Chemical Safety Alert Managing Chemical Reactivity Hazards (PDF) - PDF by qes74153


									                                                                        Office of Solid Waste           EPA 550-F-04-005
                                                                        and Emergency Response          February 2005

                                     MANAGING CHEMICAL REACTIVITY HAZARDS
                                     The Environmental Protection Agency (EPA) is issuing this Alert as part of its ongoing effort
                                     to protect human health and the environment. EPA is striving to learn the causes and
                                     contributing factors associated with chemical accidents and to prevent their recurrence. Major
                                     chemical accidents cannot be prevented solely through regulatory requirements, but by
                                     understanding the fundamental root causes, widely disseminating the lessons learned, and
                                     integrating these lessons learned into safe operations. EPA publishes Alerts to increase
                                     awareness of possible hazards. It is important that facilities, SERCs, LEPCs, emergency
                                     responders and others review this information and take appropriate steps to minimize risk.

                                     PROBLEM                                           chemical reactivity hazards, this alert
                                                                                       focuses on the management of the
                                               any materials used in                   hazards. This alert does not cover all

                                     M         industrial facilities can pose
                                               chemical reactivity hazards.
                                     Conventional management systems
                                                                                       ten essential management practices,
                                                                                       but highlights some common
                                                                                       management deficiencies.
                                     frequently do not adequately address
                                     the unique behavior of materials that             This alert assumes that the reader has
                                     may react to cause excessive                      determined that a chemical reactivity
                                     temperature or pressure excursions or             hazard exists at the facility and has:
                                     toxic or corrosive emissions.
                                                                                       •	 Explored opportunities, such as
                                     Incidents occur not only at chemical                 substituting inherently safer
                                     manufacturing and processing plants,                 chemicals, to reduce or eliminate
                                     but also at water treatment plants,                  reactivity hazards;
                                     swimming pools and spas, metal                    •	 Gathered available information
                                     processing facilities, and mechanical                from available sources such as
                                     equipment manufacturing facilities.                  MSDS.
                                                                                       •	 Completed preliminary screening
                                                                                          to identify chemical reactivity
                                     PURPOSE                                              hazards (see the EPA companion
                                                                                          alert Identifying Chemical
                                            he purpose of this alert is to

                                     T      introduce facilities to the
                                            methodology for chemical
                                                                                          Reactivity Hazards: Preliminary
                                                                                          Screening Method for additional

                                     reactivity hazard management as                   •	 Developed a matrix indicating
                                     developed by the Center for Chemical                 which chemicals react with each
                                     Process Safety (CCPS) and made                       other, including the process or
                                     available in a book Essential                        operating area where the chemicals
 Chemical Safety

                                     Practices for Managing Chemical                      are located;
                                     Reactivity Hazards. This alert is a               •	 Gained management commitment
                                     follow-on to the recent EPA alert                    to the safe operation of the facility;
                                     which discusses the CCPS method for               •	 Ensured resources are available to
                                     screening facilities for chemical                    ensure physical plant is designed
                                     reactivity hazards. While the first                  or modified as necessary to
                                     EPA alert focused on identifying                     mitigate chemical reactivity hazard

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   exposure;                                               likelihood of a serious process safety incident.
•	 Implemented a sound training program,
   operating procedures, and hazard                        March, 1997 - The facility provides an antimony
   communication program; and                              catalyst service. A 1000-pound horizontal
•	 Implemented an active safety audit program.             cylindrical container was in the process of having a
                                                           small sample drawn into an open container.
INCIDENT EXAMPLES                                          However, the handle of the quarter-turn valve
                                                           leading to the dip-leg had been removed by the
       number of incidents involving reactive              customer before returning the container of spent

A      chemicals have resulted in accidental
       chemical releases, fire, and explosions.
The following section describes several recent
                                                           catalyst. The employee opened the valve using a
                                                           vice-grip tool but was then unable to close the
                                                           valve. Escaping spent antimony catalyst was
                                                           believed to have reacted with moisture in the
                                                           atmosphere, to create hydrogen chloride. The
September, 2004 - A transport vessel containing a          incident investigation led to a management-of-
mixture of recovered monomer was observed to be            change review, revised sampling procedures and
relieving pressure via the pressure relief valve. The      training and a closed sampling system that
relief valve was lifting (relieving) as a result of the    discharges to a scrubber system. This incident
pressure in the vessel exceeding the relief valve          illustrates the need for particular attention to
setting. The increased pressure was caused by an           operations that involve removing material from the
increase in the temperature within the container.          enclosed system, such as when venting, draining or
This temperature increase was caused by a                  sampling.
polymerization reaction of the monomer mixture.
A water deluge was applied to cool the transport           July, 1994 - New steel saddles (internal saddle
vessel and minimize the vapor cloud dispersion.            shaped devices used to promote mixing) were
The accident investigation revealed a blockage in          installed in the direct-contact chiller vessel ahead
the injection feed line which obstructed the               of the chlorine compressor. The saddles should
addition of inhibitor into the monomer mixture.            have had no corrosion protection coating, but they
The immediate term procedure modifications were            did have an undetected coating of mineral oil.
to manually control the inhibitor injection and,           When the main stream of chlorine and the chilling
also, to verify inhibitor concentration after loading      material, which was also chlorine, entered the
the transport vessel. The longer term modification         chiller vessel, there was an intense exothermic
includes automatic inhibitor addition with post            reaction between the chlorine and the mineral oil
loading verification of inhibitor concentration.           which burned through the vessel wall, releasing
                                                           chlorine to the atmosphere. The subsequent
March, 2004 - Operations personnel were                    incident investigation, the management-of-change
preparing to unload a railcar of methyl chloride           review, and the operating procedure revision
when they discovered a product identification label        focused on verification that mechanical equipment
attached to the railcar dome reading “methylene            that may come into contact with chlorine is
chloride.” Because the label and placards were not         confirmed to be free of any material with which
in agreement, personnel quarantined the railcar            chlorine may react. This incident highlights the
until proper chemical verification could be made           need to consider not only process chemicals, but
with the supplier and the facility quality control         other chemicals and contaminants as well.
laboratory. The verification confirmed that the
railcar placarding for methyl chloride was correct.
Close attention to material identification used
triggered personnel to take steps to verify the
contends of the railcar, thereby reducing the

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MANAGEMENT OF REACTIVE                                         systems include:
HAZARDS                                                        Communicate and Train on Chemical
                                                               Reactivity Hazards
       he consequences of a reactive chemical

T      incident can be severe. In a 2002 study, the
       U.S. Chemical Safety Board (CSB) collected
detailed information on 167 serious incidents that
                                                               Training activities and materials should
                                                               incorporate the hazards of chemical reactivity and
                                                               provide information relevant to workers directing
occurred between 1980 and 2001. EPA reviewed                   and performing process operations. The following
CSB’s information and identified the most                      are some suggestions for improving
commonly reported management deficiencies. In                  communication and training about reactive hazards
order of frequency, the reported management                    within a facility:
deficiencies are:
                                                               •	 State not only the steps required to correctly
•	 Operating Procedures, Safe Operating Limits                    execute the operation, but also the
   and Training                                                   consequences of deviation. Develop likely
•	 Hazard Identification and Evaluation                           scenarios such as incorrect charging,
•	 Human Factors                                                  contamination of the process, or operating the
•	 Management of Change                                           process in the wrong range.
•	 Emergency Relief Equipment and Controls                     •	 Integrate information about chemical reactivity
•	 Process Design                                                 hazards into the operating procedures and
•	 Process Knowledge                                              instructions, rather than separately appending it
•	 Incident Investigation                                         to the instructions.
•	 Process Hazard Analysis                                     •	 Clearly state safe operating limits and the
•	 Safety Auditing                                                actions to be taken if operating deviations
•	 Equipment Maintenance                                          occur.
                                                               •	 Because concepts concerning reactivity hazards
In their Reactive Hazard Investigation report, CSB                may be unfamiliar to some operating staff, these
points to the limited availability of accurate                    concepts should be clearly and simply worded.
reactive chemical incident data. In spite of these             •	 Chemical reactivity hazards information should
limitations, we believe that this data set is useful in           be included in the facility’s material safety data
identifying areas of management systems that need                 sheet (MSDS) and, if necessary, described in
to be strengthened in order to address the hazards                detail in instructions accompanying the MSDS.
of reactive chemicals.                                         •	 Share training materials with all operating
                                                                  personnel, including contractors.
To assist facilities in managing these risks, the              •	 Facility management should ensure that training
Center for Chemical Process Safety (CCPS)                         is understood by employees and contractors.
sponsored the concept book Essential Practices for
Managing Chemical Reactivity Hazards and with                  Identify Process Controls and Risk
the support of its government and industry partners            Management Options
has made this book available free of charge from
the Internet. Chapter 4 of this book discusses ten             The materials receiving and transfer system should
essential practices for managing chemical                      be designed to guard against inadvertent mixing or
reactivity hazards. This alert does not cover all ten          incorrect handling.
management practices but highlights some
common management deficiencies.                                •	 Material receipt - Is a procedure in place,
                                                                  possibly sampling, to check the material
Recommendations for strengthening management                      received to ensure that it is the correct material?

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•	 Connection points- Is the connection clearly              safety, health and environmental protection should
   marked and/or color coded to guard against                be freely exchanged between organizations within
   delivering to the wrong point? Incompatible               industry and by technical societies.
   couplings may also have an application.
•	 Have piping manifolds, including sampling                 •	 Does the facility management have at least one
   lines, blow-down and venting or flaring systems              person designated to explore available
   been checked to guard against cross connections              information on chemical reactivity hazards that
   that can lead to inadvertent mixing?                         may pertain to their operations?
•	 If incompatible materials are not handled in              •	 Is information gathered from the above sources
   dedicated systems, are there positive isolation              distilled down into an understandable form and
   methods (spectacle blinds, drop-out, double                  made available to persons that may be involved
   block and bleed valve stations) used to prevent              with or exposed to the hazards of reactive
   inadvertent mixing?                                          chemicals present at the operating facility?
•	 Positive Materials Identification (PMI) - Has             •	 Is every opportunity taken to upgrade operating
   the material handling equipment been checked                 procedures and instructions as new information
   to ensure that it is suitable for the material to            becomes known?
   which it is exposed? In addition to the piping,           •	 Is facility management strongly encouraged to
   vessels, pumps and valving, the internal trim,               contribute its own new information, including
   packing, and lubrication and sealant must be                 lessons learned and near-misses to others within
   considered.                                                  industry?

Appropriate safeguards should be considered to               Conduct a Process Hazard Analysis (PHA)
minimize hazards related to storage of reactive
materials.                                                   Many methods of conducting a PHA are suitable
                                                             for assessing the hazards associated with operation
•	 Can the material deteriorate and become                   of facilities involving reactive materials or
   unstable because of the ambient temperature               mixtures. Several methods, such as “hazard and
   being too high, or too low, or because of                 operability” and “what-if,” rely on a base set of
   excessive shelf time?                                     questions for identifying risks. These base sets of
•	 If containment is breached, will materials                questions should be expanded to include aspects
   become exposed to air or water to which they              that may be unique to reactive chemicals.
   are reactive?                                             Additionally, any process change that is made
•	 Are incompatible materials stored the proper              should receive a management of change (MOC)
   distance apart, or otherwise isolated?                    review.
•	 Can breached containers allow incompatible
   chemicals to mix and react?                               Consider Abnormal Situations
•	 Has equipment used in the storage area been
   evaluated to ensure that it will not act as a heat        The severity of many chemical accidents can be
   or ignition source or cause instability (example          attributed to a reluctance to seriously consider all
   - fork-lift truck exhaust in a dusty
                     scenarios and to develop an appropriate action
                                            plans. Identifying and evaluating deviations that
•	 Are sensors and alarms located in the storage to          may occur and developing appropriate responses
   alert personnel in the event of a release or slow         must be thought out before the fact. Possible
   leak?                                                     abnormal situations must be documented and
                                                             incorporated into instructions and training for
Manage Process Knowledge                                     operating personnel and for emergency responders.
                                                             Otherwise, there is likely to be no response or an
Technical information pertaining to fire protection,         inadequate one. Some questions that should be

    Office of   Emergency Management
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considered:                                               RECOMMENDED READING
   •	 What out-of-control conditions are possible?        Essential Practices for Managing Chemical
      What remedial steps are authorized and by           Reactivity Hazards – 2003, 194 pages, – Chemical
      whom?                                               Center for Process Safety (CCPS).
   •	 What firefighting actions may be taken?
      What actions should be avoided?                     CCPS has teamed with US OSHA, US EPA, the
   •	 Is emergency response equipment                     American Chemistry Council, the Synthetic
      appropriately located and accessible in all         Chemical Manufacturers Association, and Knovel
      types of situations?                                corporation to make this important new CCPS
   •	 Which neutralizing or mitigation initiatives        concept book available for free on the Internet.
      may be taken?                                       “Essential Practices” identifies a simple process to
   •	 What secondary hazards may result from              determine if your operation may be at risk of a
      pressure relief or blow-down systems?               chemical reactivity incident, and then guides you
   •	 What contaminants are likely to be
                 to resources to manage that risk. Persons wishing
                                       free online access to this book will need to follow
                                                          a one-time sign-up procedure through Knovel,
Conduct Frequent Audits                                   CCPS's on-line book distributor, prior to gaining
                                                          access to the document.
Safety, health and environmental (SHE) audits can
serve a number of invaluable functions, including
verification that the concepts of reactive chemical       Chemical Safety Alert: Identifying Chemical
hazards are understood by operating personnel and         Reactivity Hazards Preliminary Screening
have been built into the operation. The SHE audit         Method – 2004, 5 pages -- US EPA.
may be the last line of defense against an accident.
In verifying that the management system is                The purpose of this alert is to introduce small- and
reliable, the SHE audits can also serve as an             medium-sized facilities to a simple method
excellent training activity for key personnel and for     developed by the Center for Chemical Process
“guest” audit participants. Audits provide an             Safety (CCPS), published in Essential Practices
opportunity for input from individuals in all levels      for Managing Chemical Reactivity Hazards, to
of the organizations. Audit teams must also               screen facilities for chemical reactivity hazards.
include at least one person with a good         
understanding of the methods for identifying              sourcesByFilename/flowchart.pdf/$File/flowchart.
chemical reactivity hazards. Team members                 pdf
should be familiar with the different elements of a
sound management system and be able to                    A Checklist for Inherently Safer Chemical
determine if each element is functioning as               Reaction Process Design and Operation What
intended. The effectiveness of the training               You Need to Know – 2004, 8 pages – Chemical
programs and the operating procedures should be a         Center for Process Safety (CCPS).
focal point of the audit program.
                                                          CCPS has developed this free pamphlet as a
                                                          summary of basic principles for safe operation of
                                                          chemical reaction processes.

                                                          Reactive Material Hazards What You Need to
                                                          Know – 2001, 11 pages – Chemical Center for

    Office of   Emergency Management
                                                     Page 6

Process Safety (CCPS).

CCPS has developed this free pamphlet to help
safety managers, chemists, and engineers
determine whether a process could have a chemical
reactivity hazard and what they should do to
prevent potential hazards.

OSHA Reactives Alliance

OSHA Chemical Reactivity Safety

Mary Kay O’Connor Process Safety Center–
Reactive Chemical Research

National Oceanic and Atmospheric
Administration (NOAA) Chemical Reactivity


   Contact the RCRA, Superfund & EPCRA

                Call Center at:

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