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Safety in Sulfuric Acid

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

PPE AND HSE

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

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2015 45


potentially release sulfur trioxide (SO3) va-
pors or volatile hydrocarbon vapors.
Operators must be attentive and
cautious with tanks in oleum service.
Oleum is sulfuric acid (100%) containing
around 23% free SO3. In some sulfuric
acid plants, oleum is also produced by
absorbing SO3 in concentrated sulfuric
acid, and it is common practice to locate
the oleum tanks near sulfuric acid tanks.
When oleum is introduced in a storage
tank, SO3 fumes are emitted out of the
vent, creating visible pollution and a cor-
FIGURE 3. A metal catwalk on the roof of wetted parts of radar level gages should rosive atmosphere. To curb the SO3
a storage tank provides some protection be 316 stainless steel, Alloy 20 or fumes, small-diameter packed columns
for workers, as it is unsafe for personnel
to walk directly on a tank’s shell
Teflon-lined. filled with random packings (Intallox Sad-
Some older tank farms use a type of dles are recommended) are fitted on top
tank level-measurement device called of storage tanks, as shown in Figure 2. A
a “bubbler system,” which uses instru- bleed of sulfuric acid (98%) is taken from
ment air as its medium. A small flow of the transfer-pump discharge and fed to
instrument air (forming bubbles) enters the top of the packed column to absorb
the tank near its floor through the level the rising SO3 fumes from the tank. After
probe. The air introduces some turbu- absorbing SO3 fumes, the concentrated
lence into the acid near the wall of the sulfuric acid is self-drained into the tank.
tank, which increases the corrosion
rate by disturbing the protective FeSO4 Tanks in spent-acid service
layer. Instrument air also contains mois- Fresh sulfuric acid typically contains
ture and oxygen, much of which would 98.4% acid and 1.6% water. Spent acid
likely be absorbed soon after coming typically contains 88–95% acid and up to
into contact with the acid solution [1]. 5% water, with the balance consisting of
Hence, level measurements based on hydrocarbons, including some light hy-
bubbler systems are to be avoided in drocarbons that can vaporize. A spent-
sulfuric acid storage tanks, especially in acid storage tank should be designed
spent-acid service, as air can form an and operated as if it contained volatile
explosive mixture with the volatile hydro- hydrocarbons [4].
carbons present in the acid. Special precautions are to be taken
Flow measurement is also an integral in storing spent sulfuric acid in storage
part of sulfuric acid handling. Magnetic tanks. The spent acid comes from vari-
flowmeters, Coriolis mass flowmeters, ous process industries as a byproduct
rotameters or ultrasonic flowmeters may and contains volatile hydrocarbons,
be used to measure the flow of acid which can be released during tempera-
into and out of tanks. As with level in- ture variations in the atmosphere (thermal
struments, all flow instruments are to breathing). Therefore, blanketing of the
be SIL 2 compliant. storage tanks with an inert gas, such as
carbon dioxide or nitrogen is advisable.
Switching of tank service Also, vent valves are to be provided with
Some tanks must handle various forms emergency tank venting and must be
of sulfuric acid, and switching between sized for the worst case, taking precau-
these materials introduces increased tions for scenarios such as a failure of the
risk. For instance, in some tank farms, inerting system (allowing excessive flow
tanks must be emptied to switch ma- of inert gas to enter the tank) or an exter-
terial-handling service between oleum nal fire that volatilizes hydrocarbon liquids
(an intermediate in sulfuric acid produc- in the tank. Additionally, flame arrestors
tion) and sulfuric acid or between con- should be placed in the vent line.
centrated sulfuric acid and dilute spent Tanks in spent-acid service should be
acid. These switchovers do not typically provided with a frangible roof [1]. A fran-
require cleaning or draining, simply the gible roof is a weak roof-to-shell attach-
removal of as much material as possible ment that preferentially fails over other
via pump. Each switchover represents an welded joints when subject to overpres-
opportunity to exacerbate corrosion and sure. Failure of the roof-to-shell joint pro-
46 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2015
FIGURE 4. Proper care must be taken when executing hot FIGURE 5. The same tank from Figure 4 was badly damaged after its roof exploded due to hot work
works in the presence of sulfuric acid storage tanks on the roof and the formation of hydrogen gas inside the tank while the tank was in service

vides a means to relieve overpressure ensure it is within the acceptable range,


and to avoid catastrophic failure of the typically 6.5 to 8.5.
tank and loss of its contents. Suitable valves must be placed at the
dike wall so as to divert the clean rain-
Secondary containment systems water to the dedicated rainwater drain
Special measures can be taken to en- and contaminated rainwater to an efflu-
sure that no acid escapes to the environ- ent treatment plant (ETP). Any acciden-
ment in the form of secondary contain- tally spilled acid is to be collected in spill
ment systems, including the installation tanks and neutralized properly before
of dikes. Dikes are to be built to contain disposal in the ETP.
110% of the largest storage-tank capac-
ity to contain the accidental overspill or PPE and HSE
catastrophic failure of the tanks. Dikes Although sulfuric acid itself is not flam-
must also be designed to withstand not mable, it should not be stored near
only the hydrostatic load of the liquid in organic materials, nitrates, carbides,
the tank, but also for the dynamic tidal- chlorates or metal powders. Contact
wave effect of liquid-flow load in the case between high concentrations of sulfuric
of tank failure. Acid-proof brick lining is to acid and these materials may cause ig-
be laid inside the dike so that spilled acid nition. Proper personal protective equip-
does not permeate into groundwater. In ment (PPE) and health, safety and envi-
addition to NACE RP 294-94 and API ronmental (HSE) precautions are critical
653, API Standards 650 and 620 also in any facility that handles sulfuric acid.
provide helpful guidance in the construc- Some best practices for PPE and HSE in
tion of sulfuric acid storage tanks. sulfuric acid handling are as follows:
Although dikes can be an extremely 1. Suitable eye-wash stations should
helpful measure in protection against be located near the tank farm for the
tank spills and failures, precaution must safety of personnel. The eye washers
be taken when handling the rainwater are to be tested for their functionality
that collects inside the dike area to pre- every shift.
vent environmental contamination. Col- 2. All of the flanges in the lines are to be
lected water from dikes in sulfuric acid covered with lead cladding to protect
service is acidic in nature because of the operating personnel from acciden-
the probable leaks of gases from vents tal acid leaks.
inside the dike. This can create environ- 3. Metal catwalks should be provided
mental issues if released to water bod- for working on top of tanks. Operat-
ies without correcting for pH. All rainwa- ing personnel should always use the
ter that accumulates inside the dike area catwalk and never walk directly on the
should be collected and tested for pH. If tank shell (Figure 3).
required, the pH should be adjusted to 4. All lines should be sloped toward the

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2015 47


TABLE 1. GUIDELINES FOR VALVES IN SULFURIC ACID SERVICE 4. If acid switchover (between either oleum
All of the valves in acid tank farms are to be constructed of Alloy 20
and sulfuric acid or concentrated sulfu-
ric acid and dilute spent acid) is rou-
Ball valves or plug valves are to be used for isolation purposes
tine practice in the tank farm, the vent
Copper, brass and bronze valves are not acceptable for sulfuric acid service at any concentration
valves must be sized for the worst-case
scenario of vapor release.
TABLE 2. CRITERIA FOR MATERIALS OF CONSTRUCTION FOR PIPING IN SULFURIC ACID 5. After decommissioning, the tank
SERVICE
should be re-commissioned by intro-
Fluid velocity (m/s) Material of construction Temperature limits, °C
ducing acid very slowly, so as to avoid
0–1 Carbon steel Ambient
static electricity.
0–2.5 SS 316 Ambient 6. The structural integrity of stor-
0–7 Alloy 20 60 age-tank roofs is to be inspected
For all ranges Teflon-lined pipe 200 in detail.
7. An explosion-proof hatch cover (mini-
storage tank, or toward the point of mum of 600 mm in size) should be pro-
consumption. This will prevent the vided on the tank roof.
accumulation of acid in low points in
the line, thereby eliminating possible Transfer pumps
safety hazards. Transfer pumps are used to transfer sul-
5. Operating personnel should wear furic acid from the tank farm to the end-
gloves that are loose enough to product processing plant or consuming
be easily removed in case acid plants (for example, a fertilizer plant), where
enters them. acid is fed into chemical reactors. Careful
6. Helmets should be worn at all times. To attention must be paid to these pumps.
ensure eye and face protection, a full Some recommendations for sound trans-
face shield and safety goggles are also fer-pump operations are as follows:
necessary. Goggles and a face shield 1. The transfer pumps to the consuming
are especially crucial when working in plants shall have a low-level tank trip.
a place where splashes can occur un- 2. The discharge line should be pro-
expectedly. It is essential that eye pro- vided with a pressure gage and non-
tection is provided from all angles. return valve.
7. In the event of a small spill, one 3. For the transfer of sulfuric acid from
should contain and neutralize the acid ships at a higher rate, the discharge
with lime. line should have an excess-flow check
8. Whenever a modification is carried valve to prevent accidental spillage of
out in the storage tank area, a hazard acid to the surrounding environment or
and operability (HAZOP) study should to bodies of water.
be conducted before proceeding to
implementation. Hot works in tank farms
Hot works — those tasks that require the
Venting requirements use of flames or very high temperatures,
Another crucial aspect to ensuring stor- such as welding and steel-cutting — must
age-tank safety is adequate venting. be completed with safety in mind. This is
Some best practices associated with tank especially crucial in tank farms. The fol-
venting are as follows: lowing are some guidelines for executing
1. Each sulfuric acid storage tank should hot-works tasks in facilities where sulfuric
be provided with an individual breather acid is being stored:
valve. The vent diameter is to be calcu- 1. Hot work is to be permitted only after
lated based on in-breathing, out-breath- measuring for flammable gases in the
ing and thermal-breathing requirements storage tank area. The measurement
according to API Standard 2000 [5]. of flammable gases in the storage tank
2. The vent area should be greater than area is to be done continually during
the sum of the inlet-, outlet- and drain- the hot work period.
line areas. 2. According to API RP 2009, in situa-
3. The vent (breather) valve should be tions where the work is delayed or sus-
kept at the top of the tank. At no in- pended in an area that has previously
stance should it be located at ground been pronounced gas-free, the permit
level, as it has the potential for inunda- system should specify the length of time
tion in the case of tank rupture or the beyond which oxygen and flammability
dike filling with acid or stormwater. detector tests must be repeated or the
48 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2015
permit reissued [6]. be designed with a minimum work-
3. Periodic combustible-gas and oxygen ing pressure of 14 kg/cm2 and be full-
retests (or continuous monitoring) may vacuum rated. The end fittings must
be required while hot work is proceed- be crimped or swaged. Banding is
ing. The permit should specify the not recommended. The hose-end fit-
monitoring frequency. tings should be 316 stainless steel with
4. If the hot work is to be performed on flanges or quick-connect fittings. The
the shell or roof of the storage tank, gaskets should be constructed of vir-
and if there are holes in the roof or gin Viton B materials. The user should
shell, the tank contents must be emp- have a hose-management program in
tied and purged with inert gas prior to place to ensure the integrity of hoses.
the hot work. All hoses must be dedicated to sulfuric
In many instances, non-compliance with acid service. [9]
the above measures is a main cause for Following the guidelines presented in
explosions in sulfuric acid tanks. Figures this article will help enable engineers to
4 and 5 illustrate the devastation caused safely approach the storage and han-
by not taking the proper precautions with dling of sulfuric acid. ■
hot-works tasks. Figure 4 shows a stor- Edited by Mary Page Bailey
age tank in sulfuric acid service. Figure 5
shows the same tank after a catastrophic References
explosion due to the formation of H2 gas 1. U.S. Chemical Safety and Hazard Investigation Board
during hot work. (CSB), Investigation Report — Refinery Incident,
Motiva Enterprises LLC, Delaware City Refinery,
July 17, 2001.
Pipelines, hoses and valves 2. National Association of Corrosion Engineers,
Many special design and operating con- NACE Standard RP 0294-94, Design, Fabrica-
siderations should be taken for piping, tion and Inspection of Tanks for the Storage of
Concentrated Sulfuric Acid and Oleum at Ambient
hoses and valves that are to handle sul- Temperatures, 2006.
furic acid. Table 1 provides some best 3. American Petroleum Institute, API 653 — Tank In-
practices for valves in sulfuric acid ser- spection, Repair, Alteration and Reconstruction,
November 2014.
vice. For acid-transfer lines, the pipeline
4. McKetta, J.J., “Encyclopedia of Chemical Processing and
should be of one piping class higher than Design,” CRC Press, June 1995.
required to mitigate the risk of accidental 5. American Petroleum Institute, API 2000 — Venting At-
rupture or overpressurization. mospheric and Low-Pressure Storage Tanks, 7th Ed.,
The materials of construction for pip- March 2014.
ing are dependent on fluid-flow velocities 6. American Petroleum Institute, API RP 2009 — Safe Weld-
ing, Cutting and Hot Work Practices in the Petroleum and
and quality concerns. If iron contamina- Petrochemical Industries, February 2002.
tion is a concern for the process, as in 7. American Petroleum Institute, API 570 — Piping Inspec-
the manufacture of caprolactam, carbon tion Code, November 2009.
steel is to be avoided. Polyvinyl chloride 8. NorFalco LLC, Sulfuric Acid Handbook, www.
(PVC) and chlorinated PVC are only to myh2so4.norfalco.com/documents/NorFalco_
H2SO4TechBrochure.pdf, 2007.
be used for vent lines and overflow lines.
9. DuPont Clean Technologies, Equipment Related Frequently
These pipes should not be used for liquid Asked Questions, www2.dupont.com/Clean_Technolo-
service. Table 2 provides some criteria for gies/es_MX/assets/downloads/Equipment_FAQs.pdf.
piping materials of construction based on
velocity and temperature requirements. Author
In general, piping should be inspected Koya Venkata Reddy is senior man-
visually every year. Ultrasonic thickness ager, process engineering at FACT En-
gineering & Design Organization
tests should occur biennially. Depend- (FEDO), a division of Fertilizers And
ing on the actual plant experience, an Chemicals Travancore Ltd. (FACT;
increase or decrease in the schedule of Udyogamandal 683501, Kochi,
Kerala, India; Phone: 91-484-2568763
inspection may be required. Extra at- Email: koyareddy@yahoo.com). He has
tention should be paid to elbows, tees, 24 years of experience in chemical
plant operations, including expertise in
valves and any other areas in the piping the fields of process control, process design, process risk
where flow disturbances (and erosion or analysis, HAZOP, process simulations, environmental man-
corrosion) could occur. Piping inspec- agement and plant revamps. He is a recipient of FACT’s Merit
Award. Reddy holds a Bachelor of Technology degree from
tion criteria from API 570 may be used Andhra University, Visakhapatnam and a Master of Technol-
for guidance [7]. ogy degree in project management from Cochin University of
A hose lined with polytetrafluoroeth- Science and Technology. He also received an M.B.A. in fi-
nance from Indira Gandhi National Open University (IGNOU),
ylene (PTFE) is acceptable for 93–98% Delhi. He is a lifetime member of the Indian Institute of Chem-
sulfuric acid service. The hose should ical Engineers (IIChE) and a member of the Institution
of Engineers (India).
CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2015 49