p.1 

OAR Box 1124 

Prepped by Ollie Stewart 

Document Number: 

60) ll-D-1 

Docket Number: 

A-84-44 

Printed 4/16/2008 8:13:21 AM ' Sheet 60 of 70 
IW 

'k-M-'M P" 

National Cooperative Refinery Association 

2000 SOUTH MAIN ST. • P.O. BOX 1404 • McPHERSON. KANSAS 67460 • 316/241-2340 

/.•'. 

February 21, 1985 

Mr. Jack R. Farmer 

Director, Emission Standards 

and Engineering Division 

U.S. Environmental Protection 

Agency, Office of Air Quality 

Planning and Standards 

Research Triangle Park, NC 27711 

Dear Mr. Farmer: 

This letter is in response to your January 25, 1985 letter requesting information on process equipment and associated emission control equipment subject to the "new source performance standard" 

at our McPherson, Kansas refinery. We understand that you are 

'requesting only information that is available without doing additional tests or studies, so the following responses to the questions have been prepared with that in mind. 

The format of the answers below will be the same as that of the 

questions as received in ENCLOSURE 1 in an effort not to repeat 

the questions and keep the answers as brief as possible. 

I. INTRODUCTION 

No response required. 

II. FACILITY DESCRIPTION 

Fig. I (Dwg. NCRA-F-8278) is a current drawing of our refinery fuel gas system that should be self explanatory. Sweet 

Natural Gas enters on the middle right hand side of the drawing and during this time of the year the flow rate is approximately 8 MM SCFD and is distributed as shown on the drawing. 

The flow of propane, shown entering the middle bottom of the 

drawing, is normally zero and is used only if we are unable 

to get natural gas. The refinery fuel gases are the Cat, 

Coker and Saturates Sponge Absorber gases and are shown entering the drawing in the lower left hand area. The gases 

are sour, containing approximately 2.8 mole % of H-S, and 

are sent to the High Pressure Amine absorber where all but 

50 mole ppm of the H_S is removed before the gases flow to 

the two fuel drums for distribution to the various users 

throughout the refinery. All gases that do not go direct 

to a user are blended in the Plant Fuel Drum (W-086) except 

for the 2.7 MM SCFD of gas from the Fuel Drum and 3.7 MM 

SCFD of Natural Gas that are blended in the line going to 

Snnnlvlr.a Refined Fuels FARMLAND INDUSTRIES. INC.. KANSAS CITY. MISSOURI • FARMERS UNION CENTRAL EXCHANGE. INC.. ICENEXI. SAINT PAUL. MINNES01 
P.3 

Mr. Jack R. Farmer 

February 21, 1985 

Page 2 

the FPU Heaters. The blended fuel gas in the Fuel Drum then 

exits the drum at several locations for distribution to the 

many users throughout the plant. 

Fig. II (Dwg. D-914-C621) is a process flow diagram of our 

Diesel Hydrotreating Unit that contains one of our NSPS heaters. 

Fig. Ill (Dwg. D-914-N634) is a process flow diagram of our 

Coking Unit which contains our other two NSPS heaters. 

Fig. IV is a sketch showing the many streams entering and 

leaving the Amine Unit and was the basis for the design of 

the unit. An overall sulfur balance is in the upper right 

hand corner of the drawing but flow rates and sulfur concentrations are noted on each stream. 

Fig. V is a Process Flow Diagram of the Amine Unit and contains much of the same information that is shown on Fig. 

IV, however, if there are any discrepancies Fig. V should 

be correct as it is the official design. Also noted on Fig. 

V, in red, are some typical operating flow rates which show 

that we are operating at about 75% of design. 

III. COSTS 

1. Our Amine Unit is a new unit built during 1983 and 1984 

at a cost of $4.98 MM and put onstream during June of 

1984. This $4.98 MM includes all materials and labor 

up to the time the unit was put into operation but does 

not include the initial chemical inventory. 

A breakdown of costs are as follows: 

a. Purchase Cost of Unit r 

1. All equipment and labor - $4,980,000. 

2. Initial chemical inventory - $25,500. 

b. Installation Cost 

1. Included in above. 

2. Not available. 

Annual Operating Costs 

1. Labor costs = $285,000/year including overhead 

7,125 hours at $40/hour. 
P.4 

Mr. Jack R. Farmer 

February 21, 1985 

Page 3 

d. 

2. Materials 

a. Not available - new unit. 

b. Chemicals - 5,000 gallons - $2.85/gallon. 

3. Steam - 11,000 Lbs/Hr, 55 psig, 300°F, 

$3.10/1,000 Lbs. 

1,500 Lbs/Hr, 225 psig, 400°F, 

$4.40/1,000 Lbs. 

4. Electricity = $120,000/Yr. 

5. Water - Not available. 

6. No direct fuel usage. 

7. Sulfur - $325,000/Yr. 

Key Accounting Factors 

1. Leased asset - no lifetime established. 

2. Leased asset - none established. 

3. Labor - $13.50/Hr., Management - included in #4 

below. 

4. $26.50/Hr. 

IV. REFINERY COMBUSTION DEVICES 

1. We have 36 combustion sources. 

2. Process Heaters Boilers Compressors Flares 

a. Size— 

MM BTU/Hr. Input 

b. Costs— 

Capital 

Operating MM$/Yr. 

c. Operation— 

Days/Year 

d. Other Fuels 

5 to 70 -- 50 to 150 3 to S 1 to 3 -

NA NA NA NA 

0.1-2.1 1.5-4.5 0.1-0.3 .03-.09 

350 350 350 350 

C3, Slurry C3, Slurry None None 
P.5 

Mr. Jack R. Farmer 

February 21, 1985 

Page 4 

3. NCRA has three new process heaters that are subject to 

NSPS. They are as follows: Two new Coking Heaters, 

HF-009A and HF-009B, rated 66 MM BTU/Hr. input each that 

were completed in 1983. One new Diesel Hydrotreater 

Heater, HP-012, rated 27 MM BTU/Hr. input that was completed in 1984. We complied with the NSPS by building 

an Amine Unit that removes the H2S from the fuel gas 

and by causing an Ammonium Thiosulfate plant to be built, 

across the fence, to take the H2S we generated and turn 

it into Ammonium Thiosulfate fertilizer. The H-S content of the fuel gas decreased from the former 2.0 Mole 

% H~S to the present 50 Mole ppm H2S which is a reduction of 99.75%. I would say that the cost of compliance 

was the cost of the Amine Unit which is stated above. 

a. No - built new Amine Unit. 

b. Yes - new Amine Treater. 

4. 

5. 

c. 

d. 

e. 

f. 

I 

No. 

No. 

No. 

No. 

don't know 

None. 

V. PRIMARY CONTROL (AMINE TREATERS) \ 

1. a. 17.5 MM SCFD. 

b. 880 Net - 972 Gross BTU/SCF. 

c. 100°F - 150 psig. 

d. 86.8% H2S, 12.5% C02, 0.6% N2, 0.1% CH4, 0.1% C2Hg, 

2. We only have one Amine Treater. 

a. See Fig. IV and Fig. V enclosed. 

b. Designed and built by Ford, Bacon & Davis. 

c. June 6, 1984. 

d. Design - 39.4 long tons per day, Range - 7 to 39.4 

long tons per day. 
P.6 

«. Mr. Jack R. Farmer 

February 21, 1985 

Page 5 

3. 

4. 

e. 

f. 

g. 

h. 

i. 

jk. 

8,400 hours per year. 

See Fig. V. 

30,000 gallons of 20% MEA, 

See Fig. V. 

See Fig. V. 

MEA. 

None. 

Probably none. 

The unit was only been onstrea 

5, 

6, 

7. 

8. 

been no major outages since start-up. The biggest problems to date have been freeze-ups going through the first 

winter and some foaming problems due to improper reclaimer operation. 

a. Yes, some - Amine usage 13.5 gallons per day. 

b. Still a problem but continuous anti-foam injection keeps the foam under control. 

c. Probably causing the foaming. 

d. Very minimal. 

e. None. 

No. 

Excellent for 8 months. 

UOP will inspect every two years during turnarounds. 

H_S concentrations in sweet gas from the absorbers, H2S 

and CO- loadings in the lean and rich amine streams, 

amine strength, and heat stable salts in the lean Amine. 

Low H2S concentrations in the outlet sweet gas have never 

been 5 problem to date. 

VI. SECONDARY CONTROL (SULFUR PLANTS, ETC.) 

1. The Acid Gas stream exiting the amine treater is sold 

to Kerley Industries who operates a thiosulfate plant 

and make Ammonium Thiosulfate Fertilizer. This plant 
P.7 

*>" Mr, Jack R. Farmer 

February 21, 1985 

Page 6 

was designed and built by others during 1983 and 1984 

and was started up June 6, 1984. It is designed to 

handle all of the Acid Gas we make and send to them. 

2. Owned by others and does not use amine scrubbing. 

VII. EMISSION TESTING 

1. A copy of the EPA PSD permit performance test is enclosed as Fig. VI and consists of 16 pages that should 

answer the questions presented. 

a. Approximately $6,000 including NO testing. 

b. No, by Total Source Analysis Inc. 

c. None. 

d. See Fig. Ill for the location of the sample point, 

which is on the fuel gas line to the Coking Heaters 

and is downstream of the Plant Fuel Drum, where some 

Natural Gas is blended with the refinery fuel gas. 

On that day 575 MSCFD of Natural Gas was blended 

with 14,796 MSCFD of refinery fuel gas to make the 

blend going to the Coking Heaters. 

NO testing was also performed during the same test period" and all those results are also "included in Fig. VI. 

You will note that one of the Coker Heaters did not meet 

the required NO concentrations so modifications are 

currently being made and another test has been scheduled 

in the near future. 

3. No. 

VIII. MONITORING OF EMISSIONS AND PROCESS OPERATION 

1. No response required. 

2. None. 

3. We monitor the H2S concentration at the outlet of 

the High Pressure Amine Absorber with periodic grab 

samples for our own purposes to ensure that the 

amine treater is operating properly and to ensure 

that we are in compliance with the NSPS. 

We sample once per week with a Draeger Tube unless 

operations are changed or an upset occurs and the 

need for more frequent samples is demonstrated. 

The cost is very minimal, $5 to $10 per sample, the 

accuracy is plus or minus 10%, and the only problems are frosting up of the Draeger Tube when 
P.8 

Mr. Jack R. Farmer 

February 21, 1985 

Page 7 

running a liquid propane or butane sample. This 

problem was alleviated by installing a small sample 

vaporizer. 

c. None are used. 

1. No response required. 

2. No response required. 

3. No response required. 

4. No response required. 

5. No response required. 

4. Monitoring of Process Parameters 

a. None. 

b. None. 

5. No. 

6. Don't have any instrument monitors. 

IX. GENERAL REFINERY INFORMATION 

1. The nominal size of our refinery is 70,000 BPCD and, 

except for January and February of 1985, we have been 

operating at the 70,000 BPSD level. Our current operating schedule is to run continuously, except for a four 

week major turnaround on odd numbered years and a 5 day 

Crude/Coking Unit turnaround on even numbered years. 

The quantity and sulfur content of the Sour Crude that 

we run has the largest effect on the aminestreaters. 

2. The typical wt. % sulfur in our sweet crude is 0.4% with 

a range of 0.35% to 0.45%. The typical wt. % sulfur in 

our sour crude is 1.8% with a range of 1.4% to 3.0%. • 

The higher the level of sulfur- in the crude the more 

amine we must circulate to maintain reasonable loadings 

of H_S in the rich amine and this, in turn, causes the 

heat load on the amine regenerator reboilers to be increased to maintain good stripping of the H2S from the 

lean amine. To date we see no increase in the H2S content of the.fuel gas because of more sulfur in tne crude 

oil. 

3. When we are processing sour crude some of the distillate 

streams must be desulfurized to meet sulfur specifications and amine unit costs increase directly by the 

amount of sulfur that is removed. 
P.9 

Mr. Jack R, Farmer 

February 21, 1985 

Page 8 

4. Natural Gas is blended into the refinery fuel gas system for only one reason and that being to maintain pressure on the fuel drum so there is an adequate supply of 

fuel to maintain operations. No blending is done to 

dilute H2S concentrations because the H2S concentration 

in the fuel gas leaving the amine treater is well below 

the allowable H2S concentration and can be used as fuel 

directly. 

X. GENERAL REGULATORY INFORMATION 

1. Very little, none, minimal. 

2. None. 

3. Negligible, no routine report is reguired. 

XI. CONTACTS FOR FURTHER INFORMATION 

National Cooperative Refinery Association 

H.W. Davidson, Process Engineer 

P.O. Box 1404 

McPherson, KS 67460 

Sincerely, 

NATIONAL COOPERATIVE REFINERY ASSOCIATION 

E.C. Ewing ( 

Technical Director 

/alu 

Attachments 
Jr 

P.10 

SECTION I 

INTRODUCTION 

An EPA PSD permit performance test was conducted on October 17 

and 18, 1984 at the NCRA refinery in McPherson, Kansas. NO 

performance tests for HF-009A and HF-009B were performed simultaneously on October 17, 1984 from approximately 9:30 A.M. to 

1:00 P.M. Fuel gas performance tests for SO determination were 

performed October 17, 1984 from approximately 2:00 P.M. to 8:00 

P.M. NO performance tests for HP-012 were performed October 18, 

1984 from approximately 11:30 A.M. to 2:30 P.M. All tests were 

performed in compliance with EPA standards determined at the 

pretest meeting of July 17, 1984. The following people were . 

- V 

present for the performance tests: 

John Hosman USEPA, Region VII KC, KS 

John Giar USEPA, Region VII KC, KS 

Carl Vineyard TSA, Tester Amherst, Ohio 

Bruce Woods TSA, Tester Amherst, Ohio 

Ken Sims NCRA, Process Engr. McPherson, KS 

NCRA's operation was normal for both test days with~.no upsets 

encountered. Total crude charge was approximately 70,OCH) BPD 

with 15,000 BPD to the new crude unit and 55,000 BPD to the old 

crude unit. Total reduced crude charge to HF-009A and HF-009B 

was approximately 19,000 BPD, with 4,000 BPD from the new crude 

unit and 15,000 BPD from the old crude unit. 
P.11 

INTRODUCTION 

This report presents the results of the NOx Emissions Tests 

and the H2S Fuel Gas Composition Test performed on Heaters 

HF-009A, HF-009B and HP-012 of NCRA's McPhearson, Kansas 

Refinery. 

The purpose of the tests was to determine the compliance of 

the units. The results of the tests can be found in Section 

II of this report. 

The emissions testing was performed by Total Source Analysis, 

Inc., whose main office is located at 4640 Telegraph Rd., 

Amherst, Ohio 44001. 

The tests were performed on October 17 and 18, 1984. The 

testing was performed in accordance with EPA reference 

methods as published in the July 1, 1983 Federal Register, 40 

CFR, Part 60, Appendix A -"Standards of Performance for New 

Stationary Sources" and subsequent revisions. 

The testing equipment, sampling procedures and analytical 

procedures are described in Section III of this report. The 

raw field data, plant data, equipment calibrations, lab 

enalysis reports and equations used in determining final 

results are presented in the Appendix. 
TABLE II . H2S RESULTS 

P.12 

t 

'+ 

I 

Run No. Dat e 

1 

2 

* 5 

6 

7 

prs/dsc f PPM 

10-17-8 4 

10-18-8 4 

.011 4 H\ 

.0085 \<\$ 

.0093 3./, 3 

.0050 ||.4 

.005 4 jjj^ v 

•Runs 3 and 4 were discarded due to negative concentration 

values. 

18.5 

13.8 

15.1 

8.1 

8.8 

The complete results can be found on the computer printouts 

following. 
Ity*-4 of 4 

P.13 

Client 

HYDROGEN SULFIDE CONCENTRATION 

/i/aZA <ZSV 

Project No g?4^~~^5~<-^ 

Plant Site _ 

Analysis Run By _ 

~" «oo f b 

CH2S = 0.263 

H^S (ppm) = 1.62x10* (CH2S) 

[VIT Nl - VTT NT sample -^/I T Nl - VTT NT blankj 

VmSTD 

Sampling 

Location 

Run 

No. VIT Nl VTT NT Vm(STO) 

Cone. 

H2S 

ppm 

H2S 

A 1 S'O ooq*? ^7,'7 jOJOl /sb^V^ tr>tM te,6 

/Q-iZ 

-2-

Go L-CZDSS- W'tt tO/Vl WK A//A 

£CL ,ndia

( **&*> ,o/oj AS2. 

/u/A 

DO<P>£ >?>,& 

V £L ^o ,C&\°\ y&.u .oia/ ,<&& tOO°i 3 AS",/ 

/*-/ & A ro ropq^? -ygio o/O / A7J7 oog'ci ST . I 

JL _X^. .Og

T? ^9,<? .n/oj *HSfl tpo&q jg^B 

-£U ^2^ . -^o ^ *?•<=» /D/g>/ /^L /^b_ Mt 
:H-»NNE"_ NO : S 

?SAK TIM E 

NO •> 

1 

^ 

3 

4 

5 

6 

T 

9 

9 

13 

: i*-

12 

-M3 

- M4 

15 

16 

17 

lMIN> 

1 . 197 

2.318 

3.289 

5. 156 

5.742 

6.579 

12.994 

17.090 

18.099 

20.420 

21 '. •!• 3 f 

24.459 

25.276 

26.466 

27.645 

31.208 

34.643 

PEAK 

NAME 

HYDROGEN 

ETHYLENE 

ETHANE 

OXYGEN 

NITROGEN 

METHANE 

C5=.CS + 

PROPANE 

PROPYLENE 

IS0-C4 

'Ji — -1 .-

1-BUTENE 

I SO-BUTYL 

T-BUTEN-2 

C-BUTEN-2 

IS0-C5 

N-C5 

= TOTALS = 

CHEM GROUPS: 

3UTYLENES 

HYDROCARBONS 

lUNIDEl CITIFIED 

RESPONSE 

MOL-'< 

40.455 

4.522 

15.393 

.030 

2.544 

32.02 3 

. 103 

t .376 

2.334 

.419 

. tT 5 

. 132 

. 170 

. 129 

.393 

.05 7 

• Ql I 

93.999 

.528 

56.97 1 

0.030 

SP 

GS-VlTj-

.323 

.344 

. 160 

.303 

.025 

. 177 

.033 

.021 

.030 

.308 

. Od j 

.003 

.033 

.003 

.002 

.001 

.000 

.513 

«S 

.010 

.465 

0.000 

NET 

BTU 

I 13.846 

6

7.736 

249.03 4 

3 . 033 

3. 003 

29 I . 123 

4.511 

3 1 .353 

45.737 

12.550 

i 3 . 45 r 

3.331 

4.3 49 

3.733 

2.833 

2.110 

.431 

844.572 

NORMAL I 2 

T * * 

15. 156" 

733.720 

0.030 

GROSS 

BTU 

13 1 .074 

72.339 

2"?2.273 . 

3.030 

3.033 

323.338 

4.711 

3*.628 

43.863 

13.632 • 

; > . 5 IS4.067 

5.131 

3.963 

. 2.939 

2.232 

.434 

334.3 34 

ING SUrV. 

16.220 

833.320 

0.030 

AREA 

COUNT 

233534 

19 136 5 

699353 

83 3 

88320 

3599 12 

8136 

73633 ' 

1 15369 

28J41 

Zt w Z «' i 

8?ll 

10336 

36?8 

6841 

4395 

779 

2530300 

6899360*: 

.-- • . *•'-« ' 

> . 

DETECTED PEAKS: 20 REJECTED PEAKS: 

ERRORS: 0 INSTRUMENT CONDITIONS: 0 

UNIDENTIFIED PEAK FACTORS -- RESPONSE MOL-SS = 0 SP GRAVITY = 0 

NET BTU = 0 GROSS BTU = 0 GROUP = 9 

FILE: T309 

TITLE: PT=PEAK-1 

CHANNEL NO: 3 

PEAK TABLE: PEAK-1 

SAMPLE: DHTHTRFULGA3 

TIME: 13:47 

METHOD: CARLEABS 

DATE: 292:1984 

lo-i8-e«{ 

S EAX 

NO 

1 

2 

3 

4 

5 

6 

7 

8 

9 

10 

1 1 

12 

13 

14 

TIME 

(MIN) 

2.263 

3.555 

5. 184 

5.744 

6.358 

6.494 

8.398 

8.626 

13.025 

17.27 2 

20.727 

22.412 

3 1 .842* 

35.585 

PEAK 

NAME 

C02 

ETHANE 

OXYGEN 

NITROGEN 

METHANE 

CO 

C5=.C6+ 

PROPANE 

IS0-C4 

N-C4 

IS0-C5 

N-C5 

= TOTALS = 

CHEM GROUPS: 

BUTYLENES 

HYDROCARBONS 

UNIDI INTIFIED 

RESPONSE 

MOL-St 

. 100 

5.829 

.038 

10.393 

0. 000 

8 1.099 

0.000 

.027 

. 133 

1.823 

. 164 

.310 

.066 

.018 

100.000 

_ — . . 

0.003 

89.442 

0.000 

SP 

GRAVITY 

.002 

.06 1 

.000 

. 101 

0. 000 

.449 

0.000 

.000 

.004 

.028 

.003 

.006 

.002 

. 000 

.656 

<0; — 

0.000 

.553 

0.000 

NET 

BTU 

0. 000 

94.301 

0. 000 

0.000 

0. 000 

737.271 

0. 030 

0. 000 

5.996 

42.225 

4.915 

9.323 

~~ 2.423 

.682 

397. 142 

NORMAL I 

0. 030 

897.150 

0. 030 

GROSS 

BTU 

0.000 

103.133 

0.030 . 

0.000 

0.030 

81.8.356 

X &•. 00 0 

.038 

6.262 

45.897 

5.328 

10.108 

2 .62 1 

.737 

993.000 

ZING SUM: 

• - •- -

0.030 

992.923 

0.000 

AREA 

COUNT 

3870 

251 142 

1080 

341946 

996 

230361O 

15V8 

536 

10248 

98824 

• 10446 

20257 

4458 

1255 

3050300 

653769K 

t 

*7\ • 

1|1 DETECTED PEAKS: 

E-RGRS: 0 

J.l :i'ErlT I r IED 

28 REJECTED PEAKS: 14 

INSTRUMENT CONDITI ON:: 0 

FnCTOPS -- ?ES;> 3M3I iV_-\ = 0 

^1l MET STj • i - ^ n 

SP G9M7 ! T :• = 3 
SECTION II 

PROCESS INFORMATION IN SUPPORT OF 

FUEL GAS PERFORMANCE TEST 

FUEL GAS PERFORMANCE REPORT 

Date: 

Start: 

Finish: 

10-17-84 

2:00 P.M 

8:00 P.M 

Sour Gasses to Amine Unit: 

Cat Sec Absorber Gas 

Flow Rate, Units 

Flow Factor, SCFD 

Flow Rate, SCFD 

Net Heating Value, BTU/SCF 

Flow Rate, MMBTU/HR 

Coker Sec Absorber Gas 

Flow Rate, Units 

Flow Factor, SCFD 

Flow Rate, SCFD 

Net Heating Value, BTU/SCF 

Flow Rate MMBTU/HR 

S.R. Sec Absorber Gas 

Flow Rate, Units 

Flow Factor, SCFD 

Flow Rate, SCFD 

Net Heating Value, BTU/SCF 

Flow Rate, MMBTU/HR 

Diesel Hydrotreater Separator Gas 

Flow Rate, Units 

Flow Factor, SCFD 

Flow Rate, SCFD 

Net Heating Value, BTU/SCF 

Flow Rate, MMBTU/HR 

Lean-Amine to Absorber 

Flow Rate, Units 

Flow Factor, BPD 

Flow Rate, BPD 

Absorber Pressure, PSIG 

Lean Amine to Absorber, °F 

Sour.Gas to Absorber, °F 

Rich Amine Level, Pet. 

Acid Gas to SRU 

Flow Rate, Units 

Flow Factor, SCFD 

Flow Rate, SCFD 

Net Heating Value, BTU/SCF 

Flow Rate, MMBTU/HR 

Sweet Gas to Fuel 

Flow Rate, Units 

Flow Factor, SCFD 

Flow Rate, SCFD 

Net Heating Value, BTU/SCF 

Flow Rate, MMBTU/HR 

Amine Concentration = 20.3 Pet. 

5.63 

743,500 

4,185,905 

1025 

17 8,8 

6.6 

686,000 

4,527,600 

1106 

208.6 

5.5 

1,200*, 000 

6,600,000 

602 

165.6 

1.5 

60,000 

90,000 

469 

1,8 

6.5 

600 

3900 

157 

108 

77 

61 

6.76 

94,700 

640,172 

500 

13.3 

6.6 

2,400,000 

15,840,000 

822 

542.5 
P.16 

fit?:. 

TESTING EQUIPMENT - EPA METHOD 7 (NOx) 

A Scientific Glass and Instruments Company NOx Sampler was 

used at the sampling location(s) . The NOx sampling train 

consisted basically of a heated 5 foot effective length 

borosilicate glass probe; a 2 liter borosilicete, round 

bottom, short neck boiling flask with a Pyrex 3-way, T-bore 

stopcock valve; a mercury in glass thermometer; a Dwyer Utube mercury manometer; a Gast oil-sealed vacuum pump; and 

various interconnecting hoses, fittings and valves. 

The U-tube manometer was used to monitor the internal 

pressures in the collection flasks. 

SAMPLING PROCEDURES - EPA METHOD 7 (NOx) 

A NOx sampling train was prepared at the sampling locatian(s) 

in the following manner: 25 milliliters of absorbing 

solution were added to a collection flask. A sufficient 

quantity of the absorbing solution was retained for later use 

in preparing the calibration standards. A 3-way stopcock 

valve was inserted into the collection flask and the valve 

turned to the "purge" position. Glass wool was placed into 

the inlet end of the heated sample probe. The probe was than 

placed into the flue and connected to the collection flask. 

The probe heater was turned on and the probe heated-to 

approxifnatey 250 degrees Fahrenheit. A U-tube mercury 

manometer and a vacuum pump were connected to the outlet of 

tho collection flask with a Teflon tee fitting. The stopcock 

valve and the pump valve were then turned to the "evacuate" 

positions. The collection flask was evacuated to 3 inches of 

mercury absolute pressure or less. As soon aa the flask 

evacuation was completed, tho pump valve was turned off and 

the pump was turned off. A leak—check was then performed on 

the collection flask by observing the manometer for one 

minute to determine if the pressure varied more than .4 inch 

V 
|

 :.<X-;-—. 

Ui-\JX 

of mercury. If the pressure did not vary more than the 

allowable tolerance, the leak-check was considered 

XJ acceptable. 

After the NOx sampling train was assembled, the probe 

temperature stabilized and the collection flask leakchecked, as previously described, the nitrogen oxides (NOx) 

sampling was performed. 

JM •-' . 

tv- As soon as the leak-check was completed, the stopcock valve 

I" and the pump valve were turned to the "purge" positions and 

|L; the pump turned on. After an adequate amount of time for 

;\M purging was completed, the pump valve was turned to the off 

£ position and the stopcock valve was turned to the evacuete 

V position. The difference in the mercury levels in the Utube manometer was then recorded. Immediately after this was 

^ done, the stopcock valve was turned to the sample position 

for approximately 15 seconds permitting the flue gas to enter 

the flask until the pressures in the flask and the sample 

"",' lino attained equalibrium. V • 

P.17 

f ' 

Ife 

» 

'I 

i. 

One point was sampled at the sampling location(s) from one 

sampling port. A total of "thr'ee'tes'

c runs were performed. 

Each test run consisted of four 15-second sampling periods 

The collection flask and 

jT" stopcock valve volume, collection flask temperature and 

barometric pressure wer e recorded on a field test form priorto each 15-second sampling period. 

After the completion of each 15-second sampling period, the 

following procedures were performed: The stopcock valve was 

|,: turned to the "purge" position and the collection flask wans 

I f'" 

1

r.' disconnected from the sampling probe, U-tube manometer and 

£;". vacuum pump. Tho sampling probe was left in the flue with 

|p'- the probe heater on and ready for the next sampling period, 

i " The flask was then shaken by hand for a minimum of 5 minutes. 

I4>: •• 

I I

 c • • 
P.18 

fK *~* 

ll-.'-, 

m:x 

The collection flask was transferred to a protective 

transport case and allowed to set for a minimum of 16 hours 

to stabize. At the end of the 16-hour stabilization period, 

the contents of the flask were shaken by hand for 2 minutes. 

The flask was then connected to an U-tube manometer and the 

pressure differential recorded. The flask temperature and 

the barometric pressurre were also recorded at this time. 

The contents of the flask were transferred to a leak-free 

polypropylene sample bottle. The flask was rinsed twice with 

5 milliliter quanties of deionized, distilled water and the 

rinsings added to the contents in the same bottle. Sodium 

hydroxide (1N) was added to the sample, dropwise, to adjust 

the pH between S and 12 as determined by a pH meter. The 

sample bottle was sealed, appropriately labled and the fluid 

level marked. The bottle was then transported to the 

laboratory. 

lir. 

IKV 

& 

rnaj.i/ 
^•<w jfK*.-r-irtKJWTU T^r; •*'..'VV.).; 

FLUE WALL 

-^•" Vll 

PYREX 

WOOL 

PLUG 

STOPCOCK 

© PURGE 

© EVACUATE 

© SAMPLE 

PROBE 

2000 ml 

FLASK 

rt^a 

THERMOMETER 

(? 

\ ^ SHUTOFF VALVE 

VACUUM PUMP 

MERCURY-FILLED MANOMETER 

m 

Exhibit 

NITROGEN OXIDE 

SAMPLING TRAIN 
P.20 

SUMMARY OF TEST RESULTS 

The following tables present the final results of the NOx 

emissions tests and the H2S tests performed on October 17 and 

18, 1984 at NCRA's McPhearson, Kansas refinery.. 

TABLE I. NOx RESULTS 

Run No. 

1 

2 

3 

AVG. 

Location 

HF-009A 

Date 

10-17-84 

PPM 

115 

130 

109 

118 

lbs/MMBtu 

•• 

.135 

.155 

.128 

. 139 

1 

2 

3 

AVG. 

HF-009B •=• 10-17-84 132 

147 

132 

137 

• .155 

'. \. 175 

.158 

.163 

1 

2 

3 

AVG. . 

HP-012 10-18-84 55 

51 

61 

56 

.065 

.063 

.073 

.067 
P.21 

^xy^y 

>.••'•.'•?•••'; 

Sr: 

«;-M- / TOTAL SOURCE ANALYSIS 

NOX TEST RESULTS 

K"..-:-j,-rfr. -.. 

i^TV ^*•/ ^ :& •-:...- •, . 

'.t;-*'-.-'-' •**'.' 

ICRA^".-.-

fT^'^>5--i?-"-'-

ICPHEARSON, KANSAS 

•i-S-ViTSi" 

14-050 -

JF-009A • *»*«Jr-«..!-- ~ -

**t^?r*^~ .•*. 

lUN-: NUMBER 

i&rir.--r-r •' . • 

"LASK NUMBER 

/OLUME OF FLASK 

[NITIA L TEMPERATURE 

r

INAL' : TEMPERATURE 

'•&££•?%.. •• • . 

INITIA L PRESSURE 

.•£X7.. .-:.'. .W. 7 

"INAL PRESSURE 

VOLUME SAMPLED 

MO'xIi'lN": SAMPLE 

NOX CONCENTRATION 

PAnfs.-PER MILLIO N I tX&gAiy.., 

FACTOR 

£?•?' •'• 

PERCENT 02 

OX^EMISSIONS 

MLS 

OEG. F 

DEG. F 

IN HG 

IN HG 

OSCC 

MICRO G 

LBS/DSCF 

PPM 

0SCF/MM8TU 

% 

LBS/MBTU 

1-A 

27 

2034 

42 

66 

1.3 

27.7 

1774 

341 

1.2E-05 

100 

8335 

3 

0.12 

1-B 

10 

1985 

42 

64 

1.4 

27.7 

1731 

375 

1.4E-05 

.._

 11 7 

8335 

3 

0.14 

1-C 

2 

2043 

42 

58 

1.3 

28.6 

1873 

406 

1.4E-05 

117 _ 

8335 

3 

0.14 

1-D 

12 

1950 

40 

56 

0.9 

26.6 

1689 

413 

1.5E-05 

126 

8335 

2.8 

0.14 
P.22 

JatTH0»/l"l^-»irmiMI»ATIOJ3 ©p MT\ JSt. 

erjLFistj CO:»TEMT op nna. ©AO STREAMS SW 

* S. Principle and eppfica&tfify. a.1 ^Yirart-

?Ie. Kydrosen sulfide (HcS) Is collected from 

a source in a series of midget Impingers and 

absorbed In pK 3.0 cadmium sulfate iCdSO.t 

solution to form cadmium sulfide (ICdS). 

The latter compound Is then measured iodo 

we'.rlcslly. An impinger eonl&inlns hydro* 

sen peroxide Is Included to remove SO» as . 

an inlerferins spiles. This shethod Is & revision of the KjS method originally published 

in the FEDERAL RSCISTER. Volume 39. No. 47„ 

dated Friday. March 8.197<S. 

1.2 JlppIicabiMy. This method is applicable for the. determination of the hydrogen 

sulfide content cf fuel gas streams at petroleum refineries. 

%. Ranye end sensitivity. The Sower Slmlt 

of detection Is approximately 3 ms/m" <9 

ppm). The maximum of the range is "340 

xng/m" (520 ppm). 

S. interferences. Any compound that reduces Iodine or oxidizes Iodide lon will interfere Ln this procedure, provide- It Is collected 

in the cadmium sulfate impingers. Sulfur 

dioxide In concentrations of up to 2.600 tns/ 

m" Is eliminated by the hydrogen peroxide 

solution. Thiols precipitate with hydrogen 

sulfide. In the absence of H3 . only co-'traces 

of thiols are collected. When methane- ard 

ethane-thlols at a total level of 300 ms/m° 

are present In addition to H.S. the results 

•vtmry tram 2 percent low at an K3. conce'ntration of 400 mg/m' to 14 percent high at 

an H.S concentration of 100 mg/m\ Carbon 

oxysulfids &*» a concentration of 20 percent 

does not interfere. Certain carbonyl-contalning compounds react with iodine and 

produce recurring end points. However, acetaldehyde and acetone at concentrations of 

J and 3 percent, respectively, do nol interfere. 

Entrainsd hydrogen peroxide produces a 

negative interference equivalent to 100 percent of that of an equimolar quantity ol hydrogen sulfide. Avoid the ejection of hydrosen peroxide Into the cadmium sulfate impingers. 

4. Preciyton end accuracy. Collaborative 

testing has shewn the wlthln-laboratory coefficient of variation to be 2.2 percent and 

•ihe overall coefficient of variation to be 5 

percent. The method bias was shown lo be 

—4.6 percent when only H,S was present. In 

" the presence of the Interferences cited In 

section 3. the bias was positive at low H,S 

concentrations- and negative at higher concentrations. At 230 mg H,S/ra\ the level of 

the compliance standard, the bias was 4-2.7 

percent. Thiols had no effect on the precision. 

H. Apparatus. 

B.l Sampling apparatus. 

8.1.1 Sampling line. Six to 7 mm (V« in.) 

Teflon' tublp.2 to connect the sampling 

train to the samplln? valve. 

8.1.2 Impingers. Five mldset impingers. 

each with 30 ml capacity. The Internal diameter of the Impinger tip raust be 1 mm 

a. 0.05 mm." Th* Impinger tip must be poel-

- tloned 4 to 6 mm from the bottom of the impinger. 

8.1.3 Class or Teflon connectlns tubing 

. £or the Implnaers. 

8.1.4 Ice bath container. To maintain absorbing solution at a low temperature. 

8.1.5 Drying tube. Tube packed with 8- to 

16-mesh Indleatlng-type silica gel. or equivalent, to dry the sas sample Bnd protect the 

meter tnd pump. If the silica Bel has been 

used previously, dry et l°li' C'(350' F> for 2 

hours. Ji'ew eillca gel may be used as received. Alternatively, other types of des'.ccantj (equlvn)ent or better) may bs used, 

subject to approval of the Administrator. 

NOTE.—Do not use more than 30 g of aluco 

Sel. Silica sel absorbs gases such as propane 

trom the fuel sas stream; and use of excessive amounts of eillca gel could result in 

errors in the determination of sample 

volume. 

3.1.6 Sampling valve. Keedle valve or 

equivalent to odjust sas How rate. Stainless 

Oteel or other corrosion-resistant material. 

9.1.7 Volume meter. Dry sas meter, sufficiently accurate to measure the sample 

volume within 2 percent, calibrated at the 

selected flow rate c—1.0 Ut^r/mln) and conditions sctu&lly encountered during s&mpllns. The meter shall be equipped with a 

temperature gauge WisJ thermometer or 

equivalent) capable of measuring temperature to within 3' C «.B* F). The sas meter 

ohould have o petcock. or equivalent, on fhe 

cutlet connector which cut be closed during 

the leak check. Gas volume for one revolution of the meter must not be more than 10 

liters. 

S.U Flow meter. Rotameter or equivalent, to measure flow rales in the range 

from 0.5 to 2 llters/mln (1 to « cfh). 

2.1.9 Graduated cylinder. 25 ml size. 

. 5.1.10 Barometer. Mercury, aneroid, or 

other barometer capable of measuring atmospheric pressure to within 2.5 mm Kg 

(0.1 in. Hg). In many cases, the barometric 

reading may be obtained from a nearby National Weather Service station, ln which 

case, the station value (which is the absolute baromttrlc pressure) shall be requested 

and an adjustment for elevation differences 

between the weather station and the sampling point shall be applied at a rate ol 

minus 2.5 mm Hg (0.1 in. Hg) per 30 m (ICO 

ft) elevation Increase or vice-versa for eleva-

• tion decrease. 

8.1.11 U-tube manometer..C-30 cm wate; 

column. For leak Check procedure. 

5.1.12 Rubber squeeze bulb. To pressur--

!ze train for leak check. 

5.1.13 Tee. plnchclamp. end connecting . 

tubing. Fcr leak check. 

5.1.14 Pump. Diaphragm pump, or equivalent. Insert si email surge tank between thr 

pump and rate meter to eliminate the pulsation effect of the diaphragm pump on the 

rotameter. The pump Is used for the air 

purge at the end of the sample run: tlic 

pump is not ordinarily used during sampling, because fuel sas streams are usually 

sufficiently pressurized to force sample gas 

through the train at the required flow rale. 

The pump need net be Jeak-free unless lt Is 

used for sampling. 

5.1.15 Needle valve cj critical oil'lce. To 

Bet air purge flow to I llter/mln. 

B.l.16 Tube packed with active carbon. 

To filter air during purse. 

6.1.17 Volumetric flask. One 1.000 ml. 

8.1.1B Volumetric pipette. One 15 ml. 

6.1.19 Pressure-reduction regulator. Depending on the sampling stream pressure, a 

pressure-rtdaction regulator may be ne?d?(< 

to reduce the pressure of the gas stream entering the Teflon sample line to a safe level. 

8.1.20 Cold trap. Xf condensed waler or 

amine ls present in the sample stream, e 

corrosion-resistant cold trap ehall be used 

immediately after the sample tap. The trap 

ahall not be operated below 0' C (32* F) loavold condensation of C, or C. hydrocarbons. 

6.2 Sample recovery. 

8.2.1 Sample container. Iodine flask, 

glass-stoppered: 500ml size. 

6.2.2 Pipette. 50 ml volumetric type. 

8.2.3 Graduated cylinders. One each 25 

and 250 ml. 

•Mention of trade names ol specific products does nol constitute endorsement by the 

Environmental Protection Agency. 

8.2.4 Flasks. 125 ml. Erlenmeyer. 

B.2£ Wash bottle. 

8.2.3 Volumetric flasks. Three 1.000 linL 

8.3 Analysis. 

8.3.1 Flask. 500 ml glass-stoppered lodin 

flask. 

8.3.2 Burette. 80 ml. 

8.3.3 Flaak. 125 ml. Erlenmeyer. 

B.3.4 Pipettes, volumetric. One 25 ml: Iwi 

each 50 and 100 ml. . : 

8.3.5 Volumetric flasks. One 1.000 m' 

two 500 mt * 

- 8.3.6 Graduated cylinder's. One each 1 

and 100 ml. 

0. HcogenU. Unless otherwise indicated. I 

fe intended th»t air reagents conform to th 

specifications established by Ihe Commute 

on Analytical Reagents of fhe America: 

Chemical Society, where such specification 

are available. Otherwise, use best svallab! 

grade. 

B.l Sampling. 

0X1 Cadmium sulfate absorbing sok 

tion. Dissolve 41 s of 3CdSO. BH.O and 1 

ml of 0.1 M sulfuric acid In a I -liter volume) 

rlc flask that contains approximately *« Htc 

of deionized distilled water. Dilute t 

volume with deionized water. iAitt thorougl 

Dy. pH should be 3-0.1. Add 10 drops c 

Dow-Cpmlp.g Antifoam B. Shake well befor 

use. If Antifoam B Is nol us?'d. lhe alternat 

acidified iodine extraction procedure (f-ct 

tion 7.2.2) must be used. 

6.1.2 Hydrogen peroxide. 3 ptrccn'. 

Dilute 30 percent hydrogen pfroxidt to 

percent as needed. Prepare fresh dally. 

6.1.3 Waler. Deionized. distilled to MU 

Jorm to ASTM specifications Dl 193-7: 

Type 3. Al the nptian of the analyst, th 

KMnO. test for nxidizable organic malt: 

may be omitted when high concentration 

of organic matter arc not expected lo !•• 

presente r Sample recovery. 

8.2.1 Hydrochloric acid solution (HCI 

3M. Add 240 ml of concentrated HCI (M>eci 

lc gravity 1.19) to 5C0 ml of deionized. di 

tilled waler fn a 1-liicr volumetric fl*s'' 

Dilute to 1 liter with deionized water. Mi 

thoroughly. 

0.2.2 Iodine solution 0.1 K. Dissolve 24 

of potassium Iodide (Kl) In :<0 ml of dcloi 

ized, distilled waler. Add 12.7 r of resul 

- limed Iodine (I.) to the potassium lodidt .«.< 

ltillon. Shake the mixture until the Iciiiite ' 

completely dissolved. If possible, let lhe K 

lutlon aland overnight In lhe dark. Slow:! 

dilute foe solution to 1 liter with deloniz^ 

distilled water, with swlriinfr. Filler the u 

lu'.lon i! Jl Is cloudy. Store solution in 

brcwn-glass reagent bottle. 

6.2.3 Standard Iodine solution. 0.01 N. P 

pette 109.0 ml of the 0.1 N Iodine Kilutlo 

into a41ller volumetric flask and dilute t 

volume with deionized. distilled waler. SUM 

dardlze daily as In section 8.1.1. Thb solt 

Uon must be protected from light. Reftgsr 

fcottles tnd flasks musl bt kcpl tigh'.ly Mo; 

pcred. 

S.S Analysis. 

C.3.1 Sodium thlosul/nte r.olu'.lon, Bta, 

dard 0.1 )«. Dissolve 24.8 ft of .sodium thi' 

BUlfnte pentahydrate (fta,SiO>-5H,0> or is 

3 of anhydrous sodium thiosulfate (Na&O 

in 1 liter of deionized, distilled waler fci 

add 0.01 tr of cnhydroiu .<odlum caihrma' 

(Ka,CO.) and 0.< ml of chloroform (CHCi 

to stabilize. Mix thoroughly by shsklnst i 

by aerating with nitrogen lor nplwoxlniatel 

15 minutes end store In u ^lass-stoppcri: 

reagent bo'.llc. Standardize fcs In M\-.llc 

0.1.2. 

8.3.2 Sodium thiosulfate. solution, sta: 

dard 0.01 N. Plpelie 50.0 in) of the stundai 

0.1 N thiosulfate solution Into a volumetr 

flask and dilute to SOO ml with div.l'.h 

water. 

III-Appendix A-41 
Norr.—A 0.01 N phenylatslne oxide soluI -

tion may be prepared instead of 0.01 N thiosulftte (see section 6.3.3). • . • 

6.3.3 Phenylarslne oxide solution, standard 0.01 N. Dissolve 1.80 t of phenylarslne 

oxide (C.H.AsD> in 150 ml of 0.3 N sodium 

hydroxide. After settling, decant 140 ml of 

this solution into C00 ml of distilled water. 

Bring the solution to pH S-7 with 6N hydrochloric acid and dilute to 1 liter. StandardUe as ln section 8.1.3. 

6.3.4 Starch indicator solution. Suspend ' 

10 g of soluble starch In 100 ml of deionized. 

distilled water and add IS g of potassium 

hydroxide (KOH) pellets. Stir until dissolved, dilute with 900 ml of deionized distilled waler and let sland'for 1 hour, neutralize the alkali with concentrated hydrochloric acid, vising an indicator paper similar 

to Alk&cid tesl ribbon, then add 2 ml of glat a l acetic acid as a preservative. 

Nore—Test starch indicator solution for 

decomposition by.titrating, with 0.01 N 

iodine solution. 4 ml of starch solution in 

200 ml of distilled water that contains 1 E . 

potassium iodide. If more than 4 drops of 

- the 0.01 N Iodine solution are required to 

obtain the blue color, a fresh solution must 

t e prepared. 

7. procedure. 

7.1 Sampling. 

7.1.1 Assemble the sampling train as 

thown in figure 11-1, connecting the five 

midg-t impinger* ln series. Place 15 ml of 3 

percent hydrogen peroxide solution in the 

fiwt impinger. Leave the second impinger 

empty. Place 15 ml of the cadmium sulfate 

absorbing solution ln the third, fourth, and 

fifth impingers. Place the Impinger assembly in an ice bath container and place 

crushed 1ce around the lmplngen. Add more 

Ice during th? run. if needed. 

7.1.2 Connect the rubber bulb and manometer to fir=t Impinger. as shown ln figure 

11-1. Close the petcock on the dry gas meter 

cutlet. Pressurize the train to 25-cm water 

pressure with the bulb and close off tubing 

connected to rubber bulb. The train must 

hold a 25-cm water pressure with not more 

than a 1-cm drop ln pressure in a 1-minute 

interval. Stopcock grease Is acceptable for 

sealing ground class Joints. . . 

Nore—This leak cheek procedure ls optional at the beginning of the sample run. 

but is mandatory al the conclusion. Note 

fclso that If the pump Is used for campling, it 

U recommended (but not required) that the 

pump be lez.k-cheek;d separately, using a 

*«?thod consistent with the leak-check procedure for diaphragm pumps outlined In 

section 4.1.2 of reference method 6. 40 CFR 

Part 60. Appen.dlx A. 

* 7.1.3 Purge the connecting line between 

the campling valve and first impinger. by 

disconnecting the 11ns from the first Impinger. opening the sampling valve, and allowing process gas to flow Ihroujtb the line 

for a minute or two. Then, close the sampling valve and reconnect the Une to the implr.yer train. Open the petcock cn th* dry 

pas meter outlet. Record the initial dry gas 

meter reading. 

7.1.4 Open the sampling valve and then 

adjust the valve to obtain a rale of approximately 1 llter/mln. Maintain a constant 

.(±10 percent) flow rate during the test. 

• Record the meter temperature. 

7.1.5 Sample for at least 10 min. At the 

end of the sampling time, close the sampling valve and record the final volume and 

temperature readings. Conduct a leak check 

as described in Section 7.1.2 above. • 

7.1.6 Disconnect tht impinger train irom 

the sampling line. Connect the charcoal 

tube and the pump, as shown W figure 11-1. 

c 

P.23 

urge the train (al a rate of 1 ilter/mln) 

with clean ambient air fpr 15 minutes to 

ensure that all H.S is removed from the hy-' 

dxogen peroxide. For sample recovery, cap 

the open ends and remove the Impinger 

train to a clean area that Is away from 

sources of heat. The area should be well 

lighted, but not exposed to direct sunlight. 

7.2 Sample recovery. 

7.2.1 Discard the contents of the hydrogen peroxide Impinger. Carefully rinse the 

contents of the third, fourth, and fifth impingers Into a 500 ml Iodine flask. 

Cr\ 

* VALVl ' l,N I ^'" I4»«<CIRS SIUCA Cll TU31 

ted D=^ 

HyJ«5*» f«*Jc\ '==&

==n Cr 

**^ c Su\ So 

p«r CAS MIT tft 

~»u»> 

(roRAiarvacii 

Flgur* lM.'H2$«>mf>lin}1r»in. 

.Ill-Appendix A-4 2 
P.24 

C c 

Korx—Th* Implnjsra normally hav* onljr 

& thin film of csdmlum eulfld* remaining' 

'tSiot a water rlris*. It Antifoam D w u not 

\-3-A cr U •Ijn'.flsant cuantltle* ol yallow 

cadmium eulttd* remain In th* Implnjers, 

tha tlt*m»t* r«ov»ry procedure dewribed 

bslow must b» u»*d, 

7.3.3 PIpstu exactly DO ml of 0.01 N 

lodln* solution Into a 123 ml £rl»nm»y»r 

flask. Add 10 ml of 3 M HQ to tht solution. 

Quantitatively rlns* th» acldtflsd" lodln* 

Into th> ledin* flask. Ciopp»r th* fl»5» Immediately and ahak* briefly. 

7.3.3 (Alternstv). Extract th» remslnln? 

cadmium sulfIdt from th* third, fourth, and 

fifth Jmprns»r» using th» tcldlflsd Isdln* solution. Immadistaly Af ur pourbij tht acidified lodln* Into an Iraplnjsr, otopptr It fend 

ihaks for ft fsw moments, than trarufar th* 

liquid to th* lodln* fluU. Do not trtctstor 

any rlrj» portion from on* Irr.plnjer to anothar, translsr It directly to th* lodln* flask. 

Or.cs the acidified lodln* solution hw been 

poured into any glassware containing cadmium sulfide, the container must be tightly 

stoppered at all times except when adding 

more solution, and this must be don* as 

culckly and carefully as possible. After 

adding any acidified iodine solution to the 

iodine flask, allow a few minutes for absorption of the HiS before adding any further 

rinses. P.epeat the Iodine extraction until all 

cadmium sulfide ls removed from the Impingers. Extract that part of the connecting 

classware that contains visible cadmium sulfide. 

Quantitatively rinse all of tht Iodine from 

the Impinger*. connectors, tnd the beaker 

Into the Iodine flaak ualng de!onl:ed, distilled water. Stopper ths flaak and shake 

briefly. 

7.2.3" Allow the Iodine flask to stand 

about 30 minutes in the dark for absorption 

of the HtS into the iodine, then complete 

the titration analysis as ln section 7.3. 

•Kerr.—Cautlor.l Iodine evaporates from 

acidified Iodine solutions. Samples to which 

acidified Iodine have been added may not be 

stored, but must be analyzed in the Ume 

schedule stated in section 7.2.3. 

7.2.4 Prepare a blank by tddlnj 45 ml of 

cadmium sulfate absorbing solution to en 

iodine fiask. Pipette exactly iO ml of 0.01 N 

iodine solution into » 125ml Erlenmeyer 

flask. Add 10 ml of 3 M HCl. Follow the 

same lntplnger extracting and quantitative 

rinsing procedure carried out in sample 

analysis. Stopper the flask, shake briefly, 

let stand 30 minutes In the dark, and titrate 

with tbe samples. 

Koss.—The blank must be handled by exactly the same procedure as that used for 

the samples. 

7-. Analysis. 

Nors.—Titration analysis should be conducted at the sample-cleanup area In order 

to prevent loss of Iodine from the sample. 

Titration should never be made In direct 

sunlls'nt. 

7.3.1 Using 0.01 N sodium thiosulfate solution (or 0.01 N phtnylarslne oxide, lf applicable), rapidly titrate each sample In an 

iodine fiask using gentle mixing, until solution is light yellow. Add 4 ml of starch indicator tolutlon and continue titrating slowly 

until the blu* color Just disappears. Record 

Vr,. the \olume of sodium thiosulfate solution used, or VAT. the volume of phenylarslne oxide solution used (ml). 

7.3.2 "Titrate the blanks In the same 

xazmer as the eamples. Run blanks each 

day until repllcat* vsluss 63ro* within O.OS 

tnl. Aver&a* th* repllest* titration valuo* 

which agr** within 0.05 ml. 

0. Calibration end itanicrdi. 

8.1 etandwdliatlons, 

B.l.l Btandsrdlz* th* 0.01 tf lodln* solution dally u follows: Plptltt Ss nl of th> 

lodln* solution Into ft IS) ml Erlswr.oysr 

fluk. Add 3 ml ef I M HCU Tltri*.* rapidly 

with standard 0.01 N thlcjulfat* solution or 

with 0.01 N ph*ny!a»ln» oxld* until th* tolutlon Is ll;ht yellow, u>lc; contl* mixing. 

Add four drops of starch indlci'.or solution 

and contlnu* tltratlnj slowly until th* blue 

color Just d!i»pp»m. Record Vf th* volum* 

of thbiulfst* tolutlon ussd. cr V*J. th* 

volum* of phonylwaln* oxld* tolutlon uisd 

(ml), RepsV. until ropllciU volusi asr»» 

within 0.05 ml. AVSMJ* th* rsplleat* tltration value* which tgre* within 0.01 ml and 

calculat* th* caaet normality of th* lodln* 

solution using equation 0.3. Repast tb* 

standardization dally. 

6.1.3 Standardise the 0.1 K thlosulfst* 

solution as follow* Oven-dry potassium dl-

.chromate (K.Cr.O.) at 180 to 200' C (380 to 

890" F). Weigh to ths nearest nllll-rrsm, 3 y 

of potassium dichrcmate. Transfer tho dichromate to a C00 ml volumetric flask, dissolve in deionised, distilled wster and dilute 

to exactly BOO ml. In a 600 ml lodlns flask, 

dissolve approximately 3 g of potassium 

Iodide (KI) ln 45 .ml of deloniied. distilled 

water, then add 10 ml of 3 M hydrochloric 

acid solution. Pipette to ml of th* dichromate solution into this mixture. Gently 

swirl the solution once and allow it to stand 

ln the dark for 5 minutes. Dilute the solution with 100 to 200 ml of delor.Ized distilled 

' waler. washing down the sides of the flask 

with part of the wster. Titrate with 0.1 N 

thiosulfate until the solution is l.'jht yellow. 

Add 4 ml of starch indicator and continue titrating slowly to a creen end point. Record ' 

V|. the volume of thlosuirate solution UJtd 

(ml). Repeat until replicate analysts agree 

within 0.05 ml. Calculate the normality 

using equation 0.1. Repeat the standardization each week, or after each test terles, 

* whichever time is shorter. 

8.1.3 Standardize ths 0.01 N Phenylarslne oxide (If applicable) as follows: oven 

dry potaaslum dichromate (K.Cr.O,) at 180 

to 200" C (360 to 350* F). Weigh to the nearest milligram, 2 g of the K.Cr.O,; transfer 

the dichromate to a 500 ml volumetric flask, 

dissolve in delonhed, distilled water, and 

dilute to exactly 500 ml. In a 500 ml iodine 

flask, dissolve approximately 0.3 c of potassium Iodide (XI) In 45 ml of deionized. distilled water, add 10 ml cf 3M hydrochloric 

acid. Pipette 5 ml of the K,Ci.O, solution 

Into the Iodine flask. Gently swirl the con-, 

tents of the flask once and allow lo stand In 

the dark for C minutes. Dilute tht solution 

with 109 to 200 ml of deionised. distilled 

water, washing down the tides of the flask 

with part of the water. Titrate -with 0.01 N 

phenylarslne oxide until ths solution is 

light yellow. Add 4 ml of starch Indicator 

and continue titrating slowly to a green end 

point. Record VA. the volume of phenylarslne oxide used (ml). Repeat until replicate 

analyses agree within 0.05 ml. Calculate the 

normality using equation S.2. Repeat the 

standardization each week or after each tesl 

series, whichever time is shorter. 

C.2 Sampling train calibration. Calibrate 

the sampling train ccmpone.its as follows: 

8.2.1 Dry gas meter. 

8.2.1.1 Initial calibration. The dry gait 

meter shall be calibrated before its initial 

use ln the field. Proceed as follows: First, asstmbl* th* following components In sarles: 

Drylnj tub*, needle valv*. pump, roUir.tler, 

tnd dry gu. miter. Than, le&k-chock the 

tystem u followi: Place a vacuum gsugs (at 

lssst 760 mm Hj) at tho Inlot to tho drylny 

tub* tnd pull e vscuum of 350 mm (10 In.l 

He, plus or pinch off ths outlet of the flow 

m*t«.*, and than turn off lhe pump. The 

vscuum (hall romsln ttabls for at Itu*. 30 

second). Carefully relsas* ths vacuum 

tauge before releasing the flow motor end. 

H*»t, eelibraU th* dry SM meter ut the 

•ampltnj flow ret* ipeclflod by the method) 

ts follows: Connect an appropriately sited 

wet test meter (e.g., 1 liter psr revolution) to 

th* Inlet cf th* drying tube. Mske threi independent cnllbrstlon rum, using At hu l 

fiv* revolutions of tho dry su meter par 

run. Calculat* the c&llbrallon factor. y<w;i 

test meter calibration volume divided by the 

dry cis meter volume, both volumes adjuitcd to the same reference temperature snd 

pre»»uro). for each run, and aversge the results. If any y value deviates by more than 1 

percent from the sveraje. the dry gas meter 

ls unacceptable for us:. Otherwise, use the 

avere?s as the cslibration factor for eubsrquent test runs. 

8.2.1.2 Post-test calibration check. After 

each fl'-ld Lest series, conduct a calibration 

check as Jn aecllon 8.2.1.1. above, except for 

the following variations: (a) The leak ch«V 

is nol to bs conducted, (b) three or more 

revolutions of the dry sas meter may bt 

used, and (3) only two Independent ium 

need be made. If the calibration factor doti 

not deviate by more than 5 percent from 

the JnltUI calibration factor (determined In 

section 8.2.1.1.), then the dry cas meter volumes obtained during lhe lest series ere >tceptible. lf the calibration factor deviates 

by enors than 8 percent, recalibrate the dry 

cas meter as In' section 8.2.1.1, end for th: 

calculations, use the c&llbratlon factor (Initial or recalibration) that yields the lower 

ens volume for eich test run. 

8.2.2 Thermometers. Calibrate apalrjt 

mercury-ln-slas* thermometers. 

8.2.3 Rotameter. The rotameter r.ecd not 

be calibrated, but should be denned snd 

maintained according to the munufactuitr'* 

Instruction. 

8.2.4 Barometer. Calibrate against a Insrcury barometer. 

0. Ccleufofionj. Carry oul calculations retaining nl least one exlm decimal figurebeyond that of the acquired data Round off 

results only after the flnM calculation. 

P.l Normality cf the Standard (-0.1 K) 

Thiosulfate Solution. 

N,»2.033W/V, 

where: 

Vr-Weight of K,Cr,0, used, vV,-Volume of Na£,0, solution used. ml. 

Kj-Normallty.of standard thiosulfate solution, e-eq/llter. 

2X39-Conversion factor 

(8 eq. I./nole K.Cr,0,) (1.000 ml/lllcr)/-

(204.2 g X.Cr.O,Amo!e) (10 aliquot fector) 

0.2 Normality of Standard I'henylarstne. 

Oxide Solution (Inapplicable). 

H4-0.203 9 W/V* 

where: 

W-Welght of K.Cr.O. used, gVi-Vo)ume of C.H.A.O used. ml. 

Nj-Normality of standard phenylarslne 

oxide solution. E»eq/llter. 

O.5039-Conversion factor 

Ill-Appendix A-43 
<t eq. 1,/aiole K,Cr.O,> (1.000 ml/lltert. 

(249.2 g . K,Cr.O,/mole> OOO aliquot 

factor) 

L 

P,3 

tion. 

Normality ol Standard Iodine SoluN.-N/vVV, 

where: - . ' -

: 

Ki-Normaltty of standard Iodine solution. 

B-eq/llter. 

Y,-Volume of standard Iodine tolutlon 

used. ml. 

Nt-Normallty of standard (-0.01 N) thiosulfate solution*, assumed to be 0.1 N». 8-

eq/llier. ^ , 

VT-Volume of thiosulfate solution used. aL 

NOT*.—If phenylaxslne oxide Is used 

tntsad of thiosulfate. replace Nr and VT In 

Equation 0.3 with N» and V ^ respecUvely 

(see sections 8.1.1 and 8.1.3). 

8.4 Dry Gas Volume. Correct the sample 

volume measured by the dry ess meter to 

• otandard conditions (20* C) nnd 760 mm Hg. 

V.w.»-V.Y t(T«*/T.) CP_/P;«» 

Where: 

V„w - Volume at standard conditions of gas 

sample throuzh the dry cas meter, stan-

. dard liters. 

\*.-Volume or gas sample through the dry 

eas meter (meter conditions), liters. 

T«4- Absolute temperature at standard conditions. 293" K. 

T„-Averaae dry eas meter tempertHure. *K. 

Pw-B»rometrle pressure at the sampling 

site. mmHg. 

P^-Absolute pressure at standard condl- -

• . tions. 760 mm Hg. . . 

Y - Dry cas meter calibration factor. 

0.5 Concentration of H A Calculate the 

concentration of H.S in the cas stream at 

standard conditions using the following 

equation: 

C.-KKVnN.-VnN,) sareple-

(V„N,-VnNT) blankl/V..^ 

where (metric units): * ' 

CM»» Concentration of H 3 at standard conditions, mg/dscm. 

K-Con version factor-17.04x10' 

C34.07 c'mole K£ ) (1.000 llters/m*) <1.000 

ma/g)/-(1.000 ml/liter) (2H.3 eq/mole) 

Vir-Volume of standard Iodine solution** 50.0 ml. 

N.-Normalily of standard Iodine solution, 

C-eq/liter. 

Vrr-Volume of standard (-0.01 N) sodium 

thiosulfate solution. mL 

Ki-Normality of standard sodium thiosul-

• fate solution, c-eq/liter. . 

Vw.ai-Dry Cas volume at standard conditions, liters. 

NOTX.—If phenylarslne oxide ia used Instead of thiosulfate. replace Ht

 and V n In 

Equation 9.5 with NA tJid VM. respectively 

(sse Sections 7.3.1 and 8.1.3). 

\ Stability. The absorbing solutton Is 

stable for at least 1 month. Sample recovery 

and analysis 6hould begin within 1 hour of 

sampling to minimize oxidation of the acidified cadmium sulfide. Once Iodine has been 

added to the sample, the rematnder of the 

analysis procedure must be completed ac- . 

cording lo sections 7.2.2 through 7.3.2. 

11. Bibliography. 

11.1 Determination of Hydrogen Sulfide, 

Ammonlacal Cadmium Chloride Method.. 

API Method 772-5L IrU Manual on Disposal 

Of Refinery Wastes, VoL V: Ssmpling and 

Analysts of Waste Oases and Particulate 

M titter, American Petroleum Institute, 

Washington, D.0.1954. 

11.2 Tentative Method of Determination 

of Hydrogen Sulfide and Mercaptan Sulfur 

In Natural Oaa. Natural Oaa Processors Association, Tulsa. Okla, NOPA Publication 

No. 2265-63,1095. 

11.3 Knoll, J. E.. and M. R. MldgetL Determination of Hydrogen Sulfide in Refinery Fuel Oases. Environmental Monitoring 

Series. Office of Research and Development. USEPA. Research Triangle Park. N.C. 

27711, EPA 600/4-77-007. 

11.4 Schelll. O. W„ and M. C. Sharp. 

Standardization of Method 11 at a Petit*' 

)eum Refinery, Mldweal Research Institute 

Draft Report for USEPA. Office of Research and Development. Research Trlsnjle 

Park. N.C. 27711. EPA Contract No. 65-02-

1033. Aususf 1976. -EPA 600/4-77-033* 

(Volume 1) end EPA 600/4-77-ODSb (Volume 

3). 

(Sees. Ill , 114, 301(6), Clean Air Act as 

amended (42 U.6.C.7411,7414,760).).) 

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