- , ,..

-:--- -- - - -- -- ---
TECHNOLOGY

Methodpredictshydrates
for high-pressure
gasstreams
Mahmood Moshfeghian Bushier University Iran
R.N. Maddox Consultant Stillwater, Okla.

new procedure extends
A the pressure range for
estimating hydrate for-
mation in high-pressure gas
wells such as those now be-
ing developed in the North
Sea.
The method applies for
uninhibited as well as meth-
anol and ethylene glycol in-
hibited hydrate-forming
conditions of pure compo-
nents and natural gas mix-
tures.
Accurate information con-
cerning the conditions under
which hydrates will form or
exist in a natural gas stream
are vital to the natural gas
industry. As pressure-tem-
perature conditions used for
transporting natural gas be-
come more severe, predict-
ing hydrate forming condi-
tions becomes increasingly
difficult. Addition of a hy-
drate inhibitor, such as
methanol or ethylene glycol,
further complicates reliable
prediction of hydrate-form-
ing conditions.
Fig. 1
Hydrate'ormation addition of a second materi-
The first generalized tech-
nique for predicting hydrate
al.
Over the years, many dif-
formation was presented in ferent procedures have been
1945.1 Vapor-solid equilibri-. presented for estimating hy-
urn constants were used in a drate-forming conditions
dew point-type calculation with and without inhibitors.
Also, much more has been
to estimate hydrate-forminq
conditions. An equation learned about the nature
provided an estimation of and composition of hy-
the concentration of inhibi- drates.
tor required to prevent hy- One of the most recent
drate formation. This equa- techniques3 for calculating
tion was similar to that for hydrate-forming conditions
estimating the freezing point used the basic approach of
lowering of a component by Reference 4, but obtained £0-
Table 1

HYDRATESTRUCTURE
ANDNUMBERFOR
Structure I Structure" NATURALGASCONSTITUENTS
Hydrate Calculated
Gas
N2
-structure
I
hydrate number
6.1
C02 I 6.5
H2S I 6.3
CH4 I 6.3
C2He I 8.0
C3He II 17.1
i-C4H,o II 17.1

14-Hedron 16-Hedron
(Tetrakaidecahedron) (Hexakaidecahedron) EQUATIONSANDNOMENCLATURE

Fig.2 AH -2,063
nR = IX + ~Px10-3 + /)xln P (1)
-AH 1 1
In (X H20'Y H20) = ( )
IiR T-r;; (2)

In ('Y H20) = (1-X H20)2 [B+2X ~o (A-B)) (3)

7 Nomenclature
Q;
.J:J
A. = Angstrom (10-10 m)
E A,B Constants in Margules equation
::> AH Heat of formation of hydrate, energy units/mole
c n
Q) Molecules of water per molecule of hydrate
OJ P Absolute pressure, aim
-0 R Gas constant, energy units
>.
J: ------ T Hydrate temperature in the presence of inhibitor, K.
Methane To Hydrate temperature in absence of inhibitor, K.
5.75 ~o Mole fraction of water in liquid phase
Greek Letters
5 IX,~, /) Coefficients in pressure dependency of heat of forma-
2,000 . 5,000 10,000 20,000 50,000 tion equation
Pressure, psia 'YH20 Activity coefficient of water

78 Oil & GasJournale Aug. 30, 1993

 -- ------ ----
TECHNOLOGY

Fig. 3 Fig. 4

1.2

i:.. 8
100.F II I
1.1

7S.F I I Ie<I>
Gi 'u
0u
6
50. F. I I I:;0 1.0
: (,)
u.. 25. F. I I I.>
4 't;0.9
lU O.F. <1J
:: -25. F. (;;
<U
.50. F.
2 .75. F. 0.8
-100.F.

0 0.7
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

.
Activitycoefficient
Methanol concentration, wt
OGJ .Activity coetficient
Ethylene glycol conc~ntration, wt
OGJ

gacities from Reference 5 od is an extension of the

equation of state) and heats from Reference 6.
(the Soave-Redlich-Kwong I
procedure from Reference 3
of formation for hydrates The suggested new meth-
that includes the influence
Table 2 of pressure on the enthalpy
change accompanying hy-
frURE COMPONENT
HYDRATETEMPERATURES GLYCOLPRESENT drate formation.
WITH ETHYLENE
Point Glycol, Pressure, Hydratetemperature,.F Modeldevelopment
number wt% psla Experimental Calculated Error
Hydrates are clathrates, a
Ethane
1.0 25.0 35.4 11.8 -10.4 -22.4 form of inclusion compound
2.0 25.0 73.7 20.4 20.1 -0.3 in which "guest" molecules
3.0 25.0 169.7 31.6 32.3 0.7 fit into cavities in a crystal-
4.0 50.0 34.8 -13.6 -36.5 -22.9
5.0 50.0 62.1 -5.7 -12.4 -6.7 line lattice formed by the
6.0 50.0 102.0 1.1 -0.3 -1.4 "host" molecules, but with-
Average absolute error 9.1 out chemical bonding. Hy-
Propane drates may take on two dif-
1.0 50.0 19.5 -18.2 -14.4 3.8 ferent structural forms/
2.0 50.0 29.7 -12.3 -5.2 7.1
3.0 50.0 122.0 -12.0 -3.4 6.5 each of which is composed
Average absolute error 5.8 of polyhedral cages and each
Carbon dioxide
of which has two different
1.0 50.0 67.9 -25.5 -42.8 -17.3 sized holes to accept guest
2.0 50.0 114.8 -16.7 -20.2 -3.5 molecules.
3.0 50.0 172.0 -9.9 -3.4 6.5
Average absolute error 9.1 Fig. 1 shows the tetrakai-
decahedron of Structure I
Hydrogen sulfide and the hexakaidecahedron
1.0 25.0 16.0 20.8 21.2 0.4
2.0 25.0 43.3 40.1 39.1 -1.0 of Structure II hydrates. The
3.0 25.0 92.6 50.2 52.6 2.4
4.0 50.0 14.9 -6.7 -7.3 -0.6 open circles represent the
5.0 50.0 16.5 -2.8 -5.4 -2.6 oxygen atoms in the water
6.0 50.0 40.0 13.0 11.2 -1.8 molecules, and the solid
Average absolute error 1.5
lines represent the hydrogen
bonds between them.
Table 3 With those two different
structures and with different
I DATA SOURCES
FORGASMIXTURES sized and shaped guest mol-
ecules, there is also the pos-
Component Gas 1 Gas 2 Gas 3 Gas 4 Gas 5 Gas 6
sibility of a mixed hydrate.
Nitrogen 7.00 5.96 In their body centered cu-
Carbon dioxide 14.19 3.00
Methane 84.13 71.60 93.51 89.99 74.13 84.50 bic cell, Structure I hydrates
Ethane 4.67 4.73 4.58 6.31 7.21 8.70 have 46 water molecules and
Propane 2.34 1.94 1.31 2.40 4.50 3.80
i.Butane 0.10 0.30 0.90 six large (about 5.6 A. mean
n.Butane 0.93 0.79 0.20 0.50 1.81 diameter) and two small
i.Pentane 0.10 0.10 0.87 (about 5.1 A. mean diame-
n.Pentane 0.93 0.79 0.10 0.10 0.89
n-Hexane 0.10 0.30 9.69 ter) holes for accepting guest
Reference 14 14 15 15 10 11 molecules.
I
Structure II hydrates have

Aug.30, 1993. Oil& GasJournal 79

 - -- - - - -- --- - -
TECHNOLOGY

Table4 I . The hydrate fonnation

temperature is then calculat-
HYDRATEFORMATIONTEMPERATURE
fOR METHANEAT HIGHPRESSURE ed by Equation 2.
. As suggested in Refer-
Piessure, Pure water, "C. 20% methanol, .C. ence 3, the activity coeffi-
MPa Measured Calculated Difference Measured Calculated Difference
cient can be obtained from
4.2 4.7 -5.5 -10.2
5.0 6.5 . 7.2 0.7 the Margules equation
16.8 5.5 5.6 0.1 (Equation 3).
18.0 18.3 18.2 -0.1 The constants in the Mar-
24.0 9.0 8.2 -0.8
25.5 20.7 20.8 0.1 gules equation are obtained
35.0 23.6 23.2 -0.4 from regression of the calcu-
35.9 12.1 11.2 -0.9
36.1 23.1 23.4 0.3 lated activity coefficients for
40.5 24.1 24.3 0.2 the individual inhibitors.
43.2 24.7 24.8 0.1
50.5 13.8 14.0 0.2 Fig. 3 shows the activity
54.0 26.4 26.6 0.2 coefficient for water in meth-
57.0 15.3 15.1 -0.2 anol for concentrations to
57.6 15.9 15.3 -0.6
62.0 15.9 16.0 0.1 90% by weight methanol
62.5 28.2 27.8 -0.4 15.8 16.0 0.2 and temperatures from
65.0 28.4 28.2 -0.3
75.7 18.2 18.0 -0.2 -100 to + 1000 F. Fig. 4
76.5 30.2 29.6 -0.6 shows the activity coefficient
92.0 32.0 31.3 -0.7
92.5 20.9 20.3 -0.6 for water in ethylene glycol
96.2 21.3 20.7 -0.6 for various glycol concentra-
100.0 22.0 21.2 -0.8
Average absolute error 0.3 1.2 tions to 65% by weight gly-
col and at temperatures from
-100 to + 1000 F.
Table 5 The water activity coeffi-
cient inhibitor concentration
GAS MIXTUREHYDRATETEMPERATURE
WITH METHANOLPRESENT' curves cover the full range of
available experimental data
ExPerImental temperature, "C. for inhibited hydrate fonna-
Pressure, Methanol content, wt, % Calculated temperature, "C.
MPa 0 20 40 Aqua 81M Process New mathod tion. Extrapolation beyond
11.2 19.5 21.1 20.9 19.8 the plotted lines in Figs. 3
33.7 25.4 26.7 26.5 25.3 and 4 is not recommended.
37.0 16.2 16.4 15.3 13.6
41.7 26.6 26.1 27.7 26.7 Proof
42.0 26.6 28.1 26.7
45.2 16.2 17.6 15.1 For the new model, the
49.7 17.5 18.6 15.9 basic calculation uses enthal-
50.9 28.6 29.6 28.2
56.4 17.2 19.7 17.0 pies of fonnation and water
60.0 19.9 20.2 17.6
66.0 7.8 7.8 activity coefficients correlat-
66.5 30.4 32.0 30.4 ed with the Margules equa-
66.0 30.9 30.6 tion.6 The calculations were
72.5 21.2 19.6
73.0 32.1 31.2 established and proven in
75.8 10.0 9.8 Reference 3.
76.2 31.8 31.6
78.0 10.5 10.2 When tested against the
79.4 22.5 20.6 data available in Reference 3
84.2 12.0 11.5
65.3 33.0 32.8 and compared with available
85.3 24.2 21.5 methods, the new method
87.9 33.9 33.1
92.9 34.0 33.7 provides for significantly im-
92.9 24.8 22.6 proved hydrate formation
99.6 35.0 34.4 temperature predictions
Average absolute error 1.2 1.1 0.8
over a wide range of pure
components, mixtures, tem-
a diamond lattice composed forming constituents of nat- retical value. peratures, pressures, and in-
of 136 water molecules. ural gas.7 If the number of gas mole- hibitor concentrations. Be-
There are eight large cavities The hydrate number is de- cules in the hydrate varies cause of the extensive evalu-
(about 6.7 A. mean diame- fined as the number of with pressure, the enthalpy ation of the method in Refer-
ter) and 16 small cavities moles of water per mole of of fonnation for the hydrate ence 3, only a brief summary
(about 5.0 A. mean diame- gas in the hydrate. The "ide- should also change as pres- of the results of the most
ter). al" or theoretical hydrate sure changes. The technique important of those volumi-
The crystal structure of number is 5.75 (46/8 = 5.75) suggested by in Reference 6 nous calculations will be dis-
the gas hydrate will depend for Structure I and 5.67 for for predicting hydrate for- cussed.
on the geometry of the guest Structure II. mation in presence of an in- Table 2 compares calculat-
gas molecule. Small gas mol- As shown in Fig. 2,89 hibitor can be modified as ed hydrate temperatures
ecules generally cause Struc- these ratios are achieved follows: from the new model with
ture I hydrates while large only at very high pressure. . Include a pressure de- experimental measurements
gas molecules generally At lower pressures, not all pendency in the equation for for ethane, propane, carbon
cause Structure II hydrates. available holes. are filled, the enthalpy of fonnation, dioxide, and hydrogen sul-
Table 1 shows hydrate and the hydrate number is Equation 1 (see equation and fide.1o For the most part, cal-
structures for most hydrate- larger than the ideal or thee- nomenclature box). culated and experimental
80 Oil & GasJoumale Aug. 30, 1993
 ----
r TECHNOLOGY
120
100
'"
a. 80
::i
oi
:;
'"
'" 60
CD
Q:
40
20'
I Bushier Universityin Iran. He previouslywas a professorin the
01
-10 o 10
Hydrate formationtemperature, ac.
measurements are in good
agreement.
Data for several natural
gas mixtures were used in
evaluating the new proce-
dure for calculating hydrate-
formation temperature. Ta-
ble 3 lists the compositions
of the different mixtures and
the sources for the gas mix-
ture data.
Because inhibited hydrate
data are difficult to measure,
a comparison of calculated
hydrate-forming tempera-
tures for gas mixtures with
methanol present in varying
concentrations showed that
the overall average error of
2.80 F. for the 60 data points
is within experimental error.
For Gas Mixture 5, all of
the data were in excellent
agreement whether uninhib-
ited or inhibited by metha-
nol or glycol. The overall er-
ror was 2.50 F.
Recently, Reference 11
presented very high-pres-
sure hydrate formation tem-
perature data for pure meth-
ane and also for a synthe-
sized gas mixture. The refer-
ence graphically showed
that the uninhibited meth-
ane hydrate formation tem-
perature data were in excel-
lent agreement with previ-
ously reported lower pres-
sure results in References 8,
9, 12, and 13.
Fig. 5 and Table 4 show
that calculated and experi-
mental temperatures for un-
inhibited methane are in ex-
Aug. 30. 1993. Oil & Gas Journal
20% Me OH
20 30 40
OGJ
cellent agreement. The unin-
hibited hydrate formation
data agree within an average
overall error of 0.340 C.
The calculated methanol
inhibited methane points are
also in excellent agreement
with experimental determi-
nations. The methanol in-
hibited data agree within
1.190 C., including all
points. For all but the lowest
pressure point, the average
temperature error for the
methanol inhibited points is
0.440 C.
There appears to be a pos-
sible typographical error in
the temperature reported for
the lowest pressure point. If
the minus was accidentally
.omitted and the correct tem-
perature is -4.70 c., that
value is almost exactly equal
to the calculated tempera-
ture.
Table 5 compares calculat-
ed and measured values for
hydrate formation tempera-
ture of Gas Mixture 6 in the
presence of water and with
methanol inhibitor. It also
shows calculated results for
two other available comput-
er programs for estimating
hydrate-forming tempera-
ture.
One of the other programs
fails above about 40 MPa
(5,800 psi), and the second
cannot be applied above
about 60 MPa (8,700 psi).
Even within their range of
application, the superiority
of the proposed calculation
----- - - - - - ---
Moshfeghian Maddox
Mahmood Moshfeghian is dean of the school of engineering in
chemical engineering department of Shiraz University in Iran.
Moshfeghial! received BS, MS, alld PhD degrees in chemical engineer-
ing from Oklahoma State University. He is a member of the Iranian
Institute of Chemistry & Chemical Engineering, lranian Petroleum
Institute, and AlChE.
R.N. Maddox retired from Oklahoma State University in 1986, but
remains active in professional affairs and as a consultant. He taught
for 36 years at Oklahoma State University and served as the
department head of chemical engineering from 1958 to 1977. He has
written numerous articles and books on gas and oil production.
Maddox received a BS from the University of Arkallsos, an MS from
the University of Oklahoma, and a PhD from Oklahoma State
University. All the degrees were in chemical engineering.
procedure is clearly evident Kobayashi, R., "Hydrates at
from the data in Table 5. High Pressures, Part II," AIChE
Journal, Vol. to, 1964, p. 734.
References to. Ng, H.J., Chen, CJ., and Robin-
son, D.B., "The Effect of Ethyl-
1. Katz, D.L., "Prediction of Condi-
ene Glycol or Methanol on Hy-
tions for Hydrate Formation in drate Formation in Systems Con-
Natural Gases," Trans. AIME, taining Ethane, Propane, Carbon
Vol. 160, 1945, p. 140. Dioxide, Hydrogen Sulfide, or a
2. Hammerschmidt, E.G., "For- Typical Gas Condensate," Re-
mation of Gas Hydrates in Nat- search Report RR-92, Gas Proces-
ural Gas Transmission Lines," sors Association, Tulsa, 1985.
Ind. & Eng. Chern., Vol. 26, 11. Blanc, C, and Tournier-Las-
1934, p. 851 serve, J., "Controlling Hydrates
3. Maddox, R.N., Moshfeghian, In High-Pressure Flowlines,"
M., Lopez, E., Tu, CH., Shariat, World Oil, November 1990.
A., and Flynn, A.J., "Predicting
Hydrate Temperature at High In-
12. Mcleod, H.O. Jr., and Camp-
bell, J.M., "Natural Gas Hy-
hibitor Concentration," Laurance drates at Pressures to tO,OOO
Reid Gas Conditioning Confer- psia," JPT, Vol. 13, 1961, p. 590.
ence, Norman, Okla., March 13. Holder, G.D., Corbin, G., and
1991.
Papadopoulos, K.D., "Thermo-
4. Parrish, W.R., and Prausnitz,
J.M., "Dissociation Pressures of
dynamic and Molecular Proper-
ties of Gas Hydrates from Mix-
Gas Hydrates Formed by Gas tures Containing Methane, Ar-
Mixtures," Ind. Eng. Chern. gon and Krypton," Ind. Eng.
Proc. Des. Dev., Vol. 11, 1972, p. Chern. Fund., Vol. 19, 1980, p.
26. 282.
5. Soave, G., "Equilibrium Con- 14. Ng, H.J., and Robinson, D.B.,
stants from a modified Redlich-
"Equilibrium Phase Composition
Kwong equation of state," and Hydrating Conditions in
Chern. Engr. Sci., Vol. 27, 1972, Systems Containing Methanol,
p. 1197.
Light Hydrocarbons, Carbon Di-
6. Pieroen, A.P., Recueil Trav. oxide, and Hydrogen Sulfide,"
Chim, Vol. 74, 1955.
Research Report RR-66, Gas Pro-
7. Kuustraa, V.A., and Hammer- cessors Association, Tulsa, 1983.
shaimb, E.C, Handbook of Gas 15. Ng, H.J., Chen, CJ., and Robin-
Hydrate Propertiesand Occur-
son, D.B., "The Influence of
rence, National Technical Infor- High Concentrations of Metha-
mation Service, U.S. Department nol on Hydrate Formation and
of Commerce, 1983
8. Marshall, D., Saito, R.S., and Ko-
the Distribution of Glycol in liq-
uid-Liquid Mixtures," Research
bayashi, R., "Hydrates at High Report RR-106, Gas Processors
Pressures, Part I," AIChE Jour- Association, Tulsa, 1987.
nal, Vol. to, 1964, p. 734.
9. Marshall., D., Saito, R.S., and
81