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ENVIRONMENT, HEALTH, SAFETY & SECURITY PDF

SAFETY IN SULFURIC ACID STORAGE TANKS

By Chemical Engineering | November 1, 2015

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Commonly used in the CPI, sulfuric acid requires many special precautions to ensure its safe handling and storage

Sulfuric acid, sometimes called the king of all chemicals, is widely used in the chemical process industries (CPI)
for the manufacture of various fertilizers and other chemicals. Sulfuric acid (H2SO4) is typically stored and handled
in steel storage tanks in tank farms (Figure 1) located at ports, sulfuric acid plants, fertilizer plants and so on.
Numerous incidents involving explosions and spills in sulfuric acid storage tanks have been reported worldwide.
All too often, a lack of understanding regarding the proper safety aspects required for handling and storing sulfuric
acid leads to catastrophic accidents. These incidents can result in environmental pollution, as well as injuries and
fatalities.

For example, in 2001 at a petroleum renery in Delaware, a crew of contractors was repairing grating on a catwalk
in a sulfuric acid storage-tank farm when a spark from their hot work ignited ammable vapors in one of the
Figure 1. Storage tanks in sulfuric acid service require
storage tanks. One of the acid storage tanks separated from its oor, instantaneously releasing its contents. Other
many special precautions to ensure safe operations and
tanks in the tank farm also released their contents. A re burned for approximately 30 min, and sulfuric acid
prevent accidental spills or ignitions
reached a nearby river, resulting in signicant environmental damage. One worker was killed and eight were
injured [ 1 ].

Such incidents draw attention to the vulnerability of sulfuric acid storage tanks to res and explosions, in addition to accidental spillage. These occurrences can be
avoided by understanding the various aspects of corrosion in storage tanks, inspection and venting requirements, spillage-containment systems, instrumentation,
proper materials of construction, various governing codes and standards, guidelines for hot work and so on. This article describes various problems faced in sulfuric
acid tanks and the eorts needed to mitigate them.

CORROSION CONTROL

Corrosion is one of the most prevalent issues in handling sulfuric acid. Two common corrosion mechanisms hydrogen grooving and boundary-layer corrosion
are especially dangerous in sulfuric acid service because they lead to the formation of hydrogen gas (H2), which is highly ammable, colorless, odorless and readily
ignitable. It forms an explosive mixture with air and oxygen. The lower and upper explosive limits (LEL and UEL) of H2 are 4% and 74.2%, respectively. This means
that if the concentration of H2 is between 4% and 74.2%, and if the gas mixture is ignited, it will lead to an explosion, causing potentially fatal harm and damage to
assets. Hydrogen grooving and boundary-layer corrosion are detailed in the following sections. Hydrogen grooving. Tanks for storing concentrated sulfuric acid
typically are made of carbon steel. The acid reacts with iron (Fe) in the shell, forming a protective layer of ferrous sulfate (FeSO4), while simultaneously releasing H2,
according to the following reaction:

Fe + H2SO4 FeSO4 + H2

At the inlet line, as the acid is owing into the tank, H2 bubbles oat up and come into contact with the metal. The bubbles will scrape o the iron sulfate coating,
exposing bare metal. This will form more iron sulfate and release more H2 bubbles. Eventually, the formation of H2 bubbles in the metal forms grooves or corroded

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5/17/2017 SafetyinSulfuricAcidStorageTanksChemicalEngineering
portions and is called hydrogen grooving.

Boundary layer corrosion. In tank farms, a corrosive atmosphere also prevails, as sulfur dioxide vapors from the storage tanks can combine with moisture, forming
sulfurous acid (H2SO3). This causes the tank roofs and other iron-containing materials in the vicinity to corrode.

In acid plants, the sump tanks of absorption towers contain acid analyzers that control the addition of dilute acid. If these analyzers malfunction, it can lead to an
increase in the acid temperature. If high-temperature acid is transferred to carbon-steel storage tanks, corrosion will occur at a much faster rate.

The general rate of shell corrosion of storage tanks for concentrated sulfuric acid service is approximately 5 to 20 mils per year (0.005 to 0.020 in./yr) [ 1 ]. Anodic
protection should be provided for the storage tanks to minimize the corrosion of the shell.

INSPECTION

Periodic thickness measurements of a tanks shell and roof should be carried out to ascertain whether the tank is t for service. According to the recommendations of
the National Association of Corrosion Engineers (NACE; Houston; www.nace.org) Standard RP 0294-94, an internal inspection of sulfuric acid tanks is to occur every
ve years, and an external in-service inspection is to be carried out every two years [ 2 ]. Similarly, the American Petroleum Institute (API) Standard 653 requires the
evaluation of aws, deterioration or other conditions that might aect the performance of a tank and the determination of its suitability for the intended service [ 3 ].

The periodic inspections should be performed more frequently as tanks become older. Per NACE RP 0294-94, inspection frequencies may be decided on the basis of
operating conditions, experience, inspection results, tness-for-service evaluations and risk analysis [ 2 ]. Furthermore, risk-based inspection (RBI) is to be
conducted for all tanks in addition to inspections at service intervals. Historic tank leakage and failure data are integral to RBI assessments.

INSTRUMENTATION

As previously stated, sulfuric acid spills can be extremely dangerous. Therefore, level measurement and control in storage tanks in sulfuric acid service is of the
utmost importance. First and foremost, all tanks should be provided with a level indicator. Additionally, high- and low-level switches should be provided on tanks to
contain the overspill control and to avoid vacuum conditions when pumps are transferring acid to consuming plants. All instruments are expected to be compliant
with safety integrity level (SIL) 2. For more information on SIL classications, see Tolerable Risk, Chem. Eng., Sept. 2007, pp. 6974.

For acid storage tanks, the use of radar-type level-measurement devices is recommended, along with control-room alarms. However, many facilities have installed
dierential-pressure (DP) level-measurement devices without any reported issues. The wetted parts of radar level gages should be 316 stainless steel, Alloy 20 or
Teon-lined.

Some older tank farms use a type of tank level-measurement device called a bubbler system, which uses instrument air as its medium. A small ow of instrument
air (forming bubbles) enters the tank near its oor through the level probe. The air introduces some turbulence into the acid near the wall of the tank, which
increases the corrosion rate by disturbing the protective FeSO4 layer. Instrument air also contains moisture and oxygen, much of which would likely be absorbed soon
after coming into contact with the acid solution [ 1 ]. Hence, level measurements based on bubbler systems are to be avoided in sulfuric acid storage tanks, especially
in spent-acid service, as air can form an explosive mixture with the volatile hydrocarbons present in the acid.

Flow measurement is also an integral part of sulfuric acid handling. Magnetic owmeters, Coriolis mass owmeters, rotameters or ultrasonic owmeters may be
used to measure the ow of acid into and out of tanks. As with level instruments, all ow instruments are to be SIL 2 compliant.

SWITCHING OF TANK SERVICE

Some tanks must handle various forms of sulfuric acid, and switching between these materials introduces increased risk. For instance, in some tank farms, tanks
must be emptied to switch material-handling service between oleum (an intermediate in sulfuric acid production) and sulfuric acid or between concentrated sulfuric
acid and dilute spent acid. These switchovers do not typically require cleaning or draining, simply the removal of as much material as possible via pump. Each
switchover represents an opportunity to exacerbate corrosion and potentially release sulfur trioxide (SO3) vapors or volatile hydrocarbon vapors.

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