6 Hydrates Prevention Inhibition

HYDRATES AND HYDRATE PREVENTION
HYDRATE PREVENTION
BY INHIBITION
EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION
HYDRATE PREVENTION DIFFERENT POSSIBILITIES
2014 - IFP Training
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
2014 - IFP Training
COLD
Hydrogen bonds
COURSE OUTLINE
INTRODUCTION
THERMODYNAMIC INHIBITORS
Principle
Selection criteria
Examples of field applications
Hammershmidts correlation
Application 1: Methanol (MeOH) inhibition
Application 2: Glycol (MEG or DEG) inhibition
LOW DOSAGE HYDRATE INHIBITORS (LDHI)
Overview
Kinetic Hydrate Inhibitors (KHI) Nucleation limiters OR Growth modifiers
Anti-Agglomerants (AA)
2014 - IFP Training
INTRODUCTION COMPARISON of the 2 categories of INHIBITORS

Thermodynamic Inhibitors are added in order to reduce the activity of water phase and
prevent hydrate formation
Low Dosage Hydrate Inhibitors (LDHI) will delay hydrate formation or growth but do not
stop them.
ADVANTAGES
DISADVANTAGES
Transport
Dissolves in HC
Volatile (high loss rate)
High OPEX
Thermodynamic Inhibitors
MeOH
: Methanol
Low CAPEX
MEG
: Monoethylene glycol
DEG
: Diethylene glycol
TEG
: Triethylene glycol
SALTS
(Rule of thumb: 20 g NaCl/l = 1C subcooling)
Regeneration (low loss rate)

Low OPEX
High viscosity
Crystallization risk
High CAPEX
Low cost
Natural (formation salt)
Need high quantity

Corrosion
Low quantity
High cost
LDHI (Low Dosage Hydrate Inhibitor)

: Kinetic Hydrate Inhibitor
Nucleation Limiters
Growth modifiers
Anti-agglomerants
(Mixed feedback)
2014 - IFP Training
KHI
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
THERMODYNAMIC INHIBITORS PRINCIPLE

FREEZING TEMPERATURES OF AQUEOUS SOLUTIONS OF METHANE AND SOME GLYCOLS
Eutectic behavior
2014 - IFP Training
EFFECT OF INHIBITOR INJECTION

ON HYDRATE FORMATION TEMPERATURE
2014 - IFP Training

PHYSICAL AND CHEMICAL PROPERTIES OF METHANOL AND SOME GLYCOLS
HYDRATE FORMATION INHIBITION
DEHYDRATION
Methanol
Mono-Ethylene Glycol
Di-Ethylene Glycol
Tri Ethylene Glycol
MeOH
MEG
DEG
TEG
CH3OH
C2H6O2
C4H10O3
C6H1404
kmol/kg
32.04
62.10
106.10
150.17
Normal Boiling Point (NBP)
64.5
197.3
Decomposition > 165C
244.8
Decomposition > 165C
288.0
Decomposition > 204C (400F)
Vapor Pressure at 25C
mmHg
120
0.12
< 0.01
< 0.01
Density at 25C
Density at 60C
kg/m3
kg/m3
790
-
1,110
1,085
1,113
1,088
1,123 (24C)
1,091 (66C)
Freezing Point
- 97.8
- 13.3
- 8.3
- 4.3
Viscosity at 25C
Viscosity at 60C
cP
cP
0.52
-
16.50
4.68
28.20
6.99
56.0 (24C)
8.1 (66C)
Specific heat 25C
kcal/kg.C
0.60
0.58
0.55
0.500 (24C)
Latent heat of vaporization at 1 atm.a
kcal/kg
202
129
97
Flash Point
115.6
123.9
176.7
12.0
N.B: these properties are results of laboratory test. They may differ from commercial product specifications.
2014 - IFP Training
Molecular Weight
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
THERMODYNAMIC INHIBITORS SELECTION CRITERIA
CHOICES TO MAKE
Which inhibitor?
Continuous or intermittent injection?
Regeneration?
Which concentration of regenerated (lean) inhibitor?
Amount and concentration of rich inhibitor?
DATA TO COLLECT
Flow rate?
Minimum and maximum pressure in unit?
Fluid composition (incl. heavy components)?
Minimum temperature in unit?
Water dew point specification?
2014 - IFP Training
THERMODYNAMIC INHIBITORS SELECTION CRITERIA
METHANOL:
PROVEN technique,
BUT: highly TOXIC and FLAMMABLE, important LOSSES in gas and condensate, LARGE
QUANTITIES to be injected (OPEX, logistics, regeneration), often used for TEMPORARY
inhibition at any temperature.
Glycols preferred when required permanent methanol injection > 120 l/h
GLYCOLS:
PROVEN technique,
BUT costly (CAPEX), regeneration feasible (piggy-back line), but RECLAIMING problems if
produced water is salted
MEG: Continuous inhibition at T< -10C (vaporization losses at higher temperatures)
DEG: Continuous inhibition at T> -10C (high viscosity, difficult to separate condensate
and DEG + Water)
Methanol / glycol content in condensate/LPG may be too high for refineries: sales
price to be discounted (for the field life?)
2014 - IFP Training
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
DEWATERING OF A LONG PIPELINE AFTER WATER HYDROSTATIC

TEST
2014 - IFP Training
EXAMPLE OF HYDRATE INHIBITION USING MEG IN A LTS PROCESS
2014 - IFP Training
EXAMPLES OF GAS FIELD DEVELOPMENT SCHEMES
NORTH FIELD QATAR
2014 - IFP Training

Qatargas I "DRY scheme"
NORTH FIELD
general map
South Pars 2&3 "WET scheme"
RAS
LAFFAN
0.9 BScfd
1 BScfd
2014 - IFP Training
1 BScfd
Hydrate Inhibition Process: MEG Injection

(Wet Scheme)
GAS to
Gas Treatment
CONDENSATES
To treatment
PRIMARY
SEPARATION
SALT RECLAMING
WELLHEAD PLATFORMS
(No Treatment)
Rich MEG
TANKS
FILTRATION
STORAGE
TANK
MEG
REGENERATION
Lean MEG
ONSHORE PROCESSING FACILITIES
Injection of:
MEG (Hydrate inhibition)
&
AMINE (Corrosion Inhibition)
2014 - IFP Training
PIGGY-BACK LINE

SOUTH PARS 2 & 3 PROJECT
Customer : HYUNDA
End User : TOTAL
Location : Assaluyeh (Iran)
Date : 2000
2014 - IFP Training
On-site installation of the 4 MEG Regeneration packages


MEG Regeneration Packages (ORMEN LANGE)
Dimensions:
11430 x 5460 x 17200 (H x W x L) for each
Weight:
100 tons for each
2014 - IFP Training

Salts if present in production water will accumulate in the MEG loop and eventually
result in deposits/plugging
Reclaiming is necessary to keep salts below saturation levels
Possible reclaiming technologies:
salts precipitation through evaporation
ion exchange
2014 - IFP Training
MEG Reclaiming through Ion Exchange

COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria

Overview
2014 - IFP Training
CALCULATION OF REQUIRED INHIBITOR FLOW INHIBITOR LOSSES
Volume injected = Amount in free WATER + Losses to GAS + Losses to LIQUID HC
Inhibitor losses to VAPOR phase :

GLYCOLS:
4 kg/106 Sm3 of gas,
METHANOL:
given by charts
Inhibitor losses to LIQUID phase

/m3
GLYCOLS:
0.2 kg
of hydrocarbon liquid,
METHANOL:
2 kg/m3 of hydrocarbon liquid,
GAS
LIQUID HC
LIQUID WATER
Inhibitor losses in REGENERATION system (for glycols):

GLYCOLS:
25 kg/106 Sm3 of gas (mainly due to carry-over in inlet plant separator and regenerator)
2014 - IFP Training
CALCULATION OF REQUIRED INHIBITOR FLOW Hammerschmidts

correlation
HAMMERSCHMIDT: semi-empirical correlation (1934 - 100 measurements)

W = 100 .
T . M
K i + (M . T)
OR
T =
W . Ki
100 . M W . M
W : weight % pure inhibitor in liquid water phase

T : depression of hydrate formation temperature (C)
M
Ki
: molecular weight of inhibitor (kg/ kmol)

: Hammerschmidt constant (C.kg /kmol)
Inhibitor
M (kg/kmol)
Ki (C.kg/kmol)
Correlation accuracy:
MeOH
32
1 297
MEG
62
2 220
DEG
106
2 220
good
fair
fair
Nielsen Bucklin correlation

is better for Glycols
2014 - IFP Training
Example: to protect a 15C hydrate sub-cooling what is the amount of MeOH or glycols
required to maintain in
MeOH
MEG
DEG
liquid water phase?
29.5 % Wt.
27.0 % Wt.
..
..
41.7 % Wt.
..
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
APPLICATION 1: Methanol (MeOH) inhibition

The aim of this application is to estimate the Methanol injection rate in order to avoid
hydrate formation.
Dry gas Sp.gr.:
0.7
Water content:
gas is moisture-saturated at 40C and 100 bar.a (1450 psi.a)
Operating conditions: 10C and 100 bar.a (1450 psi.a)
Gas acidity:
Sweet gas (no H2S nor C02)
Wet gas flow:
10 MSm3/day
20
.
...
Comments: the hydrate
formation temperature is higher than the operating temperature (10C),
which implies
a risk of hydrate formation in case no precautions are taken!!!
...
2014 - IFP Training
1 - Hydrate formation temperature at 100 bar.a (1450 psi.a):
2 - Estimate the amount of condensed water at operating conditions (10C and 100 bar.a).
Use the Bukaceks correlation, without density correction.
Temperature
SATURATION CONDITIONS
OPERATING CONDITIONS
40 C
10 C
Pressure
100 bar.a
Bukaceks A coefficient
.
56
121
.
9 346
Bukaceks B coefficient
267.51
.
.
70.80
H2O content of wet gas
.
829
mg/Sm3
.
164
665
.
mg/Sm3
(A)
2014 - IFP Training
Amount of condensed water at operating conditions (10C and 100 bar.a):
mg/Sm3
3 - Estimate the required MeOH concentration W of the Water/MeOH solution, to

prevent hydrate formation. Take a safety margin of 3C.
Required subcooling T, including a safety margin of 3C:
13
.
Required MeOH concentration of the Water/MeOH:
25
.
Wt %
(B)
4 - Estimate the MeOH required in condensed water, per Sm3 of wet gas.
665
.
mg/Sm3
(A)
.
25
Wt %
(B)
MeOH required in condensed water
222
.
mg/Sm3
(C)
2014 - IFP Training
Amount of condensed water at operating conditions:
APPLICATION 1: Methanol (MeOH) inhibition (losses in gas)

5 - Estimate the MeOH lost to the vapor phase.
1 lb/MMSCF = 16.9076 mg/Nm

= 16.0817 mg/Sm3
20
mg/Sm3 per Wt %
.
25
Wt %
.
MeOH lost to gas phase:
500
.
mg/Sm3
(B)
(D)
2014 - IFP Training
MeOH losses per wt% of MeOH in the MeOH/Water solution
APPLICATION 1: Methanol (MeOH) inhibition (losses in condensates)

6 - Estimate the MeOH lost to the condensates (500 mg/Sm3), assumed to be normal
octane (nC8).
Condensate content:
MeOH lost to HC liquid phase (condensates):
3
.
2014 - IFP Training
Solubility of MeOH in nC8
Wt %
500
mg/Sm3
15
.
mg/Sm3
(E)
7 Estimate the total MeOH injection rate.

MeOH required in condensed water:
222
.
mg/Sm3
(C)
MeOH lost to gas phase:
.
500
mg/Sm3
(D)
MeOH lost to HC liquid phase (condensates):
.
15
mg/Sm3
(E)
Total required MeOH:
.
737
mg/Sm3
(C+D+E)
Gas Flow rate

Total MeOH injection rate
MeOH density (at 15C)
Total MeOH injection rate
.
7 370
798
.
9.24
MSm3/day
kg/day
kg/m3
m3/day
2014 - IFP Training
10
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
APPLICATION 2: Glycol (MEG or DEG) inhibition
GLYCOL LOSSES TO LIQUID HC (NEGLIGIBLE !!!)
2014 - IFP Training

The aim of this application is to estimate MEG injection rate, for a Natural Gas Liquids
(NGL) extraction unit based on Low Temperature Separation (LTS) process .
Dry gas Sp.gr:
0.7
Water content:
LTS conditions:
gas is moisture-saturated at 40C and 70 bar.a (1015 psi.a)

4.4C and 70 bar.a (1015 psi.a)
Lean MEG:
Rich MEG:
chosen to be 80% weight (achieved by regeneration of the rich MEG solution)

chosen to be 60 % weight (after dilution of lean MEG by condensed water)
Gas acidity:
Wet gas flow:
Sweet gas (no H2S nor C02)

10 MSm3
Lean MEG (80 wt %):

MW of pure MEG:
1,104 kg/m3 (15C)

62 kg/kmol
2014 - IFP Training

.
18
1 - Hydrate formation temperature at 70 bar.a (1015 psi.a):
...
Comments: the
hydrate formation temperature is higher than the operating temperature (4.4C),
which implies a risk of hydrate formation in case no precautions are taken!!!
..
2 Is a 60% wt MEG concentration in the aqueous solution (in the LTS) enough to inhibit hydrate
formation? Justify.
Hammershmidt:
for W= 60%wt we reach a subcooling of 53.7C (> required subcooling = 18C - 4.4C)
..
Hence
there is no risk of hydrate formation in the LTS
..
3 - Estimate the amount of condensed water at LTS conditions (4.4C and 70 bar.a).
Use the Bukaceks correlation, without density correction.
SATURATION CONDITIONS
LTS CONDITIONS
40 C
4.4 C
Temperature
Pressure
70 bar.a
56 121
.
6 385
.
Bukaceks B coefficient
267.51
.
53.50
.
H2O content of wet gas
.
1 070
mg/Sm3
Amount of condensed water at LTS conditions (4.4C and 70 bar.a):

145
.
.
925
mg/Sm3
mg/Sm3 (A)
2014 - IFP Training
Bukaceks A coefficient

4 - Estimate the required flowrate of Lean MEG solution
80% x
Lean MEG
Weight
= 60% x
Rich MEG
Weight
Lean MEG
= 60% x Q Weight +
Condensed Water
Weight
Amount of condensed water at LTS conditions (4.4C and 70 bar.a):

Gas flow rate
Lean MEG
Weight
60%
x
80% 60%
925
.
10
Condensed Water
Weight
mg/Sm3
MSm3/day
.
9 250
kg/day
Injection rate of lean MEG solution
27 750
.
kg/day
Injection rate of lean MEG solution

1 104
25
.
kg/m3 (15C)
m3/day
2014 - IFP Training
Condensed water flow rate

Density of lean MEG solution
(A)
THERMODYNAMIC INHIBITORS KEY POINTS TO REMEMBER
Hammerschmidt's formula estimates the necessary inhibitor concentration

required in the aqueous phase to prevent hydrate formation. Its precision is
sufficient for methanol (which was used to develop it), and rather poor for glycols
(MEG or DEG).
The Nielsen-Bucklen equation gives better results than Hammerschmidt's formula

for Water-Glycols mixtures.
The calculation of the flow rate of methanol to be injected to inhibit hydrate

formation must take into account the methanol losses in the gas, and in the
condensates (liquid hydrocarbons) if they exist. These losses are relatively
significant!!!.
The glycol (MEG or DEG) losses in the condensates (hydrocarbon liquids), and in
the gas are low but end up becoming a non negligible part of the OPEX (Operating
Expenditure), which must thus be controlled...
2014 - IFP Training
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
LDHI OVERVIEW
DRAWBACKS OF CONVENTIONAL METHODS

High dosage rate
Need to recycle (MEG)
Topsides processing issues
Contamination of oil phase (MeOH)
HSE concerns
Salt and scale precipitation
2014 - IFP Training
LDHI OVERVIEW
Begin to be used in deepwater conditions (sub-cooling > 15C &/or BSW > 50%)
GoM (Shell)
The active material is expensive, but could be attractive due to low dosage
Remark: before deciding to use these additives, experimental testing is necessary to optimize
the active material formulation and quantify the injection rate
Types of Low Dosage Hydrate Inhibitors:

Kinetic Hydrate Inhibitors (KHI)
Nucleation limiter
Growth modifiers
Anti Agglomerants (or Dispersant)

additives
2014 - IFP Training
LDHI OVERVIEW
LDHI APPLICABILITY
VERSUS FIELD LIFE
Methanol
(MeOH)
WATER CUT
Kinetic
Hydrate
Inhibitor
(KHI)
latelife
Anti-Agglomerant (AA)
SUBCOOLING
AA
or
KHI
KHI /
MeOH
KHI
AA
or
KHI /
MeOH
midlife
SUBCOOLING
earlylife
2014 - IFP Training
TREATMENT COST PER BBL OF WATER
TREATMENT COST
VERSUS SUBCOOLING
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
KHI NUCLEATION LIMITERS & GROWTH MODIFIERS
Hydro-soluble polymers (similar to paraffin and corrosion inhibitors)
Low dosage injection (~ 0.5% wt active material vs water content)
Try to stop crystals growing (wrap round crystals growth modifiers) or delay
the crystal formation by stopping water molecules binding together (nucleation
limiters). Hydrate formation can only be slowed NOT STOPPED
Prevent hydrate formation for the time needed to transport the effluents under
hydrate region condition
Performance limited to subcooling < 10C
Available commercially through different suppliers (Clariant, Nalco/Exxon,

ISP, Akzo-Nobel, )
2014 - IFP Training
KHI STATE OF THE ART
Latest generation of products:

roughly 20F subcooling for > 48 hrs
roughly 30F subcooling for > 48 hrs in combination W / MeOH
Very system and product specific:

Cloud Point
7000
maximum pressure
salt tolerance
Stable Hydrate Region

6000
Pressure (psia)
5000
Shut-In Conditions
at Wellhead
4000
30 F Subcooling
3000
2000
2014 - IFP Training
Hydrate
Free
Region
1000
0
30
40
50
60
Temperature (F)
70
80
90
COURSE OUTLINE
INTRODUCTION
Principle
Selection criteria
Overview
2014 - IFP Training
ANTI-AGGLOMERANT (OR DISPERSANT) ADDITIVES
Hydrocarbon soluble polymers
Low dosage injection (~ 1% wt of active material vs water content)
Form water emulsion in hydrocarbon liquid
Crystals grow in water droplets but cannot group together
Independent of subcooling
Not time dependent - suitable for extended shut-ins
Require HC LIQUID phase; WC < 50 to 75%
Originally developed by IFP, SHELL
Available commercially from ONDEO

Nalco Energy Limited (Nalco/Exxon),
ISP, Akzo-Nobel, Fina Chemicals
2014 - IFP Training
LDHI KEY POINTS TO REMEMBER
2014 - IFP Training

6 Hydrates Prevention Inhibition

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HYDRATES AND HYDRATE PREVENTION

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

HYDRATE PREVENTION DIFFERENT POSSIBILITIES

2014 - IFP Training

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

HYDRATE FORMATION CONDITIONS GENERALITIES

Key points hydrates formation conditions

EP 20267_a_A_ppt_10 - HYDRATES & HYDRATE PREVENTION

2014 - IFP Training

LOW DOSAGE HYDRATE INHIBITORS (LDHI)

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

INTRODUCTION COMPARISON of the 2 categories of INHIBITORS

(Rule of thumb: 20 g NaCl/l = 1C subcooling)

Regeneration (low loss rate)

Need high quantity

LDHI (Low Dosage Hydrate Inhibitor)

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

2014 - IFP Training

LOW DOSAGE HYDRATE INHIBITORS (LDHI)

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

THERMODYNAMIC INHIBITORS PRINCIPLE

2014 - IFP Training

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

THERMODYNAMIC INHIBITORS PRINCIPLE

EFFECT OF INHIBITOR INJECTION

2014 - IFP Training

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

THERMODYNAMIC INHIBITORS PRINCIPLE

HYDRATE FORMATION INHIBITION

Tri Ethylene Glycol

Normal Boiling Point (NBP)

Vapor Pressure at 25C

Specific heat 25C

Latent heat of vaporization at 1 atm.a

2014 - IFP Training

LOW DOSAGE HYDRATE INHIBITORS (LDHI)

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

THERMODYNAMIC INHIBITORS SELECTION CRITERIA

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

THERMODYNAMIC INHIBITORS SELECTION CRITERIA

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

2014 - IFP Training

LOW DOSAGE HYDRATE INHIBITORS (LDHI)

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

DEWATERING OF A LONG PIPELINE AFTER WATER HYDROSTATIC

2014 - IFP Training

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

EXAMPLE OF HYDRATE INHIBITION USING MEG IN A LTS PROCESS

2014 - IFP Training

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

EXAMPLES OF GAS FIELD DEVELOPMENT SCHEMES

NORTH FIELD QATAR

2014 - IFP Training

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

EXAMPLES OF GAS FIELD DEVELOPMENT SCHEMES

South Pars 2&3 "WET scheme"

EP 20269_a_A_ppt_13 - HYDRATES PREVENTION - INHIBITION

2014 - IFP Training

EXAMPLES OF GAS FIELD DEVELOPMENT SCHEMES

Hydrate Inhibition Process: MEG Injection

ONSHORE PROCESSING FACILITIES

2014 - IFP Training

EXAMPLES OF GAS FIELD DEVELOPMENT SCHEMES

2014 - IFP Training