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## Document

Number: 

# 56 ) II-A- 5
Docket Number: 

# A-84-4 4

Printed 4/16/2008 8:13:21 AM

Sheet 56 of 70

# x-/EP A Agenc y aUJ 7 r P. 2
Researc h an d Developmen t EPA-600/S4-B2-05 4 August 198 2 

# Project Summary A-84-4 4


# Fiel d Evaluatio n o f Carbo n Monoxid e an d Hydroge n Sulfid e Continuou s Emissio n Monitor s a t an Oi l Refiner y

Bruc e B . Ferguso n an d Richar d E . Leste r

A n eleven-mont h fiel d evaluatio n wa t conducte d fo r fiv e hydroge n sulfid e an d fou r carbo n monoxid e continuou s emis sio n monitor s (CEMs)
. Th e H 2 S CEM s wer e installe d o n a fue l gas lin e an d th e C O CEM s wer e installe d o n a stac k fro m a fluidize d be d catalyti c crackin g uni t a t a refinery . Performanc e specificatio n tastin g wa s routinel y performe d o n th e instrument s a s the y wer e operate d an d maintaine d i n thi s fiel d 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 fullydocumented in a separate

report of the same title (see Project Report ordering

information at back). Introductio n O n Marc h 15 . 1978 . EP A promulgat e d Ne wSourc e Performanc e Standard s (NSPS ) tha t required petroleu m refinerie s t o continuousl y monito r th e carbo n mo noxid e (CO ) emission s fro m flui d cata lyti c crackin g (FCC ) units. 1 Refinerie s wer e require d als o t o continuousl y moni to r eithe r th e hydroge n sulfid e (H 2 S ) concentratio n i n fue l ga s fee d line s o r th e sulfu r dioxid e (S0 2 ) concentratio n i n th e exhaus t o

f th e boile r burnin g th e fue l gas . However , refinerie s wer e not re quire d t o instal l H 2 S o r C O continuou s emissio n monitor s (CEMs ) unti l perform anc e specification s fo r th e instrument s wer e publishe d by th e EPA . I n Apri l 1979 , th e EP A initiate d wor k t o establis h thes e specification s an d als o t o determin e th e durability , mainte nanc e requirements , an d dat a validity o f commerciall y availabl e C O an d H 2 S con tinuou s emissio n monitors . T o procure th e monitors . 3 5 vendor s o f commerciall y availabl e stac k

gas monitors fo r C O an d H 2 S wer e asked t o recommen d monitors fo r evaluation . Sixtee n di d not respond . A tota l o

f te n H 2 S an d thirtee n C O monitors wer e advance d fo r consid eration . Fro m thi s list , five H 2 S an d fou r C O monitors wer e selecte d fo r evalua tio n (Tabl e 1)
. Th e selectio n criteri a in clude d operatin g principle , engineerin g judgmen t abou t suitability fo r use a t pe troleu m refineries , an d tota l cost . Thes e nin e monitors wer e installe d i n a traile r a t th e Harmo n Engineerin g & Test in g facility i n Auburn , Alabam a an d the n transporte d t o a petroleu m refiner y fo r a n eleven-mont h fiel d evaluation . Here , th e H 2 S monitors measure d th e H 2 S concentratio n i n a fue l gas a t a poin t downstrea m of a n amin e treate r (a n H 2 S contro l device ) an d th e C O monitors measure d th e C O concentratio n i n th e exhaus t gas fro m a boile r o n a n FC C unit . A n EPA-designe d stac k gas conditionin g syste m remove d particulat e an d wate r fro m th e FC C stac k

gas a t th e samplin g por t before sendin g th e clean , dr y ga s t o a manifol d i n th e traile r (wher e i t wa s dis tribute d t o th e monitors)
. A simila r mani fol d wa s use d t o distribut e fue l ga s t o th e H 2 S monitors .P. 3

Table 1. Continuous

Emission

Monitors

Evaluated Instrument

Manufacturer

Model

Number Abbreviation Operating Principle CARBO N MONOXID E ANALYZER S Anared, Inc. Santa Barbara, CA P.O. Box 3180 Santa Barbara. CA93105 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. PA15208 HYDROGE N SULFID E ANALYZER S Bendix Corporation

Environmental and Process Instruments P.O. Drawer

831 Lewisburg, WVA24901 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, CA91776 501R

3107/2949
Optichrom

102

LIRA202 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/FlamePhotometric Detector

(GC/FPD) Lead Acetate Impregrated Paper Tape Lead Acetate Impregrated Paper Tape Gas Chromatograph/FlamePhotometric Detector

IGC/FPD)

Ultraviolet

Absorption

Th e outpu t fro m th e monitor s wa s re corde d o n a n Esterlin e Angu s P D 206 4 dat a logger , Techtra n 81 6 tap e cassett e recorde r an d a n Esterlin e Angu s multi poin t recorder . Th e multipoin t recorde r printe d th e instantaneou s monito r valu e a t 3-minut e intervals . Th e P D 206 4 rea d th e monitors ' outpu t a t 3-minut e interval s an d printe d th e averag e afte r te n readings , excep t durin g relativ e accuracy test s whe n i t rea d i t ever y minut e an d printe d th e averag e o

f 3 0 readings . Th e P D 206 4 als o initiate d dail y zero an d spa n check

s of th e monitor s wit h cali bratio n gase s an d recorde d th e results . Periodi c test s fo r relativ e accuracy , calibratio n erro r an d short - an d long-ter m drif t wer e conducte d periodicall y durin g th e fiel d evaluation . EP A Metho d 1 1 wa s th e referenc e metho d fo r th e rela tiv e accuracy test s o n th e H 2 S monitors . EP A Metho d 1 0 (NDIR) ) an d a colorimetri c metho d (leuc o crysta l violet , LCV ) bein g evaluate d durin g thi s study , wer e th e referenc e method s fo r th e relativ e accu rac y test s o n th e C O monitors . Th e result s of th e monito r evaluatio n are summarize d here . A ful l repor t de scribe s th e tes t results , th e LCV analyti ca l method , an d th e component s an d performanc e o

f th e FC C stac k

ga s condi tionin g system . Result s an d Discussion s Carbon Monoxide

CEMs Initially , th e monito r evaluatio n wa s intende d t o determin e th e ability of C O an d H 2 S monitor s t o mee t som e tenta tiv e performanc e specification s simila r t o thos e fo r NO , an d S0 2 CEMs
. How ever , afte r th e stud y wa s initiated , EPA revise d Performanc e Specificatio n 2 (NO „ an d S0 Xmonitors ) t o requir e onl y calibratio n erro r (CE ) an d relative accu racy (RA) test s fo r certification. 2 Sinc e simila r requirement s wer e expecte d t o appl y t o C O an d H 2 S monitors , th e focu s of th e fiel d evaluatio n shifte d t o concen trat e o n jus t thes e tw o requirements . Tabl e 2 summarize s th e relative accu racy result s obtaine d o n th e C O moni tors . Overall , fou r vali d relative accurac y test s were conducted o n th e C O monitors . I n thes e tests , th e referenc e metho d sample s wer e collecte d i n Tedla r bag s precede d by a n alkalin e potassiu m permanganat e solutio n fo r N0-./S0, , remova l an d sen t t o th e EP A laborator

y a t Researc h Triangl e Park , Nort h Caro lina , fo r analysi s b

y Metho d 1 0 an d th e LC V method . Sinc e th e MS A an d Anara d monitors suffere d interferenc e fro m C0 2 . 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 C0 2 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 N0 K 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).

de r ga s containin g 10 % C0 2 i n nitroge n wa s introduce d a t th e manifol d afte r eac h relative accurac y tes t an d th e mon itor' s response (pp m CO/ 1 % C0 2 ) wa s use d t o correct th e relative accurac y tes t result s fo r th e C0 2 conten t o f th e stac k gas . A s expected , th e C0 2 interferenc e remaine d quit e stead y durin g th e stud y (Anarad , 3 ppm/1 % C0 2 , MS A 1 ppm / 1%C0 2 )
. Tabl e 3 summarize s th e result s o f th e calibratio n drift (CD ) tests . Thes e test s wer e performe d i n conjunctio n wit h th e dail y zero an d spa n checks . Sinc e th e in strument s wer e not zeroe d eac h day , th e value s reporte d represen t th e dail y zer o drift vslue s correcte d fo r th e zero valu e recorde d fo r th e start o f th e 24-hou r period . Th e Applie d Automatio n performe d wel l durin g th e laborator y check-out , bu t suffere d fro m a n unknow n interferenc e i n th e FC C ga s sample . A vali d relative sccurac y tes t wa s no t complete d be caus e o f thi s an d becaus e o

f th e errati c performanc e o

f th e instrument . Testin g o f th e instrumen t wa s discontinue d afte r a factory representative wa s unabl e t o fin d th e caus e o f th e interferenc e an d unabl e t o correct th e errati c behavio r i n th e monitor' s output . Th e Mode l 294 9 NO./SO , scrubbe r supplie d wit h th e Ecolyze r wa s foun d t o b e inadequat e fo r long-ter m use o f FC C stac k gases wher e S0 2 level s o f 400 - 80 0 pp m an d NO , level s o f 100-40 0 pp m ar e encountered . Because som e o f th e scrubbers wer e exhauste d withi n Table 3. Calibration

Drift Test Results for CO Monitors Calibration

Drift'- * (%) Day Tes t 1 / 2 3 4 5 6 7 Tes t 2 1 2 3^ 4 5 6 7 Tes t 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 . i t wa s decide d t o us e the m only durin g relativ e accurac y tests . Dur in g routin e unattende d operatio n a 2 5 c m lon g x 2. 5 c m I D PV C tub e packe d wit h activate d charcoa l wa s substitute d fo r th e 294 9 scrubber . (Thi s charcoa l tub e coul d no t b e use d fo r R A tests , be caus e i t cause d a 30-minut e dela y i n th e analyzer' s respons e t o a chang e i n stac k ga s C O concentration. ) Throughou t th e fiel d study , th e FC C uni t malfunctione d a t frequen t intervals , whic h cause d th e C O leve l i n th e stac k t o ris e abov e th e spa n rang e o f th e moni tor s (100 0 ppm)
. Suc h malfunction s oc curre d durin g th e firs t tw o relativ e accu rac y test s an d i t wa s necessar y t o ad d ambien t ai r t o th e stac k ga s a t th e prob e exi t t o brin g th e C O concentratio n belo w 100 0 ppm . Sinc e thi s dilutio n signifi cantl y reduce d th e SO , an d NO , level s i n th e sample d gas , th e Ecolyze r performe d bette r tha n expecte d durin g th e test . (Th e actua l effec t o f NO , an d SO , o n th e Ecolyze r ca n b e see n b y referrin g t o RA Tes t 3 (Februar y 198 1 A ) i n Tabl e 2 - a tes t i n whic h cylinde r gase s containin g SO , an d NO , a t level s normall y expecte d i n a n FC C stac k

ga s wer e use d instea d o f dilute d stac k

gas. ) Th e Ecolyze r faile d t o complet e th e fiel d stud y becaus e o f detecto r failure . Th e detecto r faile d twic e durin g th e seve n month s th e monito r operated . Th e monito r als o experience d sever e drif t throughou t thi s seven-mont h period . Becaus e it s outpu t wa s no t compatibl e wit h th e P D 206 4 inpu t requirements . th e MS A instrumen t wa s no t operationa l unti l Jul y 1980 . Th e monito r performe d wel l i n al l th e relativ e accurac y test s afte r it s respons e fo r C0 2 i n th e sample d ga s wa s corrected . I t suffere d tw o majo r outage s (bot h o f whic h wer e correcte d b y optica l realignment ) afte r i t passe d th e firs t relativ e accurac y test . Becaus e o f thes e outage s an d th e lat e star t up , th e calibratio n erro r tes t coul d no t b e conducte d o n thi s monitor . Ther e i s n o reaso n t o suspect , however , tha t thi s monito r woul d no t hav e passe d thi s test . Th e monito r suffere d fro m rando m short-ter m drift , bu t ove r th e perio d o f a mont h it s drif t average d les s tha n 3 per cen t o f span . Th e percen t uptim e o f th e monito r wa s 8 6 percent . Th e Anara d operate d withou t mal functio n fro m th e tim e i t wa s installe d i n th e traile r (Novembe r 1979 ) unti l th e projec t wa s complete d i n April , 1980 . t t performe d wel l durin g th e relativ e accu rac y an d calibratio n erro r tests . Like th e MSA , i t sometime s suffere d fro m ran do m short-ter m drift , bu t ove r th e perio d o f a month , it s drif t average d les s tha n 3 percen t o f span . Hydrogen

Sulfide CEMs Th e agreemen t betwee n th e monitor s an d Metho d 1 1 change d radicall y durin g relativ e accurac y tests . Initially , th e monitor s showe d a negativ e bia s wit h respec t t o Metho d 11 , bu t i n earl y Feb ruar y a positiv e bia s bega n t o b e ob served . Th e agreemen t betwee n th e monitor s an d Metho d 1 1 sometime s change d drasticall y fro m on e da y t o th e next . Test s t o determin e th e caus e of thi s bia s wer e inconclusive . Whe n tw o laboratorie s simultaneousl y measure d th e H 2 S concentratio n i n th e fue l ga s th e tw o laboratorie s agree d closel y bu t thei r result s wer e significantl y differen t fro m tha t o f th e monitor s (Tabl e 4 , R A Tes t 5)
. Further , whe n th e fue l ga s wa s spike d wit h know n amount s o f H 5 S bot h th e monitor s an d th e referenc e metho d recovere d th e spike . Thus , th e caus e o f th e bia s remain s unknown . Perhap s i t resulte d fro m a combinatio n of severa l factors , includin g th e slo wre spons e o f th e monitor s an d sudde n change s o f shor t duratio n i n th e H 2 S concentratio n i n th e fue l gas . Tabl e 5 summarize s th e result s o f th e calibratio n drif t (CD ) tests . Thes e test s wer e performe d i n conjunctio n wit h th e dail y zer o an d spa n checks . Sinc e th e in strument s wer e no t zeroe d eac h day . th e value s reporte d represen t th e dail y zer o drif t value s correcte d fo r th e zer o valu e recorde d fo r th e star t o f tha t 24-hou r period . Specifi c comment s abou t th e monitor s ar e presente d below . Th e Teledyn e responde d t o man y othe r compound s presen t i n th e fue l gas . Th e interference s wer e s o sever e tha t fiel d evaluatio n wa s discontinue d o n th e monitor . I t wa s no t possibl e \ o instal l a scrubbe r tha t woul d effectivel y remov e th e majorit y o f th e interference s befor e th e instrumen t faile d completely . Th e PA I wa s no t operationa l fo r mor e tha n tw o week s despit e bein g returne d
Table 4. Summary

of H 2 S 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 %IH

2 Sf 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 %IH

2 S1' 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

Drift 9
- * (%) Test Number Tes t 1 1 2 3 4 5 6 7 Tes t 2 ; 2 3 4 5 6 7 Tes t 3 1 2 3 4 5 6 7 Tes t 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. t o th e manufacture r thre e time s fo r re pairs . A successfu l relative accuracy tes t wa s neve r obtained . Th e Bendi x operate d continuousl y fror* th e initia l start-u p unti l fina l shut - •r wit h onl y fou r brief outages . N o in ference s were detecte d durin g initia l check-out ; a possibl e negative interfer ence i n th e fue l ga s wa s indicate d bu t no t confirmed . Thi s instrumen t experi ence d th e leas

t amoun t o

f drif t o f an y o f th e CEMs
. One proble m encountere d wit h thi s in strumen t resulte d fro m th e fac t tha t i t only sampled th e fue l ga s approximatel y onc e ever y 3. 5 minutes . Thi s featur e o f th e Bendi x make s comparin g it s outpu t fo r 3 0 minute s (tota l sampl e collectio n tim e less th e 1 0 seconds) t o th e result s o f a 30-minut e Metho d 1 1 sampl e of dubiou s validity . Thi s i s particularl y tru e whe n on e considers th e sudde n change s tha t ca n occu r i n th e H 2 S leve l o f th e fue l gas . Th e Bendi x di d complet e th e fiel d stud y wit h onl y tw o majo r outage s an d ha d a percen t uptim e o f 8 9 percent . Th e Housto n Atla s suffere d frequen t mechanica l failure bu t di d complet e th e majority of th e fiel d testing . It s percen tag e uptim e wa s 7 6 percent . Th e failure s wer e primaril y i n th e sampl e dilutio n sys te m whic h employ s a Teflo n slidin g bloc k containin g a cavit y o f know n volume . A t times , th e instrumen t suffere d fro m excessive drift . Calibratio n usuall y too k

a t leas t fou r hours . Th e De l Ma r operate d fo r th e entire tes t progra m withou t mechanica l failure . However , becaus e rotameter s wer e used t o achieve a dilutio n o

f th e fue l ga

s prio r t o analysis , it s calibratio n change d whe n th e density an d viscosity o f th e fue l gas changed . Thi s fac t cause d th e instru men t t o hav e a significan t amoun t o f drift . Th e percen t uptim e wa s 9 7 percent , th e highes t o

f an y o f th e monitors . Conclusion s an d Recommendation s Th e Anara d an d MS A successfull y complete d th e eleven-mont h fiel d stud y •n d demonstrate d tha t reliabl e C O moni tor s wit h goo d drift contro l are availabl e fo r use a t petroleu m refineries . Althoug h C0 2 i s a n interferenc e wit h thes e moni tors , it s effec t i s smal l (i n term s o f th e spa n range ) an d correctable . Wate r vapo r wil l als o interfer e wit h thes e NDI R instruments , bu t i t is unlikel y tha t thes e instrument s woul d sampl e a ga s strea m tha t ha d not alread y ha d th e moisture removed . Overall , th e performanc e o f th e fiv e H 2 S monitors wa s disappointing . Tw o o f th e fiv e monitors neve r obtaine d a vali d sampl e an d a thir d suffere d frequen t malfunction . Th e absolut e agreemen t betwee n Metho d 1 1 an d al l monitor s wa s poo r an d variabl e i n eigh t o f th e te n relative accurac y tests . Sinc e th e source o f thi s differenc e i s unknown , th e us e o f H 2 S monitor s fo r complianc e purpose s canno t b e recommende d a

t thi s tim e nor ca n w e advanc e performanc e specifica tion s fo r accuracy . However , thes e monitor s ma y be usefu l fo r determinin g trend s an d fo r indicatin g th e monthl y performanc e of th e amin e treater . Fo r example , th e averag e H 2 S concentratio n fo r al l Metho d 1 1 test s (14 0 ppm ) com pare s reasonabl y wel l wit h th e averag e fo r eac h monitor : De l Ma r (13 3 ppm)
. Housto n Atla s (13 0 ppm ) an d Bendi x (11 9 ppm)
. Reference s 1 . Performanc e Standard s fo r Ne wSta tionary Sources , Federal Register, 43: 10869 , Marc h 1 5 , 1978 . 2 . Propose d Revision s t o Performanc e Specification s 2 an d 3 , FederalRegister, 46: 8359 . January 26 , 1981 .

jgJWB»-».j rP. 7

Bruce B. Ferguson

and Richard

£ . Lester

ara with Harmon

Engineering

and Testing. Inc.. Auburn, AL36830. William J. Mitchell

is the EPA Project

Officer (see below). The complete

report entitled "Field Evaluation

of Carbon Monoxide

andHydrogen 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
. GOVERNMENTPRINTIN G OFFICE:198^559-09Z/O48 9P. 8

A STUD YTO EVALUAT E CARBO N MONOXIDE AN D HYDROGE

N SULFIDE CONTINUOU S EMISSIO N MONITOR S A

T A N OI L REFINER

Y

b y Bruc e B . Ferguso

nan d Richar d E . Lester Harmo nEngineerin

g & Testin

g Auburn , Alabam

a 3683 0



### an d

W.J . Mitchel l Qualit y Assuranc e Divisio

n Environmenta l Monitorin g System

s Laborator

y Offic e o f Researc

han d Development U.S . Environmenta l Protectio nAgenc y Researc hTriangl e Park , NorthCarolin a 2771 1

EP A Contrac t No . 68-02-310 5

Prepare d Fo r QUALITYASSURANCE DIVISIO N (MD-77 ) ENVIRONMENTA

L MONITORIN

G SYSTEM S UBORATOR Y OFFIC E O

F RESEARC

H AN D DEVELOPMEN

T U.S . ENVIRONMENTA

L PROTECTIO

N AGENC Y RESEARC H TRIANGL E PARK , NORTH CAROLIN A 2771 1"W f SfT p HI ' ? " '

DISCLAIME

R

Thi s repor t ha s bee nreviewe

d b y th e Envlronmenta i Monitorin g Systems Laboratory , U.S . Environmenta l Protectio nAgenc y an d ha s bee

n approve d fo r publication . Approva l doe s no t signify tha t th

e content s necessaril y

reflec t th

e view s an d policie s o f th

e U.S . Environmenta l Protectio

nAgency , no

r doe s mentio

no f trad

e name s o

r conmercia l product s constitut e endorsemen t o r recommendatio

nfo r use .P.1 0

FOREWAR D

Measuremen t an

d nonitorin

g researcheffort s are designe d to anticipat e potentia l environmenta l problems , t o suppor t regulator y action s b

y developin

g a nin-depthunderstandin g o f th

e natur e an

d processe s tha t Impac t healthan d th e ecology , t o provid e innovativ

e mean s o f monitorin g complianc e withregulations , an d t o evaluat e th

e effectivenes s o f healthan d environmenta l protectio neffort s throug

h th e monitorin

g o f long-ter

m trends . Th

e Environmenta l Monitorin g System s Laboratory , Researc hTriangl e Park , Nort hCarolina , ha s responsibility

for : assessmen t o f environmenta l monitorin g technolog

y an d systems ; implementatio no f agencywid

e qualit

y assuranc e program s fo r ai r pollutio

nmeasuremen t systems ; an d supplyin

g technica l suppor t t o othe r group s I

nth e Agenc y includin

g th e Offic e o f Air , Nois e an d Radiation , th e Offic e o f Toxi c Substance s an d th e Offic e o f Enforcement . Th e followin

g investigatio

nwa s conducte

d a t th e reques t o f th

e Offic e o f Ai r Qualit y Plannin

g an d Standard s (OAQPS ) to determin e th e performanc e tha t ca nb e expecte

d fro m continuou s emissio nmonitor s installe

d a t petroleu

m refineries . Th

e result s o f thi s stud y wil l b e use d b y th e OAQP S t o determin e th e appropriatenes s o f thes e monitor s fo r us e at refinerie s an d to determin

e reasonabl e performanc e specifi cation s fo

r thes e monitors .

Thoma s R . Hauser , Ph.D . Director Environmenta l Monitorin g System

s Laborator

y Researc hTriangl e Park , Nort hCarolin

a



### 1 1P.1 1

ABSTRAC T

Th e U.S . Environmenta l Protectio nAgenc

y (EPA ) ha s promulgate d New Sourc e Performanc e Standard s (NSPS ) tha t requir e petroleu m refinerie s t o continuousl y monito r th

e carbo nmonoxid e (CO ) emission s fro m fluid catalyti c crackin g (FCC ) unit s an

d als o t o continuousl y nonito r either th

e hydroge

nsulfid

e (H_S ) concentratio ni nfue l ga s fee d line s o

r th e resultin

g sulfu r dioxid

e (SO- ) concentratio ni nth e boile r exhaust . However , refinerie s are not require d t o instal l H~ S o r C O continuou s emissio nmonitor s (CEMs ) unti l performanc e specification s hav

e bee npublishe

d b y th e EPA . Tentativ

e performanc e specifications , propose d b y EP A afte r laborator

y an d short-ter

m fiel d evaluations , wer e extensivel y evaluate d i na year-lon g fiel d evaluatio

nconducte

d usin g fiv e H~ S an

d fou r C O continuou s emissio n monitors . Th

e H- S CEM

s wer e installe

d o na fue l ga s lin

e an d th e C O CEMs wer e installe d o na stac k fro

m a FCC uni t a

t a neas t coas t refinery . Durin

g th e evaluation , performanc e specificatio ntestin

g wa s routinel y

performe

d o nth e instrument s a s th e instrument s wer e operated an

d maintained ina wor k environment . Th e C O CEMs wer e generall y

reliabl e an

d abl e t o mee t propose d performanc e specifications . Th e H- S CEMs wer e no t abl e t o mee t th e propose

d relativ e accurac y criteri a bu t th e differenc e inmeasure d concentratio

ncoul d no t b

e isolate

d t o th

e CEM s o r th e referenc e method .



### li lP.1 2

CONTENT S

D l sclaimer 1 Forwar d 1 1 Abstrac t ii i Figure s v Table s v i Lis t o f Abbreviation s an d Symbol s vi i 1 . Introductio

n1 2 . Summar

y an d Conclusion s 9 Carbo nMonoxid

e Manua l Metho

d 9 Carbo nMonoxid

e Monitor s 9 Hydroge nSulfid

e Monitor s 1 0 3 . Recommendation s 2 0

Carbo nMonoxid

e Continuou s Bu

i sslo nMonitor s 2 0 Hydroge nSulfid

e Continuou s Emissio nMonitor s 2 0 H. Descriptio

no f Equipment 2 2 Continuou s Emissio

nMonitor s 2 2 Ancillar

y Equipment 2 4 5 . Experimenta l Procedure s 2 9

Genera l Procedure s 2 9 Laborator

y Evaluatio

no f th e Monitor s 2 9 Fiel d Evaluatio

no f th e Monitor s 3 2 6 . Result s an

d Discussio

n3 5 Manua l C

O Metho d Development/Validatio n3 5 Evaluatio

no f Carbo

nMonoxid

e Monitor s * 0 Evaluatio

no f Hydroge

nSulfid

e Monitor s 4 8 Reference s 5 9 Appendice s A . Definitio

no f term

s 6 1 B . Tentativ

e pla nfo r th e evaluatio

no f C O an d HJS continuou s monitor s a

t refinerie s 6 3 C . Vendor s respons e t o letter fro m EP A 7 1 D . FC C emission s ga s sampl e conditionin g syste m 7 4 E . Manua l metho

d fo r measurin

g carbo nmonoxide i

nrefiner

y gase s 8 1 F . Instrument evaluatio nhistor

y 9 6



### I vFIGURE S

Numbe r Pag e 1 Sketc

ho f fiel d evaluatio nsit e 8 2 Sketc

ho f Instrumentatio ntrailer showin

g instrumen t arrangemen t 2 6 3 Plumbin

g diagra

m fo r FC C ga s distributio nto th e C O CEMs. . 2 7 i ) Plunbln

g diagra

m fo r fue l ga s distributio nto th e H. S CEMs 7 2 8 5 Zer o drif t tren d fo r Ecolyzer CE

M 4 5 6 Spa

ndrif t tren

d fo r Ecolyzer CE

M 4 5 7 Zer o drif t tren d fo r MS A CE M 4 6 8 Spa

ndrif t tren

d fo r MSA CE M 4 6 9 Zero drif t tren d fo r Anara d CE M 4 7 1 0 Spa

ndrif t tren

d fo r Anara d CE M 4 7 11 Zero drif t tren d fo r BendixCE

M 5 6 1 2 Spa

ndrif t tren

d fo r BendixCE

M 5 6 1 3 Zer o drif t tren d fo r Housto

nAtla s CE

M 5 7 USpa

ndrif t tren

d fo r Housto

nAtla s CE

M 5 7 1 5 Zero drif t tren d fo r De l Ma

r CE M 5 8 1 6 Spa

ndrif t tren

d fo r De l Ma

r CE M 5 8P. M

TABLE S

Numbe r Page 1 Tentativ

e performanc e specification s fo r C O CEM s 5 2 Tentativ

e performanc e specification s fo r H. S CEM

s 5 3 C O CEMs evaluate

d 6 i J H- S CEMs evaluate d 7 5 Dat a summar

y o f C O CEM s 1 3 6 Summar

y o f C O relativ

e accurac

y test s a

t refiner

y 1 4 7 Calibratio

ndrif t tes t result s fo r C O monitor s 1 5 8 Effec t o f C0 2 , N O , SO - an

d C O monitor s 1 6 9 Dat a summar

y o f H- S CEM

s relativ

e accurac

y test s a

t refiner y 1 7 1 0 Summar

y o f H S relativ

e accurac

y test s a

t refiner

y 1 8 1 1 Calibratio

ndrif t tes t result s fo r H- S monitor s 1 9 1 2 Change i

nabsorbanc e o f C

O reagent blan

k wit htim

e a t

roo m temperatur e 3 8 1 3 Effec t o f N

O an d S0

_ o nleuc o crysta l viole t 3 8 1 4 Compariso

nbetwee

nLC V an d NDI Rresult s o

nFCC samples.. . 3 9 1 5 Relativ

e accurac

y tes t result s o

nC O monitor s 1 5 1 6 Relativ

e accurac

y tes t result s o

nH- S monitor s 5 2 1 7 Result s o f collaborativ e R A tes t o nH- S monitor s 5 5



### v iP.1 5

LIS T O F ABBREVIATION S AN

D SYMBOL S

ABBREVIATION S
A A —

Applie

d Automatio

n CB I —

continuou s emissio nnonito r d.c . —

direc t curren t EP A ~ Environmenta l Protectio nAgenc y FCC —

fluid catalyti c cracke r FI D —

flam e Ionizatio

ndetector FP D —

flam e photometri c detector F S —

ful l scal e CC —

ga s chromatograp

h HAI —

Housto

nAtlas , Incorporate d I D —

Insid e diamete r I R—

infrare

d LC V -- - leuc o crysta l viole t MS A —

Min e Safet y Applianc e NB S —

Nationa l Burea

u o f Standard s NDI R—

nondispersiv

e infrare

d NSP S —

Ne w Sourc e Performanc e Standard s O D —

outside diamete r PAI —

Proces s Analyzers , Incorporate d pp m —

part s pe

r million PS T —

Performanc e Specificatio nTes t PV C —

polyviny l chloride R A —

relativ

e accurac

y

SYMBOL S CH ^ —

methane CH.S H —

methy l mercaptan CO —

carbo nmonoxide CO - —

carbo ndioxide H- S —

hydroge

nsulfid

e N O —

oxide s o f nitrogen SO - —

sulfu r dioxide



### vi iP.1 6

SECTIO N 1 INTRODUCTIO

N

O nMarc h15 , 1978 , EP

A promulgate

d Ne w Sourc e Performanc e Stan dard s (NSPS ) tha t require d petroleu

m refinerie s t o continuousl y moni to r th e carbo nmonoxide (CO ) •.mission s fro m fluid catalyti c crackin g (FCC ) unit s (1) . Refinerie s wer e require d t o als o continuousl y nonito r either th

e hydroge

nsulfid

e (H-S ) concentratio ni nfue l ga s fee d line s o

r th e resultin

g sulfu r dioxide (SO. ) concentratio ni nth e boile r exhaus t (1) . However , refinerie s wer e no t require d to instal l H_ S o r C O continuou s emissio nmonitor s (CEMs ) unti l performanc e specification s were publishe d b y th e EPA . Table s 1 an

d 2 present th

e tentativ

e performanc e specification s fo r bothC

O an d H- S monitor s tha t were subsequentl y propose

d b y a nEP A contractor after laborator y an d short-terme

d field evaluations . Terra s use d i nthes e table s an

d throughout th

e repor t are define d i nAppendi x A . I nth e laborator

y phase , candidat e instrument s were evaluate d to determine :

• respons e characteristic s • stabilit

y withtime , temperatur e an d flo w rat e • sensitivity

t o potentia l interference s likel y t o b e present i

nth e sample

d gas . Th e fiv e C O an d tw o H- S monitor s tha t performe d adequatel y

i nth e laborator

y wer e the

nevaluate

d fo r approximatel y

tw o month s a

t a petroleu

m refiner

y (2,3) . Onl y

on e C O monito r an

d on e H- S monito r performe

d adequatel y

i nth e field testing . I nth e cas e o f th

e C O monitors , dail y

calibratio

ncheck s wer e mandator y fo r reliabl e opera tio no f al l th

e instruments , bu t eve nwithth

e inclusio

no f dail y calibration , th

e contractor questione d th e long-ter

m reliability

o f th e C O monitors . Further , instrument malfunctions , samplin g syste

m nalfunction s an

d dat a logger malfunction s plague d th e fiel d evaluatio

n o f bot htype s o f monitor s whichresulte d i na significan t amount o f downtim e an d los t data . I nApri l 1979 , EP

A initiate

d additiona l wor

k t o determine : (1 ) Informatio

nabout long-terr

a instrument durability , dat a validity an d maintenanc e requirement s o f commercially-availabl e C O an d H- S CEMs a

t a refinery ; an

d (2 ) th

e validit

y o f th e tentativ

e performanc e specifi cation s fo

r th e instruments . I

naddition , a manua l (non-instrumental ) metho d fo r measurin

g C O wa s t o b

e develope

d an d evaluate

d to serv

e a s a nalternat e t o EP

A Referenc e Metho

d 10 .T o procur e th

e monitors , EP

A contacte

d vendor s o f C

O an d H- S con tinuou s stack ga s monitor s b y letter an

d aske d the m t o submi t informa tio nabou t th

e nonitor(s ) the

y though t woul d b

e suitabl e fo

r th e appropriat e refiner y process , th

e operatin

g principl e an

d approximat e cost . A

cop y o f tha t letter an d th e Projec t Accomplishment Pla ntha t accompanie

d i t are include

d i nAppendixB . AppendixC contain s th e vendor respons e t o th e letter and , i f the y suggeste

d a nonitor , th

e mode l number , cos t an d operatin

g principle . O f th e 3 5 vendor s contacted , 1 6 did no t respond . A tota l o f 1 0 H- S an d 1 3 C O monitor s wer e recommende d fo r consideration . Fro m thi s list , fiv

e H- S an

d fou r C O monitor s wer e selecte d fo r evaluation . Th

e pertinen t informatio nabout eac

hinstrument l s Include d i nTable s 3 an d 4 . Th

e selectio

ncriteri a (describe d i ndetai l i

nAppendi xB ) involve d tota l cost , operation/detectio nprincipl e an

d engineerin

g Judgemen t about th e likelihoo

d th e monito r woul d b

e suitabl e fo

r th e application . Fo

r example , one compan y propose

d t o us e a converte

d N O monito r fo

r measurin

g H-S , bu t di d no t consider th e likelihoo

d tha i organic s i

nth e fue l ga s woul d interfer e withth e chemiluminescenc e reaction . After receipt , th

e monitor s wer e installe d i na trailer a

t th e Harmo nEngineerin

g & Testin

g (HE&T ) facilit

y i nAuburn , Alabam

a an d wer e subjecte

d t o check s for : drift , respons e time , electroni c nois e level , interference s an d respons e variatio ndu e t o change s i

nambient temperatur e an

d sampl e flo

w rate . Th

e monitor s an

d trailer wer e the n transporte

d t o a refiner

y fo r a n11-monthfield stud y i nwhichthe

y wer e teste

d a t periodi c interval s fo r relativ

e accuracy , respons e time , calibratio

nerro r an d drift . Th e refiner

y a t whichth

e fiel d evaluatio

nwa s conducte

d ha d adde d a ne w C O boiler t o th

e FC C uni t lnearl y 197 9 to recover addi tiona l energ

y fro m th e FCC exhaus t ga s an d t o reduc e th

e C O concentra tio nl nth e ga s stream . Th

e emissio

nga s fro

m thi s uni t wa s use

d fo r th e C O CE M evaluation . A nEPA-designe

d sampl e conditionin g syste m (describe

d i nAppendi x D ) remove

d th e moistur e an

d particulat e matte r fro m th e FC C ga s a

t th e samplin g port . Th

e conditione

d ga s wa s transporte d to th

e sampl e manifol d throug

h20 0 meter s o f 0.9 5 o nI D black , nylo

ntubin

g a t a flo w rat e rangin

g fro m 8 to 1 5 Lpm . Thi s sampl e conditionin g syste m wa s installe

d l nFebruar

y 1980 , an

d wa s operate

d continuousl y

fo r eleve nweek s befor e th

e monitor s arrive

d a t th e refiner

y to allo

w tim e t o correc t an

y potentia l desig

ndeficiencie s (non e were found ) befor e attachin

g th e monitor s t o it . Thre e measurement s o f CO - an d C O concentration s performe d durin

g thi s 1 1 wee

k perio

d Indicate

d thes e compound s wer e no t affecte d b y th e sampl e conditionin g system . I

n thes e checks , inle t an d outle t sample s were take ni nTedlar bag s an

d analyze d b y NDIRtechniques .P.1 8

A aampi e manifol d wa s use d t o distribut e th e conditione

d FC C stack ga s to th

e fou r C O CEMs . Th

e distributio

nsyste m wa s designe

d t o vent exces s ga s no t require d b y th e instrument s fo

r nonna l opera tion . Th

e uni t wa s als o equippe d wit hsolenoi d valve s controlle d b y a dat a logge r fo

r automati c zero an d spa ncheck s eac

hday . Th e H- S monitor s sample d a fue l ga s lin

e at a point downstrea m o f th e amin e treate r use

d t o remov

e H- S fro

m th e fue l gas . Ifcrin g th e project , bothmonoethanolamine and* ^ diethanolamin e wer e use

d i nthe amine treater . Th e fue l ga s wa s distribute d to th

e fiv e H- S monitor s b

y mean s o f a six-por t samplin g manifol d tha t wa s supplie d continuousl y

wit h treate d fue l gas . Th

e fue l ga s wa s transporte d fro m th e samplin

g poin t t o th

e instrunentatlo

ntrailer throug

happroximatel y

10 0 m o f 0.6 3 c m O D stainles s stee l tubing . Al l instrument s wer e locate d i na 24-foo t long , ai r conditione d trailer . Figur e 1 show s th e locatio

no f th

e instrumentatio

ntraile r inrelatio

nto"th e tw o source s tha t were monitored . . Th e outpu t fro

m th e monitor s wa s simultaneousl y recorde

d o na n Esterlin

e Angu s Mode l P

D 206 4 dat a logger , Techtra nMode l 81 6 cassett e tap e recorde r an

d a nEsterlin

e Angu s multipoin t recorder . Whil e samplin g proces s gas , eac hmonitor' s output wa s rea d a t 3-minut e interval s an

d th e average value fo r 1 0 reading s wa s printe d b y th e dat a logger an

d simultaneousl y

recorde

d b y th e Techtra

nMode l 816 . Th e multipoin t recorde r printe d eac h3-n>inute readin g withou t averaging . Durin

g relativ

e accurac

y testing , th

e dat a logger measure d eac hmonitor' s outpu t a t 1-minut e interval s an d reporte

d th e average ever y 2 0 o r 3 0 minutes . A t th e beginnin

g o f th

e field evaluatio

n(Apri l 1980) , th e ten tativ e performanc e test s liste d i nTable s 1 an

d 2 were performed . Fiel d testin

g performe

d after Ma

y 1980 , however , concentrate d o nre lativ e accurac

y an d calibratio

ndrif t test s l

nrespons e t o a majo r change i

nEPA' s overal l approac ht o monitor syste m performanc e speci fications . Thi s change , formally propose

d i nth e Federa l Register(4) , involve d a drasti c simplificatio no nth e Performanc e Specificatio n Tes t (PST ) Procedur e H. Under thes e propose d PS T revision s th e onl y mandator

y test s ar e relativ e accurac

y an d calibratio

ndrift . Th

e othe r test s tha t were previousl y require

d (5 ) are no

w optional . Fiv e C O an d te nH- S relativ

e accurac

y test s wer e conducte d durin g th e 11-roont

hfiel d evaluation , but not al l monitor s wer e operationa l inal l tests . I

naddition , th

e monitor s wer e subjecte d to dail y

15 - nlnut e zer

o an d spa nchecks . Except fo r days whe

nrelativ

e accurac

yP.1 9

testin g Wa s bein

g performed , zer o an d spa ncalibration s wer e no t normall y

adjuste

d nor e ofte

ntha nweekl y

(frequently

les s tha

nonc e per nonth ) l

norde r t o provid

e dat a o

nth e drif t characteristic s o f eachinstrunent . Only th e ga s chromatograp h(GC ) instrument s were equippe d wit hautomati c zer o an d n o instrument wa s equippe d wit h automati c spa

nadjustment . Relativ e accurac

y test s o

nth e H- S monitor s use d EP A Metho d 1 1 (6 ) a s th

e referenc e nethod . Relativ e accurac

y test s o

nth e C O nonitor s wer e conducte d usin g EP A Metho d 1 0 an

d a nalternat e netho

d (describe

d i nAppendi xE ) develope d durin g thi s study . Thi s alternat e netho d ca nb e use d t o check th

e accurac

y o f C O continuou s nonitor s usin g NDI Ra s th

e measuremen t technique .



### 4P.2 0

TABL E 1 . TENTATIV E PERFORMANC E SPECIFICATION S FO

R C O CEM S

PARAMETER S SPECIFICATIO N Ka n ( a Calibration Erro r Relative Accurac y 1. 2
Precisio n Respons e Tla e (tyataai ) Outpu t Kole e Zer o Drift , 2 lour s Zer o Drift . 2 4 loura 1 Spa nDrift . 2 4 lour a Interferenc e EquIT . J5 1 C0 » a a pp a C O 10 Z Hi O a a pp a C D Operationa l Period 0-100 0 pp a <2 Z Spa n <10 Z Hea

n Mf .
~ Valu e <1 Z Spa n £1 0 Hlaute a «1 Z Span «1 Z Span <2 I Span <2.S Z Spa

n
£1 0 pp a < 5 pp a >16 8 Hour a

Expressed a t aua o f absolut e aean value plu a 9S Z confidenc e Interva l ln a aerie s o f teata . T M a valu e l a baaed o n a relativ

e cooparlaon • f th e aosltor a to eachethe r an d no t t o Method 10 . Tba tene t ar e defined in Appendi x A .

TABL E 2 . TENTATIVE PERFORMANC E SPECIFICATION S FO R H 2 S CE> S

PARAMETER S SPECIFICATIO N Rang e CalibrationErro r

1 Relative Accurac y Keapona e Tla e (STatea ) Zer o Drift , 2 lour a Zer o Drift . 2 4 lour a Spa nDrift . 2 lour a SpanDrift , 2 4 lour s Operationa l Period 1 O-3O 0 pp a <5 Z o f Each

~ Calibratio n Mixtur e <10 Z Mea n Kef . " ~ Valu e <1 5 Mlnute a <2 Z Spa n <2 Z Spa n <2 Z Spa n <2.S Z Spa

n >16 8 ROUT

a Expretae d a taua o f absolut e Bea

n valu e plu a 55 1 confidenc e Interva l i n a aerie s e f teata .

### TABL E 3 . C O CEM S EVALUATE D INSTRUMEN T MANUFACTURE R MODE L NUMBER ABBREVIATIO N OPERATIN C PRINCIPA L
Anarad . tne . P . 0 . Bo a 318 0 Sant a Barbara . CA

9310 3 teolyte r Energetic s Scienc e 8 5 Executiv e Blvd . Otvlalo n o f

Beeto n Dickinso n Cuapsii j Elasford . N

T 1052 3 5 0 I R

3l07/2«4 v Anara d
Ecolyte r Nondleperalv e Infrare d Detecto r(NDIR

) Optica l Soli dStat s Detecto r EleetrocHealea l Senso r

Applie dAutomation , tne . Psvhusk a Roa d Bartleevllle . O R7400 4 Min e Safet y

Appliance s Ceaoany 7)2 2 Need e Stree t Pittsburgh , P A

1320 8 Optlchro a 10 2

LIR A 20 2 AA1 M

MS A Cas Chroaatoftrspti/Plea s

Io n Itatio n Detecto r (CC/FID ) Nondleeeralv e Infrered / Luf tDetecto r(NDIR/Luft )

h oTABL E 4 , H a S CEM

S EVALUATE

D INSTRUMOI

T MANUFACTURE

R MODE L NUMBE R ABBREVIATIO N OPERATIN C PRINCIPA L

Bend U Envlrewaants l » Proess aIsst t P . 0 . Drawe

r83 1 Levlsburg , V . V

A 2490 1 De l He rScientific , Inc . P . 0 . BO

B «R 6 Addison , Texa s 7770

DH- W Bend U

De l Mar Ca s Chraaatetraph/Plaa s Photoaetrl c Detecto r (CC/FPD) Lea d Aeetat atapregrste 4 Pepe rTap e Housto n Atlas , Inc . 944 1 Baythom e Driv e Houston , T

X 7704 1 825R/10 2 HA I Laad Acetat e taprsgrsts d

Pape rTap e Proces s Anslyters , UOI Stat e Roa

d Princeton , M

J lac . 32-23 0 PA I Ca s Chreaetotrspn/Plea a

Photometri c Detecto r (CC/FPD ) Teledyn e Anatvtlea l Tnnt t 3) 1 W . Missio n Avenue Sa n Cabrlcl . C

A 9177 8 ut a 81 1 DNCO-20I Teledyn e Ultraviole tAbaorptlo aSAMPL E CONDITIONIN G SYSTE M

FUE L OA S PIPELIN E

FUE L OA S SAMPL E LIN E

FIGUR E 1 . SKETC

H O F FIEL D EVALUATIO N SIT E

r o coP.2 4

SECTIO N 2 SUMMAR YAN D CONCLUSION S

CARBO N MONOXIDE MANUA

L METHOD Th e analytica l portio no f th

e manua l C

O tes t metho

d develope

d i n thi s stud

y wa s biase

d 4 percent hig

hwit hrespec t to a Bendi x8501 - 5C A NDIRC O analyzer . Th

e precisio

nassociate

d wit ha singl e analysi s wa s 4. 3 percent o f th e concentratio

nfo r th e range 1 0 t o 110 0 ppm . Th e precisio

nwa s approximatel y 2. 5 percen t o f th e mea nconcentratio

n fo r analyse s performe d i ntriplicate . Thi s mean s tha t tw o analytica l result s o

nth e sam e ba g sampl e shoul d differ b y mor e tha

n8. 4 percent onl y on e tim e i n2 0 du e to chanc e alone . Th e metho d wa s significantl y affecte d b y S0 ? an d NO , s o thes e compound s wer e remove d durin g sampl e collectio

nb y bubblin

g th e ga s throug

halkalin

e potassiu

nperman ganate . Tabl e 5 summarize s th e dat a collecte

d fo r eac hC O instrumen t durin g th e study . Table s 6 an d 7 summariz e th

e relativ

e accurac

y an d calibratio

ndrif t tests , respectively . Sometimes , les s tha nth e desire d nin e manua l metho

d test s were achieve d becaus e o f leakin g Tedlar bag s an

d proces s failure . Tabl e 8 show s th e effec t o f C0 2 , N0 X an d S0 ? o

neac hmonitor' s response . Th e followin g paragraph s summariz e th

e performanc e o f eac hlnstrunent . CARBO N MONOXID E MONITOR S Applie d Automatio

nOptlchro

m 10 2 Th e monito r performe

d wel l i

nth e laborator

y checkout , but'no t i n th e fiel d evaluation . A vali d relativ

e accurac

y tes t wa s neve r achieve d becaus e o f th

e monitor' s errati c performance ; thus , it s per cen t uptim e wa s zero . Ecolyze r 310 7 Thi s monito r wa s equippe d witha

nEnergetic s Scienc e Mode l 294 9 scrubber to remov

e N O an d SO. . Originally , eac hscrubbe r cos t $21 , but b y Jun e 1980 , thi s pric e ha d increase

d t o $45 . Th

e scrubber wa s foun d t o b

e inadequat e fo

r long-terr

a us e o

nFC C gases . scrubbe r failure , whichI

ntur ncause d monito r detector failure , occurre d fro m 1 t o 2 0 day s afte r Installatio n(dependin

g o nth e N O an d SO . concentratio

nencountered) . T o protec t th

e detector an

d sav e cost , a2 5 a nlon g b y 2. 5 ca diamete r PV C pip e containin

g activate

d charcoa l was.substituted fo r th e Mode l 294 9 scrubber durin g routin

e us e an

d th e Mode l 294 9 scrubber use d onl y durin g relativ

e accurac

y tests . Th

e respons e tim

e o f th e syste m withth

e large charcoa l scrubber installe d wa s approximatel y

3 0 minute s compare d t o les s tha

n1 minut e whe

nth e Mode l 294 9 scrubbe r wa s used . A t th e S0 ? an

d N O concentration s normall y

encountere

d i na nFCC stack (50 0 pp m SO. , 20 a pp

m N O ) eve na ne w Mode l 294 9 scrubber , wa s unabl e to remov e ai l o f th

e interferin

g gase s suc

htha t th

e instrumen t coul d pas s a relativ e accurac

y tes t (See R A tes t 2/8 1 (A ) i

nTabl e 6) . Carbo ndioxide a

t 1 5 percen t b

y vo l im e did no t interfere . Th e monito r drifte

d significantl y

over a perio d o f severa l days at frequent intervals . Th e detector wa s replace d onc e durin

g th e stud y an d th e evaluatio

nstoppe

d after th

e detecto r faile

d th e secon d time . Detector failure wa s als o a proble m i nth e previou s stud

y (2) . Thi s instrument doe s no t appear t o b e suitabl e to continuousl y monito r C

O concentration s i

nFCC emissions . Mine Safety

Applianc e (MSA ) Lir a 20 2
A s received , th

e output fro

m thi s monitor wa s no t compatibl e with th e dat a logge r thus , th e laborator y check-ou t test s wer e no t complete

d befor e th

e traile r wa s sen t t o th

e refinery . A

t th e refiner y th e monito r drifte

d o na dail y

basi s but , over a month , th e zer o an d spa ndrif t frequentl y

average

d ou t t o les s tha

n3 percent . N

o interferenc e wa s foun d fro m S0

_o r N O an d only a smal l an

d constan t interferenc e wa s foun d fro m CO . ( 1 ppr

a pe r 1 percent CO.) . Althoug h th e tes t wa s no t done , wate r vapor woul d not b e expecte

d t o b e a significan t interferent . Th e monito r successfull y complete

d th e 11-mont hevaluatio

nwithonly

tw o failures , botho f whic hwer e correcte

d b y a noptica l realignment . Anara d 501- R Except fo

r th e tim e i t wa s i

ntransi t to th

e refinery , thi s moni to r operate

d continuousl y

without a

noutage fro

m October , 197 9 unti l testin g wa s complete

d i nApri l 1981 . Interference s fro m SO . an

d N O were no t experienced , but small , constan t interference s did resul t fro m CO . ( 3 pp

m pe r 1 percen t CO. ) an d fro m water ( 3 pp

m pe r 1 percen t H.O) . Sinc e th

e stack ga s wa s conditione d to yiel d a dewpoin t o f -2 0 C , wate r wa s no t a ninterferent i

nth e field tests . Th

e monitor' s outpu t wa s usuall y

mor e stabl e tha

nan y o f th e other instruments . HYDROGE N SULFIDE MONITOR S Th e H. S CEM

s wer e evaluate

d i nth e laborator

y prior t o th

e fiel d testing . Tabl e 9 summarize s th e dat a collecte d fo r eac hH. S instrument durin

g th e study . Tabl e 1 0 summarize s th e relativ

e accurac y testin g performe

d i nth e field , an

d Tabl e 1 1 summarize s th e



### 1 0P.2 6

calibratio

ndrif t tests . I

nsom e relativ

e accurac

y tests , les s tha

n nine referenc e metho d sample s wer e collecte d becaus e plan

t upset s Increase

d th e H. S concentratio

nabov e th e spa nrange o f th

e monitors . Th e followin g paragraph s summariz e th e performanc e o f eac h instrument . Bendi xMode l 777 0 Thi s monito r operate d continuousl y

fro m initia l start-u

p unti l fina l shut-dow

nwithonly

fou r brie f outages . Tw o outage s wer e cause d b y a rupture

d diaphrag

m i nth e samplin

g valve , one outage occurre d whe na noperator accidentl y shorte d a circui t i

nth e heate r contro l uni t an d th e fourthoccurre

d fro m a nobstructio

ni nth e proces s ai r supply . Interference s wer e not detecte d durin

g th e initia l checkout . However , durin

g relativ

e accurac

y tests , a possibl e interferenc e fro m somethin

g i nth e fue l ga s wa s indicate d bu t coul d no t b

e confirmed . Sinc e th

e monito r sample

d th e fue l ga s onc e ever y 3. 5 minutes , i t wa s difficul t to conduc t a relativ e accurac

y tes t whe

nth e H. S leve l i

n th e fue l ga s wa s changin g rapidl y

(a s frequentl y

occurred) . Th

e instrumen t generall y performe

d i na reliabl e manne r throughout th e evaluation . Proces s Analyzer s Incorporate d Mode l 32-23 0 Thi s monito r operate d fo r les s tha

n3 day s durin

g th e laborator

y check-ou t an

d wa s returne

d to th

e manufacture r fo

r repair s o

nthre e separat e occasions . Mechanica l failure , electronic s failure an d corrosio

no f part s prevente d th e monito r fro

m obtainin

g a vali d analysi s o f th

e fue l ga s an

d thu s it s percent uptim e wa s zero . Th

e instrument doe s no t appea r suitabl e fo

r us e i nthi s application . Teledyne Mode l 61 1 DHCO-20 X Thi s monito r wa s receive d approximatel y

3 month s later tha n scheduled , whichprevente d a complet e laborator y checkou t o f th

e monitor . A

vali d analysi s o f th e fue l ga s wa s never obtaine d becaus e o f interferenc e fro m diethanolamine an d sulfu

r compound s suc

ha s mercaptan s an

d carbony l sulfide . Th e molecula r siev e scrubbe r originall y

supplie

d withth

e monito r coul d not compensat e fo r thes e interferences . B

y th e tim e Teledyn

e supplie

d a nimprove

d scrubber , th e monitor ha

d cease d to operate ; thu s it s percent uptim e wa s zero . Th e Instrument doe s no t appear to b e suitabl e fo

r us e i

nthi s application .



### 11P.2 7

Housto nAtla s Mode l 825R/10 2 Althoug hthi s monito r suffere d frequent mechanica l failure , i t di d complet e mos t o f th e fiel d testin

g program . Th

e mos t frequent caus e o f failur e wa s th e ga s dilutio

nsystem . Thi s i s th e sam e proble m tha t affecte

d th e Housto

nAtla s instrument evaluate d i na previou s study(3) . Thi s monito r require d a minimu

m o f 4 hour s fo

r a majo r calibratio

nand , at times , wa s subjec t t o sever e drifting . San e o f th e operationa l problem s encountere

d were du

e t o operator error an d th e corrosiv

e environmen t o f th e instrunentatlo

ntrailer . Som

e dat a wer e los t becaus e th e perso

nconductin

g th e dail y

check s faile

d to replac e th

e lea d acetat e tap

e i na timel y

manner . De l Ma r Scientifi c Mode l DM- W Thi s monito r operate d fo r th e entir e tes t progra m withou t mechanica l failure . However , becaus e rotameter s were use d to achiev

e a 1:1 0 dilutio

no f th

e fue l gas , it s calibratio nchange

d whe ndensity an d viscosity

o f th e fue l ga s changed . Sudde nchange s i

nth e ga s vis cosity occurre

d durin

g som e o f th

e relativ

e accurac

y tests ; thu s th

e agreement betweenMetho d 11 an d th e monito r varie

d drasticall y

durin g som e tests . A

bia s als o seeme

d t o exis t betwee

nth e monitor an

d th e manua l metho

d tha t coul d not b e explaine

d b y viscosity

changes . Sam

e dat a were los t becaus e th e perso nconductin

g th e dail y check s faile

d t o replac e th

e lea d acetat e tap

e i na timel y

manner .



### 1 2TABL E 5 . DAT A SUMMAR YO F CO CEM S
SPECIFICATION S PROPOSED I

N REF . 2 ANARA D ECOLYZER 

### MS A A/110 2



### w UBORATOR YDAT

A Precisio

n( Z FS ) Spa nNois e ( Z FS ) Zer o Nois e ( Z FS ) H^ O Interferenc e (a s pp nCO ) 1* Z CO 2 Interferenc e (a s pp m CO ) Respons e Tim

e (seconds ) FIELD DAT

A Zer o Drift , 2 4 Hr . ( Z FS ) Zer o Drift , 2 Hr . ( Z FS ) Spa nDrift , 2 4 Hr . ( Z FS ) Calibratio

nErro r ( Z FS )

- hig h( Z FS )

- mediu m ( Z FS )

- lo w ( Z FS ) Fiel d Respons e Time , 90Z/95 Z F S (seconds ) Instrumen t Operationa l Tim e (* ) 

### < 1

< 1 a < 4 

### <1 0 ^60 0



### < 2 < 1 <2. 5 

### < 2 a a a <60 0 

### a <0. 1

<0. 1 

### 0. 5 32. 4 28. 2 

### 7. 5

2. 5 0.8 9 

### 4. 2 1. 7 9. 1 4. 7 13/1 6 

### 10 0 <0. 1

<0. 6 

### 0. 4 n/ a <0. 1 

### 5 3

9. 2 1. 3 53. 8 

### 5. 0 13. 0 

### 4. 6 45/4 7 

### 5 7 <0. 1

<0. 2 

### 0. 1 b b 4. 8

2. 2 1. 3 3. 1 b b b 11/1 3 

### 8 6 <0. 1

<0. 1 

### 0. 9 3. 0 <0. 1 

### 13 8

0. 4 0.4 2 

### 4. 3 2.6 C 6.9 C 8.4 C 242/24 2 

### 0

No t specified . Dat a no t complet e du e t o instrument malfunction . Resul t o f on

e test . Tim e th e instrument wa s producin g useabl e dat a durin g th e 11-mont

hfiel d evaluatio

nvlthou t considerin

g th e absolut e accuracy o f th e data , i.e. , withou t correctin g fo r th

e day s th

e monito r wa s ou

t o f calibration . However , if th e monito r wa s know

nt o be malfunctionin g an d no t jus t ou

t o f calibration , th

e monitor va s considere d t o b e of f line .TABL E 6 . SUMMAR YO F C O RELATIV

E ACCURACYTEST S A T REFINER Y

DAT E 9/8 0 1/8 1 2/8 1 2/8 1

Mean 

### (A ) (B ) NUMBE

RO F REFERENC E METHOD SAMPLE S 

### 5 9 9 9 . MEA

N CO CON C (* ) 

### 2 2 1 2 3 LCV * CO CON C (ppm ) 

### 8 0 40 4 507 d 

### 71 2 ECOLYZE R Z Std " 

### 5 1 4 >10 0


### e 4 0 Z [CO ]



### 3 4 17 >10 0


### e 5 0 RELATIV

E ACCURAC

Y ANARAD

b Z Std L 

### 3. 8 13 7. 7 12. 7 

### 9. 3 I

ICO ) 

### 24 1 6 7. 6 8. 9 1 4 MSA b Z Std " 

### 2. 9 1 3 4. 2 9. 7 7. 4 X

[CO J
18. 4 

### 1 6 4. 3 6. 8 1 1

b c d Thi s i s th

e avirag e o f th

e manua l metho

d result s usin

g th e letic o crysta l viole t metho d developed i nthi s study . Correcte

d fo r CO . interference . Standar d fo r CO : 50 0 ppm . Monitor s sample

d cylinde r gase s containin g 50 2 pp

m CO , 12 Z CO . an

d differen t concentration s o f N O an d SO . innitrogen . Thi s wa s don e to evaluat e th

e performanc e o f th e monitor s vhe n the y ver e samplin

g a stack ga s vit hN O an d SO . level s representativ e o f a nFC C stac k gas . Durin g th e ll-monthstudy , proces s upset s an d refiner

y equipment malfunctioncause d th e C O level s t o excee

d th e spa nrange o f th

e monitor s an

d s o it va s necessar y t o dilut e th

e stack ga s to brin

g th e CO leve l int o th

e vorkin

g range o f th

e monitor s durin

g th e relativ

e accurac y test . Dilutio

nva s obtaine

d b y introducin

g plant instrument ai r a t th e probe . Thi s dilutio

nreduce

d th e N O an d SO . level s b

y a facto

r o f 4 to 6 an

d permitted th

e Ecolyzer to obtai na naccurat e analysi s o f th e stac k gas . Monitor not operationa l becaus e o f detector failure fro m hig hSO . an

d N O level s encountere d i nTes t 2/81(A) .P.3 0

TABL E 7 . CALIBRATIO N DRIF T TES T RESULT S FO RC O MONITOR S



### DA Y

Tes t 1 

### 1 2 3 4 5 6 7 Tes t 2 

### 1 2 3 C 

### 4 5 6 7 Tes t 3 

### 1 2 3 4 5 6 7 CALIBRATIO N ECOLYZE R Zer o



### 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

• Spa

n



### 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 )

ANARA D Zer o



### 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 Spa

n



### 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 MS

A Zer o



### 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 Spa

n



### 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

* Value s lntabl e represen t th e dail y drif t a s define

d b y th e followin

g equatio

n {Calibratio

nCa s Concentratio

n- Monito r Reading ! x100 Z Monito r Spa

nValue 

### b Becaus e long-ter m drif t wa s o f primar y concern , th

e instrument s wer e not zeroe

d dally . Th

e value s inth

e tabl e hav

e been correcte

d b y th e dall y zero drift .



### 1 5TABL E 8 . EFFEC T O F C0 2 » NO x , SO j O N C O MONITOR S

DAT E
6/5/8 0 9/20/8 0 11/18/8 0 1/20/8 1 2/17/8 1 2/17/8 1

* 2/17/8 1 

## teo )

(ppm )

100 C 100 C 

## ioo c 

## ioo c
500 d 500 e 500 f MONITO RRESPONS E (ppm ) Ecolyze r Anara d


### 165 141 b 20 6 168 0 143 0 166 0 

### 149

13 9 152 14 0 544 53 8 52 3 MS

A
11 7 112 113 10 7 50 4 51 2 50 4 MONITO

RRESPONS E CORRECTE D FO R Ecolyzer Anara d


### 165 14 8 b 20 6 168 0 143 0 166 0 

### 11 3

10 1 11 6 10 4 50 8 50 2 48 7 CO 2 1 IfTERFER E MS A


### 10 5 10 0 10 1 9 5 49 2 50 0 49 2 NC ^

CO - Interference : Ecolyze r - none ; Anara d - 3 ppm/l Z C0- , MS A - 1 ppm/l Z CO- . Monito r no t operationa l becaus e o f detecto r failure . Cylinde r Analysis : 12 Z C0 2 ; 20 0 pp m NO ; 50 0 pp

m S0 2 ; balanc e Nj . Cylinde r Analysis : 12 Z C0 2 ; 40 0 pp m NO ; 0 pp

m S0 2 ; balanc e Nj . Cylinde r Analysis : 12 Z C0 2 ; 0 pp m NO ; 70 0 pp

m S0 2 ; balanc e N 2 > f Cylinde r Analysis : 12 Z C0 2 ; 20 0 pp m NO ; 50 0 pp

m S0 2 ; balanc e Nj .TABL E 9
. DATASUMMAR Y O F Hj S CEM S

SPECIFICATION S PROPOSE D IN REFERENC E BENDI X DE L MA R 

### HA I 

### PAI TELEDYNE
LABORATORY DAT

A Precisio n ( Z FS ) Spa n Nois e ( Z FS ) Zer o Nois e ( Z FS ) 10 0 Z Cf yInterferenc e ( Z FS ) 40 Z CH Ai n H 2 Interferenc e ( Z FS ) 20 0 pp mCH3S H Interferenc e ( Z FS ) Respons e Tim e (sec ) FIEL D DATA Zer o Drift , Zer o Drift , Spa n Drift , Spa n Drift , 2 4 Hr . ( Z FS )

2 Hr . ( Z FS ) 2 4 Hr . ( Z FS ) 2 Hr . ( Z FS ) Calibratio n Erro r ( Z FS )

- high ( Z FS )

- mediu

m( Z FS )

- Iov ( Z FS ) Fiel d Respons e Time , 90Z/95 Z F S (sec ) Instrumen t Operationa l Tim e (* ) a a a a a a <90 0 

## I 2 <2 ^2. 5 <2 < 5 a a a £90 0 a 0. 3

0. 4 0. 1 <0. 1 <0. 1 <0. 1 21 0

0.0 4 0.0 5 1. 7 0. 6 0. 7 6. 2 8. 0 230/23 0 8 9 4. 3

1. 1 2. 1 <0. 1 <0. 1 <0. 1 30 6

5. 2 2. 1 11. 7 3. 4 9.2 C 32 c 17 c 304/32 8 

### 9 7 2. 8

0. 9 0. 5 -0. 2 -0. 4 <0. 1 63 0

1. 6 1. 9 13. 4 13. 1 14 c 20 c 40 c 480/58 3 7 6 b

b b b b b

b b b b b b b b 0 0. 6

0. 6 2. 4 < 1 < 1 8 2 3 5

b 6. 1 b 2. 1 9.3 C 30 c 4 7 b 0

No t specified
. Dat a no t complet e du e t o Instrumen t malfunction
. Resul t o f on e tes t only
. Tim e th e instrumen t va s producin g useabl e dat a during 11-mont h fiel d evaluatio n vlthou t considering th e absolut e accurac yo f th e data , i.e. , vlthou t correcting fo r day s th e monito r va s ou t o f cali

bration
. However , i f th e monito r va s knov n t o b e malfunctionin g an d no t jus t ou t o f calibration , th e monito r vn s condidere d t o b e of f line
., TABL E 10 . SUMMAR YO F H ? S RELATIV

E ACCURAC

YTEST S A T REFINER

Y

! TES T STAR

T 

### NO . DAT E RELATIV E ACCURAC

Y NUMBE R O F METHOD 1 1 REFERENC E MEA

N H a S METHOD CON

C BENDI XHOUSTO N ATLA S UE L MA

RTELEDYNE SAMPLE S . ( ppm ) 2 std dZ (H 2 S ] * 7 . std " 2 lH 2 S] a Z std " Z [H 2 Sl * 2 std ° 2 [HjSj "

1 4/27/8 0 2 5/5/8 0 3 6/9/8 1 4 A 1/20/8 1 4 B 1/20/8 1 5 2/18/8 1 La b1 La b2 6 7 8 2/25/81 ' 2/25/8 1 3/31/81 ' 9

9 9 9 9

9 7 6 8 1 0 15 9

20 1 20 8 19 0 19 7

34. 6 31. 7 15 0 13 8 11 4 28. 9 3 9 58. 8 18. 5 16. 4

18. 1 22. 4 11. 1 33. 5 8. 3 29. 9

3 2 47. 4 16. 1 13. 7

86. 4 11 7 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

11 6 14 8

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

15 3 20 5 11 5

7 4 b b b

b b

c c 21. 5 31. 1 b

b b 11 9 6 1 b b b

b b b b b

Standar d - 16 5 pp

m H 2 S . Spa

n[H 2 S ] - Metho

d 1 1 result . Monito r no t operational . Monitor operationa l bu t no t include d i ntes t becaus e l t coul d no t b e brough t int o calibration . Fue l ga s spike

d vit hknov

namount o f H 2 S usin g HoustonAtlas , Inc . Mode l 60 1 diluter .

### TABL E 11 . CALIBRATIO

N DRIF T TES T RESULT

S FO RH. S MONITOR

S

TES T CALIBRATIO N DRIFT* * b 

### (2 ) KUMBE RBENDI X HOUSTO

N ATLA S DE

LMA R Zer o Span Zer o Spa n Zer o Span Tes t1 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 10 1 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 Tes t 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 Tes t 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 Tes t 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

* - Value e l o tabi c represen tth e dul y drif t• • define d b y Ch * followin g equatio n |Ce31bretlo n Ga

aConcentratio n - Monito rKcadlm l • 100Z Hon1to rSpa

n Valu e » * Secaua e long-tei- adrif twa ao f prlaar y concern , th e inatrunent a wer e no taeroe d dally . Th e value e l n th e tabl e hav e bee n correcte d b

y th e dall y ser o drift . 

### 1 9P.3 5

SECTIO N 3 RECOMMENDATION S

CARBO N MONOXID E CONTINUOU S EMISSIO N MONITOR S Th e Anara d an d MS A monitor s successfull y complete

d th e 11-mont

h stud y an d demonstrate

d tha t monitor s withgoo d drif t contro l ar e availabl e an

d suitabl e fo

r th e measuremen t o f C

O concentration s l

nFC C emissio ngas . Base

d o nth e result s o f thi s study , th e followin

g specification s are advance d fo r C O monitors .

• Calibratio

nDrift . Th

e CEMs calibratio

nmus t not drif t or deviat e fro

m th e referenc e valu

e o f th

e calibratio

n ga s b y mor e tha

n5 percent o f th

e establishe

d spa nvalue o f 1,00 0 pp

m over eac

h24-hou

r operatin

g period .

• Relativ

e accurac

y (RA) . Th

e R A o f th e CEMs mus t b

e n o greate r tha n2 0 percen t o f th e mea nvalu e o f th e referenc e metho

d (RM ) tes t dat a i nterm s o f th e unit s o f th e emissio

nstandar

d o r 1 5 percent o f th e applicabl e standard , whicheve r i s greater , a s calculate d usin g Equatio n2- 4 i

nReferenc e 4 an

d th e manua l C

O metho d result s a s th

e referenc e value . Th e correlatio

namon g th e referenc e metho

d an d CE M data , th

e number o f R

M test s an

d th e calculation s shoul d b e th e sam e a s thos e giveni nSectio

n7 o f Performanc e Specificatio n2(4) . Becaus e o f th

e possibility

o f leak s whe

nsamplin

g wit hTedlar bags , th

e number o f sample s take nfo r a relativ

e accurac

y tes t shoul d b e a t leas t twelv

e wit hth e optio no f discardin

g th e result s fro

m an y thre e i f i t appear s tha t leakage ha s occurred . Th e relativ

e accurac

y testin g shoul d b

e don e whil e th

e C O concentratio

nl nth e emission s i s varyin g les s tha

n1 0 percen t over th e duratio

no f th e testing . HYDROGE N SULFIDE CONTINUOU S EMISSIO N MONITOR S Th e performanc e o f th e H. S monitor s wa s disappointing . Onl y thre e o f th e fiv e monitor s wer e suftabl e fo r field us e an

d onl y on e monito r (Bendix ) ha

d a nuptim e l nexces s o f 8 5 percent . Th e othe r tw

o moni tor s tha t passe

d th e tes t suffere

d sever e drif t problems . Th e Bendi x



### 2 0P.3 6

sample d a tota l o f 1 7 time s eac hhour , but eachsampl e duratio nwa s les s on e second . Thus , th e us e o f th

e integrate

d Metho d 1 1 samplin

g approac hfo r determinin

g th e accurac

y o f thi s monito r l s questionabl e unles s th

e fue l ga s H. S concentratio nca nb e held constant . Th e absolut e agreemen t betwee nMetho d 1 1 an d al l th

e monitor s wa s poo

r an d variabl e i

neight o f th

e te nrelativ

e accurac

y test s a s show

ni nTabl e 10 . Sinc e th

e caus e o

r cause s o f thi s differenc e coul d not b e Identified , th

e us e o f H. S monitor s fo r complianc e purpose s canno t b e recommende

d a t thi s time . Th e monitor s ma

y b e useful , however , fo r determinin

g trend s an

d fo r indicatin

g amin e treate r performance , a s show nb y th e overal l agreemen t betwee

nth e average fo

r al l Metho

d 1 1 test s an

d tha t fo

r eac hmonito r (i.e. . Metho d 11-14 0 ppm , Bendix-11 9 ppm , Housto nAtlas 13 0 pp m an d De l Mar-13 3 ppm) . (Som e Metho d 1 1 test s use

d i ncalcula tin g th e abov e average s wer e not reporte d i nth e tex t o f thi s repor t becaus e the

y represente

d case s wher e plan t malfunctio

no r instrumen t failur e cause

d a relativ

e accurac

y tes t t o b

e aborte

d befor e a

nade quat e number o f sample s ha d bee nobtained) . Du e to th

e apparent bia s betwee nth e Referenc e Metho

d 1 1 test s an d th e H. S CE

M data , a

ninterferenc e to th e referenc e metho

d test s i s suspected . Additiona l evaluatio no f th e referenc e metho

d shoul d b

e performe d befor e performanc e specification s ar e develope d an d installatio

no f monitor s i s required .



### 2 1P.3 7

SECTIO N 4 DESCRIPTIO

N O F EQUIPMEN

T

CONTINUOU S EMISSIO

N MONITOR S Carbo nMonoxide Monitor s Applie d Automatio

n.Optichro

m 102 — Th e Mode l 10 2 l s a ga s chromatograp htha t use s a flam e ionizatio

n detector (FID ) to detec t methane catalyticall y produce

d fro m carbo n monoxide . Th

e oven , valve s an

d control s are locate d l na nai r purge

d modul e an

d th e programmer i s l

na separat e cabinet . A sampl e loo

p i s use d to sampl e a

nexac t volum

e o f ga s whic

hl s Injecte

d ont o th

e colum nb y a mult i por t valve . Tw o column s i

nserie s ar

e use d fo r th e separatio

n- whe

nth e C O ha s elute

d throug

hth e firs t column , i t i s backflushe

d to remov

e th e heavie r component s whil e additiona l separa tio ntake s plac e o

nth e secon d column . A

catalyti c methanator con vert s th

e C O t o methane (i

nth e presenc e o f hydroge ncarrier gas ) whic hl s detecte

d b y th e FID . Automati c zeroin

g l s accomplishe

d vi a a

naut o zer

o contro l o

nth e detector Immediately before th

e C O pea k reache s th

e detector . Span nin g i s accomplishe

d b y a serie s o f attenuatio nswitche s an

d a fin

e attenuatio

npotentiometer . Ecolyzer 3107 — Th e Ecolyze r Mode l 310 7 monitor utilize s a nelectrochemica l senso r to measur e C

O i nth e range s o f 0 t o 100 0 pp m an d 0 t o 50 0 ppm . Th e uni t utilize s a samplin g pum p an d a by-pas s to ven t unuse d sampl e aroun d th e sensor . To maintai nConstant sampl e humidity , a sal t wate r humidifer i s locate d upstrea

m o f th e detector . A

nabsorbent cartridge l s provide

d fo r th e remova l o f SO . an d N O fro m th e sampl e gas . Sampl e pressur e mus t no t excee d 2. 5 c m water a

t th e sampl e pum

p inlet . Min e Safet y Appliance s Lir

a 202 — Th e Lir a 20 2 ha s tw

o I Rlamps , a "Luft-type " infrare d detector an d gold-line

d sampl e an

d referenc e cells . On e lam p passe s throug

h th e sampl e cel l an

d th e othe r lam

p throug

hth e referenc e cell . Th e emergent radiatio

nfro m bothcell s I s directe d to a singl e detector cell . A

s th e ga s i

nth e detector absorb s radiation , it s temperatur e an d pressur e increase . A nexpansio

no f th

e ga s i nth e detector cause s th e membran

e o f a condense r microphone t o distort . Thi s distortio ni s converte

d t o a nelectrica l signa l whic hl s amplifie

d to produc e a

n output signal . Th e entir e analyzer i s kep t a t a constan t temperatur e b y a thermostaticall y controlle

d heate r an

d blower Installe

d i nth e case .


### 2 2Ar.ara d 501R — Thi s NDIRanalyze r use s unline d Plexiglas s sampl e an d referenc e cells . Th

e monito r consist s o f a singl e I Rsource , paraboli c mirrors , a chopper , a

noptica l solid stat e detector an d a noutput modul e that ca nb e separate

d fro m th e res t o f th

e monitor . HydrogenSulfide Monitor s Bendi x7770 — Th e Mode l 777 0 ga s chromatograp hmonitor s H. S usin g a nFPD . A sampl e block l s use d to injec t a volum e o f sampl e ga s ont o th e firs t column . After th

e H. S ha s elute

d throug

hth e firs t column , th

e colum n i s backflushe

d t o remov e th e heavier components . Further separatio n i s attaine

d l nth e secon d colum

nprio r t o H. S detection . Zeroin g i s automati c durin

g th e runnin

g program , bu

t a zer

o offse t contro l i s als o provide

d insid e th e programmer . Ih

e instrument cycl e tim e i s 21 0 seconds . Clean , dr y ai r i s use

d a s th e carrier gas . Proces s Analyzer s Incorporate d 32-230 — Th e Mode l 32-23 0 monitor i s a ga s chromatograp hequippe

d wit ha flam e photometri c detector (FPD ) tha t i s sensitiv e to sulfur . A volum e o f sampl e i s injecte d int o th

e analytica l colum

nfro m a sampl e loop . After th

e H. S sampl e ha s elute d pas t th

e firs t column , th e colum ni s backflushe

d t o remov e heavie r compounds . Th e H. S continue s throug hth e secon d column . A

t th e proper tim

e fo r th e H. S componen t t o elud e throug

hth e column , th

e flam e photometri c sensin g circui t i s activate

d t o detec t th

e H.S . Zeroin

g l s automati c an d occur s immediatel y

befor e th

e elutio

no f th

e pea k o f interest . Spa ni s accomplishe

d b y adjust - in

g a nattenuatio

npotentiomete r insid e th e case . Teledyn e 61 1 DMC0-20X— Thi s dua l bea

m monitor utilize s ultraviole t absorptio nto quan tif y H. S concentratio

ni nth e sample . A

12-lnch-lon

g optica l cel l ha s continuou s sampl e flow . O non e en d o f th

e sampl e cel l i s a nultra viole t sourc e an

d o nth e other en

d a detector . A

rotatin

g choppe r withtw

o filter s 180 ° apar t i s locate d betwee

nth e cel l an

d th e detector . On e o f th e filter s passe s onl y a know

nabsorptio n wavelengt hfo

r H.S , th

e other a wavelengtha t whic hH. S doe s no t absor b(referenc e beam) . Th e wavelength s ar e no t specified . Synchronizer s an

d electri c circuitr y subtrac t th

e non-H. S absorptio n (referenc e beam ) fro m th e tota l absorption . Housto nAtla s Mode l 825R/102 — Th e Mode l 825R/10 2 monitor operate s o nth e principl e o f lea d acetat e impregnate d paper tap

e reactin

g t o change colo r i nth e presenc e o f H.S . A cadmiu m sulfid

e photocel l i s use d a s a detector . Th e photocel l outpu t feed s a preamplifier . Th e outpu t o f th

e preamplifie r feed s a low-pas s filte r whic hdifferentiate s th e signa l withrespec t to time . Th e resultant differentiate d outpu t provide s a D C signa l that ha s a pea k amplitud

e directl y

proportiona l to th e Hg S concentration .


### 2 3P.3 9

T o obtai na sampl e l nth e concentratio

nrange o f measuremen t b y lea d acetat e tape , th e monitor I s equippe d witha.slidin

g bloc k dilu ter . Ihi s dilute r mixe s a measure d volum

e o f sampl e wit ha strea m o f diluen t gas . Th

e amount o f dilutio nl s adjuste

d b y varyin g th e Injec tio nfrequenc

y o f th e sample . Zero an d spa nadjustment s ar e made b y adjustin

g potentiometer s Insid e th e case . Del-Mar Scientifi c DM-W — Th e DM-W use s a lea

d acetat e impregnate d paper tap

e that i s expose d to th

e ga s strea

m a s i t move s pas t a naperture . Th

e H. S i n th e ga s strea

m cause s a blac k precipitat e (lea d sulfide ) t

o for m o n th e tape . Colo

r developmen t l s monitored b y a photocel l tha t measure s light reflecte

d of f th

e tape . Becaus e th

e DK-W normall y

operate s i

nth e 0 t o 5 0 pp

m H. S range , De l Ma r supplie

d a dilutio

nsyste m withth

e monitor . Thi s syste m wa s comprise

d o f tw

o rotameters , a mixin g chamber an

d a back pressur e regulator . Th

e fue l ga s sampl e wa s dilute d withnitroge

na t th e recommende d rati o o f 1:1 0 b y adjustin g needl e valve s o nth e rotameters . ANCILLAR

YEQUIPMEN

T Al l monitor s an

d dat a aquisitio

nequipment were installe d i na 24-foot-lon

g traile r equippe d wit hheatin

g an d ai r conditioning . Figur e 2 shows th

e locatio

no f al l equipment withi nth e mobil e labora tory . Th e C O sourc e wa s a stack o na FCC unit . Th

e C O boile r stac

k ga s contained : 150 . t o 30 0 pp m N O , 20 0 t o 60 0 pp

m SO. , som

e aci d mist , 5 0 t o 30 0 mg/m

particulat e n?atter , 1 0 t o 1 4 percen t H.O , 9 t o 1 4 percent CO. , an

d 2 0 t o 10,00 0 pp

m CO . Th

e temperatur e a

t th e samplin

g point wa s approximatel y 32 0 C (60 0 F) . Th e H. S sourc e wa s a fue l ga s pipelin e locate

d approximatel y

12 0 meter s fro

m th e trailer . Stainles s stee l tubin g (0.6 3 c

m OD ) wa s use

d t o connec t th

e ga s lin

e t o th e traile r H. S distributio nsystem . Th

e samplin g poin t wa s dow

nstea m o f a namin e treater . Vhe

nth e monitor s were firs t Installe d i nApri l 1980 , th

e treater wa s usin g diethanol amine fo

r th e remova l o f H.S , but i nMarc h1981 , th

e treate r wa s refurbishe

d an d monoethanolamine replace d th e diethanolamine . Th e H- S leve l i nth e fue l lin

e range d fro m 5 t o over 1,00 0 pp m durin g thi s study . Flui d Catalyti c Cracke r Emissio nSampler/Conditione r A nEPA-deslgne

d sampl e conditionin g syste

m wa s locate

d at th

e samplin g por t 6 0 meter s abov e groun d leve l o

nth e C O boile r stack . Th e drie d (dewpoint -20°C ) an d filtere

d sampl e wa s transporte d 20 0 meter s t o th

e traile r b

y usin g unheated , 9. 5 o nI D black , nylo

n tubing . A

detaile

d descriptio

no f th

e sampl e conditionin g syste m an d it s per - formanc e i s include d l nAppendi xD .


### 2 4P.4 0

Sampl e Distributio

nSystem

s Inth e trailer , th

e ga s sample s fro

m th e source s wer e distribute d to th e monitor s b

y usin g th e distributio

n(manifold ) system s show nln Figure s 3 an

d M. Th

e water colum

nwa s include

d o nth e C O distributio

n syste m to ensur e tha t constant pressur e wa s maintaine d lnth

e system . I naddition , a pressur e reducer wa s Include d to ensur e tha t th e Ecoly ze r inle t pressur e wa s maintained belo w 2. 5 c m water . Eac

hdistri butio nsystem

s wa s fitte

d withsolenoi d valve s o nth e spa nga s an

d nitroge nga s line s to facilitat e automati c dail y zer o an d spa ncheck s b y th e dat a aquisitio

nsystem . Dat a Acquisitio

nSystem/Automati c Zero/Spa nSyste m Eac hmonito r wa s connecte d t o th e Esterlin

e Angu s Mode l PD-206 4 dat a logger . Th

e PD-206 4 converte d th e 4 t o 2 0 m

A outpu t o f eac

h monito r t o 2 5 t o 12 5 m V an d provide

d approximatel y

a -2 5 m

V offset . Eac hInstrument the

nshowe d a respons e o

nth e PD-206 4 o f 0 t o 10 0 mV . Th e PD-206 4 i s abl e to monitor al l 1 6 channel s continuousl y o r to sca

n the m a t an y desire

d frequency . I

naddition , th

e syste

m ca nsca n selecte d channel s a

t an y desire d interva l an

d average th

e reading s fo

r eac hchanne l after th e desire

d number o f scans . Durin g th e field testing , eac

hmonitor' s output wa s scanne d ever y 3 minute s except whe n relativ e accurac

y an d calibratio

nerror test s wer e conducted . I n thos e case s sca

ntime s o f 1 minut e wer e usuall y used . After te

n scans , th

e reading s were average d an d th e result s were printe d o nth e paper tape . Th

e dat a an

d tim e o f printin

g were als o recorde d o nth e tape . Ever y 2 4 hr , th e dat a logge r automaticall y accomplishe d a zero/spa

ncheck o f th

e monitors . A

t a se t tim

e the - dat a logger close d th e contact s leadin

g t o a solenoi d valv

e i nth e sampl e distributio n system . Thi s valv e shut of f th

e sampl e ga s an

d opene d th e nitrogen (zero ) gas . After 1 5 minute s th e dat a logger too

k a singl e readin

g o n eac hchanne l an

d printe

d th e value . Th

e firs t se t o f contact s the n opene d an d a secon

d set close

d t o allo w spa nga s to enter . After 1 5 minute s th

e dat a logger agai nrea d eac hchanne l an

d printe

d th e value . Th

e secon

d se t o f contact s the nopene

d an d th e origina l progra m o f scannin

g an d printin

g resuned . EP A Referenc e Metho

d 11 wa s use

d throughout a s published . Equip men t listing s are publishe d i nth e Method.Th

e manua l metho

d fo r C O analysi s i s presente d i nAppendi xE . Al l equipmen t i s describe d therein .



### 2 5SPARE S

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M HEOUIATO S 

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### FIGUR E 2 . SKETC H O F INSTRUMENTATION TRAILE RSHOWIN

GINSTRUMEN T ARRANGEMENT .P.4 2



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_ _ I N *— ZER O OAS
. I N > ~ SPA N OA S

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PRESSUR C FLAS K

FIGURE 4 . PLUMBIN

G DIAGRA

M FO RFUEL GAS DISTRIBUTIO N T O TH E Hj S CEM SSECTIO N 5 EXPERIMENTA

L PROCEDURE S

GENERA L PROCEDURE S Calibratio

nCase s Calibratio

ngase s use

d fo r thi s evaluatio

nwere Certifie

d Maste r Gase s supplie

d b y Scot t Specialt

y Cases , Plumsteadville , PA . Calibra tio ngase s wer e selecte d t o b e 15 , 50 , an

d 9 0 percent o f th e instru ments ' spa

nrange withnitrogenbein g th e balance . Th

e gase s wer e analyze d an d certifie

d t o b e + 2 percent o f th e state d values . Metho

d 11 wa s use

d to verify

th e H. S ga s concentration s an d a BendixMode l 850 1 5C A NDIRC

O monito r calibrate d withNB S standards , wa s use d t o verify th e C O ga s concentrations . Calibratio

nProcedure s Eac hInstrumen t wa s calibrate d accordin

g t o th e manufacturer' s Instruction s b

y usin g th e appropriat e sampl e distributio nsyste

m t o Introduc e th

e calibratio

ngas . Calibratio ncurve s were generate d fo r eac hmonitor . Throughou t thi s evaluation , al l instrumenta l respons e reading s were obtaine

d fro m th e digita l millivol t outpu t o nth e Esterlin

e Angu s PD-206 4 dat a logger . Spa nan d zer o adjustment s were made o nth e Instrument s t

o produc e a proper millivol t respons e o nth e PD-206 4 dat a logger . UBORATOR YEVALUATIO N O F TH E MONITOR S Th e monitor s were evaluate d i nth e laborator

y withth

e procedure s describe

d i nth e Federa l Register(5) . Th e followin

g parameter s which are define

d i nAppendixA , wer e evaluated :



### • precisio n • nois e • respons e time s (ris e an d fall )
• H- 0 an

d CO - interferenc e fo rC

O monitor s • CR ^ an d CH^S H interferenc e fo rHg S monitor s • flo w an

d temperatur e variatio n

2 9Precisio n(Repeatability ) Precisio

ni s th

e standar

d deviatio

nabout th

e meano f repeate

d measurement s o

nth e sam

e ga s concentratio n(2) . I nthi s test , measuremen t o f th e selecte

d ga s (e.g. , aid-span ) wa s Interrupte d alternatel y

b y th e introductio no f a highe r an d a lowe r ga s concentration . Si

xstabl e reading s o f th e selecte

d ga s wer e obtaine d Inthi s manne r an

d th e precisio

nwa s calculate

d a s follows :

P - * 6

Z 1- 1 P. * - 

## 4 ( I Pa )

6 

### 1-1 * 

# ' ] (1 )

Where : P s Precisio n P . * Instrunen t respons e (ppm ) fo r th e 1 o nth e selecte

d gas . 

### t h measuremen t

Outpu t Nois e Instrumen t nois e i s a short-ter m variatio

ni ninstrument outpu t no t cause

d b y change s inoutpu t concentration . Thi s value i s "expresse

d i nconcentratio

nunit s a s th

e standar

d deviatio

nabout th

e mea n(2) . Th e tes t procedur e involve d allowin

g th e instrument t o stabiliz e o nth e ga s standar

d (either zer

o o r span ) an

d the ntakin g 2 5 reading s withi na 6 0 minut e perio d b y usin g a digita l voltmeter . Thes e reading s (expresse d Inconcentratio nunits ) wer e entere d int o th

e followin

g equation : 

# •^[l ir

# S-'*<l *s] (2 )

Where : S

r . 

### s Instrunen tNois e (ppm) 

### t h s Instrunen t Respons e fo r th e 1 readin

g (ppm )
Instrumen t Respons e Tim e Ris e tim

e I s th

e tim e Interva l betwee

nth e initia l instrunent respons e an

d 95 Xo f th

e fina l respons e after a ste p increas e i

ninput ga s concentration . Th e tes t procedur e involve d changin

g th e inpu t fro m zero ga s to a high-range spa nga s an

d determinin

g th e tim e require d to reac

h9 5 J o f th

e high-rang e spa

nga s concentration .



### 3 0P.4 6

'Fal l tim e i s th e tim e differenc e betwee n th e Initia l respons e an d 95 X o f th e fina l respons e afte raste p decreas e l n inpu tga s concentration . Th e tes tprocedur e involve d changin g th e inpu tfro m a high-rang e spa n ga s t o zer o ga s an d determinin g th e tim e require d t o reac h 5 % o f th e spa n value . T o obtai n th e prope rris e an d fal l times , th e "dead volume " i n th e sampl e line s wa s minimize d b y placin g athree-wa y stopcoc k a s nea r a s possibl e t o eac h instrument' s sampl e port . Th e sampl e ga s wa

s switche d fro

m zer o t o spa n by usin g thi s three-wa y stopcock . Th e char trecorde rwa

s use d a tit s fastes tspee d durin g th e test . Th e respons e time s wer e calculate d fro m th e stri p chart . Thre e ris e time s an d thre e fal l time s were calculate d an d th e result s o f

eac h se twer e averaged . Th

e Instrumen trespons e reporte d i n Table s 5 an d 9 i s th e large ro f

thes e tw o values . CO . and ' H.

O Interferenc e fo rC O Monitor s

— 2 2 Carbo ndioxide interferenc e wa s determine d b y usin g a Scot t blen

d o f 1 0 percent CO . i n nitrogen . Th

e respons e t

o th e introductio

no f th e 1 0 percen t CO . i s expresse d i npp m a s a n equivalen t CO concentration . Wate r interferenc e wa s determine d b y addin g water vapor whil e th e instrument wa s samplin g nitroge

n(zero gas) . Th e respons e to th

e adde d wate r vapo r wa s expresse d in pp m a s a n equivalen t C O concentration . Wate r vapor wa s adde d b y passin g nitroge

nthroug

ha flas k containin

g distille

d water . Th

e flask wa s heate

d sufficientl y t o introduc e th

e desire

d amount o f wate r vapor int o th e flowin

g ga s without causin

g condensatio

nl n either th

e sampl e line s o

r th e instru ment . Th

e wate r vapo r generator wa s calibrate d usin g EP A Metho d 4 . Methane an

d Methy l Mercapta

nInterferenc e fo

r H^ S Monitor s Methane interferenc e wa s determine d usin g 9 9 percent methane . Eac hInstrument wa s firs t zeroe d an d calibrate

d accordin

g to th

e manufacturer' s instructions . Th e methane wa s the

nintroduce

d an d the respons e wa s recorde d a s ppr

a H-S . Thi s sam

e procedur e wa s repeate d usin g 4 0 percent hydrogenin methane an d 20 0 pp

m methy l mercaptani n methane . Th

e interferenc e wa s expresse d i n pp m a s a n equivalen t H. S concentration . Variation s i

nRespons e Du e t o Change s in Temperatur e an d Sampl e Flo w Rat e Variation s i

nInstrument output cause d b y short-ter

m change s i

n ambient temperatur e wer e measure d usin g zer o an d spa ngases . Th

e tes t procedur e Involve

d allowin

g th e instrument to stabiliz e a t a give

n roo m temperature , recordin g th e respons e t

o a gas , changin

g th e temperatur e *10° C an d agai nrecordin

g th e stabilize

d response . Thi s tes t wa s performe

d usin g th e trailer' s heatin g an d ai r conditionin

g syste m to contro l th

e roo m temperature .

3 1P.4 7



### Variation s du e t o flo w rat e change s wer e studie d usin g rotameter s calibrate d wit h asoap-bubbl e flowmeter . Th e spa n ga s an

d th e flo w rat e wer e varie d fro

m approximatel y 2 0 t o 50 0 percen to f th e recommen de d sampl e flo w rate . Th e Instrumen trespons e wa s plotte d versu s th e percen to f

recommende

d flow . FIEL D EVALUATIO

N O F TH E MONITOR

S Fiel d Respons e Time Fiel d respons e tim e I s th e tim e require d fo rth e Instrumen tt o obtai n eithe r9 0 o r9 5 percen to f th e fina l instrumen trespons e afte r aste p increas e i n th e ga s concentration . In th e stud y thi s include d th e tim e involve d fo rga s flo w throug h th e sampl e conditionin g system . Th e ga s was introduce d a tth e samplin g poin tan d th e respons e tim e wa s calculate d l n amannersimila rt o tha tuse d I n th e laborator y evaluatio n o f

Instrumen trespons e time . 2-H rDrif t(Zer o an

d Span ) A t2-h rIntervals , zer o ga s (nitrogen ) was sample d b y th e monitor s unti l al l o f th e monitor s ha

d obtaine d astabl e reading ; then , th e spa n ga s wa s introduce d t o al l o f th e monitors . Th

e zer o an d spa n value s wer e recorde d by th e dat alogge ran d th e sourc e ga s was sample d agai n unti l th e nex t2-hou rinterva l wa s t o begin . At thi s tim e th e abov e procedur e wa s repeated . Thi s wa s continue d unti l fiftee n 2-hou rinterval s wer e completed . Instrumen tzer o an d spa n wer e adjuste d onl y a t24-h rinterval s durin g thi s test , an d non e o f thes e adjustment s wer e made durin g th e tim e a2-h rinterva l measuremen twa

s bein g made . Th

e 2-h rzer o drif twa s calculate d i n th e followin g manner :

Drif t(zer o o r.pan ) - ' » * I + Cl 

### ] ? 10 

### ° * r

### Instrumen tSpa n wher e 

### (3 )

- 1 " d - - - I d* - Algebria c meano f th e difference s 1- 1 d . - (Instrument reading ) - (Instrument readin g 2 hour s later )

n- Numbe r o f dat a point s (I.e. , th e number o f d

< values ) C I - 95 Z confidenc e Interva l estimat e o f th e meanvalu e 

# $ s V - £ * - (£ 

# '* ) (4 )
3 2t . . „ * Student' s t-factor , functio no f n ; i.e .

^.97 5 n 2 3 4 5 6 7 ^.97 5

12.70 6 *.30 3 3.18 2 2.77 6 2.57 1 2.44 7 8 9 1 0 1 1 1 2 1 4 1 5 2.36 5

2.30 6 2.26 2 2.22 8 2.20 1 2.16 0 2.14 5 Th e 2-hr.spa

ndrif t wa s calculate d i na nanalogou s manner , except tha t th e spa nreadin

g wa s correcte

d fo r an y zer o drif t tha t occurre d i nth e 2-h r interval . 24-Hou r Drif t (Zero an

d Span ) The dat a logger automaticall y introduce

d zer o an d spa ngase s int o th e sampl e distributio nsystem

s dail y an d th e instrument respons e wa s automaticall y

recorde

d b y th e dat a logger . Seve nconsecutiv

e value s wer e obtaine

d over a on

e wee k perio d to establis hth

e 24-h r drif t fo

r eac hmonitor . Zer

o an d spa nwere adjuste

d onl y a t 24-h r interval s o

n a na s neede

d basis . Equation s 3 an d 4 were use

d to calculat e th e 24-h r zero an

d spa ndrif t values . Calibratio

nErro r Tes t Th e calibratio

nerror tes t wa s performe d b y firs t calibratin

g eac hInstrument , the nalternatel y

introducin

g eac hcalibratio

nan d zero ga s unti l fiftee nreading s wer e obtained . Th e differenc e betwee n th e Instrument' s respons e an d th e actua l concentratio no f eac

hga s wa s the ncalculate

d usin g equation s analogou s t o 3 an d 4 . (I

nEquatio

n3 . th e calibratio

nga s concentratio

nwoul d b

e th e denominator an

d not th

e spa nvalu e o f th e instrument) . Calibratio

nDrif t Dat a fo

r thi s tes t wer e take nfro m th e dail y

zer o an d spa n checks . Zero an

d spa nadjustment s wer e mad e at weekl y or longe r intervals . Relativ e Accurac

y Th e relativ

e accurac

y o f th e C O monitor s wa s determine d usin g th e leuc o crysta l viole t we t chemica l metho d describe

d i nAppendi xE . Th

e accuracy

o f th e H. S monitor s wa s determine d usin g EP A Referenc e Metho

d 1 1 (6) . Th

e relativ

e accurac

y o f th e monitor s wa s calculate d a s describe

d i nReferenc e 4 , i.e. :



### 3 3P.4 9

r , * 4 a #* xlt

d I + CI ) X100 X, C N Relativ e Accuracy

(X ) - ^ —- —

(5 ) MeanValue o

f Referenc e Metho

d wher e d - Algebrai c meano f th e differenc e between th e referenc e method value an d th e monito r valu e C I - 95 Xconfidenc e Interva l



### 3 4P.5 0

SECTIO N 6 RESULT S AN

D DISCUSSIO

N

MANUA L C O METHOD DEVELOPMENT/VALIDATIO N EP A Referenc e Metho

d 1 0 specifie s collectin g th e emissio

nga s sampl e i

na Tedlar ba

g an d analyzin

g fo r C O b y NDIR(7) . Sinc e NDI R l s th e measuremen t principl e use d l nmos t C

O CEMs , EP

A desire d t o hav e a non-NDI Rmanua l metho d fo r checkin

g th e accurac

y o f NDIR-equippe

d CEMs . Fou

r we t chemica l C O method s previousl y describe

d i nth e literatur e (8-12 ) wer e evaluate d i nthi s study . Th e firs t metho

d evaluate

d (8 ) Involve s th

e aqueou s reductio

no f Pd(II ) b

y C O followe

d b y th e additio

no f K I t

o yield a red , tetraiodo palladlu

m (II ) complex , whic hi s the

nmeasure

d spectrophotometrlcall y t o determin

e th e amount o f Pd(II ) reduced . Th e amount o f C

O present in th e ga s sampl e i s the ncalculate

d o nth e basi s tha t tw

o mole s o f C

O reduc e on

e mol e o f Pd(II) . Althoug hthi s metho

d performe

d adequatel y inth e laboratory , i t wa s foun d unsuitabl e fo

r ga s sample s tha t containe

d eve n1 pp

m NO . Fo

r example , th

e followin

g analytica l result s (pp

m CO ) were obtaine d o nthre e Tedlar ba g sample s tha t containe

d 26 6 pp

m CO an d th e followin

g level s o f N

O innitrogen : 22 5 ppr a N O (2 7 ppm) ; 2 ppr

a N O (18 6 ppm) ; an

d 1 pp m N O (22 3 ppm) . Th

e metho d suffere d from : interferenc e b y SO . an

d organics ; sampl e instability ; poor precisio nbelo w 10 0 pp

m c O an d ha d a nonlinear absorptio

ncurve . Becaus e o f th e slownes s o f th

e reductio

no f Pd(II ) io nb y CO , th e metho d als o require

d shakin

g th e sampl e bul bfo

r 2-h r before addin

g th e KI . Fo

r thes e reasons , wor k o nthi s metho

d wa s terminated . Thre e othe r method s wer e the nevaluated . Thes e method s use d spectrophotometr

y an d th e reductio

no f Pd(II ) io

nb y C O i nthe presenc e o f gu

narabl e (9) . phosphomolybdl c acid/acetone (10 ) an d leuc o crysta l violet/potassiu m lodat e (11 , 12) . Th e gu narabl e metho

d suffere d fro m poo r precision , sampl e instability , an d interferenc e fro m lo w level s o f N

O an d SO . an

d require

d a lon

g reactio

ntim e ( 2 h r minimum) . Th

e molybdenu

m blu e reactio

nals o suffere

d sampl e stabilit

y problems , ha

d poo r precisio

nfo r C O concentration s near th e leve l o f th e standar

d (50 0 ppm ) an

d require

d a sampl e reactio ntim e o f 1 h

r a t 6 0 C • 1°C . Further , Inbothth e gu narabl e an

d phosphomolybdl c methods , th

e reactio

nproduc t i s a colloid , whichmean s tha t a strongl y

absorbin

g solutio

ncanno t b

e dilute

d t o brin

g i t int o th

e linear range o f th

e calibratio

ncurve .



### 3 5P.5 1

Th e las t metho

d evaluated , th

e leuc o crysta l viole t (LCV ) method , yield s a solubl e comple xtha t permit s sampl e dilution , ha s goo d precisio

nl nth e rang e o f 0 t o 100 0 ppm , an d i s accurat e l

nth e presenc e o f lo

w level s o f SO

p an d N O « 5 ppm) . Som

e othe r favorabl e feature s are :

• th e shakin

g reactio

ntim e ca nb e a s shor t a s 1 5 t o 2 0 minute s fo

r CO concentration s fro m 5 0 t o 1,00 0 ppo ;

• th e absorbanc e Increase s linearl y withIncrease

d shakin

g reactio ntim e u p t o 2 hours ;

• th e stock reagent s ar e stabl e an d easil y

prepared ;

• th e calibratio

ncurv e l s linear i

nth e absorbanc e rang e 0 t o 1.7 ;

• th e comple

xtha t i s forme

d absorb s i

nth e visibl e regio

n o f th e spectru

m (58 7 nm ) mor e tha

n20 0 n m fro m wher e th

e reagent s absorb . Also , th e blan k i s Initiall y negligibl e (Tabl e 12) . Sinc e th

e LC V metho d suffer s interferenc e fro m SO . an d N O a t th e concentration s encountere d i nFCC stac

k gase s (Tabl e 13) . th e effec tivenes s o f variou s scrubbin g solution s i

nreducin

g thes e compound s t o les s tha

n5 pp m (without als o removin g CO ) wa s studie

d a s a functio

n o f flo w rate , scrubbe r volune , concentratio nan d pH , ga s volune , an d SO . an d N O concentration . Th e followin

g scrubbin

g solution s wer e evaluated : 6 > percent H.O. ; 2 percen t KMnO^/ 2 percent NaOH ; 4 percen t KMn O / 4 percent NaOH ; 2. bpercent KMnO^/ 1 percen t HN O ; an d 2 percent K 2 C r 2°7 / 1 P ercen t HN0 3 ' Th e bes t scrubbin

g syste

m l s a flo

w rat e o f 0. 2 t o 0. 3 L/mi n throug hthre e Greenburg-Smit hImpingers . Th e firs t tw

o impinger s contai n40 0 m

L o f 4 percen t KMnO^/ 5 percent NaO H an d th e thir d 25 0 m

L o f thi s solution . Thi s syste m ca nreduc e th

e SO . an

d N O level s t o les s tha

n5 pp m fo r a 50-lite r ga s sampl e containin g 15 * COg , 70 0 pp

m SO . an d 50 0 pp

m NO . Sinc e th

e Impinge

r syste m als o remove s CO. , a n appropriat e volune correctio ni s require

d whe ncalculatin

g th e C O concentratio

noriginall y

present i

nth e gas . A

Fyrit e analyzer i s suitabl e fo

r measurin

g th e CO . presen t i

nth e stac k gas . Fo r fiel d sampling , th e origina l single-sample , ambient ai r metho d (12 ) wa s modifie d t o allo w th e analysi s o f man

y sample s l

na shor t perio

d o f tim

e under fiel d conditions . Sampl e stability , shakin g time , shaker type , sampl e volume , an d volum

e o f reagent wer e



### 3 6P.5 2

some ' o f th e parameter s studie dt o simplif y th e metho da s muc ha s possibl e an

da t th e same tim e t o optimiz e it s precisio nandaccurac y a t stac k C O concentrations . Th e metho dwa s validate da t th e petroleu m refiner y

i nfou r fiel d test s inwhic hth e sample s wer e passe dthroug hth e scrubbe r solutio n andcollecte dI n10-lite r Tedla r bags . Thes e ba g sample s wer e re turne dt o th e laborator y an danalyze di ntriplicat e b y th e LC V metho d andb y NDI Ro na Bendi xMode l 8501-5C A calibrate dagains t NB S certifie dC O standards . Fro m forty-on e sample s collecte dan danalyze d i nthi s manner , l t wa s determine dtha t th e manua l metho dhada consis ten t 4 percen t positiv e bia s wit hrespec t t o th e NDIR . Th e precisio n o f th e metho dwa s determine dt o b e 2. 5 percen t o f th e mea nconcentra tio nfo r a sampl e tha t containe dbetwee n1 5 and100 0 pp m C O whe nth e sampl e wa s analyze di ntriplicate . Th e Tedla r ba g sample s wer e stabl e fo r a t leas t tw o weeks . Representativ e analytica l result s ar e pre sente di nTabl e 1 4 andthe actua l metho di s describe dl nAppendi xE . Sinc e th e larges t sourc e o f erro r wa s foun dt o b e leak s around th e valv e o f th e Tedla r bags , al l bag s shoul dbe checke dfo r leak s befor e use , eithe r b y submergin g fille dbag s i nwate r o r b y pullin g a vacuu m ( 2 5 c

m H.O ) onthe ba g an dseein g l f i t wil l hol dth e vacuu m fo r a t leas t 4 hours .



### 3 7P.5 3

TABL E 12 . CHANGE I N ABSORBANC E OF CO REAGENT BLAN KWIT H TIME A T ROO

M TEMPERATURE
TIM E snic z nUTAJtATION (•In )
0 2 0 S O 4 3

• 0 10 0 12 0 I M 29 0 2S 0 22 0 M O A1S0XAAJ1CT . THI S STUD * ZITERDJC E 1 1 0.01 3 0.01 5

0.02 0 0.03 0 0.05 0

0.08 0 0.08 5 0.08 9 0.10 0 0.02 0

0.04 0

0.0 7 0.1 2

0.2 1

TABL E 13 . EFFEC T O F NO AN D SO - O N LUEC O CRYSTA L VIOLE T SAMPL E VUMBE &
1 2 2 4 S O ,

(ppa )
0 0 TO O SO O S

O

20 0 40 0 0 20 0 C

O ACTUA I SO O 

## so o so o so o (pp« )

FOOT!) 41 0 29 0 29 0 S6 0



### 3 8

.P.5 4

TABL E 14 . COMPARISO N BETWEE N LC V AN D NDI RRESULT S O N FC C SAMPLE S
TES T DAT E

SEPTEMBE

R 198 0

JANUAR Y 198 1 LC V METHOD RESULT S (pp m CO ) 

### 1

17 8 12 1 31. 1

- 78. 6 26. 5 25. 2 28. 8 16. 7 33. 0

109 4 

### 35 6 54 6 17 6 181 15 8 18 8 8 1 10 2 51 9 25 8 2

15 9 12 0 31. 0 91. 1 28. 0 24. 0 28. 0 17. 6 30. 2

100 2 

### 36 5 59 2 184 184 145 18 2 8 7 11 4 48 2 24 8 3

16 3 12 9 30. 1 76. 4 27. 8 26. 9 29. 3 16. 5 33. 2

lll l 

### 32 1

— 

### 18 2 211 15 3 18 9 7 8 11 0 53 6 26 7 A V

16 7 12 3 31. 0 82. 0 27. 0 25. 0 29. 0 17. 0 32. 0

106 9 

### 34 7 56 9 18 0 19 2 15 2 18 6 8 2 10 9 51 2 25 8 NDI R(pp m CO ) BENDI X8501-5C

A



### 14 9 11 5 34. 0 75. 0 26. 0 22. 0 27. 0 19. 0 28. 0

100 5 

### 31 5 57 5 17 8 17 5 15 5 181 6 2 9 8 53 9 23 5

3 9EVALUATIO N O F CARBO N MONOXIDE MONITOR S Fiv e relativ

e accurac

y test s wer e conducte d o nth e C O monitor s at th e refinery . Th

e result s o f thes e test s are summarize d l nTabl e 6 an d th e result s o f eachru nare presente

d i nTabl e 15 . I

nthes e tests , th e sample s fo r th e manua l metho d wer e passe d throug h Greenburg-Snit himpinger s containin g alkalin

e KMnO . solutio

n(to remov e N0 X , S0 Xan

d organics ) an

d the ncollecte

d i nTedlar bags . Al l sample s wer e collecte d fro m th e distributio

nmanifol d to ensur e tha t a sample-conditionin

g syste m malfunctio

ndid not contribut e significant error t o th e monito r validatio nprocedure . Test s t o verify

tha t C

O wa s no t los t i

nth e sampl e conditionin g syste m wer e conducte

d before eac

hrelativ

e accurac

y tes t an

d at othe r time s betweenFebruar y 198 0 an

d Apri l 1981 . Unti l September 1980 , thes e check s consiste d o f simultaneousl y collectin

g stack ga s sample s inTedlar bag s a

t th e manifol d (distributio nbox ) an

d a t th e probe , an d analyzin

g th e bag s b

y NDI Rfo

r C O an d CO . a t th e EP A laborator

y i n Researc hTriangl e Park , Nort hCarolina . I

nSeptember 1980 , a Bendi x Mode l 8501-5C

A NDI RCO . analyzer wa s installe d i nth e trailer t o con tinuousl y

measur e th

e CO . concentratio nl nth e ga s leavin

g th e mani fold . After this , th e sampl e conditioning/sampl e transpor t syste m wa s checke d monthl y

an d als o befor e eac hrelativ

e accurac

y tes t b

y analyzin

g th e stack ga s fo

r CO . usin

g a Fyrit e analyzer an d b y comparin

g th e resul t t

o th e Bendix8501-5C

A monito r reading . I f th e BendixCO . monito r value differe d b y mor e tha

n0. 5 percent fro

m th e Fyrit e value , remedia l actio nwa s take

nbefor e th

e relativ

e accurac

y tes t wa s Initiated . Th e operatio

no f th

e FCC uni t durin

g thi s 11-mont

hstud y wa s errati c due t

o FCC failure an

d proces s upsets . Th e C O level s varie

d betwee n2 0 pp

m an d 10,00 0 pp

m C O ove r a perio

d o f severa l days ; frequently , th

e particulat e emission s were muchhigher tha nth e 5 0 t o 10 0 mg/m

normall y

present . Eac

htim e a relativ

e accurac

y tes t wa s conducted , th

e C O concentratio

ni nth e stack exceede

d th e 1,00 0 pp

m spa nrange o f th

e monitors , s o plan t instrument ai r wa s introducte d a t th e prob e t o brin

g th e C O concentratio

ninto th

e operatin

g range o f th e monitors . Thi s dilutio nals o reduce

d th e N0 Xan

d S0 2 concentra tion s i nth e sampl e ga s b

y factor s o f 4 t o 10 . Durin g eac hrelativ

e accurac

y test , a cylinder ga s containin g 10 0 pp m CO , 1 2 percent CO. , 50 0 pp m SO. , an

d 20 0 pp

m N O i nN . wa s intro ducte d a t th e manifol d fo

r 3 0 mi nan

d th e monitors ' output wa s recorde d whil e th

e Tedlar ba

g sampl e wa s take

nfo r analysi s b

y th e manua l method . Thi s serve d thre e purposes . First , i t showe d ho w th e monitor s woul d perfor m whe nsamplin

g a stac

k ga s representativ e o f FC C exhaus t gases . (Recall , i t wa s necessar y t o dilut e th

e stack ga s with ai r t o brin

g th e CO leve l int o th

e range o f th

e monitors. ) Second , i t serve d a s a contro l sampl e to establis hho w constan t a monitor' s respons e wa s to th e sam e sampl e over th

e lengtho f th

e study . Third , l t provide

d a sampl e o f know nC O concentratio

nso tha t th

e accurac

y o f th e manua l metho

d (samplin

g an d analysis ) coul d b e established .


### 4 0P.5 6

Durin g eac ho f th e 30-minut e relativ e accurac

y tests , th

e monitor outpu t wa s rea

d a t 1-oinut e Intervals . Th e firs t test , conducte d in Jun e 1980 , wa s unsatisfactor y becaus e th e manua l metho d bein g evaluate

d (palladium/potasslu nIodide ) suffere d sampl e stability problem s an d Interferenc e fro m NO . Thus , th

e onl y wa y t o evaluat e monito r accurac

y I nthi s tes t (Tabl e 15 ) I s t o compar e one monitor t o anothe r (Run s 1-9 ) or t o compar e thei r respons e t o th e 10 0 pp

m C O cylinde r (Ru

n10) . However , sinc e th

e othe r fou

r relativ

e accurac

y test s wer e don

e usin g th e LC

V method , satisfactor y manua l metho d result s wer e obtained . Th

e fourthan

d fift hrelativ

e accurac

y test s wer e performe d durin g th e sam e week . Inth

e fourthtest , thre e ga s cylinder s containin

g 50 0 pp

m CO , 1 2 percent CO. , an d different level s o f SO . an d N O wer e employe

d t o see ho

w th e monitor s woul d perfor m l f samplin

g a n undilute

d FCC stack gas . As expected , th e Ecolyzer detector faile d durin g th e tes t fro

m exposur e to N0 „ an d SO . whic

hwer e no t effec tivel y remove d b y th e Mode l 294 9 scrubber . I nth e firs t thre e rela tiv e accurac

y tests , th

e Anara d an d MSA monitor s were quit e stable , but , b y th e las t tw

o tests , the

y somtlme s drifte

d u p t o 5 percen t o f spa nover severa l hours , bu t at other time s remaine d stabl e fo

r a day . Thi s drif t sometime s occurre d onl y i nth e spa nan d a t other time s onl y Inth e zer o setting . N

o explanatio

nl s availabl e fo

r th e difficulty . A s mentione

d earlier , th

e onl y proble m encountere

d withth

e LC V manua l metho

d wa s th

e tendenc

y o f th e Tedlar ba

g t o lea

k a t th e point wher e th

e valv e enter s th

e bag . Thi s wa s a significant proble m onl y i nth e fourthrelativ

e accurac

y tes t wher e ne

w sampl e bag s wer e use d an d a smal l lea

k wa s foun

d a t th e meta l washer that serve d a s a gaske t betwee nth e valv e bod y an d th e bag . Thi s lea

k onl y occurre

d whe nth e sampl e wa s withdraw nfro m th e ba g an d fo r thi s reaso

nwa s not detecte

d whe nth e bag s wer e leak-checke d b y Inflatin

g the m before use . Tw o calibratio

nerror test s wer e performed : th e firs t i

nMa y 198 0 an d th e othe r i

nJun e 1980 . Th

e result s ar

e presente

d i nTabl e 5 . Th e interferenc e o f CO . o nth e monitor s remaine

d constan t throughou t th e study . Figure s 5 throug

h1 0 sho

w th e long-ter

m zer o an d spa ndrift s i

n th e CO monitors . Thes e data , whic hwer e collecte

d fro m Ma y 198 0 t o Januar y 1981 , wer e use

d t o determin

e th e calibratio

ndrif t o f th

e Instruments . (Recal l that : (1 ) onl y th e Applie

d Automatio

nha d auto mati c zer

o an d tha t non

e o f th

e instrument s ha

d automati c spa

n correction ; (2 ) th e zer o an d spa no f th

e monitor s wer e checke d ever y 2 4 hours ; an

d (3 ) except whe

nrelativ

e accurac

y test s wer e bein

g conducted , th

e zero an

d spa no f th

e monitor s wer e neve r adjuste d a t Interval s shorter tha n1 week. )



### 4 1P.5 7

Applied Automatio

nOptlchro

m Mode l 10 2 The instrument I s comprise d o f tw

o modules , a programmer an d a GC-ove nassembly . I t wa s purchase d withou t vendor installatio nan d Interconnectin

g wirin g wa s no t furnished . Ih e instructio

nmanua l wa s furnishe

d thre e week s after th e instrument wa s received ; hence , th e nonito r wa s no t operationa l a s received . Extensiv e tim e wa s require

d t o complet e th

e Instrunent wirin g an d Instal l th

e circui t boards . Afte r th

e monito r m s wire d an d installed , numerou s startu p problem

s wer e encountered . Afte r a servicema nwa s sent b

y Applie d Automation , i t wa s determine

d tha t wire o f too smal l a gauge ha d bee nuse d fo r th e Interconnectin

g wiring . Numerou s othe r difficultie s wer e encountere d lnobtainin

g th e correc t output signal . To adjus t th

e span , a length

y procedur e requirin g a stri p char t recorde r an

d man y adjustment s i s necessary . After th e initia l spa

n adjustment , a trial-and-error metho d i s use

d fo r fin e tuning , al thoug hl t i s no t specifie d I nth e instructio

nmanual . Th e respons e tim

e i s limite

d b y the cycl e tim

e o f th e analytica l program . Th

e G C complete s a cycl e ever y 10 5 seconds . Varyin g th e flo w o r pressur e cause s n o respons e varianc e becaus e a samplin g loo p vente d a t atmospheri c pressure l s used . A nove nmaintain s a constan t temperatur e fo

r th e chromatographi c columns . Sinc e th e sampl e value l s ambien t temperatur e o r i na thermostaticall y controlle

d area , i t wa s not affecte

d b y change s l

nambient temperatur e o r sampl e ga s flo

w rate . I nJun e 1960 , a negativ

e concentratio

nwa s sometime s measure d b y th e Instrument . Afte r carefu l examinatio no f th

e chromatogram , thi s proble m wa s relate

d t o a negativ

e signa l di p tha t occurre d immediatel y befor e th

e C O pea k eluted . Severa l trip s t o th e refiner

y wer e mad e b

y HE& T personne l t o repai r th e instrument wit hn o success . I

nNovember 1960 , Applie

d Automatio

nperforme

d a servic e call . After tw o day s o f work , th

e servicema

nstil l could no t correc t th e proble

m an d further testin g o f thi s instrunent wa s discontinued . Ecolyze r 310 7 Thi s instrumen t performe d withou t failur e durin g th e laborator

y testing . Specia l provision s wer e necessar y t o ensur e tha t a sampl e pressur e o f n

o mor e tha

n2. 5 c

m wate r pressur e wa s present a t th e sampl e inle t port . Th e spa nan d zero adjustment s wer e no t responsiv e an d thu s a slo

w drif t I

nzero an

d spa nfollowe

d an y adjustmen t l

n thes e controls . Sampl e flo

w variation s fro

m 0. 5 t o 1. 5 time s th e recommende

d rat e cause d respons e variation s o f 1 0 percen t reductio nan d 3 percent increase , respectively . I nvaryin

g th e ambient temperatur e fro m 1 0 C t o 30° C n

o change i

nrespons e wa s observed .



### 4 2P.5 8

For remova l o f N

O an d SO . fro

m th e sampl e stream , a ga s scrubber cartridge (filter Mode l 2949 ) wa s supplied . Thi s wa s locate d Insid

e th e cas e an

d require

d remova l o f th

e senso r fo r replacement . Becaus e o f th e extremel y

shor t lifetim

e o f thes e filter s an d th e difficulty

in replacement , th

e filter s were relocate d outsid

e o f th e cas e durin

g th e field evaluation . Norma l lif e expectanc y o f thes e filter s i na stack ga s containin

g 50 0 pp

m SO . an

d 30 0 pp

m N O l s 1 t o 5 days . Thes e filter s cos t approximatel y $4 5 ( a considerabl e operatin g expense) . Filte r failur e cause d damage to th

e electrochemica l sensor (requirin g replacemen t a t considerabl e cost) . MS A Lir a 20 2 Th e MS A Lir a 20 2 operate

d a s received . After les s tha na wee k o f operation , th

e powe r suppl y

an d output signa l circui t board s failed . Afte r th

e board s wer e replaced , satisfactor y output i

nth e range o f 4 t o 2 0 m

A coul d not b

e obtained , despit e severa l replacement s o f eac h o f thes e circui t boards . I nJun e 1980 , a

nMS A servicema

ncorrecte

d th e problem . Instea d o f usin g th e 4 t o 2 0 m

A outpu t o

nth e instrument , h

e use d a nIsolate

d externa l converter t o conver t th

e norma l 0 t o 10 0 m V output t o 4-2 0 nA . After thi s repair , th e monito r operate

d wel l throughou t th e evaluation . Occasiona l optica l realignmen t wa s require d t o maintai n calibration . Excessiv e drif t wa s sometime s observed . Test s fo

r respons e variatio ndu e to sampl e flo

w rat e an

d ambient temperatur e change s wer e not p e forme d due to th

e lat e arriva l o f th e instrument . Anara d 501 R Thi s NDIRmonito r performe d withou t an

y difficulty

durin g th e evaluation . N

o specia l provision s wer e necessar y fo r th e sampl e ga s except tha t ther e ha d to b e free discharge fro m th e sampl e exi t port . Sampl e flo

w variatio

nfro m 0. 3 t o 5 time s th e recommende

d rat e cause

d respons e variation s o f les s tha n1 percent . Varyin g th e ambient temperatur e fro

m 10° C t o 30° C di d not affec t th e response . Carbo n dioxide an

d water did giv

e a sligh

t positiv

e interferences . Overall , th e instrunent prove

d t o b e extremel y

accurat e an

d reliable .



### 4 3P.5 9

TABL E 15 . RELATIV

E ACCURAC

Y TES T RESULT S O

N C O MONITOR

S 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 M l

U I
• 1 I H

4 U » » M t > M ti l M t
i n

* i

i * i i u i * M t

U l i n M l I M 11 1 M M

i n M l t i t t M I t . t H

t n i n t i t t t i t N 1 * IT I *J I I U

I M 11 1 • 0 1 ) M t t M l H

M M •O J I M t » I M H I • M i n

M l I M H I •1 ? M > t w M O M t M l

I M I M t l M t l 4 1 M O t t

Mt ! H O i n B l M I t i • M

H I t . I I U I t M U I t U M l

t i l M l t n M l t t l M l M l t u 4 M

M n M M I M O 110 0

u t i
r u M l H I

M l M l H I t M M l M t M i M l M l M l M i t i t • I t

m M l M t » 1 M I M t no T M T M t t ?

M 7 ti t t i t ti e M t M l M l M l M l

T U n i u t M t m TT l m m T M

M-Mlt . »m.t- 4 twt B , Mt.ll.l—. . IC V M.M 4 tM . M . -mt* «M4 . CTIIM. 1 -ft

MM : N

O nm B ; B O r m B, . M O n . B ; WlM M » , •ue l $.. Ulill f 1: 4 a-Ht k llll l -Mi l .b . lur k ,. < 4IU.1 M 1:1 0 Hi k (MIH M air . tix l ,. . 4U-nl« > li t «t. » wrna i ut . Cite*
. $ M MM . H C rf> a . u c n i B . i n B, : hi. n •. . tri t eri t . •M. 4 H O M » B . H D fm B, : I B 00, ; talMM « .

" f
• • MM : H

O H » B . B C , M B ; H C „ • H, : I B oe, : MM M I, . xm -tmmlt

M f te Mll»r.tM . R S n > I



### 44P.6 0



### — q 

# i



# _« L ^

_ 

# 1 [



## , J 

# li

ft * • *•* •a*r » fal l •a m feu Ja*» f |

I C 4 M t( t H M FIGUR E 5 . ZER

O DRIF T TREN

D FO RECOLYZE

RCEM .

* * - " 

### M l

• " V f iy

W

/* \



### - J * a 

# 4

~ r h

1 

# I

\ P * •*•»• " •• •ca»cantraiiam .

A •tele ayan fallw a « «at a lirtf .

FIGUR E 6 . SPAN DRIF T TREN D FO RECOLYZE

RCEM.

4 5P.6 1



### f ( .

' a >

. 

### f | "

t*^- > 

# A,

V j



## , 

## '.A- J i L 

# L r • « . te» M M fail* . • » 4. U IqtR . 1 • *•« • HM .



## _L] K 

## L L

_ *"aa"\ j

mm JHC 4W

7 M m «C T «o v K C J M m M M FIGUR E 7 . ZER

O DRIF T TREN

D FO RMS A CEM ,

^ 

# V

^ » i

• 

# J in n^ ul iL •

i 

# r i

_ 

# i ^

.. . 

# l L—M M 

# V BMlo tturn WUIU I

Mlt.r.tl M ,. . CM* . 4 * JUl . IM " f.U-B . m 4.1 . l.-M.t .

m ac t t

c « M n o FIGURE 8 . SPA

N DRIF T TREN

D FO RMSA CEM .



### 4 6P.6 2



## I

8

J \if[

"•V Y 

# A <

JL A "*— tlmm J «

i 

# li j ^ 

### ^cr \ 

# J A • teu ear * fatli i A . m few H—ir .



# i r

•c r mo. M C 4*

a rt i M M FIGUR E 9 . ZER

O DRIF T TREN

D FO RANARA

D CEM.

• -A*-a " ^

T i 

# m . • * S • » N . ,



### r ' • 

# u U

• 

# r r 1

1 \ 4 Sstht f It m tebdUmtma

. caJUratta * •• •Mac . A • C M • t M a •tet

v vi e li M t a

a aar a falJa n «

FIGUR E 10 . SPA

N DRIF T TREN

D FO RANARA

D CEM .



### 4 7P.6 3

EVALUATIO

N O F HYDROGE

N SULFIDE MONITOR S Th e result s o f th

e nine relativ

e accurac

y test s are summarize d ln Tabl e 10 . Th

e Individua l tes t result s ar e presente d i nTable s 1 6 an

d 17 . Fro

m a nexaminatio

no f th

e data , th

e followin

g observation s are •ade : 1 . Whentw

o laboratorie s simultaneousl y conducte

d a rela tiv e accurac

y tes t o f th

e monitors , ver

y goo d agreemen t wa s obtaine

d betwee

nth e laboratories , but thei r result s differe d significantl y

fro m th e nonitors ' result s (Tabl e 17 . R A Tes t 5) . 2 . A monito r coul d compar e wel l on e da y bu t poorl y

th e next (Tabl e 16 , R

A Tes t 4A , 48) . Th e overal l agreemen t betwee nMetho d 1 1 an

d th e monitors , a s measure d b y th e relativ e accurac

y tests , wa s quit e variabl e over th e lengtho f th

e stud y (Tabl e 16) . Thi s variability wa s als o note

d l nth e previou s short-ter m stud y (3) . 3 . Generally , th e Bendi xan d Housto nAtla s monitor s measured H^ S concentration s lower tha nMetho d 11 , bu t o

n on e occasio

n(R A Tes t 6 , Tabl e 16 ) th e Bendixmeasure

d H. S level s higher tha nMetho

d 11 . Experiment s t o determin e th e caus e o f thes e difference s wer e inconclusive . Whe nth e fue l ga s wa s spike d wit hknow n amount s o f H- S upstrea m o f th e manifold , th

e spik e wa s adequatel y

recovere

d b y bothth

e monito r (Bendix ) an d th e Metho d 1 1 procedure . Durin g thes e tests , (Februar y an d Marc h1981 ) th

e Housto

nAtla s monito r wa s not operationa l an

d th e De l Ma

r wa s driftin

g severely , a

o onl y th e Bendi xresult s wer e reliable . Th e tw o laborator

y collaborativ

e tes t (Tabl e 17 ) show s tha t th

e differenc e i

nconcentration s wa s no t due t o laborator y bia s i nMetho

d 11 . Bot

hMetho

d 11 an

d th e monitor s agree d wel l whe

nanalyzin

g H- S innitroge ncylinde r gases . 4 . Whenth

e eighteen , 30-minut e test s (Tabl e 16 , R A Tes t 4 A an d 4B ) wer e groupe d t o yiel d nin

e 1-hou

r tests , th

e relativ e accurac

y o f th e monitor s wit

hrespec t t o Metho

d 1 1 did no t improv

e significantly . Thi s indicate s tha t increasin g th e samplin g time t o 1 hr doe s no t significantl y

improv e th e result s obtained . Figure s 1

1 throug

h1 6 sho

w th e long-ter

m zer o an d spa ndrif t ob serve d i nth e Hp S monitors . Thes e data , whic hwer e collecte

d fro m Ma y 198 0 t o Januar

y 1981 , wer e use

d to determine th

e calibratio

ndrif t o f th e Instruments . (Recal l that : (1 ) onl y th e Bendi xan

d PA I ha

d automati c zero an

d tha t none o f th e instrument s ha

d automati c spa

n



### 4 8 

# JP.6 4

correction ; (2 ) th

e zero an

d spa no f th e monitor s wa s checke d ever y 2 4 hr ; an d (3 ) except whe

nrelativ

e accurac

y test s wer e bein

g done , th

e zero an d spa no f the monitor s wer e neve r adjuste d a t interval s shorter tha none week) . Bendi x777 0 Thi s instrunen t i s equippe d wit hnumerou s safet y device s includ in g automati c shutdow nan d star t u

p l f certai nhazardou s condition s exis t i nth e analyzer . A

molecula r siev

e wa s adde

d t o th e carrier ai r an d hydroge

nsuppl y

t o ensur e contaminatio nfree gases . Th e Bendi x operate d 8 9 percen t o f th e tim e durin g field evaluation . Mos t o f th e downtim e wa s attributabl e t o tw o pneumatic , valv

e failures ; th

e down tim e wa s lengthene

d du e to personne l not bein g on-sit e t o replac e th e part . Th e flo w variatio

nan d ambient temperature change test s wer e no t applicabl e t o thi s instrunent becaus e l t use d a heate

d samplin

g block t o injec t a constan t an d know nvolun e o f sampl e Int o th e chromotagrap

h column , regardles s o f th e sampl e flo

w rate . Th

e cycl e tim

e o f th

e instrunen t wa s 21 0 sec . Fo r thi s reason , th

e tim e fro m injectio

nt o 10 0 percent respons e wa s use d i nth e laborator

y evaluatio

nfo r respons e tim

e rather tha

nfro m firs t respons e t o 9 5 percen t o f th e fina l response . Th e result s o f th

e precision , drift , nois e an d calibratio

nerro r test s wer e excellent . Relativ e accurac

y testin g showe d a consistan t differenc e betwee

nth e monitor an

d Metho d 1 1 fo

r th e fue l gas . Th

e agreemen t wa s always goo d fo r H- S I

nnitrogen . A

ninterferenc e i n either th

e monito r o

r th e referenc e metho

d wa s Indicated . Proces s Analyzer s Incorporate d 32-23 0 Thi s instrumen t neve r functione d properly . Man

y hour s wer e spent troubleshootin

g circui t board s to attempt t o fin d th e caus e fo

r th e lac k o f a proper output signal . Th e schemati c wirin g diagram

s furnishe

d i nth e operatin

g an d maintenanc e manua l wer e not i nagree men t withth

e actua l wiring . Th e uni t wa s returne d t o th e manufac ture r fo

r repair . Afte r mor e tha n4 weeks , i t wa s returne d t o HEA

T an d installe

d i nth e tes t trailer o

nth e fina l da

y o f th e firs t fiel d evaluation . Befor e th e nex t schedule

d field evaluation , th e monito r agai nfaile

d du e to a wor

nsampl e valve . Th e outpu t o f th

e monito r wa s no t th e 4 t o 2 0 m A specifie

d inthe equipmen t order ; an d thu s th

e monitor wa s not compatibl e withth e dat a aquisitio

nsystem . Thus , it s output wa s recorde d o nth e narro

w recorde r supplie

d withth

e monitor . Afte r severa l breakdowns , th e nonito r wa s shu

t of f an

d it s evaluatio

nwa s discontinued .



### 4 9P.6 5



### Teledyn e 61 1 DMCO-20

X Thi s Instrunen trequire d alignmen to f th e choppe rb y usin g a n oscilloscop e prio rt o operation . Sever e instabilit y cause d b y an y movemen to rvibratio n necessitated.tha tlaborator y testin g b e don e a t nigh twhen win d o rpersonne l woul d no tcaus e movemen to f th e evaluatio n trailer . Significan tinterference s wer e cause d b y methy l mercapta n an

d othe rcompounds foun d l n fue l gas . Th e molecula rsiev e scrubbe rprovide d wit h th e Instrumen tcoul d no tcorrec tth e interference . A

n alternat e scrubbe rwa s eventuall y furnishe d bu t complet e failur e of-th e instrumen tha d alread y occurred . Becaus e o f multipl e factor s preventin g acceptabl e operatio n o f thi s monito r testin g wa

s discontinue d befor e avali d tes twas achieve d (Se e Appendix F) . Housto n Atla s 825R/10 2 Th e instrumen tperforme d properl y a s received . Th e instrument' s ga s dilutio n syste m wa s no taffecte d b y sampl e flo w rat e o rpressur e changes , bu tl twa

s affecte d by ambien ttemperatur e changes . Tha tis , increasin g th e ambien ttemperatur e decrease d th e respons e l n accor danc e wit h th e Idea l ga s law . Thi s affecte d th e accurac y o f th e dilu tion . Becaus e o f

awirin g defect , th e instrunen tdi d no toperat e durin g th e firs tfiel d tes tan d wa s returne d t o th e manufacturer . I twas rapidl y repaire d an

d returne d t o th e refinery . Extremel y larg e varianc e i n th e dail y spa n value s (1 0 t o 3 0 percent ) durin g th e firs t8 month s o f operatio n resulte d fro m wate r condensatio n i n th e sampl e ven tline . Increasin g th e downwar d slop e o f th e ven tlin e eliminate d th e problem . Th e pneumati c actuato rfo rth e dilutio n syste m faile d twic e durin g th e fiel d evaluatio n causin g monito rdowntime . N o specifi c interference s were detecte d bu tth e genera l agreemen tbetwee n Metho d 1 1 an d th e monito rwa

s no twithi n th e desire d 10-percen trange . Eac h tim e th e lea d acetat e tap e was changed , th e monito rrequire d recali bration . Thi s require d aminimu m o f 2 h rdue t o th e instrument' s slo w respons e t o calibratio n adjustment . A rol l o f tap e laste d approximatel y 1 4 days . De l Ma r Scientifi c DM- W Th e instrumen t operate d a s recieved , bu t befor e continuou s operatio

nwa s possible , th e tensio

no nth e tap e tak e u p ree l bel t ha

d t o b e increase

d b y shortenin

g th e belt . Th

e ga s dilutio

nsyste

m supplie d b y th e vendor wa s inadequate . I t wa s comprise d o f tw

o rota meter s (on

e fo r sampl e an

d on e fo r dilutio

ngas) , a mixin

g chamber an

d a back pressur e regulator . Slight change s i nsampl e ga s viscosity an d



### 5 0P.6 6

change s i

nbot haampi e an

d dilutio

nga s flo

w rat e an

d pressur e cause

d drasti c calibratio nshift s inth

e instrument . Larg e volume s o f dilutio nga s (1 0 L/min ) were specifie d b y th e manufacturer . A t thi s rate , a cylinde r o f nitroge nwoul d las t 1 day . Thus , t o conserv e gas , bothsampl e an

d dilutio

nflow s wer e reduce

d t o 1 5 percen t o f th e recommende

d rate . Advers e effect s wer e no t note d b y thi s reductio

nl n flow . Variation s I

nsampl e pressur e greate r tha n1 ps i cause

d larg e variance s i

nth e sampl e flo

w t o th e dilutio

nsystem , whichi ntur n cause d poor result s inprecision , nois e an d drif t evaluations . Th e majo r proble

m withth

e instrunent appeare d to b

e th e sampl e ga s dilutio nsystem .



### 5 1*

• •

TABL E

TZS T H O BAT E

K A T«t t1 1 2 3 4 S 6 7 • 9 ••a n
K A Tes t2 1 2 3 4 S 6 7 8 a 9 HM D K A Tet t3 1 2 3 4 S 6 7 8 9 * HM D

a " 16 . i

RELATIV E ACCURAC

Y TEST RESULT

S O N H

KETWO D 1 1 RESULT S (PP * %S ) (4/27/80 ) 16 1 11 9 16 5 17 2 16 6 16 7 16 6 15 8 .21 2 16 0 (5/3/80 ) 15 7 18 9 17 3

. 22 2 21 9 22 6 25 1 24 7 13 0 20 2 (6/9/80 ) 26 2 26 9 22 6 24 5 19 9 23 3 21 9 16 3 2 8 20 5 Din-ERENC E tHethr.4 ll-MoMt 0 T > KEXDI X BOUSTO

N ATLA S <PP« ) <PP»

)

4 3 3 7 5 2 2 5 4 7 4 2 1 3 7 2 2 3 9 3 2 4 0 4 4 2 8 3 8 3 4 £ 1 4 5 3 9 3 2

2 2 - 6 5 2 2 3 S O 2 5 4 4 1 8 2 9 12 8 3 5 4 3 7 5 8 6 8 8 11 7 2 6 1 4 7 4 8

9 9 7 6 9 6 6 7 7 3 S

O 9 1 7 4 7 8 6 1 10 2 8 6
• 2 7 8 6 2 4 7 2 8 2 8 7 9 6 3 (Continued ) i

.

5 2 2 S MONITOR S (vm fcS) OEI . MA X (PP« >

-19 7 -24 8

- 7 7 -14 1 -13 8 -13 8 -1* 7 -15 8 -15 3 -15 5

-14 3 -10 4 -12 0

- 6 7

- 6 9

- 6 4

- 3 5

- 4 3 -15 8

- 8 9

8 0 8 7 4 9 6 8 8 6 3 3 3 0 3 7 2 8 5 5P.6 8

TABL E
TES T AN D BAT E

K A Tes t4 S « 7 1 9 1 0 1 1 1 2 1 3 l i U 1 6 . RELATIV E ACCURAC

Y TES T RESULT S O

N H ? S MONITOR

S METHO D 1 1 RESULT S <PP « BjS ) '(1/20/81} * 22 2 19 5 19 0 18 8 17 1 17 9 19 5 18 2 18 6 19 0 K A Tet t4 B (1/20/811 * 1 4 1 5 1 6 1 7 1 8 1 9 2 0 2 1 2 2 B i s K A Tes t6 1 2 3 4 5 6 B i n • K A Tee t7 ( 1 2 3 4 S 6 7 • B i n • 17 4

17 7 20 3 20 9 19 8 20 8 19 8 20 6 20 3 19 7 (2/25/81} d 28 5 15 1 7 1 9 7 12 8 16 8 15 0 [2/25/81 ) 13 1 28 1 8 2 14 5 20 3 23 8 2 7 1 2 13 7 MFFEREiNC E RENDU (PP« )

S l 2 4 2 4 2 0 4 1 1 2 4 1 4 21 2 2

1 S 2 5 2 4 1 5 2 9 2 1 2 7 2 7 1 9

2 2 1 6

- 1 6 0 1 0 9

1 7 4 8 2 0 4 3 8 4 6 7 2 7 

### i i 3 8 (Continued )

5 3 (Metho d 1 1

HOUSTO N A l <PJ» )

c c 1 6 1 6 j 3 2 8 1 7 11 I S

2 8 1 8 2 8 3 0 5 4 4 7 5 7 5 6 3 3 -Hon l LAS tor ) (PP . »,S )

BE L NA K (PP» )

9 9 7 2

- 5 0

- 7 3 1 0 - 9 5 - 7 0 1

- 9 7

- 9 2

- 3 1

- 2 8

- 3 3

- 3 1

- 3 3

- 4 3 -10 8

- 5 6 ' ' T y i - j'.6 9



### TABL E 16 . RELATIVE ACCURAC YTES T RESULTS ' O N H, S MONITOR S TES T AK D METHO

D 1 1 PirrSRENC E (Metho d 11-Monltor ) (pp « IhS ) •4I E RESULTS REND U BOUSTO N ATLA S PEL MA

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

K A Tea t8 (3/31/81 )

1 0 ia n 6 4

11 6 17 1 7 0 115 15 3 21 2 7 7 7 8 8 4

- 11 4 1 3

6 1 6 1 4 0

- 9

- 1 1 5 1 2 

### 12. 8 £

• 2 7

4 2 7 0 1 0 2 6

- 2 * 4

- 1

_ 9 1 9
Fue l ga s sampl e collecte d l n aTedla rba g take n a tthi atli e and analyte d k y C C oo e da y late rshove d les s tha n 2 ppn B.S . 30-ednut e runs . c d Heroito rno toperational . Fue l ga awa

aspike d vlt h know

n aaoun to f

tjS fo ral l ai x mi .



### 5 4TABL E 17
. RESULT S O F COLLABORATIVE RATES T O NHj S MONITOR S

roe M D DAT S 11 -

(ppv HiS ) LA B 1 LA B 2 DIFFERENC E (Metho d11-Monitor ) (ppm H»S ) BENDI X HOUSTO N ATLA S LAB 1 LA

B 2 LA

B 1 U B 2 DE L HA R LA B 1 LA

B 2

O i R A Tes t 5 (2/18/81 ) 1 2 3 2 2 8 2 7 3 S I 4 3 4 4 3 — 5 4 1 3 3
« 3 3 2 9 7 3 2 2 J 8 3 1 3 2 9 2 9 3 3 Hea n3 3 3 2

* Th a referenc e Metho danalyse s _ j

- 1

- 3

- 2

- 2

- 2

- 2

- 2

- 3

- 2

var a perfon e 1 _« _

1 -1 2 1 -3 9 6 3 -3 3 9 -3 3 4 -3 1 8 -2 7 2 -3 2 5 -3 0

a dsimultaneousl y

b y 

### -t o

- « -3 3 -3 8 -3 7 -4 0 -3 4 -3 7 -3 9 -3 0 •— •

- 8 -4 1
-4 5 -4 4 -4 1 -3 6 -3 5 -3 6 -2 7

- 5 -3 8 -3 3 -4 3 -5 2 -4 3 -3 2 -6 4 -4 0
tw o dlffarcn t laboratorla a utliltin g • — . -% -4 3

— -31 -5 8 -5 2 -5 1 -6 0 -4 3

totall y aeparat c equlpaent , reagenta . an d atandard* .

•> lP.7 1

• M 

## 1

• »->

a .

•



# 1 . l-r.j, - m t• 1 . 4 . M l M M * u -Imtm. r . tf|Mm rtmJ.

•

FIGUR E 11 . ZER

O DRIF T TREN

D FO RBENDI

X CEM .

! I-M 9 

# 1 - T 1 

# """ Y ^ 

## t

• i O

1

I |
* g» * cMctatraitan .

A •l»i:r«« t fcniti— 1 •UatruMB f raHif* 4 

## 1 .i-— .

T * 

## / ]

FIGUR E 12 . SPAN DRIF T TREN D FO RBENDIX CEM.

5 6P.7 2

!

• 

## I 

# i • 

# r- U 

# J ' ft-1, L
/ 

# 1 .1—» - • a.km



### •—-I.JUh.

. A !

U l . M n tatlm.



# 1

FIGUR E 13 . ZER

O DRIF T TREN

D FO RHOUSTO

N ATLA S CEM.

aji/l.l^ X VI 

# w l J k

=•# = caJUratt. . a* * * tf.t«4B .

• M « " ec r FIGUR E 14 . SPA

N DRIF T TREN

D FO RHOUSTO

N ATLA S CEM

.

5 7P.7 3

:r t ae r tm mt

-mm -tt* mm FIGUR E 15 . ZER

O DRIF T TREN

D FO RDE L MA

RCEM .

FIGUR E 16 . SPA

N DRIF T TREN

D FRO M DE L MA RCEM .



### 5 8P.7 4

REFERENCE S

1 . Standard s o f Performanc e fo r Ne w Stationar

y Sources . Petroleu

m Refineries . Federa l Register , 43 : 10866-10873 , Marc

h15 . 1978 . 2 . Repp , N . Evaluatio no f Continuou s Monitor s fo r Carbo n Monoxide l

nStationar

y Sources . EP

A 600/2-77-063 , U.S . Environmenta l Protectio nAgency , Researc

hTriangl e Park , NC , 1977 . 15 5 pp . 3 . Maines , CD. , an d V.C . Kelly . Determinin g Laborator

y •n d Fiel d Performanc e Characteristic s o f H_ S Monitorin g Systems a s Applie

d to Petroleu

m Refiner

y Fue l Ga s Lines . Draf t Fina l Report , EPA Contrac t 68-02-2707 , Scot t Environmenta l Technology , Sa nBernandino , CA , 1978 . 4 . Standard s o f Performanc e fo r Ne w Stationar

y Sources . Propose d Revision s to Genera l Provision s an d Addition s to Appendi xA , an

d Reproposa l o f Revision s t o Appendi x B . Federa l Register , 46 : 8352 , Januar y 26 , 1981 . 5 . Standard s o f Performanc e fo r Ne w Stationar

y Sources . Appendi xB . Performanc e Specification s Federa l Register , 40 : 46250 , 46271 , Octobe r 6 , 1975 . 6 . Determinatio

no f Hydroge

nSulfide Emission s fro m Ne w Stationar

y Sources . Petroleu m Refineries . Federa l Register , 43 : 1495 , Januar y 10 , 1978 . 7 . Determinatio

no f Carbo

nMonoxid

e Emission s fro

m Ne w Stationar

y Sources . Petroleu m Refineries . Federa l Register . 39 : 9319-9323 . Marc h8 . 1974 . 8 . Allen , T.H. , an d V.J . Root . Colorimetri c Determinatio n o f Carbo

nMonoxide i

nAi r b

y A nImprove

d Palladiu

m Chloride Method . J . Biol . Chem. , 216 : 309-17 . 1955 . 9 . Anonymous , Determinatio no f Lo w Concentration s o f Carbo n Monoxide . J . Soc . Chem . Ind. , 57 : 79-82 , 1938 .



### 5 9P.7 5



### 10 . Polls , B.D. , L.B . Berger , H.H . Schrenk , Colorimetri c Determinatio n o f

Lo w Concentration s of ' C O b y Us e o f

a Palladiu m Chlorid e - Phosphomolybdl c Acid-Aceton e Reagent , Publicatio n No . 3785 , U.S . Dept . o f Interior , Bureau o f

Mines , Repor to f

Investigations , Novembe r 1944 . 16 pp . 11 . Veins , R.E . Colorimetri c Method s fo rth e Determinatio n o f C O i n Air . Thesis . Kansa s Stat e University , Manhattan , Kansa s 1973 . 3 2 pp . 12 . Lambert , J.L. , an d R.E . Veins . Induce d Colorimetri c Metho d fo rCarbo

n Monoxide Anal . Chem. , 46 : 929-93 0 1974 . " "

6 0P.7 6

APPENDI XA DEFINITIO

N O F TERM S

Calibratio

nDrif t - Th

e differenc e inth e monitor' s outpu t reading s fro

m th e establishe

d referenc e valu

e afte r a state

d perio d o f operatio

ndurin g whic hn o unschedule

d maintenance , repair , o

r adjustment ha s take nplace . Calibratio

nErro r - Th

e differenc e betwee nth e pollutan t concentratio

nIndicate

d b y th e continuou s monitorin g syste m an d th e know nconcentratio

no f th e tes t ga s mixture . Interferenc e Equivalen t - Positiv e or negativ

e respons e cause d b y a substanc e othe r tha nth e on e bein g measured . Operationa l Perio

d - A minimu m perio d o f tim

e over whic

ha measuremen t syste

m l s expecte

d t o operat e withi ncertai n performanc e specification s without unschedule d maintenance . Outpu t Nois e - Spontaneous , shor t duratio ndeviation s inth

e analyze r outpu t tha t ar e not cause d b y Input concentratio n changes . Nois e I s determine d a s th

e standar

d deviatio

n about th

e meanexpresse

d a s a percentage o f ful l scale . Precisio

n- Variatio

nabou t th e mea no f repeate

d measure ment s o f th

e sam e pollutan t concentration , expresse d a s on e standar d deviatio

nabout th

e mean . Rang e - Th

e minimu

nan d maximu

m measuremen t levels . Relativ e Accuracy

- Th e degre e o f correctnes s wit hwhichth e continuou s monitorin g syste m yield s th e valu e o f ga s concentratio

no f a sampl e relativ e t o th

e value givenb

y a define d referenc e metho

d or th e emissio

nstandard . Spa nDrif t - Th

e chang e i

nth e continuou s monitorin g sys tem' s outpu t over a state d perio d o f norma l an

d continuou s operatio

nwhe nth e pollutan t concentratio nat th

e tim e o f measuremen t l s th

e sam e know nupscal e value .



### 61P.7 7

Syste m Respons e Tim

e - Th

e tim e interva l betwee na ste

p change i

npollutan t concentratio nat th

e input t o th

e monitorin g syste

m an d th e tin e at whic h95 1 o f th e correspondin g valu e I s displaye d onth e system dat a recorder . Zer o Drif t - Th

e change i

nth e continuou s monitorin g syste m outpu t ove

r a state

d perio d o f tim

e o f norma l an

d continuou s operatio

nwhe nth e pollutan t concentratio na t th e tim e o f th e measuremen t l s zero .



### 6 2P.7 8

'!-"'( •

APPENDI XB

TENTATIV

E PU N FO RTH E EVALUATIO

N OF C O AN D H 2 S CONTINUOU S MONITOR S AT REFINERIE S



### b y
Willia m J . Mitchel l Quality Assuranc e Divisio

n Environmenta l Monitorin g System

s Laborator

y U.S . Environmenta l Protectio nAgenc y ResearchTriangl e Park , N C 2771 1

APRI L 197 9



### 6 3P.7 9

>*°«* i UNITE D STATE S ENVIRONMENTA L PROTECTIO N AGENC Y ENVIRONMENTA L MONITORIN G SYSTEM S LABORATOR Y

RESEARC H TRIANGL E PAR K NORT H CAROLIN A 2771 1 

### Apri l 26 . 197 9

Dea r W e ar e Initiatin g a program t o evaluat e th e long-ter m reliabilit y

o f continuou s monitor s fo r measurin g H- S I nfue l ga s fee dline s a t petroleu m refinerie s an d fo r measurin g C O emission s fro m flui dca t cracke r stacks . O nMarc h15 , 1978 , EP A promulgate da regulatio ntha t require dpetroleu m refinerie s t o Instal l suc hmonitors , bu t onl y afte r EP A

develope d performanc e specification s fo r thes e monitors . Th e objectiv e o f ou r program 1 s t o evaluat e tentativ e specification s recommende dfo r thes e monitor s b y

a nEP A contractor . Th e program

wil l Involv e Installin g C O and H- S stac k ga s monitor s a t a petroleu

m refiner y

an d operatin g and maintainin g thes e monitor s fo r approximatel y

on e year . Th e 197 9 Pollutio nEngineerin g Yearboo k an d Produc t Guid e indicate s tha t yo u ma y hav e on e o r mor e monitor s tha t coul d b e use di nthis study . I f thi s i s correct , w e woul dappreciat e receivin g Informatio nabou t you r monito r a s a nai d Inplannin g ou r program . Fo r you r convenienc e w e hav e enclose da nattachmen t wit hthi s lette r tha t outline s th e informatio ntha t w e need . Fo r you r Informatio nan d comment , I hav e attache da copy o f ou r tentativ e plan . We anticipat e tha t th e H- S continuou s monitor s wil l b e monitorin g a stac k ga s tha t wil l b e comprise dprimaril y o f methan e an d hydroge nand contai n30-50 0 pp m HpS , 10-50 0 pp

m mercaptan s and some SO2 . Th e C O monitor s wil l b e monitorin g a flu e ga s tha t wil l hav e th e followin g character : 25-80 0 pp m CO , 8-15 % CO? ; 200-60 0 pp m SO? , ?0 0 pp

m NO , 8-12 % H-0 , and particulat e concentration s betwee n25-15 0 mg/ m . I f yo uwis ht o submi t Informatio nabou t you r monitor(s ) o r nee d furthe r information , pleas e writ e t o m e a t th e addres s abov e o r cal l m e a t (919 ) 541-2769 . Sincerel y yours ,

William J . Mitchell , Ph.D. . Chemis t Sourc e Branc h Qualit y Assuranc e Divisio n(MD-77 ) Attachments 

## 64P.8 0

TENTATIV

E PU N FO RTH E EVALUATIO

N O F CO AN D H^ S CONTINUOU S MONITOR S A T REFINERIE S

I . BACKGROUN

D O nMarc h15 , 1978 , EP

A promulgate

d Ne w Sourc e Performanc e Stan dard s tha t require d petroleu

nrefinerie s t o continuousl y monito r th

e C O emission s fro

m flui d catalyti c cracker s an d th e H- S level s infue l ga s fee

d lines . However , a t th e tim e th e regulation s wer e promul gated , EP

A di d not hav

e performanc e specification s availabl e fo r th e C O an d H- S continuou s monitors . Therefore , th e refinerie s ar e no t require d T o Instal l th

e monitor s unti l thes e performanc e specifica tion s ar e developed . Tentativ

e performanc e Bpecification s fo r bothC

O an d H- S monitor s hav e no w bee nadvance

d base d o nlaborator

y an d field evaluation s don e b y Scot t Environmenta l Technology . I nth e laborator

y phas e o f Scott' s program , candidat e instrument s wer e evaluate d t o determine respons e characteristics , stability wit htime , temperatur e an d flo w rate , an

d sensitivity

t o potentia l Interferences ' likel y presen t l

nth e stack gas . Instrument s tha t performe d adequatel y

lnth e laborator

y wer e the nevaluate

d a t a petroleu

m refiner

y to establis hthei r field performance . Fiv e C O monitor s an

d tw o H- S monitor s wer e evaluate d a t th e petroleu

m refiner

y durin g field trial s tha t laste d approximatel y

5 5 days . Onl y

on e C O monitor an

d on e H- S monito r performe d adequately . I nth e cas e o f th

e CO monitors , dall y calibratio

ncheck s wer e manda tor y fo r reliabl e operatio no f th

e Instruments , bu

t eve nwit hth

e inclusio no f dall y calibration , Scot t questione d th e lon g ter m reliability

o f thes e monitors . Instrumen t malfunctions , samplin g syste m malfunction s an

d dat a logger malfunction s plague d thes e fiel d evaluations . Base d o nthes e studies , Scot t propose d tentativ

e performanc e spe cification s fo

r bothCO an

d H- S monitors . Th e propose

d C O monito r specification s are summarize d i nTabl e B-1 . Th

e propose

d H 2 S monito r specification s are th e sam e a s thos e describe d l nEP A Performanc e Specificatio

n2 - "Specification s an d Tes t Procedure s for SO - an d N0 X Continuou s Monitorin g System

s i nStationar

y Sources. "



### 6 5P.8 1

TABL E B- 1 RECOMMENDE

D PERFORMANCE SPECIFICATION S FO R CONTINUOU S MONITOR S O F CARBO N MONOXIDE A S APPLICABL E TO PETROLEU M REFINERIE S

PARAMETER S SPECIFICATIO N
Rang e Calibratio

nError Relativ e Accurac

y Precisio

n Respone Tim

e (Systen ) Output "Noise Zer o Drift , 2 Hour s 1
Zer o Drift , 2 4 Hour s 1 Spa n Drift , 24 Hours Interferenc e Equiv . 15 tC0 - Interferenc e Equiv . 10 J H^ O Operationa l Perio d 0-100 0 pp m £2 * Spa n j(10 5 Mea

n Ref . Valu e O J Spa n O O Minute s O tSpa n <y% Spa

n <2% Spa

n <2.5% Spa

n <\0 pp m <5 pp m 16 8 Hours Expresse d a s su

m o f absolut e mea

n valu e plu s 95 1 confidenc e interva l i n aserie s o f tests . Thi s valu e i s base d on • relativ e compariso n o f th e monitor s t o eac h othe ran d no tt o Metho d 10 . I I . PROPOSE

D PU N A . Objectiv e Establis hth

e long-ter

m operationa l performanc e (durability / reliability/accuracy ) o f CO an d H- S monitor s whe nthe monitor s are installe

d an d maintained a s directe d b y th e instrumen t manufacturer / vendor an

d fro m thi s dat a determine wha t ar e reasonabl e an d usefu l performanc e specificaion s fo r thos e monitors .


### 6 6P.8 2



### B . Duratio n o f

Projec t Th e fiel d testing wil l las t approximatel y on e year . The labora tor y testin g precedin

g th e fiel d stud

y wil l las t one t o thre e month s dependin

g o nth e problem

s encountere

d an d th e Instrument s selecte d fo r evaluation . C . Sit e SelectionCriteri a 

### Th e C O nonitor s wil l b e installe d a taflui d ca tcracke ran d th e H- S nonitor s wil l b e Installe d o n afue l ga s fee d lin e preferabl y equippe d wit h a

n amin e treate rfo rremova l o f H-S . Ih e actua l selectio n o f

th e tes tsite(s ) wil l b e nad e usin g th e followin g criteria :

1 . Attitud e o f

plan tmanagemen

ttowar d program . 2 . Accessibilit y o f sit e t o EP

A an d EP A contracto r personne l fo rinstallation , calibratio n an d maintenanc e o f

equipment . 3 . Schedule d plan tshut-down s fo rmaintenance / productio n changes , etc . 4 . Availabilit y o f

aroo m o rtraile rtha tl s suitabl e fo rinstallin g continuou s monitors , i.e. , on e tha t ca n b e maintaine d a taconstan ttemperatur e an d humidity . 5 . Availabilit y o f astable , continuou s suppl y o f electrica l power . D . EquipmentProcuremen t 1 . Continuou s Monitor s Th e continuou s nonitor s wil l b e selecte d base d primaril y on engineerin g Judgmentabou tthei rtechnica l reliabilit y an d durability , maintenanc e requirements , dat arecordin g requirements , an d avail abilit y o f

spar e parts . Specifi c criteri afo rmonito rselectio n includ e th e following :

a ) Willingnes s o f

nonito rvendo rt o cooperat e wit h EPA , e.g. , suppl y th e monitorin g syste m requeste d includin g al l pre-deliver y instrumen tcheck-out s requested . b ) Cos to f

th e nonitorin g syste m t o th e governmen ti n relatio n t o othe rnonitor s wit h simila roperatin g principles . c ) Deliver y tim e involve d I n obtainin g th e nonitor . 67d ) Anticipate d cos t o f nalntenance , calibratio nan d repai r o f th

e Instrunent Includin g availability

o f spar e parts , eas e o f on-sit e repai r an d availability o f servic e personne l fo r majo r equipment repair .
e ) Samplin

g condition s require d b y th e nonitor . I.e. , temperature , stac k ga s character , humidity , flow rate , etc. , an

d availability

o f a aultabl e sampl e conditionin g syste m fo r obtainin g th e require d samplin g conditions . f ) Existenc e o f a similar syste m o nothe r petroleu

m re finerie s an

d the demonstrate d performanc e o f the system . g ) Availability

an d cos t o f trainin

g EP A contracto r per sonne l i

nth e operatio

nan d maintenanc e o f th e noni torin g system . 2 . Stack Ca s t o Monito r Conditionin g Syste m Th e actua l samplin

g syste m require

d t o brin

g th e stac k ga s t o th e monitor s canno t b

e determine

d unti l th

e field site(s ) an d th e candi dat e monitor s ar

e selected . I f a commercially-availabl e syste m exist s tha t ca nb e obtaine

d a t reasonabl e cost , suc ha syste

m wil l b e bought . However , i f necessary , a site-specifi c sampl e conditionin g syste m wil l b e designe

d an d installe

d b y EPA . Th

e syste m Installe

d wil l mee t o

r excee d requirement s o f ever y nonito r tha t wil l b e use d i nth e evalua tion . 3 . Dat a Recordin

g Syste m I t i s anticipate

d tha t stri p char t recorder s wil l b e use d t o recor d al l dat a generate d b y th e monitors . Dat a logger s an d magneti c tape s wil l likel y

no t b e use d sinc e thes e device s hav e no t demon strate d long-ter

m operationa l stability . Similarly , manua l calibra tio nan d spa ncheck s wil l b

e a nintegra l par t o f th e progra

m rathe r tha nrelyin

g simply

o nautomati c controllers . E . Traile r for Housin g the Monitor s Monitor s requir e a well-controlled environmen t fo r operationa l stability . A

traile r o

r similar facility tha t ha s temperatur e an d humidity

control s wil l b

e use d to hous e th

e nonitors . F . Determinatio

no f Performanc e Specification s an d Operationa l Characteristic s Th e performanc e o f th e C O monitor s wil l b

e compare

d t o th

e ten tativ e performanc e specification s no w bein g advance

d b y QAQP S a s Performanc e Specificatio n4 . Th

e performanc e o f H- S monitor s wil l b e compare d to th

e nos t recent specification s fo r SO - an

d N0 „ nonitors . 

### 6 8Relativ e accurac

y performanc e test s fo r C O wil l b

e conducte

d usin g EP A Metho d 1 0 unles s ESR

L i s abl e to supply a we t chhemica l tes t netho d for CO . Th

e relativ

e accurac

y test s fo

r H- S wil l b

e conducte

d usin g EP A Metho d 11 . Initially , th e number o f sample s specifie d I nperfor nanc e Metho

d 2 for SO - wil l b e use d fo r th e H- S an

d 0 0 relativ

e accurac y tests . Spa

ncheck s an

d drif t check s wil l t> e done dail y

usin g calibratio

nga s mixture s tha t correspon d t o OJ , 25J , 50J , 75 J an d 100 J o f span . However , no t al l spa ngase s wil l b

e use d everyday . Describe

d belo w l s th e tentativ

e schedul e fo

r thes e tests . Thi s schedul e na

y change base

d o nfina l selectio

no f nonitor s an

d tes t sites : Paramete r Relativ e Accurac

y Tes t
Zero/Spa

nCheck s 0 , 50J , 100 J spa

nchec k 0 , 25J , 50J , 75J . 100J spa nchec k Respons e Time/Nois e Check Interferenc e o f othe r gase s Tim e Interva l 1 week 1 , 2 , 4 , 8 , 1 2 month s

dail y weekl y weekl y monthl y G . Tentativ

e Schedul e for Accomplishmen t o f Stud y Tas k Obtai npermissio

nt o presurve

y tentativ

e site s Complet e sit e visit s an d selec t tes t site s Orde r monitors/samplin g systems , etc . Procur e necessar

y supplie s fo

r referenc e metho

d test s 

### Complete laborator y check-ou t o f monitor s Install/check-ou tnonitor s Complet e fiel d studie s Completio n Dat e
Ma y 15 , 197 9
June 15 . 197 9

i 

### Jul y 15 . 198 1 Augus t15 , 197 9
Novembe r15 , 197 9 January 15 , 198 0 Januar y 15 , 198 1

6 9P.8 5

III . SPECIA

L MOTE S A . Eac hnonito r wil l b

e subjecte

d t o whateve r la

btest s ar e necessar

y t o deternine l f i t wil l work Ina fiel d situation . Thes e la

btest s na

y b e done b

y th e vendor befor e shippin g th e equipmen t t o th

e EP A contractor . B . Tentatively , w

e pla nto hav

e th e perso nor person s res ponsibl e fo

r naintalnln

g th e nonitor s receiv

e nonltor-specifi c trainin g fro m th e Instrumen t vendor either on-sit e or a t th e vendor' s facility . C . Base

d o ncos t an

d anticipate

d deliver

y time , spare s o f thos e component s mos t likel y t o fai l (phototubes , scrubbe r columns , switches ) wil l b e store d a t th e tes t site . D . I f possible , tw o identica l Instrument s na y b e operate

d a t th e sit e t o yiel d a

nestimat e o f instrumen t precision . Th e netho d o f standar

d addition s na

y als o b

e employe

d o noccasio

nt o chec k th

e reliability

o f th e monitors . I

nthi s case , a calibra tio nga s woul d b

e Injecte

d Int o th

e sampl e strea

m t o see i f the expecte d Increas e i

nrespons e wa s obtained .



### 7 0P.8 6

APPENDI XC VENDOR S RESPONS E T O LETTE RFRO M EPA MCAT m a o usa-ms t usrons t e o t, s norosr o WSTHUNP H corT/ofDurrn c ntwcir u Affile d Automation , toe •ertleevllle . O

K amttm tceleg y Corp . f . 0 . %n SM.

. X X 1KM leelkarac b laetr—ant e 130 0 Leghor n Stree t Nnatal a View . CA MO O aeaella e laduatrle a f . 0 . te a M l lyeae , C

O tOSAO •actaa e loetnaefita . Ise . frecea . Inetruaent e Divlala a *»O 0 Harke r tl* . fiUlartoo . C

A fM M teedt a Corporatio n bvirooaenta l an d Precea a Zaacr-uaant a Civlala n f . 0 . Dreve r 13 1 Lewiaaurg . H

V 2*M 1 fertroRa-eetal an d frecaa a Aoalyie r Karkc t DrraUn—n t CE A iBatnaaanta . lac . I S Ctwrle a Stree t Maacmd . U 07*7 } Calibrate d laatnaarnta . toe. 7) ] Sa wMil l live r loa d A r deley . « 1050 2 CaaitrarcfCocr i Cor*
. •1 0 tDtllo s Driv e ritta*ur«b . PA 1323 S Centra l Iaetriaaent a Carp
. I f ttt fix Avaau e falrfleld , H J OTOO * Dictaphon e Ca
. Detectio n fro-duct e Awdio/IJaetronlc * Divl.le n *7 S till . Stm t •tHatal x Via* . C

A MO O CD : Optlchre a 10 2 •af : Optlchre a 10 2

00 : SOO

O

CO : P 103ft * B.S : P I030 A

CO : MS- U •iS : M l

CO : M0 3 «,S : 777 0 CO : ti7t>/cc/rn >

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

CO : SJSOO/

U

CD : 14500/CC/T

C l.f : »3«00/CC/rf D

CO : «t700/HC n •,S : ftOOO/Chcailualnaacasc a

CO : StOOO/KDD

t •,S : S»710/CC/m >

aifllak . Ue . 23 7 Pu t s« > Avenu e Caa*rld|c , M 0213 * t.l . DuPon t DcNeaour a t Ca
. 100 7 Marke t Stree t HUaU|ioe
. KItTO t la-erratic . Science , lac . t 3 Caacutlv e Blvd . tJaaferd . « TIOS2 3 I X CO i Snatru
. ae t epeclfla d U (coa t ae t opacified )
•a( : *0 0 I.S
. (M00/0 V

n CO : tcelyie r 310 7 CO : IllOO/electroe h



### 7 1P.8 7

APPEND S C 

### VENDOR S RESPONS E T O LETTE RFRO M EP A ncATi n * o Uspoai t UST-ONS tC

O B. S nopost s WSHUWH T cort/optJUTin

c mvcir u Dy-eea c lance . environmenta l Product . Div . Teaaiehl p Lin e tea d Blaeeall . P

A 1*422 Ecolog y Board , lac . 92J 7 Independenc e Ave . Oataaorth . C

A •131 1 tthy l latertec h Carp . I tftoe.el tea d frlaceteo . « J OSSA

O BrvletfPeckjr d Scientifi c Initriaaent aDiv . 1*0 1 Californ U Avenue Pol e Alto . C

A 9430 4 •ortk aInetriawate . lac . 102 1 DurveaAve . - Irvine . C

A 9271 * Ibueto n Allot . IJK . ••it ) Seythorv e Driv e Bouatoft , T

X 7704 1 lafrare d leduatrie a Vketer n Dlviale n p . 0 . Bo a9* 9 Cast a karhara , C

A 9310 2 U u rBaaearc h take . lac . J0 9 K . Fairfa x Ave . to* Angela. . C

A 9003 4 la-ad . aRorthru p Ceapan y SVjae-iaytov

n Ptk a Bert h WaJaa

. P A 1945 4 Nilo y lab-or e torlea , lac . • 71 5 Electroni c Driv e B . Springfield . U 2213 1 •da aSafet y Appllaac e Ca . •0 0 Pen n Cente rtlvd . Plttaaurgh , P

A 1S23 S Monito rLake . lac . 101» 0 Scrlpp a-tenc

h Blvd . Sen Diego . C

A 9213 1 Procea aAnalyiere , lac . 110 1 Stat e toa d Princeton , B

J 01*4 0 Hilto n to y Cuapaii

j Plo w Contro l Div . 20 5 Ivylaa d toe d Ivylaad , P

A 1117 4 Teledyne . lac . Analytica l Io.truaent e Div . 93 ) V . Ri.elo e Driv e Ba e Ckrial . C

A 9177 t •2SH-107 W 722S-102

70 3 t.S : S7200/P b A c B.S : S12,OS9/PhAc- *

CO : S19tS/RDXa

lir a20 2
CO : lof tdetecto r B.S : Be tepaelfle d
CO : 24-222- 4 B.S : 12-23 0 CO: S4400/KB U
CO : S7000/RSD

L l.i : CC/T O
CO : 94100/CC/T C B.S : S99O0/CC/TT

D

CO: 930 0 B.S : ti l DHCO-2Q

X CO : StS00/»I t

B.S : S4700/U

V Tfcera o tlectro n Carp . trviroeacnta l In,tru e 10 1 Sawt h Stree t Bofklntea . HA 0174 9 •t a Mv . 

### 72P.8 8

APPENDI X C VENDOR S RESPONS E T

O LETTE

RFRO M EP A BKATIVI • o Bisr-oas

t USPORS Z C D B. S nopos o wntw-a w COn/OPOUTIM C PtlKCXP

U

Tracer , lac . Saatruaaa tDlvlale n •SO O Traco rlen e Anatla . X

X 7972 1 •fceter n Beeeerc h aa d Develepaen tltd . 131 3 - 44t h Ave. , B I Calgar y Alt a
l e i Ma rScientifi c P . 0 . Bo

a4S 4 Addiaoo . T

X 7300 1 Anarad , Inc . P . 0 . Bo

a 314 0 •ant e Serhere , C

A 93I0 S •fl :

MX CD : A

B SOl k B.S : S4700/PkA c

co : tjsoormn
* Orginall y prepoaad , hutwlae n col d orderin g Del Ma rChe y offere d th e S2SR-102N .



### 73P.8 9



### APPENDI X D FC C EMISSION

S GA S SAMPL E CONDITIONIN

G SYSTE M Th e stac kga s was conditione d a tth e stac kt o remove particulate , aci d nls tan

d noisture . Th

e ga s conditionin g syste m wa s house d I n a neta l cas e 5 5 c

m b y 7 6 on b y 3 3 cn . Th e syste m (Figur e D-1 ) consiste d o f th e followin g parts : 1 . Probe . S S 202 , lengt h 13 0 on , O D 5. 1 cm , I

D 4.9 " cm , slot s 2 t o 4 a

n wid e cu tl n th e 4 0 c m neares tth e ti p an d covere d wit h Balsto n Typ e 20/80- A microfibe rfilte r (5. 1 c m I D by 4 5 c

m long) , glas s wool plu g l n prob e tip ; an d stee l plat e welde d 5 c m fro m th e en

d t o attac h prob e t o por tflang e an

d prob e extensio n (Figur e D2) . 2 . Prob e Extension . Aluninu m pipe , 2 8 c

n long , 1 0 c o OD

, on e end welde d t o a l uninu n plat e (t o attac h extensio n t o probe ) an

d othe rend externall y threade d t o accommodat e pip e cap . Eac

h sid e containe d apiec e o f aluninu m tubin g 2. 5 c

m O D b y 8 c

m lon g t o allo w sampl e t o pas s fro m prob e int o th e ga s conditionin g syste m an d t o allo w astac ksampl e t o b e withdraw n int o aTedla rbag . Th e botto m o f

th e extensio n containe d apiec e o f aluninu m tubin g 1. 6 -c

m O D b y 5 c

m lon g fo rattachin g a6 0 c m U-shape d drain . Thi s drai n continuousl y remove d condensat e fro

m th e prob e extensio n whil e maintainin g a wate rsea l t o preven tambien tai rfro m enterin g th e system . 3 . Balsto n 20/80- A Filte rHousin g (SS304 ) wit h type 200-8 0 Grad e D an d Type 200-3 5 S S filte rsuppor tcor e filter . Ga s passe d fro

m insid e t o outsid e t o coalesc e wate ran d remove smal l particulates . A U-tra p wa s attache d t o th e botto m t o allo w continua l drainin g o f th e condensate . 4 . Balsto n 97S 6 Filte rHousin g (SS316 ) wit h 050-05C H micro fibe rfilter s (1. 2 c m I D b y 3. 1 c

m long) . On

e o f thes e filter s wa

s added t o th e syste m December5 , 1980 , t o reduc e pluggin g o f

th e Perm

aPure dryer ; th e secon d was adde d January 9 , 1981 . 5 . Perm

aPure Mode

l PD-1000-24 S (20 0 tubes , 6 0 c n long) . Tw o connecte d i n serie s t o remove moisture . A pressur e regulato rwa

s use d t o maintai n drye rpurg e ai ra taflo w o f 1 7 L/mi n a t2 t o 3 psi .

7 4P.9 0



### 6 . Pump

. AD I Mode l 19320- T dual-stag e (wit h Carpente r2 0 head s t o reduc e corrosion) . Teflon-coate d diaphram an d Vito n valv e gaske tan d discs . Th

e single-stag e pum

p use d originall y woul d b e adequat e fo rmos tsystems . 7 . Tubing . S S 31 6 betwee n prob e extensio n an d Balsto n 97S 6 filter , polypropylen e betwee n 97S 6 filte ran d puap . 8 . Sampl e Line . 20 0 n long , 0.9 5 on I D b y 1. 2 c

m OD , blac k nylon , unheated . 9 . Balsto n 20/80- A Filte rHousin g wit h Type 20/80- A Grad e D , nicrofibe rfilter . Locate d immediatel y i n fron to f th e traile rt o remove fin e particulate . Th e overal l performanc e o f th e ga s conditionin g syste m wa s ver y good . Problem s an

d change s tha toccurre d betwee n Februar y 11 , 1960 an d Apri l 28 , 1981 , ar e summarize d i n Tabl e D-1 . I n general , th e followin g comment

s ar e noted : 1 . Polypropylen e tubin g wa s foun d t o b e superio rt o stainles s stee l tubing . Th e latte rreacte d wit h th e stac kga s t o yiel d afin e particulat e tha tcollecte d a t bend s an d elbow s i n th e conditionin g system . 2 . Th e Balsto n 20/80- A filte rwas difficul tt o disassembl e i n th e fiel d due t o it s larg e diamete ran d th e lac ko f larg e wrenches . 3 . Th e U-shape d drain s worked well , bu tcar e shoul d b e take n t o preven tfreezing ; eithe rb y wrappin g th e drai n wit h heatin g tap e o rb y usin g hea tradiatin g fro m th e stack . 4 . Fro m Februar y 18 , 1981 , t o Apri l 28 , 1981 , th e syste m worke d withou tfailur e o rmaintenanc e a tasamplin g rat e o f 5 t o 8 L/min . Vhe n disassemble d o

n Apri l 28 , 1981 , th e Perm

aPure drye rinle tcontaine d no particulate , th e Balsto n 20/80- A filter s wer e unbroken , th e pum p inle t diaphram containe d areddis h syruplik e liqui d (p H les s tha n one ) tha tabsorbe d wate rrapidl y upon exposur e t o th e ambien tair . A

n anio n analysi s showed tha tth e onl y anio n presen twa

s sulfate . 5 . Th e syste m describe d was constructe d t o provid e asampl e flo w rat e o f

6 t o 1 5 L/mi n t o th e traile rwit h aminimu m syste m respons e time . Formos tapplications , aflo w rat e o f 1 L/mi n woul d b e sufficient ; thu s on e PD-750-2 4 Inc h (100-tube ) Perm aPure drye rmigh tb e adequat e fo r

7 5P.9 1



### nos tapplications . Thi s woul d resul ti n aconsiderabl e savings . I

n addition , th e prob e extensio n an d th e Balsto n 20/80- A filte rl n th e sample cas e eoul d b e replace d with aroalle runit s withou tadversel y affectin g th e aampi

e conditionin g systen . Prob e filte rintegrit y wa s maintaine d a s lon g a s th e slotte d sid e o f th e probe wa s facin g downstream . Vhe n th e probe wa

s rotate d 9

0 s o tha tonl y hal f

th e slotte d sid e o f th e prob e wa

s facin g downstream , ahol e aboutone c m l n diamete r forme d I n th e filte ra tapoin tabout35 c m fro m th e tip . A glas s woo

l plu g l n th e prob e als o helpe d kee p th e prob e clear .

7 6aa-H i 2 STAG E "AD r DIAPHRA M PUM P

T O SAMPLE •DISTRIBUTION SYSTE M 

# « 

# ^— * * - V PURMA-PUR E GA S DRYER S SAMPLE PR08 E IN-8TAC KFILTE R /,//M//////////hW///l V M " •

{ - a r a |

1 BALSTO N TYP E 8 0 FILTE R



# \^r WATE

RTRA P A DRAI N

FIGURE D-1 . SCHEMATI C DRAWIN G O F SAMPL E CONDITIONIN G SYSTEM .P.9 3

FIGURE D-2 . PROBE , PROB E EXTENSIO N AN D BALSTO

N 20/80- j A FILTER .



### 7 8TABL E D-1 . MAINTENANCE/REPAIRO F STAC KGAS CONDITIONIN G SYSTE M O F FCCU



### v o 9

a 

## vm tnt tm

vn
an d/1 9 %na
9/ 3 im pn vn tm 19/1 1 j a ^ 

# J

mL.

m»
• 3

S

t 9
7
1 1
1 1

9 9 » 

### 1- f I

94

. • * e
9 S

i d

1 7 I I I t I S
1 1

I f 1 7 • 

# 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

1 7 1 7

1 7

9 1 9 1 9 1 7 1 9 I S 1 7 I I 1 9 1

ACTIVITY : iMtelle d .jrttea . *ee e .lette d aid e fecia l dewntre * vlt h flea , aee l ple a l e tip . M l W-7T 9 Uklat . Pmm UmpH « t «OI-MJI0 Tvill i ee . rKlrcelatla n lytta a t a centre l flaw . f 1e > rv,trlcte d k

y tim fre y pevda r a t P* « Inlet . *a*ec* d S t 71 9 tekln e krteee * **P end po p wit * pely*re*yleae . C i a t pmm evtla t m d I n .tac k

7 S pre k y POI« . 'len t aenlte r ree d M pan . Sytla e \ttk-t*>Kkt4 a t 9 Inc * *» . P.vdi r analytli : la : II I {t-.l); Anle n $0^ , p

M candmtate 7.7 . Caw-Pu n at . freen . IIMH I pw a rvtlrcelatle n ayata a tocevae velv e leetlnf . Pe t *-tn » I n t a eeltet t tend»n»et. . 9ret a ea a lectin * e t te a •olalr d prat e W an d IIWIII I fl.t i m l pla t t e .e e effec t e n pertlcelat e fllUrln p efficiency . Prek e elver . C

9 .tec * 1 4 pea , C

O . t pmm

evtlr l J l ppa . f*9 perf . ai r lin e eccleantl y cteMt f af f l y iaa>i m e t plant . Sytt M fal l t f eate r ke t Mil l pawta* . 9rativ d *yet « • aim l ai r Hn* . eat i n te a .tea e ajpa

a (MI-IIUOT ) t e fiv e 1 9 9* 1 preater e a t traile r U acteaajedet a Calle d teteaatte a aenlta r reaelreaent. . Ilnt* d teklD f raatrlcttn f fle a Int e paep . arplace d cracke d prek e flttar . rpek

a ka * aael t pertlcele U dapeelt . 9a t aa a ne t eccludad . Hen t C 9 wr y Mfk . PH

l a 1: 9 ditatla n mi— to krln e 0 9 Int e epa a reaf t a f aenlter . 9 1 le t te n >y*te a reae* * **m% IWO . tat attain s prek

e eaten.te n aavlppad wtt h 9 drai n ant e ante . Sytte a Ot . Inatatle d CO
. aanlta r I n trelltr . tattere d r^twe d pa wdlaphrt a a a aaaa Itttt . RtpfftCt vttw f pM ^ •"M*"'**aB j WC1 I H I R M PVpW-PVV . M M frf( P MPMi l V N NMV . lin e pleaped . traine d I J 1 fre e f-90- 1 filter , laapl a fle e aete r (retaaeter ) kel l cerreded . keten d t-et—t n fi w •y*ta a vlthee t repteceeent . —



### (Continued )

It o a*a

### TABL E D-1 . MAINTENANCE/REPAI RO F STACKGA S CONDITIONINGSYSTE M O F FCC U

o o o 199 9 11/7 7 11/1 9 U/ 9 I S 1/ 9 VH

1/1 9
v n tm
l/ M 4/79 1 *

k *

a
• n

t 9 1

-

- *
•

-

- 9
7 I
I

1
•

• 1 t

a • •
i

a

a i activit y

** • Intt t pleeaa dait hgree ndapeatt . Anatytl . aimed : (7:1: 1 fa r ftiMiCr) , aalt a M | tn d»t . M RJ I (9 * att0M| . Hr.ivre dtanpl . fle a eiln f tP O purg e ai r rataeater . trek e filte r hedhet e InIt . Irtttced . 77 9 partiall y planed , tapttcedt

-PP 1999-79*9 9 (f l c a a 19 9 tdket ) att * ta t n fJO-t t (C l c a a 10 9 take.) , trplacedpw a heed . (JUS? ) vlt hCerpente r 7 0 heed* . 10 1 Inle t take , e a fcethPP 9 plaea a •al e l a prek e fitter . Hate d971 9 filte r keteat nf-99- 1 ta d7* 9 t a redac t ptaatln f tt 779 .

V-drtl na nprek e eetenale ncentalnadfrtit a tendmiett . 9rtlaed . 9tp1tce d979 9 fitter , ttvea t ctatalnt dtigh t prep partlcetatt . Drai ne n7-19- 1 filte r tpp.rtiitl y freiene a 1-19-0 1 tlltwtn a cendnttt t t a fil l tyttt a Inctedta f eeeplla a Hat . «Mi r fret e a t nigh t ke t thevr ddaring day

. a CO . lavet i daring day verv nerval , aeptace df-00- 1 an d f-W- 7 fitter, . 7-99- 1 •rl , cewre dvlt hfr*e n.line . f-80- J ca»tredvlt hgrey poxdtr . int

filte r ceverv

dait ht'»«n/|i. y

pevd.1 1 . replace d filte r a l trek e filte r he d helt . npttct dtn d rttttt dprah t t t titttt dtl * fe e In f eeaattreaa . M flea , ata l l a prtt e tip . ftrt .her t .actla ne f prek e filte r e neal t ende f preke , t e the t I t teethe dth a prek e eatdaale a c w

t e pravld a eddttleea t filtering . N t lerpave r tyttt a t a etlllt t atact' i redltr t hea t t a prtita t Treating a f ctadtmatt . 9a t taatttf Up t a a prak t .ita m Iandrain . Tere t ai r rtfalata r hed tter t eee n t t 7 } p.1 . take 1 a drye r r«ptered . Sea t t*t t tTt t plagged . htptita d I t 799-4 t vlt h t 7 0 I00O-74

S 770 . fa t te e 97 M flttei t I n terltt . Ta l Iai.te a 4 5 C filte r eaanatree e e f pwa p end felleve d vlt h Miltne y nt n t e centra l f le vt e 9 lee . Sy.U a Mil l ftnctleelaa . Prat t clttr . » , Har t lfl , » , atnlfal d 111 . Jytte e .til t fwclltntng . C9 , .tac t 1» , (9. atnlfal d IS
. •eaeve d pyitat .P.9 6

APPENDI XE MANUA L METHO D FO RMEASURIN

G CARBO N MONOXIDE I

N REFINER

YGASE S

1 . PRINCIPL E AN

D APPLICABILITY 1. 1 Principl e A nIntegrate

d sampl e i s extracte d fro m th e ga s stream , passe d throug hhydroge

nperoxid

e an d alkalin

e permanganat e solution s an d collecte

d i na Tedlar bag . Th e carbo nmonoxide (CO ) concentratio ni n th e sampl e i s measured spectrophotometrlcall y usin g th e reactio

no f C O wit ha palladiu

m chlorlde/leuc o crysta l violet/potassiu m lodat e solution . 1. 2 Applicability Thi s metho

d i s applicabl e fo r determinin

g C O emission s fro

m stationar

y sources . 2 . RANG

E AN D SENSITIVITY 2. 1 Range . A s written , th e netho

d applie s t o ga s sample s tha t contai n2 0 t o 100 0 pp m CO . Sample s containin g i nexces s o f 100 0 ppr a C O ca nb e analyze

d b y reducin

g either th

e ga s volune o

r th e shakin

g time . Sample s containin g les s tha

n2 0 pp

m ca nb e analyze

d b y Increasin g th e volum e o f sampl e reacte d wit hth e palladiu m chloride/leuc o crysta l violet/potassiu m lodat e solutio no r b y increasin

g th e shakin

g tim e o r frequency . However , i f suc hchange s ar e mad e i

nth e procedure , th

e linearity

o f th e absorptio

ncurv e ous t b e checke

d under thes e conditions . 2. 2 Sensitivity . Sensitivit y depend s o

nshakin g time , shakin g frequency , ga s volun e an d shap e o f reactio

nvesse l an

d canno t b e specifie

d absolutely . A

s written , th

e sensitivity

o f th e metho d i s approximatel y

1 0 pp o CO . 2. 3 Interferin

g Agents . Sulfu

r oxides , nitri c oxide , an d other acid gase s whichinterfer e withth e reaction , are remove d fro m th e ga s sampl e durin

g sampl e collection . Thes e gase s are remove d b y passin g th e sample

d ga s throug

ha •• » percent potassiu

m permangate/5-percen t sodiu m hydroxide solution . Carbo ndioxide doe s no t interfer e withth e reaction , but , becaus e i t i s remove d b y th e scrubbin

g solution , it s concentratio

nmus t b

e measure

d an d a nappropriat e volum e correctio

n made .



### 8 1P.9 7

4 . fUECISION , ACCURAC YAN D STABILITY 4. 1 Precision . Th e estimate

d intralaborator

y standar

d deviatio

no f th e metho d I s 2. 5 percen t o f th e meanfo

r ga s sample s analyze d l n triplicate . Thi s estimate , whic happlie s to th

e concentratio

nrange 2 0 t o 100 0 ppm , wa s determine d fro m 22 sample s collecte d a t a petroleu

m refinery . Th e interlabortor y precisio nha s no t bee n established . 4. 2 Accuracy . O

nth e average , th

e manua l metho

d result s wer e biase d 4 percent hig

hfo r 22 sample s analyze d b y a nNDI Rcalibrate

d wit hNB S standards . Th

e manua l metho

d wa s biase

d 5 percen t hig

hwhe nuse d t o analyz e certifie

d calibratio

nga s mixture s tha t containe d SO. , NO , C0 2 , an d 10 0 t o 50 0 pp

m C O l nnitrogen . 4. 3 Stability . Th e individua l component s o f th e colorimetri c reagent ar e stabl e fo

r at leas t on

e month , bu

t th e colorimetri c reagent mus t b e use d withi n3 hour s afte r preparatio nt o avoid excessiv e blan k correction . For optimu m accurac

y th e sample s mus t b

e reacte

d an d analyze d n o later tha

n3 hour s after th

e colorimetri c reagent ha s bee n prepared . 5 . APPARATU S 

### 5. 1 Sampling (Figur e E-1 ) 5.1. 1 Probe . Stainles s steel , sheathe d Pyrex glas s o requiva lent , equippe d wit h aglas s wool plu g t o remove particulat e matter . 5.1. 2 Impinger . Thre e Greenburg-Srolth impinger s connecte d i n serie s wit h leak-fre e connections . 5.1. 3 Pump. Leak-fre e pump, Meta l Bellow s Mode l 11 0 o requiva len twit h stainles s stee l an d Teflo n part s t o yiel d aflo w rat e o f 0. 2 t o 0. 4 L/min . 5.1. 4 Surg e Tank . Installe d betwee n th e pum p an d th e rat e mete r t o eliminat e th e pulsatio n effec to f th e pum

p o n th e rat e meter . 5.1. 5 Rat e Meter . Calibrate d rotameter , o requivalent , t o measur e flo w rate s betwee n 0 t o 0. 4 L/min . 5.1. 6 Flexibl e Bag . Tedlar , o requivalent , wit h acapacit y o f 1 0 liters . Ba

g mus tb e leak-free . 5.1. 7 Valve . Needl e valve , o requivalent , t o adjus tflo w rate . 5.1. 8 Fyrit e Analyzer , o requivalent , t o measur e CO - concentra tio n t o withi n +0. 5 percen taccuracy .

8 2P.9 8

5. 2 Analytica l 5.2. 1 Spectrophotometer . Singl e or doubl e bea m absorbanc e at 58 9 nm . Sli t widthshoul d not excee d 2 0 nm . t o measur e

5.2. 2 Vacuu

m Gauge . U-tub

e manometer , 1 mete r (3 6 in.) , with 1-n m divisions , or othe r gaug e capabl e o f measurin g pressur e t o withi n ±2. 5 n s H

g (0.10 ) in . Hg) . 5.2. 3 Pump . Capabl e o f evacuatin g th e ga s reactio

nbul bto a pressur e equa l to o r les s tha

n7 5 m nH g ( 3 in . Hg ) absolute , equippe d withcoars e an

d fin e flo w contro l valves . 5.2. 4 Barometer . Mercury , aneroid , o r other baromete r capabl e o f measurin

g atmospheri c pressur e to withi n2. 5 o nH g (0. 1 inHg) . I n man y cases , th

e barometri c readin g ma y b e obtaine

d fro m a nearb

y nationa l weathe r servic e station , i nwhic hcas e th

e statio

nvalue (whic hi s th

e absolut e barometri c pressure ) mus t b e requested . A

n adjustment fo

r elevatio

ndifference s betwee nth e weathe r statio

nan d samplin g point mus t the

nb e made a

t a rat e o f miniu s 2. 5 m m H g (0. 1 in . Hg ) pe

r 3 0 m

(10 0 ft ) elevatio nincrease , or vic e vers a fo r elevatio

ndecrease . 5.2. 5 Reactio

nBulbs . Pyre

xglass , 100-12 5 m L wit hTeflo

n stopcock , leak-fre e a t 65 0 m nHg . Designe

d s o tha t 1 0 m

L o f th

e colorimetri c reagent ca nb e adde d an d remove

d easil y

an d accuratel y (Figure E-2) . Commerciall y availabl e ga s sampl e bulb s suc has Supelc o #2-216 1 an

d Alltec

h#701 2 ca

nals o b

e used . 5.2. 6 Volumetri c Pipettes , graduate

d pipette . Clas s A , 4 m L an d 1 0 m L an d 1 mL

5.2. 7 Volumetri c Flasks . 10 0 m L

• 5.2. 8 Graduat e Cylinder . 100 0 mL . 5.2. 9 Shake r Table . Reciprocating-stroke typ e suc ha s Eberbac k Corp . Mode l 6015 . A rockin g ar m or rotary-motio

ntyp e shaker may

als o b e used . Th

e shaker mus t b

e large enoug

hto accommodat e a t leas t si

x ga s sampl e bulb s simultaneously . I t ma y b e necessar

y t o construc t a tabl e to

p extrusio

nfo r mos t commercia l shaker s t o provid e sufficien t spac e fo

r si xbulb s (Figure E-3) . 5.2.1 0 Spectrophotomete r cells . 1 c m pathlength .



### 8 3P.9 9

6. 0 REAGENT S 6. 1 Samplin

g 6.1. 1 Alkaline Permanganat e Solution . Prepar e b y dissolvin

g 4 0 grams o f AC S reagen t grad e aodiu

nhydroxide an

d 5 0 grams o f AC S reagent grade potassiu m permanganat e I

n1 liter o f distille d water . Thi s i s sufficien t fo r removin

g N O an d SO p fro m 5 0 liter s o f ga s containin

g 15 ? CO. . 6. 2 Analysi s 6.2. 1 Stoc k Solution s 6.2.1. 1 Potassiu

m lodate . AC S reagent grade , or equivalent . 6.2.1. 2 Sodiu

a Chloride . AC S reagent grade , o r equivalent . 6.2.1. 3 Palladiu m Chloride . AC S reagen t grade , o r equivalent .

6.2.1. 4 Sodiu

m Monohydroge nPhosphat e Heptahydrat e (Na-HPO^ H 0) . AC S reagent grade , o r equivalent . 6.2.1. 5 Leuc o Crysta l Viole t (4,4',4 " methylidynetri s (N,N dimethylanillne)) . Eastma nKoda k Compan

y Stoc k No . 33651 . 6.2.1. 6 Phosphori c Acid (85J) . AC S reagen t grade , or equivalent . 6.2. 2 Vorkin

g Solution s 6.2.2. 1 Sodiu m Monohydroge n Phosphat e (0.1M)
. Dissolv e 2.6 8 gram s i n 10 0 m L o f distilled , deionize d water . Thi s solutio n i s stabl e indefinitely .

6.2.2. 2 Sodiu m Tetrachloropalladate(II ) Solutio n (0.005M)
. Dissolv e 0.088 7 gram s o f palladiu m chlorid e an d 0.059 5 gram s o f sodiu m chlorid e l n 5 0 m L distilled , deionize d wate r an d dilut e t o 10 0 mL . Thi s solutio n i s stabl e fo r a t leas t on e month . I f a brow n preclpat e form s i t ca n b e dissolve d b y addin g a fe wcrystal s o f sodiu m chloride .

6.2.2. 3 Leuc o Crysta l Viole t Solution
. Dissolv e 0.025 6 gram s leuc o crysta l viole t i n 8 0 m L wate r containin g 0.25*i L o f 85 X phosphori c aci d an d dilut e t o 10 0 mL . Thi s solutio n i s stabl e fo r a t leas t on e month .

6.2.2. 4 Potassiu m lodat e Solutio n (0.1M)
. Dissolv e 2.1 4 gram s o f potassiu n lodat e i n 10 0 m L o f distille d deionize d water . Thi s solutio n l s stabl e indefinitely .

8 4

» j ufw^y ^ \m» LTV^T'-?^ .p. 1

€.2.2.5Colorimetri c Solution . Pipe t 4. 0 m L eacho f potas siu m lodat e solutio n(6.2.2.4) , leuc o crysta l viole t solutio n (6.2.2.3 ) an

d sodiu m tetrachloropalladat e (II ) solutio n(6.2.2.2 ) Int o a 10 0 m

L vo l inetri e flask . Pipe t 0. 6 mL sodiu m monohydroge

nphospat e solutio n(6.2.2.1 ) int o th e flas k an

d dilut e t

o volune . Thi s solutio n shoul d b

e use d withi n3 hour s o f preparatio nt o minimiz e th

e contribu tio no f th

e blan k an d th e sampl e absorbance . Ihi s i s sufficien t volum e t o analyz e thre e stack ga s sample s i ntriplicate . 6.2.2. 6 Standar

d Ga s Mixtures . Traceabl e t o NB S standard s an d containin

g betwee

n10 0 an

d 100 0 pp

nC O i nnitrogen . Th

e calibra tio ngase s shal l b

e certifie

d b y th e manufacture r to b e withi n•

_2 percent o f th

e specifie

d concentration . 7. 0 PROCEDURE 7. 1 Sampling . Evacuat e th e Tedlar ba

g completel y

usin g a vacuu

m pump . Assembl e th e apparatu s a s show ni nFigure E-1 . Loosely pac k glas s woo l lnth e ti p o f th e probe . Plac e 40 0 m L alkalin e permanganat e solutio n(6.2.1 ) i

nth e firs t tw

o impinger s an

d 25 0 m L in th e third . Connec t th e pum p t o th

e thir d impinger an

d follo

w thi s withth e surge tan

k an d th e rat e meter . D

o not connec t th

e Tedlar ba

g t o th e syste m a t thi s time . Leak-check th

e samplin

g syste

m b y pluggin

g th e prob e inle t an

d observin

g th e rat e mete r fo

r flow . I f flo

w i s indicate

d o nth e rat e meter , d

o not procee

d further unti l th e lea k i s foun

d an d corrected . Inser t th

e prob e Int o th

e stack an

d dra w sampl e throug

hth e syste m at 30 0

_ • 5 0 mL/mi nfo

r 5 minutes . Connec t th e evacuate

d Tedla

r ba g to th e system , recor

d th e tim e an d sampl e fo

r 3 0 minutes , o

r unti l th

e Tedlar ba

g I s nearl y

full . Recor

d th e samplin

g time , th

e barometri c pressur e an

d th e ambient temperature . Purg e th e syste

m a s abov

e Immediatel y

befor e eac

hsample . Th e samplin

g syste

m abov e i s adequat e fo

r removin

g sulfu

r an d nitroge noxide s fro

m 5 0 liter s o f stac k ga s whe

nth e concentratio

no f eac hi s les s tha

n1,00 0 pp

m an d th e C0 ? concentratio nl s les s tha

n 15% . Th

e sample s i

nth e Tedlar ba

g shoul d b

e stabl e fo

r a t leas t one month , l f th

e ba g i s leak-free . 7. 2 Ancillar

y Method s Measur e th

e CO . content l

nth e stack t o th

e neares t 0.5 % eac h tim e a C O ba g sampl e i s collected . A gra bsampl e analyze

d b y th e Fyrit e analyzer l s acceptable .



### 8 5P. 2

7. 3 Analysi s Assembl e th

e syste m show ni nFigur e E- 4 an

d recor d th e informa tio nrequire

d i nTabl e E- 1 a s l t i s obtained . Pipe t 10. 0 mL o f th e colorimetri c reagent (6.2.2.5 ) i neac hga s reactio

nbul b(5.2.5 ) an

d attachth

e bulb s t o th

e system . Ope

nth e stopcock s o

nth e ga s bulb s but leav

e th e valv e o nth e Tedlar ba

g closed . Tur

no nth e pump , fully openthe coarse-adjus t flo w valv e an d slowl y

openth

e fine-adjus t valv e unti l th

e vacuu m i s a t leas t 55 0 m

m Hg . No

w clos e th

e coars e adjus t valv

e an d observ

e th e manomete r t o b

e certai ntha t th

e syste m i s leak-free . Wal t a minimu m o f tw o minute s an

d l f th

e pressur e ha s decrease

d les s tha

n1 mm , procee

d a s describe

d below . I f a lea k l s present , fin

d an d correc t i t befor e proceedin g further . Recor d th e vacuu m pressur e t o th

e neares t 0. 1 m

m H g an d clos e of f th e ga s bul bstopcock . Ope nth e Tedlar ba

g valv e an d allo w th e syste m t o com e to atmospheri c pressure . Clos e th e ba g valve , ope

nth e pum p coars e adjus t valv e an d evacuat e th

e syste

m again . Repea t thi s fill/excavatio

nprocedur e at leas t twic e an d the nclos e of f th

e pum p coars e adjus t valve , ope nth e Tedlar ba

g valv e an d let th

e syste m fil l t o atmospheri c pressure . Ope nth e stopcock s o

nth e ga s bulb s an

d le t th e entir e syste

m com e to atmospheri c pressure . Clos e th e ga s bul b stopcocks , remov

e th e bulb s an

d plac e the

m o nth e shaker tabl e wit h thei r mai naxi s either paralle l to o r perpendicular to th e plan e o f th e tabl e top . Recor d th e roo m temperatur e an

d th e barometri c pressur e (neares t 0. 1 m m Hg ) after eac

hse t o f ga s bulb s i s filled . A t leas t on

e se t o f bulb s fro

m a Tedlar ba

g containin

g a know

nconcentratio

no f C O in nitrogenmus t b

e use d eac htim e a se t o f sample s I s shaken . Improve d accurac y wil l b

e obtaine

d l f tw

o standard s ar e Include d eac htime . Also , to avoi d cros s contaminatio no f samples , th

e bul bfillin

g syste m mus t b e purge d withanbient ai r fo r severa l minute s betwee nsamples . Shak e th e sample s fo

r 2 5 minute s l f th

e expecte

d concentratio

nl s les s tha

n60 0 pp

m an d fo r 2 0 minute s l f i t l s between60 0 an d 1,00 0 ppm . Plac e th

e content s o f eac

hbul bi

na labele

d tes t tub

e o r othe r suitabl e vessel . Measur e th

e absorbanc e o f eac hsampl e a

t 58 9 n

m usin g wate r a s th e reference ; als o measur e th e absorbanc e o f th e unreacte d colorimetri c reagent use d fo r tha t se t o f sample s t o serv e a s a reagent blank . Rejec t th e analysi s i f th

e blan k absorbanc e i s greate r tha n0.1 . Th e absorbanc e curv

e i s linear t o a

nabsorbanc e o f 1.8 . I f th e sampl e absorbanc e exceed s this , th e sampl e ca

nb e dilute

d withth

e colorimetri c reagent .



### 8 6P. 3

The reactio

nbetweenC

O an d th e colorimetri c solutio ni s slow . Fo r example , unshake nsample s se t aside fo r one hou

r afte r fillin

g sho w n o significan t absorbance . 8. 0 CALIBRATIO

N AN D QUALITYASSURANC E 8. 1 Ga s Bul bCalibration Weig hth e empt y bul bt o th

e neares t 0. 1 gram . Fil l th e bul bwit

h distille

d water an

d agai nweig

hto th e neares t 0. 1 gram . Subtrac t th e tar e weight an

d calculat e th

e volum

e i nliter s to thre e significant figure s usin

g th e density

o f wate r (s t th

e measuremen t temperature) . Recor d th e volum e o nth e bul bor , alternately , etcha nidentificatio

n number o

nth e bul ban

d recor d th e volum e l na notebook . 8. 2 Rat e Mete r Calibratio n Assembl e th

e syste m a s show

ni nFigur e E- 1 (th

e impinger s ma

y b e removed ) an

d attacha volune mete r t o th e prob e inlet . Se t th

e rota mete r at 30 0 mL/min , recor d th e volune o

nth e volune meter , star t th e pum p an d pul l ga s throug

hth e syste m fo r 1 0 minutes . Recor d th e fina l volum e o nth e volune mete r an

d determin

e th e volun e o f ga s tha t passe d throug hth e system . Repea t thi s procedur e fo r a t leas t tw

o other flo

w rate s between10 0 an d 50 0 mL/mi nan

d prepar e a calibratio ncurv e for th e rat e meter . 8. 3 Spectrophotomete r Calibratio n The calibratio

ncurv e i s establishe

d for eac

hbatcho f sample s shake na t th

e sam e tim e b y runnin

g standard s alon

g withth

e stack samples . Fo

r highes t accurac

y tw o set s o f standard s shoul d b e run , but acceptabl e result s hav e bee nobtaine

d whe nonl y on e se t o f standard s wa s use

d pe r batc ho f samples . 8. 4 Qualit y

Assuranc e 8.4. 1 Syste

m Shakin g Tim e Befor e fiel d sample s ar e analyzed , th e linearit y o f th e absorptio

ncurv e a s a functio

no f shakin

g tim e mus t b

e establishe

d fo r th e analytica l system . Thi s ca nb e accomplishe

d a s follows : Fil l a Tedlar ba

g witha C

O concentratio

na t leas t a s hig

ha s th

e highes t leve l expecte

d to b e encountere

d i nth e field samples . Fil l a t leas t si xga s bulb s wit hga s fro m th e ba g a s describe

d i nSectio

n7. 3 an

d se t the m o na shaker . After shakin g ha s bee

ninitiate

d remov

e tw o bulb s a

t 1 5 minutes , tw

o at 3 0 minute s an d tw o a t 6 0 minute s an d measur e th

e absorbanc e o f eac hsolution . Calculat e th e absorbanc e pe

r



### 8 7P. 4



### volum e o f

ga s (SA ) accordin g t o Equatio n E- 1 (Sectio n 9.2 ) fo reac h sampl e an

d determin e th e averag e S A fo ral l sample s wit h Identica l shakin g times . Plo tthi s averag e S A versu s th e shakin g tim e t o determin e th e linearit y o f th e absorptio n curve . Us e thi s dat at o determin e th e shakin g tim e an d sampl e volum e require d fo rsampl e analysis . 6.4. 2 Sampl e Bag-LeakChecks Whil e abag-lea kchec ki s require d subsequen tt o ba g use , i t shoul d als o b e don e befor e th e bag i s use d fo rsampl e collection . Th e ba g shoul d b e leak-checke d I n th e Inflate d an d deflate d conditio n accordin g t o th e followin g procedures . Connec tth e ba g t o awate r manomete ran

d pressuriz e th e bag t o 5 t o 1 0 c m H- 0 ( 2 t o 4 inche s H^O) . Allo w th e ba g t o stan d fo r6 0 minutes . An y displacemen ti n th e wate rmanomete rindicate s aleak . No w evacuat e th e ba g wit h a leakles s pun

p tha ti s connecte d o n th e downstream sid e t o aflo w indicatin g devic e suc h a s a0 t o 10 0 mL/mi n rotamete ro ra

n impinge r containin g water . Whe n th e bag i s completel y evacuated , no flo w shoul d b e eviden tl f

th e ba g I s leakless . 9. 0 CALCULATION S 9. 1 Abbreviation s an d Symbol s S A c Sampl e absorbanc e pe r volune o f ga s lnbul b C0 B r Concentratio no f C O i nTedlar ba

g (ppm , dr

y basis ) CO - . « Concentratio no f C O instack (ppm , dr y basis ) FC0

_« Volun

e fractio

no f C0

_l

nstack B y s Moistur e conten t o f ga s lnba g 9. 2 Calculationo f C O 9.2. 1 Calculatio

no f S A Calculat e th

e sampl e absorbanc e per volum e o f ga s (SA ) fo

r each ga s bul b(Equatio

nE-1 ) an

d recor d th e valu e I nTabl e E-1 . Calculat e th e averag e S

A fo r eachba

g sampl e an

d compare th

e thre e vslue s t o th e average . I f an

y singl e value differ s b y mor e tha

n1 0 percent fro

m th e average , rejec t thi s value an d calculat e a ne

w averag e usin

g th e tw o remainin

g values . (E-1 ) c i • I Sampl e Absorbanc e Corrected for Blank ! J Barometri c Pressur e 1 I Bul bVolum

e - Volum

e Reagen t J [Sampl e Pressur e inBul bJ



### 88 .P. 5

9.2. 2 Calculatio

no f C O Concentratio

ni nBa g 9.2.2. 1 Singl e Standar d Shakenwit hSample s Calculat e th

e C O concentratio

nl nth e ba g usin g Equation s E- 2 an d E-3 . I f condensat e i s visibl e i nth e Tedlar bag , calculat e B usin g Tabl e E- 1 an

d th e temperatur e an

d barometri c pressur e i nth e roo m wher e th

e analysi s wa s done . I f condensat e I s not visible , calculat e B usin

g th e temperatur e an

d barometri c pressur e a t th e samplin g site .

_. m Vapo r pressur e o f wate r l

nbag ,

_- . v Barometri c pressur e

C0

_ Bag 

# [ pp

m C O i nstd I I Averag e S

A sampl e ,

_- *
1-B w J Averag e S

A st d l ; 9.2.2. 2 Tw

o Set s o f Standard s ShakenwithSample s Construc t a grap

ho f concentratio

nversu s th

e average S

A fo r eachstandar

d forcin

g th e curv e throug

hth e origin . Determin e th e C O concentratio

ni neac hTedlar ba

g stac k sampl e usin

g th e average S

A fo r eac hsampl e an

d correc t fo

r th e amount o f moistur e present ( B ) . 9.2. 3 Calculatio

no f Stac

k C O (dr y basis ) Calculat e th

e C O inth e stack usin

g Equatio

nE-4 .

C0 Stac k ' C0 Ba g (1
- F C0 2 > < E "* > 10. 0 BIBLIOGRAPH

Y Lambert , J.L. , an

d R.E . Welns . Induce d Colorimetri c Metho d fo r Carbo nMonoxide . Anal . Chem. , 46 : 929-930 , 1974 .



### 8 9P. 6

TABL E E-1 .

TEMPERATUR

E ( 6 C )


### 4 6 8 1 0 1 2 1 4 1 6 1 8

~ 2 0 

### 22 2 4 2 6 2 8 3 0 MOISTUR E CORRECTIO

N

VAPO RPRESUR

E H 2 0 (m m 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

9 0 

# JGLAS S WOO L FILTE R

AMBIEN T TEMPERATUR E BAT H QUIC KDISCONNEC T

— - VALV E O N BA

G

FIGUR E E-1 . C

O SAMPLIN

G TRAIN

T J ^ 1P. 8

DIMENSION S I N cm)

1. 9

FICUR E E-2 . CA S REACTIO N BUL B (0. 1 liter )



### '9 2P. 9

FIGUR E E-3 . ADAPTO RFO RHOLDIN

G GAS BULB S O

N SHAKE RTABL E



### 9 3•UL B SHUTOF F VALVE S

SAMPL E IULB S FIN E ADJUST COARS E ADJUS T VALVE ^

f VflLV E

— " VEN T 

### BA GSHUT OF F VALV E 'A*\ VACUU M

PUM P

TEDLA R SAMPL E BA G
FICUR E E-4 . CA S BUL B FILLINGSYSTE M

. OPJ 1

'O l> J ' m9Oi Q i <z a

Q

s o

© 9 3 b i c

aa 6 5 a ? * * u C kc ^ sn w
o



# 2

C M 0 c a

c J 

# r m
I ~ 

# I jfc o 6 J o 

## 1 $ 

# s i I o ca I c=

» 

## a 

# s

o9 5

-J iP.1 2

APPENDI XF

INSTRUMEN

T EVALUATIO

N HISTOR Y

1/4/8 0 1/22/8 0 2/2/8 0 2/4/8 0 3/10/8 0 3/31/8 0 4/2/8 0 4/3/8 0 4/10/8 0
4/16-4/17/8 0 4/21/8 0 4/25/8 0 

### 6/9/8 0 7/3/8 0
9/18/8 0
11/10-11/12/8 0



### ECOLYZE R310 7 10/18/7 9 4/16-4/17/8 0 4/21/8 0 4/27/8 0 4/28/8 0 APPLIE D AUTOMATION OPTICHROM 10 2 

### Instrumen treceive d vit h n o Instructio n manual . Instructio n manua

l received , starte d wirin g Instrument . Powe rsuppl y failed . Ne w powersuppl y failed . Incorrec toutpu tfoun d (overloaded) . Powe r suppl y failed . Servicema n fro

m Applie d Automatio n arrive d t o repai rinstrument . Instrumen trepaired , powe rsupply , outpu t board an d temperatur e controlle rreplaced . Outputi s negative . Outpu tproble m fixe d by reversin g wirin g t o outpu tboard an

d b y movin g aresisto ron i tt o anothe rposition . Transporte d t o refiner y i n trailer . Instrumen tturne d backon . Fus e ble w i n heate rcircuit . Zer o respons e varyin g badly . Negativ e pea

kbefor e C

O pea kon chromatogram detected . Chromatograms sen tt o manufacture r a s ai d l n troubleshooting . Condensatio n i n FI

D cause d corrosio n t o inter na l parts . Monito rshu tof f unti l manufac turer' s servic e representativ e call . Applie d Automatio n servicema n trie d t o repai r monito r- was unsuccessful . Monito rshu t down .

Instrumen treceived . Checked out . blem s found i n laborator y checkout . Transporte d t o refiner y i n trailer . Instrumen tturne d on . Mode l 294 9 filte rfailed . Replaced . Mode l 294 9 filte rfailed . Replaced . N o pro 9 6P.1 3



### 5/3/8 0 5/8 0 9/18/8 1 1/17/8 1 2/17/8 1

ANARA D 501- R 10/2/7 9 4/16-4/17/8 0 4/21/8 0

MS A LIR A 20 2 Mode l 294 9 filte rfailed . Replaced . Larg e carbo n filte radded t o monito rsampl e lin e (replace s Mode l 294 9 filter ) t o exten d operatio n time . Electrochemica l cel l goin g bad . Spa n contro l wa s unabl e t o spa n monitor . Ne w electrochemica l cel l installed , monito r zeroe d an

d spanned . Mode l 294 9 filte rfailur e cause d electrochemica l cel l t o fall . Monito rremove d fro m evaluation .
Instrumen treceive d an d checke d ou ti n labora tor y withou tproblems . Transporte d t o refiner y i n trailer . Instrumen tstarte d up . N o problem s o routage s occurre d befor e testin g wa s complete d i n Apri l 1981 .
11/2/8 0 1/14/8 0 2/27/8 0

3/3/8 0

3/4/8 0

3/11/8 0 3/10-4/3/8 0

4/15/8 0 4/16-4/17/8 0 4/21/8 0 4/21-5/1/8 0 Instrumen tno toperationa l a s received . Pu tint o operation . Apparen tfailur e o f

outpu tboard . Outpu tha d worke d previousl y (on PD-2064 ) bu toutpu tno w les s tha n 4 mA

. Calle d MSA

. Ne w outpu tboar d ordered . Ne w outpu t boar

d arrived , installed . Outpu t stil l no t correct ; MSA suggeste

d checkin

g outpu t b

y voltag e drop acros s a resistor . Output seeme

d t o be oka

y b y thi s method , bu t powe r suppl y

boar d faile d soo nafter test . Ordere d ne w power supply . MS A suggeste

d tha t output proble

m coul d b

e solve d b y installin

g a matchin g circui t betwee

nth e MSA instrumen t an d th e dat a logger . Power suppl y

boar d arrived . Electronic s expert , R . Burdine , mad e severa l visit s to ascertai noutpu t proble m an d buil t a circui t t o correc t problem . Hi s conclusio n wa s tha t suc

ha circui t wa s not needed , bu t tha t output boar

d wa s ba

d (again) . Ne

w boar d ordered . Ne w boar d arrived , no t teste d (trailer packe

d fo r moving) . Transported to refiner y intrailer . Instrument starte

d up . Output stil l bad . Instrumen t off . MS A contacte

d fro m Auburn .



### 9 7P. M



### 5/1/8 0 5/2/8 0
5/3-5/2 0 6/9/8 0 6/9-6/16/8 0 9/18/8 0

TELEDYN E 61 1 DMCO-20

X 2/8 0 

### 3/13/8 0

4/16-4/17/8 0 4/21/8 0 4/29/8 0 5/1/8 0 5/7/8 0

9/18/8 0 11/2/8 0

BENDI X777 0 1/3/8 0 2/14/8 0 D . Tlskiewl c o f MS A cam e t o chec k problem . Accordin

g t o hi s meter , outpu t wa s 4-2 0 mA . Mr . Tlskiewl c said tha t matchin g circui t wa s needed . MSA-Pittsburg hwoul d fin

d an d sen d one . Instrumen t off . N

o wor k o n matchin

g circuit . Matchin g circui t receive d an d installe

d b y MSA serviceman . La bevaluatio

ncomplete

d i n field . Spa nan d zero adjustment no t possible . Complet e optica l alignmen t restore d performance . Instrumen t continue d t o operat e normall y throughou t th

e remainin

g par t o f th

e evalua tion .

Instrumen t receive d withn

o instruction s o

n ho w to Instal l o

r us e molecula r siev e canis ters . Initia l setu

p an d adjustment . Dimensiona l instability

noted : ver

y sensitiv

e to eve

nthe slightes t change o f attitude withrespec t t o horizonta l - eve

nmicroscopi c change s signi ficant . Transporte

d t o refiner

y i n trailer . Instrumen t turne

d o n an d interferenc e i

n fue l ga s noted . Molecula r siev

e Installe

d o n sampl e line . N

o effec t o

n sampl e concentration . Impossibl e t o zero an d spa ninstrument . Molecular siev

e removed . 2-hou r drif t R

A Tes t spoile

d b y ver y hig h sampl e concentration . Instrument readou t di d no t change before , durin g o r after perio

d o f hig hconcentration . Monito r shu

t of f du

e t o lack o f reliabl e dat a cause d b y interference . Molecula r siev

e receive

d fro m Teledyne . When installed , n

o startu

p wa s possibl e becaus e o f optica l syste

m failure .

Instrumen t received . Connection s t o ga s service s made , instrument starte d up . Severa l tub e fitting s insid

e leake d an d ha d t o b

e tightened . Initia l adjustmen t made (ove ntemp , flows , etc.) .



### .9 8P.1 5

3/11/8 0

3/21/8 0 4/1/8 0 4/16-4/17/8 0 4/21/8 0 5/7/8 0 11/5/8 0

12/15/8 0 2/25/8 1 Interna l plumbin g modifie

d to accept separat e source s fo r valv e an d heate r air . Vhe n instrumen t wa s restarted , ove nheate r wa s inadvertentl y

shorte

d causin

g destructio

no f TRIA C l n heate r contro l circuit . Ne w TRIAC s ordered . Part s arrive

d but prove

d t o b e wrong . Correc t part s ordered . Correc t part s received , installe d success fully . Instrument restarted . Transporte

d to refiner

y i htrailer . Instrument starte

d back up . 2-hou r drif t R

A Tes t spoile

d du e to hig

hH-S . Instrusent syste

m recovere

d fro m hig hH. S i

n about 4 hours . * Monitor failur e fro m 2 week s previou s cause d b y diaphrag

m o n sampl e valve . New par t ordered . Diaphrag

m replaced . Monitor operatin g pro perly . Sampl e valv

e diaphrag

m rupture

d an d repaired . Instrument operate d properl y

throughou t th

e remainin

g field evaluation . DEL MA R SCIENTIFI C EM- W 2/10/8 0 4/16-4/17/8 0 4/21/8 0

5/7/8 0 Monito rreceive d an d set-up . Transporte d t o refiner y i n trailer . Instrumen tturne d on . Pressure/flo w problem s noted . Sensitivit y criticall y dependen to n flo w (whic h varie s wit h pressur e an d ga s viscosity) . Ver y hig h H. S concentratio n encountere d i n fue l ga s a t10:0 0 am. Analyze rdi d no tre - cove runti l nex tday . Instrumen toperate d properl y throughou tstudy , bu tga s dilutio n syste m wa s not - appropriat e fo rfue l ga s dilution . HOUSTO N ATLA S 825/102 R 12/14/7 9 1/20/8 0 4/16-4/17/8 0 4/21/8 0

4/23/8 0 Instrunen t received . Instrunent setup . Transporte

d t o refiner

y i n trailer . Instrument turne

d on . Outpu t overload s dat a logger . Tap

e doe s no t advance . Ordere d ne w output/cycl e tim

e board . Ne w boar d arrived . N

o effect . Time r rela y ordered .



### 9 9

.P.1 6

4/28/8 0 5/1/8 0
5/5/8 0 5/8/8 0 5/8/8 0 9/11/8 0 9/18/8 0 11/2/8 0 1/6/8 1
3/31/8 1 Rela y received . N

o effect . Abraha m Asperl c o f HA I arrive d to trouble shoot . Did not fin d problem . Too

k analyzer back . Asperl c Informe

d us o f wirin

g mistake to dat a logger . Sen

t instrument back t o us . Instrumen t arrive

d withwirin

g instructions . Instrument turne

d o n- works . Monito r sent to manufacture r fo r repair . Monitor returne

d b y manufacturer . Housto nAtla s servicema

nfoun d caus e o f drif t t o b e condensatio

ni nvent line . Dilutio nsyste m breakdown . Circui t boar d in stalle d backward s b

y contractor personnel . Ne w par t delivered . Monitor failur e du

e to corrosio

ni ntimer . PROCES S ANALYZER S INCORPORATE D 32-23 0 12/20/7 9 1/80-3/8 0
5/9/8 0 6/9/8 0 8/28/8 0 9/18/8 0 10/1/8 0 11/5/8 0 Instrumen t received . Instrumen t no t operationa l - many circui t card s exchange

d withmanufacturer . Instrument eventuall y

returne

d fo r repair . Monitor returne

d fro m manufacture r allowe d t o war m u p unti l nex

t sit e visit . Monitor brokendow ndurin

g 1-mont

hwarmup . Returne d t o manufacturer . Monitor returne

d t o manufacturer . Monitor returne

d t o field test , 4 t o 2 0 m A outpu t not functioning . Monito r stoppe

d operating . Monitor failure cause d b y wearout o f 1 0 por t valve . Monitor shu t dow nan d remove

d fro m further testing .



### 10 0P.1 7 (firfeass mod fnstructioai

on the ievant %tfart eotnpletias) 1 . REPOR TWO . 3 . RECIPIENT' S ACCESSIO N NO .

a. TITL E AN O OUDTITL G FIEL D EVALUATIO

N O FCARBO

N EPOXID E AN

D HYDROGE

N SULFID E CONTINUOU S EMISSIO N KQ242TOR S A T A N Oil REFINER Y 7 . AUTWORI8 J R . S . Jeste r and 3
. 3
. Ferguso n (Harsen ) W . J . Mitchel l (EPA ) 3 . RCPOR T©AT S
£ . PERFORMIN G ORGANISATIO N COO E )
. PERFORMIN G ORGANIZATIO N REPOR TNO .

3 . PERFORMIN G ORGANISATIO N NAM E AN O ASDRGB S Harao n Engineerin g an d Testin g 3o x 220 7 Aubur n Industria l Pa? k Auburn D A L SS§1 0 h e . PROGRA M GLdMEN TMO .
IfWrSoTdTOAEYTEEANTwo - (S8-02-S40 5 13 . SPONSORIN G AGENC V NAM E AN O AOORES S Environmenta l Monitorin g System s Laboratory Offic e o f Researc h on d Developaen t U.S . Environmenta l Protectio n Agenc y Researc h Triangl e Park , N C 2771 1 (13
. TvP E O f REPOR TAN O PERIO D COVERE D 

### Fina l 14 . SPONSORIN G AGENC V COO E EP A600/0 8 19 . SUPPLEMENTAR Y WOTd S T o b e publishe d a s a n OR D Projec t Repea t 18 . AOSTRAC T An eleve n aont h fiel d evaluatio n wa s don e o n fiv e hydroge n sulfid e an d fou r carbo n monoxid e aonitor s locate d a t a n oi l refinery
. Th e hydroge n sulfid e aonitor s sample d a fue l ga s fee d Sin e an d th e carbo n monoxid e monitor s sample d th e emission s froma flui d ca t cracke r (FCC)
. Tw o o f th e fou r carbo n monoxid e monitor s operate d ove r th e eleve n aont h perio d an d showe d goo d agreemen t wit h th e Seuc o crysta l viole t (LCV ) we t chemica l aetho d develope d fo r th e purpos e o f checking monito r accuracy , fh e LC V aetho d an

d th e specia l stac k ga s conditioning systememploye d t o remov e aois

tur e an d particulat e fromth e FC C stac k ga s ar e als o described
. Th e ga s conditioning systemoperate d fo r 1 4 aonth s withou t a aajo r failure
. Non e e f th e fiv e hydroge n sul

fid e aonitor s wa s foun d acceptable
. Tw o o f th e fiv e neve r obtaine d a vali d sampl e an d th e othe r thre e di d no t agre e wel l wit h th e EP AReferenc e Metho d 1 1 during relativ e accurac ytesting
.



# k KE V WORD S AN D DOCUMEN TANALYSI S DESCRIPTOR S b.lOENTl f IERS/OPE N ENDE D TERM S C
. COSAT l Field/Crou p Stac k ga s conditionin g syste a Carbo n aonoxid e aonitor s Hydroge n sulfid e aonitor s Fue l ga s fee d lia e Carbo n sonoxid e we t cheaica l oetho d Leuc o crysta l viole t EP AMetho d 11 1 JEff i 10 . DISTRIBUTIO N STATEMEN T RELEAS E T O PUBLI C 16 . SECURIT Y CLAS S (Thii Report/ UNCLASSIFIE D 2 0 SECURIT Y CLAS S (Thiipast) UNCLASSIFIE D 2 1 . NO . Of PAGE S
33 . PRIC E

EP A P» o 2226- 1 (Qo*
. d-T? ) Pnawiou o aoiTie wi o ©Do©LQ f a

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