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Document Number: 

37) ll-A-11 

Docket Number: 

A-90-19 

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A-90-19 

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EPA AIR DOCKET 

, na.ii.ir.wmn j 

992 PJ 

_JC | 

)CKET | 

, ENGINEERING 

AND COST STUDY 

F AIR POLLUTION CONTROL 

FOR THE 

PETROCHEMICAL INDUSTRY 

VOLUME 8: VINYL CHLORIDE 

MANUFACTURE 

BY THE BALANCED PROCESS 

by 

R.G. Bellamy and W.A. Schwartz 

Houdry Division 

Air Products and Chemicals, Inc. 

P . O. Box 427 

Marcus Hook, Pennsylvania 19061 

Contract No. 68-02-0255 

EPA Project Officer: Leslie Evans 

Prepared for 

ENVIRONMENTAL PROTECTION AGENCY 

Office of Air and Waste Management 

Office of Air Quality Planning and Standards 

Research Triangl e Park , North Carolina 27711 

July 1975 
P.3 

i 

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 supplies permit - from the 

Air Pollution Technical Information Center, Environmental Protection 

Agency, Research Triangl e 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 

Houdry Division of Air Products and Chemicals, Inc. , Marcus Hook, 

Pennsylvania 19061, in fulfillment of Contract No. 68-02-0255. The 

contents of this report are reproduced herein as received from 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-h 

n 
p

j

 VCM-l 

P.4 

!• 

T - I. Introduction 

The production of vinyl chloride monomer (VCM) has become 

a big volume business. Some of the older existing plants 

are in the 150 to 200 million pounds per year capacity 

range. It is believed that virtually all new plants will 

be designed to produce in excess of 500 million pounds of 

VCM per year. ^' This is because the economics of production definitely favor large volume raw material supply and 

large equipment. Almost all the VCM produced goes into 

the manufacture of polyvinyl chloride (PVC). A very small 

amount is used as an intermediate to manufacture methyl 

chloroform (CH3*CCl3), a specialty solvent. A small 

quantity was previously used in special aerosol sprays 

(insecticides, fungicides, etc.) but this use has recently 

been banned in the United States. Therefore the growth of 

VCM is exactly tied to the growth of PVC. In 1973 total 

U.S. production of VCM exceeded 4.7 billion pounds.(2) 

Over ninety percent of the vinyl chloride monomer produced 

in- the United States is obtained by cracking dichloroethane. 

An older process using acetylene and hydrogen chloride feed 

has been virtually completely replaced by the dichloroethane 

route because of the high cost of acetylene. The capacity 

of acetylene type plants is about 10-12% but actual production 

from them is much less. 

In most cases, overall vapor emissions from the cracking 

operation are small in quantity. The vapor emissions do 

include a small amount of VCM. The problems of VCM air 

emissions in these plants are similar to those encountered 

in PVC production. However, VCM plants have one big advantage, 

they employ a continuous process as opposed to the PVC batch 

type processes. This means that VCM emissions from these 

plants are considerably less per unit of production. 

This report concentrates on VCM emissions, not hydrocarbon 

and particulate losses. It also contains information on VCM 

losses from ethylene dichloride (EDO- plants_using the 

oxychlorination process. This latter information was not 

included in a previous in-depth study of the oxychlorination 

process. (4) Prior to January 1974 it was not known that VCM 

was carcinogenic at low concentrations (under 500 PPM). Because 

of this, EDC manufacturers had not attempted to analyze or 

report the presence of VCM in the oxychlorination vent streams. 

The emission losses used in the present report are based on 

information obtained prior to September 1974. There has been 

much money and effort spent to reduce VCM emission losses from 

EDC and VCM manufacture since that time as well as much improvement made in the detection of low concentrations of VCM (under 

10 PPM). VCM emissions have undoubtedly been substantially 

reduced since the summer of 1974. 
VCM-2 

P.5 

II. Commercial Processes 

Acetylene and hydrogen chloride are used as starting 

materials in the oldest commercial process. In this country, 

this is a minor process because economics favor ethylene 

as a raw hydrocarbon feedstock over acetylene. However, 

there are two plants still using this process. 

The reaction is as follows: 

C2H2 + HC1 > CH2 « CHC1 

The reaction is catalyzed by mercuric chloride (10%) on an 

activated carbon base and is carried out at 195 to 285°F. 

The reactants are fed at a 1:1 mol ratio and the reaction m^ 

goes to approximately 98 to 99% completion. The reaction 

is very exothermic and temperature must be controlled carefully. The reactor pressure is low ( 2.5 atm.) for safety 

reasons. Acetylene becomes increasingly hazardous 

(explosively) at elevated pressures. If acetylene could be 

produced nearly as cheaply as ethylene (say within a half 

a cent per pound), this process could compete with ethylene 

process as there are no major by-products to consider. 

However at the current differential of 5 to 10 cents per 

pound, the use of acetylene is too expensive to consider 

for any new plants and makes existing plants marginal. 

Figure VC-1 shows a simplified flow diagram for the acetylene 

process. Plants VC-7 and VC-9 are the only plants surveyed 

in this study that use the acetylene process. 

In the principal process currently used to produce VCM, dry 

dichloroethane (also named ethylene dichloride) is dehydrochlorinated to vinyl chloride in a cracking furnace. 

The chemical reaction is as follows: 

CH2CICH2CI > CH2 = CHC1 + HC1 

The dichloroethane for this cracking operation is normally 

produced by two commercial processes. One is the direct 

chlorination of ethylene with chlorine: 
I I [ i I t 1 .- j _f '• t ' i: ' A \. i 

• 7 r 

TABLE VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-1 

Plant Capacity, Million Lbs.Ar.: 500 

Process: Balanced EDC 

Source 

Area 

7a . 

7a 

C 

D 

1*1 

Description 

EDC Distillation Column 

EDC Distillation Column 

Transfer and Loading Losses 

Sampling Losses 

Fugitive Losses 

Total 

Type Of 

Emission 

Control 

Device 

il] 

Control 

Device 

Catalog 

I.D, No. 

VMD-1 

VMD-1 

VMD-1 

VMD-17 

VCM Emissions 

Lbs./Lb. Prod. Tons/fr. 

.000175 

.000354 

.000048 

.000001 

9 

.000578 

< 

O 

l 

144.5 

Notes: 

(1 

[2\ 

$ 

Vent from EDC column in associated direct chlorination unit. 

Vent from EDC column in associated oxyhydrochlorinatlon unit, 

Flow sampling loops. 

No estimate of fugitive emission given - no material balance 
TABLE VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-2 

Plant Capacity, Million Lbs.Ar.: 300 

Process: Pyrolysis of EDC 

Source 

Area 

B 

C 

D 

F 

F&G 

Notes 

(i) 

Description 

Water 

Loss 

Released From Neutralizer 

Dock & RR Tank Car Loadin 

Sampling (3) 

Neutralizers and Filters (4) 

Dryers and. process Vessels (4) 

Fugitive 

Total 

® 

a pi 

(5) 

Type Of 

Emission 

Control 

Device 

Control 

Device 

Catalog 

I.D. No. 

VMD-1 

VMD-2 

VMD-17 

VMD-1 

VMD-1 

VCM Emissions 

Lbs./Lb. Prod, 

.000015 

.001214 

.000001 

.000002 

. oooo32 

Tons/Yr. 

< 

o 

I 

.001264 189.6 

Vent from flash pot releasing. 

All major VCM emission streams returned to absorber to be recycled in EDC streams. 

This loss will drop to approximately .000174 by mid 1975 when dock loading losses 

are connected to system. 

Sampling losses minimized by sampling loop. 

Intermittent emissions. 

No estimate or material balance given. 

*""") *"! *~1 X~w 
i . L i._- i 

TABLE VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: vc-3 

Plant Capacity, Million Lbs.Ar.: 

Process: Balanced EDC 

840 

Source 

Area 

A 

C 

D 

Description 

Scrubber Vent Stack -

Collects From 8 Areas 

Loading Arms and Loading Areas 

Flare 

Sampling 

Fugitive (1) 

Total 

Type Of 

Emission 

Control 

Device 

• 

None 

Control 

Device 

Catalog 

I.D.No. 

VMD-1 

VMD-3(2) 

Lbs 

VCM 

./Lb. PJ 

.002355 

.000048 

.000023 

.000052 

.002478 

Emissions 

•od. Tons Ar . 

1040.7 

VCM-15 

Notes: 

(1) 

(2) 

Calculated by analogy from emission factors taken from "Control Techniques for Hydrocarbon and 

Organic Solvent Emissions From Stationary Sources", Natural Air Pollution Administration, 

Publisher Number AP-68, March 1970. 

A refrigeration device, VMD-4, is used to condense some of the vapors prior to the flare. No 

data are given as to conditions or type of equipment. 

XI 

co 
TABLE VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-4 

Plant Capacity, Million Lbs.Ar, 

Process: Balanced EDC 

730 

Source 

Area Description 

Type Of 

Emission 

Control 

Device 

Control 

Device 

Catalog 

I.D. No. 

VCM Emissions 

Lbs./Lb. Prod TonsAr' 

Main Stack 

Loading Losses 

Fugitive (1) 

Total 

VMD-1 

VMD-4 (2) 

.001368 

.001929 

9 

.003297 1203.4 

< 

o 

3 

<T> 

Notes; 

(1) No estimate given or material balance made. 

(2) Some type of condensing system is noted but no information is given of conditions 

or type of equipment. 

r—1 1—1 r r J CO 
* I \ I J t_ J *. J L I I J I i I, J I J «- I - 1 I 

TABU VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-6 

Plant Capacity, Million Lbs.Ar, 

Process: Pyrolysis of EDC 

320 

Source 

Area Description 

Type Of 

Emission 

Control 

Device 

Control 

Device 

Catalog 

I.D.No. 

VCM Emissions 

Lbs./Lb. Prod. Tons Ar . 

A 

C 

D 

G 

Light Column Vent 

Tank Car Loading 

Sampling 

Cleaning, Inspections, Etc. 

Fugitive (1) 

Total 

of Vessel 

VMD-1 

VMD-17 

000040 

000486 

000001 

000088 

000615 

< 

n 

se 

i 

104.6 (2) 

Notes; 

(1) No estimate or material balance given. Statement made that fugitive emissions are very low 

due to constant monitoring and good housekeeping. 

(2) Based on data provided in June 1974 report. Correspondence with the manufacturer subsequent 

to the completion of this study indicates total VCM loss may have been as much as ten times 

higher than value shown. 

11° 
TABLE VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-7 

Plant Capacity, Million Lbs.Ar . 

Process: Acetylene 

300 

Source 

Area 

C 

D 

Description 

Loading Losses, Max, 

Sampling 

Flar e Stack, 

Fugitive 

Total 

Type Of 

Emission 

Control 

Device 

m 

Control 

Device 

Catalog 

I.D. No. 

VMD-17 

VMD-3 

Notes: 

(1) This loss estimated by observation as a probable maximum, 

I 

r — T B 

VCM Emissions 

Lbs./Lb. Prod 

.000030 

.000001 

0 

.000365 

.000396 

Tons A r 

59.4 

< n 2 

l 

M 

CO 

V" .57 JT% 
TABLE VC-3 

NATIONAL EMISSION INVENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-8 

Plant Capacity, Million Lbs.Ar.: 100 

Process: Balanced EDC 

Source 

Area Description 

D 

F 

H 2 

Sampling 

Dryers 

Oxychlorination Vent 

Waste Heat0Boiler Scrubber Vent (1) 

Fugitive \di 

Total 

Type Of 

Emission 

Control Device 

Control 

Device 

Catalog 

I ,D. No. 

VMD-17 

VMD-1 

VMD-1 

VMD-6 

Lbs 

VCM Emissions 

./Lb. Prod. 

.000038 

.000003 

.001272 

.000019 

.000152 

TonsAr. 

VCM-19 

.001484 74.2 

Notes: 

(1) Most of the main vents of the VCM plant are vented to a waste heat boiler along 

with waste streams from other processes. 

(2) By material balance. 
TABLE VC-3 

NATIONAL EMISSION INyENTORY FOR VCM MANUFACTURE 

Plant Code Number: VC-9 

Plant Capacity, Million Lbs.Ar. 

Process: Acetylene 

275 

Source 

Area 

•E " 

Description 

Vent Reactor 

Fugitive (2) 

Total 

Vent (!) 

Type Of 

Emission 

Control 

Device 

Control 

Device 

Catalog 

I.D. No. 

VCM Emissions 

Lbs./Lb. Prod 

VMD-1 & VMD-4(3) .003561 

.001515 

.005076 

TonsAr 

698.O 

< 

o 3 

l 

rO 

O 

Notes: 

(1) 

(2) 

(3) 

A secondary reactor is incorporated 4.n this plant to reduce to£al VCM emissions, but 

it also has a monetary value in reducing losses significantly. 

Estimated from material balance. 

No details are given other than the vent are cooled to less than 40°F. 

-4'Jp 
I *L1 

TABLE VC-7 

DIRECT FIRED BOILER PLUS SCRUBBER EMISSION CONTROL SYSTEM FOR 

5 3 0 MM LBS./YR . OXYCHLORIWATIOW PROCESS VENT GAS STREAM 

Cotnponent 

Carbon Dioxide 

Carbon Monoxide 

"ltrogen 

Oxygen 

Kfthane 

ethylene 

Ethane 

ethylene Dlchlorlde 

Ethyl Chloride 

Vinyl Chloride 

Water 

Hydrochloric Acid 

Chlorine 

Nitrogen Oxides 

Sodiun Hydroxide 

Sodium Chloride 

Total Lbs./Hr. 

SCFM 

80°F Comb. Air 

Natural Gas 

Process Vent 

Gas (100°Fy 

Process 

Vent Gas 

l

'HS 

52,706 

2,962 

130 

318 

435 

454 

386 

101 

Combustion 

Air 

26,752 

8,126 

Natural 

Gas 

54 

527 

120 

Incinerator 

Flue Gas 

7,784 

79,511 

3,971 

Quench 

Water 

Caustic 

Feed 

Scrubber 

Reject 

Scrubber 

Effluent 

7,784 

79,511 

3,973 

59,531 

13,085 

550° F 

Flue Temp. 

460 

35,338 

Quench 

Water 

701 

3,680 

609 

11 

4 

95,570 

21,230 

27,524 

27,524 

Feed Water 35,500 Lbs./hr. (240°F) 

Steam at 245 PSIG (Sat.) 

33,800 Lbs./Hr. 

». Blowdovm 1,700 Lbs./Hr. (404°F) 

Packed Tower 

678 

678 

Flue Gas 

140° F 

Caustic Feed 

19,034 

991 

.20,025 

Reject 

}'I0° F 

12,474 

1 

4 

103,747 

24,210 

< 

Boiler