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# OAR Box 1784 Prepped by Ollie Stewart



### Document

Number: 

# 19 ) ll-A- 1 Docket Number: 

# A--84-4 4

Printed 10/31/2008 8:05:38 AM Sheet 19 of 143P. 2 APTD-135 2 a 

# ff-A-i 

# BACKGROUN D INFORMATIO N FO R PROPOSE D NE W SOURC E PERFORMANC E STANDARDS :

Asphal t Concret

e Plant s Petroleu m Refinerie s Storag e Vessel s Secondar y Lea d Smelter s an d Refinerie s Bras s o r Bronz

e Ingo t Productio n Plant s Iro n an d Stee l Plant s Sewag e Treatmen t Plant s

Volum e 1 , MAI N TEX T

U . S . ENVIRONMENTA L PROTECTIO N AGENC Y Offic e o f Ai r an d Wate r Program s Offic e o f Ai r Qualit y Plannin g an d Standard s Researc h Triangl e Park , Nort h Carolin a 2771 1

Jun e 197 3P. 3



### TECHNICA

L REPOR T NO . 8 - PETROLEU

M REFINERIES , BURNING O F GASEOUS FUEL S SUMMARY O F PROPOSE D STANDAR D Th e propose dstandar do f performanc e fo r

petroelu mrefinerie s will limi t emission s o f

sulfu r dioxid e fro mproces s heaters , boilers , an dwast e ga s disposa l system s tha t bur n proces s ga s generate din th e refinery . Th e propose dstandar ddoe s no t appl y t o extraordinar y situations , suc h a s emergenc y ga s releases , o r t o th e burnin g o f

liqui do r soli dfuel s i n th e sam e heater s an dboilers . Th e propose dstandar dwill limi t sulfu r dioxid e emission s t o th e atmospher e fro mheaters , boilers , an dflare s b y specifyin g tha t th e fue l ga s burne dshal l contai n n o mor e tha n 23 0 mg/Nm 3 o f hydroge n sulfide , o r

0.1 0 gr/dscf , unles s resultan t combustio n gase s ar e treate di n amanne r equall y effectiv e in preventin g th e releas e o f sulfu r dioxid e t o th e atmosphere . Complianc e wit

h th e standar di s base dupo n measuremen t o f th e hydroge n sulfid e concen tratio n in th e fuel ga s o r

th e sulfu r

dioxid e concentratio n i n th e exi t gases . Th e propose dstandar d i s equivalen t

t o asulfu r

dioxid e conten t

o f approximatel y 2 0 gr/10 0 sc f o f fue l ga s burned . Burnin g suc h fuel wil l resul t

i n aconcentratio n o f

1 5 t o 2 0 pp mo f

sulfu r dioxid e i n th e combustio n products . Th e regulatio n woul dhav e th e effec t o f requirin g hydroge n sulfid e remova l fro mal l refinery

generate dfuel gase s use dt o fire ne w boiler s an dheaters . Th e extracte dsulfu r compound s canno t b e burne di

n flares , heaters , o r

an y othe r

source s unles s th e contro l device s use d(fo r example , flu e ga s scrubbers ) ar e equall y effectiv e a s fue l desulfurization . EMISSION S FRO M PETROLEU M REFINERIE S Refinery processes , suc h a s distillatio n an dflui dcatalyti c cracking , produc e substantia l quantitie s o f

"proces s gas " (Figur e 8 ) tha t ma y contai n mor e tha n 5 percen t hydroge n sulfid e b y volume . If

thi s untreate dga s i s burne di n heaters , boilers , o r flares , substantia l quantitie s o f sulfu r dioxid e will b e emitte dt o th e atmosphere . Monoethanolamin e (MEA ) an ddiethanolamin e (DEA ) scrubbin g unit s (Figur e 9 ) ar e widel y use dt o remov e th e hydroge n sulfid e fro mbot h refiner y proces s gase s an dnatura l gas. 1 In addition , ne w processe s tha t emplo y othe r

scrubbin g medi aar e bein g applie dt o refinery proces s gases . Th e propose dstandar dwil l requir e owner s an doperator s o f ne w facilitie s t o reduc e th e hydroge n sulfid e conten t o f refinery-derive dfue l gase s t o level s tha t ar e consisten t

with thes e technologies . Fo r mos t suc h gases , th e propose dlimi t represent s a reductio n o f

mor e tha n 9 9 percen t

i n sulfid e levels . Fo r

afue l ga s equivalen t

t o methane , th e resultan t emissio n o f

1 6 pp msulfu r

dioxid e i s roughl y equivalen t ;t o 4h e burnin g o f

fue l oi l containin g 0.0 4 percen t sulfu r b y weight . Approximatel y 1 millio n ton s o f sulfu r charge dt o U.S . refinerie s coul dno t b e accounte dfo r

i n 1970 . Th e majorit y o f

thi s sulfu r

wa s probabl y burne dan demitte dt o th e atmospher e a s sulfu r dioxide . I f

al l source s wer e controlle dt o th e leve l o f th e standard , thes e emission s woul db e reduce db y 9 5 percent . (Mos t o f th e differenc e betwee n th e 99 + percen t mentione di n th e precedin g paragrap h an d9 5 percen t i s th e resul t

o f losse s in conversio n o f

th e recovere dgase s int o sulfu r o r sulfuri c acid. ) 2 5A t th e presen t

time , onl y on e loca l regulatio n restrict s sulfu

r dioxid e emission s fro

mth e burnin g o f refiner y proces s gas . Som

e Stat e an dloca

l agencie s hav e propose dregulation s wit h limit s rangin g fro

m1 0 t o 5 0 grain s o

f hydrogen sulfide per

10 0 scf o f fue l ga s burne d(1 9 t o 94 grain s o f sulfu r dioxid e per

10 0 scf) . P. 4

GA S

CRUD E ATMOSPHERI C TOWE R GA S COMPRESSIO N PROCES S GA S

NAPTH A HYDR0TREATE R PROCES S CA S 

# m

GA S OIL S CATALYTI C CRACKIN G 

# U M VACUU M TOWE R

CRUD E DISTILLATIO N RESIDUU M DELAYEDCOKE R CA S 

# f GA

S COMPRESSIO N SOU R PROCES S GA S T O AMIN E TREATIN G

ABSORPTIO N & FRACTIO N UNI T 

# I

SOU R PROCES S GA

S TO AMIN E TREATIN G

Figur e 8 . Petroleu m refiner y proces s ga s system . RATIONAL

E FO RPROPOSE

D STANDAR

D Th e propose dsulfu

r dioxid e standar di s consisten t wit h th e capabilit

y of awel l designe dan d properl y operate damin e treatin g uni t tha t i s use dto scrub typica

l refiner y proces s gase s a

t th e moderat e pressure s availabl e i n th e refinery. 2 ' 4 Amine treatin g technology i s wel l demonstrate d an dha s been widel

y usedt o reduc e hydrogen sulfide concentrations , uuga s stream s t alevel s les s than tha t require dt o mee

t th e propose dstandard . ' ' I Thre e refinerie s wer

e visitedb

y EP A representatives , an dinformatio n wa s obtaine do

n th e operatio n of

amin e systems . Al

l system s wer

e state dto b e operatin g wit h exit ga s concentration s o

f les s tha n 1 3 grain s o

f hydrogen sulfide pe

r 10 0 scf . Diethanolamin e (DEA) an dmonoethanolamin e (MEA ) scrubber s ar e foun

di n almos t ever y U.S . refinery , an

dhundred s ar e operate di

n natura l ga s fields throughou t

th e country . Amine treatin g i s usedto reduc e th e hydrogen sulfide conten t of natura l ga s to th e pipelin e specificatio n leve l o f 0.2 5 gr/100 scf

. I t woul db e difficult , however , t o consistentl y achiev e thi s leve l i n arefiner y wher e treatin g pressure s ar e lowe r than i n natura l ga s 2 6P. 5

SOUR PROCES

S GA S J ABSORBE R WATE R

AMIN E Figur e 9 . Petroleu m refiner y proces s ga s treatin g unit . fields , sinc e highe r

treatin g pressure s favo

r hydrogen sulfide removal . Th e refiner y gase s als o contai n unsaturate dhydrocarbon s no t usuall y foun di

n natura l gas . Thes e unsaturate s ten dt o accelerat e foulin g of

th e amin e solution s an dt o reduc e scrubbin g efficiency . Ther e i s n o discernibl e differenc e i

n plan t hardwar e o r

desig n operatin g parameter s fo r a n amin e treatin g uni t designe dt o trea t

refiner y proces s ga s t o 10 , 50 , o r 10 0 grain s o f hydrogen sulfide pe r

10 0 scf. 2 " 4 Exi t ga s level s ar e apparentl y associate dwit h operatin g practices ; astandar dequivalen t t o 1 3 grain s of hydroge n sulfide pe r

10 0 sc f require s goo doperatin g practic e an dhas , therefore , been chosen a s th e basi s fo

r th e standard . Th e propose dstandar di s expresse din term s of hydrogen sulfide , but

ca n b e measure da s eithe r hydroge n sulfide i n th e fue l ga s o r tota l sulfu

r compound s in stac k

gases . Proces s ga s stream s als o contai n smal l amount s of

othe r sulfu r compounds , whic

h ar e no t remove db

y th e amin e scrubbin g system . Thes e material s wouldb e include di n th e tota l sulfur

compound s measured . ENVIRONMENTA

L IMPAC T O F PROPOSE

D STANDAR

D Du e t o therma l an dchemica l degradation , amin e solution s requir e periodi c replacemen t o r treatment . I n ME

A treatin g systems , i t

i s commo n practic e t o sen dacontinuou s slipstreamo f amin e solutio n t o aheate dreclaimer . There , causti c sod ai s a,dde d an dME A i s disassociate dfro

m complex salts , distilled , an dreturne dt o th e regenerato r tower . As the'sal t

conten t in th e reclaime r increases , i t

i s necessar

y t o purg e th e salt s an drecharg e th e reclaimer . Fo r atypical 200,000

- bbl/da y refiner

y producin g 3 0 x 10 6 dsc f

o f proces s gas , abou t

200 0 lb/mont h of

waste salt s ma

y b e formed . Wate r

i s adde dt o reduc e th e viscosit y of sal t slurr y befor e disposal b

y incineratio n o r landfill . Diethanolamin e ha s ahighe r boilin g poin t

tha n ME A an dcanno t

b e similarl y treated . Usual practic e i s t o continu e operatin g unti l th e solutio n i s spen t an dth e hydroge n sulfide conten t of treate dga s reache s undesirabl e levels . Th e entir e solutio n i s the n replace dwit h fresh solution . In th e typica l refiner y cite dabove , approximatel y 50,00 0 gallon s o f solutio n containin g 2 0 percen t DE A an d1 0 percen t

complex salt s wouldhav e t o b e removedannually . 2 7P. 6

ECONOMI

C IMPAC T O F PROPOSE

D STANDAR

D Treatmen t

o f th e variou s refiner

y ga s an dliqui dstream s t o contro l produc t qualit y i s a commonl y accepte dan dnecessar

y practice . Consultatio n wit h severa l engineerin g companie s tha t desig n amin e absorptio n systems , whic h ar e th e mos t

commonl y usedcontro l devices , indicate s tha t ther e coul db e a2 t o 5 percen t increas e i

n investment

cost , but no discernabl e differenc e i n operatin g costs , betwee

n ane w plan t designe dt o mee

t th e equivalent

o f 1 3 grain s o

f hydrogen sulfid e pe r 10 0 sc f an dane w on e designe dt o meet

10 0 grain s of

hydrogen sulfide pe r

10 0 sc f (typica l curren t practice) . Therefore , ther e i s asmall increas e i n amin e treatin g cos t

t o refiner s a s a resul t o f th e propose dstandard . In addition , increase doperato r effor t an dattentio n ma

y b e require dt o maintai n th e desig n efficienc y o f th e proces s durin g actua l operation . Becaus e thi s cos t facto r i s quit e variabl e dependin g o n th e individual company' s presen t operatin g practic e an d shoul db e o

f mino r consequence , it

ha s no t been quantified . I f

th e refine

r choose s t o ru n a

n increase dvolum

e o f ga s throug h a

n existin g amin e absorptio n system , h e ma y incu r cost s i n upgradin g th e existin g syste mt o mee t

th e propose dstandard . Becaus e eac h syste mmus t b e examine dindividually t o determin e th e cos t o f upgrading , n o attemp t

ha s been mad e t o giv

e cost s fo r thi s typ e o

f modification . It i s th e inten t

o f th e propose dstandar dtha t hydrogen-sulfide-ric h gase s exitin g th e amin e regenerato r

b e directe dt o a

n appropriat e recover

y facility , such a s aClau s sulfu r plant . A medium

siz e refiner

y tha t processe s crud e oil containin g 0.9 2 weigh t percen t sulfur , th e nationa l averag e i n 1968 , woul

dhav e a n emissio n potentia l o

f ove r 10 0 tons/da y o

f sulfu r dioxid e (5 0 tons/da y o

f sulfur ) fro mth e amin e regenerator . Th e annualize dcos t wa s calculate dfo

r arang e o f Clau s plan t sizes . A discontinuit

y occur s i n th e cost-capacit

y curv e at abou t 1 0 lon g tons/day . Th e reaso n fo r th e discontinuit

y i s tha t fo r plant s u p t o abou t

1 0 long tons/day , les s costl y prefabricate dpackag e unit s ca n b e used . Unit s producin g more tha n 1 0 lon g tons/da y ar e generall y field-erectedan d considerabl y mor

e expensive . For eac h siz e unit , th e require dsulfu r sale s pric e t o break

eve n was calculated . A

t asale s pric e of $20/lon g ton , th e break-even siz e fo r packag e Clau s unit s i s abou t 5 lon g tons/day . Th e plan t investment

fo r a5-long-ton/da

y packag e Clau s uni t

i s abou t $90,00 0 exclusiv e o

f possibl e future investment

fo r contro l of th e sulfu r dioxid e i n th e tai l gas . Th e break-even siz e (a t asulfu r pric e of $20/lon g ton ) fo

r field-erectedClau s unit s i s abou t 1 5 lon g tons/day , whic h represent s a

n investment

o f abou t $350,000 . N o dat aar e presente dt o sho w th e cos t

tha t refinerie s wouldincu r

i f thei r hydroge n sulfide remova l system s wer

e require dt o meet

th e 0.2 5 gr/10 0 scf

achieve db

y plant s processin g natura l gas . Ther e ar e severa

l reason s wh

y on e shoul dno t

compar e natura l ga s processin g plant s wit h refiner y fue l ga s systems . Th e natura l ga s plan t processe s ga s at

ahig h pressure , wit

h astabl e ga s composition , an dwit

h lo w level s of

impurities . Thes e condition s allow bette r hydroge n sulfid e absorption . Refiner

y ga s i s at

lowe r pressure , ha s avariabl e composition , an dha s avariet y o f impuritie s tha t

reduc e th e abilit

y o f a n absorptio n syste

mt o reac h th e lo

w level s o

f hydroge n sulfide achieve di

n anatura l ga s plant . Th e refiner y gas.pressur e coul db e increase dat ahig h cost , but othe r limitation s woul

dstil l prevent

th e absorptio n syste

mfro machievin g th e lo

w level s foun d in natura l ga s plants . Cos t dat ahav e no t

been develope dfo

r higher pressur e absorptio n systems , bu t th e smal l incremental reductio n i

n hydroge n sulfide wouldmak e suc h asyste mhighly questionabl e fro ma cost-effectiv e poin t

of view. . . •.,-,» . „ r 

### REFERENCE S FO R TECHNICA L REPOR T NO . 8 1 . Kohl , A.L . an dF.C . Riesenfeld . Ethanolamine s fo r Hydroge n Sulfid

e an dCarbo n Dioxid e Removal . In : Ga s Purification . Ne w York , McGra

w Hil l Company , Inc. , 1960 . 2 . Thompson , H.L . Privat e communicatio n t o R.K . Burr , U.S . Environmental Protectio n Agency , Researc h Triangl e Park , N.C . UOP , Proces s Division , De s Plaines , 111 . Novembe r 15,1971 . 2 8P. 7

3 . Parnell , D.C . Privat e communicatio n t o R.K . Burr , U.S . Environmental Protectio n Agency , Researc h Triangl e Park , N.C . Ford , Baco n an dDavi s Texas , Garland , Texas . January 4 , 1972 . 4 . Mayes , J.R . Private communicatio n t o R.K . Burr , U.S . Environmental Protectio n Agency , Researc h Triangl e Park , N.C . Graf f Engineerin g Corporation , Dallas , Texas . January 6,1972 .

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