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CHAPTER 3

PROCESS DESIGN AND SAFETY


3.1 Safety
3.2 Case study on process design and safety
3.3 Chemistry and separations
3.4 Unit ratio material balance
3.5 Detailed flow sheet

Chemical Engineering Design


Course Outcome

Ability to explain and identify process design and safety.

Chemical Engineering Design


3.1 SAFETY

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Safety

The safe design and operation of


facilities is of paramount
importance to every company that
is involved in the manufacture of
fuels, chemicals and
pharmaceuticals

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Safety & Environment
Processes must meet acceptable safety and environmental
performance standards because:

• It is required by law

• The costs (human, social, economic) of non-compliance


can be catastrophic

• Lax attitudes are reflected in insurance premiums, stock


prices

• Moral and ethical obligations

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Major Chemical Plant Safety Legislation
• The Occupational Safety and Health Act (OSHA); 29 U.S.C.
651 et seq. (1970)
– Employers must provide a place of employment free from recognized
hazards to safety and health, such as exposure to toxic chemicals,
excessive noise levels, mechanical dangers, heat or cold stress, or
unsanitary conditions.

• The Emergency Planning & Community Right-To-Know Act


(EPCRA); 42 U.S.C. 11011 et seq. (1986)
– To help local communities protect public health, safety, and the environment
from chemical hazards.

• The Toxic Substances Control Act (TSCA); 15 U.S.C. s/s 2601


et seq. (1976)
– Allows EPA to track industrial chemicals and ban their manufacture or import

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Chemical Plant Hazards
• To design a safe process or product we need to
understand and mitigate the associated hazards

• Materials hazards
– Toxicity
– Flammability
– Incompatibility (corrosivity and reactivity)

• Process hazards
– Overpressure
– Explosions
– Loss of containment
– Noise

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Materials Hazards

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Materials Hazards: Toxicity
• Almost every chemical is toxic if you get enough of it

• Chemical plants tend to have large enough amounts to cause


serious concern for workers and local residents

• Process design needs to consider


– Elimination or substitution of the most hazardous compounds
– Prevention of releases
– Containment
– Disposal (via effective collection or vent systems)
– Ventilation
– Emergency procedures

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Toxicity Definitions
• Acute Effects
• Symptoms develop rapidly (e.g. burns to skin after direct contact)
• Normally the result of short-term exposures

• Chronic Effects
• Symptoms develop over a long period of time (e.g. cancer)
• Often but not always the result of long-term exposure
• Chronic conditions usually persist or recur frequently

• LD50
• Lethal dose at which 50% of test animals are killed
• Usually expressed in mg/kg body mass
• Indicates acute effects only

• Threshold Limit Value (TLV) or Permissible Exposure Limit (PEL)


• Concentration that it is believed the average worker can safely be exposed to for
40 hr work week
• Recommended PEL values are published by OSHA
http://www.osha.gov/SLTC/healthguidelines/
• Recommended TLV values are provided by the American Conference of
Government Industrial Hygienists http://www.acgih.org/home.htm
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Toxicity Data
• Examples:
Compound PEL (ppm) LD50 (mg/kg)

Carbon monoxide 50 1807


Carbon disulfide 20 3188
Chlorine 1 239
Chlorine dioxide 0.1 292
Chloroform 50 1188
Cyclohexane 300
Dioxane 100 4200
Ethylbenzene 100 3500
Formic acid 5 1100
Furfural 5 260
Hydrogen chloride 5 4701
Hydrogen cyanide 10 3.7
Isopropyl alcohol 400 5045
Toluene 100 5000
Xylene 100 4300
Source: OSHA
Ethanol LD50 = 3450 (oral, mouse) 7060 (oral, rat) 1440 (intravenous, rat)

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Toxic Substance Control Act (TSCA)
• TSCA (15 U.S.C. s/s 2601 et seq., 1976) is USEPA’s version of the Food
and Drug Act.
• Allows EPA to regulate the 75,000 chemical substances used in industry
(including confidential materials)
• TSCA requires extensive review before approval is given by USEPA to
manufacture, import and sell a new (i.e., never before made) chemical in
the USA.
• Under TSCA, USEPA can ban or restrict the import, manufacture and use
of any chemical
• Under TSCA, anyone has a right and obligation to report information
about new or alleged health/environmental effects caused by a chemical.

• Section 5 of TSCA requires submitting a pre-manufacture


notice (PMN) to EPA 90 days before manufacturing or
importing any new chemical
• Electronic version of PMN form can be downloaded from EPA
https://cdx.epa.gov/ssl/pmn/download.asp

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Materials Hazards: Flammability
• A fire requires three things:
– A sufficient amount of fuel
– A sufficient amount of oxidant
– A source of ignition (but not always - see autoignition)

• Possible ignition sources include


– Electrical equipment such as motors, actuators
• Usually specified as flame-proof or non-sparking when fuels are present
– Open flames from furnaces, incinerators & flare stacks
– Static electricity
• From any flow, hence pipes, vessels & flanges are always grounded
– Miscellaneous sources
• Matches, lighters & mobile phones are usually banned

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Flammability Definitions
• Flash point
• The lowest temperature at which the material will ignite from an open
flame
• Function of vapor pressure and flammability limits

• Autoignition temperature
• Temperature at which the substance ignites in air spontaneously
• Indicates maximum temperature the material can be heated to in air,
e.g., in drying

• Flammability limits
• Highest and lowest concentrations in air at normal temperature and
pressure (ntp) at which a flame will propagate through the mixture
• Vary widely for different materials

• Data can be found in Materials Safety Data Sheets (MSDS) or safety


handbooks, e.g.:
Lewis, R.J., Sax’s Dangerous Properties of Industrial Materials, 10 th Edn., John Wiley & Sons
Inc., New York, 1999. ($595 for 3 volumes, so check the library!)
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Flame Suppression
• Flame arrestors (flame traps) are specified on vent lines of equipment
that contains flammable materials to prevent a flame from
propagating back from the vent

• Various proprietary designs are available

• Basic principle:
– Provide high metal surface area to act as a sink for heat and free radicals

Enardo detonation
flame arrestors
Source: Enardo LLC
www.Enardo.com

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Materials Hazards: Incompatibility
• Mixtures of incompatible materials may undergo violent
reaction (exothermic, temperature runaway)
– Acids and bases
– Acids and metals
– Fuels and oxidants
– Free radical initiators and epoxides, peroxides, unsaturates, …

• Incompatibility with materials of construction can lead to


loss of containment
– Corrosion of vessels, internals, instruments
– Softening of gaskets, seals, linings

• Materials incompatibility is one of the major sources of


incidents

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Materials Safety Data Sheets
• Material Safety Data Sheets (MSDSs)
must be provided to employees and
customers by law in the U.S.A. (OSHA
Hazard Communication Standard 29 CFR Part
1910.1200)

• MSDS contains the information needed


to begin analyzing materials and
process hazards

• Most MSDSs contain a disclaimer


stating that the user should also make
their own evaluation of compatibility and
fitness for use

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Materials Safety Data Sheet
Example: Ethylene Dichloride
(Source: Fisher Scientific)
Material Safety Data Sheet
1,2-Dichloroethane, extra dry, water <50 ppm
ACC# 00220
Section 1 - Chemical Product and Company Identification
What’s in an
MSDS Name: 1,2-Dichloroethane, extra dry, water <50 ppm MSDS?
Catalog Numbers: AC326840000, AC326840010, AC326841000, AC326842500
Synonyms: Ethylene dichloride; 1,2-Ethylene dichloride; Glycol dichloride; EDC;
sym-Dichloroethane; 1,2-Dichloroethane; Ethylene chloride.
Company Identification:
Acros Organics N.V.
• Chemical
One Reagent Lane
Fair Lawn, NJ 07410
name
For information in North America, call: 800-ACROS-01
For emergencies in the US, call CHEMTREC: 800-424-9300 • Synonyms
Section 2 - Composition, Information on Ingredients • Manufacturer
contact info
CAS# Chemical Name Percent EINECS/ELINCS
• Composition
107-06-2 1,2-Dichloroethane >99.9 203-458-1

Hazard Symbols: T F
Risk Phrases: 11 22 36/37/38 45

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 3 - Hazards Identification

EMERGENCY OVERVIEW
Appearance: colorless liquid. Flash Point: 56 deg F. Warning! Flammable liquid
and vapor. May cause central nervous system depression. May cause liver and
kidney damage. May cause cancer based on animal studies. Causes eye and skin
irritation. Causes respiratory tract irritation. Irritant. May be harmful if swallowed. • Summary of
Target Organs: Central nervous system, liver, eyes, skin.

Potential Health Effects


major hazards
Eye: Causes eye irritation. Vapors may cause eye irritation. May cause chemical
conjunctivitis and corneal damage.
Skin: Causes skin irritation. May be absorbed through the skin. May cause irritation
and dermatitis. May cause cyanosis of the extremities.
Ingestion: May cause central nervous system depression, kidney damage, and liver
damage. May cause gastrointestinal irritation with nausea, vomiting and diarrhea.
May cause effects similar to those for inhalation exposure. May be harmful if
swallowed.
Inhalation: Inhalation of high concentrations may cause central nervous system
effects characterized by nausea, headache, dizziness, unconsciousness and coma.
Causes respiratory tract irritation. May cause liver and kidney damage. Aspiration
may lead to pulmonary edema. Vapors may cause dizziness or suffocation. Can
produce delayed pulmonary edema. Exposure to high concentrations may produce
narcosis, nausea and loss of consciousness. May cause burning sensation in the
chest.
Chronic: Possible cancer hazard based on tests with laboratory animals. Prolonged
or repeated skin contact may cause dermatitis. Prolonged or repeated eye contact
may cause conjunctivitis. May cause liver and kidney damage. Effects may be
delayed.

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 4 - First Aid Measures

Eyes: Immediately flush eyes with plenty of water for at least 15 minutes,
occasionally lifting the upper and lower eyelids. Get medical aid.
Skin: Get medical aid. Flush skin with plenty of water for at least 15 minutes while
removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion: Never give anything by mouth to an unconscious person. Get medical
aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4
cupfuls of milk or water.
Inhalation: Remove from exposure and move to fresh air immediately. If not
breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical
aid. Do NOT use mouth-to-mouth resuscitation.
Notes to Physician: Treat symptomatically and supportively.

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 5 - Fire Fighting Measures

General Information: As in any fire, wear a self-contained breathing apparatus in


pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear.
Vapors may form an explosive mixture with air. During a fire, irritating and highly
toxic gases may be generated by thermal decomposition or combustion. Use water
spray to keep fire-exposed containers cool. Flammable liquid and vapor. Approach
fire from upwind to avoid hazardous vapors and toxic decomposition products.
Vapors are heavier than air and may travel to a source of ignition and flash back.
Vapors can spread along the ground and collect in low or confined areas.
Extinguishing Media: For small fires, use dry chemical, carbon dioxide, water spray
• Flammability
or alcohol-resistant foam. For large fires, use water spray, fog, or alcohol-resistant
foam. Water may be ineffective. Do NOT use straight streams of water. data
Flash Point: 56e deg F ( 13.33 deg C)
Autoignition Temperature: 775 deg F ( 412.78 deg C) • NFPA ratings
Explosion Limits, Lower:6.2%
Upper: 15.9%
NFPA Rating: (estimated) Health: 2; Flammability: 3; Instability: 0

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 6 - Accidental Release Measures

General Information: Use proper personal protective equipment as indicated in


Section 8.
Spills/Leaks: Absorb spill with inert material (e.g. vermiculite, sand or earth), then
place in suitable container. Avoid runoff into storm sewers and ditches which lead to
waterways. Clean up spills immediately, observing precautions in the Protective
Equipment section. Remove all sources of ignition. Use a spark-proof tool. Provide
ventilation. A vapor suppressing foam may be used to reduce vapors.

Section 7 - Handling and Storage


Handling: Wash thoroughly after handling. Remove contaminated clothing and wash
before reuse. Ground and bond containers when transferring material. Use spark-
proof tools and explosion proof equipment. Avoid contact with eyes, skin, and
clothing. Empty containers retain product residue, (liquid and/or vapor), and can be
dangerous. Keep container tightly closed. Do not pressurize, cut, weld, braze, solder,
drill, grind, or expose empty containers to heat, sparks or open flames. Use only with
adequate ventilation. Keep away from heat, sparks and flame. Avoid breathing vapor
or mist.
Storage: Keep away from heat, sparks, and flame. Keep away from sources of
ignition. Store in a tightly closed container. Keep from contact with oxidizing
materials. Store in a cool, dry, well-ventilated area away from incompatible
substances. Flammables-area. Storage under a nitrogen blanket has been
recommended.

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 8 - Exposure Controls, Personal Protection

Engineering Controls: Facilities storing or utilizing this material should be equipped


with an eyewash facility and a safety shower. Use adequate general or local
explosion-proof ventilation to keep airborne levels to acceptable levels.
Exposure Limits

Chemical Name ACGIH NIOSH OSHA - Final PELs

1,2-Dichloroethane 10 ppm TWA


1 ppm TWA; 4 mg/m3
TWA 50 ppm IDLH
50 ppm TWA; 100
ppm Ceiling • OSHA PEL
data
OSHA Vacated PELs: 1,2-Dichloroethane: 1 ppm TWA; 4 mg/m3 TWA
Personal Protective Equipment
Eyes: Wear chemical goggles.
• Required PPE
Skin: Wear appropriate protective gloves to prevent skin exposure.
Clothing: Wear appropriate protective clothing to prevent skin exposure.
Respirators: A respiratory protection program that meets OSHA's 29 CFR 1910.134
and ANSI Z88.2 requirements or European Standard EN 149 must be followed
whenever workplace conditions warrant a respirator's use.

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 9 - Physical and Chemical Properties


Physical State: Liquid
Appearance: colorless
Odor: chloroform-like
pH: Not available.
Vapor Pressure: 100 mm Hg @29 deg C
Vapor Density: 3.4 (Air=1)
Evaporation Rate:6.5 (Butyl acetate=1)
Viscosity: Not available.
Boiling Point: 81-85 deg C
Freezing/Melting Point:-35 deg C
Decomposition Temperature:Not available.
Solubility: Insoluble.
Specific Gravity/Density:1.25 (Water=1)
Molecular Formula:C2H4Cl2
Molecular Weight:98.96

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 10 - Stability and Reactivity


• Known
Chemical Stability: Stable at room temperature in closed containers under normal
storage and handling conditions.
Conditions to Avoid: Light, ignition sources, excess heat, electrical sparks.
incompatible
Incompatibilities with Other Materials: Aluminum, bases, alkali metals, ketones,
organic peroxides, nitric acid, strong oxidizing agents, strong reducing agents, liquid
materials
ammonia, amines.
Hazardous Decomposition Products: Hydrogen chloride, phosgene, carbon
monoxide, irritating and toxic fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported.

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Example: Ethylene Dichloride

Section 11 - Toxicological Information


RTECS#:
CAS# 107-06-2: KI0525000
LD50/LC50:
CAS# 107-06-2:
Draize test, rabbit, eye: 63 mg Severe;
Draize test, rabbit, eye: 500 mg/24H Mild;
• Acute effects
Draize test, rabbit, skin: 500 mg/24H Mild;
Inhalation, rat: LC50 = 1000 ppm/7H;
Oral, mouse: LD50 = 413 mg/kg;
Oral, rabbit: LD50 = 860 mg/kg;
Oral, rat: LD50 = 670 mg/kg;
Skin, rabbit: LD50 = 2800 mg/kg;<BR.

Carcinogenicity:
CAS# 107-06-2:
ACGIH: A4 - Not Classifiable as a Human Carcinogen
California: carcinogen; initial date 10/1/87
NIOSH: potential occupational carcinogen
• Chronic effects
NTP: Suspect carcinogen
OSHA: Possible Select carcinogen
IARC: Group 2B carcinogen
Epidemiology: IARC Group 2B: Proven animal carcinogenic substance of pote ntial
relevance to humans. IARC Group 2B: No data availa ble on human carcinogenicity,
however sufficient evi dence of carcinogenicity in animals.
Teratogenicity: See actual entry in RTECS for complete information.
Reproductive Effects: No information found.
Neurotoxicity: No information found.
Mutagenicity: No information found.
Other Studies: See actual entry in RTECS for complete information.
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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 12 - Ecological Information

Ecotoxicity: Water flea Daphnia: 218mg/L; 48H; Bluegill/Sunfish: 430mg/L; 96H;


Static Fathead Minnow: 136mg/L; 96H; Static No data available.
Environmental: Terrestrial: Smaller releases on land will evaporate fairly rapidly.
Larger releases may leach rapidly through sandy soil into groundwater. Aquatic: If
released to surface water, its primary loss will be by evaporation. The half-life for
evaporation will depend on wind and mixing conditions and was of the order of hours
in the laboratory. However a modeling study using the EXAMS model for a eutrophic
lake gave a half-life of 10 days. Atmospheric: Will degrade by reaction with hydroxyl
radicals formed photochemically in the atmosphere. Half-life over one month.
Physical: Not expected to biodegrade or bioconcentrate.
Other: For more information, see "HANDBOOK OF ENVIRONMENTAL FATE AND
EXPOSURE DATA."

Section 13 - Disposal Considerations

Chemical waste generators must determine whether a discarded chemical is


classified as a hazardous waste. US EPA guidelines for the classification
determination are listed in 40 CFR Parts 261.3. Additionally, waste generators must
consult state and local hazardous waste regulations to ensure complete and accurate
classification.
RCRA P-Series: None listed.
RCRA U-Series: CAS# 107-06-2: waste number U077.

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Materials Safety Data Sheet
Example: Ethylene Dichloride

Section 14 - Transport Information

Canada
US DOT IATA RID/ADR IMO
TDG
No
Shipping ETHYLENE
information
Name: DICHLORIDE
available.
Hazard Class: 3
UN Number: UN1184
Packing Group: II

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Materials Safety Data Sheet
Example: Ethylene Dichloride
Section 15 - Regulatory Information

US FEDERAL

TSCA
CAS# 107-06-2 is listed on the TSCA inventory.
Health & Safety Reporting List
CAS# 107-06-2: Effective Date: 6/1/87; Sunset Date: 6/1/97
Chemical Test Rules
None of the chemicals in this product are under a Chemical Test Rule.
Section 12b
• U.S. regulatory
None of the chemicals are listed under TSCA Section 12b.
TSCA Significant New Use Rule
None of the chemicals in this material have a SNUR under TSCA.
information
SARA

CERCLA Hazardous Substances and corresponding RQs


CAS# 107-06-2: 100 lb final RQ; 45.4 kg final RQ
SARA Section 302 Extremely Hazardous Substances
None of the chemicals in this product have a TPQ.
SARA Codes
CAS # 107-06-2: acute, chronic, flammable.
Section 313
This material contains 1,2-Dichloroethane (CAS# 107-06-2, 99 9%),which is subject
to the reporting requirements of Section 313 of SARA Title III and 40 CFR Part 373.
Clean Air Act:
CAS# 107-06-2 is listed as a hazardous air pollutant (HAP). This material does not
contain any Class 1 Ozone depletors. This material does not contain any Class 2
Ozone depletors.
Clean Water Act:
CAS# 107-06-2 is listed as a Hazardous Substance under the CWA. CAS# 107-06-2
is listed as a Priority Pollutant under the Clean Water Act. CAS# 107-06-2 is listed as
a Toxic Pollutant under the Clean Water Act.
OSHA:
None of the chemicals in this product are considered highly hazardous by OSHA.
STATE
CAS# 107-06-2 can be found on the following state right to know lists: California,
New Jersey, Pennsylvania, Minnesota, Massachusetts.
The following statement(s) is(are) made in order to comply with the
California Safe Drinking Water Act: WARNING: This product contains 1,2-
Dichloroethane, a chemical known to the state of California to cause cancer.
California No Significant Risk Level: CAS# 107-06-2: 10 ug/day NSRL

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Materials Safety Data Sheet
Example: Ethylene Dichloride

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols:
TF
Risk Phrases:
R 11 Highly flammable.
R 22 Harmful if swallowed.
R 36/37/38 Irritating to eyes, respiratory system
and skin.
• Foreign regulatory
R 45 May cause cancer.

Safety Phrases:
information
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
S 53 Avoid exposure - obtain special instructions
before use.

WGK (Water Danger/Protection)


CAS# 107-06-2: 3
Canada - DSL/NDSL
CAS# 107-06-2 is listed on Canada's DSL List.
Canada - WHMIS
This product has a WHMIS classification of B2, D2A, D2B.
Canadian Ingredient Disclosure List
CAS# 107-06-2 is listed on the Canadian Ingredient Disclosure List.
Exposure Limits
CAS# 107-06-2: OEL-ARAB Republic of Egypt:TWA 5 ppm (2 mg/m3) OEL-A
USTRALIA:TWA 10 ppm (40 mg/m3) OEL-AUSTRIA:TWA 20 ppm (80 mg/m3) OEL
-BELGIUM:TWA 10 ppm (40 mg/m3) OEL-DENMARK:TWA 1 ppm (4 mg/m3);Skin
OEL-FINLAND:TWA 10 ppm (40 mg/m3);STEL 20 ppm (80 mg/m3);CAR OEL-FRAN
CE:TWA 10 ppm (40 mg/m3) OEL-GERMANY;Carcinogen OEL-HUNGARY:STEL 4 m
g/m3;Carcinogen OEL-JAPAN:TWA 10 ppm (40 mg/m3) OEL-THE NETHERLANDS:
TWA 50 ppm (200 mg/m3) OEL-THE PHILIPPINES:TWA 50 ppm (200 mg/m3) OE
L-RUSSIA:TWA 10 ppm OEL-SWEDEN:TWA 1 ppm (4 mg/m3);STEL 5 ppm (20 mg/
m3);Skin;CAR OEL-SWITZERLAND:TWA 10 ppm (40 mg/m3);STEL 20 ppm (80 mg
/m3) OEL-TURKEY:TWA 50 ppm (200 mg/m3) OEL-UNITED KINGDOM:TWA 10 ppm
(40 mg/m3);STEL 15 ppm (60 mg/m3) OEL IN BULGARIA, COLOMBIA, JORDAN,
KOREA check ACGIH TLV OEL IN NEW ZEALAND, SINGAPORE, VIETNAM check A
CGI TLV

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Example: Ethylene Dichloride

Section 16 - Additional Information

MSDS Creation Date: 10/19/1998


Revision #6 Date: 4/17/2002
The information above is believed to be accurate and represents the best information currently available to us.
However, we make no warranty of merchantability or any other warranty, express or implied, with respect to
such information, and we assume no liability resulting from its use. Users should make their own investigations to
determine the suitability of the information for their particular purposes. In no event shall Fisher be liable for any
claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential
or exemplary damages, howsoever arising, even if Fisher has been advised of the possibility of such damages.

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Test: MSDS
• A freight train has just derailed. It was pulling ten rail
tankers of ethylene dichloride from your plant. The local
fire chief calls the plant asking what should be done.

• What do you do?

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Role of MSDS in Process Design
• Always collect MSDS of all components used in the process at as
early a stage as possible
• Sources: manufacturers, manufacturer’s web sites, libraries, etc.
• Because of disclaimers, it is worth checking > 1 source
• Good starting points are http://www.msdssearch.com/ or
http://www.siri.org/msds

• Use MSDS information to improve intrinsic safety of process


• Eliminate incompatible mixtures
• Substitute less hazardous chemicals when possible (e.g. toluene
instead of benzene as solvent)

• Ensure that design meets regulatory requirements


• Vapor recovery
• Other emissions

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Design for Materials Hazards
• Substitution – use something less toxic and hazardous

• Containment
• Sound design of plant and equipment
• For example, use welded joints instead of flanges

• Prevention of releases
• By design of equipment and disposal systems

• Ventilation
• Use open plant structure or engineered ventilation system

• Disposal
• Effective vent stacks and scrubbers
• Collection and treatment of run-off water and liquid from relief systems

• Provision of emergency equipment


© 2012 G.P. Towler / UOP. For educational use in conjunction with
Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Hazards

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Hazards: Overpressure
• Occurs when mass, moles or energy accumulate in a
contained volume (or space with restricted outflow)

• Rate of accumulation determines the pressure rise

• Process controls may not be able to respond quickly


enough

• If pressure is not relieved by pressure safety valve then


outcomes could include
– Vessel rupture
– Explosion
– Other loss of containment

• See following lecture for design for overpressure


© 2012 G.P. Towler / UOP. For educational use in conjunction with
Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Hazards: Fires & Explosions

• A fire requires a flammable mixture and an ignition


source

• Fires in chemical plants can quickly lead to damage to


control systems and equipment, causing overpressure,
loss of containment and explosions

• Fire protection guidelines are given in several standards


(see Ch10)
– NFPA 30, API RP 2001, API Publ 2218

• Legal requirements for fire protection are set by OSHA


(29 CFR 1910 L)

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Sources of Ignition
• Can you think of possible sources of ignition on a
chemical plant?
– Sparking of electrical equipment
• Motors, actuators, lighting, electric heaters, …
– Process flames
• Furnaces, flare stacks, incinerators
• These should always be sited well away from plant, usually upwind
– Static electricity
• See API RP 2003 and NFPA 77
– Lightning
– Vehicles (engines, electrical systems and exhausts)
– Portable electrical devices
– Welding and cutting equipment
– Miscellaneous sources (matches, lighters, etc. are usually
banned)
© 2012 G.P. Towler / UOP. For educational use in conjunction with
Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Electrical Systems
• The use of electrical equipment in chemical plants is
regulated by law (OSHA standard 29 CFR 1910.307) and by
industry design codes
• National Electrical Code NFPA 70
• NFPA standards 496, 497, API RP 500, 505

• NFPA 70 defines classified areas in which flammable


materials may be present at high enough concentrations to
be ignitable (see Ch10)
• Specific precautions must be taken depending on the classification
• Equipment must be designed and installed in accordance with code

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Electrical Systems
• Codes should be consulted
before selecting equipment for
use in classified areas

• Codes also govern electrical


maintenance work (NFPA 70B).
Companies usually have strict
“Lock-out, tag-out” procedures
to prevent electric shock
accidents

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Hazards: Explosions
• An explosion is the sudden, catastrophic release of
energy causing a pressure wave (blast wave)

• Explosions can be caused by ignition of a flammable


mixture
– Liquid
– Vapor
– Solid (e.g., finely dispersed dust)

• Explosions can also be caused by release of thermal


energy
– Boiler rupture
– BLEVE (boiling liquid expanding vapor explosion)
© 2012 G.P. Towler / UOP. For educational use in conjunction with
Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Explosion Definitions
• Deflagration
– Combustion zone propagates at (subsonic) flame speed, usually < 30 m/s
– Pressure wave generated usually < 10 bar
– Principal heating mechanism is combustion

• Detonation
– Combustion zone propagates at supersonic velocity, 2000 – 3000 m/s
– Pressure wave up to 20 bar
– Principal heating mechanism is shock compression
– Usually requires confinement or a high-intensity source
– Deflagration can turn into detonation when propagating along a pipe

• Expansion factor
– Measure of the increase in volume resulting from combustion
– E = (molar density of reagents)/(molar density of products)
– Maximum value of E is for adiabatic combustion

• Flame speed
– The rate of propogation of a flame front through a flammable mixture, with respect to a fixed
observer

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Explosivity Properties
Vol% gas at Maximum Adiabatic Autoignition
Flammability Limits (vol%) Expansion
Fuel Formula max flame flame speed flame Temp temperature
factor
Upper Lower speed (m/s) (K) (ºC)
Hydrogen H2 4.0 75 54 22.1 2318 6.9 400
Methane CH4 5.0 15 10 2.8 2148 7.5 601
Ethane C2H6 3.0 12.4 6.3 3.4 2168 7.7 515
Propane C3H8 2.1 9.5 4.5 3.3 2198 7.9 450
n-Butane C4H10 1.8 8.4 3.5 3.3 2168 7.9 405
Pentane C5H12 1.4 7.8 2.9 3.4 2232 8.1 260
Hexane C6H14 1.2 7.4 2.5 3.4 2221 8.1 225
Heptane C7H16 1.1 6.7 2.3 3.4 2196 8.1 215
Acetylene C2H2 2.5 80 9.3 14.8 2598 8.7 305
Ethylene C2H4 2.7 36 7.4 6.5 2248 7.8 490
Propylene C3H6 2.4 10.3 5 3.7 2208 7.8 460
Butylene C4H8 1.7 9.7 3.9 3.8 2203 7.9 385
Benzene C6H6 1.3 7.9 3.3 5 2287 8.1 560
Cyclohexane C6H12 1.3 8.0 2.7 4.2 2232 8.1 245

Dugdale, D. An introduction to Fire Dynamics, Wiley, New York, 1985


© 2012 G.P. Towler / UOP. For educational use in conjunction with
Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Explosions: Design Implications
• Design to prevent explosions from happening

• Prevent formation of explosive mixtures whenever


possible
– Operate outside flammability envelope

• Consider confined explosion as a pressure relief


scenario and ensure that PRV is sized to allow adequate
relief load to prevent detonation

• Use flame suppressors to prevent deflagration from


propagating into detonation

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Hazards: Loss of Containment

• The primary means of protecting the public from toxic chemicals is


containment by the plant itself

• Loss of containment can occur due to:


– Pressure relief
– Operator error (e.g. leaving a sample point open)
– Poor maintenance procedures
• Failure to drain and purge properly
• Failure to put everything back together properly
– Leaks from degraded equipment
• Corrosion
• Damaged seals, gaskets

• These are mostly operational issues, but design may need to provide
for secondary containment if the potential impact of a release is high

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Process Hazards: Noise
• Chemical plants can be very noisy, especially compressors, turbines,
motors and solids handling

• Chronic effects include permanent damage to hearing

• Sound is measured in decibels, defined by:

 RMS sound pressure  Pa  


Sound level  20 log10  5  dB
(Note: log scale)  2  10 

• Ear protection should be required in areas where noise > 80 dB

• Permanent damage can be caused by noise > 85 dB

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
Questions ?

© 2012 G.P. Towler / UOP. For educational use in conjunction with


Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design