# OAR Box 1851

Prepped by Keeia Richards



## Document

Number: 

# 35 ) ll-A- 9 Docket Number: 

# A-90-1 9

Printed 11/19/200811:19:51 AM Sheet 35of 41 P. 1

### P. 2


# i ! I
. 

# A-90-1 9 ll-A- 9 

# ENGINEERING (II m 

# AN D COST STUDY

_ [_EP AA/RT^np^p j 

# OF AI RPOLLUTION CONTROL FO RTH E PETROCHEMICA

L INDUSTR

Y VOLUM E 6 : ETHYLEN

E OXIDE MANUFACTUR

E B Y DIRECT OXIDATIO

N O F ETHYLEN

E

b y
ve 

### D
. E
. Field , R
. C
. Ba/ley , F
. B
. Higgins , Jr.
. J
. A
. Lee , R
. Newirth , an dJ
. W
. Pervie r '•* » 

### * Houdr y Divisio n 4 

### Ai r Product s an dChemicals , Inc
. fS P.O
. Bo x 42 7 Marcu s Hook , Pennsylvani a1906 1
Contrac t No
. 68-02-025 5
EP AProjec t

Officer : Lesli e B
. Evan s Prepare dfo r 

## ENVIRONMENTA L PROTECTIONAGENC Y Offic e o f

Ai r an dWast e Managemen t Offic e o f

Ai r Qualit y Plannin g an dStandard s Researc hTriangl e Park , Nort hCarolin a2771 1

Jun e 197 5P. 3



### Thi s repor t

i s issue db y th e Environmenta l Protectio nAgenc y t o repor t technica l dat ao

f interes t

t o alimite dnumbe r of readers

. Copie s ar e availabl e fre e of

charg e t o Federa l employee s , curren t contractor s an dgrantees , an dnonprofi t organization s - a s supplie s permi t - fro m th e Ai r Pollutio nTechnica l Informatio nCenter , Environmenta l Protectio n Agency , Researc hTriangl e Park , Nort hCarolin a27711 ; or , fo r a fee , fro mth e Nationa l Technica l Informatio nService , 528 5 Por t Roya l Road , Springfield , Virgini a22161
.

Thi s repor t

wa s furnishe dt o th e Environmenta l Protectio nAgenc y b y Houdr y Division/Ai r Product s an dChemicals , Inc
. , Marcu s Hook , Pennsylvani a19061 , i nfulfillmen t of Contrac t

No
. 68-02-0255
. Th e content s o.

f thi s repor t

ar e reproduce dherei nas > receive dfro mHoudr y Division/Air " Product s an dChemicaj s , Inc-
. Th e opinions , findings , an dconclusion s expresse dar e those*.o f th e autho r

an dno t

nerfessaril y thos e o f th e Environmenta l Protectio nAgency
. Mentio no f compan y o r produc t

name s i s no t

t o b e .considere da s a nendorsemen t b y th e Environmenta l Protectio nAgency
. 3



### .

Publicatio nNo
. EPA^50/3-73-006- f

n 

# rPlan tE M Cod aNo . Capacit y - Ton aEtO/Yr . Rang e o f

Productio n - X

o f Mas . Eaiaalon at o Ataospher e Straa a

Flo v - Lba./Hr . Flow Characteristi c - Continuou s o r Intermitten t I f Intermitten t - Hrs./Yr . Compositio n- Ton/To nEt O Oayge n Nitrogen , Argo n CO , Staaa i HO , C i - C ^ & Highe rHydrocarbon s Particulate s Ven tStack s Numbe r Heigh t- Fee t Disaste r- Inche s Exi tGa s Temperatur e - ° F SCFM/Stac k Emissio n Contro l Device s Analysi s Dat e o rFrequenc y o f Samplin g Ta p Locatio n Typ e o fAnalysi s Odo rProble m S__ar y o f

Ai rPollutant s Hydrocarbon s - Ton/To n Et O Aerosol s - Ton/To n Et O NO , - Ton/To n Et O SO , - Ton/To n Et O C O • Ton/To n Et O Typ e o f Proces s •Fue l TABL E EO- 3 NATIONA L EMISSION S INVENTOR Y ETHYLEN E OXID E B YDIREC T OXIDATIO N

o
'Absorbe r Wast e ca s 116,35 2 Continuou s

1.70473 6

0.04982 4

1 5 0 2 4 40 0 23.16 7 13- 1

330,00 0
Strippe r Tai l Ca e 1,09 6 Continuou s

0.00015 4 0.00151 2 0.01462 4

0.00073 9

1 5 2 2 11 0 16 4

Continuou s fo rEt O Easy , automati c GC . M S N o

Ai rOxidatio n Onc e pe ryea r Eaa y GC , M S N o 0.03611 7

Trace * Pag e 1 o f 5

Reabsorbe r Vent Ca s 3,67 1 Continuou s

0.00070 0 0.13732 8 0.00236 8 0.00644 4 1 3

100 . - 2 00 0

Wate r Scrubbe r

Vent C« f 68 2 Con t inuou s

0.00166 0 0.00458 2 0.01503 6 0,00004 3 0.00595 2

9 5 57 9 Non e
Dall y Easy , i n lin e C C No

0

_Oxidatio n 11 4 Non e
Neve r N o t4 p Non e N o 0.01240 3



### < - y I " 1 5 ] V - i | \

### I J

Plan tEP

A Cods No . Capacit y - Ton s EtO/Yr . Rang e o f

Productio n - 7 o f

Mas . Emission s t o Atmospher e Strea m Flo v- Lbs./Hr . Flo vCharacteristi c- Continuou s o rIntermitten t i f Intermitten t- Hrs./Yr . Compositio n - Ton/To n Et O Oxygen Nitrogen , Argo n CO 2 Steam NO , C | - C 4 & Highe rHydrocarbon s Particulate s Ven tStack s Nuabe r Heigh t- Fee t Diamete r- Inche s Exi tGa s Temperatur e - ° F SCFM/Stack Emissio n Contro l Device s Analysi s Dst e o rFrequenc y o f Samplin g Ta p Locatio n Typ e o f Analysi s Odo rProble m Summer y o f Ai rPollutant s Hydrocarbon s - Ton/To n Et O Aerosol s - Ton/To n Et O NO , - Ton/To n Et

O SO , - Ton/To n Et

O C O - Ton/To n Et

O Typ e o f Proces s *Fue l gaa . •flncluda a.00053 8 fugitiv e C2 = losses . TABL E EO- 3 NATIONA L EMISSION S INVENTOR Y ETHYLEN E OXID E P YDIREC T OXIDATIO N 13- 3 40.00 0
Cas Turbin e Exhaus t 87,22 3 Continuou s 0.5238 0 6.977 5 1.087 1 0.1339 0

1 4 8 . y 45 0 's i 18,80 0 A? : Reabsorbe r Ven tCa s 1,23 9 Con tinuous- . 0.0026 2 0.02059 0 0.09475 0 0.00036 0 0.00557 4 0.00005 3 0 1 15 0 4 11 0 20 0 Reseto r

Ven t 475.00 0 Continuo u
0.04500 9 7.0492 7 1.2375 1 0.00051 7 0.00127 0
1 5 0 6 ' x8 ' 44 0 100.00 0 

# i J

Neve r * Difficult ^ 2 pe r da y Eas y Ye s \ 0.00557 4

Ai r Oxidatio n 1 pe rhou r Eas y C C N o Pag e 2 o f 5 13- 7 22 5 00 0 +47 . Recover y Syste m Ven tScrubbe r 5.00 0 Continuou s
0.00236 2 0.01985 8 0.08053 3
0.00804 6
1 4 5 4 9 5 1.05 0

3 pe ryea r Bom b - difficul t M S N o Reacto r Ven t 52. 5 Con t inuou s

0.00003 1 0.00075 5 0.00010 0

0 00004 7

Continuou s Eas y C C t6 No

Ai r Oxidatio n Heate r Ven t 1 6 Con ti nuou s

0.0003 2

, Non e Non e W t Balanc e N o 0.00841 3 0.00051 7 0.000229 * 13- 4

11 0 00 0 +4"/ . C0 2 Purg e Ven t 69,17 3 Cor.tinuou

B

1.161 0 1 589 0 0.00321 7

0.003755+

Oo Oxidatio nPlan tEP

A Code No . Capacit y - TonaEtO/Yr . Rang e o f

Productio n - X

o f Max. Emission s t o Atmospher e Strea m
Flo v- Lbs./Hr . Flo vCharacteristi c- Continuou s o r i f Intermitten t- Hrs./Yr . Compositio n - Ton/To n Et O Oxyge n Nitrogen , Argo n CO j Stea a HO , C j - C 4& Highe rHydrocarbon s Particulate s Ven tStack s Numbe r Migh t- Fee t Diamete r- Inche s Exi tGa s Teaparatur e - « p SCTM/Stac k Emissio n Contro l Device s Analysi s Dat e o rFrequenc y o f Samplin g Ta p Locatio n Typ e o f

Analysi s Odo rProble m Suaaar y o f

Ai rPollutant s Hydrocarbon s - Ton/To n Et O Aeroaol s - Ton/To n Et O NO , - Ton/To n It O S O , - Ton/To n Et O C O - Ton/To n Et O Typ e o f Proces s Intermitten t

,

X . 

## £•• •

, y '

- -• • • Ga s Turbin e Exhaus t 76.00 0 Continuou s
0.0157 8 2 266 0 0.7555 0
0 00276 4
1 • 4 5

. 3 0 61 0 16,55 0

- 2 pe rmont h Easy , us e 0 G C N o



## I ° TABLE E0- 3 NATIONA

L EMISSION S INVENTOR Y ETHYLEN

E OXIDE BY DIREC T OXIDATION

13- 5 100,00 0

• Recover y Sectio n Ven t 3.10 0 Continuou s
0.00116 4 0.0138 5 0.1068 0
0.00215 5
1 3 5 4 10 0 4 8 0

i 2 pe rmont h (bu t Oraa tbom b Easy , automati c G C N o Et O monito r Pag e 3 o f 5

•

continuously ) Absorbe r Ca p 5.50 0 Continuou s
0.01074 8 0 1792 0 0 02628 4
0 00376 8

Certai n conponent u continuousl y Eas y G C N o 0 00868 7 - 'EO-12

Ai r Oxidatio n



### I 1

_ _ "I 1 I i

TABL E EO- 3 NATIONA L EMISSION S INVENTORY ETHYLEN E OXID E BYDIREC T OXIDATIO N Pag e 4 o f 5 Plan tEP

A Cod e No . Capacit y - Ton s EtO/Yr . Rang e o f

Productio n - X

o f Emission s t o Atmospher e Strea m Max . Cycl e Ga s Exhaus t 13- 6 18,00 0

Mi xCa s Exhaus t From Scrubbe r Heate r an d Fue l Vent ? Flo v- Lbs./Hr . Flo vCharacteristi c- Continuou s o rIntermitten t i f Intermitten t- Hrs./Yr . Compositio n - Ton/To n Et O Oxyge n Nitrogen , Argo n CO 2 Stea m NO , C i - C4 & Highe rHydrocarbon s SO , Ven tStack s Numbe r Heigh t- Fee t Diamete r- Inche s Exi tGa s Temperatur e - F o SCFM/Stac k Emissio n Contro l Device s • 

# fc 0.3547 4 5.8496 0 0.9197 1 0.3518 1

, 0.0629 7 0.00172 8 0.0221 9 0.09472 0 0.00062 5 0.00381 9 O.00130 1 0.00000 4

Analysi s Dat e o rFrequenc y o f Samplin g Ta p Locatio n Typ e o f Analysi s Odo rProble m •r y o f Ai rPollutant s Hydrocarbon s - Ton/To n Et O Aerosol s - Ton/To nEt O NO , - Ton/To nEt O SO , - Ton/To nEt O C O - Ton/To nEt O Occasiona l Eas y Orsat , C H N o Onc e pe r mont h Eas y Orsat , CH

. N o 0.06809 0
0.00000 4 Typ e o f Proces s Ai rOxidatio nP. 8 EO-1 4

TABL E EO- 3 LIS T O F ABBREVIATION S I NANALYSE S Shee t 5 o f 5

' ' '• " m

aa , i i | > —- a m i mum ! , i

_ i . . i . » G C - Ga s Chromatograp h
M S - Mas s Spectroscop e Orsa t - Conventiona l orsa t fo r CO2 , 0 2 , C2H 4 C H - Ethylen e oxid e byreactio n wit h MgCl 2 t o for mchlorohydri n



# [
[ 

# c [ [ [P. 9 EO-1 5

TABL E E0-4 A TYPICA L VEN T GA S COMPOSITION S

FO R 20 0 M M LBS./YR
. ETHYLEN E OXID E PRODUCTIO N

USIN G AI R OXIDATIO N
MAI NPROCES S VEN T GA S

Componen t Nitroge n Oxyge n Methan e Ethan e Ethylen e Ethylen e Oxid e Carbo n Dioxid e Avg . Mo l % Reporte d Rang e i n Compositio n 

### 86. 7 2. 9 0. 0 0. 1 1. 6 0.0 1 8. 7 8 0 - 9 0

0. 5 - 4. 5 0 - 0. 9 0 - 0. 1 T R - 2. 3 0 - 0.0 1 0-1 0 Averag e Flo wRat e

Mol/Hr
. Lb.s./Hr
. 4,69 5 15 7 0 5 8 7 0 . 47 1 100.0 0 5,415. 4 

### 13 1 5
2 1 9 15 8 ,46 0 ,02 4 0 15 0 ,43 6 1 7 ,78 2 ,86 9 32,40 2 SCF M 29. 3 Avg . Mo l Wt . C0 2 RIC H PURG E GA S

Componen t Nitroge n Oxyge n Ethylen e Ethylen e Oxid e Carbo n Dioxid e 

### Avg . Mo l 1 8 2 4. 5 0. 5 7 5 100. 0 %



### ' 47 5 SCFM Reporte d

Rang e i n Compositio n 1 3 - 2 5 1 - 2 6 2. 5 - 8. 0 0 - 1. 0 6 2 - 8 0
38. 7 Avg . M Averag e

Mol/Hr
. 14. 2 1. 6

• 3. 6 0. 4 59. 3 79. 0 Fl

c D WRat e Lbs./Hr
. 39 8 5 1 10 1 1 7 2,49 1 3,05 8



# ] NOTE : Bot h stream s o n a wate r fre e basis
.



# " J•** • 

### E0-1 6

TABLE_J0^4B
20 0
MAI NPROCES S VEN

T GA S Componen t Nitrogen , Argo n(M

W= Oxyge n Methan e Ethan e Ethylen e Ethylen e Oxid e Carbo nDioxid e TYPICA LVEN T GA S COMPOSITION

S M M LB S 

### (1,3 )

39.2 ) ./YR
. USIN G FO R ETHYLEN EOXID E OXYGE NFEE D

Mo l % 16. 2 7. 3 1. 5 14. 2 13. 5 0.00 5 47. 4 100. 0 11 4 SCF M PRODUCTIO

N



### F L Mol/Hr

. 

### 3.0 9 1.3 9 0.2 9 2.7 0 2.5 7 0.00 1 9.0 2 19.0 6 36. 8 Avg
. o

w Rat e

Mo l W t Lbs./Hr

. 12 1 4 4 5 8 1 7 2 0.0 4 ' 37 9 70 2
• C0 2

### RICH PURG

EGA S (1,2,3 ) Componen t Oxyge n Ethan e Ethylen e Carbo n Dioxid e FlowRat e Mo l 7 . 0.0 2 0.1 2 0.1 6 99.7 0 . 100.0 0 3,00 6 SCF M Mol/Hr
. ••.••Voti-'
. 

### 0. 1 0. 6 0. 8 500. 9 

## ?

502. 4 42.0

- Avg . Mo l Wt: .



### Lbs.VHr
. n 

# ~ T 1 8 2 2 21.03 8 21,08 1

(1 ) Base d o n one questionnair e - othe r oxyge n proces s doe s no t hav e an y appreciabl e ven t othe r than CO 2 an d wate r (on

e questionnaire)
. _Me_thari e i s added afte r the reactor s t o buil d u p a backgroun

d o f iner t ga s i n the recycl e strea

ma t reacto r condition s bu t a combustibl e ga s a t boile r conditions
. (2 ) Compositio n an

d quantityadjusted t o includ e futur e change s a s indicated o n the questionnaire
. p.1 0 

# t [

s .

(3 ) Bot h streams o n a wate r fre e basis
.P.1 1

1 

### EO-1 7
3 . Turbin e Exhaus t Many , i f no t al l o f th e plant s surveye dus e natura l ga s fuele d turbine s t o fee dai r an dethylen e t o th e process . Sinc e th e turbine s whic hdriv e th e compressor s ar e no t 10 0 percen t efficient , som e unburne dhydrocarbon s escap e t o th e ai r fro m thi s exhaust . I t ca n b e a considerabl e portio no f th e tota l hydrocarbo nemissions . A larg e variatio ni nthi s strea m ha s bee nreporte d(Tabl e EO-3) . B . Intermitten t Ai r Emission s

N o dat a give nalthoug hsom e plant s repor t flarin g o r ventin g ga s durin g upsets . On e operato r reporte demptyin g th e syste m t o th e flar e o n e o r tw o time s pe r yea r fo r abou t thre e hour s eac htime . C . Liqui dWaste s

Mainl y water , wit hsmal l percentag e o f organics , al l o f whic h appea r t o b e adequatel y treate db y

conventiona l in-plan t biologi c system s fo r mos t respondents . On e responden t reporte dinorgani c salt s (presumabl y

fro m th e CO 2 recover y

section ) i nthi s stream . D . Soli dWaste s

Non e reporte dalthoug hon e responden t allude s t o th e presenc e o f abou t 0.00 4 lbs . o f "sludge'Vlb . Et Oleavin g th e plan t a s par t of , th e wast e wate r stream . N o furthe r dat a wer e given . E . Odor s •

No t on e responden t reporte dan y odo r proble m

o nan y stream . Th e onl y referenc e t o odo r wa s th e indicatio nthat , i f ther e wer e a nodo r detectable , i t woul db e ethylene . Actuall y thi s respons e i s no t surprisin g because :

• J1 . Th e hydrocarbo nconten t o f th e vas t majorit y o f al l th e ven t stream s i s quit e low . ..,-r . ^ 0 1 "'-.•' • 

### ! 2 . Ethylen e i s a colorles s swee t smellin g gas . I nlo w con centration , i.e. , les s tha ntw o percent , i t i s doubtfu l i f o n e coul ddetec t a nodo r directl y i nth e ven t stream . A s th e ven t ga s mixe s wit hth e surroundin g air , an dth e ethylen e

— 

### become s mor e dilute , th e possibilit y o f a nodo r proble m fade s away . Th e absenc e o f an y detectabl e odo r doe s no t mea ntha t ther e ar e n o hydrocarbo nemissions . Ethylen e oxid e o nth e othe r han dha s a pungen t irritatin g odor . N o on e eve ns o muc ha s indicate da nethylen e oxid e odo r problem . Again , no t surprising . Ethylen e oxid e i s th e desire dproduc t an d

— 

### th e odo r o f Et Omean s los s o f a valuabl e commodity . T o allo w continuou s los s o f Et Owoul djus t no t mak e goo deconomi c sens e an d an y odo r proble m

associate dwit hethylen e oxid e woul db e temporar y « • an dmos t probabl y du e t o a sever e upse t o r equipmen t failure . 

# J

### E0-1 8 

# 1 IV . Emissio n Contro l Device s an d System s

A . Emissio n Contro l Device s o n Mai n Proces s Ven t 1 . Absorber s an d Scrubber s

2 . Catalyti c Conversio n Unit s FM 2 

# L - [ Th e mai n ethylen e oxid e absorbe r ven t ga s o n al l plant s i s recycle d t o th e process . Th e secondar yo r purg e absorbe r ven t ga s T~ i s normall yth e mai n proces s ven t fo r th e ai r oxidatio n plant s 1 ^ ai d th e oxyge n fee d plants
. Tw o ai r oxidatio n proces s respondent s catalyticall yconver t thi s dilut e hydrocarbo n strea mt o N2 , CO2 , 0 2 

### an d H2 O an d driv e proces s tubine s wit hth e ho t compresse d gas . Th e othe r fiv e respondent s ven t thi s strea mt o th e air
. 

# r


# r On e o f thes e latte r plant s (als o ai r oxidation ) supplie d dat a o n j thei r purg e absorbe r an d i t ha s bee n include d o n Tabl e EO- 5 fo r th e sak e o f completeness
. Actuall yal l plant s hav e thi s absorber-scrubbe r bu t onl yon e gav e dat a o n it
. Strictl yspeaking , i t i s a necessar y proces s contro l device
. I t i s identifie d a s 00 2 o n Tabl e EO-5 . Wate r i s th e absorbin g medium
. Ethylen e oxid e absorbers/scrubber s d o a n excellen t jo bi n removin g Et O fro m th e off-ga s stream . Efficiencie s o f 99.9+7 . ar e no t uncommon . Ethylen e oxid e i s ver ysolubl e i n wate r an d a wel l designe d scrubbe r shoul d perfor m

well
. However , a wate r scrubbe r wil l no t remov e an y appreciabl e ethan e o r ethylen e fro mth e ven t ga s an d a s suc hthi s represent s th e majo r sourc e o f ai r pollutio n fo r th e process . Unles s thi s strea mi s catalyticall ycombuste d t o CO 2 an d water , i t wil l contribut e substantia l quantitie s o f hydrocarbon s t o th e ai r i n a strea mgenerall yto o dilut e t o bur n b yitself
. Ven t ga s scrubber s usin g wate r t o recove r ethylen e oxid e ar e use d b ytw o respondent s (se e Tabl e EO-5 ) o n th e CO 2 purg e strea m o f ai r oxidatio n processes . Her e agai n th e efficienc yo f ethylen e oxid e recover yi s goo d bu t efficienc yi s poo r i n term s o f tota l hydrocarbo n emissions
. Thi s CO 2 purg e strea mi s th e smalle r o f th e tw o mai n ven t streams . 

# r

r 1 

### Thes e unit s ar e designe d t o conver t th e ethylen e conten t (abou t tw o percent ) o f th e absorbe r ven t ga s t o CO 2 an d wate r an d t o hea t th e ga s j strea ma t 100-20 0 PSI Gfro mambien t temperatur e u p t o 1300 ° F . Th e ga s i s the n use d t o driv e a ga s turbin e an d exhaust s a t abou t 600 ° F t o a stack
. Dat a o n thes e unit s cam e fro mtw o ai r oxidatio n processes . [ ~ L Atypica l catalys t woul d consis t o f activate d preciou s metal s (probabl yplatinum ) uniforml ycoate d o n a mattin g o f hig hnicke l , _ chrom e allo ymeta l ribbins
. Sel f supportin g catalys t mat s ar e mounte d j i n a hollo wcylindrica l configuration
. Th e catalys t tub e i s surrounde d * " b ya cylindrica l baffl e tha t direct s th e incomin g ga s t o th e to p o f th e vesse l wher e ga s burner s prehea t th e ga s t o reactio n temperature . Th e | ~ heate d ga s the n passe s ove r th e catalys t wher e th e ethylen e react s wit hL th e oxyge n i n th e ga s an d heat s th e mas s o f th e ga s t o abou t 1300 ° F . Th e converte r outle t temperatur e control s th e firin g o f th e prehea t burners
.TABL EEO- 5 CATALO G O F EMISSIO N CONTRO L DEVICE S Pag e I o f 2

ABSORBERS/SCRUBBER S EP A Cod e No . fo rplan tusin g Flo wDiagra m (Fig

. No ) Strea m I . D . Devic e I . D . No
. Contro l Emissio no f Scrubbing/Absorbin g Liqui d Typ e - Spra y

Pscke dColum

n Trs y Colua n Scrubbing/Absorbin g Liqui dRat e - GP M Desig nTemperatur e (Operatin g Temperature ) ° F Gs s Rat e - SCF M

(lb./hr. ) T- T Height , Fee t Diamete r - Fee t Washe dCase s t o Stac k Stac k Heigh t - Fee t Stac k Diamete r - Inche s Installe dCos t - Mat'l . & Labo r - $ Installe dCoa t Baae do n'"year " - $ Installe dCos t - c/lb
. Operatin g Coa t - Annua l - $ (1972 ) Valu e o f Recovere dProduc t - $/Yr . Ne t Operatin g Cos t - c/lb . Efficienc y

- I - S E Efficienc y

- 1 - SER R

*Fo r tota l hydrocarbons . **Fo r recovere dEtO . 13. 6 (EO-l)-l O 00 2 Ethylen e Oxid e Wate r

3 0 10 0 30 0 3 2 2 Ye s 6 2 3 Unknov n

No t Availabl e

99.9 9 97.05 * 13. 6 (EO-l)-l O 00 1 Ethylen e Oxid e Wate r

8 0 20 0 650 0 5 7 5 3. 5 Ye s 3 8 8 Unknov n

No t Availabl e

98. 5 56.9 * 1 3 7 (EO-l)-l O 10 1 Ethylen e Oxid e Vate r

X 15 0 Ambien t 116 7 4 0 3 . 5 Ye s 4 5 4 24.00 0 196 8 0.005 3 S250 0 $225,000* * (Credi t - 0.049 ) 95. 3 66.2 *INCINERATION DEVICES EP A Cod e No . fo rplan tusin g Flo wDiagra m (Fig . No. ) Strea m I . D . Devic e I . D . No . Typ e o f Compoun

dIncinerate d Typ e o f Devic e Materia l Incinerated , Lb./Hr . (SCFM ) Auxiliar y

Fue l Req'd . (excl . pilot ) Typ e Rat e - BTU/Hr . Devic e o r Stac kHeigh t - Fee t Installe dCos t - Mat'I . & Labo r - $ Installe dCos t Base don"year " - $ InstalledCos t - c/lb . Operatin g Coa t - Annua l - $/Yr . Operating Coa t - c/lb . Efficienc y

- X - CC R Efficienc y

- X - SERR TABL E EO- 5 CATALO GO F EMISSION CONTRO L DEVICE S ( 1 )

13- 3 (EO-l)-l O 10 1 Hydrocarbon s Catalyti cConverte r (20,000 ) CH . 19 7 x C I 1 9 5 7 $74,00 0 196 4 0.092 5 (Credi t (Credi t 10 0 10 0 1 0 6 13- 4 (E0-2)- 9 Hydrocarbon s Flar e Stac k Normall y

Zer o

12 5
$20,000 ) 0.025 ) 10 0 (2 ) 10 0 (2 ) Pag e 2 o f 2

13- 5 (Eo-l)-l O 10 1 Hydrocarbon s Catalyti c Converte r 76.00 0 Natura l Ga s 3 x \0 b 4 5 S300.00 0 196 6 0.1 5 $42.00 0 0.02 1 94. 7 94 . 7

(1 ) Plan t 13- 7 als o reporte d(subsequen t t o thei r complete dquestionnaire ) a catalyti c converte r o n the reacto r ven t shov n i n Tabl e E0-3 . Huwever , the ydi d no t giv e coa t o r perfromanc e dat a o nth e unit . (2 ) Flar e show

na s burnin g completel y t o CO 2 an

dH2O .

r--~ i « - 

### r— \ T \ 1 \ 

### , ^ ^ }P.1 5 

# J J J

. ] ] ] ] ] ] ] ] ] ] ] ] ] EO-2 1

Th e above i s a descriptio no f on e typ e o f catalyti c converter . Ther e ar e othe r design s bu t they follo w the genera l patter ndescribed . Insom e case , i t may

b e necessary

t o injec t smal l quantitie s (roughl y 0. 4 mo l 7« ) o f methan e o r natura l ga s plu s som e ai r i norde r t o insur e complet e combustio ni nthe converter . Thes e unit s ar e rathe r large , seve nto eigh t fee t indiamete r an d1 5 t o 2 0 fee t long .

~ ] ( Tabl e E0- 6 give s a materia l balanc e fo r catalyti c incineratio no f

_ j a lea nhydrocarbo nven t stream . Sectio nVI I cover s the cos t effective nes s o f thi s control . Actua l cos t dat a fo r catalyti c converter s ar e

- » presented , a s give nb y the respondents . 3 . Othe r Combustio nDevice s Fo r thos e ven t stream s whic har e readil y combustible , a stea m boile r coul db e usedto conver t th e hydrocarbo nconten t t o CO 2 an dwate r an

d recove r som

e o f the wast e hea t a s steam . Sinc e ethylen e oxid e plant s ar e ne t stea

m producer s du e t o th e exothermi c hea t o f reaction , i t ma y b e uneconomica l t o runye t anothe r stea m boile r ona wast e strea m an d have t o transpor t th e stea m fro m the proces s are a t o wher e i t ca nb e used . I nthi s case , a therma l incinerato r coul dconver t the ven t ga s strea m t o CO o an dwate r an

deliminat e emission s o f hydrocarbon s to the air . Onl y on e responden t indicate s us e o f th e mai nproces s ven t strea m i na stea

m boile r bu t n

o operatin g dat a wer e given . This , o f course , i s th e cas e wher e methan e i s addedt o the recycle . No one indicate d us e o f a therma l incinerato r s o i t i s difficul t t o accuratel y predic t equipmen t performanc e inthes e tw o applications . Tabl e EO- 7 an dEO- 8 give materia l an

dhea t balanc e dat a for combustio no f a fairl y ric h hydrocarbo nven t stream . No dat a ar e include dfo r therma l incineratio n or stea m generatio no f a leanhydrocarbo nstrea m (belo w th e lowe r flammabilit y

limit ) becaus e suc htreatmen t i s impractica l an d uneconomic . 4 . Flar e Syste

m On e responden t (oxygenoxidatio nprocess ) report s onthe us e o f a flar e syste

m (only durin g emergencies ) an dclaim s 10 0 percen t efficiency . It.wa s no t reporte dwhethe r or no t supplementa l fue l wa s used . Generally , a "flar e system " i s understoo dt o mea na combustio nstac k tha t doe s no t requir e supplementary fue l excep t for pilo t lights . O nthe othe r hand , a plum e burne r i s one whic hi s burnin g a ga s tha t i s normall y clos e t o o r below

it s lowe r flammable-limi t an dthu s require s a continuou s suppl y o f supplementa l fuel . I t i s normall y assume dtha t neithe r a flar e stac k no r a plum e burne r wil l achiev e mor e thanabou t 9 0 percen t combustio nefficiency . Th e oxyge noxidatio nven t ga s show ni nTabl e E0- 7 wil l suppor t combustio nan

dcoul dbe flared . However , i t i s unlikel y tha t combustio n woul db e complete . I t i s mor e likel y tha t abou t 1 0 percen t o f the heating valu e wil l b e los t i nthe for m o f carbo nmonoxid e an dunburne d o r cracke dhydrocarbons . I f the plan t ha s anexistin g flar e fro m anothe r process , additiona l supplementa l fue l migh t no t b e required , dependin g upo nthe heating valu e o f tota l flaredgases . I nan y case , however , imprope r firing coul dresul t i nNOxformation .EO-2 2

TABL E EO- 6 AI RFEE D PLANT CATALYTI C INCINERATION (1 )
MATERIAL BALANCE . LB./HR . Combustio nAi r Flu e Ga s (3 ) 14,66 3 131,85 8 4,45 7 21 2 0 T R 0 T R 0 TR 0 0 0 30,75 4

' 0 -6. 4 0 3.56 0 161,93 3 • 19,12 0 181,05 3 (1 ) - Combine dcombustible s ar e 1.6 7 percen t b y volume vs . 2. 7 percen t lea nlowe r •"limi t for ethylen e i nair . Catalyti c incineratio ni s necessary t o hol d • combustio nchambe r temperatur e i nth e 1300 ° t o 1500 ° range . 0 . (2 ) Combine dprocess , stream , mai nven t plu s CO 2 vent , wate r fre e basis . (3 ) Unburne dhydrocarbon s reporte da s "trace " i nflue gas . One responden t reporte d20 0 t o 30 0 pp m i nflue

< gas - bu t hi s ven t ga s strea m differe dfro

m tha t show

nabove . Flu e ga s ha s 0. 5 percen t exces s O 2 a s pe r respondne t experienc e wit hcatalyti c converters . • Componen t
N 2



## ° 2 CH 4

C 2 H 6 C 2 H 4 

### Et O 

## co 2 NOx(4 )
H 2 0 " Proces s Ven t Ga s ( - 131,85 8 5,07 5 

### 0 15 0 2,53 7 

### 3 4 22,27 3 

### 6. 4 ' P . 1 6



# 7

(4 ) 4 0 ppm .P.1 7
EO-2 3

Componen t
N 2 , A



## ° 2 CH4
C 2 H 6 C 2 H 4 

### Et O 

## co 2 

### NO x H 2 

### 0 OXYGE N TABL E FEE D PLANT . EO- 7

STEA M GENERATIO

N OVERAL L MATERIA

L BALANC E Proces s Ven t Ga s (2 ) 

### 12 1 4 4 

### 5 8 1 7 2 0.0 4 

### 37 9 

### 0 LB .

Com b /HR
. ustio n 2,10 2 

### 63 9 

### 0 0 0 0 0 0 0 Ai r 

# ( D Flu e Ga s

2,22 3

• 11 4 

### T R T R T R T R 

### 82 7 T R 

### 25 0 70 2 2,74 1 3,44 4 (1 ) 2 0 percen t exces s 0 2 « (2 ) Wate r fre e basi s combine d combustible s ar e 27. 6 percen t wel l ove r th e lowe r limi t fo r ethylene
. Thi s strea mwil l suppor t combustion
. Othe r Dat a - Hea t Balanc e

a . Hea t o f combustio n o f methane , ethane , ethylen e i n stream
- 3,221,07 8 BTU/Hr
. b
. Les s sensibl e heat , 85 ° y570 ° (stac k temperature)

- 439,02 0 BTU/Hr
.
c . Ne t hea t availabl e fo r steamgeneratio n 2,782,05 8 B>TU/Hr
. d
. Stea mavailabl e a t 750 ° F , 45 0 PSI G a t 2,26 1 Lbs./Hr
. 75c/100 0 lbs. , credi t i s $14,85 0 pe r yea r

# T 

# r r r

i i i P.1 8 EO-2 4

• TABL E EO- 8 OXYGE N FEE D PLANT THERMAL INCINERATION MATERIAL BALANC E

Thi s sam

e strea

m whe nthermall y

incinerate dwit h2 0 percen t exces s 0 2 wil l give the sam

e product s o f combustio na s a stea m generato r bu t th e heatin g valu e o f the stac k ga s wil l b e lost . Anincinerato r fo r thi s strea m wil l cos t les s tha nhal f o f a comparabl e stea m generato r bu t the ne t operatin g cos t i s som e 2 5 percen t higher . Se e Tabl e E0-7 .

# . ; A " : . P . 1 9 

## E0-2 5 - 1

B . C0 2 Ric hPurg e Ga s |

Thi s stream , whic haverage s aroun d30 0 SCF M

for a typica l 20 0 L— f M M lbs./yea r plant , i s normall y vente ddirectl y

t o th e ai r b

y al l I respondents . Fo r ai r oxidatio nplants , th e strea m contain s abou t 7 0 vol . % C0 2 an

d5-67 . hydrocarbon s an dcanbe incinerated . The bes t solutio nwoul dbe t o combin e thi s ven t strea m wit hth e mai n proces s ven t strea m sinc e i t i s a smal l flo w an ddispos e o f bot h stream s together . On e responden t plan s t o d o jus t this , feeding | th e C0 2 ric hstrea m t o a catalyti c converte r alon g wit hthe mai n*• • ' proces s ven t an

dvirtuall y

eliminatin g emission s fro m th e plant . 

# i i

Fo r the oxyge nfeedplants , thi s strea m contain s wate r vapor , 30-5 0 percen t C0 2 an donl y trace s o f hydrocarbons . Hence , thes e plant s probabl y

hav e no nee dt o trea t thi s strea m an y further . On e responden t usuall y dispose s o f thi s strea m by sellin g i t t o a noff sit e consume r for it s carbo ndioxid e content , bu t wha t i s done wit h th e hydrocarbo nconten t i s un-reported . C . By-Produc t Disposa l 1 . Wast e Wate r From 0.00 7 t o 0. 9 gallon s o f wast e wate r pe r lb . ethylen e oxid e ar e produce dwit hthe large r plant s consumin g the leas t water/Lb . product . Dat a o ncontaminant s i nth e wast e stream s ar e very sketch

y bu t ar e probabl y

ethylen e glyco l (mainly ) acetaldehyd e an dmiscellaneou s hydrocarbons . Al l respondents , sav e one , trea t thi s stream i nplan t befor e discharge . Thi s strea m i s biodegradabl e an dpresent s no unusua l operatin g problems . 2 . Wast e Solid s N o wast e solid s wer e reported .

• 3 . Miscellaneou s * T
No othe r by-product s were reported . D . Bes t Availabl e Pollutio nContro l System

The bes t contro l system for a nai r oxidatio nethylen e oxid e plan t i s t o feedbot hth e mai nproces s ven t an dth e C0 2 purg e ven t t o a catalyti c converte r an duse th e ho t gase s fro m thi s uni t t o powe r feedturbine s t o th e process . Wit hthi s set-up , emission s fro m th e plan t ven t stream s shoul donl y be N 2 , 0 2 , C0 2 wit hpossibl e trace s . , o f hydrocarbon s an dNOx . Th e questionnaire s indicat e tha t severa l plant s ar e plannin g t o instal l thi s typ e o f system . Oxyge nfeed plant s ar e differen t tha nai r feedplant s because th e CO 2 purg e ven t whic hi s reporte da s essentiall y hydrocarbo nfree , i s th e large r stream , an

dprobabl y

ca nb e vente ddirectl y t o th e ai r wit hlittl e o r no effec t o nth e pollutio nlevel . I t i s als o apparentl y pur e enoug h t o b e sol da s C0 2 . The mai nproces s ven t fro m thes e plant s i s smal l bu t i s combustible . I t ca nbes t be dispose do f by burnin g i na stea m generato r wit hrecover y o f th e hea t a s steam . I f stea m i s no t neede d an dthe ga s canno t easil y be transporte delsewhere , i t may be dispose d o f i na therma l incinerato r wit ha simila r reductio ni nemission s a s th e stea

m generator , bu t wit hno energy recovery . 

# t

L r

# — J P.2 0 E0-2 6

On e o f the ai r oxidatio nprocesse s feature s introductio no f methan e a s a n"inert " backgroundga s i nthe recycl e strea m in contras t t o othe r oxyge nprocesse s whic hhav e no methan e addition . Th e relativel y

ric hmai nproces s ven t ga s fro m thes e plant s ca n b e sen t t o the plan t boiler s a s supplementa l fuel , eve nthoug hthe methan e doe s no t oxidiz e a t reacto r conditions . Whethe r o r no t the C0 2 purg e ven t fro m eithe r typ e o f oxyge nplan t ca nb e vente dshoul db e dtermine db y a nEPA sampling program . I f not , i t coul dconstitut e a proble m becaus e i t i s to o larg e to b e combine d wit hth

e mai nproces s ven t for incineratio neithe r i nth e plan t boiler , the stea

m generato r or the therma l incinerator . Th e dilutio n effec t woul drende r the combine dstrea m non-combustible .



# L :E0-2 7

V . Nationa l Emissio nInventory Base do nthe emissio nfactor s show ni nTable EO-3 , th e tota l emission s fro m th e ethylen e oxid e plant s surveye dwere estimate dan dar e summarize di n Table E0-9 . Usin g Tabl e E0-9 , the tota l approximat e emission s fro m al l U.S . ethylen e oxid e plant s ar e a s follows :
Componen t Hydrocarbon s Particulate s NOx SO x Averag e Emission s T/ T Ethylen e Oxid e 0.0204 8 0.00000 7 0.00006 6 0.00003 1
Tota l = 0.02058 4 Tota l Emission s (1 ) M M Lbs./Yea r 85.8 3 0.0 3 0.2 8 0.1 3 86.2 7
I f al l ai r feedplant s catalyticall y converte dthei r mai nproces s ven t gase s t o C0 2 an

dH 2 0 an

duse dthe ho t exhaus t t o driv e th e plan t feedturbines , (als o cuttin g th e turbin e emission s abou t i nhalf ) an doxyge nfeedplant s incinerate dthei r mai nproces s ven t i na stea m generator , tota l emission s woul d b e reduce dt o the followin g approximat e values :
Componen t P.2 1 

# r i

Hydrocarbon s Particulate s NOx SOx Averag e Emission s (2 ) T/ T Ethylen e Oxid e 0.004 9 0.00000 7 0.000 1 0.00003 1 Tota l Emission s ( i M M Lbs./Yea r 20.5 3 0.0 3 0.4 2 0.1 3
Tota l = 0.00503 8 21.1 1 (1 ) Basi s 4,19 1 M M lbs . Et O pe r yea r i n1972 . (2 ) Se e als o Tabl e EO-16 .

• •*• - j_"*?.*"._!r.«-" -

### Emissio n

Hydrocarbon s Particulate s NOx SO x C O

Hydrocarbon s Particulates , SOx , C O Et O

Absorbe r Ven t Ga s 0.011 8

NO x Recovery

Sectio n Vent s 0.000 6

Reabsorbe r 0.006 4 Ni l Ni l

OXYGE N

' C0 2 

### Purg e i TABL E E0

-

EMISSIONSOURC E 9

SUMMAR Y TON/TONETHYLENE OXID E AI R OXIDATION

Sourc e Ven t Ga s Scrubbe r Turbin e Outle t Exhaus t 0.002 3 0.013 2 0.0000 1

OXYGE NOXIDATION Ven t Ga s

OXIDATIO

NPLANT S WIT H \Jent PLANT S

PLANTS *

METHANE Reacto r o r

Heate r Ven t 0.000 6

0.000 1 0.0000 5 C0 2 

### Purg e

Ven t 0.0000 1

Wate r Scrubbe r Ven t 0.006 0 Ni l Ni l

ADDITION * Fugitiv e L o sse s Figitiv e Emission s 0.0000 1 Tota l

0.028 5 0.0000 1 0.000 1 0.0000 5

Tota l 0.012 4 Ni l Ni l

Tota lEO-28



### Hydrocarbon s Particulates , NO

x SOx , C O 0.003 2 0.000 6 Ni l ° Ni l Ni l Ni l 0.003 8 Ni l Ni l
*Dat a fro

mon e responden t only
.P.2 3 E0-2 9

VI . GroundLeve l Ai r Qualit y Determinatio n Tabl e EO- 3 present s a summar y o f ai r emission s dat a fo r variou s surv

e e d ethylen e oxid e plants . Thi s tabl e include s emission s fro m the mai nproces s vent , C0 2 purg e vent , turbin e exhausts , reacto r hea t transfe r flui dven t an d a nestimat e o f fugitive emissions . Informatio nregardin g vapo r losse s fro m produc t storag e have no t bee nincluded , bu t losse s fro m thes e storag e facilitie s shoul db e ld& for th e following reasons : (a ) Al l plant s reportin g dat a o nthei r storag e facilitie s hav e re frigerated , coole dand/o r pressur e (iner t blanket ) storag e fo r ethylen e oxide . Hence , emission s shoul db e negligible . On e plan t blanket s the ethylen e oxid e wit hnatura l ga s t o preven t los s o f EtO . Th e blanketin g ga s usuall y goe s t o a flar e whe n the tank "breathes" . A los s o f blanketin g ga s i s unavoidabl e bu t wil l contribut e virtuall y no ai r emission s i f i t i s flared properly . (b ) Som

e plant s tak e ethylen e oxid e directl y t o a glyco l plan t an da s suc hhave no storag e facilitie s for thi s product . Tabl e EO- 3 provide s operatin g condition s an dphysica l dimension s o f th e variou s ven t stacks . Th e EPA wil l us e thi s informatio ntogethe r wit hthe ai r emissio ndat a t o calculat e groun dleve l concentratio nfor late r reporting .

# J7 

# J P.2 4 

### EO-3 0

VII . Cos t Effectivenes s o f Control s A cos t analysi s for alternativ e method s o f reducin g ai r pollutio nfro m th e mai nproces s vent s o f a typica l 20 0 M M lbs . pe r yea r ethylen e oxid e plan t i s show nonTable s EO-1 0 an dEO-11 . Tabl e EO-1 0 represent s dat a fro m plant s usin g ai r feedwhil e Tabl e EO-1 1 show s simila r dat a fo r oxyge noxidatio nplants . A . Investmen t Purchase dcost s o f stea m generators , therma l incinerator s an d catalyti c incinerator s wer e obtained.from curren t vendo r quote s fo r simila r package dtyp e units . Cost s fo r th e catalyti c converte r represen t actua l dollar s reporte dfro m respondent s questionnair e

- ; up-date dt o 1973 . 

# j B . Operatin g Expens e Unles s dat a wer e availabl e fro m th e respondent , w e used : 1 . Depreciatio n- 1 0 yea r straigh t line . 2 . Interes t - 6 percen t ontota l capita l 3 . Maintenanc e - 3 percen t o f investment . 4 . Labo r - One-quarte r o f a ma nassume dfo r boiler s (stea m generator ) an

done-eight hma nfo r incinerators . 5 . Utilitie s - Base do nth e Gul f Coas t area . Th e table s show

tha t i f th e steam

ca nb e used , a stea m generato r i s a cheape r metho dt o us e tha na therma l incinerato r for a noxyge noxidatio n tt process . A

properl y

designe dtherma l incinerato r ha s th e advantag e ove r a •* • flar e i ntha t les s NO xshoul db e produced . • I t steam coul dno t b e use do r c c 

### . „ V * ' transporte dt o othe f proces s area s economically , a therma l incinerato r woul d " o b % th e bes t methbdto " us e t o reduc e emissions .

However , tn e ai r proces s ven t stream s ar e no t readil y combustible . I n thi s case , th e bes t solutio nappear s t o b e t o catalyticall y incinerat e th e 0 

### ven t gas . Two respondent s .indi^eatg dtha t thi s wa s don e wit hth e mai nproces s ° ven t gas . Th e ho t gase s fro m th e converte r (catalyti c incinerator ) ar e use d t o driv e the process, , ai r compresso r turbin e drives . Th e literatur e say s tha t almos t every

manufacture r use s these"-gase s t o driv e turbine s fo r th e plant s bu t i f so , onl y

tw o respondent s s o indicate dan dgav e supportin g engineerin g data . If"on e tak e credi t for.th e heatin g valu e o f th e ga s burne dwhic hi s ' use dt o powe r some o f th e proces s feedturbines , th e analysi s show s tha t thi s cos t saving s wil l jus t abou t off-se t th e operatin g an dcapita l charge s fo r a catalyti c converte r i na 20 0 millio nlbs./yea r ethylen e oxid e plant . Al l plant s reportin g stor e ethylen e oxid e eithe r unde r refrigeratio n o r pressur e (N ^ natura l gas) . Al l hav e vapo r conservatio nsystem s an dnon e ven t t o th e atmospher e directly. . A s such , ther e doe s no t appea r t o b e anythin g furthe r necessar y fo r th e storag e facilities .# *' . •

TABL E E0-1 U COS T EFFECTIVENES S O F CONTROL S
Chemica l Tota l U . S . Installe d Capacity , Tons/Yr . (a ) Tots l U . S . Production , Tons/Yr . (a ) Principa l Proces s Percentag e o f

Tota l U . S . Production , Approximat e Averag e Plan tCapacity , Tons/Yr . Emissio n Strea m Emissio n Contro l Devic e Flo v Rate , SCFM

, Basi s Averag e Plan tSiz e Ton/To n Ethylen e Oxid e Capacit y N0 X so 2 C O co 2 N2+ Argo n ° 2 H, 0 Hlsc . H

C Unidentifie d Particulate s Ethylen e Oxid e Installe d Cos tRelativ e t o Emissio n Contro l Devic e Delivere d Cos t Installatio n Tota l capita l Operatin g Cost , $/Yr . Depreciatio n (1 0 years ) Interea to n Capita l (6%) Catalys tReplacemen t(estimated ) Maintenanc e (3 1 o f capital ) ^ Labo r($4.85/man-hour ) Utilitie s Power , lc/KV

H Fuel , 40c/M

M BT U (pilo tgas ) Proces s Vater , lOc/ M Gal . Boile rFee d Vater , 30c/ M Gal . Tota l utilitie s Tota l Operatin g Cost s Heatin g Valu e Credi t(g ) u NetOperatin g Cos t Mai nProces s Non e 32,40 2 Non e Non e Non e 0.8664 5 5.7579 6 0.2200 5 (j ) 0.1132 7 Non e 0.0007 4

0 AI ROXIDATION PROCES S Ethylen e Oxid e 2,100,00 0 2,100,00 0 Ai r Oxidatio n .7 6 100,00 0 Ven t Catalyti c (f ) Incineratio n

Non e Non e Non e 1.2225 5 6.3509 3 0.0085 8 0.1496 2 T R Non e T R $158,00 0 67,00 0 $225,00 0 $ 22,50 0 13,50 0 5,00 0 6,60 0

. 4,90 0 (1/ 8 man ) 20 0 50 0 (c ) 0 0 $ 70 0 $ 53,40 0 50,00 0 $ 3,40 0 Non e 48 0 Non e (b ) Non e T R 0.1091 1 0.0174 3 0.0023 0 (j ) 0.0044 2 Non e (d ) 0.00074 . <o

C0 2 Ric h Purg e Cas Catalyti c Incinerato r fa )

TR Non e Non e 0.1244 8 0.0667 5 0.0007 0 0.0063 1 T R Non e TR $12,00 0 8.00 0 $20,00 0 2,00 0 1,20 0 50 0 60 0

20 0 50 0 (c ) 0 0 70 0 5,00 0 1,00 0 4,00 0 

### , ?

(a ) Estimat e fo r 1973 . (b ) Exceptio n- on e responden t report s 4 0 PP M N O i na ven t containin g n o othe r pollutan t vapors . (c ) Hea t exchang e incorporate dfor sustaine doxidation ; pilo t onl y during portio no f start-u psequence . Start-upfue l required . (d ) Exceptio n- on e responden t report s "les s tha nthre e lbs./hr . (o f particulates) , primaril y carbon , smal l quantitie s of Iro nan d chlorine" . (e ) Incineratio nfigure s ar e estimate dfor additio no f facilitie s vher e non e exis t i ncurren t practice . Th e inclusio no f thes e figure s i s no t t o b e construe daa a n indicatio ntha t the facilitie s Bhoul dor shoul dno t b e installed . (f ) Dat a fro

m tvo respondent s shove dabou t $85,00 0 purchase dcos t i n196 4 - 1966 , update dt o $150,00 0 i n197 3 sn

destimate d$225,00 0 installe dcost . (g ) Credi t o f 0.025c/lb . o f EtO/yea r take nfro m ne t heatin g valu e o f ga s burne dan d usedt o pove r turbines . (h ) Stream s ar e belo v lea nlove r Limi t fo r combustion . Therma l incineratio nor Incineratio ni na steam boile r voul drequir e excessiv e firebox temperature s for complet e combustion , (i ) Installe dcos t base dondat a fro m tvo respondents . Correcte dt o 20 0 millio nlbs./yea r vi a the "0. 6 factor " an d up-date dfro

m 196 5 cost s using O&CJ Constructio nCoa t Index . (j ) Mai nProces s Ven t an d C0 2 Ven t o nvate r fre e basis . , "

I0 1TABL E EO- U COS T EFFECTIVENES S O F CONTROL S OXYGE N OXIDATION

PROCES S
Chemica l Tota l U . S . Installe d Capacity , Tons/Yr . v a ) Tota l U . S . Production , Tons/Yr . (a ) Principa l Proces s Percentag e o f

Tota l U . S . Production , Approximat e Averag e Plan tCapacity , Tons/Yr . Emissio n Strea m Emissio n Contro l Devic e Flo vRate , SCF

M Averag e Plan tSiz e Ton/To n Ethylen e Oxid e Capacit y N0 X S0 - C O co 2 N 2+ Argo n ° 2 H 2 0 Misc . H

C Unidentifie dParticulate s Ethylen e Oxid e C0 2 Ric hPurg e Ga s Non e 5,78 2 Non e Non e Non e 0.9214 7 Non e 0.0001 3 (e ) 0.0009 6 Non e Non e Ethylen e Oxid e 0 0 Oxyge n 5 M

M 5 M M Oxidation 2 4 100,00 0 Non e

69 9 Non e Non e Non e 0.0166 0 0.0053 0 0.0019 3 (e ) 0.0069 2 Non e TR Mai nProces s Ven t Steam Generato r (c ) (b ) T R Non e T R 0.0362 2 0.0973 7 0.0049 9 0.0109 5 T R Non e Non e Th e rm a 1 70 2 (b ) T R Non e T R 0.0362 2 0.0973 7 0.0049 9 0.0109 5 TR Non e Non e Incinerato r (c )

InstalledCos t Relativ e t o Emissio nContro l Devic e Delivere dCos t Installation Tota l Capita l Operating Cost , $/Yr . Depreciatio n(1 0 years ) Interes t o nCapita l (6% ) Catalys t Replacemen t (Estimated) Maintenanc e (3 % o f capital ) Labo r ($4.85/man-hour ) Utilitie s Power , lc/KW

H (estimated ) Fuel , 40c/M

M BT U(pilo t gas ) Proces s Water , 10c/ M Gal . Boile r Fee

dVater , 30c/ M

Gal . Tota l Utilitie s Tota l Operatin g Cost s Stea m Generation , 75c/ M Lbs . (credit ) Ne t Operatin g Cost s 20,00 0 20,00 0 40,00 0 4,00 0 2,40 0 0 1,20 0 9,70 0 ( ^ man ) 20 0 1,50 0 0 70 0 2,40 0 19,700/Yr . ($13,800/Yr. ) 5,900/Yr . 8,00 0 8,00 0 16,00 0 1,60 0 1,00 0 0 50 0 4,90 0 (1/ 8 man ) 10 0 1,50 0 0 0 1,60 0 9,600/Yr . 9,600/Yr . (a ) Estimatedfor 1973 . (b ) Basi s 20 % "exces s air" . (c ) Stea

m generatio nan

dincineratio nfigure s ar e estimate dfo r additio no f facilitie s vher e none exis t i ncurren t practice . Th e inclusio nof thes e figure s i s no t t o be construe da s a nIndicatio ntha t th e facilitie s shoul do r shoul dno t b e installed . (d ) Cos t o f stea

m generato r an

dtherma l incinerato r fro m A.P.C.I . (Catalytic , Inc.) compan y files . (e ) Vent s o nvate r fre e ba a is .EO- 3 3

VIII . Sourc e Testin g

Plant s 13- 3 and 13- 5 wer e th e onl yplant s tha t reporte d a catalyti c converte r i n operatio n whe n th e questionnaire s wer e completed
. Dat a fro m thes e tw o plant s indicat e tha t a catalyti c converte r i s a n excellen t pollutio n contro l device
. I f th e dat a presente d bythes e respondent s ca n b e substantiate d bya samplin g progra mand i f th e hydrocarbo n emissio n reductio n i s a s complet e a s i s claimed , thi s devic e coul d b e classifie d a s th e bes t demonstrate d emissio n contro l system . I t ha s sinc e bee n reporte d b ya n officia l o f plan t 13- 7 tha t the yals o hav e a catalyti c converter , althoug h thi s wa s no t clea r fro mth e questionnaire
. P.2 7 

# L

u Responden t 13- 4 show s on e strea mwhic h i s quit e ric h i n hydrocarbon s a s goin g t o a stea mgenerator . (N o dat a o n operatio n o f thi s uni t wer e given. ) Th e strea mi s burne d t o generat e stea muse d elsewhere
. I t woul d no t b e valuabl e t o sourc e tes t thi s strea ma s i t represent s a uniqu e process , • - becaus e methan e i s fe d int o th e proces s stream s t o buil d u p a n iner t backgroun d ga s i n th e recycle
. However , sinc e thi s plan t i s a n oxyge n fee d plan t and r report s ver ylo whydrocarbon s i n th e CO 2 purg e ga s vent , a samplin g progra m(
_ t o verif ythi s coul d b e o f value
.P.2 8 

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IX . Industr yGrowt h Projectio n Curren t U.S . capacit yfo r ethylen e oxid e productio n i s estimate d a t 4,19 1 M M lbs./yea r an d i s projecte d t o increas e t o 6,80 0 M M Lbs./yea r by 1985 . (Se e Figur e EO-3 )
B yfar , th e larges t us e fo r ethylen e oxid e i s i n th e productio n o f ethylen e glycol
. Probabl ytwo-third s o f al l th e ethylen e oxid e produce d goe s int o glyco l manufacture
. Ehylen e glycol' s largest , bu t slowes t growin g end us e i s anti-freez e whic h account s fo r abou t 7 0 percen t o f th e ethylen e glyco l produced
. Anothe r are a o f increase d us e o f glyco l i s i n polyeste r fibe r an

d fil mproduction
. Th e second larges t marke t fo r ethylen e oxid e i s nonioni c surface-activ e agent s whic h consum e 10-1 5 percen t o f th e ethylen e oxid e production
. Ethoxylate d mixe d linea r alcohol s (component s i n biodegrababl e detergents ) hav e bee n th e majo r contributo r t o thi s us e o f ethylen e oxid e i n recen t years . Glyco l ethers , th e thir d larges t en d us e o f ethylen e oxid e ha s exhibite d th e fastes t rat e o f growt h a s a consume r o f th e oxide
. Mos t o f thi s growt h ca n b e attribute d t o th e us e o f ethylen e glyco l monomethy l ethe r a s a je t fue l additive
. Ethanolamine s follo wglyco l ether s a s th e nex t larges t consume r o f ethylen e oxide
. Th e fastes t growin g us e fo r thes e ethanolamine s ha s bee n i n th e manufactur e o f surfac e activ e agents , e.g. , diethanolamin e condensate s o f conconu t oi l acid s and lauri c acid
. Fift h i n siz e o f ethylen e oxid e consumptio n i s diethylen e glyco l whos e majo r end us e i s i n polyurethan e an d unsaturate d polyeste r resins
. Ethylen e oxid e i s als o consume d i n th e manufactur e o f numerou s othe r chemical s suc h a s ethy l acrylate , cholin e an d cholin e chloride , acrylonitril e (probabl yno t bein g use d commerciall ynow) , hydroxyethy l cellulose , hydrox

yethy l starch , polyethylen e oxid e resins , fumigant s and foo d sterilants
. Aconservativ e growt h rat e fo r ethylen e oxid e throug h 198 5 o f fou r percen t pe r yea r ha s bee n estimated
. I t i s base d mainl yo n Figur e EO- 3 whic h show s th e growt h o f ethylen e oxid e productio n sinc e 1940 . I n th e earl y1970s , by fa r th e dominan t proces s ha s bee n direc t oxidatio n a s oppose d t o th e olde r chlorohydri n process . Al l ne wgrowt h ha s bee n projecte d t o b e vi a th e direc t oxidatio n route . Agoo d averag e plan t siz e i s 20 0 M M lbs./yea r and a s suc h about
. 1 5 ne wunit s wil l hav e t o b e buil t betwee n no wand 1985 . (Se e Tabl e EO-12 ) Th e pric e histor yo f ethylen e oxid e i s interesting
. Fro m194 0 t o th e mi d fifties , i t showe d a smal l increas e eac h yea r unti l th e direc t oxidatio n proces s reall ybega n t o catc h on . Fro m195 5 t o th e present , ther e ha s bee n a steadydro p i n pric e fro m15c/lb
. t o 7.5c/lb
. i n mi d 197 3 despit e a genera l ris e i n price s i n th e economy . Th e chlorohydri n proces s i s onl yeconomi c whe n th e pric e o f ethylen e i s greate r tha n si x time s tha t o f th e chlorin e pric e an d i s als o mor e economica l whe n ethylen e oxid e price s ar e high
. A t lo wethylen e oxid e prices , th e direc t oxidatio n rout e give s a bette r retur n o n ethylen e an d wit h lo wethylen e prices, th e direc t oxidatio n proces s ha s completel ytake n ove r th e productio n o f ethylen e oxide
.P.2 9 

### E0-3 5

, FIgUR E EG^ l 

# c

### Curren t

Capacit y 4,19 1 Margina l

Capacit y 35 6 Curren t

Capacit y On-Stream i n 197 5 3,83 5 TABL E

NUMBE R O F NE W

Deman d 198 5 6,80 0 EO-1 2

PLANT S BY 198 5

Capacit y 198 5 6,80 0 Capacit y

t o b e Adde d 2,96 5 Economi c

Plan t Siz e 20 0 Numbe r

o f Ne w Unit s 1 5 m

o i t o O N 

### NOTE : Al l capacitie s i nmillion s o f pound s pe r

year .

C OP.3 1 EO-3 7

X . Plan t Inspectio nProcedure s Th e larges t sourc e o f emission s fro m anethylen e oxid e plan t woul db e hydrocarbons , chiefl y ethylene . Thes e hydrocarbo nemission s ar e sometime s vente da s a ver

y dilut e strea

m o f hydrocarbon s i na larg e amoun t o f nitrogen , CO 2 an dsom e oxygen . Th e vente dga s strea m shoul db e below

the lowe r ex plosive limi t o f ethylen e inair . A . Ther e i s no eas y way t o tes t for th

e presenc e o f hydrocarbon s i na n air-C0 2 strea

m othe r thana chromatographan dthi s i s no t generall y a portabl e instrument . A quick , albei t rathe r qualitativ e tes t fo r th e presenc e o f ethylen e i s odor . Ther e shoul db e no odo r detectable . Ethylen e ha s a swee t odo r an dtast e bu t i t i s no t a strong odor . Ethylen e ha s no loca l or chroni c irritan t rating . I f the odo r o f ethylen e i s detectable , the uni t i s probabl y upse t an

dventin g improperly . Th e norma l tw o percen t ethylen e + on e percen t i nth e ven t ga s probabl y

wil l no t be detectabl e b y smell . Th e absenc e o f an y swee t odo r doe s no t mea ntha t ther e ar e zer o emissions . B . Ethylen e oxide , o nthe othe r hand , i s quit e detectabl e b y odor . I t i s irritating t o the eye s an dnos e an

di s classifie da s anacut e loca l irritant . I nhig hconcentrations , i t numb s the sens e o f smell . I t i s toxi c an

dshoul dno t b e inhaledalthoug hi t i s non-cumulativ e i nthe bod

y an di s no t a chroni c poison . I f the odo r o f ethylen e oxid e i s detectable , chance s ar e tha t the purg e reacto r absorbe r (o r the secondary

absorber/scrubber ) i s upse t an dno t functionin g properly . I f woul db e advisabl e t o discus s the following wit hplan t officials . 1 . Prope r flo

w o f absorbin g mediu m - water . 2 . Prope r temperatur e o f the absorbin g mediu m an dthe scrubber . 3 . Deposit s o f materia l o nthe packing o f the absorbe r whic hcoul d fou l the scrubbe r internall y an dcaus e by-passing . 4 . Markedl y

differen t temperatur e an dpressur e o f the feedga s t o the scrubbe r thandesign . Sinc e ethylen e oxid e i s the desire dproduc t an di s bein g recovere di n rathe r dilut e for

m fro m the reacto r effluen t gases , pruden t managemen t o f the plan t woul dinsis t tha t every bi t o f ethylen e oxid e b e recovered . I t i s jus t no t economica l t o los e ethylen e oxid e du e t o imprope r scrubbe r operation s s o thes e instance s shoul db e rare . C . Stack s shoul db e checke dfo r particuTat e emissio nan dNO xb y

opacity . Al l stack s shoul db e practicall y colorles s bu t agai na clea r stac k doe s no t mea nno hydrocarbo nemission s becaus e ethylen e an drelate d compound s ar e colorless . D . Flares , i f any , shoul db e smokeles s an donl y a rathe r substantia l upse t shoul dcaus e smok e here . However , putting a dilut e strea m o f hydro carbon s througha flar e below th e lowe r combustibl e limi t o f the strea m wil l resul t i na clea nflar e bu t no reductio ni nhydrocarbo nemissions . E . Incinerator s - I f therma l incinerator s ar e provide do nan y o f th e ven t streams , a visua l chec k o f the stac k ga s shoul db e made . Th eP.3 2 

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stac k shoul db e nearl y clear , i f no t completel y clear . Sinc e th e fee dstrea

m t o the incinerato r i s liabl e t o b e below it s combustibl e limit , one shoul dchec k t o se e i f adequat e supplementa l fue l i s being burne dto properl y combus t the ven t gas . Desig nspecification s shoul d b e comparedt o actua l operatin g condition s sinc e ther e probabl y wil l b e n o visibl e clue i nth e stac k effluent . Som e chec k point s woul dbe : 1 . Burne r inth

e combustionzon e shoul db e operating . 2 . Combustio nzone temperatur e i nthe designrange . 3 . Stac k ga s temperatur e i nth e desig nrange . 4 . Proces s ga s valve s ope nt o the incinerator . A catalyti c incinerato r or converte r ma y als o b e used . I nfact , thi s typ e o f devic e i s mor e likel y t o be encountere dtha na therma l incinerator . Generally , the off-ga s fro m the converte r wil l b e used t o powe r a turbin e befor e exhausting t o th e air . Th e sam

e point s shoul db e checkedonth e catalyti c converte r a s onth e therma l incine i tor . Supplementa l fue l may or may

no t b e usedo

na catalyti c incinerator . Lo g dat a onoperatio no f bot htype s o f incinerator s shoul db e reviewed , especiall y i f stac k ga s analyse s ar e availabl e vi a a chromatographan

drecorde dintermittentl y o r continuously . Hydro carbon s i nthe stac k ga s shoul db e virtuall y ni l (sa

y 0. 2 percen t o r les s an dzer o i f possible) .P.3 3 EO-3 9

XI . Financia l Impac t Tabl e EO-1 3 present s a nestimat e o f the cos t o f ethylen e oxid e manufactur e b y bot hanai r oxidatio nproces s an db y anoxyge noxidatio nprocess . The differenc e i nmanufacturin g cos t may no t be a s grea t a s th e tabl e shows at 20 0 M M lbs./yea r (i.e. , the 0.48c/lb . may b e onthe highside ) bu t the literatur e indicate s a smal l advantag e fo r the " ai r proces s at capacitie s ove r abou t 10 0 M

M lbs./year , a brea k eve na t 60-7 0 M

M lbs . an

da smal l edg e for th e O 2 proces s i nsmalle r plants . Th e minimu m economica l plan t siz e i s reporte dt o b e abou t 2 5 M M lbs./year . Tabl e EO-1 4 wa s calculate db y usin g the ai r oxidatio nproces s a s outline d i nTabl e E0-13 , bu t adding emissio ncontro l facilitie s t o reduc e hydrocarbo n ventin g t o nea r zer o wit ha catalyti c converte r o nthe tw o mai nproces s streams . Thi s represent s the mos t feasibl e ne w ai r oxidatio nfacilit y a t 20 0 M M lbs . pe r yea r productio nan dvirtuall y

no emissions . Credi t for powe r derive dfro

m the incinerato r gase s wa s take na s 0.25c/lb. , base do n dat a i nthe questionnaires . Cos t o f buildin g a new 20 0 M M lbs./yea r ai r oxidatio nethylen e oxid e plan t wit hgoodpollutio ncontro l facilitie s woul d reduc e profit s afte r taxe s b y abou t 1. 5 percent . Tabl e EO-1 5 wa s calculate db y usin g th e oxyge noxidatio nproces s a s outline di nTabl e E0-13 , bu t adding emissio ncontro l facilitie s t o reduc e hydrocarbo nventin g t o nea r zer o wit ha nincinerato r an

dstea m generator . Thi s represent s the mos t feasibl e new oxyge noxidatio nfacilit y at 20 0 M

M lbs./yea r productio nan dvirtuall y

no emissions . Ne t operatin g cos t i s onl y $5,900/year . Cos t o f buildin g a ne w 20 0 M M lbs./yea r oxyge noxidatio n ethylen e oxid e plan t wit hgoo dpollutio ncontro l facilitie s woul dreduc e profit s afte r taxe s b y abou t eigh t percent . A sensitivit y

analysi s wa s performe dfor th e catalyti c incineratio n installatio ni nthe ai r oxidatio nproces s (Tabl e E0-14b) . Installe dcos t o f the pollutio ncontro l facilit y wa s varie d+ 5 0 percen t an dit s effec t on th e R.O.I , calculated . Th e 6. 8 percen t R.O.I , wa s foun dt o var

y fro m 6. 5 t o 7. 1 percent . A comparabl e calculatio no nthe operatin g cos t sensitivit y woul dresul t invariation s o f simila r magnitud e becaus e the saving s i noperatin g cost s throughthe additio no f a catalyti c converte r ar e approximatel y equa l t o th e increase dcapita l charges . I f bot hsensitivitie s wer e applie dsimultaneously , they soul dnearl y

off-se t eac hother . Sensitivitie s wer e no t calculate dfo r th e oxyge noxidatio nproces s becaus e the extr a capita l involve di s onl y $40,00 0 o na $5,200,00 0 plan t an dthe extr a operatin g cos t i s onl y $20,000/yea r ona $14,540,000/yea r total . Thus , i t wa s judgedtha t th

e sensitivitie s ar e no t significant . Tabl e E0-1 6 i s a pro-form a balanc e shee t fo r the tw o abov e cases . A constan t selling pric e o f 7.5c/lb . for ethylen e oxid e wa s used . Capita l requirement s for the mos t feasibl e ne w plant s ar e abou t $225,00 0 highe r wit h ai r oxidatio nan

dabou t $40,00 0 highe r wit hoxyge noxidatio ntha nfor existin g typ e plants . Inadditio nt o the financia l impac t o f the propose dmos t feasibl e ne w plant s a definit e positiv e environmenta l impac t woul dresult . No t onl y woul d2,05 0 ton s o f hydrocarbon s pe r 20 0 MM lbs./yea r plan t no t b e vente d t o th e atmospher e (fo

r 1985 , 1 5 ne

w plant s woul dven t 30,75 0 ton s o f hydro carbon s pe r yea r i f no t controlled ) bu t a nenerg y savings.coul dbe realize dP.3 4 

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i f the ho t gase s wer e use dt o driv e som

e o f th

e proces s turbine s o r generat e steam . i

~ For 1985 , installatio no f emissio ncontro l facilitie s an dutilizatio no f j th e powe r generate dwoul db e equa l t o a saving s o f abou t thre e billio ncubi c

— ' fee t o f ga s pe r year .

### EO-4 1 

# u

TABL E EO-1 3 ETHYLENE EXISTIN G PROCES S DIREC T MANUFACTURIN G COS T Ra wMaterial s Ethylen e (4.0c/lb. ) Oxyge n ($15/ton ) Catalys t & Chemical s Labo r Maintenanc e @ 5 % o f Investmen t Utilitie s
INDIREC T MANUFACTURIN G COS T OXID I



### FO R 20 0 : MANUFACTURIN

G COST * ATYPICA

L M M LB./YR
. 

## o 2 

### C/LB
. 

### 3. 8 1. 0 0. 2 0.3 1 0.1 3 0.6 0 6.0 4 FACILITY

S/YR
. 

### AI R

C/LB
. $/YR
. 

### 3. 8 0. 0 0. 2 0.3 1 0.2 5 0.6 0

. 5.1 6

0.3 4

0.2 6 0.0 6 0.3 2 6.7 0 520,00 0 0.3 4

0.5 0 0.1 1 0.6 1 6.1 1 1,000,00 0 Plan t Overhead @ 1107 . o f Labo r FIXE D MANUFACTURIN

G COS T Depreciatio n - 1 0 yea r str . line Insuranc e & Prop . Ta x 2.37 . o f Inv .
MANUFACTURIN

G COS T GENERA L EXPENSE S Administratio n (37 . o f Mfg
. Cost ) Sale s (17 , o f Mfg
. Cost ) Researc h (27 . o f Mfg
. Cost ) Financ e (67 , o f Investment ) TOTA L COS T PRODUC T VALU E Ethylen e Oxid e @ 7.5c/lb
. Profi t befor e Taxe s NPA T (527. ) Cas h Flo w RO I
*Take n fro

mliteratur e "Petrochemica l Industry : Market s & Economics " up-date d an d scaled u

p t o 20 0 M M lbs./yea r using "0. 6 Factor " o n capita l for bot h 0 2 

### an d Ai r Fee d Plants
. Base d o n 197 3 dollars
. 0.2 0 0.0 7 0.1 3 0.1 5 7.2 5 14,500,00 0

15,000,00 0 500,00 0 240,00 0 760,00 0 4.67 . 

### 0

0 0 0
_ 

### 6 1 8 0 6 1 2 

### _3 0 7 7 13,540,00 0

15,000,00 0 1,460,00 0 700,80 0 1,700,80 0 7.07 .