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Chemical Process Safety

Chapter 3: Industrial Hygiene

Laws and regulatory agencies

Industrial Hygiene
Government Regulations
1. Laws are enacted by Congress and signed by the
President. They are published in the United
States Code (USC). The laws do not have details
on implementation.
2. The applicable government agency develops and
proposes a regulation. The regulation contains
the details on implementation. It is published in
the Federal Register and a comment period and
hearing is normally held.
3. The Final Rule is published in the Federal
Register and the Code of Federal Regulations.
Government Regulations
US Congress creates Laws ex, Clean Air & Water Acts

Various federal organizations are authorized to develop

regulations, standards, expectations for compliance and
Environmental Protection Agency (EPA)
Occupational Safety & Health Administration (OSHA)
State and local regulatory agencies are also involved in
implementation, compliance & enforcement
New facilities & retrofits must obtain approvals / permits
from appropriate agencies
Globally similar principles, but wide variation in
processes & expectations
Government Regulations
The two regulations most applicable to chemical
plants are:
Occupational Safety and Health Administration
29 CFR 1910.119 Process Safety Management of
Highly Hazardous Chemicals

Environmental Protection Agency (EPA):

40 CFR Part 68 Risk Management Programs
US Regulations
Process Safety Management of Highly Hazardous Chemicals
(OSHA, 1992)
- general requirements for managing hazardous substances; with
focus to protect on-site people
- 14 major sections: process safety information, process hazard
analysis, management of change, audits, employee participation,

Risk Management Plan (EPA, 1996)

- aimed at decreasing number & magnitude of accidental releases of
toxic & flammable substances, with focus to protect off-site people
& environment
- applicable to facilities producing greater than a threshold amount of
hazardous substances
- 4 major elements: hazard assessment, prevention program,
emergency response & handling and sharing of this information
OSHA Highlights Table 3-2
Employers MUST admit OSHA compliance
officers into sites for inspection, with no
advanced notice, but warrant may be
OSHA can inspect safety and health records
Criminal penalties CAN be invoked
OSHA can request shut down of facilities
- 14 major sections -
Employee Participation Process Safety
Process Hazard Information
Analysis Operating Procedures
Training Contractors
Pre-startup Safety Mechanical Integrity
Review Management of Change
Hot Work Permit Emergency Planning
Incident Investigation Trade Secrets
Compliance Audit

List of hazardous substances and threshold

quantities (Appendix A)
Risk-based criteria
General duty and obligation to identify hazards
and maintain a safe workplace (regardless of
presence of hazardous substance)
Loss prevention (in the interest of company)
Employee Participation
Written plan of action

Consult with employees on the conduct and

development of process safety programs

Provide access to (Process Hazard Analysis) PHAs and all

other information developed for the process safety

Objective: Accountability
Process Safety Information

Technology Information: Process Flow Diagrams, Process Chemistry,

Maximum Inventory, Safe Upper and Lower Limits, Consequences
of Deviation
Chemical Information: Physical Data, Toxicity Information, Permissible
Exposure Limits, Reactivity Data, Corrosivity Data, Thermal and
Chemical Stability Data, Hazardous Effects of Inadvertent Mixing
Equipment Information: Materials of Construction, Piping and
Instrument Diagrams, Electrical Classification, Relief Systems
Design and Design Basis, Ventilation System Design, Design Codes
Employed, Material and Energy Balances, Safety Systems

Objective: Knowledge and Control of the Operation

(Host Employer Responsibilities)
Host employer must:
Consider Safety Records in Selecting Contractors
Inform Contractors of Potential Process Hazards
Explain the Facility's Emergency Action Plan
Evaluate Contractor Safety Performance
Maintain Injury/Illness Log for Contractors Working in
Process Areas

Objective: Knowledge and Control of the Operation

(Contractor Employer Responsibilities)
Contractor employer must:
Train Their Employees in Safe Work Practices and
Document That Training
Assure That Employees Know About Potential Process
Hazards and Emergency Action Plan
Assure That Employees Follow Safety Rules of Facility
Advise Employer of Hazards

Objective: Knowledge and Control of the Operation

Operating Procedures
Written Operating Procedures which are specific to the
person or persons for each of the facility's operating areas
The Procedures Must Address Each of the Following:
Initial Startup
Normal Operation
Temporary Operations
Emergency Operations
Normal Shutdown
Startup Following Turnaround

Objective: Knowledge and Control of the Operation

Operating Procedures (cont)
Written Operating Procedures which are specific to the
person or persons for each of the facility's operating areas
The Procedures Must Address Each of the Following:
Operating limits and consequences of deviations,
Safety and health considerations,
Hazardous properties of the chemicals,
Exposure precautions,
Engineering and administrative controls,
Quality control specifications for all chemicals,
Special or unique hazards, and
Safety control systems and functions.

Objective: Knowledge and Control of the Operation

Safe Work Practices

Hot Work Permit

Fire Prevention and Protection Requirements
Safe Conduct of Operating, Maintenance, and
Modification Activities
Control of Materials and Substances
Control of Access to Process Areas

Objective: Knowledge and Control of the Operation

Training and Certification

Certified Training Must be Provided to all Personnel

Responsible for Operating the Facility.

Training Should Include:

Initial Training
Refresher and Supplemental Training
Communication of Facility / Process Changes
Contractor Training

Objective: Knowledge and Control of the Operation

Process Hazards Analysis
PHA Should be Performed at Least Every Five Years to
Minimize the Likelihood of Occurrence and the Consequence
of a Dangerous Substance Release
Recommended Methods:
What If (what could go wrong)
Checklist (specific issues)
What If/Checklist
HAZOP (rigorous, hazards and operability study)
FMEA (failure modes and effects analysis)
FTA (fault tree analysis)
Need timely resolution of issues identified by PHA

Objective: Hazards Identification and Control of Hazards

Management of Change

Establish and Implement Written

Management of Change Procedures Which
Technical Basis (except for in-kind replacement)
Impact on Safety and Health
Modifications to Operating Procedures
Necessary Time Period for the Change
Authorization Requirements

Objective: Hazards Identification and Control of Hazards

Pre-startup Safety Review

Pre-Startup Safety Review for New and

Modified Facilities
Construction is in Accordance with Design
Safety, Operating, and Emergency Procedures in
Resolution of PHA Recommendations
Employees and contractors have been trained

Objective: Hazards Identification and Control of Hazards

Mechanical Integrity
Establish and Implement Written Procedures to Maintain the
Mechanical Integrity of:
o Pressure Vessels and Storage Tanks
o Piping Systems
o Relief and Vent Systems
o Emergency Shutdown (ESD) Systems
o Controls, Alarms, and Interlocks

Includes written procedures, training on preventative

maintenance, schedule for inspections / testing, process to
correct deficiencies, and process to ensure equipment &
spare parts are being maintained.

Objective: Hazards Identification and Control of Hazards

Emergency Planning and Response

Establish and Implement an Emergency Action

Plan generally includes written procedures,
internal and external notifications, by & to
whom, training & drills, and timeframe

Objective: Accidents and learning from

Incident Investigation
Incidents that Result in or Could Reasonably have
Resulted in a Major Accident Must be Investigated.
Incident Investigation Report:
Date of Incident
Team knowledgeable of process
Date Investigation Began
Recommendations to reduce hazards and likelihood of
future incidents

Objective: Accidents and learning from accidents

Compliance Audits

Conduct Audit Every Three Years

Audit Team
Determine Appropriate Response to Each
Correct Deficiencies
Retain Two Most Recent Audits
General duty for facilities to:
o Identify hazards that may result from releases
o Design and maintain a safe facility
o Minimize the consequences of releases

Required EPA to:

o Promulgate a list of substances with threshold quantities
o Develop a risk management program rule
Risk Management Plan (EPA, 1996)

Aimed at decreasing number & magnitude of

accidental releases of toxic & flammable
Focus to protect off-site people &
Applicable to facilities producing greater than
a threshold amount for each of 140 hazardous
Implement risk management program
1. Hazard assessment
o Five year accident history
o Worst case scenario .. 10 minute release of largest
quantity of regulated chemical
o Alternative release scenario .. more likely to occur
than worst case

Off-site consequence analysis

2. Prevention program
3. Emergency response program
4. Onsite documentation
Requirements similar to OSHA PSM requirements.
Implementation of RMP
Facilities must comply with either:
o Program 1: no offsite accident history, no public receptors in
worse case circle, emergency response with local responders,
limited hazards analysis reqd
o Program 3: facilities reqd to comply with OSHA PSM, most
significant RMP requirements
o Program 2: similar to Program 3 but less stringent Prevention
Program reqd
List rule amendments: 140 listed chemicals; exemption for
gasoline and crude oil, exemption for the outer
continental shelf, threshold quantity (TQ) for mixtures,
and exemption for explosives
RMP & PSM Differences
RMP: 11 elements PSM: 14 elements
Regulates off-site people & Regulates workplace
environment Employee participation
Risk Assessment: release Hot work permits
consequences Contractors
Info to community
ERP: notification of
community, responders
U.S. Chemical Safety Board

Independent federal agency, since 1998

Authorized by CAA amendments of 1990
Mission: prevent chemical incidents
Investigates chemical incidents, determine
root causes, issue safety recommendations to
government, companies, unions, trade
Regulations and Safety Standards

Meeting the regulations is not sufficient

Safety at the speed limit depends on
Regulations alone do not make us safe
Safety requires knowledge, experience, and
engineering judgment
Beyond regulatory compliance
Industrial hygiene
Concerns conditions related to workplace injury and sickness
e.g: exposures to toxic vapors, dust, noise, heat, cold, radiation,
physical factors, etc.

ANTICIPATION Expectation of hazard existence

IDENTIFICATION Presence of workplace exposure

EVALUATION Magnitude of exposure

CONTROL Reduction to acceptable levels

Chemical plants & labs: requires co-operation from industrial

hygiene, safety & plant operations people
Requires study of
Operating instructions
Equipment description
Chemical properties MSDSs


liquids physical state / vapor pressure
vapors TLVs
dusts temperature sensitivity
noise rate and heat of reaction
radiation by-products
temperature reactivity with other chemicals
mechanical explosion limits

RISK ASSESSMENT: potential for hazard to result in an accident

Industrial Hygiene

Identification, evaluation, and control of occupational

conditions which cause sickness and injury

Monitoring of toxic airborne concentrations

Reduction of toxic airborne vapors through ventilation
Selection of proper Personal Protective Equipment (PPE)
Development of procedures for handling hazardous
materials & wastes
Monitoring and reduction of noise, heat, radiation, and
other physical factors
A - Identification of Hazards
Information of interest
Potential hazards (vapor, dust, noise)
Entry mode of toxicant (inhalation, )
Potential impact (skin, lungs, eyes,)
Health information (threshold limit values, reactivity, explosive
see p 79 Tables 3-7 & 3-8
Material Safety Data Sheets
o Lists physical properties of substance that may be required to
determine potential hazards
o Available from chemical manufacturers, commercial source, or
on-site compilation
Standard 16 section format per Chemical Manufacturers
Chemical Product and Company Identification
Composition, Information on Ingredients
Hazards Identification
First Aid Measures
Fire Fighting Measures
Accident Release Measures
Handling and Storage
Exposure Controls, Personal Protection
Physical and Chemical Properties
Stability and Reactivity
Toxicological and Ecological Information
Disposal Considerations
Transport , Regulation, and Other Information
B - Evaluation of Hazards

Extent & degree of employee exposures in the

Taking into account existing controls and their
effectiveness, as well as potential process upsets
Evaluate both during design phase, as well as
sampling during operation to assess effectiveness of
Compare exposure data with health standards TLVs,
PELs, IDLH concentrations
Types of exposures ?
Evaluation of Hazards
Potential Exposures:
1. Single volatile toxicant
2. Multiple ..
3. Dust
4. Noise
5. Toxic vapors in enclosure, with ventilation
6. Vaporization of liquid
1 - Single Volatile Toxicant
Evaluation by monitoring
Continuous : 1 tw

TWA C (t )
where: 8 0
C(t) is concentration in ppm or mg/m3 of the chemical in the air,
tw is the worker shift time in hours
Thus if monitoring shows that the TWA is greater than the TLV-TWA, or if
the worker is exposed to the TLV-TWA to more than 8 hrs, the worker is

Intermittent monitoring is often done, since continuous

monitoring is not always possible
C1T1 C 2 T2 ...... C n Tn
8 hours
Evaluating Volatiles
Monitoring air concentrations Variation in time and place

Time Weighted Average

Continuous: TWA C ( t )dt ppm or mg/m3
8 0


0 tw
Evaluating Volatiles
Intermittent: TWA C i Ti
8 1
Time (hr) Conc. (ppm)
0 100
1 100

1.9 95
2.5 90
0 1 1.9 2.5 3.1 3.8 4
3.1 80
3.8 70
Evaluating Volatiles
Additive effect multiple toxicants: 1 (TLV TW A ) i

C i equivalent
Mixture: (TLV TW A ) mix 1

i mix

Then exposure is OK.

Problem: The presence of an additional chemical reduces the
exposure concentrations. If you are not aware of the presence of
an additional chemical then you might be overexposed when you
think you are OK!
2 - Multiple Volatile Toxicants

Assume that the effects of the chemicals together are additive.

Two approaches for calculations:
Approach 1 - Total Exposure Factor, TEF
Ci is average concentration of i and (TLV-TWA)i is the threshold
limit value for i.

If TEF > 1, personnel are overexposed.

2 - Multiple Volatile Toxicants
Approach 2 - TLV-TWA for Mixture
(TLV TWA) mix

If the sum of the concentrations of the toxicants exceeds

(TLV-TWA)mix, people overexposed.
Note: TLVs may not always be additive, as with mixtures of
toxicants with different effects (e.g., acid vapor mixed with
dissimilar material)
Example Problem
Air contains 4 ppm CCl4 and 25 ppm 1,2-dichloroethane.
Are the workers overexposed?
TLV-TWA of CCl4 = 5 ppm
TLV-TWA of 1,2-dichloroethane = 200 ppm
4 25
(TLV TWA ) Mixture 31.35
4 25

5 200

Thus, Ci 29 31.35, so (TLV - TWA) Mixture is not exceeded.

Another method,
Ci 4 25
0.925 1, so workers are not overexpose d.
(TLV TWA) i 5 200
3 - Dust Exposure
Dust particles in the size range 0.2 to 0.5 microns present
the greatest hazard to lungs
Larger particles unable to penetrate lungs
Smaller particles are mostly exhaled
Calculations are performed similar to that for volatile
vapors. Instead of ppm, units are mppcf (million parts
per cubic foot).
Assumes that larger particles are not absorbed may not
be true
4 - Noise Exposure
Measured in decibels (dB) - 10 log10
Thus, if a sound is ten times as intense as another, it has
an intensity level ten dB greater
Absolute sound scale in dBA is defined by establishing an
intensity reference. For convenience, the hearing
threshold is set at 0 dBA
Permissible noise exposures are given in Table 3-10 (eg,
90 dBA for 8 hour exposure)
Calculation procedures are similar as vapors with dBA
used for ppm and hours for concentration
Exposure to Noise (Table 3-10)
Source Intensity (dB)

Riveting (painful) 120

Passing Truck 100

Noisy Office 80

Whisper 20
Some Noise Data Comparisons
50 refrigerator 40 quiet office, library 40 quiet residential area
50 electric toothbrush 50 large office 70 freeway traffic
50-75 washing machine 65-95 power lawn mower 85 heavy traffic, noisy restaurant
50-75 air conditioner 80 manual machine, tools 90 truck, shouted words
50-80 electric shaver 90 tractor 95-110 motorcycle
55 coffee percolator 90-95 subway 100 snowmobile
55-70 dishwasher 95 electric drill 100 school dance, boom box
60 sewing machine 100 factory machinery 110 disco
60-85 vacuum cleaner 100 woodworking class 110 busy video arcade
60-95 hair dryer 105 snow blower 110 symphony concert
65-80 alarm clock 110 power saw 110 car horn
70 TV audio 110 leaf blower 110-120 rock concert
70-80 coffee grinder 120 chain saw, hammer on nail 112 personal cassette player on high
70-95 garbage disposal 120 pneumatic drills, heavy machine 117 football game (stadium)
75-85 flush toilet 120 jet plane (at ramp) 120 band concert
80 pop-up toaster 120 ambulance siren 125 auto stereo (factory inst'ld)
80 doorbell 125 chain saw 130 stock car races
80 ringing telephone 130 jackhammer, power drill 143 bicycle horn
80 whistling kettle 130 air raid 150 firecracker
80-90 food mixer or processor 130 percussion section at symphony 156 cap gun
80-90 blender 140 airplane taking off
80-95 garbage disposal 150 jet engine taking off 162 fireworks (at 3 feet)
110 baby crying 150 artillery fire at 500 ft. 163 rifle
110 squeaky toy held close 166 handgun close to the ear
180 rocket launching from pad 170 shotgun
5 - Toxic Vapor Exposure in Enclosure
Enclosure Volume, V Concentration of Volatile, C

Ventilation Rate, QV Volatile Rate Out, kQVC

(Volume/Time) (Mass/Time)

Evolution Rate of Volatile, Qm


Total mass of volatile vapor = VC

Accumulation of mass of volatile vapor = d(VC) V dC
dt dt
Mass rate of evolution of volatile specie = Qm
Mass rate of volatile out = kQvC, where k is the non-ideal
mixing factor
Toxic Vapor Exposure
Mass balance:
V Qm kQv C
Qm = source
Qv = ventilation rate (vol/time);
k = mixing factor (variable)

At steady state: C
k Qv
Toxic Vapor Exposure
Convert C to ppm in air, Cppm to estimate average
conc. of a gas in a volume V at absolute pressure P
with a source term Qm and ventilation rate Qv.
Qm RgT 6
C ppm 10
k Qv PM
where the ideal gas law is assumed.

Represents a worker standing near a pool of volatile

liquid, standing near an opening to a storage tank

Local concentration can range widely.

Toxic Vapor Conc. Below TLV

Mixing factor, k, varies from 0.1 - 0.5, (= 1 for

perfect mixing). If not known, use the worst
practical mixing case or use 0.1.

Use this model to determine the minimum

ventilation rate to achieve avg. Conc < TLV.
Consider vapor sampling at several locations.

Ventilation: not too high (expensive) or too

low (insufficient margin for upsets)
6 - Estimation of Vaporization Rate of Liquids
Vaporization rate of a liquid: Q m (Psat - P)
where, Psat is the saturation vapor pressure of liquid at specified
temperature , and P is the partial pressure of the vapor in
the bulk stagnant gas above the liquid.

From Hanna and Drivas, MKA(P sat - P)

where, M is the molecular weight, K is the mass transfer coefficient, R
is the gas constant, A is the area of the pool, and TL is the
absolute temperature of the liquid.
For many situations when Psat is much greater than P and
using the Cppm equation, we have
KAP sat
C ppm X 10 6
kQ v P
Estimation of Vaporization Rate of Liquids (Contd)
The gas mass transfer coefficient, K aD 2/3
where a is a constant and D is the gas phase diffusion coefficient

Taking a ratio of mass transfer coefficients between the species

of interest and a reference species, usually water, we have
K aD 2/3
K o aD o Do
The gas phase diffusion coefficients are in turn calculated from
molecular weights, i.e., 1/ 2 1/ 3
D Mo Mo
, therefore , K K
Do M
Water is frequently the reference, with a mass transfer
coefficient of 0.83 cm/sec and M=18. Therefore,
K 2.1752 M
C Control of Hazards
Two types of control of workplace
o environmental control reducing exposure /
concentration via enclosure, ventilation, wet
methods & housekeeping; see Table 3-12, p
100 .
o PPE providing a protection barrier via ear
plugs, gloves, see Table 3-13, p 101
Standard PPE is generally: hard hat, safety
shoes and glasses & gloves
Respirators compromise a workers ability and should
only be used:
o Temporary
o in an emergency
o as last resort
Standards for using respirators fit testing, periodic
inspections, correct application, training &
Table 3-14, p. 102 lists various respirators from masks,
cartridges and canisters, to self-contained breathing
apparatus (SCBA, which are not dependent on
environment for oxygen).
The most common control method, used to dilute containment
below target concentration & remove before workers exposed
Most common method, since it:
Quickly removes dangerous concentrations of flammable and/or toxic
Can be highly localized reducing amt of air moved & equipment size
Equipment readily available and easily installed
Can be added to existing facility

Composed of fans and ducts, with fans producing small

pressure drop, preferably located at exhaust pulling air out.
Two options: Local and Dilution ventilation
Ventilation in Hoods
Local ventilation, with positive or negative pressure to
remove contaminants
Preferred because it eliminates or greatly reduces worker
Minimal airflow required
Visibility and containment for fire or explosion
Volumetric flow rate is determined assuming plug flow,
rectangular, A = LW, u = air velocity:

Qv A u L W u
Dilution Ventilation
Used when local ventilation is not possible; note worker is
always exposed, but to diluted concentrations with < TLV,
Contaminant in open area and not highly toxic
Air is used as a diluent to reduce levels
Calculate needed ventilation rate
Qm RgT
Qv 106
k C ppm PM

See Table 3-15, p 108 for non-ideal mixing factor k.

Ventilation Problem

A drum contains 42 gallons of toluene. If the

lid is left opened (lid diameter = 3 feet),
determine the time required to evaporate all
the toluene in the drum. The temperature is
85oF. Estimate the concentration of toluene
(in ppm) near the drum if the local ventilation
rate is 1000 ft3/min. Pressure: 1 atm.
Ventilation Problem - Solution
MKAP sat
Qm ( Eq. 3 12)
ln( P sat ) A ( Appendix E or other appropriate reference)
ln( P ) 16.0137
( where T is in K and P sat in mm Hg )
53.67 T
16.0137 36.0 mm Hg 0.7 psi
53.67 302.78

Mass transfer coefficient,

1 1
M 3
cm 18 3 cm ft
K K o o 0.83 0.48 0.016
M sec 92 .13 sec sec
Ventilation Problem - Solution

A D2 (3 ft ) 2 7.07 ft 2
4 4

lb ft
7.07 ft 0.7 psi
92.13 0.016
lbmole sec
psi ft 3 sec

10.73 o
545 R
lbmole R

lb ft 3
Total mass of toluene V (42 gal ) 0.866 62.4 3 303.4 lb
ft 7.48 gal

303.4 lb
So, time to evaporate all toluene 68.8 hrs
0.0012 lb

Ventilation Problem - Solution
KAP sat

0 .016
ft 60 sec

sec min

7. 07 ft2
0.7 psi
C ppm 10 6
kQv P ft 3 k
k 1000 14.7 psi

So, for k 0.1, C ppm 3173, and for k 0.5, C ppm 634.6

(Compare with TLV TWA of toluene 100 ppm)

Alternate Control Methods?
DILUTION Dilution below target concentration
Mixing factor k see Table 3-12
Problems: Requires high air flow and energy
costs. Workers always exposed

LOCAL Remove contaminant before exposure workers minimal air flow

P 0 .0 1 atm
eliminates exposure
containment device
limited workspace

Target Velocity:

100-124 ft/min

Negative Positive
Bypass laboratory hood
pressure ventilation
Velometer for Measuring Flow
Hood Operation

Red liquid level indicates

proper hood function.
Evaluating Noise

Relative Noise Intensity -10 log (dB) I 0 hearing threshold
Permissible exposure (h)





Table 3-10

Similar calculations
1 as volatiles
60 70 80 90 100 110 120

Noise Reduction Rating
Noise Reduction Rating (NRR) is the measurement,
in decibels, of how well a hearing protector reduces
noise as specified by the EPA.
The higher the NRR number the greater the noise
Noise Reduction Ratio (NRR)
Used for Personal Protective Equipment:
A particular hearing protector has an NRR of 18. If
the ambient noise level is 95 dba, what is the worker

Sound Measuring
Hearing Protection
Measuring Volatile Concentrations

Colorimetric Tubes
Measuring Volatile Concentrations
Measuring Volatile Concentrations
Filter unit, usually contains
activated charcoal.

This unit goes with the worker

and is better at measuring the
actual exposure to that

Battery powered air pump.

Table 3-12 Control

Design / Environmental

Enclosures Contain process

Local ventilation Hoods
Dilution ventilation Locker rooms for contaminated clothes
Wet methods Minimize dust by water sprays
Good housekeeping Keep toxics contained

Personal protection Last defense: always

compromises workers