A-IIS.9.

7 Recovery and Purification of HFC by Distillation [PROC]

(Ralph N. Miller, DuPont, January 1997)

Your company, BIG-D CHEMICALS, is a major producer of pentafluoroethane (CF3CHF2), which

is also known as hydrofluorocarbon 125 or HFC-125. HFC-125 is one of the new ozone-friendly
fluorocarbons, and it is a replacement for chloropentafluoroethane (CF3-CClF2) or CFC-115 in many
refrigerant applications.

In the production of HFC-125, some CFC-115 is produced, and this material must be removed from
the HFC-125 product. In addition, hydrochloric acid (HCl) is always produced as a byproduct, and
it must be recovered as a reasonably pure stream for the process to be attractive.

Your new job with BIG-D is to find the most economical process to recover HFC-125 from a mixture
which contains HFC-125, HCl, and CFC-115. The HFC-125 product must contain no more than 100
ppm-wt of other organic impurities (e.g., CFC-115, HCFC-124, etc.) and the acidity level (as HCl)
must not exceed 10 ppm-wt. In addition, the process will be more economically attractive if you can
recover anhydrous HCl which contains no more than 10 ppm-wt of organic impurities. If you are
unable to meet the anhydrous HCl purity specification, the HCl must be absorbed in water (35 wt%)
and subsequently air stripped to remove the organic impurities. Aqueous HCl solutions are a drug
on the market and have essentially no value; the absorption route is used only to avoid neutralization
and waste disposal costs. Organics in the air stripper offgas must be collected and disposed of in an
environmentally acceptable manner (e.g., incineration).

For the process to be economical, CFC-115 must be recovered and recycled to the reactor. Although
recycle CFC-115 may contain up to 5 wt% HFC-125, there is a cost penalty associated with HFC-
125 recycle, so you will probably want to minimize HFC-125 in the CFC-115 stream. The recycle
CFC-115 may also contain up to 1 wt% HCl; there is no cost penalty associated with HCl recycle at
this level.

The composition of the feed stream to the new recovery/purification process is: HFC-125 5,000 pph,
CFC-115 500 pph, HCl 2,000 pph (available as a saturated vapor at 275 psig). The feedstock value
of this stream is $2.50/lb.

The values of the various product and byproduct streams are as follows:

HFC-125 product (100 ppm organics, 10 ppm HCl) $5.00/lb

HFC-125 in CFC-115 recycle 3.50/lb
Recycle CFC-115 2.50/lb
Anhydrous HCl (<10 ppm organics) 0.15/lb
Aqueous HCl (<100 ppm organics) 0.02/lb

The following utilities and services will be available as/when needed at the battery limits of the new
purification facility. Costs are in 1997 dollars.

Cooling tower water $0.09/1,000 gal *1

150-psig steam $5.00/1,000 lb *1

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 50-psig steam $4.00/1,000 lb *1
Cooling tower water $0.09/1,000 gal *1
Raw water makeup $0.55/1,000 gal *1
-25°C Refrigeration $0.12/hr/ton *2
-45°C Refrigeration $0.20/hr/ton *2
Electricity $0.065/kWhr *1

*1 Includes allocated investment.

*2 Includes electrical costs for compressors and circulating pumps. Costs for required cooling
water or allocated investment are not included. Compression requirements: -25 °C Refrig.
= 2.4 Hp/ton; -45°C Refrig. = 3.6 Hp/ton.

BIG-D's fluorochemicals facility is located on the U.S. Gulf Coast. The new plant will be situated
adjacent to an existing fluorochemicals manufacturing plant and will share some common facilities
(i.e., control room, maintenance shops, technical office building, etc.). Storage facilities exist for
both anhydrous and aqueous HCl. Except for the above, all equipment will be new (i.e., there is no
used/existing equipment available for your use). You can assume an operating utility of 85% (7,446
hours per year) for both new and existing facilities.

CFC-115 (nbp = -39.1°C) and HFC-125 (nbp = -48.1°C) can be removed from HCl (nbp = -77.5°C)
by conventional distillation; this process is energy intensive and requires low temperatures, but it has
been demonstrated in the laboratory. BIG-D's research people have been very creative and have also
developed an extractive distillation process for recovering HFC-125 and making high-purity
anhydrous HCl. The extractive distillation process requires more equipment but uses less energy.
Potential extractants are HCFC-123 (CF3-CHCl2), which is valued at $3.00/lb, and HCFC-124 (CF3-
CHClF), which is valued at $3.50/lb. These materials are available on site as pressurized liquids at
10°C and 100 psig.

Your assignment is to develop both conventional and extractive distillation processes for recovering
HFC-125 and HCl from the specified feed mixture. You will need to develop optimum flow sheets,
size and cost equipment for each case, and compare the economics of the two processes. Your flow
sheets should include energy recovery (heat integration) as appropriate. You will also need to
develop a control strategy for your preferred case; the control scheme should address start-up and
shut-down conditions as well as steady-state operation.

Notes

1. CFC-115, HFC-125, and HCFCs 123 and 124 are nonflammable and noncorrosive. Carbon steel
is a satisfactory material of construction for pressure vessels; if the temperature is less than 0°C
(either operating or upset conditions), a Charpy impact test is required. HCl may be handled in
either stainless steel or low-temperature carbon steel (Charpy impact tested) equipment.

2. On the U.S. Gulf Coast, cooling towers will supply water at about 31°C in the summertime. This
should be the design basis for any water-cooled condensers or heat exchangers. The CTW supply
temperature is about 10°C during the coldest months. CTW is high in chlorides (due to
evaporation) and is quite corrosive.

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3. The largest distillation column on the plant site is 150 ft tall. It was designed by the Plant Manager
when he was a junior engineer a number of years ago. He is quite proud of this column, and he
often points it out to new visitors to the site. You probably don't want to change this (or his
feelings about you).

4. If any of the new process steps operate under vacuum, you should assume there will be air leakage
into the process. While this is not a safety hazard, you will need to include facilities to remove
inerts from the HFC-125 product.

5. Purity requirements for the new HFC products are much more stringent than for your current CFC
products. As a result, analytical techniques have <italic>not yet been fully developed <roman>to
analyze for low levels of some trace impurities. BIG-D's analytical chemists are currently
working to develop more sensitive analytical methods to identify other impurities.

6. Thermodynamics/physical property information will be provided for the chemical species which
are not available in your simulator's database.

Reference

“Process for Separating HCl and Halocarbons,” U.S. Patent 5,421,964, assigned to E.I. DuPont de
Nemours and Company, Wilmington, DE (June 6, 1995).

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