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inthePresenceofHydrates
TechnologyEvaluationReport
University of Utah, Salt Lake City - Milind Deo, Jules Magda and Rich Roehner
Contents
Executive Summary ........................................................................................................................ 3
Background ..................................................................................................................................... 5
Technology Review Methodology.................................................................................................. 5
Technologies ................................................................................................................................... 6
Cold Flow.................................................................................................................................... 6
Pigging ...................................................................................................................................... 11
Internal Coatings ....................................................................................................................... 13
Chemical Inhibition .................................................................................................................. 14
Sonic Methods .......................................................................................................................... 16
Biodegradation and other methods ........................................................................................... 17
Coiled Tubing and Active Heating ........................................................................................... 18
Summary of Findings from Deepstar 6302 ............................................................................... 19
Summary of Economics of Cold-Flow from Deepstar 7901-8 ................................................. 21
Ranking Criteria (1-10 on each) ................................................................................................... 22
Proposed Research ........................................................................................................................ 23
Proposed Laboratory Evaluation(s) .......................................................................................... 23
Key References ............................................................................................................................. 26
Appendix Literature Review Reports and Presentation ............................................................. 29
Executive Summary
Technologies for enabling transport of crude oil under cold flow environments were examined.
The focus was on finding game changing technologies using single uninsulated tiebacks and/or
export lines. For subsea tieback, technologies capable of handling both the hydrate and wax
deposition problems at the same time are needed. However, the scope of this project is limited to
wax deposition issues. We will perform some exploratory experiments to study the influence of
hydrates.
A relatively new concept of cold flow has been proposed and discussed in some recent patents,
papers and reports. In this approach, the flowing steam is cooled to sea-water temperatures, and
is seeded with hydrates and/or wax particles. The increased deposition area internal to the flow,
and significant reduction of the radial thermal flux are considered responsible for reducing
deposition on pipeline walls. Bench-scale experiments have demonstrated the effectiveness of
the concept for hydrates, waxy oils and in cases involving the formation of both hydrates and
waxes. In terms of fundamental basis for the technology and range of applicability, cold flow is
further along for hydrates than for wax. In comprehensive Deepstar reports, questions
concerning the applicability of wax cold flow technology, and the economics of transporting
slurries have been raised. There is also a need to answer fundamental questions concerning
slurry creation, particle morphology and mixture rheology. Even so, cold flow is one of the
technologies that might make long-distance unisulated tiebacks possible in deepwater, and is
being considered for further evaluation.
Pigging technologies are critical for pipeline management in deepwater. There have been a
number of advances in pigging technologies including pigs capable of crawling upstream. These
types of pigs and subsea pig launching schemes are expected to provide the necessary backup for
commercial implementation of cold-flow technologies.
Three types of thermal management options are available. Insulation and active heating are
currently being used, but are expensive. In-situ heat and gas generation methods (by using
chemicals causing an exothermic reaction) are not likely to be applicable in the deepwater
offshore United States due to types of chemicals involved and due to other control issues.
Chemical injection has also been used as a wax/hydrate mitigation strategy. The science and
practice of chemical injection is advanced. However, the mitigation strategies are typically
designed to address specific chemical compositions and conditions. Very few studies address
mitigating waxes and hydrates at the same time. It is unlikely that an inexpensive chemical
injection strategy could be used to design cold flow. Targeted chemical injection would always
be part of the total solution.
Different types of coatings have been proposed for preventing or minimizing deposition. The
flowing conditions also impact deposition. We found that in general, coatings are not effective
in preventing deposition and will not be applicable to cold flow.
Sonic, magnetic, microwave and biodegradation methods are in various phases of research.
These technologies will not be applicable for long-distance cold flow applications in their current
states of development.
Based on our evaluation, we propose a fundamental evaluation of the cold flow concept. The
research program we propose will consist of the following elements.
Background
The purpose of this project is to develop a fundamental understanding of alternatives for
preventing wax formation in deep water, uninsulated subsea pipelines. This project involves two
phases: (1) a comprehensive literature review concerning flow in subsea pipelines, hydrate and
wax formation, and methods designed to prevent or mitigate deposition; and (2) experimental
evaluation of one or two of the most promising technologies/concepts based on the review.
Unique challenges are associated with transporting hydrocarbon fluids through long subsea
pipelines associated with deepwater oil and gas production. Wax precipitation in these flow lines
due to the cold temperatures is a serious problem. One way of preventing wax precipitation in
long subsea lines is to insulate them; an expensive solution. A number of other wax control
technologies have been proposed, some of which are being employed commercially. These
include mechanical methods such as pigging, chemical injection technologies, and thermal
management strategies, which focus on preventing the problem. One concept that has been tested
recently but has not been implemented commercially, is a process termed cold flow. The idea
is to engineer a controlled formation of slurry made up of hydrate and/or wax particles. Flow of
the oil-water mixture can be managed in the presence of this slurry. The seed particles in the
slurry act as nucleation sites and prevent or minimize further wax deposition in areas that might
restrict flow.
In previous studies, no single strategy had proven to be completely effective in preventing and/or
remediating the problem. There was a need to carefully evaluate all available technologies and
select one or two for further evaluation. The purpose of this study is to identify gaps and
challenges, associated with each option for preventing wax precipitation in un-insulated
pipelines. The general approach will be to look at broad classes of technologies: mechanical
methods (e.g., cold seeding, sonic methods, scrapers (pigs), internal pipe coatings, coiled tubing
services, etc.), chemical methods (e.g., inhibitor and solvent injections to prevent or minimize
the rate of wax deposit accumulation), and thermal management techniques (which provide the
necessary heat input to prevent deposition).
Technologies
Cold Flow
The deposition of the wax and/or hydrates consists of two separate, but interdependent
components precipitation and deposition.
Precipitation is primarily controlled by
thermodynamics, while deposition is impacted by heat, mass and momentum transfer processes.
Cold flow takes advantage of the fact that while there may be solids present in the liquid being
transported, driving forces for the deposition of these solids is either minimized or eliminated.
The concept of cold seeding is illustrated in Figure 1. The oil is cooled temperatures around the
seawater temperature in a mechanical device. Generally, the wax appearance temperature (WAT)
of the oil is greater than the seawater temperature. As a result, certain amount of wax precipitates
in the device. The solids formed are then transported as a slurry along with the associated liquid.
With the fluid temperature equal or near the seawater temperature, the presence thermal flux is
minimized or eliminated. This thermal flux is considered the main driving force for wax
deposition, leading to a belief that further deposition in the pipeline would be minimized.
Furthermore, the WAT of the liquid is likely to be considerably lower in comparison to that of
the original oil due to the fact of the heaviest paraffinic components are out of solution.
Detailed studies of cold seeding for waxy oils were reported in Deepstar Report 4202-b2.
Nenniger Engineering, Inc. (NEI) designed and built an apparatus for collecting wax deposits in
the laboratory, and to test the seeding concept. The seed dose provided a particulate surface area
of four times the wall area. An 80% reduction of wax deposition rates was observed. At lower
temperatures, the inventory of naturally occurring suspended waxy solids increased in the oil,
and the seeds became less effective. In the proof of concept testing phase of this project,
synthetic seeding (polyethylene powder) was employed.
Tflow = Twater
Figure 1: The concept of cold seeding is to cool the oil sufficiently to precipitate some solids and
transport the resulting slurry in the pipeline.
Several publications (Merino-Garcia and Correra, 2008) describe the mechanical device for
making the cold slurry. A prominent invention described in a patent is shown in Figure 2.
Precipitated Wax
Wax Eater
Cold Slurry
T = 3~4 oC (Seabed)
Hot Oil
Figure 2: A concept for making the slurry in wax cold flow applications. The device is known as
Wax Eater.
In the Wax Eater the hot oil enters a loop that is maintained at colder temperatures to cause
solids precipitation. A pig goes around the loop scraping the wax and placing it in slurry. The
7
cold slurry is transported out of the loop. The mechanical operations of the loop, including the
temperatures to which the incoming fluids are cooled, stability of the pig to circulate and scrape
the wax, etc. were cited as some issues that needed improvement.
Other cooling and wax removal approaches have also been proposed and have the tested at
various levels. High Shear Heat Exchanger (Fung, 2003) was proposed wherein the turbulence
generated in the device was adequate to remove solids. No experimental evidence was available
to understand the range of validity and limitations of this concept.
The concept of causing wax precipitation by using the Joule Thompson effect was proposed by
Knowles, Jr. et al. (1986). The concept is illustrated in Figure 3. The concept has not been tested
extensively. High velocities at the point of constriction may be sufficient to disengage the
formed wax and transport it as slurry.
Another Method of
Creating A Slurry
Dissolved Wax
Precipitated Wax
Gas
Shell Process
Figure 3: The flash cooling concept utilizing the Joule Thompson effect to bring upon solids
precipitation.
Cold Flow Applied to Hydrates
Cold flow technology as applied to hydrates has been discussed in a number of papers and
patents (please refer to Appendix 1). Turner and Talley (2008) published a comprehensive paper
on formation of hydrate slurries and on factors affecting the flow of slurries. Nonadhesive
hydrate slurries were formed and these exhibited reasonable viscosities in a flow loop when
formed under certain conditions. They observed that the factors that favor formation of low8
viscosity hydrate slurries include high Reynolds Number, and high mass transfer and heat
transfer rates. The effects of other operational parameters like velocities and liquid loading were
also examined. Mixing devices for the creation of appropriate slurries were also identified in this
study. Hydrate slurry formation and some flow characteristics of the slurry have been reported
by researchers at the Norwegian University at Science and Technology. Some of the basic
particle formation characteristics and rheological slurry properties required for transport were
described by Andersson and Gudmundsson (1999). Excellent research on hydrates has been
carried out over a long period of time at the Colorado School of Mines by Dr. Sloan and his
group. In one of their recent publications (Boxall et al, 2008), they described some new
analytical procedures for characterizing hydrate particles.
Cold Flow Applied to Hydrates and Wax
The concept of cold flow has also been proposed and tested to address hydrate problems. Lund
et al. (1999) created slurries consisting of hydrate particles. The particles act as seeds for particle
growth preventing deposition and plugging of both wax and hydrates. The technology and
applications to crude oils containing waxes and hydrates has patented by SINTEF has been
discussed in a number of publications and in some Deepstar reports. Larsen et al. (2007)
describe Cold Flow as a system in which hydrocarbon production fluids are flowing at
thermodynamic equilibrium in uninsulated pipelines, without the help of chemical modifiers
(thermodynamic or kinetic gas hydrate inhibitors, low-dosage anti-agglomerants, or wax
modifiers), and without the help of active or passive heating or heat-retention schemes. The
flowing slurry comprises of inert particles (e.g. gas hydrates and/or wax particles). Numerous
experiments were carried out. The 1 diameter loop was operable with reconstituted well fluids
and with an appropriate gas phase added to adjust hydrate equilibrium conditions. Several crude
oils from different oil provinces around the world (Gulf of Mexico, and West of Africa) were
Cold Flow tested in this facility.
The baseline tests for wax and hydrate deposition were carried out first. About 0.6wt% of the
total wax was deposited and the maximum allowable water content in hydrate tests was 4%. In
all the experiments, the seeds were already added to the cold fluid. The nature of the seeds,
morphology, etc. was not reported. An order of magnitude reduction in wax deposition was
observed under cold flow conditions. In experiments with hydrates and wax, a ten-fold increase
in water handling capability was observed.
In summary, the cold-flow hydrate technology appears to be further along than the cold-flow
wax technology. At bench-scale, the technology has been demonstrated and appears applicable
over a wide range. Scientific basis for the technology is sound. There have been some
publications that describe control of wax and hydrates with cold-flow. Some Deepstar reports
have raised questions about the feasibility of cold-flow wax and about the economics of hydrate
slurry pumping. Even with these questions, cold-flow technology may make it possible to run
9
long uninsulated tiebacks. There are still fundamental questions concerning slurry creation,
thermodynamics, slurry properties and restart. We plan to address these fundamental questions
in the Phase II of this project.
10
Pigging
Pigging commonly refers to passing engineered solids through a pipeline in order to clean and/or
inspect the pipeline. The status of pigging technology has been heavily reviewed in both the
Deepstar and open literature (Listed in the Reference). In particular, the need for development of
reliable single trip pigging operations to eliminate the use of round trip pigging and dual
flowlines has been highlighted (Deepstar Report CTR 4303-1, 2000 and Deepstar Report CTR
6302, 2004) as essential for pushing the feasible lengths of subsea tie-backs. The amount and and
character of the solid deposits which could result during cold flow will likely affect these single
trip pigging operations; thus these effects must be quantified. In particular, the frequency and
typical mission parameters of cold flow-single pigging has yet to be well identified. At least one
cold flow seeding technology is relying on pigging technology to help create the cold flow slurry
(DSV CTR 5201-3a, 2001), and this type/design of pig may or may not be the best type of pig to
run in the longer subsea-tieback line itself.
A force balance for a scraper pig has been described in the literature (reference 1) as follows:
Ft = Fb + Fs + Fws
Where,
Ft = Total Force to move Pig (Static force for constant velocity, no acceleration).
Fb = Baseline force (frictional) between Pig and Pipe Wall
Fs = Breaking force of wax (gel strength?)
Fws = Frictional force between Wax Plug and Wax Deposit
Ideally these forces should be quantified from field pigging data of cold flow demonstration /
pilot scale tests for different flows (i.e. multiphase, export oil, etc.). From this type of data, and
other typical flow assurance evaluations, guidelines can be prepared for allowable pigging
interval/frequency. Specific design of pigging methods for generation of cold flow slurries such
as the wax eater (Deepstar CTR 5201-3a, 2001) can be envisioned based upon identification of
characteristics and trade-offs of various cold seeding methodologies for creating cold flow
slurries.
Once the above information is available, mechanical designs for pigging tools which incorporate
the latest technological developments for dealing with traditional concerns such as multiple
diameter lines, subsea launching, and flow bypass could be completed. Novel designs such as
employing ice pigs (Robins, 2003 and Shire et al., 2005.) can also be more effectively
considered.
11
12
Internal Coatings
Internal coatings are used to prevent wax crystals and particles from precipitating onto the
internal walls of pipelines. Common coatings are phenolics, epoxies, phenolic-epoxies,
polyurethanes, nylon, and Teflon (Buck, 2006, DEEPSTAR DSIIA A906-1, Volume 1). In
theory, the chemical nature of the coatings should work to prevent wax-surface molecular
interaction; in experiments and field tests, however, physical parameters turn out to be more
important in determining the effect of the coatings on deposition (Buck, 2006 and Efner, 1996,
DEEPSTAR 3205-1). In addition, many tests have shown that the insulator nature of some of
these coatings does more to prevent deposition than its chemical nature (Efner, 1996,
DEEPSTAR 3205-2 and Hsu, 1997, DEEPSTAR 3205-3). Surface finishing for smoothness in
an effort to reduce fluid-pipe friction has failed in every test to prevent deposition, and various
studies have concluded that internal coatings have no effect whatsoever on preventing wax
deposition (Efner, 1996, DEEPSTAR 3205-1).
One study in particular, however, has shown that nylon coatings seem to decrease wax
deposition at high flow rates and temperatures close to the cloud point temperature (Hsu, 1997).
This may be of interest in cold flow technologies, but it will need to be determined if the
deposition reduction holds for slurries below pour point. Also, wax-hydrate interaction with
nylon coatings has not been tested. All other coating technologies would be insufficient for cold
flow systems.
Ranking for application to cold flow conditions would be 1-3, with the only consideration given
to nylon coatings after additional testing as previously recommended. The scientific basis works
in theory, but physical application counters the theory, resulting in a rank of 2. Cost is a definite
concern with application due to the large amount of needed specialty material, giving a rank of 3.
There is an enormous range of possible failure, resulting in a rank of 1 (again, consideration
should be given to nylon).
13
Chemical Inhibition
Properties of chemicals affecting pour point depression are described by Mankan and Ziegler
(2001). Usually, these are polymers of certain characteristics.
The enhancement of interaction between the inhibitor polymers and waxes in oil is
important.
The polymer backbone has a slight effect on the pour point depression.
The pendant chain carbon number has an optimum with respect to its effectiveness.
The polymer molecular weight has no significant impact.
Properties of solvents to keep the polymer in solution are also important.
The performance of wax inhibitors with different oils (Garcia et al. 1998) is shown in Table 1.
The performances of wax inhibitor polymers improve when they are used in accordance with the
oil composition.
Table 1. Impact of oil composition on the effectiveness of the wax inhibitors
Item
Effective
Ineffective
low
high
Quantity of C24+
Wax distribution
Bimodal
Monomodal
Pedersen and Rnningsen (2003) showed the effect of wax crystal modifiers on WAT, pour point
and viscosity. The chemicals used were polyalkyl methacrylate, copolymer of ethylene and vinyl
acetate (EVA), polymeric fatty ester, copolymer of polyalkyl acrylate and vinyl pyridin, mixture
of EVA and copolymers of maleic acid anhydrate and -olefin. Major viscosity reduction was
observed in the temperature range of 10-25oC for all the cases of the chemical doping up to 1000
ppm. This result provides proof that the chemicals prevent the formation of wax network by
interacting with waxes of the carbon number range from C21-C45.
The effect of chemical structure on pour point depression is tabulated in Table 2 as an example.
The chemical doping of acrylate polymers results in significant reduction of pour point compared
with the addition of ethylene vinyl acetate (Lindeman and Allenson, 2005).
14
Table 2. Performance of different classes wax inhibitors. The tests were performed with 1000
ppm of additives in the same crude oil (the pour point of oil used was 18 oC without inhibitors)
Ethylene vinyl acetate
Ester-type
ELVAX 150
ELVAX 240
Polyacrylate
Polynethacrylate
Molecular
weight
87,767
82,900
97,730
103,900
Tm (oC)
60-63
70-74
53
48
Degree
of
Crystalinity, %
50-55
20-26
-12
-15
Polymer
10
Some low-dosage chemicals for prevention of hydrates and waxes are common. There is not a
lot in the open literature about the nature and mechanism of these chemicals.
Chemical inhibition alone would not be applicable to cold-flow. Targeted chemical injection
will be part of a total solution for wax/hydrate management and remediation. Even though
general solutions can be structured for oils of wide-ranging compositions and for a variety of
conditions, chemical injections are designed to address specific oils, conditions and problems.
Scientific basis on the mechanisms is available for some chemicals, but most knowledge
concerning applicability is empirical. The upfront cost of developing a chemical solution can be
high, and the associated remediation cost can be significant depending on the
15
Sonic Methods
Sonic management methods are not common. The concept is to position an ultrasonic generating
device adjacent to production tubing to disintegrate wax formed at the walls (Towler et al.,
2007). Ultrasonic waves also increase the temperature of the flowing oil (in the laboratory
experiments).
A number of reports on wax detection methods are available. Deepstar (2A)A212_1 identifies
methods of monitoring hydrates and solid paraffins in subsea flowlines, specifically to detect the
presence, deposition, and buildup. In Deepstar 2A A906_1v2 a method of measuring wax
deposition thicknesses are reported. In Deepstar 3208-2, it was determined that acoustic
techniques for removing paraffin in pipes are not effective or practical.
Sonic methods have been tested at bench scales. Scientific basis for their effectiveness has not
been established. It is not clear if these methods would work with hydrates and wax. As a result,
this technology has been rated low in our evaluations for applicability, scientific basis and cost.
16
17
18
The pipeline is designed with insulation so that flow remains above the wax appearance
temperature along the entire length of the line during steady state flow. Ideally temperature will
be above the wax appearance temperature so that precipitation and deposition does not occur.
Dual flowlines are another standard option that allow introduction of pigs from the surface
facility. Wax removal pigs can be pushed out one line and then flowed back the other with wells
shut in.
An oversized is designed for anticipated wax build-up during its design life and wax is allowed
to deposit.
The flowline is heated as necessary to prevent wax deposition. This method would generally be
combined with some insulation.
Chemicals are injected into the line at the well end to ensure that wax deposition does not occur
in the line.
The mitigation technologies examined in this study with ranks are listed below.
Upstream crawling pig powered by flow through annular turbines in the pig body. The pig
carries rotating cutter blades on the nose to remove wax. It can also be configured to return with
flow as a conventional pig.
Coiled tubing with a pig mounted on the end. The tubing is pulled through the flowline by the
pig.
A coiled tubing apparatus that allows the introduction of hydrochloric acid and ammonia. The
two chemicals mix to produce heat and nitrogen.
Go-Flo (6)
A combination of chemical, mechanical and thermal treatments can be applied using the
apparatus to clear blockages. A coiled tubing apparatus that uses composite tubing to reduce
friction and a crawler to tow the coiled tubing through the line.
Single flowline with a Subsea Pig Launcher (SPL) opersating wax removal pigs. Valve systems
would be used to moderate the pig motion in multiphase flow.
A pig with combination heat generation using slugs of hydrochloric acid and ammonia.
An SPL launched pig with a jet cleaning head to remove wax. The pig employs active braking to
control motion and reduce the pig velocity below the flow velocity as it moves downstream.
With flow shut in, a cleaning pig is driven out the flowline while returns flow through the
auxiliary line.
A sequence of increasingly aggressive pigs are launched onstream from an SPL to clean the line.
At the inlet to the flowline a looped section of pipe with a continually circulating pig cools the
fluid and precipitates the wax. The pig scrapes the wax from the wall of the pipe and the wax
then flows in suspension through the pipeline.
The major finding in this study was that none of the mitigation technologies were as reliable or
robust as the benchmark, single insulated line option. The most promising technology to run a
20
single unisulated line over long distances was identified to be the crawler pig. The cold-flow
wax-eater technology received the lowest (most unfavorable) rank, primarily due to the
assumption that the technology will not work in the presence of hydrates, and that hydrate
mitigation chemicals would be required.
Figure 4: The scenarios considered in Deepstar 7901-8 for production to beach alternatives, and
the basic economic parameters.
21
Technology
Implementatio Range of
Cold Flow Scientific
n over several Applicabi Cost
Applicability Basis
hundred miles lity
Overall
Rank
Comments
A "must-use" mitigation technology. Coldflow will be implemented with pigging backup options.
Good scientific basis and possibility of longdistance implementaiton. Range of
applicability neeeds testing and costs could be
higher than the benchmark
Usually combined with advanced pigging.
May be less applicable over long distances
Applicable technology. Sound technical and
scientific basis. Concerns are long-diatance
viability and cost
Also a must-use mitigation option. Usually
case specific and can be expensive
Pigging
10
10
10
8.8
Cold Seeding
7.2
Coiled Tubing
6.8
Active Heating
10
6.8
Chemical Inhibition
5.2
Internal Coatings
3.6
Sonic Methods
2.8
Biodegradation
Magnetic Methods
1.8
Microwave Methods
1.8
22
Proposed Research
Wax and hydrate control methods which could allow use of longer (over 10 miles total length)
uninsulated tie-backs or export lines, without requirements for parallel flowlines and round trip
pigging potentially offer significant reductions in CAPEX for future deepwater production
strategies. However, fundamental concepts and hypotheses need better quantification and
demonstration to validate their actual performance in the field. This literature review has
determined that a combination of technologies:
pigging,
active heating
chemical inhibition/dissolution,
offer the best potential for reliable wax & hydrate control operations including start-up,
maintenance, and changing production environments. Of these three technologies, the seeding
and cold flow technology currently has the largest gaps in fundamental concepts. If these can be
identified and better understood, it may allow for subsequent development.
Gaps in fundamental emphasis areas identified in seeding and cold flow include but are not
limited to:
Mass, Heat, Momentum Transport Influence of seeding method and flow conditions
upon resulting wax/hydrate slurry rheological properties, reduction in solid deposition
attributable to cold flow conditions, and unknown start-up and shutdown/shut-in concerns
(pipeline restart issues).
Thermodynamics & Kinetics Relationship of hydrate and wax precipitation processes,
degree of resulting fluid saturation and effects of residual latent heat release and transfer
to the environment.
Relating these gaps to differences in produced reservoir fluids, water cut levels, and export
pipeline conditions then allows the envisioned cold flow technology to have basic design
concepts for needed facilities; including selection of appropriate pigging and chemical treatment
technologies.
23
1. Evaluate fluid rheological behavior (slurry) for differences in seeding methods and
process conditions, and different combinations of oil types and gas contents. Laboratory
systems and experiments envisioned include:
a. Flow characteristics via constant stress rheometer
b. High pressure bench-scale-flow-loop for creation and measurement of cold flows
c. PIV studies of fluid flows, solid particle morphology, and deposition mechanisms
d. SEM evaluation of produced wax/hydrate/ice solids
2. Evaluate degree of saturation (depletion of wax forming compounds in the liquid phase)
provided for differences in seeding methods and process conditions, and different
combinations of oil types and gas contents, and resulting potential for reduction in solid
deposition under cold flow conditions. Laboratory systems and experiments envisioned
include:
a. FT-IR spectroscopy and HTGC for evaluation of solid wax content / available
liquid wax for potential deposition. We would perform these experiments with
parent crude oils and with oils progressively depleted of high molecular weight
waxes (which are expected to form the seeds in one version of cold-flow
application).
b. SARA analysis via HPLC of any crude oil solids deposited under cold flow
conditions.
3. Examine two different types of slurry creation methods, with and without hydrates.
Tentatively, the two methods would be:
a. A bench-scale wiped-film heat exchanger shown in Figure 5. Crude oil wax
slurries could be generated subsea after the wellhead by passing the hot oil
through a bank of subsea heat exchangers. Using cold sea water as the heat sink,
the hot oil could be lowered close to sea temperature while removing deposited
wax from the oil side of the exchanger using a wiped film type design.
Preliminary designs of these exchangers could be developed using existing heat
transfer design practices, to see if such designs could be economical.
Laboratory/bench scale tests can look at the characteristics of slurries produced in
such a manner.
b. A system to inject cold streams into hot streams to produce solids, and study
characteristics of the solids.
24
Insulation
MOTOR
Pump
Figure 5: Concept of a wiped-film heat exchanger which we will use in this phase of the project
to study solid/slurry creation.
4. Conduct comprehensive evaluation of restart methods for cold flow technologies.
25
Key References
Andersson, V., and Gudmundsson, J.S. (1999). Flow Experiments on Concentrated Hydrate
Slurries. SPE Paper 56567 prepared for presentation at the 1999 SPE Annual Technical
Conference and Exhibition held in Houston, Tx, 3-6 October 1999.
Boxall, J., Greaves, D., Mulligan, J., Koh, C., and Sloan, E.D. (2008). Gas Hydrate Formation
and Dissociation from Water-in-Oil Emulsions Studied Using PVM and FBRM Particle
Size Analysis. Proceedings of the 6th International Conference on Gas Hydrates,
Vancouver, British Columbia, Canada, July 6-10, 2008.
Buck, E. (1996). Paraffin Prevention by Coatings. DEEPSTAR Report, DAIIA CTR A906-1
(Volume 1). April 1996.
Deepstar Report, CTR 640, Pipeline/Flowline Pigging Strategies. H.O. Mohr Research &
Engineering, August 1994.
Deepstar Report, DSIIA CTR A212-1. Paraffin and Hydrate Detection Systems. April 1996.
Deepstar Report, DSIIA CTR A906-1 (Volume II). Deepstar Crude Petroelum Production
Enhancement Investigation. July 1996.
Deepstar Report, DSIII CTR 3208-2. Apparatus and Technique for the Evaluation of Magnetic
Conditioning As a Means of Retarding Wax Deposition in Petroleum Pipelins. June 1999.
Deepstar Report, DSIV CTR 4202-b1, Multidiameter Pig Tests. April 2000
Deepstar Report, DSIV CTR 4202-b2. Cold Seeding Lab Experiments. April 2002.
Deepstar Report, DSIV CTR 4202-b6, Mechanics of Wax Removal. November 2000.
Deepstar Report, DSV CTR 5201-3a, Deepstar V Project: Black Box Survey (Produced-Stream
Conditioner Enabling Single Bare Pipe Transport). October 2001.
Deepstar Report, DSVI CTR 6302, Subsea Pigging Technology for Flow Assurance. January
2004.
Deepstar Report, SCIV CTR 4303-1, Pigging of Deepwater Flowlines. January 2000.
Efner, H.F. (1996). Coatings for the Prevention of Paraffin Deposition: Cold Finger Screening
Studies. DEEPSTAR Report, DSIII CTR 3205-1. Phillips Petroleum Company, 1996.
Efner, H.F. (1996). Coatings Studies and Testing. DEEPSTAR Report, DSIII CTR 3205-2.
Phillips Petroleum Company, 1996.
26
Fung, G.S., Amin, R.M., Kalpakci, B., Fleyfel, F., and OSullivan, J.F. (2003). Method for
Reducing Solids Build-up in Hydrocarbon Streams Produced from Wells. U.S. Patent
6656366. December 2.
Hsu, J.J.C. (1997). Effect of Coatings on Wax Deposition Under Turbulent Flow Conditions.
DEEPSTAR Report, DSIII CTR 3205-3. October 1997.
Knowles, Jr., W.T. (1986). A Stream of Gas and Waxy Crude is Cooled by Expansion in a
Choke and Form a Stable Slury. U.S. Patent 4697426. October 6.
Kotlar, H.K., Wentzel, A., Throne-Holst, M., Zotchev, S., and Ellingensen, T. (2007). Wax
control by Biocatalytic Degradation in High-Paraffinic Crude Oils. SPE 106420 paper
prepared to present at the International Symposium on Oilfield Chemisty, Houston, TX,
28 February 2 March, 2007.
Larsen, R., Lund, A., Argo, C., and Makogon, T. (2007). Cold Flow A Simple Multiphase
Transport Solution for Harsh Environments. 18th International Oil Field Chemistry
Symposium, 25-28 March, 2007, Geilo, Norway.
Lund, A., Lysne, D., Larsen, R., and Hjarbo, K.W. (1999). Method and Sytem to Transport a
Hydrocarbon Fluid Containing Water. Patent PCT/NO99/00293, September 21.
Mendes, P., Braga, A., Azvedo, L., and Correa, K. (1999). Resistive Force of Wax Deposits
During Pigging Operations, ETCE99-6671, Presented at 1999 Energy Technology &
Conference Meeting of ASME's Petroleum Division, Houston, TX, 1999.
Merino-Garcia, D., and Correra, S. (2008). Cold Flow: A Review of a technology to Avoid Wax
Deposition, Pet. Sci. Tech., 26: 446-459.
Quarini, J., and Shire, S. (2007). A Review of Fluid Driven Pipeline Pigs and Their Applications,
Proc. IMechE Vol. 221, Part E: J. Process Mechanical Engineering. 2007.
Quintero III, I., Murphy, B., Maddox, J., Noddin, J., and Coles, R. (2008). Unique Application of
Coiled Tubing and Inflatable Packer Technology Leads to Successful Deoiling of
Damaged Pipeline in Gulf of Mexico, SPE 113792 paper prepared to present at the
SPE/ICoTA Coiled Tubing and well Intervention Conference and Exhibition, The
Woodlads, TX, 1-2 April, 2008.
Robins, L. (2003). On-Line, Non-Intrusive Diagnostic Techniques for Pipeline Inspection and
Flow Assurance., Published by the Pigging Products and Services Association, 2003.
27
Shire, S., Quarini, J., and Ayala, R. (2005). Experimental Investigation of the Mixing Behaviour
of Pumpable Ice Slurries and Ice Pigs in Pipe Flows, Proc. I MechE, Vol. 219 Part E: J.
Process Mechanical Engineering, 2005.
Tordal, A. (2006). Pigging of Pipelines with High Wax Content, Publication of Pigging Products
and Services Association, 2006.
Towler, B.F., Chejara, A.K., and Mokhatab, S. (2007). Experimental Investigation of Ultrasonic
Waves Effects on Wax Deposition During Crude Oil Production. SPE 109505 paper
prepared to present the SPE Annual Technical Conference and Exhibition, Anaheim, CA,
11-14 November 2007.
Turner, D., and Talley, L. (2008). Hydrate Inhibition via Cold Flow No Chemicals or
Insulation. Proceedings of the 6th International Conference on Gas Hydrates, Vancouver,
British Columbia, Canada, July 6-10, 2008.
Urdahl O., Brnes, A.H., Kinnari, K.J., and Holme, R. (2004). Operational Experience by
Applying Direct Electrical Heating for Hydrate Prevention. SPE Production & Facilities,
August 2004, pp161-167. (SPE 85015)
Wang, Q., and Sarcia, C. (2001). An Experimental Study on Mechanics of Wax Removal in
Pipelines, Paper SPE 71544 paper prepared to present in the SPE Annual technical
Conference and Exhibitin, New Orleans, LA, 30 September 3 October, 2001.
28
29
10
11
12
13
14
15
Citation
Yang, X., Kilpatrick, P., Asphaltenes and Waxes Do Not Interact Synergistically
and Coprecipitate in Solid Organic Deposits, Energy & Fuels, 2005, 19, 13601375.
Venkatesan, R., Ostlund, J., Chawla, H., Wattana, P., Nyden, M., Folger, H., The
Effect of Asphaltenes on the Gelation of Waxy Oils, Energy & Fuels, 2003, 17,
1630-1640.
Garcia, M., Crude Oil Wax Crystallization. The Effect of Heavy n-Paraffins and
Flocculated Asphaltenes. Energy & Fuels, 2000, 14, 1043-1048.
Kim, S., Myerson, A., Thermodynamic Properties of Supersaturated Solution and
Their Use in Determination of Crystal Growth Kinetic Parameters., ACS
Conference Proceedings - Crystal Growth of Organic Materials, Myerson, A.,
Editor, American Chemical Society, Washington D.C., August 27-31, 1995, pages
157-162, Printed 1996.
This experimental study used a model oil in a bench scale model pipeline outfitted with Laser Light Scattering (LLS) equipment to illuminate particles in a flow test section, and Particle Image Velocimetry (PIV) to obtain
Todi, S., Deo, M., Experimental and Modeling Studies of Wax Deposition in Crude- radial velocity profiles. This study only covered low Reynolds number flows - laminar flows, and was unable to obtain deposit thickness. The study is important because it included "cold pipe-cold oil" conditions with low or
Oil-Carrying Pipelines, OTC 18368, 2006 Offshore Technology Conference,
zero heat flux to the environment. Deposition was observed for the case of no heat flux (as long as system was below the WAT) and was attributed to Brownian motion as shear dispersion seemed to locate the majority of
Houston, TX, May 2006.
partlcles in an annular area away from the pipe wall. .
This academic dissertation documents the experimental work in reference 5, and presents modeling results for the same experimental systems. The model covers both laminar and trubulent conditions, and matches
results predicted by the model of Burger & Perkins (Burger, E., Perkins, T., Striegler, J., Studies of Wax Deposition in the Trans Alaska Pipeline, JPT, June 1981) well. Key modeling conclusions include: The model did not
Todi, S., Experimental and Modeling Studies of Wax Deposition in Crude Oil
include a rigorous thermodynamic model capable of predicting Solid-Liquid-Equilibrium (SLE) and thereby the composition of the deposit formed along with aging phenomena. The model does predict that deposition from
Carrying Pipelines., Ph.D. Dissertation, University of Utah, January 2005.
particle flux to the wall is expected to increase when going from laminar to turbulent flow.
This paper describes a regular solution model which predicts (no tuning required) wax AND asphaltene precipitation for Alaska North Slope crude oil based on APSC / TAPS-COS crude oil characterization methods. This
Leelavanichkul, P., Deo, M., Hanson, F., Crude Oil Characterization and Regular model has not been commercially developed.
Solution Approach to Thermodynamic Modeling of Solid Precipitation at Low
Pressure., Petroleum Science and Technology, Vol. 22, No. 7 & 8, 973-990, 2004.
This paper provides a critical review of all wax deposition models in the literature as of 2003. The important conclusion of this review is that based on the comparison of various models to experimental data, molecular
Azvedo, L., Teixeira, A., A Critical Review of the Modeling of Wax Deposition
diffusion may not be the predominant deposition mechanism in all physical situations. Because of this, the paper recommends detailed observations at controlled conditions to help clarify detailed observations and the
Mechanisms, Petroleum Science and Technology, Vol. 21, No's 3 & 4, 2003, 393- relative importance of various potential deposition mechanisms. This review also clarifies an apparent error in the papers of Burger and Perkins which identified shear dispersion as a contributing mechanism when in fact it
408.
was actually Brownian motion.
Garcia, M., Urbina, A., Effect of Crude Oil Composition and Blending on Flowing This paper investigated the effect of n-paraffin molecular weight distribution on wax precipitation. Through an experimental program involving 16 oils from Venezuelea it was found that oils with boader distributions of nProperties, Petroleum Science and Technology, Vol. 21, No.'s 5 & 6, 863-878,
parraffins exhibited lower Wax Precipitation Temperatures and that injection of light condensates also improved WPT's.
2003.
This paper describes a laboratory wax deposition testing device (a cold spot tester) which was used to investigate wax deposition from a model oil systems as well as a North Sea Crude Oil. The advantages demonstrated
by this device are the small sample size and short test times required as opposed to flow loops. Also, the wax deposits are easily removed and analyzed for composition in the laboratory. All test conditions involved "hot oil
(above WPT) - Cold Pipe (Below WPT)". Several important qualitative results identified in this paper: wax deposition under these conditions appears to be driven by thermal mass transfer as pure diffusive flux could not
provide the amount of deposits obtained during the short testing times (diffusion coefficients are very small), and increases in fluid velocity (provided by a stirrer in the fluid chamber) were observed to decrease the amount
Wu, C., Wang, K., Shuler, P., Tang, Y., Creek, J., Carlson, R., Cheung, S.,
of paraffin deposition. One final note is that "no flow" testing with the stirrer off produced the same type of deposits - and this was attributed to higher temperature gradients in the no flow condition. Age hardening
Measurement of Wax Deposition in Paraffin Solutions, AICHE Journal, Vol. 48,
(increasing paraffin content in the deposit) was observed to occur in this test apparatus as well, with increased paraffin contents resulting from testing conditions with higher fluid velocities. The North Sear crude oil results
No. 9, Sept. 2002, 2107-2110.
qualitatively mirrored those for the model oil.
Lopes-da-Silva, J., Coutinho, J., Analysis of Isothermal Structure Development in This paper introduces the concept of modeling the nucleation and subsequent crystal growth of solid wax in crude oil with the Avrami Model.
Waxy Crude Oils under Quiescent Conditions, Energy & Fuels, Web Release
10/24/07, ef700357.
This paper describes the SLE thermodynamic model used in the wax deposition model described in Reference ST-7-15. The model is the end result of model development by J. Coutinho, and is available as a commercial
model - "WAXtracker" described at http://path.web.ua.pt/wax/wax.html. The model is described as a predictive local composition model, needing NO tuning based on measured WPT's or other SLE data. This version of
Coutinho's model uses the SRK-EOS where previous model versions used other so called LCVM formulations of EOS. The actual predictions of the SRK-EOS for activity coefficients are modified in such away to correct
for what the authors believe is an overprediction of non-ideal behavior, so that the calculated activity coefficients for n-paraffin components are more in line with ideal solution behavior - this may be questionable. The solid
wax phase is treated as a non-ideal solution (unlike most other models), and uses the UNIQUAC to estimate excess Gibbs Free Energy (which is minimizede to obtain solution).
Coutinho, J., Edmonds, B., Moorwood, T., Szcsepanski, R., Zhang, X., Reliable
Wax Predictions for Flow Assurance, Energy & Fuels, 20, 1081-1088, 2006.
Coutinho, J., Daridon, J., The Limitations of the Cloud Point Measurement
Techniques and the Influence of the Oil Composition on Its Detection, Petroleum
Science and Technology, Vol. 23, 1113-1128, 2005.
Larsen, R., Lund, A., Argo, C., Makogon, T., Cold Flow - A Simple Multiphase
Transport Solution for harsh Environments, 18th International Oil Field Chemistry
Symposium, 25-28 March 2007, Geilo, Norway.
U.S. Patent No. 4,697,426, Choke Cooling of Oil, Shell Western E&P Company,
October 6, 1987.
The paper points out the problems with many cloud point (aka WPT, WAT, etc.) measurement techniques, and makes a logical identification that good practice should include development, and review of fluid compositions
and exploratory modeling.
This paper describes the "Cold Flow" concept - where crude oil containing light ends and black oil is cooled to produce a slurry of cold liquid oil with entrained ice, hydrates, solid wax and asphaltenes. The hope is that this
slurry will not be prone to deposition of solids on the pipe wall owing to the lack of temperature/diffusive driving force, and that the pipeline would exhibit better restart charactaristics after a prolonged shutdown owing to
less interaction amongst solids.
This patent describes a method of producing "Cold Flow" by injecting natural gas into black oil.
16
17
18
19
20
21
22
23
24
U.S. Patent No. 4,441,987, Dewaxing Process using Agitated Heat Exchanger to This patent describes a method of producing "Cold Flow" using a heat exchanger process to create a slurry which could be transportable by pipeline rather than filtered fro wax removal.
Chill Solvent-Oil and Wax Slurry to Wax Filtration Temperature, Exxon Research &
Engineering Company, April 4, 1984.
International Publication Number WO 2004/059178 A2, Method and System for
This international patent describes the "Cold Flow" concept using a cold recycle stream to cool a wellhead flow and create the pipeline slurry.
Transporting Flows of Fluid Hydrocarbons Containing Wax, Asphaltenes, and/or
Other Precipitating Species. SINVENT A/S, BP Exploration Operating Company,
Limited., BP America Inc., July 15, 2004.
Gudmundsson, J., Cold Flow Hydrate Technology, 4th International Conference on This paper summaraizes NTNU's initial work on hydrates slurries, including development of slurries in laboratory, and resultant slurry rheology for hydrate/water and hydrate/water/diesel slurries.
Gas Hydrates, May 2002, Yokohama, Japan.
This report described Phase 1 results of a seeding experiment undertaken by Nenninger Engineering Inc., and Marathon Oil Company. These experiments showed that wax deposition rates
Deepstar Report CTR 4202-B2, Cold Seeding Lab Experiments, April 2000.
could be reduced by seeding crude oils with waxy solids.
Deepstar Report CTR 4203-3a, Flowloop Tests on Pompano and Troika, April
2000.
Data acquired in this work indicate that Pompano and Troika oils have a significant natural ability to resist hydrate plugging.
Subsea, wellhead, produced-stream conditioner enabling single bare pipe transport (CEBPT) without chemical inhibition for hydrates and wax offers one way of lowering
Deepstar Report CTR 5201-3a, Black Box Survey, October 2001.
the cost of deepwater development systems with long tiebacks from wellheads to surface facilities. Ideas and work to date by SINTEF and KBR are presented.
Deepstar Report CTR 5201-3b, Black Box Survey, October 2001.
General release of Deeptstar CTR 5201-3b.
This study addressed the feasibility of transporting a hydrate slurry in subsea flowlines. While it does not directly relate to cold flow seeding technology it is relevant because it describes problems encountered in creating a
Deepstar Report CTR 5201-4, Hydrate/Wax Slurry Transport Tests, June 2003.
hydrate slurry in a pilot plant situation. Specifically it documents the need for a "reliable hydrate slurry maker".
Deepstar Report CTR 7901-8, Produce to the Beach Alternatives - Hermit Field
This work compared a single stage subsea processing system (Case 5) and multiphase Cold Slurry Flow systems (Cases 6A & 6B) economics to the Semisubmersible Base Case 2A scenario for the 10,000 fsw GOM
Development Studies, November 2005.
Hermit Field conditions.
Experiments were conducted to systematically investigate how gas hydrates are related to other flow assurance factors and how these interactions could affect the performance of antiagglomerate hydrate inhibitors (AAHI).
Shuqiang Gao, Investigation of Interactions between Gas Hydrates
It was demonstrated that one type of solid precipitate can promoteand exacerbate others. It was also shown that the elimination of one issue can alleviate other associated risks
and Several Other Flow Assurance Elements, Energy Fuels, 2008, 22, 31503153.
25
26
Nichita, D., Bessieres, D., and Daridon, J., Calculation of Joule-Thomson Inversion
Curves for Multiphase Systems with Waxy Solid-phase Precipitation, Energy &
Fuels, 2008, 22, 4012-4018.
Fidel-Dufour,A., Herr, J., Formation and Transportation of Methane Hydrate
Slurries in a Flow Loop reactor : Influence of a Dispersant. 4th International
Conference on Gas Hydrates, Yokohama : Japan (2002).
This paper presents a method for JTIC calculation in multiphase systems, based on isenthalpic flash calculations, with emphasis on mixtures with solid-phase precipitation. Effects of the presence of a solid phase on the
JTIC can be very important.
This paper presents the experimental results obtained from a new flow loop reactor in which methane hydrate particles are crystallized in water droplets transported in a oil flow. The final goal of this apparatus is to couple
the rheology with the Particle Size Distribution of water droplets and gas hydrate during crystallization and to observe the influence of dispersants and/or kinetics additives.
Reference No.
3
4
This paper was the result of the University of Tulsa JIP. This study involved "model" pigs in "model" pipelines ( 3" ID, 21 ft long). The pigs were
pulled through the pipeline at constant speed using an electric wench equiped with a load cell to measure pulling force required. In this way a force
balance can be obtained and interpretations of pigging parameters such as pig design and frequency can be related to wax characteristics such as
thickness, and total solid content. The study found a typical wax removal process follows 4 distinct phases: 1.) pre-plug phase, 2.) wax build up
phase, 3.) wax plug phase, 4.) wax production phase. The frictional force between the wax deposits and the wax plug accumulated in the frontof the
pig can be significant to the total force required to push the pig - and appears to dominate in long pipelines. The thicker the deposit, and/or the
harder the deposit, the force required to break the wax off is increased. Shape and material of the pig has a profound effect on pigging performance
Wang, Q., Sarcia, C., An Experimental Study on Mechanics of Wax Removal in
- with disc pig design giving the best removal efficiency.
Pipelines, SPE 71544, 2001.
Per reference 100 above: "They have developed a procedure utilizing finite element technique to solve the momentum equations based on the two
Mendes, P., Braga, A., Azvedo, L., Correa, K., Resistive Force of Wax Deposits
different load models and compression test results. Their procedure is at best qualitative and only gives an estimate for the minimum differential
During Pigging Operations, ETCE99-6671, Presented at 1999 Energy Technology & pressure needed to remove the accumulated wax. Furthermore, the experimental shear stress determination using compression test may not be
Conference Meeting of ASME's Petroleum Division, Houston, TX, 1999.
suitable for a substance line wax and wax-oil mixture."
Tordal, A.(Statoil ASA, Stavanger, Norway), Pigging of Pipelines with High Wax
Content, Publication of Pigging Products and Services Association, 2006.
This document provides guidelines for "best practice" regarding pigging of pipelines with high wax content.
This paper describes the basics involved in using radioisotopes as tracers, and provides case studies of applications. A specifc example is provided
Robins, L. (Tracerco), On-Line, Non-Intrusive Diagnostic Techniques for Pipeline
for an NGL pipeline where variation in pig velocities identified the location (and character) of pipeline deposits.
Inspection and Flow Assurance., Published by the Pigging Priducts and Services
Association, 2003.
7
8
This paper gives a review of the current state-of-art in pigging technologies. It includes descriptions for all current pig designs including non-solid/gel
Quarini, J., Shire, S., A Review of Fluid Driven Pipeline Pigs and Their Applications, pigs and ice block pigs. Gel pigs can be used to pickup debris and water from a pipeline, and / or to deliver specific dosages of wax and/or
Proc. IMechE Vol. 221, Part E: J. Process Mechanical Engineering, 2007.
corrosion inhibitors.
The objectives of the study were threefold:* Review deepwater pipeline pigging technology and industry experience;, * Address the impact of
pigging requirements on floating production andsubsea production system designs; * Provide design guidance applicable to Deepstar in particular,
Deepstar CTR 640, Pipeline/Flowline Pigging Stratagies, H.O. Mohr Research &
and deepwater Gulf of Mexico production systems in general. The report summarizes the state-of-art circa 1994. Pig type and frequency of pigging
Engineering, August 1994.
were identified as obvious critical concerns, along with factors influencing system design and operation.
Texas A&M University evaluation of Multidiameter Pigging issues. Preliminary evaluation of a leaf spring design was undertaken and found to be
Deepstar CTR 4202-b1, Multidiameter Pig Tests, April 2000
not very promising.
Deepstar CTR 4202-b6, Mechanics of Wax Removal, November 2000.
Deepstar Report CTR 6302, Subsea Pigging Technology for Flow Assurance,
January 2004.
This study addresses alternatives to the conventional approach used in deepwater development of providing dual flowlines, which allows roundtrip
pigging for flow assurance. Specifically, the study developed comparative evaluations for reasonable systems for 5 to 10 mile tie-back cases.
10
Number
010918
Title
Evaluating New Chemicals
and Alternatives for
Mitigating Hydrates in Oil &
Gas Production
Author(s)
Pickering, P.F., B. Edmonds, R.A.S.
Moorwood, R. Szczepanski, M.J. Watson
00049172
00071550
Conversion of Water to
Hydrate Particles
SPE-111903-MS
Year Synopsis
2001 Discusses hydrate formation with detail in
hydrate-forming chemicals; evaluates the
effectiveness of various hydrate-inhibiting
methods, namely Thermodynamic and
Kinetic Hydrate Inhibitors and Anit1998 Prevention of hydrate plugging achieved
by creating an emulsion slurry in pipelines
using natural surfactants such as
asphaltenes. Waxes also considered;
evidence indicates higher wax content
allow for higher watercuts in streams.
2001 Details specifics in regards to hydrate
growth in a cooled well stream. Hydrate
seeds grow in a controlled manner and
draw out free water from the stream.
Some applications to industry presented.
2007 Discusses flow assurance strategies for
dealing with hydrates and wax deposition
separately. Geometries, flow conditions,
etc. all necessary for evaluations of each
case. Various strategies for hydrate and
wax management presented.
2007 Internal coatings for wax deposition
prevention are only marginally effective;
once wax deposition occurs, the coatings
have little to no further effect. Vacuum
insulation improve heat retention and
reduce heat transfer greatly through
pipeline walls, aiding to reduce cooling
rates, thus reducing wax deposition and
2007 Insulation and other materials studied to
determine heat transfer qualtiies to reduce
cooling along pipelines to prevent hydrate
and wax formations.
Paper #
(2) 640_1
Title
Pipeline/Flowline Pigging
Strategies
Author
MOHR RESEARCH
(2) 931_1
(2) 932_1
Paragon Engineering
Services, Inc.
Year
Summary
1994 Pigging strategies set forth with respective
purposes, successes and problems with each
method. Various types of pigs presented with
photographs and schematics. Intelligent pigs
1994 Following are for a subsea well for a 50-mile
flowline to shallow water fixed platform or to
floating production systems. Chemically
removing or preventing paraffin deposits from
subsea wellbores, flowlines, and pipelines
during operation and shutdown. Used at 4k ft of
water. Recommended: wax crystal modifiers and
offers highest degree of success. Usually
mechanical and/or thermal methods used.
Further suggestions: Hot oil or water with
dispersants and/or solvents. Wax crystal
1994 Assorted thermal techniques and scenarios
explored; heat tracing, hot annular fluid injection
effectively control paraffins duing both flow and
shutdown in wellbores; cost not used as an
elimination factor - further work is suggested;
wellbore insulation technologies examined vacuum insulated tubing included - fishing
Keyword
Pigging
Thermal
(2)933_1
(2) 934_1
(2A)208_1
TFL, Through
Flowline, pigging, coil
tubing, reach rods,
paraffin,
Paraffin, Chemical,
Thermal, Mechanical
blockage, paraffin,
hydrate, gas hydrate
blockages, unblock
line, blockage location,
Paragon Engineering
Services, Inc.
Lionel M. Fontenette
Exxon company
Deepstar, Texaco
Hydrates, Paraffin,
Detection
Paraffin, Hydrate,
Chemical Inhibitor,
Insulation
Paraffin, deposition of
paraffin, carbon
number, Bulf of Mexico
Paraffin, Chemical
Inhibitor
Monger-McClure, T.G.,
Marathon Oil Company
Paraffin, deposition,
modeling
Buck, E.
Paraffin deposition,
modeling
Internal Coatings
3202-1
Pipeline Blockage
Remediation
Radoil, Inc
3205-1
3205-2
3205-3
Hsu, J.J.C.
ultrasonic, acustic,
energy, paraffin
thickness
Microwave
Internal Coatings
Internal Coatings
Internal Coatings
3206-1
Molecular Simulations,
Inc
3208-1
3208-3
3213-1
4201-a1
Gregory J. Hatton
Paraffin, wax,
deposition, crystal,
molecular modeling,
inhibitors
Chemical Inhibitor
Acoustic, Other
Methods
Differential scanning
calorimeter,
projects, Wyoming,
Colorado, lab tests,
fluid systems
4201-b1
4201-c1-1
E. Diatzikis, A. Mendez of
ABB Elictric Systems
Tech Institute in NC with
Cheveron as the technical
sponsor.
4201-c1-2b Laboratory-based
Simultaneous Measurement
of Distributed Pressure and
Temperature in an Optical
Fibre
Parker, T. and M.
Farhadiroushan
Pressure
Measurement
Pressure
Measurement,
Temperature
Measurement
4201-c2-1
4201-c2-2
4201-c4
4201-c5
Schwartz, C.J.,
Southwest Research
Institute
Hydrates, Paraffin,
Detection, Acoustic
paraffin buildup,
magnetostrictive,
paraffin thickness
detection
Paraffin, Detection
4202a2
4202-b1
4202-b5
Paraffin Deposition
Workshop
Radoil, Inc
wax crystal
modifications, cloud
point, thermodynamic
modeling, deposition,
crystallization,
4202-b-3a
4202-b-3b
4202-b-3c
4203-a3
Asphaltene Studies
Workshop
Asphaltene
2000 Series of presentations and workshops on
asphaltenes and other flow-related subjects
presented in full, including measures of
remediation (coatings, chemical inhibitors, etc)
for asphaltenes; interactions between
asphaltenes and solids; geochemical aspects of
asphaltenes; role of aggregation in fils,
emulsions, foams, and precipitation; dissolution
of ashpaltenes using amphiphile/alkane
Prediction of Asphaltene
Deposition
Flocculant, PRI,
deposition,
asphaltene, FloryHuggins, stability,
4203a-3a
4203-b1
4303-1
Pigging of Deepwater
Flowlines (Final Report)
Flow assuracne
design
5201-3a
Produced-Stream
Conditioner Enabling Single
Bare Pipe Transport
5201-4
Hydrate/Wax Slurry
Transport Tests
5306-1
Paraffin, Hydrate,
Conditioning, NonChemical Inhibitor,
Pigging
Hydrate, Slurry
RPSEA DW 1201
Project Objectives
A comprehensive literature review
concerning flow in subsea pipelines,
hydrate and wax formation
formation, and methods
to prevent deposition.
An experimental program to evaluate two
of the most promising technologies for
preventing wax formation
Technology Criteria
1 Is the technology as defined, applicable to cold1.
cold2.
3.
4.
5.
flow conditions?
What is the scientific basis of the p
proposed
p
method?
How easy/difficult
y
would it be to deploy
p y the
method over several hundred miles of pipe?
Under what conditions is the method likely to
fail? (range of applicability)
What are preliminary cost estimates?
Outline
Literature review highlights
Individual technology discussion
A
Analysis
l i
Technology evaluation proposal
Literature Review
Extensive Deepstar literature
Scattered SPE papers
M t reports
Most
t emphasize
h i what
h t works
k and
d
what does not work less effort on
f d
fundamental
t l mechanisms
h i
and
d
understanding
Deepstar Studies
Current Practice
Coiled
C il d ttubing,
bi
h
heatt ttracing
i and
d iinsitu
it h
heatt generation
ti also
l used
d
SGN (5)
Jetstream pig (10)
Go--Flo (6)
Go
CTR 6302
CTR-6302
Evaluation Summary
Cold Seeding
g and Production Chilling
g
Literature
Larson et al., 2007, Cold Flow - A Simple Multiphase Transport Solution
for Harsh Environments, 18th International Oil Field Chemistry
Symposium, 25
25--28 March 2007, Geilo
Geilo,, Norway
25 other papers on subjects ranging from cold flow wax applications to
effect
ff t off asphaltenes
h lt
to
t hydrate
h d t transport
t
t to
t waxwax-hydrate
h d t ttransportt
reviewed
Tflow = Twater
Precipitated Wax
Cold Slurry
T = 3~4 oC (Seabed)
Wax Eater
Hot Oil
Another Method of
Creating A Slurry
Di
Dissolved
l d Wax
W
Precipitated Wax
Gas
Shell Process
Adapted from Correra, et al (2008)
Pigging
gg g
Literature
Esmaeilzadeh et al., 2006, Modeling of Pig Operations in Natural gas
and Liquid Pipelines, SPE 102049
15 other papers, patents, Deepstar reports reviewed
Crawler Pig
Subsea launcher
Power Pig
Progressive Pigging
Chemical Injection
Literature
25 references reviewed lot of Deepstar work
Soni et al., Energy and Fuels 2008 Performance
based design of PP depressants and wax crystal
modifiers
Definitely effective with specific additives for specific oils
Applicable to cold flow
Extensive testing not a lot of public literature
Possible scientific basis not often reported
Range of applicability questionable due to the specific
testing aspect of the technology
Very few studies with wax and hydrates
Polymer backbone:
backbone: a slight effect on pour point depression
Effective
Ineffective
Low
High
Quantity of C24+
< 32%
> 52%
Wax distribution
Bimodal
Monomodal
Ester
Polymer
ELVAX 150
ELVAX 240
Polyacrylate
Polymethacrylate
Molecular
weight
87,767
82,900
97,730
103,900
Tm (oC)
60-63
70-74
53
48
Degree of
Crystalinity, %
50-55
20-26
10
-12
-15
*Pour point of the crude oil is 18 oC. The data above were obtained after 100 ppm addition.
Data Sources: SPE 93090
Hydrates: THI vs
vs. LDHI
Type
Act
Dosage
amount
(water basis)
10 to 40 vol%
0.25 to 5 vol%
CAPEX
OPEX
High
Low
Ch i l
Chemical
M OH MEG
MeOH,
V i
Various
polymers
l
Internal Coatings
Coatings are not effective as paraffin deposition inhibitors. The
reduction in paraffin deposits, observed with coated test specimens,
is due to the reduction in heat flux caused by the insulating nature of
the coating. A linear relationship exists between the coating
thickness and the percent reduction in paraffin deposits.
Coating chemistry did not play a significant role in reducing the
deposition of wax. This became especially evident when the deposit
reduction was normalized on a per mil of coating thickness basis.
Surface finish (or roughness) did not play a significant role in this
study. The coatings with glossy, smooth, and matte finishes
performed identically.
Under turbulent or highhigh-shear flow conditions, coating may have
different effect on wax deposition - nylon decreased wax deposition
at temperatures close to cloud point at high velocities (an
exception); teflon increases wax deposition at higher flows
Biodegradation
Biodegradation
Kotlar
Kotlar,, et al., 2007, Wax control by Biocatalytic Degradation in HighHighParaffinic Crude Oils,, SPE 106420
Economics (CTR(CTR-7902)
Overall Goal
Current Practice
Si l flflowline
Single
li iinsulated
l t d
Dual
ua flowline
o
e roundtrip
ou d p p
pig
g
7.2
Pigging
8.8
CoiledTubing
6.8
ActiveHeating
7.4
ChemicalInhibition
5.2
InternalCoatings
3.6
SonicMethods
2.8
MagneticMethods
1.8
MicrowaveMethods
1.8
Biodegradation
What we do know
Hydrate
Hydrate--wax solution is a multi
multi--pronged
approach
Back--up strategie
Back
strategie(s)
(s) are often required
Cold seeding reduces deposition in both
hydrates, waxes and hydratehydrate-wax solutions
Coatings are not practical
A chemical solution to coldcold-flow appears
unlikelyy
Sonic--magnetic
Sonic
magnetic--biodegradation methods need
significant
g
development
Phase II Evaluation
Cold transport fundamental analysis and
experimental validation
Wax slurries
Hydrates
y
Dynamics of wax and hydrates
Range
g of applicability
pp
y
Mechanical aspects of slurry makers (paper
study)
Coupling coldcold-flow with advanced pigging
technologies (paper study)
A detailed proposal to the steering committee in
four weeks
Acknowledgements
Dr. Kyeongseok Oh
Dr
Mark Jemmett and Dave Johnson
Jim
Ji Chit
Chitwood
d
Oris Hernandez
Members of the steering committee