Chemical and Petroleum Engineering, Vol. 43, Nos.

12, 2007

CRYOGENIC ENGINEERING, PRODUCTION AND USE

OF INDUSTRIAL GASES, REFRIGERATION ENGINEERING
PROVISION OF EXPLOSION PROOF AIR SEPARATION
UNITS UNDER CONTEMPORARY CONDITIONS

V. I. Fainshtein

Modern methods are considered for providing explosion proof air separation units (ASU); measures
required for providing explosion proof ASU are given; explosions in installations equipped with complete
air purification units before its supply to low-temperature separation are analyzed; technological reasons
are considered for the occurrence of explosion hazard conditions in condenser-reboilers.

Prevention of explosions is one of the main problems that it is necessary to resolve in creating and operating air separation units (ASU).
The possibility of the occurrence of explosion hazard conditions in ASU is due to presence within the processing air
of contaminants that by accumulating in condenser-reboilers and other parts of installations form mixtures that are an explosion hazard in liquid oxygen. In addition, explosion hazard conditions arise when fuel substances within the intra-unit space
are impregnated with liquid oxygen due to leakage from equipment and pipelines.
At the start of the 1980s, Kriogenmash on the basis of scientific research and test construction work introduced
methods into production for calculation and technical solutions providing ASU that operate reliably under all known conditions for the contamination of processing air. Simultaneously, standard documents were created controlling the requirements
for explosion hazard safety in designing ASU and during equipment operation.
In particular, safety laws were developed for the production and use of air distribution products (PBPRV-88) and
affirmed by the Federal Mining and Industrial Inspectorate of Russia.
Modern Methods for Providing Explosion Proof ASU. Prevention of explosions caused by the accumulation in
equipment of explosion hazard components contained in processing air is achieved by fitting installations with explosion hazard safety systems providing thorough purification of processing air from dangerous contaminants, preliminary purification
of production flows, constant purification of liquid oxygen, and also output from the installation of the required part of oxygen in liquid form.
Alongside this, production measures are carried out reducing to a maximum the intensity of explosion hazard contaminants on heat-liberating surfaces during evaporation of liquid oxygen and excluding passage of dangerous contaminants
into subsequent equipment.
Quite a high level of explosion protection for ASU is achieved by equipping them with complete purification units
(CPU) for air before its entry into the low-temperature section. With the use of CPU, air is purified not only from undesirable contaminants (moisture and carbon dioxide), but also the majority of explosion hazard substances.
Kriogenmash has developed and introduced a set of measures for provision of explosion proof ASU operation:
purification of separated air from dangerous impurities on synthetic zeolites;
Kriogenmash OAO, Balashika, Moscow Region. Translated from Khimicheskoe i Neftegazovoe Mashinostroenie,
No. 2, pp. 2023, February, 2007.
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0009-2355/07/0102-0096 2007 Springer Science+Business Media, Inc.

TABLE 1
Number of explosions connected with accumulation of hydrocarbons
ASU

Nature of explosions
Up to 1963 19641969 19691974 19751979 19801984 19851995

Low pressure

Large explosions

Microexplosions in condensers

47

178

176

31

Medium and high pressure

Large explosions

95

15

16

Medium pressure with CPU

Large explosions

adsorption purification of liquid oxygen in a circulation loop;

continuous flow for condenser-reboilers;
operation of condenser-reboilers in a favorable hydrodynamic regime;
systematic thawing of equipment operating with high contents of explosion hazard contaminants;
monitoring for the content of explosion hazard contaminants in sections of production flows with greatest enrichment by them;
exclusion of any organic materials from the space between units;
exclusion of the possibility of access of cryogenic liquid to expansion filters;
effective separation of produced oxygen from liquid droplets;
fulfilment of special requirements in pipeline assembly;
banning operation with leaking fixtures.
As a result of this work, the frequency of ASU explosions and accidents within Russia and territory of the previous
USSR in 19641995 decreased tenfold (Table 1).
The following data are known for the number of explosions for the ASU of overseas firms (approximately from
1964) connected with accumulation of hydrocarbons [1]:
three large explosions accompanied by destruction not only of the unit but also neighboring structures;
eight local explosions whose consequences did not emerge beyond the limits of the separation unit housing;
thirty six microexplosions leading to development of leakage in the steam generating channels of oxygen evaporators.
Analysis of Explosions in Units Fitted with Air CPU. CPU were first used more than 25 years ago in medium and
high pressure ASU. Only two explosions have been noted, occurring about 20 years ago in medium pressure ASU operating
in an oil processing enterprise. Before 1997, in low pressure ASU fitted with zeolite CPU for air there were no explosions
connected with accumulation of explosion hazard contaminants.
However, in 1997 two large accidents became known as a result of which the ASU fitted with CPU in Bintulu
(Malaysia) and Fushun (China) [2] were completely taken out of service. The situation and results of the investigation of these
accidents have been considered in [3, 4].
The explosion in Bintulu occurred in one of the largest oxygen units in the world with production of 2500 tons/day
that operated in combination with a petrochemical complex. As a result of the explosion in the main condenser-reboiler and
subsequent ignition in liquid oxygen of four aluminum lamellar-ribbed assemblies of the condenser and part of the aluminum
packing of the upper column the housing of the separation unit was destroyed and there was considerable damage to surrounding equipment. Twenty people were injured. The total energy of the explosion was estimated as 4.2 GJ.
The unit was equipped with condenser-reboilers with a descending flow of evaporated fluid. There was no adsorber
circulation circuit. The flow-through of an condenser-reboiler was in all 0.02%, and this gave rise to considerable concentration of explosion hazard contaminants in liquid oxygen, i.e., 5000 greater than in the air being processed.
The reason for the explosion was accumulation in the condenser-reboiler of dangerous components, i.e., incomplete
combustion products formed during prolonged forest fires, as a result of which during one and a half months visibility in the
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region of unit location was reduced to the level of 20 m. It is well known that this low visibility corresponds to an aerosol
concentration in air of 2050 mg/m3. In this case in the unit, processing about 300 thousand m3/h of air, the delivery of
aerosol at the inlet to the air filters was 615 kg/h.
During forest fires, there is a considerable amount of unoxidized solid particles of the soot type in the air. The smoke
formed is a combination of aerosols of all types (dust, smoke, fog) and is a variety of smog. The dispersed composition of
such aerosols is mainly in the range 0.11 m. Air containing such a significant amount of aerosols cannot be purified effectively in filters installed ahead of the compressor. It is impossible to expect a high efficiency for separation of these aerosols
in zeolite purification units and a circulation adsorber.
Thus a considerable amount of aerosol entered the liquid oxygen and accumulated within it. Even if 1% of aerosol
contained in processing air enters the liquid oxygen, then over a month in condenser-reboilers tens of kilograms of aerosols
may accumulate consisting to a considerable degree of unoxidized fuel particles that are an explosion hazard in liquid oxygen.
A layer of fuel dust, accumulated on the surface of steam generating channels, reached an explosion hazard thickness and by starting burning of the deposits led to ignition of the thin-walled aluminum structures and almost instantaneous
evaporation of a considerable amount of liquid oxygen. Analysis showed that the content of monitored hydrocarbons in liquid oxygen did not exceed the standard.
The explosion in Fushun occurred in the ASU with a productivity of both 6000 m3/h of oxygen and 6000 m3/h of
nitrogen, that operated within an industrial complex in order to prepare and process ethylene.
The center of the explosion was in the region of the main condenser. As a result of the explosion and subsequent
burning in liquid oxygen of part of the aluminum lamellar-ribbed condenser assembly and part of the aluminum regular packing of the upper column, and evaporation of a considerable amount of liquid oxygen, the housing of the unit was destroyed
and there was considerable damage to equipment outside the air separation unit (four people were killed, and 31 were
injured). The total energy of the explosion was estimated at 0.8 GJ whose trotyl equivalent is 1750 kg.
The unit was equipped with lamellar-ribbed condenser-reboilers with natural circulation and a circulation circuit
adsorber. The reason for the explosion was entry into the ASU of a considerable amount of ethylene connected with discharge
into the atmosphere of gas containing 46% ethylene from the unit for preparing ethylene dioxide located at a distance of
103 m from the air intake compressor. The difference in the height of the discharge of ethylene into the atmosphere and the
air intake was 9 m. For a long time before the accident, the wind direction was very unfavorable.
Before the explosion, the oxygen unit operated in a discharge regime in view of the suspension of a requirement for
oxygen. No take-off of oxygen occurred. For 9 h before the accident, the level of liquid oxygen in the main condenser
decreased to 5060% of a totally charged assembly.
Normally, the ethylene content in the air is very small, and therefore accumulation of an explosion hazard amount of
ethylene in the condenser-reboilers was assumed to be hardly probable. The ethylene was only held in a small amount in the
CPU and the circulation circuit adsorbers. In the case in question, as a result of an extremely high content of ethylene in air
there was accumulation of it in the transfer channels of a condenser-reboiler. Explosion of a comparatively small amount of
ethylene (about 500600 g) led to burning of about 1000 kg of aluminum. In [6], this explosion is only connected with processing air extremely contaminated with ethylene that was observed immediately before the accident. Apparently in the Fushun
case an increased content of hydrocarbons in the air and operation of condenser-reboilers in an unfavorable regime occurred
repeatedly in the past, and this also led to accumulation of significant amounts of hydrocarbons on the steam generating surfaces of the condenser-reboilers.
Thus, both accidents occurred during operation of units under conditions of extreme contamination of the processing air by explosion hazard contaminants.
Main production reasons for the occurrence of explosion hazard conditions in condenser-reboilers:
in the Bitulu unit use of condenser-reboilers with a descending flow of evaporated liquid (irrigation type) within
which it is very complicated to exclude rapid accumulation in the steam generating channels of contaminants contained in evaporated oxygen and the very low flow of the main condenser;
in the Fushun unit operation of condenser-reboilers with an extremely low level of liquid oxygen that led to operation of the steam generating channels in a dry regime and caused rapid accumulation of hydrocarbons within them;
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TABLE 2
Average efficiency of purification (%) from hydrocarbons
Ethylene

CPU
Regenerators

Ethylene

Propane

Propylene

Acetylene

C4C5

10

5060

6070

>98

>95

40

4060

5070

Up to 80

Up to 90

Adsorbers in still fluid flow

3040

4060

6080

Up to 95

Up to 80

System of regenerators-adsorbers in still fluid flow

50

60

70

Overall ethylene content.

lack in technical documentation of instructions about not operating the unit under conditions of extreme air contamination or an operating sequence of the unit under these conditions;
insufficiently effective monitoring of the content in liquid oxygen of explosion hazard contaminants specific for an
industrial region within which the unit operates or errors of the servicing personnel.
As a result of analysing the Air Liquide standard [5] and documents [1, 6] prepared by the European Industrial Gases
Association (EIGA), specialists of Kriogenmash have established that the principles and recommendations for providing
explosion proof condenser-reboilers, formulated by the leading Western firms after these explosions, are hardly different from
the principles and technical decisions realized in Kriogenmash over the last 20 years [79]. However, in these publications
insufficiently detailed consideration is given to the process of occurrence of explosion hazard conditions during evaporation
of oxygen in condenser-reboilers and possibilities for reducing the intensity of this process.
The explosion at Bintulu confirmed the danger for ASU not only of gaseous explosion hazard contaminants, but also
fuel aerosols and dust contained in processing air. In addition, after the explosions in question the danger should finally be
acknowledged of using in rectification columns regular packing of this layer aluminum and the laminar-ribbed reboilers.
The possibility of combustion of thin aluminum plates in liquid oxygen has been well known for a long time. The possibility of their ignition under conditions of an industrial unit has been assumed to be almost improbable.
It should be noted that in order to prevent explosions similar to those in question a set of measures should be carried for providing an explosion proof ASU developed by Kriogenmash.
Monitoring of Air Contamination. Accumulated experience of operating ASU with CPU has shown that the
probability of the occurrence of explosions has decreased many times. However, use of CPU for air and correspondingly
exclusion from the unit of regenerator assemblies or reverse heat exchangers and adsorbers in the flow of still fluid has
markedly reduced the efficiency of protecting units from such hydrocarbons as ethylene and propylene. For example, the
proportion of ethylene entering the low-pressure column with presence in the device of regenerators and adsorbers in
the flow of still fluid is normally not more than 50% of the content in processing air [7], whereas in units with CPU this
proportion is more than 80%.
Some data about the efficiency of different means and systems for removing explosion hazard contaminants are provided in Table 2.
Normally, the content of hydrocarbons of the C2C3 group in atmospheric air is markedly less than the content with
which occurrence of explosion hazard conditions in a unit is possible. However, extreme contamination of processing air with
such hydrocarbons may be very dangerous (and this is confirmed by the Fushun explosion) as a result of an unusual situation
in production and technical facilities located within the region of an air separation station and its air intake. This primarily
relates to the possible discharge into the atmosphere of hydrocarbons and other explosion hazard contaminants during stoppages or with a change in operating regime for chemical and production units and installations. Therefore, in enterprises operating ASU systematic monitoring of the air basin is important as laid down by its safety rules, i.e., it is necessary to evaluate
systematically contamination of air supplied to the ASU and to predict its possible changes taking account of operating conditions for the equipment and other facilities located on an industrial site, and also development of an industrial region. It is
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natural that this work should be performed together with the overall planner responsible for interaction of enterprises of an
industrial region and departments for health and ecological inspection.
In performing monitoring, apart from metallurgical, chemical, and petrochemical production it is also necessary to
consider such facilities as automobile roads, parking places for motor transport and locomotives, central heating and power
plants, smoking dumps and waste piles, depots and storage of petroleum products, gas pumping compressor stations, gas
pipelines protection valves, etc.
As applied to ASU atmospheric air contamination should be evaluated for the average and maximum permissible
content of contaminants in 4, 8, and 24 h of operation.
Monitoring should be performed for all contaminants indicated in the technical documentation for ASU supply
(standard contaminants) and other explosion hazard contaminants specific for an industrial region within which the unit is
located.
In standard nomenclature for monitored contaminants there is explosion hazard contaminants (hydrocarbons);
blocking contaminants (CO2 and N2O); contaminants that may have a deleterious effect on air ASU zeolite (sulphur compounds, HCl, and others).
The limiting content of a contaminant in air is controlled by the ASU workers and indicated in the technical tasks
for creating a unit, contracts, technical-commercial proposals, and also in operational documentation.
Monitoring includes:
composition of a list of products and facilities located in an industrial area discharging into the atmosphere explosion hazard substances, including technical prescription with an estimate of the weight discharge under the most
unfavorable operating regime for these products and facilities in both standard and in accident situations. This list
should be renewed systematically;
provision for calculations of scattering of contaminants in the atmosphere and determination of their maximum
possible concentrations in the area of the air intake for an oxygen unit under the most unfavorable weather conditions (planned monitoring);
comparison of the results of calculations with standards and adoption of the corresponding solutions;
provision (as required) of instrument analysis of the content of individual contaminants in air entering the unit with
different wind directions and other weather conditions and explanation of the possibilities for reducing contamination of the incoming air by transfer from a remote air intake to a local air intake, or vice versa.
If planned monitoring of the air basin indicates that air contamination does not exceed standards, then during ASU
operation instrument monitoring for the content of contaminants in processing air is not performed, but only the constant of
contaminants in liquid oxygen is constantly monitored according to the operating regulations. By comparing chromatograms
from analyzers, it is also possible to obtain specific information about changes that occur in contamination of the processing
air. This operation should be performed regularly by laboratory workers.
If it is established that air contamination may exceed the standards, then the operational organization should take the
required measures for reducing the content of explosion hazard contaminants in processing air and to consider operationally
the build-up of a situation with workers of the unit. Simultaneously there should be reinforced monitoring for operation of
the system providing an explosion proof unit and for fulfilling operational requirements.
In conclusion, it is necessary to emphasize that the probability of explosions in modern ASU is very small, but it
really exists and it is governed by specific local conditions. It is necessary to continue improving systems providing explosion proof ASU taking account of the specific conditions for air contamination and in accordance with structural and production features of the equipment created and operated.

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Safe operation of reboilers/condensers in air separation units, IGC EIGA Document 65/99/E, New issue IGC
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