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Storage Tanks
Commonly used in the CPI, sulfuric acid requires many special precautions to ensure
its safe handling and storage
Koya Venkata
Reddy
FACT Engineering and
Design Org. (FEDO)
IN BRIEF
CORROSION CONTROL
INSPECTION
INSTRUMENTATION
SWITCHING OF TANK
SERVICE
TANKS IN SPENT-ACID
SERVICE
SECONDARY
CONTAINMENT SYSTEMS
VENTING REQUIREMENTS
S
TRANSFER PUMPS ulfuric acid, sometimes called the FIGURE 1. Storage tanks in sulfuric acid serice require many
“king of all chemicals,” is widely used special precautions to ensure safe operations and prevent
HOT WORKS IN TANK accidental spills or ignitions
in the chemical process industries
FARMS
(CPI) for the manufacture of vari- storage tanks separated from its floor, instan-
PIPELINES, HOSES AND ous fertilizers and other chemicals. Sulfuric taneously releasing its contents. Other tanks
VALVES acid (H2SO4) is typically stored and handled in the tank farm also released their contents.
in steel storage tanks in tank farms (Figure A fire burned for approximately 30 min, and
1) located at ports, sulfuric acid plants, fertil- sulfuric acid reached a nearby river, result-
izer plants and so on. Numerous incidents ing in significant environmental damage. One
involving explosions and spills in sulfuric acid worker was killed and eight were injured [1].
storage tanks have been reported world- Such incidents draw attention to the vul-
wide. All too often, a lack of understanding nerability of sulfuric acid storage tanks to
regarding the proper safety aspects required fires and explosions, in addition to accidental
for handling and storing sulfuric acid leads to spillage. These occurrences can be avoided
catastrophic accidents. These incidents can by understanding the various aspects of cor-
result in environmental pollution, as well as rosion in storage tanks, inspection and vent-
injuries and fatalities. ing requirements, spillage-containment sys-
For example, in 2001 at a petroleum refin- tems, instrumentation, proper materials of
ery in Delaware, a crew of contractors was construction, various governing codes and
repairing grating on a catwalk in a sulfuric standards, guidelines for hot work and so
acid storage-tank farm when a spark from on. This article describes various problems
their hot work ignited flammable vapors in faced in sulfuric acid tanks and the efforts
one of the storage tanks. One of the acid needed to mitigate them.
44 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2015
Corrosion control Inspection
Corrosion is one of the most prevalent is- Periodic thickness 98% sulfuric acid
sues in handling sulfuric acid. Two common measurements of a
corrosion mechanisms — hydrogen groov- tank’s shell and roof
ing and boundary-layer corrosion — are should be carried out LT
S03 absorber
especially dangerous in sulfuric acid service to ascertain whether Oleum
because they lead to the formation of hy- the tank is fit for ser-
drogen gas (H2), which is highly flammable, vice. According to the
colorless, odorless and readily ignitable. It recommendations of
forms an explosive mixture with air and oxy- the National Asso-
gen. The lower and upper explosive limits ciation of Corrosion
(LEL and UEL) of H2 are 4% and 74.2%, re- Engineers’ (NACE;
spectively. This means that if the concentra- Houston; www.nace.
tion of H2 is between 4% and 74.2%, and if org) Standard RP
the gas mixture is ignited, it will lead to an 0294-94, an internal
explosion, causing potentially fatal harm and inspection of sulfuric
damage to assets. Hydrogen grooving and acid tanks is to occur Oleum storage tank
boundary-layer corrosion are detailed in the every five years, and
following sections. an external in-service inspection is to be FIGURE 2. Oleum, a product
Hydrogen grooving. Tanks for storing con- carried out every two years [2]. Similarly, the of sulfuric acid plants, creates
safety issues in storage tanks
centrated sulfuric acid typically are made American Petroleum Institute (API) Standard due to the presence of sulfur
of carbon steel. The acid reacts with iron 653 requires the evaluation of flaws, deterio- trioxide (SO3) fumes
(Fe) in the shell, forming a protective layer ration or other conditions that might affect the
of ferrous sulfate (FeSO4), while simulta- performance of a tank and the determination
neously releasing H2, according to the of its suitability for the intended service [3].
following reaction: The periodic inspections should be per-
formed more frequently as tanks become
Fe + H2SO4 → FeSO4 + H2 older. Per NACE RP 0294-94, inspection
frequencies may be decided on the basis of
At the inlet line, as the acid is flowing into operating conditions, experience, inspection
the tank, H2 bubbles float up and come into results, fitness-for-service evaluations and
contact with the metal. The bubbles will risk analysis [2]. Furthermore, risk-based in-
scrape off the iron sulfate coating, exposing spection (RBI) is to be conducted for all tanks
bare metal. This will form more iron sulfate in addition to inspections at service intervals.
and release more H2 bubbles. Eventually, the Historic tank leakage and failure data are inte-
formation of H2 bubbles in the metal forms gral to RBI assessments.
grooves or corroded portions and is called
hydrogen grooving. Instrumentation
Boundary layer corrosion. In tank farms, a As previously stated, sulfuric acid spills can
corrosive atmosphere also prevails, as sulfur be extremely dangerous. Therefore, level
dioxide vapors from the storage tanks can measurement and control in storage tanks in
combine with moisture, forming sulfurous sulfuric acid service is of the utmost impor-
acid (H2SO3). This causes the tank roofs tance. First and foremost, all tanks should
and other iron-containing materials in the vi- be provided with a level indicator. Addition-
cinity to corrode. ally, high- and low-level switches should be
In acid plants, the sump tanks of absorp- provided on tanks to contain the overspill
tion towers contain acid analyzers that con- control and to avoid vacuum conditions
trol the addition of dilute acid. If these ana- when pumps are transferring acid to con-
lyzers malfunction, it can lead to an increase suming plants. All instruments are expected
in the acid temperature. If high-temperature to be compliant with safety integrity level
acid is transferred to carbon-steel stor- (SIL) 2. For more information on SIL clas-
age tanks, corrosion will occur at a much sifications, see Tolerable Risk, Chem. Eng.,
faster rate. Sept. 2007, pp. 69–74.
The general rate of shell corrosion of stor- For acid storage tanks, the use of radar-
age tanks for concentrated sulfuric acid ser- type level-measurement devices is recom-
vice is approximately 5 to 20 mils per year mended, along with control-room alarms.
(0.005 to 0.020 in./yr) [1]. Anodic protection However, many facilities have installed dif-
should be provided for the storage tanks to ferential-pressure (DP) level-measurement
minimize the corrosion of the shell. devices without any reported issues. The