Pembentukan hydrat

What is the Impact of Water Content on the Dew Point and Hydrate Phase Behavior?

In a past Tip Of The Month (TOTM), we have shown that one of the first issues to be
resolved by a facilities engineer working in a gas plant or gas production facility is
where the process is operating with respect to the phase diagram. A general
knowledge, if not a detailed knowledge, will allow the design engineer and the facilities
operator to make intelligent decisions that have significant impact on the profitability
of a gas production facility.
The best way to prevent hydrate formation (and corrosion) is to keep the pipelines,
tubing and equipment dry of liquid water. In this TOTM we will demonstrate how the
water dew point and hydrate formation curves are shifted along a conventional phase
envelope as natural gas is dehydrated.
Case Study:
In order to demonstrate the phase behavior of natural gases containing water and the
impact of water content on the water dew point and hydrate formation temperatures,
lets consider the natural gas shown in Table 1. To generate the diagrams in this TOTM,
we used ProMax [1] based on the Peng-Robinson equation of state (PR EOS) [2].
Table 1. Dry gas composition
Component
C1
C2
C3
iC4
nC4
Sum

Mole %
80.0
10.0
4.0
3.0
3.0
100.0

Results and Discussion:

Figure 1 presents the phase envelope, hydrate formation and water dew point curves of
this gas with a water content of 0.06 mole percent, equivalent to 28.5 lbm/MMSCF (456
kg/106 Sm3). Notice that up to a pressure of about 414 psia (2854 kPa), the water dew
point curve is slightly to the left of the hydrate formation curve. This indicates that the
gas is under-saturated with water at pressures below this point. This also means that it
is thermodynamically unstable and will not form a free aqueous phase. All the water is
converted to hydrate and this state is referred to as meta-stable equilibrium. For
more detail on this meta-stable state, see December 2010 TOTM. Similar behavior is
demonstrated in Figure 2 for which the water content was reduced to 0.0427 mole
percent, equivalent to 20.3 lbm/MMSCF (324.6 kg/106 Sm3). In this case the water dew
point and hydrate formation curves intersect at a higher pressure of 1000 psia (6895
kPa). Below this pressure, the gas is under-saturated and has a meta-stable equilibrium
state. Therefore, the water dew point curve is to the left of the hydrate formation
curve, but above the intersection pressure it moves to the right of the hydrate
formation curve where the water content is above saturation.

Figure 3 presents the superimposition of Figures 1 and 2 having water dew point and
hydrate formation curves for two different water contents (0.06 and 0.0427 mole%).
Notice the hydrate formation curves for both cases coincide with each other for
pressures of 1000 psia (6895 kPa) and higher.
Figure 4 presents the phase envelope along with the water dew point and hydrate
formation curves for the same gas as the water content was reduced to 0.0427, 0.03,
0.0148, and 0.00422 mole % corresponding to 20.3, 14.2, 7, 2 lb m/MMSCF (324.6, 228,
112, 32 kg/106 Sm3), respectively. Notice for all the cases where the gas is undersaturated with water, the water dew point curves are located to the left of the
corresponding hydrate formation curves. Under these conditions the equilibrium state is
thermodynamically unstable (meta-stable) and will not form a free aqueous phase.
However, if the water content is above saturation point, then the water dew point will
position to the right of the corresponding hydrate formation curve and free water will
form under stable condition.

Conclusions:
We have demonstrated the impact of the water content on the phase behavior of a
natural gas. The emphasis was placed on the interaction of the water dew point and
hydrate formation curves. It was shown that the relative location of the water dew
point and hydrate curves with respect to each other is a strong function of the water

content. It was also shown for the cases where water content is above saturation point,
the water dew point curve locates to the right of the hydrate curve. Under this
condition free water forms and then hydrates may form if conditions are right. This is
what is normally expected and shown in text books. However, if the water content is
under-saturated, the water dew point curve will be located to the left of the hydrate
formation curve and the equilibrium state is thermodynamically unstable (meta-stable)
and will not form a free aqueous phase.
As discussed in last months TOTM, facility engineers have to determine how this
behavior affects their operations. These phase envelopes suggest that, at low water
concentrations, hydrates may form even though free water is not present. Indeed, this
phenomenon has been observed. At cryogenic conditions, when the water is removed
by molecular sieves, the amount of metastable water is so small it should not cause
operational issues.
To learn more about similar cases and how to minimize operational problems, we
suggest attending the John M. Campbell courses; G4 (Gas Conditioning and Processing)
and G5 (Gas Conditioning and Processing-Special).
John M. Campbell Consulting (JMCC) offers consulting expertise on this subject and
many others. For more information about the services JMCC provides, visit our website
at www.jmcampbellconsulting.com, or email your consulting needs
to consulting@jmcampbell.com.
By: Dr. Mahmood Moshfeghian
Reference:
1. ProMax 3.2, Bryan Research and Engineering, Inc, Bryan, Texas, 2010.
2. Peng, D. Y. and Robinson, D. B., I. and E. C. Fund, Vol. 15, p. 59, 1976.

Supercharged methanol cuts hydrates

The formation of hydrates in natural gas wells and
pipelines presents a serious concern to oil and gas
producers. Hydrate deposits form solid plugs, reducing
production and ultimately shutting in the well. Costly,
labor-intensive intervention is required to remove the
hydrate blockages and return the well to production.
Traditional usage of methanol to inhibit hydrate formation
has been ineffective.
Improved solutions using low dosage hydrate inhibitors
(LDHI) in conjunction with methanol
have been developed by Baker Petrolite (BPC). The
solution, referred to as Supercharged Methanol, reduces
chemical requirements, resulting in:
Graph 1. The shaded area represents the
operating conditions where hydrates are
unstable and predicted not to form. The area
left of the curve is where hydrates are stable. A
system operating in this region is at risk for
hydrate formation. The red line is referred to
as the Hydrate Equilibrium Curve for the
system. (All graphics courtesy of Baker
Petrolite)

 Reduced hydrate formation;

Reduced costs;
Reduced exposure of personnel to hazardous situations; and
Increased production efficiency.
These benefits reduce lifting costs and improve operating profits.
Production issues
Gas hydrates in natural gas systems are comprised of water and low-molecular-weight gas
molecules. For each production system, hydrate equilibrium curves can be prepared which
take into account gas and water compositions. These curves show the conditions of
temperatures and pressures at which hydrates are thermodynamically stable and likely to
occur.
A wide variety of conditions can exist in a given oil and
gas system. Some of these conditions move a system or
well from the hydrate free zone into the hydrate formation
zone. They include:
High operating pressures;
Sub-surface cool zones (permafrost or aquifers); and
Seasonal surface issues (winter or rainy season).
There are several viable ways to remove a well or system
from the hydrate formation zone:
Reduce operating pressures;
Increase operating temperatures; and
Remove water.
Another approach is to use chemicals which act as hydrate
inhibitors, shifting the hydrate equilibrium curve to the
left, moving the system to the hydrate-free zone.

Graph 2. This graph shows an example of a

well operating at 1,500 psi and 50F (10C),
conditions which are inside the hydrate
formation zone. The subcooling is
approximately 18F (7.7C).

The most commonly used chemical for this purpose is

methanol, a thermodynamic hydrate inhibitor (TDI). If
used in correct quantities, methanol prevents hydrates from forming. Methanol
requirements may be >50% by weight of the produced water. Hydrate-prediction software
can calculate amounts of methanol required, taking into account production, operating
conditions, and chemical compositions of water and gas.
Other chemicals that work at lower rates than TDI, LDHI, are available. LDHI are
classified as
either Kinetic Hydrate Inhibitors (KHI) or AntiAgglomerants (AA). KHI products affect the time it takes
hydrates to form. They delay hydrate formation, allowing
production to flow out of the hydrate-formation zone. AA
products behave differently, allowing hydrate crystals to
form but limiting their size and keeping them oil-wet. This
allows them to pass through the system without forming
deposits. AA products inhibit systems for extended time
periods, making them especially suited for deepwater
projects.

Graph 3. Methanol injection shows a

substantial change in subcooling.

Problems with methanol

While methanol is an effective TDI, there are issues associated with it. Foremost are
environmental and regulatory concerns due to the high amounts required to control
hydrates.
Wells operating in the hydrate formation zone may require high concentrations of methanol
based on water production. For such a well producing 50 b/d of water, 700 gallons of
methanol per day are needed. This requires:
Extremely large bulk tanks on site;
Hazardous material permits; and
Monitoring hazardous air pollutants (HAP) and volatile organic compound (VOC)
emissions.
Safety/environmental hazards are also present when transporting and handling the
methanol.
High financial risk is incurred due to the volatility of the methanol market. Since methanol
price is tied to natural gas price, as gas prices increase, methanol prices increase. Increased
global demand for methanol causes steep price increases. In a single year, the methanol
price may double, making it difficult to plan hydrate- treatment costs. In situations like
these, the tendency is to reduce methanol usage to stay within budget.
Inadequate methanol usage leads to problems as identified by M.H. Yousif (SPE, Westport
Technology Center Int., Effect of Under-Inhibition With Methanol and Ethylene Glycol on
the Hydrate-Control Process, SPE Production & Facilities, August 1998). Studies show
that hydrate molecules and line blockages form more readily in systems using insufficient
quantities of methanol. By reducing methanol amounts, producers may be exacerbating
hydrate formation, creating additional production problems.
Other methanol related problems:
Methanol contributes to corrosion by absorbing and carrying oxygen;
Methanol is a bacterial food source;
it causes water quality and separation problems;
It adversely affects foamers/surfactants used to deliquify wells; and
Refinery issues can result in downgrading of oils and condensates.
Problems with injection systems
Perhaps the weakest link in controlling hydrates with chemicals is the injection system
itself. Regardless of type of chemical inhibitor used, rules apply:
Inhibitors wont work unless injected into the system;
Inhibitors need to be injected at the proper effective
dosage; injecting too much adds additional cost, and not
injecting enough may exacerbate problems;
Inhibitor supply tanks must be refilled (or tank empties
and hydrate plugging occurs).
Several issues have been identified which impair a
chemical injection program: pumps get
air-locked and dont inject inhibitor, rates are set higher
than expected, the inventory is used up prior to

Case 1. Supercharged methanol offers a

substantial gain in well performance.

replenishing the supply, injection lines break, power failures occur, lightning strikes, etc.
Maintaining and inspecting injection systems is labor-intensive. In remote locations
containing thousands of gas wells, it is impossible to insure system reliability.
As a consequence, injection systems arent adequately monitored, resulting in:
Not injecting correct inhibitor amounts;
Failing to change injection rates when conditions change;
Pump failures;
Not inspecting injection systems due to weather;
Failing to replenish chemical inventories;
Forgetting to turn pumps on;
Air-locked pumps; and
Chemical losses due to tank ruptures or line leaks.
For producers, it adds up to losses in revenue, higher operating expenses, environmental
compliance issues and reduced profits.
Hydrate remediation
A variety of methods are used to remediate hydrate problems. When hydrates form,
operators must increase temperatures, reduce pressures or chemically melt plugs.
Remediation efforts expose field workers to unforeseen hazards, as the exact location and
extent of the problem is generally unknown. Injuries and fatalities have occurred owing to:
High pressure buildups on one side of the plug, launching the plug when pressure is
released on the other side;
Highly compressed hydrate plugs causing lines to rupture when heat is applied to the
outside of the pipe (182 cf compressed gas equals 1 cf hydrate).
Released downhole hydrate plugs shooting out through the well head.
Released hydrate plugs in pipelines traveling at
extreme speeds and shooting out of bends in the pipeline.
Additionally, labor costs and lost production due to venting
the wells to the atmosphere to depressurize lines is
extremely costly.
Improved solutions
Working with industry consortia, Baker Petrolite sought to
find the most cost-effective solutions for hydrate control.
Case 2: Revenues increased more than $500 a
Oil and gas production systems are complex with many
day when the proper methanol treatment was
variables. To study the problems and develop solutions,
applied.
BPC uses state-of-the-art laboratory testing methods which enable researchers to evaluate
performance under conditions matching those found in production systems. Specialized
high pressure, thermally controlled test vessels are used to create hydrates in the
laboratory. Software models are employed to predict theoretical treatment rates for TDIs.

Baker Hughes Production Quest has developed solutions to improve hydrate inhibitor
injection systems. These include:

 Pump controllers, insuring injection of exact amounts of hydrate inhibitor; and

Tank level sensors monitoring chemical inventory 24/7.
The controllers and sensors provide automatic, real-time injection system coverage. Alarms
are triggered when processes fail, notifying operators immediately so the problems can be
fixed. These chemical automation systems
have helped producers reduce failures, increased worker safety and improved operating
profitability.
Results from field trials
The results from two field trials performed are presented below. LDHIs were combined
with methanol to improve performance of the hydrate-control program. This combination
product was injected in conjunction with the chemical automation system for improved
control of the injection system. Overall results indicate that hydrate formations were
reduced and system failures declined. Program benefits include:
Improved logistics
- Reduced chemical injection;
- Smaller tankage requirements with increased time between deliveries;
- Reduced costs; and
- Better cost management.
Chemical injection automatically adjusted to conditions
- Instantaneous notification of problems; and
- Changes in system conditions triggering automatic notification.
Improved HSE performance
- Reduced risk due to remediation techniques employed at the field level;
- Reduced road time to/from site; and
- Reduced environmental impact (wildlife disturbance).
Improved profitability
- Reduced total operational cost;
- Increased production.
Case #1
A gas producer in southwest Wyoming experienced severe hydrate problems in a gas well.
The hydrate plugs required high levels of maintenance, and the well produced below
expectations. Continuous injection of methanol failed to control the problem. The remote
location of the well required extensive labor and engineering support to keep the well
running.
The remoteness of Wyoming gas fields makes manual monitoring injection systems
difficult, if not impossible, to do on a timely basis.
Consequently, the producer experienced high operating and remediation costs, production
losses, and lower than expected production. The hydrate remediation also increased safety
risks and environmental concerns.

The service company and producer assessed the problem to determine subcooling in the
well. Hydrate-modeling simulations were run to determine amounts methanol needed. Lab
studies selected HI-M-PACT 5557 KHI as the ideal product to use in conjunction with the
methanol and foamer. The methanol was supercharged with the addition of HI-M-PACT
5557 KHI and applied continuously down the back side of the well, resulting in a
production increase of more than 350 Mcfd.
As a direct result of the LDHI program, production stabilized, treatment efficiency
increased and safety risks were reduced significantly. The customer realized an increase in
revenues of almost US $12,000 per month and a more than 4,000% return on investment.
Also realized was a decrease in workover costs, manpower requirements and engineering
time, and expenses were minimized because the existing chemical system (i.e., storage
tank, pump, etc.) were utilized. The customer maintains lower volume of chemical on site,
reducing Superfund Amendments & Reauthorization Act reporting and making inventory
easier to maintain. Reduced methanol usage lowered hazardous air pollutants at
evaporation ponds.
Case #2
Another Wyoming gas producer was plagued with hydrate problems in gas wells. Although
costly remediation efforts were repeatedly performed to remove hydrate plugs, the well
continued to produce below projections. Continuous injection of methanol was applied, but
it failed to bring the wells performance to an acceptable level.
As a result, the customer experienced high maintenance costs and production losses, and
financial performance was below plan. Safety concerns during the remediation of the
hydrate plugs and the excessive engineering time dealing with hydration remediation were
also issues.
The service company and the producer assessed the problem. Hydrate-model simulations
and lab tests were run to determine the optimal chemical amounts. Based on the tests, HIM-PACT 5458 KHI was selected as the most favorable KHI to use with the methanol. The
results were a supercharged methanol/KHI product that proved highly successful for the
customer.
Utilizing the treatment program, gas production increased more than 65%, and revenues
increased more than $500 a day. The return on investment was almost 4,800%, and the
payback period was about 29 minutes.