DEQ-CFW_00086578

Vinyl Ethers North Air Emissions Inventory
EVE Process Emissions
Page 1 of 13
H
H
2007 AIR EMISSIONS INVENTORY SUPPORTING DOCUMENTATION
Emission Source ED No: NS-B
Emission Source Description: VE-North EVE Manufacturing Process
Process & Emission Description: The VE-North EVE 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 EVE 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 EVE 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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Vinyl Ethers North Air Emissions Inventory
EVE Process Emissions
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0 Point Source Emissoon Determinatlon
11
is
A. Hexafluoropropylene (HFP) -
HF Potential:
HFP is a VOC without the potential to form HF
Ouantity Released
HFP is a byproduct present in the HFPO 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
HFP vented based on
HFP vented based on
HFP vented based on
HFP vented from Condensation Reactor:
0.17 kg HFP x
0.50 kg CndRx
HFP vented from Crude Receiver
0.00 kg HFP x
15.91 kg CrRec
HFP vented from Foreshots Receiver
0.00 kg HFP x
0.14 kg FsRec
VOC Emissions
CAS No.116-15-4
Q17kgHFP
OSOkgCond?xVentFlo
0 kg HFP
15.91 kg CrudeRecetver Vent
0 kg HFP
0.14 kg ForeshotsReceiverVen
871 kg total Condensation Reactor vent stream (22266FG).
16,876 kg total Crude Receiver vent stream (22701FG).
124 kg total Foreshots Receiver vent stream (22826FG).
871 kg CndRx = 304 kg HFP
16,876 kg CrRec = 0 kg HFP
124 kg FsRec = 0 kg HFP
304 kg from Condensation Reactor
0 kg from Crude Receiver
0 kg from Foreshots Receiver
304 kg HFP = 304 kg VOC
668 Ib VOC
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Vinyl Ethers North Air Emissions Inventory EVE Process Emissions
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B. HexafiuoropropyIene oxide (HFPO)
HF Potential:
BFPO is a VOC without the potential to form BF
Quantit�Released
HFPO unreacted in condensation is vented to the WGS.
HFPO vented per the process flowsheet
Vented from the Condensation Reactor:
Vented from the Crude Receiver
Vented from the Foreshots Receiver
HFPO vented based on
HFPO vented based on
HFPO vented based on
MO vented from Condensation Reactor-
0. 13 kg BFPO x
0.50 kg CudRx
HFPO vented from Crude Receiver
0.00 kg HFPO x
15.91 kg CrRec
HYPO vented from Foreshots Receiver
0.00 kg HFPO x
0.14 kg FsRec
VOC Emissions
CAS No. 428-59-1
0.13 kg HFPO
0.50 kg Cond Rx Vent Flow
0 kg HFPO
15.91 kg Crude Receiver Vent
0 kg HFPO
0.14 kg ForeshotsReceiverVen
871 kg total Condensation Reactor vent stream (22266FG).
16,876 kg total Crude Receiver vent stream (22701FG).
124 kg total Foreshots Receiver vent stream (22826FG).
871 kg CndRx = 224 kg HFPO
16,876 kg CrRec = 0 kg BFPO
124 kg FsRec = 0 kg HFPO
224 kg from Condensation Reactor
0 kg from Crude Receiver
0 kg from Foreshots Receiver
224 kg HFPO =
224 kg VOC
492 lb VOC
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Vinyl Ethers North Air Emissions Inventory
C. Pertluoro-2-Propoxy Propionyl Fluoride (HFPO Dimer)
HF Potential:
Therefore, each 1 kg of HFPO Dimer generates
Quanti y Released
Before -control HFPO Dimer vented per the process flowsheet
ach mole of HFPO Dimer MW = 332 can generate 1 mole of HF MW = 20).
1 moleDimer 20g HF 1 moleHF _ 0.06k Hi
1kgDimen 332gDimer 1 moleHF lmoleDimer g
0.060 kg of HF
Vented from the Condensation Reactor.
0.05 kg HFPODimer
Vented from the Crude Receiver
Vented from the Foreshots Receiver
BFPO Dimer vented based on
BFPO Dimer vented based on
BFPO Dimer vented based on
EVE Process Emissions
Page 4 of 13
CAS No. 2062-98-8
0.50 kg Cond Rx Vent Flow
0 kg HFPODimer
15.91 kg Crude Receiver Vent
0 kg HFPODimer
0.14 kg ForeshotsReceiverVen
871 kg total Condensation Reactor vent stream (22266FG).
16,876 kg total Crude Receiver vent stream (22701 FG).
124 kg total Foreshots Receiver vent stream (22826FG).
Before control BFPO Dimer vented from Condensation Reactor:
0.05 kg HFPO Dimer x 871 kg CndRx =
0.50 kg CndRx
HFPO Dimer vented from Crude Receiver
0.00 kg BFPO Dimer x 16,876 kg CrRec =
15.91 kg CrRec
BFPO Dimer vented from Foreshots Receiver
0.00 kg HYPO Dimer x 124 kg FsRec =
0.14 kg FsRec
Total before -control HFPO Dimer vented =
After -control emissions utilizing the 99.6% control efficient Waste Gas Scrubber (WGS):
VOC Emissions 88 kg Dimer
Waste Gas Scrubber x (100%-99.6%)
0.35. kg Dimer
HF Equivalent Emissions
0.35 kg Dimer
x 0.060 kg HF/kg Dimer
0.02 kg HF
88 kg HFPO Dimer
0 kg BFPO Dimer
0 kg BFPO Dimer
88 kg HFPO Dimer
0.35 kg VOC
0.78 Ib. VOC
0.05 lb. HF
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Vinyl Ethers North Air Emissions Inventory EVE Process Emissions
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D. Tetratluoroethylene (TFE)
HF Potential:
TFE is a VOC without the potential to form BF
Quantity Released
TFE is a byproduct that can be formed in the ADR system. It is an inert in VE-North that is
vented to the WGS.
TFE vented per the process flowsheet
CAS No.116-14-3
0 kg TFE
Vented from the Condensation Reactor: 0.50 kg Cond Rx Vent Flow
0.18 kg TFE
Vented from the Crude Receiver 15.91 kg Crude Receiver Vent
0 kg TFE
Vented from the Foreshots Receiver 0.14 kg Poresh OhRe ceiver Ven
TFE vented based on 871 kg total Condensation Reactor vent stream (22266FG).
TFE vented based on 16,876 kg total Crude Receiver vent stream (22701FG).
TFE vented based on 124 kg total Foreshots Receiver vent stream (22826FG).
TFE vented from Condensation Reactor:
0.00 x 871 kg CndRx = 0 kg TFE
0.50 kg TFE
kg CndRx
TFE vented from Crude Receiver
0.18 x 16,876 kg CrRec = 186 kg TFE
15.91 kg TFE
kg CrRec
TFE vented from Foreshots Receiver
0.00 x 124 kg FsRec — 0 kg TFE
0.14 kg TFE
kg FsRec
VOC Emissions 0 kg from Condensation Reactor
+ 186 kg from Crude Receiver
+ 0 kg from Foreshots Receiver
186 kg TFE = 186 kg VOC
408 lb VOC
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Vinyl Ethers North Air Emissions Inventory EVE Process Emissions
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E. Methyl Perfluoro (5-Muoroformyl)
-4-Oxahexanoate) (MAE)
HF Potential:
r-
sh mole of MAE (MW = 322) can generate 1 mole of HF (MW = 20).
k MAE 1 moleMAE 20g HF 1 moleM7 _ 0.062kgID
g 3229M E 1 moleHF 1 moleMAE
Therefore, each 1 kg of mAt generates
Quantity Released
Before -control MAE vented per the process flowsheet
Vented from the Condensation Reactor.
Vented from the Crude Receiver
Vented from the Foreshots Receiver
MAE vented based on
MAE vented based on
MAE vented based on
CAS No. 69116-72-9
0.062 kg of HF
0kgMAE
0.50 kg Cond .Rx Vent Flow
0 kg MAE
115.91 kg CrudeRecetver Vent
0.04 kg MAE
0.14 kg ForP.sh0tsR6cetverYen
�j
871 kg total Condensation Reactor vent stream (22266FG).
16,876 kg total Crude Receiver vent stream (22701FG).
124 kg total Foreshots Receiver vent stream (22826FG).
Before control MAE vented from Condensation Reactor.
0.00 kg MAE x 871 kg CndRx = 0 kg MAE
0.50 kg CndRx
MAE vented from Crude Receiver
0.00 kg MAE x 16,876 kg CrRec — 0 kg MAE
15.91 kg CrRec
MAE vented from Foreshots Receiver
0.04 kg MAE x 124 kg FsRec = 33 kg MAE
0.14 kg FsRec
Total before -control MAE vented = 33 kg MAE
After -control emissions utilizing the 99.6% control efficient Waste Gas Scrubber (WGS):
VOC Emissions 33 kg MAE
Waste Gas Scrubber x (100%-99.6%)
0.13 kg MAE 0.13 kg VOC
0.29 Ib. VOC
HF Equivalent Emissions
0.13 kg MAE
x 0.062 kg HF/kg MAE
0.01 kg HF 0.02 lb. HF
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Vinyl Ethers North Air Emissions Inventory
F. Propanoic Acid, 3-[1-[Dlfluoro [ (Trifluoroethenyl)
oxy] Methyl]-1,2,2,2 Tetrafluoroethoxy]-2,2,3,3
Tetrafluoro-, Methyl Ester (EVE)
HF Potential:
EVE is a VOC without the potential to form 11F
Quantity Released
EVE vented per the process flowsheet
EVE Process Emissions
Page 7 of 13
CAS No. 63863-43-4
0 kg EVE
Vented from the Condensation Reactor: 0.50 kg Cond Rx Vent Flow
0kgEVE
Vented from the Crude Receiver 15.91 kg Crude Receiver Vent
0.Okg EVE
Vented from the Foreshots Receiver 0.14 kg Foresh otsRe ceiver Ven
EVE vented based on 871 kg total Condensation Reactor vent stream (22266FG).
EVE vented based on 16,876 kg total Crude Receiver vent stream (22701FG). .
EVE vented based on 124 kg total Foreshots Receiver vent stream (22826FG).
EVE vented from Condensation Reactor:
0.00 x
871 kg CudRx
0 kg EVE
0.50 kg EVE
kg CndRx
EVE vented from Crude Receiver
16,876 kg CrRec =
0 kg EVE
0.00 x
15.91 kg EVE
kg CrRec
EVE vented from Foreshots Receiver
0.005 x
124 kg FsRec =
4 kg EVE
0.14 kg EVE
kg FsRec
VOC Emissions
0 kg from Condensation Reactor
+
0 kg from Crude Receiver
+
4 kg from Foreshots Receiver
=
4 kg EVE =
4 kg VOC
9 lb VOC
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Vinyl Ethers North Air Emissions Inventory EVE Process Emissions
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40 G. Tetraglyme (TTG)
The emissions of Tetraglyme is based on a mass balance.
QuantAy Released
CAS No.143-24-8
326 kg TTG introduced into processes
209 kg TTG transferred to HIC waste tank
117 kg TTG unaccounted for and assumed emitted
257 Ib. Tetraglyme
Emissions of TTG from EVE = 257 lb. Tetraglyme
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C7
Vinyl Ethers North
r
H. Carbon Monoxide (CO)
HF Potential:
CO can not form BF
Air Emissions Inventory
Quantity Released
CO is a byproduct from the Agitated Bed Reactor system.
vented to the WGS.
CO vented per the process flowsheet
EVE Process Emissions
Page 9 of 13
CAS No. 630-08-0
0kgCO
0.50 kg Cond Rx Vent Flow
Vented from the Condensation Reactor.
0.59 kg CO
Vented from the Crude Receiver 14.91 kg Crude Receiver Vent
0kgCO
Vented from the Foreshots Receiver 0.14 kg ForeshotsRecezverVen
CO vented based on 871 kg total Condensation Reactor vent stream (22266FG).
CO vented based on 16,876 kg total Crude Receiver vent stream (22701FG).
CO vented based on 124 kg total Foreshots Receiver vent stream (22826FG).
CO vented from Condensation Reactor.
0.00 kg CO x 871 kg CndRx = 0 kg CO
0.50 kg CndRx
CO vented from Crude Receiver
0.59 kg CO x
15.91 kg CrRec
CO vented from Foreshots Receiver
0.00 kg CO x
. 0.14 kg FsRec
CO Emissions
16,876 kg CrRec
124 kg FsRec
0 kg from Condensation Reactor
624 kg from Crude Receiver
0 kg from Foreshots Receiver
624 kg CO =
624 kg CO
0 kg CO
1,377 lb CO
(not a VOC)
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I. VOC Summary
Nafion Compound Name
Before Control
Generated
After Control
Stack Emissions
VOC
Ib/yr
HF
Ib/ r
kg/yr
lblyr
A.
BYP
304
669
669
B.
BFPO
224
493
493
C.
=O-Dimex
88
194
0.78
0.10
D.
TFE
186
409
409
E.
MAE
33
73
0.29
0.04
F.
EVE
4
9
9
G.
TTG
117
257
257
K.
ADN
1,167
2,573
2,573
Total
2,122
4,678
4,413
0.14
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Vinyl Ethers North Air Emissions Inventory EVE Process Emissions
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J. Total Emission Summary"
0 ** All Emissions in this table represent "After Control' emissions.
Nafion Compound
p
Name
Process
Emissions
lb/
Equipment
Emissions (Note 1)
lb/
Maintenance
Emissions (Note 2)
lb/
Total
Emissions
lW/yr
A.
HFP
669
3
0
672
B.
HFPO
493
91
4
589
C.
HFPO-Diener
1
5
1
7
D.TFE
409
0
0
409
E.
MAE
0
33
4
38
F.
EVE
9
181
179
370
G.
TTG
257
4
0
261
RICO
(not a VOC)
1,377
K.
ADN
39
2
2,573
•
DAE
52
6
58
•
ITAE
2
0
3
Mbff
7
1
7
*
hydro -EVE
9
8
17
*
iso-EVE
14
12
26
Total
1,839 1
440
218
6,407
Note 1 - See section titled "Equipment Emissions" for details
Note 2 - See section titled "Maintenance Emissions" for details
H CO not realistically expected through equipment or maintenance emissions. Not a VOC
K ADN total based on material balance, see section K.
Not normally emitted from the process as a routine stack emission
E
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Vinyl Ethers North Air Emissions Inventory . EVE Process Emissions
Page 12 of 13
The estimated BF equivalent emissions were determined by multiplying the
Molecular weight of BF/Molecular weight of the acid fluoride, 1 mole acid fluoride generates 1 mol BF
For Example:
20 lb/mol BF X 5 lb/yr Equipment BFPO -Diener = 0.312 lb/yr HF
332 lb/mol BFPO -Diener
The estimated BF equivalent emissions from Maintenance Emissions were determined by multiplying the
Molecular weight of HF/Molecular weight of the acid fluoride, 1 mole acid fluoride generates 1 mol BY
20 lb/mol BF X 0.64 lb/yr Maintenance HFPO-Dimer = 0.038 lb/yr BF
332 lb/mol BFPO-Dimer
HF Equivalent Emissions
Nafion Compound
Name
Process
Emissions
lb/
Equipment
Emissions
Ib/
Maintenance
Emissions
Ib/ r
Total
Emissions
lb/yr
C.
HFPO-Dimer
0.103
0.312
0.038
0.453
E.
IMAE
0.040
2.066
0.254
2.360
•
DAE
2.117
0.257
2.373
*
TAE
0.069
0.008
0.077
*
MNIF
0.847
0.104
0.951
Total
0.14
5.41
0.66
6.22
* Not normally emitted from the process as a routine stack emission
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Vinyl Ethers North Air Emissions Inventory EVE Process Emissions
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K. Adiponitrile
HF Potential
CAS No. 111-69-3
ADN is a VOC and Hazardous Air Polluntant without the potential to form BE
Quantity Released
ADN emissions based on 3,256 kg ADN fed
VE North ADN Sent to waste Hydrocarbon tank =
VOC Emission
3,256 kg ADN fed
- 2,089 kg ADN to H/C waste
1,167 kgADN lost = 1,167 kg VOC
2,573 lb VOC
ADN only used during an EVE Campaign
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2,089 kgs H/C waste
DEQ-CFW 00086590