R.V.

COLLEGE OF ENGINEERING, BANGALORE-560059

(Autonomous Institution Affiliated to VTU, Belgaum)

Department of Chemical Engineering

STORAGE OF SULPHURIC ACID WHILE TRANSPORTATION

SELF STUDY REPORT

SUBMITTED BY: SUBMITTED TO:

Himanshu Sahni Dr. Basavaraja R J
1RV16ME141 (Associate Professor)
INTRODUCTION

Sulfuric acid is a highly corrosive mineral acid that challenges traditional storage options. This pungent,
colorless to slightly yellow viscous liquid is dyed dark brown during production to alert people to its hazards.
The biggest challenge in working with sulfuric acid is that it is an aggressive oxidizer. This challenges the
strength and design of many storage tanks. Poly Processing’s tanks and fittings can be combined specifically to
store sulfuric acid and reduce the risks.

Manufacturing Process

 Lead chamber process

 Contact process

Contact Process

The contact process has three major steps:

 Step – I: Production of Sulphur Dioxide

S (Sulphur)   +   O2 (Oxygen)   +   Δ (Heating)    →    SO2 (Sulphur dioxide)

4FeS (Iron pyrites)   +   7O2 (Oxygen)   +   Δ (heating)    →    2Fe2O3 (Ferric
Oxide) + 4SO2 (Sulphur dioxide)

 Step -II: Formation of Sulphur Trioxide

2SO2 (Sulphur dioxide)   +   O2 (Oxygen)   +   V2O5 (Catalyst)   →    SO3 (Sulphur trioxide)

 Step -III: Conversion of Sulphur Trioxide into Sulphuric Acid

SO3 (Sulphur trioxide)   + H2SO4 (Sulphuric acid-98%)    →    H2S2O7 (Pyrosulphuric acid/Oleum)
 H2S2O7 (Pyrosulphuric acid/Oleum)    + H2O (Dilution)    →     2H2SO4 (Sulphuric acid)

Lead Chamber Process

Lead Chamber process is one of the most common manufacturing strategies that results in around
50-60 B grade acids.

2SO2   +   O2    →   2SO3

SO3   +   H2O   →    H2SO4

Physical Properties 

 Sulphuric acid is a thick, colorless and an oily fluid.

 It has a specific gravity of 1.84 at 298 K.

 The boiling point of the acid is 611 K. It attributes its higher boiling point and thickness to
hydrogen bonding.

 The strong acid reacts with water vigorously releasing quite a lot of heat. Therefore, you
must never add water to sulphuric acid. Instead, you should add the acid to water, slowly
with proper stirring.

Chemical Properties 

 Sulphuric acid is a strong dibasic acid. It is diprotic and ionizes in two stages in the
aqueous solution.

 It is highly corrosive and reactive and is soluble in water. Sulphuric acid has a very high
oxidizing power and thus, acts as a strong oxidizing agent. It has very low volatility.

 We use this acid as a part of the preparation of more volatile acids from their comparing
salts because of its low volatility.

 Concentrated sulphuric acid is a very strong dehydrating agent. This property is utilized as
a part of drying many wet gases which do not react with the acid.

 It additionally expels water from natural mixes like starches.

 As it is a good oxidizing agent, it can oxidize both non-metals as well as metals. It itself
reduces to Sulphur dioxide.
HEALTH HAZARDS:

Acute Effects

A. Ingestion -
Mucosal as well as severe esophageal corrosive injury. Chemical burns of the mouth,
pharynx and stomach can develop. Injury may be severe and cause death.

First Aid - Do not induce vomiting. Dilute the acid immediately by drinking large quantities of
water or milk.

B. Inhalation - Severe pulmonary edema and pneumonitis can result from inhalation of
Sulphuric acid. Pre-existing lung disease may be aggravated by exposure. Ulcerations of nose,
throat and larynx.

First Aid - Remove from exposure area to fresh air immediately. If breathing has stopped, give
artificial respiration.

C. Dermal - Ulcerations of skin. Sulphuric acid will probably not be absorbed through skin.

First Aid - Remove contaminated clothing and shoes immediately. Wash affected area with soap
or mild detergent and large amounts of water until no evidence of
the chemical remains.

D. Eyes - Sulphuric acid induces chemical burns on contact with human eyes that can lead to
irreversible corneal damage.

First Aid - Wash eyes immediately with large amounts of water, until no evidence of the
chemical remains (at least 15-20 mins).

Chronic Effects

A. Carcinogenicity - none reported.

B. Mutagenicity - none reported.

C. Toxicity - Prolonged or repeated exposure may result in respiratory impairment and

bronchitis. Mucosal membranes severely damaged following repeated exposures.
 HOW TO CHOOSE THE BEST STORAGE TANK FOR SULFURIC ACID  
The highly corrosive nature of sulfuric acid tests the limits of today’s storage systems. There are
three considerations when choosing an ideal storage tank—the acid’s corrosiveness, molecular
weight, and the concentration being used. 

 Corrosiveness. Because it is an aggressive oxidizer, safeguards are required to prevent

polyethylene tanks from becoming brittle and cracking, which could result in leaks or failure of
the storage tank. 
 Molecular Weight. With a molecular weight of 98.079 g/mol, sulfuric acid is an
extremely heavy chemical that will test the mechanical integrity of any material. 
 Concentration. This acid displays different properties depending upon the concentration
being used. It’s used in three main concentrations, based on the end-use application, those are
93-98%, 80 to 92%, and 80%.

STORAGE TANK RECOMMENDATIONS FOR SULFURIC ACID

Through a combination of innovative features, Poly Processing overcomes the storage challenges of sulfuric
acid with an ideal storage system that contains these features: 

 Antioxidant System. When storing sulfuric acid, it’s important to verify the hoop stress rating and
understand the specific gravity ratings to make sure the resins used in the storage tank provide a margin of
safety. Poly Processing’s next generation OR-1000™ system bonds the XLPE with an antioxidant inner
surface, minimizing oxidation, reducing the potential for fault and maximizing life span. 
 Cross-linked polyethylene tanks. With their robust load tolerance, cross-linked polyethylene tanks
can handle the chemical’s heavy weight. Also, the Specific Gravity Rating of 2.2 spg. keeps the tank rigid and
gives the end user a built in safety factor. 
 High-density cross-linked polyethylene (XLPE). The XLPE molecular bonding and thick tank wall
are particularly important in the bottom third of the tank, where high levels of load are concentrated. 

HANDLING OF SULPHURIC ACID

WARNING/CAUTION

Sulphuric acid is a strong corrosive and care should be taken to prevent contact with metals,
amines, and alkalis which could cause the release of sulphuric dioxide gas and toxic or corrosive
fumes.
EXPOSURE LIMITS

The airborne permissible exposure limit (PEL) for Sulphuric acid is 5 ppm in a 8 hour work day.
A concentration of 100 ppm is considered to be immediately dangerous to life or health (IDLH).

FIELD HANDLING AND USE

Because of the potential to release toxic vapors, Sulphuric acid should never be opened, mixed,
or transferred to other containers at any time while inside a vehicle or in any other small
enclosure without a mechanism to vent all fumes to the outside. A Materials Safety Data Sheet
(MSDS) should be in the possession of the user at all times and made available to those working
with this chemical. The MSDS for Sulphuric acid is to be in the laboratory and field files
containing all pertinent MSDS. The MSDS files should be clearly labeled and readily accessible
to all personnel.

TRANSPORTATION

Sulphuric acid should never be transported in other than a plastic coated glass container,
accurately labeled, and properly stored within the vehicle to prevent shifting, spillage, or
breakage. Containers of Sulphuric acid carried in vehicles in warm climates should be placed in
coolers to protect them from excessive heat. Although Sulphuric acid has a boiling point of 110
degrees C (230 degrees F) it should be transported at room temperature to minimize a buildup of
gas pressure in the container.

CONTINGENCY SPILLS AND RESPONSE

During operational use, transportation, and wherever an accidental spill is likely to occur, each
laboratory and field unit should have, as part of their required emergency equipment, sufficient
absorbent materials, such as sodium bicarbonate, soda ash or lime, to handle small spills. Do not
allow run-off to contaminate water supplies or nearby creeks or rivers. Do not attempt cleanup
unless wearing skin, eye, and respiratory protection. Since Sulphuric acid has a pH less than 1,
discarded material is a hazardous waste (Environmental Protection Agency (EPA) Hazardous
Waste No. D002,
40 CFR 261.22) including empty Sulphuric acid containers. Waste material should be stored in a
safe area and clearly marked for special disposal by a recycling contractor. Record how much of
the chemical was spilled and the method of clean up and proper disposal, as required by
hazardous waste regulations.
PERSONAL PROTECTIVE EQUIPMENT:

Because Sulphuric acid is a strong corrosive, an acid-resistant apron, gloves, and face shield or
protective eyewear should be worn at all times while pouring, mixing, or transferring this
chemical. Handling of Sulphuric acid must be in a well-ventilated area or under a fume hood for
approved acids.

STORAGE:

Sulphuric acid should be kept in a tightly closed container and stored in chemical area that is
compatible with other chemicals. Store in a secure, well-ventilated area, that is well marked, and
away from the general work population. Do not store near oxidizing
materials.

DISPOSAL:

Spilled or used Sulphuric acid is considered a hazardous waste and must be handled accordingly.
It must be properly labeled and disposed of by a hazardous waste contractor. Storage should be
in an assigned area that is away from general worker population, and well-marked, well
ventilated and not subject to heat cycles.
By diluting Sulphuric acid to 5 percent volume to volume or less, and neutralizing it with
NAHCO3 to a neutral pH, the solution is no longer corrosive and can, in some jurisdictions, be
disposed of down the drain.

PRELOADING PRECAUTIONS & LOADING SULFURIC ACID

 IBC code compatibility chart strictly prohibits water in adjacent compartment to

Sulphuric acid as you are aware if both come in contact with each other will generate a
violent reaction. It is therefore recommended that the during loading of sulphuric acid
adjacent ballast tanks to be always stripped dry to the maximum efficiency of the
ballasting equipment used.
 Sulphuric Acid is normally carried in stainless steel tanks with a minimum concentration
of 90% and at temperatures not exceeding 35C.
 Highly concentrated, sulphuric acid may be carried in mild steel tanks, but only after
obtaining special permits from the class.
 It is highly recommended that Chemical suits to be worn by all the deck hands involved
in the cargo handling.

PREPARATIONS FOR LOADING

  The tank must be cleaned to "Visual Water White Standard" and free of any residues
from previous cargoes, chlorides and any other foreign matters.
 A thorough inspection of the tank's lower areas and tank top must be carried out, with
special emphasis on steel defect detection. Any suspected areas, and welding seams, must
be "dye- checked" for cracks.
 Heating coils to be pressure-tested for leaks, blown empty and dried with nitrogen. The
tank must be dry before loading is permitted.
 The surrounding cofferdams and double bottoms must be empty and dry.

DISCHARGING SULFURIC ACID

Because of the high specific gravity of Sulphuric Acid, very high pump pressure may be
experienced. In such cases care must be taken not to quickly open or close valves in the pump
system as this causes pressure surges that may rupture lines or hoses.

CLEANING AND SLOP

Sulphuric Acid in 30-70% concentrations is non-oxidizing and attacks the steel rapidly,
particularly at elevated temperatures. When concentrated Sulphuric Acid is diluted the reaction is
exothermic and the temperature of acid will rapidly increase. If the tank is cleaned with
inadequate quantities of water, the acid will become hot, as it is diluted, and rapid attack will
occur on the stainless steel until sufficient water is introduced.

Large quantities (preferably fresh water) must be put into the tank to rapidly pass the dangerous
concentration range and heat increase. Preferably if stainless steel hoses were used on the
manifold for discharge should be replaced with non-stainless steel acid resistant hose(s) before
the cleaning operation starts.

CLEANING PROCESS

 Preferably, fresh water should be used as cleaning medium but if not available large
amounts of sea water must be used/added to the tank. Cleaning must start as soon as
possible after discharge, but do not commence cleaning unless slop disposal is available,
either to shore or as per Marpol regulations.
 Sulphuric Acid slops should normally not be kept on board as diluted acid slops are very
aggressive to all metals. In cases where acid slops must be retained on board, consult the
Ship Operator for advice.
 Cleaning with water (adding water to acid) will generate much heat with release of
Hydrogen gas.
 Cleaning must be started with as much water as possible introduced into the tank from
the beginning.
  Continuously drain the tank, do not allow acid/water mixture to collect in the tank. Do
not stop cleaning before a litmus paper check of the drain water reads neutral. 6. If
seawater was used, the tank must be immediately desalted with freshwater or di-water.
 Ensure that the line systems, including the vent system, are cleaned out and free of any
acid remains.
 Flush out the heating coils with freshwater and check for acidity using litmus paper.

CONCLUSION

Proper tank design is crucial to successful and safe sulfuric acid storage. There are many many storage
solutions out there which is why it is vital to choose the proper tank configuration. Selecting the right tank
configuration can impact the safety of your employees, the protection of your environment, and the cost of
protecting your investment.

Many people think that if a tank can store water, it can store a chemical. Although a water tank could
potentially store a chemical for a limited amount of time, its design falls short of preventing leaks and other
dangerous situations.

Don’t rely on a water tank to do the job of a tank designed for sulfuric acid storage. This is unwise and could
cost irreparable damage to business. Instead, work with tank experts that can help choose or design the right
solution for the business.