Safe Handling and Storage of

Styrene Monomer

Americas Styrenics LLC

24 Waterway Avenue, Suite 1200
The Woodlands, TX 77380 USA
+1-844-512-1212
© Americas Styrenics LLC 2020
 Environmental, Health & Safety Policy

Americas Styrenics is committed to safety excellence. We strive to make optimal use of the
resources that we consume and to minimize emissions and waste.

We challenge ourselves to be a safer, more environmentally-conscious organization. We are

committed to manufacturing, handling, transporting and disposing of chemical products
safely. Americas Styrenics cares about the communities where we live and work by creating
a culture that puts safety above all and enacts responsible environmental practices.
 TABLE OF CONTENTS

PRODUCT STEWARDSHIP POLICY …………….…………………………………………. 1

INTRODUCTION ……………………………….……………………………………..……………. 2

PART 1 PROPERTIES OF STYRENE MONOMER

Physical Properties of Styrene Monomer ……………………………...………………….. 3

References ………………………..…………………………………………………………. 7
Analytical Methods ……………………...………………………...………………………… 8

PART 2 SAMPLING AND HANDLING

PATE 1
Training ………………………………………..………………………………..………..…… 9
Recommended Practice for Sampling Styrene ………………………...……………..…. 9
Sampling Devices ………………………………………………………………….………… 10
Static Electricity and Grounding ………………………..………………………………….. 10
Product Loading and Unloading Requirements ………………..…………....…………… 10
Safety References ……………………...…………………………………………………… 11

PART 3 STYRENE MONOMER STORAGE

Polymerization in Storage ……………………………..………………….…………………. 12

Prevention of Polymerization ……………………………………………………………... 12
Handling Runaway Polymerizations ………………………………………………………. 12
TBC Inhibitor Test Comparison Card …………………………………………..…………. 13
Inhibition ..……………………………………………………………………………………... 13
Oxygen Requirements ..……………………………………………………………………... 15
Addition of TBC to Stored Monomer ……..……………………………………..………….. 18
Polymer Formation During Storage ...………………………………..…………….……… 18
Color Problems ……….………………………………………………….…………………… 18
Particulate Matter .……………………………………………………………………………. 19
Drums ………………………………………………………………………………………….. 19
Tanks ..………………………………………………………………………..……………….. 19
Piping ..………………………………………………………………………..……………….. 22
Pumps .………………………………………………………………………..……………….. 22
Valves .………………………………………………………………………..……………….. 23
Gaskets ………..……………………………………………..……………………………….. 23
Filters ..……………………………………………………..………………………………….. 23
Hoses …..…………………………………………………….……………………………….. 23
O-Rings ……………………………………………………..………………………………… 23
Procedure for Coating Tanks …………………..…………..……………………………….. 23
API Design References ……………..……………………………………………………….. 24
PART 4 ACCIDENTAL RELEASE, FIRE AND HEALTH

Accidental Release Measures ………………………………...…………………………….. 26

Spills …….………………..……………………………………………………………………. 26
Disposition .……………….…………………………………………………………………… 27
Fire Hazards ……….…………………………………………………………………………. 27
Flammability …………………………………………………………………………………… 27
Explosive Mixtures .…………………………………………………………………………... 27
Fires ……………………………………………………………………………………………. 28
Personal Protective Equipment and Occupational Exposure Limits ….………………… 28
Health Hazards and First Aid ………………………………………………………………... 29
Environmental Hazards .……………………………………………………………………... 30

PART 5 TRANSPORTATION INFORMATION AND REGULATORY PROFILE

Transportation Information ...………………………………………………………………… 31

Drums ………………………..………………………………………………………………… 32
Regulatory Profile …………………………….………………………………………………. 33
Revision Statements ………………………………….……………………………………… 34

PART 6 APPENDIX

Glossary of Terms, Abbreviations and Organizations ……………………………………. 35

 PRODUCT STEWARDSHIP POLICY

Americas Styrenics LLC is committed to good stewardship of our products. We manage

product stewardship issues by providing customers, distributors, and traders with information
regarding potential hazards and appropriate safe use and handling of our products. We will
continuously review health, safety, environmental, and regulatory issues as they relate to
Americas Styrenics' customers and markets.

We will meet our product stewardship commitments through the effective implementation of
our Operational Excellence Management System (OEMS). Successful implementation of this
management system will ensure that health, safety, and environmental protection are an
integral part of designing, manufacturing, marketing, distributing, using, recycling, and
disposing of our products.

The information contained in this technical bulletin is not intended to, nor does it,
amend or replace the Safety Data Sheet (SDS) for Styrene Monomer. The most current
Safety Data Sheet can be obtained from Americas Styrenics by calling +1-844-512-
1212 or from the Americas Styrenics web site (www.AmSty.com) and should be
carefully reviewed prior to working with this product.

Copyright August 2020

Americas Styrenics LLC
All Rights Reserved

AUGUST 2020 1
 INTRODUCTION
Americas Styrenics LLC is the third largest producer of styrene monomer in North America and
one of the largest producers of polystyrene.

Styrene was first developed in 1928, and is now one of the most important monomers produced
by the chemical industry. It serves as a building block of the plastics industry. The conventional
method of producing styrene involves the alkylation of benzene with ethylene to produce
ethylbenzene, followed by dehydrogenation of ethylbenzene to styrene. Styrene undergoes
polymerization to produce a wide variety of polymers and copolymers. Styrene is readily
polymerized and copolymerized by both batch and continuous processes (mass, emulsion,
suspension and solution polymerization).

Americas Styrenics manufactures Styrene Monomer at its plant in St. James, Louisiana. The
St James plant was originally owned by Gulf Oil Chemical Company and has been in operation
since 1971. The plant has been ISO 9001 certified since 1994. St. James has been an OSHA
VPP Star site since 2000.

DISCLAIMER:

THIS GUIDE DOES NOT OVERRIDE, AMEND, OR REPLACE OFFICIAL PUBLICATIONS,

CURRENT SAFETY REGULATIONS, TECHNICAL DATA SHEETS, SAFETY DATA SHEETS, OR
COMMERCIAL TERMS OF SALE. THIS GUIDE SHOULD NOT BE CONSIDERED RECOGNIZED
AND GENERALLY ACCEPTED GOOD ENGINEERING PRACTICES (RAGAGEP). AMERICAS
STYRENICS LLC (“AMSTY”) MAKES NO GUARANTEE AS TO THE ACCURACY OR EFFICACY OF
THE CONTENT IN THIS GUIDE. AMSTY REPORTS INFORMATION TO THE BEST OF ITS
KNOWLEDGE, BUT IT MAKES NO WARRANTY OF ANY KIND, EITHER EXPRESSED OR IMPLIED,
INCLUDING THE WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE, WITH RESPECT TO THE USE OR APPLICABILITY OF THIS INFORMATION. THE USER
ASSUMES ALL RISK AND LIABILITY ASSOCIATED WITH THE USE OF INFORMATION IN THIS
GUIDE, AND AMSTY DISCLAIMS ALL LIABILITY WITH REGARD TO SUCH USE.

2 AUGUST 2020
 PART 1

PROPERTIES OF STYRENE MONOMER

Physical Properties of Styrene Monomer

The data contained in this section have been obtained experimentally or derived from the chemical
literature referenced at the end of the section.

Property Value

Autoignition Temperature (in air)1 490 °C (914 °F)

Boiling Point: 2,10 760 mm Hg 145.14 °C (293.25 °F)

100 mm Hg 82.4 °C
30 mm Hg 54.7 °C
10 mm Hg 33.6 °C
1 mm Hg -1.6 °C

Color Colorless

Corrosivity Noncorrosive to metals except to copper and alloys

of copper.

Critical Pressure (pc)3 39.5 atm (580 psia)

Critical Temperature (tc)3 374.4 °C (706 °F)

Critical Volume (Vc)3 0.369 L/mole

Cubical Coefficient of Expansion (per °C)4 9.710 x 10-4 at 20 °C

9.805 x 10-4 at 30 °C
9.902 x 10-4 at 40 °C

Decomposition Temperature No data available

Density of Liquid, (in air)5 Temp. (°C) g/cc lb/US Gal.

0 0.9230 7.7031
10 0.9138 7.6263
20 0.9046 7.5496
30 0.8954 7.4728
40 0.8862 7.3960
50 0.8770 7.3192

Dielectric Constant of Liquid6 Temp. (°C) ∈

20 2.4257
40 2.3884
60 2.3510

Electrical Conductivity at 25 °C 2.8 x 10-14 mhos/cm

Entropy of Gas at 25 °C (S°)2 82.48 kcal/(g-mole)-dy.

AUGUST 2020 3
 Property Value

Evaporation Rate (Butyl Acetate = 1) 0.49

Flammability (Solid, Gas) Not Applicable

Flammability Limit – Upper 6.1 % (V)

– Lower 1.1 % (V)

Flash Point:7 (Tag closed cup) 31 °C (88 °F)

(Tag open cup) 37 °C (98 °F)

Free Energy of Formation of Gas at 25 °C (∆Gf°)2 51.10 kcal/(g-mole)

Freezing Point2 -30.628 °C (-23.13 °F)

Heat of Combustion Gas at Constant Pressure, -1018.83 kcal/(g-mole)

25 °C, to form gaseous products (∆Ho)2

Heat of Formation:2 gas at 25 °C (∆Hf°) 35.22 kcal/(g-mole)

liquid at 25 °C (∆Hf°) 24.83 kcal/(g-mole)

Heat of Polymerization at 90 °C (∆H)8 -17.8 kcal/(g-mole)

Heat of Vaporization at 145.1 °C10 8.82 kcal/(g-mole)

Henry’s Law Constant (H) at 25 °C11 0.00275 atm m3/(g-mole)

Kinematic Viscosity at 25 °C 0.8 mm2/s

Molecular Weight 104.14 g/(g-mole)

Odor Aromatic

Odor Threshold 0.1 ppm

Partition Coefficient: 2.95 log P(o/w)

n-Octanol / Water at 25 °C

pH Not Applicable

Physical State at Room Temperature Liquid

Refractive Index:4 Temp. (°C) ND

0 1.5579
10 1.5523
15 1.5495
20 1.5467
25 1.5439
30 1.5410
40 1.5354
50 1.5298
60 1.5242

4 AUGUST 2020
 Property Value

Relative Density2 (°C) g/cc

0 0.9250
10 0.9158
20 0.9066
30 0.8974
40 0.8882
50 0.8790
60 0.8698
70 0.8605
80 0.8513
90 0.8421
100 0.8329

Relative Vapor Density (Air = 1) at 20 °C 3.6

Solubility of Oxygen (from air) in Styrene Temp. (°C) ppm

15 53
25 50
35 45

Solubility: Styrene in Water9 Temp. (°C) (g/100 g H20)

0 0.018
20 0.029
40 0.040
60 0.051
80 0.062

Solubility: Water in Styrene9 Temp. (°C) (g/100 g styrene)

0 0.020
20 0.060
40 0.100
60 0.140
80 0.180

Solubility in:10 Acetone ∞

CS2 ∞
Benzene ∞
Ether ∞
n-Heptane ∞
Ethanol ∞

Specific Heat8 (°C) (cal/g-°C)

0 0.4004
20 0.4131
40 0.4269
60 0.4421
80 0.4590
100 0.4774

AUGUST 2020 5
 Property Value

Specific Heat (vapor)2 Temp. (°C) Cp (cal/g-°C)

0 0.256
25.0 0.280

Surface Tension8 (°C) dynes/cm

0 34.5
20 32.3
40 30.0
60 27.8
80 25.6
100 23.5

Thermal Conductivity Temp. °C (°F) BTU/(hr.ft2 °F)

0 (32) 0.080
25 (77) 0.079
50 (122) 0.076
75 (167) 0.0735
100 (212) 0.0708
150 (302) 0.063
200 (392) 0.0598

Vapor Pressure2 Temp. (°C) mm Hg

0 1.15
10 2.34
20 4.50
30 8.21
40 14.30
50 23.87
60 38.41
70 59.78
80 90.31
90 132.82
100 190.63
110 267.62
120 368.22
130 497.39
140 660.64
150 864.00
160 1113.97

Viscosity4 Temp. (°C) (Centipoise)

0 1.040
20 0.763
40 0.586
60 0.470
80 0.385
100 0.326
120 0.278

Volumetric Shrinkage upon Polymerization 17%

(typical)

6 AUGUST 2020
References

1. G. W. Jones, G. S. Scott, and W. E. Miller, Bureau of Mines Report of Investigations 3630.

2. American Petroleum Institute Research Project 44, “Selected Values of Properties of

Hydrocarbons and Related Compounds”.

3. “Physical Constants of Hydrocarbons C1 to C10”, ASTM Special Technical Publication No.

109A (1963).

4. “Kirk-Othmer Encyclopedia of Chemical Technology”, (2nd Ed.), Vol. 19, Interscience, New
York, 1968, p. 56-57.

5. Calculated using ASTM D1555-09 tables.

6. J. Petro and C. P. Smyth, J. Amer. Chem. Soc., 80, 73 (1958).

7. Manufacturing Chemists Association Chemical Safety Data Sheet SD-37 (Rev. 1971), p. 5.

8. R. H. Boundy and R. F. Boyer (Eds.), “Styrene: Its Polymers, Copolymers, and Derivatives”,
Reinhold, New York, 1952, Ch. 3.

9. W. H. Lane, Ind. Eng. Chem. (Anal. Ed.), 18, 295, (1946).

10. R. R. Dreisbach, “Physical Properties of Chemical Compounds”, Vol. 1, Am. Chem. Soc.,
1955, p. 159.

11. K. Bocek, Experimetia, Suppl 23: 231-40 (1976).

AUGUST 2020 7
Analytical Methods
The following ASTM methods are recommended for the analysis of styrene monomer:

1. D1209 Color of Clear Liquids (Platinum-Cobalt Scale)

2. D1364 Water in Volatile Solvents (Karl Fischer Reagent Titration Method)

3. D2119 Aldehydes in Styrene Monomer

4. D2121 Polymer Content of Styrene Monomer

5. D2340 Peroxides in Styrene Monomer

6. D4052 Density and Relative Density of Liquids by Digital Density Meter

7. D4176 Free Water and Particulate Contamination in Distillate Fuels (Visual Inspection
Procedures)

8. D4590 Colorimetric Determination of p-tert-Butylcatechol in Styrene Monomer by

Spectrophotometry (a)

9. D5135 Analysis of Styrene by Capillary Gas Chromatography

10. D5386 Color of Liquids using Tristimulus Colorimetry

11. D6229 Standard Test Method for Trace Benzene in Hydrocarbon Solvents by Capillary Gas
Chromatography

12. D7375 Trace Quantities of Water in Aromatic Hydrocarbons and Their Mixtures by
Coulometric Karl Fisher Titration

13. D7504 Standard Test Method for Trace Impurities in Monocyclic Aromatic Hydrocarbons by
Gas Chromatography and Effective Carbon Number

14. D7704 Standard Test Method for Total Aldehydes in Styrene Monomer by Potentiometric
Titration

15. D8005 Standard Test Method for Color of Clear Liquids (Platinum-Cobalt Scale)

16. E1064 Standard Test Method for Water in Organic Liquids by Coulometric Karl Fischer
Titration

(a) AmSty routinely provides TBC Test Comparison Cards to customers (upon request) for
estimating inhibitor levels. Please contact your Account Management Specialist or Sales
representative for information.

8 AUGUST 2020
 PART 2

SAMPLING AND HANDLING

Training Recommended Practice for

Sampling Styrene
In any workplace where styrene is handled,
used, stored or transported, a training This information is provided for use in
program must be implemented to ensure establishing sampling and handling
worker’s awareness of styrene properties, procedures. This information should only be
toxicity, and safety procedures. The training utilized in conjunction with an existing health
program should include the following: and safety program and cannot be used as a
substitute for expert safety and medical
1. Properties and health hazards of styrene. advice.

2. Styrene physical hazards including the Take extreme care to prevent spills. In case
potential for fire and explosion. material is spilled, wash contaminated areas
thoroughly with large quantities of water and
3. Styrene’s primary routes for entry into collect the liquid in the plant chemical waste
body. system.

4. Safe work and good housekeeping SAMPLING:

practices.
Samples may be taken through the manway
5. The importance of protection from styrene opening by means of a clean, dry 1-qt (1-L)
contact; the proper clothing and cleaning glass bottle held in a clean, dry sheath of
requirements. nickel or stainless steel attached to a long rod
or lightweight chain of the same material. Fit
6. Signs and symptoms of styrene exposure the bottle with a stopper to which is attached a
and action to be taken and medical light metal chain. Lower the bottle to near the
conditions aggravated by exposure to bottom of the tank and pull out the stopper with
styrene. a sharp jerk of the chain. Raise it at such a rate
that it is about three fourths full when it
7. The care that must be taken whenever emerges from the liquid. Stopper the bottle
and wherever styrene is used, handled, before attempting to rinse the material from
stored and transported. the outside. Label the sample bottle according
to OSHA Regulations. Note: Fresh air and
8. Emergency procedures for leaks, spills, other personal protective gear may be
and fires, including protective clothing to required depending on predetermined
be worn in such instances. exposure limits.

9. The availability of written styrene usage, Emphasis should be placed on cleanliness

health hazard and training program and dryness. Both the sample bottle and its
procedures. holder must be CLEAN AND DRY. Transfer
the sample to a dry, dark brown bottle for
It is recommended that this training program storage. A suitable bottle for storing the
should be part of a worker’s initial training and sample is known as a “Boston Round”. The
should be scheduled at least annually closure should be a screw cap with a Teflon
thereafter. or aluminum foil liner.
Additional accidental release, fire and health If new bottles are used, first rinse them
information is presented in a subsequent thoroughly with acetone or methanol and then
section of this guide. dry in a hot-air oven. Hold in a desiccator while

AUGUST 2020 9
cooling to ambient temperature. Protect them Static Electricity and Grounding
from dirt or moisture by enclosure in a
polyethylene bag. Rinse used bottles very Static electricity can cause difficulties such as
thoroughly with water, detergent, and solvents fires and explosions unless certain
and then treat as new bottles. precautions are observed. Styrene monomer
has a high volume resistivity, and can pick up
The sampling system should be bonded to the and hold a static charge during transfer
tank manway (e.g. by resting the chain on the operations. Key operations which have the
lip of the manway) prior to sampling. potential of generating a flammable
atmosphere and/or static charge include tank
REFERENCE DOCUMENTS: and container filling, splash filling, tank
cleaning, sampling, gauging, switch loading,
ASTM D3437: Practice for Sampling and filtering, mixing/agitation, and vacuum truck
Handling Cyclic Compounds operations. To minimize the hazard of static
electricity during these operations, bonding
ASTM E300: Practice for Sampling Industrial and grounding may be necessary, but may not
Chemicals by themselves be sufficient. For more
information, refer to OSHA Standard 29 CFR
ANSI Z 288.1: Flammable and Combustible 1910.106, “Flammable and Combustible
Liquids Code Liquids”, National Fire Protection Association
(NFPA) 77, “Recommended Practice on Static
API RP 500A: Classification of Locations for Electricity” and/or the American Petroleum
Electrical Installations in Petroleum Refineries Institute (API) Recommended Practice 2003,
“Protection Against Ignitions Arising Out of
OSHA Regulations, 29 CFR, Paragraphs Static, Lightning, and Stray Currents”.
1910.1000 and 190.2000
The use of insulating flanges or non-insulating
U.S. DOT Regulations, 49 CFR, hoses are recommended for marine
Transportation Subchapters B and C, Parts vessel/shore connections.
171-179
Submerged filling is recommended for all
flammable liquids. The inlet line should
Sampling Devices discharge at, or near, the bottom and make
electrical contact with the tank to eliminate
Quality control within the process industry is of uncontrolled electrical discharge.
prime importance. This demands stringent
checks, not only of the finished product, but Operators wearing rubber-soled shoes,
also throughout the various stages of particularly on certain composition floors
production, distribution and use. made of good insulating materials, may pick
up considerable static electricity.
The need for representative samples plays a
critical role in ensuring product quality, yet
sampling directly often includes the risks of Product Loading and Unloading
exposure to the operator as well as Requirements
contamination and pollution to the environment.
Use of a system such as the DOPAK sampling When loading or unloading a vessel or barge:
method for process samples and HERMetric
Sampler for tank samples significantly reduces Refer to current ISGOTT and USCG rules.
such risks. Texas Sampling Inc. also markets
closed loop sampling systems. When loading or unloading tank cars:

1. Use only clean, oil- and dirt-free, spark-

resistant tools and implements.

10 AUGUST 2020
2. Make sure the tank car’s internal pressure Safety References
has been relieved before removing the
manhole or outlet valve cap. The following publications are excellent
references for styrene monomer handling
3. Visually inspect hoses and fittings prior to information:
use.
Manual Sheet TC-4,
4. Ground the tank car before connecting Chemical Manufacturer’s Association
any part of it to the unloading lines or Recommended Practice for Unloading
equipment. Loading and unloading lines Flammable Liquids from Tank Cars
should be continuously bonded during
loading/unloading. NFPA 30
Flammable and Combustible Liquids Code
5. Purging all lines with nitrogen prior to
transfer of product reduces risk of flash NFPA 70
fires. National Electrical Code

6. Unload the car through the dome NFPA 77

connection or through the bottom outlet. Recommended Practice on Static Electricity
Check carefully for leaks.
API RP 2003
7. Use of air pressure to unload tank cars is Protection Against Ignitions Arising Out of
not recommended. If pressure must be Static, Lightning, and Stray Currents
used, the operator should demonstrate
caution and only use an inert gas such as
nitrogen.

8. Use an approved pump to unload the tank

car. If the car does not have an eductor
(discharge) pipe, insert a pipe through the
open dome and pump its contents out
through the pipe.

9. Carefully vent the car through a flame

arrester during unloading.

10. If unloading is interrupted, disconnect all

unloading connections, close all valves
tightly and securely apply all other
closures.

11. Tank cars should be cleaned and

prepared for shipment in accordance with
DOT regulations prior to releasing.

AUGUST 2020 11
 PART 3

STYRENE MONOMER STORAGE

The prevention of polymer build-up is the The important point is that polymerization may
primary concern in the storage of styrene occur spontaneously in storage tanks.
monomer. Prevention of color formation is also Depending on the quantity of material being
important, but this is normally caused by stored, serious consequences may result.
contamination such as rust. Low
temperatures, maintaining proper inhibitor and
dissolved oxygen levels, correct construction Prevention of Polymerization
materials, and good housekeeping are all
important factors in maintaining a long shelf Polymerization during storage may be
life. prevented by close attention to monomer
temperature, inhibitor level, polymer content
Contact AmSty (+1-844-512-1212) with and oxygen content. Determinations of
questions regarding Styrene Monomer inhibitor content, oxygen level in the vapor
inhibition and inhibitor testing. space, polymer content, and monomer
temperature should be made on a routine
basis. Styrene-containing vessels should be
Polymerization in Storage protected from external sources of heat.
Running pumps against closed valves (dead-
Styrene polymerizes slowly at normal ambient heading) should be avoided. Care should be
temperatures but very rapidly at elevated taken that vents, valves, pressure-relief
temperatures. Styrene polymerization is devices, gauges, and controls do not become
initiated by heat, lack of inhibitor and dissolved plugged with polymer.
oxygen, and contact with peroxides and other
free-radical initiators, ionic initiators, and
redox initiators. Polymerization can take place Handling Runaway
in storage as well as under more controlled Polymerizations
conditions. The polymerization process is
exothermic, evolving 288 BTU/lb (17.8 The action to take will depend on how far the
kcal/g-mole). If this evolved heat cannot be runaway has proceeded. The beginning of a
dissipated rapidly enough, the temperature of runaway polymerization may be identified by
the monomer will rise, increasing the rate of an increase in monomer temperature
polymerization and, with it, the rate of (particularly if monomer temperature exceeds
evolution of heat. The temperature may rise to
ambient or rises more than 3 °F (1.6 °C) in one
the point where the reaction becomes very
day). The higher the temperature, the further
rapid and self-sustaining (a runaway
the runaway has progressed and the more
polymerization). Normally, temperatures
difficult to stop. Decisions concerning what
above 149 °F (65 °C) are needed to initiate
actions to take must be made on-site, but
runaway polymerizations.
AmSty may be contacted for guidance at
+1-844-512-1212. The following suggestions
During a runaway polymerization, the
are listed approximately in the order
temperature will reach and exceed the boiling
recommended for halting a runaway
point of styrene. The vapor may erupt violently
polymerization and dealing with an advanced
from the tank vents or, if the vents are plugged
runaway:
or too small, it can create enough pressure to
rupture the tank. As the liquid polymerizes and
1. Add up to 0.5% TBC and aerate. Aeration
becomes more viscous, vapor bubbles may
can be accomplished by bubbling in air, or
become trapped, expanding the liquid and
stirring the product while exposed to air.
causing spills or rupture of the tank.
Facilities storing and handling styrene

12 AUGUST 2020
 monomer should have TBC inhibitor on as an antioxidant and prevent polymerization
hand in case of emergency. by reacting with oxidation products in the
monomer. Note: Sufficient oxygen must be
2. Reduce temperature of tank with water present for inhibition. In the absence of
spray. If the tank is insulated, the insulation oxygen, polymerization will proceed as if no
should be removed as quickly as possible inhibitor were present.
and prior to spraying with water. Use ice, if
feasible, but not in the product directly, as The TBC level should be checked at regular
it will tend to remove the TBC. If placed in intervals (See Table 2B of this section).
the product, ice should be in a sealed metal Additional inhibitor should be added to
container. maintain a safe level.

3. Keep vessel vented. The time required for TBC concentrations to

fall to a dangerously low level varies greatly
4. Dilute with ethylbenzene or toluene, if tank because of different storage and handling
is not venting and product temperature is conditions. The depletion rates in actual
below 231 °F (110 °C), to retard storage may be appreciably faster or slower
polymerization and reduce viscosity. depending on the set of environmental
conditions. Factors which affect depletion of
5. If possible, remove product from tank TBC are heat, water and air; with heat being
before it solidifies, to save the tank. Use the most important.
drums, diked area, or float on water in a
pond or confined area. If the inhibitor has been depleted and
polymerization has begun, inhibitor should be
added immediately. If unstable monomer is
TBC Inhibitor Test Comparison not treated promptly, it may become
unsalvageable.
Card
Additional inhibitor should be added when
The AmSty TBC Inhibitor Test Comparison
inhibitor levels drop below 10 ppm to maintain
Card can be used to estimate inhibitor levels
adequate inhibition. Normal levels are 10-15
under laboratory and field conditions. This
ppm, but some customers may require up to
Test Comparison Card may be obtained by
100 ppm because of unique storage
contacting your Sales representative or by
conditions or process requirements. After
mailing a request to:
addition, the storage tank should be
recirculated until inhibitor is uniformly mixed
Americas Styrenics LLC
and testing shows that target levels have been
24 Waterway Avenue
achieved. The tank should also be aerated to
Suite 1200
provide the proper amount of dissolved
The Woodlands, TX 77380
oxygen. Refer to Table 3A or 3B to determine
the proper amount of inhibitor to add.
Note: TBC Specification analysis must be
performed using ASTM Method D4590.
The relatively small quantities of TBC required
to raise the inhibitor level in stored monomer
can most easily be added by using an 85 %
Inhibition TBC / 15 % Methanol blend or a concentrated
stock solution in the monomer or other solvent.
TBC (4-tert-Butylcatechol) is customarily Concentrated stock solution has an indefinite
added to styrene to prevent polymer formation storage life when stored in the dark at normal
and oxidative degradation during shipment ambient temperatures.
and subsequent storage.
A TBC concentrate for use in increasing the
Inhibitors prevent polymerization in two ways: inhibitor level in styrene monomer can be
(1) they can react with and deactivate the free prepared by dissolving 704 grams of pure TBC
radical in a growing chain, and (2) they can act in 1 gal of styrene monomer (186 gram/liter).

AUGUST 2020 13
At this concentration, 1 cc of the concentrate Styrene vapors in storage tanks are not
will raise the level of inhibitor 1 ppm in a drum inhibited and can polymerize on roofs of
of styrene having a net weight of 410 lb storage tanks and around vents. Vapor space
(186 kg). Table 3A lists the amount of inhibitors are available but are not viewed as
concentrate required to increase the inhibitor being adequately effective.
level of bulk quantities by 10 ppm.

Table 1
Effect of Inhibitor and Oxygen on the Shelf Life
of Styrene at Various Temperatures

Monomer 12 ppm TBC 50 ppm TBC

Temperature Saturated with Air Less than 3 ppm O2 Saturated with Air
60 °F (15.6 °C) 6 months 10 to 15 days 1 year
85 °F (29.4 °C) 3 months 4 to 5 days 6 months
110 °F (43.3 °C) 8 to 12 days Less than 24 hours Less than 30 days

Table 2A
Suggested Monitoring Schedule for
Styrene Bulk Storage

Monomer Temperature Daily

Table 2B
Suggested Testing Schedule for
Styrene Bulk Storage

Monomer Temperature Frequency Key Properties

Polymer ASTM D2121
80 °F (26.7 °C) or Higher Twice a week
Inhibitor ASTM D4590
Color ASTM D5386
70 – 79 °F (21.1 – 26.1 °C) Weekly
Aldehydes ASTM D2119
Peroxides ASTM D2340
Below 70 °F (21.1 °C) Bi-weekly
Appearance ASTM D4176

14 AUGUST 2020
 Table 2C
Suggested Inspection Schedule for
Styrene Bulk Storage

Inspection Frequency
Air Vents
Vacuum Pressure Relief
Flame Arrester Quarterly
Foam Reservoir should be
inspected for polymer
Tank Interior Every three (3) years, if coated
Annually, if uncoated

Oxygen Requirements
The problem presented by air is complex. TBC
is not an effective inhibitor for styrene monomer
in the complete absence of dissolved oxygen.
Excessive amounts of oxygen in the storage
tank, on the other hand, may lead to other
serious storage and handling problems.

Monomer vapors above the liquid level in the

tank are uninhibited. These uninhibited vapors
and condensed monomer droplets are readily
oxidized on contact with air. These droplets
containing oxidation products will polymerize
quite rapidly and adhere to the rusted, porous
surfaces of unlined steel tanks. They form
stalactites on the roof and coat the sidewalls
above the liquid level.

Complete elimination of oxygen from the vapor

space will lead to depletion of dissolved oxygen
from the liquid monomer. If this dissolved
oxygen is greatly reduced, the TBC inhibitor
becomes ineffective and rapid polymerization
of the stored monomer will take place. If an inert
gas blanket such as nitrogen is used,
provisions should be made to aerate the
monomer once a week for approximately 30
minutes, or until the oxygen level again reaches
saturation. An alternative is to recirculate
product and inject air at a rate of approximately
1-2 ft3/hr/million lb (0.06-0.12 m3/hr/million kg)
of styrene monomer (Orbisphere Laboratories
Oxygen Analyzer is suitable for measuring
dissolved oxygen content).

AUGUST 2020 15
 TABLE 3A
cc of Concentrate (TBC in Styrene) Required for 10 ppm TBC in Styrene*
(186 g TBC/liter Styrene)

Gallons
0 100 200 300 400 500 600 700 800 900
Styrene

cc of Concentrate Required

0 ― 20.4 40.7 61.1 81.4 101.8 122.1 142.5 162.8 183.2

1000 204 224 244 265 285 305 326 346 366 387

2000 407 427 448 468 488 509 529 549 570 590

3000 611 631 651 672 692 712 733 753 773 794

4000 814 834 855 875 895 916 936 957 977 997

5000 1018 1038 1058 1079 1099 1119 1140 1160 1180 1201

6000 1221 1241 1262 1282 1303 1323 1343 1364 1384 1404

7000 1425 1445 1465 1486 1506 1526 1547 1567 1587 1608

8000 1628 1648 1669 1689 1710 1730 1750 1771 1791 1811

9000 1832 1852 1872 1893 1913 1933 1954 1974 1994 2015

10000 2035 2056 2076 2096 2117 2137 2157 2178 2198 2218

* Calculated using styrene density in air at 20 °C

16 AUGUST 2020
 TABLE 3B
cc of Concentrate Required to Increase TBC in Styrene by 1 ppm*
(85 % TBC and 15 % Methanol)

Gallons
Styrene 0 100 200 300 400 500 600 700 800 900

cc of TBC Required

0 ― 0.4 0.8 1.1 1.5 1.9 2.3 2.6 3.0 3.4

1000 3.8 4.2 4.5 4.9 5.3 5.7 6.1 6.4 6.8 7.2

2000 7.6 7.9 8.3 8.7 9.1 9.5 9.8 10.2 10.6 11.0

3000 11.4 11.7 12.1 12.5 12.9 13.2 13.6 14.0 14.4 14.8

4000 15.1 15.5 15.9 16.3 16.7 17.0 17.4 17.8 18.2 18.5

5000 18.9 19.3 19.7 20.1 20.4 20.8 21.2 21.6 22.0 22.3

6000 22.7 23.1 23.5 23.8 24.2 24.6 25.0 25.4 25.7 26.1

7000 26.5 26.9 27.3 27.6 28.0 28.4 28.8 29.1 29.5 29.9

8000 30.3 30.7 31.0 31.4 31.8 32.2 32.6 32.9 33.3 33.7

9000 34.1 34.4 34.8 35.2 35.6 36.0 36.3 36.7 37.1 37.5

10000 37.9 38.2 38.6 39.0 39.4 39.7 40.1 40.5 40.9 41.3

* Calculated using styrene density in air at 20 °C

Example: Current TBC level = 8 ppm; desired TBC level = 15; Difference = 7 ppm; Volume = 5900 gallons of styrene

22.3 (from table) X 7 = 156 cc of TBC required

AUGUST 2020 17
Addition of TBC to Stored Monomer specification of 15 by ASTM D5386 has been
set for many styrene end uses.
Styrene monomer in storage should be
checked periodically for TBC content and Color may develop in several ways:
additional inhibitor added as required (see
previous section on Inhibition). A good policy is 1. Copper or copper-containing alloys can
to add additional inhibitor when the level drops form soluble copper salts when contacted
to the minimum specification level. The TBC by styrene. These will impart a green or
content of styrene monomer in storage should blue-green color to the monomer and may
never be allowed to be depleted or remain also inhibit its polymerization.
below the 10 ppm level. The storage tank (or
drum) should always be recirculated or mixed 2. Highly-colored styrene oxidation products
after inhibitor is added. This ensures uniform may form in the liquid monomer or be
blending of the TBC and supplies an adequate introduced by polymer falling into or
amount of dissolved oxygen in the monomer for dissolving from the walls and roof of the
effective inhibition. Caution must be exercised storage tank.
when handling TBC. See information on
toxicological properties and safe handling of 3. TBC may oxidize to form highly-colored
TBC as well as the manufacturer’s SDS. reaction products.

Table 3B lists the amount of concentrate 4. Iron, usually originating from rust in tanks
required to increase the bulk quantity by 1 ppm. or in piping, may react or complex with TBC
The amount of inhibitor required to achieve the at the ppm level to give styrene a yellow or
assured inhibition level can also be calculated yellow-green color.
using Table 3A.
5. Styrene lying stagnant in a line may
develop color and, if flushed into a tank,
Polymer Formation During Storage may make the entire tank off color.

The polymer formed under storage conditions Color problems in storage can be minimized by:
will be discolored, cross-linked, and high in
peroxides, aldehydes, and other oxidation 1. Avoiding use of copper or copper-alloyed
products. Deposits of contaminated polymer material in contact with styrene monomer.
could eventually produce serious color and
polymer problems in monomer stored under air 2. Paying careful attention to the oxygen level
in unlined steel tanks. Internal reflux, (the in the styrene and in the vapor space above
vaporization and condensation due to normal the styrene.
temperature differentials) will dissolve small
amounts of this polymer and carry it back into 3. Employing proper tank design and
the tank, thereby increasing both the polymer maintenance to avoid rust and polymer
content and the color of the stored monomer. build-up on tank walls and roof.

Polymer formed in tanks also creates difficult 4. Applying good transfer practices.
removal and cleaning problems. If stalactites
are allowed to grow, their weight may damage Color in styrene monomer can be reduced to
the roof or roof-supporting structure of large acceptable limits by:
vertical storage tanks.
1. Distilling the colored monomer.

2. Blending with non-colored styrene. Caution

Color Problems should be used, however, since color does
not always blend proportionately. Small
Styrene in storage occasionally develops color trial blends should be made to determine
which can be carried into the polymerization the feasibility of this approach.
product. For this reason, a maximum color

18 AUGUST 2020
3. Passing the styrene over silica gel or Tanks
alumina. This method has the
disadvantage of removing the TBC In designing bulk storage facilities, certain
inhibitor, which must be replaced. Acidic or basic factors must be considered. Styrene
highly-activated alumina may cause the monomer can be stored for relatively long
styrene to polymerize. Verify the periods of time if simple, but carefully
applicability of the material selected by prescribed conditions are met. In addition to the
using a small bench scale test. usual precautions taken with flammable liquids
against fire and explosion hazards, precautions
must be taken against conditions that will
Particulate Matter promote the formation of polymer and oxidation
products. To accomplish this, the design and
Styrene should be free of particulate matter construction of a satisfactory bulk storage
when it is polymerized. Although some system for styrene requires careful
particulate matter in styrene originates from consideration to eliminate excessive
outside contamination via the receiving-transfer temperatures and to prevent contamination
system, it is also formed by the reaction of with polymer from infrequently used lines and
concentrated TBC solutions with iron. This may other equipment. Figures 1 and 2 show two
occur in lines which have contained styrene but different types of storage installations.
have been blown dry.
A self-supporting type dome roof is
Particulate matter in styrene may be avoided recommended for vertical storage tanks. This
by: type of construction simplifies the installation of
linings and permits rapid drainage of
1. Paying careful attention to cleanliness. uninhibited condensed vapors back into the
liquid monomer, thus reducing the polymer and
2. Properly coating the inside of tanks and stalactite problem. Roof and sidewall openings
transfer lines which may contain high above the normal liquid levels in the tank
concentrations of TBC or which may be should be of large diameter and the number
blown dry after carrying TBC-inhibited kept to a minimum.
styrene. Stainless steel vessels and lines
are also recommended. Large diameter openings are easily lined and
can also be used for dual-service purposes
3. Filtering styrene to remove particulate where feasible.
matter before storage, shipment, or use.
Insulation and refrigeration of storage tanks is
recommended for environments where
Drums temperatures exceed 75 °F (23.9 °C) for long
periods of time.
Drums of styrene monomer should not be
permitted to stand in the sun for more than a Most consuming locations insulate storage
short period of time. As soon as possible after tanks to dampen the effect of high daytime
being received, drums should be moved to a temperatures but do not install refrigeration due
cool, shaded area. In hot weather, drums can to cost.
be cooled with a water spray. It is also
advisable that inventories be kept to a minimum Lined carbon steel tanks are generally used for
during summer months and that monomer is the bulk storage of styrene monomer. Vertical
stored no longer than necessary. Adding storage tanks are commonly used for large
additional TBC during hot weather is also volume storage. Horizontal tanks are equally
recommended. Styrene should be stored in satisfactory for bulk storage, but are generally
white drums that reflect sunlight as a means to used for smaller installations. The inlet and
control temperature. outlet lines for these tanks are normally located
near the bottom. To facilitate mixing where
external refrigeration is employed, it is
recommended that either the outlet line or the

AUGUST 2020 19
inlet line operate through a floating swing-pipe, Baked Phenolic
adjusted so that the monomer is always either
1. Heresite P403L Heresite Protective
withdrawn or discharged a few inches below
Coatings
the surface. Warm monomer is withdrawn from
the top, circulated through the chiller, and
2. Phenguard 930, PPG Protective &
discharged at the bottom, cooling the tank from
935, and 940 Marine Coatings
the bottom up.

This type of system will also perform

satisfactorily where the outlet and inlet lines are Modified Phenolic Epoxy
reversed and the pump withdraws monomer 1. Amercoat 346 PPG Coatings Europe
from the bottom, circulates it through the chiller
and discharges through the swing-pipe near
the surface. Eddy currents induced by Epoxy Novolac
temperature differences between the chilled
monomer and the stored monomer lead to 1. Devchem 253 Akzo Nobel
relatively uniform mixing.

Tank linings have proven quite successful in Other equivalent or comparable coatings are
controlling or reducing polymer and stalactite undoubtedly available and may be equally
formation. A tight, non-porous, non-wettable, satisfactory, but it would be advisable to check
smooth surface prevents retention and their resistance characteristics and obtain
attachment of the condensed uninhibited information on their performance for this
monomer droplets, and they rapidly drain back application from the manufacturer before use.
into the inhibited liquid monomer before Rubber-based linings should not be used.
polymerization takes place. Baked phenolic,
modified epoxy and inorganic zinc silicates Requirements of diking, tank spacing, and
have proven satisfactory for this purpose. other features pertaining to safety are detailed
Baked phenolic and modified epoxy coatings in guidelines set by the National Fire Protection
are nonconductive, however, and it is Association (see NFPA 30). These, as well as
recommended that the bottom and lower 6 to 8 local building codes and governmental
inches (15 – 20 cm) of vertical storage tanks be regulations, should be consulted since some
coated with inorganic zinc silicate linings to requirements vary with the size and
provide electrical grounding. configuration of an installation.

Table 4 lists some suppliers and specific

products for the various types of coatings.

Various coatings applied with TBC have

reportedly been effective in controlling polymer
growth inside storage tanks (including the
vapor space) and reducing maintenance.
Specific coatings and the suppliers (who will
supply specific directions for preparing and
applying these coatings) are listed in Table 4.

TABLE 4
Types of Coatings and Suppliers

Inorganic Zinc Silicate Primer

1. Dimetcote 6 PPG Industries Europe

20 AUGUST 2020
AUGUST 2020 21
All electrical equipment associated with the 5. All newly installed styrene pipelines should
tank should conform to the National Electrical be pressure tested by an approved method
Code (NFPA 70). before insulation is applied.

6. Bellow valves are recommended for 2-inch

Piping (5 cm) and smaller lines to eliminate
emissions from packing.
Piping is normally of carbon steel, although
stainless steel and aluminum may also be
used. Copper and copper-containing alloys Pumps
in contact with styrene must be avoided.
Stainless steel pipe is recommended for Centrifugal pumps are preferred for styrene
concentrated TBC solutions, but steel pipe service. They should be fitted with closed
lined with baked phenolic coating, Teflon®, or impellers and mechanical seals.
the equivalent can also be used to reduce
formation of particulate matter. The pump manufacturer can recommend the
proper pump if the following parameters are
All piping should be sloped and have no known: 1) flow rate, 2) size and length of
pockets where styrene can become stagnant. suction and discharge lines, 3) suction and
All low points should be provided with drains or discharge pressures and, 4) the styrene
some other means of removing the monomer. monomer temperature. A drain valve should be
Above-ground piping should be insulated and installed at the lowest point in the system so
properly grounded. Provision should be made that the pump and all piping can be completely
either for circulating styrene through all lines or drained before any maintenance work is done.
for blowing them empty with nitrogen. Do not Totally enclosed fan cooled motors are
leave styrene in blocked lines because thermal recommended. However, local fire and
expansion could damage valves and seals and insurance codes should be consulted to
the monomer is more likely to become oxygen determine if an explosion-proof motor must be
and inhibitor depleted. used.

Flanged or welded connections are suggested. All pump motors should meet National
For larger piping, butt welded fittings are Electrical Code standards (NFPA 70).
preferred. Socket weld fittings are preferred for
small connections. The following practices are recommended to
minimize the possibility of pump leakage.
All storage tanks and loading points should be
fitted with sampling points. Never use brass, 1. Mechanical seals in conformance with API
bronze, or any line material containing copper. RP 682. Tandem seals with barrier fluid are
recommended.
The following are recommended practices in
engineering pipelines for styrene: 2. Pumps in conformance with API Standard
610.
1. Lines smaller than 1-inch (2.5 cm) should
not be used. 3. The pump should be designed so that the
pump bearings will be able to carry thrust
2. A minimum of flanged connections should at no flow. Consider selecting non-metallic
be used on styrene pipelines. Flanges (PEEK) wear rings to minimize damage if
should be avoided due to leak potential. the pumps run dry.

3. Styrene lines should not be buried because 4. The pump shaft should be highly polished.
of the difficulty of checking for leakage.
5. Pumps should not be subjected to forces
4. All lines should be sloped so that they can beyond specified pump tolerances.
be completely drained for maintenance.

22 AUGUST 2020
6. Vibration monitoring with automatic pump Flexible metal hoses are widely used and
shutdown may be applicable in certain recommended but require special care to
situations. prevent damage during use.
Styrene monomer should not be allowed to
remain in any hose after use because the
Valves monomer will polymerize and form undesirable
reaction products. Promptly drain and clean
Ball valves with Viton® seats are satisfactory for these lines after each use. Ethylbenzene or
styrene service under ambient storage toluene may be used to clean these lines.
conditions. Gate valves are less satisfactory but
they are usually less expensive and may be All lines must be adequately grounded to
used. discharge static electricity.

All hoses should have suitable pressure and

Gaskets temperature ratings and be grounded to
discharge static electricity.
Garlock GRAPH-LOCK, Garlock Gylon
3500 Series, Teflon, Viton B, Durlon 9000N,
Grafoil GHE, or their equivalents are O-Rings
satisfactory for flanged connections at ambient
conditions. Reinforced graphite composite Viton GF-S, Viton B, Teflon, or their
gaskets are also recommended. Gaskets made equivalents are recommended.
of rubber or other styrene-soluble materials
should be avoided.
Procedure for Coating Tanks

Filters All internal surfaces should be coated (except

for the floor and bottom of the vertical walls
Since small amounts of foreign matter may below the normal liquid level) to prevent
enter storage tanks from various sources, a accumulation of static electricity. This includes,
filter in the transfer piping between the tank(s) in addition to the tank, all internal surfaces of
and processing equipment is recommended. nozzles, manholes, manhole covers, internal
Cartridge type filters with a fine or medium fittings and all surfaces that may contact the
replaceable cartridge or bag filters are liquid contents of the tank or be exposed to
suggested. Polyester, Nomex, Rayon and vapors from the liquid. If any internal fittings are
Nylon fiber filters are compatible with styrene. of non-ferrous metal, they should be removed
and replaced when the lining is completed.
Filter cartridges should be inspected and
replaced periodically. All sharp edges and high points should be
ground smooth and rounded to a minimum
radius of 1/8-in (3.2 mm). Welded seams need
not be ground flush; however, welds should be
Hoses free from undercuts or pinholes. If either exists,
they should be ground out, filled with weld
If hoses are needed for loading or unloading
metal or epoxy putty, and ground smooth. Weld
operations, they should be flexible and
spatter beads should be removed by grinding
chemical-resistant. A satisfactory type is
or by the sand blasting which follows.
Goodyear, rough-bore, style WH-7 with Viton®
tube, or the equivalent. Multi-layered
All internal surfaces to be lined should be
polypropylene and Teflon® are also
sandblasted to the degree defined as “White
recommended.
Metal Blast” by Steel Structures Painting
Council Specification SP-5-63. Anchor pattern
depth should conform to a minimum of 1.5 mils
and a maximum of 2 mils. Loose material such

AUGUST 2020 23
as sand, grit, dust, or any foreign matter should application work since the solvents are also
be removed from the tank, preferably by use of flammable. Ventilation should be maintained at
an industrial vacuum cleaner. all times while personnel are in enclosed areas
and for thirty minutes to an hour after lining
The first coating should be applied within eight work has been completed for the day. An
hours after sandblasting is completed. It must adequate number of air changes must be
be applied before any rust appears or “turning” provided to keep solvent vapors below lower
occurs in the “White Metal Blast” zone. explosive limits. After lining work has been
Otherwise, re-blasting to the “White” condition completed, forced-air ventilation should be
will be necessary. maintained until all solvent fumes have been
removed.
1. A brushed prime coat should be applied to
all welds, rounded edges and other Personnel should never be permitted to
irregular surfaces, working the paint well enter an empty tank which has been used
into the metal. for Styrene Monomer until the requirements
of OSHA confined space standard (29 CFR
2. Apply a full sprayed coat of primer over 1910.146) have been met and the safe entry
brushed surfaces. Allow to dry overnight. recommendations of API Standard 2015
Dry film thickness should be 1.5 – 2.5 mils. have been met including, but not limited to,
required concentrations for oxygen and
3. Apply one sprayed coat of intermediate limitations on concentrations of styrene.
primer to all surfaces. Allow to dry
overnight. The total dry film thickness of Specific bulk storage designs must
this and the preceding coat should be 3 – 4 conform to insurance underwriter’s codes
mils. (Note: some colored primers may and local fire and building regulations.
dissolve in styrene and discolor it unless Critical design, placement, installation and
the primer is completely covered by maintenance requirements are usually
subsequent coats of paint.) addressed in these codes and regulations
and must be followed.
4. Apply one sprayed coat of finish paint to all
surfaces. Allow to dry overnight. The total
dry film thickness following this step should API Design References
be 4.5 – 6 mils.
API Petroleum Institute
Recommendations of the paint manufacturer 1220 L Street, NW
regarding mixing, thinning, etc. should be Washington, DC 20005 USA
followed. Curing and drying times should be in
accordance with the paint manufacturer’s Part I - Design
recommendations.
API RP 520: Sizing, Selection and Installation
The completed lining should be free of of Pressure-relieving Devices in Refineries
pinholes, abrasions or other breaks in film
continuity, runs, sags and overspray. Each coat Part II - Installation
should be inspected after it has dried and
before the following coat is applied). API Standard 601: Metallic Gaskets for
Raised-Face Pipe Flanges and Flanged
Warning - The solvents used in these paints Connections (Double-Jacketed Corrugated and
can be toxic if breathed or absorbed in large Spiral-Wound)
quantities. They may also cause dermatitis in
some individuals. Consequently, it is API Standard 620: Design and Construction of
recommended that personnel wear supplied-air Large, Welded, Low-Pressure Storage Tanks
respirators and protective clothing while
working. Forced-air ventilation should be API Standard 650: Welded Steel Tanks for Oil
provided during blast-cleaning and lining- Storage

24 AUGUST 2020
API Standard 2000: Venting Atmospheric and
Low-Pressure Storage Tanks; Non-refrigerated
and Refrigerated

API RP 2003: Protection Against Ignitions

Arising Out of Static, Lightning, and Stray
Currents

API RP 2028: Flame Arresters in Piping

Systems

API RP 2210: Flame Arresters for Vents of

Tanks Storing Petroleum Products

API RP 2350: Overfill Protection for Storage

Tanks in Petroleum Facilities

API Standard 2015: Requirements for Safe

Entry and Cleaning of Petroleum Storage
Tanks

API Standard 653: Tank Inspection, Repair,

Alteration, and Reconstruction

AUGUST 2020 25
 PART 4

ACCIDENTAL RELEASE, FIRE AND HEALTH

Although the handling of Styrene Monomer is then be responsible for coordinating an

considered to present a low degree of health appropriate response to the transportation
risk, exposure to this product should always be incident.
minimized. Extensive experience has shown
that this monomer can be handled safely if its Eliminate all sources of ignition in the vicinity of
toxicological properties are clearly understood the spill or released vapor. Stop the source of
and proper precautions are practiced. the leak or release. Clean up releases as soon
as possible, observing personal protection
Safety Data Sheets for styrene are available precautions (see below). Contain liquid to
from AmSty to help customers further satisfy prevent further contamination of soil, surface
their own safe handling and disposal needs and water or groundwater. Styrene is expected to
OSHA Hazard Communication Rule be toxic to aquatic organisms. Avoid
requirements. Such information should be contaminating soil or releasing this material into
requested and studied prior to working with this sewage or drainage systems and bodies of
product. Please call AmSty at +1-844-512-1212 water. Clean up small spills using appropriate
to request the SDS for Styrene Monomer, or techniques such as sorbent materials or
download it from www.AmSty.com. NOTE: pumping. Where feasible and appropriate,
This guide is not a substitute for the SDS. remove contaminated soil. Follow prescribed
procedures for reporting and responding to
The following briefly summarizes the larger releases. The Reportable Quantity (RQ)
toxicological information. The precautions under CERCLA Section 302.4 is 1000 lb
recommended are general in nature because (453.6 kg). USA regulations require reporting
specific recommendations can be made only spills of this material that could reach any
when the conditions of handling are known. surface waters. The toll-free number for the
U.S. Coast Guard National Response Center is
(800) 424-8802.
Accidental Release Measures
If a transportation incident involving styrene Spills
does occur, the Chemical Transportation
Emergency Center (CHEMTREC) should be If styrene has been spilled, it can be removed
contacted for immediate assistance. safely for disposal. Before attempting to clean
CHEMTREC is a public service organization up the spill, be sure that the flow of liquid has
established by the American Chemistry Council been stopped and that all sources of ignition
to provide assistance in hazardous material are eliminated. Small spills (non-marine) can be
incidents. FOR A CHEMICAL EMERGENCY removed by covering the spill with sand or a
CALL CHEMTREC AT (800) 424-9300 toll suitable absorbent. Some absorbing agents,
free in the United States, Canada, Puerto such as untreated clays and micas, will cause
Rico, and the Virgin Islands. For emergency an exothermic reaction which might ignite the
calls outside the United States call monomer. For this reason, absorbing agents
+1.703.741.5970. should be tested for their effect on
polymerization of the monomer before they are
CHEMTREC will provide the caller preliminary used on large spills.
emergency assistance in the form of Safety
Data Sheet (SDS) information. In all cases, Contact local environmental or health
once CHEMTREC determines the incident authorities for approved disposal of the
involves an AmSty material, CHEMTREC will absorbing agent. If the spill is on a hard surface,
immediately contact the Americas Styrenics’ the area should be scrubbed with soap and
Emergency Response representative, who will

26 AUGUST 2020
water after the bulk of the monomer has been Electrical Hazards: Class 1, Group D
removed.
Larger spills should be contained within a dike, Behavior in Fire: Vapor is heavier
and water pumped into the area immediately. than air and may
This will prevent the monomer from soaking travel a considerable
into the ground and will allow it to be pumped distance to a source
off the water layer for recovery. of ignition and flash
back. At elevated
Styrene is toxic to aquatic organisms and temperatures, such
should be kept out of sewage and drainage as in fire conditions,
systems and all bodies of water. polymerization may
take place, which
may lead to
Disposal container explosion.

All disposal procedures are to be carried out in Burning Rate: 5.2 mm/min.
strict conformance to federal, state and local
regulations. Styrene monomer, and absorbent NFPA Fire Hazard Rating: 3
containing styrene, must be incinerated in an
approved designated furnace. Please contact
AmSty if additional assistance is required. Flammability
Styrene Monomer is classified by both OSHA
Fire Hazards 29 CFR 1910.26 and the National Fire
Protection Association (NFPA) Code 30 as a
This product presents a fire hazard. The liquid Class IC flammable liquid. The National Electric
evaporates and forms vapor (fumes) which can Code (NFPA 70) refers to styrene as a Class I,
catch fire and burn with explosive violence. Group D material.
Invisible vapor spreads easily and can be set
on fire by many sources such as pilot lights, Styrene will burn and requires the same
welding equipment, and electrical motors and precautions against fire and explosion hazards
switches. that commonly apply to other combustible and
flammable liquids. The flammability properties
For fires involving this material, do not enter of styrene are indicated in the Physical
any enclosed or confined fire space without Properties section (Part 1, Pages 3-6).
proper protective equipment. This may include
a self-contained breathing apparatus to protect
against the hazardous effects of normal Explosive Mixtures
products of combustion or oxygen deficiency.
Normal combustion forms carbon dioxide and Styrene vapor is heavier than air and could
water vapor; incomplete combustion can travel considerable distances to an ignition
produce carbon monoxide. Extinguish fires with source and flash back to the source. It is
foam, dry chemical or carbon dioxide. Use important to prevent the formation of explosive
water in flooding quantities as fog; solid or combustible mixtures, and to take
streams of water may be ineffective. Cool precautions to avoid ignition of any such
exposed containers with water. mixtures.

Flash Point: 31 °C (88 °F) Closed Styrene handling areas should be well
Cup ventilated and motors must be explosion-proof.
ALL TANK CARS, TANK TRUCKS, HOSE
Autoignition Temp.: 490 °C (914 °F) CONNECTIONS AND OTHER EQUIPMENT
MUST BE GROUNDED FOR THE SAFE
Flammable Limits in Air: 0.9 - 6.8 Vol % DISCHARGE OF STATIC ELECTRICITY.
Storage tanks and other containers that have

AUGUST 2020 27
been emptied of monomer must be flushed out Fires
with steam, nitrogen, or water to remove
monomer vapor. The tank atmosphere should Locations that depend on local fire companies
be tested before the tank is entered or worked should provide them with information
on with welding equipment. concerning the properties of styrene, their
operations and details (including diagrams) of
The dangers of fire and explosion are real storage vessels, quantities stored and other
because styrene can form explosive mixtures in pertinent details.
air at room temperatures. Precautions should
be taken to ensure that no ignition of vapors Fires involving styrene monomer can be safely
can occur, especially where elevated extinguished with foam, dry chemical, or carbon
temperatures are involved. dioxide. Water fog can also be used, however,
a water stream is not an effective extinguishing
Precautions include: agent for styrene. If electrical equipment such
as motors, open hot plates, or open electrical
1. Regular equipment inspections switches are involved, foam should be used
with caution. When burning, styrene gives off
2. Immediate repair of leaks toxic by-products, such as carbon monoxide
gas. For this reason, breathing of fumes,
3. Good ventilation smoke, and gas from a styrene fire should be
avoided. Do not enter any enclosed or confined
4. Proper facilities to contain spills quickly fire space without full protective equipment,
which include a self-contained breathing
5. Use of special alloy, non-sparking tools apparatus.

6. Periodic tests of pressure equipment Personnel conducting the cleanup should be

trained to satisfy OSHA Hazardous Operations
7. Elimination of all possible ignition sources and Emergency Response Standard 29 CFR
1910.120 requirements.
It is also important, at all times, to prevent the
formation of explosive or combustible mixtures After the fire has been put out, any residual
at other than normal pressures and monomer should be secured in proper storage
temperatures. While the actual operating or cleaned up to prevent loss to the
conditions may be outside the explosive limits, environment. If significant product is lost
the vapor system may pass through the contact your local environmental agency.
explosive range in reaching the desired
operating conditions. Thus, a vacuum
impregnation at 50 °C and 100 mm Hg pressure
involves a non-explosive mixture of styrene Personal Protective Equipment and
vapor and air. However, during the evacuation Occupational Exposure Limits
step from atmospheric pressure to 100 mm
pressure, the system goes through the Wear safety glasses with side shields as a good
explosive range. If the evacuation is performed safety practice when working with styrene.
at 20 °C and the system is then heated to Wear impervious protective clothing to prevent
50 °C, the explosive range will be avoided skin contact. Selection of protective clothing
completely. may include gloves, apron, boots and complete
facial protection and will depend on operations
If the system is properly flushed with nitrogen conducted. Users should determine acceptable
or other inert gases (helium, carbon dioxide) performance characteristics of protective
prior to evacuation, or if such gases are used clothing. Consider physical requirements and
for pressurizing, all such dangers are reduced. other substances present when selecting
protective clothing. Suggested materials for
protective gloves include Viton, Polyethylene-
Ethylene Vinyl Alcohol laminated film, and

28 AUGUST 2020
Polyvinyl Alcohol (PVA) (avoid contact with persists. Discard contaminated clothing and
water; PVA deteriorates in water). shoes or thoroughly clean before reuse.

Determine if airborne concentrations are below INGESTION: Harmful or fatal if swallowed.

the recommended exposure limits. If not, select Because of its low viscosity, styrene can
a NIOSH/MSHA-approved organic vapor directly enter the lungs if swallowed or if
respirator that provides adequate protection subsequently vomited. Once in the lungs it is
from measured concentrations of this material. very difficult to remove and can cause severe
Use a positive-pressure, air-supplying injury or death. First Aid: If swallowed, do not
respirator if there is potential for uncontrolled induce vomiting. Give the person a glass of
release, if exposure levels are not known, or if water or milk to drink and get immediate
other circumstances exist where air-purifying medical attention. Never give anything by
respirators may not provide adequate mouth to an unconscious person.
protection.
Note to Physician: Ingestion of this product or
The OSHA Permissible Exposure Limit (time- subsequent vomiting may result in aspiration of
weighted average) is 100 ppm. The styrene light hydrocarbon liquid, which may cause
industry, represented by SIRC, CFR, CI, ICPA pneumonitis.
and NMMA has agreed to establish a voluntary
program with OSHA to comply with an 8-hour INHALATION: Most humans can detect the
time-weighted average occupational exposure odor of styrene vapor at around 2-5 ppm and,
limit of 50 ppm and a 15-minute limit of 100 at around 100 ppm, begin to feel discomfort due
ppm. The American Conference of to eye and nose irritation. The vapor or fumes
Governmental Industrial Hygienists (ACGIH) from this material may cause respiratory
recommends a Threshold Limit Value (TLV) of irritation, including coughing or difficulty
20 ppm (8-hour time-weighted average) and a breathing. Breathing this material at
Short Term Exposure Limit (15 min) of 40 ppm. concentrations above the recommended
exposure limit may cause central nervous
OSHA Permissible Exposure Limit: system effects, including drowsiness,
Time Weighted Average (TWA) = 100 ppm dizziness, headache, nausea, vomiting,
weakness, loss of coordination, blurred vision,
ACGIH Threshold Limit Value: confusion, or disorientation. At extreme
Time Weighted Average (TWA) = 20 ppm exposure, central nervous system effects may
include respiratory depression, tremor or
convulsions, loss of consciousness, coma or
Health Hazards and First Aid death. Several epidemiology studies involving
over 90,000 workers in the styrene, polystyrene
STYRENE: and reinforced plastics industries together
show no increased cancer risk from
EYE CONTACT: Styrene is not expected to occupational exposure to styrene. Styrene may
cause prolonged or significant eye irritation. cause cancer in laboratory animals (mice only),
First Aid: If styrene gets into the eyes, no but the available information is inadequate to
specific first aid measures are required. As a determine if this material can cause cancer in
precaution, remove contact lenses, if worn, and humans. Repeated inhalation of this material at
flush eyes with water. concentrations above the recommended
exposure limit may cause damage to the liver
SKIN CONTACT: Contact with the skin causes based on animal data. Although damage to the
irritation which may include pain, reddening, olfactory cells in the nose has been found in
swelling, and blistering. Skin contact may mice and rats, reinforced plastics workers
cause drying or defatting of the skin. Styrene is exposed to an average of 26 ppm of styrene
not expected to cause an allergic skin showed no evidence of impairment in the ability
response. First Aid: If skin contact should to detect or identify odors. Information from
occur, wash skin immediately with soap and human experience and the results of animal
water and remove contaminated clothing and studies suggest no significant risk of birth
shoes. Get medical attention if irritation defects or reproductive toxicity of styrene in

AUGUST 2020 29
humans. First Aid: If a person should Environmental Hazards
accidentally be overcome or experience any ill
effects caused by breathing styrene, move the Styrene is expected to be toxic to aquatic
exposed person to fresh air. If not breathing, organisms. Styrene is expected to be readily
give artificial respiration. If breathing is difficult, biodegradable.
give oxygen. Get medical attention if symptoms
continue.

See the SDS for styrene for a more complete

discussion of the toxicity of styrene.

4-TERT-BUTYLCATECHOL (TBC):

TBC is typically added to styrene monomer to

inhibit polymer formation and oxidative
degradation during storage and shipment.
Typically, product is inhibited when TBC levels
are between 10-15 ppm, but if long storage
times or high temperatures are anticipated,
product is inhibited up to 100 ppm. Many
customers store limited quantities of TBC
concentrate or solid TBC for emergency use.

TBC is extremely corrosive to the skin and

eyes, and may be absorbed through the skin in
toxic amounts. TBC is a known skin sensitizer
and may cause depigmentation of the skin.
Once an individual has become sensitive, even
exposure to very small amounts can cause a
response. Concentrated solutions in styrene
can be expected to cause greater irritation than
would be expected from just the monomer.
Slight damage to the liver has been reported in
a rat feeding study.

Personnel should wear goggles and/or a full

face shield and protective clothing including
gloves and apron made of Viton while working
with TBC or its concentrated solutions. It should
not be pipetted by mouth. In case an accidental
contact with TBC or its strong solutions should
occur, it should be removed immediately from
the skin by washing with soap and plenty of
water; for eyes, flush them with plenty of water
for at least 30 minutes and get medical
attention immediately.

PLEASE CONSULT THE SDS FOR TBC

PRIOR TO HANDLING THIS CHEMICAL.

30 AUGUST 2020
 PART 5

TRANSPORTATION INFORMATION AND REGULATORY PROFILE

Transportation Information
LABELING:

Containers should be labeled in accordance with applicable OSHA and DOT requirements.

Identification numbers are required on each side and each end if the packaging capacity is 1000 gallons
or more; on two opposing sides if the packaging capacity is greater than 119 gallons but less than 1000
gallons. Markings for non-bulk packaging (119 gallons or less) include the proper shipping name,
identification number preceded by UN or NA, the technical name if applicable, and the consignee or
consignor’s name and address.

Labels are required on non-bulk packages and must be located on the same surface and near the
marking.

Placards are required on each side and each end of bulk packaging.

Requirements concerning marking, labeling, placarding, and the preparation of shipping papers vary
somewhat depending on the transport mode, packaging configuration, and quantity of hazardous
material being transported.

Marking, labeling, and placarding requirements are explained in detail in 49 CFR 172 Subparts D, E,
and F respectively. Subparts E and F show sample labels and placards. Labels and placards applicable
to flammable liquids are required for styrene monomer. Bulk containers should remain placarded when
emptied unless the special requirements of Subpart F are met.

CHEMICAL DESIGNATIONS:

U. S. Coast Guard Compatibility Class: Aromatic Hydrocarbon

Formula: C6H5CH=CH2
UNI/UN Designation: 3.0/2055
DOT ID No.: 2055
CAS Registry No.: 100-42-5

INTERNATIONAL MARITIME ORGANIZATION (IMO):

Proper Shipping Name: Styrene Monomer, stabilized

Class 3
UN Number UN 2055
Symbol Flammable Liquid
Pollution Category C
European Behavior Classification F, E, R (Floater, Evaporator, Reactide)

AUGUST 2020 31
SHIPPING INFORMATION:

Grades of Purity: 99.9%

Storage Temperature: Ambient
Inert Atmosphere: No requirement
Venting: Open (flame arrester)

Hazard Classifications

Code of Federal Regulations Flammable Liquid NAS Hazard Rating

Category for Bulk Water Transportation

Fire 3

Health
Vapor Irritant 2
Liquid or Solid Irritant 2
Poisons 2

Water Pollution
Human Toxicity 1
Aquatic Toxicity 3
Aesthetic Effect 2

Reactivity
Other Chemicals 2
Water 0
Self-Reaction 3

NFPA HAZARD CLASSIFICATION:

Category Rating

Health Hazard (Blue) 2

Flammability (Red) 3
Reactivity (Yellow) 2

WATER POLLUTION:

Harmful to aquatic life in very low concentrations

Fouling of shoreline
May be dangerous if it enters water intakes
Notify local health and wildlife officials
Notify operators of nearby water intakes

Drums
The UN Standard 1A1 steel, non-removable head drum should be used to transport styrene monomer.
The performance-oriented standards for the 1A1 are described in 49 CFR 178 Subpart M. For styrene
monomer the following level three tests must be performed: hydrostatic pressure, leak proof, drop,
stacking, and vibration.

When the drums used to ship styrene monomer are emptied, they should be immediately triple rinsed
with a suitable solvent. The drums should not be cut or punctured prior to complete cleaning.

32 AUGUST 2020
If over packing is used, the inner drum must be isolated from the outer drum as described in 49 CFR
173 Subpart E and must be segregated on the vehicle as described by 49 CFR 177 Subpart C.

Regulatory Profile
STYRENE:

1) ODCs: Contains Class 1 or Class 2 Ozone Depleting Chemicals (ODCs)? NO

2) TSCA: Is this product or its components subject to any of the following TSCA requirements of 40
CFR, Part:

707 (Export Notifications) (12b) NO

712 (Chemical Information Reporting) (8a) NO
716 (Health & Safety Data Reporting) (8d) NO
721 (Significant New Use) (5e) NO
723.50 (Low Volume Exemption) NO
720.36 (R&D Exemption) NO
720.38 (Test Marketing Exemption) NO
723.25 (Polymer Exemption) NO
790 (Health and/or Environmental Effects Testing (4e) NO

Is this material distribution under limitations of a 5(e) or 5(f) Consent Order? NO

Have there been any Section 8(e) submissions for this material? YES

3) International Registration: Are all components of this material listed on the following
international inventories?

TSCA (United States) YES

DSL (Canada) YES
EINECS (Europe) YES (EINECS reg. no. 202-851-5)
METI (Japan) YES
AICS (Australia) YES
PICCS (Philippines) YES
KMOE (Korean) YES (KMOE reg. no. 3-1289)

4) FDA: Do FDA regulations permit use of this material as a direct or indirect food additive?

INDIRECT YES (21 CFR 177.1640)

Limited to 1.0 WT% as residual styrene monomer in General Purpose Polystyrene (GPPS) or 0.5
WT% in High Impact Polystyrene (HIPS).

5) HAZARDOUS METALS: Does the sum of the concentration levels of lead, cadmium, mercury
and hexavalent chromium present in this material exceed 100 ppm by weight? NO

6) ADDITIONAL REGULATORY INFORMATION: See AmSty SDS for Styrene Monomer, Section
15 for additional regulatory information.

AUGUST 2020 33
Revision Statements
July 2011

1. Updated EH&S Policy, inside cover

2. Updated page 8 with Sales Specification values
3. Updated list of Analytical ASTM test methods, page 9
4. Updated Flammability Limits, page 28
5. Various editorial corrections

November 2016

1. Updated AmSty logo, phone numbers and overall format

2. Updated EH&S Policy
3. Removed Sales Specification
4. Updated Product Stewardship Policy
5. Updated Introduction
6. Updated Physical Properties list
7. Updated References list
8. Updated Analytical Methods list
9. Updated Tables 1, 2B, 3A and 3B
10. Updated lists of approved materials for Gaskets and O-rings

August 2020

1. Updated Copyright Date, and updated ODMS to OEMS, Page 1.

2. Updated Introduction, Page 2. Revised Note to Disclaimer with revised text.
3. Updated Revision Date in footer.

34 AUGUST 2020
 PART 6

APPENDIX

Glossary of Terms, Abbreviations and Organizations

ACGIH American Conference of Governmental Industrial Hygienists

ANSI American National Standards Institute

API American Petroleum Institute

ASTM American Society for Testing and Materials

Bonding The connection of two or more conductive objects by means of a conductor

(most commonly a wire or metal plate)

CERCLA Comprehensive Environmental Response, Compensation, and Liability Act

CFR Code of Federal Regulations

CG Coast Guard

CHEMTREC Chemical Transportation Emergency Center

DOT Department of Transportation

EPA Environmental Protection Agency

FDA Food & Drug Administration

IMO International Maritime Organization

ISGOTT International Safety Guide for Oil Tanker and Terminals

ISO International Organization of Standardization

MSHA Mine Safety and Health Administration

NFPA National Fire Protection Association

NIOSH National Institute for Occupational Safety and Health

OSHA Occupational Safety and Health Administration

ppm Parts per million

RQ Reportable Quantity

AUGUST 2020 35
SDS Safety Data Sheet

SIRC Styrene Information and Research Center

SQC Statistical Quality Control

TWA Time-Weighted Average

UN United Nations

USCG United States Coast Guard

WT% Weight percent

36 AUGUST 2020