Cryogenic spill protection and mitigation*

J. M o o r h o u s e and P. R o b e r t s t
Research and Technology Division, British Gas plc, M=dlands Research Station, Wharf Lane, Sohhull B91 2JW, UK tResearch and Technology Diwslon, British Gas plc, Technology Apphcat=ons Department, 326 High Holborn, London WC1V 7PT, UK A range of practical measures are reviewed which can be adopted for preventing detecting, or m=t=gatmg against spdlages of cryogemc hqulds from containment Specific examples of such measures are examined which are drawn from experience within the LNG industry and which may also find apphcatlon within other mdustnes

Keywords cryogen,c I,qu,ds, safety, LNG

The purpose of this Paper is to give a brief overview of the hazards associated with spills of cryogenic liquids, and of the measures which are available to detect spills and to mitigate their consequences The Paper is based to a large extent on experience within British Gas and other gas industries world wide, thus, there is a bias towards specific measures adopted to deal with spdls of hquefied natural gas (LNG) Measures are included, however, which are apphcable to other cryogenic hqmds The principal concern from spills of cryogemc hqulds results from the low hquld temperatures and from the vapour evolved as the released hqmd receives heat from the surroundings The flammablhty of the vapour presents an ad&Uonal concern in the case of a hquld such as LNG Obviously, the best prachce would be to prevent spills of cryogenic llqmds from occurring m the first place This topic is covered briefly below If spills ofcryogemc hqulds do occur, then it is desirable that they be isolated as soon as possible, this problem is also addressed Ifspdls cannot be ~solated quickly, then it may be necessary to adopt measures to mitigate their effects Such measures (detailed below) may include protection for equipment and matermls and dewces to reduce the extent of the vapour cloud produced following a spill To quantify the potentml benefits of some of these measures, this Paper also includes some results from a theoretical case study carried out by Brmsh Gas The effects of different bund geometries and surfacing materials on the extent of vapour cloud travel following an L N G spill from a storage tank into an impoundment area have been studied

Spdl prevent=on
The basic principle behind avoidance of spills of cryogenic liquids is to pay proper attention to design and construction standards and to operating procedures and malnten*Paper presented at the Br=t=shCryogemcs Council Symposium on the Safe Storage and Handhng of Cryogemc L=qulds, London, UK, 8 March 1988
0011-2275/88/120838 09 $03 00 (, 1988 Butterworth & Co (Pubhshers) Ltd

ance schedules Instrumentation is one key area Storage tanks for cryogenic liquids would normally be fitted with one or two level sensing devices which would be m o m tored either regularly or continuously during any filling or transfer operation These are generally complemented by single or multi tier alarm systems to warn of overfilling, the final tier may be hnked to an automatic isolation of the tank fill line Level sensing devices include simple floats, temperature sensitive capacitors, differential pressure gauges and ultrasonic detectors which locate the liquid surface Exposed sections of plpework, for example, between storage tanks and isolation valves, where unchecked spills could occur may be protected physically, either by using double integrity pipe or enclosing the sections in housings to protect against impact Perhaps one of the most obvious areas for potential leaks to occur is during transfer of cryogenic hqmds between storage tanks and road tankers or marine carriers Road tanker transfer is usually accomplished via flexible hoses (as illustrated in Fzgure la) whilst marine transfer operations generally employ articulated loading/unloading arms (Ftgure lb) although flexible hoses may also be used If a road tanker or marine carrier were to move during transfer, rupture of the unloading hose or arm, and spillage of liquid, could occur Wheels of road tankers are commonly chocked during transfer to avoid movement In addition, flexible hoses can be fitted with automatic uncoupling and isolation devices, for example, the valves at either end of a flexible hose could be held open by gas pressure, the gas being supplied via a sleeve around the hose, or through a parallel line, so that gas pressure would be lost and the valves closed in the event of the tanker moving away Marine transfer arms are commonly fitted with movement detectors which automatically isolate the arm in the event of excessive arm travel I In addition, some L N G facilities employ powered emergency release couplings which can shut down and disconnect the arm in a few seconds, thus preventing damage to the arm These devices comprise two ball valves, operated hydraulically, enclosing a quick release coupling

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Cryogemcs 1988 Vol 28 December

Cryogemc spdl protectton and mtttgatton J Moorhouse and P Roberts

a

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Figure I Automattc Bolatton systems for road and marine tankers (a) Road tanker hose failure protection system, (b) d,agram of art=culated marine unloading arm

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~-- Sell S{IF Ftgure 2 Schematic dmgram showing the fibre optic spill detect=on system (a) Refractwe index v e r s u s temperature Coohng of sheath of fibre results m increased refractive index and increased attenuatton of hght transm=tted (b) Schematfc dtagram of system installed m a catchment area

Spill detection and Isolation

The devices available to detect sDlls of cryogemc hqulds fall into two broad categories temperature sensors to detect the cold liquid, and gas detectors to warn of the presence of the vapour evolved Until fairly recently, only one type of temperature sensor the &screte, single-point measurement device was in common usage This category comprises thermocouples and thermal resistance thermometers The dmadvantage of single point devices is that each detects a spill only if it reaches the specific location of the sensor Hence, if single-point dewces are used, they should obviously be located at points where any spilled llqmd is likely to collect Channels and slopes can be used to direct spilled hquld to chosen catchment areas (see later), in which case temperature sensors can usefully be set into the floors of the channels The sensors may also be located beneath plant ~tems where leaks are more hkely to occur (e g pumps, vaporizers, flanges, etc ), m the bunds surrounding storage tanks, or between the walls of double-walled tanks More recently, a different type of device, which is capable of detecting a low temperature at any point along its length, has become available Two examples of this type are cold strip detectors and fibre-optic systems The former type may comprise a tube of conducting hquid 2 s or a strip of thermistor beads, whose electrical resistance increases as the temperature decreases, the latter type (Fzgure 2) relies on the change m the ablhty of a fibre-optic cable to transmit hght when it is cooled below a certain temperature, and unlike the thermistor type device does not require any electrical supplies m the area where spills

are likely (This Is an important consideration in the case of a flammable fluid such as LNG) A proven fibre-optic system has been developed jointly by British Gas plc and Pilklngtons 4 The main advantage of these detectors over the fixed point type is that they will sense contact w~th cold hqmd at any posmon along their entire length, rather than at a specific location, this is especially advantageous lf~t is difficult to predict where spills are hkely to occur, or if there are a large number of potential leak sources (e g along the length of a flange-jointed plpehne) The second category of spillage detection devices are gas detectors and, as noted above, they may need to be specifically calibrated for a particular fluid of concern Various types of detector are available for LNG, the most common being catalytic combustion, semiconductor or thermal conductivity types CatalyUc combusUon detectors are sensmve to any flammable gas semiconductor detectors and thermal conductivity instruments will detect a variety of flammable and non-flammable gases The first two of these three types are more sensmve to low gas concentrations Gas detectors will only m o m t o r concentratlons at specific, discrete points, and their principal use is to measure concentration levels inside buildings and structures, however, they can be used for outdoor apphcaUons ff they are located very close to potentml spill sources 5 A general method to detect gas releases over a

C r y o g e m c s 1 9 8 8 Vol 28 D e c e m b e r

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Cryogemc spill protection and mitigation J Moorhouse and P Roberts

wide plant area would be the use of laser tracking, but the authors are not aware of any instance of this being used on a site handling cryogenic fluids 6'7 The above sensors and detectors can be complemented by visual observation, either directly by itinerant site personnel, or indirectly by closed circuit television Visual observation would normally be used to confirm signals from detection devices, rather than as a primary detection measure in itself Contact of exposed surfaces with cryogenic hqulds can lead to rapid temperature reduction and can lead to embrlttlement in the case of carbon steels, so it is most important that spills in the vicinity of unprotected steel equipment be detected and isolated as quickly as possible In this respect, temperature sensors have an obvious advantage over gas detectors (since the vapour is not evolved instantaneously), so the former are to be preferred where practicable In addition, gas detectors may need to be specific to the particular fluid in question, whereas temperature sensors will be equally effective for any cryogenic liquid In addition, it is important that the spill detection devices be hnked to automatic isolation of the release where this is appropriate and especially where unprotected steel structures are at risk
j Flange box

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F=gure3 Schematic diagram showing spillage protection at source an impoundment area Examples are shown in

Ftgure 3,

Protection of equipment
Contact of a cryogenic liquid with metalhc and nonmetallic objects will cause rapid cooling and consequent shrinkage Concrete has been shown to have the ability to withstand L N G whilst carbon and low alloy steels are particularly vulnerable This is because they are subject to a ductile to brittle transition at low temperatures It is necessary, therefore, to consider protecting specific items against any contact with cryogens In the case of bare mild steel in contact with a cryogen such as L N G the rate of temperature drop upon contact is about 0 6 K s - 1 for each 12 m m thickness of steel The presence of a thin paint layer on the steel increases this is about 2 4 K s - 1 for each 12 m m of steel thickness since the paint layer allows the establishment of nucleate type boiling with consequently higher heat transfer rates to the hquid In the case of a spillage of significant quantities the primary emergency will not normally be aggravated by the additional failure of piping systems or equipment Sound judgement is, therefore, necessary on each situation as to whether some method of mitigation or protection is necessary Clearly any system which is essential to deal with the primary emergency is likely to be a priority case for protection Protection measures can be split into three categories depending upon their location 1 protection at or adjacent to a potential source of spillage Measures can be adopted at the source to contain a leakage, hence reducing any m o m e n t u m of the release and preventing a trajectory onto a potential target This is normally achieved by providing boxing, mesh or shrouds around items such as flanged joints, valves, bellows, etc In such cases it is desirable to provide a preferred leak path from within the boxing or shroud so as to conduct the leaking fluid to a safe location This may be achieved by piping or channelling directly or via a sump which drains into

protection at a position between the source and a target Where the possibility arises of a spillage being directed onto a vulnerable object, particularly where there may be a number of potential sources, it is convenient to provide measures such as shields, drip trays, trenches, sumps or water curtains to intercept flow of a leakage, through the air or along the ground The design and location will clearly be based upon the location, type and pressure of the source Examples are shown in Ftgure 4, and protection at or on the target (1 e the equipment to be protected) Protection of the target itself is usually most easily achieved and economical when it is small in size Apart from taking specific measures to remove the target wherever possible, two approaches are feasible, these are the direct insulation of the target (e g using concrete, insulating concretes, resin-based insulating concretes, cellular glass, polyurethene, alumlnlum, or cryogenic steels), or the provision of heating (e g using a water film) In the latter case this will need to be provided on a continuous basis This is because the rate of cooling upon contact with cryogen is too rapid to be overcome by subsequent heating Examples are shown in Figure 5

Protection measures applied on L N G ships and berths can provide a broad illustration of the techniques available, these include the placement of drip trays and Impoundment in manifold areas, sloping of deck plating, the use of cryogenic steels or alumlnlum sheeting, and the application of continuous water films In the selection of any measures for the protection of equipment, a vital factor to consider is the duration for which protection is required For example, this may need to be sufficient to allow time for isolation, evacuation of staff, or to initiate other amehoratlve measures A further factor to consider, particularly in the design of measures such as insulation, is that whenever there is a spillage of a flammable material there is a risk of fire, and there are benefits, therefore, if any measure that is installed can

840

Cryogemcs 1988 Vol 28 December

Cryogenic spill protectmn and mitigation J Moorhouse and P Roberts

Shmhl
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system Figure 6 Examples of vanous bunds and dykes

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Figure 5 Schematic dsagramshowing spillage protection devices adjacent to targets (a) Tank roof protect=on, (b) plant protection
cater for the potentml problems induced by both cold and hot exposure

Sptll c o n t a i n m e n t
If spills of cryogenic hquids occur from process equipment, plpework or storage tanks, the effects can be reduced by using physical systems to contain or direct the leaked material In particular, storage tanks containing flammable cryogenic hqmds such as L N G are invariably surrounded by dykes or bunds, or secondary outer walls, to hold any spdled liquids 8 In addition, process equipment such as pumps may be located in or adjacent to catchment areas, and plpework may run above or beside channels or trenches Dykes, bunds or secondary containment walls around storage tanks, examples of which are illustrated in Ftgure 6 are generally designed to hold the entire contents of a full tank (even though such a large spill is very unlikely to occur) Codes of practice for L N G installations require dyke capacities to exceed 100% of tank contents io Two

principal types of containment are m common usage for flammable cryogenic storage shallow dykes or high walled bunds The former comprise earthen or reinforced concrete walls, typically only a few metres in height, the latter consist of prestressed concrete walls, usually at least half the height of the tank, which are located within a few metres of the outer tank walls The latest generation of tank designs for L N G take this concept one stage further, an integral outer concrete wall, which forms part of the tank itself, provides the secondary containment With the shallow dyke design, xf a very unhkely major spill were to occur, the released liquid would cover a relatively large area, meaning that vaporization could be rapid, high walled bunds minimize the liquid surface area, and thus help to suppress vaporlzauon However, the shallow dyke configuration does allow more scope for measures to be adopted to deal with smaller, more credible, spills, principal examples are primary Impoundment areas, sloping of bund floors or channels Primary impoundment areas are pits or mini-dykes which are designed to contain spills typically less than about 10 % of a full tank's contents Sloping of bund floors not only helps to direct liquid away from the storage tank but also helps to minimize the hquld surface area from a continuous spdl, thus reducing the rate of vapour generauon (see the case study later) Channelhng can be used to collect hqmd from the more likely release sources (e g flanges) and direct these small spills to areas away from tanks and p]pework These containment measures apply principally to above-ground storage, however, tanks may be partially or

Cryogenics 1988 Vol 28 December

841

Cryogentc spdl protectton and mitigation J Moorhouse and P Roberts

totally buried, in which case impoundment may not be needed In the case of non-flammable cryogenics, the provision of secondary containment may not always be considered necessary, even for above-ground storage Impoundment areas around process equipment generally comprise concrete kerbs to contain 'design' spills They are, therefore, normally designed to cater for the maximum process flow for the fixed duration reqmred for reliable detection of the failure and isolation of the equipment The floor area under the equipment may be sloped to take any spilled liquid away from the equipment itself These measures help to reduce the consequences of such spills, allowing smaller on and off-site separation &stances, and minimize the chance of escalation to a larger release Plpehnes for transfer of cryogenic flammable liquids may be provided with channels to contain any spilled liquids The channels may be located beneath the pipelines but a better arrangement is to construct a graded area below the pipe so that liquid may run away to a trench running alongside This will minimize the possiblhty of damage to the line in the event of an ignited release Such a catchment trench may be compartmentahzed along its length to reduce the surface area of liquids from a smaller spill Catchment will be effective only if spills are directed into the appropriate area To achieve this, flanges and other more likely leak sources may need to be surrounded by metal plates or casing, or by mesh shrouds, to reduce the m o m e n t u m of a release Maximum vaporization rates for splllages of L N G onto impervious non-metalhc materials such as concretes11 are 05 k g m - 2 s It is evident that after a period of about 20 rain the rate of vaporization during the 'ground heating phase' falls to about 3% of the initial value After this time heating of the liquid by convection from the air starts to become more important, this mode of heating being driven by the temperature difference between the wind and the liquid For cryogens, such as L N G and LOX, ground heating IS the dominant means of generating vapour and this determines the maximum extent of the vapour cloud In the case of liquids with boiling points close to ambient (e g Butane) the convective heating is more important It is possible to reduce the rate of vapour evolution of a cryogen during the ground heating phase by changing the thermal properties of the grade surface It must be recognized, however, that this will lead to spilled cryogen being present for a longer period and this may be a disadvantage Typical materials such as concrete and sod have high conductlvltles due to their high density, and In the latter case due to ItS high porosity Insulating concretes can provide a reduced rate of heat transfer provided that they are non-porous and of low denslty1112 Three types of materials are available, detailed below
denstty cement-based concretes These materials are made in a similar way to convenUonal concrete except that a low density aggregate is used in place of conventional aggregates Expanded clay, polystyrene particles and vermiculite have all been used The performance of these low density materials is strongly dependent upon the water content, which must be kept to a minimum in order to maintain good insulation Two methods have been found to be effective at limiting water absorption to a maximum of about 10% by volume, these being the use of a styrene-butadlene rubber solution integral with the mix, or a silicone d a m p proofing agent applied after curing, and subsequently at appropriate intervals A thickness of a few centlmetres of insulating concrete is required and this is consistent with the minimum thickness of a layer which can be successfully installed Thermal conductlvltles of typical materials lie in the range 0 3 4 ) 6 W m -1 K -~ (compared with 2-4 W m - 1 K - 1 for standard dry concretes) Low

Vapour control
Once a spillage has been safely contained within an impoundment area it may be desirable to take further measures to minimize the consequences of subsequent vapour evolution Two approaches may be considered the rate of vapour evolutmn may be reduced, either by minimizing the area of contact with the substrate, or by reducing the rate of vapour generation per unit area, the dispersal of the evolved vapour may be enhanced, thus reducing travel distances to non-hazardous concentrations

Vapour evolution
If a spillage of a cryogenic liquid occurs onto a surface which is initially at ambient temperature, then heat will be transferred from the ground into the hquld This heat will raise the spilled hquld to its bolhng point and then cause the liquid to vaporize The rate of vaporization, which decreases rapidly with time as heat is withdrawn from the ground, is dependent upon the lnltlal temperature difference between the cryogen and the ground, AT, and the thermal properties of the surface as
m = BATt -~

Resm-based materials

where m = mass vaporization rate per unit area of surface, B = a measure of the effective thermal properties of the surface, and t = time from initial contact

These materials are made by mixing a hghtwelght aggregate (glass, perhte, or even air bubbles) with a resin (polyester or epoxy) binder There is considerable scope for selecting the final material density and thermal properties by selecting appropriate aggregates and mix ratios, and the use of a resin ensures very high resistance to water absorption Due to the flammability of resins a fire retardant agent is required for flammable cryogens The cost of these materials is high, particularly for epoxy resins, but only thin layers are required (about 10 mm) to provide effective insulation Direct casting is possible on horizontal surfaces whereas other surfaces will require precast panels Thermal conductlvltles he in the range 0 24) 4 W m - 1 K - 1

Foamed polyurethane

Thlsmaterlalexhlblts excellent thermal properties but particular care is needed in seahng it so as to prevent moisture ingress Other factors are that

842

Cryogemcs 1988 Vol 28 December

Cryogemc sptll protectton and mcttgatton J Moorhouse and P Roberts

it requires a flame retardant, complete bonding is difficult and protection against sunlnght ns necessary to prevent degradation by ultraviolet radmtlon All the above three types of maternal may find applncation for the insulation of the surfaces of impounding areas Each will be effective provnded that it maintains a bond to the substrate and water absorption ~s minimized ~3 During the 'convective heating phase' heat transfer from the ground is not significant and, therefore, insulation of bund surfaces is not effective The rate of convective heating can, however, be reduced by providing a barrier at the liquid surface Such a barrier may consist of a floating granular material or an aqueous foam Granular matemals will reduce the effective surface area of the lnqmd and will also prevent the extraction of the vapour Matermis such as foamed glass 14 is can be effective, and have an additional benefit in that for splllages of flammable cryogens, they can also rapndly provnde a high degree of fire suppressnon High expansnon ratno aqueous foam has been attempted as a means of reducing convective heating/6 In practice this suffers from the &sadvantage that drainage of water from the foam can enhance vapornzatlon rates, although the foam can enhance dispersion (see below) An additional means by whnch vapomzaUon of a spillage can occur ns upon contact with vessels, steelwork and other eqmpment This should be prevented whenever possnble (as &scussed prevnously) Insulation can again be used here to reduce rates of vaporization as well as to protect eqmpment, the polyurethane type of insulation is generally most suntable here Also of importance is the need to prevent the occurrence of standing water due to ram or water from fire water mains in any part of an impoundment area This can reduce a very high rate of evaporation of a cryogenic liquid Provided that impoundment areas are properly drained and excessive contact between spilled INmd and plant is avoided then for cryogens, the overall safety distance is determined almost entnrely by the rate of heat transfer from the ground
100

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Distance fr{)m b(iurt.~. (ml F i g u r e 7 Influence o f a vapour barner on vapour cloud travel d~stances w i t h o u t v a p o u r barner, spill 019, 6 4 m s 1 O, With vapour bamer, spill 020, 5 7 m s 1 Source 2000 m 3 in a 13 m hMgh tent of 14m radms*

Vapour dtsperston
In addition to the measures described above to reduce the rates of evolution of vapour from a cryogemc spill, techniques are available to enhance the &sperslon of the evolved vapour and thus reduce vapour travel distances The available techniques can be usefully dlvnded into two broad categomes passive (le dormant) systems requiring no physical intervention by the operator, and actnve systems which need to be actnvated manually or automatically when a spill occurs Passive systems for dispersal of vapour comprise physical barriers (or so-called vapour fences) located to contain clouds of dense vapour Examples might be effective use of snte topography, planting rows of trees, or erecting specially designed fences at strategic locations such as on the top of a shallow dyke surrounding a cryogenic storage tank 17 Some research into the effectiveness of such de~lces has been undertaken, an example of which is shown in Figure 7 It would appear that a correctly placed vapour fence may reduce flammable vapour travel distances and sometimes significantly reduce concentrations close to the dyke in low wind speeds

and may also reduce concentrations further downwind The l'horney Island trials is provide data for comparison of the effects of such obstacles on dispersion of both instantaneous and continuous types of release There is some evidence that such barriers are slightly less effective at higher wind speeds, and they would not be effective for very large spills, such as major tank failures In addition, it should be noted that the &stances to low concentration levels may not be reduced significantly by vapour fences 19 A further factor to note when considering any form of vapour fence is that it may interfere with the free dispersal of the vapours from the plant area A balanced view of the advantages and disadvantages, therefore, needs to be taken before adopting such a measure Active systems to enhance vapour dispersion generally comprise sprays or jets whose purpose is to induce turbulence and entrain air into the vapour cloud The most common such system is the water spray barrier or curtain, which comprises a set of parallel or divergent jets located either close to spill sources or near Items of equipment or areas where vapour ingress should be prevented 2 The use of such devices is not restricted to facflmes handling cryogens, water spray bamers are, in fact, used quite widely in chemical plants As with vapoui fences, research work has shown that water sprays can be very effective m reducing local vapour concentrations ff
*Data taken from Dawes M E and Smgh S J H a z M a t e r (1985)

Cryogemcs 1988 Vol 28 December

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Cryogenic sp/ll protection and mittgat/on J Moorhouse and P Roberts

placed close to the release source in low wind speeds, up to about 3 m s - 2, but they are believed to be less effective at high wind speeds 21 It is also believed that they do not tend to reduce vapour travel distances to low concentratlons to any great extent The detailed design of a water barrier - e g nozzle configuration, nozzle spacing, jet direction (upwards, downwards, angled) - is extremely Jmportant 2L22 Water barriers are mainly used to deal with small releases, their use for very large spills is unproven and would cause problems with water drainage and disposal It should be noted that, if water falls directly onto a pool of cryogenic liquid, the vapour evolution rate will be substantially increased Variations of the above technique are steam or gas spray barriers, which are designed to function In a similar w a y 2 3 ' 2 4 An alternative way of enhancing vapour dispersion might be to apply a high expansion foam to the surface of a cryogenic pool This would not suppress vaporization to any noticeable extent for a cryogenic liquid, since most of the heat leak to the pool in the initial period following a spillage is through the ground Use of a low or medium expansion foam could actually increase the vaporization rate by providing heat to the surface of the pool (see above) However, high expansion foams could serve to warm cryogenic vapours and introduce some turbulence, thus enhancing dispersion Such foams are commonly deployed on sites handling flammable cryogens, although their primary purpose is normally for fire suppression rather than vapour dispersion Regular application of foam is needed to make up for the rate of foam drainage and breakdown by the cold vapours or a shallow dyke, but in each case the bund is able to hold not less than 100% of the tank contents high walled bund a 50 000 m 3 tank was selected as representative of current bulk storage, the tank being provided with a roof outlet via a submerged p u m p The circular prestressed concrete bund was chosen to be 2600 m 2 i n area and 25 6 m in height, and shallow bund - a 50 000 m 3 tank was again selected but with a bottom side wall outlet The bund is provided with a primary impoundment area of 2100 m 2 within a total area of 7500 m 2 The base of the bund was considered to be flat In addmon, a case was considered in which the bund floor was provided with a slope of I in 40. In order to examine the merits of such a simple modification This was intended to allow a spillage to accumulate with the minimum contact area between the liquid and the bund surface

Spillage scenarios
A 'design' spillage rate was considered in each case, which is that specified in the N F P A 59A Code as the basis for determination of separation distances 9 For the tank in the high walled bund, with no penetrations below the liquid level, the design spillage rate was considered to be that from an outlet line rupture releasing cryogen at the maximum pumping rate for a period of l0 mln (taken to be 0 15 m 3 s -z) For the tank in the shallow bund, with a penetration below liquid level and no in-tank valve, the design spillage rate was considered to be that from the complete rupture of the outlet line, the flow rate being determined by the hydrostatic head of liquid in the tank, until the tank was empty (Maximum rate = 1 54 m 3 s reducing to 1 46 m 3 s-x after 1 h)

Case study
To compare the relative effectiveness of some of the practical measures for vapour control which are discussed in this Paper, a case study was carried out This study was intended as a theoretical study, without any consideration of the cost of the measures considered or of the likelihood of the failure scenarios selected The sole purpose of the study was to allow a consideration In a quantitative way of the various measures which can be used to reduce vapour cloud travel distances when studying impoundment design and siting Whether this is considered necessary or desirable for any particular case is clearly outside the scope of this Paper The study assumed that the cryogen which is spilled is L N G , but the general principles of the study are relevant to all cryogens for which vaporization due to ground heating dominates The basic details are as follows a spillage is considered to occur which is directed into and contained within an Impoundment area, the L N G is at its boiling point and upon contact with the surface of the Impoundment area it starts to vaporize N o vaporization ofhquld is assumed to occur whilst the liquid flows down drainage channels As the vapour is evolved it is dispersed by the wind

Bund materials
The high walled bund was considered to be constructed of conventional concrete The shallow bund was considered to have soil walls and a soil base As an additional case, the soil base was considered to have a loose layer of granite pebbles at the surface, as is sometimes installed to assist water drainage

Bund insulation materials

Bund Insulation materials offer a direct way of reducing vaporization rates Materials meeting the rigorous requirements for continuous outdoor exposure were selected For vertical surfaces, insulation with a lightweight concrete was adopted For horizontal surfaces, where a high resistance to water take-up is required, a resin based lightweight concrete was selected In one of the cases an idealized insulation material ('super' Insulating concrete) was selected, having much better properties than the conventional lightweight concretes This was included In order to determine whether there are any advantages in developing even better insulation materials Details of the two types of bulk storage facility together with location of the Insulation materials are shown in Figure 8a and b

Bund des/gn
Two types of bulk storage faclhty were considered in this study, these being those utilizing either a high walled bund

844

Cryogenics 1988 Vol 28 December

Cryogentc sptll protectton and mtttgatton J Moorhouse and P Roberts

a

) Total impoundment area = 7500 rtl"

[ nbLllatlon

~ ~ /
Max,mum ieakage rate \~"

t mary Impounulnen~ff
of area 2100 m2 //

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COflCre'Le hulqd

\
Ltghtw~mjaqt
In

tank
Rcsm based

corlct Ct.t~ Insulatlor)

pump Maxtmum leakage rate = 0 15 m 3 s 1

Bond area = 2600 m 2

selected to ensure that the comparisons are fair and realistic One parUcular aspect was difficult to model the addmonal influence of the gravel on top of the so~l surface This was done by allowing for the extra surface area of the gravel which lmtlally enhances the rate of evaporation of cryogen, but any effect of gravel on pool spreading was ignored No allowance was made for the contact of L N G with any other objects or surfaces other than the bund This will depend upon the manner and source of leakage and its effect will be to exaggerate the benefits of bund insulation Further, no allowance was made for the influence of obstacles which'lend to increase mixing and reduce dispersion distances This omission does not invalidate the conclusions drawn on the relatwe effects of each of the measules examined The calculations of vapour cloud travel distances was carried out for one weather condition for all cases considered (5 m s-1 wind, neutral atmospheric stablhty conditions Pasqudl/G]fford Category D) The results of the calculations are shown m Tahle 1 The figures are presented as a proportion of the distance for a selected base case (an outlet hne failure mto a soft bund with gravel) which is assigned a value of umty

F i g u r e 8 Schematic dmgram of installations considered m the case study (a) Storage installation w i t h shallow bund, (b) storage installation wMth h~gh walled concrete bund

Fmdmgs of the case study

On the basis of the figures presented in Table 1 It Is possible to make the following observations (in quahtatlve terms, slmdar findings would be expected for other weather conditions) 1 considerable reductions m vapour dispersion distances are obtained by use of insulation on shallow bunds, or by use of concrete htgh walled bunds Further reductions are possible by insulation of high walled bunds Any further reductions which could be achieved by developing even better insulation materials are not of s]gmficance, some reductions in vapour dispersion d~stances are achieved by removal of loose pebbles from a shallow bund, but greater reductions are achievable by means of msulauon, and

The B values for the various bund materials selected for use m th~s study are as follows
B value (kg m 2 s '-) Sod Standard concrete Lightweight concrete Resin concrete "Super' insulating concrete 06 0 58 0 14 0 1 0 07 Assumed average water content* (% by volume) 33 67 50 0 0

These values were used as input to a model for calculating the total rate of vapour from a spdlage

Vapour dlsperston calcula#ons

The purpose of the case study is to compare the relative merits of various practical measures This was done by calculating the maximum vapour cloud travel distance to the lower flammable hm]t (5% by volume for L N G vapour) for each spillage scenario The vapour cloud travel d]stances were calculated by matching the results from a pool spread and vaporization model (which predicts pool size and vapour generation as a function of time) with a dense gas dispersion model The techmque is described in detail elsewhere 25 26 It was assumed that dispersion took place over flat, unobstructed, terrain Various assumptions were made m order to perform these calculations However in all cases these were
*Values based on data from outdoor exposure tests

T a b l e 1 Comparison of relative vapour travel distances to the lower flammable limit for spills mto various types of containment a Bund type Bund material Relatwe vapour travel dmtance 0 16 0 06 0 04 1 0 0 0 00 80 21 20

High walled bund

Standard concrete Insulated Super insulated Soil base w i t h gravel Soil base Insulated base Sloping soil base

Shallow dyke

aF~gures are presented as a proportion of the distance for a base case the shallow soil bund with a loose gravel floor covering The insulated bund uses resin concrete on horizontal surfaces and lightweight cement-based concrete on vertical surfaces All cases are for a 'design outlet line spill in 5 m s 1 wind speed and D atmospheric stability (neutral)

Cryogenics 1988 Vol 28 December

845

Cryogentc sptll protectton and mttlgatton J Moorhouse and P Roberts

3 equivalent reducttons m vapour cloud travel distances to those provtded by the use of insulation can be obtained for the spills considered into shallow bunds by sloping of the bund floor, provided that the liquid can be efficiently channelled into the lowest point of the bund without excesstve contact with other surfaces 5 Johanson, K A Design of a gas monitoring system AICHE Lovs
Prevention (1976) l0 15

6 Eng (1984) 407 41 7 Herbert, F Onhne laser detection of gases Electron Po~er (1983)
29 (4) 314-316

Herbert, F Detection of fugitive emission using laser beams Chem

8 Parker, R O LNG &ke design Paper presented at the 3rd 9 10 11

12 Conference m Natural Gas Research and Technology, Dallas, (1974) Standard for the Productton Storage and Handhng of Ltquefied Natural Ga~ (LNG) NFPA 59 A National Fire Protection Assooatlon (1985) Liquefied Natural Gas Facthttev Federal Safety Standards 49 CFR 193 Federal Register (1980) Lung, R Z J , Moorhouse J and Paul G J Waterproof insulation materials Paper presented at Institution of Chemical Engineers Seventh Symposium on Process Hazards, Manchester, UK (1980) Moorhouse, J and Carpenter, R.J Factors affecting vapour evolution rates from hquefied gas spills Paper presented at the Symposium on Refinement of Estimates of the Consequences of Heavy Toxic Vapour Release, Institution of Chemical Engineers, North Western Branch, UMIST, Manchester, UK (1986) McClune,C R and Moorhouse,J The Development of Waterproof Insulation Materials based on Lightweight Concrete Mag Concrete Research (1981) 33 (114) 27-36 Lev, Y A Novel method for controlhng LNG pool fires Fzre Technol (1982) 275-284 Lev, Y UK Patent GB 2048449A An Installation for the Storage of Ltquefied Gases (1980) Prugh, R W Gmdehnes for vapor release mitigation Plant Operations Prog (1987) 6 (3) 171-174 Kothan, K M and Meroney, R M Acceleratton ddutton ofhquefied natural gas plumes with fences and vortex generators Final Report CER81-82KMK-RNM79 for Gas Research Institute, Contract No 5014-352-0203, Colorado State Umverslty, Fort Collins, Colorado, USA (1982) J Haz Mater (1985) l l , (1987) 16 Special Issues devoted to proceedings of 1st and 2nd Symposia on the Heavy Gas Dispersion Trials at Tborney Island (See, m particular, Dawes, M E and Smgh, S J Haz Mater 11 301-324 and Danes, M E and Inman, P J Haz Mater 16, 149-172) Brighton, P M W and Prince, A J Overall properties of the heavy gas clouds m the Thorney Island Phase II trials J Haz Mater (1987) 16 103-138 McQumd, J and MOndle, K The scope for reductmn of the hazard of flammable or toxic gas plumes Paper presented at the Seminar on Toxic and Flammable Gas Clouds Hazards and Protection, Institute of Mechamcal Engineers, London, UK (1982) Mondle, K The use of water spray burners to disperse spills of heavy gases Plant~Operation Proo (1985) 4(4) Snuth, J M The use of upward &rected water sprays to disperse heavy gas clouds Paper presented at the Symposmm on Heavy Gas Releases - - Dlspersmn and Control, Institute of Chemical Engineers, European Branch, Utrecht (1984) Rulken, P F M. The apphcatlon of steam curtains for the dilution of gas clouds Paper presented at the Symposmm on Heavy Gas Release - - Dispersion and Control, Institute of Chemical Engineers, European Branch, Utrecht (1984) Rulkens, P M e t al The application of gas curtains for diluting flammable gas clouds to prevent their lgmtlon Paper presented at the 4th Loss Prevention Symposmm, Harrogate, UK (1983) Cox, R A and Carpenter, R.J Further development of a dense vapour cloud dispersion model for hazard analysis Paper presented at the Battelle Institute Symposmm on Heavy Gases and Risk Analysis, Frankfurt, FRG (1979) Bradley, C I e t al Recent development of a simple box-type model for dense vapour cloud &spersmn Paper presented at the Battelle Institute Second Symposium on Heavy Gases and Rssk Analysm, Frankfurt, FRG (1982)

Whtlst reductions in vapour dispersion distances can be achieved using the techniques discussed, it should be recogntzed that these arise primarily due to a slower rate of evaporation of the cryogenic liquid As a consequence the spilled liquid will be present for a longer period, which may be a disadvantage

Summary
This brief review hlghhghts some of the principal measures which are either currently adopted, or are suitable for adoption, to mlUgate the effects of spills of cryogenic liquids Whilst the measures have been drawn from experience with liquefied natural gas they are likely to be equally applicable to other cryogens It is evident from the logical sequence in which various measures have been presented, i e spill prevention, detectmn, tsolatlon, eqmpment protection and spill containment, that there is considerable opportunity for breaking a chain of events which may prevent a small incident escalating into one which lS more severe The results of a case study serve to quantitatively demonstrate the potential reductions in vapour cloud travel distances to be gained from some of these safety measures However, no attempt has been made to justify any of these in terms of costs, since this will depend upon the particular locahty and site conditions Constderatlon needs to be given both to the relative costs of measures discussed in this review, and to their effectiveness in any pamcular situation, in order to determine the optimum solution for the storage or process facility being considered
13
14 15 16 17

18

19 20

21

Acknowledgements
The authors would like to thank their colleagues in British Gas for their valuable contributions towards the Paper This Paper is published by permission of British Gas plc

22

23

References
1 Destgn and Constructton Spectficatlon for Marme Loadmg Arms OCIMF, Wltherby and Co Ltd, London, UK (1980) 2 UK Patent BP 1450 047 Method and Devwefor the Detectmn of a Fadure on a Cold lnsulatton System (1976) 3 UK Patent BP 1493 124 A Devwefor Detectmg a Fadure m an ln~ulatlon System m partwular m the lnsulatton System of a Crvogenw Tanl~ (1977) 4 Place, J D and Pinchbeck, D Fibre Optic Sensors for the gas industry Commumcatlon 1269 IGE (1985)

24 25

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Cryogemcs 1988 Vol 28 December