DEQ-CFW_00068542

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DuPont Fluoroproducts
22828 NC Highway 87 W
Fayetteville, NC 28306-7332
January 19, 2009
Mr. Steven F. Vozzo
NCDENR — Division of Air Quality
Fayetteville Regional Office
225 Green Street — Suite 714
Fayetteville, NC 28301
SUBJECT: Notice of Violation/Notice of Recommendation for Enforcement
NCGS 143-215.108 "Control of Sources of Air Pollution; Permits Required"
DuPont Company - Fayetteville Works
North Carolina Air Permit No. 03 73 5T3 3
Duart Township, NC, Bladen County 06/09-00009
Dear Mr. Vozzo:
This is the requested response to your letter dated January 6, 2009. The subject Notice of
Violation/Notice of Recommendation for Enforcement ("NOV/NRE") was issued by the
NCDENR Division of Air Quality ("DAQ") Fayetteville Regional Office as a result of the
DuPont Company - Fayetteville Works ("DuPont") operating three finished product container
decontamination processes without an air permit.
The NOV/NRE requested that DuPont respond to DAQ with the actions taken to bring about
compliance with the above violation. Additionally, DAQ asked that six specific pieces of
information be provided in the response. The three decontamination processes are addressed
individually below.
HFPO Product Container Decontamination Process (ID No. NS-N)
The following addresses the six specific pieces of information for this process:
1. A general description of the process
DuPont ships its finished product hexafluoropropylene oxide ("HFPO") to customers in one -
ton cylinders (200 gallon capacity), UN T50 portable tanks (260 gallon capacity), and ISO
tank containers (4,480 gallon capacity). When empty, these containers are returned from the
customer back to the DuPont Company — Fayetteville Works facility where they are reused.
When these containers are returned, the container is full of residual gaseous product.
E.I. du Pont de Nemours and Company
DEQ-CFW 00068542

*Mr. Steven F. Vozzo
Page 2 of 9
NCDENR —DAQ
January 19, 2009
Because of the concern of the residual HFPO rearranging into unwanted byproducts and
contaminating fresh product placed into the container, the returned containers are
decontaminated via the HFPO Product Container Decontamination Process (ID No. NS-N)
by evacuating all residual product. The containers are alternately filled with nitrogen gas and
then put under vacuum several times to remove the residual product. The product containers
are vented to a gaseous absorber (NCD-Hdrl), but since the product is not water soluble,
none of the emissions are controlled and all are assumed to vent to the atmosphere.
2. A description of the pollutants being emitted from the process
The HFPO Product Container Decontamination Process emits the following compounds:
Compound
CAS No.
ApproximateConcentration
hexafluoropropylene oxide
428-59-1
98%
hexafluoropropylene
116-15-4
<0.5%
trifluoromethane
75-46-7
<1 %
carbon dioxide
124-38-9
<1%
Hexafluoropropylene oxide and hexafluoropropylene are only regulated as volatile organic
compounds ("VOC"). Tfluoromethane and carbon dioxide are unregulated compounds.
3. An explanation of how the violation was discovered
During a yield project meeting, improvement ideas were being evaluated. A calculation was
performed to estimate annual losses from the decontamination of returned HFPO product
containers. While reviewing the results, it was realized by the engineer responsible for
determining the monthly emissions from the HFPO Manufacturing Process that the container
venting was not accounted for in the annual air emissions inventory. A review of the HFPO
Product Container Decontamination Process determined that it was a stand-alone process that
should be listed in the site's Title V air permit.
To rectify the aforementioned oversight, an application to add the HFPO Product Container
Decontamination Process as an emission source to the subject Title V air permit was
immediately prepared and submitted to DAQ.
4. The startup dates and modification dates, if applicable, of the operation
The HFPO Product Container Decontamination Process has been in operation since the
startup of the HFPO Manufacturing Facility in 1980. When the HFPO Manufacturing
Facility was modified in 1997 which increased both its production capacity and potential
DEQ-CFW 00068543

Mr. Steven F. Vozzo
NCDENR — DAQ
January 19, 2009
Page 3 of 9
VOC emissions by two -fold, the HFPO Product Container Decontamination Process would
have seen a similar increase of returned product containers, and hence a similar increase of
potential VOC emissions, at that time. When the HFPO Manufacturing Facility was
modified in 2006 which increased both its production capacity and potential VOC emissions
to the current level, the HFPO Product Container Decontamination Process would have seen
a similar increase of returned product containers, and hence a similar increase of potential
VOC emissions, at that time.
5. The calculated potential emission of the operation -prior to and following any process
modification
The HFPO Product Container Decontamination Process has been in operation since the
startup of the HFPO Manufacturing Facility in 1980. Through back calculations and
assuming the emissions from the HFPO Product Container Decontamination Process are
relatively linear to the current known emissions, the potential to emit from this process would
have been approximately 37.5 tons per year of VOC during the period from 1980 until 1997.
When the HFPO Manufacturing Facility was modified in 1997 which increased both its
production capacity and potential VOC emissions by two -fold, the HFPO Product Container
Decontamination Process would have seen a similar increase of returned product containers,
and hence a similar increase of potential VOC emissions, at that time. Based on this fact,
through back calculations and assuming the emissions from the HFPO Product Container
Decontamination Process are relatively linear to the current known emissions, the potential to
emit from this process would have been approximately 75 tons per year of VOC during the
period from 1997 until 2006.
The HFPO Manufacturing Facility was modified in 2006, which increased its capacity to the
current level, which is greater than any time in the past. The 2006 modification resulted in a
PSD avoidance limit for the HFPO Manufacturing Facility. Assuming the HFPO
Manufacturing Facility is running at the rate which would equate its emissions to equal the
PSD avoidance limit, and assuming the emissions from the HFPO Product Container
Decontamination Process are relatively linear to the current known emissions, then the
potential to emit from this process would be approximately 100 tons per year of VOC during
the period since 2006.
6. The actual emissions for the operation for at least two years prior to any process
modifications and two years following the modifications
The DuPont Company's records retention guidelines for normal business information is three
years. As such, information regarding the actual number and types of containers handled in
the HFPO Product Container Decontamination Process (ID No. NS-N) is limited to the years
2006 through 2008.
For this three-year period, the actual emissions from the HFPO Product Container
Decontamination Process are as follows:
DEQ-CFW 00068544

'Mr. Steven F. Vozzo
NCDENR — DAQ
January 19, 2009
Year
VOC Emissions
(tons)
2006
39.2
2007
36.6
2008
33.8
Actions taken to reduce actual emissions from this process
Page 4of9
As a result of a request by the DuPont Company — Fayetteville Works, one customer has
tentatively agreed to allow the HFPO Manufacturing Facility to load new product directly into
ISO tank containers without the container first being decontaminated. This change, which is
contingent on not adversely affecting product quality, will reduce the VOC emissions from the
HFPO Product Container Decontamination Process by at least 50%.
Vinyl Ethers North Product Container Decontamination Process (ID No. NS-O)
The following addresses the six specific pieces of information for this process:
1. A general description of the process
DuPont ships its finished product perfluoropropyl vinyl ether ("PPVE"), ester vinyl ether
("EVE"), perfluorinated sulfonyl vinyl ether ("PSEPVE"), and perfluoro-2-propoxy
propionyl fluoride ("HFPO Dimer") to customers in DOT 4BW, 4BA, and 3AA cylinders
(57 gallon, 15 gallon, and 13 gallon capacities respectively) and one -ton cylinders (200
gallon capacity). When empty, these containers are returned from the customer back to the
DuPont Company — Fayetteville Works facility where they are reused. When these
containers are returned, the container is full of residual gaseous product.
Because of the contamination concern for fresh product placed into the container, the
returned containers are decontaminated via the Vinyl Ethers North ("VE North")
Decontamination Process (ID No. NS-O) by evacuating all residual product. The containers
are alternately filled with nitrogen gas and then put under vacuum several times to remove
the residual product. The product containers are vented to a gaseous absorber (NCD-Hdrl),
but since the three vinyl ethers are not water soluble, none of those emissions are controlled
and all are assumed to vent to the atmosphere. The gaseous absorber would effectively
control 99.6% of the HFPO Dimer emissions.
2. A description of the pollutants being emitted from the process
EVE and PSEPVE are products produced in two separate production campaigns at the VE
North Manufacturing Facility. PPVE and HFPO Dimer are produced in a third campaign.
These four products are shipped in their own dedicated finished product containers.
DEQ-CFW 00068545

1
Mr. Steven F. Vozzo Page 5 of 9
NCDENR — DAQ
January 19, 2009
The VE North Product Container Decontamination Process emits the following compounds:
Compound
CAS No.
Approximate
Concentration
perfluoropropyl vinyl ether
428-59-1
>99%
ester vinyl ether
116-15-4
>98%
perfluorinated sulfonyl vinyl ether
75-46-7
>98%
perfluoro-2-propoxy propionyl fluoride
2062-98-8
>99%
The VE North finished products PPVE, EVE, PSEPVE, and HFPO Dimer are regulated as
volatile organic compounds ("VOC"). Since HFPO Dimer is a water-soluble acid fluoride,
DuPont also includes it as a source of hydrogen fluoride emissions for the North Carolina air
toxics program. As such, emissions of HFPO Dimer from the VE North Product Container
Decontamination Process will be reported as the molar equivalent of hydrogen fluoride,
which has a facility -wide limit in Section 2.2(B)(2) of the subject permit.
3. An explanation of how the violation was discovered
During a yield project meeting, it was realized that the emissions associated with the
decontamination of returned HFPO product containers were not accounted for in the annual
air emissions inventory. Following this discovery, it was determined that the emissions
associated with the decontamination of returned vinyl ether product containers also were not
accounted for in the annual air emissions inventory. A review of the VE North Product
Container Decontamination Process determined that it was a stand-alone process that should
be listed in the site's Title V air permit.
To rectify the aforementioned oversight, an application to add the VE North Product
Container Decontamination Process as an emission source to the subject Title V air permit
was immediately prepared and submitted to DAQ.
4. The startup dates and modification dates if applicable, of the operation
The VE North Product Container Decontamination Process has been in operation since the
startup of the VE North Manufacturing Facility in 1980. The VE North Manufacturing
Facility was modified prior to 1994, and this modification established the current PSD
avoidance limit of 68.9 tons VOC per year. Therefore, the actual emissions from the VE
North Manufacturing Facility at the time of this modification would have been 28.9 tons
VOC per year. When the VE North Manufacturing Facility was modified, the VE North
Product Container Decontamination Process would have seen a similar increase of returned
product containers, and hence a similar increase of potential VOC emissions, at that time.
DEQ-CFW 00068546

Mr. Steven F. Vozzo
NCDENR — DAQ
January 19, 2009
Page 6 of 9
5. The calculated potential emission of the operation prior to and following any process
modification
The VE North Product Container Decontamination Process has been in operation since the
startup of the VE North Manufacturing Facility in 1980. When the VE North Manufacturing
Facility was modified prior to 1994, which increased its capacity to the current level and
established the current PSD avoidance limit, the VE North Product Container
Decontamination Process would have seen a similar increase of product containers, hence a
similar increase of potential air emissions, at that time.
The current potential to emit for the VE North Product Container Decontamination Process
has been determined to be 20.6 tons VOC per year. The VE North Manufacturing Facility's
actual emission rate prior to the pre-1994 modification was 28.9 tons VOC per year. The VE
North Manufacturing Facility's average emission rate for the period from 2006 to 2008 was
approximately 42 tons VOC per year. Through back calculations and assuming the historical
emissions from the VE North Product Container Decontamination Process are relatively
linear to the current known emissions, and assuming the potential emissions are relatively
linear to the actual emissions, then the potential to emit from this process would have been
approximately 14 tons per year of VOC during the period from 1980 until the pre-1994
modification.
6. The actual emissions for the operation for at least two years prior to any process
modifications and two years following the modifications
The DuPont Company's records retention guidelines for normal business information is three
years, which would limit actual information to the years 2006 through 2008. However, a
search of DuPont's records also found the VE North product shipping information for 2005.
As such, information regarding the actual number and types of containers handled in the VE
North Product Container Decontamination Process is limited to the years 2005 through 2008.
For this four-year period, the actual emissions from the VE North Product Container
Decontamination Process are as follows:
Year
VOC Emissions
(tons)
2005
4.1
2006
3.8
2007
4.8
2008
4.1
DEQ-CFW 00068547

I
'Mr. Steven F. Vozzo Page 7 of 9
NCDENR — DAQ
January 19, 2009
Vinyl Ethers South Product Container Decontamination Process (ID No. NS-P)
The following addresses the six specific pieces of information for this process:
1. A general description of the process
DuPont ships its finished product perfluoromethyl vinyl ether ("PMVE") and perfluoroethyl
vinyl ether ("PEVE") to customers in one -ton cylinders (200 gallon capacity), ISO tank
containers (4,480 gallon capacity), and DOT 413W, 4BA, and 3AA cylinders (57 gallon, 15
gallon, and 13 gallon capacities respectively). When empty, these containers are returned
from the customer back to the DuPont Company — Fayetteville Works facility where they are
reused. When these containers are returned, the container is fall of residual gaseous product.
Because of the contamination concern for fresh product placed into the container, the
returned containers are decontaminated via the Vinyl Ethers South ("VE South")
Decontamination Process (ID No. NS-P) by evacuating all residual product. The containers
are alternately filled with nitrogen gas and then put under vacuum several times to remove
the residual product. The product containers are vented to a gaseous absorber (NCD-Hdr2),
but since the products are not water soluble, none of the emissions are controlled and all are
assumed to vent to the atmosphere.
2. A description of the pollutants being emitted from the process
PMVE and PEVE are products produced in two separate production campaigns at the VE
South Manufacturing Facility. These two products are shipped in their own dedicated
finished product containers.
The VE South Product Container Decontamination Process emits the following compounds:
Compound
CAS No.
Approximate
Concentration
perfluoromethyl vinyl ether
1187-93-5
>99%
perfluoroethyl vinyl ether
10493-43-3
>99%
PMVE and PEVE are only regulated as volatile organic compounds ("VOC").
3. An explanation of how the violation was discovered
During a yield project meeting, it was realized that the emissions associated with the
decontamination of returned HFPO product containers were not accounted for in the annual
air emissions inventory. Following this discovery, it was determined that the emissions
associated with the decontamination of returned vinyl ether product containers also were not
accounted for in the annual air emissions inventory. A review of the VE South Product
DEQ-CFW 00068548

Mr. Steven F. Vozzo
NCDENR — DAQ
January 19, 2009
Page 8 of 9
Container Decontamination Process determined that it was a stand-alone process that should
be listed in the site's Title V air permit.
To rectify the aforementioned oversight, an application to add the VE South Product
Container Decontamination Process as an emission source to the subject Title V air permit
was immediately prepared and submitted to DAQ.
4. The startup dates and modification dates if applicable, of the operation
The VE South Product Container Decontamination Process has been in operation since the
startup of the VE South Manufacturing Facility in 1996. The VE South Manufacturing
Facility has not been modified since its startup. Therefore the VE South Product Container
Decontamination Process has not been expanded since its 1996 startup.
5. The calculated potential emission of the operation prior to and following any process
modification
The potential to emit for the VE North Product Container Decontamination Process has been
determined to be 15.7 tons VOC per year. This potential emission rate is unchanged from the
process' startup in 1996.
6. The actual emissions for the operation for at least two years prior to any process
modifications and two years following the modifications
The DuPont Company's records retention guidelines for normal business information is three
years, which would limit actual information to the years 2006 through 2008. However, a
search of DuPont's records also found the VE South product shipping information for 2005.
As such, information regarding the actual number and types of containers handled in the VE
South Product Container Decontamination Process is limited to the years 2005 through 2008.
For this four-year period, the actual emissions from the VE South Product Container
Decontamination Process are as follows:
Year
VOC Emissions
(tons)
2005
10.6
2006
9.2
2007
9.6
2008
9.7
DEQ-CFW 00068549

Mr. Steven F. Vozzo
NCDENR — DAQ
January 19, 2009
Actions taken to bring about compliance
4
Page 9 of 9
When DuPont discovered the HFPO, VE North, and VE South Product Container
Decontamination Processes were not addressed in the subject Title V air permit, an application to
modify the subject air permit to add these processes emission sources was immediately prepared
and submitted to DAQ. As a result of this action, the modified air permit was authorized and
issued by DAQ on January 15, 2009, and now includes these three sources.
If you have any questions regarding this letter, or if you need additional information, please call
me at [phone].
DEQ-CFW 00068550