HIRA – Assignment 2

NAVEEN PRAKASH NEELAKANTAN

500080594

Enumerate all possible ways in which chemical process safety may be compromised due to
chemical reactivity of materials being handled at CPP.

1. Thermal decomposition of raw materials, intermediates, products and by-products.

2. Exothermic runaway reaction leading to fire and explosion.
3. Side reactions.
4. Incorrect order of addition.
5. Use of expired materials/reactants for the reaction process.
6. Due to loss of purity of the catalyst used.
7. Misloading of reactants.
8. Lack of knowledge about the reaction.
9. Improper handling of the reactants and materials.
10. Inadequate operational procedures, including proper training.
11. Inadequate design for heat and pressure removal.
12. Inadequate control systems and emergency relief systems.
13. Improper safety auditing.
14. Improper maintenance of the equipment.
15. Management of change.
16. Improper Hazard Identification and Evaluation.
17. Accumulation of products and by-products resulting in corrosion of the equipment.
18. Self-heating of powdery solids when exposed in air.

Highlight the importance of chemical reaction hazard in light of past accidents.

CHEMICAL REACTION IN CONTACT WITH AIR:

At about 8:30 a.m. on October 3, 1982, a fire occurred at a VLSI manufacturing plant at Kiyotake-cho,
Miyazaki Prefecture, burning the ceiling of a partly two-story ferro-concrete building. Two
employees were seriously injured, two lightly injured, and one fireman was overcome by toxic gas.
The cause was thought to have been the spontaneous ignition of silane (SiH4) leaking into the air.

Because of this accident, the importance for –

• classes on the safety of semiconductor gases are now held frequently

• guidelines for the safe handling of semiconductor gases have been established.

CHEMICAL REACTION IN REACTOR:

1. An accident (August, 1970) which occurred during the process of coproducing m-benzenesulfonic
acid and toluene sulfonic acid by the simultaneous sulfonation of benzene and toluene in the same
reactor. One person was killed and 6 wounded.

At the final step of the reaction, when toluene at 110 o C was charged into the reactor, the stirrer
stopped. After the repair of the stirrer, stirring was resumed, but the vapor blew out and an
explosion occurred.
Although sulfonation has been thought to be of a lower exothermic potential than nitration, it has
given rise to many unexpected accidents from a variety of causes: the reaction sometimes does not
start smoothly; sulfonic acid at high temperature decomposes with a considerable heat generation;
and the flammable mist blown off can catch fire.

2. In 1948, a fire took place in a nitrocellulose warehouse in France. For a period of sixteen years
after this accident, production of nitrocellulose was prohibited in Great Britain and France. In the
U.S.A. and the U.S.S.R. it was also temporarily prohibited.

Nitrocellulose is dangerous because of its properties: liability to spontaneous ignition; and, when
dry, liability to ignition by spark, impact, or friction, to electrostatic charging, and to heat
accumulation leading to ignition followed by very quick burning. This accident was caused by ignition
due to impact or friction during production.

To prevent such accidents, an improved purification method to produce stable nitrocellulose (Abel,
Great Britain, 1869) and methods of handling nitrocellulose wet with water or alcohol have been
developed; wetting with about 20% of water or alcohol reduces the flammability of nitrocellulose
and makes its burning much milder.

SELF-IGNITION WHILE HANDLING:

At about 6:05 p.m. on May 14, 1980, at a chemical plant in Saitama Prefecture, an explosion making
a huge roaring sound occurred which killed two persons, injured 13, and damaged the glass plates in
the windows of 390 houses in the surrounding area. The explosion was caused during the handling
of the chemical 5-CT(5-Chloro-l,2,3-thiadiazole).

It was found that 5-CT readily ignites in a container with percussion or friction, readily explodes once
ignited, and drastically explodes upon being heated by the surroundings, having an explosive power
of about 80% of the high-performance explosive TNT.

RUNAWAY REACTION:

At about 0:40 p.m. on July 10, 1976, at a chemical plant in northern Italy, a safety plate of a reactor
fractured, blowing the leaking substance into the sky as a white cloud. The cloud was carried on the
wind toward the town of Seveso and was conveyed to the ground there by falling rain. The
substance leaked contained the highly toxic material dioxin, which was formed by the runaway
reaction.

Several days after this happened, cows, pigs, and other farm animals, bleeding at the nose, died one
by one. Then people, as many as 220,000, complained of exanthema, contact dermatitis, and
nausea. This highly toxic substance, dioxin, is an especially difficult problem because it is not
produced during a normal reaction but only during an abnormal reaction.

Importance of information on the –

• Management system and the organisation

• Information on the Plant and the Site
• Information on the technological and process aspects
• Identification and accidental risk analysis and prevention methods
• Information on measures for protection and mitigation.
What are the ways and means available for gauging and minimizing the extent of threat posed by
chemical reaction hazard?

1. Know the heat of reaction for the intended and other potential chemical reaction.
To identify all potential reactions that could occur in the reaction mixture and
understand the heat of reaction of those reactions. This can be done by using calorimeters,
from existing energy balance, through the supplier of the reactants, etc.

2. Calculate the maximum adiabatic temperature rise for the reaction mixture.
This is calculated by assuming there is no heat removal and that the reactant’s
reaction is 100%. If the maximum adiabatic temperature exceeds the reaction boiling point
the reaction is capable of generating pressure is a closed vessel. So proper control measures
had to be taken by installing relief valve systems.

3. Determine the stability of all individual components of the reaction mixture at the maximum
adiabatic reaction temperature.
This is done to identify if any of the individual components of the reaction mixture
can decompose at theoretical temperatures. If any of the components decompose at the
maximum adiabatic temperature, you will have to understand the nature of decomposition
and proper control measures had be taken such as pressure relief systems.

4. Determine the heat addition and heat removal capabilities of the reactor.
This is done to understand the impact of variation in conditions on heat transfer
capability. The factors such as reactor fill level, agitation, fouling of internal and external
heat transfer surfaces, etc. are taken into consideration.

5. Identification of the potential reaction contamination.

This is done to consider the possible contaminants which are present everywhere in
a plant environment, such as air, water, rust, oil and grease. Also, catalytic effects of trace
metal ions such as sodium, calcium, and others commonly present in process water are
taken into consideration.

6. Identification of the heat source connected to the reaction vessel and determining the
maximum temperature limits.
In this case if the maximum temperature is higher than the maximum adiabatic
reaction temperature, review the stability and reactivity information with respect to the
maximum temperature to which the reactor contents could be heated by the vessel heat
sources.

7. Know the minimum temperature at which the reactors mixture starts getting cooled.
This is done to so as to ensure the cooling effect of the reactor. The point at which
the cooling of mixture inside the reactor vessel is identified so as to calculate the cooling
time of any reaction and to ensure the safety of the reaction in the reactor in such a way
that it does not exceed the maximum adiabatic temperature.

8. For the plant scale reactor vessel consider the temperature in higher gradient compared to
pilot plant reactor, as the heat of reaction may be higher because of various factors like heat
of bulk reaction, agitators heat, external heat, etc.
9. Understand the rate of all chemical reactions in the reactor.
This is done to understand how fast the reactants are consumed and generally how
the rate of reaction increases with temperature. This can be tested by Thermal Hazard
Calorimetry Testing.

10. To consider the possible vapour-phase reactions. These might include combustion reactions,
other vapor phase reactions such as the reaction of organic vapours with chlorine
atmosphere, and vapor phase decomposition of materials such as ethylene oxide or organic
peroxide.

11. Understanding the hazards that the reaction could pose due to intended and unintended
reactions.
This is done to ensure that if there is any possibility of intended reaction or any unintended
reaction to form any corrosive products, toxic gases, viscous materials or any such materials
which will affect the pipe linings, reactor vessel or any equipment. So if any of these are
found, determine what is it is, how it is formed and what are the impacts that it may have on
the system.

12. It’s better to do a reactivity chemistry hazard analysis.