Banff2013 Session5

May 12-14, 2013
High Salinity Produced Water Treatment

Made Economically Viable
Presented by:
Nathan Hancock
Director, R&D
Outline
• Where are the limitations of RO?
• What are Osmotically Driven Membrane Processes
(ODMPs)?
• What is the Oasys® membrane brine concentrator
(MBC)?
• Permian Basin and Marcellus Shale Trials
• What’s next?
© Copyright Oasys Water, Inc. www.oasyswater.com

RO Has Limitations
31.28 US$/m3
Source: Elimelech, et al., Science, 2011

0.76 US$/m3
What happens when
the water looks like this?
© Copyright Oasys Water, Inc. www.oasyswater.com Source: GWI, DesalData.com

3
Sources of Challenging Water
• Upstream Extractive Industry: O&G and Mining
– Shale oil (SAGD and tailings leachate)
– Shale gas and CBM produced water
– Drilling muds
– Acid mine drainage and dilute rare earth minerals harvesting
• Power
– Cooling tower blowdown
– Flue gas desulphurization
• Landfill Leachate
• Pharma and food products (esp. concentrates)
• Processing of future biofuel stocks (esp. algae)

4
Osmotically Driven Membrane Processes
Selective Mixing
DP=Dp
Hancock, Cath 2011

Brine Feed
Osmotic Dilution
or Concentration

Selective Mixing
Water Purification
Critical Innovation
Draw Solution
Reconcentration Draw
Feed
Solution
• Thermal
• Pressure (NF/RO)
• Magnetic
• Chemical
Membrane
Critical Innovation
Forward Osmosis

Water Purification with Oasys® FO
Membrane Brine Concentrator (MBC)
Advantages: Limitations:
 Robust • 1st Gen system requires
 Capital efficient pretreatment for hardness
 Fundamental energy advantage • High product quality,
 Demonstrated process but not distillate
• Feed: 50k – 150k mg/L • High solvent loading should be
• Concentrate: >220k mg/L avoided
Oasys Membrane Innovation
Oasys Patent – Forward Osmosis Membranes: US 8,181,794 B2
Coday, Cath, et al. ES&T, 2013
Adopted from McCutcheon et al. 2004
Oasys
Conditions: 6 M-C NH3/CO2 DS (a) = 58 g/L NaCl DS

28 g/L NaCl Feed (b) = 60 g/L seawater DS
8
What Makes Oasys FO Interesting
Robust architecture: Source: Oasys Water
• Effective at high salinity

– Substantial water flux
– Advantaged w.r.t. BPE and retrograde
solubility
– Non-metallic components
Excellent pretreatment

9
What Makes FO Interesting
Robust architecture:
Source: Mi, et al., JMS, 2011

 Effective at high salinity
• Excellent pretreatment
– Low T & P operation
– Minimal compaction of colloidal
material on membrane
– Substantial barrier to both TSS and TDS
– Not sensitive to surfactants or surface
tension modifiers
Source: Hickenbottom, et al., JMS, 2013

10
The Membrane Brine Concentrator:
A Paradigm Shift in Near ZLD
Thermal
Crystallizer
Specific Energy, kWh/m3
• Energy to boil water

30
Membrane • Exotic metals
Brine • High recovery
• Limited Recovery Concentrators
• High Pressure
20
• Simple/modular OASYS MBC MBC
v1.0 • High Recovery
• Simple/Modular
10 OASYS MBC v2.0 • No Boiling/Low Pressure
High Efficiency RO
FO/RO
SWRO
0
1% 2% 3% 4% 5% 10% 25% 50% 75%
% Total Dissolved Solids

11
Demonstration Projects – Produced Water
> 1,200 hours of operation > 400,000 liters of water treated
12
Marcellus Shale Produced Water
Marcellus Water Quality
Avg. 65% Water Recovery
(Raw | MBC Feed | Brine | Product)
SDI5
MBC Feed: >8
Boron
Feed: >10 mg/L
Prod: <0.5 mg/L

NORM
Feed: 170 pCi/L
Prod: <1 pCi/L
Concentration, mg/L
Process Data:
Water Flux And Solute Recovery
• No makeup draw solutes
added
• Sustained 65% water recovery of
73,000 mg/L TDS feed with FO • Minor fluctuations due to
non-optimized boiler cycling
Aqeuous Carbon Concentraiton, mol/L

5 80% 8 4.0
Nitrogen to Carbon Molarity Ratio

70% 7 3.5
4
Water Flux, L/m -hr
60%
Water Recovery
6
2
3.0
3 50%
5
40% 2.5
2 4
30%
2.0
3
20%
1 1.5
Water Recovery 2 Carbon Molarity
10%
Water Flux N:C Ratio
0 0% 1 1.0
0 20 40 60 80 100 0 20 40 60 80 100
Time, hr Time, hr
Permian Process Data
300,000 10# Brine
6,000
Brine Goal
Product Concentration, ppm

Not to Exceed
250,000 5,000
Concentration, ppm
200,000 4,000
150,000 3,000
100,000 2,000
1,000 1,000
0 0
Feed Brine Product
97% water flux recovery

Permian Water Quality
Average Water Recovery: 60%
(Raw | MBC Feed | Brine | Product)
Strontium
Feed: 400 mg/L
Prod: <0.05 mg/L
Sulfate
Feed: 450 mg/L
Prod: <1 mg/L
Concentration, mg/L
Economic Advantage vs Evaporation
Gen 1 System: Oasys ClearFloTM MBC
• Capex: 40% advantage
• Energy: 30-50% less compared to forced circulation MVC
• Utilization: Stable operation results in >90% vs. 70-75% for
evaporation
• Net result: ~60% total cost advantage

Conclusions
• MBC cost effective alternative to evaporation
• Successful projects validated viability of product

Conclusions
• Next step to integrate technology discontinuities
Saturated CaCO3 and Mg(OH)2
• >1,000 mg/L TSS (all inorganics)
• Also treated SiO2 up to
500 mg/L for 50 hours
• Operated at pH of 7 & 9
• No difference in system
performance

Conclusions
• Next step to integrate technology discontinuities
• Highly Commended by GWI for Industrial Reuse
Project of the year!

Thank You
Contact information:
Nathan Hancock, PhD
Director, R&D
nhancock@oasyswater.com
May 12-14, 2013
Carrier gas extraction for modular desalination of

industrial brines
Prakash Narayan Govindan

Co-founder, Gradiant Corporation
14th May 2013
Contributors:
Professor John Lienhard and students (MIT); Dr. Anurag Bajpayee and
co-workers (Gradiant Corp)
Basic concept of the carrier gas extraction system:
desalination at low temperature and atmospheric pressure
Carrier gas
(humidified)
Th
Packed bed
Heater
Humidifier Dehumidifier
Carrier gas
Brine reject Pure water, Saline stream in,

out, ṁb ṁpw ṁw,i ,To
1/12
CGE technology is simple, membrane-less, and robust under
high TDS water
Fundamental Improvements
• Multi-stage bubble column device for an order of magnitude lower CAPEX
• Novel method to attain multi-stage evaporator efficiencies in a single stage
• Decoupling of the valuable heat transfer surface from the sacrificial surface on which
concentration occurs
2/12
Multistage bubble column for low cost condensation
even in the presence of non-condensable gases
10 times higher heat rates than regular dehumidifiers at

similar effectiveness
Brings down condenser area requirement to MED
levels!!
3/12
Thermodynamic balancing to attain low thermal energy
consumption
Thermal energy consumption brought down to 6-

stage MED levels!!
4/12
A revolutionary modular solution to industrial brine
concentration issues
Rendering of field deployable

500 bbl/day system
• Skid mounted, modular, scalable system for varying feed water rates
• One module = 100 bbl./ day
• Process can use any form of low temperature heat
5/12
Technology Validation
 Developed over 5 years at M.I.T. through laboratory, bench-

scale and prototype testing
 Reliable operations of demonstration unit at pilot scale

meeting all performance objectives
 Several barrels of oil-field waste successfully treated from all

around the US
 Several barrels of other industry wastewater treated
Performance metric Target Results

Product Water (TDS) Discharge levels (<500 ppm) Achieved
Flow rate 10 bbl. /d Achieved
Field Sample Water Treated (TDS) > 200,000 ppm Achieved
Water Recovery Rate > 85% Achieved
Proof of Concept at Pilot Scale Achieved
6/12
Liquid Concentration of high salinity industrial brines
(>100,000 ppm): the sweet spot
High cost, high recovery (> 80%)
low cost , high recovery
lower cost, low recovery (<60% at >10 g/L)
7/12
IP Position and Strategy
• Intellectual Property
 Strong IP Position with 5 issued patent
 9 pending patents
 Global patent protection
• Licensing/ Partnerships
 Potential for technology development/ licensing partnerships for varied regions/
applications
IP Subject Matter Areas Patent Activity Number of Filings

Process (5) 2009 2
Apparatus (2) 2012 2
Methods (6) 2012 5
Chemical (1) 2012 5
Total Patents Filed 14
8/12
Pressing need for brine concentration in unconventional oil and gas
plays: focus market
Large market for high salinity brines;

Working with E&P companies; exploring other partnerships
9/12
Translation of technology and expertise to different applications and
regions
Chemical plant brines Seawater desalination
Solvent mining Tanning brines
Potential for technology development/ sub-licensing partnerships
10/12
Commercialization schedule
Full-scale
Commercial
roll-out
System
integration and
Increasing Value/Reducing Risk
commercial
pilot deployment
Pilot scale
Demonstration
Unit Core Activities: Core Activities:
Draft design o In train unit tested in field
Bench-scale  Grade V cost estimate o Development agreements
Demonstration Core Activities: o Field testing finalized
Unit Proved at commercial o 3rd party licensing
scale
 High TDS runs
 High recovery
Proof of  Process configuration
Finalized
Concept
Pure water product
2008 2009-2012 2012-2012 2013-2014 2014+
11/12
• Carrier gas extraction is positioned to become a leading brine
concentration technology
• Invented and developed by Gradiant’s founders at MIT
• Current focus on produced water treatment application
• Licensing and partnership opportunities in other industries
• Strong relationships within water and oil and gas industries
• Fundamental understanding of water treatment science and technology
govindan@gradiantcorp.com | +1 479 236 2709

12/12
May 12-14, 2013
Innovative FO Filtration and ZLD Technology

for Oil & Gas Waters
Keith Lampi - COO
© Copyright 2013 Hydration Systems, LLC www.htiwater.com

Hydration Technology Innovations
Focus on Forward Osmosis
• Membrane R&D
• Commercial membrane
manufacturer (CTA and
TFC)
• Spiral element and plate
and frame manufacturer
• Pilot fabrication and
operations
• Systems integrator
• Mobile wastewater tolling

The Technology Platform - Forward Osmosis
Fouling of the membrane
skin layer in a hydraulic
pressure driven process
like RO/NF is intrinsically
different than in an
osmotically driven
process like FO. FO
fouling is more topical
and therefore easy to
clean.
• Advantages over pressure driven membrane processes (RO, NF, UF, MF).
• Less energy intensive – powered by natural osmosis.
• More robust – membrane fouling is easily reversible.
• Higher water recovery – reduces waste stream disposal volume.
• Synergistic with RO – improves overall process efficiency and reduces the cost of treatment.
• Opens new markets to advanced membrane treatment – frac water flow-back, on-site pure water
(OPW) management, industrial process water reclamation, RO pretreatment, etc.

One of the Sweet Spots for FO –
HTI Technology & Humanitarian Relief
In the first hours and days of any disaster – one

of the greatest needs is a safe clean water
supply - but yet the most difficult to provide

HydroPacks – Hydration Solution for
Early Stage Disaster Response
Easy to transport by air, ground or
even canoe. Simple to use, high
purity, high acceptance and the
ability to be used in any water
source.

The HydroPack
The Basics of Osmotic Filtration
When full, contains

½ liter of a pure,
nutrient drink
Place in any water
Thin envelope source to self-hydrate User then pokes with
with a membrane overnight straw and drinks
side - filled with a
nutrient powder Logistical benefits: 15 to 1 weight and volume reduction,
provides nutrients while purifying local water sources
Forward Osmosis – Basic Flow Diagram
FO Membrane Element
Draw
Solution Feed
Solution
Osmosis is the flow of water across a semi-permeable membrane

(MEMBRANE) from a solution of lower osmotic pressure (FEED) to a
solution of higher osmotic pressure (DRAW SOLUTION).

Forward Osmosis Membrane
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis RO/FO

Forward Osmosis
• FO membrane – RO rejection properties, hydrophilic (surface contact 60o), smooth rejection

surface, low “S” structural parameter value while maintaining physical integrity (strength).
• HTI – specializes in an embedded support design (minimal “S” value) for both cellulosic and
polysulphone TFC membranes. In general, CTA is more resistant to fouling and has lower ICP
over TFC membranes, but TFC resists caustic pHs and for non-fouling streams has higher fluxes
• For most Oil and Gas Waste Waters – HTI employs CTA membranes because of the fouling
nature of the high concentrations of TSS, COD, BOD, turbidity and hydrocarbons

What Makes a Good Draw Solution
• high drawing power (osmotic potential)

• “free” & part of a process that needs dilution (hydraulic fracturing
brine) or can be readily disposed of (diluted seawater),
• easily re-concentrated, contained and controlled via an
economical process such as RO or nano-filtration or waste heat
• minimal back diffusion across the membrane
• chemically compatible with membrane and system components
• inexpensive and readily available
• non-toxic
• stable under heat and changing pH’s
• serve multi-purposes, such as an anti-microbial agent

Sweet Spots for FO
• A concentrated stream (e.g., saturated brine) needs to be diluted

and a highly fouling wastewater is available (Drilling waste
dewatered for dilution of brine for frac). FO becomes a mass
exchanger for water.
• A stream is so fouling that reverse osmosis (RO) requires either
too much cleaning or pretreatment (Produced water filtration).
FO becomes a very effective pretreatment process for RO, which
is then used to re-concentrate the draw solution and extract the
clean water.
• A draw solution is “free” (Produced water as draw solution to
filter seawater for flooding)
• A reconcentration step is “free”, such as a cooling tower process
where evaporative energy from the cooling tower both
concentrates and provides cooling at the same time.

HTI’s core competency is rooted in a deep understanding
of membrane filtration and separation processes and a
focus on development and commercialization of specialty
polymer membrane materials and products
• Flat sheet woven backing
OsMemTM Forward Osmosis • Flat sheet non-woven backing
membrane
• Spiral modules
SepraMemTM ultrafiltration
• Plate and frame systems
membrane
• Hollow fiber (tubular and capillary)
• Specialty osmotic devices

Proven high performance – low fouling membrane
configurations mean minimal or no pretreatment
• High cross flow velocity
• Ultra smooth hydrophilic membrane surface (oleophobic)
• Specialized feed spacers
• Unique spiral membrane configurations
• Spacer-less designs
• Multi-element per housing for packing density
• Aerated plate and frame configurations
chevron style feed spacer

HTI – CSXF Cyclonic Swirl Cross Flow
Advantages of HTI CSXF Membrane Filtration

• FO or UF filtration
• Designed for high TSS feed streams
• No feed spacers to plug
• Self cleaning cyclonic swirl cross flow feed
• Interchangeable membrane discs – easily maintained
• Durable industrial design
• Solids blow down ports

Hydration Technology Innovations
Numerous Partnerships Advancing Forward Osmosis
• Industry Partner with Colorado School of

Mines - “Novel Engineered Osmosis
Technology: A Comprehensive Approach
to the Treatment and Reuse of Produced
Water and Drilling Wastewater”
• Funded by the US DOE and administered

through RPSEA (Research Partnership for
a Secure Energy for America)
• Funding with industry match exceeds $2M

Feed: Example of Produced Water (Colorado Rocky)
Conventional waste water management has focused on transportation and deep well
injection. Where waste heat is available, thermal evaporation is also employed. If
water reuse is a goal – must use other treatment techniques.
Produce Water Constituents Key Effluent Specifications

Contaminants Average Range
Fe < 10 ppm
Aromatics 60 0 - 120
TPH GRO (mg/l) (*) 400 30 - 1300 TDS < 400 ppm
TPH DRO (mg/l) 750 7 - 5000 TSS < 30 ppm

TSS (mg/l) 1000 200 - 2000
Hydrocarbon < 20 ppm
CO2 (mg/l) 70 0 - 120
pH 6.5 5-8 Bacterial control 100%
TDS (mg/l) 25000 15000 - 60000 pH 6.0 - 7.5

Total Organic Acids (mg/l) 400 200 - 600
Bicarbonate (mg/l) 700 100 - 1500
To achieve desired outcome
Chloride (mg/l) 16000 6000 - 38000
Sulfate (mg/l) 90 10 - 300
(especially TDS), an osmotic
Barium (mg/l) 35 5 - 110 membrane, or a thermal or
Iron (mg/l) 50 1 - 300 electrolysis process must be
Sodium (mg/l) 10000 300 - 18500 employed
(*) Total Petrochemical Hydrocarbons (gasoline and diesel range organics)

Feed: Traditional Treatment Processes for
Water Reuse
Oil and grease hydrocarbons If waste minimization and reuse is
• Flotation (DAF) the goal – a combination of
• Adsorption treatment processes is required –
• Electrocoagulation
with TDS remediation (such as RO)
• Centrifugal (hydrocyclone)
as one of the final steps.
TSS
• Clarifier
• Media Filter
• DAF This is where FO fits in well as a
Hardness, Iron, Boron tandem treatment process
• Lime softener before RO or evaporation. The
• Ion exchange
• Membranes (UF)
non-fouling nature of FO
• Chemical oxidation minimizes pretreatment needs.
TDS
• RO
• Evaporation / crystallization
• Electrodialysis / electrolysis

Long Putts for FO
If the waste water stream is “clean” enough that no or

minimal pretreatment is required for RO – then FO is
most likely not a good choice - just use RO
If the FO process requires extensive pretreatment – then

you are not taking advantage of the non-fouling
properties of FO
If the draw solution recovery is costly and cumbersome

due to high TDS feed or complex process steps

Top Ten FO Business Opportunities
Oil & Gas Wastewater
Food & Beverage and Life Sciences
Landfill Leachate
Impaired Water Cooling Tower Make-up
Osmotic Bioreactor
Anaerobic Centrate Concentration
Marine Grey/Wastewater Concentration
RO Desalination Pre-Treatment/Dilution
Brine Production & Solution Mining
Pressure Retarded Osmosis

OIL & GAS WATER AND WASTEWATERS
• Low-Fouling, Low-Energy FO
Process
• Highest Water Recovery/Quality
• Handles High TSS Feed with
Minimal Pretreatment
• Mobile and Scalable

Wastewater Treatment Optimization
Course Chemical Designer

No Course Filtration Treatment & Chemicals & FO / RO /
Treatment Filtration w/ Dilution Separation Separation Evaporation
(Poor) Reclaimed Oilfield Waste Water Quality (High)
(Low) Reclaimed Wastewater Treatment cost (High)
(High) Down-hole Quality Risks (reuse) / Environmental Risks (discharge) (Low)
High Scale, High Scale, Mod. Scale, Mod. Scale, Low Scale, Ultra-Low
High Mod. Mod. Low Low Scale,
Bacteria, Bacteria, Bacteria, Bacteria, Bacteria, No Bacteria,
High Mod. Low Low Ultra-Low No
Suspended Suspended Suspended Suspended Suspended Suspended
Solids, Solids, Solids, Solids, Solids, Solids
High TDS High TDS Mod TDS Mod TDS Mod TDS Low TDS

Three Primary Types of E&P Wastewater
a challenging market
1. Drilling Fluids
(Typically oil bearing low TDS, high turbidity/suspended solids) The chemistry, volume, rate, and
• Water-based mud logistical timing of each type of fluid
• Rig supply water is unique to EACH well
2. Completion Fluids
(Moderate TDS time dependent, gels, moderate turbidity, moderate scaling)
• Stimulation fluid (upstream frac water)
• Flow back (downstream frac wastewater)
• Work-over fluid
3. Production Fluids
(High TDS dependent upon geologic formation, low turbidity, highly scaling)
• Geological saltwater produced with the hydrocarbons
E & P water volumes are high and water reuse solutions are desired - suggesting an attractive
business opportunity. However operators continue to seek lower cost solutions for difficult to
treat water and constantly evaluate water quality trade-offs of (1) cost, (2) HC production risk
and (3) environmental risk.

Advantages of FO
• Allows reuse of otherwise unrecoverable wastewater
• Primary reclamation process is driven by alternative energy (osmotic
gradient-drive)
• Selective FO filtration rejects unwanted solutes and solids from the waste
stream without complicated pre-treatments or fouling
• Economically competitive with conventional disposal
• Better permeate water quality than most other sources
• Mobile and scalable

Initial HTI Focus on Drilling Fluid Recycling for
Well Stimulation (Frac)
• Prior to the gas production phase, a salt brine is often
used to “frac” a well to maximize production.
• In this case FO allows for use of the osmotic energy in
the salt to filter and recycle drilling wastewater that
would be otherwise destined for disposal.

Forward Osmosis Drilling Wastewater Recycling
May 12-14, 2013

Recycling Drilling
Wastewater for Reuse as
Completion Fluid
Dozens of Haynesville and Eagle Ford shale
projects completed since January 2010.
Range from 2000 bbls reclaimed up to
37,000 bbls reclaimed from a single drilling
site.

HTI’s Hybrid FO/RO Oil & Gas Wastewater Recycling
Producing Fresh Water from Drilling, Flowback and
Produced Waters
HTI- HICORTM Reverse Osmosis

High concentration osmotic
regeneration (HICOR)
Example: HTI’s Hybrid FO/RO Filtration/Recycle
Drilling Wastewater Cost Metrics
FO recycle process:
Drilling waste volume 25,000 bbl
FO water recovery percentage 82 %
Water recovered / recycled 20,500 bbl
Total OPEX (under $0.06 / gal - $0.015/liter) $ 50,548 (includes equipment amortization
overhead and profit)
Disposal and trucking of
un-recoverable drilling waste $ 16,962 $3.76 bbl (wastewater)
Total FO recycle process cost $ 67,510 $3.29 bbl (clean water)
Traditional disposal and fresh water process:

Fresh water acquisition and transportation $ 37,846 $1.85 bbl (fresh water)
Disposal and trucking of drilling waste $ 85,577 $3.42 bbl (wastewater)
Total traditional process cost $123,423
Net cost savings: $ 55,913

45% reduction over conventional methods

EVAPORATIVE REDUCTION & CRYSTALLIZATION
THERMAL SOLUTIONS FOR WASTE MANAGEMENT
•Solute Concentration
•Solidification/Crystallization
•Zero Liquid Discharge
•Wastewater Elimination or
Reduction
•Enhanced Process Cooling
•Low Temperature and Non Scaling

HTI’s Evaporative Reduction & Crystallization (ERC)
How Does It Operate?

• It is an air driven, evaporative technology
• The air evaporation affords low temperature operation at atmospheric pressure
• ERC employs unique scaling and fouling free heat and mass transfer technology
Modular & Scalable Units Evaporate 400 bbl/d

HTI - ERC Process Diagram
Humid
Air Outlet
Evaporative Reduction & Crystallization
Ambient Dual Stage Crystallizing

Air Inlet Evaporation Chamber
Conventional Heat
Exchanger
Ambient Cold Waste Water Cold Transfer Fluid Cold Return
Air Inlet
Thermal
Source
Warm Waste Water Warm Transfer Fluid Waste Heat
Immiscible Heat
Feed Exchanger
Water
Solids
Unique Low Temperature, Non Scaling, Crystallizing Technology

HTI - ERC: Waste Heat Harvest
Waste Heat Sources
• Engine jacket cooling water
• Engine auxiliary cooling water
• Engine exhaust
• Compression intercooling and
aftercooling
Gas Compression Reciprocating Engine
Engine Jacket and Auxiliary Heat Harvest Compression Intercooling Heat Harvest

HTI - ERC: Seed and Release Fill for Mass Transfer
Brine Distributes
Splashing From Above
Thin Flexible Top

Section Sheds Salts
And Directs Brine To
The Flexible Evap Panels
Flexible Evap
Panels Oscillate
In The Airflow
Permitting Salt
Growth and Release

HTI - ERC Technology – What Makes it Unique?
• Does not consume energy from the heat cycle of a plant

• Employs low cost, otherwise useless, plant waste heat
• Operates in a similar fashion to a cooling tower thereby providing efficient
cooling service
• Non-scaling, sterile crystallization does not require biocides, chemical scale
inhibitors or dispersants
• Operates at low temperatures
• Atmospheric pressure operation; no pressure vessels and associated hardware
• Low pressures and temperatures permits construction from corrosion free,
lightweight, inexpensive plastics
• Modular Installation is possible, easing project growth and providing load
following capability
• Full ZLD solids crystallization or solute concentration operating modes are
available

Pressure Membrane Systems
HTI – SepraMemTM
High Solids Ultra-filtration
Geological Produced Water
Electrocoagulation Effluent
Cutting Fluids
Specialty Emulsified Oil Water Separations
HTI – HICORTM Reverse Osmosis

High Pressure High Rejection Reverse
Osmosis (RO) for Draw Solution Re-
Concentration
HTI – HIPURTM Reverse Osmosis

Low Pressure High Rejection Brackish Water
Reverse Osmosis (RO) Systems

May 12-14, 2013
Thank You
Keith Lampi, COO
541.917.3335
klampi@htiwater.com

Low Cost High Recovery Brackish Water
Desalination in a Novel Hybrid Pilot Plant
Ben Sparrow, CEO

Contact: Malcolm Man, VP Business Development
malcolm.man@saltworkstech.com
CONFIDENTIAL Copyright © 2012 Saltworks Technologies Inc.

Less solubles:
CaSO4, BaSO4, MgSO4, CaCO3, etc
Reverse Osmosis Systems experience

challenges with Red Columns

Albertan Basal Brackish Water: chemistry, pH=8.4
Parameters Units 7/23/2012
Total Dissolved Solids mg/L
Total Suspended Solids mg/L
Total Hardness (calc) mg CaCO3/L
Bicarbonate mg CaCO3/L
Carbonate mg CaCO3/L
Hydroxide mg CaCO3/L
Barium mg/L
Boron mg/L
Calcium mg/L
Chloride mg/L
Copper mg/L
Fluoride mg/L
Iron mg/L
Lithium mg/L
Magnesium mg/L
Manganese mg/L
Nitrate-N mg/L
Phosphorus mg/L
Potassium mg/L
Reactive Silica mg/L
Selenium mg/L
Silicon mg/L
Sodium mg/L
Strontium mg/L
Sulphate mg/L
Zinc mg/L

ZLD: I
Remove Protect RO & Brine

Remove
multivalent remove some Desalt Management
“bits”
ions and/or organics
adjust pH Evaporator/
RO Brine Crystalizer
Concentrated
discharge Brine or Solids
Lime or
Pre- Microfiltration
Ion
screen / Ultrafiltration
Exchange Fresh water
Reverse
Sludge and/ Osmosis (RO)
or acid / Backwash
caustic regen discharge
waste

ZLD: II
Objective:
• Develop reliable, lowest total cost of ownership ($/m3) treatment train
• Maximize recovery (limit discharge) from a membrane system
• Avoid chemical precipitation & ion exchange waste volumes + HSE concerns

ElectroChem-RO
Reverse Osmosis ElectroChem ElectroChem-RO Hybrid
Water flux via pressure Salt flux via electrical ElectroChem softening of
through semi-permeable potential through ion RO feed and concentration
membrane exchange membranes of RO brine reject
CONFIDENTIAL Copyright © 2008 - 2013 Saltworks Technologies Inc.

ElectroChem Configurations
Conventional Configuration Salatworks “ElectroChem” Configuration
Electrodialysis Reversal: EDR 1.0 High Concentration EDR 2.0
- Two compartment stack - Arrangement for high concentration
- Saltworks’ novel ion exchange membrane:
ductile, high multivalent transference, pH1-13
- Positive seal modular stack
- Self cleaning controls
Anion exchange
Concentrate
~80K ppm
Cathode
Electrolyte
Product
~5K ppm
Product
Concentrate
Product
Concentrate
Electrolyte
Anode
membrane
Cation exchange
membrane
+
-
+
-
+
-
+
CONFIDENTIAL

ElectroChem-RO: Bench
Reverse Osmosis Unit ElectroChem Stack Integrated ElectroChem RO Unit
• Fully automated bench process plant

• 24-7 operation over 12 months
• Confirm chemistry, recovery, long-duration operation
• Brine discharge @ 100-125K ppm; recovery 80-85%

ElectroChem-RO: Pilot
Reverse osmosis reject
Brine discharge
Salt
Pre- transfer Fresh water
Feed
treatment (RO permeate)
ElectroChem Reverse
(softening) Osmosis (RO)
• 50 m3/day containerized plant

• Pre-treat by Sedimentation-MF-UF
• Full automation and DAQ
• Brine discharge @ 100-125K ppm; recovery 80-85%

PFD: ElectroChem-RO-SaltMaker
DPT
241
CIT FIT
221 231
Sedimentation PT PT
A
Inlet Break Tank 261 262
Microfiltration Ultrafiltration
B (MF) C (UF)
Raw Water
Input P-231
D
UF Backwash
CIT
Q 212
O
CIT S
FI PT SaltMaker
CIT 421 424 211
C 421
Tank M N P
Brine or
ElectroChem-RO Solids
Salt Transfer
421
P-421
IT
FI PT
Brine Reject
CIT 422 422
422 CIT
AT K L
311
(pH)
D 422 R
421
ET
Tank P-422
FI PT
425 425 Freshwater
I J
ElectroChem
316
PI
P-425
G H
FIT PT
312
FIT
P CIT 311 311
Tank 425 RO Permeate
E RO
CIT PIT (Freshwater)
312 312
P-311 F
UV
UV
“Kidney Loop” P-251

Pre-treatment: Sedimentation – MF – UF
Untreated Post Break Tank Post Bag Filter Post UF
19.9
20
18
16
14
12
10 10
10
7.7 7.7 7.8
8
4 3.0
2.0
2 1.5 1.3
0 0
0
Total Suspended Solids (mg/L) Turbidity (NTU) Calcium (mg/L)

UV: Naphthenic Acid Fouling Mitigation
Parameter (mg/L) Pre-UV Treatment Post UV Treatment

Naphthenic Acids 24.3 <1.0
Dissolved Organic Carbon 18.5 33.7
Total Organic Carbon 16.6 30.1
Benzene <0.00050 <0.00050
Ethylbenzene <0.00050 <0.00050
Toluene <0.00050 <0.00050
Xylenes <0.00075 <0.00075
EPH10-19 <0.25 <0.25
EPH19-32 <0.25 <0.25
Volatile Hydrocarbons
(VH6-10) <0.10 <0.10
VPH (C6-C10) <0.10 <0.10

RO Sample Data
Untreated RO
Parameter (mg/L) RO Feed RO Brine Permeate
pH 8.02
EPH C10-C19 <100
EPH C19-C32 <100
Oil and Grease - Total <1
Total Dissolved Solids 230
Total Organic Carbon 6.0
Bicarbonate (as CaCO3) 65
Boron 3.66
Calcium 0.08
Carbonate (as CaCO3) <1
Chloride 74
Hardness (as CaCO3) 3
Magnesium 0.64
Manganese <0.001
Reactive Silica 0.46
Sodium 129
Sulfate <0.5

ElectroChem: Sample Data

ElectroChem: Sample Data

ElectroChem: single pass desalination & soften data
Parameter (mg/L) Stack Feed Stack Outlet % Decrease
pH -
Total Organic Carbon 43.4%
Total Dissolved Solids 38.7%
Barium 57.1%
Bicarbonate (as CaCO3) 12.6%
Boron No Change
Calcium 84.4% +
Carbonate (as CaCO3) 59.6%
Chloride 27.1%
Lithium 27.0%
Magnesium 71.3%
Manganese 50.0% +
Reactive Silica No Change
Sodium 35.3%
Strontium 68.4%
Sulfate 27.0%

SaltMaker: low cost, modular, robust, highly impaired waters

SaltMaker: freshwater & solids from highly impaired waters
• Low temperature thermal process (<85 deg C)
• Reliability: no membranes, non-metallic wetted parts
• Modular design: rapid dispatch & service
•
•
Electric or thermal drive
Applications:
CONFIDENTIAL
– Recover freshwater (< 200ppm TDS) from highly
impaired waters: high salinity, organics, or hydrocarbons
– Brine concentration & zero liquid discharge
– Concentrate and desalt waste water with little to no
pre-treatment
CONFIDENTIAL
SaltMaker modules
loaded by forklift

SaltMaker Results
SaltMaker SaltMaker
Parameter SaltMaker Feed Concentrate Freshwater
pH 8.09
Total Dissolved Solids 40
Total Organic Carbon 3.1
Naphthenic Acid <0.2
EPH C10-C19 0.14
EPH C19-C32 <0.1
Oil and Grease <1
Barium 0.0010
Bicarbonate (as CaCO3) 28
Boron 0.045
Calcium 0.09
Carbonate (as CaCO3) <1
Chloride 23.8
Lithium 0.0035
Magnesium 0.35
Manganese <0.001
Nickel <0.0005
Potassium 0.2
Reactive Silica <0.01
Selenium 0.0008
Sodium 14.1
Strontium 0.0029
Sulphate <0.5

ZLD Economics: 1000 m3/day ->$3.4/m3 inlet
• ElectroChem-RO: 80-85% recovery @ $2.25/m3
• SaltMaker: 90%++ recovery @ $4.45/m3
Pre-treatment: MF-UF ElectroChem-RO SaltMaker: Waste heat driven
Recovery 0.98 0.8 0.95
Inlet Capacity (m3/day) 1000 1000 200
Equipment Capital $ 180,000 $ 1,200,000 $ 1,350,000
Site Installed Capital $ 288,000 $ 1,920,000 $ 2,160,000
Per m3 SaltMaker Per m3 Plant
Inlet Inlet
Levelized Capital ($/m3) @ 8% 20 yrs $ 0.09 $ 0.60 $ 3.35 $ 0.67
Energy Consumption (kWh/m3 inlet) 0.4 15 8
Energy Cost ($/m3) $ 0.03 $ 1.20 $ 0.64 $ 0.13
Non-Energy Operating Cost ($/yr) $ 50,000 $ 150,000 $ 150,000
Non-Energy Operating Cost ($/m3) $ 0.15 $ 0.46 $ 0.46 $ 0.09
Sub-System Total Cost of Ownership ($/m3) $ 0.27 $ 2.25 $ 4.45 $ 0.89
Plant Total Cost of Ownership ($/m3 plant inlet) $ 3.41

Total Cost of Ownership: techno-economic map
HYDROCARBONS
(ppm)
ORGANICS
(ppm)
SALTMAKER: EVAPORATE & CONDENSE
TCO: $6 - 60/m3
HEAVY OILS (>C10)
600
20
ELECTROCHEMICAL
LIGHT OILS (<C10)
TCO: $0.1 - 2.5/m3

3
REVERSE OSMOSIS*
1
TCO: $0.9 - 2.3/m3
SALINITY (ppm) 100,000 200,000 SOLIDS
HARDNESS (ppm) 400 2,000

Desal Project Considerations
• Total cost of ownership: capital + operating + energy
• Energy: source, cost, impact
• Chemicals: Health, Safety & Environment + cost
• Disposal: brine, sludge, waste
• Operations: variability, complexity

Water Treament Chemistry & Intelligent Controls
PRE-TREATMENT RO/NF MEMBRANES ELECTROCHEM SALTMAKER

Various processes H2O permeable membranes Ion exchange membranes Non membrane
Off the shelf Off-the-shelf w/ Saltworks Saltworks proprietary Saltworks proprietary

improvements
Products & Technologies: Products & Technologies: Products & Technologies: Products & Technologies:
- Clarification & flotation - Reverse osmosis - Thermo-Ionic - SaltMaker Thermal
- UV oxidation - Nanofiltration - Membrane based softener - SaltMaker Electric
- Media filtration - Advanced controls - Electrodialysis
- Micro & Ultrafiltration - Hybrids
- Electrocoagulation
Applications: Applications:
Applications: Applications: - RO hybrid for high recovery - Highly impaired waters
- Particulates, organics, oil & - Brackish water & seawater - Produced water - Brine concentration
grease removal - Low organics & < 80K ppm - Enhanced oil recovery - Solids production
- All water types & applications saltwater - Advanced separations - Waste heat → fresh water

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May 12-14, 2013

High Salinity Produced Water Treatment

© Copyright Oasys Water, Inc. www.oasyswater.com

Source: Elimelech, et al., Science, 2011

© Copyright Oasys Water, Inc. www.oasyswater.com Source: GWI, DesalData.com

© Copyright Oasys Water, Inc. www.oasyswater.com

Hancock, Cath 2011

© Copyright Oasys Water, Inc. www.oasyswater.com

© Copyright Oasys Water, Inc. www.oasyswater.com

Coday, Cath, et al. ES&T, 2013

Adopted from McCutcheon et al. 2004

Conditions: 6 M-C NH3/CO2 DS (a) = 58 g/L NaCl DS

• Effective at high salinity

© Copyright Oasys Water, Inc. www.oasyswater.com

Source: Mi, et al., JMS, 2011

Source: Hickenbottom, et al., JMS, 2013

• Energy to boil water

% Total Dissolved Solids

> 1,200 hours of operation > 400,000 liters of water treated

Aqeuous Carbon Concentraiton, mol/L

Nitrogen to Carbon Molarity Ratio

Product Concentration, ppm

97% water flux recovery

© Copyright Oasys Water, Inc. www.oasyswater.com

© Copyright Oasys Water, Inc. www.oasyswater.com

© Copyright Oasys Water, Inc. www.oasyswater.com

© Copyright Oasys Water, Inc. www.oasyswater.com

© Copyright Oasys Water, Inc. www.oasyswater.com

Carrier gas extraction for modular desalination of

Prakash Narayan Govindan

Brine reject Pure water, Saline stream in,

10 times higher heat rates than regular dehumidifiers at

Thermal energy consumption brought down to 6-

Rendering of field deployable

• One module = 100 bbl./ day

• Process can use any form of low temperature heat

 Developed over 5 years at M.I.T. through laboratory, bench-

 Reliable operations of demonstration unit at pilot scale

 Several barrels of oil-field waste successfully treated from all

 Several barrels of other industry wastewater treated

Performance metric Target Results

Proof of Concept at Pilot Scale Achieved

low cost , high recovery

lower cost, low recovery (<60% at >10 g/L)

IP Subject Matter Areas Patent Activity Number of Filings

Total Patents Filed 14

Large market for high salinity brines;

Chemical plant brines Seawater desalination

Solvent mining Tanning brines

Potential for technology development/ sub-licensing partnerships

2008 2009-2012 2012-2012 2013-2014 2014+

• Invented and developed by Gradiant’s founders at MIT

• Current focus on produced water treatment application

• Licensing and partnership opportunities in other industries

• Strong relationships within water and oil and gas industries

• Fundamental understanding of water treatment science and technology

govindan@gradiantcorp.com | +1 479 236 2709

Innovative FO Filtration and ZLD Technology

© Copyright 2013 Hydration Systems, LLC www.htiwater.com

© Copyright 2013 Hydration Systems, LLC www.htiwater.com

© Copyright 2013 Hydration Systems, LLC www.htiwater.com

In the first hours and days of any disaster – one

© Copyright 2013 Hydration Systems, LLC www.htiwater.com