DEPARTMENT OF CHEMICAL ENGINEERING

Purification of Salt and Brackish

Water
By: Gene Thiers & Tony Pavone
Antofagasta, Chile 2015
 Relevant instructor credentials
• Gene Thiers – Cofounder & chief technology
officer (CTO) of advanced water purification
technology company (SylvanSource Inc)
• Tony Pavone – Process engineer for industrial
water purification & wastewater treatment
plants (industrial sector, not municipal sector)
• We could describe Sylvan technology – but
then we would have to kill you!
Middle East thermal desalination plants
 SylvanSource Inc.
• Advanced thermal distillation technology
• Multi-stage
• Performance claims
– Low energy consumption
– Low capital cost intensity
– High operating reliability
– Low sensitivity to feed water quality
– Minimal requirement for rotating machinery
 Table of Contents (1 of 2)
• Introduction
• Contaminants of concern
• Salt water content
• Alternative business objectives
• Technology options
• Reverse osmosis
• MED-Multi effect distillation
• MSF-Multistage flash distillation
 Table of Contents (2 of 2)
• Comparison of commercial technologies
• Low volume commercial technologies
• Not yet commercial technologies
• Summary
 Introduction (1 of 4)
• World has plenty of water!
• 99.9% of natural water is salty or brackish
• Amount of water recycled is < 1%
• Basic options for removing dissolved salt
– Heat via boiling/condensing
 Introduction (2 of 4)
• Chemical precipitation using anionic and/or cationic
charged chemical additives
• Filtration across small pore surface (membrane) with
or without help of electricity
 Introduction (3 of 4)
• Electrodialysis and electrophoresis use ions to
enhance membrane filter separation
• Ions are organized to create an electric
potential between positive & negative
electrodes
 Introduction (4 of 4)
• Chemical absorption/adsorption (ion exchange resins)
• Basic thermodynamics
– It takes 1000 Btu to boil 1 pound of water
– It takes 0.65 kwh to boil 1 kg of water
– Objective is to boil more than once with same
amount of energy
– Coefficient of effectiveness (COE): How many times
you can boil 1 pound of water with only 1000 Btu of
energy
 What’s the Problem???
–Growing population requires more clean water
–Industry requires both more water and purer
water
–Global water supply dropped by 33% since
1970
–Water tables dropping
–Salt water incursions
–Saline in ground water
 Contaminants of concern in salt or brackish water (1 of 3)

• Floating material • Skim with clarifiers

• Gross solid material
• Suspended solids
• Low density solids
• Filterable solids
• Remove by gravity
• Agglomerate with
chemicals, then filter
• Agglomerate using air
flotation (DAF) & skim
• Pressure filter using
sand/charcoal
 Contaminants of concern in salt or brackish water (2 of 3)

• Biological material • Treat biologically (Biox)

• Oxidize (Cl2, O3, UV,
H2O2)
• Multi-valent dissolved • Micro-filtration
ions contributing • Precipitate by chemical
hardness addition (lime
– Sulfates softening, alum)
– Silicates
• Ultra and/or nano
– Carbonates
filtration
 Contaminants of concern in salt or brackish water (3 of 3)

• Mono-valent dissolved • Distillation

ions (NaCl) • Reverse osmosis
Salt content in major water sources
• Ocean water = 3% NaCl (33,000-35,000 ppm)
• Inland & shallow seas = 3-5 % NaCl
• Brackish subsurface aquifers= 0.1 to 2% NaCl
• Allowable NaCl content in usable water
– Drinking water: < 250 ppm
– Process water: < 100 ppm
– Boiler feed water: < 2 ppm
Global desalination capacity is accelerating
globally
Regional distribution of desalting capacity
globally
Distribution of desalination capacity by
application
Geographic regions with significant new
desalination capacity
 Alternative business objectives require
different technologies
• Purify feed water to meet user needs
– Drinking water typically uses chemical treatment
and reverse osmosis
– Boiler feed water uses RO in combination with ion
exchange, or electrophoresis
– Medical applications use electrodialysis
• Clean up wastewater for suitable discharge
– Chemical treatment prior to discharge
– RO for recycle
 Special applications use low tech options

• Mining industry in hot • Evaporation ponds

and dry areas
• Oil industry for • Chemical precipitation
produced water and simple distillation
• Pharma industry for • Incineration
pathogen protection
Desalting high volume technology options

• Reverse osmosis (RO)

• Multi effect distillation (MED)
• Multi stage flash distillation (MSF)
Generic approach to desalting
 Post treatment objectives
• Adjust pH to 8-9
• Add ‘taste promoters’ to drinking water
– Add small amount of CaCO3
– Bubble in air
• Disinfect if required
• Re-aerate or de-gas depending on end use
Fundamental reverse osmosis (RO) process

• Pre-treatment to remove solids, organics, and

hardness multi-valent ions
• Pressurize feed water to about 1000 psia
• Force feed water through RO membrane
cartridges
• Permeate (half of feed) is clean water
• Raffinate is high pressure reject water (half of
feed)
Reverse osmosis simple schematic drawing
 RO configuration can be optimized using
multi-stages
• Most high volume RO processes use 2-stage
RO cartridge system
• 1st stage is lower pressure (500 psi) to process
lower concentration feed water
• 2nd stage is high pressure (1000 psi) to process
higher concentration 1st stage raffinate
 Osmotic pressure considerations
• Natural driving force is osmotic pressure caused
by difference in salt concentration between
clean side and salty side
• Osmotic pressure causes flow from clean side to
salty side to equalize salt concentration on both
sides
• Reverse osmosis uses mechanical pressure in
opposite direction to overcome osmotic pressure
and flow water from salt side to clean side
Typical osmotic pressures to overcome by
RO
• Increased flux rate requires significantly higher
pressure than osmotic pressure
• Osmotic pressure is a function of salt
concentration: high concentration requires high
pressure
Osmotic pressure considerations
 Conventional RO membrane materials of
construction
• Historically asymmetric organic polymers
• Originally interfacial polymerization of m-
phenylene diamine & trimesoyl chloride
• Structured as hollow fibers or spiral wound
sheets
• Commercial RO membranes are either
cellulose acetate or polysulfone & polyamide
(composite)
US RO membrane suppliers
Asymmetric cellulose acetate membrane
structure
Aromatic polyamide membrane structure
Spiral wound RO membrane configuration
Hollow fiber RO membrane configuration
Scanning electron microscope cross section
of hollow fiber membrane
Nominal membrane pore diameter
(Angstroms)
Potential new RO membrane materials
• Nano pore zeolites
• Thin film nano composites
• Single tube nano-carbon
• Forward osmosis
Pre-treatment for RO membrane systems

• Claims to improve membrane lifetime from 3 years

to 5-10 years
• Claims to nearly eliminate catastrophic failures of
membranes
• pH adjustment
• Usually includes pressure filtration (sand/AC) or PP
cartridges, biological treatment, then micro-
filtration
• Pre-treatment represents about 1/3 of total capital
investment
 Historic causes for catastrophic RO
membrane failures
• Power failure stops flow (flow across
membrane must be continuous)
• Di-valent ion breakthrough physically plugs
membrane pores
• Biological growth on membrane surface plugs
membrane pores
• Excess oxidant use causes brittle membrane
surface failure
Improved energy recovery RO technology

• High pressure reject water spins turbine that

drives feed water pumps
Improvements to RO membrane modules

• More selective membrane materials permit

operation at lower pressure (lower energy)
• Comprehensive pre-treatment increases
lifetime of membrane modules (5-10 yrs)
• Individual membranes cartridges are built at
larger sizes (6 inches to 12 inches to 18 inches)
Conventional RO operating plants
MSF simplified schematic
MSF details
Multi stage flash (MSF) distillation process
schematic
 MSF basic principles (1 of 2)
• Steam is injected into 1st stage tank (highest
temp & highest pressure)
• Steam flashes some of the brine pool at the
bottom of the tank
• The flashed material condenses against colder
brine in tube bundle
• Condensate product collected below tube
bundle
 MSF basic principles (2 of 2)
• 1st stage brine pool pumped to 2nd stage
operating at lower temp and lower pressure
• At lower pressure, more of the brine pool will
vaporize at lower boiling temperature
• Vaporized brine condensed against colder
brine in tube bundle
• Condensate product captured
• Steam ejector creates vacuum for all stages
Large thermal desalination plants are
integrated with power plants
Multi effect desalination (MED) process
schematic
MED tube bundle details – can be arranged
vertically or horizontally
 MED basic description (1 of 2)
• Brine is fed to each stage in parallel rather
than in series in MSF
• As in MSF, all stages operate under vacuum
conditions
• Steam in injected into 1st stage tube bundle
where conditions are highest temp & high
pressure
 MED basic description (2 of 2)
• Steam produced in 1st stage fed to tube bundle
in 2nd stage operating at lower temp and lower
pressure
• Steam produced in 1st stage condenses in
tubes causing more brine to vaporize
• Condensate recovered as project
• Steam produced in 2nd stage is fed to 3rd stage
to vaporize more brine
Multi effect desalination (MED) municipal
scale operating plants
 Large scale MED and MSF distillation
characteristics
• Low pressure steam is typical energy source
• Steam usually sourced from adjacent power
plant
• Individual stages operate under vacuum
(steam jet ejector or vacuum pump)
• Typical plant has 20-40 stages
• Typical ∆T per stage is 3-5 oC
• Metallurgy is titanium
Historic MED and MSF distillation operating
problems
• Scale formation on heat transfer surfaces
substantially reduces coefficient of
effectiveness, driving up cost to make clean
water
• Corrosion on all wetted surfaces has required
high cost alloys
• Plugging of flow pathways has caused non-
scheduled shut-downs for clean out
 Vapor compression distillation
• Inlet feed steam is at highest pressure and
temperature in unit
• In subsequent stages, both the pressure and
temperature decrease
• Adding a mechanical compressor increases both the
pressure and temperature of steam
• Compressor improves coefficient of effectiveness
• Capital cost of compressor is compensated by
better energy efficiency created by higher COE
Vapor compression schematic drawing
Vapor compression characteristics
• Low pressure steam produced from brine is
fed to single stage centrifugal compressor
• Compressor increases both steam pressure
and steam temperature
• At new high temp and pressure, this steam
can be re-used at front end (1st stage) of
distillation train
Single stage vapor compression distillation
schematic
Single stage vapor compression distillation

• Usually used with toxic or high concentration

aqueous slurries
• Increases brine concentration well beyond
what is possible with normal thermal systems
• Metallurgy is usually high cost titanium
• Justified when brine disposal costs are high
– Trucking to remote disposal site
– Deep well injection disposal
 Comparison of commercially available
technologies

* Source: German Federal Industry for the Environment

 Low volume commercial technologies
• Ion exchange (IEX) and electrophoresis used in
combination with RO for high purity boiler feed
water in power plants
• IEX also used to ‘polish’ boiler blow down for recycle
to steam drum
• IEX system contains separate canisters of anionic and
cationic (Amberlite) resin
• Ions in feed water attached to resin sites
• Resin re-generated with strong acid and strong base
Not widely commercialized technologies (1
of 2)
• Evaporation by humidification
– Dry air passed through scrubber of salty water to
evaporate via humidification
– Humidified air then passed across tube bundle of
colder water to condense humidity
– Air re-heated and recycled
Not widely commercialized technologies (2
of 2)
• Israeli water trench technology
– 3 trenches dug into ground and coated
– Salty water pumped through center trench
– Above center trench is transparent plastic film
– Sunlight evaporates water from center trench
– Water vapor condenses on inside surface of plastic
film
– Condensed water drips into side trenches are
captured as product water
 SUMMARY
• Demand for clean water from salt water increasing in
quantity and purity
• RO, MED and MSF represent largest desalting commercial
scale plants
• Technology improvements have substantially reduced cost
to produce desalted water
• Each technology has specific benefits and deficiencies that
when applied to a specific application determine
competitiveness
• Unrealistic performance claims require comprehensive
due diligence!!!