Risk and Safety Blog

Terrorism Risk Insurance Act Exclusions: Gray Coverage Areas

The U.S. Government has extended the Terrorism Risk Insurance Act (TRIA) to 2014. TRIA is intended to support insurance companies in case the claims from a terror incident go above a certain threshold.

What is interesting are the exclusions used by the government for this reinsurance.

Domestic vs. International Terrorism

Insured losses are covered under TRIA only if the event is certified by the Treasury Secretary is a foreign act of terrorism

Thus, TRIA-type policy would not cover  an event like the 1995 Oklahoma City bombing since it would be considered domestic terrorism.

What if the terror incident was committed by  a citizen acting on behalf of a foreign person? For example, the 2005 London bombing were attributed to UK citizens and Pakitan citizens. If this were to occur in the U.S., will it qualify for TRIA coverage?

Chemical, Biological, Radiological, and Nuclear (CBRN) Terrorist Attacks

Losses resulting from CBRN are covered by TRIA only if such perils are specifically covered in the original property and business interruption insurance policy. Typically, this is not the case.

The above exclusions represent significant uncertainties  in terms of TRIA-coverage and can hurt the insurance agencies. Is the government being smart about the exclusions? What can I say…the house always wins!!!

Posted in Insurance, Security | No Comments »

A Proposed Classification for Reactive Chemicals

The reactivity of a chemical or a mixture is normally assessed by thermal analysis. Thus the thermal analysis data forms the basis of risk mitigation decisions. What does the thermal analysis data tell us and how to base risk mitigation decisions? How to tell which compositions are more reactive and should be scrutinized closely?

Missing from the current body of knowledge is a simple classification to help rank compositions in order of their reactivity.

The National Fire Protection Association (NFPA) 704 recommends Instantaneous Power Density (IPD) – a product of heat of reaction and rate of reaction – to rank reactive chemicals. Although IPD appears intuitive it is difficult to obtain accurate kinetic parameters based on calorimetric data. The calculation of kinetic parameters requires additional work for the user and can be time consuming.

I believe there can be a simpler way to classify reactive chemicals based on heat of reaction and onset temperature determined during thermal analysis.

• Heat of reaction: The energy of reaction, often due to decomposition or polymerization, is the net heat released during a reaction and clearly has to be a factor in identifying reactive hazards. The lower this energy the less energy that is available for detonation. Therefore I like to think of heat of reaction as thermodynamic parameter representing potential energy that can be released; however, it does not tell you “how fast” the energy will be released.
• Onset temperature: The temperature at which a system first exhibits significant exothermic activity is called the onset temperature (To) and denotes a rate of a significant chemical reaction to be measured by the calorimeter. The detected onset temperature is thus a measure of the reaction kinetics. Therefore onset temperature can be used as kinetic parameter for classifying reactive chemicals.

Heat of reaction is representative of the energy release potential of a substance and the onset temperature is a measure of the rate of energy release, therefore I suggest that these two parameters can be combined to develop a hazard index.

The most hazardous chemicals are in Class I, since they decompose at lower temperatures (less than 200 C) and release large amounts of heat (greater than 700 cal/g). These are also the chemicals that are more likely to decompose violently and should be carefully handled and thoroughly tested. Chemicals in Class II also lie in the high hazard category since they release large amounts of energy, but chemicals in Classes III and IV pose medium and low risk, respectively. Thus any chemical or mixture with thermal analysis data can be ranked using the above classification.

Detailed description of the classification is available in the following Chemical Engineering Progress paper.

Posted in Reactive Chemicals | No Comments »

Preventing Pipeline Ruptures

The major cause of natural gas pipeline rupture is not corrosion or material defect but external damage.

External damage is the damage to pipeline during digging, pilling, ground work, etc. by heavy equipment such as anchor, bulldozer, excavator, or plough.  Moreover typically the external damage is from third party construction activities and not the pipeline owner-operator.

Based on the European Gas Pipeline Failure Data, you should expect one external damage every 2800 miles of pipeline annually.

External damage to smaller pipes is more frequent than larger diameter pipelines.  The two major factor affecting external damage are pipeline wall thickness and depth of cover.

Pipeline Wall Thickness

Based on the European Gas Pipeline Failure Data, no external damage was observed on pipelines with a wall thickness of more than 15-mm.

Depth of Cover

As the depth of cover increases, external damage from third party to the pipeline reduces.

This begs the obvious question, if construction activities are the largest contributors of pipeline rupture, why is it difficult to prevent pipeline ruptures from third party damage?

Posted in Failure Data, LNG, Natural Gas Pipelines | 1 Comment »

Industrial Safety in Slumdog Millionaire Nation

According to the International Labor Organization (ILO), there were 11 deaths every 100,000 workers in India in 2005. This number was two in the US and 0.01 in Japan. What is scary is that the number of fatalities may be significantly underestimated because of absence of a formal accident tracking system. I suspect the situation in other developing nations isn’t significantly different.

Why is the fatality rate in the industrial sectors in the developing nations so high?

Are risks being transplanted as the manufacturing shifts to developing countries ?

Are the high GDP growth-rates tainted in blood?

Here are couple of well-researched  articles on status of industrial safety in India and coal mining safety in China:

India’s Work Sites Unsafe, Accident Prone

Black Hole of China

Posted in Chemical Accidents, Process Safety, Regulations | No Comments »

Group Additivity Approach for Estimating Reactive Hazards

During process development or plant operation it is often necessary to estimate energy of reaction based on chemical formulae representation alone. This heat of decomposition represents the potential energy that can be released and is therefore a measure of explosion potential. One can therefore envision that estimation of heats reaction based on chemical similarities should be possible similar to Benson’s group additivity for estimating heats of formation.

I have compiled heats of polymerization and heats of formation from a variety of sources. You can use the functional groups from these tables to estimate heats of reaction for your system of interest.

Heats of Polymerization

Heats of Reaction - Carbon Containing Groups

Heats of Reaction - Nitrogen Containing Groups

Functional Group	Structure	Mean -∆H	Min...Max
In a ring	-N-N-	24	4-72
Imidazole	N-C-N	31	10-51
Tetrazole		50	33-84
Trizene	-N=N-N<	50	33-84
C-Nitro	-C-NO2	75	60-130
O-Nitro	-O-NO2	110	105-115
N-Nitro	-N-NO2	100	93-108
Nitroso	-N=O-	48	33-70
N-Oxide	-N-O-	34	21-51
Oxime	>N-OH	34	25-68
Oxazole	N-C-O	19	8-43
Isocyanate	-N=C=O	15	12-18

Examples

1. Heat of polymerization for Styrene

To predict heat of polymerization I will use –C=C-.
Mean – 20 kcal/mol
Min – 12 kcal/mol
Max – 22 kcal/mol

Thus we estimate heat of polymerization of Styrene to be 217 cal/g [Range 130-239 cal/g]. The experimental heat of reaction for styrene is 151 cal/g.

2. Heat of reaction for Propylene oxide

To predict heat of polymerization I will use value for epoxide group.
Mean – 20 kcal/mol
Min – 17 kcal/mol
Max – 24 kcal/mol

Thus we estimate heat of polymerization of propylene oxide to be 343 cal/g [Range 292-412 cal/g]. The experimental heat of reaction for styrene is 266 cal/g.

To test the values in the two tables, I predicted reaction energies for 105 compounds.

For the 105 compound test set the average absolute error was 87 cal/g. I therefore believe that you can predict heats of reactions within 100 cal/g using the proposed values.

Knowing the heat of reaction for a compound gives you an idea of its explosion potential. As a rule of thumb, if the heat of reaction  is greater than 750 cal/g, the compound is packing high energy.

Posted in Reactive Chemicals | No Comments »

OSHA NEP Fines

OSHA inspected 42 refineries between June 2007 - February 2009. Below is a summary of violations for 30 refineries.

The average penalty for each violation is $ 5,650.

The average penalty per refinery is $ 98,300.

Contrast these numbers with $700 million that cost BP for fatality and personal injury claims related to the Texas City incident.

Is there something wrong with this picture?

Posted in OSHA PSM, Regulations | No Comments »

Equipment Failure Modes

An existing equipment in a refinery may display flaws/damages that either existed during manufacturing or were induced during service. Let us briefly look at pre-service flaws and service-induced deterioration.

Pre-Service Flaws

Equipment flaws from pre-service lifetime are often discovered during in-service inspection because in-service inspection techniques are much detailed than during original construction. Typical pre-service flaws are:

• Material production flaws
• Welding related flaws
• Fabrication related flaws
• Heat treatment related flaw

In-Service Deterioration

Typically, following damages are seen in in-service refinery equipment:

• General and local metal loss due to corrosion and/or erosion
• Surface connected cracking (SCC)
• Subsurface cracking
• Microfissuring/microvoid formation
• Metallurgical changes

During fitness-for-service assessments it is important to determine the cause of damages so that to understand potential future degradation. Based on the understanding of the degradation mechanism necessary mitigation measures can be put in place.

Posted in Failure Data, Reliability | No Comments »

Systematic Evaluation of Reactive Chemical Hazards

Evaluation of reactive chemical hazards can range from simple paper-based calculations to highly complex testing and modeling. This post is aimed to help you formulate a systematic strategy for evaluating reactive chemical hazards in your facility.  I will divide the various approaches in three tiers - simple to complex.

Tier I . Theoretical Screening

At the onset, you should try to answer the question - Is there potential reactive chemistry?

To answer this question you can make use of variety of tools:

• functional groups indicative of reactivity hazards
• using group contribution method to estimate energy of reaction
• develop incompatibility matrix
• reactivity data avaiable through MSDS or Bretherick’s Handbook

Tier II. Experimental Screening

Experimental screening involves the conduct of experimental tests to gauge the thermal hazard of materials and processes. The goal of these tests is to verify theoretical values identified previously as well as provide additional information by which the materials and processes may be characterized.

Experimental screening can be divided into three different areas of concern,

• Reactivity: DSC, DTA, TGA
• Mechanical sensitivity: Drop weight test, blasting cap test
• Thermal sensitivity: DSC, DTA, TGA, Konen test

Differential Scanning Calorimetry (DSC) is the work-horse of the industry in determing thermal sensitivity and reactivity.

Tier III. Detailed Testing and Modeling

Experimental analysis involves the conducting thermal hazard analysis tests to verify previous results as well as identify reaction rates and kinetics. The goal of this level of testing is to verify calculated and experimental results and provide additional information by which the materials and processes may be characterized.

Detailed testing is usually conducted using advanced calorimeters such as

• Advanced Reaction Calorimeter (ARC) from TIAX
• Automated Pressure Tracking Adiabatic Calorimeter (APTAC) from TIAX
• Vent Size Package (VSP) from Fauske and Associates

These tests generate data for input into the development of a kinetic model.

By combining experimental data and kinetic model, one can now predict behavior of the reactive system with confidence.

Posted in Reactive Chemicals | No Comments »

Is the Chemical Safety Board (CSB) Positively Impacting Process Safety?

CSB’s approach to chemical accident investigation is a step further than OSHA’s. CSB gathers background information about the accidents, performs a detailed root cause study, and makes recommendations to appropriate stakeholders. Great approach to a complex issue…but CSB’s strategy following the investigation leaves a lot to be desired.

The hope from CSB’s accident investigations is that the lessons learnt will prevent other manufactures commit similar errors. For CSB’s investigation to be helpful in accident prevention, the recommendations that come out of CSB’s investigations must have following traits:

1. Clear and actionable
2. Who should take the action
3. How the action be implemented

Most of CSB’s recommendations appear to be non-specific and vague.

Non-Specific Recommendations

CSB’s recommendations are not directed to the appropriate stakeholder in many cases and are often too vague.

As an example, below are lessons learnt from CSB’s investigation of explosion at Syntron LLC (2006). I’m only pasting first few lines (pg. 14-15)…you can get the details in the pdf.

1. Manufacturers should take a comprehensive approach, and identify and characterize reactive hazards;
2. Chemical manufacturers and others with reactive chemistry operations should control changes to batch recipes, including key operating conditions
3. Manufacturers with reactive chemistry operations should document the performance requirements and capabilities of process equipment
4. Train Personnel on Hazards and Procedures
5. Manufacturers should implement an effective emergency plan

All the above statements are basically telling manufactures to “be safe” without giving them any concrete tools to implement the recommendations. Furthermore, these are all known safe-work practices and are covered under current PSM requirements.

CSB’s most recent report on T2 reactive explosion contains TWO recommendations to the American Institute of Chemical Engineers (AIChE) and Accreditation Board for Engineering and Technology (ABET) to introduce a course on reactive chemicals at the engineering bachelor level. OMG…half-a-million dollars or more of investigation for this trivial recommendation!

Communication of Recommendations

Let us say that CSB does have actionable recommendations then further consideration should be given to the message and how it is communicated. Thick reports in “dull” English may not be the optimum way to reach the desired audience. Nowadays creating videos and audio-podcast is not expensive. iPod and YouTube represent a great way to reach audience and capturing their attention; however, the key again is the message. Look at the following YouTube video from CSB about maintaining safety during recession…it is advising you to “be safe” without providing any insights on how to do so.
The issue isn’t just the tools…the issue is depth of the message.

Final Word

CSB has to significantly distill its lessons learned from accident investigations to create practical information valuable to workers and the process industries. Generic recommendations and generic safety messages will not help future accident prevention.

CSB has an incredible opportunity to impact process safety community across the world and a bit of upfront strategic planning will go a long way. Unfortunately, from what I have seen so far the CSB does not have the depth or the vision to make valuable contribution towards worker safety within the process industries.

Posted in Chemical Accidents, Process Safety, Regulations | 2 Comments »

Where’s the Training Material from OSHA Grants?

Interesting post by John “Dust Explosion” Astad.

Where’s the Beef? Previous Training Material

Posted in Regulations, Training | No Comments »