EPA-450/3-73-006-i
July 1975
ENGINEERING
AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE
PETROCHEMICAL INDUSTRY
VOLUME 9:
POLYVINYL CHLORIDE
MANUFACTURE
U.S. ENVIRONMENTAL PROTECTION AGENCY
OHire ol Air anil Wasle Management
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
-------
EPA-450/3-73-006-1
ENGINEERING
AND COST STUDY
OF AIR POLLUTION CONTROL
FOR THE
PETROCHEMICAL INDUSTRY
VOLUME 9:
POLYVINYL CHLORIDE
MANUFACTURE
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 Triangle Park, North Carolina 27711
July 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 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.
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-i
11
-------
In-Depth Study
of
POLYVINYL CHLORIDE PRODUCTION
Contract No. 68-02-0255
Prepared For
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Prepared By
Houdry Division
Air Products and Chemicals, Inc.
P. O. Box 427
Marcus Hook, Pennsylvania 19061
Houdry
Division
-------
TNTRODUCTION TO SERIES
oared for the Environmental
This document is one of a /^les Prep in determining those
Protection Agency (EPA) to assist ^ should be promul-
petrochemical processes ^ °£ wh^ch stan produced by 12 distinctly
Sated. A total of nine petrochemical s, p of in_depth
Afferent processes has been «^ed for th ^^^ iht
study. These processes are .^i^re impact on air quality.
The ten volumes of this -ries repo
acrylonitrile,
processes in a
vinyl chloride monomer.
lack,
(two proces.es xn
in a single
chloride ana
-------
AC KNOWLEDGEMENT S
The study reported in this volume, by its nature, relied
on the fullest cooperation of the companies engaged in the
production of polyvinyl chloride. This was given at a
particularly difficult time as all the companies were in
the midst of an all out effort to reduce all vinyl chloride
monomer emissions to a minimum. Without their information
this report could not have been written. We, therefore,
list the participating companies to acknowledge their
cooperation and assistance.
American Chemical Corporation*
Borden, Incorporated
Continental Oil Company
Firestone Plastics Company
General Tire & Rubber Company
B. F. Goodrich Chemical Company
Goodyear Tire & Rubber Company
Great American Chemical Corporation
Hooker Chemical Corporation
Keysor-Century Corporation
National Starch & Chemical Compciny
Pantasote Company of New York, Inc.
Stauffer Chemical Company
Tenneco Chemicals
Union Carbide Corporation
Uniroyal Chemical Company
Universal PVC Resins, Incorporated
Air Products and Chemicals, Inc.
*Subsidiary of Stauffer Chemical Company
We also acknowledge the help of numerous manufacturers of
equipment.
-------
TABLE OFCONTENTS
Section
I.
II.
III.
IV.
V.
VI.
VII.
VIII.
IX.
X.
Title
Chemistry1?? polymerization
Commercial Processes
Commercial Products
on inventory
industrial Growth projection
Emission Control Devices
Development Goals
Page Number_
PVC-1
PVC-4
PVC-6
PVC-20
PVC-21
PVC-7^
PVC-75
PVC-78
PVC-86
PVC-93
Title
Polyvinyl Chloride Plant - Suspension
Polyvinyl Chloride Plant - Dispersion
Page Number
PVC-7
PVC-9
PV-8
ofpVC Manufacturing Plants
ssa si :ffia- ss-
Suspension Process Total Emissions
Dispersion Process Total Emissions PVC-76
Polyvinyl Chloride Resins Yearly
PVC-77
Table
PV-1
PV-2
PV-3
PV-4
PV-5
PV-6
PV-7
PV-8
PV-9
Title
Material Balance
Material Balance
Material Balance
Bulk Process
Plants
National Emission Inventory For
ugitive
Page Number_
PVC-1^
PVC-15
PVC-16
PVC-17
PVC-18 & 19
PVC-22 Thru 63
PVC-67 & 68
PVC-70
PVC-72
-------
TABLE OF CONTENTS
(CONTINUED)
Table Title Page Number
PV-10 Catalog of Emission Control Devices PVC-85
PV-11 PVC Manufacturing Cost for a Typical PVC-87
Existing 200 MM Lb./Yr. Facility
PV-12 Model Plant I Incorporating Moderate PVC-88
Emission Control Devices
PV-13 Model Plant II Incorporating Extensive PVC-90
Emission Control Devices
PV-14 PVC Manufacturing Cost for a Typical PVC-92
Model I Plant
PV-15 PVC Manufacturing Cost for a Typical PVC-93
Model II Plant
PV-16 Estimate of VCM Emissions from Model PVC-94
Plants
-------
FVC-1
I. introduction
l . -.
Polyvinyl chloride (FVC) resins ^.^^S^St .
plastic compounds from the pur t££ting with minor (< 10*)
endless variety of ™d"i£a;£ vinylidene chloride, vinyl
founts of ^polymers such a s v iny ^ e ^ The resins
acetate, ethylene, prop ylene or J stabilizers,
-8 d
V asphalt tiles
less than
some 40 years
presence of a suitable ig- rubber or
sSr- -^e
rws sssrrv s Jjgsi.
1950S)
= «T!»^ S
s^^.'^^%£^sls%"0
production of rigid PVC P^JJ^ied PVC plastics depend
s asrs.
desired properties.
resins used in the various
°f
ere or in
homopolymers.
The most portent co^ercial coders of
are those with vinyl acetate Tne nig aj.e us£d
resins with an acetate content of aoo f^ster processing
flow properties compared
-------
PVC-2
with those of conventional homopolymers. Copolymers contain-
ing over 8$ vinyl acetate flow even more readily under the
application of heat and pressure and are, therefore, favored
in the production of phonograph records. The copolymers also
are capable of binding particularly large amounts of mineral
fillers and pigments, a capability utilized in the production
of vinyl-asbestos floor tile. Because the solubility in
esters and ketones of vinyl chloride copolymers with an
acetate content of 10-20$ is much greater than that of homo-
polymers, these resins are used in solution coating.
The commercial copolymers of vinyl chloride with ethylene and
propylene contain 1-8$ of ethylene or propylene and are
predominantly used in the manufacturing of unplasticized
(rigid) FVC products. Such copolymers can be processed
faster and have better impact strength than comparable
homopolymers, without any sacrifice in dimensional stability
and other important performance properties,,
Copolymers of vinyl chloride with vinylidene chloride are more
soluble in solvents than homopolymers and they are good film
formers. The few resins of this type that are on the market
today are, therefore, mostly used in specialty coatings (in
solution and, in some applications, in latex or emulsion form).
A few latex PVCs or copolymers of vinyl chloride and ethyl,
n-butyl, or 2-ethylhexyl acrylate are used in the production
of wall coverings, nonwovens, and house paint. The latexes
are 50 percent solid colloidal dispersions in water.
Postchlorinated FVC homopolymer resins have; long been in
existence but were of little commercial importance until
recently. Products made from them have better heat resistance
(and higher densities) than products made from ordinary PVC
resins. The main application for these resins is in residen-
tial hot water pipe.
In 1973 the production of PVC resins was 4,,423,400,000 pounds.
As there was a tight supply, this was probably all consumed.
Based on production figures since 1962, the growth curve is
shown in Figure PV-7 on page PVC-76 and indicates a projection
of growth to 1985. However two important factors have inter-
jected themselves recently into the picture which may change
this growth projection. One, is the energy crisis which
could curtail the supply of ethylene and discourage projected
expansions. (This has actually occurred.) Another factor
is the recent discovery (January 1974) of the carcinogenic
nature of vinyl chloride and the current uncertainty of how
OSHA and EPA regulations will effect the profitability of
manufacturing PVC resins. In any case, both factors will
probably inhibit the growth of PVC, perhapss very drastically.
-------
PVC-3
A third factor that has reduced the demand for PVC resins
is the current temporary slump in the building industry.
It cannot be overemphasized that the emissions shown in
this report are based on data obtained by the reporting
plants prior to August 1974. Many, if not all, the plants
have made considerable progress in reducing emission since
that time so that the emissions shown are those of a
transition period and do not reflect current emissions.
This is true of fugitive losses as well as known streams
as the industry has tightened up their losses in all
respects.
-------
pvc-4
II. Chemistry of Polymerization
The polymerization of vinyl chloride can occur in two ways,
one in a head-to-tail fashion,
£CH2CHClCH2CHCl3"
n
or head-to-head or tail-to-tail configuration,
n
Research has shown that the head-to-tail position is greatly
favored and closely represents the actual polymer.
The terminal groups can be saturated, unsaturated or radical
fragments from the initiator or solvent, depending on the
chain transfer activity of the various groups .
Saturated end groups are formed by chain transfer with
monomer and polymer and by termination through
disproportionation :
CHC12
Unsaturated chain ends are due to termination by dispro-
portionation and to chain transfer to monomer:
-CH2CHC1CH = CHClj — CC1 = CH2J -CH2CHC1CH = CH2
Initiator or solvent (chain-transfer agent) fragments,
represented by R, can be incorporated in the terminal group :
— CH2R; — CHC1R
Due to the high transfer activity of the monomer, about 60$
of the polymer molecules are estimated to have unsaturated
end groups. For the same reason, the percentage of chain
ends containing initiator fragments is low; the amount of
solvent fragments depends upon its transfer activity.
Long-chain branching can be caused by the incorporation of
the terminal double bond of a polymer molecule into a growing
chain:
-------
FVC-5
•CHgCHCl. + CHCl - CH-—-»*—CH2CHC1CHCHC1 •
or by intermolecular chain transfer to polymer:
-CH2CH2C1 +^-CH2CCl<
Xntra.olecular ^.
formation of short side chains.
-CH2CHC1CH2CHC1CH2 ^ — -CH2CHC1CH2CC1
C1HC- /CHCl CH
"^
CH2
CH2C1
-------
PVC-6
III. Commercial Processes
Polyvinyl chloride is primarily produced by one of the
following four processes.
A. Suspension Polymerization
Figure PV-1 persents a simplified flow diagram for the
suspension process. This process is by far the most common
process used to manufacture PVC resins (78% of total
capacity). It is likely to remain so for many years although
it may gradually decline as bulk polymerization becomes more
common and presumably more economic.
The precise mechanism of suspension polymerization is
still being investigated and there is no accepted theory to
explain all the observed phenomena. The general overall
process involves the suspension of liquid vinyl chloride
(requires pressures of 75 to 300 psig) in a continuous
water phase. A free radical catalyst is used to initiate
the polymerization reaction. This catalyst, is dissolved in
the VCM feed. Various suspending agents are used along
with continuous agitation to keep VCM droplets small and
dispersed. The polymerization occurs in the VCM droplets
and proceeds to around 85-90% completion. Efforts are
being made, with some success, to drive the reaction to
near completion (95-99%) using different initiators.
Reactor vessel sizes used in older plants were in the
3000-6000 gallons capacity range. The trend in the last
three years has been to go to much larger reactors (15,000
to 35,000 gallons) and to switch from glass lined reactors
to stainless steel vessels.
The heat of polymerization is removed from the
reactor system to maintain the desired operating tempera-
ture (about 50°C).
After the polymerization reaction has been completed,
the batch may be dropped to a stripper tank where the
monomer is stripped from the slurry,although some plants
strip in the reactor. The effectiveness of the stripping
controls the amount of VCM subsequently lost in all equip-
ment downstream of stripper.
After being stripped, the slurry is then transferred
to a blend tank where it is mixed with other batches of
slurry to produce a more uniform product. From the blend
tank the slurry is passed through a centrifuge to remove as
much water as possible and then into a rotary dryer, the
discharge of which is classified and stored in silos. Some
companies make only the raw PVC resin and sell to companies
-------
rv i
.
POLYVINYl CHLORIDE PLANT
PROCESS
VCM
CONDENSER
/ VCM >y
( RECOVERY
V TANK J
VCM FROM
TANK CAR
-------
PVC-8
the raw resin
B. Dispersion (Emulsion; Process
process is basicaly very stala to ^f "' W-2- Thls
unit from dissolved vinyl cSortde L f ' fartS a poly
picked up by the micelles Tn i??* °m vinyl chloride
ces Tn *
chain reaches its finastaee af 1 ? C?Se the
saee a
emulsifier molecules ingta« to tS rt,0f«^mlcelle with the
sizes obtained by dispersion ™?JS • i?lde* The Particle
than those obtained by suspensJonoi1^^" ^ much smaller
reason the most commonly *ml™S S^r!^Zation- Por th^s
drying which ensures SaLtSJSS %2 ??°d f?r drying is sPray
Approximately 13* of total tn^fi iJ1^ particle sizes-
devoted to iJL^r^ is
C. Bulk Polymerization
ScSSs^^ ^53^
expense of suspension process as th^?i°n ?°Uld be at the
processes complte for ££«£ S.^^JU th6Se tW°
The suspension of PVC in
-------
FlGUKfc
PQLYVINYL CHLORIDE PLANT
niSPERSlON PROCESS
VCM A
CONDENSER
» I
/VCNJ\
( RECOVERY)
V TANK J
/^DISTILLED \
WCMSTORAGE/
VCM FROM
TANK CAR
1
rum * r% \y i»» ^^11B__— I
TANK CAR ^ 1 J »-
VCM A VCM
STORAGE ) EVAPORATOR (OPTIONAL)
TANK (2)7
WEIGHT
TANK
CO MONOMER
TANK CARS
ANK CARS^ 1
/COMONOMERN
( STORAGE
V TANKS (2V
WEIGHT
TANK
(2)
CONO.
J
STRIPPER
(3)
COMP.
REC. VCMCOND.
a CONIP.
A°
BLEND
TANK
(3)
SPRAY
DRYER
BATCH
REACTOR
(18)
INITIATOR +
SUSPENDING ft
SURFACE ACTIVE
AGENTS
PUMP
SOLUTION MIXING
TANK ft CHARGE PUMP
CLEANINGS
a
VO
f
OVER
SIZE
HOLDING
BINS
BAGGER
(3)
SILOS
(12)
TO BULK
"SHIPPING
TO WAREHOUSE
-------
FIGURE PV-3
FLOW SHEET FOR POLYVINYL CHLORIDE
BULK PROCESS
INITIATOR
NITROGEN
B
PRE-PO
cONDENSER
PRE POLYMERIZATION
REACTOR
COMPRESSOR
00
VACUUM
IFILTER
6
B
RECYCLE
CONDENSER
A
MONOMER
PUMP
POST POLYMERIZATION
REACTOR
PRESS REDUCER
AUTOCLAVE
AIR
-D— **
BAG
FILTER
COLLECTOR
SCREEN
RESIN
HOPPER
i
H
O
-------
PVC-11
part of the vinyl chloride.
After the desired yield ^
monomer is stripped by vacuum and returned
recovery system. As there is not wat ure condenser
involved, it xs P08""6*^ VCMT However , off -setting
(-35°C) to recover most of the vuxu » autoclave
this particular advantage's the fact that ^ after
reactor for the final PJ^S^JSS, storage and shipping
every run. ^he final c la ssiti ±n the preceeding
operations are "milar to tnos ^ ^ since there 1S no
off in water effluents.
D. Solvent Polymerization
ESS
(0.01 to 0.5%)
off and the
. . .
by flash evaporation and the reooverea remarkably pure
- — desirable.
othSr processelTand so is limited to
justify a higher cost.
•v,-m-w 4-hat- solvent polymerization could
There is a possibility that solventp * used in
process (-20°C
or less).
A flow sheet for a typical solvent polymerization plant
is shown in Figure PV-4.
PV-l thru PV-^presentJypical^e^ate^al balances
air emission
-------
FIGURE PV-4
POLYVINYL CHLORIDE
SOLVENT PROCESS
MIXED
SOLVENT a
MONOMER
STORAGE
CO MONOMER*
INITIATORS
CO NT
FILTER
RECEIVING
FLASH
EVAPORATOR
CJ CJ
STORAGE
S!LO
STORAGE
SILO
JO GRINDER
OR SCRAP
ro
BAGGING a
SHIPPING
BAGGING 8
SHIPPING
-------
PVC-13
.
plus the lifted data ^om t »« £ization proOesses
Sis^dHt di ticuttSOtoVprodPuceyfirm material balances
f" these three particular processes.
Tables PV-1 thru --%?r fat feeastcckthreefoirerts
poUeri^ion^ciss^re^the -posite appears to
be true for the dispersion process.
It should be noted that the solvent P^^^nt
balance is based on one set of ^ f^resentative of the
and for this reason may n°£ °e ^ruiy P process it
process.. However sx nee this -^^cont ^ ^ ^ ^
is conceivable that v<-M emis^ (Continuous
primarily. )
The high feedstock requirement s a
hi0herselince this process
oter that for the suspension process.
ssi- '
these units
-------
PVC-14
TABLE PV-1
POLYVINYL CHLORIDE
NET MATERIAL BALANCE
FOR SUSPENSION PROCESS
(TONS/TON OF PVC CAPACITY)
INPUT
Vinyl Chloride Monomer (VCM)
Comonomer
Initiators
.Suspending Agents
Surface Active Agents
Total Input
Stream I.D.
on Simplified
Flow Diagram
1
2
3
3
3
Polymer
Ingredients
0.98-1.05
0.01-0.08
1.0598
Other
0.0009
0.0010
0.0003
0.0022
OUTPUT
PVC Homopolymer and Co-Polymer
Waste Solids and Liquids
Fugitive Emissions
Reactor Vent
Stripper or Slurry Tank Vent
Monomer Reclaim Vent Condenser
Blend Tank
Centrifuge Vent
Effluent From Dryer Collectors
Fines From Silo Collectors
Fines From Baggers Collectors
Fines From Bulk Loading Collectors
Monomer Storage
Safety Valve Vents
Total Output
4
5
B
C
D
E
F
G
G
G
G
A
B
PVC
1.0000
0.0100
0.0009
0.0010
0.002?
0.0006
-0.0037
0.0006
1.0275
VCM
0.0020.
0.008l(
O.ooi4
0.0032
0.0048
0.0042
0.0013
•0.0070
0.0005
0.0020
0.0345
(1) Assumed split on total fugitive emissions.
-------
PVC-15
TABLE PV-2
POT.YVINYL CHLORIDE
WET MATERIAL BALANCE
WOP DISPERSION PROCESS
(TONS/TON OF PVC CAPACITY)
INPUT
Vinyl Chloride Monomer (VCM)
Comonomer
Initiators
Suspending Agents
Surface Active Agents
Total Input
OUTPUT
PVC Homopolymer and Co-Polymer
Waste Solids and Liquids
Fugitive Emissions
Reactor Vent (1)
Stripper or Slurry Tank Vent
Monomer Reclaim Vent Condenser
Blend Tank
Effluent From Dryer Collectors
Fines From Silo Collectors
Fines From Baggers Collectors
Fines From Bulk Loading Collectors
Monomer Storage
Safety Valve Vents (1)
Total Output
Stream I.D.
on Simplified
Flow Diagram
1
2
3
3
3
4
5
B
c
D
E
G
G
G
G
A
B
Polymer
Ingredients
0.89-1.00
0.01-0.12
1.1039
PVC
0.0009
1.0475
Other
0.0009
0.0020
0.0003
0.0032
VCM
1.0000
0 . 0200
0.0013
o.oi8o
0 . 0020
0.0053
o.oio6
0.0015
0.0123
0.0050
0.0034
> 0.0241
0.0005
0.0022
0.0596
(1)
Assumed split based on data received for suspension process
-------
PVC-16
TABLE PV-3
POLYVINYL CHLORIDE
NET MATERIAL BALANCE
FOR BULK POLYMERIZATION
(TONS/TON OF PVC CAPACITY)
INPUT
Vinyl Chloride Monomer (VCM)
Initiators
Total Input
Stream I.D.
on Simplified Polymer
Flow Diagram Ingredients Other
1
2
1.0372
1.0372
O.OOQC
0.0009
OUTPUT
PVC Homopolymer
Waste Solids and Liquids
Fugitive Emissions(2)
Reactor Vent (1)
Monomer Reclaim Vent Condenser
Safety Valve Vents (1)
Fines From Silo Collectors
Fines From Baggers Collectors
Fines From Bulk Loading Collectors
Monomer Storage
Total Output
I
B
D
B
G
G
G
A
PVC
1.0000
0.0050
0.0047
0.0041
1.0138
VCM
0.0047
0.0008
0.0150
0.0010
0.0023
0.0005
0.0243
(1) Assumed split based on data received for suspension process.
(2) Assumed split to be 50% VCM and 50% PVC.
-------
FVC-17
TABLE FV-4
POT.WTMYL CHLORIDE
MATERIAL BALANCE
FOR SOLVENT POLYMERIZATION
(TONS /TON OF PVC CAPACITY!
INPUT
Vinyl Chloride Monomer (VCM)
Comonomer
Initiators
Total Input
Stream I.D.
on Simplified
Flow Diagram
1
2
3
Polymer
Ingredients
0.93-1-0°
0.01-0.08
1.0169
Other
0.0009
0.0009
OUTPUT
PVC Homopolymer and Co-Polymer
Waste Solids and Liquids
Fugitive Emissions
Reactor Vent (3)
Stripper or Slurry Tank Vent
Monomer Reclaim Vent Condenser
Effluent From Dryer Collectors
Fines From Silo Collectors
Fines From Baggers gJlleJt?".torB
Fines From Bulk Loading Collectors
Monomer Storage
Safety Valve Vents (3)
Total Output
PVC
B
C
D
G
G
G
G
A
B
1.0000
ii)
1.0044
VCM
0.0001
o.ooos
0.0050
0.0005
0.0031
I
y0.0083
0.0001
0.0006
0.0134
No information available.
Si?'based on data received for suspension process.
-------
PVC-18
TABLE PV-5
SUMMARY OF U.S. POLYVINYL CHLORIDE PLANTS
(1)
Company
Location
Published
Capacity,
MM Lbs./Yr,
Air Products and Chemicals,
Inc. (Plastics Division)
American Chemical Corp.
(owned by Stauffer
Chemical Company)
Borden Inc.
Borden Chemical, Division
Continental Oil Co.
Conoco Plastics Division
Diamond Shamrock Corp.
Diamond Shamrock Chemical
Co., Subsidiary Plastics
Division
Ethyl Corporation
Industrial Chemicals Div.
The Firestone Tire &
Rubber Co., Firecstone
Plastics Co. Division
The General Tire &
Rubber Co., Chemical/
Plastics Division
The B.F. Goodrich Co.
B.F. Goodrich Chemical
Co., Division
The Goodyear Tire &
Rubber Co., Chemical
Division
Great American Chemical
Corporation
Calvert City, Ky. 150
Pensacola, Florida 50
Long Beach, California 150
Illiopolis, Illinois 140
Leominster, Mass. 180
Aberdeen, Miss. 285
Oklahoma City, Okla. 240
Delaware City, Del. 100
Deer Park, Texas 270
Baton Rouge, La. 180
Perryville, Maryland 230
Pottstown, Pa. 270
Ashtabula, Ohio 125
Point Pleasant, W. Va. 50
Long Beach, Calif. 140
Henry, Illinois 140
Louisville, Kentucky 340
Avon Lake, Ohio 140
Pedricktown, N.J. 170
Plaquemine, Louisiana 100
Niagara Falls, N.Y. 100
Fitchburg, Mass. 40
-------
PVC-19
TABLE PV- 5
SUMMARY OF U-S- POLYVINYL CHLORIDE PLANTS U
(CONTINUED)
Company
Keysor-Century Corp.
Monsanto Company,
Monsanto Polymers &
petrochemicals Company
National Starch &
Chemical Corporation
Occidental Petroleum Corp.
Hooker Chemical Corp.,
Subsidiary Ruco Division
01in Corporation,
Thompson Plastics Co. Div.
Pantasote Company
Roblntech
Stauffer Chemical Co.
Plastics Division
Tenneco Chemicals, Inc.
(A major component of
Tenneco Inc.), Tenneco
Plastics Division
Union Carbide Corp.
Chemicals & Plastics Div.
Uniroyal, Inc., Uniroyal
Chemical Division
Location
Saugus, Calif.
Springfield, Mass.
Meredosia, Illinois
Burlington, N.J.
Hicksville, N.Y.
Assonet, Mass.
Passaic, N.J.
Point Pleasant, W. Va.
Painesville, Ohio
Delaware City, Del.
Burlington, N.J.
Flemington, N.J.
Texas City, Texas
South Charleston, W. Va,
Painesville, Ohio
Published
Capacity,
MM Lbs./Year
35
70
10
180
15
150
60
90
250
175
165
70
240
160
UK)
TOTAL CAPACITY
5,400
-------
PVC-20
IV. Commercial Products
PVC resins are compounded into a wider variety of products
than most any other plastic. They range from emulsions and
caulks to clear films and rigid structural shapes. PVC
resins are used to make both flexible and rigid foams with
a wide range of density. They have one big advantage over
most foams as they are generally rated "self-extinguishing"
in fire ratings while other foams need considerable
"doctoring". The chemical inertness of PVC makes it an
excellent material for pipe and exterior building forms
and coatings (on steel and aluminum). It can be made
flexible as leather or as rigid as glass. It can be made
clear or most any color desired.
Compounded PVC resins are converted to end products by
several processes. Extrusion is used to produce both
rigid extrusions (e.g., pipe and conduit, siding and
window sashes) and flexible extrusions (e.g., electrical
wire insulation, garden hose, and packaging film).
Rigid vinyl sheets are generally produced on calendars
which produce more than eight million pounds per year
of film and sheet products.
Dispersions or plastisols are used for fabric coating
(either on knife machines, roller coaters, or casting
machines), and in the production of low-cost type of vinyl
floor tile in which plastisol is cast on a felt base.
Plastisols are also used in rotational molding (e.g., for
toys and traffic cones) and in the dipping and hot-spraying
of tool handles and appliance parts.
The use of compression molding for PVC resins is restricted
to the production of phonograph records. Injection molding
of rigid PVC has been developed largely in the 1960s and is
mostly employed in the production of pipe fittings, and to
a much smaller extent in the production of parts for
communications equipment, business machines and toys.
A complex and still emerging technology in the processing
of compounded PVC resins is the blow-molding of containers.
-------
PVC-21
V. Plant Emissions
Table PV-6 shows individual plant capacity figures and
emission data for most of the major U.S. plants producing
PVC. Emissions from these plants are as follows:
A. Continuous Air Emission
1. VCM Recovery System Inerts Vent (Source Area D)
The VCM recovery system is where all the VCM vapors
drawn off the stripper (and at times from the reactor)
are compressed and condensed to recover most of the
unreacted monomer for recycling to the polymerization
reaction. This is a major emission stream for most
plants, not because of total stream volume which is
low, but because of high concentration of vinyl
chloride. It results from the necessity to purge
inerts from the monomer recovery system. Emissions can
be reduced by condensing under pressure and low tempera-
ture cooling (10° to -30°F). It can be even more
effectively reduced by using a vent scrubber or carbon
adsorber. The reported vent streams in this category
are shown as source area D in Figures PV-1 through PV-4
and Tables PV-1 through PV-6. Losses range from 0.0001
to 0.01 Ibs. VCM/lb. product.
2. Dryer Stacks and Miscellaneous
Solid Handling Vents (Source Area G)
The dryer vent is continuous but the amount of VCM
emission varies widely from plant to plant. If the
stripping of VCM at the strippers is done effectively
then the emission at the dryer stack is less. However
if the stripping is done poorly over 20% of the total
emission can occur here. It is a difficult stream to
control with add on devices because the volume of air
(13,000 to 25,000 ACFM per 5,000-10,000 pounds per hour
of dry PVC product) is large, the concentration of VCM
low (less than 0.1%) and the air is at 15QOF with a high
moisture content. These figures are typical for rotary
dryers which are used in most suspension type plants.
Losses range from 0.0005 to 0.006 Ibs. VCM/lb. product.
Spray dryer exhaust gas flow is similar to that of
a rotary dryer except the stream is generally larger,
hotter and more nearly saturated with moisture. Spray
dryers are generally used in dispersion plants although
a few are also used in suspension plants.
After the PVC solids are dried, they are most often
transported in the plant via pneumatic conveying systems
The air conveying streams are not laden with moisture
and are at ambient temperatures but their volumes are
very high and the VCM concentration much lower than in
the dryer stream (0-15 PPM VCM) .
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
Plant Code Number: A-l
Plant Capacity, Million Lbs./Yr.
Process• Suspension
95
Source•
Area Description
A RR Car Unloading
A Barge Unloading
A Transfer Pumps, Valves, Etc,
D&H Reactor Vacuum System (1)
B Reactor Ventilating System
D Recovery System
E Slurry Tanks
G Dust Collector
G Silos
Total
Loss To Water Systems (2)
Reactors
Strainers
Slurry Tanks
Centrifuges
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
(3)
(3)
Emissions
Lbs./Lb
VCM
.0003
.0006
.0007
.0605
.0008
.002?
.0112
.0055
.001
.0833
1.85X10-8
1.85X10-8
1.85X10-9
1.5X10-5
. Prod .
PVC
5X10-5
4.6x10-6
5.46-5
Tons Ar.
VCM PVC
14.25
28.5
33.25
2873.75
38.0
128.25
532.0
261.25 2.37
47.5 0.22
3956.75 2.59
8.79X10-f
8.79X10-4
8.79X10-5
0.7125
T1
<
o
1
ro
KJ
1.5X10-5
0.714
Notes; (1)
Loss very high here. Have just installed improvements that should reduce VCM emissions
by one-third. This would bring it down to about .04 Ibs./lb. prod, which is still higho
This also includes fugitive losses.
Loss to water systems so low that they have insignificant impact on total VCM loss.
Standard vacuum, compression and condensing system used to recover VCM for economic reasons.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-2
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
58.4
Source
Area Description
A RR Car Unloading
A Transfer Pumps, Valves, Etc,
D Reactor Vacuum System (1)
B Reactor Ventilation System
D Recovery System
E Slurry Tanks
G Dust Collector
G Silos
Total
Loss To Water Systems
Reactor
Strainers
Slurry Tank
Centrifuge
Type Of
Emission
Control
Device
(2)
(2)
Control
Device
Catalog
I.D.No.
Emissions
Lbs./Lb. Prod.
VCM PVC
Tons AT.
VCM
.0003
.0009
.026
.0013
.0027
.0112
.0055
.001
5X10-5
8.76
26.28
759.2
37.96
327^04
160.6
29.2
1.95X10-8
1,95X10-0
1.95X10-0
1.53X10-5
PVC
n
i
NJ
OJ
o0489(2) 5.5X10-5 1427.88 1.59
Notes- fl) This is main point of VCM emission. They are looking for improvements to reduce the loss.
Could also stand improvements in slurry tank vent losses. Fugitive emissions included here.
(2) Standard vacuum, compression and condensing system used to recover VCM for economic reasons
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-3
Plant Capacity, Million Lbs./yr.:
Process: Suspension
175
Source
Area
B
Dl
L2
E
Gl
G2
H
Description
Upset Losses Avg. on Cont. Basis
Recovery System Condenser Vent (1)
Recovery System Condenser Vent (1)
Tank Vent
Dryer Vent
Silo Vents
Fugitive
Total
* No PVC loss data are given.
Type Of
Emission
Control
Device
(3)
(3)
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM PVC
.0006 *
.0075
.0003
.0025
.0035
.0002
.0088 (4)
Tons/Yr.
VCM PVC
52.56
657.0
26.28
219.0
306.6 v
17.52 <
770.00 ^
.0234
2048.96
Notes: (V.
(2)
(3)
(4)
Major emission control device is monomer recovery system (vacuum stripper) which was just
installed in May 1974. It is not clear if above emission figure is before or after this
device was installed. (Presumably "after")
Considering installation of gas holder for collection of emissions at DI and possibly B
and E followed by a scrubber system. GI and G2 emissions would be reduced with improved
vacuum system at DI,
Standard vacuum, compression and condensing system used to recover VCM for economic reasons,
Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-4
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
120
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
Emissions
Source•
Area Description
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
G Dust Collector
E Blend Tank Vent
E Blend Tank Vent
E Blend Tank Vent
C Slurry Tank Vent
Total
Notes: (1} All losses are computed from total throughput (120 M/year).
(2) No fugitive losses are estimated or even implied which could explain the low total emission.
(3) No VCM recovery system vent losses given, they could be included in this emission loss.
Lbs./Lb
VCM
. 00021 W
.00032
.00001
.00038
.00036
.00489
.00036
.00033
.00021
.00489
.01196(2)
. Prod.
PVC
.00026
.00006
.00018
.00017
.00003
.00008
.00010
.00048
.00004
.00005
.00001
.00004
.00026
.00176
Tons/yr.
VCM
12.6
19.3
0.7
23.4
22.3
299.3
22.3
20.2
12.6
299.3
732.0
PVC
15.7
3.7
11.0
10.2
1.8
5.1
5.8
29.6
2.6
2.9
0.4
2.6
16.1
107.5
o
I
Ul
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-5
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
75
Source
Area Description
G Exhaust From Dust Collector
F Centrifuge
VCM In Resin
D Vent Condenser
E Slurry Tank Vent
B Reactor Vent
E Blow Down Tank Vent
B Reactor Cleaning
F Slurry Filtration
Total (2)
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
(1)
Emissions
Lbs./Lb
VCM
.00400
.000003
.00090
.00600
.00005
.000003
.0000008
. Prod.
PVC
.00009
.00030
.00006
Tons AT.
VCM PVC
150.0
- 3«
33.8
225.2
1.9
—
-
11.
2.
4
3
3
o
I
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-6
Plant Capacity, Million Lbs.Ar.:
Process: Suspension
75
Source-
Area Description
B Reactor Safety Valves(3)
B Reactor Jets
D Stripper jets
D Recovery Condenser Vent
E Blend Tank Vent
G Dryer Vents
D Purification Condenser Vent
B Reactor Exhaust System
B Reactor Purge System
H Fugitive(4)
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
Emissions
Lbs./Lb. Prod.
VCM PVC(l)
(3)
VCD-1&2
.0144
.0032
.0003
.0015
.0015
.0018
.0020
.0019
7.45x10-6
.00015
.0091 (2) .0091
.02145
.0235
Tons A*.
VCM
120.0
11.25
56.25
56.25
67.5
75.0
71.25
0.28
5.63
341.3
804.7
pvc(i)
540.0
Notes t (1)
(2)
(3)
(4)
Total PVC loss from material balance and known losses is .0308 Ibs./lb. prod, or 1155
tons per year.
Considerable improvement is envisioned here when they switch to much larger reactors.
Their estimate is about a 40 to 50% total drop in VCM emissions.
Extra cooling used to condense VCM vapors beyond normal system. This is an emission
control device to control emissions as well as for economic reasons.
Assumed 50% VCM, 50% PVC.
a
i
to
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-7
Plant Capacity, Million Lbs.Ar.:
Process: Suspension
Source
Area Description
D Recovery Condenser Vent
E Blend Tank Vent Blower
D Reactor Jets
D Stripper jets
G Dryer Discharge (3)
G Silos
G Bagging Machine
G Bulk Loading
B Safety Valves
H Fugitive
Total
135
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCD-1&2
Emissions
Lbs./Lb. Prod.
VCM
.0015(2)
.0060
.0067
.0018
.0009
-
—
-
.0040
.0089 (5)
.0297
PVC
(1)
-
_
.0063
.00055
.00022
.00034
-
.0089
.01631
Tons /Yr .
VCM
101.25
405.0
452.25
121.5
60.75
-
_
.
270.0
600.75
2011.5
PVC
(1)
_
_
425.25
37.125
14.85
22.95
600.75
1100.925
Notes: s (1) Known losses plus fugitive losses from material balance indicate 0.0389 Ibs./lb. PVC prod.
or a total of 2626 tons of solid loss per year.
(2) Now equipment on order (delivery late 1974) to improve efficiency from 99.5$ to 99.9$.
This will reduce total VCM loss to .0003 at this point.
(3) Considerable improvement will result from installation of new type cyclones of 99.9$
efficiency as compared to present 99.5$. Equipment is on site and will be installed
shortly.
(4) In addition to standard vacuum, compression and condensing system a two-stage low
temperature condensing system is used (40°F water and 0°F freon or glycol). This is an
emission on control device as well as an economic device.
(5) Assumed 50% VCM, 50% PVC.
o
i
to
00
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-8 ( ^
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
Source
Area Description
B Safety Relief Devices
D Reactor Evacuator
E Blending Tanks
D Recovery System Vent (3)
G Cyclones & Bag Filters
Solid & Liquid Wastes
H Fugitive (2)
Total
225
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
VCD-2
Emissions
Lbs./Lb
VCM
.0024
.0043
.0054
.0041
.0027
.0134(4)
.0323
. Prod .
PVC
.0012
.004?
.0141
.0134
.0334
Tons AT.
VCM
270.0
483.75
607.5
461.25
303.75
1507.5
3633.75
PVC
135.0
528.75
1586.25
1507.5
3757.5
Notes: (1) All plants at location have a standard section covering control devices. Only parts of
this section apply to each individual plant.
(2) The only indication that fugitive emissions are being reduced is in the standard section
on control devices that says an organic vapor detection device is being used to locate
VCM leaks. It is stated that it can detect VCM levels below odors detection but does not
indicate how sensitive it is.
(3) Standard vacuum, compression and condensation system used to recover VCM for economic
reasons.
(4) Assumed 50% VCM, 50% PVC.
TJ
O
I
N>
VO
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-9
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
175
Source-
Area Description
B Safety Relief Devices
B Reactor Evacuator
E Blending Tanks
D Recovery System Vent
G Cyclones & Bag Filters
H Fugitive (2)
Total
Type Of Control
Emission Device
Control Catalog
Device (i) I.D.No*
(3)
VCD-2
Emissions
Lbs./Lb. Prod.
VCM
.0012
.0072 ,
.0048
.0003
.0071
.0077 (4)
PVC
.0001
.0015
.0077
Tons/Yr.
VCM
104.7
636.4
420.5
30.2
626.8
673.8
PVC
7.4
131. 4 <
673.8 i
.0283
.0093
2492.4
812.6
Notes: (1) All plants at location have a standard section covering control devices
this section apply to each individual plant. <-ontro± devices
(2) The only indication that fugitive emissions are being reduced
Only parts of
(3) In addition to standard vacuum
condensing is used which makes
(4) Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-10
Plant Capacity, Million
Process: Suspension
Source
Area Description
B Safety Relief Devices
B Reactor Evacuators
E Blend Tank
D Recovery System Vent
G Cyclone & Bag Filters
Solid & Liquid Losses
H Fugitive (2)
Total
120
Type Of Control
Emission Device
Control Catalog
Device(l) I.D. No.
VCD-3
Emissions
Lbs.
VCM
.0016
.0067
.0053
.0087
.0002
.0053
.0275
/Lb. Prod.
PVC
.0009
.0013
.0053
0)6). 0275
TonsAr.
VCM
98.6
412.2
325.9
535.2
12.3
325.4
1650.0
PVC
55.2
79.7
325.4
1650.0
>n
<
i
GJ
.0553
.0350
3359.6
2110.3
Notes:
(1)
(2)
3)
*)
(5)
All plants at location have a standard section covering control devices. Only parts of
this section apply to each individual plant.
The only indication that fugitive emissions are being reduced is in the standard section
on control devices that says an organic vapor detection device is being used to locate
VCM leaks. It is stated that it can detect VCM levels below odors detection but does not
indicate how sensitive it is.
High fugitive emission.
Standard vacuum, compression and condensing system used to recover VCM for economic
reasons.
Assumed 50% VCM, 50% PVC.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-ll
Plant Capacity, Million Lbs./yr.: 80
Process: Suspension
Source-
Area Description
B Safety Devices
B Reactor Evacuations
E Blend Tanks
D Recovery Condenser Vent
G Cyclones & Bag Filters
Solid & Liquid Losses
H Fugitive (2)
Total
Type Of Control
Emission Device
Control Catalog
Devicefil I.D. No.
(3)
Emissions
Lbs./Lb
VCM
.0043
.0024-
.0012
.0052
.0052
.0090
.0061(4)
.0334
. Prod.
PVC
.0006
.0024
.0090
.0061
.0181
Tons /yr.
VCM
164.25
92.0
45.6
197.5
200.2
344.7
233.5
1277.8
PVC
22.3
90.7^
3^4.7 <
233.5 ?
NJ
691.2
Notes; (1) All plants at location have a standard section covering control devices. Only parts of
this section apply to each individual plant.
(2) The only indication that fugitive emissions are being reduced is in the standard section
on control devices that says an organic vapor detection device is being used to locate
VCM leaks. It is stated that it can detect VCM levels below odors detection but does not
indicate how sensitive it is.
(3) Standard vacuum, compression and condensing system used to recover VCM for economic
reasons.
(4) Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-12
Plant Capacity, Million Lbs.Ar.r 113
Process: Suspension
Source-
Area Description
B Safety Relief Devices
B Reactor Evacuators
E Blending Tanks
D Recovery Condenser Vent (3)
G Cyclone & Bag Filters
Solid & Liquid Losses
H Fugitive (2)
Total
(1)
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
VCD-2
Lbs./Lb. Prod.
VCM
.0004
.0022
.0060
.0007
.0093
.0046
.0052 (4)
.0284
PVC
.0002
.0012
.0046
.0052
.0112
Tons AT.
VCM
23.6
124.8
337.3
41.2
525.6
261.5
294.1
1608.1
FVC
11.8
64.8 ^
261.5 <
294.1 /„
LO
632.2
Notes ; (1)
- *
(3)
(4)
All plants at location have a standard section covering control devices. Only parts of
this section apply to each individual plant.
The only indication that fugitive emissions are being reduced is in the standard section
on control devices that says an organic vapor detection device is being used to locate
VCM leaks. It is stated .that it can detect VCM levels below odors detection but does not
indicate how sensitive it is. . .
Standard vacuum, compression and condensation system used to recover VCM for economic
reasons .
Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-
Plant Capacity, Million Lbs./Yr.: 42
Process: Suspension
Source
Area
D
G
H
Description
Recovery System Vent
Bag Filters
Fugitive
Total
Type Of Control
Emission Device
Control Catalog
Device I.D.No.
Emissions
Lbs./Lb
VCM
.00203
.0002
.0086(2)
.01083
. Prod.
PVC
*
.0086
.0086
Tons/Yr .
VCM
42.9
4.2
181.7
228.8
PVC
181.7
181.7
* No data are given for PVC losses. Fugitive loss noted is assumed.
n
i
U)
Notes: (1) No emission devices installed at this plant now but all being considered for future
No mention of type.
(2) Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-l4
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
150
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM PVC
Tons/Yr.
VCM
PVC
NO SATISFACTORY DATA
o
to
ui
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-15 C1)
Plant Capacity, Million Lbs./Yr.: 175
Process: Suspension
Source-
Area
D
G
G
G
G
G
G
G
G
G
G
G
A
A
B
D
Q
H
H
Notes:
Description
Recovery System Vent (2)
Primary Dust Collector
Primary Dust Collector
Secondary Dust Collector
Secondary Dust Collector
Silo Collectors
Bag Filters
Bag Filters
Bag Filters
Bag Filters
Bag Filters
Bag Filters
Transfer System
Transfer System
Vacuum Jet Steam
Recycle on VCM Recovery System
Conveying Losses
Transfer Losses
Emission from Hood Over Callender
Transfer Losses to Trucks & RR Cars
Building Emissions
Fugitive
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM PVC
.001086
.00395 .000429
.00528 .000573
.000049 .000429
.000049 .000573
.000025 .00100
.000213
.000025 .000068
.000213
.000049 .000049
.000053
.000034
.000018
.000049
.000049
.002122
.003800
.000049
.000035
.001135
.000667(3). 000667
TonsAr
VCM
95.0
345.6
462.0
4.3
4.3
2.2
_
2.2
_
4.3
_
_
_
_
4.3
18^.7
332.5
3.1
99.3
58.3
.
PVC
_
37.5
50.1
37.5
50.1
87.5
18.6
5.9
18.6
4.3
4.6
3.0
1.6
4.3
_ <
n
_ i
4.3^
-
_
58.3
.018320 .004417 1603.1
386.2
(1) Dataware complete and coverage of control devices excellent. Should discuss as exemplary
(2) Lower vacuum used than normal, no data are given for condensing conditions but the low
emission indicates that some cooling or chilling is involved. ±m>™> DU^ tne j.ow
(3) Assumed 50% VCM, 50% PVC .
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-l6
Plant Capacity, Million Lbs.Ar.:
Process: Suspension
Source
Area Description
B Reactor Vents
C Stripper Vents During Evacuation^)
C • Stripper Ventd)
E Slurry Storage Vent
D Recovery System
G Bag Filters
H Fugitive
Total
Type Of Control
Emission Device
Control Catalog
Device I.D. No.
VCD-3
Emissions
Lbs./Lb
VCM
.0056
.0018
NA
NA , .
.0008U)
.0046
.0070 (3)
.0198
. Prod.
PVC
*
.0070
.0070
Tons/Yr.
VCM PVC
112.0
36.0
16.0
92.0
140.0 140
396.0 140
.0
.0
* No data for PVC losses are given.
o
i
u>
Notes:
(l) This VCM loss is low compared to most recovery system losses. May be due to use of
scrubber system.
(2) Slurry tank (actually blend tank) is air evacuated continuously to keep concentration
of VCM vapors low.
(3) Assumed 50% VCM, 50% PVC.'
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-17-1, A-17-2, A-17-3
Plant Capacity, Million Lbs./Yr.: 125
Process: Suspension
Source
Area Description
A RR Car Unloading
A Storage Vent
A Charge Line Filter
B Reactor
B Reactor Vent & Fouling
D Recovery System, Seal Water
D Recovery System Tank Vent
D Recovery System Drain
E Blend Tank Vent & Drain
F Cyclones & Bag Filters
D Recovery System Vent (2)
D . Recovery System Degassing (2)
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
VCD-9
Lbs./Lb. Prod.
VCM PVC
Total
(3)
.0002
.0001
.0002
.00474
.0042
.0004
.0001
.0001
.0004
.00425
.00066
.00544
.02079
Tons A"r.
VCM
PVC
12.5
6.75
12,5
296.25
262.5
25.0
6.75
6.75
25.0
265.6
41.25
340.0
1300.9
v
n
i
u>
00
* PVC data not determined for this composite tabulation,
Notes:
(3)
This is a composite tabulation of three (3) suspension systems at one plant.
These recovery system losses were noted for only one of the suspension systems
(A-17-2). The losses for that system (A-17-2) are inordinantly high while the
losses for the other two systems (A-17-1 and A-17-3) are low. Normal vacuum,
compression and condensation system used for economic reasons.
No fugitive losses noted.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-l8 ' '
Plant Capacity, Million Lbs.Ar.: 117
Process: Suspension
Source•
Area Description
D&H Monomer Recovery Vent & Fugitivev2)
G Bag Filters (3)
B Reactor Vent
E Blend Tank Vent
C Stripper
F Centrifuge
Sampling
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM
.01407
.01134
.00250
.00350
_
-
-
.03141
PVC
.00100
.00353
.00087
.00102
.00048
.00020
.00710
Tons AT.
VCM
823.1
663.4
146.3
204.8
-
-
0
1837 06
PVC
58.5
206.5
50.9
59.7
28.1
11.7
415.4
o
OJ
VD
Notes:
(I)
This is a composite tabulation of two (2) suspension systems at one plant.
Fugitive emissions are included with monomer recovery system losses as the material
balance for the whole process is made here.
(3) High loss here indicates high VCM content of slurry to centrifuge and dryer.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-19
Plant Capacity, Million Lbs./yr.: 82
Process: Suspension
Source
Area Description
D&H Monomer Recovery Vent & Fugitive!1)
G Bag Filters
B Reactor
E Blend Tank
C Stripper
F Centrifuge
Sampling
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
Tons AT.
VCM
PVC
VCM
.0190
.0080
.0025
.0035
.0330
.0010
.0055
.0015
.0008
.0007
.0002
.0097
779.0
345.1
107.8
151.0
PVC
43
237
34
30
64.7
8.2
1382.9 417.9
*>.
O
Notes r (1) Fugitive emissions are included with monomer recovery system losses as the material
balance for the whole process is made here.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-20
Plant Capacity, Million Lbs./Yr.t 225
Process: Suspension
Source
Area Description
D Monomer Recovery Vent
B Reactor Vent
B Reactor Effluent, Water Stream
E Slurry Tank Vent (1)
G Dryer Vent
P Centrifuge, Water Stream
G Bag Filters (2)
G Bag Filters
G Bag Filters
H Fugitive
• Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb
VCM
.00119
.00311
.00032
.00681
.01317
.00149
—
_
-
.00541(4)
.03150
. Prod. Tons AT.
PVC VCM
133.9
- fox 349.9
.00319(3) 36.0
.00010 766.1
.00037, .1481.6
.00081(3) 167.6
.00037
.00001
.00001
.00541 608.6
.01027 3543.7
PVC
„
358.9(3)
11.3
41.6
9l.l(3)
41.6
1.1
1.1
608.6
1155.3
o
I
Notes: (1) Improved degassing system proposed which should help to reduce VCM loss, a slurry tank
vent and also from dryer vent, in fact all downstream VCM emissions from the slurry tank.
(2) No VCM emissions are indicated for bag filters and so are probably reflected in fugitive
emission.
(3) Not a potential air emission, therefore excluded from total.
(4) Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-21
Plant Capacity, Million Lbs./Xr.: 115
Process: Suspension
Source
Area Description
A RR Car Unloading
B Reactor Vent
C Stripper Vent (4)
D Monomer Recovery
E Slurry Vent
G Dryer
F Centrifuge
F Sifter
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCD-4&10
VCD-4
VCD-1,2&4
VCD-4
Emissions
Lbs./Lb. Prod.
VCM PVC
.0010
.0040
.0001
.0005
.0030
.0106
.0010
.0020
.0035
.0005
.0040
.0110
Tons Ar.
VCM
60.0
120.0
235.6
8.8
27.6
180.0
PVC
60.0
120.0
210.0
30.0
240.0
*»
NJ
632,0 660.0
Notes:
(1} VCM emissions have been shown by areas and include fugitive losses „
(2) This plant has a gas holder for miscellaneous VCM vapors and contains them
extremely well,,
(3) They are going to a solvent cleaning system which will eliminate normal opening
and closing (3-6 batches)' of reactor to one or two per year.
(4) This loss is due to losses inherent in the evacuation system.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-22
Plant Capacity, Million Lbs.Ar.: 108.6
Process: Suspension
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Source
Area Description
A RR Car Unloading
H Emission From Storage Building
A Transfer Pump
B. Reactor Vent
B Reactor Vacuum System
D VCM Recovery Condenser
H Polymerization Building Vents
H Storage Tank Vent Building
H Vent Fan
C Reactor Safety Valve & Rupture Disc
D Condenser Vent
H Building Vent
G Bag Filters
G Bag Filters
G Bag Filters
G Apron Dryers
G Apron Dryers
G Bag Filters
E Slurry Tank Vent(l)
G Rotary Dryer
E Slurry Tank (i)
F Centrifuge
G Bag House Dryer
G Bag House
G Bag House
G Bag House
H Fugitive
Total
Notes: (1) These so-called "slurry tanks" are actually blend tanks,
Lbs./Lb.
VCM
.000080
.000066
.000722
.000200
.012258
.001661
.001252
.000099
.000795
.004302
.000675
.000784
.000042
.000042
.000009
.001770
.000127
.001610
.000907
.ooi64i
.000062
.000039
.000579
.000343
.000090
.000016
.005363(2)
.035534
Prod.
PVC
^
—
—
_
_
—
-
_
—
—
-
_
.000649
.000157
-
.000102
_
—
—
.000079
-
—
.001282
.000171
.000039
.000520
.005363
.008362
Tons AT.
VCM
4.34
3.58
39.21
10.86
665.76
90.21
68.00
5.38
43.18
233.65
36.66
42.58
2.28
2,28
0.49
96.13
6.90
87.44
49.26
89.13
3.37
2.12
31.^5
18.63
4.89
0.87
291.28
1929.93
PVC
^^
-
-
_
^
<
. 0
i
— *»
u>
—
—
-
_
35.25
- 8.53
' 5.5^
-
_
_
4.29
-
_
69.63
9.29
2.12
28.24
291.28
454.17
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-23
Plant Capacity, Million Lbs./yr.: 235
Process: Suspension
Source
Area Description
A VCM Receiver, Fresh
D VCM Receiver, Recovered (1)
D VCM Receiver, Mixed
A VCM Receiver, Fresh
D VCM Receiver, Recovered (1)
D VCM Receiver, Mixed
A Strainer
E Blend Tank
E Blend Tank
G Bag Filters
G Resin Silos
G . Resin Silos
G Resin Silos
G Exhaust From Compounding Lines
H Fugitive
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
Emissions
Lbs./Lb. Prod.
VCM PVC
.00003 *
.00005
.00005
.00015
.00007
.00030
.00020
.00044
.00388
,01399(2)
.00002
.00001
.00001
.000015
.01012(4)
Tons A"r .
VCM PVC
3.9 *
5.7
6.1
17.1
8.8
35.9 2
23.7 o
52.6 i
459.9 **
1659.0(2)
2.7
1.3
0.9
1.8
1200.7
.02936
3480.7
* No data are given for PVC losses.
Notes: (1) New refrigerated condenser system to be installed this year will reduce these losses
about 85$.
(2) Ineffective stripping of VCM from latex causes high VCM emission here. Also makes
fugitive losses greater.
(3) Emission control procedure section identical for both plants A-23 and A-24.
(4) Assumed 50% VCM, 50% PVC.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-24
Plant Capacity, Million Lbs./Jfr.:
Process: Suspension
220
Source-
Area Description
D Recovery System Vents
B Reactor Dump Screen
C Slurry Tank Vent (3)
B Reactor Cleaning Exhauster
G Dryer Exhaust (1)
G Silos
H Fugitive
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
Emissions
(1)
Lbs./Lb. Prod.
VCM PVC
.000005 *
.001022
.002492
.002250
.005388
.000103
.006255(4)
TonsAr.
VCM PVC
0.4 *
113-9
275.9
245.3
595.7 v
11.4 <
688.5 1
017515
1931.1
* No data are given for PVC losses.
Notes; (1)
(2)
(3)
(4)
Less losses here than sister plant (A-23) perhaps due to higher temperature used to
eliminate VCM from latex.
Emission control procedure section identical for A-23 and A-24. .
Continuous exhauster on b.oth slurry and blend tanks to prevent VCM buildup in vapor
space.
Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-25
Plant Capacity, Million Lbs.Ar.: 120
Process: Suspension
Source
Area Description
B Reactor Fouling
B Course Material & Lost Batches
D VCM Recovery Vent (1)
B Spillage
H Process Leaks
E Slurry Tank Vent
F Centrifuge
G Dryer Spillage
G Dryer Exhaust
G RR Car Spillage
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb
VCM
.000015
.000022
.013^32
.000003
.000650
.000204
.000058
.000029
.003351
.000001
. Prod.
PVC
.002657
.004015
-
.000650
_
_
.000752
.026025
.000767
.002227
Tons/Yr.
VCM
0.9
1.3
805.9
0.2
39.0
12.3
3.5
1.8
201.0
0.1
PVC
159-4
240.9
-
39.0
—
_
45.1
156L5
46.0
133.6
*a
n
i
£*•
(Ti
.017765 .037093 1066.0 2225.5
Notes; (1) The loss at this point is 75$ of total loss noted.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-26
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
175
Source
Area Description
B Reactor Vents
D VCM Recovery System (1)
C Stripper Vents (2)
E Slurry Vent
G Dryer
G Product Transfer
H Reactor Room Vents, Fugitive
H Misc. Fugitive (Matl. Balance)
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I .P. No.
Emissions
Lbs./Lb
VCM*
.0012
.0013
.0048
.0042
.0058
.0025
.0017
.0042
. Prod .
PVC*
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-2?
Plant Capacity, Million Lbs./Yr.:
Process: Suspension
220
Source•
Area Description
B Reactor Vents
D VCM Recovery System (1)
C Stripper Vents (2)
E Slurry Vents
G Dryer
G Product Transfer
H Reactor Room Vents, Fugitive
H Misc. Fugitive (Material Balance)
Total
Type Of Control
Emissions
Control rat.Rlng Lbs./Lb. Prod.
Device I.D. No. VCM*
.00119
.00150
.00154
.00561
.00711
.00158
.00170
.00520
PVC*
_
-
_
.00115
.00012
_
-
Tons AT.
VCM*
13L9
166.2
170.7
621.7
787.9
175.9
188.4
587.3
PVC*
..
_
_
127.4
13.3
-
13
^j
1
00
.02553 .00127 2830.0 140.7
* Emissions to air only,
Notes; (1) We have no information on' system used but as the emission is very low, system must be
considered excellent.
(2) Exhauster reducing VCM vapor accumulation in vapor space.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: A-28
Plant Capacity, Million
Process: Suspension
23
Source
Area
B
C
C
G
H
Description
Reactor Vents
Stripper Clean Out
Stripper Operation (3
Bag Filters
Fugitive
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D.No.
Emissions
Lbs./Lb.
VCM
.001?
.0016
.0199
.0030
.0105
.0367C1)
Prod. Tons/Yr.
PVC VCM PVC
* 19.5
18.4
228.8
3^.5
120.7
421.9
No loss data for PVC are given.
Notes; (1) Overall loss is high due mainly to high loss from stripping operation and fugitive
losses. From brief description of process it appears that vacuum and condensing
equipment is minimal.
2) Evacuation to keep VCM vapor concentration low.
3) Includes VCM recovery system.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: s-1
Plant Capacity, Million Lbs./Yr
Process: Dispersion
40
Source
Area
B
B
D
B
E
G
G
H
Description
Type Of
Emission
Control
Device
,(1)
Operating Upset
Reactor Vent
Recovery System Vent
Filter Cleaning
Blend Tank Vents
Dryer Filter Cleaning
Dryer Vent(2)
Fugitive Lossesv3J
To Sewer
To Landfill
To Landfill
TOTAL
Control
Device
Catalog
I.D. No.
VCD-2
Emissions
Lbs./Lb. Prod.
VCM
.00300
.00060
.00469
. 00020
.00500
. 00005
.01774
.01000
__
._
__
.04128
PVC
_ mm
—
—
—
—
.00320
,00020(2)
— —
.10000
.05290
.10000
.25612
Tons AT.
VCM
57.8
12.0
93.7
4.0
99.9
1.0
35^.8
199.7
— —
—
822.9
PVC
_ —
—
—
—
—
65.7
4.4
—
2001.7
1055.6
2001.7
5129.1
<
n
i
Ul
o
Mores:
(I)
(3)
These losses seern unusually high.
These losses are very high and indicate a poor stripping system or lack of heat
in final VCM removal cycle.
Fugitive losses somewhat high.
Along with normal vacuum and compression system, a low temperature Brine cooling system
is used to keep emission at this point low.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-2
Plant Capacity, Million Lbs.Ar.
Process: Dispersion
7.7
Source
Area
B
B
E
Description
(1)
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Reactor Slowdown
Reactor Evacuation
Hold Tank Displacement
TOTAL
Lbs./Lb.
VCM
. 00205
,00068
.00011
.00284
Prod.
PVC
*
— —
TonsAr
VCM
7.9
2.6
0.4
10.9
.
PVC
—
— ~
* No data on product loss are given.
Notes: (l) Material balance closed without any report of fugitive emissions.
(2) Total emissions extremely low but all products are sold as liquid latices so no drying
is involved which may account for such low emissions.
o
i
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-3
Plant Capacity, Million Lbs./Yr.t 27
Process: Dispersion
Source
Area Description
B Reactor Vent
C Stripper Vent
E Slurry Storage Vent (4)
D Recovery System Vent
G Bag Filters
H Fugitive
TOTAL
*No data are given for PVC losses.
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCD-3
Emissions
Lbs./Lb. Prod.
VCM PVC
.0056(1) *
.0018
.0015
.0008
.0350(2)
.0116(3)
.0563
Tons AT.
VCM PVC
75.6
24.3
20.3
10.8
472.5
156^6
760.1
Notes
SI
This figure does not agree with #/Hr figures even allowing for hours in operation.
Loss of VCM through bag filters is extremely high, indicating poor stripping of
VCM in stripper.
Fugitive emission somewhat high and no mention is made of how calculated.
Continuous air evacuation from blend tank (here called slurry tank) to keep VCM
vapor concentration from building up.
ti
n
i
NJ
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-4
Plant Capacity, Million Lbs./Yr.: 40 V1)
Process: Dispersion
Source
Area Description
D&H Recovery System and Fugitive
B Reactor Vent
C Slurry Tank Vent (3)
G Bag Filter From Dryer
G Micropulverizer
G Bag Filters-Silos-Shipping
Sampling
TOTAL
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb,
VCM
.0246(2)
.0025
.0002
.0094
.0367
, Prod.
PVC
.0050
.0195
.0018
.0050
.0018
,0026
.0357
Tons AT.
VCM
492.0
50.0
4.0
188.0
734.0
PVC
100.0
390.0
36.0
100.0
36.0
52.0
714.0
•V
<
o
i
Ul
U)
Notes:'
(I)
Based on 350 Day/STr.
Based on a material balance. While heat and vacuum are used in this recovery system
the loss is very high^ perhaps refrigerated cooling would help.
(3) Change over losses only.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-5
Plant Capacity, Million Lbs./Yr.:
Process: Dispersion
11
Source•
Area Description
A Tank Car Unloading
A VCM Storage Vent
A Charge Filter
B Reactor Vent and Waste
D Seal Water
B Accumulated Vapor
C Latex Transfer Screen(4)
E Blow and Blend Tanks
E Blend Tank Heel
G Bag House
B Degassing Jet
Misc. Spillage, Waste, Etc
TOTAL
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb
VCM
.0003
.0001
.0003
.0060
.0005
.0001
.0574
.0039
__
.0536
.0395
—
.1610(1)
. Prod.
PVC
M M
__
.0129
__
__
.0753
.0001
.0026
.0008
--
.0222
.1137(2)
Tons AT.
VCM
1.4
0.7
1.4
32.9
2.8
0.7
315-7
21.8
__
294.7
217.5
--
889.6
PVC
_• «
--
— —
69.5
—
—
414.0
0.7
14.0
5.6
--
122.0
625.8
'"d
<
o
1
Ul
tfs.
Notes:
This is an abnormally high VCM loss.
Very high PVC loss.
Combining the two losses indicates that about one-quarter (25$+) of the initially
charged VCM is loss to. atmosphere and solid waste. Although this is a small
giant it is hard to believe such high losses.
vidently there is no VCM recovery system used.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-6
Plant Capacity, Million Lbs./Yr.:
Process: Dispersion
3.5
Source
Area Description
A Tank Car Unloading
A VCM Storage
A Charge Filter
B Reactor
D Seal Water
C Latex Screen and Blow Tank
E Blend Tank
G Bag House
B Reactor Degassing Jet
Solid and Liquid Wastes
TOTAL
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM
PVC
.0003
.0001
.0003
.0066
.0007
.0914
.0042
.0871
.0716
.2623
,0238
,0001
,0885
.0011
.0287
.1422
Tons AT.
VCM
0.5
0.3
0.5
11.4
1.2
158.7
7-3
151.1
124.3
455-3
PVC
41.2
0.3
153.5
2,0
13
<
O
I
ui
U1
Notes: This plant is the same as B-5 only this operation is a co-polymer dispersion rather than
a homo-polymer dispersion. Losses are abnormally high even for a small operation. The
emission figures indicate that close to one million pounds of VCM is loss to the air to
produce three and a half million pounds of PVC.
Same notes apply as B-5
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-7
Plant Capacity, Million Lbs.Ar.:
Process: Dispersion (1)
Source
Area
A
D
H
C
G
Description
Storage Tank Vent
Scrubber Vent
Fugitive
Flash Pot Vents (2)
Dryer Exhaust
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
VCD-3
Emissions
Lbs./Lb. Prod.
VCM PVC
.0007
.0021
.0009
.0112
.0008
.0157
Tons Ar.
VCM
190.9
PVC
o
i
ui
* No product losses reported.
Notes: (1) This is a unique product and can be considered a dispersion process,
(2) Atmospheric vent to stack.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-8
Plant Capacity, Million Lbs./Yr
Process: Dispersion
Source
Area Description
B Reactor Vent
C Stripper Clean Out
C Stripper Operation (5
E Slurry Vent
D Recovery System
G Bag Filters
H Fugitive
Total
26
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM PVC
,0074 *
•0035,,,
.1061V1)
.0024
.0008
.0313(2)
,012?
Ton s AT.
VCM PVC
96.2
^5.5
1379.3
31.2
10.4
406.9
165.1
.1642(3)
2134.6
13
n
i
Ul
* No data for PVC losses are given.
Notes:
(3)
Very high VCM loss (see E-2).
Higher loss than most plants.
Hard to believe that l/6th of total vinyl chloride is emission to atmosphere.
Evacuation to keep VCM vapor concentration low.
No VCM recovery, just vacuum jet steam evacuation.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-9
Plant Capacity, Million Lbs./Yr.: 15
Process: Dispersion
Source
Area
Description
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM
PVC
Tons AT.
VCM
PVC
H
Fugitive (1)
.0436
327.1
Total
.0436
327.1
* No solid PVC waste data are given.
n
i
Ul
CO
Notes: (1) All emissions are considered fugitive. Indicated figure (0.0436) obtained from overall
material balance (4.1$ VCM emission: 4.1/94.0 = .0436 Ibs. VCM emission per pound of
product produced). Only latices made, no drying systems involved.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: B-IO' '
Plant Capacity, Million Lbs./Yr.:
Process: Dispersion
Source
Area
C
G
B
H
15
Description
Stripper Vents
Plastic System Vent
Reactor Room Vents
Misc. Fugitive (Material Balance)
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.(2)
VCM*
Tons/Yr.
.02314
.00030
.00220
.00220
.02784
PVC*
(3)
VCM*
208.7
PVC*
(3)
n
* Air emissions only.
Notes:
This unit makes latices only.
Product averages 83$,PVC,figures based on total pounds of product,
No PVC losses to atmosphere.
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
Plant Code Number: C-l
Plant Capacity, Million Lbs./Yr.: 32
Process: Bulk
Source
Area Description
B Safety & Relief Valves C1)
B Reactor Vents
D Recovery System Vent(2)
G Bag Filters
H Scrap & Waste
H Fugitive
Total
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Lbs./Lb. Prod.
VCM
PVC
.002784
.007865
.002000 .002784
.000716 .006446
.003973(3).003973
,017338 .013203
Tons AT.
VCM
45.1
127.5
1.4
281.0
PVC
45.1
103.6
64.4
213.1
13
$
I
-------
TABLE FV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
Plant Code Number: C-2
Plant Capacity, Million Lbs.Ar.: 1Q5
Process: Bulk
(CONTINUED)
Source
Area Description
D Recovery System Pump VentC-1-)
D Recovery System Tank Vent
D Recovery System Pump Seal Water
G Bag Filters
B Reactor Vents
Reactor Cleanings
Spillage & Scrap
H Fugitive
Total
Type Of Control
Emissions
Emission Device ....,...,.,
r.nrvhrnT mt.nlng LbS./Lb. Prod .
Device I.D. No. VCM
.01502
.00184
.00029
.00018
.00104
_
—
.00823(2)
PVC
-
-
_
..
.01168
.00083
.00823
Tons AT.
VCM
788.4
96.4
15.3
9.6
54.8
—
431.9
PVC
.
-
_
_
613-2
43.8
431.9
.02660 -02074 1396.4 1088.9
o
i
Notes (1)Recovery system has high emission losses. Improvement in condensing and degassing system
might help and is proposed for near future.
(2)Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE
(CONTINUED)
>lant Code Number; C-3
>lant Capacity, Million Lbs.Ar.: 168
'rocess; Bulk
Source-
Area Description
D Recovery System Vent
A Storage Vent
D Recovery System - Caustic Scrubber
A Transfer Filter
B First Stage Reactor Vent
D Transfer Filter
B Vacuum System on Reactors
G Bag Filters Before Screening
G Bag Filters to Silos
G Bag Filters to Screen
G Powder Blender
G Silos
G Bagging Hopper
G RR Car Loading
H Fugitive
B Emergency Venting
Total
Type Of
Emission
Control
- Device
Control
Device
Catalog
I.D. No.
VCD-2
Emissions
Lbs./Lb,
VCM
.001564
.000068
.000052
.000016
.000008
.000026
.001669
.001251
.000991
.00041?
.0010^3
.000010
.000005
.000005
.002529 (2)
.000443
, Prod.
PVC
.000104
.002034
.001043
.000417
.000209
.000502
,oooio4
.002529
Tons AT.
VCM
131.4
5.7
4.4
1.3
•0.7
2.2
140.2
105.1
83.2
35.0
87.6
0.9
0.4
0.4
212.4
37.2
PVC
8.83
n
|
170. 8 £
IXJ
87.6
35.0
17.5
43 8
8.8
' 212.4
.010097 .006942
848.1
584.7
Notes:
(1) This plant seems to be an exemplary one with excellent emission controls.
(2) Assumed 50% VCM, 50% PVC.
-------
TABLE PV-6
NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE
(CONTINUED)
Plant Code Number: D-l
Plant Capacity, Million Lbs.Ar.
Process: Solvent
24
Type Of
Emission
Control
Device
Control
Device
Catalog
I.D. No.
Emissions
Source
Area Description
A Solution Storage
D VCM Vent Scrubber VCD-3
F Centrifuge
A Solid Feed Tank
B Precipitation Tank
C Slurry Tank (2)
C Slurry Tank
G Drying Stages
G Drying Stages
G Drying Stages
Vacuum Transfer
G Bin Storage
D Crude Solvent Storage
D Crude Solvent Storage
D Crude Solvent Storage
D Extractor
D
D Extract Storage
D Vinyl Acetate Still
D Vinyl Acetate Storage
D Solvent Still
D Solvent Storage
D Aldehyde Column
D Non-Solvent Still
D Non-Solvent Storage
H Fugitive
Total
Notes: (1) Low emissions but there is no other solvent process to compare with it to indicate if
this is normal for this type process.
(2) Atmospheric vents to keep tanks at atmospheric pressure.
Lbs./Lb.
VCM
.000001
.000074
.000014
.000028
.001130
.000282
.000212
.006532
—
.001765
•
.001388
.000245
.000011
—
mm
.000706
.000035
.000060
.000056
.000247
.012786
Prod.
FVC
p
u
o
CO
H
CO
o
o
fc
0
Tons/Yr.
VCM FVC
0.9
0.2
0.3
13.6
3.4
2.5
78.4 '
(
21.2
_
16.7
2.9
0.1
—
•*
8.5
0.4
0.7
0.7
3.0
153.5
-------
PVC-64
Particulate PVC emissions are also associated with
these vent streams. However, with cyclones and bag
filters the particulate emissions are relatively small
in amount (approximately 0.004 Ibs./lb. of product).
3. Centrifuge Vent (Source Area F)
In many cases there is a centrifuge vent associated
with the suspension process. The magnitude of the VCM
emission in this vent depends on the efficiency of
upstream stripping. Reported values range between
0.00001 and 0.004~lbs. of VCM/lb. of PVC product.
4. Blend Tank (Source Area E)
The blend tank emissions vary widely from plant to
plant and depend markedly on the efficiency of the
stripping operation. The volume is very low and it can
be tied into the stripping system in order to eliminate
any direct emission to the outside air.
Blend tank emissions are only associated with the
suspension and dispersion type processes and in these
plants the reported VCM losses vary between 0.0001 and
0.007 Ibs./lb. of PVC product.
B. Intermittent Air Emissions
1. Unloading and Charging Facilities (Source Area A)
There is a certain amount of VCM emission at
virtually all unloading facilities. Most plants
unload under pressure and most vapors are kept
enclosed, but there is always some emission plus losses
at pumps, valves, meters, etc. The same is true for
weigh tanks, meters and pumps used to charge reactors.
None of these emissions are controlled other than using
good practices consistent with handling of a toxic
liquified gas. Reported VCM losses from these sources
range from 0.0004 - 0.001 Ibs./lb. of PVC product.
2. Reactors (Source Area B)
There are several possible emission streams from the
reactors. During operation, if a run-away reaction
occurs, it is generally stopped by releasing the pressure
and venting to stacks (one company uses a gas holder).
This vent contains a high concentration of VCM but only
lasts for 5 to 15 minutes and occurs infrequently.
Several companies are working on (may have it worked
out by now) a "short stopping reaction" that would make
"blow down" unnecessary.
-------
PVC-65
A more frequent reactor emission occurs when the
vessel is purged and during cleaning. Normally after
the polymerization reaction is completed and the batch
is removed, VCM vapors are pulled from the reactors by
a vacuum system and a new charge is added. However, the
reactors must be cleaned periodically (every two to six
batches). This means each reactor is opened every one
to three days for about three hours for cleaning. This
causes emissions which are normally kept down by
pulling a vacuum on the reactor and compressing and
condensing the removed vapors. During the actual
cleaning operation, a substantial air stream is blown
through the vessel to help protect the worker(s) in
the reactor from VCM exposure. The amount of VCM in
the vented air stream is very low (5 to 50 ppm) and
would present the same problems of emission control as
do the dryer and conveying air systems. New improved
methods of cleaning reactors such as water jet or
solvent cleaning systems greatly reduce these emissions
or a water purge can be used to push the VCM remaining
after the reaction is over to the recovery system.
Total reported VCM emissions from the reactors
normally varies between 0.001-0.01 Ibs./lb. of PVC
product, with the lowest values (0.001-0.003 Ibs./lb.
associated with the bulk and solvent polymerization
processes. If no equipment is provided to recover VCM
from the reactor vent the VCM emissions can be as high
as 0.04-0.08 Ibs./lb. of PVC product.
3. Safety Valves (Included in Source Area B)
Occasionally a run-away condition in the reactor
can cause the relief valves to open resulting in VCM
emissions. Most of the surveyed plants did not report
emissions from this source. However, the few plants
that did report these losses showed VCM emission
figures of 0.0004-0.004 Ibs./lb. of PVC product. Since
these emissions are for a short period on a very
infrequent basis they represent a rather large
instantaneous rate.
4. Strippers (Source Area G)
The emissions from a stripper are generally completely
contained in the overall vacuum, compression, condensation
cycle of the VCM recovery system and present no particular
problem. However in some plants the stripper is opened
to the atmosphere following the vacuum step in order to
repressure the vessel and dump the batch to the blend
tank. This can result in some VCM emission. In plants
employing a monomer recovery system the reported VCM
emissions associated with the stripping operation vary
between zero and 0.005 Ibs./lb. of PVC. If no recovery
-------
PVC-66
system is used these losses can be as high as 0.1
lbs./lb. of PVC. All but one of the few plants that
do not have monomer recovery systems are small
capacity units (3-11 million PPY PVC).
C. Fugitive Emissions
It has been assumed that "Fugitive Emissions" cover
all air emissions that are not diverted to a simple vent
or stack from the equipment itself. They are caused by
leaks at pumps, flanges, filters, strainers, seals, etc.,
and can be reduced greatly by "good housekeeping". It
would be possible to eliminate pump packing or seal
leakage by the use of "canned pumps" at some expense in
old plants but with less expense in new units. The
principal problem with "fugitive emissions" is to keep
them low at all times. These emissions can be reasonably
under control one minute and suddenly increase greatly.
Only good maintenance, with the accent on preventive
maintenance, can keep fugitive emissions at a reasonable
low level.
Table PV-7 lists all the reported fugitive VCM
emissions for the various PVC plants. The only truly
meaningful "fugitive emission" is one that is arrived
at from a material balance after accounting for all
known emissions and discharges. It is difficult to be
certain that all wastes (solid, liquid and dissolved)
have been included in the overall material balance.
If some of these losses are omitted, the reported
fugitive air emissions are high. It is also difficult
to determine the exact composition of these air emissions.
In most of the survey reports these losses are shown
as VCM. Based upon the "snow field" appearance around
the plants undoubtedly some of these emissions are
particulate PVC. For this study an arbitrary assumption
has been made that material balance losses are 50% VCM
and 50% PVC waste. This was assumed by the producers
of Plants A-6 through A-13 and considered reasonable
by several other manufacturers.
While the reported fugitive emissions (VCM) for the
individual plants vary over a wide range, Table PV-7 shows
that the average VCM fugitive emission for the suspension,
dispersion and bulk processes are similar (0.005-0.01 Ibs./
Ib. of PVC). As might be expected, fugitive emissions
for the solvent process appear to be much lower
(0.00025 lbs./lb. of PVC).
-------
TABLE PV-7
SUMMARY OP FUGITIVE EMISSIONS
VCM Emissions
Plant
Method Determined
Suspension Process
A-l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A-ll
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-21
A-22
A-23
A-24
A-25
A-26
A-2?
A-28
Quantity not specified separately
Quantity not specified separately
Material balance
No
No
By
By
By
By
By
By
By
By
No
Close
Close
indicated fugitive loss, but there is material balance
fugitive losses reported - no material balance
difference
difference
difference
difference
difference
assumed 50$ VCM, 50$ PVC
assumed 50$ VCM, 50$ PVC
assumed 50$ VCM, 50$ PVC
assumed 50$ VCM, 50$ PVC
assumed 50$ VCM, 50$
assumed 50$ VCM, 50$
PVC,
PVC,
difference
difference - assumed 50$ VCM^ 50$ PVC
difference - assumed 50$ VCM, 50$ PVC
emission data given
check on all emissions
check on all emissions
No specific value given
Quantity not specified separately
Quantity not specified separately
Unidentified losses from material balance
Quantity not specified separately
Fugitive emissions are "guesstimate"
Fugitive by material balance
Fugitive by material balance
Process leaks (method not given)
Material balance
Material balance
Material balance
By Mfgr.
By Mfgr.
By Mfgr.
By Mfgr.
By Mfgr.
By Mfgr.
By Mfgr.
By Mfgr.
Lb/Lb of Prod. Tons/Yr
0.0091
0.0089
0.0134
0.0077
0.0275
0.0061
000052
0.0086
0.0018
Subtotal
Wt. Average
0.005M1)
0.0083
0.0101
0.0063
0.0006
0.0059
0.0069
0.0105
o.0081
770.0
341.3
600.7
1,507.5
673.8
1,650.0
233.5
294.1
181.7
157.6
140.0
608.6
450.4
1,200.7
688.5
39.0
516.1
775.7
120.7
10,949.9
o
I
-HO
VCM and 50% PVC.
-------
TABLE PV-7
SUMMARY OF FUGITIVE EMISSIONS
(CONTINUED)
VCM Emissions
Plant
Method Determined
Lb/Lbs of Prod
Dispersion Process
B-l
B-2
B-3
B-4
B-5
B-6
B-7
B-8
B-9
B-10
Material balance
None reported - produce
Method not specified
Quantity not specified
Not specified
Not specified
liquid latex only
separately
Unusual product and process
Material balance
All emissions considered fugitive - no effective control device
Material balance, manufacture latices only
Subtotal
Wt. Average
0.0100
-
0.0116
-
-
-
0.0009
0.0127
0.0436
0.0022 (D
0.0119
Tons/Yr
199.7
—
—
—
—
—
10.8
165.1 „
327.1 <
16.5 ?
CTl
875.8 oo
Bulk Process
C-l
C-2
C-3
Solvent
D-l
Material balance
Material balance
Material balance
Process
Material balance
Subtotal
Wt. Average
Total VCM Emissions ,„>
0.0047(D
0.0082 (1)
0.0025(D
0.0047
0.00025
76.0
431.9
212.4
720.3
3.1
12,549.1
Wt. Average Emissions
0.0079
Notes:
(1) All fugitive emissions have been considered 50% VCM and 50% PVC waste.
(2) For all plants listing fugitive emissions.
-------
PVC-69
Total reported air emissions for the various PVC plants vary
over a wide range. Part of this variation can be explained
by the differences in processing schemes and the amount of
emission control equipment employed. However, there are many
apparent inconsistencies in the data. These are possibly
caused by not including all sources of emission in the
survey reports and also distributing material balance losses
to the incorrect source. It is usually difficult to
ascertain average emission rates for batch type processes
especially if there are many vent streams involved and some
of these represent large volume flow rates with variable
low concentration emissions.
Table PV-8 and Figure PV-5 show the distribution of reported
total VCM emissions in the various suspension type PVC
plants. Table PV-9 and Figure PV-6 show the same information
for the dispersion type plants. The statistical data shown
in these tables and curves is completely random and merely
indicates the wide variations from plant to plant at this
time. Since we are not at all certain that all emissions
have been reported and we know that some plants have
admittedly only reported a part of their emissions, we
cannot even obtain a reliable average or mean.
D. Solid and Liquid Waste
These waste products arise from such operations as
vessel cleaning, screening and spillage. The solid material
is disposed of via landfill or contract haulage. These
losses normally are between 0.001 to 0.03 Ibs. of PVC per
Ib. of PVC product with the associated VCM losses about
one-tenth of these values.
E. Waste Water
Process waste water arises from sources such as
centrifuging and VCM stripping. Only a few plants reported
information regarding waste water. The VCM emissions
associated with this water reject range from 0.00001 to
0.001 Ibs./lb. PVC.
-------
TABLE PV-8
Code
No.
A-l
A-2
A- 3
A- 4
A- 5
A-6
A-7
A- 8
A- 9
A-10
A-ll
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-21
A-22
A-23
A-24
A-25
A-26
A-27
A-28
Total VCM
Emission
.0833
.0489
.0234
.01196
.01096
.02145
.0297
.0323
.0283
.0553
.0334
.0284
.01083
--
.01832
.0198
.02079
.03141
.0330
.03150
.0106
.03553
.02936
.01752
.01777
.0257
.02553
.0367
Rank
No.
27
25
11
4
3
10
17
20
14
26
22
15
2
—
7
8
9
18
21
19
1
23
16
5
6
13
12
24
Notes;
(1) *2 = VCM emissic
variance and stc
(2) Percentile used
of Occurrence Curve.
STATISTICAL
EVALUATION
OF PVC MFGR
'S EMISSIONS
FOR SUSPENSION PLANTS
Rank
No.
27
25
11
4
3
10
17
20
14
26
22
15
2
7
8
9
18
21
19
1
23
16
5
6
13
12
24
Rank
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Code
No.
A-21
A-13
A- 5
A- 4
A-24
A-25
A-15
A-16
A-17
A-6
A- 3
A-27
A-26
A- 9
A-12
A-23
A-7
A-18
A-20
A- 8
A-19
A-ll
A-22
A-28
A-2
A-10
A-l
Total VCM
Emission
.0106
.01083
.01096
.01196
.01752
.01777
.01832
.0198
.02079
.02145
.0234
.02553
.0257
.0283
.0284
.02936
.0297
.03141
.03150
.0323
.0330
.0334
.03553
.0367
.0489
.0553
.0833
.77173
squared; used to calculate
:ard deviation.
space data
correctly
on Probability
2(D
I2
00011236
00011729
00012012
00014304
00030695
00031577
00033562
00039204
00043222
00046010
00054756
00065178
00066049
00080089
00080656
00086201
00088209
00098659
00099225
00104329
nm noann
\J\JJ-\JU^*~t\S
00111556
00126238
00134689
00239121
00305809
00693889
02817105
Mean
Variance
Std. Dev
Percentile
3.57
7.14
10.71
14.29
17.86
21.43
25.00
28.57
32.14
35.71
39.29
42.86
46.43
50.00
53.57
57.14
60.71
64.29
67.86
71.43
•71; nn
* ~s • w v
78.57
82.14
85.71
89.29
92.86
96.43
0.02858
0.00023512
0.01533
(2)
O
I
-------
66-66
6'66 8'66
66 86
S6 06
08 Oi 09 09 Ofr OE OZ
01
t s-o z'o ro so-o
TO'O
IQ'O
8'66 6'66
66-66
-------
TABLE PV-9
Code
No.
B-l
B-2
B-3
B-4
B-5
B-6
B-7
B-8
B-9
B-10
STATISTICAL EVALUATION OF PVC MFGR'S
Total
Emissions
0.04128
0.00284
0.0563
0.0367
0.1610
0.2623
0.0157
0.1642
0.0436
0.02784
Rank
NO.
5
1
7
4
8
10
2
9
6
3
FOR DISPERSION
Rank
No.
1
2
3
4
5
6
7
8
9
10
TYPE PLANTS
Code
No.
B-2
B-7
B-10
B-4
B-l
B-9
B-3
B-5
B-8
B-6
EMISSIONS
Total
Emissions
0.00284
0.0157
0.02784
0.0367
0.04128
0.0436
0.0563
0.1610
0.1642
0.2623
0.81176
X2
00000807
00024649
,00077507
,00134689
,00170404
,00190096
,00316969
,02592100
.02696164
.06880129
.13083513
Percen-
tile
9.091
18.182
27.273
36.364
45.455
54.545
63.636
72.727
81.818
90.909
Mean = 0.08118
Variance = 0.00721552
Std. Dev. = 0.0849
Note: If we eliminate B-5,- 6 and 8 because of abnormally high values, the statistical
numbers are:
n
i
-j
ro
Mean = 0.03163
Variance = 0.00035655
Std. Dev. = 0.01888
-------
TOTAL VCM EMISSIONS, PERCENT
-------
PVC-74
VI. National Emission Inventory
Based upon the emissions shown in Table PV-6, total
approximate VCM air emissions from the surveyed PVC
manufacturing plants (approximately 4.0 billion Lbs/Yr
PVC capacity) are as follows:
VCM Emissions
Process T/T of PVC T/YR
Suspension 0.0280 48,599.6
Dispersion 0.0625 6', 534.1
Bulk 0.0166 2,525.5
Solvent 0.0128
0.0288 57,812.7
Based on an estimated 4.9 billion Lbs/Yr PVC production
rate in the U.S. during 1974, the total VCM emissions
from PVC manufacturer are estimated to be approximately
70,000 Tons/Yr.
It should be noted that most PVC plants are run at near
maximum capacity throughout the year which tends to
stabilize emissions. However, because of higher cooling
water and air temperatures during the summer months ,
VCM emissions are somewhat higher at that time of the
year.
-------
PVC-75
VII. Industry Growth Potential
The growth of polyvinyl chloride has been fairly steady
over the past three decades. The main process used
was the dispersion (emulsion) method until the 1950's
when the suspension process became predominant. The
solvent process has been in existence for a long time
(started in the 1930's) but is currently used by only
one company so it is unlikely to expand much. The
newest commercial process is the bulk process and it
will probably expand far more than the suspension
process if it proves to be more economic (as claimed
by its licensor) and if_ VCM emissions can be more
easily controlled.
Figure PV-7 indicates the growth rate of PVC (all
processes) from 1962 to date (3) (1973 last production
figure(4) and projects future growth to 1985. As
noted on the figure, the growth rate has been 11.8%
from 1962 through 1973. A diminished growth rate of
4.9% is projected to 1985. There are several factors
that lead one to believe the growth of PVC will slow
down significantly. One is the "energy crisis" which
could limit the raw material availability, another is
the drastic slow down in domestic construction, and
the third is the discovery of the carcinogenic nature
of vinyl chloride monomer. This last factor has
stopped its use as a container material for liquor,
food stuffs, etc. It probably has curtailed its use
(film form) as a food wrap and could well injure its
saleability in other areas. Another factor that is
impossible to evaluate at this writing is the
future manufacture of PVC with the new OSHA Standard
(January 1, 1975). No company would build a new plant
if they thought they could not meet the OSHA Standard
and most now feel they could not.
Figure PV-8 shows the location of existing PVC
manufacturing plants.
-------
SEMI-LOGARITHMIC 359-51
KEUFFEL & ESSER CO. HADE IN USA
I CYCLE X 7O DIVISIONS
FV
f««?:J
3T
O
~<:
0
o
c
g
o
I
o>
1C
'Jl
tt
^k-J-M-U-
^
T
-n
•t=P
o
D
S
«
S
»
§
VO
-p
x
UL
r
t^
-------
o
Figure FV-8 - Location of PVC Manufacturing Plants
-------
PVC-78
VIII. Emission Control Devices
Any device used to reduce emissions significantly and is
not used for any other reasons (primarily economic) is
considered an Emission Control Device. In other words,
it can not be profitable or it would be considered a
necessary adjunct to the process. In the case of the
commercial production of polyvinyl chloride resin there
are a remarkably few devices that can be considered truly
Emission Control Devices under this definition. However,
there are some devices that are used for economic reasons
that can be made far more effective than the economics of
the process would dictate and such refinements could
properly be called Emission Control Devices. This is
because the producer is primarily trying to reduce the
emission of VCM to a minimum (1 ppm in the working
environment).
In addition to devices, there are a number of procedures
(real and possible) that are in their entirety an
Emission Control Device even though it is a process
procedure rather than a specific piece of equipment. In
fact in the case of reducing VCM emission to a minimal
value, these procedures are more important than the usual
control devices.
We will first list equipment and then procedures including
known and used methods as well as projected devices and
procedures.
A. Control Devices
VCD-1 - Improved Stripping
The stripping of VCM from the latex in the suspension
and dispersion processes is the most important proce-
dure in respect to all subsequent downstream emissions.
Whatever VCM is not removed here will, in all probability,
wind up as an air emission. Most plants have a vacuum
system and then compress and condense the VCM vapors to
make a substantial recovery of unreacted VCM. Ideally
the vacuum pulled should equal the vapor pressure of
the water at the temperature used for the polymerization.
This would normally be about 25" vacuum (5" Hg absolute
pressure) at 135°F. Actual operating pressure is
slightly higher in order to minimize foaming. The
difference between using a vacuum of 25" Hg vs. 15" Hg
vacuum means a reduction of VCM of about 0.0028 Ibs
VCM/lb product downstream from the stripper. This is
with normal cooling water of about 80°F. This does
not necessarily reduce the total VCM emissions to the
air unless adequate cooling and compression or absorption
is used to collect the VCM from this vacuum system.
-------
PVC-79
The vapors from the vacuum pump are compressed to
about 75 psig, and condensed (85°F or lower) before
being vented. This type of high vacuum (>20" vac.)
system is employed by plants A-15, A-18, A-19 and
A-22. Probably other plants, which provided insuf-
ficient details of their vacuum system, also use
this type of low pressure evacuation.
A system suitable for a 200 million pound per year
plant, capable of pulling 25" vacuum and compressing
to 75 psig can be bought for about $200,000 to
$225,000. Installed cost with necessary condenser
would be about $750,000. (This is about twice the
amount spent for the average system normally used up
to now which pull 10" to 15" Hg vacuum.) Power
requirement for the low pressure vacuum pump and
compressor would be 80 KWH/hr. Approximately 35 GPM
of cooling water is required for the condenser.
VCD-2 - Refrigeration for Vacuum Recovery System
In order to increase VCM recovery from the vacuum
system some manufacturers (A-6, A-22 and C-3) cool
the net vent streams to -15 to -30°F. VCM emission
loss (at 25" vac.) without refrigeration would be
0.005 Ibs. of VCM/lb. PVC. Cooling the vent to -30°F
recovers approximately 80% of this material. For a
200 million pounds per year PVC plant a 5 ton refrigera-
tion unit would be required. This would cost about
$70,000 (installed). Power requirements for this unit
would be about 15 KWH/hr.
VCD-3 - VCM Recovery System Vent Scrubber
Another effective way to minimize emissions from the
VCM recovery system is to pass the compressed vent
gases (inerts and VCM vapors) through a scrubber using
a liquid having good solvency for VCM and that can be
separated from the VCM. This is done at several
plants (A-16, A-28, E-3, B-7 and D-l) with resulting
low emission losses from this source, see Table PV-10.
For a 200 million pounds per year plant, typical feed
to the scrubber would be about 115 Ibs./hr. of VCM.
Assuming compression and water cooling is used ahead of
the scrubber for VCM recovery, the scrubber feed will be
available at 75 psig and 85°F and contain a maximum of
70 mol.% VCM (on an instantaneous basis, average
composition 10% or less). A 20 ft. by 12 inch diameter
packed tower should be able to obtain 96% recovery of
VCM from this vent stream. Based on an average emission
-------
PVC-80
rate of 0.005 Ibs. of VCM/lb. PVC product for a plant
without a scrubber approximately one million pounds
of VCM will be recovered (at lOC/lb. equivalent to
$100,000 per year). The installed investment cost
for the scrubber-stripper system and associated pumps
and heat exchangers would be approximately $125,000.
Utility requirements for the model plant size scrubber
would be 5 KWH/hr., 500 Ibs./hr. of 400-600 psig steam
and 40 GPM of cooling water.
VCD-4 - Gas Holder
Only one plant is using a gas holder at this time (A-21)
and it is interesting to note that it has the lowest
total VCM emission of any of the plants where the data
can be considered reasonably complete (0.0106 Ibs. of
VCM/lb. of PVC product). This particular plant vents
relief valves and rupture disks from compressors,
reactors, strippers, etc.; reactor purge lines, miscell-
aneous vents from weigh tanks, storage tanks, pumps,
condensers, knockout pots, etc.; vacuum pump discharge
from stripping tank, and manual reactor vents into the
gas holder. The vapors from the gas holder are compressed,
chilled and condensed VCM is returned to VCM storage.
It is estimated that the installed cost for the gas
holder and associated compression and heat exchange system
for a 200 million pound PVC plant would be approximately
$950,000. Utility requirements would consist of 40 KWH/hr.,
and 25 GPM of cooling water.
In some cases, safety regulations may prevent sending
pressure relief valve vents to the gas holder. In
these plants, it would be desirable to provide separate
pressure control instrumentation for automatic venting
to the gas holder when pressure increases to somewhat
below the relief valve set pressure. In this way
prsssure upsets can be handled without opening the
safety valves.
VCD-5 - Carbon Adsorption
The use of activated carbon has been demonstrated
experimentally as a way to reduce VCM emissions. It
certainly could be used on the outlet vent of the VCM
recovery system where the concentrations are high (over
10% VCM) and possibly prove to be reasonably economic
in this service. How effective it would be on the
outlet of a rotary dryer is conjecture, as the outlet
temperature ranges from 140 to 160°F and the VCM
concentration is less than 0.1% with air volumes of
13,000 to 25,000 ACFM per 5,000-10,000 pounds per
hour of dry PVC product. The economics would represent
-------
PVC-81
a direct added cost as the recovery value of the VCM
would be significant. Also, the excess amount of water
vapor would limit the adsorption capacity severely.
To adsorb 50 ppm of vinyl chloride vapors from a dry
air stream of 18,000 ACFM at 150°F and atmospheric
pressure requires about 1,200 cubic feet (19 tons)
of activated carbon for an 8-hour adsorption cycle.(a)
This assumes half of the carbon is in service while
the remainder is being regenerated. The regeneration
would probably be done with steam at elevated pressure
(50 psig) followed by effluent cooling (to 100°F) for
VCM condensation and recovery (60 lbs./8-hr. cycle).
As indicated, the above carbon requirements are based
on processing a dry vent stream. A dryer vent of this
magnitude would contain about 16,000 Ibs. of water
per 8-hour period. This water will undoubtedly increase
the amount of activated carbon required.
There is some question as to how many times the
activated carbon can be regenerated. Experimentally
it has been regenerated at least fifteen times without
any loss in adsorptive capacity.(7) However, because
of the large volume of activated carbon involved it
is important to know the ultimate life of this material.
Because of uncertainties as to the amount of carbon
involved and ultimate carbon life it is difficult to
develop meaningful economics for this form of emission
control device at this time.
VCD-6 - Thermal Incineration
Thermal incineration of the vent stream from a VCM
recovery system is impractical compared to other devices
as there is nothing to offset the high investment and
fuel requirement. Other devices recover VCM for reuse
and thereby partially pay for the increased investment
and operating cost. The fuel value of the incinerated
VCM streams is negligible.
The incineration of the air from a rotary dryer containing
15 to 100 ppm of VCM is possible albeit costly. Fuel
requirement is large as the VCM contributes an insigni-
ficant amount of combustible and the air is fairly well
saturated with water vapor. In addition, a large
scrubber system may be required to remove the small
amount of hydrogen chloride formed.
The equation for the reaction is:
2 CH2:CH Cl + 5 02 » 4 C02 + 2 H20 + 2 H Cl
(a) Calculated based on published data of Calgon Corp.
-------
PVC-82
In order to conserve energy it would be necessary
to employ feed-effluent heat exchange or generate
steam with the incinerator effluent. Commercial
incinerators with high heat recovery (75-80%) will
have an installed cost of 10-15 dollars per cubic
foot per minute of feed gas.(6) Therefore, the
incineration of the combined vent streams from a
200 million pound per year capacity plant (200,000
SCFM) would take a minimum capital investment of
$3,000,000 and consume about 95 million Btu/hr. of
fuel (based on 85% heat recovery) and approximately
365 KWH/hr. would be required for induced draft fans.
It should be noted that there is some doubt if the
VCM will be completely burned in the incinerator.
At the very low concentration of VCM involved
combustion efficiency could be low.
VCD-7 - Catalytic Incineration
It is possible to catalytically incinerate to similar
levels obtained with a thermal unit. The catalytic
facility would operate at lower temperature
(800-1000 versus 1800°F) and therefore require less
heat recovery and consume less fuel. The somewhat
lower initial investment and fuel saving would be
offset by catalyst replacement costs and the danger
of catalyst fouling and poisoning.
VCD-8 - Canned Pumps
An important source of fugitive emissions is from
pump glands and seals on liquid VCM pumps. This
source could be eliminated by the use of canned
pumps. In a new plant they would increase the
capital cost of pumps about 35%. In an established
plant, it would be a direct cost increase. They
normally reduce maintenance costs but when they
go "bad" the pump must be replaced so on an overall
maintenance cost basis the canned pump represents
little or no advantage. Canned pumps could be
installed systematically in a preventive maintenance
program and reduce pump emission to "zero". Incre-
mental cost for installing canned pumps in a new
200 million pound per year PVC plant would be
approximately $10,000. Replacing pumps in the same
size existing plant would cost about $30,000.
-------
PVC-83
B. Procedures
VCD-9 - Solvent Cleaning
One of the principal sources of intermittent emissions
is from the opening and closing of the reactors. A
method to reduce this emission is to solvent clean
the reactors. There are several solvents that are very
efficient, such as tetrahydrofuran, dimethyl formamide,
and ethylene dichloride. The use of any of these
solvents does introduce a possible emission problem but
since they are all liquids at normal temperatures, these
emissions are much easier to contain and control than VCM,
One company (A-17) does use a solvent system and the
following economics have been given, all converted to
a 200 million pound per year plant.
Capital Investment $300,000
Solvent Purified 6 x 106 Gals/Yr.
Loss 1% (99% Eff.) 6 x 104 Gals/Yr.
1.253 x 8.34 x 6 x 104 6.27 x 105 Lbs/Yr.
@ 9-l/2C/Lb. $59,600/Yr.
Utilities
50 PSIG Steam 3.762 x 10^ Lbs/Yr.
Cooling Water 12.0 x 1Q6 Gals/Yr.
Electricity 2.5 x 1Q3 KWH/Yr.
Chemical & Misc. Supplies $2,500/Yr.
Labor 7% of Battery Limits
Capital Investment $ll,200/Yr.
Plant A-17 uses the solvent system to clean the reactors
after every three or four batches.
In addition to reactor cleaning, the solvent should be
considered for cleaning pipes, pumps, vessels, etc. As
with reactor cleaning, the major problem is associated
with separation of the solvent from the PVC resin.
VCD-10 - Water Purge of Reactors
A method used (in conjunction with a gas holder) to
reduce VCM emissions from reactors is to thoroughly
purge all the VCM vapors to the gas holder by filling
the reactor with water. The water is recycled so that
there is no VCM loss to water after the initial charge.
This purging is only done in preparation for cleaning
the reactor (every 3 to 6 batches).
-------
PVC-84
Cost for the water purge system should be less than
$200,000 for the model size plant.
VCD-11 - Leak Detection
In order to detect and eliminate leaks as soon as they
occur, it is necessary to continuously monitor specific
areas for VCM vapors. In a 200 million pounds per year
PVC plant, four or five ten-point monitors are required
to provide reasonable coverage. These monitors
(chromatographs) cost about $20,000 per unit installed.
The associated alarm and signal system costs another
$30,000 and a data processing system another $40,000
to $90,000. This brings the equipment, cost up to $150,000
to $200,000. To follow up on alarms, the part time
services of a man and portable VCM detector ($5,000)
is required. The system more often than not requires
the full time assistance of a pipe fitter to minimize
leakage. In addition, the full time services of an
instrument man is necessary to keep the chromatographs
in operation.
To monitor battery limits and off site VCM concentrations
requires personnel and equipment, but the cost varies
markedly and indeterminantly due to wide differences in
frequency of testing and number of locations tested.
-------
Note;
TABLE PV-10
CATALOG OF EMISSION CONTROL DEVICES *
Plant
No.
A-6
A-7
A-8
A-9
A-10
A-10
A-12
A-16
A-17
A-21
A-21
A-21
B-7
C-l
D-l
Device
No.
VCD-1&2
VCD-1&2
VCD-2
VCD-2
VCD-2
VCD-3
VCD-2
VCD-3
VCD-9
VCD-1&2
VCD-4
VCD-9
VCD-3
VCD-2
VCD-2&3
Lbs. VCM/Hr.
In
1809
4620
416
65
Out
13
23
104
7
122
53.8
2.0
27.4
29.0
74
99.3
99.5
75
75
85
96
99.2
Remarks
-30°F cooling
Conditions not given
Conditions not given
Conditions not given
-70°F cooling
EDC scrubbing medium
Conditions not given
30 plate col. 13'V 34" high 70 psig
Use EDC as solvent, closed system
No conditions or rates given except discharge
No conditions or rates given except discharge
No conditions or rates given except discharge
No conditions or medium given
No temp, given for refrigeration unit
Cooled to 14°F, acetone is scrubbing medium
o
CO
tPdthH- ±n the Process °r have plans to reduce VCM emissions
listed those that were in actual service at the time the reports were made!
We have only
-------
PVC-86
IX. Model Plant
It should be noted here that most PVC plants have
undoubtedly done much to reduce fugitive losses during
the past year. This also applies to many procedures
where far more care is now exercised to minimize VCM
emissions. This takes time and the results are certainly
not completely reflected in the emissions reported as of
June or July of 1974. For this reason our Model Plant
"set up" may indicate higher input VCM content to certain
devices or higher fugitive losses than are actually the
case today. Table PV-11 presents economics for a typical
existing 200 million pound per year PVC plant without VCM
emission control devices.
Table PV-12 provides incremental investment, utility and
manpower requirements for the same size plant with a
moderate amount of emission control equipment. This
facility (Model Plant I) employs the following devices
and procedures to reduce VCM emissions.
1. VCD-1 Improved Stripping
2. VCD-2 Refrigeration of VCM Recovery System Vent
3. VCD-8 Canned Pumps
4. VCD-11 Leak Detection Program
The best way to reduce VCM losses downstream from the
stripper (or the reactor if stripping is done there) is
to strip the latex as thoroughly as possible of residual
VCM. As the polymerization goes to about 95% completion
at best, it is economical to recover most of the VCM.
It is possible to recover 99% of the VCM if a vacuum of
about 25" Hg (5 in. Hg absolute) can be pulled on the latex
and the vapors are compressed and chilled (-30°F) under
pressure (70 psig) and care has been taken to minimize leaks
into the system. This is not easy to do even with the proper
vacuum-compression equipment due to foaming problems. This
is particularly true of dispersion latices as they foam
far more readily than suspension latices. Considerable
work is being done on this problem and our Model Plant
devices assume considerable success in this area. The
low temperature refrigeration is necessary so that the
inerts that must be vented from the system can be discharged
with a minimum VCM loss.
The vacuum system should be flexible enough so that it can
be used to evacuate VCM vapors from other vessels such as
reactors, blend tanks, etc., whenever necessary to minimize
VCM emissions to the air.
The replacement of all pumps handling liquid VCM with canned
pumps should reduce variable fugitive emissions which occur
with some frequency due to packing or seal failures on
regular centrifugal pumps.
-------
PVC-87
TABLE FV-ll
PVC MANUFACTURING COST FOR A TYPICAL
EXISTING 200 MM LB./YR. FACILITY
Direct Manufacturing Cost ^/Lb. FVC $Ar.
Raw Material
Vinyl Chloride @ 10^/Lb. 10.10
Vinyl Acetate @ 19^/Lb. 0.75
Additives @ 22-1/2^/Lb. 0.90
Initiator @ $1.65/Lb. 0.1?
Labor @ 20 X 5.65 X 8/Shift 0.49
Maintenance (5$ of Invest.) 0.55
Utilities o.4o
IsTiJo"
Indirect Manufacturing Cost
Plant Overhead (110$ Labor) 0.54
Laboratory (25$ Labor) 0.12
0.66
Fixed Manufacturing Cost
Depreciation (10 Yr. Straight Line) 1.10
Insurance & Property Tax (2.3$ Invest) 0.25
1735
Total Manufacturing Cost 15.37 30 740 000
General Expenses
Administration (3$ of Mfg. Cost) 0.46
Sales (1$ of Mfg. Cost) 0.15
Research (2.5$ of Mfg. Cost) 0.38
Finance (6$ of Investment) 0066
1751
Total Cost 17.02 34,040,000
Product Value, PVC 24.00 48,000,000
Profit Before Taxes 6.98 13,960,000
Profit After Taxes (52%) 3>35 6,700,000
ROI (NPAT X 100/Plant Investment) 30.4$
-------
PVC-88
TABLE PV-12
200 MM LBS/YEAR PLANT
MODEL PLANT I INCORPORATING
MODERATE EMISSION CONTROL DEVICES
Capital Increase for Emission Control Devices
VCD-1 High Vacuum and Compr. for Max.
VCM Stripping
VCD-2 Refrigeration on Condenser to -30°F
VCD-8 Substitute Canned Pumps
VCD-11 Monitoring for VCM Emissions
Total Capital Investment Increase
$ 750,000
70,000
10,000
175,000
$1,005,000
Increase in Operating
Cost and Energy Requirements
Control Device
VCD-1
VCD-2
VCD-8
VCD-11
Total
GPM
Cooling Water
35
35
Electric
Power
KWH/HR.
80
15
95
Labor 2-1/2 Men/Shift
Annual Cost = 2.5x5.65x8760
= $125,000
-------
PVC-89
Table^PV-13 presents incremental economic factors for a
facility (Model Plant II) which includes extensive VCf
emission control equipment. This plant incorporates the
same control devices as Model Plant I except the refrigera-
tion unit is replaced with a lean oil scrubber on the VCM
recovery system vent. In addition it includes the use of
a gas holder (VCD-4) and solvent cleaning of reactors.
The use of a scrubber to control VCM emissions from a VCM
recovery system has proven effective in several plants
(A-10, A-16, B-3, B-7, and D-l) and ensures a very low VCM
emission to the atmosphere. (Less than .0010 Ibs VCM/lb product)
Only one plant (A-21) reported using a gas holder (VCD-4).
It is interesting to note that this particular plant has the
lowest VCM emission of all the suspension plants that have
given reasonably complete emission data. They also use a
water purge for reactors (VCD-10). All controllable emissions
(to vents, stacks, etc.) are sent to the gas holder. They are
then compressed and sent to the VCM recovery system. (Resulting
atmospheric vent contains less than 0.005 Ibs VCM/lb product.)
Only one plant (A-17) reported the use of solvent cleaning of
reactors (VCD-9) as standard procedure. Several plants are
experimenting or trying to develop a workable system but are
having difficulty separating the solvent from the polymer
efficiently and economically. This cleaning system could
significantly reduce sporadic VCM emissions"caused by
frequent openings and cleanings of many reactors. (Less
than .002 Ibs VCM/lb product emitted with control device.)
The model plants as presented do not include any devices
to handle VCM emissions from dryers or downstream processing
areas. The use of activated carbon is a possibility but it
remains to be proven if it is practical. It might well be
of value for dispersion plants where it is difficult to
strip the latices effectively at the strippers. However
most dispersion plants use spray dryers which means an
effluent air stream with more moisture content, higher
temperatures and large volumes. All of which increase the
quantity of activated carbon requirement. It is also not
clear as to how to handle the effluent from the adsorber
during regeneration.
Incineration has not been used in the model plants because
of the large fuel requirement and the fact that emissions,
such as HC1, S02 and NOX, not now emanating from PVC plant,
would be formed in significant amounts.
Scrubbing of the large volume air streams with low VCM
content has not been considered. There are no data available
to indicate that an equilibrium condition exists favorable
for a significant reduction of VCM by scrubbing; not to
mention the tremendous size of equipment involved with its
incumbent high cost.
-------
PVC-90
TABLE PV-13
200 MM LBS./YEAR PVC PLANT
MODEL PLANT II INCORPORATING
EXTENSIVE EMISSION CONTROL DEVICES
Capital Increase for Emission Control Devices
High Vacuum and Compr. for Max.
VCM Stripping
Scrubber for VCM Recovery System Vent
Gas Holder
Substituting Canned Pumps
Solvent Cleaning of Reactors
VCD-1
VCD-3
VCD-4
VCD-8
VCD-9
VCD-11 Monitoring for VCM Emissions
Total Capital Investment Increase
$ 750,000
125,000
950,000
10,000
300,000
175,000
$2,310,000
Increase in Operating
Cost and Energy
Re qu i r erne n t s
Control Device
VCD-1
VCD-3
VCD-4
VCD-8
VCD-9
VCD-11
Total
Cooling Electric
Steam Water Power Chemicals
Lbs/Hr GPM KWH/Hr $/Yr
500
35
40
25
15
115
80
5
40
1
126
62,100
62,100
Labor 3 Men/Shift
Annual Cost
3 x 5 . 65 x 8760
$150,000
-------
PVC-91
Tables PV-14 and PV-15 present economics for the Model I
and Model II plants.
Table PV-16 presents an estimate of VCM emissions fron
the suspension PVC process incorporating the emission
control devices employed in the model plants. The
reduction in emissions shown for the Model II plant can
be readily accomplished with present technology. Any
substantial further reduction in VCM emissions will
require additional research and process development effort,
-------
PVC-92
TABLE PV-14
PVC MANUFACTURING COST FOR A TYPICAL
MODEL I PLANT, 200 MM LBS./YR. PRODUCTION
Direct Manufacturing Cost
Raw Materials
Vinyl Chloride @ 10C/Lb.
Vinyl Acetate @ 19«/Lb.
Additives @ 22^e/Lb.
Initiators @ $1.65/Lb.
Labor @ 22^ x 5.65 x 8/Shift
Maintenance (5% of Investment)
Utilities
Indirect Manufacturing Cost
Plant Overhead (110% Labor)
Laboratory (25% Labor)
Fixed Manufacturing Cost
Depreciation (10 Yr. Straight Line)
Insurance & Property Tax (2.3% Investment)
Total Manufacturing Cost
General Expenses
Administration (3% Mfg. Cost)
Sales (1% Mfg. Cost)
Research (2.5% Mfg. Cost)
Finance (6% of Investment)
Total Cost
C/Lb. PVC $/Yr.
10.10
0.75
0.90
0.17
0.55
0.58
0.41
13.46
0.61
0.14
0.75
1.15
0.26
1.41
15.62
0.47
0.16
0.39
0.69
1.71
17.33
31,240,000
34,660,000
Product Value PVC
Profit Before Taxes
Profit After Taxes (52%)
ROI (NPAT x 100/Plant Investment)
24.00
6.67
3.20
48,000,000
13,340,000
6,400,000
27.8%
-------
PVC-93
TABLE PV-15
PVC MANUFACTURING COST FOR A TYPICAL
MODEL II PLANT, 200 MM LBS./YR. PRODUCTION
Direct Manufacturing Cost
Raw Materials
Vinyl Chloride @ lOC/Lb.
Vinyl Acetate @ 19
-------
PVC-94
TABLE PVC-16
ESTIMATE OF VCM EMISSIONS FROM MODEL PLANTS (SUSPENSION)
VCM EMISSIONS, TONS/TON OF VCM
Source
Area
A
B
C
D
E
F
G
Fugitive
Plant Without
Control Devices
.0030
.0030
.0032
.0048
.0042
.0013
.0070
.0080
Model Plant I Model Plant II
.0015
.0020
.0010
.0015
.0015
.0002
.0030
.0050
.0005
.0005
.0010
.0003
.0005
.0002
.0010
.0030
Total
0345
.0157
.0070
-------
PVC-95
x- Research and Development Goals
Technoloqical research and development will be concerned
with reducing vinyl chloride emissions to very low values
as compared with the current emission level. One of the
major sources of emissions is the vent to remove inerts
from the VCM recovery system. More development should be
done on an economical system for scrubbing this vent
stream with a liquid from which VCM can be easily
stripped and liauified for reuse.
Another important emission source is the reactor, not
during polymerization, but when it is being cleaned. All
reactors in the suspension and dispersion process tend to
build up PVC on the walls and agitator. Most plants still
clean by hand, a few of the newer plants (or reactors) are
equipped with water jet lances for self cleaning but even
these must be mechanically cleaned at times. This means
that whenever a reactor is cleaned, it is open and there
is some VCM emission regardless of the care taken. A aood
solvent cleaning system is desirable. There are several
?hpVn?nhiSf£ W°? Wel1 (&imeth^ formamide, tetrahydrofuran)
The problem has been to separate the solvent from the dis-
solved PVC economically. The development of an economical
system would certainly be a bier aid towards the reduction
of ambient VCM emissions.
difficulties associated with efficient strippina
of VCM from the latex is the tendency of latices to foam. '
Dispersion latices are particularly bad because of their
high soap content. The most obvious approach is the
addition of foam breakers (silicones, alcohols, etc.)
Another approach is the use of mechanical foam breaking
devices incorporated into the stripper. Any improvement
in _ this area could result in a marked reduction of VCM
emissions downstream of the stripper. Also, there are a
number of heat exchangers (falling film, wiped film
multiple effect, etc.) that might "make efficient and
economically feasible, the removal of 99+% of the VCM
from the _ latex if it were possible to keep the latex from
coagulating. Both areas of study, heat exchange devices
and stable emulsions, under riaorous conditions are ones
that could result in significant reductions of downstream
emissions, plus a reduction in the VCM content of the
product PVC resin. ' '
-------
PVC-96
REFERENCES
1. "PVC Chemical Profile", Chemical Marketing Reporter,
May 20, 1974.
2. Albright, L. F., "Processes for Major Addition - Type Plastics
and Their Monomers", McGraw Hill, Inc., New York, N.Y., 1974,
3. "Chemical Economics Handbook", Stanford Research Institute,
September 1972 and September 1973.
4. U.S. Tarriff Commission, March 6, 1974.
5. "Current Prices of Chemicals and Related Materials",
Chemical Marketing Reporter, November 11 j, 1974.
6. Private communications with Roy F. Weston, Inc., Consulting
Engineers, West Chester, Pennsylvania„
7. "Controlling Vinyl Chloride Emissions with Granular Activated
Carbon", Bulletin 23-200, Calgon Corporation, Pittsburgh,
Pennsylvania, 1974.
-------
APPENDIX J[
BASIS OF THE STITHY
I. Industry Survey
The study which led to this document was
about selected production processes that are
Industry. rru- -1- - • •
ground knowledge and dir esupport^
and ofse t !"«"««"* P™"-* in the United States,
the most immediate need was to studv ^ pr°CeSSeS' ^ was obvious that
processes that produce the most Dotation T" ^T' faSt°St gr°»th
chemicals (as p^duced b a totallf } Siff^8^611*171 ^ following 32
for study: different processes) were selected
Acetaldehyde (two processes)
Acetic Acid (three processes)
Acetic Anhydride
Acrylonitrile
Adipic Acid
Adiponitrile (two processes)
Carbon Black
Carbon Disulfide
Cyclohexanone
Ethylene
Ethylene Bichloride (two processes)
Ethylene Oxide (two processes)
Formaldehyde (two processes)
Glycerol
Hydrogen Cyanide
Maleic Anhydride
Nylon 6
Nylon 6,6
"Oxo" Alcohols and Aldehydes
Phenol
Phthalic Anhydride (two processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Terephthalic Acid (1)
Toluene Di-isocyanate (2)
Vinyl Acetate (two processes)
Vinyl Chloride
(1) Includes dimethyl terephthalate.
(2) includes .ethylenediphenyl and polyethylene polyphenyl isocyanates
was the6 reuUeratie^erts ZZ™*? ?* ^ ^ °f information,
EPA's industry Advisory Co^mittef Aft* T" ' Mr ^^^ 3nd the
Management and Budget , tbeT^stLnaf^ reC6lVing aPP^val from the Office of
most of the chemicfls listed aboieTh^ T*+ **? tO Sel6Cted Prod"c"s of
questionnaires formed tne bLs f^ what h K ^ frOm the returned
These have been separately pubUshed In fo^ ?'" ***** "SurVey
b, c, and d and entitled «s«v« ^Reports on A r™?'
Petrochemical mdustry - VolSS I II " EmiSSi°nS frora the
-------
1-2
The purpose of the survey reports was to screen the various petrochemical
processes into the "more" and "less - significantly polluting processes".
Obviously, significance of pollution is a term which is difficult if not
impossible to define because value judgements are involved. Recognizing this
difficulty, a quantitative method for Significant Emission Index (SEI) was
developed. This procedure is discussed and illustrated in Appendix II of
this report. Each survey report includes the calculation of an SEI for the
petrochemical that is the subject of the report. These SEl's have been
incorporated into the Emission Summary Table that constitutes part of this
Appendix (Table I). This table can be used as an aid when establishing
priorities in the work required to set standards for emission controls on
new stationary sources of air pollution in accordance with the terms of the
Clean Air Amendments of 1970.
The completed survey reports constitute a preliminary data bank on each
of the processes studied. In addition to the SEI calculation, each report
includes a general introductory discussion of the process, a process description
(including chemical reactions), a simplified process flow diagram, as well as
heat and material balances. More pertinent to the air pollution study, each
report lists and discusses the sources of air emissions (including odors and
fugitive emissions) and the types of air pollution control equipment employed.
In tabular form, each reports summarizes the emission data (amount, composition,
temperature, and frequency); the sampling and analytical techniques; stack
numbers and dimensions; and emission control device data (types, sizes, capital
and operating costs, and efficiencies).
Calculation of efficiency on a pollution control device is not necessarily
a simple and straight-forward procedure. Consequently, two rating techniques
were developed for each type of device, as follows:
1. For flares, incinerators, and boilers a Completeness of Combustion Rating
(CCR) and Significance of Emission Reduction Rating (SERR) were used.
2. For scrubbers and dust removal equipment, a Specific Pollutant
Efficiency (SE) and a SERR were used.
The bases for these ratings and example calculations are included in
Appendix III of this report.
II. In-Depth Studies
The original performance concept was to select a number of petrochemical
processes as "significant polluters", on the basis of data contained in
completed questionnaires. These processes were then to be studied "in-depth".
However, the overall time schedule was such that the EPA requested an initial
selection of three processes on the basis that they would probably turn out
to be "significant pollufers". The processes selected in this manner were:
1. The Furnace Process for producing Carbon Black.
2. The Sohio Process for producing Acrylonitrile.
3. The Oxychlorination Process for producing 1,2 Dichloroethane
(Ethylene Bichloride) from Ethylene.
-------
Ac«t«ldehyde vl« Ethylene
via Kthanol
Acetic Acid via Methanol
via Butane
via Acetaldehyde
beetle Anhydride via Acettc Acid
^crylonltrile (9)
Wiptc Acid
kdlp.>nitrlle via Butadiene
via Adipic Acid
;arbon Black
:«rb >n Bisulfide
Jycl >hexanone
)lme:hyl Terephthalate (+TPA)
!tfty lene
ithylen. Dichlorlde via Oxychlortn.tlon
.... _. vl" Direct Chlorlnation
• try .ene Oxide
onnldehyde via Silver Catalyat
via Iron Oxide Catalyat
lyc,..rol via Epichlorohydrin
ydrogen Cyanide Direct Procens
»cc;'«nate»
ale.c Anhydride
ylon 6
ylon 6,6
KO jYoceaa
hencil
tithilic Anhydride via 0-Xylene
via Naphthalene
igh Denalty Polyethylene
>v I'«n»ity Polyethylene
)ly[ropylene
'lytyrene
ilyvinyl Chloride
yrene
yrtne-Butadiene Rubber
nyl Acetate via Acetylene
via Kthylene
nyl Chloride
Totala
Hydrocarbons
1,227.6
Participates
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
0.01
0
5.1
1.9
2.3
1.4
0.1
0.4
12
0.07
1.6
0
0
_0.6
49.1
TABLE I
EMISSIONS SUI4MRY
ESTIMATED (l) CUimgNT
•4> Oxides of Nitrogen
0
0
0.01
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
_0
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
0.02
0
0
0
0
0
2.6
0
0
0
0
1.2
0
' 0
0.9
0
0
0
P«ge 1 of 3
MM LBS./YEAR
94.2
4,852.6
Total
1.1
27
0.01
54
7.4
8.6
385
30
66.4
0.54
4.060
5.1
148
146.5
17.6
117.3
29
86.2
131
50.6
16
0.91
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
Total WeUhted <5
86
27
1
3,215
490
253
15,000
1,190
3.200
30
17,544
120
5,700
7.460
1,240
7,650
2,300
6,880
1.955
2.070
1,280
56
231
2,950
90
330
440
1.940
422
160
6,400
6,100
2,950
1,650
5 ,700
355
870
425
TR
1.460
6,225.9 <7>
110.220
Probably has up to 10;, low blaa.
„
-------
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Hethanol
via Butane
via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonitrlle (9)
Adiplc Acid
Adlponitrile via Butadiene
via Adiplc Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Bichloride via Oxychlorination
via Direct Chlorlnation
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Eplchlorohydrln
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Pheno1
Phthallc 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
Hydrocarbons (')
1.2
0
0
0
12.2
0.73
284
0
10.5
0
64
0.04
77.2
73.8
14.8
110
34.2
32.8
14.8
17.6
8.9
0
1.2
31
0
0
3.86
21.3
0.3
0
210
262
152
20
53
3.1
1.85
4.5
0
26.3
Participates
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
TA1LE I
EMISSION SUMMARY
ESTIMATED ADDITIONAL <2>
(*) Oxides of Nitrogen
0
0
0.04
0
0
0
8.5
19.3
47.5
0.04
2.8
0.03
0
0.07
0.2
0
0
0.15
0
0
0
0
0
0
0
0
0.05
0
0.8
0
0
0
0
0
0
0.1
0
0
TR
0
AIR EMISSIONS IN
Sulfur Oxides
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
1980. MM LBS./YEAR
Carbon Monoxide
0
0
0
0
2.5
1.42
304
0.09
0
0
1,590
0
85.1
42.9
0.2
25
0
0
66.7
17.0
0
0
85
241
0
0
14.3
0
113
0
0
0
0
0
0
0
0
0
0
0
Page 2 of 3
Total
1.2
0
0.04
0
14.7
2.15
596
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
o
216
267
152.5
21.47
63
3.25
2.34
4.5
TR
27.2
Total Weighted (5-*)
96
0
2
o
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
Q
225
2,720
194
318
325
1,704
1,100
17,200
21,300
12,190
1,640
4,840
225
170
360
TR
2,170
79,5
Totals 1.547.2 55,9 ,,rJ 8Q 5 Z(5B8 ^^ ,
(1) In most Instances numbers are based on less than !007. survey. All based on engineering judgement of best current control. Probably has up to 107. lov bias
(2) Assumes future plants will employ best current control techniques. P
(3) Excludes methane, includes H2S and all volatile organlcs.
(4) Includes non-volatile organics and inorganics.
(5) Weighting factors used are: hydrocarbons - 80, partlculates - 60, NO, - 40, SOX - 40, and CO - I.'
(6) Referred to elsewhere In this study as "Significant Enisslon Index" or "SEI".
(7) Totals are not equal across and down duv to rouuHng.
(9) See sheet 1 of 3.
134,213 <7>
-------
TABLE __!
EMISSIONS SUMMARY
Acetaldehyde vU Ethylene
via Ethanol
Ace:lc Acid via Methanol
via Butane
via Acetaldehyde
Ace:lc Anhydride via Acetic Acid
Acrylonltrile (9)
Adlplc Acid
Adlponltrlle via Butadiene
via Adlplc Acid
Carl. on Black
Cart. on Olaulflde
CycJohexanone
Dim. thy 1 Terephthalate (+TPA)
Ethjlene
Ethjlene Dlchlortde via Oxychlorln
Oxide
.tlon
Chl«'"««°n
'or.aldehyde via Stiver Cataly.t
via Iron Oxide Cataly»t
lycerol via Eplchlorohydrln
X^rogen Cyanide Direct Procea.
Bocyanates
»t«lc Anhydride
Iflon 6
'lot 6,6
to Procega
lenol
'thilic Anhydride via O-Xylene
via Naphthalene
gh Den.lty Polyethylene
« Penalty Polyethylene
lyiropylene
'y 'tyrane
lyioyl Chloride
•n:ne
rune-Butadiene Rubber
X Acetate via Acetylene
via Ethylene
y. Chloride
Totala
Page 3 of 3
Total by 19«n
(10)
Total Velehted (3)
i QHn
Eatlmated Number o£ Nev Plants
• (1973 - 1980)
244,420 <7>
6
0
4
0
3
3
5
7
4
3
13
2
10
8
21
8
10
15
40
12
1
0
10
6
10
10
6
11
6
0
31
41
32
23
25
9
4
1
4
10
&cl^e.f«tnLr!"incUdes1 H^'aVall vo^m""0"'™1"'"""^""- b"ed °" Cn8lneerlnR 'ud«eTOnt °f beat current control.
rot^ue^re°not*eVuere ^ thl* *C>ldy ** "SI8nlf leant "mls'ion Index""0* " 4°.'. S°x " 2°' a"d CO " l~
Total Estimated Capacity
MM Lbs./year
Current
1,160
400
1.020
875
1,705
1,165
1,430
435
280
3,000
871
1.800
2,865
22.295
4,450
5,593
4,191
5,914
1,729
245
412
1,088
359
486
1,523
1,727
2,363
720
603
2,315
5,269
1,160
3,500
4,375
5,953
4,464
206
1,280
5,400
1.800
500
2.015
2,100
3,700 (8)
2.200
845
550
5,000 (8)
1.100
3,600
5,900
40,000
8,250 (8)
11.540
6,800 (8)
9,000
3,520 (8)
380
202
2,120
720
1,500
3,000
3,000
4.200
1,800 (8)
528
8,500
21,100
5,800
6,700
8,000
10,000
5,230
356
2,200
13,000
Probably has up to 107! lov bias.
Sea aheet 1 of 3
*>* to anticipated future .hut dovn of «rglnal pl.nt..
-------
1-6
In order to obtain data on these processes, the operators and/or
licensors of each were approached directly by Air Products' personnel.
This, of course, was a slow and tedious method of data collection because
mass mailing techniques could not be used, nor could the request for data
be identified as an "Official EPA Requirement". Yet, by the time that OMB
approval was given for use of the Industry Questionnaire, a substantial
volume of data pertaining to each process had already been received. The
value of this procedure is indicated by the fact that first drafts of these
three reports had already been submitted to the EPA, and reviewed by the
Industry Advisory Committee, prior to the completion of many of the survey
reports.
In addition, because of timing requirements, the EPA decided that
four additional chemicals be "nominated" for in-depth study. These were
phthalic anhydride, formaldehyde, ethylene oxide and high density
polyethylene. Consequently, five additional in-depth studies were
undertaken, as follows:
1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.
2. Air Oxidation of Methanol in a Methanol Rich Process to
produce Formaldehyde over a Sliver Catalyst. (Also, the
subject of a survey report.)
3. Air Oxidation of Methanol in a Methanol-Lean Process to
produce Formaldehyde over an Iron Oxide Catalyst.
4. Direct Oxidation of Ethylene to produce Ethylene Oxide.
5. Low pressure catalytic polymerization of Ethylene.
The primary data source for these was the Industry Questionnaire,
although SEI rankings had not been completed by the time the choices
were made.
In addition separate "In-Depth" studies were made on Polyvinyl
Chloride (PVC) and Vinyl Chloride Monomer (VCM) using data obtained
from a separate survey made in the summer of 1974.
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[I REPORT N0~
EPA-450/3-73-006-i
__^
a. RECIPIENT'S ACCESSION-NO.
AUTHORls)
Polyvinyl
'. W. A. Schwartz
."^^^^O^A^E-Z^JFTSB^EST
P. 0.'BoxV427°n/Al> Pr°duCtS and Che^cals, Inc.
Marcus Hook, Pennsylvania 19061
11.
68-02-0255
Standards
Research Triangle Park, N.C. 27711
. SUhHLtMtNTARY NOTES"
=»ntre, system
of p0lyvinyl
DESCRIPTORS
ir Pollution
3lyvinyl Chloride
nyl Chloride
ilorohydrocarbons
Petrochemical Industry
Polymer Manufacture
STATEMENT'
J^ATU-ield/Group
7A
7B
7C
11G
13B
13H
I^I.IMO. OF PAGES"
>rm 2220-1 (9-73)
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INSTRUCTIONS
1. REPORT NUMBER
Insert the EPA report number as it appears on the cover of the publication.
2. LEAVE BLANK
3. RECIPIENTS ACCESSION NUMBER
Reserved for use by each report recipient.
4. TITLE AND SUBTITLE
Title should indicate clearly and briefly the subject coverage of-the rep
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