Appendix 15

MTBE Product Safety Bulletin

European Fuel Oxygenates Association

www.efoa.org
 METHYL TERTIARY BUTYL ETHER

DRAFT COPY

DEVELOPED BY
THE ENVIRONMENTAL, HEALTH AND SAFETY DEPARTMENT

LYONDELL CHEMICAL COMPANY

1221 McKinney Street
Houston, TX 77010
Draft Product Safety Bulletin

OUR MISSION
ARCO Chemical Company will produce
chemicals, related products, and services in a
manner that enhances value for our stockholders,
customers, employees, and the public.

To achieve this mission, we will:

manage our assets to produce a superior return

on our stockholders' investment;

sell high-quality, competitive products and provide

superior service to customers;

create an environment for employees that fosters

personal growth and allows individuals to
achieve their full potential; and

operate our facilities in an environmentally

responsible manner, provide a safe work place for
our employees, and produce only those products
we believe to be safe for customer use.

Lyondell Chemical Company

Page 2 of 59
Draft Product Safety Bulletin

FOREWORD

Lyondell Chemical Company is dedicated to continuous improvement in product health, safety and
environmental performance. Included in this effort is a commitment to support our customers by
providing guidance and information on the safe use of our products. For Lyondell Chemical,
environmentally sound operations, like environmentally sound products, make good business sense.

Lyondell Chemical Company Product Safety Bulletins are prepared by our Environmental, Health and
Safety Department with the help of experts from our manufacturing and research facilities. The data
reflect the best information available from public and industry sources. This document is provided to
support the safe handling, use, storage, transportation and ultimate disposal of our chemical products.

This Product Safety Bulletin should be evaluated to determine applicability to your specific
requirements. Please make sure you review the government regulations, industry standards and
guidelines cited in this bulletin that might have an impact on your operations.

Lyondell Chemical Company is ready to support our customers' safe use of our products. For
additional information and assistance, please contact your Lyondell Chemical Company customer
representative.

Dan Smith
President and
Chief Executive Officer

Lyondell Chemical Company

Page 3 of 59
Draft Product Safety Bulletin

IN CASE OF A TRANSPORTATION EMERGENCY, CALL:

ACNL, Rotterdam, The Netherlands (Country Code 31 )

or
ARCO Chemie, Fos sur Mer, France (Country Code 33)

(0) 18-194-72-00

(0) 42-47-5100

FOR MORE INFORMATION ABOUT OUR PRODUCT, CALL:

ARCO Chemical Europe Inc., Maidenhead, U.K. (Country Code 44)

(0) 628-77-5000

This bulletin is provided as a service without charge to our customers and contractors and should be utilised at their own discretion and
risk. It is intended for persons with specialised knowledge and technical skills, which are required for proper understanding and
interpretation of the information contained herein. The information was obtained from sources believed to be reliable and is based on
industry practices prevailing at the time of compilation, which are subject to change and may be subject to variance.

The information in this bulletin is provided without any warranty, expressed or implied, regarding its accuracy and completeness.
Recipients are expected and advised to undertake their own inquiry and study, and be trained in the environmental, health and safety
requirements of the product. Customers and contractors should also be familiar with applicable international, national and local laws
and regulations. References to a specific product line or any list of suppliers is provided as a matter of convenience, and is not an
endorsement or recommendation of a particular brand or company. In addition, the information was prepared and is to be used only for
this product. If the product is used as a component in, or in combination with, another product, the information may not be accurate or
applicable.

For the above reasons, and because the conditions and methods of handling, storage, use and disposal of the product are beyond our
control and may be beyond our knowledge, we do not assume any responsibility and expressly disclaim any liability for loss, damage or
expense arising out of or in connection with the use of the information set forth herein, and the handling, storage, use or disposal of the
product.

This document contains dated material. Recipients are advised to evaluate the timeliness of information cited. The latest revision of this
Product Safety Bulletin can be obtained by contacting ARCO Chemical Customer Service

Lyondell Chemical Company

Page 4 of 59
Draft Product Safety Bulletin

TABLE OF CONTENTS

1. GENERAL INFORMATION 6.6 MATERIAL DATA SAFETY SHEETS

6.7 LOCAL EMERGENCY PLANNING
1.1 PRODUCT IDENTIFICATION 6.8 NATIONAL REGULATIONS
1.2 PHYSICAL PROPERTIES
1.3 TYPICAL VALUES 7 ENVIRONMENTAL
1.4 INSTABILITY HAZARDS
1.5 REACTIVITY HAZARDS 7.1 AIR QUALITY CONSIDERATIONS
7.2 WATER QUALITY
7.3 WASTE MANAGEMENT
2. OCCUPATIONAL HEALTH

2.1 HAZARD ASSESSMENT 8 PRODUCT STORAGE

2.2 OCCUPATIONAL EXPOSURE LIMITS
2.3 FIRST AID 8.1 STORAGE TANKS
2.4 MEDICAL MANAGEMENT 8.2 UNLOADING INSTALLATIONS

3. PERSONAL SAFETY AND HEALTH 9 TRANSFER OPERATIONS

3.1 SITE FACILITIES 9.1 WORK PREPARATION

3.2 HYGIENE PRACTICES 9.2 TANK CARS
3.3 RESPIRATORY PROTECTION 9.3 TANK TRUCKS
3.4 CHEMICAL PROTECTIVE CLOTHING 9.4 MARINE TRANSPORT
3.5 DIRECT READING INSTRUMENTS
3.6 AIR SAMPLING AND ANALYSIS
10. TANK CLEANING AND EQUIPMENT
REPAIR
4. ENGINEERING
10.1 WORK PREPARATION
4.1 BULK STORAGE 10.2 CONTROL OF HAZARDOUS
4.2 PIPING ENERGY
4.3 ELECTRICAL AREA CLASSIFICATION 10.3 CONFINED SPACE ENTRY
4.4 PUMP SPECIFICATIONS 10.4 EQUIPMENT CLEANOUT
4.5 INSTRUMENTATION 10.5 MAINTENANCE AND INSPECTION
4.6 RELIEF REQUIREMENTS
4.7 LEAK DETECTION DEVICES
4.8 MATERIAL REQUIREMENTS 11. TRANSPORTATION REGULATORY
4.8 VAPOUR CONTAINMENT SYSTEM REQUIREMENTS

11.1 CLASSIFICATION
5. FIRE SAFETY 11.2 MARKING, LABELLING, AND
PLACARDING
5.1 FIRE AND EXPLOSION HAZARD 11.3 PACKAGING
5.2 FIRE PREVENTION 11.4 TRANSPORTATION EMERGENCIES
5.3 FIRE SUPPRESSION
5.4 FIRE FIGHTING
12. APPENDICES

6 HAZARD COMMUNICATION I CONVERSION FACTORS

II NAMES OF MANUFACTURERS
6.1 WORKER TRAINING III NIOSH METHOD 1615
6.2 HAZARDS IV REFERENCES
6.3 METHODS OF DETECTION V REGULATORY SUMMARY
6.4 METHODS OF PROTECTION VI GLOSSARY
6.5 LABELLING

Lyondell Chemical Company

Page 5 of 59
Draft Product Safety Bulletin

1. GENERAL INFORMATION
Lyondell Chemical Company is the world's This bulletin deals only with ''neat'' (greater
leading producer of methyl tertiary butyl ether than 90 percent) MTBE. The information
(MTBE). We are pleased to share more than provided in the figures and tables of Section
a decade of experience in the manufacture, 1.2 is based on high purity MTBE and may
handling, and shipment of MTBE with vary with product composition. Blended
customers who use MTBE as a fuel gasoline that contains lower levels of MTBE
component. is generally handled in the same manner as
hydrocarbon-only gasoline and requires no
This bulletin contains information on the extraordinary precautions. Please contact
properties of MTBE and provides our Lyondell Chemical Europe Inc., Maidenhead,
recommendations regarding its receipt, U.K. (Country Code 44) (1) 628-77-5000 or
unloading, storage, transfer, processing, and, your Lyondell Chemical regional sales office
as necessary, disposal. This bulletin is for additional information.
intended to help our customers safeguard
worker and community health and safety, 1.1 Product Identification
and protect the environment in accordance
with national regulations. Chemical Name: 2-methoxy-2- methyl-
propane
MTBE is a chemically stable, flammable, and
highly volatile liquid. Although it is relatively
non-toxic to humans, it behaves as an Chemical Family: Alkyl ethers
anaesthetic when very high vapour Common Names: MTBE
concentrations are inhaled. Methyl tert-butyl ether
tert-Butyl methyl ether
Bulk quantities of MTBE should be received, CAS# : 1634-04-4
stored, processed, and disposed of only in Formula: C5H12O
facilities designed for those purposes.
Storage systems should be inspected for 1.1.1 Applications
elastomer compatibility before introducing
MTBE for the first time. After initial
Lyondell Chemical Company's MTBE was
inspection, storage systems should be
originally used commercially as a gasoline
operated as outlined in this bulletin.
octane enhancer to replace lead in gasolines
Appropriate emergency notification and
sold in the United States and Europe. New
response systems for fire and spill
requirements for cleaner burning gasolines
management should be in place at each
have expanded the MTBE market. When
facility where MTBE is received, stored, or
gasoline containing MTBE is used in
used. MTBE should be handled only by
automobiles, the oxygen inherent in the
workers trained in safe handling methods
MTBE contributes to more complete
and response to emergencies such as spills
combustion of carbon monoxide and
or fires.
hydrocarbons, resulting in lower emissions of
these pollutants.
The water solubility of MTBE, its effect on
some elastomeric polymers, and firefighting
foam requirements are different than those
for gasoline. Lyondell Chemical Company
believes that, except for these differences,
design and operation standards applicable to
gasoline storage and handling facilities also
apply to MTBE. These differences are
reflected in recommendations presented
throughout this bulletin.

Lyondell Chemical Company

Page 6 of 59
Draft Product Safety Bulletin

1.2 Physical Properties

Table 1-1

MTBE PHYSICAL PROPERTIES**

Property Value Property Value

Physical State Liquid Heat/Fusion 1816.4 cal/mol
@-108.6ºC 3269.6 BTU/lbmol
Colour Colourless Heat/Vaporisation Figure 1-5
Boiling Pt. 55.2ºC Heat Capacity of Figure 1-6
131.4ºF Sat’d Liquid
Freezing Pt. -108.6ºC Enthalpy of Sat’d Figure 1-7
-163.5ºF Liquid
Density @ 25ºC 0.735 g/cc Heat Capacity of Figure 1-8
Sat’d Vapour
Density of Figure 1-1 Enthalpy of Sat’d Figure 1-9
Sat’d Liquid And Table 1-2 Vapour
Vapour Density Figure 1-2 Surface Tension Figure 1-10
Vapour Pressure Table 1-3 Thermal Conduct. Of Figure 1-11
Sat’d Liquid
Viscosity of Sat’d Figure 1-3 Thermal Conduct. Of Figure 1-12
Liquid Vapour
Visc. of Vapour Figure 1-4 Flash Point (TCC)* -29ºC
-20±1ºF
Index/Refraction 1.3692 Auto Ignition 374ºC
@ 20ºC 705ºF
-1
Coeff./Cubical 0.00078ºF Upper Flam. Limit* 8.5 vol%
Expansion @68ºF
Crit. Temperature 224.0ºC Lower Flam. Limit* 1.5 vol%
435.2ºF
Crit. Pressure 3.43 Mpa Solubility/MTBE in Water: 4.3 wt%
497.6 psia @20ºC Alcohol: ∞
Ether: ∞
Crit. Volume 3.7323 cc/g Solubility/water in MTBE: 1.4 wt%
3
0.0598 ft /lb
Crit. Compress. 0.273 Sat. Conc. In Air @ 32.9 mol%
25ºC 59.9 wt%
-30
Acentric Factor 0.2661 Dipole Moment 4.54 x 10 C●m
Heat/Combustion, -805.2 Kcal/mol Dielectric Constant 2.6
Liquid @ 25ºC
-10
Heat/Formation, -67.68 Kcal/mol Conductivity 1.21x10 mhos/cm
Vapour @ 25ºC
Heat/Formation, -74.94 Kcal/mol
Liquid @ 25ºC

** The information provided in this table and the other figures and tables of Section 1.2 is based
on high purity MTBE except where indicated by * for fuel grade.

Lyondell Chemical Company

Page 7 of 59
Draft Product Safety Bulletin

Figure 1-1
D e n s ity o f S a tu ra te d L iq u id a s a F u n c tio n o f T e m p e ra tu re

0 .9 0

0 .8 8

0 .8 6

0 .8 4

0 .8 2

0 .8 0

0 .7 8

0 .7 6
0 .7 4
Density (g/cc)

0 .7 2

0 .7 0

0 .6 8

0 .6 6
0 .6 4

0 .6 2
0 .6 0

0 .5 8

0 .5 6

0 .5 4

0 .5 2
0 .5 0
-1 0 0 -8 0 -6 0 -4 0 -2 0 0 20 40 60 80 100 120 140 160 180

T e m p e r a tu re ( o C )

Table 1-2

Methyl t-Butyl Ether Density as a Function of Temperature

Temperature Lbs. Per U.S. Sp Gr to 60ºF Temperature Lbs. Per U.S. Sp Gr to 60ºF
ºC ºF Gallon ºC ºF Gallon
4.4 40 6.313 1.0153 21.7 71 6.165 0.9915
5.0 41 6.308 1.0145 22.2 72 6.160 0.9907
5.6 42 6.303 1.0137 22.8 73 6.155 0.9899
6.1 43 6.299 1.0130 23.3 74 6.150 0.9891
6.7 44 6.294 1.0122 23.9 75 6.145 0.9883
7.2 45 6.289 1.0115 24.4 76 6.140 0.9875
7.8 46 6.284 1.0107 25.0 77 6.135 0.9868
8.3 47 6.280 1.0100 25.6 78 6.131 0.9860
8.9 48 6.275 1.0092 26.1 79 6.126 0.9852
9.4 49 6.270 1.0084 26.7 80 6.121 0.9844
10.0 50 6.265 1.0077 27.2 81 6.116 0.9836
10.6 51 6.261 1.0069 27.8 82 6.111 0.9828
11.1 52 6.256 1.0061 28.3 83 6.106 0.9820
11.7 53 6.251 1.0054 28.9 84 6.101 0.9812
12.2 54 6.246 1.0046 29.4 85 6.096 0.9804
12.8 55 6.242 1.0038 30.0 86 6.091 0.9796
13.3 56 6.237 1.0031 30.6 87 6.086 0.9788
13.9 57 6.232 1.0023 31.1 88 6.081 0.9780
14.4 58 6.227 1.0015 31.7 89 6.076 0.9772
15.0 59 6.223 1.0008 32.2 90 6.071 0.9764
15.6 60 6.218 1.0000 32.8 91 6.066 0.9756
16.1 61 6.213 0.9992 33.3 92 6.061 0.9748
16.7 62 6.208 0.9985 33.9 93 6.056 0.9740
17.2 63 6.203 0.9977 34.4 94 6.051 0.9732
17.8 64 6.199 0.9969 35.0 95 6.046 0.9724
18.3 65 6.194 0.9961 35.6 96 6.041 0.9716
18.9 66 6.189 0.9954 36.1 97 6.036 0.9708
19.4 67 6.184 0.9946 36.7 98 6.031 0.9700
20.0 68 6.179 0.9938 37.2 99 6.026 0.9692
20.6 69 6.174 0.9930 37.8 100 6.021 0.9684
21.1 70 6.170 0.9922

Lyondell Chemical Company

Page 8 of 59
Draft Product Safety Bulletin

Figure 1-2

D e n s ity o f V a p o u r @ 1 A tm o s p h e re
a s a F u n c tio n o f T e m p e ra tu re

4 .0

3 .8

3 .6
Density of Vapour x 10 (g/cc)

3 .4

3 .2
3

3 .0

2 .8

2 .6

2 .4

2 .2

2 .0

1 .8
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280

T e m p e ra tu re ( o C )

Table 1-3

Vapour Pressure of Methyl t-Butyl Ether

as a Function of Temperature
Temperature Vapour Pressure Temperature Vapour Pressure
ºC ºF Mm HG psia Psig ºC ºF mm Hg psia Psig
-20.00 -4.00 26.19 0.51 90.00 194.00 2110.46 40.81 26.11
-15.00 5.00 35.23 0.68 95.00 203.00 2398.26 46.37 31.68
-10.00 14.00 46.76 0.90 100.00 212.00 2714.52 52.49 37.79
-5.00 23.00 61.31 1.19 105.00 221.00 3060.92 59.19 44.49
0.00 32.00 79.48 1.54 110.00 230.00 3439.17 66.50 51.81
5.00 41.00 101.91 1.97 115.00 239.00 3851.02 74.47 59.77
10.00 51.00 129.35 2.50 120.00 248.00 4298.24 83.11 68.42
15.00 59.00 162.60 3.14 125.00 257.00 4782.66 92.48 77.79
20.00 68.00 202.53 3.92 130.00 266.00 5306.13 102.60 87.91
25.00 77.00 250.10 4.84 135.00 275.00 5870.59 113.52 98.82
30.00 86.00 306.32 5.92 140.00 284.00 6478.03 125.26 110.57
35.00 95.00 372.30 7.20 145.00 293.00 7130.51 137.88 123.19
40.00 104.00 449.17 8.69 150.00 302.00 7830.19 151.41 136.72
45.00 113.00 538.16 10.41 155.00 311.00 8579.34 165.90 151.20
50.00 122.00 640.55 12.39 160.00 320.00 9380.34 181.39 166.69
55.00 131.00 757.65 14.65 165.00 329.00 10235.71 197.93 183.23
55.09 131.17 760.00 14.70 0 170.00 338.00 11148.16 215.57 200.87
60.00 140.00 890.85 17.23 2.53 175.00 347.00 12120.54 234.37 219.68
65.00 149.00 1041.57 20.14 5.44 180.00 356.00 13155.94 254.39 239.70
70.00 158.00 1211.28 23.42 8.73 185.00 365.00 14257.69 275.70 261.00
75.00 167.00 1401.47 27.10 12.40 190.00 374.00 15429.39 298.36 283.66
80.00 176.00 1613.68 31.20 16.51 195.00 383.00 16674.94 322.44 307.75
85.00 185.00 1849.48 35.76 21.07 200.00 392.00 17998.60 348.04 333.34

Lyondell Chemical Company

Page 9 of 59
Draft Product Safety Bulletin

Figure 1-3

V iscosity of Saturated Liquid as a function of Tem perature

0.9 0

0.8 5

0.8 0

0.7 5

0.7 0

0.6 5
Viscosity (cps)

0.6 0

0.5 5

0.5 0

0.4 5

0.4 0

0.3 5

0.3 0

0.2 5

0.2 0
-40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35 40

o
Tem perature ( C )

Figure 1-4

Viscosity of Vapour @ 1 Atmosphere

as a Function of Temperature

1.50

1.45

1.40

1.35
Viscosity of Vapour x 10 (cps)

1.30
2

1.25

1.20

1.15

1.10

1.05

1.00

0.95

0.90

0.85

0.80
60 80 100 120 140 160 180 200 220 240 260 280 300

o
Temperature ( C)

Lyondell Chemical Company

Page 10 of 59
Draft Product Safety Bulletin

Figure 1-5

Heat of Vaporisation as a Function of Tem perature

80

78

76

74

72
Heat of Vaporisation (cal/g)

70

68

66

64

62

60

58

56

54

52

50
50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150

Tem perature ( o C)

Figure 1-6

H eat C apacity of Saturated Liquid

as a function of Tem perature

0.5 40

0.5 35

0.5 30
Heat Capacity of Saturated Liquid (cal/g C)
o

0.5 25

0.5 20

0.5 15

0.5 10

0.5 05

0.5 00

0.4 95

0.4 90

0.4 85

0.4 80

0.4 75

0.4 70

0.4 65

0.4 60
-30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55

o
Tem perature ( C )

Lyondell Chemical Company

Page 11 of 59
Draft Product Safety Bulletin

Figure 1-7

Enthalpy of Saturated Liquid

as a function of Temperature

120

110

100

90
Enthalpy of Saturated Liquid (cal/g)

80

70

60

50

40

30

20

10

-10

-20

-30

-40
-100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180

o
Temperature ( C)

Reference : Saturated Liquid MTBE at O°C

Figure 1-8

H e a t C a p a c ity o f V a p o u r (Id e a l G a s )
a s a F u n c tio n o f T e m p e ra tu re

0 .4 7

0 .4 6

0 .4 5

0 .4 4
Heat Capacity of Vapour (cal/g°C)

0 .4 3

0 .4 2

0 .4 1

0 .4 0

0 .3 9

0 .3 8

0 .3 7

0 .3 6

0 .3 5

0 .3 4

0 .3 3

0 .3 2
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

T e m p e r a tu r e ( o C )

Lyondell Chemical Company

Page 12 of 59
Draft Product Safety Bulletin

Figure 1-9

Enthalpy of Saturated Vapour

as a function of Tem perature

160

150

140
Enthalpy of Saturated Vapour (cal/g)

130

120

110

100

90

80

70

60

50
-100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180

o
Tem perature ( C)

Reference : Saturated Liquid MTBE at O°C

Figure 1-10

Surface Tension
as a Function of Tem perature

23

22

21

20

19
Surface Tension (dynes/cm)

18

17

16

15

14

13

12

11

10

5
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

Tem perature ( o C)

Lyondell Chemical Company

Page 13 of 59
Draft Product Safety Bulletin

Figure 1-11

Therm al Conductivity of Saturated Liquid

as a Function of Tem perature

1.32
2

1.30
Thermal Conductivity of Saturated Liquid (cal/hr cm

1.28

1.26

1.24

1.22

1.20

1.18
C/cm)

1.16

1.14
o

1.12

1.10

1.08

1.06

1.04

1.02

1.00
-50 -45 -40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55

Tem perature ( o C)

Figure 1-12

Therm al Conductivity of Vapour @ 1 Atm osphere

as a Function of Tem perature

0.22

0.21

0.20
Thermal Conductivity of Vapour

0.19

0.18
(cal/hr cm C/cm)

0.17

0.16
2o

0.15

0.14

0.13

0.12

0.11

0.10

0.09
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

o
Tem perature ( C)

Lyondell Chemical Company

Page 14 of 59
Draft Product Safety Bulletin

1.3 Typical Values

TYPICAL COMPOSITION
(Range, wt.%)

MTBE, purity 96.5 - 97.5

Diisobutylene,
Triisobutylene,
and t-Butyl Alcohol 0.5- 1.0
Methanol 0.04 - 0.3
C4 Hydrocarbons0. 2- 1.6
C5 Hydrocarbons NIL - 0.5
Other NIL - 0.3
Water Content <0.05

To assist in the use of this document, a series

of conversion factors are assembled in
Appendix I.

1.4 Instability Hazards

MTBE is chemically stable; it does not
polymerise, nor will it decompose under normal
conditions of temperature and pressure. Unlike
most ethers, MTBE does not tend to form
peroxides (auto-oxidise) during storage.

1.5 Reactivity Hazards

MTBE is non-reactive. It does not react with air,
water, or common materials of construction.
The reactivity of MTBE with oxidising materials
is probably low. However, without definitive
information, it should be assumed that MTBE
reacts with strong oxidisers, including
peroxides.

MTBE may hydrolise in the presence of some

acids. MTBE is very stable in the presence of
reducing agents and reactive monomers.

Lyondell Chemical Company

Page 15 of 59
Draft
2. OCCUPATIONAL HEALTH
2.1 Hazard Assessment
A careful review of all the toxicological studies
completed to date have clearly shown that MTBE
does not present any significant health hazard at
the levels measured in the workplace or at the
levels measured in drinking water which has been
contaminated by leaking underground storage
tanks. In fact, only minimal toxicity can be induced
in animals at exposure levels several fold higher
than the highest levels measured in the workplace
and hundreds of times higher than in the most
contaminated drinking water.
In animal experiments, MTBE has been studied
using single exposure, repeated daily exposures
and recently, mice and rats were exposed to MTBE
for their lifetime. The most predominant effect noted
in all these studies was the induction of drowsiness
and motor inco-ordination at the higher dose or
exposure levels, usually well above 400 ppm. It was
also noted that the animals recovered quickly and
completely within a very short time, even at levels of
800 ppm. This finding was consistent with the data
from metabolism studies which showed that MTBE
was rapidly metabolised and eliminated from the
body. Other acute studies indicated that MTBE
would be considered to be a moderate skin irritant
and to be irritating to the eye. There were no
indications that MTBE would be a skin sensitiser.
In summary, the evidence from all the animal
studies show that there is only minimal toxicity
associated with exposure to MTBE at the levels that
can be expected in the workplace or in the routine
use of the chemical. Since the average odour
detection threshold of MTBE is very low (0.051
ppm) and MTBE does have a terpene like odour,
there would be sufficient warning of the presence of
MTBE to preclude any significant hazard from
overexposure.
IPCS** conclusions : The World Health
Organisation has reviewed the health effects on
MTBE and concludes that it is unlikely that MTBE
alone induces adverse health effects in the general
population under common exposure conditions*.
• WHO, Methyl Tertiary-butyl ether. Env. Health
Criteria 206, **International Programme on
Chemical Safety 1998 – ISBN 92 4 157 206 X
Product Safety Bulletin
2.1.1 Acute Effects of Over Exposure
The single exposure (acute) effects of MTBE have
been studied in many species of animals - mice,
rats, rabbits and monkeys. The findings from all
species have indicated that MTBE is a primary
irritant to the skin and eye with an oral LD50 of 3.5
grams/kilogram body weight and the inhalation
LC50 is approximately 35,000 ppm. The chemical is
only slightly absorbed through the skin so that no
definitive lethal dose can be determined by this
route of administration. All of these studies clearly
indicate that MTBE is only slightly toxic by single
exposures.
2.1.2 Neurotoxicity
MTBE has many pharmacological properties which
are similar to the anaesthetic gas diethyl ether, but
MTBE is several times less effective as an
anaesthetic than "ether". At very high exposure
levels, MTBE will cause animals to become sedated
and ataxic (drunk-like movements). Rats were
studied for possible neurotoxicity and
neurobehavioural toxicity after exposure to 800,
4000 or 8000 ppm of MTBE. Some behavioural
changes were noted at one hour after exposure to
either 4000 or 8000 ppm but the effects were
completely reversed within 6 hours. No significant
changes were seen after the 800 ppm dose. As can
be expected with an anaesthetic like chemical, the
lower doses of MTBE increased slightly the motor
activity of the rats while the highest dose decreased
the activity. The neuro-behavioural changes noted
after 13 weeks of exposure were similar to those
seen after a single 5 hour exposure. MTBE is not
considered to be neuro-toxic nor will it induce any
permanent neuro-behavioural changes.
Lyondell Chemical Company
Page 16 of 59
Draft
2.1.3 Reproductive and Developmental
Toxicity
MTBE has been studied for possible effects on
reproduction and for effects on the developing
foetus. Even at the highest exposure level tested
(8000 ppm), MTBE did not have any adverse
effects on the reproductive capability of either the
male or the female rat. The latest study was carried
out over two generations of rats and there were no
significant effects reported on the many parameters
measured.
Additionally, MTBE has been studied in pregnant
mice, rats and rabbits to ' determine if the chemical
would have any adverse effect on the developing
fetus. The single adverse finding was reported from
the mice exposed to 8000 PPM MTBE during
pregnancy, however, there were no adverse
findings at lower exposure levels (4000 or 1000
PPM). The adverse finding was an increased
incidence of cleft palate in the offspring of the high
dose female mice. The occurrence of cleft palate in
mice is not an unusual finding especially in
pregnant mice which are subjected to stress. MTBE
at 8000 PPM could be sufficient to cause a
significant level of stress as was evidenced by an
increase in the blood levels of corticosteroids in
other experiments.
Pregnant rabbits exposed to the same levels of
MTBE did not show any adverse effects in their
offspring.
These many studies show that MTBE would be
considered neither a reproductive nor a
developmental toxin.
2.1.4 Genetic Toxicology
MTBE has also been studied in several assays
designed to uncover the potential of a chemical to
alter genetic material. MTBE did not cause any
mutagenic responses in any of the assays except
for one portion of the mouse lymphoma assay. In
this particular assay, a positive response was seen
only when the cells were incubated with an enzyme
preparation (S-9). S-9 contains some, but not all, of
the usual enzymes found in the liver of the whole
animal. Further experimentation with MTBE and the
S-9 preparation showed that MTBE was not
completely broken down by the limited enzymes
present and, unlike the metabolism in the whole
animal. methanol and formaldehyde were formed
Product Safety Bulletin
by the S-9. Methanol and formaldehyde are known
to be positive mutagens in the mouse lymphoma
assay. The preponderance of evidence from other
mutagenic assays clearly shows that MTBE does
not affect genetic material and is not considered to
be a mutagen.
2.1.5 Chronic Effects of
Overexposure/Carcinogenicity
Chronic toxicity studies have been completed for
MTBE. In these studies B6C3F1 mice and F344
rats were exposed to 400, 3000, or 8000 ppm
MTBE vapours 6 hours/day, 5 days/week for life.
Few adverse effects were noted for either rats or
mice.
Male and female mice exposed to 8000 PPM MTBE
vapours developed a slightly higher incidence of
benign liver tumours during their lifetime. No other
adverse effects or increases in tumour incidences
were found.
Male and female rats exposed to MTBE vapours
developed an increased incidence of chronic
progressive kidney damage - an effect typically
noted in ageing rats. These effects were most
severe in 3000 and 8000 ppm exposure groups and
were accompanied by an increased incidence of
kidney tumours (males only). These findings are
consistent with kidney damage associated with
accumulation of protein in cells - an effect which
may be unique to the male rat. Benign testicular
tumours were numerically increased in high-dose
MTBE male rats, but this is an age-related lesion
which typically occurs in a very high proportion of
control untreated rats.
All of these effects either occur in tissues prone to
the development of tumours or may occur by a
mechanism not considered relevant to humans.
IARC has reviewed the available data on MTBE and
concluded that "there is limited evidence in
experimental animals for the carcinogenicity of
methyl tert-butyl ether”. According to IARC, MTBE
is not classified as to its carcinogenicity in humans
(Group 3). *
* IARC 1999, Methyl tert-butyl ether, p 339-382
IARC Monograph, International Agency for
Research on Cancer.
Lyondell Chemical Company
Page 17 of 59
Draft
2.2 Occupational Exposure Limits
In the USA, the American Conference of
Governmental Industrial Hygienists have
established a Threshold Limit Value (TLV) of 40
PPM over 8 hours.
In the Netherlands, the 8 hour Occupational
Exposure Limit is 50 ppm as it is in Sweden also.
In the UK, the Occupational Exposure Standard is
25 ppm over 8 hours.
2.2.1 Warning Properties
MTBE is a clear, colourless liquid with a strong,
terpene odour. Its odour threshold is very low,
average detection threshold 0.051 ppm, which
provides sufficient warning to prevent exposure to
the Occupational Exposure Limits above.
2.3 First Aid
When an emergency arises, employees should
approach the accident site with caution. Do not
become a casualty. Employees should understand
emergency procedures and know where rescue
equipment and emergency contact numbers are
located before the need arises.
Personnel providing assistance to a victim should
be cautious not to contaminate themselves by
touching the victim's clothing unless wearing
appropriate protective apparel. The removal of
clothing from the victim is important to minimise
continued skin contact, and to prevent continued
volatilization of MTBE during transport to an
emergency care facility. Emergency transport
services should be equipped to provide flushing of
the skin and eyes, especially when the victim is
complaining of burning or irritation.
2.3.1 Eye Contact
Anyone whose eyes are splashed with liquid MTBE
should flush them immediately with large amounts
of cool water for at least 20-30 minutes, periodically
lifting the lower and upper lids to enhance flushing.
Following irrigation, evaluation by a health
professional is advised.
Product Safety Bulletin
2.3.2 Skin Contact
Anyone splashed by liquid MTBE should flush
affected areas thoroughly with water from a safety
shower or other running stream of water. While
under the shower, the exposed person should
remove all contaminated clothing, rings, watches,
shoes, or anything else that would prevent complete
flushing. All skin areas exposed to liquid MTBE
should then be washed with soap and water.
If skin reddening is noted, the exposed person
should seek medical attention.
Clothing should not be reused before laundering.
Leather articles should not be reused unless
completely dry and essentially free of MTBE odour.
2.3.3 Inhalation
If overcome from inhalation of MTBE, victim should
be moved from contaminated atmosphere into fresh
air at once by persons properly equipped with
appropriate personal protective equipment (PPE).
Treat for shock if necessary. If victim has stopped
breathing, administer cardiopulmonary resuscitation
(CPR) immediately. Appropriately trained first aid
individuals, or medically qualified personnel, should
administer CPR. Caution should be used to prevent
responder exposure to MTBE from the victim. Once
revived, keep the victim warm and calm. Seek
prompt medical attention.
2.3.4 Ingestion
Anyone who has swallowed MT8E should be given
a pint or more of lukewarm water, but only if the
exposed person is completely conscious and alert.
Vomiting should not be induced; the risk of lung
damage exceeds other hazards. If vomiting occurs,
have the person position their head below waist
level to minimise the risk of aspiration into the
lungs. Otherwise, chemical pneumonitis or
bronchitis can result. Seek prompt medical
attention.
Lyondell Chemical Company
Page 18 of 59
Draft
2.4 Medical Management
Good practice, and legislation in some countries,
dictates that employers should provide for medical
personnel in cases of medical emergency and/or
employee illness. In the absence of a clinic or
hospital facility in close proximity, the employer may
have on site persons who are adequately trained in
appropriate first aid techniques to handle medical
emergencies.
If no medical personnel are located at the facility,
contact should be made with an occupational health
physician and hospital emergency room to plan for
medical emergencies. Hospital selection should be
based upon proximity and the hospital's ability to
handle chemical emergencies. Copies of the
Material Safety Data Sheets (MSDS) and the
Product Safety Bulletin for MTBE should be
provided to, and reviewed with, medical personnel.
2.4.1 Initial Medical Screening
Prospective employees who will work with or
around MTBE should be medically evaluated to
determine pre-existing conditions that may be
aggravated by exposure to MTBE.
Individuals could be stressed by wearing personal
protective equipment, which may include respiratory
protection and chemical protective clothing (see
Sections 3.3 and 3.4). Some employees are
claustrophobic when placed in full facemask
respiratory protection, full containment suits, or
when entering confined spaces. :
Wearing personal protective equipment, such as
respiratory protection and chemical protective
clothing, can potentially cause a significant increase
in the work of the cardio-respiratory systems.
Employees required to wear respiratory protection
should be evaluated and approved for work by a
medical professional. The medical decision is based
upon the practitioner's judgement, but commonly
involves a targeted medical history and physical
with particular reference to the cardio-respiratory
system, pulmonary function studies, and an
assessment of cardio-respiratory fitness.
While MTBE is not known as a liver toxin in
humans, the importance of this organ in the
biotransformation and detoxification of foreign
substances should be considered before exposing
persons with impaired liver function. Similarly,
Product Safety Bulletin
MTBE is not known as a kidney toxin. However, due
to the importance of this organ in the elimination of
toxic substances, special consideration should be
given to those with impaired renal function.
A specific protocol for initial medical examination
should be developed by an occupational health
physician before employing individuals who may be
exposed to MTBE.
2.4.2 Periodic Screening
Persons who work regularly with MTBE should
receive routine medical evaluations. Periodic
medical screening is an effective tool for the
identification and prevention of occupational
disease. Employers should consult their
occupational health physician to determine the
specific protocol to be followed.
2.4.3 Medical Management of Over-
exposure Cases
In general, persons over-exposed to MTBE should
be provided supportive treatment with maintenance
of respiration until the anaesthetic effect of MTBE
has subsided.
In case of ingestion of MTBE, the patient should be
monitored-carefully for respiratory depression and
apnoea. Respiratory support should be available at
all times. If the patient is already coughing upon
arrival at the medical facility, aspiration may have
already occurred. Arterial blood gases should be
monitored in cases of severe aspiration pneumonitis
to assure adequate ventilation.
A patient over-exposed to MTBE by inhalation who
develops a cough or has difficulty in breathing
should be evaluated for respiratory tract irritation,
bronchitis or pneumonitis. Humidified, supplemental
oxygen with assisted ventilation should be
administered as required. Additionally, the patient
should be treated as recommended.
No specific medical monitoring or treatment is
indicated for eye or skin exposure to MTBE once
first-aid measures have been taken.
Lyondell Chemical Company
Page 19 of 59
Draft
3. PERSONAL SAFETY AND
HEALTH
3.1 Site Facilities
MTBE is a highly volatile liquid and should be
handled in systems that safely contain or capture its
vapours. Where MTBE vapours can be released,
local ventilation should be used to limit MTBE
vapour concentrations in workplace air.
In storage, transfer, and processing areas where
workers might come in contact with MTBE liquid,
quick-drenching facilities and equipment, including
emergency showers and eyewash stations, should
be provided. These units should be installed, tested,
and maintained according to appropriate
local/national standards and best industry practice.
Workers should be provided with washing facilities
for cleaning before consuming food or beverages
and before using tobacco or cosmetics. Properly
ventilated areas should be provided where workers
can take breaks and eat meals. Such areas should
be separate from those in which MTBE or other
chemicals are handled.
While showering is not required for persons working
with MTBE, a shower facility may be useful in first-
aid procedures for dermal exposure.
Contaminated work clothing should be stored and
laundered separately from every-day street clothing.
Laundry facilities for contaminated work clothing
may be provided on site, or other arrangements can
be made off site for laundering.
3.2 Hygiene Practices
Proper personal hygiene practices such as the
following should be used by those working with or
around MTBE:
• Do not consume/use or store food, tobacco, or
cosmetics where MTBE is used or stored.
• Wash hands with soap or detergent and water
after handling MTBE.
• Wash hands before eating, smoking, drinking,
applying cosmetics, or using toilet facilities.
Work clothing that has been contaminated by MTBE
liquid should be thoroughly air dried before it is
placed in a laundry hamper. Elastomeric protective
Product Safety Bulletin
clothing (gloves, hoods, boots, and aprons) should
be washed with detergent and water after each use,
then water-rinsed and hung up to dry in a well-
ventilated area. Respirators should be
decontaminated and stored according to the
manufacturer's instructions and the site's written
respiratory-protection procedures.
Leather goods, such as belts, wallets, and shoes,
contaminated with MTBE should be air-dried until
free of MTBE odour before reuse or should be
disposed of properly as contaminated waste (see
Section 7.3).
3.3 Respiratory Protection
Engineering controls should be used where feasible
to prevent workers from overexposure to airborne
MTBE vapour. However, if engineering controls are
not technically feasible, are being installed, or fail to
control exposure and need to be supplemented,
respiratory protection may be provided for
employee protection. Respirators may also be
needed for non-routine operations such as confined
space entry into tanks and in emergency situations
arising from spills/leaks and fire/explosions
involving MTBE. Table 3-1 provides guidance for
respirator selection.
Workers who could be affected by exposure to
higher MTBE vapour concentrations (say above the
WEEL guide of 100 ppm as a TWA8) should wear
respirators. If respirators are necessary, a complete
respiratory protection program that includes
training, maintenance, inspection, fit testing,
medical surveillance, cleaning, and evaluation
should be implemented. The respiratory protection
program should meet any local/national
requirements and best industry practice standards.
The use of contact lenses should not be permitted
during respirator use in an Immediately Dangerous
to Life and Health (IDLH) atmosphere, confined
space entry, emergency operations or other similar
activities. If eyeglasses are necessary, eyeglass
inserts (spectacle attachments) designed for the
specific respirator can be obtained.
Lyondell Chemical Company
Page 20 of 59
 Draft Product Safety Bulletin

Table 3-1

METHYL TERTIARY BUTYL ETHER

RESPIRATORY PROTECTION SELECTION GUIDE
Condition Minimum Respiratory Protection* Required above 100 ppm

A chemical cartridge respirator with a full face piece and organic

Vapour Concentration vapour cartridge(s).

1000 PPM OR Any supplied-air respirator with a full face piece, helmet or hood.
LESS
Any self-contained breathing apparatus with a full face piece.

A gas mask with a chin-style or a front- or back-mounted organic

5000 PPM OR LESS vapour canister.

A powered air-purifying respirator with organic vapour cartridges.

Any supplied-air respirator with a full face piece, helmet, or hood.

Any self-contained breathing apparatus with a full face piece.

A supplied-air respirator operated in pressure-demand or other

positive pressure mode with a full face piece, helmet, or hood.

Self-contained breathing apparatus with a full face piece operated in

GREATER THAN pressure-demand or other positive pressure mode.
5000 PPM
A combination respirator which includes a supplied-air respirator with a
OR full face piece operated in pressure-demand or other positive pressure
or continuous-flow mode and an auxiliary self-contained breathing
ENTRY INTO apparatus operated in pressure-demand or other positive pressure
UNKNOWN mode.
CONCENTRATIONS
Self-contained breathing apparatus with a full face piece operated in
FIRE FIGHTING pressure-demand or other positive pressure mode.

Any gas mask providing protection against organic vapours.

ESCAPE
Any escape self-contained breathing apparatus.

* Only approved equipment should be used.

Lyondell Chemical Company

Page 21 of 59
Draft
3.4 Chemical Protective Clothing
Personal protective equipment (PPE) should be
provided to prevent overexposure of personnel
who might come in contact with MTBE during
handling, spill management, or firefighting.
Chemical protective clothing (CPC) should be
selected according to expected working conditions
and the potential for contact with liquid or vapour.
Chemical protective ensembles range from long-
sleeved, washable clothing and safety glasses,
safety helmets, and safety shoes to chemical
protective suits, gloves and boots, and respiratory
protection. Material selection should take into
account the chemical properties of MTBE. Factors
to consider include permeability, chemical
resistance, strength, flexibility, thermal limits,
cleanability, and durability. After the conditions of
potential exposure are determined, the guidelines
in this section can be used.
3.4.1 Eye Protection
Eye-protective equipment should meet
appropriate national/industry specifications.
Laboratory workers handling only small quantities
of MTBE should wear, at a minimum, either safety
glasses or chemical goggles. A face shield
provides additional protection if worn together with
glasses or goggles. Chemical goggles should be
worn by anyone who might be exposed to liquid
MTBE in storage, transfer, maintenance, and
processing operations.
Individuals wearing contact lenses while working
with or around MTBE should wear chemical
goggles at all times. The potential increase in risk
of eye injury to contact lens wearers exposed to
chemicals has not been determined. Therefore, a
conservative approach in selecting eye protection
is recommended.
3.4.2 Head Protection
Safety helmets should be worn where there is
danger from falling objects or overhead leaks and
spills. Helmets should meet the appropriate
national/industry specifications for protection.
Manufacturers have adapted helmets so that ear
protection and face shields may be easily
attached. If, due to the specific circumstances, a
helmet is not required, a hood made of chemically
impervious material may be worn.
Product Safety Bulletin
3.4.3 Foot Protection
Heavy overboots should be provided and worn
over leather shoes or boots to protect the leather
from contamination. Leather items may absorb
MTBE, thereby increasing the risk of dermal (skin)
exposure. Rubber boots should be worn under
trouser legs to prevent MTBE from entering the
boot.
Where the potential for falling objects exists, steel-
toed rubber boots or safety shoes with overboots
should be worn. The steel-toed shoes/boots
should meet the appropriate national/industry
specifications. Boots that become tom during use
should be replaced.
3.4.4 Skin Protection
Impervious protective clothing suitable for a
particular work activity should be worn. Clothing
can range from gloves and an apron to a full-
containment suit.
MTBE was tested against a variety of chemical
protective clothing (CPC) materials. Protective
clothing and gloves made of nitrile, butyl rubber or
polyvinyl alcohol should provide protection from
contact with liquid for at least 6 hours (see Table
3-2). However, the quality and thickness of the
CPC may vary between manufacturers.
Therefore, manufacturer specific MTBE
permeation data should be obtained and
evaluated before selection.
Where the potential for exposure to MTBE liquid
exists, workers should wear a liquid tight
containment suit or slicker suit. These suits are
designed to protect employees from skin contact
with MTBE. All suits should be routinely inspected
to identify any damage or wear. If damage is
observed, exit the contaminated area and replace
the clothing.
Protective clothing used in a contaminated
environment should be properly decontaminated
prior to handling by unprotected individuals and
reuse. To decontaminate the protective clothing
wash with a mild soap/detergent and water.
Lyondell Chemical Company
Page 22 of 59
Draft Product Safety Bulletin

Table 3-2

METHYL TERTIARY BUTYL ETHER

PERMEATION TEST DATA’
Concentration: Neat
Resistant Material Thickness (cm) Breakthrough Permeation Rate
Time (hours) (1lg/cm2 min)
NITRILE NBR 0.054 > 6.0 < 0.90
NEOPRENE (UNSUPPORTED) 0.038 ** > 9000
NEOPRENE (SUPPORTED) NA ** > 9000
POLYVINYL ALCOHOL NA > 6.0 *** < 90
(SUPPORTED)
POLYVINYL CHLORIDE NA ** > 9000
NATURAL RUBBER 0.048 ** > 9000

*1990 Ansell Edmont Chemical Resistance Guide. This information should be used as a guideline for material
selection. Contact manufacturer for specific product information.

**Breakthrough time not determined; material rapidly degraded.

***Polyvinyl Alcohol is soluble in water.

3.5 Direct Reading Instruments

MTBE is readily analysed by a variety of direct
reading instruments. The advantage of using
direct reading instruments is that real-time
analysis and instantaneous air concentrations can
be determined. The value of a real-time analysis,
in terms of prevention of injury and illness, is
considerable.
Direct reading instruments that have been
successfully used to measure MTBE are
combustible gas indicators, infrared
spectrophotometers, flame ionisation detectors
and photo-ionisation detectors. Appendix II
contains a partial list of product vendors. Limits of
detection vary between these instruments and
should be evaluated to ensure proper use. The
proper selection, calibration, use and
interpretation of direct reading instruments
requires the services of a professional industrial
hygienist or other knowledgeable person.
The National Institute for Occupational Safety and
Health (NIOSH) has developed Method Number
1615 for sampling and analysis of MTBE (see
Appendix III). The method recommends sampling
with standard sized coconut charcoal tubes and
analysis by gas chromatography.
These methods for air sampling and analysis are
the primary means to determine worker exposures
over extended periods. When considering the use
of these methods for determination of employee
exposure, it is important that a monitoring
program is developed by professional industrial
hygienists. This program should include the
sampling strategy, quality assurance and
statistical analysis of results.

3.6 Air Sampling and Analysis

When assessing worker exposure to MTBE, an
extended sampling period is desirable. The most
common method of air sampling is collection on a
sorbent media over an extended period of time.
Air is drawn at a predetermined rate by a
sampling pump into a charcoal tube.

Lyondell Chemical Company

Page 23 of 59
 Draft
4. ENGINEERING
This section should be considered as a guideline,
not a design handbook. The user should exercise
competent engineering judgement and use
qualified professions to meet specific
requirements.
This section applies only to the specific material
identified in Section 1.0 General Information.
Mixtures of MTBE with other materials may require
additional engineering studies to determine the
applicability of the information in this section.
4.1 Bulk Storage
Installations should conform to local operating
permit and national requirements. All equipment
should be designed, constructed and installed to
appropriate engineering codes of practice.
The construction of low pressure MTBE storage
tanks should be in accordance with American
Petroleum Institute (API) 620 and 650 (see
Appendix IV for references). Higher pressure
storage vessels should comply with American
Society of Mechanical Engineers (ASME) Code,
Section VIII, Division 1 or equivalent. Liquid MTBE
should enter through the bottom of the tank.
Incoming liquid should be prevented from free
falling through the tank vapour space (see Section
8). If fitted with a top entry filling pipe, then the
vertical pipe should extend to within 100 mm of the
tank or sump base and be fitted with a syphon
breaker.
4.2 Piping
Piping and piping components should comply with
the latest edition of American Society of
Mechanical Engineers/American National
Standards Institute (ASME/ANSI) B31.3 or
equivalent.
4.3 Electrical Area Classification
Electrical equipment and wiring installations used
where MTBE is stored or handled should conform
to the appropriate area electrical safety
classification.
4.4 Pump Specifications
Centrifugal : Any carbon steel API 610 type,
designed with mechanical seals and elastomeric
secondary seals compatible with MTBE.
Product Safety Bulletin
Rotary : Any type made for hydrocarbon service
with mechanical seals. This type of pump should
be checked regularly for gear wear.
4.5 Instrumentation
Independent high level alarms and/or shutdowns
should be provided to avoid overflow of MTBE
storage vessels. All instrumentation should
conform to the appropriate area classification.
4.6 Relief Requirements
The requirements of API PP-2000 should be
followed for low pressure vertical storage tanks.
Flame arresters, when required, should follow the
requirements of API RP2210. Pressure relieving
systems for pressure vessels are defined in API
520, parts 1 and 2.
4.7 Leak Detection Devices
Secondary containment areas in confined spaces
should be monitored with instrumentation able to
detect the lower flammability limit of MTBE in air.
Instruments that have been successfully used to
measure MTBE are combustible gas indicators,
infrared spectrophotometers, flame ionisation
detectors and photo-ionisation detectors (see
Section 3.5).
4.8 Material Requirements
Elastomeric polymers used for seals, gaskets,
wipers, O-rings, and packing should be selected
carefully. Polymers that are satisfactory for use
with gasoline may be unsatisfactory for MTBE
service. Polymers that are generically identical
sometimes perform differently in parts fabricated
by different manufacturers. Parts constructed of
® ®
Viton A, Viton GF, and Fluorel are generally not
recommended for MTBE service because they
frequently swell, soften, or otherwise deteriorate.
The choice of materials should be governed by
compatibility with MTBE. Listed below are
materials commonly used in MTBE service. Other
materials may be suitable. We recommend that
elastomer vendors are consulted for
recommendations.
Lyondell Chemical Company
Page 24 of 59
Draft Product Safety Bulletin

4.8.1 Gaskets
® ®
Flat Ring (sheet) : Durabla Nitrile , or Grafoil
GHE.

Spiral Wound : Flexitallic CG, 100% graphite filled.

4.8.2 Pipe-Thread
®
Teflon tape.

4.8.3 Pump Seals

Component materials for mechanical seals should
include :

Stationary Faces : tungsten carbide

Rotating Faces : carbon

® ®
Elastomers : Kalrez 1050, Chem-raz , nitrile or
Teflon.

4.8.4 Valve Packing

Die-formed Rinqs : 100% graphite, top and
bottom. Ring to be braided carbon yarn.

Bonnet Gasket: metal reinforced flexible graphite.

4.8.5 Hoses
Flexible : Stainless steel, spirally wound Teflon
filled, hoses or braided hoses lined with cross-
linked polyethylene.

4.8.6 Floating-Roof Tank Seal System

Primary vapour seals : Urethane foam log with
Buna-N/vinyl nylon envelope.
®
Secondary wiper seals : Conservatek surlyn,
ionomer resin.

4.9 Vapour Containment System

The requirements of API RP-2000 should be
followed for low pressure vertical storage tanks.
Flame arresters, when required, should follow the
requirements of API RP2210.

Lyondell Chemical Company

Page 25 of 59
Draft
5.FIRE SAFETY
5.1 Fire and Explosion Hazard
MTBE is classified by the UN Committee of
Experts and other regulatory bodies as a highly
flammable liquid (see Appendix IV for references).
The flash point of MTBE is -20°F (-28.9°C). If an
ignition source is present at any temperature
above -20°F (-28.9°C), airborne vapours of MTBE
between 1.5 percent and 8.5 percent by volume
can bum or explode. MTBE can auto-ignite if its
temperature reaches 815°F (435°C). MTBE
vapour density is three times greater than that of
air; vapour may travel a considerable distance to a
source of ignition and then flash back.
The incomplete combustion of MTBE, as in an
oxygen-deficient atmosphere, can generate
carbon monoxide, a lethal gas with poor warning
properties. The products of complete combustion
are carbon dioxide and water.
Transferring or processing MTBE can cause static
electricity charges. Electrostatic potentials can
accumulate if liquid MTBE flows through unbonded
piping or filter media, or if it falls freely through the
air. When accumulated static electricity is
discharged, it can ignite flammable vapours.
5.2 Fire Prevention
MTBE storage and handling areas should be kept
free of ignition sources, including heat, sparks,
flames, and static electricity. Such areas should be
designed to prevent ignition or exposure to fire
(see Section 8.2).
Each facility handling MTBE should adopt a
comprehensive program for fire prevention. The
following management systems contribute to an
effective fire prevention program:
• instrumentation and electrical equipment and
wiring installations used where MTBE is
stored or handled should conform to the
appropriate area electrical safety classification
and appropriate standards of design,
construction and installation.
• maintenance of effective bonding and
grounding of metallic storage or receiving
containers and pipework.
Product Safety Bulletin
• design of vessels, transfer and process
systems to prevent spills, leaks, or vapour
releases.
• periodic scheduled inspection, testing, and
maintenance, including relevant record
keeping, of all safety-critical items; e.g.,
sensors, alarms, controls and flame arresters.
• inspection and maintenance of elastomeric
parts.
• use of trained and qualified operating and
engineering personnel to work with MTBE and
equipment.
• enforcement of a strict ''No Smoking'' policy in
MTBE storage or handling areas.
• use of stringent welding, cutting and burning
(hot work) permit systems.
5.3 Fire Suppression
An alcohol-resistant, low-expansion, aqueous film-
forming foam (AFFF-AR) can be used to fight fires
and to blanket unignited spillage. Foams suitable
for this application are manufactured by a number
of companies (see Appendix II). MTBE may be
more difficult to blanket than other solvents. Foam
manufacturers' specific recommendations for use
should be followed.
Water may be ineffective in fighting MTBE fires.
Water can sometimes be used to extinguish MTBE
fires when several co-ordinated hose streams are
used to sweep the flames from the surface of the
burning liquid. This approach should be used only
by experienced firefighters working under
favourable conditions. Water spray can also be
used to disperse vapours, protect firefighters,
absorb heat, and protect exposed structures and
adjacent storage areas.
Lyondell Chemical Company
Page 26 of 59
Draft Product Safety Bulletin

Portable fire extinguishers should be placed near

MTBE storage and handling areas. Workers
should be trained in the use of portable fire
extinguishers. Dry chemical or foam extinguishers
should be used to fight MTBE fires. Information on
how to select, use, distribute, inspect, maintain,
and recharge portable fire extinguishers should be
obtained from expert technical sources; e.g., fire
engineers, local fire authorities and fire protection
companies.

5.4 Fire Fighting

Facilities that rely on local authority fire brigades
should provide them with information on MTBE
operations and storage, including details of
storage locations and quantities of MTBE present.
Drills should be conducted periodically with the fire
brigade, and facility information should be updated
regularly.

Facilities using internal fire brigades should ensure

that their organisation, personnel qualifications,
firefighting equipment, and training requirements
should meet appropriate local/national
requirements.

Firefighters should use full protective clothing and

equipment, including a self-contained breathing
apparatus (see Section 3).
Detailed advice on attacking and fighting
petroleum-type fires can be found in API
Publication 2021.

If MTBE is involved in a fire, unauthorised

personnel should not enter the fire area and
should be evacuated from the area downwind of
the fire. MTBE fires should be fought from a safe
distance, preferably upwind.

When closed containers of MTBE are exposed to

heat or flames, firefighters should apply water. If
exposed surfaces cannot be wetted within the first
several minutes of exposure, it may be prudent to
set up water monitors and evacuate workers.
Evacuation should also be considered if cooling
efforts are hampered by inadequate water
supplies.

After a fire has been extinguished, any residual

MTBE should be cleaned up to prevent another
fire or environmental contamination. Individuals
involved in this work should be thoroughly trained
in proper techniques, be correctly protected and
use the appropriate equipment.

Water runoff from MTBE fires may be subject to

operating permit and local/national regulations
covering environmental releases and ignitable
hazardous waste (see Section7).

Lyondell Chemical Company

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6. HAZARD COMMUNICATION
Employees should be informed of the potential
hazards of chemicals in the workplace. Employers
who use hazardous chemicals, including MTBE, in
their workplace should develop written programs
and train employees on the potential hazards and
protective measures.
Local communities should also be informed of the
hazards and emergency response plans.
6.1 Worker Training
As a user of MTBE, an employer should provide
information and training to employees on its
hazards, the methods for detecting releases and
methods of protection from exposure. This
information should be included in your Hazard
Communication Training Program. To assist you in
this effort, the following summary information is
provided.
6.2 Hazards
MTBE is a liquid with a relatively low boiling point
and moderate vapour pressure. Its liquid and
vapours are flammable and will burn or explode.
MTBE vapours, which are heavier than air, can
travel long distances along the ground and remain
in unventilated, low areas.
Workers can be exposed to MTBE through
inhalation, skin or eye contact. If inhaled in high
concentrations, MTBE may cause anaesthetic
effects. Skin and eye contact with MTBE can cause
slight irritation, depending on the duration of
contact. For a complete discussion of the health
effects of MTBE, see Section 2.
6.3 Methods of Detection
MTBE is a clear, colourless liquid with a strong,
terpene odour. It has a very low odour threshold,
average detection threshold 0.051 PPM, which is
sufficient to warn of possible exposure.
To determine MTBE concentrations in air,
measurements can be made using air sampling
equipment. A variety of instruments are available to
provide instantaneous or continuous monitoring of
MTBE concentrations in air.
Product Safety Bulletin
Direct reading instruments including combustible
gas indicators, infrared spectrophotometer, and
flame and photo-ionisation detectors (see Section
3.5) can be used to monitor for MTBE. When
assessing worker exposure to MTBE, personal
breathing zone samples should be collected (see
Section 3.6) for comparison with desired levels.
6.4 Methods of Protection
Hazard Communication Training should include
information on methods of protection that can be
used by employees handling MTBE. This should
include the engineering and administrative controls
employed, as well as the personal protective
clothing and equipment (PPE) to be worn (see
Sections 3.3 and 3.4).
6.5 Labelling
Lyondell Chemical provide health and safety
information on their MSDS. Basic information is also
provided on the Tremcard which accompanies each
road delivery (see Figure 6-1).
Containers of MTBE or mixtures containing MTBE
in concentrations greater than or equal to 1%
should be labelled in accordance with the
requirements of any national regulations and
relevant transportation codes. Transport labelling
requirements for MTBE are presented in Section
11.2.
Each vessel into which MTBE is transferred should
be clearly identified with its contents and the
hazards of the materials it contains. Many firms
elect to employ the National Fire Protection
Association (NFPA) 704, Standard System for the
Identification of the Fire Hazards of Materials
(Hazard Diamond) as a means of in-plant
communication to workers, contractors and
firefighters. The appropriate numerical hazard
classifications for MTBE are as follows:
Lyondell Chemical Company
Page 28 of 59
Draft Product Safety Bulletin

Figure 6-1
TRANSPORT EMERGENCY CARD (Road) CEFIC TEC (R) 30G30
09/1985 Rev:1

Class 3 ADR
Item 3b
CARGO
FLAMMABLE LlQUIDS HAVING A FLASH-POINT BELOW 21°C NOT TOXIC AND NOT CORROSIVE

Name of substance(s): MTBE

• Usually colourless liquid with perceptible odour
• Completely miscible with water

NATURE OF HAZARD
• Highly flammable (flash-point below 21°C)
• Highly volatile (boiling point below 65°C)
• The vapour is invisible heavier than air and spreads along ground
• May form explosive mixture with air particularly in empty uncleaned
receptacles
• Heating will cause pressure rise severe risk of bursting and explosion
• The vapour may have narcotic effect
• The liquid or vapour may cause irritation to eyes skin and air passages

BASIC PERSONAL PROTECTION

• Goggles giving complete protection to eyes
• Plastic or synthe0c rubber gloves and boots
• Eyewash bottle with clean water
======================================================================================
IMMEDIATE ACTION BY DRIVER - Notify police and lire brigade
• Stop the engine
• No naked lights. No smoking
• Mark roads and wam other road users
• Keep public away from danger area
• Keep upwind
======================================================================================
SPILLAGE
• Shut off leaks if without risk
• Use low-sparking handtools and explosion-proof electrical equipment
• Prevent liquid entering sewers, basements and workpits. Vapour may create explosive atmosphere
• Contain or absorb leaking liquid with sand or earth or other suitable material. Consult an expert
• Wam everybody – explosion hazard. Evacuate if necessary
• If substance has entered a water course or sewer or contaminated soil or vegetation advise police
FIRE
• Keep container(s) cool by spraying with water it exposed to fire
• Extinguish preferably with dry chemical foam or waterspray
• Do not use water jet
FIRST AID
• If substance has got into the eyes, immediately wash out with plenty of water for several minutes
• Remove soaked clothing immediately and wash affected skin with soap and water
• Seek medical treatment when anyone has symptoms apparently due to inhalation or contact with skin
or eyes
• In case of bums immediately cool affected skin as long as possible with cold water
__________________________________________________________________________________________
Additional information

Lyondell Chemie Nederland, B.V. OTHER ITEMS: TELEX:29618 ARCO NL Hl No.:33

THEEMSWEG 14 ROTTERDAMIBOTLEK TELEX:29744 ACNE NL UN No.2398
P.O. BOX 7195, 3000 HD ROTTERDAM TELEFAX:(0)1819 17658
THE NETHERLANDS PHONE NUMBER: (0235)834800 for UK only*

**IN CASE OF EMERGENCY CONTACT IMMEDIATELY**

********** Lyondell Chemie Nederland, B.V.**********

COPYRIGHT Prepared by CEFIC, (CONSEIL EUROPEEN DEL L’INDUSTRIE CHIMIQUE, EUROPEAN

BY CEFIC CHEMICAL INDUSTRY COUNCIL) from the best knowledge available, no responsibility is accepte
that the information is sufficient or correct in all cases
30G30 APPLIES ONLY DURING ROAD TRANSPORT ENGLISH

Lyondell Chemie Nederland, B.V. Theemsweg 14 – 3197 KM Rotterdam/Botlek – Netherlands

Lyondell Chemical Company

Page 29 of 59
Draft Product Safety Bulletin

• Health (Blue): 1 be reviewed in order to assess the applicability of

• Fire (Red): 3 these regulations to the use of MTBE.
• Reactivity (Yellow): 0
• Other (White): None

6.6 Material Safety Data Sheets (MSDS)

To comply with the requirements of EEC Directive
91/155/EEC, a Lyondell Chemical MSDS is
provided to customers with the first order and after
any change or revision to the MSDS. The MSDS is
the primary means for providing information about
the safe storage, handling, use, and ultimate
disposal of LYONDELL Chemical products. The
MSDS for MTBE is a valuable source of health and
safety information, but it may not supply the specific
information needed for some uses of MTBE. If the
MSDS does not completely meet your needs,
contact Lyondell Chemical through customer
service at Maidenhead, U.K. (Country Code 44)
(0)628-77-5000 or your regional sales office for
further information.

Lyondell Chemical MSDSs are available in several

languages and formats. Downstream sales of
MTBE or materials containing MTBE are the
distributor's responsibility, but Lyondell Chemical
will support hazard communication efforts involving
MTBE.

6.7 Local Emergency Planning

Facilities which use or store MTBE should notify
their local emergency response authorities and
work with them to develop emergency response
plans. Companies within the EEC should comply
with the requirements of Directive 96/82/EC relating
to major accident hazards of certain industrial
activities including production and storage sites
covering emergency planning and information
communication to the public. Countries outside the
EEC may have equivalent legislation.

Companies should check their local and national

regulations and ensure that they comply with the
requirements.

Because MTBE is classified as a hazardous

chemical due to its flammability, facilities using or
storing it should submit a copy of the MSDS and
other relevant details to the relevant authority.

MTBE may also be subject to reporting of releases

to the air, water, soil, or disposal sites.

6.8 National Regulations

National regulations may have different or more
stringent requirements regarding Hazard
Communication. Countries within the EEC will have
legislation, whilst others will have equivalent
legislation, protecting workers from the hazards of
exposure to chemicals. National regulations should

Lyondell Chemical Company

Page 30 of 59
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7. ENVIRONMENTAL
MTBE is a flammable and volatile liquid at ambient
temperatures (vapour pressure = 204 mm Hg at
20°C). Spills and leaks require prompt response to
minimise the risk of fire and/or explosion, as well as
fugitive air emissions. Operating permit and
local/national requirements should be reviewed to
ensure that reporting requirements for spills of
MTBE are complied with.
MTBE is soluble in water (4.3 wt. percent) and is
miscible with most organic solvents. It is
biodegradable by acclimatised bacterial
populations, but surface waters and wastewater
treatment plants should be protected from spills. A
laboratory study indicated that anaerobic
degradation of MTBE in soils occurred only in soils
containing low organic matter under mildly acidic
conditions. The primary pathways for MTBE
removal from soils are probably through
volatilisation from shallow soils and solubilisation by
infiltrating water.
Limited bio-concentration experiments indicate that
MTBE is largely excreted from mammals through
exhalation within two days as unchanged MTBE.
Toxicological testing indicates that MTBE is of low
toxicity and is not a carcinogen or teratogen. Based
on its water solubility and rapid excretion rate,
MTBE probably does not accumulate in plants and
animals.
7.1 Air Quality Considerations
MTBE is classified as a Volatile Organic Compound
(VOC) and national pollution control authorities
should be consulted to identify particular
requirements including any related to ozone
depletion targets and/or minimisation of fugitive
emissions. Such requirements may also form part of
operating permit conditions and/or local regulations
and cover recording and specific work practices.
7.2 Water Quality
MTBE should not be discharged to sewers, surface
water systems or the ground (where it may
eventually find its way into water systems).
Operating permit and local/national regulations
usually prohibit such discharges (see also Section
7.3.1) and facilities should ensure that such
requirements are met. Discharges into sewers may
create a fire or explosion hazard in sewers or at the
treatment works, or may pass through the treatment
works or interfere with its normal operation.
Product Safety Bulletin
As with other regulatory areas, relevant regulations
and operating permit requirements should be
checked.
7.3 Waste Management
7.3.1 Spills and Leaks
Facilities using MTBE should implement a sound
spill-prevention and emergency response plan. This
plan should address issues such as the following:
• spill-detection methods emergency-notification
procedures
• community contacts for notification and advice on
evacuation needs
• fire prevention and protection provisions for spill
containment and cleanup
• environmental protection
• compliance with applicable national and local
regulations or laws.
Facilities that store or handle MTBE should be
designed to contain and/or control spills from
process areas and loading and unloading
operations. Soil, surface water, and groundwater
contamination from an accidental spill of MTBE can
be minimised by the installation of curbs, sumps,
and impervious containment areas. Containment
areas should be designed and constructed of
impermeable materials such as concrete, synthetic
liners, or compacted clay. Concrete should be
underlaid with an impermeable liner, and only
compatible epoxy sealants should be used on
cracks and concrete joints.
Concrete curbing with a minimum one percent slope
or earth diking with a minimum two percent slope
from the point of the potential spill to a collection
basin or sump should be used to retain MTBE
within the containment area, minimising worker
exposure and overall environmental impact. The
total volume of the containment area should be
adequate to handle a worst-case release of MTBE.
For storage tanks, the capacity of the containment
area is generally the volume of the largest storage
tank in the diked area but local regulatory
authorities may have different requirements. Design
of the diking or curbing should also provide an
allowance for accumulated rainfall or water used to
control fires.
Lyondell Chemical Company
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Pumps, piping, and equipment designed to operate
within potential spill areas should be compatible
with MTBE (see Section 4) and free of potential
ignition sources.
If possible, all pumps and ancillary equipment
should be located outside the primary containment
area and should be provided with curbing to collect
drips, leaks, and minor spills. Drain valves can be
included in the design, however, during normal
operations, all drain valves should be closed.
MTBE is considered a "hazardous substance" arid
in the event of an MTBE release any reporting
requirements should be complied with.
Any accidental discharge of MTBE or process
waste containing MTBE into the public sewer or
water system should be reported immediately to
relevant local authorities. The discharge should be
diluted with copious quantities of water to reduce
the fire and explosion hazard. In the event of an
MTBE spill, all non-essential personnel should be
evacuated and all ignition sources extinguished
immediately. After donning the appropriate personal
protective equipment (see Section 3), the spill
should be covered with firefighting foam (see
Section 5.3) to minimise potential fire hazard from
vaporisation of the MTBE. Depending on the
volume and location of the spill, it can be recovered
by vacuum truck or absorbed with solid sorbent and
placed in drums for disposal. All power equipment
used in cleanup must meet appropriate electrical
safety codes for areas where flammable liquids and
vapours are present. The use of water for cleanup
should be minimised, but residual MTBE should be
flushed with water into a sump or collection area for
subsequent treatment or disposal.
Soil contaminated with MTBE should be excavated
and transported to a permitted hazardous-waste
treatment or disposal facility. Contaminated water
may have a low flash point depending on the
concentration of MTBE and therefore be considered
ignitable hazardous waste and disposal or
treatment is subject to specific regulatory
requirements. Other materials contaminated with
MTBE may be ignitable and should be treated as
hazardous until proven otherwise.
Because of its solubility in water and relatively low
organic carbon partitioning coefficient (Koc = 11),
MTBE is fairly mobile in soil and should be
prevented from migrating to groundwater when
feasible. Once in the groundwater, MTBE tends to
migrate faster than most other volatile hydrocarbons
and is typically present at the leading edge of a
groundwater contaminant plume.
7.3.2 Waste Classification
Solids and liquids, containing MTBE, should be
treated as hazardous waste because of the
characteristic of ignitability.
Product Safety Bulletin
7.3.3 Waste Handling and Storage
National regulations which apply to the handling,
storage and disposal of hazardous waste must be
complied with. In the EEC these will meet the
requirements of Directives 91/156/EEC and
91/689/EEC covering waste management, waste
disposal and environmental protection. Countries
outside the EEC may have similar legislation which
should be reviewed.
Transportation of hazardous wastes for disposal at
authorised, registered sites, must comply with
national legislation and the relevant transportation
Code (see Section 11).
Workers involved in the handling, storage,
transportation and disposal of hazardous waste
must be thoroughly trained, suitably protected (see
Section 3) and familiar with all relevant information
and legislative requirements.
MTBE users who generate, store, reclaim or tender
for transportation or disposal of any hazardous
waste should review all applicable regulations.
Operating permits and national/local regulations
may contain specific requirements regarding the
storage of hazardous waste. In particular these may
specify the storage in approved containers which
should then be kept in clearly identified, separate
areas designed so that any spillage of waste is
collected. Containers stored in such facilities should
be clearly labelled, dated and periodically
inspected. Detailed records should be kept.
MTBE is an extremely flammable liquid and is
therefore hazardous when discharged to the
environment. In areas where MTBE may be
released or handled, access should be limited to
authorised personnel only.
7.3.4 Waste Treatment and Disposal
MTBE, or hydrocarbon liquids containing MTBE,
may be burned on-site as fuel for energy recovery.
There may be specific national regulatory
requirements for boilers and furnaces that burn low
flash point waste fuels for energy recovery; these
regulations should be consulted for specific
requirements. Permitted hazardous waste
incinerators can also be used for disposal of MTBE
or hydrocarbon liquids containing MTBE.
Aqueous wastes, containing low concentrations of
MTBE, may be treated in a well-operated and
acclimatised biological wastewater treatment plant.
Sufficient equalisation capacity should be provided
to minimise shock loads to the treatment plant.
Aqueous wastewaters may also be discharged to a
municipal treatment system with local authority
approval. As with other highly volatile materials,
extreme care should be taken to ensure that no
separable hydrocarbons are discharged into the
sewer system.
Lyondell Chemical Company
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Laboratory studies have demonstrated that MTBE is

biodegradable by well-acclimatised aerobic micro-
organisms. Process wastewater streams, containing
MTBE and other constituents, should be evaluated
for biodegradability in laboratory tests prior to
introduction into a wastewater treatment plant to
ensure that permit effluent limitations can be
achieved.

As with other highly volatile hydrocarbons, MTBE is

easily volatilised in aerobic wastewater treatment
plants. Some regulatory bodies may regulate
fugitive emissions from industrial wastewater
treatment plants and pre-treatment may be required
to remove the more volatile constituents in the
wastewater. MTBE can be readily removed from
wastewater by steam or air stripping should pre-
treatment be required to reduce the MTBE
concentration in wastewater prior to biological
treatment.

Drums and other containers used for MTBE should

be drained and thoroughly rinsed to be considered
non-hazardous. Rinse water generated by this
washing should be collected and disposed of
properly. It may be advisable to complete a
certificate of cleaning that documents that the
containers have been appropriately cleaned and
can be reused. Any container that has not been
completely water-washed should be considered a
potential fire or explosion risk and should not be cut,
burned, soldered, or welded. Containers which have
been emptied and which are to be transported, are
considered as hazardous, and must comply with the
relevant transport regulations, unless they have
been thoroughly cleaned and certified clean by a
competent, authorised person.

Lyondell Chemical Company

Page 33 of 59
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8. PRODUCT STORAGE
The considerations for the design and construction
of storage facilities for MTBE include its
flammability, toxicity, potential effects to the
environment, and risks to worker health. The
specific design requirements for facilities receiving
and storing MTBE depends upon several factors,
including types of containers used, mode of delivery
to the facility, processing methods, amounts stored
and handled, quantities of other nearby flammable
or combustible materials handled, the character of
the adjacent community, and risks posed by
adjacent facilities. The proper design and
construction of storage and handling facilities
requires consultation with competent professional
engineers.
Users of MTBE should perform formal process
safety reviews to determine appropriate safeguards
to be incorporated into facility design.
8.1 Storage Tanks
Considerations on site selection and tank spacing
include proximity to other flammable material
storage facilities, nearby ignition sources,
firefighting accessibility, and the potential
consequences of a release beyond the plant
boundaries. Installations should comply with
operating permit requirements and relevant
local/national regulations.
Lyondell Chemical generally stores bulk quantities
of MTBE in fixed-head tanks equipped with internal
floating roofs operating at atmospheric pressure
(see Figure 8-1). Such tanks protect MTBE from
water contamination - a threat to quality better than
open-topped, floating-roof tanks. Fixed-head tanks
combined with vapour management systems may
also be used.
Outside storage tanks should be diked to contain
potential spills. A reliable water supply should be
available, in adequate pressure and volume, to
meet the fire demands of the particular situation.
The degree to which MTBE-containing equipment is
protected may be based on a number of criteria
which include: storage and usage volumes,
temperatures, pressures, material handling
procedures, proximity to vulnerable structures and
personnel, and the availability of outside support
(see Section 5.4).
Whenever flammable liquids are stored or
transferred, their containers and systems should be
effectively bonded and grounded to prevent static
electricity. Instrumentation and electrical equipment,
suitable for use with flammable liquids, must be
designed, installed and maintained to avoid
providing a source of ignition, and must conform to
the appropriate area classification.
Product Safety Bulletin
Tanks should be situated within containment
systems which are capable of both the detection
and control of releases. Consult API 2350 for proper
design considerations for overfill prevention.
8.1.1 Vapour Management System
Well maintained internal floating roof systems
minimise the VOC emissions from storage vessels
containing MTBE.
Any tank or vessel that receives, stores, or
processes MTBE and is not equipped with a floating
roof should be connected to a vapour-management
system unless it is designed to prevent release of
MTBE under all normal conditions. Vapour-
destruction systems, such as flares, and collection
systems, such as carbon adsorbers, are used for
vapour management. Design and management of
carbon adsorbers should be of a high standard,
particularly when manifolded vapour collection
systems are used, to avoid the creation of hot spots
which may result from oxidation of certain other
adsorbed chemicals, e.g. ketones. Flaring is the
most common method of disposing of vented MTBE
vapours (refer to or sump API RP-521 and API
Standard 2000).
Headers connecting tanks to common vapour-
management devices should be equipped with
appropriate flash-back prevention devices
8.2 Unloading Installations
Unloading areas should be designed, maintained
and operated with special consideration for fire
protection, worker safety and environmental
protection. Instrumentation should be considered for
off-loading stations to warn operators of the
potential for overfilling the storage tank and also
that a totally independent device shuts off flow
whenever overfill is imminent. Neither device is to
be used as a regular operating tool for tank level
determination. As part of the off-loading procedure,
the shutoff device should be regularly tested.
Loading points should be located away from all
equipment and tanks. Electrical wiring and devices
should comply with the requirements of the area
classification. Piping should comply with the latest
version of American Society of Mechanical
Engineers/American National Standards Institute
(ASME/ANSI) B31 ''Chemical Plant and Petroleum
Refinery Piping" or equivalent.
Adequate illumination (daylight/artificial lighting)
must be provided and no attempt should be made
to discharge containers, open or close attachments
or connect/disconnect the system if visibility is not
adequate.
Lyondell Chemical Company
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Figure 8-1

The unloading area should be curbed to divert

spillage into a controlled drainage system and
prevent run-off into surrounding areas. The surface
of the unloading areas under and around the bulk
transport vessel should be constructed with an
impermeable membrane or ballast installed over an
impermeable barrier suitable for the retention of
MTBE. The drainage surfaces should be Ditched
towards a collection basin sump.

Lyondell Chemical Company

Page 35 of 59
Draft
MTBE should be transferred and handled according
to written operating procedures developed for the
specific facility. This section includes guidelines
used by Lyondell Chemical in its handling of MTBE.
Operating procedures should address the hazards
associated with this material (see Section 6), the
selection of personal protective clothing and
equipment (see Section 3), and fire-prevention
methods (see Section 5). Only workers trained in
proper operating procedures should handle MTBE.
Unloading systems dedicated to MTBE service are
recommended. If multiple-use systems are used,
MTBE quality should be protected by ensuring that
lines and equipment are free of water, then cleared
with a compatible hydrocarbon, such as unleaded
gasoline. All systems must be bonded and
grounded.
Flexible unloading hoses (see Section 4) are
generally used to connect the unit's fixed piping to
the tank car or truck. Unloading hoses, fittings, and
gaskets or O-rings should be inspected before each
transfer. Hoses should be stored in a protected
location when not in use with their ends capped.
Although it is a common practice to open the
manway cover on a rail tank car/tank truck during
unloading of MTBE, Lyondell Chemical does not
recommend this. Not only are MTBE vapours
emitted to the atmosphere but replacing liquid,
pumped from the container, with air will, at some
stage during the unloading operation create a
flammable/explosive mixture in the container.
Lyondell Chemical suggests the use of a vapour
return line from the receiving tank or a pressure-
regulated nitrogen make-up supply as shown in
Figures 9.1 and 9.3. This will ensure the
replacement of displaced liquid with MTBE/nitrogen
mixture from the inerted storage tank (nitrogen if the
tank has an internal floating roof and fixed head) or
nitrogen. The suggested unloading procedures
reflect this preferred mode of operation.
9.1 Work Preparation
When unloading vessels or containers, workers
should have the following equipment and supplies
available:
• Functional local eyewash stations and safety
showers
• Non-sparking tools
• Unloading block valve
• Stainless steel double-braided accordian type
hose
• Grounding connectors
• Nitrogen supply with pressure regulator and check
valve.
9.2 Tank Cars
Lyondell Chemical MTBE tank cars (see Figure 9-1)
are normally bottom-unloaded by gravity or
pumping. The following procedures are comparable
Product Safety Bulletin
to those used by Lyondell Chemical for unloading
tank cars and can be used as a basis for site-
specific procedures. A suggested unloading
checklist is provided in Figure 9-2.
9.2.1 Unloading Procedures
The unloading procedures for tank cars are as
follows:
1. Gather all necessary equipment. For tank car
unloading, also include:
• wheel chocks
• safety barrier, flag and warning signs
• derailer
2. Position the tank car correctly with respect to
the unloading station, then set its brake and
chock one wheel on both sides.
3. Place warning signs at both ends of the car
between rails. Place an additional sign at the
rail-siding switch.
4. Place a derailer on the rail siding between the
car and the siding switch.
5. Be sure that the receiving tank's ullage
(available space) is sufficient to receive the full
load with room to spare after the transfer is
complete.
6. Unless the receiving tank is equipped with a
floating roof, be sure that the breathing vent is
connected to an effective means of vapour
collection, such as a flare, or vapour return to
unloading container.
7. Identify all pipelines so that proper valve
alignment can be made.
8. Connect ground cable to car and check for
continuity of connections.
9. Check bill of lading and tank car labels. Make
sure that they identify the car's contents as
MTBE.
10. Determine that the unloading station's spill
collection sump drain is closed, and that the
sump is substantially free of accumulated
liquid.
11. Connect vapour return line or nitrogen make-up
line to vapour/nitrogen valve.
12. Attach flexible unloading hose to the car's
bottom outlet valve after ensuring that all parts
including gaskets and rings are in good
condition.
13. Set valves in fixed piping to begin the transfer
and inform production supervisor transfer is
about to start.
Lyondell Chemical Company
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14. Open car's external (lower) bottom valve.
15. Open car's internal bottom valve. Check
carefully for leakage. If any is noted, take
remedial action.
16. Start transfer pump (if used).
17. Immediately make a visual check for leaks,
especially at places where seals and O-rings
are present; shut down immediately and take
remedial action if leaks are observed.
18. Check that receiving tank's level is rising at the
expected rate for the transfer system.
19. Monitor the transfer. When the tank car is
empty, close pump discharge valve and
immediately shut off pump. Blow lines empty
with nitrogen and inert empty tank car with
nitrogen for return journey.
20. Close valves connecting pump and transfer line
to receiving tank.
21. Close the carts internal and external bottom
outlet valves, and vapour return/nitrogen
valves.
22. Disconnect unloading hose, taking precautions
to catch residual MTBE for proper disposal.
Store clean, empty hoses in protected location
with ends capped/covered .
23. Check all valves/connections are
closed/blanked/sealed/not leaking.
9.2.2 Release of Empty Car
The following steps complete the process of
unloading tank cars:
1. Disconnect the ground cable.
2. Remove the wheel chocks, derailer, and
warning signs/barriers.
3. Check tank-car placards and labels comply
with RID requirements for return trip.
4. If there were any mechanical problems with the
tank car, or seals were broken or absent,
advise relevant Lyondell Chemical supplier
plant LCNL, Rotterdam, The Netherlands
(Country Code 31) (0) 18-1 94-72-O0 or
Lyondell Chimie, Fos sur Mer, France (Country
Code 33) (0) 42-47-5100.
9.3 Tank Trucks
Lyondell Chemical ships MTBE in ADR certified
stainless-steel tank trucks. They are normally
unloaded by pumping through a valve located at the
bottom of the truck (see Figure 9-3), although
gravity discharge is permissible.
Product Safety Bulletin
The following procedures are comparable to those
used by Lyondell Chemical for unloading tank
trucks and can be used as a basis for developing
site-specific procedures for unloading MTBE.
A suggested unloading checklist is provided in
Figure 9-4.
9.3.1 Unloading Procedures
The unloading procedures for tank trucks are as
follows:
1. Instruct driver to position tank truck for
unloading at designated station, then set
brakes, shut off engine, and leave cab. The
driver should put battery master switch to 'OFF'
and remain in attendance throughout
unloading.
2. Safeguard truck from nearby traffic by putting
up road barriers or warning lights signs.
3. Chock both sides of one tank truck wheel.
4. Connect ground cable and check for electrical
continuity.
5. Check delivery details, truck labels, etc. to
confirm contents are MTBE.
6. Inspect hoses, pump, and valves for
cleanliness and operability. Ensure that
gaskets and O-rings are in good condition.
Make sure all auxiliary equipment is operating
properly.
7. Determine that the receiving storage tank has
sufficient capacity to hold the entire contents of
the tank truck.
8. Identify all pipelines so that proper valve
alignment can be made.
9. Unless the receiving tank has a floating
roof, determine that the tank's breathing
vent is connected to an operating flare,
other vapour-collection device or vapour
return.
10. Determine that the unloading station's spill-
collection sump drain is closed and
substantially free of accumulated liquid.
11. Connect vapour return line or nitrogen make-up
line to vapour/nitrogen valve.
12. Connect a flexible unloading hose to bottom
discharge valve connector.
13. Set valves in fixed piping to begin the transfer
and inform production supervisor transfer is
about to start.
14. Open tank truck’s external (lower) bottom
valve.
Lyondell Chemical Company
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Figure 9-1

Lyondell Chemical Company

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Methyl tertiary Butyl Ether

Unloading Checklist

o Tank Car Number: Date:

o Operator: Time AM / PM

Prior to Unloading Tank Car Yes No

o Wheels Chocked and Hand Brakes Engaged ...................................................................

o All Fire Equipment in Place and Functional ......................................................................
o Derailer, Flag Signs, Safety Systems in Place ..................................................................
o Delivery Details, Material Verified......................................................................................
o Storage Tank Capacity and Tank Car Liquid Level Determined before Transfer .............
o Proper Piping Alignment Made and Checked ...................................................................
o Product Hose and Fittings Visually Inspected Prior to Use ...............................................
o Eyebath and Safety Shower Flushed and Ready..............................................................
o Ground Cable to Car Connected and Checked for Continuity ..........................................
o Vapour Return/Nitrogen Make-up Connected ..................................................................
o Transfer Started and System Visually Checked for Leaks ................................................
o Qualified Operators in Attendance during Transfer ..........................................................

After Unloading Tank Car ............................................................................................... Yes No

o When Tank Car is Empty, Shut Down the Pump ..............................................................

o Unioading Line Valve Closed to the Storage Tank............................................................
o Tank Car Liquid Unloading Valve Closed, Empty Car Inerted for Return .........................
o Transfer Line Disconnected and Residual Liquid Collected..............................................
o Valves Closed/Blanked, All Connections Checked for Leaks ...........................................
o Ground Cable Disconnected .............................................................................................
o Flag, Safety Systems and Derailer Device Removed .......................................................
o Wheel Chocks Removed ..................................................................................................
o Tank Car Placards, Labels Correct for RID Return Trip ...................................................

Advise ARCO Chemical Supplier Plant of Any Mechanical Problems ................................

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15. Open tank truck’s internal bottom valve. Check
carefully for leakage. If any is noted, take
remedial action.
16. Start transfer pump (if used).
17. Immediately make a visual check for leaks,
especially at places where seals and O-rings
are present. If leaks are observed, shut down
immediately and take remedial action.
18. Check that receiving tank's level is rising at the
expected rate for the transfer system.
19. Monitor the transfer. When the tank truck is
empty, close pump-discharge valve and
immediately shut off pump. Purge lines/hoses
through to tank to ensure they are empty.
20. Close valves connecting pump and transfer line
to receiving tank (and vapour return if
applicable). Inert empty tank truck with nitrogen
for return journey unless nitrogen makeup or
vapour return from inerted storage has been
used.
21. Close the trailer's internal and external bottom
outlet valves.
22. Disconnect unloading hose, taking precautions
to catch residual MTBE for proper disposal.
Store clean, empty hose in a protected location
with ends capped/covered.
23. Close and secure the manway cover (if
applicable). Check for leaks and take any
necessary remedial action.
9.3.2 Release of Empty Truck
The following steps complete the process of
unloading tank trucks:
1. Disconnect the ground cable. Remove the
wheel chocks and traffic-control devices.
2. Ensure that tank truck placards for the return
trip meet ADR requirements.
3. Release the vehicle to the driver, who should
return battery master switch to normal position.
4. If there were any mechanical problems with the
tank truck, advise Lyondell Chemical relevant
supply plant, LCNL, Rotterdam, The
Netherlands (Country Code 31) (O) 18-194-72-
00, or Lyondell Chimie, Fos sur Mer, France,
(Country Code 33) (O) 42-47-5100.
9.4 Marine Transport
A customer considering receipt of MTBE by water
for the first time should contact Lyondell Chemical
Europe Inc., Maidenhead, UK (Country Code 44)
(1) 628-77-5000 or the regional sales office for
specific requirements.
Product Safety Bulletin
MTBE handling in marine transport is similar to that
required for other flammable liquid hydrocarbons
such as gasoline.
However, a number of areas may be different and
should be evaluated before handling MTBE. These
areas are:
1. Materials Compatibility - As discussed in
Section 4, materials requirements for neat
MTBE should be reviewed.
Specifically, check compatibility of loading
hoses and tank and compartment liners or
coatings.
2. Water Solubility - MTBE and water are
somewhat miscible in each other. Contact with
water should be avoided to maintain product
quality. Also, any water contaminated with
MTBE should be evaluated for waste
classification (Section 7) and proper disposal.
3. Fire Foams - As discussed in Section 5, fire
foams should be evaluated to determine if
alcohol resistant foams are required.
4. Exposure - Any vented marine transfer
operations should be monitored to insure that
vapour exposure is below the limits discussed
in Section 3. Exposure to high levels of MTBE
can result in anaesthetic-like effects (see
Section 2).
Although MTBE has low atmospheric reactivity,
vapour recovery during marine loading/unloading
operations may be utilised, particularly in areas
where regulations governing emissions or ozone
depletion may require such measures. Such
equipment must be designed, installed and
maintained to the standards of appropriate
engineering codes and regulations. Flame arresters
designed to prevent the passage of flames should
be maintained to ensure they remain clear and their
effectiveness continues.
If inerting is considered necessary, MTBE can be
blanketed in tanker transport. Nitrogen is an
acceptable blanketing material. Combustion product
gas blanketing should be done with care; soluble
combustion product gas components can possibly
cause increases in MTBE colour or sulphur.
In the case of a marine spill, MTBE's volatility
makes it very similar to gasoline. However, because
of MTBE's partial water solubility, some of the
spilled MTBE will dissolve into the water. The
amount that dissolves will depend on a number of
factors including air and water temperatures and
turbulence. General spill handling guidelines are
given in Section 7.
Independent inspectors or surveyors take quality
and quantity measurements to ensure that MTBE is
loaded only into uncontaminated tanks. Tanks or
compartments are generally acceptable if their
Lyondell Chemical Company
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Figure 9-3

Lyondell Chemical Company

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Methyl tertiary Butyl Ether

Unloading Checklist

o Tank Truck Number: Date:

o Operator: Time AM / PM

Prior to Unloading Tank Truck Yes No

o Truck Safeguarded with Road Barriers/Warning Lights ....................................................

o Wheels Chocked and Parking Brakes Engaged, Engine/Battery switched OFF .............
o Ground Cable to Truck Connected and Checked for Continuity .......................................
o Storage Tank Capacity Checked, Delivery Details Checked to Confirm Contents ...........
o Proper Piping Alignment Made and Checked ...................................................................
o Product Hose and Fittings Visually Inspected Prior to Use ...............................................
o Eyebath and Safety Shower Flushed and Ready, Fire Equipment in Place .....................
o Vapour Return/Nitrogen Make-up Connected ..................................................................
o Transfer Started and System Visually Checked for Leaks ................................................
o Qualified Operators in Attendance during Transfer ..........................................................

After Unloading Tank Truck ............................................................................................ Yes No

o When Tank Truck is Empty, Shut Down the Pump ...........................................................

o Unloading Line Valve Closed to the Storage Tank............................................................
o Tank Truck’s Internal and External Bottom Outlet Valves Closed.....................................
o Transfer Line Disconnected and Residual Liquid Collected..............................................
o Truck Inerted, Valves/Fittings Checked for Leakage.........................................................
o Ground Cable Disconnected .............................................................................................
o Placards Proper for Shipment as ADR ..............................................................................
o Wheel Chocks Removed ..................................................................................................

Advise ARCO Chemical Supplier Plant of Any Mechanical Problems

Lyondell Chemical Company

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previous cargoes were materials that are suitable

for blending in gasoline (excluding benzene).
Lyondell Chemical has detailed guidelines available
for inspectors.

Because of the solubility of water in MTBE,

marine/shore transfer systems should be checked
to insure dryness before MTBE transfer begins. Low
spots in lines may hold water. In addition, water
should not be used to clear lines or displace MTBE.

As with other hazardous materials, only trained,

authorised personnel should undertake the
unloading of barges or ships that contain hazardous
material such as MTBE.

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10. TANK CLEANING AND
EQUIPMENT REPAIR
10.1 Work Preparation
Proper preparation for cleaning or maintaining
MTBE storage vessels and equipment is necessary
to prevent fire or harm to workers or the
environment. Only fully trained workers should
clean or repair MTBE tanks and equipment.
A hazardous-work permit system should be
established before any maintenance or inspection
activities involving hot work, line breaking, or
confined-space entry are performed. A permit
should identify all job related hazards and include a
work plan to address them. Facilities should use
engineering controls and appropriate personal
protective equipment (see Section 3).
Before opening, tanks and equipment that
contained MTBE should be emptied of all liquid by
draining at low points. Tanks and equipment should
then be purged with an inert gas, then air, to a
vapour management system, or they should be
flushed with water.
Eyewash and safety showers should be located
near the work area. Appropriate fire extinguishing
equipment should be present (see Section 5.3).
10.2 Control of Hazardous Energy
A facility's procedures for controlling hazardous
energy sources should comply with the
requirements of operating permit and national
regulations. These procedures should be used to
protect workers in areas where MTBE vessels or
equipment are cleaned, maintained, or entered.
After MTBE has been purged, positive measures
should be taken to ensure that all potential sources
of MTBE or hazardous energy are physically locked
out and affected persons notified. Personal
protective equipment should be worn by workers
who might be exposed to MTBE residue.
10.3 Confined Space Entry
A confined space can be defined as "a space which
by design has limited openings for entry and exit
and unfavourable natural ventilation, and which is
not intended for continuous employee occupancy."
Tanks and other process vessels are confined
spaces. Before workers enter a confined space,
they should obtain a hazardous-work permit. The
permit should include provisions for controlling
hazardous energy. The confined space atmosphere
should be tested before entry and continuously
monitored during work.
Workers should not enter confined spaces where
the MTBE vapour concentrations exceed 25 percent
of its lower flammable limit of 1.5 percent by volume
(4000 ppm). Respiratory protection should be worn
whenever the MTBE concentration exceeds the
Product Safety Bulletin
exposure limits listed in section 2.2 or the oxygen
concentration is less than 19.5 percent (see Section
3).
An employee entering a confined space should be
in continuous communication with a standby person
equipped and trained for emergency rescue.
10.4 Equipment Cleanout
To protect product quality, Lyondell Chemical
recommends that MTBE storage tanks be clean and
dry before being placed in service initially or after
repair. The following procedure is commonly used
to clean out a storage tank:
• Remove all grease and oils using soap or
detergent and water, then rinse to a neutral pH
with clean water.
• Remove all loose rust and scale.
• Dry tank walls and clean the bottom of all solids
and water.
The tank should then be purged with nitrogen equal
to at least three times the tank's volume to prevent
an explosive mixture during filling of the tank with
MTBE. After out of service equipment has been
padded with nitrogen gas, the manways should be
marked as follows: ‘’DANGER DO NOT ENTER -
INERTED WITH N2."
10.5 Maintenance and inspection
Regular inspection, testing, and preventive
maintenance schedules should be followed for
equipment critical to fire safety, environmental
protection, worker safety, and community well-
being. This equipment includes fire-protection and
firefighting equipment, flame arresters, overflow
prevention or detection systems, ventilation
systems, emergency-relief systems, emission-
control equipment, vapour detection systems, and
alarms.
The inspection program should include periodic
visual inspection of equipment and storage areas
for signs of deterioration, leaks, or malfunctions.
Elastomeric parts, such as wiper seals on tanks'
floating roofs, pump packing, O-rings, and flexible
hoses, that contact MTBE should also be inspected
regularly. The frequency of inspection should be
based upon experience. Visible parts in transfer
systems should be inspected each time they are
used. Visual inspection can be augmented by the
use of instruments that detect MTBE vapours (see
Section 3.5).
Lyondell Chemical Company
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11. TRANSPORTATION
REGULATORY REQUIREMENTS
The Distribution Safety Program of Lyondell
Chemical has been implemented in accordance
with our commitment to Responsible Care. This
programme covers storage, handling and
distribution of chemicals and includes the selection,
and auditing, of high quality contractors, as well as
ensuring that containers used comply with the
appropriate regulatory transport codes.
The carriage of MTBE is regulated by the following
codes covering the mode shown:
Air- Dangerous Goods Regulations of the
International Air Transport Association (IATA) and
the Technical Instructions of the International Civil
Aviation Organisation (ICAO).
Sea - IMDG Code of the International Maritime
Organisation (IMO).
Inland Waterways - ADN Regulations of the United
Nations Economic Commission for Europe (ECE)
and the ADNR, covering the Rhine.
Road - ADR Regulations of the United Nations
Economic Commission for Europe.
Rail - RID Regulations of the Central Office for
International Rail Transport (OCTI).
Not every authorised packaging is addressed in this
chapter. Lyondell Chemical has selected transport
routes and modes in concert with packaging
configurations to develop and implement risk
reduction alternatives.
The above codes describe authorised procedures to
properly package, mark, label, placard and
document shipments. These procedures depend
upon the quantity and type of hazardous material
and the method of transport of the substance.
Container filling levels must conform to Code
requirements and also to the transportation laws of
the countries involved in a journey; e.g., maximum
gross weight/axle loading restrictions of transit
countries for a road delivery.
Lyondell Chemical recommends that those offering
hazardous materials for transport be trained in the
proper application of these regulations.
11.1 Classification
MTBE is listed by the UN Recommendations on the
Transport of Dangerous Goods; therefore, it is
designated as a hazardous material for
transportation purposes.
MTBE is assigned a hazard classification of 3 with a
packaging group (PG) designation of 11. The
designation PG II implies that the degree of danger
present is relatively high. The substance
identification number is UN 2398.
Product Safety Bulletin
The substance identification or UN number is the
same for all modes. Other classifications are as
follows:
The hazard identification number (HIN), situated in
the upper part of the identification label on
containers, where required, with the substance or
UN number undemeath, is sometimes known as the
Kemler number.
It is made up of a sequence of class numbers and
gives a warning of the dangers to expect if the
substance is released. Doubling of a number
indicates an intensification of that particular hazard.
Numbers can also be added to show secondary
risks.
For MTBE, the HIN is 33 showing it is a highly
flammable liquid.
Ship IMDG - HIN 33 - Hazard class: 3.1 Barge
ADNR - Hazard class IIIa, (3), 1a, K1n Road ADR -
HIN 33 - Class 3 - item number 3(b) Rail RID - HIN
33 - Class 3 - item number 3(b)
11.2 Marking, Labelling and Placarding
General and specific requirements concerning
marking, labelling, placarding and the preparation of
shipping papers are found in the relevant Code.
A flammable liquid label and hazard identification
placard are required (see Figures 11-1 and 11-2).
Each bulk packaging, that is
required to be placarded when it contains a
hazardous material must remain placarded when it
is emptied, until it has been emptied and cleaned
and certified free of MTBE by an authorised,
competent person.
11.3 Packaging
11.3.1 Tank Trucks
Lyondell Chemical transports MTBE in ADR-
certified stainless steel tank trucks. Bottom outlets
of the cargo tank are equipped with internal self-
closing stop-valves meeting ADR requirements.
Requirements for the design, construction, test and
inspection of cargo tanks, test and inspection
markings, and reporting and record retention
requirements, can be found in ADR Appendix B1a,
Class 3. These regulations should be reviewed in
detail to establish inspection protocols for tank
trucks used in the transport of MTBE. Details of
capacity, pressures, etc. are held by the Logistics
department of the supplier plant.
For your convenience suggested tank truck
unloading procedures can be found in Section 9.2.
Lyondell Chemical Company
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11.3.2 Tank Cars
Tank cars used to transport MTBE are designed,
constructed and operated to RID requirements and
marked in accordance with Appendix VIII of RID.
Details of capacity, pressure, etc. are held by the
Logistics department of the supplier plant.
11.3.3 Marine Transportation
Sea transport must comply with the requirements of
the IMO regulations given in IMDG Code and
Marpol 73/78 (Regulations for the Control of
Pollution by Noxious Liquid Substances in Bulk or
Annex III relating to packaged forms, portable
tanks, road or rail tankers).
Vessel owners must also comply with IMO Code for
the Construction and Equipment of Ships Carrying
Dangerous Chemicals in Bulk (the BCH Code). An
independent surveyor is employed for quality and
quantity measurements to ensure that the MTBE is
loaded in uncontaminated tanks.
Product Safety Bulletin
11.3.4 Air Transportation
MTBE may be transported domestically and
internationally by air in specific packaging and
quantities. These specific requirements should be
reviewed thoroughly prior to offering MTBE for
intentional air transport as the IATA Code is issued
annually and is only valid for that year of issue.
The IATA and ICAO requirements must be met for
intentional shipment.
11.4 Transportation Emergencies
Lyondell Chemical markets its products in a manner
which is considerate of the health and safety of
customers, transporters, the general public, and the
environment. However, even with the best of
preparations, emergencies can occur.
All Lyondell Chemical Material Safety Data Sheets
(MSDS) contain 24 hour telephone numbers:
- supplier plant LCNL, Rotterdam, The Netherlands
(Country Code 31) (0) 18-1 94-72-00
- supplier plant Lyondell Chimie, Fos Sur Mer,
France (Country Code 33) (4) 4247-51 00.
The Emergency Response System was established
to provide an efficient and responsible means of
minimising effects of an incident by providing
emergency assistance. The locations/situations
covered include in-transit accidents (vehicle
rollovers, road accidents, tank car derailments),
transport container damage and/or leaks, difficulties
at customers' facilities, leaks or spills in distribution
terminals or tollers' facilities, and exposure under
any and all circumstances.
Notification is received at the plant and directed to
one of a group of trained co-ordinators. The
emergency number is staffed 24 hours a day, every
day of the year. After receiving the emergency
information, the co-ordinator will immediately call
back the person originally requesting assistance.
If the situation is serious enough to warrant it, the
co-ordinator will inform Lyondell’s Maidenhead
Crisis Management Centre, and the Lyondell Crisis
Management Plan, with all its resources, will be
implemented immediately.
11.4.1 Reporting Requirements
Lyondell Chemical require all their contractors
(transporters, distributors, tollers) to report all
incidents involving Lyondell products, whether
damage/harm is caused or not. Each incident is
investigated and action decided upon to try and
prevent a reoccurrence. The procedure also
includes follow-up and monitoring phases. This is in
addition to, and does not replace, any statutory
reporting requirements.
Lyondell Chemical Company
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Lyondell Chemical Company

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Lyondell Chemical Company

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APPENDIX II

NAMES OF MANUFACTURERS

Manufacturer's Name
Fire Fightinq Foam
AFFF-AR Angus Fire Armour
Eau et Feu (Reims, France)
3M Industrial Chemical Products

Combustible Gas Detectors

TLV Sniffer Bacharach

Explosimeter MSA

Infrared Spectrophotometers
MIRAN 1B2 The Foxboro Company
MIRAN 1BX
MIRAN 101
MIRAN 103
MIRAN 1B
MIRAN 1A

Flame lonisation Detectors

Century OVA 128 The Foxboro Company
Century OVA 108

Photoionisation Detectors
Photovac's TIP Photovac International Corp.

HNU Model Pl01 HNU Systems Inc.

Lyondell Chemical Company

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APPENDIX III
NIOSH METHOD 1615

ISSUED: 8/15/90
FORMULA: CH30C(CH3)3
M.W.: 88.15
OSHA: No permissible exposure limit
NIOSH: No recommended exposure limil
3
ACGIH: No threshold limit value (1 ppm = 3.6 mg/m 0 NTP)
PROPERTIES*: liquid; d 0.74 g/mL @ 20°C
BP 55.2°C
VP 32.6 kPa (245 mm Hg) @ 25°C
SYNONYMS: MTBE; CAS #163-04-4

SAMPLING MEASUREMENT
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID
(two charcoal tubes in series; front
400 mg; back 200 mg) ANALYTE: methyl tert-butyl ether (MTBE)

DESORPTION: 2 mL CS2, 30 min

FLOW RATE: 0.1 to 0.2 L/min

VOL -MIN: 2 L @ 10 ppm INJECTION VOLUME: 1µ, split ratio 60:1

-MAX: 96 L
SHIPMENT: routine
SAMPLE STABILITY: at least 5 days @ 25°C,
3 weeks @ -7°C (92% recovery) [1]
TEMPERATURE -INJECTION: 200°C
-DETECTOR: 250°C
-COLUMN: 0°C for 7 min; 5°C/min
to 25°C, and then 25°C/min to
250°C (hold S min)

FIELD BLANKS: 10% of samples CARRIER GAS: He, 1 to 2 mL/min

ACCURACY COLUMN: fused silica capillary, 50-m x 0.3-mm ID,

0.5-µm film of bonded dimethytsilicone gum
RANGE STUDIED: not studied (polydimethylsiloxane)

BIAS: not significant [I] CALIBRATION: standard solutions of MTBE in CS2

OVERALL PRECISION (S,): not determined RANGE: 0.06 to >10 mg per sample [1]

ESTIMATED LOD: 0.02 mg per sample [1]

PRECISION (Sp): 0.033 @ 9 µg9 to ≅ 10 mg per sample

[1]

3
APPLICABILITY: The working range is 0.2 to ,35 ppm (0.75 to 125 mg/m ) for an 80-L air sample. This
method is designed for the determination of MTBE in gasoline and may be used for the determination of other
components of gasoline.

INTERFERENCES: 2,3-Dimethylbutane may interfere if initial chromatographic temperatures are higher than
0°C

OTHER METHODS: This is a new method [1].

•Physical properties for Lyondell Chemical Company product are listed in Table 1-1.

Lyondell Chemical Company

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REAGENTS: EQUIPMENT:
1. Sampler: Two glass tubes in tandem, each 8
1. Methyl tert-butyl ether, reagent grade. cm long, 8-mm OD, 6-mm ID, flame sealed
2. Carbon disulfide*, reagent grade. ends with plastic caps, containing activated
3. Calibration stock solution, 7.41 mg/mL. coconut shell charcoal held by plugs of silated
Dilute 40 µL methyl tert-butyl ether to glass wool (front tube = 400 mg, back tube =
4.00 mL with carbon disulfide. 200 mg).
4. Helium, prepurified. 2. Personal sampling pump, 0.1 to 0.2 L/min with
5. Hydrogen, prepurified. flexible connecting tubing.
6. Air, compressed, filtered. 3. Gas chromatograph with sub-ambient cooling,
7. Liquid nitrogen or carbon dioxide for flame ionization detector.
sub-ambient cooling of GC oven. 4. Vials, 5-mL, 2-mL with PTFE-lined crimp caps.
5. Pipettes, TD, 4-, 2- and 1-mL.
6. Syringes, 1 -mL, 250-, 100-, 25- and 1 0-µL.

•see SPECIAL PRECAUTIONS

SPECIAL PRECAUTIONS: Methyl tert-butyl ether and carbon disulfide are extremely
flammable (flash points -28.9°C and -30°C respectively. Carbon disulfide is also toxic.
Work with these compounds in a hood.
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler in line.
2. Immediately before sampling, break the ends of the sampler tubes. Connect smaller tube to
personal sampling pump with flexible tubing and to larger tube with a short piece of plastic tubing.
3. Sample at an accurately known flow rate between 0.1 and 0.2 L/min for a sample size of 2 to 96 L.
4. Separate the tubes, cap, and pack securely for shipment. Chilling of the samples is necessary if
they are not expected to be analysed within five days.

SAMPLE PREPARATION:
5. Add 2.0 mL carbon disulfide to 5-mL vials. Loosely cap vials.
6. Place front and back sorbent sections in separate vials. Discard glass wool and foam plugs.
Immediately cap each vial.
7. Allow to stand 30 min with occasional agitation.

CALIBRATION AND QUALITY CONTROL:

8. Calibrate daily with at least seven working standards.
a. Prepare standards in capped vials by mixing various volumes (i.e., S to 230 µL) of calibration
stock solution with carbon disulfide to a total volume of 4.00 mL to obtain concentrations in the
range of 0.010 to 5 mg/mL.
b. Analyse together with samples and blanks (steps 11 and 12).
9. Determine the desorption efficiency (DE) at least once for each lot of charcoal used for sampling
in the calibration range (step 8). Prepare three tubes at each level plus three media blanks.
a. Use the 400-mg charcoal tube for DE determination. Hold charcoal in the tube by silanized glass
wool.
b. Prepare three DE stock solutions by mixing 4, 40, and 160 µL of methyl tert-butyl ether and
making up a total volume to 4.00 mL with carbon disulfide to produce corresponding
concentrations of 0.741, 7.41 and 29.62 µg/µL.
c. Inject 24 µL of the 0.741 µ/µL stock solution, 7 and 19 µL of the 7.4t µg/µL solution, 7, 11, and 14
µL of the 29.62 µg/µL stock solution onto the tubes near the glass wool plug and draw clean air
through the tubes at 0.1 L/min for 1 to 2 minutes.
d. Seal tube with plastic caps. Allow to stand overnight.
e. Desorb (steps 5 through 7) and analyse together with working standards (steps 11 and 12).
f. Prepare a graph of DE vs. mg of MTBE recovered.
10. Analyze three quality control blind spikes and three analyst spikes to insure that the calibration
curve and DE are in control.

MEASUREMENT:
11. Set gas chromatograph according to manufacturer's recommendations and to conditions given on page
1615-1. Inject sample aliquot manually using solvent flush technique or with an auto sampler.
NOTE: 1. If the sample peak area is above the linear range of the working standards, dilute an aliquot of the
described liquid with CS2, reanalyse, and apply the appropriate dilution factor in calculations.
2. These conditions are recommended for the determination of MTBE in gasoline. An initial
temperature lower than 0°C will produce better peak resolution but longer analysis time.
12. Measure peak area.

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CALCULATIONS:
13. Detemnine the mass, mg (corrected for DE) of MTBE found in the sample front (W f) and back (W b) sorbent
sections, and in the average media blank front (Bf) and back (Bb) sorbent sections.
NOTE: If W b > W f /1 0, report breakthrough and possible sample loss.
14. Calculate concentration, C, of MTBE in the air volume sampled, V (L):
3
(W f + W b – Bf - Bb) x 10
3
C= --------------------------- mg/m
V

EVALUATION OF METHOD:

A calibration curve in the concentration range 0.74 to 111 mg/mL MTBE in carbon disulfide indicated a linear
correlation with a coefficient of 0.9998 and Sp of 3.3% [1]. Other calibration curves at lower concentrations,
covering the recovery/stability range, i.e. 9.3 to 426 µg/mL MTBE in CS2, indicated linear correlation coefficients
>0.998. The LOD and LOO values varied between 18 to 22 µg/mL and 36 to 73 µg/mL respectively.

A six-level, 31-day storage stability study, conducted at -7°C, in the range 17.8 to 415 µg MTBE in gasoline
spiked on 400 mg charcoal tubes, indicated recoveries of 99.0 ± 4.3% for the first day, 93.2 ± 2.0% for the 17th
day, 91.9 ± 7.1% after 23-day storage and 89.0 ± 5.2% after 31-day storage. A five-day room temperature
stability study at 415 ~9 MTBE in gasoline spiked in 400 mg charcoaMubes indicated a 100.0 ± 4.6% recovery.

Four charcoal tubes spiked with 415 µg MTBE in gasoline had air drawn for six hours at 100 mL/min and then
were stored at -7°C for five days indicating 103.6 ± 9.0% recovery. No sample loss occurred due to breakthrough
at the 415-µg per sample MTBE level.

Charcoal tubes which were spiked with 10 mg MTBE in gasoline and which had 6 to 78L of air drawn through
them did not indicate any breakthrough of MTBE. Light hydrocarbons i.e. n-butane and isopentane, which are not
retained by the charcoal, did break Ihrou9h.

REFERENCES:

[1] Palassis, J. Method Development Efforts for MTBE, NIOSHJDPSE, Measurement Research Support Branch,
Cincinnati, Ohio, 1989 paper presented at the Annual Meeting of Federation of Analytical Chemistry and
Spectroscopic Societies (FACSS), Chicago, IL (October 4, 1989).

METHOD REVISED BY: John Palassis, NIOSH/DPSE

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APPENDIX IV

REFERENCES
ACGIH

American Conference of Governmental Industrial Hygienists 6500 Glenway Avenue, Bldg. D-7 Cincinnati, OH
45211-4438

ACGIH; Threshold Limit Values and Biological Exposure Indices

AIHA

American Industrial Hygiene Association

2700 Prosperity Avenue, Suite 250
Fairfax, VA 22031

WEEL; Workplace Environmental Exposure Level Guide

ANSI

American National Standards Institute

11 West 42nd Street
New York, New York 10036

ANSI B16.21; Non-Metallic Flat Gasket for Pipe Flanges

ASME:/ANSI B31.3; Chemical Plant and Petroleum Refinery Piping

API

American Petroleum Institute

1220 L Street, N.W.
Washington, DC 20005

API RP-520; Recommended Practice for the Design and Installation of Pressure-
Relievinq System in Refineries - Part I - Design

API RP-520; Sizing, Selection and Installation of Pressure-Relievinq Devices in

Refineries - Part II - Installation

API RP-521; Guide for Pressure-Relievinq and Depressurinq Systems

API 610; Centrifuqal Pumps for General Refinery Service

API 620; Recommended Rules for the Desiqn and Construction of Larqe Welded, Low-
Pressure Storage Tanks

API 650; Welded Steel Tanks for Oil Storaqe

API RP-2000; Ventinq Atmospheric and Low-Pressure Storaqe Tanks

API RP-2021; Guide for Fiqhtinq Fires In and Around Petroleum Storaqe Tanks

API RP-2028; Flame Arresters in Pipinq System

API RP-2210; Flame Arresters for Vents of Tanks Storinq Petroleum Product

API 2350; Overfill Protection for Petroleum Storaqe Tanks

ASME

American Society of Mechanical Engineers United Engineering Center

345 East 47th Street
New York, New York 10017

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ASME Code, Section VIII, Division 1; Boiler and Pressure Vessel Code

ASME/ANSI B31.3; Chemical Plant and Petroleum Refinery Pipinq

ECE

United Nations Economic Commission for Europe

Palais des Nations
1211 Geneva 10
Switzerland

ADN; Requlations Governinq the Transport of Danqerous Goods by Inland Naviqation in Europe Except
on the Rhine

ADR; Requlations Concerninq the International Carriaqe of Dangerous Goods by Road (ADR)

EU (ex- EEC)
European Union (Formerly European Economic Community)
Office for Official Publications of the European Communities
2 rue Mercier
L-2985 Luxembourg

91/155/EEC; Provision of specific information to industrial recipients of dangerous substances or

preparations

91/156/EEC; Waste management including recovery, disposal and environmental protection

91/689/EEC; Hazardous waste management including transportation. disposal and public/environmental

protection.

IATA

International Air Transport Association

1155 Mansfield Street
Montreal 113, P.Q., Canada

IATA; Danqerous Goods Requlations

ICAO

International Civil Aviation Organisation

1000 Sherbrooke Street West
Suite 400
Montreal, Quebec, Canada H3A,2R2

ICAO; Technical Instructions for Safe Transport of Danqerous Goods, By Air

IMO

International Maritime Organisation

Albert Embankment
London SE,1
England

IMDG; International Maritime Danqerous Goods Codes, Volumes 1, 11, 111, IV, V

IMO; Intentional Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in
Bulk

Marpole 73/78:

Annex II: Requlations for the Control of Pollution by Noxious Liquid Substances in Bulk

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Annex III: Regulations for the Prevention of Pollution by Harmful Substances Carried by Sea in
Packaged Forms, or in Freight containers, Portable Tanks or Road and Rail Wagons

NFPA

National Fire Protection Association

8atterymarch Park
Quincy, Massachusetts 02269

NFPA 704; Standard System for the Identification of the Fire Hazards of Materials

NIOSH

National Institute for Occupational Safety and Health US Department of Health, Education and Welfare 4676
Columbia Parkway Cincinnati, Ohio 45226

Method 1615: Methyl tert-butyl ether

OCTI

Central Office for International Rail Transport

Thunplatz
3006 Bern
Switzerland

RID: Requlations Concerninq the International Carriage of Dangerous Goods by Rail (RID)

UN

United Nations
First Avenue and Forty-second Street
New York, NY 10017

Recommendations on the Transport of Dangerous Goods

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APPENDIX V

REGULATORY SUMMARY
METHYL TERTIARY BUTYL ETHER

The following summary presents some of the international laws and enabling
regulations that require review prior to handling, storage or distribution of methyl
tertiary butyl ether (MTBE). This overview of the regulations is not and should not be
construed as an all inclusive source of information. In addition, other international
laws and regulations may be applicable.
Australia

Listed on Australian Inventory of Chemical Substances

Canada

Canadian Workplace Hazardous Materials Information System (WHMIS)

WHMIS established requirements for classifying hazardous substances that will be used in the
workplace and for preparing MSDSs and container warning labels.

MTBE does not appear on the WHMIS ingredient disclosure list.

Canadian Domestic Substances List

MTBE is listed.

European Economic Community

European Inventory of Existing Commercial Chemical Substances (EINECS)

MTBE is listed on EINECS - number 216 653 1. Listing on EINECS is accepted by certain other
European countries which have adopted EINECS as their base inventory; i.e. Austria, Finland,
Switzerland.

Directive 96/82/EC. Major accident hazards of certain industrial activities, including production and
storage sites covering emergency planning and information communication to the public.

Directives: 89/391/EEC and 91/383/EEC. Provision of information to workers, training, medical

surveillance, protection and prevention services.

U.S.A.

Department of Transportation (DOT)

The Hazardous Materials Transportation Act of 1974 gave the Department of Transportation authority to regulate
the transportation of hazardous materials in interstate commerce. DOT regulates such matters as classification,
packaging and hazard communication (labelling). DOT also has established spill notification requirements.
Regulations governing the transport of hazardous materials can be found at 49 CFR 172 and 173.

MTBE is listed as a DOT hazardous material (49 CFR 172.102), identification #UN2398, Packing Group II

Occupational Safety and Health Administration (OSHA)

The following OSHA regulations apply to MTBE:

29 CFR 1910.106, Subpart H; Storage of flammable and combustible liquids

29 CFR 1910.155, Subpart l; Fire protection relative to flammable or combustible

29 CFR 1910.164; Fire detection systems required when MTBE is in use

29 CFR 1910.1000, Subpart Z; Permissible Exposure Limits No established standards.

29 CFR 1910.1200; Hazard Communication Standard

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Toxic Substances Control Act (TSCA)

The Toxic Substances Control Act gives EPA authority to regulate production, use, labelling, distribution, and/or
disposal of chemical substances and mixtures; to delay production; to ban or restrict manufacturing or marketing
of existing or new chemical substances which present an unreasonable risk of injury to health or the environment;
to require testing, record keeping, and reporting. All manufacturers. importers, processors, distributors, and
disposers of chemical substances subject to the law are affected by its provisions and implementing regulations.

Section 4 Test Rules (40 CFR 799.5000) - MTBE is the subject of a testing consent order for health effects
testing.

Section 8(b) Chemical Substances Inventory - MTBE is listed (Vol. l., page 103, 1985 Edition)

Section 8(d) Health & Safety Data Reporting (40 CFR 716) - MTBE was listed by
rule effective 12/15/86; reporting is required until 12/15/96.

Section 12(b) Export Notification (40 CFR 707, Subpart D) - MTBE is listed and export notice to the EPA is
required under the regulations.

Information on TSCA regulations can be obtained from the TSCA Assistance Office at EPA; 202/554-1404.

Miscellaneous

National Fire Protection Association (NFPA) Hazard Rating

The NFPA ratings assign a numeric value to specific aspects of each hazard. Ratings for MTBE are as follows:

Health: 1. Materials only slightly hazardous to health. It may be desirable to wear self-contained breathing
apparatus.

Flammability: 3. Materials which can be ignited under almost all normal temperature conditions. Water may be
ineffective because of the low flash point.

Reactivity: 0. Materials which (in themselves) are normally stable, even under fire exposure conditions, and which
are not reactive with water. Normal fire fighting procedures may be used.

Additional information on the NFPA hazard rating system can be obtained from the National Fire Protection
Association, Batterymarch Park, Quincy, MA 02269; phone 800/344-3555.

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APPENDIX VI

GLOSSARY
ADN/ADNR Regulations Governing the Intemational Carriage of Dangerous Goods on European
Inland Waterways/the Rhine

ADR European Agreement Conceming the International Carriage of Dangerous

Goods by Road

AFFF-AR aqueous film-forming foam, alcohol resistant

AIHA American Industrial Hygienists Association

ANSI American National Standards Institute

API American Petroleum Institute

Apnoea transient cessation of respiration

ASME American Society of Mechanical Engineers

ASTM American Society for Testing and Materials

BOD biochemical oxygen demand

Bonding the connection of two or more conductive objects by means of a conductor(most

commonly a wire or metal plate)

CFR Code of Federal Regulations

CGI combustible gas indicators

COD chemical oxygen demand

Confined Space an area that by design has limited openings for entry and exit. A confined space has
unfavourable natural ventilation and is not intended for continuous worker occupancy.

CPC chemical protective clothing

DOT U.S.A. Department of Transportation

ECE United Nations Economic Commission for Europe

EEC European Economic Community

EPA Environmental Protection Agency

Flash Point the minimum temperature at which a liquid gives off vapour in sufficient concentrations to
form an ignitable mixture with air near the surface of the liquid.

GAC granular activated carbon

Grounding the connection of one or more conductive objects to the ground; a specific form of
bonding. Grounding is also referred to as earthing.

HAP hazardous air pollutant

IATA International Air Transport Association

ICAO International Civil Aviation Organisation

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IDLH immediately dangerous to life and health; the airborne concentration of a toxic material
from which one could e5cape within 30 minutes without any escape-impairing symptoms
or any irreversible health effects.

IM intermodal

IMDG International Maritime Dangerous Goods

IMO International Maritime Organisation

LFL lower flammability limit

MSDS material safety data sheet

MTBE methyl tertiary butyl ether

NFPA National Fire Protection Association

NIOSH National Institute for Occupational Safety and Health

OSHA Occupational Safety and Health Administration

DVA organic vapour analyser

PPE personal protective equipment

Ppm parts per million

SCBA self-contained breathing apparatus

TOC total organic carbon

TWA time-weighted average

Ullage the available space in the tank of a tank car or truck

UN United Nations

Vapour Pressure the pressure exerted by a volatile liquid while under defined equilibrium conditions. Vapour
pressure is usually measured in millimeters of mercury (mm Hg).

VOC volatile organic compound

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