Design strategies with respect to hazardous materials
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DESIGN STRATEGIES WITH RESPECT TO HAZARDOUS MATERIALS. THE NATURE OF RISK IN INDUSTRIAL FACILITIES. http://www.bls.gov/iif/oshwc/cfoi/cfch0008.pdf. FATAL WORK INJURIES. http://www.bls.gov/iif/oshwc/cfoi/cfch0008.pdf. FATAL WORK INJURIES. http://www.bls.gov/iif/oshwc/cfoi/cfch0008.pdf.

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DESIGN STRATEGIES WITH RESPECT TO HAZARDOUS MATERIALS

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DESIGN STRATEGIES WITH RESPECT TO HAZARDOUS MATERIALS


THE NATURE OF RISK IN INDUSTRIALFACILITIES

http://www.bls.gov/iif/oshwc/cfoi/cfch0008.pdf


FATAL WORK INJURIES

http://www.bls.gov/iif/oshwc/cfoi/cfch0008.pdf


FATAL WORK INJURIES

http://www.bls.gov/iif/oshwc/cfoi/cfch0008.pdf


THE NATURE OF RISK IN INDUSTRIAL FACILITIES

  • COMPARISON VALUES - DEATHS/100,000 WORKERS

    • IN 1912, 21 (18,000 - 21,000 DEATHS)

    • IN 1992, 4.2 (TRIPLE THE NUMBER OF WORKERS)


SUMMARY OF MAJOR INCIDENTS2,3

  • 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) - DIOXIN6

    • 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) - DIOXIN6

    • PLUME SPREAD OVER AN AREA THAT CONTAINED OVER 100,000 PERSONS AND IMPACTED OTHER MUNICIPALITIES WITH A POPULATION OF 17000

    • 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 MANUFACTURING8

    • 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 MANUFACTURING8

    • TRACED TO A NUMBER OF POSSIBLE SOURCES9

    • 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 DESIGN10,11

  • 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 EFFICIENT12


GENERAL FACTORS TO REDUCE REACTOR RISKS13


GENERAL FACTORS TO REDUCE REACTOR RISKS13


COMPARISON OF REACTOR ALTERNATIVES


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 FLUIDS14,15


SUBSTITUTION

  • HEAT TRANSFER

  • FOR LOW TEMPERATURE HEAT TRANSFER REPLACE OZONE SCAVENGING FLUIDS (FREONS) WITH ALTERNATES (N2, PROPANE, HYDROFLUOROCARBONS)16


SUBSTITUTION

  • SOLVENT REPLACEMENT

    • USE WATER-BASED PAINT IN PLACE OF SOLVENT-BASED PAINTS

    • USE OF WATER-BASED SOLVENTS OR CO2 IN CHIP MANUFACTURING PROCESSES17,18 (OFTEN WITH IMPROVED PRODUCT PERFORMANCE)


ATTENUATION

  • MODIFY CONDITIONS TO MINIMIZE THE IMPACT OF HAZARDOUS EVENTS19

    • 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 REACTION20


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 OPERATIONS21

    • 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 1910.119


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


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