You are on page 1of 4

World Oil

®
Originally appeared in APRIL 2015 issue, pgs 73-78. Used with permission.

FLOW ASSURANCE

Non-toxic paraffin remover returns


flow to long-plugged GOM pipeline
Conceived from chemistries in other
Fig. 1. Chart depicting the departing pipeline pressure, 14 days
industries, a non-toxic paraffin removal prior to losing communication, as well as the point at which
agent has shown that it can restore flow to blockage occurred.
severely plugged pipelines

ŝŝKEVIN AYERS and CHARLIE TALLEY, Ideal Energy Solutions, LLC


A granular derivative of chemistries conceived for use in the
food services and brewing industries, re-formulated as a paraf-
fin removal agent, has effectively restored oil flow in a severely
plugged Gulf of Mexico pipeline that had been slated for de-
commissioning.
In less than two days of intermittent pumping and soaking,
the aqueous-activated solution, acknowledged as the industry’s
only non-toxic paraffin remover, had established full commu-
nication on a 1.43-mi., inter-platform flowline that had been
out of commission for 10 months. Nearly the full length of the
8-in. flowline, in just under 127 ft of water in the Vermilion area Over the years, the numerous economic and HSE is-
offshore Louisiana, was determined to be plugged by paraffin sues associated with paraffin build-up are equaled only by
wax, Fig. 1. Previously, a number of high-pressure pumping at- scores of chemical and mechanical remediation efforts that
tempts, using conventional solvents, had proved unsuccessful, have been advanced with widely mixed results.1,2,3,4,5 For in-
leaving the operator little choice but to plan on converting a stance, typical chemical treatments, including line heating,
6-in. water line to transfer oil between the two platforms. warm solvents, hot oil treatments and conventional wax in-
Unlike traditional solvents, the multi-patented technology, hibitors, are largely ineffective in longer pipelines, and when
comprising a proprietary blend of surfactants, is not only non- temperatures fall to 40°F and below. Pipeline lengths and
hazardous and temperature-independent, but its density and any bends present, likewise, restrict coiled tubing interven-
composition effectively lower surface tension, allowing the so- tion, which is otherwise relatively effective, but comes with
lution to penetrate between the blockage and pipe wall, as well a high cost and risks.
as throughout the micro-cracks within the wax deposit itself. Generally described as a white or colorless soft solid, paraf-
A specially formulated and controlled, oxygenated alkaline fin is derived from hydrocarbons, coal or shale, and comprises
composition acts on the adhesion intrinsic to paraffin, effec- a mixture of hydrocarbon molecules containing anywhere
tively dislodging the wax into chunks that can flow easily out from 20 to 40 carbon atoms (Cx). Paraffin build-up can either
of the pipeline, and be collected for disposal. Furthermore, the occur naturally with the flow of crude through the pipeline, or
solution is activated by either freshwater or seawater, making through mechanical practices, such as vacuum pumping or the
it equally effective in both onshore and offshore applications. injection of stimulating chemicals and some solvents.
Even at moderate temperatures, paraffin displays limited
PREVAILING PARAFFIN ISSUES solubility when in contact with most types of inorganic sol-
The deposition of paraffin wax and its closely related cousin, vents, and is virtually insoluble in aqueous solutions. Once the
asphaltenes, in flowlines and associated production components temperature of the streaming oil falls below the cloud point,6
has long been regarded globally as one of the industry’s most which in crude oil is also defined as the wax appearance tem-
expensive and difficult-to-mitigate flow assurance issues. In the perature (WAT), the end paraffin components begin to crys-
U.S., alone, it is estimated that paraffin deposition costs operators tallize into solid wax particles. Thus, deposition typically oc-
upward of $2 billion/yr in restricted or delayed production, of- curs when the wax entrained with oil contacts any surface that
ten-fruitless remediation attempts, and pressure-induced equip- has a temperature below the cloud point and has a heat sink.
ment damage. While paraffin wax can manifest itself in any on- Crystallization also is accompanied by a phenomenon that
shore or shallow-water pipeline, the costs and removal difficulties in colloid science is described as the zeta potential,7 which
are magnified appreciably in the colder subsea temperatures of propagates the stickiness that makes paraffin wax so enor-
remote deepwater tie-backs and other flowlines. mously difficult to remove, once deposited. The sticky par-
World Oil® / APRIL 2015 73
FLOW ASSURANCE

Fig. 2. Dislodged paraffin being pumped from the 1.3-mi pipeline (left) and a portion of the removed wax collected (right) during the
removal process.

ticles will attach to each other as though coated with glue, ing the brass filter plates at a rate of 1,000 ppm of free copper
as well as along the pipeline wall. Obviously, the longer the per wash, while also destroying the digestive bacteria in the
particles are allowed to coagulate, the larger and more es- brewer’s waste treatment systems.
tablished the blockage, until eventually the entire cross-sec- A series of tests resulted in a novel, and highly effective,
tional flow area of the line is plugged, and production halts. hydration technique that isolated the surfactants from the vol-
Moreover, even before the line is completely blocked, the atile sodium percarbonate in a dry formulation, while elimi-
buildup of paraffin and asphaltene wax along the pipe wall nating the copper discharge. The then-newly patented formu-
propagates roughness that increases the pumping pressures lation laid the groundwork for its eventual use in the oil field,
required to move production and places tremendous strain on with its capacity to remove all beer deposits and microorgan-
pumping equipment. isms, and do so at colder temperatures, lower concentrations
The HSE risks, as well as the temperature restrictions and and faster than the previous cleaner.
other limitations of conventional chemical and mechanical That earlier work served as the springboard for its current
remediation methodologies, prompted development of the use, when it was discovered that a precise combination of sur-
non-toxic additive for the removal of paraffin wax. factants in a alkaline system, in tandem with neutralizing oxy-
gen, could remediate paraffin/asphaltene deposits.
ECLECTIC DEVELOPMENT HISTORY
The origin of what evolved into the uniquely engineered, CORE FORMULATION PRINCIPALS
paraffin removal solution followed a rather circuitous route, Compared to most conventional solvents, one of the key
that included formulations specially modified for the food differentiators of the new additive is lowering of the surface
service and beer brewing sectors. Two of the seven patents tension, commonly linked to interfacial tension, which is vi-
covering what is now an effective oilfield paraffin remedia- tal to the agent’s emulsification properties. Primarily, interfa-
tion agent reflect its earliest roots,8,9 during which a prototype cial tension penetrates the adhesive forces between the liquid
formulation was shown to completely break down fossilized phase of one surface and either a solid, liquid or gas phase of
vegetable matter. another substance. In a series of internal tests, the interface is
The earliest precursor of the current formulation was de- a cleaning solution that “wets” a surface on an incline, where-
veloped in 1995, in the form of a high-foaming detergent, upon the degree of wetting is measured.
based on sodium metasilicate and sodium phosphates, which Consider that, as measured by the Kruss Bubble Pressure
proved highly effective in removing extremely dense black Test, tap water at room temperature exhibits a surface tension
protein stains left on stainless steel from the production of re- force of around 76 dynes/cm, far more than the 42.3 dynes/
fried beans. That work also led to a promising new compound, cm of diesel. At 5% solution, the new paraffin remover mea-
sodium percarbonate—a combination of hydrogen peroxide sures 22.2 dynes/cm. Quite simply, in an oil-water combina-
hydrated on soda ash—which, unfortunately, exhibited ex- tion, by adding a blend of surfactants to the aqueous phase,
treme volatility in the presence of organic material having 14% the oil molecules tend to orient themselves into alignment
available peroxide. with the water molecules, resulting in miscibility, or the for-
At the behest of a major brewery, the basic research was mation of a homogenous fluid.
expanded a year later with the conception of an alkaline clean- Furthermore, the formulation of specially blended surfac-
er to replace the standard sodium hydroxide-based product tants optimizes the hydrophilic-lipophilic balance (HLB),
used to remove bacterial contamination from cold filtering defined as a measure of the degree to which a surface active
units. The standard cleaning compound was actually dissolv- agent is hydrophilic or lipophilic, meaning it is either attracted
74 APRIL 2015 / WorldOil.com
FLOW ASSURANCE

Fig. 3. The platform layout for the paraffin remover injection. Fig. 4. The layout onboard the M/V Abigail Claire support vessel.

of surfactants and other elements. This resulted in a slightly


oxygenated system, whereas oxygen was released over an 8-to-
24-hr period to negate the zeta potential, and the stickiness of
paraffin and asphatelene waxes.
The newly formulated solution was field-tested on an
to water or to oil. Using this type of combined surfactant is onshore pipeline—30% of which was plugged by paraffin—
advantageous in drawing organics into the water phase. where it proceeded to remove 100% of the blockage in 24 hr.
What results is a solution with a density higher than that of Afterward, the technology was selected to hopefully re-estab-
any production fluids or solvents in the pipeline. Thus, once lish communication on the 7,550-ft Gulf of Mexico inter-plat-
introduced, the heavier solution displaces the lighter fluids, as form pipeline.
it migrates down the line and within the wax deposit, with no Over 10 months, four high-pressure injections of a phenyl-
length, geometric or temperature limitations. arsine oxide (PAO) solvent had failed to dislodge the extreme
Moreover, the smaller carbon chains, specifically C13–C18, wax build-up. One of the unsuccessful attempts involved
intrinsic to paraffin deposition, comprise open-chain satu- pumping the PAO solvent at pressures exceeding 1,200 psi,
rated hydrocarbons that are virtually non-reactive and critical whereas prior to losing communication, the normal operating
to soap and surfactant chemistry. Therefore, coalescing high pressure in the flowline was 75–85 psi. Meanwhile, operation-
alkalinity with the correct surfactant package clears the way al logs showed the pipeline, which was installed with a riser
for emulsifying and sulfonating the shorter-chain alkanes, and configuration comprising four 5R bends, had not been pigged
in so doing, generate simple soap lubricants. The simple soap for 17 years.
generated by sulfonating a small portion of the material pres-
ent in the oil then becomes water-soluble and begins to break DATA-DRIVEN REMEDIATION STRATEGY
apart the paraffin plug. Much of the pre-job data analysis dealt with ascertaining
To further clarify, the production of a simple soap requires the composition and location of the blockages. An acousti-
only a base and an organic fatty acid, which, in the case of cal survey had isolated the blockage at 469 ft from its point-
crude oil, includes naphthenic acid (R(CH2)nCOOH). When of-origin on one platform, with possible blockage also 467 ft
this and other organics come into contact with the reactive from the initiation point on the other platform. Initially, it was
sodium carbonate (Na2CO3) of the new paraffin remedia- believed that the shutdown resulted from bacteria-induced in-
tion additive, it generates this standard chemical acid base ternal corrosion and from metal filings from scale buildup at
reaction with: the riser elbow, on the side of one of the platforms. An earlier
R(CH2)nCOOH+Na2CO3→R(CH2)nCOONa+NaHCO3 analysis of a deposit sample suggested a mixture of only 17%
(Naphthenic (Sodium (Sodium (Sodium paraffin, with iron oxides making up 83% of the deposition.
acid) carbonate) naphthanate) bicarbonate) However, an evaluation of historical treater pressure data
In addition, earlier studies at M.I.T. suggested elemental strongly indicated that the 8-in. line, more than likely, con-
oxygen under pressure could modify n-paraffins. Taking that tained significant paraffin deposition along its entire length.
investigation further, elemental oxygen, which alone is highly Reinforcing that supposition is the fact that paraffin and
effective at neutralizing the zeta charge of paraffin, was com- similar wax deposits tend to accumulate over time, thus the
bined in a single chemical package with the synergistic effects increasing treatment pressure volumes documented in the his-
76 APRIL 2015 / WorldOil.com
FLOW ASSURANCE

respectively. The only other required additions to both plat-


Fig. 5. Pumping pressure chart, showing the decrease in pressure forms were a 2-in. flange and ball valve installed on the bottom
once full communication was established. of the pig trap, and a 2-in hose connecting the pig trap to the
1,600 MPT, Fig. 3. As a contingency, a 2-in. hot tap was installed on
1,400 both risers, though the solution can be injected into the pipe-
1,200 line from any point on the platform offering sufficient entry.
1,000 The 220-ft M/V Abigail Claire support vessel, which served
800 as the operational base, likewise required only three 500-bbl
Psi

600
tanks to collect both the solid and flushed liquids, a 350-gal
mixing tote, two 550-gal product storage totes and a 50-bbl
400
seawater clean-out tank. The solution would be injected from
200
0
the vessel via a PE5 pump, fitted with a 3-in. air diaphragm
1:15 1:25 1:35 1:45 1:55 2:05 2:15 2:25 2:35 2:45 2:55 3:05 3:15 pumps for mixing and priming the main pump, Fig. 4.
pm pm pm pm pm pm pm pm pm pm pm pm pm As programmed, the treatment schedule provided for
Time of day
varying the injections between the two platforms, with inter-
mittent static periods where the working solution would be al-
torical treater pressure documentation and the field’s oil line lowed to soak and act upon the deposit. During the operation,
history reports. The comparative analysis showed disparity in pumping pressures ranged from 500 psi to a high of 1,350 psi,
the reported operating pressure, the accuracy of which would with equally fluctuating line pressures, Fig. 5.
further confirm pressure increases attributed to a severe Within two hours of soaking, the line pressure had equal-
flow restriction. ized significantly between the two platforms, suggesting that
Furthermore, as supporting data were inconclusive as to the wax was being dislodged. Afterward, with just over one
the presence of microbiological matter, it was presumed that hour of continuous pumping at a final rate of 2 bbl/min., the
any internal corrosion likely was caused by produced water, blockages were totally removed, and full communication was
rather than bacteria. While a sample analysis by a third-party established. After two pigging runs, the line was flushed clean
lab revealed significant amounts of iron oxides, given the long- with seawater.
static condition of the flowline, it was likely that rust along
REFERENCES
the pipe wall comingled with the deposition, making it non- 1. Goodman, N. T., and N. Joshi, “A tale of two flowlines—Paraffin plugging and remediation,” SPE
representative of the actual plug. paper 166196, presented at the SPE Annual Technical Conference and Exhibition, New Orleans,
La., Sept. 30-Oct.2, 2013.
After evaluating the accumulated data, it was surmised 2. Mokhatab, S., and B. Towler, “Wax prevention and remediation in subsea pipelines and flow-
that the deposition contained considerably higher concen- lines,” World Oil, Novemer 2009.
3. Mansoori, G. A., “Modeling of asphaltene and other heavy organic depositions,” Journal of Petro-
trations of paraffin and formation materials than suggested leum Science and Engineering, April 8, 1996.
by the deposit analysis. Thus, a remediation strategy was 4. Bailey, J. C., and S. J. Allenson, “Paraffin cleanout in a single subsea flowline using xylene,” SPE
paper 125131, SPE Projects, Facilities & Construction, Vol. 4, March 2009
developed accordingly. 5. Biswas, S. K., S. Bateja, M. Sarbhai, V. Kukreti, D. Rana and T. Misra, “Application of microbial
The treatment plan called for injecting the solution at each treatment for mitigating the paraffin deposition in down hole tubulars and surface flowlines of
wells—A success story,” SPE paper 154662, presented at SPE Oil and Gas India Conference and
end of the pipeline, where its specially formulated density and Exhibition, Mumbai, India, March 28-30, 2012.
composition would allow the solution to migrate to the block- 6. Sadeghazad, A., G. A. Sobhi, R. Christiansen and M. Edalat, “The prediction of cloud point
temperature: In wax deposition,” SPE paper 64519, presented at SPE Asia Pacific Oil and Gas
ages. Once the dislodged production fluid had been collected Conference and Exhibition, Brisbane, Australia, Oct. 16-18, 2000.
in designated tanks, the solution would be allowed to settle 7. Jacobasch, H. J., F. Simon and P. Weidenhammer, “Adsorption of ions onto polymer surfaces and
its influence on zeta potential and adhesion phenomena,” Colloid and Polymer Science, Vol. 276,
in the line until a pressure drop was observed, suggesting the pp 434-442, June 1998
plugged material had either been penetrated, or released. Once 8. Talley, C. B., “For cleaning food apparatus,” U.S. Patent No. 5663132 A., issued Sept. 2, 1997.
9. Talley, C. B., “Non-caustic cleaning composition comprising peroxygen compound and specific
the pressure dropped, and after a sufficient volume of the par- silicate, and method of making same in free-flowing, particulate form,” US Patent No. 5789361,
issued Aug. 4, 1998.
affin removal solution had been injected, pressure would be
applied from the farthest platform to determine whether the
KEVIN AYERS is COO of Ideal Energy Solutions, a
plugging material had, indeed, been released. At that point, position he has held for two years. He has more than
additional solution would be injected until full communica- 15 years of experience developing and managing a
tion had been restored between the two platforms. diverse group of companies, including biotech and
chemical manufacturing concerns. Mr. Ayers holds a
BS degree in finance, with a chemistry minor, from
PROJECT RECAP Louisiana State University (LSU).
Communication was first established in 8 hr, and after only
CHARLIE TALLEY is the chief developmental chemist
44.5 bbl of solution had been pumped; full communication for Ideal Energy Solutions and the developer of the
was restored after 45 hr of pumping and an aggregate 133 bbl WellRenew paraffin removal technology. With more
of solution. Judging from the removal of a cumulative 284 bbl than 48 years of experience in the chemical specialty
and microbiological areas, he has held a number of
of solids and sludge, and considering the total capacity of the developmental and management positions in a wide
8-in. line is 397 bbl, it was determined that 72% of the pipeline range of industrial and consumer organizations,
including developmental chemist for Frac-Chem, technical V.P. for
had been plugged, Fig. 2. the Tionicon Group of Chicago, Ill., developmental chemist for Force
Notably, the equipment rig-up prior to the initial injection Industries of Broussard, La. , as well as developmental work for food,
was relatively straightforward, with each platform requiring brewing and agricultural-related companies. He holds seven patents
and frequently conducts seminars and training on product
only a 50-bbl marine portable tank (MPT) and a 25-bbl cut- applications. Mr. Talley holds a BS degree in chemistry from
tings box to collect flowback and dislodged paraffin solids, Philadelphia University.
Article copyright © 2015 by Gulf Publishing Company. All rights reserved. Printed in U.S.A.
78 APRIL 2015 / WorldOil.com
Not to be distributed in electronic or printed form, or posted on a website, without express written permission of copyright holder.