Clathrate Desalination Method Applied to Produced Waters: Methodology & Results
Patrick Baldoni-Andrey, Hervé Nabet, Matthieu Jacob, Pierre Pédenaud, Philippe Glénat Pascal Le Melinaire, Bruno Mottet
producedwaterevents.com Presentation outline
- Context and Stakes
- Material and Methods
- Results
-Conclusion and Perspectives
2 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com The context –The E&P concerns Context and Stakes Water associated CAPEX & OPEX: regulatory constraints require efficient water treatments
and the stakes are huge! Water production in the oil industry is 3 times the amount of produced oil!
80
3 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Key Numbers for Total Context and Stakes
Injection water
Reinjection ≈ 55% mainly seawater
If you cannot manage water, you cannot produce oil ! 4 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Rationale for Produced water desalination Context and Stakes
- Chemical Enhanced Oil Recovery
- Fresh water Enhanced Oil Recovery
- Recycling of produced water in the petroleum process (ex : Steam Assisted Gravity Drainage)
- Minimize impact of water disposal in the environment onshore
- Potential reuse, access to new resources
- Low cost and innovative desalination (no evaporation, no pressure, …)
- Value creation with low level calories
5 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com The Missing Link… Context and Stakes
LOW TDS HIGH TDS (Total Dissolved Solids) Crystalliser t Combined evaporation & n
e salt precipitation m t
a Evaporation e r r T e t
a f o W
t a e s S o C Reverse Osmosis (RO )
20,000 40,000 260,000 TDS (mg/l) producedwaterevents.com 6 Produced Water desalination – Sugar Land – 18jan2017 Energy – Rules of Thermodynamics Context Thermic Process and Stakes ΔH Gas Phase vaporization H20 : 2257 Purification kJ/kg Vapor
Membrane
Liquid Phase x 10
Effluent Concentration Cold Process
Δ H Solid Phase crystallization of hydrate 284 kJ/kg Crystals 10 times less energy required
7 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com GAS HYDRATE-CLATHRATE Context and Stakes ( P,T Zone ) Clathrate - Crystals
Natural Synthetic
Cage – Structures depend on host molecule
n H 0 H20-pure 2 ( apex of cage ) Hydration number = n host M
CH4 ( Host Molecule )
Crystal => No place for impurities inside the crystal producedwaterevents.com Cyclopentane Hydrate Material Methods • Liquid – No more Gas • C5H10 No pressure Host molecule • High T (+7°C vs Ice) • High hydration number : 17 H20 • Hydrate floats: d = 0.98 • Low cyclopentane Solubility : < 100 ppm • Low density: C5H10 d = 0.95 C H hydrate 5 10 • Abundant / Unexpensive crystals Dissociation Curve(P,T) • Widely used in many industries.
producedwaterevents.com 9 Produced Water desalination – Sugar Land – 18jan2017 Patented Technology Context and Stakes Benefits: Use of activated carbons soaked -Greater surface of contact: with Cyclopentane C5H10 and water
Without activated carbons With activated carbons -Rapid kinetics n o n i e 10 o 10 t i r a t u a e t -Lower energy footprint l e a l c r Exothermic peak c 5 e 5 u u p
lasts 80 minutes N N m
e -Helps Collecting Cyclopentane 0 T 0 0 50 100 150 200 250 300 0 50 100 150 200 250 300 -Trace of Cyclopentane: Time in minutes Instantaneous Nucleation : < 1 mn below detection limit
Exothermic: Hydrate Crystallisation
Endothermic: Active Carbon Desorption producedwaterevents.com BGH Process Material Recycled C5H10 + Activated Carbon Methods
Recycled – C5H10 - carbons 1) Crystallization 3) Mixing 1) Cristallisation: 3) Melting: The more crystals you make,
T° T° the more pure water you collect 2) 2)Separation Separation C5H10-Carbons Cold Hot C °
e r u t a
input r Input e p m
Waste water, e Wastewater,industrial effluent, salt T effluent,water,… Wastewater,saline water effluent, OutputOutput1: Purified2 Water OutputOutput 2: 1 Puirified saline water Output concentrate ( left over, Ice Forming Curve concentratesalts,..ect) (Mother water Hydrate Forming Curve liquor , salts,..)
producedwaterevents.com 11 Produced Water desalination – Sugar Land – 18jan2017 Operating at Eutectic Point Material Methods • Brine concentration up to saturation C °
e r u t
• Co-crystallization of hydrate and salt a r e p
m Salt + e • Concentrate Output in solid form T solution ( precipitated crystal of salts ) Salt + solution
• ZLD Technology (Zero Liquid Discharge) Salt concentration
Hydrate Crystals
Saturated brine
NaCl crystals producedwaterevents.com 12 Produced Water desalination – Sugar Land – 18jan2017 Real produced water samples Material Methods
• Crucial to have real samples for organic and mineral content
ANGOLA T ANGOLA G NETHERLANDS NETHERLANDS NIGERIA LYBIA
• TDS : 0.1 - 193 g/L (Total Dissolved Solids) • [oiw] : 0 - 136 mg/L (oil in water) • DOC : 55 – 425 mg/L (Dissolved Organic Carbon)
13 producedwaterevents.com Produced Water desalination – Sugar Land – 18jan2017 Batch Mode Material Methods 1) Crystallization 2) Separation 3) Dissociation Cyclopentane + Activated Carbon Cyclcopentane 100 µm Water Saline water Apparatusfilter Concentrate Filtrate
14 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Produced Water 1 : Netherlands Results
cake 20°C Conductivity mS/cm TDS Feed 66.2 40g/L Feed -1°C Desalinated Water 40.0 - 40%
Filtrate
15 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Produced Water 2 : Lybia Results
cake 20°C Conductivity mS/cm TDS Feed 84.0 63g/L Feed -3°C Desalinated Water 51.7 - 47%
Filtrate
16 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Produced Water 3 : Angola G Results
cake Conductivity mS/cm TDS Feed 98.9 74g/L Feed -5°C 20°C Desalinated Water 41.4 - 58%
Filtrate
17 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Produced Water 4 : Angola T Results
cake Conductivity mS/cm TDS Feed 181.8 186g/L Feed -9°C 20°C Desalinated Water 130.4 - 28%
Filtrate
18 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Effect on the other ions : Produced Water 3 Angola G Results
Removal Efficiency Conductivity mS/cm TDS Feed 98.9 74g/L Desalinated Water 41.4 - 58%
• Main ions are removed with the same efficiency as conductivity • Ca, Na and Cl are in g/L and other ions in mg/L
19 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Conclusion
• Whatever the composition of produced water, formation of hydrate crystals happens in few minutes
• Desalination performances range from 30% to 60% in batch mode
• Removal of other ions, metals are similar. Globally not ion-dependant.
• Filtration process seems to be the key step to improve removal efficiency
20 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Way Forward
Increase the readiness of the process
• From batch to continuous process
• Optimisation of filtration stage – understand how the thermodynamics impact the crystal shape – link the crystal shape to the dehydration efficiency – Better understand the role of activated carbon in the system
21 Produced Water desalination – Sugar Land – 18jan2017 producedwaterevents.com Thank you for your attention
Questions
22 producedwaterevents.com