DEQ-CFW_00088113

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Emissions of APFO from Pack -out
Total Volume displaced
per day (ft3)
267
Number of batches
85
C7F15COOH*NH4 per
year
0.44
Ibs of Ammonia per yr
1.4807
Scrubbing Efficiency of 98%
C7F15COOH*NH4 per
year
0.01
Scrubbing Efficiency of 0%
jibs of Ammonia per yr
0.03
Room Emissions going to stack
year average ppb from
air monitoring samples 0.546
MW of APFO
414
air turnover rate
ft3/min)
11000.0
Ibs of C7F15COOH*NH
to Room in 2004
3.38
Ibs of Ammonia to
Room in 2004
1.06
Ibs of Ammonia to
Room in 2004 from spill
washes
30.00
Ammonia Tote Emissions
Each drum weight (Ibs) 312.89
Number of NH4 drums
2004 92
Ibs emitted with 0%
scrubbing 2878.6
For breathing losses on ammonia
tote and connections made and
broken, add additional 30 pounds
of NH3 vented into room.
Theoretical ammonia used for
campaign was X pounds. Portion
of this is estimated to be evolved
while neutralizing. Assume 10% of
total for this years calculations
(NOTE: the following are just example calculations, different numbers may have been used)
For Ammonia Salt formation and Filling Totes to Scrubber
Assume 1000 gallons for reactor 2
Assume 1000 gallons of tote volume
Total Volume displaced per day = 334ft3
Assume 20-weight % solution of ammonia salt
Assume addition of ammonia water either first or in parallel with addition of acid form
Molar ratio of water to APFO is 92/1. We will assume with this molar ratio that the APFO
Vapor pressure is reduced by a factor of 10
APFO (pure) vapor pressure is 3 mm Hg
(259ft3) / (359ft3/lb-mole) ❑ (3 mm Hg) / (10*760) ❑ (433 lb/lb-mole)
= 0.123 pounds per batch of C7F15COOH
= 1.35 pounds of C7F15COOH
equivalent ammonia from above 0.005 pounds or 1.8 pounds
Emissions to Room going to stack
These are calculated from the room emission samples taken from Jennifer Locklear. The average APFO allowance per 8
hour period is .56 parts per billion. This is used to calculated APFO going to the stack.
(((average ppb from air monitoring for the year of interest )/1000)*12.187*MW)/293K = mg/m3
MW = 414
mg/m3 * .0283 = mg/ft3*2.2x 10e-6 = Ib/ft3
11000 ft3/min is the room air turnover rate
NH3
Assume 1000 hours of inventory
.0132 Ib/hr point emissions * number hours ran in the year *( MW of NH3/ MW APFO) =
For breathing losses on ammonia tote and connections made and broken, add additional 30 pounds of NH3 vented into
room. Theoretical ammonia used for campaign was 431 pounds. Portion of this is estimated to be evolved while
neutralizing. Assume 10% of total for this years calculations or 43.1 pounds emitted to scrubber at 0% efficiency.
DEQ-CFW 00088113

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emissions of c-tt acid i-rom
# of Vaporizations
85
# of vents per Batch
1
Volume of Tank(ft3)
58.32
# C-8 Acid vented per Batch
0.25
Scrubbing Efficiency of 98%
C-8 acid Vented in 2004 from Hydrolysis
(Ibs)
0.42
For the vaporization we pull down to -13 psia PFOA and nitrogen.
The volume of vaporizer is 300 gallons (assuming 1/3 full), the volume of the receiver tank is 200
gallons (assuming completely empty), the volume of 115ft of pipe/ condensers is (assuming 1/3
full and 70 + 10 + 35 ft of 4" ID piping). With the respective full or empty assumptions, the
vaporizer is 180 gallons or 24ft3, the receiver is 200 gallons or 26.7 ft3, and the 115 ft of piping is
7.62 M. Thereby, making the total volume of the vaporization system is 58.32 ft3.
Vapor pressure of PFOA at 55 C (the temp of condenser ) is 0.0322 psia (11-28-2001 Muthu)
If we neglect effect of pressure we are under estimating emissions.
58.32 ft3 at 14.7 psia is (0.05832 psia/14.7 psia) * (58.32 ft3/359 ft3)*414 lb/lb mole=0.390
pounds/batch initial.
58.32 ft3 at 0.7 psia is equivalently 8.20 pounds/batch. tanking average assume 4.3 pounds goes
into scrubber on each evacuation.
From our experience the PFOA rises up to 20 ppm in scrubber. Scrubber volume is 1500 gallons.
This is 12450 pounds times 20 ppm is 0.249 pounds.
Theoretical calculations indicate 0.4 lb/batch . Practical scrubber measurements indicate a ppm
rise of 20. This is 0.249 lb/batch. Emissions to environment are less than 1 % of these values
from previous testing or less than 100 pounds per year.
DEQ-CFW 00088114

0 H2SO4 Emissions
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Breathing Losses
Volume of Vapor
Breathing From
Tank(U) 174
Breathing Losses
from Sulfuric Acid
Tank in 2004 (Ibs) 0.07
r-rnisswns uvm ruing
Volume of
Tank(U)
349
Ibs emitted per fill
0.0015
Number of Tank
Fills in 2004
6
Ibs emitted in
2004
0.009
Breathing Losses Assumptions:
Sulfuric Acid Tank sits and breathes between 20 @ and 30 C 365 days per year. Assume 2000
gallons of acid, 2000 gallons of free board space. We will breathe
With 20,000 pounds of acid in storage, the volume is 20,000.0 Ib/114.47 Ib/ft3=174 ft3 of vapor
which breathes.
From 3-64 Table 3-13 of the Chemical Engineers Handbook 5th edition, the vapor pressure of
90% acid (worse case than 95% acid) is 0.0117 mm hg
(0.0117 mm Hg/760 mm Hg)* 98 lb/lb mole*(174 ft3/359 ft3/lb mole)*(20/273 C)*365
days/year=0.07 pounds of breathing losses per year.
Filling Assumptions:
When 40,000 pounds of acid is delivered, the volume is 40,000.0 Ib/114.47 Ib/ft3=348.7 ft3 of
vapor.
From 3-64 Table 3-13 of the Chemical Engineers Handbook 5th edition, the vapor pressure of
90% acid (worse case than 95% acid) is 0.0117 mm hg
(0.0117 mm Hg/760 mm Hg)* 98 lb/lb mole*(348.7 ft3/359 ft3/lb mole)=0.0015 pounds/fill
DEQ-CFW 00088115

0 APFO SUMMARY PAGE
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Total Emission by Pollutant
VOC
Entering
Scrubber
(Ibs)
Exiting
Scrubber
(Ibs)
Exiting
From
Room***
(Ibs)
Working
Losses
(lb)
Combined
Vent to
Stack (Ibs)
C5F11COF*
9.1
0.182
0.0
0.0
0.2
C7F15COF(Note 1)
437.6
8.8
0.0
0.0
8.8
C7F15COOH(Note 2)
134.3
11.8
0.42
0.0
12.2
C7F15COOH*NH4(Note 3)
0.72
0.01
6.8
0.0
6.8
C8F171
22.6
22.6
0.0
0.0
22.6
Total VOC Ibs
50.6
Total VOC (tons)
0.03
HAP/TAP
Entering
Scrubber
(Ibs)
Exiting
Scrubber
(Ibs)
Exiting
From
Room***
(Ibs)
Working
Losses
(Ib)
Combined
Vent to
Stack (Ibs)
S03
1862.2
91.3
36.4
0.0
127.72
S02
482.0
23.7
8.7
0.0
32.39
HF
19.3
0.068
0.0
0.0
0.07
H2SO4 in Process****
22.2
111.8
22.4
0.0
134.24
H2SO4 in Tank (Note 4)
0.0
0.0
0.0
0.08
0.08
NH3"
5757.2
5757.2
62.2
0.0
5819.42
* Foreshot Material is mostly C51711 COF.
** NH3 Component is only present in APFO Neutralization. We have assumed 0%
efficiency through scrubber.
*** Room Air is combined with scrubber flow. Stack is 85 ft high, 19" tip, 11,500 scfm, 100
FPS.
**** H2SO4 emissions primarily as S03 emissions, assuming hydrolysis to the acid in the
process.
Stack Testing was performed in June 2003 during oxidation and distillation operations, and
indicated annual values of less than 100 pounds per year of all perfluorooctanoic acid and
acid fluoride compounds, using a modified EPA Method 5. Samples for this performance
testing were collected by Precision Air Inc of Delaware. From this testing, emissions over
this period would total 25 pounds or less over 90 day period for the combined class of
materials specified in Note 1 & 2 below. Stack testing was not performed with separator,
neutralization or pack -out operations in progress due to scheduling.
Note 1. Perfluorooctanoyl fluoride (C7F15COF) is CAS# 335-66-0
Note 2. Perfluorooctanoic acid (C7F15CO2H) is CAS# 335-67-1
Note 3. Ammonia Perfluorooctanoate is CAS# 3825-26-1
Note 4. Exiting the storage tank into atmosphere.
DEQ-CFW 00088116