DESIGN STRATEGIES WITH RESPECT TO HAZARDOUS MATERIALS

THE NATURE OF RISK IN INDUSTRIAL FACILITIES

FATAL WORK INJURIES

FATAL WORK INJURIES

THE NATURE OF RISK IN INDUSTRIAL FACILITIES COMPARISON VALUES - DEATHS/100,000 WORKERS –IN 1912, 21 (18, ,000 DEATHS) –IN 1992, 4.2 (TRIPLE THE NUMBER OF WORKERS)

SUMMARY OF MAJOR INCIDENTS 2,3 FLIXBOROUGH, ENGLAND (1974) - CYCLOHEXANE MANUFACTURING AS A NYLON PRECURSOR 4,5 – VAPOR CLOUD EXPLOSION –KILLED 28 PEOPLE –CAUSE APPEARED TO BE DESIGN FOR TEMPORARY PIPING SYSTEM

FLIXBOROUGH

SUMMARY OF MAJOR INCIDENTS SEVESO, ITALY (1976) - DIOXIN 6 – TCP (2,4,5-TRICHLOROPHENOL) REACTOR EXPLODED RELEASING TCDD, (2,3,7,8- TETRACHLORODIBENZO-p-DIOXIN –THIS MATERIAL WAS A COMPONENT IN AGENT ORANGE

SUMMARY OF MAJOR INCIDENTS SEVESO, ITALY (1976) - DIOXIN 6 – PLUME SPREAD OVER AN AREA THAT CONTAINED OVER 100,000 PERSONS AND IMPACTED OTHER MUNICIPALITIES WITH A POPULATION OF –PRIMARY IMPACT WAS FEAR OF LONG- TERM EFFECTS AND OVERCOMING INITIAL TRAUMA –COULD BE THE SOURCE OF SARA TITLE III REQUIREMENTS

SUMMARY OF MAJOR INCIDENTS MEXICO CITY, MEXICO (1984) - LPG (LIQUID PETROLEUM GAS) TERMINAL – A BLEVE (BOILING LIQUID EXPANDING VAPOUR EXPLOSION) 7 –650 DEATHS –6400 INJURIES –PLANT DAMAGE = $31.3 MILLION

SUMMARY OF MAJOR INCIDENTS BHOPAL, INDIA (1984) - PESTICIDE MANUFACTURING 8 – UNEXPECTED CHEMICAL REACTION WHEN WATER ENTERED AN MIC (METHYL ISOCYANATE) STORAGE TANK –RELEASED ABOUT 40 TONS OF MATERIAL OVER A 2 HOUR PERIOD –SPREAD OVER A LOCAL POPULATION OF ABOUT 900,000 –ESTIMATED 3800 DEAD AND 11,000 DISABLED

SUMMARY OF MAJOR INCIDENTS BHOPAL, INDIA (1984) - PESTICIDE MANUFACTURING 8 – TRACED TO A NUMBER OF POSSIBLE SOURCES 9 –FAILURE TO MAINTAIN SAFETY SYSTEMS –INADEQUATE DESIGN OF SAFETY SYSTEMS –MIS-OPERATION OF THE FACILITY

SUMMARY OF MAJOR INCIDENTS PASADENA, TEXAS (1989) - POLYETHYLENE MANUFACTURING – POLYETHYLENE REACTOR EXPLOSION –KILLED 23 PEOPLE AND INJURED 130 –TRACED TO EITHER A SEAL FAILURE ON THE REACTOR AND/OR USE OF INEXPERIENCED MAINTENANCE PERSONNEL

EXAMPLE OF INCIDENT BHOPAL RELEASE –HOW IT OCCURRED –HOW IT WAS ANALYZED –RESULTING CHANGES

FUNDAMENTALS OF PROCESSES THERMODYNAMICS – CONSERVATION OF MASS AND ENERGY MASS IS NEITHER CREATED OR DESTROYED ENERGY IS NEITHER CREATED OR DESTROYED

FUNDAMENTALS OF PROCESSES THERMODYNAMICS – PROCESSES REQUIRE CHANGING CONDITIONSSYSTEMS MOVE TOWARDS A NEW EQUILIBRIUM THE RATE DEPENDS ON THE CHEMICAL AND MECHANICAL PROPERTIES OF THE SYSTEM WATER DOES NOT FLOW UPHILL WITHOUT A BOOST

FUNDAMENTALS OF PROCESSES EXAMPLE OF ETHANOL DISTILLATION

FUNDAMENTALS OF PROCESSES ENERGY/MATERIAL QUALITY CHANGES – ENERGY MAY BE ADDED OR REMOVED TO INITIATE A SYSTEM CHANGE WHEN ENERGY IS ADDED, IT FLOWS THROUGH THE SYSTEM TO BE CONSERVED, BUT IT IS DEGRADED IN QUALITY

ENERGY QUALITY CHANGES EXAMPLE OF HYDROELECTRIC POWER PLANT

ENERGY QUALITY CHANGES EXAMPLE OF HYDROELECTRIC POWER WATER CHANGES ITS EQUILIBRIUM POSITION WITH A RESULTANT CHANGE IN POTENTIAL ENERGY AND POWER PRODUCTION WATER IN THE RIVER CANNOT BE USED TO DRIVE THE TURBINE BECAUSE IT IS AT A LOWER POTENTIAL ENERGY LEVEL

MATERIAL QUALITY CHANGES PURE CHEMICALS THAT ARE DISPERSED IN WATER (SOLUBLE IN WATER) CANNOT BE RETURNED TO THEIR ORIGINAL PURITY WITHOUT USING ENERGY –DISTILLATION - ENERGY TO VAPORIZE/CONDENSE –CRYSTALLIZATION - ENERGY TO FREEZE/MELT –ADSORPTION OR ADSORPTION - ENERGY TO REGENERATE

REACTIONS –RESULTS IN FORMATION OF NEW CHEMICAL SPECIES –ELEMENTS ARE CONSERVED, BUT NEW MOLECULES MAY BE FORMED –REACTIONS CAN BE SINGLE, IN PARALLEL OR IN SERIES –MOLAR RELATIONSHIPS EXIST BETWEEN REACTANTS AND PRODUCTS

REACTIONS EXAMPLE OF METHANE COMBUSTION: –STOCHIOMETRIC REACTION

REACTIONS STOCHIOMETRIC REACTION WITH AIR FOR THE OXIDANT

REACTIONS REAL REACTIONS MAY NOT GO TO COMPLETION MAY REQUIRE AN EXCESS OF ONE COMPONENT TO COMPLETELY REACT THE OTHER

REACTIONS METHANE COMBUSTION WITH 130% EXCESS AIR

REACTIONS PARALLEL ETHANE COMBUSTION REACTIONS WITH 200% EXCESS AIR AND INCOMPLETE COMBUSTION

REACTIONS MOST REACTIONS DO NOT GO TO COMPLETION COMBUSTION CAN HAVE PRIMARY PRODUCTS OF CO2, H2O AND N2 BYPRODUCTS CAN INCLUDE CO, UNBURNED HYDROCARBONS, NOx, AND SO2 IN SMALLER QUANTITIES

REACTIONS OTHER TYPES OF OXIDATION-REDUCTION REACTIONS

REACTIONS OTHER TYPES OF NON-REDOX REACTIONS:

SEPARATION PROCESSES PROCESSES TO SEPARATE COMPONENTS, BEFORE OR AFTER REACTIONS PROCESSES TO CONCENTRATE COMPONENTS THE DRIVING FORCES FOR MOST OF THESE PROCESSES ARE –CHEMICAL EQUILIBRIUM –MECHANICAL –RATE DEPENDENT

SEPARATION PROCESSES PROCESS EFFICIENCY IS RELATED TO THE DEVIATION REQUIRED FROM AMBIENT CONDITIONS –THE MORE CHANGE REQUIRED, THE LESS THE EFFICIENCY –THE LESS CHANGE REQUIRED, THE HIGHER THE EFFICIENCY ALL HAVE POTENTIAL HAZARDS ASSOCIATED WITH THEM

TRANSPORT PROCESSES USED TO MOVE MATERIAL BETWEEN PROCESS OPERATIONS PUMPS TURBINES CONVEYORS GRAVITY PNEUMATIC

STORAGE OPERATIONS RAW MATERIALS FINISHED GOODS INTERMEDIATES OFF-SPEC MATERIALS

CONTROL SYSTEMS PROCESSES FOR NORMAL OPERATION –CONTINUOUS OPERATIONS –BATCH OPERATIONS START-UP

CONTROL SYSTEMS PROCESSES FOR NORMAL OPERATION –CONTINUOUS OPERATIONS –BATCH OPERATIONS START-UP SHUTDOWN –PROCESS INTERRUPTION –ROUTINE SHUTDOWN –EMERGENCY SHUTDOWN

CONTROL SYSTEMS SAFETY SYSTEMS –OUT-OF-RANGE CONDITIONS –INTERLOCKS BETWEEN UNITS

INHERENTLY SAFE DESIGN 10,11 TECHNIQUES THAT REDUCE THE RISKS ASSOCIATED WITH OPERATIONS EQUIPMENT FAILURE SHOULD NOT SERIOUSLY AFFECT SAFETY, OUTPUT OR EFFICIENCY

MINIMIZATION OF THE INTENSITY REDUCE QUANTITIES OF MATERIALS MAINTAINED IN INVENTORIES AND IN THE PROCESS –QUANTITIES IN INVENTORIES REDUCED CAPITAL COSTS REDUCED MAINTENANCE LESS MATERIAL TO PARTICIPATE IN A REACTION HAZARDOUS REACTANT BE MANUFACTURED ON SITE FROM LESS HAZARDOUS PRECURSORS

REACTORS SMALLER REACTORS TYPICALLY HAVE LESS MATERIAL IN PROCESS HAVE BETTER CONTROL OF HEAT TRANSFER AND CAN BE MORE EFFICIENT 12

GENERAL FACTORS TO REDUCE REACTOR RISKS 13

COMPARISON OF REACTOR ALTERNATIVES

CONTINUOUS REACTORS HAVE SMALLER INVENTORIES THAN BATCH REACTORS TUBULAR REACTORS HAVE SMALLER INVENTORIES THAN TANK REACTORS THIN FILM REACTORS HAVE SMALLER INVENTORIES THAN TUBULAR REACTORS GAS PHASE REACTORS HAVE LESS INVENTORY THAN LIQUID PHASE REACTOR

SUBSTITUTION USE OF SAFER NON-REACTIVE CHEMICALS MAY DECREASE EFFICIENCY MAY ALSO DECREASE COSTS

SUBSTITUTION HEAT TRANSFER FOR HIGH TEMPERATURE HEAT TRANSFER USE WATER OR MOLTEN SALTS IN PLACE OF HYDROCARBON- BASED HEAT TRANSFER FLUIDS 14,15

SUBSTITUTION HEAT TRANSFER FOR LOW TEMPERATURE HEAT TRANSFER REPLACE OZONE SCAVENGING FLUIDS (FREONS) WITH ALTERNATES (N 2, PROPANE, HYDROFLUOROCARBONS) 16

SUBSTITUTION SOLVENT REPLACEMENT –USE WATER-BASED PAINT IN PLACE OF SOLVENT-BASED PAINTS –USE OF WATER-BASED SOLVENTS OR CO 2 IN CHIP MANUFACTURING PROCESSES 17,18 (OFTEN WITH IMPROVED PRODUCT PERFORMANCE)

ATTENUATION MODIFY CONDITIONS TO MINIMIZE THE IMPACT OF HAZARDOUS EVENTS 19 –ADDITION OF INERT COMPONENT TO SYSTEM CAN DILUTE THE POSSIBLE INTENSITY OF A REACTION –MODIFIED CATALYSTS CAN REDUCE THE TEMPERATURES AND PRESSURES REQUIRED FOR THE REACTION 20

ATTENUATION STORAGE OPTIONS –LIQUIFIED GASES STORED AT CRYOGENIC TEMPERATURES STORED AT ATMOSPHERIC PRESSURE USES SMALLER VOLUMES THAT GAS STORAGE TEMPERATURES ARE FREQUENTLY BELOW IGNITION TEMPERATURES IN AIR

ATTENUATION STORAGE OPTIONS –MINIMIZE STORAGE BY ON-SITE PRODUCTION HYDROGEN GENERATED BY ELECTROLYSIS OR PARTIAL OXIDATION OF NATURAL GAS CHLORINE GENERATION ON SITE

ATTENUATION STORAGE OPTIONS –STORAGE IN LESS NOXIOUS FORMS CHLORINE FOR POOLS GASEOUS STORAGE LIQUID STORAGE SOLID FORM (Cyranuric Acid) DILUTED SOLID FORM (Cyranuric Acid WITH INERT FILLER)

LIMITATION OF THE EFFECTS OPERATE PROCESSES IN STAGES TO AVOID PROCESS CONDITIONS THAT CAN LEAD TO EVENTS –MULTIPLE STAGES FOR OPERATIONS 21 –CHANGING THE SEQUENCE OF REACTIONS CAN REDUCE HAZARDS –ELIMINATION OF UNNECESSARY STEPS TO SIMPLIFY THE PROCESS

SIMPLIFICATION SIMPLIFIED CONTROL INSTRUMENTATION –EVERY CONTROL LOOP CAN FAIL –ELIMINATION OF THE NEED FOR A CONTROL LOOP THROUGH EQUIPMENT DESIGN –ANOTHER APPROACH IS TO MAKE CERTAIN THAT CONTROL INSTRUMENTATION SENSORS ARE SEPARATE FROM ALARM INSTRUMENTATION SENSORS

EXAMPLE OF USE OF SPECIAL MATERIALS OF CONSTRUCTION OXYGEN COMPRESSORS

EXAMPLE OF USE OF SPECIAL MATERIALS OF CONSTRUCTION IF THE COMPRESSOR ROTOR GOES OUT OF BALANCE, IT WILL RUB AGAINST THE STATOR AND CAUSE A FIRE FIRE EMITS INTENSE THERMAL RADIATION COMPRESSOR IS EQUIPPED WITH VIBRATION SENSORS COMPRESSOR WAS INSTALLED IN A SEALED HOUSING PARTS THAT WOULD RUB FIRST WERE FABRICATED FROM SILVER, A METAL THAT WILL MELT BEFORE IT IGNITES

HAZARDOUS ANALYSIS STUDIES PROCESSES DEVELOPED TO IDENTIFY PROBLEMS INHERENT IN PROCESS DESIGNS.

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS INTENTS DEFINE PROCESS HAZARDS –HUMAN FACTORS ANALYSIS –SAFETY & HEALTH IMPACTS OF LOSS OF CONTROL DETERMINE HISTORY OF INCIDENTS IN RELATED FACILITIES CONFIRM ADEQUACY OF OPERATING, ENGINEERING AND ADMINISTRATIVE CONTROLS EVALUATE IMPACT OF FACILITY SITING

ANALYSES ARE NOW REQUIRED FOR PROCESSES SARA TITLE III - COMMUNITY RIGHT TO KNOW AS PER EPA DEVELOPED 40CFR67, RISK MANAGEMENT PROGRAM OSHA REGULATION CFR

HAZOP - (HAZARD AND OPERABILITY STUDY) EXAMINES CONDITIONS AT DIFFERENT LOCATIONS IN THE FACILITY RESULTS IN A REPORT WITH LIST OF CHANGES FOR PROCESS DEFINITION OF PROCESS HAZARDS CLARIFICATION OF OPERATING PROCEDURES

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS ASSEMBLE ANALYSIS TEAM - WHO HAVE NECESSARY PROCESS EXPERIENCE AND KNOWLEDGE –DESIGN ENGINEERS –OPERATORS –MATERIALS SPECIALISTS –EH&S SPECIALISTS –MAINTENANCE PERSONNEL

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS COLLECT DATA –DESIGN DRAWINGS –EQUIPMENT DRAWINGS, CALCULATIONS AND SPECIFICATIONS –MAINTENANCE INFORMATION –MSDS DEFINE PROCESS NODES –BREAK PROCESS INTO AREAS FOR ANALYSIS –LOCATE THESE ON A SET OF DRAWINGS

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS ANALYZE PARAMETERS FOR EACH NODE –PURPOSE OR INTENT PROCESS FUNCTIONS PROCESS VARIABLES HUMAN INTERACTION - HOW IS THE OPERATOR INTEGRATED INTO THE OPERATION OF THE PROCESS AT EACH NODE.

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS DEFINE RISK - SEVERITY AND PROBABILITY –DETERMINE CAUSE – EQUIPMENT FAILURE –OPERATOR ERROR –ENVIRONMENTAL CHANGES –EXTERNAL IMPACTS

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS ESTIMATE SEVERITY

SEQUENCE OF EVENTS FOR A HAZOPS ANALYSIS PREDICT FREQUENCY OF EVENT

HAZARDS ANALYSIS (HAZAN) STUDY STARTS WITH THE SAME INFORMATION AND TEAM AS THE HAZOPS STUDY EXAMINES THE RESULT OF FAILURE OF EQUIPMENT OR CONTROLS –INDIVIDUAL - SINGLE JEOPARDY –MULTIPLE - DOUBLE JEOPARDY

HAZARDS ANALYSIS (HAZAN) STUDY CAN BE ORGANIZED WITH FAULT TREE (FTA)

HAZARDS ANALYSIS (HAZAN) STUDY FAULT TREE SYMBOLS FAULT TREES USE PROGRAMMING SYMBOLS FOR EACH TYPE OF JUNCTION

FAULT TREE EXAMPLE - NO PAPER FOR BREAKFAST

PRIMARY SOURCES OF CATASTROPHIC EVENTS HUMAN ERROR MISLABELING TRIP FAILURES STATIC ELECTRICITY WRONG MATERIAL OF CONSTRUCTION FAULTY OPERATING PROCEDURES UNEXPECTED REVERSE FLOW COMPUTER CONTROL PROBLEMS IGNORANCE