DEQ-CFW_00086591

Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Determination
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2007 AIR EMISSIONS INVENTORY SUPPORTING DOCUMENTATION
isEmission Source ID No: NS-B
Emission Source Description: VE-North PPVE Manufacturing Process
Process & Emission Description: The VE-North PPVE manufacturing process is a continuous chemical
reaction. All emissions from the process are vented through the Nafion Division Waste Gas Scrubber
(Control Device ID No. NCD-Hdr) which has a documented control efficiency of 99.6% for all acid fluoride
compounds. Some emitted compounds are assumed to pass completely through the scrubber, so the control
efficiency for those compounds is assumed to be 0%. The control of emissions of specific compounds will
be addressed and detailed in the following pages.
The PPVE process in VE-North emits compounds in the acid fluoride family. In the presence of water (such
as in atmospheric moisture), these acid fluorides can eventually hydrolyze to hydrogen fluoride. For the
purpose of this emissions inventory, a conservative approach will be taken and the acid fluorides will be
reported both as a VOC and as the equivalent quantity of hydrogen fluoride.
Basis and Assumptions:
- The PPVE process flowsheet is the basis for relative concentrations of before -control emissions of
gaseous wastes.
- Calculations of point source emissions are based on actual vent flow totals taken from the IP21 Historian.
- All emission determination calculations are available on the EXCEL spreadsheet found at
S:/Everyone/martinas/Emissions/2007/VEN Air Emissions 2007.xls.
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DEQ-CFW 00086591

Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Determination
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Point Source Emisslon Determination
A. Hexafluoropropylene (HFP)
HF Potential:
HFP is a VOC without the potential to form HF
Quantity Released
HFP is a byproduct present in the BFPO feed. It is an inert in VE North that is
vented to the WGS.
HFP vented per the process flowsheet
Vented from the Condensation Reactor.
Vented from the Crude Receiver
Vented from the Foreshots Receiver
Vented from the Stripper
0.05 kg HFP
2.35 kg CondRxVentFlo
0.01 kg HFP
13.97 kg Crude Receiver Vent
0,01 kg HFP
1.06 kg ForeshotsReceiverVen
30 kg HFP
100 kg Stripper Vent
HFP vented based on
5,698 kg total Condensation Reactor vent stream (22266FG).
HFP vented based on
6,666 kg total Crude Receiver vent stream (22701FG).
HFP vented based on
1,308 kg total Foreshots Receiver vent stream (22826FG).
HFP vented based on
14,123 kg in the Stripper vent stream (22231FC).
HFP vented from Condensation Reactor:
0.05 kg HFP x
5,698 kg CndRx = 132 kg HFP
2.35 kg CndRx
HFP vented from Crude Receiver
0.01 kg HFP x
6,666 kg CrRec = 23 kg HFP
3.97 kg CrRec
HFP vented from Foreshots Receiver
0.01 kg HFP x
1,308 kg FsRec = 11 kg HFP '
1.06 kg FsRec
HFP vented from Stripper
30 kg HFP x
14,123 kg Strpr = 4,237 kg HFP
100 kg Strpr
VOC Emissions
132 kg from Condensation Reactor
+ 23 kg from Crude Receiver
+ 11 kg from Foreshots Receiver
4,237 kg from Stripper
4,403 kg HFP = 4,403 kg VOC
9,707 lb VOC
CAS No.116-15-4
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Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Determination
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B. Hexafluoropropylene oxide (REPO)
HF Potential:
HFPO is a VOC without the potential to form HF
Quantity Released
HFPO unreacted in condensation is vented to the WGS.
CAS No. 428-59-1
BFPO vented per the process flowsheei
0.11 kg HFPO
Vented from the Condensation Reactor:
12.35
kg Cond Rx Vent Flow
Vented from the Crude Receiver
13.97
0 kg HFPO
kg Crude Receiver Vent
O kg HFPO
Vented from the Foreshots Receiver
1.06 kg ForeshotsReceiverVen
Vented from the Stripper
60 kg HFPO
100 kg Stripper Vent
BFPO vented based on
5,698 kg total Condensation Reactor vent stream (22266FG).
BFPO vented based on
6,666 kg total Crude Receiver vent stream (22701FG).
BFPO vented based on
1,308 kg total Foreshots Receiver vent stream (22826FG).
HFP vented based on
14,123 kg in the Stripper vent stream (22231 FC).
HFPO vented from Condensation Reactor:
0.11 kg HFPO x
5,698 kg CndRx = 276 kg HFPO
2.35 kg CndRx
HFPO vented from Crude Receiver
0.00 kg BFPO x 6,666 kg CrRec
3.97 kg CrRec
HFPO vented from Foreshots Receiver
0.00 kg HFPO x 1,308 kg FsRec
1.06 kg FsRec
HFP vented from Stripper
60 kg HFPO
100 kg Strpr
VOC Emissions
r�
x 14,123 kg Strpr
0 kg HFPO
0 kg HFPO
= 8,474 kg BFPO
276 kg from Condensation Reactor
+ 0 kg from Crude Receiver
+ 0 kg from Foreshots Receiver
+ 8,474 kg from Stripper
= 8,749 kg HFPO = 8,749 kg VOC
19,288 lb VOC
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Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Determination
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C�
C. Perfluoroproplonyl fluoride (PPF)
HF Potential:
ach mole of PPF MW =166 can generate 1 mole of HF MW = 20).
1 kg PPF-1 molePPF 20g HF 1 moleHF = 0.120kgHU
166g PPF 1 moleHF 1 molePPF
Therefore, each 1 kg of PPF generates 0.120 kg of HF
Qnanti y Released
Before -control PPF vented per the process flowsheet
Vented from the Condensation Reactor: 2.14 kg PPF
12.35 kg Cond Rx Went Flow
Vented from the Crude Receiver 0 kg PPF
13.97 kg Crude Receiver Vent
0 kg PPF
Vented from the Foreshots Receiver 1.06 kg ForeskotsReceiverVmn
Vented firom the Stripper 10 kg PPF
100 kg Stripper Vent
PPF vented based on 5,698 kg total Condensation Reactor vent stream (22266FG).
PPF vented based on 6,666 kg total Crude Receiver vent stream (22701FG).
PPF vented based on 1,308 kg total Foreshots Receiver vent stream (22826FG).
PPF vented based on 14,123 kg in the Stripper vent stream (22231 FC).
Before control PPF vented from Condensation Reactor:
2.14 kg PPF x 5,698 kg CndRx = 5,180 kg PPF
2.35 kg CndRx
PPF vented from Crude Receiver
0.00 kg PPF x 6,666 kg CrRec = 0 kg PPF
3.97 kg CrRec
PPF vented from Foreshots Receiver
0.00 kg PPF x 1,308 kg FsRec = 0 kg PPF
1.06 kg FSRec
PPF vented from Stripper
10 kg PPF x 14,123 kg Strpr = 1,412 kg PPF
100 kg Strpr
Total before -control PPF vented = 6,593 kg PPF
After -control emissions utilizing the 99.6% control efficient Waste Gas Scrubber (WGS):
CAS No. 42241-7
VOC Emissions 6,593 kg PAF
Waste Gas Scrubber x (100%-99.6%)
26 kg PAF = 26 kg VOC
58 lb. VOC
HF Equivalent Emissions 26 kg PAF
x 0.120 kg HF/kg PAF
3 kg HF = 7.0 lb. HF
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Vinyl Ethers North
Air Emissions Inventory PPVE Process Emissions Determination
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D. Tetrafluoroethylene (TFE)
0 HF Potential:
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TIE is a VOC without the potential to form BF
Quantity Released
TFE is a byproduct that can be formed in the ABR system. It is an inert in VE-North that is
vented to the WG$.
TIE vented per the process flowsheet
0 kg TFE
Vented from the Condensation Reactor 12.35 kg Cond Rx Vent Flow
2.17 kg TFE
Vented from the Crude Receiver 3.97 kg Crude Re ceiver Vent
0.0045kgTFE
Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiverVent
0 kg TFE
Vented from the Stripper 100 kg Stripper Vent
TFE vented based on 5,698 kg total Condensation Reactor vent stream (22266FG).
TFE vented based on 6,666 kg total Crude Receiver vent stream (22701FG).
TFE vented based on 1,308 kg total Foreshots Receiver vent stream (22826FG).
TFE vented based on 14,123 kg in the Stripper vent stream (22231 FC).
TIE vented from Condensation Reactor:
0.00 kg TFE x 5,698 kg CndRx = 0 kg TFE
2.35 kg CndRx
WE vented from Crude Receiver
2.17 kg TFE x 6,666 kg CrRec = 3,642 kg TFE
3.97 kg CrRec
TFE vented from Foreshots Receiver
0.0045 kg TFE x 1,308 kg FsRe c = 6 kg TFE
1.06 kg FsRec
TFE vented from Stripper
0 kg TFE x 14,123 kg Strpr = 0 kg TFE
100 kg Strpr
VOC Emissions 0 kg from Condensation Reactor
+ 3,642 kg from Crude Receiver
+ 6 kg from Foreshots Receiver
+ 0 kg from Stripper
3,648 kg TFE = 3,648 kg VOC
8,042 lb VOC
CAS No.116-14-3
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Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Determination
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E. Pertluoropropyl vinyl ether (PPVE)
HF Potential:
PPVE is a VOC without the potential to form HF
Quantity Released
PPVE vented per the process flowsheet
CAS No.1623-5-8
0 kg PPVE
Vented from the Condensation Reactor: 2.35 kg Cond Rx Vent Flow
0.50 kg PPVE
Vented from the Crude Receiver 13.97 kg Crude Re cei,,er Vent
0.88 kg PPVE
Vented from the Foreshots Receiver 11.06 kg ForeshotsReceiverVent
0 kg PPVE
Vented from the Stripper 100 kg Stripper Vent
PPVE vented based on 5,698 kg total Condensation Reactor vent stream (22266FG).
PPVE vented based on 6,666 kg total Crude Receiver vent stream (22701FG).
PPVE vented based on 1,308 kg total Foreshots Receiver vent stream (22826FG).
PPVE vented based on 14,123 kg in the Stripper vent stream (22231FC).
PPVE vented from Condensation Reactor:
0.00 kg PPVE x 5,698 kg CndRx = 0 kg PPVE
2.35 kg CndRx
PPVE vented from Crude Receiver
0.50 kg PPVE x 6,666 kg CrRec = 848 kg PPVE
3.97 kg CrRec
PPVE vented from Foreshots Receiver
0.88 kg PPVE x 1,308 kg FsRec = I,084 kg PPVE
1.06 kg FsRec
PPVE vented from Stripper
0 kg PPVE x 14,123 kg Strpr = 0 kg PPVE
100 kg Strpr
VOC Emissions 0 kg from Condensation Reactor
+ 848 kg from Crude Receiver
+ 1,084 kg from Foreshots Receiver
+ 0 kg from Stripper
= 1,932 kg PPVE = 1,932 kg VOC
4,259 lb VOC
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Vinyl Ethers North Air Emissions Inventory PPVE Process Emissions Determination
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F. Perfluoro-2-butene (C4)
HF Potential:
C4s are VOCs without the potential to form BF
Quantity Released
C4s are perfluorobutenes that are byproducts from the Agitated Bed Reactor system.
They are inerts in VE-North that are vented to the WGS.
C4s vented per the process flowsheet
0 kg Cos
Vented from the Condensation Reactor: F35 kg Cond Rx Vent Plow
0.01 kg C4s
Vented from the Crude Receiver 13-97 kg Crude Re ceiver Vent
0.15 kg C4-s
Vented from the Foreshots Receiver 1.06 kg ForeshotsReceiverVent
0 kg C4s
Vented from the Stripper 100 kg Shipper Vent
C4s vented based on 5,698 kg total Condensation Reactor vent stream (22266FG).
C4s vented based on 6,666 kg total Crude Receiver vent stream (22701FG).
C4s vented based on 1,308 kg total Foreshots Receiver vent stream (22826FG).
C4s vented based on 14,123 kg in the Stripper vent stream (22231FC).
C4s vented from Condensation Reactor:
0.00 kg C4s x 5,698 kg CndRx = 0 kg C4s
2.35 kg CndRx
C4s vented from Crude Receiver
0.01 kg C4s x 6,666 kg CrRec = 15 kg C4s
3.97 kg CrRec
C4s vented from Foreshots Receiver
0.15 kg C4s x 1,308 kg FsRec = 184 kg C4s
1.06 kg FsRec
C4s vented from Stripper
0 kg C4s x 14,123 kg Strpr = 0 kg C4s
100 kg Strpr
VOC Emissions 0 kg from Condensation Reactor
+ 15 kg from Crude Receiver
+ 184 kg from Foreshots Receiver
+ 0 kg from Stripper
200 kg C4s = 200 kg VOC
440 lb VOC
CAS No. 360-894
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G. Perfluoropentene (CS)
HF Potential:
C5s are VOCs without the potential to form BF
4uantit�Released
C5s are perfluoropentenes that are byproducts from the Agitated Bed Reactor system.
They are inerts in VE-North that are vented to the WGS.
C5s vented per the process flowsheet
0 kg CSs
Vented from the Condensation Reactor 12.35
kg Cond Rx Vent Flow
0 kg C5s
Vented from the Crude Receiver
3.97 kg Crude Receiver Vent
0.02 kg CSs
Vented from the Foreshots Receiver
11.06
kg ForeshotsReceiverVent
Vented from the Stripper
0 kg C5s
100 kg Stripper Vent
C5s vented based on 5,698
kg total Condensation Reactor vent stream (22266FG).
CSs vented based on 6,666
kg total Crude Receiver vent stream (22701FG).
CSs vented based on 1,308
kg total Foreshots Receiver vent stream (22826FG).
C5s vented based on 14,123
kg in the Stripper vent stream (22231FC).
C5s vented from Condensation Reactor:
0.00 kg C5s x
5,698 kg CndRx = 0 kg C5s
2.35 kg CndRx
C5s vented from Crude Receiver
0.00 kg C5s x
6,666 kg CrRec = 0 kg C5s
3.97 kg CrRec
C5s vented from Foreshots Receiver
0.02 kg C5s x
1,308 kg FsRec = 22 kg C5s
1.06 kg FSRec
C4s vented from Stripper
0 kg CSs x
14,123 kg Strpr = 0 kg C5s
100 kg Strpr
VOC Emissions
0 kg from Condensation Reactor
+ 0 kg from Crude Receiver
+ 22 kg from Foreshots Receiver
+ 0 kg from Stripper
= 22 kg C5s = 22 kg VOC
49 lb VOC
CAS No. 376-974
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H. Carbon Monoxide (CO)
HF Potential:
CO can not form BF
Quantity Released
CO is a byproduct from the Agitated Bed Reactor system.
This inert in VE-North that are vented to the WGS.
CO vented per the process flowsheet
0 kg CO
Vented from the Condensation Reactor 12.35 kg Cond Rx Vent Flow
1.27 kg CO
Vented from the Crude Receiver 3.97 kg Crude Receiver Vent
0kgCO
Vented from the Foreshots Receiver 1.06 kg ForeshotsRecetver Vent
0 kg CO
Vented from the Stripper 100 kg Stripper Vent
CO vented based on 5,698 kg total Condensation Reactor vent stream (22266FG).
CO vented based on 6,666 kg total Crude Receiver vent stream (22701FG).
CO vented based on 1,308 kg total Foreshots Receiver vent stream (22826FG).
CO vented based on 14,123 kg in the Stripper vent stream (22231FC).
CO vented from Condensation Reactor.
0.00 kg CO x 5,698 kg CndRx = 0 kg CO
2.35 kg CndRx
CO vented from Crude Receiver
1.27 kg CO x
3.97 kg CrRec
CO vented from Foreshots Receiver
-0.00 kg CO x
1.06 kg FSRec
CO vented from Stripper
0 kg CO x
100 kg Strpr
CO Emissions
6,666 kg CrRec =
1,308 kg FsRec =
14,123 kg Strpr =
0 kg from Condensation Reactor
2,138 kg from Crude Receiver -
0 kg from Foreshots Receiver
0 kg from Stripper
2,138 kg CO =
CAS No. 630-08-0
2,138 kg CO
0 kg CO
0 kg CO
4,713 Ib CO (not a VOC)
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Vinyl Ethers North
Air Emissions Inventory
PPVE Process Emissions Determination
Page 10 of 13
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E
I. VOC Summary
Nafion Compound Name
Before Control
Generated
After Control.
Stack Emissions
kg/yr lblyr
VOC
lblyr
HF
lblyr
A.
HFP
4,403
9,707
9,707
B.
HFPO
8,749
19,288
19,288
C.
PPF
6,593
14,534
58
7.0
D.
TFE
3,648
8,042
8,042
E.
PPVE
1,932
4,259
4,259
F.
C4
200
440
440
G.
C5
22
49
49
K
AN
4,357
9,606
9,606
Total
29,904
65,926
51,450
7.0
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Air Emissions Inventory
PPVE Process Emissions Determination
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J. Total Emission Summary**
** All Emissions in this table represent "After Control' emissions.
Nafion Compound Name
Process
Emissions
lb/
Equipment
Emissions (Note')
lb/
Maintenance
Emissions (Note2)
Ib/
Total
Emissions
lb/yr
A.
HFP
9,707
5
0
9,712
R.
)FPO
19,288
360
18
19,666
C.
PPF
58
10
1
69
D.
TFE
8,042
0
0
8,042
E.
PPVE
4,259
590
553
5,403
F.
IC4
440
57
75
572
G.
C5
49
0
0
49
H.
CO (not a VOC)
0
0
4,713
K.
AN
148
7
9,606
*
BFPO-Dimer
271
37
308
*
jBFPO Trimer
7
1
7
Total
41844 1
1,447
692
58,147
Note 1 - See section titled "Equipment Emissions" for details
Note 2 - See section titled "Maintenance Emissions" for details
CO not realistically expected through equipment or maintenance emissions
AN total based on material balance, see section K.
* Not normally emitted from the process as a routine stack emission
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BF Equivalent Emissions
Naflion Compound Name
Process
Emissions
lb/
Equipment
Emissions
lb/
Maintenance
Emissions
lb/
Total
Emissions
lb/yr
C.
PPF
7
1.2
0.15
8.35
*
BFPO -Diener
16.3
2.20
18.54
*
HFPO Trimer
0.3
0.03
0.29
Total
7
18
2.38
27.19
* Not normally emitted from the process as a rounne stacx emission
The estimated BF equivalent emissions were determined by multiplying the
Molecular weight of BF/Molecular weight of the acid fluoride, I mole acid fluoride generates 1 mol BF
For Example:
20 lb/mol BF X 10 lb/yr Equipment PPF = 1.2 lb/yr BF
166 lb/mol PPF
The estimated BF equivalent emissions from Maintenance Emissions were determined by multiplying the
Molecular weight of BF/Molecular weight of the acid fluoride, I mole acid fluoride generates 1 mol BF
For Example:
20 lb/mol BF X 1.23 lb/yr Maintenance PPF = 0.15 lb/yr BF
166 lb/mol PPF
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Y— Acetonitrile (AN)
CAS No. 75-05-8
HF Potential
AN is a VOC and Hazardous Air Polluntant without the potential to form HF.
Quantity Released
AN emissions based on
11,541 kg AN fed
Hydrocarbon waste sent to Hydrocarbon waste tank
= 7,140 kgs WC waste
PPVE generated during the year
168,387 kg PPVE
Assume that:
5% of spent acetonitrile are fluorocarbons.
AN portion of hydrocarbon waste stream:
7,140 kg to H/C waste
x 1-(.1
6,783 kg AN to H/C waste
Material Balance
Based on total Vinyl ether produced 168,387 kg PPVE
Assume
90% Crude is needed to generage that amount of PPVE
70% of AF going to ABR is needed to create the Crude
Feed going to A13R is 1,500 ppm AN
1,000,000
Therefore:
168,387 kg PPVE
\ 0.90 Crude
\ 0.70 AF
x 0.0015 ppm AN in Feed to ABR
401 kg AN
VOC Emission
11,541 kg AN fed
- 6,783 kg AN to H/C waste
401 kg AN to ABR
4,357 kg AN = 4,357 kg VOC
9,606 Ib VOC
AN only used during a PPVE Campaign
Total AN = 9,606 . Ib VOC
E,
DEQ-CFW 00086603