Chrmirul Enginrrring Sctence, Vol. 43, No. Printed tn Great Britain.

10. pp. 2661

2612.

1988.

cclc9 2509,RR S3.oOf0.00 8, 1988 Pergamon Press plc

COMPUTATIONS

OF THE FORMATION HYDRATES

OF GAS

JAN

MUNCK and STEEN SKJOLDJ0RGENSEN CALSEP A/S, Lyngby, Denmark and

PETER RASMUSSEN Instituttet for Kemiteknik, DTH, Bygning 229. 2800 Lyngby,
(First received 19 August 1987; accepted in rer;isrd,fiwm

Denmark 1988)

28 Murch

Abstract-A simple method for predicting the formation of gas hydrates is described. The hydrate-forming compounds may be pure gases or constitute a mixture like a natural gas or an oil. The influence of inhibitors like alcohols, glycols or salts on the hydrate formation is accounted for by a very flexible and robust program based on the method. The calculated results are found to compare well with experimental results for a wide variety of pure compounds and mixtures, including two North Sea reservoir fluids.

I. INTRODUCTION

Gas hydrates are solid inclusion compounds which may be formed where light hydrocarbons and/or some other light gases and water are in contact at temperatures below approximately 310 K. As the hydrates may exist far above the freezing point of water they can cause plugging of pipes, nozzles and separation equipment which would not be foreseen by considering the possibility of ice formation alone. The risk of hydrate formation may be reduced by reducing the water content of the hydrocarbon mixture. It is, however, necessary to reduce the water content significantly, so that the partial pressure of water in the mixture is below the very low equilibrium pressure above the gas hydrate. Another and much preferred alternative is therefore to lower the temperature at which hydrates may be formed by adding a socalled inhibitor. Inhibition is quite analogous to freezing-point depression and the compounds causing the largest freezing-point depressions for water are also the most powerful inhibitors. Alcohols, glycols and salts are examples of good inhibitors and methanol is the most commonly used. The most important questions to be answered when checking for possible hydrate formation under given operating conditions are:

(1) Is there any risk of hydrate formation? (2) What is the maximum permissible water content
without hydrate formation? formation (3) How are the hydrate
changed by the addition

using the most common alcohol, glycol and salt inhibitors. Illustrations of the phase behavior of hydrates are shown in Figs 1 and 2. Figure 1 illustrates the situation for a pure hydrateforming gas. The solid curves are three-phase loci representing equilibria between hydrate (H), gas (G or L2) and water (1 or Ll). Points B and C are four-phase points. The dot and dash line indicates the effect of adding an inhibitor. The three-phase curve is shifted towards lower temperatures at constant pressure. The slope of the CD section may be positive or negative since it depends on differences in (partial) molar volumes of the components in the different condensed states. These differences are very small and the CD section will therefore be almost vertical. For a mixed gas the situation may become slightly more complex due to the possible interference with the phase envelope of the gas mixture. In Fig. 2 the lines AB, BC and DE represent three-phase loci while four phases coexist on line CD and at point B. The procedure developed in this work for gas hydrate calculations does not include any real new theory. However, various previously published methods have been modified and combined in a consistent way resulting in a simple method with a very broad range of applicability.
2. A FEW FACTS ABOUT HYDRATES

conditions

of inhibitors?

The model described in the following sections answers these questions for all natural gas/petroleum mixtures

To

whom

correspondence

should

be addressed.

Water can form two types of host lattices in addition to the well-known condensed states: liquid and ice. These lattices are not intrinsically stable, but may become sufficiently stabilized when a certain fraction of the lattice cavities are occupied by guest molecules. Some physical constants for the two lattice types are given in Table I. Only gases of rather modest size and appropriate geometry can enter the cavities. Table 2 indicates the
266 1

2662

JAN MUNCK

et al.

Table 1. Some physical constants of the two possible water structures in hydrates H + L2

Property Number of H,O molecules per unit cell Number of small cavities per unit cell Number of large cavities per unit cell Cavity diameter (A) Small Large

Structure

Structure 2

46

136

16

273.15 T(K)

7.95 8.60

7.82 9.46

Fig. 1. Coexistence curve for hydrate (H), gas (G), liquid hydrate-forming compound (L2). ice (I) and liquid aqueous solution (Ll) in the case of a pure hydrate-forming compound: (- . - . -) coexistence curve when hydrate formation is inhibited, e.g. by MEOH; (- - - - -) vapor pressure of the pure hydrate-forming compound.

H, is equal to the chemical potential of water in phase c(, which can be ice (I), an aqueous solution (Ll) or gaseous water. A hydrate-forming substance or mixture in a gas (G) or liquid phase (L2) will also be present. The model used for the chemical potential qf water in the hydrate phase is the well-known van der Waals and Platteeuw (1959) adsorption model which has been used, e.g. by Parrish and Prausnitz (1972) and Erickson (1983): phase,

$=#+RT~viln i= 1, 2, K=l, 2,.

L .

(1-p) , NCAV

(2)

. . , NCOMP.

In this equation p refers to a hypothetical empty lattice state. vi is the number of cavities of type i. UKi denotes the probability of a cavity of type i being occupied by a hydrate-forming molecule of type K. According to the Langmuir adsorption theory this probability is calculated from
273.15 T(K)

Y,,=cK&( j=l,2,...,NCOMP

1 +Fcih)

(3)

Fig. 2. Coexistence curve for hydrate (H), gas (G), liquid hydrate-forming compounds (L2), ice (I) and liquid aqueous solution (Ll) in the case with a mixture of hydrate-forming compounds: (- - - -) phase envelope for the hydrate-forming compounds, (0) critical point.

gases
vidual

of interest
and gas.

to

typical

natural stabilized

gas/petroleum by each indi-

calculations

the cavities

wheref, is the fugacity of hydrate-forming component K and CKi is the adsorption constant at the temperature specified. Many previous workers select a cell potential to calculate the CKis. However, this complex approach does not eliminate the necessity for adjustable parameters. In the present model the Langmuir constants are simply considered to be temperature-dependent according to Cxi=(A,,IT) exp (B,ilT). (4)

3. THEORY

The calculations in this work are based on the following equilibrium criterion between water in the hydrate phase and water in a coexisting phase, Z: pH=p= i.e. the chemical potential of water in the (1) hydrate

This form may be derived from a square-well cell potential (Parrish and Prausnitz, I972), but it has been chosen here only because it offers a convenient twoparameter approach. The AKi and BKi parameters are found by a parameter estimation using a large number

Computations
Table 2. Gases of interest

of the formation

of gas hydrates in

2663

in natural gas hydrate formation and their occurrence the different cavities of the water structure Occupies Structure Small cavity I Large cavity + + + + + + + + cavities of type Structure Small cavity + 2 Large cavity + + + + + + + +

Compound Cl c2 c3 C4 iC4 CO, N, H,S Methane Ethane Propane Butane Isobutane Carbon dioxide Nitrogen Hydrogen sulphide

+ _ _ _ _ + + +

Table Property A&W AH,,(W AH,(ice) A V,,(liq) A V,,(ice) AC,(liq)

3. Physical

constants Unit J/mol J/mol J/mol cm/mol cmjmol Jjmol/k

used for the evaluation Structure 1264 -4858 1151 4.6 3.0 39.16 1

of eq. (7)+ Structure 883 -5201 808 5.0 3.4 39.16 2

A~~~,(liq)denotes the difference in the chemical potential of water in the empty hydrate lattice and in the liquid state at 273.15 K. AH,(liq) is the corresponding enthalpy difference. AH,(ice) denotes the difference in the molar enthalpy of water in the empty hydrate lattice and in the ice state at 273.15 K. AV,(liq) and AV,(ice) represent volume differences. AC,(liq) is the molar heat capacity ditkrence. Ajl,(ice) and AC,(ice) are set to zero.

data points as explained in the following section. John et al. (1985) recently used a Kihara potential model for the derivation of the Langmuir constants. The chrmicol pottwtiul ofwatrr in the r-phusr may in general be written as ofexperimental

,u~= /F+ R T In (f,/f,,)

(5)

where cc is the chemical potential of pure water as ice or liquid water at temperature T and pressure P,,ft, is the fugacity of water in the r-phase and,f$ the fugacity of ice or liquid water. By combination of eqs (I), (2) and (5) one gets
(l-~Y~i>i (6)

In this equation A,LL, denotes the difference in the chemical potential of water in the empty hydrate lattice and in ice or liquid water at T, = 273. IS K. AH, is the corresponding enthalpy difference, AC, the heat capacity difference and AV the volume difference. The pressure P, is the vapor pressure at To. Since P, is very small compared to P P, = 0 is used. The temperature dependence of the PV term is averaged by using ;r;=(T+273.15)/2. (8)

the difference between the chemical potentials of pure water as an empty lattice and as ice or liquid water at pressure P and temperature T. Based on classical thermodynamics and the assumptions given below one can write

It is seen that the left side of eq. (6) represents

#--PO
RT

APO
RT,

+J

-_ dP. ~0 R7-

s -?,

r AH, + AC, (TRTZ

T,)

dT

(7)

Holder et al. (I 980) have used a modified form of eq. (7) which eliminated the need for calculating the average temperature from eq. (8). AV and AH, are both considered to be pressureindependent because the pressure effects on condensed phases are small. AI/ is considered to be temperatureindependent, while the temperature dependence of the enthalpy term is taken into account by means of a constant molar heat capacity difference AC,. The constants shown in Table 3 are used for the evaluation of eq. (7). The constants are identical to the ones used by Erickson (1983) except for the molar heat capacity, which in the present approach is considered to be independent of temperature. Combination of eqs (6) and (7) gives the final

2664

JAN MUNCK

et ~1.

equation A&
RT +

- AH,+AC,(T-T&T

s
AV

s T,

RT2

Prausnitz (1986). For electrolyte inhibitors the activity coefficients are calculated from the extended UNIQUAC model dcvcloped by Sander ef al. (1986).

-dP=ln o RT

(f,/!X)-~vi
I

In

(I

-;yKi)-

f9)

Hydrocarbon

phase

(G and L2)

a-Phase:

ice (I)

In this case Ap(,, AH,, AC, and AV represent the differences between the empty lattice and ice. At the same time the first term on the right side of eq. (9) will vanish.
x-Phase: liquid aqueous phase (Ll)

In this case Ap,. AH,, AC, and AV represent the difference between the empty lattice and liquid water. For substances like hydrocarbons, nitrogen and hydrogen sulphide the solubility in water is very low. This solubility is neglected. If no inhibitor has been added Ll is considered as pure liquid water. The first term on the right side of eq. (9) will therefore vanish. The solubility of carbon dioxide cannot be neglected. From Henrys constants found in Wilhelm and Battino (1973) Wilhelm et al. (1977) and Weber (1984) it is possible to calculate the solubility of carbon dioxide (xcoJ at the given temperature and pressure. It is now assumed that Raoults law may be used for the aqueous phase and hence that f ,/f , = x, = 1 - xCOlr where x, is the mole fraction of water in Ll. The Henrys constant as a function of temperature is given by In HCo2.r = HA, + HB,/T+
HC,

For the hydrate-forming substances and the other components in the G or L2 phases the fugacities are calculated by means of the SoaveeRedlich-Kwong (SRK) equation of state (Soave, 1972). This equation was chosen partly because of its popularity in hydrocarbon phase equilibrium computations and partly because a very powerful characterization procedure is available for the application of the SRK equation to mixtures containing heavy hydrocarbons (Pedersen et al., 1985). The G and L2 phases are in general considered to be water-free which means that the fugacities needed for the calculation of Yki in eq. (3) can be directly calculated from known compositions of the G or L2 phases. Equation (9) may now be used to calculate corresponding values of pressure P and temperature T for equilibrium between phases H, I, G, or H, Ll, G, or H, Ll, L2. If a phase stability test (Michelsen, 1982) shows that two hydrocarbon phases exist the equilibrium will be between phases H, Ll, G and L2.

Maximum formation

permissible

water

content

without

hydrate

. In T+ HD, . T.
(10)

If a hydrocarbon mixture at a given pressure P and temperature Tcontains water, there may be the risk of hydrate formation. The maximum permissible content of water is found from eq. (9) in the following way. The fugacity f, is calculated as
VP P, exp ~ RT

For mixtures containing methanol Henrys constant is calculated as

as inhibitor

the

f,=

(13)

In HCo2 =

c XI

In Hco~, I

(11)

where the subscript I is used for water and methanol. The coefficients used for the evaluation of Henrys constant in water and methanol are given in Table 4. For mixtures with added inhibitors the first term on the right side of eq. (9) can be written as In Z./X) = In (x,Y,) (12)

where P, is the vapor pressure of ice or liquid water and V0 is the corresponding molar volume ( V for ice = 19.6 cm3/mol, V for liquid water = 18.0 cm3/mol). The vapor pressure P, is calculated as In P,=a+h/T
(14)

where y, is the activity coefficient of water. For nonelectrolyte inhibitors the activity coefficients are calculated using the UNIQUAC equation (Abrams and Prausnitz, 1975) as proposed by Anderson and Table 4. Coefficients
HA Wm)
used

with values of a and h estimated from experimental vapor pressure data (Handbook of Chemistry and Physics, 198 I-1982). For P, measured in atmospheres the values are for ice
a=

17.372, h= -6141

for the evaluation of the Henrys constant

eq. (10)

of

HB (atm K)
- 8764.5 - 1783.5

(atm/ln
-21.726 0

HC

HD
K) @tm/K) 1.1055 0 x 10-A

MEOH

Hz0

160.27 10.87

Computations

of the formation

of gas hydrates

2665

and for liquid water a=14.484,

substances b=

-5351

K.

The values of the fugacities for the hydrate-forming and for water are calculated from the SRK equation of state. An iterative solution of eq. (9) will give the desired water content.
4. PARAMETER ESTIMATION

The data base used for the parameter estimation is described in Table 5. In most cases parameters for a group of gases were estimated simultaneously. This in connection with the broad data base used ensures parameters of sufficient physical significance to provide accurate predictions for mixtures not covered by the experimental data. The parameters obtained appear in Table 6. The root mean squared temperature deviations for the 489
points exceed The in the data 2.0 K. pressure base is 0.66 K. Very few deviations

The parameters needed to calculate the Langmuir constants [eq. (4)7 were estimated by adjusting the A and B parameters to experimental data.

covered by the data base range be-

Table

5. Data used to establish parameters

A and Bt

Data base
Parameters estimated Gas No. of data points Inhibitor (methanol) Reference

Structure 1 Cl: four parameters C2: two parameters N,: four parameters

Cl Cl c2 c2 N, CI fC2 ClfN, C2+C3 Cl +C2+C3

13 5 25 4 28 21 39 7 4

l-3 4 5-7 4 3, 8 9, 10 11 12 12

Structure 1 H,S: four parameters CO,: four parameters

H,S H,S Cl +H,S

CO, Cl +co, Cl fCO,+H*S

I4 5 10 23 6 12

+ -

13 4 14 15, 16 17 18 19922 19, 23, 24 10, 25 10, 24, 26 10, 27 4 12 23

Structure 2 C 1: four C2: two C3: two iC4: two C4: two

parameters parameters parameters parameters parameters

c3 ic4 Cl +c3 Cl +ic4 c1+c4 Cl +c3 C2tC3 Cl +C2+C3+ iC4+C4+C5

24 5 33 24 30 4

+ -

35 12

Structure 2 CO,: four parameters N,: four parameters

c3 + co, C3+N, Cl +C2+C3+ CO, + N,

36 39 18

15 29 28

Structure 2 H,S: four parameters

Cl +C3+H,S

13

30

Four parameters are needed for compounds which can enter both small and large cavities. Only two parameters are needed for compounds which can enter only large cavities. I, Roberts et al. (1940); 2, Frost and Deaton (1946a); 3, Marshall et al. (1964); 4, Ng and Robinson (1983); 5, Deaton and Frost (1937); 6, Deaton and Frost (1938); 7, Deaton and Frost (1940a); 8, van Cleef and Diepen (1960); 9, Holder (1976); 10, Campbell and McLeod (1961); 11, Jhaveri and Robinson (1965); 12, Holder and Hand (1982); 13, Selleck et al. (1952); 14, Noaker and Katz(l954); 15, Robinson and Metha (1971); 16, Berecz and Balla-Achs (1983); 17, Unruh and Katz (1949); 18, Robinson and Hutton (1967); 19, Holderand Godbole(l982);20, Deaton and Frost (1940b); 21, Frost and Deaton (1946b); 22, Wilcox et al. (1941); 23, Roudher and Barduhn (1969); 24, Wu et al. (1976); 25, Deaton and Frost (1946); 26, Ng and Robinson (1976a); 27, Ng and Robinson (1976b): 28, Wilcox er al. (1939); 29, Ng er al. (1977-1978); 30, Schroeter et al. (1983).

2666 Table 6. Parameters

JAN MUNCK et al. A and B for the calculation of Langmuir constants [eq. (4)]

Small cavity ..____

Large cavity
Ax IO3

Gas
Cl c2 c3 ic4 c4 N, CO, H,S

Structure 1 2 1 2 2 2 2 1 2 I 2 1 2

A x lo3 Watm) 0.7228 0.2207 0.0 0.0 0.0 0.0 0.0 1.617 0.1742 0.2474 0.0845 0.0250 0.0298 3187 3453 0.0 0.0 0.0 0.0 0.0 2905 3082 3410 361.5 4568 4878

Watm) 23.35 100.0 3.039 240.0 5.455 189.3 30.51 6.078 18.00 42.44 851.0 16.34 87.2 2653 1916 3861 2967 4638 3800 3699 243 1 1728 2813 2025 3737 2633

Table 7. kij values to be used in the SRK equation for interactions between H,O and other components Component kij 0.08 0.25 0.03 0.55 0.51 0.50 0.53 0.53 0.50

co*
H,S Cl c2 c3 ic4 c4 C5f

N2

tween 0 and 500 atm (even higher for NJ and the temperature vary between 250 and 305 K. Some of the binary interaction parameters, k,, in the SRK equation were estimated based on experimental vapor phase water contents for the relevant hydrates. Only interactions between water and hydrocarbon gases and carbon dioxide were estimated. All other kij values were adopted from Reid et al. (1977). The estimated parameters appear in Table 7. The UNIQUAC interaction parameters used for the prediction of inhibitor effects are based on freezing point depression data. The parameters are shown in Table 8.

T IK) Fig. 3. Calculated coexistence curves for methane, hydrate and aqueous solutions of MEOH. Experimental data points: Roberts et al. (1940), Frost and Deaton (1946a), Ng and Robinson (1983), Holder (1976), Campbell and McLeod (1961), Ng and Robinson (1984a).

Computations

of the formation (1986)

of gas hydrates

2667

Table 8. UNIQUAC

parameters (aij) for interactions

between water and inhibitors to be used in the model of Sander et al.

Inhibitor*

MEOH a12
%I 431.0 -313.02

ETOH
196.5 -252.1

EG
- 129.7 -- 124.3 -

PG
439.9 186.7 -

DEG
41.46 195.3

TEG 258.4 - 273.5 solution -

Na+
1411.3 8 I 58.5

Ca2 +
-2912.6 -461.8 -. values

Cl-461.0 -437.5 NaCl=

For -407.7, *For

the interaction parameter CaCI, = -480.8. abbreviations see text.

(hi, ,) between

the salt ions

in aqueous

the following

are used:

5. IMPLEMENTATION 10 0

OF THE

MODEL

wt % EC

A computer program based on the model has been developed for the calculation of diagrams of the type shown in Figs 1 and 2. For gas mixtures the algorithms developed by Michelsen (1982) are used to check for stability of the mixture under consideration; this ensures correct prediction of the number of phases present. Furthermore, for situations corresponding to Fig. 2 the phase envelope is calculated according to Michelsens ( 1980) procedure. For mixtures containing heavy hydrocarbons (C7+) the method has been interfaced with the characterization procedure developed by Pedersen rt al. (1985). The program provides a simple but very useful and robust method for checking complex flow sheets for
the risk of hydrate formation. At any new set of conditions

266

270

274

278

T (K) Fig. 4. Calculated coexistence curves for propane, hydrate and aqueous solutions of EG. Experimental data points: Ng et al. (1982), Verma (1974), Wilcox et al. (1939).

questions
The are

the method can like the ones indicated

which (MEOH), are ethanol

important answer in Section I.

in the program

inhibitors

included

methanol

glycol

(EG),

propylene

glycol

(ETOH), (PC), di-

ethylene and tri-

200

0 -

,500

-E a 5 100.0 50.0 l /

0.0 270.0

I 275.0

I 280.0 285

I 0 290

I 0

I 295.0

I 300.0

T(K)

Fig. 5. Calculated coexistence curve for a seven-component mixture. ( l ) Experimental data points: Ng and Robinson (1984~). Mixture composition (mole %): N,=5.96, CO,= 14.18, Cl =71.61. C2=4.73. C3= 1.94, nC4 = 0.79. nC5 = 0.79.

2668

JAN MUI VCK

et

al.

ethylene glycol (DEG and TEG), and sodium calcium chlorides (NaCl and CaCl,).
6. RESULTS AND DISCUSSION

and

The calculated coexistence curves for hydrates of pure methane and pure propane are shown in Figs 3 and 4 which also show the influence of the addition of methanol or ethylene glycol as the inhibitor. The agreement between the experimental and calcu-

lated values is good even up to high concentrations of inhibitor in the aqueous phase. Point B-in Fig. 3 is a four-phase point with an equilibrium between ice (I), water (Ll), hydrate (H) and methane (G). Figures 5 and 6 represent multicomponent mixtures. In Fig. 6 the phase envelope is also given. This means that the experimental points in Fig. 6 correspond to the equilibrium between hydrate (H), aqueous solution (Ll) and liquid gas mixture (L2).

150.0

1200

90.0 -z z a 60.0

T(K)

Fig. 6. Calculated coexistence curve for a four-component mixture. (a) Experimental data points: Ng and Robinson (1976a). (-) Calculated phase envelope. Mixture composition (mole O/O): CO, = 25.5, C2= 17.0, C3 = 38.6, iC4 = 18.9.

50
200.0 l

35

Owt%MEOH

150.0

I t

E 4 e 100.0

50

0 I-

0.c ,2: 30

I
c 3
240

250

260

0 T(K)

270.0

280.0

290

300

Fig. 7. Calculated coexistence curves for a seven-component mixture and aqueous solutions of MEOH. (0) Experimental data points: Ng and Robinson (1984b). (. -) Phase envelope. Mixture composition (mole %): N,=5.26, CO,=13.37, Cl =73.90, C2=3.85, C3=2.02, &4=0.X0, &5=0.X0.

Computations

of the formation of gas hydrates

2669

Figure 7 shows the results for a seven-component mixture. The addition of methanol is seen to lower the decomposition temperatures in a given pressure range so much that one enters into the phase envelope and thereby a four-phase region (H, G, Ll and L2). The agreement between the calculated and experimental values is good even at a very high methanol concentration. Figure 8 shows the effect of using CaCl, as inhibitor for the formation of hydrate from a natural gas mixture. No experimental data could be found for comparisons. Figures 9 and 10 show experimental and calculated

results for the conditions where hydrates are formed from two North Sea reservoir fluids. The molar composition of the two mixtures are given in Table 9. AIso shown in Fig. 9 are results where the hydrate formation has been inhibited by addition of EG. In Fig. 10 are shown similar results where MEOH is used as inhibitor. It is seen that the experimental and the calculated results agree very well. Table 10 and Figs 11 and 12 show experimental and calculated vaiues of the water content in hydrocarbons can which are in equilibrium in a hydrocarbon with hydrate. content This which water content represents the maximum

be accepted

or hydrocarbon

700.0

20

10

0wt%CaC12

600.0

500.0 F 5 a

400.0

300.0

200.0

100.0

0.0 240.0

250.0

260.0

270.0 T(K)

280.0

290.0

300.0

Fig. 8. Calculated coexistence curves for natural gas, hydrate and aqueous solutions of CaCI,. (0) Experimental data points: Campbell and McLeod (1961). Mixture composition (mole %): Cl =90.6, C2=6.6, C3=1.8, ic4=0.5, nC4=0.5.

3000

20

0 wt

% EG

Fig. 9. Calculated coexistence curves for a North Sea oil in the presence of aqueous solutions of EG: (a) experimental hydrate point, (0) experimental bubble point, (-) calculated hydrate curve, (- . -) calculated bubble point curve. Experimental data points: Ng et al. (1987). CES
43:10-H

2670
300.0 -

JAN MUNCK er al.

29 16 Owt%MEOH

250.0

200.0

260 0

270 0

280 0 T(K)

290 0

I 300 0

Fig. 10. Calculated coexistence curves for a North Sea gas condensate in the presence of aqueous solutions of MEOH: (0) experimental data point, ( -) calculated hydrate curves. Experimental data points: Ng et ul. (I 987).

0.0
240 0

1
250.0
260

I
0 T(K)

I
270 0

I
290.0

Fig. 11. Water

content [x,,. (mole fraction)] in liquid propane in equilibrium with hydrate at 7.62 atm: (0) experimental data from Sloan er ul. (1986). (-) predicted water content.

Table 9. Compositions of the North Sea reservoir fluids for which hydrate results are shown in Figs 9
and Component N, CO, Cl c2 c3 ic4 10 [Ng et ul. (1987)] Mixture 0.16 2.10 26.19 8.27 7.50 1.83 4.05 1.85 2.45 45.60 90.2 A Mixture 0.64 3.11 73.03 8.04 4.28 0.73 1.50 0.54 0.60 7.53 32.4 B

mixture seen that calculated noticed pressure

without there and that and

a possible is a good

hydrate agreement

formation. between It should

It

is be

the both while

the experimentak

results.

for these two-phase calculations temperature have to be specified,

only pressure or temperature calculation of the three-phase Figs l-10.

can be specified for the coexistence curves in

nC4
iC.5 PIGS C6+ Molecular weight

7.

CONCLUSlON the formation The data calculations have been where of gas hyare compare estimated

A method drates well possible with

for

predicting developed.

has been since

experimental the

comparisons

parameters

Computations Table

of the formation

of gas hydrates in equilibrium with hydrate

267 1

10. Water content of liquid hydrocarbon at 34.05 atm

Hydrocarbon composition (mole %) Ethane Propane Ethane Propane Ethane Propane Methane Ethane Propane Pentane Sloan 10.2 89.8 64.6 35.4 91.5 8.5 10.1 4.4 26.1 59.4 et al. (1986).

Water Temperature (K) 247.75 273.45 263.45 276.15 263.95 274.95 264.05 270.65

concentration (mole %) Predicted 0.0084 0.0127 0.0054 0.0140 0.0053 0.0121 0.0054 0.0090

Experimental 0.0095 0.0137 0.0064 0.0161 0.0057 0.0 134 0.0056 0.0 124

450.0 l 400.0 c 350.0 300.0

P = 34.01

atm

T(K) Fig. 12. Water content [x, (mole fraction)] in a gaseous mixture of methane (mole fraction 0.0531) and propane (mole fraction 0.9469) in equilibrium with hydrate at various pressures (P) and temperatures (T): (e, A, tl, 0) experimental data from Song and Kobayashi (1982), (- -) predicted water content. from a very large data for gas base. The method with combines well-known

existing

models

hydrates

liquid models like UNIQUAC and the SRK equation of state. The procedure is robust and the checks for phase stability are based on the algorithms developed by Michelsen (1982). This means that no a priori information about the actual phases has to be provided. Acknowledgements-The authors are pleased to thank K. S. Pedersen and F. Fogh for fruitful discussions and for help in the computations. The support of Teknologiradet, Denmark, is gratefully acknowledged.
NOTATION A B

.r

AC,

heat

capacity

difference

fugacity

AH NCAV NCOMP
V AV

Y Y p
V

enthalpy difference number of cavities number of components molar volume of water (ice or liquid) volume difference mole fraction in aqueous phase probability of a filled cavity activity coefficient chemical potential number of cavities

Subscripts i

a, b
C

Langmuir constants [es. (L4)1 Langmuir

parameters in vapor pressure

adsorption constant

expression

K
0 W

type of cavity component at reference temperature water

273.15

2672

JAN

MVNCK

et al.
Ng, H.-J. and Robinson, D. B., 1983, GPA Research Report RR-66. Ng, H.-J. and Robinson, D. B., 1984a, CPA Research Report, RR-74. Ng, H.-J. and Robinson, D. B., 1984b, The influence of Methanol on Hydrate Formation at Low Temperatures. GPA Research Report, RR-74. Ng: H.-J. and Robinson, D. B., 1984c, AIChE National Meeting Atlanta, GA, 1 l-14 March. Ng, H.-J., Robinson, D. B. and Chen C.-J., 1982, Hydrate forming conditions in the presence of methanol and ethylene glycol. Paper prepared for the 32nd Annual Meeting of the Canadian Society of Chemical Engineering, 15 July. Noaker, L. J. and Katz, D. L., 1954, Trans. AIME 201, 235. Parrish, W. R. and Prausnitz, J. M., 1972, Ind. Engng Chem. Process Des. Dev. 11, 26. Pedersen, K. S., Thomassen, P. and Fredenslund, Aa., 1985, Ind. Engng Chem. Process Des. Dev. 24, 948. Reid, R. C., Prausnitz, J. M. and Sherwood, T. K., 1977, The Properties oJGases and Liquids. McGraw-Hill, New York. Roberts, 0. L., Brownncombe, E. R. and Howe, L. S., 1940, Oil Gas J. 37. Robinson, D. B. and Hutton. J. M., 1967, J. Can. Petrol. Technol. 6. Robinson, D. B. and Metha, B. R., 1971, J. Can. Petrol. Technol. 32. Roudher, 0. S. and Barduhn, A. J. 1969, Desalination 6, 25. Sander, B., Fredenslund Aa. and Rasmussen, P., 1986, Chem. Engng Sci. 41, 1171. Schroeter, J. P., Kobayashi, R. and Hildebrand, M. A., 1983, Ind. Engng Chem. Fundam. 22, 361. Selleck. F. T., Carmichael, L. T. and Sage, B. H., 1952, Ind. Engng Chem. 44, 2219. Sloan. E. D.. Bourrie. M. S.. Snarks. K. A. and Johnson. J. J.. 1986, Fluid Phase Equilihrib 29. 233. Soave, G., 1972, Chrm. Enqng Sci. 27, 1197. Song, K. Y. and Kobayashi, R., 1982, Ind. Enyng Chem. Fundam. 21, 391. Unruh, C. H. and Katz, D. L., 1949, Perroi. Trans. AIME 186, 183. van Cleef, A. and Dicpcn, G. A. M., 1960, Reel Trav. chim. 79, 582. van der Waals, J. H. and Platteeuw, J. C.. 1959, Adu. them. Phys. 2, 1. Weber, W., 1984, Ph.D. thesis, Technical University of Berlin. Verma, V. J., 1974, Ph.D. thesis, University of Michigan, Ann Arbor, Ml. Wilcox, W. L., Carson, D. B. and Katz, D. L., 1939, Ind. Engng Chem. 33, 662. Wilcox, W. L., Carson, D. 8. and Katz, D. L., 1941, Trans. AIME Technical Publication No. 1371. Wilhelm, E. and Battino, R., 1973, Chem. Rev. 73, 1. Wilhelm, E., Battino, R. and Wilcock, R. J., 1977, Chem. Rev. 77, 219. Wu, B. J., Robinson, D. B. and Ng. H.-J., 1976, J. them. Thermodyn. 8, 461.

Superscripts
H 0 c( P hydrate ice or liquid non-hydrate water phase

empty

Iattice

REFERENCES

Abrams, D. S. and Prausnitz, J. M., 1975. A.1.Ch.E. J. 21, 116. Anderson, F. E. and Prausnitz, J. M., 1986, A.1.Ch.E. J. 32, 1329. Berecz, E. and Balla-Achs, M., 1983, Gas Hydrates. Elsevier, Amsterdam. Camnbell. J. M. and McLeod. H. 0.. 1961, Trans. AIME 222, 596. Deaton, W. M. and Frost, E. M., 1937, Oil Gas .l. 36, 75. Deaton, W. M. and Frost, E. M., 1938, Gas 14, 31. Deaton, W. M. and, Frost, E. M., 1940a. Gas 16, 28. Deaton, W. M. and Frost, E. M., 1940b, Proc. natn Gas Dep. AGA 122. Deaton. W. M. and Frost. E. M.. i946, U.S. Bureau of Mines Monograph 8. Erickson. D. D.. 1983. Development of a natural gas hydrate predicrion computer program. M.Sc. thesis, Colorado School of Mines. Frost, E. M. and Deaton, W. M., 1946a. Oil Gus J. 170. Frost, E. M. and Deaton, W. M., 1946b. Proc. natn Gas Dep. AGA 49. Handbook of Chemistry and Physics, 1981-1982, 62nd Edition. Chemical Rubber Publishing, OH. Holder, G. D., 1976, Ph.D. thesis, University of Michigan, Ann Arbor, MI. Holder, G. D. and Godbole, S. P., 1982, A.I.Ch.E. J. 28, 930. Holder, G. D., Corbin, G. and Papadopoulos, K. D., 1980, Ind. Engng Chem. Fundam. 19, 282. Holder, G. D. and Hand, J. H.. 1982, A.1.Ch.E. J. 28, 440. Jhaveri, J. and Robinson, D. B., 1965, Can. J. them. Engng 43, 75. John, V. T., Papadopoulos, K. D. and Holder, G. D., 1985, A.1.Ch.E. J. 31, 252. Marshall, D. R., Sainto, S. and Kobayashi, R., 1964, A.1.Ch.E. J. 10, 202. Michelsen. M. L.. 1980. Fluid Phase Equilibria 4, 1. Michelsen, M. L., 1982, Fluid Phase E&ilihria 9, 1. Ne. H.-J.. Chen. C.-J. and Sieterstad T., 1987, Hydrate ?ormation and inhibition in gas condensate and hydrocarbon liquid systems. AIChE Meeting, Houston, TX, 1 April. Ng, H.-J., Petrunia, J. P. and Robinson, D. B., 1977-1978, Fluid Phase Equilibria 1, 283. Ng, H.-J. and Robinson, D. B., 1976a. Ind. Engng Chem. Fundam. 15, 293. Ng, H.-J. and Robinson, D. B., 1976b, A.1.Ch.E. J. 22, 656.