Office of Research and Sponsored Programs

Hydrate Flow Performance JIP

16th Semi-Annual Advisory Board Meeting

Brochure and Presentation Slide Copy

Pushing the Hydrate Phase Envelope

Principal Investigators
Dr. Michael Volk
Emmanuel Delle-Case

November 2010
Confidential

1.0 Pushing the Hydrate Phase Envelope Executive Summary

Mike Volk
1.1 Scope of Work
The results from the prior phase of study show that to some degree hydrates can be transported and
there may be a safe zone of operation where hydrates could be transported in the hydrate domain.
The gas and liquid restart studies showed that liquid holdup was over estimated with current simulators
while the low pressure hydrate formation tests in the jumper showed being able to predict this hold up is
critical in that a relatively small amount of water plugged the jumper upon restart and little is known
about mixing of the inhibitors upon displacement. CFD models were developed and the holdup
predictions were improved by 50 % showing promise for further development.
Hydrate plugs were characterized and dissociated. Current models were found to be adequate for
dissociation by heating but the depressurization model was not applicable because the dissociation
was not uniform. No inhibitor model exists but a first generation model was developed during the prior
phase of study.
The prior phase of study quantified the hydrate plugging risks while the work in this phase of study will
try to quantify how far into the hydrate envelope production can go. The work consists of four tasks
supported by 40 experimental runs with the hydrate flow loop and 90 runs in the jumper facility. The
experimental work will be performed in the University of Tulsas Hydrate Flow Loop Testing Facility.
1.2 Tasks
Task 1: Hydrate transportability during steady-state operations
Determine parameters affecting transportability
Determine maximum transportable hydrate fraction with & without use of chemicals
Determine and correlate pressure drops
Task 2: Hydrate risk and inhibition during restart operations
Conduct inhibitor displacement experiments in the 3 jumper facility
o MEG and MeOH
o Brine: Fresh and 14% salinity
o THI superficial velocity: 0.05 to 1 ft/s
Measure THI concentration profile in jumper
Compare experimental data with CFD simulations
Validate findings with hydrate experiments
Task 3: Conduct Hydrate Formation Studies on Under-inhibited Systems
Interface development and hydrate growth
o Cyclopentane and propane
o Un-inhibited, under inhibited and inhibited systems
o MEG and MeOH
o Induction time
o Wall deposition and aggregate size distributions

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November 2010

o Liquid droplet/hydrate particle interactions

Adhesive forces between under-inhibited water and hydrate formers (CSM)
Relations between forces and observations

Task 4: Improved dissociation modeling

Conduct depressurization and inhibitor dissociation experiments
Modify dissociation model to account for non-uniform pressure dissociation
Develop robust and reliable DEH dissociation model that can analyze and quantify the risk
involved
Convert first generation inhibitor model into a robust model
Desired results from this work include:
Operating envelope for hydrate transportability
CFD model / engineering tool to assist in the design process of future jumper installations.
Universal dissociation model for heating, depressurization or inhibitors.
The schedule for completing the complex and interrelated tasks is shown in Figure 1. The study will last
two years, finishing in 2011. Figure 1.1 also shows when significant deliverables in the form of reports,
model validations, and data will be provided to the participants. Those activities colored in green are
completed while those colored in blue are scheduled.

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November 2010

Figure 1.1 Task Chart for Pushing the Hydrate Phase Envelope Studies

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November 2010

1.3 Activity Summary

The progress for the four projects is discussed below.
Project 1 Hydrate Transportability
From recent flow loop studies conducted at the University of Tulsa, as well as analysis of past
experiments, it appears that hydrates can be transported safely, without inhibitor, with a solid fraction
between 5% and 25% depending on operating conditions. Accurate predictions of pressure drops and
maximum transportable hydrate solid fractions are a necessary step for integration into existing
simulation codes and a critical step towards slurry flow technology. Better confidence in these
predictions and existing slurry flow models is needed before such technology can be deployed in the
field. The purpose of this study is to provide this increased confidence level in slurry flow technology by
focusing on the following aspects:

Identify the operating parameters that have a strong effect on flowing pressure drops.
Identify a safe maximum transportable hydrate fraction and its dependency on operating
parameters.
Correlate when possible the frictional pressure drops with solid hydrate fraction in the flow
stream and other relevant parameters if needed.

These findings would result in better use of existing models and better pressure drop modeling, in an
increased confidence in the feasibility and limitations of hydrate transportability.
The focus of the experiments this reporting period was to understand the effects of different parameters
on hydrate transportability for Natural Gas-Water experiments. Natural Gas-Water tests were chosen to
segregate the effects of oil chemistry on transportability. Twenty-two steady state experiments were run
and pressure drops were plotted as a function of hydrates in the liquid for each of these experiments.
From the shortcomings in analysis, modifications were made to the flow loop, new experimental
procedures were determined and additional experiments were run to characterize the fluid and also
check for the effect of heat transfer. Experiments to understand rheology were also conducted.

Project 2 THI Displacement: Mixing and Modeling

The risk of hydrate formation causing blockage of production lines and subsea equipment has become
a matter of major concern during the last few years as offshore developments move into deeper waters
with lower seabed temperatures and higher fluid pressures. Subsea jumpers are particularly
susceptible to hydrate plugging due to their characteristic configuration, which consist of small
diameters (in comparison with production and distribution lines) and low spots where the water is prone
to accumulate and eventually form hydrates. Current operational procedures to avoid hydrate plugging
of subsea jumpers include insulation, electrical heating, dead crude oil displacement and injection of
thermodynamic inhibitors. The latter is the most common of these methods, and solutions of methanol
and glycol (MEG) are often employed.

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November 2010

Design procedures are needed that reduce the risk of hydrate plugging, protects system integrity and
offers a means to control the amount of chemicals to be used, while keeping the CAPEX and OPEX
within acceptable project economic limits.
The objectives of these THI displacement, mixing and CFD model development studies are:

Conduct jumper experiments to gain a better understanding of the interactions between density
difference and viscosity for thermodynamic inhibitors.
Quantify the suitability and effectiveness of MEG and methanol in jumper flushing procedures.
Utilize CFD modeling to obtain better insight into the complex physical phenomena of jumper
inhibition.

Modifications to the previous jumper facility were completed this period in order to begin the THI
water mixing experiments as well as the hydrate tests using cyclopentane. A stainless steel tank was
set for holding the methanol and MEG and a chemical resistant gear pump and a Micromotion
flowmeter were connected to complete the inhibitors injection system.
Twenty four experiments using MEG and fresh water have been conducted. The initial water volumes
for all tests were approximately 34 and 17 gallons, which correspond to full and half liquid loading
conditions, respectively. Inhibitor velocities varied from 0.05 ft/s (1 gpm) to 0.91 ft/s (20 gpm) and
equivalent volumes of 1 and jumper were injected for each case.
CFD simulations were performed using FLUENT 5.3 and the model was set up using the Species
Transport equations. The computational mesh uses 592,000 cells. A 2D structured grid was
considered, which consists of quadrilateral cells only. This particular type of mesh is recommended for
regions of high gradients in the flow field. At the zone near the inhibitor inlet, the mesh is denser to
capture the features associated to the entrance of the fluid to the jumper; while in the rest of the
geometry the grid is coarser. The meshing process was carried out using Gambit 5.0.

Project 3 Understanding Hydrate Formation Mechanisms in Under-inhibited Systems

This project characterizes interface development and hydrate growth in under-inhibited conditions with
cyclopentane and propane. Tests will be run in a clear pipe at low pressure. Independent variables will
be water cut, inhibitor concentration, subcooling level, and mixing rate. We will look at the induction
time, total formation time, and formation rate. We will determine whether or not the hydrates deposit on
the pipe walls and measure aggregate sizes and size distribution as visibility allows. Adhesion forces
between under-inhibited water and cyclopentane will be measured through a sub-contract with
Colorado School of Mines. Interactions between liquid droplets and hydrate particles will be recorded
with high-speed video. The adhesion forces will be related to experimental observations. Any hydrate
plugs that form will be characterized (porosity and permeability) and dissociated with MEG or MeOH.
The literature review on under inhibition of hydrates was completed this period. Taking the results from
the literature into account, an experimental program was developed for the propose project. The design
of the facility was completed and bids for construction of the facility were sought. The bids were
reviewed and a contractor was chosen. Construction will begin in November. This facility includes an 8
long, 3 ID glass test section which is jacketed by a 7 long, 6 ID pyrex pipe. The test section can be

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November 2010

rocked (in horizontal position) or bubbled (in vertical position). The material for the test cell was
ordered.
Project 4 Comprehensive Dissociation Model
Work on hydrate dissociation modeling is limited. Peters (1999) modeled the two-sided hydrate
dissociation with a radial moving boundary. The model is capable of predicting the hydrate dissociation
time and the total time for plug melting. CSMPlug is the plug dissociation computer program generated
out of the initial two-sided dissociation model of Peters, extended by Bollavaram (2003) for one-sided
dissociation and for electrical heating by Davies et al (2005). The model is based on Fouriers law of
heat transfer in cylindrical coordinates and takes into account hydrate, ice, and water phases. This
model is used by industry. The University of Tulsa has developed an extensive hydrate plug database
for melting, depressurization and inhibitors. Comparison of CSMPlug predictions to this database
shows good agreement for heat dissociation but not for depressurization because the experiments
show non-uniform dissociation. No model is available for inhibitors.
This project will develop a numerical model to simulate and understand the physics and risks of hydrate
remediation processes by electrical heating/thermal dissociation. The starting point is TUs heating
dissociation model. The proposed model will eventually account for changes in porosity and
permeability of hydrates during dissociation. Pressure buildup, accompanying equilibrium changes, and
hydrate thermal expansivity will be included. A thermodynamics package will be incorporated, and
water will be allowed to refreeze. Two modes will be available: constant pressure and pressure
buildup. A comprehensive analysis will be conducted to study the risk of pressure buildup in the
pipelines that are perceived to be associated with the direct electrical heating techniques for hydrate
remediation.
An overall dissociation model will be developed that will include an inhibitor model and combine all of
TUs models into one program. The inhibitor model will be guided from knowledge gained in Project 3.
TUs current heating model will be replaced by the model developed in this study when it is
demonstrated to be better than the current model. Validation experiments will be done in the flow loop
for dissociation by inhibitors and depressurization, and the models will be improved based on these
tests. Then the heating, depressurization, and inhibitor models will be packaged together into one
program.
A literature review related to the available DEH techniques and models was conducted. Two commonly
referred to models were identified; one by CSM and the other by Mehta at Shell. The assumptions and
limitations were identified and an effort to develop a 2D model that provides conservative predictions of
pressure buildup before and after dissociation was begun.
1.4 % Completed: 40%
1.5 Conclusions/Observations
Hydrate Transportability: Repeatability of experiments was between 20-37% for hydrate fractions up
to 8% for the 62.5% liquid loading, 3.9 ft/s mixture velocity, 40F/hr cooling rate, constant mass tests.
The experiments were repeatable provided the pressure-temperature profile was repeatable. The subcooling at hydrate onset is uncontrollable and this led to the variation in results. The phenomenon
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observed in the tests which slug is similar to what is observed with heavy oil flow in that there is no flow
between slugs. Hydrate transportability for 90% liquid loading tests was increased to a Solid Liquid
Ratio of around 60% through constant mass stage gas/mass addition experiments. This indicates that
Solid Liquid Ratio and pressure drop cannot be criteria to determine up to what fraction hydrates are
transportable.
The effect of heat transfer on the flow loop for experiments with one leg chilled and with the other leg
quasi-insulated appeared to be insignificant other than at hydrate onset; that is, there was no significant
wall effect seen due to heat transfer.
New phenomena were observed for tests with gas injection from the bottom for 90% Liquid loading.
Gas bubbles are coated with hydrates by the time they reach the gas water interface. Once they reach
the interface, jamming phenomenon is observed in the gas portion of the pipe. Rheology experiments
for natural gas-water hydrate slurries exhibited pseudo plastic behavior at mixture velocities below 6 ft/s
and above 6 ft/s; the mixture adhered to the Bingham plastic model.
THI Mixing and Displacement: Experimentally, higher inhibitor velocities (v > 0.45 ft/s) contributed to
displacement of the water as a slug. Uniform radial MEG concentrations were measured in the 2nd low
spot at high injection rates. However, lower velocities (v < 0.2 ft/s) promoted mixing of the inhibitor with
the water phase. Concentration profiles over time fit the classical trend given by the convectiondiffusion equation. The repeatability assessment showed that the current sampling procedure allowed
obtaining experimental concentration data within 5% and 11% uncertainty. For MEG displacement
equivalent to a jumper volume, lower velocities contributed to a better inhibition of the water present
in the low spots. Since the mixing front is longer at low injection rates, the dispersion of the ethylene
glycol is greater.
CFD 2D simulations employed the species transport equations allowing modeling the mixing
phenomenon of MEG and water at low velocities (0.05 ft/s) during jumper restart. Experimental trends
were reproduced with a deviation of 10%. Conversely, large errors were obtained at intermediate and
high injection rates. Diffusion effects were found to be significant at short times, whereas at longer
times transport of MEG into the water phase dominated the inhibition mechanism.
Dissociation Studies: A dissociation model was built from first principles. From this effort it was
concluded that it may be necessary to include the dissociation chemistry in the continuity and energy
equations (to couple the diffusivity and energy equations). This will require a more complex solution
procedure but should lead to better numerical stability and shorter computation times.
1.6 Future Work
Hydrate Transportability: Detailed analysis will include simulations run in OLG and Flowasta to check
the various effects observed in the experiments. Simulations will include a sensitivity study of the effect
of parameters such as sub-cooling, attractive forces, slip. Comparisons will be drawn between
simulations and experimental data to try and point out the shortcomings of the existing models and the
phenomenon that the existing models cannot capture. Further natural gas-water experiments will be
conducted to check the effect of liquid loading, gas composition, pressure, salinity, velocity, under
inhibited systems at low velocities and hydrocarbon phase on the transportability of hydrates. Additional
experiments on cooling rate using the computer ramp will be considered. Extrapolation of experimental
results will be made to real field situations to see how the results compare.

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THI Mixing and Displacement: Experiments to evaluate the effect of brine salinity on MEG dispersion
will be conducted as will gas restart cases when jumper volume of inhibitor is displaced. The facility
will then be modified to carry out static runs (bottom injection in riser, top injection in riser). The test
apparatus will then be used to conduct low and high velocity experiments using methanol.
A CFD sensitivity analysis (Grid size) will be conducted. Simulations of the effect of temperature (25C
vs. 4C) will be made as will a performance of the VOF (Volume of Fluid) model in predicting the
displacement mechanism of the water phase at high inhibitor velocities. Once the methanol
experiments have been run an evaluation of methanol behavior during jumper flushing at low and high
rates will be conducted.
OLGA will be used to assess the performance of a transient 1D model in predicting the local
concentration of thermodynamic inhibitors in the water phase during restart. Scale-up studies using
larger geometries after the CFD model is validated will be conducted using 6, 8 and 10 jumper
configurations considering the same velocities and compare concentration profiles.

Understanding Hydrate Formation Mechanisms in Under-inhibited Systems: The

construction of the test facility will be completed and shakedown experiments will be conducted.
Experiments at atmospheric pressure (with hydrate former as cyclopentane) will be conducted in order
to observe the interaction development and hydrate growth in un inhibited and inhibited systems. The
independent variables that will be studied are water cut, inhibitor concentration, sub cooling level and
mixing rate. Experiments at lower inhibitor concentrations using Methanol (MeOH) and mono ethylene
glycol (MEG) will then be conducted. A high speed video camera will be used to record the hydrate
formation and deposition.
Dissociation Studies: During this phase, additional depressurization tests will be conducted to verify
the depressurization model. These will be followed by runs with extended MEG, methanol and nitrogen
dissociation experiments using large volume of inhibitor with increased injection rates The construction
of the test facility will be completed and shakedown experiments will be conducted. Experiments at
atmospheric pressure (with hydrate former as cyclopentane) will be conducted in order to observe the
interaction development and hydrate growth in un inhibited and inhibited systems. The independent
variable that will be studies are water cut, inhibitor concentration, sub cooling level and mixing rate.
Experiments at lower inhibitor concentrations using Methanol (MeOH) and mono ethylene glycol (MEG)
will then be conducted. A high speed video camera will be used to record the hydrate formation and
deposition.. For these experiments the density of MEG will be measured while draining liquid and for
the nitrogen tests the composition of vented gas will be measured. The first generation inhibitor model
will be converted into a more robust model and then validated using the results of the planned
experiments.
For the comprehensive model the future work is running validation experiments in the flow loop and
chaining individual cells together into a longer plug, to allow an inhibitor concentration gradient along
the plug.
A 2-D DEH model will be developed that provides conservative predictions of pressure buildup before
and after dissociation. This model will allow pressure buildup and account for changing dissociation

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temperature, interface with PVTSIM (for variable gas composition), study the effect of variable porosity,
permeability changing with space and account for thermal mass, non uniform heating or hot spot. The
user will be able to define length to diameter ratio of the plug, type of hydrate structure, variable
porosity, and permeability, mass of hydrate and trapped phases, heat flux, ambient temperature, initial
temperature, and be able to introduce a hot spot in a given section of pipe. The user will be able to run
the model in both the pressure buildup mode (closed system) and the constant pressure mode
(controlled). Experiments will be conducted to form exclusively S-I and S-II hydrates in the 3 flow loop
to obtain thermal dissociation data. The final step would be validation of the model to experimental
data.

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