DEQ-CFW_00086654

Nafion Liquid Waste
Air Emissions Inventory
Page 1 of 7
•
•
•
2007 AIR EMISSIONS INVENTORY SUPPORTING DOCUMENTATION
Emission Source ED No.:
Emission Source Description:
Process & Emission Description:
NS-E
Nafion Liquid Waste Stabilization
The Nafion liquid waste stabilization is a continuous system of storage with batch
neutralization. To comply with the regulatory requirements of RCRA SubPart CC, neither the
storage tank nor the reactor vent during normal operating conditions. All venting from this
system occurs as a non -routine maintenance activity, which is detailed in the following pages.
All emissions from this system are vented through the Nafion Division Waste Gas Scrubber
(Control Device ID No. NCD-Hdrl) which has a documented control efficiency of 99.6%
for acid fluoride compounds. The control of emissions of specific compounds will be
addressed and detailed in the following pages.
The Nafion liquid waste stabilization process emits compounds in the acid fluoride family.
In the presence of water, these acid fluorides will eventually hydrolyse to hydrogen fluoride.
For the purpose of this emissions inventory, a conservative approach will be take and the acid
fluorides will be reported both as a VOC and as the equivalent quantity of hydrogen fluoride.
Basis and Assumptions:
- For the HF emissions the entire gas flow is assumed to be HF
- The VOC emissions are assumed to be 30% COF2 and 70% TAF
- The reactor and storage tank are assumed to have the same concentration.
- The ideal gas law is used.
Information Inputs and Source Inputs:
Information Input Source of Inputs
Weight of Tank IP21 (H3450WG and H3606WG)
Category and Reason for Emission Waste Mechanical Facilitator
Point Source Emissions Determination:
Shown on the following pages
Fugitive Emissions Determination:
Shown on the following pages.
Prepared by Dianne L. Fields 5/9/2008
DEQ-CFW 00086654

Nafion Liquid Waste
Air Emissions Inventory
Page 2 of 7
•
•
0
Stack Emissions from Maintenance Activity or Emergency Activity
Background
Before performing maintenance on the reactor or storage tank, the pressure from the system
is vented to the Division WGS. Each vent is recorded in IP21 by the weight before and after
the vent. There can be times when the pressure in either the reactor or storage tank rises rapidly
due to reaction. During these times if the pressure rises above 700 kpa in either tank, a pressure
control valve can be opened to vent the tank to avoid the relief valve opening. See chart below.
Date
Tank
Category
Reason
Tank Weight
Initial
(kg)
Final
kg
10/20/07
Storage Tank
Maintenance
Shutdownwork
285
200
10/21/07
Reactor
Maintenance
Shutdownwork
3740
3641
11/27/07
Stora eTank
Emer enc
Pressures ike
688
674
Sample calculation using maintenance activity dated 10/20/07
Initial Weight minus
285 kg minus
Final Weight equals
200 kg equals
kg vented to Division WGS
85 kg vented to WGS
Assume that all of the above is VOC emissions This assumption also overstates the true emissions
as inerts, such as nitrogen are not counted.
After -control emissions utilizing the 99.6% control efficient Waste Gas Scrubber (WGS):
Percentage of acid fluoride VOCs removed by the WGS = 99.6%
Percentage of acid fluoride VOCs vented from the WGS = 100% minus 99.6%
Percentage of acid fluoride VOCs vented from the WGS = 0.4%
Therefore, VOCs vented to the atmosphere from the ###### maintenance activity is equal to:
Amount of VOCs vented to WGS: 85 kg of VOC
Percentage of VOCs vented from the WGS: x 0.4%
Quantity of VOCs vented from the WGS: = 0.34 kg VOC
= 0.7496 lb VOC
Prepared by Dianne L. Fields 5/9/2008
DEQ-CFW 00086655

Nafion Liquid Waste Air Emissions Inventory Page 3 of 7
Stack Emissions from Maintenance Activity (cont.)
VOC Emissions by Compound
Assume that the vapor is 30% COF2 and 70% TAR This assumption is based on process
knowledge of the system.
Quantity of VOCs vented from the WGS (see previous page) = 0.7496 lb VOC
COF2 (carbonyl fluoride) CAS No. 353-50-4
Sample calculation using maintenance activity dated 10/20/07
VOC emissions would be equal to:
0.750 lb VOC 0.30 lb COF2 = 0.2249 lb COF2
lb VOC
TAF (telomeric acid fluoride) CAS No. 690-43-7
(perfluoro-3,5,7, 9,11-pentaoxadodecanoyl fluoride)
• Sample calculation using maintenance activity dated 10/20/07
•
VOC emissions would be equal to:
0.750 lb VOC 0.70 lb TAF = 0.5247 lb VOC
lb VOC
Prepared by Dianne L. Fields 5/9/2008
DEQ-CFW 00086656

Nafion Liquid Waste Air Emissions Inventory
Stack Emissions from Maintenance Activity (cont.)
0
•
HF Potential
Assume that the vapor is 30% COF2 and 70% TAF. This assumption is based on process
knowledge of the system.
COF2 (carbonyl fluoride)
Page 4 of 7
CAS No. 353-50-4
Each mole of COF2 ( MW = 66) can generate 2 moles of HF (MW =20)
1 lb COF2 1 mole COF2 20 lb HF 2 moles HF = 0.606 lb of HF
66 lb COF2 mole HF 1 mole COF2
Therefore, each 1 lb of COF2 generates 0.606 lb of HF
TAF (telomeric acid fluoride)
(perfluoro-3,5,7, 9,11-pentaoxadodecanoyl fluoride)
CAS No. 690-43-7
Each mole of TAF (MW = 330) can generate 1 mole of HF (MW =20)
1 lb TAF 1 mole TAF 20 lb HF 1 moles HF = 0.061 lb of HF
330 lb TAF mole HF 1 mole TAF
Therefore, each 1 lb of TAF generates 0.061 lb of HF
Sample calculation using maintenance activity dated 10/20/07
Quantity of VOCs vented from the WGS (see Page 2) = 0.7496 lb VOC
HF equivalent emissions would be equal to:
0.750 lb VOC 0.30 lb COF2 0.606 lb HF = 0.1363 lb HF
lb VOC lb COF2
0.750 lb VOC 0.70 lb TAF 0.061 lb HF = 0.0318 lb HF
lb VOC lb TAF
Therefore, HF vented to the atmosphere from the ###### maintenance activity is equal to:
0.1363 lb HF + 0.0318 lb HF = 0.1681 lb HF
Prepared by Dianne L. Fields 5/9/2008
DEQ-CFW 00086657

Nafion Liquid Waste
Air Emissions Inventory
Page 5 of 7
•
•
•
Stack Emissions from Maintenance Activity (cont.)
Calculation page
Date
Tank
Category
Reason
Weight of Tank
Emitted
VOC
(lb)
Emitted
HF
(lb)
Initial
(kg)
Final
(kg)
10/20/07
Storage Tank
Maintenance
Shutdown work
285
200
0.750
0.168
10/21/07
Reactor
Maintenance
Shutdown work
3740
3641
0.873
0.196
11/27/07
Storage Tank
Emergency
Pressure spike
688
674
0.123
0.028
Total Emissions 1 1.75 1 0.39
Total VOC — 1.75 lb
VOC = 0.0009 ton STACK EMISSIONS
Total JHF = 0.39 lb STACK EMISSIONS
Speciated VOC Stack Emissions
The VOC emissions from the Waste Liquid Stabilization process is assumed to be comprised
of 30% by weight of COF2 and 70% by weight of TAF. The emission of these compounds
from each of the following events is determined simply by multiplying the total emitted VOC
by 30% to determine the COF2 emission and 70% to determine the TAF emission.
Date
Tank
Category
Reason
Emitted
VOC
(lb)
Emitted
COF2
(lb)
Emitted
TAF
(lb)
10/20/07
Storage Tank
Maintenance
Shutdown work
0.750
0.225
0.525
10/21/07
Reactor
Maintenance
Shutdown work
0.873
0.262
0.611
11/27/07
Storage Tank
Emergency
Pressure spike
0.123
0.037
0.086
Total Emissions 1 1.75 1 0.52 1.22
Prepared by Dianne L. Fields 5/9/2008
DEQ-CFW 00086658

•
•
Is
Nafion Liquid Waste Air Emissions Inventory
Fugitive Emissions Leak Rates for Process Equipment
Using the following table, the Fugitive Emissions Rates will be calculated:
Emission Factors
Component Service b/hr/com onent)
Pump Seals Light Liquid 0.00115
Valves Light Liquid 0.00036
Flanges All 0.00018
VOC Fugitive Emissions from Equipment Components
2 Pump Seals x o.00115 lb/hr/pumpseal =
148 Valves x 0.00036 lb/hr/valve =
45 Flanges x 0.00018 lb/hr/flange =
Total VOC Emissions from Equipment Leaks =
Total Annual Fugitive VOC Emissions:
0.0023
lb/hr VOC
0.0533
lb/hr VOC
0.0081
lb/hr VOC
0.0637 lb/hr VOC
0.0637 lb/hr VOC x 8760 hr/year = 557.84 lb VOC for 2005
0.2789 tons VOC
Speciated Fugitive VOC Emissions by Compound:
Assume that the emissions are 30% COF2 and 70% TAF. This assumption is based
on process knowledge of the system.
557.8 lb VOC 0.30 lb COF2 = 167.35 lb COF2
lb VOC
557.8 lb VOC 0.70 lb TAF = 390.49 lb TAF
lb VOC
See Page 3 for HF equivalents calculation:
557.8 lb VOC 0.30 lb COF2 0.606 lb HF = 101.42 lb HF
lb VOC lb COF2
557.8 lb VOC 0.70 lb TAF 0.061 lb HF = 23.666 lb HF
lb VOC lb TAF
101.42 lb HF + 23.666 lb HF = 125.1 lb HF
Prepared by Dianne L. Fields 5/9/2008
Page 6 of 7
DEQ-CFW 00086659

Nafion Liquid Waste Air Emissions Inventory
Page 7 of 7
•
Emission Summary
A. VOC Emissions by Compound ound and Source
Stack
Fugitive
Total
Nafion®
CAS Chemical Name
CAS No.
Emissions
Emissions
Emissions
Compound
(lbs)
(lbs)
(lbs)
C0172
Carbonyl fluoride
116-14-3
0.52
167.4
167.9
TAF
Perfluoro-3,5,7, 9,11-
690-43-7
1.22
390.5
391.7
pentaoxadodecanoyl fluoride
Total VOC (lb)
559.6
Total VOC (ton)
0.28
B. Toxic Air Pollutant Summary
Stack
Fugitive
Total
Nafion®
CAS Chemical Name
CAS No.
Emissions
Emissions
Emissions
Compound
(lbs)
(lbs)
(lbs)
HF
Hydrogen fluoride
7664-39-3
0.39
125.1
125.5
Prepared by Dianne L. Fields 5/9/2008
DEQ-CFW 00086660