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 6 Produced desalination Water – Sugar Land – 18jan2017 Cost of Treatment Reverse Osmosis (RO Osmosis ) Reverse LOW TDS LOW 20,000 Sea Water The Missing Link… Missing The 40,000 Evaporation Evaporation HIGH TDS TDS HIGH (Total Dissolved (Total Solids) producedwaterevents.com 260,000 Combined evaporation & evaporationCombined Crystalliser saltprecipitation TDS (mg/l) TDS and Stakes Context 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 with Cyclopentane with soaked carbons of activated Use Temperature10 0 5 Without activated carbons 0 50 100 Time in minutesin Time Nucleation Endothermic: Active Endothermic: Exothermic 150 lasts Exothermic peak 200 80 minutes 80 250 : Hydrate Crystallisation Hydrate : 300 10 Instantaneous 0 5 Carbon DesorptionCarbon 0 With activated carbons activated With Patented Technology Technology Patented 50 100 Nucleation Nucleation : < 1< mn : Nucleation 150 200 250 300 below detection limit below detection of Cyclopentane: -Trace Collecting -Helps Cyclopentane - - andC5H10 water of contact: surface -Greater Benefits: Lower energy footprint energy Lower kinetics Rapid producedwaterevents.com and Stakes Context 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.