Int. J. Hydrogen Enerfly Vol. 4. pp. 559-569 Pergamon Press Ltd.

1979, Printed in Great Britain International Association for Hydrogen Energy

0360-3199 79 1201-0559 $412.00/0

PHYSICAL, CHEMICAL AND ENERGY ASPECTS OF UNDERGROUND HYDROGEN STORAGE

P. O. CARDEN and L. PATERSON Department of Engineering Physics, Research School of Physical Sciences, The Australian National University, Canberra, A.C.T., Australia

(Receivedfor publication 26 July 1979)

Abstract--Large scale energy storage is becoming an important consideration as we turn more towards nuclear power and the utilization of renewable sources such as solar energy. Underground storage of hydrogen in aquifers has been suggested as an inexpensive method of providing the required energy storage. With this theme in mind, the losses associated with gas storage in aquifers are discussed. These losses include physical leakage of gas, loss of gas through underground chemical reactions and the energy requirements associated with storing and recovering the gas. Although underground storage of hydrogen appears a most promising solution to the problem of large scale energy storage it is shown that much work remains to be done to confirm this. For example, better estimates of hydrogen diffusion through water saturated porous media are required. 1. I N T R O D U C T I O N UNDERGROUND storage of hydrogen gas is a possible means of inexpensive, large-scale energy storage. Energy storage is becoming a problem of increasing importance both with regard to nuclear power and to renewable energy sources. In the former case, as more electrical power is produced by nuclear means the role of the nuclear station moves from being a base load plant towards providing also the power peaks of short duration. Since nuclear stations are expensive (although low in running costs), it is clearly uneconomical to employ some of them only during periods of peak demand and to have ; them idle the rest of the time. Such a situation would be avoided if a smaller number of nuclear plants could be employed in conjunction with an economical means of storing the energy output in times o f surplus for use during times of peak demand. With regard to renewable sources such as wind and solar energy, it is not so much the variability i of the consumer that is the problem but rather the source. The reason for providing storage is to reduce i the amount of fossil fu$11sd back-up plant that would otherwise be required in order to offset t h e variability of both the source and the consumer's demand. One of the attractions of underground storage of hydrogen is that the potential capacity is immense i and it is provided by nature at no cost. The cost of providing access wells tends to be related to the! rate of storing energy rather than the quantity of energy stored. Thus long term seasonal storage m a y be economically feasible and this would allow the new energy sources to stand completely independent! of fossil fuelled back-up plants. The underground storage of hydrogen is also relevant to several developing technologies whichi involve mixtures of hydrogen with other gases, such as carbon monoxide, carbon dioxide, methane! and nitrogen. Examples of these technologies are the underground gasification of coal, the storage i of"synthetic" natural gas and the storage of gas mixtures employed in the thermochemical transportl of energy [1-4]. Underground reservoirs of particular importance for the storage of pressurized hydrogen are the i water bound ones known as confined aquifers. These may be defined as water-bearing, porous sedi-I mentary formations comprising a permeable layer bounded above and below by impermeable layers. The upper layer is referred to as the cap layer. A schematic of an aquifer storage reservoir is shown in Fig. 1. As gas is pumped into an aquifer, water is displaced and must be accommodated elsewher~ The vastness of sedimentary basins allows this displaced water to be accommodated by thd compressibility of water and rock. Our discussion will be limited to such aquifers which generall)l include depleted natural gas reservoirs. The possibility also exists for storage in dissolved salt caverns in mined or natural caverns and in underground cavities induced by nuclear explosions. 559

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P. O. CARDEN AND L. PATERSON

5:.. '~ ~:'~'Y;': -"" ~

" ""~;"":"~ ~"'" ~ ; >~'~"!~:;~:~:'~ " ~ : ~ ......

//~,/~///~i

FIG. 1. Illustration of gas storage in an anticlinal trap. It is important to distinguish the confined aquifer that is suitable for hydrogen storage from the near-surface aquifer, or phreatic aquifer, often used for water supply purposes. The phrcatic aquifer is bounded above by the water table. It is necessary to drill through the phreatic aquifers to gain access to the lower confined aquifers. Well casings are designed to prevent the leakage of gas past or through them, and should therefore leave the near-surface water uncontaminated. There is a considerable body of industrial experience that indicates the nature of the problems which may be encountered in storing hydrogen. Most of this experience is derived from the natural gas industry, where gas is n o t o n l y extracted from natural reservoirs, but is often cleaned and then stored in other underground reservoirs prior to consumption. The helium industry provides another source of experience. Since both hydrogen and helium are particularly prone to leaking through molecular sized crevices, the experience in the U.S.A. where helium is discovered and stored in underground reservoirs is especially relevant. So too is the experience of Gaz de France who, from 1957 to 1974, stored gas mixtures containing up to 5 0 ~ hydrogen in a reservoir near Paris (Beynes) [5]. Unfortunately the hydrogen loss during storage was not measured. Underground storage of hydrogen gas has been proposed by several authors, e.g. [6-10], but until now little attention has been focused on actual investigations of this concept. Waiters [11] has considered some of the technical and environmental aspects of underground hydrogen storage by making comparisons with existing natural gas storage, and has concluded that there should be no insurmountable technical problems. Natural gas storage was developed when natural gas was very inexpensive, and much of what we know about natural gas storage was learned by experience rather than by an actual understanding of the physical processes. It would be advantageous for the physical processes of underground storage to be well understood because hydrogem iland will continue to be relatively expensive, and therefore optimum selection and utilization of reservoirs will be desirable. It is with this in mind that the various loss mechanisms in an underground gas storage reservoir, particularly as they relate to hydrogen, are discussed in this paper. These losses can be broadly classified into two types: once only, or capital, losses and continuous, or operating, losses; but, before these losses are discussed, it will be helpful to introduce some of the concepts and terminology which will be used. 2. DESCRIPTION There are several types of aquifer traps suitable for hydrogen gas storage, an example being the anticlinal trap illustrated in Fig. 1. Access to the reservoir would probably be by a number of standard fined wells of about 20 cm diameter. As gas is introduced into a reservoir at a pressure above the natural pressure, water and rock are compressed, and water is displaced away from the wells. This water displacement has an associated time constant which depends on the ground's resistance to water flow. Experience with natural gas storage demonstrates that aquifers typically behave over periods of months as constant pressure, variable volume reservoirs and over periods of days as fixed volume, variable pressure reservoirs. These times are, however, subject to wide variations depending on many factors such as reservoir geometry, porosity and permeability. Secondary wells connected to an above ground water reservoir would aid water movement.

CHEMICAL AND ENERGY ASPECTS OF UNDERGROUND HYDROGEN STORAGE 2.1.

561

Terminolooy

The portion of rock not occupied by solid matter is cared the void space and is either filled by liquid or gas. Porosity, a macroscopic quantity, is defined as the ratio of the volume of the void space to the bulk volume. Nearly all flow that occurs in an underground gas reservoir can be described by Darcy's law (e.g. see Bear [12]):
q = k--~P ( p + OZ), p v \P

(1)

where q is the specific fluid discharge (or effective bulk fluid velocity, in units of m s- 1), k is the permeahility of the medium,/t is the viscosity of the fluid, p is the pressure, p is the fluid density, # is the gravitational constant and z is the height above a horizontal reference plane. Permeability is defined! through this equation and, for single phase flow, is a function only of the porous medium. The following are representative of the magnitudes of permeabilities for several types of medium in units of i darcy (1 darcy = 9.8697 x 10 -13 mZ)l": 10s-101 for pervious gravels and clean sand; 1fix-10 -3 for semipervions free sands, silt and sandstone; and 10-3-10-8 for impervious unweathered clays, dolomite and granite. When two fluids are present in the porous medium, for example water and hydrogen, the relative! permeability with respect to one of them is less than the single fluid value. This effect is illustrated ini Fig. 2. In the case where both fluids are moving through the medium, as is the case at the boundary of the stored gas bubble (Fig. 1), the combined permeability will be less than the single fluid value.i This effect tends to keep the transition zone between predominant gas saturation and predominant liquid saturation fairly localized in space.

0 Wofer soturafion

100%

FIG. 2. Schematic of the qualitative nature of relative permeabilities. In practice, after a storage cycle we may expect all parts of the swept medium to contain a propor i tion of both fluids. This is due to the phenomenon of residual saturation which refers to the quantity of one of the fluids held in place principally by surface tension after the bulk of that fluid is displaced by the second fluid. (Residual saturation is treated in Section 3.) In the general case of two fluid flow, the mobility of a fluid 1 is defined as:
i

/,t t

I" Darcy is the unit most often used by reservoir engineers and is based on a definition of I darcy = 1 m centipoise/(l atm x 1 s).

562

P.O. CARDEN AND L. PATERSON

where k I is the permeability to fluid 1 at residual saturation of fluid 2, and #1 is the viscosity of fluid 1. 2.2. The geometry of the gas "bubble" The concept of a gas bubble as shown in Fig. 1 is rather naive. The interface between two fluids, for example hydrogen and groundwater, is stable or unstable depending on the relative magnitudes of the viscous, interfacial and gravitational forces and the direction of movement of the interface. Instability occurs in horizontal flow when the mobility of the displacing fluid is greater than the mobility of the displaced fluid. This instability may cause long fingers of the displacing fluid to penetrate the displaced fluid, hence the term "fingering". Such is the case when hydrogen or natural gas displaces water (but not when water displaces hydrogen or natural gas). The concept of fingering in a gas reservoir is illustrated in Fig. 3. Initial experiments with models in our laboratory suggest that fingering in a hydrogen reservoir would be essentially similar to that in a natural gas reservoir despite the viscosity differences between the two gases. The viscosity difference between water and gas, rather than the viscosity ratio, seems to be the factor dominating fingering.

_
/

SURF/~

~-~WTRTRTD AEAUAE S
FIo. 3. The concept of "fingering" in an underground storage reservoir. Fingering has been identified as a problem in natural gas storage [13]: it can for example cause a high rate of gas travel "down-structure" toward spill points. (Synclines are spill points in anticlinal traps.) Sometimes fmgering may be so pronounced that the injection rate must be severely curtailed, and this excessively lengthens the time required for bubble growth. Moreover, the fingering process leaves some water undisplaced quite close to the bottom of the well and consequently it is often difficult to obtain water-free gas recovery. Computer simulations of water displacement by gas in the development of aquifer storage [14] indicate that steeply dipping structures and thick sands will help to inhibit fingering. These simulations also indicate that reservoir heterogeneity plays a key role in fingering. However, defining heterogeneity is a problem in itself (e.g. [15]). Fingering is of particular importance to our study because of its deleterious effect on diffusion losses, pumping losses, losses due to residual gas saturation and solution into connate and groundwater. 3. ONCE ONLY LOSSES 3.1. Cushion gas For a storage facility to be economical and still meet consumer demands, it must be able to release hydrogen to the withdrawal wells at relatively high rates. If the reservoir were to operate isobarically,

CHEMICAL AND ENERGY ASPECTS OF UNDERGROUND HYDROGEN STORAGE

563

similarly high rates of inflow of groundwater would be necessary in order to displace the gas, but permeabilities are generally insufficient to allow this to occur. Consequently, the reservoir behaves like a vessel whose volume is constrained to change comparatively slowly, and in which gas expansion takes place during withdrawal. Both flow and reservoir pressure therefore diminish with time. Thus, at the be~nning of the next charging period, there will still remain a residual quantity of gas in the reservoir known as the cushion gas. A cushion of about one-third of the total gas capacity of the reservoir will need to be invested for the entire operating life of the storage facility according to Waiters [11], and this is one of the main capital expenses of an underground storage facility. 3.2. Cushion gas recovery Upon eventual abandonment of the reservoir, some of the cushion gas may be recovered: that which is not trapped either on the microscopic or macroscopic scale. Cushion gas recovery is therefore a negative once-only loss, but of probable low monetary value because profits in the future are customanly discounted to the present by accountants. The trapped cushion gas takes the form of undissolved gas pockets ranging in size from many meters down to the dimensions of the rock pores. The latter are classed as microscopic in this discussion, and the former macroscopic, The amount of gas trapped will depend on reservoir heterogeneity, final gas recovery rate and fluid and rock properties such as density, viscosity, relative permeability and surface tension. 3.2.1. Macroscopic gas trapping. Although the mechanisms for macroscopic gas trapping in reservoirs are complex, the physical processes are well understood, and it is therefore possible to learn a great deal from studies using computer models. For example, Knapp et al. [16] have shown that cushion gas recovery increases with increasing recovery rate. Moreover, the ability of an aquifer to produce water through a connecting well, known as aquifer strength, plays an important part in determining the amount of cushion gas recovered; the amount recovered decreasing with increasing aquifer strength. These simulations also show that recovery is very dependent on reservoir heterogeneity. 3.2.2. Microscopic gas trapping. When water displaces a gas in a porous medium, a certain amount (typically 20 %) of the gas is trapped in pores; this is known as the residual gas saturation. The mechanism for this can be illustrated by imagining part of a porous medium as a conglomerate of contiguous cavities interconnected by relatively minute windows where they touch. Gas will be trapped in those i cavities whose windows are so small that the capillary pressures exceed the driving pressure differentials across them. This loss is enhanced whenever the gas "bubble" sweeps different regions on successive cycles. When a gas reservoir is abandoned, a considerable portion of the cushion gas is lost in this manner. 3.3. Solution via connate water When gas displaces water there is an analogous residual water saturation. The trapped water is called the connate water. Ways in which this water may be trapped are shown in Fig. 4. This irreducible connate water will be exposed to the storage gas, which will dissolve in it and quickly form a saturated solution. Thus a portion of the original gas is lost in this manner. If, for example, connate water were to take up 20 % of the pore volume, and if one assumes that this connate water becomes saturated with hydrogen, then about 0.4 % of the gas in the first charge of stored gas will be irretrievably lost in this manner. As the reservoir subsequently empties and unsaturated groundwater replaces gas, the dissolved gas in the connate water will diffuse into the groundwater and will be carried away when the reservoir next fills with gas. However, it is quite likely that the same groundwater will return next cycle tel receive more dissolved gas from the connate water, in which case the concentration of dissolved gas in the groundwater will approach closer to saturation with each cycle. A simpler extension of the above I calculation shows that, in the example given, the groundwater would be over 90 % saturated after 11 cycles and 99 % saturated after 20 cycles. But this simple mechanism may be impeded by the i presence of a saturated water layer at the gas bubble boundary. As the reservoir fills with gas, this!

564

P. O. CARDEN AND L. PATERSON

[]

6AS

WATER

[] R C OK

FIG.4. Ways in which water (or gas) can be trapped in rock (a) in by-passed pores, and (b) in dead-end pores.

saturated layer sweeps through the medium and may leave behind connate water already saturated with gas. If this occurs, little of the newly stored gas will be lost by solution into the connate water and this loss mechanism will be much slower than the above calculation suggests. The picture portrayed is based on the concept of reversible flow of groundwater, i.e. the notion that in regions sufficiently remote from the boundary of the gas "bubble" groundwater will travel the same path to and fro from cycle to cycle. This concept itself needs to be verified even though there are strong theoretical reasons to believe it is correct. The amount of loss due to solution into connate water will probably be markedly dependent on the extent of fingering. This is because gravitational and boyancy forces will cause the ideally reversible water flows associated with fingering to be converted to circulatory currents or eddies. Thus, not only will the water displaced by the fingers become saturated, but also the water between the gas fingers. 3.4. Diff~ion into groundwater Geological factors and the ultimate effect of boyancy on the geometry of stored gas bubbles will cause almost all large reservoirs to possess relatively small vertical dimensions and large horizontal dimensions. A very large surface area of caprock is therefore likely to be exposed to gas or saturated groundwater during a storage cycle. In either case, the lower layer of caprock will be kept close to saturation and diffusion of dissolved gas will take place vertically in practically immobile water. There will also be a similar diffusion loss downwards. There will also be a "horizontal" diffusion loss in the mobile groundwater beyond the region effected by connate water solution (which is itself beyond the region containing fingers), but this will be relatively insignificant in most cases as the following calculations will show. The diffusion equation is Oc a---t= DV2c' (3)

where c is the concentration of the diffusing species and D is the diffusivity; c will take the value of the saturated solution at the boundary and will generally decrease as the distance to the boundary increases. The solubility of hydrogen is less than the solubility of methane, but hydrogen has a higher diffusivity. According to Henry's law, the solubility of hydrogen, on a volume basis, is independent of pressure and can be derived from the solubility at atmospheric pressure. At atmospheric pressure 1.9 vols hydrogen dissolve in 100 vois water at 16C. Solubility decreases with temperature. We will take the value for the diffusion constant of hydrogen in water as 5 x 10 -s cm2/s, the value at 1 atm [17], and assume it is independent of pressure. It is expected that the diffusion constant will actually decrease with pressure as the molecular spacing of the water decreases, but this remains to be verified by experiment. Other mechanisms may act to increase the diffusion coefficient. For example, experiments by Pandey et al. [18] for helium and Chen et al. [19] for nitrogen and methane indicate that it is likely that the effective diffusion coefficient of liquid saturated porous cores will be higher than for open space liquid. The reasons for this are not yet clear. If the same sort of increase occurs for hydrogen, then an increase in losses of up to an order of magnitude could be expected. Clearly this is another area where more work is required.

CHEMICAL AND ENERGY ASPECTS OF UNDERGROUND HYDROGEN STORAGE

565

The losses through diffusion will decrease with time because the water surrounding the gas in the reservoir will gradually approach saturation. Consequently, the hydrogen concentration gradients will decrease and this will inhibit further diffusion of dissolved hydrogen. F o r instance, consider a storage aquifer in the shape of a right cylinder with the axis of symmetry vertical. In theory, the best dimensions for such an aquifer would have the height equal to the diameter as this would give the greatest volume for the least surface area, and hence the least diffusive loss. However, as we have already observed, in practice gas reservoirs are not of very great height. The gas reservoirs in the Cooper Basin, Australia, for example, have a typical height of 7 m [20]. If it is assumed that the diameter is many times larger than the height and the porosity is 0.2, then Fig. 5 shows the percentage loss of gas/yr from a 7 m high reservoir. This calculation is based on the assumption that the gas remains dormant underground and the adjacent mobile groundwater contains no dissolved hydrogen. But a cycling reservoir would be expected to have about the same loss since, although on the average the reservoir would be only half full, vertical diffusion from the saturated groundwater would be an additional compensating loss. Note that most of the diffusion leakage occurs early in the lifetime of the reservoir and hence our reason for including it as a capital loss rather than as a continuous loss. The total once only diffusion loss, for this example, would he expected to be of the order of 2 % of the storage capacity.
1.5 % |ost 1.0

05

[ 5

I 10

I 15 years

Fio. 5. Accumulated gas lose due to diffusion in a dormant reservoir. The assumptions which lead to this curve are given in Section 3.4.

3.5. Contamination of stored gas Hydrogen gas taken from storage is expected to contain water vapour and contaminant gases that have come out of solution from the ground water. The energy loss associated with the removal of water vapour is properly considered as an operating loss. However, the removal of gases is considered as a once only loss because it is expected that the proportion of these contaminants in the hydrogen will decrease with time and that their total quantity will be eventually limited. This limiting effect closely parallels the limitation on the total loss of hydrogen due to solution in water, In fact, the process of contaminant gases coming out of solution at the interface, and the subsequent diffusion of dissolved contaminant gas to the interface is almost exactly complementary to the loss mechanisms for hydrogen already discussed. The total quantity of contaminant will depend on the solubility and the degree of water saturation with respect to each component gas. With nitrogen, for example, the maximum total quantity by

566

P. 0. CARDEN AND L. PATERSON

volume is likely to be of the order of 1% of the swept storage volume (i.e. the number of volumes of nitrogen that can be dissolved in one volume of water), but for hydrogen sulphide perhaps 100 % or more is possible. There is a dearth of information in this area and much scope for new work at elevated pressures. Despite the fact that the contamination processes are incompletely understood it may be stated with fair certainty that the degree of contamination will be generally less than that of natural gas derived from discovery wells. We may be confident therefore that the technology exists to remove contamination in a treatment plant and that the associated costs will be acceptable. 3.6. Underground chemical reactions The possibility of reactions between hydrogen and the hydrocarbons in a depleted petroleum reservoir was identified by Waiters [11]. He remarked, however, that all the potential reactions should be too slow at reservoir temperatures and in the absence of catalysts to present any problems. Unsaturated hydrocarbons in natural gas are virtually non-existant, so hydrogenation will be no problem. Cracking of carbon-carbon bonds, and in particular the reaction C2H 6 + H 2 -* 2CH4, will need the most attention. There also exists the possibility of hydrogen reacting with materials found underground. For example, a reaction of hydrogen with sulphur, being exothermic, could cause serious overheating and would also cause the release of unpleasant smelling and poisonous hydrogen sulphide. Care would have to be taken to ensure no such minerals were in the vicinity of a hydrogen storage reservoir. However, hydrogen sulphide often occurs in natural gas and may be removed in a process called sweetening. 4. O P E R A T I N G LOSSES Operating losses can be divided into two types: material losses of hydrogen, which are essentially constant for each cycle or which continue at a uniform rate, and energy losses sustained in the transfer of gas in and out of storage. 4.1. Material losses 4.1.1. Caprock leakaoe. In a gas storage reservoir the caprack retains the gas by virtue of capillary forces at the gas water interface. The water saturated caprock contains much smaller pores than the underlying gas permeated aquifer and hence capillary pressures in the caprock will be much higher than in the gas storage region. Generally speaking, the pressure required to cause water to begin draining from a porous medium is called the "threshold pressure" and is indicated by the letter A in Fig. 6, but caprock has a much higher threshold pressure than is shown in this diagram. When the threshold pressure of the caprock is exceeded, gas will commence driving water out of the caprock and a leak will develop. Threshold pressures for hydrogen and natural gas will be the same because they depend on capillary pressure. However, once a significant leak has begun, channel flow, or fingering, would be expected to develop [21] in the manner already described for the reservoir rock in Section 2.2. Hydrogen would therefore be expected to leak considerably faster than natural gas after the threshold pressure is exceeded. It is the normal practice, however, to avoid this situation by not exceeding the threshold pressure in gas storage systems. 4.2. Energy losses 4.2.1. Pumping losses in the wells. The capacity of a well connecting a gas reservoir to the surface depends on the allowable flow rate into or out of the well. One of the limitations to flow rate is friction pressure drop. The allowable friction pressure drop depends on the ratio of the power loss through friction to the power being transmitted in the flowing gas. The latter may be obtained by assuming that the chemical energy of the hydrogen is recovered and converted to electrical power by a process such as the burning of hydrogen in a gas/steam turbine to generate electricity. The friction power loss may be equated to the electric power required by the well head pumps. If we assume that the allowable power ratio is 1%, that hydrogen has a chemical energy density of 10.6 M J m -3 at 1 atm, and that

CHEMICAL AND ENERGY ASPECTS OF UNDERGROUND HYDROGEN STORAGE

567

_4
o3 , 2

i
"5 . , 'tO I OJ

20% Woter soturotion

9O%

FIO. 6. Capillary pressure vs water saturation diagram (based on Bear [24]) showing the relationship between (a) residual water saturation, (b) residual gas saturation, (c) threshold pressure (denoted by A), and (d) capillary hysteresis. the conversion efficiency of chemical energy to electrical energy is 0.25 we find that, by taking the product of all these factors, the friction pressure drop must be limited to 13 % of the nominal systerh pressure. Consequently, if the latter is 300 atm then friction must be no greater than 40 atm. These figures also include a factor of 0.5 allowing for the fact that it is necessary to pump down and then up the well. In order to gain an insight into the magnitude of the components of friction pressure drop let us first assume that it is predominantly due to flow along the well liner. It can be shown, using the general equation for pipe flow:

Ap = -~ f -~ pQ2,

(4)

wherefis the friction factor (taken as 0.014), L is the length of pipe, d is the diameter of the pipe, p is the gas density (22 k g m - 3 at 300 arm) and Q is the volume flow rate, that for a 20 cm diameter liner 3000 m long a flow of approximately 1.3 m 3 s-1 (equivalent to 4.1 GWt) corresponds to a pressure drop of 40 atm. This pressure drop could be modified by altering the flow or the diameter of the well. It is to be noted that this component is very sensitive to changes in well diameter. 4.2.2. Pumpin0 losses in the porous medium. A second component of friction pressure drop is due to flow through the permeable sedimentary layer. Pressure drop here will depend on the permeability of the medium, the depth of drilling into the medium and the diameter of the drilling (which can be made larger than the well diameter through a number of processes, such as hydraulic fracturing). As an example we present the results of a calculation based on (1) for a permeability of 1 darcy (a fine sand), a drill depth of 7 m, drill diameter 20 cm and an effective radius of the gas "bubble" of 100 m. The calculation shows that a flow of 2.9 m 3 s - 1 corresponds to a pressure drop of 40 atm. Thus i t can be seen that generally most of the frictional pressure drop will occur in the well itself. This, o f course, varies from situation to situation. 4.2.3. Capillary hysteresis~ As a gas-water interface passes through the various pores and constric-i tions of a porous medium, the meniscus will be subjected to local expansions and contractions as the[ cross-section changes during the motion. Consequently the meniscus is compelled to adopt instan-[ taneous shapes which represent considerable departures from equilibrium. Under some circumstances[ this is accompanied by appreciable energy dissipation, which is the source of capillary hysteresis [22]. [ Capillary hysteresis is illustrated in Fig. 6. In the general operation of a gas storage reservoir, this loss! should be insignificant compared to the pumping losses (see Table 1).

568

P. O. CARDEN AND L. PATERSON Table 1. Summary Of losses

of reservoir Souroe Cushion gas Solution via connate water Diffusion Pumping capacity ~ 33 ~ 2 ~ 2 ~ 1 per cycle

5. C O N C L U S I O N It appears there are no insurmountable physical or chemical problems associated with underground hydrogen storage in sedimentary formations; rather, the problems are of economical optimization in which the cost of hydrogen will play an important role. With regard to capital expenditure, major items are the costs of the well and above ground equipment. However, the relative importance of these will ultimately depend on scale and advances in technology. This is not so for the single remaining major item: the cost of the cushion gas which appears to be irreducible. However, some of the initial investment for this may be recovered upon abandonment of the reservoir. The major operating loss is the frictional loss in the well itself, with lesser frictional losses in the porous storage space. The well operating losses could be converted to more of a capital loss by the choice of larger diameter weUs or by the use of more wells. Irrespective of this, pumping losses are far less than those encountered in the method of storing energy involving pumping water to elevated dams (known as pumped storage). Pumping losses for these systems are typically 35 % [23]. Although underground storage of hydrogen appears a most promising solution to the problem of large scale energy storage, many areas need further investigation. The diffusion rate of hydrogen through water saturated porous cores needs to be measured, and the effect that hydrogen's low viscosity will have on both fingering and the geometry of the gas bubble needs to be investigated. It is anticipated that further study will be done in these areas. Chemical reactions that may occur underground also need to be investigated.

REFERENCES I. P. O. CARDER,A Large Scale Solar Plant Based on the Dissociation and Synthesis of Ammonia, Australian National University, Department of Engineering Physics, Energy Conversion Technical Report No. 8, Canberra, Australia (1974). 2. P. O. CARt)EN,Corradiation using the reversible ammonia reaction, So/. Energy 19, 365 (1977). 3. A.F. HZLOESRA~rr,Solar tower thermochemical energy cycles, Hydrogen Energy Fundamentals Symp.-Course, Miami, Florida (1975). 4. W. HAFELE, Energy choices that Europe faces: a European view of energy, Science 84, 360 (1974). 5. L'AssociationTechnique du Gaz en France, 62 Rue de Courcelles, 75008, Paris (1957, 1958, 1961, 1962, 1965, 1975). 6. D. P. GREGORY,The Hydrogen Economy, Scient. Am. 228 (1) 13 (1973). 7. J. O'M. BOCKRZS,Energy: The Solar Hydrogen Alternative, Australia and New Zealand Book Company, Sydney, Australia, p. 218 (1975). 8. C. J. KIPPENHAN~ R. C. CORLETT, Hydrogen energy storage for electrical utility systems, Hydrogen Energy Part B, Plenum Press, New York (1975). 9. D. A. MATINS,Hydrogen Technologyfor Energy. Noyes Data Corp., Park Ridge, New Jersey, p. 23, (1976). 10. G. D. SAUT~R,Hydrogen energy--its potential promises and problems. Proc. 1st Worm Hydrogen Energy Conference, Miami Beach, Florida, 1-3 March 1976. 11. A. B. WALTEgS,Technical and environmental aspects of underground hydrogen storage. Proc. 1st World Hydrogen Energy Conference, Miami Beach, Florida, 1-3 March 1976. 1". J. BEAR.Dynamics of Fluids in Porous Media, Elsevier, New York, p. 123 (1972).

CHEMICAL AND ENERGY ASPECTS OF U N D E R G R O U N D H Y D R O G E N STORAGE

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13. M. R. TEK, J. O. WILKES, D. L. KATZ, D, A. SAVILLE, B. D. BHALLA L. G. SHERMAN, New Concepts in Underground Storage of Natural Gas, American Gas Association, New York, p. 2 (1966). 14. K. H. COATS & J. G. RICHARDSON, Calculation of water displacement by gas in development of aquifer storage, Soc. Pet. Eny. J., 105-112 0une 1967) 15. O. A. ALPAV, A practical approach to defining reservoir heterogeneity, J. Pet. Technol., 841-848 (1972). 16. R. M. Kr~APP, J. H. HENDERSON, J. R. DEMPSLr& K. H. COATS, Calculation of gas recovery upon ultimate depletion of aquifer storage, J. Pet. Technol., 1129-1132 (1968). 17. G. A. RATCLIFF,The measurement of diffusivities of gases in liquids, Chemeca 70, Butterworths, Sydney, p. 94 (1970). 18. G. H. PANDEr, D. L. KATZ & M. R. TEK, Diffusion of fluids through porous media with implications in petroleum geology, Am. Assoc. Petrol. Geol. Bull. 58 (2) 291 (1974). 19. L. L. C-MEN,D. L. KATZ & M. R. TEK, Binary gas diffusion of methane-nitrogen through porous solids, AIChE Jl 23 (3) 336-341 (1977). 20. D. BLAIR, Delhi International Oil Corporation. Private communication. 21. L. K. THOMAS, D. L. KATZ & M. R. TEK, Threshold pressure phenomena in porous media, J. Soc. Petrol. Eng. 8 (2) 174-184 (1968). 22. S. LEVINE,P. REED, G. SHUTTS& G. NEALE, Sotlle aspects of wetting/dewetting of a porous medium, Powder Technol 17, 163-181 (1977). 23, M. MASUDA& T. SHINTOMI, Superconducting magnetic energy storage, Cryogenics 607-612 (1977). 24, J. BEAR, op. cit., p. 451.