### P. 1



# OAR Box 1851 Prepped by Keeia Richards



# Document

Number: 

# 31 ) ll-A- 5
Docket Number: 

# A-90-1 9

Printed 11/19/200811:19:51 AM Sheet 31 of 41

# P. 2



# _ J
r 

# J


# , - J

, J

, J
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# , J

. J

. J l 

# A-90-1 9 ll-A- 5 

# ENGINEERIN

G AN D COS T STUD Y O F AI RPOLLUTIO

N CONTRO

L FO RTH E PETROCHEMICA

L INDUSTR

Y VOLUM

E 3 : ETHYLEN

E DICHLORID

E MANUFACTUR

E B Y OXYCHLORINATIQfliTT P

; . _• s- - 

# ll_i !
b y 

# FP A AI R DOCKE T W

. A

. Schwartz , F

. G

. Higgins , Jr * J

. A

. Lee , R

. Newirth , an dJ

. W

. Pervio r

Houdr y Divisio n Ai r Product s an dChemicals , Inc

. P.O

. Bo x 42 7 Marcu s Hook

. Pennsylvani a1906 1

Contrac t No

. 68-02-025 5

EP A Projec 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 , N

. C

. 2771 1

Novembe r

197 4 •



# I

# 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

o f readers

. Copie s ar e availabl e fre e o f charg e t o Federa l employees , curren t contractor s an dgrantees , an dnonprofi t organizations

- a s supplie s permit-fro mth e Ai r Pollutio nTechnica l Informatio n Center , Environmenta l Protectio nAgency , Researc hTriangl e Park , Nort h Carolin a27711 ; or , fo r afee , fro mth e Nationa l Technica l Informatio nService , 528 5 Por t

Roya l Road , Springfield , Virgini a22161

.

•a



# Thi s repor t

wa s furnishe dt o th e Environmenta l Protectio nAgenc y b y th e Houdr y Divisio no f

Ai r Product s an dChemicals , Inc

. , i nfulfillmen t o f Contrac t No

. 68-02-0255

. Th e content s o f thi s repor t

ar e reproduce dherei na s receive d fro mth e Houdr y Divisio no f Ai r Product s an dChemicals , Inc

. Th e opinions , findings , an dconclusion s expresse dar e thos e o f th e autho r

an dno t

necessaril 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 n Agency

.

Publicatio nNo

. EPA-450/3-73-006- C



# tt 

# u IL

n

# 1

6



### * Plan tCod

a»•_• > Dat aoo-etrea m ' Capacity , Tonao f

Ethylen e Dichlorlda/Tr . Averag e Production , Ton aEDC/Yr . Rang e I n Production , I o f Has . By-product* . Tona/Yr . Mixe d Chlorinate d H C Emission * t o Atmoepher e Strea m Flo w(a) , Lba./Hr . Plo wCharactarlatlc a I f Intermittent , Hra . o f Flov/Yr . Composition . T/ T D C Particulat e Carbo n Dioxid e Carbo n Monoxid e HItroga n Oxyge n Methan e

. Ethylan a •Ethen e /Ethylen e Dlchlorld e Mon o & Dlchloroacatylen a Ethy l Chlorid e Viny l Chlorid e Dlchlor o Ethylen e Chlorofor m Carbo n Tetrachlorid e Wate r- Aromati cSolven t Chlorine * Hydroge n Chlorid e Sampl e Tap Locatio n Dat ao rFrequenc y o f Samplin g Typ e o f Anelyel e Odor Colo r Ven tStack a Nuabe r Heigh t Diamete r Exi tGee Temp. , ° P SCF M pe rStac k(a ) Typ e o f Emissio n Contro l Dat e Installe d 'Tote l Emlealone , Ton/To n ED C Hydrocarbon * Particulate * & Aeroeol e (b ) 

### NO, C O TABL E ED-3 A SUK7E O O F u . s . oxYCHLOXiMtia riur n AN D ATMOSPHERI

C EMISSION

S FRO M THES E FACILITIE S 5t- l 196 8 236,35 0 0 

### N o aaaaona l variatio n •a .


### Precee e Van tDlatlllatlo n Ven t 45,00 0 1,70 0 Contlnuou aContlnuou a

0.03 2 »••

• 0.00 8 . 0.71 0 0.000 3 (c 

### > 0.01 8 0.01 1 0.0000 1 0.00 6 0.0000 3 0.03 3 0.000 2 0.01 2 0.007 7 0.00 8 , 0.006 2 0.000 7 0.008 0 0.006 4 0.001 0 0.000 8

Befor e 6 efte rcontac tcondense rAccessibl e Continuou s fo r0 2 

### . CO j 6 C 2 

### " , othe r*4 tlmes/Yr . HC' e onc e pe rday , C O 6 tlmea/Yr . C C . C.C . Ho— aNotbeyon d plen tboundar y
I 1 50 ' 10 ' .1*0 " 6 " . 3 2 8 0 9,90 0 13 5 Contac tCondense r 196 8

• i 

### 0.08 8 0.00 1
V 

### 0.00 8



## *> Pag e 1 p f 7 32- 2
130,00 0 130.00 0 N o seasona l variatio n

Procee s Ven t 36.10 0 Contlnuou a

0.03 * 0.00 8 * 1.04 8 0.00 7 0.00 2 0.00 9 0.00 4

Accessibl e Oraa t6/dey,C.C . t/vfc .

' Oraa t6 C.C . Non e

1 

### 27'6 " 8 " 8 0 

### 8,00 0 Condense r1-10 °F l

0.01 5 

# 9

o

0.00 8 1P.4Plen tCod e Numbe

r Dat e on-atrce m Capeclty , Ton e o f Ethylen e Dlchlorlde/Yr . Averag e Production , Ton e EDC/Yr . Reng e I n Production , X o f Mas . By-producta , Tona/Yr . Mixe d Chlorinate d H C Emission s t o Atmospher e Strea m Flo v (a) , Lbs./Hr . Flo w Cherecterlsttc s i f Intermittent , Hra . o f Flov/Yr . Composition . T/T ED C Particulat e Carbo n Dioxid e Carbo nMonoxid e Nitroge n Oxygo n Methan e Ethylan a Ethan e Ethylen e Dlchlorld e Mon o & Dlchloroacatylen a Ethy l Chlorid e Viny l Chlorid e Dlchlor o Ethylen e Chloroform Carbo nTetrachlorid e Vete r Aromati c Solven t Chlorin e Hydroge nChlorid e Sampl e Ta p Locatio n Dat e or Frequenc y o f Samplin g Typ e o f Analysi s Odo r Colo r Ven t Steck e Numbe r Heigh t Diamete r Exi t Ga s Temp. , ° F SCF M pe r Stec k <• ) Typ e o f Emissio nContro l Dat e Instslle d

. Tota l Emissions , Ton/To nED C Hydrocarbon s Particulate s & Aeroeol s < b > N0 „ • SO , * C O TABL E ED-3 A CONT'IT . Sl'RVE Y O F U . S . OXYCHLORINATIO N PLANTS AN D ATMOSPHERIC EMISSION S FRO M THES E FACILITIE S 52- 3 196 8 115,00 0 115,00 0 N o sessona l varletlo n

Proces s Ven t 18.30 0 Continuou s

0.01 0 0.00 5 0.60 4 0.01 9 0.00 5 0.00 8 0.01 7
0.01 1

T R<« > Non e afte r scrubber , ecceaslbl e ta p befor e scrubbe r Scrubbe r feed3- 6 tlmeo/yr . C.C . Occeslona l HC l

I 76 - l " . ; 8 0 3.98 0 . Scrubbe r 196 8 -197 1 Causti c Scrubbe r Ven t 9 0 Continuou s

0.0000 1 0.0000 3 0.0011 8 0.0000 8
0.0001 2 0.0001 5 0.0014 4
0.0001 4 0.0000 1 0.0000 1 0.0000 2 0.0000 3 Pag e 2 o f 7

0.04 4

0.00 5 Dryln RToverOvri'd . 1 2

_Continuou s

0.0000 1 0.0000 2 0.0000 7 0.0000 1
0.0001 6 0.0001 7

Condense r 197 2 Emergenc y Ven t 

## 1720 0 Intermitten t 6

0.004 5 0.002 3 0.265 2 0.008 5 002 0 .003 4 0.007 6
0.004 9

0.0000 9 N o prob l Tvlc e i n C.C . Non e

1 49 ' 2 n 10 0 1 3 e

m Dec . 197 1 Acces s

Nots s

None

1 72 ' 2 " 6 0 2. 6 lbl e

ye t (I, 0.000 4

Accessibl e 4 tlsM arecentl y C.C . HC l vlthl n batter y limi t

1 73 ' 7 " 4 0 2,00 0



## —•• *' ; « . 

# r— \

# "__

T

__ J I I I I

_ _ -

Plan t Cod a
Dat e on-stres m Cepeclcy , Ton s o f Ethylen e Dlchlorlde/Y r Avereg e Production , Ton e EDC/Yr . Rang e i nProduction . Xo f Max . By-producta , T/ T D C Mixe dChlorinate dB C Emission s t o Atmoashar e Stream Flo v <•> . Lba./Rr . Flo v Characterletle a I f Intermittent . Hra . o f Flov/Ya . Composition , T/ T ED C Particulat e Carbo nDioxid e Carbo nMonoxid e Nitroge n Oxyge n Methan e Ethylen e Ethan e Ethylen e Dlchlorld e Mon o 6 Dlchloroecetylen e Ethy l Chlorid e Viny l Chlorid e Dlchlor o Ethylen e Chloroform Carbo nTetrechlorld a Wate r Aromati c Solven t Chlorin e Hydroge nChlorid e Sampl e To p Locatio n Dat e o r Frequenc y o f Samplin g Typ e o f Anelyel e Odo r Colo r Ven t Stock s Numbe r H e I ght Diamete r Exi t Ca s Tea*. , ° F SCF M per ' Stac k I'vp e Em i salon s Contro l Det e Installe d Tota l Emissions , Ton/Ton'ED C Hydrocarbon s Particulate s & Aerosol s ( b ) NO , SO , C O 52- 4

107.50 0 TABL E ED-3 A CONT'D . SURVE Y O F U . S . OXYCHLDR I NATIO N PLAnT S AN D ATMOSPHERI

C EMISSION S FRO

M THESE FACILITIE S

52- 5
196 3 Pag e 3 o f 7

2n d quarte r 20 1 belo v eve . 4t h" " abov e ava .

Absorbe r Ven t 33,80 0 Contlnuou a

0.06 8 0.01 2 1.02 5 0.10 0 0.03 8 0.00 6 

### 0.02 2 

## ( D

0.000 4
Pipe d t o continuou s analyse r Ever y 1 3 minute s C.C . Non a

1 175 ' 8 " 5 0 7,50 0
(n ) 0.02 8



### 0.01 2 330.00 0 N o aaaaona l variatio n

0.007 5 

## (J )
Abaorbe rVen tAbsorbe rVen tWast e Wate rStrippe rOvh'd . Wast e Wate rStrippe rOvh'd . 71.00 0 31,00 0 7 7 2 5 Continuou s Continuou s Contlnuou aContlnuou a Heed e Colum n Ven t



### 0.02 5

. 0.00 6 0.74 8 0.07 1 0.00 8 0.00 4 0.00 1 0.00 2 0.00 5

0.00 2 0.33 0 0.03 3 0.00 4 0.00 2 0.00 1 0.000 3 X

. X X



### 0.0000 3

> 0.0003 6

0.000 5

Accessibl e 4 pe r hou r
C.C . No proble m

1 150 ' l'O " 6 5 15.90 0 Dem i ate r 196 3 0.000 2

Accessibl e 4 pe r hou r
C.C . No proble m

1 150 " 1'2 " 7 0 6.95 0 Dem i ste r 196 7 0.00000 6

Non e Neve rsample d
Non e No proble m

1 40 ' 2 " 5 5 12. 5 Refrlg . Cond . 196 3
0.01 1



### 0.00 8 0.0000 5

0.0000 5



### 0.00000 2

Non e Neve raample d Non e N o proble m

1 5 0 ' 3 " 5 5 5 Refrlg . Cond . 196 7 12 0 Contlnuou a



### 0.000 2

Non e Neve rsemple d Non e N o proble m

1 150 ' 2 " 5 5 1 7 Refrlg . Cond . 196 6

## . •

Plan tCod e Numbe r Det e on-atree m Capeclty , Ton s o f

Ethylen e Dlchlorlde/Yr . Avereg e Production , Ton s EDC/Yr . Reng e I n Production , X o f Max . By-producta , T/ T ED C Mixe d Chlorinate d H C Emission s t o Atmoepher e Strea m Flo v<•> , Lbs./Hr . Flo vCharacterlatlc a I f Intermittent , Hrs . o f Flov/Tr . Composition , T/ T EDC Particulat e Carbo n Dioxid e Carbo n Monoxid e Nitroge n Oxyge n Methan e Ethylen e Ethan a Ethylen e Dlchlorld e Mon o 6 Dlchloroacetylen e Ethy l Chlorid e Viny l Chlorid e Dlchlor o Ethylan a Chlorofor m Carbo n Tetrechlorld e Wate r Aromati cSolven t Chlorin e Hydroge n Chlorid e Sampl * Ta p Locatio n Det e o rFrequenc y o f Samplin g Typ e o f Analyal a Odo r Colo r Ven tStack a Numbe r Heigh t Diamete r Exi tGe aTemp. , ° F SCF M pe rStac k Typ e EaUeslon aContro l Det e Inetelle d Tote l Emisalona , Ton/To n EDC Hydrocarbon s Partlculate e 6 aerosol s ( ' SO , C O TABL E ED-3 A CONT'D . SURVE Y O F U . S . OXYCHLORINATIO N PLANT

S AN D ATMOSPHERIC EMISSION S FRO M THESE FACILITIE S 52- 6
196 8 85,00 0 1s tquarte r20 X belo v eve . 2n d " ebov e ev e

Absorbe rVen tStrippe rVen tHeed s Colua n Ven t 21,20 0 24 5 12 0 Contlnuou e Contlnuou aContlnuou a

N i l 0.04 7 0.01 3 0.87 5 0.000 6 0.002 8 0.06 9 0.00 8 0.00 3 0.002 9 0.000 2 0.00 2 <e )

^ 0 002 3 0.00 9 0.008 3 0.000 4 0.00 3 0.000 1
Pipe d t o contlnuou e enelyser . Non e Non e O2 - Continuoua , Other aever y 1 3 mln . Neve reenple d Neve raemple d Ethylen e contlnuou e C.C . + IH fo rethylen e . Non e Non e Non aNon e Non e

1 ' 1 1 6 5 ' 35 ' 35 ' 6 " . 4 " 2 " 5 5 10 0 10 0 4.66 0 ' 6 7 18. 5 Deulatei
- U

Separato r 196 8
0.02 0 N i l

0.01 3 

## * —

Peg e 4 o f

7

Emergenc y Ven t 22,20 0 Intermitten t 18 0
N i l

1.038 3 (d )

0.026 2 0.000 1 (k)

0.081 1 0 001 1

Non e Neve rse—ple d Non e Non e

1 5 0 ' 8 " 5 0 4.78 0 

## -



# ?

a — Ls »B _

_ 

# I

• H Plan tCod e Numbe r

_ • Det e on-stree m H Cepaclty . Ton ao f Ethylen e Dlchlorlde/Yr , B J Avereg e Production , Ton e EDC/Yr . B J Reng e I n Production , X o f Max . • By-products , t/ T ED C

• Mixe d Chlorinate d H C B Emlealon at o Atmospher e


### • Strea m
• Flo v<•> . Lba./Rr . 1 Flo vCharacterletl c
• I f

Intermittent , Rre . o f Flov/Tr . • Compoaltlon , T/ T ED C 1 Particulat e B Carbo n Dioxid e B Carbo n Monoxid e H Nitroge n B J Oxyge n H Methan e H Ethylen e B J Ethan e B Ethylen e Dlchlorld e B Mon o 6 Dlchloroecetylen e
• Ethy l Chlorid e 1 Viny l Chlorid e B Dlchlor o Ethylen e B Chlorofor m B Carbo n Tetrachlorid e B Vote r 1 Aromati cSolven t H Chlorin e H Hydroge n Chlorid e

• Sampl e Ta p Locatio n 1 Det e o rFrequenc y o f Semplln g 

# • 1 Typ e o f

Analysi s B Odo r B N Colo r
• Ven tSteck e B Numbe r
• Heigh t B Diamete r fl Exi tGe e Temp. , ° F B SCF

M pe rStoc k(a l B Typ e o f

Emission s Contro l B Det e Installe d B Tota l Emissions , T/ T ED C B j Hydrocarbon s B Psrticulste s & Aerosol s < b > 

# 1 ! f

TABL E ED-3 A CONT'D . SURVE Y O F U . S . OXYCHLORINATIO N PLANT

S AN D ATMOSPHERIC EMISSION S FRO M THESE FACILITIE S
32- 7 197 1 287,00 0

45.20 0 < l > Contlnuou a

0.00 8 0.00 4 0.57 9 0.02 5 0.00 4 0.00 4 0.00 5

0.000 2 Inconvenien t Scrubbe rFee d - Continuou s Scrubbe rVen t- Continuou s fo rCI 2 G.C . & Ultrevlole tSpec . No tbeyon d plen tboundar y - Cl j & HC l (ln >

1 * » 135 ' 3 0 " Ambien t 10,00 0 <' ) ' Wete rScrubbe r
(n ) * 0.01 3

0.00 4 0 52- 8

246.00 0

36.20 0 ( l > Contlnuou a

0.00 7 0.004 ' 0.54 1 0.02 3



# . 0.00 4 0.00 4 0.00 5

0.000 1 Inconvenien t Scrubbe rFee d - Continuou s Scrubb'e rVen t- Ver y Infrequen t C.C . No tbeyon d plen tboundar y - Cl j 6 HC l *" '

1 a s 135 ' 3 0 " Ambien t 3.00 C O ) Wete rScrubbe r
(n ) 0.01 3

• 0.0O 4 

# ' 1 - I .

Peg e 5 o f

7
52- 9
50,00 0

7,70 0 " ) Contlnuou e

0.00 8 0.00 4 0.56 6 0.02 4 0.00 4 0.00 4 0.00 5

0.000 2 Inconvenien t Scrubbe rFee d - Contlnuou e Scrubbe rVen t- Ver y Infreouen t 

# cc . No tbeyon d plen tboundar y - Cl j aHC l '• '

1 <» 75 ' 1 8 - 24 " Ambien t 1.70 0 <* > Wate rScrubbe r
(n ) 0.01 3

0.00 4 

# /10-1 

# « •Plan t Cod e Numbe r

Det e on-stree m Capacity , Ton e o f Ethylen e Dlchlorlde/Yr . Averag e Production , Ton s EDC/Yr . Rang e i nProduction , Xo f Max . By-producta . T/ T ED C Mixe d Chlorinate d H C Emission s t o Atmospher e Stream Flov <•> . Lbs./Hr . Flov Characterlatlc a I f Intermittent , Hro . o f Flov/Yr . Composition , T/ T ED C Particulat e Carbo nDioxide " Carbo nMonoxid e Nitroge n Oxyge n Methan e

. Ethylan a | Ethan e 1 Ethylen e .M<_-e__d a I Mon o 6 Dlchloroacatylen e ( Ethy l Chlorid e i Viny l Chlorid e Dichlor o Ethylen e Chloroform Carbo nTetrechlorld e Wete r Aromati c Solven t Chlorin e Hydroge nChlorid e Seapl e Ta pLocatio n Dat e o r Frequenc y o f Samplin g Typ e o f Analyel e Odo r Colo r Ven t Steck e Numbe r Heigh t Diamete r Exi t Ca s Temp. , ° F SCFM pe r Stoc k Typ e Emission s Contro l Det e Installe d Tots l Emissions , Ton/To nED C Hydrocarbon s Psrtlculete s 6

> Aerosol s (b ) NO , SO , C O TABL E ED-3 A CONT' D SURVE Y O F I 1

. S

. OXYCHLORINATIO N PLANT

S AN D ATMOSPHERI C EMISSION S FRO M THES EFACILITIE S



### 52-1 0 Pag e 6 o f 7

196 7 118,62 5 118.62 5 N o seaaona l verlatlo n

Proces s Ven t 1,45 0 Continuou s

0.011 9
0.016 7

0.012 8 0.000 2 0.006 5 000 7 003 3 000 7 000 2 srgooc y Ven t Intermitten t

0 0 0 0 0.0000 4
0.000 6

Ven t unde r vacuum Fal l o f 197 1
C.C . 

### ED C vithl n better y limit s (8 ) Ca n b e don e Neve rSample d

Non e

26 0 

### Scrubbe r 196 7 1 75 ' 8 " 7 5 

## (_ ) 0.02 4 100 0 fh > 

### Scrubbe r 196 7

T J CO

# J P.1 0 

## ED-1 6

TABL E ED-3 A FOOTNOTE S 

# Pag e 7 o f 7 (a ) Base do naverag e productio nrat e i f available , otherwis e base do ndesig n capacity . (b ) Include s HC l an

dcarbo ntetrachloride , (c ) Air . (d ) Include s oxygen . (e ) Norma l feedt o scrubbe r contain s 0.000 8 ton s HCI/to nEDC . Hovever , durin g reacto r 8t«Ft-u p(max . 3 0 min. , 2 4 time s pe r year) , feedca ncontai na s muc ha s 0.5 0 ton s HCl/to nEDC . Durin g emergenc y condition s suc ha s powe r failure , whe nscrubbe r become s ineffective , mos t o f thi s HC l wil l b e vente dt o the atmosphere . Duratio ni s normall y 3- 5 minute s require dt o secur e plant . (f ) Recover y

uni t no t pu t i noperatio nunti l afte r plan t survey . (g ) Durin g start-up , feedt o scrubbe r contain s 0.16 3 ton s o f nitroge npe r to n o f ED C productio ncapacit y an d0.10 6 ton s o f HC l pe r to no f EDC . Duratio n i s approximatel y

2 0 minutes . Durin g emergenc y venting , th e ven t contain s a smal l amoun t o f organi c material . (h ) Represent s nitroge nflo w durin g start-up . (i ) Absorber-strippe r ma y shu t dow

nfor undetermine dperio ddurin g whic htime ED C conten t inden t increase s t o thre e time s valu e shown . (j ) Sen t t o off-sit e disposa l plant . , (k ) Include s methan e an dethane . (1 ) Represent s norma l flo w fro m ED C unit . Actua l tota l ven t fro m stac k include s stream s fro

m othe r unit s i nVC M

plant . Ven t ga s compositio n show ni s base do nanalysi s o f scrubbe r feedga s fro m ED C oxychlorinatio n unit . I t ha s bee nassume dtha t wate r scrubbe r remove s containe dHC l (0.0000 4 T/ T EDC) . (m ) Onl y

durin g plan t upset . (n ) Surve y

dat a doe s no t includ e informatio nregardin g ai r emission s resultin g fro m ED C purification . I t shoul dbe note dtha t flov rate s an

dcomposition s shov

nfor intermitten t stream s represen t emission s durin g floving conditio nan dno t yearl y average dvalues . The tota l plan t emissio nfigure s shov nar e average d emission s for extende dperiod s o f operation .

## P.1 1



# 1 

# J



# J J
j ED-3 5

I f liqui dchlorinate dby-product s ar e t o b e burned , th e effluen t shoul db e sent t o a nefficien t HC l remova l syste m o r usedt o produc e desirabl e chlorinate dhydrocarbons .
I nfutur e oxychlorinatio nplant s tha t us e tonnag e oxygen , al l hydrocarbo nvent streams fro m th e EDC plan t coul db e sent to th e sam e incinerato r an

dHC l recovery

system . Floating roo f storag e tank s inal l ne w plant s woul dreduc e EDC losse s fro

m produc t storag e facilities .
F . Industr

y Researc hEffort s
Curren t industr

y effor t i nai r pollutio ncontro l center s aroun d developmen t o f mor e selective catalyst s whic hwil l reduc e th e amoun t o f chlorinate dby-product s an dincreas e ethylen e conversion . Individua l manufacturer s ar e involve dinstudie s regarding th e following :
1 . Developing market s for chlorinate dcompound s rejecte di n produc t distillatio nsection . 2 . Remova l o f chlorinate dhydrocarbon s fro m wate r rejec t streams . 3 . Recovery

o f ven t materia l fro m produc t storag e tanks . 4 . Method s o f reducing ethylen e emission s during catalys t conditibning . 5 . Additiona l direc t chlorinatio nstage s t o reduc e ethylen e emissions .

### P.1 2



## ED-3 6

V . Nationa l Emissio nInventory
Base duponth

e emissio nfactor s show ninTabl e ED-3A , th e tota l approximat e emission s fro

m U.S . manufactur e o f EDC i noxychlorinatio nplant s ar e a s follows :

Componen t Hydrocarbon s Ethylen e Tota l Othe r Non-Methan e Hydrocarbon s (c ) Particulate s & Aerosol s ( d 

## ) CO Averag e Emission s (a ) T/ T o f EDC
0.005 5
0.022 4 ©.000 1 0.0064 ' 0.034 4 ' # Tota l Emission s ( b 

## ) M M lbs./yr .

18. 8
76.3 *
• 0. 4 , 21. 8 117. 3
The abov

e figure s d o no t includ e an y emission s resulting fro m off-sit e processing o f wast e wate r an drejec t hydrocarbo nstreams . I t shoul db e noted tha t abou t 5 5 percen t o f th e oxychlorinatio nED C productioni s i nplant s tha t di dno t sho

w produc t fractionatio nfacilitie s i nth e surve y reports , se e Tabl e ED-3A . Sinc e al l o f thes e particula r plant s als o produc e viny l chlorid e monomer , i t i s assumedtha t an y undesirabl e impuritie s i nthe ED C ar e rejected i nth e downstrea

m VC M facilities . I noxychlorinatio nplant s tha t purif y ED C (98.5-9 9 wt . percen t produc t purity) , th e hydrocarbo nemission s resultin g fro m produc t fractionatio nequa l abou t 0.00 5 T/ T EDC . I f thi s typica l figur e i s usedto projec t losse s for plant s whic hdi dno t sho w purificatio nfacilities , hydrocarbo nemission s woul db e 9, 4 millio npound s pe r yea r highe r thanvalu e shown . Ethylen e dichlorid e productio nrat e i s fairl y constan t throughou t the year . However , severa l plant s di drepor t slightl y lowe r productionduring the firs t quarte r of-CW

e yeaY . . I naddition , sinc e cooling wdter , an dproduc t storag e temperature s ar e highe r inth e summer , it i s expecte dtha t emission s woul dbe slightl y

above averag e durin g the warme r months. ' ,

(a ) Weighte daverag e base do nindividua l plan t emissio nfactor s an dEDC productio nfigures . (b ) Base don1,705,00 0 tons/yr . tota l ED C productio nb y the oxychlorinatio nprocess , (c ) Include s 0.0U0 6 T/ T o f EDC assumedt o be emittedfro m produc t storag e tanks . (d ) Aerosol s includ e HC l an dcarbo ntetrachloride . 

# JTABL E ED-1 3

Typ e o f Pollutio n Contro l

EDC . Production , * A > Tona/Yr .

Pol-ttan t<* > Hydrocarbons : Ethylen e Othe rNon-Methan e Hydrocsrbon s Perticulete s U

Aerosol s *• ' NO x C O Averag e Emission s 

## T/ T

0.005 5 0.022 4 < G )
0.000 1

0.006 4 0.034 4 Presen t

4.20 5 Tote l Syste m
,00 0

Emission s M M Lb s

46. 3 188. 4 0 . 8

53. 8 289. 3 ./Yr . 

# •

Weighte d Emission s
3,70 0 15,07 0 5 0

5 0 18,87 0 < F > Averag e ESTIMATE D 196 5 AI REMISSION S FO R ALTERNAT

E CONTRO

L SYSTEM

S Existin g Plant e

Emission s T/ T



# . 0.000 7 0.000 9 0.000 1

0.001 7 (G ) 1,705.00 0

Tote l Emission s M M Lbs./Yr .

o
2 . 4 2 . 9 0 . 4 

# sT T (D ) 

# |

1 Weighte d : Emission s ; 

# |

19 0 | 17 5 ' 1 5

38 0 W Hos t

Aversg e Emission s T/ T

0.000 1

0.000 1 Feaaibl e Modification s

Ne wPlant e O 2,500,00 0 Tote l •mission s Weighte d M M Lbs./Yr . Emission s

0 . 6 2 5


### 5T 6 25 

# 1 | Averag e
; Emission s f T/ T j 1 

## i

, 0.000 3 0.000 4 0.000 1

0.000 8 Tots l <».• >

4,205,00 0 Tota l Emission s M M Lbs./Yr .

2 . 4 2 . 9 1. 0


## 6 3 Weighte d

•mission s 

# 1 19 0 i 17 5 4 0

40 5 <* > 

# ?

(A ) Estimate d productionb y oxychlorlnatlo nprocess . (B ) Exclude s emission s resulting fro m off-sit e produc t fractionationan dby-produc t dlapoaal . (C ) Include s HC l an dcarbo ntetrachloride . (D ) Assume s ai l existing plant s modifie d t o Incorporate d therma l incinerator s sn dscrubber s o nproces s vent stresm plu s distillatio nven t condenaer a an dplum e burnera . (E ) New

plant s assiune

d t o contai nfloatin g roo f produc t storag e tank s an dbase dontherma l Incineratio no nproces s sn

ddistillatio nven t a t ream s wit hwast e hea t boile r sn dcausti c scrubbe r wit hdistillatio nven t condense r befor e Incineration .
(F ) Significan t EmissionIndex , whic hl a baae d o nth e following weighting factora : Hydrocarbo n- 80 , Particulate s • 60 , NOx- 40 , an dC O - 1 . (Se e Appendix ) (C ) Include s O.00U 6 T/ T o f ED C loa t fro m produc t storag e tsnk s i nexistin g units .

## ED-5 4

XIII . Emissio nContro l Deficiencie s

Technica l deficiencie s whic hhinde r reducin g the leve l o f emission s includ e the following :
A . Proces s Chemistry an dKinetic s
I nth e oxychlorinatio nprocess , a cupri c chlorid e catalys t i s usedt o produc e EDC . Base dupo nexperimenta l dat a i t i s believe dtha t the reactio n proceed s b

y formatio no f anethylene-oxyge ncomplex , whic hi s subsequentl y chlorinate dt o ethylen e dichlorid e b y eithe r HC l or cupri c chloride . Th e rat e determinin g ste pi s th e ethylen e oxidatio nreaction . The amoun t o f ethylen e dichlorid e produce di s influence db y the relative concentratio no f fee dcomponents , reacto r residenc e tim e an dothe r operatin g conditions . 1 . Reacto r Feed (a ) Ethylen e •
Unsaturate dhydrocarbo nimpuritie s i nthe ethylen e fee dca n reac t wit hHC l forming undesirabl e chlorinate dby-products . Therefore , i norde r t o minij)i^e^|| ; pollutio nan dmaximiz e productivit y

i t i s d-esirable°t o us e hig hpurit y ethylene . I nal l bu t on e plant , ethylen e feedcontain s les s than ' on e percen t impurities . I nthe on e cas e (52-1 ) wher e lo w purit y

fee d (82-9 2 percen t ethylene ) i s utilized , chlorinate dan dnon-chlorinate d 'hydrocarbo nemission s ar e substantiall y highe r tha nwit hth e

- conventiona l feed . I nsom e case s economic s dictat e using som e excess , ethylen e t o insur e highHC l conversion . Thi s exces s olefi ni s normall y vente dt o the atmosphere , bu t coul dprobabl y b e recovere db

y a direc t chlorinatio nstep . (b ) Oxyge nConcentratio n
Al l bu t on e oxychlorinatjLo nuni t use s ai r a s a sourc e o f oxygen . By

utilizin g pur e oxyge nift j 

## place.~> f air. , 01an t 52-1 0 . ha a bee nabl e t o reduc e th e volume o f ven t gas . Eve nthough the total * quantit y o f hydrocarbo nemission s ar e simila r t o thos e fo r the othe r units , mos t o f thi s materia l consist s o f unconverte dethylene . Beside s containin g les s chlorinate d material , i t shoul dbe les s difficul t an dcheape r t o contro l the quantit y

o f emission s fro m this'source . (c ) Hydroge nChlorid e ' " . °

o 

## Again , dependin g upo neconomics , som e exces s HC l ma

y b e fe d t o th e reactor s t o insur e hig hethylen e conversion . On e publishe d articl e ^ indicate s tha t exces s HC l lead s t o the formatio no f unwante dchlorinate dby-products . 2 . Reacto r Operatin g Condition s

Reacto r operatin g condition s influenc e ethylen e conversio nrat e an dt o a certai nexten t the amoun t o f non-selectiv e products . Sinc e P.1 4 

# I I L

# I

TABL E I

(3 ) Hydrocarbon s v' 1. 1 0 0 4 0 6. 1 3. 1 18 3 0 11. 2 0 15 6 0.1 5 7 0 9 1 1 5 95. 1 2 9 85. 8 23. 8 25. 7 1 6 0 . 5 1. 3
' 3 4 0 0 5.2 5 24. 3 0 . 1 0 7 9 7 5 37. 5 2 0 6 2 4 . 3 9 . 4 5. 3 0 17. 6 1,227. 6 

# '» •

C i Particulate s

0 0 0 0 0 0 0 0 . 2 4.7 ' 0 . 5 8 . 1 0 . 3 0 1. 4 0 . 2 0 . 4 0 0 0 0 0 0 0 . 8 0 1. 5 5 . 5 0.0 1 0 5 . 1 1. 9 2 . 3 1. 4 0 . 1 0 . 4 1 2 0.0 7 1. 6 0 0 0 . 6 49. 1 ' EMISSION S SUMMAR Y

ESTIMATE

D t 1 ) CURREN

T >(*») Oxide s



# ' o f

Nitroge n 0

. 0 

## "o.o i 0.0 4 0 0 . 5. 5 29. 6 50. 5 0.0 4 6. 9 0. 1 0 0 . 1 0. 2 0 0 0 . 3 0 0 0 0.4 1 0 0 0 0 0.0 7 0 0 . 3 0 0 0 0 0 0 0.1 4 0 0 T R 

# J ) 94. 2 AIREMISSIONS .

Sulfu rOxide s 0 0 0 0 0 0 0 0 0 0 21. 6 4 . 5 0 1. 0 2 . 0 0 0 0 . 1 0 0 0 0 0.0 2 0 0 0 0 0 2 . 6 0 0 0 0 1. 2 0 0 0 . 9 0 0

_ 0 33. 9 M

M LBS./YEA R Carbo n Monoxid e 0 2 7 0 1 4 1 . 5 . 19 6 0 . 0 0 3,87 0 0 77 . 5 3 0 . 2 1 . 0 0 10 7 2 4 . 0 0 8 6 26 0 0 0 19 . 0 4 3 . 4 5 0 0 0 0 0 0 0 0 0 0 4,852 . 3 5 1 4

5 2 8

2 9

5 6

6 Pag e 1 o f 3

Tota l
1. 1 2 7 0.0 1 5 4 7. 4 8 . 6 38 5 3 0 66. 4 0.5 4 4,06 0 5 . 1 14 8 146. 5 17. 6 117. 3 2 9 66. 2 13 1 50. 6 1 6 0.9 1 8 8 29 4 1. 5 5 . 5 24. 8 24. 3 51. 7 4 7 81. 3 76. 4 37. 6 21. 6 7 4 4 . 5 1 2 5 . 3 T R 18. 2 6,225- 9 (7 > 

# -

Tota l Weighte d < 5

8 6 2 7 1 3,21 5 49 0 25 3 15,00 0 1,19 0 3,20 0 3 0 17,54 4 12 0 5,70 0 7,46 0 1,24 0 7,65 0 2,30 0 6,88 0 1.95 5 2,07 0 1,28 0 5 6 23 1 2,95 0 9 0 33 0 4 4 0 1,94 0 42 2 16 0 6,40 0 6,10 0 2,95 0 1,65 0 5,70 0 35 5 87 0 42 5 T R• 1.46 0 110,22 0 ( 7 > Acetaldehyd e vi a Ethylen e

vi a Ethano l Aceti c Aci d vi a Methano l

vi a Butan e vi a Acetaldehyd e Aceti c Anhydrid e vi a Aceti c Aci d Acrylonitril e (9 ) Adipi c Aci d Adiponitril e vi a Butadien e

vi a Adipi c Aci d Carbo nBlac k Carbo nDisulfid e Cyclohexanon e Dimethy l Terephthalat e (+TPA ) Ethylen e Ethylen e Dichlorid e vi a Oxychlorinatio n vi a Direc t Chlorinatio n Ethylen e Oxid e Formaldehyd e vi a Silve r Catalys t

vi a Iro

nOxid e Catalys t Glycero l vi a Epichlorohydri n Hydroge nCyanid e Direc t Proces s Isocyanate s Malei c Anhydrid e Nylo n6 Nylo n6, 6 Ox o Proces s Pheno 1 Phthall c Anhydrid e vi a 0-Xylen e vi a Naphthalen e Hig hDensit y

Polyethylen e Lo w Densit y

Polyethylen e Polypropylen e Polystyren e Polyviny l Chlorid e Styren e Styrene-Butadien e Rubbe r Viny l Acetat e vi a Acetylen e

vi a Ethylen e Viny l Chlorid e
Total s (1 ) Inmos t Instance s number s ar e base d onles s than100"/ . survey . Al l base don ' engineerin g judgemen t o f bes t curren t control . Probabl y ha s u pt o 107 . lo

w blaa . (2 ) Assume s futur e plant s wil l employ bes t curren t contro l techniques . * • (3 ) Exclude s methane , include s H2 S an dal l volatil e organics . '?•"'•• • (4 ) Include s non-volatil e organic s an d inorganics . (5 ) Weightin g factor s use dare : hydrocarbon s - 80 , particulate s - 60 , N0 X - 40^ , S0 X- 20 , an dC O - 1 . (6 ) Referre d to elsewher e i nthi s stud

y a s "Significan t Emissio nIndex " or "SE1" . (7 ) Total s are no t equa l acros s an d dow ndu e t o rounding . * • • (9 ) Emission s basedo nwha t i s no

w anobsolet e catalyst . Se e Repor t No . EPA-450<*3-73-OObbto r up-to-dat e information .TABL E I EMISSIO NSUMMAR Y j> ag e 2 o f 3
ESTIMATE D ADDITIONA L < 2 > AI R EMISSION S IN1980 , M M LBS./YEA R Hydrocarbon s (-

^ Particulate s ^ ' Oxide s o f Nitroge n Sulfu r Oxide s Carbo n Monoxid e Tota l Acetaldehyd e vi a Ethylen e

vi a Ethano l Aceti c Aci d vi a Methano l

vi a Butan e 

### vi aAcetaldehyd e Aceti cAnhydrid e vi aAceti cAci d Acrylonitril e (9 ) Adipi cAci d Adiponitril e vi aButadien e

vi aAdipi cAci d Carbon Blac k Carbon Disulfid e Cyclohexanon e Dimethy l Terephthalat e (+TPA) Ethylen e Ethylen e Dichlorid e vi aOxychlorinatio n vi aDirec tChlorinatio n Ethylen e Oxid e Formaldehyd e vi aSilve rCatalys t

vi aIro n Oxid e Catalys t Glycero l vi aEpichlorohydri n Hydrogen Cyanid e Direc tProces s Isocyanate s Malei cAnhydrid e Nylo n 6 Nylo n 6, 6 Ox o Proces s Pheno l Phthali cAnhydrid e vi aO-Xylen e

vi aNaphthalen e High Densit y Polyethylen e Lo wDensit y Polyethylen e Polypropylen e Polystyren e Polyviny l Chlorid e Styren e Styrene-Butadien e Rubbe r Viny l Acetate,vi aAcetylen e

vi aEthylen e Viny l Chlorid e Total s .0 4

. 2 

### 1. 2 0 0 0 12: 2 0.7 3 28 4 o ; ' 10. 5 0 6 4 

### 0 . 77 . 73. 8 14. 8 11 0 34. 2 32. 8 14. 8 17. 6 8. 9 0 

### 1. 2 3 1 0 0 3 . 21 . 0 . 0 21 0 26 2 

### 15 2 2 0 5 3 3. 1 1.8 5 4. 5 0 26. 3 

### 1.547. 2 .8 6

. 3

. 3 

### 0

0 0 0 0 0 0 0.1 4 4. 4 0. 5 3. 3 0.0 7 0 1. 1 0. 2 0. 5 0 0 0 0 0 0 0. 7 0 3. 2 5. 3 0.0 1 0 13; 2 0 6. 2 5 0. 5 0.3 4 1 0 0.0 5 0.3 1 0 0 0. 9 55. 9 .0 7

. 2 

### 0 0 0.0 4 0 0 0 8. 5 19. 3 47. 5 0.0 4 2. 8 0.0 3 0 0
. 0
. 0 0 

### 0.1 5 0 0 0 0 0 0 0 0 0 0 0 . 0 0 0 0 0 0 

## 6 . 0 0 T R 0 0 5

79, 5 0 0 0
• 0 0 0 0 0 0 0 8. 9 1. 1 0 0.8 4 61. 5 0 0 0.0 5 0 0 0 0 0.0 2 0 0 0 0 0 6. 8 0 0 0 0 1.1 3 0 0 0.1 8 0 0 0 0 0 0 0 2 . 1 . 30 4 0 . 0 0 1,59 0 0 85 . 42 . 0 . 2 5 0 0 66 . 17 . 0 0 8 5 24 1 0 0 14 . 0 11 3 0 0 0 0 0 0 0 0 0 0 0 5 4 2
0 9

1 9 2

7 0

3 1. 2

0 0.0 4 0 14. 7 2.1 5 59 b 19. 5 62. 4 0.5 4 1,67 0 1.2 4 16 2 118. 7 7 7 13 6 34. 2 3 3 81. 5 34. 6 8. 9 0 8 7 27 2 3. 2 5. 3 18. 2 21. 3 13 4 0 21 6 26 7 152. 5 21.4 7 6 3 3.2 5 2.3 4 4. 5 TR 27. 2 80. 5 2,58 8 

### 4,351. 9 Tota l WeiRhte d ( 5



### . 6 

### >

(1 ) I n mos tinstance s numbers ar e base d on les s tha n 1007 . survey . Al l base d on engineerin g judgemen to f bes tcurren tcontrol . Probabl y ha s u p t o 107

. lo w bias . (2 ) Assume s futur e plant s wil l emplo y bes tcurren tcontro l techniques . (3 ) Exclude s methane , include s H2 S an d al l volatil e organics . (4 ) Include s non-volatil e organic s and"inorganics . (5 ) Weightin g factor s use d are : hydrocarbon s - 80 , particulate s - 60 , N0 X

### - 40 , S0 X

### - 40 , an d C O - 1 . (6 ) Referre d t o elsewher e i n thi s stud y a s "Significan tEmissio n Index " o r"SEI" . (7 ) Total s ar e no tequa l acros s an d dow n du wt o rounding' . (9 ) Se e shee t1 o f

3 . 9 6 0 2 0 98 0 6 0 23,00 0 77 9 

### 3,01 0 3 0 7,20 0 3 0 6.26 0 6,04 0 2,43 0 

### 8.80 0 2.74 0 2.65 0 

### 1,25 0 1.44 5 70 0 0 22 5 2,72 0 19 4 31 8 12 5 1,70 4 

### 1.10 0 0 17,20 0 21,30 0 12,19 0 1,64 0 4.84 0 22 5 17 0 36 0 T R 2.17 0 134,21 3 < 7 >

## 4 —

## •-—

> 

## f—

« r 

## --- . r

## • • • - • • • - - - i

• TABL E I 1 EMISSION S SUMMAR Y

• J O ' | Emission s ( 2 _) , M M Lbs . /Yea r
I Tota l b y 198 0 Tota l Weighte d ( 5 ) b y 198 0
1 Acetaldehyd e vi aEthylen e 2. 3 18 2 v i aEthano l 2 7 2 7 Aceti cAci d vi aMethano l 0.0 5 3

v i aButan e 5 4 3,21 5 v i aAcetaldehyd e 2 2 1,47 0 Aceti cAnhydrid e vi aAceti cAci d .10. 8 31 3 Acrylonitril e (9 ) 98 0 38,00 0 Adipi cAci d 5 0 1,97 0 Adiponitril e vi aButadien e 128. 8 6,21 0

v i aAdipi cAci d 1. 1 6 0 Carbo n Blac k5,73 0 24,74 0 Carbo n Disulfid e 6. 3 15 0 Cyclohexanon e 31 0 11,96 0 Dimethy l Terephthalat e (+TPA ) 26 5 13,50 0 Ethylen e 9 4 3,67 0 Ethylen e Dichlorid e vi aOxychlorinatio n 25 3 16,45 0 v i aDirec tChlorinatio n 6 3 5,04 0 Ethylen e Oxid e 12 0 9,53 0 Formaldehyd e vi aSilve rCatalys t212. 5 3,20 5

v i aIro n Oxid e Catalys t8 5 .3,51 5 Glycero l vi aEplchlorohydri n '• 2 5 2,00 0 Hydroge n Cyanid e Direc tProces s " 0. 5 (10 ) 2 8 (10 ) Isocyanate s 17 5 45 6 Malei cAnhydrid e 56 6 5,67 0 Nylo n 6 4. 7 J 28 4 Nylo n 6, 6 10. 8 65 0 Ox o Proces s • 4 3 76 5 Pheno l 4 6 (3,64 0 Phthali cAnhydrid e vi aO-Xylen e 18 6 1,52 2 v i aNaphthalen e 4 7 16 0 Hig h Densit y Polyethylen e 29 7 23,60 0 Lo wDensit y Polyethylen e 34 3 27,40 0 Polypropylen e 19 0 15,14 0 Polystyren e 4 3 3,?9 0 . Polyviny l Chlorid e 13 7 10,54 0 Styren e 7. 4 61 0 Styrane-Butadien e Rubbe r1 4 1,04 0 Viny l Acetat e vi aAcetylen e 9. 8 78 5

v i aEthylen e T RT R Viny l Chlorid e 4 5 3.63 0
Total s 10,60 5 (7 ) 244,42 0 (7 ) (1 ) I n mos tinstance s number s ar e base d on les s tha n 1007 . survey . Al l base d o n engineerin g judgemen t (2 ) Assume s futur e plant s wil l emplo y bes tcurren tcontro l techniques . (3 ) Exclude s methane , include s H2 S an d al l volatil e organics . (4 ) include s non-volatil e organic s an d inorganics . (5 ) Weightin g factor s use d are : hydrocarbon s - 80 , particulate s - 60 , N0 X-'40 , S0 X- 20 , an d C O - 1

• (6 ) Referre d t o elsewher e i n thi s stud y a s "Significan tEmissio n Index " o r"SEI" . 1 (7 ) Total s ar e no tequa l acros s an d dow n du e t o rounding . 1 (8 ) B

y 1985 . 1 (9 ) Se e shee t1 o f J 1 (10 ) Du e t o anticipate d futur e shu tdow n o f margina l plants . 

# •"* " " | " f t. / a1 a

Estimate d Numbe ro f Ne w (197 3 - 1980 )
b 0 4 0 3 3 5 7 4 3 1 3 2 1 0 8 2 1 8 1 0 1 5 4 0 1 2 1 0 1 0 6 1 0 1 0 6 1 1 6 0 3 1 4 1 3 2 2 3 2 5 9 4 I 4 1 0

o f bes tcurren tcontrol . 

# • 1
t t t m *

Pag e 3 o f

3 Tota l E Plant s Curren t

1 , lb O 96 6 4 0 0 1,02 0 87 5 1,70 5 1,16 5 1,43 0 4 3 5 28 0 3,00 0 87 1 1,80 0 2,86 5 22,29 5 4,45 0 5,59 3 4,19 1 5,91 4 1,72 9 24 5 4 1 2 1,08 8 35 9 4 8 6 1,52 3 1,72 7 2,36 3 72 0 60 3 2,31 5 5,26 9 1,16 0 3,50 0 4,375 . 5,95 3 4,46 4 2 0 6 1,28 0 5,40 0

Probabl y ha s u p t o 107 . 4 • t >

m

stimate d Capacit y M M Lbs./Yea r B v 198 0 2,46 0 96 6 1,80 0 50 0 2,01 5 2.10 0 3,70 0 (8 ) 2,20 0 84 5 55 0 5,00 0 (8 ) 1,10 0 3,60 0 5,90 0 40,00 0 8,25 0 (8 ) 11,54 0 6,80 0 (8 ) 9,00 0 3,52 0 (8 ) 38 0 20 2 2,12 0 72 0 1,50 0 3,00 0 3,00 0 4,20 0 1,80 0 (8 ) 52 8 8,50 0 21,10 0 5,80 0 6,70 0 8,00 0 10,00 0 5,23 0 35 6 2,20 0 13,00 0

lo wbias . 

# 7 : ^

*

>



# »- * U n