17

Gas Hydrates

Hydrocarbon gas and liquid water combine to fonn solids resembling

wet snow at temperatures somewhat above the temperature at which
water solidifies. These solids are called gas hydrates. They are one of a
form of cornplexes known as clathrates. This phenomenon particularly
interests those in the petroleum industry because these solids can form at
temperatures and pressures normally encountered in producing and
transporting natural gases.
Gas Hydrate Formatlon
Gas hydrates behave as solutions of gases in crystalline solids rather
than as chemical compounds. The main framework of the hydrate crystal
is formed with water molecules. The hydrocarbon molecules occupy void
spaces within the lattice of water molecules.
Hydrate formation is physical rather than chemical in nature. Apparently, no strong chemical bonds are formed between the hydrocarbon and
water molecules. Actually, the hydrocarbon molecules are free to ro tate
within the void spaces.
Toe water framework seems ice-like because of comparable heats of
forrnation. However, the crystal lattice is somewhat different than ice
since an ice lattice provides no space for even the smallest hydrocarbon
molecule.
Two types of hydrate crystal lattices are known. Each contains void
spaces of two different sizes. One lattice has voids sized to accept small
molecules such as methane and larger molecules such as propane at a
ratio of about two small molecules to one large molecule. The other
lattice accepts methane molecules and medium-sized molecules--such as
ethane-at a ratio of about three mediums to one small.
Although gas hydrates appear to be solid solutions rather than
chemical compounds, a specific number of water molecules is associated
474

475

Gas Hydrates

,._

...

44-~"'5WR'~$~

......
t
~

"'-~

. ,_

: d~<>lt(ICfileC\

Q,

U\8!i

~#'~$#'$'.#.#

:,~
1

jl,ll,l,

7//#/$#////#n'#/#/#r.

ctfJtl,OIQS

I)

tt,CJ

Dl1CMt11

~-

(t,He.boC.l'flll

.,~
rr-at,dD!iC\

u,-"'4"'-

Fig. 17-1. Maximum length of molecule which forms gas hydrates and
the water-to-gas ratio in the hydrate crystal. Several molecules of the
same maximum dimension which do not form hydrates are also given.
(From Handbook of Natural Gas Engineering by Katz, et al. Copyright
1959 by McGraw-Hill Book Company. Used with permission of McGrawHill Book Company.)

with each gas molecule. This is dueto the framework of the crystal. The
ratio depends primarily on the size of the gas molecule.
Figure 17-1 shows a number of gases which form hydrates, along
with the maximum length of each molecule in angstrom units and the
approximate ratio of water molecules to gas molecules in the resulting
crystals.1 Not only the size of the gas molecule but also its isomeric
configuration control whether or not hydrate will form. For example, isobutane readily forros hydrate, but the longer n-butane molecule forros
hydrate only at temperatures slightly above the freezing point of water.
Yet, in the presence of other gases with smaller molecules, the n-butane
molecules readily enter the hydrate. This indicates that n-butane molecules occupy the larger voids in the crystal lattice once hydrate formation
begins.

Conditions For Gas Hydrate Formation

The most important consideration in hydrate formation is that liquid

water must be present for hydrate to form. Even with liquid water present
a metastable equilibrium can exist between water and gas at conditions of

PETROLEUM

476

FLUIDS

Hy

TiNnpefl;iture

Fig. 17-2. Hydrate portian of the phase diagram of a typical mixture of

water and a light hydrocarbon.
pressure and temperature for which hydrate forrnation could occur. But,
once seed crystals are formed, hydration occurs readily.
Seed crystals be gin to forrn at temperatures 3 to 1 OF lower than the
hydrate-forming temperatures discussed later in this chapter. 2 Or, at a
given temperature, seed crystals start forming at 300 or more psi above
hydrate-forming pressure. However, dust or rust particles may act like
seed crystals in initiating hydrate formation.
A portian of the phase diagram for a mixture of water and a light
hydrocarbon is given in Figure 17-2. The line Q2C separates the region
in which liquid water and hydrocarbon gas exist from the region in which
liquid water and hydrocarbon liquid exist. None of the phases is pure; ali
contain slight amounts of the other substance according to their mutual
solubility.
Line Q2C is parallel to and slightly above the vapor-pressure line for
the pure hydrocarbon. The dashed Iine to the left of point Q2 is simply an
extension of the vapor-pressure Iine of the hydrocarbon. Point C is the
three-phase critica! point at which the properties of the hydrocarbon gas
and liquid merge to form a single hydrocarbon phase in equilibrium with
liquid water.
The line Q1Q2 separates the area in which liquid water and hydrocarbon gas exist from the area in which liquid water and hydrate exist. This
line represents the conditions at which gas and liquid water combine to
form hydrate.

477

Gas Hydrates

Point Q2 is a quadruple point. At Q2, four phases are in equilibrium:

Iiquid water, hydrocarbon liquid, hydrocarbon gas, and solid hydrate.
Toe almost vertical line extending from point Q2 separates the area of
liquid water and hydrocarbon Iiquid from the area of liquid water and
hydrate.
Q1, which occurs at approximately 32F, is also a quadruple point
representing the point at which ice, hydrate, liquid water, and hydrocarbon gas exist in equilibrium. The vertical line extending from point Q1
separates the area far hydrate and liquid water from the area far hydrate
and ice.
The line of major interest on this phase diagram is the Iine Q1Q2,
which represents the equilibrium between hydrocarbon gas, liquid water,
and hydrate.

12,000
10,000
8000

,~

6000

,,,.

1/

_/

4000

-~
~w
.
,.
. -...-

2000

1/

1000
800

1/

i 600

1 :..,

:!-400

~ :...-

200

,;A

ftht?.n!
;

/"

..,,/,,.
,1 /

100

ao

'

Io

60

p,DiJO."'

--

40

10

20

et~

-- .). ff~l

.-- '"'r
/

..J

30

40

.50
60
Temptroturt d.!IJ ~

70

80

90

Fig. 17-3. Hydrate-forming conditions for paraffin hydrocarbons. (From

Handbook of Natural Gas Engineerngby Katz et al. Copyright 1959 by
McGraw:.Hm Book Company. Used with permission of McGraw-Hill Book
Cornpany.)

PETROLEUM

478

FLUIDS

Figure 17-3 shows the ~

lines for the five hydrate-forming
hydrocarbon constituents of natural gas.1 Portions of the vapor-pressure
lines of the hydrocarbons and parts of the vertical lines from Q1 and Q2
also are shown. Pressures and temperatures along the~
line for each
hydrocarbon indicate conditions for which hydrate formation occurs for
mixtures of that hydrocarbon with liquid water. Methane forms hydrate
at much higher temperatures than the larger hydrocarbons. However, the
pressure required for hydrate formation becomes significantly lower as
molecular size increases.
Figure 17-4 gives a comparison of the hydrate-formation lines of
methane and propane with the hydrate-formation lines for mixtures of
these two hydrocarbons. 3 Note that very small quantities of the larger
hydrocarbon in the mixtures cause large reductions in the pressures
required to initiate hydrate formation.
A mixture of 40% methane and 60% propane forms hydrate at
pressures nearly as low as pure propane, but hydrate forms at much
higher temperatures than for pure propane. Thus, mixtures of methane
and larger hydrocarbons retain the high hydrate-forming temperatures of
methane and approach the lower hydrate-forming pressures of the larger
molecules.
This fact is confirmed by the data given in Figure 17-5.1 This figure
shows the hydrate-forming conditions for several natural gases along
1500

1000
/

IOO

"

'lY

tp

:" V
V,p7 ./. /

'

..

.. ,,,

.. -

,r

,r

100

11 ~

#.~

,..__ 'o',-7,
~

lO

,o

"

"'

"'

"'

Fig. 17-4. Hydrate-formation conditions of methane-propane mixtures.

(Deaton and Frost, U.S. Bureau of Mines, Monograph 8, 1946, 20 ..
Courtesy, Bureau of Mines, U.S. Department of the Interior.)

479

Gas Hydrates

,,

10,000
8000

1/

6000

/e

4000
3000
0

;;

2000

c..

"'~

1000
~ 800
a.
600
400

100
30

, ,,v

300

200

V
I

;r

1/

~ ~

/J

/,1 V

{!

V
,

,,

~~~ 1/IJ V
~~

j ~

,,

//

Ir

/~

V/

~ ~
~ ~
40

50
60
70
Temperoture, deg F

80

90

Fig. 17-5. Hydrate-forming conditions for natural gases. Symbols A

through E represent gases of increasing specific gravity. (From Hendbook
of Natural Gas Engneering by Katz et al. Copyright 1959 by McGraw-Hill
Book Company. Used with permission of McGraw-Hill Book Company.}

with the hydrate-formation line for methane. Toe pressures at which

hydrate formation occurs are significantly lower for the natural gases
than for methane. The natural gases with higher specific gravities (that
is, gases with more of the heavier hydrocarbons) form hydrates at much
lower pressures than the lighter gases.
The data are incomplete at the higher temperatures, but apparently all
the gases form hydrates at temperatures somewhat above 70F.
Figure 17-6 was developed from the data of Figure 17-5.4 Figure
17-6 is a correlation of hydrate-forming conditions for natural gases
with various specific gravities, This figure can be used to estmate the
conditions under which hydrates will form. Toe resulting hydrate
formation conditions must be used with caution because there is a great
discrepancy between the limited published data and the correlation
shown in Figure 17-6. 5 Toe differences in hydrate-forming pressures

480

PETROLEUM FLUIDS

6000
4000
~ 3000

1/

1/)
(L

15 00

oc

10

IX

1.1...
iJJ

600

--

,,

'<a:

400

~7

///

/
/

iJJ

::::>
~

o: ~.

o:

!E

'/ji

///

///
'//
/

--

a: 2

//J

C7m'
i7
. t'h o/.
oc
5: ~# ////

,vg

/!$

,,, ,,, ,,,,"'

/

.,r)"

80 ~

6(
4

q;//W
/

~/

~/

//

tL-=

i-----

40

---~+~+.+

----

,___

1----------~--

.SO
60
70
TEMPEAATURE. f

1-------~

80

---

9'.)

Fig. 17-6. Hydrate-forming conditions for natural gases. (Katz, Trans.,

AIME, 160, 140. copyright 1945 SPE-AIME.)
between the available data and the correlation in Figure 17-6 range from
about 10% at the higher specific gravities to as much as 35% at the lower
specific gravities. 5 Given a value of pressure, the error in the estmate of
hydrate-forming temperature could be 5F or more.
Figure 17 -6 is for sweet gases. The presence of hydrogen sulfide and
carbon dioxide shifts the lines to the right. This results in an increase in
the hydrate temperature for a given pressure or a decrease in hydrate
pressure for a given temperature.
EXAMPLE 17-1: A O. 7 specific gravity natural gas is to be compressed
to 500 psia and cooled to 50F. Is there a possibility
of hydrate formation under these conditions?

Gas

Hydrates

481

Solution
Yes. Figure 17-6 indicates that a O. 7 specific gravity gas forms
hydrates at temperatures below 56F at a pressure of 500 psia if
liquid water is present.
lnhibitionof Gas Hydrate Formation

The presence of dissolved solids in the water reduces the temperatures

at which natural gases forro hydrates. Figure 17-7 gives values to reduce
the temperatures estimated from Figure 17-6 to account for the effect of
dissolved solids in the water. 1
The water which condenses from natural gas at surface conditions is
pure water. Often an inhibitor is added to this water to lower the hydrate-

20

/ '/

18

'!
lj

16

/ '!

...
o

~14

//

f /

JI/
/ J
~~1!::;

,,

1/

1//

,,

...
'

!} <t
/

/,'/

V/
01~ V

Fig. 17-7. Oepression of hydrate-formation temperaturas by inhibitors.

(From Handbook of Natural Gas Engineering by Katz et al. Copyright
1 !159 by McGraw-Hill Book Company. Used with permission .ot McGrawHiI Book Company.)

482

PETROLEUM

FLUIDS

2s,,........--.---------,,-----,----,.--,

,:. aol----!--------,1-+----l-----+----4

!i
~

'r+++:ri

:;1s1----1-----

!!

;
.!!

~--+---

tal-----+

',':---+------<

a sl--~,_____!---~~!-----1----+-----,

10

20

30

lnhlbltor conc-enlHUoaI Uquld.

40
wt '%

Fig. 17-8. Depression of hydrate-formation temperatures with methanol

and diethylene glycol. (Data from USBM Mono. 8, 32 and Scauzillo,
Chem. Eng. Prog. 52, 324.)

forming temperature. The effectiveness of two inhibitors is shown in

Figure 17-8. Methanol is obviously the better inhibitor, but diethylene
glycol, HO(C2H40)2H, often is used because the volatility of methanol
causes high methanol loss to the gas.
EXAMPLE 17-2: The liquid water in contact with the gas of Example
17-1 contains 35% by weight diethylene glycol. Will
hydrate form?
Solution
Probably not. The diethylene glycol reduces the hydrate-forming
temperature by about 12F to about 44"F. See Figure 17-8.
The presence of liquid hydrocarbons with a hydrocarbon gas also
lowers hydrate-forming temperatures.2 Figure 17-9 indicates this depression in hydrate-forming temperatures. The figure represents a gas
with specific gravity less than 0.6 and is probably not sufficiently

483

Gas Hydrates

Gas-oil ratio, scf/STB

Fig. 17-9. Effects of the presence of liquid hydrocarbons on hydrateforming temperaturas. (Adapted from Scauzillo, Chem. Eng. Prog. 52,
1956, 324.)
accurate for use as a general correlation. However, it does give an
indication of the inhibiting effect of the presence of hydrocarbon liquid.
Gas Hydrate Formation Caused by Reduction of Pressure

Reducing pressure at normal surface conditions, such as across a

choke, causes a reduction in the temperature of the gas. This temperature
reduction could cause the condensation of water vapor from the gas. lt
also could bring the mixture of gas and liquid water to the conditions
necessary for hydrate formation.
The temperature reductions accompanying pressure reductions have
been calculated for typical natural gases. These results combined with
the hydrate-formation conditions given in Figure 17-6 provide calculation charts giving the maximum reduction in pressure to which a natural
gas can be subjected prior to the onset of hydrate formation. 4 Figures
17 -1 O through 17-14 give these calculation charts for natural gases of
various specific gravities. Their use is relatively simple.
The charts are entered at the intersection of the initial pressure and the
initial temperature. The lowest pressure to which the gas can be
expanded without danger of hydrate formation is obtained from the
abscissa directly below this intersection.

PEfROLEUM FLUIDS

484

The intersection of the final pressure with the dashed line gives the
temperature to be expected after expansion to that pressure. The accuracy
of these charts is limited by the accuracy of Figure 17-6.

EXAMPLE 17-3: The pressure and temperature on a 0.7 specific

gravity natural gas are 3,000 psia and ]60F. To
what pressure can this gas be expanded without
danger of hydrate formation and to what temperature will the gas be cooled as a result of the
expansion?

0,000

trs

I'\

fn,tl(J/ flfJlplrOfllf't, ~

r''/

1/

'

\.

\ \
\

I
160

JJ

...-."
-~ __. ..... ,{// / 1/J/
__ ....
//1
~ / //
- L,..- ~jlJt.- __ ....
- -~ !}-

4000

~--

_..i..,

l.,,~

l.,

2000

c.-

,f/9....

l.--#2-

c.fl-' _..
JE

..-

_E!--

s- i7

400

l,()()

l.,,

,.,.
....__. .....

l.,,~

'i V

>

,,..,, //

'

,:<r

/
/

j2,''
/

//
/

13()

.,/

100

150

200

l,()()

400
600 800 1000
F"nl l)rtnare, psia

1500 2000

3000 4000

Fig. 17-10. Permissible expansion of 0.6 specific gravity gas without

hydrate formation. (Katz, Trans., AIME, 160, 140. Copyright 1945 SPEAIME.)

485

Gas Hydrates

10

"

r-;

000

<,

,aJ,

<,

6000
5000 fnltfo/ ffmperot11re

f~

\~

11iY

t>

300o

20

,J /

L.----;~

90

000

--
70

EOO

__,.,.

50~ _......- /

400

soo.___

~50

200

1/

./

500

//

' \ ' 1\.

\

1/

1,

"1/

L,
L.-

L.- L.,.,L,

--

L..::L.- ..,i.-

') J i/ /1 J /, 1,/
'// 1// 1// /
vhV/ ;,>

0 V
~

1, /

~'~
~bP.
,10

---~J9!!V

-r,
--IT1!
'-1;0

500

150

'

'\
'\

'

1,

-- ,_

,/

....!2... 1:,/

Jy /

100'

100

150

200

300

4100
600 800 1000
finol prtss.rt, ~o

1500 2000

3000 4DOD

Fig. 17-11. Permissible expansion of O. 7 specific gravity gas without

hydrate formation. (Katz, Trans., AIME, 160, 140. Copyright 1945 SPEAJME.)

Solution
Enter the ordinate of Figure 17 ~ 11 with an initial pressure of 3000
psia, Move horizontally to the 160F isotherm. Move vertically to
the abscissa, 580 psia, which is the lowest final pressure precluding
hydrate formation. The intersection of a final pressure of 580 psia
with the dashed line gives 59F, which is the temperature after
expansion to 580 psia.
Exercises

17-1. Methane and Iiquid water are in contact at

Do you expect hydrate to form? Explain
answer.
17-2. Suppose the gas of Exercise 17-1 contains
Do you expect hydrate to form? Explain
answer.

4000 psia and 60F.

the reason for your
10 mole% propane.
the reason for your

PETROLEUM FLUIDS

486

eooo

.......
-...,

v ~

.__

_l!!!-

ir

. Y/

--

tsO

2000
IS

600

'500

_.........

so

..

200
/

IOO /
KJO

/'

//
V //

--

~--

V// V/

./,

;..,
./

V/
/

1./

,.., ~
(.

//
1

'

1
;
1

300

Vi

v"

200

o/
/
ISO

I JI 1/ J /

/..,

V /

.......... 'j/

...-- .,,....,..

......... V //

9Q

'//// /

ft-

----1

/,f

10 __., --

4--

t::: ........ t;:r,

_J!9..

e--

JJ.2-,JO ........

l<IOD

\ \

'

1)

160---

o11'l!7 /

soeo l::.....J4.1',,,1t11~tore~ ~

lOOO

_\

cOO

IOOO

" "'

... "'

400

600

r--

800

fitw:lli,rn"Wt"1t1 psio

1
1

t000

1SOO

X>OO

3000

Fig. 17-12. Permissible expansion of o.a specific gravity gas without

hydrate formation. (Katz, Trans., AIME, 160, 140. Copyright 1945 SPEAIME.)

17- 3. Suppose the liquid water of Exercise 17-1 contains 20 wt %

solids. Will hydrate form? Explain the reason for your answer.
17-4. Methane and liquid water are in contact at 1500 psia and 60F.
Do you expect hydrate to form? Explain the reason for your
answer.
17-5. Suppose the methane of Exercise 17-4 contains 5 mole %
propane. Will hydrate form? Explain the reason for your answer.
17-6. A 0.7 specific gravity gas is handled in a gas gathering system.
Sorne liquid water is present. At what pressures is hydrate
formation possible when the temperature is 70F?
17- 7. The liquid water of Exercise 17-6 contains 1 O wt % solids. At
what pressures is hydrate formation possible when the temperature is 70F?
17-8. A 0.75 specific gravity gas is collected in a gathering system. The
pressure in the gathering system is 1000 psia. The liquid water in
the gathering system condensed from the produced gas (0%

Gas Hydrates

487

...J

<
::

~4

ee

32

./

1--

50

-~
/

1!0 IOO

.,.

_ ......./

1/

1.:::

I~

---

150 200

300 400

600 600 KXXl 15CXI

FINAL PRESSURE,

PS IA

2000

3fXO

Fig. 17-13. Permissble expansion of 0.9 specific gravity gas without

hydrate formation. (Katz, Trans., AIME, 160, 140. Copyright 1945 SPEAIME.)

solids). At what temperatures is hydrate formation possible?

The gathering system of Exercise 17-8 must be protected from
hydrate formation to a temperature of 40"F. Methanol will be
added to the liquid water. What concentration must the methanol
reach to inhibit hydrate formation?
17-10. What concentration of diethylene glycol is required to inhibit
hydrate formation to 40F in Exercise 17-8?
17-11. Tubinghead conditions of a dry gas well are 2600 psia and
l lOF. The gas has specific gravity of 0.600. Sorne water
condenses from the gas during production. Gas pressure is
reduced through a choke to 1200 psia. Is there a possibility of
hydrate formation?
17 -9.

488

PETROLEUM

ooo

4000

r--.,--.

'-

--- --

00

_...--

50

"
roe
80

::

r----

'ro

~ 3_

,,/
60

60 IOO

'

'
'

,,, I J

//

'/

~./

/'

I I '' /
1} I
I

.,
'

,,

___.

/W
;,

//

,,

se

100

..

~ t-t>

60

/
/

:.-:.--

30
2

_J

' 1
11
u 1I 1,
',::

------- -- vv , , ,
- .,,
-------- ::1~

160

i \\\
1 1 ~ \
\ \i'
l
1
1 1 ~ 1 :

.... ~ V/~
/
e---' V i-t-

170

.oo
90
s:

' '"
'

J/

l.---"

"'
"'

-c 4~

vv
~

TEMPERAiU~F

zooo

_/

2ZO

5000

5_

'

'\.
<,

FLUIDS

,,

__.,

1/'

,'

ISO 200 300 400

600 600 KlOO
FINAL PRESSURE, PSIA

l500 2000

3000

Fig. 17-14. Permissible expansion of 1.0 specific gravity gas without

hydrate formation. (Katz, Trans., AIME, 160, 140. Copyright 1945 SPEAIME.)

17-12. A 0.70 specific gravity gas is expanded through a choke.

Upstream conditions are 3000 psia and 150F. What is the
lowest pressure to which the gas can be expanded prior to onset
of hydrate formation? What is the temperature at this pressure?
References

l. Katz, D.L., et al.: Handbook of Natural Gas Engineering,

McGraw-Hill Book Co., Inc., New York City (1959).
2. Scauzillo, F.R.: "Inhibiting Hydrate Formations in Hydrocarbon
Gases," Chem. Eng. Prog. (Aug. 1956) 52, 324-328.
3. Deaton, W.M. and Frost, E.M., Jr.: Gas Hydrates and Their
Relation to the Operation of Natural Gas Pipelines, Monograph
Series, USBM, (1946) 8.