Phenyl formaldehyde resinsdisaster (case study)

By Sonali Chavan Harshavardhan Chaudhari Saurabh Das Rohit Deora

Phenyl formaldehyde resins

The reaction of phenol or substituted phenol with an aldehyde, in the presence of an acidic or basic catalyst is used to prepare phenolic resins. Uses: Phenolic resins are used in adhesives, coatings, and molding compounds.
OH NaOH OH (CH2OH)n1

(n1+n2) HCHO (CH2OH)n2

Heat of reaction: -180 cal/g Two step process: 1. Methylolation 2. Salification

Process description
Reaction in stirred vessel with condensor. Provision for heating and cooling. T=60oC, 37% wt. aq. formaldehyde + caustic soda, Phenol in molten state. Stoichiometric amount of Caustic soda (30% wt. solution) addition over 30 mins at 50oC. Emergency relief on the reactor is usually provided by rupture disks.

 Type of catalyst used, the ratio of reactants, and the reaction conditions determine the molecular structure and physical properties. Highly exothermic and sensitive to a variety of physical and chemical conditions. Heat generated by the reaction increases the reaction rate generating more heat. Reaction rate is typically an exponential function of temperature Pressure of the system will increase suddenly due to the vigorous evaporation of liquid. Internal Pressure > Ultimate tensile strength Thermal runaway !!!

Phenol-Formaldehyde Reaction Incidents at Various Companies

Date
Sep 10, 1997

State
OH

Description
A 8,000 gallon reactor exploded during production of a phenol-formaldehyde resin.

Effect
1 worker fatality, 4 employees injured, 3 firefighters treated for chemical burns. Evacuation of residents for several hours.
Residents evacuated for 5 hours.

Aug 18, 1994

OH

Pressure buildup during manufacture of phenolic resin, pressure increased, rupture disks popped. Product was released through emergency vent. The cause of accident was reported as failure to open condensate return line. A 13,000 gallon reactor exploded during production of a phenol-formaldehyde resin. Explosion occurred during initial stages of catalyst addition. Temperature increased in chemical reactor, releasing phenol formaldehyde resin. Manufacture of phenolic resins and thermoset plastics; release of phenol and formaldehyde from process vessel. Manufacture of phenolic resins; release of phenol and phenolic resin from process vessel; operator error cited as cause. Specialty paper manufacturing; release of phenolic resin and methanol from process vessel.

Feb 29, 1992

GA

4 employees injured, 1 seriously. 1 firefighter treated for chemical burns. Evacuation of 200 residents for 3 hours. None reported. None reported. 1 injured.

Nov 11, 1991 Oct 16, 1989 Aug 28, 1989

OH WI NY

Jul 25, 1989

VA

None reported.

Case study
On September 10, 1997 the Georgia- Pacific Resins plant in Columbus experienced a large explosion in a resin kettle (reactor). 8,000-gallon batch reactor The explosion resulted from a runaway reaction in Kettle No. 2. The reactors safety systems failed to contain the rapidly expanding gases

What happened?
An operator charged raw materials and catalyst to the reactor and turned on steam to heat

the contents.
A high temperature alarm sounded and the operator turned off the steam. There was a large, highly energetic explosion. Separation of the top of the reactor from the shell.

A nearby holding tank was destroyed and another reactor was partially damaged.
Operator killed, 4 injured, 3 firemen burned severely. Occupational Safety and Health Administration slapped the company with $400000 fine. Residents within a mile radius of the facility were evacuated. People complaining of burning of skin, rashes, sore throat, headaches, breathing problems due to bronchitis, burning of throat, and nausea.

Cause
All the raw materials and catalyst were charged to the reactor at once followed by the addition of heat. Heat generated exceeded the cooling capacity of the system Excessive pressure generated by a runaway reaction. Pressure generated could not be vented through the emergency relief system.

Runaway due to
Accumulation of Formaldehyde Deviation from process Poor agitation Improper heating or cooling

Lessons learned
Thorough hazard assesment Complete identification of reaction chemistry and thermochemistry Administrative controls Temperature control Addition of raw materials Emergency relief Learning from accident history and near misses

Steps To Reduce Hazards

Modify processes to improve inherent safety. Minimize the potential for human error. Understand events that may lead to an overpressure and eventually to vessel rupture. Use lessons learned. Evaluate Standard Operating Practices. Evaluate employee training and oversight. Evaluate the effectiveness of the emergency relief system.

Social Impact
Concerns regarding future accidents: Fear that the GPRI plant will experience another serious accident The railroad and other plants in the area could also have a chemical accident Concern that residents wouldnt even know if an accident takes place (no alarm) Residents have no information on what to do in the event of an accident (evacuation?) Concern that a warning will come too late Concerns about children at school or children being caught in a vapor cloud Concern for elderly and sick people who may not hear or respond to a warning When we see fire trucks or hear a loud noise, we dont know what is going on

Social Impact
Concerns regarding air emissions and odors Reports of chemical smells and/or burning eyes Experiences with odors, burning eyes, and visual plumes from the plant Concern about formaldehyde emissions from Georgia Pacific Plant Awareness that formaldehyde is highly toxic General concern that air in the area is not healthy Awareness of other emission sources in area (including large numbers of trucks) Concern that high rates of asthma and other illness that may be attributable to air emissions Concern that Ohio EPA doesnt do enough to reduce air pollution in the area