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ASU-12-11-BOC

ASU Hydrocarbon Safety and Reboiler Operation

ASU Hydrocarbon Safety and Reboiler Operation


Purpose and Scope
Hydrocarbon Safety
Background
Air Contaminants
Sources of Hydrocarbons
Carbon Dioxide and Nitrous Oxide Contamination
Hazards of Hydrocarbons
Control and Removal of Hydrocarbons
Re-boiler Sump Analysis
Contaminant Action Levels
Inlet Air Analysis
Testing for Hydrocarbons
Acetylene Testing
Plant Operation at High Oxygen Purity
Hydrocarbon Risk Assessment
Condenser / Re-boiler Operation
Types of Re-boiler
Dry and Dead-End Boiling
Re-boiler Operation
Documents Referenced

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Purpose and Scope


Purpose

This chapter describes the hazards from hydrocarbon accumulation in ASUs. It explains the sources
and accumulation of contaminants and the actions that should be taken to minimise the hazard.

Scope

This chapter applies to ASUs and cryogenic oxygen generators across BOC worldwide. The target
audience is operators, managers and engineers.
Although the mandatory requirements in this standard do not strictly apply to other re-boilers within
air separation plants, such as argon re-condensors and main re-boilers in nitrogen generators, the
general principles and recommendations do apply.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Hydrocarbon Safety
Background
General

Two major incidents occurred in the air separation industry in 1997 at Bintulu in Malaysia and
Fuchun in China. To see a picture of the Bintulu incident, click here.

The exact cause of these events is complex, however both developed in the re-boilers and were the
result of hydrocarbon accumulation coupled with operating issues in the re-boilers. The events
involved explosive combustion of aluminium used in the construction of the re-boilers and
distillation column and caused destruction of the ASU and injuries and extensive damage in areas
outside of the ASU. Both plants used a low-pressure gas compression cycle with minimal liquid
purges and with Molecular Sieve PPUs for the removal of moisture and carbon dioxide at the front
end. Other design and operating features of the plants and local atmospheric contamination
contributed to the severity of the incidents.
As a result of these incidents an Operations and Engineering Directive No. 06/99 'Hydrocarbon
Contamination in ASUs' was issued. Material from this directive is incorporated into this chapter.
The material in this chapter has been kept up-to-date with best practice from the industry and should
always take precedence over the content of the O&ED where any discrepancies exist.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Accumulation of
hydrocarbons

Hydrocarbons entering ASUs accumulate in a number of areas:

main re-boiler

oxygen evaporators ( eg ICO T-38)

rich liquid adsorbers

liquid oxygen adsorbers

dead legs in the piping (as a result of localised boiling leading to contaminant concentration).

If the concentration of these hydrocarbons is allowed to build, potentially explosive mixtures can be
formed.

Localised
hydrocarbon
accumulation

Plugging components such as carbon dioxide and nitrous oxide can accumulate to the point where
they are deposited as solids and thus potentially block exchanger passes. These blockages in turn can
lead to localised hydrocarbon accumulation.

Air Contaminants
Contaminants in
air feed

Safe design and operation of a cryogenic air separation plant depends on proper management of
contaminants as they pass into and through the ASU. The bulk of the air and some trace components
are separated to yield desired products such as oxygen, nitrogen, argon, as well as helium, neon,
krypton or xenon. Some components freeze out at cryogenic temperatures and could cause
operational or safety problems due to blockage of small passages or tubes. Other components can be
concentrated within the air separation plant and form flammable mixtures with oxygen or enriched
air. Still other components may be corrosive and lead to increased operating problems and reduced
plant life.
The table below lists many components present in air that could cause problems in air separation
plants. The components are classified according to the primary problems they cause.

Plugging Components

Flammable or Reactive Components

Corrosive Components

Moisture (H2 O)

Methane (CH4 )

Sulfur Dioxide (SO2 )

Carbon Dioxide (CO2 )

Acetylene (C2 H2 )

Sulfur Trioxide (SO3 )

Nitrous Oxide (N2 O)

Ethylene (C2 H4 )

Hydrogen Sulfide (H2 S)

Ethane (C2 H6 )

Chlorine (Cl2 )

Propylene (C3 H6 )

Hydrochloric Acid (HCl)

Propane (C3 H8 )

Ammonia (NH3 )

Oxides of Nitrogen (NOx )

Other Chlorides

Ozone (O3 )

Other Sulfur Compounds

Other hydrocarbons including aerosols of non-volatile


hydrocarbons (eg. wood smoke)

Corrosive
components

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Corrosive components have the potential to chemically attack the materials exposed. Corrosion may
weaken the affected equipment and in addition corrosion products could build up and plug up critical
equipment. However this is rare and in terms of re-boiler safety the risks are low and therefore the
corrosive components will not be considered further in this document.
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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Plugging and
Flammable or
Reactive
components

Plugging components, while not safety issues by themselves, can accumulate and cause dry boiling
or dead end boiling and hydrocarbon buildup in re-boilers. Dry boiling is a process where a liquid is
fully vaporised causing all of the higher boiling point components in the liquid to concentrate and
precipitate.
Hydrocarbons or plugging components entering the cryogenic section of the plant will accumulate in
the re-boilers sumps. If contaminant concentrations are allowed to build up, they can form explosive
mixtures with oxygen or, in the case of inert contaminants, solidify and plug passages of the reboiler once their solubility limits have been reached locally. Such plugging by inert contaminants
can lead to local accumulation of hydrocarbons.
Note that hydrocarbons might also accumulate at other locations such as:

rich liquid adsorbers,

LO adsorbers,

vaporising product circuits of main heat exchangers,

and through dead end boiling in piping dead legs.

It is therefore essential that the more hazardous of these contaminants be removed from the feed air
stream before they enter the distillation column, and that the maximum concentration for the
remaining contaminants is limited, particularly in column sumps and re-boilers.
See: Condenser / Re-boiler Operation (Page 21).
Alarm levels and
actions for
continuous
analysis

Where continuous air analysis is fitted to a plant an alarm should be set at three times the design, or
normal, level of the contaminants being measured.

Trip levels and


actions for
continuous
analysis

The plant must be shut down if the level of the contaminants being measured rises to ten times the
design, or normal, level for more than one hour.

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If the alarm level is exceeded, monitor the impact on the plant through regular sump analysis
focussing on hydrocarbons, carbon dioxide and nitrous oxide.

The plant must be shut down immediately if the level of contaminants rises to 20 times the design,
or normal, level.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Sources of Hydrocarbons
Areas of high
pollution

ASUs are generally designed for normal atmospheric contamination levels. The air should be
analysed before the plant is designed and built, and a survey and risk assessment should be
undertaken of the location of the plant relative to contamination sources.
Where the plant is located in close proximity to acetylene plant, chemical plant or refineries a
risk assessment is especially important even where the normal level of contamination in air is
low.
These plants will have fault conditions where venting of product is inevitable and this should be
anticipated.
An assessment of the potential for local industry to contaminate the air should be undertaken
annually or sooner if new sources of potential pollutants are identified.
Analysers for detecting hydrocarbons and nitrous oxide are not routinely installed on ASUs but
should be considered, especially on plants with low (<10%) liquid purge rates, as part of the
hydrocarbon risk assessment.

Hydrocarbon
The hydrocarbons methane, ethane, ethylene, acetylene, propane and propylene are commonly found
concentrations in in air. A survey of several ASU sites has found the following average and maximum concentrations.
air
The table illustrates the wide variation between average and maximum concentration. Plant design

will normally have allowed for short periods of operation (typically 2 hours in 24 hours) at the
higher concentration.
Component

Combustion
products

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Average concentration
(vpm)

Maximum concentration
(vpm)

Methane

2.0

26

Acetylene

<0.05

0.6

Ethylene

<0.05

2.6

Ethane

<0.05

4.6

Propylene

<0.05

0.9

Propane

<0.05

9.8

Butane

<0.05

9.5

Combustion products contain the following components at higher level than in normal air:

carbon monoxide, CO

methane, CH4

other hydrocarbons, CxHy

nitrous oxide, N2 O

carbon dioxide, CO2 , and

aerosols.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Aerosols

Aerosols are particles with diameters of 0.1 micron or below. The potential sources of aerosols
include airborne contaminants and lube oil from machines. These particles are only effectively
removed by electrostatic precipitation and so are not necessarily removed in the air separation
process.
If haze appears as a consequence of combustion, particularly if present for days rather than hours,
extreme caution should be exercised. In such cases, the following actions are recommended:

operate the re-boiler at full submergence,

maximise purge rates to reduce contaminant concentrations, and

increase the frequency of the sump liquid analysis.

Recent industry research has concluded that the purge is not effective in removing aerosols from the
bath and that aerosols are not removed during deriming (thawing), therefore the plant ultimately has
a lifetime limit for aerosols introduced into the plant.
Therefore continued operation in an atmosphere of haze presents additional risk and guidance should
be sought from the Process Safety Peer Team or Group SHEQ.

Hydrocarbon
solubility

Most hydrocarbons have low solubility in liquid oxygen.


When the concentration of the hydrocarbon exceeds its solubility limit in liquid oxygen, a second,
usually solid, phase is formed. This causes the hydrocarbon to accumulate until hazardous quantities
may be present.
Acetylene has a solubility in liquid oxygen of about 5 vpm. Above this concentration (called the
solubility limit), solid acetylene will be formed and an explosion hazard will be created.
Conversely, methane and ethane mix completely with liquid oxygen so that no second phase is
formed whatever the concentration.
Ethylene, propane and higher molecular weight hydrocarbons may occur in concentrations above
their solubility limit and can create a hazard.

Contaminant
accumulation

Contaminants which are not removed by the PPU or cryogenic adsorbers will pass through the
heat exchangers and distillation system to the oxygen re-boiler sump of the low pressure
column . Because they are essentially insoluble in cryogenic oxygen gas they will accumulate in the
oxygen liquid and will only be removed in the liquid oxygen stream leaving the sump. For example,
if the liquid oxygen purge is 0.5% of total oxygen production (approximately 0.1% of air feed) then
the sump concentration of contaminant will be 1000 times that in the air feed to the cold box.
The exception to this is methane which is sufficiently soluble in oxygen vapour to be removed with
the oxygen gas product.

Non-combustible
contaminants

Other noncombustible contaminants, such as water vapour, nitrous oxide and carbon dioxide also
have low solubilities and may block passages in:

heat exchangers, or

the condenser / re-boiler.

Partial or complete blockage of oxygen vaporising exchangers can result in safety problems because:

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the surface of the exchanger may be allowed to boil dry, and

hydrocarbon accumulation in the exchanger may result, even if the hydrocarbon is soluble in
the sump liquid. The hydrocarbon accumulation can lead to an explosion.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Sources of
contamination

Major sources of air contamination to air separation plants are:

vents

stacks

flares

disposal areas

process leaks

exhaust from internal combustion engines, generators or boilers

lubrication system vents, and

any other combustion processes.

Chemical and petroleum processes on adjoining properties, and other processes within the air
separation plant complex site, must be carefully considered as possible contamination contributors.
Acetylene-generating equipment, and carbide storage and disposal, must not be located in proximity
to air separation plants. The location of liquid fuel stores should be considered carefully to avoid
risk either to the ASU or to the fuel store from an incident at the ASU.

Air intakes

Air intakes to the plant should be protected from the ingestion of local contamination from sources
of combustion products. To decrease the discharge of contaminants in the immediate vicinity of the
plant air intakes, signs must be posted that prohibit parking or operation of internal combustion
engines.
Vehicles, diesel engines or other fume producers such as:

fires,

incinerators, or

boilers

must not be allowed to operate continuously within 30 metres (98 feet) of an air compressor intake.
Where unavoidable on RHE plants, continuous acetylene tests must be taken at the air separation
unit.
Painting in the vicinity of a compressor air intake is only allowed under controlled conditions.
Propane tankers, whether full or empty, must not be parked within 30 metres of an air compressor
intake.

Incomplete
removal of
contaminants by
PPUs

PPUs are designed to remove water and carbon dioxide from the inlet air to the ASU. They also
completely remove hydrocarbons acetylene, propylene and butane and partially remove ethylene
propane and nitrous oxide. The PPU does not remove methane, ethane or aerosols.
Maloperation or excessive extension of the PPU cycle may lead to breakthrough of carbon dioxide.
This is also an indication of possible breakthrough of nitrous oxide and hydrocarbons, in particular
ethylene and propane.
If this occurs then it is recommended that the sump hydrocarbon concentration should be measured
frequently and if necessary the liquid purge on a gas plant should be increased to its maximum (to
reduce the contaminant concentration). Acetylene would only be released from a PPU in extreme
circumstances.
See: Carbon Dioxide and Nitrous Oxide Contamination (Page 9).

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Contaminants
introduced by
equipment

Lubricants from the plant's mechanical equipment lubrication systems (compressors, pumps or
expanders) are possible contaminants of the process stream. The design should give positive
separation of oil-lubricated bearings from the process stream by the use of:

distance pieces

seals

labyrinths

vents

and purges.

Purge, vent, and seal gas systems must be operational on such equipment when the lubricating
system is operating to prevent contamination of the process fluid.

Lubricating oils

Lubricating oils have a very low solubility in liquid oxygen. The oil floats as solid on the surface of
the liquid oxygen and clings to the sides of the tank when the liquid level drops.
Because of this, conventional analysis of a liquid sample is unable to detect the presence of oil
contamination. The only reliable method of analysis is to empty the tank and either:

wash and analyse the tank cleaning liquid, or

inspect the tank visually.

Carbon Dioxide and Nitrous Oxide Contamination


Hazards of CO2
breakthrough

Carbon dioxide and nitrous oxide solidify in cold sections of the plant including exchangers and the
condenser.
In molecular sieve (PPU) plants, carbon dioxide is preferentially adsorbed over nitrous oxide and
light hydrocarbons. When CO2 breaks through a PPU, even at low levels such as 1 vpm, it indicates
that contaminants such as propane, ethylene and nitrous oxide are also passing through the PPU and
entering the cold box.

Evidence of CO2
or N2 O
breakthrough

Whenever breakthrough of CO2 is suspected samples of sump liquid should be taken and inspected
for a cloudy appearance. This would indicate the presence of insoluble carbon dioxide and/or
nitrous oxide. In this case the sump purge should be maximised and the carbon dioxide
concentration of the sump should be analysed.

Action if
blockage occurs

All blockages of lines or filters service must be investigated thoroughly.

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If a blockage occurs, arrange:

sump analysis, and

measurement of carbon dioxide and nitrous oxide levels.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Carbon dioxide

The solubility of CO2 in liquid oxygen is 4 ppm. Exceeding this level in the condenser can lead to
plugging of passages and dead-end boiling.
Carbon dioxide may be detected in a liquid oxygen sample taken from the condenser using infrared
spectroscopy or other methods.
On molecular sieve (PPU) plants carbon dioxide in the air is usually measured at the PPU outlet. On
RHE plants carbon dioxide contamination may be inferred from changes in the reversing heat
exchanger mid-point and cold end temperatures.

Nitrous oxide

Nitrous oxide occurs naturally in air at values between 0.3 and 0.4 ppm. Higher concentrations may
be encountered in the vicinity of industrial combustion equipment such as gas turbines, in the
vicinity of wastewater treatment plants and in tropical areas with decaying vegetation. It is only
partially removed by PPUs, but is removed to very low levels by cryogenic adsorbers.
Its solubility in liquid oxygen at re-boiler sump conditions is about 150 ppm.

Solubility rules

The concentration of any contaminant must not exceed 50% of its solubility in the liquid or vapor
phase at any point in the process.
For Thermosyphon type reboilers then this limits CO2 to 3 ppm and N2 O to 80 ppm - if these limits
are exceeded action should be taken to reduce the concentration. If the concentration continues to
rise towards the solubility limit, the plant must be shut down.
For Downflow type reboilers then tighter limits on CO2 and N2O already apply, (see the
Thermosyphon Contaminant Limits table in Contaminant Action Levels (Page 14)).
A further solubility limit may control when CO2 and N2 O are present together, as explained below.

CO2 and N2O


present together

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Contaminants CO2 and N2 O form a co-crystalline solid when both are present and they separate from
solution. This causes a mutual reduction in solubility of each pure component. To ensure solubility
the concentration of the CO2 /N2 O mixture must be within the boundary shown below. Action
should be taken if the concentration exceeds the boundary, and if the concentration continues to rise
the plant should be shut down.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Acceptable Solubility Range for CO 2/N2O Mixtures

Hazards of Hydrocarbons
Combustible
contaminants

Trace quantities of contaminants (particularly hydrocarbons) in the process air can affect the safe
operation of an air separation plant. Since these plants are normally located in industrial areas, some
contamination from industrial and/or chemical operations can be expected. Early identification of
these contaminants and the concentration levels at which they may be present permit the
development of process designs and operational techniques to deal with them.
The contaminants of greatest concern include those combustible with oxygen and those with low
solubility in liquid oxygen, which cause them to collect (or concentrate) in oxygen-rich liquids.
Hydrocarbons, in general, are hazardous and acetylene in particular is of concern because of its low
solubility and high reactivity with liquid oxygen.

Extreme hazard

Because of the very high reactivity of hydrocarbons in liquid oxygen, even small quantities can
detonate. On most occasions this leads only to damage to the re-boiler or vaporiser.
When larger quantities of hydrocarbon are present it is possible to cause ignition of aluminium or
even stainless steel which then provides the fuel for a massive explosion.
High oxygen purity increases the rate of combustion of aluminium because of a reduced amount of
inert gas (argon) at the combustion interface. A number of BOC plants are known to be operating at
purities in the vicinity of 99.9% O2 where the plant has not specifically been designed for operation
at this higher purity. Specific operating requirements to mitigate this additional risk are given in
Plant Operation at High Oxygen Purity (Page 18).
Accumulation of hydrocarbons is prevented by operating the plant in accordance with its design and
taking protective action in the event that excursions occur.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Acetylene

Acetylene is a major concern in ASUs. It can concentrate as an unstable solid in the condenser
section and can decompose explosively without the need for an ignition source. Acetylene is
removed from ASUs by the front-end purification system or by cryogenic adsorbers.

Control and Removal of Hydrocarbons


Prevent
accumulation

Every effort must be made to prevent hydrocarbons from entering the plant through the air inlet as
these can accumulate and constitute a hazard.
The accumulation if it does occur will be in:

Condenser / reboiler bath

the condenser bath of an oxygen production plant

adsorbers, or

the exchanger passes vaporising the waste liquid on nitrogen generators or the liquid oxygen
product in internal compression plants.

The condenser/re-boiler sump should be checked on a regular basis depending on the plant location.
If concentrations in excess of the recommended limits are discovered, the liquid must be drained and
vaporised in the disposal system. The re-boiler bath must then be replenished.
See: Condenser / Re-boiler Operation (Page 21).

Nitrogen
generators

Care must be taken during the plant thaw to ensure all accumulated hydrocarbons are gradually
purged from the system as the exchanger is warmed.

Problem plants

Oxygen plants are highly susceptible to hydrocarbon accumulation if:

there is little or no liquid off take from the main and/or auxiliary re-boiler sump, or

it is operated in a gas only mode, especially if cold requirements are being made up by liquid
injection.

On such plants analysis of hydrocarbon accumulation should be completed every shift, and the
necessary steps taken to deal with any excessive concentration.

Liquid oxygen
purge

All plants, whether RHE, PPU or other, must have continuous liquid purge rates of at least 0.5% of
the total oxygen production. Liquid oxygen product and liquid oxygen that is boiled in the main
exchanger of internal compression plants can be considered as liquid purge. Oxygen boiled in
thermosyphon re-boilers external to the column system (as on ICO plants, for instance) cannot be
considered as liquid purge. Purge flows should be established daily and should be recorded. If the
purge flow is blocked, it should be re-established within 60 minutes using a drain line.

Batch removal of
liquid

On small plants batch removal of liquid purge is acceptable as the smaller liquid flow rates are below
practical measurement limits. Batch purges should be taken at least every 8 hours. Batch removal of
liquid must be carried out by first building up liquid levels and then restoring them to normal. In
this case, the quantity of purge taken, on average, must still meet the requirement of at least 0.5% of
the total oxygen production.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Contaminant
removal by
adsorption

Water vapour, carbon dioxide, nitrous oxide and other contaminants are removed by adsorption at
ambient or cryogenic temperatures. The adsorbers remove acetylene and hydrocarbons heavier than
and including propane. Adsorbed hydrocarbons are removed from the adsorption media by
periodically reactivating the beds.
It should be noted that some hydrocarbons are not removed in the molecular sieve adsorber process.
For further information, see: Operation of Hydrocarbon Adsorbers (in ASU-02-04).

DANGER
Adsorbers are the key to the protection of the process from hydrocarbon build-up in oxygen rich
sections of the plant. Reactivation procedures should be followed precisely. The regeneration
temperatures and frequency should not be adjusted from those advised in the plant suppliers
operating manual. Inadequate reactivation of hydrocarbon adsorbers can lead to a build-up of
contaminants and explosive reaction with oxygen.
See: ASU-12-08 : Adsorbers and Gel Traps

Plant thawing
(deriming)

ASUs must be derimed at regular intervals in order to remove any residual impurities that may have
accumulated in the plant during operational upsets. Because the re-boiler is the component most
likely to accumulate hydrocarbons, it must be derimed with particular care.
Indications of a need to derime or to increase the deriming frequency are:

Abnormal pressure drops

High hydrocarbon level in intake

Frequent switching problems with reversing exchangers

Repeated instances of carbon dioxide breakthrough from PPUs or reversing heat exchangers

Unusual environmental conditions

Numerous unplanned plant shutdowns e.g. power failures

See: ASU-19-01 : Thawing.

Re-boiler Sump Analysis


Testing re-boiler
sump liquid

Re-boiler sump liquid must be sampled on a regular basis and analyzed for the presence of
hydrocarbons, CO2 and N2 O.
Plants with effective re-boiler purge rates below 5% of the total oxygen production must be sampled
every 3 months.
Other plants must be sampled twice a year.
New plants must be sampled every 3 months for the first year of operation. Sampling can then be
extended if the purge rate is above 5%.

Re-boiler sump
analysis

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A risk assessment must be carried out to determine whether there is a need for the installation of
continuous re-boiler sump analysis in the following scenarios.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

An ASU that produces less than 10% of its total oxygen product as liquid from the sump
of the LP column.
For this process the risk is in exceeding contaminant solubility or flammability limits in the
sump liquid.
Re-boiler sump liquid analysis should include hydrocarbons, CO2 and N2 O.

An ASU with a PPU that produces 100% of its total oxygen capacity as liquid from the
LP column sump which is then vaporized in the main heat exchangers at less than 7
bara pressure.
The required analysis concentration ranges for this case are set by the vapor phase solubility
of the contaminants at the vaporization pressure.
Re-boiler sump liquid analysis should include CO2 and N2 O.

Note 1

If less than 100% liquid is withdrawn from the re-boiler sump and/or a separate vaporizer pot is used
at any oxygen product pressure, then the expected maximum contaminant concentration in the
system should be calculated using the expected feed air composition to the cold box. A continuous
analyzer should be considered for CO2 or N2 O if the calculated concentration exceeds 25% of the
controlling liquid or vapor phase solubility.

Note 2

If the point of maximum concentration for hydrocarbons, CO2 and N2 O is not the re-boiler sump,
then contaminant analysis should be calculated for the point of highest concentration.
Some examples to evaluate are:

the argon condenser (RB28) bath in an argon producing plant;

the liquid oxygen storage tank for a plant with LO injection and continuous pumped
vaporization from storage through the main exchangers;

the LO trailer when used for liquid assist.

In these cases periodic batch sampling may be considered sufficient based on the risk assessment for
the specific situation.

Contaminant Action Levels


Operating limits
for sump
contaminants

The allowable limits on contaminant concentrations in the re-boiler sump are given in the tables
below. They are limits beyond which the plant should not be operated.
The normal operating concentrations should be significantly lower than these values and trending of
contaminants should be undertaken regardless of the frequency of sampling.
If at any time ant of the measured contaminant exceeds 4 to 5 times its expected normal or historical
value then there should be an alarm indicating the need to investigate and understand the cause. Any
other change of contaminant concentration, regardless if magnitude, should also be investigated and
understood.
Short term actions to be taken in the event of an alarm whilst the cause is being investigated include:

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increase the liquid purge rate (to reduce contaminant concentration),

take more frequent analysis samples (if on-line analysis is not installed) and

switchover the liquid phase adsorbers (if present)

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Contaminant
The allowable limits on contaminant concentrations in the sump, for Thermosyphon type re-boilers,
limits for
are given in the table below:
thermosyphon reboiler designs

Liquid Oxygen Thermosyphon Re-boiler


Operation at 1.2 bar abs
Max Allowable Concentration (vpm)
Contaminant

Shutdown Limit

CO2

Carbon Dioxide*

N2 O

Nitrous Oxide*

100

C2 H2

Acetylene

0.5

C3 H6

Propylene

35

C2 H4

Ethylene

200

C3 H8

Propane

100

C2 H6

Ethane

250

CH4

Methane

500

C4 hydrocarbons

Total Hydrocarbons

500

* Reduced limits apply if both carbon dioxide and nitrous oxide are present together See: Carbon
Dioxide and Nitrous Oxide Contamination (Page 9).

Contaminant
The allowable limits on contaminant concentrations in the sump, for Downflow or Linde Hybrid
limits for
Re-boiler designs, are given in the table below:
downflow or
Linde Hybrid reboiler designs

In Liquid Oxygen Downflow Re-boiler


Operation at 1.2 bar abs
Max Allowable Concentration (vpm)
Contaminant

Shutdown Limit
Shutdown

CO2

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Carbon Dioxide

0.5

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

N2 O

Nitrous Oxide

5.0

C2 H2

Acetylene

0.5

C3 H6

Propylene

C2 H4

Ethylene

15

C3 H8

Propane

C2 H6

Ethane

15

CH4

Methane

500

C4 hydrocarbons

Total Hydrocarbons (as CH4 )

500

Inlet Air Analysis


Monitoring air to
plant

Monitoring of air into the plant is an acceptable technique for identifying changes from normal, and
may be used to infer a maximum concentration build-up in the liquid oxygen sump. However direct
measurement of hydrocarbon levels in liquid oxygen is often practiced as the levels of concentration
are more easily detected.
If air monitoring is used:

Action to be
taken

the alarm levels should be set to between 3 and 5 times the normal methane values in the air

the instantaneous shutdown levels should be set to 20 times normal values, and

the plant must also be shutdown if the level exceeds 10 times normal values for a period in
excess of one hour.

When unacceptable hydrocarbon levels are apparent, the operational alternatives must be
considered, such as increased purge, increased re-boiler operating level, plant shutdown, and
dilution or disposal of contents.
Analysis should be repeated every shift until the concentration falls below the action level stated
above.
For plants fitted with cryogenic adsorbers, the adsorbers must be changed over and the adsorber
taken out of service must be reactivated.

Shutdown

When the shutdown limit is reached, liquid oxygen transfer to storage must stop. The plant must be
shut down and the condenser sump must be drained to waste.
Note

Liquid oxygen must be disposed of via a disposal system where a concentration of oxygen
can not accumulate, and which has suitable warning notices or is otherwise made
inaccessible.

See: Safe Disposal of Cryogenic Liquids (in ASU-18-01)

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Heavy
hydrocarbons

Limits are not given for heavier hydrocarbons as these are basically insoluble in oxygen and will not
be detected by analysis.
If there is any indication of the presence of heavy hydrocarbons (such as an oil residue in an
evaporated plant liquid sample), the plant must be shut down and washed with an approved cleaning
agent. Expert assistance should be sought from Global Operations before any decision to clean
process plant is made.
Heavy hydrocarbon contamination may be suspected through reduced performance of PPU or heat
exchangers or increased pressure drop across heat exchangers, for example. Gross contamination
may be detected using oil wipes and ultraviolet light.

Methane

Methane is usually the most significant naturally occurring hydrocarbon present in the air, and can
mask the presence of other more hazardous hydrocarbons.

Vaporisation in
main heat
exchanger

Internal compression plants compress product oxygen by pumping liquid from the sump of the LP
column re-boiler and vaporizing the product in the main heat exchanger.
During this process low boiling contaminants must remain soluble in the vapor phase at the stream
dew point temperature.
In some circumstances the above rule is overly restrictive - for instance when the last droplets of
liquid to evaporate can be calculated to contain high hydrocarbon concentrations. In this case the
concentration of hydrocarbons must be less than 10% of flammability.

Testing for Hydrocarbons


Testing for
hydrocarbons

The best practical method in most cases for detecting hydrocarbons is to measure Total
Hydrocarbons (THC) in the liquid oxygen with action level set as in the table above.
See: Testing for Hydrocarbons (Page 17).

Total
hydrocarbon
analysis

Total hydrocarbon (THC) analysers work by first converting all the hydrocarbons present in the
sample into methane. The methane level is then measured and the result is given as a methane
equivalent. Hence one part of propane (C3 H8 ) will be measured as three parts of methane (CH4 ).

Testing for
individual
hydrocarbons

Gas chromatography techniques may be used to detect for individual hydrocarbons.

Partial
vaporisation

Care must be taken in sampling liquids to avoid partial vaporisation and distillation of the liquid in
sample lines.

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Acetylene Testing
Acetylene testing Acetylene is completely removed by front end adsorbers using molecular sieve, and is preferentially

adsorbed over carbon dioxide. Hence, even in case of carbon dioxide breakthrough, there is little
risk of acetylene passing through into the process. For this reason acetylene testing is not mandated
on this type of plant.
Therefore, testing for acetylene is only applicable for plants fitted with reversing heat exchangers, or
where storage purities are being checked.
For regenerator and reversing heat exchanger plants routine testing of acetylene in the condenser and
in storage must be carried out each shift and recorded in the log.

Reducing test
frequency

Unless the plant is on the site of an acetylene storage or production plant, acetylene testing can be
relaxed on the basis of historical evidence, as follows. Shift analysis should be taken over the first
three months of operation, and if this demonstrates no evidence of acetylene, routine testing of the
re-boiler sump and LO storage may then be taken weekly.
Records of the three-month validation must be maintained for the life of the plant.

Detecting
acetylene

Acetylene can be detected in a sample of liquid oxygen drawn from the condenser sump using the
Ilsovay method. In this test oxygen is bubbled through a specific reagent and the resultant colour of
the mixture is compared to a chart to determine the acetylene content.
For details of the test method, see: Testing for Acetylene (in ASU-03-07).
Note:

This test is acetylene specific, and a negative result does not indicate the absence of other
hydrocarbons. Molecular sieve plants in particular may have a build up of other
hydrocarbons without the presence of acetylene.

Plant Operation at High Oxygen Purity


Background

High oxygen purity increases the rate of combustion of aluminium because of a reduced amount of
inert gas (argon) at the combustion interface. A number of BOC plants are known to be operating at
purities in the vicinity of 99.9% O2 where the plant has not specifically been designed for operation
at this higher purity.
Whilst operating at high purity is unlikely to increase the likelihood of having an ignition, it could
dramatically increase the severity if an ignition were to occur.

Avoidance

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To avoid the hazards of running at high purity then plants should not be run at purities above
99.9%. Where operation at higher purities is unavoidable, eg. for contractual reasons then this must
be considered in the hydrocarbon risk assessment.

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ASU Hydrocarbon Safety and Reboiler Operation

Additional
requirements
when operating
at high purity
(>99.9%)

To mitigate the additional risk of operating at high purity, the installation of an on-line sump
analyser(s) should be considered as part of the overall risk assessment process.
The liquid oxygen purge flow from the re-boiler sump must exceed 5% of total oxygen production
(1% of plant air feed).
Normal operating re-boiler submergence level must not be lower than 100%.
The maximum potential allowable steady O2 purity must not exceed 99.95% O2 taking into account
the accumulated inaccuracies of the analyser and the calibration process.

Hydrocarbon Risk Assessment


Introduction

The purpose of the hydrocarbon risk assessment is to ensure that site and plant specific risks have
been properly assessed and mitigated. This process should ensure the safe operation of re-boilers
and adsorbers in air separation units within BOC.
The risk assessment should be lead by a process safety expert, usually the Zone Platform Manager or
appointed delegate.

Requirements for Hydrocarbon risk assessments should be carried out on all ASUs and Cryogenic O2 generators. The
carrying out
risk assessment examines all risk factors, which could affect the likelihood, and severity, of an
Hydrocarbon risk ignition in a re-boiler.
Assessments

Hydrocarbon risk assessments must be carried out to support any extension to the mandatory 3 year
thaw period (see ASU-19-01 : Thawing).

Template

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A template for carrying out the hydrocarbon risk assessments has been agreed by the Process Safety
platform and must be used when carrying out hydrocarbon risk assessments. When used globally
across BOC ASU plants, it will provide consistency and achieve best practice in safe and efficient
operation. A Word version of the Hydrocarbon Risk Assessment Template
(http://bocweb16.processplants.boc.com/documentum/dctmVDMkII/VD.asp?ObjectID=0998968180
139b56&template=49&RFrame=DisplayVD__DB.asp&SB=False&ON=Hydrocarbon Risk
Assessments&AP=ps_intranet) can be downloaded from the BOC Intranet.

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ASU Hydrocarbon Safety and Reboiler Operation

Scope

Outcomes

The risk assessment uses a checklist to ensure all of the mandatory IMSS requirements are in place
and to assess all of the site and plant risk factors including;

Air contamination

Plant pre-purifiaction systems

Re-boiler liquid sump purges

Cryogenic adsorbers

Re-boiler submergence

Foreign material contamination

Long term contaminant accumulation

Liquid analysis

Other risk escalation factors (eg. downflow re-boilers, high purity plants with packed columns,
Krypton-Xenon attachments, etc.)

Other risk mitigation factors (eg. low O2 purity, small or remote location plants, etc.)

The output of the risk assessment may require a number of additional risk mitigation measures.
These are detailed in IMSS and may include:

On-line hydrocarbon analysis of air entering the plant

On-line analysis of sump liquid for CO2 and/or N2O and/or hydrocarbons

Increased or decreased thaw frequencies

Additional training, monitoring or maintenance requirements

Risk rating and


Depending on the assessment of all of the risk factors, the plant will be assessed as being a Low,
thaw frequencies Medium or High risk.

Extensions to periods between plant thaws will only be permitted on thermosyphon re-boiler design
plants which have been assessed as low or medium risk (see ASU-19-01 : Thawing.)
The nominal periods based on the three categories of risk are:

Low Risk Plants - 9 years

Medium Risk Plants - 6 years

High Risk Plants - 3 years

No plant must run beyond a 10 year period without a thaw.


The actual periods will be determined by the hydrocarbon risk assessment and can take into account
local planned maintenance requirements.
Overall risk ratings of a plant may increase or decrease over time dependent on changes in risk
factors.

Periodic review

The assessments must be reviewed annually by the local site / Process Manager.
The assessments must be reviewed 3 yearly by Zone Process Safety Manager.
A job has been created in Maximo to schedule these reviews.

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ASU Hydrocarbon Safety and Reboiler Operation

Formal sign-off
and retention of
document

Hydrocarbon risk assessments and the overall risk rating must be approved by the Zone Process
Safety Manager.
Electronic versions of the hydrocarbon risk assessment, and the 3 yearly revisions, must be saved by
the Process Safety Manager into the Process Safety EDMS collection
(http://bocweb16.processplants.boc.com/documentum/dctmVDMkII/VD.asp?ObjectID=0998968180
139b56&template=49&RFrame=DisplayVD__DB.asp&SB=False&ON=Hydrocarbon Risk
Assessments&AP=ps_intranet).
This must include all supporting information, (such as liquid analysis results, level transmitter
calculations, maintenance records etc.,) or as a minimum, a summary of that information.

Condenser / Re-boiler Operation


Types of Re-boiler
Description

The re-boiler condenser in the low-pressure column of an air separation plant is a heat exchanger that
condenses nitrogen vapours against boiling liquid oxygen.

Thermosyphon
re-boilers

In thermosyphon re-boilers the oxygen in the bath (open passages) vaporises against the condensing
gaseous nitrogen of the high-pressure column. The oxygen, in liquid phase at the lower part of the
re-boiler, vaporises progressively in the passage as it flows up the core. The effect of the difference
of density (which is higher for the sump liquid than for the two-phase mixture within the exchanger
passages) generates an upward flow of the oxygen (thermosiphon effect).
Any hydrocarbons in solution with the liquid oxygen entering the passages concentrate progressively
in the liquid phase, as an increasing part of the oxygen is vaporised.
As the two-phase mixture flows up and through the top of the open passages of the re-boiler core, a
significant amount of unvaporised liquid drops back to the bath. This is referred to as liquid recirculation. The re-boiler level controls the amount of liquid recirculation. Higher re-boiler levels
cause higher flows through the re-boiler and higher liquid re-circulation. The circulation keeps the
surfaces wet and contaminant free.
The diagram below shows the basic process.

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Downflow reboilers

In a downflow re-boiler, liquid oxygen is fed to a distributor located at the upper part of the reboiler. The liquid flows in a downward direction through the oxygen passages. Vaporised oxygen
flows from the bottom of the exchanger along with excess liquid at or above the minimum rate
specified by the supplier. Gaseous nitrogen from the high-pressure column is condensed in the
nitrogen passages.
Contaminant concentration in the liquid oxygen increases progressively as the oxygen vaporises in
the passage. A sufficient amount of excess liquid oxygen flowing from the bottom of the core
passages ensures that the maximum contaminant content of the liquid oxygen in the passages does
not reach dangerous levels. The control of this excess liquid is therefore essential.
The flow rate to the downflow re-boiler provided by the recirculating pump must always be kept at
the nominal value specified by the plant designer, even at a reduced plant capacity operating mode.

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Special restrictions apply to allowable contaminant concentrations for down flow re-boilers, and
assistance should be sought from the plant designer in establishing acceptable contaminant levels.
Down flow re-boilers should not be used with reversing plants because of the risk of continuous
acetylene accumulation.
Liquid phase LO adsorbers are required on any plant with down flow re-boilers that does not take all
oxygen product from the re-boiler sump as internally compressed liquid or as liquid product.

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Linde Hydrid re- There are a number of Hybrid type re-boilers built by Linde (from 2003) for BOC which have a
boiler
both downflow and thermosyphon re-boilers in the low pressure column.
arrangement

The design was project specific, but has now been repeated on a number of plants. It was created
because the column diameter and cold box dimensions were based on a previous design. With the
given column diameter, the downflow re-boiler is the largest economic size that can be installed
(which relates to brazing capacity, duty variation with block length etc.) The extra heat duty
required is supplied by the small trim thermosyphon re-boilers.

Dry and Dead-End Boiling


Dead-end boiling

Dead end boiling is a condition occurring in thermosyphon re-boilers where, due to blockages, the
flow of liquid is restricted within the channels of the re-boiler, thereby reducing the removal of
impurities by the flushing action of the liquid. This phenomenon can also occur in cavities and
sections of piping where oxygen-enriched liquid may be trapped and vaporised by heat leak.

Dry boiling

Dry boiling is a condition occurring in thermosyphon re-boilers where due to inadequate re-boiler
submergence, the liquid entering the re-boiler is totally vaporised, thereby concentrating any less
volatile impurities by extremely high factors and causing dissolved contaminants to deposit as solids.
This is also known as dry vaporisation.

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Re-boiler Operation
Condenser / reboiler operation

Condenser / re-boiler operation is considered critical for all ASUs and nitrogen generators with bath
type re-boilers where oxygen concentration in the liquid can be over 70%.
The maximum concentration of contaminants in the process typically occurs on the boiling side of
the re-boiler condenser.
Acetylene, CO2 and N2 O have low solubilities in cryogenic liquid so solid can separate at quite low
concentrations and may be trapped and collect in the small cavities of the re-boiler.

Condenser / reboiler levels

Re-boiler level controls the liquid oxygen flow through the re-boiler and the liquid recirculation rate.
If the re-boiler level and re-circulation flow rate are high, the concentration of hydrocarbons in the
passages remains limited, and dangerous accumulation in the passages is unlikely.
If the re-circulation flow rate is reduced or eliminated completely by lowering the re-boiler level, the
local hydrocarbon concentration in the passages increases significantly. At some concentration, a
second, hydrocarbon-rich liquid phase may separate, or deposits of solid hydrocarbons may build up
in the re-boiler passages.
Operating at low recirculation also allows any solid (perlite, molecular sieve, silica gel, carbon
dioxide, nitrous oxide) that may be entrained in the liquid to settle out at the vapour/liquid interface
within the core. This could result in blocking/plugging of passages and potential dead end
boiling.

Warning

Accumulation or deposition of hydrocarbons within the passages cannot be detected by


analyses of the re-boiler sump liquid, or by any other method.

Need to maintain
correct level

When operating the re-boiler bath below a specific level with respect to the core height, the liquid
oxygen can completely vaporise as it flows up the passages. This phenomenon of no re-circulation
flow is called "dry vaporisation" or dry boiling. Increasing this liquid level allows the recirculation flow to re-establish itself.
Maintaining the correct liquid level for thermosyphon re-boilers keeps the liquid recirculation high
and minimizes the chances of contaminant buildup. The liquid level must be maintained for
operation at all plant capacities.

Normal operating Operating the condenser/re-boiler block at the correct level of submergence is critical to prevent
level
concentration/build up of contaminants in the oxygen passages.

Condensers must be operated at a level calculated to achieve 100% submergence, unless design
information for the plant permits a lower level, subject to a minimum normal operating level of 80%
submergence.
Ensure the level does not reach the GO off take as this can result in liquid becoming entrained and
carried over into the warm end pipework.
Note:

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Condenser level and submergence level are not the same. Indicated level for 100%
submergence may be calculated using the procedure below.

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Calculating
submergence
level

The submergence level may be different from the level indication and calculations must be made to
determine the relationship between them.

Worked example

The diagram below shows dimensions of a typical re-boiler, and a table giving the density of liquid
oxygen at different column pressures.

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Hence 100% submergence of the re-boiler actually occurs when the level indication shows 85.1%.

Low level alarms

Low level alarms and trips should be fitted to prevent hazardous operating conditions.
A low level alarm should be set at the point corresponding to 85% of normal operating level. The
normal operating level will be between 80 and 100% submergence, depending on the requirements
described in 'normal operating level' above.
A plant shutdown trip should be set at 50% submergence of the re-boiler (not 50% of normal
operating level).
A short time delay, no greater than 5 minutes, may be built into both the alarm and trip functions so
that short transients in liquid level do not cause plant alarms and shutdowns. A manual override to
the trip with automatic reset after one hour may be provided for startup.
On manned plants the condenser level may be run below alarm level for up to 60 minutes whilst
remedial action is taken. This is especially relevant during cold plant start-ups and disturbances.
If level is not re-established above alarm level after 60 minutes the plant must be shut down.

Calibration of
Accurate calibration of the re-boiler level transmitter is key to proper control of re-boiler
level instruments submergence. Best practice is to range the level transmitter so that 0% is the bottom of the re-boiler

and 100% is the top of the re-boiler. For the example above, ranging the level transmitter so that 0
water gauge corresponds to -15% level indication and so that 120 water gauge corresponds to 120%
level indication would give direct readout of submergence. In this case the level indication for the
GO offtake and for the upper level tap will be well above 100%. The level indication for the GO
offtake and for the upper level tap should be available to the operator at the control console.
For sites with multiple ASU plants, or ASU plants which are remotely operated, then the reboiler
level must be displayed as a % submergence of the block. This reduces the risk of confusion for the
plant operator.
If re-boiler level is not ranged to correspond with submergence, the level indication corresponding to
50%, 80% and 100% submergence should be established. These values should be displayed along
with the actual sump level for the plant operator.
Lines other than the appropriate impulse lines for level transmitters should not be used for re-boiler
level determination without the written approval of a competent person/authority. Determination of
the appropriate span and range when other lines are used is tricky. Improper setting of the level can
lead to operation at low submergence and potential hydrocarbon build-up.
The re-boiler level transmitter must be calibrated at annual intervals or according to manufacturers
recommendations, whichever is sooner.

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Re-boiler purge

Hydrocarbons are not likely to accumulate to high concentrations in plants that produce a significant
percentage of their oxygen as a liquid product from the sump. In internal compression plants,
oxygen withdrawn from the low-pressure column sump as liquid, pumped to elevated pressure and
vaporised in the main exchanger external to the column system can also be considered as liquid
product for contaminant removal (purge) calculations.
If a plant produces only a gaseous oxygen product (taken directly off the column) or a very small
amount of liquid, a measurable amount of liquid must be removed from the re-boiler sump to limit
contaminant concentrations to acceptable levels. The contaminants controlled by the purge include
light hydrocarbons (particularly C2 H4 , C3 H8 and C2 H6 ), as well as N2 O and CO2 .
The purge flow from the re-boiler sump should be calculated to achieve the minimum allowable
contaminant concentration. In any event it must exceed 0.5% of total O2 production.

Adsorbers

Cryogenic adsorbers are installed on many ASUs, either liquid phase on liquid oxygen and/or rich
liquid streams or as gas phase gel traps on the air stream to the column. Such adsorbers, normally
using silica gel, remove certain hydrocarbons, and in particular acetylene, as well as carbon dioxide
and nitrous oxide. In particular adsorbers are used extensively on regenerator and reversing heat
exchanger plants where these contaminants are known to be carried through into the process.

Plants where
In plants with front-end molecular sieve adsorbers (PPUs) acetylene is completely removed, as is
adsorbers are not most of the carbon dioxide, though some other hydrocarbons are not.
required

In such plants a liquid purge may be adequate to reduce concentrations of contaminants to acceptable
levels and cryogenic adsorbers are often not installed.

Sudden changes
or plant upsets

Sudden changes in plant operating conditions or plant upsets may temporarily change the re-boiler
liquid levels. During these changes, the submergence level may be allowed to drop to 30% lower
than normal for only short periods of time without seriously affecting the safe operation of the unit.
If the 100 percent submergence level cannot be restored, the operator must shut down the air
separation unit.

Action on cold
shutdown

Particular attention must be given to the re-boiler liquid level when the air separation plant is shut
down. If the submergence level falls to below 50%, the operator must either:

dispose of all of the liquid from the re-boiler, or

if liquid is available and means are provided, liquid may be added to the plant to maintain
proper liquid levels and to dilute contaminants.

When starting a plant containing liquid after a cold shutdown, special care must be taken to prevent
the evaporation of existing plant liquid.

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Indications of
contaminant
build-up

Deviations from normal temperatures and pressures in the cryogenic exchangers indicate that
contaminant build-up is occurring and that thawing is necessary.
Blockages of lines or filters, particularly in liquid oxygen lines, should be investigated thoroughly
since such blockages could indicate high levels of CO2 or nitrous oxide, which could also be plating
out undetected in the re-boiler. Analysis of the re-boiler sump liquid for carbon dioxide, nitrous
oxide and hydrocarbons should be done when such blockages occur.
An increasing contaminant level in the distillation column and plant liquids indicates that either:

the purge has decreased

the air quality is deteriorating,

the PPUs or reversing heat exchangers or cryogenic adsorbers need maintenance, or

the plant must be thawed.

For information on thawing, see: ASU-19-01 : Thawing.

Actions Checklist Maintain a purge of liquid oxygen from the sump of the re-boiler of at least 0.5% of the total oxygen
in the event of
production.
contaminant
Note: Liquid oxygen product taken from the sump can be considered as a purge.
build-up

Increasing the purge helps reduce the contaminant levels.

Take more frequent samples if on-line analysis is not possible.

Complete re-boiler sump analysis regularly.


Monitor the impact on the plant through regular sump analysis focussing on hydrocarbons, carbon
dioxide and nitrous oxide
Regenerator plants and RHE plants must:

routinely analyse for acetylene on a daily basis and

maintain records of the results.

if acetylene is detected it must immediately be reported to the site manager.

Raise the re-boiler level until the re-boiler is fully submerged.

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Ensure the level does not reach the GO off take as this can result in liquid becoming entrained
and carried over into the warm end pipework.

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ASU-12-11-BOC
ASU Hydrocarbon Safety and Reboiler Operation

Documents Referenced

IGC Document 65/99/E Safe Operation of Re-boilers/ Condensers in Air Separation


Units
This is a globally harmonised document which forms the basis for BOC standards
BOC Process Plants Standards

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00000-T-G-001

Air Feed Quality and Contaminants in Cryogenic ASUs

00000-T-G-407

Contaminant Analysis Requirements for ASUs

00000-T-G-600

Safe Design for Contaminants in Cryogenic Air Separation

00000-N-G-001

Re-boiler Level Transmitter Calibration in Cryogenic Air


Separation Plants

00000-P-D-548

Hypodermic Type Liquid Analysis Sampling Probe for


Al. Lines Assembly

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