we COURSE MATERIAL SUBJECT NAME: SAFETY IN CHEMICAL INDUSTRY SUBJECT CODE: IS-107 CERTIFICATE COUSRE IN INDUSTRIAL SAFETY (Duration: 1 Year) Conducted By ConnectIT Solutions Flat No:302, Madhu Construction, Opp Sindhu Travels, SR Nagar, Hyderabad — 5000038mE ; AB cep ens EB oe : oeCONTENTS Topic No. Topic Name Page No. T Place of Safety in Chemical Industry 1 2 “Types of Chemical Hazards and Controls AI 24 3 Criteria for Siting and Layout of Chemical Plants and A Plant Area Classification 4 UN Classification of Hazardous Goods 7 04 5 Compatibility of Chemicals 7 15 6 ‘Chemical Labelling eG 1617 7 Safety in Fertilizerindustry 18 8 Safety in Pesticide Industry 19-23 9 Safety in Polymer Plants ee 24-26 10 Safe Storage and Handling of Flammable, Corrosive and aa Toxic Chemicals Ti “Transportation of Hazardous Material By Different ? Mais oS 33-38 2 Transfer of Chemicals By Pipelines within and Outside aa installations, Above and Under Ground B Safe Procedure of Start up and Shutdown Procedures 45-50 it Material Safety Data Sheets Laat 51-62 is Work Permit System a ie 63-68 16 Tnspection techniques for Plants, Reaction vessels, Check Lists for routine inspection, Checklist for specific. 69-74 maintenance and breakdown. 7 Pressure Vessels (Fire and Unifired) ae 75-93 18 Safe Storage and Handling of Chlorine 94.97 1 ‘Safe Storage and Handling of Ammonia A 98.99 20 Safe Storage and Handling of LPG 7 100-101 2 ‘Safe Storage and Handling of EO 102-103, 2 ‘Safe Storage and Handling of Gas Cylinders 104-106 2 Corrosion & Erosion 107-112 24 Dow and Toxicity Indices 113-117 25 Pipelines — Identification-color code 118-126 26 Precautions in the case of Processes or operations involving explosives or flammable dusts, gases, vapours 127-153 etc 27 Hazards in Unit Operations & Unit Process and Safety 154-189 B Fire & Explosion O 190-225 29 Previous Questions & Examination Papers 26-24818107- Safety in Chemical Industry 1. PLACE OF SAFETY IN CHEMICAL INDUSTRY ‘Though safety in each field is of equal importance, safety in chemical field needs more attention because of its specific nature. Chemical safety seems more complicated than civil, mechanical or electrical safety because each chemical has many properties, many processes, many hazards and many controls. The state, pressure, temperature, process parameters etc., are also changeable. Many hazard data and complete reaction documents are still not available. Many hazards are known after the accident only as in case of Bhopal and so many incidents only as in case of Bhopal and so many incidents. Engineering controls may not be possible or available at many places. Control devices and personal protections are inadequate many times. Waming devices may either not be available or not be functioning. well. All these diversified working conditions and operational situations pose many dangers which need their proper knowledge and attention followed by proper safety measures and proper preventive as well as corrective maintenance. Bhopal accident is remarkable. It caused more than 2500 deaths, many more injuries, after-effects and become world famous attracting everybody's attention toward chemical safety. It has opened the eyes and shaken the governments and all safety people to wake up. Many expert committees have been formed and safety reports are published. The factories act, is rapidly amended to include many matters on chemical safety. Many seminars have been held and the chemical wave is still continued, This shows the significance of chemical safety. Certificate Course in Industrial Safety Page L1S107- Safety in Chemical Industry 2, TYPES OF CHEMICAL HAZARDS AND CONTROLS. People working in chemical factories and dwelling nearby are exposed to various types of chemical hazards. Inflammable, explosive, toxic, corrosive, reactive, radioactive, oxidising, reducing, decomposing, incompatible and hidden hazardous nature of chemicals ‘poses material or property hazards. In process, chemical and physical change, chemical reaction, pressure, temperature, level, flow, quantity and other parameters create process hazards. The vessels and equipment in which the chemicals are stored, handled or processed, pose vessel hazards. The inadequate, defective, under-designed or wrongly modified control devices or failure thereof cause control hazards. Fire or explosion causes fire hazards. Effluent disposal and gaseous emissions bring pollution and toxic hazards. Leaks, spills and splashes because handling hazards. Absence, non-use or failure of fire fighting equipment, personal protective equipment, emergency control devices reveal accident and emergency hazards. All other unsafe working conditions and unsafe actions pose a variety of hazards that all need to be prevented and controlled, Many safety measures are available to ‘deal with above hazards, Identification of hazards and contents, properties, quantity of chemicals, their content minimisation, proper storing, handling and packing; auto control, recording and waming devices for level, pressure, vacuum, temperature, flow, feed, speed, cooling, heating, stirring, discharge, contamination; remote control. devices, proper ventilating, exhaust, scrubbing, neutralising, inactivating and incinerating devices; monitoring, measuring, recording, tripping, correcting, and controlling system, fire fighting and personal protective equipment, emergency and disaster management, engineering controls and well designed process and plant layout and fully safe actions of workpeople are utmost necessary to fight these hazards and to control over them. Some types of hazards anti controls are as _ follows: Health (Toxic) Hazards: a) Types of effeets are- Allergy, Invitation, Oxygen deficiency (asphyxiation), Systemic poisoning (Eg. damage to liver, kidney, CNS, reproductive system ete.), Cancer, Damage to airborne foetus (teratogenesis), Genetic effects on future generations (mutagenesis), Dust effect (pneumoniosis). Some effects are acute (Jocal or short term) and some are chronic (long term, delayed or after repeated exposures). Certificate Course in industrial Safety Page 215307: Safety in Chemical Industry b) Factors creating effeets are ~ Type of concentration of chemical, combined effects of mixtures, properties of the ‘material including its toxicity, Work methods, Nature of exposure (short term, long term) Routes of entry (through nose, mouth or skin) and Individual susceptibility. Fire and Explosion Hazards: Heat generation due to chemical reaction, Open flame, Radiant heat, Friction, Spontaneous combustion, Electric current, Static electricity and fuel or Solvents like Low flashpoint and low boiling point liquids, Gases and Solids (dusts, powders, lumps, crystals) Biological Hazards: Biohazards refer to plants, insects, animal and human pathogens that pose a potential risk to the health of humans, animals and also to the environment. Their ill effect isthe illness through infection or disruption of the environment. They can be unique to a specific oy fuga i Skin Infections | _ Skin Infections occupation or may affect the general public as | , Skim Infections | Skin epidemic (¢.g. cold virus) or spread from person} Animalhandlers | bartenders cana as farmers Canny workers: to person like highly publicised AIDS, Panera coe : is possible in bio- | Food processors Dishewashers Occupational exposure is possible in bio- | Feed pr a Iaboratory work, hospitals, nursing or medical Parsiti Viral ‘Skin Infection: Skin h He research, farming, agriculture, slaughterhouses, | agriculture Dayoan a <. Grain handlers Dentists ‘meat cutting and. iB ete. ‘Harvesters Medica) Biological infections and parasitic | Livestock workers | practitioners 7 Longsh ui andl diseases are caused by contact with domestic, | Sto Sennen ete laboratory and other animals occupations of such Diohazards are: abattoirs, agriculture, animal attendants, bone and bone meal processing, butchers, dairy, forestry, hair, bristle processing, ivory hom processing, Jaboratory animals, hospitals, slaughter house, farms, gardens, chemical factories, meat packers, poultry, sewerage workers, stock farming, tanneries, veterinary work, wild life management, wood industry, transport and handling of animals etc. Disease-class wise worker groups are as under: Diseases caused by biological agents are: Anthrax, Brucellosis, catarrh, erysipeloid, herpes virus infections, infections hepatitis, leishmaniasis, leptospirosis, lymphocytic choriomeningitis, mice infection, Q fever, rabies (dog bite, hydrophobia), rat bite fever, ringworm, salmonellosis, toxoplasmosis, TB and asthma. Certificate Course in Industral Safety Page1S107-Safety in Chemical industry Biohazards can enter into body through inhalation, ingestion, injection or skin contact. ‘The type and virulence of the organisms and the individual's body resistance can decide whether or not the person may contract the disease. If other chemical or physical hazards are combined in the environment, the combined effect can be enhanced. Thus other environmental stresses may cause additive or synergistic effect. Viral oncology (tumour) research can provide information on risk of cancer due to viruses. Safety and Control Measures: These are necessary to prevent health effects of toxic, highly infectious or oncogenic bio-agents. A written control plan including instructions for awareness, emergency action, safe procedure for handling, first-aid and reporting is useful. Employees should be immunised by effective vaccine if available. Vaccination is effective against smallpox, tetanus, yellow fever, diphtheria and hepatitis B. Proper placement and medical surveillance are also important. Pre-placement medical examination can give a baseline reference. Work assignment records should be maintained. Pregnant women working in oncogenic virus laboratories should be counselled at the earliest possible time. They should be transferred to a nonvirological department if possible. Good housekeeping, quick decontamination of place and equipment, ‘sterilisation, cleaning by germicide, use of PPE, no eating, drinking, smoking etc. In work areas, display of biobazard symbol, animal care and handling, bio-safety cabinets (local exhaust ventilation), effective filtration of room-air, ultraviolet air locks and door barriers to separate areas of unequal bio-risks, change rooms, safety showers, effluent treatment etc., are important safety measures. AIDS (Acquired Immune Deficiency Syndrome) caused by HIV (Human Immunodeficiency Virus) reduces body's ability to fight infections. Diagnosis of white blood cells (WBC), no sexual contact with AIDS partner, avoidance of intravenous drugs and medical treatment are useful. Atomic Radiation Hazards Radioactive substances and Radiation processes (X-ray, NDT, Nuclear power plant etc.) cause severe health hazards. General Preventive & Control Measures: Six Basic Principles 1. Elimination of substance, process or exposure of hazard. 2. Substitution of safer alternative. 3. Distance, Guard, Enclosure, Isolation, Shielding or Segregation of hazardous process. Ventilation, general & local exhaust. Personal Protective Equipment and Personal hygiene. ae Certificate Course in industrial Safety Page41S107- Safety in Chemical Industry 3. CRITERIA FOR SITTING AND LAYOUT OF CHEMICAL PLANTS AND PLANT AREA CLASSIFICATION 1. PLANT SITING AND LAYOUT ‘+ Rural, urban and mixed areas, low population density of high population density ‘© Ifhazard is toxic gas release, effect of distance to reduce gas concentrations 2. PLANT LAYOUT CONSIDERATIONS Segregation of different risks + Separation of flameproof and non-flame proof areas as per Factories Act and Tariff Advisory committee ‘+ Segregation of plants having explosion potentials, keeping costs on utilities low ‘© Minimisation of vulnerable pipe work a © Containment of accidents ~ + Efficient and safe construction of match factories light roof construction + Facilitation of process operations + Efficient and safe maintenance ~ clear distances to facilitate this ‘© Minimisation of personal injuries —_minimum no. of operators at time working behind barrier walls, with mirrors to observe processes + Safe control room design ~ entrance to be guarded by blast wall + Emergency control facilities - ECC Disaster Plan + Congregation points, security problems, fire fightin facilities inside factory and in neighbourhood, access plant for emergency services 3. Flow Principles = © Process layout © Functional layout + Materials always on the more in a straight forwards manner + Materials flow to follow process flow design + Importance of efficient materials holding quantities necessity of large inventories 4, Layout Techniques + Method study for best layout + Use of 2 dimensional and 3 dimensional templates + Algebraic matrix to determine minimum cost of material handling movements 5. Site Layout + Preliminary layout Certificate Course in Industrial Safety PageD18107- Safety in Chemical Industry + Main layout topography, weather, environment, transport, power, water and effluent services, legal constraints 6. Segregation of Areas : Zones 0,1 and 2 - * Class A,B and C as per Petroleum Act ‘Classification of flammable liquids — as per NFPA. + Safe separation distances — for bulk storages as per Petroleum Act (Underground — above ground), as per SMPV Rules under Explosives Act depending upon proportion of chemicals stored and quantities stored — distance between vessels — different types of transformers * Protection screen walls ~ no double tier storages * Vapour travel barriers walls ~ blast walls + Dished ends of vessels not to face each other 7. SERVICES / UTILITIES 7 * Boiler, Thermic Fluid Heater, Compressors, Electric sub-station, Pumping stations, transformers 8. EFFLUENTS DISPOSAL ‘+ Incinerators, biological treatment, liquid and acid effluents + Hazardous solid wastes disposal ~ Hazardous waste management rules 9, Traffic + Types of trafic inside work areas # Adequate space for road tankers parking + Parking of employees and visitors vehicles + Parking lots— angular, parallel parking : © Outwards traffic to merge slowly into the main road traffic i Rail lines inside work areas © Entry into plants form main and side roads 10, Emergencies © ECC, Congregation points + Emergency service vehicles parking + Ring main —Hydrant system 1, Security PageO * Boundary fence, gate house, watch and word training Certificate Course in Industrial Safety1S107- Safety in Chemical Industry 12, Plot Layout Earthquakes thunderstorms © Types of ventilation — natural, artificial, safety, vacuum exhaust, A/c ~ heating toxics, ventilation fiom fire, health and comfort points of view 13, Hazards © Earthquakes, thunderstorms + Types of ventilation - natural, artificial , safety, vacuum exhaust, A/c- heating toxics, ventilation from fire, health and comfort points of view 14, Fire Fighting Facilities ‘+ Typesmumal aids schemes 15, Equipment layout, * General considerations, corrosive materials 16. Control Rooms ‘© General considerations, ventilation, inlet of air from nearly plant areas, control facilites, layout construction 17. Pipe work layout + May bern as a double layer bed — service lies on top upper and process lies on lower duct, compatibility of adjacent pipe work, splash guards for acid/alkali splashes through flanged joints * Sample points at 1m above floor and not at eye level, ‘© Pipe bridges over roads should be minimum necessary ~ no damage by truck forklifts and mobile cranes * Discharge from pressure vessels, relief system (valves and bursting rapture discs) to be piped away in a closed system. Some scrubbing may also be necessary — limitations : 18, Storage Layouts «Flammable liquids / gases — at atmospheric pressure and under pressure + Controls should not allow flammable liquids or heavy vapour to collect in a depression + Kerbs, dyke walls — principles e.g. LPG Vessels full of liquids are very heavy, hence site should have good load bearing characteristics + Segregation of storages from process areas ~ minimum 15 meters Certificate Course in industrial Safety Page71S107- Safety in Chemical Industry + Storage area should be in groups ~ groupings should be such as to allow common building, common fire fighting facilities for each group * Access on all 4 sides of each bund area, if materials are highly hazardous, terminals should be near the entrance may be at site boundary, provided it does not affect neighbours installations * Monitoring of storage conditions provision of wind socks Certificate Course in Industrial Safety15107- Safety in Chemical Industry 4, UN CLASSIFICATION OF HAZARDOUS GOODS ‘We come across a no. of chemical sin our day today life. Early in the moming we use toothpaste, we use soap for bath and washing clothes, we use detergents also, we use LPG for cooking, we use petrol or diesel for our vehicles, and we use acids and phenyl for washing toilets. We use poisonous chemicals like insecticides so on and so forfn. Many more Tee? examples can be given of the use of chemicals in our daily life, There are hundreds and ‘ : A wun wOmO™ thousands of chemicals and every day some new chemicals are being synthesized. Itis highly Gifficult to study these chemicals individually. Hence classification of chemicals is essential, so that they can be studied in a group.Different criteria’s are applied for classification of chemicals, e.g Organic and inorganic chemicals, metals and non metals; natural and synthetic, petrochemicals, jes pigmens, pharmaceaticals, ete United Nations recommendations on the transport of dangerous goods have classified these ~ chemicals into Nine Classes. ‘These recommendations aim at presenting a basis scheme of provision that will allow national and international regulations governing the various modes of transport within it in a uniform fashion. It should be noted that the numerical order of the classes is not that of the degree of danger. + CLASS1 — :Explosives Division 1.1 - Explosives with a mass explosion hazard, Division 1.2 - Explosives with a projection hazard. Division 13 - Explosives with predominately fire hazard. 5 Division 1.4 - Explosives with no significant blast hazard, = Division 1.5 - Very insensitive explosives Division 1.6 - Extremely insensitive explosive articles * CLASS2 — : Gases Division 2.1: Flammable Gases Division 22: Non flammable Gases Division 23: Poison (Toxic) Gases © CLASS3 — : Flammable Liquids Division 3.1 - Flashpoint below - 18°C (O°F) Division 3.2 - Flashpoint 18°C and above but less than 23°C (73°F) Division 3.3 - Flashpoint of 23°C and up to 61°C (141 °F) Page Certificate Course in industrial Safety1S107- Safety in Chemical Industry * CLASS4 — : Flammable Solids, Spontaneously Combustible Materials and Materials that are dangerous when wet Division 4.1 - Flammable Solids Division 42 - Spontaneously Combustible Materials Division 43 - Materials that are dangerous when wet + CLASSS _: Oxidizers and Organic Peroxides Division 5.1 - Oxidizers Division 5.2 - Organic Peroxides * CLASS6 —_ : Poisonous and Btiologic (Infectious) Mateiials Division 6.1 - Poisonous Materials Division 6.2 - Etiologic (Infectious) Materials * CLASS7 _: Radioactive Materials * CLASS8 —: Comosives * CLASS9 —_ : Miscellaneous Hazardous Materials See IS: 1446 for classification of dangerous goods. Arrangement for loading and unloading of the liquid has to be well designed. It is preferred to load toxic.and flammable material from the bottom. It is preferable to provide a discharge pump on the tank, oR Drums, crates and cylinders are also transported by trucks. The important thing to see is : that the chemical is securely packed so that spillage does not occur on the road and the toxic vapors are not released. The cylinders or drums should be securely lashed so that they do not oe fall off the truck and cause danger. The driver and the attendant should be fully conversant with the nature of the material and the hazards involved; and trained to handle the situation. Page LQ Certificate Course in Industrial Safety1S107- Safety in Chemical Industry Class 1: Explosives ertitory of the US. Information on this graphic changes depending on which, [Explosive Dangerous Goods have compatibility group letters assigned to facilitate segregation [transport. The letters used range from A to S excluding the letters I, M, O, P, Qand R. The example above} Ishows an explosive with a compatibility group "A" (shown as 1.1A). The actual letter shown would depend| lon the specific properties of the substance being transported, For example, the Canadian Transportation of Dangerous Goods Regulations provides a description o: |compatibility groups. 1.1 Explosives with a mass explosion hazard Ex: TNT, dynamite, nitro-glycerine. 1.2 Explosives with a severe projection hazard. 1.3 Explosives with a fire, blast or projection hazard but not a mass explosion hazard. 1.4 Minor fire or projection hazard (includes ammunition and most consumer fireworks). 1.5 An insensitive substance with a mass explosion hazard (explosion similar to 1.1) 1.6 Extremely insensitive articles. ‘The United States Department of Transportation (DOT) regulates hazmat transportation within the} 1.1 — Explosives with a mass explosion hazard. (nitroglycerin/dynamite) 1.2— Explosives with a blast/projection hazard. 1.3 — Explosives with a minor blast hazard, (rocket propellant, display fireworks) 1.4— Explosives with a major fire hazard. (consumer fireworks, ammunition) 1.5 — Blasting agents. 1.6 — Extremely insensitive explosives, vision” of explosive is shipped] Hazardo Hazardous Hazard us Materials Materials ous Materials Class 1; Class 1.1 fe oe Explosives Explosives Cates ass Explosion Hazard [BlasvProjection Hazard Hazardo Hazardous Hazard us Materials Materials ous Materials Class 1.3; Chss 1.4; = clase Explosive: Explosives aoe ee cane is Agents Ainor Blast Hazard ajor Fire Hazard lasting Agents Hazardous q Materials * ‘Class 1.6; Explosives ixtremely Insensitive Explosives Certificate Course in Industrial Safety1S107- Safety in Chemical Industry __Class 2: Gases : a] ave subsidiary risk classes; poisonous or corrosive. Gases which are compressed, liquefied or dissolved under pressure as detailed below. Some gases} 2.1 Flammable Gas: Gases which ignite on contact with an ignition source, such as acetylene andl hydrogen. 22 Non-Flammable Gases: Gases which are neither flammable nor poisonous. Includes thi cryogenic gases/liquids (temperatures of below -100°C) used for cryopreservation and rocket wt such as nitrogen and neon. 2.3 Poisonous Gases: Gases liable to cause death or serious injury to human health if inhaled; examples are fluorine, chlorine, and hydrogen cyanide. Hazardo Hazardous Hazard us Materials Materials ous Materials Class 2.1;| Class 2.2; Class Flammable Gas Nonflammable Gas peck ias Hazardo Hazardous us Materials \ Materials Class 2.2: > Class 2.3; Oxygen Inhalation __ Hazard (Alternative (Altemative Placard) Placard) Class 3: Flammable Liquids [Flammable liquids included in Class 3 are included in one of the following packing groups: Packing Group I, if they have an initial boiling point of 35°C or less at an absolute pressure of 101.3} kPa and any flash point, such as diethyl ether or carbon disulfide; Packing Group HU, if they have an initial boiling point greater than 35°C at an absolute pressure off 101.3 kPa and a flash point less than 23°C, such as gasoline (petrol) and acetone; or Packing Group Ul, if the criteria for inclusion in Packing Group I or II are not met, such as keros: and diesel. Note: For further details, check the Dangerous Goods Transportation Regulations of the} country of interest, Hazardo Hazardous Hazard us Materials Materials Br ous Materials Class 3; Class. Aree Class 3; Flammable Combustible ae Fuel oil Liquids (Alternate Placard) (Altemate Placard) Hazardous a Materials | Class 3: Gasoline} (Alternate Placard) Certificate Course in Industrial Safety15107- Safety in Chemical Industry Class 4: Flammable Solids. Hazardous Materials Class Spontaneously Combustible Solids 42; aa substances that are easily ignited| Flammable Solids: Solidl/4.2 Spontaneously Combustible: Solid) lsubstances that ignite spontaneously| land readily combustible|(aluminium alkyls, white phosphorus). (nitrocellulose, magnesium, safety| ,or strike-anywhere matches). Hazard ous Materials Class 43: Dangerous when Wet 4.3. Dangerous when Wet:| Solid substances that emit al lammable gas when wet or react violently with water] (sodium, calcium, potassium, calcium carbide). Class 5: Oxidizing Agents and Organic Peroxides Hazardo us Materials Class 5.1; Oxidizing Agent| ‘Hazardous Materials 5.2: Organie Peroxide ing Agent [5.1 Oxidizing agents other than| ‘organic peroxides (caleium| jpypochlorite, ammonium nitrate, hydrogen peroxide, potassium] permanganate), |cumene hydroperoxide). [5.2 Organic peroxides, either in liquid or solid form (benzoyl peroxides, Class 6: Toxic and Infectious Substances A Hazardous Materials _ 4 = n : Class 6.1: Poison Hazardous Materials Class 6.2: Biohazard 61a Toxie substances which are liable to cause death or serious injury. to} human health if inhaled, swallowed oi by skin absorption (potassium) cyanide, mercuric chloride). 6.1b (Now PGIII) Toxic substances, which are harmful to human health] (NB this symbol is no longer authorized by the United Nations) (pesticides, methylene chloride). 6.2 Biohazardous substances; the World Health Organization] (WHO) divides this class into two categories: Category A: Infectious; and Category B: Samples (virus cultures, pathology specimens, used intravenous needles). op ar Certificate Course in industrial Safety15107- Safety in Chemical Industry Class 8: Corrosive Substances Class 9: Miscellaneous Class 7: — Radioactivel [Substances Hazardo ‘us Materials Class 7: Radioactive ‘Hazardous Materials Class Conpsive 8; Hazard ous Materials Class 9:| Miscellaneous [Radioactive substances comprise| lsubstances or a combination o' lsubstances which emit ionizing| [radiation (uranium, plutonium). [Corrosive substances are substances that can dissolve organic tissue or} Jseverely corrode certain metals: 8.1 Acids: — sulfuric hydrochloric acid 82 — Alkalis: potassium] hydroxide, sodium hydroxide . acid, [Hazardous substances that do) hnot fall into the other categories \@sbestos, air-bag inflators, sel inflating life rafts, dry ice). Page L 4 Certificate Course in Industrial Safety1S107- Safety in Chemical Industry 5. COMPATIBILTIY OF CHEMCIALS Compatible Chemical means which can be stored or handled with that chemical to which it is compatible. Incompatible chemical means which should not be stored or handled with that chemical to which its incompatible. While storing chemicals, it is necessary to know the incompatibles — those that react exothermally with one another. For example, fuels and reducing agents are incompatible with oxidizing agents. No two incompatibles should be stored together. Some of these incompatible chemicals are: Acid Chemicals versus Basic Chemicals — Free acids like HCI, H»S0,,, CHs COOH or chemicals like potassium bisulphate should not be stored with bases like ammonia, lime, soda, metal oxides, etc Ammonium Salts versus Basic Oxides or Carbonates — These will react, may be with tragic end like fire or explosion; hence should not be stored together Bleaching Powder versus Turpentine — Bleaching powder liberates chlorine, which reacts exothermally with ammonia, ammonium carbonate or unsaturated organic substances like turpentine or linseed oil. This may be a source of fire. Hence adequate care should be taken while storing such chemicals. ‘A following table gives an elaborate list of incompatible chemicals ( Annexust 4) Certificate Course in industrial Safety Page L5Acetone Acetylene Alkali and alkaline earth metals (suchas powdered aluminum or magnesium, calcium, lithium, sodium, potassium) Ammonia (anhydrous) ‘Ammoniumnitrate Aniline Axsenical compounds Aides ‘Bromine Calcium oxide Carbon (activated) Carbon tetrachloride Chlorates (Chromic acid and chromium trioxide Chlorine es Copper “Ac LIST OF INCOMPATIBLE CHEMICALS Chemical Acetic acid nin Incompatible with Chrisie, nitric acid hydroxy] compounds, ethylene glycol, ‘perelori sid, peroxides, permanganates Concent and sulphuric cid mixtures Clorn, tromine, coppe, Murine, iver, mercury ‘Wat, catbor tetrachloride or other chlorinated hydrocarbons, carbon oxide, alopens ‘Meret (ramp, in nianometers), chlorine, calcium hypochlorite, “iodine; bromine, hydrofluoric acid (anhydrous) Acids, powdredmetals,lammable liquids, chlortes, nitrates, sulphur, $inely divided organic combustible materials ‘itre sci hydrogen peroxide Atiy reducing agent Acids See chlorine Water Calcium hypochlorite, all oxidizing agents Sodiam Ammoniv salts, acids, powdered metals, sulphur, finely divided ‘organic or combustible materials ‘Acetic acid naphthalene, camphor, glycerol, aleoho,ammable liquids in general, ‘Atnmonia, aetylene, butadiene, butane, methane, propane (or other petroleum gases), hydrogen, sodium carbide, benzene, finely divided metals turpentine Ammonia, ethane, phosphine, hydrogen sulphide ‘Acetylene, hydrogen peroxide aChemicat Cumene hydroperoxide Cyanides Flammable iquds Fluorine Hydrocarbons (such as butane, propane, benzene) Hydrocyanic acid Hydrofluorie acid (anhydrous) Hydrogen sulphide Hypochlorites Iodine Mercury Nitrates: Nitric acid (concentrated) Nitvites ‘Nitroparaffins Oxalieacid Ooyeen Perchloricacid Peroxides, organic Phosphorous (white) Potassium, Potassium chlorate ‘Potassium perchlorate (see also chlorates) Potassium permanganate Selenides Silver Sodium Sodium nitrite Sodium peroxide Sulphides: Sulfie acid ‘ellurides NOTE — The flloing list i nota complet Incompatible with ‘Acids (organic or inorganic) Acids 1S 4209: 2013 Ammoniumnitrate, chromic acid, hydrogen peroxide, ntti acd, sodium, peroxide, halogens Allothercheinicals *Flootine, chlorine, bromine, chromic acid, sodium peroxide ‘Nite acid, alkali Ammovia (aqueous or anhydrous) Fumingnitric acid, oxidizing gases Acids, activated carbon Acetylene, ammonia (aqueous or anhydrous), hydrogen Acetylene, fulminie acid, ammonia Acids Acetic acid, aniline; chromie acid, hydrocyanic acid, hydrogen sulphide, lammoable liquids and gases, copper, brass any heavy metals Acids Inorganic bases, amines Silve mercury ils, grease, hydrogen, flammeble liquids, solids or gases Acetic anhydride bismuth and its alloys, alcohol, paper, wood, grease, oils Acids (organic or Air, oxygen, alkalis, reducing agents Carbon tetrachloride, carbon dioxide, water Sulphuric and other acids Sulphuric and other acids ), avoid friction, store cold Glycerol ethylene glycol, benzaldehyde, sulphuric acid Reducing agents Acetylene, oxalic acid, tartare acid, ammonium compounds, fulminic acid Carbon tetrachloride, carbon dioxide, water Ammonjumnitrate and other ammonium salts Ethyl or methyl alcohol, glacial ‘acetic acid, acetic anhydride, benzaldehyde carbon disulfide glycerin, ethylene glyco, ehylacetate, rmethylacetate furfural Acids ‘Potassium chlorate, potassium perchlorate, potassium permanganate (imilar compounds of light metals, such as sodium, itium) Reducing agents of incompatible; this as wo be uted only at pute1S107- Safety in Chemical industry 6. CHEMICAL LABELLING Chemical container labels inform us about identity of the content, its potential hazards, manufacturer's contact information, PPE necessary and other information, Labelling standards and requirements are established by several agencies like Department of ‘Transportation (DOT), NFPA, OSHA, ANSI, HMIS and ISO. DOT diamond shaped labels are required on all shipping packages containing hazardous materials and wastes. Larger DOT placards must be visible on all bulk packages, freight containers, rail cars, etc. Strict guidelines specify the size, colour, appearance and content of DOT labels. ‘The National Fire Protection Association (NFPA) of USA has developed the familiar four colour diamond hazards identification system for chemicals. Each coloured section of the diamond represents a different hazard labelled with the numbers 0-4 to rate the severity of the hazards (4 being the most severe). Chemical Labelling: Chemical container labels inform us about identity of the content, its potential hazards, manufacturer's contact information, PPE necessary and other: information. Labelling standards and requirements are established by several agencies like Department of ‘Transportation (DOT), NFPA, OSHA, ANSI, HMIS and ISO. DOT diamond shaped labels are required on all shipping packages containing hazardous materials and wastes. Larger DOT placards must be visible on all bulk packages, freight containers, rail cars, etc, Strict guidelines specify the size, colour, appearance and content of DOT labels, ‘The National Fire Protection Association (NFPA) of USA has developed the familiar four colour diamond hazards identification system for chemicals. Each coloured section of the diamond represents a different hazard labelled with the numbers 0-4 to rate the severity of the hazards (4 being the most severe). Certificate Course in Industrial Safety Page 1615107- Safety in Chemical industry eran {Combose that aig 2007) FIRE 2 CATION. \hatbe eso or amore bhp git fatga «2007 {LNARKING - Conde ipa on stn impo ees ano <7 4 DANGER -vRtrpayapome ot dipie ea aan condone ‘bu ea aro ate bd Boab Wh, Pap «73°F Common Specific NFPA Hazards OX Oxidizer ACID Acid ALK Alkali (Base) COR Corrosive W_ Water-Reactive {use no wat) Radioactive Certificate Course in industrial Safety Page L 715107- Safety in Chemical Industry 7. SAFETY IN FERTILIZER INDUSTRY Fertilisers are natural (manure) or artificial. Artificial fertilisers are produced in chemical plants ‘and they may be organic or inorganic, nitrogenous, phosphatic, potash and trace clement fertilisers, In the warehousing stage, phosphate, potassium-salt and other dust are released. In chemical processing plant, air pollution by toxic gases (fluorine compounds, H,S0s, NO, HCL, CO and NF gases) and dust, high air temperature and noise are noticed, Closed and efficient ventilation is necessary. In finishing processes, weighting, bagging and storing, gaseous emissions and fluorine compounds are released. Phosphates and other raw material contain 10% or more fiee silica which may cause pneumoconiosis. The just of soluble fertilisers causes irritation, Where ammonia is used, safety measures for ammonia storage tanks, its pipelines, CO detection and alam, safety from synthesis gas and ammonia, handling and changing of catalyst, safety aspect in air separation unit, gasification section, carbon extraction system, safety in nitro phosphate and nitric acid plants, safety in coal handling, LSHS plants, Naphtha tank farm and process area are utmost required, Other safety measures are: 1. Mechanisation and automation of production processes, provision of remote control, careful assembly and safe operation of equipment and heat insulation. 2. Process segregation and walls and floor covering to absorb fluorine compounds. 3. General ventilation, exhaust ventilation of enclosed plant, cleaning of exhaust air and waste water. 4, Breaking of oversize coal and removal of stones, metal pieces ete, from the coal before feeding them to boilers Education and personal hygiene Use of PPE and safety showers Safety and sanitary supervision Pre and post medical examination including radiographs of the locomotors system and lungs. IS : Fertiliser - Glossary 1304, sampling and tests 6092, bagged, handling and storage 5985, mixtures 7863, 9024, effluents - tolerances 2590, treatment and disposal 9841, application equipment glossary 9855, metering mechanism plate type 12599, feed roller type 12613, Urea ammonium phosphate based 8359, nitro phosphate based 7131, seed drills 6316, 6813, Phosphatic fertiliser industry, Limits of emissions 8635. Certificate Course in Industrial Safety Page L81S107- Safety in Chemical industry 8 SAFETY IN PESTICIDE INDUSTRY Pesticide is a chemical used to destroy an organism detrimental to hanuman interest. It includes insecticides, fungicides, herbicides, - rodenticides, bactericides, matricides, 2 nematocides, moluscide. They are generally halogenated (Cyclodienes, Bischlorophenyls, cycloparaffins, Organo-chlorines and chlorinated trepanises) or organ phosphorus (Parathion, marathon, TEPP, OMPA, DDVP, abate, ciodrin ete.) type. They are classified as extremely hazardous, highly hazardous, moderately hazardous, slightly hazardous, ete According to WHO, pesticides are classified as under. Class 1A Extremely hazardous: Chass 18. - Highly hazardous Class = Moderately hazardous oy Chess I - Slightly hazardous ne Organo-Chlorine Pesticides are used as insecticides, herbicides, nemotocides, fungicides and fumigants. Some examples are DDT, Aldrin, Di-eldrin, Endim, Heptachlor, Isodrin, Endsulfon. Organo-Phosphors pesticides are used to control insects, acaridst, melathion ethion, chlorpyrifos, phorate. Following points are important while using pesticides. 1. Lethal dose of pesticide indicating its killing strength and its health hazards. 2. Method of use or application 3. Route of absorption 4, Equipment by which it is applied 5, Formulation 6. Marking, labelling and safe disposal of containers 7. Storage of pesticides 8. Mixing of pesticides 9. Use of PPE 10. Protection by distance, wind direction, duration of handling and change of working method. Page 19 Certificate Course in Industrial Safety18107-Safety in Chemical industry Statutory Provisions: Schedule 24, Rule 95, APFR give statutory provisions for manufacture and handling of dangerous pesticides. ‘The measures include prohibition of employment of women and young persons, air space of 500 m h more per person, efficient exhaust draft on charging, discharging, blending and powder or liquid preparation, sound and sloping floor with gutters and drainage, daily washing workbenches of stainless steel, waste container with lid and waste disposal by burning, safe disposal of empty containers, no manual or direct handling, protective clothing and their daily washing, medical facilities including doctor and antidotes and medical ‘examination — pre employment, quarterly examin ation and record in Form 28, APFR additional interval of 10 minutes before each meal and before the end of the day’s work, ‘washing and bathing facilities with at least 50% bathrooms and | place for 5 workers w clean towels, in workrooms cloak room for clothing and PPE, mess room with in-charge person Schedule 24, Rule 95, APFR defines "Dangerous pesticides” as agents used for the purpose of controlling, destroying or repelling any pest or for preventing growth or mitigating effects of such growth including any of its formulations which is considered toxic under and is covered by Insecticides Act, 1968 & Rules made there under. Annexure-I, Cautionary Placard is similar in all above three State Rules and is reproduced below: Cautionary Placard 1. Pesticides are generally poisonous substances. 2. Therefore in rooms where these are handled- a. Do not chew, eat, drink or smoke; keep food or drink away from pesticides. b. Use the protective wear supplied e.g. gloves, aprons, clothes, boots, etc. 3. Before meals or when any part of the body has come in contact with the pesticides, wash with soap and water. Before leaving the factory, take a bath and change your clothing Do not use any container that has contained a pesticide as a pot for food or drink. Do not handle any pesticide Ivit.11 bare hands; Use a handled scoop. Avoid spilling of any pesticide on body, floor or table. Maintaill scrupulous cleanliness of body and clothing and of your surroundings. 0. In case of sickness like nausea, vomiting or giddiness, inform the manager who will make necessary arrangements for treatment, Certificate Course in industrial Safety Page201S107- Safety in Chemical Industry Effects and Controls: Pesticides and agrochemicals enter into the body through inhalation, ingestion or skin absorption. They are classified as toxic, harmful, corrosive, irritant, flammable, explosive or oxidising. Toxicity is mostly denoted by LDso or LCso values. All agrochemicals should be labelled, transported safely and correctly stored in a room (locked and cool). Containers should be opened only after wearing comect respirator (positive air pressure), neoprene or plastic hand gloves, aprons, boots ete, Protective clothing is always essential while handling pesticides. Inhalation of vapour should be avoided. Contact with skin, eyes and clothing should also be avoided. Contaminated clothing should be immediately changed; the entire body should be thoroughly washed with soap and water. After working with pesticides, shower bath should be taken and clothing should be changed. Contaminated equipment should be cleaned with soap orsoda ash, Local exhaust ventilation on filling line must be effective. ‘Types of effects may be acute (immediate) or chronic (prolonged or slow delayed). Some common symptoms are - dizziness, headache, shaking and weakness. More toxic effects may cause convulsions, irrational behaviour or unconsciousness, First-aid treatment includes - removal of affected person to a safe, clean and airy place, washing of the part affected and to put the person in recovery position (slipping on shoulder). On swallowing, vomiting should be induced if person is in consciousness. ‘Medical charcoal and plenty of water may also be given. Effect of organo-phosphorous pesticides is to reduce cholinesterase level in body and it can be noticed by pin-point in pupils (eyes). Blood cholinesterase activity test should be carried out every 15 days. If the level is found less than 62.5%, the worker must be transferred to another place where no exposure is possible. After medical treatment and safe report lie can be put back to his plant, But meantime the engineering controls should be provided or revised to eliminate the exposure, Leakage and spillage must be removed. Defect in PPE should be checked and removed. An Office Circular dated 27-7- 1995 of Factory Inspection Office, Bharuch, sent to pesticide factories, seems to be more important and suggests following safety measures: 1. For filling bottles or small containers of liquid, granules or powder, automatic filling machines with closed chamber and attached local exhaust ventilation must be used. Weighing, plugging and sealing operations and conveyor movement should also be Certificate Course in industrial Safety Page2 118107- Safety in Chemical Industry ‘automatic and under suction chamber so that a worker has not to touch anything and no spillage, vapour or dust shall touch his body. 2. To fill barrel or big container a chamber with exhaust hood and ventilation should be used, 3, To contain or collect leaking liquid small bund and pit shall be provided. Spilled pesticide should be neutralised or washed with dry clean cloth and stored in a dust-bin with spring-lid. Then it should be safely disposed or burnt out. 4, Workers engaged to shift move, clean or park the filled (plugged) container or to clean any spillage, shall be given goggles, long sleeved shirt and pent, good quality rubber hand gloves, waterproof suit or apron, gumboot and air-line respirator. Safety showers and bath rooms shall be provided. ‘5. Mliterate, untrained and temporary contract. Workers aire exposed to more risk, ‘Therefore such training should be given to them so that they call read or understand the necessary precautions. 6. Pedestal or positive air fan removes the vapour or dust from one worker to another. ‘Therefore it is inadvisable, Exhaust or negative air suction and air-line respirators are the effective remedies. Exhaled air should be passed through carbon bed filter or effective absorber and final vent discharge should be within safe limit. 7. Regular air monitoring at work place, PPM record and leakage checking are necessary. 8. A record of full name, address, signature, date of joining and photograph of all the workers at the time of first employment are useful to detect cases of delayed effects or after-service effects. 9. If pre-employment and subsequent medical examination shows blood cholinesterase level less than 62.5%, that worker should not be employed in pesticide work, If RBC level is also low, the worker should be kept away for 3 months from such process. Sufficient stock of PAN, Atropine etc. (antidotes) should be kept in the factory first- aid centre. 10. The workers must be aware that in case of symptoms (dizziness, headache, vibration, vomit etc.), which doctor they have to approach. They will follow the medical advice. 11. In each shift, qualified and trained supervisor shall strictly supervise the working conditions, work habits, methods, and use of PPE, washing, cleaning and no smoking, eating or drinking in work area, Certificate Course in industrial Safety pagel1S107- Safety in Chemical Industry Specified medical treatment is as under: 1 rays In case of skin contact of organophorous, it should be immediately treated with solution of 5-10% ammonia or 2-5% chloramines. Give injection atropine sulphate according to age, 2 to 4 mg intravenous. or intramuscular. Continue this injection every 5 to 10 minutes till pupil’s size and heart beats become normal. Give injection PAM (2-Pyridine Aldoxime Meth chloride) in glucose slowly. Toxogonin is a condensation product of pyridine Aldoxime and dichlorimethly ether Maintain fluid and electrolyte balance. Give antibiotic medicine to prevent secondary infection. Give Frusemide if lungs are swallowed or water filled. If breathing stops, artificial respiration must be tried till doctor comes. The patient should be kept in a cool and quiet place. Give oxygen if difficulty is in breathing. If breathing trouble is more, the victim should be shifted to hospital and put on ventilator. Certificate Course in Industrial Safety Page2 318107- Safety in Chemical Industry 9. SAFETY IN POLYMER PLANTS. In organic chemistry certain giant molecules such as starch, rubber, plastic or resin, synthetic fibres, cellulose, proteins are called polymers and plants manufacturing them are polymer plants. Thus rubber manufacturing plant, synthetic yarn (nylon, terylene ete.) unit, plastic, resin or silicon making factory or a starch manufacturing factory can be called a polymer plant. ‘The polymer (bigger) molecules are built up of smaller units joined together and form a repeating structure. The repeating structure or the recurring unit in a given molecule is called the monomer, and the entire molecule composed of several such repeating units is called a polymer. Thus we can say that rubber is a polymer of isoprene, starch of alpha-glucose and cellulose of Beta-glucose. Polymerisation process is of three types (1) Addition polymerisation i.e, the combination of monomers either of the same kind or different kind by a process of addition involving no loss of fragments, for example, ethylene-polythene. (2) Copolymerisation involves two different types of monomers, for example vinyl chloride with vinyl acetate (3) Condensation polymerisation means the combination of monomers by a process involving loss of a simple fragment or a molecule of water. ‘The terminal units of the polymer chain may be different from the units inside, For example, polyester from a di-alcobol and di-acid. The alkyd resins are such polymers obtained from phthalic acid and glycol or glycerol. Linear polymers are thermoplastic and cross-linked polymers are thermosetting. Polymers Proteins, starch and cellulosic fibres, a a Rubber ‘Synthetic tic Plastics plastics and resins are used to make Spots SybetcPa thousands of industrial products. The Notuml 1 1 Rayon Cetulase variety and names of polymers are many, Synthetic Nylon plastics only a few are mentioned below: Naps ee ae Butadiene ‘Feeylene Bakelite) Paint vehicles Polyester ~—-Vinyl plastics vq Allyl resins Phenolic resins Epoxy resins Acrylate resins Polystyrene resins Lacquers Silicon ‘Teflon Pagel 418107- Safety in Chemical Industry Hazards and Controls Mostly the polymerisation processes are carried out in totally enclosed system and therefore the hazards are reduced too much extent. Machinery is also mostly enclosed. The hazards are possible from exposure to raw materials, leakage and spillage, dusts and fumes, hot surfaces and radiant heat, noise and vibration and heat and humidity. Chemicals like formaldehyde and caprolactam throat. High temperature and pressure of thermic fluid (¢.g. Dowtherm) oil heating system “Thay cause burn and sometimes fire. Extrusion machines have hot surfaces which need ing burning in eyes, nose and insulation to prevent bum injury and hopper feeder to prevent hand contact with screw conveyor inside. Cutting machines for plastic, rubber and other hard substances need safety guard on cutting blade and machine drives. Charging of toxic materials (powder or liquid) need enclosed system with local and room exhaust fans and necessary respirators. “was noticed in polymerisation workers. Another chemical di methyl formaide (DMF) causes digestive effects, abdominal pain, skin effect and pancreatitis to workers exposed to it. (eg. Spimingbaihandsoventianks). SSCS _ Styrene monomer, acetone (used in cleaning) and organic peroxide catalysts used in _making polyester resins may eause Bre and explosion. Styrene vapour may cause narcosis ffeets on head, nose and throat). To control such vapour, dilution ventilation and spray booth are necessary. TLV is more critical than the LEL of styrene (Styrene monomer-phenylethylene or vinylbenzol ~ CSHB, TLV 50 ppm or 215 mg/m3, STEL 100 ppm or 425 mg/m3, LEL 1.1%, UEL 6.1%, FP-3300, VD 3.6). The inhalation dose of styrene can be measured by analysis of exhaled air (gas chromatography). Solvent storage should be kept away, covered metal containers should be used to collect solvent wastes, electric fitting should be flameproof and smoking must be probibited. Direct contact of peroxide catalysts should be avoided, Neoprene or plastic gloves are not affected by solvents. Itching from fibrous glass particles can be minimised by good housekeeping, ventilation, use of long sleeves, barrier creams and frequent washing with soap and water. Ethylene, propylene and other olefin members to make polyolefin’s (polymer) are 1 propylene and -yperpasa due to prolonged exposure to dilefins have ben epote, ATuminum ally ae ‘weak anaesthetics at a concentration above 60%. Freezing burns due {o lig > Freezing bums due 4 Certificate Course in industrial Safety Page2DSeeger eens it causes burns. Adequate body PPE should be given to workers. 18107- Safety in Chemical industry flammable in air and explosive in water, their fumes may cause lung damage and in solution Ethylene, propylene and butylenes are gases at room temperature, highly flammable or explosive when mixed with air or oxygen and large fires of olefins are difficult to extinguish. In case of fire, their supply should be stopped, fire should be allowed to burn out and adjacent structures be cooled by water. Small fires may be controlled with CO, or DCP extinguishers. Polystyrene is made by polymerisation of styrene and other monomers. They are flammable. Polymerisation process is highly exothermic and uncontrolled reaction may reach explosive siage. Cooling and pressure relief devices on vessels are essential, Foamed polystyrene is also flammable. Most of the chemicals are toxic. Therefore leakage should be prevented by quick maintenance and enclosed system. Female workers exposed to polystyrene production showed disturbed menstrual cycles, sexual activity, distributed pregnancy and child d birth. Biological indicators are blood styrene Tevel and styrene metabolites in urine. Polystyrene dust may cause weight loss and erythrocyte, leucocyte or hepatic changes. Polystyrene process should be fully enclosed, automated or remote-controlled. Manual handling should be replaced by mechanical one, leakage should be stopped, local exhaust ventilation on air contamination, respiratory and other PPE to the workers and their medical examinations are necessary. In making various types of synthetic rubbers, solvents like hexane, styrene, butadiene, chloroprene, acrylonitrile, toluene diisocyanate (TDI) and other esocyanates in making elastomers, ethylene dichloride (EDC), methyl chloride, ethylene, propylene etc. are used. Safety measures are required depending on properties of these dangerous chemicals, their splashes and leakage, pressure release) machine parts, entry into vessels, cuts and buns, fll from height and on the floor. Health hazards are possible in handling raw rubber containing extender oil and carbon black. During fire CO hazard is also possible. Workers should be made aware of all these hazards and properly trained. Gas detectors with alarms, welding permit, vessel entry permit, exposure measurement, good ventilation, rubber gloves, eye protection, hearing protection and washing facilities are also required. “Thus depending on a type of polymer plants, a variety of control measures are applicable. Certificate Course in Industrial Safety Page2.615107- Safety in Chemical Industry 10. SAFE STORAGE AND HANDLING OF FLAMMABLE, CORROSIVE AND TOXIC CHEMCIALS Storage tanks of dangerous chemicals must be constructed and controlled properly. Safe inventory must be maintained, Content should be minimum possible, Necessary safety fittings on the tanks should be provided. LPG tanks and tanks of other flammable or toxic chemicals must have proper safety devices. Toxic gases should be kept in liquefied state if possible. Cooling media and device, safety valves, pressure gauges, temperature gauge, scrubber, level or content indicator, flare, water curtain, toxic exposure sensors and alarms, emergency bypass, safe discharge and collection, ete. should be provided as per requirement, Name and quantity must be clearly mentioned to assess the hazard potential. Barrels, carboys, glass vessels must be kept, handled and used in safe manners. Use emergency kits, tools ete. where necessary, All the vents of storage ranks of low boiling. chemicals should be connected to an appropriate condenser or scrubber. Altemate power (e.g. DG set) must be kept ready to run the cooling system; scrubber etc., in case the main power fails. Safety measures of some specific chemicals are stated below Handling of Flammable Liquids General guidelines for loading/unloading liquids are as under: 1. Take care of adverse weather conditions. 2. Safe access to the top of the trailer tank car. 3. Suitable fire extinguishers. 4, Where air pressure is needed or other gases such as nitrogen, adequate hose lines should be provided with reducing valves. Pressure should be as minimum as possible. Soundness of the pipe line and joints should be checked. Breakable pipes should not be used for toxic chemical. 5. Steam lines, if heating is necessary. eee 7. “Adequate personal protective equipment should be provided. 6. Personnel discharging duty should be in the vicinity. + 8. Emergency shower and eye washer should be provided. Certificate Course in industrial Safety Page2 718107- Safety in Chemical Industry 9. Ensure that sufficient space is available in the receiving tank. 10, Training of personnel necessary. 11. Avoid mixing of chemicals. Take full precautions, 12, Routine thorough check-up procedures. 13, Proper identification on discharge lines. 14, Barthing for transferring flammable liquids. Muffler on exhaust pipe. 15, Truck/tanker should be fixed by brakes or wheel blocks and engine stopped while Joading or unloading Flammable liquids are easily ignited and difficult to extinguish. Their vapours form explosive mixtures with air. Flammable liquids in unopened containers offer only moderate fire risk. They however, become severe fire hazard when containers are open or leaky. Before handling, containers should be carefully inspected and damaged or leaky containers, if any, be segregated. Containers should not be dropped, rolled or so handled as to risk damage to them. Safe handling of Solvents: A solvent is generally a liquid at room temperature, capable of dissolving another» substance without reacting with it or chemically altering it! Solvents are classified as Solvents are classified hydrocarbon, Halogenated, Protic or Aprotic solvents. hydrocarbon, Halogenated, Protic or Aprotic solvents. wk. From safety point of view flash point, toxicity and be to form explosive peroxides on degradation are important properties of solvents. Boiling and freezing points determine maximum reaction temperature and useful liquid range. Low water solubility can simplify phase separations, solvent drying operations and running anhydrous reactions. The ability to azeotropically remove water can also be a very useful characteristic. While transferring solvents grounding and bonding of metal tanks and container are necessary. Inert gas (nitrogen or argon) blanketing of vessels and flameproof electrical fitting and apparatus are essential. Solvents which can generate explosive peroxides upon exposure to air and light should be stored in a cool dark place. Chlorinated hydrocarbons can emit highly toxic vapours. Therefore workers should wear a necessary respirator. Good Certificate Course in Industrial Safety page2B15107- Safety in Chemical Industry ventilation should be provided. MSDS should be studied. Less hazardous substitutes should be selected. Guidelines to restrict storage quantity should also be followed. ‘Handling of Flammable Gases Gases are generally contained in cylinders, in the compressed liquefied or dissolved state, Flammable gases will pose the hazard when they leak or escape from their containers. Also when a gas is subjected to a high pressure, it could burst the container with serious consequences. In handling and storage it must be ensured that the cylinders are protected from damage or deterioration and heat. Some of the precautions to be taken are outlined below. Cylinders should not be dropped, dragged, rolled on their side or permitted to strike one another or other surface violently. When removable caps are provided for valve protection, such caps should be in place at all times except when cylinders are in use. It is safer to use suitable trucks to move them even through short distances. They must not be lifted by their cap or with the aid of rope or chain slings. A safe cradle on platform with guard rails should be used for the purpose. Cylinders should not be used as rollers, or supports for any purpose other than to contain the contents as received. Storage room for the cylinders should be dry, cool and well ventilated. Where practical, they should be of fire resistant construction. Highly flammable solvents, combustion waste materials, corrosives and cylinders of oxygen should not be stored near cylinders containing flammable gases. In outdoor locations they should be kept off the ground on a raised concrete pad or non-combustible rack and sheltered from sun by means of non- combustible canopy. Handling of Flammable Solids A large variety of solid materials used in industries and at other places present fire risk. Flammable solid materials become particularly hazardous under certain conditions. Some possess the ability of being easily ignited by extemal sources such as sparks and flame. Some other is liable to heat spontaneously and ignites. Certain materials have the properly of releasing flammable gases when in contact with water. In the handling and storage of various flammable solids apart from taking normal precautions, additional precautions will have to be taken to guard against the hazard posed due to condition or circumstances under which flammable materials may became severe fire risk. Certificate Course in Industrial Safety Page2915107-Safety in Chemical Industry Bales of Cotton and Jute hemp represent some of the solid materials which are asily ignited. With an ignition source, the fire initially flashes over fibres on the surface and then travels at a slower rate between bales and into individual bales. Ignition source may be electricity, mechanical sparks, smoking, matches ete. Bales should be protected from such source. Electrical wiring in a warehouse for the bales should be installed in a rigid metal conduit for protection against mechanical damage. Spark producing electrical equipment including switches, fuses, and circuit breakers should be in dust tight enclosures. Ware-house to be of non combustible construction with floors Sloping to prevent accumulation of water. Sizes to be not too large and about 3m wide aisles space to be maintained between piles. With bales of jute, at least 1m wide space should be left along the walls and with bales of other fibres, at least 0.8m wide gap is to be left. The height of the pile should be limited taking into account the floor loading capacity and the weight of bales when soaked with water. In any case at least Im head clearance is to be maintained between the top of the piles and the deflectors or sprinklers. Bituminous coal represents flammable solids liable to spontaneous combustion. It absorbs oxygen from the air and the absorption is more rapid when the coal if freshly mined or contains much fine dust. Moisture adds oxidation. Coal should not be stored in contact with sources of external heat or over trenches manhole covers and similar surfaces which may allow movement of air through piles. In yards, piles height to be limited to 3m with low grade coal and 5m with best grade coal. Where bins are used for storage, these should be of non-combustible material with the structure roofed over to protect the coal from rain, The space above the coal should have adequate ventilation to prevent concentration of gases given off by the coal. Calejum carbide and Alkali metals are some of the solids which when in contact with water liberate flammable gases. In some cases the gases released may be ignited from the heat of reaction. These liberate are to be packed in air tight containers and stored in dry cool and well ventilated building of non combustible or fire resistant construction. They should be separated from combustibles, oxidising agents and mineral acids. ‘Handling of Corrosive Chemicals Corrosive chemical will cause severe damage when in contact with living tissue or, in case of leakage, will materially damage or even destroy the surrounding they come in contact with. It is likely to cause a fire when in contact with organic matter or Certificate Course in Industrial Safety Page 01S107- Safety in Chemical Industry certain chemicals. Certain corrosive substances have other more serious hazardous properties (toxicity, flammability etc.) and are commonly classed as toxic or flammable etc. rather than as corrosive. Important corrosive substances are: acids and anhydrous alkalis, halogens and halogen salts, organic halides, organic acid halides, ester and salts. When in contact with human tissues, most corrosive substances will produce chemical ‘bums, while certain other substances (as Chromic acid) produce deep ulceration. Many corrosive substances have a defeating action on the skin and may cause dermatitis. The safeguards against these hazards are: 1. Preventing or minimising contact between corrosive substances and skin, mucous membranes and eyes. Corrosive substances should not be allowed to come in contact with materials that may react, All the containers, pipes, apparatus, installations and structures used for the manufacture, storage, transport or use of these substances may be protected by suitable coatings, impervious to and unaffected by corrosives. All containers or receptacles should be clearly labelled to indicate their contents and should bear the danger symbol for corrosives. A high standard of maintenance and good housekeeping is essential. Adequate ventilation and exhaust arrangement whether general or local, should be provided whenever corrosive toxic gases or dust are present. Personal protective devices should be used depending upon the nature of work viz. (@) Corosion-resistant and impervious suits, or hand-gloves, aprons etc. (b) Respirator, gas mask or self contained breathing apparatus, (c) Barrier cream when exposure is not severe. First aid treatment facilities should be provided and all concerned should be instructed to follow safe practices such as (a) Prolonged washing with water (b) Removing contaminated clothing (c) Seeking immediate medical help. ots Certificate Course in industrial Safety Page L18107- Safety in Chemical industry Handling of toxic chemicals es Read MSDS to know toxic properties of unknown chemicals and list out on precautions necessary. Toxic exposure through inhalation, ingestion, absorption or injection can cause health hazards and damage to a body parts. Therefore, their safe handling and use of PPE is utmost necessary. Training should be given to workers to understand chemical labelling and safety instruction. Discharge of toxic waste, container and contaminated substance should be done in a safe manner and at permitted place, paged 2 Certificate Course in industrial Safety15107- Safety in Chemical Industry 11. TRANSPORATION OF HAZARDOUS MATERIAL BY DIFFERENT MODES ‘Transportation is by road, rail, water or air. Containers are mostly standardised to ensure safety during transit, When a truck or tanker meets with accidents or leaks on the way, it creates problem. Fire explosion can cause harm to public or property. Corrosive or toxic chemical can cause harm to public, animals, birds and environment, Sometimes grave emergency is created. Warning to public, speedy rescue operation, evacuation and calling helping hands may become necessary. While considering transportation of chemicals one has to consider the physical and chemical properties of the product being handled, whether it is a solid, a powder, a liquid or a gas under pressure; the type of packing, hazards, and the mode of transport available. Before transfer or transportation of chemicals, their modes of packaging should be considered. Modes of Packaging ‘* Glass bottles and earboys are some of the oldest packaging available for corrosive liquids, solvents etc. Some of the bulk industrial materials still being transported in bottles are Bromine, Mercury etc. The laboratory reagents and pure grade chemicals are also transported in glass bottles of various sizes. Many corrosive chemicals like Nitric acid, shulphurylchloride, Thionylchloride ete., are transported in glass carboys holding 25-50 kg of the material. These glass bottles and carboys have to be properly protected against shocks. Wooden crates for carboys, plastic or paper packing for bottles is usual. Dangerous chemicals are further protected by packing in clay or other absorbent material so that in case the bottle breaks, the chemical is absorbed and causes least damage. + Plastic bottles, jars, carboys and drums: These could be constructed out of polythene either of low density or high density, PVC or other materials. Quite a lot of chemicals ranging from laboratory chemicals to industrial raw material are being packed and transported in plastic containers. These containers may be further protected by wooden cases. The material must be correctly chosen, Several tragedies have occurred, because, on long storage the plastic containers became brittle and the chemical leaked Out. Steel drums in various size have been used for storage and transportation of solvents and chemicals. Even corrosive chemicals like chlorosulphonic acid are shipped in steel containers. This is quite a common packing for chemicals of all description; and Certificate Course in Industrial Safety Page3 318107- Safety in Chemical industry quite economical too. Recently polythene and PVC liners, as well as polythene lined drums, have been made available and these are used for packing even highly corrosive materials like hydrochloric acid. Proper sealing of the drums is essential. Bags of various types: Jute bags and paper bags are used for the innocuous chemicals like Soda ash, Salt, etc, Polythene lined jute bags have been used for the materials which need to be protected against moisture. Woven high density polythene bags are being used for packing corrosive and water sensitive materials like Caustic Soda and Caustic Potash. Obviously this packing cannot stand piercing and must be well protected and handled such that the bags are not damaged. In transport, the bags must, be properly stacked and secured. Cases under pressure in cylinders: Quite a few gases like chlorine, Sulphur dioxide, ammonia, Ethylene oxide, Oxygen etc., are sold in cylinders containing quantities ranging from 50-100 KGs. Stee! cylinders are the commonest, but various kinds if Tinings are also given for special products. The rules governing the design, testing and filling of cylinders are quite elaborate and must be followed. ‘Tank cars for bulk transport of chemicals are very common, particularly for petroleum products, solvents, acids and alkali solutions. Tanks can be made of various ‘materials of construction such as steel, stainless steel, rubber lined FRP or FRP lined, lead lined or any other special construction. The tank cars could be in various sizes, holding 5-10 tons for road transport or 20-50 tons or more for rail transport. Now a day’s long tankers/trailers have been used to carry more weight. (FRP- fiber glass reinforced plastic). The tank cars should be properly designed and fabricated to meet the service condition. Contamination should be avoided, as it could be dangerous for the product as well as the tanker. Good arrangement for receiving the chemical as, well as discharging should be provided. Vent valves and arrangements to prevent static electricity build up when handling solvent, are a must. Gases under pressure such as liquefied natural gas, chlorine, etc. Are also transported by tank cars. Then FFE and PPE should be carried with the vehicle and their safety rules should be followed. Certificate Course in Industrial Safety paged 41S107- Safety in Chemical Industry TRANSPORTATION BY DIFFERENT MODE: Some Safety Aspects Of Transaction By Different Modes Are As Under: Railroad Transportation : It accounts for quite a large proportion of the chemicals transportation. The greatest hazard in this mode of transportation is that because of the far flung operations, it is not possible to train everyone connected with the operation in the proper case to be taken, Proper labelling of hazards involved is a help. Derailment and accidents are other hazards. ‘The preventive measures are, (a) improved design of the tankers and the couplers, (b) limitations on the size of the tanks, (¢) positioning of the hazardous chemicals away from the locomotive (4) avoiding bunching together of hazardous chemicals (¢) proper labelling of content and the hazardous nature of the chemicals. A serious risk is that an accident may occur at a place which is not easily accessible and where competent guidance may not be available. In the USA Dan organisation (CHEMETREC) has been set up to deal with such cases. ‘Transportation of Explosives by Rail: Such rules (Railway Red Tariff Rules 62 to 74) are as under : ‘No explosives other than safety fuses and fireworks shall be transported by rail except in the van specially constructed for the carriage of explosives and approved by the Chief Controller of Explosives and the Railway Board. Label ‘Explosive’ on each side of the carriage shall be affixed. Carriage containing explosives shall be kept away from the engine (other than electric locomotive) and close coupled to the adjoining carriage not loaded with explosives or other flammable or hazardous substances ‘Not more than 10 carriages containing explosives shall be attached to any one train. Not more than 5 carriages of explosives shall be loaded or unloaded at any one time at any railway station, No explosive shall be transported any passenger or mixed train. Safety fuses for blasting, explosives of the third class (nitro compounds) in the form of cartridges and not exceeding 2.5 kg in weight, detonators up to 200 (each weighing up to 225 gms) and sporting powders and propellants in double packing as prescribed, can be transported by passenger or mixed trains. Certificate Course in industrial Safety Page3 51S107- Safety in Chemical Industry Explosive consignment shall be received at the specified railway premises only, during sunrise and sunset and by an authorised railway servant only. Shunting of carriages containing explosives shall be carried under the supervision of authorised officer. Shunting speed shall not exceed 8 km/hr and no loose shunting will take place. The packages shall be removed by the consignee within 12 hours of day light following their arrival. The Station Master shall keep the packages at a safe distance and covered with tarpaulins or other suitable material. No explosive shall be carried except by rail across any railway bridge. This rule is not applicable to carry safety fuses or gunpowder or nitro compound up to 5 kg or ammunition Class-6, Division 2 and 3. Intemational Regulations conceming carriage of dangerous goods by rail (RID) and British Railways list of dangerous goods and conditions of acceptances also provide rail transport guidelines, ‘ Road Transportation: Road tankers are constructed in a wide variety of materials like steel, stainless steel, lined material and FRP construction. Sometimes they need to be heated or cooled, Road tankers and their fastenings should be capable of absorbing following forces — + In the direction of travel-twice the total weight * Vertically downwards-twice the total weight * Vertically upwards-total weight * Horizontally at right angles to direction of travel total weight The service equipment such as valves, fittings, gauges etc. should be protected against, impact. Three types of independent stop valves - internal, extemal and blind flange- are required. For certain gases like HF, shell opening at bottom is not permitted. Fusible plug to operate below 93°C is suggested in case of petroleum tanker. Spark arrester on exhaust, a portable fire extinguisher, TREMCARD emergency kit and instructions to driver are also necessaiy. Display of class labels on goods package (e.g. box, drum) and carriage (e.g. vehicle, truck, tanker) are compulsory wr 129 and 134 respectively. Emergency Planning for Transport of Hazardous Chemical: Various directives and recommended action have been issued by international organisations like UN Committee of experts on the transport of dangerous goods, Certificate Course in Industrial Safety Page3 61S107- Safety in Chemical Industry European Economic Committee (EEC), US Department of Transport ete. They need special labels or notices on packages or on vehicles, display of correct technical name of the chemical, special signs or plates, instruction in writing to the drivers ie. ‘TREMCARD (Transport Emergency Card), safe packing conditions, particulars in transport documents, display of supplier's name, address and phone number including phone number from where specialist advice can be available: ‘The content of a ‘Tremcard! should include name of cargo (material), nature of its hazard, protective devices including PPE and emergency action to (1) inform Police and Fire Brigade (2) Spill or gas control (3) Fire control and (4) First aid ‘The transporter should carry ‘Emergency kit’ containing tool kit, emergency lighting, fire extinguisher, protective clothing, breathing equipment and first-aid kit. Proper training to drivers of hazardous chemicals is legally required. Safety checklist, or transport vehicles shall be prepared and used, Tremcard should be given to workers, Emergency Action: In case of toxic release: Driver of hazardous cargo should be trained to handle small emergencies. Inform police, fire brigade and manufacturer. ‘Takeout TREMCARD, MSDS ete. from vehicle and give it to police. ‘Vehicle should be taken in open area and parked away from thickly populated area. Cordon the area around leak. Stop traffic and keep people away from the vehicle. Leaking liquid can be contained in bunds of sand/earth. Small leaks can be plugged by wooden peg. Ifa leak is from cylinder valve it can be capped by yoke clamp A leaking cylinder can be turned so as to bring leaking portion in gas phase. ‘Water is not to be added on leaking cylinder spill if chemical is éorrosive. Use water sprays, fogs to absorb toxic vapour cloud. Evacuate the downwind area in case of large toxic leakage. Jn case of inflammable chemicals: Park vehicle on the road side Stop engine Inform police, fire brigade and manufacturer Certificate Course in Industrial Safety Page 71S107- Safety in Chemical Industry Takeout TREMCARD, MSDS etc. From vehicle and give it to police. jon the area, stop traffic and keep people away. Do not smoke. Ignition source to be avoided. In case of fire, try to extinguish it with fire extinguisher. ‘Try to stop leak by cutting off the source, close valve. «Keep the tank coo! by water sprays to avoid explosion. go LDP, o * Surrounding area should be checked for explosion possibility and evacuated if necessary. Water Transport: * Quite a lot of chemicals are transported by ocean going ships and on river tugs, Crude oil petroleum products, natural gas and other dangerous goods are some of the biggest, bulk commodities in international commerce. Because of their huge quantities involved, spillage and leakage can create gigantic pollution problems, besides. a fire hazard. There have been several mishaps of this type. Tanker design has assumed special safeguards being made to prevent accidental spillage. ‘When solid chemicals are transported, care should be taken that the material will not cake up because on moisture, so that it may require to be emptied pneumatically. ‘When carrying drums or cylinders they should be properly lashed so as not to break loose. In river transport, spillage of chemicals may canse very serious pollution problems. The carriage of dangerous goods by sea is day by clay increasing. about 400 million tonnes cargo enters world seabome trade every year, of which about 100 million tonnes are dangerous goods in packaged form. More than one lakh types of hazardous chemicals are transported by sea. They include solid, liquid and gases in bulk © Main information required are proper shipping name and UN No., chemical name, formula, properties and observations, classification, packing, labelling, stowage and segregation, angle of repose, MFAG (Medical First Aid Guide) table number and special emergency procedure and action to be taken, Certificate Course in Industrial Safety Paged 8& of 15107- Safety in Chemical Industry 12. TRANSFER OF CHEMICALS BY PIPELINES WITHIN AND OUTSIDE INSTALLATIONS, ABOVE AND UNDER GROUND AND SUBMARINES Chemical are transfer by pipelines and also by different types of containers. Their Safety aspects are stated below. 1. Pipeline Transfer Pipelines are required to carry a variety of materials such as water, steam, air, oil, gas (inert or toxic, vapour or compressed), brine, solvent and other liquid gaseous chemicals. From storage tanks to process vessels, from process vessels to product tanks and from there to filling (loading) points, pipelines are required. They may be above ground, underground or as per requirement, Pipe work may be of cast iron, mild steel, stainless steel, lead, copper, plastic ie. PVC, PP, HDPE, rubber, canvas, glass, FRP, glass lined, rubber lined, Teflon coated, asbestos cement, RCC, stone, ceramic etc. 1. Criteria for Piping Installation: Main factors are - material of construction, design and layout, supports and clamps, welding or flange joints, packing and gaskets, valves and other fittings, easy approach and ‘working platform and testing and maintenance. Material of construction is selected depending on nature (comosivity, toxicity, flammability etc.), quantity (weight, flow, pressure) and other parameters like temperature, viscosity, colour, expansion etc. Thickness of pipe, its quality, welding pattern, flanging are to be considered while selecting for high pressure and temperature, For extremely hazardous chemicals, pipes are tested for inter granular corrosion and certified before used. Illustration is applied to preserve heat and tracing (contact tubing) for supplying heat to the inner material, Various Codes like Indian Standards (hundreds of Indian Standards are prescribed for variety of pipes, their fittings, couplings, threads, colour-code ete., see BIS Handbook), British Standards (e.g. BS 1710, 1319, 537, 4159) and International Standards ISO R 508 for colours for pipes for inland installations and on board ship. Indian Boiler Regulations also provide details for pipe selection, design, fabrication and testing for boiler purposes. 2, Safety Aspects of Pipe work : Generally probability of leakage from pipelines is proportional to the length of pipelines, number of joints, valves, vents, bleeds, drains etc. and complexity such as number of pump connections, recycle streams, hours of working, ete. Therefore it is advisable to 1. Minimise pipe length, branches and joints, and flanges on vacuum lines. Certificate Course in industrial Safety 4 Page3 91S107- Safety in Chemical Industry. Z ay ots 2. Provide welding joints for highly lammuble or toxic chemical, good ook and guned packing, ‘lang guard to deflect leak downward, flexibility to allow thermal expansion, bellows subjected to axial movement, drains and traps at visible places, removable plugs on sample points, adequate pipe supports, walkways, platforms or working place, proper slopping for draining, overhesd clearance for vehicle movement (about 6 m),ergonomie design for valves to be operated and gauges to be seen, earthing and bonding to remove ‘Static charge due to flow, overflow retum from measuring vessel to a storage tanks, painting with colour coding (1S: 2379) and cathodic protection where required. More pipe work in dyke is not desirable, particularly with hazardous chemical, as it may be trapped in fire in the dyke. Similarly pipelines of flammable or toxic chemical should ‘not be laid in tunnel, as its leak may spread from one area to another. Electric cables or hot | ines and flammable gas or liquid lines should not run side by side, Solvent line should not be Serer peer a ae ere ee eee Piping arrangement should be such that in case of failure at any point, the system can ‘be quickly isolated by closing valves without distbing the rest of the-system, Flushing arrangement should be provided for easy start up and maintenance, Pipe alleys should not run over the walking alleys, normal layout should be near the walls or in sides. To allow for. thermal expansion special joints or loops should be provided. Emergency control valves should be easily accessible. By-pass valves should be within easy reach, Auto control valve should have bypass or manual valve which may be required in the event of failure of auto control valve. Particularly at the outlet of bulk storage of hazardous chemicals manual and remotely controlled auto isolation valve both should be provided as near as possible to the outlet. Pressure relief device, liquid seal, manual vent valve ete. should be provided to depressurise the system where necessary. Many different types of valve exist. It is essential to choose the type best suited for the particular operation it has to perform, For instance, if ball valves are to be fitted in a high pressure position, they should be trunnion mounted. Where positive segregation of products is required, say at a multi-produet manifold, it is essential to provide block and bleed valves for continuous monitoring of valve seats and seals. For positive isolation some form of soft seat willl a wedge gate action is desirable. Pumps must be designed not only to suit the immediate pipeline requirements, but should take into account future ‘opments .Thus, it may be necessary to stipulate a pump ‘casing pressure much higher than the pump Gan generate, if series or boosting, pumping is envisaged. Care should be taken to ensure that additional or larger impellers can be fitted as Certificate Course'ip industrial Safety * page4 01S107- Safety in Chemical Industry the system demand glows. The maximum operating pressure for the pump mechanical seals should match the pump capabilities. It may be necessary to provide product filtration to protect the minimum clearance of the pump moving parts, particularly on modem high efficiency pumps. Flexible pipes, joints and hoses should be safe, sound and properly tested. Bolted clips are preferred to jubilee clips. Proper supports or hangers are necessary. Glass piping, equipment or gauge needs extemal protection to protection against external impact or intemal bursting and flying fragments coming out. Layout drawings of piping and fitings should be maintained and corrected when any changes are incorporated, 33)50 Use of plastic piping is increasing, When itis used for hazardous gas like hydrogen, LPG, chlorine ete, utmost care is required to ensure safe joint. ‘Nomnally metal compression fittings (Fings and nuts) are used, Softer ring is preferred over hard compression ring, Nut should not be loosened. It should be frequently checked for leakage. When any leakage is noticed, first the supply cylinder valve should be closed instead of operating any electric switch or spark generating device ‘Semi-conductive material for hoses preferred over non-conductive or good conductive material to avoid static electricity. The conductance should be between 10 to 10* mho. Failure of packing in valves stems or flange gaskets, opening the wrong valve or failure to depressurise the system before opening the joint and un insulated steam or hot lines can_ fous osidents. Remedial measures are splash guard, replacement of gasket, tagging and and proper training and supervision. In above ground pipe work which remains isolated during normal operations, thermal relief system should be provided to protect against increasing ambient temperature, _ ‘Underground Pipelines ERGO Petroleum products, crude oil, and natural gases are some of the more important nes, The sae may vary where up o 50” dlameter i Pipelines are laid'for long distances, often across national boundaries. Rooster stations are largely automatic stations requiring very fail-safe devices. The pipelines are usually burled about 1 meter underground and must be protected against corrosion. Leakage is likely to occur. The pipelines have to be checked constantly the biggest danger to pipeline come from outside sources like unauthorised digging and from corrosion, Pipelines should be given special additional protection at various points along the route as road and river crossings. Generally, they may be placed at a a greater depth beneath rivers Certificate Course in industal Safety Page4 1|S107- Safety in Chernical Industry and ditches to allow for dredging or ditch deepening. Concrete protection slabs may be onal auch to i placed above the pipe to warm anyone who may excavate in the area. If the ground is particularly stony or rock filled, sand may be imported to cover the pipeline or a special protective wrap may be used. During construction of a pipeline, all welds are visually examined. Generally, a percentage is radio graphed to ensure that there is no cracking or undue slag intrusion and that there is suitable fusion between the weld and the parent metal. The pipeline is wrapped to pfotect it against corrosion once itis buried. The wrapping is normally tested by a 15,000 volt pressure test to ensure there are no holes in it, Additionally, an impressed current cathodic protection system is superimposed to protect against subsequent wrapping damage due to stones, roo, et. . Pipeline control systems should be capable of recognising and measuring leak conditions and initiating the appropriate action to shut down the system and minimise the ‘amount of product leaked. “Precautions in Breaking Pipelines: Following precautions are necessary while opening or breaking any pipeline: 1. Prepare work permit. Tag the joint or portion to be broken. Precautions 2, Close of lock the isolation valves to stop flow in the line to be opened. Isolate the area, 3. Stop pump and lock motor. Remove fuse so that motor cannot be started, 4, Drain, vent and cool the line completely. See that the pressure is zero and the pipe is cool. 5. Wear PPE like hand gloves, face shield, apron, respirator etc. depending on chemical. Keep fire extinguishers ready. 6. Support the line on both the sides of joint. If it can fall, hold it by a lifting machine. Flange muts and bolts should be opened slowly. A temporary flange guard should be put so as to protect from splashes or dripping. First the farthest nut-bolt should be loosened so that splash if any may not come toward the body. Dripping, if any, should be allowed fully. Then the adjacent nut bolts should be opened. To separate flanges, a metal wedge may be used if necessary. Final bolt will be opened only after completion of dripping. Spark should be avoided. 7. After removing choking by scrapping, digging or drilling, the removed section of the line, valve etc. Should be decontaminated by water, air or purging inert gas. Ifthis not possible, it should be tagged with waming, indicating the contaminant. Certificate Course in industrial Safety page4 215107- Safety in Chemical Industry 8. Use stable platform. Working by sitting on other pipelines, ladder or structure is risky. 9. Safety shower, running water hose, fire extinguisher, absorbent ete. should be kept ready for use. 10. More precautions should be taken while opening dead lines or pipes whose content is. not known. 11. Direct cutting by hacksaw or gas flame without knowing the content is hazardous Flammable, corrosive or toxic content must always be removed first In-Plant Transfer: From storage at production place, chemicals are, transferred or transported to an user place or another storage place. It may be from one place to another outside place or within the factory premises. : Chemicals are transferred in solid, liquid or gaseous forms. Solids are transferred in lumps or powder form and may generate dust, for which dust compression or extraction system is necessary. Liquids are transferred by gravity, pumping or by water, air or inert gas pressure. Splashes from vessels, pipes, joints, pumps, glands, valves and cracks are possible. Control of flow rate, safety showers, absorbents and personal protective equipment become necessary. Gases can leak through cylinders, valves, pipes, joints, vessels, gauges ete. Flow rate control, scrubber, condenser, venting and safe discharge are essential. . Through pipelines: Most plants have a system of storage tanks for liquids or even materials which can be easily melted. The liquids are pumped measuring tanks from where they are charged to the reactors. Safe practice is to pump to the measuring tank and an overflow line returning to the tank. ‘The pipelines can be of various materials, depending upon the nature of chemicals handled steel, stainless steel, polythene, polypropylene, PVC, glass, lead, glass lined, rubber lined. The pipelines should be well laid, giving adequate support, provision for maintenance, and painted for correct identification, as per IS : 2379 Pipelines carrying LPG and flammable material should be properly bonded and earthed Isolation valves should be provided for easy control in case of breakage and maintenance. . Drums: While bandling liquids from drums, the material can be emptied by sucking into a measuring vessel or by pumping out, using a small pump that could go into the bung opening, or by a gear pump. Air pressure should not be used, more so with toxic or corrosive liquids. Transfer by vacuum and using necessary PPE is the best procedure. Certificate Course in Industrial Safety Page4318107- Safety in Chemical Industry Solids can be discharged into reactors by drum tilters or emptied onto specially designed screw conveyor. Cut drums should not be invariably used. They can cause plenty of accidents, as workers are not careful to hammer down the sharp edges. Partially used drums must be covered, special protection should be taken to preserve the chemical and the product identified. : Empty drums are not really empty, if they have been used for solvents unless specially cleaned. Dangerous chemicals like Dimethyl sulphate, benzyl chloride, etc. require elaborate cleaning to really wash out the traces of harmful ingredients. 3. Naked earboys and glass bottles should never be transported. They should be transported in wooden crates or cases, properly closed and handled to avoid damage to the container. yh 2oterne? 4, Plastic Carboys are very easy to handle and sturdy. Special spouts are usually provided to prevent spillage. 5. Conveyor belts are frequently employed for handling large quantities of chemicals, ‘When dealing with organic powders, steps should be taken to see that static charge is not generated. 6. Pneumatic conveyors are increasingly used for transportation from one place to another within the plant. 7. Gas cylinders should be handled with the right type of tackle, trolley and certainly not thrown down. They should be protected against the heat and impact. When kept vertical, they should be clamped or tied to prevent fall, Certificate Course in Industrial Safety page44-18107- Safety in Chemical industry 13. SAFE PROCEDURE OF START UP AND SHUT DOWN PROCEDURES Introduction “Operating procedures tells how the plant is to be operated safely within design parameters and deviations from normal operating condition.” Unsafe operating procedures in industries often result into accidents, Opportunities for hazard arise whenever process conditions are changed. The frequency of such changes may be reduced by building in process reliability and stable operating conditions. All possible activities other than normal operation must be identified and safe procedure must be developed and established and documented after thorough investigation of process dynamics. The operator spends his most of the time in control room and patrolling the plant so as to observe any abnomnalities and to deal with plant upsets. Therefore, plant operators should have manual of normal and immediate alarm procedures and should know which abnormal conditions require action and by whom. Maintenance engineer should have different manual, mostly on a technical base and specifying the release procedure by which they are allowed to work on the plant unit. ‘There is not once manual, but many, each appropriate to its user and each specifying in some detail the user’s freedom of action, The contents of manual require careful consideration, particularly at the lower levels of operator. If the answer to the following questions could be ‘no’ consideration may need to be given to more Training or more reliable instrumentation or simpler alarm arrangements: «Is it clear that the plant can go wrong as well as operate correctly? ‘© Does the operator realize the potential hazard? © Can he read, write and figure with sufficient competence? ‘* By his colleagues and by the next member in the management, maintenance and emergency teams? Not all the problems are related to unsophisticated workforce. Even on quite complex plants, it is not always clear from the alarm signal. ‘© Which alam is sounding © Whether is it high or low alarm «Holding action while it is investigated © Urgency of the alarm Certificate Course in industrial Safety page4 51S107- Safety in Chemical Industry Although many plants have computer control and many other large plants do not. For these, understanding of all levels of their own jobs, a good level of communication is essential. It is particularly important for the system to afford good control of situations like construction or modification. The integrity may be degraded by plant modification unless they are closely controlled. The Flixborough disaster was caused by a modification which had reduced the plant integrity. Hence the plant modification requires a system to identify, check & record modifications. STANDARD OPERATING PROCEDURES ‘The operating procedures are normally formulated during the plant design and are modified as necessary during the plant commissioning and operation. Different company has different instructions documents, Operators should have sufficient information to operate their task in normal & emergency situations but not so much about related matters that they become confused. However some of the standard operating procedures are as follows: Procedure for plant start-up © Initial start-up © Start-up of plant section when rest of plant down. + Start-up of plant section when other plant on stream © Start-up after maintenance ‘© Start-up after emergency shutdown © Lighting of furnace/flare Different modes of shutdown © normal shutdown © Partial shutdown © Emergency shutdown © Manual controV/remote control identification process © instruction for deviation in process parameters ~ Procedure for product quality, handling of materials, effective use of energy. = Procedure to control omissions of effluents & their treatment - Procedure for recycling of intermediate streams/regeneration of beds/eatalyst etc, Certificate Course in Industrial Safety Page4 61S107-Safety in Chemical Industry - Operating procedure of each unitfequipment giving how it is to be operated with design condition, - Sampling procedure & laboratory analysis at numerous stages of process ~ Procedure for making equipment safé to enable maintenance work. - Maintenance Procedure (Development of check list for preventive maintenance) + Modification Procedure ~ Safety manual/order/safe practices ~ Emergency control procedure and Auditing & review of procedure. STARTUP PROCEDURE The start-up & shutdown of plant must proceed safety & easily & should be flexible enough to be carried out in several ways. The operating limits of the plant must not be exceeded and dangerous mixtures must not be formed as a result of abnormal states of concentration, pressure, temperature, phase, reactants, catalyst and product. Control system must not operate out of their normal range, Mechanical, electrical, instrumentation faults may also appear during start-up. 1, e.g. sulphuric acid '1.84) will sink, This information is useful for spill or fire control. 11, Vapour Density (air = 1) : It is the vapour weight per unit volume. In MSDS it is given as the ratio of the density of a gas or vapour to the density of air, The air density is 1.293 gm/, but here it is considered as 1 for easy comparison of gases. Lighter gases (Vd<1, e.g. ammonia 0.59) will go up (vise) in the air and heavier gases page 5 (Vd>1, e.g. chlorine 2.49) will come down on the bottom. This information is useful for ventilation design and evacuation (emergency) activity. Certificate Course in Industrial Safety15107- Safety in Chemical Industry 12, Boiling Point: gas. Below this point the liquid can evaporate to form vapour but at the BP the it is that temperature at which the material changes from a liquid to a change from liquid to vapour is faster. This increases the vapour concentration and its pressure. This condition poses higher risk of fire, explosion or toxicity. 13, Thermal Decomposition products: If the material decomposes (breaks down) without boiling, the temperature at which it decomposes is given with the word ‘dec’. Some of the decomposition products are hazardous. The thermal decomposition products may be quite different from the chemicals formed by burling the same material (hazardous combustion products).. Information regarding thermal decomposition is useful to design ventilation system where a material may be heated. 14, Hazardous Decomposition Products: They are formed when a material decomposes (without heating) because it is unstable or reacts with common material like water or air (oxygen). This information is useful to design storage and handling procedures. For example, phosgene decomposes into corrosive and toxic fumes of HCL and CO because of heating or coming into contact of water or steam. Here HCI and CO are hazardous decomposition products. ; 15, Hazardous Combustion Products: These are the chemicals which are formed when a material bums. They may be toxic, flammable, smoke, carbon particles or other hazards. Their amount varies according to temperature and oxygen(air) available. "They may be different from the thermal decomposition products. This information is useful lo decide the fir; fighting material and procedure. 16. Melting Point : It is that temperature at which a solid material melts and becomes a liquid. This information is useful for storage and handling purpose. A melted material may distort a container. 17. Freezing Point: It is that temperature at which a liquid material freezes and becomes solid, This information is useful for storage and handling purpose. A frozen material may burst acontainer. 18. Vapour Pressure: It is the pressure (mm of Hg) upon atmosphere of the vapour of a material at a fixed temperature (e.g. 20 °C). Higher vapour pressure indicates higher concentration and therefore higher hazard due to fire or inhalation. 19, Solubility: It is the ability of a material to dissolve in water or another liquid (solvent). It may be expressed as a ratio or described by words like insoluble, very soluble, sparingly soluble or miscible, This information is useful to decide a Certificate Course in Industrial Safety Pageo 61S107- Safety in Chemical Industry scrubbing media, spill control or fire fighting material and procedure, Such solvent should not be hazardous, 20. Scrubbing neutralising or inactivating media : These are those materials (liquids) which dissolve or react with the hazardous material (gas, liquid or solid) to dul Lilush its hazardous exposure e.g, caustic, lime, water etc. If this is not possible, proper absorbent may be used e.g. sand, sponge rubber etc. 21. pH : It is a measure of the acidity or alkalinity (basicity) of a material when dissolved in water. It is expressed in a scale from 0 to 14 as under : Strong acidic Weak acidic pH 2 5 8 Neutral n 1 Weak basic 4 Strong basic This information is useful to select a neutralising material for scrubbing or effluent treatment or spill control. 22. Flash Point: It is the lowest temperature at which a materiel gives off enough vapour near its surface to form a flammable air vapour (gas) mixture so that it can be ignited iff a spark is available, The lower flash point indicates higher hazard as it can cause fire at a lower temperature. It is expressed as Closed Cup (CC) or Open Cup (OC). CC value is stightly less than the OC value. 23. Auto-ignition Temperature: It is the lowest temperature at which a material begins to bum in air without any contact of spark or flame. During heating if the material decomposes, the decomposed chemical may auto-ignite at some other temperature, Different test methods give different auto-ignition temperatures for the same material. ‘Therefore this value is an estimate. The material should be stored, processed or handled well below its auto-ignition temperature to avoid the risk of self fire or explosion. ‘Substances liable to spontaneous combustion are those liable to spontaneous heating under normal conditions or to heating up on contact with air and being then liable to catch fire. 24, Flammable or Explosive Limits (LEL/UEL): The lowest concentration (percentage in ait) of gas or vapour which will burn or explode if ignited is called the Lower Certificate Course in Industrial Safety PageD 718107- Safety in Chemical Industry Explosive (or Flammable) Limit ie, LEL or LFL. ‘The upper concentration (percentage in ait) of gas or vapour which will burn or explode if ignited, is called the Upper explosive (or Flammable) Range. The fire or explosion risk within this range but not out of it, Below LEL the gas-air mixture is too lean to ignite and above UEL itis too rich to ignite. 25. TDG Flammability : Transport of Dangerous Goods (TDG) classifies the materials according to their flammability as under — 2.1 Flammable gas. 3 Flammable liquid (Subclasses 3.1, 3.2 and 3.3 based on flash point). 4.1 Flammable solid. 42 Spontaneously combustible material. 4.3 Material which gives off a flammable gas on contact with water. 26. Explosion Data (Sensitivity) : It gives explosive properties of a material e.g. low, moderate or high. It gives two types of sensitivity : Explosion sensitivity to impact — It indicates whether or not the material will bun or explode on shock or friction, and Explosion sensitivity to static electricity — It indicates how readily the material can be ignited by an electric spark or static discharge. 27. Explosive Material: An explosive material is that material which can explode on impact or by electric spark. Schedule-1 of Manufacture, Storage and import of Hazardous Chemicals Rules, 1989 defines explosives as those chemicals which explode under the effect of flame, heat or photo-chemical conditions or which are more ‘sensitive to shocks or friction than dinitrobenzene (old definition) or pyrotechnic substance (firework) or which is capable of producing gas at such temperature, pressure and speed to cause damage to surroundings or exothermic reaction by heat, light, sound, gas, smoke or their combination (new definition). 28. Combustible and Flammable Material : Flammable solid, liquid or gas which can catch fire and bum rapidly or explosively are flammable materials. The terms combustible and flammable both indicates the ability of a material to burn, Any material that will bum at any temperature is combustible by definition, Flammable are a special group of combustible materials that ignite easily and burn. Certificate Course in industrial Safety Paged 8B1S107- Safety in Chemical Industry 29. Corrosive Materi: rapidly. For example, NaCl, CCI, and CO2 are non-combustible while sugar, cellulose and ammonia are combustible but non-flammable. It can attack (corrode) metals or human tissues such as skin or eyes, Structure or inetal container may become weak and eventually collapse or leak. ‘Skin, eyes or other body Paris can be badly affected (buming) by corrosive materials. Acids, halogen gases, chlorides, caustic; phenol etc. Are corrosive. 30. Hazardous Polymerisation: A polymer is a natural or man-made material formed by 3. combining units called monomers, into long chains. e.g. styrene is the monomer for polystyrene. Polymerisation is the process of forming a polymer by combining monomers into long chains. Uncontrolled polymerisation can be hazardous, as it can cause heat, pressure or explosion. Some chemicals can polymerise on their own without warming, others upon contact with water, air or common chemicals, Vinyl chloride rapidly polymerises in presence of Light, air or heat. Therefore polymerising conditions should be controlled properly. Inhibitors (negative catalysts or compounds that retard or stop an undesired chemical reaction such as polymerisation, oxidation, corrosion etc.) are normally added to products to reduce or eliminate the possibility of hazardous polymerisation. Pyrophorie Material : Any liquid or solid that will ignite spontaneously in air at about 54.4 °C (130 OF). Titanium dichloride and phosphorous are examples of pytophoric solids, tributylaluminium and related compounds are pyrophoric liquids. Sodium, butyllithium and lithium hydride are spontaneously flammable in moist air as they react exothermically with water. Such materials nu s t be stored in inert gas or under kerosene. Some alloys (barium, misch metal) are called pyrophoric because they spark when slight friction is applied. Pyrotechnic materials mean fireworks. Catalysts of pyroplioric material which can burn in normal air, are replaced in the atmosphere of nitrogen blanketing. The workers have to wear self breathing apparatus while doing such job, because in the atmosphere of about 90% nitrogen, oxygen is insufficient for breathing. 32, Oxidiser and Peroxide: It is a compound that spontaneously evolves oxygen either at room temperature or under slight heating. Oxidisers include peroxides, chlorates, per chlorates, nitrates and permanganates. These can react vigorously at ambient temperatures when stored near or in contact with reducing materials (that will remove Certificate Course in Industrial Safety Page 9ro 18107- Safety in Chemical Industry oxygen or add hydrogen) such as cellulosic and other organic compounds. Storage areas should be well ventilated and kept as cool as possible. Peroxides release atomic (nascent) oxygen readily. They pose fire hazards in contact with combustible materials, especially under high temperature conditions. ‘They are used as oxidising agents, bleaching agents and initiators of polymerisation. Oxidizing substances are not necessarily combustible themselves but by giving oxygen they contribute to combustion of other materials. Organic Peroxides contain bivalent 0-0-structure, are thermally unstable and may undergo exothermic self-accelerating decomposition. 33. Chemical Stabil Chemical stability is the ability of a material to remain unchanged in the presence of heat, moisture or air, An unstable compound may decompose, polymerise, bum or explode under normal environmental conditions. Special precautions are required to store or handle unstable materials. For examples, CS, decomposes in light and bums due to heat, spark, flame or fiiction arid gives off toxic fumes of SOx. Caprolectum liberates NOx fumes due to heating. TNT explodes due to heavy shock or by heating. Thus conditions disturbing stability must be known. 34, Incompatibility: Compatibility means the ability of two or more materials to exist in close and permanent association indefinitely. Liquids and solids are compatible if the solid is soluble in the liquid. Water is compatible with alcoho! (because it is miscible) A stable compound does not easily decompose or react readily. but not with gasoline (e.g. petrol). Incompatibility means disability to co-exist permanently. Therefore incompatible materials should not be stored or kept together. For example, toluene reacts violently with some acids, plastic or rubber, therefore, these substances should be kept away. Incompatible materials can cause a fire, explosion, toxic release, violent reaction, and polymerisation or destroy the structure or function of a product, This information is useful for storage and handling purposes. 35. Reactivity: Two or more chemicals can react with each other and give reaction products. e.g. 2Hy + 0, = 2HO. A single chemical can react with air or water (Which are also chemicals) and give the product. e.g. phosphorous burns in air and gives its oxides (P03 P20), sulphur bums and gives SO. ete. Certificate Course in Industrial Safety Page1S107- Safety in Chemical Industry Reactions are exothermic when they evolve heat and are endothermic when they need heat to maintain them. A reversible reaction is one in which the reaction product is unstable and goes back to the original substance spontaneously. In MSDS we are concerned with the hazardous reaction or reactive material which can cause fire, explosion, toxic release or violent reaction with air, water or ‘common chemicals or under environmental conditions. Phosphorous, CS2, Sodium metal, acids (reactive with metals) etc. are known for their reactivity. This information is useful for storage, handling and process safety purposes. Reactivity Hazard Data includes stability, reactivity with water and a list of other incompatible chemicals. 36. Hazardous Reaction Products: These must be known for the safety of process, workers and environment, Here products are more important than the reaction because of their hazardous nature. e.g. Chlorine reacts with alcohol and forms explosive alkyl hypochlorite. If toxic fumes are to be generated, scrubbers are required, if flammable vapours are generated, inert gas blanketing is required and earthing of the vessel also becomes necessary. If reaction products are highly poisonous like NaCN, HCN ete., they are to be handled in a closed system, 37. Health Hazard Data: It includes toxicological information, LDs or LCso, carcinogenic or mutagenic potential, likely methods of exposure (inhalation, ingestion, skin absorption). Should also include signs and symptoms of exposure. TLV and STEL are given in 2" Schedule of the Factories Act. LDsy and LC;are given in 1 Schedule of the MSIHIC Rules for the purpose of major accident hazard. LDsp for insecticides are given in Rule 19 of the Insecticide Rules for labelling purpose. Lower these values, higher the toxicity. LDso up to 200 mg/kg and LCy up to 10 mg/l can cause major hazard. By local exhaust ventilation toxic gas, dust or vapour must be captured and effective PPE must be wom by the workers. Above STEL, SBA is desirable. 38. Physical Property Data: Includes information such as appearance, odor, density, boiling point, melting point, vapor pressure, evaporation rate (suually relative to n- butyl acetate), ete, 39. Fire and Explosion Hazard Data: Includes information such as flash point, auto ignition temperature, explosive limits in air, recommended fire extinguishing media and fire fighting measures. Certificate Course in industrial Safety Page 11S107- Safety in Chemical industry 40. Handling and Storage Precautions: Special storage requirements, list of ‘compounds from which to be separated. 41, Accidental Release Response Measures: Appropriate equipment and procedures for cleaning up a spill or other release. 42. First Aid Measurers: Actions to take upon exposure to misiimize possible injury (induce vomiting, flush with cold water, remove to fresh air, etc.). 43, Ecological Information and Disposal Consideratioy disposal, precautions for disposal. 44, Transport information: Any limitations or precautions for packaging and shipping 3: Recommended means of safety, DOT shipping information, UN hazard class, packaging group, etc. 45, Regulatory Information: Any special considerations based on_classification under TSCA, OSHA, Clean Water Act, ete. 46. Tremeard: Transport Emergency Cards are to be given to the drivers carrying dangerous goods for emergency information which may be needed at any time during joumey. The cards contain short information on nature of chemical, hazards involved, protective devices, emergency action for fie, spillage, leakage, first Certificate Course in industrial Safety PageOZ,1S107- Safety in Chemical Industry 15, WORKPERMIT SYSTEM Work permit is generally required for non routine dangerous work. For routine or regular work of operation, maintenance or repair, permit is not required. It is required to censure safe work procedure to avoid any accident or risk during the work. Statutory Provision: Following provisions should be referred while designing a work permit: i) The Factories Act 1948 — a) Section 36 - Precautions against dangerous fumes. Section36-A. Precautions regarding use of portable electric light. b) Section37- Work in confined space where explosive or inflammable atmosphere is possible. ii) The Petroleum Rules 1976 - Rule 98 - Repair and maintenancé of pipeline. Rule 172- Maintenance work in refineries iii) Electricity Rules - Rule 36(2)- working on electric line or apparatus iv) IS 15001:2000 Annex-A Para 4.2.5- Records for work permit (5) IS 14489- 1998 Annex-C - Effectiveness of work permit system The objectives, methodology, issue of permit, its execution and termination, foreseeing of hazards and arrangement for their Controls, testing and certification of working atmosphere, use of tools personal protective equipment, first-aid and rescue equipment and training of workers for such work are the common factors in any type of work permit application. Its sole purpose is to save life and avoid accident. Hazardous substances are many. They may be explosive, flammable, toxic, hot, and corrosive and may be in the form of dust, gas, vapour, steam, hot oil etc. They pose high degree of hazards, have caused many accidents world-wide and need strict safety precautions while working with them, Other factors being common, the vital part of devising any safety work permit is to concentrate on typical hazards involved and then to apply their remedial measures. Material Safety Data Sheet will expose property hazards. Storage, process and vessel conditions can reveal their specific hazards and due consideration to all such hazards is necessary before devising any substance wise work permit. Normally hazardous works of maintenance or modification need work permit system. It is given —for_~—the-~—following =— category «= of-—works: Certificate Course in industrial Safety Page6 31S107- Safety in Chemical Industry Operations Excavation, vessel entry, workin; at height, hot work, welding cuttin; uipment removal, pipe breaking, line breaking, lining in furnace, waste disposal, ship breaking and cutting. Equipment Electrical, pneumatic, hydraulic lifting machine, crane, sprinkler or hydrant system. Hazardous area Explosive, flammable, corrosive, radioactive or toxic atmosphere. Time Overtime or after hours work. * General and special hazards both should be considered. For example, work with flammable dust, gas, vapour or liquid requires flameproof equipment and avoidance of all sources of ignition, but depending upon the class of fire, specific fire extinguisher is required. Work with a toxic dust or gas needs local exhaust or capture device, but depending on type (e.g. chlorine, phosphine, CO) and concentration, specific respirator is required. © Work with corrosive acid needs acid roof hand gloves, goggles and apron, but depending on fumes given by it (e.g. HC1, SOs, nitrous fumes) specific respirator is required. Work with hot substance requires shielding and hand protection but depending on its nature (¢.g. steam, oil, molten metal, liquid glass, hot. Surface), the specific type: of hand protection (cotton, leather, asbestos) can be selected. Working on a fragile roof needs a crawling board, substantial platform or support and a safety belt but height, place and, position will decide the type of ladder or platform and type of anchoring as specific requirement. Work with dust requires exhaust or suction device but the type (Eg. Sand, coal dust, wood dust, chemical power, bio-organism) and size (microns) decide specific type of respirator. © Knowledge of appropriate solvents, scrubbing media, absorbers and inactivating substances is always useful while preparing work permit for any specific substance. © Knowledge of right type of tool, tackle, equipment and instrument helps in suggesting work with safety. + Work permit to demolish or repair any tank, vessel or equipment needs special precautions. Inner content should be identified and removed before allowing any hot work. The atmosphere must be rendered non-flammable. Residues lie not only on the bottom but also on the walls and may evolve volatile material and catch fire. Polymer Certificate Course in Industrial Safety PageO 418107- Safety in Chemical Industry residues normally lie on the upper walls or the roof. To remove such residues first requirement is to clean them. Cleaning can be performed by hand cleaning, machine cleaning or steaming out. Bottom residues can be covered by water or protein foam as blanketing. Inverting is also possible but this needs oxygen reduction below 10% to carry out any hot work on the tank. + Where liquid content (residues) is of low flash point (eg. 40°C ), the tank may be fully filled with water and then cold cutting (using pneumatic chisel) method may be applied. Cutting should start from the top and proceed foward bottom. Here the vapour space is minimised, resulting in tum, minimisation of the hazard. But the tank should be capable of withstanding the water load. * In another type of method, high expansion foam (e.g. 40 m3 /min) can be used as a blanket. Heat exchanger containing flammable vapour can be filled with water and crushed for demolition. i + However it should be noted that all such techniques require special knowledge and need of an expert/competent person. Permit for Vessel Entry: ‘* AP Foctories Rules, 1950 R/u 95, Sch XV, Chemical Works Part-I (0) defines “Confined Space” means any space by reason of its construction shall as well as in relation to the nature of the work carried therein and where hazards to the persons entering into or working inside exist or are likely to develop during working. © Safe entry in any confined space like pit, sump, vessel, vat, tank, chamber, furnace, oven, pipe, flue, gutter or isolated and unknown place needs work permit system. The hazards of work are toxic or flammable gas inside, asphyxiating atmosphere, accidental inflow of chemical or starting of agitator ete, * More danger is foreseeable when any gas or vapour - visible or invisible, having odour or not heavier than air (vapour density > 1) is suspected in die confined space. Fatal cases have been reported. No person should enter or allow another person to enter such situation without going through the following steps : = Report the need of such entry to higher officer whose duty is to prepare and sign a necessary work permit for such work. + Work permit will be prepared after observing the situation from outside, allowing the vessel to be cooled and giving full thought to all the safety points to be incorporated. Certificate Course in Industrial Safety Page5,15107- Safety in Chemical industry If it is an underground pit, sump, chamber or lank having no connections except a manhole at the top, the manhole should be opened after wearing a self breathing apparatus, free air movement and venting should be allowed for some time and then the gas test and the Oxygen level test should be carried out. Toxic gas should be safely driven out by air purging and a flammable gas by nitrogen purging. The worker doing this job should be experienced and wearing self breathing apparatus. Such work should be carried out during day time with good natural lighting. While replacing any flammable gas or hydrocarbons, sources of ignition must have been removed and non-flameproof electric lighting/ fitting de-energised. Only a flameproof torch may be used. To avoid static electricity, airline should be bonded with the metal of the vessel. ‘Afier evacuating gases as above, again their level (ppm in case of toxic gas and percentage in air LEL-in case of flammable mixture) should be measured and brought down to a safe level. But this is not sufficient. Oxygen content should also be measured and it should be more than 18%, otherwise specific instruction of SBA shall be mentioned in the work permit. If it is a vessel, tank, reactor, pipe or other space having nozzles and connections, first top and bottom, vent and drain/flush valves should be opened to discharge lighter and heavier gases. Inlet connections should be isolated, blinded or removed from joint. By nitrogen purging inner gases should be fully pushed out. Then the: vessel should be washed and drained by steam and water if it is not incompatible. Then the manhole and other top and bottom connections should be removed making the top-bottom nozzles fully open for better (cross) ventilation and lighting. This ensures that neither heavier nor lighter gases will remain inside and free entry of air will keep the space breathable. Otherwise positive air supply should be provided. If it is not possible to open any joint except manhole, the procedure stated in para 3 and 4 should be followed. After ensuring ambient- condition and isolation or disconnection of inlet lines, opening maximum nozzles possible (at least flush bottom drain and top vent), removing or isolating any common connection (e.g. header or common vent or scrubber line) and measuring gas and oxygen content to a safe level, electric connections (e.g. driving motors for stirrer, pump, blower, exhaust, vacuum or any ingress or egress of material) shall be removed (by removing fuses and indicated by Certificate Course in Industrial Safety PageO6