DEQ-CFW_00086703

C7
General explanation:
Semi -works is a research & development area that operates under a wide range of conditions. Emissions are calculated for each individual
campaign. In all cases, material balances are used to determine emissions. Since all emissions occur within the semi -works facility, they
are all assumed to be point source emissions via the process stack SW-1. The only emissions calculated for SW-2 are acid fluoride
emissions associated with running melt flow samples under the lab hood.
Polymerization Campaign Emissions Determination:
The production and raw material information is entered for each campaign on a worksheet. The individual sheets in this workbook
are copies of the completed worksheets for each campaign. Data in green fields is entered when applicable for the polymerization campaign.
The other cells are calculated cells. The emissions for the campaign are calculated at the bottom of the worksheet. For the annual
emissions calculations, the emissions from these campaigns are totaled onto a summary sheet. In this workbook, that is called
"Campaign Summary". A summary by month is found on "Year End Summary".
Example Mass Balance Calculations for polymerization campaigns: (using 5-SXF-1.1 worksheet for example)
The emissions are determined by mass balance around the system. Data used in the calculation is obtained from production records and
entered into the worksheet. The following is entered into the worksheet after each campaign:
1) Enter the starting material at the beginning of the campaign. This would include any material in the recovery tank and condensate
tank. The composition of the material in each tank is determined by lab analysis and/or on-line GC.
2) Enter the amount of initiator added to the system, based on integrator on initiator feed. The concentration of initiator is determined
by lab analysis.
3) Enter the amount of TFE added to the system, based on the integrator for TFE feed.
4) Enter the amounts of solvent (E2, F1.13) and monomer (PSEPVE) added to the system during the campaign. Drum weights
before and after the campaign are used to determine this.
Enter starting and addition data as described in steps 1-4 above in the green shaded areas.
Spreadsheet sums all inputs for each component in right hand column (column M)....see embedded comments for details

Starting Material
Item
Recovery
Monomer
Condensate
Initiator
Addition
Addition
Addition
Addition
Tank
Tank
Tank
Tank
(TFE)
(E2)
(PS)
(F113)
Weight (Kg):
0.00
0.00
0.00
20.08
114.39
0.00
97.00
666.00
0.00
Compositions:
%E2
0.00%
94.00%
96.00%
0.00%
100.00%
0.00%
0.00%
0.00%
%PSEPVE
8.00%
6.00%
0.00%
100.00%
0.00%
45.00%
%TFE
0.00%
0.00%
100.00%
0.00%
0.00%
0.00%
0.00%
%F113
92.00%
0.00%
0.00%
0.00%
0.00%
100.00%
55.00%
%Inititiato
0.00%
0.00%
4.00%
0.00%
0.00%
0.00%
0.00%
Totals
Weights
E2
0.00
0.00
0.00
19.28
0.00
0.00
0.00
0.00
0.00
19.3
PSEPVE
0.00
0.00
0.00
0.00
0.00
0.00
97.00
0.00
0.00
97.0
TFE
0.00
0.00
0.00
0.00
114.39
0.00
0.00
0.00
0.00
114.4
F113
0.00
0.00
0.00
0.00
0.00
0.00
0.00
666.00
0.00
666.0
Inititiator
0.00
0.00
0.00
0.80
0.00
0.00
0.00
0.00
0.00
0.8
5) Enter the amount and composition of material in the recovery tank, condensate tank, in collection drum, or held up in the
system at the end of the campaign.
Spreadsheet sums all inputs for each component in right hand column (column M).... similar to above
Ending Material
Item
Recovery
Condensate
Drained
Tank
Tank
E2 tank
to drum
Holdup
Tank level Qet oft)
Weight (Kg):
200.00
107.00
85.00
0.00
0.00
Compositions
%E2
3.89%
4.69%
100.00%
4.69%
72.00%
%PSEPVE
7.50%
6.92%
6.92%
28.00%
%TFE
0.00%
0.00%
0.00%
%F113
87.79%
88.20%
88.20%
0.00%
%Inititiato
0.00%
0.00%
0.00%
Totals
Weights
E2
7.78
0.00
5.02
0.00
3.99
0.00
0.00
16.8
PSEPVE
15.00
0.00
7.40
0.00
5.88
0.00
0.00
28.3
TFE
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.0
F113
175.58
0.00
94.37
0.00
74.97
0.00
0.00
344.9
Inititiator
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.0
6) Enter total weight of polymer produced, and average EW.

•
7) Enter approximate weight (5 kg) of adhesions on vessel walls and in piping.
with an EW of 1700.
8) Enter amount and composition of slurry left over at the end of the campaign.
saturation of initiator and limited TFE present during shutdown conditions,
The adhesions are assumed to be pTFE
The EW is assumed to be 1080 as a result of over
Production
Item
Polymer Adhesion Slurry
s
Weight (Kg):
138.30 5.00 0.00
Compositions
EW
1470 1700 1000
%Polymer
1 1 0.1
1
%E2
0.72
%PSEPVE
0.28
%TFE
0
%F113
0.79011
Totals
Weights
Polymer
138.30 5.00 0.00
143.3
E2
0.00 0.00 0.00
0.0
PSEPVE
41,96 1.31 0.00
43.3
TFE
96.34 3.69 0.00
100.0
F113
0.00 0.00 0.00
0.0
VE in PoIM
41.96 1.31 0.00
The total for each component added, remaining, and production output as calculated in column M for each section of the
spreadsheet above is duplicated in the table below. Emissions are difference between amount consumed and amount in product.
Material Balance Summar
Compound
Added Remaining Used Production Other
Totals
E2
19.3 16.8 2.5 0.0
2.5
PSEPVE
97.0 28.3 68.7 43.3
25.4
TFE
114.4 0.0 114.4 100.0
14.4
F113
666.0 344.9 321.1 0.0
321.1
Inititiator
0.8 0.0 0.8 0.0
0.8
The final section of the spreadsheet summarizes the reportable emissions in pounds for SW-1. Refer to embedded
comments for details.

•
Lbs of Emissions
SW-1
VOC's 94.8lbs
F-113 706.4lbs
AF's 2.766lbs
9) Enter in the number of melt flow samples processed in the semi -works lab during the campaign. This is entered in the green box
under SW-2. If all samples are sent to the mfg lab, this will be zero.
SW-2
# of MF samples 0
grams emissions 0 g
Ibs of emissions 0.0000 lb
Example Mass Balance Calculations for slurry reclaim campaigns:
The slurry reclaim process is used to recover valuable solvent and monomer from drums of polymer slurry. The semi -works flash dryer
is used to flash off the solvent and monomer liquid into a vapor state, so that the solids can be collected in a bag filter. The vapors are then
condensed back into liquid which can be reclaimed. Due to a high nitrogen (noncondensible) flow, some of the solvent and monomer escapes
the condenser as vapor to the SW-1 stack. A mass balance approach is used to determine how much vapor has been lost, so that this can
be included in annual air emissions summary.
Here is a summary of the material balance calculation.
1) Weight of drums processed through the system are recorded. The reported composition of the drums is used to determine
VOC and F113 content. Solids and other non -recoverable waste are backed out, based on a material balance on
solids (polymer and waste collected).
2) Any fresh E2 solution used for startup of the flash drying system is accounted for in the balance.
3) Outputs include weight of reclaimed liquid collected in drums, weight of solid polymer collected, and weight of solid waste
in drums.

Example Mass Balance Calculations for TFESK campaigns;
The production of TFESK requires the use of TFE. TFE emissions and potential TFESK emissions are estimated based upon a material
balance around the system. Data used in the calculation is obtained from production records for each campaign and entered into the worksheet.
The following is entered into the worksheet after each campaign:
1) Enter the amount of TFE received; minus the amount required to produce the product.
2) Enter the number of bacthes dried during the month.
3) Enter the amount of TFESK solids removed from the oven.
4) Enter the average amount of dried TFESK collected per batch for the campaign being reported.
Outputs from the material balance include the estimated emissions of TFE and TFESK

2007 Air Emmisions Inventory for SW-1 and SW-2 in pounds (Ibs)
SW--1
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Total
Month
1
2 3
4 5
6 7
8 9
10 11
12
VOC's
240.45
0.00
65.59
154.77
168.51
45.28
0.00
209.03
0.00
164.83
0.00
968.04
2017
F113
738.66
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
738.7
AF's
4.11
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.59
6.7
HCl
0.00
0.00
0.00
0.00
0,00
0.00
0.19
0.00
0.17
0.00
0.00
0.00
0.4
Qtr's
1st Qtr.
2nd Qtr.
3rd Qtr.
4th Qtr.
Total
VOC's
306.0
368.6
209.0
1132.9
2017
F113
738.7
0.0
0.0
0.0
738.7
AF's
4.11
0.00
0.0
2.59
6.7
HCI
0.00
0.00
0.36
0.00
0.4
SW-2
(Only record emissions in support of SW polymerization operations)
Jan Feb Mar Apr May Jun
Jul
Aug
Sep
Oct
Nov
Dec
Total
VOC's
0.0 0.0 0.0 0.0 0.0 0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
F113
0.0 0.0 0.0 0.0 0.0 0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
AF's
0.0 0.0 0.0 0.0 0.0 0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.000
Qtr's
1st Qtr.
2nd Qtr.
3rd Qtr.
4th Qtr.
Total
VOC's
0.0
0.0
0.0
0.0
0.0
F113
0.0
0.0
0.0
0.0
0.0
AF's
0.000
0.000
0.00
0.00
0.000