# OAR Box 1851

Prepped byKeeia Richards



### Document

Number: 

# 37 ) ll-A-1 1 Docket Number: 

# A-90-1 9

Printed 11/19/200811:19:51 AM

• Sheet 37 of 41 p. 1P. 2 

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

# i sei so«i l ^ lllll i^ ' " • '" 2 EP A AI R DOCKE

T , na.ii.ir.wm n j 

## 99 2 PJ _JC | )CKE T| 

# , ENGINEERING AN D COS T STUD Y F AI RPOLLUTION CONTRO L FO RTH E PETROCHEMICA

L INDUSTR

Y VOLUM E 8 : VINY

L CHLORID

E MANUFACTUR

E B Y TH E BALANCE

D PROCES S

b y R.G . Bellam y an dW.A . Schwart z

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 AProjec t

Officer : Lesli e 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

Jul y 197 5P. 3

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

interes t

t o alimite dnumbe r of readers . Copie s ar e availabl e fre e o f

charg e t o Federa l employees , curren t contractor s an d grantees , an dnonprofi t organization s - a s supplie s permi t - fro mth 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 Divisio nof

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 na s receive dfro mHoudr y Divisio nof

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 of 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 .

Publicatio nNo . EPA-450/3-73-006- h

n

### p j 

### VCM- l P. 4

! • T - I . Introduction

The productio n o f viny l chlorid e monome r (VCM ) ha s becom e a bi g volum

e business . Som

e o f the olde r existing plant s ar e in th

e 15 0 t o 20 0 millio n pound s pe r yea r capacit y range . I t i s believe d tha t virtuall yal l ne wplant s wil l be designe d t o produc e i n exces s o f 50 0 millio n pound s o f VCM pe r year . ^'

Thi s i s becaus e the economic s o f produc
tion definitel yfavo r larg e volume ra wmateria l suppl yan d larg e equipment . Almos t al l the VC M produce d goe s int o the manufactur e o f polyviny l chlorid e (PVC) . Aver ysmal l amoun t i s use d a s a n intermediat e t o manufactur e methy l chlorofor

m(CH3*CCl3) , a specialt ysolvent . Asmal l quantit ywa s previousl yuse d i n specia l aeroso l spray s (insecticides , fungicides , etc. ) bu t thi s us e ha s recentl y bee n banne d i n the Unite d States . Therefor e the growt ho f VCM i s exactl ytied t o the growt ho f PVC . I n 197 3 tota l U.S . productio n o f VCM exceede d 4. 7 billio n pounds.(2 ) Ove r ninet ypercen t o f the viny l chlorid e monome r produce d in
- th e Unite d State s i s obtaine d b ycracking dichloroethane . A n olde r proces s using acetylen e an d hydroge n chlorid e feed ha s bee n virtuall ycompletel yreplace d b ythe dichloroethan e rout e becaus e o f the hig hcos t o f acetylene . Th e capacit y o f acetylen e typ e plant s i s abou t 10-12 % bu t actua l productio n fro mthemi s muc hless . I n mos t cases , overal l vapo r emission s fro mthe cracking operatio n ar e smal l i n quantity . The vapo r emission s d o includ e a smal l amoun t o f VCM . Th e problem s o f VC M ai r emission s i n thes e plant s ar e simila r t o thos e encountere d i n PV C production . However , VC M plant s have on e bi g advantage , the yemploya continuou s proces s a s oppose d t o the PV C batc h typ e processes . Thi s mean s tha t VC M emission s fro m thes e plant s ar e considerabl yles s pe r uni t o f production . Thi s repor t concentrate s o n VC M emissions , no t hydrocarbo n an d particulat e losses . I t als o contain s informatio n on VCM losse s fro

methylen e dichlorid e (EDO
- plants_using th e oxychlorinatio n process . Thi s latte r informatio n wa s no t include d i n a previou s in-dept hstud yo f the oxychlorinatio n process . ( 4 ) Prio r t o Januar y197 4 i t wa s no t know n tha t VC M wa s carcinogeni c a t lowconcentration s (under 50 0 PPM) . Becaus e o f this , EDC manufacturer s had no t attempte d t o analyz e o r repor t the presenc e o f VC M i n the oxychlorinatio n ven t streams . The emissio n losse s use d i n the presen t repor t ar e base d o n informatio n obtaine d prio r t o Septembe r 1974 . Ther e ha s bee n muc hmoneyan

d effor t spen t t o reduc e VC M emissio n losse s fro m EDC an d VC M manufactur e sinc e tha t tim e a s wel l a s muc himprove
men t mad e i n the detectio n o f lowconcentration s o f VC M (under 1 0 PPM) . VC M emission s hav e undoubtedl ybee n substantiall y reduce d sinc e the summe r o f 1974 .VCM- 2 P. 5

II . Commercia l Processe s Acetylen e an

d hydroge n chlorid e ar e use d a s starting material s i n th e oldes t commercia l process . I n thi s country , thi s i s a mino r proces s becaus e economic s favo r ethylen e a s a rawhydrocarbo n feedstoc k ove r acetylene . However , ther e ar e two plant s stil l using thi s process . Th e reactio n i s a s follows :

C2H 2 + HC 1 > CH 2 « CHC 1 The reactio n i s catalyze d b ymercuri c chlorid e (10% ) on a n activate d carbo n bas e an d i s carrie d ou t a t 19 5 t o 285°F . The reactant s ar e fed a t a 1: 1 mo l rati o an d the reactio n m^ goe s t o approximatel y9 8 t o 99 % completion . The reactio n i s veryexothermi c an d temperatur e mus t b e controlle d care fully . Th e reacto r pressur e i s low( 2. 5 atm. ) fo r safety reasons . Acetylen e become s increasingl yhazardou s (explosively ) a t elevate d pressures . I f acetylen e coul d b e produce d nearl ya s cheapl ya s ethylen e (sa ywithi n a hal f a cen t pe r pound) , thi s proces s coul d compet e wit hethylen e proces s a s ther e ar e n o majo r by-product s t o consider . Howeve r a t the curren t differentia l o f 5 t o 1 0 cent s pe r pound , the us e o f acetylen e i s to o expensive t o conside r fo r an yne wplant s an

d make s existing plant s marginal . Figur e VC- 1 show s a simplifie d flowdiagra mfo r th e acetylen e process . Plant s VC- 7 an d VC- 9 ar e the onl yplant s surveye d i n thi s stud

ytha t us e th e acetylen e process . I n the principa l proces s currentl yused t o produc e VCM , dry dichloroethan e (als o name d ethylen e dichloride ) i s dehydro
chlorinate d t o viny l chlorid e i n a cracking furnace . Th e chemica l reactio n i s a s follows :

CH2CICH2C I > CH 2 = CHC 1 + HC 1 The dichloroethan e fo r thi s cracking operatio n i s normall y produce d b

ytw o commercia l processes . On e i s the direc t chlorinatio n o f ethylen e wit hchlorine :I I [ i I t 1 . - j

_ f '• t ' i : ' A \. i 

## • 7 r



### TABL E VC- 3 NATIONA L EMISSIO

NINVENTOR

Y FOR VC M MANUFACTURE
Plan t Cod e Number : VC- 1 Plan t Capacity , Millio

nLbs.Ar. : 50 0 Process : Balance d EDC Sourc e Are a 7 a . 7 a C D 

# 1*

1 Descriptio n ED C Distillation Colum n ED C Distillation Colum n Transfe r an

d Loadin

g Losse s Samplin g Losse s Fugitive Losse s Tota l Typ e O f Emissio n Contro l Devic e 

# il] Contro l

Devic e Catalo g I.D , No . VMD- 1 VMD- 1 VMD- 1 VMD-1 7 VC M Emission s

Lbs./Lb . Prod . Tons /fr. .00017 5 .00035 4 .00004 8 .00000 1 9 

### .00057 8 < O l 

### 144. 5
Notes : ( 1 [2\ $ 

### Ven t fro

mEDC colum

n i n associated direc t chlorination unit . Ven t fro

mEDC colum

n i n associate d oxyhydrochlorinatlon unit , Flowsamplin

g loops . N o estimat e o f fugitive emissio n given - n o materia l balanc eTABL E VC- 3 NATIONAL EMISSIO NINVENTORY FO R VC M MANUFACTUR E
Plan t Code Number : VC- 2 Plan t Capacity , MillionLbs.Ar. : 30 0 Process : Pyrolysi s o f ED C
Sourc e Are a B C D F F& G

Note s 

# (i ) Description Wate r Los s Release d Fro m

Neutralize r Doc k & R

R Tan k Ca r Loadi n Samplin g (3 ) Neutralizer s an

d Filter s (4 ) Dryer s and . proces s Vessel s (4 ) Fugitiv e Tota l 

# ®

a p i 

### (5 ) Typ e O f Emissio n Contro l Devic e Contro l

Devic e Catalo g I.D . No . VMD- 1 VMD- 2 VMD-1 7 VMD- 1 VMD- 1 VC M Emission s

Lbs./Lb . Prod , .00001 5 .00121 4 .00000 1 .00000 2



### . oooo3 2 Tons/Yr .

< 

### o I .00126 4 189. 6
Ven t fromflas hpo t releasing . Al l majo r VC M emissio n stream s returne d t o absorbe r t o b e recycle d i n ED C streams . Thi s los s wil l dro p t o approximatel y.00017 4 b ymi d 197 5 whe n doc k loading losse s ar e connecte d t o system . Samplin g losse s minimize d b ysamplin g loop . Intermitten t emissions . No estimat e o r materia l balanc e given .



# *""" ) 

# *" ! *~1 

# X~ wi. L i._
- i
TABL E VC- 3 NATIONA L EMISSIO NINVENTOR Y FO R VC M MANUFACTUR E
Plant Cod e Number : vc- 3 Plant Capacity , MillionLbs.Ar. : Process : BalancedED C 84 0

Sourc e Are a A C D Description

Scrubbe r Ven t Stac k - Collect s Fro m

8 Area s Loadin g Arm s an

d Loadin g Area s Flar e Samplin g Fugitiv e (1 ) Tota l Typ e O f Emissio n Contro l Devic e

• Non e Contro l

Devic e Catalo g I.D.No . VMD- 1 VMD-3 (2 ) Lb s VC M ./Lb . P J .00235 5 .00004 8 .00002 3 .00005 2 .00247 8 Emission s

•od . Ton s Ar .

1040. 7VCM-15

Notes : (1 ) (2 ) Calculate d b

yanalogyfromemissio n factor s take n from"Contro l Technique s fo r Hydrocarbo n and Organi c Solven t Emission s Fro mStationarySources" , Natura l Ai r Pollutio n Administration , Publishe r Numbe r AP-68 , Marc h1970 . Arefrigeratio n device , VMD-4 , i s use d t o condens e some o f th e vapor s prio r t o th e flare . N o dat a ar e give n a s t o condition s o r typ e o f equipment .

X I c oTABL E VC- 3 NATIONA L EMISSIO NINVENTORY FO R VC M MANUFACTUR E
Plant Code Number : VC- 4 Plant Capacity , Millio nLbs.Ar , Process : Balance d ED C 73 0

Sourc e Are a Descriptio n Typ e O f Emissio n Contro l Devic e Contro l

Devic e Catalo g I.D . No . VC M Emission s

Lbs./Lb . Pro d TonsA r ' Mai n Stac k Loadin g Losse s Fugitiv e (1 ) Tota l VMD- 1 VMD- 4 (2 ) .00136 8

.00192 9 9 .00329 7 1203. 4 < o 3 <T >

Notes ; (1 ) N o estimat e give n o r materia l balanc e made . (2 ) Som e typ e o f condensin g syste mi s note d bu t n o informatio n i s give n o f condition s o r typ e o f equipment .

r— 1 1— 1 r 

# r J C O* I \ I Jt

_J* . JL I I JI i I , JI J« - I - 1 I
TAB UVC- 3 NATIONA L EMISSIO NINVENTOR Y FO R VC M MANUFACTUR E
Plan t Cod e Number : VC- 6 Plan t Capacity , Millio n Lbs.Ar , Process : Pyrolysi s o f ED C 32 0

Sourc e Are a Descriptio n Typ e O f Emissio n Contro l Devic e Contro l

Devic e Catalo g I.D.No . VC M Emission s

Lbs./Lb . Prod . Ton s Ar . A C D G Ligh t Colum n Ven t Tank Ca r Loadin g Sampling Cleaning , Inspections , Etc . Fugitiv e (1 ) Tota l o f Vesse l VMD- 1 VMD-1 7 00004 0 00048 6 00000 1 00008 8
00061 5 < n se i 104. 6 (2 )

Notes ; (1 ) N o estimat e o r materia l balanc e given . Statemen t mad e tha t fugitiv e emission s ar e ver ylo w du e t o constan t monitorin g an d goo d housekeeping . (2 ) Base d o n dat a provide d i n Jun e 197 4 report . Correspondenc e wit hth e manufacture r subsequen t t o th e completio n o f thi s stud yindicate s tota l VC M los s ma yhav e bee n a s muc ha s te n time s highe r tha n valu e shown .

11 °TABL EVC- 3 NATIONALEMISSIO NINVENTOR YFO RVC

M MANUFACTUR

E 

### Plan tCodeNumber : VC- 7 Plan tCapacity , Millio nLbs.Ar . Process : Acetylen e 30 0


### Sourc e Are a C D Descriptio n

Loadin g Losses , Max, Samplin g Flar e Stack , Fugitiv e Tota l Typ e O f Emissio n Contro l Devic e 

# m Contro l Devic e Catalo g I.D . No . VMD-1 7 VMD- 3

Notes : (1 ) Thi s los s estimate d byobservatio n a s a probabl e maximum , 

# I

r — T B VC M Emission s Lbs./Lb . Pro d .00003 0 .00000 1 0 

### .00036 5 .00039 6 Ton s A r

59. 4 < n 2 l M C O



# V" .5 7 JT %TABL E VC- 3 NATIONA L EMISSIO NINVENTOR Y FO R VC M MANUFACTUR E
Plan t Cod e Number : VC- 8 Plan t Capacity , Millio n Lbs.Ar. : 10 0 Process : Balance d ED C
Sourc e Are a Descriptio n D F H 2 Samplin g

Dryer s Oxychlorinatio n Ven t Wast e Heat 0 Boile r Scrubbe r Ven t (1 ) 

### Fugitive \ d 

### i Tota l Typ e O f Emissio n Contro l Devic e Contro l

Devic e Catalo g I ,D . No . VMD-1 7 VMD- 1 VMD- 1 VMD- 6 Lb s VC M Emission s

./Lb . Prod . .00003 8 .00000 3 .00127 2 .00001 9 .00015 2 TonsAr .VCM-19 .00148 4 74. 2
Notes : (1 ) Mos t o f th e mai n vent s o f th e VC M plan t ar e vente d t o a wast e hea t boile r alon g wit hwast e stream s fromothe r processes . (2 ) Bymateria l balance .TABL E VC- 3 NATIONA L EMISSIONINyENTOR Y FO R VC M MANUFACTUR E
Plan t Cod e Number : VC- 9 Plan t Capacity , MillionLbs.Ar . Process : Acetylen e 27 5

Sourc e Are a

• E " Descriptio n

Ven t Reacto r Fugitiv e ( 2 ) Tota l Ven t (! ) Typ e O f Emissio n Contro l Devic e Contro l

Devic e Catalo g I.D . No . VC M Emission s

Lbs./Lb . Pro d VMD- 1 & VMD-4(3 ) .00356 1 .00151 5 .00507 6 TonsA r

698. O <



### o 3 l r O O

Notes : (1 ) (2 ) (3 ) Asecondaryreacto r i s incorporate d 4. n thi s plan t t o reduc e to£a l VC M emissions , bu t i t als o ha s a monetar yvalu e i n reducin g losse s significantly . Estimate d frommateria l balance . N o detail s ar e give n othe r tha n th e ven t ar e coole d t o les s tha n 40°F . 

# -4'J p

# I 

# *L 1

TABL E VC- 7 DIREC T FIRE D BOILE RPLU S SCRUBBE REMISSIO N CONTROL SYSTE M FOR 5 3 0 M M LBS./YR . OXYCHLORIWATIO WPROCES S VEN T GA S STREA M Cotnponen

t Carbo nDioxid e CarbonMonoxid e "ltroge n Oxyge n Kfthan e ethylen e Ethan e ethylen e Dlchlorld e Ethy l Chlorid e Viny l Chlorid e Wate r Hydrochlori c Aci d Chlorin e Nitroge nOxide s SodiunHydroxid e Sodiu m Chlorid e Tota l Lbs./Hr . SCF M

80° F Comb . Ai r Natura l Ga s Proces s Ven t Ga s (100°F

y Proces s Ven t Ga s l 

## 'HS 52,70 6 2,96 2 13 0 31 8 43 5 45 4 38 6 10 1 Combustio n

Ai r
26,75 2 8,12 6 Natura l

Ga s
5 4 52 7 12 0 Incinerato r

Flu e Ga s 7,78 4 79,51 1 3,97 1 Quenc h

Wate r Causti c

Feed Scrubbe r

Rejec t Scrubbe r

Effluen t 7,78 4 79,51 1 3,97 3

59,53 1 13,08 5

550 ° F Flu e Temp . 46 0

35,33 8 Quenc h Wate r 70 1 3,68 0 60 9 1 1 4 95,57 0 21,23 0 27,52 4

27,52 4

Fee dWate r 35,50 0 Lbs./hr . (240°F ) Stea m a t 24 5 PSI G(Sat. ) 33,80 0 Lbs./Hr .

» . Blowdov

m 1,70 0 Lbs./Hr . (404°F ) Packe dTowe r 67 8 67 8
Flu e Ga s 140 ° F
Causti c Feed 19,03 4

99 1 .20,02 5

Rejec t }'I0° F 12,47 4 1 4 103,74 7 24,21 0 <

Boile r