cycles and flame sensing.
Mixing Section
The mixing section of the unit was designed to blend the incoming gas
stream with the hot gases from the burner system or to blend hot and cold
incoming exhaust when the bypass is functioning. In addition, it supports
the catalyst bed allowing it to expand and contract through a slip joint into
the conversion section attached to the heat exchanger. The burner is mounted
at the inlet to the mixing section. The total unit is externally insulated
and weatherproofed.
Instrumentation
Control of the exhaust flow through the system is by means of manual
valves and is external to the abatement system. Operation of the system
therefore is restricted to controlling temperatures and alarming if the sys-
tem goes out of control.
Four temperature indicator controllers are on the system. The first is
placed before the catalyst bed to monitor incoming temperature. The second
unit controls the burner system modulating the gas stream to a temperature of
440°-450°C. In addition it will shut the burner system down completely above
that temperature. Under normal operating conditions the system will float
above 450°C but below 565°C without control. If the temperature goes above
565°C a third temperature control will open a bypass valve which allows the
exhaust to bypass the heat exchanger and reduce the inlet temperature. A
fourth controller is an overtemperature unit which will shutdown the burner
system if it has continued to operate by a malfunction. It will also sound
an alarm so that the operators will know that the temperature in the system
has reached a level where the total system should be corrected or bypassed.
27
-------
This part of the control requires manual reset.
V
TEST PROGRAM
The test program began in July, 1979, and has now become a part of a
continuous monitoring system of the process. The program was conducted so
that samples were obtained once or twice a week. Each test reading is an
average of two samples. Grab samples were used on both the inlet and exhaust
from the abatement system. Difficulty in separating the hydrocarbon compo-
nents in the packed columns of the gas chromatograph prevented acceptable
data from being obtained until October so that the program was extended until
February, 1980, to achieve a six-month program.
Testing on the full-scale system as compared to the pilot systems was
restricted. Very little variation of temperature or flow was obtained as the
system was abating a plant under steady state conditions. Minor variations
in feed conditions and plant operating conditions did vary the inlet pollut-
ant concentrations as shown in the data. Within these ranges, little or no
effect was found in the outlet or abated concentrations.
As an additional part of this program, a one day test was conducted to
determine the NOx level in the exhaust stream.
ANALYTICAL TECHNIQUES -
All testing used grab sample techniques and the analysis was by gas
chromatography. This work was carried out by plant personnel and is detailed
in Appendix D-l. This includes a discussion of quality control.
An exception to the above was the NOx test which was conducted by
Environmental Consulting and Testing Services using the chemiluminescence
technique. This technique is described in Appendix D-2.
RESULTS AND DISCUSSIONS
Operation of the catalytic incinerator has been, with minor exceptions,
reasonably constant from July, 1979, until March, 1980. Flow rate through
3 33
the system averaged 5211 m /h with a high of 5709 m /h and a low of 4588 m /h
3
except for a two week period in January when it averaged 3093 m /h. Inlet
temperatures averaged 241°C with a high of 271°C and a low of 195°C while
28
-------
outlet temperatures averaged 536°C with a high of 571°C and a. low of 430°C.
Complete test data for the full-scale unit is contained in Appendix B.
Analytical problems both at the beginning and end of the testing pre-
vented a uniform set of data from being taken. Initially, the carbon monoxide
readings of the outlet analysis were found to be greatly influenced by the
absorption column of the chromatograph. This was corrected in the latter
part of October. Data for this questionable period on carbon monoxide outlet
is not given. Data for inlet and outlet analysis for formaldehyde and meth-
anol increased unreasonably after mid-January. Subsequent investigation
showed that part of the absorption media was blown out of the column with
particles carried over into the chromatograph. After installation of a new
column, and a recalibration of the unit, it was found that the formaldehyde
was 14 ppm and the methanol was 6 ppm in the outlet stream.
Complete data was obtained for November 30, December 18, January 11,
and March 13, 18, and 25. Conversion efficiencies for these dates were
97.9%, 98.5%, 98.3%, 97.9%, 98.3 %, and 98.0%. Refer to Summary Table 4.
A study of the inlet data from November through February, shows values
that are typical of a Foraiox* type plant. Values for CO range from 3390 ppm
to .8050 ppm, dimethyl ether ranged from 2420 ppm to 5150 ppm, methanol had a
low of 201 ppm anid a high of 1890 ppm.. Formaldehyde was less than 75 ppm
with one exception. . -. . ', ' ... .... . .
Carbon monoxide and dimettily ether are the most -difficult compounds to
convert completely. Data on these for; the outlet condition was obtained for
all runs from November through February. Carbon monoxide averaged 50.6 ppm
while dimethyl ether averaged 96.5 ppm. It is interesting to note that vari-
ances from the average bear no relationship to inlet concentrations or flow
conditions.
Although only six complete data points were obtained during the test-
ing, the reasonably constant outlet concentrations of carbon monoxide and
dimethyl ether and the latter information on formaldehyde and methanol indi-
cate the catalytic incinerator has been operating in the range of 97.9% to
98.5% conversion of the exhaust pollutants over a one year period without
change.
The results of the NOx testing indicated an inlet of 11 ppb and an
outlet of 12.3 ppb. The background reading was 9 ppb. It is evident NOx is
29
-------
TABLE 4. FULL-SCALE TEST DATA SUMMARY
Test
Date
11/30/79
12/18/79
1/11/80
3/13/80
3/18/80
3/25/80
Flow Rate
fin /h)
4945
5149
2957
-
4124
4590
Outlet Temp.
(°Cl
540
532
540
-
505
510
Removal Efficiency *?0
CO
98.9
99.1
99.3
99.0
99.0
99.0
CH3OH
97.2
98.6
99.2
93.2
98.9
97.1
CH OCH3
96.8
97.2
96.6
96.6
96.7
96.5
HCHO
95.0
98.6
97.0
98.6
99.1
98.7
Overall
97.9
98.5
98.3
97.9
98.3
98.0
-------
not being generated in the abatement, system.
31
-------
SECTION 5
ECOMONIC COMPARISON
The annual cost of operating an air pollution abatement system depends
on the level of abatement required. Catalytic systems have been built to
achieve effluents in the low part per trillion range as in trituim systems;
however, in general, most abatement systems operate on a basis of removing
95%-99% of the pollutants. Both thermal and catalytic systems achieve these
levels.
A good illustration of the difference in cost between a 95% and a 99%
removal is thermally to compare residence time and catalytically to compare
2
catalyst volume. Data presented by Rolke indicates in a thermal unit the
residence time at 99% removal would be approximately six times that at 95%.
The catalyst volume which is calculated from the concentrations
„ •, ^ „ i i Inlet Concentration
Catalyst Volume f^j In Tr-rs——-7; ——•—
J Outlet Concentration
would increase about 50 percent for the same removal efficiencies. Constant
temperatures were assumed in both cases.
A second consideration in determining annual cost is a balancing of
operating expenses with capital costs. The major capital cost item which
influences operating cost is the heat exchanger. For low concentration
hydrocarbon exhaust streams preheating the inlet stream with the outlet
stream is most important. Heat exchangers which return 40% of the exhaust
heat to the inlet gas represent approximately 30% of the material cost in
building a system. Increasing the efficiency of the heat exchanger to 60%
would double its cost.
An additional operating cost is the power consumed to move the exhaust
through the abatement system. This becomes most critical in sizing heat
exchangers and catalyst beds.
The economic comparison of a thermal and catalytic system presented
32
-------
here is limited to a comparison of units with the similar efficiencies of
operation, reduction of pollutants9 and material costs. The capital and
annual cost of operating an air pollution abatement system is shown in
Table 5.
Capital Cost
The purchase cost of the catalytic units are based on construction
techniques used in incinerator systems Engelhard has already sold. Updated
costs of these units have been used to develop the purchase prices shown in
Table 3. In order to obtain the closest comparision, the thermal units were
estimated using the same construction techniques, the same burners, instru-
mentations and type of heat exchangers. Blowers were not included in the
estimates. • . '
Flow schematics (Figures 11, 12, 13, & 14) are indicative of such type
system. The units are completely skid mounted, prewired, and piped, ready
to convert to the plant piping. Ductwork which is part of the unit (i.e.,
that included in the schematics) may be shipped separately, as well as the
heat exchangers of the larger units due to shipping size limitations.
Annual Cost .
. An annual.cost comparison depends on many factors. These factors vary
in different areas and with the .economic climate.. The values shown in
Table 4 are for comparison of catalytic versus thermal, systems and should
not be used as a basis for cost estimating a specific application.
The following assumptions were made in conducting the economic
analysis:
1. See Table 6 for technical basis.
2. Installation costs are assumed to equal the purchase price.
3. Catalyst replacement is included on a three year basis. Test
results indicate this as a minimum catalyst life.
4. Natural gas fuel at $.50 per therm.
5. Interest on capitals 10%.
33
-------
TABLE 5,
CAPITAL AND ANNUAL COSTS ($)
PLASTIC PRINTING
Capacity
(m3/h)
Purchase
Installed
Capital Cost
Capital Recovery*
(16.3%)
Catalyst Repl.
Maintenance (2%)
Fuel
Annual Cost
Catalytic
16,992 33,984
186,000
186,000
372,000
60,600
19,300
7,500
36,500
123,900
271,000
271,000
542,000
88,300
38,600
10,800
73,000
210,700
Thermal
16,992
177,000
177,000
. 354,000
57,700
-
7,100
107,500
172,300
33,984
247,000
247,000
494,000
80,500
-
9,900
214,000
304,400
FORMALDEHYDE
Catalytic
8,496 16,992
150,000
150,000
300,000
48,900
10,500
6,000
-
65,400
207,000
207,000
414,000
67,500
20,900
8,300
-
96,700
Thermal
8,496
135,000
135,000
270,000
44,000
-
5,400
198,000
247,400
16,992
174,000
174,000
348,000
56,700
-
7,000
370,000
433,700
*Capital Recovery Factor of 16.3% is based on 10% interest over a 10 year period.
-------
TABLE 6. COST COMPARISON FACTORS
PLASTIC FILM PRINTING SYSTEMS
Air inlet 2l°C.
Dryer inlet 93°C.
Catalyst bed exhaust 315°C.
Thermal incinerator exhaust 760 C.
Gas BTU content causes 28 C rise.
Heat exchanger 41% efficient.
No thermal losses except to stack.
Heat exhanger catalytic - Corten steel.
Heat exchanger thermal - stainless steel.
FORMALDEHYDE. SYSTEMS
Air inlet 21°C. .
Catalyst bed exhaust 510 C.
. Thermal .incinerator exhaust 760 C.
Gas BTU content causes 289 C rise.
Heat exchanger 41% efficient.
No thermal losses except to stack.
Heat exchanger - stainless steel.
35
-------
PREHEATER
CATALYTIC
ABATER
-ft*
HEAT
EXCHANGER
SOLVENT
DRYER
STACK
h
Figure 11. Flow Schematic. Plastic Printing Plant - Catalytic Abatement System
-------
STACK
THERMAL
INCINERATOR
HEAT
EXCHANGER
AIR
Figure 12. Flow Schematic. Plastic Printing Plant - Thermal Incinerator
-------
OJ
00
PREHEATER
STACK
h
CATALYTIC
ABATER
HEAT
EXCHANGER
.WASTE STREAM
Figure 13. Flow Schematic. Formaldehyde Plant - Catalytic Abatement System
-------
STACK
THERMAL
INCINERATOR
HEAT
EXCHANGER
WASTE
STREAM
Figure 14. Flow Schematic. Formaldehyde Plant - Thermal Incinerator
-------
REFERENCES
Trends, Pollution Engineering., Volume 10, Number 11,
November 1978, 9 pp.
Rolke, R. W., et al. Afterburner Systems Study. EPA,
EHS-d-71-3, Shell Development Company, Emeryville,
California, pp 19.
Chemists Dictionary, D. Van Nostrand Co., Inc.,
New York, 1st Ed, 1953, pp 134.
40
-------
APPENDIX A
PILOT UNIT TESTS
Table A-l: Preliminary Testing
Table A-2: Preliminary Testing
Table A-3: One Month Test
Table A-4: Two Month Test
Table A-5: Three Month Test
Table A-6: Five Month Test
41
-------
TABLE A-l: PRELIMINARY TESTING
Date
Time
Measurement No.
Flow Rate.Cm /h)
Space Velocity x
1 flnn
Catalyst Inlet
Temp. (°C)
Catalyst Outlet
Temp. ( C)
Catalyst Press.
Drop (Pa)
Inlet Analysis (ppm
Ethanol
N-Propanol
N-Propyl Acetate
Outlet Analysis (ppi
Ethanol
N-Propanol
• N-Propyl Acetate
Tin
0929
-1
8.3
49
371
402
622
374
194
11.2
)
0.98
0,41
0.25
7/17
1001
2
11.9
70
371
406
846
374
194
11.2
1.61
0.61
0.25
7/17
1030
3
15.3
90
371
407
1120
374
200
13.4
1.50
1.30
0.92
7/17
1305
4
14.6
86
316
360
996
466
220
20.0
1.75
1.97
1.08
7/17
1400
5
11.9
70
316
362
871
469
239
24.0
2.02
1.89
0.70
7/17
1430
6
8.5
50
316
362
572 .
456
228
27.0
1.94
0.85
0.76
7/17
1500
7
5. 1
30
313
360
373
464
219
34.0
1.06
0.26
0.22
7/17
1643
8
_JLJL
30
260
316
249
456
225
33. C
1.81
9.84
0.84
42
-------
TABLE A-2: Preliminary Testing
Date
Time
Measurement No.
3
Flow Rate (m /h
Space Velocity
Catalyst Inlet Temp.(°C)
Catalyst Outlet Temp.(°C)
Catalyst Press Drop (Pa)
Inlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
)utlet Analysis (ppm)
Ethanol
N-Prqpanpl
N-Propyl .Acetate
7/18
1320
9
11.9
70
266
316
747
250
159
7.3
3.49
2.04 .
0.48
7/18
.1352
10
8.5
50
291
313
498
247
148
4.5
2.44
1.11
0.35
7/18
1515
11
•5.1
30
277
. 311
249
254
176
4.5
0.55
0.. 12
0.10
7/19
1021
12
5.1
30
338
354
249
274
185
4.5
0.65
0.45 '
0.25
7/19
1200
13
8.5
50
346
371
498
279
184
4.5
1.76
0..7.3
0.10
7/19
1115
14
12.2
72
340
368
747
277
182
4.0
3.04
1.63
0.37
43
-------
TABLE A-3: ONE MONTH TEST
Date
Time
Measurement No.
Flow Rate (m3/h)
Space Velocity x 1000
Catalyst Inlet Temp.(°C)
Catalyst Outlet Temp.(°C)
Catalyst Press. Drop (Pa)
Inlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Outlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
8/15
1221
1
11.9
70
327
365
747
489
367
30.3
5.82
3.80
1.48
8/15
1301
2
8.5
50
327
368
622
466
345
36.5
3.68
1.98
0.81
8/15
1346
3
5.1
30
333
368
373
404
306
33.4
1.34
0.65
0.08
8/15
1542
4
11.9
70
230
260
622
443
371
36.2
2.70
7.6
15.0
8/15
1614
5
8.5
50
232
260
373
459
374
30.0
2.95
3.45
9.50
8/15
1642
6
5.1
30
227
260
249
405
319
24.6
1.0
1.06
4.43
8/16 !
1112
7
11.9
70.
285
316
747
488
298
27.7
8.03
10.5
2.30
8/16
1138
8
8.5
50
288
316
498
509
315
26.1
6.1
6.9
1.44
8/16
1303
9
5.1
30
282
316
249
510
333
24.5
1.19
1.2
0.2
-------
TABLE A-4: TWO MONTH TEST
Date
Time
Measurement No.
Flow Rate (m3/h)
Space Velocity x 1000
Catalyst Inlet Temp.(°C)
Catalyst Outlet Temp.(°C)
Catalyst Press. Drop (Pa)
Inlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Heptane
Outlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Heptane
9/17
1420
1
12.1
71
337
371
747
456 .
458
11.5
1.3
2.8
1.15
0.4
0.04
9/17
1445
. 2
8.5
50
335
.371
.809
; 522
.448 .
•26.5 '••'.
32.5
• . 2. 7
0.39
0.26
: -0.89
9/17
1545
3
- 5.1
30
326
'- 371
373
522
461
23.3
20.9
0.4
0.33
0.1
0.5
9/18
0925
4
11.7
69
285
316
747
413
346
16.8
8.4
7.4
7.4
1.1
1.0
9/18
0957
5
8.5
50
288
316
498
433
362
13.6
4.5
4.6
4.2
0.57
0. 72
9/18 .
1005
6
4.9
29
285
313
249
373
346
11.2
3.5
2.6
2.0
0.1
0.07
9/18
1208
7
11.7
69
232
260
622
413
346
16.8
11.8
12.9
10.4
?!6
7.7
9/18
1253
8
8.5
50
229
263
373
494
365
21.9
20.0
9.2
10.4
8.8
8.4
9/18
1357
9
5.1
'. 30
241
257
249
509
371
20.9
17.8
1.7
0.8
1.4
1.3
-------
TABLE A-5: THREE MONTH TEST
Date
No. of Samples Averaged
Measurement No.
Flow Rate (m /h)
Space Velocity x 1000
Catalyst Inlet Temp.(°C)
Catalyst Outlet Temp.(°C)
Catalyst Press. Drop (Pa)
Inlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Heptane
Total Organics
Outlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Heptane
Total Organics
10/10
6
1
11.9
70
337
371
647
474
274
29
20.8
646
8.2
.1
1.1
*
15
10/10
4
2
8.5
50
337
371
498
492
306
27
12.6
608
4.4
.1
.1
*
12
10/10
3
3
5.1
30
327
362
299
503
306
31
19.3
618
1.0
.1
.1
*
12
10/11
3
4
11.9
70
279
316
622
458
312
26
21.0
609
•
12.8
11.5
3.5
3.5
35
10/11
3
5
8.5
50
285
316
498
450
324
30.2
9.4
623
8.9
7.2
2.1
3.4
31
10/11
3
6
5.1
30
271
316
249
429
330
32.3
48
630
1.1
0.6
0.5
1.1
30
10/11
3
7
11.9
70
238
266
622
382
366
20.4
26
610
16.4
18.3
9.6
11
106
10/11
4
8
8.5
50
230
260
373
389
365
14.5
12.9
557
9.5
10.3
7.1
4.9
79
10/11
3
9
5.1
30
232
260
249
431
373
10.4
9.1
582
1.5
1.3
4.0
2.0
73
*Not readable due to interference of background
-------
TABLE A-6: FIVE MONTH TEST
Date
Time
Measurement No.
3
Flow Rate (m /h)
Space Velocity x 1000
Catalyst Inlet Temp. (°C)
Catalyst Outlet Temp. (°C)
Catalyst Press. Drom (Pa)
Inlet Analysis (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Heptane
Outlet Analysis . (ppm)
Ethanol
N-Propanol
N-Propyl Acetate
Heptane
12/11
1458
1
11.9
70
330
371
560
536
250
45
A
7.0
3.5
1.7
*
12 /.ll
1615
:. 2.
8.5
50 ";
330
37:1
436'
581
297
; 42.
•''*• ;
2.77
.1*41
0.51
• • *
12/12
1019
3
5.1
30
319
365
249
. 505
253
24.6
38.1
1.1
0.45
. 0.04
0.38
12/12
1117
4
11.9
70
260
321
498
527
273
20.6
28.0
11.6
7.47
3.1
4.12
12/12
1230
5
8.5
50
260
319
249
476
288
29.1
15.0
5.23
3.6
2.0
. 1.22
12/12
1318.
6
5.1
30
252
319
249
483
287
31.3
•27.0
1.4
0.7
0.3
0.45
12/12
1453
7
11.9
70
221
260
436
546
303
51.4
29.0
21.9
13.6
28.7
22.0
12/12
1515
8
8.5
50
224
265
324
538
305
54.2
24.6
13.7
7.77
21.9
12.2
12/12
1540
9
5.1
30
221
260
199
542
310
51.4
21.7
2.1
0.77
11.3
5.0
* Operating Difficulty prevented analysis
-------
APPENDIX B
FULL SCALE TEST
Table B-l: July - August Testing
Table B-2: September - October Testing
Table B-3:' November - December Testing
Table B-4: January Testing
Table B-5: February - March Testing
48
-------
TABLEB-l: JULY - AUGUST TESTING
DATE
7/19
7/20
7/24
7/27
7/31
8/03
8/08
8/10
8/14
8/17
INLET ANALYSIS
CO
(ppm)
NA
7300
6610
NA
4820
3630
3910
5220
NA
6520
HCHO
(ppm)
91*
91*
91*
91*
91*
91*
91*
91*
91*
91*
DME
(ppm)
NA
4260
4030
2750
3040
2360
4930
3450
NA
4560
MeQH
(ppm)
NA
260
195
151
148
NA
163
209
NA
NA
FLOW
KATE -
(ra3£h.)
5386**
5386**
5081
5318
5200
• ' ' ' .'•'' '
5386
5234
5268
.5217
5709
INLET
TEMP.
(°C>
243
233
228
229
238
240
241
238
224
263
OUTLET
TEMP.
(°C)
552
538
523
527
538
543
545
538
515
571
OUTLET ANALYSIS
CO
(ppm)
HCHO
(ppm)
< I
<1
< 1
< 1
-------
TABLE B-2: SEPTEMBER - OCTOBER TESTING
DATE
9/07
9/11
9/13
9/14
9/17
9/26
9/27
9/28
10/08
INLET ANALYSIS
CO
(ppm)
6600
5100
NA
5100
NA
NA
4700
2260
NA
HCHO
(ppm)
NA
55
NA
287
NA
NA
NA
NA
NA
DME
(ppm)
2720
2200
NA
1600
NA
NA
2850
NA
NA
MeOB
(ppm)
**
**
ft*
**
**
ft*
ft*
ftft
**
FLOW
RATE
(m3yh)
5318
5437
5098
5251
5149
5471
5132
5251*
5064
INLET
TEMP.
(°C)
232
243
250
266
232
260
232
260
232
OUTLET
TEMP.
(°C)
515
538
555
538
527
515
527
515
532
OUTLET ANALYSIS
CO
(ppm)
HCHO
(ppm)
<: 1
-.1
21
<1
<1
<1
<1
<1
<1
DME
(ppm)
53
54
111
86
-------
TABLE B-3: NOVEMBER - DECEMBER TESTING
DATE
11/06
11/09
11/13
11/16
11/27
11/30
12/11
12/14
12/18
INLET ANALYSIS
CO
(ppm)
3390
3750
3700
5050
4140
3830
4600
6440
HCHO
(ppm)
<-75
< 20
< 75
< 75
< 36
< 75
< 20
72
DME
(ppm)
2480
2920
2740
2680
2420
3135
3520
3230
MeQH
(ppm)
1890
480
480
690
461
330
650
FLOW
RATE:
(jn3/h)
4808 :
\5199
5437
5267
4945
5200
4996
5369
5149
INLET
TEMP.
(°c)
230
230
238
232
240
240
240
229
237
OUTLET
TEMP.
(°C)
531
528
538
530
538
540
540
531
532
' OUTLET ANALYSIS
CO
(ppm)
44
48
62
48
55
44
94
69
58
HCHO
(ppm)
< 4
< 4
< 4
<4
<4
<4
-------
TABLE B-4: JANUARY TESTING
DATE
1/04
1/08
1/11
1/15
1/18
1/22
1/25
INLET ANALYSIS
CO
(ppm)
4820
5350
6100
8050
5095
4970
6980
HCHO
(ppm)
< 20
< 55
263
DME
(ppm)
3388
3480
3360
5150
3185
3290
4200
MeOH
(ppm)
201
221
263
FLOW
RATE
(m3/h)
2940
2991
2957
3178
3245
5166
5335
INLET
TEMP.
(°C)
255
258
255
248
258
250
248
OUTLET
TEMP.
(°C)
540
544
540
520
543
555
558
' OUTLET ANALYSIS
CO
(ppm)
34
42
40
40
37
55
62
HCHO
(ppm)
< 1
< 2
<2
DME
(ppm)
106
120
115
122
119
100
105
MeOH
(ppm)
8
Ul
N>
-------
TABLE :B-5: FEBRUARY - MARCH TESTING
DATE
2/01
2/05
2/08
2/20
2/22
3/13
3/18
3/25
INLET ANALYSIS
CO
(ppm)
5050
5580
4730
5390
5540
4360
4355
4830
HCHO
(ppm)
206
1490
589
DME
(ppm)
3230
2470
3860
4480
2950
3340
3110
3090
Me OH
(ppm)
436
931
476
.FLOW
RATE
(m3/hj
5369
4979
.5352
4588
4865:-
4124
4590
INLET
TEMP.
(°C)
225
195
251
230
230
212
220
OUTLET
TEMP.
(°C)
570
430
570
532
558
505
510
OUTLET ANALYSIS
CO
(ppm)
45
57
42
32
55
43
44
49
HCHO
(ppm)
14
16
17
DME
(ppm)
96
128
113
92
98
113
103
108
MeOH
(ppm)
6
8'
6
-------
APPENDIX C
ANALYTICAL METHODS - PILOT UNIT TEST
TEST METHOD C-l
54
-------
TEST METHOD C-l; METHOD OF TESTING EMISSION GASES FROM A PILOT CATALYTIC
UNIT INSTALLED ON AN INK DRYER AT WARWICK, NEW JERSEY
1.0 SCOPE
This method covers the analyses of ethanol, n-propyl alcohol, n-propyl
acetate, heptane and total organics in the air exhausting from an ink
dryer before and after catalytic oxidation.
2.0 METHOD OF TEST
Gas chromatography with flame ionization detection. Calibration was
accomplished with prepared standards of ethyl alcohol, proply alcohol,
proply acetate, heptane, and hexane.
3.0 EQUIPMENT
Gas chromatographs (1) Carle Model 9700 and Varian Model 1200. Carle
gas sampling valves, air moving pumps and accessory items. Supply
gases for the operation of the gas chromatographs, air, hydrogen and
nitrogen. •
4;.0 OPERATING PARAMETERS • . .
, . Column Oven. V .. : : ' 100°C' . ; :. .,,-•'.
Detector ' ' l'50°C FID ; '
: #'
Carrier . N2 at 35cc/min.
Combustion Gas . R~ 30 cc/min,
Air 300 cc/min.
Column FFAP 10 ft, 1/8" O.D.
Catalytic Incinerator 3-7 SCFM; Inlet 450°-650°F
Parameter Outlet 500°-700°F, pressure of
inlet and outlet will be 0-4" w.c.
5.0 OPERATING PROCEDURE
The samples of air to be analyzed are drawn to the gas sample valve
through non-absorbing teflon tubing by pumps. On signal, the sample
valves are switched and the analysis begun. Prepared gas standards
are used for the calibration of both gas chromatographs. Calibration
is to be made at the beginning and end of the testing for. each day.
The instrument output is recorded on a single 2-pen strip chart
55
-------
recorder for ease of data comparison. The total hydrocarbon analysis
is determined by sampling the vapors in the usual manner, then back-
flushing all components to the detector for a measure of all components.
The calibration is achieved with prepared hexane gas standards.
6.0 REPORTING
The data is in the form of chromatographic recordings which are ana-
lyzed by the area comparison technique with known samples and reported
on data sheets. A total of nine (9) tests are run, each portraying
three (3) different space velocities at three (3) different tempera-
tures .
A minimum of three samples at each of these points are analyzed to
verify identical recordings but only one set of recordings is reported.
(Exception: the data for the three month test is an average of the
three or more samples.)
56
-------
APPENDIX D '
ANALYTICAL METHODS - FULL SCALE TEST
TEST METHOD D-l
TEST METHOD D-2
57
-------
TEST METHOD D-l
Method of Testing Emission Gases from
Engelhard Catalytic Unit Installed on
Formaldehyde Absorber Plant #2
Columbus, Ohio
1. SCOPE
1.1 This method covers the determination of carbon monoxide, formal-
dehyde, demethyl ether, and methyl alcohol in absorber emission
gases leading into and exiting an Engelhard catalytic unit by
using gas chromatography.
This method can determine gas concentrations from 2% by weight
down to 1 ppm. The method utilizes external standards for COS
HCHO, (CH ) 20, and CH» OH all in the gas phase.
SUMMARY OF METHOD
2.1 This method is intended for routine sampling and analysis of
absorber emission gases. Directions are given for the collection
of grab samples.
2.2 The gas analysis is performed in two parts each part using 0.5 ml
samples. Carbon monoxide is analyzed by separation with a molec-
ular sieve column. The remaining organic gases are separated on
a Poropak T column.
Both columns are operated isothermally. The detector is a flame
ionization type with a nickel reducing catalyst to methanate
formaldehyde and carbon monoxide in order to enhance their detect-
ability. All peaks are thus detected as methane.
SIGNIFICANCE
3.1 The measurement through monitoring emission gases prior to enter-
ing and after exiting the Engelhard catalyst unit provides data
for assessing the effectiveness of the unit in reducing atmos-
pheric pollutants emitted by the formaldehyde absorber.
58
-------
4. APPARATUS
4.1 Gas chromatograph equipped for isothermal operation at up to 250°C.
4.2 Flame ionization detector with linear response characteristic for
hydro carbons from 10 ppm to 10% by volume. •
4.3 Six-port sample valves equipped with 0.5 sec sample loops.
4.4 Columns
4.4.1 Poropak T columns 1/8 inch OD stainless steel 22 feet in
length packed with 100/120 mesh material which has been
acetone washed and preactivated.
4.4.2 Mole sieve column 1/8 inch OD stainless steel 11 feet in
length packed with 80/100 mesh water washed 5 X material
which is preactivated at 310°C for 12 hours under helium
flow.
4.5 Temperatures
4.5.1 Sample Valves .. 250°C
4.5.2 Detector 300°C
4.5.3 Injection Ports.150°C
4.5.4 Nickel Catalyst 350°C
. 4.5.5 Column Oven 145°C
4.6 Carrier gas is nitrogen, zero grade gas certified for total hydro-
carbons as CH, to be below 0.5 ppm.
4.6.1 Mole sieve column flow rate 30ml/min
. 4.6.2 Poropak T column flow rate 30ml/min
4.7 Detector Gas
4.7.1 Hydrogen, Prepurified 99.95% IU . .
4.7.2 Air-breathing .quality, cleany dry, .and oil.free
4.8 Standard Gases
Carbon monoxide and dimethyl ether standards in nitrogen obtained
from M. G. Scientific Gases, Somerville, New Jersey.
4.8.1 Aluminum Tank #1 97.1 ppm CO
19.6 ppm DME
4.8.2 Aluminum Tank #2 21.2 ppm Co
20.1 ppm DME
4.9 Sampling Syringes
4.9.1 50cc Glass Syringes
4.9.2 50cc Disposable Plactic Syringes
4.10 Recorder: 10 inch wide strip chart recorded. A HP 7123A with
1 millivolt full scale sensitivity or its equivalent. Chart
speed 4 inch per minute.
59
-------
SET UP AMD CALIBRATION
L
5.1 6ajt Connections
5.1.1 Connect zero grade nitrogen up to carrier gas inlet on gas
chromatograph. Set supply pressure to 100 psi.
5.1.2 Connect prepurified 99.95% hydrogen to F.I.D. fuel inlet
to detector set supply pressure to 28 psi.
5.1.3 Connect air which is clean, dry, and oil free to F.I.D.
oxidizer inlet to detector. Set supply pressure to 28 psi.
5.2 Connect 10 inch strip chart recorder to F.I.D. electrometer sensi-
tive to 3x10 amps.
5.3 Connect columns to appropriate six-port sampling valves.
5.4 Install nickel catalyst tube between columns and detector.
5.5 Begin nitrogen flow through colunns, catalyst tube and detector
at 30ml/min ± 5ml per minute as measured with a soap film flow
meter.
5.6 After purging system with nitrogen for 30 minutes set zone tem-
peratures as follows:
Injection Ports 150°C
Column Oven 145°C
Sample Valves 250°C
5.7 When temperature of zones have stabilized check flow rate of col-
umns and readjust to 30ml/min.
5.8 Begin hydrogen flow with head pressure of 28 psi. Check for flow.
5.9 Begin air flow with head pressure of 28 psi. Check for flow.
5.10 Shut off hydrogen and air.
5.11 Set temperature of remaining zones:
Nickel Catalyst Tube 350°C
Detector 300°C
5.12 When temperatures stabilize turn air and hydrogen on and ignite
flame of F.I. detector.
5.13 Allow detector to equilibrate for 24 hours.
5.14 After 24 hour equilibration time turn recorder on and zero
base line with electrometer controls.
Drift of base line should be less than 1% per hour.
CALIBRATION
6.1 Calibration Standards
60
-------
6.1.1 Carbon monoxide: CO -Certified calibration gases purchased
from M. G. Scientific are used.
1% CO standard ± 0.01% for Inlet
100 ppm CO ± 1 ppm for Outlet
20 ppm CP ± 0.1 ppm for Outlet
6.1.2 Dimethyl ether: DME -Certified calibration gases purchased
from M. G. Scientific are used.
1% DME standard ± 0.01% for Inlet
20 ppm DME ±0.1 ppm for Outlet
6.1.3 Methyl Alcohol: MeOH '
Reagent grade methyl alcohol purged with dry nitrogen at
constant temperature to yield know concentration of MeOH
in nitrogen -gas sample.
500 ppm MeOH for Inlet
35 ppm MeOH for Outlet
6.1.4 Formaldehyde: HCHO
Formaldehyde concentrate 50% or 30% as analyzed by Sulfite
method (See attachment #1).
Purge mixture of water containing known weight % HCHO with
dry nitrogen at constant temperature.
150 ppm HCHO standard for Inlet
35 ppm HCHO standard for Outlet
6.2 Calibration Procedure - Bottled Gases
6.2.1 Purge sample loops with low flqw of bottled calibration
•'.•"'' . • gases..' . '..''. • ....':'• • : •:•••.: '.....•
,'.-.':.;:•'.• ••' •' .• ; . 10 to 20 ml./mln "."..",'.,-. :..-'••• '.." ' ."- ' ' ," •.' ' V;' '
6.2.2 Inject sample onto mole sieve column for carbon monoxide
calibration.
6.2.3 Record peak height, width of peak at h peak height and
retension time from injection, attenuation and range
from electrometer. Adjust attenuation to maximize peak
height while remaining on scale.
6.2.4 Calculate peak area by
Area = H x W
6.2.5 Calculate response factor for carbon monoxide.
ppm CO or % from tank standard
co = H x W
CO CO
6.2.6 Purge sample loops with bottled gas.
6.2.7 Inject sample onto Poropak T column for dimethyl ether.
6.2.8 Follow instruction given in steps 6.2.3 and 6.2.4 for DME.
61
-------
6.2.9 Calculate response factor for dimethyl ether.
RF™-, = % or ppm DME from tank standard
DMc. - •••* • - — -
TJME X DME
6.3 Calibration Methyl Alcohol
6.3.1 Set up gas scrubber containing 500 ml reagent grade methyl
alcohol.
6.3.2 Purge system with dry nitrogen 20 to 30 ml per minute.
6.3.3 Flush 50cc syringe with flow from scrubber saturated with .
methyl alcohol record temperature of vapor. Fill syringe
with vapor.
6.3.4 Purge sample loops with vapor in syringe.
6.3.5 Inject sample onto Poropak T.
6.3.6 Follow instructions given in steps 6.2.3 and 6.2.4 for
methyl alcohol.
6.3.7 Calculate % for methyl alcohol in vapor.
j M OH= Part^-al pressure MeOH x 100
atmospheric pressure of day (or 760mm)
Partial pressure MeOH = Antilog of the log1f,P
38.324
6.3.8 Calculate response factor for MeOH.
x WMeOH
6.4 Calibration Formaldehyde
6.4.1 Prepare a solution of known weight % formaldehyde in water.
Analyze a portion of this solution by attachment #1 pro-
cedure.
6.4.2 Place solution prepared in step 6.4.1 into gas scrubber
and purge slowly with nitrogen as in step 6.3.1.
6.4.3 Flush 50cc syringe with HCHO saturated nitrogen, record
temperature of solution.
6.4.4 Fill 50cc syringe with nitrogen from gas scrubber saturated
with HCHO
6.4.5 Flush sample loops and inject sample onto Poropak T column .
6.4.6 Record retension time, peak height and peak width. See
steps 6.2.3 and 6.2.4.
62
-------
6.4.7 Calculate % formaldehyde in nitrogen vapor.
% HCHO = partial pressure HCHO x 100 _
atmospheric pressure of day in mm
Partial pressure HCHO = antilog of the
mm 10
Log1(JPimnHCHO = 9.942 - 0.953 (0.488) W/10- ^21
W = HCHO concentration in percent by weight
T = absolute temperature "Kelvin
6.4.8 Calculate response factor for HCHO.
RF = % HCHO _
HCH° " • BHCHQ X WHCHO
6.4.9 Limits of step 6.4.7.
Temperature is to be below 60 °C for all concentrations and
for temperature between 60° and 100°C applies only to
concentration below 20% by weight.
6.5 The response of a hydrogen flame ionization detector is linear
from 0.01 ppm to 10 ppm for GI through C,. paraffinic and olefinic
hydrocarbons. It is assumed the linear range for CO, DME, MeHO,
HCHO is linear form 10 ppm to 10,000 ppm (1%) due to the presence
of the nickel catalyst tube with a 0.5 sec sample loop.
7. PROCEDURE
7.1. Sampling of Gases
7.1.1- Grab samples are taken of all, gas samples.
7.1.2-.. Fill 5Qcc. syringe with gas to be samples and. flush out
syringes. ' ;' •
7..1.3 Fill syringe with sample gas and return to lab for analy-
sis.
7.2 Location of Sampling Point
7.2.1 Engelhard Inlet samples are taken from the bottom of the
formaldehyde absorber demister tank.
7.2.2 Engelhard Outlet samples are taken from the bottom of the
Engelhard Catalytic Unit.
7.3 Running Samples
7.3.1 Mark recording chart with date, name of sample (Inlet or
Outlet) sample type CO or DEM, HCHO, MeOH.
7.3.2 Flush sample loops with sample. See steps 7.1.1 through
7.1.3. '
7.3.3 Inject sample for CO onto mole sieve.
7.3.4 If attenuation must be adjusted to keep pen on scale
resample.
63
-------
7.3.5 Inject sample for DME, HCHO, and MeOH onto Poropak T
column.
7.3.6 If attenuation must be adjusted to keep pen on scale
resample.
7.3.7 Record peak height and width according to procedure out-
lines in steps 6.2.3 and 6.2.4.
8. CALCULATIONS
8.1 The concentration of each gas in the chromatograph is determined
from the response factor for the gas as determined in the cali-
bration section part 6.
8.2 ppm CO = H x W x RFpn x Range x Attenuation
L*L) wU L»U
8.3 ppm HCHO = \CEO x WHCHO X RFHCHO X Ran§e x Attenuation
8.4 ppm DME = H^ x WDME x RFDME x Range x Attenuation
8.5 ppm MeOH = 1 x W x RFMeOH x Range x Attenuation
9. AIRFLOW
9.1 Record Inlet temperature of air to Engelhard Catalyst unit in
"Fahrenheit.
9.2 Record Outlet temperature of air from Engelhard Catalyst unit in
"Fahrenheit.
9.3 Record methyl alcohol flow rate in gallons per minute to formal-
dehyde plant #2.
9.4 Record 0- percentage of air flow to formaldehyde plant #2.
9.5 Determine SCFM air flow through formaldehyde plant #2.
Record back pressure in-psi for plant #2 blower and then refer to
Chart #1.
9.6 Determine SCFM air flow across Engelhard Catalyst bed. Revised
1/18/80.
V =AF (4727.9-(43.001)(%Ogin) _
A* bL/m 3844.2+(AF) (25. 961)- (1.2633) (%02in)
(MeOHGpM)
- 34. 039 (MeOH)
GPM
AF =Air flow to formaldehyde catalyst plant #2
SCFM
%0 = Oxygen percentage in air flow to formaldehyde catalyst
plant #2
64
-------
10. REPORTING
10.1 Compile data for each month on attached form. Form #1.
10.2 Each day's data should contain the following:
Date
ppm CO ppm Co
ppm ECHO Inlet ppm HCHO Outlet
ppm DME ppm DME
ppm MeOH ppm MeOH
Flow Rate MeOH
Inlet Temperature °F
Outlet Temperature °F
65
-------
ATTACHMENT #1 GPAM 100.1
Issued 4/1/77
DETERMINATION OF FORMALDEHYDE CONTENT
(SODIUM SULFITE METHOD)
SCOPE;
This method is for the determination of formaldehyde content of aqueous
solutions of formaldehyde.
PRINCIPLE;
This method is based on the quantitative liberation of sodium hydroxide when
formaldehyde reacts with sodium sulfite to form the formaldehyde-bisulfite
addition product.
APPARATUS AND REAGENTS;
a. Analytical balance.
b. 2 ml volumetric pipet
c. 250 ml iodine flasks
d. 50 ml buret
e. 1M sodium sulfite. Dissolve 126 g Na SO (anhydtous) in about 950 ml
distilled water. Add a few drops of thymolphthalein indicator and
neutralize. Make up 1000 ml. This solution should be made frequently
in small quantities to avoid loss of strength due to oxidation. Solu-
tion over three weeks old should not be used.
f. IN sulfuric acid. Standardize as follows:
1) dry reagent grade Na-CO for 1 hour at 270-300°C. Cool in desicator.
2) weigh, by difference, triplicate samples of 2g each within ± 0.2 mg
and transfer quantitatively to 250 ml flasks.
3) dissolve each sample in 50 ml distilled water.
4) titrate with the acid to be standardized to pH 5.0 or to methyl orange
end point.
5) titrate a blank of 50 ml distilled water in the same manner as 4°
6) calculate normality as follows:
WEIGHT OF Na0CO_ X 1000
Normality= ; 2 3 ___.
(Av. ml titrant for Na CO solution-mi titrant for blank 53.00
g. Thymolphthalein indicator. Dissolve 0.1 g thymolphthalein in 100 ml
h. 0.1 N NaOH
66
-------
PROCEDURE:
a. Place 25 ml distilled water in a 250 ml -iodine flask and add 5 drops of
thymolphthalein indicator.
b. Weigh the stoppered flask to the nearest 0.001 g.
c. Add a 2 ml formaldehyde sample, keeping the pipet tip below the water
surface.
d. Immediately restopper the flask and reweigh to the nearest 0.001 g.
e. Neutralize the solution with 0.1 N NaOH.
f. Add 75 ml of 1 M Na?SO_ solution, this solution being first added around
the stopper which is lifted to allow a portion to enter the flask. This
procedure should prevent the loss of formaldehyde.
g. Mix thoroughly and titrate the liberated NaOH with 1 N H SO, until the
blue, color just disappears.
h. Run a blank in the same manner using the same amounts of reagents, adding
water to match the total volume of the titrated solution.
CALCULATION:
TT4. „ - T , , , (ml acid used - ml acid in blank) (N of acid) 3.003
Wt. % formaldehyde = r-rr—£ r^
. wexght of sample
INTERPRETATION; . . ;
Formaldehyde solutions sold by Georgia-Pacific Chemical normally range from
37-50% formaldehyde content.
67
-------
CO
-'
INLET ANALYSIS
PPM
CO
PPM
HCHO
PPM
DME
PPM
MeOH
•<
FLOW
RATE
SCFM
INLET
TEMP.
OUTLET
op
OUTLET ANALYSIS
PPM
CO
PPM
HCHO
O
PPM
DME
PPM
MeOH
-------
ADDENDUM
ITEM #1 Please note that the statement-regarding the ability of the nickel
• catalyst to methanate formaldehyde quantitatively in Section 2.2 has
not been documented by laboratory personnel nor are specific refer-
ences detailing this step available to the laboratory at this time.
ITEM #2 Regarding Inlet and Outlet levels for carbon monoxide Section 6.1.1,
dimethyl ether Section 6.1.2, methyl alcohol Section 6.1.3, and
formaldehyde Section 6.1.4 these values are based on information
contained in a memo to R. C. Moehl from N. Magnussaii dated March 14,
1978.
ITEM #3 Regarding Section 1.1 and Section 6.5 dealing with dynamic linear
range of the detector these are estimates based on Ken Dunder's
experience and not documented in any report at this time.
ITEM #4 Regarding Section 6.4.7 the equation for the vapor pressure of form-
aldehyde is taken from Walker's work on formaldehyde Srd.ed.,
Pages 114 and 115.
ITEM #5 Regarding Section 6.3.7 the equation for the vapor pressure for
methyl alcohol is taken from an undated memo by Barbara Richard.
No references are given. •
ITEM #6 Regarding Section 9.6 the equation to determine the volume of air
flow across the Engelhard catalyst bed is taken from calculations
performed by Tom Moehl in an undated memo based on equations sup-
plied by Al Buckingham in a memo to Ken Dunder dated May 18, 1979.
No references, are given.
ITEM #7 Regarding frequency of sampling please refer to the following
letters:
To: Ken Dunder From: Norm Martin, Engelhard Industries
Dated: May 30, 1979 Test Specifications: TS-34
To: Norm Martin From: Ken Dunder, Georgia-Pacific Corporation
Dated: June 6, 1979.
69
-------
------- |