Case Studies: Treatment Technologies for Industrial Water ReuseSteve Gluck, Freeport, TX; Aaron Johnson, Bob Goltz, Midland, MI; Jessica Shu, Edina, MNCornelius Groot, Terneuzen, NL; Tim Finley, Freeport, TX

Dow Chemical

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Herbert Dow and George Westinghouse collaborated on the steam regenerator and industrial co-generation in 1906

Dow’s CEO, Dr. Leland Doan; President John F. Kennedy; and Dr. A.P. Beutel of Dow Texas Division, send the signal to start operation of the very first seawater to fresh water conversion plant in the U.S. >>White House, June 21, 1961.

Photograph courtesy of Post Street Archives

"Today is an important step towards the achievement of one of man's oldest dreams, to secure fresh water from salt water. I can think of no cause and no work which is more important not only to the people of this country, but to people all around the globe, especially those who live in deserts or on the edge of oceans.”

- President John F. Kennedy

Overview

Activity highlight in Freeport TX for Water Reuse and Conservation

Reuse journey in Terneuzen, Netherlands

Tarragona, Spain- “Freeing up the river” with industrial water reuse

New membranes for Orange County Water District

Removing Water Soluble Organics from Produced Water

Produced Water reuse in Wyoming

Summary points

Freeport Manufacturing

• 1950s – Drought Dow installs local reservoirs Water supply contract for existing/future reservoirs in

Brazos Basin

1990s- Population Growth In entire Brazos Basin adds stress on water reserves

in reservoir storage

2000s- Water Conservation Dow begins water conservation/supply improvement

projects Dow procures additional land for local storage

Today- Drought Freeport site adds entire waste water discharge from

City of Lake Jackson to feed supply

Manufacturing

Municipality

Reservoir

Reservoir

Freeport Water Recycle and Conservation

100,000 gpm withdrawn from Brazos River- Goal to reduce by 10%

Added role of Strategy Director

Hosted facility-wide contest to raise drought awareness and identify conservation activities

37 contest entries

winner reduced usage by 400 gpm

Held Water Symposium with local Petrochemical Council and Municipalities to share conservation strategies

Dow’s collaboration with its employees, local governments, and peers helped the Texas operation exceed its goal by reducing water

consumption by 10.6%

Freeport Water Conservation Implementation

Action Savings (gpm)

Recycle cooling water at chlorine plant and air compressor 1,300

Use seawater for cooling tower 200-600

Modify reservoir and demin water plant 1,600

Upgrade plant product softened water infrastructure 2500

Reuse Lake Jackson wastewater 2500

Tarragona’s Water Crisis

Province of Tarragona struggled with water shortage for many years

Urban, tourist and industrial activities concentrated in area < 200 km²

Chronic water supply shortages were solved with water transfer from Ebro Delta irrigation district. Transfer now completely allocated in Summer. System unable to accept new water demands.

Province decided to reuse reclaimed water from two urban wastewater treatment plants to supply Industrial Petrochemical Area.

Supply replaces freshwater from Ebro River, releasing volume for drinking water supply to the population.

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Process Flow Diagram

DiscFilter®

Sand

Filter

Waste

Water

Product water

1st PassRO

Antiscalant

2nd Pass ROACTIFLO®

Multimedia

Filter

UV

Design and implementation by VeoliaWater Solutions & Technology

19,000 m3/d, <0.8 mg/l NH3

Dow Terneuzen, the Netherlands

City of Terneuzen

Dow site

DOW RESTRICTED - For internal use onlyInformation

Dow site

Biesbosch

Flanders

Zeeland – land in water Dow and its fresh water supply

Municipal Wastewater

Treatment Plant (Water Board)

Evides desalinates using FilmtecEW/BW membranes

High purity fresh water

Dow uses fresh waterfor high pressuresteam production

Various plants discharge a mixture offresh and salt wastewater – Dow issegregating salt and fresh water streams aiming to reclaim fresh water for reuse

Salt wastewater

Fresh wastewater

Biologicaltreatment of fresh wastewater

Biological Treatment of salt wastewaterSalt wastewater is discharged

to the river after treatment

After treatment fresh water is being reused as feed water for cooling towers

Water evaporatesin cooling towers

Dow processes are cooled with water

Fresh water used In households

1ste cycle

3e cycle

2e cycle

Biesbosch

Naphtha Cracker‐3 Cooling Towerfed with > 50% WWTP effluent recycle

2‐3 million m³/year

Integrated urban & industrial watercycle WWTP with MBR to feed industrial RO

Integrated urban & industrial watercycleWWTP with MBR to feed industrial RO (2010)

City effluent upgraded to ultra pure water used in Dow Hydrocarbons Cracker

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Bos-atlasPg 38

Dow Terneuzen Site Water ReuseDescriptionDow’s second largest plant globally, reuses municipal household wastewater twice in its manufacturing process

Sustainability Profile• Dow accepts 10,000 m³ of water every 24

hours and purifies more than 70 percent of it to generate steam and feed manufacturing plants

• Reduced energy use equivalent to lowering CO2 emissions by 5,000 tons per year

• Process reduces the energy use for water purification by 65 percent

AWARD WINNER

Int. Conf. on Information Systems Innovation

“Most Innovative Corporate Social Responsibility Project”

2008

Water Goal for Terneuzen

“Dow Terneuzen is depending on supply of fresh water to continue its operations”

2010 status• 35% supply from Biesbosch area (major potable water source for SW

region)• 65% supply with internal and external reuse water

2015 goal• 80% supply with reuse water

2020 goal• 100% supply with reuse water

Orange County Water District

Low E RO technology for expansion

Barrier Wells

SpreadingBasins

Santa AnaRiver

UVRO

UV

MicrofiltrationOCSDEffluent

Orange County Water District’s (OCWD) Groundwater Replenishment System (GWRS)

• World’s largest advanced water purification system for indirect potable reuse

• Current capacity: 70 mgd = 15,750 RO membranes

• Expansion: 30 mgd = 6,300 RO membranes => Dow’s XFRLE‐400/34i

• 60% of all energy usage consumed by RO

Membrane Specific Flux

(gfd/psi)

Feed Pressure

(psi)

Specific Energy

(kWh/kgal)

Cost/yr ($USD/yr)

Savings/yr ($USD/yr)

XFRLE-400/34i

0.125 94 1.07 2.02 million $270,000

Current membrane

0.11 107 1.21 2.29 million - -

Summary  of Trial Results

XFRLE RO demonstrated excellent, repeatable performance in terms of enhanced permeability and high 

rejection  XFRLE provides a projected OPEX savings of 

~$270,000/yr over the membrane currently used in the 70 mgd system

Newer Membrane UpdateFlux improvement= 13%

Specific E=1.00 kWhr/000 gal

Potential savings of $400k

Water Soluble Organics

Conventional de-oiling technologies• Produced Water systems are designed to meet O&G specs

• Success is defined by measurement chosen

• Remove free, dispersed and emulsified oil in produced water

• Generally not effective for water soluble and semi-soluble petroleum hydrocarbons.

Awareness of WSO is being driven by

• Tightening Environmental regulations

• Impact of residuals on advanced treatment technologies

Off-site Disposal On-siteRegeneration

Media Activated Carbon Regenerable Adsorbent

Rate of Removal 10 lbs/hr 10 lbs/hr

240 lbs/day consumed 24 hr Regeneration Cycles

Media Requirement 86,400 lbs per year 2 x 240 lbs media

Cost of Media $216,000/yr@$2.5/lb with disposal

$20,000 initial fillEvery 3-5 years

Carbon is cheap to buy but expensive to use

Why Improve on Activated Carbon?

Synthetic Adsorbents

Synthetic adsorbents can be engineered to overcome the shortcomings of Activated Carbon

How much can they remove? • Loading similar to AC

High Surface Area • Adsorption & desorption rates• >1,100 m2/gram-polymer

How fast is regeneration?

Treatment

99.9% removal of GROs92.4% removal of DROs98.4% removal of TPHs

TPH (ppm) 20,000 bwpd 50,000 bwpd 100,000 bwpd

200 $128,000 $320,000 $640,000

500 $320,000 $800,000 $1.6 Million

1000 $640,000 $1.6 Million $3.2 Million

(assume a value of recovered NGLs of $80/bbl)

Recovered Condensates, NGLS can offset some or all of the OPEX

Value of Recovered HydrocarbonsLight Hydrocarbons – BTEX, GRO, DRO and TPH all have potential

value as salable products (annual)

Trends Driving Water Innovations

• Shale gas & oil development will spur manufacturing

• “New Water” for manufacturing requires reuse and seawater desalination

• Arable land diminishing, water scarcity

• Ag must double production to meet demand by 2050

• Infrastructure and Transportation

• People are using 3x as much water as they did 50 years ago

• Consumerism

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Summary

Water reuse- all case studies required partnerships as success enablers

Technology from simple to complex highlighted

Civil Engineering and Permitting

System designs with technology components

Complex integration schemes

Advanced and sophisticated components

DOW FILMTEC™

RO ElementsAMBER™ Ion Exchange Resin

DOW™

Ultrafiltration Modules

TEQUATIC™ Fine Particle Filter

DOW™

EDI Modules

ADSORBSIA™

Media

DOWEX™ Ion Exchange Resin

CATALYSIS & CHEMICAL

PROCESSING

FOOD & BEVERAGE POWER GENERATION

MINING & HYDROMETALLURG

Y

WASTEWATER & REUSE

RESIDENTIAL & COMMERICIAL

MUNICIPAL & DESALINATION

PHARMACEUTICALINDUSTRIAL WATER

Prod

uct

Plat

form

sM

arke

ts S

erve

d

OILFIELD WATER

™Trademark of the Dow Chemical CompanyClean Filtration Technologies, LLC is a wholly Owned Subsidiary of The Dow Chemical Company

Dow Water & Process Solutions

Specific Energy Trends in Brackish Water Desalination

Substantial improvements in membrane now are leading to smaller returns in energy savings due to other contributing factors

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Thermodynamic Minimum

No membrane resistance, Infinite Capital Cost

FILMTECTM ECO Membranes Novel Low Energy Membranes

• Next generation membrane technology allowing a true step-change in performance

• Novel low energy elements enable new levels of rejection, breaking the old thinking patterns between low energy and high rejection membranes

• Energy savings >30+% with 99.7% salt rejection

• Fundamental technology innovation protected with over dozen patents 0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.13 0.18 0.23 0.28 0.33 0.38 0.43

B ‐Salt p

ermeability (GFD

)

A ‐Water Permeability ( GFD)

GEN I

GEN II

GEN III

BW NFLE

HRLE, XFRLE 

BW30HR, BW30XFR 

LC‐LE 

GEN II2009

BW 30, FR

LE

XLE 

XLE

GEN I1990s

ECO

GEN III2012

INNOVATION In Polyamide Chemistry

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TEQUATICTM PLUS Fine Particle FilterIdeally Suited for High Solids Water

Optimized Design For High TSS Continuous Cleaning Cross-flow Filtration Centrifugal Separation Settling and Solids Collection

Performance Filtration to 10m Operation upto 10,000 TSS

Markets Industrial WW and Reuse Oilfield Water

TEQUATIC™ PLUS Filter

1. Centrifugal force pushes dense particles outward

2. Vortex chamber continuously cleans filter

3. Solids are recirculated

4. Settled solids are purged

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