Transcript Slide 1
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 Fouling Tendency Fouling Tendencies vs Permeate Flux 8 6 m 3/h 6 4 15m 3/h 2 0 10 15 20 25 30 35 Flux in Liters-M2-Hour 40 Normal Cross Flow Fouling Rate High Cross Flow Fouling Rate Acid reclamation concentration with Acid RO or purification with Modified NF Membranes • Sulfuric • Boric • • • Nitric Hydrochloric Hydrofluoric • • • Phosphoric Acetic Citric 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 3 2200 m /hr 117.5 ppm CN WAD Returned to Extraction Gold Recovery Carbon Column RO 3 1750 m /hr after Chlorine Treatment Discharged into Environment 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 0.3 65.1 1 RO of gold-cyanide complex concentration 99% WAD Cyanide Removal at pH >10.5 Au CN CN WAD Gold Cyanide Complex Rejected 96.5+% RO Membrane Water with trace amount of Cyanide 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 AuCN CuCN Copper Complex Rejected 98.5+% NF Membrane Gold Cyanide Transmission 100% Copper-Gold fractionation process Heap Au CN Cu CN Preg Soln CN Cu CN Copper Recovery Special NF Au CN Gold Recovery CN Cu Special RO To Discharge Au Recovery CASE STUDY: Copper and sulfuric acid rejection with special RO membrane-elements at PhelpsDodge Feed 1.23 g/l CuSO4 Sulfuric Acid 10 g/l Rejected 100 g/l RO Membrane Transmission Water and Trace Amount of Acid 18 years of operation of EMS® systems at Freeport McMoRan (Phelps-Dodge) Rod Mill – El Paso, Texas 1-2% H 2SO 4 1,230 ppm CU pH .8 3 18 m /hr 1% Acid 500 ppm Cu 3 1.3 m /hr <.01% Acid 3 ppm Cu 3 14.7 m /h Rinse Water for Rod Mill Acid RO 1 10-12% H 2SO 4 8,000-9,000 ppm Cu 3 2 m /hr 55 Bar 45°C .1% Acid 35 ppm Cu 3 16 m /h Acid RO 2 ZERO-DISCHARGE SYSTEM To Scrap Copper Dissolving Process Tank 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 Water and Sulfuric Acid Transmission CuSO4 and FeSO4 Both Rejected RO Membrane Transmission AMD Copper Recovery Process 1,000 gpm From AMD Pit 4,000 gpm 700 ppm Copper 20,000 ppm Iron pH 0.9 1,000 gpm Concentrate 2,000 gpm 1,400 ppm Copper 40,000 ppm Iron pH 0.9 1,000 gpm 1,000 gpm Permeate 2,000 gpm <10 ppm Copper <50 ppm Iron 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 Surge Tank pH 4.0 4,000 - 10,000 ppm Sodium Carbonate Ferric Sulfate Precipitate Sludge Hauled from System Filter Press Lime pH 9.8 Sodium Sulfide Clarification Precipitate pH Adjust 7.0 Difficult to Discharge and Meet Specs Refinery layout with membrane system followed by precipitation Concentrate to Existing Precipitation Modified RO Membrane RO Permeate 80% Recovery Volume Reduced by 80% Mixing & Clarifying Tanks To Surface Discharge Media II Media I Liquid Returned to Feed for RO Filter Press Sludge Hauled Re-refined Capital and operating costs: Precipitation vs. Membrane-Media Cap Cost Chemicals Sludge disposal per m3 Total sludge generated per m3 Total Op cost per m3 treated Precipitation Membrane-Media $1M $300K $2.61 per m3 $ .15 * $26.53 $1.35 19.24 Kg 2.88 Kg $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 .05 Cu .073 .01 Fe .986 .10 Mn 3.33 .05 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 Boiler Feed Make-up 33 M3/hr 33 Proprietary and Confidential 35 M3/hr Nanofiltration 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 Alkaline Mine Drainage Pond Hollow-Fiber UF Backwashable 600 m3/hr 50 m3/h To Evaporator Special Construction RO 550 m3/hr Clean Permeate <100 ppm Sent to Mill as Process Water 36 Proprietary and Confidential Application 2 CLC Well Water Treatment and Reinjection • 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 9597.5% Backwash Recovered or Sent to Seeded Reactor Hollow Fiber UF 75 m3/h 750 m3/h Wells To Evaporator 25 m3/h 50 m3/h For Re-injection Special RO 90% Recovery Special RO 60 Bar 66% Recovery 675 m3/h For Re-injection Hollow Fiber UF Seeded Reactor Sludge to Filter Press Case Study Waihi Gold Overview Process PDF for Newmont Waihi Gold EMS Turbidity MMF With Backwash 9 Filters Feed 240 M3/H 10-25C ORP 1 micron Bag Filters Duplex on Each Skid AntiScalant Oxygen Scavenger Bisulfite or Thiosulfate Solution PI PI pH TDS High Pressure < 400 psi Low Pressure < 200 psi 240 M3/H Turbidity 2 Skids of Low Pressure HF Each capable of 120 M3/H Feed at 75% Recovery 2 Skids Concentrator HF High Pressure 30 M3/H back to Each capable of 30 M3/H 60 M3/HFeed at 50% Recovery 30 M3/H 180 M3/H TDS 210 M3/H Permeate to Discharge Tailings Pond Waihi Overview Process PDF for Newmont Waihi Gold EMS Turbidity MMF With Backwash 9 Filters Feed 240 M3/H 10-25C ORP 1 micron Bag Filters Duplex on Each Skid AntiScalant Oxygen Scavenger Bisulfite or Thiosulfate Solution PI PI pH TDS High Pressure < 400 psi Low Pressure < 200 psi 240 M3/H Turbidity 2 Skids of Low Pressure HF Each capable of 120 M3/H Feed at 75% Recovery 2 Skids Concentrator HF High Pressure 30 M3/H back to Each capable of 30 M3/H 60 M3/HFeed at 50% Recovery 30 M3/H 180 M3/H TDS 210 M3/H Permeate to Discharge Tailings Pond Tapered Array for Primary System 1st Stage 2nd Stage 9 Vessels In Parallel 120 m3/h 5 Vessels In Parallel 30 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 30 m3/h 15 m3/h Per vessel 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 Ion Feed Permeate Concentrate Discharge Limit µg/l (ppb) µg/l (ppb) µg/l (ppb) 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 NA Chrome 5.5 1.6 16.8 NA Selenium 54.9 0.63 143.5 NA Antimony 85.5 .82 272.8 NA Copper 2.9 0.11 12.5 NA Zinc 3.4 0.3 12.5 NA Waihi Gold Membrane Plant 240 m3/h Membrane Plant 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 Alarm High Level Shut-down Low Inlet Pressure Stop & High Pressure Alarm • High Level Alarm • High Level Shut-down • High Pressure Stop & High Flow Stop (and Alarm) Tapered Array for Primary System 1st Stage 2nd Stage 9 Vessels In Parallel 120 m3/h 5 Vessels In Parallel 30 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 30 m3/h 15 m3/h Per vessel 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 Ion Feed Permeate Concentrate Discharge Limit µg/l (ppb) µg/l (ppb) µg/l (ppb) 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 NA Chrome 5.5 1.6 16.8 NA Selenium 54.9 0.63 143.5 NA Antimony 85.5 .82 272.8 NA Copper 2.9 0.11 12.5 NA Zinc 3.4 0.3 12.5 NA Waihi Gold Membrane Plant 240 m3/h Membrane Plant 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 50-100 ppm Oil & 40 ppm S.S. Equilization Tank collects all run-off water from Refinery perimeter Heat Exchanger raises temperature to 45°C 5% volume back to Collection Tank 95% discharged into Manila Bay 0 ppm Oil & S.S. ULTRA-FILTRATION M-Series <50-100 ppm Oil & <25 ppm S.S. Conventional Filtration 50-micron Coal Bed Methane produced water process Iron & Barium control Equilization Tank collects produced water from new methane gas wells Screen Filtration 50-micron 10% Concentrate to evaporation pond 90% surface discharge quality RO Permeate Low-fouling RO Cartridge Filtration 20-micron followed by 5-micron Husky Oil produced water Hydrophilic UF – Process Overview Concentrate returned to Knock-out Tank Knock-out Tank Ultrafilic UF Oil & Suspended Solids-free Permeate to re-use as formation flood water 90+% recovery Methane Dissolved Air Flotation 25-50 micron Bag Filter Current SAGD Process – lowquality steam generator makeup and high blow-down volumes & sludge WAC Weak Acid Cation IX Hot Lime Sludge Disposal 15 to 30% Blow-down saturated in Silica-to deep well reinjection 10% returned to Hot Lime Steam Generator Filtration 5-micron followed by 1-micron SAGD Membrane Process – 3-pass RO Permeate for boiler feed 20 psi 95% Recovery Nano-filtration 85°C 300 psi 100% Recovery Ultra-filtration 85°C Reverse Osmosis 85°C 100 psi 95% Recovery Permeate for Steam Generator or conventional package boiler (less expensive) Bench test results: 85°C • Feed 2600 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 3-pass (UF-NF-RO) Membrane System Feed 5-10% deep well or hot lime disposal 25% back to RO RO Permeate 90-95% of Initial Feed Low Silica, Hardness & TDS Existing NEW OPTION because of high-quality RO Permeate 97-99% Steam Conventional high-pressure steam boiler 75% as steam Steam Generator 1-3% 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) Return to Produced Water storage tank From Devon Produced Water Storage Acid 60 psi Concentrate to disposal Ultra-filtration 130°F 1st Pass Nano-filtration 2nd Pass 350 psi Reverse Osmosis 3rd Pass 60 - 48 psi = 12 psi net driving pressure 175 psi Concentrate to disposal Permeate to surface discharge Lab test results: Ultrafiltration 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 • Total Energy – 720 hp $ 1.85M USD $ 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 RO Permeate 3400 bbl/d Suitable for re-use Frac-Flowback 4000 bbl/d Concentrate 600 bbl/d Utilizes ultra-high-pressure RO machines capable of 1500 psi 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 N2 Exhaust • N2 Supply Pretreatment – an Important Component 1 gpm, IGF Skim Water WSF Backwash 1 gpm Nominal 13 gpm UF Conc Bleed Chem Tote Chem Tote Anti Scalant Tote UF WSF IGF 115 gpm UF Perm UF Feed Tank, 500 bbl Frac Tank 130 gpm, 20 psi, 129 gpm, 45 psi 128 gpm, 15 psi UF Wash Skid N2 Exhaust Blending Tank, 500 bbl Frac Tank N2 Supply Frac-Flowback Plant Process Flow Diagram 1 gpm, IGF Skim Water 3 gpm Blowdown 12 gpm NF Conc WSF Backwash 1 gpm Nominal 600 bbl/day Waste Tank, 500 bbl Frac Tank 13 gpm UF Conc Bleed Chem Tote 4,000 bbl/day 117 gpm Frac Flow-Back Water, 30,000 TDS Blending Tank, 500 bbl Frac Tank Chem Tote Anti Scalant Tote Anti Scalant Tote UF UF Feed Tank, 500 bbl Frac Tank Receiving Tank 500 bbl Frac Tank Blending Tank, 500 bbl Frac Tank 130 gpm, 20 psi, 1,000 bbl/day 103 gpm NF Perm 129 gpm, 45 psi 128 gpm, 15 psi Evaporator (existing) HF 3,400 bbl/day 2,400 bbl/day 72 gpm HF Perm HF Feed Tank, 500 bbl Frac Tank NF Feed Tank, 500 bbl Frac Tank NF Wash Skid 100 gpm Permeate for Devon Take-Off HF Perm Tank, 500 bbl Frac Tank 103 gpm 50 psi 115 gpm 50 psi UF Wash Skid Blending Tank, 500 bbl Frac Tank 31 gpm HF Conc NF 115 gpm UF Perm 500 gpm, (Periodic) 130 gpm (Average) 1,000 bbl/day 29 gpm Condensate WSF IGF 17 gpm Waste for Devon Take-Off HF Wash Skid 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