Membrane Separations & System Technologies and Case Studies Larry A. Lien

Overview of MDSs Process Membrane Expertise Hollow Fiber Microfiltration (MF) .1 to 1 micron Bacteria Ultrafiltration (UF) 6K to 100K MWCO Proteins Thin Film UF 500, 1K, 2K & 3K MWCO Rejects Ferric Iron, Dyes & Small Colloids Nanofiltration (NF) 150 to 500 MWCO Divalent salts rejected 99% but transmits salts or acids RO / EMS® 50 to 150 MWCO Rejects all salts and acids 99+%

Typical spiral-wound element construction: 20 cm x 100 cm (30 m2) High temperature – 140°C High pH – 14 Low pH – 0 High viscosity – 300 Centipoise @ 90°C High solids (soluble and suspended) Ultra-high pressures – 200 Bar

Spiral Wound Technology

Cross Flow Filtration Important Parameters Feed Spacer Turbulence Promoter Feed Vector Permeate Vector Keeping this ratio Low will minimize Fouling Our system is designed to keep this ratio to minimize fouling and reduce the cleaning frequency

Permeate Rate Does Effect Fouling

Acid reclamation concentration with Acid RO or purification with Modified NF Membranes Boric Phosphoric Acetic Citric Sulfuric Nitric Hydrochloric Hydrofluoric

Caustic high-pH environments with special RO and NF membranes Operated RO in high-pH cyanide solutions for 8 years’ special construction to meet waste water processing needs Recovery of 5-20% caustic solution with NF membranes with special construction for Aluminum Refinery processes

Case Studies for Why the Mining and Metal Refinery Industry should use Membrane Technology Recovery of metals Recovery of acids or caustic Recovery of energy Reduction of disposal costs

CASE STUDY: Yanacocha Gold mining heap leach water balance issue at Yanacocha, Peru First RO Water Treatment system installed in 2003 Currently, 2,750 m3/hr of barren leach solution is treated and discharged safely into the environment Most original membrane-elements installed in 2003 are still operating effectively Payback <4 months with gold recovery

Yanacocha process overview Heap Leach Cyanide Solution Mining Gold Extraction Merrill-Crowe Gold Recovery Carbon Column 117.5 ppm CN WAD Returned to Extraction 1750 m 3 /hr after Chlorine Treatment Discharged into Environment 2200 m /hr RO

Yanacocha Water Quality Ion mg/L Feed mg/L Permeate mg/L Concentrate mg/L Discharge Limit mg/L pH 10.1 8.0 9.7 6.0–9.0 CN WAD 46.7 <.05 117.5 0.2 Arsenic 0.4 <.01 1.5 0.5–1.0 Mercury 0.0025 <.0005 0.0076 0.002 Nitrite 5.19 0.09 17.11 Nitrate 27.5 0.64 89.8 Copper 3.1 0.1 11.6 0.3 Zinc 17.2 65.1 1

RO of gold-cyanide complex concentration

1000 m3 Plant at MYSRL – Yanacocha Norte, Peru

Comments from Newmont’s Operators at Yanacocha Meets water quality discharge standards (including nitrites and nitrates not regulated) Allows for future safe operation and expansion Increased Gold and Silver recovery in membrane concentrates (Au and Ag rejected at 96.5% rate by the membranes – especially important during upset conditions) Cyanide recovery for re-use Chlorine consumption reduced by 75%, and overall operating cost is 70% less than that of a conventional precipitation plant EASY TO OPERATE

NF fractionation of gold and copper-cyanide complex

Copper-Gold fractionation process Special NF Gold Recovery Special RO Copper Heap Cu CN Cu CN Au CN Preg Soln To Discharge Au Recovery

CASE STUDY: Copper and sulfuric acid rejection with special RO membrane-elements at Phelps-Dodge

18 years of operation of EMS® systems at Freeport McMoRan (Phelps-Dodge) Rod Mill – El Paso, Texas 2 SO 4 8,000-9,000 ppm Cu 2 m 3 /hr Acid RO 2 1-2% H 1,230 ppm CU pH .8 18 m 1% Acid 500 ppm Cu 1.3 m Acid RO 1 55 Bar 45°C To Scrap Copper Dissolving Process Tank ZERO-DISCHARGE SYSTEM <.01% Acid 3 ppm Cu 14.7 m /h Rinse Water for Rod Mill .1% Acid 35 ppm Cu 16 m

CASE STUDY: Freeport McMoRan (Phelps-Dodge) Acid Reference System installed in 1992 400 m3/day x 2 (two-pass system), total of 800 m3/day as Product 70 Bar capability All Stainless 316 with Viton Elastomers – Victaulic and O-rings Two-pass system to achieve product quality desired

Copper and Iron rejection with special Modified RO membrane-elements

AMD Copper Recovery Process

CASE STUDY: AMD application at Cananea de Mexico Recovery of Copper directly from EMS® concentrate EMS® process paid for itself within 6 months via copper recovery Allowed mine to open new reserves from an old 1890s mine shaft that would otherwise have flooded

CASE STUDY: Asarco Refinery Wastewater Reclamation Project Legacy refinery with ground water pollution issues after 100 years of operation Precipitation system installed in 1985 – $1M capital and huge operating costs Membrane system installed in 1993 preceding precipitation – reduced volume to precipitation system from 6 m3/hr to 1 m3/hr

Copper Refinery Precipitation Process Prior to Addition of Membrane System

Refinery layout with membrane system followed by precipitation Modified RO Membrane Concentrate to Existing Precipitation Volume Reduced by 80% RO Permeate 80% Recovery To Surface Discharge Media II Media I Liquid Returned to Feed for RO Mixing & Clarifying Tanks Filter Press Sludge Hauled Re-refined

Capital and operating costs: Precipitation vs. Membrane-Media Cap Cost $1M $300K Chemicals $2.61 per m3 $ .15 * Sludge disposal per m3 $26.53 $1.35 Total sludge generated per m3 19.24 Kg 2.88 Kg Total Op cost per m3 treated $29.15 $1.82 * Membrane cleaning and media regeneration

Final Permeate Water Analyses Feed mg/l Permeate mg/l As 10.1 .081 Cd 14.5 .05 Zn 33.5 .01 Pb 3.07 Cu .073 Fe .986 .10 Mn 3.33 Total Metals 67.9 .583 99.14% Extraction

Sun Metals Zero Discharge Project New Zinc Refinery in Townsville, Australia $A 0.5 Billion Investment Zero Discharge Permitting Because Townsville is on Great Barrier Reef After Construction Commenced Sun Discovered Their Plant Effluent Could contain up to 30 ppm of Boron Conventional Precipitation Could Not Remove Boron 32 Proprietary and Confidential

Sun Metals Zero Discharge Zinc Refinery Low pH Process Water From Zinc Refinery – Peabody Water Lime Pond (Saturated CaSO4 ) 40 M3/hr To Evaporation Ponds Reverse Osmosis Nanofiltration 35 M3/hr Boiler Feed Make-up 33 M3/hr 33 Proprietary and Confidential

Cobre Los Crucas Seville, Spain Application 1 New Mine Copper Open Pit Mine Alkaline Mine Drainage from Rainy Season Contaminated with Arsenic, Fluoride and Boron Zero Liquid Discharge Facility Application 2 To Maintain Static Hydraulic Pressure on Open Pit Ground Water is Pumped from Wells around the Perimeter of the Pit These “Water Wells” once they reach the surface must be treated for high levels of Arsenic, Fluoride and Boron Clean Permeate Re-injected into Ground Water Membrane Plants Operate at 95-97% Recovery and the Concentrate is Evaporated

Application 1 CLC Alkaline Mine Drainage

Application 1 Cobre Los Crucas Copper Mine Alkaline Mine Drainage Pond Hollow-Fiber UF Backwashable 600 m3/hr 550 m3/hr Clean Permeate <100 ppm Sent to Mill as Process Water 50 m3/h To Evaporator Special Construction RO 36 Proprietary and Confidential

Application 2 CLC Well Water Treatment and Re-injection Perimeter Wells Drilled around Open Pit Pump Ground Water that must be Treated before Re-injection

Application 2 Cobre Los Crucas ZLD Process Flow Diagram EMS Plant Recovery 95-97.5% Backwash Recovered or Sent to Seeded Reactor Hollow Fiber UF 75 m3/h Special RO 90% Recovery 750 m3/h 675 m3/h Seeded Reactor Wells For Re-injection To Evaporator 25 m3/h Special RO 60 Bar 66% Recovery Hollow Fiber UF 50 m3/h For Re-injection Sludge to Filter Press

Case Study Waihi Gold Overview Process PDF for Newmont Waihi Gold EMS High Pressure < 400 psi Low Pressure < 200 psi Turbidity ORP pH 30 M3/H back to Tailings Pond AntiScalant Oxygen Scavenger Bisulfite or Thiosulfate Solution 210 M3/H Permeate to Discharge MMF With Backwash 9 Filters Feed 240 M3/H 10-25C 1 micron Bag Filters Duplex on Each Skid 2 Skids of Low Pressure HF Each capable of 120 M3/H Feed at 75% Recovery Concentrator HF High Pressure 30 M3/H Feed at 50% Recovery PI PI 240 M3/H 60 M3/H TDS 30 M3/H 180 M3/H TDS

Waihi Overview Process PDF for Newmont Waihi Gold EMS High Pressure < 400 psi Low Pressure < 200 psi Turbidity ORP pH 30 M3/H back to Tailings Pond AntiScalant Oxygen Scavenger Bisulfite or Thiosulfate Solution 210 M3/H Permeate to Discharge MMF With Backwash 9 Filters Feed 240 M3/H 10-25C 1 micron Bag Filters Duplex on Each Skid 2 Skids of Low Pressure HF Each capable of 120 M3/H Feed at 75% Recovery Concentrator HF High Pressure 30 M3/H Feed at 50% Recovery PI PI 240 M3/H 60 M3/H TDS 30 M3/H 180 M3/H TDS

Tapered Array for Primary System 1st Stage 2nd Stage 9 Vessels In Parallel 5 Vessels In Parallel 30 m3/h 120 m3/h Exit Volume From Each 6 m3/h 90 m3/h Ave 22.2 l/m2/h (l-m-h)

Tapered Array for Concentrator System 1st Stage 2nd Stage 2 Vessels In Parallel 1 Vessel 15 m3/h Per vessel 30 m3/h High Exit Velocity Less Fouling Exit Volume15 m3/h 15 m3/h Ave 22.2 l/m2/h (l-m-h)

Water Quality for Selected Ions of Interest Based on System Performance Feed Permeate Concentrate   Discharge Limit µg/l (ppb) pH 9.5 10.5 8.7 6.0-9.0 CN WAD 690 144 720 NA Arsenic 50 2 1.5 Chrome 5.5 1.6 16.8 Selenium 54.9 0.63 143.5  NA Antimony 85.5 .82 272.8 Copper 2.9 0.11 12.5 Zinc 3.4 0.3

Waihi Gold Membrane Plant 240 m3/h Permeate Storage Prior to Discharge

Important Operating Parameters Turbidity Feed TDS Permeate TDS Feed Pressure Delta P ORP Permeate Pressure or Flow High Level Alarm High Level Shut-down Low Inlet Pressure Stop & High Pressure Alarm High Pressure Stop & High Flow Stop (and Alarm)

Tapered Array for Primary System 1st Stage 2nd Stage 9 Vessels In Parallel 5 Vessels In Parallel 30 m3/h 120 m3/h Exit Volume From Each 6 m3/h 90 m3/h Ave 22.2 l/m2/h (l-m-h)

Tapered Array for Concentrator System 1st Stage 2nd Stage 2 Vessels In Parallel 1 Vessel 15 m3/h Per vessel 30 m3/h High Exit Velocity Less Fouling Exit Volume15 m3/h 15 m3/h Ave 22.2 l/m2/h (l-m-h)

Water Quality for Selected Ions of Interest Based on System Performance Feed Permeate Concentrate   Discharge Limit µg/l (ppb) pH 9.5 10.5 8.7 6.0-9.0 CN WAD 690 144 720 NA Arsenic 50 2 1.5 Chrome 5.5 1.6 16.8 Selenium 54.9 0.63 143.5  NA Antimony 85.5 .82 272.8 Copper 2.9 0.11 12.5 Zinc 3.4 0.3

Waihi Gold Membrane Plant 240 m3/h Permeate Storage Prior to Discharge

Oil & Gas Experiences

Case studies Shell Refinery – oily waste water treated and discharged Coal Bed Methane Produced Water, 2500 bbls/day discharged to the environment Husky Oil Produced Water re-used as flood water SAGD Produced Water re-used as steam make-up Produced Water from Gas direct discharge Frac-Flowback Barnett Shale re-used as Frac make-up High-TDS Bakken Produced Water for re-use

Shell Oil Refinery surface waste water system

Coal Bed Methane produced water process

Husky Oil produced water Hydrophilic UF – Process Overview

Current SAGD Process – low-quality steam generator make-up and high blow-down volumes & sludge

SAGD Membrane Process – 3-pass RO Permeate for boiler feed

Bench test results: 85°C Feed 2600 mg/L Permeate 24 mg/L Ca.............. 6.3 mg/L Mg............. 1.63 mg/L Silicon....... 66 mg/L Fe .............. 1.5 mg/L TDS............ 2500 mg/L TOC............ 293 mg/L Permeate 24 mg/L Ca………….. .45 mg/L Mg…………. [undetectable] Silicon……. 1.8 mg/L Fe ………….. [undetectable] TDS………… 24 mg/L TOC……….. 12.5 mg/L

Membrane SAGD Process Eliminate Hot Lime, new Steam Generation option, high recovery <5-10% blow-down

Gas Well produced water Produced Water from a Devon Energy natural gas production facility in New Mexico Water temperature: 130-140°F Capacity: 7500 GPD Operational for 12 months

Produced Water – 3-pass membrane process (UF, NF, RO)

Lab test results: Ultra-filtration process Feed Ca………………. 632 mg/L Mg……………… 68 mg/L Sodium………. 3137 mg/L Sulfate……….. 2907 mg/L Chlorides……. 3915 mg/L pH………………. 5.95 TDS…………….. 10,833 mg/L Cond*………... 16,400 µm hos TOC……………. 29 mg/L Oil & Grease. 80 ppm Permeate Ca………………. 576 mg/L Mg……………… 148 mg/L Sodium………. 3201 mg/L Sulfate……….. 2944 mg/L Chlorides……. 4118 mg/L pH………………. 6.33 TDS…………….. 11,158 mg/L Cond*………... 16,700 µm hos TOC……………. 11.9 mg/L Oil & Grease. [undetected]

Lab test results: Nano-filtration process Feed Ca………………. 632 mg/L Mg……………… 148 mg/L Sodium………. 3137 mg/L Sulfate……….. 2944 mg/L Chlorides……. 4118 mg/L pH………………. 6.33 TDS…………….. 11,158 mg/L Cond*………... 16,700 µm hos TOC……………. 11.9 mg/L Oil & Grease. [undetected] Permeate Ca………………. 98 mg/L Mg……………… 16 mg/L Sodium………. 3201 mg/L Sulfate……….. 50 mg/L Chlorides……. 3976 mg/L pH………………. 6.43 TDS…………….. 6,835 mg/L Cond*………... 12,050 µm hos TOC……………. 7.71 mg/L Oil & Grease. N/A

Lab test results: Reverse Osmosis process Feed Ca………………. 98 mg/L Mg……………… 16 mg/L Sodium………. 3201 mg/L Sulfate……….. 50 mg/L Chlorides……. 3976 mg/L pH………………. 6.43 TDS…………….. 6,835 mg/L Cond*………... 12,050 µm hos TOC……………. 7.71 mg/L Permeate Ca………………. 10 mg/L Mg……………… 0 mg/L Sodium………. 339 mg/L Sulfate……….. 3 mg/L Chlorides……. 483 mg/L pH………………. 6.39 TDS…………….. 933 mg/L Cond*………... 1,690 µm hos TOC……………. 2.85 mg/L

Projected Energy Costs – 24,000 bbl/day (3,790 m3/d) Cost for a 3-pass system $ 1.85M USD Total Energy – 720 hp $ 0.0422/bbl Based on an electric cost of $0.08/kwh USD (equal to $0.317 m3/d) Operating Costs $ 0.08/bbl Membranes, chemicals, etc. – estimated

Frac-Flowback Scope MDS will provide an Membrane Separation plant to process 4,000 bbl/day of frac-flowback water MDS will build, own, operate and maintain plant for 3-year period Objectives Continuous treatment of 4,000 bbl/day of frac-flowback water Production of 3,400 bbl/day of final permeate water Low chloride, TDS & TOC levels Production of 600 bbl/day of final concentrate water Low hardness & TOC levels, high chloride & TDS levels Concentrate to deep well injection, evaporation pond Overall water recovery: 85% (3,400 bbl/day from 4,000 bbl/day)

MDS Process Plant Water Balance

Pretreatment – an Important Component Pretreatment of feed water is important in order to minimize membrane fouling and ensure consistent plant performance 3-stage pretreatment process Induced Gas Flotation (IGF): removes bulk oils, polymers and suspended solids Reduces insoluble oil and suspended solids from ~200 ppm to ~20 ppm Walnut Shell Filtration (WSF): polishing removal of oils, polymers and suspended solids Reduces insoluble oil and suspended solids from ~20 ppm to ~2 ppm Ultra-filtration (UF): 0.01 µm pore size for final polishing of oils, polymers and suspended solids No additional solids generated

Frac-Flowback Plant Process Flow Diagram

What makes MDS Systems Design Unique? Special membranes and element construction Special system design Special operating procedures based on intimate knowledge of the installation’s water Special cleaning procedures 28 years of process membrane systems experience Not just another bench test result – commercial applications running daily at significant volumes