Document 6RZaZzB83Rn1E3DqgYkoXXDr3
BEGoodrich
progress
IN VINYL CHLORIDE CONTAINMENT
A Report By The B.F.Goodrich Company
Additional copies are available from: Corporate Communications The B.F.Goodrich Company 500 S. Main St. Akron. Ohio 44318
CCD 12-475
December 4.1975
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0ACKGROUND he B.F.Goodrich Company was
Tfaced with a number of serious and difficult decisions when we discovered, in January, 1974, that three of our employees who had worked for many years in our Louisville. Ky., poly vinyl chloride plant had died from a rare form of liver cancer, angiosarcoma. Subsequently, additional cases were identified and reported among poly vinyl chloride production workers in plants of various companies in the United States, Canada, Europe and Japan. In all these plants polyvinyl chloride (PVC), a solid resinous polymer which is the base material for the vinyl plastic industry, is produced from vinyl chlo ride (VC), a reactive gaseous monomer. Goodrich has produced PVC since 1937, Prior to 1974. its programs to provide a safe work environment in keeping with known scientific data already had re duced the concentration of VC gas ex posure to an average of less than 100 parts per million (ppm). The angio sarcoma discovery, however, added a new dimension to the problem of VC confinement. The Company took immediate action. We informed our employees, appro priate government officials, customers, others in industry and the public of all pertinent facts. We searched medical records and medical examination re ports of all employees who could have been exposed to vinyl chloride to as certain the existence of physical abnor malities. We began immediately to re examine our manufacturing operations -- to explore, in the light of the tech nology that was then available or could 4 be developed in the short term, all pos * sible ways to confine VC inside equip ment and prevent its escape. With faith in our technological ability and with great concern for worker safety, the Company made the decision to con tinue both with PVC production and with plans for expansion at the Louisville Plant.
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In May. 1974. the Company announced it had undertaken the most intensive re search and development program in its history, involving more than 130 scien tists, engineers and technicians, with the aim of containing vinyl chloride gas. To date, these company technologists have devoted 425.000 man-hours to these pro jects. This does not include the thousands of hours devoted by plant and support personnel on monitoring, training, med ical examinations and other aspects of finding solutions to these problems.
We now estimate that the total capital expense required to comply with VCM standards of the Federal Occupational Safety and Health Administration and the expected Environmental Protection Agency vinyl chloride standards will amount to an estimated $42 mil lion over the period 1974 to 1977, inclu sive. This is the figure we estimated one year ago. It may be possible to meet our goals and reduce the $42 million figure by 10 to 15 per cent through technological developments resulting from our research, development and engineering programs.
Goodrich Programs
Today, The B.F.Goodrich Company can report considerable progress in these programs.
While all goals have not yet been fully achieved, the Company is operating its five U.S. PVC plants, as well as its VC monomer manufacturing facility at Cal vert City. Ky.. well within the strict reg ulations established by OSHA. It is also supplying PVC resins with such a minute content of residual vinyl chloride monomer (RVCM) that the possibility of VC exposure from their use is virtually eliminated.
The Company is confident, based on extensive sampling data, that it will be able to operate its plants in compliance with expected requirements of the Envi ronmental Protection Agency (EPA) reg ulating VC emissions to the environment. We also expect to continue supplying PVC
compound* for wide usage in food pack aging which can meet proposed standards for approval by the Food and Drug Ad ministration (FDA).
Goodrich programs have been designed to reduce vinyl chloride escape, however it may occur, to the very lowest achievable levels, and to assure a wide margin of safety for our employees, workers in cus tomers' plants, and ultimate users of PVC products. These programs are in three major categories:
1. Reduction or elimination of possible exposure to employees in plants.
2. Reduction of residual vinyl chloride monomer in PVC resins and com pounds leaving its plants, to lower the possibility of exposure in trans portation, in customers' processing plants and in finished products.
3. Reduction of VC emissions in air and water from its plants.
Reduction of Plant Efxposures
Because of primary concern for em ployee safety, the reduction of exposures in plants was the first area of concentra tion. Before January, 1974, the Company already had reduced exposure levels in its plants far below the then-existing govern ment standards (500 ppm) and the levels recommended by the American Confer ence of Governmental and Industrial Hy gienists (ACGIH), which were 200 ppm. By the time OSHA issued its new tempo rary standard of 50 ppm in April, 1974. the Goodrich plants were operating below this level and the Company had made decisions on programs designed to reduce exposure levels still further.
The permanent standard proposed by OSHA as published in the Federal Reg ister on May 10,1974, could, in the opinion of B.F.Goodrich, have led to a shutdown of the PVC industry. This was also the viewpoint of the industry, as expressed through the Society of the Plastics Indus try (SPI). Reasons behind the opinion were practical ones, as follows:
1. The proposed standard was ambig uous in its establishment of "nondetectable" levels. As written, these
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could have been interpreted as in
dicating permissible exposure of 1.0 ppm or 0.5 ppm, or as requiring no exposure whatsoever.
2. The four types of respiratory equip ment listed as acceptable for pro tection against vinyl chloride were all to be self-contained. Such equip ment would have been totally im practical because weight and bulk of tanks, hoses, etc. would have severely limited worker mobility. Further, the limited air supply in self-con tained equipment, enough for only 30 minutes, would have required re supply so frequently that these sys
tems also would have been imprac tical.
3. Protective clothing called for in the proposed standard would have
placed additional unacceptable re straints on worker mobility. This clothing also would have exposed the wearer to severe heat stress, particu larly when worn in confined areas and where the work required sub stantial physical effort.
Within established Federal procedures, and in open hearings and in open records.
Goodrich and industry experts provided extensive technical information on con trol of industrial gases under pressure and work practices, and realistic information on the possibilities for engineering con trols.
The permanent OSHA standard is sued on October 5, 1974, is stringent, but is more realistic and much less ambigu
ous, and sets forth detailed specific para
meters for industry action. It requires that worker exposures be no more than 1 ppm on a time-weighted average for 8 hours, and no more than 5 ppm for any 15-minute period. Under the standard, respira tors are made available to all workers. Until April 1. 1976, their use is optional up to 25 ppm, but is required at higher levels. After April 1, 1976, respirators are mandatory for exposures above the 1- and 5-ppm levels.
As one of the first steps in its intensified program. Goodrich quickly developed monitoring systems to measure ambient VC levels in work atmospheres on a con tinuing basis. These systems have been continuously improved and now are very
accurate and reliable. Portable monitoring devices were re used to enable engineers to locate
Quickly leaks or sources of vinyl chloride in plants. Since VC gas is continuously under pressure in the PVC manufacturing operations, even the smallest apertures in the hundreds of valves, flanges or similar equipment in plants can release the gas into the work atmosphere.
Another of the first tasks was to locate all these sources and make them as leakproof as possible. In many cases, this re quired the development or special pro curement of new. more highly engineered pumps, flanges and gasketing materials, and also extensive re-engineering of pip ing systems to reduce the number of pos sible leak sources.
Still another step was the installation of new ventilation systems in buildings in which PVC operations are conducted. This substantially reduced VC in work areas where it was most likely to concen trate. Automatic alarm systems were in stalled to indicate if VC concentrations should reach levels requiring respirators, or evacuation of personnel until an emer-
New Reactor Cleaning Technology
PVC manufacture from VC in existing plants is a batch operation in which re actors are charged, emptied and recharged repeatedly, and in which solid material normally deposits or builds up on reactor interiors during each batch reaction. Re actors are large, sealed pressure vessels in which vinyl chloride gas is converted (polymerized) into the solid polyvinyl chloride resin, or plastic. Reactor cleaning to remove this build-up between charges has. in the past, been a principal source of worker exposure to VC, because unre-
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acted VC gas in the reactors is entrapped within the solid deposits. Before 1974 on* efforts had been directed to reducing
posure from reactor cleaning. Goodrich then had already developed and patented and was using in its plants and licensing others to use. its Hydraulic Reactor Cleaner (HRC). This equipment, by auto
mated mechanical means, greatly re duced frequency and duration of reactor entry and manual cleaning.
We are now able to report that our re search program has resulted in a fur ther major accomplishment in preventing such exposure to an extent heretofore un attainable. This is the invention, devel opment and proving out in production plants of what is called the Goodrich "Clean Reactor Technology", It involves the combination of new processes, tech niques and materials for treating interiors of used or new reactors to prevent solid deposits and build-up even after a large number of charges. This new technology, with related improvements and practices, includes continued use of HRC's but after many charges instead of after each charge, and more complete evacuation of vapors in reactors before they are opened. It vir tually eliminates the possibility of worker exposure to VC from reactor emptying and cleaning operations.
Our goal is a completely closed, auto mated and essentially leak-proof reaction system which will require no reactor open ing or entry except for periodic mainte nance.
Goodrich is now operating its PVC plants, as well as its vinyl chloride mono mer plant, with levels of VC in the work area of between 1 and 3 ppm. These are average levels, and exposure to employees as measured by personal monitoring is considerably lower. With the use of respi ratory equipment when required, worker exposure can be kept below the levels called for by the OSHA standard.
Respirator Use and
Employee Education
The Company also has made advances
in the technology and use of respirators. Ail available types were tested to make
sure that inhalation of any VC could be prevented, and to select types which would
cause the least discomfort and inconven ience to workers. At this time, the Com
1 pany has adopted air-fed respirators for uge in most operations when necessary.
J Other types, such as air-packs, are pro vided for special situations. The OSHA standard calls for employee
education and training on precautionary measures relating to reduced exposure to
vinyl chloride. Goodrich has carried on such training programs at its Calvert City vinyl chloride monomer plant and all
five PVC manufacturing plants. Prog-
grams were built around on-the-job train ing sessions and special slide films and ed ucational bulletins, and have received praise from Federal and state agencies for
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Reduction of VC in Product
The second major category of progress
is the reduction of residual vinyl chloride
monomer in PVC resins and compounds
produced in Goodrich plants. In the past,
chiefly because of the comparatively large
size and other properties of the molecules
in PVC, very small amounts of unreacted
vinyl chloride have remained entrapped
in the resin, or polymer. These amounts
are reduced when resins are mixed with
other ingredients to make compounds,
and then are reduced still further during
processing into finished products in cus
tomers' plants.
The OSHA standard extends to pro
cessor plants. Goodrich, in cooperation
I with many customers using its various PVC resins and compounds, has mea
1
sured vinyl chloride release to the air around processing equipment. Levels were
found to be very low compared with those
in PVC production plants and have been
lowered markedly in the past year.
Both OSHA and the National Institute
of Occupational Safety and Health
(NIOSH) have stated that they saw no
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problem with VC exposure from finished goods However, a question has raised about the possible mim-at^IT, vinyl chloride into food from DarW*,, f materials made of PVC compounds.
In September, 1975. the Food and Dru Administration proposed new regulatin'*1* affecting the use of PVC in a number " r food-contact applications. Under the* proposals. PVC resins and compound* fabricated into bottles, blister pack * boxes, and other semi-rigid and rigid packaging that comes in contact with food would no longer have FDA approval The regulation would continue to permit PVC use in pliable film-type wraps, gas kets, cap liners, pipe, tubing and packag. ing coatings.
It should be noted that the FDA action to date is only a proposal, not a final reg ulation, and comments on the proposal are being received for consideration. Two comments are worth special mention in this regard.
First, as we announced last May, our Company is producing new PVC bottle compounds containing significantly less than one part per million (ppm) of VC. The Company has been unable to detect vinyl chloride, by analytical methods sen sitive to 50 parts per billion (ppb), in foodsimulating solvents when the package is fabricated from compounds containing 1 ppm or less of residual vinyl chloride.
Secondly, the FDA proposal leaves the door open for suppliers or users of PVC packaging materials to submit food addi tive petitions and secure FDA approval if their supporting data demonstrates there would be no reasonable expectation that vinyl chloride would become a component of the packaged food. Should the present proposed regulations become final. Good rich believes that packaging materials fabricated from its new PVC compounds will meet this criterion for approval.
New Stripping Columns Developed
A major factor in our Company's abil ity to produce PVC compounds that are extremely low in vinyl chloride content
has been the development of a new imaroved continuous method of stripping vinyl chlonde from PVC resin during its
manufacture, as announced by the Com
pany on August 26. In the new process, resin made in slurry form from VC in a group of reactors is continuously fed into the top f an especially designed stripping
column countercurrent to steam fed at the bottom of the column. As the column is operated under controlled conditions,
the steam rises to the top, picking up al
most all the VC in the resin flowing down ward. The VC is collected and recovered
for reprocessing, while the stripped slurry is removed at the bottom. Virtually all the remaining VC is removed in drying
of the slurry. Goodrich is now installing the new
stripping columns in ail of its PVC plants
and. as a result, we are producing general purpose resins with an ultra-low residual VC monomer content -- in Ranges below
I ppm. It is believed that processors and fabricators using these resins will not have
to establish regulated areas in their plants
under the OSHA regulations. Regulated
areas are those in which the time-weighted
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Plant Environment
The Goodrich stripping technology is also a key to progress in the third category of reduction of VC losses, that is, escape to the environment. Since the stripping operation continuously recovers and re cycles all but traces of the VC present in the PVC resin as it comes from the reac tors, there is a substantial reduction in the amount of VC which could be discharged to the environment with the air from the dryer or with effluent from other down stream operations.
In other respects, progress in reduction ofVC in the work placehas been achieved, while avoiding forcing the VC out of the plant into the surrounding environment. Goodrich environmental engineers at each plant, as well as the corporate envi ronmental staff, have carefully analyzed in-plant control measures for their effect
on VC concentrations in air
w_.
effluents. Steps have been taken wh
appropriate to collect exhaust air and r2.
move even small amounts of contains
VC. and VC has been stripped and re covered from effluent process water. Con! trol of leaks in equipment has, of course reduced losses in venting air from the plants as well as in work areas.
The air surrounding the Goodrich Vr plant and PVC plants has been sampled scientifically, with regard to meteoro logical conditions and other factors, and tested for VC content at periodic intervals Levels have been much lower than in the work place, due to the rapid mixing of ex-
haust air with the much greater volume of ambient air, and also the actual break down of VC molecules when released to the atmosphere.
At present, the levels of VC in the out side air at points adjacent to Goodrich plants are of the order of a few hundredths of one part per million. Effluents leaving the plants contain only a few parts per million. As the new stripping technology is installed in all PVC plants and tech
nological improvements are incorporated in the VC monomer plant at Calvert City, emissions of VC will become even lower.
At about the same time Goodrich environmental engineers began concen trating on reduction of VC in the envi ronment, the technical branch of EPA
started a study of the possible establish ment of federal emission standards under the authority of the Clean Air Act. At the request of EPA. Goodrich has worked closely with its experts in supplying emis sion data, setting up atmospheric testing areas and procedures and providing en
gineering and economic data on possible control technology.
Availability of Technology
Even though the technology we have developed is proprietary, and could give Goodrich a competitive advantage, the
Company considers it our responsibility to make it available on an unrestricted basis to all competitors in the PVC and
. yj chloride industry in the States and abroad. Modest license
tee* will partially offset Goodrich s large research, development and engineering
^Several license agreements have aleady been signed on the stripping col umn technology, and considerable interst has been shown by producers, here and g broad, in the newer clean reactor sys tems. We are also supplying new contain
ment technology to licensees, worldwide, of our vinyl chloride monomer processes.
The Future of PVC
The Company has stated several times that capital expenditures, operating costs, research and development costs and maintenance connected with VC control, plus continuing medical surveillance, has added to the production costs of its PVC materials. As the new technologies are adopted in all production opefations and further experience is gained, greater ef ficiency and reductions in unit operating costs should be significant.
Because of the versatility and compar atively low price of PVC, it is the second largest plastic in sales volume in the U.S. It is estimated that U.S. industry capacity will exceed 5 billion pounds in 1975, and 7 billion pounds in 1980.
We are now confident that, with the employment of the new VC confinement technologies, the use of PVC will continue to grow, and Goodrich intends to main tain its leadership position in this indus try.
VC containment programs have, at least for the present, somewhat reduced capacity at existing Goodrich PVC plants. However, new capacity at the Louisville. Ky., plant, which will start production in January, will more than make up the dif ference and provide capacity to meet in creased customer requirements for the next few years.
These new facilities embody all the improved technology for VC loss reduction
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which the Company has developed. With
the use of very large reactors, the number of valves, pumps, flanges and other for
mer leak sources has been substantially
reduced. New stripping columns, reactor
cleaning systems and many other new
developments are being installed. Good
rich engineers believe that this new facil
ity will be as good as or better than any
other PVC plant in the United States in
prevention of employee exposure or escape
of VC into the environment, or residual
VC in product.
We intend to continue our efforts to re
duce VC exposure resulting from all our
operations and products, and to continue
our research and development efforts to
refine our techniques and develop new
ones. We face the possibility that, because
of the long latency period, we will see
other cases of angiosarcoma resulting from
heavy exposure in the past.
But we now feel sure that the chances
are extremely remote of this disease re
sulting from VC exposure in our current
operations.
The B.F.Goodrich Company December 4,1975