l32 ro water extra

8/20/2019 L32 RO Water Extra

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Oilfield BrinesOilfield Brines ConversionConversion

o reso res a er a er

Lecture # 32?Lecture # 32?

Maria A. Barrufet


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Tentative AgendaTentative Agenda

Problem that triggered this researchProblem that triggered this research

Strategy to solve the problem and make it a revenueStrategy to solve the problem and make it a revenuesourcesource

Objectives and TasksObjectives and TasksEngineering Design and OptimizationEngineering Design and Optimization

Oil/water and reverse osmosis separation processesOil/water and reverse osmosis separation processesData collection and analysisData collection and analysisProcess inte rationProcess inte ration

FutureFutureDiscussionsDiscussions


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ProblemsProblemsIncreasin costs of dis osal of waste brine fromIncreasin costs of dis osal of waste brine from

oil and gas production operationsoil and gas production operationsPermian Basin produces over 400 mil lion gallons ofwa er per ayEquivalent to the daily use of water in the city ofHouston

Limited sources of fresh water for communitiesLimited sources of fresh water for communitiesand industryand industry

Oilfield brines unacceptable for irrigation,Oilfield brines unacceptable for irrigation,industrial, or municipal useindustrial, or municipal use


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Our Proposed SolutionOur Proposed Solution--

Convert oilfield brines to irrigation and freshConvert oilfield brines to irrigation and freshwaterwaterDesign and build portable units for waterDesign and build portable units for watertreatmenttreatment

Accommodate variation in input stream Accommodate variation in input streamcharacteristicscharacteristicsPlan for automated operation, reliability andPlan for automated operation, reliability andsafetysafety


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Not a simple desalination task…Not a simple desalination task…

integration and adaptation of differentintegration and adaptation of differenttechnologiestechnologies

Suspended solidsSuspended solids

Emulsified oil (s)Emulsified oil (s) Remote locations away from distributionRemote locations away from distributionnetworksnetworksDifferent types and concentrations of dissolvedDifferent types and concentrations of dissolvedsolids (TDS)solids (TDS)


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Total Dissolved Solids (TDS)Total Dissolved Solids (TDS)


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Generalized Brine ConversionGeneralized Brine ConversionProcessProcess

Oil W aste-b

Biocide/Chem.

CX-101

Centrifugal ExtractionS-107

Oil Waste-a

Flow Splitting

Coalescer / OS-101

Oil Separation

P-13 / CY-101

Hydrocyclone

Source BrineP-9 / FSP-103

Flow Splitting

S-106 S-108

S-109 S-110

O1

S-111

Oil W aste-c

Organo Clay / OC

S-103

S-104

Permeate

Holding Tank / Vt Reverse Osmosis / ROReject

S-112

Disposal


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Suspended/Dissolved SolidSuspended/Dissolved SolidSeparation LevelsSeparation Levels

Micro Filtration ( MF) (10- 0.1 μm)Bacteria sus ended articles

Ultrafiltration ( UF ) (0.05-0.005 μm)Colloids, macromolecules

Nanofilt ration ( NF ) (5e -3-5.e -4 μm)Sugars, dyes, divalent salts

Reverse Osmosis ( RO ) (1.e -4-1e -5 μm)Monovalent salts, ionic metals

Water


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Natural Osmosis PrincipleNatural Osmosis PrincipleSelective barrier Selective barrier

Selective Membrane

Osmotic Pressure

C,Tf r=


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Reverse Osmosis PrincipleReverse Osmosis Principle

OSMOSIS REVERSE OSMOSIS

Applied

Head = OsmoticPressure

Semi-permeableMembrane

Pressure

Initial Brine

ConcentratedBrine

or pure water

Water FlowWater Flow


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Membrane Configurations andMembrane Configurations andMaterialsMaterials

S iralS iral--wound modulewound module

Hollow fiber moduleHollow fiber module


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TerminologyTerminologyRejectionRejection

FP C/C1R TransmembraneTransmembranepressurepressure

PRF P

2PP

TMP ⎥⎦

⎤⎢⎣

⎡ =, ,, ,

or concentrate ratesor concentrate rates-- PF

(volumetric rate/area)(volumetric rate/area)

JJ ww = flux of permeate= flux of permeateCC

Fx

y P


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Reverse Osmosis GoverningReverse Osmosis GoverningEquationsEquations

PvCD www = ~RTtw

kT

= r

=pww r 6= ,


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Osmotic PressureOsmotic PressureOsmotic Pressure vs TDS**

500

600 s i a ) T = 200 F

400

s s u r e

( =

200 o t

i c P r

r

0 O s ,

TDS %


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Osmotic Pressure as a FunctionOsmotic Pressure as a Functionof Concentration (T = 70of Concentration (T = 70 ooF)F)

ComponentComponent 2%2% 5%5% 10%10% 15%15%

Sucrose (Sucrose ( 342342 )) 24 *24 * 6363 134134 215215

Glucose (Glucose ( 180180 )) 4848 127127 264264 405405SeawaterSeawater 220220 550550 12051205

NaCl (NaCl ( 58.558.5 )) 250250 620620

..

KK22SOSO 44 ((174.3174.3 )) 9292 235235 470470

M SOM SO 120.4120.4 6565 168168 352352

Molecular weight in ( ) * Pressure in (psia)Molecular weight in ( ) * Pressure in (psia)


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Brine CharacteristicsBrine Characteristics

TOC up to 5,000 ppm (dissolved and emulsified)TOC up to 5,000 ppm (dissolved and emulsified)

,,

Desired Output:Desired Output:

Oil (TOC) < 20 ppmOil (TOC) < 20 ppm

,,adsorption, centrifuge, NF, RO…adsorption, centrifuge, NF, RO…


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Process Components andProcess Components andStreamsStreams

-

Oil Wa ste-bBiocide/Chem.

CX-101

Centrifugal ExtractionP-9 / FSP-103

Flow Splitting

-

S-102S-105

Source Brine

S-103

S-101

Organo Clay / OC

Holding Tank / Vt Reverse Osmosis / RO

S-104

Permeate

S-112

Reject

Disposal


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ObjectivesObjectivesMaximize ermeate roductionMaximize ermeate roduction

Minimize waste volume (concentratedMinimize waste volume (concentratedbrinebrineEliminate bottlenecksEliminate bottlenecks

Enable semiEnable semi- -continuous o eration loncontinuous o eration lonbatch cycles)batch cycles)Provide lowProvide low- -cost process, maintenance,cost process, maintenance,and operationand operationMinimize manual intervention (automate)Minimize manual intervention (automate)Portable, reliable, controllablePortable, reliable, controllable


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Oil/Water SeparationOil/Water Separation

Oil adsorption inOil adsorption inpacked columnspacked columns

organoc ayorganoc aypellets)pellets)


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Oil Emulsion & AnalysisOil Emulsion & Analysis


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Measurement of Oil in WaterMeasurement of Oil in WaterCalibration IssuesCalibration Issues

eren o con am nan s requ reeren o con am nan s requ rerecalibration of the equipmentrecalibration of the equipmentEquipment response linear up to 1,000 mvEquipment response linear up to 1,000 mv

Dilutions needed for water samples withDilutions needed for water samples withhigh oil concentrations (>200 ppm)high oil concentrations (>200 ppm)TimeTime--consuming techniqueconsuming technique


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Schematics of the CoalescingSchematics of the CoalescingMediaMedia

Coalescer MediaCoalescer Media

TankTank Coalescer Coalescer


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33-- to 10to 10--Fold Oil ConcentrationFold Oil ConcentrationReductionReduction

y = 0.3217ey = 0.3217e 0.5219x0.5219x

RR22 = 0.9437= 0.94371128028011440440 800800 ppmppm

1600 ppm1600 ppm

y = 0.2499ey = 0.2499e 0.4702x0.4702x

RR22 = 0.9911= 0.9911

0.358x0.358x800800

960960

11120120

l l ] , ] , p p m

p p m

6400 ppm6400 ppm

y = . ey = . e ..

RR22 = 0.9934= 0.9934

320320

480480

640640 [ [ O i O i

y = 0.1166ey = 0.1166e..

RR22 = 0.7767= 0.7767

00

160160

0.20.2 0.70.7 1.21.2 1.71.7 2.22.2 2.72.7 3.23.2

Q, L/minQ, L/min


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Adsor tion Ex eriments Adsor tion Ex erimentsPacking organoclayPacking organoclay

uuFlow loop and sampleFlow loop and sample

Sample collection andSample collection and

Modeling oil adsorptionModeling oil adsorption

raterateBreakthrough timesBreakthrough times


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Organoclay Before & After OilOrganoclay Before & After Oil Adsorption Adsorption


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Sharp front indicates higherSharp front indicates higherefficiencyefficiency

xpe r men

0.8

1

i o n C fin al / C in iti al

0.6 o n c e n

t r a

i o )

outletC0.4

/ C f ( o i l c r a

inletC

0

. C i

Time (minu te s)


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OC Adsorption ModelingOC Adsorption Modeling

Process governed by mass-transfer

First-order kineticsens v y ana ys s o res ence me


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Second Column Brings OutletTOC Below Limit

Oil Adsorp tion Performance

100.0

125.0

, p p m

50.0

.

u t l e t T O C

P-1 / GMF-101

OC Filtration

P-2 / GMF-102

OC Filtration

S-115

0.0

.

0.0 50.0 100.0 150.0 200.0 250.0

O

t me, ours

Column 1 Column 2 TOC Limit, ppm Feed TOC, ppm


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Desalination (RO)Desalination (RO)

1.3 gpm (OC)

FeedPermeate

en ng orageReverse Osmosis Recycle


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RO SystemRO System - - Pilot Unit UsedPilot Unit Used


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RO ExperimentsRO Experiments - - SpecsSpecs

- -

TMP (600 – 1000 psi)= 2m

Recycle on/off

Inlet TDS (0 – 40,000ppm)Feed rate (6 – 14


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Recovery Decreases withPressure, Increasing Flow Rate

Feed = Pure Water

0.30

0.35

c t i o n

0.20

0.25

o v e r y

f r a

6 gpm

8 gpm

0.05

0.10

.

m e a

t e r e 10 gpm

0.000 200 400 600 800 1000

Transmem brane ressure si

P e


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Increasing Salt FurtherDecreases Recovery

,

0.20 t i o n

0.12

.

o v e r y

f r a

6 gpm

8 gpm

0.04

.

m e a

t e r e 10 gpm

0.00450 550 650 750

Transmembrane pressure, psi

P e r


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Increasing TMP Increases SaltRejection

Feed = 40,000 mg/L NaCl99.00

97.00

98.00

c t i o n ,

%

6 gpm

8 m

96.00 S a l

t r e j

10 gpm

95.00550 600 650 700 750 800

,


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Salt Rejection Improves at LowerConcentration

Feed = 10,000 mg/L NaCl99.60

%

98.80

99.20

e j e c

t i o n ,

6 gpm

8 gpm

98.40 S a l

t10 gpm

98.00250 350 450 550 650 750

Transmembrane ressure, si


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RO Data SummaryRO Data Summary

– – ,,

TMP range 200TMP range 200 –– 800 psia800 psia

Data points triplicate (yesData points triplicate (yes— —3 repetitions)3 repetitions)Over 450 data pointsOver 450 data pointsUncertaintyUncertainty ++ 0.5 % in permeate0.5 % in permeate

concentration measurement andconcentration measurement and + + 1.5% in1.5% inrate measurementrate measurement


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Least Squares RegressionLeast Squares Regression

⎥⎤

⎢⎡ ⎞⎛ ⎞⎛ ⎞⎛ 6

aTDS4

aTDS2a

TMP

⎥⎦

⎢⎣

⎟ ⎠

⎜⎝ ⎠⎝

⎟ ⎠

⎜⎝ FJ

5TMP3F

J1w

Total TDS rejectionTotal TDS rejection

⎥⎥

⎢⎢

⎟⎟

⎜⎜+⎟

⎠ ⎞⎜

⎝ ⎛ +

⎟⎟

⎜⎜= 6

FJ

TDS5

b4bTMPTDS

3b2

FJ

TMP1

bR


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Rejection Model Matches RealData

Membrane: SWC1- 4040NaCl Rejection % (Error Bars 0.5%)

100+

98

99

i c t e d

95

96 P r e

d

9494 95 96 97 98 99 100


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Permeate Flow Model MatchesReal Data

Membrane: SWC1- 4040

Permeate Flow as % of Feed (Error Bars 1.5%)30 +

20

25

i c t e d

5

10 P r e

d

00 5 10 15 20 25 30

xper men a


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Scenario 1: ConstantScenario 1: Constant- -Feed TDSFeed TDS

Propose desired permeate (freshwater) rate orPropose desired permeate (freshwater) rate ora y pro uc ona y pro uc on

Select transmembrane pressureSelect transmembrane pressure (greater than(greater than Δππ))Obtain required membrane areaObtain required membrane area A A mmSelectSelect L / AL / A

Obtain required feedObtain required feed- -flow rateflow rate


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Operating Conditions DesignOperating Conditions Design

100000 30

/

25

v W A

mqP =15000 gal/day

10000

L/A=25 m -1

10000 - w S

) P A

m

15

20

) k

/ ( 1 - w S

)

5000

400015

20

5 . 5 9 v W

( 1

10

( q P / ( q F - q

2000

10008

10

1000 0

5 0 . 0 2

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

(1 -ΔΠ

/Δ

P)


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Begin Design

Set u O erat in Condi tions:Pump specifications, q F, T, and Brine Composition

Evaluate: r b , m w, w s ,p, v w

Set ΔP and desired qP

(gal/day)

Δ

Stageso a ne va ue or x-ax s - - π Δ an q P

evaluate A m from left y-axis

Propose L/A (m -1)

Obtain q F from right y-axis

No NoIs q F within allowed

range

Yes

End


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Design ExampleDesign Example

Given rocess arameters and desired outcomeGiven rocess arameters and desired outcomeTDSTDS == 18,000 ppm18,000 ppmTT == 160160 °° FF

qq PP == 5,000 gal/day5,000 gal/day

SolutionSolutionΔππ = 192 psi= 192 psi

== 22 ..ProposePropose - - L/AL/A == 15 m15 m --11Right axisRight axis qq FF = 69,000 gal/day= 69,000 gal/day (7%)(7%)


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Scenario 2 (more likely)Scenario 2 (more likely)

For aFor a variablevariable salt concentration in the feedsalt concentration in the feed

(caused by recycling of concentrate)(caused by recycling of concentrate)

Given membrane area, feed rate, and TMPGiven membrane area, feed rate, and TMP

Estimate permeate volume and batch timeEstimate permeate volume and batch time

Number of units requiredNumber of units required

Series/parallel configurationSeries/parallel configurationPartial/ful l recycle, makePartial/full recycle, make- -up streamsup streams


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Example Results From RO DesignExample Results From RO Design

== ,,

1 RO unit (A1 RO unit (A mm = 70 ft= 70 ft 22)) ..

Holding tank volume 50Holding tank volume 50 75 gallons75 gallonsFeed rate = 6 GPMFeed rate = 6 GPMTMP = 750 psiaTMP = 750 psia

Full recycleFull recycle


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Example Results From RO DesignExample Results From RO Design

Batch ends whenBatch ends when ,,

1.3 gpm (OC)

VVtt > 75 gallons> 75 gallonsVV

tt< Feed rate< Feed rate

Feed

Permeate TDS >Permeate TDS >Blending / Storage

Reverse Osmosis Recycle

Permeate

500 ppm500 ppm


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Transient Behavior Transient Behavior Cumulative Permeate Production & Recovery Efficiency

250.0 0.880.0Cumulative & Instantaneous Permeate Concentration

350.0Inst - m

150.0

200.0

G a l

l o n s

0.50.6

.

P + R )

70.0

m e , g a

l

250.0

300.0Cum - ppm

100.0

o d u c t

i o n ,

0.3

0.4

R E =

P / (

50.0

.

T a n

k V o l

150.0

200.0

T D S

, p p m

0.0

50.0 P

0

0.1

.

40.0 H o l

d i n g

50.0

100.0

0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Time, hrs30.00.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

0.00.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

,,


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TMP analysis (600, 800, 1000 psia)TMP analysis (600, 800, 1000 psia)Specifications

RO - SWC-1-4040 - 6GPM - (70SF)

250.0

300.0 e d ,

50.0

100.0

150.0

200.0

P e r m e a

t e P r o

d u

g a l l o n s 600 psia

800 psia

1000 psia

Specifications- - - - -.

0.00 1.00 2.00 3.00 4.00 5.00

time, hours

20000.0

30000.0

40000.0

50000.0

d T D S

, p p m

600 psia

800 psia

0.0

10000.0

0.00 1.00 2.00 3.00 4.00 5.00

time, hours

F e e 1000 psia

SpecificationsRO - SWC-1-4040 - 6GPM - (70SF)

40.0

60.0

80.0

l d i n g

T a n k

u m e , g a

l l o n s

600 psia

800 psia

1000 psia

0.0

.

0.00 1.00 2.00 3.00 4.00 5.00

time, hours

H V o l


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TMP AnalysisTMP Analysis

Increase size of Increase size of


1.0

1.2

i e n c y

holding tankholding tankUse two tanksUse two tanks0.0

0.20.4

0.6

.

R e c o v e r y

E f f i c

600 psia

800 psia

1000 psia

Increase feed rateIncrease feed ratefrom OC trainfrom OC train

0.00 1.00 2.00 3.00 4.00 5.00

time, hours

u …u …resize OC columnsresize OC columns


0.30

0.40

F r a c

t i o n

OC columnsOC columns0.10

0.20

0.00 1.00 2.00 3.00 4.00 5.00

P e r m e a t e

800 psia

1000 psia

time, hours


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RO Performance: Feed RateRO Performance: Feed Rate Analysis Analysis

= = - ,

0.30

0.35

r a c t

i o n

6 gpm

0.15

0.20

0.25

P e r m e a

t e 8 gpm

10 gpm

12 gpmMembrane Performance (TMP=1000 psia , 6GPM)

0.00 0.50 1.00 1.50 2.00

time, hours

0.25

0.30

0.35

e F r a c

t i o n

Vt (50-150)

0.15

0.20 P e r m e a

t Vt (100-150)

Vt (150-150)

. . . . . . .

time, hours


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Design ScenariosDesign Scenarios

Batch TDS (F) Permeate TDS(P) Recovery TDS Volume Units Feed TMP

(h) (ppm) Tank (N,C),

3.92 32728 282 174 0.79 5000 50,75 2,1 6 8004.03 32241 291 204 0.80 5000 50,75 2,1 8 8004.13 31880 299 212 0.80 5000 50,75 2,1 10 8002.07 35920 137 237 0.65 10000 50,75 2,1 6 8002.12 35526 141 287 0.65 10000 50,75 2,1 6 8002.17 35245 145 305 0.66 10000 50,75 2,1 6 8000.47 39357 25 436 0.29 25000 50,80 2,1 6 8000.88 39594 47 439 0.28 25000 100 150 2 1 6 800 0.75 39422 82 424 0.52 25000 100,150 2,2 6 8000.65 39426 108 411 0.72 25000 100,150 2,3 6 8000.50 36660 115 374 0.83 25000 100,150 2,4 6 8000.42 39242 91 422 0.55 25000 100,150 4,4 6 800

. . , ,

0.58 39557 126 434 0.37 25000 200,300 4,4 6 8000.60 39415 130 560 0.38 25000 200,300 4,4 8 8000.52 39026 166 356 0.52 25000 200,300 4,4 8 10000.75 11497 342 27 0.91 5000 200,300 4,4 8 1000


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ScaleScale- -Up IssuesUp Issues

S-110S-115

P-1 / GMF-101

OC Fil tration

P-2 / GMF-102

OC Fil tration P-3 / RO-101

Reverse OsmosisS-102

S-113

S-114

S-116

P-4 / RO-102

Reverse OsmosisP-11 / FSP-101

S-101

S-103

S-104

S-106

-

P-5 / RO-103

Reverse Osmosis

P-9 / V-101

Holdin g TankP-10 / V-102

Storage

S-105

P-12 / V-103

Permeate

S-108

S-109S-117

P-6 / RO-104

Reverse Osmosis S-111

S-112

S-118

S-119

P-7 / GMF-103

OC Fil trationP-8

OC Fil tration

kk


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Future WorkFuture Work

materials at higher pressurematerials at higher pressure--

membrane specificationsmembrane specifications

accommodate different packingaccommodate different packing --

Analyze scaling, fouling Analyze scaling, fouling

F W kF W k


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, , ,, , ,

aging)aging)Monitorin cleanin fre uenc and a entsMonitorin cleanin fre uenc and a entsPrevention (extend membrane life)Prevention (extend membrane life)

Permeate

Flux

Cleaning

F W kF W k


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wa er separa on wwa er separa on whydrocycloneshydrocyclones

No chemicals or cleaning neededNo chemicals or cleaning needed

costcostNo Movin PartsNo Movin Parts Recycle optionsRecycle options

Vi iVi i 20202020 d b dd b d


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VisionVision 20202020 and beyond…and beyond…

Work with local, state and federal agencies toWork with local, state and federal agencies toincorporate this new process into permittedincorporate this new process into permittedoperationsoperationsDevelo new and faster online sensors for TDSDevelo new and faster online sensors for TDSand for selected metals (biosensors,and for selected metals (biosensors, nano nano--sensors)sensors)

continuous operationcontinuous operation

Analyze hybrid RO systems Analyze hybrid RO systems – – Wind powerWind power,,

Evaluate beneficial uses of waste (roadEvaluate beneficial uses of waste (roaddesalting, construction materials, landscaping)desalting, construction materials, landscaping)

I t di i li PI t di i li P


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Interdisciplinary ProgramInterdisciplinary Program

Fi i l S tFi i l S t


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Financial SupportFinancial Support

CONACYT (Mexico, A&M)CONACYT (Mexico, A&M) , ,, ,

ChevronTexaco)ChevronTexaco)o ymer en ureso ymer en ures

TWRITWRI

l32 ro water extra

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