Bony Budiman

GAS HYDRATE
INHIBITOR
BONY BUDIMAN
2021
Bony Budiman

COMMON QUESTIONS

• What is hydrate, and what is the effect in the gas

field ?
• What is hydrate inhibitor, KHI and LDHI ?
• How to handle hydrate ?
• Field cases !
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• HYDRATE MANAGEMENT
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 Bony Budiman

OBJECTIVE

• Refresh simple definition of

hydrate
• Sharing implication of hydrate
in the gas field
• Sharing hydrate inhibitor
mechanism
• Sharing some field cases

Cortesy picture : Safety Problems Caused by Hydrate Formation in Deepwater Production Operation, Susana Leon Caceres, Texas A&M University, 2017
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• TREATMENT METHOD
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 HYDRATE

 Ice-like solids
 Small hydrocarbon molecules trapped inside
water “cages”
 Not exactly “pure” organics
 About 85% water and 15% hydrocarbon
 Can trap a large amount of organic deposits or liquids
by agglomeration
 Need four basic elements to survive
 Water (constituent)
H  Gas (constituent)
O H  High pressure (condition)
C H
 Low temperature (condition)
H
H
H
WHERE DO HYDRATES FORM?

• Occurrence of hydrate plug is usually

between well, wellhead and platform

• Downstream of a choke or other valve where

there is a pressure drop (and subsequent cooling
effect).

• In pipelines where gas flows over or bubbles

through liquid pools.

• During shut-in's and startup conditions the flow and

mixing regimes favors hydrate formation.

• During well tests and drilling operations there can

be high gas velocities and water mixing allowing for
hydrate generation.

• Any location where gas & water flow under cold

conditions
 WHY ARE HYDRATES A PROBLEM?

• Rapidity of Plug Formation  Production Loss

• Time and resources required to mitigate plugs

• Production loss due to shut-ins

• Exacerbate other flow problems

• i.e. combination wax and hydrate plugs

• Safety Risk

Picture courtesy of Petrobras (Brazil)

 Bony Budiman

SAFETY RELATED TO HYDRATE – PIPER ALPHA

• On July 6 1988, a worker removed the pressure safety valve

from Pump A but the job not completed until end of dayshift
(6 p.m) and let PSV missed.
• At 9:45 p.m., the second shift was faced with a hydrate
buildup that blocked the gas compression system The
blockage resulted in failure of Pump B, which would halt all
offshore production unless Pump A could be restarted
• At 9:55 p.m, due to lack of communication and procedure,
Pump A (which not yet ready) restarted
• Gas leaked, then ignited an uncontrollable fire.
• 167 Piper Alpha crewmen and rescue personnel were lost.

Courtesy picture : https://www.bbc.com/news/uk-scotland-22840445

 WHEN DO HYDRATES FORM?

 Thermodynamically favor hydrates once

curve is crossed from hydrate free to
hydrate zone
 Parameters affecting hydrate formation :

Courtesy picture : Evaluating New Chemicals and Alternatives for Mitigating Hydrates in Oil and Gas 10
Production, Pickering et.al,
 HOW HYDRATE FORMED :

Presence of the four As time continues and the conditions are right,
elements required to the clusters start to share faces and build upon
make hydrates (low each other (like Lego) and full cages develop.
Gas starts to dissolve in This starts the process of agglomeration,
temperature, high
pressure, water and gas)
the water phase. At this building more and more hydrate structures. Critical growth occurs when the size of
point, the system is just This may initially look like slushy snow (small the clusters (agglomerates) reach a critical
but no gas molecules are
entering the hydrate pellets of hydrates dispersed in the produced
dissolved in the
curve and the hydrate size (8-30nm). At this stage, rapid growth
water phase. . fluids).
cages are forming and (also known as catastrophic
dissolving. growth) follows. Expect plugging to occur
The cages are easily
formed, broken and
quickly after this. At this stage the hydrate
reformed (constantly would appear as a compact ice plug.
undergoing change).
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• HYDRATE MANAGEMENT
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 Bony Budiman

HYDRATE MANAGEMENT

Courtesy Picture : https://www.researchgate.net/figure/Hydrate-risk-management-framework-illustrating-the-importance-of-no-hydrate-control_fig1_332616959

Bony Budiman

BASIC CONCEPT OF CHEMICAL TREATMENT

• There are 3 types of chemicals used to inhibit hydrate formation : thermodynamic, kinetic
and anti agglomerants.
• Chemicals considered since it will not change the process and facilities, just ensure the
injection facilities are ready to use.
• There are 3 types od hydrate inhibitor that currently used :
• Thermodynamic Hydrate Inhibitor
• Low Dosage Hydrate Inhibitor
• Kinetic Hydrate Inhibitor
• Anti Agglomerants.
Bony Budiman

Hydrate
Chemical
Inhibitor

Thermodynamic Low Dosage

Hydrate Hydrate
Inhibitor (THI) Inhibitor (LDHI)

Anti-
Kinetic Hydrate
MEG Methanol Agglomerant
Inhibitor (KHI)
(AA)
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• HYDRATE MANAGEMENT
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 Bony Budiman

THERMODYNAMIC HYDRATE INHIBITORS (THI)

• THI s inhibit hydrate formation by shifting the hydrate phase boundary to

lower temperature and higher pressure,
• Examples – Monoethylene Glycol (MEG), Methanol, Ethanol
• Why
• Low risk
• Ease of recommendation

• Why Not
• Methanol in crude penalties
• Volume requirements
• Oxygen and corrosion
• Cost (MEG)
• Induce scale/salt deposition
• Significant losses to oil phase

Courtesy picture : Hydrate Formation and Inhibition in Offshore Natural Gas Processing, Alexandre Mendonça Teixeira et.al,
Natural Gas Processing. SpringerBriefs in Petroleum Geoscience & Engineering. Springer, Cham, 2017
 Bony Budiman

THE REQUIREMENT OF THI

• The Hammerschmidt equation beside

𝐶 ∗ 𝑊 could be used to determine the amount of
inhibitor needed to prevent hydrate
∆𝑇 = formation
𝑀 ∗ (100 − 𝑊) • The equation was based upon more than
100 natural gas hydrate
• measurements with inhibitor
∆T = hydrate depression, (Teq - Toper) oF, concentrations of 5 - 25 wt% in water with
C = constant for a particular inhibitor (2,335 for MeOH; 2,000 for MEG) high accuracy; tested against 75 data points,
W = weight per cent of the inhibitor in the liquid, the average error in ∆ T was 5%.
M = molecular weight of MeOH (32) or MEG (62).
 Bony Budiman

EXERCISE OF HAMMERSCHMIDT EQUATION

• Estimate the methanol

Solution :
concentration needed to DT = Temperature Depression (50oF - 39oF= 11 F),
o

provide hydrate inhibition M = Molecular Weight for Methanol (= 32)

C = Constant for Methanol (= 2335)
at 450 psia and an ocean
W = Weight Percent Inhibitor
floor temperature of 39oF 𝐶 ∗ 𝑊 100 ∗ 𝑀 ∗ ∆𝑇
or
for a gas composed of ∆𝑇 = 𝑊 =
𝑀 ∗ (100 − 𝑊) 𝑀 ∗ ∆𝑇 + 𝐶
uninhibited hydrate
formation conditions of 100∗32∗11
50oF 𝑊 = = 13.1%
32∗11 +2335
Bony Budiman

EFFECTIVENESS OF THI

• In the same concentration, MeOH and

NaCl provide similar high subcooling
but NaCl has consideration of corrosion
and deposition effect
• MeOH usually cheaper than MEG, but
MEG is easier to recover. For long term
and high requirement, MEG is preferred
since it could be recovered back.
Bony Budiman

LOW DOSAGE HYDRATE INHIBITOR

• The name came from its lower dosage

compare to MEG or Methanol in inhibit
hydrate
• There are two type of LDHI : Kinetic
Hydrate Inhibitor (KHI) and Anti
Agglomerates (AA).
• KHI works by delay the kinetic (hydrate
reaction velocity) meanwhile AA prevent
crystal growth to agglomerate
KINETIC HYDRATE INHIBITORS-KHI (1)

• Polymers that associates with the

hydrate cage and delays nucleation
to remain virtually hydrate free
• KHI slow the rate of hydrate
formation by binding to the surface
of the growing hydrate crystal in
the early stages of nucleation. This
prevents the hydrate particle from
reaching its critical size (the size at
which particle growth becomes
thermodynamically stable).
Bony Budiman

KHI (2)

• Why
• No oil phase necessary
• Hydrate free operation
• Dose rates for KHI are between 0.1% to 5% based on water production rates
• Why Not
• Ceases to function when subcooling is over 20°F
• Difficult to prevent Structure I hydrate
• May not be compatible with some production chemicals especially corrosion inhibitors
• Cloud point can cause incompatibilities
• Time limitation
ANTI AGGLOMERATE (AA) - 1

• Contains surfactant, a hydrophilic

head and a hydrophobic tail.
• AA allow hydrate formation to
occur but they work to prevent
agglomeration of the particles so
that the hydrate crystals never
grow large enough to plug flowlines.
• AA's disperse the hydrate crystals
in the oil or condensate phase and
in this respect, the hydrates are
transported as a slurry.
Bony Budiman

ANTI AGGLOMERATE (AA) - 2

• Why
• Dose rates for AA’s are between 0.5% to 3% based on water production rates.
• No subcooling limitation
• No time limit
• Compatible at high temperatures and salinities
• Compatible with other production chemicals
• Blending possible with other production chemicals
• Dramatically reduced volume compared to methanol

• Why Not
• Oil phase necessary
• The water cut should be no greater than 40-50%.
• May create foaming and water in oil emulsion.
Bony Budiman

THERMODYNAMIC HYDRATE INHIBITOR

PROS
 Field Proven  10-100% dosage
 Excessive storage
 Full inhibition requirements
 Can melt hydrate  Excessive
 Freeze point contamination (water
washing of crude
depression (icing) required)
 Can be  SH&E issues
reclaimed/reused  Methanol flash point
 Commodity  Handling constraints

CONS
Bony Budiman

LOW DOSAGE HYDRATE INHIBITOR

PROS

<3% dosage (on  Subcooling limitation

water) (KHI only)
 Hold time limits (KHI
Minimal storage only)
No hydrocarbon  System challenges
(liquid hold-up, high
contamination temperature)
Environmentally Cannot melt
friendly hydrates
Lower capital Cannot melt ice

CONS
expense Likely one time usage
Bony Budiman

HYDRATE INHIBITOR SELECTION

• Rocking Cell
• Autoclaves
 Bony Budiman

ROCKING CELL

• It consists of two test cells with a maxi operating pressure of 20 MPa

• Each cell (volume 20 ml) contains a stainless steel ball that provides agitation and two
proximity sensors which record the ball running time.

• A pressure transducer is connected to each cell to monitor the pressure inside the cell.

• The inner diameter of each cell and diameter of the steel ball are 1.27 cm and 1.02 cm

• During the rocking, the balls run back and forth and enhance mixing of the mixtures in
the cells.

• Once the cell is blocked by hydrates, the ball will be prevented from moving.

• The temperature of the water bath is controlled by a chiller and checked by a

thermocouple (accuracy 0.1oC).

Courtesy picture : https://www.researchgate.net/figure/Sapphire-rocking-cell-setup_fig2_320110623

Bony Budiman

AUTOCLAVES

• Autoclave tests are performed by adding water (or brine) and

condensate (or oil) to the autoclave at ambient temperature and
pressure.
• The KHI is then dosed and the autoclave cooled to the test
starting temperature. The autoclave is then pressurized to the
test pressure using a synthetic gas mixture equivalent to the field
gas.
• Hydrate formation is detected by a sharp decrease in the
pressure in the autoclave due to the incorporation of the gas
molecules into the denser hydrate structure
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• HYDRATE MANAGEMENT
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 Bony Budiman

MONITORING

• The aim of monitoring is to ensure

the treatment method provide safe
operation in term of technical and
cost.
• Hydrate safety margin determined by
the developed hydrate monitoring
techniques could act as traffic lights to
help the operators have a better
control of hydrate inhibition

Courtesy Picture : Developing a Hydrate-Monitoring System, B. Tohidi, SPE, A. Chapoy, and J. Yang, Heriot-Watt University, 2017
 Bony Budiman

MONITORING METHOD

• Freezing-Point Depression Method. The presence of chemical additives in water, will disrupt the hydrogen
bonding between the water molecules by molecular interaction and as result will depress the freezing point of
water. It is understood that freezing-point depression can reflect the presence of chemical additives, and therefore
could be correlated with gas-hydrate phase boundary
• Velocity-Conductivity Technique. This method determine concentration of salts and hydrate inhibitors based on
measurement of the electrical conductivity and acoustic velocity in produced water. After feeding the measured salt
and inhibitor concentrations, the measured temperature, and the given hydrocarbon composition, the hydrate phase
boundary is predicted by a well-proven thermodynamic model
• Water Content Technique. Water content in vapour is related to temperature, pressure, gas composition. The
water content method was developed to determine equivalent concentrations of salts and inhibitors at given
temperature and pressure conditions and gas composition. Then the hydrate phase boundaries can be predicted by
the same model using the known salt concentration and the determined equivalent inhibitor concentration
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• HYDRATE MANAGEMENT
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 Bony Budiman

CASE 1 : KHI FOR BACKUP START UP - TOTAL

SOUTH PARS
• South-Pars Phases 2&3 development in Iran is a “wet
scheme” base design
• No process is performed offshore, all the produced
fluids are directly sent to shore through two 32” 109
km long sea lines
• Located at 3000 m depth below sea level
• The Condensate Gas Ratio (CGR) is 49.5 bbl/MMSCF
and Water Gas Ratio (WGR) is 0.88 bbl/ MMSCF
• The production is 1,000 MMSCF of dry gas and 40,000
bpd of condensate

Courtesy Picture : https://www.offshore-technology.com/projects/southpars/attachment/southpars4/

 Bony Budiman

CASE 1 : KHI FOR BACKUP START UP - TOTAL

SOUTH PARS
• It can be seen that the operating range is outside the hydrate
region in summer, while it enters the region in winter.
• According to the design basis, the maximum sub-cooling which can
be faced is 8°C in winter.
• The main protection of hydrate is MEG and MDEA for corrosion
inhibition.
• A few weeks before the Field start-up, i.e. December 2001, it was
found that one MEG piggy back line had been accidentally ruptured.
• The deployment of the MEG + MDEA base case was then
postponed and the decision to start the field using concomitant
injection of KHI & CI was taken

Courtesy Picture : SPE 88751 : South-Pars Phases 2 and 3: The Kinetic Hydrate Inhibitor (KHI) Experience Applied at Field Start-up
 Bony Budiman

CASE 1 : KHI FOR BACKUP START UP - TOTAL

SOUTH PARS
• The KHI injection at a dose of 1% wt. versus
produced water then decreased down to
0.75% wt
• The injection of KHI was 208 days in sea
line 1 and for 80 days in sea line 2.
• After this period, the basic design
MEG+MDEA was permanently restored
• At picture beside, the latest KHI dose is
around 0.75% wt meanwhile the MEG dose
is around 55% wt.

Courtesy Picture : SPE 88751 : South-Pars Phases 2 and 3: The Kinetic Hydrate Inhibitor (KHI) Experience Applied at Field Start-up
Bony Budiman

CASE 2 : METHANOL OPTIMIZATION

• The gathering system (GS) for this study spans approximately 125
miles and collects gas from wells using a local low pressure system
• The gas is then compressed from 600 to 800 psia.
• The GS is a wet gas system designed for hydrate inhibition with
methanol.
• At each booster compressor station, methanol is injected with
periodic rate adjustments based on the gas flow through each station.
• The GS and wells located with 4 seasons.
• It has shown that the system must be inhibited down to a
temperature of about 20°F in winter and about 40°F in summer

Courtesy Picture : Optimizing Methanol Usage For Hydrate Inhibition In A Gas Gathering System, Keith A.
Bullin and Jerry A. Bullin, Bryan Research & Engineering, Inc. Bryan, Texas U.S.A., 2004
Bony Budiman

CASE 2 : METHANOL OPTIMIZATION

• Average MeOH injection is 28 – 37 gallons/mmscf

• The GS has Methanol Recovery Unit (MRU) so
the injected volume of MeOH has no significant
Opex
• In 2001, the MRU had problem and shall be
shutdown for repaired.
• New calculation of MeOH immediately calculated
to reduce the OPEX.
Bony Budiman

CASE 2 : METHANOL OPTIMIZATION

• The basic idea is : the requirement of MeOH to

suppress the hydrate free zone shall be different in
winter and summer.
• The first step is calculate hydrate formation
temperature at each booster station as shown at
picture beside.
• The hydrate formation temperature is about 61 to
65°F for almost every station
Bony Budiman

CASE 2 : METHANOL OPTIMIZATION

• Based on calculation, the new injection dose of

MeOH is as described at picture beside
• For example, at Well C-102 at summer the
MeOH dose is 19.2 gallon/mmscf and at winter
is 35.4 gallons/mmscf
• Overall, the average dose at summer is 10.5
gallons/mmscf and at winter is 15.3 gallon/mmscf.
Decrease from 28-37 gallons/mmscf before
optimization program
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• HYDRATE MANAGEMENT
• HYDRATE INHIBITOR APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
Bony Budiman

SUMMARY

• In very simple definition : Hydrate is hydrocarbon trapped in the water cage

• Hydrate will cause several problem from equipment damage, production loss and fatality
• Some chemicals already proven to inhibit hydrate :
• Thermodynamic Hydrate Inhibitor such as MEG and Methanol
• Low Dosage Hydrate Inhibitor
• Kinetic Hydrate Inhibitor
• Anti Agglomerant

• Continues study based on monitoring shall be conducted to find better treatment or to

reduce operational cost
SUMMARY (1)
 Bony Budiman

REFERENCES

• Gas Hydrates -Strategies for Prevention, Training Seminar for Indonesia Customers by Clariant
• Evaluating New Chemicals and Alternatives for Mitigating Hydrates in Oil and Gas Production, Pickering et.al,
• Handout of Hydrate Chemistry, Champion Technologies
• Offshore Hydrate Engineering Handbook, E. Dendy Sloan, Jr., Center for Hydrate Research, Colorado School of Mines, Golden, Colorado 80401, 1988
• Safety Problems Caused by Hydrate Formation in Deepwater Production Operation, Susana Leon Caceres, Texas A&M University, 2017
• Developing a Hydrate-Monitoring System, B. Tohidi, SPE, A. Chapoy, and J. Yang, Heriot-Watt University, 2017
• SPE 88751 : South-Pars Phases 2 and 3: The Kinetic Hydrate Inhibitor (KHI) Experience Applied at Field Start-up, Philippe Glénat, SPE, Jean-Louis Peytavy,
Total, Nick Holland-Jones, SPE, Martin Grainger, Clariant, 2004
• Optimizing Methanol Usage For Hydrate Inhibition In A Gas Gathering System, Keith A. Bullin and Jerry A. Bullin, Bryan Research & Engineering, Inc. Bryan,
Texas U.S.A., 2004
• Hydrate anti-agglomeration and synergy effect in normal octane at varying water cuts and salt concentrations, Sanbao Dong, Abbas Firoozabadi, Elsevier
Ltd., 2017