p.1 

OAR Box 1124 

Prepped by Ollie Stewart 

Document Number: 

56) II-A-5 

Docket Number: 

A-84-44 

Printed 4/16/2008 8:13:21 AM Sheet 56 of 70 
x-/EPA 

Agency aUJ 7 r 

P.2 

Research and Development EPA-600/S4-B2-054 August 1982 

Project Summary 

A-84-44 

Field Evaluation of Carbon 

Monoxide and Hydrogen 

Sulfide Continuous Emission 

Monitors at an Oil Refinery 

Bruce B. Ferguson and Richard E. Lester 

An eleven-month field evaluation wat 

conducted for five hydrogen sulfide and 

four carbon monoxide continuous emission monitors (CEMs). The H2S CEMs 

were installed on a fuel gas line and the 

CO CEMs were installed on a stack from 

a fluidized bed catalytic cracking unit at 

a refinery. Performance specification 

tasting was routinely performed on the 

instruments as they were operated and 

maintained in this field environment. 

This Project Summary was developed 

by EPA's Environmental Monitoring Systems Laboratory. Research Triangle 

Park. NC. to announce key findings of 

the research prefect that is fully documented in a separate report of the same 

title (see Project Report ordering information at back). 

Introduction 

On March 15. 1978. EPA promulgated New Source Performance Standards 

(NSPS) that required petroleum refineries 

to continuously monitor the carbon monoxide (CO) emissions from fluid catalytic cracking (FCC) units.1

 Refineries 

were required also to continuously monitor either the hydrogen sulfide (H2S) 

concentration in fuel gas feed lines or the 

sulfur dioxide (S02) concentration in the 

exhaust of the boiler burning the fuel 

gas. However, refineries were not required to install H2S or CO continuous 

emission monitors (CEMs) until performance specifications for the instruments 

were published by the EPA. 

In April 1979, the EPA initiated work 

to establish these specifications and 

also to determine the durability, maintenance requirements, and data validity of 

commercially available CO and H2S continuous emission monitors. To procure 

the monitors. 35 vendors of commercially available stack gas monitors for 

CO and H2S were asked to recommend 

monitors for evaluation. Sixteen did not 

respond. A total of ten H2S and thirteen 

CO monitors were advanced for consideration. From this list, five H2S and four 

CO monitors were selected for evaluation (Table 1). The selection criteria included operating principle, engineering 

judgment about suitability for use at petroleum refineries, and total cost. 

These nine monitors were installed in a 

trailer at the Harmon Engineering & Testing facility in Auburn, Alabama and then 

transported to a petroleum refinery for 

an eleven-month field evaluation. Here, 

the H2S monitors measured the H2S 

concentration in a fuel gas at a point 

downstream of an amine treater (an H2S 

control device) and the CO monitors 

measured the CO concentration in the 

exhaust gas from a boiler on an FCC unit. 

An EPA-designed stack gas conditioning 

system removed particulate and water 

from the FCC stack gas at the sampling 

port before sending the clean, dry gas to 

a manifold in the trailer (where it was distributed to the monitors). A similar manifold was used to distribute fuel gas to the 

H2S monitors. 
P.3 

Table 1. Continuous Emission Monitors Evaluated 

Instrument Manufacturer Model Number Abbreviation Operating Principle 

CARBON MONOXIDE ANALYZERS 

Anared, Inc. 

Santa Barbara, CA 

P.O. Box 3180 

Santa Barbara. CA 93105 

Ecolyzer 

Energetics Science 

85 Executive Blvd. 

Elmsford. NY 10523 

Applied Automation, Inc. 

Pawhuska Road 

Bartlesville, OK 74004 

Mine Safety Appliances Company 

7522 Neade Street 

Pittsburgh. PA 15208 

HYDROGEN SULFIDE ANALYZERS 

Bendix Corporation Environmental 

and Process Instruments 

P.O. Drawer 831 

Lewisburg, WVA 24901 

Del Mar Scientific. Inc. 

P.O. Box 486 

Addison, TX 

Houston Atlas, Inc. 

9441 Baythorne Drive 

Houston, TX 77041 

Process Analyzers, Inc. 

1101 State Road 

Princeton, NJ 08540 

Teledyne Analytical Instruments 

333 VV. Mission Avenue 

San Gabriel, CA 91776 

501R 

3107/2949 

Optichrom 102 

LIRA 202 

Anarad 

Ecolyzer 

AA102 

MSA 

7770 

DM-W 

825R/102 

32-230 

611 DMC0-20X 

Bendix 

Del Mar 

HAI 

PAI 

Teledyne 

Nondispersive Infrared 

Detector (NDIR) 

Electrochemical Sensor 

Gas Chromatograph/Flame 

Ionization Detector (GC/FID) 

Nondispersive Infrared/Luft 

Detector (NDIR/Luft) 

Gas Chromatograph/Flame Photometric Detector (GC/FPD) 

Lead Acetate Impregrated 

Paper Tape 

Lead Acetate Impregrated 

Paper Tape 

Gas Chromatograph/Flame Photometric Detector IGC/FPD) 

Ultraviolet Absorption 

The output from the monitors was recorded on an Esterline Angus PD 2064 

data logger, Techtran 816 tape cassette 

recorder and an Esterline Angus multipoint recorder. The multipoint recorder 

printed the instantaneous monitor value 

at 3-minute intervals. The PD 2064 read 

the monitors' output at 3-minute intervals and printed the average after ten 

readings, except during relative accuracy 

tests when it read it every minute and 

printed the average of 30 readings. The 

PD 2064 also initiated daily zero and 

span checks of the monitors with calibration gases and recorded the results. 

Periodic tests for relative accuracy, 

calibration error and short- and long-term 

drift were conducted periodically during 

the field evaluation. EPA Method 11 

was the reference method for the relative accuracy tests on the H2S monitors. 

EPA Method 10 (NDIR)) and a colorimetric 

method (leuco crystal violet, LCV) being 

evaluated during this study, were the 

reference methods for the relative accuracy tests on the CO monitors. 

The results of the monitor evaluation 

are summarized here. A full report describes the test results, the LCV analytical method, and the components and 

performance of the FCC stack gas conditioning system. 

Results and Discussions 

Carbon Monoxide CEMs 

Initially, the monitor evaluation was 

intended to determine the ability of CO 

and H2S monitors to meet some tentative performance specifications similar 

to those for NO, and S0 2 CEMs. However, after the study was initiated, EPA 

revised Performance Specification 2 

(NO„ and S0X monitors) to require only 

calibration error (CE) and relative accuracy (RA) tests for certification.2 Since 

similar requirements were expected to 

apply to CO and H2S monitors, the focus 

of the field evaluation shifted to concentrate on just these two requirements. 

Table 2 summarizes the relative accuracy results obtained on the CO monitors. Overall, four valid relative accuracy 

tests were conducted on the CO monitors. 

In these tests, the reference method 

samples were collected in Tedlar bags 

preceded by an alkaline potassium permanganate solution for N0-./S0,, 

removal and sent to the EPA laboratory 

at Research Triangle Park, North Carolina, for analysis by Method 10 and the 

LCV method. 

Since the MSA and Anarad monitors 

suffered interference from C02. a cylin-
P.4 

Table 2. 

Date 

9/80 

1/81 

2/81 (A) 

2/81 (B) 

Mean 

Summary of CO Relative Accuracy Tes 

Number of Mean LCV 

Reference CO2 CO 

Method Cone Cone 

Samples (%) (ppm) 

6 

9 

9 

9 

2 

2 

12 

3 

80 

404 

607" 

712 

ts at Refinery 

Ecolyzer 

% Stdc % ICO] 

ff 34 

14 17 

>100 >100 

• • 

40 60 

Relative Accuracy 

Anarad* 

%St<* 

3.8 

13 

7.7 

12.7 

9.3 

%/C0] 

24 

16 

7.6 

8.9 

14 

MSA 

%Std' 

2.9 

13 

4.2 

9.7 

7.4 

D 

%IC0] 

18.4 

16 

4.3 

6.8 

11 

* This is the average ofthe manual method results using the leuco crystal violet method developed in this study. 

•* Corrected for C02 interference. 

c Standard for CO: 500 ppm. 

•dMonitors sampled cylinder gases containing 502 ppm CO, 12% CO2 and different concentrations of NO and SO2 in nitrogen. This 

was done to evaluate the performance ofthe monitors when they were sampling a stack gas with NO, and SO 2 levels representative 

of an FCC stack gas. During the 11-month study, process upsets and refinery equipment malfunction caused the CO levels to exceed 

the span range of the monitors and so it was necessary to dilute the stack gas to bring the CO level into the working range of the 

monitors during the relative accuracy test. Dilution was obtained by introducing plant instrument eir at the probe. This dilution reduced 

the N0K end SO 2 levels bye factor of 4 to 6 and permitted the Ecolyzer to obtain an accurate analysis of the stack gas. 

• Monitor not operational beceuse of detector failure from high SO2 and NO levels encountered in Test 2/81 (A). 

der gas containing 10% C02 in nitrogen 

was introduced at the manifold after 

each relative accuracy test and the monitor's response (ppm CO/1 % C02) was 

used to correct the relative accuracy test 

results for the C02 content of the stack 

gas. As expected, the C02 interference 

remained quite steady during the study 

(Anarad, 3 ppm/1% C02 , MSA 1 ppm/ 

1%C02 ). 

Table 3 summarizes the results of the 

calibration drift (CD) tests. These tests 

were performed in conjunction with the 

daily zero and span checks. Since the instruments were not zeroed each day, the 

values reported represent the daily zero 

drift vslues corrected for the zero value 

recorded for the start of the 24-hour 

period. 

The Applied Automation performed 

well during the laboratory check-out, but 

suffered from an unknown interference 

in the FCC gas sample. A valid relative 

sccuracy test was not completed because of this and because of the erratic 

performance of the instrument. Testing 

of the instrument was discontinued after 

a factory representative was unable to 

find the cause of the interference and 

unable to correct the erratic behavior in 

the monitor's output. 

The Model 2949 NO./SO, scrubber 

supplied with the Ecolyzer was found to 

be inadequate for long-term use of FCC 

stack gases where S02 levels of 400-

800 ppm and NO, levels of 100-400 

ppm are encountered. Because some of 

the scrubbers were exhausted within 

Table 3. Calibration Drift Test Results for CO Monitors 

Calibration Drift'- * (%) 

Day 

Test 1 

/ 

2 

3 

4 

5 

6 

7 

Test 2 

1 

2 

3^ 

4 

5 

6 

7 

Test 3 

1 

2 

3 

4 

S 

6 

7 

' Values in 

Ecolyzer 

Zero 

1.4 

0.3 

0.2 

0.6 

0.4 

0.9 

1.2 

0.2 

0.2 

0.7 

0.2 

0 

0.1 

0.1 

0.1 

0.3 

0 

0.1 

3.1 

2.2 

0.7 

Span 

0.4 

4.4 

1.7 

1.0 

0.7 

0.9 

1.6 

7.2 

0.1 

10.8 

0.2 

1.6 

0.9 

0.3 

0.1 

3.4 

0.4 

0.9 

2.7 

2.8 

0.9 

Anarad 

Zero 

1.7 

0.2 

0.2 

1.0 

2.0 

2.1 

3.2 

2.4 

0.2 

0.4 

0.4 

1.1 

01 

0.5 

0.9 

1.3 

0 

0.6 

0.4 

0.4 

0.2 

Span 

0.1 

2.4 

1.6 

0.2 

0.8 

1.5 

4.5 

0.7 

4.4 

3.4 

0.3 

0.4 

1.9 

1.0 

0.6 

1.7 

0.7 

1.1 

1.1 

0.1 

0.1 

MSA 

Zero 

0.6 

0.9 

1.2 

1.4 

2.5 

3.3 

2.9 

0 

1.7 

5.4 

1.3 

2.5 

0.2 

0.1 

0.2 

0.2 

0.4 

0.7 

1.8 

4.2 

0.9 

Span 

0.1 

1.2 

2.0 

0.8 

6.2 

3.0 

0 

0.9 

2.4 

1.3 

3.6 

3.7 

1.1 

1.7 

1.2 

1.2 

0.1 

1.2 

2.8 

1.1 

2.8 

teble represent the daily drift as defined by the following equation 

[Calibration Gas Concentretion - Monitor Reading x 100% 

Monitor Span Value 

* Because long-term drift was of primary concern, the instruments were not zeroed daily. 

The values in the table have been corrected by the daily zero drift. 

e

 Instrument recalibration was performed this date. 
P.5 

24-hours. it was decided to use them 

only during relative accuracy tests. During routine unattended operation a 2 5 

cm long x 2.5 cm ID PVC tube packed 

with activated charcoal was substituted 

for the 294 9 scrubber. (This charcoal 

tube could not be used for RA tests, because it caused a 30-minute delay in the 

analyzer's response to a change in stack 

gas CO concentration.) 

Throughout the field study, the FCC 

unit malfunctioned at frequent intervals, 

which caused the CO level in the stack to 

rise above the span range of the monitors (100 0 ppm). Such malfunctions occurred during the first two relative accuracy tests and it was necessary to add 

ambient air to the stack gas at the probe 

exit to bring the CO concentration below 

100 0 ppm. Since this dilution significantly reduced the SO, and NO, levels in 

the sampled gas, the Ecolyzer performed 

better than expected during the test. 

(The actual effect of NO, and SO, on the 

Ecolyzer can be seen by referring to RA 

Test 3 (February 1981 A) in Table 2 - a 

test in which cylinder gases containing 

SO, and NO, at levels normally expected 

in an FCC stack gas were used instead of 

diluted stack gas.) 

The Ecolyzer failed to complete the 

field study because of detector failure. 

The detector failed twice during the 

seven months the monitor operated. The 

monitor also experienced severe drift 

throughout this seven-month period. 

Because its output was not compatible 

with the PD 206 4 input requirements. 

the MSA instrument was not operational 

until July 1980 . The monitor performed 

well in all the relative accuracy tests 

after its response for C0 2 in the sampled 

gas was corrected. It suffered two major 

outages (both of which were corrected 

by optical realignment) after it passed 

the first relative accuracy test. Because 

of these outages and the late start up, 

the calibration error test could not be 

conducted on this monitor. There is no 

reason to suspect, however, that this 

monitor would not have passed this test. 

The monitor suffered from random 

short-term drift, but over the period of a 

month its drift averaged less than 3 percent of span. The percent uptime of the 

monitor was 86 percent. 

The Anarad operated without malfunction from the time it was installed in 

the trailer (November 1979) until the 

project was completed in April, 1980 . tt 

performed well during the relative accuracy and calibration error tests. Like the 

MSA, it sometimes suffered from random short-term drift, but over the period 

of a month, its drift averaged less than 3 

percent of span. 

Hydrogen Sulfide CEMs 

The agreement between the monitors 

and Method 11 changed radically during 

relative accuracy tests. Initially, the 

monitors showed a negative bias with 

respect to Method 11 , but in early February a positive bias began to be observed. The agreement between the 

monitors and Method 11 sometimes 

changed drastically from one day to the 

next. Tests to determine the cause of 

this bias were inconclusive. When two 

laboratories simultaneously measured 

the H2S concentration in the fuel gas 

the two laboratories agreed closely but 

their results were significantly different 

from that of the monitors (Table 4, RA 

Test 5). Further, when the fuel gas was 

spiked with known amounts of H5S 

both the monitors and the reference 

method recovered the spike. Thus, the 

cause of the bias remains unknown. Perhaps it resulted from a combination of 

several factors, including the slow response of the monitors and sudden 

changes of short duration in the H2S 

concentration in the fuel gas. 

Table 5 summarizes the results of the 

calibration drift (CD) tests. These tests 

were performed in conjunction with the 

daily zero and span checks. Since the instruments were not zeroed each day. the 

values reported represent the daily zero 

drift values corrected for the zero value 

recorded for the start of that 24-hour 

period. Specific comments about the 

monitors are presented below. 

The Teledyne responded to many 

other compounds present in the fuel gas. 

The interferences were so severe that 

field evaluation was discontinued on the 

monitor. It was not possible \o install a 

scrubber that would effectively remove 

the majority of the interferences before 

the instrument failed completely. 

The PAI was not operational for more 

than two weeks despite being returned 

Table 4. Summary of H2S Relative Accuracy Tests at Refinery 

Test 

Number 

1 

2 

3 

4A 

4B 

5 

— 

6 

7 

e 

Start 

Date 

4/27/80 

5/5/80 

6/9/81 

1/20/81 

1/20/81 

2/18/81 

Lab 1 

Lab 2 

2/25/81" 

2/25/81 

3/31/81" 

Number 

of 

Reference 

Method 

Samples 

9 

9 

9 

9 

9 

9 

7 

6 

8 

10 

Method 11 

Mean HjS 

Cone 

Ippm) 

159 

201 

208 

190 

197 

34 6 

31.7 

150 

138 

114 

Bendix 

%std28.9 

39 

58.8 

18.5 

16.4 

18.1 

22.4 

11.1 

33.5 

8.3 

%IH2Sf 

29.9 

32 

47.4 

16.1 

13.7 

86.4 

117 

12.2 

40.2 

12.0 

Relative 

Houston Atlas 

%std* 

b 

t 

47.1 

13.8 

30.0 

24.4 

28.9 

c 

c 

b 

% IHjSf 

b 

b 

37.9 

12.0 

25.1 

116 

148 

e 

e 

b 

Accuracy 

Del Mar 

%std> 

25.1 

52.4 

45.8 

28.4 

48.9 

32.0 

39.4 

c 

e 

21.5 

% [HjSf 

25.9 

43 0 

36.3 

24.7 

40.9 

153 

205 

c 

c 

31.1 

Teledyne 

%std* 

115 

74 

b 

b 

b 

b 

b 

b 

b 

b 

% IH2S1' 

119 

61 

b 

b 

b 

b 

b 

b 

b 

b 

• Standard 165 ppm HjS. IHjS) * Method 11 result. 

* Monitor not operational. 

c

 Monitor operational but not included in test because it could not be brought into calibration. 

" Fuel gas spiked with known amount of HjS using Houston Atlas. Inc. Model 601 diluter. 
P.6 

Teble 5. Calibration Drift Test Results for HjS Monitors 

Calibration Drift9- * (%) 

Test 

Number 

Test 1 

1 

2 

3 

4 

5 

6 

7 

Test 2 

; 

2 

3 

4 

5 

6 

7 

Test 3 

1 

2 

3 

4 

5 

6 

7 

Test 4 

1 

2 

3 

4 

5 

6 

7 

* Velues in 

Bendix 

Zero 

0 

0 

0 

0 

0.1 

0.1 

0 

0 

0 

0 

0.2 

0.1 

1.0 

0.1 

0.1 

1.0 

0.2 

0.2 

0.1 

4.2 

4.2 

0 

0 

0 

0 

0 

0 

— 

Span 

0.7 

0.7 

1.1 

1.1 

9.2 

8.1 

0.7 

1.1 

0 

0.7 

0.4 

2.6 

1.1 

0.4 

1.8 

0.7 

0.7 

1.5 

1.5 

2.9 

4.0 

0.7 

0 

0.7 

0 

0 

0.4 

-

Houston Atlas 

Zero 

0.1 

0.3 

0.4 

0.1 

0.3 

0.1 

6.9 

3.5 

1.4 

4.5 

4.2 

1.0 

0.6 

— 

0.1 

0.3 

1.7 

5.2 

7.6 

5.9 

2.1 

3.1 

0.7 

0.7 

0 

0 

0 

0.3 

Span 

6.3 

4.5 

0.3 

1.0 

13.9 

13.9 

2.9 

10.8 

26.0 

3.5 

3.1 

12.8 

1.4 

11.5 

4.9 

1.0 

15.6 

21.5 

— 

4.9 

5.2 

3.8 

6.6 

0.7 

0.7 

6.6 

0 

10.4 

Del Mar 

Zero 

12.5 

9.6 

19.5 

0.7 

4.8 

0 

2.6 

6.6 

4.4 

1.5 

1.5 

1.5 

0 

4.0 

1.1 

0.4 

1.1 

10.7 

9.9 

0 

1.5 

0.4 

0.7 

0 

0.6 

2.0 

— 

— 

Span 

21.3 

30.9 

52.6 

101 

44.0 

3.3 

8.1 

34.2 

26.5 

2.6 

2.6 

1.8 

0 

4.8 

7.4 

6.6 

8.5 

6.6 

18.4 

6.3 

3.7 

1.1 

3.7 

0 

4.8 

12.1 

— 

— 

table represent the daily drift as defined by the following equation 

{Calibration Gas Concentration -Monitor Reading x 100% 

Monitor Span Value 

b

 Because long-term drift was of primary concern, the instruments were not zeroed daily. 

The values in the table have been corrected by the daily zero drift. 

to the manufacturer three times for repairs. A successful relative accuracy 

test was never obtained. 

The Bendix operated continuously 

fror* the initial start-up until final shut-

• r with only four brief outages. No inferences were detected during initial 

check-out; a possible negative interference in the fuel gas was indicated but 

not confirmed. This instrument experienced the least amount of drift of any of 

the CEMs. 

One problem encountered with this instrument resulted from the fact that it 

only sampled the fuel gas approximately 

once every 3.5 minutes. This feature of 

the Bendix makes comparing its output 

for 30 minutes (total sample collection 

time less the 10 seconds) to the results 

of a 30-minute Method 11 sample of 

dubious validity. This is particularly true 

when one considers the sudden changes 

that can occur in the H2S level of the fuel 

gas. The Bendix did complete the field 

study with only two major outages and 

had a percent uptime of 89 percent. 

The Houston Atlas suffered frequent 

mechanical failure but did complete the 

majority of the field testing. Its percentage uptime was 76 percent. The failures 

were primarily in the sample dilution system which employs a Teflon sliding 

block containing a cavity of known 

volume. At times, the instrument suffered from excessive drift. Calibration 

usually took at least four hours. 

The Del Mar operated for the entire 

test program without mechanical failure. 

However, because rotameters were used 

to achieve a dilution of the fuel gas prior 

to analysis, its calibration changed when 

the density and viscosity of the fuel gas 

changed. This fact caused the instrument to have a significant amount of 

drift. The percent uptime was 97 percent, the highest of any of the monitors. 

Conclusions and 

Recommendations 

The Anarad and MSA successfully 

completed the eleven-month field study 

•nd demonstrated that reliable CO monitors with good drift control are available 

for use at petroleum refineries. Although 

C02 is an interference with these monitors, its effect is small (in terms of the 

span range) and correctable. Water 

vapor will also interfere with these NDIR 

instruments, but it is unlikely that these 

instruments would sample a gas stream 

that had not already had the moisture 

removed. 

Overall, the performance of the five 

H2S monitors was disappointing. Two of 

the five monitors never obtained a valid 

sample and a third suffered frequent 

malfunction. The absolute agreement 

between Method 11 and all monitors 

was poor and variable in eight of the ten 

relative accuracy tests. Since the source 

of this difference is unknown, the use of 

H2S monitors for compliance purposes 

cannot be recommended at this time nor 

can we advance performance specifications for accuracy. However, these 

monitors may be useful for determining 

trends and for indicating the monthly 

performance of the amine treater. For 

example, the average H2S concentration 

for all Method 11 tests (140 ppm) compares reasonably well with the average 

for each monitor: Del Mar (133 ppm). 

Houston Atlas (130 ppm) and Bendix 

(119 ppm). 

References 

1. Performance Standards for New Stationary Sources, Federal Register, 

43: 10869, March 1 5, 1978. 

2. Proposed Revisions to Performance 

Specifications 2 and 3, Federal Register, 46: 8359. January 26, 1981. 

jgJWB»-».jr 
P.7 

Bruce B. Ferguson and Richard £. Lester ara with Harmon Engineering and 

Testing. Inc.. Auburn, AL 36830. 

William J. Mitchell is the EPA Project Officer (see below). 

The complete report entitled "Field Evaluation of Carbon Monoxide and Hydrogen Sulfide Continuous Emission Monitors at an Oil Refinery." (Order No. 

PB 82-227 406; Cost: S 12.00. subject to change) will be available only from: 

National Technical Information Service 

5285 Port Royal Road 

Springfield. VA 22161 

Telephone: 703-487-4650 

The EPA Project Officer can ba contacted at: 

Environmentel Monitoring Systems Laboratory 

U.S. Environmental Protection Agency 

Reseerch Triangle Park. NC 27711 

* U . S. GOVERNMENT PRINTING OFFICE:198^559-09Z/O489 
P.8 

A STUDY TO EVALUATE CARBON MONOXIDE 

AND HYDROGEN SULFIDE CONTINUOUS EMISSION 

MONITORS AT AN OIL REFINERY 

by 

Bruce B. Ferguson and 

Richard E. Lester 

Harmon Engineering & Testing 

Auburn, Alabama 36830 

and 

W.J. Mitchell 

Quality Assurance Division 

Environmental Monitoring Systems Laboratory 

Office of Research and Development 

U.S. Environmental Protection Agency 

Research Triangle Park, North Carolina 27711 

EPA Contract No. 68-02-3105 

Prepared For 

QUALITY ASSURANCE DIVISION (MD-77) 

ENVIRONMENTAL MONITORING SYSTEMS UBORATORY 

OFFICE OF RESEARCH AND DEVELOPMENT 

U.S. ENVIRONMENTAL PROTECTION AGENCY 

RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711 
"Wf SfTp HI ' ?" ' 

DISCLAIMER 

This report has been reviewed by the Envlronmentai Monitoring 

Systems Laboratory, U.S. Environmental Protection Agency and has been 

approved for publication. Approval does not signify that the contents 

necessarily reflect the views and policies of the U.S. Environmental 

Protection Agency, nor does mention of trade names or conmercial 

products constitute endorsement or recommendation for use. 
P.10 

FOREWARD 

Measurement and nonitoring research efforts are designed to 

anticipate potential environmental problems, to support regulatory 

actions by developing an in-depth understanding of the nature and 

processes that Impact health and the ecology, to provide innovative 

means of monitoring compliance with regulations, and to evaluate the 

effectiveness of health and environmental protection efforts through 

the monitoring of long-term trends. The Environmental Monitoring 

Systems Laboratory, Research Triangle Park, North Carolina, has 

responsibility for: assessment of environmental monitoring technology 

and systems; implementation of agencywide quality assurance programs 

for air pollution measurement systems; and supplying technical support 

to other groups In the Agency including the Office of Air, Noise and 

Radiation, the Office of Toxic Substances and the Office of 

Enforcement. 

The following investigation was conducted at the request of the 

Office of Air Quality Planning and Standards (OAQPS) to determine the 

performance that can be expected from continuous emission monitors 

installed at petroleum refineries. The results of this study will be 

used by the OAQPS to determine the appropriateness of these monitors 

for use at refineries and to determine reasonable performance specifications for these monitors. 

Thomas R. Hauser, Ph.D. 

Director 

Environmental Monitoring Systems Laboratory 

Research Triangle Park, North Carolina 

11 
P.11 

ABSTRACT 

The U.S. Environmental Protection Agency (EPA) has promulgated 

New Source Performance Standards (NSPS) that require petroleum 

refineries to continuously monitor the carbon monoxide (CO) emissions 

from fluid catalytic cracking (FCC) units and also to continuously 

nonitor either the hydrogen sulfide (H_S) concentration in fuel gas 

feed lines or the resulting sulfur dioxide (SO-) concentration in the 

boiler exhaust. However, refineries are not required to install H~S 

or CO continuous emission monitors (CEMs) until performance 

specifications have been published by the EPA. Tentative performance 

specifications, proposed by EPA after laboratory and short-term field 

evaluations, were extensively evaluated in a year-long field 

evaluation conducted using five H~S and four CO continuous emission 

monitors. The H-S CEMs were installed on a fuel gas line and the CO 

CEMs were installed on a stack from a FCC unit at an east coast 

refinery. During the evaluation, performance specification testing 

was routinely performed on the instruments as the instruments were 

operated and maintained in a work environment. The CO CEMs were 

generally reliable and able to meet proposed performance 

specifications. The H-S CEMs were not able to meet the proposed 

relative accuracy criteria but the difference in measured 

concentration could not be isolated to the CEMs or the reference 

method. 

lil 
P.12 

CONTENTS 

Dl sclaimer 1 

Forward 11 

Abstract iii 

Figures v 

Tables vi 

List of Abbreviations and Symbols

 vi i 

1. Introduction 1 

2. Summary and Conclusions 9 

Carbon Monoxide Manual Method 9 

Carbon Monoxide Monitors 9 

Hydrogen Sulfide Monitors 10 

3. Recommendations 20 

Carbon Monoxide Continuous Bui sslon Monitors 20 

Hydrogen Sulfide Continuous Emission Monitors 20 

H. Description of Equipment 22 

Continuous Emission Monitors 22 

Ancillary Equipment 24 

5. Experimental Procedures 29 

General Procedures 29 

Laboratory Evaluation of the Monitors 29 

Field Evaluation of the Monitors 32 

6. Results and Discussion 35 

Manual CO Method Development/Validation 35 

Evaluation of Carbon Monoxide Monitors *0 

Evaluation of Hydrogen Sulfide Monitors 48 

References 59 

Appendices 

A. Definition of terms 61 

B. Tentative plan for the evaluation of CO and HJS continuous 

monitors at refineries 63 

C. Vendors response to letter from EPA

 71 

D. FCC emissions gas sample conditioning system 74 

E. Manual method for measuring carbon monoxide in refinery 

gases

 8 1 

F. Instrument evaluation history 96 

Iv 
FIGURES 

Number Page 

1 Sketch of field evaluation site 8 

2 Sketch of Instrumentation trailer showing instrument 

arrangement 26 

3 Plumbing diagram for FCC gas distribution to the CO CEMs.. 27 

i) Plunblng diagram for fuel gas distribution to the H.S 

CEMs 7 28 

5 Zero drift trend for Ecolyzer CEM 45 

6 Span drift trend for Ecolyzer CEM 45 

7 Zero drift trend for MSA CEM 46 

8 Span drift trend for MSA CEM 46 

9 Zero drift trend for Anarad CEM 47 

10 Span drift trend for Anarad CEM 47 

11 Zero drift trend for Bendix CEM 56 

12 Span drift trend for Bendix CEM 56 

13 Zero drift trend for Houston Atlas CEM 57 

U Span drift trend for Houston Atlas CEM 57 

15 Zero drift trend for Del Mar CEM 58 

16 Span drift trend for Del Mar CEM 58 
P.M 

TABLES 

Number Page 

1 Tentative performance specifications for CO CEMs 5 

2 Tentative performance specifications for H.S CEMs 5 

3 CO CEMs evaluated 6 

iJ H-S CEMs evaluated 7 

5 Data summary of CO CEMs 13 

6 Summary of CO relative accuracy tests at refinery 14 

7 Calibration drift test results for CO monitors 15 

8 Effect of C02, NO , SO- and CO monitors 16 

9 Data summary of H-S CEMs relative accuracy tests at 

refinery 17 

10 Summary of H S relative accuracy tests at refinery 18 

11 Calibration drift test results for H-S monitors 19 

12 Change in absorbance of CO reagent blank with time at 

room temperature 38 

13 Effect of NO and S0_ on leuco crystal violet 38 

14 Comparison between LCV and NDIR results on FCC samples... 39 

15 Relative accuracy test results on CO monitors 15 

16 Relative accuracy test results on H-S monitors 52 

17 Results of collaborative RA test on H-S monitors 55 

vi 
P.15 

LIST OF ABBREVIATIONS AND SYMBOLS 

ABBREVIATIONS 

AA — Applied Automation 

CBI — continuous emission nonitor 

d.c. — direct current 

EPA ~ Environmental Protection Agency 

FCC — fluid catalytic cracker 

FID — flame Ionization detector 

FPD — flame photometric detector 

FS — full scale 

CC — gas chromatograph 

HAI — Houston Atlas, Incorporated 

ID — Inside diameter 

IR — infrared 

LCV --- leuco crystal violet 

MSA — Mine Safety Appliance 

NBS — National Bureau of Standards 

NDIR — nondispersive infrared 

NSPS — New Source Performance Standards 

OD — outside diameter 

PAI — Process Analyzers, Incorporated 

ppm — parts per million 

PST — Performance Specification Test 

PVC — polyvinyl chloride 

RA — relative accuracy 

SYMBOLS 

CH^ — methane 

CH.SH — methyl mercaptan 

CO — carbon monoxide 

CO- — carbon dioxide 

H-S — hydrogen sulfide 

NO — oxides of nitrogen 

SO- — sulfur dioxide 

vii 
P.16 

SECTION 1 

INTRODUCTION 

On March 15, 1978, EPA promulgated New Source Performance Standards (NSPS) that required petroleum refineries to continuously monitor the carbon monoxide (CO) •.missions from fluid catalytic cracking 

(FCC) units (1). Refineries were required to also continuously 

nonitor either the hydrogen sulfide (H-S) concentration in fuel gas 

feed lines or the resulting sulfur dioxide (SO.) concentration in the 

boiler exhaust (1). However, refineries were not required to install 

H_S or CO continuous emission monitors (CEMs) until performance 

specifications were published by the EPA. 

Tables 1 and 2 present the tentative performance specifications 

for both CO and H-S monitors that were subsequently proposed by an EPA 

contractor after laboratory and short-termed field evaluations. Terras 

used in these tables and throughout the report are defined in Appendix 

A. 

In the laboratory phase, candidate instruments were evaluated to 

determine: 

• response characteristics 

• stability with time, temperature and flow rate 

• sensitivity to potential interferences likely to be 

present in the sampled gas. 

The five CO and two H-S monitors that performed adequately in the 

laboratory were then evaluated for approximately two months at a 

petroleum refinery (2,3). Only one CO monitor and one H-S monitor 

performed adequately in the field testing. In the case of the CO 

monitors, daily calibration checks were mandatory for reliable operation of all the instruments, but even with the inclusion of daily 

calibration, the contractor questioned the long-term reliability of 

the CO monitors. Further, instrument malfunctions, sampling system 

nalfunctions and data logger malfunctions plagued the field evaluation 

of both types of monitors which resulted in a significant amount of 

downtime and lost data. 

In April 1979, EPA initiated additional work to determine: (1) 

Information about long-terra instrument durability, data validity and 

maintenance requirements of commercially-available CO and H-S CEMs at 

a refinery; and (2) the validity of the tentative performance specifications for the instruments. In addition, a manual (non-instrumental) 

method for measuring CO was to be developed and evaluated to serve as 

an alternate to EPA Reference Method 10. 
To procure the monitors, EPA contacted vendors of CO and H-S continuous stack gas monitors by letter and asked them to submit information about the nonitor(s) they thought would be suitable for the 

appropriate refinery process, the operating principle and approximate 

cost. A copy of that letter and the Project Accomplishment Plan that 

accompanied it are included in Appendix B. Appendix C contains the 

vendor response to the letter and, if they suggested a nonitor, the 

model number, cost and operating principle. 

Of the 35 vendors contacted, 16 did not respond. A total of 10 

H-S and 13 CO monitors were recommended for consideration. From this 

list, five H-S and four CO monitors were selected for evaluation. The 

pertinent information about each instrument ls Included in Tables 3 

and 4. The selection criteria (described in detail in Appendix B) 

involved total cost, operation/detection principle and engineering 

Judgement about the likelihood the monitor would be suitable for the 

application. For example, one company proposed to use a converted NO 

monitor for measuring H-S, but did not consider the likelihood thai 

organics in the fuel gas would interfere with the chemiluminescence 

reaction. 

After receipt, the monitors were installed in a trailer at the 

Harmon Engineering & Testing (HE&T) facility in Auburn, Alabama and 

were subjected to checks for: drift, response time, electronic noise 

level, interferences and response variation due to changes in ambient 

temperature and sample flow rate. The monitors and trailer were then 

transported to a refinery for an 11-month field study in which they 

were tested at periodic intervals for relative accuracy, response 

time, calibration error and drift. 

The refinery at which the field evaluation was conducted had 

added a new CO boiler to the FCC unit ln early 1979 to recover additional energy from the FCC exhaust gas and to reduce the CO concentration ln the gas stream. The emission gas from this unit was used for 

the CO CEM evaluation. 

An EPA-designed sample conditioning system (described in Appendix 

D) removed the moisture and particulate matter from the FCC gas at the 

sampling port. The conditioned gas was transported to the sample 

manifold through 200 meters of 0.95 on ID black, nylon tubing at a 

flow rate ranging from 8 to 15 Lpm. This sample conditioning system 

was installed ln February 1980, and was operated continuously for 

eleven weeks before the monitors arrived at the refinery to allow time 

to correct any potential design deficiencies (none were found) before 

attaching the monitors to it. Three measurements of CO- and CO 

concentrations performed during this 11 week period Indicated these 

compounds were not affected by the sample conditioning system. In 

these checks, inlet and outlet samples were taken in Tedlar bags and 

analyzed by NDIR techniques. 
P.18 

A aampie manifold was used to distribute the conditioned FCC 

stack gas to the four CO CEMs. The distribution system was designed 

to vent excess gas not required by the instruments for nonnal operation. The unit was also equipped with solenoid valves controlled by a 

data logger for automatic zero and span checks each day. 

The H-S monitors sampled a fuel gas line at a point downstream of 

the amine treater used to remove H-S from the fuel gas. Ifcring the 

project, both monoethanolamine and*^ diethanolamine were used in the 

amine treater. 

The fuel gas was distributed to the five H-S monitors by means of 

a six-port sampling manifold that was supplied continuously with 

treated fuel gas. The fuel gas was transported from the sampling 

point to the instrunentatlon trailer through approximately 100 m of 

0.63 cm OD stainless steel tubing. 

All instruments were located in a 24-foot long, air conditioned 

trailer. Figure 1 shows the location of the instrumentation trailer 

in relation to"the two sources that were monitored. . 

The output from the monitors was simultaneously recorded on an 

Esterline Angus Model PD 2064 data logger, Techtran Model 816 cassette 

tape recorder and an Esterline Angus multipoint recorder. While 

sampling process gas, each monitor's output was read at 3-minute 

intervals and the average value for 10 readings was printed by the 

data logger and simultaneously recorded by the Techtran Model 816. 

The multipoint recorder printed each 3-n>inute reading without 

averaging. During relative accuracy testing, the data logger measured 

each monitor's output at 1-minute intervals and reported the average 

every 20 or 30 minutes. 

At the beginning of the field evaluation (April 1980), the tentative performance tests listed in Tables 1 and 2 were performed. 

Field testing performed after May 1980, however, concentrated on relative accuracy and calibration drift tests ln response to a major 

change in EPA's overall approach to monitor system performance specifications. This change, formally proposed in the Federal Register(4), 

involved a drastic simplification on the Performance Specification 

Test (PST) Procedure H. Under these proposed PST revisions the only 

mandatory tests are relative accuracy and calibration drift. The 

other tests that were previously required (5) are now optional. 

Five CO and ten H-S relative accuracy tests were conducted during 

the 11-roonth field evaluation, but not all monitors were operational 

in all tests. In addition, the monitors were subjected to daily 15-

nlnute zero and span checks. Except for days when relative accuracy 
P.19 

testing Was being performed, zero and span calibrations were not 

normally adjusted nore often than weekly (frequently less than once 

per nonth) ln order to provide data on the drift characteristics of 

each instrunent. Only the gas chromatograph (GC) instruments were 

equipped with automatic zero and no instrument was equipped with 

automatic span adjustment. 

Relative accuracy tests on the H-S monitors used EPA Method 11 

(6) as the reference nethod. Relative accuracy tests on the CO 

nonitors were conducted using EPA Method 10 and an alternate nethod 

(described in Appendix E) developed during this study. This alternate 

nethod can be used to check the accuracy of CO continuous nonitors 

using NDIR as the measurement technique. 

4 
P.20 

TABLE 1. TENTATIVE PERFORMANCE 

SPECIFICATIONS FOR CO CEMS 

PARAMETERS SPECIFICATION 

Kan (a 

Calibration Error 

Relative Accuracy 

1.2 

Precision 

Response Tlae (tyataai) 

Output Kolee 

Zero Drift, 2 lours 

Zero Drift. 24 loura1 

Span Drift. 24 loura 

Interference EquIT. 

J51 C0» aa ppa CO 

10Z HiO aa ppa CD 

Operational Period 

0-1000 ppa 

<2Z Span 

<10Z Hean Mf . 

~ Value 

<1Z Span 

£10 Hlautea 

«1Z Span 

«1Z Span 

<2I Span 

<2.SZ Span 

£10 ppa 

<5 ppa 

>168 Houra 

Expressed at aua of absolute aean value plua 

9SZ confidence Interval ln a aeries of teata. 

T M a value la baaed on a relative cooparlaon 

•f the aosltora to each ether and not to 

Method 10. Tba tenet are defined in Appendix 

A. 

TABLE 2. TENTATIVE PERFORMANCE 

SPECIFICATIONS FOR H2S CE>S 

PARAMETERS SPECIFICATION 

Range 

Calibration Error 

1 Relative Accuracy 

Keaponae Tlae (STatea) 

Zero Drift, 2 loura 

Zero Drift. 24 loura 

Span Drift. 2 loura 

Span Drift, 24 lours 

Operational Period 

1 

O-3O0 ppa 

<5Z of Each 

~ Calibration 

Mixture 

<10Z Mean Kef. 

"~ Value 

<15 Mlnutea 

<2Z Span 

<2Z Span 

<2Z Span 

<2.SZ Span 

>168 ROUTa 

Expretaed at aua of absolute Bean value plua 

551 confidence Interval in a aeries ef teata. 
TABLE 3. CO CEMS EVALUATED 

INSTRUMENT MANUFACTURER MODEL NUMBER ABBREVIATION OPERATINC PRINCIPAL 

Anarad. tne. 

P. 0. Boa 3180 

Santa Barbara. CA 93103 

teolyter 

Energetics Science 

85 Executive Blvd. 

Otvlalon of Beeton Dickinson Cuapsiij 

Elasford. NT 10523 

50 IR 

3l07/2«4v 

Anarad 

Ecolyter 

Nondleperalve Infrared 

Detector (NDIR) 

Optical Solid Stats Detector 

EleetrocHealeal Sensor 

Applied Automation, tne. 

Psvhuska Road 

Bartleevllle. OR 74004 

Mine Safety Appliances Ceaoany 

7)22 Neede Street 

Pittsburgh, PA 13208 

Optlchroa 102 

LIRA 202 

AA1M 

MSA 

Cas Chroaatoftrspti/Pleas 

Ion Itation Detector 

(CC/FID) 

Nondleeeralve Infrered/ 

Luft Detector (NDIR/Luft) 

ho 
TABLE 4 , HaS CEMS EVALUATED 

INSTRUMOIT MANUFACTURER MODEL NUMBER ABBREVIATION OPERATINC PRINCIPAL 

BendU Envlrewaantsl » Proessa Isstt 

P. 0. Drawer 831 

Levlsburg, V. VA 24901 

Del Her Scientific, Inc. 

P. 0. BOB «R6 

Addison, Texas 

7770 

DH-W 

BendU 

Del Mar 

Cas Chraaatetraph/Plaas 

Photoaetrlc Detector 

(CC/FPD) 

Lead Aeetata tapregrste4 

Peper Tape 

Houston Atlas, Inc. 

9441 Baythome Drive 

Houston, TX 77041 

825R/102 HAI Laad Acetate taprsgrstsd 

Paper Tape 

Process Anslyters, 

UOI State Road 

Princeton, MJ 

lac. 32-230 PAI Cas Chreaetotrspn/Pleaa 

Photometric Detector 

(CC/FPD) 

Teledyne Anatvtleal Tnntt 

3)1 W. Mission Avenue 

San Cabrlcl. CA 91778 

uta 811 DNCO-20I Teledyne Ultraviolet Abaorptloa 
SAMPLE CONDITIONING SYSTEM 

FUEL OAS PIPELINE 

FUEL OAS SAMPLE LINE 

FIGURE 1. SKETCH OF FIELD EVALUATION SITE 

ro 

co 
P.24 

SECTION 2 

SUMMARY AND CONCLUSIONS 

CARBON MONOXIDE MANUAL METHOD 

The analytical portion of the manual CO test method developed in 

this study was biased 4 percent high with respect to a Bendix 8501-

5CA NDIR CO analyzer. The precision associated with a single analysis 

was 4.3 percent of the concentration for the range 10 to 1100 ppm. 

The precision was approximately 2.5 percent of the mean concentration 

for analyses performed in triplicate. This means that two analytical 

results on the same bag sample should differ by more than 8.4 percent 

only one time in 20 due to chance alone. The method was significantly 

affected by S0? and NO, so these compounds were removed during sample 

collection by bubbling the gas through alkaline potassiun permanganate. 

Table 5 summarizes the data collected for each CO instrument 

during the study. Tables 6 and 7 summarize the relative accuracy and 

calibration drift tests, respectively. Sometimes, less than the 

desired nine manual method tests were achieved because of leaking 

Tedlar bags and process failure. Table 8 shows the effect of C02, N0X 

and S0? on each monitor's response. The following paragraphs 

summarize the performance of each lnstrunent. 

CARBON MONOXIDE MONITORS 

Applied Automation Optlchrom 102 

The monitor performed well in the laboratory checkout, but'not in 

the field evaluation. A valid relative accuracy test was never 

achieved because of the monitor's erratic performance; thus, its percent uptime was zero. 

Ecolyzer 3107 

This monitor was equipped with an Energetics Science Model 2949 

scrubber to remove NO and SO.. Originally, each scrubber cost $21, 

but by June 1980, this price had increased to $45. The scrubber was 

found to be inadequate for long-terra use on FCC gases. scrubber 

failure, which In turn caused monitor detector failure, occurred from 

1 to 20 days after Installation (depending on the NO and SO. 

concentration encountered). To protect the detector and save cost, a 
25 an long by 2.5 ca diameter PVC pipe containing activated charcoal 

was.substituted for the Model 2949 scrubber during routine use and the 

Model 2949 scrubber used only during relative accuracy tests. The 

response time of the system with the large charcoal scrubber installed 

was approximately 30 minutes compared to less than 1 minute when the 

Model 2949 scrubber was used. At the S0? and NO concentrations 

normally encountered in an FCC stack (500 ppm SO., 20a ppm NO ) even a 

new Model 2949 scrubber, was unable to remove ail of the interfering 

gases such that the instrument could pass a relative accuracy test 

(See RA test 2/81 (A) in Table 6). Carbon dioxide at 15 percent by 

vol ime did not interfere. The monitor drifted significantly over a 

period of several days at frequent intervals. The detector was 

replaced once during the study and the evaluation stopped after the 

detector failed the second time. Detector failure was also a problem 

in the previous study (2). This instrument does not appear to be 

suitable to continuously monitor CO concentrations in FCC emissions. 

Mine Safety Appliance (MSA) Lira 202 

As received, the output from this monitor was not compatible with 

the data logger thus, the laboratory check-out tests were not 

completed before the trailer was sent to the refinery. At the 

refinery the monitor drifted on a daily basis but, over a month, the 

zero and span drift frequently averaged out to less than 3 percent. No 

interference was found from S0_ or NO and only a small and constant 

interference was found from CO. (1 ppra per 1 percent CO.). Although 

the test was not done, water vapor would not be expected to be a 

significant interferent. The monitor successfully completed the 

11-month evaluation with only two failures, both of which were 

corrected by an optical realignment. 

Anarad 501-R 

Except for the time it was in transit to the refinery, this monitor operated continuously without an outage from October, 1979 until 

testing was completed in April 1981. Interferences from SO. and NO 

were not experienced, but small, constant interferences did result 

from CO. (3 ppm per 1 percent CO.) and from water (3 ppm per 1 percent 

H.O). Since the stack gas was conditioned to yield a dewpoint of 

-20 C, water was not an interferent in the field tests. The monitor's 

output was usually more stable than any of the other instruments. 

HYDROGEN SULFIDE MONITORS 

The H.S CEMs were evaluated in the laboratory prior to the field 

testing. Table 9 summarizes the data collected for each H.S 

instrument during the study. Table 10 summarizes the relative 

accuracy testing performed in the field, and Table 11 summarizes the 

10 
P.26 

calibration drift tests. In some relative accuracy tests, less than 

nine reference method samples were collected because plant upsets 

Increased the H.S concentration above the span range of the monitors. 

The following paragraphs summarize the performance of each 

instrument. 

Bendix Model 7770 

This monitor operated continuously from initial start-up until 

final shut-down with only four brief outages. Two outages were caused 

by a ruptured diaphragm in the sampling valve, one outage occurred 

when an operator accidently shorted a circuit in the heater control 

unit and the fourth occurred from an obstruction in the process air 

supply. 

Interferences were not detected during the initial checkout. 

However, during relative accuracy tests, a possible interference from 

something in the fuel gas was indicated but could not be confirmed. 

Since the monitor sampled the fuel gas once every 3.5 minutes, it was 

difficult to conduct a relative accuracy test when the H.S level in 

the fuel gas was changing rapidly (as frequently occurred). The 

instrument generally performed in a reliable manner throughout the 

evaluation. 

Process Analyzers Incorporated Model 32-230 

This monitor operated for less than 3 days during the laboratory 

check-out and was returned to the manufacturer for repairs on three 

separate occasions. Mechanical failure, electronics failure and 

corrosion of parts prevented the monitor from obtaining a valid 

analysis of the fuel gas and thus its percent uptime was zero. The 

instrument does not appear suitable for use in this application. 

Teledyne Model 611 DHCO-20X 

This monitor was received approximately 3 months later than 

scheduled, which prevented a complete laboratory checkout of the 

monitor. A valid analysis of the fuel gas was never obtained because 

of interference from diethanolamine and sulfur compounds such as 

mercaptans and carbonyl sulfide. The molecular sieve scrubber 

originally supplied with the monitor could not compensate for these 

interferences. By the time Teledyne supplied an improved scrubber, 

the monitor had ceased to operate; thus its percent uptime was zero. 

The Instrument does not appear to be suitable for use in this 

application. 

11 
P.27 

Houston Atlas Model 825R/102 

Although this monitor suffered frequent mechanical failure, it 

did complete most of the field testing program. The most frequent 

cause of failure was the gas dilution system. This is the same 

problem that affected the Houston Atlas instrument evaluated in a 

previous study(3). This monitor required a minimum of 4 hours for a 

major calibration and, at times, was subject to severe drifting. Sane 

of the operational problems encountered were due to operator error and 

the corrosive environment of the instrunentatlon trailer. Some data 

were lost because the person conducting the daily checks failed to 

replace the lead acetate tape in a timely manner. 

Del Mar Scientific Model DM-W 

This monitor operated for the entire test program without 

mechanical failure. However, because rotameters were used to achieve 

a 1:10 dilution of the fuel gas, its calibration changed when density 

and viscosity of the fuel gas changed. Sudden changes in the gas viscosity occurred during some of the relative accuracy tests; thus the 

agreement between Method 11 and the monitor varied drastically during 

some tests. A bias also seemed to exist between the monitor and the 

manual method that could not be explained by viscosity changes. Same 

data were lost because the person conducting the daily checks failed 

to replace the lead acetate tape in a timely manner. 

12 
TABLE 5. DATA SUMMARY OF CO CEMS 

SPECIFICATIONS 

PROPOSED IN 

REF. 2 ANARAD ECOLYZER MSA A/1102 

w 

UBORATORY DATA 

Precision (Z FS) 

Span Noise (Z FS) 

Zero Noise (Z FS) 

H^O Interference (as ppn CO) 

1*Z CO2 Interference (as ppm CO) 

Response Time (seconds) 

FIELD DATA 

Zero Drift, 24 Hr. (Z FS) 

Zero Drift, 2 Hr. (Z FS) 

Span Drift, 24 Hr. (Z FS) 

Calibration Error (Z FS) 

- high (Z FS) 

- medium (Z FS) 

- low (Z FS) 

Field Response Time, 90Z/95Z FS 

(seconds) 

Instrument Operational Time (*) 

<1 

<1 

a 

<4 

<10 

^600 

<2 

<1 

<2.5 

<2 

a 

a 

a 

<600 

a 

<0.1 

<0.1 

0.5 

32.4 

28.2 

7.5 

2.5 

0.89 

4.2 

1.7 

9.1 

4.7 

13/16 

100 

<0.1 

<0.6 

0.4 

n/a 

<0.1 

53 

9.2 

1.3 

53.8 

5.0 

13.0 

4.6 

45/47 

57 

<0.1 

<0.2 

0.1 

b 

b 

4.8 

2.2 

1.3 

3.1 

b 

b 

b 

11/13 

86 

<0.1 

<0.1 

0.9 

3.0 

<0.1 

138 

0.4 

0.42 

4.3 

2.6C 

6.9C 

8.4C 

242/242 

0 

Not specified. 

Data not complete due to instrument malfunction. 

Result of one test. 

Time the instrument was producing useable data during the 11-month field evaluation vlthout 

considering the absolute accuracy of the data, i.e., without correcting for the days the 

monitor was out of calibration. However, if the monitor was known to be malfunctioning and 

not just out of calibration, the monitor vas considered to be off line. 
TABLE 6. SUMMARY OF CO RELATIVE ACCURACY TESTS AT REFINERY 

DATE 

9/80 

1/81 

2/81 

2/81 

Mean 

(A) 

(B) 

NUMBER OF 

REFERENCE 

METHOD 

SAMPLES 

5 

9 

9 

9 

. MEAN 

CO 

CONC 

(*) 

2 

2 

12 

3 

LCV* 

CO 

CONC 

(ppm) 

80 

404 

507d 

712 

ECOLYZER 

Z Std" 

5 

14 

>100 

e 

40 

Z [CO] 

34 

17 

>100 

e 

50 

RELATIVE ACCURACY 

ANARADb 

Z StdL 

3.8 

13 

7.7 

12.7 

9.3 

I ICO) 

24 

16 

7.6 

8.9 

14 

MSAb 

Z Std" 

2.9 

13 

4.2 

9.7 

7.4 

X [COJ 

18.4 

16 

4.3 

6.8 

11 

b 

c 

d 

This is the avirage of the manual method results using the letico crystal violet method developed 

in this study. 

Corrected for CO. interference. 

Standard for CO: 500 ppm. 

Monitors sampled cylinder gases containing 502 ppm CO, 12Z CO. and different concentrations 

of NO and SO. in nitrogen. This was done to evaluate the performance of the monitors vhen 

they vere sampling a stack gas vith NO and SO. levels representative of an FCC stack gas. 

During the ll-month study, process upsets and refinery equipment malfunction caused the 

CO levels to exceed the span range of the monitors and so it vas necessary to dilute the 

stack gas to bring the CO level into the vorking range of the monitors during the relative 

accuracy test. Dilution vas obtained by introducing plant instrument air at the probe. 

This dilution reduced the NO and SO. levels by a factor of 4 to 6 and permitted the 

Ecolyzer to obtain an accurate analysis of the stack gas. 

Monitor not operational because of detector failure from high SO. and NO levels encountered 

in Test 2/81(A). 
P.30 

TABLE 7. CALIBRATION DRIFT TEST RESULTS FOR CO MONITORS 

DAY 

Test 1 

1 

2 

3 

4 

5 

6 

7 

Test 2 

1 

2 

3

C 

4 

5 

6 

7 

Test 3 

1 

2 

3 

4 

5 

6 

7 

CALIBRATION 

ECOLYZER 

Zero 

1.4 

0.3 

0.2 

0.6 

0.4 

0.9 

1.2 

"0.2 

0.2 

0.7 

0.2 

0 

0.1 

0.1 

0.1 

0.3 

0 

0.1 

3.1 

2.2 

0.7 

• 

Span 

0.4 

4.4 

1.7 

1.0 

0.7 

0.9 

1.6 

7.2 

0.1 

10.8 

0.2 

1.6 

0.9 

0.3 

0.1 

3.4 

0.4 

0.9 

2.7 

2.8 

0.9 

DRIFT*'

 b (Z) 

ANARAD 

Zero 

1.7 

0.2 

0.2 

1.0 

2.0 

2.1 

3.2 

2.4 

0.2 

0.4 

0.4 

1.1 

0.1 

0.5 

0.9 

1.3 

0 

0.6 

0.4 

0.4 

0.2 

Span 

0.1 

2.4 

1-6 

0.2 

0.8 

1.5 

4.5 

0.7 

4.4 

3.4 

0.3 

0.4 

1.9 

1.0 

0.6 

1.7 

0.7 

1.1 

1.1 

0.1 

0.1 

MSA 

Zero 

0.6 

0.9 

1.2 

1.4 

2.5 

3.3 

2.9 

0 

1.7 

5.4 

1.3 

2.5 

0.2 

0.1 

0.2 

0.2 

0.4 

0.7 

1.8 

4.2 

0.9 

Span 

0.1 

1.2 

2.0 

0.8 

6.2 

3.0 

0 

0.9 

2.4 

1.3 

3.6 

3.7 

1.1 

1.7 

1.2 

1.2 

0.1 

1.2 

2.8 

1.1 

2.8 

* Values ln table represent the daily drift as defined by the 

following equation 

{Calibration Cas Concentration - Monitor Reading! x 100Z 

Monitor Span Value 

b 

Because long-term drift was of primary concern, the instruments 

were not zeroed dally. The values in the table have been 

corrected by the dally zero drift. 

15 
TABLE 8. EFFECT OF C02» NOx, SOj ON CO MONITORS 

DATE 

6/5/80 

9/20/80 

11/18/80 

1/20/81 

2/17/81 

2/17/81 

* 2/17/81 

teo) 

(ppm) 

100C 

100C 

iooc 

iooc 

500d 

500e 

500f 

MONITOR RESPONSE (ppm) 

Ecolyzer Anarad 

165 

141 

b 

206 

1680 

1430 

1660 

149 

139 

152 

140 

544 

538 

523 

MSA 

117 

112 

113 

107 

504 

512 

504 

MONITOR RESPONSE CORRECTED FOR 

Ecolyzer Anarad 

165 

148 

b 

206 

1680 

1430 

1660 

113 

101 

116 

104 

508 

502 

487 

CO2 1 IfTERFERE 

MSA 

105 

100 

101 

95 

492 

500 

492 

NC^ 

CO- Interference: Ecolyzer - none; Anarad - 3 ppm/lZ C0-, MSA - 1 ppm/lZ CO-. 

Monitor not operational because of detector failure. 

Cylinder Analysis: 12Z C02; 200 ppm NO; 500 ppm S02; balance Nj. 

Cylinder Analysis: 12Z C02; 400 ppm NO; 0 ppm S02; balance Nj. 

Cylinder Analysis: 12Z C02; 0 ppm NO; 700 ppm S02; balance N2> 

f Cylinder Analysis: 12Z C02; 200 ppm NO; 500 ppm S02; balance Nj. 
TABLE 9. DATA SUMMARY OF HjS CEMS 

SPECIFICATIONS 

PROPOSED IN 

REFERENCE 

BENDIX DEL MAR HAI PAI TELEDYNE 

LABORATORY DATA 

Precision (Z FS) 

Span Noise (Z FS) 

Zero Noise (Z FS) 

100 Z Cfy Interference (Z FS) 

40Z CHA in H2 Interference (Z FS) 

200 ppm CH3SH Interference (Z FS) 

Response Time (sec) 

FIELD DATA 

Zero Drift, 

Zero Drift, 

Span Drift, 

Span Drift, 

24 Hr. (Z FS) 

2 Hr. (Z FS) 

24 Hr. (Z FS) 

2 Hr. (Z FS) 

Calibration Error (Z FS) 

- high (Z FS) 

- medium (Z FS) 

- Iov (Z FS) 

Field Response Time, 90Z/95Z FS (sec) 

Instrument Operational Time (*) 

a 

a 

a 

a 

a 

a 

<900 

I

2 

<2 

^2.5 

<2 

<5 

a 

a 

a 

£900 

a 

0.3 

0.4 

0.1 

<0.1 

<0.1 

<0.1 

210 

0.04 

0.05 

1.7 

0.6 

0.7 

6.2 

8.0 

230/230 

89 

4.3 

1.1 

2.1 

<0.1 

<0.1 

<0.1 

306 

5.2 

2.1 

11.7 

3.4 

9.2C 

32c 

17c 

304/328 

97 

2.8 

0.9 

0.5 

-0.2 

-0.4 

<0.1 

630 

1.6 

1.9 

13.4 

13.1 

14c 

20c 

40c 

480/583 

76 

b 

b 

b 

b 

b 

b 

b 

b 

b 

b 

b 

b 

b 

b 

0 

0.6 

0.6 

2.4 

<1 

<1 

82 

35 

b 

6.1 

b 

2.1 

9.3C 

30c 

47 

b 

0 

Not specified. 

Data not complete due to Instrument malfunction. 

Result of one test only. 

Time the instrument vas producing useable data during 11-month field evaluation vlthout considering 

the absolute accuracy of the data, i.e., vlthout correcting for days the monitor vas out of calibration. However, if the monitor vas knovn to be malfunctioning and not just out of calibration, 

the monitor vns condidered to be off line. 
, TABLE 10. SUMMARY OF H?S RELATIVE ACCURACY TESTS AT REFINERY 

! TEST START 

NO. DATE 

RELATIVE ACCURACY 

NUMBER 

OF METHOD 11 

REFERENCE MEAN HaS 

METHOD CONC BENDIX HOUSTON ATLAS UEL MAR TELEDYNE 

SAMPLES . (ppm) 2 stdd Z (H2S] * 7. std" 2 lH2S]aZ std" Z [H2Sl* 2 std° 2 [HjSj" 

1 4/27/80 

2 5/5/80 

3 6/9/81 

4A 1/20/81 

4B 1/20/81 

5 2/18/81 

Lab 1 

Lab 2 

6 

7 

8 

2/25/81' 

2/25/81 

3/31/81' 

9 

9 

9 

9 

9 

9 

7 

6 

8 

10 

159 

201 

208 

190 

197 

34.6 

31.7 

150 

138 

114 

28.9 

39 

58.8 

18.5 

16.4 

18.1 

22.4 

11.1 

33.5 

8.3 

29.9 

32 

47.4 

16.1 

13.7 

86.4 

117 

12.2 

40.2 

12.0 

b 

b 

47.1 

13.8 

30.0 

24.4 

28.9 

c 

b 

b' 

b 

37.9 

12.0 

25.1 

116 

148 

c 

c 

h 

25.1 

52.4 

45.8 

28.4 

48.9 

32.0 

39.4 

25.9 

43.0 

36.3 

24.7 

40.9 

153 

205 

115 

74 

b 

b 

b 

b 

b 

c c 

21.5 31.1 

b 

b 

b 

119 

61 

b 

b 

b 

b 

b 

b 

b 

b 

Standard - 165 ppm H2S. Span [H2S] - Method 11 result. 

Monitor not operational. 

Monitor operational but not included in test because lt could not be brought into calibration. 

Fuel gas spiked vith knovn amount of H2S using Houston Atlas, Inc. Model 601 diluter. 
TABLE 11. CALIBRATION DRIFT TEST RESULTS FOR H.S MONITORS 

TEST CALIBRATION DRIFT**

 b (2) 

KUMBER BENDIX HOUSTON ATLAS DEL MAR 

Zero Span Zero Span Zero Span 

Test 1 

1 0 0.7 0.1 6.3 12.5 21.3 

2 0 0.7 0.3 4.5 9.6 30.9 

3 0 1.1 0.4 0.3 19.5 52.6 

4 0 1.1 0.1 1.0 0.7 101 

5 0.1 9.2 0.3 13.9 4.8 44.0 

6 0.1 8.1 0.1 13.9 0 3.3 

7 0 0.7 6.9 2.9 2.6 8.1 

Test 2 

1 0 1.1 3.5 10.8 6.6 34.2 

2 0 0 1.4 26.0 4.4 26.5 

3 0 0.7 4.5 3.5 1.5 2.6 

4 0.2 0.4 4.2 3.1 1.5 2.6 

5 0.1 2.6 1.0 12.8 1.5 1.8 

6 1.0 1.1 0.6 1.4 0 0 

7 0.1 0.4 - 11.5 4.0 4.8 

Test 3 

1 0.1 1.8 0.1 4.9 1.1 7.4 

2 1.0 0.7 0.3 1.0 0.4 6.6 

3 0.2 0.7 1.7 15.6 1.1 8.5 

4 0.2 1.5 5.2 21.5 10.7 6.6 

5 0.1 1.5 7.6 - 9.9 18.4 

6 4.2 2.9 5.9 4.9 0 6.3 

7 4.2 4.0 2.1 5.2 1.5 3.7 

Test 4 -

1 0 0.7 3.1 3.8 0.4 1.1 

2 0 0 0.7 6.6 0.7 3.7 

3 0 0.7 0.7 0.7 0 0 

4 0 0 0 0.7 0.6 4.8 

5 0 0 0 6.6 2.0 12.1 

6 0 0.4 0 0 

7 0.3 10.4 

*- Valuee lo tabic represent the duly drift •• defined by Ch* 

following equation 

|Ce31bretlon Gaa Concentration - Monitor Kcadlml • 100Z 

Hon1tor Span Value » 

* Secauae long-tei-a drift waa of prlaary concern, the inatrunenta 

were not aeroed dally. The valuee ln the table have been 

corrected by the dally sero drift. 

19 
P.35 

SECTION 3 

RECOMMENDATIONS 

CARBON MONOXIDE CONTINUOUS EMISSION MONITORS 

The Anarad and MSA monitors successfully completed the 11-month 

study and demonstrated that monitors with good drift control are 

available and suitable for the measurement of CO concentrations ln FCC 

emission gas. Based on the results of this study, the following 

specifications are advanced for CO monitors. 

• Calibration Drift. The CEMs calibration must not drift 

or deviate from the reference value of the calibration 

gas by more than 5 percent of the established span value 

of 1,000 ppm over each 24-hour operating period. 

• Relative accuracy (RA). The RA of the CEMs must be no 

greater than 20 percent of the mean value of the 

reference method (RM) test data in terms of the units of 

the emission standard or 15 percent of the applicable 

standard, whichever is greater, as calculated using 

Equation 2-4 in Reference 4 and the manual CO method 

results as the reference value. 

The correlation among the reference method and CEM data, the 

number of RM tests and the calculations should be the same as those 

given in Section 7 of Performance Specification 2(4). 

Because of the possibility of leaks when sampling with Tedlar 

bags, the number of samples taken for a relative accuracy test should 

be at least twelve with the option of discarding the results from any 

three if it appears that leakage has occurred. The relative accuracy 

testing should be done while the CO concentration ln the emissions is 

varying less than 10 percent over the duration of the testing. 

HYDROGEN SULFIDE CONTINUOUS EMISSION MONITORS 

The performance of the H.S monitors was disappointing. Only three 

of the five monitors were suftable for field use and only one monitor 

(Bendix) had an uptime ln excess of 85 percent. The other two monitors that passed the test suffered severe drift problems. The Bendix 

20 
P.36 

sampled a total of 17 times each hour, but each sample duration was 

less one second. Thus, the use of the integrated Method 11 sampling 

approach for determining the accuracy of this monitor ls questionable 

unless the fuel gas H.S concentration can be held constant. The 

absolute agreement between Method 11 and all the monitors was poor and 

variable in eight of the ten relative accuracy tests as shown in Table 

10. Since the cause or causes of this difference could not be 

Identified, the use of H.S monitors for compliance purposes cannot be 

recommended at this time. 

The monitors may be useful, however, for determining trends and 

for indicating amine treater performance, as shown by the overall 

agreement between the average for all Method 11 tests and that for 

each monitor (i.e.. Method 11-140 ppm, Bendix-119 ppm, Houston Atlas130 ppm and Del Mar-133 ppm). (Some Method 11 tests used in calculating the above averages were not reported in the text of this report 

because they represented cases where plant malfunction or instrument 

failure caused a relative accuracy test to be aborted before an adequate number of samples had been obtained). 

Due to the apparent bias between the Reference Method 11 tests 

and the H.S CEM data, an interference to the reference method tests 

is suspected. Additional evaluation of the reference method should be 

performed before performance specifications are developed and 

installation of monitors is required. 

21 
P.37 

SECTION 4 

DESCRIPTION OF EQUIPMENT 

CONTINUOUS EMISSION MONITORS 

Carbon Monoxide Monitors 

Applied Automation .Optichrom 102— 

The Model 102 ls a gas chromatograph that uses a flame ionization 

detector (FID) to detect methane catalytically produced from carbon 

monoxide. The oven, valves and controls are located ln an air purged 

module and the programmer is ln a separate cabinet. A sample loop is 

used to sample an exact volume of gas which ls Injected onto the 

column by a multi port valve. Two columns in series are used for the 

separation - when the CO has eluted through the first column, it is 

backflushed to remove the heavier components while additional separation takes place on the second column. A catalytic methanator converts the CO to methane (in the presence of hydrogen carrier gas) 

which ls detected by the FID. 

Automatic zeroing ls accomplished via an auto zero control on the 

detector Immediately before the CO peak reaches the detector. Spanning is accomplished by a series of attenuation switches and a fine 

attenuation potentiometer. 

Ecolyzer 3107— 

The Ecolyzer Model 3107 monitor utilizes an electrochemical 

sensor to measure CO in the ranges of 0 to 1000 ppm and 0 to 500 ppm. 

The unit utilizes a sampling pump and a by-pass to vent unused sample 

around the sensor. To maintain Constant sample humidity, a salt water 

humidifer is located upstream of the detector. An absorbent cartridge 

ls provided for the removal of SO. and NO from the sample gas. 

Sample pressure must not exceed 2.5 cm water at the sample pump inlet. 

Mine Safety Appliances Lira 202— 

The Lira 202 has two IR lamps, a "Luft-type" infrared detector 

and gold-lined sample and reference cells. One lamp passes through 

the sample cell and the other lamp through the reference cell. The 

emergent radiation from both cells Is directed to a single detector 

cell. As the gas in the detector absorbs radiation, its temperature 

and pressure increase. An expansion of the gas in the detector causes 

the membrane of a condenser microphone to distort. This distortion is 

converted to an electrical signal which ls amplified to produce an 

output signal. The entire analyzer is kept at a constant temperature 

by a thermostatically controlled heater and blower Installed in the 

case. 

22 
Ar.arad 501R— 

This NDIR analyzer uses unlined Plexiglass sample and reference 

cells. The monitor consists of a single IR source, parabolic mirrors, 

a chopper, an optical solid state detector and an output module that 

can be separated from the rest of the monitor. 

Hydrogen Sulfide Monitors 

Bendix 7770— 

The Model 7770 gas chromatograph monitors H.S using an FPD. A 

sample block ls used to inject a volume of sample gas onto the first 

column. After the H.S has eluted through the first column, the column 

is backflushed to remove the heavier components. Further separation 

is attained ln the second column prior to H.S detection. Zeroing is 

automatic during the running program, but a zero offset control is 

also provided inside the programmer. Ihe instrument cycle time is 210 

seconds. Clean, dry air is used as the carrier gas. 

Process Analyzers Incorporated 32-230— 

The Model 32-230 monitor is a gas chromatograph equipped with a 

flame photometric detector (FPD) that is sensitive to sulfur. A 

volume of sample is injected into the analytical column from a sample 

loop. After the H.S sample has eluted past the first column, the 

column is backflushed to remove heavier compounds. The H.S continues 

through the second column. At the proper time for the H.S component 

to elude through the column, the flame photometric sensing circuit is 

activated to detect the H.S. Zeroing ls automatic and occurs 

immediately before the elution of the peak of interest. Span is 

accomplished by adjust- ing an attenuation potentiometer inside the 

case. 

Teledyne 611 DMC0-20X— 

This dual beam monitor utilizes ultraviolet absorption to quantify H.S concentration in the sample. A 12-lnch-long optical cell has 

continuous sample flow. On one end of the sample cell is an ultraviolet source and on the other end a detector. A rotating chopper 

with two filters 180° apart is located between the cell and the 

detector. One of the filters passes only a known absorption 

wavelength for H.S, the other a wavelength at which H.S does not 

absorb (reference beam). The wavelengths are not specified. 

Synchronizers and electric circuitry subtract the non-H.S absorption 

(reference beam) from the total absorption. 

Houston Atlas Model 825R/102— 

The Model 825R/102 monitor operates on the principle of lead 

acetate impregnated paper tape reacting to change color in the 

presence of H.S. A cadmium sulfide photocell is used as a detector. 

The photocell output feeds a preamplifier. The output of the 

preamplifier feeds a low-pass filter which differentiates the signal 

with respect to time. The resultant differentiated output provides a 

DC signal that has a peak amplitude directly proportional to the HgS 

concentration. 

23 
P.39 

To obtain a sample ln the concentration range of measurement by 

lead acetate tape, the monitor Is equipped with a.sliding block diluter. Ihis diluter mixes a measured volume of sample with a stream of 

diluent gas. The amount of dilution ls adjusted by varying the Injection frequency of the sample. Zero and span adjustments are made by 

adjusting potentiometers Inside the case. 

Del-Mar Scientific DM-W— 

The DM-W uses a lead acetate impregnated paper tape that is 

exposed to the gas stream as it moves past an aperture. The H.S in 

the gas stream causes a black precipitate (lead sulfide) to form on 

the tape. Color development ls monitored by a photocell that measures 

light reflected off the tape. 

Because the DK-W normally operates in the 0 to 50 ppm H.S range, 

Del Mar supplied a dilution system with the monitor. This system was 

comprised of two rotameters, a mixing chamber and a back pressure 

regulator. The fuel gas sample was diluted with nitrogen at the 

recommended ratio of 1:10 by adjusting needle valves on the 

rotameters. 

ANCILLARY EQUIPMENT 

All monitors and data aquisition equipment were installed in a 

24-foot-long trailer equipped with heating and air conditioning. 

Figure 2 shows the location of all equipment within the mobile laboratory. 

The CO source was a stack on a FCC unit. The CO boiler stack gas 

contained: 150. to 300 ppm NO , 200 to 600 ppm SO., some acid mist, 

50 to 300 mg/m particulate n?atter, 10 to 14 percent H.O, 9 to 14 

percent CO., and 20 to 10,000 ppm CO. The temperature at the sampling 

point was approximately 320 C (600 F). 

The H.S source was a fuel gas pipeline located approximately 120 

meters from the trailer. Stainless steel tubing (0.63 cm OD) was used 

to connect the gas line to the trailer H.S distribution system. The 

sampling point was down steam of an amine treater. Vhen the monitors 

were first Installed in April 1980, the treater was using diethanolamine for the removal of H.S, but in March 1981, the treater was 

refurbished and monoethanolamine replaced the diethanolamine. The H-S 

level in the fuel line ranged from 5 to over 1,000 ppm during this 

study. 

Fluid Catalytic Cracker Emission Sampler/Conditioner 

An EPA-deslgned sample conditioning system was located at the 

sampling port 60 meters above ground level on the CO boiler stack. 

The dried (dewpoint -20°C) and filtered sample was transported 200 

meters to the trailer by using unheated, 9.5 on ID black, nylon 

tubing. A detailed description of the sample conditioning system and 

its per- formance is included ln Appendix D. 

24 
P.40 

Sample Distribution Systems 

In the trailer, the gas samples from the sources were distributed 

to the monitors by using the distribution (manifold) systems shown ln 

Figures 3 and M. The water column was included on the CO distribution 

system to ensure that constant pressure was maintained ln the system. 

In addition, a pressure reducer was Included to ensure that the Ecolyzer inlet pressure was maintained below 2.5 cm water. Each distribution systems was fitted with solenoid valves on the span gas and 

nitrogen gas lines to facilitate automatic daily zero and span checks 

by the data aquisition system. 

Data Acquisition System/Automatic Zero/Span System 

Each monitor was connected to the Esterline Angus Model PD-2064 

data logger. The PD-2064 converted the 4 to 20 mA output of each 

monitor to 25 to 125 mV and provided approximately a -25 mV offset. 

Each Instrument then showed a response on the PD-2064 of 0 to 100 mV. 

The PD-2064 is able to monitor all 16 channels continuously or to scan 

them at any desired frequency. In addition, the system can scan 

selected channels at any desired interval and average the readings for 

each channel after the desired number of scans. During the field 

testing, each monitor's output was scanned every 3 minutes except when 

relative accuracy and calibration error tests were conducted. In 

those cases scan times of 1 minute were usually used. After ten 

scans, the readings were averaged and the results were printed on the 

paper tape. The data and time of printing were also recorded on the 

tape. 

Every 24 hr, the data logger automatically accomplished a 

zero/span check of the monitors. At a set time the- data logger closed 

the contacts leading to a solenoid valve in the sample distribution 

system. This valve shut off the sample gas and opened the nitrogen 

(zero) gas. After 15 minutes the data logger took a single reading on 

each channel and printed the value. The first set of contacts then 

opened and a second set closed to allow span gas to enter. After 

15 minutes the data logger again read each channel and printed the 

value. The second set of contacts then opened and the original 

program of scanning and printing resuned. 

EPA Reference Method 11 was used throughout as published. Equipment listings are published in the Method.The manual method for CO 

analysis is presented in Appendix E. All equipment is described 

therein. 

25 
SPARES 

Kl 

M SC 

OASES 

CABWET 

AIM 

HEOUIATOS i /wnco AUTOMATION 

DEI MAN BENOfX 

8TANDARO OASES 

nooci 

W

3 ( M.SBO* J 

WU 

BUBBLES 

S • 

/ ooo-n i 

.HEATER 

TEIEOYNE CO BOX ECOLYZER 

FIGURE 2. SKETCH OF INSTRUMENTATION TRAILER SHOWING INSTRUMENT ARRANGEMENT. 
P.42 

e* — i S 

H 

*|-+II] 

—&Htyh-&^&h 

§—&-=•£<}-

m 

o 

CJ 

CQ 

< 

o 

6 

27 
K> 

09 

SPARC >•• 

SAMPLE __ 

IN *— 

ZERO OAS . 

IN >~ 

SPAN OAS _ 

IN >~ 

lp»'t] 

TO 

TO TO TO HOUSTON TO 

TEIEOYNC DEI MAR BENDIX ATIAS PAI 

•&SAMPLC 

IsHut-orr 

«0.T 

i 

BO? no* 

£ 

so? BO.l 

I 

f 

CONSTANT 

PRESSURC 

FLASK 

FIGURE 4. PLUMBING DIAGRAM FOR FUEL GAS DISTRIBUTION TO THE HjS CEMS 
SECTION 5 

EXPERIMENTAL PROCEDURES 

GENERAL PROCEDURES 

Calibration Cases 

Calibration gases used for this evaluation were Certified Master 

Gases supplied by Scott Specialty Cases, Plumsteadville, PA. Calibration gases were selected to be 15, 50, and 90 percent of the instruments' span range with nitrogen being the balance. The gases were 

analyzed and certified to be +2 percent of the stated values. Method 

11 was used to verify the H.S gas concentrations and a Bendix Model 

8501 5CA NDIR CO monitor calibrated with NBS standards, was used to 

verify the CO gas concentrations. 

Calibration Procedures 

Each Instrument was calibrated according to the manufacturer's 

Instructions by using the appropriate sample distribution system to 

Introduce the calibration gas. Calibration curves were generated for 

each monitor. 

Throughout this evaluation, all instrumental response readings 

were obtained from the digital millivolt output on the Esterline Angus 

PD-2064 data logger. Span and zero adjustments were made on the 

Instruments to produce a proper millivolt response on the PD-2064 data 

logger. 

UBORATORY EVALUATION OF THE MONITORS 

The monitors were evaluated in the laboratory with the procedures 

described in the Federal Register(5). The following parameters which 

are defined in Appendix A, were evaluated: 

• precision 

• noise 

• response times (rise and fall) 

• H-0 and CO- interference for CO monitors 

• CR^ and CH^SH interference for HgS monitors 

• flow and temperature variation 

29 
Precision (Repeatability) 

Precision is the standard deviation about the mean of repeated 

measurements on the same gas concentration (2). In this test, 

measurement of the selected gas (e.g., aid-span) was Interrupted 

alternately by the introduction of a higher and a lower gas 

concentration. Six stable readings of the selected gas were obtained 

In this manner and the precision was calculated as follows: 

P -

* 

6 

Z 

1-1 

P.* - 4 ( I Pa) 

6 1-1 * 

'] (1) 

Where: P s Precision 

P. * Instrunent response (ppm) for the 1 

on the selected gas. 

th measurement 

Output Noise 

Instrument noise is a short-term variation in instrument output 

not caused by changes in output concentration. This value is 

"expressed in concentration units as the standard deviation about the 

mean (2). 

The test procedure involved allowing the instrument to stabilize 

on the gas standard (either zero or span) and then taking 25 readings 

within a 60 minute period by using a digital voltmeter. These 

readings (expressed In concentration units) were entered into the 

following equation: 

•^[lirS-'*<l *s] (2) 

Where: S 

r. 

s Instrunent Noise (ppm) th 

s Instrunent Response for the 1 reading (ppm) 

Instrument Response Time 

Rise time Is the time Interval between the initial instrunent 

response and 95X of the final response after a step increase in input 

gas concentration. The test procedure involved changing the input 

from zero gas to a high-range span gas and determining the time 

required to reach 95 J of the high-range span gas concentration. 

30 
P.46 

'Fall time is the time difference between the Initial response and 

95X of the final response after a step decrease ln input gas 

concentration. The test procedure involved changing the input from a 

high-range span gas to zero gas and determining the time required to 

reach 5% of the span value. 

To obtain the proper rise and fall times, the "dead volume" in 

the sample lines was minimized by placing a three-way stopcock as near 

as possible to each instrument's sample port. The sample gas was 

switched from zero to span by using this three-way stopcock. The 

chart recorder was used at its fastest speed during the test. The 

response times were calculated from the strip chart. Three rise times 

and three fall times were calculated and the results of each set were 

averaged. The Instrument response reported in Tables 5 and 9 is the 

larger of these two values. 

CO. and' H.O Interference for CO Monitors 

— 2 2 

Carbon dioxide interference was determined by using a Scott blend 

of 10 percent CO. in nitrogen. The response to the introduction of 

the 10 percent CO. is expressed in ppm as an equivalent CO 

concentration. 

Water interference was determined by adding water vapor while the 

instrument was sampling nitrogen (zero gas). The response to the 

added water vapor was expressed in ppm as an equivalent CO 

concentration. Water vapor was added by passing nitrogen through a 

flask containing distilled water. The flask was heated sufficiently 

to introduce the desired amount of water vapor into the flowing gas 

without causing condensation ln either the sample lines or the instrument. The water vapor generator was calibrated using EPA Method 4. 

Methane and Methyl Mercaptan Interference for H^S Monitors 

Methane interference was determined using 99 percent methane. 

Each Instrument was first zeroed and calibrated according to the 

manufacturer's instructions. The methane was then introduced and the 

response was recorded as ppra H-S. This same procedure was repeated 

using 40 percent hydrogen in methane and 200 ppm methyl mercaptan in 

methane. The interference was expressed in ppm as an equivalent H.S 

concentration. 

Variations in Response Due to Changes in Temperature and Sample Flow 

Rate 

Variations in Instrument output caused by short-term changes in 

ambient temperature were measured using zero and span gases. The test 

procedure Involved allowing the instrument to stabilize at a given 

room temperature, recording the response to a gas, changing the 

temperature *10°C and again recording the stabilized response. This 

test was performed using the trailer's heating and air conditioning 

system to control the room temperature. 

31 
P.47 

Variations due to flow rate changes were studied using rotameters 

calibrated with a soap-bubble flowmeter. The span gas and the flow 

rate were varied from approximately 20 to 500 percent of the recommended sample flow rate. The Instrument response was plotted versus the 

percent of recommended flow. 

FIELD EVALUATION OF THE MONITORS 

Field Response Time 

Field response time Is the time required for the Instrument to 

obtain either 90 or 95 percent of the final instrument response after 

a step increase in the gas concentration. In the study this included 

the time involved for gas flow through the sample conditioning system. 

The gas was introduced at the sampling point and the response time was 

calculated ln a manner similar to that used In the laboratory 

evaluation of Instrument response time. 

2-Hr Drift (Zero and Span) 

At 2-hr Intervals, zero gas (nitrogen) was sampled by the 

monitors until all of the monitors had obtained a stable reading; 

then, the span gas was introduced to all of the monitors. The zero 

and span values were recorded by the data logger and the source gas 

was sampled again until the next 2-hour interval was to begin. At 

this time the above procedure was repeated. This was continued until 

fifteen 2-hour intervals were completed. Instrument zero and span 

were adjusted only at 24-hr intervals during this test, and none of 

thes e adjustments were made during the time a 2-hr interval 

measurement was being made. The 2-hr zero drift was calculated in the 

following manner: 

Drift (zero or .pan) - ' » * I + Cl] ? 10

r ° * Instrument Span 

where 

(3) 

- 1 " 

d - -- I d* - Algebriac mean of the differences 

1-1 

d. - (Instrument reading) - (Instrument reading 2 hours later) 

n - Number of data points (I.e., the number of d< values) 

CI - 95Z confidence Interval estimate of the mean value 

$s V- £ * - (£ '*) (4) 

32 
t. . „ * Student's t-factor, function of n; i.e. 

n ^.975 

2 

3 

4 

5 

6 

7 

^.97 5 

12.706 

*.303 

3.182 

2.776 

2.571 

2.447 

8 

9 

10 

11 

12 

14 

15 

2.365 

2.306 

2.262 

2.228 

2.201 

2.160 

2.145 

The 2-hr.span drift was calculated in an analogous manner, except 

that the span reading was corrected for any zero drift that occurred 

in the 2-hr interval. 

24-Hour Drift (Zero and Span) 

The data logger automatically introduced zero and span gases into 

the sample distribution systems daily and the instrument response was 

automatically recorded by the data logger. Seven consecutive values 

were obtained over a one week period to establish the 24-hr drift for 

each monitor. Zero and span were adjusted only at 24-hr intervals on 

an as needed basis. Equations 3 and 4 were used to calculate the 

24-hr zero and span drift values. 

Calibration Error Test 

The calibration error test was performed by first calibrating 

each Instrument, then alternately introducing each calibration and 

zero gas until fifteen readings were obtained. The difference between 

the Instrument's response and the actual concentration of each gas was 

then calculated using equations analogous to 3 and 4. (In Equation 3. 

the calibration gas concentration would be the denominator and not the 

span value of the instrument). 

Calibration Drift 

Data for this test were taken from the daily zero and span 

checks. Zero and span adjustments were made at weekly or longer 

intervals. 

Relative Accuracy 

The relative accuracy of the CO monitors was determined using the 

leuco crystal violet wet chemical method described in Appendix E. The 

accuracy of the H.S monitors was determined using EPA Reference Method 

11 (6). The relative accuracy of the monitors was calculated as 

described in Reference 4, i.e.: 

33 
P.49 

r , *4 a #*x ltd I + CI) X 100X ,CN 

Relative Accuracy (X) - ^ —- — (5) 

Mean Value of Reference Method 

where 

d - Algebraic mean of the difference between 

the reference method value and the monitor 

value 

CI - 95X confidence Interval 

34 
P.50 

SECTION 6 

RESULTS AND DISCUSSION 

MANUAL CO METHOD DEVELOPMENT/VALIDATION 

EPA Reference Method 10 specifies collecting the emission gas 

sample in a Tedlar bag and analyzing for CO by NDIR (7). Since NDIR 

ls the measurement principle used ln most CO CEMs, EPA desired to have 

a non-NDIR manual method for checking the accuracy of NDIR-equipped 

CEMs. Four wet chemical CO methods previously described in the 

literature (8-12) were evaluated in this study. 

The first method evaluated (8) Involves the aqueous reduction of 

Pd(II) by CO followed by the addition of KI to yield a red, tetraiodopalladlum (II) complex, which is then measured spectrophotometrlcally 

to determine the amount of Pd(II) reduced. The amount of CO present in 

the gas sample is then calculated on the basis that two moles of CO 

reduce one mole of Pd(II). Although this method performed adequately 

in the laboratory, it was found unsuitable for gas samples that 

contained even 1 ppm NO. For example, the following analytical 

results (ppm CO) were obtained on three Tedlar bag samples that 

contained 266 ppm CO and the following levels of NO in nitrogen: 225 

ppra NO (27 ppm); 2 ppra NO (186 ppm); and 1 ppm NO (223 ppm). The 

method suffered from: interference by SO. and organics; sample 

instability; poor precision below 100 ppm cO and had a nonlinear 

absorption curve. Because of the slowness of the reduction of Pd(II) 

ion by CO, the method also required shaking the sample bulb for 2-hr 

before adding the KI. For these reasons, work on this method was 

terminated. 

Three other methods were then evaluated. These methods used 

spectrophotometry and the reduction of Pd(II) ion by CO in the 

presence of gun arable (9). phosphomolybdlc acid/acetone (10) and 

leuco crystal violet/potassium lodate (11, 12). The gun arable method 

suffered from poor precision, sample instability, and interference 

from low levels of NO and SO. and required a long reaction time (2 hr 

minimum). The molybdenum blue reaction also suffered sample stability 

problems, had poor precision for CO concentrations near the level of 

the standard (500 ppm) and required a sample reaction time of 1 hr at 

60 C • 1°C. Further, In both the gun arable and phosphomolybdlc 

methods, the reaction product is a colloid, which means that a 

strongly absorbing solution cannot be diluted to bring it into the 

linear range of the calibration curve. 

35 
P.51 

The last method evaluated, the leuco crystal violet (LCV) method, 

yields a soluble complex that permits sample dilution, has good 

precision ln the range of 0 to 1000 ppm, and is accurate ln the 

presence of low levels of SOp and NO « 5 ppm). Some other favorable 

features are: 

• the shaking reaction time can be as short as 15 to 20 

minutes for CO concentrations from 50 to 1,000 ppo; 

• the absorbance Increases linearly with Increased shaking 

reaction time up to 2 hours; 

• the stock reagents are stable and easily prepared; 

• the calibration curve ls linear in the absorbance range 

0 to 1.7; 

• the complex that is formed absorbs in the visible region 

of the spectrum (587 nm) more than 200 nm from where the 

reagents absorb. Also, the blank is Initially 

negligible (Table 12). 

Since the LCV method suffers interference from SO. and NO at the 

concentrations encountered in FCC stack gases (Table 13). the effectiveness of various scrubbing solutions in reducing these compounds to 

less than 5 ppm (without also removing CO) was studied as a function 

of flow rate, scrubber volune, concentration and pH, gas volune, and 

SO. and NO concentration. The following scrubbing solutions were 

evaluated: 6> percent H.O.; 2 percent KMnO^/2 percent NaOH; 4 percent 

KMnO /4 percent NaOH; 2.b percent KMnO^/1 percent HNO ; and 2 percent 

K2C r2°7/1 Percen t HN0 3' 

The best scrubbing system ls a flow rate of 0.2 to 0.3 L/min 

through three Greenburg-Smith Impingers. The first two impingers 

contain 400 mL of 4 percent KMnO^/5 percent NaOH and the third 250 mL 

of this solution. This system can reduce the SO. and NO levels to 

less than 5 ppm for a 50-liter gas sample containing 15* COg, 700 ppm 

SO. and 500 ppm NO. Since the Impinger system also removes CO., an 

appropriate volune correction is required when calculating the CO 

concentration originally present in the gas. A Fyrite analyzer is 

suitable for measuring the CO. present in the stack gas. 

For field sampling, the original single-sample, ambient air 

method (12) was modified to allow the analysis of many samples ln a 

short period of time under field conditions. Sample stability, 

shaking time, shaker type, sample volume, and volume of reagent were 

36 
P.52 

some' of the parameters studied to simplify the method as much as 

possible and at the same time to optimize its precision and accuracy 

at stack CO concentrations. 

The method was validated at the petroleum refinery in four field 

tests in which the samples were passed through the scrubber solution 

and collected In 10-liter Tedlar bags. These bag samples were returned to the laboratory and analyzed in triplicate by the LCV method 

and by NDIR on a Bendix Model 8501-5CA calibrated against NBS 

certified CO standards. From forty-one samples collected and analyzed 

in this manner, lt was determined that the manual method had a consistent 4 percent positive bias with respect to the NDIR. The precision 

of the method was determined to be 2.5 percent of the mean concentration for a sample that contained between 15 and 1000 ppm CO when the 

sample was analyzed in triplicate. The Tedlar bag samples were stable 

for at least two weeks. Representative analytical results are presented in Table 14 and the actual method is described ln Appendix E. 

Since the largest source of error was found to be leaks around 

the valve of the Tedlar bags, all bags should be checked for leaks 

before use, either by submerging filled bags in water or by pulling a 

vacuum ( 25 cm H.O) on the bag and seeing lf it will hold the vacuum 

for at least 4 hours. 

37 
P.53 

TABLE 12. CHANGE IN ABSORBANCE OF CO REAGENT 

BLANK WITH TIME AT ROOM TEMPERATURE 

TIME snic z 

nUTAJtATION 

(•In) 

0 

20 

SO 

43 

• 0 

100 

120 

IM 

290 

2S0 

220 

MO 

A1S0XAAJ1CT. 

THIS STUD* ZITERDJCE 11 

0.013 

0.015 

0.020 

0.030 

0.050 

0.080 

0.085 

0.089 

0.100 

0.020 

0.040 

0.07 

0.12 

0.21 

TABLE 13. EFFECT OF NO AND SO- ON LUECO 

CRYSTAL VIOLET 

SAMPLE 

VUMBE& 

1 

2 

2 

4 

S O , 

(ppa) 

0 

0 

TOO 

SOO 

SO 

200 

400 

0 

200 

CO 

ACTUAI 

SOO 

soo 

soo 

soo 

(pp«) 

FOOT!) 

410 

290 

290 

S60 

38 

. 
P.54 

TABLE 14 . COMPARISON BETWEEN LCV AND NDIR RESULTS ON FCC SAMPLES 

TEST 

DATE 

SEPTEMBER 

1980 

JANUARY 

1981 

LCV METHOD RESULTS (ppm CO) 

1 

178 

121 

31.1 

- 78.6 

26.5 

25.2 

28.8 

16.7 

33.0 

1094 

356 

546 

176 

181 

158 

188 

81 

102 

519 

258 

2 

159 

120 

31.0 

91.1 

28.0 

24.0 

28.0 

17.6 

30.2 

1002 

365 

592 

184 

184 

145 

182 

87 

114 

482 

248 

3 

163 

129 

30.1 

76.4 

27.8 

26.9 

29.3 

16.5 

33.2 

llll 

321 

— 

182 

211 

153 

189 

78 

110 

536 

267 

AV 

167 

123 

31.0 

82.0 

27.0 

25.0 

29.0 

17.0 

32.0 

1069 

347 

569 

180 

192 

152 

186 

82 

109 

512 

258 

NDIR (ppm CO) 

BENDIX 8501-5CA 

149 

115 

34.0 

75.0 

26.0 

22.0 

27.0 

19.0 

28.0 

1005 

315 

575 

178 

175 

155 

181 

62 

98 

539 

235 

39 
EVALUATION OF CARBON MONOXIDE MONITORS 

Five relative accuracy tests were conducted on the CO monitors at 

the refinery. The results of these tests are summarized ln Table 6 

and the results of each run are presented in Table 15. In these 

tests, the samples for the manual method were passed through 

Greenburg-Snith impingers containing alkaline KMnO. solution (to 

remove N0X, S0X and organics) and then collected in Tedlar bags. All 

samples were collected from the distribution manifold to ensure that a 

sample-conditioning system malfunction did not contribute significant 

error to the monitor validation procedure. 

Tests to verify that CO was not lost in the sample conditioning 

system were conducted before each relative accuracy test and at other 

times between February 1980 and April 1981. Until September 1980, 

these checks consisted of simultaneously collecting stack gas samples 

in Tedlar bags at the manifold (distribution box) and at the probe, 

and analyzing the bags by NDIR for CO and CO. at the EPA laboratory in 

Research Triangle Park, North Carolina. In September 1980, a Bendix 

Model 8501-5CA NDIR CO. analyzer was installed in the trailer to continuously measure the CO. concentration ln the gas leaving the manifold. After this, the sample conditioning/sample transport system was 

checked monthly and also before each relative accuracy test by 

analyzing the stack gas for CO. using a Fyrite analyzer and by 

comparing the result to the Bendix 8501-5CA monitor reading. If the 

Bendix CO. monitor value differed by more than 0.5 percent from the 

Fyrite value, remedial action was taken before the relative accuracy 

test was Initiated. 

The operation of the FCC unit during this 11-month study was 

erratic due to FCC failure and process upsets. The CO levels varied 

between 20 ppm and 10,000 ppm CO over a period of several days; 

frequently, the particulate emissions were much higher than the 50 to 

100 mg/m normally present. Each time a relative accuracy test was 

conducted, the CO concentration in the stack exceeded the 1,000 ppm 

span range of the monitors, so plant instrument air was introducted at 

the probe to bring the CO concentration into the operating range of 

the monitors. This dilution also reduced the N0X and S02 concentrations in the sample gas by factors of 4 to 10. 

During each relative accuracy test, a cylinder gas containing 100 

ppm CO, 12 percent CO., 500 ppm SO., and 200 ppm NO in N. was introducted at the manifold for 30 min and the monitors' output was 

recorded while the Tedlar bag sample was taken for analysis by the 

manual method. This served three purposes. First, it showed how the 

monitors would perform when sampling a stack gas representative of FCC 

exhaust gases. (Recall, it was necessary to dilute the stack gas with 

air to bring the CO level into the range of the monitors.) Second, it 

served as a control sample to establish how constant a monitor's 

response was to the same sample over the length of the study. Third, 

lt provided a sample of known CO concentration so that the accuracy of 

the manual method (sampling and analysis) could be established. 

40 
P.56 

During each of the 30-minute relative accuracy tests, the monitor 

output was read at 1-oinute Intervals. The first test, conducted in 

June 1980, was unsatisfactory because the manual method being 

evaluated (palladium/potasslun Iodide) suffered sample stability 

problems and Interference from NO. Thus, the only way to evaluate 

monitor accuracy In this test (Table 15) Is to compare one monitor to 

another (Runs 1-9) or to compare their response to the 100 ppm CO 

cylinder (Run 10). 

However, since the other four relative accuracy tests were done 

using the LCV method, satisfactory manual method results were 

obtained. The fourth and fifth relative accuracy tests were performed 

during the same week. In the fourth test, three gas cylinders 

containing 500 ppm CO, 12 percent CO., and different levels of SO. and 

NO were employed to see how the monitors would perform lf sampling an 

undiluted FCC stack gas. As expected, the Ecolyzer detector failed 

during the test from exposure to N0„ and SO. which were not effectively removed by the Model 2949 scrubber. In the first three relative accuracy tests, the Anarad and MSA monitors were quite stable, 

but, by the last two tests, they somtlmes drifted up to 5 percent of 

span over several hours, but at other times remained stable for a day. 

This drift sometimes occurred only in the span and at other times only 

In the zero setting. No explanation ls available for the difficulty. 

As mentioned earlier, the only problem encountered with the LCV 

manual method was the tendency of the Tedlar bag to leak at the point 

where the valve enters the bag. This was a significant problem only 

in the fourth relative accuracy test where new sample bags were used 

and a small leak was found at the metal washer that served as a gasket 

between the valve body and the bag. This leak only occurred when the 

sample was withdrawn from the bag and for this reason was not detected 

when the bags were leak-checked by Inflating them before use. 

Two calibration error tests were performed: the first in May 1980 

and the other in June 1980. The results are presented in Table 5. 

The interference of CO. on the monitors remained constant throughout 

the study. 

Figures 5 through 10 show the long-term zero and span drifts in 

the CO monitors. These data, which were collected from May 1980 to 

January 1981, were used to determine the calibration drift of the 

Instruments. (Recall that: (1) only the Applied Automation had automatic zero and that none of the instruments had automatic span 

correction; (2) the zero and span of the monitors were checked every 

24 hours; and (3) except when relative accuracy tests were being 

conducted, the zero and span of the monitors were never adjusted at 

Intervals shorter than 1 week.) 

41 
P.57 

Applied Automation Optlchrom Model 102 

The instrument Is comprised of two modules, a programmer and a 

GC-oven assembly. It was purchased without vendor installation and 

Interconnecting wiring was not furnished. Ihe instruction manual was 

furnished three weeks after the instrument was received; hence, the 

nonitor was not operational as received. Extensive time was required 

to complete the Instrunent wiring and Install the circuit boards. 

After the monitor m s wired and installed, numerous startup problems 

were encountered. After a serviceman was sent by Applied Automation, 

it was determined that wire of too small a gauge had been used for the 

Interconnecting wiring. Numerous other difficulties were encountered 

ln obtaining the correct output signal. 

To adjust the span, a lengthy procedure requiring a strip chart 

recorder and many adjustments is necessary. After the initial span 

adjustment, a trial-and-error method is used for fine tuning, although lt is not specified In the instruction manual. 

The response time is limited by the cycle time of the analytical 

program. The GC completes a cycle every 105 seconds. Varying the 

flow or pressure causes no response variance because a sampling loop 

vented at atmospheric pressure ls used. An oven maintains a constant 

temperature for the chromatographic columns. Since the sample value 

ls ambient temperature or in a thermostatically controlled area, it 

was not affected by changes ln ambient temperature or sample gas flow 

rate. 

In June 1960, a negative concentration was sometimes measured by 

the Instrument. After careful examination of the chromatogram, this 

problem was related to a negative signal dip that occurred immediately 

before the CO peak eluted. Several trips to the refinery were made by 

HE&T personnel to repair the instrument with no success. In November 

1960, Applied Automation performed a service call. After two days of 

work, the serviceman still could not correct the problem and further 

testing of this instrunent was discontinued. 

Ecolyzer 3107 

This instrument performed without failure during the laboratory 

testing. Special provisions were necessary to ensure that a sample 

pressure of no more than 2.5 cm water pressure was present at the 

sample inlet port. The span and zero adjustments were not responsive 

and thus a slow drift In zero and span followed any adjustment ln 

these controls. 

Sample flow variations from 0.5 to 1.5 times the recommended rate 

caused response variations of 10 percent reduction and 3 percent 

increase, respectively. In varying the ambient temperature from 10 C 

to 30°C no change in response was observed. 

42 
P.58 

For removal of NO and SO. from the sample stream, a gas scrubber 

cartridge (filter Model 2949) was supplied. This was located Inside 

the case and required removal of the sensor for replacement. Because 

of the extremely short lifetime of these filters and the difficulty in 

replacement, the filters were relocated outside of the case during the 

field evaluation. Normal life expectancy of these filters in a stack 

gas containing 500 ppm SO. and 300 ppm NO ls 1 to 5 days. These 

filters cost approximately $45 (a considerable operating expense). 

Filter failure caused damage to the electrochemical sensor (requiring 

replacement at considerable cost). 

MSA Lira 202 

The MSA Lira 202 operated as received. After less than a week of 

operation, the power supply and output signal circuit boards failed. 

After the boards were replaced, satisfactory output in the range of 

4 to 20 mA could not be obtained, despite several replacements of each 

of these circuit boards. 

In June 1980, an MSA serviceman corrected the problem. Instead 

of using the 4 to 20 mA output on the instrument, he used an Isolated 

external converter to convert the normal 0 to 100 mV output to 4-20 

nA. After this repair, the monitor operated well throughout the 

evaluation. Occasional optical realignment was required to maintain 

calibration. Excessive drift was sometimes observed. 

Tests for response variation due to sample flow rate and ambient 

temperature changes were not pe formed due to the late arrival of the 

instrument. 

Anarad 501R 

This NDIR monitor performed without any difficulty during the 

evaluation. No special provisions were necessary for the sample gas 

except that there had to be free discharge from the sample exit port. 

Sample flow variation from 0.3 to 5 times the recommended rate caused 

response variations of less than 1 percent. Varying the ambient 

temperature from 10°C to 30°C did not affect the response. Carbon 

dioxide and water did give a slight positive interferences. Overall, 

the instrunent proved to be extremely accurate and reliable. 

43 
P.59 

TABLE 15 . RELATIVE ACCURACY TEST 

RESULTS ON CO MONITORS 

JS. 

m 

' T W (J — CO)* 

». f i | tfrtjoj. 

M t. l » IM.. . H ) 

I 

H TM . ) O M tl) 

f 

» tM , 4 Wrt. il ) 

^ TM. I CFrt. 11) 

! 

> 

* 

* i 

> i 

u 

t * 

I 

I 

> 

I 

u 

Ml 

U I 

• 1 

I H 

4 U 

»» 

Mt 

>M 

til 

Mt 

in 

* i 

i * 

i 

i 

u 

i * 

M t 

U l 

in 

M l 

I M 

111 

MM 

in 

M l 

t i t 

t M 

I t . 

t H 

tn 

i n 

t i t 

t t i 

t N 

1 * 

ITI 

*JI 

I U 

I M 

111 

•0 

1) 

M 

t t 

M l 

H 

MM 

•OJ 

I M 

t » 

I M 

H I 

• M 

i n 

M l 

I M 

H I 

•1? 

M> 

tw 

MO 

M t 

M l 

I M 

I M 

t l 

M 

t l 

41 

MO 

t t 

Mt! 

HO 

i n 

B l 

M 

I t i 

• M 

H 

I t . 

I I 

U 

I t 

M 

U 

It 

U 

M l 

t i l 

M l 

t n 

M l 

t t l 

M l 

M l 

t u 

4M 

Mn 

M M 

I M O 

1100 

u ti 

ru 

M l 

H I 

Ml 

Ml 

H I 

tM 

Ml 

Mt 

Mi 

Ml 

Ml 

Ml 

Mi 

t i t 

• It 

m 

Ml 

Mt 

» 1 

MI 

Mt 

no TM 

TM 

t t ? 

M7 

tit 

t i t 

tie 

Mt 

Ml 

Ml 

Ml 

Ml 

TU 

n i 

ut Mt 

m TTl 

m 

m TM 

M-Mlt. »m.t- 4 twt B , Mt.ll.l—. . 

ICV M.M4 tM. M . -mt* «M4 . 

CTIIM. 1 -ft MM: NO nm B ; BO r m B, . MO n . B ; WlMM » , 

•ue l $.. Ulill f 1:4 a-Htk llll l -Mil .b . 

lurk ,.< 4IU.1M 1:10 Hik (MIH M air. 

tix l ,. . 4U-nl«> lit «t.» wrna i ut . 

Cite*. $M MM. HC rf> a . uc ni B . in B,: hi. n •.. 

tri t 

erit 

. • M.4 HO M» B . HD fm B, : I B 00,; talMM «. " f 

•• MM : HO H» B . BC , M B ; HC „ • H,: IB oe,: MM M I, . 

xm -tmmlt Mf te Mll»r.tM. RS n > I 

44 
P.60 

— q 

i 

_«L ^ _ 

1 

[ 

, J 

lift 

*• *•*• a*r» fall • a 

m feu Ja*»f 

| 

IC 4M t(t HM 

FIGURE 5 . ZERO DRIFT TREND FOR ECOLYZER CEM. 

* * -" M l •" Vf 

iyW 

/* \ 

- J * 

a 

4 

~r 

h 

1 \ I P* •*•»• " 

••• ca»cantraiiam. 

A • tele ayan fallwa « «ata 

lirtf . 

FIGURE 6 . SPAN DRIFT TREND FOR ECOLYZER CEM. 

45 
P.61 

f 

( . 

' a 

> 

. 

f 

| " 

t *^-> 

A, V 

j 

L , '.A-J i Lr 

• 

« . te» M M fail* . 

•» 4.U IqtR . 

1 • *•« • HM. 

_L] K L L _ 

*"aa"\j 

mm JHC 4W7 M m «CT «ov KC JM m MM 

FIGURE 7 . ZERO DRIFT TREND FOR MSA CEM, 

^ V 

^ 

» i 

• J 

inn ^ uli L 

• 

i 

ri 

_ i 

^ 

... 

l 

L—M M 

V 

BMlot turn WUIU I 

Mlt.r.tlM ,. . CM*. 

4 * JUl. IM" f.U-B. 

m 4.1. l.-M.t. 

m act tc «M no 

FIGURE 8. SPAN DRIFT TREND FOR MSA CEM. 

46 
P.62 

I 

8 

J

\if[ 

"•VY A 

< 

JLA "*—tlmmJ 

« 

i 

li 

j ^ 

^cr 

\ 

J 

A • teu ear* fatlii 

A. m few H—ir. 

ir 

•cr mo. M C 4*a rti M M 

FIGURE 9 . ZERO DRIFT TREND FOR ANARAD CEM. 

• 

-A*-a "^ 

T 

i 

m•* S •». N 

., 

r' 

• 

uU 

• 

rr 1 

1 

\ 

4 

Ssthtf It m tebdUmtma 

. caJUratta * •• • Mac . 

A • C M 

• t M 

a • tet 

v 

vie li M ta 

a aara falJan « 

FIGURE 10 . SPAN DRIFT TREND FOR ANARAD CEM. 

47 
P.63 

EVALUATION OF HYDROGEN SULFIDE MONITORS 

The results of the nine relative accuracy tests are summarized ln 

Table 10. The Individual test results are presented in Tables 16 and 

17. From an examination of the data, the following observations are 

•ade: 

1. When two laboratories simultaneously conducted a relative accuracy test of the monitors, very good agreement 

was obtained between the laboratories, but their results 

differed significantly from the nonitors' results (Table 

17. RA Test 5). 

2. A monitor could compare well one day but poorly the next 

(Table 16, RA Test 4A, 48). The overall agreement 

between Method 11 and the monitors, as measured by the 

relative accuracy tests, was quite variable over the 

length of the study (Table 16). This variability was 

also noted ln the previous short-term study (3). 

3. Generally, the Bendix and Houston Atlas monitors 

measured H^S concentrations lower than Method 11, but on 

one occasion (RA Test 6, Table 16) the Bendix measured 

H.S levels higher than Method 11. Experiments to 

determine the cause of these differences were 

inconclusive. When the fuel gas was spiked with known 

amounts of H-S upstream of the manifold, the spike was 

adequately recovered by both the monitor (Bendix) and 

the Method 11 procedure. During these tests, (February 

and March 1981) the Houston Atlas monitor was not 

operational and the Del Mar was drifting severely, ao 

only the Bendix results were reliable. The two 

laboratory collaborative test (Table 17) shows that the 

difference in concentrations was not due to laboratory 

bias in Method 11. Both Method 11 and the monitors 

agreed well when analyzing H-S in nitrogen cylinder 

gases. 

4. When the eighteen, 30-minute tests (Table 16, RA Test 4A 

and 4B) were grouped to yield nine 1-hour tests, the 

relative accuracy of the monitors with respect to Method 

11 did not improve significantly. This indicates that 

increasing the sampling time to 1 hr does not 

significantly improve the results obtained. 

Figures 11 through 16 show the long-term zero and span drift observed in the HpS monitors. These data, which were collected from 

May 1980 to January 1981, were used to determine the calibration drift 

of the Instruments. (Recall that: (1) only the Bendix and PAI had 

automatic zero and that none of the instruments had automatic span 

48 

J 
P.64 

correction; (2) the zero and span of the monitors was checked every 24 

hr; and (3) except when relative accuracy tests were being done, the 

zero and span of the monitors were never adjusted at intervals shorter 

than one week). 

Bendix 7770 

This instrunent is equipped with numerous safety devices including automatic shutdown and start up lf certain hazardous conditions 

exist in the analyzer. A molecular sieve was added to the carrier air 

and hydrogen supply to ensure contamination free gases. The Bendix 

operated 89 percent of the time during field evaluation. Most of the 

downtime was attributable to two pneumatic, valve failures; the downtime was lengthened due to personnel not being on-site to replace the 

part. 

The flow variation and ambient temperature change tests were not 

applicable to this instrunent because lt used a heated sampling block 

to inject a constant and known volune of sample Into the chromotagraph 

column, regardless of the sample flow rate. The cycle time of the 

instrunent was 210 sec. For this reason, the time from injection to 

100 percent response was used in the laboratory evaluation for 

response time rather than from first response to 95 percent of the 

final response. 

The results of the precision, drift, noise and calibration error 

tests were excellent. Relative accuracy testing showed a consistant 

difference between the monitor and Method 11 for the fuel gas. The 

agreement was always good for H-S In nitrogen. An interference in 

either the monitor or the reference method was Indicated. 

Process Analyzers Incorporated 32-230 

This instrument never functioned properly. Many hours were spent 

troubleshooting circuit boards to attempt to find the cause for the 

lack of a proper output signal. The schematic wiring diagrams 

furnished in the operating and maintenance manual were not in agreement with the actual wiring. The unit was returned to the manufacturer for repair. After more than 4 weeks, it was returned to HEAT 

and installed in the test trailer on the final day of the first field 

evaluation. Before the next scheduled field evaluation, the monitor 

again failed due to a worn sample valve. 

The output of the monitor was not the 4 to 20 mA specified in the 

equipment order; and thus the monitor was not compatible with the data 

aquisition system. Thus, its output was recorded on the narrow 

recorder supplied with the monitor. After several breakdowns, the 

nonitor was shut off and its evaluation was discontinued. 

49 
P.65 

Teledyne 611 DMCO-20X 

This Instrunent required alignment of the chopper by using an 

oscilloscope prior to operation. Severe instability caused by any 

movement or vibration necessitated.that laboratory testing be done at 

night when wind or personnel would not cause movement of the 

evaluation trailer . Significant interferences were caused by methyl 

mercaptan and other compounds found ln fuel gas. The molecular sieve 

scrubber provided with the Instrument could not correct the 

interference. An alternate scrubber was eventually furnished but 

complete failure of-the instrument had already occurred. Because of 

multiple factors preventing acceptable operation of this monitor 

testing was discontinued before a valid test was achieved (See 

Appendix F). 

Houston Atlas 825R/102 

The instrument performed properly as received. The instrument's 

gas dilution system was not affected by sample flow rate or pressure 

changes, but lt was affected by ambient temperature changes. That is, 

increasing the ambient temperature decreased the response ln accordance with the Ideal gas law. This affected the accuracy of the dilution. 

Because of a wiring defect, the instrunent did not operate during 

the first field test and was returned to the manufacturer. It was 

rapidly repaired and returned to the refinery. 

Extremely large variance in the daily span values (10 to 30 

percent) during the first 8 months of operation resulted from water 

condensation in the sample vent line . Increasing the downward slope 

of the vent line eliminated the problem. 

The pneumatic actuator for the dilution system failed twice 

during the field evaluation causing monitor downtime. No specific 

interferences were detected but the general agreement between Method 

11 and the monitor was not within the desired 10-percent range. Each 

time the lead acetate tape was changed, the monitor required recalibration. This required a minimum of 2 hr due to the instrument's slow 

response to calibration adjustment. A rol l of tape lasted 

approximately 14 days. 

Del Mar Scientific DM-W 

The instrument operated as recieved, but before continuous 

operation was possible, the tension on the tape take up reel belt had 

to be increased by shortening the belt. The gas dilution system 

supplied by the vendor was inadequate. It was comprised of two rotameters (one for sample and one for dilution gas), a mixing chamber and 

a back pressure regulator. Slight changes in sample gas viscosity and 

50 
P.66 

changes in both aampie and dilution gas flow rate and pressure caused 

drastic calibration shifts in the instrument. Large volumes of 

dilution gas (10 L/min) were specified by the manufacturer. At this 

rate, a cylinder of nitrogen would last 1 day. Thus, to conserve gas, 

both sample and dilution flows were reduced to 15 percent of the 

recommended rate. Adverse effects were not noted by this reduction ln 

flow. 

Variations In sample pressure greater than 1 psi caused large 

variances in the sample flow to the dilution system, which in turn 

caused poor results in precision, noise and drift evaluations. The 

major problem with the instrunent appeared to be the sample gas 

dilution system. 

51 
* 

• 

• 

TABLE 

TZST HO 

BATE 

KA T«tt 1 

1 

2 

3 

4 

S 

6 

7 

• 

9 

••an 

KA Test 2 

1 

2 

3 

4 

S 

6 

7 

8 a 

9 

HMD 

KA Tett 3 

1 

2 

3 

4 

S 

6 

7 

8 

9* 

HMD 

a " 

16. 

i 

RELATIVE ACCURACY TEST RESULTS ON H 

KETWOD 11 

RESULTS 

(PP* %S) 

(4/27/80) 

161 

119 

165 

172 

166 

167 

166 

158 

.212 

160 

(5/3/80) 

157 

189 

173 

. 222 

219 

226 

251 

247 

130 

202 

(6/9/80) 

262 

269 

226 

245 

199 

233 

219 

163 

28 

205 

Din-ERENCE tHethr.4 ll-MoMt 0T> 

KEXDIX BOUSTON ATLAS 

<PP«) <PP») 

43 37 

52 25 

47 4 

21 37 

22 39 

32 40 

44 28 

38 34 

£1 45 

39 32 

22 - 6 

52 23 

SO 25 

44 18 

29 128 

35 43 

75 86 

88 117 

26 1 

47 48 

99 76 

96 67 

73 SO 

91 74 

78 61 

102 86 

•2 78 

62 47 

28 28 

79 63 

(Continued) i. 

52 

2S MONITORS 

(vm fcS) 

OEI. MAX 

(PP«> 

-197 

-24 8 

- 77 

-14 1 

-13 8 

-13 8 

-1*7 

-15 8 

-15 3 

-155 

-14 3 

-104 

-120 

- 67 

- 69 

- 64 

- 35 

- 43 

-158 

- 89 

80 

87 

49 

68 

86 

33 

30 

37 

28 

55 
P.68 

TABLE 

TEST AND 

BATE 

KA Test 4 

S 

« 

7 

1 

9 

10 

11 

12 

13 

l i U 

1 6 . RELATIVE ACCURACY TEST RESULTS ON H?S MONITORS 

METHOD 11 

RESULTS 

<PP« BjS) 

'(1/20/81} * 

222 

195 

190 

188 

171 

179 

195 

182 

186 

190 

KA Tett 4B (1/20/811 * 

14 

15 

16 

17 

18 

19 

20 

21 

22 

B i s 

KA Test 6 

1 

2 

3 

4 

5 

6 

B i n • 

KA Teet 7 ( 

1 

2 

3 

4 

S 

6 

7 

• 

B i n 

• 

174 

177 

203 

209 

198 

208 

198 

206 

203 

197 

(2/25/81} d 

285 

151 

71 

97 

128 

168 

150 

[2/25/81) 

131 

281 

82 

145 

203 

238 

27 

12 

137 

MFFEREiNCE 

RENDU 

(PP«) 

Sl 

24 

24 

20 

4 

11 

24 

14 

21 

22 

1 

S 

25 

24 

15 

29 

21 

27 

27 

19 

22 

16 

- 1 

6 

0 

10 

9 

17 

48 

20 

43 

84 

67 

27 

i i 

38 

(Continued) 

53 

(Method 11 

HOUSTON Al 

<PJ») 

c 

c 

16 

16 

j 

3 

28 

17 

11 

IS 

2 

8 

18 

28 

30 

54 

47 

57 

56 

33 

-Honl 

LAS 

tor ) (PP . »,S) 

BEL NAK 

(PP») 

99 

72 

- 5 

0 

- 7 

3 

10 

- 9 5 

- 7 0 

1 

- 97 

- 92 

- 31 

- 28 

- 33 

- 31 

- 33 

- 43 

-108 

- 56 

' ' T y i - j 
'.69 

TABLE 16. RELATIVE ACCURACY TEST RESULTS' ON H,S MONITORS 

TEST AKD METHOD 11 PirrSRENCE (Method 11-Monltor) (pp« IhS) 

•4IE RESULTS RENDU BOUSTON ATLAS PEL MAR 

(pp . BjS) (pp.) (pp . , (nm) 

KA Teat 8 (3/31/81) 

10 

ian 

64 

116 

171 

70 

115 

153 

212 

77 

78 

84 

- 114 

13 

6 

16 

14 

0 

-9 

-1 

15 

12 

12. 

8 

£ 

• 

27 

42 

70 

10 

26 

-2 

* 

4 

-1 

_9 

19 

Fuel gas sample collected ln a Tedlar bag taken at thia tli e and analyted 

ky CC ooe day later shoved less than 2 ppn B.S. 

30-ednute runs. 

c 

d 

Heroitor not operational. 

Fuel gaa waa spiked vlth known aaount of tjS for al l aix mi . 

54 
TABLE 17. RESULTS OF COLLABORATIVE RA TEST ON HjS MONITORS 

roe M D 

DATS 

11-

(ppv HiS) 

LAB 1 LAB 2 

DIFFERENCE (Method 11-Monitor) 

(ppm H»S) 

BENDIX HOUSTON ATLAS 

LAB 1 LAB 2 LAB 1 U B 2 

DEL HAR 

LAB 1 LAB 2 

Oi 

RA Test 5 (2/18/81) 

1 23 

2 28 27 

3 SI 43 

4 43 — 

5 41 33 

« 33 29 

7 32 2J 

8 31 32 

9 29 33 

Hean 33 32 

* Tha reference Method analyses 

_j 

-1 

-3 

-2 

-2 

-2 

-2 

-2 

-3 

-2 

vara perfone 

1 _«_ 

1 -12 

1 -39 

6 

3 -33 

9 -33 

4 -31 

8 -27 

2 -32 

5 -30 

ad simultaneously by 

-to 

-« 

-33 

-38 

-37 

-40 

-34 

-37 

-39 

-30 

•—• 

-8 

-41 

-45 

-44 

-41 

-36 

-35 

-36 

-27 

-5 

-38 

-33 

-43 

-52 

-43 

-32 

-64 

-40 

two dlffarcnt laboratorlaa utlilting 

• — . 

-% 

-43 

— 

-31 

-58 

-52 

-51 

-60 

-43 

totally aeparatc equlpaent, reagenta. and atandard*. 

•>l 
P.71 

•M 

1 

• »-> 

a 

. 

• 

1. l-r.j,-

m 

t • 1. 

4. M l M M 

* u -Imtm. 

r. tf|Mm 

rtmJ. 

• 

FIGURE 11 . ZERO DRIFT TREND FOR BENDIX CEM. 

! 

I-M9 1-

T 1 

"""Y ^ t 

• 

iO 

1 I 

| 

* 

g»* cMctatraitan. 

A • l»i:r«« t fcniti— 

1 • UatruMBf raHif*4 

1 

.i-— . 

T* 

/] 

FIGURE 12 . SPAN DRIFT TREND FOR BENDIX CEM. 

56 
P.72 

! 

• I 

i 

• 

r-U 

J' ft-1, L 

/ 

1 

.1—» -

• 

a .km 

•—-I.JUh.. A ! 

U 

l. Mn tatlm. 

1 

FIGURE 13 . ZERO DRIFT TREND FOR HOUSTON ATLAS CEM. 

aji/l.l^X VI 

wl Jk 

=•# = 

caJUratt.. a** * 

tf.t«4B . 

• M « " ecr 

FIGURE 14 . SPAN DRIFT TREND FOR HOUSTON ATLAS CEM. 

57 
P.73 

:rt aer tm mt -mm -tt* mm 

FIGURE 15. ZERO DRIFT TREND FOR DEL MAR CEM. 

FIGURE 16. SPAN DRIFT TREND FROM DEL MAR CEM. 

58 
P.74 

REFERENCES 

1. Standards of Performance for New Stationary Sources. 

Petroleum Refineries. Federal Register, 43: 

10866-10873, March 15. 1978. 

2. Repp, N. Evaluation of Continuous Monitors for Carbon 

Monoxide ln Stationary Sources. EPA 600/2-77-063, U.S. 

Environmental Protection Agency, Research Triangle Park, 

NC, 1977. 155 pp. 

3. Maines, CD., and V.C. Kelly. Determining Laboratory 

•nd Field Performance Characteristics of H_S Monitoring 

Systems as Applied to Petroleum Refinery Fuel Gas Lines. 

Draft Final Report, EPA Contract 68-02-2707, Scott 

Environmental Technology, San Bernandino, CA, 1978. 

4. Standards of Performance for New Stationary Sources. 

Proposed Revisions to General Provisions and Additions 

to Appendix A, and Reproposal of Revisions to Appendix 

B. Federal Register, 46: 8352, January 26, 1981. 

5. Standards of Performance for New Stationary Sources. 

Appendix B. Performance Specifications Federal Register, 

40: 46250, 46271, October 6, 1975. 

6. Determination of Hydrogen Sulfide Emissions from New 

Stationary Sources. Petroleum Refineries. Federal 

Register, 43: 1495, January 10, 1978. 

7. Determination of Carbon Monoxide Emissions from New 

Stationary Sources. Petroleum Refineries. Federal 

Register. 39: 9319-9323. March 8. 1974. 

8. Allen, T.H., and V.J. Root. Colorimetric Determination 

of Carbon Monoxide in Air by An Improved Palladium 

Chloride Method. J. Biol. Chem., 216: 309-17. 1955. 

9. Anonymous, Determination of Low Concentrations of Carbon 

Monoxide. J. Soc. Chem. Ind., 57: 79-82, 1938. 

59 
P.75 

10. Polls, B.D., L.B. Berger, H.H. Schrenk, Colorimetric 

Determination of Low Concentrations of' CO by Use of a 

Palladium Chloride - Phosphomolybdlc Acid-Acetone 

Reagent, Publication No. 3785, U.S. Dept. of Interior, 

Bureau of Mines, Report of Investigations, November 

1944. 16 pp. 

11. Veins, R.E. Colorimetric Methods for the Determination 

of CO in Air. Thesis. Kansas State University, 

Manhattan, Kansas 1973. 32 pp. 

12. Lambert, J.L., and R.E. Veins. Induced Colorimetric 

Method for Carbon Monoxide Anal. Chem., 46: 929-930 

1974. "" 

60 
P.76 

APPENDIX A 

DEFINITION OF TERMS 

Calibration Drift - The difference in the monitor's output 

readings from the established reference value after a stated 

period of operation during which no unscheduled maintenance, 

repair, or adjustment has taken place. 

Calibration Error - The difference between the pollutant 

concentration Indicated by the continuous monitoring system 

and the known concentration of the test gas mixture. 

Interference Equivalent - Positive or negative response 

caused by a substance other than the one being measured. 

Operational Period - A minimum period of time over which a 

measurement system ls expected to operate within certain 

performance specifications without unscheduled maintenance. 

Output Noise - Spontaneous, short duration deviations in the 

analyzer output that are not caused by Input concentration 

changes. Noise Is determined as the standard deviation 

about the mean expressed as a percentage of full scale. 

Precision - Variation about the mean of repeated measurements of the same pollutant concentration, expressed as one 

standard deviation about the mean. 

Range - The minimun and maximum measurement levels. 

Relative Accuracy - The degree of correctness with which the 

continuous monitoring system yields the value of gas 

concentration of a sample relative to the value given by a 

defined reference method or the emission standard. 

Span Drift - The change in the continuous monitoring system's output over a stated period of normal and continuous 

operation when the pollutant concentration at the time of 

measurement ls the same known upscale value. 

61 
P.77 

System Response Time - The time interval between a step 

change in pollutant concentration at the input to the 

monitoring system and the tine at which 951 of the 

corresponding value Is displayed on the system data 

recorder. 

Zero Drift - The change in the continuous monitoring system 

output over a stated period of time of normal and continuous 

operation when the pollutant concentration at the time of 

the measurement ls zero. 

62 
P.78 

'!-"'( • 

APPENDIX B 

TENTATIVE PUN FOR THE EVALUATION OF CO 

AND H2S CONTINUOUS MONITORS AT REFINERIES 

by 

William J. Mitchell 

Quality Assurance Division 

Environmental Monitoring Systems Laboratory 

U.S. Environmental Protection Agency 

Research Triangle Park, NC 27711 

APRIL 1979 

63 
P.79 

>*°«*i 

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 

ENVIRONMENTAL MONITORING SYSTEMS LABORATORY 

RESEARCH TRIANGLE PARK 

NORTH CAROLINA 27711 

April 26. 1979 

Dear 

We are Initiating a program to evaluate the long-term reliability of 

continuous monitors for measuring H-S In fuel gas feed lines at petroleum 

refineries and for measuring CO emissions from fluid cat cracker stacks. 

On March 15, 1978, EPA promulgated a regulation that required petroleum 

refineries to Install such monitors, but only after EPA developed 

performance specifications for these monitors. The objective of our 

program 1s to evaluate tentative specifications recommended for these 

monitors by an EPA contractor. 

The program will Involve Installing CO and H-S stack gas monitors at 

a petroleum refinery and operating and maintaining these monitors for 

approximately one year. The 1979 Pollution Engineering Yearbook and 

Product Guide indicates that you may have one or more monitors that could 

be used in this study. If this is correct, we would appreciate receiving 

Information about your monitor as an aid In planning our program. For your 

convenience we have enclosed an attachment with this letter that outlines 

the information that we need. 

For your Information and comment, I have attached a copy of our 

tentative plan. We anticipate that the H-S continuous monitors will be 

monitoring a stack gas that will be comprised primarily of methane and 

hydrogen and contain 30-500 ppm HpS, 10-500 ppm mercaptans and some SO2. 

The CO monitors will be monitoring a flue gas that will have the following 

character: 25-800 ppm CO, 8-15% CO?; 200-600 ppm SO?, ?00 ppm NO, 8-12% 

H-0, and particulate concentrations between 25-150 mg/m . 

If you wish to submit Information about your monitor(s) or need 

further information, please write to me at the address above or call 

me at (919) 541-2769. 

Sincerely yours, 

William J. Mitchell, Ph.D.. Chemist 

Source Branch 

Quality Assurance Division (MD-77) 

Attachments 

64 
P.80 

TENTATIVE PUN FOR THE EVALUATION OF CO 

AND H^S CONTINUOUS MONITORS AT REFINERIES 

I. BACKGROUND 

On March 15, 1978, EPA promulgated New Source Performance Standards that required petroleun refineries to continuously monitor the 

CO emissions from fluid catalytic crackers and the H-S levels in fuel 

gas feed lines. However, at the time the regulations were promulgated, EPA did not have performance specifications available for the 

CO and H-S continuous monitors. Therefore, the refineries are not 

required To Install the monitors until these performance specifications are developed. 

Tentative performance Bpecifications for both CO and H-S monitors 

have now been advanced based on laboratory and field evaluations done 

by Scott Environmental Technology. In the laboratory phase of Scott's 

program, candidate instruments were evaluated to determine response 

characteristics, stability with time, temperature and flow rate, and 

sensitivity to potential Interferences' likely present ln the stack 

gas. Instruments that performed adequately ln the laboratory were 

then evaluated at a petroleum refinery to establish their field 

performance. 

Five CO monitors and two H-S monitors were evaluated at the 

petroleum refinery during field trials that lasted approximately 55 

days. Only one CO monitor and one H-S monitor performed adequately. 

In the case of the CO monitors, dally calibration checks were mandatory for reliable operation of the Instruments, but even with the 

inclusion of dally calibration, Scott questioned the long term 

reliability of these monitors. Instrument malfunctions, sampling 

system malfunctions and data logger malfunctions plagued these field 

evaluations. 

Based on these studies, Scott proposed tentative performance specifications for both CO and H-S monitors. The proposed CO monitor 

specifications are summarized in Table B-1. The proposed H2S monitor 

specifications are the same as those described ln EPA Performance 

Specification 2 - "Specifications and Test Procedures for SO- and N0X 

Continuous Monitoring Systems in Stationary Sources." 

65 
P.81 

TABLE B-1 

RECOMMENDED PERFORMANCE SPECIFICATIONS FOR 

CONTINUOUS MONITORS OF CARBON MONOXIDE AS 

APPLICABLE TO PETROLEUM REFINERIES 

PARAMETERS SPECIFICATION 

Range 

Calibration Error 

Relative Accuracy 

Precision 

Respone Time (Systen) 

Output "Noise 

Zero Drift, 2 Hours 

1 

Zero Drift, 24 Hours 

1 

Span Drift, 24 Hours 

Interference Equiv. 15t C0-

Interference Equiv. 10J H^O 

Operational Period 

0-1000 ppm 

£2* Span 

j(105 Mean Ref. Value 

OJ Span 

OO Minutes 

O t Span 

<y% Span 

<2% Span 

<2.5% Span 

<\0 ppm 

<5 ppm 

168 Hours 

Expressed as sum of absolute mean value plus 951 confidence 

interval in a series of tests. This value is based on • 

relative comparison of the monitors to each other and not to 

Method 10. 

I I. PROPOSED PUN 

A. Objective 

Establish the long-term operational performance (durability/ 

reliability/accuracy) of CO and H-S monitors when the monitors are 

installed and maintained as directed by the instrument manufacturer/ 

vendor and from this data determine what are reasonable and useful 

performance specificaions for those monitors. 

66 
P.82 

B. Duration of Project 

The field testing will last approximately one year. The laboratory testing preceding the field study will last one to three months 

depending on the problems encountered and the Instruments selected for 

evaluation. 

C. Site Selection Criteria 

The CO nonitors will be installed at a fluid cat cracker and the 

H-S nonitors will be Installed on a fuel gas feed line preferably 

equipped with an amine treater for removal of H-S. Ihe actual 

selection of the test site(s) will be nade using the following 

criteria: 

1. Attitude of plant management toward program. 

2. Accessibility of sit e to EPA and EPA contractor 

personnel for installation , calibration and 

maintenance of equipment. 

3 . Scheduled plant shut-downs for maintenance/ 

production changes, etc . 

4. Availability of a room or trailer that ls suitable 

for installing continuous monitors, i.e. , one that 

can be maintained at a constant temperature and 

humidity. 

5. Availabilit y of a stable , continuous supply of 

electrical power. 

D. Equipment Procurement 

1. Continuous Monitors 

The continuous nonitors will be selected based primarily on 

engineering Judgment about their technical reliability and durability, 

maintenance requirements, data recording requirements, and availability of spare parts. Specific criteria for monitor selection 

include the following: 

a) Willingness of nonitor vendor to cooperate with EPA, 

e.g. , supply the monitoring system requested 

including al l pre-delivery instrument check-outs 

requested. 

b) Cost of the nonitoring system to the government in 

relation to other nonitors with similar operating 

principles. 

c) Delivery time involved In obtaining the nonitor. 

67 
d) Anticipated cost of nalntenance, calibration and 

repair of the Instrunent Including availability of 

spare parts, ease of on-site repair and availability 

of service personnel for major equipment repair. 

e) Sampling conditions required by the nonitor. I.e., 

temperature, stack gas character, humidity, flow 

rate, etc., and availability of a aultable sample 

conditioning system for obtaining the required 

sampling conditions. 

f) Existence of a similar system on other petroleum refineries and the demonstrated performance of the 

system. 

g) Availability and cost of training EPA contractor personnel in the operation and maintenance of the nonitoring system. 

2. Stack Cas to Monitor Conditioning System 

The actual sampling system required to bring the stack gas to the 

monitors cannot be determined until the field site(s) and the candidate monitors are selected. If a commercially-available system exists 

that can be obtained at reasonable cost, such a system will be bought. 

However, if necessary, a site-specific sample conditioning system will 

be designed and installed by EPA. The system Installed will meet or 

exceed requirements of every nonitor that will be used in the evaluation. 

3. Data Recording System 

It is anticipated that strip chart recorders will be used to 

record all data generated by the monitors. Data loggers and magnetic 

tapes will likely not be used since these devices have not demonstrated long-term operational stability. Similarly, manual calibration and span checks will be an integral part of the program rather 

than relying simply on automatic controllers. 

E. Trailer for Housing the Monitors 

Monitors require a well-controlled environment for operational 

stability. A trailer or similar facility that has temperature and 

humidity controls will be used to house the nonitors. 

F. Determination of Performance Specifications 

and Operational Characteristics 

The performance of the CO monitors will be compared to the tentative performance specifications now being advanced by QAQPS as 

Performance Specification 4. The performance of H-S monitors will be 

compared to the nost recent specifications for SO- and N0„ nonitors. 

68 
Relative accuracy performance tests for CO will be conducted using EPA 

Method 10 unless ESRL is able to supply a wet chhemical test nethod 

for CO. The relative accuracy tests for H-S will be conducted using 

EPA Method 11. Initially, the number of samples specified In perfornance Method 2 for SO- will be used for the H-S and 00 relative 

accuracy tests. Span checks and drift checks will t>e done daily using 

calibration gas mixtures that correspond to OJ, 25J, 50J, 75J and 100J 

of span. However, not all span gases will be used everyday. 

Described below ls the tentative schedule for these tests. This 

schedule nay change based on final selection of nonitors and test 

sites: 

Parameter 

Relative Accuracy Test 

Zero/Span Checks 

0, 50J, 100J span check 

0, 25J, 50J, 75J. 100J span check 

Response Time/Noise Check 

Interference of other gases 

Time Interval 

1 week 

1, 2, 4, 8, 12 months 

daily 

weekly 

weekly 

monthly 

G. Tentative Schedule for Accomplishment of Study 

Task 

Obtain permission to presurvey 

tentative sites 

Complete site visits and select 

test sites 

Order monitors/sampling 

systems, etc. 

Procure necessary supplies for 

reference method tests 

Complete laboratory check-out 

of monitors 

Install/check-out nonitors 

Complete field studies 

Completion Date 

May 15, 1979 

June 15. 1979 

i 

July 15. 1981 

August 15, 1979 

November 15, 1979 

January 15, 1980 

January 15, 1981 

69 
P.85 

III. SPECIAL MOTES 

A. Each nonitor will be subjected to whatever lab tests are 

necessary to deternine lf it will work In a field situation. 

These lab tests nay be done by the vendor before shipping the 

equipment to the EPA contractor. 

B. Tentatively, we plan to have the person or persons responsible for naintalnlng the nonitors receive nonltor-specific 

training from the Instrument vendor either on-site or at the 

vendor's facility. 

C. Based on cost and anticipated delivery time, spares of 

those components most likely to fail (phototubes, scrubber 

columns, switches) will be stored at the test site. 

D. If possible, two identical Instruments nay be operated 

at the site to yield an estimate of instrument precision. The 

nethod of standard additions nay also be employed on occasion to 

check the reliability of the monitors. In this case, a calibration gas would be Injected Into the sample stream to see if the 

expected Increase in response was obtained. 

70 
P.86 

APPENDIX C 

VENDORS RESPONSE TO LETTER FROM EPA 

MCATm 

ao usa-mst 

usronst eo t,s norosro WSTHUNPH corT/ofDurrnc ntwciru 

Affiled Automation, toe 

•ertleevllle . OK 

amttm tcelegy Corp. 

f. 0. %n SM. 

. XX 1KM 

leelkaracb laetr—ante 

1300 Leghorn Street 

Nnatal a View. CA MOO 

aeaellae laduatrlea 

f . 0 . tea M l 

lyeae, CO tOSAO 

•actaae loetnaefita. Ise . 

frecea. Inetruaente Divlalaa 

*»O0 Harker tl* . 

fiUlartoo. CA fM M 

teedta Corporation 

bvirooaental and Preceaa 

Zaacr-uaanta Civlalan 

f . 0. Drever 131 

Lewiaaurg. HV 2*M1 

fertroRa-eetal and frecaaa 

Aoalyier Karkct DrraUn—nt 

CEA iBatnaaanta. lac. 

IS Ctwrlea Street 

Maacmd. U 07*7} 

Calibrated laatnaarnta. toe. 

7)] Saw Mill live r load 

Ar deley. « 10502 

CaaitrarcfCocri Cor*. 

•10 tDtllos Drive 

ritta*ur«b. PA 1323S 

Central Iaetriaaenta Carp. 

I f ttt fix Avaaue 

falrfleld , HJ OTOO* 

Dictaphone Ca. Detection fro-ducte 

Awdio/IJaetronlc* Divl.len 

*7S till . Stm t 

•tHatalx Via*. CA MO O 

CD: Optlchrea 102 

•af: Optlchrea 102 

00: SOOO 

CO: P 103ft* 

B.S: P I030A 

CO: MS- U 

•iS: M l 

CO: M03 

«,S: 7770 

CO: ti7t>/cc/rn> 

a,.. ti).ooo/cc/m> 

CO: SJSOO/U 

CD: 14500/CC/TC 

l.f: »3«00/CC/rfD 

CO: «t700/HCn 

•,S : ftOOO/Chcailualnaacasca 

CO: StOOO/KDDt 

•,S : S»710/CC/m> 

aifllak . Ue . 

237 Put s«> Avenue 

Caa*rld|c, M 0213* 

t.l . DuPont DcNeaoura t Ca. 

1007 Market Street 

HUaU|ioe . K ItTOt 

la-erratic. Science, lac. 

t 3 Caacutlve Blvd. 

tJaaferd. «T IOS23 

IX COi Snatru. aet epeclflad U (coat aet opacified) 

•a(: *00 I.S. (M00/0V 

n CO: tcelyier 3107 CO: IllOO/electroeh 

71 
P.87 

APPENDS C 

VENDORS RESPONSE TO LETTER FROM EPA 

ncATin 

*o Uspoait 

UST-ONSt CO B.S noposts WSHUWHT cort/optJUTinc mvciru 

Dy-eeac lance. 

environmental Product. Div. 

Teaaiehlp Line tead 

Blaeeall. PA 1*422 

Ecology Board, lac. 

92J7 Independence Ave. 

Oataaorth. CA •1311 

tthyl latertech Carp. 

It ftoe.el tead 

frlaceteo. «J OSSAO 

BrvletfPeckjrd 

Scientific Initriaaenta Div. 

1*01 CalifornU Avenue 

Pole Alto. CA 94304 

•ortka Inetriawate. lac. 

1021 Durvea Ave. -

Irvine. CA 9271* 

Ibueton Allot. IJK. 

••it) Seythorve Drive 

Bouatoft, TX 77041 

lafrared leduatriea 

Vketern Dlvialen 

p. 0. Boa 9*9 

Casta karhara, CA 93102 

U u r Baaearch take. lac . 

J09 K. Fairfax Ave. 

to* Angela.. CA 90034 

la-ad. a Rorthrup Ceapany 

SVjae-iaytovn Ptka 

Berth WaJaa. PA 19454 

Niloy lab-ore torlea, lac. 

• 715 Electronic Drive 

B. Springfield. U 22131 

•daa Safety Appllaace Ca. 

•00 Penn Center tlvd. 

Plttaaurgh, PA 1S23S 

Monitor Lake. lac. 

101»0 Scrlppa -tench Blvd. 

Sen Diego. CA 92131 

Proceaa Analyiere, lac . 

1101 State toad 

Princeton, BJ 01*40 

Hilton toy Cuapaiij 

Plow Control Div. 

205 Ivylaad toed 

Ivylaad, PA 11174 

Teledyne. lac. 

Analytical Io.truaente Div. 

93) V. Ri.eloe Drive 

Bae Ckrial. CA 9177t 

•2SH-107W 

722S-102 

703 

t.S: S7200/Pb Ac 

B.S: S12,OS9/PhAc-* 

CO: S19tS/RDXa 

lira 202 

CO: loft detector 

B.S: Bet epaelfled 

CO: 24-222-4 

B.S: 12-230 

CO: S4400/KBU 

CO: S7000/RSDL 

l.i : CC/TO 

CO: 94100/CC/TC 

B.S: S99O0/CC/TTD 

CO: 9300 

B.S: ti l DHCO-2QX 

CO: StS00/»It 

B.S: S4700/UV 

Tfcerao tlectron Carp. 

trviroeacntal In,true 

101 Sawth Street 

Bofklntea. HA 01749 

•ta Mv. 

72 
P.88 

APPENDIX C 

VENDORS RESPONSE TO LETTER FROM EPA 

BKATIVI 

•o Bisr-oast 

USPORSZ CD B.S noposo wntw-aw COn/OPOUTIMC PtlKCXPU 

Tracer, lac . 

Saatruaaat Dlvlalen 

•SOO Tracor lene 

Anat la. XX 79721 

•fcetern Beeeerch aad 

Develepaent ltd. 

1313 - 44th Ave., BI 

Calgary Alta 

l e i Mar Scientific 

P. 0. Boa 4S4 

Addiaoo. TX 73001 

Anarad, Inc. 

P. 0. Boa 3140 

•ante Serhere, CA 93I0S 

•fl: 

MX CD: AB SOlk 

B.S: S4700/PkAc 

co: tjsoormn 

* Orginally prepoaad, hut wlaen cold ordering Del Mar Chey offered the S2SR-102N. 

73 
P.89 

APPENDIX D 

FCC EMISSIONS GAS SAMPLE CONDITIONING SYSTEM 

The stack gas was conditioned at the stack to remove particulate, 

acid nlst and noisture. The gas conditioning system was housed In a 

netal case 55 cm by 76 on by 33 cn. The system (Figure D-1) consisted 

of the following parts: 

1. Probe. SS 202, length 130 on, OD 5.1 cm, ID 4.9" cm, 

slots 2 to 4 an wide cut ln the 40 cm nearest the tip 

and covered with Balston Type 20/80-A microfiber filte r 

(5.1 cm ID by 45 cm long), glass wool plug ln probe tip; 

and steel plate welded 5 cm from the end to attach probe 

to port flange and probe extension (Figure D2). 

2. Probe Extension. Aluninum pipe, 28 cn long, 10 co OD, 

one end welded to al uninun plate (to attach extension to 

probe) and other end externally threaded to accommodate 

pipe cap. Each side contained a piece of aluninum 

tubing 2.5 cm OD by 8 cm long to allow sample to pass 

from probe into the gas conditioning system and to allow 

a stack sample to be withdrawn into a Tedlar bag. The 

bottom of the extension contained a piece of aluninum 

tubing 1.6 -cm OD by 5 cm long for attaching a 60 cm 

U-shaped drain. This drain continuously removed 

condensate from the probe extension while maintaining a 

water seal to prevent ambient air from entering the 

system. 

3. Balston 20/80-A Filter Housing (SS304) with type 200-80 

Grade D and Type 200-35 SS filte r support core filter . 

Gas passed from inside to outside to coalesce water and 

remove small particulates. A U-trap was attached to the 

bottom to allow continual draining of the condensate. 

4. Balston 97S6 Filter Housing (SS316) with 050-05CH microfiber filter s (1.2 cm ID by 3.1 cm long). One of these 

filter s was added to the system December 5, 1980, to 

reduce plugging of the Perma Pure dryer; the second was 

added January 9, 1981. 

5. Perma Pure Model PD-1000-24S (200 tubes, 60 cn long). 

Two connected in series to remove moisture. A pressure 

regulator was used to maintain dryer purge air at a flow 

of 17 L/min at 2 to 3 psi. 

74 
P.90 

6. Pump. ADI Model 19320-T dual-stage (with Carpenter 20 

heads to reduce corrosion). Teflon-coated diaphram and 

Viton valve gasket and discs. The single-stage pump 

used originally would be adequate for most systems. 

7. Tubing. SS 316 between probe extension and Balston 97S6 

filter , polypropylene between 97S6 filte r and puap. 

8. Sample Line. 200 n long, 0.95 on ID by 1.2 cm OD, black 

nylon, unheated. 

9. Balston 20/80-A Filter Housing with Type 20/80-A Grade 

D, nicrofiber filter . Located immediately in front of 

the trailer to remove fine particulate. 

The overall performance of the gas conditioning system was very 

good. Problems and changes that occurred between February 11, 1960 

and April 28, 1981, are summarized in Table D-1. In general, the 

following comments are noted: 

1. Polypropylene tubing was found to be superior to 

stainless steel tubing. The latter reacted with the 

stack gas to yield a fine particulate that collected at 

bends and elbows in the conditioning system. 

2. The Balston 20/80-A filte r was difficult to disassemble 

in the field due to its large diameter and the lack of 

large wrenches. 

3. The U-shaped drains worked well, but care should be 

taken to prevent freezing; either by wrapping the drain 

with heating tape or by using heat radiating from the 

stack. 

4. From February 18, 1981, to April 28, 1981, the system 

worked without failure or maintenance at a sampling rate 

of 5 to 8 L/min. Vhen disassembled on April 28, 1981, 

the Perma Pure dryer inle t contained no particulate, the 

Balston 20/80-A filter s were unbroken, the pump inle t 

diaphram contained a reddish syruplike liquid (pH less 

than one) that absorbed water rapidly upon exposure to 

the ambient air . An anion analysis showed that the only 

anion present was sulfate. 

5. The system described was constructed to provide a sample 

flow rate of 6 to 15 L/min to the trailer with a minimum 

system response time. For most applications, a flow 

rate of 1 L/min would be sufficient; thus one PD-750-24 

Inch (100-tube) Perma Pure dryer might be adequate for 

75 
P.91 

nost applications. This would result in a considerable 

savings. In addition, the probe extension and the 

Balston 20/80-A filter ln the sample case eould be 

replaced with aroaller units without adversely affecting 

the aampie conditioning systen. Probe filter integrity 

was maintained as long as the slotted side of the probe 

was facing downstream. Vhen the probe was rotated 90 

so that only half the slotted side of the probe was 

facing downstream, a hole about one cm ln diameter 

formed In the filter at a point about 35 cm from the 

tip. A glass wool plug ln the probe also helped keep 

the probe clear. 

76 
aa-Hi 

2 STAGE "ADr 

DIAPHRAM PUMP 

TO SAMPLE 

•DISTRIBUTION 

SYSTEM 

« ^—* * -V 

PURMA-PURE 

GAS DRYERS 

SAMPLE PR08E IN-8TACK FILTER 

/,//M//////////hW///l 

V M" •{ 

- a r a| 

1

 BALSTON TYPE 80 FILTER 

\^r WATER TRAP A DRAIN 

FIGURE D-1. SCHEMATIC DRAWING OF SAMPLE CONDITIONING SYSTEM. 
P.93 

FIGURE D-2. PROBE, PROBE EXTENSION AND BALSTON 20/80-j A FILTER. 

78 
TABLE D-1 . MAINTENANCE/REPAIR OF STACK GAS CONDITIONING SYSTEM OF FCCU 

vo 

9 

a 

vm 

tnt 

tm 

vn 

an 

d/19 

%na 

9/3 

im 

pn 

vn 

tm 

19/11 

j a ^ 

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mL. 

m» 

• 

3 

S 

t 

9 

7 

11 

11 

9 

9 

» 

1-f 

I 

94. 

•* 

e 

9 

S 

id 

17 

II 

It 

IS 

11 

If 

17 

• 

i 

e 

• 

e 

* 

8 

« 

• fc O 

3 

• 

•9-

k 

K ft. 

d » 

• 

fc. 

* 

I 

•m 

1 

I 

* 

1 

a 

V 

• 

• •* * 

I 

8 

• t . 

• 

> 

& 

fc. 

• 

tf* 

fc. 

.•? 

o t 

17 

17 

17 

9 

19 

19 

17 

19 

IS 

17 

I I 

19 

1 

ACTIVITY: 

iMtelled .jrttea. *eee .letted aide fecial dewntre* vlth flea, aeel plea le tip. M l W-7T9 Uklat. Pmm UmpH «t 

«OI-MJI0T villi ee. rKlrcelatlan lyttaa ta centrel flaw. 

f 1e> rv,trlcted ky tim frey pevdar at P*« Inlet. *a*ec*d St 719 teklne krteee* **P end pop wit* pely*re*yleae. Ci 

at pmm evtlat md In .tack 7S pre ky POI«. 'lent aenlter reed M pan. Sytlae \ttk-t*>Kkt4 at 9 Inc* *». P.vdir 

analytli: la: III {t-.l); Anlen $0^, pM candmtate 7.7. Caw-Pun at. freen. 

IIMH I pwa rvtlrcelatlen ayataa tocevae velve leetlnf. Pet *-tn » In ta eeltett tend»n»et.. 9reta eaa lectin* et tea 

•olalrd prate W and IIWIII I fl.t i m l plat te .ee effect en pertlcelate fllUrlnp efficiency. Preke elver. C9 .tec* 

14 pea, CO .t pmm evtlrl Jl ppa. 

f*9 perf. air line eccleantly cteMtf aff ly iaa>im et plant. SyttM fall tf eater ket Mil l pawta*. 9rativd *yet« • 

aim l air Hn*. 

eat in tea .teae ajpaa (MI-IIUOT) te five 19 9*1 preatere at trailer U acteaajedeta Called teteaattea aenltar 

reaelreaent.. 

Ilnt*d teklDf raatrlcttnf flea Inte paep. arplaced cracked preke flttar. rpeka ka* aaelt pertlceleU dapeelt. 9at aaa 

net eccludad. 

Hent C9 wry Mfk. PH la 1:9 ditatlan mi— to krlne 09 Inte epaa reaft af aenlter. 91 let ten >y*tea reae** **m% 

IWO. 

tat attains preke eaten.ten aavlppad wtth 9 drain ante ante. 

Syttea Ot. Inatatled CO. aanltar In trelltr. 

tattered r^twed paw dlaphrta aa aaaa Itttt. 

RtpfftCtv ttw f pM ^ •"M*"'**aBj WC1I H I RM PVpW-PVV. MM frf(P MPMi l VN NMV. 

line pleaped. trained I J 1 free f-90-1 filter, laapla flee aeter (retaaeter) kell cerreded. ketend t-et—tn fi w 

•y*taa vltheet repteceeent. — 

(Continued) 

Ito 

a*a 
TABLE D-1. MAINTENANCE/REPAIR OF STACK GAS CONDITIONING SYSTEM OF FCCU 

oo 

o 

1999 

11/77 

11/19 

U/9 

I S 

1/9 

VH 

1/19 

vn 

tm 

l/M 

4/79 

1 

* 

k 

* 

a 

• 

n 

t 

9 

1 

-

-

* 

• 

-

-

9 

7 

I 

I 

1 

• 

• 

1 

t 

a 

• 

• 

i 

a 

a i 

activity 

**• Inttt pleeaad aith green dapeatt. Anatytl. aimed: (7:1:1 far ftiMiCr), aalta M | tnd »t . M RJI (9* att0M|. 

Hr.ivred tanpl. flea eilnf tPO purge air rataeater. 

treke filter hed hete In It. Irtttced. 779 partially planed, tapttced t -PP 1999-79*99 (fl ca a 199 tdket) att* tat 

n fJO-tt (Cl ca a 109 take.), trplaced pw a heed. (JUS?) vlth Cerpenter 70 heed*. 101 Inlet take, ea fceth PP9 plaeaa 

•ale la preke fitter. Hated 9719 filter keteatn f-99-1 tad 7*9 ta redact ptaatlnf tt 779. 

V-drtln an preke eetenalen centalnad frtita tendmiett. 9rtlaed. 9tp1tced 9799 fitter, ttveat ctatalntd tight prep 

partlcetatt. 

Drain en 7-19-1 filter tpp.rtiitly freien ea 1-19-01 tlltwtna cendntttt ta fill tyttta Inctedtaf eeepllaa Hat. «Mi r 

frete at night ket thevrd daring day .a CO. laveti daring day verv nerval, aeptaced f-00-1 and f-W-7 fitter,. 7-99-1 

•rl, cewred vlth fr*en .line. f-80-J ca»tred vlth grey poxdtr. int filter cevervd aith t'»«n/|i.y pevd.11. replaced 

filter al 

treke filter hed helt. npttctd tnd rtttttd praht tt tittttd tl * fee Inf eeaattreaa. M flea, atal la prtte tip. ftrt 

.hert .actlan ef preke filter en ealt end ef preke, te thet It teethed tha preke eatdaalea c w te pravlda eddttleeat 

filtering. 

N t lerp aver tyttta ta etllltt atact'i redltrt heat ta prtitat Treating af ctadtmatt. 9at taatttf Upt aa prakt 

.itam Ian drain. 

Teret air rtfalatar hed ttert eeen tt 7} p.1. take 1a dryer r«ptered. Seat t*t t tTtt plagged. htptitad I t 799-4t 

vlth t 70 I00O-74S 770. fat tee 97M fltteit In terltt. Tal Iai.tea 45 C filter eaanatreee ef pwap end felleved 

vlth Miltney nt n te central f lev te 9 lee. 

Sy.Ua Mil l ftnctleelaa. Pratt clttr. » , Hart lfl , » , atnlfald 111. 

Jyttee .til t fwclltntng. C9, .tact 1» , (9. atnlfald IS . •eaeved pyitat. 
P.96 

APPENDIX E 

MANUAL METHOD FOR MEASURING 

CARBON MONOXIDE IN REFINERY GASES 

1. PRINCIPLE AND APPLICABILITY 

1.1 Principle 

An Integrated sample is extracted from the gas stream, passed 

through hydrogen peroxide and alkaline permanganate solutions and 

collected in a Tedlar bag. The carbon monoxide (CO) concentration in 

the sample is measured spectrophotometrlcally using the reaction of CO 

with a palladium chlorlde/leuco crystal violet/potassium lodate 

solution. 

1.2 Applicability 

This method is applicable for determining CO emissions from 

stationary sources. 

2. RANGE AND SENSITIVITY 

2.1 Range. As written, the nethod applies to gas samples that 

contain 20 to 1000 ppm CO. Samples containing in excess of 1000 ppra 

CO can be analyzed by reducing either the gas volune or the shaking 

time. Samples containing less than 20 ppm can be analyzed by 

Increasing the volume of sample reacted with the palladium 

chloride/leuco crystal violet/potassium lodate solution or by 

increasing the shaking time or frequency. However, if such changes 

are made in the procedure, the linearity of the absorption curve oust 

be checked under these conditions. 

2.2 Sensitivity. Sensitivity depends on shaking time, shaking 

frequency, gas volune and shape of reaction vessel and cannot be 

specified absolutely. As written, the sensitivity of the method is 

approximately 10 ppo CO. 

2.3 Interfering Agents. Sulfur oxides, nitric oxide, and other acid 

gases which interfere with the reaction, are removed from the gas 

sample during sample collection. These gases are removed by passing 

the sampled gas through a ••» percent potassium permangate/5-percent 

sodium hydroxide solution. Carbon dioxide does not interfere with the 

reaction, but, because it is removed by the scrubbing solution, its 

concentration must be measured and an appropriate volume correction 

made. 

81 
P.97 

4. fUECISION, ACCURACY AND STABILITY 

4.1 Precision. The estimated intralaboratory standard deviation of 

the method Is 2.5 percent of the mean for gas samples analyzed ln 

triplicate. This estimate, which applies to the concentration range 

20 to 1000 ppm, was determined from 22 samples collected at a 

petroleum refinery. The interlabortory precision has not been 

established. 

4.2 Accuracy. On the average, the manual method results were biased 

4 percent high for 22 samples analyzed by an NDIR calibrated with NBS 

standards. The manual method was biased 5 percent high when used to 

analyze certified calibration gas mixtures that contained SO., NO, 

C02, and 100 to 500 ppm CO ln nitrogen. 

4.3 Stability. The individual components of the colorimetric reagent 

are stable for at least one month, but the colorimetric reagent must 

be used within 3 hours after preparation to avoid excessive blank 

correction. For optimum accuracy the samples must be reacted and 

analyzed no later than 3 hours after the colorimetric reagent has been 

prepared. 

5. APPARATUS 

5.1 Sampling (Figure E-1) 

5.1.1 Probe. Stainless steel, sheathed Pyrex glass or equivalent, equipped with a glass wool plug to remove particulate matter. 

5.1.2 Impinger. Three Greenburg-Srolth impingers connected in 

series with leak-free connections. 

5.1.3 Pump. Leak-free pump, Metal Bellows Model 110 or equivalent with stainless steel and Teflon parts to yield a flow rate of 0.2 

to 0.4 L/min. 

5.1.4 Surge Tank. Installed between the pump and the rate meter 

to eliminate the pulsation effect of the pump on the rate meter. 

5.1.5 Rate Meter. Calibrated rotameter, or equivalent, to 

measure flow rates between 0 to 0.4 L/min. 

5.1.6 Flexible Bag. Tedlar, or equivalent, with a capacity of 10 

liters. Bag must be leak-free. 

5.1.7 Valve. Needle valve, or equivalent, to adjust flow rate. 

5.1.8 Fyrite Analyzer, or equivalent, to measure CO- concentration to within +0.5 percent accuracy. 

82 
P.98 

5.2 Analytical 

5.2.1 Spectrophotometer. Single or double beam 

absorbance at 589 nm. Slit width should not exceed 20 nm. 

to measure 

5.2.2 Vacuum Gauge. U-tube manometer, 1 meter (36 in.), with 

1-nm divisions, or other gauge capable of measuring pressure to within 

±2.5 ns Hg (0.10) in. Hg). 

5.2.3 Pump. Capable of evacuating the gas reaction bulb to a 

pressure equal to or less than 75 mn Hg (3 in. Hg) absolute, equipped 

with coarse and fine flow control valves. 

5.2.4 Barometer. Mercury, aneroid, or other barometer capable of 

measuring atmospheric pressure to within 2.5 on Hg (0.1 in Hg). In 

many cases, the barometric reading may be obtained from a nearby 

national weather service station, in which case the station value 

(which is the absolute barometric pressure) must be requested. An 

adjustment for elevation differences between the weather station and 

sampling point must then be made at a rate of minius 2.5 mm Hg (0.1 

in. Hg) per 30 m (100 ft) elevation increase, or vice versa for 

elevation decrease. 

5.2.5 Reaction Bulbs. Pyrex glass, 100-125 mL with Teflon 

stopcock, leak-free at 650 mn Hg. Designed so that 10 mL of the 

colorimetric reagent can be added and removed easily and accurately 

(Figure E-2). Commercially available gas sample bulbs such as Supelco 

#2-2161 and Alltech #7012 can also be used. 

5.2.6 Volumetric Pipettes, 

graduated pipette. 

Class A, 4 mL and 10 mL and 1 mL 

5.2.7 Volumetric Flasks. 100 mL 

• 5.2.8 Graduate Cylinder. 1000 mL. 

5.2.9 Shaker Table. Reciprocating-stroke type such as Eberback 

Corp. Model 6015. A rocking arm or rotary-motion type shaker may also 

be used. The shaker must be large enough to accommodate at least six 

gas sample bulbs simultaneously. It may be necessary to construct a 

table top extrusion for most commercial shakers to provide sufficient 

space for six bulbs (Figure E-3). 

5.2.10 Spectrophotometer cells. 1 cm pathlength. 

83 
P.99 

6.0 REAGENTS 

6.1 Sampling 

6.1.1 Alkaline Permanganate Solution. Prepare by dissolving 40 

grams of ACS reagent grade aodiun hydroxide and 50 grams of ACS 

reagent grade potassium permanganate In 1 liter of distilled water. 

This is sufficient for removing NO and SOp from 50 liters of gas 

containing 15? CO.. 

6.2 Analysis 

6.2.1 Stock Solutions 

6.2.1.1 Potassium lodate. ACS reagent grade, or equivalent. 

6.2.1.2 Sodiua Chloride. ACS reagent grade, or equivalent. 

6.2.1.3 Palladium Chloride. ACS reagent grade, or 

equivalent. 

6.2.1.4 Sodium Monohydrogen Phosphate Heptahydrate 

(Na-HPO^H 0). ACS reagent grade, or equivalent. 

6.2.1.5 Leuco Crystal Violet (4,4',4" methylidynetris (N,Ndimethylanillne)). Eastman Kodak Company Stock No. 33651. 

6.2.1.6 Phosphoric Acid (85J). ACS reagent grade, or 

equivalent. 

6.2.2 Vorking Solutions 

6.2.2. 1 Sodium Monohydrogen Phosphate (0.1M). Dissolve 

2.68 grams in 100 mL of distilled , deionized water. This solution i s 

stable indefinitely. 

6.2.2. 2 Sodium Tetrachloropalladate(II) Solution (0.005M). 

Dissolve 0.0887 grams of palladium chloride and 0.0595 grams of sodium 

chloride ln 50 mL distilled , deionized water and dilut e to 100 mL. 

This solution is stable for at least one month. I f a brown preclpate 

forms i t can be dissolved by adding a few crystals of sodium chloride. 

6.2.2. 3 Leuco Crystal Violet Solution. Dissolve 0.0256 

grams leuco crystal violet in 80 mL water containing 0.25*iL of 85X 

phosphoric acid and dilut e to 100 mL. This solution is stable for at 

least one month. 

6.2.2. 4 Potassium lodate Solution (0.1M). Dissolve 2.14 

grams of potassiun lodate in 100 mL of distille d deionized water. 

This solution l s stable indefinitely. 

84 

»j ufw^y ^ \m» LTV^T'-?^ . 
p.1 

€.2.2.5 Colorimetric Solution. Pipet 4.0 mL each of potassium lodate solution (6.2.2.4), leuco crystal violet solution 

(6.2.2.3) and sodium tetrachloropalladate (II) solution (6.2.2.2) Into 

a 100 mL vol inetrie flask. Pipet 0.6 mL sodium monohydrogen phospate 

solution (6.2.2.1) into the flask and dilute to volune. This solution 

should be used within 3 hours of preparation to minimize the contribution of the blank and the sample absorbance. Ihis is sufficient 

volume to analyze three stack gas samples in triplicate. 

6.2.2.6 Standard Gas Mixtures. Traceable to NBS standards 

and containing between 100 and 1000 ppn CO in nitrogen. The calibration gases shall be certified by the manufacturer to be within •_ 2 

percent of the specified concentration. 

7.0 PROCEDURE 

7.1 Sampling. Evacuate the Tedlar bag completely using a vacuum 

pump. Assemble the apparatus as shown in Figure E-1. Loosely pack 

glass wool ln the tip of the probe. Place 400 mL alkaline 

permanganate solution (6.2.1) in the first two impingers and 250 mL in 

the third. Connect the pump to the third impinger and follow this 

with the surge tank and the rate meter. Do not connect the Tedlar bag 

to the system at this time. 

Leak-check the sampling system by plugging the probe inlet and 

observing the rate meter for flow. If flow is indicated on the rate 

meter, do not proceed further until the leak is found and corrected. 

Insert the probe Into the stack and draw sample through the system at 

300 _• 50 mL/min for 5 minutes. Connect the evacuated Tedlar bag to 

the system, record the time and sample for 30 minutes, or until the 

Tedlar bag Is nearly full. Record the sampling time, the barometric 

pressure and the ambient temperature. Purge the system as above 

Immediately before each sample. 

The sampling system above is adequate for removing sulfur and 

nitrogen oxides from 50 liters of stack gas when the concentration of 

each is less than 1,000 ppm and the C0? concentration ls less than 

15%. The samples in the Tedlar bag should be stable for at least one 

month, lf the bag is leak-free. 

7.2 Ancillary Methods 

Measure the CO. content ln the stack to the nearest 0.5% each 

time a CO bag sample is collected. A grab sample analyzed by the 

Fyrite analyzer ls acceptable. 

85 
P.2 

7.3 Analysis 

Assemble the system shown in Figure E-4 and record the information required in Table E-1 as lt is obtained. Pipet 10.0 mL of the 

colorimetric reagent (6.2.2.5) in each gas reaction bulb (5.2.5) and 

attach the bulbs to the system. Open the stopcocks on the gas bulbs 

but leave the valve on the Tedlar bag closed. Turn on the pump, fully 

open the coarse-adjust flow valve and slowly open the fine-adjust 

valve until the vacuum is at least 550 mm Hg. Now close the coarse 

adjust valve and observe the manometer to be certain that the system 

is leak-free. Walt a minimum of two minutes and lf the pressure has 

decreased less than 1 mm, proceed as described below. If a leak ls 

present, find and correct it before proceeding further. 

Record the vacuum pressure to the nearest 0.1 mm Hg and close off 

the gas bulb stopcock. Open the Tedlar bag valve and allow the system 

to come to atmospheric pressure. Close the bag valve, open the pump 

coarse adjust valve and evacuate the system again. Repeat this 

fill/excavation procedure at least twice and then close off the pump 

coarse adjust valve, open the Tedlar bag valve and let the system fill 

to atmospheric pressure. Open the stopcocks on the gas bulbs and let 

the entire system come to atmospheric pressure. Close the gas bulb 

stopcocks, remove the bulbs and place them on the shaker table with 

their main axis either parallel to or perpendicular to the plane of 

the table top. 

Record the room temperature and the barometric pressure (nearest 

0.1 mm Hg) after each set of gas bulbs is filled. At least one set of 

bulbs from a Tedlar bag containing a known concentration of CO in 

nitrogen must be used each time a set of samples Is shaken. Improved 

accuracy will be obtained lf two standards are Included each time. 

Also, to avoid cross contamination of samples, the bulb filling system 

must be purged with anbient air for several minutes between samples. 

Shake the samples for 25 minutes lf the expected concentration ls 

less than 600 ppm and for 20 minutes lf it ls between 600 and 1,000 

ppm. Place the contents of each bulb in a labeled test tube or other 

suitable vessel. 

Measure the absorbance of each sample at 589 nm using water as 

the reference; also measure the absorbance of the unreacted 

colorimetric reagent used for that set of samples to serve as a 

reagent blank. Reject the analysis if the blank absorbance is greater 

than 0.1. 

The absorbance curve is linear to an absorbance of 1.8. If the 

sample absorbance exceeds this, the sample can be diluted with the 

colorimetric reagent. 

86 
P.3 

The reaction between CO and the colorimetric solution is slow. 

For example, unshaken samples set aside for one hour after filling 

show no significant absorbance. 

8.0 CALIBRATION AND QUALITY ASSURANCE 

8.1 Gas Bulb Calibration 

Weigh the empty bulb to the nearest 0.1 gram. Fill the bulb with 

distilled water and again weigh to the nearest 0.1 gram. Subtract the 

tare weight and calculate the volume in liters to three significant 

figures using the density of water (st the measurement temperature). 

Record the volume on the bulb or, alternately, etch an identification 

number on the bulb and record the volume ln a notebook. 

8.2 Rate Meter Calibration 

Assemble the system as shown in Figure E-1 (the impingers may be 

removed) and attach a volune meter to the probe inlet. Set the rotameter at 300 mL/min, record the volune on the volune meter, start the 

pump and pull gas through the system for 10 minutes. Record the final 

volume on the volune meter and determine the volune of gas that passed 

through the system. Repeat this procedure for at least two other flow 

rates between 100 and 500 mL/min and prepare a calibration curve for 

the rate meter. 

8.3 Spectrophotometer Calibration 

The calibration curve is established for each batch of samples 

shaken at the same time by running standards along with the stack 

samples. For highest accuracy two sets of standards should be run, 

but acceptable results have been obtained when only one set of 

standards was used per batch of samples. 

8.4 Quality Assurance 

8.4.1 System Shaking Time 

Before field samples are analyzed, the linearity of the 

absorption curve as a function of shaking time must be established for 

the analytical system. This can be accomplished as follows: Fill a 

Tedlar bag with a CO concentration at least as high as the highest 

level expected to be encountered in the field samples. Fill at least 

six gas bulbs with gas from the bag as described in Section 7.3 and 

set them on a shaker. After shaking has been initiated remove two 

bulbs at 15 minutes, two at 30 minutes and two at 60 minutes and 

measure the absorbance of each solution. Calculate the absorbance per 

87 
P.4 

volume of gas (SA) according to Equation E-1 (Section 9.2) for each 

sample and determine the average SA for all samples with Identical 

shaking times. Plot this average SA versus the shaking time to 

determine the linearity of the absorption curve. Use this data to 

determine the shaking time and sample volume required for sample 

analysis. 

6.4.2 Sample Bag-Leak Checks 

While a bag-leak check is required subsequent to bag use, it 

should also be done before the bag is used for sample collection. The 

bag should be leak-checked In the Inflated and deflated condition 

according to the following procedures. Connect the bag to a water 

manometer and pressurize the bag to 5 to 10 cm H-0 (2 to 4 inches 

H^O). Allow the bag to stand for 60 minutes. Any displacement in the 

water manometer indicates a leak. Now evacuate the bag with a 

leakless punp that is connected on the downstream side to a flow 

indicating device such as a 0 to 100 mL/min rotameter or an impinger 

containing water. When the bag is completely evacuated, no flow 

should be evident lf the bag Is leakless. 

9.0 CALCULATIONS 

9.1 Abbreviations and Symbols 

SA c Sample absorbance per volune of gas ln bulb 

C0B r Concentration of CO in Tedlar bag (ppm, dry basis) 

CO- . « Concentration of CO in stack (ppm, dry basis) 

FC0_ « Volune fraction of C0_ ln stack 

By s Moisture content of gas ln bag 

9.2 Calculation of CO 

9.2.1 Calculation of SA 

Calculate the sample absorbance per volume of gas (SA) for each 

gas bulb (Equation E-1) and record the value In Table E-1. Calculate 

the average SA for each bag sample and compare the three vslues to the 

average. If any single value differs by more than 10 percent from the 

average, reject this value and calculate a new average using the two 

remaining values. 

(E-1) 

ci • I Sample Absorbance Corrected for Blank! J Barometric Pressure 1 

I Bulb Volume - Volume Reagent J [Sample Pressure in Bulb J 

88. 
P.5 

9.2.2 Calculation of CO Concentration in Bag 

9.2.2.1 Single Standard Shaken with Samples 

Calculate the CO concentration ln the bag using Equations E-2 

and E-3. If condensate is visible in the Tedlar bag, calculate B 

using Table E-1 and the temperature and barometric pressure in the 

room where the analysis was done. If condensate Is not visible, 

calculate B using the temperature and barometric pressure at the 

sampling site. 

_ . m Vapor pressure of water ln bag ,_ -. 

v Barometric pressure 

C0_ Bag [ppm CO in stdI I Average SA sample ,_ -* 

1-Bw J Average SA std

 l ; 

9.2.2.2 Two Sets of Standards Shaken with Samples 

Construct a graph of concentration versus the average SA for 

each standard forcing the curve through the origin. Determine the CO 

concentration in each Tedlar bag stack sample using the average SA for 

each sample and correct for the amount of moisture present (B ). 

9.2.3 Calculation of Stack CO (dry basis) 

Calculate the CO in the stack using Equation E-4. 

C0Stack ' C0Bag (1-FC02> <E"*> 

10.0 BIBLIOGRAPHY 

Lambert, J.L., and R.E. Welns. Induced Colorimetric 

Method for Carbon Monoxide. Anal. Chem., 46: 929-930, 

1974. 

89 
P.6 

TABLE E-1 . 

TEMPERATURE 

(

6C) 

4 

6 

8 

10 

12 

14 

16 

18 

~ 2 0 

22 

24 

26 

28 

30 

MOISTURE CORRECTION 

VAPOR PRESURE 

H2 0 (mm Hg) 

6.1 

7.0 

8.0 

9.2 

10.5 

12.0 

13.6 

15.5 

17.5 

19.8 

22.4 

25.2 

28.3 

31.8 

90 

J 
GLASS WOOL 

FILTER 

AMBIENT 

TEMPERATURE 

BATH 

QUICK DISCONNECT 

—- VALVE ON BAG 

FIGURE E-1 . CO SAMPLING TRAIN 

TJ 

^1 
P.8 

DIMENSIONS IN cm) 

1.9 

FICURE E-2. CAS REACTION BULB (0.1 liter) 

'92 
P.9 

FIGURE E-3. ADAPTOR FOR HOLDING GAS BULBS ON SHAKER TABLE 

93 
•ULB SHUTOFF VALVES 

SAMPLE IULBS 

FINE ADJUST COARSE ADJUST 

VALVE^ f VflLVE 

—" VENT 

BAG SHUTOFF VALVE 

'A*\ VACUUM 

PUMP 

TEDLAR 

SAMPLE BAG 

FICURE E-4. CAS BULB FILLING SYSTEM 

.O 
PJ1 

' O l> J 

' m9 Oi Q i <z a 

Q 

so 

©9 

3

bi ca a 

6 5 a 

? ** u 

Ck c^ sn w 

o 

2 

CM 

0 

ca 

cJ 

r 

m 

I 

~ 

I jfco 

6J o 

1$ si I o 

ca I c=» 

a s 

o95 

-Ji 
P.12 

APPENDIX F 

INSTRUMENT EVALUATION HISTORY 

1/4/80 

1/22/80 

2/2/80 

2/4/80 

3/10/80 

3/31/80 

4/2/80 

4/3/80 

4/10/80 

4/16-4/17/80 

4/21/80 

4/25/80 

6/9/80 

7/3/80 

9/18/80 

11/10-11/12/80 

ECOLYZER 3107 

10/18/79 

4/16-4/17/80 

4/21/80 

4/27/80 

4/28/80 

APPLIED AUTOMATION OPTICHROM 10 2 

Instrument received vith no Instruction 

manual. 

Instruction manual received, started wiring 

Instrument. 

Power supply failed. 

New power supply failed. 

Incorrect output found (overloaded). Power 

supply failed. 

Serviceman from Applied Automation arrived to 

repair instrument. 

Instrument repaired, power supply, output 

board and temperature controller replaced. 

Output is negative. 

Output problem fixed by reversing wiring to 

output board and by moving a resistor on it to 

another position. 

Transported to refinery in trailer . 

Instrument turned back on. 

Fuse blew in heater circuit. 

Zero response varying badly. 

Negative peak before CO peak on chromatogram 

detected. Chromatograms sent to manufacturer 

as aid ln troubleshooting. 

Condensation in FID caused corrosion to internal parts. Monitor shut off until manufacturer's service representative call . 

Applied Automation serviceman tried to repair 

monitor - was unsuccessful. Monitor shut 

down. 

Instrument received. Checked out. 

blems found in laboratory checkout. 

Transported to refinery in trailer . 

Instrument turned on. 

Model 2949 filte r failed. Replaced. 

Model 2949 filte r failed. Replaced. 

No pro96 
P.13 

5/3/80 

5/80 

9/18/81 

1/17/81 

2/17/81 

ANARAD 501-R 

10/2/79 

4/16-4/17/80 

4/21/80 

MSA LIRA 202 

Model 2949 filte r failed. Replaced. 

Large carbon filte r added to monitor sample 

line (replaces Model 2949 filter ) to extend 

operation time. 

Electrochemical cell going bad. Span control 

was unable to span monitor. 

New electrochemical cell installed, monitor 

zeroed and spanned. 

Model 2949 filte r failur e caused 

electrochemical cell to fall . Monitor removed 

from evaluation. 

Instrument received and checked out in laboratory without problems. 

Transported to refinery in trailer . 

Instrument started up. No problems or outages 

occurred before testing was completed in 

April 1981. 

11/2/80 

1/14/80 

2/27/80 

3/3/80 

3/4/80 

3/11/80 

3/10-4/3/80 

4/15/80 

4/16-4/17/80 

4/21/80 

4/21-5/1/80 

Instrument not operational as received. 

Put into operation. 

Apparent failure of output board. Output had 

worked previously (on PD-2064) but output now 

less than 4 mA. Called MSA. New output board 

ordered. 

New output board arrived, installed. Output 

still not correct; MSA suggested checking 

output by voltage drop across a resistor. 

Output seemed to be okay by this method, but 

power supply board failed soon after test. 

Ordered new power supply. MSA suggested that 

output problem could be solved by installing a 

matching circuit between the MSA instrument 

and the data logger. 

Power supply board arrived. 

Electronics expert, R. Burdine, made several 

visits to ascertain output problem and built a 

circuit to correct problem. His conclusion 

was that such a circuit was not needed, but 

that output board was bad (again). New board 

ordered. 

New board arrived, not tested (trailer packed 

for moving). 

Transported to refinery in trailer. 

Instrument started up. Output still bad. 

Instrument off. MSA contacted from Auburn. 

97 
P.M 

5/1/80 

5/2/80 

5/3-5/20 

6/9/80 

6/9-6/16/80 

9/18/80 

TELEDYNE 611 DMCO-20X 

2/80 

3/13/80 

4/16-4/17/80 

4/21/80 

4/29/80 

5/1/80 

5/7/80 

9/18/80 

11/2/80 

BENDIX 7770 

1/3/80 

2/14/80 

D. Tlskiewlc of MSA came to check problem. 

According to his meter, output was 4-20 mA. 

Mr. Tlskiewlc said that matching circuit was 

needed. MSA-Pittsburgh would find and send 

one. 

Instrument off. No work on matching circuit. 

Matching circuit received and installed by 

MSA serviceman. 

Lab evaluation completed in field. 

Span and zero adjustment not possible. Complete optical alignment restored performance. 

Instrument continued to operate normally 

throughout the remaining part of the evaluation. 

Instrument received with no instructions on 

how to Install or use molecular sieve canisters. 

Initial setup and adjustment. Dimensional 

instability noted: very sensitive to even the 

slightest change of attitude with respect to 

horizontal - even microscopic changes significant. 

Transported to refinery in trailer. 

Instrument turned on and interference in fuel 

gas noted. 

Molecular sieve Installed on sample line. No 

effect on sample concentration. Impossible to 

zero and span instrument. 

Molecular sieve removed. 

2-hour drift RA Test spoiled by very high 

sample concentration. Instrument readout did 

not change before, during or after period of 

high concentration. 

Monitor shut off due to lack of reliable data 

caused by interference. 

Molecular sieve received from Teledyne. When 

installed, no startup was possible because of 

optical system failure. 

Instrument received. 

Connections to gas services made, instrument 

started up. Several tube fittings inside 

leaked and had to be tightened. Initial 

adjustment made (oven temp, flows, etc.). 

.98 
P.15 

3/11/80 

3/21/80 

4/1/80 

4/16-4/17/80 

4/21/80 

5/7/80 

11/5/80 

12/15/80 

2/25/81 

Internal plumbing modified to accept separate 

sources for valve and heater air. Vhen 

instrument was restarted, oven heater was 

inadvertently shorted causing destruction of 

TRIAC ln heater control circuit. New TRIACs 

ordered. 

Parts arrived but proved to be wrong. Correct 

parts ordered. 

Correct parts received, installed successfully. Instrument restarted. 

Transported to refinery ih trailer. 

Instrument started back up. 

2-hour drift RA Test spoiled due to high H-S. 

Instrusent system recovered from high H.S in 

about 4 hours. * 

Monitor failure from 2 weeks previous caused 

by diaphragm on sample valve. New part 

ordered. 

Diaphragm replaced. Monitor operating properly. 

Sample valve diaphragm ruptured and repaired. 

Instrument operated properly throughout the 

remaining field evaluation. 

DEL MAR SCIENTIFIC EM-W 

2/10/80 

4/16-4/17/80 

4/21/80 

5/7/80 

Monitor received and set-up. 

Transported to refinery in trailer . 

Instrument turned on. Pressure/flow problems 

noted. Sensitivity critically dependent on 

flow (which varie s with pressure and gas 

viscosity). 

Very high H.S concentration encountered in 

fuel gas at 10:00 am. Analyzer did not re -

cover until next day. Instrument operated 

properly throughout study, but gas dilution 

system was not- appropriate for fuel gas 

dilution. 

HOUSTON ATLAS 825/102R 

12/14/79 

1/20/80 

4/16-4/17/80 

4/21/80 

4/23/80 

Instrunent received. 

Instrunent setup. 

Transported to refinery in trailer. 

Instrument turned on. Output overloads data 

logger. Tape does not advance. Ordered new 

output/cycle time board. 

New board arrived. No effect. Timer relay 

ordered. 

99 

. 
P.16 

4/28/80 

5/1/80 

5/5/80 

5/8/80 

5/8/80 

9/11/80 

9/18/80 

11/2/80 

1/6/81 

3/31/81 

Relay received. No effect. 

Abraham Asperlc of HAI arrived to troubleshoot. Did not find problem. Took analyzer 

back. 

Asperlc Informed us of wiring mistake to data 

logger. Sent instrument back to us. 

Instrument arrived with wiring instructions. 

Instrument turned on - works. 

Monitor sent to manufacturer for repair. 

Monitor returned by manufacturer. 

Houston Atlas serviceman found cause of drift 

to be condensation in vent line. 

Dilution system breakdown. Circuit board installed backwards by contractor personnel. 

New part delivered. 

Monitor failure due to corrosion in timer. 

PROCESS ANALYZERS INCORPORATED 32-230 

12/20/79 

1/80-3/80 

5/9/80 

6/9/80 

8/28/80 

9/18/80 

10/1/80 

11/5/80 

Instrument received. 

Instrument not operational - many circuit 

cards exchanged with manufacturer. Instrument 

eventually returned for repair. 

Monitor returned from manufacturer allowed to 

warm up until next site visit. 

Monitor broken down during 1-month warmup. 

Returned to manufacturer. 

Monitor returned to manufacturer. 

Monitor returned to field test, 4 to 20 mA 

output not functioning. 

Monitor stopped operating. 

Monitor failure caused by wearout of 10 port 

valve. Monitor shut down and removed from 

further testing. 

100 
P.17 

(firfeass mod fnstructioai on the ievant %tfart eotnpletias) 

1. REPORT WO. 3. RECIPIENT'S ACCESSION NO. 

a. TITLE ANO OUDTITLG 

FIELD EVALUATION OF CARBON EPOXIDE AND HYDROGEN 

SULFIDE CONTINUOUS EMISSION KQ242TORS AT AN Oil 

REFINERY 

7. AUTWORI8J 

R. S. Jester and 3. 3. Ferguson (Harsen) 

W. J. Mitchell (EPA) 

3. RCPORT ©ATS 

£. PERFORMING ORGANISATION COOE 

). PERFORMING ORGANIZATION REPORT NO. 

3. PERFORMING ORGANISATION NAME ANO ASDRGBS 

Haraon Engineering and Testing 

3ox 2207 

Auburn Industrial Pa?k 

AuburnD AL SS§10 

h e . PROGRAM GLdMENT MO. 

IfWrSoTdTOAEYTEEANTwo-

(S8-02-S405 

13. SPONSORING AGENCV NAME ANO AOORESS 

Environmental Monitoring Systems Laboratory 

Office of Research ond Developaent 

U.S. Environmental Protection Agency 

Research Triangle Park, NC 27711 

(13. TvPE Of REPORT ANO PERIOD COVERED 

Final 

14. SPONSORING AGENCV COOE 

EPA 600/08 

19. SUPPLEMENTARY WOTdS 

To be published as an ORD Project Repeat 

18. AOSTRACT 

An eleven aonth field evaluation was done on five hydrogen sulfide and four 

carbon monoxide aonitors located at an oil refinery. The hydrogen sulfide aonitors 

sampled a fuel gas feed Sine and the carbon monoxide monitors sampled the emissions 

from a fluid cat cracker (FCC). Two of the four carbon monoxide monitors operated 

over the eleven aonth period and showed good agreement with the Seuco crystal violet 

(LCV) wet chemical aethod developed for the purpose of checking monitor accuracy, 

fhe LCV aethod and the special stack gas conditioning system employed to remove aoisture and particulate from the FCC stack gas are also described. The gas conditioning 

system operated for 14 aonths without a aajor failure. None ef the five hydrogen sulfide aonitors was found acceptable. Two of the five never obtained a valid sample and 

the other three did not agree well with the EPA Reference Method 11 during relative 

accuracy testing. 

k KEV WORDS AND DOCUMENT ANALYSIS 

DESCRIPTORS b.lOENTlf IERS/OPEN ENDED TERMS C. COSATl Field/Croup 

Stack gas conditioning systea 

Carbon aonoxide aonitors 

Hydrogen sulfide aonitors 

Fuel gas feed liae 

Carbon sonoxide wet cheaical oethod 

Leuco crystal violet 

EPA Method 111 

JEffi 

10. DISTRIBUTION STATEMENT 

RELEASE TO PUBLIC 

16. SECURITY CLASS (Thii Report/ 

UNCLASSIFIED 

20 SECURITY CLASS (Thiipast) 

UNCLASSIFIED 

2 1 . NO. Of PAGES 

33. PRICE 

EPA P» o 2226-1 (Qo*. d-T?) Pnawiouo aoiTiew io ©Do©LQf a 

——**— — „