Mark V, Inc.

Dear Ms. Roth:

I commend the New Jersey Department of Environmental Protection for recognizing that the hazards of reactive chemicals are not adequately protected against under current regulations and for taking the bold action of proposing a regulation that will provide safeguards against these hazards.  As I am sure you are aware, other States and the Federal Government are watching the DEP’s actions very closely and may well use the regulation you develop as a model for changes to their own regulations.  Thus the regulation that you implement will likely be the basis that many other regulations are modeled after.  I would like to help the DEP achieve their goal of developing a comprehensive regulation that will protect the people of New Jersey, and in developing a model regulation that other States and the Federal Government can pattern their own regulations after.

I am a chemical engineer, and former Plant Manager, and Vice President and General Manager of a chemical company headquartered in Edison, New Jersey.  I understand that the chemical marketplace is very competitive and that there is continuous emphasis on reducing manufacturing costs.  I also know from personal experience that many managers in the chemical industry think that compliance with safety and environmental regulations is just a hole that you throw money into and for which you receive no return.  When this is the attitude of management, they are correct because they create a self fulfilling prophecy;  they do no more than they think they can get away with and establish inadequate safety and environmental programs.  On the other hand, the enlightened managers that really do place an emphasis on complying with safety and environmental regulations find that not only do their incident rates go down, but the frequency and severity of catastrophic episodic incidents are significantly reduced or eliminated.  These managers also find that their manufacturing costs are reduced because their plants run more efficiently and reliability.

Throughout my 36 year career, I have been heavily involved in all aspects of process safety including risk assessment and accident investigation.  Since starting my own process safety consulting business in 1996, I continue to work primarily in these two areas.  Like the U.S. Chemical Safety and Hazard Investigation Board, I have found that the majority of catastrophic episodic incidents have involved reactive chemicals.  And like the CSB, I have been dismayed that these chemicals are not adequately covered under current regulations. 

I have listened to industry representatives at your hearings state that industry can not afford complying with any new regulations.  I know from experience however, that most of the successful companies are already evaluating the hazards of reactive chemicals and incorporating safeguards into their processes to protect against those hazards.  They are doing this not because some regulation requires it, there is not currently any such regulation, but because they know that it is in the best interest of their company to do so.  Most of the smaller companies will have less work to do to comply with the regulation, and therefore less cost, just due to the nature of their business and the limited activities that they will need to perform, or have performed, to comply with the regulation.  It may be true that some companies that are poorly managed, or have limited resources will find this proposed regulation to be burdensome to them.  One of the most important functions of government is to protect its citizens from unnecessary risks, as is the intent of the proposed regulation.  If there is a demand for the services or products produced by these poorly managed or insufficiently staffed companies that are burdened by the proposed regulation, another company will fill the void left by them.

I have reviewed the technical aspects of the proposed changes to the Toxic Catastrophe Prevention program and find that it is a significant step towards improving the safety of those that live and work near chemical processing facilities.  The DEP has incorporated a methodology for identifying reactive hazardous materials and for ensuring that sufficient safeguards are provided to protect the public from those hazards.  I find however, that the methodology is not comprehensive.  There are significant classes of hazardous materials that are not currently listed that must be incorporated.  For example, aluminum powder, a water reactive material with a NFPA instability rating of 1, played a significant role in the explosions that occurred at both Napp and Morton.  However, it is not covered by the proposed regulation.  Neither are most other Water Reactive, Pyrophoric or NFPA instability Rating 1, 2, or 3 materials.  It is these types of chemicals that are involved in most of the catastrophic episodic incidents that these rules are intended to prevent.  They must be included in the chemicals covered by this act.  For your convenience, I have enclosed copies of my reference materials.

My suggestions on how the rules can be improved follow:

The introductory text states that the distance to the endpoint where the effects of an incident are to be evaluated is 100 meters.  I have not found a reference to this value in the proposed changes and presume that this value is currently used.  In many cases, however, the hazardous chemicals are much closer to the public than 100 meters.  Again, refer to Napp and Morton.  This distance is very important with regard to explosions since their effects diminish quickly with distance (blast overpressure diminishes with the cube root of the distance).  I suggest using 100 meters, or the fence line, whichever is closer.

7:31-1.5 State Definitions:

1.      Flammable material.  Flammable materials are normally considered to be those materials that have a flash point under 100 deg. F.  However, in chemical processing units, combustible materials (those with a flash point of 100 deg. F or greater) are often processed above their flash point and within their flammable range.  These combustible materials therefore have all of the hazards normally associated with flammable materials.  It is therefore common practice among safety professionals to treat combustible materials as flammable, if they are present in the process within 30 deg. F of their flash point  This convention is also required by OSHA’s regulation covering Flammable and Combustible Materials:

a.       29 CFR 1910.106(a)(18)(iii):

                                                                           i.      When a combustible liquid is heated for use to within 30 deg. F. (16.7 deg. C.) of its flashpoint, it shall be handled in accordance with the requirements for the next lower class of liquids.

The NFPA also recognizes the need to consider the storage or processing temperature of a combustible material when determining the safeguards that need to be provided:

b.      NFPA 30  Flammable and combustible materials, Appendix A.1.2:

                                                                           i.      The volatility of a liquid is increased by heating. Where Class II or Class III liquids are exposed to storage conditions, use conditions, or process operations where they are naturally or artificially heated up to or above their flash points, additional fire safety features, such as ventilation, separation from ignition sources, diking, or electrical area classification, might be necessary.

Therefore it is imperative that the DEP require that all materials that are present, or potentially present, in a process be covered if they are within 30 deg. F of their flash point.  This concept needs to be incorporated, as appropriate, through out the Act.

2.      Change the definition of functional group to:  ““Molecular Structure”  means the manner in which functional groups and atoms are interconnected with atomic bonds to form molecules.  Compounds with similar molecular structures usually have similar thermochemical (reactive) properties”.

General Note:  The proper term to use is molecular structure.  Functional group is only one of the characteristics that are used in identifying the molecular structures that predict reactivity.  Search and replace functional group with molecular structure.

3.      Change the definition of “Heat of Reaction” or ΔH_R to:  “The amount of heat that is released (by convention a negative value) or absorbed (by convention a positive number) when a chemical reaction takes place with an efficiency of 100%, usually expressed in calories per gram of one of the reactant materials”.  More specifically, the heat of reaction is the energy content of the reaction products minus the energy content of the reactants.  This can be obtained numerically by subtracting the heats of formation of the reactants from the heats of formation of the products with the reactants and products in the state (liquid, vapor, solid, in solution or not) they will be in during the reaction being evaluated.  (More accurate definition)

4.      Add:  “Heat of Explosion” or “ΔH_E” means to:  “The amount of heat that is released (by convention a negative number) when a reaction takes place explosively.  This value is equivalent to the Heat of Reaction times the efficiency of the reaction.  When a reaction takes place explosively, all of the reactants do not react because the reactants are dispersed by the initial explosive force or not all of the reactant is present within its flammable or explosive concentration.  ΔH_E = ΔH_R x Percent reacted”.  (More accurate definition and needed to define the term as used in the Act)

5.      Change the definition of “Inherently Safer Technology” means to:  “a process which is designed to minimize or eliminate the potential for an EHS incident by utilizing techniques that include, but are not limited to:  1)  Minimizing the amount of EHS stored on site and used in the process;  2)  Substituting a non-hazardous or less hazardous material for the EHS used in the process;  3)  Operating the process under less hazardous conditions (i.e.:  low temperature instead of high temperature, low pressure instead of high pressure);  4)  Designing the process equipment so that it can contain the EHS under the worst case scenario (i.e.:  using a pressure vessel that has a Maximum Allowable Working Pressure (MAWP) that is greater than the highest pressure that can possibly be produced under the worst case condition).  Designs of this type are much less susceptible to incidents caused by human errors.”  (More accurate definition)

6.      Change the definition of “Reactive Hazard Substance (RHS) Mixture” means to:  “a combination of substances, containing at least one EHS, intentionally mixed in a process vessel and is capable of undergoing an exothermic chemical reaction which produces toxic or flammable EHSs or energy where the value of the heat of reaction is greater than (more negative) or equal to -100 calories per gram of RHS Mixture.  RHS Mixtures include a reactant, product, or byproduct that is a chemical substance or a mixture of substances Listed in Table I, Parts A, B, C, or D, Group I, or having one or more of the molecular structures specified in Table I, Part D, Group II”.  (Definition is consistent with the convention used by the engineering and scientific community that will be evaluating the regulation and the available data.  Inclusion of materials listed in other tables as needed to include all RHSs as discussed below)

7:31-2.2(b)2.:  Worst Case Release Quantity:  Change “the greatest amount contained in a single vessel” to:  “The greatest amount contained in a single vessel, or group of interconnected vessels where there are no isolation valves between the vessels, or if isolation valves are present, they are normally in the open position”.  (If vessels are interconnected, the entire amount present is subject to release or explosion)

7:31-2.2(b)3i:  Change “The heat of combustion of the RHS or RHS Mixture” to:  “The heat of reaction of the RHS or RHS Mixture”.  (Heat of combustion is a special type of heat of reaction, and the DEP should not limit this to only that type of reaction)

7:31-2.2(b)3ii:  Change “100% yield factor for an RHS Mixture in a process vessel” to:  “All of the RHS Mixture reactants in the process vessel are assumed to react”.  (Clarification)

7:31-2.2(b)3iii:  Change “28% yield factor for a Table I, Part D, Group I RHS in a storage vessel” to:  “For compounds shown in Table I, Part D, Group I, that are contained in a storage vessel, assume that 28% of the reactants react”.  (Clarification)

7:31-2.2(c):  Flammable compounds listed in Table I, Parts A, B, or C are by definition reactive materials.  If there is the potential for the leak of a flammable material, there is the potential for a vapor cloud explosion.  If the material is a liquefied gas, it has the potential for a BLEVE and vapor cloud explosion.  To exclude these materials from the requirements established for reactive materials leaves a huge gap in the program that can lead to disastrous results.  Consider exempting only those compounds that exhibit only toxic hazards and which have been previously evaluated.

7:31-3.1(c)1i:  Process flow diagrams may be simplified to be useful in training and performing hazard evaluations.  However, the Piping and Instrument Diagrams (P&IDs) must be accurate and complete.  At a minimum they must show:  All equipment, including comprehensive descriptions and specifications;  all piping, including size, line numbers and specifications;  all instrumentation and controls;  all interlocks;  and a lot more.  For your convenience, I have attached a P&ID checklist that I use during audits of process safety information for compliance with the PSM regulation and the RMP rule.  Change the wording to require “accurate and up-to-date P&IDs”.

7:31-3.1(c)1.ii(3):  The rate of energy release is a function of temperature.  Therefore, change:  “and rate of energy release to”:  “and rate of energy release as a function of reaction temperature”.

7:31-3.1(c)3 Subchapter 3.  40 CFR 68.52 Operating procedures.  The DEP provided notice that there was to be a hearing on March 17 to review these proposed changes.  Was this notice published in the 100 plus languages that are spoken in New Jersey?  If someone who doesn’t understand English came to the hearing and wanted to comment, were you prepared to provide an interpreter so that all present could understand?  What if there were several people there that only spoke something other than English?  Will the Final Rule be published in the 100 plus languages that are spoken in New Jersey?  The only place I know of that tries to handle this situation is the United Nations, and they employ hundreds of interpreters.  Are you proposing that the chemical industry hire translators?  This issue is a lot bigger than just operating manuals;  it pertains to the whole concept of communications.

Chemical process units are run by teams of individuals that continuously interact with each other.  If they cannot communicate with each other, you will have a situation that is much worse than the hazards presented by reactive chemicals.  The chemical plant operators need to be able to read and understand the instructions placed in the log book by the supervisor.  Likewise, the supervisor needs to be able to understand the significant things that transpired during the shift that are recorded in the log book by the operator.  The operators must be able to communicate with each other so that they work together as a team, and not independently.  Consider the case where the control room operator instructs the outside operator to start the spare cooling water pump because the operating pump shutdown unexpectedly.  The operator can’t understand the instruction because he speaks a different language, and as a result the reactor temperature rises resulting in a runaway reaction and explosion, leaving 7 people killed and 35 seriously injured.  The only way to avoid this situation is to:  hire only those that are fluent in, and can read and write in English (if the individual wants to work in the chemical plant he will first have to go to school to learn English), and to provide all operating manuals, training, logbooks, log sheets, hazard analyses, management of change, pre-startup safety reviews, maintenance instructions, etc. in English.  Again, failure to have employees that can speak, read and write English is an invitation for disaster.  Consider deleting the sentence stating that operating procedures will be written in a language that the operator can understand.  I have worked in about a dozen chemical facilities in Texas.  They all employ Mexican Americans and Asians.  However, each has a safety policy that requires that all employees be able to speak, read and write in English.  They also require that all business related communication be in English.  I believe that this is the correct and safe approach to this issue. 

7:31-3.4:  General Comment:  The term “accident” has several implied meanings and connotations that may or may not be appropriate for a particular incident.  That is why safety professionals prefer to use the term “incident”.  Consider replacing all occurrences of “accident” with” incident”.

7:31-3.4.iii  Change “The basic and contributory causes” to:  “The root causes and contributing causes”.  (To be consistent with current safety professional terminology)

7:31-3.5(a)4  Change “the names and affiliation of the hazard review participants” to:  “The names, position, and affiliation of the hazard review participants”.  (The position of the participant helps to clarify what skills and knowledge the individual brings to the analysis.  This can be useful in determining if the appropriate people participated)

7:31-3.5(a)  Add an item after item 7:  Documentation that shows that the safeguards provided or proposed achieve the level of risk required by the company.  (A risk assessment is required to determine if the safeguards have sufficient reliability and number of layers of protection to achieve the low levels of risk required by the company for the potential degree of adverse consequences.  It is never adequate to say that, for instance, there is a pressure relief valve on the tank, therefore it can not be overpressured and rupture.  If the consequences of vessel rupture can lead to loss of life, additional safeguards are required (i.e.:  pressure monitoring and alarms, temperature monitoring and alarms, a redundant pressure relief device, etc.).  Means for performing these analyses are well understood by safety professionals.  Note that the risk analysis suggested here is not the same as the risk analysis to be performed to determine the impact of a release on the public.)

7:31-4.1(c)8 Operating Procedures:  Delete “If the EHS Operators do not understand English, the operating procedures shall be written in the language that the operators understand”.  (Refer to 7:31-3.1(c)3 above)

7:31-4.1(c)24ii:  :  The temperature at which instability initiates and the kinetic data needs to be determined using established engineering practices.  Change “Thermodynamic and reaction kinetic data including: heat of reaction,  temperature at which instability (uncontrolled reaction, decomposition, and/or polymerization) initiates, and rate of energy release data” to “Thermodynamic and reaction kinetic data including:  heat of reaction; onset temperature at which the rate of temperature change due to uncontrolled reaction, decomposition, change in molecular structure, or polymerization exceeds 0.01 °C/min.;  the rate of pressure rise (dP/dt);  and the rate of temperature rise (dT/dt);  all of which are to be corrected to a thermal inertia of 1.0 (Ψ = 1.0);”

7:31-4.5(b):  Change “to determine the frequency of inspections and tests and to evaluate equipment reliability” to:  “to determine the required frequency for inspections and tests and to evaluate equipment reliability”.  (DEP is interested in not only how often they do their testing and inspections but how often it should be done based on the analysis of their testing and inspection results)

7:31-4.9(b)4iii:  Change “The basis and contributory causes” to:  “The root causes and the contributory causes”.  (Makes the terminology consistent with that used by safety professionals)

7:31-6.2(g):  Change “functional groups” to:  “molecular structure”  (refer to general note in definitions section)

7:31-6.2(g):  Change “ΔH” to:  “ΔH_R”  (Accuracy and consistency)

7:31-6.2(h):  Change “the greatest amount of RHS Mixture contained in a process vessel” to:  “The greatest amount of RHS Mixture contained in a single vessel, or group of interconnected vessels where there are no isolation valves between the vessels, or if isolation valves are present, they are normally in the open position.  (If vessels are interconnected, the entire amount present is subject to release or explosion)

Table I, Part D, Group I:  Consider adding those compounds that NFPA considers a Rating1, 2 or 3 instability hazard.  Referring to NFPA 704 Table 7.2  Degrees of Instability Hazards:  it can be seen that Rating 1, 2 and 3 compounds exhibit violent chemical changes (reactions) that can be explosive in nature at elevated temperatures and/or pressures.  Those elevated temperatures and pressures are frequently present in chemical processes during normal operation and/or credible abnormal conditions.  These are also the chemicals that are involved in most of the reactive chemical incidents.  The U.S. Chemical Safety and Hazard Investigation Board reported in there public hearing on May 30, 2002 in Patterson, New Jersey that 39% of the reactive chemical incidents investigated involved NFPA 1, 2, and 3 materials.  It is therefore imperative that these compounds be covered by this Act.

7:31-6.3(a) Table I, Part D, Group II:

1.      Change “Functional Groups” to “Molecular Structures”.  (Refer to general note under definitions above)

2.      Except as noted below, all of the materials shown in this table are appropriate in that they indicate instability.  However, several molecular structures need to be added: 

C=C-R                       Aziridines (With two C-N bonds)

  N

CN₂⁺                        Diazonium salts (carboxylates, perchlorates, sulfates, sulfides and derivitives, tetrahaloborates and triodides)

N=N-N-H                   Triazenes

N=N-N-CN

N=N-N-OH

N=N-N-NO

N-N=N-C=C              Triazoles (With C-N bonds)

N-N=C-N=C

C=C-NO₂                    Nitroalkenes

O-X=O                        Halites, halite salts

O-X-O₃                       Perhalates

N-X₃                            Nitrogen trihalide

(Refer to Bretherick, 1986, 70-71; Bretherick, 1990. 1477-1824)

3.      Items 23, 24:  Add:  Ar-O-O-H;  Ar-O-O-C;  Ar-O-O-Ar (to be comprehensive)

4.      Item 31:  Should this represented as: H₅N₂⁺Z^-, or should this structure be added as an alternate form?

5.      Item 34:  Should this be represented as:  H₃N→M⁺EO_N^-, or should this structure be added as an alternate form?

6.      Items 40, 41, 42:  The structures shown are for the polymer, not the reactive monomer that can form the polymer.  The monomers are included in the lists which follow.

7.      All of the molecular structures shown in Table I, Part D, Group II represent materials that are extremely hazardous.  However, it is not comprehensive.  Many of the compounds commonly used in the chemical industry can create extreme reactive hazards such as explosions under normal operation and/or credible upset conditions.  Again, this is consistent with the findings of the U.S. Chemical Safety and Hazard Investigation Board.  There are numerous other compounds and structures that must be added to Table I, Part D, Group II:

a.       Peroxide forming materials:  Peroxides are extremely unstable compounds, are also initiators of other energetic reactions and are included in Table I, Part D, Group II.  Several types of materials readily react to form peroxides.  These materials must be included in Table I, Part D, Group II, or a similar table.

                                                                           i.      Structures Susceptible to Peroxide Formation:

(Bretherick 1986, 72-73;  National Research Council, 1981, 63-64;  National Research Council, 1983, 244-245).

b.      Pyrophoric Materials:  Pyrophoric materials react violently when exposed to air to cause fires and/or explosions.  These materials must be included in Table I, Part D, Group II, or a similar table.

                                                                           i.      Examples of Pyrophoric materials:

(Bretherick, 1986, 71-72;  Britton, 1989;  Cardillo and Nebuloni, 1992;  National Research Council, 1983, 240-241;  Sax and Lewis, 1987, 985)

c.       Water reactive materials.  Water reactive materials react violently with water to cause fires and/or explosions.  The NFPA includes water reactivity in the hazard descriptions of materials shown in NFPA 49.  These materials must be included in Table I, Part D, Group II, or a similar table.

(NFPA 49, 1994; NFPA 325M, 1994)

7:31-6.3(b)1:  Delete this exemption.  Inhibitors are nothing more that a safeguard.  Their reliability however is not very good.  Most inhibitors decompose at a rate which is dependant on time and temperature.  Safeguards are required to ensure that the temperature of the material containing the inhibitor is maintained below a specified upper limit, and for a time not exceeding its decomposition rate at that temperature.  In addition, periodic analyses will be required to determine the concentration of the inhibitor in the material and to verify that the inhibitor is active.  Means need to be provided to add additional inhibitor when necessary.  Pressure and temperature monitoring needs to be provided to warn of a runaway reaction, and to activate safeguards, for those instances where the material does react unexpectedly.  Therefore, the only way to ensure that the proper concentration of inhibitor is present is to have all of the equipment, procedures, and training needed to ensure that it is there.  The best way to achieve this is to have them covered by the regulation.  I have investigated three incidents in the past few years dealing with explosions that resulted from the inhibitor not being present.  Eleven people were killed in these incidents and hundreds were injured.  Please delete this exemption.

7:31-6.3(b)2:  Change to be consistent with the proposed definition.  Change to:  “An RHS Mixture is a combination of substances, including at least one EHS, intentionally mixed in a process vessel and is capable of undergoing an exothermic chemical reaction which produces toxic or flammable EHSs or energy where the value of the heat of reaction is greater than (more negative) or equal to -100 calories per gram of RHS Mixture.  RHS Mixtures include a reactant, product, or byproduct that is a chemical substance or a mixture of substances having one or more of the molecular structures specified in Table I, Part D, Group II”.  (Definition is consistent with the convention used by the engineering and scientific community that will be evaluating the regulation and the available data)

7:31-6.3(b)2i:  The heat of reaction is the difference in energy level of the products and reactants.  Heat of combustion is a special; case of heat of reaction where the material reacts with oxygen.  Heat of decomposition is another special case of heat of reaction where the material reacts with itself and decomposes.  It is important that the owner use the heat of reaction for the reaction that is being considered.  In some cases, there are multiple reactions that could take place and each may need to be considered.  For example:  1-3 butadiene can react with itself to form polymers, it can react with itself to form dimmers and trimers, it can burn, it can decompose.  The heat of reaction in each case is different.  As currently written, someone might use the heat of combustion for butadiene when they should be using the heat of polymerization.  This can pose problems.  Change to:  “The heat of reaction, heat of combustion, heat of decomposition, or heat of explosion, as appropriate for the reaction being evaluated, shall be used in accordance with iv below”.

7:31-6.3(b)2ii:  The heat of reaction is the difference in energy level between the products and the reactants.  If the products are in a solution, the heat of solution or dilution needs to be considered in order to obtain an accurate value for the heat of reaction.  The heat of solution or dilution can be significant in some chemical reactions and even overshadow the heat of reaction without solution.  Omitting the affects of heat of solution and heat of dilution may exclude some materials from coverage, or put them into a lower classification than where they should be.  Delete this item.

7:31-4.2(c):  Change “Heat of Reaction (Exothermic) (-ΔH_R) to:  “Heat of Reaction (ΔH_R).  Chance values in the table accordingly (i.e.:  from “100 ≤ -ΔHR ≤ 200” to:  “-100 ≤ ΔHR ≤ -200”.  ( To be consistent with common scientific and engineering practices and to prevent confusion of scientists and engineers)

7:31-7.2(a)3iv:  An EHS listed on Table I Part A, B, or C as a flammable material has by definition, the potential to be explosive.  Vapor cloud explosions and BLEVEs can be devastating.  In four vapor cloud explosions that I have investigated in the past few years, there were eighteen people killed and hundreds injured.  It is therefore imperative that the reactive hazards of these flammable materials be evaluated and safeguards provided as appropriate, just as for the materials listed in Table I, Part D.  Please make the changes necessary to incorporate these materials into the RHS program.

Please feel free to contact me if I can be of further assistance.

Peter Howell

Peter Paul Howell, PE