Chapter 24

Health, Safety, and Environment

NMSU Chemical Engineering
Ch E 452
 Why Worry about Safety?
38 Year DuPont Fatality Summary (1955-92)

non-process related
process related
crushing trauma
suffocation
cause

chemical burn incidents

toxic ingestion fatalities
fires
explosions

0 20 40 60 80 100
number of occurrences
 Risk Assessment
Activity OSHA Incident Rate Fatal Accident Rate Fatality Rate
(injuries & deaths (deaths per 108 h) (deaths / person / yr)
/200,000 h)

Working in Chemical Industry 0.49 4

Staying at Home 3

Working in Steel Industry 1.54 8

Working in Construction 3.88 67

Traveling by Car 57 170 x 10-6

Rock Climbing 4000 40 x 10-6

Smoking (1 pack per day) 5000 x 10-6

Being struck by Lightning 0.1 x 10-6

 Regulations and Agencies
• Rules and regulations arise from governmental (OSHA, NIOSH,
EPA, DOT, MSHA) and non-governmental agencies (AIChE, API,
ASTM, NFPA, etc.)
• Federal government rules are published in the Federal
Register (FR) and the Code of Federal Regulations (CFR).
• Important Standards include
– OSHA Act and Air Contamination Standard – give exposure limits
– Hazard Communication Standard – “worker Right to Know” or
HazCom. Specifies proper labeling of containers and availability of
Material Safety Data Sheets (MSDS).
 Worker Exposure

• Workers
– OSHA Time weighted average
• Permissible Exposure Limit over 8 hr day
• Threshold Limit Values (ACGIH)
– NIOSH – Recommended Exposure Limits
– Short Term Exposure Limit – 15 minute exposure
• Public
– EPA – CAA, CWA, SARA
– DOT
• MSDS
 Fires and Explosions

• Combustion - rapid oxidation

– At room temp rate usually low
– Increases rapidly with temperature
– Below auto-ignition temperature – remove heat and
returns to room temperature
• Auto-ignition temperature
– above this temperature combustion is sustained when
heat source removed.
– Energy to heat small region to above A-I temp is called
the ignition energy – very small
 Fires and Explosions

• Flammability (or explosive) Limits

– LFL (LEL) – min concentration of fuel in oxidant
(usually air) that will support combustion
– UFL (UEL) - max concentration of fuel in oxidant
(usually air) that will support combustion
– MOC – relates to “inerting”
 Fires and Explosions

• Explosion – rapid combustion in which the pressure

waves formed propagate the combustion. Waves
compresses and heats flammable mixture to its AI
temperature.
– Deflagraton (< speed of sound)
– Detonation (> speed of sound)
• Vapor cloud explosion
• BLEVE (boiling-liquid expanding vapor-cloud explosion
– rapid expansion of vapor can cause a massive shock
wave)
 Fires and Explosions

• Runaway reaction
– Insufficient heat removal from exothermic
reaction  LOCA (loss of cooling accident)
– Use a small or large T for cooling medium?
• Over-pressure
– Pressure relief valves
– Bursting discs
 Inherently Safe Design

• Substitution – avoid
• Intensification – use less
• Attenuation – less hazardous conditions
• Containment – do not let out
• Control Leaks – emergency isolation
• Survive Leaks – fire protection, etc.
General Duty Clause of the Occupational
Safety & Health Act of 1970
• Section 5(a)1 requires that every working man and woman
must be provided with a safe and healthful workplace:
• “Each employer shall furnish to each of his employees
employment and a place of employment which is free from
recognized hazards that are causing or are likely to cause
death or serious physical harm to his employee’s”
• Translation: The employer is obligated to protect employees
from recognized hazards for which there is not an OSHA
standard which applies to the situation or if hazards still exist
after compliance with a standard.
How to Read OHSA Regulation
Numbering System
e.g., 29CFR/1910/Subpart H/1910.119/(i)/(2)/(ii)

Title 29 CFR Department of Labor

Part 1910 Occupational Safety & Health
Subpart H Hazardous Materials
Section 1910.119 PSM of Highly Hazardous Chemicals
Paragraph (i) Pre-Startup Safety Review
Subparagraphs (2) (ii) Safety, operating, maintenance,
emergency procedures...”
Process Safety Management (PSM)
(29 CFR 1910.119)
Legal Requirements of PSM
contained within subpart H, Hazardous Materials
coverage by this reg is triggered by any of the following:
– having specified threshold quantities of a chemical from the
list of PSM regulated chemicals,
– inventory of 10,000 lbs of a flammable liquid or gas, except
for hydrocarbon fuels used solely for workplace
consumption as a fuel, and flammable liquids stored in
atmospheric tanks which are kept below their boiling points
without chilling or refrigeration,
– explosives manufacture, or
– pyrotechnics manufacture.
29 CFR 1910.119
• Section H contains requirements for preventing or
minimizing the consequences of catastrophic
releases of toxic, reactive, flammable, or explosive
chemicals.
• Standards for dealing with hazards in storage,
handling, and processing highly hazardous materials.
• Focus is on all stages of design, development, and
operation of a facility. PSM must be communicated
to and accepted by all employees of the facility.
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– hazards of chemicals used in the process (MSDS

meeting requirements of 29 CFR 1910.1200 (g) )
including; permissible exposure limits, toxicity, physical
data, reactivity data, corrosivity data, thermal and
chemical stability data, and the hazardous effects of
inadvertent mixing;
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– the technology of the process, including PFD, process

chemistry, maximum intended inventories, safe upper
& lower limits of operation (temperature, pressures,
flows, compositions), health/safety consequences of
deviations from limits;
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– the equipment of the process, including; materials of

construction, relief system design and design basis,
P&IDs, ventilation system, design codes and standards
used, material and energy balances, safety systems
(interlocks, detection, suppression);
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to
– a process hazard analysis (PHA), including one or more: What-if,
Checklist, Hazard and Operability Study (HAZOP), Failure Mode
Effect Analysis (FMEA), Fault Tree Analysis (FTA). PHA must
address process hazards, previous incidents, engineering and
administrative controls and consequences of their failure, siting,
human factors, qualitative evaluation of effects of failures on
employees. Analysis performed by a team of experts. A system to
address the findings put in place. Analysis reviewed every five
years. Documentation retained for the life of the process;
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– written operating procedures, including: steps for each

phase of operations; (initial startup, normal operations,
temporary operations, emergency shutdown,
emergency operations, normal shutdown, startup
following turnaround or emergency shutdown);
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– operating limits, including consequences for deviation

from limits and steps to correct or avoid deviations,
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– safety and health information including hazard

information, precautions to prevent explosion,
engineering and administrative controls, personal
protective equipment, measures taken in the event of
an exposure, control of hazardous chemical
inventories;
Items expressly addressed in 29 CFR 1910.119
(1) Process safety information for many aspects of the
process must be developed and maintained,
including information regarding or pertaining to

– safety systems and their functions.

Items expressly addressed in 29 CFR 1910.119
2. Operating Procedures will always be readily available
3. Operating Procedures will be periodically reviewed
4. Safe practices will be developed (e.g., lock-out/tag-out)
5. Training will be provided and documented for each employee
involved in operating the process at the time of assignment
and on a periodic refresher basis.
6. Regarding contractors, employers shall; evaluate safety
performance/programs of a contractor prior to selecting;
provide hazards communications to the contractors; provide
details of the site emergency action plan; limit contractor
access to process area; periodically evaluate contractor
performance; maintain illness and injury log for contract
employees;
Items expressly addressed in 29 CFR 1910.119
7. Perform a pre-startup safety review for new or modified
process facilities prior to the introduction of hazardous
chemicals to the process, confirming construction is in
accordance with specification; safety, operation,
maintenance, & emergency procedures in place; PHR
recommendations have been addressed; training is complete
8. Written procedures, describing how mechanical integrity will
be maintained for equipment, training on such maintenance,
and testing documentation for pressure vessels & storage
tanks, piping & valves, relief & vent systems emergency
shutdown systems, controls, alarms & interlocks, pumps
9. Hot work permit issuance according to 1910.252(a)
Items expressly addressed in 29 CFR 1910.119
10. Written management of change procedures for
process chemicals, technology, equipment and
facilities; prior to making change, consider technical
basis for proposed change, the impact of change on
safety and health, modifications to operating
procedures, time required for changes,
authorization requirements; prior to startup after
change, consideration to retraining of operators,
crafts, contractors, update safety data, modify
operating procedures
11. Incident investigation
12. Emergency action plan
 Process Hazards Reviews
• Process Hazards Reviews (PHR) are a systematic,
comprehensive study of a process, performed by a
cross-sectional team of employees using recognized
analysis methods to:
– identify process hazards
– identify way in which each hazardous incident may occur
– evaluate likelihood of each incident and the consequences
of it occurring
– develop practical recommendations to eliminate/control
identified hazards
 PHR Team
• Chairman
– arranges for process description
– assures comprehensive and intensive review
– provides documentation and communication
• PHR Resource - individual familiar with PHR procedure,
documentation,...
• Remaining Team Composition
– operations (hands-on operating experience, previous incidents)
– technical (process basis and limits)
– maintenance (inspections, equipment history)
– specialists (as needed for instruments, mechanical, control, etc.)
– consultants (as needed for process safety and fire protection)
 PHR Pre-Review Preparation
• select review team, define scope of the review
• assemble up-to-date process information
• all process drawings (current)
• relevant past reviews and incident reports
• all relevant safety data (MSDSs, regulations,
reports,...)
• familiarize team members with process
 PHR Review
1. Divide process into independent segments (if
possible)
2. Identify all hazards and list for each segment
3. Select appropriate analysis method for each hazard
4. Analyze hazards
5. Develop Recommendations
6. Compile final report w/ responsibilities/timing on all
recommendations
7. Present results for management/operations
approval
8. Track and implement recommendations
 PHR Methods
• What-If
• Checklist
• Hazard and Operability Study (HAZOP)
• Failure Mode and Effect Analysis (FMEA)
• Fault Tree Analysis
 What-IF

• based on spontaneously formulated questions

by the review team for the specific process
under consideration
• unstructured, unbounded, time-driven, based
on questioner’s experience
 Checklist

• based on an established checklist of items to

consider
• based on retrospective experience
• no universal checklist exists, relies on finding
appropriate list
• concise summary of important items
 HAZOP
• structured study of specified deviations from design
conditions
• model driven and bounded, flexible, good for novel situations
• identifies hazards, does not develop solutions
• requires trained team leader
• timing
– meetings last ~ 2½-3 hours each, not to exceed 2 meetings per week
– 1 meeting per P&ID (depending on complexity)
– requires a preliminary hazard study & analysis be performed
• requires reasonably firm model (drawings)
• assumes good design
• looks for deviations from design conditions
 HAZOP

• Intention - How process is designed to operate

• Deviation - From operating specifications
• Cause - How deviation might occur
• Consequence - Of deviation with reasonable
causes
• Hazard - Consequences that could cause
dangerous situation
 HAZOP guide words
 more of - any relevant physical parameter than there should
be (i.e., more flow, more pressure, more temperature, etc.)
 less of - opposite of more of
 none of - none of a system parameter when there should be
 reverse - the logical opposite (i.e., reverse flow)
 part of - system composition different from what it should be
 as well as - more things present than should be (i.e., as well
as a vapor phase when only liquid phase should be present)
 other than - total substitution of a fluid or material
 special - process need other than normal operation (start-up,
shutdown, maintenance, provision for services failures, spare
equipment,...)
 HAZOP Method
use guide-words to consider consequences of deviations

GUIDE WORDS SYSTEM

more of PARAMETERS
loss of flow rate
none temperature
reverse pressure
part of viscosity
as well as concentration
other duration (time)

deviation from
cause consequences
design conditions
 HAZOP Guide Word Deviation Matrix
more of less of none of reverse part of as well as other than

low wrong contaminant wrong

flow high flow no flow back flow
flow conc s material

high low
temp
temp temp

high low
pres
pressure pressure

too long, too late, miss a backward action extra actions

time wrong time
too late too soon step step missed initiated

separate matrix can be generated for electrical systems: current,

voltage, frequency, phase, start-up/shutdown, interference, power
failure…
  Deviations Consider

pump racing, delivery vessel pressure lost, suction pressurized, scale dislodged, leak in heat exchanger, loss of
High Flow
automated control, operator error
pump failure, scaling of delivery, presence of foreign body or sediment, poor suction condition, cavitation, leak in heat
Low Flow
exchanger, drain leaking, valve jammed, loss of automated control, operator error
pump failure, delivery vessel/main overpressurized, gas locking, blockage, presence of foreign body, scale, sediment,
No Flow
suction vessel empty, loss of automated control, operator error, failure of joint, valve, pipe, trap, bursting disk, relief valve

P Reverse Flow Pump failure, pump reversed, delivery vessel/main overpressurized, poor isolation, gas locking, surging, back siphoning
I
P High/Low Pressure boiling, cavitation, freezing, chemical breakdown, flashing, condensation, sedimentation, scaling, foaming, gas release,
E
L High/Low Temperature priming, exploding, imploding, changes in viscosity, density, external fire, weather conditions, hammer
I
N Static Buildup source of ignition, personnel shock
E
High/Low Concentration changes in proportion of mixture, in water or solvent content
Wrong Material ingress of air, water, steam, fuel, lubricants, corrosion products, other process materials from high pressure system,
Contaminations leakage through heat exchangers, gas entrainment, spray, mist, etc.
vacuum, pressure testing with harmless material
Testing
concentration of reactants, intermediates, abnormal flows, temperatures, pressures, etc.
Commissioning
purging, venting, sweetening, drying, washing, access, spares.
Maintenance
Should this pipeline be considered for special attention?
High Reaction
frothing, other reaction, runaway reaction, gassing, exothermic, endothermic, enrichment, catalyst
V Low Reaction
E
S
High Mixing
S agitator failure, vortex, layering, erosion
E Low Mixing
L
S High Level
flooding, pressure surges, corrosion, sludge
Low Level

B Failure of Power, Air,

O consider part and total failures and compound failures
T Steam, Nitrogen, Water,
consider lighting of plant and instrument panels, power for alarms, and local and general failure action of controls
H Fuel, Vacuum, and Vents
 HAZOP Procedure
select a line or vessel

explain design intention NO

all
lines & YES
select guide word vessels done
done
?
develop meaningful deviation

list causes, consequences, NO

and protections
all
guide
evaluate need for risk
words
control recommendation YES
used
?
Table 24.5. HAZOP for the Feed Heater of the Hydrodealkylation (HDA) Process
Process Unit: H-101, Feed Heater, Figure 1.3
6
Intention: To provide feed to the Reactor (Stream 6) at 600ºC.
4

fg air

Guide Word Deviation Cause Consequence Action

No No flow (Stream 4)
 No O2 in combustion
products
 
 No flow (Stream 6)
 No benzene in Stream
6 off to R-101 and loss of
 No fuel gas flow
 No flame
blockage in line Fluid in H-101 overheats Consider an interlock on fuel
gas flow
Rich fuel:air mixture Unburned fuel and CO None. O2 analyzer with self-
in combustion products checking circuit controls ratio
reliably
O2 analyzer malfunction Potentially rich fuel:air 
mixture
Heat tubes burst Explosion Interlock with sudden P
drop alarm and shutdown
C-101 not working Hydrogen:Toluene ratio Maintain spare compressor C-
101
hydrogen to fuel gas
Supply pipe rupture Cold shot to R-101, Interlock with process
quenching reaction shutdown
Momentary loss of fuel gas Explosive mixture Automatic flame detection
with re-ignition cycle
 Failure Mode & Effect Analysis
(FEMA)
• based on an investigation of the potential of
individual component failures
• component/steps driven
• flexible, good for novel situations
• requires accurate model and personnel
experienced in FMEA technique
 FEMA Objectives
• identify component failures which may
cause/contribute to hazardous events
• identify component failures which may have multiple
effects on the system (common mode failures)
• evaluate adequacy of safeguards, recommend
corrections
• identify hazards which require further, possibly
quantitative, analysis to facilitate decisions regarding
the extent of improvements required
• document to assure continuity for future review teams
 FEMA Concept
• assumes “normal mode” is okay
• How could this component fail? and
How does failure affect the system?
• rating assigned to each failure reflecting severity and
probability of risk
 0 = system fails safe or only inconsequential results
 1 = reasonable potential for serious injury or small property loss
 2 = reasonable potential for a single fatality, multiple serious
injuries or a significant property loss or business interruption
 3 = reasonable potential for multiple deaths, large
property/business loss
 FEMA Concept
1. identify a component
2. determine how it can fail
3. determine immediate effect of failure (does it cause a process
variable to change, start a problem, defeat a protection system?)
4. determine reasonable worst catastrophe that failure could be
involved in
5. rate the catastrophe (0-3)
6. define failure as inhibitor or enabler
7. determine how often failure occurs
8. determine how the failure mode is detected
9. identify what protections are used to prevent failure
10. determine need for further action
FEMA Worksheet
 Fault Tree Analysis
• logical model and quantification of an identified
major process hazard event

• Advantages
– aids decision-making with quantitative evaluation
– shows only the failures that lead to the top event
– models human failures and process chemistry
• Disadvantages
– time consuming
– difficult to obtain realistic failure rates
– limited scope
 FTA Procedure
• identify an undesired incident (top event)
• model all source causes of top event
• assign appropriate failure rates to source
causes
• calculate top event frequency
• evaluate acceptability of calculated top event
frequenc
 FTA Procedure
identify top event

construct the fault tree develop improvements

analyze qualitatively NO

make
decision:
analyze quanitatively acceptable
?

YES

accept system
FTA Nomenclature
 FTA Construction
• select the TOP EVENT
• list all necessary, immediate and sufficient causes
– necessary - show all required conditions
– immediate - show direct causes, not jumping ahead
– sufficient - show only required causes, no extras
• define cause types as system, basis source, or normal
source cause
• select gate type
• place causes under gate and connect causes to gate
with lines
• repeat for every subevent until no subevents remain
 Reduce TOP EVENT Frequency
• additional safety devices: rupture discs, relief
valves, interlocks
• improved design: fail safe or redundant
systems
• increased testing frequency: instruments,
mechanical devices
• additional warnings: instruments, alarms
• improved operating procedures, training,
ergonomics,...
PHR Method
Selection
Decision
Tree