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SPE 28507 State-of-the-Art Survey on Hydrate Formation

M.A. Hight, Texaco Inc.

Copyright 19S4, Sedety TIM

of Petroleum

Engineers,

Inc. end Exhibition held in New ~leans, ~! LJ.SJL, 25-26 SaPtember 1994

rI
follewing review of information contained of Petroleum Engineers and are subject to cerrecfion by the author(s). officers, or membm. Papers preeanted at SPE maatings are aubjact to to an abafracf of not more than ~ w~ds. Illuatrationa may not ~ COP~ Librarian, SPE, P.O. BOX 833S36, RlchardWn, TX 75~3-3SW. U.S.A. in an abstract submitted by the author(a). Contents of the paper, The material, as presented, cfces not nacesaarily reflect publication review by Editorial CommittWa of the Society The a~ra~ shoufd cont~n ~nsPic@Jus ackn0w~9ment Teiex 1W45 SpEUT.

paper wss prepared for presentation

at the SPE 69th Annual Technical Conference by an SPE Program Commlttae

This papar was ealactaci for presentation

as presented, have not b%en reviewed by the seciety any position of the ~iety of Petroleum Engineers, its of petroleum Engineers. permission to COPYis restricted of where and by whom the paper is presented. Write

Abstract
The formation of hydrates in wells and pipelines can seriously hamper production operations since hydrates ... ., .I:___ T1..a can completely mock fiOwIIIIe>. III= $a.rnntinn ,Ull, lull=,, (-if ~. hvd[~~~~ ,., is due to the presence of water along with certain low molecular weight gases. To avoid hydrate blockages it is imperative to first know under which temperature and pressure conditions hydrates will form. This can be predicted by computer models based on the fluid composition. This study predicts hydrate formation conditions for a range of live oils by computer simulation and determines the sensitivity of several physical properties.

therefore causing the same types water lines in winter conditions.

of problems

as with

in order to avoid hydrate problems it is imperative to and pressure first know under which ?ew,perGfwe conditions hydrates will form. The hydrate formation conditions are dependent upon the fluid composition , *,~----:cnm. t- h,, and can be determmeci nom me ~urrlpuwlw[ ~, computer models. Hydrate formation conditions can then be compared with the pressures and temperatures expected in the wells and flowlines. If operating conditions will be in the hydrate formation region, then plans to prevent hydrate formation can be made. One way to prevent hydrate blockages is to avoid the temperature and pressure conditions under which they form. This can be accomplished by insulating or burying pipelines to reduce heat losses and sizing flowlines to maintain higher flow velocities and reduce pipeline residence time. However with deeper reservoirs, the resulting fluid flow paths become so long that a tremendous range of pressure and temperature conditions are encountered and this method is not feasible. Often hydrate conditions cannot be avoided and other precautions must be taken. These include removal of water or removal of hydrate-forming components, or addition of hydrate-inhibiting chemicals. wfJter removal usually requires the additional handling of large amounts of produced water which for offshore operations often means separate flowlines and may

Introduction
Hydrate formation occurs in the presence of water along with certain low molecular weight components that are commonly found in petroleum production. Hydrateforming gases that are common in reservoir fluids are methane, ethane, propane, butane, nitrogen, carbon dioxide, and hydrogen sulfide. Hydrates are solid crystals of water that form around small vapor molecules. They form as hydrogen-bonded water molecules in the form of cages trap the gas molecules inside. These single solid crystals propagate until large crystal masses have formed. Hydrates have physical propetiles similar to ordinary ice, except that they form at temperatures much higher than normal freezing conditions. As with ice, the water expands as it changes from a liquid to solid state,

References

and illustrations

at end of paper 439

STATE

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SPE 28507

h !mg dktmces. Removal of M be ecmmh! hydrate-forming components invorves Iowefing the pressure to release the light components from the heavier liquid components and usually requires subsequent compression and/or pumping to transport the fluid long distances from the separation point. The addition of hydrate inhibitors is successful, but expensive and Classical problems. environmental increases thermodynamic hydrate inhibitors that have been used
successfully are sodium chloride and other electrolytes, methanol and monoethylene glycol. These are used alone or in combination with each other. Removal of hydrate-forming components by separation will not be a complete removal and therefore will tend only to shift the equilibrium line at which hydrates will form. For lighter reservoir fluids this separation will probably not be beneficial. For heavier fluids, separation may reduce but not eliminate the need for inhibitors. Two types of chemical inhibition have been developed for the petroleum industry. The first, referred to as thermodynamic inhibition, is based on a shift in the phase equilibrium to pressures and temperatures outside the field operating conditions in order to avoid the formation of hydrates. The second method, called kinetic inhibition, deals with affecting the crystal growth rates so that once formed, small hydrate crystals will not agglomerate and can move along with the fluid stream without forming blockages. Thermodynamic inhibitors have been used successfully for many years aithough cosis can be proiiibitiw, especially for moving fluids long distances from offshore areas. Quantities of methanol required are often in the range of 20 to 30 weight percent methanol in the water phase. Kinetic inhibitors will be needed in orders of magnitude smaller quantities, but the chemicals and methods are still in the development and testing phases. Limits of effectiveness are not yet defined to the point of practical application without high risk. The mechanism of thermodynamic inhibition stems from the increased competition for the water molecules by the inhibitor molecules or ions. In order to be effective, inhibitors must be in the liquid water phase. Any volubility in the vapor or liquid hydrocarbon phases must be accounted for and considered in calculating inhibitor refi:]irements. .=-.. . . .. ... .

small cavity and the two others are large cavitie Cavity (a) in Figure 1 is composed of five-sided fac and there are twelve of these faces. Thus this cavity h the notation 512. Cavity (b) also has twelve five-side faces but has a six-sided face on both the top and t bottom of the cage. It is denoted 51262. Cavity (c) h four six-sided faces in addition to the twelve small on and is labeled 51262.
Ths .mr-rll .- m-jvitv ,,, --,..-. ...., iS the basic

building

block

of bo

structures. Structure I is composed of two of the II cavities and six of the 51262 cavities. Structure composed of sixteen of the 52 and eight of the 51 cavities. In structure L the 512 cavities are linked throug the vertices and in structure II the 512 cavities are link through face sharing. These cavities are not stable as pure larger than ice cavities and will supported by the presence of guest large percentage of the cavities. If components are available. they will fill stabilize the hydrate crystals.

water. They a collapse if n molecules in hydrate-forming the cavities a

to The occupation of hydrate cavities is determined large degree by the size, chemical nature, and sha of the hydrate-forming guest molecule. The formatio of hydrates occurs at an interface of hydrocarbon flu and liquid water. This can be either a free-gas-liquid interface, a liquid hydrocarbon-liquid water interfac or a fluid hydrocarbon-adsorbed water interface. D to the limited solubilities of hydrocarbons and water each other, fermcdior! of hydrates in either the water hydrocarbon liquid is unlikely.

Small cages must be filled by small molecules such methane, nitrogen and hydrogen sulfide. As pu components methane, ethane, carbon dioxide, a hydrogen sulfide will each form structure I hydrates. In mixture, however, structure II hydrates will usually formed with the smaller molecules the small caviti su and stabilizing the hydrates with larger molecules as propane and iso-butane in the larger cavities.

The rate of hydrate formation in processing equipmen and pipelines is largely unknown. The effects of flu velocities and flow regime also remain to investigated. Since hydrate formation takes place water-hydrocarbon fluid interfaces it follows that flo regime will affect hydrate formation tendencies.

Background
Petroleum-related hydrates belong to either of two crystal structures, called structure I and structure Il. On a molecular basis, these crystals contain at least 85 percent water. The three basic cavities that compose these two structures are pictured in Figures 1 as presented by Sloan(1). The apex of each angle represents a water molecule and the lines between them represent hydrogen bonds. Structures I and II in are composed of mixtures of the three cavities. Cavity (a) is considered a

Hydrate Curve Generation

The purpose of this portion of the study is to generat hydrate equilibrium curves for a variety of fii.kk a observe whether a trend exists based on some physic or chemical property of the fluid. If trends can be see then a generalized curve or equation can com%km ueveioped to predict hrydrate kiirn@~fi based on a single fluid property. This will g approximate information useful for screening purpos

440

SPE28507 when detailed available. information is not needed

MARGARET or is not

A. HIGHT

Hydrate Curves
Hydrate equilibrium Curves have been generated for the compositions described in Tables 1 to 3. These are shown in Figures 3 to 5. The region to the right of each curve represents the hydrate free region. The area to the left represents the conditions under which hydrates will form. The point at which the slope of the curve changes sharply is the bubble point. The curve below the bubble point represents the presence of two liquid phases (hydrocarbon and water), hydrate crystals, and vapor. The curve above the bubble point represents hydrates plus the two liquid phases. This portion of the curve is a straight, nearly vertical line that shows very little pressure effect on the hydrate formation temperature. The Garden Banks fluid because of its intermediate gravity is plotted on all hydrate curves (solid black line) for easier comparison from one set of curves to another. Figure 3 displays the hydrate equilibrium curves for all the dry gases. These curves fall into two groups: one with hydrogen sulfide and one without. The sour gas curves lie from 20 to 28 degrees to the right for the same pressure than the other gases. The sour gases can form hydrates at 88 to 90 OF degrees over a wide range w-c Tha <a tr ames show very little change with fif ~, mr=~~l -, .,-,--,,, + ---~----.. pressure above 1000 psia. A comparison with the phase envelopes for these gases in Figure 6 illustrates that for pressures below 1400 psia these gases are in the two-phase region. Only West Swan and Wilson Ranch remain outside the phase envelope in the vapor region. These are also the two fluids that have the least tendency for hydrate formation. Equilibrium curves for the gas condensates is shown in Figure 4. All of the seven fluids, fall into a range of curves representing a narrow band with orIly about one degree difference in temperature for each pressure. The eKept kx Wki= curves faii neariy on top of each dki the bubble points differ. Figure 5 shows hydrate equilibrium predictions for the remaining heavier fluids. Of these fluids, North Arne is the only fluid that has very little tendency for hydrate formation due to its low bubble point pressure.

Each hydrate equilibrium curve represents the pressure and temperature conditions under which hydrates will form if free water is present. Each hydrate locus is a curve with temperature along the x-axis and pressure along the y-axis. The pressures and temperatures making up the region to the right of each curve is the hydrate-free region. All the conditions to the left of the curve lie in the hydrate-forming region. These hydrate curves are useful in conjunction with hydraulic simulation of wells and pipelines. The hydraulic models will predict pressures and temperatures all along the fluid flowpaths for the various rates, water cuts, and compositions to be expected. Plotting the pipeline or wellbore conditions on the hydrate plot will show under which conditions and in which locations hydrates can be expected if the hydrate-forming region will be entered.

Computer Simulation Model

A commercially available computer program was used to generate hydrate curves based on the fluid compositions. The program is written specifically to predict hydrate formation in mixtures of iiyr5~OC~ibO~S and associated materials. The program can be used to predict hydrate forming conditions in the presence of an aqueous liquid, a gas, and/or a non-aqueous liquid. The program is a state-of the-art program that will predict the entire hydrate formation pressure-temperature locus either with or without inhibitors. The base program is based on the scheme suggested by Parrish and Prausnitz (2), which was modified and extended by Ng and Robinson (3,4). The gas hydrate routine is based on a procedure developed by Ng and Robinson (5). The Peng-Robinson equation of state (6) is used for all property calculations throughout. The program allows fluid streams to be defined with as many as 20 components. The components may consist of discrete components as well as petroleum fractions or pseudo-components. The program has a database of 28 pure components including those common to hydrocarbon reservoirs. This model has previously been validated against laboratory data for several of the fluids presented in this study.

Fluid Compositions
Hydrate curves were generated for seventeen different reservoir fluids representing a range from black oil fluids to gas condensates and dry gases. Figure 2 presents the phase envelopes for some of the fluids to show the range of Yhe fluids sfudiea are of fiuids used. The compositions shown in Tables 1 to 3, respectively for dry gases, gas condensates and black oils. Physical properties for all fluids are shown in Table 4.

Senslthdty to Physical Properties

Results of the hydrate curves were studied to determine which properties. if any would categorize the fluids into types of hydrate curves. Some of the properties looked at were the specific gravities of the vapor and liquid, . . -1--- .1-. ..,-:..- k+. U. A ~~= Wclgl II>, II m the lllUIGUUIUI ~CiSjOii iG?KM Cd percentage of hydrate forming components present in the fluid stream. Figure 7 shows hydrate formation tendencies of some of the hydrate-forming molecules when they are present

441

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as pure components alone. Tables 1to 3 show that all fluids except North Arne and the dry gases nave from 44 to 87 mole percent methane and all have from 3 to 10 percent ethane. Table 1 shows that the sweet dry gases have over 75 mole percent methane and about 90 mole percent combination of methane, ethane and propane yet the hydrafe formafion tendencies are much different than for the pure components. At a pressure of 2000 psia these gases will form hydrafes at 68 to 70 F yet the pure

Ieauli>

represent ---..14- Ull --

the separator vapor. Figure 9 shows the same - >el . -iI mug la p!d.

components

form hydrates

below 60 F at this pressure.

The sour gases all contain about 30 mole percent hydrogen sulfide and over 30 mole percent methane. A comparison of these curves with that of pure hydrogen sulfide shows the same trend with the same shape of curve and the same shift to the right from the other curves that have no hydrogen sulfide. This difference in hydrate formation tendencies between pure components and mixtures has also been observed in Iaborafory work. Dramatic increases in hydrate stabilities have been observed with the addition of larger-molecule gases to methane gas. As pure components, the small molecules (methane, ethane, carbon dioxide, and hydrogen sulfide) will form Structure I hydrates, but in mixtures will form Structure II hydrates. These pure component hydrates are formed with only one size cavity being occupied. With mixtures, both the large and small cavities will be occupied and this appears to lend stability to the hydrate crystals. Also certain components can act as help gases to increase the hydrate-forming capability of other components. This has been observed with both oxygen and nitrogen. One fact became apparent in surveying the results. That is that the total fluid stream properties must be considered rather than just the vapor phase or the API gravity. The interaction between the liquid and vapor stream is important, even though the hydrate-forming components will be in greater concentrations in the vapor phase. None of the Table 4 properties of the separate vapor and liquid phases could be consistently correlated with the hydrate equilibria. In order to study some of the differences between the vapor and the wellstream reservoir fluids, a process simulator was used to generate compositions of four of the fluids separated at standard conditions. These compositions are shown in Table 5. Only the vapor compositions were used to generate hydrate curves for these fluids. The fluids chosen for these runs were those with lower percentages of light hydrocarbons.

The four fluids shown all have low percentages of the light hydrocarbons before separation. The vapor stream compared to the two-phase stream shows a greater tendency for hydrate formation in all cases. Results for N. Arne indicate a change from the least tendency for hydrate formation to the greatest of the four fluids with separation. The other fluids exhibit the same trend but different magnitudes of change. N. Arne may exhibit different behavior because its composition is not adequately defined since the reservoir fluid has 71 percent C7 plus components and it has the largest change in its bubble point. If N. Arne is neglected, the other three fluids show a decreasing tendency for hydrate formation with decreasing vapor specific gravity. This can be compared with Figure 10 which is a published chart (1) of hydrate-formation tendencies based on gas specific gravity. The comparison, with an expanded scale, is shown in Figure 11. The solid dashed lines represent specific gravities of 0.7, 0.8, 0.9 and 1.0. These results indicate good agreement, with the largest difference being only one F for the Ewing Banks fluid. This limited sampling of data indicates that separator vapor specific gravity can characterize hydrate formation tendencies as long as this information is not used to characterize full wellstream data. Figure 12 is a semi-log plot of the six gases compared with the hydrate prediction for gases. The symbols represent the three sweet gases and the dashed lines represenf the hydrate prediction chart lines. The Brookeland line is slightly above where it should be for a specific gravity of 0.726. W. Swan (specific gravity 0.68) lies on the 0.60 line and Wiison Ranch (gravity 0.6.4) iies in between 0.60 and 0.68. The order of the two gases is reversed from what the specific gravities would predict. The three sour gases in the lower portion of the plot fall well below the 1.0 line even though their specific gravities are only slightly greater than 1,0. Of the eleven hydrate curves characterizing the condensates and black oils, the only property that correlates well with the hydrate formation tendency is the molecular weight of the total fluid stream. The similar hydrate curves shown in Figures 4 and 5 represent a range of fluid molecular weights from 29 to 78. Shasta (molecular weight = 29) has one of tine lowest molecular weights and shows the greatest tendency for hydrate formation, N. Arne on the opposite end of the scale has a molecular weight of 189 and the least tendency for hydrates. Ewing Banks >.~ith ~ meiecuiar w-iriht ..-. V... nf -. 147 . .. falls in between N. Arne and the lighter fluids. Garden Banks with a molecular weight of 79 falls just to the left of the 31 to 78 range. With seven curves behaving similarly, enough data was available for a good curve fit. An exponential curve fit a=van of $h~ .,the following .,, S!m!br f!ikk ShOWd

Figure 8 is a plot of the hydrate curves for Harald, N. Arne, Garden Banks, and Ewing Banks. Both curves from the ccmap+nr CQrnpQSiNQnS (TQble ~) and the reservoir .,y ---- vrmnr .-r-. compositions are shown. These fluids represent a vapor gravity. The solid lines range of 0.7 to 0.93 specific ------**L_ .---m, ..:. f~u,~~ ~n~ ,, ,= +hc. Antt*r4 repw3seril 111= Ie>clvull !ines l r-

.
SPE28507 MARGARET A. HIC;HT 5

regression data listed in Table 5. The data from Harald and Green Canyon fluids were not used in the curve fit #.. Ra. ant CApUl I-I I IS cm above the bubbie pOh~. The i~Wlhil~ shown in the Table 3 for the equation where y represents pressure in psia and x is the temperature in F.

by as much as 18 degrees for the 100-psia separation and seven degrees for the high pressure separation. !hese are offset somewhat by the shift to the right in the equilibrium line for the vapor curves by as much as 4 degrees at some pressures for the low pressure separation and about 1 degree for the 1300-psia separation. These separator curves show that for compositions

y = aebx
The exponents from the individual curve fits were averaged. The resulting plot of the generalized curve is Shown in F&W= I ~ a!~ng with the Staffjord and Valdemar fluids. The curve is about 1 degree off for the average in the pressure range up to 2000 psia. Above this pressure there is a greater deviation from the high side and the However, it is ~uwe fl? is neariy the same as the IOW curve. on the conservative side at points where it does deviate. For comparison the equations with the highest and lowest a-values are also plotted.

where separation can result in a significant reduction in the bubble point, a decrease in hydrate formation ~emlPe:aydre~ can be ~xp~cted for the liquid stream. This will be partially offset by an increase in the hydrate formation temperature in the vapor stream.

Conclusions Separation Effects

Since hydrates are formed at the interface between hydrocarbon phases (either vapor or liquid) and the free water phase, it follows that vapor-liquid separation will affect hydrate formation tendencies. Predictions were made for three fluids separated at pressures of 100 and 1300 psia. Figure 14 shows the difference in hydrate tendencies for the Shasta fluid on separation at 100 and 1300 psia. The solid line represents the reservoir fluid before separation. The dashed lines show the liquids at the two separator pressures and the dotted lines show the vapor streams at the two pressures. The vapor curves show an increased hydrate tendency of about 1 degree for pressures above 500 psia. The separator pressure makes no appreciable difference. The liquid curves show less tendency for hydrates by 1 degree for the higher pressure and 3 degrees at the 100-psia separator pressure when compared with the reservoir fluid. Separation effects for the Statfjord fluid are shown Figure 15. Separation at 1300 psia shows less than degree change for both the liquid and vapor streams. 100 psia, separation shows a 3 degree shift to the left the liquid hydrate equilibrium curve and 1 degree shift the right for the vapor line. in 1 At in to Of the eleven gas condensates and black oils evaluated, seven had hydrate formation curves that were within 1F of each other for a given pressure below the bubble point. Molecular weights of these similar fluids ranged from 31 to 78. Full wellstream fluids cannot be categorized by the specific gravity of the vapor since liquid, if present, will influence hydrate formation tendencies. Of the properties studied, the property which best categorizes hydrate formation tendency is the molecular weight of the fluid including both liquid and vapor phases. If vapor-liquid separation can result in a significant reduction in the bubbie point, a de~iease in hydrate formation temperatures can be expected for the liquid stream. This will be partially offset by an increase in the hydrate formation temperature in fhe vapor stream. Hydrate tendencies of light hydrocarbon components in a mixture are much different than the tendencies for the components if pure. The components influence each other and can cause a change in the type of structure formed and in the stability of the hydrate crystals. Hydroaen sulfide has a dominant effect gases-and results in hydrate equilibrium similar to pure hydrogen sulfide. on sour curves

All liquid streams in Figures 14 and 15 have bubble points above 2000 psia and hydrate curves below this point are based on a two-phase hydrocarbon stream. Both fluids have methane concentrations above 50 mole percent at both pressures, therefore keeping the bubble points high. The presence of other hydrocarbons along with methane increases the stability of the hydrate crystals. Figure 16 shows separation effects for the Garden Banks fluid. In this case, bubble points for the liquid stream are shifted to below 1200 psia and there is a significant shift to the left in the hydrate equilibrium line. Curves are shifted

References
Hydrates 1) Sloan, E. D., Jr., Clathrate Gases, Marcel Dekker, Inc., New York, 1990 of Natural

Prausnitz, W.R. and J.M. Prausnifz, *Dissociation 2) Pressure of Gas Hydrates Formed by Gas Mixtures. Ind. Eng. Chem. Process Des. Develop., 11, 26(1972).

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3) Ng, H.-J. and D.B. Robinson, The Measurement and Prediction of Hydrate Formation in Liquid HydrocarbonWater Systems, Ind. Eng. Chem. Fund., 15, 293(1976). 4) Ng, H.-J. and D.B. Robinson, The Prediction of Hydrate Formation in Condensed Systems, AIChE J., 23, 477(1977). 5) Ng, H.-J. and D.B. Robinson, Method for Predicting the Equilibrium Gas Phase Water Content in Gas-Hydrate Equilibrium, Ind. Eng. Chem. Fund., 19, 33(1980). 6) Peng, D.-Y., and D.B. Robinson, A New Two-Constant Equation of State, Ind. Eng. Chem. Fund., 15, 59(1976).
C02

Table 2 Compositions for Gas Condensates

Shas 1 I 0.919 1 Stat.
1 i

Ersk
I

Vald 1.19 I

Jolt.

G.C. I 0.05

Har. I 1.160

1.144 I I

4.78

0.17

61.66

I 52.38 I 3.86 5.16 1.59 1

I 44.28 I 7.779 I 7.009 1.300 1 3.230 I 0.960 1.570 I 2.570 26.64

I
I
I

C2 C3 i-C4

! I 1

7.15 4.49 0.613

! 7.654 3.864 0.564 [

10.73 1 5.11 0.99 I 1.76 1 0.79 0.89 1.29 10.88 1 I I

7.116 I 4.726 0.600

7.81 4.35 0.95

I
I
I

1 2.150 I 0.950 1.550 0.84 1.15 I 1.91 18.52

n-C4 I i-C5 n-C5 C6 C7+

1.634 0.409 0.715 I 1.022 6.946

I 1.479
0.338 0.661 0.783 6.868

2.00
I

3.17 I .86 2.11 4.13 25.60

I 2.150 16.69

I
Table 1 Compositions for Dry Gases I
C. B.

I Brook
C02
I N2 H2S 1 I 0.59 0.00 4.70

I w Sw I W Ran I
I I I 8.21 0.46 O.(XI I I I 0.67 0.05 0.00 I I I

Aker
3.15 2.50 33.50 I I

I
I

Neal
4.97

5.98 6.18 29.20

I 1.44
I 38.50

I I I

Table 3 Compositions for Black/Heavy Oils

Brent C02 1.93 G.B. Occl N. Ame

E. Banks

C2 C3 i-C4

I ]

10.38 3.48 0.64

I I

4.97 1.29 0.19 0.24 0.07 0.05 I I

8.80 1.91 0.26 0.29 0.09 0.04 I 1 0.06 0.07 I I I I I ] I I I I

6.48
I

9.04 I 8.19 1.37 I 1.83 I I 0.50 0.61 I

6.75
I

9.62 1.08 1.34 0.51 0.49 0.46 0.11

\ 10.23 ~ 1.42

C2

9.58

6.75

2.94

I n-C4 i-C5 n-C5 1 C6 C7 C8 I I I 0.12 0.06 0.07 I I 0.96 0.32 0.24

I
I I

I
] I I

I 1.56
I 0.53 0.57 i

I I I

=aa=
n-C4 I 3.5 I 2.25

3.32

%--t+
2.160 1.m

1.42
0.86 0.68 1.79 37.45

I I I I

I 0.61 I I

0.08 0.09

I
!

0.58 0.26 I I

0.48

=&&
C6 I 2.18
C7+ ! 72.79

* 1.290
I
I

2.85
23.47

2.700 71.137

I 0.00 I o.oo I 0.,2 I 0.27 I 0.49

SPE28507

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A. HIGHT

Table 4 Properties at Standard Conditions

Vapor Liquid Total Stream GOR Fiuid Brook W.sw W. Ran Aker C.B. Neal Shasta Stat Erskine Vald. Jell G.C. Har. Brent G.B. N. Am sp. Gr. 0.7266 0.6846 0.6359 1.000 1.04 0.189 0.7370 0.7102 0.8321 0.8297 0.7574 0.8289 0.9356 1.1239 0.7916 0.8470
Mc! %! sp. ~.~. &@l Wt

Table 5 Vapor and Liquid Compositions of Separator Fluids

1 1 I I

Comp #

Harald , Vap. Liquid

N. Ame 1 Vap. Liquid

Garden I Vap.

B.

Ewing B. 1 Vap.

I
~02 \2
c1

Liquid

Liquid

Mol Wt -

SCF/B -

! 2.221I 0.038I 1.X6 I 0.02,10.00 I 0.00 I 0.350 I 0.006 1.709

65.44 0.003 0.471 0.879 69.00 0.002 0.504 3.452 74.55 0.004 0.417

21.05 19.8 18.5

0.674
85.401

0.031
0.553

h2 k3 -C4

I 11.31 i 0.472 I 9.671

I 1.502

i 12.42 I 0.521 I 9.194 t 0.343 ! 5.449 I 0.218 9.386 1.567 3.262 +

29.0
30.2 31.6 21.35 20.58 24.11 24.04 21.94 24.014 27.11 32.561 22.93 24.54 I 20.284

0.748 0.8035 0.7852 0.7496 0.8451 0.8261 0.07456 0.8639 0.8728 0.7627 0.9333

125.54 156.99 162.02 192.42 214.79 166.74 187.62 241.22 228.14 231.41 I 331.53

29.00 30.71 40.13 53.93 62.69 69.66 78.22 72.68 79.46 189.27 ] 146.84 ]

9964 8447 4874 2386 1945 1393 1123 1983 1331 111 544

I 1.458
0.630 1.879

F#
-C4
3.744

1.614 0.649
2.165 1.261

=-k=
1.424 0.541 2.548 + 1.469

1.707 I 1.002

-C5

0.8142

0.704 0.461 + 1.440

E5.lE
0.466 ] 0.992

+
3.284 1.025 I 7.633

-4=

E. B.

0.7001

Table 6 Regression Dat for Exponential Curve Fit I of Seven Similar Hydrate Formation Curves I Number I Corr. I I I ll. la I ofpoints mid Coef. 0.0;37 31 0.9934 5.829 Statfjord 41 0.0897 4.257 Erskine 0.9942 26 Valdemar 0.9968 0.0848 5.596 Joliet 0.9977 0.0837 5.9054 25 0.9996 0.0841 5.358 20 Gr. Can. 34 Brent 0.9960 0.0900 3.902
Haald 0.9996 0.0853 4.898 20

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Figure 1. Hydrogen-Bonded Water CaviU* that form Clathrate Hydrates

Figure 2. Phase Enveiope for Fiuids Studied

@@@

(a)
Small Cavity

(b)
Large Cavities

(c)

Figure 3. Hydrate Equilibrium Curves for Dry Gases

Figure 4. Hydrate Equilibrium Cuwes *fir Iur e-e - r.mwhnsatas w. ---- .--.-

r]

G. Mb E18khe .. . .. . H9dd -. St811im-d

imm E ~ 1,s00
l:~>y~!::d

ii

/) I :~-! 40 m & ~ Tanpombm dq F

shL

Wdanm .bIliOl G.

CUW

a4Gsow~@J

SJ

Figure 5. Hydrate Equilibrium Curves for Biack OilS

Figure 6. Phase Enveiope for Gases

/220-

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Figure 7. Hydrate Equilibrium Curves for Pure Components

.. . ManmO

Figure 8. Reservoir Fluid vs.Separator Vapor Hydrate Equilibrium Curves

am, -, --2,500 g z,~ = , m *
e=

,
*Oti

,V
:e9 ::

_
N. km

Etharm . ..... ! I i Proplme NtiOgen Carbon D* -.

g 1,500 i & I,ooo 5W Om

I I

~
..

.------.-.V...7---7
70s0 impuduro, dq F

G.Eants

.3uUii --

.-

2 1=
G9

G. S8nlfs E. Sanka Maid

,%0 @

:%* ,=..

N.&m .. . ..

. ,**ws@@:$ xl Tonq)omtum

G. sank= ...*..

E. Sanka

40

70

dq F

Figure 9. Log Plot of Reservoir Fluid vs. separator Vapor Hydrate Curves *M
201YI I,ooo gw : ..: G .:9
G :#

Figure 10. Pressure-Temperature Curves for Predicting Hydrate Formation ~

.000

/1

/,

.u6U6111.

N. Arm G. Sdm E. Emnlu mm N. km ... . . G. Sao!m ..* E. Banks

jm

,w.& ..;.*. G ;D ,ti.:. a ,r... ,..,.* :..0. ..:0. ,-. @ .*.*::O. e

100 ;/ 50 30

40

50 Tunpodum

60 d~

70

Figure 11. Log Plot of Reservoir Fluid vs. Separator Vapor Hydrate Curves

Figure 12. Hydrate EquilibriumCurves for Dry Gases

- -.,

A
,.. -.
55

Harold

G._Banks . . . . ... . . . . .... , , e =-... KS

:-F . . . . ..* .-.. ./. #. ... ..

200 .-.. ..*.:::
. .. .

. ...

...-... -.:- ......

1.0

lCO -

/
50 -

---

40

45

50

An

45

50

55

L
W. R;nch .
G

W. Swan

BfookkNMl

447

10

STATE

OF THE ART SURVEY

ON HYDRATE

FORMATION

SPE28507

Figure 13. Comparison of Actual Hydrate Curves with Curve-fit Data

Figure 14. Shasta Hydrate Curves for Reservoir and Separator Fiuids

:R i1.500
f & 1,000 Soo 0

/
L-

/ =
L_
Hbh . ..... -. 50 60 70

:-H K=i,

40

40

dqfWF mIII&turo,

P.

----

-Au

-.4 u

U.,A.Aa
nyui am

m ,Fune fnr
UUI r=IWO

Rrmnrvnir
-.-. . . ..

Figure

la.

akmp

and Separator Fluids

Figure 16. Garden Banks Hydrate Curves for Reservoir and Separator Fiuids
3.oal I Y 2,S00 ; j z,~ a f g ! ! 1,000 J S20 j 4 /.#4t # ..*. i Y.4 n. #.;....D..e. .~-e:=. Vapa @ P=1300 ;

.*. \#II
.

-r

i
4 {:!

:6 .: i .f

No ~p. _ Uq@d @ yl~

Uquid @

1,s00 -

n ---Uqula

Soo

II ?52
40 Ea 60 m 1-a

4::. 40

o ~

m
T=. dwwF

Tunpuatum. dw F

u
gg P=loo Va--w-@ P=loo

... ..

448