DEQ-CFW_00086029

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HFPO Manufacturing Process Non -Point Source Emissions
Page 1 of 12
Non -point Source Emission Determination:
Non -point source emissions include equipment emissions and maintenance emissions. Equipment emissions are due to leaks from 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
Avera a Vessel Contents
Line 6 Line 6 Line 4
k /hr
Total
% of
contents
% VOC
% HF
HF
Potential
% overall HF Potential
0.606
0.172
0.11
0.081
02
1
2.41
2.4
1 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%
0.40/6
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
x
x
500
500
495.9 1
1495.9
30.6%
30.6%
30.6%
0.606
30.6%
TAF
x
Ix
335
3351
3321
1002
20.5%
20.5%
20.5%
0.606
20.5%
TAF
x
x
479
4791
476.31
1434.3
29.4 %
29.4 %
29.4 %
0.606
29.4
Total
48 55.2
94.7%
87.4%
82.3%
1 1.0%
Assume that: 95% of process materials are VOCs;
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.
erage HF roien uai 0.504
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 712.699 lb VOC generated
x 8784 hr/month**31-day month x (100%-95%) scrubber efficiency
x 0.880 lb. A/F VOC/lb. EE = 35.635 lb/month VOC emitted
= 712.699 lb/month VOC generated
From non-acid fluorides: 0.092 lb. EE/hr
x 8784 hr/month**31-day month
x 0.070 lb. Non-A/F VOC/lb. EE
= 56.692 lb/month VOC
Barricade HF: 0,092 lb. EE/hr
x 8784 hr/month
x 0.504 lb. HF/lb. EE
x (100%-95%) scrubber efficiency
= 20.409 lb/month HF
Total Barricade VOC Emissions:
35.635 lb/month VOC
+ 56.692 lb/month VOC
= 92.327 lb/month VOC
DEQ-CFW 00086029

HFPO Manufacturing Process
Non -Point Source Emissions
Page 2 of 12
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2. Fugitive Emissions From Distillation System #1
Emissions are vented from equipment located in tower and are vented through stack.
From W1208078 HFPO Flowsheet:
Material
VOC
HF
Average Vessel Contents
% of
contents
% VOC
% HF
HIF
Potential
% overall
HF Potential
Line 8 k /hr
0.606 1
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
x
99.9
38.81 %
38.8%
HFA
x
1
0.39%
0.4%
PMFF
x
9.6
3.73%
3.7%
3.7%
0.606
3.7%
PMAF
ix
x
x
3.8
1.48%
1.5%
1.5%
0.110
1.5%
PMCP
5.1
1.98 %
TFF
x
x
TAF
x
x
TAF
x
x
TAF
x
x
Total
257.4
1
1 94.7%1
87.4%1
1 82.3%1
1.0%1.
1.5%
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 lb/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
x 8784 hrlmonth
x 0.950 lb. VOC/lb. EE
375.516 lb/month VOC
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:
HF: 0.045 lb. EE/hr
x 8784 hrlmonth
x 0.121 lb. HF/lb. EE
47.829 lb/month HF
Material
VOC
HF
Avera a Vessel Contents k /hr
% of
contents
% VOC
% HF
HIF
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
x
99.6
96.7
96.7
293
30.79%
30.79%
HFA
x
1
1
0.11%
0.11%
PMFF
x
x
9.6
9.61
1.01%1
1.01%1
1.01%
0.6061
PMAF
x
x
3.8
3.8
0.40%
0.40%
0.40%
0.11
0.40%
PMCP
5.1
5.1
10.21
1.07%
W ater
360
360
KO H
40
1 40
Total
951.5
56.9%
2.1%
0.7/
­Y� 1.1-1...
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
Pump 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 8784 hr/month
x 0.570 lb. VOC/lb. EE
626.611 lb/month VOC
HF: 0.125 lb. EE/hr
x 8784 hr/month
x 0.008 lb. HF/lb. EE
= 8.795 lb/month HF
DEQ-CFW 00086030

• HFPO Manufacturing Process
Non -Point Source Emissions
Page 3 of 12
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B. Equipment Emissions Outside Buildings (Fugitive Emissions)
1. Fugitive Emissions From Distillation System #2
From W1208078 HFPO Flowsheet:
Material
VOC
HF
Avera a Vessel Contents k /hr
% of
contents
% VOC
% HF
Line 18
Line 23
Total
02
COF2
x
Ix
PAF
x
Ix
HFP
x
1
74.5
73.8
148.3
3.18%
3.18%
HFPO
x
95.8
7.7
103.5
2.22 %
2.22 %
HFA
x
PMFF
x
x
PMAF
x
x
PMCP
5.1
5.1
10.21
0.22%
Toluene
x
2200
2200
44o0
94.38 %
94.38 %
Total
46621
0.00 %
Assume that : 100 wt. % of the process material are VOCs (most of the mass is toluene CAS No. 108-88-3)
0 wt. % of the liquid is HF.
Valve emissions: 155 valves x 0.00039 Ib/hr/valve
= 0.060 Ib/hr FE
Flange emissions: 300 flanges x 0.00018 Ib/hr/flange
- 0.054 Ib/hr FE
Pump emissions: 1 pump x 0.00115 Ib/hr/pump
= 0.001 Ib/hr FE--------- -
Total fugitive emission rate
- 0.116 Ib/hr FE
VOC: 0.116 lb. FE/hr HF:
0.116 lb. FE/hr
x 8784 hr/month
x 8784 hr/month
x 1.00 lb. VOC/lb. FE
x 0.0 lb. HF/lb. FE
= 1015.43 lb/month VOC (assume all is toluene)
- 0.00 lb/month HF
2. Fugitive Emissions From HFP Storage and Feed
Assume that: This system contains only HFP, so 100 wt. % of the process material are VOCs
HFP has no potential to form HF, so 0 wt. % of the liquid is HF.
Valve emissions: 120 valves x 0.00039 Ib/hr/valve = 0.047 Ib/hr FE
Flange emissions: 135 flanges x 0.00018 Ib/hr/flange = 0.024 Ib/hr FE
Total fugitive emission rate = 0.071 Ib/hr FE
VOC: 0.071 lb. FE/hr
x 8784 hr/month
x 1.00 lb. VOC/lb. FE
= 624.54 Ib/month VOC
3. Fugitive Emissions From Benzene
HF: 0.071 lb. FE/hr
x 8784 hr/month
x 0.0 lb. HF/lb. FE
0.00 Ib/month HF
Basis: Fugitive emissions are determined via mass balance, i.e. any mass of benzene unaccounted for in the mass balance will be
assumed to be air emissions.
Assume that: Benzene introduced into the process is mostly destroyed by reaction.
Ratio of emissions to benzene used = 1.9 lb emission/368 lb benzene used
(2002) (Future)
Calculations: 1.92 Ibs benezene = 3.61 Ibs Toluene
1126145 kg fresh HFP 2,117,586 kg fresh HFP
Benzene introduced to process:
Benzene emissions:
510.380952 Ibs
510.380952 Ibs
x 1.90 lb emission
368 lb benzene
2.64 lb benzene emission
DEQ-CFW 00086031

HFPO Manufacturing Process
Non -Point Source Emissions
Page 4 of 12
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4. Fugitive Emissions From Toluene
Basis: 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 first day of month:
Toluene added to process:
Toluene inventory in process as of last day of month:
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:
+ 3715 lb
+ 14076 lb
4479 lb
0 lb
128 lb injected into product
9602 lb
- 0lb
0 lb
0 lb
3582 lb toluene = 3582 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
92.33
20.41
A-2
Distillation System #1
375.52
47.83
A-3
Scrubbing, Dryers, Stripper Column
626.61
8.795
B-1
Distillation System #2
1015
B-2
HFP Storage and Feed
624.54
B-4
Toluene System
3582.00
Total
1 1094.451
77.031
5221.97
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)
lb/month VOC
I lb/month HF
lb/month VOC
I lb/month HF
2,1891
154
10,4441
0
Total HF emissions: 154 Ibs HF from outside building
+ 0 Ibs HF from inside building
= 154 Ibs HF
Total VOCs generated inside building: 712.70 lb VOC from Reactor, Distillation Column, #1 Recycle Tank
+ 375.52 lb VOC from Scrubber, Dryers, Stripper Column
+ 626.61 lb VOC from Scrubber, Dryers, Stripper Column
1714.83 lb VOC generated (before control device)
Conservative amount (total x 2) 3430 lb VOC generated (before control device)
DEQ-CFW 00086032

• HFPO Manufacturing Process
Non -Point Source Emissions
Page 5 of 12
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II. Maintenance Emissions
Background
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 =
Contents =
Tank pressure = 10 psig =
Tank temperature = ambient = 77 deg F =
R=
n = PV/RT
n = 24.7 psia x 401 ft3
10.7 psia-ft3/lbmol/R 537 R
401 ft3
100 % HFP (MW=150 lb/Ibmol)
24.7 psis
537 R
10.73 psia-ft3/lbmol/R
1.72 Ibmol HFP
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; Here, any scheduled cleanings
will be recorded. This will usually occur during the annual outage.
258 lb HFP
x 0 cleanings/year
0 lb/month HFP
VOC from HFP Storage Tank = 258 lb VOC per cleaning
x 0 cleanings/year
0 Ib/month VOC
DEQ-CFW 00086033

• HFPO Menufacturing Process
Non -Point Source Emissions
Page 6 of 12
B. Distillation System #2
When maintenance clearing is required for the column and 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. For the purposes of these calculations, the average operating pressure and total volume are
used.
Calculations:
PV = nRT
Tank Volume = 3300 gal = 441 ft3
Contents = 50 % HFP (MW=150 lb/Ibmol)
(Conservative approximation based off of 40 % HFPO (MW=166 Ib/lbmol)
vessel contents and volatility of compounds) 10 % Toluene (MW=92 lb/Ibmol)
Average system pressure = 20 psig = 34.7 psia
Average system temperature = 30 deg F = 490 R
R = 10.73 psia-ft3/lbmol/R
n = PV/RT
n = 34.7 psia x
10.7 psia-ft3/lbmol/R
2.91 Ibmol material x
441 ft3
2.91 Ibmol material
x 150 lb HFP =
Ibmol HFP
2.91 Ibmol material x 40 % HFPO x
490 R
50 % HFP
218 lb HFP
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; All scheduled cleanings will be recorded here. This will usually occur
during the annual outage.
218 lb HFP 193 lb HFPO
x 2 cleanings/year x 2 cleanings/year
= 437 Ib/yr HFP = 387 Ib/yr HFPO
VOC from Distillation system #2 = 412 lb VOC
x 2 cleanings/year
823 Iblyr VOC
DEQ-CFW 00086034

HFPO Manufacturing Process
Non -Point Source Emissions
Page 7 of 12
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C. 'Rest of the Process"
The rest of the HFPO process contains HFP, HFPO, and both low and high vapor pressure acid fluorides (acid fluorides 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
W130878 :
44 wt% HFP
56 wt% HFPO
Calculations:
PV = nRT
Tank Volume =1100 gal =
Contents =
Average system pressure
Average system temperature = 77 deg F =
R=
n = PV/RT
n = 100 psia x 147 ft3
10.7 psia-ft3/lbmol/R 537 R
147 ft3
44 wt% HFP (MW=150 Ib/Ibmol) _
56 wt% HFPO (MW=166 lb/Ibmol) _
100 psia
537 R
10.73 psia-ft3/lbmol/R
2.55 Ibmol material
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; All scheduled cleanings will be recorded here. This will usually occur
during the annual outage.
180 lb HFP 224.5 lb HFPO
x 2 cleanings/year x 2 cleanings/year
360 Ib/yr HFP = 449 Ib/yr HFPO
VOC from 'Rest of the Process" = 404.3 lb VOC
x 2 cleanings/year
= 808.6 Ib/yr VOC
DEQ-CFW 00086035

• HFPO NFenufacturing Process
Non -Point Source Emissions
Page 8 of 12
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E. Total fugitive Emissions from Maintenance Work
Source
lb/month HFP
lb/month HFPO
lb/month VOC
II -A
HFP Storage and Feed
0
0
11-B
Distillation System #2
437
1,646
2,083
11-C
"Rest of the System"
360
449
809
II-D
HFPO Storage System
0
0
0
Total
796
2,095
2,891
III. Non -Point Source VOC Emission Summary
Nafion®
Compound
Point -Source
Emissions
Ibs
Stack Emissions
Fugitive Emissions
Total
Inside Emissions
(Ibs)
Outside
Emissions (Ibs)
Maintenance Emissions
ibs)
Ibs
COF2
1,321
59
283
1,664
PAF
956
43
205
1,204
TFF
334
15
72
421
TAF
334
15
72
421
HFP
37,368
1678
8006
796
47,848
HFPO
8,436
379
1807
2095
12,717
Benzene
2.64
3
Toluene
3582
3,582
Total
48,751
2,1 39
14,029
2,891
67,860
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.
For example: the stack emission of PAF was 956 Ibs
with the total stack emission of VOCs being 48,751 Ibs
The total outside fugitive emission (minus benzene & toluene) was 10,443.95 Ibs VOC
956 Ibs PAF x 10,443.95 fugitive VOC = 205 lb fugitive PAF emissions
48,751 Ibs VOC
DEQ-CFW 00086036

HFPO Wnufacturing Process
Non -Point Source Emissions
Page 9 of 12
D. HFPO Storage System
The HFPO Storage section consists of two HFPO Storage Tanks and the associated equipment to contain final product. When
maintenance clearing is required for these tanks, the liquid inventory is transferred to other tanks, 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 HFPO vapors remaining at 10 psig.
#1 HFPO Storaqe Tank Calculations:
PV = nRT
Tank Volume = 6640 gal =
Contents =
Tank pressure = 10 psig =
Tank temperature = ambient = 0 deg C =
R=
n = PV/RT
n = 24.7 psia x
10.73 psia-ft3/lbmol/R
4.17 Ibmol HFPC
#2 HFPO Storaqe Tank Calculations:
PV = nRT
Tank Volume = 19970 gal =
Contents =
Tank pressure = 10 psig =
Tank temperature = ambient = 0 deg C =
R=
n = PWRT
n = 24.7 psia x
10.73 psia-ft3/IbmollR
12.54 Ibmol HFP x
888 ft3
100 % HFPO (MW=166 Ib/lbmol)
24.7 psia
490 R
10.73 psia-ft3/lbmol/R
888 ft3 = 4.17 Ibmol HFPO
490 R
x 166 lb HFPO = 693 lb HFPO = 693 lb VOC per cleaning
Ibmol HFPO
2670 ft3
100 % HFPO (MW=166 lb/Ibmol)
24.7 psia
490 R
10.73 psia-ft3/lbmol/R
2670 ft3 = 12.54 Ibmol HFP
490 R
166 lb HFP = 2082 lb HFP = 2082 lb VOC per cleaning
Ibmol HFP
Total HFPO Storage Tank VOC Emissions:
693 lb HFPO from #1 Storage Tank
x 0 cleanings/month
= 0 lb/month HFP
0 Ib/month VOC from HFPO Stroage Tank Cleaning
•
2082 lb HFPO from #2 Storage Tank
x 0 cleanings/month
= 0 lb/month HFP
DEQ-CFW 00086037