NATURAL INHIBITION OF HYDRATES

FORMATION BY CRUDES
Philippe Glénat & Romain Devoisselle
OPS/EXP/PRD/GFP
NO MASSIVE HYDRATE FORMATION IN STATIC CONDITIONS

in case of fresh water + natural gas

gas (no liquid hydrocarbon)
@ 19°C sub-cooling at 110 bar
& in static conditions
what happens ? Nothing !

HYTRALOOP
very few water CSIRO-Perth (Western Australia)

hydrates  massive hydrate formation occurs

crystals only when mixing

- Hydrates formation requires energy/mixing  risk exists at restarts

@ high P
gas hydrate & low T
C1, C2, C3, iC4, nC4,
former + water HYDRATE
iC5, N2, CO2, H2S

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 HYDRATES FORMATION MECHANISMS WITH MIXING

● What happens inside P&T hydrate zone with mixing ?

PLUG
Hydrates growth
with agglomeration
induction period no AA-LDHI
(no hydrates) Hydrates
growth
period In case of “do-nothing”:
can be
o plugging risk is sure for gas/condensate
* very short for
o but is definitely not systematic for crudes (case study)
gas/condensate natural AAs present in crudes & presence of carrier phase
* very long for crudes [95% mass of crude components are not hydrate formers]

KHI-LDHI to boost
hold-time Hydrates growth
(Kinetic Hydrate Inhibitor) without agglomeration
with AA-LDHI (Anti-Agglomerant)
 “hydrate plug prevention”
low viscosity liquid slurry
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HYDRATE FORMATION & DISSOCIATION CURVES

● Thermodynamic Hydrate curve is dissociation # not formation curve

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HYDRATE KINETICS

● KHI-LDHI (Kinetic Hydrate Inhibitor) on the market since 1990 for

gas/condensate fields

● At TOTAL:

● Excellent know-how for gas/condensate fields

● 1st application at South-Pars 2&3 in Iran in 2002
● 1st base case solution: Dolphin in Qatar (2.2 bcfd / 600 kboepd) since 2007

● But never tested for crudes ...

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HYDRATE KINETICS FOR KHI-LDHIS & GAS/CONDENSATES
CRYSTAL GROWTH INHIBITION (CGI)
● CGI for KHI-LDHIs selection at TOTAL published 2011 TOTAL & HWU
- Principle: determine regions inside hydrate P&T zone where hydrates immediately
start to form = RGR (Rapid Growth Region) & where hydrates take significant time
before forming (= induction time or hold-time)

condensate
+ RGR
KHI-LDHI
Test s with constant mixing

exponential
hold-time
evolution
from 0 to ∞

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HYDRATE NATURAL KINETICS FOR CRUDES: ZINIA-2
2013

● STATOIL know-how for years but no publications by today

- Lab tests in 2013 by Statoil for ZINIA (XT thermal insulation concerns)
- results appear to be very similar to CGI approach
200

180 hold time t=0 hold time t=18h

160

140
x x Statoil comments:
• no influence of WC
pressure [bar]

120
RGR hold time • influence of production chemicals
t= infinite
100 x xx (act on IFT) but 2nd order
80 • influence of GOR due to change in
ZINIA-2 composition then hydrate curve
60
x
water 50 g/L (e.g. gas lift) : but just leads to
40
GOR=50 zones displacements
20 Test s with constant mixing • Reminder: no direct relation
no GL
0 between red zone & line plugging
0 2 4 6 8 10 12 14 16
temperature [°C] risk

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 HYDRATE NATURAL KINETICS FOR CRUDES: DALIA-304
2014

Dalia 706 & Dalia

Blend give same
results:
HT= hold-time
- RGR detection at
10°C sub-cooling
- Induction time at
field sub-cooling
4.5°C SC
(4.5°C) > 6 days
- Induction time at 6.5°C SC
intermediate SC 10°C SC
(6.5°C) > 6 days

- Same results if 6
days shut-in prior Test with constant mixing

to 6 days mixing

Flow Assurance Days 2014 - 13 - 14 November - Pau 8

 HYDRATE NATURAL KINETICS FOR CRUDES: DALIA-304
2014

● While risk inside hydrate zone lasts only 8 hours during restart

PI data from
Nov 2013
planned SD
Restart
with line
full of DO

from F.Papot
ECP study
09Jul2014

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HYDRATE NATURAL KINETICS FOR CRUDES: TEMPA ROSSA
2014

Hydrate Zone Mapping – TR1 crude – 50g/L @ 20%WC GOR=55-75

ops
cond.

Lower P = Deeper RGR

(high P is conservative)

Tests with constant mixing

 soon: tests on TR-2 crude

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NATURAL HYDRATE INHIBITION OF CRUDES

● No massive hydrate formation in static conditions (whatever phases)

● Ability of crudes to prevent hydrate formation seems widespread

- shown so far on these Total crudes
Zinia-2 & Acacia (by Statoil) Dalia 706 & Dalia Blend
Tempa Rossa (TR1) Gengibre (indirect tests)
- new tests on-going: Zinia 3 & (Zinia2+Zinia3) & Tempa Rossa 2

● Reminder: there is no such delay for condensate & gas systems !

● It is NOT a “magic bullet” to switch to “do-nothing” for every Oil field

● Natural hydrate protection of crude is dependent of crude, GOR, water

salinity, phases present, production chemicals, ...
 case by case approach is compulsory !

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NATURAL HYDRATE INHIBITION OF CRUDES

● Valid only when crude is present  not valid for just water & gas
- water put in contact with crude remains not inhibited (recently checked)

● At field level, the green zone can only be

- Localised : consider line geometry / beware of cold water accumulation +
RBGL (down sloping line) or wells (up sloping line)
- Field life limited e.g. can disappear with seawater breakthrough

● But red zone (instantaneous hydrate formation) is not equivalent to

instantaneous HYDRATE PLUG as hydrates transportability remains
fully possible by crudes
- Hydrates quantity depends on water & gas amounts present, crude, waters...
 on-going HQ actions
- AA-LDHI can still be required to ensure hydrates transport
 on-going HQ actions

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HYDRATE NATURAL KINETICS FOR CRUDES: ACACIA
2013
hold time t=0 hold time t=12h
x
ACACIA
STATOIL results
x x
ACACIA
water 30 g/L

x xx x GOR=300

no GL

x
x

Tests with constant mixing

Acacia (Pazflor Oligocene) has only limited natural kinetics ability

AA-LDHI injection is required to ensure hydrates transportability

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HYDRATE PLUG PREVENTION TOOLS

● Natural hydrate inhibition of crudes is another “tool” for hydrate plug

prevention (mitigation) together with
- Proper & detailed hydrate risk assessment
- Study of transportability of hydrates once formed

● New “Hydrate tools” can be used to adapt Operating Philosophy

- Adapt conservative Design rules to actual hydrate risk conditions
• check Hydrate risk with present P&T & GOR & Water salinity
- Will simplify operations & can lead to shortfalls reductions (e.g. faster restarts)

● Can help to change design towards “good enough”: on-going exercise…

● Production inside hydrate P&T zone requires CARE & KNOWLEDGE

Flow Assurance Days 2014 - 13 - 14 November - Pau 14

 Bedankt
gracias Terima Kasih
Cám ơn
谢谢
Thank you

merci
спасибо

Obrigado
‫ﺷﻛﺭﺍ‬
Tusen takk
Flow Assurance Days 2014 - 13 - 14 November - Pau 15
 DISCLAIMER and COPYRIGHT RESERVATION
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BACK-UP

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HYDRATE CELL EQUIPMENT AT PRD/GFP

• 80% liquid filling

• specific mixer at very high rpm (1300)
• hydrate formation by gas consumption, P decrease, T increase
• eventual plug when too much hydrates by blockage of rotating mixer

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HYDRATE INDUCTION TIME RESULTS VS GOR
200 200

150 150

pressure [bar]

pressure [bar]
GOR=100 100 100 GOR=150
50 50

GOR = 100 GOR = 150

0 0

ZINIA
0 5 10 15 20 0 5 10 15 20
temperature [° C] temperature [° C]

200 200
STATOIL results
150 150
pressure [bar]

pressure [bar]
100 100
GOR=200 GOR=300
50 50

GOR = 200 GOR = 300

0 0
0 5 10 15 20 0 5 10 15 20
temperature [° C] temperature [° C]
ZINIA-2
200 200
water 50 g/L
150 150
pressure [bar]

pressure [bar]

GOR=500 GOR=750
100 100

50 50

GOR = 500 GOR = 750 Tests with constant mixing

0 0
0 5 10 15 20 0 5 10 15 20
temperature [° C] temperature [° C]

200 200

150 150
pressure [bar]

pressure [bar]

GOR=1000 100 100

GOR=1250
50 50

GOR = 1000 GOR = 1250

0 0
0 5 10 15 20 0 5 10 15 20
temperature [° C] temperature [° C]

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DALIA-P304 FIELD & LAB CONDITIONS

Field LAB
mainly CAMELIA DALIA 706 (UMC)
crude
& few UMC Dalia Blend from FPSO
80 g/L
water 80 g/L
(lowest from 3 Y)
WC 30% 30% & 80%

GOR (Sm3/Sm3) 50-150 35-45

P (bar) 60 60 - 80
CI (Norust 5130) 90 ppm vs w 90 ppm vs w
hydrate subcooling
4.25°C 4.5°C
60 bar & 4°C
restart high mixing

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SUMMARY OF DALIA-P304 LAB RESULTS

● Same results with 2 “most representative & available” crudes

● In field conditions of 60 bar & 4°C & salty water (80g/L):

- no possible hydrate formation during static conditions
- upon restart, hydrates start to massively form only after >3 to 6 days
- demonstrated for WC going from 30 to 80% (max tested)

 Recommendation to TEPA
Consider the “do nothing” option, as long as during restarts
- fluids transit inside hydrate zone is ≤ 3 days (12 hours required)
- fluids are at WC ≤ 80%
- sub-cooling ≤ 6.5°C for a P range between 60 to 80 bar

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