Hydrates

By Sherry Oyagha

28th August, 2020

 Outline
 Introduction
 Why Hydrates May Cause Safety Problems
 Areas Where Hydrates Form in an Offshore System
 Conditions Necessary for Hydrate Formation
 Estimation of Hydrate Formation Conditions
 Estimating the Hydrate Inhibitor
 Hydrate Occurrence due to Expansion through Valves or Restrictions
 Hydrate Control Through Chemical Inhibition
 Hydrate Control Through Heat Control
 Summary of Rules of Thumb in Hydrate Prevention

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 Introduction
 Natural gas hydrates are crystals formed by water with natural gases and
associated liquids, in a ratio of 85 mole % water to 15% hydrocarbons.
 The hydrocarbons are encaged in ice-like solids which do not flow, but rapidly
grow and agglomerate to sizes which can block flow lines.
 Hydrates can form anywhere and anytime that hydrocarbons and water are
present at the right temperature and pressure such as in wells, flow lines, valves
and meter discharges.
 The low temperatures and high pressures of the deep-water environment cause
hydrate formation, as a function of gas and water composition.
 In a pipeline, hydrate masses usually form at the hydrocarbon-water interface,
and accumulate as flow pushes them downstream. The resulting porous hydrate
plugs have the unusual ability to transmit some degree of gas pressure, while
3 they act as a flow.

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 Why Hydrates May Cause Safety Problems

Safety issues may arise if hydrates are present in a system due to the following
characteristics of hydrates;
1. Hydrate densities are like that of ice, a dislodged hydrate plug can be a
projectile with high velocities. Such velocities and masses provide enough
momentum to cause two types of failure at a pipeline restriction, obstruction or
sharp change in direction. These problems are;
• Hydrate impact can fracture pipe
• Extreme compression of gas can cause pipe rupture downstream of the
hydrate path.
2. Hydrates can form either single or multiple plugs, with no method to predict
which will occur.
3. Hydrates contain as much as 180 volumes (STP) of gas per volume of hydrate.
4 When hydrate plugs are dissociated by heating, any confinement causes rapid
gas pressure increases.

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 Why Hydrates May Cause Safety Problems

Safety Hazard of Moving Hydrate Plug and High Pressure Trapped

by Hydrates

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 Why Hydrates May Cause Safety Problems

 Line failure due to hydrate plug is more prevalent when;

• Long lengths of pressurized gas are trapped upstream
• Low downstream pressures provide less cushion between a plug and
restriction.
• Bends exist downstream of the plug
 Safety recommendations when dealing with hydrate blockages are;
• Always assume multiple hydrate plugs, there may be pressure between the
plugs.
• Attempting to move ice (hydrate) plugs can rupture pipes and vessels.
• While heating a plug is not normally an option for a subsea hydrate, any
heating should be done from the end of a plug rather than the middle.
• Heating a subsea plug is not recommended due to the inability to determine
6 the end of plug as well as provide for gas expansion on plug heating.
• Depressuring a plug gradually from both ends is recommended.

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 Conditions Necessary for Hydrate Formation

1.   Free water and natural gas

Gas molecules ranging in size from methane to butane are hydrate components,
including CO2, N2, and H2S. The water in hydrates can come from free water
produced from the reservoir, or from water condensed by cooling the gas
phase.
2. Low temperature
Hydrates can easily form at as well as the higher temperatures of shallower
water, at high pressure.
3. High Pressure
This is commonly the cause of hydrate formation. At , common natural
gases form hydrates at pressures as low as 100psig. At 1500psig, common
gases form hydrates at .
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 Areas Where Hydrates Form in an Offshore System

1. Hydrate Formation in the Well

 Hydrate formation in wells is an abnormal occurrence, arising during drilling of
the well or shut-in/start-up of the well.
 Hydrates form only in unusual circumstances, such as pressurizing the well with
water or with an aqueous acid solution.
 In offshore well drilling usin water-based drilling fluid, hydrates can form and
plug blow-out preventors, kill lines, etc. when a gas bubble (kick) comes into
the drilling apparatus.
 The following rule of thumb are used by Exxon in considering hydrate forming
with drilling fluids;
• When hydrates form solids, they remove water from the mud, leaving a solid
barite plug.
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 Areas Where Hydrates Form in an Offshore System

• A well shouldn’t be designed to operate outside the hydrate region only if

flow conditions are maintained. If the well will be in the hydrate formation
region at static conditions, flow will stop at some period and the well
operation will be jeopardized
• Several hours may be required for hydrate formation and blockage to occur
• As of October 1988 Exxon used salt at the saturation limit range of 150 to
170 g/l to prevent hydrate formation
• The Table below gives a guideline for hydrate formation at different depths

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 Areas Where Hydrates Form in an Offshore System

2. Hydrate Formation in a Flowline

 Pipeline pressure and temperature conditions are predicted using a pipe
prediction program such as OLGA or PIPEPHASE.
 At short pipeline distances, hydrates may not form as the hot flowing gas
retains its high temperature but at further distance, the pipeline is cooled, the
gas associated with water, stands the risk of forming hydrates.
 At long distances there is also sufficient residence time for the entrained water
further increasing the risk of hydrate forming.
 To prevent hydrate formation, inhibitors like methanol are injected. Hydrate
inhibition occurs in the aqueous liquid not in the vapor or condensate.

10 3. Hydrates in Platform Processes

 The three objectives a platform process are;
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 Areas Where Hydrates Form in an Offshore System

• Gas, water, oil separation. The oil phase will then have a low vapour
pressure. Water is discharged into the ocean.

• To dehydrate the gas to a water content below 7 lbm/MMscf before injection

into the pipeline to shore.

• To compress the gas for transport to land.

 Water separation and gas dehydration are vital for hydrate prevention, so
if the system cools into the hydrate pressure-temperature, hydrate formation is
prevented due to insufficient water.
 Thus the pipeline gas water content is kept below its water dew point at the
lowest temperature so free water will not condense from the gas phase.
 Hydrate formation is not a significant problem in the oil export pipeline because
11 relatively few hydrate formers (nitrogen, C1-C4 and CO2) are present and the
water content is low.
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 Areas Where Hydrates Form in an Offshore System

 In process systems, at the valve through which gas passes to the compressors,
there us substantial pressure reduction which causes cooling, making this point
susceptible to hydrate formation.
 Also, instrument gas lines require pressure drops from the header, making this
point susceptible to hydrate formation.

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 Estimation of Hydrate Formation Conditions

  First, calculate the pressure at which hydrates form at the lowest deep ocean
temperature (F), if the pipeline pressure is greater, then inhibition may be
considered in the pipeline design and operation.
 A Rule of Thumb is at F, hydrates will form in a natural gas system if free water
is available and the pressure is greater than 166psig.
 The rule of thumb shows that most offshore pipelines exceed hydrate formation
conditions indicating that;
• Gas drying and/or inhibition is needed for ocean pipelines with temperatures
approaching F.
• A more accurate estimation procedure should normally be considered
• Hydrate formation pressures are dependent upon the gas composition and
are sensitive to the amount of propane present.
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 Estimate of Hydrate Formation Conditions
 As a second approximation of hydrate formation the design/facilities engineer
should perform two calculations:
i. A pipeline pressure-temperature flow simulation should be done to find the
conditions between the wellhead and the platform separators.
ii. Hydrate formation conditions can be calculated, determining pressures and
temperatures of vapor and aqueous liquid inhibited by various amounts
(including 0wt%) of methanol (MeOH) or monoethylene glycol (MEG).
 The intersection of the above two lines will determine the pressure and
temperature at which hydrates will form in a pipeline.

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 Estimate of Hydrate Formation Conditions
Hydrate Formation Conditions by the Gas Gravity Method
 The simplest method to determine the hydrate formation temperature and
pressure is via gas gravity.
 The gas gravity is the molecular weight of the gas divided by that of air.

 The gas gravity is calculated and the temperature of a point on the pipeline is
specified.
 Using the gas gravity and temperature the pressure at which hydrates will form
is read from the Katz Chart which shows the hydrate formation curves for
various gas gravity.
 This method is only an approximation, a more accurate method requires
computer calculations.
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 Estimating the Hydrate Inhibitor Needed

Estimating
  the Hydrate Inhibitor Needed in the Free Water Phase
 The gas gravity chart may be combined with the Hammerschmidt equation
given below to estimate the hydrate depression temperature for several
inhibitors in the aqueous liquid,

Where:
∆T = hydrate depression, F
C = constant for a particular inhibitor (2,335 for MeOH; 2,000 for MEG)
W = weight per cent of the inhibitor in the liquid
M = molecular weight of MeOH (32) or MEG (62).

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 Estimating the Hydrate Inhibitor Needed
Amount of Inhibitor Injected Into Pipeline
 While the Hammerschmidt equation enables estimation of the wt% MeOH or
MEG needed in the free water phase, three other quantities are necessary to
estimate the amount of inhibitor injected into the pipeline:
• The amount of the free water phase
• The amount of inhibitor lost to the gas phase
• The amount of inhibitor lost to the condensate phase.
 The amount of the free water phase is multiplied by the wt% inhibitor from the
Hammerschmidt equation. These three quantities are discussed below.

1. Amount of Water Phase

 The water phase has two sources; produced water and water condensed from
the hydrocarbon phases.
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 Estimating the Hydrate Inhibitor Needed
 The amount of produced water can only be determined by data from the well,
with an increasing amount of water production over the well’s lifetime.
 Water condensed from the hydrocarbon phases may be calculated. The water
content of condensates is usually negligible, but water condensed from gases
can be substantial.
 The amount of water condensed is the difference in the inlet and outlet gas
water contents, multiplied by the gas flow rate.
 An inlet gas water content analysis is used, if available. Then the water content
of the outlet gas may be subtracted from the inlet gas to determine the
water condensed per MMscf of gas.

2. Amount of Inhibitor Lost to the Gas Phase

 The amount of MeOH or MEG loss into the gas phase should be considered using
18 the following Rules-of-Thumb.

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 Estimating the Hydrate Inhibitor Needed
i.   At F and pressures greater than 1000psia, the maximum amount of methanol
lost to the vapor phase is 1 lbm MeOH/MMscf for every weight % MeOH in the
free water phase.
ii. At 39 oF and pressures greater than 1000 psia, the maximum amount of MEG
lost to the gas is 0.002 lbm/MMscf.

3. Amount of Inhibitor Lost to the Liquid Phase

 Two general Rules-of-Thumb can be applied to inhibitor losses in the
condensate.
i. Methanol concentration dissolved in condensate is usually0.5 wt%.
ii. The mole fraction of MEG in a liquid hydrocarbon at F and pressures greater
than 1000 psia is 0.03% of the water phase mole fraction of MEG.
19
 Methanol is a much more effective inhibitor than ethylene glycol on a weight
basis and it is less viscous, thus it is mostly used.
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 Hydrates Due to Expansion through Valves or Restrictions

 When water wet gas expands rapidly through a valve, orifice or other
restriction,
hydrates form due to rapid gas cooling through Joule-Thomson expansion this
commonly occurs in fuel gas or instrument gas lines.
 Hydrate formation with high pressure drops can occur in well testing, start-up,
and gas lift operations, even when the initial temperature is high, if the
pressure drop is very large.
 The Rule of Thumb states that Natural gases cool upon expansion from
pressures below 6000psia; above 6000 psia the temperature will increase upon
expansion.
 Virtually all offshore gas processes cool upon expansion, since only a few
reservoirs and no current pipelines or process conditions are above 6000 psia.

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 Hydrates Due to Expansion through Valves or Restrictions

Joule Thomson Chart  A Joule Thomson chart is used to

determine;
i. The maximum pressure expansion
without risking hydrate formation.
ii. The minimum initial temperature that will
permit expansion without danger of
hydrates.
 Softwares are more accurate than the
chart. HYDOFF is the software used. It
also gives an estimate of the amount of
methanol inhibitor required.
 The software XPAND is used to calculate
the second J-T expansion line (calculated
21 through an EOS) which intersects the
hydrate formation line.
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 Hydrates Due to Expansion through Valves or Restrictions

 XPAND is used to calculate the discharge temperature of the natural gas upon
expansion by using inputs of the upstream valve pressure, temperature and gas
composition to calculate the downstream gas temperature at a given discharge
pressure.
 Pipeline hydrate plugs are frequently porous, thus depressurization from one
side can result in J-T cooling as gas flows through the plug. Expansion across a
hydrate plug yields identical results to expansion across a valve.
 Expansion from a condition which has a hydrate plug will only cause the
downstream portion of the plug to progress further into the hydrate region.

Methods to Prevent Hydrate Formation on Expansion

 To prevent expansion into the hydrate region in the case of flow through a
22 restriction, one of four options may be considered;

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 Hydrates Due to Expansion through Valves or Restrictions

1. Methanol Addition

Methanol can be injected into the fuel supply line upstream of the control valve to
prevent hydrate formation downstream of the valve. To determine the amount of
methanol to be injected, the following steps are followed;

i. Determine the water condensation with expansion

ii. Determine the mass of MeOH Required in the Water Phase

iii. Determine the mass of MeOH Lost to Condensate and Vapor

iv. Calculate Total Mass of MeOH Needed

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 Hydrates Due to Expansion through Valves or Restrictions

 Fuel gas lines can be placed in parallel to

2. Parallel Gas Expansion provide more than one gas expansion.
  If one control valve becomes plugged with
hydrates and shut down, the second gas line is
then opened while the first line is depressurized
for hydrate dissociation.
 By doing this, it is hoped that flow can be
maintained in one fuel gas line without the
need for hydrate inhibition.
 The capital cost is doubled however, and there
is the risk that the parallel valve may become
hydrated before the plug is removed from the
initial line.
24  This solution addresses the effect of hydrate
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formation rather than its cause.
 Hydrates Due to Expansion through Valves or Restrictions

3. Dehydration of Inlet Gas

 If the gas inlet is dry such that its dew point is low enough, this will prevent
hydrate formation..
 Cost wise, this is the best method if hydrate prevention
 It is good design practice to place both fuel gas and instrument gas lines
downstream of a TEG drying unit or a molecular sieve adsorption tower.

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 Hydrate Control Through Chemical Inhibition

There are two major techniques of hydrate inhibition described below.

A. Thermodynamic Inhibition by Methanol and Monoethylene Glycol
 This method totally prevents hydrate formation
 Two major kinetic inhibitors are used; Methanol and Monoethylene Glycol (MEG)

i. Methanol
 Of all hydrate inhibitors, methanol is the most widely used, it is also the best
and most cost effective of all alcohols.
 Hydrate inhibition abilities are less for larger alcohols (i.e. methanol > ethanol >
isopropanol).

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 Hydrate Control Through Chemical Inhibition
 Methanol is vaporized into the gas stream of a pipeline, then dissolves in any
free water accumulation to prevent hydrate formation.
 WELLTEMP can be used to predict the flowing temperature and pressure of the
methanol injected just like PIPEPHASE or OLGA.
 The downhole methanol injection point is placed at the well depth for which the
well temperature and pressure are predicted to cross into the hydrate formation
region.
 Methanol is lost by dissolving in the vapor or oil/condensate phases should be
taken into account.

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 Hydrate Control Through Chemical Inhibition

Methanol Injection and Recovery

 Injected methanol is
recovered in a
distillation column
 Recovery is possible in
the vapour phase
using cryogenic
process, this process is
expensive.
 Methanol loss can lead
to substantial costs

28
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 Hydrate Control Through Chemical Inhibition
ii. Monoethylene Glycol (MEG)
 MEG is used more than the other glycols (DEG and TEG) because it has a lower
viscosity and is more effective per pound.
 MEG has a higher molecular weight and a lower volatility than methanol, so it
may be recovered and recycled more easily on platforms. Also MEG losses to the
vapor and oil/condensate phases are very small relative to methanol
 Thus MEG is most applicable for small water fractions when gas and
oil/condensate fractions are very high.
 It is a rule of thumb that Monoethylene glycol injection is used when the
required methanol injection rate exceeds 30 gal/hr.
 Unlike methanol, MEG’s low vapor pressure requires that it be atomized into a
pipeline.
29
 After injection, MEG is retained with the water phase and provides no hydrate
protection above the water level.
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 Hydrate Control Through Chemical Inhibition

MEG Injection and Recovery  Due to it’s high viscosity and

density, MEG is seldom used to
dissociate a hydrate plug unless
the injection point is vertically
above a hydrate plug.
 MEG is recovered with water
(typically at 60-80 wt%) at the
bottom of the column.
 Salt also concentrates in MEG
regenerator bottoms (due to low
salt vapor pressure) when salt
water is produced in the well
30 stream inhibited by MEG.

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 Hydrate Control Through Chemical Inhibition
Comparison of Methanol and Glycol Inhibitor Attributes

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 Hydrate Control Through Chemical Inhibition
B. Kinetic Control by Anti-Agglomerants and Kinetic Inhibitor
i. Anti-Agglomerants
 With this inhibition mechanism, hydrate droplets form, and both gas and water
are consumed, but hydrates are prevented from agglomerating to larger hydrate
masses capable of plugging pipelines.
 Anti-agglomerant inhibitors are particularly effective in preventing hydrate
plugging or flow stoppages such as shut-ins, with subsequent cooling and
restarting.
 A rule of Thumb states that the Use of anti-agglomerant requires a substantial
oil/condensate phase. The maximum water to oil ratio for the use of an anti-
agglomerant is 40:60 on a volume basis.
32  Weaknesses of the method include toxicity concerns, the need to break
emulsions, and the need to recover the expensive dispersant additive.
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 Hydrate Control Through Chemical Inhibition

Anti-Agglomerants in a Pipeline

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 Hydrate Control Through Chemical Inhibition
ii. Kinetic Inhibition
 Kinetic inhibition of hydrate growth has a different mechanism than that of anti-
agglomerants.
 kinetic inhibitors prevent hydrate crystal nucleation and growth without
emulsifying in a hydrocarbon phase.
 Prevention of nucleation prevents hydrate crystals from growing to a critical
radius. Growth inhibition maintains hydrates as small crystals, inhibiting
progress to larger crystals.
 Kinetic inhibitors are commonly polymers with several chemical formulas.
 Each of the chemicals has a polyethylene backbone, connected to pendant
groups typically containing an amide (-N-C=O) linkage, frequently within a five
or seven member ring.
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 Hydrate Control Through Chemical Inhibition
Formulas of Some Kinetic Inhibitors
  As the inhibitor adsorbs on the hydrate crystal, the
pendant group penetrates specific sites (cages) of a
hydrate crystal surface while the polymer backbone
extends along the surface
 In order to continue growing, the crystal must grow
around the polymer; otherwise crystal growth is
blocked
 One of the first kinetic inhibitors developed was
polyvinylpyrrolidone (PVP)
 A Rule-of-Thumb states that PVP may be used to
inhibit pipelines with subcooling less than for flow
35 lines with short gas residence times (less than 20
min)
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 Hydrate Control Through Chemical Inhibition
Guidelines for Use of Kinetic or Thermodynamic Inhibitors

1. If the field is mature, record the current hydrate prevention strategy. Record
the existing or planned procedures for dealing with an unplanned shutdown.

2. Obtain an accurate gas, condensate, and water analyses during a field drill test.
Estimate how these compositions will change over the life of the field. Estimate
the production rates of gas, oil, and water phases over the life of the field.

3. Generate the hydrate pressure-temperature equilibrium line with several

prediction methods. If the operating conditions are close to the hydrate line,
confirm the prediction with experiments.

4. Determine the water production profile over field life.

5. Consider the pipeline topography along the ocean floor to determine where
36 water accumulations will occur at dips, resulting in points of hydrate formation.

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 Hydrate Control Through Chemical Inhibition
6.   Simulate the pipeline pressure-temperature profile using a simulator such as
OLGA or Pipesim to perform hydraulic and heat transfer calculations in the well,
flow lines and separator over the life of the field.

7. Determine the water residence times in all parts of the system, especially in
low points of the pipeline.

8. Estimate the subcooling ∆T (at the lowest temperature and highest pressure)
relative to the equilibrium line over all parts of the system, including fluid
separators and water handling facilities. List the parts of the system which
require protection.

9. If ∆T < , consider the use of kinetic inhibitors. If ∆T > , consider the use of
standard thermodynamic inhibitors or anti-agglomerants.

37 10. Perform economic calculations (capital and operating expenses) for four options
of drying, methanol, monoethylene glycol, and kinetic inhibitors.

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 Hydrate Control Through Chemical Inhibition

11. Determine if inhibitor recovery is economical.

12. Design the system hardware to measure temperature and pressure at pipe inlet
and outlet, water monitor for rates at receiving facility etc.

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 Hydrate Prevention Through Heat Control
 The
  retention of reservoir heat is one of the most efficient means of hydrate
prevention.
 Because all reservoirs contain water and because water acts as a heat sink
due to a high heat of vaporization, fluids at the wellhead are typically at
temperatures from to .
 When the reservoir fluid flows through a deep ocean pipeline with an outer
temperature at , the temperature can quickly cool into the hydrate
region.
 If the pipeline were shut-in, the system would rapidly cool to the ambient
conditions.

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 Hydrate Prevention Through Heat Control

 At the low ambient temperatures, hydrate problems are particularly severe and
blockages may occur, particularly when the system is re-started.
 It is good operating practice to inject large quantities of MeOH or MEG into the
pipeline before a planned shut-in.
 Hydrates can be prevented in pipelines by three types of heat control;

i. Burying the pipeline to provide heating and insulation by the ocean floor
 Pipeline burial is a good means of providing pipeline insulation and protection

 The degree of insulation in pipeline burial depends upon the thermal gradient in
the earth along the pipeline route, the pipeline depth and the water temperature
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 Hydrate Prevention Through Heat Control

Pipeline Insulation Methods ii. Insulating the pipeline,

 Three methods are used;
o Non-jacketed insulation
o Pipe-in-pipe systems
o Bundling systems.
 The pipe-in-pipe (PIP) system is the
most thoroughly tested of the 3 types.
The flow pipe is within an outer pipe
with either insulation
or vacuum between the two pipes
 Bundled flow lines are more cost
41
effective.
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 Hydrate Prevention Through Heat Control

iii. Pipeline Heating

 Three methods are

used for pipeline
heating

• Bundled Pipeline

• A Combination Pipe

• Direct Electric Heating

Direct Electric Heating

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 Summary of Rule of Thumbs in Hydrate Prevention

Rule
  of Thumb 1: At , , hydrates will form in a natural gas system if free water is
available and the pressure is greater than 166psig.

Rule of Thumb 2: For long pipelines approaching the ocean bottom temperature
of , the lowest water content of the outlet gas is given by the below table:

Rule of Thumb 3: At and pressures greater than 1000 psia, the maximum
amount of methanol lost to the vapor phase is 1 lbm MeOH/MMscf for every
weight % MeOH in the free water phase.

Rule of Thumb 4: At and pressures greater than 1000 psia, the maximum
43 amount of MEG lost to the gas is 0.002 lbm/MMscf.

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 Summary of Rule of Thumbs in Hydrate Prevention

Rule of Thumb 5: Methanol concentration dissolved in condensate is 0.5 wt %.

Rule of Thumb 6: The mole fraction of MEG in a liquid hydrocarbon at 39 oF and

pressures greater than 1000 psia is 0.03% of the water phase mole fraction of
MEG.

Rule-of-Thumb 7: Natural gases cool upon expansion from pressures below

6000psia; above 6000 psia the temperature will increase upon expansion. Virtually
all offshore gas processes cool upon expansion, since only a few reservoirs and no
current pipelines or process conditions are above 6000 psia.

Rule-of-Thumb 8: It is always better to expand a dry gas than a wet gas, in

order to prevent hydrate formation in unusual circumstances, e.g. changes in
upstream pressure due to throughput changes.

44 Rule-of-Thumb 9: Where drying is not a possibility, it is always better to take a

large pressure drop at a process condition where the inlet temperature is high.

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 Summary Rule of Thumbs in Hydrate Prevention

Rule-of-Thumb
  10: Monoethylene glycol injection is used when the required
methanol injection rate exceeds 30 gal/hr.

Rule-of-Thumb 11: Use of anti-agglomerants requires a substantial

oil/condensate
phase. The maximum water to oil ratio (volume basis) for the use of an anti-
agglomerant is 40:60 on a volume basis.

Rule-of-Thumb 12: PVP may be used to inhibit pipelines with subcooling less
than for flow lines with short gas residence times (less than 20 minutes).

Rule-of-Thumb 13: VC-713, PVCap, and co-polymers of PVCap can be used to

inhibit flow lines at subcooling less than , with water phase residence times up to
30 days.

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