# OAR Box 1851 Prepped by Keeia Richards



# Document

Number: 

# 32 ) ll-A- 6 Docket Number: 

# A-90-1 9

Printed 11/19/2008 11:19:51 AM Sheet 32 of 41 p. 1

# " 1 f 

# I


# r r r

j A-90-1 9 ll-A- 6 EPA-450/3-73-OO6-D 

# t_tl_* ENGINEERING AN D COST STUD OF AI RPOLLUTION CONTRO L H FO RTHE rPETROCHEMICAL INDUSTR Y VOLUM E 2 : ACRYLONITRIL

E J MANUFACTUR E 

# J- 

# > ' ' b y J 

# |

. W.A

. Schwartz , F.B
. Higgins , Jr
. , J
. A

. Lee , R
. Newirth , an dJ
. W
. Pervie 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 LPROTECTIO N AGENC Y Offic e o f

Ai r an dWast e Managemen t Offic e o f

Air'Qualit y Plannin g an dStandard s Research,Triangl e Park , N
. C

. 2771 1

Februar y 197 5

# 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 d grantees , an dnonprofi t organization s - a s suppile s permi t - fro mth e Ai r Pollutio nTechnica l Informatio nCenter , Environmenta l Protectio nAgency , Researc hTriangl e Park , Nort hCarolin a27711 ; or , fo r afee , 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 th e Houdr y Divisio nof Ai r Product s an dChemicals , Inc
. , i nfulfillmen t of Contrac t

No
. 68-02-0255

. Th e content s of thi s repor t

ar e reproduce d herei na s receive dfro mth e Houdr y Divisio nof Ai r Product s an dChemicals , Inc
. Th e opinions , findings , an dconclusion s expresse dar e thos e of th e autho r

an dno t necessaril y thos e of

th e Environmenta l Protectio n Agency

. Mentio no

f compan y o r

produc t name s i s no t

t o b e considere d a s a nendorsemen t

b y th e Environmenta l Protectio nAgency

.

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

n

## 1 I 1 . 1 ,
_L

°
Plan tCod e Numbe r Dat e on-strea m Capacity , Ton s o f

Aerylonitrile/Yr . Averag e Production , Tons/Yr . Rang e i n Production , 7 . o f Max . Operatin g Kange , % o f Max . Prod . By-product s (Net ) HCN, Tons/Yr . Oil s & Polymers , Tons/Yr . Emission s t o Atmospher e Strea m
Flow , (a ) Lbs./Hr . Flo vCharacteristi c I f Intermitten t- Hrs./Yr . o f Flo w Composition , Tons/To n Aerylonitrll e Particulat e Carbo n Dioxid e Carbo n Monoxid e Ammoni a Methan e Ethan e & Ethylen e Propylen e Propan e H—Irocyanl e _s_ t Acrylonltrll e (AN ) Acetonltrll e (ACN ) Oxygenate d Hydrocarbon s ' Nitroge n Oxyge n Sulfu rOxide s Nitroge n Oxide s Wate r Sampl e Ta p Locatio n

• Dat e o rFreq . o f

Samplin g Typ e o f Analysi s Particulat e HC , CO , C0 2& Inert B NO x Odo r Colo r Ven tStack s ' Number Heigh t Diamete r SCF M pe rstac k< a

) Emissio n Contro l Devic e Demiste r Condense r Other s Tots l Emission s Hydrocarbon s

. Particulate s NO , SO , C O TABL E "AN-3 A SURVE Y O F U . S . ACRYLONITRIL E PLANT

S AN D ATMOSPHERI

C EMISSION S FRO

M THES E FACILITIE S 

## > 51- 1

196 5 100,00 0 (1 ) 100,00 0 N o Seasona l variatio n

'50-10 0 i s ) \ 20,00 0 4,00 0 0 4,00 0 Absorbe rVen tAbsorbe rVen t (Durin g Start-up ) 285,00 0 62,50 0 <- o) Continuou s Intermitten t 8

. T

K 0.29 4 . 0.05 0 0.18 0 f • .'0.03 2

o 0.03 2
0.04 7 " 0.00 8 0.12 4 0.03 0 <" ) 0.00 2 < b > 0.00 4 0.02 9 0.22 5 0.00 6 < b > 0.00 8 9.72 6 1.67 6 0.86 5 . 0.24 5
0.60 5 0.30 5 Accessibl e Sampl e Lin e fro m Reactg rEffluen tDuct s 

# » - Continuou s Fo rA

N other s twic e awee kCont . Monito ro f O , Calc' d Non e (d ) Non e Essentiall y Odorles s Sligh tOdo r Appearanc e o f

steam , No Residua l Plum e

1 200"0 " 2'6 " 12 0 45 0 64,60 0 14,30 0 X Shee t

Produc t Fractionato rVen t 11 0 Continuou s

0.000 4 (b ) 0.000 3 < b > 0.00 4 (c ) 

# * Elevate d f. Difficul tt o Reac h Non e Calc' d

Unknow n
1 58'0 " 2 " 10 0 2 5

X Flar e (Distillatio n Lt . Ends ) Incinerato r(By-produc tHC N 6 . ACN

) 0.20 9 T R 0.00 7 0 . 18 0 o £ 6

Incinerato r Flu e Ca s 110,00 0 f > Continuou s
T R X 0.000 3

0.0000 2

X
0.007 3 X Sampl e Lin e t o Groun d Leve l Twic e aMont h Non e ( e ) ( e ) o Non e Smokeles s 

## « 1 135'0 " 6'0 " 160 0 24,00 0 

# ^ T ^ T " "

•

Flar e
./£ . 1.30 0 Variabl e

X



# £

r — o

X X
X Non e
Calc' d

Non e Smokeles s 1 275'0 " 1'8 " >150 0 ai26 5TABL E AN-3 A SURVE Y O F U . S . ACRYLONITRIL E PLANT

S AN D ATMOSPHERI

C EMISSION S FRO

M THES E FACILITIE S Shee t2 o f 6 Plan tCod e Numbe r 51- 2 Dat e on-strea m Capacity , Ton s o f

Acrylonitrile/Yr . Averag e Production , Tons/Yr . Rang e i n Production , 7. o f Max . Operatin g flange, '/. o f Max . Prod . By-product s (Net ) HCN , Tons/Yr . Acetonitrile , Tons/Yr . Oil s & Polymers , Tons/Yr . Emission s t o Atmospher e Strea m
Flow , <•*> Lbs./Hr . Flo w Characteristi c

. i f Intermitten t - Hrs./Yr . o f Flo w Composition , Tons/To nAcrylonitril e particulat e Carbo nDioxid e Carbo nMonoxid e Ammoni a Methan e Ethan e & Ethylen e Propylen e Propan e Hydrocyani c Aci d Acrylonitril e (AN ) Acetonitril e (ACN ) Oxygenate dHydrocarbon s Nitroge n Oxyge n Sulfu r Oxide s Nitroge nOxide s Wate r Sampl e Ta pLocatio n Dat e o r Freq . o f Samplin g Typ e o f Analyst s Particulat e HC , CO , C0 2 & Inert s N0 X Odo r Colo r Vent Stack s Numbe r Heigh t Diamete r Exi t Ca s Temp. , ° F SCFM pe r stac k < a > Emissio nContro l Devic e Demiste r Condense r Other s Tota l Emission s Hydrocarbon s b Particulate s NO x• SO , C O 196 5 125.00 0 100,00 0 N o Seasona l Variatio n

7,00 0 3,20 0

Absorbe r Ven t
200,00 0 Continuou s

0.50 8 0.17 8

0.05 2 0.14 4 0.000 5 0.000 4 0.00 8 7.22 2 0 . 30 3

Absorbe r Ven t Nitroge nComp'd . onc e a week , other s i n197 1

Non e

50,00 0 i Non e CLC.* " Silver ! Nitrat e

1 „ ' - • . ' , 200'0 " 2'6 " % 11 0 • Titratio n ( f "* O Absorbe rVen t (Durin g Start-up ) 140,00 0 <°> Intermitten t 6- 8
0.08 0 0.04 0

0.02 6 0.02 7 0.03 4 0 . 60 8 0.01 7 5.18 5 0.21 8

30*00 0 Incinerato r Flu e Ga s (K ) 46,70 0 Con ti nuou s

O

. 28 2

« 0.00000 1

1 0 

### 0 0 25 1 17 4 0000 1 16 0 Use d 130 ' cran e M < irch . 197 1 Non e CL C < f > '" > Silve rNitrat e Titratio n ' f ^ Non e
1 lOO'O " 12'0 " 1.60 0 10,35 0

Flar e (Distillatio n Lt . F.nd s * p ) , 2 Incinerator s (by-produc tHC N & ACN

) 0.20 6 0.0000 1 

## I 0.17 8 Flar e ?,65 0 Intermitten t

0 01 4

0.07 8 0.00 2 T R 0 Oi l Non e
Calc' d

1 JOO'0 " 2'0 " 1.00 0 ^60 0

T J U lTABL E AN-3 A SURVE Y O F U . S . ACRYLONITRIL E PLANT

S AN D ATMOSPHERI

C EMISSION S FRO

M THES E FACILITIE S Shee t3 o f 6 Plan tCod e Numbe r Dat e -on-stres m Capacity , Ton s o f

Aerylonitrile/Yr . Averag e Production , Tons/Yr . Rang e i n Production , X o f Max . Operatin g Range , X o f Max . Prod . By-product s (Net, ) HCN , Tons/Yr . Acetonitrile , Tons/Yr . 0il 6 & Polymers , Ton6/Yr . Emission s t o Atmospher e Strea m Flow , (a ) Lbs./Hr . Flo w Characteristi c i f Intermitten t - Hrs./Yr . o f Flo w Composition , Tons/To nAcrylonitril e Particulat e CarbonDioxid e CarbonMonoxid e Ammoni a Methan e Ethane & Ethylen e Propylen e Propan e Hydrocyani c Aci d Acrylonitril e (AN ) Acetonitril e (ACN ) Oxygenate dHydrocarbon s Nitroge n Oxyge n Sulfu r Oxide s Nitroge nOxide s Wate r Sampl e Ta pLocatio n Dat e or Freq . o f Samplin g Type o f Analysi s Particulat e HC , CO , CO . & Inert s N O Odo r X Colo r Ven tStack s Numbe r Heigh t Diamete r Exi tGa s Temp. , ° F SCF M pe rstac k( a ) Emissio n Contro l Devic e Demiste r Condense r Other s Tots l Emission s Hydrocarbon s Particulate s N0 X S0 X C O 51- 3 196 5 87.50 0 N o Seasona l Variatio n

16,00 0

Absorbe r Ven t 225,00 0 Continuou s

0.45 0 0.18 7 0.00 1 0.00 8 0.05 0 0.03 5 0.00 6 Absorbe rVen t (Durin g Start-up ) N . A . (q ) Intermitten t 1 5

0.26 4
0.21 6 0.00 8

9.13 3 0.85 6
0.38 3 Absorbe rVen tSampl e Lin e t o Groun d Leve l A N onc e ever y thre e months , othe rH.C . muc h les s frequen t Non e G.C . Non e N o proble m

200'0 " 2'6 " 10 5 50,00 0 Flar e 4,10 0 Continuou s

N o proble m
1 200'0 " 2 "6 " Flsro e <120 0 < k )

Flar e (Distillatio n Lt . Ends) , 2 Incinerato r(By-product s ( 1 ) 0.10 1
0.02 6 0.18 7 Incinerato r Flu e Ga s 400,00 0 (Max. ) <J > Intermitten t

X X

X Non e No t Sample d Non e X X 0.02 6
X Non e No t Sample s Non e

No proble m


### 1 104'0 " 9'0 " 160 0 88,00 0 (Max. ) ( J >TABL EAN-3 A SURVE Y O FU
. S

. ACRYLONITRIL EPLANTS AN D ATMOSPHERIC EMISSION S FRO M THES EFACILITIE S Shee t 4 o f 6 Plan t Cod e Numbe r Dat e on-stream Capacity , Ton s o f

Acrylonitrile/Yr . Averag e Production , Tons/Yr . Rang e I n Production , 7 . o f Max . Operatin g Range , 7 . o f Max . Prod . By-product s (Net ) HCN, Tons/Yr . Acetonitrile , Tons/Yr . Oil s & Polymers , Tons/Yr . Emission s t o Atmospher e Stream Flow , (a ) Lbs./Hr . Flow Characteristi c i f Intermitten t - Hrs./Yr . o f Flow Composition , Tons/To nAcrylonitril e Particulat e Carbo nDioxid e .Carbo nMonoxid e Ammoni a Methan e Ethan e & Ethylen e Propylen e Propan e Hydrocyani c Aci d Acrylonitrile(AN ) Acetonitril e (ACN ) Oxygenate dHydrocarbon s Nitroge n Oxyge n Sulfu r Oxide s Nitroge nOxide s Wate r Sampl e Ta pLocatio n Dat e o r Freq . o f Samplin g Typ e o f Analysi s Particulat e HC , CO , 

## N° x Odo r Colo r Ven t Stack s Numbe r Heigh t Diamete r Exi t Ga s Temp. , ° F SCF M pe r stac k *•• ) Emissio nContro l Devic e Demlste r Condense r Other s Tota l Emission s Hydrocarbon s Particulate s NO , SO x C O CO , an

dInert s 51- 4 197 0 110,00 0 110.00 0 Virtuall y

N o Seasona l Variatio n
20,00 0

Absorbe r Ven t 300,00 0 Continuou s Absorbe r Ven t (Durin g Start-up ) N . A . Intermitten t 2 0.00 1 0.35 0 0.16 7

0.00 1 0.05 0 0.03 5 0.00 4 0.00 9 0.00 3 0.000 4 8.77 4 0.76 3 (m )

0.78 7 Absorbe r Ven t Sampl e Lin e t o Cround Leve l Onc e a Wee k
Non e GL C NH 3 + HCN

b y Titratio n N o problem
1 224'0 " 3'0 " 11 3 69,00 0 Incinerato r Flue Ca s 98,00 0 Variabl e O )

0.31 7

2.29 0

0.000 4 (r ) 0.70 9 Sampl e Ta pAvail . Neve r Sampled Non e

No proble

m Produc t Recover y Flar e Ven t 2,50 0 Continuou s

0.01 8

1 lOO'O " 7'6 " 160 0 21,00 0 ( D

Incinerato r (Distillatio nLt . End s ^') , 2 Flare s

0.10 2 0.000 4 0.16 7 0.06 7

0.0000 1 < r > 0.00 5 Non e Neve r Sample d Non e

No proble m

150'0 " 1'4 " 54 0 HCN Storag e Flar e Ven t 75 0 Continuou s

0.00 4

0 02 0

0 0000 1 (D 0 00 2 Non e Neve r Sample d Non e

N o probl e

1 lOO'O " 6 " 17 0

4 — ^ 1

## P. 8 

# y i 

# r AN-1 4

Tabl e AN-3 A

Footnote s Shee t 5 o f 6 (a ) We t ga s flo

w rat e base do

nacrylonitril e averag e productio nrat e i f available , otherwis e base do ndesig ncapacity . (b ) Assume dcompositio no f "miscellaneous " component . (c ) Air . (d ) Onl y

acrylonitril e (AN ) i nabsorbe r ven t ga s i s measure ddirectl y (b y ga s chromatograph) . Flo w an dcompositio nar e calculate dvalue s base do n measure dflows o f air , propylen e an dammoni a int o th e proces s an

do n analysi s o f th

e reacto r effluent . Thi s analysi s i s b y a combinatio n o f we t chemistry , physica l separatio nan dchromatographi c techniques . (e ) Analyze dfor N0 X

## pe r metho d7 - Determination s o f Nitroge nOxid e fro m Stationar y

Sources , Federa l Register , vol . 36 , No . 247 , Decembe r 23 , 1971 . HC N an dNH 3 b

y Draege r tubes . (f ) Ga s strea

m i s scrubbed . Scrubbe r solutio ni s analyse dfor HCN 'silve r nitrat e titration ) A N an dAC N (b y gas-liqui dchromatography) . Scrubbe dga s i s analyse dfor othe r component s b y chromatograph (N 2 b y difference) , (g ) Flo

w rat e an

dcompositio nbase donburnin g approximatel y 407 , o f by-produc t HCN . Incinerato r designe dt o bur nal l by-product s an d19 0 gp

m o f wast e water . Presentl y al l wast e wate r (30 0 gpm ) plu s a majo r portio no f the by-produc t AC N

ar e sen t t o dee pwel l disposal . (h ) Shel l procedur e for sulfur oxides . (i ) Compan

y als o ha s a 92,50 0 TP Yplan t a t som e location . Approximat e emission s for thi s uni t ar e a direc t proratio no f value s show nfor th

e slightl y large r plant . (j ) No norma l flow . Incinerato r onl y useddurin g emergenc y period s whe n wast e was hwate r streams containin g (NHA^SO/H , 

## an dby-produc t AC N

ar e diverte dfro

m dee pwel l disposa l (onc e a year) - an dHC N canno t be sen t

. , t o storag e (almos t n o chanc e o f thi s occurring) . (k ) Maximu

m flo w o f 58,00 0 SCF M

durin g emergency . Thi s include s combustio n o f fee dpropylen e (0.33 1 tons/to nAN ) whe nsourc e o f hea t fo r propylen e vaporizatio ni s los t (occur s abou t onc e every tw o year s fo r tw

o hours) . Als o durin g schedule d shut-dow nvaporizer s ar e vente dt o flare . Thi s ven t i s abou t 257 , o f emergenc y flow . (1 ) Represent s norma l flo w fro m burnin g som

e by-produc t nitroge ncompound s rejecte di nproduc t recovery sectio nincludin g 5 0 tons/mont hHCN . Occasionall y

durin g proces s upset s tota l by-produc t HC N i s sen t t o thi s incineration . Whe nthi s occur s flo w i s increase dto 95,00 0 SCFM . O n anaverag e 10 0 tons/mont ho f HCN i s burne di nthi s incinerator . (m ) Compositio ni s approximatel y 4 9 wt . 7

„ acetaldehyde , 327 , aceton e an d19 % acrolein . (n ) Include s 0.00 5 tons/to no f miscellaneou s compound s no t identified .

## P. 9 

# AN-1 5

v . * Tabl e AN-3 A

Footnote s (Continued ) Shee t 6 o f 6 (o ) Thi s conditio nrepresent s th e operatio ndurin g start-u po f on e reactor . Whil e flow

conditio nan

dcompositio nchang e durin g the start-up , thes e dat a represen t averag e values . Start-u ptim e normall y

require s a maximu

m o f on e hour . Dat a show ni s for start-u po f on e reacto r o f a tw o reacto r plant . I f othe r reacto r i s on-stream tota l ven t wil l contai nindicate d flo w plu s 507 . o f norma l absorbe r ven t show ni nprecedin g column . Onan average , eigh t reacto r start-up s pe r yea r ar e expected . (p ) I naddition , HC N i s diverte dfro

m incinerator s t o flar e abou t onc e a year . Propylen e storag e tank s reliev e t o flar e oninfrequen t basis . 0 

# (q ) Same a s commen t (o ) excep t thi s plan t ha s five reactors . I f othe r reactor s ar e on-stream , tota l ven t wil l contai nindicate dflow plu s 807 , o f norma l i absorbe r ven t show ni nprecedin g column . (r ) Calculate dvalu e base do nU . S . Dept . o f HE W factor s fo r calculatin g emission s fro

m burnin g natura l gas . (s ) I nthe nea r futur e al l by-produc t HC N wil l b e burned . r - (t ) Flow

base do nburnin g al l by-produc t HC N an dACN .



# r I t shoul db e note dtha t flow rate s an

dcomposition s show

nfo r intermitten t \__ stream s represen t emission s durin g flowin g conditio nan dno t yearl y

average d^ values. t 

# Th e tota l plan t emissio nfigure s show nqr e average demission s fo r r 

# extende dperiod s o f operation . ;