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OTC 8235


of Hydrates

in Shut-down


in Offshore


Y.F. Makogon, SPE, Texas A&M University

Copyright 1996, society of Petroleum Engineers, mc Thm paper was wepared for p4esentabon at the Offshore technology Conferemcs held m Hcuston, Texas, 6-9 May 19S6 TPIS pqmr was seiecied for prasentabon by the OTC Program Commdtee followng rewew of infommtion con!aimd in K n abstract submitted by the autfwr(s) Ccntents of the paper, as presented, have not been rewewwd by the Offshwe Tectmc40gy Ccmference and are subject ICIccfredion by the author(s) The material, as presented, does not naessanly reflect any pos!ticmof the Offslwwe Technology Conference or Ils ofhcars Parmlswon to copy IS restrcted to an abstracl of not more than XIO wc+ds Illustrakms may nol ba cop!ed The abstr~t shdd contain conep!cuous acknowledgment of where and by whom the paper was pmseflted

Abstract Operation of oil and gas pipelines in deep-sea is sharply complicated by the formation of gas hydrates. The experience indicates that large gas hydrate plugs in gas and oil pipelines form most actively during the period of unforeseen long shutins. In static conditions three types of hydrate crystals form: surface-contact films and massive hydrates which form by sorption of gas and water molecules on the surfaces of growing crystals; bulk diffusional whisker-like which form both in the volume of gas, and in the bulk of liquid water through sorption of molecules on the growing crystal surface and by tunnel sorption of molecules at the base of the crystal; gel-like soft crystals which form in the bulk of liquid water at a deficiency of dissolved gas in water. Under the P-T conditions of hydrate formation there may be a simultaneous formation of crystals and decomposition of other crystals. Equilibrium content of gas dissolved in water which is in contact with a solid hydrate surface is lower than in water which is in contact with free gas. Introduction Gas hydrate is a metastable mineral. Its formation, stable existence and decomposition depend on pressure, temperature, and the compositions of water and gas. Gas hydrates are inclusion compounds, solid solutions, in which water is the solvent. Molecules of water tied together by hydrogen bonds form a space tilling lattice. Mobile molecules of gases, or volatile liquids are absorbed, or incorporated in the cavities of the water lattice. Gas hydrates are widespread in nature. They easily form in technological systems of production, transportation and processing of gases, Natural gas hydrates are a tremendous source of energy. Resources of hydrocarbons accumulated on earth in a hydrate state are estimated as 1.5*10t6 m. Several

countries have already started to implement intensively their programs for development of gas hydrate deposits. An intensive growth of oil and gas production is accompanied by putting the fields in sub-Arctic regions and deep offshore into operation. At that the thermodynamic characteristic of the technological systems of hydrocarbon production and transportation almost always corresponds to the conditions of hydrate formation. There is a knowledge about numerous cases of large hydrate plugs formation in wells and gas pipelines. Analysis of the facts about the formation of large hydrate plugs in wells and oil or gas pipelines reveals that the most dangerous periods of time are the unplanned long shut-ins. Expenses for the prevention of hydrate formation are 1015%.of the production cost. According to Savidge (I), on an average gas or gas-condensate field annual expenses for hydrate prevention are 5 to 15 million US $. Expenses for removal of a complete hydrate plug in a well or a gas or oil pipeline offshore are usually several millions of US dollars. At that the shut-in losses for up to several months must be taken into account. In a number of cases the formation of a hydrate plug in a pipeline halts the production of oil and gas on the whole field for the complete period of hydrates removal. Unfortunately, there is no clear understanding about the conditions of hydrate plugs formation both in wells and in pipelines. It should be emphasized that the kinetics of hydrate formation and decomposition remains to be one of the most complex and least studied one in the problem of gas hydrates. This work presents the results of experimental investigation performed in the gas hydrate laboratory of the Petroleum Engineering Department, and the Offshore Technology Research Center at the Texas A&M University. The presented results of studying the kinetics and morphology of hydrate crystals do not pretend to reveal all the aspects of hydrate plug formation. However, they will aid a more proper understanding of the hydrate formation process and designing of the more effective means of preventing hydrates. As a result of this work a dependence of the gas volubility in water on temperature and pressure was determined at hydrate stability conditions. Three types of hydrate crystals were found: growing on interface, bulk-divisional, and soft gel-like. All three types of crystals may form simultaneously at equal P-T conditions. The property of hydrate crystals to dissolve in water (2) at the hydrate stability conditions was


2 QTc 8235


confirmed. The direction of hydrate forrners diffusion during hydrate formation and many forms and rates of crystal growth were revealed. Only several results obtained during the study of hydrate formation processes are presented due to the brevity of the paper volume. Experimental Technique A high-pressure cell of an original design was used. This cell allowed to conduct a complex investigation of both formation and decomposition of hydrate in static and in dynamic conditions (Fig. 1). The cell volume was variable from 820 to 1020 cm, operating pressure - up to 200 kg/cm2. The cell had five round windows with diameter of 84.6 mm for visual observation, a system of temperature control in gaseous and in liquid phases with an accuracy of 0.05 C, and a pressure control system with an accuracy of 0.1 A. The cell was equipped with a special mechanism which allowed to determine the dynamics of phase correlation of components during hydrate formation without disturbing of the P-T and kinetic conditions. The obtained results were obtained for methane Ultra High Purity CGA Ouher 350 (LB-170) obtained from Matheson Gas Production Inc., and a double-distilled water. The cell pressure could be kept constant, or preset-varying with supplying gas into the gas volume, or by bubbling gas through a layer of water. Pressure could also be controlled by an injection of a fresh water, or of water pre-saturated with gas through a ALCOTT-760 HPLC 390 micro pump with a water flowrate of 0.01 -1.0 cm3/min. Water could be supplied into the cell in a bulk liquid or in a microdispersed state with a pressure drop at the throttle of up to 200 kg/cm2. The reactor cell was equipped with a remote magnetic stirrer with a speed of 0.5 - 10 rev./see, and a mechanical system providing the creation of a free gas-water interface at a rate equal to the rate of a hydrate film formation. The cell allows to study the morphology of crystals, to conduct direct measurements of thickness of the formed hydrate film, and to determine various properties of hydrates. Types of Hydrate Cqstals The earlier studies of the kinetics and morphology of gas hydrates (2- 10) have indicated that the start of hydrate formation always occurs at the free gas-water interface (with a gaseous or a liquefied gas). At that microcrystals of critical size rCrare formed. The critical radius of such crystals depends on many factors and is determined as (3, 8, 11) 2rsT,> Q(T,> -To)= 20V ~ ~= ................... 2dfh


(1) 750

Magnitude of the surface energy o is a function of pressure, temperature, composition, and the state of interface. Fig. 2 presents the dependence of the surface tension at the methanewater interface on pressure and temperature, Growth of microcrystals which formed at the methanewater interface is accompanied by the formation of a complete hydrate film on the whole surface of a tlee gas-water interface (Fig. 3). Thickness of the forming film depends on pressure, degree of subcooling, composition of the forming hydrate. With pressure the required initial degree of subcooling decreases, and with the decrease of the degree of subcooling the rate of nuclei formation and the rate of the hydrate film formation decrease. For example, the radial rate of hydrate film growth on a methane-water interface at a pressure of 84 kglcmz and a temperature of 6.6 C is 3 cm/min. For a comparison, the growth rate of needle-like crystals in similar conditions may reach 36 to 70 cm/min., and the rowth rate of F whiskery crystals may range from 0,1 to 1.7*1O crdmin. The rate of hydrate formation at a free gas-water interface is determined mostly by the rate of heat removal. After the hydrate formation on the interface, the interracial process becomes a bulk diffusion-dependent process. At that the rate of hydrate accumulation is determined mostly by the diffusion of water through a hydrate film (3,4) because of the difference between the diffusion coefficients of water and gas molecules. Three types of hydrate crystals may form simultaneously at the same external P-T conditions: a) massive - on the surface of the formed hydrate crystals by sorption of water and gas molecules (Fig. 4); b) soft gel-like crystals; c) whiskery (thread-like) crystals. Whiskery crystals grow both in the gas, and in the aqueous phases. Whiskery crystals grow as linear or twisted mono-rays or colonies, with or without branches. The whiskery crystals usually develop in the points of dislocations on the surface of the formed hydrate in the gas phase. At that the crystal growth is caused by the axial dislocation(s) with a finite screw component which creates a non-curing growth step at the crystal top (Fig. 5) or at the crystal base. Crystal formation proceeds by a sorptional addition to the growing step (12). The rate of crystal growth by addition of molecules to a growing surface can be very high, but the time of formation is short (shooting crystals) and is determined by the water vapor content in the gas phase, difference between the chemical potentials of water molecules dissolved in gas and in a hydrate lattice. When an equality of these chemical potentials is reached, the process of crystal formation stops. The linear dimension of such crystals varies broadly from fractions of a millimeter to several centimeters. During a consequent diffhsive influx of water molecules to the gas phase the formation of new whiskery or massive hydrate crystals may resume (Fig. 6). Whiskery hydrates may form simultaneously from a tunneling influx and a diffisive influx of hydrate forming

molecules to the base of growing crystals (Figs. 7). By solving the equation of diffusion


~2~(xJ). ~(xt)+/v.

,.,., ............... ...(2)


we can determine the rate of whiskery hydrates formation. Such crystals have a high initial growth rate with a consequent decrease in the rate. Usually, whiskery crystals form afier the formation of a hydrate film on the gas-water interface in the points of contact of the hydrate film with sharp angles of a hydrophilic surface in the points where capillary forces are the most expressed. In these points water is at the pressure which is lower than the vapor pressure by the amount of the capillary pressure, and favorable conditions for whiskery hydrates formation are created. Shift of the phase transition pressure APs due to the effect of capillary pressure Pc can be written as

./w, ...................................................... . . ....(3)

=%( dP<

The shift APS equals to the product of the derivative dPs/dPc and the capillary pressure. Whiskery crystals which form during the tunnel sorption of molecules, grow actively both into the gas volume and into water (Fig. 7). The rate of formation of such crystals is determined by the coefficient of the tunnel sorption of molecules and the length of the sorption channels. The variation of the linear growth rate of whiskery hydrates with time is shown in Fig. 8 During a complex study of the kinetics and phase correlations of the gas-water system it was determined (2) that the content of gas dissolved in water decreases significantly as a result of blockage of the gas-water interface by the forming hydrate, and as a result of a sharp change in the surface tension forces at the gas-water and hydrate-water interfaces. Fig. 9 presents the data for the dependence of dissolved methane content on temperature and pressure in the bulk of subcooled water which is in contact with a free gas, and with hydrate surface in Fig. 10. As it is seen on Fig. 10, the deficiency of gas content in water in presence of hydrate increases with subcooling. Deficiency of the gas content in water causes an active dissolution of whiskery hydrate crystals which formed in the bulk of water, We did not observe the dissolution of the hydrate film which formed at the hydrate-water interface even during the long tests - up to 260 hours. The dissolution of the whiskery crystals is accompanied by the increase of the gas content in water for a certain amount. However, at that the gas content in water does not reach the equilibrium value for a free water, and a dynamic equilibrium gas content in water is established which is controlled by the diffusive fluxes and the chemical potential of the gas molecules in different states. 751

Fig. 11 shows a series of photographs which illustrate the sequence of dissolution of the colony of whiskery hydrate crystals in water. During this experiment both temperature and pressure were kept constant both during the period of formation and during the period of dissolution of crystals. The cell temperature was 6.6C below the hydrate equilibrium temperature at the pressure of 98 kg/cm2. The time for the complete dissolution of the whiskery crystals in water was 66 hours. We should emphasize that we didnt observe any sublimation of the whiskery crystals into the gas phase. On the contrary, we observed their active formation due to the diffusive influx of water molecules and the sorption of the gas molecules. Simultaneously with the dissolution of the whiskery crystals in the conditions of deficit of dissolved gas, at certain conditions gel-like crystals formed in the bulk of water under the hydrate film (Fig. 12). Their nature is yet to be studied. After establishing the conditions for hydrate decomposition, the first to decompose were the gel-like crystals, followed by the massive crystals and the hydrate film on water. The whiskery crystals were the most stable and decomposed the last. In dynamic conditions of a gas and water flow in pipelines hydrates form as films or on gas bubbles with the size varying between fraction of millimeter to several millimeters. Such accumulations are highly hydrophilic, and during stirring are always covered by a water film. Thickness of the liquid film on the surface of hydrate depends on pressure, temperature, and the mixture composition. Presence of a liquid film on the surface of hydrates sharply decreases the particle adhesion and coagulation of gas-hydrate further bubbles. The transformation of gas contained inside a bubble in to the hydrate state occurs not due to the diffusion of gas through a hydrate film, but on the contrary, because of the diffusion of water molecules into the bubble (3, 8). As our research has indicated, during an active mixing of methane and water at the pressure of 50 - 100 kg/cm2 at hydrate formation temperatures, gas-hydrate bubbles with the diameters of 0.3-5 mm accumulated intensively. An upsidedown cone of gas-hydrate bubbles in liquid water formed (Fig. 13). Keeping these accumulations of bubbles at a subcooling of 5 - 7 C did not result in the formation of a compete monolith for 30-40 hours. Hydrate accumulations in its volume remained fluffy, consisting of separate bubbles. However, at the upper boundary of the bubbles accumulations a complete hydrate film formed. In static conditions during pipeline shut-ins thickening of the hydrate film over a mass of gas hydrate bubbles proceeds slowly, and is controlled by the intensity of water molecules diffusion through the hydrate film. The rate of hydrate accumulation during the diffusive influx of water through a hydrate film was reported earlier (3, 4, 8). Favorable conditions for the formation of whiskery hydrates may occur in the points of contact of gas-hydrate bubbles with a pipeline surface, Under certain conditions the


whiskery hydrates may completely block the pipeline within several hours. However, the most dangerous period for a complete pipeline blockage by a hydrate plug is the start-up period after a long shut-in, when separate accumulations of hydrates may be carried by the flow and accumulate in a section of the pipeline with a local solid or a fluid resistance for the flow. Conclusion Despite the existence of a number of recommendations for prevention of hydrates formation, hydrate plugs do form in wells and gas or oil pipelines. Tremendous material resources are expended for hydrate plugs removal. State of the matter is that today the problem of hydrate kinetics hasnt been solved yet for static and for dynamic conditions. Both the processes of accumulation and decomposition of different hydrate crystals occur at the P-T conditions of hydrate formation. Most quickly hydrates form on a free gas-water interface. Depending on certain conditions, hydrates may block a pipeline within hours, or not to plug it for days at equal thermodynamic conditions. The start-up periods atler long shut-ins are most dangerous and hard to control with regard to complete hydrate plug formation in wells and in pipelines in deep offshore. Complete hydrate plugs form especially readily from partially decomposed separate hydrate accumulations when pressure is increased in cold shut-in pipelines. Nomenclature D= coefficient of diffusion, cm2 S-l \ = experimental fugacity of component j at temperature T, kg cm-z f~j = equilibrium fugacity of component j at temperature T, kg cm-2 Ap = chemical potential difference in forming one mole of hydrate from the bulk solution (11 ), J mole- NO= specific content of water molecules adsorbed per unit surface per unit time, mole cm-2 s-l N= number of water molecules adsorbed per unit surface, mole cm-z Ni~ = molar fraction of dissolved component in water rtw = number of water molecules per gas molecule Pc = capillary pressure, kg cm-Z (P-P@) = overpressure beyond the equilibrium value, kg/cm2 Q= heat of crystallization, J mole-i Qi = molar fractions of guests in the hydrate cages of i on a water free basis type R= universal gas constant o = surface energy, J cm-z Tp = equilibrium temperature of crystallization, C TO = temperature of the crystallization process, C ~ = time of crystal formation, s Vi = partial molar volume of component i, m3 mole V~ = molar volume of gas hydrate, cm3 mole- V~ = molar volume of hydrate, cm3 mole- 752

VW= molar volume of water, cm3 mole Acknowledgments

The author thanks his colleagues of the Petroleum Engineering Department and Offshore Technology Research Center, Texas A&M University for the presented opportunity to conduct unique experimental research, and Professor E. D. Sloan for a detailed discussion of the obtained results,

1. Savidge, J.L.: Fluid Properties Research, 24 GRID, Fall (1995). 2. Makogon, Y.F., Khalikov. G.A.,: SoIubility of Gases in Water in Presence of Phase Transitions, Gomoe Delo, AlmaAta ( 1971). 3. Makogon, Y.F.: Hydrates of Natural Gas (in Russian), Ned~ Moscow (1974). 4. Makogon, Y.F.: Hydrates of Natural Gas, PennWell, Tulsa (1981). 5. Bishnoi, P.R., and Vysniauskas, A.: Kinetics of gas Hydrate Formation, Pt., Chicago (1980). 6. Englezos, P.A.: Model for the Formation Kinetics of gas Hydrates, Calgary (1986), 7. Austvik, T., Lund, A., Lysne, D., Lindberg, E., Loken, K.: Hydrate Formation in Flowing Fluids, Trondheim ( 1990). 8. Sloan, ED.: Clath-a(e Hydrates of Natural Gases, Marcel Dekker, Inc., New York ( 1990). 9. Jamahsddin, A. K., Kalogerakis, N., Bishnoi, P.R.: iHydrate Plugging Problems in Undersea Natural Gas Pipelines Under Shutdown Conditions, J.P.S.&E., 5, Amsterdam (1991). 10. Nerheim. A.R., Svartas, T. M., !%muelson, E. J.: Investigation of Hydrate Kinetics, 2nd Intl. OPE Conf. (1992). II. Englezos, P.A., Kalogerakis, N., Dholabhai, P. D., Bishnoi, P.R.: Kinetics of Formation of Methane and Etharre Hydrates, Chem.Eng.Sci.,42,(1987). 12. Berezhkov& G.V,: Thread-1ike Crysta/s (in Russian), Nauka, MOSCOW (1969),

Fig. 1 Schematic of the apparatus for studying the gas-water phase ratios and kinetics of hydrate formation. 1- reactor cell; 2- windows for visual control; 3- magnetic stirrer 4- magnetic stirrer drive; 5- compensation system of liquid withdrawal; 6- system of measuring phase ratios; 7- system of injected liquid pre-treatment; 8- two-layer elastic vessel; 9- liquid water; 10 -gas G - high pressure gas source; P - pressure control system; t - temperature controller.

I-+-2.5 8000, I 1+5

Ixp;l I I


t . .








Temperature, C

Fig. 2 Safice tension (u, din/cm) free water-methane dependence of pressure and temperature.

Fig. 5 Photograph of methane P=77 kg/cm2, T=5.6 C. 753






. . ..-_







. . .. ! I

----4+- , ._.__: I

: .!.:.:.. ;.. , ,. 4.!~ ::_. ... i I,:--:. *..



.- .-. .


l\ I

... .. .. .

:-.:. I.- .._--, -:. . ...









1 G TIME. b

Fig. 8 Variation of the iinear growth rate of whiskety methane hydrates with time.

v, cmlg




Fig. 9 Dependence of the solubiiity of methane in water on pressure and temperature with a free interface.


n -. p
0 a



:: .. . :.:

s m


A-rm O-*C