DEQ-CFW_00087901

HFPO Manufacturing Process 2004 Emissions Point Source Emission Determination
Page 2 of 7
349 kg COF2 = 349 kg VOC
= 769 lb. VOC
HF Eouivalent Emissions 349 kg COF2
x 0.606 kg HF/kg COF2
211 kg HF = 466 lb. HF
•
•
DEQ-CFW 00087901

�J
NFPO Manufacturing Process
F. Perfluoromethylcyclopropane (PMCP)
Oxygen (02)
Fluoroform (CF31-11)
Carbon Dioxide (CO2)
2004 Emissions Point Source Emission Determination
Page 7 of 7
CAS No. 379-16-8
CAS No. 7782-44-7
CAS No. 75-46-7
CAS No. 124-38-9
PMCP, 02, CF3H, and CO2 are not VOCs nor do they have potential to make HF. Since they are not
reportable emissions, the calculations are not shown here.
G. Point Source Summary
Nafion Compound Name
Before Control
After Control
After Control
VOC Generated
Stack Emissions
Stack Emissions
k / r VOC
Ib/ r VOC
Ib/yr VOC
Iblyr HF
ton/yr VOC
Ton/HF
A.
COF2
87,184
192,205
769
466
0
0
B.
PAF
65,088
143,492
574
99
0
0
C.
Acid Fluoride Solvent TFF
30,840
67,990
272
164.8
0
0
Acid Fluoride Solvent TAF
30,840
67,990
272
0
D.
HFP
10,261
22,621
22,621
11
E.
IHFPO
10,319
22,748
22,748
11
Total
234,531 1
517,046
1 47,256
1
24 1
0
DEQ-CFW 00087902

HFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 1 of 8
Non -point Source Emission Determination:
point source emissions include equipment emissions and maintenance emissions. Equipment emissions are due to leaks
valves, flanges, and pumps. If these leaks occur outside of a building, they are considered fugitive emissions.
Maintenance emissions are due to opening up vessels for maintenance and though some of this equipment is located indoors,
to be conservative it will be assumed that all maintenance emissions are fugitive emissions.
I. Equipment Emissions
Equipment Emissions are a function of the number of emission points in the plant (valves, flanges, pump seals). For the
equipment emission calculations the inventory shown below is conservative and based on plant and process diagrams. Note that
the calculations below include equipment emissions (EE) inside buildings (which become stack emissions or SE) as well as
equipment emissions outside buildings (fugitive emissions or FE).
A. Equipment Emissions Inside Buildings (Stack Emissions)
1. Equipment Emissions from Reactor, Distillation Column, #1 Recycle Tank:
Emissions are vented from equipment located in the barricade and are vented through the barricade scrubber. Barricade
scrubber is 95% efficient for control of acid fluorides. From W1208078 HFPO Flowsheet:
•
Material
VOC
HF
Aver a
Line 6
a Vessel Contents
Line 6 Line 4
k /hr
Total
% of
contents
% VOC
% HF
HF
Potential
% overall
HF Potential
0.606
0.172
1 0.11
0.081
02
2.4
2.4
4.8
0.1 %
COF2
x
x
33.7
33.7
67.4
1.4%
1.4%
1.4%
0.606
1.4%
PAF
x
x
25.5
25.5
51
1.0%
1.0%
1.0%
0.172
1.0%
HFP
x
76.4
76.4
152.8
3.1%
3.1%
HFPO
x
100.1
100.1
200.2
4.1%
4.1%
HFA
x
1
1
2
0.0%
0.0%
PMFF
x
x
9.6
9.6
19.2
0.4%
0.4%
0.4%
0.606
0.4%
PMAF
x
x
18.4
18.4
14.5
51.3
1.1%
1.1%
1.1%
0.11
1.1%
PMCP
86.6
86.6
80.5
253.7
5.2%
TFF
x
x
50.3
50.3
50
150.6
3.1%
3.1%
3.1%
0.081
3.1%
TAF
IX
IX
500
5001
495.9
1495.9
30.6%
30.6%
30.6%
0.606
30.6%
TAF
Ix
Ix
335
3351
3321
1002
20.5%
20.5%1
20.5%9
0.606
20.5%
TAF
Ix
Ix
1 4791
4791
476.31
1434.31
29.4%
29.4%1
29.4%1
0.606
29.4%
Total
I
I
I
I
1 1
4885.21
94.7%1
87.4%1
1
82.3%
1.0%
1.1%
3.1%
Assume that: 95% of process materials are VOCs; Average HF Potential 0.504
88% are acid fluorides with 95% controlled in the barricade scrubber;
7% are non-acid fluorides with 0% controlled in the barricade scrubber.
100% of the liquid is 0.504 weight fraction HF.
Barricade:
Valve emissions:
119 valves x 0.00039 Ib/hr/valve
= 0.046 Ib/hr EE
Flange emissions:
248 flanges x 0.00018 Ib/hr/flange
= 0.045 Ib/hr EE
Pump emissions:
1 pump x 0.00115 Ib/hr/pump
= 0.001 Ib/hr EE
Total equipment emission rate
= 0.092 Ib/hr EE
Barricade VOC:
From acid fluorides:
0.092 lb. EE/hr
710.751 lb VOC generated
x 8760 hr/year
x (100%-95%) scrubber efficiency
x 0.880 lb. A/F VOC/lb. EE
= 35.538 lb/yr VOC emitted
= 710.751 Ib/yr VOC generated
From non-acid fluorides:
0
Barricade HF:
x
x
0.092 lb. EE/hr
8760 hr/year
0.070 lb. Non-A/F VOC/lb. EE
56.537 Ib/yr VOC
0.092 lb. EE/hr
x 8760 hr/year
x 0.504 lb. HF/lb. EE
x (100%-95%) scrubber efficiency
20.353 Ib/yr HF
Total Barricade VOC Emissions:
35.538 Ib/yr VOC
+ 56.537 Ib/yr VOC
= 92.075 Ib/yr VOC
DEQ-CFW 00087903

HFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 2 of 8
2. Fugitive Emissions From Distillation System #1
sions are vented from equipment located in tower and are vented through stack.
W1208078 HFPO Flowsheet:
Material
VOC
HF
Avera a Vessel Contents
% of
contents
% VOC
% HF
HF
Potential
% overall
HF Potential
Line 8 k /hr
0.606
0.172
0.11
02
2.4
0.93%
COF2
x
x
33.7
13.09%
13.1 %
13.1 %
0.606
13.1 %
PAF
x
x
25.5
9.91%
9.9%
9.9%
0.172
9.9%
HFP
x
76.4
29.68%
29.7%
HFPO
Ix
1 99.9
38.81%
38.8%
HFA
x
1
0.39%
0.4%
PMFF
x
x
9.6
3.73%
3.7%
3.7%
0.606
3.7%
PMAF
x
x
3.8
1.48%
1.5%
1.5%
0.110
1.5%
PMCP
5.1
1.98%
TFF
x
x
TAF
x Ix
TAF
Ix
x
TAF
Ix Ix
Total I
1
1
257.4 1
1
94.7%1
87.4%
Average HF Potential 0.121
Assume that: 95 wt. % of the process material are VOCs;
100% of the liquid is 0.121 weight fraction HF.
Valve emissions: 60 valves x 0.00039 Ib/hr/valve = 0.023 Ib/hr EE
Flange emissions: 120 flanges x 0.00018 Ib/hr/flange = 0.022 Ib/hr EE
Total equipment emission rate = 0.045 Ib/hr EE
VOC: 0.045 lb. EE/hr HF: 0.045 lb. EE/hr
x 8760 hr/year x 8760 hr/year
x 0.950 lb. VOC/lb. EE x 0.121 lb. HF/lb. EE
374.490 Ib/yr VOC 47.698 Ib/yr HF
3. Equipment Emissions From Scrubber, Dryers, and Stripper Column
Emissions are vented from equipment located in tower and are vented through stack.
From W1208078 HFPO Flowsheet:
Material
VOC
HF
Averai
ie Vessel Contents k /hr
% of
contents
% VOC
% HF
HF
Potential
% overall HF Potential
Line 6
Line 11
Line 12
Total
0.606
0.172
0.11
02
COF2
PAF
x
x
6.5
6.5
0.68%
0.68%
0.68%
0.172
0.68%
HFP
x
75.8
75.8
75.8
227.4
23.90%
23.90%
HFPO
Ix
99.6
96.7
96.7.
293
30.79%
30.79%
HFA
x
1
1
0.11%
0.11%
PMFF
x
x
9.6
9.6
1.01%
1.01%
1.01%
0.606
1.01%
PMAF
x
x
3.8
3.8
0.40%
0.40%
0.40%
0.11
0.40%
PMCP
5.1
5A
10.2
1.07%
Water
360
360
KOH
40
40
Total
951.5
567%
2.1%
0.7%
Average HF Potential 0.008
Assume that: 57 wt. % of the process material are VOCs;
100% of the liquid is 0.008 weight fraction HF.
Valve emissions: 171 valves x 0.00039 Ib/hr/valve = 0.067 Ib/hr EE
Flange emissions: 312 flanges x 0.00018 Ib/hr/flange = 0.056 Ib/hr EE
Pub emissions: 2 pumps x 0.00115 Ib/hr/pump = 0.002 Ib/hr EE
.Total equipment emission rate = 0.125 Ib/hr EE
VOC: 0.125 lb. EE/hr
x 8760 hr/year
x 0.570 lb. VOC/lb. EE
624.899 Ib/yr VOC
HF: 0.125 lb. EE/hr
x 8760 hr/year
x 0.008 lb. HF/lb. EE
= 8.771 Ib/yr HF
DEQ-CFW 00087904

HFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 4 of 8
4. Fugitive Emissions From Toluene
0s: Fugitive emissions are determined via mass balance, i.e. any mass of toluene unaccounted for in the mass balance
will be assumed to be air emissions.
Assume that: 95% of raw ingredient becomes waste
Mass Balance:
Toluene inventory in process as of January 1:
Toluene added to process:
Toluene inventory in process as of December 31:
Toluene destroyed in process:
Toluene shipped off with product:
Toluene removed from process as a solid waste:
Toluene released to air via permitted stack:
Toluene released to process wastewater:
Toluene released to the ground (spill):
Unaccounted for difference in mass:
+ 2628lb
+ 26819 lb
- 3632lb
- 0 lb
- 119 lb injected into product
- 16774 lb
- 0 lb
- 0 lb
- 0 lb
= 8922 lb toluene = 8922 lb VOC
In section B-1, fugitive emissions from distillation system #2, the assumption was made that all of the fugitive
emissions were toluene. As the mass balance above shows the unaccounted for toluene, the amount calculated
in section 3 is extremely conservative. Therefore, for the purpose of toluene and VOC emissions, the amount
actually vented will be reported based on the mass balance calculation.
5. Total Equipment Emissions
Emission Source
Inside Emissions
Outside Emissions
Stack Emissions
(Fugitive Emissions
lb VOC
lb HF
lb VOC
lb HF
A-1
Reactor, Distillation Columns, #1 Recycle Tank
92.07
20.35
A-2
Distillation System #1
374.49
47.70
A-3
Scrubbing, Dryers, Stripper Column
624.90
8.771
B-1
Distillation System #2
1013
B-2
HFP Storage and Feed
622.84
B-4
Toluene System
8922.00
Total
1 1091.461
76.821
10557.491
0.00
In order to be conservative, the calculated values will be multiplied by a factor of 2.
Conservative amount (total x 2)
Inside Emissions
Outside Emissions
Stack Emissions
(Fugitive Emissions
Ib/yr VOC
I Ib/yr HF
Ib/yr VOC
I Ib/yr HF
2,1831
154
21,1151
0
Total HF emissions: 154 Ibs HF from outside building
+ 0 Ibs HF from inside building
154 Ibs HF
Total VOCs generated inside building: 710.75 lb VOC from Reactor, Distillation Column, #1 Recycle Tank
+ 374.49 lb VOC from Scrubber, Dryers, Stripper Column
+ 624.90 lb VOC from Scrubber, Dryers, Stripper Column
= 1710.14 lb VOC generated (before control device)
Conservative amount (total x 2) 3420 lb VOC generated (before control device)
DEQ-CFW 00087905

NFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 5 of 8
H. Maintenance Emissions
�kground
During preparation of equipment for maintenance, a vessel is first de -inventoried of liquid (to another process vessel),
then de -pressurized (to a vacuum), then nitrogen is used for a series of pressurize/vent-down cycles until a vessel is
fume free. For the purpose of estimating emissions from vessel preparation, the plant can be broken down into three
sections: HFP Storage and Feed, HFPO Distillation system #2, and everything else. Below are the definitions,
assumptions, and calculations of maintenance emissions for each section.
A. HFP Storage and Feed
The HFP Storage section consists of the two HFP Storage Tanks and the associated equipment to transfer HFP into
the tanks. When maintenance clearing is required for these tanks (scheduled once per year), the liquid inventory is
transferred to the other tank, the vapors are compressed into the tank (down to 10 psig), and then the residue is
evacuated to the Nafion® Division Waste Gas Scrubber. The emissions to the atmosphere, therefore, are the HFP
vapors remaining at 10 psig.
Calculations:
PV = nRT
Tank Volume = 3000 gal = 401 ft3
Contents = 100 % HFP (MW=150 Ib/Ibmol)
Tank pressure = 10 psig = 24.7 psia
Tank temperature = ambient = 77 deg F = 537 R
R = 10.73 psia-ft3/lbmol/R
RT _
n = 24.7 psia x 401 ft3 1.72 Ibmol HFP
10.7 psia-ft /lbmolUR 537 R
1.72 Ibmol HFP x 150 lb HFP = 258 lb HFP = 258 lb VOC per cleaning
Ibmol HFP
Clearings/year: Each tank scheduled once per year; two tanks is two clearings/year scheduled; to be conservative,
assume one extra clearing a year, so three clearings performed per year.
VOC from HFP Storage Tank =
•
258 lb HFP
x 3 clearings/year
774 Ib/yr HFP
258 lb VOC per cleaning
x 3 clearings/year
774 Ib/yr VOC
DEQ-CFW 00087906

HFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 6 of 8
B. Distillation System #2
e n
maintenance clearing is required for the column and tanks (scheduled once per year), the liquid inventory is
ferred to the other tank, the vapors are compressed into the tank (down to 10 psig), and then the residue is
evacuated to the Nafion® Division Waste Gas Scrubber. For the purposes of these calculations, the average
operating pressure and total volume are used.
Calculations:
PV = nRT
Tank Volume = 3300 gal =
Contents =
(Conservative approximation based off of
vessel contents and volatility of compounds)
Average system pressure = 20 psig =
Average system temperature = 30 deg F =
R=
441 ft3
50 % HFP (MW=150 lb/Ibmol)
40 % HFPO (MW=166 lb/Ibmol)
10 % Toluene (MW=92 lb/Ibmol)
34.7 psia
490 R
10.73 psia-ft3/lbmol/R
n = PV/RT
n = 34.7 psia x 441 ft3 =
10.7 psia-ft3Abmol/R 490 R
2.91 Ibmol material x 50 % HFP x
2.91 Ibmol material
150 lb HFP = 218 lb HFP
Ibmol HFP
2.91 Ibmol material x 40 % HFPO x 166 lb HFPO = 193 lb HFPO
Ibmol HFPO
2.91 Ibmol material x 10 % Toluene x 92 lb Toluene = 27 lb Toluene
Ibmol Toluene
As stated previously, toluene amounts are calculated by mass balance. The amount vented calculated by mass
balance will be used for toluene and VOC emisssions.
Total VOC per cleaning:
218 lb HFP
193 lb HFPO
412 lb VOC
Clearings/year: Each tank scheduled once per year; to be conservative, assume one extra clearing a year, so two
clearings per year.
218 lb HFP
x 2 clearings/year
437 Ib/yr HFP
VOC from Distillation system #2 = 412 lb VOC
x 2 clearings/year
= 823 Ib/yr VOC
•
193 lb HFPO
x 2 clearings/year
= 387 Ib/yr HFPO
DEQ-CFW 00087907

HFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 7 of 8
C. "Rest of the Process"
rest of the HFPO process contains HFP, HFPO, and both low and high vapor pressure acid fluorides (acid
ides are organic compounds which release HF when exposed to the atmosphere). The calculations below do not
include the low-pressure acid fluorides because at temperatures at which the vessels are prepared for maintenance
the concentration of the low vapor pressure acid fluorides is very low. The high vapor pressure acid fluorides are not
included because they are assumed to go to the WGS during decontamination. Though some of the process is
located inside buildings, to be conservative it will be assumed that all emissions are fugitive emissions.
Assume that: Pressure is vapor pressure of HFP/HFPO at ambient temperature (HFP and HFPO have the same
vapor pressures)
Composition HFP to HFPO of vapor space in equipment is equivilant to ratio in line 11 of HFPO
Flowsheet W 130878 :
44 wt% HFP
56 wt% HFPO
Calculations:
PV=nRT
Tank Volume = 1100 gal =
Contents =
Average system pressure
Average system temperature = 77 deg F =
R=
147 ft3
44 wt% HFP (MW=150 Ib/Ibmol) _
56 wt% HFPO (MW=166 lb/Ibmol) _
100 psis
537 R
10.73 psis-ft3/lbmol/R
n = PV/RT
0 n = 100 psia x 147 ft3 = 2.55 Ibmol material
10.7 psia-ft3/lbmol/R 537 R
47 mol% HFP
53 mol% HFPO
2.55 Ibmol material x 47 % HFP x 150 lb HFP = 180 lb HFP
Ibmol HFP
2.55 Ibmol material x 53 % HFPO x 166 lb HFPO = 224.5 lb HFPO
Ibmol HFPO
Total VOC per cleaning: 179.9 lb HFP
+ 224.5 lb HFPO
= 404.3 lb VOC
Clearings/year: Each tank scheduled once per year; to be conservative, assume one extra clearing per year, so two
clearings per year.
180 lb HFP
x 2 clearings/year
360 Ib/yr HFP
VOC from "Rest of the Process" = 404.3 lb VOC
x 2 clearings/year
= 808.6 Ib/yr VOC
•
224.5 lb HFPO
x 2 clearings/year
449 Ib/yr HFPO
DEQ-CFW 00087908

HFPO Manufacturing Process 2004 Emissions Non -Point Source Emissions
Page 8 of 8
D. Total fugitive Emissions from Maintenance Work
•
Source
Ib/yr HFP
Ib/ r HFPO
Ib/yr VOC
II -A
HFP Storage and Feed
774
774
II-B
Distillation System #2
437
387
823
II-C
"Rest of the System"
360
449
809
Total
1,5701
835
2,406
III. Non -Point Source VOC Emission Summary
Nafion®
Compound
Point -Source
Emissions
Ibs
Stack Emissions
Fugitive Emissions
Total
Inside Emissions
(lbs)
Outside
Emissions (Ibs)
Maintenance
Emissions Ibs)
Ibs
CO F2
769
36
344
1,148
PAF
574
27
256
857
TFF
272
13
122
406
TAF
272
13
122
406
HFP
22,621
1045
10107
1570
35,343
HFPO
22,748
1051
10165
835
34,799
Benzene
1.60
2
Toluene
8922
8,922
Total
47,256
2,183
30,039
2,406
81,883
Note: Speciated emissions (except for benzene, toluene, and maintenance emissions) were estimated by assuming
that each compound's emission concentration was equal to the compound's stack emissions fraction of the total stack
emissions.
example: the stack emission of PAF was 574 Ibs
with the total stack emission of VOCs being 47,256 Ibs
The total outside fugitive emission (minus benzene & toluene) was 21,114.98 Ibs VOC
574 Ibs PAF x 21,114.98 fugitive VOC =
47,256 Ibs VOC
•
256 lb fugitive PAF emissions
DEQ-CFW 00087909