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# OAR Box 1784 Prepped by Ollie Stewart



### Document

Number: 

# 47 ) ll-B-6 Docket Number: 

# A-84-4 4

Printed 10/31/2008 8:05:40 AM Sheet 47 of 143P. 2 UNITE D STATE S ENVIRONMENTA LPROTECTIO N AGENCY; ~£x

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## ~< S 

## H m188 5 

## A-84-4 4

MEMORANDU M SUBJECT : Tri pRepor t " - Maratho nPetroleum

Refinery , Garyville , Louisian a FROM : Nanc y

D . McLaughlin , Environmenta l Enginee r Standard s Documentatio nSection , ISB,"ESE D(MD-13 ) 

### TO : Kennet hR . Durkee , Chie f

Standard s Documentatio n-Section , ISB , ESE D(MD-13 ) I

. PURPOSE : Th e purpos e o fth e visi t was t o becom e familia rwit h th e operatio n o f?.min ° treatin g unit s an d t cdiscus s Marathon' s experiences , wit h th e refiner yfue l 35 s NSPS

. I I

. TIH E AN

D PLACE : •v.:30- 1 2:0.'

. ?.rn

. Mover.ibe ri.'S , 198 4 2;dr&t ho.-i Petroleu m Company Geryv i lie , Louisian a III

. ATTENuEF.S : U.S . Environveni:?) ! Protectio n Auenc v ^anc yD . i3cl.ai.qhlin Charle s fi . Seama n Pebbl e K . Well s Env i ronHsnta l Enginee r Env i ronm°nta l Eng i nc-er Environmenta l Protectio nSpecialis t Maratho nPetroleu mCompan y Blak e Harmo n Su e Shaughness y Ke n L . Wilke y Environmenta l Coordinato r Refinin g Enginee r Associat e Refinin a Enginee r

EP AFor m 1320- 1 (12-70 ) CONCURRENCE S SYMBO L k SURNAM E k DAT E k SPS/j?3 S 

### -W-JUu^/M- -ZJKL/ZL OFFICIA L FIL E COP Y GP O : 198 3 O - 403-20 1P. 3

IV

. DISCUSSION : Summar yo fActivitie s Charli e Sedman , Debbi e Wells , an d I arrive d a tth e refiner ya t 8:3 0 a.m . W

e firs t .me

t wit h Maratho n nersonne l fo rabou ttwo-and-one-hal f hour s t o discus s th e routin e operatio n o fthei ramin e treaters , th e reliabilit yan d performanc e o fth e amin e treaters , an d Marathon' s experience s wit h th e refiner yfue l ga s NSPS

. Followin g th e discussion , w e observe d th e amin e treatin g are a an d th e refinery' s centra l contro l room . W e the n visite d th e wastewate rtreatmen tare a fo rDebbi e Well s t o becom e familia rwit h thi s par to fth e refinery

. Th e discussio n her e emphasize d contro l o fai remission s fro m wastewate rtreatmen tuni t processe s an d th e NSP S tha ti s currentl ybein g develope d fo rthi s ai r emissio n source . Vi e lef t th e refiner yaroun d 12:00

. Th e informatio n i n thi s repor treflect s th e discussion s durin g ou r •visi t an d a subsequen tfollow-u p phon e conversatio n o n Decembe r14

. Genera l Refiner yInformatio n Marathon' s refiner yi n Garyville , Louisiana , i s th e newes tgrass-root s refiner yi n th e country
. I twa s designe d i n 197 4 an d starte d operatio n i n 1976

. Th e origina l refiner ywas designe d b yUO P and

. constructe d b yParson s Engineering

. Ther e was a majo rexpansio n i n 1D79 whe n a flui d catalyti c crscMn g unit , alkylatio n unit , amin e treater , staurat e ga s plant , sn d butan n iscmerizatio n uni t"-vr e added

. Th e contracto rfo rthi s expansio n was Fluor

. Th e re^in^r yha s a nomina l capacit yo^ 255,00 0 barrel s o fcrud e psr day

. Th o refiner ywas designe d fo rani usuall yrun s hig h sulfu rcrud e (greate rthe n ?

percen tsulfur)

. Amin e Treatin g System s X- ^ Thi s refiner

yha s two separat e amin e treating systems . Th e firs t system , whic hwa s installe d wit hth e origina l refinery , use s monoethanolamin e (MEA ) an

d wa s buil t b

yParson s aroun

d 1976 . The secon d syste mwhic hwa s par t o f th o 197.-

? refiner

yexpansio n use s diethanolamin e (DEA) , an d wa s designe d b

y Exxo n an

d constructe d b

yFluo r Engineering . Th e HEAsysteminclude s on e strippe r an d five absorbers : two fo r hydrotreate r recycl e gas , on e fo r liqui d propan e gas , on e fo r th e vacuu m towe r off-gas , an

d on e fo r fue l gas . Abou t 8 millio n scf/da yo f ga s srq treate d in th e MEAunit . Thi s represent s 2 5 t o 5 0 percen t o f th e tota l fue l r?. s produce d i n th e refinery . Abou t 2 0 percen t o f th e amin e in th e MEAsystemi s use d fo r th e fue l ga s treatment .P. 4

Th e pressur e o f th e fuel ga s i nth e ME A uni t i s maintaine

da t 6 5 psig . Th e H2 S leve l i

nth e inle t strea

m range s fro

m 3 t o 1 2 percent ; there i s littl e or n o CO ? i nth e inle t stream . Th e wide range o f inle t H2 S concentration s i s du e t o variation s i nth e typ e o f crud

e oi l bein

g charged . Th

e outle t concen tratio n o f Hg S fromth e ME Aroutinel yaverage s abou t 10 0 ppmv , bu t agai n thi s concentrat e fluctuate s du e t o change s in th e crud e type . Th e MEAuni t i s generall yoperating a t design expectation s an d ther e hav e bee n n o significan t operating problems . Ther e ar e n o foaming problem s a t thi s time . MEAlosse s ar e minor , abou t 60 0 lbs/da you t o f a baselin e operating inventor

yo f abou t 29,00 0 gallons . Th e ME Auni t use s a precoa t filter , reclaimer , an

d flas hdru

mt o remov e an

yccntaminents . (Hydrocarbon s i n amin e ha d been a problembu t tha t ha s been minimize d wit hth e flas hdrum. ) Th e DE Asysteminclude s on e strippe r an d tw o absorbers : on e fo r fue l gas , an d on e fo r a propane/butane/propylene/butylen e mixture . Abou t 1 5 millio n scf/da yo f fue l ga s ar e treate d i n th e DEAunit , representing 5 0 t o 7 5 percen t o f th e tota l fue l ga s produce d i n th e refinery . Abou t 9 0 percen t o f th e amin e in t h e OF

Asystemi s used fo r th e fue l ga s treatment . Th e pressur e o f th e fue l ga s int o th e DE Auni t i s maintaine d a t IC O psig . Th e compositio n o f th e inle t fue l ga s strea mstay s fairl yconstan t sinc e i t i s coming fro

ma ^or e constan t sourc e (th e FCCU) . Th e H^S

leve l in th e inle t strea mi s abou t 3 percen t wit hsom e CO2 . Maratho n ha s never , teste d fo r othe r sulfur compound s an d doe s no t thin

k the yar e presen t in significan t quantities . Th e outle t concentratio n o f Hp S fro mth e DEAi s routinel yles s than 1 0 ppmv , ranging u

p t o 2 0 ppmv . Th e J

l " Ai s operating at onl y2 0 t o 3 0 percen t o f it s design level . Th e curren t circulatio n rat e i s P,00 0 barrels/dayvs . a design rat e o f 27,00 0 L .arr°lf./ , : ! ay . I f i t wer e a t ful l load , Maratho n estimate d th e H^ S outle t concentratio n coul d ris e t o 10 0 np-.y . Operating at sucha lowleve l ha ? cause d som* : operating problems . DEAlosse s ar?. significant , abou t 1,50 0 lbs / 6dy out o Y ? ! baselin e inventoryo f abou t 27,00 0 gallons . Thes e hig hlosse s ar e rop^rt^'H

ydu o t o amin e entrainmen t in th e liqui d treater . Ther e ar e n o fcaiv.iri

g o r contaminatio n problems . Th e DEAuse s precoa t an d carbo n filter s an d a flas h6mr:<t o remov e th e impuritie s whic hmigh t caus e foaming problems . Hot hamin o treating system s hav e a n excellen t reliabilit yrecord . Seldom •ha s eithe r uni t bee n off-lin e except fo r schedule d shutdowns . However , problem s hav e bee n experience d wit hcorrosio n insid e th e amin e treaters , piping , an d exchangers . T o ensur e th e amin e treater s ar e operating properly , Maratho n sample s t^ e outlet s wit hOraege r tube s e^'ery fou r hours , &nd

sample s the ric

han ^ lea

n amin e one ? a da

yfo r percen t amine , Ho S concentration , an d hydrocarbo n contamination . Th e importan t variabl e operating parameter s whic hca n be se t b yth e operato r ar e th e amoun t o f stripping stea man d th e temperatur e an d circulatio n rat e o f th e amine . Th e temperatur e o f th e amin e in th e lowP. 5

pressur e ME Auni t i s particularl y critical . A

20° F swingi ntemperatur e ca n caus e th e outle t H2 S concentratio nt o excee dspecification s (15 0 ppmv) . Th e pressur e strea

m inth e ME Auni t 1 s a nimportan t parameter , bu t i t i s se t b y th e pressur e o f the refinery fue l ga s system . The amoun t o f fue l ga s flowin g t o th e amin e treate r varie s wit hth e crud e charge . Base donth e fue l ga s rate , th e outle t concentrations , an d th e amin e sampl e results , th e amin e circulatio n rate s ar e adjuste d any"tim e th e ga s rat e or outle t concentratio n change s significantly . ' Typica l operatin grange s are liste dbelow : Paramete r Absorbe r pressur e (psig ) LeanAmin e Temperatur e (°F ) Amin e i n Absorben t (weigh t percent ) 

### ME A

H? S i n amin e (moles/mole ) lea n ric h 

### DE A 6 5 

### 100 5 t o 1 8 

### 0. 1 0. 4 18 0



### 130 1 4 t o 1 7 0.0 5 

### 0. 4 In general , i f operate d a t desig n levels , th e DE Auni t woul d b e cheape r t o operat e tha n th e ME Aunit . This'i s becaus e DE Ai s easie r t o stri p •an d ca n b e operate d a t a highe r concentratio n tha n MEA . Maratho n operate s tw o separat e amin e system s becaus e neithe r syste mha s sufficien t capacit y t o handl e al l treatin g withi n th e refiner yand becaus e i t i s convenien t t o Operat e bot hlo wand hig hpressur e fue l ga s treaters . At thi ? tim e Maratho n i s no t considerin g switchin g amine s base d o n th e curren t performanc e o f th e amin e treaters . However , Maratho n i s no t satisfie d wit hth e performanc e o f thei r Beavo n Stretfor d tai l ga s treate r and i s considerin g changin g fro^

- DE At o a tertiar yamin e (MDEA ) t o b e abl e t o trea t th e Clau s tai l gs s i n th e curren t amin e treater . Currently , th e snin « treat.r. r off-ga s i s route d t o tw o 22 S LT/ D Clau s unit s followe d b ya 1 2 LT/L 1 Ssavo n Stretfor d tai l ga s unit . Combustio n Sources . Becaus e th e entir e refiner ywa s constructe d afte r th e refiner yfue l ga s NSP S too k effect , al l th e combustio n source s ir . th e refiner yar e subjec t t o th e standard . Ther e ar e 2 2 affecte d combustio n source s i n th e refinery : 2 flares , 2 boilers , 2 incinerators , and 1 6 proces s heaters . Refiner yFue l Qa s Syste mand Natura l Qa s Blendin g Al l o f th e refiner yfue l ga s and natura l ga s tha t i s use d inth e refinery i s firs t combine d i n a commo n mi xdru m befor e bein g distribute dt o th e variou s combustio n sources . Thu s Maratho n ca n demonstrat e complianc e fo r th e entir e fue l ga s syste m(i.e. , al l th e affecte d combustio n sources ) b ymonitorin g a t thi s on e location . Th e combine d strea mi s compose d o f fue l ga s fro m tw o separat e amin e treatin g systems , natura l gas , and exces s platforme r gas . Abou t 6 0 percen t o f th e refinery' s energ yneed s i s supplie d b yrefiner yfue l gas ; th e remainde r i s fro m fue l oi l or

natura l gas .P. 6

Th e relativ e amoun t o f eac hauxiliar yfue l tha t i s use d depend s upo n th e relativ e cost . Currently , natura l ga s i s preferre d and use d whe n possibl e becaus e o f it s availabilit yand lo wcost . (Not e tha t Maratho n did . no t star t usin g natura l ga s a t th e refiner yunti l a fe wmonth s ago. ) Emissio n Monitorin g and Exces s Emission s Report s T o demonstrat e complianc e wit hth e refiner yfue l ga s NSPS , th e combine d strea mi s sample d thre e time s a da yusin g Draege r tubes . Maratho n ha s ha d n o significan t problem s a t thi s refiner ywit hmeetin g th e NSPS , (0.1 0 gr/dsc f o r 16 0 ppmv) . I n general , ther e hav e bee n onl y2 o r 3 mino r excursion s abov e th e standar d fo r 2 o r 3 hour s eac hquarter . I n th e past , th e concentratio n o f H? S i n th e combine d fue l strea m routinel yrange d fro m2 0 t o 2 5 ppmv . Thus , Maratho n ca n easil ymee t th e NSP S withou t addin g natura l gas . Sinc e Maratho n ha s begu n t o blen d significan t amount s o f natura l gas , th e concentratio n i n th e sample d strea mha s decrease d proportionall yt o th e volum e o f natura l ga s added . Emission"Test s Emissio n performanc e test s wer e conducte d o n th e treate d fue l ga s whe n th e refiner ybega n it s initia l operatio n and afte r th e expansion . Maratho n personne l di d no t hav e th e tes t report s readil yavailable , bu t agree d t o provid e thes e report s later . Blak e Harmo n di d note , however , tha t th e test s wer e don e o n stream s directl yafte r th e amin e treaters , no t afte r blendin g wit han ynatura l gas . Th e refiner ydi d no t begi n usin g auxiliar ynatura l ga s unti l a fe wmonth s ago . Cos t o f Complyin g wit hNSP S r.srathon personne l ^i ^ not . hav e a breakdow n o f th e cost s the yincu r t o comrjl ywitY 1 thi s NSPS . Th e majo r component , o f course , i s th e capita l and operatin g cost s o f th e amin e treate r syste mand it s associate d sulfu r recover yunit . Th e cos t o f monitorin g wa s estimate d a s on e hou r per da yfo r fiel d testinn , plu s S bfo r testin n suonlie s eac hday(S2/Draeqe r tube ; 3 tubes / o&y). Th e administrativ e cos t o f recordkeepin g and reportin g fo r jus t th e refiner yfue l ga s HSP S wa s considere d relativel ylow , althoug hi t i s difficul t t o separat e ou t th e administrativ e cos t o f on e NSP S fro mal l th e othe r environmenta l reportin g tha t i s required . Stat e Regulation s I n additio n t o th e federa l HSP S limitation s o n th e leve l o f H2 S i n th e fue l gas , S0 ^ emission s fro mcombustio n source s ar e als o regulate d b ya Louisian a Stat e standar d whic hlimit s th e sulfu r conten t o f fue l oi l t o 0. 7 percen t b

yweight . Th e Stat e ha s adopte d th e federa l NSP S fo r fue l ga s b yreference .P. 7

««cjj r

Comment s o r Problem s wit hNSP S Maratho npersonne l voice da few complaint s abou t th e refinery fue l ga s NSPS . I

ngeneral , they

fel t th e NSP S leve l (16 0 pp m H2S ) wa s technologicall y feasible . However , the y fel t i t wa s unrealisti c an ddisproportionall y

costl y t o contro l th e leve l o f H^ S infue l ga s t o sucha lo w leve l whe ncompare dt o th e othe r source s o f SO 2 emissions . They woul dprefe r a "bubble " approach . Maratho nwoul dlik e a -bubbl e fo r SO 2 emission s fo r th e entir e refinery . It woul dbe operationall y an deconomicall y

beneficia l i f th e NSP S fo r refinery fue l ga s coul dh e waive dunde r a "bubble " approach . V . SUMMARY : The plan tvisi twa

s very informativ e fo rus , an d Maratho n personne l were helpful

. Becaus e th e Maratho n refiner yi s a new , grass-root s refinery , th e tw o amin e treatin g system s ar e representativ e o fnew , state-of-the-ar t technolog yan d operations

. Maratho n personne l indicate d tha tnon e o fth e informatio n tha twa

s discusse d durin g ou rvisi twa s considere d proprietary

. Attachmen t cc : D . Wells , SD B

ESFD/ISB/SDS/NDHcLaughlin/cbaker/bjoverma n x559 5 Rm . 75 2 MU12/21/8 4 Projec t 83/0 3 Fil e AI P 8.1.15. 2 Disk : NMcLaughli n 1 Retype d 2/25/8 5 ch bAttachmen t 1 P. 8

Su e Shaughness y Refinin g Enginee r Louisian a Refinin g Divisio n Maratho n Petroleu m Compan y P.O

. Bo xA C Garyville , Louisian a 7005 1 Telephon e 504/535-224 1

Ke n L Wilkey Associat e Refinin g Enginee r Louisian a Refinin g Divisio n Maratho n Petroleu m Compan y P.O

. Bo xA C Garyville , Louisian a 7005 1 Telephon e 504/535-224 1