United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 79-NHF-13a
September 1980
Air
Urea Manufacture
Emission Test Report
Agrico Chemical
Company
Blytheville, Arkansas
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REPORT ON PROCESS EMISSIONS TESTS
AT THE AGRICO CHEMICAL COMPANY
UREA MANUFACTURING FACILITY
IN BLYTHEVILLE, ARKANSAS
(DECEMBER 1978)
REPORT 79-NHF-13a
Thomas M. Bibb
EPA Project Manager
Clyde E. Riley
EPA Technical Manager
EPA Contract #68-02-2820
Work Assignment #11
TRC Project No. 0988-E80-01
Willard A. Wade III, P.E.
Senior Project Manager
Eric A. Pearson
Project Scientist
Margaret M. Fox
Project Chemist
July 31, 1980
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PREFACE
The work reported herein was performed by personnel from TRC Environmental
Consultants, Inc. (TRC), the GCA/Technology Division (GCA), Agrico Chemical
Company, Blytheville, Arkansas (Agrico), and the U.S. Environmental Protection
Agency (EPA).
The scope of work, issued under EPA Contract No. 68-02-2820, Work Assign-
ment Number 11, was under the supervision of the TRC Project Manager, Mr.
Willard A. Wade III. Mr. Eric A. Pearson of TRC was responsible for summariz-
ing the test and analytical data presented in this report. Sample analysis
was performed at the Agrico, Blytheville, Arkansas plant under the direction
of Ms. Margaret M. Fox, and at the TRC laboratory in Wethersfield, Connecticut
under the direction of Ms. Joanne M. Marchese.
Stephen K. Harvey of GCA was responsible for monitoring the process opera-
tions during the emissions testing program. GCA personnel were also respon-
sible for preparing Section 3.0, Process Description and Operations, and
Appendix G of this report.
Personnel of Agrico Chemical Company, Blytheville, Arkansas, whose assist-
ance and guidance contributed greatly to the success of this emissions testing
program included Mr. Jesse Boggan, Environmental Coordinator, Mr. James
Kilpatrick, Chief Chemist, and Mr. Deryl Beiard, Chemist.
Mr. Eric A. Noble, Office of Air Quality Planning and Standards, Indus-
trial Studies Branch, EPA, served as Test Process Engineer and was responsible
for coordinating the process operations monitoring.
Mr. Gary D. McAlister, Office of Air Quality Planning and Standards, Emis-
sion Measurement Branch, EPA, served as Lead Chemical Engineer and was respon-
sible for developing and evaluating the analytical procedures used on this
program.
-11-
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Mr. Clyde E. Riley, Office of Air Quality Planning and Standards, Emission
Measurement Branch, EPA, served as Technical Manager and was responsible for
coordinating the emission test program.
-111-
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TRC-Environmental Consultants, Inc.
Willard A. Wade III, P.E.
Project Manager
July 31, 1980
NOTE: Mention of trade names or commercial products in this publication does
not constitute endorsement or recommendation for use by the Environmen-
tal Protection Agency.
-IV-
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TABLE OF CONTENTS
SECTION
PAGE
1.0 INTRODUCTION 1
1.1 Background 1
1.2 Measurement Program 1
1.3 Description of Report Sections 4
2.0 SUMMARY OF RESULTS 5
2.1 Granulator "C" Scrubber Outlet Gas Stream 5
2.2 Comparison of TRC and Agrico Scrubber
Outlet Gas Stream Analyses 9
2.3 Scrubber Liquor Sampling Results 15
2.4 Urea Audit Samples - Comparison
of TRC and Agrico Analyses 17
3.0 PROCESS DESCRIPTION AND OPERATIONS . 20
3.1 Process Equipment 20
3.2 Process Operation 22
4.0 LOCATION OF SAMPLING POINTS 31
4.1 Granulator C Scrubber Outlet 31
4.2 Scrubber Liquor Sampling Locations 31
5.0 SAMPLING AND ANALYSIS METHODS 34
5.1 EPA Reference Methods Used in This Program .... 34
5.2 Urea and Ammonia Sampling and Analysis 35
5.2.1 Sampling 35
5.2.2 Sample Recovery and Preparation 37
5.2.3 Sample Analysis 38
5.2.3.1 Analysis by TRC 38
5.2.3.2 Analysis by Agrico 40
5.3 Formaldehyde Sampling and Analysis 41
5.4 Insoluble Particulate Sampling and Analysis .... 41
5.5 Scrubber Liquor Sampling and Analysis 42
5.5.1 Sampling, Sample Recovery and Preparation ... 42
5.5.2 Sample Analysis 43
5.6 Urea Audit Samples - TRC and Agrico Analysis ... 44
5.6.1 Analysis by TRC 44
5.6.2 Analysis by Agrico 45
APPENDICES
A-l
A-2
Computer Printout Test Results
Granulator C Scrubber Outlet
Sample Equations and Example Calculations
Field Data Sheets
-v-
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TABLE OF CONTENTS (Continued)
APPENDICES (Continued)
C Sampling and Analysis Procedures
C-l Urea Procedures
C-2 Ammonia Procedures
C-3 Formaldehyde Procedures
D Analytical Data
D-l Data Analysis Summaries
D-2 Chemical Laboratory Notebook
D-3 Scrubber Liquor Analysis Times
E TRC/Agrico Joint Analyses
E-l Agrico Field Sample Analyses
E-2 TRC Audit Sample Analyses
E-3 Agrico Audit Sample Analyses
F Sampling Train Calibration Data
G Process Operators Log
H Project Participants
I Scope of Work
Work Assignments
Technical Directives
-vi-
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LIST OF TABLES
TABLE PAGE
2-la Summary of Urea, Ammonia and Formaldehyde Emissions
from the C Granulator Scrubber Outlet at Agrico
Chemical Company (English Units) 6
2-lb Summary of Urea, Ammonia and Formaldehyde Emissions
from the C Granulator Scrubber Outlet at Agrico
Chemical Company (Metric Units)
2-2 Insoluble Particulate Analysis Results from the
C Granulator Scrubber Outlet at Agrico Chemical Company . 10
2-3 TRC and Agrico Urea Analysis Results from the C
Granulator Scrubber Outlet at Agrico Chemical Company . . 11
2-4 TRC and Agrico Ammonia Analysis Results from the C
Granulator Scrubber Outlet at Agrico Chemical Company . . 13
2-5 C Granulator Scrubber Liquor Analysis Results
from Agrico Chemical Company 16
2-6 Results from Urea Audit Sample Analyses Performed
by TRC and Agrico at Agrico Chemical Company,
Blytheville, Arkansas 18
3-1 Average Values and Ranges for Process and Control
Equipment Operating Parameters During Emission Test
Runs at Agrico Chemical Company, Blytheville,
Arkansas 24
3-2 Variability of Three Process Operating Parameters
During Emission Test Runs at Agrico Chemical Company,
Blytheville, Arkansas 26
3-3 Comparison of Product Rates Calculated by Equation 1
and Production Rates Calculated from Corrected
Totalizer Readings During the October 1978 Emission
Tests at Agrico Chemical Company, Blytheville,
Arkansas > 29
-vii-
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LIST OF FIGURES
PAGE
Granulator Exhaust Ducting and Scrubbers at
Agrico Chemical Company, Blytheville, Arkansas
3-1 Urea Manufacturing - Agrico Chemical Company,
Blytheville, Arkansas 21
3-2 Joy Tubulaire Scrubber - Agrico Chemical Company,
Blytheville, Arkansas 23
4-1 Locations of C Granulator Scrubber Outlet Test
Ports and Points at Agrico Chemical Company in
Blytheville, Arkansas 32
4-2 Joy Tubulaire Scrubber - Agrico Chemical Company,
Blytheville, Arkansas 33
5-1 Modified EPA Particulate Sampling Train August 18,
1977, Federal Register 36
-viii-
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1.0 INTRODUCTION
1.1 Background
Section 111 of the Clean Air Act of 1970 charges the Administrator of the
United States Environmental Protection Agency (EPA) with the responsibility of
establishing Federal standards of performance for new stationary sources which
may significantly contribute to air pollution. When promulgated, these
standards of performance for new stationary sources (SPNSS) are to reflect the
degree of emission limitation achievable through application of the best
demonstrated emission control technology. Emission data, collected from
controlled sources in the particular industry of concern, provide a portion of
the data base used by EPA to develop SPNSS.
EPA's Office of Air Quality Planning and Standards (OAQPS) selected the
Agrico Chemical Company urea manufacturing plant in Blytheville, Arkansas, as
a site for an emissions test program. The program was designed to provide a
portion of the emission data base required for SPNSS. In addition, emission
samples obtained during this program were used as part of a urea analysis
method investigation. The results of this investigation are presented in the
EPA report 79-NHP-13 "Development of Analytical Procedures for the
Determination of Urea from Urea Manufacturing Facilities".
EPA engaged TRC to measure urea, ammonia and formaldehyde in the exhaust
gas of the granulator "C" scrubber at the Agrico urea plant. This report
presents the results of this sampling program conducted under EPA contract
#68-02-2820 and Technical Directives #1 and.12.
1.2 Measurement Program
The measurement program consisted of emissions tests performed by TRC at
the Agrico Chemical Company urea manufacturing facility in Blytheville,
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Arkansas, on December 18 and 19, 1978.
The Agrico plant produces granulated urea for industrial and fertilizer
A
use. The urea is produced by three Spherodizer granulators which operate
continuously 24 hours a day, 7 days a week, as production demands. Each
granulator has its own impingement-type water scrubber. Granulator exhaust
air is ducted through the scrubber and fan and then discharged from a stack.
Air flow through the granulator to the constant flow scrubber is controlled
with a dilution damper which varies the ratio of dilution air to exhaust gas.
A schematic of the granulators1 exhaust gas ducting and emission control
system is shown in Figure 1-1.
The measurement program consisted specifically of the following:
1. Six one-hour emissions tests at the "C" granulator scrubber outlet.
Sampling was.performed for urea, ammonia, formaldehyde and insoluble
particulate in the outlet gas stream.
2. Sampling of the scrubber inlet and outlet liquor at the beginning and
end of each emissions test run.
The scrubber outlet gas stream and scrubber liquor samples were analyzed
within 24 hours for urea and ammonia and within 20 days for formaldehyde and
insoluble particulate. The urea and ammonia analyses of the gas stream
samples were performed by TRC and Agrico, for comparison purposes. Urea
analyses were performed using the Kjeldahl (with preliminary distillation)
method.
Two identical sets of twelve urea audit samples were prepared by TRC
according to specific EPA instructions. One set was analyzed by TRC, the
other by Agrico; both analyses took place within 12 hours of sample
preparation. While both analyses were performed using the Kjeldahl total
nitrogen method (without preliminary distillation), the final ammonia content
(from which the urea content was calculated) was determined by nesslerization
-2-
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WET
SCRUBBER
"ff€)
STACK —
FAN —
STAC
FAN
CONTROL
ROOM
ni ITI FT
UU 1 LL. 1
AMPLING —
nnnTC
r UK 1 o
o
V^X
/
^r-£
— ^
|
T
LcTAP
U— DILUTION
r AIR
t
— WET
—. ^ SCRUBBER
^—DILUTION
r AIR
t
. WET
/ SCRUBBER
^i — DILUTION
r AIR
L.
^
',
',
'<,
/
X
/
/
J
\
',
'
2
^
GRANULATOR "A"
,.. Ufll I
GRANULATOR "B "
GRANULATOR "C"
FIGURE 1-1: GRANULATOR EXHAUST DUCTING AND SCRUBBERS AT
AGRICO CHEMICAL COMPANY IN
BLYTHEVILLE, ARKANSAS
-3-
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by TRC, and by titration by Agrico.
All sampling and measurements made at this facility were performed during
times of normal urea production process operation, as described in Section
3.0, Process Description and Operations. The urea production rate from the
"C" granulator during these tests was approximately 400 tons/day. TRC
personnel were responsible for performing the above emissions testing and
sampling. Concurrently, GCA was responsible for monitoring and recording
pertinent process operation parameters. During the testing program the plant
was producing fertilizer grade urea.
1.3 Description of Report Sections
The following sections of this report contain the summary of results
(Section 2.0), process description and operations (Section 3.0), location of
sampling points (Section 4.0) , and descriptions of sampling and analysis
methods (Section 5.0). Audit sample results are contained in Section 2.0.
Detailed information on methods and procedures, and all field and laboratory
data, are contained in their associated appendices, as noted in the Table of
Contents.
r-4-
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2.0 SUMMARY OF RESULTS
This section presents the results of the emissions tests performed in
December 1978 at the Agrico Chemical Company urea manufacturing plant in
Blytheville, Arkansas. Testing was performed on the gas stream exiting, and
on the liquor streams entering and exiting, the granulator "C" scrubber.
2.1 Granulator "C" Scrubber Outlet Gas Stream
The data from the granulator "C" scrubber outlet gas stream emissions
tests are shown in Table 2-1. The urea and ammonia data represent the
analyses performed by TRC at the Agrico laboratory within 24 hours of sample
collection; the formaldehyde analyses were performed at TRC within 20 days of
sample collection.
The urea and ammonia analyses included a common preliminary distillation
step during which hydrolysis of some urea to ammonia is known to occur. The
commonly used conversion factor is: 7 percent of the urea converts to ammonia
during this preliminary distillation . The data in Table 2-1 are
appropriately corrected to account for this conversion, using the 7 percent
factor.
These scrubber outlet gas stream data differ considerably from the data
obtained by TRC during emissions tests on the granulator "A" scrubber at this
facility in October 1978. While the average ammonia gas stream concentration
(grains/DSCF) in December is about 80% that in October, the urea
concentrations in December are 3 times those of October; and the December
formaldehyde concentrations are 16 times those of October. These differences
may result in large part from differences in the granulators at this Agrico
Standard Methods of Water and Wastewater Analysis, APHA, AWWA, WPCF,
14th edition, 1975 p. 408.
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TABLE 2-la (English)
SUMMARY OF UREA, ANMONIA, AND FORMALDEHYDE EMISSIONS PROM THE C GRANULATOR
SCRUBBER OUTLET AT AGRICO CHEMICAL COMPANY, BLYTIIEVILLE, ARKANSAS
Run Number Runl Run 2 Run3 Run4 Run 5 Run6 Average
Bate 12-18-78 12-19-78 12-19-78 12-19-78 12-19-78 12-19-78
Volume of Gas Sampled (DSCF).3 34.93 34.44 32.62 33.14 32.41 33.62 33.53
Volumetric Flowrate (DSCFM) " 55180 54720 51130 52910 51730 53750 53237
Average Gas Temperature fT) 92 102 104 " 103 105 104 102
Percent Moisture 6.0 3.8 5.1 4.9 3.1 3.8 4.5
Percent Isokinetic 107.2 106.7 108.2 106.2 106.2 106.1 106.8
Production Rate (Tons/Hour) 15.46 15.08 15.08 15.08 15.08 15.08 15.14
Urea Data c
Total Sample Weight (Milligrams) 63.0 96.3 36.0 51.5 30.8 50.3 54.7
Grains/DSCF 0.02779 0.04306 0.01697 0.02391 0.01464 0.02304 0.02511
Pounds/fbur 13.14 20.19 7.438 10.85 6.492 10.61 11.46
Pounds/Ton 0.850 1.339 0.4932 0.7195 0.4305 0.7036 0.7569
Ammonia Data
Total Sample Weight (Milligrams) 420.7 324.4 591.5 346.2 320.7 303.5 384.5
Grains/DSCF 0.1855 0.1451 0.2792 0.1609 0.1524 0.1390 0.1766
Pounds/Hour 87.72 68.02 122.36 72.95 67.56 64.04 80.57
Pounds/Ton 5.674 4.511 8.114 4.837 44.80 4.247 5.322
Formaldehyde Data e
Total Sample Weight (Milligrams) 3.90 4.70 3.30 4.24 2.05 3.14 3.56
Grains/DSCF 0.001719 0.002102 0.001558 0.001970 0.000974 0.001438 0.001635
Pounds/Hour 0.8131 0.9856 0.6827 0.8934 0.4318 0.6625 0.7460
Pounds/Ton 0.0526 0.06536 0.04527 0.05924 0.02863 0.04393 0.04927
Dry standard cubic feet e 68°F and 29.92 inches Mg.
Dry standard cubic feet per minute.
c Kjeldahl Analysis method with preliminary distillation, corrected for urea to ammonia conversion.
Nessler analysis method with preliminary distillation, corrected for urea to ammonia conversion.
Chromotropic Acid Analysis Method.
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TABLE 2-lb (Metric)
SUMMARY OF UREA, AMMONIA, AND FORMALDEHYDE EMISSIONS FROM THE C GRANULATOR
SCRUBBER OUTLET AT AGRICO CHEMICAL COMPANY, BLYTIIEVILLE, ARKANSAS
Run Number
Date
Volume of Gas Sampled (ton3)
Volumetric Flowrate (NmVmin)
Average Gas Temperature (°C)
Percent Moisture
Percent Isokinetic
Production Rate (Mg/lbur)
Urea Data
Total Sample Weight (mg)
Grams/Nm3
Kg/Hour
Kg/Mg
Ammonia Data
Total Sample Weight (mg)
Grams/Nm3
Kg/Hour
Kg/Mg
Formaldehyde Data e •
Total Sample Weight (mg)
Grams/Nm3
Kg/ltour
Kg/Mg
Run 1
12-18-78
0.98922
1562.7
33
6.0
107.2
14.025
Run 2
12-19-78
0.97534
1549.7
39
3.8
106.7
13.681
Run 3
12-19-78
0.92380
1448.0
40
5.1
108.2
13.681
Run 4
12-19-78
0.93852
1498.4
39
4.9
106.2
13.681
Run 5
12-19-78
0.91785
1464.99
41
3.1
106.2
13.681
Run 6
12-19-78
0.95212
1522.2
40
3.8
106.1
13.681
63.0
0.06356
5.958
0.425
420.7
0.4244
39.79
2.857
3.90
0.00393
0.36882
0.01315
96.3
0.09851
9.159
0.669
324.4
0.3320
30.86
2.256
4.70
0.00481
0.44707
0.03268
36.0
0.03883
3.374
0.247
591.5
0.6389
55.50
4.057
3.30
0.00356
0.30967
0.02264
51.5
0.05472
4.921
0.360
346.2
0.3681
33.09
2.419
4.24
0.00451
.40525
0.02962
30.8
0.03349
2.945
0.215
320.7
0.3488
30.64
2.240
2.05
0.00223
0.19586
0.01432
50.3
0.05271
4.813
0.352
303.5
0.3180
29.05
2.124
3.14
0.00329
0.30051
0.02197
Average
0.94957
1507.7
39
4.5
106.8
13.735
54.7
0.05746
5.198
0.378
384.5
0.4041
36.55
2.661
3.56
0.00374
0.33839
0.02464
Normal cubic meters 9 20°C, 760 mm Hg.
Normal cubmic meters per minute.
Kjeldahl analysis method, corrected for. urea to ammonia conversion.
Nessler analysis method with preliminary distillation, corrected for urea to ammonia conversion.
Chromotropic Acid analysis method.
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plant. The three granulators (A, B, and C) in operation at this facility are
not identical and, according to Agrico personnel, do have different operating
characteristics. In particular, the lifting flights in granulator "C" are
larger than those of "B" and "A". These devices help move the prills along
inside granulators, and the larger ones in granulator "C" may have contributed
to the noticeably higher plume opacity from "C" than from "A" and "B", as
noted by Agrico personnel. The higher opacity presumably reflects different
granulator operating characteristics.
The sampling train used during the December tests differed from that of
the October tests in that the December impingers contained only water, while
water and acid impingers were used in October. As a result, the ammonia
collection efficiency may have been less than optimum during the December
tests. If so, then the actual December ammonia concentrations themselves may
equal or exceed those of October.
In December the ammonia analyses were performed both by direct
nesslerization and by nesslerization with preliminary distillation^ ; the
two methods agreed within 10 percent (see Section 2.2). In October, direct
nesslerization was used.
The same formaldehyde analysis method was used in December and in October
(chromotropic acid method). A probable reason for the higher December
formaldehyde results is contaminated distilled water. The water used in
December for impinger charging and sample analysis was deionized through a
resin which subsequently was found to contain significant amounts of
formaldehyde.
The urea analysis methods differed between October and December: the
Kjeldahl method was used in December, and the p-dimethylaminobenzaldehyde
method was used in October. The differences between these two methods,
(1) ibid. pp. 407 ff.
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however, would not account for more than a very small fraction of the observed
disparity between the October and December urea concentrations.
The insoluble particulate analysis results of the granulator "C" scrubber
outlet gas stream tests are shown in Table 2-2. These data indicate that the
insoluble particulate content of the outlet gas stream is insignificant.
2.2 Comparison of TRC and Agrico Scrubber Outlet Gas Stream Analysis
The TRC and Agrico granulator "C" scrubber outlet analysis results are
shown together in Tables 2-3 (urea results) and 2-4 (ammonia results). The
TRC urea data were obtained directly using the Kjeldahl with preliminary
distillation method^ '. The Agrico urea data were obtained indirectly
through separate Kjeldahl (total nitrogen)' ' and distillation/titrimetric
(ammonia nitrogen)' ' analyses; urea was then calculated by subtracting
ammonia nitrogen from total nitrogen. Both corrected and uncorrected data are
shown in Tables '2-3 and 2-4 (corrected for conversion of urea to ammonia
during distillation, as discussed in Section 2.1).
The urea data in Table 2-3 show that on the average the Agrico results are
30% higher than the TRC results. Run by run, however, there is no consistency
between the TRC and Agrico data; the Agrico results vary from much higher to
much lower than the TRC results. There is no immediately evident reason for
the differences between the two sets of data. The indirect method of analysis
used by Agrico is susceptible to inaccuracy, since errors in the component
analysis (for total nitrogen and ammonia nitrogen) may be compounded when urea
nitrogen is calculated by subtraction. The Agrico analysis data (Appendix E)
show that relatively small titrant volumes were used in these titration
analyses: the total nitrogen titrant volumes ranged from 5.8 ml to 13.5 ml;
U) ibid. pp. 437 ff.
(2) ibid. pp. 417 ff.
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TABLE 2-2
INSOLUBLE PARTICULATE ANALYSES RESULTS FROM TIE
"C" GRANULATOR SCRUBBER OUTLET GAS STREAM AT
AGRIOO CHEMICAL COMPANY, BLYTHEVIL1.E, ARKANSAS
I
h-1
o
Run Number
Date
Volume of Gas Sampled (DSCF)a
Volumetric Flowrate (DSCFM)
Total Sample Weight (Milligrams)
Pounds/Hour
Run 1
12-18-78
34 .93
55180
2.08
<0.001
Run 2
12-19-78
34.44
54720
1.82
<0.001
Run 3
12-19-78
32.62
51130
0
0
Run 4 Run 5 Run 6 Average
12-19-78 12-19-78 12-19-78 12-19-78
33.14
52910
0.18
<0.001
32.41
51730
33.62
53750
1.13
<0.001
33.53
53237
0.87
<0.001
aDry Standard Cubic Feet e 68°F, 29.92 inches Hg.
Dry Standard Cubic Feet per minute.
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TABLE 2-3
TRC AND AGRICO UREA ANALYSIS RESULTS
FROM "C" GRANULATOR SCRUBBER OUTLET GAS-STREAM
AT ACRICO CHEMICAL COMPANY, BLYTI1EVILLE, ARKANSAS
Run Number
Date
Run 1
12-18-78
Run 2
12-19-78
Volume of Gas Sampled (DSCF),
Volumetric Flowrate (DSCFM) °
Production Rate (Tons/hour)
Urea Analysis By:
TRC
34.93
55180
15.46
Agrico
Uncorrected
Corrected Uncorrected
Corrected
34.44
54720
15.08
TRC
Uncorrected Corrected
Agrico
Uncorrected Corrected
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/Hour
Pounds/Ton
Run Number
Rate
Volume of Gas Sampled (DSCF).
Volumetric Flowrate (DSCFM)
Production Rate (Tons/hour)
Urea Analysis By:
58.9
0.02597
12.28
0.794
63.0
0.02779
13.14
0.850
175.5
0.07754
36.67
2.372
188.7
0.08338
39.43
2.551
TRC c
Run 3
12-19-78
32.62
51130
15.08
Agrico
90.0
0.04024
18.87
1.251
96.3
0.04306
20.19
1.339
11.8
0.00529
2.480
0.164
12.7
0.00569
2.667
0.176
TRC
Run 4
12-19-78
33.14
52910
15.08
Agrico
Uncorrected
Corrected Uncorrected
Corrected
Uncorrected Corrected
Uncorrected Corrected
Total Sample Weight (Milligrams) 33.6
Grains/DSCF 0.01586
Pounds/Hour 6.951
Pounds/Ton 0.461
36.0
0.01697
7.438
0.493
26.4
0.01249
5.474
0.363
28.3
0.01343
5.886
0.390
48.1
0.02235
10.14
0.672
51.5
0.02391
10.85
0.719
104.8
0.04880
22.13
1.468
112.7
0.05247
23.80
1.578
aOry standard cubic feet § 68°F, 29.92 inches Hg.
wry standard cubic feet per minute.
CTRC urea analysis by Kjeldahl with preliminary distillation. Corrected = uncorrected * 1.07.
Agrico urea analysis by total Kjeldahl nitrogen minus ammonia nitrogen = urea nitrogen. See Section 3.2 for details on data reduction and correction.
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TABLE 2-3 (Cont.)
TRC AND AGRICO UREA ANALYSIS RESULTS
FROM "C" GRANULATOR SCRUBBER OUTLET GAS-STREAM
AT AGRICO CHWICAL COMPANY, BLYTHEVILLE, ARKANSAS
Rim Number
Date
Run 5
12-19-78
Run 6
12-19-78
Volume of Gas Sampled (DSCF). a
Volumetric Flowrate (DSCFM) D
Production Rate (Tons/hour)
Urea Analysis By:
TRC
32.41
51730
15.08
Uncorrected
Agrico
Corrected Uncorrected
Corrected
33.62
53750
15.08
TRC
Agrico
Uncorrected Corrected
Uncorrected Corrected
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/Hour
Pounds/Ton
28.8
0.01368
6.067
0.402
30.8
0.01464
6.492
0.430
19.7
0.00938
4.159
0.276
21.2
0.01009
4.472
0.297
47.0
0.02153
9.917
0.658
50.3
0.02304
10.61
0.704
60.3
0.02768
12.75
0.846
64.8
0.02976
13.71
0.910
Run Number
Average
Volume of Gas Sampled (DSCF). a
Volumetric Flowrate (DSCFM)
Production Rate (Tons/hour)
Urea Analysis By:
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/Hour
Pounds/Ton
TRC
Uncorrected
51.1
0.02347
10.71
0.707
33.53
53237
15.14
Corrected
54.7
0.02511
11.46
0.757
Agrico
Uncorrected Corrected
66.4
0.03056
13.95
0.921
71.4
0.03286
15.00
0.990
aDry standard cubic feet e 68°F, 29.92 inches Hg.
Dry standard cubic feet per minute.
CTRC urea analysis by Kjeldahl with preliminary distillation. Corrected = unconnected * 1.07.
Agrico urea analysis by total Kjeldahl nitrogen minus ammonia nitrogen = urea nitrogen. See Section 3.2 for details on data reduction and correction.
-------
TABLE 2-4
TRC AND AGRICO AMMONIA ANALYSIS RESULTS
FROM "C" GRANULATOR~SrRTJBBER OTTLET GAS-STREAM
AT AGRIOO CHEMICAL COMPANY, BLYTIIEVILLE, ARKANSAS
Run Number
Date
Volume of Gas Sampled (DSCF) a
Volumetric Flowrate (J1SCFM) D
Production Rate (Tons/hour)
Ammonia Analysis By:'
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/I bur
Pounds/Ton
Run Number
Date
Volume of Gas Sampled (DSCF).
Volumetric Flowrate (DSCFM)
Production Rate (Tons/hour)
Ammonia Analysis By:
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/Hour
Pounds/Ton
DN
403.7
0.1780
84.17
5.444
DN
369.6
0.1745
76.46
5.070
TRC C
Dist.-N
Uncor reeled
423.2
0.1866
88.24
5.708
TRC
Dist.-N
Uncorrected
592.9
0.2799
122.65
8.133
Run 1
12-18-78
34.93
55180
15.46
Dist.-N
Corrected
420.7
0.1855
87.72
5.674
Run 3
12-19-78
32.62
51130
15.08
Dist.-N
Corrected
591.5
0.2792
122.36
8.114
Agrico d
Dist.-T Dist.-T
Uncorrected Corrected
464.1 456.6
0.2050 0.2017
96.98 95.41
6.273 6.172
Agrico
Dist.-T Dist.-T
Uncorrected Corrected
381.5 380.4
0.1805 0.1800
79.10 78.9
5.245 5.230
Run 2
12-19-78
34.44
54720
15.08
TRC
Agrico
DN
332.6
0.1487
69.74
4.625
Dist.-N
Uncorrected
328.2
0.1468
68.82
4.564
Dist.-N
Corrected
324.4
0.1451
68.02
4.511
Dist.-T
Uncorrected
484.7
0.2172
101.9
6.755
Dist.-T
Corrected
484.2
0.2170
101.8
6.748
Run 4
12-19-78
33.14
52910
15.08
TRC
Agrico
Dist.-NDist.-N Dist.-T Dist.-T
DN Uncorrected Corrected Uncorrected Corrected
362.8
0.1686
76.45
5.070
348.2
0.1618
73.37
4.865
346.2
0.1609
72.95.
4.837
369.4
0.1720
78.01
5.173
364.9
0.1699
77.06
5.110
aDry standard cubic feet § 68°F, 29.92 inches Hg.
Dry standard cubic feet per minute.
CTRC ammonia analysis done by direct nesslerization (DN) and distillation/nesslerization (Dist.-N). Correction is for urea to ammonia conversion.
Corrected = uneorrected - 0.07 * corrected urea/1.765.
Agrico ammonia analysis done by distillation/titration (Dist.-T). Correction is for urea to ammonia conversion. See Section 3.2 for details
iuii emu currecLiou.
-------
TABLE 2-4 (Cont.)
TRC AND AGRIOO AMMONIA ANALYSIS RESULTS
FROM "C" GRANULATOR SCRUBBER GUI LET GAS-STREAM
AT AGRIOO CHEMICAL COMPANY, B1.YT11EVILLE, ARKANSAS
Run Number
Date
Run 5
12-19-78
Run 6
12-19-78
Volume of Gas Sampled (DSCF)
Volumetric Flowrate (DSCFM) c
Production Rate (Tons/hour)
Ammonia Analysis by:
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/Hour
Pounds/Ton
TRC c
32.41
51730
15.08
33.62
53750
15.08
Agrico
DN
341.6
0.1623
71.96
4.772
Dist.-N
Uncorrected
321.9
0.1530
67.81
4.497
Dist.-N
Corrected
320.7
0.1524
67.56
4.480
Dist.-T Dist.-T
Uncorrected Corrected
353.7 352.9
0.1684 0.1680
74.68 74.51
4.952 4.941
TRC
Agrico
Dist.-N Dist.-N Dist.-T Dist.-T
DN Uncorrected Corrected Uncorrected Corrected
301.5
0.1381
63.62
4.219
305.5
0.1399
64.46
4.275
303.5
0.1390
64.04
4.247
300.7
0.1380
63.59
4.217
298.1
0.1368
63.04
4.181
Run Number
Volume of Gas Sampled (DSCF) ?
Volumetric Flowrate (DSCFM)
Production Rate (Tons/hour)
Ammonia Analysis By:
Total Sample Weight (Milligrams)
Grains/DSCF
Pounds/1 lour
Pounds/Ton
DN
352.0
0.1617
73.76
4.872
TRC
Average
33.53
53237
15.14
Agrico
Dist.-NDist.-N Dist.-T Dist.-T
Uncorrected Corrected Uncorrected Corrected
386.7
0.1776
81.03
5.352
384.5
0.1766
80.57
5.322
392.4
0.1806
82.41
5.465
389.6
0.1793
81.82
5.426
aDry standard cubic feet e 68°F, 29.92 inches llg.
Dry standard cubic feet per minute.
'"TRC ammonia analysis done by direct nesslerization (DN) and distillation/nesslerization (Dist.-N). Correction is for urea to ammonia conversion.
Corrected = uncorrected - 0.07 * corrected urea/1.765.
Agrico ammonia analysis done by distillation/titration (Dist.-T). Correction is for urea to amnonia converstion. See Section 3.2 for details
on data reduction and correction.
-------
the ammonia nitrogen titrant volumes ranged from 5.4 ml to 11.5 ml. In order
to minimize titration errors, TRC has found that titrant volumes of at least
20 ml should be used. For these reasons, and because the TRC data are more
consistent, the TRC urea data are considered more accurate.
The ammonia data in Table 2-4 show that on the average, the TRC and Agrico
results are in close agreement. TRC utilized two analysis methods: direct
nesslerization and nesslerization with preliminary distillation. Agrico
utilized the titration method with preliminary distillation.
2.3 Scrubber Liquor Sampling Results
Two samples were collected from both the inlet and the outlet liquor
streams of the granulator "C" scrubber during each emission test run. At the
end of each test run the individual samples obtained during that run were
combined into two composite samples: one inlet sample and one outlet sample.
These were then analyzed by TRC for urea and ammonia at the Agrico laboratory,
and for formaldehyde and insoluble particulate at TRC. The analysis results
are shown in Table 2-5. Procedural difficulties precluded obtaining any
reliable insoluble particulate data. The same analysis methods used on the
scrubber gas stream samples were also used on the scrubber liquor samples.
And the same distillation correction factor was applied to the urea and
distilled ammonia data. Because the urea concentrations in the outlet liquor
greatly exceed the ammonia concentrations, the "corrected" outlet ammonia
concentrations are negative. This result illustrates the potential inaccuracy
inherent in this correction method when it is applied to samples containing
large concentrations of urea.
The urea, direct nesslerization ammonia and formaldehyde data in Table 2-5
generally agree with the data obtained during the October 1978 emissions tests
on the granulator "A" scrubber at this Agrico facility. Two exceptions are,
-15-
-------
TABLE 2-5
"C" GRANULATOR SCRUBBER LIQUOR ANALYSIS RESULTS
FROM AGRIOO dlMCAL COMPANY, BLYTHEVILLE, ARKANSAS
INLET (ppm)
Run Number
Date
Urea Data a
Uncorrected
Corrected
Ammonia Data
Direct Nesslerization
Dist. - N (uncorrected)h
Dist. - N (corrected) c
Fbrnialdeliyde Data
Run Number
Date
Urea Data a
Uncorrected
Corrected
Ammonia Data
Direct Nessleriration
Dist
Dist
. - N (unconnected)
. - N (corrected) c
1
12-18-78
29387
31444
7300
8167
6920
18.25
1
12-18-78
458900
491020
2110
14650
**
2
12-19-78
38830
41548
A
6800
5152
38.00
2
12-19-78
434630
46510
A
10650
**
3
12-19-78
38830
41548
*
7000
5352
38.00
3
12-19-78
498610
53350
*
8800
AA
4
12-19-78
28858
30878
5900
6050
4825
14.25
OUTLET (ppm)
4
12-19-78
423600 '
453250
2400
11400
AA
5
12-19-78
35079
37535
*
6600
5111
16.89
5
12-19-78
483170
516990
*
9200
A*
6
12-19-78
35962
38479
A
6200
4674
14.63
6
12-19-78
454490
486300
A
8350
AA
Average
34491
36905
6600
6803
5339
23.34
Average
458900
491020
2255
10508
AA
Formaldehyde Data
<0.05
0.21
0.21
0.19
0.30
0.19
0.22
a Kjeldahl with preliminary distillation analysis method. Correction applied for urea to ammonia conversion. Corrected = uncorrected * 1.07.
b Nessler analysis method with preliminary distillation.
c Correction for urea to ammonia conversion. Corrected = uncorrected - 0.07 * corrected urea/1.765.
d Chromotropic Acid Analysis method.
* Analysis not performed.
** Correction for urea to ammonia conversion yields negative values.
Note: Insoluble particulate measurements were not accurate and are not presented. See Section 3.2 for details.
-------
however, worthy of note:
o Inlet ammonia concentration - in October the average inlet ammonia
concentration was 13900 ppm; the average in Table 2-5 is 6600 ppm
(direct nesslerization).
o Outlet urea concentration - in October the average outlet urea
concentration was 689,400 ppm; the average in Table 2-5 is 458,900
ppm (uncorrected).
The higher outlet gas stream urea grain loading in these December tests
compared to the October tests should be reflected in a higher scrubber liquor
urea concentration. If, however, scrubber "C" is less efficient than scrubber
"A", then the urea data are reasonable. The December and October gas stream
ammonia data are comparable, which would tend to indicate that the liquor
ammonia results should also be comparable. If, however, much of the ammonia
in the liquor comes from the breakdown of urea, then the ammonia liquor data
are reasonable. The inlet and outlet liquor ammonia data (direct
nesslerization) also show evidence of ammonia stripping, whereby ammonia in
the liquor is transfered (presumably) to the gas stream.
2.4 Urea Audit Samples - Comparison of TRC and Agrico Analyses
TRC and Agrico each analyzed a different set of twelve urea samples, each
set prepared by TRC according to specific EPA instructions. Both analyses
were performed at the Agrico laboratory within 12 hours of sample prepara-
tion. The TRC audit sample set was analyzed using the total Kjeldahl nitrogen
method with no preliminary distillation, ending with nesslerization . The
Agrico audit sample set was analyzed using the same total Kjeldahl nitrogen
method, but ending with titration. The results of the urea audit sample
analyses are shown in Table 2-6.
ibid. pp. 437 ff.
-17-
-------
TABLE 2-6
RESULTS OF UREA AUDIT SAMPLE ANALYSES
PERFORMED BY TRC AND AGRICO
AT AGRICO CHEMICAL COMPANY, BLYTtlEVILLE, ARKANSAS
CD
Audit
Sample
1
2
3
4
5
6
7
8
9
10
11
12
TRC Analysis*
Actual Urea
Sample Weight
(rag)
A
100.71
311.98
598.36
5.64
11.60
40.40
2.60
6.84
9.42
5.40
4.30
30.16
As
Measured
(mg)
B
94.04
288.90
568.75
5.44
11.15
38.69
2.43
6.49
8.96
4.90
3.93
27.93
Error a
(*)
-6.6
-7.4
-4.9
-3.5
-3.9
-4.2
-6.5
-5.1
-4.9
-9.3
-8.6
-7.4
AGRICO Analysis**
Actual Urea
Sample Weight
(mg)
C
100.54
292.78
598.08
5.26
9.64
42.48
2.04
6.16
9.54
5.96
4.18
31.32
Measured As
Nitrogen
(mg)
D
96.3
281.1
582.4
3.6
11.8
38.6
1.1
5.0
9.5
5.3
3.9
27.4
Equivalent
Urea b
(mg)
E
206.4
602.4
1248.0
7.7
25.3
82.7
2.4
10.7
20.4
11.4
8.4
58.7
Error c
(%)
105
106
109
46.4
162
94.7
17.6
73.7
114
91.3
101
87.4
Average
-6.0
92.9
Percent error
E = I) * 60/28
Percent error
(100 * B/A) - 100
(100 * E/C) - 100
* TRC Analysis by total Kjeldahl nitrogen method, ending with Nesslerization. No preliminary distillation.
** Agrico analysis by total Kjeldahl nitrogen method, ending with Titration. No preliminary distillation.
-------
The TRC analysis results average 6.0 percent lower than the actual urea
sample weights, and each sample analysis is less than the actual. It was
initially thought that the consistently low results were due to the blank
correction. Discounting the blank correction in the analysis calculation
however, yields an overall +5.0 percent error, indicating that factors other
than the blank correction may also be involved in the consistently low (blank
corrected) results.
The Agrico analysis results average 92.9 percent higher than the actual
urea sample weights and the reason for this large error is not immediately
evident. These analyses were concluded with with titration, and the Agrico
analysis data (Appendix E) indicate that very low titration volumes were often
used (seven of the twelve titrations required less than 6 ml of titrant). TRC
has found that larger titrant volumes (at least 20 ml) are necessary in order
to help minimize errors during titration. A disadvantage of the titration
method is that the entire sample is used for one titration; consequently, if
an error is made or if a result is suspect, there is no possibility of
re-analysis.
Because the titration results are reported as mg nitrogen, conversion of
mg nitrogen to mg urea is required and is performed stoichiometrically: 2
moles (28 grams) of nitrogen are contained in 1 mole (60 grains) of urea. The
underlying assumption for using this conversion (and for not using preliminary
distillation, for that matter) is that all the nitrogen in the samples
originated as urea.
-19-
-------
'The TRC analysis results average 6.0 percent lower than the actual urea
sample weights, and each sample analysis is less than the actual. It was
initially thought that the consistently low results were due to the blank
correction. Discounting the blank correction in the analysis calculation
however, yields an overall +5.0 percent error, indicating that factors other
than the blank correction may also be involved in the consistently low (blank
corrected) results.
The Agrico analysis results average 92.9 percent higher than the actual
urea sample weights and the reason for this large error is not immediately
evident. These analyses were concluded with titration, and the Agrico
analysis data (Appendix E) indicate that very low titration volumes were often
used (seven of the twelve titrations required less than 6 ml of titrant). TRC
has found that larger titrant volumes (at least 20 ml) are necessary in order
to help minimize errors during titration. A disadvantage of the titration
method is that the entire sample is used for one titration; consequently, if
an error is made or if a result is suspect, there is no possibility of
re-analysis.
Because the titration results are reported as mg nitrogen, conversion of
mg nitrogen to mg urea is required and is performed stoichiometrically: 2
moles (28 grams) of nitrogen are contained in 1 mole (60 grains) of urea. The
underlying assumption for using this conversion (and for not using preliminary
distillation, for that matter) is that all the nitrogen in the samples
originated as urea.
-19-
-------
3.0 PROCESS DESCRIPTION AND OPERATIONS
3.1 Process Equipment
This Agrico urea manufacturing facility employs three rotary drum
granulators designed by C&I Girdler as the solids forming devices. A single
urea solution synthesis process supplies all three granulators. A schematic
of the urea manufacturing process is shown in Figure 3-1, showing one of the
three granulators and related equipment.
The concentrated molten urea, referred to as melt, leaves the solution
synthesis process and is pumped to the granulators. The molten urea is
sprayed onto a bed of solid urea "seed" particles at the higher end of the
inclined granulator. Lifting flights inside the granulator cause the solid
urea "seed" particles to continually fall through the molten sprays and a
counter-current flow of cooling air. The molten urea solidifies on these
"seed" particles, increasing their size. As the particles grow in size, they
eventually spill over a retaining dam into the collection section of the
granulator.
Cooled granules leaving the rotary drum granulator are screened. Oversize
granules are crushed, combined with undersize granules, and returned in solid
form to the bed of material at the spray end of the granulator as make-up
"seed". Product-size granules are conveyed to a bulk storage warehouse.
The airstream through the granulators entrains significant quantities of
urea and recovery of this material is essential for this solids formation
technique to be economically viable. A Joy Turbulaire "Type D" scrubber is
employed with each granulator to remove most of the particulate from the
granulator exhaust. After passing through the granulator, the air is drawn by
a fan through the scrubber and out a stack.
-20-
-------
i
N3
STACK
NH,
CO,
SOLUTION
SYNTHESIS
PROCESS
SCRUBBER LIQUOR
STACK
—L_\
FAN
SCRUBBER LIQUOR INLET
ROTARY DRUM
GRANULATOR
ADDITIVE
COOLING AIR
PRODUCT TO
WAREHOUSE
FIGURE 3-1: UREA MANUFACTURING - AGRICO CHEMICAL COMPANY,
BLYTHEVILLE, ARKANSAS
-------
This scrubber can be operated at varied pressure drops by adjusting the
scrubber liquor level. In order to meet particulate emission limitations,
this plant operates the scrubbers at a pressure drop in excess of 14 inches
W.G. Cleaned process condensate from the urea synthesis operation is used as
make-up scrubber liquor. The urea concentration of the liquor is maintained
at 45 percent to 50 percent. Scrubber liquor is returned to the solution
synthesis process for urea recovery. A schematic of the scrubber, depicting
air and liquor flow streams, is shown in Figure 3-2.
3.2 Process Operation
Emission testing was conducted by TRC on the exhaust from the "C"
granulator scrubber. During each emission test run, GCA monitored and
recorded process and control equipment operating parameters to ensure that the
process operated at representative, steady-state conditions. GCA also
obtained composite scrubber inlet and outlet liquor samples from the "C"
granulator scrubber during the test runs.
During the emissions testing on December 18 and 19, 1978, fourteen process
parameters were monitored in order to determine granulator production rate and
process stability. Relative parameter values, expressed as a percent of the
mean value over the two-day testing period, are shown in Table 3-1. Urea melt
temperature and the "C" granulator inlet and outlet air temperature values are
considered confidential. Appendix G contains all raw data values.
The data in Table 3-1 show that some parameters remained relatively
constant, while others varied considerably over the two test periods. The
parameters which varied the most are the Urea Solution Tank Level on the 19th,
the Additive Feed Rate on both days, and the Scrubber Liquor Level on both
days. The high value for the Spray Nozzle Pressure was 12.4 and 14.0 percent
-22-
-------
AIR EXHAUST
TO STACK
FAN
SCRUBBER
AIR INLET
MAKE-UP
•« X-SCRUBBER
LIQUOR
t
INLET
X
SAMPLING
LOCATIONS
OUTLET—*X
TO SYNTHESIS
SECTION
SCRUBBER LIQUOR
PUMP
FIGURE 3-2: JOY TURBULAIRE SCRUBBER - AGRICO CHEMICAL COMPANY,
BLYTHEVILLE, ARKANSAS
-23-
-------
TABLE 3-1
AVERAGE VAIAJES AND RANGES TOR PROCESS AND CONTROL EQUIPMENT
OPERATING PARAMETERS WIRING EMISSION TEST RUNS
AT AGRICO CHEMICAL COMPANY, BLYTItEVILLE, ARKANSAS
Parameter
Ammonia Feed Rate
Urea Solution Tank Level
Additive Feed Rate
Urea Melt Temperature
Granulator Spray Nozzle Pressure
Granulator Inlet Air Temperature
Granulator Outlet Air Temperature
i
NJ
-p-
' Scrubber Liquor Level
Scrubber Fan Amps
Scrubber Liquor Temperature
Scrubber Liquor Feed Rate
Scrubber Outlet Air Temperature
Symbol
NH3 Feed
TK-101
AFU
UMT
GSPC
AIGf
AOGT
SLI.
SFA
SLT
ISLF
AOS
12/18/78
Mean*
98
93
95 .
t
103
t
t
104
100
93
$
93
l:55p-4:10p
Range*
98-102
91-94
82-106
t
97-109
t
t
90-111
99-102
93-94
*
*
89-93
12/19/78
Mean*
101
102
102
t
99
t
t
98
100
102
*
*
103
9:05a-5:20p
Range*
98-103
91-124
78-116
t
93-106
t
t
85-104
99-102
100-107
*
*
100-105
*Values expresses as percentages of overall mean values for both test periods.
tConfidential Readings.
*Readings were inaccurate or monitoring device was broken during test period.
-------
higher than the low reading on the 18th and 19th, respectively. Since melt
throughput is proportional to the square-root of the pressure drop, the
highest throughputs were only 6.0 percent and 6.9 percent higher than the
lowest throughput for each day.
The recorded values for Urea Solution Tank Level, Additive Feed Rate, and
Scrubber Liquor Levels varied enough to merit further scrutiny. Mean values,
standard deviations, and variation ranges of these three parameters during the
six sampling runs are shown in Table 3-2. Although all three exhibit
significant fluctuations in mean value from run to run, only the Additive Feed
Rate readings varied substantially over the course of a single run (a single
run lasted 1 hour).
It is important to point out that readings for all three of these
parameters are uncalibrated values. In the case of the Additive Feed Rate,
the value is followed to maintain steady conditions; for the two liquid
levels, the plant attempts to keep the readings at values which they know from
experience correspond to the design levels. It is not known to what extent
fluctuations in the readings reflect variations in the actual parameters. For
instance, does a 10 percent change in the Scrubber Liquor Level reading
reflect a 10 percent change in actual scrubber liquor depth or does the
monitoring device scale cover only a fraction of the total depth? In this
case, the actual fluctuation in the liquor depth is far less than that
depicted by the readings. The extent to which fluctuations in Scrubber Liquor
Depth readings affect the air passage above the sump, and hence the airstream
velocity, is not known.
Production rate data initially appeared ambiguous. The production
totalizer readings for the "C" granulator, when corrected using the correction
factor developed during tests conducted October 9 to 13, 1978, yielded
-------
TABLE 3-2
VARIABILITY OF THREE PROCESS OPERATING PARAMETERS DURING EMISSION TESTS RUNS
AT AfiRICO CHEMICAL COMPANY, BLYTHEVILLE, ARKANSAS
ON
I
TK-101 Urea Solution Tank Level
Run Number
1
2
3
4
5
6
Date
12/18
12/19
12/19
12/19
12/19
12/19
Time Span*
l:55p-3:00p
9:05a-10:20a
ll:00a-12:00p
l:10p-2:10p
2:55p-3i55p
4:10--5:20p
Standard
Mean Deviation Range*
_
16.1 0
15.3 0
16.1 0
17.3 0
19.5 0
_
.45 94-100
.24 95-98
.20 96-99
.68 99-112
.65 112-124
APR Additive Feed Rate
Mean
2
3
3
2
2
3
.8
.3
.2
.6
.8
.0
Standard
Deviation
0.29
0.11
0.13
0.16
0.27
0.24
Range*
82-106
106-117
106-117
80-97
81-108
85-106
SLL Scrubber Liquor Level
Mean
42.2
39.1
40.0
38.0
39.1
35.4
Standard
Deviation
0.51
0.19
0.32
0.89
0.86
1.37
Range*
107-111
101-102
102-104
99-106
97-103
85-95
*Range values are expressed as percentages of the overall average for the entire testing period.
tTijne spans are meant to encompass the period when sampling occurred and are not start and finish
times for the actual sampling.
-------
unrealistic production rates. It was evident that the "C" totalizer had been
adjusted since those tests. A new correction factor was therefore developed
for the "C" granulator totalizer (as detailed in Appendix G) , and production
rates were recalculated. These calculated production rates appeared to be
more reasonable but were not used because they are valid only if the
correction factor for the "A" granulator totalizers did not change. Product
totalizers are not considered to be accurate production rate indicators by
plant personnel, who use them mostly to indicate changes in production rates.
Spray nozzle pressure was then selected as a more valid indicator of
production rate. It is a reasonably good method if the physical
characteristics of the urea melt do not change significantly from day to day
and if the characteristics of the spray nozzles do not change substantially
due to wear or urea buildup.
One of the important concepts on which the original correction factors
were based was that the urea melt spray conformed to the orifice equation and
that, therefore, the flow rate through each nozzle was proportional to the
square root of the pressure drop across the nozzle. Carrying this concept one
step further, and applying the assumptions of constant melt properties and
constant nozzle characteristics, production rates can be calculated using the
simplified orifice equation:
G = K v&P* (1)
where
G = Melt flowrate, tons/minute
K = Empirical constant, tons/(Minute • psig/2 )
AP = Pressure drop across nozzles, psig.
The constant K is a function of fluid, nozzle, and flow properties which
are assumed constant for this sytem. The constant K was calculated to be
-27^
-------
0.0434 based on data collected at Agrico during the October 9-13, 1978 tests.
A comparison of production rates as calculated by totalizer readings and
production rates calculated from nozzle pressure readings is presented in
Table 3-3 for granulators A, B and C for the October emissions tests. The
average difference between these production measurement methods was 2.6% for
all granulators and 2.7% for granulator "C".
Assuming that no significant change occurred in nozzle or melt
characteristics between the October 1978 and the December 1978 test dates, the
value of 0.0434 can be used in Equation (1) to calculate average production
rates for 18 December and 19 December, 1978. The results are shown below:
PRODUCTION RATES OF "C" GRANULATOR DURING DECEMBER 1978 TESTS
BASED ON EQUATION (1)
Dec.
Dec.
Date
18, 1978
19, 1978
Time
l:55p-4:10p
9:05a-5:20p
Average
P, psig
35.2
33.6
G
Tons/Min.
0.257
0.252
G
Ton/Day
371
362
To assure that the scrubber on the "C" granulator was operating properly
during testing, scrubber liquor samples were taken during each emission test
run. Agrico preferred that their personnel draw the necessary scrubber liquor
samples. GCA observed the sample collection and took immediate custody of the
samples. Inlet and outlet liquor samples were taken at the beginning and end
of each test run and these samples were then analyzed for urea, ammonia,
formaldehyde and percent solids. The sampling locations are shown in Figure
3-2. The actual times that the samples were collected are listed in
Appendix G.
-28-
-------
TABLE 3-3
COMPARISON OF PRODUCTION RATES CALCULATED BY EQUATION 1
AND PRODUCTION RATES CALCULATED FROM CORRECTED TOTALIZER READINGS
DURING THE 9-13 OCTOBER 1978 EMISSIONS TESTS
AT AGRICO CHEMICAL COMPANY, BLYTIIEVILLE, ARKANSAS
"A" GRANULATOR
Gt
(tons/min)
0.270
0.273
0.270
0.276
0.277
0.294
i, 0.248
"f 0.270
0.273
0.260
0.247
AP
Spray
nozzles
(psig)
40.5
40.5
40.0
40.0
40.5
41.0
37.5
35.5
40.5
38.0
37.0
G*
(tons/min)
0.276
0.276
0.274
0.274
0.276
0.278
0.266
0.259
0.276
0.268
0.264
Error
(*)
2.2
1.1
1.5
0.7
0.4
5.4
7.3
4.1
1.1
3.1
6.9
Gt
(tons/min)
0.275
0.279
0.278
0.285
0.281
0.289
0.254
--
0.265
0.260
0.253
"B" GRANULATOR
flP
Spray
nozzles
(psig)
41.0
40.5
39.0
40.0
40.5
42.0
35.0
—
39.5
34.5
33.5
G*
(tons/min)
0.278
0.276
0.271
0.274
0.276
0.281
0.257
—
0.273
0.255
0.251
Error
(*)
1.1
1.1
2.5
3.9
1.8
2.8
1.2
—
3.0
1.9
0.8
Gt
(tons/min)
0.278
0.280
0.270
0.292
0.286
0.285
0.267
0.276
0.264
0.278
0.277
"C" GRANULATOR
fiP
Spray
nozzles
(psig)
41.0
41.0
40.5
43.0
42.0
42.0
36.5
38.0
40.0
36.5
35.5
G*
(tons/min)
0.278
0.278
0.276
0.285
0.281
0.281
0.262
0.268
0.274
0.262
0.259
Error
(*)
0.0
0.7
2.2
2.4
1.7
1.4
1.9
2.9
3.8
5.8
6.5
Gt - Production rate based on corrected totalizer readings.
G* - Production rate based on empirical equation using pressure drop across spray nozzles,
(See Equation 1).
Error = | ( £fj- 1 X 100
-------
Scrubber operating parameters were also recorded during the emission test
runs in order to monitor the stability of this device. The variation of these
parameters is shown in Table 3-1. The higher operating temperatures recorded
on December 19 probably reflect the higher ambient air temperature that
occurred that day. The ambient air temperature on December 19 was 15-20°
higher than on December 18. The affect of temperature on collection
efficiency is not known.
-30-
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4.0 LOCATION OF SAMPLING POINTS
This section presents descriptions of the sampling locations used, during
the emissions testing program at the Agrico Chemical Company urea
manufacturing plant in Blytheville, Arkansas on December 18 and 19, 1978.
4.1 Granulator C Scrubber Outlet
The cleaned gases exiting the scrubber unit are ducted to an induced draft
fan adjacent to the emission control unit. The fan discharge is directed
vertically through a steel stack to the atmosphere. The "C" scrubber 60-inch
I.D. outlet stack was fitted with two 4-inch I.D. pipe-flanged sampling ports
positioned 90 degrees apart in a horizontal plane. The two ports were located
65 feet (13 stack diameters) downstream of the fan outlet, and 20 feet (4
stack diameters) upstream of the stack discharge. Since these port locations
met the "eight and two diameters" criteria for distance from flow
disturbances, six sampling points were chosen for each axis.traverse, for a
total of twelve sampling points as specified by EPA Reference Method 1.
Figure 4-1 shows a cross-sectioned view of the duct at the sampling location
and lists the exac± distance of each sampling point from the outside flange
edge.
4.2 Scrubber Liquor Sampling Locations
Granulator C scrubber liquor samples were collected from the liquor
make-up line (cleaned process condensate from the urea synthesis operation)
and from the return liquor line downstream from the circulating pump. Figure
4-2 shows these sampling locations.
-------
I
LO
20'
65'
5'
SCRUBBER OUTLET
PORTS
SCRUBBER
FAN
A - LOCATION OF TEST PORTS
65-3/4"
NORTHEAST
TRAVERSE POINT
NO.
1
2
3
4
5
6
TRAVERSE POINT DISTANCE
OUTSIDE EDGE OF NIPPLE
8-5/8
14-3/4
23-3/4
48-1/8
57
53-1/8
FROM
(IN.)
B - LOCATION OF TEST POINTS
FIGURE 4-1: LOCATIONS OF "C" GRANULATOR SCRUBBER OUTLET TEST PORTS AND POINTS AT
COMPANY INJ^YTHJ^LE .JVBKANSAS
-------
AIR EXHAUST
TO STACK
FAN
SCRUBBER
AIR INLET
MAKE-UP
X-SCRUBBER
LIQUOR
X
SAMPLING
Z/ LOCATIONS
OUTLET
SCRUBBER LIQUOR
PUMP
TO SYNTHESIS
SECTION
FIGURE 4-2: JOY TURBULAIRE SCRUBBER - AGRICO CHEMICAL COMPANY,
BLYTHEVILLE, ARKANSAS
-33-
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5.0 SAMPLING AND ANALYSIS METHODS
This section presents general descriptions of sampling and analysis
procedures employed during the emissions testing program conducted at the
Agrico Chemical Company, Blytheville, Arkansas, urea manufacturing facility
during December 18 and 19, 1978. Details of sampling and analysis procedures
are contained in Appendices C and D.
5.1 EPA Reference Methods Used in This Program
The following EPA Reference Methods were used during this emission testing
program. These methods are taken from "Standards of Performance for New
Stationary Sources", Appendix A, Federal Register, Volume 42, No. 160,
Thursday, August 18, 1977, pp 41755 ff.
o Method 1 - Sample and Velocity Traverses for Stationary Sources
This method specifies the number and location of sampling points
within a duct, taking into account duct size and shape and local flow
disturbances. In addition, this method discusses the pitot-nulling
technique used to establish the degree of cyclonic flow in a duct.
o Method 2 - Determination of Stack Gas Velocity and Volumetric Flowrate
This method specifies the measurement of gas velocity and flowrate
using a pitot tube, manometer and temperature sensor. The physical
dimensions of the pitot tube and its spatial relationship to the
temperature sensor and any sample probe are also specified.
o Method 4 - Determination of Moisture Content in Stack Gases
This method describes the extraction of a gas sample from a stack and
the removal and measurement of the moisture in that sample by
condensation impingers. The assembly and operation of the required
sampling train is specified.
o Method 5 - Determination of Particulate Emissions from Stationary
Sources
This method specifies the isokinetic sampling of particulate matter
from a gas stream utilizing techniques introduced in the above three
methods. Sample collection and recovery, sampling train cleaning and
calibration, and gas stream flowrate calculation procedures are
specified.
-34-
-------
5.2 Urea and Ammonia Sampling and Analysis
5.2.1 Sampling
The outlet gas stream of the granulator C scrubber was sampled at points
located in accordance with the relationship, detailed by EPA Method 1, of the
sampling ports to upstream and downstream flow disturbances. The velocity of
the duct gas was measured using S-type pitot tubes constructed and calibrated
in accordance with EPA Method 2.
The sampling train used on this sampling program is shown in Figure 5-1
and is a modification of the standard EPA Method 5 particulate sampling
train. The modifications used were: altered impinger sequence, absence of a
filter, use of a teflon line and maintenance of the probe temperature at about
10 F above stack temperature.
The sampling train shown in Figure 5-1 consists of a nozzle, probe, teflon
line, five impingers, vacuum pump, dry gas meter, and an orifice flow meter.
The nozzle is stainless steel and of buttonhook shape. The nozzle was
connected to a 5/8-inch stainless steel glass-lined probe. Following the
probe, the gas stream passed through a 3/8" I.D. Teflon line into an ice
bath/impinger system.
The first three impingers each contained 100 ml of deionized distilled
water. The fourth impinger remained empty while the fifth was filled with 200
grams of indicating silica gel to remove any remaining moisture.
Leaving the last impinger, the sample gas stream flowed through flexible
tubing, a vacuum gauge, needle valve, pump, and dry gas meter. A calibrated
orifice and inclined manometer completed the sampling train. The stack
velocity pressure was measured with an inclined manometer and an S-type pitot
tube constructed, calibrated and used in accordance with EPA Reference Method
2. Stack temperature was monitored by a thermocouple attached to the probe
and connected to a potentiometer. A nomograph was used to determine the
-35-
-------
STACK WALL -
THERMOMETER
LEGEND
1 - NOZZLE 7
2 - PROBE 8
3 - TEFLON LINE 9
4 - ICE BATH 10
5 - FLEXIBLE LINE 11
6 - VACUUM GAGE 12
NEEDLE VALVE
PUMP
DRY GAS METER
ORIFICE
PITOT TUBE & INCLINED MANOMETER
POTENTIOMETER
FIGURE 5-1: MODIFIED EPA PARTICULATE SAMPLING TRAIN
AU|Ngf
-------
orifice pressure drop required for any measured pitot velocity pressure and
stack temperature in order to maintain isokinetic sampling conditions.
Test data recorded included test time, sampling duration at each traverse
point, pitot pressure, stack temperature, meter volume, meter inlet-outlet
temperature, and orifice pressure drop.
5.2.2 Sample Recovery and Preparation
At the completion of each test run the train was leak-checked. The
impinger sample volumes were measured and then the nozzle, probe, flexible
teflon line, the first four impingers and their connecting glassware were
rinsed with distilled deionized water. The impinger samples were combined
with these washes and placed in a glass jar with a teflon-line cap.
At the Agrico laboratory, the silica gel from the fifth impinger was
weighed to ^ 0.1 g. The combined impinger sample was filtered through a
pre-weighed glass-fiber filter. The filter was rinsed with distilled
deionized water to prevent solids from drying out. The filtrate and filter
rinses were then combined and the total volume was measured in a graduated
cylinder.
Approximately 100 ml of this sample was set aside for formaldehyde
analysis at TRC. Another portion was removed for immediate analysis (within
24 hours of collection) for urea and ammonia at the Agrico laboratory by both
TRC and Agrico. The remaining sample was itself split into two portions;
these latter portions were returned to TRC for additional urea analysis method
investigations. These investigations are described in the EPA Report
79-NHF-13 "Development of Analytical Procedures for the Determination of Urea
from Urea Manufacturing Facilities".
-37-
-------
5.2.3 Sample Analysis
5.2.3.1 Analysis by TRC
A portion of each of the emission tests samples was analyzed for urea and
ammonia by TRC at the Agrico laboratory within 24 hours of sample collection.
The urea analysis was done with the Kjeldahl method (with preliminary
distillation, ending with nesslerization); the ammonia analysis was done by
direct nesslerization and by nesslerization with preliminary distillation.
The preliminary distillation was a step common to the Kjeldahl urea and
distillation/nesslerization ammonia analyses. Sodium borate and sodium
hydroxide were added to a portion of the sample to act as a buffer and to
bring the pH to 9.5 or greater. The sample was then distilled, and the
distillate (containing the ammonia) was collected in a boric acid solution.
To this solution was added the nessler reagent, and after full color
development the absorbance of this solution was measured with a
spectrophotometer. To the distillation residue was added the Kjeldahl
digestion reagent which converts organic nitrogen (urea) to ammonia. This
(converted) ammonia was then distilled into an acid solution and analyzed by
nesslerization as above.
Sample absorption measurements were converted to ammonia concentration
through a calibration curve prepared with a series of standard ammonia
solutions. Urea concentrations were calculated by multiplying the organic
nitrogen ammonia concentrations by the stoichiometric factor 60/34.
Direct nesslerization ammonia measurements were made by adding the nessler
reagent directly to a portion of the sample, awaiting full color development,
and taking the absorbance reading with the spectrophotometer. A separate
calibration curve was prepared for the direct nesslerization measurements.
One complication of the preliminary distillation step to remove ammonia is
the hydrolysis of urea to ammonia that occurs during the distilltion. It has
-38-
-------
been estimated that about 7 percent of the urea in a sample is converted to
ammonia during the preliminary distillation step.^ Therefore, the
indicated urea concentration multiplied by 1.07 equals the actual urea
concentration. At the same time, the indicated ammonia concentration must be
reduced by a stoichiometrically equivalent amount. Since 2 moles (34 grams)
of ammonia are formed from the hydrolysis of 1 mole (60 grams) of urea, the
ammonia correction equation is as follows:
Aa = Ai - (Ua * 0.07 * 34/60)
where Aa = actual ammonia concentration
Ai = indicated ammonia concentration
Ua = actual urea concentration
If the actual urea concentration is small relative to the ammonia
concentration, then these corrections are insignificant. However, if urea
concentrations are large (as, for example, in scrubber liquor streams)
compared to ammonia concentrations, then the ammonia corrections are
unrealistic, and result in negative actual ammonia concentrations (see Section
2.3 and Section 5.5).
Because urea was the species of concern in this emissions testing program,
the impingers in the sampling train contained only water. In order to most
efficiently capture ammonia, however, the gas stream should be bubbled through
an acid solution; in a neutral or basic solution ammonia will tend to remain
as a gas and will tend to leave the solution. For this reason, the ammonia
Standard Methods of Water and Wastewater Analysis, APHA, AWWA, WPCF,
14th edition, 1975 p.408
-------
collection efficiency of this sampling train may have been less than optimum,
and the ammonia concentrations shown in Sections 2.1 and 2.2 may be less than
the ammonia concentrations that actually existed in the scrubber outlet gas
stream.
5.2.3.2 Analysis by Agrico
A portion of the same samples analyzed by TRC were analyzed for urea and
ammonia by Agrico personnel at the Agrico laboratory within 24 hours of sample
collection. The urea analyses were done with the indirect Kjeldahl method,
ending with distillation and titration; the ammonia analyses were done by
distillation and titration.
For these analyses two equal aliquots of sample were used. The first
aliquot was buffered and distilled into a boric acid solution in the same
manner as was done by TRC. Color indicator was then added to the distillate
solution, and this solution was then titrated with standard 0.02N sulfuric
acid until the proper indicator color was obtained. The sample ammonia
nitrogen (N ) concentration is calculated directly from the volume of
3
standard acid used in this titration.
The second aliquot was digested with the Kjeldahl digestion reagent to
convert all organic nitrogen to ammonia. This solution was then distilled
into a boric acid solution, and this distillate solution was then titrated and
the total nitrogen (N ) concentration of the sample was calculated from the
titrant volume, as described above.
The sample urea concentration was calculated by subtracting the ammonia
nitrogen concentration from the total nitrogen concentration, and converting
this difference (organic nitrogen) to urea stoichiometrically. The
calculation procedure, including corrections for the conversion of urea to
-40-
-------
ammonia during distillation, is as follows:
Nu = Nfc - Na = mg urea nitrogen (uncorrected)
N * 60/28 = mg urea (uncorrected)
U = (NU * 60/28)(1-k) = mg urea (corrected)
where k = 0.07
and 60/28 = stoichiometric factor.
Na * 17/14 = mg ammonia {uncorrected)
A = (N * 17/14) - (k * U/1.765) mg ammonia (corrected)
a
where 1.765 = 60/34 = stoichiometric factor.
The factor k represents the standard 7 percent correction for urea to ammonia
conversion during distillation.
As was noted in Section 2.2, the titrant volumes used by Agrico were
relatively small (ranging from 5.8 ml to 13.5 ml for the total nitrogen
analyses and from 5.4 ml to 11.5 ml for ammonia nitrogen) . Larger titrant
volumes (at least 20 ml) are recommended in order to minimize titration errors.
5.3 Formaldehyde Sampling and Analysis
The same samples collected, recovered and prepared as described in
Sections 5.2.1 and 5.2.2 were analyzed for formaldehyde as well as urea and
ammonia. ' The sample portions set aside for formaldehyde measurement were
analyzed at TRC within 20 days of sample collection using the chromotropic
acid method.
5.4 Insoluble Particulate Sampling and Analysis
The combined impinger samples (probe and glassware rinses and impinger
contents) were filtered through a pre-weighed glass-filter at the Agrico
-41-
-------
laboratory. The filters were returned to TRC in sealed petri dishes. They
were then desiccated for at least 24 hours and then weighed to a constant
weight. Constant weight is defined as two consecutive weighings, taken at
least 6 hours apart, which agree within 0.5 mg. This analysis took place
within 20 days of sample collection.
5.5 Scrubber Liquor Sampling and Analysis
5.5.1 Sampling, Sample Recovery and Preparation
During each of the six emissions test runs performed on the granulator C
scrubber outlet, scrubber liquor inlet and outlet samples were collected in
glass jars with teflon-lined caps. The jars were half-filled about 15 minutes
into a test run, and then the remaining half was filled about 15 minutes
before the end of the run.
Because of time constraints, only samples from test runs 1 and 4 were
filtered (to remove all undissolved solids) and analyzed for urea and ammonia
at the Agrico laboratory within 24 hours of sample collection. All samples
were then returned to TRC, and the samples from test runs 2, 3, 5, and 6 were
filtered and analyzed for urea and ammonia with 72 hours of sample collection.
A portion of each sample was set aside for formaldehyde analysis; these
analyses were performed along with the formladehyde analyses of the scrubber
gas stream samples within 20 days of sample collection.
A change in the work assignment scope of work resulted in there being an
insufficient supply of pre-weighed glass-fiber filters to filter all the
samples as quickly as possible after sample collection. In some cases,
therefore, inlet and outlet liquor samples were filtered through the same
filter; filtrates were kept separate and these twice-used filters were rinsed
thoroughly between sample filtrations. Samples 3, 5, and 6 were filtered in
-------
this way. The exact volume of each filtered sample was not measured, so
solids concentration calculations were based on the approximate volume of the
sample jars (about 400 ml) . For these reasons little confidence is placed in
the measured insoluble particulate concentrations of the scrubber liquor
samples.
5.-5.2 Sample Analysis
The scrubber liquor samples were analyzed for urea, ammonia and
formaldehyde in the same manner and with the same analysis methods as the
scrubber outlet gas stream samples (Sections 5.2 and 5.3). Much larger
dilutions were required for the liquor samples, however, because of the much
greater ammonia and urea concentrations in the liquor than in the gas stream
(see Appendix D for dilution factors). Consequently, errors or inaccuracies
inherent in the analysis procedures may be magnified in the liquor sample
analyses.
Because the urea concentrations in the outlet liquor samples are much
greater than the ammonia concentrations, the corrected ammonia concentrations
(corrected for conversion of urea to ammonia during the preliminary
distillation step) for the outlet samples are negative. This result indicates
that the 7 percent correction factor (as discussed in Section 5.2) is
inappropriate for high concentration urea samples. The actual rate of
hydrolysis of urea may be a function of the absolute urea concentration or of
the relative urea to ammonia concentration. Further investigation of this
problem, over a wide range of urea concentrations, is needed.
-43-
-------
5.6 Urea Audit Samples - TRC and Agrico Analyses
Two sets of twelve urea audit samples, each set ranging from about 2 mg to
about 600 mg, were weighed at TRC in tared vials on a 5-place analytical
balance and then brought to Agrico for analysis during the December 1978
emissions test program. TRC and Agrico each analyzed one set of the sample
sets. The TRC analyses were performed with the Kjeldahl method ending with
nesslerization; the Agrico analyses were performed with the Kjeldahl method
ending with titration. In both cases, no preliminary distillation was
performed since the only source of nitrogen in the audit samples was urea.
The analyses were performed within 12 hours of dilution of the urea
samples. In each set, the first six samples were diluted with 400 ml
distilled, deionized water; the last six were diluted with 250 ml IN sulfuric
acid. This was done to simulate the water and acid impingers normally used in
a urea particulate sampling train.
5.6.1 Analysis by TRC
The TRC audit sample set was prepared and analyzed at the Agrico
laboratory during the December 1978 field program. Kjeldahl digestion reagent
was added to an aliquot of each audit sample solution, converting all organic
nitrogen to ammonia. The ammonia was then distilled into a boric acid
solution, nessler reagent was added and the absorbance of the distillate
solution was measured in a spectrophotometer. Absorbance was converted to
ammonia concentration with a calibration curve prepared from the absorbances
of standard ammonia solutions. A reagent blank was analyzed in the same
manner as the audit samples.
The measured ammonia concentrations were converted to urea concentrations
-------
as follows:
urea (mg) = ammonia (mg) * 60/34,
utilizing the stoichiometric relationship between moles of ammonia and moles
of urea.
As noted in Section 2.4, the TRC analysis results agreed with the actual
audit sample weights within 6 percent, on the average. The measured urea
contents were all less than the actual contents, ranging from 3.9 percent to
9.3 percent lower. Eliminating the blank correction brought the average error
to +5 percent, ranging from -5.9 percent to +22.3 percent. The blank
correction is therefore considered appropriate. There is no noticeable
difference between the analysis results of the first six samples {water
diluted) and the last six (acid diluted). A breakdown of each sample analysis
is shown in Appendix E.
5.6.2 Analysis by Agrico
The Agrico audit sample set was prepared and analyzed at the Agrico
laboratory on January 4 and 5, 1979. The Agrico analyst diluted each sample
to one liter with the appropriate diluent (water and acid). The Kjeldahl
digestion and distillation was performed in the same way as the TRC analysis.
Final total nitrogen content was determined by adding a color indicator to the
distillate solution and titrating with standard acid. The indicated mg
nitrogen were then converted to mg urea as follows:
mg urea = mg nitrogen * 60/28,
utilizing the stoichiometric relationship between moles of nitrogen and moles
of urea.
The Agrico results averaged 92.9 percent higher than the actual audit
sample urea content, ranging from 17.6 percent higher to 162 percent higher.
-45-
-------
These results could reflect errors in several areas, including standardization
of the titration acid and contamination during digestion and distillation.
Only one blank was run, and this may not have been representative of the
entire sample set analyzed over 2 days. Seven of the twelve analyses had
titrant volumes less than 6 ml; usually a titration should utilize at least 20
ml in order to minimize the possibility of error. A variation in the
indicated blank titrant volume (1.7 ml) would significantly effect the results
of the low titrant volume samples.
-46-
-------
APPENDIX A
COMPUTER PRINTOUT TEST RESULTS
Includes:
A.I Granulator C Scrubber Outlet
A.2 Sample Equations and Example Calculations
-------
APPENDIX A.I
GRANULATOR C SCRUBBER OUTLET
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST
TRC PROJECT 82988-01
MO
UNIT TESTED
DATE AND TIKE OF TEST
SAMPLING LOCAT ION
NAME OF FIRM
LOCATION OF FIRM
POLLUTANTS SAMPLED
UNIT c
DEC 18 1978 1500 TO 1607
SCRUBBER OUTLET
AGRICO -EPA
8LYTHEV1LLE ARK
UREA AND AMMONIA
3AROMETRIC PRESSURE. IN HG
DUCT AREA. SO FT
NOZZLE DIAMETER. IN
PITOT CALIBRATION COEFFICIENTS 1
2
3
DRY GAS METER CALIBRATION FACTOR,
FINAL LEAK RATE. CF M
TONS. PER HOUR, PRODUCT
29 ,8»i
18.98
0.185
0.839
0.000
0.000
0.990
0.014
O.OQO
I BY VOLUME DRY BASIS
COMPOSITION OF DUCT GAS.
CA3B ON~ DIOXIDE
OXYGEN
CA3BON MONOXIDE
NITROGEN
UREA, AMMONIA, FORMALDEHYDE COLLECTED. MG
H20 IMPIVGERS
H2SO«4 IMPISC-ERS
TOTAL
AMOUNT OF yATER
IM»INGERS
SILICA GEL
UREA AMMONIA-DIR
0.6040E 02 0.4037E 03
O.OOOOE 00 O.OOOOE 00
0.6040E 02 O.M037E 03
COLLECTED. GRAMS
0.00
21 .00
0.00
79 .00
AMMONIA-DIST
0.<4232E 03
G.OOOOE 00
O.U232E 03
35 .0
12.0
FORMALDEHYDE
0.3900E 01
O.OOQOE oo
0.3900E 01
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST 40
TRC PROJECT 82988-01
INT TIME
1 5 .0
2 5.0
3 5.0
4 5.0
5 5.0
6 5.0
1 5.0
2 5.0
3 5.1
4 5.0
5 5.0
6 5.0
FINAL METER VOLUME 183.52
VEL HEAD
IN H20
0.91QO
0.9400
0.9000
d. 9000
0.8400
C.6300
0.9600
0.9900
0.9700
0 .8600
0.8300
0.6900
ORIFICE
PRESS
IN H20
1 .0500
1 .0800
1 .0200
1 .0200
0 .9700
0 .8500
1 .1000
1 .1500
1 .1100
1 .0100
0.9600
0.8100
METER
INLET
DEG F
b3.
53.
53.
52.
52.
51.
' 54.
54.
54.
54.
53.
54.
TEMPS
EXIT
DEG F
55 .
53.
53.
52.
51 .
51 .
53.
53.
54.
54.
53.
54.
DUCT STAT
PRESS
IN H20
-0.40
-0.40
-0 .40
-0.40
-0 .40
-0.40
-0.48
-D.48
-0.48
-0.48
-0.48
-0 .48
DUCT
TEMP
DEG F
94.
92.
91 .
89 .
86.
86.
91 .
94.
95.
95 .
94.
94.
IN ITIAL
MET ER V OL
CU FT
154.23
157.00
159.92
162.20
165 .56
163.52
171 .18
174.12
177.10
180.20
182.97
185 .76
P CYC
R AMG
B .
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
-------
TEST DATA -- UP EA , AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
— TEST NO
UNIT C
AGRICO -EPA
SCRUBBER OUTLET
DEC 13 1978 1500 TO 1607
H EAD . IN H20 EXP
.5 ......
STANDARD CONDITION TEMPERATURE.
STANDARD CONDITION PRESSURE.
TOTAL SAMPLING TIME. MINUTES
AVERAGE SQUARE ROOT VELOCITY
AVERAGE ORIFICE PRESSURE DROP
AVERAGE METER TEMPERATURE. DEC
AVERAGE DUCT STATIC PRESSURE. IN H 20
AVERAGE DUCT TEMPERATURE. OEG F
TOTAL SAMPLE VOLUME. DACF
TOTAL SAMPLE VOLUME. D SCF
WATER VAPOR VOLUME. DSCF
MOISTURE CONTENT OF DUCT GAS. PERCENT
MOLE FRACTION OR Y GAS
MOLECULAR WEIGHT - DRY STACK GAS ....
MOLECULAR WEIGHT - STACK GAS
AVERAGE STACK PRESSURE. IN HG
DUCT VOLUMETRIC FLOW. ACFM
DUCT VOLUMETRIC FLOW. DSCFM
AVERAGE DUCT VELOCITY. FPM
EXCESS AIR. PERCENT -Q
AVERAGE DUCT GAS DENSITY. LB S/ACF
ISOKINETIC FACTOR. PERCENT
0.
0.
C.
0.
0.
0.
-0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
-Q.
0.
0.
6800E
299 2E
601 OE
9300E
1013E
530HE
(4400E
9175E
3429E
3 <*9 3 E
221 2E
595 6E
9'<»0«»E
288ME
2819E
2981E
6155E
5518E
3213E
1458E
02
02
02
00
01
02
00
02
02
02
01
01
00
02
02
02
05
05
04
05
6976E-01
1072E
03
UREA IN H20
UREA IN H2SOH
T OT AL US E A
AMMON IA-DIRECT-IN H20
AMMONIA-DIRECT-IN H2SO«»
TOTAL AMMONIA-DIRECT
AMMON IA-DISTILL ED-IN H20
AMMONIA-DISTILLED-IN H2S04
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2S01
TOTAL FORMALDEHYDE
GR/
ACF
0.2392E-01
O.OOOOE 00
0.2392E-01
0.1599E 00
O.OOOOE 00
0.1599E 00
0.1676E 00
O.OOOOE 00
0.1676E 00
0.1545E-02
O.OOOOE 00
0.15H5E-02
EMISSION DATA
GR/
DSCF
0.2668E-01
O.OOOOE 00
0.2668E-01
0.1783E 00
O.OOOOE 00
0.1783E 00
0.1869E 00
O.OOOOE 00
0.1869E 00
0.1723E-02
O.OOOOE 00
0.1723E-02
LBS/
HR
0.1262E 02
O.OOOOE 00
0.1262E 02
0.8M35E 02
O.JOOOE 00
0.8435E 02
0.8842E 02
O.OOOOE 00
0.83'»2E 02
0.81 48E 00
0.3000E 00
0.81 *»8E 00
O.CM/5
0.0000
0/8435
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
— TEST SO
UNIT C
AGRICO -EPA
SCRUBBER OUTLET
DEC 18 1978 1500 TO 1607
STANDARD CONDITION TEMPER
STANDARD CONDITION PRESSU
TOTAL SAMPLING TIME, MINU
AVERAGE SQUARE RROT WELOC
AVERAGE ORIFICE PRESSURE
AVERAGE METER TEMPERATURE
AVERAGE DUCT STATIC PRESS
AVERAGE DUCT TEMPERATURE.
TOTAL SAMPLE VOLUME. DM3
TOTAL SAMPLE VOLUME. DNM3
WATER VAPOR VOLUME. DNM3
AVERAGE STACK GAS PRESSURE.
DUCT VOLUMETRIC FLOW. A
DUCT VOLUMETRIC FLOW. 0
AVERAGE DUCT VELOCITY. M/M
VVERAGE DUCT GAS DENSITY.
UREA IN H20
UREA IN H2S04
TOTAL UREA
AMMONIA-DIRECT-IN H20
AMMONIA-D IRECT-IN H2S01
TOTAL AHMONIA-D IRECT
AMMONIA-DISTILL ED-IN H20
AMMON IA-D ISTILLED-IN H2SO«*
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2S01
TOTAL FORMALDEHYDE
R E
IT
V MFflfl - MM
DROP. MM u ? n
. p PR r .
UR
H 2
0 FXf> -S
0.2000E 02
0.7600E 03
0 ,6ni nr n?
n .t
I&A7F
• ni
0.1
-n .1
169E 02
i i RF n?
c ,
/M
MM H G
M
0 .1
n .1
7*»3 E 04
=if,^F nt4
d.QRRUF 07
MG/
AM3
0.5«»7i»E
0. OOOOE
0
0
0
0
0
0
0
0
0
0
.5<»7<»E
.3659E
.OOOOE
.3659E
.3836E
.OOOOE
.3836E
.3535E
•OOOOE
.3535E
02
00
02
03
00
03
03
00
03
01
00
01
0
Q
0
0
0
0
0
0
0
0
0
0
EMISSION DATA
MG/
DNM3
.6106E 02 0
.030QE 00 0
•
•
•
•
*
•
•
*
•
6106E
M081E
OOOOE
t*081E
M278E
OOOOE
<*278E
39
-------
TEST DATA -- UREA, AMMONIA, FORMALDEHYDE ~ TEST WO
TRC PROJECT 82988-01
Uf T TESTED
OA.E AND TIME OF TEST
SAMPLING LOG AT ION
WAME OF FIRM
LOCATION OF FIRM
POLLUTANTS SAMPLED
UNIT C
DEC 19 1978 0905
SCRUBBER OUTLET
AGRICO -EPA
8LYTHEVILLE ARK
UREA AND AMMONIA
TO 1 01 1
BAROMETRIC PRESSURE. IN HG
DUCT AREA. SO FT
NOZZLE DIAMETER . IN
PITOT CALIBRATION COEFFICIENTS 1
2
3
DRY GAS METER CALIBRATION FACTOR
FINAL LEAK RATE. CFM
TONS PER HOUR, PRODUCT
29 .71
18 .98
0.185
0.839
0.000
0.000
0.990
0.000
0.000
BY VOLUME DRY 8 ASIS
COMPOSITION OF DUCT GAS
CARBON DIOXIDE
OXYGEN
CARBON MONOXIDE
NITROGEN
UREA, AMMONIA, FORMALDEHYDE COLLECTED. MG
H20 IMPIMGERS 0
H2SOM IMPINGERS 0
TOTAL 0.9000E
UREA
.9000E
•OOOOE
AMMONIA-DIR
02 0.333DE 03
00 0.OOOOE 00
02 0.3330E 03
AMOUNT OF WATER COLLECTED. GRAMS
IHPINGERS
SILICA GEL
0.00
21 .00
0.00
79 .00
AMMONIA-DIST
0.3290E 03
0.OOOOE 00
0.3290E 03
23 .0
5 .6
FORMALDEHYDE
0.t»700E 01
O.OOOOE 00
0.<*700E 01
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST NO
TRC PROJECT 82988-01
IT T
i 5
? 5
5 5
I 5
; 5
i 5
5
> 5
5 5
4 5
i 5
i 5
IME
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
VEL HEAD
IN H20
0.9700
0.9500
0.9000
0.8400
0.7503
0.6300
0.9300
0.9500
0.9300
0.8100
0.7400
0.6900
ORIFICE
PRESS
IN H20
1 .1900
1 .1500
1 .0900
1 .0000
0.9100
0 .7600
1 .1100
1 .1500
1 .1100
0.9800
C .9000
0.8200
METER
INLET
DEG F
58.
53.
60.
61 .
60.
60.
60.
61.
62.
61 .
62.
60.
TEMPS
EXIT
DEG F
59.
59.
60.
59.
59.
60.
59.
60.
61 .
61 .
62.
61 .
DUCT STAT
PRESS
IN H20
-0.41
-0.41
-0.41
-0.41
-0.41
-0.41
-C.38
-0.38
-0.38
-0.38
-0.38
-0.38
DUCT
TEMP
DEG F
98.
102.
103.
102.
101 .
100.
101 .
103 .
104.
102.
102.
101 .
IN IT I
METER
CU FT
193
196
199
202
205
207
210
213
21 6
219
222
225
AL
VOL
.43
.30
.31
.26
.11
.86
.51
.39
.44
.47
.36
.10
P
R
B
1
1
1
1
1
1
1
1
1
1
1
1
CYC
AYG
0.
0.
0.
o.
o.
0.
0.
0.
0.
o.
o.
o.
\L METER VOLUME 227.85
-------
TEST DATA —
UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
— TEST HO
UnIT C
AGRICO -EPA
SCRUB3ER OUTLET
DEC 19 1973 0905 TO 1011
STANDARD CONDITION TEMPERATURE. OEG F
STANDARD CONDITION PRESSURE. IN HG ...
TOTAL SAMPLING T IME. MINUTES ,
AVERAGE SQUARE ROOT VELOCITY HEAD. IN
AVERAGE ORIFICE PRESSURE DROP. I* H20
AVERAGE METER TEMPERATURE. DEC F ....,
AVERAGE DUCT STATIC PRESSURE. IN H 20 ,
AVERAGE DUCT TEMPERATURE. DEG F ......
TOTAL SAMPLE VOLUME. DACF ,
TOTAL SAMPLE
H20 EX?
MOLE
MOLECULAR
WATER VAPOR VOLUME. DSCF ....
MOISTURE CONTENT OF DUCT GAS.
FRACTION DRY GAS
WEIGHT - DRY STACK GAS
MOLECULAR WEIGHT - STACK GAS ....
AVERAGE STACK PRESSURE. IN HG ...
DUCT VOLUMETRIC FLOW. ACFM
DUCT VOLUMETRIC FLOW. DSCFM
AVERAGE DUCT VELOCITY. FPM
EXCESS AIR. PERCENT
AVERAGE DUCT GAS DENSITY. LBS/ACF
ISOKINETIC FACTOR. PERCENT
0,
0,
0,
•6800E
• 2992E
•6000E
0.9119E
0.1014E
O.bOl2E
-0.3950E
,101 6E
.3U42E
,3«m<«E
• 1316E
• 3762E
,962<»E
0.288ME
0.28t3E
0.2968E
0.6096E
0.5'172E
0.3212E
-0.14E8E
0,
0
0,
0,
0,
0
02
02
02
00
01
02
00
03
02
02
01
01
00
02
02
05
05
04
05
0.6882E-01
0.1"067E 03
EMISSION DATA
UREA IN H20
UREA IN H2S01
TOTAL UREA
AMMONIA-D JRECT-IN H20
AMMONIA-DIRECT-IN H2SOH
TOTAL AMMONIA-DIRECT
AMMONIA-DISTILLED-IM H20
AMMONIA-DISTILL ED-IN H2S04
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2SOt»
TOTAL FORMALDEHYDE
ACF
0.3620E-01
O.OOOOE 00
0.3620E-01
0.1339E 00
O.OOOOE on
0.1339E 00
0.1323E 00
O.OOOOE 00
0.1323E 00
0.1890E-02
O.OOOOE 00
0.1890E-02
GR/
OSCF
Q.«*033E-01
O.COOOE 00
0.1033E-01
0.1192E 00
O.OOOOE 00
0.1U92E 00
00
O.OOOOE 00
0.1 «47««E 00
0.2106E-02
O.OOOOE 00
0 .2106E-02
LBS/
MR
0.1891E 02
O.OOOOE 00
0.1891E 02
0.&998E 02
O.OOOOE 00
0.6998E 02
0.fa9mE 02
O.OOOOE 00
0.691UE 02
0.?877E 00
O.OOOOE oc
0.?877E 00
LBS/
TO.S
0.1&91E 02
o.craooE oo
E 02
02
O.CXDOOE 00
0.4998E 02
0.69LAE 02
O.OOOOE 00
0.69mE 02
0.98T7E DO
O.OQDOE 00
0.9/87 7 E 00
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
~ TEST NO
UNIT C
A6RICO -EPA
SCRU83ER OUTLET
DEC 19 1978 0905 TO 1011
STANDARD CONDITION TEMPER
STANDARD CONDITION PRESSUI
TOTAL SAMPLING T IME, MlNU
AVERAGE SQUARE RROT VELOC
AVERAGE ORIFICE PRESSURE
AVERAGE METER TEMPERATURE
AVERAGE DUCT STATIC PRESS
AVERAGE DUCT TEMPERATURE.
TOTAL SAMPLE VOLUME. DM3
TOTAL SAMPLE VOLUME. DNM3
WATER VAPOR VOLUME. ON M3
AVERAGE STACK GAS PRESSURE
DUCT VOLUMETRIC FLOW. A
DUCT VOLUMETRIC FLOW. D
AVERAGE DUCT VELOCITY. M/M
VVERAGE DUCT GAS DENSITY
UREA IN H20
UREA IN H2SO««
TOTAL U3EA
AMMONIA-DIRECT-IN H20
AMMON IA-DIRECT-IN H2S01
TOTAL AMMONIA-DIRECT
AMMON IA-DISTILLED-IN H20
AMMON IA-D 1ST ILL ED-IN H2SO<»
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H 20
FORMALDEHYDE IN H2SO«t
TOTAL FORMALDEHYDE
R E
TF
IT
Y H EAD i
np . MM
. n FR r .
• MM
H20
• • Q .2000E 02
n .7 ftRDF nx
H2° F"*B -^ - -
R . b & i i F n i
p. MM n?n ".....
.. -R - 1
562E 02
RR^ F R?
E ,
/M
MM H G
f^
726E 04
scnr RU
0
0
0
0
0
0
0
0
0
0
0
0
MG/
AM3
.8284E
.OOOOE
.3284E
.3065E
•OOOOE
.3065E
.3028E
.OOOOE
.3028E
.U326E
•OOOOE
.1326E
EMISSION DATA
MG/
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
Q
0
0
DNM3
.9229E
.OOOOE
.9229E
.3415E
.OOOOE
.3415E
.3374E
.OOOOE
.337ME
.4819E
.OOOOE
.4819E
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
0
0
0
KG/
HR
.8587E
.OOOOE
.85 87 E
.5177E
.OOOOE
.3177E
.31 39E
.OOOOE
.3139E
.«*<» 8<4E
.OOOOE
• 4181E
102E n1
01
00
01
02
00
02
02
00
02
00
00
00
KG/
0
0
0
o
0
0
0
0
0
0
0
0
MT
.378/E
.OOOOE
»yl 83 E
.1 *»0/uE
• CQOOE
.J/MOOE
.138XE
.OOOOE
.VS83E
.1975E
.0000E
.1/75E
02
00
02
03
CO
03
03
00
03
U 1 1
oq
Ol1
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST NO
TRC PROJECT 82988-01
UNIT TESTED
DATE AND TIME OF TEST
SAMPLING LOCATION
NAME OF FIRM
LOCATION OF FIRM
POLLUTANTS SAMPLED
UNIT C
DEC 19 1973 1100 TO 1 205
SCRUBBER OUTLET
AGRICO -EPA
BLYTHEVILLE ARK
UREA AND AMMONIA
3AROMETRIC PRESSURE. IN HG
DUCT AREA. SO FT
NOZZLE DIAMETER. IN
PITOT CALIBRATION COEFFICIENTS 1
2
3
DRY GAS METER CALIBRATION FACTOR,
FINAL LEAK RATE. CF M
TONS PER HOUR, PRODUCT
29 .68
18.98
0.185
0.839
0.000
0.000
0.990
0.000
0.000
BY VOLUME DRY B ASIS
COMPOSITION OF DUCT GAS
CARBON DIOXIDE
OXYGEN
CARBON MONOXIDE
NITROGEN
UREA, AMMONIA, FORMALDEHYDE COLLECTED. MG
0
21
0
,00
,00
,00
H20 IMPIVGERS 0
H2SOt IMPI.VGERS 0
TOTAL 0.3360E
UREA
• 3360E
.OOOOE
AMMONIA-DIR
02 0.3700E 03
00 0.OOOOE 00
02 0.3700E 03
AMOUNT OF WATER COLLECTED. GRAMS
IMMNGERS
SILICA GEL
79 .00
AMMONIA-DIST
0.5«»20E 03
Q.OCOOE 00
0.5*42CE 03
32.0
5 .6
FORMALDEHYDE
0.3300E 01
Q.COCOE 00
0.330CE 01
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST
TRC PROJECT 82988-01
MO
NT
1
2
3
4
5
6
1
2
3
14
5
6
TIME
5 .0
5 .0
5 .0
5 .0
5 .0
5.0
5.0
5 .0
5 .0
5 .0
5.0
5 .0
VEL HEAD
IN H20
0.9400
0.9500
0.8700
0.6800
0.6800
0.6200
0.7500
0.3000
0.76CO
0.7500
0.6800
0.6000
ORIFICE
PRESS
IN H20
1 .1300
1 .1500
1 .0600
0.8300
0 .8300
0.7600
0.9100
0 .9600
0.9300
0.9100
0 .8300
0.7300
METER
INLET
DEG F
61.
65.
65.
64.
61 .
61 .
65.
65.
65 .
65.
65 .
65 .
TEMPS
EXIT
DEG F
64.
64.
65 .
65 .
63.
64.
65.
65 .
65.
65.
65 .
65 .
DUCT
PRE
IN H
-0
-0
-0
-0
-0
-0
-0
-0
-0
-0
-0
-0
STAT
SS
20
.43
.43
.43
.43
.43
.43
.36
.36
.36
.36
.36
.36
DUCT
TEMP
DEG F
102.
105.
105 .
105 .
102.
102.
103 .
104.
106.
106.
107 .
105.
IN IT IAL
MET ER V OL
CU FT
227.94
230.80
233.80
236.69
239.35
241 .96
244.6?
247.23
250.10
252.78
255.55
25 3 . 1 5
P
R
6
1
1
1
1
1
1
1
1
1
1
1
1
CYC
AN6
0
0
0.
OJ
o:
0.
o1
0.
0.
0
0.
0*
FINAL METER VOLUME
260.85
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
— TEST NO
UNIT C
A6RICO -EPA
SCRUBBER OUTLET
DEC 19 1978 1100 TO 1205
STANDARD CONDITION TEMPERATURE. DEG F
STANDARD CONDITION PRESSURE. IN HG
TOTAL SAMPLING T IME. MINUTES
AVERAGE SQUARE ROOT VELOCITY HEAD. IN H20 EX? .5 ....
AVERAGE ORIFICE PRESSURE DROP. IN H20
AVERAGE METER TEMPERATURE. DEG F
AVERAGE DUCT STATIC "PR ESSURE. IN H20
AVERAGE DUCT TEMPERATURE. DEG F
TOTAL SAMPLE VOLUME. DACF
TOTAL SAMPLE VOLUME. DSCF
WATER VAPOR VOLUME. DSCF
MOISTURE CONTENT OF DUCT GAS. PERCENT
MOLE FRACTION DRY GAS
MOLECULAR WEIGHT - DRY STACK GAS
MOLECULAR WEIGHT - STACK GAS
AVERAGE STACK PRESSURE. IN HG
DUCT VOLUMETRIC FLOW. ACFM
DUCT VOLUMETRIC FLOW. D S CF M
AVERAGE DUCT VELOCITY. FPM
EXCESS AIR. PERCENT -0
AVERAGE DUCT GAS DENSITY. LBS/ACF
ISOKINETIC FACTOR. PERCENT
0.
0.
0.
0.
0.
0.
-0.
0.
o.
0.
0.
0.
0.
0.
0.
0.
G.
C.
0.
-0.
0.
0.
6800E
299 2E
6000E
8676E
9192E
643 7 E
3950E
1013E
3 29 IE
3262E
1770E
5117E
9185E
2881E
2828E
2965E
5813E
5'113E
3063E
l'«»58E
02
02
C2
00
00
02
00
03
02
02
Cl
01
00
02
02
02
05
05
oq
05
6806E-01
1082E
03
UREA IN H20
UREA IN H2SO<+
T OT AL US E A
AMMONIA-DIRECT-IN H20
AMMON IA-DIRECT-IN H2SO«»
TOTAL AMMONIA-DIRECT
AMMON IA-DISTILLED-IM H 20
AMMONIA-DISTILLED-IN H2S04
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2S01
TOTAL FORMALDEH YDE
GR/
ACF
0.1398E-01
O.OOOOE 00
0.1398E-01
0.1539E 00
O.OOOOE 00
0.1539E 00
0.2255E 00
O.OOOOE 00
0.2255E 00
0.1373E-02
O.OOQOE 00
O.U73E-02
EMISSION DATA
GR/
DSCF
0.1590E-01
O.COOOE 00
0.1590E-01
0.1750E 00
O.OOOOE: oo
0.1750E 00
0.256*»E 00
O.OOOOE 00
0.2564E 00
0.1561E-02
O.OOQOE 00
0.1561E-D2
LBS/
HR
O.fa9 65 E 01
O.OOOOE 00
0.6965E 01
0.7670E 02
O.OOOOE 00
0.7670E 02
0.11 21E 03
O.OOOOE 00
0.11 2«»E 0?
0.68«»1E 00
O.OOOOE 00
0.6811E 00
0.7/67
D.OOQ
0/767
0.1T2
O.dOO
0/112
0.684
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
— TEST MO
UNIT C
A6RICO -EPA
SCRUBBER OUTLET
DEC 19 197S 1100 TO 1205
STANDARD CONDITION TEMPE
STANDARD CONDITION PRESS
TOTAL SAMPLING TIME, MIN
AVERAGE SQUARE RROT VELO
AVERAGE ORIFICE PRESSURE
AVERAGE METER TEMPERATURE.
AVERAGE DUCT STATIC PRESS
AVERAGE DUCT TEMPERATURE.
TOTAL SAMPLE VOLUME. 0 M3
TOTAL SAMPLE VOLUME. DNM3
WATER VAPOR VOLUME. ON M3
AVERAGE STACK GAS PRESSURE.
DUCT VOLUMETRIC FLOW. A
DUCT VOLUMETRIC FLOW. ON M3
AVERAGE DUCT VELOCITY. M/M
VVERAGE DUCT GAS DENSITY
UREA IN H2C
UREA IN H2SOM
TOTAL USE A
AMMONIA-DIRECT-IN H20
AMMONIA-DIRECT-IN H2S01
TOTAL AMMONIA-DIRECT
AMMON IA-DISTILL ED-IV H20
AMMONIA-DISTILL ED-IV H2S04
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H 20
FORMALDEHYDE IN H2SO<*
TOTAL FORMALDEHYDE
R F .
TFS
ITY
MM HG
wFan .
DROP - MM
. D
URE
DE
C f f
, MM
H20
H20
0.2QOOE 02
0.7600E 03
0.6'nnnF n?
n .t
t^7^F
• nt .
0.1
-it. i
79 9 E 07
nnTF n
•>
E ,
/M
MM HG
0 ."7
0.1
n .1
r57 1 L
• n
\
616E Of
«i«»ftF nu
0.
0.
0.
0.
0.
Q.
Q.
Q.
0.
Q.
0.
0.
MG/
AM3
3199E
OOOOE
3199E
3523E
OOOOE
3523E
5160E
OOOCE
51&OE
31«»2E
OOOQE
31H2E
EMISSION DATA
MG/
DNM3
02
00
02
03
00
03
03
00
03
01
00
01
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0 .
3637E
COOQE
3637E
1005E
OOOOE
«»005E
5868E
OOOOE
5868E
3572E
OOOOE
3572E
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
0
0
0
.31
.00
.31
.34
Q .1
KG/
HR
62E
DOE
62E
82E
.OOOOE
.3M82E
.51
.00
.51
01 E
DOE
DIE
.31 06E
.QOOOE
.31 06E
09 OF n
01
00
01
02
00
02
02
00
02
00
00
00
0
0
0,
«
0
0
0
0
0
0
0
0
cy
\
K
I
.!/*•»
• DOC
f*
.ysi
i
.2/2H
m
a
-------
TEST DATA -- UREA, AMMONIA, FORMALDEHYDE — TEST NO
TRC PROJECT 82988-01
UNIT TESTED
OATE AND TIME OF TEST
SAMPLING LOCAT ION
NAME OF FIRM
LOCATION OF FIRM
POLLUTANTS SAMPLED
UNIT C
DEC 19 1978 1300 TO 1 11 2
SCRUBBER OUTLET
AGRICO -EPA
BLYTHEVILLE ARK
UREA AND AMMONIA
BAROMETRIC PRESSURE. IN HG
DUCT AREA. SO FT
NOZZLE DIAMETER. IN
PITOT CALIBRATION COEFFICIENTS 1
2
3
ORY GAS METER CALIBRATION FACTOR
FINAL LEAK RATE. CF M
TONS PER HOUR, PRODUCT
29 .68
18 .98
0 .185
0.839
0.000
0.000
0.990
0.000
0.000
COMPOSITION! OF DUCT GAS
CARBON DIOXIDE
OXYGEN
CARBON MONOXIDE
NITROGEN
* BY VOLUME DRY B ASIS
0.00
21 ,00
0 .00
79 .00
UREA, AMMONIA, FORMALDEHYDE COLLECTED. M6
H20 IMPI^JGERS 0
H2SOH IMPINGERS 0
TOTAL 0.<»810E
UREA
,«4810E
• OOOOE
AMMONIA-DIR
02 0.3630E 03
00 O.OOOOE 00
02 C.3630E 03
AMOUNT OF WATER COLLECTED. GRAMS
IMPINGER S
SILICA GEL
AMMON IA-DIST
0.3H90E 03
O.OOOOE 00
0.3M90E 03
30.0
5 .9
FORMALDEHYOE
O.M240E 01
O.OOOOE 00
0.1240E 01
-------
TEST DATA -- UREA, AMMONIA, FORMALDEHYDE — TEST NO
TRC PROJECT 82938-01
NT
1
2
3
4
5
6
1
2
3
4
5
6
TIME
5.0
5.0
5.0
5.0
5 .0
5 .0
5 .0
5 .0
5 .0
5 .0
5 .0
5.0
VEL HEAD
IN H20
0.6100
0.7800
0.9000
0.7600
0.7300
0.6200
0.9300
0.9800
0.9600
0.8500
0.8000
0.7400
ORIFICE
PRESS
IN H20
0 .7300
0.9200
1 .0500
0.9100
0.8700
0.7400
1 .0900
1 .1500
1 .1400
1 .0000
0.9400
0 .8300
METER
INLET
DE6 F
68.
68.
67.
65.
64.
65 .
67.
67.
67.
68.
67.
67.
TEMPS
EXIT
DEG F
68.
68.
68.
67.
66.
66.
68.
68.
68.
68.
67 .
67.
DUCT STAT
P3ESS
IN H 20
-0 .12
-0.42
-0.42
-0 .42
-0.42
-0 .42
-0.48
-0.48
-0 .48
-0 .48
-0 .48
-0.48
DUCT
TEMP
DEG F
103.
106.
106.
101 .
99.
100.
103 .
104.
104.
105.
105 .
103 .
IN IT IAL
METER VOL
CU FT
261 .00
263.35
266.07
263.95
27 1 . 7 4
274.43
277.06
279.94
283.01
286.08
289 .00
29 1 . 7 8
P CYC
R AMG
B
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
1 0
FIMAL METER VOLUME
294.61
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST NO
TRC PROJECT 82988-01
UNIT C
A6RICO -EPA
SCRUBBER OUTLET
DEC 19 1978 1300 TO 1<412
AVERAGE SQUARE ROOT VELOCITY HEA3. IN H20 EX? .5 ..
AVERAGE DUCT VELOCITY. FPM
.... -O.tSCOE
OT> Q 7 1 C
.... C.3154E
02
02
02
00
00
02
00
03
02
02
01
01
00
02
u z
02
05
05
C*»
05
-01
03
EMISSION DATA
UREA IN H20
UREA IN H2SOt»
T OT AL US E A
AMMONIA-OIRECT-IN H20
AMMONIA-DIRECT-IN H2S01
TOTAL AMMONIA-DIRECT
AMMONIA-DISTILL ED-IN H20
AMMONIA-DISTILL ED-IN H2S04
TOTAL AMMONIA-DISTILLED
;
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2S01
TOTAL FORMALDEHYDE
GR/
ACF
0.1979E-01
O.OCOOE 00
0.1979E-01
0.119<*E 00
O.OOOOE 00
0.1t»9<*E 00
0.1<»36E 00
O.OOOOE 00
0.1M36E 00
0.1745E-02
O.OOOOE 00
0.1715E-02
GR/
DSCF
0.2239E-01
O.OOOOE 00
0.2239E-01
0.1690E 00
O.OOOOE 00
0.1690E 00
0.1625E 00
O.OOOOE 00
0.1625E 00
0.197«*E-02
C.OOOOE 00
0.1974E-02
LBS/
HR
0.1015E 02
O.DOOOE 00
0.1015E 02
o^eeiE 02
O.QCOOE 00
0.7664E 02
0.7368E 02
O.OOOOE oo
C.7368E 02
0.3951E 00
O.OOOOE 00
0.8951E 00
LB
...
0.1/01
O.yOOO
o/i ay
0.7/6
o.o/oo
0 J766
0.7/36
C.,000
0/73^
O.S'VS
0 yOQO
0.895
-------
TEST DATA —
UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
— TEST
UNIT C
AGRICO -EPA
SCRUBBER OUTLET
DEC 19 1978 1300 TO 1412
STANDARD CONDITION TEMPE
STANDARD CONDITION PRESS
TOTAL SAMPLING TIME, MIN
AVERAGE SQUARE R R OT VELO
AVERAGE ORIFICE PRESSURE
AVERAGE METER TEMPERATURE.
AVERAGE DUCT STATIC PRESS
AVERAGE DUCT TEMPERATURE.
TOTAL SAMPLE VOLUME. DM3
TOTAL SAMPLE VOLUME. DNIM3
WATER VAPOR VOLUME. DNM3
AVERAGE STACK GAS PRESSURE.
DUCT VOLUMETRIC FLOW. A
DUCT VOLUMETRIC FLOW. 0
AVERAGE DUCT VELOCITY. M/K
VVERAGE DUCT GAS DENSITY
UREA IN H20
UREA IN H2S04
TOTAL UREA
AMMONIA-DIRECT-IN H20
AMMONIA-OIRECT-IN H2S04
TOTAL AMMONIA-DIRECT
AMMONIA-D 1ST ILL ED-IN H20
AMMONIA-DISTILLED-1N H2SO«»
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H 2SO«t
TOTAL FORMALDEHYDE
ATU
RE i
TES
IT Y
DUO
IJ^E
DE
F ,
/M
T /M
M
RE 0 E
K r
H EAD .
P • MM
EG C .
. MM H
MM H G
MM
H20
20 .
H20 EX? .
\
5 . .
•
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
MS/
AM3
1529E
OOOOE
1529E
3118E
OOOOE
3118E
3236E
OOOOE
3286E
3992E
OCOOE
3992E
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
0
0
0
EMISSI
MG/
DNM3
.5121E
.OOOOE
.512tE
.3867E
.OOOOE
.3867E
.3718E
.OOOOE
.3718E
.1517E
.OOOOE
.1517E
ON D
02
00
02
03
00
03
03
00
03
01
00
01
ATA
0
0
0
0
0
0
0
0
0
0
0
0
.. 0 .
. . 0 .
KG/
HR
.1610E
.OOOQE
.1610E
.3179E
.OOOOE
.3179E
.33 15 E
.OOOOE
.33 15E
.1061E
2000E
76QnF
600
151
211
HE
OE
7F
1 9 t|7F
111
395
951
3E
8E
flF
9387E
02
03
02
01
02
02
02
02
00
nn
1786E-01
753DF n^
1 69
1 19
9 61
1 09
01
00
01
02
00
02
02
00
02
00
SE
8E
IE
3E
01
01
03
K
-tt
0.2fl5
O.J30.Q
.OOOOE 00
.1Q61E
00
0/2
D.I
o.cr
°/1
O.I/
O./}
041
o.v
OyO
o;i
m
?3
(
§/
f
I
I
79
-------
TEST DATA —
UREA, AMMONIA, FORMALDEHYDE — TEST MO
TRC PROJECT 82988-01
UNIT TESTED
DATE AND TIME OF TEST
SAMPLING LOCATION
NAME OF FIRM
LOCATION OF FIRM
POLLUTANTS SAMPLED
UNIT C
DEC 19 1978 1150
SCRUBBER OUTLET
AGRICO -EPA
BLYTHEVILLE ARK
UREA AND AMMONIA
TO 1553
BAROMETRIC PRESSURE. IN HG
DUCT AREA. SQ FT
MOZZLE DIAMETER . IN
PITOT CALIBRATION COEFFICIENTS 1
2
3
DRY GAS METER CALIBRATION FACTOR.
FINAL LEAK RATE. CF K
TONS PER HOUR, PRODUCT
29 .63
18 .98
0.185
0.839
0.000
O.COD
0.990
0.002
0.000
COMPOSITION OF DUCT GAS. X BY VOLUME DRY BASIS
CARBON DIOXIDE 0 .GO
OXYGEN 21 .00
CARBON MONOXIDE 0.00
NITR OGEN 79 .00
UREA, AMMONIA, FORMALDEHYDE COLLECTED. MG
H20 IMPIMGERS 0
H2S04 IMPINGERS 0
TOTAL 0.2840E
UREA
,28«»OE
• OOOOE
AMMONIA-DIR
02 0.3<»20E 03
00 O.OQOOE 00
02 0.3M20E 03
AMOUNT OF WATER COLLECTED. GRAMS
IMPINGERS
SILICA GEL
AMMON IA-DIST
0.3230E 03
O.OOOOE 00
Q.3230E 03
18.0
3 .9
FORMALDEHYDE
0.2050E 01
O.OOOOE 00
0.2050E 01
-------
TEST OATA — UREA, AMMONIA, FORMALDEHYDE — TEST
TRC PROJECT 82988-01
NT
1
2
3
4
5
6
1
2
3
4
5
6
TIME
5 .0
5 .0 -
5 .0
5 .0
5.0
5 .0
5 .0
5 .0
5 .0
5.0
5.0
5 .0
VEL HEAD
IN H 20
o.9qoo
0.9200
0.8500
0.6200
0.5900
0.5000
0.7000
0.7800
0.9100
0.8200
0.7700
0.6300
ORIFICE
PRESS
IN H20
1 .1100
1 .0900
1 .0000 •
0 .7400
0.7000
0 .6000
0.8300
0.9200
1 .0800
0.9700
0.9200
0.7400
METER
INLET
OEG F
67.
67.
67.
67.
67.
67.
68.
69.
69 .
69.
69.
69.
TEMPS DUCT SI AT
EXIT PRESS
DEG F
67.
67.
67 .
67.
67.
67 .
69.
69 .
69.
69.
69.
69 .
DUCT INITIAL P CYC
TEMP METER V OL R ANG
IN H 20 DEG F
-0 .39
-0.39
-0 .39
-0.39
-0 .39
-0 .39
-0 .i»2
-0 .42
-0.42
-0.42
-0.42
-0.42
105.
105 .
105.
1G4.
105.
103 .
105.
105.
105 .
106.
106.
104.
CU FT B
294.70
297.58
300.60
3C3.5C
306.10
303.55
31 0.96
313.49
3 1 6 . 25
319.22
322.10
324.91
1
1
1
1
1
1
1
1
1
1
1
1
0.
0*
o.
o.1
0.
o.
0..
0.
o.
o.
o.
o.
FIMAL METER VOLUME
327.68
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
-- TEST NO
UNIT C
AGRICO -EPA
SCRUBBER OUTLET
DEC 19 1978 1450 TO 1553
IN H20 EX? .5
STANDARD CONDITION TEMPERATURE. DEG
STANDARD CONDITION PRESSURE. IN HG
TOTAL SAMPLING T IKE. MINUTES
AVERAGE SQUARE ROOT VELOCITY HEAD
AVERAGE ORIFICE PRESSURE DROP, in HZO
AVERAGE METER TEMPERATURE. DEG F ....
AVERAGE DUCT STATIC PRESSURE. IN HZO
AVERAGE DUCT TEMPERATURE. OEG F
TOTAL SAMPLE VOLUME. DACF .
TOTAL SAMPLE VOLUME. DSCF
WATE.R VAPOR VOLUME. DSCF
MOISTURE CONTENT OF DUCT GAS. PERCENT
MOLE FRACTION DRY GAS
MOLECULAR WEIGHT - DRY STACK GAS ....
MOLECULAR WEIGHT - STACK GAS
AVERAGE STACK PRESSURE. IN HG .......
DUCT VOLUMETRIC FLOW. ACFM
DUCT VOLUMETRIC FLOW. DSCFM
AVERAGE DUCT VELOCITY. FPM ...
EXCESS AIR. PERCENT -0
AVERAGE DUCT GAS DENSITY. LB S/ACF
ISOKINETIC FACTOR. PERCENT ......
C
0
0
0
0
C
-0
0
C
0
G
0
0
0
0
C
0
0
0
-0
0
0
.6800E
.2992E
.6000E
.8637E
.8917E
.6796E
.tfOSOE
.1 043E
.3298E
.32M1E
.1031E
.3083E
.9692E
.2881F
.2351E
.2960E
.5772E
.5173E
.3011 E
.1158E
.6842E
.1062E
02
02
02
no
GO
02
00
03
02
02
01
01
00
02
02
02
05
05
04
05
-01
03
EMISSION DATA
UREA IN H20
UREA IN H2S04
T OT AL UR E A
AMMON IA-DIRECT-IN H20
AMMONIA-DIRECT-IN H2S01
TOTAL AMMONIA-DIRECT
AMMONIA-DISTILL ED-IN H20
AMMONIA-DISTILLED-IM H2S04
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2SO«*
TOTAL FORMALDEHYDE
GR/
ACF
0.1212E-01
O.OOOOE 00
0.1212E-01
Q.1459E 00
O.OOOOE 00
0.1459E 00
0.1378E 00
O.OOOOE 00
0.1378E 00
0.87<46E-03
O.OOOOE 00
0.87<48E-03
GR/
DSCF
0.1352E-01
O.OOOOE 00
0.1352E-01
0.1628E 00
O.OOOOE 00
0.1628E 00
0.1538E 00
O.OOOOE 00
C.1538E 00
0.9760E-03
O.OOOOE 00
0.97bOE-03
L3S/
HR
0.5995E 01
O.OOOOE 00
0.5995E 01
0.7220E 02
O.OOOOE 00
0.7220E 02
0.6819E 02
O.OUOOE oo
0.6819E 02
0.4328E 00
O.OOOOE 00
O.H328ET 00
LB:
TOf
0.5^9!
O.rfoO!
0/5 99 5
O.EFOOf
0/722(
0.681'
o/oooc
1.681?
-------
TEST DATA —
UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82983-01
— TEST NO
UNIT C
A6RICO -EPA
SCRUBBER OUTLET
DEC 19 1978 1450 TO 1553
STANDARD CONDITION TEMPE
STANDARD CONDITION PRESS
TOTAL SAMPLING TIME, MIN
AVERAGE SQUARE R R OT VELO
AVERAGE ORIFICE PRESSURE
AVERAGE METER TEMPERATURE.
AVERAGE DUCT STATIC PRESS
AVERAGE DUCT TEMPERATURE.
TOTAL SAMPLE VOLUME. DM3
TOTAL SAMPLE VOLUME. DNM3
WATER VAPOR VOLUME. DNM3
AVERAGE STACK GAS PRESSURE.
DUCT VOLUMETRIC FLOW. AM3
DUCT VOLUMETRIC FLOW. ON M
AVERAGE DUCT VELOCITY. M/M
VVERAGE DUCT GAS DENSITY.
UREA IN H20
UREA IN H2SO*t
TOTAL U3EA
AMMONIA-DIRECT-IN H20
AMMON IA-DIRECT-IN H2SO«t
TOTAL AMMONIA-DIRECT
AMMON IA-D I STILL ED -IN H20
AMMONIA-DISTILL ED-IM H2SO«*
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2SOf
TOTAL FORMALDEHYDE
RE.
TE^
IT
DR •,
Y
n
. n
UR -
F
DP
i. c.2nnnF n?
•finnf
• r,^
HEAD. MM H20 EXP.5 .....
EG C
120
0.1
iT^TF
• m
0.?7fc«;F 07
-R .1
99 8F n?
n?<} F
• n?
E.
MM HG
M
635f nt»
u^ f
- nu
0
0
0
0
0
0
0
0
0
0
0
0
.
.
.
.
.
.
•
.
•
.
.
.
KG/
AM3
2773E
OOOOE
2773E
33«»OE
OOOOE
33<40E
315HE
OOOOE
3154E
2002E
OOOOE
2002E
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
0
0
0
EM
.3
.0
.3
.3
ISSION DATA
MG/
DNM3
09«»E
OQOE
094E
726E
.OOOOE
.3
.3
.0
.3
726E
519E
OOOE
519E
.223«»E
.0
.2
OOOE
23 4 E
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
0
0
0
KG/
HR
.2722E
.OOOOE
.27 22E
.3278E
.OOOOE
.3278E
.3096E
.OOOOE
.3096E
.19 65 E
•OOOOE
.1965E
01
00
01
02
00
02
02
00
02
00
00
00
• nl
w •*•
K(
ft
0.1 lP
0 . OyO 0 f
o./ili
/ <
0.1/HU'
0 JUQ^
o/mj
0.13V
o , n/6W
0 «1 3 •
/
/
0 . 8/6W
o ./jol
0/86^
-------
TEST DATA -~ UREA, AMMONIA, FORMALDEHYDE — TEST
TRC PROJECT 82988-01
UNIT TESTED
OATE AND TIME OF TEST
SAMPLING LOCATION
VAME OF FIRM
LOCATION OF FIRM
POLLUTANTS SAMPLED
UNIT C
DEC 19 1978 1608
SCRUBBER OUTLET
AGRICO -EPA
BLYTHEVILLE ARK
UREA AND AMMONIA
TO 1715
3AROMETRIC PRESSURE. IN HG
DUCT AREA. SO FT
MOZZLE DIAMETER . IN
=»ITOT CALIBRATION COEFFICIENTS 1
2
3
DRY GAS METER CALIBRATION FACTOR.
FINAL LEAK RATE. CF M
TONS PER HOUR, PRODUCT
29 .63
18 .98
0.185
0.839
0.000
0.000
0.990
0.000
0.000
COMPOSITION OF DUCT GAS. t BY VOLUME DRY BASIS
CARBON DIOXIDE 0.00
OXYGEN 21 .00
CARBON MONOXIDE 0.00
NITROGEN
UREA, AMMONIA, FORMALDEHYDE COLLECTED. MG
H20 IMPINGERS
H2SO*» IMPINGERS
TOTAL
UREA AMMONIA-DIR
0.f700E 02 0.3020E 03
-O.OOOOE 00 O.OOOOE 00
0.<»700E 02 0.3020E 03
AMOUNT OF WATER COLLECTED. GRAMS
IMPINGERS
SILICA GEL
79 .00
AMMON IA-D 1ST
0.3060E 03
O.OOOOE 00
0.3060E 03
23 .0
5 .5
FORMALDEHYDE
0.3140E 01
O.OOOOE 00
0.3140E 01
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST
TRC PROJECT 82988-01
NT
1
2
3
4
5
6
1
2
3
4
5
6
TIME
5 .0
5.0
5.0
5.0
5 .0
5.0
5 .0
5 .0
5.0
5 .0
5 .0
5 .0
VEL HEAD
IN H20
0.9700
0.9400
0.9100
0.7200
0.6900
0.6100
0.9500
0.9400
0.9800
0.8100
0.72CO
0.6100
ORIFICE
PRESS
IN H20
1 .1500
1 .1100
1 .0800
0 .8600
0.8100
0.7300
1 .1200
1 .1100
1 .1600
0.9600
0.8600
0.7300
METER
INLET
DEC F
68.
67.
67.
67.
67.
66.
66.
66.
66.
66.
65.
65.
TEMPS DUCT STAT
EXIT PRESS
DEG F
68.
68.
68.
67 .
67 .
66.
66.
66.
66.
66.
66.
65.
DUCT INITIAL P CYC
TEMP METER VOL R A>tG
IN H20 DEG F
-0.44
-C .44
-C .44
-0 .44
-0.44
-0.44
-0.49
-0.49
-0 .49
-0.49
-0 .49
-0.49
100.
105 .
106.
105 .
104.
103 .
104.
105 .
105 .
106.
105.
103 .
CU FT 8
323.00
330.73
333.90
336.82
339.60
342.30
344.82
347.77
350.82
353.90
356.80
359.50
1
1
1
1
1
1
1
1
1
1
1
1
U.
0.
o.
o.
c.
o.
0.
0.
o.
o.
o.
o.
FINAL METER VOLUME
362.11
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE — TEST NO
TRC PROJECT 82988-01
UNIT -C
AGRICO -EPA
SCRUBBER OUTLET
DEC 19 1978 1608 TO 1715
STANDARD CONDITION TEMPERATURE. DEG F '
STANDARD CONDITION PRESSURE. IN HG
TOTAL SAMPLING T IME. MINUTES
AVERAGE SOUARE ROOT VELOCITY HEAD. IM H20 EXP .5 ....
AVERAGE ORIFICE PRESSURE D?OP. IM H2o
AVERAGE METER TEMPERATURE. DEG F
AVERAGE DUCT STATIC PRESSURE. IN H 20
AVERAGE DUCT TEMPERATURE. DES F
TOTAL SAMPLE VOLUME. DACF -
TOTAL SAMPLE VOLUME. DSCF
WATER VAPOR VOLUME. DSCF
MOISTURE CONTENT OF DUCT GAS. PERCENT
MOLE FRACTION DRY GAS
MOLECULAR WEIGHT - DRY STACK GAS
MOLECULAR WEIGHT - STACK GAS
AVERAGE STACK PRESSURE. IN HG
DUCT VOLUMETRIC FLOW. ACFM
DUCT VOLUMETRIC FLOW. OSCFM
AVERAGE DUCT VELOCITY. FPM
EXCESS AIR. PERCENT -C
AVERAGE DUCT GAS DENSITY. LBS/ACF
ISOKINETIC FACTOR. PERCENT
0.
0.
0.
D.
0.
Q.
-0.
0.
0.
0.
0.
C.
0.
0.
0.
0.
0.
G.
0.
-C.
0.
0.
6800E
299 2E
6000E
9027E
9733E
6646E
•4650E
10f2E
311 IE
3362E
1311E
3837E
961 6E
288*»E
2842E
2960E
6039E
5375E
3182E
M58E
02
02
02
00
00
02
00
03
02
02
01
01
00
02
02
02
05
05
0<«
05
6828E-01
1061E
03
EMISSION DATA
UREA IN H20
UREA IN H2S04
TOTAL USE A
AMMONIA-DIRECT-IN H20
AMMONIA-DIRECT-IN H2S01
TOTAL AMMONIA-DIRECT
AMMONIA-DISTILLED-IN H 20
AMMONIA-DISTILLED-IN H2SO«»
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2S01
TOTAL FORMALDEH YDE
GR/
ACF
0.1920E-01
D.OOOOE 00
0.1920E-01
0.1234E 00
O.QOOOE 00
0.1231E 00
0.1250E 00
O.OOOOE 00
0.1250E 00
0.1283E-02
O.OCOOE 00
0.1283E-02
GR/
DSCF
0.2157E-01
O.OOOOE 00
0.2157E-01
0.1386E 00
O.OOOOE 00
0.1386E 00
0.11D1E 00
O.OOOOE 00
0.1 40*»E 00
0.1 4H1E-02
O.COOOE CO
0.1 441E-Q2
L3S/
HR
Q.?937E 01
O.OOOOE 00
0.9937E 01
0.&385E 02
O.OOOOE 00
0.6385E 02
0.6470E 02
O.OOOOE 00
0.6<«70E 02
0.6639E 00
O.OCOOE 00
0.6639E 00
TO/N
0.9737
o.otioo
0.^937
0.6385
0 7*6000
0.6385
0.6^70
0.0/000
0.^170
0.^639
CyCOOO
0.6639
-------
TEST DATA — UREA, AMMONIA, FORMALDEHYDE
TRC PROJECT 82988-01
-- TEST NO
UNIT C
AGRICO -EPA
SCRUB 3 ER OUTLET
DEC 19 1978 1608 TO 1715
STANDARD CONDITION TEMPE
STANDARD CONDITION PRESS
TOTAL SAMPLING TIME, MlN
AVERAGE SQUARE RROT VELO
AVERAGE ORIFICE PRESSURE
AVERAGE METER TEMPERATURE.
AVERAGE DUCT STATIC PRESS
AVERAGE DUCT TEMPERATURE.
TOTAL SAMPLE VOLUME. DM3
TOTAL SAMPLE VOLUME. ONM3
WATER VAPOR VOLUME. DNM3
AVERAGE STACK GAS PRESSURE.
DUCT VOLUMETRIC FLOW. A
DUCT VOLUMETRIC FLOW. ON M3
AVERAGE DUCT VELOCITY. M/M
VVERAGE DUCT GAS DENSITY
UREA IN H20
UREA IN H2SOM
T OT AL U* E A
AMMONIA-DIRECT-IN H20
AMMONIA-DIRECT-IN H2SO«t
TOTAL AMMONIA-DIRECT
AMMONIA-DISTILL ED-IN H20
AMMONIA-DISTILL ED-IM H2S01
TOTAL AMMONIA-DISTILLED
FORMALDEHYDE IN H20
FORMALDEHYDE IN H2S04
TOTAL FORMALDEHYDE
ATI!
R E •
TES
ITY
RE. DE
MM HG
H F API -
0 3 0 P - MM
• D
UR E
OF
E ,
/M
H
. MM H
MM HG
6 C
MM
H20
20 .
H20 EX P. 5 .....
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
MG/
AM3
4394E
OOOOE
4394E
2823E
OOOOE
2823E
2861 E
OOOOE
2861 E
2935E
OOOOE
2935E
EMISSION DAT
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
0
0
0
0
MG/
DNM3
.4936E
.OOOOE
.4936E
.3172E
.OOOOE
.3172E
.3214E
.OOOOE
.3 21 HE
.3298E
.OOOOE
• 3298E
A
. . 0
,?nnnF
7
f,nnF
.fcnnriF
455 OE
2U7 ?F
1
1
4
9
9
91 HE
1 81 E
660E
c,71 F
379 9 E
7=;i 7F
1
1
9
1
71 OE
5 22E
69 8 E
09 IE
02
03
02
01
02
02
02
02
00
CO
-01
03
04
04
03
01
KG/ K"(
02
00
02
03
00
03
03
00
03
01
00
01
0
0
0
0
0
0
0
0
Q
0
0
0
HR
.4512
.0000
.4512
.2899
E
C
E
E
.QOOOE
.2899
r
.2937E
.OOOOE
.2937
• SOI1*
.0000
.3014
E
E
r
E
01
00
01
02
00
02
02
00
02
OC
00
00
flj
0.1 4P
O.OyOOC
0./9^
C .1 271
o.0q^
0/12B
0.1/9'
o.^c*
oyfap
c.i/A
o./oB
0 .1 37
FS01 STOP 00000 00000006
-------
APPENDIX A.2
SAMPLE EQUATIONS AND EXAMPLE CALCULATIONS
-------
EMISSION CALCULATION SY>30LS
La - Allowable leak rate, era
Vm . - Total meter sample volume, ft
T_ , - Total sampling time, niin
L - Final leak rate of sampling train, cfm
Vmc , - Total volume sampled corrected for excessive leakage, ft
total *
Y - Dry gas meter calibration factor, dimensionless
o
T , - Standard temperature, F
~ °T.
Tm - Average dry gas meter temperature, F
avg»
P - Barometric pressure, "Tig
bar
AH - Average orifice pressure drop, "H^O
P , - Standard pressure, "Hg
V_ - Volume of liquid collected in impingers, ml
Vc_ - Volume of liquid collected in silica gel, grams
SG
J* - Molecular weight of stack gas, Ib/lb-aole
w
%C02 - Percent CO- by volume (dry basis), %
%CO - Percent CO by volume (dry basis), %
£N. - Percent II. by volume (dry basis) , %
%0
7 - Percent 0- by volume (dry basis), %
D - Average duct gas density, Ibs/ft
s t
Ps - Average duct static pressure, "H-0
Ts_ - Average duct temperature, F
avg
EA - Excess air, 7.
V - Average duct velocity, ft/min
C - Pitot tube coefficient, dimensionless
?
i
(/
-------
EMISSION CALCULATION SYMBOLS (cont'd)
Q - Duct volunecric flow rate, acnn
Q , - Ducc volumetric flow rate, corrected to dry standard conditions, dscfa
D^ - Nozzle diameter, inches
F - F factor, DSC7/MM BTU
£H - Percent by weight of hydrogen in fuel
1C - Percent by weight of carbon in fuel
ZS - Percent by weight of sulfur in fuel
SN - Percent by weight of nitrogen in fuel
20 - Percent by weight of oxygen in fuel
GCV - Gross calorific value of fuel, BTU/lb.
C - Actual particulate concentration, grains/acf
Cs - 'Particulate concentration, grains/dscf
ER - Particulate emission rate, Ibs/hr
E - Particulate emissions, Ibs/MM BTU
Cs (§. 12% CO- - Particulate concentration, grains/dscf Q 12% CO-
C @ 50% EA - Particulate concentration, grains/dscf 9 50% EA
\C_ - Particulate concentration, lbs/1000 duct gas
C^ 8 12%C02- Particulate concentration, lbs/1000 Ibs § 12% C02
CL. 3 50% EA - Particulate concentration, Ibs/'lOOO Ibs @ 50% EA
24 - Total particulata collected, nig
-------
2- fl
1/^0
1. Allowable Leak Rate
La - 0.02 cfm or 0.04 vm total
T
total
0.04 Vm total 0.04 x
which ever is less.
total
(oO.O
La = 0,0 3O cfm
2. Correction for Excessive Leak Rate
Lp = O-OOO cfm
if Lp > La use nc total in place of m total in all subsequent
equations.
V . = V , - (Lp - La) T
me total m total total
mc total
ff
3. Volune of Sample Measured by Dry Gas lleter, Corrected to Standard Conditions
r- > AH avg"
V . , ,. = V , Y f std 4 450
in total (std) m total
"m avg 4- 460y
13.6
std
\ total (std) = 3^4 1 x
Vm total (std) = 34-1 8 dscf
/68 •»- 460\
l^O.I-f 460 j
i.Q I
+ 13.6
29.92
- 34-,42 ^ i.oloU
4. Moisture Content of Duct Gas
% H20 = 0.04707 (7I 4- VSG)
m total (std) 4- 0.04707 (V.J. 4
=-0.04707 (2S-CM-
-f- 0.04707
--73 2
x 100
,x 100
-------
5. Molecular Weight of Stack Gas
(0.44 x 7. C02) + (0.28 x 7. C0)+(0.28 r. 7. :?2) + (0.32 •/. %
(0.44 x 0 )+(0.28 x O )+(0.28 x 7 9 ) + (0.32 x 1\ )
1.18 ( ~ H20
(i"T3-)+o.is c 3.7?
Ms
Ib/lb-mole
6. Average Duct Gas Density
Ps avg
D =• 0.0458 x l*s /bar +13.6
st
ls avg + 460
-o.'-fo
Dst = °'0458 x
sc
T-'' + 13.6 J x 29.37
I ol. ^ T 460
lbs/ft3
7. Excess Air
. 100 f% °2 - 0.5 % CO 1
|_0.264 % N2 - (I 02 - 0.5% CO)J
r - 0-5 ^ : i
[_0.264 x - ( - 0.5 x )J
EA = 100
EA =
8. Average Duct Velocity
V = 5129.4 C (/AP)avg
s avg -r 460
V = 5129.4 x
s
,
bar s a
13
iVg |
.6 /
Ms
5" I ft/min
-------
9. Duct Volumetric Flow Rate
Q - V x A
x s s
Q
Q
10. Duct Volumetric Flow Rate, Corrected to Dry Standard Conditions
/ _ _ \ /T \ /P PS avg'
n n fi " H2° \ /std + 460 \ /bar +13.6
Qstd = Q I1' -Tob~) IT TTT:) \~T~
\ / _\ s avg + 460/ \ std
68 + 460
460 29-92
Q . = 5,. dscfm
'StQ
11. Isokinetic Factor
= 5.67 (Ts avg + 460)(Vm std)
V x T . . % H2°l ^(Dti)2 x 0.7854
bar OO 144
5.67 ( [t '-U
iJA_"\ /C'^')2 x 0.7854
13.6 J \ ~ 100 J ( 144
I =
12. F - Factor ( [\| /\-.
• 1.53%
GCV
F = 106(3.64% H + 1.53% C -5- 0.57% S + 0.14% N - 0.46% 0)
F = 106(3.64 x +1.53 x +0.57 x +0.14 x -0.46 x
F = DSCT/MM BTO
-------
13. Actual, Particulars Concentration
A
fr \(P -s avg\/ 1 "~—\
c =, 0-01543 x Kn j std + 660J V par + 13.6 M 100 /
v
stdv s avg •*• 460 std
0.01543 x 1
-------
18. Particulate Concentration Corrected to Dry Standard Conditions
and 50Z Excess Air
C"
@ 12% C02 x 0.10A-(Tstd + 460)
"Lb *• 2 (0.44 x % C02) + (0.28(% CO + %H2)) + (0.32 x %02)
x 0.104 (528)
=
C L A C°
Lb 2 (0.44 x ) + (0.28( + )) -r (0.32 x
@ 12Z C02 = lbs/1000 Ibs dry corrected to 122 C02
21. Particulate Concentration Eased on Duct Gas Weight Corrected to 50% Excess Air
r 'a in- FA = Cs @ 50% EA x 0.104 (Tstd + 460)
u "
(0.44 x %C02) + (0.28(%CO + %N2)) -r (0.32 x %02) ( Nfr
c
-------
APPENDIX B
FIELD DATA SHEETS
-------
iTLE
n /1
Project No.
Book No. _L
. 1
Page No..
. . Proceeded.. ~f~~o ..
•'..___........ pfokle^s ._ Pa^f7
..- ._.'/ :;.:.,.: .,1.4; i
e.a
.6 «~
* U." ...-
. /%/iO/Mefdv
.Probe- l'i\t
f> io
"/-o
u/
y
a -
&..:.
hod
K/dS,
ib le.
fi C
-------
Irn Ha
lant L
•cat Mo
nnplln
'urpoee
late
»« rTCt *•' / C f~>
ocatlon fclvttaf l/Jlr> $
. /
1
g Loco
of Tet
/?
**• r*"" • —
:lon
Crr-rtfcU^
\t.6lr#n j
/ /
feater S' f R*.
Port
j
7r
Probt
Silli
Sill
L'k
Point
/
1
'^
f
>'
6
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2.
^
^
>
^~
Time
Mln
5;
M
fl
LJ
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t
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5-
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O
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P
C
P
P
L
p
P
0
0
0
i
8
Pump
rAorlfi
Aabli
rf~Bar 1
Probi
Fllti
9
10
Velocity
AP
In l«20
4
1
,7
7
i
3
f>
Cj
f
£
£
£
5"
5
'f
J
5T
3
1
5
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4
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4-
23
24
25
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out *r
i
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t
I
t
i
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5
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5-
5"
f
r
r
>'
f
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r
5"
5
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f
/
^
J
^
f
^
Cleaning Patch ' A'/ /
11.0 Collected
?£"
II.O Condition <—/'
Probe Heater Setting
/.O
Nomograph ^s f *• '
In. C Factor » /Q ' i
X Pltot
Coefficient > > 3^ /
•In. Orifice All. /, a 4/*"
»/~^VO
mln. Teat Start Time ~£fffSpr /**• L~<^.s
ampa Teat End Tine / 6 O /
Box Temp Setting AS/-A
26'
2?T28
29
30
PSTACK
In II20
-•
J,
tl
r
~
1
(
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,f
i /
X-
V
/
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^
%
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32
33
34
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TSTACK
•F
1
1
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^
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t
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1
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so
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Vac.
In llg
Q-,0
A., Q
4D
Q-D
4,0
IS
4-3
>~0
£c
4,L
3~
-------
>. , FIELD DATA SHEETS /Af ! Nomograph _
•Irn Name nQ^tCO Pump Ho. X? / Probe Diameter *//?5 In. C Factor - 77
'lant Location (>l\~hl^^l)r' Ak . Orifice No. /S~~3 Assumed Moisture 6 X Pilot Coefficient fj?j¥_
'cst Mo. 2. Ambient Temp & (J °F Teat Duration £ Cs "In. Orifice AHA />O/
inapllng Location ^ fak£^J^^)U7Bor Proas 2~/, // "llg Traverse Point Interval £ mln. Teat
•urpoae of Test ( t\f£tf Probe Ident. No. ?? */* Probe Heater Setting ^ / £x amps Teat
late /2-/M ' / ?$ Filter Ident. No. d///* Dox Temp Sattl"8 //s//£f- Leak
fester —
7
3
0
i
5"
s
5-
^
5"
i
f
i
^
0
O
0
0
2
(9
C
6
o
c
•J
12
13
14
15
All
In 11.0
~(
O
1
V
V
1
,
o
o
j
_
o
p
7
7
/
/
f
/j
i
9
5
f
(5
/
£
/
L
/
5
1
^
Z
Q
0
O
0
o
0
jT
t^-
0
0
i
0
o
18
19
20
TM
In 'F
i
l
i
i
i
i
i
i
/-
7
j^
•)
6.
Jnb
6
£>
$
6
£
#
%
O
L
o
0
5
/
"L
/
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0
23
24
25
TM
Out *F
t
i
i
i
j
1
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jf
c
6
f
£
^
7
<5
5
/
6'
f
7
C)
t
f
0
L
i
26
27 28
29
30
PSTACK
In H20
f
': '
(
-
4
•
—
'
—
(
I
,^
(
»
3
i •
i —
^
s
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32
33
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-------
APPENDIX C
SAMPLING AND ANALYSIS PROCEDURES
Includes:
C.I Urea Procedures
C.2 Ammonia Procedures
C.3 Formaldehyde Procedures
-------
APPENDIX C.I
UREA PROCEDURES
-------
APPENDIX A - REFERENCE TEST METHOD
METHOD 28 - DETERMINATION OF PARTICULATE (UREA)
EMISSIONS FROM UREA PLANTS
1.' Applicability and Principle
1.1 Applicability. This method applies to the determination of
particulate emissions as urea from urea manufacturing facilities.
1.2 Principle. A gas sample is extracted isokinetically from
the stack. The ammonia is removed from the sample by boiling, and
the particulate emissions are determined as urea by a colorimetric
procedure.
••— M
2. Apparatus -
2.1 Sampling Train. A schematic of the sampling train used in
this method 1s shown in Figure 28-1; it is similar in construction to
Method 5. The sampling train consists of the following components.
2.1.1 Probe Nozzle, Probe Liner, Pitot Tube, Differential
Pressure Gauge, Metering System, and Barometer. Same as Method 5,
sections 2.1.1, 2.1.2, 2.1.3, 2.1.4, 2.1.8, and 2.1.9 respectively.
Stainless steel probe liners may also be used.
2.1.2 Impingers. Five impingers connected in series as shown
in Figure 28-1. For the second and third impinger, the tester shall
use the Greenburg-Smith design with standard tips. For the first,
fourth, and fifth impingers, the tester may use the Greenburg-Smith
design, modified by replacing the tips with a 1.25 cm (0.5 in.) ID
-------
glass tube extending to 1.25 cm (0.5'in.) from the bottom of the
flask. Similar collection systems, which have been approved by
the Administrator, may be used.
2.2 Sample Recovery. The following equipment is needed:
2.2.1 Probe-Uner and Probe-Nozzle Brushes, Graduated Cylinder
and/or Balance, Plastic Storage Containers, and Rubber Policeman.
Same as Method 5, sections 2.2.1, 2.2.5, 2.2.6, 2.2.7, respectively.
2.2.2 Wash Bottles. Glass wash bottles are recommended;
polyethylene wash bottles may be used at the option of the tester.
2.2.3 Sample Storage Containers. Chemically resistant,
borosllicate glass bottles, 500-ml or 1000-ml. Screw cap liners
shall either be rubber-backed Teflon or shall be constructed so as
to be leak-free. (Narrow mouth glass bottles have been found to be
less prone to leakage). Alternatively, polyethylene bottles may
be used.
2.2.4 Funnel. Glass or Polyethylene.
2.3 Analysis. For analysis, the following equipment is needed.
2.3.1 Pipettes. Volumetric type, 0.5-ml, 2-ml, 5-ml, 8-ml,
10-ml, 20-ml, and. 25-ml.
2.3.2 Volumetric Flasks. 25-ml, 100-ml, 250-ml, 500-ml, and
1000-ml.
2.3.3 Graduated Cylinder. 100-ml.
. 2.3.4 Distillation Apparatus.
2.3.4.1 Flasks or Beakers. At least two, 800-ml.
2.3.4.2 Hot Plate. Capable of heating the distillation flasks
to 120°C (248°F).
-------
~\
2.3.5 Spectrophotometer. To measure absorbance at 420
nanometers.
2.3.6 Sample Cells. Two matched absorbance cells to fit
the Spectrophotometer.
3. Reagents
Use ACS reagent-grade chemicals or equivalent, unless
otherwise specified.
3.1 Sampling and Sample Recovery. The reagents used in
sampling and sample recovery are as follows:
. 3.1.1 Silica Gel, Crushed Ice, and Stopcock Grease. Same
as Method 5, sections 3.1.2, 3.1.4, 3.1.5, respectively.
. 3.1.2 Water. Deionized distilled to conform to ASTM
specification D 1193-74, type 3. At the option of the analyst,
the KMNO, test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be
present. .
.3.1.3 Sulfuric Acid, 1 N. Slowly add 28 ml of concentrated
sulfuric acid to 800 ml of deionized distilled water in a 1-liter
flask and dilute to exactly 1 liter with deionized distilled water.
3.2 Analysis. The reagents need for analysis are listed
below*.
3,2.1 Water. Same as 3.1.2.
3.2.2 Sodium Hydroxide (NaOH), 10 N. Dissolve 40 g of NaOH
in a 100-ml volumetric flask and dilute to exactly 100 ml with
deionized distilled water.
-------
3.2.3 Sodium Hydroxide 6 N. Dissolve 240 g of NaOH in 800 ml
of deionized distilled water in a 1-liter flask. Dilute to exactly
1 liter with deionized distilled water.
3.2.4 Sodium Hydroxide, 1 N. Dissolve 40 g of NaOH in 800 ml
of deionized distilled water in a 1-liter flask and dilute to exactly
•
1 liter with deionized distilled water.
3.2.5 Sodium Hydroxide, 0.1 N. Dilute 100 ml of 1 N NaOH to
exactly 1 liter with deionized distilled water.
3.2.6 Borate Buffer. Dissolve 2.5 g of sodium tetraborate
CNagB^Oy) or 4.8 g of the decahydrate (Na^Oy . 10 H20) in 500 ml
of detonized distilled water in a 1-liter volumetric flask. Add 88 ml
of 0.1 N NaOH solution, and dilute to exactly 1 liter with deionized
distilled water. , . .
~*" *i
3.3.7 Sulfuric Acid,.! N. Same as 3.1.3.
3.3.8 Ethyl Alcohol, 95 percent.
3.3.9 p-dimethylaminobenzaldehyde.
3.3.10 Hydrochloric Acid, Concentrated.
3.3.11 Urea Solution, 2.5 mg/ml. Dissolve 2.500 g of urea in
500 ml of deionized distilled water in a 1-liter flask and dilute to
exactly 1 liter with deionized distilled water.
3.3.12 Urea Color Reagent. Dissolve 2.000 g of
p-dimethylaminobenzaldehyde in a mixture of 100 ml of 95 percent
ethyl alcohol and 10 ml of concentrated hydrochloric acid.
-------
4. Procedure
4.1 Sampling. Because of the complexity of this method,
testers should be trained and experienced with the test procedure
to insure reliable results.
4.1.1 Pretest Preparation. Follow the general procedure given
in Method 5, section 4.1.1, except omit the directions for the filter.
4.1.2 Preliminary Determinations. Follow the general procedure
given in Method 5, section 4.1.2.
4.1.3 Preparation of Sampling Train. Follow the general
procedure given in Method 5, section 4.1.3, except place 100 ml of
deionized distilled water in each of the first three impingers, place
100 ml of 1 N H2S04 in the fourth impinger, and place the preweighed
silica gel in the fifth impinger. Assemble the train as shown in
Figure 28-1. : '
4.1.4 Leak Check Procedures. Follow the leak-check procedures
given in Method 5, sections 4.1.4.1 (Pretest Leak Check), 4.1.4.2
(Leak-Check During Sampling Run) and 4.1.4.3 (Post-Test Leak-Check).
4.1.5 Sampling Training Operation. Follow the general procedure
given in Method 5, section 4.1.5. For each run, record the data
required on a data sheet such as the one shown in Method 5, Figure 5-2.
4.1.6 Calculation of Percent Isokinetic. Same as Method 5,
section 4.1.6.
4.2 Sample Recovery. Begin proper cleanup procedure as soon
as the probe is removed from the stack at the end of the sampling
period. Allow the probe to cool.
-------
When the probe can be safely handled, wipe off all external
participate matter near the tip of the probe nozzle, and place a
cap over it to prevent losing or gaining participate matter. Do
not cap off the probe tip tightly while the sampling train is
cooling down as this would create a vacuum, thus drawing water from
the impingers into the probe. •
Before moving the sampling train to the cleanup site, remove
the probe from the sample train, wipe off the silicone grease, and
cap the open outlet of the probe. Be careful not to lose any
condensate that might be present. Wipe off the silicone grease from
the impinger inlet where the probe was fastened and cap it. Remove
the umbilical cord from the last impinger and cap the.impinger.. If
a flexible line is used between the first impinger or condenser and
the probe, disconnect the line at the probe and let any condensed
water or liquid drain into the impingers or condenser. Either
ground-glass stoppers, plastic caps, or serum caps may be used to
close these openings.
Transfer the probe-impinger assembly to the cleanup area. This
area should be clean and protected from the wind so that the chances
of contaminating or losing the sample will be minimized.
Inspect the train prior to and during disassembly and note any
abnormal conditions. Treat the samples as follows:
4.2.1 Container No. 1. Taking care to see that dust on the
outside of the probe or other exterior surfaces does not get into
the sample, quantitatively recover particulate matter or any condensate
from the probe nozzle, probe fitting, and probe liner, by washing
-------
these components with water and placing the wash in a glass
container. Perform the water rinses as follows:
Carefully remove the probe nozzle and clean the inside surface
by rinsing with water from a wash bottle and brushing with a Nylon
bristle brush. Brush until the water rinse shows no visible
particles, after which make a final rinse of the inside surface
with water.
Brush and rinse the inside parts of the Swagelok fitting with
water in a similar way until no visible particles remain.
Rinse the probe liner with water by tilting and rotating the
probe while squirting water into its upper end so that all inside
surfaces will be wetted with water. Let the v/ater drain from the
lower end into the-sample container. A funnel (glass or polyethylene)
may be used to aid in transferring liquid washes to the container.
Follow the water rinse with, a probe brush. Hold the probe in an
inclined position, squirt water into the upper end as the probe
brush is being pushed with a twisting action through the probe;
hold a sample container underneath the lower end of the probe, and
catch any water and particulate matter which is brushed from the
probe. Run the brush through the probe three times or more until
no visible particulate matter is carried out with the water or
until none remains in the probe liner on visual inspection. With
stainless steel or other metal probes, run the brush through in
the above prescribed manner at least six times since metal probes
have small crevices in which particulate matter can be entrapped.
-------
Rinse the brush with water, and quantitatively collect these
washings in the sample container. After brushing, make a final
water rinse of the probe as described above.
It is recommended that two people clean the probe to minimize
sample losses. Between sampling runs, keep brushes clean and
protected from contamination.
4.2.2 Container No. 2. Mark the liquid level of the container
to determine later if leakage occurred during shipment. Cap and
seal the containers and identify. Measure to the nearest j^l ml and
record the volume of the first three impingers. Then transfer the
contents to the container. Rinse the first three impingers and the
connecting glassware with water, and add the rinse water to the
container. Mark the level of the liquid on the container and identify
the sample container.
4.2.3 Impinger No. 4. Measure to the nearest +_ 1 ml and record
the volume of the fourth impinger. Discard the liquid.
4.2.4' Container No. 3. Note the color of the indicating silica
gel to determine if it has been completely spent and make a notation
of its condition. Transfer the silica gel from the fifth impinger
to its original container and seal. The tester may use a funnel
and rubber policeman as aids in transferring the silica gel. It is
not necessary to remove the small amount of dust particles that may
adhere to the impinger wall and are difficult to remove. Since the
gain in weight is to be used for moisture calculations, do not use
any water or other liquids to transfer the silica gel. If a balance
-------
is available in the field, the tester may follow the procedure for
container No. 3 in section 4.3.2. •
4.2.5 Water Blank. Save a portion of the deionized distilled
water used for cleanup as a blank. Take 200 ml of this water directly
from the wash bottle being used and place it in a glass sample
container labeled "water blank."
4.3 Analysis. Record the data required on a sheet such as the .
one shown in Figure 5-3 of Method 5. Handle each sample container
as follows:
4.3.T 'Containers No. 1 and 2. Note the level of liquid and
confirm on the analysis sheet whether or not leakage occurred during
transport. If a noticeable amount of leakage has occurred, either
void the sample or use methods, subject to the approval of the
,Administrator, to correct the final results. Measure the liquid
either yolumetrically to t_ 1 ml or gravimetrically to +_0.5 g, and
record on the data sheet. Combine the contents of both containers
in a 500-ml volumetric flask, and dilute to exactly 500 ml with
deionized distilled water. Distill the sample following the
procedure in 4.3.4.
4.3.2 Container No: 3. Weigh the spent silica gel (or silica
gel plus impinger) to the nearest 0.5 g using'a balance. This step
may be conducted in the field.
-------
4.3.3 "Water Blank" Container. Measure water in this
container either volumetrically or gravimetrically and record on
the data sheet. Distill the sample following the procedure in
4.3.4.
4.3.4.1 Preparation of Sample. Pipette a 100-ml aliquot
of sample into a 1-lfter flask or beaker, and add 400 ml of
deionized distilled water. Then add 25 ml of borate buffer, and
adjust the pH to 9.5 with 6N NaOH using short-range pH paper to
measure the pH. Heat the flask to boiling and boil until the
volume is reduced to about 75 ml. (Caution: Conduct this step
under a hood.} Transfer the remaining sample to a 100-ml
volumetric flask and dilute to exactly 100 ml with deionized
distilled water. "
4,3.4.2 Analysis. Treat the sample and blank as follows:
Pipette 10 ml into a 25-ml volumetric flask and add 10 ml of the
urea color reagent. Dilute to exactly 25 ml with deionized
distilled water. Mix well and allow to stand for at least
10 minutes for full color development. Measure the absorbance of
the solution of 420 nm using the blank solution as a zero reference.
If the absorbance exceeds that of the 5.00-yg/ml urea standard,
prepare another sample using less than a 10-ml aliquot.
5.''Calibrations
5.1 Sampling Train. Calibrate the sampling train components
according to the indicated section of Method 5. Probe Nozzle (5.1);
-------
Pi tot Tube (5.2); Metering System (5.3); Temperature Gauge (5.5);
Leak-Check of the Metering System (5.6); and Barometer (5.7).
5.2 Determination of Spectrophotometer Calibration Factor K.
Add 0.0, 1.0, 5.0, 10.0, 15.0, 20.0 and 25.0 ml of the standard urea
solution to a series of six 250-ml volumetric flasks. Then follow
the distillation and analysis procedures described for the samples
in section 4.3.4 of this method. Each standard at the time of
analysis will contain 0, 0.100, 0.500, 1.00, 1.50, 2.00, and 2.50 mg
respectively. The calibration procedure must be repeated each day
that samples are analyzed. Calculate the Spectrophotometer calibration
factor as follows:
A, + 5A, + IDA, + ISA. + 20A, + 25A
K - 0.100 ] 2 3
+ A22 + A3
Where:
K = Calibration factor.
A, = Absorbance of the 0.100 mg standard.
A2 = Absorbance of the 0.500 mg standard.
A, = Absorbance of the 1.00 mg standard.
*3
A- 3 Absorbance of the 1.50 mg standard.
Ac 3 Absorbance of the 2.0 mg standard.
Ac ° Absorbance of the 2.50 mg standard.
-------
6. Calculations
"6.1 Average Dry Gas Meter Temperature and Average Orifice
Pressure Drop, Dry Gas Volume, Volume of Water Vapor, Moisture
Content, Isokinetic Variation, and Acceptable Results. Using
data from this test, same as Method 5, sections 6.2, 6.3, 6.4,
6.5, 6.11, and 6.12 respectively.
6.2 Mass of.Urea. Calculate the total weight of urea
collected in the sample by Equation 28-1.
Kc
Where:
m = Mass of urea collected, mg.
K - = Spectrophotometer calibration factor.
A - Absorbance of sample.
A « Absorbance of the water blank.
Yai a- Volume of sample aliquot analyzed, ml.
V 0-. a Total volume of solution in which the sample is
contained, ml.
6,3 particulate Concentration: Calculate the particulate
(urea), concentration as follows:
m(std)
. 28-2
-------
Where:
c = Particulate (urea) concentration at dry
standard conditions, g/dscm (gr/dscf).
m = Mass of urea collected, g.
^m(std) a Vo^ume °^ gas samPTfi measured by dry gas meter,
corrected to standard conditions, dscm (dscf).
Kg =1.0 for metric units.
= 0.4370 for English units.
7.' Bibliography
1. American Public Health Association. Standards Methods for
the Examination of Water and Wastewater, 13th Edition.
Washington, D.C. 1974. pp. 226-232.
2. Watt, George W. and Joseph D. Chrisp. Spectrophotometric
. - .»- • •>» • • •
Method for Determination of. Urea. Analytical Chemistry. 2£:452-453.
1954.
3. Same as Method 5, Citation 1 through 9 of section 7.
-------
4 OJI-
NITROGEN, KJELDAHL, TOTAL
Method 351.3 (Colorimetric; Titrimetric; Potentiometric)
STORET NO. 00625
1. Scope and Application
M This method covers the determination of total Kjeldahl nitrogen in drinking, surface and
saline waters, domestic and industrial wastes. The procedure converts nitrogen
components of biological origin such as amino acids, proteins and peptides to ammonia,
but may not convert the nitrogenous compounds of some industrial wastes such as
amines, nitro compounds, hydrazones, oximes, semicarbazones and some refractory
tertiary amines.
1.2 Three alternatives are listed for the determination of ammonia after distillation: the
titrimetric method which is applicable to concentrations above 1 mg N/liter, the
Nesslerization method which is applicable to concentrations below 1 mg N/liter; and the
potentiometric method applicable to the range 0.05 to 1400 mg/1.
1 .3 This method is described for macro and micro glassware systems.
2. Definitions "
2.1 Total Kjeldahl nitrogen is defined as the sum of free-ammonia and organic nitrogen
compounds which are converted to ammonium sulfate (NH4)2SO4, under the conditions
of digestion described below.
2.2 Organic Kjeldahl nitrogen is defined as the difference obtained by subtracting the free-
ammonia value (Method 350.2, Nitrogen, Ammonia, this manual) from the total
Kjeldahl nitrogen value. This may be determined directly by removal of ammonia before
digestion.
3. Summary of Method
3.1 The sample is heated in the presence of cone, sulfuric acid, K2SO4 and HgSO4 and
evaporated until SO3 fumes are obtained and the solution becomes colorless or pale
yellow. The residue is cooled, diluted, and is treated and made alkaline with a hydroxide-
thiosulfate solution. The ammonia is distilled and determined after distillation by
Nesslerization, titration or potentiometry.
4. Sample Handling and Preservation
4.1 Samples may be preserved by addition of 2 ml of cone. H2SO4 per liter and stored at 4°C.
Even when preserved in this manner, conversion of organic nitrogen to ammonia may
occur. Preserved samples should be analyzed as soon as possible.
5. Interference
5.1 High nitrate concentrations (10X or more than the TKN level) result in low TKN
values. The reaction between nitrate and ammonia can be prevented by the use of an
anion exchange resin (chloride form) to remove the nitrate prior to the TKN analysis.
Approved for NPDES
Issued 1971
Editorial revision 1974 and 1978
351.3-1
-------
6. Apparatus
6.1 Digestion apparatus: A Kjeldahl digestion apparatus with 800 or 100 ml flasks and
suction takeoff to remove SO3 fumes and water.
6.2 Distillation apparatus: The macro Kjeldahl flask is connected to a condenser and an
adaptor so that the distillate can be collected. Micro Kjeldahl steam distillation
apparatus is commercially available.
6.3 Spectrophotometer for use at 400 to 425 nm with a light path of 1 cm or longer.
7. Reagents ' .
7.1 Distilled water should be free of ammonia. Such water is best prepared by the passage of
distilled water through an ion exchange column containing a strongly acidic cation
.exchange resin mixed with a strongly basic anion exchange resin. Regeneration of the
column should be carried out according to the manufacturer's instructions.
NOTE 1: All solutions must be made with ammonia-free water.
7.2 Mercuric sulfate solution: Dissolve 8 g red mercuric oxide (HgO) in 50 ml of 1:4 sulfuric
acid (10.0 ml cone. H2SO4 : 40 ml distilled water) and dilute to 100 ml with distilled
water".
7.3 Sulfuric acid-mercuric sulfate-potassium sulfate solution: Dissolve 267 g K2SO« in 1300
ml distilled water and 400 ml cone. H2SO4. Add 50 ml mercuric sulfate solution (7.2) and
dilute to 2 liters with distilled water.
7.4 Sodium hydroxide-sodium thiosulfate solution: Dissolve 500 g NaOH and 25 g
Na2S2O3»5H:O in distilled water and dilute to 1 liter.
7.5 Mixed indicator: Mix 2 volumes of 0.2% methyl red in 95% ethanol with 1 volume of
0.2% methylene blue in ethanol. Prepare fresh every 30 days.
7.6 Boric acid solution: Dissolve 20 g boric acid, H3BO3, in water and dilute to 1 liter with
distilled water.
7.7 Sulfuric acid, standard solution: (0.02 N) 1 ml = 0.28 mg NH3-N. Prepare a stock
solution of approximately 0.1 N acid by diluting 3 ml of cone. H2SO4 (sp. gr. 1.84) to 1
liter with CO2-free distilled water. Dilute 200 ml of this solution to 1 liter with CO2-free
distilled water. Standardize the approximately 0.02 N acid so prepared against 0.0200 N
Na2CO3 solution. This last solution is prepared by dissolving 1.060 g anhydrous Na2CO3,
oven-dried at 140*C, and diluting to 1 liter with CO2-free distilled water.
NOTE 2: An alternate and perhaps preferable method is to standardize the
approximately 0.1 N H2SO4 solution against a 0.100 N Na2CO3 solution. By proper
dilution the 0.02 N acid can the be prepared.
7.8 Ammonium chloride, stock solution: 1.0 ml = 1.0 mg NHr-N- Dissolve 3.819 g NH4C1
in water and make up to 1 liter in a volumetric flask with distilled water.
7.9 Ammonium chloride, standard solution: 1.0 ml = 0.01 mg NHj-N. Dilute 10.0 ml of the
stock solution (7.8) with distilled water to 1 liter in a volumetric flask.
7.10 Nessler reagent: Dissolve 100 g of mercuric iodide and 70 g potassium iodide in a small
volume-of distilled water. Add this mixture slowly, with stirring, to a cooled solution of
160 g of NaOH in 500 ml of distilled water. Dilute the mixture to 1 liter. The solution is
stablefor at least one year if stored in a pyrex bottle out of direct sunlight
351.3-2
-------
NOTE 3: Reagents 7.7, 7.8, 7.9, and 7.10 are identical to reagents 6.8, 6.2, 6.3, and 6.6
described under Nitrogen, Ammonia (Colorimetric; Titrimetric; Potentiometric-
Distillation Procedure, Method 350.2).
8. Procedure
8.1 The distillation apparatus should be pre-steamed before use by distilling a 1:1 mixture of
distilled water and sodium hydroxide-sodium thiosulfate solution (7.4) until the distillate
is ammonia-free. This operation should be repeated each time the apparatus is out of
service long enough to accumulate ammonia (usually 4 hours or more).
8.2 Macro Kjeldahl system
8.2.1 Place a measured sample or the residue from the distillation in the ammonia
determination (for Organic Kjeldahl only) into an 800 ml Kjeldahl flask. The
sample size can be determined from the following table:
Kjeldahl Niirogen Sample Size
in Sample, mg/1 ml
0-5 ' 500 .
5-10 , 250
10-20 100
20-50 50.0
50-500 . 25.0
Dilute the sample, if required, to 500 ml with distilled water, and add 100 ml
suifuric acid-mercuric sulfate-potassium sulfate solution (7.3). Evaporate the
mixture in the Kjeldahl apparatus until SO3 fumes are given off and the solution
. turns colorless or pale yellow. Continue heating for 30 additional minutes. Cool the
residue and add 300 ml distilled water.
8.2.2 Make the digestate alkaline by careful addition of 100 mi of sodium hydroxide -
thiosulfate solution (7.4) without mixing.
NOTE 5: Slow addition of the heavy caustic solution down the tilted neck of the
digestion flask will cause heavier solution to underlay the aqueous suifuric acid
solution without loss of free-ammonia. Do not mix until the digestion flask has
been connected to the distillation apparatus.
8.2.3 Connect the Kjeldahl flask to the condenser with the tip of condenser or an
extension of the condenser tip below the level of the boric acid solution. (7.6) in the
receiving flask.
8.2.4 Distill 300 ml at the rate of 6-10 ml/min., into 50 ml of 2% boric acid (7.6)
contained in a 500 ml Erlenmeyer flask.
8.2.5 Dilute the distillate to 500 ml in the flask. These flasks should be marked at the 350
and the 500 ml volumes. With such marking, it is not necessary to transfer the
distillate to volumetric flasks. For concentrations above 1 mg/1, the ammonia can
be determined titrimetrically. For concentrations below this value, it is determined
colorimetrically. The potentiometric method is applicable to the range 0.05 to 1400
. - mg/1.
351.3-3
-------
8.3 Micro Kjeldahl system
8.3.1 Place 50.0 ml of sample or an aliquot diluted to 50 ml in a 100 ml Kjeldahl flask
and add 10 ml sulfuric acid-mercuric sulfate-potassium sulfate solution (7.3).
Evaporate the mixture in the Kjeldahl apparatus until SO3 fumes are given off and
the solution turns colorless or pale yellow. Then digest for an additional 30
minutes. Cool the residue and add 30 ml distilled water.
8.3.2 Make the digestate alkaline by careful addition of 10 ml of sodium hydroxide-
thiosulfate solution (7.4) without mixing. Do not mix until the digestion flask has
been connected to the distillation apparatus.
8.3.3 Connect the Kjeldahl flask to the condenser with the tip of condenser or an
extension of the condenser tip below the level of the boric acid solution (7.6) in the
receiving flask or 50 ml short-form Nessler tube.
8.3.4 Steam distill 30 ml at the rate of 6-10 ml/min., into 5 ml of 2% boric acid (7.6).
8.3.5 Dilute the distillate to 50 ml. For concentrations above 1 mg/1 the ammonia can be
determined titrimetrically. For concentrations below this value, it is determined
colorimetrically. The potentiometric method is applicable to the range 0.05 to 1400
mg/1.
8.4 Determination of ammonia in distillate: Determine the ammonia content of the distillate
titrimetrically, colorimetrically, or potentiometrically, as described below.
8.4.1 Titrimetric determination: Add 3 drops of the mixed indicator (7.5) to the distillate
and titrate the ammonia with the 0.02 N H2SO4 (7.7), matching the endpoint
against a blank containing the same volume of distilled water and H3BO3 (7.6)
solution.
8.4.2 Colorimetric determination: Prepare a series of Nessler tube standards as follows:
ml of Standard
1.0 ml = 0.01 mg NH3-N mg NH3-N/50.0 ml
0.0 0.0
0.5 . 0.005
1.0 0.010
2.0 0.020
4.0 0.040
5.0 0.050
8.0 0.080
10.0 0.10
Dilute each tube to 50 ml with ammonia free water, add 1 ml of Nessler Reagent
(7.10) and mix. After 20 minutes read the absorbance at 425 nm against the blank.
From the values obtained for the standards plot absorbance vs. mg NH3-N for the
standard curve. Develop color in the 50 ml diluted distillate in exactly the same
manner and read mg NH3-N from the standard curve.
. 8.4.3 Potentiometric determination: Consult the method entitled Nitrogen, Ammonia:
Potentiometric, Ion Selective Electrode Method, (Method 350.3) in this manual.
8.4.4 It is not imperative that all standards be treated in the same manner as the samples.
It is recommended that at least 2 standards (a high and low) be digested, distilled,
351.3-4
-------
and compared to similar values on the curve to insure that the digestion-distillation
technique is reliable. If treated standards do not agree with untreated standards the
operator should find the cause of the apparent error before proceeding.
9. Calculation
9.1 If the titrimetric procedure is used, calculate Total Kjeldahl Nitrogen, in mg/1, in the
original sample as follows:
TKN, mg/1 = (A - B)N x F x 1,000
where:
A = milliliters of standard 0.020 N H2SO4 solution used in titrating sample.
B = milliliters of standard 0.020 N H2SO4 solution used in titrating blank.
N = normality of sulfuric acid solution.
F = milliequivalent weight of nitrogen (14 mg).
S = milliliters of sample digested. ' . -
If the sulfuric acid is exactly 0.02 N the formula is shortened to:
TVV. n (A - B) x 280
TKN, mg/1 = - 5
9.2 If the Nessler procedure is used, calculate the Total Kjeldahl Nitrogen, in mg/1, in the
original sample as follows:
_,XT _ Ax 1,000 B
TKN , mg/1 - - - x --
where:
A = mg NH3-:N read from curve.
B = ml total distillate collected including the H3BO3.
C = ml distillate taken for Nesslerization.
D = ml of original sample taken.
9.3 Calculate Organic Kjeldahl Nitrogen in mg/1, as follows:
Organic Kjeldahl Nitrogen = TKN -
-------
9.4 Potentiometric determination: Calculate Total KjeldahJ Nitrogen, in mg/1, in the
original sample as follows:
TKN, mg/1 = -I x A
where:
ta»
A = mg NHj-N/1 from electrode method standard curve.
B = volume of diluted distillate in ml.
D = ml of original sample taken.
10. Precision
10.1 Thirty-one analysts in twenty laboratories analyzed natural water samples containing
exact increments of organic nitrogen, with the following results:
Increment as
Nitrogen, Kjeldahl
mg N/liter
0.20
0.31
s 4.10
4.61 '
Precision as
Standard Deviation
mg N/liter
0.197
0.247
1.056
1.191
Accuracy as
Bias,
+ 15.54
+ 5.45
+ 1.03
- 1.67
mg N/liter
+0.03
+0.02
+0.04
-0.08
(FWPCA Method Study 2, Nutrient Analyses)
Bibliography
1. Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 437,
Method 421 (1975).
2. Schlueter, Albert, "Nitrate Interference In Total Kjeldahl Nitrogen Determinations and Its
Removal by Anion Exchange Resins", EPA Report 600/7-77-017.
351.3-6
-------
APPENDIX C.2
AMMONIA PROCEDURES
-------
U>rjJ
-------
5. Apparatus
5.1 An all-glass distilling apparatus with an 800-1000 ml flask.
5.2 Spectrophotometer or filter photometer for use at 425 nm and providing a light path of 1
cm or more.
5.3 Nessler tubes: Matched Nessler tubes (APHA Standard) about 300 mm long, 17 mm
inside diameter, and marked at 225 mm ±1.5 mm inside measurement from bottom.
5.4 Erlenmeyer flasks: The distillate is collected in 500 ml glass-stoppered flasks. These
flasks should be marked at the 350 and the 500 ml volumes. With such marking, it is not
necessary to transfer the distillate to volumetric flasks.
6. Reagents
6.1 Distilled water should be free of ammonia. Such water is best prepared by passage
through an ion exchange column containing a strongly acidic cation exchange resin
mixed with a strongly basic anion exchange resin. Regeneration of the column should be
carried out according to the manufacturer's instructions.
NOTE 1: All solutions must be made with ammonia-free water.
6.2 Ammonium chloride, stock solution: 1.0 ml = 1.0 mg NH3-N. Dissolve 3.819 g NH4C1
in distilled water and bring to volume in a 1 liter volumetric flask.
6.3 Ammonium chloride, standard solution: 1.0 ml = 0.01 mg. Dilute 10.0 ml of stock
solution (6.2) to 1 liter in a volumetric flask.
6.4 Boric acid solution (20 g/1): Dissolve 20 g H3BO3 in distilled water and dilute to 1 liter.
6.5 Mixed indicator: Mix 2 volumes of 0.2% methyl red in 95% ethyl alcohol with 1 volume
of 0.2% methylene blue in 95% ethyl alcohol. This solution should be prepared fresh
every 30 days.
NOTE 2: Specially denatured ethyl alcohol conforming to Formula 3 A or 30 of the U.S.
Bureau of Internal Revenue may be substituted for 95% ethanol.
6.6 Nessler reagent: Dissolve 100 g of mercuric iodide and 70 g of potassium iodide in a small
amount of water. Add this mixture slowly, with stirring, to a cooled solution of 160 g of
NaOH in 500 ml of water. Dilute the mixture to 1 liter. If this reagent is stored in a Pyrex
bottle out of direct sunlight, it will remain stable for a period of up to 1 year.
NOTE 3: This reagent should give the characteristic color with ammonia within 10
minutes after addition, and should not produce a precipitate with small amounts of
ammonia (0.04 mg in a 50 ml volume).
6.7 Borate buffer: Add 88 ml of 0.1 N NaOH solution to 500 ml of 0.025 M sodium
tetraborate solution (5.0 g anhydrous Na2B«O7 or 9.5 g Na2B4O,»10H2O per liter) and
dilute to 1 liter.
6.8 Sulfuric acid, standard solution: (0.02 N, 1 ml = 0.28 mg NH3-N). Prepare a stock
solution of approximately 0.1 N acid by diluting 3 ml of cone. H2SO4 (sp. gr. 1.84) to 1
liter with CO2-free distilled water. Dilute 200 ml of this solution to 1 liter with CO2-free
distilled water.
NOTE 4: An alternate and perhaps preferable method is to standardize the
approximately 0.1 N H2SO4 solution against a 0.100 N Na2CO3 solution. By proper
dilution the 0.02 N acid can then be prepared.
350.2-2
-------
6.8.1 Standardize the approximately 0.02 N acid against 0.0200 N Na:CO3 solution.
This last solution is prepared by dissolving 1.060 g anhydrous Na:CO3( oven-dried
at 140°C, and diluting to 1000 ml with CO,-free distilled water.
6.9 Sodium hydroxide, 1 N: Dissolve 40 g NaOH in ammonia-free water and dilute to 1 liter.
6.10 Dechlorinating reagents: A number of dechlorinating reagents may be used to remove
residual chlorine prior to distillation. These include:
a. Sodium thiosulfate (1/70 N): Dissolve 3.5 g Na2S2O3»5H2O in distilled water and
dilute to 1 liter. One ml of this solution will remove 1 mg/1 of residua] chlorine in
500 ml of sample.
b. Sodium arsenite (1/70 N): Dissolve 1.0 g NaAsO2 in distilled water and dilute to 1
liter.
7. Procedure
7.1 Preparation of equipment: Add 500 ml of distilled water to an 800 ml Kjeldahl flask. The
addition of boiling chips which have been previously treated with dilute NaOH will
prevent bumping. Steam out the distillation apparatus until the distillate shows no trace
of ammonia with Nessler reagent.
7.2 Sample preparation: Remove the residual chlorine in the sample by adding
dechlorinating agent equivalent to the chlorineVesidual. To 400 ml of sample add 1 N
NaOH (6.9), until the pH is 9.5, checking the pH during addition with a pH meter or by
use of a short range pH paper.
7.3 Distillation: Transfer the sample, the pH of which has been adjusted to 9.5, to an 800 ml
Kjeldahl flask and add 25 ml of the borate buffer (6.7). Distill 300 ml at the rate of 6-10
ml/min. into 50 ml of 2% boric acid (6.4) contained in a 500 ml Erlenmeyer flask.
NOTE 5: The condenser tip or an extension of the condenser tip must extend below the
level of the boric acid solution-
Dilute the distillate to 500 ml with distilled water and nesslerize an aliquot to obtain an
approximate value of the ammonia-nitrogen concentration. For concentrations above 1
mg/1 the ammonia should be determined titrimetrically. For concentrations below this
value it is determined colorimetrically. The electrode method may also be used.
7.4 Determination of ammonia in distillate: Determine the ammonia content of the distillate
titrimetrically, colorimetrically or potentiometrically as described below.
7.4.1 Titrimetric determination: Add 3 drops of the mixed indicator to the distillate and
titrate the ammonia with the 0.02 N H2SO4, matching the end point against a blank
containing the same volume of distilled water and H3BO3 solution.
350.2-3
-------
7.4.2 Colorimetric determination: Prepare a series of Nessler tube standards as follows:
ml of Standard
1.0 ml = 0.01 mg NHj-N . mg NH3-N/50.0 ml
0.0 0.0
0.5 0.005
1.0 0.01
2.0 0.02
3.0 0.03
4.0 0.04
5.0 0.05
8.0 . 0.08
10.0 ' • 0.10
Dilute each tube to 50 ml with distilled water, add 2.0 ml of Nessler reagent (6.6)
and mix. After 20 minutes read the absorbance at 425 nm against the blank. From
the values obtained plot absorbance vs. mg NH3-N for the standard curve.
Determine the ammonia in the distillate by nesslerizing 50 ml or an aliquot diluted
to 50 ml and reading the absorbance at 425 nm as described above for the
standards. Ammonia-nitrogen content is read from the standard curve.
7.4.3 Potentiometric determination: Consult the method entitled Nitrogen, Ammonia:
Selective Ion Electrode Method (Method 350.3) in this manual.
7.5 It is not imperative that all standards be distilled in the same manner as the samples. It is
recommended that at least two standards (a high and low) be distilled and compared to
similar values on the curve to insure that the distillation technique is reliable. If distilled
standards do not agree with undistilled standards the operator should find the cause of
the apparent error before proceeding.
8. Calculations
8.1 Titrimetric
/i viu vi Ax 0.28 x 1,000
mg/1 NHj - N = 5 •
where:
A = ml 0.02 N H2SO4 used.
S = ml sample.
8.2 Spectrophotometric
mg/1 NHj - N = A_x^000 x B.
where:
A = mg NH3-N read from standard curve.
B = ml total distillate collected, including boric acid and dilution.
C = ml distillate taken for nesslerization.
D = ml of original sample taken.
350.2-4
-------
8.3 Potentiometric
mg/t NH, - N =
500
D
xA
where:
A = mg NHj-N/1 from electrode method standard curve.
D = ml of original sample taken.
9. Precision and Accuracy
9.1 Twenty-four analysts in sixteen laboratories analyzed natural water samples containing
exact increments of an ammonium salt, with the following results:
Increment as
Nitrogen, Ammonia
mg N/liter
0.21
0.26
1.71
1.92
Precision as
Standard Deviation
mgN/liter
0.122
0.070
0.244
0.279
Accuracy as
Bias,
-5.54
-18.12
+0.46
-2.01
Bias,
mg N/liter
-0.01 ^
-0.05
+0.01
-0.04
(FWPCA Method Study 2, Nutrient Analyses)
Bibliography
1. Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 410,
Method 4ISA and 418B (1975).
2. Annual Book of ASTM Standards, Part 31, "Water", Standard D1426-74, Method A, p .237
(1976).
350.2-5
-------
APPENDIX C.3
FORMALDEHYDE PROCEDURES
-------
,?AFT *-"•
TENTATIVE METHOD FOR [)(j [JQT" Q[JQT£ QR £{!£
ISOKINETIC DETERMINATION OF POLLUTANT LEVELS
IH THE EFFLUENT OF FORMALDEHYDE MANUFACTURING FACILITIES
1." Principle:
1.1 General: An air sample is drawn isokixietically through an
impinger train containing water as the scrubbing medium. Formaldehyde
methanol and dimethyl ether are scrubbed from the pas. A jgiass bomb
is conuBCtoci-frftei I!lia su"UL'biiitr->ffip4fK!erG e^d—bef-ere—fehe-s-H-fcg-oel
irs-tnay Le'CD'T
1.2 Formaldehyde: The analysis consists of reacting an aliquot
of the impinoer solution with chremotropic - sulfuric acid reagent to
form a purple cnrornogen. This resulting solution is analyzed colorime-
trically using a spectrophotometer at 580 nm; the absorhance of the
colored scl'jtfcn is prcporticncl tc the quar.t-ity cf fGmalo'ehydc Ir. the
solution.
•
1.3 Methanol: An aliquot of the scrubber solution is reacted with
potassium permanganate oxidizing all methanol present to formaldehyde.
The total formaldehyde is then determined colorimetrically. The back-
ground formaldehyde content as determined by (1.2) is then subtracted
out and the methanol content determined.
1.4 Dimethyl ether: An aliquot of the scrubber solution is analyzed
for dimethyl ether using a gas chromatograph wi-th a flame ionization de-
tector.
1.5 Grab sample: Using a Hamilton syringe, 20 ml of water is in-
jected into the glass bomb. The bomb is shaken and the liquid removed
-------
and analyzed for methanol, formaldehyde, and dimethyl ether to check
impinger efficiency. A sample of the remaininq gas is analyzed for
dimethyl ether.
2. Applicability:
2.1 This method is applicable for the determination of formalde-
hyde, methanol and dimethyl ether in the effluent of formaldehyde rranu-
facturinq facilities.
DRAFT
DO NOT QUOTE OR CITE
-------
3. P^ange:
3.1 Formaldehyde: .05 yg/ml - 2.0 pg/ml; Based on impinger solution
3
of 600 ml and 60 Ft gas collected: 6 - 240 ppnr, upper limit is easily
extended by diluting aliquot taken.
4. Sensitivity: unknown
5. Precision:
5.1 Formaldehyde: +_ 5?
6. Collection Efficiency:
6.1 Formaldehyde 95%
7. Interferences
7.1 Formaldehyde: This rr.ethcd ic specific for formaldehyde although
other hydrocarbons in concentrations in excess of formaldehyde to the
•
order of 10:1 will give interferences in absorbance readings:
Saturated Aldehydes <.01% (+)
Unsaturated Aldehydes 1 - 2?(+)
Ethanol, High Alcohols, Olefins (-)
Phenols (8:1 excess) 10-20%(-)
Ethylene, Propylene (10:1 excess) 5-10 (-)
Aromatics (15:1 excess) 15% (-)
Hethanol (10,000:1 excess) -None
Nitrogen Oxides* " (.-)
7.2 Methanol; same as above
7.3 Dimethyl ether; unknown
if**-
*Use of Aqueous bisulfite solution as the scrubbing medium wilY"reduce
interference of nitrogen oxides.
DO NOT QUOTE OR CiTE
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4
8. Apparatus:
8.1 Sampling;
8.1.1 Stainless steel nozzle
8.1.2 Pyrex probe - heated
8.1.3 Pi tot tube; s - type
8.1.4 Glass impingers: 2 Greenburg-Smith, 1 modified Green-
burg -Smith, 1 silica gel
8.1.5 Glass sample tube with side adapter for syringe; 250ml,
(Fisher Catalog 2 11-134-190)
8.1.6 Metering - Vacuum System as required to maintain an iso-
kinetic sampling rate
O 1 7 MO<-OW>T nrt _ U a pi i inn ^i/c+-£*m sic v»nni'i **iv! +r\ ^h+'a'Sn n>«aK earn—
^ » • • • • «»»»• ° ' ' S •b*Wv«b«"^ ~*J «* • ^ -]•* it ww vw Vb««*tt> -, •• «>. ./*....
pie.
8.2 Sample recovery
8.2.1 Probe brush
8.2.2 Wash bottle
8.2.3 Graduated cylinder
8.2.4 Glass sample storage jars
8.3 Analysis
8.3.1 Spectrometer capable' of measuring absorbance of the color
developed solution at 580 nm. ]
1
8.3.2 .Hamilton syringe for removal of sample from grab sample
bomb.
DO NOT QUOTE OR CITE
-------
.8.3.3 Gas chromatoqraph
8.3.4 Flame ionization detector
8.3.5 Recorder
DRAF
DO NOT QUOTE Oil CITE
-------
9. Reagents:
9.1 Sampling
9.1.1 Distilled water
9.1.2 Silica gel
9.1.3 Crushed ice
9.2 Sample recovery
9.2.1 Distilled water
9.3 Analysis: Formaldehyde
J ~— 9.3.1 Chromotropic acid reagent: Dissolve 0.10 g of 4,5
dihydroxy-2, 7 -'naphthalene-disulfonic acid disodium salt (Eastman
Kodak Co. Cat. No. P230) in water and dilute to 10 ml. Filter, if
necessary: store in brown bottle. Hake fresh weekly.
9.3.2 Sulfuric acid: Concentrated reagent grade
* 9.3.3 Formaldehyde standard solution "A": (I'mq/ml). Dissolve
4.4703 g sodium frsrmaldehyde bisulfite (Eastman PG 450) in distilled
water and dilute to 1 liter. Stable for one month.
) 9.3.4 Formaldehyde standard solution "B": (K'yq/ml) Dilute 1
ml of standard solution "A" to 100 ml with distilled water. Make fresh
1
daily. ... j
r. '/ " I
v 9.3.5 Iodine (0.1 N, approximate): Dissolve 25 g of potassium
*.
iodide in about 25 ml of water. Adjd 12.7g of iodine and dilute to 1 liter.
9.3.6 Iodine (0.01 N): Dilute 100 ml of the 0.1 N iodine solution
to 1 liter. Standardize against sodium thiosulfate.
DRAFT
DO NOT QUOTE OR CiTE
-------
^9.3.7 Starch solution, 1 percent: Make a paste of 1 cj of
soluble starch and 2 ml of water. Slowly add the paste to 100 ml of
boiling v/ater. Cool, add several ml of chloroform as a preservative,
and store in a stoppered bottle. Discard when a mold growth is notice-
able.
'•' 9.3.8 Sodium carbonate buffer solution: Dissolve 80 a of
anhydrous sodium carbonate in about 500 ml of v/ater. Slowly add 2P ml
of glacial acetic acid and dilute to 1 liter.
*' 9.3.9 Sodium bisulfite, 1 percent: Dissolve 1 q of sodium
bisulfite in 100 ml of v/ater. Prepare fresh weekly.
9.4 Analysis: Methanol
9.4,1 Same as formaldehyde analysis (9.3) plus:
9.4.2 Potassium permanganate solution: Dissolve 1 n A.R.
•
potassium permanganate in water and dilute to 100 ml with v/ater.
9.4.3 Ethanol solution: Prepare a 5 percent (volume) solution
of methanol - free ethanol in water. '•
9.4.4 Dilute phosphoric acid: Dilute 25 ml phosphoric acid
(r
(85%) to 100 ml with water.
«
9.4.5 Hydrogen peroxide solution: Prepare a solution containinq
approximately 1.5 percent w/v HgCL ^ ~ vo^urnes peroxide).
\ 9.5 Analysis: Dimethyl ether ;^V
—- • • :.J
9.5.1 Chromotographic column: 10% triethyl acetyl citrate..
DO NOT QUOTE OR CITE
-------
8
10. Procedure:
10.1 Sampling
10.1.1 The sample train is assembled as shown in Figure 4.
Each of the two impingers (Greenburg-Smith) is filled with TOO ml dis-
tilled water. The third impinger is left dry and the fourth impinger
contains approximately 200 gm silica gel.
10.1.2 A minimum sample of 60 Ft is collected isokinetically
as per EPA Method 5 at a rate of 0.5 to 1.0 CFM.
10.1.3 Halfway through the sample run the valve to the glass
bomb is opened and the glass bomb is purged at a rate of 1 LPN for two
minutes. The stopcocks at both ends of the gas sample tube are simul-
taneously c'losed. The vacuum source to tne sample tube and the valve to
the main sample train are closed off.
10.2 Sample Recovery
10.2.1 The gas sample tube is removed from the sample train
and stored.
10.2.2 The liquid from each impinger is stored in a separate
sample collection jar. .
'5
10.2.3 The probe and impingers are sparingly washed with
water (It is important to dilute the sample as little as possible.) and
the wash from each impinger is added to the sample collection jar for that
\
impinger. The probe wash is stored separately.
10.2.4 The weight gain in the silica gel is recorded.
f\Mi I
DO NOT QUOTE OR CITE
-------
9
10.3 Analytical: Formaldehyde
10.3.1 Measure and record the volume of each of the sample
solutions.
10.3.2 Pipette a 4 ml aliquot from each of the sampling solu-
tions into glass stoppered test tubes. A blank containing 4 ml of dis-
tilled v/ater must also be run. [If the formaldehyde content of the ali-
quot exceeds the limit of the method a smaller aliquot diluted to 4 ml
with distilled water is used.]
10.3.3 Add 0.1 ml of 1 percent chromotropic acid reagent to
the solution and mix.
10.3.4 To the solution pipette slov/ly and cautiously 6 ml of
uunueilird Leu iuifUi"iC dC'iJ. Ti'ie Solution beCGffifcrs fcrXti"£.iTicMy nut dliP'tno
the addition of the sulfuric acid. If the acid is not added slowly, some
loss of sample could occur due to spattering.
10.3.5 Allow to cool to room temperature. 'Read at 580 nm in
a suitable spectrophotometer using a 1cm cell. „
10.3.6 Determine the formaldehyde content of the sampling.solu-
tion from a curve previously prepared from standard formaldehyde solutions.
•
10.4 Analysis: Methanol
i
10.4.1 Pipette a 4 ml aliquot from each'of the sampling solu-
•
tions into glass stoppered test tubes. A blank containing 4 ml of distilled
v/ater must also be run. (If the methane! content exceeds the limit of the
method a smaller aliquot diluted to 4 ml with distilled water is used.
Dp p. r--i-
rtar i
DO NOT QUOTE OR CiTE
-------
10
10.4.2 Add .5 ml ethanol solution, 2.5 ml potassium per-
manganate solution, and .5 ml phosphoric acid solution. Mix and allow
to stand for 1 hour.
10.4.3 Add hydrogen peroxide solution drop by drop until
the solution is colorless.
10.4.4 Proceed with formaldehyde analysis (10.3.3)
10.5 Analysis: Dimethyl ether
10.5.1 Using Hamilton syringe take aliquot of sample solutions
and inject into gas chromatograph.
10.6 Analysis: Gas sampling tube
10.6.1 Using Hamilton syringe inject 20 ml of distilled water
into tho canmlino tii|io. Syirl dp.d shskp for 15 roinutes.
10.6.2 Remove two 4 ml aliquots using syringe and analyze for
formaldehyde and methanol using the already mentioned procedures.
10.6.3 Remove two samples, one liquid and one aas, using the
Hamilton syringe and analyze for dimethyl ether by gas chromatography.
DRAF
DO NOT-QUOTE OR CITE i
-------
11
11. Calibration:
11.1 Standardization of formaldehyde solution
11.V.I Pipette 1 ml of formaldehyde standard solution "A"
into an iodine flask. Into another flask pipette 1 ml of distilled
water. This solution serves as the blank.
11.1.2 Add 10 ml of 1 percent sodium bisulfite and 1 ml of
1 percent starch solution.
11.1.3 Titrate with 0.1 M iodine to a dark blue color.
11.1.4 Destroy the excess iodine with 0.05 N sodium thiosul-
fate.
11.1.5 Add 0.01 N iodine until a faint blue end point is
reached.
11.1,6 The excess inorganic bisulfite is now completely oxi-
dized to sulfate, and the solution is ready for the as'say of the formalde-
hyde bisulfite addition product.
11.1.7 Chill the flask in an ice bath and add 25 ml of chilled ,
sodium carbonate buffer. Titrate the liberated sulfite with 0.01 N iodine,
using a microburette, to a faint blue end point. The amount of iodine added
*
in this step must be accurately measured and recorded.
11.1.8 One ml of 0.0100 M iodine is equivalent to 0.15 ma of
formaldehyde. Therefore, since 1 ml of formaldehyde standard solution was
titrated, the ml of 0.01 N iodine used in the final titration multiplied
by 0.15 mg gives the formaldehyde concentration of the standard solution in
mg/ml.
DO NOT QUOTE OR CIT
-------
DRAFT
u J NOT QUOTE OR CITE
12
11.2 Preparation of standard curve, formaldehyde
11.2.1 Pipette 0, C.I, 0.3, 0.5, 0.7, 1.0, and 2.0 ml of
standard solution "B" into glass stoppered test tubes.
11.2.2 Dilute each standard to 4 ml with distilled water.
11.2.3 Develop the color as described in the analytical pro-
cedure (10.3)
11.2.4 Plot absorbance against microorams of formaldehyde in
the color developed solution.
1 2 . Calculations:
12.1 Formaldehyde
12.1.1 Correct the volume of air sampled to the volume at
standard conditions.
Vs . V x (
12.1.2 Calculate concentration of formaldehyde in the sample.
(volu,e) .
V = Volume Sampled, (Liters)
V = Volume S.T.P,' (Liters)
S.T.P = 70eF, 29.92"Hg
P = Barametric Pressure, "Hg-
P = Meter Pressure, "Ho
m
. T = Meter Temp., °F
C = pg of formaldehyde in aliouot (from calibration curve)
S = Total ml of sampling solution
A = Ml of aliouot taken from sampling solution
MW = Molecular weight of formaldehyde, 30.03
24.15 = Ml of formaldehyde gas in one millimole P S.T.P.
-------
DRAF
.DO NOT QUOTE OR CITE
13
12.2 Methanol
12.2.1 The total yg formaldehyde read from the absorbance
is equal to the formaldehyde originally in the sample plus the for-
maldehyde formed from oxidation of methanol. Therefore, from the total
jig formaldehyde in the aliquot, subtract the yg of background formalde-
hyde present in an.aliquot of equal size (previously determined).
This is the yg formaldehyde in the aliquot formed
from the oxidation of methanol. 1
i.'
12.2.2 M CM ,30.03N
H FH (32T04)
12-2.3 ». . (M) (S) (24.15)
C " (A) (Vs) (Ml-?)
v/here: M = Methanol content, yg
Me = Methanol concentration of air sample (ppm)
Fm = Formaldehyde from oxidation of methanol, yg
S = Total volume sample solution, ml
A = Aliquot taken from sample solution, ml
V = Air sample volume P S.T.P., liters
M = Molecular v/eight of methanol, 32.04
S.T.P = 708F, 29.92 "Hg
24.15 = ml of methanol gas in one millimole G> S.T.P.
12.3 Dimethyl ether I
12.3.1 Notcompleted yet.
-------
DRAFT
"DO MOT QUOTE OR CiTE
14
13. Major References:
13.1 Cares, Janet Walker; "Determination of Formaldehyde by
the Chromotropic Acid Method in the Presence of Oxides of Nitroaen;"
Amer. Ind. Hyp. Jour; July, 1968.
13.2 "Determination of Formaldehyde: Chromotropic Acid Method,"
PHS Standard Methods.
13.3 "Tentative Method of Analyses for Formaldehyde Content of
the Atmosphere (Colorimetric Method);" Health Life Science Journal;
Vol. 7 #1; Jan.,1970.
13.4 Walker, J. F.; Formaldehyde; Reinhold Publishing Co.; 3rd
Edition: 1964.
•• •> r r.j..^.i n,»j.j ir-n...,, •><• H u ay- 1* •» n«.»* TT I%..._U.«.
lO.y I CUCI O I I'.Cy I i uci , Vuiunlc JW , numUSl fr/ , i ai v 1.1, i'<_utH.i.Gi
23, 1971.
13.6 "Method for the Determination of Toxic Substances in Air:
Methanol (Adopted 1949); International Union of Pure and Applied Chemistry,
London, 1959.
-------
APPENDIX D
ANALYTICAL DATA
Includes:
D.I Data Analysis Summaries
D.2 Chemical Laboratory Notebook
D.3 Scrubber Liquor Sampling Times
-------
APPENDIX D.I
DATA ANALYSIS SUMMARIES
-------
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-------
APPENDIX D.2
CHEMICAL LABORATORY NOTEBOOK
-------
TRC - THE RESEARCH CORPORATION OF NEW ENGLAND
Report of Chemical Analysk Alon-Routine Samples
riienr ]=, f rr | Moratory Nr>!
Contract No: *& ^. v # # — fl~LU
Typ» Sample- FilTPr Fn«l Oil SnHimpnt Impingpr nfhpr J&r^C/ n-lJ *> \st (-. %"
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Sample Number
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Analysis No. 1
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-------
Report of Chemical Analysi. Mon-Routine Samples
Contract No: O ,A /OO '" O\ (3sa/si.t£t> — ' Date Received: 7 X?-^?-^ -~^&r
Reviewed by: Date Reonrted:
Report to: l\}f}(Si)
Typp R^mp|p; FjltPr Flip) Oil SpHimpnt Impjnrjpr r»(hpr cy*OJl/*yU&-&?LL .'Cj/y-XX-
£? ^7/*7o
Sample Number
Location
Analysis No. 1
^^^
-6^x
V,7*
3,3o
v^y
a^
3//^
Analysis No. 2
£^Li4,o
l«.^ ^ /*«.
-3«X>
-3o
•ft
Analysis No. 4
Analysis No. 6
TLV
Analyzed by:
Form CL-OO12
-------
Project No. g-
14
Book No.$£2££ii TITLE ft a i CO -
A ft
From Poge No.
O
To Pag<
Witnessed & Understood by me.
Date
Invented by
Recorded by
Date
-------
TITLE
Book
From Page No ___
-/-/
T- ' ~
f=> v •
\ ^ <
/*/
-------
16
Project No.£2h£rPI
Book NQ.SS9gg-l TITLE Q^fltr.O
.From Poge No.
(7
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:r.essed & Understood by me,
Date
Invented by
Recorded by
Date
-------
Project No.
Book No.-3f2M.-l TITLE
age No..
00
II
/, l »*»_;.
&V.O
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73.
//if/Tr
(3>~^
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&
& Understood by me.
Date
Invented by
Recorded by
Date
*#'
/1
To Page No..
-------
Project No. %Zi3%
Book No. SZ9ffJ^ \ TITLE A<5fl\rr>
/7?
To race No.
itnessed & Understood by me.
Date
Invented by
Recorded by
Date
-------
22
Project No. %g,?gg-O\
Book No. .83988-1 TITLE
A
ic,e> - ESST
>m Poge No.
/oo
$(00
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£.00
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-------
TITLE
iec? No.
No.
From Page No.
"
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1-745"
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(/
To Page No
V/itnessed & Understood by me,
Date
Invented by
Recorded by
Date
-------
24
Project No. 3&2£2-^1
Book No. %&88'l TITLE
- ft £SZ
Im Poge No.
irf I
„ .-.
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To Pace No.
\Jjitnessed & Understood by me,
Date
Invented by
Recorded by
Date
-------
63
Project No. ?593B~^I
Book No. 83988-1 TITLE /\g.c?\r.r>-figg>€T
From Poge No.
V 0 !
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63?
'
Witnessed & Understood by me,
.1,1
| L
C/Vex'>
Date
, d" */ S~
Invented by
Recorded by
2.01
S
0.5"
/•«*
3/.o
nJ
, b
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fv
-------
I
Filter Number
y 1401
Moil-;
MOfi
7 Anici
y
222
Initial Weight (g)
IW3
Initials
•aosi
6
^
Date Wei
r
-------
-------
74
Project
Book No
om Page No r$JL/i
CU->^h£J^ &&**_ Jby Sto cX ^JL
-------
ITl F ^ *.(>-<-- (b l.
f* , V
Project No
Book
•o.-r, ?c = *
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To Page No
Witnessed & Understood by me,
Date
Invented by
Recorded by
Date
-------
APPENDIX D.3
SCRUBBER LIQUOR SAMPLING TIME
-------
SCRUBBER LIQUOR SAMPLING TIMES
AGRICO CHEMICAL COMPANY, BLYTHEVILLE, ARKANSAS
Sampling Time (CST)
Date
12-18-78
12-19-78
12-19-78
12-19-78
12-19-78
12-19-78
Run
1
2
3
4
5
6
First Sample
1405
0925
1120
1320
1515
1627
Second Sample
1445
1000
1148
1400
1548
1700
-------
APPENDIX E
TRC/AGRICO JOINT ANALYSES
Includes:
E.I Agrico Field Sample Analysis
E.2 TRC Audit Sample Analysis
E.3 Agrico Audit Sample Analysis
-------
APPENDIX E.I
AGRICO FIELD SAMPLE ANALYSIS
-------
,-4
-------
3 0-3
3
- .3 1 o *#'{
^
^^
. /y»
0
- 3/5,
3/3.
.o
^
-------
I <€AJT
#lK
cf-t
/o
,J
_
-Vv
~-
-------
re required,
solve 134 g
iia-frcc dis-
,nc IhSO...
in prepared
•juric oxide,
. Dilute the
cp at a tein-
/ent crystal-
tr>r solution.
inn thiiKiil-
NaOl I and
imonia-frcc
I I.
See Section
'lime: Place
(><)-ml kjcl-
iiiniple si/.e
l:
pic Size
ml
50
DO
50.0
25.0
eto 30()ml
Uld 25 ml
I until pi I
iss beads or
1ml. Ifdc-
I determine
•natively, if
ned I'y the
residue in
INORGANIC NON-METALS (400)
the distilling llnsk lor the organic nitro-
gen determination. For sludge and sedi-
ment samples weigh vvet sample in a
crucible or weighing hottle, transfer the
contents to a kjcldahl flask, and deter-
mine total kjcldahl nitrogen. Follow a
similar procedure for ammonia nitrogen
determination and organic nitrogen de-
termined hy difference. Determinations
of organic and total kjcldahl nitrogen on
dried sludge and sediment samples are
not accurate because drying results in
loss of ammonium salts.
c. Digestion: Cool and add carefully
50 ml digestion reagent (or substitute 10
ml cone IhSCh, 6.7 g K2SC>4, and 1.5
ml mercuric sulfate solution). If large
quantities of nitrogen-free organic mat-
ter are present, add an additional 50 ml
digestion reagent for each gram of solid
matter in the sample. After mixing, heat
under a hood or with suitable ejection
equipment to fumes of SCb and con-
tinue to boil briskly until the solution
clears (becomes colorless or a pale straw
color). Then digest for an additional 30
min. Let flask and contents cool, dilute
to 300 ml with ammonia-free water,
and add 0.5 ml phenolphthalcin in-
dicator solution and mix. Tilt the flask
and carefully add sufficient (approxi-
mately 50 ml/50 ml digestion reagent
used) hydroxidc-thiosulfate reagent to
form an alkaline layer at the bottom of
the flask.
Connect the flask to the stcamed-out
distillation apparatus and shake the flask
to insure complete mixing. Add more
hydroxide-thiosulfate reagent in the pre-
scribed manner if a red phenolphthalein
color fails to appear at this stage.
d. Distillation: Distill and collect 200
ml distillate below the surface of 50 ml
boric acid solution. Use plain boric acid
solution when the ammonia is to be de-
NITROGEN (ORGANIC)
termincd hy ncssleri/.ation and use in-
dicating boric acid for a titrimetric fin-
ish. Extend the tip of the condenser well
below the level of boric acid solution and
do not allow the temperature in the con-
denser to rise above 29 C. Lower the
collected distillate free of contact with
the delivery tube and continue dis-
tillation during the last minute or two to
cleanse the condenser.
e. Final ammonia measurement: De-
termine the ammonia by either nessleri-
zation or titration.
I) Nesslerization—Mix the distillate
thoroughly and measure a 50.0-ml por-
tion or less. Complete the determination
as described in Nitrogen (Ammonia),
Section 4!8B.4/>-e.
2) Titration—Titrate the ammonia
in the distillate as described in Nitrogen
(Ammonia), Section 4l8D.4c.
/ Blank: Carry a blank through all
the steps of the procedure and apply the
necessary correction to the results.
439
5. Calculation
a. Nesslerization finish:
mg/1 organic N =
A XI. OOP
ml sample
H
C
where/l = mg N found colorimetrically,
B = ml total distillate collected including
the HjBOs, and C=ml distillate taken
for ncsslcriznrion. •
b. Titrimetric finish:
mg/l organic N
(D-E)X280
ml sample
where D = m\ IhSO-i titration for
sample and Z: = ml 1I.-SO4 filiation for
blank.
6. Precision and Accuracy
Three synthetic unknown samples
containing varying organic nitrogen
concentrations and other constituents
Vr«tf
TABLE 42 1 :l. PRECISION AND ACCURACY DATA FOR ORGANIC NiIRO<;KN
Sample
1
2
3
No. of
Labora-
tories
26
29
15
26
31
16
26
30
16
Organic
Nitrogen
Concen-
tration
**'//
200
800
1 ,500
Relative Standard Deviation
Ncsslcr
1'inish
%
94.8
52.1
43.1
Titri-
metric
Finish
%
104.4
44.8
54.7
Calculation of
Total Kjcldahl
N Minus
Ammonia N
%
68.8
52.6
45.9
Relative Error
Messier
I'inish
%
55.0
12.5
9.3
Titn-
meiric
I'inisI)
%
70.0
3.7
22.6
Calculation of
Toi.il Kjcldahl
N Minus
Ammonia N
%
70.0
8.7
4,0
1 •!*:
*' :•, n
-------
APPENDIX E.2
TRC AUDIT SAMPLE ANALYSIS
-------
Client:.
Contract No:_
Reviewed by:.
Report to:
JO
TRC - THE RESEARCH CORPORATION OF NEW ENGLAND
Report of Chemical Analysi: Alon-Routine Samples
Laboratory No:
Date Received:
Date Reported:
Type Sample: Filter
Fuel Oil
Sediment
Impinger
Other
Sample Number
3
Location
Analysis No. 1
Analysis No. 2
Analysis No. 3
Analysis No. 4
Analysis No. 6
7.^0%
TLV
V
3.55
7
7,
9
9.4
2
/o
II
y,
Analyzed by:
k0012fl
-------
12
P.oject No.
Book No.
- TITLE
From
-I
JOCts^-cJ-Sis
So
^ /A//
•-;
/o
//
3 «•
vv
ToF=ge^
Witnessed & Understood by me,
\
Date
Invented by
Recorded by
Date
-------
I I I
13
TITLE
,Af=>ft ir^O - fi gj
P ro j=ci No. QjS-/yd
Book NQ.9a?gg
From Pcge No..
3, /V/
o
O
/ 6 tf
i o rage fNO^^.
Witnessed & Understood by me,
Date
Invented by
Recorded by
Date
I
1
-------
TITLE Q^GldC? • P f=A£
Book No.
r
From Poge No..
- o
/uo
u
7
~f
I
0
JO
iA\
•D^CiA mrrw- 'X^^ xO , Q . AQ^t, QvTfitMlX cCsrfAj
-------
i I I
TITLE QGRICO - RsSET
Project No. &?9g
Book
"tr^L^/Tn^ ikia.
-------
TITLE
AsRiro -Pg-.g,£T
Project No.
Book No.
J>
To Poge No._
Witnessed & Understood by me.
Date
Invented by
Recorded by
Date
-------
APPENDIX E.3
AGRICO AUDIT SAMPLE ANALYSIS
-------
Rtport of Chemical Analysi: Mon-Routine Samples
Client:.
Contract No:.
Reviewed by:
Report to:
"4 '/
Laboratory No:.
Date Received: .
Date Reported:.
Type Sample: Filter
FIIP! Oil
RpHimpnt
Impinger
Sample Number
Location
Analysis No. 1
Analysis No. 2
Analysis No. 3
Analysis No. 4
Analysis No. 6
TLV
1 rj
3
y
7-7
. 3?
f.tv
vv.yy
I'/
6./6
7-3/70 %
/o
/X3
3.9
Analyzed by: Jfc ^
Form CL-O012
-------
#'/
V /97?
J r
1/0-3-/. 7
?r
. .- ^
1
4
~>D. <~- 1 "7 i
T
-i > «r,fn~\
Tt)
-------
?./- '.7
/CO
.1,7
f,
k
-.
-------
APPENDIX F
SAMPLING TRAIN CALIBRATION DATA
-------
DATE II /2. 7/7 7
~^~~^~jr*^^^^^m^j>
INSPECTION REPORT
ELFRED MACHINE COMPANY
VIH
FORM 13
-------
DATE //
INSPECTION REPORT
S.O. NUMBER _.
PART NO
TOOL NO
J — 7
/ XI
ELFRED MACHINE COMPANY
CUSTOMER P.O. NO.
PURCHASED FROM
NO. PIECES ORDERED
7 J <£ Y
TOOL NAME
Actual in 3 Places
1st PIECE INSPECTION
PARTIAL INSPECTION
COMPLETE INSPECTION
REJECTED
re-:.', i:
-------
©
DATE I//it/71
' I
INSPECTION REPORT
ELFRED MACHINE COMPANY
CUSTOMER P.O. NO.
/ 1 £ 7
S.O. NUMBER
PART NO
TOOL NO
PURCHASED FROM
P,O
. PIECES ORDERED NO. PIECES RECEIVED
.rr-/
PART
TOOL NAME
Actual in 3 Places
Average
Date/Initls
Actual in 3 Places
Averae
Date/Tn-ifl s
3-
1st PIECE INSPECTION
PARTIAL INSPECTION
COMPLETE INSPECTION
D
n
ACCEPTED
REJECTED
-------
DATE
///£
-------
a).
DATE
2*7/77
INSPECTION REPORT
ELFRED MACHINE COMPANY
rilSTOAAFR / /S C_ ~ //Hf /^fiZX&ftfW C4/IX: r.
S O NUMBER ^
STOMER P.C
RCHASED FF
/ < — NO. PIECES O
PART NO. / O
.^ . PART NAME
TOOL NO -S^ S /
Actual in 3 Places
• ^T2J £) — • VJ^/Q ' 7S&Q
1 7ffci ~~ i "Zf&£~~ 7&J&
'7^9? - -7joo <-.7s?&
^yg^-.WSS-.VYSo
,
Average
.7SOQ
,7&^
s / >J ^ C
*^^y g> ^^
TC
Date/Initls
>ytf/v^^5wJ
/>> /!&£${
//v7?/^^//'
'/^/ff^g
1st PIECE INSPECTION Q
PARTIAL INSPECTION Q ACCEPTED
COMPLETE INSPECTION R^""
REJECTED
)OL NAME _
Actual
) NO /'Of
?OM ^"Z/v^y^^? pn NO
RDERED / NO. PIECES RECEIVED /
^T/STC. A/0 t.Zt-/£-
in 3 Places
'
-^~
/
Average
••
^
Date/Tm' tl .s.
^
^^X- ^
^^ w
,v<^^I\^V
^ INSPEC^TOR/.r^'' ^^ "
^^> " """
-»"
-------
DATE
INSPECTION REPORT
ELFRED MACHINE COMPANY
rtisTOMFp 1 fcC --//-/£ fc£.SFili\
TC
Date/Initls
%/nsM
• 1st PIECE INSPEOTON Q
PARTIAL INSPECTION Q ACCEPTED
COMPLETE INSPECTION Q^
" REJECTED
kRT NAME
)OL NAME
Actual
/•f?7
> NO /*->//
OM y^rZ./-/O.-./3 po NO
JDERED / N(
D. PIECES RE
CEIVED /
'
in 3 Places
•
-/
Average
.. rffc
Dare/Tnl t]| sr
i , '\(^-1"'>^^*
^ .^^>1' ' c^^
; INSPECTOR .3^- p ^ "
/^L\ ""
v ^^ '. .) "V.,
-------
DATE 12/11/76 . ORIFICE NO D3 NAME SRICHARDSON
BAROMETRIC PRESSURE 30.29 IN HG DRV 6AS METER NO 3
?*********************************************************************£********]
*FICE GAS VOLUME TEMPERATURE
MANOMETER WET TEST DRY GAS WET TEST DRY GAS METER
SETTING METER METER METER INLET OUTLET AVERAGE TIME
IN WATER CU FT CU FT F ~ F ' F F MIN RATIO DHO
************************************************************************* ********^
0.5 5.0 4.97 72.5 69.0 67.0 68.0 12.5 1.00 1.76
1.0 5.0 *.99 72.5 68.0 66.0 67.3 9.0 0.99 1 .8«4
\.
2.0 1C.O 9.97 72.5 69.0 67.0 68.0 12.9 0.99 1.88
3.0 10.0 9.96 72.<4 70.0 68.0 69.0 10.6 0.99 1.88
«.**** 7* ******************** ********** ************************************** ******
AVERAGE 0.99 1.8
-------
***************************************************************************
*
*
*
*
*
*4
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
**
***********
D ATE
.
. STAND
******
NO. OF SCR
1
2
3
4
5
i
1
2 >
3
4
5
« CPCS»=0.
***********
THE RESEARCH CORPORATION
CLIENT EPA
CHARGE NO. 2988 T
******************************
CALIBRATION
TYPE S PILOT
12/11/78 TEHP.(F»- 55 .0
ARD PITOT NO. CE-1
******************************
STANDARD
EENS DELTA P "•• U.C. D
0.100
0.200
0.300
0.400
0.500
REVERSE (S) PITOT AND
0.100
0.200
0.300
0.400
0.500
99SQRTCDELTA P(STANOARD) / DEL
******************************
OF NEW ENGL
ESTER T1RONE
************
DATA
TUBE
B ARO.PR
SERIAL
************
TYPE S
EL T A P • • U .
o»i *»o
0*280
0.420
0.460
0*695
AVER
RERUN TEST
0.1 40~
0*280
0.410
0.450
0.680
AVER
TA PCSI)
************
AND
********************
ES.CIN.HG) =30.52
NO. 44
***************
COEFFICIENT
C . * CP ( S )
0.837
0.837
0.837
0.923
0.840
AGE CP(S) 0.855
0.837
0.837
0.847
0.933
0.849
AGE CP(SI 0.861
********************
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
^0 EXIT
-------
*
*
*
*
*
*
*4
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
THE RESEARCH CORPORATION
CLIENT EPA
CHARGE NO. 2988 T
****************************************
• _ -^
{: CALIBRATION
TYPE S PILOT
DATE 12/11/78 TEMP.CF)= 55.0
STANDARD PITOT NO. CE-1
************************************
STANDARD
NO. OF SCREENS DELTA P ••U.C. D
1 0.100
2 0.200
3 0.300
4 0.400
5 0.500
REVERSE C S) PITOT AND
\
1 0.100 .
2 0.200
3 0.300
4 0.400
5 0.500
* CPCS)=0.99SQRT*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
t
*
*
*
*
.00 EXIT
-------
APPENDIX G
AGRICO PROCESS OPERATIONS LOG
-------
LIST OF PARAMETERS RECORDED DURING TESTING
TK-101
AFR
UMT
GSP-C
AIGT
AOGT
SLL
SFA
SOWTC
PWTC
SLT
ISLF
AOS
NH3 Feed
Urea Solution Tank Level
Additive Feed Rate
Urea Melt Temperature, °F (confidential)
"C" Granulator Urea Spray Nozzle Pressure, psig
Temperature of "C" Granulator Inlet Air, °F (confidential)
Temperature of "C" Granulator Outlet Air, °F (confidential)
"C" Granulator Scrubber Liquor Level
"C" Granulator Scrubber Exhauster Fan Amps
Weigh-belt totalizer for "C" Granulator Outlet Urea
Weigh-belt totalizer for "C" Granulator Product Urea
Granulator Scrubber Liquor Temperature, °F
"C" Granulator Scrubber Liquor Feed Rate, gpm
Temperature of "C" Granulator Scrubber Exit Air, °F
Feed Rate of NH3 to Urea Synthesis Process
GCA/TECHNOLOGY DIVISION O0A
-------
SUMMARY OF PROCESS ANP CONTROL EQUIPMENT PARAMETERS
O
°\
m
n
§
o
12/18/78 l:55p-4:10p
Parameter
Urea Solution Tank Level
Additive Feed Rate
Urea Melt Temperature
Spray Nozzle Pressure
Granulator Inlet Air Temp.
Granulutor Outlet Air Temp.
Scrubber Liquor Level
Scrubber Fan Amps
Scrubber Liquor Temperature
Scrubber Liquor Feed Rate
Scrubber Outlet Temp
Ammonia Feed Rate
Symbol
TK-101
AFR
UMT
CSPC
A1CT
AOGT
SLL
SFA
SLT
ISLF
AOS
Nil 3 Feed
Units
*
*
Op
psig
°F
oF
*
amps
°F
*
oF
*
Mean Standard
Value Deviation
15.5
2.8
(-2)t
35.2
(+0.5)t
(-12.4)t
40.5
68.9
86.7
*
83.6
8.47
0.15
0.26
-
1.21
-
-
2.88
0.54
0.46
*
1.20 '
0.115
Minimum
Value
15.0
2.4
(-6) +
33
(0)t
(-18) t
35
68
86
!
80
8.4
Maximum
Value
15.5
3.1
(+1K
37
(+l)t
(0)f
43
70
87
t
84
8.8
12/19/78 9:
Mean Standard
Value Deviation
16.9
3.0
(+0.6)t
33.6
(+11. 5) t
(-14.5)t
38.2
69.0
95.2
f
92.3
8.65
1.59
0.32
-
1.35
-
-
1.84
0.84
1.10
t
1.30
0.136
05a-5:20p
Minimum Maximum
Value Value
15.0
2.3
(-4)i
31.5
(+8.5)t
(-28)t
33
68
93
J.
T
90
8.45
20.5
3.4
(+5)^
36
(+1.6)7
(+3)^
40.5
70
96
T
94
8.9
Uncnlibrnted readings, used as check for steady conditions.
'Confidential readings, values listed represent the difference from an arbitrarily
chosen confidential base Figure.
^Readings Inaccurate or monitoring device broken .during test period.
O
©
-------
Sample Calculations
GCA/TECHNOLOGY DIVISION
-------
Correction factors for "B" and "C" Granulators'
The method for determining the correction factor for these two Granulators
was based on the assumption that the correction factor for "A" Granulator was
correct for all test periods during 9 October through 13 October 1978. By
assuming that the correction factor is correct, we have also accepted the
assumptions made in calculating that correction factor; most notably that there
is no significant difference between the spray nozzles in the three granulators
nor in the melt passing through those nozzles. Furthermore, it is assumed that
flow through a spray nozzle is proportional to the square root of the pressure
drop across that nozzle. Based on these assumptions, the production rate for
a single Granulator .can be determined by multiplying the total production rate
by the square root fraction, (SRF) where:
SRF = /APx . (A-l)
APa" + v/AP^~ + v^AP"
AP = pressure drop across nozzle
A,B,C (subscripts) = refer to Granulators."A", "B", and "C"
X (subscript) = refers to Granulator of interest, "A", "B",
or "C"
Assuming that the correction factor for the "A" Granulator is correct,
the total production for a given run can be calculated by multiplying the
production rate for "A" based on corrected totalizer readings by the inverse
of the SRF for "A" for that run, (x = A in Equation A-l). This total production
rate is then multiplied by the SRF for "B" and the SRF for "C" to get the actual
production rates for those Granulators during this run. These rates are then
divided by the production rates based on the uncorrected totalizer readings to
yield correction factors for "B" and "C" Granulators. Correction factors,
formulated by this technique, were used to calculate the production rates for
"B" and "C" Granulators from totalizer readings in Table 2.
GCA/TECHNOLOGY DIVISION ®$
-------
Copy of Raw Data Recorded
During Emission Tests
OCA/TECHNOLOGY DIVISION
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APPENDIX H
PROJECT PARTICIPANTS
-------
PROJECT PARTICIPANTS
Agrico Chemical Company
Blytheville, Arkansas
December 18 and 19, 1978
TRC
Willard A. Wade III, Project Manager
Reed W. Cass, Project Engineer
Eric A. Pearson, Project Scientist
Stephen F. Richardson, Test Team Leader
Margaret M. Fox, Chemist
Joanne M. Marchese, Chemist
GCA
Steven K. Harvey
Agrico Chemical Company
Jesse Boggan, Environmental Coordinator
James Kilpatrick, Chief Chemist
Deryl Beiard, Chemist
EPA _ " "
Clyde E. Riley, Technical Manager
Daniel Bivins
Eric A. Noble
Gary D. McAlister
-------
APPENDIX I
SCOPE OF WORK
Includes:
Work Assignments
Technical Directives
-------
V/ORX ASSIGNMENT ' '• " i'C.v-rr ~'v • •
• . » ^
. • •. , B
,'- ' " EHViabj/asNTAL PROTECTION AGENCY
Research Triangle Pzrfc. N.C.
•
• • • •
T>7I-e- Conduct Emission -Test' Program -at an
Plant ' ' . . . '
277J1
Urea- Manufacturing
V
e^ACO-NTOACTfia
' ""63-02-2.820
cornnAcro*
TRC of New England
ASSiCNAJErtr NO . .
ASSI£NM£Nr CHftXGe NO. .
DATE • ' • •:•
5P£Cs7B ', -.; ; '
The Contractor-shall perform an emission test program in accordance with
the basic contract scope of work for the Emission Measurement Branch, and as set
forth .in the attached "Source Sampling and Analysis Schedule" at the following "site:
• . Company:. Agrico Chemical • ' .
Location: Blytheville, Ark". ', '. .
Industry: .Ammonium Fertilizer
:. Project i'!o..: 79-NHF-13 ••• '
The Emission Measurement Branch's Technical Manager is Clyde E. Riley.
Mail Drop -13, EMB, ESED,' OAQPS, Research Triangle Park, .North Carolina.27711. .' _
Upon.notification of approval of the proposed source, test report," the Contractor'
shall provide 25 copies of the final.report with appendices. • - ' '.
ATr Q?
GOVERNU3NT fSTlMATS
SSTK.!ATB
200
3 months
March Yl, 1Q7Q
Clyde E. Riley £,£?..
//- .3 3 -7J
COO=
ESED/EMB
i,.-5 (919
541-5243-
OATC
• 11 /30/78
DATS
'i':r. O'fiCf a
/-?-/
<-.-o-.-.-i ;QC.'.:J-MT
-------
Figure 1
Agrico Co./The William:; Co., Blytheville, Arkansas
SVPl
TP1
r_
Scrubber
Dilution
Air
TP2
SW-2
TP7 Urea Formaldehyde
Recycled Fines
Air
Drunr Granule tor
Solution Urea
-------
... .,-,OE SAMPLING AND ANALYSIS SCHEDULE
See Figure 1
i~pl ing
ji.it
P2
I
letol
;.'o. of
6
Aljquots
San
Afi
Ont
Sec
Th/
the
SW-1
SW-2
pie an
pr roii
porti
one po
<-. P CO 1
y shal
6
6
Socplc
Type
Urea
P articulate
hall be col'
ilysis shall
-tlpHon of at
Dn shall be
"tion shall
1 1 ] n n c; shall
1 be analyze
Scrubber
Solution Jn
Scrubber
Solution Out
Sapling"
1* tiicd
Modified
EPA-5
ected from e
be conducted
a] us is rpmai
reatad with
e treated wi
HP rPt»rnpH
by m Kjel
Compos i/e
Composite
U'"i;iJiiy fi>ii::c: • l.oit^Jn/ uocJlion;
_J\gr ico Chemical Bly.thev tile, Ark.
muusiry: Process: Control C^ui?:'.ent:
— Ammonium Fertilizer • -Ur-ea-GMnulator . Scrubber --
Somplc
Collected
J»Z . • .
CTR .
ch of the
within 21-
ii no s/imnl
saturated
;h concent
-n thP TRP
lahl urea
EPA
EPA
Mill ten
.. Tir.«
fiO
above 6 :
hours of
PS shall
nercuric
Mitilnum Has
VOU-.1X! j
30
amples
collectio
,P split i
:hloride (
rated sulyurip acid
i
Tab and Jllowpd to
nethod op
N. A.
N. A.
.„ -
:e .qyery t
N. A.
N. A.
,/
Initial Analysis
Type Method
Urea
Mass
Urea
Mass
i on each o
ito 2 equal
approximate
(approxima
stand at. r
vo days for
Percent
Solids
Percent
Solids
KjeldahT
jeldahl
: the H20 "S
portions a
ly 2 ml per
tely 2 ml p
)on\ tempera
urea conte
Filtration
Filtration
6y
**
CTR,
Agrico
amples.
id treatec
liter of
ir liter c
ture for i
it during
ulK
CTR
Fina] Analysis
Type Method
Ammonia
•. •.
with a st«
water)
f water)
period of
this perio(
Urea
NH.,
Urea
MU .
(EPA)
Nessler
--
bilizer.
20 days; hi
•
Kjeldahl
Nessler
Kjeldahl
MPSS! pr
.
CTR
., i
!
•wever
CTR
CTR
CTR
r.Tk
.
:TP-
5ar.pl Ino Roqytrcd
i-tor.
1. Sampling shall be psrforned with t 101 Uoklnctlc conditions.
2. J'othods arc CPA unless Indicated otherwise,
3. Inpinoers and analysis of impfr.ger catch will be per the fWeral Rt-clitep, Voluro 35,
' »«,* 1*LQ P^^^ rf Y..™»J... *.._ ^t \ <\ -t\ ^ ..*** _T^^ ^ _-."*_ " > *~~~* L » n i • A
-------
Prujr-ct f.'o. 79-UMF-13
A. Urea Method Development Instructions
1. Contractor shall determine stability conditions for the following
six urea solution concentrations. TRC shall use the Kjeldahl urea
method to analyze for urea content and the Messier method to
determine the ammonia content.
a. 40 mg of urea per liter of water
b. 100 rng of urea per liter of water
c. 40 mg of urea per liter of v/ater with 2 ml of saturated mercuric
chloride solution added
d. 100 mg of urea per liter of v/ater with 5 ml of saturated mercuric
chloride solution added
e. 40 mg of urea per liter of water with 2 ml of concentrated
.sulfuric acid added
f. 100 mg of urea per liter of water with 5 ml of concentrated
sulfuric acid added.
These solutions shall be allowed to stand at room temperature for a
period of 20 days; however, they shall be analyzed once every 2 days
for urea and ammonia content. Questions regarding these instructions
or the urea and ammonia analysis procedures shall be directed to
Mr. Gary McAlister at 919-541-5276.
2. Contractor shall prepare two duplicate sets of "dry" urea audit
samples. Each set shall contain 12 individual urea samples.
Both sets of samples shall be forwarded to the Agrico Chemical
plant in Blytheville, Arkansas, by TRC personnel. One set of
samples shall be analyzed by Agrico personnel and the second set
shall be'a'nalyzed by TRC_personnel. •'•• '. '"••'' .-'... . -- ~ ''•'•"' .-
-------
3. Agrico audit sample analysis shall be performed .iccording to
methods and procedures employed while analyzing th'e urea samples
generated during the October 9, 1978, EPA test program.
4. TRC audit analysis shall be performed using the Kjeldahl urea
method as directed by Mr. Gary McAlister, EPA.
5. Contractor shall specify procedures directing Agrico personnel
to dilute the 12 audit samples with solutions of water and/or
IN ^SO^. Audit sample analyses shall be conducted within 12 hours
after dilution. The 12 audit samples shall be prepared and diluted
as follows:
Dilute With 400 mis HgO ' Dilute with 250 mis IN H-SO.
No. 1 100 mg urea . No. 7 2 mg urea
No. 2 300 mg urea • - "•' : No. 8 5 mg urea
No. 3 600 mg urea No. 9 10 mg urea
No. 4 5 mg urea Mo.10 5 mg urea
No. 5 10 mg urea No.11 4 mg urea
No. 6 40 mg urea No.12 30 mg urea
B. Agrico Test Program
1. Contractor shall collect six urea particulate samples from one of
the operating granulator outlet stacks. Samples shall be collected
using isokinetic sampling conditions for a period of approximately
1 hour. The collection train shall consist of a probe heated to
.•-'•-• stack temperature",; a flexible teflon line, and five impingers. " .
.;• The first,three impingers shall each be prefilled with 100 mis
-------
Dist. H.,0, the fourth sh;ill rwnain empty, and the fifth shall
contain approximately 200 gins of silica gel. The second and
third shall b<» of the Greenburg-Smith design v/ith standard tips.
The first," fourth, and fifth shall be modified with a 1/2" tube.
2. Cleanup shall consist of measuring the solution volumes and rinsing
the probe, flex line, and impinger several times (3) with Dist.
HpO. Afterwards the water samples shall be filtered through a
prewei'ghed fiber glass filter using a Buchner funnel and vacuum
pump.
3. Analysis shall consist of weighing the liquid samples initially.
Afterward two equal aliquots shall be withdrawn. One aliquot shall
be analyzed for urea and ammonia by Agrico personnel using the Kjeldahl
urea method. The second aliquot shall be analyzed for urea'a'nd'.
ammonia by TRC personnel using the Kjeldahl method as directed by
EPA. Sample analysis shall be conducted within 24 hours of collection
of all samples. . .. -
After the two analysis aliquots have been withdrawn the remaining
.*
sample volumes shall be split into two equal portions and treated
with a stabilizer solution. One portion shall.be combined with a
saturated mercuric chloride solution (approximately 2 mis per liter
of water). The second portion shall be combined with concentrated
sulfuric acid (approximately 2 mis per liter of water).
-------
4. Those r.olutions shall be returned to the TRC laboratory and
allowed to stand~at room temperature for a period of 20 days;
however, they shall be analyzed by. the Kjeldahl urea method once
every 2 days during this period* for urea and ammonia content.
5.' The preweighed glass fiber filters used to filter the water
solutions shall be returned to the TRC laboratory, dried and
weighed for undissolved solids.
6. Contractor shall separate and report all Research and Development
data -in a separate EPA proposed draft report. These method and
evaluation data shall not be included in the Agrico NSPS report.
Contractor shall submit 3^ copies of the proposed R&D final report
directly to Mr. J. E. McCarley, EMB, ESED, Hail Drop 13, Research
-Triangle Park, N. C. 27711. The separate R&D report shall be
entitled "Development of Analytical Procedures for the Determination
of Urea from Urea Manufacturing Facilities" and listed under
Project No. 79-NHF-13.
-------
Project Number
Contractor •
EMISSION MEASUREMENT BRANCH
TECHNICAL DIRECTIVE NO. • 1 •
79-NHF-13 .
Date February 16,. 1979
TRC of New England
Contract Number 68-02-2820
Technical Manager Hyde E. Riley '_
Verbal Directions Given To Hill Wade
Work Assignment Number
Directive:
1. The Contractor shall perform formaldehyde analysis on each of the six urea
particulate samples.
Clyde E. Riley
Technical Manager, EMS
/Section Chief, EKB
-------
EMISSION MEASUREMENT BRANCH
TECHNICAL DIRECTIVE NO. 2
Project Number 79-NHF-13
Contractor
Date March 21, 1979
TRC of New England
Contract Number
68-02-2820
Work Assignment Number
n
Technical Manager Clyde E. Riley
Verbal Directions Given .To Mr- wil1
Directive:
See attached pages.
CJL.
TechiXcal Manager, EMB Y
Section Chief, EM/
-------
Work Mssign.f.eni :.o. il
Contractor shall perform the following evaluation analyses:
1. Prepare an urea standard solution containing 2mg urea /ml H^O
*.' *
Weigh 0.2000g of urea into a 100 ml volumeteric flask and dilute.
to 100 ml with deionized, distilled H^O.
2. Prepare an ammonia standard solution containing 20 mg NHL/ml hLO
Weigh 31.4lOOg of NH.C1 into a 500 ml volumeteric flask and dilute
to 500 ml with deionTzed, distilled H^O.
3. Prepare nine samples from the above standards as follows:
Sample Nos. ml of Urea Std. ml of NH3 Std. Total Volume ml
15 0 100
25 0 200
3 15 0 200
4 10 0 100
5 10 1 200
6 10 5 200
75 5 100
8 5 25 100
9 5 50 100
Note: Samples must be analyzed within 24 hours after being prepared.
4. Analyze the nine samples using the colorimeteric (p-aminobenzaldehyde)
procedures. Use samples 1,2,3, and 4 to prepare a standard curve.
5. Calculate the measured values for the remaining samples 5 through 9.
6. Data shall be presented in mg urea/ml of solution along with the
standard curve.
If additional information is required please contact Mr. Gary McAlister at
919/541-2237.
cc: Gary McAlister
File: 79-NHF-13
-------
\
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
February 13, 1980
Mr. Will Wade
TRC of New England
125 Silas Deane Highway
Wethersfield, Connecticut 06109
Reference:
Dear Will
EPA Contract No. 68-02-2820, Assignment No. 11, Agrico Chemical,
Blytheville, Arkansas, EMB Report No. 79-NHF-13
This correspondence is to document the enclosed Technical Directive
instructions for conducting an evaluation of slope linearity for standard
urea curves.
It has come to our attention that the standard curve slope may change
with low-urea concentrations. In order to verify this conjecture Mr. Gary
McAlister has requested that curves for two sets of standard samples, be
compared. The first set of standard samples will range from 50 mg urea/liter
to 250 mg urea/liter. The second set will range .from 1 mg urea/liter to
30 mg urea/liter. Standard solutions containing the following urea concen-
trations will be used to establish the two curves.
Set No. 2
Set No. 1
1. 50 mg urea/liter
2. 100 mg urea/liter
3. 150 mg urea/liter
4. 200 mg-urea/liter
5. 250 mg urea/liter
TRC shall prepare and analyze the standard solutions as follows.
Samples containing urea and deionized distilled water shall be made
up in 100 ml volumeter!c flasks.
1.
2.
5!-
6.
7.
r—
1 mg urea/liter
2 mg urea/liter
5 mg urea/liter
7 mg urea/liter"
10 mg urea /I iter
20 mg urea/liter
30 mg urea/liter
-------
Samples shall be analyzed by the P-dimethylaminobenzaldehyde colorimeteric
procedure. Do not boil off the samples as there should be no impurities
present to interfere with the a-ialyses^.
Establish calibration curve No. 1 using urea results obtained from
Set No. 1 samples.
Determine urea concentrations from calibration curve No. 1 using
measured values obtained from Set No. 2 samples.
Establish calibration curve No. 2 using urea results obtained from
Set No. 2 samples.
Compare the slope of the No. 1 curve to the slope of the No. 2 curve.
Please report your conclusions and recommendations- along with a summary
of the data to me by March 14, 1980. These data will be used to establish
guidelines for the upcoming prill tower test in St. Helens, Oregon.
If you have any questions regarding these instructions or require additional
information, please do not hesitate to contact me.
Sincerely yours,
Clyde E.
Field Testing Section
Emission Measurement Branch
Enclosure
cc: Gary McAlister
Marge Fox, TRC
-------
EMISSION MEASUREMENT BRANCH
TECHNICAL DIRECTIVE NO. - 4
Project Number 79-NHF-13 . Date Feb. 12, 1980
Contractor • TRC of'New England
Contract Number 68-02-2820. Hork Assignment Number 11
Technical Manager Clyde E. Riley
Verbal Directions Given To Mr. Reed Cass • • • • •
Directive: •
Contractor shall determine slope linearity for standard urea curves using the
following sets of samples.
Set No/ 1 " ' . Set No. 2
1. 50 mg urea/liter 1. 1 mg urea/liter
2. 100 mg urea/liter 2. 2 mg urea/liter
3. 150 mg urea/liter 3. 5 mg urea/liter
4. 200 mg urea/liter 4. 7 mg urea/liter
5. 250 mg urea/liter 5. 10 mg urea/liter ; .
_ 6. 20 mg urea/liter
» " 7. 30 mg urea/liter '
Contractor shall prepare and analyze samples per instructions presented
in February 12, 1980 correspondence to Mr. Will Wade.
€
Technical Manager,
Section Chief, EfiB
I/
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