Chapter 11 Hydrates

Chapter 11: Hydrates
11.1 Problem
Formation of natural gas hydrates can present a serious problem in oil and gas production.
Hydrates are crystalline, ice-like solids that form when small gas molecules, such as methane,
ethane, and propane, are trapped in hydrogen-bonded water cages under high-pressure and lowtemperature conditions, as shown in Figure 1. These conditions are often encountered in
deepwater operations, such as subsea flowlines carrying wet gases and in cold-weather
operations in northern climates.
Figure 1. Structures of natural gas

The problem of natural gas hydrates has been well known to those working in the gas
production, storage, and transportation industries for many years. Formation of gas hydrates can
also be a problem in crude oil production and transportation. As little as 1% water cut is
sufficient to form a hydrate plug in some oil producing systems for example, in Statoils
Tommeliton field blockages formed from a hydrate slurry with less than 1% water cut.
Formation of hydrate plugs is very fluid dependent. While some oil/water systems form hydrates
and/or plugs almost instantaneously with low water cut, other oil/water systems may have
difficulty forming hydrate plugs even at water cut as high as 50%. All water has the potential to
be transformed into hydrates if the condition is right, i.e., low temperature and high pressure.
Oil Field Chemicals Training Manual
11-2
Property of Nalco Energy Services
Confidential & Proprietary DO NOT DUPLICATE

Although the phenomenon of gas hydrates was first studied as early as 1811, the existence of
hydrates was first confirmed by Villard in 1888. In the 1930s, Hammerschmidt discovered
hydrates as a pipeline plugging agent and developed an equation (see section 11.7) to predict the
hydrate depression temperature.
The problems associated with the formation of gas hydrates can include:
Reduction in the gas throughput.
Plugging of flow lines.
Increased pressure differences across the gathering system.
Erosion.
Damage to downstream equipment.
Increased safety concerns.
Unlike other plugging agents that require a substantial amount of time to accumulate in
pipelines, such as sand, paraffin wax, or scale, hydrate formation is rapid (often requiring only
hours to plug a pipeline) and, in some cases, catastrophic. Therefore, prevention of hydrate
formation is the key strategy for hydrate control in deepwater production. Figure 2 shows the
pictures of hydrates found in pig traps.
Figure 2. Hydrates plugs formed in the pipelines, courtesy of Statoil (left) and Petrobras (right)
Gas hydrates can form in various parts of the subsea production system. Hydrates have been
found in downhole tubing, wellhead trees, manifolds, jumpers, flowlines, and risers. A hydrate
plug can cause a major interruption to the flow of produced fluids. Since most of the deepwater
subsea wells are extremely productive, some as high as 100 MMSCF/day, this interruption can
be very costly to the operator.

11-3

Hydrate plugs in subsea environments can be difficult to remove, often requiring the gradual
lowering of pressure in the line to allow the plug to thaw. This can be very time-consuming and
often dangerous because a dislodged hydrate plug can act as a high-speed projectile, damaging
the downstream equipment. Other remedial techniques, such as heating, coiled tubing, and
chemical, have also been used.
11.2 Theory
Natural gas hydrates are crystals formed by water with small gas molecules
and associated liquids in a ratio of 85 mol% water and 15 mol%
hydrocarbons. Gas hydrates have been called the burning ice. This is due to
the fact that gas hydrates are, in fact, host water cages containing guest
gas molecules. These combustible gas molecules can be easily burned (Figure
3), leaving behind liquid water. The host cages, which contain many different
sizes of cavities, are formed by water molecules hydrogen bonded to one
another. These cages are thermodynamically unstable when the cavities are
empty. However, as soon as some small molecules occupy the cages, they
become thermodynamically stable and turn into solids, i.e., hydrates, as soon
as some small molecules occupy the cavities.
Figure 3. Burning
hydrates
The dimension of these cavities fits very well with the size of the small gas
molecules, such as methane, ethane, propane, butane, pentane, hexane, nitrogen, carbon dioxide,
and hydrogen sulfide. Some larger molecules, such as cyclohexane and methylcyclopropane,
can also fit into the larger cavities. Some molecules like benzene can also promote hydrate
formation even though the molecules themselves may not fit into the cavities.
There are several different structures possible (type I, II, and H) for the hydrate crystals as was
shown in Figure 1. The most common structure found in the oil and gas fields is Type II
hydrates. In contrast, Type H hydrates are created mostly in the laboratory environment. Type I
hydrates are formed predominantly in a methane-rich environment (> 99 mol% methane). The
presence of a small amount of heavier components in natural gas, such as 0.5 mol% propane,
will make Type II the predominant structures. This is the reason why Type II is the most
commonly observed structure in the field.
Having the right components (natural gas and water) is not sufficient to form stable hydrates.
The condition must also be right. The favorable condition is low temperature and high pressure,
which is typical of deepwater offshore operation. Unlike ice formation that occurs around 0C,
hydrate formation can occur at as high as 20C if the pressure is high enough. Indeed, the
hydrate equilibrium temperature increases with increasing operating pressure (see Figure 4). At
a typical seabed temperature of 4C, the hydrate equilibrium temperature can be as low as 170
psi.

11-4
11.3 Formation of Hydrates

The following four components must be present for gas hydrate crystal formation to take place:
1.
2.
3.
4.
Natural Gas
Water
High pressure
Low temperature
The requirement for gas is easily met in all petroleum production systems. The water
requirement is usually interpreted to mean water in the liquid phase. Water in the liquid phase
can be either produced water or water condensed from gas subjected to temperatures below the
dew point.
The low-temperature and high-pressure requirements are met by many of the systems that are in
operation today. Exactly how low the temperature has to be, or how high the pressure has to be
to form hydrates, is governed by the hydrate equilibrium curve for the particular system. A
typical curve is shown in Figure 4 on the next page. This curve shows the hydrate region to the
left of the curve and the non-hydrate region to the right.

11-5
Figure 4. Typical Hydrate Equilibrium Curve

12000
10000
Pressure
(psia)
Hydrate
Region
8000
Arrow A
6000
Non-hydrate
Region
4000
Arrow B
2000
Arrow C
0
30
40
50
60
70
80
90
100
Temperature (F)
The severity of hydrate formation is a function of the degree of temperature inside the hydrate
region at which the system operates at a given pressure. This is referred to as the degree of
subcooling: the higher the degrees of subcooling, the more severe the potential for hydrate
formation. In the hydrate phase equilibrium curve in Figure 4, the system is operated at a
temperature of 60F and 5,500 psi. At the operating pressure, the hydrate equilibrium
temperature is 80F. The system operates at 20F of subcooling. There are two possible
solutions to remedy the hydrate problem if the producer desires to operate in the non-hydrate
region:
1. (Figure 4 Arrow A) Increase the temperature of the system. This would move the
operating temperature from the current point in the hydrate region to some point to the right,
outside the hydrate region.
2. (Figure 4 Arrow B) Lower the operating pressure.
Of course, these two options can be used at the same time by increasing the temperature while
reducing the pressure, as shown by Arrow C.

11-6

The presence of acid gasses such as carbon dioxide or hydrogen sulfide in the system can shift
the hydrate curve to the right, as shown in Figure 5. Thus, the presence of these gasses can
exacerbate the hydrate formation situation and make prevention more difficult. While hydrate
inhibitors will still work under these conditions, often a higher dosage is required.
Hydrate Formation Curves

10000
9000
Pressure (psia)
8000
7000
6000
H2S
No H2S Present
5000
N2
4000
3000
2000
1000
0
30
40
50
60
70
80
Temperature (F)
Figure 5. The effect of H2S on hydrate equilibrium curve

11-7
90
11.4 Prevention of Hydrates

As mentioned in the previous section, four essential elements are needed for hydrate formation:
the presence of natural gas (e.g., methane), the presence of water, the condition of low
temperature, and the condition of high pressure. The absence of any of these four elements
would make hydrate formation impossible. For example, the element of low temperature can be
removed from the equation by proper heat management techniques using external heating or
thermal insulation. Similarly, lowering the pressure by choking-back the production can reduce
the tendency for hydrates to form in a production system. Water, another necessary element in
hydrate formation, can be removed by dehydration of the natural gas.
Although all of these methods can theoretically prevent hydrate formation, some may not be
feasible or desirable in the field, especially in offshore environments. For instance, dehydration
may not be an option for offshore operation due to space or weight/load limitations for the
processing equipment. Therefore, to transport the unprocessed, wet hydrocarbon production
streams, operators often rely on other alternatives such as heat management or chemical
inhibition.
11.4.1 Methanol and Glycol

The two most commonly used chemical inhibitors are methanol and ethylene glycol. These
inhibitors shift the hydrate equilibrium condition so that the operating condition falls outside of
the hydrate formation region. Take Figure 6 on the next page as an example.

11-8
3000
35 wt%
MeOH
2700
No
Inhibitor
45 wt%
MEG
2400
operating condition
@ 1,500 psi and 40F
Pressure (psi)
2100
1800
D
30F subcooling
1500
A
C
1200
900
600
300
0
30
35
40
45
50
55
60
65
70
75
80
Temperature (F)
Figure 6. Hydrate equilibrium curves with and without chemical inhibitors

The hydrate equilibrium curve for the given system is shown as the dashed line. The condition at
which the system is being operated is 1,500 psi and 40F (point A). At such a high pressure, the
hydrate equilibrium temperature is estimated to be 70F (point B). This means that the system is
operated in the hydrate region with 30F (i.e., 70 - 40 = 30) subcooling. In order to operate this
system out of the hydrate region, methanol (MeOH) or ethylene glycol (MEG) can be injected.
If 35 wt% methanol (based on total produced water) is injected into the system, the hydrate
equilibrium curve is shifted to the solid line on the left. Consequently, the operating condition
falls to the right of the hydrate equilibrium curve, meaning that the condition is out of the hydrate
region. The corresponding hydrate equilibrium at 1,500 psi is now 34F (point D), which is
lower than the current operating temperature. Alternatively, one can inject 45 wt% ethylene
glycol (based on total produced water) to move the hydrate equilibrium curve to the solid line on
the right, effectively lowering the hydrate equilibrium temperature to 35F (point C). Note that
methanol is more effective than ethylene glycol on a per weight basis due to its lower molecular
weight (32 versus 62).

11-9

Both methanol and ethylene glycol are often classified as thermodynamic inhibitors because of
their ability to shift the hydrate equilibrium curve toward higher pressures and lower
temperatures by changing the activity of water molecules. The effective concentration is very
high, typically ranging from 10 wt% to 60 wt% (based on total produced water) as a function of
subcooling. The higher the subcooling is, the higher the effective concentration must be.
Methanol and ethylene glycol are the most popular choices because of their low cost and
widespread availability. However, methanol usage also has some drawbacks. The drawbacks
include flammability, toxicity, and due to the large volumes required to treat the hydrates, large
storage requirements are necessary in the field. Glycols are generally not as toxic or flammable,
but the cost of glycol is higher than methanol. Glycols are also less effective than methanol and
require more energy to pump due to their higher viscosity
11.4.2 Low Dosage Hydrate Inhibitors

Recently, a new group of non-thermodynamic chemical inhibitors has been developed. These
chemicals are very different from the traditional thermodynamic inhibitors because they do not
shift the thermodynamic equilibrium of hydrate formation. Instead, these inhibitors interfere
with the process of hydrate formation. Since the effective dosages of this new type of chemical
inhibitors are much lower than those required for thermodynamic inhibitors, the inhibitors are
usually classified as low dosage hydrate inhibitors (LDHI). The effective concentration for
LDHI typically ranges from 500 ppm to 2% of the total amount of water being treated. Nalco
has developed a group of effective LDHI and marketed them as FREEFLOW technology (see
Figure 7).
Figure 7. Logos of FREEFLOW program based on the LDHI technology

11-10

11.4.2.1
Mechanism of Kinetic Hydrate Inhibitors
Some LDHI effectively interfere with the nucleation

and crystallization of hydrate molecules, thus
extending the time required to form hydrates (known
as induction time). These products are referred to as
kinetic hydrate inhibitors (KHI). Examples of these
products include EC6441A, EC6451A, EC6481A,
EC6491A, and EC6504A. These products are mainly
polymer-based materials in an aqueous-based solvent
system. The extension of induction time is a function
of subcooling. The induction time increases
exponentially as the degree of subcooling decreases.
As a rule of thumb, FREEFLOW can effectively treat
condensate systems up to 23F subcooling and black
oil systems up to 18F subcooling for at least 48
hours protection, meaning that hydrates will not form
for at least 48 hours. In some systems where the
subcooling is low (e.g., 10F), the induction time can
be as long as a week or more. Hydrocarbon also
plays an important role in varying the induction time.
For example, KHI has successfully treated a system
with a subcooling as high as 30F.
Figure 9. Molecular structures of

some KHI polymers
Details of the hydrate control mechanism by

KHI are largely unknown. Molecular
modeling has been carried out to study the
interaction between the KHI polymers and
the hydrate lattice. It is thought that the
polymer chain anchors on the hydrate lattice
through the oxygen atoms. The pendant
groups displace the gas molecules from the
cavities and the polymer chain blocks the
enclosure of the cages. This type of
interaction disrupts the stable hydrate
formation that otherwise will take place in a
much shorter time frame. When the
induction time is exceeded, the polymers are
eventually displaced to allow more
thermodynamically stable hydrates to form.
Figure 10. The interaction of hydrate lattice
with KHI polymers.

11-11

11.4.2.2
Mechanism of Anti-agglomerates
Another type of LDHI can modify hydrate particles by adsorbing on or incorporating into the
hydrate crystals. These chemicals have at least one long hydrocarbon chain to help the hydrate
particles disperse in the hydrocarbon medium such that they do not agglomerate but stay
dispersed as a slurry. For this reason, these chemicals are referred to as anti-agglomerants (AA),
and the presence of a significant amount of hydrocarbon phase, typically in excess of 60% oil
cut, is necessary. Figure 11 shows an illustrative mechanism of how AA works in the production
systems.
Figure 11. Hydrate control mechanism for antiagglomerants in the pipeline.

11-12

11.4.2.3
Comparison of KHI to AA
There are both advantages and disadvantages associated with the use of AA and KHI. In general,
AA can handle a higher degree of subcooling and sustain a longer shut-in period. However, these
chemicals are typically more toxic than KHIs. A minimum of oil cut, usually 50% to 70%, is
needed for an AA to work. AAs may also cause production problems, such as bad water quality
and emulsions. Also, pumping the resulting hydrate slurries can become an issue for the
operation due to the concerns of erosion, over-pressure, oversize pump availability/operability,
increased energy consumption, and lack of experience. In contrast to AA, KHI is more
environmentally friendly, requires no oil to make it work, and provides a hydrate-free
environment. However, the present KHI technology is limited to a lower degree of subcooling
and a shorter shut-in period (limited to the maximum induction time extendable).
The following table shows a quick summary of the advantages and disadvantages of AA and
KHI.
Advantages
Disadvantages
Kinetic Hydrate Inhibitors (KHI)

Requires no oil
Environmentally friendly
Anti-agglomerates (AA)
Higher degrees of subcooling
than KHIs
Hydrate free operations
Sustain longer shut-in periods
Lower degree of subcooling than

AAs
Higher toxicity than KHIs
Shorter shut-in period than AAs
Requires minimum 50% oil to

work
Potential water quality problems
or emulsions
Pumping hydrate slurry requires
larger pumps, more service time,
and more energy

11-13
11.5 Return on Investment

Some important key performance indicators for hydrates include:
Cost per BW treated
Pressure differential on pipeline
Hydrate related failure downtime
Conformance to monitoring
Chemical usage versus actual
11.6 System Survey

The Hydrate Inhibitor Questionnaire (section 11.6.1) and HydraCalc (11.6.2) can make the
system survey process relatively easy. A section of the technical questionnaire is shown below.
The HydraCalc computer-based model is a proprietary Nalco tool used in evaluating the
potential for and the severity of a hydrate situation. These tools will aid you in collecting the
design basis, system operating parameters, and other information required for making a thorough
assessment of your customers hydrate challenge. They can also be used to develop the final
recommendation.
For some applications, it is necessary to have detailed modeling performed by research scientists
highly skilled at this practice. It may also require physical testing in the Flow Assurance
Laboratory. The information collected in the technical questionnaire can be passed along to
Nalco marketing and research teams and used for this purpose. However, in many cases, the
severity of the conditions can be determined in the field and the recommendation be made right
there. HydraCalc can be used for this purpose.

11-14
11.6.1 Hydrate Inhibitor Questionnaire

IMPORTANT questions to be answered:
A short description of your application, for example
Hydrate inhibitor is needed for a 10, 55-mile subsea pipeline that carries wet gas from
the subsea manifold to the processing platform.
Pressure and temperature profiles, for example
The inlet pressure is 3,000 psi and the arrival pressure at the platform is 2,300 psi.
The fluid leaves the manifold @ 110F and its temperature decreases to 40F seabed
temperature after the first 3 miles. The temperature rises to 50F at the platformboarding valve.
Chemical injection, for example
How and where to be injected?
If injected through the umbilical, how long and what size is the umbilical? What is the
material for the wetted part of the umbilical?
What is the temperature at the injection point?
Production rates (gas, water, and condensate), for example
85 MMSCFD gas with 50 BWPD and 20 BOPD
Gas composition, for example
Component
N2
CO2
C1
C2
C3
Percent
5%
3%
80%
5%
2%
Component
i-C4
n-C4
i-C5
n-C5
Total

11-15
Percent
2%
1.5%
1%
0.5%
100%
11.6.2 HydraCalc
HydraCalc is a proprietary Nalco Excel-based program that requires only minimal input. The
Nalco representative along with the customer, if appropriate, uses this program in the field. It
provides a quick and accurate determination of the potential and the severity of a hydrate
challenge. It also provides estimated Methanol consumption and KHI requirements. The
program operates as follows:
1. After opening the HydraCalc program, the operator must first press ctrl-F to activate the
macros.
2. The company and stream or well name is entered for reference.
3. Enter the coldest expected system-operating temperature in degrees Fahrenheit (F). If this
data is not available, use 40F. Few applications will be lower than that. As temperatures
approach 32F, freezing becomes a concern, and low dosage hydrate inhibitors do not protect
against ice. Using the lowest possible temperature will increase the severity of the
application and lead to errors on the conservative side.
4. Enter the corresponding operating pressure in pounds per square inch (psi). If unsure, use the
maximum pressure for the system. Similar to the temperature, using the higher pressure will
increase the severity of the application and cause error on the conservative side.
5. Enter the gas production rate in million standard cubic feet per day (MMSCFD).
6. Enter the gas specific gravity. There are two choices for gas gravity. The operator can use
the second page of the spreadsheet to calculate the gravity by entering mole percent of the
individual components. In this case, the calculated gas gravity will show in the calculation
table automatically. If the gas gravity is available, it can be entered directly into the
calculation table. However, the link to the composition spreadsheet will be lost.
7. Enter the oil production in barrels of oil per day (BOPD).
8. Enter the API gravity of the crude, which is used to determine if it is black oil or a
condensate system.
9. Enter the total water production rate in barrels of water per day (BWPD).
10. Choose the type of brine: fresh or saline. Fresh brine should be used if the total dissolved
solids (TDS) of the water is not known. This will result in a worst-case-scenario calculation.
If you choose the Saline option, the calculations will be carried out using 3.5 % TDS.
As the inputs are made, the calculations will run automatically.
If Caution appears in the place of the hydrate inhibitor dosage, then the conditions may be too
severe for the kinetic inhibitors. Please contact Marketing or Research to discuss. This doesnt
necessarily mean that the kinetic inhibitors will not perform, but it does mean that a closer look
is warranted.

11-16

11.6.2.1
HydraCalc Example
Please press ctrl-F to activate Macro first.

Input Parameters (in red)*
Company Name
Stream/Well Name
Coldest Operating Temperature
Corresponding Operating Pressure
Gas Production Rate
Gas Specific Gravity
(If you dont know the value, please fill out the composition worksheet
and let the program calculate it for you.)
Oil Production Rate
API Gravity of Oil
Total Water Production Rate
What is the type of brine, Fresh or Saline?
ABC Oil Company

Pipeline
55F
2,000 psi
100 MMSCF/D
0.5864
32 BOPD
35
10 BWPD
Fresh
Results and Recommendations

Hydrate Equilibrium Temperature
Degree of Subcooling
Methanol Volume Required
FREEFLOW EC6481A Volume Required
FREEFLOW EC6491A Volume Required
*
Input parameters here are shown in boldface type.

11-17
68.0F
13.0F
511 GPD
4 GPD
7 FPD
Gas Gravity Calculation

Please Input the mol% of each component and the MW of the plus (C10+) fraction
ABC Oil Company

Component
N2
28.01
0.37
Avg MW
0.10365
CO2
44.01
0.07
0.03081
H2S
34.00
0.00
0.00000
methane
16.04
97.67
15.66920
ethane
30.07
0.55
0.16539
propane
44.10
0.38
0.16757
i-butane
58.12
0.15
0.08719
n-butane
58.12
0.15
0.08719
i-pentane
72.15
0.09
0.06494
n-pentane
72.15
0.08
0.05772
n-hexane
86.18
0.15
0.12927
n-heptane
96.00
0.14
0.13440
n-octane
107.00
0.10
0.10700
n-nonane
121.00
0.08
0.09680
n-decane
320.00
0.01
0.03200
500
0.01
0.05000
C10+
MW
Mole%
Total
100.00
Gas Gravity
0.5864

11-18
16.98311
11.7 Product Selection

In the 1930s, Hammerschmidt discovered hydrates as a pipeline plugging solid and developed
the following equation to predict the degree of subcooling as a function of inhibitor
concentration. Today, the Hammerschmidt equation remains as a very useful tool to quickly
assess the amount of thermodynamic inhibitor required for hydrate inhibition at a given degree of
subcooling.
CW
T = (Hammerschmidt equation)
M (100 - W)
Where:
T = degree of subcooling, (Thydrate equiliburium - Toperating), in F
C = constant for a particular inhibitor (2,335 for methanol or 2,000 for ethylene glycol)
W = weight percent of the inhibitor in the aqueous phase
M = molecular weight of inhibitor (32 for methanol or 62 for ethylene glycol)
11.7.1 Hydrate Prediction Programs

Recently more accurate methods using computer modeling have been developed to build the
hydrate equilibrium curve for a specific system. Nalco uses the three most popular industrial
standard programs to estimate the hydrate equilibrium curve and, thus, the severity of the
operating condition in terms of its hydrate potential. These programs are PVTSim developed by
Calsep, Multiflash developed by Infochem, and CSMHYD developed by Colorado School of
Mines. A simplified calculation was developed and included in the HydraCalc program to be
used by the field personnel. Alternatively, the hydrate equilibrium curve can be measured in the
laboratory by tracking the hydrate dissociation temperature as a function of pressure. The
predicted curve is very accurate for the condensate system, generally within 1F error. However,
large variations have been seen for the black oil systems due to potential interference that has not
yet been fully identified and built into the models.
Once the degree of subcooling is determined from the hydrate equilibrium curve and the
operating condition, chemical inhibitor is selected and the dosage is decided based on the
minimum effective concentration required. For KHI, the minimum effective concentration is a
function of the degree of subcooling. For AA, the minimum effective dosage is dependent upon
the hydrocarbon in the system. Regardless of AA or KHI being selected, it is better to verify the
performance of LDHI in the laboratory to assure its effectiveness. Indeed, most customers
would require some kind of laboratory testing before approving a product.

11-19
11.7.2 LDHI Laboratory Tests

Several kinds of laboratory test systems have been used for evaluating LDHI. These can be
grouped into small-scale test equipment and large-scale simulation systems. All of these test
systems are designed to operate at high pressures and low temperatures, some with visual
capability. Autoclaves and rocking cells are small-scale test equipment; the flow loop and wheel
loop are large simulation systems. The criteria for passing the performance test are different for
each LDHI. To pass the test, KHI must inhibit hydrate formation for a minimum of a certain
number of hours (typically 48 hours) at a specified subcooling or operating condition. The
performance of AA is measured visually, although some may use viscosity or torque
measurement as a quantitative and auxiliary tool. Acceptable AA performance must demonstrate
free-flowing liquid containing tiny, dispersible hydrate particles.
Autoclave tests are typically carried out in high-pressure vessels with multiple duplicates. The
vessels are typically equipped with agitation devices, cooling jackets, as well as pressure,
temperature, and/or torque sensors. Some may also have windows for visual inspection. A
picture of the autoclave system is shown in Figure 12.
Figure 12. Picture of autoclaves for LDHI testing

11-20

The performance of KHI is usually measured by the induction time allowed at a given
concentration. The induction time for hydrate formation is measured by monitoring the onset of
hydrate formation, which will trigger a temperature spike (due to exothermic reaction) and a
pressure drop (due to gas consumption) in a constant T/P experiment, as seen in Figure 13.
Multiple duplicates are important to account for the expected variations in the measured
induction time. It is known that all nucleation processes, including hydrates, are stochastic and,
as such, require multiple duplicates to get a statistical average. The performance of AA in the
autoclaves is assessed by visual inspection using the criteria stated above.
18
45
16
40
TEMPERATURE (C)
35
12
30
10
25
onset of hydrate formation
20
15
10
temperature
2
0
0
500
1000
1500
2000
2500
TIME (Mins)
Figure 13. Temperature and pressure profiles of autoclave test of hydrate

formation in the presence of KHI

11-21
3000
PRESSURE (Bar)
no hydrate formation
14

Rocking cell tests are typically performed in a small high-pressure cylinder made out of sapphire
tube. A ball is placed inside the tube to provide agitation as the tube is being rocked. The
measurement criteria are the same as those of the autoclave test. The main difference is that the
shear force and the fluid mixing in the rocking cells are much less than those provided by the
autoclave due to the mild rolling action of the ball. The rocking cells are typically placed in a
constant temperature bath to achieve the low temperature. Figure 14 shows a picture of the
rocking cell test unit located in Sugar Land, Texas.
Figure 14. Picture of rocking cells for hydrate inhibitor evaluation.

If the candidate LDHI passes the performance tests in the small-scale laboratory unit, a largescale simulation system is commonly used to verify the performance prior to scheduling a field
trial. The most commonly used simulation systems are high-pressure flow loop and highpressure wheel loop. High-pressure wheel loop was developed by Statoil to study the flow of
production fluids in a closed conduit, such as subsea pipelines. Various types of chemicals,
including LDHI, have been tested in this loop to assess the effect of these chemicals on the fluid
behavior.

11-22

A picture of the wheel loop is shown in Figure 15 along with hydrates formed inside the viewing
window. The loop is usually made out of steel pipe shaped into a circle. The loop is mounted on
a shaft connected to a motor and a torque sensor. Some loops are equipped with viewing
windows to allow visual observation of the fluids inside. A camera is typically mounted on the
windows to record the visible changes throughout the experiment. The whole assembly is
housed in a temperature-controlled chamber in which the temperature is cooled to simulate the
cold deepwater environment. One fundamental difference between the wheel loop and the fluid
flowing in the pipeline is that the wheel loop has a moving pipe and relatively stagnant fluids,
instead of fluids moving in a fixed pipe. In addition to visual observation of hydrate formation,
some other variables are also monitored, such as pressure change or gas uptake.
Figure 15. Pictures of wheel loop in a cold chamber and hydrates in the viewing section

11-23

A flow loop is probably the most realistic,
large-scale pipeline simulation system built
to study fluid behavior and chemical
performance. Flow loops of various sizes
and designs have been built. Pictures of
some flow loops for hydrate studies are
shown in Figure 16. These loops are
typically operated at high pressure and low
temperature for hydrate studies. Some are
housed in a temperature-controlled
chamber similar to those used for the wheel
loop. Some have a cooling jacket around
the pipe to control temperature. The
differential pressure around the loop is
monitored constantly. Any increase in
differential pressure can be indicative of
hydrate build-up. Some flow loops also
have viewing ports to allow visual
inspection or videotaping of the
experiment.
Figure 16. Flow loops in IFP (top), SWRI (bottom left) and ExxonMobil (bottom right)

11-24
11.8 Application Guidelines

The selection and design of a hydrate control program based on LDHI technology is discussed in
sections 11.6 System Survey and 11.7 Product Selection. Laboratory tests to confirm the LDHI
performance and to measure the effective concentration are also discussed. It is equally
important to address several implementation issues before and during the deployment of any
LDHI program in deepwater operations. These issues may not be as pertinent in land-based gas
systems.
11.8.1 Material Compatibility

Material and chemical compatibility of LDHI with the system being treated is a key factor to
determine whether the specific LDHI can be deployed. Material compatibility involves both
metallic and non-metallic materials. The active species in most KHI formulations is mostly
polymers that are inert to common materials used in the oil and gas fields. Therefore, the solvent
packages used in the formulations usually determine the compatibility of the finished products
with the existing materials. Most of the kinetic inhibitors are formulated in aqueous base
solvents, such as water and alcohols. These are the same fluids as those encountered in the
conventional systems treated with thermodynamic inhibitors. Therefore, no additional materials
requirement is needed for implementing the KHI program. Anti-agglomerants, on the other
hand, can be formulated to be either water-soluble or oil-soluble. The active components are
generally more reactive than the KHI polymers. Therefore, the material and chemical
compatibility of AA is less predictable.
11.8.2 Chemical Compatibility

Chemical compatibility of LDHI with other production chemicals can vary greatly. Therefore, it
is important to carry out compatibility studies to investigate the effect of LDHI on the
performance of existing chemicals. The effect of the existing chemicals on the LDHI
performance is equally important. The most frequently used production chemicals, especially in
subsea pipelines, are corrosion inhibitors, scale inhibitors, and paraffin inhibitors. These
chemicals are formulated either in aqueous base solvents or in hydrocarbon solvents.
Most water-soluble chemicals do not interfere with KHI. As a result, neither the performance of
KHI nor the performance of water-soluble chemicals is affected. For example, no adverse effect
has been observed between KHI and water-soluble corrosion or scale inhibitors. Oil-soluble
chemicals present a different challenge. These chemicals can affect the performance of KHI at
very high concentrations (e.g., > 1,000 ppm). However, the interference can be eliminated in the
presence of hydrocarbon liquids. The interference is attributed to the accumulation of these oilsoluble species at the interface where KHI is acting to inhibit hydrates. Presence of hydrocarbon
liquids facilitates these interfering species to partition back to the oil phase, leaving KHI at the
interface to perform its duty.

11-25

It is important to point out that the distinction of chemical interference based on the solubility of
chemicals is simply a general trend observed thus far. A few exceptions to this trend have also
been observed. Chemical interference of AA by other production chemicals is common. It is
recommended that both physical stability and the chemical compatibility be tested in the
laboratory prior to a field trial. The former testing involves mixing all the treatment chemicals in
the umbilical simulation for the stability under deepwater conditions. The latter testing involves
the performance check in the presence of all potential interfering chemicals.
11.8.3 KHI Lowest Critical Solution Temperature (Cloud

Point)
Another issue of concern is unique to the use of KHI. Kinetic hydrate inhibitors contain
polymers that typically exhibit an inherent property called the lowest critical solution
temperature (LCST). The lowest critical solution temperature is the point when polymers begin
to precipitate form the solution and is very strongly dependent on the solvent used. For this
reason, LCST is sometimes referred to as the cloud point, similar to the cloud point (or wax
appearance temperature, WAT) of wax precipitation.
For example, the LCST of EC6481A is greater than 100C when in its proprietary solvent
package; however, the LCST drops considerably to 50C when the product is injected to the
produced fluid where the solvent for the polymers is changed to brine. The LCST of polymers
used in KHI ranges from 100F to greater than 150F, depending on the chemistry of the
polymer and the salinity of the brine. Concerns were often raised with respect to the hot
injection, such as to the downhole tubing where the temperature could exceed the LCST.
This issue was addressed through formulation technique and simulation studies in the laboratory.
Most KHI packages have been specially formulated so that the finished products remain clear
and stable at temperatures above 100C. Therefore, no precipitation problem is expected in the
injection line or umbilical. However, as the inhibitor enters the produced stream where it gets
further diluted in the brine, the LCST can be substantially reduced by the change of solvent. It is
possible to have polymers precipitated from the solution if the LCST falls below the fluid
temperature. Laboratory simulation work shows that, at a typical concentration (< 5,000 ppm),
KHI polymers precipitate as very tiny species that are very well dispersed in the produced fluids
and continue to migrate downstream. It is unlikely that these highly dispersed species will
deposit under the dynamic flowing condition. These polymers are dissolved easily back to the
solution as soon as the downstream temperature drops below the LCST.

11-26
11.8.4 Solvent Stripping by Gas of LDHI

Similar to the application of any other production chemicals, the possibility of solvents being
stripped by the produced gas must be assessed. Some produced gases can be relatively dry
because the operating temperature is above their water dew point or hydrocarbon dew point. In
such cases, the dry gas has the tendency to strip all the solvents away from the inhibitor, leaving
behind the active species as solid residues. This not only stops the transport of inhibitors to
where it needs to be but also creates a potential plugging problem. Therefore, the
water/hydrocarbon saturation level in the gas phase must be properly assessed before the LDHI
injection. If the produced gas is expected to be under-saturated with water or hydrocarbon, one
of the following three approaches can be attempted to solve the problems:
Pump additional solvents.
Apply special LDHI with a low vapor pressure solvent.
Inject LDHI at locations where temperature is below the dew point.
11.8.5 Physical Properties of LDHI

Physical properties such as flash point, pour point, and viscosity are important issues not to be
overlooked. Among them viscosity is the most critical property that is difficult to be
compromised because of the hardware limitation. Due to the difference in chemistry, AA is
usually less viscous than KHI. The viscosity of KHI formulations increases with the polymer
concentration and molecular weight. To meet this challenge, most KHI packages are formulated
to keep the viscosity low enough for practical use. Viscosity directly affects the pressure drop
across the chemical line and the overall pressure rating of the line. The higher the viscosity, the
more powerful the injection pump and the higher the pressure rating required for the injection
line. Some low viscosity kinetic inhibitors have been successfully formulated to achieve a
viscosity of 15-20 cP at 20C and 25-30 cP at 4C. These low viscosity products are the most
desirable KHI for long subsea pipelines with a small diameter umbilical and a higher KHI
demand.
11.8.6 Injection Maintenance Caution

If LDHI is to replace the existing thermodynamic program, care must be taken to ensure that the
current injection rate is maintained, as if the thermodynamic inhibitors are still being pumped,
until the thermodynamic inhibitors are completely flushed out of the injection line. If the initial
injection rate was turned down before the LDHI reaches to the other end, the produced fluid can
be severely under-treated resulting in rapid hydrate formation. The initial volume (or injection
time) required to flush the existing inhibitors can be readily estimated from the dimension of the
chemical line and the injection rate.

11-27
11.9 Field Monitoring

Proper and constant monitoring of the inhibitor performance is the key to the success of the
LDHI program. Although some prototypes may be under development, there is no standard
hydrate probe in the market reliable and practical enough for on-line detection of hydrates.
The effectiveness of hydrate control programs still relies on the analysis of some indirect but
essential indicators. Most of these indicators are indeed being used in the monitoring program
for traditional thermodynamic inhibition programs.
The first key issue is to make sure that LDHI is delivered where it needs to be and distributed
evenly throughout the system. In the case of subsea flowlines, the operator can look for the
break-through of LDHI at the other end of the line. Depending upon the specific type of LDHI
being used, different indicators, such as foaming, haziness, or discoloration, can be used to
confirm the break-through. Once the break-through of LDHI is confirmed, samples can be taken
to measure the residual chemical concentration. It is not uncommon to see the residual chemical
concentration lower than the target value due to incorrect water production rate or inevitable
adsorption onto solids. If this happens, the operator can check other indicators described below
to decide whether to continue to adopt the current rate or to boost the injection rate to reach the
target concentration.
Increased pressure drop across the pipeline is a good indicator of hydrate formation. The
increase in pressure drop can result from a partial blockage and/or increased viscosity due to
hydrate slurry. If KHI is used for hydrate control, the pressure drop across the pipeline is
expected to have little or no change. If AA is used for hydrate control, one should expect a
small increase in pressure drop due to slurry formation. However, the pressure drop should
remain as a constant after the initial hydrate formation. Any continuous increase in pressure
drop is a sign of blockage caused by agglomeration of hydrate particles.

11-28

Excessive pressure fluctuation is also a good indicator that solid hydrates might be entrained in
the fluid stream, as shown in Figure 17. However, both pressure drop and pressure transient can
also be affected by changes in the production rate, which alone can lead to increased pressure
drop or excessive fluctuations without formation of hydrates. Fouling Index is often used to
eliminate or reduce the effect of changes in production rates from the pressure drop monitoring.
Figure 17 shows two types of pressure drop increases that occur with hydrate blockage of lines.
The left chart shows the gradual increase in pressure drop, which would occur if hydrates form
an ever-decreasing cross-section for the fluid to pass through. The right chart shows the more
typical case of multiple spikes in pressure drop before the ultimate blockage. These spikes are
indicative of particles in the cycle being stuck and released prior to the total blockage.
If KHI is being pumped to the pipeline where pigging is capable, the pipeline should be pigged at
a desired frequency. The fluids collected in the pig trap should be inspected for any presence of
hydrates. Excessive degassing of water can be an indication of a minute amount of hydrates
formed in the pipeline, even though solid hydrates may not be spotted in the pig trap. Regular
pigging is also recommended for the systems treated with AA. Pigging allows the stagnant
hydrate slurry to be removed before it becomes permanently stuck to the wall.
The effectiveness of KHI can also be monitored by observing any sudden drop or gradual
decrease in water production rate. The loss of water may indicate the consumption of water
caused by hydrate formation. The aforementioned indicators are suggested as a tool for the
operators to effectively monitor the performance of LDHI in their systems.

11-29

Chapter 11 Hydrates

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Chapter 11 Hydrates

Hochgeladen von

Copyright:

Verfügbare Formate

Chapter 11: Hydrates