Raul Antonio di Toto Italmatch Chemicals S.p.A.

1. STRICTLY CONFIDENTIAL
2023 MIDDLE-EAST OILFIELD CHEMICALS | ABU DHABI
ECO-INHIBITORS
INNOVATING HYDRATE MANAGEMENT
Raul Antonio Di Toto | r.ditoto@italmatch.com
15th February 2023

2. Italmatch Chemicals at a glance

3. Italmatch Chemicals: a story of success

4. Italmatch Chemicals: a story of success

5. Gas Hydrates in O&G
✓ Hydrate formation is a crucial issue for the Oil & Gas
industry:
• Significant operational and integrity risks
• Low temp, high pressure conditions
• Highest risk at start up and shut down
✓ Hydrates are ice-like structures where the water
cage can host a small organic molecule
✓ Different structures exist depending on the guest
species, pressure & temperature
• Type 1
• Type 2
• Type H

6. Gas Hydrates in O&G – Deepwater Horizon Blowout
✓ Deepwater Horizon accident happened in 2010, resulting
in the largest accidental oil spill in history
✓ Eleven men died
✓ 507 million liters of oil spilled into the Gulf of Mexico over
87 days, coating nearly 1000 km of coastline
✓ Dramatic impact on birds and marine life
✓ Recent study* and simulations address the accident to
the formation of hydrates in the drilled well
✓ When the hydrate plug suddenly loosened, a rapid gas
expansion and pressure built up underneath the gas
hydrate plug occurred, allowing the plug to move like a
“bullet” in a gun barrel
* New lessons from the worst oil spill disaster ever (norwegianscitechnews.com)

7. TYPE 1 TYPE 2 MECHANISM
THI
Methanol,
MEG, …
Shift of the thermodynamic envelop curve of hydrate formation
LDHI KHI Delay of hydrate formation, for a specific sub-cooling and shut-in time
LDHI AA Hydrate is allowed to build-up in form of ice slurry
Chemical Inhibition & Prevention of Gas Hydrates in O&G
THI: Thermodynamic Hydrate Inhibitor
LDHI: Low Dosage Hydrate Inhibitor
KHI: Kinetic Hydrates Inhibitors
AA: Anti Agglomerants
Among all the prevention methodologies currently available, chemical treatment is probably the most-effective:

8. Thermodynamic Hydrates Inhibitors
T, °C
P,
atm
20
10
0
- 15
17
34
51
68
CSMHYD Model
10% MeOH – CSMHYD
20% MeOH – CSMHYD
Experimental
10% MeOH-Exp.
20% MeOH-Exp.
No MeOH
Unsafe region
(Hydrate)
Safe region
(no Hydrate)

9. Thermodynamic Hydrates Inhibitors
T, °C
P,
atm
20
10
0
- 15
17
34
51
68
CSMHYD Model
10% MeOH – CSMHYD
20% MeOH – CSMHYD
Experimental
10% MeOH-Exp.
20% MeOH-Exp.
10% MeOH No MeOH
Unsafe region
(Hydrate)
Safe region
(no Hydrate)

10. Thermodynamic Hydrates Inhibitors
T, °C
P,
atm
20
10
0
- 15
17
34
51
68
CSMHYD Model
10% MeOH – CSMHYD
20% MeOH – CSMHYD
Experimental
10% MeOH-Exp.
20% MeOH-Exp.
20% MeOH 10% MeOH No MeOH
Unsafe region
(Hydrate)
Safe region
(no Hydrate)

11. Kinetic Hydrates Inhibitors
T, °C
P,
atm
20
10
0
- 15
17
34
51
68
CSMHYD Model
Experimental
No MeOH
Unsafe region
(Hydrate)
Safe region
(no Hydrate)
KHIs allow a temporary “safety window”, for a specific sub-cooling and holding-time
ΔT = sub-cooling

12. TYPE 1 TYPE 2 PROS CONS
THI Methanol,
MEG, …
• Cheap/readily available
• Field proven & effective
• Working on a wide T, P range
• On the PLONOR List
• Flammable
• Toxic
• Under environmental fate scrutiny
• Application dosage >30%
• Logistic
• CAPEX for reclamation unit
LDHI KHI • The most used LDHI
• Readily available polymers
• Cheaper than AAs
• Logistic
• Application dosage still “% level”
• Not always suitable for severe
conditions
• More expensive than THIs
LDHI AA • Suitable for severe conditions
• Application dosage
• Very expensive
• Highly toxic
• Non-biodegradable
Chemical Inhibition and Prevention of Gas Hydrates in O&G

13. Chemical Inhibition & Prevention of Gas Hydrates in O&G
MeOH’s bulk offshore vessel MEG reclamation unit LDHI’s injection skid
Thermodynamic Hydrate Inhibitors LDHI

14. • Prof. Kelland – University of Stavanger – developed a new range of LDHI and co-funded Eco Inhibitors
• On 2019, Italmatch Chemicals acquired Eco Inhibitor’s IP, with the purpose to industrialize and commercialize three
innovative LDHI technologies
TRADE NAME CHEMISTRY UNIQUE VALUE PROPOSITION
1. Green AA ECO GAA007 B Amine derivative The 1st Yellow 1 Category AA for Norway
2. KHI SYNERGIST ECO KS6 Organic Salt
It allows cheaper KHI formulations or higher KHI
performance, beyond current limits.
It replaces >50% of polymer KHI in blends
3. GREEN KHI ECO K530 Fish Protein The only natural KHI, as green as it gets!
ECO-INHIBITORS LDHI Portfolio

15. Hydrates Inhibition tests
Sapphire Rocking cell Autoclave
Steel Rocking cell

16. Hydrates Inhibition test – Sapphire Rocking cell
Parameters recorded during Rocking Cell tests:
• System Temperature
• Individual cell pressure (KPI for KHI)
• Ball travel time (KPI for AA)
• Visual observations / photo & video imaging (KPI for AA)

17. Hydrates Inhibition test – Sapphire Rocking cell visual observation
• 1 low viscous slurry
• 2 high viscous slurry
• 3 blockage can be removed by shear (< 10 min)
• 4 blockage can be removed by extended shear
(> 10 min)
• 5 blockage cannot be removed by shear
 A No hydrates occur
 B Hydrates occur according to pressure drop, but
cannot be seen
 C Hydrates occur but are very small size and fine
dispersed
 D Hydrates occur and build small size
agglomerations (< 2mm) that do not stick to the
wall
 E Hydrates occur and build agglomerations (>
2mm) that do not stick to the wall, but partially
block the ball
 F Hydrates occur and build agglomerations that
do not stick to the wall but block the ball
 G Hydrates occur and build deposit on the wall
that block the ball
 H All water forms a massive hydrate deposition
The visual aspect of the hydrate slurry is ranked according to below classification:

18. ECO GAA007 B – Performance (1/3)
18
ECO GAA007 B: the first readily biodegradable Anti-Agglomerant

19. ECO GAA007 B – Performance (2/3)
19

20. ECO GAA007 B – Performance (3/3)
20
• Starting temperature: 24°C
• Target subcooling: 12°C
• Pressure: 136 bar (to be adjusted in order to match target subcooling)
• Water cut: 40-50-60-70%
• Gas phase: 78.4% Methane 10.2% Ethane, 7.0% Propane, 3.0% Carbon
Dioxide, 0.7% iso-Butane
• Water phase: Formation water / Condensed water 50:50, 25:75, 10:90
and 90:10
• Organic phase: oil field sample
Formation water composition
Ion
Concentration
(mg/L)
Na+ 21002
Ca2+ 2724
Mg2+ 223
Fe (total) 43
Sr2+ 444
Ba2+ 1500
K+ 700
Cl- 42708
SO4
2- 0
Total
alkalinity
15.9

21. ECO GAA007 B – Performance (3/3)
21
Water Cut F-Water DI-Water Dose Rate Rating Result
40% 90% 10% 2,5% B1 pass
40% 50% 50% 2,5% D1 pass
40% 25% 75% 2,5% D1 pass
40% 10% 90% 2,5% F5 fail
50% 50% 50% 3,5% C1 pass
60% 50% 50% 3,5% E1 pass
70% 90% 10% 3,5% B1 pass
70% 90% 10% 2,5% B1 pass
70% 50% 50% 3,5% H5 fail
70% 50% 50% 5,0% F5 fail
70% 25% 75% 3,5% H5 fail
70% 10% 90% 2,5% G5 fail
• Impact of salinity and water cut
• Better results at lower water cut
and/or high salinity
Note: steady state conditions

22. ECO GAA007 B – Ecotox. Profile
Endpoint Method/Protocol Result
Biodegradation OECD 306 >60% in 28 days
Bioaccumulation OECD 107 (modified) Log POW = 2.3
Algal toxicity
ISO10253:2016(E)
Skeletonema sp.
EC50 0.207 mg/L (WAF)
Crustacean toxicity
ISO14669:1999
Acartia sp.
LC50 6.56 mg/L (WAF)
Fish toxicity
OSPAR Limit test - Commission 2006
Cyprinodon variegatus
Limit (96h) > 0.207 mg/L
(WAF)
Sediment reworker
OSPARCOM guidelines (2006)
Part A Corophium volutator
10 days LC50 6800 mg/kg
CONFIDENTIAL
Contact author for details

23. Business Case | Pipeline Application | ECO GAA007B
Field conditions
Gas (e3m3/d) 5.5
Oil (m3/d) 11
Water (m3/d) 17
Water cut (%) 50-60
HET (hydrate formation temperature - °C) 13
Highest expected pressure (kPa) 2900
Normal operating temperature (°C) 4
Lowest expected temperature (°C) -10
Target subcooling (°C) 9 (23)
Gas Hydrate mitigation technology
Methanol AA
Estimated consumption
(software sym.)
Estimated AA consumption
(MT/y - assuming 2% dose rate)
4,000 MT/y 110 MT/y
Saving on chemicals: 0.75M$/y, without considering
logistic (Methanol), risk & service co. margin (AA)
Methanol: risks and additional costs related to
flammability and huge volumes shipped offshore
20ft Iso tank – 16,000L
x 350 for MeOH x 8 for AA

24. ✓ ECO KS6 makes traditional KHI cost of treatment more affordable by
→ Boosting current KHI performance to new levels
→ Replacing > 50% of polymer KHI in blend
→ No foaming, no emulsification observed
STEEL ROCKING CELL
KHI Synergist – ECO KS6

25. ✓ ECO K530 is the natural KHI coming from from fish waste
✓ Circular economy, ESG compliant
✓ Idea came from anti-freeze proteins (AFPs) in fish that prevent ice crystal growth in the bloodstream at subzero temperature
✓ Patented process developed to isolate and partially hydrolyze proteins in fish waste
Green KHI from Fish Waste - ECO K530

26. ✓ Can be ranked in the PLONOR list or, at worst, it will get Yellow and Gold ranking for North Sea Offshore
applications
✓ Performance tests:
a. Steel Rocker Rig (Constant Cooling mode 1ºC cooling rate, DI Water,75bar)
→ Sub-cooling of 8.4ºC with 0.5% ECO K530
b. Sapphire Rocker Rig
Isothermal (aqueous/33% + condensate/36bar)
→ 7ºC sub-cooling w/o hydrates in 14 days
c. No significant emulsioning, limited foaming tendency
KHI ppm To, °C Ta, °C
No additive 16.9 16.6
Std KHI 5000 4.5 4.0
ECO K530 5000 8.5 7.9
Green KHI from Fish Waste - ECO K530

27. Conclusion and remarks
27
✓ Hydrate formation among the most challenging technical and safety issues in O&G
✓ Learning how to prevent and handle hydrates is a step forward in Flow Assurance management
✓ Currently available technologies are characterized by high risk for operators and high environmental impact
✓ Eco-Inhibitors technologies minimize operational risks and environmental impact while keeping an effective
control of hydrates and reducing carbon footprint of the treatment

28. 28
Thank You !