Paraffins-101

Shekhar Khandekar
Global Flow Assurance Manager
Content

• Flow assurance
• Paraffin – chemistry and operational issues
• Factors affecting wax deposition
• Analysis methods
• Remediation methods – mechanical and thermal
• Prevention methods – chemical
• Field application and monitoring
The Overview Of Chemical Treatment to Ensure Flow Assurance

• Flow assurance is an engineering analysis process to assure

hydrocarbon fluids are transmitted economically from the reservoir to
the end user over the life of a project in any environment.
• Knowledge of fluid properties and utilization of thermal-hydraulic
analysis of the system helps develop strategies for controlling solids
such as hydrates, wax, asphaltenes, and scale
• Develop a strategy to ensure chemical treatment will overcome
unforeseen operational issues or challenges not overcome by design
engineering
Typical Issues Needing Review

A. Determine potential for

1) difficult emulsion “soaps”
2) wax precipitation
3) asphaltene precipitation
4) scale deposits
5) hydrates
6) high sand production
7) souring
8) corrosion
9) foaming
10)slugging
B. Look at multiphase flow aspects (hydraulics)
 Confidential
Flow Assurance Challenges

Flow Assurance

Hydrates Waxes and

Scale Corrosion Naphthenates
Asphaltenes

Calcium Metal
Carbonate and Microbial Naphthenate Carboxylate
Sulphate Corrosion Scales Emulsions

CO2, H2S, O2
Sulphides
Corrosion

Oxides and Flow Induced

Halides Corrosion

5
What is Wax ( or Paraffin or Paraffin Wax)
H H H H H
H C
H
C
H
C
H
C
H
C
H
H
Straight Chain

C C C C C C C
C
Branched Paraffins
C

C
C C

C C
C C C C C C C
Cyclic Paraffins
C
C C

C C
C
Wax Forming Compounds

• Waxes consist of branched (iso), cyclic, and straight chain

(normal) alkanes having chain lengths in excess of 17 carbon
atoms and potentially up to and over C100
• Distribution of waxes depends on the individual crude oil, but
generally above C20, the amount of any single carbon number
paraffin decreases exponentially
• Normal paraffins are generally the more abundant species
• Iso and cyclic paraffins may also be present in significant
quantities
Operational Issues- Wax

• Deposition on the pipe wall surfaces, among other equipment, causes

reduced throughputs
• Increases pressure loss
• Higher emulsion viscosity
• Gravity settling where waxy layers or sludge are formed in the bottom of
storage tanks, shipping and process
• Higher solids in the system leads to increased pigging frequency and lower
production rates
• Co-precipitation with asphaltenes – plugging, emulsion, and viscosity issues
• Low temperature viscosity behaviour
• Subsea flow lines: the build-up of solid waxy layers on the pipe walls. These
layers, if allowed to form, require periodic removal to avoid blockages or
reduced throughputs.
Why is Paraffin a Problem?

• Straight chain paraffins Melting Point Melting Point

have high melting points n-Paraffin
°C °F
• Lead crystallization at high C20 37 98
temperature
C25 52 125
• Progressive crystallization
as temperature decreases C30 64 147
• Corresponding iso and C35 74 165
cyclic paraffins have very
low melting points and do C40 81 178
not cause any problems
Major Causes that Lead to Paraffin Deposition

Commingling of
incompatible fluids

Low temperature
enhances deposition
Large pressure drops
enhance deposition
Deposition Sites

Transportation

Storage
Wellhead Upgrading
Refining

Reservoir
Process of Paraffin Precipitation
• Paraffins remain soluble in oil under reservoir conditions
• As hydrocarbon fluids are produced from the reservoir, they will
inevitably cool and undergo changes in pressure
• As a consequence of any changes, high molecular weight
components of the oil have the potential to precipitate as solids
(including paraffins)
• Paraffins can crystallize and potentially cause a host of operational
problems anywhere throughout the production and export system
• Waxes can solidify in the bulk oil as discrete particles or crystals
and condense onto cooled surfaces such as pipe walls and
tubulars
Precipitation Can Lead to Deposition – A Complex Process

• When the wall temperature is at

or below the wax appearance
Chemistry temperature (WAT)
• When fluid temperature is higher
than the wall temperature
Thermodynamics Heat Transfer
• Softer deposits under laminar
flow and harder under turbulent
Fluid Dynamics

flow
• Deposit aging occurs over time
• May result in plugging
Paraffin Deposition Sites

• Downhole: formation face, liner, perfs, pumps, tubing

• Surface equipment: chokes, valves, gauges
• Manifolds, flow lines, cool spots
• Vessels
• Coolers
• Storage tanks (especially prone to wax sludge)
• Tankers

Paraffin deposition can take place anywhere in the system

Factors Affecting Wax deposition

• Fluid composition
• Temperature/cooling rate
• Pressure
• Paraffin concentration
• Molar mass of paraffin molecules
• Occurrence of nucleating material such as asphaltenes, formation
fines, and corrosion products
• Water-oil ratio
• Shear environment
Oil Composition
• Wax precipitation is sensitive to the waxy crude composition.

• Normal paraffins are flexible hydrocarbon molecules and tend to cluster together
and precipitate from crude oil as wax solids.

• The iso-paraffins are branched molecules; however, they tend to delay the
formation of wax nuclei and usually form unstable wax solids.

• Aromatics are known solvents for paraffin waxes.

• Impurities and/or other amorphous solids (such as asphaltenes) in the oil usually
induce wax nucleation process, since they tend to lower the energy barrier for
forming the critical wax nucleus.
Oil Water Ratio

• The primary effect of water-oil ratio is related to changes in the rate of

fluid production with changes in water cut.
• Increased fluid production rates involve higher wellhead temperature
and less wax deposition; whereas, decreased fluid production would
have the opposite effect.
• Water tends to increase the water wettability of metal surfaces, thereby
reducing the likelihood of wax and crude contact with the metal surface.
• Water being a conductor of heat will reduce the deposition
Shear Environment

• The shear environment can either delay or induce wax deposition

depending on the regime (i.e., turbulent vs. laminar) of flow and/or
agitation.
• In high-shear environments, the ability of wax constituents to congeal
and reach a pour point or to plug a tube is diminished as the nucleation
process is disrupted
• In a low-shear environment (i.e., laminar flow or close to
equilibrium/static condition), the flexible paraffinic molecules tend to be
aligned adjacent to one another in the direction of the flow, thereby
inducing/speeding the nucleation/clustering process. Hence, the
severity of flow line plugging is usually observed to increase for low
shear environments.
Wax Plugs
How to Predict Paraffin Problems

• One of the most critical steps in identifying and quantifying flow

assurance risks is fluid sampling.
• To understanding flow assurance risks, ask the following:
– What is the fluid composition?
– Is there a potential for wax deposition?
– Is the potential for asphaltene deposition high, medium, or low?
– Will the fluid gel when the temperature is low enough after a system shutdown?
– How much energy will be required to re-mobilize the fluid once it is gelled?

Important: sample the representative fluid transported by pipeline

Fluid Sampling

• No matter how accurate the lab measurements and interpretations

are, if the fluids do not represent the real production fluids, wrong
conclusions may be drawn.
• Any flow assurance mitigation strategies based on wrong
conclusions will work improperly and the pipeline and subsea
system will encounter severe operational risks.
• Fluid samples can be obtained from downhole and/or from the
surface separator.
• Downhole samples are the primary samples for PVT and flow
assurance measurements. Surface separator samples are usually
treated as back-up and can be used as bulk samples for process
or reservoir design.
Paraffin Analysis Methods ( Analytical/Operational)
• Total wax in crude oil
• Wax appearance temperature (cloud point)
– Cross polarization microscopy
– DSC
– Filter plugging
– FTIR
• Gas chromatography (HTGC)
• Pour point
• Dynamic viscosity measurements
• Yield stress measurements (for pipeline restart values)
• Deposition testing
Total Wax in Crude Oil

• High wax content (>10 percent) can indicate potential fluid flow and
restart problems.

• Wax content is a parameter which has no direct use in designing a

production system.

• Most precipitation tests are performed at approx. -35 degC. This is

substantially lower than most operating temperatures; for example,
the actual amount of solid wax present in an oil at seabed
temperature may be less than 25% of the total wax content.
Wax Appearance Temperature
• The WAT is the temperature that sets the solubility limit of the wax
molecules for a particular hydrocarbon system at specified pressure.
• Below the wax appearance temperature, wax molecules start to
precipitate and crystallize.
• WAT is also referred to as cloud point (CP) or the wax precipitation
temperature (WPT).
• Distinction between thermodynamic and experimental WAT.
– Thermodynamic WAT: the highest temperature at which solid wax
exists at a specified pressure
– Experimental WAT: the temperature at which a minimum amount of
wax is detectable by the particular detection technique.
Cross Polarisation Microscopy

Test method consists of determining the WAT of a crude oil by measuring

the temperature at which wax crystals can be seen via microscopy under
cross-polarized light.
 CPM Images: WAT vs. WDT
50°C 41°C(~WAT) 5°C 35°C

WAT
40°C 30°C 45°C 55°C

WDT

20°C 5°C 57°C(~WDT) 60°C

UOP wax content ~ 5 wt%

High Temperature Gas Chromatography

• Provides a carbon number

distribution in the crude
mixture
• Helps in determining the
nature and severity of
problems
• Aids in selection of the Carbon number distribution
appropriate chemical 6.00

treatment Weight %
5.00

4.00

• Quantitative technique 3.00

2.00

• Requires small sample 1.00

0.00

volume
0-5

100
105
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
Carbon Number
 Pour Point

• Wax precipitation occurs below WAT.

• Crude gradually solidifies as the temperature drops and more wax
precipitates causing the wax gel to thicken.
• The crude pour point is reached when the oil stops moving as oil is
trapped within the wax gel.
• ASTM D97 is the technique used for the pour point of stock tank oil
samples.
Yield Stress Measurements

• The presence of wax causes crude oil to exhibit pseudo plastic

behaviour. Depending on the quantity of wax present, crude oil has a
definitive yield point.
• Function of shear rate and temperature
• Increases with decrease in temperature
• Critical from operational point of view. A higher temperature flow is
normal and pumping pressure is low. A decrease in temperature
viscosity increases and pumping pressure increases. If the flow is
suspended, then the wax crystal structure builds up and the yield point
must be overcome to restart the flow
Yield Stress Measurements

• Pipelines normally operate at a certain design pressure (generally

between 1500-2000 psi/100-150 bar)
• If the yield stress is more than the design pressure, the pipeline may
not be able to withstand that pressure.
• If the pumps do not have a capacity to attain the required pressure, the
flow may not be started again.
Yield Value for Shut-in Crude
Dynamic Viscosity Measurements

• Crude oils are often non-Newtonian fluids

• Viscosity is an interpretation of torque
• Important tool to study the behaviour of
crude oil under normal flow conditions
• Viscosity measurements are conducted on
crude samples subjected to different
pretreatments. This provides information
on the range of viscosities that could be
encountered under operating conditions.
Viscosity Measurements

• Single point viscosity tests

• Controlled rate ramp: record viscosity at different shear rates
between a maximum and a minimum
• Up and down ramp: vary shear rate at a given temperature and
record viscosity at each shear rate
• Record viscosity over a period of time at given shear rate
• Record viscosity in a predefined temperature range at a particular
shear rate
Deposition Testing – Cold finger

• Particularly useful when system

experiences paraffin problems in
spite of low pour point
• Oil is gently agitated about the
cold finger with a magnetic stirrer;
oil is maintained at a temperature
above its cloud point
• Amount of deposit collected will
be a measure of deposition
problems in the pipeline
• Duration of test from 2 to 48 hours
Mechanical Removal of Paraffins

• Hot oil: melts and dissolves wax

• Hot water: same principle as hot oil, but dispersant must be
used to disperse the melted wax
• Steam: clears flow lines
• Heaters: dropped on wire lines to melt wax in tubing
• Scrapers: regular use keeps tubing clean
• Pigs: scrape wax from flow lines regularly
Hot Oiling
• Oil is drawn from a source tank and
transported to the well site where it is
circulated through a heater to maintain a
maintain temperature between 150oF and
300oF.
• Oil may be pumped into the flow line initially
to clear the paraffin from the wellhead area,
with the remainder of the oil being pumped
into the annular space of the well.
• In the annulus, hot oil heats the tubing from
the outside in. Paraffin wax deposited on
tubing walls loosens up, softens or melts,
and begins to mobilse.
• The hot oil never directly contacts the
paraffin in the tubing
• The hot oil continues to fall to the bottom of
the well, losing heat as it moves through the
system. The injected oil is produced back
after several hours
• Hot oilers commonly draw oil the oil needed
for hot oiling from the storage tanks nearest
the wells to be treated.
• These tanks will usually contain high
quantities of paraffins. Tanks are usually the
coolest part of the system. Precipitation of
paraffins in the storage tanks will make the
bottoms of the tanks paraffin-rich due to the
paraffin having a higher density than oil.
• Can also contain Iron sulphide, clay, sand,
iron oxide
• When this high paraffin oil reaches the
bottom of the well bore, it may cool to a
temperature low enough to start re-
depositing paraffin and contained solids
Hot Watering
• Used as an alternative to hot
oiling
• Higher heat capacity of water
allows more heat to be reached
at the bottom
• Doesn’t contain contaminants
that may be present in hot oil
• Cost effective
• Plain hot-water treatments cannot provide
the solvency available with hot oiling
• Surfactant packages need to be added to
aid the dispersion of wax into the
water phase.
• Hot-water/surfactant combinations produce
very large water-wet particles of wax that
may accumulate at the interface causing
emulsion issues
• The re-solution of water-wet waxes requires
substantially greater amounts of demulsifier
than the two-phase water and oil normally
handled by heater treaters.
• For the surfactant to be effective it has to
come in contact with “melted” paraffin
Scraping
• Periodic scraping is used where hot
oiling cannot be used
• Same cost as hot oiling.
• Scraping physically removes paraffin
without melting; this avoids re-
deposition, but it may cause plugging
• Scraping is well established - it is the
technique of choice in some areas.
• Scraping requires no handling of low
flash point chemicals.
• If deposits are very hard, scraping can
be augmented by a chemical soak.
• Scraping is not as efficient as hot oiling
(about 2/3 as effective).
• The minimum charges for periodic
scraping can be uneconomical for
isolated wells.
• Large chunks of paraffin may settle in
flow lines and cause blockage.
• The metal-to-metal contact roughens
the tubing wall, which encourages
deposition. (It has been shown that
paraffin deposits do not adhere well to
shiny metal surfaces, but do adhere to
roughened surfaces.)
Pigging

• A pig is defined as "A

device that moves through
the inside of a pipeline for
the purpose of cleaning,
dimensioning, or
inspecting." This definition
covers in excess of 500
different designs and types
of pigs.
Pigging a Pipeline

Construction and commissioning

• After a pipeline is built, running pigs removes any debris left
in the line from new construction (lunch boxes, tools, welding
rods, dead animals)
• Removes mill scale and welding icicles
• During hydro testing, used for watering and dewatering and
then drying
• Verifies the ovality of the pipeline
Pigging a Pipeline

Operation and maintenance

• Tool for planning future pipeline maintenance strategies
• Removes obstructions or unwanted material, including
paraffin, scale, dust, and condensed liquids, during normal
operations
• Maintains internal pipe diameter and smoothness to
minimise frictional losses of the flowing product, thus
reducing running costs of pumping/compression
• Removes the liquids in wet gas systems, and the
accumulated water in product pipelines
• Minimize corrosion with an application inhibitors, especially
in liquid pipeline systems
Pigging a Pipeline

Inspection
• Detects metal loss from erosion/corrosion (internal and
external)
• Detects cracks and other defects
• Monitors geometry and profile
Polly Pigs (Foam)
• Various densities (light to heavy)
• Standard length is twice the diameter
Advantages
• Compressible, expandable, light weight, and flexible
• Travels through multiple diameter pipelines
• Goes around bends and short radius 90º bends
• Makes abrupt turns in tees so laterals can be cleaned
• Travels through valves with as little as a 65% opening
• Inexpensive.
Disadvantages
• One-time use product
• Shorter run length
Pigging Goals
Project goals
• Environmentally sound oil & gas production

• Goal: Reduction in amount of paraffin carryover

• Safe handling with no HSE related issues

• Limited Production Impacts

How achieved
• Scheduled Maintenance Pigging

• Improved Chemical Inhibition

Paraffin Control Additives
Types of Paraffin Chemicals

• Paraffin solvents
– Remove existing deposits
– Enhance crude solvency
• Paraffin dispersants
– Assist in removal of existing deposits
– Prevent deposition
• Paraffin inhibitors/ crystal modifiers
• Pour point depressants
Paraffin Cleaners

• Paraffin solvents
– Blends of aromatic, aliphatic, and mutual solvents designed to solubilise
wax deposits.
– Requires long contact time

• Paraffin dispersants
– Water wetting surfactants used in conjunction with water, oil, or paraffin
solvents to enhance deposit removal
Chemical Solvents

• Remove paraffin deposits by dissolving the paraffin.

• Attacks the crystal from the outside in. A good solvent dissolves
paraffin molecules off the surface, regardless of their structure or
the size and melting point of the molecule.
• Increased effectiveness with increased temperature and agitation.
• Higher volume necessary because the solvent itself is removing
the paraffin deposit, it is necessary to use a solvent volume
sufficient to accomplish complete dissolution
• Effective in removing blockage from flow lines, depending on the
degree of blockage.
Paraffin Dispersants

• Prove more effective than solvents when more than a 20% water cut
is present, generally.
• Will not remove paraffin when injected on a continuous basis. Instead,
dispersants are used to prevent paraffin deposition in systems that
have been cleaned by mechanical, thermal, or chemical means.
• Work by coating the paraffin crystal and the metal surfaces, thus
causing the paraffin crystals to repel each other and the metal
surfaces. This approach to paraffin control does not prevent the
paraffin crystals from forming, but merely keeps them from forming a
solid deposit and keeps them moving with the crude.
• Formulated in chemical solvents with surfactants (nonionic/
cationic/anionic).
Paraffin Inhibitors

Pour point depressants / paraffin inhibitors

• Modifies wax crystal shape and growth
• Reduces crude pour point
• Reduces crude viscosity and pumpability
• Reduces heating demands
• Reduces pipeline restart pressures after shut-in periods
• Prevents paraffin deposition
• Reduces cloud point
Resolving Paraffin Related Issues in the Field

• Collect field information about the problem

• Design and implement lab tests
• Interpret the lab results as they relate to the field problem
• Identify available application methods
• Achieve the desired results
• Review the economics and effectiveness
Collecting Field Information

• Identify the problem, where it occurs, and how it affects the

production system.
• Record the system operating parameters and configuration. Include
details for temperature profile, flow rates, and equipment make up.
• Collect environmental and operating conditions and procedures.
• Discover how the problem is currently handled, how it was handled
and the effectiveness, and the costs involved.
• Identify the desired method of treatment and application.
• Find out the desired results of the treatment.
Design, Implementation and Interpretation of Lab Tests

• Analyse field information to assess the cause and effect of the paraffin
problem. With this determination completed, the appropriate laboratory
evaluation program can be designed.
• Test sequence typically involves preliminary tests, such as pour point,
carbon number distribution analysis, cloud point, and deposit analysis.
• Conduct additional specific testing, such as cold finger deposition tests
and flow loop (model pipeline) tests.
• Interpretation of results should be related to field parameters. Field
diagrams should be included where applicable
Achieve Desired Results through Monitoring

Paraffin Inhibitor
• Pressure drop changes
• Flow rate changes
• Scraper frequency
• Pigging frequency
• Cleaning frequency
• Spool pieces
• Temperature at outlets
• Operator perception
Review Effectiveness and Economics

• Review chemical effectiveness using laboratory and field

information
• Methods should be relevant to field operations
• “cost effectiveness “ should be measured by comparison with
no treatment scenario including
– Down time ,deferred production
– Cost of failures
– Cost of replacements