SAFETY IN CHEMICAL ENGINEERING

GROUP MEMBERS ARUN C S C SRINESH ROHITH KRISHNAN

CONTENTS
Introduction Run away reactions in Engineering Causes of run away reactions Risk assessment Evaluating reaction hazards Major incidents- Seveso and Chernobyl Effects Prevention

INTRODUCTION
Thermal runaway refers to a situation where an increase in temperature changes the conditions in a way that causes a further increase in temperature, often leading to a destructive result In the chemical process industry, raw materials are converted into commercial products. Exothermic chemical reactions can lead to a thermal runaway if the heat generation rate exceeds the heat removal rate. The runaway itself is characterised by an exponential increase in the rate of heat generation, temperature and pressure.

Pressure build-up during the runaway is caused by an increasing vapour pressure of liquid components and by the production of noncondensable gases. Apart from the loss of reactor inventory due to an uncontrolled conversion process, a runaway reaction may lead to severely damaged equipment or even a physical explosion if pressure build-up inside the reactor exceeds the design pressure.

RUNAWAY REACTIONS IN ENGINEERING

In chemistry (and chemical engineering), this risk is associated with strongly exothermic reactions that are accelerated by temperature rise. In electrical engineering, thermal runaway is typically associated with increased current flow and power dissipation, although exothermic chemical reactions can also occur under some conditions. Thermal runaway can occur in civil engineering, notably when the heat released by large amounts of curing concrete is not controlled. In the science of astrophysics, thermal runaway of thermonuclear fusion in the cores of massive stars can cause Type I supernova explosions.

CAUSES OF RUNAWAY REACTIONS

Most possible occurrence of a runaway reaction: During a cooling problem like choking of condenser used for cooling Failure of cooling water due to electrical or mechanical failure of pumps, Inadequate cooling water pressure or high cooling water temperature

An analysis of thermal runaways in the UK has indicated that incidents occur because of: Inadequate understanding of the process chemistry and thermochemistry; Inadequate design for heat removal; Inadequate control systems and safety systems Inadequate operational procedures, including training.

Runaway reactions can also prevail from less evident matters Occurrence of hot spots in a chemical reactor or reactor wall Failure of a stirrer Accumulation of reactants Loss of solvent in reflux systems, fire etc, An intentional chemical conversion process, selfheating Failure of valves which can be used for addition of reactants at the required flow rate or discharge of hot materials.

CHEMICAL PROCESS RISK ASSESSMENT

A typical assessment will involve: Defining the process, operating conditions and plant Identifying the hazards Evaluating the risks arising from the hazards and deciding whether existing precautions are adequate or more should be done Selecting and specifying appropriate safety measures Implementing and maintaining the selected safety measures.

The assessment should be sufficient to identify the potential hazards and to investigate their causes. Where possible, hazards should be avoided. As the process design develops, foreseeable deviations from the normal process, such as equipment failure or operator error, should be considered. You may need to follow a structured method for identifying hazards, such as a hazard and operability study (HAZOP), particularly when the plant or processes are highly hazardous, complex or involve new technology.

EVALUATING REACTION HAZARDS

In order to determine the hazards of a reaction, you need information on the chemistry and thermochemistry of the reaction. This includes: The possibility of thermal decomposition of raw materials, intermediates, products and by-products; Whether exothermic runaway can occur The rate and quantity of heat and gas produced by the reaction. As it is not safe to test unknown reactions in a full-size reactor, various techniques and tests have been developed to provide predictive data.

The main methods are: Literature data and calculation, to give preliminary information; Basic screening tests, such as differential scanning calorimetry or carius tube; Isothermal calorimetry (mainly to measure reaction kinetics and heats of reaction); Adiabatic calorimetry (mainly to examine runaways); and Relief vent sizing tests.

MAJOR INCIDENTS
1947 Texas City disaster from overheated ammonium nitrate in a ship's hold Disastrous release of a large volume of methyl isocyanate gas from a Union Carbide plant in Bhopal India in 1984 Seveso disaster-where thermal runaway heated a reaction to temperatures such that in addition to the intended 2,4,5-trichlorophenol, poisonous 2,3,7,8-tetrachlorodibenzo-p-dioxin was also produced, and was vented into the environment after the reactor's rupture disk burst

CHERNOBYL DISASTER

The Chernobyl disaster was a nuclear accident that occurred on 26 April 1986 at the Chernobyl Nuclear Power Plant in Ukraine. It is considered the worst nuclear power plant accident in history, and is one of only two classified as a level 7 event on the International Nuclear Event Scale

Even when not actively generating power, nuclear power reactors require cooling, typically provided by coolant flow, to remove decay heat. Pressurized water reactors use water flow at high pressure to remove waste heat. After an emergency shutdown, the core still generates a significant amount of residual heat There had been concerns that in the event of a power grid failure, external power would not have been immediately available to run the plant's cooling water pumps.

Chernobyl's reactors had three backup diesel generators but there will be power gap and this was unacceptable, and it had been suggested that the rotational energy of the steam turbine and residual steam pressure could be used to generate electricity

The test focused on the switching sequences of the electrical supplies for the reactor. The test procedure was to begin with an automatic emergency shutdown. No detrimental effect on the safety of the reactor was anticipated, so the test program was not formally coordinated with either the chief designer of the reactor or the scientific manager. Instead, it was approved only by the director of the plant (and even this approval was not consistent with established procedures). According to the test parameters, the thermal output of the reactor should have been no lower than 700 MW at the start of the experiment. If test conditions had been as planned, the procedure would almost certainly have been carried out safely; the eventual disaster resulted from attempts to boost the reactor output once the experiment had been started, which was inconsistent with approved procedure.

As the experiment began, the four pumps were active. The steam to the turbines was shut off, and a run down of the turbine generator began. As the momentum of the turbine generator decreased, the water flow rate decreased, leading to increased formation of steam voids (bubbles) in the core which reduced the ability of coolant to absorb heat. As the temperature went up the power output of the reactor also increased Control rods were used to control the rate of reaction.

A bigger problem was a flawed graphite-tip control rod design, which initially displaced coolant before inserting neutron-absorbing material to slow the reaction. As a result, the control rods actually increased the reaction rate in the lower half of the core. A few seconds after the start of the insertion of control rods, the core overheated, and seconds later this overheating resulted in the initial explosion

NEW SAFETY LAWS AFTER CHERNOBYL

Permission of technical experts were made mandatory before any test run. All reactors should undergo power failure test and other possible test before being used in a plant. More responsibility were given to technical experts during test run. Safety symbols were made mandatory.

SEVESO DISASTER

The Seveso disaster was an industrial accident that occurred around 12:37 pm July 10, 1976, in a small chemical manufacturing plant approximately 15 km (9.3 mi) north of Milan in the Lombardy region in Italy

The chemical 2,4,5-trichlorophenol was being produced there from 1,2,4,5-tetrachlorobenzene by the nucleophilic aromatic substitution reaction with sodium hydroxide. The 2,4,5-trichlorophenol was intended as an intermediate for hexachlorophene.

This reaction must be carried at a temperature above that of the normal process utilities that were available, so it was decided to utilize the exhaust steam from the electricity turbine on site, and pass that around an external heating coil on the reactor. This exhaust steam was at 12 bar and 190C, resulting in a reaction mixture at 158C (with a boiling point of 160C). Safety testing showed onset of an exothermic side reaction at 230C

On this occasion the batch process was interrupted prior to finishing the final step of removal of ethylene glycol by distillation, due to an Italian law requiring shutdown of plant operations over the weekend. Other parts of the site started to close down as batches finished, and no more were started. This caused the load on the turbine to fall dramatically, resulting in the exhaust steam temperature rising to around 300C, heating the reactor wall above the level of the liquid to the same temperature.

This batch was then stopped by isolating the steam, and turning off the stirrer. The residual heat in the jacket then heated the upper layer of the mixture next to the wall to the critical temperature (which was actually only 180C, 50C lower than believed), starting a slow runaway decomposition, and after seven hours a rapid runaway reaction ensued when the temperature reached 230C

The relief valve eventually opened and 6 tonnes of material were distributed over an 18 km2 area, including 1 kg of 2,3,7,8tetrachlorodibenzodioxin which is normally seen only in trace amounts of less than 1 ppm (parts per million). However, in the higher-temperature conditions associated with the runaway reaction, TCDD production apparently reached 100 ppm or more

EFFECTS
Emergency slaughtering commenced to prevent TCDD from entering the food chain 1600 people of all ages were found to suffer from skin diseases An excess mortality from cardiovascular and respiratory diseases was uncovered,

EFFECTS OF THERMAL RUNAWAY

A runaway exothermic reaction can have a range of results from the boiling over of the reaction mass, to large increases in temperature and pressure that lead to an explosion. If flammable materials are released, fire or a secondary explosion may result. Hot liquors and toxic materials may contaminate the workplace or generate a toxic cloud that may spread off-site. There can be serious risk of injuries, even death, to plant operators, and the general public and the local environment may be harmed At best, a runaway causes loss and disruption of production, at worst it has the potential for a major accident, as the incidents at Seveso and Bhopal have shown.

PREVENTION, INTERVENTION AND EFFECT REDUCTION

The prevention of runaway reactions with advice on issues such as: Safe operation conditions, process monitoring or intrinsically safer design. In those cases where runaway hazards cannot be eliminated, applicability of intervention techniques such as inhibitor or coolant injection can be investigated or requirements for effect reduction (usually vent requirements for pressure relief) can be determined.

SAFETY MEASURES You can ensure safe operation in a number of ways, by using: Inherently safer methods, which eliminate or reduce the hazard; process control, which prevents a runaway reaction occurring; and

ELECTRICAL FAULTS

Pharmaceutical industry or chemical industry uses a variety of flammable solvents which can be ignited electrical fault Short circuits resulting in sparks, arcing, overheating of electrical cables light fixtures etc are some of the electrical faults that resulted in fires Inappropriate electrical fittings in hazardous areas where specialized electrical fittings like flame proof, intrinsically safe are to be used have also caused huge fires Static charges generated by the transfer of solvent through a non conducting medium have the potential to cause fires

INHERENT SAFETY

Where possible, you should first eliminate or reduce hazards by inherently safer design. For example: replace hazardous materials with safer ones:have less unreacted material in the reactor, eg using a continuous process instead of a batch reactor: use a semi-batch method (in which one of the raw materials is added over time) instead of a batch process; and/or.use a heating medium which has a maximum temperature that is too low for the reaction mixture to decompose.

PROCESS CONTROL
Process control includes the use of sensors Alarms trips and other control systems that either take automatic action or allow for manual intervention to prevent the conditions for uncontrolled reaction occurring. Specifying such measures requires a thorough understanding of the chemical process involved, especially the limits of safe operation.

PROTECTIVE MEASURES
Protective measures do not prevent a runaway but reduce the consequences should one occur. They are rarely used on their own as some preventive measures are normally required to reduce the demand upon them. As they operate once a runaway has started, a detailed knowledge of the reaction under runaway conditions is needed for their effective specification. You can: design the plant to contain the maximum pressure-fit emergency relief vents and ensure vented material goes to a safe place crash cool the reaction mixture if it moves outside set limits; add a reaction inhibitor to kill the reaction and prevent runaway; or dump the reaction into a quenching fluid.

SELECTING THE BASIS OF SAFETY

The basis of safety for a chemical reaction is the combination of measures which are relied upon to ensure safe operation. The measures you choose for a particular case will depend on a number of factors, including: how easy it is to prevent runaway; how applicable the various methods are how compatible the measures are with plant operation. In practice, you may not be able to eliminate all hazards by inherently safer methods and may choose to add control measures to further reduce risk and back these up with protection, such as a vent, to deal with the residual risk. Such a combination of methods is common. As a runaway incident may affect the environment, you should also consider whether your measures are adequate to comply with environmental law.

REFERENCES

Barton JA and Nolan PF 1989 Incidents in the chemical industry due to thermal runaway chemical reactions Hazards X: Process Safety in Fine and Speciality Chemical Plants- IChem 115: 3-18