44

Danger of Improper Process Controls

I am afraid of snakes. But the two things that I fear most are as follows:
• Hydrofluoric acid (HF) used in refinery alkylation units as a catalyst to make isooctane
for gasoline.
• A cloud of LPG (propane).
HF acid will penetrate skin and destroy bones. Clouds of LPG (propane or butane) form a
white mist, that being heavier than air, drifts across the ground searching for a source of
ignition. At which point, it will detonate with a destructive radius of ¼–½ mile. I have been
personally responsible for generating four giant clouds of LPG in Texas City in the 1970s.
• A ¾00 nipple broken off while pulling a plug on an alkylation unit contactor by an
operator using a 1600 pipe wrench.
• A 200 drain blew out due to an operator opening it too far when it was partly plugged
with hydrates (i.e., hydrocarbon-water solid ice).
• A nonstress relieved weld blew out on an 800 carbon steel pipe which had been exposed
to weak sulfuric acid.
• A 400 elbow in liquid propane service blew out massively. The elbow was below a huge
depropanizer reflux drum, which emptied to the atmosphere.
Only in the last incident, did the vapor cloud find a source of ignition. In the subsequent
detonation, the giant American Oil refinery East Plant was devastated. Also, my career at
American Oil was adversely impacted.

Alkylation Unit HF Stripper

About 5% of the gasoline produced in the United States is made in HF alkylation units.
A by-product of such units is refinery-grade propane produced as the bottom product
of the alky unit’s HF stripper (see Fig. 44.1). This stripper tower serves two functions:
• First—To strip out ethane to meet the 2% maximum ethane specification for refinery
grade HD-5 LPG (i.e., propane).
• Second—To strip HF acid out of the propane and recycle the HF acid back into the Alky
Unit Isobutane recycle stream.
The control scheme shown in Fig. 44.1 had been designed by a major contractor whose
office is located in the United States, just south of my former home in Chicago, for a
mid-sized refinery in New Jersey. I have participated in the operation and design of a

Understanding Process Equipment for Operators and Engineers. https://doi.org/10.1016/B978-0-12-816161-6.00044-8 341

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342 UNDERSTANDING PROCESS EQUIPMENT FOR OPERATORS AND ENGINEERS

350 psig

Vent
15#
Steam
Steam
Pass trap
partition
baffle No flow

Condensate

FIG. 44.1 Steam condensate diverted to deck drain.

dozen similar units, and had never questioned the intrinsic safety of the process design or
the process controls.
But there is something that I, and the Chicago Engineering Contractor, should have
questioned. That being, the 15 psig steam supply to the reboiler. Indirectly, this 15 psig
was the cause of the accident which I’ll describe in detail.

Carbonates in Boiler Feed Water

Even demineralized BFW has residual carbonates, which decompose into CO2 when
steam is generated in a boiler. Inside the tubes of a reboiler, the steam will condense,
but the CO2 will accumulate as a noncondensable gas. With time, corrosive carbonic acid
is formed, which causes leaks in the carbon steel tubes. Venting from the top of the chan-
nel head (Valve #1 shown in Fig. 44.1) will not vent off the accumulated CO2. It will just
vent off the 15 psig steam supply. The CO2 will not be separated from the 15 psig steam
until the steam is condensed to water. Basically, this means the noncondensable vent must
be located just underneath the channel head Pass Partition Baffle (see Fig. 44.1).

Reboiler Channel Head Pressure

The reader may be puzzled as to why the process controls shown in Fig. 44.1 would be
quite reasonable for 50 psig steam, but manifestly dangerous for 15 psig steam.
What’s the difference?
 Chapter 44 • Danger of Improper Process Controls 343

It has to do with the steam condensate collection header pressure. Typically, this pres-
sure is 20–30 psig. When using 50 psig steam, this is not a problem. The pressure in the
channel head is large enough to flow into the condensate line. But for the 15 psig supply
steam, allowing for losses across the steam inlet control valve, and the reboiler tubes and
outlet nozzle, the condensate pressure is likely to be 10 psig or less.
A loss of reboiler duty due to condensate back-up would result, which could only be
restored by the operators draining the steam condensate to the deck. This was precisely
the action that the operators in the New Jersey refinery were forced to do to maintain the
efficiency of the HF stripper and the required reboiler duty.

Consequences of Tube Leak

The shell side of the reboiler operated at 350 psig. The tube side operated at about 10 psig.
The tubes were immersed in liquid propane. The surface area of the reboiler was far larger
than required, until a tube leak developed due to the carbonic acid attacking the carbon
steel tubes.
The liquid propane, at 350 psig, blew through the leak, flashed, and stopped the flow of
the 15 psig steam. With the loss of steam flow, the reboiler heat duty declined. Hydrofluo-
ric acid, no longer being stripped out, fell into the bottom of the tower.

Condensate Drain Valve

Had the steam condensate been flowing into the condensate collection header, the LPG
and HF vapors would have been vented from the atmospheric vent located on the steam
condensate collection drum, which exhausted at 60 ft above grade. This outcome would
have been quite dangerous in itself, as propane is heavier than air.
But, as the steam condensate was being drained to the concrete pad, the liquid LPG and
hydrofluoric acid blew out and enveloped the Alkylation Unit in a cloud of propane and
HF. The cloud of combustible vapors did not ignite. The operators, alerted by a local com-
bustible gas monitor, donned their HF protective gear, blocked-in the condensate drain
valve, and shut down the unit without injury to refinery personnel, and before the toxic
vapor cloud could spread to the surrounding residential community. The plant had a
rather lucky escape.
However, I recall that in the 1970s, in Texas City, I also escaped from the consequences
of an LPG vapor cloud three times. But, my luck ran out the fourth time, when the 400 elbow
on the reflux drum outlet line failed. “God watches over the feeble minded,” but only up to
some point. Then, we had best take corrective action ourselves, as there is a limit even to
divine mercy.

Retrofit Design
To correct this situation, I proposed two alternates to the refinery. Both options would
eliminate the dangerous practice of draining steam condensate to the ground.
344 UNDERSTANDING PROCESS EQUIPMENT FOR OPERATORS AND ENGINEERS

350 psig

50#
steam

Steam
Pass Vent trap
partition
baffle

Condensate

FIG. 44.2 Steam condensate flows to condensate collection line.

Both options (see Fig. 44.2) included relocation of the noncondensable (i.e., CO2) vent just
beneath the channel head pass partition baffle.
The simplest option was to replace the 15 psig steam with 50 psig. This would allow the
channel head pressure to overcome the pressure in the condensate collection line. This
was the option that was adopted by the refinery.
A more complex option was to install a condensate pump and drum, and pump the
condensate. This more expensive option would allow the continued use of the low value
15 psig steam but was rejected by the refinery due to capital cost considerations.

Steam Trap
Both the existing and the new designs used a steam trap and relied on pressuring the con-
densate into the condensate collection line. For lower pressure steam, it’s best to avoid the
problem of flashing (i.e., vapor lock) downstream of the trap, by pumping the condensate,
rather than just relying on the pressure in the channel head. Further, steam traps often
prove to be unreliable. However, if no condensate recovery is required, I will use a steam
trap, and drain the condensate into the sewer, but only for nonhazardous services.
Note that the steam condensate cannot be simply drained without holding some back
pressure. Just allowing condensate to blow-out to atmospheric pressure, would greatly
diminish the reboiler’s heat transfer efficiency, due to blowing the condensate seal.
 45
Process Plant Safety

The major long-term cost of running a refinery, or I expect, any process plant, is safety. Not
the occasional “lost time injury” or occasional fatality. I am referring to incidents such as:
1. The BP, Texas City Raffinate Splitter Explosion—15 killed
2. The Unocal Amine—LPG Absorber—20 killed
3. The Amoco Asphalt Oxidizer Fire and Explosion—3 killed
4. The BP Deep Water Horizon—11 killed
5. Union Carbide—Bhopal—10,000 killed
These were multibillion dollar incidents, all of which I am personally familiar with were
the result of operators and process engineers making entirely avoidable design and/or
operational errors.
The incident at Bhopal was the result of an effort to avoid loss of production due to the
marginal design of a pump’s mechanical seal. It destroyed the Union Carbide Corporation
and killed 10,000 people.
The incident near my home in New Orleans, cost BP $20,000,000,000 (United States),
killed 11 people and spilled 5,000,000 barrels of crude oil into the Gulf of Mexico.
Often, I am retained as an expert witness in these sorts of catastrophes. The one com-
mon thread seems to be, that at some critical point in the decision-making process, that a
middle-level management person selects the wrong path, because he or she did not
understand how the equipment worked, and therefore could not foresee the ultimate
consequences of their decision.
I’ve made that sort of mistake four times at my Alkylation Unit in Texas City. I got away
with it the first three times. But, the fourth time, the law of averages prevailed, with a
resulting butane vapor cloud detonation. But that was in 1976. I’m much smarter now.

Sulfuric Acid Alky Operation

From 1974 to 1976, I was the operating supervisor of the world’s largest alky unit with a
capacity of 26,000 BSD of alkylate production. Between 1974 and 1976, four incidents
occurred, all on the same isobutane refrigerant depropanizer tower, that provide a
cautionary tale worth sharing with younger process engineers and operating supervisors.
I had worked for American Oil for 10 years as a process design engineer before being
promoted to my position in 1974 at the Texas City Sulfuric Acid Alkylation Unit. The alky
depropanizer processed an isobutane refrigeration recycle stream containing several

Understanding Process Equipment for Operators and Engineers. https://doi.org/10.1016/B978-0-12-816161-6.00045-X 345

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