Gas Hazards in the Petrochemical Industry Posted on 09 February, 2010 | Tags: Plant Safety Although flammable and toxic

gas hazards are generally well understood by operators, technicians and safety personnel working within the petrochemical industry, continuous training and refreshment of knowledge is essential to avoid potential incidents linked to complacency or misguided actions. At times, new personnel may be assigned work activities in potentially hazardous areas with only very brief training in the basics of gas hazards and the operation of detection equipment. A basic introduction to gases and associated hazards in the petrochemical industry is important for the safety personnel working in the Petrochemical Industry. Behavior of Gases Different gases have different densities. Heavy gases like Hydrogen Sulphide have higher densities have the tendency to sink, whereas lighter gases because of their lesser densities tend to rise. But due to their constant motion there is continuous mixing of gases and these do not form separate layers as in case of liquids. In a room when a natural gas (methane) leak is there, the gas will tend to rise as it is lighter than air. This happens in perfectly still conditions but in case of presence of any air currents, there will be an increase in mixing. But the constant motion results in a considerable concentration of methane even at the floor level. Air is a mixture of gases and its composition is reasonably constant. This it is usually considered as a single gas, which simplifies the measurement of toxic and flammable gases for safety and health applications. Combustion of Gases Combustion (Burning) is a simple chemical reaction in which a substance reacts in the presence of oxygen present in the atmosphere and produces heat. Most of the organic compounds are combustible in nature. Hydrocarbons are the simplest form of organic compounds having carbon and hydrogen atoms. These are the main constituents of crude oil and gas and highly combustible in nature. Methane is the simplest of all the hydrocarbons having one Carbon and four Hydrogen atoms. This is the first compound in the family of alkenes. Physical properties of alkanes change with increase in number of carbon atoms in the hydrocarbon molecule. Hydrocarbons with up to four carbon atoms are gases, those with five to ten carbon atoms in liquid are volatile liquids, and heavier fuel oils have carbon atoms between eleven to eighteen and number of carbon atoms in lubricating oils range between nineteen to forty. Tars and waves have longer hydrocarbon chains.

During combustion, simple hydrocarbons react with oxygen from the atmosphere to produce carbon dioxide and water. In case of incomplete combustion due to lack of oxygen, carbon monoxide is also produced. Complex organic compounds contain elements such as oxygen, nitrogen, sulphur, chlorine bromine or fluorine and on burning the products of combustion include other compounds as well. E.g. Combustion of hydrocarbons like Oil and Coal results in production of Sulphur dioxide (SO2) because of the sulphur content present in these hydrocarbons. Similarly combustion of chlorine containing hydrocarbons such as Methyl chloride or Poly Vinyl Chloride (PVC) results in production of Hydrogen chloride (HCl). A mixture of compounds is likely to be encountered in most of industrial environments wherever there is a risk of explosion or fire because of the presence of flammable gases or vapors. Raw materials for the Petrochemicals Industry are mixture of chemicals that are processed to manufacture products for usage. Crude oil that is the main raw material is processed to extract various products through Fractional Distillation. Fractions further undergo processes like Catalytic Cracking to produce chemicals for processing industry. Flammable hazards are thus likely to be represented by many substances on a typical Petroleum Refining Plant. Explosive Risks A source of ignition, typically a spark and oxygen are required to ignite a gas. For ignition, the concentration of gas or vapor in air must be at a level such that the fuel and oxygen can react chemically. Power of explosion depends on the fuel and its concentration in the atmosphere. Relationship between Air, Ignition and fuel is depicted in the 'Fire Triangle' The concept of 'Fire Tetrahedron ' is fairly a new concept to illustrate the risk of fires being sustained due to chemical reaction. With most types of fires the original concept of 'Fire Triangle' model works very well and removal of one of the elements (Fuel, Oxygen or Ignition Source) of the triangle can prevent occurrence of fire. But there are exceptional cases of fire when burning of metals like Lithium or Magnesium are involved. These metals can react with water in an exothermic reaction resulting in production of flammable Hydrogen gas. In such circumstances using water to extinguish the fire could lead the mixture to become hotter and result in explosion. Not all the concentrations of flammable gas or vapor in the air result in burning or explosions. Lower Explosive Limit (LEL) is the lowest concentration of Fuel in air that will burn. For most of flammable gases, it is lesser than 5 percent by volume. Hence the risk of explosion is higher for even relatively low concentrations of gas or vapor escape into the atmosphere. Alarm Levels Flammable gas detection equipment is generally designed to provide a warning of flammable risks before the gas reaches its lower explosive limit. The first alarm level is generally set at 20% LEL, with a

second-stage alarm at 40-60%LEL. In some applications such as gas turbine monitoring alarms may be set as low as 5%LEL. LEL levels are currently defined in three standards ISO 10156, EN 61779-20 and IEC 60079.LELs are obtained as per the original ISO standards lists when the gas is in a static state. LELs listed in the EN and IEC standards were obtained with a stirred gas mixture that resulted in lower LELs in some cases because some gases proved to be more volatile when in motion. Toxic Risk Under many circumstances, gases and vapors that are released from Petrochemical Processing activities have harmful effects. The workers may get exposed to the toxic emissions directly or indirectly through inhalation, swallowing or absorption through the skin. Prolonged exposure to harmful substances may result in developing of chronic illnesses such as cancer even after many years. Many toxic substances are dangerous to health in concentrations as little as 1ppm (parts per million). Given that 10,000 ppm is equivalent to 1% volume of any space, it can be seen that an extremely low concentration of some toxic gases can present a hazard to health.

It is worth noting that most flammable gas hazards occur when the concentration of gases or vapours exceed 10,000ppm (1%) volume in air or higher. In contrast, toxic gases typically need to be detected in sub-100ppm (0.01%) volume levels to protect personnel. Toxic substances that are gaseous in nature are especially dangerous because these are often invisible and odorless. Ambient temperature, pressureand ventilation patterns significantly influence the behaviour of a gas leak and their physical behavior is not always predictable. Hydrogen sulphide for example is particularly hazardous; although it has a very distinctive 'bad egg' odour at concentrations above 0.1ppm, exposure to concentrations of 50ppm or higher will lead to paralysis of the olfactory glands rendering the sense of smell inactive. This in turn may result in the assumption that the danger has cleared. Prolonged exposure to concentrations above 50ppm will result in paralysis and death.

Although the definitions for maximum exposure concentrations of toxic gases vary according to country, limits are generally time weighted, as exposure effects are cumulative. The limits stipulate the maximum exposure during a normal working day. Gas Detection Systems It is important to note that whereas portable gas detection instruments measure and alarm at the TWA (time-weighted alarm) levels, instantaneous alarms are also set at the same numerical values to provide early warning of an exposure to dangerous gas concentrations. Workers are often under risk of gas exposure in situations where atmospheres cannot be controlled, such as in confined space entry applications where alarming at TWA values would be inappropriate. Both flammable and toxic gases pose serious hazards in petrochemical processing facilities. Multi gas mixtures are also a common danger especially in confined spaces. Fixed gas detectors can be positioned in strategic zones and operatives undertaking maintenance or cleaning work. hot work areas in confined spaces should always be fitted with portable gas detectors. Depending on the application, diverse range of gases like Methane (CH4), Hydrogen sulphide (H2S), Nitrogen oxides (NOx), Chlorine (Cl2) and Oxygen (O2) can be present during the process application. Crowcon Gas Detectors Crowcon offers a very wide range of portable and fixed gas detectors for virtually any application in the petrochemical industries. The company also offers control systems for monitoring multiple arrays of fixed detectors, and gas sampling systems, which use pumps or compressed air-driven vacuum generators to extract air/gas samples from the area to be monitored and present the samples to one or more gas sensors. Most gas detectors, including Crowcon's, should be calibrated every six months to ensure optimum operation. However, a new range of IR (infrared) detectors allow users to extend maintenance checks to once every 12 months - and this only requires a 'gas test', not full re-calibration, which is more time consuming. 'Bump-test' stations and intelligent instrument management hubs, such as Crowcon's Checkbox, also enable simple day-to-day testing of portable gas detectors and easy management of maintenance cycles. All Crowcon's instruments are designed with for a minimum 10 year life-span. Sensor life depends on technology, with 2-3 years typical for electrochemical cells and oxygen sensors and 5 years+ for IR sensors. Future Trends It is likely that both portable and fixed hydrocarbon gas detectors will use IR sensors rather than the traditional catalytic bead (pellistor) sensors currently used in most detectors. IR sensors provide increased reliability, more dependable operation and increased life-times when compared to pellistors. The cost of IR sensors has fallen in the past few years, and a commercial case can easily be made for

switching to IR technology. Crowcon is leading the way in this new technology. Its new IR flammable gas detector, the IREX, was specifically designed to replace pellistor type flammable gas detectors and results in significantly faster response times and greatly reduced zero drift compared to pellistor detectors. Capable of detecting methane, butane, propane and many other hydrocarbons, the IREX is specifically designed for applications such as offshore platforms, refineries, gas storage and distribution networks, sewage treatment plants and certain manufacturing processes such as aerosol production.