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

2. 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+%

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

4. Spiral Wound Technology

5. 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

6. Permeate Rate Does Effect Fouling

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

8. 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

9. 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

10. 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

11. 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

12. 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

13. RO of gold-cyanide complex concentration

14. 1000 m3 Plant at MYSRL – Yanacocha Norte, Peru

16. 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

17. NF fractionation of gold and copper-cyanide complex

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

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

20. 18 years of operation of EMS® systems at Freeport McMoRan (Phelps-Dodge) Rod Mill – El Paso, Texas2 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

21. 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

23. Copper and Iron rejection with special Modified RO membrane-elements

24. AMD Copper Recovery Process

25. 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

27. 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

28. Copper Refinery Precipitation Process Prior to Addition of Membrane System

29. 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

30. 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

31. 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

32. 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

33. 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

34. 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

35. Application 1 CLC Alkaline Mine Drainage

36. 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

37. 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

38. 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

39. 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

40. 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

41. 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)

42. 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)

43. 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
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

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

45. 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)

46. 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)

47. 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)

48. 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
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

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

50. Oil & Gas Experiences

51. 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

52. Shell Oil Refinery surface waste water system

53. Coal Bed Methane produced water process

54. Husky Oil produced water Hydrophilic UF – Process Overview

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

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

57. Bench test results: 85°C Feed 2600 mg/L Permeate 24 mg/L
Ca mg/L
Mg mg/L
Silicon mg/L
Fe mg/L
TDS mg/L
TOC mg/L
Permeate 24 mg/L
Ca………… mg/L
Mg…………. [undetectable]
Silicon……. 1.8 mg/L
Fe ………….. [undetectable]
TDS………… 24 mg/L
TOC……… mg/L

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

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

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

61. Lab test results: Ultra-filtration process
Feed
Ca……………… mg/L
Mg……………… 68 mg/L
Sodium……… mg/L
Sulfate……… mg/L
Chlorides…… mg/L
pH………………
TDS…………… ,833 mg/L
Cond*……… ,400 µm hos
TOC…………… mg/L
Oil & Grease ppm
Permeate
Ca……………… mg/L
Mg……………… mg/L
Sodium……… mg/L
Sulfate……… mg/L
Chlorides…… mg/L
pH………………
TDS…………… ,158 mg/L
Cond*……… ,700 µm hos
TOC…………… mg/L
Oil & Grease. [undetected]

62. Lab test results: Nano-filtration process
Feed
Ca……………… mg/L
Mg……………… mg/L
Sodium……… mg/L
Sulfate……… mg/L
Chlorides…… mg/L
pH………………
TDS…………… ,158 mg/L
Cond*……… ,700 µm hos
TOC…………… mg/L
Oil & Grease. [undetected]
Permeate
Ca……………… mg/L
Mg……………… 16 mg/L
Sodium……… mg/L
Sulfate……… mg/L
Chlorides…… mg/L
pH………………
TDS…………….. 6,835 mg/L
Cond*……… ,050 µm hos
TOC…………… mg/L
Oil & Grease. N/A

63. Lab test results: Reverse Osmosis process
Feed
Ca……………… mg/L
Mg……………… 16 mg/L
Sodium……… mg/L
Sulfate……… mg/L
Chlorides…… mg/L
pH………………
TDS…………….. 6,835 mg/L
Cond*……… ,050 µm hos
TOC…………… mg/L
Permeate
Ca……………… mg/L
Mg……………… 0 mg/L
Sodium……… mg/L
Sulfate……… mg/L
Chlorides…… mg/L
pH………………
TDS…………… mg/L
Cond*……… ,690 µm hos
TOC…………… mg/L

64. Projected Energy Costs – 24,000 bbl/day (3,790 m3/d)
Cost for a 3-pass system $ 1.85M USD
Total Energy – 720 hp $ /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

65. 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)

66. MDS Process Plant Water Balance

67. 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): µm pore size for final polishing of oils, polymers and suspended solids
No additional solids generated

68. Frac-Flowback Plant Process Flow Diagram

69. 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