HYDRATES AND HYDRATE PREVENTION

PART 2 : HYDRATE FORMATION

CONDITIONS

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

COURSE OUTLINE

INTRODUCTION

HYDRATE FORMATION CONDITIONS

PREDICTION OF HYDRATE FORMATION

HYDRATE FORMATION CURVES
CASE OF SOUR GASES
USE OF SIMULATION SOFTWARE

HYDRATE PLUG REMOVAL

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

INTRODUCTION WHAT ARE THEY?

Solids

Looks like ice

Composed of water
+

at least one other compound

EP 20267_a_A_ppt_10 - HYDRATES & HYDRATE PREVENTION

2012 - IFP Training

IT IS NOT ICE !

INTRODUCTION WHAT ARE THEY?

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

INTRODUCTION WHAT ARE THEY?

HYDRATES consist of hydrocarbons trapped inside lattice

of water molecules

Increase structure STABILITY (like a ball inside a box)

Create operating problems because, at elevated pressures,

they can exist at higher temperatures than ice (e.g; 4C @
12 bar or 20C @ 100 bar)

One cubic foot of gas hydrate contains 160 cubic feet of

gas at standard temperature and pressure

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

COURSE OUTLINE

INTRODUCTION

HYDRATE FORMATION CONDITIONS

PREDICTION OF HYDRATE FORMATION

HYDRATE FORMATION CURVES
CASE OF SOUR GASES
USE OF SIMULATION SOFTWARE

HYDRATE PLUG REMOVAL

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

HYDRATE FORMATION CONDITIONS GENERALITIES

3 CONDITIONS are required for hydrate formation:

Presence of LIQUID water (free, dissolved or emulsified)
Presence of light hydrocarbons (from C1 to C4), or acid gas (CO2, H2S) or Nitrogen
High enough P and/or Low enough T conditions (depending on the nature & composition of gas)

May occur naturally underground, at & below seabed

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

HYDRATE FORMATION CONDITIONS GENERALITIES

Key points hydrates formation conditions

To get some hydrates you need 4 things :

another compound

WATER

EP 20267_a_A_ppt_10 - HYDRATES & HYDRATE PREVENTION

A GAS

PRESSURE

2012 - IFP Training

COLD

Hydrogen bonds

HYDRATE FORMATION CONDITIONS IFP RESERCH FACILITIES

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

COURSE OUTLINE

INTRODUCTION

HYDRATE FORMATION CONDITIONS

PREDICTION OF HYDRATE FORMATION

HYDRATE FORMATION CURVES
CASE OF SOUR GASES
USE OF SIMULATION SOFTWARE

HYDRATE PLUG REMOVAL

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

HYDRATE FORMATION CURVE Influence of GAS COMPOSITION (Specific Gravity)

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

COURSE OUTLINE

INTRODUCTION

HYDRATE FORMATION CONDITIONS

PREDICTION OF HYDRATE FORMATION

HYDRATE FORMATION CURVES
CASE OF SOUR GASES
USE OF SIMULATION SOFTWARE

HYDRATE PLUG REMOVAL

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

EFFECT OF H2S AND CO2 ON HYDRATE FORMATION CONDITIONS Ref. GPSA

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

HYDRATE FORMATION TEMPERATURE FOR GASES CONTAINING H2S

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

COURSE OUTLINE

INTRODUCTION

HYDRATE FORMATION CONDITIONS

PREDICTION OF HYDRATE FORMATION

HYDRATE FORMATION CURVES
CASE OF SOUR GASES
USE OF SIMULATION SOFTWARE

HYDRATE PLUG REMOVAL

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

USE OF SIMULATION SOFTWARE

These methods are based on fundamentals equations of phase equilibrium

When hydrates form, T, P and chemical potential of H2O have the same values in gas,
liquid water and solid hydrate phases

Computer simulation programs are superior both in accuracy and ease of

extrapolation

Remark : PRO II does not take into account the amount of water present in the gas
It always calculates hydrate formation assuming the presence of free water is present.
It always assume that the gas is water saturated, i.e. it increases the gas water content if
not at water saturation

MULTIFLASF of INFOCHEM is based on experimental data

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

Accurate hydrate formation temperature of HC mixtures in presence of free water with

salts, MeOH, glycols (MEG,DEG,TEG).

USE OF SIMULATION SOFTWARE

- EXAMPLE OF COMPUTER SIMULATION RESULTS -

Hydrates Formation & Water Dew-Point Curves

160
140

100
80
60
40
20
0
0

20

40

60

80

Temperatue (C)
Hydrate Curve

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

Water Dew Point

100

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Pressure(bar abs)

120

OVERVIEW OF HYDRATE PREVENTION

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

COURSE OUTLINE

INTRODUCTION

HYDRATE FORMATION CONDITIONS

PREDICTION OF HYDRATE FORMATION

HYDRATE FORMATION CURVES
CASE OF SOUR GASES
USE OF SIMULATION SOFTWARE

HYDRATE PLUG REMOVAL

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

Key points hydrates formation conditions

To get some hydrates you need 4 things :

another compound

A GAS

COLD

PRESSURE

EP 20267_a_A_ppt_10 - HYDRATES & HYDRATE PREVENTION

2012 - IFP Training

WATER

HYDRATE PUG REMOVAL

Increasing the temperature to remove a hydrate blockage is not usually practical

since the blockage has to be first located and then heating equipment applied to
the blockage area. Nevertheless, this method can be applied in particular cases.

A pipeline plugged with hydrates can be unplugged by reducing the pipeline

pressure on both sides of the plug.

Reducing the pressure on only one side is EXTREMELY DANGEROUS!!! The solid
hydrate plug can break loose. Then the pipeline pressure drives the ice-hard
hydrate plug towards the lowered pressure side at very high velocity. When the
hydrate hits a bend or restriction, it can break the pipe and even unearth a buried
pipeline. Such accidents have resulted in loss of lives and extensive equipment
damage.

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

P = 70 bar

2011 - IFP Training

P = 100 bar

HYDRATE PUG REMOVAL SAFETY HAZARDS

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

HYDRATE PUG REMOVAL SAFETY HAZARDS

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

HYDRATE PLUG REMOVAL EXAMPLE OF PROCEDURE

1st step:
Reduce slowly by steps the pipeline pressure on both sides of the plug, one side down to a pressure near atmospheric
pressure, other side down a pressure of a few bars (< 6 bar).

4 to 5
bar

Patm
Hydrate plug

Quick gas depressurization could generate a gas cooling to negative temperature values (Joule-Thompson expansion),
which favors ice formation and extends the melting period of the hydrate plug.
To prevent this event it is a good practice to control the gas temperature during depressurization.

2nd step:
Inject methanol to the upper pressure pipeline side when the pressure value starts to decrease.
The small flow brings the methanol towards the hydrate plug and favors by contact his dissociation.

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

Methanol can dissolve existing hydrates to few degrees. It is not the case with glycol: glycol can
prevent hydrates, but cannot attack or dissolve hydrates already present

QUIZ
True
The presence of moisture (water at vapor state) is enough to form hydrates, when combined with gas molecules
at a low enough temperature and high enough pressure

False

..
For
hydrate formation, the presence of LIQUID water is needed

The higher the density of a gas the higher its hydrate formation temperature (at a given pressure)

..
Hydrate formation temperature increases as specific gravity of gas increases

The presence of H2S in the gas increases the hydrate formation risks

..
Presence
of H2S increases hydrate formation temperature at a given pressure

Hydrate removal can be done safely by depressurization of downstream side of the flowline

..
Depressurization shall be performed gradually on BOTH sides, in order to avoid flow line rupture.

2011 - IFP Training

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

WHAT YOU SHOULD KEEP IN MIND?

Hydrates are composed of a water lattice, in which light hydrocarbons (C1, C2, C3, iso-C4) or impurities (H2S, CO2) are embedded
(Clathrates). The specific gravity of hydrates varies from 0.96 to 0.98

Hydrates could:
BLOCK flowlines, chokes, valves, instrumentation,
FOUL and PLUG heat exchangers,
ERODE chokes, control valves, turbo-expanders.

The formation of hydrates in natural gas requires

1. high enough pressure and low enough temperature conditions (depending on the composition of the effluent)
2. the presence of LIQUID water

For a given pressure, the temperature and thus the risks of hydrate formation iare higher if the density of the gas increases

The presence of H2S increases the risks of hydrate formation

Hydrate formation starts slowly. However, this phenomenon accelerates exponentially and ends up by blocking the
installations. Regular monitoring to detect the beginning of hydrate formation is thus more than recommended

Eliminating a hydrate plug is hazardous and can be very difficult

The main ideas to prevent hydrate formation are:

Lower the pressure (depressurization) and/or increase temperature (thermal insulation, heating)
Inhibition by injection of chemicals (MeOH, MEG, DEG, KHI)

Removing hydrates by depressurization could require days of flow interruption.

EP 20267_b_A_ppt_02 - HYDRATES & HYDRATE PREVENTION

2011 - IFP Training

Lower the Water Dew Point by removing moisture (dehydration)