CM4310: Chapter 3 September 11, 2006

Chemical Process Safety Government Regulations

Chapter 3: Industrial Hygiene
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
The two regulations most applicable to
chemical plants are:
• Occupational Safety and Health
Administration (OSHA):
29 CFR 1910.119 “Process Safety Management
of Highly Hazardous Chemicals”
OSHA
OSHA: Occupational Safety and Health
Administration
Force of law with respect to on-site workplace
hazards / accidents. Jurisdiction is only on the plant
site, not off-site.

• Environmental Protection Agency (EPA):

40 CFR Part 68 “Risk Management Programs”

Process Safety / Risk Management

EPA
• Management Systems • Pre-Startup Safety Reviews
• Employee Participation • Mechanical Integrity EPA - Environmental Protection Agency
• Process Safety • Safe Work Practices
Handles releases outside the plant site.
Information • Management of Change
• Process Hazard • Emergency Planning and
Analysis Response
• Operating Procedures • Incident Investigation
• Training • Compliance Audits
• Contractor Safety
See Table 3-4

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CM4310: Chapter 3 September 11, 2006

Industrial hygiene
EPA RMP Concerns conditions related to workplace injury and sickness
e.g: exposures to toxic vapors, dust, noise, heat, cold, radiation,
physical factors, etc.
Risk Management Plan:
• Considers offsite impacts due to fires / explosions / toxic ANTICIPATION Expectation of hazard existence
release.
• Must identify hazards. IDENTIFICATION Presence of workplace exposure

• Must perform consequence analysis. EVALUATION Magnitude of exposure

CONTROL Reduction to acceptable levels

See Table 3-4
Chemical plants & labs: requires co-operation from industrial
hygiene, safety & plant operations people

Identification Evaluating Volatiles

Requires study of Monitoring air concentrations Variation in time and place
CHEMICAL PROCESS • Process design
• Operating instructions
OPERATING CONDITIONS • Safety reviews Time Weighted Average
• Equipment description
OPERATING PROCEDURES t
• Chemical properties MSDS’s 1 w
8 ∫0
Continuous: TWA = C ( t )dt ppm or mg/m3
POTENTIAL HAZARDS HAZARD DATA n
• liquids • physical state / vapor pressure
• vapors • TLV’s
Conc.
• dusts • temperature sensitivity
• noise • rate and heat of reaction
• radiation • by-products
• temperature • reactivity with other chemicals
• mechanical • explosion limits
0 tw
RISK ASSESSMENT: potential for hazard to result in an accident TimeÆ

Evaluating Volatiles Evaluating Volatiles

dk: hai chat ko tong hop doc tinh
i
Ci
1 i ∑ (TLV − TW A ) <1

∑CT
Additive effect multiple toxicants:
TWA =
1 i
Intermittent: i

8 1 i i ∑C i equivalent
Mixture: (TL V − TW A ) m ix = 1
i
⎛ C ⎞
Time (hr) Conc. (ppm) ∑1 ⎜⎝ T LV −iTW A ⎟⎠
i

0 100
1 100
C If ∑ C < (TLV − TWA)
i mix

Æ
1.9 95 Then exposure is OK.
2.5 90 Problem: The presence of an additional chemical reduces
0 1 1.9 2.5 3.1 3.8 4 the exposure concentrations. If you are not aware of the
3.1 80 presence of an additional chemical then you might be
TimeÆ
3.8 70 overexposed when you think you are OK!

2
CM4310: Chapter 3 September 11, 2006

Estimating Volatiles Estimating Volatiles

Relevant for design purposes: • enclosed spaces
Average conc. steady state C = Qm/kQv
• open containers
• filling of vessels More convenient in terms of ppm:
• spill area
Vv ⎛m /ρ ⎞
C ppm = × 10−6 = ⎜ v v ⎟ × 106
Ventilation rate Volatile rate out Vb ⎝ Vb ⎠
Qv (m3/s) kQvC (kg/s) ⎛ mv ⎞⎛ Rg T ⎞
= ⎜ ⎟⎜ ⎟ ×10
6

⎝ Vb ⎠ ⎝ PM ⎠
Q m RT
Qm (kg/s) C ppm = × 10 6 Equation (3-9)
Evolution rate kQ v P M

Ideal mixing k=1

dC
Mass Balance: V = Qm − kQv C Non-ideal k = 0.1- 0.5 Leads to higher concentrations
dt If evolution rate increases or ventilation decrease, concentration
will increase.

Example Step 1: Determine evaporation rate in lb/min

During a degreasing operation involving
⎛ 10 gal ⎞ ⎛ 1 ft ⎞ ⎛ 62.4 lb m ⎞ ⎛ 1 hour ⎞
3
trichloroethylene, 10 gallon of TCE evaporates per 8-
hour shift. Qm = ⎜ ⎟⎜ ⎟⎜ ⎟ (1.46 ) ⎜ ⎟
⎝ 8 hour ⎠ ⎝ 7.48 gal ⎠ ⎝ ft ⎠ ⎝ 60 min ⎠
3

Data: MW = 131.4, T = 537oR, P = 1 atm

Specific gravity of liquid = 1.46 Qm = 0.254 lb m / min

Ventilation Rate, Qv = 1000 ft**3/min

Step 2: Apply Equation (3-9) What ventilation rate required to reduce below
Qm RT
PEL?
C ppm = × 10 6
kQ v PM
Assume k = 0.1 (worst case)
⎛ lb m ⎞ ⎛ ft 3 atm ⎞
⎟ ( 537 R ) x 10
o 6 Use Equation 3-9, calculate Qv
⎜ 0.254 ⎟ ⎜ 0.7302
⎝ ⎠⎝
o
min lb-mole R⎠
C ppm =
⎛ lb m ⎞ ⎛ ft 3 atm ⎞
⎟ ( 537 R ) x 10
⎛ ft 3 ⎞ ⎛ lb m ⎞
⎟ (1 atm ) ⎜ 131
o 6
k ⎜1000 ⎟ ⎜ 0.254 ⎟⎜ 0.7302
⎝ min ⎠ ⎝ lb-mole ⎠ ⎝ min ⎠ ⎝ lb-mole o R ⎠
50 ppm =
( 0.1)( Qv )(1 atm ) ⎛⎜131
760 lb m ⎞
C ppm = 0.1 ≤ k ≤ 0.5 ⎟
k ⎝ lb-mole ⎠
@ k = 0.1 C ppm = 7, 600 ppm Qv = 152,000 ft3/min
@ k = 0.5 C ppm = 1,520 ppm Other control methods?
PEL is 50 ppm, STEL is 200 ppm

3
CM4310: Chapter 3 September 11, 2006

Ventilation
Alternate Control Methods
DILUTION Dilution below target concentration
Mixing factor k see Table 3-12
Problems: Requires high air flow and energy
• Reduce tank surface area, A costs. Workers always exposed
• Use a hood LOCAL Remove contaminant before exposure workers minimal air flow

• Provide a lid to the container Δ P ≈ 0 .0 1 atm

• Use a different solvent • eliminates exposure

• containment device
• shield
• Provide personal protective equipment (ppe) • limited workspace

(Last resort!)
100 ft/min

Negative Positive
Bypass laboratory hood
pressure ventilation

Velometer for Measuring Flow

Hood Operation Evaluating Noise

NOISE PROBLEMS ARE COMMON IN CHEMICAL PLANTS

Å Red liquid level indicates Relative Noise Intensity = -10 log

I
(dB) I 0 = hearing threshold
I0
proper hood function. (dBA)
9
Permissible exposure (h)

speech

factory

painful

8
traffic

office

5
Table 3-8
4

2
Similar calculations
1 as volatiles
0
60 70 80 90 100 110 120

dBA

4
CM4310: Chapter 3 September 11, 2006

Noise Reduction Ratio (NRR)

Exposure to Noise (Table 3-7)
Used for Personal Protective Equipment:
Source Intensity (dB)
A particular hearing protector has an NRR of 18.
If the ambient noise level is 95 dba, what is the
Riveting (painful) 120
worker exposure?
Passing Truck 100 95 dba - 18 dba = 77 dba

Noisy Office 80
Sound Measuring DeviceÆ
Whisper 20

Hearing Protection Vaporization

SOURCE TERM:
MKA Sat MKA Sat
Qm = α ( P Sat − P ) = ( P − P) ≈ P (kg/s)
RTL RTL
A = area for mass transfer Qm
C = Eqn. 3-7
kQ v
KAP Sat
Enclosure with TL = T C ppm = × 10 6 Eqn. 3-14
kQ v P
1
⎛M ⎞ 3
Estimating mass transfer coefficient: K = K0 ⎜ 0 ⎟ Eqn. 3-18
⎝M ⎠
K water = 8.3 ×10−3 m/s

M = 18

Filling Vessels Measuring Volatile Concentrations

Total Volatiles = Evaporation + Displacement

Qm = Qm1 + Qm 2 (kg/s)
Qm
Qm2
M P Sat
Q m1
Q m = (φ rf V c + K A ) Eq. 3-23
R TL
P Sa t
if TL = T C pp m = (φ rf V c + K A ) × 10 6 Eq. 3-24
kQ v P

Splash filling: φ=1

Subsurface filling: φ = 0 .5

Colorimetric Tubes
KA often small compared to displacement

5
CM4310: Chapter 3 September 11, 2006

Measuring Volatile Concentrations Measuring Volatile Concentrations

Å Filter unit, usually contains
activated charcoal.

This unit goes with the worker

and is better at measuring the
actual exposure to that person.

Å Battery powered air pump.

Table 3-9 Control Legacy of the Past!

CHEMICAL PLANT CONTROL TECHNIQUES

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

Legacy of the Past! Promise of the Present!