SAFE HANDLING OF LIQUID

CARBON DIOXIDE CONTAINERS

THAT HAVE LOST PRESSURE
Doc 164/20
Revision of Doc 164/10

EUROPEAN INDUSTRIAL GASES ASSOCIATION AISBL

AVENUE DE L’ASTRONOMIE 30 • B – 1210 BRUSSELS

Tel: +32 2 217 70 98
E-mail: [email protected] • Internet: www.eiga.eu
 Doc 164/20

SAFE HANDLING OF LIQUID CARBON

DIOXIDE CONTAINERS THAT HAVE
LOST PRESSURE

As part of a programme of harmonisation of industry standards, the European Industrial Gases Association
(EIGA) has issued EIGA Doc 164, Safe Handling of Liquid Carbon Dioxide Containers that have Lost
Pressure, jointly produced by members of the International Harmonisation Council and originally published
by the Compressed Gas Association (CGA) as CGA G-6.7, Safe Handling of Liquid Carbon Dioxide
Containers that have Lost Pressure.

This publication is intended as an international harmonised standard for the worldwide use and application
of all members of the Asia Industrial Gases Association (AIGA), Compressed Gas Association (CGA),
European Industrial Gases Association (EIGA), and Japan Industrial and Medical Gases Association
(JIMGA). Each Association’s technical content is identical, except for regional regulatory requirements and
minor changes in formatting and spelling.

Disclaimer
All technical publications of EIGA or under EIGA's name, including Codes of practice, Safety procedures and any other technical
information contained in such publications were obtained from sources believed to be reliable and are based on technical
information and experience currently available from members of EIGA and others at the date of their issuance.

While EIGA recommends reference to or use of its publications by its members, such reference to or use of EIGA's publications by
its members or third parties are purely voluntary and not binding.

Therefore, EIGA or its members make no guarantee of the results and assume no liability or responsibility in connection with the
reference to or use of information or suggestions contained in EIGA's publications.

EIGA has no control whatsoever as regards, performance or non performance, misinterpretation, proper or improper use of any
information or suggestions contained in EIGA's publications by any person or entity (including EIGA members) and EIGA expressly
disclaims any liability in connection thereto.

EIGA's publications are subject to periodic review and users are cautioned to obtain the latest edition.

 Reproduced with permission from the Compressed Gas Association. All rights reserved

EUROPEAN INDUSTRIAL GASES ASSOCIATION AISBL

Avenue de l’Astronomie 30 B 1210 Brussels Tel +32 2 217 70 98
E-mail: [email protected] Internet: www.eiga.eu
EIGA DOC 164/20

Table of Contents
1 Introduction ...................................................................................................................................... 1
2 Scope and purpose ......................................................................................................................... 1
2.1 Scope .................................................................................................................................... 1
2.2 Purpose ................................................................................................................................. 1
3 Definitions ........................................................................................................................................ 1
3.1 Publication terminology ......................................................................................................... 1
3.2 Technical definitions .............................................................................................................. 2
4 Basis ................................................................................................................................................ 4
5 Warning ........................................................................................................................................... 4
6 Properties of carbon dioxide............................................................................................................ 5
7 Temperature and pressure ............................................................................................................ 11
8 Physiological effects of carbon dioxide ......................................................................................... 11
8.1 General................................................................................................................................ 11
8.2 Effects of inhaled carbon dioxide ........................................................................................ 12
8.3 Physical effects of overexposure to carbon dioxide ............................................................ 12
8.4 Regulatory standard ............................................................................................................ 12
8.5 Safety precautions .............................................................................................................. 13
8.6 Rescue and first aid ............................................................................................................ 13
9 Specific hazards ............................................................................................................................ 14
9.1 General................................................................................................................................ 14
9.2 Dry ice blocking ................................................................................................................... 14
9.3 Low temperature effects on materials ................................................................................. 14
9.4 Trapped liquid ..................................................................................................................... 14
9.5 Overfilling containers ........................................................................................................... 15
9.6 Personnel overexposure ..................................................................................................... 15
9.7 Thermal expansion and contraction .................................................................................... 15
10 Hazards of carbon dioxide container re-pressurisation ................................................................. 15
10.1 Movement of transportable containers ................................................................................ 15
10.2 Hazards ............................................................................................................................... 16
10.3 Specific precautions ............................................................................................................ 17
11 Preliminary procedures for returning de-pressurised containers to service .................................. 18
11.1 Personnel requirements ...................................................................................................... 19
11.2 Provisions for alternate source ........................................................................................... 19
11.3 De-pressurised container evaluation .................................................................................. 19
11.4 Facts to consider in evaluating re-pressurisation methods ................................................. 19
12 Guidelines for evaluation of the condition of a de-pressurised container ..................................... 20
12.1 Container pressure greater than 1380 kPa (200 psi) .......................................................... 21
12.2 Container pressure less than 1380 kPa (200 psi) but greater than 416 kPa (60.4 psi) ...... 21
12.3 Container pressure less than 416 kPa (60.4 psi) ................................................................ 22
12.4 Special low-temperature containers .................................................................................... 22
12.5 Uninterruptible applications ................................................................................................. 22
13 Recommended re-pressurisation methods ................................................................................... 23
13.1 Recommendations and continuous monitoring ................................................................... 23
13.2 Carbon dioxide gas pressurisation up to 690 kPa (100 psi) (Method 1) ............................. 23
13.3 Recirculation of warmed liquid (Method 2) .......................................................................... 25
13.4 Hot gas warming at no pressure (Method 3)....................................................................... 26
13.5 Unassisted natural re-pressurisation (Method 4) ................................................................ 27
14 Re-pressurisation methods—not recommended........................................................................... 27
EIGA DOC 164/20

14.1 Transfer liquid carbon dioxide into the container to melt the dry ice and warm the liquid—
not recommended ............................................................................................................... 27
14.2 Pressure building vaporiser/internal heater method only—not recommended ................... 28
14.3 Transferring carbon dioxide vapour into the vapour connection of the de-pressurised
container—not recommended ............................................................................................. 28
14.4 Remove liquid carbon dioxide from the container and transfer to cargo tanks—not
recommended ..................................................................................................................... 28
14.5 Manual removal of dry ice—not recommended .................................................................. 28
15 Suggested measures to prevent container de-pressurisation ....................................................... 28
15.1 Backpressure regulating valve ............................................................................................ 28
15.2 Direct to process vaporiser ................................................................................................. 29
15.3 Low pressure alarm ............................................................................................................. 29
15.4 Remote monitoring .............................................................................................................. 29
15.5 Diverter valve on pressure relief devices ............................................................................ 29
15.6 Pressure relief device discharge piping design................................................................... 29
15.7 Signage ............................................................................................................................... 30
16 References .................................................................................................................................... 30
17 Additional references ..................................................................................................................... 31
Appendix A—EN pressure vessel material design information (Informative) ....................................... 32
Appendix B—ASME Boiler and Pressure Vessel Code, Section VIII, Division 1 Rules for Construction
of Pressure Vessels [1] (Informative) ............................................................................................ 35
Appendix C—Flow chart for Methods 1 through 4 ................................................................................ 38
Tables
Table 1 Physical constants of carbon dioxide ......................................................................................... 6
Table 2 Thermodynamic properties of saturated carbon dioxide solid, liquid and vapour phases (U.S.
customary units) ...................................................................................................................................... 8
Table 3 Thermodynamic properties of saturated carbon dioxide solid, liquid and vapour phases (SI
units)........................................................................................................................................................ 9
Table 4 Carbon dioxide container pressure/wall stress relationships ................................................... 16
Table 5—Typical quantities of carbon dioxide and times needed for container re-pressurisation ....... 20
Figures
Figure 1 Phase diagram for carbon dioxide ............................................................................................ 7
Figure 2 Typical caution sign ................................................................................................................ 13
Figure 3 Examples of incorrect and preferred pressure relief device installations on liquid carbon
dioxide piping ........................................................................................................................................ 15
Figure 4 Allowable pressure temperatures in an ASME liquid carbon dioxide container (pre-1976
safety factor 4X) .................................................................................................................................... 17
Figure 5 Allowable pressure temperature in an ASME liquid carbon dioxide container (pre-1998 safety
factor 4X, post-1998 safety factor 3.5X) ............................................................................................... 17
Figure 6 De-pressurised container evaluation form .............................................................................. 19
Figure 7 Method 1, Step 1 partial reliquification of solid carbon dioxide (dry ice) container
pressurisation with vapour up to 690 kPa (100 psi) .............................................................................. 24
Figure 8 Recirculation of warmed liquid to 1380 kPa (200 psi) ............................................................ 26
Figure 9 Circulation of warm vapour at no pressure to sublime dry ice (Method 3) ............................. 27
Figure 10 Typical protective measures to prevent container de-pressurisation ................................... 30
Figure 11 Examples of caution signage ................................................................................................ 30

Amendments to 164/10

Section Change
Editorial to align style with IHC associations
Extensive technical update
8.4 Removal of ACGIH reference

Note: Technical changes from the previous edition are underlined.

Note: Appendices A, B and C (Informative) are for information only.
EIGA DOC 164/20

1 Introduction

This publication is one of a series compiled by the Compressed Gas Association, Inc. (CGA) the
European Industrial Gases Association (EIGA), Asia Industrial Gases Association (AIGA), and Japan
Industrial and Medical Gases Association (JIMGA) to satisfy the demand for information on the
production, handling, storage, transportation, and use of compressed and liquefied gases, cryogenic
liquids, and related products.

2 Scope and purpose

2.1 Scope

The scope of this publication is concerned primarily with the safe re-pressurisation of stationary or
transportable liquid carbon dioxide containers made of low alloy carbon steels and having a minimum
design metal temperature (MDMT) greater than –78.9 °C (–110 °F).

2.2 Purpose

The purpose of this publication is to provide information to personnel to ensure that carbon dioxide
containers that have lost pressure and could contain solid carbon dioxide (dry ice) or liquid carbon
dioxide at temperatures less than the MDMT are safely re-pressurised before being returned to service.

Examples are given of re-pressurisation procedures for containers manufactured under the ASME
Boiler & Pressure Vessel Code, Section VIII, Division 1 (ASME Code), EN 13445-3, Unfired pressure
vessels Part 3 Design, EN 13458-2, Cryogenic vessels–Static vacuum insulated vessels–Part 2 Design,
fabrication, inspection and testing, and AD 2000 Code [1, 2, 3, 4]. 1

3 Definitions

For the purpose of this publication, the following definitions apply.

3.1 Publication terminology

3.1.1 Shall

Indicates that the procedure is mandatory. It is used wherever the criterion for conformance to specific
recommendations allows no deviation.

3.1.2 Should

Indicates that a procedure is recommended.

3.1.3 May

Indicates that the procedure is optional.

3.1.4 Will

Is used only to indicate the future, not a degree of requirement.

3.1.5 Can

Indicates a possibility or ability.

1 References are shown by bracketed numbers and are listed in order of appearance in the reference section.

1
EIGA DOC 164/20

3.2 Technical definitions

3.2.1 Auto-refrigeration

Lowering of the temperature of carbon dioxide as the pressure reduces to maintain temperature and
pressure equilibrium.

3.2.2 Brittle

Property of a material that causes it to break under load with little or no deformation.

3.2.3 Coincident temperature

Corresponding temperature for a substance at a given pressure at equilibrium.

3.2.4 Compressed gas

Substance existing only as a gas at a given temperature and pressure.

3.2.5 Condensation

Process by which a gas converts to a liquid.

3.2.6 Container

Insulated pressure vessel manufactured in accordance with a design standard, for example the ASME
Code for the storage of liquid carbon dioxide, EN 13458, or EN 13445 [1, 3, 2].

NOTE Container is interchangeable with vessel or tank.

3.2.7 Critical size

Size of a flaw in the container material that causes an uncontrolled increase of the length of a crack
while under constant stress.

3.2.8 De-pressurisation

Reduction of pressure in a container resulting in a container temperature less than the minimum design
metal temperature (MDMT) or the solidification of the carbon dioxide.

NOTE Typical causes are the overdrawing of a pressure building vaporiser, leaks, or a pressure relief device that
did not reseat properly.

3.2.9 Dry ice

Common name for solid carbon dioxide.

NOTE Its temperature is –78.5 °C (–109.3 °F) at atmospheric pressure.

3.2.10 Ductile

Property of a material that defines its ability to deform under load without breaking.

3.2.11 Elastic

Property of a material that defines its ability to deform under load without being permanently deformed.

2
EIGA DOC 164/20

3.2.12 Equilibrium

Physical state of a substance where the temperature and pressure will not change without an energy
exchange.

3.2.13 Low-alloy carbon steel

Steel relatively low in carbon containing small amounts of other elements to enhance strength, ductility,
and toughness.

3.2.14 Maximum allowable working pressure (MAWP)

Maximum gauge pressure permissible at the top of a vessel in its operating position for a designated
temperature.

3.2.15 Melting

Process by which dry ice converts to a liquid.

3.2.16 Minimum design metal temperature (MDMT)

Lowest temperature at which a container is designed to operate at a given pressure.

3.2.17 Nil ductility transition temperature (NDTT)

Temperature less than which metals are brittle enough to fracture.

3.2.18 Plastic deformation

Deformation of a material that will remain permanent after removal of the load that caused it.

3.2.19 Pressure building vaporiser

Heat exchanger that vaporises liquid carbon dioxide from the container and returns it to the container
as vapour to increase or maintain the pressure.

3.2.20 Qualified carbon dioxide technician

Person who by reason of education, training, and experience knows the properties of carbon dioxide; is
familiar with the equipment used to store, transfer, and use carbon dioxide; and understands the
precautions necessary to safely use carbon dioxide equipment.

3.2.21 Re-pressurisation

Process of restoring a container to its design parameters when it has lost pressure and is less than its
MDMT.

3.2.22 Sublimation

Process of changing from the solid phase directly to the gas phase without passing through the liquid
phase.

3.2.23 Toughness

Ability of a metal to absorb energy and undergo plastic deformation before fracturing.

3
EIGA DOC 164/20

3.2.24 Transportable container

Liquid carbon dioxide container meeting the requirement of a local or national authority that allows the
container to be moved on public roads and highways while under pressure.

3.2.25 Triple point

Temperature and pressure at which a material exists simultaneously as a solid, liquid, and gas.

NOTE For carbon dioxide, the triple point is –56.6 °C, (–69.9 °F) and 416 kPa (60.4 psia). 2

3.2.26 Ultimate tensile strength

Maximum stress level a material can sustain without fracturing.

3.2.27 Upset condition

Any condition outside the normal design parameters.

3.2.28 Vaporisation

Process by which liquid carbon dioxide is converted to a gas.

3.2.29 Yield strength

Stress at which a material exhibits a specified limiting deviation from the proportionality of stress to
strain. The deviation is expressed in terms of strain, percent offset, total extension under load, etc. [6,
7].

4 Basis

The basis for this publication is actual testing performed under the auspices of CGA, who sponsored
extensive testing on a horizontal 50-ton capacity carbon dioxide storage container in 1992 and 1993.
The purpose of the testing was to obtain pressure, temperature, and flow rate data to allow CGA to
evaluate prospective procedures that could be used to return a de-pressurised carbon dioxide container
to normal service. Many different re-pressurisation procedures were in use by the carbon dioxide
industry, and the purpose of the testing was to evaluate their safety. Many years of experience in both
North America and Europe support the testing done by CGA in 1992 and 1993.

These procedures and recommendations are intended to be the best available knowledge of carbon
dioxide and its safe use by the industry. No single re-pressurisation technique or procedure can be used
for every container in service.

5 Warning

It is critical that persons attempting to return a carbon dioxide container from an upset condition (low
pressure) be aware of the hazards involved, the metallurgical properties of the container, the quantity
of liquid in the container before the upset, and the physical site conditions in order to choose the safest
and best procedure for the circumstances.

A carbon dioxide container that has cooled less than its MDMT should be re-pressurised only by a
qualified carbon dioxide technician. Knowledge of the container metallurgy and the properties of carbon
dioxide are essential. The potential for catastrophic failure of a de-pressurised container being re-
pressurised is much greater than normal if not properly handled.

2 kPa shall indicate gauge pressure unless otherwise noted as (kPa, abs) for absolute pressure or (kPa, differential)

for differential pressure. All kPa values are rounded off per CGA P-11, Guideline for Metric Practice for the
Compressed Gas Industry [5].

4
EIGA DOC 164/20

6 Properties of carbon dioxide

Carbon dioxide is a colourless, odourless, slightly acidic gas that is approximately 50% heavier than air.
It is non-flammable and will not support combustion. The physical constants of carbon dioxide are
summarised in Table 1. Carbon dioxide can exist as a solid, liquid, gas, or supercritical fluid, depending
upon conditions of temperature and pressure.

Carbon dioxide at its triple point exists simultaneously as a liquid, gas, and solid at –56.6 °C and 518
kPa, abs (–69.9 °F and 75.1 psia). Any change in pressure or temperature causes carbon dioxide to
revert to a two-phase condition (see Figure 1).

Carbon dioxide at its critical point exists simultaneously as a liquid, gas, and supercritical fluid at
31.1 °C and 7381.8 kPa, abs (87.9 °F and 1070.6 psia). At pressures and temperatures greater than
the critical point, carbon dioxide exists only as a supercritical fluid.

See Tables 2 and 3 for the thermodynamic and physical properties of carbon dioxide.

At temperatures and pressures less than the triple point, carbon dioxide can be either a solid (dry ice)
or a gas, depending upon conditions. Dry ice at a temperature of –78.5 °C (–109.3 °F) and at
atmospheric pressure transforms directly to a gas (sublimes) without passing through the liquid phase.
Lower temperatures result if dry ice sublimes at pressures less than atmospheric.

At temperatures and pressures greater than the triple point and less than 31.1 °C (87.9 °F), carbon
dioxide liquid and gas can exist in equilibrium in a closed container. Within this temperature range, the
pressure in a closed container holding carbon dioxide liquid and gas in equilibrium bears a definite
relationship to the temperature. Carbon dioxide cannot exist as a liquid greater than its critical
temperature of 31.1 °C (87.9 °F), regardless of the pressure.

5
EIGA DOC 164/20

Table 1 Physical constants of carbon dioxide

U.S. Units SI Units

Chemical formula CO2 CO2
Molecular weight 44.01 lb/lb-mol 44.01 kg/kg-mol
Vapour pressure
at 70 °F (21.1 °C) 838 psi 5778 kPa
at 32 °F (0 °C) 491 psi 3385 kPa
at 2 °F (–16.7 °C) 302 psi 2082 kPa
at –20 °F (–28.9 °C) 200 psi 1379 kPa
at –69.9 °F (–56.6 °C) 60.4 psi 416 kPa
at –109.3 °F (–78.5 °C) 0 psi 0 kPa
Density of the gas
at 70 °F (21.1 °C) and 1 atm 0.1144 lb/ft3 1.833 kg/m3
at 32 °F (0 °C) and 1 atm 0.1234 lb/ft3 1.977 kg/m3
Specific gravity of the gas
at 70 °F (21.1 °C) and 1 atm (air = 1) 1.522 1.522
at 32 °F (0 °C) and 1 atm (air = 1) 1.524 1.524
Specific volume of the gas
at 70 °F (21.1 °C) and 1 atm 8.741 ft3/lb 0.5457 m3/kg
at 32 °F (0 °C) and 1 atm 8.104 ft3/lb 0.5059 m3/kg
Density of liquid, saturated
at 70 ° F (21.1 °C) 47.6 lb/ft3 762 kg/m3
at 32 °F (0 °C) 58.0 lb/ft3 929 kg/m3
at 2 °F (–16.7 °C) 63.3 lb/ft3 1014 kg/m3
at –20 °F (–28.9 °C) 66.8 lb/ft3 1070 kg/m3
at –69.9 °F (–56.6 °C) 73.5 lb/ft3 1177 kg/m3
Sublimation temperature (1 atm) –109.3 °F –78.5 °C
Critical temperature 87.9 °F 31.1 °C
Critical pressure 1070.6 psia 7381.8 kPa, abs
Critical density 29.2 lb/ft3 468 kg/m3
Triple point –69.9 °F at 75.1 psia –56.6 °C at 518 kPa, abs
Latent heat of vaporisation
at 32 °F (0 °C) 100.8 Btu/lb 234.5 kJ/kg
at 2 °F (–16.7 °C) 119.0 Btu/lb 276.8 kJ/kg
at –20 °F (–28.9 °C) 129.6 Btu/lb 301.4 kJ/kg
Latent heat of fusion at –69.9 °F (–56.6 °C) 85.6 Btu/lb 199 kJ/kg
Weight of liquid at 2 °F (–16.7 °C) 8.46 lb/gal 1014 kg/m3
Latent heat of sublimation at –109.3 °F (–78.5 °C) 245.5 Btu/lb 571.0 kJ/kg

6
EIGA DOC 164/20

5000 (34 480)

4000 (27 580)

3000 (20 680)

2000 (13 790)

1000 (6900)

800 (5520)
Liquid
region
600 (4140)
Critical
500 (3450) point
400 (2760)

300 (2070)
Pressure in psia (kPa absolute)

200 (1380)

Solid Vapor
region region
100 (690)

80 (552)

60 (414)
50 (345)
Triple
40 (276) point

30 (207)

20 (138)

14.7 psia

10 (69)

8 (55)

6 (41)
5 (34)

4 (27)

3 (21)

2 (14)

1 (7)
°F −160 −140 −120 −100 −80 −60 −40 −20 0 20 40 60 80 100 120 140
°C −106.7 −95.6 −84.4 −73.3 −62.2 −51.1 −40 −28.9 −17.7 −6.7 4.4 15.6 26.7 37.8 48.9 60

Temperature

Figure 1 Phase diagram for carbon dioxide

7
EIGA DOC 164/20

Table 2 Thermodynamic properties of saturated carbon dioxide solid, liquid and vapour phases
(U.S. customary units)

Pressure Density Specific

Enthalpy 1) Entropy 1)
volume
Temp
lb/ft3 ft3/lb Btu/lb Btu/(lb)(°R)
°F
psia psi solid or solid or solid or
vapour vapour vapour
liquid liquid liquid
–150 1.793 26.26 2)
99.7 41.81 53.55 305.50 0.3394 1.1530
–140 3.171 23.46 2) 99.2 24.41 56.36 306.90 0.3483 1.1318
–130 5.405 18.92 2) 98.8 14.69 59.22 308.30 0.3571 1.1126
–120 8.923 11.75 2) 98.3 9.131 62.15 309.62 0.3658 1.0945
–110 14.34 7.725 2) 97.5 5.829 65.16 310.81 0.3743 1.0770
–109.3 14.70 0.000 97.5 5.683 65.38 310.90 0.3748 1.0758
Solid and Vapour

–105 17.94 3.244 97.2 4.708 66.69 311.45 0.3786 1.0687

–100 22.28 7.584 96.9 3.814 68.24 312.01 0.3829 1.0606
–95 27.67 12.97 96.6 3.103 69.80 312.50 0.3872 1.0527
–90 34.14 19.44 96.2 2.531 71.41 312.89 0.3915 1.0449
–85 41.63 26.93 95.7 2.074 73.01 313.11 0.3959 1.0372
–80 50.58 35.88 95.3 1.714 74.63 313.22 0.4002 1.0292
–75 61.72 47.02 94.9 1.418 76.28 313.29 0.4045 1.0215
–70 74.76 60.06 94.4 1.182 77.96 313.42 0.4089 1.0151
–69.9 75.13 60.43 94.4 1.157 78.01 313.42 0.4112 1.0150
Triple point
–69.9 75.13 60.43 73.53 1.157 163.6 313.42 0.6308 1.0150
–68 78.48 63.78 73.30 1.117 164.4 313.49 0.6318 1.0128
–66 82.34 67.64 73.05 1.060 165.3 313.58 0.6340 1.0107
–64 86.35 71.65 72.79 1.011 166.1 313.67 0.6362 1.0088
–62 90.50 75.80 72.54 0.9659 167.0 313.76 0.6384 1.0070
–60 94.76 80.06 72.28 0.9254 167.9 313.85 0.6406 1.0053
–58 99.15 84.45 72.01 0.8876 168.8 313.94 0.6427 1.0038
–56 103.7 89.00 71.76 0.8501 169.6 314.03 0.6448 1.0024
–54 108.4 93.70 71.49 0.8145 170.5 314.12 0.6469 1.0010
–52 113.2 98.50 71.23 0.7809 171.4 314.23 0.6490 0.9996
–50 118.2 103.50 70.97 0.7489 172.3 314.33 0.6511 0.9982
–48 123.4 108.70 70.71 0.7184 173.2 314.44 0.6533 0.9967
–46 128.8 114.10 70.44 0.6896 174.1 314.57 0.6555 0.9952
–44 134.3 119.60 70.16 0.6622 175.0 314.68 0.6577 0.9938
–42 140.0 125.30 69.88 0.6361 175.9 314.78 0.6599 0.9924
Liquid and Vapour

–40 145.9 131.20 69.60 0.6113 176.8 314.89 0.6621 0.9910

–38 152.0 137.30 69.33 0.5876 177.7 314.98 0.6642 0.9897
–36 158.1 143.40 69.04 0.5648 178.7 315.09 0.6663 0.9883
–34 164.6 149.90 68.76 0.5432 179.6 315.20 0.6684 0.9869
–32 171.2 156.50 68.48 0.5227 180.5 315.31 0.6704 0.9855
–30 178.0 163.30 68.20 0.5031 181.4 315.40 0.6725 0.9842
–28 184.9 170.20 67.92 0.4844 182.3 315.49 0.6746 0.9829
–26 192.1 177.40 67.64 0.4665 183.2 315.58 0.6767 0.9817
–24 199.6 184.90 67.35 0.4492 184.3 315.67 0.6788 0.9805
–22 207.2 192.50 67.06 0.4325 185.2 315.74 0.6810 0.9793
–20 215.0 200.30 66.77 0.4166 186.1 315.81 0.6831 0.9781
–18 223.1 208.40 66.47 0.4014 187.0 315.86 0.6852 0.9769
–16 231.3 216.60 66.17 0.3868 188.1 315.92 0.6873 0.9756
–14 239.8 225.10 65.87 0.3731 189.0 315.95 0.6894 0.9743
–12 248.7 234.00 65.56 0.3599 189.9 315.99 0.6916 0.9730
–10 257.6 242.90 65.25 0.3473 191.0 316.01 0.6937 0.9717
–8 266.9 252.20 64.93 0.3351 191.9 316.01 0.6958 0.9704
–6 276 3 261.6 64.62 0.3233 193.0 316.01 0.6979 0.9691
–4 285.8 271.1 64.29 0.3119 193.9 315.99 0.7000 0.9678
–2 295.7 281.0 63.96 0.3010 194.9 315.95 0.7022 0.9666
+0 305.8 291.1 63.63 0.2906 195.8 315.92 0.7043 0.9654
2 316.3 301.6 63.30 0.2805 196.9 315.88 0.7064 0.9642
4 327.0 312.3 62.97 0.2707 198.0 315.83 0.7085 0.9629
6 337.9 323.2 62.64 0.2613 198.9 315.76 0.7106 0.9616
8 349.0 334.3 62.30 0.2523 200.0 315.68 0.7127 0.9603
10 360.5 345.8 61.99 0.2436 200.9 315.59 0.7148 0.9589
12 372.2 357.5 61.69 0.2353 202.0 315.50 0.7169 0.9575
14 384.3 369.6 61.32 0.2273 203.0 315.40 0.7190 0.9561
16 396.5 381.8 61.02 0.2196 204.1 315.27 0.7211 0.9547

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EIGA DOC 164/20

Pressure Density Specific

Enthalpy 1) Entropy 1)
volume
Temp
lb/ft3 ft3/lb Btu/lb Btu/(lb)(°R)
°F
psia psi solid or solid or solid or
vapour vapour vapour
liquid liquid liquid
18 409.0 394.3 60.67 0.2122 205.2 315.13 0.7232 0.9533
20 421.9 407.2 60.32 0.2050 206.3 314.96 0.7253 0.9520
22 435.1 420.4 59.91 0.1980 207.4 314.80 0.7275 0.9507
24 448.7 434.0 59.57 0.1911 208.4 314.62 0.7297 0.9493
26 462.5 447.8 59.17 0.1845 209.5 314.42 0.7319 0.9479
28 476.6 461.9 58.78 0.1783 210.6 314.19 0.7341 0.9465
30 490.8 476.1 58.40 0.1722 211.7 313.90 0.7363 0.9450
32 505.5 490.8 58.02 0.1663 212.8 313.58 0.7385 0.9434
Liquid and Vapour

34 520.5 505.8 57.59 0.1602 214.0 313.20 0.7407 0.9417

36 536.0 521.3 57.12 0.1542 215.1 312.77 0.7429 0.9399
38 551.7 537.0 56.70 0.1482 216.4 312.28 0.7452 0.9380
40 567.7 553.0 56.29 0.1425 217.4 311.76 0.7475 0.9360
42 584.0 569.3 55.89 0.1372 218.7 311.20 0.7598 0.9340
44 600.8 586.1 55.44 0.1321 220.0 310.63 0.7521 0.9321
46 617.8 603.1 54.95 0.1273 221.2 310.05 0.7544 0.9302
48 635.2 620.5 54.43 0.1226 222 5 309.47 0.7568 0.9283
50 652.9 638.2 53.91 0.1181 223.7 308.90 0.7593 0.9264
52 671.2 656.5 53.45 0.1138 225.0 308.32 0.7618 0.9246
54 689.7 675.0 52.95 0.1095 226.4 307.75 0.7643 0.9227
56 708.6 693.9 52.37 0.1054 227.7 307.13 0.7668 0.9207
58 727.9 713.2 51.81 0.1014 229.1 306.49 0.7694 0.9187
60 747.6 732.9 51.17 0.09752 230.6 305.78 0.7720 0.9166
62 767.7 753.0 50.47 0.09372 232.0 305.03 0.7746 0.9145
64 788.3 773.6 49.78 0.08999 233.5 304.22 0.7773 0.9123
66 809.3 794.6 49.08 0.08631 235.1 303.35 0.7801 0.9100
68 830.8 816.1 48.39 0.08261 236.7 302.45 0.7830 0.9077
70 852.7 838.0 47.62 0.07894 238 3 301.52 0.7861 0.9053
72 875.0 860.3 46.80 0.07535 240.3 300.51 0.7894 0.9030
74 897.8 883.1 45.90 0.07173 242.1 299.39 0.7930 0.9006
76 921.1 906.4 44.94 0.06811 244.3 298.10 0.7970 0.8982
78 945.1 930.4 43.90 0.06411 246.4 296.57 0.8013 0.8957
80 969.5 954.8 42.67 0.06013 248.9 294.75 0.8060 0.8924
82 994.5 979.8 41.23 0.05603 251.5 292.46 0.8112 0.8881
84 1020 1005 39.59 0.05171 254.7 289.67 0.8170 0.8821
86 1046 1031 37.03 0.04711 259.0 285.64 0.8249 0.8737
87.9 1071 1056 29.21 0.03423 272.7 272.70 0.8483 0.8483
1)
Based on 0 for the perfect crystal at absolute zero temperature, –273.15 °C (–459.67 °F).
2)
Inches of mercury below atmospheric pressure.

Table 3 Thermodynamic properties of saturated carbon dioxide solid, liquid and vapour phases
(SI units)

Pressure Density Specific Enthalpy 1) Entropy

volume
Temp
°C kg/m3 m3/kg x 10–3 kJ/kg kJ/(kg)(K)
kPa kPa
absolute gauge solid or solid or solid or
vapour vapour vapour
liquid liquid liquid
–102 11.36 –89.97 1597 2837 123.5 710.1 1.415 4.841
–100 13.97 –87.36 1595 2327 125.8 711.3 1.428 4.809
–98 17.15 –84.18 1593 1916 128.2 712.4 1.442 4.777
–96 20.95 –80.38 1591 1583 130.5 713.6 1.455 4.746
–94 25.49 –75.84 1588 1314 132.9 714.8 1.469 4.716
Solid and Vapour

–92 30.89 –70.44 1585 1095 135.3 715.9 1.482 4.687

–90 37.27 –64.06 1582 917.3 137.7 717.1 1.495 4.658
–88 44.76 –56.57 1579 771.9 140.2 718.2 1.508 4.630
–86 53.53 –47.80 1576 651.3 142.6 719.3 1.521 4.603
–84 63.77 –37.56 1573 550.7 145.1 720.4 1.534 4.376
–82 75.72 –25.61 1569 467.1 147.6 721.4 1.548 4.550
–80 89.62 –11.71 1565 397.7 150.1 722.4 1.561 4.523
–78.5 101.3 0.0 1562 354.7 152.1 723.1 1.569 4.504
–78 105.7 4.4 1561 339.8 152.7 723.4 1.574 4.498
–76 124.2 22.9 1558 291.1 155.3 724.4 1.586 4.473

9
EIGA DOC 164/20

Pressure Density Specific Enthalpy 1) Entropy

volume
Temp
°C kg/m3 m3/kg x 10–3 kJ/kg kJ/(kg)(K)
kPa kPa
absolute gauge solid or solid or solid or
vapour vapour vapour
liquid liquid liquid
–74 145.6 44.3 1554 249.9 157.9 725.4 1.599 4.449
–72 170.0 68.7 1549 215.1 160.5 726.3 1.612 4.425
Solid and Vapour

–70 198.1 96.8 1545 185.7 163.1 727.1 1.625 4.402

–68 230.2 128.9 1541 160.8 165.8 727.7 1.638 4.378
–66 267.0 165.7 1536 139.5 168.4 728.1 1.651 4.353
–64 308.9 207.6 1532 121.1 171.1 728.4 1.664 4.328
–62 356.7 255.4 1527 105.1 173.9 728.6 1.677 4.304
–60 409.8 308.5 1522 91.23 176.7 728.7 1.690 4.281
–58 467.1 365.8 1517 81.00 179.5 728.8 1.703 4.262
–56.6 518.0 416.7 1513 72.22 181.4 729.0 1.722 4.250
Triple point
–56.6 518.0 416.7 1178 72.22 380.5 729.0 2.641 4.250
–56 531.7 430.4 1176 71.10 381.5 729.1 2.643 4.244
–54 578.9 477.6 1168 64.72 385.2 729.5 2.659 4.229
–52 629.5 528.2 1161 59.78 388.9 729.8 2.675 4.215
–50 683.6 582.3 1154 55.41 392.5 730.2 2.691 4.203
–48 741.0 639.7 1146 51.36 396.2 730.6 2.707 4.192
–46 801.9 700.6 1139 47.63 399.9 731.1 2.723 4.181
–44 866.3 865.0 1131 44.20 403.7 731.5 2.739 4.170
–42 934.3 833.0 1123 41.05 407.5 732.0 2.756 4.160
–40 1006 904.7 1115 38.16 411.3 732.4 2.772 4.149
–38 1082 981 1107 35.52 415.1 732.9 2.788 4.139
–36 1162 1061 1099 33.11 419.0 733.3 2.803 4.129
–34 1246 1145 1091 30.90 422.9 733.7 2.819 4.119
Liquid and Vapour

–32 1335 1234 1083 28.87 426.8 734.1 2.835 4.109

–30 1429 1328 1074 27.00 430.8 734.4 2.851 4.100
–28 1527 1426 1066 25.27 434.8 734.7 2.867 4.091
–26 1630 1529 1057 23.66 438.8 734.9 2.883 4.081
–24 1739 1638 1048 22.16 442.8 735.0 2.899 4.072
–22 1852 1751 1039 20.76 446.9 735.0 2.915 4.062
–20 1971 1870 1030 19.45 451.0 735.0 2.931 4.053
–18 2095 1994 1021 18.24 455.1 734.9 2.947 4.044
–16 2226 2125 1011 17.13 459.3 734.7 2.963 4.034
–14 2362 2261 1002 16.09 463.6 734.4 2.979 4.024
–12 2503 2402 991.9 15.11 467.8 734.1 2.994 4.014
–10 2649 2548 982.0 14.19 472.2 733.6 3.010 4.004
–8 2804 2703 971.8 13.34 476.6 733.0 3.027 3.993
–6 2964 2863 961.5 12.54 481.1 732.2 3.043 3.983
–4 3131 3030 951.5 11.79 485.6 731.4 3.059 3.973
–2 3305 3204 940.7 11.07 490.3 730.5 3.076 3.962
0.0 3485 3384 929.4 10.38 495.0 729.4 3.092 3.950
2.0 3673 3572 917.4 9.703 499.8 727.7 3.109 3.937
4.0 3869 3768 905.0 9.046 504.7 725.4 3.126 3.923
6.0 4071 3970 892.1 8.435 509.8 723.1 3.143 3.908
8.0 4282 4181 878.0 7.878 515.0 720.8 3.161 3.894
10.0 4501 4400 863.6 7.375 520.4 718.5 3.179 3.879
12.0 4730 4629 848.2 6.900 525.9 716.1 3.198 3.864
14.0 4966 4865 831.9 6.446 531.6 713.5 3.217 3.849
16.0 5210 5109 814.3 6.006 537.6 710.5 3.236 3.833
18.0 5464 5363 795.5 5.577 543.8 707.2 3.256 3.817
20.0 5727 5626 775.2 5.157 550.4 703.5 3.278 3.800
22.0 6001 5900 753.6 4.745 557.8 699.4 3.303 3.783
24.0 6285 6184 728.9 4.337 566.0 694.6 3.331 3.765
26.0 6581 6480 696.4 3.914 575.4 688.2 3.364 3.745
28.0 6890 6789 655.7 3.460 586.3 679.1 3.403 3.710
30.0 7211 7110 593.1 2.910 602.5 664.4 3.454 3.658
31.1 7382 7281 467.9 2.137 634.3 634.3 3.552 3.552

1)
Based on 0 for the perfect crystal at zero Kelvin (–273.15 °C).

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EIGA DOC 164/20

7 Temperature and pressure

The temperature of liquid carbon dioxide and its container decreases as the pressure decreases due to
auto-refrigeration. The temperature and phases of the container contents during de-pressurisation can
be accurately determined by using the known pressure and the phase diagram shown in Figure 1. A
conversion from liquid to dry ice begins to occur at 416 kPa (60.4 psi) with a coincident temperature of
–56.6 °C (–69.9 °F). This is the triple point where gas, liquid, and dry ice exist in equilibrium. As gas
continues venting, energy is extracted from the liquid to generate the gas and solid required to maintain
equilibrium. This converts more liquid to a solid. This process continues as long as venting occurs with
temperature and pressure remaining constant, until only gas and dry ice remain. Continued venting less
than the triple point causes the pressure and temperature to continue to decline until at 0 kPa (0 psi) a
temperature of –78.5 °C (–109.3 °F) is reached.

Container pressure losses can be caused by such things as a relief valve opening and failing to reclose,
the rapid withdrawal of large volumes of carbon dioxide vapour, or the failure of a pressure building
vaporiser. In the case of road tankers, pressure loss can occur due to single hose filling at customer
tanks.

Carbon dioxide container owners and operators need to understand that the pressure/temperature
equilibrium relationship does not apply when a container is being re-pressurised to return to normal
service. It is possible for a container to be at 2070 kPa (300 psi) and to have liquid and dry ice at
–56.6 °C (–69.9 °F) in the container because it is not at equilibrium. The liquid temperature will
eventually warm up and the vapour pressure will decrease until they stabilise, but this can take days or
weeks to occur.

Carbon dioxide storage containers are typically designed and constructed in accordance with the ASME
Code, which is the recognised standard for pressure vessel construction in the United States and
Canada [1]. The ASME Code provides a safety factor of 3.5, which means that at its maximum working
pressure, the material is stressed to only 28.6% of its ultimate tensile strength. Carbon dioxide
containers are typically fabricated using low-alloy carbon steels.

Low-alloy carbon steels at design operating conditions are both strong (have high tensile strength) and
ductile. These materials remain strong as they become cold but become less ductile. A decrease in
operating temperature can result in the container reaching its nil ductility transition temperature (NDTT).
This means that a material that is normally considered ductile becomes brittle at temperatures less than
the NDTT. This condition is fully reversible when the metal temperature rises greater than the NDTT.
As the temperature decreases, the container material also shrinks and can produce localised stresses.
Ductile materials can accommodate localised stresses by slight deformation. The material will stretch
in that area and not fail. Brittle materials are not able to stretch locally at low temperatures and can
catastrophically fail. If a crack or material defect reaches a critical size in a pressurised brittle container,
there is a greater likelihood of a total container failure similar to breaking a glass jar. Ductile materials
can fail, but generally not catastrophically because the material tends to stretch, possibly crack and
leak, but does not come apart.

Carbon dioxide is stored in insulated containers as a liquefied compressed gas. Normal container
operating pressures range from 1380 kPa to 2070 kPa (200 psi to 300 psi), which corresponds to an
equilibrium temperature of–28.9 °C (–20 °F) and –16.1 °C (3 °F) respectively.

In North America, the majority of the containers in refrigerated carbon dioxide service are fabricated
using low-alloy carbon steels such as SA-212, SA-515, SA-516, and SA-612. Containers manufactured
before 1990 typically had an MDMT of –28.9 °C (–20 °F). When the container wall is at an operating
temperature colder than the MDMT, it is out of its intended operating condition.

8 Physiological effects of carbon dioxide

8.1 General

The physiological effects of carbon dioxide are unique because carbon dioxide is a product of normal
metabolism, a requirement of the body’s normal internal chemical environment, and an active
messenger substance in the linking of respiration, circulation, and vascular response to the demands
of metabolism both at rest and in exercise.

11
EIGA DOC 164/20

The respiratory control system maintains carbon dioxide pressure at a relatively high level of
approximately 50 mm Hg pressure in the arterial blood and tissue fluids. This maintains the acidity of
the tissue and cellular fluids at the proper level for the essential metabolic reactions and membrane
functions. Changes in the normal carbon dioxide tissue pressure can be damaging. If tissue pressure
becomes excessively low, which can occur from hyperventilation, failure of critical neuromuscular
function or loss of consciousness can occur.

Inhaled carbon dioxide produces the same physiological effects as metabolically produced carbon
dioxide. As the carbon dioxide tissue pressure rises from inhaling carbon dioxide, the body responds by
using respiratory and adaptive processes to adjust to the change. These adaptive processes are limited
and cannot cope with severe exposures that cause pH change to the body fluids.

Toxic effects of carbon dioxide, namely severe and disruptive acidosis, occur when high concentrations
of carbon dioxide are inhaled.

Blood and cellular fluids are actually solutions of sodium bicarbonate containing numerous other
substances. Severe exposure to carbon dioxide forms carbonic acid in the blood for which the sodium
bicarbonate is not very effective as a buffer. The decrease in pH has a toxic effect because the neural
control systems are excessively driven, and this toxic effect is rapid. It is important to note that these
effects are independent of the amount of oxygen in the atmosphere being breathed.

The effects produced by inhaling low and moderate concentrations of carbon dioxide are physiological
and reversible, but the effects of high concentrations are toxic and damaging [8].

8.2 Effects of inhaled carbon dioxide

The response to carbon dioxide inhalation depends on degree and duration of exposure, and it varies
greatly even in healthy normal individuals. The medical term for the physiological effects of excess
carbon dioxide in the blood is hypercapnia. Carbon dioxide can be dangerous even when normal oxygen
levels are present. Low concentrations of inspired carbon dioxide can be tolerated for a considerable
period without noticeable effect, or merely cause an unnatural feeling of shortness of breath. Sustained
exposure to 5% carbon dioxide produces stressful rapid breathing. When the level of inspired carbon
dioxide exceeds 7%, the rapid breathing becomes laboured (dyspnoea) and restlessness, faintness,
severe headache, and dulling of consciousness occurs. At 15%, unconsciousness accompanied by
rigidity and tremors occurs in less than 1 minute, and in the 20% to 30% range it produces
unconsciousness and convulsions in less than 30 seconds. The reason these effects occur quickly is
that the carbon dioxide diffuses in the tissue fluids at a rate approximately 20 times more rapidly than
oxygen. High concentrations of carbon dioxide can asphyxiate quickly without warning and with no
possibility of self-rescue regardless of the oxygen concentration.

8.3 Physical effects of overexposure to carbon dioxide

Skin, mouth, or eye contact with dry ice, which has a temperature of –78.5 °C (–109.3 °F) can cause
severe frostbite, skin lesions, corneal burn, or more serious injury from deep freezing of the tissues.
Liquid discharging from a container produces high-velocity carbon dioxide snow particles, which are
abrasive in addition to being cold and can cause similar injuries.

8.4 Regulatory standard

Carbon dioxide is naturally present in the atmosphere at about 0.035% by volume. The Occupational
Safety and Health Administration (OSHA) standard for maximum allowable concentration, in air in the
workplace is 0.5% for 8 continuous hours of exposure. OSHA lists an 8-hour Time-Weighted Average–
Permissible Exposure Limit (TWA–PEL) of 5000 ppm (9000 mg/m3) for carbon dioxide [9]. TWA–PEL
is the exposure limit that shall not be exceeded by the 8-hour time-weighted average in any 8-hour work
shift of a 40-hour work week. See Title 29 of the U.S. Code of Federal Regulations (29 CFR) Parts
1910.1000, Table Z-1 [9].

Also, exposures greater than the TLV–TWA up to the STEL should not be longer than 15 minutes and
should not occur more than 4 times per day. There should be at least 60 minutes between successive
exposures in this range [9]. In Canada, similar limits are mandated by provincial legislation.

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EIGA DOC 164/20

For more information, see the gas supplier’s safety data sheet [10].

Rationale for exposure limits being less than those for a simple asphyxiant can be found in EIGA SI
24/17 Carbon Dioxide Physiological Hazards – “Not just an Asphyxiant” [11].

8.5 Safety precautions

Appropriate warning signs shall be placed at the entrance to confined areas where high concentrations
of carbon dioxide gas can accumulate. Some countries regulate the minimum size of the sign. For
example, in the United States, NFPA 55, Compressed Gases and Cryogenic Fluids Code, requires the
sign to be at least 200 mm (8 in) wide and 150 mm (6 in) high see Figure 2 [12].

Figure 2 Typical caution sign

Carbon dioxide monitoring shall be performed prior to entering any confined space or low area in which
carbon dioxide gas could have accumulated. The carbon dioxide shall be removed by ventilation to a
concentration below 3% (see 8.4) or a supplied-air respirator shall be donned before entering the
confined space or low area (see 29 CFR 1910.146) [9]. For further information see personnel
overexposure in CGA G-6, Carbon Dioxide [13].

NOTE The 3% concentration is for U.S. jurisdictions with exposure time not to exceed 15 minutes. Lower
concentrations would apply for longer exposure times in the U.S. The maximum allowed concentrations can be
different in other jurisdictions.

WARNING: Supplied-air respirators shall only be used by authorised personnel with appropriate training
and qualification for use of these respirators. Cartridge-style respirators shall not be substituted for
supplied-air respirators.

8.6 Rescue and first aid

Do not attempt to remove anyone exposed to high concentrations of carbon dioxide without using proper
rescue equipment or you can also become a casualty. According to OSHA rescuers account for over
60% of confined space fatalities. If the exposed person is unconscious, obtain assistance and use the
established emergency procedures.

If a person has inhaled large amounts of carbon dioxide and is exhibiting adverse effects, move the
exposed individual to fresh air at once. If breathing has stopped, perform artificial respiration. Only
qualified personnel may give oxygen to the victim. Keep the affected person warm and at rest. Get
medical attention as soon as possible. Fresh air and assisted breathing is appropriate for all cases of
overexposure to gaseous carbon dioxide. With prompt response to a carbon dioxide emergency,
recovery is usually complete and uneventful.

If dry ice or compressed carbon dioxide gas comes in contact with the skin or mouth, stop the exposure
immediately. If frostbite has occurred, obtain medical attention. Do not rub the area. Immerse in warm
water (38 °C to 41 °C [100 °F to 105 °F]), until it appears to be back to the normal skin tone and feels
warm.

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EIGA DOC 164/20

9 Specific hazards

9.1 General

Personnel handling liquid carbon dioxide should be thoroughly familiar with the hazards associated with
this product. There are several conditions in which extreme danger to personnel and equipment can
exist. The following describes these conditions and offers procedures and guidelines to prevent
dangerous conditions from developing.

9.2 Dry ice blocking

Liquid carbon dioxide in a hose or pipe flows like water. However, when the pressure is reduced to less
than the triple point, the liquid changes into a mixture of vapour and dry ice. Dry ice can create a
blockage or plug when formed in a pipe or hose.

The pressure behind or within a plug can increase as the dry ice sublimes until the plug is forcibly
ejected or the hose or pipe ruptures. A dry ice plug can be ejected from any open end of a hose or pipe
with enough force to cause serious injury to personnel from the impact of the dry ice plug or the sudden
whip of the hose or pipe as the plug ejects, or both. To prevent dry ice blockage, the liquid carbon
dioxide shall be purged from the hose or pipe before reducing the pressure less than the triple point.
This can be done by supplying carbon dioxide vapour to one end of the hose or piping system to
maintain the pressure greater than the triple point while removing the remaining liquid from the other
end.

9.3 Low temperature effects on materials

The low temperature effect caused by reducing the pressure of a saturated liquid carbon dioxide
(auto-refrigeration) is another hazard. If the pressure is reduced to atmospheric pressure, the
temperature can be as low as that of dry ice [–78.5 °C (–109.3 °F]). At dry ice temperatures, many
materials used in hose and piping systems can become brittle and fail if highly stressed. Materials used
in the construction of carbon dioxide transfer systems including hoses should be compatible with liquid
carbon dioxide and the temperature and pressure conditions encountered.

9.4 Trapped liquid

When liquid carbon dioxide is forced to occupy a fixed volume such as between two closed valves or
within a valve, its pressure increases as it warms and expands. As the temperature continues to
increase, the pressure of the trapped liquid can exceed what the piping and hoses can withstand. This
can cause the hose or piping to rupture with possible injury and property damage.

All liquid carbon dioxide piping shall be equipped with pressure relief devices (PRDs) if the piping is
located in the part of the system where liquid can be trapped such as between manual valves, control
valves, check valves, etc. Trapping can occur through manual isolation during maintenance or by
operation of automatic devices. These PRDs shall be set to discharge within the design pressure of the
part of the system they protect and should discharge into a well-ventilated area. The PRDs shall be
installed on a riser pipe extended from the cold liquid piping to create a vapour trap and prevent water
ice from accumulating inside the PRD and allow any condensation to drain, see Figure 3.

14
EIGA DOC 164/20

Figure 3 Examples of incorrect and preferred pressure relief device installations on liquid
carbon dioxide piping

9.5 Overfilling containers

When liquid carbon dioxide is stored in a container and there is no product withdrawal, heat leak causes
the temperature and pressure to rise and the liquid to expand. For a given temperature increase, the
pressure rises at a faster rate if the container is liquid full compared to a container that still has a vapour
space. These characteristics shall be considered while planning re-pressurisation of the container.

9.6 Personnel overexposure

When carbon dioxide is used in an enclosed area, ventilate the area adequately to maintain a safe
working environment for personnel. Carbon dioxide in the gaseous state is colourless and odourless
and not easily detectable. Since gaseous carbon dioxide is 1.5 times denser than air, it will be found in
greater concentrations in confined areas or low levels. Therefore, ventilation systems should be
designed to exhaust from the lowest level and allow make-up air to enter at a higher point. Do not
depend on measuring the oxygen content of the air because carbon dioxide can be dangerous even
with adequate oxygen for life support. For additional information, see Section 8.

9.7 Thermal expansion and contraction

For conventionally insulated (i.e., polyurethane insulation, not vacuum insulated) tanks on saddles,
provisions should exist to accommodate the thermal movements caused by the low temperature cycle.
The provisions to include making sure the sliding saddle is free to accommodate both expansion and
contraction and that the connected piping has sufficient flexibility for the expected movement. Restricting
the movement of these tanks can cause excessive stress to the tank saddles and shell wall.

10 Hazards of carbon dioxide container re-pressurisation

10.1 Movement of transportable containers

Prior to the start of any re-pressurisation process, transportable containers should be in a secure and
suitably equipped location, to allow re-pressurisation in accordance with one of the re-pressurisation
methods in this publication. If it is necessary to move a transportable container to a secure and suitably
equipped location when the container or portions of it are less than its MDMT, an assessment should
be made whether the transportable container can be safely moved. The amount of lading, internal
pressure, component temperature, container support configuration, stresses during movement,
distance to be moved, etc., shall be included in the assessment. It is recommended that any remaining
liquid be discharged before movement, leaving only a residual pressure of approximately 34.5 kPa
(5 psi) during movement. This assessment should also consider placing the container and running gear
on a flatbed trailer during transport to minimise structural stress on the container.

15
EIGA DOC 164/20

10.2 Hazards

De-pressurisation of a container and the resulting auto-refrigeration that occur will not likely result in the
brittle fracture of an otherwise sound container. The highest stresses in the container are caused by the
internal pressure exerted by the product. As the pressure and temperature decrease, the pressure-
induced stresses also decrease.
Table 4 shows the relationship of the container wall stress and the internal pressure for both an ASME
and EN carbon dioxide container. The ASME container is constructed from SA 516-70N having a tensile
strength of 70 000 psi (483 MPa) with an MAWP of 350 psi (23.8 bar). The ASME Code requires a
safety factor of 3.5; therefore the maximum allowable stress at MAWP is 70 000/3.5 = 20 000 psi. The
EN example is constructed from a material having a guaranteed yield strength of 355 MPa (51 500 psi).
EN 13458-2 uses a safety factor of 2.8; therefore the maximum allowable stress at the MAWP of 22 bar
(319 psi) is 225.6 MPa [3].

NOTE The yield strength is the stress value corresponding to the 0.2% of the proof stress for carbon steel.

A pressure vessel risk assessment shall be performed by a qualified carbon dioxide technician prior to
choosing a container re-pressurisation technique. This assessment shall include the following: the
design code of the container, the ductility of the materials of construction, and wall stresses. Those
users with vessels other than ASME-designed vessels shall perform a comparable assessment to
ensure safe re-pressurisation. See Appendix A for an example of an assessment for an EN-designed
vessel and Appendix B for an ASME-designed vessel.

Table 4 Carbon dioxide container pressure/wall stress relationships

Equilibrium carbon dioxide Wall stress in container due to internal

Internal pressure
temperature pressure
ASME 1) 3) EN 2) 3)
psi kPa Bar °F °C
psi MPa MPa
350 2413 24.1 13 –11 20 000 138 ——
319 2199 22 5 –15 18 250 125.8 225.6
300 2069 20.7 3 –16 17 143 118 212.2
250 1724 17.2 –8 –22 14 286 98.4 176.8
200 1379 13.8 –20 –29 11 429 78.8 141.4
150 1034 10.3 –35 –37 8571 59.1 106.1
100 690 6.9 –53 –47 5714 39.4 71.8
60 414 4.1 –69 –56 3429 23.6 56.1
0 0 0 –110 –78.9 0 0 0
1)
At lower equilibrium temperatures/pressures and using the ASME Code and Figure UCS 66.1, it can be shown that the
allowable reduction in MDMT is colder than the equilibrium temperature at reduced pressures [1]. See Figures 4 and 5 as
examples for typical liquid carbon dioxide containers, which show the allowable temperature as a function of reduced
pressure.
2)
See Figure A-1 for additional information for EN-designed vessels.
3)
ASME example is for SA-516-70 with an MAWP of 350 psi (23.8 bar) and safety factor of 3.5. EN example is for
EN 13458-2 with an MAWP of 22 bar and safety factor of 2.8 [3]. The result is that the EN tank has a thinner wall and
stresses are higher for the same diameter and a given pressure.

16
 EIGA DOC 164/20

Low Alloy Steels – MDMT of –20 °F

30

Carbon dioxide
10 pressure/temperature
curve

-10
-20
CGA/EIGA
-30 repressurization
Temperature (°F)

procedure

-50
Carbon dioxide Outside ASME 0.7 in thick wall at
triple point Code 350 MAWP
-70
(safety factor 4X)

-90

-110
0 50 100 150 200 250 300 350
MAWP
Internal pressure (psig)
NOTE Steels used for carbon dioxide containers included SA-212, SA-515, SA-516 (as rolled), and SA-612 (as
rolled).

Figure 4 Allowable pressure temperatures in an ASME liquid carbon dioxide container (pre-
1976 safety factor 4X)

Normalized SA-516 & SA-612 - MDMT of -40 °F

30 Carbon dioxide
pressure/temperature
curve
10

0.7 in thick walll at

-10 350 MAWP
(safety factor 4X)
pre-1998
-30
Temperature (°F)

0.7 in thick wall at

-50 350 MAWP
Carbon dioxide (safety factor 3.5X)
triple point post-1998
-70

Outside ASME CGA/EIGA

-90 repressurization
Code
procedure
-110
0 50 100 150 200 250 300 350
MAWP
Internal pressure (psig)

Figure 5 Allowable pressure temperature in an ASME liquid carbon dioxide container (pre-1998
safety factor 4X, post-1998 safety factor 3.5X)

10.3 Specific precautions

Dangerous conditions can be caused by artificially increasing the pressure in a container that is
de-pressurised and auto-refrigerated to less than the container material’s NDTT. A carbon dioxide
container at a pressure less than 416 kPa (60.4 psi) should be assumed to be at a temperature less
than –69.9 °F (–56.6 °C) in a brittle condition and should be protected from impact. Movement of
stationary containers should be avoided. Movement of transportable containers in brittle condition is
addressed in 10.1.

17
EIGA DOC 164/20

Most carbon dioxide containers fabricated before 1976 in North America used coarse grain steels that
have poor low temperature characteristics (see Figure 4). These containers remain in service and
require special care when performing re-pressurisation. Consideration should be given to installing
backpressure control valves to prevent excessive vapour withdrawal, which is a common cause of
de-pressurisation. CGA recommends that the life of these vessels not be extended by overhauling, see
CGA PS-5, CGA Position Statement on the Suitability of Carbon Steel Containers for Stationary Carbon
Dioxide Storage [14].

These containers were manufactured using SA-212 or SA-515 low-alloy steels with an MAWP of 2410 kPa
to 2500 kPa (350 psi to 363 psi) in accordance with the ASME Code, which allowed MDMTs of –29 °C
(–20 °F) without any impact testing. The ASME Code was revised in 1987 to reflect the fact that similar
low-alloy steels did not have adequate ductility at temperatures colder than–12 °C (10 °F). They were,
and still are, within the ASME Code to operate at temperatures as cold as –29 °C (–20 °F).

Figure 4 illustrates where the pressure/temperature equilibrium curve for carbon dioxide passes through
the zone outside the ASME Code at equilibrium temperatures between –20 °F and –44 °F (–29 °C and
–42 °C) and corresponding equilibrium pressures of 200 psi and 120 psi (1380 kPa to 830 kPa).

Nevertheless, the re-pressurisation procedure outlined in Section 13, Method 1 followed by Method 2
are acceptable for the following reasons:
• The pressure vessel safety factor of these containers is 4:1 versus the 3.5:1 safety factor adopted
in 1987, which provides an additional level of safety;
• The stress level in the container wall from 830 kPa to 1380 kPa (120 psi to 200 psi) ranges from
33% to 55% of the design stress of the vessel. This means that even if operating in a brittle condition,
the stress level is less than 8.3% to 13.7% of the ultimate strength of the material;
• The containers were typically fabricated with fractional inch thickness plate compared to the present
day rolled to thickness plate. This effectively increased the container wall thickness thereby
increasing the factor of safety beyond the minimum 4:1 required by ASME;
• The containers are protected from impact and external damage by insulation and an outer jacket,
reducing the potential risk of a brittle failure caused by external stresses; and
• There have been no known failures or incidents on containers that have used these
re-pressurisation methods.

In addition, the following conditions shall be met:

• re-pressurisation procedure is performed by a qualified carbon dioxide technician;
• procedure is continuously attended and monitored for unusual circumstances; and
• after completing the procedure, do not fill the container over 80% of rated capacity the first time
(see Section 13).

CAUTION: Improper re-pressurisation of a container that is in a brittle condition can result in

catastrophic failure.

Escaping carbon dioxide can create an asphyxiation hazard in poorly ventilated spaces. Take adequate
precautions before entering such an area (see Section 9).

11 Preliminary procedures for returning de-pressurised containers to service

Prior to the start of the re-pressurisation of a container, follow these procedures:

• Discontinue all carbon dioxide withdrawal;
• Close all service withdrawal valves and do not return the container to service until it is equal to or
greater than the MDMT;
• Shut off all pressure building vaporiser(s) and do not introduce pressure from another source;
• Do not move stationary, fixed location containers;
• Do not subject the de-pressurised container to impact;

18
EIGA DOC 164/20

• Verify that provisions to accommodate the thermal movements caused by the low temperature cycle
have not been compromised (for example, by rust on sliding plates). This applies to conventionally
insulated tanks on saddles (i.e., polyurethane insulation, not vacuum insulated), where visible;
• Verify piping attached to a vessel does not show signs of unusual movement; and
• Determine if the container has residual liquid in addition to the expected dry ice.

11.1 Personnel requirements

A qualified carbon dioxide technician should determine the reason for loss of pressure and correct the
problem before proceeding with re-pressurisation procedures.

Re-pressurisation should only be attempted by a qualified carbon dioxide technician or persons

knowledgeable in the container design and physical properties of carbon dioxide. Safe, tested
procedures should be developed for each case before proceeding with re-pressurisation.

11.2 Provisions for alternate source

Returning a container to service can be a lengthy process, so arrangements may have to be made for
an alternate source of carbon dioxide. Depending on the amount of dry ice in the container and the size
of the container, a considerable amount of carbon dioxide can be required for the re-pressurisation
procedure. An evaluation should be made and an adequate source of carbon dioxide provided for this
procedure.

11.3 De-pressurised container evaluation

The container and its related piping, markings, Manufacturer’s Data Report (U-1A), recent fill records,
recent product use records, and events leading up to de-pressurisation should be investigated before
proceeding with re-pressurisation. The ASME data plate can be found on the container in one of a
number of locations such as on the legs, head, or manway. For an example of a de-pressurised
container evaluation form see Figure 6.

Manufacturer Year Built Man. Serial No.

Natl Bd No. Type Material MAWP
Minimum Design Metal Temp °F At psi Impact Test
ASME Code Capacity Pressure In Container
Liquid Level External Appearance

Piping External Appearance (e.g., frosted/water ice build-up or ambient temperature)

Signs of Product Discharge or Leakage

Last Known Contents Level Date Time
Last Known Pressure Date Time
Known Use Since Last Known Contents Level
Estimated Product Withdrawal Since Last Known Contents Level

Figure 6 De-pressurised container evaluation form

11.4 Facts to consider in evaluating re-pressurisation methods

Approximately 50% of the carbon dioxide in the container is lost during a complete de-pressurisation.

To re-liquefy and warm 0.45 kg (1 lb) of dry ice to approximately 1030 kPa (150 psi) saturated liquid,
4.1 kg to 4.5 kg of 1720 kPa (9 lb to 10 lb of 250 psi) saturated liquid is required.

Approximately 0.45 kg of –17.8 °C (1 lb of 0 °F) carbon dioxide vapour is required to return 0.45 kg (1
lb) of dry ice to about 1030 kPa (150 psi) saturated liquid. Some of the dry ice in the container melts
and changes to liquid. The liquid level increases until the residual dry ice becomes completely
submerged in the liquid. At this point, the container pressure increases, and continued addition of vapour

19
EIGA DOC 164/20

can result in unsafe container pressures greater than the triple point as the heat transfer is reduced
because the vapour is no longer in direct contact with the dry ice. Additional energy is required to melt
the remaining solid and warm the liquid and the container wall.

The liquid level gauge (using differential pressure or floats) cannot be relied upon when a container has
been de-pressurised less than its design temperature and contains dense liquid, snow, or dry ice.

Several carbon dioxide cargo tanks can be required to supply sufficient carbon dioxide vapour to
complete the re-pressurisation procedure (see Table 5).

A heat exchanger, a pump, and a source of energy can be required to complete the procedure outlined
in 13.2.

During re-pressurisation, dry ice becomes submerged in liquid carbon dioxide at pressures greater than
60.4 psi (416 kPa); therefore pressure can no longer be used as an indicator of container temperature.

Pressure greater than that calculated using the ASME Code and Figure UCS 66.1 should not be applied
to a vessel if the vessel’s material is likely to be colder than the MDMT [1].

Table 5—Typical quantities of carbon dioxide and times needed for container re-pressurisation

Time required to warm

Time to re-liquefy
CO2 vapour the liquid from
residual dry ice and
required to Number of –45.6 °C to –29 °C
Quantity of warm the liquid to Quantity of
pressurise to full 20 ton (–50 °F to –20 °F)
liquid CO2 in –28.8 °C (–20 °F) liquid CO2 in
690 kPa CO2 cargo 690 kPa to 1380
container before 1380 kPa (200 psi) using container after
(100 psi) tanks (kPa 100 psi to 200 psi)
de-pressurisation a 6 kW heater re-pressurisation
required using a 6 kW heater
(Section 13.2) (Section 13.3)
(Section 13.2)
(No dry ice present)
6 ton 1110 lb 503 kg 0.5 10 hr 3.3 ton 4.2 hr
14 ton 2590 lb 1175 kg 1.2 23.3 hr 7.6 ton 10.3 hr
30 ton 5550 lb 2517 kg 2.5 50 hr 16.3 ton 22 hr
50 ton 9250 lb 4196 kg 4.2 83.3 hr 27.1 ton 36.5 hr
NOTES
1 Container fully de-pressurised to atmosphere.
2 Flow rates as high as 54 kg/min (120 lb/min) were observed in tests using cargo tanks as the vapour source. To complete
this step, approximately 185 lb of vapour is required per ton of liquid carbon dioxide (92.3 kg/tonne) that was in the container
before de-pressurisation. If full 20 ton cargo tanks are the vapour supply source, then 0.084 cargo tanks per ton of liquid
de-pressurised is required.
• Example: 50 tons of liquid de-pressurised to 0 psi would require:
185 lb/ton (83.9 kg/0.91 tonne) x 50 ton (45.4 tonnes) = 9250 lb of carbon dioxide vapour (4096 kg) (column 2); or
0.084 x 50 = 4.2 cargo tanks to pressurise to 100 psi (690 kPa) (column 3).
• Example: A container that is totally de-pressurised should require about 10 kWh/ton liquid to melt all the dry ice and
warm the liquid to 200 psi (1380 kPa), i.e., a container with 30 tons of liquid fully de-pressurised can be returned to
200 psi (1380 kPa) using a 6 kW heater in about 50 hrs:
10 kWh/ton x 30 ton/6 kW = 50 hr (column 4).
• Example: The energy required to warm liquid carbon dioxide is approximately 0.28 kWh/ton °F. A container with 10
tons of liquid at 131 psi (900 kPa) (–40 °F/–40 °C) requires 112 kWh to warm up to 291 psi (2010 kPa) (0 °F/
–17.8 °C). (Temperature difference is 40 °F):
0.28 kWh/ton °F x (0 - [–40] °F) x 10 ton = 112 kWh.

12 Guidelines for evaluation of the condition of a de-pressurised container

A container that is less than the pressure corresponding to its MDMT, typically 1380 kPa (200 psi),
needs to be evaluated before proceeding. It is possible that the container is empty (no liquid) or it could
hold cold liquid, a mixture of cold liquid and dry ice, or just dry ice. One of the most common causes of
container pressures declining to less than 1380 kPa (200 psi) is an empty container. All of the liquid is
consumed and only vapour pressure remains in the container. An empty container is not an upset
condition but shall be treated as such until a proper evaluation is completed. The following guidelines

20
EIGA DOC 164/20

should be used by a qualified carbon dioxide technician before proceeding with re-pressurisation and a
return to normal service.

Pressure cannot be the sole determinant of pressure vessel wall temperature during re-pressurisation
(see 11.4). Dry ice and colder liquid tend to settle to the bottom of the container. This could maintain
the temperature of the pressure vessel steel at the bottom of the container at the triple point when the
coincident pressure/temperature charts would predict otherwise. Industry testing has shown that the
shell and head metal, away from the nozzles being used to warm the tank, can be 10° C (50 °F) or more
colder than that predicted by the coincident carbon dioxide temperature charts corresponding to the
tank’s pressure gauge reading. This sets up the potential for tank failure if a slow and gradual procedure
is not used while raising the tank’s pressure.

12.1 Container pressure greater than 1380 kPa (200 psi)

The container is probably acceptable for normal service. However, if the container was de-pressurised
earlier and the pressure continues to decrease over time with no product removal, cold liquid or dry ice
are likely present. Do not maintain in normal service until all facts are known (see Section 11).

12.2 Container pressure less than 1380 kPa (200 psi) but greater than 416 kPa (60.4 psi)

The following procedure should be performed to determine whether the container is empty (no liquid
present):
a) Check the consumption records to determine whether the container could possibly be empty;
b) Check liquid valve and piping for signs of frost, which can indicate the presence of liquid carbon
dioxide or dry ice; and
c) Confirm that the container is empty by opening either the liquid fill valve or a liquid use valve. If
ONLY vapour exits, the container is empty and can be filled in accordance with CGA G-6.4, Safe
Transfer of Liquefied Carbon Dioxide in Insulated Cargo Tanks, Tank Cars, and Portable Containers
[15]. If liquid exits from either liquid valve or, if the piping is obstructed by dry ice blockages, then
low-temperature liquid and/or dry ice are present. See 13.1, 13.2, and 13.3 for further guidance.

12.2.1 Container minimum design metal temperature of –29 °C (–20 °F)

Containers holding liquid at pressures less than 1380 kPa (200 psi) are in an upset condition and are
colder than the minimum design condition. Re-pressurise using the procedures outlined in 13.4 and
13.5.

12.2.2 Container minimum design metal temperature of–40.0 °C (–40 °F)

Containers with pressures greater than 970 kPa (140 psi) can be returned to service. Containers with
pressures less than 970 kPa (140 psi) are in an upset condition and require the re-pressurisation
procedures as outlined in 13.4 and 13.5.

12.2.3 Container minimum design metal temperature of –46 °C (–50 °F)

Containers with pressures greater than 724 kPa (105 psi) can be returned to service. Containers with
pressures less than 720 kPa (105 psi) are in an upset condition and require the re-pressurisation
procedures in 13.4 and 13.5.

12.2.4 Containers with other minimum design metal temperature values

Containers with other MDMT values can be returned to service at pressures greater than the
corresponding equilibrium carbon dioxide pressure (see Figure 1). Containers with temperatures less
than the MDMT are in an upset condition and require the re-pressurisation procedures in 13.2 and 13.3.

21
EIGA DOC 164/20

12.3 Container pressure less than 416 kPa (60.4 psi)

The container could be empty of all liquid with vapour pressure only. The following procedure should be
performed to determine whether the container is empty (no dry ice present):
a) Check the consumption records to determine whether the container could possibly be empty;
b) Check liquid valve and piping for signs of frost, which can indicate the presence of liquid carbon
dioxide or dry ice;
c) Check the pressure and liquid level gauge for accuracy. Pulsations in the liquid level gauge can be
an indication of the presence of dry ice;
d) Pressurise the container to 690 kPa (100 psi) with vapour (see 13.2). If the container pressure stays
at 414 kPa (60 psi) for any length of time during this pressurisation, dry ice is present inside the
container; and
e) Open either the liquid fill valve or a liquid use valve and see if only vapour exits. If the liquid piping
is obstructed by dry ice or discharges liquid, then the tank contains dry ice and shall be re-
pressurised using methods given in Section 13.

12.4 Special low-temperature containers

Containers made of materials that remain ductile at –78.5 °C (–109.3 °F) (for example TC/DOT-4L
containers made of type 304 stainless steel) may be returned to service without some of the precautions
necessary for containers made of materials that do experience a loss of ductility less than –28.9 °C
(–20 °F). The ASME data plate of such vessels should clearly identify them as having an MDMT colder
than –78.5 °C (–109.3 °F).

Testing has demonstrated that dry ice still exists although the pressure is greater than the point where
it would exist if the contents were in an equilibrium condition. Even though some dry ice exists in the
container, it is likely that the pressure building vaporiser can be activated and the container returned to
service. Do not fill to the normal liquid carbon dioxide level. The first fill after a container has lost pressure
should not exceed 80% of normal full. This allows room for any residual dry ice to melt and convert to
liquid that will expand close to the normal 100% fill level. A container with residual dry ice will be overfull
at designed conditions if filled to the normal fill settings. The procedures suggested in this section only
apply to containers with an MDMT less than –78.5 °C (–109.3 °F).

12.5 Uninterruptible applications

There are special carbon dioxide container applications where large volumes of liquid or vapour are
discharged for fire protection, inerting, and purging. The design intent for fire prevention applications is
to discharge either a large portion or the entire liquid contents, of the container contents during a short
period. The container pressure will decrease while product is removed if no additional vaporisation is
provided. The typical range to which the pressure would decrease would be 1724 kPa (250 psi) to as
low as 1034 kPa (150 psi). This is typically a designed and expected condition, that may be less than
the MDMT, and is tolerable due to the coincident lower pressure and the low frequency of occurrence.
Operators of such systems shall use procedures in this publication to return any container that has
decreased to less than its MDMT to a safe and normal condition prior to refilling the container or
returning to normal service.

Some vapour inerting and purging applications protect containers or processes storing flammable or
explosive mixtures, which cannot withstand a supply interruption. Those systems typically have back
up measures to protect the container or process, but the designer should consider the expected failure
modes of the system and design accordingly. For some examples, see NFPA 86, Standard for Ovens
and Furnaces; API Standard 2000, Venting Atmospheric and Low-pressure Storage Tanks; or ATEX
Directive 2014/34/EU, Equipment and protective systems intended for use in potentially explosive
atmospheres [16, 17, 18].

22
EIGA DOC 164/20

13 Recommended re-pressurisation methods

13.1 Recommendations and continuous monitoring

The following recommendations are provided based on the information available at the time of
publication. Each instance needs to be evaluated by a qualified carbon dioxide technician. The
de-pressurisation of a container is an upset condition. The assumption is made that only a pressure
gauge, contents-level gauge, and liquid/vapour fill lines are available to the technician. It is also
assumed that little or no instrumentation is available; limited electric power or alternate heat sources
exist; cargo tanks are probably the only external sources of carbon dioxide vapour; and the container
needs to be returned to normal service as rapidly as possible.

Monitoring by a qualified carbon dioxide technician is required during re-pressurisation. Any sign of
leakage, unusual noise, or other unexplained occurrence during these procedures is reason to
discontinue re-pressurisation and take other appropriate action.

Method 1 followed by Method 2 is the preferred method under most circumstances. Methods 3 and 4
are alternatives that may be appropriate in some circumstances such as when Methods 1 and 2 are not
safe or practical given the container, site conditions, and equipment available.

The flow chart in Appendix C is provided as an aid in deciding the best method to use for
re-pressurisation.

13.2 Carbon dioxide gas pressurisation up to 690 kPa (100 psi) (Method 1)

NOTE This re-pressurising method can be used on most ASME-designed tanks but may not be applicable for
EN or other design codes with lower factors of safety. The user shall determine if this technique is acceptable
(see the examples in 10.2, Appendix A, and Appendix B to determine the extent of the safe domain).

This procedure is step one of a two-step process outlined here and in 13.3. It is used to partially liquefy
any dry ice inside a container when the pressure has decreased less than 416 kPa (60.4 psi).

Connect a hose from the vapour phase of a supply tank to the liquid phase of a de-pressurised container.
A manifold similar to Figure 7 is suggested. The de-pressurised container pressure control regulator
should be set at 690 kPa (100 psi), and the pressure relief regulator on the supply tank should be set
no less than 621 kPa (190 psi) or at the pressure coincident with the supply tank MDMT. Full-time
monitoring of pressure gauges and manual control of pressure and flow is an acceptable alternative
(Figure 7 alternative manual method). Purge the hose and manifold.

Pressurise the container to 690 kPa (100 psi) with carbon dioxide vapour from cargo tank(s) or other
external vapour source (see Table 5 for typical quantities/cargo tanks required). The pressure in the
cargo tank will decrease rapidly if there is no vaporiser, which is the reason that multiple cargo tanks
may be required. The residual liquid in the cargo tank will auto-refrigerate and should be maintained at
a pressure that will not subject the next delivery customer’s container to liquid colder than its MDMT.

Slowly open the valves connecting the supply tank and the de-pressurised container. A single supply
tank and vaporiser may be used as a vapour source instead of several cargo tanks.
CAUTION: Do not let the supply tank pressure fall below the pressure coincident with the MDMT of the
supply tank. Without an external pressure building vaporiser, the supply tank pressure can fall to the
point that the re-pressurisation operation must be stopped until the supply tank pressure is restored.
Large quantities of carbon dioxide can be required (see Table 5).

The external vapour can be added as fast as the piping and hoses allow. If the container liquid piping
is blocked by dry ice, the vapour equalisation line should be used (see Figure 7). The vapour
condenses, which causes the dry ice to melt. Adding vapour alone does not guarantee re-liquefying all
of the dry ice. The liquid level rises until all of the exposed dry ice is submerged. At this point, the
container pressure increases rapidly because the incoming vapour cannot contact the dry ice directly.
The carbon dioxide technician completing this step should expect the container pressure to increase to
the triple point (416.4 kPa [60.4 psi]) and hold at that pressure for an extended period of time and then
rapidly increase to the final 100 psi (689.5 kPa). The liquid level gauge could show a reading but is
probably not accurate.

23
EIGA DOC 164/20

When the vapour pressure in the de-pressurised container approaches 690 kPa (100 psi), do not
assume that the dry ice is completely melted. The container will have a significant amount of dry ice at
–56.6 °C (–69.9 °F) remaining. The rising pressure seems to indicate the entire contents are greater
than –56.6 °C (–69.9 °F), but experimentation has shown that the rate of condensation slows and the
pressure begins to rise when the dry ice becomes covered with liquid. As long as dry ice remains in the
container, the container is likely to be colder than its MDMT and should be treated accordingly.

PRESSURE
MANUAL RELIEF DEVICE
METHOD DEPRESSURIZED
CO2 CONTAINER

VAPOR

LIQUID

NORMAL
FILL DRY ICE
CONNECTIONS

CARGO TANK AUTOMATIC PRESSURE

RELIEF DEVICE
or CIRCUIT DEPRESSURIZED
CONTAINER
CO2 CONTAINER

VAPOR Closes at 190 Closes at

psig 100 psig
LIQUID VAPOR

NORMAL DRY ICE

FILL
CONNECTIONS

Figure 7 Method 1, Step 1 partial reliquification of solid carbon dioxide (dry ice) container
pressurisation with vapour up to 690 kPa (100 psi)

(Refer to 13.2 and 15.1)

The vapour pressurisation step described in the previous paragraph should not be used to increase the
container pressure greater than 690 kPa (100 psi), and the vapour supply container shall be maintained
greater than its MDMT. The first step of the re-pressurisation is now complete and the second phase
can begin (see 13.3).

The advantages of carbon dioxide gas pressurisation up to 690 kPa (100 psi) are:
• Carbon steel pressure vessels subject to pressure levels less than 690 kPa (100 psi) are unlikely
to fail in a catastrophic manner at dry ice temperatures. Table 4 indicates that a container with a
2410 kPa (350 psi) MAWP and a pressure of 690 kPa (100 psi) has a stress level in the steel wall
of 39.4 MPa (5714 psi). Therefore, it is safe to pressurise such a container to 690 kPa (100 psi) with
no risk of brittle fracture. At 690 kPa (100 psi), testing shows that there is enough liquid in the
container to allow liquid to be pumped as recommended in 13.3; and
• No lost product.

The disadvantages of carbon dioxide gas pressurisation up to 100 psi (690 kPa) are:
• Requires large volumes of vapour to partially re-liquefy the dry ice. To pressurise a container from
atmospheric pressure to 690 kPa (100 psi), the vapour required per unit mass of de-pressurised
liquid is 92.3 kg/tonne (185 lb/ton). In most cases, electric vaporisers are not large enough to
complete this step rapidly;
• Only practical carbon dioxide vapour source readily available is from cargo tanks. Typical cargo
tanks do not have a vaporiser or auxiliary heat source available, and therefore have a limited
quantity of vapour available. Full cargo tanks are the best source but can deliver no more than 50
kg of vapour per tonne of liquid (100 lb/ton). The vapour removed from cargo tanks is supplied by
the auto-refrigeration of the liquid carbon dioxide. Vapour removal shall be limited to keep the
pressure greater than the corresponding cargo tank MDMT; and
• Insufficient warming of liquid. It does not provide the circulation of the liquid to ensure that all the
dry ice is melted in a reasonable time, so recirculating liquid as described in 13.3 is necessary.

24
EIGA DOC 164/20

13.3 Recirculation of warmed liquid (Method 2)

This procedure is step two and shall be preceded by the one listed in Section 13.2 unless the container
pressure is equal to or greater than 690 kPa (100 psi).

NOTE Valves, nozzles, and piping can be blocked (or become blocked) with dry ice even after carbon dioxide in
the container is partially liquefied (see 9.2).

WARNING: Re-circulation of liquid causes the temperature and pressure of containers fabricated with
coarse grain steels to pass through the zone outside the ASME Code as illustrated in Figure 4 [1]. This
procedure requires continuous supervision by a qualified carbon dioxide technician to monitor pump
flow, heat input, and vessel protection from shock and/or impact for a slow, controlled pressure rise.

Liquid carbon dioxide is pumped from either the liquid fill or a liquid use line through a vaporiser/vapour
heater. The warmed liquid is returned to the container through the vapour fill connection (see Figure 8).
Typical pump capacities range from 7.6 l/min to 37.9 l/min (2 gal/min to 10 gal/min) and typical heater
capacities range from 3 kW to 18 kW. The preferred procedure is to pump liquid from one end of the
container and to return the warmed liquid to the opposite end, if such a connection is available.

The circulating operation should continue until the container pressure exceeds the pressure coincident
with the MDMT or 1380 kPa (200 psi). The product heating and circulation can be discontinued at this
time. When the pressure remains stable for 2 hours or is rising, the container contents should be at or
near equilibrium. The container then may be returned to service.

The container level gauge is typically not accurate until all the dry ice has melted.

Do not fill the container over 80% of rated capacity the first time after completing this procedure. This
allows sufficient volume for the expansion of the cold liquid if residual dry ice remains inside the
container. The container pressure and level should be monitored until normal operation is observed.

The advantages to re-circulation of warmed liquid are:

• Minimises the possibility that the vapour pressure in the container will exceed the equilibrium
pressure of the circulated liquid. Any dry ice in the container will gradually melt. The liquid circulation
causes a mixing action minimising temperature gradients throughout the container;
• Relatively fast – a container can be returned to normal service in one or more days;
• Uses equipment readily available within the carbon dioxide industry. This procedure can be
accomplished using only the two fill connections; and
• No lost product.

The disadvantages of recirculation of warm liquid are:

• Requires bringing extra equipment to the site, which adds set up time;
• Requires a compatible electric or energy supply with sufficient capacity to supply the pump and
heater. Most carbon dioxide containers have an electric supply for the refrigeration unit that can be
temporarily disconnected and used for the process; and
• Requires time varying from hours to days depending on the circumstances.

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EIGA DOC 164/20

Alternate return line

Pressure relief device

Depressurized CO2 container

Normal fill
connections

Pressure relief device Vapor

Alternate return
Bypass connections
Liquid Dry ice

Heater
Pump

Figure 8 Recirculation of warmed liquid to 1380 kPa (200 psi)

13.4 Hot gas warming at no pressure (Method 3)

This procedure is the safest for containers fabricated with coarse grain steels because it does not go
into the unsafe zone as illustrated in Figure 4.

Remove the container from service. If the container is greater than 416 kPa (60.4 psi), remove all the
remaining liquid carbon dioxide through a liquid connection (see 9.2). De-pressurise completely through
a vapour connection.

Inject large quantities of warm, dry air or gas through an open manway or product-use connections and
vent to the atmosphere.

Drain condensed moisture from the container and piping. Dry, clean, and purge after all the dry ice has
sublimed. Pressurise the container with carbon dioxide vapour and fill as required for a first fill (see CGA
G-6.4) [15].

The advantage of hot gas warming at no pressure is there are no container rupture hazards during the
heating process.

The disadvantages of hot gas warming at no pressure are:

• discharges all remaining carbon dioxide;
• can create large volumes of carbon dioxide gas creating a possible asphyxiation hazard;
• requires approximately 276 800 kJ/tonne (238 000 Btu/ton) of liquid in the container before
de-pressurisation if complete conversion to dry ice has occurred;
• requires cleaning and purging of the container to remove moisture and contaminants; and
• may require entry through the manway with confined space entry safety restrictions and procedures.

A variation of hot gas warming at little or no pressure is to reduce the tank pressure to near atmospheric
pressure and then use a compressor or blower to circulate and heat carbon dioxide vapour in a closed
loop. The pressure will increase as the dry ice sublimes, but the pressure rise is limited by a pressure
regulator set to near ambient pressure, relieving to atmosphere. See Figure 9.

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EIGA DOC 164/20

Figure 9 Circulation of warm vapour at no pressure to sublime dry ice (Method 3)

13.5 Unassisted natural re-pressurisation (Method 4)

Remove the container from service, close all valves, and install a pressure control device to maintain
the container’s pressure at 690 kPa (100 psi). Ambient heat entering through the insulation will melt the
dry ice and warm the resulting liquid to normal operating conditions.

This is a slow and gradual process. Pressure cannot be used to determine the liquid temperature during
re-pressurisation because dry ice and colder liquid tend to settle to the bottom of the container. This
could maintain the temperature at the bottom of the container at the triple point irrespective of the
pressure. This method should only be used if the pressure in the container is limited to 690 kPa
(100 psi) (see Note 1 and 2 of Table 4).

The advantage of unassisted natural re-pressurisation is that it is self-regulating.

The disadvantages of unassisted natural re-pressurisation are:
• It is extremely slow;
• May require up to 30 days depending upon the quantity of product, the ambient temperature, and
the quality of the insulation; and
• May take longer in a vertical container than in a horizontal container. While both types of containers
can stratify (cold liquid or dry ice below a warm upper layer of liquid), vertical containers are
especially prone to this condition.

14 Re-pressurisation methods—not recommended

Some of the following procedures are known to have been used for re-pressurisation in the past. Actual
tests performed by CGA indicated that they are ineffective or unsafe and are therefore not
recommended.

14.1 Transfer liquid carbon dioxide into the container to melt the dry ice and warm the liquid—
not recommended

The reasons that this method is not recommended are:

• Only works with partially filled containers (approximately 10% full before de-pressurisation). More
than a full 20 tonne carbon dioxide trailer is required to restore a 50 tonne container back to service
if it contains 10% of liquid just before de-pressurisation;
• No assurance that all the dry ice will melt after the liquid is added. The container can become
overfilled after the dry ice melts; and
• May not be able to inject liquid through lines blocked by dry ice.

27
EIGA DOC 164/20

14.2 Pressure building vaporiser/internal heater method only—not recommended

The reasons that this method is not recommended are:

• Dry ice can still exist in areas away from the heater. The container pressure will not reliably indicate
product and container temperature;
• Can rapidly increase the vapour pressure in the container without melting the dry ice or warming
the liquid in areas away from the heater;
• No liquid circulation to melt dry ice or warm liquid away from the vaporiser; and
• Can cause the heating element to overheat or burn out inside an extremely cold and brittle
container. Dry ice in the liquid supply piping (see 9.2) to an external vaporiser or the bridging of dry
ice surrounding the internal heater could prevent the heater from being properly submerged in liquid
causing overheating.

14.3 Transferring carbon dioxide vapour into the vapour connection of the de-pressurised
container—not recommended

The reasons that this method is not recommended are:

• Will warm up container contents only when incoming vapour can directly contact dry ice or snow.
The pressure rises rapidly when dry ice is covered by liquid, and further melting of the dry ice or
warming of the liquid is extremely slow;
• Cannot restore container to service by this method alone; and
• Does not promote any mixing of the liquid.

14.4 Remove liquid carbon dioxide from the container and transfer to cargo tanks—not
recommended

The reasons that this method is not recommended are:

• requires contents to be in a liquid state before transfer;
• requires cargo tanks with a suitable MDMT; and
• requires a container with a suitable MDMT to receive the cold liquid from the cargo tank.

14.5 Manual removal of dry ice—not recommended

The reasons that this method is not recommended are:

• freezing and asphyxiation hazards to personnel; and
• requires confined space entry procedures

15 Suggested measures to prevent container de-pressurisation

Owners and operators of carbon dioxide containers should consider installing safeguards and alarm
measures to avoid a loss of pressure. Most of these events are caused by excessive vapour withdrawal
from the container which in many cases is linked to a loss of vaporisation capacity. Depending on the
application and equipment specifications, one or more of the following measures may be considered for
installation, see Figure 10.

15.1 Backpressure regulating valve

Install a back-pressure regulating valve on the vapour use line, set greater than or equal to a pressure
corresponding to the MDMT of the container (1379 kPa [200 psi] setpoint for an MDMT of –28 °C
[–20 °F]). The regulator would close at container pressures no less than the corresponding minimum
designed allowable operating temperature, shutting off flow of carbon dioxide from the container.

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EIGA DOC 164/20

15.2 Direct to process vaporiser

System designers should consider use of direct to process vaporisers for high vapour use. Withdrawing
vapour from the top of the container relies on the pressure building vaporiser. The pressure building
vaporiser may not be adequate to maintain container pressure at high vapour withdrawal rates.

15.3 Low pressure alarm

Install an audible and/or visual low-pressure alarm connected to the container head space to locally
alert the operator of low container pressure. This is typically set at a pressure corresponding to a
temperature greater than the MDMT and less than the pressure building vaporiser range to allow the
operator time to apply corrective action.

15.4 Remote monitoring

Install local or external telemetry that will generate a low-pressure alarm at a monitored location in order
to dispatch a carbon dioxide technician to diagnose the cause of the low container pressure.

15.5 Diverter valve on pressure relief devices

Replace a single PRD with a 3-way diverter valve and dual PRDs to allow isolation of a defective PRD
failed in the open position. This is in reference to the main container PRD, not ancillary PRDs such as
PRDs on the pressure building vaporiser.

15.6 Pressure relief device discharge piping design

Evaluate discharge piping orientation and configuration on PRDs to prevent thrust caused by
discharging PRDs from unscrewing or damaging the PRDs. This could cause the PRDs to detach from
the container or fail in the open position, resulting in the loss of container pressure.

Orient discharge piping to prevent

HV12 unscrewing or damage of PRD (TYP)
PCV5
200 psi

Vapor
to
customer
Antenna

PSL Carbon dioxide

PTL 4
container
6
Telemetry

E100

Vapor
to
customer
E200
NOTE For additional details and equipment, see CGA G-6.1, Standard for Insulated Liquid Carbon Dioxide
Systems at Consumer Sites [19].
TAG No Item Function
E100 Pressure building vaporiser Allows limited vapour withdrawal
E200 Direct-to-process vaporiser Allows high vapour withdrawal
PCV5 Back pressure regulating valve Stop vapour removal at low pressure

29
EIGA DOC 164/20

PSL4 Low pressure alarm Alert user to low pressure

PTL6 External telemetry Alert technician of low pressure
HV12 3-way diverter Allows relief device replacement

Figure 10 Typical protective measures to prevent container de-pressurisation

15.7 Signage

Install warning signage on the container indicating normal operating pressure and the dangers of low
operating pressure/temperature. Examples of a sign appropriate for a tank with an MDMT of –29°C
(–20 °F) are shown in Figure 11.

DO NOT OPERATE TANK AT DO NOT OPERATE TANK AT

PRESSURES LESS PRESSURES LESS
THAN 200 psi (-20F) THAN 1379 kPa (-28C)
Call 1-800-xxx-xxx Call 1-800-xxx-xxx

Figure 11 Examples of caution signage

16 References

Unless otherwise specified, the latest edition shall apply.

[1] ASME Boiler & Pressure Vessel Code, American Society of Mechanical Engineers,
www.asme.org

[2] EN 13445-3 Unfired pressure vessels. Part 3 Design, www.cen.eu

[3] EN 13458-2, Cryogenic vessels—Static vacuum insulated vessels–Part 2 Design, fabrication,

inspection and testing, www.cen.eu

[4] AD 2000 Merkblatt W10 Werkstoffe für tiefe Temperaturen Eisenwerkstoffe, Carl Heymanns
Verlag KG, Luxemburger Strasse 449, D-50939 Cologne

[5] CGA P-11, Guideline for Metric Practice in the Compressed Gas Industry, Compressed Gas
Association, Inc. www.cganet.com

[6] ASTM A370, Standard Test Methods and Definitions for Mechanical Testing of Steel Products,
ASTM International. www.astm.org [PC 27576]

[7] EN 10028-1, Flat products made of steels for pressure purposes - Part 1: General requirements
www.cen.eu

[8] Quinn, E.L. and Charles L Jones, Carbon Dioxide, p. 97, American Chemical Society Monograph
Series, Reinhold Publishing Corp. www.umi.com

[9] Code of Federal Regulations, Title 29 (Labor) Part 1910, U.S. Government Printing Office.
www.gpo.gov

[10] EIGA Doc 919, Guidelines for the Preparation of Safety Data Sheets, European Industrial Gases
Association, Inc. www.eiga.eu

[11] EIGA SI 24 Carbon Dioxide Physiological Hazards – “Not just an Asphyxiant”, European
Industrial Gases Association, Inc. www.eiga.eu

[12] NFPA 55, Compressed Gases and Cryogenic Fluids Code, National Fire Protection Association.
www.nfpa.org

30
EIGA DOC 164/20

[13] CGA G-6, Carbon Dioxide, Compressed Gas Association, www.cganet.com

[14] CGA PS-5, CGA Position Statement on the Suitability of Carbon Steel Containers for Stationary
Carbon Dioxide Storage, Compressed Gas Association, Inc. www.cganet.com

[15] CGA G-6.4, Safe Transfer of Liquefied Carbon Dioxide in Insulated Cargo Tanks, Tank Cars, and
Portable Containers, Compressed Gas Association, Inc. www.cganet.com

[16] NFPA 86, Standard for Ovens and Furnaces, National Fire Protection Association. www.nfpa.org

[17] API Standard 2000, Venting Atmospheric and Low-pressure Storage Tanks, American Petroleum
Institute. www.api.org

[18] ATEX Directive 2014/34/EU, Equipment for potentially explosive atmospheres, European
Commission. www.ec.europa.eu

[19] CGA G-6.1, Standard for Insulated Liquid Carbon Dioxide Systems at Consumer Sites,
Compressed Gas Association. www.cganet.com

[20] EN 13445-2, Unfired pressure vessels – Part 2: Materials, www.cen.eu

[21] EN 10028-3, Flat products made of steels for pressure purposes—Part 3: Weldable fine grain
steels, normalized, www.cen.eu

17 Additional references

EN 14197 Parts 1-3, Cryogenic vessels—Static non-vacuum insulated vessels, www.cen.eu

EIGA Doc 66, Refrigerated CO2 storage at users' premises, European Industrial Gases Association.
www.eiga.eu

31
EIGA DOC 164/20

Appendix A—EN pressure vessel material design information

(Informative)
A1 EN standard pressure vessel

Both EN examples in Figure A-1 illustrate a 33 ton carbon dioxide pressure vessel, service pressure =
22 bar, outside diameter = 2460 mm, minimum wall thickness = 11.8 mm. Example 1 is manufactured
with a steel having a minimum impact value of 27 J at –40 °C with an MDMT of –81 °C based upon
Figure A-2. Example 2 is manufactured with a steel having a minimum impact value of 27 J at –20 °C
with an MDMT of –61 °C based upon Figure A-2. Information for Examples 1 and 2 are labelled with a
number 1 and number 2 inside of a red rectangle in the diagrams. In both cases, the vessels have not
been post weld heat treated.

Figure A-1—EN allowable MDMT conditions for a carbon dioxide container being re-pressurised

Determine the guaranteed impact properties of the steel at the lowest temperature in the material
certificate or the material standard; in Example 1 it is 27 J at –40 °C and in Example 2 it is 27 J at
–20 °C.

Determine the wall thickness of the tank, the guaranteed yield stress (Re) of the steel used and whether
the vessels has been heat treated after welding; for both examples given in Figure A-1 with no post
weld heat treatment, Re = 355 N/mm2 and thickness equal to 11.8 mm.

For Example 1, the vessel can be operated at temperatures lower than –81°C, but only when the stress
levels are less than 50 MPa per EN 13445-2, Unfired pressure vessels – Part 2: Materials [20]. For
Example 2, the vessel can be operated at temperatures lower than –61°C, but only when the stress
levels are less than 50 MPa in accordance with EN 13445-2 [20].

The pressure that corresponds to a stress (S) of 50 MPa can be determined using the following formula:

P = S • 2e
D

Where:

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EIGA DOC 164/20

P = 0.48 MPa (4.8 bar) internal pressure

S = 50 MPa (stress level where lower operating temperature is allowed)

e = 11.8 mm wall thickness

D = 2460 mm diameter

EN 13445-2 allows the operation of pressure vessels 40 °C colder than the MDMT as long as the wall
stresses are less than 50 MPa [20]. The vessel in Example 1 could operate as cold as –121 °C at
pressures less than 4.8 barg, which is well below the coldest dry ice temperature of –78 °C (i.e., –81 °C
MDMT – 40 °C allowable temperature reduction = –121 °C minimum operating temperature at reduced
pressure). The vessel in Example 2 could operate as cold as –101 °C at pressures less than 4.8 barg,
which is well below the coldest dry ice temperature of –78 °C (i.e., –61 °C MDMT – 40 °C allowable
temperature reduction = –101 °C minimum operating temperature at reduced pressure).

The labelled lines in Figure A-1 were determined using EN 13445-2. Any operating conditions colder
than –81°C (for Example 1) and greater than 4.8 barg would be in the brittle zone according to the EN
13445-2. Any operating conditions colder than –61°C (for Example 2) and greater than 4.8 barg would
be in the brittle zone according to EN 13445-2 [20]. The brittle zone as shown by the shaded area, for
Example 1, in Figure A-1 shall be below the temperature/pressure curve for carbon dioxide (red dotted
line) to allow safe operation of the tank during re-pressurisation. As shown in Figure A-1, for Example
1, the blue line is above the shaded area: Method 1 can be used in this example. As shown in Figure
A-1, for Example 2, the blue line starts below the shaded area: Method 1 cannot be used in this example;
either Method 3 or 4 shall be used.

Test thickness (mm)

Actual temperature (°C)

Charpy test (>=27J) temperature (°C)

Figure A-2—Design reference and impact test temperatures as welded condition for and
EN pressure vessel, 310 N/mm2 < Rp ≤ 360 N/mm2 : 27 J

310 N/mm2 < Rp ≤ 360 N/mm2: 27 J

Rp = proof stress
NOTE In example 1, the minimum acceptable temperature according to the material certificate is –40 °C, but
because the wall thickness of the tank is approximately 10 mm, the tank can be used at normal stress (or service
pressure) down to –81 °C. In example 2, the minimum acceptable temperature according to the material
certificate is –20 °C, but because the wall thickness of the tank is approximately 10 mm, the tank can be used at
normal stress (or service pressure) down to –61° C.

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EIGA DOC 164/20

A2 AD 2000 Merkblatt pressure vessel

Check the type of the tank material and guaranteed impact properties of the steel at the lowest
temperature in the material certificate or the material standard; for example, fine grained steel P355ML1
its impact properties are 27 J at –40 °C [4].

Check the MAWP and wall thickness of the tank and if the tank has been heat treated after welding; for
example, no heat treatment and thickness equal 11.8 mm.

Select the load case for the lowest expected operation temperature for the tank material on AD 2000
Merkblatt W10, Table 1, Column 4, 5, or 6 which will be –78.5 °C if dry ice is in the tank: for example,
load case II has to be considered for the material P355NL1 because it allows a lowest operation
temperature of –110 °C [4].

NOTE Load case II may be selected for all low temperature fine grained steels of the grades P355NL1/2 or
P355ML1/2 according to EN 10028-3, Flat products made of steels for pressure purposes—Part 3: Weldable fine
grain steels, normalized, because their allowable operating temperature is less than –90 °C [21].

Select the allowable pressure loads for the tank based on the wall thickness of the tank shell and their
heat treatment according to AD 2000 Merkblatt W10, Table 2 and/or Clause 3 [4]. As a general rule
heat treatment is not required for wall thicknesses less than 20 mm if the test certificate shows sufficient
impact properties for low temperature as required in the material standard.

The required test temperature is also indicated in Table 1, Column 9 of AD 2000 Merkblatt W10 [4].
Example for the material P355NL1 is –40 °C.

For wall thicknesses equal or less than 10 mm the allowable pressure load is limited up to 75% of the
calculation pressure (MAWP).

For wall thicknesses greater than 10 mm and equal or less than 20 mm the allowable pressure load is
limited up to 50% of the calculation pressure (MAWP): for example, a tank with a thickness of 11.8 mm
and a MAWP of 22 bar may be pressurised up to 11 bar.

NOTE Load case I is allowed for temperatures less than the triple point for some materials. Nevertheless, the
allowable pressure in the tank should be only increased during the re-pressurisation procedure if the temperature
of the tank wall is measured and well above the allowable value.

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EIGA DOC 164/20

Appendix B—ASME Boiler and Pressure Vessel Code, Section VIII, Division 1
Rules for Construction of Pressure Vessels [1] (Informative)

B1 General
An assessment of an ASME coded vessel to determine if the re-pressurisation methods in this
publication are suitable for a given pressure vessel can be performed using industry experience or more
formal methods. For carbon steel vessels a common assessment method would be to use the UCS-66
“Materials” section of the ASME Code. That is the method this appendix will discuss, as the resources
and personnel to perform this analysis are widely available. When appropriate, an assessment using
methods such as API-579, ASME Code Section XI or other brittle fracture mechanics analysis method
can be performed.

ASME Code stamped pressure vessels currently in service vary in the Edition and Addenda they were
built to. The materials of construction also vary. The first step in assessing an ASME coded vessel is to
acquire information regarding the construction, manufacture, repair, or alteration of the vessel. This
shall include a copy of the ASME Data Report and a copy of any National Board Reports on Repairs or
Alterations. This could also include a photo of the ASME nameplate and a photo of any Repair or
Alteration nameplates. A copy of the fabrication drawing is very useful, but unless the Data Report is
unclear, not necessary. Obtaining other information on the size of the vessel, horizontal or vertical, etc.
will allow judgements to be made about the accuracy of the information acquired.

This appendix discusses pressure vessels manufactured using carbon steel shell and head materials,
permitted by section UCS of the ASME Code. Pressure vessels manufactured using materials permitted
by section UHT of the ASME Code can be assessed using similar methods to those used for UCS
material but are outside the scope of this appendix. Section UHT materials are more likely to be
encountered in cargo tank applications than in stationary tank applications. Pressure vessels using
austenitic stainless steel for the shell and heads frequently have lower MDMTs than carbon steels and
are beyond the scope of this appendix. Section UHA of the ASME code should be consulted for
austenitic stainless-steel vessels.

When assessing an ASME pressure vessel to determine the applicability of this document, it is best to
obtain guidance from someone familiar with the code and in particular UCS-66 since the ASME Code
has varied over the years. The example in this appendix is specific to a particular edition/addenda of
the code. In evaluating other designs, other editions/addenda of the code may apply.

Pre-1987 carbon steel pressure vessels, including for carbon dioxide service, were assigned a generic
MDMT of –20 °F. Prior to 1987, the ASME Code required the material to be Charpy impact tested for
any pressure vessel that had an MDMT colder than –20 °F. When a generic –20 °F MDMTs has been
applied, a more sophisticated analysis may need to be performed.

The thickness, material specification and heat treatment of each of the materials in the pressure vessel
must be determined prior to using UCS-66. The heat treatment of usual concern is whether the material
is normalised or not, and whether the vessel is post weld heat treated. If normalizing has not been
performed the steel is considered as-rolled. SA-612 and SA-516 are available either as-rolled or
normalised and both have been used in vessels for liquid carbon dioxide service. If the ASME Data
Report does not state the material is normalised it is considered as-rolled.

At equilibrium conditions, for liquid carbon dioxide service, the colder the vessel’s internal temperature,
the lower the vessel’s internal pressure. The lower vessel internal pressure produces a lower required
thickness in the vessel components. Since the wall thickness does not change, this can allow lower
MDMTs at lower pressures, which may be colder than the MDMT shown on the pressure vessel data
plate.

When assessing each component of a pressure vessel, it is necessary to determine the Figure UCS-66
curve its material belongs to. See Table B-1 for the curve listed for the material/heat treatment condition
combinations listed.

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EIGA DOC 164/20

NOTE SA-212 is a material removed from the ASME Code long before UCS-66 was added to the code. Its
assignment to Curve A is based on industry reference material. The use of UCS-66 for a vessel made using SA-
212, would need the concurrence of the person performing the UCS-66 assessment.

Table B-1— Example on UCS-66 curve selection

Material Specification Heat Treatment Status UCS-66 Curve

SA-212 As-rolled Curve A

SA-515-70 As-rolled Curve A
SA-516-70 As-rolled Curve B
SA-612 As-rolled Curve B
SA-516-70 Normalized Curve D
SA-612 Normalized Curve D

B2 UCS-66 Example

The ASME Code example in Figure B-1 illustrates a UCS-66 review of a horizontal 30 ton pressure
vessel in liquid carbon dioxide service, manufactured to the 2015 Edition of the ASME Code. The
pressure vessel has a MAWP of 350 psi with a normal operating pressure in the 280 psi to 310 psi
range. The inside diameter is 78 in with the shell having a nominal thickness of 0.61 in and the 2:1
elliptical heads having a minimum thickness of 0.60 in. Radiography has been performed to allow the
shell long seams and heads to have a joint efficiency of 1.0. In this example, the pressure vessel was
designed with no corrosion allowance (corrosion allowance equals 0.0 in). The shell and heads are
made of SA-612, normalised steel (no impact testing performed). SA-612 normalised steel is listed as
a Curve D material in the notes to Figure UCS – 66 “Impact Test Exemption Curves”.

Figure B-1—Allowable MDMT conditions for the carbon dioxide container in this example
being re-pressurised

The MDMT of this vessel at 350 psi using UCS-66 is –51 °F. In this example the shell governs for
MDMT, i.e. the shell is the component with the warmest MDMT and all other pressure parts have an
equal or colder MDMT. Per Figure UCS-66, 0.61 in Curve D material has a MDMT of –49.7 °F. The
required shell thickness for this vessel with a MAWP of 350 psi plus a hydraulic head of 3 psi is

36
EIGA DOC 164/20

0.6015 in. Figure UCS-66.1 allows a colder MDMT when the ratio of the required thickness to the
nominal/minimum thickness is less than 1.0. Using the ratio of 0.6015/.61 = .98606, Figure UCS-66-1
allows a further reduction of 1.5 °F in the MDMT. The final MDMT at 350 psi is –49.7 + –1.5 = –51.2
which is rounded to –51 °F.

Line 2 in Figure B-1 follows the same process in the previous paragraph, only increments of lower
pressure are used to determine the required shell thickness at each pressure increment. The ASME
code only allows MDMTs of –55 °F and warmer until the stress level is reduced to 35% of allowable
stress. Line 1 in Figure B-1 is a plot of the coincident saturation temperature of liquid carbon dioxide
versus the pressure at that temperature. For liquid carbon dioxide service, the colder the vessel’s
internal temperature, the lower the vessel’s internal pressure. The lower vessel internal pressure
produces a lower required thickness in the vessel components which can allow lower MDMTs, at the
lower pressures, than the MDMT shown on the pressure vessel data plate.

The 2015 Edition of the ASME Code allows a MDMT no lower than –155 °F when the ratio of required
thickness to nominal/ minimum thickness is 35% or less. (The 35% ratio applies to the vessels built to
the 1998 Edition, 1999 Addenda through the current code. A 0.40 ratio would apply to vessels built to
the 1987 Edition, No Addenda through the 1998 Edition, No Addenda). For this example, 35% of 0.61
= 0.2135 in. This vessel at 0.2135 in thickness would allow a design pressure of 126 psi, minus a 3 psi
hydraulic head, would give us a pressure gauge reading of 123 psi. Therefore, Line 2 in Figure B-1 has
a vertical drop from –55 °F to –155 °F at 123 psi.

A review of Figure B-1 shows the pressure vessel’s ASME allowable MDMT boundary (Line 2) is colder
than the pressure/temperature relationship for this re-pressurisation procedure shown in Line 3.
Therefore any of the methods for re-pressurisation presented in this publication could be used on this
pressure vessel.

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EIGA DOC 164/20

Appendix C—Flow chart for Methods 1 through 4

Figure C-1—Decision process for tank re-pressurisation per Section 12 and 13

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EIGA DOC 164/20

Figure C-2—Method 1 re-pressurisation with vapour then Method 2, circulate liquid per 13.2
and 13.3

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EIGA DOC 164/20

Figure C-3—Method 3 re-pressurisation by hot warming at no pressure per 13.4

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EIGA DOC 164/20

Figure C-4—Method 4 re-pressurisation by natural ambient heat gain per 13.5

41