DEQ-CFW_00088408

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DEQ-CFW 00088408

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Form D: Process Information (Page 1 of 2) Facility ID# 0900009
North Carolina Department of Environment and Natural Resources
Division of Air Quality
1998 Annual Air Pollutant Emissions Inventory
1. Source ID No(s): NS-1 (NS-A in Title V)
3. Process Description: HFPO Manufacturing Process
4. Operational Schedule:
Hour per
Day
Day per
Week
5. Start Hour of Process: Continuous
6. Percentage Annual Throughput:
Dec -Feb 32
7. Maximum Process
Rate per Hour: (ex:
gal/hr, mmcf/hr)
Mar -May 23
C«Z�7 `►1 �.l_�L�I►1t11�
include units
2. Permit Item No(s): 3(b)
Weeks per
Year
June -Aug 25
8. Annual Process
Throughput:
(ex: lb/yr, gal/yr)
9. Capture Efficiency (% of Process Emissions Vented Through Control Device): 100%
Hours per CONF.
Year
Sept -Nov 20
CONFIDENTIAL
include units
10. Control Device Descriptions Primary Caustic Scrubber NCD-1 (Title V NCD-Hdr1)
Secondary
11. Combined Control Device Efficiency (%): 99.6%
12. ANNUAL FUEL USAGE (e.g. Coal, oil, wood, natural gas, etc.) - Use additional sheets if necessary
'fype trf Fuel Usird
Amount (gstl,,tensx mzricflyear}1uufur
ff
DEQ-CFW 00088409

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Form D: Process Information (Page 2 of 2) Facility ID# 0900009
Actual Emissions per Pollutant Listed for Source Described Above:
Attach calculations and documentation of emission factors or other estimation methods used.
Source ID # NS-1
""
Per Ton Pollutant: TSP PM-10 SO2 NOx VOC CO
81.9
Actual Emissions: Tons/year 33.28
***All Other HAPs/TAPs as listed in Appendix C or Appendix D (use additional sheets if necessary)***
***All Other HAPs/TAPs as listed in Appendix C or Appendix D (use additional sheets if necessary)***
PollutantAiurnbei
Aotu {Llrcac
Ctrrizents
Chlorine
7782-50-5
Fluorine
7782-41-4
Hydrazine
302-01-2
Hydrogen Chloride
7647-01-0
Hydrogen Fluoride
7664-39-3
794
Hydrogen Sulfide
7783-06-4
Lead Compounds
LEADCPDS
Methyl Chloroform
71-55-6
Methylene Chloride
75-09-2
Ozone
10028-15-6
Perch Ioroethylene
127-18-4
Phosphine
7803-51-2
Toluene
108-88-3
2,237
Information on Page 2 of Form D cannot be held confidential.
DEQ-CFW 00088410

1998 Annual Air Pollutant Emissions Inventory
T. M. Lis
Page 7
0 Fugitive Emissions
Fugitive Emissions are a function of the number of emission points in the plant (valves,
flanges, pump seals). For the fugitive emission calculations the inventory shown below is
conservative and based on plant and process diagrams.
Note that a new barricade was started up in July with a 95% efficient barricade scrubber.
Calculations
1. Reactor, Distillation column, # 1 Recycle Tank:
Composition: Assume 100% VOC w/ 85% being reactive in the barricade scrubber.
Given that: 45 wt.% of the liquid is 60.6 wt.% HF,
45 wt.% of the liquid is 6 wt.% HF,
and 10 wt.% of the liquid is 0 wt.% HF
then assume that 100% of the liquid is 30 wt. % HF.
Barricade:
Valve emissions: 119 X 0.0004 lb./hr. = 0.0481b./hr.
Flange emissions: 248 X 0.00021b./hr. = 0.05 lb./hr
Pump emissions: 1 X 0.001 lb./hr. = 0.001 lb./hr.
Barricade VOC: (0.099)(8760)(0.15) + (0.099)(8760)(0.85)(0.05) = 167
Barricade HF: (0.099)(8760)(0.3)(0.05) = 13
Total barricade emissions:
VOC: 167 lbs.
HF: 13 lbs.
2. Distillation System # 1 (excluding NS-1 LG line)
Composition: 55 wt.% VOC, 5 wt.% HF
Valve Emission: 40 X 0.0004 lb./hr. = 0.016
Flange Emission: 75 X 0.0002 lb./hr. = 0.015
Total Emission:
VOC: (0.031)(8760)(0.55) = 150 lbs.
HF: (0.031)(8760)(0.05) = 14 lbs.
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DEQ-CFW 00088411

1998 Annual Air Pollutant Emissions Inventory
T. M. Lis
Page 8
! 3. NS-1 L5 line
Composition: 100 wt.% VOC, 40 wt.% HF
Valve Emission: 20 X 0.0004 lb./hr. = 0.008
Flange Emission: 45 X 0.0002 lb./hr. = 0.009
Total Emission:
VOC: (0.017)(8760)(1) = 1491bs.
HF: (0.017)(8760)(0.4) = 601bs.
4. Scrubbing System, drying system, distillation system #2
Composition:
Valve Emission:
Flange Emission:
Pump Emission:
Total Emission:
VOC:
HF: 0
100 wt.% VOC, 0 wt.% HF
171 X 0.0004 lb./hr. = 0.0084
312 X 0.0002 lb./hr. = 0.0624
2 X 0.001 lb./hr. = 0.002
(0.0728)(8760)(1) = 638 lbs.
5. Distillation system #2
Composition:
Valve Emission:
Flange Emission:
Pump Emission:
Total Emission:
VOC:
HF: 0
100 wt.% VOC (most of the mass is toluene), 0 wt.% HF
155 X 0.0004 lb./hr. = 0.062
300 X 0.0002 lb./hr. = 0.06
1 X 0.001 lb./hr. = 0.001
(0.123)(8760)(1) = 1078 lbs. (assume all is toluene)
6. HFP Storage and Feed
Composition:
Valve Emission:
Flange Emission:
Total Emission:
VOC:
HF: 0
100 wt.% VOC, 0 wt.% HF
120 X 0.0004 lb./hr. = 0.048
135 X 0.0002 lb./hr. = 0.027
(8760)(0.075)(1) = 657 lbs.
TOTAL HFPO PLANT FUGITIVE EMISSIONS
In order to be conservative, the calculated values will be multiplied by a factor of 2.
VOC: (2839)(2) = 56781bs. (3.38 tons)
HF: (87)(2) = 174 lb.
Toluene: (1078)(2) = 2156 lb.
DEQ-CFW 00088412

1998 Annual Air Pollutant Emissions Inventory
T. M. Lis
Page 9
is 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.
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 other tank (down to 10 psig), and then the residue is evacuated to the
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 cu. ft.
Contents = 100% HFP (MW = 150 lb/ lbn oi)
Tank pressure = 10 psig = 24.7 psia
Tank temperature = ambient = 77 F = 537 R
R = 10.73 psia-ft3- lb., -R
n = PV/RT = 1.72 lb., = 258 lb VOC
Clearings/year: Each tank once per year; two/year scheduled, allow three per year.
VOC from HFP Storage tank = 0.39 tons.
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DEQ-CFW 00088413

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1998 Annual Air Pollutant Emissions Inventory
T. M. Lis
Page 10
Distillation System #2
When maintenance clearing is required for the column and tanks, the liquid inventory is
transferred out using the pressure in the vessel, the vapors are compressed into the other tank
(down to 10 psig), and then the residue is evacuated to the Waste Gas Scrubber. For the
purposes of these calculations the average operating pressure and total volume are used.
The composition of the vapor space of the columns is mostly HFP and HFPO, with some
toluene. For the purposes of this calculation, the average concentrations are 50 mol% HFP,
40 mol% HFPO, and 10 mol% toluene.
a,FAno .11411
System Volume = 3300 gal = 441 cu. ft.
VOC Contents = 50% HFP (MW = 150 lb/ lb.1)
40% HFPO (MW = 166 lb/ lbmo1)
10% toluene (MW = 92 lb/ lbmol)
Average system pressure = 20 psig = 34.7 psia
Average system temperature = 30 F = 490 R
R = 10.73 psia-ft3- lbmo, -R
n = PV/RT = 2.91 lbmo, = 218 lb HFP, 27 lb toluene,
193 lb HFPO, 438 lb VOC
Clearings per year: once per year scheduled, allow for two per year.
VOC from Distillation System #2: 876 lb.
"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
1) at temperatures at which the vessels are prepared for maintenance the concentration of the
low vapor pressure acid fluorides is very low and 2) what acid fluorides are present are
scrubbed with 99.6% efficiency in the Waste Gas Scrubber. The high vapor pressure acid
fluorides are not included because they are assumed to go to the waste gas scrubber anyway
and if the system is down the creation of these acid fluorides stops, so the total flow of these
compounds is less than what is permitted during operation. For the purposes of this
calculation the composition in the vapor space of this equipment is 47 mol% HFP and 53
mol% HFPO. The pressure is the vapor pressure of HFP/HFPO at ambient temperature.
DEQ-CFW 00088414

1998 Annual Air Pollutant Emissions Inventory
T. M. Lis
Page 11
0 Calculations:
PV=nRT
System Volume = 1100 gal = 147 cu. ft.
VOC Contents = 100%
w/ 47 mol% HFP (MW = 150 lb/ lbmoj), 53 mol% HFPO (MW = 166)
Average system pressure = 100 psia
Average system temperature = 77 F = 537 R
R = 10.73 psia-ft3- lb., -R
n = PV/RT = 2.321bmo, = 164 lb HFP, 204 lb HFPO, 368 lb VOC
Clearings/year: System total once per year scheduled, allow three per year.
VOC from "Rest of the Process" = 1104 lb = 0.55 tons
TOTAL EMISSIONS FORM MAINTENANCE WORK
VOC: 0.39 tons + 0.44 tons + 0.55 tons = 1.38 tons
Toluene = 81 lb.
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DEQ-CFW 00088415