Section 5

WATER-HYDROCARBON BEHAVIOR
TABLE OF CONTENTS
PAGE #
WATER CONTENT 5.1
Liquids 5.1
Gases 5.5
Hydrates 5.5
Hydrate Inhibition 5.6
HYDRATE INHIBITION IN LOW TEMPERATURE PROCESSING PLANT 5.8
Valve Expansion Plant (LTS or JfT Plant) 5.9
Glycol Inhibition 5.10
LIST OF FIGURES
FIGURE # PAGE #
5.1(a) Solubility of Water in Hydrocarbons - SI Units 5.2
5.1(b) Solubility of Water in Hydrocarbons - English Units 5.2
5.2(a) Water Content of Gas - SI Units 5.3
5.2(b) Water Content of Gas - English Units 5.4
5.3(a) Hydrate Formation Conditions - SI Units 5.7
5.3(b) Hydrate Formation Conditions - English Units 5.7
5.4 Typical Mechanical Refrigeration Plant 5.9
5.5 Typical LTS Plant 5.9
5.6(a) Glycol-Water Freezing Point Curves - SI Units : 5.11
5.6(b) Glycol-Water Freezing Point Curves - English Units 5.11
RAVVA OIL AND GAS OPERATIONS 5.i
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WATERHYDROCARBON BEHAVIOR
NOTES:
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5.ii
CAIRN ENERGY INDIA PTY LTD
Section 5
WATER-HYDROCARBON BEHAVIOR
WATER CONTENT
Liquids
Although we normally think water and oil do not mix, a small amount of water will dissolve in
oil and other petroleum products. The solubility of water in various hydrocarbons is shown in Figures
5.1(a) and 5.1(b). As you can see from the figures, more water will dissolve as the temperature rises.
This is an important factor in making __ They normally are
made in a refinery or gasoline plant af'il"remperature around 38<;. [lOOF]. Ifwater is present in the
manufacturing or extraction process, the products (gasoline, LPG, etc.) will be saturated with water. If
the product cools in a fuel tank, some water will drop out because its solubility is less at a lower
temperature. Free water in afuel systemcan cause problems.
Since most petroleumproducts are used for fuel, water must be removed from them if there is a
likelihood that they will cool below the temperature at which they are processed. Water is removed by
cooling the liquid or with dehydration equipment.
The water content curves shown in Figures 5.2(a) and 5.2(b) are for water that actually is
dissolved in the hydrocarbon. The only way it can be removed is by cooling the liquid or drying it. A
shake-out test made on a sample of crude oil to determine its water content measures the free or excess
water in the oil. This is the water removed in a crude oil dehydration process. The soluble water
remains in the oilduring the shake-out.
r
\ .
\
Example5.1: A fuel tank on a farm holds 2000 liters [500 U.S. gallons] of propane. How much
water would drop out in the tank if it is filled with wet propane at 38e [lOOF]
and later cools to lOoe [50F]?
WatercontentofC
3
at 38C [lOOF]
Watercontentof C
3
at 100C[50F]
Waterdropout (Difference)
Volumeof C
3
in tank
TotalWater Dropout
SI Units English Units
0.176 glliter 0.70 qtJlOOO gal
0.046 glliter 0.20 qtJ1000 gal
0.130giliter 0.68 qtJlOOO gal
2000 liters 500 gal
2000 x 0.130 0.68 x 500/1000
=260 grams = 0.34 qt
or 0.26 liters
RAVVA OIL AND GAS OPERATIONS 5.1
WATER-HYDROCARBON BEHAVIOR
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Figure5.1(a) Solubility of Water inHydrocarbons- SI Units
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Figure5.1(b) Solubility ofWater in Hydrocarbons- English Units
CAIRN ENERGY INDIA PTY LTD 5.2
WATER CONTENT
)
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WaterDewPoint,C
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Figure5.2(a) WaterContent of Gas - 81Units
RAVVA OIL AND GAS OPERATIONS 5.3
3000
WATERHYDROCARBON BEHAVIOR
I:::'
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\ '
2000
600
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500
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Figure 5.2(b) Water Content of Gas - English Units
--,
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CAIRN ENERGY INDIA PTY LTD
2
WATER CONTENT
Gases
Natural gas or other hydrocarbon vapors contain water in a vapor state (steam) just as air holds
water in the form of humidity. The amount of water that gas will hold depends upon the temperature
and pressure as shown in Figures 5.2(a) and 5.2(b). Water must be removed from gas to prevent
condensation in a pipeline or fuel consuming equipment.
The most common use of the gas-water content curves are in designing and/or checking opera-
tion of gas dehydration facilities.
Example 5.2: Gas enters a dehydration plant at a pressure of 4000 kPa [580 psi] and a tempera-
ture of 38C [lOOF]. The flow rate is three million m
3/d
[106 MMscf/d]. How
much water can the gas contain?
Gas Temperature
Gas Pressure
From Figures 5.2(a) and 5.2(b), water con-
tent at temperature and pressure
Gas flow rate
Total water in gas
51 Units
38C
4000 !cPa
1480 kg/million m
3
3 million m
3
/d
1480 x 3
= 4440 kg/d
English Units
100F
580 psi
921b/MMcf
106 MMcf/d
92 x 106
= 9752 Ibid
A common form used to express water content of gas is the dewpoint. 1:J:le__
temperature at which water will condense from gas. The relative humidity of gas at its dewpoint
. ",........ / ........ v ........ / ........ / ......../ ....... .... / .......... _- .........__ .,r" ... .-.-..... ./... /,.....-..... ....
temperature is 100%. If gas containing water vapor is cooled, the temperature at which liquid first
starts to form is the dewpoint.
The quantity of water vapor contained in gas at its dewpoint will depend upon the gas pressure.
Figures 5.2(a) and 5.2(b). indicate the amount of moisture gas can contain at various temperatures and
pressures. When gas is at its dewpoint, its water content will be that shown on the curves.
Example 5.3: Gas leaving a dehydrator has a water content of 64 kg/million m
3
[4 IbINIMcf].
Pressure is 5500 kPa [800 psi]. What is its dewpoint?
Refer to Figures 5.2(a) and 5.2(b). Move up the left scale until you reach the water content ... 64 kg
[4 lb]. At this point, move horizontally to the right until you intersect the pressure ... 5500 kPa [800
psi]. Move down vertically to the temperature scale and read -lODe [14F].
Figures 5.2(a) and 5.2(b). are to be used for "pipeline quality" gases. This means the gas
contains small amounts of H
2S,
CO
2
and heavy hydrocarbons. For sour gases, different correlations are
required. Gases with H
2S
and CO
2
can hold more water than sweet gases.
Hydrates
Hydrocarbon fluids exhibit a peculiar characteristic under certain conditions of temperature and
pressure when free water is present. A substance known as a hydrate will form. A hydrate is a frozen
mixture of water and hydrocarbons that forms at a temperature well above the freezing point of water.
Its physical form will vary from a gelatinous mush to solid ice. It can completely block a line or
vessel, causing severe pressure drop, flow interruption, or even rupture.
RAVVA OILAND GAS OPERATIONS 5.5
WATER-HYDROCARBON BEHAVIOR
A hydrate forms only in the presence of light hydrocarbon molecules (n-butane and smaller),
CO
2
and H
2S.
Water must be present in a liquid form. The approximate temperature and pressure at
which hydrates form is shown in Figures 5.3(a) and 5.3(b). Hydrate formation is composition depend-
ent and these curves should be used as a guideline only for other compositions. More detailed calcula-
tions can be found in other references.
Free water must be present for hydrates to form. If the gas is properly dehydrated, no hydrate
win form. Also, if a sufficient amount of alcohol or glycol is added to gas, hydrate formation can be
prevented. This is called hydrate inhibition.
Hydrates are of particular concern to gas processing plant operators because most plants have
refrigeration facilities to chill the gas to a temperature well below the hydrate formation point. If the
gas is not dehydrated or the hydrates are not inhibited, hydrates can form in the heat exchangers and
can completely block the flow.
The best way to avoid hydrate problems is to:
1. Dehydrate the gas.
2. Use chemical inhibition (alcohol or glycol).
3. Keep the system temperature above the hydrate temperature.
If hydrates have started to form in the system and the gas flow is not completely blocked, they
can usually be removed by injecting methanol into the gas flow. Methanol injection ports are often
installed upstream of heat exchangers, valves and turboexpanders in refrigeration systems for this rea-
son. Hydrate formation is usually detected by measuring the differential pressure across the equipment.
A rise in L),p indicates hydrate formation.
If the gas flow has been completely stopped by the hydrate plug, the system must be depres-
sured and allowed to warm to ambient temperature so that the hydrate will melt. The depressurization
step must be done very carefully so that differential pressure is not allowed to build up across the
hydrate plug. This L),p may cause the hydrate plug to break free and move through the piping at very./
high speeds. Severe damage and injury may result from these hydrate "bullets."
Hydrate Inhibition
As discussed earlier, there are three primary methods of preventing hydrate formation in a gas
production/processing system.
1. Dehydrate the gas.
2. Keep the temperature of the gas above the hydrate point.
3. Inject a hydrate inhibitor.
Method (1) is the most positive method since it removes the water from the gas. If free water
cannot condense out in a gas system, hydrates cannot form. Method (1) is not always the most eco-
nomical method of preventing hydrates however. Sometimes, due to the high cost of installing a dehy-
dration unit, methods 2 or 3 are preferred.
Method 2 is often used in gas production facilities to keep the gas temperature above the
hydrate point downstream of the production choke. Water-bath heaters are frequently used to heat the
gas. These are usually applied on a well-by-well basis. This method of preventing hydrates is obvi-
ously not effective in gas processing, especially low temperature processing.
Method 3 is a very common method of preventing hydrates in both gas production and process-
ing facilities. An inhibitor is a chemical that lowers the freezing point of water. (Lowering the freez-
CAIRN ENERGY INDIA PTY LTD 5.6
WATER-HYDROCARBON BEHAVIOR
ing point is the same as lowering the hydrate point.) Several chemicals can be used. The most com-
mon inhibitors are: .' .,
- : ~ .,>
y<V Ethylene glycol'
~ /
//2. Diethylene glycol
3. Methanol ~ /
Ethylene glycol is by far and away the most common inhibitor in gas processing. Diethylene
glycol is used occasionally, but its high viscosity is a problem in low temperature gas processing.
Methanol is very popular for inhibiting hydrates on an intermittent basis in production facilities. It has.
two main disadvantages, however. First, it cannot be recovered and all the methanol injected is lost
either in the gas stream or the produced water. Secondly, most of the methanol injected vaporizes into
the gas and does nothing to prevent hydrates. As a result the methanol injection rates can be quite
high.
Methanol is cheaper than glycol and mixes more easily with the gas and water. This makes it
very popular in production facilities for inhibiting hydrates on a temporary basis (usually in the winter-
time) and for breaking hydrates which have already formed.
We will discuss hydrate inhibition in this manual assuming that the inhibitor is ethylene glycol.
Any time the word glycol is used in this section it will refer to ethylene glycol (EG).
HYDRATE INHIBITION INLOWTEMPERATURE
PROCESSING PLANT
(
When gas is processed in certain types of low temperature processing plants, glycol injection is
frequently used to prevent hydrate formation in the heat exchangers and the cold separator. Mechanical
refrigeration plants and valve expansion plants (often called Jff or LTX units) typically use glycol
injection systems. Glycol injection has been used to inhibit hydrates to temperatures as low as -40C
[-40F].
Ethylene glycol is injected into the stream as it enters heat exchangers in which the gas tem-
perature is lowered. It mixes with water, which condenses from the gas as it is cooled, and thereby
prevents the hydrate from forming. The glycol is recovered in the low temperature separator. It is
diluted with water that condenses as the gas is chilled. The diluted solution (rich glycol) flows to a
reconcentrator, where the condensed water is boiled out. The reconcentrated glycol (lean glycol) is then
pumped back to the injection points.
Figure 5.4 shows a typical mechanical refrigeration gas processing plant.
Inlet gas flows through a gas-to-gas exchanger where it is partially cooled with chilled gas
leaving the plant. Glycol is injected into the inlet gas stream entering the gas-to-gas exchanger. The
partially cooled inlet gas and glycol flowing out of the exchanger then enter a chiller where its tem-
perature is lowered to the desired point with refrigerant - usually propane or Freon. Glycol is also
injected into the gas stream entering the chiller.
The stream leaving the chiller is a mixture of gas, glycol, and liquid hydrocarbons. It flows to
a low temperature separator where the liquids fall to the bottom. Cold gas leaves the separator and
flows through the gas-to-gas exchanger where it partially cools the inlet gas. The outlet gas from the
exchanger usually enters a pipeline.
CAIRN ENERGY INDIA PTY LTD 5.8
".t\
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WATER CONTENT
I.' .:":' .
"
20000
18000
16000
14000
<,
ro
12000
o,

OJ
10000
::;
lfJ
lfJ
OJ
0::
8000
6000
4000
2000
0
20 -10 o 10 20 30 40
Temperature,C
I
I
i
I
I
I
I
,
II t t>
", .....;)",,-
I
,}
'" Hydrates
[1>':-
I
,...-'-
_i?'
""I-
k '
:/

I ."-"-
NoHydrates
\
....
.>
.'.
I


'*
.1
,
[/ ',\ ......... ... " v
y

,\
e(
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,,' ,
V :-, .:
..
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.I'
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;
I
"""'"
Figure 5.3(a) HydrateFormation Conditions- 81Units
\
3000
2500
2000
ro
'en
0-
eD
1500
::;
lfJ
lfJ
OJ
0::
1000
500
- --- ._.
II
"
II
II
I
Hydrates
I
I
NoHydrates
J

v
io'"
io'"
o
o 10 20 30 40 50 60 70 80 90 100
Temperature,of
Figure 5.3(b) Hydrate Formation Conditions- English Units
RAVVA OIL AND GAS OPERATIONS 5.7
HYDRATE INHIBITION IN LOW TEMPERATURE PROCESSING PLANT
Refrig.
Outlet
Vapor
Gas
Gas-Gas
Exchanger
30C
[86 OF]
Inlet
Gas
Lean
Glycol
.l,

24C
[76 OF]
-18C
[0 OF]
Liquid
Refrig.
Hydrocarbon
Rich Glycol to Reconcentrator
Figure 5.4 Typical Mechanical Refrigeration Plant
Glycol, being heavier than liquid hydrocarbon, collects in the bottom of the low temperature
separator and flows to a reconcentrator to remove the dilution water that condensed when the gas was
chilled.
Liquid hydrocarbons that collect in the low temperature separator flow to other processing
facilities to stabilize or segregate the various hydrocarbons in the stream.
Valve Expansion Plant (LTS or J/TPlant)
In a valve expansion plant the glycol injection system is identical to that in a refrigerated plant
except that there is only one heat exchanger (gas-to-gas exchanger) and the expansion across the valve,
rather than a chiller, provides the secondary cooling for the gas. Figure 5.5 presents a typical LTS plant
showing the glycol injection points.
\
Outlet
Gas
30C
-7 C
[86 OF]
[20 OF]
-lnlet
Gas-Gas
Gas
Exchanger
-18C
i
1
[0 OF]
Hydrocarbon
Rich Glycol to Reconcentrator
Figure 5.5 Typical LTS Plant
RAVVAOILANDGAS OPERATIONS 5.9
WATER-HYDROCARBON BEHAVIOR
GlycolInhibition
Although ethylene glycol is commonly used as an anti-freeze to prevent water from freezing in
automobile engines, some mixtures of glycol and water will freeze at temperatures which occur in low
temperature processing plants. In fact, pure ethylene glycol freezes at a temperature of-6C [22F]. J
Consequently, the concentration of glycol that is injected in the gas stream must be carefully controlled'
so that itwill not freeze when it passes through the low temperature exchangers.
Figures5.6(a) and 5.6(b) indicate the freezing points ofvarious glycol-watermixtures.
As you can see from the glycol freezing point curves, a glycol concentration of 90% (10%
water) will freeze at a temperature of -25C [-13F]. A solution containing 47% glycol and the bal-
ance water will freeze at the same temperature. If a low temperature plant chills gas to -25C[_13P],
the concentration ofglycol used for injecting in the exchangers to prevent hydrate from forming must
be above 47% and less than 90%, orthe glycol will freeze.
The concentration of the lean EG solution injected into the exchanger is typically around 75 wt%. The
concentration of the rich EG solution taken out of the cold separator can be detennined from the
Hammerschmidtequation below.
(lOO)(d)(M)
.(d)(M)+ K

Where: d = hydrate depression, C[OF] (hydratetemperature- systemtemperature)
M = molwtofinhibitor EG = 62
(
DEG = 106 \
Methanol= 32
K = constant 1300 ifdisinDC
2340 if d is inOF
The concentration calculated in the above equation is the minimumconcentration ofrich inhibi-
tor. If the actual concentration is less than this, freezing will occur. It is usually best to inject enough
inhibitor sothat therich inhibitorconcentrationis greaterthan thenumbercalculated above.
Once the rich concentration has been determined, the inhibitor injection rate may be calculated
from the equation below.
'\ ) y.J\)
)
(
--:---:;
("(\1
9; .- -ro I .....
\ -',/
Where: mr = massofinhibitor, kg [Ib]
\ (\... , < '1'\'\ >.f\!
massofliquid water, kg [Ib]
XL = leaninhibitorconcentration, wt% r: A 'jJI
XR = richinhibitorconcentration, wt%
\6,'/C:;V'
. ,,'. In the above equation the term XL - XR is called the glycol dilution ,; \ :::\\"'? .\
vi./ ,\' . ..
-,
j/ The actual glycol injection rate in the previous example would be higher than the calculated
amount. The reason for this is the injection rate is the lowest possible rate needed to prevent hydrates.
1/
Tobe on the safe side most people inject a higher glycol rate to be sure all of the glycol mixes with the
gas. One way to estimate this higher rate is to assume a lower glycol dilution. For example, the /
-:
minimum required dilution is 20%, but the actual injection rate would be calculated on a 10-15%
dilution.
5.10 CAIRN ENERGY INDIA PTY LTD
HYDRATE INHIBITION IN LOW TEMPERATURE PROCESSING PLANT
o
-10
U
0
a)

::J
1ij

-20
CD
a.
E

;..

-30
Shaded Areas lndi-
cate Freezing Zone
20 40 60 80 100
Percent Glycol in Glycol Water Solution
Figure 5.6(a) Glycol-Water Freezing Point Curves - 81 Units
o
Percent Glycol in Glycol Water ..
,
Shaded Areas Indi-
cate Freezing Zone
.-,- -
'. ,-
I
'\
0 20 40 60 80 10
20
-20
40
LL
o


CD 0
a.
E

I)
Figure 5.6(b) Glycol-Water Freezing Point Curves - English Units
\.
RAVVA OILAND GAS OPERATIONS 5.11
WATER-HYDROCARBON BEHAVIOR
Example 5.4: A gas flow rate of 2 x 10
6
std m
3/d
[70 MMsef/d] is to be cooled from 40C
[104F] to -10C [14F] in a refrigeration system. How much 75 wt% EG must
be injected to prevent hydrate formation in the heat exchanger if the exchanger
pressure is 5800 kPa [840 psia]?
Step 1 - Determine hydrate temperature of gas.
SI from Figure 5.3(a)
English from Figure 5.3(b)
T
H
= I5.5C
T
H
=60F
Step 2 - Calculate the amount of free liquid water which condenses in system.
From Figure 5.2(a)
Water Content In 40C [104F]
From Figure 5.2(b)
Water Content Out -10C [14F]
Water Condensed
per day
51 Units
1137 kgl10
6std
m
3
(1137)(2) =2274 kg/d
English Units
74 IblMMscf
4 IblMMscf
701bIMMscf
(70)(70) =4900 Ibid
Step 3 - Calculate the minimum rich EG solution concentration.
51 Units
X
R
= (100)(25.5)(62) = 55%
(25.5)(62) + 1300
English Units
X
R
= (100)(46)(62) = 55%
(47)(62) + 2340
Step 4 - Calculate the minimum amount of inhibitor to be injected per day.
51 Units
(2274)(55) = 6250 kg/d
(75 - 55)
English Units
(4900)(55) = 13475 Ibid
(75 - 55)
NOTES:
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CAIRN ENERGY INDIA PTY LTD