Saint-Gobain Ceramic Materials Saint Gobain SiC Membranes for Produced Water December 10th, 2014 Nathalie Elkhiati Fabiano Rodrigues Karen Dwyer Aberdeen
Saint-Gobain Group Silicon Carbide Characteristics Saint-Gobain Liquid Filtration membranes Applications Tests
Compagnie de Saint-Gobain Saint-Gobain, one of the world s top 100 leading industrial corporations OPERATIONS IN 64 COUNTRIES SALES 42.025 bn Nearly 190,000 EMPLOYEES 2013 Sales Recurring net income Capital expenditure Free cash flow bn 42.0 1.0 1.4 1.2 3
Business Sectors in Saint-Gobain Group Compagnie de Saint-Gobain Innovative Materials Construction Products Building Distribution Packaging Verallia 4
Ceramic Materials All businesses producing grains and powders, ceramic components and refractories, specialty crystals and associated systems Ceramic refractory products for industrial furnaces 65 manufacturing facilities In 18 countries Approximately 6,400 employees Engineered ceramic grains, powders, beads and slurries for industrial applications Silicon Carbide, Alumina, Zirconia, Diamond, Boron Nitride Ceramic medias for the oil and gas extraction (proppants) and the chemical industry (catalyst carriers) Crystals for detection and defense applications Quartz for aeronautical and industrial applications 5
Experience in Silicon Carbide Materials Vertical Integration of SiC - a key Differentiator: Manufacturing SiC, Processing of Raw Materials, Structure property Control of SiC Porous SiC ceramics Crystar : Recrystallized SiC (RSiC) Advancer Annasicon RTH: Nitride bonded SiC (NSiC) Oxide bonded SiC Dense SiC ceramics Silit : Reaction bonded, infiltrated (SiSiC) Hexoloy : directly sintered (SSiC) Saint-Gobain Confidential Information
Liquid Filtration 7
Sintered Silicon Carbide materials Sintered Pure silicon carbide Porosity : < 5% Grain size 2 to 20 µm Recrystallized Pure silicon carbide Porosity : 30 to 50% Reaction Bonded I Silicon / carbon residues Porosity : 5 to 10% Reaction Bonded II Silicon carbide and Silicon Porosity : < 1% Si: 5 to 12% Oxide- Bonded Porosity 10 to 20% Nitride- Bonded Porosity : 8 to 15% (<1% by 2nd firing in air) 8
R-SiC as a filtration membrane material Recristallized Silicon Carbide (RSiC) basics Material consolidated at high T (> 2200 C) through sublimation of fine SiC particles that condensate at large SiC grains boundaries Pure (>99%), strong SiC grain boundaries significantly different from oxide, nitride or other SiC materials high porosity structure (OP > 40%) very good flux 9
RSIC benefits as membrane material Saint-Gobain RSiC filters bring specific advantages for water treatment Low weight: intrinsic density of 3.2 g/cm3 and high open porosity (40%) High erosion resistance Weak organic matter adsorption for low reversible and irreversible fouling High corrosion resistance for harsh chemical cleaning Chemical stability (ph 0 to ph 14) NB : Reversible fouling: retained species removable by water back flushing Irreversible fouling: not removable by water back flushing (CIP only) 10
Silicon carbide membranes for surface water filtration (from literature) Comparison between ceramic and polymeric membrane permeability and fouling using surface water Low reversible and irreversible fouling due to weak organic matter adsorption 11
Advantages of SiC as a membrane material (from literature) UF and MF SiC membranes exhibit higher water permeability and less fouling tendency compared to ceramic oxide and polymer membranes This behavior results from Micro-structural and surface chemistry properties of SiC membranes Surface behavior and specific porosity Structure of SiC membranes allow straightforward and effective cleaning processes such as backwash, backflush and CIP. 12
R-SiC membranes SG standard products Shape to be disclosed only under NDA. Cylindrical Rectangular CFT CFT CFT D = 144 mm W = 148 mm 41-52-3.6 25-31-3 25-16-5 Geometry Configuration Dead-end Dead-end Cross-flow Cross-flow Cross-flow Channels Dh [mm] 2 2 3.6 3 5 Carrier d50 [µm] 5 5 25 25 25 Carrier OP [%] 45 45 45 45 45 Membrane d50 [nm] 250 250 250 or 1000 250 to 1000 250 or 1000 Maximal length [mm] 1000 1000 1200 1200 1200 Filtration area / length 8.1 m²/m 11 m²/m 0.59 m²/m 0.30 m²/m 0.25 m²/m Customization of shape and membrane pore size possible under customers request (if large volume) Range of average membrane pore size (d50): 250 to 3000 nm Channels hydraulic diameter 3 mm and 5 mm for dead-end products, 3-7 mm for cross-flow products Saint-Gobain Proprietary Information - Confidential 13
Cross-flow: Typical Pore Size Distribution (Hg-intrusion) Membrane: 250 nm Carrier: 25 µm 14
Introduction HPR products Dead-end and cross flow R-SiC membranes Dead-end configuration Membrane Open porosity = 40% Average pore size = 200-3000 nm Carrier Open porosity = 40% Average pore size = 5-30 µm Cross-flow configuration P 1 feed feed concentrate P 1 P 2 filtrate P 2 Higher compactness Lower energy consumption (only 1 pump) More sensitive to cleaning operations filtrate P 3 Self-cleaning action from axial flow More mature technology Higher energy consumption (recirculation pump) 15
R-SiC for dead-end filtration 148x148x1000 mm³ 25x1178mm³ 16
Filtration tests with synthetic PW Filtration tests with synthetic produced water Water composition Mineral oil: 300 ppm + emulsifiers Clay (RR40, d50 < 1 µm): 100 ppm Salt (NaCl): 4000 ppm Mix prepared with DI water in Ultra Turrax stirrer Tri-modal PSD: 0.8 µm, 3 µm, 20 µm Operating parameters Water temperature: 40 C Cross-flow speed: 1.5 m/s Backwash: several conditions tested Membrane Average pore size (nominal): 250 nm or 1µm Membrane geometry: 25-16-5 (DH5) or 25-31-3 (DH3) length = 1178 mm Total filtration area: 0.9 m2 for Dh5, 1.05 for Dh3 Test duration: 20-70 hours 17
Filtration tests with synthetic PW Feed Filtrate 250 nm 18
Filtration tests with synthetic PW Comparison SG R-SiC 250nm vs. TiO2/ZrO2 200nm Same cross-flow speed and TMP for both test conditions SG SG R-SiC membrane shows 25% higher permeability than ZrO 2 /TiO 2 membrane 19
Sain-Gobain Expertise : Post-mortem analysis of used membranes Observation and characterization of fouling layer 1.8 cps/ev 1.6 1.4 1.2 Cl Te S Fe 1.0 O Al Cl Te C Na Si S Ca Ca 0.8 Fe 0.6 0.4 0.2 0.0 2 4 6 8 10 12 14 kev 20
Water Treatment Testing for Fracking Projects vary based on fixed site versus mobile treatment units Dependent on geography, concentration of wells, water condition, costs, Cost of water treatment versus cost of clean water, transportation and disposal varies Market evolving quickly for water treatment still searching for improved, cost effective methods Short duration (8 hour runs) field testing with SiC membranes performed to date Extended testing planned to confirm ongoing performance
Field Test Locations Bakken Marcellus Uinta Barnett
Thank you! 23