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Complementary Material

Oilfield Brines Conversion


t Fresh
to
F
h Water
W t
Lecture # 32?
PETE 310
Maria A. Barrufet

Tentative Agenda
g
Problem that triggered
gg
this research
Strategy to solve the problem and make it a revenue
source
Terminology (Basic principles)
Objectives and Tasks
Engineering Design and Optimization
Oil/water and reverse osmosis separation processes
Data collection and analysis
Process integration
g

Future
Discussions

Problems
Increasing costs of disposal of waste brine from
oil and gas production operations
Permian Basin produces over 400 million gallons of
water
t per d
day
Equivalent to the daily use of water in the city of
Houston

Limited sources of fresh water for communities


and industry
Oilfield brines unacceptable for irrigation,
industrial, or municipal use

Our Proposed Solution


Reuse water onon-site
Convert oilfield brines to irrigation and fresh
water
Design and build portable units for water
treatment
Accommodate variation in input stream
characteristics
Plan for automated operation, reliability and
safety

Not a simple desalination task


Processing oilfield brines requires
integration and adaptation of different
technologies
Suspended solids
Emulsified oil (s)
Multiple point sources
Remote locations away from distribution
networks
Different types and concentrations of dissolved
solids (TDS)

Total Dissolved Solids ((TDS))

Generalized Brine Conversion


Process
Biocide/Chem.

Oil Waste-b
Oil Waste-a
S-107

Source Brine

O1Coalescer / OS-101

S-106

CX-101
Centrifugal Extraction

S-108

Oil Waste-c

P-9 / FSP-103

Oil Separation

Flow Splitting

Flow Splitting

P-13 / CY-101
S-111

Hydrocyclone

S-109

S-103

Organo Clay / OC
Permeate
S-104

Reverse Osmosis / RO

Holding Tank / Vt

Reject
S-112

Disposal

S-110

Suspended/Dissolved Solid
Separation Levels
Micro Filtration (MF) (10- 0.1m)
Bacteria, suspended particles
Ultrafiltration (UF) (0.05-0.005m)
Colloids, macromolecules
Nanofiltration (NF) (5e-3-5.e-4 m)
Sugars, dyes, divalent salts
Reverse Osmosis (RO) (1.e-4-1e-5 m)
Monovalent salts, ionic metals
Water

Natural Osmosis Principle


Selective barrier

Selective Membrane

Osmotic Pressure

( )

r
= f T , C

Reverse Osmosis Principle


OSMOSIS

REVERSE OSMOSIS

Head = Osmotic
Pressure
Applied
Pressure
Semi-permeable
Membrane
Diluted Brine
Initial Brine
or pure water
Water Flow

Concentrated
Brine

Water Flow

Membrane Configurations and


Materials
Spiral--wound module
Spiral

Hollow fiber module

Terminology
gy
Rejection
T
Transmembrane
b
pressure
Feed,
Feed permeate,
permeate reject
or concentrate rates
scale--up use fluxes
For scale
(volumetric rate/area)
Jw = flux of permeate

R = 1 CP / CF
P + PR
TMP = F
PP

P
x

C
F

Reverse Osmosis Governing


Equations

~
Dw Cw v w (P )
Jw =
RTt
Dw =

kT
6 w rp

( )

r
= f T , C

Osmotic Pressure
Osmotic Pressure vs TDS**
Osm
motic Pre
essure (p
psia)

600
T = 200 F
500

T = 100 F

400
300

( )

r
= f T ,C

200
100
0
0

3
TDS %

Osmotic Pressure as a Function


of Concentration (T = 70 oF)
Component

2%

5%

10%

15%

Sucrose (342
(342))

24 *

63

134

215

Glucose (180
(180))

48

127

264

405

Seawater

220

550

1205

NaCl (58.5
(58.5))

250

620

KCl (74
((74.6
74.6)
74 6)
6)

170

455

965

K2SO4 (174.3
174.3))

92

235

470

g 4 (120.4
120.4))
MgSO

65

168

352

Molecular weight in ( )

* Pressure in (psia)

Brine Characteristics
Input Waste Product:
TOC up to 5,000 ppm (dissolved and emulsified)
TDS up to 100,000 ppm

Desired Output:
Water (TDS) < 500 - 15 ppm
Oil (TOC) < 20 ppm

Technology: Coalescing media,


media Organoclay
adsorption, centrifuge, NF, RO

Process Components and


Streams
Biocide/Chem.

Oil Waste-b
S-107

CX-101
Centrifugal Extraction

S-102
P-9 / FSP-103

S-105

Flow Splitting

S-101

Source Brine

S-103

Organo Clay / OC

Permeate
S-104

Holding Tank / Vt

S-112

Reverse Osmosis / RO
Reject

Disposal

Objectives
j
Maximize permeate production
Minimize waste volume (concentrated
brine))
Eliminate bottlenecks
Enable semisemi-continuous operation
p
(long
( g
batch cycles)
Provide low
low--cost process, maintenance,
and operation
Minimize manual intervention (automate)
Portable, reliable, controllable

Oil/Water Separation
Coalescing media

Oil adsorption in
packed columns
(
(organoclay
l
pellets)

Oil Emulsion & Analysis


y

Measurement of Oil in Water


Calibration Issues
Different
Diff
t oil
il contaminants
t i
t require
i
recalibration of the equipment
E i
Equipment
response linear
li
up to 1,000
1 000 mv
Dilutions needed for water samples with
high oil concentrations (>200 ppm)
Time--consuming technique
Time

Schematics of the Coalescing


Media

Coalescer Media

Pump
Tank

Coalescer

3- to 1010-Fold Oil Concentration


Reduction
1600

800 ppm
1600 ppm
3200 ppm
6400 ppm

1440
1280

[Oill], ppm

1120
960

0.5219x

y = 0.3217e
2
R = 0.9437

0.4702x

y = 0.2499e
2
R = 0.9911

800

0.358x

y = 0.1949e
0 1949
2
R = 0.9934

640
480
320

0 2027x
0.2027x

y = 0.1166e
2
R = 0.7767

160
0
0.2

0.7

1.2

1.7

2.2
Q, L/min

2.7

3.2

Adsorption
Experiments
p
p
Packing organoclay
column
col mn
Flow loop and sample
preparation
Sample collection and
TOC Analysis
Modeling oil adsorption
Bed dimensions and
rate
Breakthrough times

Organoclay Before & After Oil


Adsorption

Sharp front indicates higher


efficiency
E
Expe
rime
i
ntt 12

C i / Cf (oil co
oncentrattion
rattio)

C final / C initial
0.8

Coutlet 0.6
Cinlet 0.4
02
0.2
0
0

50

100
150
Time (minute s)

200

250

OC Adsorption Modeling
g
Negligible axial dispersion
Process governed by mass-transfer
resistance
First-order kinetics
S
Sensitivity
iti it analysis
l i to
t residence
id
time
ti

Second Column Brings Outlet


TOC Below Limit
Oil Adsorption Performance
Two OC Columns In Series

Outlet TOC, ppm

125.0
100.0
75 0
75.0

S 115
S-115

50.0

P-1 / GMF-101

P-2 / GMF-102

OC Filtration

OC Filtration

25.0
0.0
0.0

50.0

100.0

150.0

200.0

250.0

ti
time,
hours
h
Column 1

Column 2

TOC Limit, ppm

Feed TOC, ppm

Desalination ((RO))

1.3 gpm (OC)

Feed
Permeate
Bl di
Blending
/ Storage
St
Reverse Osmosis

Recycle

RO System
y
- Pilot Unit Used

RO Experiments - Specs
SWC-1-4040
SWC 1 4040 spiral
TMP (600 1000 psi)
Am = 70 ft 2
Recycle on/off
Inlet TDS ((0 40,000
ppm)
Feed rate (6 14
GPM)

Recovery Decreases with


Pressure, Increasing Flow Rate
Perrmeate rec
covery fraction

Feed = Pure Water


0.35
0.30
0.25

6 gpm

0.20

8 gpm

0 15
0.15

10 gpm

0.10
0.05
0.00
0

200

400

600

800

pressure,, psi
p
Transmembrane p

1000

Increasing Salt Further


Decreases Recovery
Perrmeate rec
covery frac
ction

Feed = 30,000
30 000 mg/L NaCl
0.20
0 16
0.16
6 gpm

0.12

8 gpm
0 08
0.08

10 gpm

0.04
0.00
450

550

650

Transmembrane pressure, psi

750

Increasing TMP Increases Salt


Rejection
Feed = 40,000 mg/L NaCl

Salt reje
ection, %

99.00
98.00
6 gpm
97.00

8 gp
gpm
10 gpm

96.00
95.00
550

600

650

700

750

Transmembrane pressure
pressure, psi

800

Salt Rejection Improves at Lower


Concentration
Feed = 10,000 mg/L NaCl
Salt rrejection, %

99.60
99.20
6 gpm
98.80

8 gpm
10 gpm

98.40
98.00
250

350

450

550

650

pressure,, psi
p
Transmembrane p

750

RO Data Summary
y
TDS range from 0 40,000
40 000 ppm
TMP range 200 800 psia
Feed rate 6 to 10 gpm
Data points triplicate (yes
(yes3 repetitions)
Over 450 data points
Uncertainty + 0.5 % in permeate
concentration measurement and + 1.5% in
rate measurement

Least Squares Regression


g
Permeate flux

TMP
J = a
1 J
w
F

a
a
2
TDS
TDS
4

+a
+a

5 J
3 TMP

a
6

Total TDS rejection


TMP
= b
1 J
F

b
b
2
TDS
TDS
4

+b
+b

3 TMP
5 J

b
6

Rejection Model Matches Real


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

100

Predicted

99
98
97
96
95
94
94

95

96

97
Experimental

98

99

100

Permeate Flow Model Matches


Real Data
Membrane: SWC1- 4040
Permeate Flow as % of Feed
(Error Bars + 1.5% )
30

Pred
dicted

25
20
15
10
5
0
0

10

15
E
Experimental
i
t l

20

25

30

Scenario 1: ConstantConstant-Feed TDS


Propose desired permeate (freshwater) rate or
d il production
daily
d ti
Select transmembrane pressure (greater than
))
Ob i required
Obtain
i d membrane
b
area Am
Select L / A
Obtain required feedfeed-flow rate

Operating
g Conditions Design
g
30

qP =15000 gal/day

25

L/A=25 m-1

5.59 v W (1-w S) PAm /

10000

20

20
5000
4000

10000

15

15
3000
2000

10

10
8
1000

1000

0
0.3

0.4

0.5

0.6

0.7

(1 - / P)

0.8

0.9

1.0

0.028
8(qP/(qF-qP
P)k /(1-w S) v W Am

100000

Begin Design
Set up
p Operating
p
g Conditions:
Pump specifications, qF, T, and Brine Composition

Evaluate: rb, mw, ws,


p, vw

Design
Stages

Set P and desired qP (gal/day)

With obtained
bt i d value
l for
f x-axis
i - (1-/P)
(1 /P) and
d qP
evaluate Am from left y-axis

Propose L/A (m-1)

Obtain qF from right y-axis

No

Is qF within allowed
range
Yes
End

No

Design
g Example
Given p
process parameters
p
and desired outcome
TDS
T
TMP
qP

=
=
=
=

18,000 ppm
160 F
500 psia
5,000 gal/day

Solution
= 192 psi
Left axis Am = 39
39.53
53 m2
Propose - L/A =
15 m-1
Right axis qF = 69,000 gal/day (7%)

Scenario 2 (more likely)


For a variable salt concentration in the feed
(caused by recycling of concentrate)
Given membrane area,, feed rate,, and TMP
Estimate permeate volume and batch time

Design issues
Number of units required
Series/parallel configuration
Partial/full recycle, makemake-up streams

Example Results From RO Design


Initial TDS = 5,000
5 000 ppm
1 RO unit (Am = 70 ft2)
Flow rate from OC train is = 1
1.3
3 gpm
Holding tank volume 50 75 gallons
Feed rate = 6 GPM
TMP = 750 psia
Full recycle

Example Results From RO Design


Batch ends when
Feed > 40,000
40 000 ppm
1.3 gpm (OC)

Vt > 75 gallons
Vt < Feed rate

Feed
Permeate
Blending / Storage

Permeate TDS >


500 ppm

Reverse Osmosis

Recycle

Transient Behavior
Cumulative
& Instantaneous
Permeate
Concentration
Cumulative
Permeate
Production
& Recovery
Efficiency
0.8

TDS, ppm

HoldingPrroduction,
Tank Volu
ume,
gal
Gallons

350.0

300.0
200.0
70.0

Inst - pp
ppm

07
0.7

Cum - ppm

0.6

250.0
150.0

0.5

200.0
100.0
150.0
50.0

0.4

60 0
60.0

0.3
02
0.2

50.0
100.0

0.1

40.0
0.0
50.0
0.00
30.0
0.0
0.0
0.00

RE = P/((P+R)

80.0
250.0

0
0.50

0.5
0.50

1.00

1.0
1.00

1.50

2.00

2.50

Time, hrs
1.5
2.0
1.50
2.00

3.00

2.5
2.50

Volume Permeate
Produced
Time hrs
Time,
hrs
Time
Time,

3.50

3.0
3.00

3.5
3.50

TMP analysis (600, 800, 1000 psia)


300.0
250.0
200.0

600 psia

150.0

800 psia

100.0

1000 psia

50.0
0.0
0
0
0.00

Specifications
RO - SWC
SWC-1-4040
1 4040 - 6GPM - (70SF)
1.00

2.00

3.00

4.00

5.00
Feed TDS, ppm

Permeate Produc
ced,
gallons

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

time, hours

50000.0
40000.0
30000.0

600 psia

20000.0

800 psia

10000.0

1000 psia

0.0
0.00

Ho
olding Tank
Volu
ume, gallons

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

60.0

600 psia

40.0

800 psia
1000 psia

20 0
20.0

1.00

2.00

3.00

time, hours

4.00

2.00

3.00

time, hours

80.0

0.0
0.00

1.00

5.00

4.00

5.00

Recovery Effic
ciency

TMP Analysis
y
Specifications
RO - SWC-1-4040 - 6GPM - (70SF)

1.2
1.0
08
0.8

600 psia

0.6

800 psia

0.4

1000 psia

0.2
0.0
0.00

1.00

2.00

3.00

4.00

5.00

time, hours

Specifications
RO - SWC-1-4040 - 6GPM - (70SF)
Permeate F
Fraction

0.40
0.30
600 psia
800 psia

0.20

1000 psia
0.10
0.00

1.00

2.00

3.00

time, hours

4.00

5.00

Increase size of
holding tank
Use two tanks
Increase feed rate
from OC train
b t
but
resize OC columns
Increase number of
OC columns

RO Performance: Feed Rate


Analysis
Membrane Performance (TMP=1000
(TMP 1000 psia , Vt=
Vt 50
50-75
75 gallons)

0.30
6 gpm
0 25
0.25

8 gpm
10 gpm

0.20
0.15
0.00

12 gpm

Membrane Performance (TMP=1000 psia, 6GPM)


0.50
0.35

Permeate
e Fraction

Permeate F
Fraction

0.35

0.30

1.00

1.50

2.00

time, hours

Vt (50-150)

0.25

Vt (100-150)
0.20
0.15
0 00
0.00

Vt (150-150)

1 00
1.00

2 00
2.00

3 00
3.00
time, hours

4 00
4.00

5 00
5.00

6 00
6.00

Design
g Scenarios
Batch
Time
(h)

TDS (F)
(ppm)

Permeate
(gal)

TDS(P)
(ppm)

Recovery
Efficiency

TDS
(initial)
(ppm)

Volume
Holding
Tank (N,C)

Units
(OC,RO)
(OC
RO)

Feed
gpm

TMP
psia

3.92
4.03
4.13
2.07
2.12
2.17
0.47
0.88
0.75
0.65
0.50
0.42
0 32
0.32
0.58
0.60
0.52
0.75

32728
32241
31880
35920
35526
35245
39357
39594
39422
39426
36660
39242
38960
39557
39415
39026
11497

282
291
299
137
141
145
25
47
82
108
115
91
69
126
130
166
342

174
204
212
237
287
305
436
439
424
411
374
422
426
434
560
356
27

0.79
0.80
0.80
0.65
0.65
0.66
0.29
0.28
0.52
0.72
0.83
0.55
0 40
0.40
0.37
0.38
0.52
0.91

5000
5000
5000
10000
10000
10000
25000
25000
25000
25000
25000
25000
25000
25000
25000
25000
5000

50,75
50,75
50,75
50,75
50,75
50,75
50,80
100,150
100,150
100,150
100,150
100,150
100 150
100,150
200,300
200,300
200,300
200,300
,

2,1
2,1
2,1
2,1
2,1
2,1
2,1
2,1
2,2
2,3
2,4
4,4
44
4,4
4,4
4,4
4,4
4,4
,

6
8
10
6
6
6
6
6
6
6
6
6
6
6
8
8
8

800
800
800
800
800
800
800
800
800
800
800
800
800
800
800
1000
1000

Scale--Up Issues
Scale
S-115

S-110
S-116

P-1 / GMF-101

P-2 / GMF-102

OC Filtration

OC Filtration

S-113

S-102

S-114

P-3 / RO-101
Reverse Osmosis
S 107
S-107

S-103
P-4 / RO-102

S-101

S-106

Reverse Osmosis
P-11 / FSP-101 S-104
Flow Splitting
P-10 / V-102

P-9 / V-101

Storage

Holding Tank

S-108

Permeate

S-105
P-5 / RO-103
S-109

Reverse Osmosis

S-117

S-112

S-119
S-118
P-6 / RO-104
Reverse Osmosis
P-7 / GMF-103

P-8

OC Filtration

OC Filtration

P-12 / V-103

S-111

Future Work
Experiments with other membrane
materials at higher pressure
Expand RORO-model design for other
membrane specifications
Continue OC experimental design to
accommodate different packing
Analyze membranemembrane-regeneration cycles
Analyze scaling, fouling

Future Work
Membrane fouling: Causes (scale, oil, pH,
aging)
Monitoring,
g, cleaning
g frequency
q
y and agents
g
Prevention (extend membrane life)

Permeate
Flux

Cleaning

Time

Future Work
Oil/ t separation
Oil/water
ti with
ith
hydrocyclones
High separation efficiency
No chemicals or cleaning needed
Low maintenance and operating
cost
No Moving Parts
Recycle options

Vision 2020 and beyond


y
Work with local, state and federal agencies to
incorporate this new process into permitted
operations
Develop
p new and faster online sensors for TDS
and for selected metals (biosensors, nano
nano-sensors)
Develop and implement control algorithms for
continuous operation
Analyze hybrid RO systems Wind power
driven,
driven solar power
Evaluate beneficial uses of waste (road
desalting, construction materials, landscaping)

Interdisciplinary
y Program
g

Financial Support
DOE
CONACYT (Mexico, A&M)
GPRI (Marathon,
(Marathon Total Fina
Fina,
ChevronTexaco)
P l
Polymer
Ventures
V t
TWRI

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