DEQ-CFW_00087273

Form D6
Engineering Analysis to Document Emissions
For Oleum Storage tank and Delivery Piping to Reactor:
Emissions are accounted for in this process from flanges and valves throughout the process:
Accounting for emissions from flanges, we have 40 flanges and valves around the entire oleum system. Wherever
possible, we have used welded pipe to eliminate flange leaks. There are no valves on the bottom of the tank. The
feed line to the reactor will be drained back to the tank when not in use to minimize the potential for plugging from
the unintended polymerization of S03. Using rates of 0.0002 lb/br for both flanges and valves, counting 40 each, we
find:
(80 valve/flange connections) x 0.0002 lb/hr S03 = 0.0161b/hr S03
Over 365 days/year and 24 hours/day we have: (365 days/year) x (24 hours/day) x 0.0002 lb/hr =140 lb/year S03.
Note that pump is immersed inside tank, therefore no seals to leak.
Reactor System:
Around the reactor system we count 40 flanges and valves and a pump to deliver starting material C$F17I to reactor.
Ten valves and flanges for CsF17I system, 100% VOC
Valve Emissions: 10 x 0.0002 lb/hr = 0.002 lb/hr
Flange Emissions: 10 x 0.00021b/hr = 0.0021b/hr
For U17I = 0.0041b/br:
Total for year = 4300 hours/year = 17.5 pounds per year. No equivalent BF
For S03 and C71715COF around reactor, assume 50 wgt % each from reactor & neutralization staging tank:
Twenty Valves & Flanges
Valve Emissions = 20 x 0.00021b/br = 0.0041b/br (50% each S03 and C7F15COF)
Flange emissions = 20 x 0.002 lb/hr=0.0041b/hr (50% each S03and C7F15C0F)
Total S03 = 0.004 lb/hr x 4300 hours = 17.5 pounds per year
Total C7F15COF = 0.004 lb/hr x 4300 hours =17.5 pounds per year
EquivalentBF = (17.5 pounds C7F15C0F) x (201b/lb-mole HF) / (416 lb/lb-mole C7F15COF)
= 0.8 pounds per year equivalent BF
E
DEQ-CFW 00087273

Form D-6
I*
Engineering Analyses to Document Emissions
Flange & Pump Emissions around Simple Neutralization Tank
This vessel receives 65% oleum, iodine, sulfur dioxide and a minor amount of C7F15COF.
S02 & I2 both form low vapor pressure complexes with S03 from our experience with this chemistry. Sulfur dioxide
in the neutralizer is converted to the water-soluble sulfate by its reaction with I2 to form HI. C7F15COF is converted
to BF and C7F15COOH. S03 is converted to H2SO4.
In actual practice, waste oleum described above will be dropped to neutralization tank over ten hour period.
The species described may also be converted to the associated sodium salts. (We may operate either in a hydrolysis
mode or neutralization mode). For calculations here we have used hydrolysis. as a worst case.
Over 1/3 of a typical day, the pressure in this tank could rise above ambient and have the component of S02 present
in the vapor space. Calculating emissions from flanges & seals:
Modeling
40% H2SO4, 30% S02, 30% S03
One (1) 20-inchmanway x 0.00081b/hr = 0.00081b/hr
One (1) mechanical seal for agitator x 0.001 lb/hr = 0.001
Three (3) pump seals, three flanges x 0.003 lb/hr = 0.009
Six (6) 2-inch nozzles & valves x 0.0004 lb/hr = 0.0024
Total Emissions from Equipment Leaks = 0.01321b/hr
8760 hours/year x 0.01321b/hr = 115.6 pounds per year
46.6 pounds per year H2SO4
34.5 pounds per year of S02
34.5 pounds per year of S03
DEQ-CFW 00087274

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Engineering Analyses to Document Emissions
Distillation Column Leaks out of IIanges/valves
(Column does not have any leaks out while operating under vacuum)
Modeling 100 % C7F15COF
10" Column-6 Flange sets 6 x 0.0004 lb/br = 0.00241b/br, 4000 hours x 0.0024 lb/br = 9.6 lb/year
(Under vacuum 4760 brs)
Twenty 2" or smaller nozzles,
(Misc. transmitters) 20 x 0.00021b/br = 0.00401b/br, 4000 hours * 0.004 lb/hr = 16 lb/year
(Under vacuum 4760 hrs)
Three (3) pumps 3 x 0.001 lb/br = 0.003 lb/hr, 3 x 8760 hours = 26.28 pounds/year
Total Flange Leaks per year from distillation = 9.61b/year + 161b/year + 26.281b/year = 51.9 pounds/year
Equivalent HF = 51.9 lb/year x (201b/lb-mole) / (416 lb/lb-mole) = 2.51b/year of hydrogen fluoride
L-1
s
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Form D-6 Cont.
Engineering Analyses to Document Emissions
Emissions from Blowing down of hoses on tank truck to clear prior to disconnection
Modeling Component 100% S03
Prior to disconnecting lines of the tanker we purge them with hot N2 back to the storage tank to minimise the
pooling of liquid olewn When this volume of N2 flows back to the 90F tank, it carries with it the partial pressure of
S03. From figure 2 of DuPont publication "Sulfur Trioxide and Oleum Storage and Handling, the vapor pressure
Of S03 over 65% oleum @ 90F is 210 mm Hg.
From Thomas L. Muller, PE of DuPont Chemical Solutions Enterprise, Sulfur Products, 10 scfm for ten minutes for
the liquid line and five minutes for the vapor line is sufficient to clear these lines. That equates into 150 Otank car
change -out. This equates into:
(210 mm Hg/760 mm Hg) x (80 lb/lb-mole) x (150 0 359 ft3/lb-mole) = 9.23 pounds.
This blow -down may need to be taken over a 15-minute period since the scrubbing system "pound per hour"
capacity is limiting. Instantaneous 10-minute hourly rate here would be 6 x 9.23 = 55 pph.
Purged separately, instantaneous rate would be 2/3 of this value or 36 pph. Taking six tank cars in 2005 emissions from this source would be 9.231b/truck x 6 trucks/year — 55.41b/year
Emissions from level transmitter N2 purge. (Carries away SO
3 vapors
Assume 2 scfh x 8760 hours=17,520 fO
(17,520 ft3 / 359 ft3/ib-mole) x (210 mm Hg / 760 mm Hg) x 80 lb/lb-mole = 1078 lb/yr S03 into scrubber
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Adjusting for molecular weight of air versus fluorochemical for this basis (9/22/95 BFPO expansion Project Permit)
We will calculate an inlet leak rate of air.
(16 flanges/valves) x 0.0006 pounds/hr x (28.8/166) x (220 days/year) x (24 hours/day)
= 8.79 pounds/year of air leakage into Vessel
(8.8 pounds/year / 28.81b/ft3)= 0.305 lb. moles/year
Vapor pressure of C7F15COOH at 55C for an approach temperature, assume 10 mm Hg
Assuming vacuum of 140 mm Hg, partial pressure of 1.6 mm Hg
(1.6/140) x (0.305 lb-moles/year) x (411 lb/lb-mole) = 1.43 pounds/year (before -controls) exit condensor
Scrubbing efficiency for this component is expected to be 98% so actual VOC emissions would be about 0.028
DEQ-CFW 00087277