CHAPTER 4 GAS HYDRATES AND THEIR PREVENTION Gas hydrates are representatives of a class of compounds known as clathrates or inclusion

compounds. Natural gas and crude oil normally reside in reservoir in contact with connate water. Water can combine with low-molecular weight natural gases to form a solid, hydrate, even if the temperature is above water freezing point. Hydrates are considered as nuisance because they block transmission lines, plug blowout preventers, jeopardize the foundation of deepwater platforms and pipelines, cause tubing and casing collapses, and foul process heat exchangers, valves, and expanders. Hydrates act to concentrate hydrocarbons; 1 cuft of hydrates may contain as much as 180 SCF of gas. Large natural reserves of hydrocarbons exist in hydrated form, both in deep oceans and in the permafrost. Evaluation of these reserves is highly uncertain, yet even conservative estimates indicate that there is perhaps twice as much energy in the hydrated form as in all other hydrocarbon sources combined. This chapter is intended to provide the basic information needed for engineering purposes about hydrates. 4.1 WATER CONTENT OF NATURAL GAS When natural gas leaves the reservoir, it flows up the wellbore, which has lower temperatures than the reservoir, and hence the gas saturated with water will tend to yield a liquid water condensate. Pressure drop also affects the water content, but this effect during flow up a wellbore is smaller than that of temperature. Figure 4.1 shows a chart giving the water content of natural gases saturated with water vapor. Plotted on this graph is an equilibrium curve of hydrate formation, which should be a function of gas composition. Determination of water content by this chart produces an error not exceeding 4%, which is acceptable for engineering purposes. As seen in Figure 4.1, the water content of a natural gas increases with the increase in temperature and decreases with increase in pressure. Moreover, the water content of natural gases drops with an increase in their molecular weight and with an increase in the water salinity. The two auxiliary graphs shown in Figure 4.1 are for finding the correction factors for the molecular weight (gas density), C and water salinity (Cs). Let us now look at analytical methods, which allow us to find the water content of natural gases in a selected range of pressures and temperatures. The most suitable analytical method is Bukacek's method permitting the determination of water 2 0 content within a pressure range from 1 to 700 kgf/cm and of temperature range from -40 to 230 C. The error by this method does not exceed 4%. The following expression is used for finding gas water content:
1

24

W= where

A +B P

(4.1)

A, B = coefficients, function of temperature. The values of A and B are given in Table 4.1. 2 P = gas pressure, kg/cm Table 4.1 Coefficients for Equation 4.1

In view of the fact that Equation 4.1 was obtained for natural gases with a specific gravity of 0.6 in contact with fresh water. For finding the water content of gases with a different gravity and of gases in contact with mineralized water, the Equation 4.1 takes the following form: W =( A + B)C C s P 25 (4.2)

C, Cs = Correction factors for gas gravity and salinity of water. The correction factors C and Cs can be obtained from the insert graphs of Figure 4.1. It is also possible 2 to obtain the salinity correction, Cs from Equation 4.3 . C s = 1 4.920 10 3 S 1.762 10 4 S 2 (4.3)

where S is the salinity in weight percent. Figure 4.3 agrees with existing graphical correlation to within 1%. 4.2 WHAT IS A GAS HYDRATE? Natural gas hydrates are two or multi-component non-stoichiometric crystalline compounds where one of the components is always water. Gas hydrates exist due to the ability of water molecules to form a lattice structure, through hydrogen bonding, stabilized by small, non-polar gas molecules. By the inclusion of the gaseous component, the structure, which alone is thermodynamically unstable, becomes stabilized. Gas molecules are physically enclosed in the cavities of the water lattice, and they are released from the cavities only under appropriate circumstances, when the water lattice breaks down. Thus, the gas components filling the cavities are not directly bonded to the water molecules of the framework. It is for geometrical reasons that they cannot leave the hydrogen-bonded water molecule lattice until it collapses. Gas hydrates of interest to the hydrocarbon industry are composed of water and the following eight molecules: Methane Ethane Propane iso-Butane Carbon dioxide Nitrogen Hydrogen sulphide normal-Butane

Hydrates normally form in one of the small, repeating crystal structures, shown in Figure 4.2. Structure I (sI), a body-centered cubic structure and forms with natural gases containing molecules smaller than propane. Structure II (sII), a diamond lattice within a cubic framework, forms when natural gases or oils contain molecules larger than ethane but smaller than pentane. Structure H (sH) has been found 3 recently . sH hydrates are unique since they form in the presence of a light gas such as methane and 4 molecules typically in oils and condensates . Several sH formers such as methylcyclopentane, methylcyclohexane, neohexane, and adamantane are indigenous to petroleum. Preliminary studies demonstrate the possible occurrence of sH hydrate as the most stable hydrate structure for certain multi-component systems. Table 4.2 provides a hydrate structure summary for sI, sII and sH. The "small" cavities of all structures 12 are pentagonal dodecahedra (5 ) formed by the water molecules. The "large" cavities of sI are 12 2 tetradecahedra, formed by 2 opposing hexagons and 12 pentagons situated between them (5 6 ); in sII 12 4 they are hexadecahedra, constructed from 4 hexagons and 12 pentagons (5 6 ). Structure H has a 3 6 3 second dodecahedron, the 4 5 6 cavity, which is built of three quadrates, six pentagons and three 12 8 hexagons. The largest cavity, the 5 6 cavity, is built of twelve pentagons and eight hexagons. Figure 5 4.3 depicts the five cavities of hydrate structures . 26

Each of the cavities in either structure may contain only one guest molecule. The cavity occupied is a function of the size ratio of the guest molecule within the host cavity. Table 4.3 shows the size ratio of 6 several common gas molecules within each of the four cavities . Note that a size ratio approximately 0.9 is necessary for the stability of a simple hydrate, given by the superscript "". When the size ratio exceeds unity, the molecule will not fit within the cavity and the structure will not form. When the ratio is significantly less than 0.9 the molecule cannot lend stability to the cavity to cause formation. Table 4.3 indicates which of the gaseous compounds found in typical petroleum mixtures may enter hydrate cavities. Table 4.2 Some physical constants of hydrate structures.
Property Number of H2O molecules/unit cell Number of 512 cavity Number of 51262 cavity Number of 51264 cavity Number of 435663 cavity Number of 51268 cavity Diameter of 512 cavity, Diameter of 51262 cavity, Diameter of 51264 cavity, Diameter of 435663 cavity, Diameter of 51268 cavity, Structure I 46 2 6 5.0 5.8 Structure II 136 16 8 5.0 6.47 Structure H 34 3 2 1 5.0 5.0 9.0

Table 4.3 Ratio of molecular diameters to cavity diameters for some molecules forming sI and sII hydrates.
(Molecular diameter)/(Cavity diameter) Cavity type Structure I Structure II Molecule Guest diameter () 512 51262 512 51264 * Ne 2.97 0.604 0.516 0.606 0.459 Ar 3.8 0.772 0.660 0.775 0.599 Kr 4.0 0.813 0.694 0.816 0.619 N2 4.1 0.833 0.712 0.836 0.634 O2 4.2 0.853 0.729 0.856 0.649 CH4 4.36 0.757 0.889 0.675 0.886 H2S 4.58 0.931 0.795 0.934 0.708 CO2 5.12 1.041 0.889 1.044 0.792 C2H6 5.5 1.118 0.955 1.122 0.851 C3H8 6.3 1.276 1.090 1.280 0.971 i- C4H10 6.5 1.321 1.128 1.325 1.005 7.1 1.443 1.232 1.447 1.098 n-C4H10* Indicates the cavity occupied by the simple hydrate former. * Indicates that a molecule will not form hydrates as a single component, because it is too small (or too large) to stabilize a cavity. Note: If a molecule enters the small cavities of a structure, it will also enter the large cavities.

27

4.3 PHASE EQUILIBRIA The hydrates of natural gases are solid compounds containing a number of gas components. The range of existence and the properties of hydrates indicate that the nature of the gas, the state of the water, the pressure and the temperature determine the initial conditions of gas hydrate formation. The formation conditions are generally given by means of phase diagrams in P vs. T plots. Figure 4.4 illustrates the phase behavior of a pure hydrate forming gas. Line AB represents equilibria between hydrate (H), gas in gaseous form (G), and ice (I). Line BC represents equilibria between hydrate (H), gas in gaseous form (G), and liquid water (L1). Line CD represents equilibria between hydrate (H), gas in liquid form (L2), and water in liquid form (L1). Line EF represents the vapor 7 pressure of the pure hydrate forming compound . For a mixed gas, the situation may become slightly more complicated, due to possible intersection of the hydrate curve with the phase envelope of the gas mixture. This is illustrated in Figure 4.5. The lines AB, BC and DE correspond to the lines AB, BC, and CD in Figure 28. At the line CD in Figure 29, hydrate (H), gas in gaseous form (G), gas in liquid form (L2), and water in liquid form (L1) are in 7 equilibrium . The crystal lattice filled by gaseous mixtures is more compactly filled than the hydrates formed by the individual gas components, and the resulting hydrate structure is more stable than those of the hydrates of system containing only one gas component. Figure 4.6 shows the effects of higher hydrocarbons on the formation of methane hydrate . It indicates that, with the exception of normal-butane the effect of the hydrocarbons in reducing the pressure of methane hydrate increases with the increase in length of carbon chain. The effects of ethane and 9 propane on the formation pressure of methane have been obtained by using a computer program 6 called CSMHYD developed by Sloan (Figure 4.7). The calculations were done at the temperature of 15 C. Figure 4.7 shows that the propane is very effective on the methane hydrate formation pressure with a concentration of less than 3% in the mixture. 4.4 PREDICTIONS OF CONDITIONS FOR HYDRATE FORMATION 4.4.1 Approximate Method for Sweet Gases As a first approximation, the data presented in the Gas Processors Suppliers Association (GPSA) charts shown in Figures 4.8 through 4.12 can be used. These charts do not account for the presence of H2S and CO2. Hydrate formation can be divided into two categories: 1) hydrate formation due to a decrease in temperature (or increase in pressure) with no sudden expansion (or compression), such as in flow strings and surface lines; 2) hydrate formation due to sudden expansion, such as in flow-provers, orifices, chokes, and backpressure regulators. For hydrate formation of type 1, Figure 4.13 can be used for predicting the approximate pressuretemperature conditions for hydrate formation. Figures 4.8 to 4.12 are used for estimating hydrate formation conditions for situations of type 2. In particular, these figures are used for determining the permissible expansion, without hydrate formation, of a gas with a given gravity.
8

28

4.4.2 Vapor-Solid Equilibrium Ratio Method The Vapor-Solid Equilibrium Ratio (K-value) method is an early method for calculating hydrate6,10,11 forming conditions using vapor-solid equilibrium constants . Katz et al. reasoned that hydrates were the equivalent of solid solutions and not mixed crystals. They postulated that hydrate-forming conditions could be calculated from empirically determined vapor-solid equilibrium constants: K s = where y = mole fraction of a hydrocarbon in the gas on a water-free basis. xs = mole fraction of the hydrocarbon in the solid on a water-free basis. The hydrate forming conditions should satisfy: y xs (4.4)

y K vs

=1

(4.5)

This procedure is like the dew point calculation for complex gas mixtures. K-charts for methane, ethane, propane, iso-butane, normal-butane, hydrogen sulfide, carbon dioxide, and nitrogen are available for predicting the hydrate-forming points from gas composition (Figures 4.14-4.21). Poetmann et.al. utilized CSMHYD hydrate prediction program to calculate vapor-solid equilibrium ratios for structures I and II for various natural gas systems. From the generated, charts were constructed for each natural gas component. Structure I charts consist of methane, ethane, carbon dioxide, and hydrogen sulfide. Structure II consists of the same component as Structure I with the addition of propane, iso-butane, and normal-butane. Polynomial regression analysis was used to curve fit the computer generated Kvs values for both structures. These equations can be programmed and used to predict the hydrate forming conditions for natural gases. Tables 4.4 and 4.5 lists the hydrate equilibrium ratio equations for Structure I and Structure II, respectively. 4.5 METHODS OF HYDRATE PREVENTION Fundamentally there are four ways to prevent hydrates from forming: 1. Reducing the pressure below that of the hydrate formation for the given temperature; 2. Maintaining the temperature of the gas flow above the hydrate formation temperature for the given pressure; 3. Reducing the dew point of water vapor in the gas flow below the operating temperature (drying the gas); 4. Introducing various substances (alcohols, electrolytes) into gas flow, which lower the hydrate formation pressure. This chapter examines only the third and fourth processes of hydrate prevention.
12

29

30

31

32

33

4.5.1 Hydrate Control through Water Removal (Dew Point Lowering) Except in arctic conditions, the maximum water content of gas is specified as 4 lbm/MMSCF; typically the water content is 2.25 lbm/MMSCF. After the free water is separated from the gas stream, two processes are commonly used to lower the dew point by removing dissolved water. In the first process, contacting the gas with a compound, typically tri-ethylene glycol (TEG), which removes water through hydrogen bonding, lowers the water concentration. In the second process, the gas is contacted with a solid, such as molecular sieve, alumina or silica gel, which selectively adsorbs water. In general solid desiccants are placed in parallel packed bed adsorbers through which gas is passed. One adsorber is used to remove water from the gas while the parallel unit is being regenerated at high temperature or cooling. In recent years molecular sieves have gained popularity due to their advantages of providing extremely low dew points, high adsorption of water and unlike silica gel, they are not damaged by liquid water. 4.5.2 Hydrate Control through Use of Chemicals Frequently inhibitors are injected into processing lines as a means of hydrate control by both the breakage of hydrate hydrogen bonds and the competition for available water molecules. The more frequently used inhibitors are strong polar fluids, such as methanol, the ethylene glycols, and ammonia, arranged in order of decreasing usage frequency. Of the above three chemicals, the uses of methanols and the ethylene glycol are pervasive. While ammonia is more than twice as effective as methanol, it is only used in cases of severe hydrate blockage, due to the reaction of NH3 with CO2 in the gas to form plugs of solid ammonium carbonate, bicarbonate and carbamate. The handling of ammonia is also an important safety consideration. The use of inhibitors shifts the three-phase (Lw-H-V) equilibrium curve to higher pressures and lower temperatures as shown in Figure 4.22 by relative positions of the solid (inhibited) line to the dashed line. The theoretical principles of inhibition of hydrate formation have been discussed in several papers. 13 Hammerschmidt proposed the first empirical equation to find the required concentration of an inhibitor X, in an aqueous solution, for lowering the hydrate formation temperature by a given amount, o F): T = KX 100M - MX (4.5)

from where X= 100 T K + T M (4.6)

where M = inhibitor's molecular weight, K = constant, depending on the type of solution. 34

Experimentally determined values of K and molecular weights of inhibitors are given in Table 4.6. Table 4.6 Physical constants of inhibitors. Component Methanol Ethylene Glycol Diethylene Glycol Triethylene Glycol Molecular weight 32 62.07 106.12 150.17 K-value 2335 2700 4000 5400

Whether methanol or a glycol is used for hydrate depression, there are three possible phases into which the inhibitor may distribute. 1. the aqueous phase where the hydrate inhibition occurs, 2. the vapor hydrocarbon phase, where the inhibitor may be lost, as in the usual case of methanol injection, and 3. the liquid hydrocarbon phase, which has appreciable solubility for both methanol and glycols. Depending upon the temperature and pressure, all three of the fluid phases may be present, or either the vapor or the liquid hydrocarbon may be missing. The concentration of the inhibitor in the aqueous phase is addressed by Hammerschmidt equation. The 14 loss of inhibitor to the vapor phases may be determined from Figure 4.23 for methanol, or from 15 Figure 4.24 for glycols. The low temperature data, which are available for methanol and glycol solubility in hydrocarbons, are presented in Figures 4.25 and 4.26, respectively. The injected methanol concentration is normally > 98 wt%, while the typical ethylene glycol injected into pipelines often falls in the range 65-75 wt%. 4.6 HYDRATES IN THE EARTH Because hydrates concentrate methane by a factor of 170 and because as little as 10% of the recovered energy is required for dissociation, hydrate reservoirs have been considered as a substantial future energy resource. The initial part of this section deals with the estimates of the extent of natural gas in in-situ hydrates, as well as the location and requirements for their formation. The second part deals with a case study of hydrate production and the economics of recovery of gas from hydrates. 4.6.1 Extent and Location of Natural Gas Hydrate Deposits In 1965, Makogon announced the observation of gas hydrates in permafrost regions of the Soviet Union. Today it is recognized not only that hydrates are wide-spread in outer continental margins of the oceans and portion of the region of permafrost, but also that economics dictate that recovery of gas from hydrate must be postponed for a number of years. Knowledge of the occurrence of in situ gas hydrates is very incomplete, and is obtained from both direct and indirect evidence. In permafrost regions, hydrate evidence is limited to drillings and associated well logs and cores, whereas seismic methods as a less direct but relatively inexpensive 35
16

means of sensing on continental margins. Table 4.7 provides a decade of estimates of natural gas hydrates in the geosphere. All of the estimates of natural gas hydrates are not well defined, and therefore somewhat speculative. It appears however that the most recent estimates, made by independent investigators through different methods are converging on very large values of gas reserves in the hydrated form. Even the most conservative 17 estimates of gas in hydrates in Table 4.7 indicate their enormous energy potential. Kvenvolden 16 3 indicated that the 10000 Gigatons or 1.8x10 m of carbon in hydrates might surpass the available carbon in the global carbon cycle by a factor of two. Table 4.8 compares the carbon in hydrates with the sources of other global carbon cycle. Table 4.7. Estimation of Methane in In-Situ Hydrates (m )
Permafrost 13 5.710 13 3.110 13 3.410 13 1.410 13 1.010 Oceanic 15 5-2510 15 3.110 18 7.610 16 1.010 18 5.71.810 Reference 18 19 20 21 22 17
3

Table 4.8. Amounts of Carbon in Global Cycle

Source Hydrate Fossil fuels (Natural gas, coal, oil) Terrestrial soil, detritus, peat Marine dissolved materials Terrestrial biota The atmosphere Amount (Gigaton) 10000 5000 1960 980 830 3.6
17

Figure 4.27 shows the locations in the global map where there is some evidence of in-situ hydrates . One of the locations indicated as a hydrate bearing site is the Black Sea. Analysis of the actual 23 pressure-temperature environment in the deep part of the Black Sea Basin , taking into account theoretical data and the results of the Glomar Challenger, indicates P-T conditions favorable for the formation of gas hydrates, beginning from a water depth of 700-750 m for pure methane and 300-500 m for natural gas with a specific gravity of 0.6. Figure 4.28 shows potentially gas-bearing regions of the zone of hydrate formation in the Black Sea basin. Analysis of data gives the predicted gas reserves of 3 20-25 trillion m of gas. The major difficulty in considering hydrates as actual reserves stems from the solid, dispersed character of hydrates themselves. The recovery of gas from hydrates is more complex than that from a normal gas reservoir. In addition, while an energy balance of the dissociation of pure hydrates is very favorable, the hydrates may be dispersed in the sediments, which will mitigate their economic recovery.

36

Only four conditions are necessary for hydrate formation, 1. 2. 3. 4. Adequate gas molecules to stabilize most of the hydrate cavities, Sufficient water molecules to form the cavity, A temperature within the hydrate phase equilibrium region, and A pressure within the hydrate phase equilibrium region.

Figures 4.29 and 4.30 are arbitrary examples of the depths of hydrate phase stability in permafrost and in oceans, respectively. In each figure the dashed lines represent the thermal gradients as a function of depth. The slopes of the dashed lines are discontinuous both at the base of the permafrost and the water/sediment interface, where new sediment thermal conductivities cause new thermal gradients. The solid lines were drawn from the methane hydrate phase equilibria data, with the pressure converted to depth assuming hydrostatic conditions in both the water and sediment. In each diagram the intersections of the solid and dashed lines bound the depths of the hydrate stability fields. In both Figures 4.29 and 4.30, a small addition of heavier natural gas components, such as propane or iso-butane, will cause the hydrate stability region to increase due to a displacement of the phase boundary line away from the geothermal gradient line. In neither case, however hydrates have been found at sediment depths greater than 2000 m, due to the high temperatures resulting from the geothermal gradient. 4.6.2 Gas Recovery from Hydrates at Messoyakha: A Case Study While the Messoyakha hydrate field is the only available example for gas production from hydrate, the hydrates have been produced from this field semi-continuously for over 17 years. The field is located in the north-east of western Siberia, close to the junction of the Messoyakha River and the Yenisei River, 250 km west of the town of Norilsk, as shown in Figure 4.31. Figure 4.32 provides a cross-section of the field, showing the hydrate deposit to be overlying the free gas zone. The depth temperature plot of Figure 4.33 shows the hydrate layer to extend to the intersection of the 281 K geotherm. The gas in the hydrate zone is both in the free and the hydrated 22 state. Makogon provides the most recent information regarding the properties of the field, as tabulated in Table 4.9. The Messoyakha field has been produced through inhibitor injection and depressurization, as well as combinations of the two. The inhibitor injection tests, presented in Table 4.10, frequently gave dramatic short-term increases in production rates, due to hydrate dissociation in the vicinity of each injected wellbores. Makogon indicates that of all the complex studies during the 19 years of the production life of the Messoyakha field, the most informative results came from an analysis of the reservoir pressure change as a function of the gas withdrawal rate. A diagram showing pressure and gas production as a function is shown in Figure 4.34, with the accompanying pressure-temperature relationship in Figures 4.35a,b. 22 While Figure 4.35a may represent the measured pressure-temperature values far away from the 6 hydrate, Poettmann suggested that the values in the neighborhood of the hydrate interface are better represented by Figure 4.35b, for reasons given below.
22

37

38

In Figure 4.35, the following initial points are used, AB = hydrate equilibrium line; C = temperature at the top of the pay zone; D = temperature at a level of gas and water contact; E = average gas-hydrate temperature; F = temperature at boundary surface between gas and gas-hydrate reserves; G = minimum pressure at which gas hydrates are stable; H = beginning dissociation pressure for gas hydrates. As the production of the field was begun from 1969 to mid-1971, the pressure decreased from E in Figure 4.35 to just above the hydrate dissociation point at H. During this period only free gas was produced because the pressure was above the hydrate equilibrium value. With the pressure reached the hydrate equilibrium value at point H, the hydrates began to dissociate, adding the shaded portion to the gas production curve at the lower half of Figure 4.34. The top half of Figure 4.34 shows the reservoir pressure was maintained at a higher value (solid line 2) than the expected pressure (dashed line 3) due to addition of gas to the reservoir by the hydrates. After point H 22 in Figure 4.35a, Makogon indicated that the pressure away from the hydrate decreased below the equilibrium value, with a slight decrease in temperature. The pressure at the hydrate interface in Figure 4.34b however, should not deviate from the equilibrium line, unless all of the hydrates were dissociated. Consequently the pressure and temperature at the hydrate interface decreased along the equilibrium curve as the reservoir was depressurized. Between the third and sixth year of the field development there was probably a pressure drop between the hydrate interface, from H to L in Figure 4.35b, and the measured pressure from H to L in Figure 4.35a, due to the flow of gas in porous media. As the Messoyakha reservoir attained the pressure at point L (Figure 4.35), the average pressure stabilized for two years to point M, indicating that the volume of gas recovered was replenished by gas liberated from hydrate. The difference between curves I and J in Figure 4.34 indicates that the total gas produced (curve I) was slightly less than the gas liberated by the hydrates (curve J). At point M, the reservoir was shut in, while other higher pressure gas reservoirs were produced. During that period, the average pressure of the reservoir began to rise from point M to point N in Figure 4.35b. The difference in Figure 4.34 indicates that gas continued to be liberated by the hydrates until the reservoir pressure was uniform at point F of the line in mid-1981. As the average gas pressure approached equilibrium value the amount of gas produced decreased exponentially. Since 1982 there has been a modest production of the Messoyakha reservoir. The amount of gas withdrawn has been equivalent to the amount of gas liberated from the hydrate. The total amount of gas liberated from hydrates thus far has amounted to 36% of the total gas withdrawn from the field. REFERENCES 1. Bukacek, R.F., "Equilibrium Moisture Content of Natural Gases" Research Bulletin IGT, Chicago, vol 8, 198-200 (1959). 2. McCain, W.D. Jr., The Properties of Petroleum Fluids, second edition, PennWell Books, Tulsa, 525-528 (1989). 3. Ripmeester, J.A., Tse, J.S., Ratcliffe, C.I., Powell, B.M., Nature, vol 325, 135-136 (1987). 39

4. Mehta, A.P., Sloan, E.D.Jr., "Structure H Hydrates: The state-of-the-art", Proceedings 2 International Conference on Natural Gas Hydrates, Toulouse, France, 1-9 (1996).

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5. Lekvam, K., Kinetics of Natural Gas Hydrates, Ph.D. Dissertation, University of Aalborg and Hogskolen at Stavanger, August 1995. 6. Sloan, E.D., Jr., Clathrate Hydrates of Natural Gases, 2 edition, Marcel Dekker Inc., New York (1998). 7. Pedersen,K.S., Fredenslund, Aa., Thomasson, P., Properties of Oils and Natural Gases, Gulf Publishing Company, Houston, Texas (1989). 8. Carson, D.B., and Katz, D.L., "Natural Gas Hydrates", Petroleum Transactions, AIME, 146, pp.150-158 (1942). 9. Gudmundsson, J.-S., and Parlaktuna, M., Gas-in-Ice Concept Evaluation, University of Trondheim, The Norwegian Institute of Technology, (1991). 10. Wilcox, W,I., Carson, D.B., and Katz, D.L., Natural Gas Hydrates, Ind. Eng. Chem., 33, pp. 662 (1941). 11. Carson, D.B., and Katz, D.L., "Natural Gas Hydrates", Petroleum Transactions, AIME, 146, pp.150-158 (1942). 12. Poettmann, F.H., Sloan, E.D., Mann, S.L., McClure, L.M., "Vapor-Solid Equilibrium Ratios th for Structure I and II Natural Gas Hydrates" Proceedings 68 Annual GPA Convention, March 13-14, San Antonio, Texas (1989). 13. Hammerschmidt, E.G., Gas, 15(5), pp.30 (1939). 14. Nielsen, R.B., and Bucklin, R.W., Hydrocarbon Processing, p.71, April (1983). 15. Polderman, L.D., "The Glycols as Hydrate Point Depressants in Natural Gas Systems", Proc. Gas Conditioning Conference, Norman, OK (1958). 16. Makogon, Y.F., Gazov. Promst., 5, 14 (1965). 17. Kvenvolden,K.A., "Methane Hydrate-A Major Reservoir of Carbon in the Shallow Geosphere", Chemical Geology, 71,41 (1988). 18. Trofimuk, A.A., Cherskiy, N.V., and Tsatev, V.P., Future Supply of Nature-made Petroleum and Gas, R.F.Meyer,ed., 919, Pergamon Press, New York (1977). 19. McIver, R.D., Long-Term Energy Resources, R.F. Meyer and J.C. Olson, eds., Pitman, Boston, 1, 713, (1981). 20. Dobrynin, V.M., Korotajev, Yu.P., and Plyuschev, D.V., Long-Term Energy Resources, R.F. Meyer, Ed., 727, Pitman, Boston (1981). 21. Meyer, R.F., Long-Term Energy Resources, R.F. Meyer and J.C. Olson, eds., 49, Pitman, Boston (1981). 22. Makogon, Y.F., "Natural Gas Hydrates: The State of Study in the USSR and Perspectives for Its Use", paper presented at The Third Chemical Congress of North America, Toronto, Canada, June 5-10 (1988). 40
nd