Chemical Process Safety

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Friday, March 25, 2022

Determination of explosive properties of a material (starting material, raw materials, finished products)

 

There are various ways of finding out the explosivity of a material. Explosivity of a material can be identified theoretically and also practically with the help of lab instrument (like fall-hammer test). However, liquids can’t be tested using lab equipment. Hence, for explosivity properties for liquids, one shall strictly depend on theoretical method and/or other literatures sources.

1.1  Identification of high energy/ explosive substances functional groups present

Energetic substances in general, can be identified by the presence of hazardous molecular structures such as Peroxide groups, nitro groups, azo groups, double and triple bonds, and ring deformation and steric hindrance all influence the stability of a molecule. Compilations of energetic groups have been published in “Bretherick’s Handbook of Reactive Hazards”.

The below table lists a number of groups that have relatively weak bonds and that release

substantial energy upon cleavage. The list is not exhaustive. The listing does, however, provide assistance in screening chemical structures for determining which should be investigated further before consideration of handling, even in small quantities.

Table 1: list of functional groups known to release high energy on cleavage or change during reaction

Compounds containing

Examples

Carbon (no Nitrogen or Oxygen)

•C=C-C=C dienes

•C=C=C allenes

•triple bonded carbons alkenynes, alkynes, haloalkynes, polyalkynes

•halo-aryl metals & haloarenemetal Ï€ complexes (Ar-Metal-X & X-Ar-Metal)

Compounds containing

Examples

Carbon and Nitrogen

C-N=N-C azo compounds

C linking N rings triazoles, aziridines, nitriles, diaziridines

CN2 diazo compounds

C-N3 alkyl, aryl azides

C-N=N-N triazenes

C triple bond N dicyanogen

Carbon and Oxygen

 

C linking O rings oxiranes

C-O-OH alkyl hydroperoxides

(-CMe2O-O-)3 trimeric acetone peroxide

C-O-O-C dialkyl peroxides

Carbon, Nitrogen and Oxygen

C-N=O nitroso compounds

C-NO2 nitro compounds

C-O-NO2 alkyl nitrites

C-O-NO2 alkyl nitrates

C=NOH oximes

C-N=N-O- arenediazoates, bis(arenediazo) oxides

C(NO2)2 -polynitroalkyl compounds

CO.O-N=O acyl nitrites

CO.O-NO2 acyl nitrates

C triple bond N--O nitrile oxides

Containing Nitrogen and Oxygen

NO nitrogen oxide

NO2 Nitrogen dioxide or N2O4 dinitrogen tetroxide

H2NOH hydroxylamine and salts

N2O dinitrogen oxide

N2O5 dinitrogen pentoxide

Nitrogen and Other Elements

N-X N-halogen compounds

N-metal N-heavy metal compounds

-NF2 difluoroamino compounds

-N-S- nitrogen-sulfur compounds

Halogens, Oxygen, and Other Elements

-O-X hypohalites

-O-X-O2 halates

N-Cl-O3 perchlorylamide salts

O-X-O halites, halogen oxides

O-X-O3 perhalates, halogen oxides

Explanatory note: The presence of one of the mentioned groups in the molecule does not necessarily imply that the substance is hazardous. For instance, a molecule that contains a nitro group attached to a long aliphatic chain does not show significant explosive properties. On the other hand, tri-nitro methane, which consists of three nitro groups attached to a methane group, does have dangerous explosive properties. "Diluting" the active groups by increasing the molecular weight decreases the explosive potential.

However, the initial absence of unstable groups is no guarantee for long-term stability of the compound. For example, some aldehydes and ethers are easily converted to peroxides by reaction with oxygen from air. Organic peroxides represent a class of unstable materials while monomers represent a class of substances that can self-react by polymerization if not properly inhibited and if the temperature is not properly maintained.

1.2  Determination of explosivity theoretically

Oxygen balance (OB or OB%):

It is an expression that is used to indicate the degree to which an explosive can be oxidized. If an explosive molecule (as mentioned in section 5.1.1) contains just enough oxygen to form carbon dioxide from carbon, water from hydrogen atoms, all of its sulfur dioxide from sulfur, and all metal oxides from metals with no excess, the molecule is said to have a zero oxygen balance. The molecule is said to have a positive oxygen balance if it contains more oxygen than is needed and a negative oxygen balance if it contains less oxygen than is needed; the combustion will then be incomplete, and large amount of toxic gases like carbon monoxide will be present. The sensitivity, strength, and brisance of an explosive are all somewhat dependent upon oxygen balance and tend to approach their maxima as oxygen balance approaches zero.

The oxygen balance is calculated from the empirical formula of a compound in percentage of oxygen required for complete conversion of carbon to carbon dioxide, hydrogen to water, and metal to metal oxide.

The procedure for calculating oxygen balance in terms of 100 grams of the explosive material is to determine the number of moles of oxygen that are excess or deficient for 100 grams of a compound.

Oxygen balance calculation formula is -

 

Where,

X = Number of atoms of carbon

Y = Number of atoms of hydrogen

Z = Number of atoms of oxygen

M = Number of atoms of metal (metallic oxide produced)

MW = Molecular weight of the material/powder

The criteria for determining the severity from the OB calculation is:

Note: The evaluation of the hazard potential based on the oxygen balance is not an absolute rating, but only an indicator.

Almost all the recognized detonating explosives have oxygen balances between -100 and +40 (e.g. glycerol trinitrate = +3.5). Any substance with an oxygen balance more positive than -200 should be tested as a potential high risk, and explosivity testing should be carried out (mentioned in section 5.1.3)

 

 

Exercise:

Let’s calculate the oxygen balance for TNT (tri-nitro-toluene)

Chemical formula = C6H2(NO2)3CH3

Molecular weight = 227.1

X = 7

Y = 5

Z = 6

M = 0

Therefore,

 

 

Conclusion: OB is found to be -73.97. TNT falls under the high severity (as per the scale mentioned above) for potential explosive. TNT is a well-known explosive. But for an unknown material even after getting the OB as high severity, experimentally it has to be confirmed whether the material is really an explosive or not.

Note: Why oxygen balance shouldn’t be performed for all the chemicals can be explained by taking an example of MDC (Dichloromethane). Using the formula, OB for MDC can be obtained as-56.5. As per severity scale MDC falls under high severity, but in reality, MDC is not an explosive. Hence, before taking any material for OB exercise it has to be checked whether it is a candidate for OB exercise or not with the help of table 1.

1.3  Determination of explosivity or shock sensitivity of a material using BAM fall-hammer

It is very important know whether a material is shock sensitive or not. Shock sensitive materials are to be stored separately with certain conditions. This can be measured with the help of an equipment called BAM Fall Hammer.

It is also known from several sources that every powder or material is not a candidate for shock sensitivity test. A powder/material is said to be a candidate for shock sensitivity test only if it satisfies either of the two conditions mentioned below -

·      An exotherm or decomposition quantifying over 800 J/g from DSC result (and/or)

·      Presence of any explosive groups (or plosophores) in the chemical structure of the molecule (e.g. nitro, azide, peroxy groups as mentioned in table 1)

BAM Fall Hammer:

Test procedure:




A small sample (50-60 mg) is enclosed in an impact device (Part B in the above diagram). The sample filled impact device is placed on the anvil and the drop weight (Part A in the above diagram) is released from a defined height. The drop weight usually weighs in the range of 1 kg, 5 kg, 10 kg and the height can be adjusted. The potential energy due to free fall of the drop weight is supplied to the compound and can be calculated.

Result and interpretation:

The result of this experiment is either positive (shock sensitive) or negative (not shock sensitive). But if the result is positive then the potential energy required to create the shock sensitivity can be calculated using the formula PE= m x g x h, where (PE: potential energy in Joules, m : mass of the drop weight in kgs, g : acceleration due to gravity 9.8 m/sec2, h : height of the fall of the drop weight).

Basis of safety:

If a material is found to be shock sensitive in nature, then following measures can be taken-

·      Do not store at heights

·      Do not isolate the material (if it is intermediate or final product). It is safe to keep the material in a solution form

·      If it is a reagent or raw material, then explore for alternative of that material

·      If it is intermediate, then explore alternate route of synthesis if material isolation is inevitable.

·      If the material is a final product, then it shouldn’t undergo any kind of powder processing operations (such as milling, sifting etc.). Drying if required to be conducted at utmost care, no FBD & spray drying operations.

·      If specific particle size is required for final product, then during final crystallization step itself it has to be brought and it shouldn’t be pushed to size reduction operations like milling.

1.4  Flow chart for explosivity screening procedure




Chemical Reactivity Hazard Evaluation

 

1.0  Scope and Purpose

This document outlines the general approach undertaken to identify, assess and evaluate the chemical reaction hazards associated with chemical processes. It should be noted that this document is not intended to be a standard operating procedure, but an outline of the generalized working principles and documentation of the rationale used.

This guideline is directed to those personnel involved in research & development, process hazards analysis (Process safety lab), kilo lab and commercial plant operations. It is also useful to those involved in process hazard analysis and process safety management.

2.0  Objective

·         increase awareness of potential chemical reaction hazards associated with chemical manufacture in batch and semi-batch processes

·         help in the assessment of risks from chemical reactions, and advise on how to prevent and control these risks

·         provide a systematic approach for the design, operation and control of chemical reactions in batch and semi-batch processes

·         advise on safe management procedures and appropriate precautions to prevent or reduce injuries and damage caused to property or the environment associated with chemical manufacture; and

·         advise on maintenance, training and information needs to prevent and control chemical reaction hazards

3.0    Definition of terms

Activation energy: the constant Ea in the exponential part of the Arrhenius equation associated with the minimum energy difference between the reactants and an activated complex (transition state), which has a structure intermediate to those of the reactants and the products, or with the minimum collision energy between molecules that is required to enable a reaction to take place; it is a constant that defines the effect of temperature on reaction rate.

Adiabatic: a system condition in which no heat is exchanged between the system and its surroundings; in practice, near adiabatic conditions are reached through good insulation.

Adiabatic induction time: the delay time to an event (spontaneous ignition, explosion, etc.) under adiabatic conditions starting at operating conditions.

Adiabatic temperature rise: maximum temperature increase (readily calculated, that can be achieved) which would occur only when the substance or reaction mixture decomposes completely under adiabatic conditions.

Apparent activation energy: the constant Ea that defines the effect of temperature on the global reaction rate.

Autocatalytic reaction: reaction in which the rate is increased by the presence of one or more of its intermediates and/or products.

Batch reactor: reactor in which all reactants and solvents are introduced prior to setting the operating conditions (e.g., temperature and pressure).

Decomposition energy: the maximum amount of energy which can be released upon decomposition.

Decomposition temperature: temperature at which decomposition of a substance occurs in a designated system; it depends not only on the identity of the substance but also on the rate of heat gain or loss in the system.

Deflagration: a release of energy caused by a rapid chemical reaction in which the reaction front propagates by thermal energy transfer at subsonic speed

Detonation: a release of energy caused by an extremely rapid chemical reaction of a substance in which the reaction front propagates by a shock wave at supersonic speed.

Endothermic reaction: a reaction is endothermic if energy is absorbed; the enthalpy change for an endothermic reaction is a positive value.

Enthalpy of reaction: the net difference in the enthalpies of formation of all of the products and the enthalpies of all of the reactants; heat is released if the net difference is negative.

Exothermic reaction: a reaction is exothermic if energy is released; the enthalpy change for an exothermic reaction is a negative value.

Hazard: a chemical or physical condition that has the potential for causing harm or damage to people, property, or the environment.

Isothermal: a system condition in which the temperature remains constant; this implies that heat internally generated or absorbed is quickly compensated for by sufficient heat exchange with the surroundings of the system.

Onset temperature: temperature at which a detectable temperature increase is first observed due to a chemical reaction; it depends entirely on the detection sensitivity of the specific instrument involved; scale-up of onset temperatures and application of rules-of-thumb concerning onset temperatures are subject to many errors.

Phi-factor: a correction factor which is based on the ratio of the total heat capacity of a vessel and contents to the heat capacity of the contents; the Phi-factor approaches one for large vessels.

Quenching: Abruptly stopping a reaction by severe cooling or by catalyst inactivation in a very short time period; used to stop continuing reactions in a process thus preventing further decomposition or runaway.

Rate of reaction: technically, the rate at which conversion of the reactants takes place; the rate of reaction is a function of the concentrations and the reaction rate constant; in practical terms, it is an ambiguous expression that can describe the rate of disappearance of reactants, the rate of production of products, the rate of change of concentration of a component, or the rate of change of mass of a component.

Runaway: a thermally unstable reaction system which shows an accelerating increase of temperature and reaction rate which may result in an explosion.

Time to maximum reaction rate: the measured time to the maximum reaction rate during a runaway or rapid decomposition; the specific result is highly contingent on the test method used.

Venting: an emergency flow of vessel contents out of the vessel thus reducing the pressure and avoiding destruction of the unit from over-pressuring; the vent flow can be single or multiphase, each of which results in different flow and pressure characteristics.

1.0    Introduction

Any chemical process will involve chemicals and its interactions and equipment in which it is processed. This interaction of chemical within equipment possess some degree of hazard which needs to be understood to control or eliminate the risk. Hence it is important to understand what the parameters which determines safe chemical process are and what are chemical reaction hazards.

4.1    Parameters that determines the design of the safe chemical processes

Three parameters that is chemicals (its intrinsic properties), Reactions rates (Kinetics) and Hardware (equipment) determines the design of safe chemical process as depicted below.

                                        Fig 1: Parameters that determine safe chemical processes

·      Potential energy of chemicals involved: Design of a safe process requires an understanding of the inherent energy (exothermic release/endothermic absorption) during chemical reactions. This information can come from the literature, from thermochemical calculations, or from proper use of testing equipment and procedures. The potential pressure that may be developed in the process is also a very important design consideration.

·      Rates of the reaction/ decompositions: this depends upon temperature, pressure and concentration. Rates of reaction during the normal/ abnormal process conditions must be determined to design safer processes.

·      Plant process equipment and design:Any heat that is generated by the reaction must be removed adequately, and any gas production must be managed. The effects and requirements of scale-up (that is, the relation between bench-scale and plant equipment) must be considered.

4.2    Chemical Reaction Hazards

·      Chemical Reaction Hazards are the hazards that result from uncontrolled chemical reactions.

·      An uncontrolled chemical reaction can be defined as one in which the heat generated by the reaction is greater than the heat which can be removed to the surroundings (plant heat transfer systems)

This results in the temperature of the reaction mixture increasing, which results in an increase in the rate of reaction. This in turn leads to a further increase in the rate of heat generation. When the temperature reaches the boiling point (and/or) decomposition temperature, pressure generation rate can exceed the venting capacities of the plant system resulting in an explosion.

·      Runaway reactions can therefore start slowly but accelerate, until finally it can result in an explosion.

Chemical Reaction Hazards are the result of 3 main parameters:

Ø  The thermal instability of starting/raw materials, reaction mixtures and products.

Ø  Rapid exothermic reactions that raise the reaction temperature to decomposition or violent boiling.

Ø  Rapid gas evolution.

Fig 2: Overview of pathway of Chemical Reaction Hazards

Note: It is the pressure that results in a chemical reaction hazard incident and not the heat. However, the uncontrolled heat leads to pressure generation by the above scenarios.