OAR Box 1851 

Prepped by Keeia Richards 

Document Number: 

32) ll-A-6 

Docket Number: 

A-90-19 

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

p.1 
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A-90-19 

ll-A-6 

EPA-450/3-73-OO6-D 

t_tl_* 

ENGINEERING 

AND COST STUD 

OF AIR POLLUTION CONTROL 

H FOR THE 

r PETROCHEMICAL INDUSTRY 

VOLUME 2: ACRYLONITRILE 

J MANUFACTURE 

J - > ' 

' b y 

J 

| . W.A. Schwartz , F.B . Higgins, Jr . , 

J. A. Lee, R. Newirth, and J. W. Pervie r 

Houdry Division 

Air Products and Chemicals, Inc . 

P . O. Box 427 

Marcus Hook, Pennsylvania 19061 

Contract No. 68-02-0255 

EPA Project Officer: Leslie B . Evans 

Prepare d for 

ENVIRONMENTAL PROTECTION AGENCY 

Office of Air and Waste Management 

Office of Air'Quality Planning and Standards 

Research,Triangle Park , N. C. 27711 

February 1975 
This report is issued by the Environmental Protection Agency to report 

technical data of interest to a limited number of readers. Copies are 

available free of charge to Federal employees, current contractors and 

grantees, and nonprofit organizations - as suppiles permit - from the Air 

Pollution Technical Information Center, Environmental Protection Agency, 

Research Triangle Park, North Carolina 27711; or, for a fee, from the 

National Technical Information Service, 5285 Port Royal Road, Springfield, 

Virginia 22161. 

This report was furnished to the Environmental Protection Agency by 

the Houdry Division of Air Products and Chemicals, Inc. , in fulfillment 

of Contract No. 68-02-0255. The contents of this report are reproduced 

herein as received from the Houdry Division of Air Products and Chemicals, 

Inc. The opinions, findings, and conclusions expressed are those of 

the author and not necessarily those of the Environmental Protection 

Agency. Mention of company or product names is not to be considered 

as an endorsement by the Environmental Protection Agency. 

Publication No. EPA-450/3-73-006-b 

n 
1 I 1 . 1 ,_ L 

° 

Plant Code Number 

Date on-stream 

Capacity , Tons of Aerylonitrile/Yr . 

Average Production, Tons/Yr. 

Range in Production, 7. of Max. 

Operating Kange, % of Max. Prod. 

By-products (Net) 

HCN, Tons/Yr. 

Oils & Polymers, Tons/Yr. 

Emissions t o Atmosphere 

Stream 

Flow, (a) Lbs./Hr . 

Flov Characteristi c 

If Intermittent - Hrs./Yr . of Flow 

Composition, Tons/Ton Aerylonitrll e 

Particulat e 

Carbon Dioxide 

Carbon Monoxide 

Ammonia 

Methane 

Ethane & Ethylene 

Propylene 

Propane 

H—Irocyanle _s_ t 

Acrylonltrll e (AN) 

Acetonltrll e (ACN) 

Oxygenated Hydrocarbons 

' Nitrogen 

Oxygen 

Sulfur Oxides 

Nitrogen Oxides 

Water 

Sample Tap Location 

• Date or Freq. of Sampling 

Type of Analysis 

Particulat e 

HC, CO, C02 & InertB 

NOx Odor 

Color 

Vent Stacks 

' Number 

Height 

Diameter 

SCFM per stack <a) 

Emission Control Device 

Demister 

Condenser 

Others 

Totsl Emissions 

Hydrocarbons 

. Particulate s 

NO, 

SO, 

CO 

TABLE "AN-3A 

SURVEY OF U. S. ACRYLONITRILE PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

> 

51-1 

1965 

100,000 (1) 

100,000 

No Seasonal variatio n 

'50-100 

i s) 

\ 20,00 0 

4,00 0 

0

 4,00 0 

Absorber Vent Absorber Vent 

(During Start-up ) 

285,00 0 62,500 <-o) 

Continuous Intermittent 

8 

. TK 

0.29 4 . 0.05 0 

0.18 0 f • .' 0.032 

o 0.03 2 

0.04 7 " 0.00 8 

0.12 4 0.03 0 <") 

0.00 2 <b> 0.004 

0.02 9 0.225 

0.00 6 <b> 0.00 8 

9.72 6 1.676 

0.86 5 . 0.245 

0.605 0.305 

Accessibl e Sample Line from Reactgr Effluen t Ducts 

»- Continuous For AN other s twic e a week Cont. Monitor of O, 

Calc'd 

None 

(d) 

None 

Essentiall y Odorless Sligh t Odor 

Appearance of steam, No Residua l Plume 

1 

200"0" 

2'6 " 

120 450 

64,600 14,300 

X 

Sheet 

Product 

Fractionato r Vent 

110 

Continuous 

0.000 4

 (b ) 

0.000 3 <b> 

0.00 4

 (c ) 

* 

Elevated f. 

Difficul t t o Reach 

None 

Calc'd 

Unknown 

1 

58'0 " 

2" 

100 

25 

X 

Flar e (Distillatio n Lt. Ends) Incinerato r (By-product HCN 6. ACN) 

0.209 

TR 

0.007 

0. 180 

o£ 6 

Incinerato r 

Flue Cas 

110,00 0 f > 

Continuous 

TR 

X 

0.000 3 

0.0000 2 

X 

0.007 3 

X 

Sample Line 

t o Ground Leve l 

Twice a Month 

None 

( e ) 

( e ) o 

None 

Smokeless 

« 

1 

135'0" 

6'0" 

1600 

24,00 0 

^ T ^ T "" 

• 

Flar e 

./£. 1.300 

Variabl e 

X 

£ 

r— 

o 

X 

X 

X 

None 

Calc'd 

None 

Smokeless 

1 

275'0 " 

1'8" 

>1500 

ai26 5 
TABLE AN-3A 

SURVEY OF U. S. ACRYLONITRILE PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES Sheet 2 of 6 

Plant Code Number 51-2 

Date on-stream 

Capacity, Tons of Acrylonitrile/Yr . 

Average Production, Tons/Yr. 

Range in Production, 7. of Max. 

Operating flange, '/. of Max. Prod. 

By-products (Net) 

HCN, Tons/Yr. 

Acetonitrile , Tons/Yr . 

Oils & Polymers, Tons/Yr. 

Emissions t o Atmosphere 

Stream 

Flow, <•*> Lbs./Hr. 

Flow Characteristic 

. if Intermittent - Hrs./Yr. of Flow 

Composition, Tons/Ton Acrylonitrile 

particulate 

Carbon Dioxide 

Carbon Monoxide 

Ammonia 

Methane 

Ethane & Ethylene 

Propylene 

Propane 

Hydrocyanic Acid 

Acrylonitrile (AN) 

Acetonitrile (ACN) 

Oxygenated Hydrocarbons 

Nitrogen 

Oxygen 

Sulfur Oxides 

Nitrogen Oxides 

Water 

Sample Tap Location 

Date or Freq. of Sampling 

Type of Analysts 

Particulate 

HC, CO, C02 & Inerts 

N0X 

Odor 

Color 

Vent Stacks 

Number 

Height 

Diameter 

Exit Cas Temp., °F 

SCFM per stack <a> 

Emission Control Device 

Demister 

Condenser 

Others 

Total Emissions 

Hydrocarbons b 

Particulates 

NOx • 

SO, 

CO 

1965 

125.000 

100,000 

No Seasonal Variation 

7,000 

3,200 

Absorber Vent 

200,000 

Continuous 

0.508 

0.178 

0.052 

0.144 

0.0005 

0.0004 

0.008 

7.222 

0. 303 

Absorber Vent 

Nitrogen Comp'd. once a week, others in 1971 

None 

50,000 

i None 

CLC.*" 

Silver ! Nitrat e 

1 „' -

•. ', 200'0" 

2'6 " 

% 110 • 

Titratio n (f "* 

O 

Absorber Vent 

(During Start-up) 

140,000 <°> 

Intermittent 

6-8 

0.080 

0.040 

0.026 

0.027 

0.034 

0. 608 

0.017 

5.185 

0.218 

30*000 

Incinerato r 

Flue Gas (K ) 

46,70 0 

Cont i nuous 

O. 282 

« 0.00000 1 

1 

0 

0 

0 

251 

174 

00001 

160 

Used 130' crane 

M< irch. 1971 

None 

CLC <f> '"> 

Silve r Nitrat e Titratio n ' f^ 

None 

1 

lOO'O" 

12'0 " 

1.60 0 

10,35 0 

Flare (Distillatio n Lt. F.nds * p ) , 2 Incinerator s (by-product HCN & ACN) 

0.206 

0.0000 1 

I 

0.17 8 

Flar e 

?,650 

Intermitten t 

0 014 

0.078 

0.002 

TR 

0 Oil 

None 

Calc'd 

1 

JOO'0" 

2'0 " 

1.000 

^60 0 

TJ 

Ul 
TABLE AN-3A 

SURVEY OF U. S. ACRYLONITRILE PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES Shee t 3 of 6 

Plant Code Number 

Date -on-stresm 

Capacity, Tons of Aerylonitrile/Yr . 

Average Production, Tons/Yr. 

Range in Production, X of Max. 

Operating Range, X o f Max. Prod. 

By-products (Net,) 

HCN, Tons/Yr. 

Acetonitrile , Tons/Yr . 

0il 6 & Polymers, Ton6/Yr. 

Emissions to Atmosphere 

Stream 

Flow,

 (a ) Lbs./Hr. 

Flow Characteristic 

if Intermittent - Hrs./Yr. of Flow 

Composition, Tons/Ton Acrylonitrile 

Particulate 

Carbon Dioxide 

Carbon Monoxide 

Ammonia 

Methane 

Ethane & Ethylene 

Propylene 

Propane 

Hydrocyanic Acid 

Acrylonitrile (AN) 

Acetonitrile (ACN) 

Oxygenated Hydrocarbons 

Nitrogen 

Oxygen 

Sulfur Oxides 

Nitrogen Oxides 

Water 

Sample Tap Location 

Date or Freq. of Sampling 

Type of Analysis 

Particulate 

HC, CO, CO. & Inerts 

NO 

Odor

 X 

Color 

Vent Stacks 

Number 

Height 

Diameter 

Exit Gas Temp., °F 

SCFM per stack ( a) 

Emission Control Device 

Demister 

Condenser 

Others 

Totsl Emissions 

Hydrocarbons 

Particulate s 

N0X 

S0X 

CO 

51-3 

1965 

87.500 

No Seasonal Variation 

16,000 

Absorber Vent 

225,000 

Continuous 

0.450 

0.187 

0.001 

0.008 

0.050 

0.035 

0.006 

Absorber Vent 

(During Start-up ) 

N. A. (q) 

Intermitten t 

15 

0.264 

0.21 6 

0.00 8 

9.133 

0.856 

0.383 

Absorber Vent Sample 

Line t o Ground Leve l 

AN once every thre e months, othe r H.C. much less frequent 

None 

G.C. 

None 

No problem 

200'0 " 

2'6 " 

105 

50,00 0 

Flar e 

4,10 0 

Continuous 

No problem 

1 

200'0" 

2 "6" 

Flsroe 

<120 0 < k ) 

Flar e (Distillatio n Lt. Ends), 2 Incinerato r (By-products

 ( 1

 ) 

0.10 1 

0.026 

0.187 

Incinerator 

Flue Gas 

400,000 (Max.) <J> 

Intermittent 

X 

X 

X 

None 

Not Sampled 

None 

X 

X 

0.026 

X 

None 

Not Samples 

None 

No problem 

1 

104'0" 

9'0" 

1600 

88,000 (Max.)

 (J> 
TABLE AN-3A 

SURVEY OF U. S. ACRYLONITRILE PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES Sheet 4 of 6 

Plant Code Number 

Date on-stream 

Capacity , Tons of Acrylonitrile/Yr . 

Average Production, Tons/Yr. 

Range In Production, 7. of Max. 

Operating Range, 7. of Max. Prod. 

By-products (Net) 

HCN, Tons/Yr. 

Acetonitrile, Tons/Yr. 

Oils & Polymers, Tons/Yr. 

Emissions to Atmosphere 

Stream 

Flow, 

(a) Lbs./Hr. 

Flow Characteristic 

if Intermittent - Hrs./Yr. of Flow 

Composition, Tons/Ton Acrylonitrile 

Particulate 

Carbon Dioxide 

.Carbon Monoxide 

Ammonia 

Methane 

Ethane & Ethylene 

Propylene 

Propane 

Hydrocyanic Acid 

Acrylonitrile(AN) 

Acetonitrile (ACN) 

Oxygenated Hydrocarbons 

Nitrogen 

Oxygen 

Sulfur Oxides 

Nitrogen Oxides 

Water 

Sample Tap Location 

Date or Freq. of Sampling 

Type of Analysis 

Particulate 

HC, CO, 

N°x 

Odor 

Color 

Vent Stacks 

Number 

Height 

Diameter 

Exit Gas Temp., °F 

SCFM per stack *••) 

Emission Control Device 

Demlster 

Condenser 

Others 

Total Emissions 

Hydrocarbons 

Particulates 

NO, 

SOx 

CO 

CO, and Inerts 

51-4 

1970 

110,000 

110.000 

Virtually No Seasonal Variation 

20,000 

Absorber Vent 

300,000 

Continuous 

Absorber Vent 

(During Start-up) 

N. A. 

Intermittent 

2 

0.001 

0.350 

0.167 

0.001 

0.050 

0.035 

0.004 

0.009 

0.003 

0.0004 

8.774 

0.763 

(m) 

0.787 

Absorber Vent Sample 

Line to Cround Level 

Once a Week 

None 

GLC 

NH3 + HCN by Titration 

No problem 

1 

224'0" 

3'0" 

113 

69,000 

Incinerator 

Flue Cas 

98,000 

Variable O ) 

0.317 

2.290 

0.0004

 (r ) 

0.709 

Sample Tap Avail. 

Never Sampled 

None 

No problem 

Product Recovery 

Flare Vent 

2,500 

Continuous 

0.018 

1 

lOO'O" 

7'6" 

1600 

21,000 (D 

Incinerator (Distillation Lt. Ends ^') , 2 Flares 

0.102 

0.0004 

0.167 

0.067 

0.00001 <r> 

0.005 

None 

Never Sampled 

None 

No problem 

150'0" 

1'4" 

540 

HCN Storage 

Flare Vent 

750 

Continuous 

0.004 

0 020 

0 00001 (D 

0 002 

None 

Never Sampled 

None 

No proble 

1 

lOO'O" 

6" 

170 

4 — ^1 
P.8 

y 

i r 

AN-14 

Table AN-3A Footnotes Sheet 5 of 6 

(a) Wet gas flow rate based on acrylonitrile average production rate if 

available, otherwise based on design capacity. 

(b) Assumed composition of "miscellaneous" component. 

(c) Air. 

(d) Only acrylonitrile (AN) in absorber vent gas is measured directly (by 

gas chromatograph). Flow and composition are calculated values based on 

measured flows of air, propylene and ammonia into the process and on 

analysis of the reactor effluent. This analysis is by a combination 

of wet chemistry, physical separation and chromatographic techniques. 

(e) Analyzed for N0X per method 7 - Determinations of Nitrogen Oxide from 

Stationary Sources, Federal Register, vol. 36, No. 247, December 23, 1971. 

HCN and NH3 by Draeger tubes. 

(f) Gas stream is scrubbed. Scrubber solution is analysed for HCN 'silver 

nitrate titration) AN and ACN (by gas-liquid chromatography). 

Scrubbed gas is analysed for other components by chromatograph 

(N2 by difference), 

(g) Flow rate and composition based on burning approximately 407, of by-product 

HCN. Incinerator designed to burn all by-products and 190 gpm of waste 

water. Presently all waste water (300 gpm) plus a major portion of the 

by-product ACN are sent to deep well disposal. 

(h) Shell procedure for sulfur oxides. 

(i) Company also has a 92,500 TPY plant at some location. Approximate emissions 

for this unit are a direct proration of values shown for the slightly 

larger plant. 

(j) No normal flow. Incinerator only used during emergency periods when 

waste wash water streams containing (NHA^SO/H, and by-product ACN are 

diverted from deep well disposal (once a year)- and HCN can not be sent 

. , to storage (almost no chance of this occurring). 

(k) Maximum flow of 58,000 SCFM during emergency. This includes combustion 

of feed propylene (0.331 tons/ton AN) when source of heat for propylene 

vaporization is lost (occurs about once every two years for two hours). 

Also during scheduled shut-down vaporizers are vented to flare. This 

vent is about 257, of emergency flow. 

(1) Represents normal flow from burning some by-product nitrogen compounds 

rejected in product recovery section including 50 tons/month HCN. 

Occasionally during process upsets total by-product HCN is sent to this 

incineration. When this occurs flow is increased to 95,000 SCFM. On 

an average 100 tons/month of HCN is burned in this incinerator. 

(m) Composition is approximately 49 wt. 7„ acetaldehyde, 327, acetone and 19% 

acrolein. 

(n) Includes 0.005 tons/ton of miscellaneous compounds not identified. 
P.9 

AN-15 

v. 

* Table AN-3A Footnotes (Continued) Sheet 6 of 6 

(o) This condition represents the operation during start-up of one reactor. 

While flow condition and composition change during the start-up, these 

data represent average values. Start-up time normally requires a maximum 

of one hour. Data shown is for start-up of one reactor of a two reactor 

plant. If other reactor is on-stream total vent will contain indicated 

flow plus 507. of normal absorber vent shown in preceding column. On an 

average, eight reactor start-ups per year are expected. 

(p) In addition, HCN is diverted from incinerators to flare about once a year. 

Propylene storage tanks relieve to flare on infrequent basis. 

0 

(q) Same as comment (o) except this plant has five reactors. If other reactors 

are on-stream, total vent will contain indicated flow plus 807, of normal 

i absorber vent shown in preceding column. 

(r) Calculated value based on U. S. Dept. of HEW factors for calculating 

emissions from burning natural gas. 

(s) In the near future all by-product HCN will be burned. r-

(t) Flow based on burning all by-product HCN and ACN. 

r 

It should be noted that flow rates and compositions shown for intermittent \__ 

streams represent emissions during flowing condition and not yearly averaged ^ 

values.t The total plant emission figures shown qre averaged emissions for r 

extended periods of operation. ;