Complementary Material

Oilfield Brines Æ 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 dday
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 on-

on-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 CX-101
Centrifugal Extraction

Source Brine S-106 S-108

O1Coalescer / OS-101
P-9 / FSP-103 Oil Waste-c
Oil Separation
Flow Splitting

Flow Splitting P-13 / CY-101

S-111 Hydrocyclone S-109 S-110
S-103

Organo Clay / OC

Permeate
S-104

Reverse Osmosis / RO
Holding Tank / Vt
Reject
S-112

Disposal
Suspended/Dissolved Solid
Separation Levels

Micro Filtration (MF) (10- 0.1μm)

Bacteria, suspended particles

Ultrafiltration (UF) (0.05-0.005μm)

Colloids, macromolecules

Nanofiltration (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
Natural Osmosis Principle
Selective barrier

Selective Membrane

Osmotic Pressure
( ) r
Δπ = f T , C
Reverse Osmosis Principle

OSMOSIS REVERSE OSMOSIS

Head = Osmotic
Pressure
Applied
Pressure
Semi-permeable
Membrane
Diluted Brine
Initial Brine or pure water
Concentrated
Water Flow
Water Flow Brine
Membrane Configurations and
Materials
Spiral--wound module
Spiral

Hollow fiber module

Terminology
gy
Rejection R = 1 − CP / CF
T
Transmembrane
b
pressure ⎡ P + PR ⎤
TMP = ⎢ F ⎥ − PP
⎣ 2 ⎦
Feed,
Feed permeate,
permeate reject
or concentrate rates
scale--up use fluxes
For scale F P

(volumetric rate/area)

Jw = flux of permeate y P C C
x F
Reverse Osmosis Governing
Equations

Dw Cw v w (ΔP − Δπ )
~
Jw =
RTt

Dw =
kT
6πμ w rp
( )
r
Δπ = f T , C
Osmotic Pressure
Osmotic Pressure vs TDS**
600
psia)

T = 200 F
500
T = 100 F
essure (p

400

300
motic Pre

200 r
Δπ = f T ,C ( )
Osm

100

0
0 1 2 3 4 5 6
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
MgSO 120.4)) 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
S-102
Centrifugal Extraction S-105
P-9 / FSP-103
Flow Splitting

Source Brine S-101

S-103

Organo Clay / OC
Permeate
S-104

Holding Tank / Vt Reverse Osmosis / RO

S-112
Reject

Disposal
Objectives
j
Maximize permeate production
Minimize waste volume (concentrated
brine))
Eliminate bottlenecks
Enable semi-
semi-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 10-
10-Fold Oil Concentration
Reduction
1600

1440 800 ppm y = 0.3217e

0.5219x

1280 1600 ppm 2

R = 0.9437

1120 3200 ppm 0.4702x

y = 0.2499e
6400 ppm 2
R = 0.9911
960
[Oill], ppm

800
0.358x
y = 0.1949e
0 1949
640 2
R = 0.9934
480
320 0 2027x
0.2027x
y = 0.1166e
160 2
R = 0.7767
0
0.2 0.7 1.2 1.7 2.2 2.7 3.2

Q, L/min
Adsorption
p Experiments
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
1
C final / C initial
oncentrattion

0.8

Coutlet 0.6
rattio)
C i / Cf (oil co

Cinlet 0.4

02
0.2

0
0 50 100 150 200 250
Time (minute s)
OC Adsorption Modeling
g

Negligible axial dispersion

Process governed by mass-transfer
resistance
First-order kinetics
S
Sensitivity
iti it analysis
l i tot residence
id time
ti
Second Column Brings Outlet
TOC Below Limit
Oil Adsorption Performance
Two OC Columns In Series
125.0
Outlet TOC, ppm

100.0

75 0
75.0 S 115
S-115

P-1 / GMF-101 P-2 / GMF-102

50.0 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
Recycle
Reverse Osmosis
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 Æ on/off
Inlet TDS ((0 – 40,000
ppm)
Feed rate (6 – 14
GPM)
Recovery Decreases with
Pressure, Increasing Flow Rate
Feed = Pure Water
0.35
covery fraction

0.30
0.25
6 gpm
0.20
8 gpm
0 15
0.15
Perrmeate rec

10 gpm
0.10
0.05
0.00
0 200 400 600 800 1000
Transmembrane p
pressure,, psi
p
Increasing Salt Further
Decreases Recovery
Feed = 30,000
30 000 mg/L NaCl

0.20
ction
covery frac

0 16
0.16

0.12 6 gpm
8 gpm
Perrmeate rec

0 08
0.08 10 gpm
0.04

0.00
450 550 650 750
Transmembrane pressure, psi
Increasing TMP Increases Salt
Rejection
Feed = 40,000 mg/L NaCl
99.00
ection, %

98.00
6 gpm
97.00 8 gp
gpm
Salt reje

10 gpm
96.00

95.00
550 600 650 700 750 800
Transmembrane pressure
pressure, psi
Salt Rejection Improves at Lower
Concentration
Feed = 10,000 mg/L NaCl
99.60
Salt rrejection, %

99.20
6 gpm
98.80 8 gpm
10 gpm
98.40

98.00
250 350 450 550 650 750
Transmembrane p
pressure,, psi
p
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—
(yes—3 repetitions)
Over 450 data points
Uncertainty + 0.5 % in permeate
concentration measurement and + 1.5% in
rate measurement
Least Squares Regression
g

Permeate flux
⎡ a a ⎤
⎢ ⎛⎜ TMP ⎞ 2 ⎛ TDS ⎞ 6 ⎥
a
⎟ ⎛ ⎞
+a ⎜ ⎟
TDS 4
J = ⎢a +a ⎜ ⎟ ⎥
w 1⎜ J ⎟ 3 ⎝ TMP ⎠ 5⎜ J ⎟
⎢⎣ ⎝ F ⎠ ⎝ F ⎠ ⎥⎦

Total TDS rejection

⎡ ⎛ b
⎞ 2 b ⎛ TDS ⎞ 6 ⎤⎥
b
⎢ ⎜ TMP ⎟ ⎛ ⎞
+b ⎜ ⎟
TDS 4
R = ⎢b +b ⎜ ⎟ ⎥
1⎜ J ⎟ 3 ⎝ TMP ⎠ 5⎜ J ⎟
⎢⎣ ⎝ F ⎠ ⎝ F ⎠ ⎥⎦
Rejection Model Matches Real
Data
Membrane: SWC1- 4040
NaCl Rejection % (Error Bars + 0.5% )
100
99
98
Predicted

97
96
95
94
94 95 96 97 98 99 100
Experimental
Permeate Flow Model Matches
Real Data
Membrane: SWC1- 4040
Permeate Flow as % of Feed (Error Bars + 1.5% )
30

25

20
dicted

15
Pred

10
5

0
0 5 10 15 20 25 30
E
Experimental
i t l
Scenario 1: Constant-
Constant-Feed TDS

Propose desired permeate (freshwater) rate or

d il production
daily d ti
Select transmembrane pressure (greater than Δπ
Δπ))
Ob i required
Obtain i d membrane
b area Am
Select L / A
Obtain required feed-
feed-flow rate
 Operating
g Conditions Design
g
100000 30

qP =15000 gal/day 25

P)k /(1-w S) v W Am
L/A=25 m-1
10000
5.59 v W (1-w S) PAm /

20
20
5000
4000
10000 15 15

8(qP/(qF-qP
3000
2000
10 10
8
1000
6

0.028
5

1000 0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(1 - ΔΠ /Δ P)
 Begin Design

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

Evaluate: rb, mw, ws,

p, vw
Design
Set ΔP and desired qP (gal/day)
Stages
With obtained
bt i d value
l forf x-axisi - (1-π/ΔP)
(1 /ΔP) and
d qP
evaluate Am from left y-axis

Propose L/A (m-1)

Obtain qF from right y-axis

Is qF within allowed
No range No

Yes

End
Design
g Example
Given p
process parameters
p and desired outcome
TDS = 18,000 ppm
T = 160 ° F
TMP = 500 psia
qP = 5,000 gal/day

Solution
Δπ = 192 psi
Left axis Æ Am = 39 53 m2
39.53
Propose - L/A = 15 m-1
Right axis Æ 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, make-
make-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 Æ75 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
Recycle
Permeate TDS > Reverse Osmosis
500 ppm
Transient Behavior
Cumulative
Cumulative & Instantaneous
Permeate Permeate
Production Concentration
& Recovery Efficiency
80.0
250.0 0.8
350.0
Inst - pp
ppm 07
0.7
300.0
gal

200.0
70.0
Gallons

Cum - ppm 0.6

ume,

RE = P/((P+R)
250.0 0.5
150.0
Tank Volu

60 0
60.0
TDS, ppm
HoldingPrroduction,

200.0 0.4
100.0 0.3
150.0
50.0
02
0.2
50.0
100.0 0.1
40.0
0.0
50.0 0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
30.0
0.0
Time, hrs
0.0
0.00 0.5
0.50 1.0
1.00 1.5
1.50 2.0
2.00 2.5
2.50 3.0
3.00 3.5
3.50
Volume Permeate
Time
Time, Produced
Time hrs
Time, hrs
 TMP analysis (600, 800, 1000 psia)
Specifications
RO - SWC-1-4040 - 6GPM - (70SF)
300.0
ced,

250.0
Permeate Produc

200.0 600 psia

gallons

150.0 800 psia

100.0 1000 psia
50.0 Specifications
0.0
0 0 RO - SWC
SWC-1-4040
1 4040 - 6GPM - (70SF)
50000.0
0.00 1.00 2.00 3.00 4.00 5.00

Feed TDS, ppm

40000.0
time, hours
30000.0 600 psia
20000.0 800 psia
10000.0 1000 psia

0.0
0.00 1.00 2.00 3.00 4.00 5.00
Specifications
RO - SWC-1-4040 - 6GPM - (70SF) time, hours

80.0
ume, gallons
olding Tank

60.0
600 psia
40.0 800 psia
1000 psia
20 0
20.0
Volu
Ho

0.0
0.00 1.00 2.00 3.00 4.00 5.00
time, hours
 TMP Analysis
y
Specifications
RO - SWC-1-4040 - 6GPM - (70SF)
1.2
ciency

1.0
08
0.8
Increase size of
Recovery Effic

600 psia
0.6
0.4
800 psia holding tank
1000 psia
0.2
0.0 Use two tanks
0.00 1.00 2.00 3.00 4.00 5.00
time, hours Increase feed rate
from OC train
Specifications
RO - SWC-1-4040 - 6GPM - (70SF)
b t
but…
0.40
resize OC columns
Fraction

0.30
600 psia Increase number of
Permeate F

800 psia
0.20
1000 psia OC columns
0.10
0.00 1.00 2.00 3.00 4.00 5.00
time, hours
 RO Performance: Feed Rate
Analysis
Membrane Performance (TMP=1000
(TMP 1000 psia , Vt=
Vt 50
50-75
75 gallons)
0.35
Fraction

0.30
6 gpm
Permeate F

0 25
0.25 8 gpm
10 gpm
0.20
12 gpm
Membrane Performance (TMP=1000 psia, 6GPM)
0.15
0.00 0.35
0.50 1.00 1.50 2.00
e Fraction

time, hours
0.30
Vt (50-150)
0.25
Permeate

Vt (100-150)
0.20 Vt (150-150)

0.15
0 00
0.00 1 00
1.00 2 00
2.00 3 00
3.00 4 00
4.00 5 00
5.00 6 00
6.00
time, hours
Design
g Scenarios
Batch TDS (F) Permeate TDS(P) Recovery TDS Volume Units Feed TMP
Time (ppm) (gal) (ppm) Efficiency (initial) Holding (OC,RO)
(OC RO) gpm psia
(h) (ppm) Tank (N,C)
3.92 32728 282 174 0.79 5000 50,75 2,1 6 800
4.03 32241 291 204 0.80 5000 50,75 2,1 8 800
4.13 31880 299 212 0.80 5000 50,75 2,1 10 800
2.07 35920 137 237 0.65 10000 50,75 2,1 6 800
2.12 35526 141 287 0.65 10000 50,75 2,1 6 800
2.17 35245 145 305 0.66 10000 50,75 2,1 6 800
0.47 39357 25 436 0.29 25000 50,80 2,1 6 800
0.88 39594 47 439 0.28 25000 100,150 2,1 6 800
0.75 39422 82 424 0.52 25000 100,150 2,2 6 800
0.65 39426 108 411 0.72 25000 100,150 2,3 6 800
0.50 36660 115 374 0.83 25000 100,150 2,4 6 800
0.42 39242 91 422 0.55 25000 100,150 4,4 6 800
0 32
0.32 38960 69 426 0 40
0.40 25000 100 150
100,150 44
4,4 6 800
0.58 39557 126 434 0.37 25000 200,300 4,4 6 800
0.60 39415 130 560 0.38 25000 200,300 4,4 8 800
0.52 39026 166 356 0.52 25000 200,300 4,4 8 1000
0.75 11497 342 27 0.91 5000 200,300
, 4,4
, 8 1000
Scale--Up Issues
Scale
S-115
S-110

S-116
S-113
P-1 / GMF-101 P-2 / GMF-102
OC Filtration OC Filtration
P-3 / RO-101
S-102
S-114 Reverse Osmosis

S 107
S-107
S-103

S-101 P-4 / RO-102 S-106

Reverse Osmosis
P-11 / FSP-101 S-104
Flow Splitting
P-10 / V-102 P-9 / V-101 S-108
P-12 / V-103
Storage Holding Tank
S-105 Permeate
P-5 / RO-103
S-117 Reverse Osmosis S-109

S-119 S-112

S-118

P-6 / RO-104
Reverse Osmosis S-111

P-7 / GMF-103 P-8

OC Filtration OC Filtration
Future Work

Experiments with other membrane

materials at higher pressure
Expand RO-
RO-model design for other
membrane specifications
Continue OC experimental design to
accommodate different packing
Analyze membrane-
membrane-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 withith
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