Membrane Separations

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Membrane Separations System Technologiesand
Case Studies

• Larry A. Lien

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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
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Typical spiral-wound element construction
20 cm x 100 cm (30 m2)

• High temperature 140C
• High pH 14
• Low pH 0
• High viscosity 300 Centipoise _at_ 90C
• High solids (soluble and suspended)
• Ultra-high pressures 200 Bar

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Spiral Wound Technology
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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
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Permeate Rate Does Effect Fouling
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Acid reclamation concentration with Acid RO
orpurification with Modified NF Membranes

• Boric
• Phosphoric
• Acetic
• Citric

• Sulfuric
• Nitric
• Hydrochloric
• Hydrofluoric

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Caustic high-pH environments with specialRO 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

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Case Studies for Why the Mining and Metal
Refinery Industryshould use Membrane Technology

• Recovery of metals
• Recovery of acids or caustic
• Recovery of energy
• Reduction of disposal costs

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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 lt4 months with gold recovery

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Yanacocha process overview
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Yanacocha Water Quality
Ionmg/L Feedmg/L Permeatemg/L Concentratemg/L Discharge Limitmg/L
pH 10.1 8.0 9.7 6.09.0
CN WAD 46.7 lt.05 117.5 0.2
Arsenic 0.4 lt.01 1.5 0.51.0
Mercury 0.0025 lt.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
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RO of gold-cyanide complex concentration
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1000 m3 Plant at MYSRL
Yanacocha Norte, Peru
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Comments from Newmonts 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

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NF fractionation of gold and copper-cyanide
complex
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Copper-Gold fractionation process
Au Recovery
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CASE STUDY Copper and sulfuric acid rejection
with special RO membrane-elements at Phelps-Dodge
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18 years of operation of EMS systems at Freeport
McMoRan (Phelps-Dodge) Rod Mill El Paso, Texas
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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

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Copper and Iron rejection with specialModified
RO membrane-elements
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AMD Copper Recovery Process
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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

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CASE STUDY Asarco Refinery WastewaterReclamatio
n Project

• Legacy refinery with ground water pollution
  issues after 100 yearsof 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

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Copper Refinery Precipitation Process Prior
toAddition of Membrane System
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Refinery layout with membrane systemfollowed by
precipitation
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Capital and operating costs Precipitation
vs. Membrane-Media
Precipitation 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
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Final Permeate Water Analyses
Feedmg/l Permeatemg/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
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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

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Proprietary and Confidential
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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
35 M3/hr
Boiler Feed Make-up
33 M3/hr
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Proprietary and Confidential
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Cobre Los CrucasSeville, 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

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Application 1CLCAlkaline Mine Drainage

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Application 1Cobre Los Crucas Copper
MineAlkaline Mine Drainage
Special Construction RO
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Proprietary and Confidential
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Application 2 CLCWell Water Treatment and
Re-injection

• Perimeter Wells Drilled around Open Pit Pump
  Ground Water that must be Treated before
  Re-injection

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Application 2 Cobre Los CrucasZLD Process
Flow Diagram EMS Plant Recovery 95-97.5
Backwash Recovered or Sent to Seeded Reactor
75 m3/h
Hollow Fiber UF
Special RO 90 Recovery
750 m3/h
675 m3/h
Seeded Reactor
Wells
For Re-injection
25 m3/h
To Evaporator
Special RO 60 Bar 66 Recovery
Hollow Fiber UF
50 m3/h
Sludge to Filter Press
For Re-injection
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Case Study Waihi Gold Overview Process
PI
PI
240 M3/H
60 M3/H
TDS
30 M3/H
180 M3/H
TDS
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Waihi Overview Process
PI
PI
240 M3/H
60 M3/H
TDS
30 M3/H
180 M3/H
TDS
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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)
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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)
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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

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Waihi Gold Membrane Plant240 m3/h
Membrane Plant
Permeate Storage Prior to Discharge
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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)

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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)
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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)
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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

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Waihi Gold Membrane Plant240 m3/h
Membrane Plant
Permeate Storage Prior to Discharge
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• Oil Gas Experiences

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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

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Shell Oil Refinery surface waste water system
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Coal Bed Methane produced water process
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Husky Oil produced water Hydrophilic UF
Process Overview
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Current SAGD Process low-quality steam
generator make-up and high blow-down volumes
sludge
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SAGD Membrane Process 3-pass RO Permeate for
boiler feed
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Bench test results 85C

• 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

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Membrane SAGD Process

• Eliminate Hot Lime, new Steam Generation option,
  high recovery lt5-10 blow-down

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Gas Well produced water

• Produced Water from a Devon Energy natural gas
  production facility in New Mexico
• Water temperature 130-140F
• Capacity 7500 GPD
• Operational for 12 months

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

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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

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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

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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

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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)

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MDS Process Plant Water Balance
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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

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Frac-Flowback Plant Process Flow Diagram
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What makes MDS SystemsDesign Unique?

• Special membranes and element construction
• Special system design
• Special operating procedures based on intimate
  knowledge of the installations water
• Special cleaning procedures
• 28 years of process membrane systems experience
• Not just another bench test result commercial
  applications running daily at significant volumes