RPSEA1201ControllingWaxDeposition

inthePresenceofHydrates
TechnologyEvaluationReport
University of Utah, Salt Lake City - Milind Deo, Jules Magda and Rich Roehner

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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

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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.

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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.

Evaluation of the thermodynamics of mixtures containing waxes

Study of the fundamentals of particle/slurry creation

Examination of the morphology of the particles formed

Restart behavior of oils with precipitated waxes

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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).

Technology Review Methodology

Each of the technologies described in the next few sections consists of the following elements.

Description of the technology and how it works

Technical gaps
The state of development of the technology and its availability
Effectiveness of the technology, when used in a cold-flow deepwater subsea application
Review of literature

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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.

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 How does cold seeding work?
Dissolved Wax
Precipitated Wax

Sea Water at temperature, Twater

Tflow > WAT Tflow = Twater

Cold Flow Equipment

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 Hot Oil

T = 3~4 oC (Seabed) Periodic pigging to remove deposits

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
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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
Dissolved Wax
Creating A Slurry
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 low-
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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

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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.

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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.

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In summary, pigging is the mainstay of remediation technologies and would be considered a
must-use technology for long-distance tiebacks. Option to pig the line as a backup must be
available to ensure a robust cold-flow system. However, effectiveness of pigs in cold-flow
situations has not been tested extensively.

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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).

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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

Normal / (cyclo + iso) low high
Quantity of C24+ Less than 32% Higher than 52%
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).

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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

Polymer
ELVAX 150 ELVAX 240 Polyacrylate Polynethacrylate
Molecular
87,767 82,900 97,730 103,900
weight
Tm (oC) 60-63 70-74 53 48
Degree of
- - 50-55 20-26
Crystalinity, %
Pour point (oC) 10 4 -12 -15

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

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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.

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Biodegradation and other methods
Even though bio-degradation has been a well-researched technology, microbial recovery of waxy
crude oils from oil reservoirs, limited emphasis has been placed on these methods for pipeline
remediation. This may be due to the fact that microbial processes are typically slower than what
might be required for fast(er) pipeline operations. Wax control by biocatalytic degradation of
high-paraffinic crude was recently reported by Hans Kristian Kotlar et al. 2007. They isolated a
strain of Acinetobacter and studied the degradation of long-chain alkanes. The applicability of
the method under flowing conditions, and in other environments will have to be investigated.

Some other methods such as microwave detection and remediation methods were looked at in
Deepstar and patent literature. None of these methods appear to be applicable to cold flow over
long distances. Even with significant developments, these methods will have to address
dispersion of agents and mixing in pipelines. At the current time, the technologies have neither
been demonstrated, nor do they have a good scientific basis. As a result, these technologies have
been rated low on all of our evaluation criteria.

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Coiled Tubing and Active Heating
The coiled tubing technology is becoming more prevalent in solving flow assurance problems
(Quintero et al. 2008). The technical applicability of the method is oftentimes limited by
pipeline dimensions and geometry. The coiled tubing options along with pigging have been
discussed in detail in Deepstar 6302, a summary of which is provided in the following section.

Dual insulated flow lines, is an industry standard for managing wax/hydrate problems. Single
insulated buried lines (like the Macher tie-backs) are also seen. Chemicals are part of the flow
assurance solution in these cases. For single insulated lines, subsea pig launchers are part of the
design, although not very common. In some instances heated, dual flowline designs are used.
One example of such design is the King field. Active heating in this case is provided by
circulating a mixture of glycol-water mixture.

In the Huldra-Veslefrikk pipeline field (hydrate in condensate production), a direct electrical

heating (DEH) through electrical current was applied to generate heat through the steel pipeline
wall. The electric power cable strapped to the thermally insulated pipeline (polypropylene coated
super-martensitic steel, 13% Cr, 2% Mo) in a piggyback configuration. Fluid temperature
generated by DEH was maintained at greater than the equilibrium temperature of hydration
formation. Pipeline was 8 diameter and ten miles long. Safety and reliability were issues due to
aging or accidental shorts. This technology has seen limited application, and is not
recommended for long distance tie-backs (Urdahl et al., 2004).

The applicability of active heating as a wax/hydrate management technology is well established.

The question is implementation over long distances and cost. In terms of scientific basis and
applicability these technologies are ranked high on our list but the cost is likely to be
prohibitive.

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Summary of Findings from Deepstar 6302
Kellog, Browm and Root (KBR) performed a comprehensive evaluation of 15 benchmark and
wax mitigation technologies and came up with comprehensive rankings for the technologies
evaluated. All of the technologies considered wax mitigation and did not specifically address
hydrates. The benchmark technologies that they looked with the ranking assigned are
summarized below.

Single insulated pipe (1)

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 flowline roundtrip pig (3)

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.

Single pipe wax in place (7)

An oversized is designed for anticipated wax build-up during its design life and wax is allowed
to deposit.

Single flowline heat (9)

The flowline is heated as necessary to prevent wax deposition. This method would generally be
combined with some insulation.

Single flowline chemical treat (11)

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.

Crawler pig (2)

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 Thrust and Carry (TAC) pig (4)

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Coiled tubing with a pig mounted on the end. The tubing is pulled through the flowline by the
pig.

SGN (Nitrogen Generation System) (5)

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.

Subsea pig launcher (8)

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.

Jetstream pig (10)

A pig with combination heat generation using slugs of hydrochloric acid and ammonia.

Power pig (12)

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.

Auxiliary line (13)

With flow shut in, a cleaning pig is driven out the flowline while returns flow through the
auxiliary line.

Progressive pigs (14)

A sequence of increasingly aggressive pigs are launched onstream from an SPL to clean the line.

Wax eater (cold-flow) (15)

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

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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.

Summary of Economics of Cold-Flow from Deepstar 7901-8

This Deepstar report offers some insight concerning cold flow economics if slurry transport were
to be adapted. Produce to the Beach scenarios compared in this report conclude that using cold
slurry technology and multiphase pumps provide a robust facility solution. This solution does not
deliver the projected performance of the more technically challenging Subsea Processing
scenario or the IRR of the Base Case, which was the conventional dual line to the platform and
export lines to the beach. One of the primary reasons for this conclusion was that the cold-flow
technology with slurry transport would take longer to produce the same volume. The different
scenarios considered and the basic economic parameters are compared in Figure 4.

Figure 4: The scenarios considered in Deepstar 7901-8 for production to beach alternatives, and
the basic economic parameters.
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Ranking Criteria (1-10 on each)
1. Is the technology as defined, applicable to cold-flow conditions?
2. What is the scientific basis of the proposed method?
3. How easy/difficult would it be to deploy the method over several hundred miles of
pipe?
4. Under what conditions is the method likely to fail? (range of applicability)
5. What are preliminary cost estimates?

Based on these criteria, the following are our rankings of the technologies evaluated.

Table 4: Technology evaluation using the ranking criteria provided in the proposal guidelines

Implementatio Range of
Cold Flow Scientific Overall
n over several Applicabi Cost Comments
Applicability Basis Rank
Technology hundred miles lity
A "must-use" mitigation technology. Cold-
Pigging 10 10 9 10 5 8.8 flow will be implemented with pigging back-
up options.
Good scientific basis and possibility of long-
distance implementaiton. Range of
Cold Seeding 9 8 7 5 7 7.2
applicability neeeds testing and costs could be
higher than the benchmark
Usually combined with advanced pigging.
Coiled Tubing 7 9 3 8 7 6.8
May be less applicable over long distances
Applicable technology. Sound technical and
Active Heating 9 10 5 7 3 6.8 scientific basis. Concerns are long-diatance
viability and cost
Also a must-use mitigation option. Usually
Chemical Inhibition 5 6 5 5 5 5.2
case specific and can be expensive
Long-distance viability is the strongest
Internal Coatings 3 2 9 1 3 3.6
attribute. Weak scientific basis and high cost.
Not enough data to indicate even proof of
Sonic Methods 1 2 7 1 3 2.8
concept.
Biodegradation 2 1 1 1 5 2 Shown not be applicable in Deepastar work.
Magnetic Methods 1 3 1 1 3 1.8 Not enough proof of viability.
No proof. Even if fundamentally applicable,
Microwave Methods 3 3 1 1 1 1.8
difficult to implement

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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:

seeding and cold flow,

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.

Proposed Laboratory Evaluation(s)

This study proposes the following laboratory evaluations to begin to fill the gaps identified in
fundamental emphasis areas:

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
Appendix Literature Review Reports and Presentation

29
 December 31, 2007
Rev. 0

RPSEA 1201 - Cold Seeding References

Ref. No. Citation
Yang, X., Kilpatrick, P., Asphaltenes and Waxes Do Not Interact Synergistically
1 and Coprecipitate in Solid Organic Deposits, Energy & Fuels, 2005, 19, 1360-
1375.
Venkatesan, R., Ostlund, J., Chawla, H., Wattana, P., Nyden, M., Folger, H., The
2
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
3
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
4 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.
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
5
Oil-Carrying Pipelines, OTC 18368, 2006 Offshore Technology Conference,
Houston, TX, May 2006.
6
Todi, S., Experimental and Modeling Studies of Wax Deposition in Crude Oil
Carrying Pipelines., Ph.D. Dissertation, University of Utah, January 2005.
Leelavanichkul, P., Deo, M., Hanson, F., Crude Oil Characterization and Regular model has not been commercially developed.
7
Solution Approach to Thermodynamic Modeling of Solid Precipitation at Low
Pressure., Petroleum Science and Technology, Vol. 22, No. 7 & 8, 973-990, 2004.
Azvedo, L., Teixeira, A., A Critical Review of the Modeling of Wax Deposition
8
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.
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 n-
9 Properties, Petroleum Science and Technology, Vol. 21, No.'s 5 & 6, 863-878,
2003.
10
Wu, C., Wang, K., Shuler, P., Tang, Y., Creek, J., Carlson, R., Cheung, S.,
Measurement of Wax Deposition in Paraffin Solutions, AICHE Journal, Vol. 48,
No. 9, Sept. 2002, 2107-2110.
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.
11 Waxy Crude Oils under Quiescent Conditions, Energy & Fuels, Web Release
10/24/07, ef700357.
12
Summary / Key Points
These authors found no evidence for any intermolecular interaction between waxes and asphaltenes, and instead they propose that asphaltenes are merely contained in the solid wax as occluded oil. However the deposits
from which this analysis was based upon were not generated by wax crystallization/precipitation.
This paper presents experimental results for a model oil system which shows that the presence of asphaltenes hinders the gelation mechanism. The addition of asphaltenes in small proportions (~0.1 wt%) resulted in a
significant decrease in the gelation temperature, and decrease in the yield stress. High concentrations of asphaltenes resulted in a macroscopic phase separation: a deposit consisting of asphaltenes and paraffins
separated out of the liquid. The gelation temperature is the temperature where enough solid wax has precipitated that the fluid exhibits a yield stress using a controlled stress rheometer.
The author presents the results of experimental work done with model oil systems which shows that flocculated asphaltenes generate wax crystallization sites, which results in an increase in the wax precipitation
temperature exhibited by the oil. The study also showed that the presence of flocculated asphaltenes interferes with the crystal inhibition mechansim of a maleic anydride crystal modifier.
This paper presents equations for crystal growth rates expressed in terms of fundamental driving force of crystallization calculated from the activity of supersatrurated solutions and compared to expressions derived from
thermodynamic concentration differences.
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
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
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
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
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
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
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
was actually Brownian motion.
parraffins exhibited lower Wax Precipitation Temperatures and that injection of light condensates also improved WPT's.
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
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
(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
qualitatively mirrored those for the model oil.
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 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
13 Techniques and the Influence of the Oil Composition on Its Detection, Petroleum and exploratory modeling.
Science and Technology, Vol. 23, 1113-1128, 2005.
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
14 Larsen, R., Lund, A., Argo, C., Makogon, T., Cold Flow - A Simple Multiphase
less interaction amongst solids.
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, This patent describes a method of producing "Cold Flow" by injecting natural gas into black oil.
15
October 6, 1987.
 December 31, 2007
Rev. 0

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.
16 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
17
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
18
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
19
2000. Data acquired in this work indicate that Pompano and Troika oils have a significant natural ability to resist hydrate plugging.
20 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.
21 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
22
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".
23 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.
24 Shuqiang Gao, Investigation of Interactions between Gas Hydrates 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).
and Several Other Flow Assurance Elements, Energy Fuels, 2008, 22, 3150- 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
3153.
25 Nichita, D., Bessieres, D., and Daridon, J., Calculation of Joule-Thomson Inversion 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
Curves for Multiphase Systems with Waxy Solid-phase Precipitation, Energy & JTIC can be very important.
Fuels, 2008, 22, 4012-4018.
26 Fidel-Dufour,A., Herr, J., Formation and Transportation of Methane Hydrate 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
Slurries in a Flow Loop reactor : Influence of a Dispersant. 4th International 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.
Conference on Gas Hydrates, Yokohama : Japan (2002).
 December 31, 2007
Rev. 0

RPSEA 1201 - Pigging References

Reference No. Citation Summary / Key Points

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
1 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
Wang, Q., Sarcia, C., An Experimental Study on Mechanics of Wax Removal in 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
Pipelines, SPE 71544, 2001. - with disc pig design giving the best removal efficiency.
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
2
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
3
Content, Publication of Pigging Products and Services Association, 2006. This document provides guidelines for "best practice" regarding pigging of pipelines with high wax content.
Robins, L. (Tracerco), On-Line, Non-Intrusive Diagnostic Techniques for Pipeline This paper describes the basics involved in using radioisotopes as tracers, and provides case studies of applications. A specifc example is provided
4 Inspection and Flow Assurance., Published by the Pigging Priducts and Services for an NGL pipeline where variation in pig velocities identified the location (and character) of pipeline deposits.
Association, 2003.
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
5 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,
6
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
7
Deepstar CTR 4202-b1, Multidiameter Pig Tests, April 2000 not very promising.
8 Deepstar CTR 4202-b6, Mechanics of Wax Removal, November 2000. Provides detail of reference 1.
Brown & Root Energy Services (BRES) and Halliburton Energy Services (HES) jointly performed this study on the pigging of deepwater production
flowlines.The study includes basic information, equipment requirements,procedures etc. applicable to deepwater pigging operations; with emphasis
placed upon selection between round trip (RT) versus single trip (ST) systems. Several case studies were presented. Of special interest to Cold
9 Flow, was the lack of existing or planned pigging systems which are specifically designed to operate in the high solids content environments
envisioned. In particular it was noted a current (in 2000) ~10 mile limit for subsea tiebacks based on limitations of current pigging systems seems to
corrleate with this. The current status of the "Active Pig Technology" attributed to Shell E&P and Transglobal Ltd., Houston, Texas should be
Deepstar Report CTR 4303-1, Pigging of Deepwater Flowlines, January 2000. investigated further.

10 Deepstar Report CTR 6302, Subsea Pigging Technology for Flow Assurance, This study addresses alternatives to the conventional approach used in deepwater development of providing dual flowlines, which allows roundtrip
January 2004. pigging for flow assurance. Specifically, the study developed comparative evaluations for reasonable systems for 5 to 10 mile tie-back cases.
Number Title Author(s) Year Synopsis
010918 Evaluating New Chemicals Pickering, P.F., B. Edmonds, R.A.S. 2001 Discusses hydrate formation with detail in
and Alternatives for Moorwood, R. Szczepanski, M.J. Watson hydrate-forming chemicals; evaluates the
Mitigating Hydrates in Oil & effectiveness of various hydrate-inhibiting
Gas Production methods, namely Thermodynamic and
Kinetic Hydrate Inhibitors and Anit-
00049172 Multiphase Transportation: Leporcher, E.M., J.L. Peytavy, Y. Mollier, J. 1998 Prevention of hydrate plugging achieved
hydrate plugging prevention Sjoblom, C. Labes-Carrier by creating an emulsion slurry in pipelines
through crude oil natural using natural surfactants such as
surfactants asphaltenes. Waxes also considered;
evidence indicates higher wax content
allow for higher watercuts in streams.
00071550 Conversion of Water to Larsen, R., V. Andersson, K.W. Hjarbo 2001 Details specifics in regards to hydrate
Hydrate Particles 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.
SPE-109670-MS-P Flow Assurance Challenges Kopps, R., R. Venkatesan, J. Creek, A. 2007 Discusses flow assurance strategies for
in Deepwater Gas Montesi dealing with hydrates and wax deposition
Developments separately. Geometries, flow conditions,
etc. all necessary for evaluations of each
case. Various strategies for hydrate and
wax management presented.
SPE-111006-PA-P An Application of Vacuum- Singh, P., J. Walker, Hyun Su Lee, S. 2007 Internal coatings for wax deposition
Insulated Tubing (VIT) for Gharfeh, B. Thomason, D. Blumer prevention are only marginally effective;
Wax Control in an Arctic once wax deposition occurs, the coatings
Environment 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
SPE-111903-MS Use of Thermal Insulation to Owodunni, O.L., J.A. Ajienka 2007 Insulation and other materials studied to
Prevent Hydrate and determine heat transfer qualtiies to reduce
Paraffin Wax Deposition cooling along pipelines to prevent hydrate
and wax formations.
Paper # Title Author Year Summary Keyword
(2) 640_1 Pipeline/Flowline Pigging MOHR RESEARCH 1994 Pigging strategies set forth with respective Pigging
Strategies purposes, successes and problems with each
method. Various types of pigs presented with
photographs and schematics. Intelligent pigs
(2) 931_1 Chemical Methods to Control Paragon Engineering 1994 Following are for a subsea well for a 50-mile pigging, wax crystal
Paraffins Services, Inc. flowline to shallow water fixed platform or to modifiers, dispersants,
floating production systems. Chemically solvents
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
(2) 932_1 Thermal Methods to Control Paragon Engineering 1994 Assorted thermal techniques and scenarios Thermal
Paraffins Services, Inc. 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
(2)933_1 Paraffin and Asphaltene Sea Troll Engineering, Inc 1994 Mechanical state-of-the-art methods for paraffin TFL, Through
Control by Mechanical and asphaleten control in subsea wells. Flowline, pigging, coil
Methods Methods studied are as follows: Through tubing, reach rods,
Flowline (TFL) or pumpdown hydraulic well paraffin,
servicing, wireline, pigging, coiled tubing and
reach rods. Deepstar disadvantages: low temp
which promotes early paraffin deposition.
Complex remedial and maintenance problems in
Gulf of Mexico reservoirs that could complicate
paraffin control. TFL is expensive to equip for
subsea production systems. Circulation path is
required for propulsion and control of TFL tools.
Wireline not used because of cost and
mechanical problems in application of subsea
wells. No doubt that paraffin can be
successfully controlled by mechanical methods
(2) 934_1 Paraffin Waxes in Subsea Barth, J.R. - Exxon 1992 Treating wax in subsea and floating production Paraffin, Chemical,
and Floating Production Production Research systems are different than conventional platform Thermal, Mechanical
Systems Company and on-shore developments; wax precipitation
characteristics explored briefly; characterization
of waxy crude including WAT, PP;brief mention
of numberical modeling; chemical, thermal, and
(2A)208_1 Methods to Clear Blocked Texaco DeepStart 200 1995 39 cases of paraffin blockages and 16 of hydrate blockage, paraffin,
Flowlines Committee blockages identified with 45 of the 55 hydrate, gas hydrate
successfully removed. Common blockage blockages, unblock
removal methods: apply pressure (back flow or line, blockage location,
forward flow), circulate hot fluids, apply heat,
coiled tubing injected from platform end
(occasionally). When none of these successful,
line was cut and cleaned or removed and
replaced. Gas hydrate blockages required
venting the gas from both sides of the plug to
prevent the plug from acting like a projectile.
Topside or shore methods of heat or methanol
(2A) A212_1 Paraffin and Hydrate
Detection Systems
(2A)A900_2 Jolliet Pipeline Remediation
Study
(2A) A900_3 Paraffin/Hydrate Inhibition
Study - Phase Two
(2A) A900_4 Paraffin Deposition
Characterization Study
(2A) A902_1 Round-Robin Study of
Paraffin Inhibitor Selection
Methods
Paragon Engineering 1996 Identifies methods of monitoring hydrates and Hydrates, Paraffin,
Services, Inc. solid paraffins in subsea flowlines, specifically to Detection
detect the presence, deposition, and buildup;
crystal (in flow) detection: ultrasonic, NMR,
gamma ray techniques explored in detail -
currently being used is acoustic and/or sand
monitoring to detct solids in flow; methods for
detecting precipitation: pipe-external ultrasonic,
dielectric fluid contacting systems;
acoustical/pigging for remediation; blockage
location systems using compressibility of fluids,
pressure change/fluctuation systems, acoustical
Tret S Brown and Larry D. 1992 Report covering a paraffin blockage that had
Harrison from Conoco been depositing for over a year. A pig was
launched and became stuck. The pig was
Brown, T.S., Conoco 1992 Paraffin/hydrate mitigation techniques explored; Paraffin, Hydrate,
evidence of some chemical inhibitors Chemical Inhibitor,
intensifying paraffin problems; hydrate, paraffin, Insulation
and ashpaltenes together make analysis difficult;
use of nitrogen as an insulating material in the
annulus appears to have reduced parrafin
Lionel M. Fontenette 1994 Study to determine the solid make up of Paraffin, deposition of
Exxon company paraffins, asphaltenes, or a combination of both. paraffin, carbon
Each deposition composition must be number, Bulf of Mexico
determined to manage blockages. Results:
Paraffin is the main deposit problem in the Gulf
of Mexico. Exxon should focus on finding
resolutions to paraffin problems in deep water
before looking at asphaltenes or the
combination. The following were the tests
conducted: % asphaltene, %solids, %wax,
Deepstar, Texaco 1996 Deposition, rheology, and pour point depression Paraffin, Chemical
are effective methods in determining the quality Inhibitor
of chemical paraffin inhibitors; deposition is most
(2A) A902_1 Paraffin Inhibitor Selection Baker Performance 1995 Data generated on oil screening including Cloud pour point, cloud point,
Recommendations Volume II Chemicals Gulf Coast point on: blank oil, oil with 500ppm of each carbon chains, round-
Regional Lab and product. Pour point on: blank oil, 500 ppm of robin test
Champion Technologies, each product. Cold finder evaluation on 500 and
Inc 750 ppm of eachproduct, paraffin content and %
BS and W on oil samples. These were round-
robin tests to "develop and evaluate test
procedures which would be useful for the
evaluation of products in this and similar
inaccessible locations". Carbon chains were
between C-14 - C-32. Conclusion: The best
seem to be samples A-2 and E-2 after the
vaious tests performed (pour point screeding
and testing, cold finger testing, viscosity profile,
(2A) A903_1 Paraffin Inhibitor Selection Monger-McClure, T.G., 1996 Thermodynamic model testing addresses Paraffin, deposition,
Recommendations Marathon Oil Company paraffin deposition predictions for two wellbore modeling
Thermodynamic Model cases; significant limitations exist in using the
Testing - Volume 1 thermodynamic models, including correctly
identifying composition and interaction -
(2A) A903_1 Paraffin Inhibitor Selection
Recommendations-
thermodynamic Model
Testing
Texaco, BP, BHP
Petroleum, Conoco,
Exxon, Kerr-McGee
corportation, Marathon Oil
Company, Mobile E&P
Technical Center, Phillips,
Petroleum co, Shell Oil,
AsphWax, Inc, Calsep
A/S, Computer Modeling
Group, DB Robinson
Research Ltd., Hycal
energy Research
Laboratories Ltd,
Reservoir Engineering
Research Insitiute, Texas
A & M University,
1996 Vaious amounts of data collected from the afore
seen companies. An oil sample with 13% water
of form tight emulsion had the water removed by
adding 500 ppm Tretolite F46 de-emulsifier,
heated to 190 F 6-8 hours, cool and pipette
water off top. Drops water content to <1%.
Other samples: Nov 13, 1994: bubble point
found. Analysis with Low Temp Fractional
distilation, cryoscopy, gas chromatography,
Chain Rotators correlation. Data found on pg 94-
99. the majority of the pages are concerning
bubble point, viscosity, and the methods used to
find these values. The values are not the same
and have some variations. Solubilities of crude
oil were determined as well along with the size
of the carbon chains. Nenniger Engineering info
on pg 361+. " Measuring high molecular weidht
paraffins in crudes and solubility oof paraffins in
crudes and solvents. " Paraffin solubility is
sensitive to temp and MW. Paraffin noted up to
C-81. "At 30-50 C solubility of paraffins
decreases rapidly as MW of paraffin increases"
Gas chromotograph shows 1.66% wt of C-17+
paraffin in Deepstart Crude Oil "A". Cloud point
difficult at 53 C b/c of kinetic effects. Other
results of "A" show cloud point temp of 95 F and
at temps less than 9 F wax precipitation
increases sharply. Also, sample "B" was
tested. Could point severly effected by cooling
rate and cloud point is a very imprecie
measurement of equil thermodynamic models.
Recommends equilibrium thermodynamic wax
(2A) A903_2 Kinetic Model Testing -
Volume 1
(2A) A903_2 Kinetic Model Testing
Appendices
(2A) A906_1 Paraffin Prevention by
Coatings
Merrill, L. S., Marathon Oil 1996 Kinetic model used to predict wax buildup in Paraffin deposition,
Company flowing pipelines and wellbores; predictions did modeling
not agree well with field observations; a
particular well had an internally coated tube and
showed possible deposition effects i.e. more
deposition in the time allotted; some cases
Merrill, L. S., Marathon Oil 1996 Models to determine the deposition pigging, ST32, ST10,
Company measurements in 3 crude oils with varying pipe "A", "D", paraffin
wall temperatures similar to the field. Predicted deposition
were the wax deposition profile, total volume of
wax, pressure drop increase and temperature
profiles. These were performed for crude oil "A"
and "D". Differences between the two crude oils
is deposition tendencies. The tests show the
temperature profiles, wax buildup, etc over 7+
days at 2.4 BBLS. Pressure drops were quite
different from the two crudes. Results: Expects
well remediation at least every two weeks for
crude "D". Conoco Inc provided data on
DeepStart crude "C" in flowline, including wax
deposition profile, total volume of wax and
pressure drop increase at weekly intervals. Inlet
flowline reported at 70 F and paraffin is prediced
to deposit immediately as it enters the flowline.
Pigging would be required weekly. If temps
increse to 101 F, which may be possible,
paraffin deposition rates will increase
considerably and pigging would be required to
every other day. Computational models have
been developed to predict paraffin rates of build-
up (further info on pg 32). BP offered a
Buck, E. N t i cani prevent
1996 Coatings l h or significantly
i li i reduce
l ti ith Internal Coatings
paraffin deposition, but conditions necessary are
speculative; findings show that physical
parameter may be more important than chemical
parameter - surface roughness is only
(2A) A906_1 Crude Petroleum Production Texaco
Enhancement Investigation
(2A) A906_1 Microwave Measurement of
Oil and Paraffin
3202-1 Pipeline Blockage
Remediation
3205-1 Coatings for the Prevention
of Paraffin Deposition: Cold
Finger Screening Studies
3205-2 Coating studies and Testing - Efner, H. F., Phillips
Generalized Version
3205-3 Effect of Coatings on Wax
Deposition Under Turbulent
Flow Conditions
1996 A method to detect wax thickness on the inside ultrasonic, acustic,
of a pipe through ultrasonic high frequency energy, paraffin
acoustic energy. Problems from reflection of thickness
waves off the metal pipe caused some
problems. These problems were corrected and
the team was successful in detecting the wax
and then the oil in a lab experiment. However,
Ng, W.C., C.A. Avalle, 1996 Microwave material measurements used to Microwave
C.C. Shang determine the electromagnetic properties of oil
and paraffins; done to determine if possible to
detect location, thickness of blockages, also as
Radoil, Inc 1998 Collected data including: pipeline geometries
(bends, corkscrew turns, bore changes, etc) for
existing pipelines in Gulf of Mexico. Info used to
create computer programs that make test loops
representing typical 5 mile segments of subsea
pipeline. Conclusion: More data was collected
Efner, H. F., Phillips 1996 Experiment involving 39 separate coatings; Internal Coatings
Petroleum Company primary effect was reduction in paraffin depsoits
due to insulation effects; no correlation of
coating chemistry or surface finish with paraffin
reduction; flouropolymers and siloxanes were
1996 Cold finger screening method used; reduction in Internal Coatings
Petroleum Company paraffin deposits due to insulation; under
turbulent or high-shear flow conditions, coating
may have different effect on wax deposition. A
highly insulated coating may work in specialized
Hsu, J.J.C. 1997 Cold finger screening method used; reduction in Internal Coatings
paraffin deposits due to insulation; under
turbulent or high-shear flow conditions, coating
may have different effect on wax deposition -
concluded that nylon decreases wax deposition
3206-1 Paraffin Inhibitor Modeling
3208-1 Novel Deposition Control
Program - Verify Solvent
Recycling Process for Wax
Deposition Management
3208-3 Acoustic Tool Testing for Radoil Tool Company, Inc
Removal of Paraffin Deposits
From Tubulars
3213-1 ASTM Wax Appearance
Point Initiative
4201-a1 Test Engineer Final Report
SwRI Project 04-8217
Molecular Simulations, 1997 Final report from Molecualr Simulations, Inc on Paraffin, wax,
Inc "molecular modeling to improve the petroleum deposition, crystal,
industry's ability to predict the performance of molecular modeling,
paraffin deposition inhibitors and to design new inhibitors
inhibitors having improved performance."
Molecular models created to explain
thermodynamic properties and how they're
calculated. "Model for the action of polymeric
deposition inhibitors...developed." Wax analyzed
with QSAR methods allowing the best
correlations to the data. Algorithm developed to
describe the "adsorption isotherms for inhibitors
on paraffin crystal surfaces." the hope is to
design and inhibitor that matches the inhibitor in
Hsu, J.J.C., L.A. 1997 Pentane dilution tested as a wax-reducing Chemical Inhibitor
Washington solvent; not recommended for pipelines with
long sections below 60 F; pentane dilution has
negligible effect on WAT, but may decrease high
molecular weight content in the deposits, leading
to softening; reduces oil viscosity, significant
1996 Detailed photographs of pipeline plugs, tools, Acoustic, Other
and equipment used; Branson Hom had little Methods
effect on removing/dissolving paraffin in the
breaker testing; "logging" style acoustic tool had
Jim Tacket of Marathon 1998 Standard wax appearance points between 0-60 Differential scanning
and James Coleman of C with no more than 2% water wt and on both calorimeter,
ARCO transparent and opaque light stabilized oils.
This is mainly an appendix of safety, materials,
and procedure explaining that the wax/oil
Gregory J. Hatton 1998 The test engineer project was to develop a field projects, Wyoming,
test to address "deepwater GOM hydrate Colorado, lab tests,
plugging issues." This report discusses the fluid systems
piping, the system set ups of the various tests in
4201-b1 Deepstar Paraffin Field Tests Jack J. C. Hsu
4201-c1-1 Distributed Pressure
Measurement Inside Oil
Pipelines Based on the Fiber
Optic Brillouin Scattering
Technique: A Proff-of-
Concept Demonstration
4201-c1-2a Laboratory and Land well-
based optical measurement
of Distributed pressure and
temperature.
4201-c1-2b Laboratory-based
Simultaneous Measurement
of Distributed Pressure and
Temperature in an Optical
Fibre
2000 Leter from a visit of Jim Chitwood, Tom Chen, CBI, paraffin field tests
Tom Williams and Jack J. C. Hsu to understand
the field situation at CBI and make plans for
paraffin field tests. This report discusses the
options with the pros and cons of pipe diameter
Diatzikis, E., A. Mendez 1998 Invesitigation of the feasibility of measuring Pressure
hydrostatic pressure indie oil pipelines using a Measurement
fiber optic distributed pressure sensing
technique based on Brillouin scattering
technique of detecting axial strains along fiber;
fiber coating with combination of silicone and
nylon at .9 mm diameter gave most successful
pressure sensitivity - all fiber samples and
E. Diatzikis, A. Mendez of 2000 Phase II of discrete hydrostatic pressure
ABB Elictric Systems measurements with a fiber optic distributed
Tech Institute in NC with strain measuring the system. The second phase
Cheveron as the technical is to demonstrate fully distributed pressure
sponsor. measurements by deploying a fiber down the
wellbore of an in-land well. New fibers had an
increase in pressure sensitivity of approximately
62% from phase I. Temp sensitivity increased
3.6%. The psi range decreased to 15-21 psi.
The method can detect forward, reverse, flow,
no-flow, and differences in flow rate. Pressure
tests are feasable but temperature is still an
Parker, T. and M. 2000 Temperature cross-sensitivity introduced Pressure
Farhadiroushan pressure errors in fiber-optic pressure Measurement,
measurements; new technique of measuring Temperature
both temperature and pressure by measuring Measurement
both power and frequency of Brillouin light being
4201-c2-1 Acoustic Monitoring of Flow- Kutlik, R.L., Chevron 1997 Hydrate runs performed to create hydrate Hydrates, failed test,
Assurance Factors - Phase I Research and formation using black oil. The runs did not lab test
Technology Company create adequate hydrate formation and the
mechanical equipment noise overwhelmed the
sensitive acoustic transducers with low freq
noise. It was decided that further work should
be conducted on another site: Louisiana or
Colorado were suggested. It was later decided
4201-c2-2 Acoustic Monitoring of Flow- Kutlik, R.L., Chevron 2000 APOC studies to demonstrate hydrophone- Hydrates, Paraffin,
Assurance Factors Research and detectable passive-acoustic effects occurred in Detection, Acoustic
Technology Company, B. response to hydrate formation, multiphase-flow
Bridge, Entelek ACM regimes, waxing, valve status; wax-related
issues show promise in detectability and further
4201-c4 Initial Demonstration of MSS Nondestructive Evaluation 1999 Testing was performed on Magnetostrictive paraffin buildup,
Technology for Monitoring Science and Technology sensor (MsS) technology was tested to provide magnetostrictive,
the Development of Paraffin Division initial information about potential capability of paraffin thickness
on Piping detecting paraffin and its buildup in deep-sea detection
piping. This technology has been in
development for 5+ years. The technology
utilizes a magnetostrictive force to develop a
guided wave (at ultrasonic frequencies) in the
pipe. The tests were successful; paraffin was
4201-c5 Monitoring the Thickness of Schwartz, C.J., 1999 Use of magnetostrictive sensor (MsS) used to Paraffin, Detection
Paraffin Build-Up in 4-Inch Southwest Research detect wax buildup using waves at ultrasonic
Diameter Pipe Institute frequencies; wall discontinuities will scatter or
reflect the guided wave; use of an impacting
device for inducing flexural vibration with use of
accelerometers for measurement of response
4202a2 Depressuring Tool - Phase 2 Bollavaram, P., Selim, 2000 Research on hydrate plug removal through Hydrate plug, hydrate
Hydrate Plug Dissociation by M.S., Sloan Jr., E.D. pressure reduction. Hydrate dissociatoin by two- plug removal, two-
Method of Depressurization sided depressurization was conducted in lab sided
with a 36 in by 1 in pipe with L/D of 36; depressurization,
previously L/D of 4. It was shown that hydrate radial dissociation
plugs dissociate radially and that plug length is
not nearly important as plug radius for porous
plugs; hydrate plug length usually exceeds
diameter by several orders of magnitude.
Preliminary results on one-sided
depressurization indicates dissociation
mechanism is a strong function of system
4202-b1 Multi-Diameter Pig Test Radoil, Inc 2000 Radoil was contracted to manufacture and test Pig, multi-diameter pig,
multi-diameter pigs and contracted with Texas Petal Type Pig, Angled
A&M Univ. to study these pigs in a remote Leaf spring Pig
subsea location within a 3 in ID pipeline,
expanded, and return in an 8 in ID pipeline while
cleaning the bore. The student designed pig
buckled in the pipeline causing it to be immobile.
The angled leaf spring pig and a Radoil
4202-b5 Paraffin Deposition 2000 This is a overview of a workshop for paraffin wax crystal
Workshop deposition with the deepstart IV project. The modifications, cloud
workshop was designed to allow for an point, thermodynamic
exchange of theories and ideas on the science modeling, deposition,
of paraffin deposition. Cloud point measurement crystallization,
and thermodynamic modeling was deemed
sufficient and accurate. Field and experimental
data are needed for deposition rate predictive
tools. Lab tests need to be developed better to
predict and quantify wax crystallization and
deposition. Data acquisition complicate
experimental modeling. Understanding how wax
initially forms has yet to be solved and improved
porcedures and predictions for experimental
4202-b-3a Asphaltene Studies Texaco, various authors
Workshop (see presentations for
details)
4202-b-3b
4202-b-3c Prediction of Asphaltene Buckley, J.S.; Hirasaki,
Deposition G.J.; Chapman, W.G.
Contributors: Wang, J.,
Fan, T., Padilla, H., Ting,
D. (all from Rice
University).
4203-a3
2000 Series of presentations and workshops on Asphaltene
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
2001 35 oil samples were provided for testing of Flocculant, PRI,
asphaltene stability, including refractive index of deposition,
oil and solubility parameters at onset conditions asphaltene, Flory-
for quantitative description. Experimental Huggins, stability,
observations include the tendency of oils in
sample set to adhere to polished hermatite
surfaces and for asphaltic material to deposit
and plug on stainless steel capillary tubes. An
unusual number of oils from deepstar produce
fine asphaltic particles before first aggregates
appear. The most distinguishing characteristic
of many oils in the group is the tendency to form
asphaltic fine particles over a wide range of
solvent conditions before the onset of aggregate
formation is reached. The Flory-Huggins
solubility model is used b/c it uses RI values.
All oils tested adhere to hematite under low pH,
low ionic strength aqueous phase and in the
presence of synthetic sea water. Higher pH
made some distinctions between diff oils and
solutions in AMN. Deposition occured on some
4203a-3a Flow Loop Tests on Troika Matthews, P.N., Notz, 2000 Both Troika and Pompano are black oil, sub-sea Plug flow formation,
and Pompano Oils P.K., Prukop, G., tie back systems in the Gulf of Mexico. The oil demulsifier, water cut,
Widener, M.W. at these locations have significant natural ability Troika, Pompano,
to resist hydrate plugging. Plugging did not hydrate, brine, NaCl.
occur until 38.9% and 45% water cut
respectively. It has been found that some oils
have a natural tendency to resist hydrate plug
formation. Hydrates form redily in these oil but
are suspended in a continuous oil phase, flow as
a slurry and do not agglomerate into a plug.
Pompano oil plugged after 48.9% water cut
reached with dP (dP=change in pressure) of 49
psi(5.5 fold increase). When Pompano was
treated with demulsifier the results didn't change
4203-b1 Flow Assurance Design 2001 This is a guideline for flow assurance design. Flow assuracne
Guidline The listings of this document are as such: Flow design
assurance, design process, fluid properties and
phase behavior, multiphase flow, steady-state
hydraulic simulation and line sizing, termal
modeling, transient operations, hydrates,
paraffin waxes, asphaltenes, emulsions, scale,
4303-1 Pigging of Deepwater Brown and Root Energy 2000 A report that includes basic information, Pigging, Round trip,
Flowlines (Final Report) Services/Halliburton equipment requirements, procedures etc Single trip, chemical
Energy Services applicable to deepwater pigging operations, injection, deep water,
including flowlines. The report can be hlepfl to offshore.
operators in selecting an appropriate pigging
solution consistent with the specific field
parameters. Tests were performed for four
different hypothetical deepwater fields in 10,000
feet of water and included oi and gas fields in
large and samll size. Production oil with high
GOR and wax and cloud point was used, as well
as production gas with condensate and high
water content for potential hydrate formation.
Hydraulic analysis showed that flowlines over 10
5201-3a Produced-Stream Hatton, G. J., SwRI, V.R. 2001 CEBPT without chemical inhibition for hydrates Paraffin, Hydrate,
Conditioner Enabling Single Kruka, VRK Technologies and wax; SINTEF and KBR participated fully in Conditioning, Non-
Bare Pipe Transport this study; SINTEF's model involves pumping a Chemical Inhibitor,
"cold" recycle with intermittent injection of free Pigging
and warm water into the flow loop; KBR calims
to model all aspects of system including waxy
5201-4 Hydrate/Wax Slurry Barajas, A.M., R.A. Hart 2003 Oil-hydrate slurry tested in various flow loop Hydrate, Slurry
Transport Tests arrangements; experiments not carried out for
as long a time as desired; oil-hydrate slurry
mixed together using diesel, naptha, and natural
gas; no mention of wax or long-chain paraffins in
document; hydrate particles tended to
accumulate in U-tubes; suggest using plastic
beads of appropriate size and density to
5306-1 Study Opertaional Aspects of Mentor Subsea 2004
Single Line Pigging Technology Services, J.
Wax Control In the Presence of
Hydrates

Department of Chemical Engineering

University of Utah

Milind Deo
Jules Magda
Rich Roehner

RPSEA DW 1201
 What is cold flow?
Transport of oil in single uninsulated
pipeline over large distances (tens to
hundreds of miles) while managing wax
and hydrate (and other) deposition and
plugging problems
 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
Phase II-- Information Gathering
Description of the technology and how it
works
Technical gaps
The state of development of the
t h l
technology and
d its
it availability
il bilit
Effectiveness of the technology, when
used in a cold-
cold-flow deepwater subsea
application
 Technology Criteria
1 Is the technology as defined, applicable to cold-
1. cold-
flow conditions?
2. What is the scientific basis of the p
proposed
p
method?
3. How easy/difficult
y would it be to deploy
p y the
method over several hundred miles of pipe?
4. Under what conditions is the method likely to
fail? (range of applicability)
5. 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 andd
understanding
Deepstar Studies
 Current Practice

Single insulated line Dual line Roundtrip

pigging

Coiled
C il d ttubing,
bi h
heatt ttracing
i and
d iinsitu
it hheatt generation
ti also
l used
d
Benchmark (Current) Technologies
and Rank (C
(CTR-6302)
(CTR-
Single flowline insulated (1)
Dual flowline roundtrip pig
g ((3))
Single flowline wax in place (7)
Single flowline heat (9)
Single flowline chemical treat (11)
Other Single flowline methods
evaluated
Crawler (2) SGN (5)
Coiled TAC pig (4) Jetstream pig (10)
Subsea pig launcher Go--Flo (6)
Go
(8)
Power pig (12)
Auxiliary line (13)
Progressive pigs (14)
Wax eater (cold flow)
(15) CTR 6302
CTR-6302
Evaluation Summary
Cold Flow Wax Eater Version
Low CAPEX
In 6302, considered inapplicable in
presence of hydrates
High OPEX (due to hydrate mitigation) and
risk
i k off failure
f il puts
t the
th technology
t h l att the
th
bottom of the list
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 wax-
wax-hydrate
h d t ttransportt
reviewed
Technology demonstrated at bench/pilot scale with wax-
wax-
h d t mixtures
hydrate i t
Good scientific basis
Absence of a thermal flux
Removal of higher molecular weight waxes
Possibility of flowable slurries with high solids loading
Range of applicability good; needs further evaluation
 How does cold seeding work?
Dissolved Wax
Precipitated Wax

Sea Water at temperature, Twater

Tflow > WAT Tflow = Twater

Cold Flow Equipment

Adapted from Correra, et al (2008)

 Precipitated Wax
Wax Eater

Cold Slurry Hot Oil

T = 3~4 oC (Seabed) Periodic pigging to remove deposits

Adapted from Correra, et al (2008)

 Another Method of
Di
Dissolved
l d Wax
W
Creating A Slurry
Precipitated Wax
Gas

Shell Process
Adapted from Correra, et al (2008)
Nenninger Cold Flow Work (CTR 4202-
4202-b2)

Wax only
Seeding (polyethylene) reduces deposition
Deposition depends primarily on super
super--
saturation
Deposit thicknesses are not an effective
ff
indicator
Seeding may not be necessary at low oil
temperatures
Questions heat flux models
 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
Mainstay of wax remediation technologies
Effectiveness and range of applicability not in question
A number of studies on best practices,
practices optimization
optimization, round-
round-trip
pigging, etc.
Hardness of deposits and pigging efficiency
Goes hand in hand with depositional studies to design
frequency of pigging
Some advances instrumented devices for location,,
hardness, type, etc.
Advanced Pigging Technologies

Crawler Pig
Subsea launcher Power Pig

Progressive Pigging
Heat and Thermal Management
Active heating
g ((flowline
flowline,, export
p line,, etc))
Cendejas
Cendejas,, et al., 2006, Thermal Design of Wells Producing Highly
Viscous Oils in Offshore Fields of Gulf of Mexico, SPE 103903
Heat management
g strategies
g discussed in several p
papers
p
A number of papers on insulation
Applicable to cold flow
I t iti
Intuitive
Would require good planning
May
ay have
a e to
o be e
evaluated
a ua ed o
on a case by case bas
basis
s
 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
 Factors Affecting Wax Inhibitors

Interaction enhancement between the inhibitor polymers and

waxes in oil
Polymer backbone:
backbone: a slight effect on pour point depression
Length of the pendant chains:
chains: existence of effective (optimal)
length
Polymer molecular weight:
weight: No significant effects on the pour
point depression with the polymers with same backbone and
side chain length but different molecular weights
Solvent or polymer diluents
diluents:: Polymers are waxy and often solid
phases at ambient conditions. Need good solvents for them to
be effective
 Dependence of Chemical Inhibition on
Crude Oil Composition

Waxes in Oil Effective Ineffective

Normal / (cyclo + iso) Low High

Quantity of C24+ < 32% > 52%

Wax distribution Bimodal Monomodal

* Source: SPE 49200

 Effective Wax Inhibitors

Ethylene vinyl acetate Ester

Polymer
ELVAX 150 ELVAX 240 Polyacrylate Polymethacrylate

Molecular
87,767 82,900 97,730 103,900
weight

Tm (oC) 60-63 70-74 53 48

Degree of
- - 50-55 20-26
Crystalinity, %

Pour point (oC) 10 4 -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
Thermodynamic Hydrate Inhibitor Low dosage Hydrate Inhibitor
Type (THI) (LDHI)

Shifts the thermodynamic Delays nucleation or modifies

Act equilibrium of hydrate formation hydrate crystals

Dosage
amount 10 to 40 vol% 0.25 to 5 vol%
(water basis)
CAPEX
High Low
OPEX

Ch i l
Chemical M OH MEG
MeOH, V i
Various polymers
l

Different types of LDHI Kinetic, Anti-agglomerates, etc.

 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 high-
high-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
 Sonic Management Methods
Acoustic techniques to remove paraffin in pipes appear not be
practical (CTR-
(CTR-3208)
A number of other Deepstar reports on use of ultrasound for
detection
Sonic management methods (other papers)
Towler et al., 2007, Experimental Investigation of Ultrasonic
Waves Effects on Wax Deposition
p Duringg Crude Oil Production,,
SPE 109505
Possible applications to cold flow
Tested under limited conditions
Limited scientific understanding
Extensive testing necessary to ascertain range of applicability
 Biodegradation

Biodegradation
Kotlar
Kotlar,, et al., 2007, Wax control by Biocatalytic Degradation in High-
High-
Paraffinic Crude Oils,, SPE 106420
Empirical science for the most part
Limited testing
Di t ib ti and
Distribution d mixing
i i off microbes
i b withith mixtures
i t
Likely to be expensive
Magnetic Conditioning (3208-
(3208-2)
Good discussion on instrumentation, etc.
Magnetic fields didn't have an effect when
oriented p
perpendicular
p to fluid flow
Para
Para--Mag and UF3 devices (parallel) depressed
WAT slightly
g y (by
( y a degree
g or so))
Significant development required
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
Single uninsulated line
Cold-flow
Subsea-pig
Single flowline heat Crawler pig
Sub-sea processing
Chemical support
Single flowline chemical
treat

Single
g flowline wax in
place
Our Preliminary Ranking Using the RFP
Criteria

Cold Seeding 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 2
 Proof of Concept Testing
This phase will evaluate the most
promising cold-
cold-flow wax management
technologies as identified on Phase 1
technologies, 1,
through more detailed investigations and a
proof--of
proof of--concept testing program
program.
 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 hydrate-
hydrate-wax solutions
Coatings are not practical
A chemical solution to cold-
cold-flow appears
unlikelyy
Sonic--magnetic
Sonic magnetic--biodegradation methods need
significant
g development
 What we do not know well
Fundamentals of wax-
wax-hydrate slurry
formation
Cooling and heat transfer requirements
Thermodynamics of slurry mixtures
Morphology
Agglomeration characteristics
Yield
Yi ld b
behavior
h i
Rheology
Range
R off applicability
li bili
 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 cold-
cold-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