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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
SpecificationsRO - SWC-1-4040 - 6GPM - (70SF)
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
SpecificationsRO - SWC-1-4040 - 6GPM - (70SF)
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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Future WorkFuture Work
, , ,, , ,
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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Future WorkFuture Work
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