P.1 

OAR Box 1851 

Prepped by Keeia Richards 

Document Number: 

31) ll-A-5 

Docket Number: 

A-90-19 

Printed 11/19/200811:19:51 AM Sheet 31 of 41 
P.2 

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A-90-19 

ll-A-5 

ENGINEERING AND COST STUDY 

OF AIR POLLUTION CONTROL 

FOR THE PETROCHEMICAL 

INDUSTRY VOLUME 3: 

ETHYLENE DICHLORIDE 

MANUFACTURE 

BY OXYCHLORINATIQfliTTP 

; . _ • s- -

ll_i! 

by 

FPA AIR DOCKET 

W. A. Schwartz, F. G. Higgins, Jr* 

J. A. Lee, R. Newirth, and J. W. Pervior 

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 

Prepared for 

ENVIRONMENTAL PROTECTION AGENCY 

Office of Air and Waste Management 

Office of Air Quality Planning and Standards 

Research Triangle Park, N. C. 27711 

November 1974 

• 

I 
This report is issued by the Environmental Protection Agency to report technical 

data of interest to a limited numbe r of readers. Copies ar e available free 

of charge to Federal employees, current contractors and grantees, and nonprofit 

organizations- as supplies 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. 

•a 

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-C 

tt 

u 

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n 
1 

6 

* Plant Coda »•_• > 

Data oo-etream ' 

Capacity, Tona of Ethylene Dichlorlda/Tr. 

Average Production, Tona EDC/Yr. 

Range In Production, I of Has. 

By-product*. Tona/Yr. 

Mixed Chlorinated HC 

Emission* to Atmoephere 

Stream 

Flow (a), Lba./Hr. 

Plow Charactarlatlca 

If Intermittent, Hra. of Flov/Yr. 

Composition. T/T D C 

Particulate 

Carbon Dioxide 

Carbon Monoxide 

HItrogan 

Oxygen 

Methane 

. Ethylana 

•Ethene 

/Ethylene Dlchlorlde 

Mono & Dlchloroacatylena 

Ethyl Chloride 

Vinyl Chloride 

Dlchloro Ethylene 

Chloroform 

Carbon Tetrachloride 

Water -

Aromatic Solvent 

Chlorine* 

Hydrogen Chloride 

Sample Tap Location 

Data or Frequency of Sampling 

Type of Anelyele 

Odor 

Color 

Vent Stacka 

Nuaber 

Height 

Diameter 

Exit Gee Temp., °P 

SCFM per Stack (a) 

Type of Emission Control 

Date Installed 

'Totel Emlealone, Ton/Ton EDC 

Hydrocarbon* 

Particulate* & Aeroeole

 (b ) 

NO, 

CO 

TABLE ED-3A 

SUK7EO OF u. s. oxYCHLOXiMtiar iur n 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

5t-l 

1968 

236,350 

0 No aaaaonal variation 

•a. 

Preceee Vant Dlatlllatlon Vent 

45,000 1,700 

Contlnuoua Contlnuoua 

0.032 »••• 

0.008 . 

0.710 0.0003

 (c> 

0.018 

0.011 0.00001 

0.006 0.00003 

0.033 0.0002 

0.012 0.0077 

0.008 , 0.0062 

0.0007 

0.0080 

0.0064 

0.0010 

0.0008 

Before 6 efte r contact condenser Accessible 

Continuous for 0 2 . COj 6 C2", other *4 tlmes/Yr. 

HC'e once per day, CO 6 tlmea/Yr. 

C C . C.C. 

Ho—a Not beyond plent boundary 

I 1 

50' 10' 

.1*0" 6" 

. 3 2 80 

9,900 135 

Contact Condenser 

1968 

•i 

0.088 

0.001 

V 

0.008 

*> 

Page 1 pf 7 

32-2 

130,000 

130.000 

No seasonal variation 

Procees Vent 

36.100 

Contlnuoua 

0.03* 

0.008 

* 1.048 

0.007 

0.002 

0.009 

0.004 

Accessible 

Oraat 6/dey,C.C. t/vfc. 

' Oraat 6 C.C. 

None 

1 

27'6" 

8" 

8 0 

8,000 

Condenser 1-10 °Fl 

0.015 

9 

o 

0.008 1 

P.4 
Plent Code Number 

Date on-atrcem 

Capeclty, Tone of Ethylene Dlchlorlde/Yr. 

Average Production, Tone EDC/Yr. 

Renge In Production, X of Mas. 

By-producta, Tona/Yr. 

Mixed Chlorinated HC 

Emissions to Atmosphere 

Stream 

Flov (a), Lbs./Hr. 

Flow Cherecterlsttcs 

if Intermittent, Hra. of Flov/Yr. 

Composition. T/T EDC 

Particulate 

Carbon Dioxide 

Carbon Monoxide 

Nitrogen 

Oxygon 

Methane 

Ethylana 

Ethane 

Ethylene Dlchlorlde 

Mono & Dlchloroacatylena 

Ethyl Chloride 

Vinyl Chloride 

Dlchloro Ethylene 

Chloroform 

Carbon Tetrachloride 

Veter 

Aromatic Solvent 

Chlorine 

Hydrogen Chloride 

Sample Tap Location 

Date or Frequency of Sampling 

Type of Analysis 

Odor 

Color 

Vent Stecke 

Number 

Height 

Diameter 

Exit Gas Temp., °F 

SCFM per Steck <•) 

Type of Emission Control 

Date Instslled 

. Total Emissions, Ton/Ton EDC 

Hydrocarbons 

Particulates & Aeroeols <b> 

N0„ 

• SO, 

* CO 

TABLE ED-3A CONT'IT. 

Sl'RVEY OF U. S. OXYCHLORINATION PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

52- 3 

1968 

115,000 

115,000 

No sessonal varletlon 

Process Vent 

18.300 

Continuous 

0.010 

0.005 

0.604 

0.019 

0.005 

0.008 

0.017 

0.011 

TR <«> 

None after scrubber, ecceaslble tap before scrubber 

Scrubber feed 3-6 tlmeo/yr. 

C.C. 

Occeslonal HCl 

I 

76-

l" . ; 

80 

3.980 . 

Scrubber 

1968 -1971 

Caustic Scrubber Vent 

90 

Continuous 

0.00001 

0.00003 

0.00118 

0.00008 

0.00012 

0.00015 

0.00144 

0.00014 

0.00001 

0.00001 

0.00002 

0.00003 

Page 2 of 7 

0.044 

0.005 

DrylnR ToverOvri'd. 

12 

_ Continuous 

0.00001 

0.00002 

0.00007 

0.00001 

0.00016 

0.00017 

Condenser 

1972 

Emergency Vent 

17200 

Intermittent 

6 

0.0045 

0.0023 

0.2652 

0.0085 

0020 

.0034 

0.0076 

0.0049 

0.00009 

No probl 

Tvlce in 

C.C. 

None 

1 

49' 

2

n 

100 

13 

em 

Dec. 1971 

Access 

Not ss 

None 

1 

72' 

2" 

60 

2.6 

lbl e 

yet (I, 

0.0004 

Accessibl e 

4 tlsMa recently 

C.C. 

HCl vlthln battery limit 

1 

73' 

7" 

40 

2,000 

— • • *'; «. r—\ 
"__T __J 

I I 

I I _ _ -

Plant Coda 

Date on-stresm 

Cepeclcy, Tons of Ethylene Dlchlorlde/Yr 

Averege Production, Tone EDC/Yr. 

Range in Production. X of Max. 

By-producta, T/T D C 

Mixed Chlorinated BC 

Emissions to Atmoashare 

Stream 

Flov <•>. Lba./Rr. 

Flov Characterletlea 

If Intermittent. Hra. of Flov/Ya. 

Composition, T/T EDC 

Particulate 

Carbon Dioxide 

Carbon Monoxide 

Nitrogen 

Oxygen 

Methane 

Ethylene 

Ethane 

Ethylene Dlchlorlde 

Mono 6 Dlchloroecetylene 

Ethyl Chloride 

Vinyl Chloride 

Dlchloro Ethylene 

Chloroform 

Carbon Tetrechlorlda 

Water 

Aromatic Solvent 

Chlorine 

Hydrogen Chloride 

Sample Top Location 

Date or Frequency of Sampling 

Type of Anelyele 

Odor 

Color 

Vent Stocks 

Number 

He I ght 

Diameter 

Exit Cas Tea*., °F 

SCFM per' Stack 

I'vpe Emi salons Control 

Dete Installed 

Total Emissions, Ton/Ton'EDC 

Hydrocarbons 

Particulates & Aerosols (b) 

NO, 

SO, 

CO 

52- 4 

107.50 0 

TABLE ED-3A CONT'D. 

SURVEY OF U. S. OXYCHLDRI NATION PLAnTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

52-5 

1963 

Page 3 of 7 

2nd quarter 201 belov eve. 

4th " " above ava. 

Absorber Vent 

33,800 

Contlnuoua 

0.06 8 

0.01 2 

1.025 

0.10 0 

0.03 8 

0.00 6 

0.022 (D 

0.0004 

Piped t o continuou s analyse r 

Every 13 minute s 

C.C. 

Nona 

1 

175 ' 

8" 

50 

7,50 0 

(n) 

0.02 8 

0.012 

330.00 0 

No aaaaonal variatio n 

0.007 5 (J) 

Abaorber Vent Absorbe r Vent Waste Water Strippe r Ovh'd. Waste Water Strippe r Ovh'd. 

71.00 0 31,00 0 77 25 

Continuous Continuous Contlnuoua Contlnuoua 

Heede Column Vent 

0.025 . 

0.006 

0.748 

0.071 

0.008 

0.004 

0.001 

0.002 

0.005 

0.002 

0.330 

0.033 

0.004 

0.002 

0.001 

0.0003 

X . 

X 

X 

0.00003 

> 0.00036 

0.0005 

Accessible 

4 per hour 

C.C. 

No problem 

1 

150' 

l'O" 

65 

15.90 0 

Demi ate r 

1963 

0.0002 

Accessible 

4 per hour 

C.C. 

No problem 

1 

150" 

1'2" 

70 

6.95 0 

Demi ste r 

1967 

0.000006 

None 

Never sampled 

None 

No problem 

1 

40' 

2" 

55 

12.5 

Refrlg . Cond. 

1963 

0.01 1 

0.008 

0.0000 5 

0.0000 5 

0.000002 

None 

Never aampled 

None 

No problem 

1 

5 0 ' 

3 " 

55 

5 

Refrlg . Cond. 

1967 

120 

Contlnuoua 

0.0002 

None 

Neve r sempled 

None 

No problem 

1 

150 ' 

2" 

55 

17 

Refrlg . Cond. 

1966 
. • 

Plant Code Number 

Dete on-atreem 

Capeclty , Tons of Ethylene Dlchlorlde/Yr . 

Averege Production, Tons EDC/Yr. 

Renge In Production, X o f Max. 

By-producta, T/T EDC 

Mixed Chlorinated HC 

Emissions t o Atmoephere 

Stream 

Flo v <•>, Lbs./Hr . 

Flov Characterlatlc a 

If Intermittent , Hrs. o f Flov/Tr . 

Composition, T/T EDC 

Particulat e 

Carbon Dioxide 

Carbon Monoxide 

Nitrogen 

Oxygen 

Methane 

Ethylene 

Ethana 

Ethylene Dlchlorld e 

Mono 6 Dlchloroacetylen e 

Ethyl Chloride 

Vinyl Chloride 

Dlchlor o Ethylana 

Chloroform 

Carbon Tetrechlorld e 

Water 

Aromatic Solven t 

Chlorine 

Hydrogen Chloride 

Sampl* Tap Location 

Dete or Frequency of Sampling 

Type of Analyal a 

Odor 

Color 

Vent Stacka 

Number 

Height 

Diameter 

Exit Gea Temp., °F 

SCFM per Stack 

Type EaUeslona Control 

Dete Inetelle d 

Tote l Emisalona, Ton/Ton EDC 

Hydrocarbons 

Partlculate e 6 aerosols

 ( ' 

SO, 

CO 

TABLE ED-3A CONT'D. 

SURVEY OF U. S. OXYCHLORINATION PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

52- 6 

1968 

85,00 0 

1st quarte r 20X belo v eve . 

2nd " ebove ev e 

Absorber Vent Strippe r Vent Heeds Coluan Vent 

21,20 0 245 120 

Contlnuoue Contlnuoua Contlnuoua 

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 0023 

0.00 9 0.008 3 0.000 4 

0.00 3 0.000 1 

Piped t o contlnuou e enelyser . None None 

O2 - Continuoua, Othera ever y 13 mln. Never eenpled Never aempled 

Ethylen e contlnuou e 

C.C. + IH fo r ethylen e . None None 

Nona None None 

1 ' 1 1 

6 5 ' 35 ' 35 ' 

6" . 4" 2 " 

55 100 100 

4.66 0 ' 67 18. 5 

Deulatei- U Separato r 

1968 

0.02 0 

N i l 

0.01 3 

* — 

Pege 4 o f 7 

Emergency Vent 

22,20 0 

Intermitten t 

180 

N il 

1.038 3

 (d ) 

0.026 2 

0.000 1

 (k) 

0.081 1 

0 0011 

None 

Never se—pled 

None 

None 

1 

5 0 ' 

8" 

50 

4.78 0 

-

? 

a— 

Ls» 
B _ _ 

I 

• 

H Plant Code Number 

_ • Det e on-stree m 

H Cepaclty . Tona of Ethylene Dlchlorlde/Yr , 

BJ Averege Production, Tone EDC/Yr. 

BJ Renge In Production, X of Max. 

• By-products, t/ T EDC 

• Mixed Chlorinated HC 

B Emlealona t o Atmosphere 

• Stream 

• Flo v <•>. Lba./Rr . 

1 Flo v Characterletl c 

• If Intermittent, Rre. o f Flov/Tr . 

• Compoaltlon, T/T EDC 

1 Particulat e 

B Carbon Dioxide 

B Carbon Monoxide 

H Nitroge n 

B J Oxygen 

H Methane 

H Ethylen e 

BJ Ethane 

B Ethylene Dlchlorlde 

B Mono 6 Dlchloroecetylen e 

• Ethyl Chloride 

1 Vinyl Chloride 

B Dlchlor o Ethylene 

B Chloroform 

B Carbon Tetrachlorid e 

B Vote r 

1 Aromatic Solvent 

H Chlorine 

H Hydrogen Chloride 

• Sample Tap Location 

1 Det e or Frequency of Sempllng 

• 1 Type o f Analysis 

B Odor 

BN Color 

• Vent Steck e 

B Number 

• Height 

B Diameter 

fl Exit Gee Temp., °F 

B SCFM per Stock (al 

B Type of Emissions Control 

B Det e Installe d 

B Tota l Emissions, T/T EDC 

B j Hydrocarbons 

B Psrticulste s & Aerosols <b> 

1 

! f 

TABLE ED-3A CONT'D. 

SURVEY OF U. S. OXYCHLORINATION PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

32- 7 

1971 

287,00 0 

45.20 0 <l> 

Contlnuoua 

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 

Scrubber Feed - Continuous 

Scrubbe r Vent - Continuous for CI2 

G.C. & Ultrevlole t Spec . 

Not beyond plent boundary - Clj & HCl

 (ln> 

1 

*» 135 ' 

3 0 " 

Ambient 

10,00 0 <') ' 

Weter Scrubber 

(n) * 

0.01 3 

0.00 4 

0 

52- 8 

246.00 0 

36.20 0 (l> 

Contlnuoua 

0.00 7 

0.004 ' 

0.54 1 

0.02 3 

. 

0.00 4 

0.00 4 

0.00 5 

0.000 1 

Inconvenient 

Scrubber Feed - Continuous 

Scrubb'er Vent - Very Infrequen t 

C.C. 

Not beyond plent boundary - Clj 6 HCl *"' 

1 

a s 135 ' 

3 0 " 

Ambient 

3.00C O ) 

Weter Scrubber 

(n) 

0.01 3 

• 

0.0O4 

' 1 - I . 

Pege 5 of 7 

52- 9 

50,00 0 

7,700 " ) 

Contlnuoue 

0.00 8 

0.00 4 

0.56 6 

0.02 4 

0.00 4 

0.00 4 

0.00 5 

0.000 2 

Inconvenient 

Scrubber Feed - Contlnuoue 

Scrubber Vent - Very Infreouen t 

cc . 

Not beyond plent boundary - Clj a HCl '• ' 

1 

<» 75 ' 

18 - 24" 

Ambient 

1.700 <*> 

Water Scrubber 

(n) 

0.01 3 

0.00 4 

/ 10-1 «• 
Plant Code Number 

Dete on-streem 

Capacity, Tone of Ethylene Dlchlorlde/Yr. 

Average Production, Tons EDC/Yr. 

Range in Production, X of Max. 

By-producta. T/T EDC 

Mixed Chlorinated HC 

Emissions to Atmosphere 

Stream 

Flov <•>. Lbs./Hr. 

Flov Characterlatlca 

If Intermittent, Hro. of Flov/Yr. 

Composition, T/T EDC 

Particulate 

Carbon Dioxide" 

Carbon Monoxide 

Nitrogen 

Oxygen 

Methane 

. Ethylana 

| Ethane 

1 Ethylene .M<_-e__da 

I Mono 6 Dlchloroacatylene 

( Ethyl Chloride 

i Vinyl Chloride 

Dichloro Ethylene 

Chloroform 

Carbon Tetrechlorlde 

Weter 

Aromatic Solvent 

Chlorine 

Hydrogen Chloride 

Seaple Tap Location 

Date or Frequency of Sampling 

Type of Analyele 

Odor 

Color 

Vent Stecke 

Number 

Height 

Diameter 

Exit Cas Temp., °F 

SCFM per Stock 

Type Emissions Control 

Dete Installed 

Totsl Emissions, Ton/Ton EDC 

Hydrocarbons 

Psrtlculetes 6> Aerosols 

(b) 

NO, 

SO, 

CO 

TABLE ED-3A CONT'D 

SURVEY OF I1. S. OXYCHLORINATION PLANTS 

AND ATMOSPHERIC EMISSIONS FROM THESE FACILITIES 

52-10 

Page 6 of 7 

1967 

118,625 

118.625 

No seaaonal verlatlon 

Process Vent 

1,450 

Continuous 

0.0119 

0.0167 

0.0128 

0.0002 

0.0065 

0007 

0033 

0007 

0002 

srgoocy Vent 

Intermittent 

0 

0 

0 

0 

0.00004 

0.0006 

Vent under vacuum 

Fall of 1971 

C.C. 

EDC vithln bettery limits 

(8) 

Can be done 

Never Sampled 

None 

260 

Scrubber 

1967 

1 

75' 

8" 

75 

(_) 

0.024 

1000

 fh > 

Scrubber 

1967 

TJ 

CO 
J 

P.10 

ED-16 

TABLE ED-3A FOOTNOTES Page 7 of 7 

(a) Based on average production rate if available, otherwise based on design 

capacity. 

(b) Includes HCl and carbon tetrachloride, 

(c) Air. 

(d) Includes oxygen. 

(e) Normal feed to scrubber contains 0.0008 tons HCI/ton EDC. Hovever, during 

reactor 8t«Ft-up (max. 30 min., 24 times per year), feed can contain as 

much as 0.50 tons HCl/ton EDC. During emergency conditions such as 

power failure, when scrubber becomes ineffective, most of this HCl will be 

vented to the atmosphere. Duration is normally 3- 5 minutes required to 

secure plant. 

(f) Recovery unit not put in operation until after plant survey. 

(g) During start-up, feed to scrubber contains 0.163 tons of nitrogen per ton 

of EDC production capacity and 0.106 tons of HCl per ton of EDC. Duration 

is approximately 20 minutes. During emergency venting, the vent contains 

a small amount of organic material. 

(h) Represents nitrogen flow during start-up. 

(i) Absorber-stripper may shut down for undetermined period during which time 

EDC content indent increases to three times value shown. 

(j) Sent to off-site disposal plant. , 

(k) Includes methane and ethane. 

(1) Represents normal flow from EDC unit. Actual total vent from stack 

includes streams from other units in VCM plant. Vent gas composition 

shown is based on analysis of scrubber feed gas from EDC oxychlorination 

unit. It has been assumed that water scrubber removes contained HCl 

(0.00004 T/T EDC). 

(m) Only during plant upset. 

(n) Survey data does not include information regarding air emissions resulting 

from EDC purification. 

It should be noted that flov rates and compositions shovn for intermittent 

streams represent emissions during floving condition and not yearly 

averaged values. The total plant emission figures shovn are averaged 

emissions for extended periods of operation. 
P.11 

1 

J 

J 

J 

j 

ED-35 

If liquid chlorinated by-products are to be burned, the effluent 

should be sent to an efficient HCl removal system or used to produce 

desirable chlorinated hydrocarbons. 

In future oxychlorination plants that use tonnage oxygen, all 

hydrocarbon vent streams from the EDC plant could be sent to the same 

incinerator and HCl recovery system. 

Floating roof storage tanks in all new plants would reduce EDC 

losses from product storage facilities. 

F. Industry Research Efforts 

Current industry effort in air pollution control centers around 

development of more selective catalysts which will reduce the amount 

of chlorinated by-products and increase ethylene conversion. Individual 

manufacturers are involved in studies regarding the following: 

1. Developing markets for chlorinated compounds rejected in 

product distillation section. 

2. Removal of chlorinated hydrocarbons from water reject 

streams. 

3. Recovery of vent material from product storage tanks. 

4. Methods of reducing ethylene emissions during catalyst 

conditibning. 

5. Additional direct chlorination stages to reduce ethylene 

emissions. 
P.12 

ED-36 

V. National Emission Inventory 

Based upon the emission factors shown in Table ED-3A, the total approximate 

emissions from U.S. manufacture of EDC in oxychlorination plants are as 

follows: 

Component 

Hydrocarbons 

Ethylene 

Total Other Non-Methane 

Hydrocarbons (c) 

Particulates & Aerosols (d) 

CO 

Average Emissions 

(a) 

T/T of EDC 

0.0055 

0.0224 

©.0001 

0.0064' 

0.0344 ' 

# 

Total Emissions (b) 

MM lbs./yr. 

18.8 

76.3* 

• 0.4 , 

21.8 

117.3 

The above figures do not include any emissions resulting from off-site 

processing of waste water and reject hydrocarbon streams. It should be noted 

that about 55 percent of the oxychlorination EDC production is in plants that 

did not show product fractionation facilities in the survey reports, see 

Table ED-3A. Since all of these particular plants also produce vinyl chloride 

monomer, it is assumed that any undesirable impurities in the EDC are rejected 

in the downstream VCM facilities. In oxychlorination plants that purify EDC 

(98.5-99 wt. percent product purity), the hydrocarbon emissions resulting 

from product fractionation equal about 0.005 T/T EDC. If this typical figure 

is used to project losses for plants which did not show purification facilities, 

hydrocarbon emissions would be 9,4 million pounds per year higher than value shown. 

Ethylene dichloride production rate is fairly constant throughout the year. 

However, several plants did report slightly lower production during the first 

quarter of-CWe yeaY. . In addition, since cooling wdter, and product storage 

temperatures are higher in the summer, it is expected that emissions would be 

slightly above average during the warmer months.' , 

(a) Weighted average based on individual plant emission factors and EDC 

production figures. 

(b) Based on 1,705,000 tons/yr. total EDC production by the oxychlorination process, 

(c) Includes 0.0U06 T/T of EDC assumed to be emitted from product storage tanks. 

(d) Aerosols include HCl and carbon tetrachloride. 

J 
TABLE ED-13 

Type of Pollutio n Control 

EDC. Production, *A> Tona/Yr. 

Pol-ttan t <*> 

Hydrocarbons: 

Ethylene 

Other Non-Methane 

Hydrocsrbons 

Perticulete s U Aerosols *• ' 

NOx 

CO 

Average 

Emissions 

T/T 

0.0055 

0.0224 <G) 

0.0001 

0.0064 

0.0344 

Present 

4.20 5 

Tote l 

System 

,00 0 

Emissions 

MM Lbs 

46. 3 

188.4 

0 . 8 

53. 8 

289. 3 

./Yr . 

• 

Weighted 

Emissions 

3,700 

15,070 

50 

50 

18,870 <F> 

Average 

ESTIMATED 1965 AIR EMISSIONS 

FOR 

ALTERNATE CONTROL SYSTEMS 

Existin g Plant e 

Emissions 

T/T 

. 

0.0007 

0.0009 

0.0001 

0.0017 

(G) 

1,705.00 0 

Tote l 

Emissions 

MM Lbs./Yr . 

o 

2 . 4 

2 . 9 

0 . 4 

sTT 

(D) 

| 

1 

Weighted : 

Emissions ; 

| 

190 | 

175 ' 

15 

380 W 

Host 

Aversge 

Emissions 

T/T 

0.0001 

0.0001 

Feaaibl e Modification s 

New Plant e O 

2,500,00 0 

Tote l 

•mission s Weighted 

MM Lbs./Yr . Emissions 

0 . 6 25 

5T6 25 

1 

| Average 

;

 Emissions 

f T/T 

j 

1 

i 

, 0.0003 

0.0004 

0.0001 

0.000 8 

Totsl <».•> 

4,205,00 0 

Tota l 

Emissions 

MM Lbs./Yr . 

2 . 4 

2 . 9 

1.0 

6 3 

Weighted 

•mission s 

1 

190 i 

175 

4 0 

405 <*> 

? 

(A) Estimated production by oxychlorlnatlon process. 

(B) Excludes emissions resulting from off-site product fractionation and by-product dlapoaal. 

(C) Includes HCl and carbon tetrachloride. 

(D) Assumes ail existing plants modified to Incorporated thermal incinerators snd scrubbers on process vent stresm plus distillation vent condenaera and plume burnera. 

(E) New plants assiuned to contain floating roof product storage tanks and based on thermal Incineration on process snd distillation vent at reams with waste heat boiler 

snd caustic scrubber with distillation vent condenser before Incineration. 

(F) Significant Emission Index, which la baaed on the following weighting factora: Hydrocarbon - 80, Particulates • 60, NOx - 40, and CO - 1. (See Appendix) 

(C) Includes O.00U6 T/T of EDC loat from product storage tsnks in existing units. 
ED-54 

XIII. Emission Control Deficiencies 

Technical deficiencies which hinder reducing the level of emissions 

include the following: 

A. Process Chemistry and Kinetics 

In the oxychlorination process, a cupric chloride catalyst is used to 

produce EDC. Based upon experimental data it is believed that the reaction 

proceeds by formation of an ethylene-oxygen complex, which is subsequently 

chlorinated to ethylene dichloride by either HCl or cupric chloride. The 

rate determining step is the ethylene oxidation reaction. 

The amount of ethylene dichloride produced is influenced by the relative 

concentration of feed components, reactor residence time and other 

operating conditions. 

1. Reactor Feed 

(a) Ethylene • 

Unsaturated hydrocarbon impurities in the ethylene feed can 

react with HCl forming undesirable chlorinated by-products. 

Therefore, in order to minij)i^e^||; pollution and maximize 

productivity it is d-esirable°to use high purity ethylene. In all 

but one plant, ethylene feed contains less than' one percent 

impurities. In the one case (52-1) where low purity feed 

(82-92 percent ethylene) is utilized, chlorinated and non-chlorinated 

'hydrocarbon emissions are substantially higher than with the 

- conventional feed. In some cases economics dictate using some 

excess, ethylene to insure high HCl conversion. This excess 

olefin is normally vented to the atmosphere, but could probably 

be recovered by a direct chlorination step. 

(b) Oxygen Concentration 

All but one oxychlorinatjLon unit uses air as a source of 

oxygen. By utilizing pure oxygen iftjplace.~>f air., 01ant 52-10 . 

haa been able to reduce the volume of vent gas. Even though 

the total* quantity of hydrocarbon emissions are similar to 

those for the other units, most of this material consists of 

unconverted ethylene. Besides containing less chlorinated 

material, it should be less difficult and cheaper to control 

the quantity of emissions from this'source. 

(c) Hydrogen Chloride ' " . ° 

o 

Again, depending upon economics, some excess HCl may be fed 

to the reactors to insure high ethylene conversion. One published 

article ^ indicates that excess HCl leads to the formation of 

unwanted chlorinated by-products. 

2. Reactor Operating Conditions 

Reactor operating conditions influence ethylene conversion rate 

and to a certain extent the amount of non-selective products. Since 

P.14 

I 

I 

L 
I 

TABLE I 

(3) Hydrocarbons

 v ' 

1.1 

0 

0 

40 

6.1 

3.1 

183 

0 

11.2 

0 

156 

0.15 

70 

91 

15 

95. 1 

29 

85. 8 

23. 8 

25. 7 

16 

0 . 5 

1.3 

' 34 

0 

0 

5.25 

24. 3 

0 . 1 

0 

79 

75 

37. 5 

20 

62 

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 

12 

0.0 7 

1.6 

0 

0 

0 . 6 

49. 1 ' 

EMISSIONS SUMMARY 

ESTIMATED t 1) CURRENT 

>(*») Oxides 

' 

of Nitrogen 

0 

. 0 

"o.oi 

0.04 

0 

0 . 

5.5 

29. 6 

50. 5 

0.04 

6.9 

0.1 

0 

0 .1 

0.2 

0 

0 

0 . 3 

0 

0 

0 

0.41 

0 

0 

0 

0 

0.07 

0 

0 . 3 

0 

0 

0 

0 

0 

0 

0.14 

0 

0 

TR 

J) 

94.2 

AIR EMISSIONS. 

Sulfur Oxides 

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 

MM LBS./YEAR 

Carbon Monoxide 

0 

27 

0 

14 

1. 

5. 

196 

0 . 

0 

0 

3,87 0 

0 

77. 

53 

0 . 

2 1 . 

0 

0 

107 

2 4 . 

0 

0 

86 

260 

0 

0 

19. 

0 

4 3 . 

45 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

4,852 . 

3 

5 

14 

5 

2 

8 

2 

9 

5 

6 

6 

Page 1 o f 3 

Tota l 

1.1 

27 

0.0 1 

54 

7.4 

8 . 6 

385 

30 

66. 4 

0.54 

4,06 0 

5 . 1 

148 

146.5 

17. 6 

117.3 

29 

66. 2 

131 

50. 6 

16 

0.9 1 

88 

294 

1.5 

5 . 5 

24. 8 

24. 3 

51. 7 

47 

81. 3 

76. 4 

37. 6 

21. 6 

74 

4 . 5 

12 

5 . 3 

TR 

18. 2 

6,225- 9

 (7 > 

-

Tota l Weighted <5 

86 

27 

1 

3,21 5 

490 

253 

15,000 

1,190 

3,20 0 

30 

17,54 4 

120 

5,70 0 

7,46 0 

1,240 

7,65 0 

2,30 0 

6,88 0 

1.955 

2,07 0 

1,28 0 

56 

231 

2,95 0 

90 

330 

4 4 0 

1,94 0 

422 

160 

6,40 0 

6,10 0 

2,95 0 

1,65 0 

5,70 0 

355 

870 

425 

TR • 

1.46 0 

110,22 0 ( 7> 

Acetaldehyde via Ethylene 

via Ethanol 

Acetic Acid via Methanol 

via Butane 

via Acetaldehyde 

Acetic Anhydride via Acetic Acid 

Acrylonitrile (9) 

Adipic Acid 

Adiponitrile via Butadiene 

via Adipic Acid 

Carbon Black 

Carbon Disulfide 

Cyclohexanone 

Dimethyl Terephthalate (+TPA) 

Ethylene 

Ethylene Dichloride via Oxychlorination 

via Direct Chlorination 

Ethylene Oxide 

Formaldehyde via Silver Catalyst 

via Iron Oxide Catalyst 

Glycerol via Epichlorohydrin 

Hydrogen Cyanide Direct Process 

Isocyanates 

Maleic Anhydride 

Nylon 6 

Nylon 6,6 

Oxo Process 

Pheno1 

Phthallc Anhydride via 0-Xylene 

via Naphthalene 

High Density Polyethylene 

Low Density Polyethylene 

Polypropylene 

Polystyrene 

Polyvinyl Chloride 

Styrene 

Styrene-Butadiene Rubber 

Vinyl Acetate via Acetylene 

via Ethylene 

Vinyl Chloride 

Totals 

(1) Inmost Instances numbers are based on less than 100"/. survey. All based on' engineering judgement of best current control. Probably has up to 107. low blaa. 

(2) Assumes future plants will employ best current control techniques. *• 

(3) Excludes methane, includes H2S and all volatile organics. '?•"'••• 

(4) Includes non-volatile organics and inorganics. 

(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, N0 X - 40^, S0X - 20, and CO - 1. 

(6) Referred to elsewhere in this study as "Significant Emission Index" or "SE1". 

(7) Totals are not equal across and down due to rounding. * • • 

(9) Emissions based on what is now an obsolete catalyst. See Report No. EPA-450<*3-73-OOb b tor up-to-date information. 
TABLE I 

EMISSION SUMMARY j>age 2 of 3 

ESTIMATED ADDITIONAL <2> AIR EMISSIONS IN 1980, MM LBS./YEAR 

Hydrocarbons (-^ Particulates ^ ' Oxides of Nitrogen Sulfur Oxides Carbon Monoxide Total 

Acetaldehyde via Ethylene 

via Ethanol 

Acetic Acid via Methanol 

via Butane 

via Acetaldehyde 

Acetic Anhydride via Acetic Acid 

Acrylonitrile (9) 

Adipic Acid 

Adiponitrile via Butadiene 

via Adipic Acid 

Carbon Black 

Carbon Disulfide 

Cyclohexanone 

Dimethyl Terephthalate (+TPA) 

Ethylene 

Ethylene Dichloride via Oxychlorination 

via Direct Chlorination 

Ethylene Oxide 

Formaldehyde via Silve r Catalyst 

via Iron Oxide Catalyst 

Glycerol via Epichlorohydrin 

Hydrogen Cyanide Direct Process 

Isocyanates 

Maleic Anhydride 

Nylon 6 

Nylon 6,6 

Oxo Process 

Phenol 

Phthalic Anhydride via O-Xylene 

via Naphthalene 

High Density Polyethylene 

Low Density Polyethylene 

Polypropylene 

Polystyrene 

Polyvinyl Chloride 

Styrene 

Styrene-Butadiene Rubber 

Vinyl Acetate,via Acetylene 

via Ethylene 

Vinyl Chloride 

Totals 

.04 

.2 

1.2 

0 

0 

0 

12:2 

0.73 

284 

o; ' 

10.5 

0 

64 

0. 

77. 

73.8 

14.8 

110 

34.2 

32.8 

14.8 

17.6 

8.9 

0 

1.2 

31 

0 

0 

3. 

21. 

0. 

0 

210 

262 

152 

20 

53 

3.1 

1.85 

4.5 

0 

26.3 

1.547.2 

.86 

.3 

.3 

0 

0 

0 

0 

0 

0 

0 

0.14 

4.4 

0.5 

3.3 

0.07 

0 

1.1 

0.2 

0.5 

0 

0 

0 

0 

0 

0 

0.7 

0 

3.2 

5.3 

0.01 

0 

13;2 

0 

6.2 

5 

0.5 

0.34 

10 

0.05 

0.31 

0 

0 

0.9 

55.9 

.07 

.2 

0 

0 

0.04 

0 

0 

0 

8.5 

19.3 

47.5 

0.04 

2.8 

0.03 

0 

0 . 

0 . 

0 

0 

0.15 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0. 

0 

0 

0 

0 

0 

0 

6. 

0 

0 

TR 

0 

05 

79,5 

0 

0 

0 

• 0 

0 

0 

0 

0 

0 

0 

8.9 

1.1 

0 

0.84 

61.5 

0 

0 

0.05 

0 

0 

0 

0 

0.02 

0 

0 

0 

0 

0 

6.8 

0 

0 

0 

0 

1.13 

0 

0 

0.18 

0 

0 

0 

0 

0 

0 

0 

2. 

1. 

304 

0. 

0 

0 

1,590 

0 

85. 

42. 

0. 

25 

0 

0 

66. 

17. 

0 

0 

85 

241 

0 

0 

14. 

0 

113 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

5 

42 

09 

1 

9 

2 

7 

0 

3 

1.2 

0 

0.04 

0 

14.7 

2.15 

59b 

19.5 

62.4 

0.54 

1,670 

1.24 

162 

118.7 

77 

136 

34.2 

33 

81.5 

34.6 

8.9 

0 

87 

272 

3.2 

5.3 

18.2 

21.3 

134 

0 

216 

267 

152.5 

21.47 

63 

3.25 

2.34 

4.5 

TR 

27.2 

80.5 2,588 4,351.9 

Total WeiRhted ( 5.

6

> 

(1) In most instances numbers are based on less than 1007. survey. All based on engineering judgement of best current control. Probably has up to 107. low bias. 

(2) Assumes future plants will employ best current control techniques. 

(3) Excludes methane, includes H2S and all volatil e organics. 

(4) Includes non-volatile organics and"inorganics. 

(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, N0X - 40, S0X - 40, and CO - 1. 

(6) Referred to elsewhere in this study as "Significant Emission Index" or "SEI". 

(7) Totals are not equal across and down duw to rounding'. 

(9) See sheet 1 of 3. 

96 

0 

2 

0 

980 

60 

23,000 

779 

3,010 

30 

7,200 

30 

6.260 

6,040 

2,430 

8.800 

2.740 

2.650 

1,250 

1.445 

700 

0 

225 

2,720 

194 

318 

125 

1,704 

1.100 

0 

17,200 

21,300 

12,190 

1,640 

4.840 

225 

170 

360 

TR 

2.17 0 

134,21 3 <7> 
4 — •-—> f—« r --- . r • • • - • • • - - - i 

• TABLE I 

1 EMISSIONS SUMMARY 

•J O ' 

| Emissions ( 2_), MM Lbs. /Year 

I Total by 1980 Tota l Weighted ( 5) by 1980 

1 Acetaldehyde vi a Ethylene 2. 3 182 

v i a Ethanol 27 27 

Aceti c Acid vi a Methanol 0.0 5 3 

v i a Butane 54 3,21 5 

v i a Acetaldehyde 22 1,470 

Aceti c Anhydride vi a Aceti c Acid .10.8 313 

Acrylonitril e (9) 980 38,00 0 

Adipi c Acid 50 1,970 

Adiponitril e vi a Butadiene 128.8 6,21 0 

v i a Adipi c Acid 1.1 60 

Carbon Black 5,730 24,74 0 

Carbon Disulfid e 6. 3 150 

Cyclohexanone 310 11,96 0 

Dimethyl Terephthalat e (+TPA) 265 13,50 0 

Ethylene 94 3,67 0 

Ethylene Dichloride vi a Oxychlorinatio n 253 16,45 0 

v i a Direc t Chlorinatio n 63 5,04 0 

Ethylene Oxide 120 9,53 0 

Formaldehyde vi a Silve r Catalyst 212. 5 3,20 5 

v i a Iron Oxide Catalyst 85 .3,51 5 

Glycerol vi a Eplchlorohydrin '• 25 2,00 0 

Hydrogen Cyanide Direc t Process " 0. 5 (10) 28 (10) 

Isocyanate s 175 45 6 

Maleic Anhydride 566 5,67 0 

Nylon 6 4. 7 J 284 

Nylon 6,6 10.8 650 

Oxo Process • 43 765 

Phenol 46 (3,640 

Phthali c Anhydride vi a O-Xylene 186 1,522 

v i a Naphthalene 47 160 

High Density Polyethylene 297 23,60 0 

Low Density Polyethylene 343 27,40 0 

Polypropylene 190 15,140 

Polystyrene 43 3,?9 0 . 

Polyvinyl Chloride 137 10,54 0 

Styrene 7.4 610 

Styrane-Butadiene Rubber 14 1,040 

Vinyl Acetat e vi a Acetylen e 9. 8 785 

v i a Ethylene TR TR 

Vinyl Chloride 45 3.63 0 

Totals 10,605

 (7 )

 244,42 0

 (7 ) 

(1) In most instance s numbers ar e based on less than 1007. survey . All based on engineerin g judgement 

(2) Assumes future plants wil l employ best current contro l techniques. 

(3) Excludes methane, include s H2S and al l volatil e organics. 

(4) include s non-volatil e organic s and inorganics. 

(5) Weighting factor s used are : hydrocarbons - 80 , particulate s - 60, N0X -'40 , S0X - 20 , and CO - 1 

• (6) Referred to elsewher e in this study as "Significan t Emission Index" or "SEI". 

1 (7) Totals are not equal across and down due to rounding. 

1 (8) By 1985. 

1 (9) See sheet 1 of J 

1 (10) Due to anticipate d futur e shut down of marginal plants. 

•"* " "| "f 

t ./ a 1 a 

Estimated Number of New 

(1973 - 1980) 

b 

0 

4 

0 

3 

3 

5 

7 

4 

3 

13 

2 

10 

8 

21 

8 

10 

15 

4 0 

12 

1 

0 

10 

6 

10 

10 

6 

11 

6 

0 

31 

41 

32 

23 

25 

9 

4 

I 

4 

10 

of best current control . 

• 1 

t t t m * 

Page 3 of 3 

Tota l E 

Plants 

Current 

1 , lbO 

966 

4 0 0 

1,020 

875 

1,705 

1,165 

1,43 0 

4 3 5 

280 

3,00 0 

871 

1,800 

2,86 5 

22,29 5 

4,45 0 

5,59 3 

4,19 1 

5,91 4 

1,729 

245 

4 1 2 

1,088 

359 

4 8 6 

1,523 

1,727 

2,36 3 

720 

603 

2,31 5 

5,26 9 

1,16 0 

3,50 0 

4,375 . 

5,95 3 

4,46 4 

2 0 6 

1,280 

5,40 0 

Probably has up to 107. 

4 • t > 

m 

stimated Capacity 

MM Lbs./Year 

Bv 1980 

2,46 0 

966 

1,800 

500 

2,01 5 

2.10 0 

3,70 0 (8 ) 

2,20 0 

845 

550 

5,000 (8 ) 

1,100 

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 ) 

380 

202 

2,12 0 

720 

1,500 

3,00 0 

3,00 0 

4,20 0 

1,80 0 (8) 

528 

8,50 0 

21,10 0 

5,80 0 

6,70 0 

8,00 0 

10,00 0 

5,23 0 

356 

2,20 0 

13,00 0 

low bias . 

7 :^ 

* 

> 

»-* Un