May 12-14, 2013

Innovating Advanced Oil-Water

Separation and Desalination
Technologies for Produced Water
Treatment and Reuse
Eric M.V. Hoek1 and Subir Bhattacharjee2
1 UCLA NanoMeTeR Lab, Department of Civil & Environmental Engineering,
Institute of the Environment & Sustainability, California NanoSystems Institute
2 University of Alberta, NSERC Industry Research Chair for Water Quality
Management in Oil Sands, Department of Mechanical Engineering
UCLA Nanomaterials and Fundamentals
Membrane Technology
Research Laboratory

Colloid & Interface

Science

Membrane
Technology

Electrochemical Nanomaterials &

Prof. Eric M.V. Hoek Technology Nanotechnology
NanoMeTeR Lab Director
(310) 206-3735 [ofc]
emvhoek@ucla.edu
Renewable Energy Antimicrobial & Appli
Production Antifouling Materials
nanometer.ucla.edu

Environmental
Protection & Desalination and Kidney Dialysis &
Remediation Water Purification Protein Filtration
 Nanocomposite RO membranes
Our early research on membrane formation focused on
the creation of TFN RO membranes
which eventually led to the creation of a new RO
membrane manufacturer.

www.nanoh2o.com
 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned UCLA WPE

State of the technology Today

Summary & discussion

???
 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned UCLA WPE

State of the technology Today

Summary & discussion

???

5
Original Motivation = Produced Water
In 2007/2008, Subir took
sabbatical at UCLA and
introduced me to produced
water treatment.

Management of this water

has become a critical factor
driving the economics of oil
and gas production,
particularly EOR & fracing
operations.
 Composition of PW or flowback fluids

Frac Conventional
flowback HCs PW
water Water
EOR
produce
Tailings
d fluids Solids Drilling
water
Steam mud
flooding
PW

Origins & proportions of these three phases dictate the nature of PW

 Research Approach
Water treatment problem

Perceived to be:
Microscale Phenomena/ Fundamental Processes
Low
Industry ApproachChemical
risk,
Physical
short
Fouling, deposition, aggregation, separation, etc.
path

Find ways to get existing

technologies to work
 Research Approach
Water treatment problem

Perceived to be:
Fundamental Processes
High
Our Approach Chemical
risk,
Physical
long
Separation, efficiency, economics, etc.
path

Find the best possible way

to solve the problem
 Our clean slate approach
What have we evaluated for oil/water separation?
Chemical processes
Emulsion and reverse-emulsion chemistry
Chemical and electrochemical coagulation
Mechanical processes
Gravity based sedimentation and flotation
Centrifugation and cyclonic separation
Filtration processes
Media filtration (wallnut shells, GAC, organo-sand, organo-clay,
polymer, coalescer, etc.)
Membrane filtration (MF/UF/NF, polymeric/ceramic)
Hybrid processes
Hybrid centrifugal and cyclonic flotation
Hybrid electro-coagulation/centrifugation
Hybrid centrifugal membrane filtration
Summary of O/W Separation Research
Water chemistry governs OiW emulsion droplet size and
stability (DLVO theory works)
Emulsion droplet size governs separation by mechanical &
filtration technologies (Stokes would be pleased)
Mechanical separation performance is enhanced by heat
and chemistry (classical Schulze-Hardy behavior)
Membrane filtration is the most effective technology for
polishing dilute OiW emulsions to low O&G levels
Oil tolerance/clean-ability/robustness key practical factors
Ceramic membranes generally preferred but very expensive
 After the Deepwater Horizon oil spill occurred, all attention
turned to application of oil/water separation to oil spill cleanup

Motivation / Research Hypothesis:

Spend more time booming, skimming & collecting oil by
rapidly dewatering oil contained in OSRV storage tanks
Less downtime, more effective collection of spilled oil

Courtesy: Thomas Azwell, UC Berkeley

 Effects of Mixing (Ejection from Backflow Preventer + Wave Action)
with and without Dispersant Injection on Centrifuge Performance
Clean seawater Oil slick on seawater Oil slick after mixing Mixing + dispersant

0 100,000 100,000 100,000

ppm ppm ppm ppm

Scope and Objectives:

Prepare mechanically mixed and chemically dispersed oil-in-seawater
emulsions
10 wt % light crude oil in raw Pacific ocean water
1 and 5 wt% sodium dodecyl sulfate (to simulate dispersant)
Evaluate oil-water separation efficiency of bench scale centrifugal separator
Evaluate water polishing efficiency of commercial and UCLA hand-cast
ultrafiltration (UF) membranes
 Effects of Mixing (Ejection from Backflow Preventer + Wave Action)
with and without Dispersant Injection on Centrifuge Performance
Clean seawater Oil slick on seawater Oil slick after mixing Mixing + dispersant

0 100,000 100,000 100,000

ppm ppm ppm ppm

100

80
Number

60
w/ 1% SDS
w/o SDS
40

20

0
1 10 100 1000 10000
Size, nm
 Effects of Mixing (Ejection from Backflow Preventer + Wave Action)
with and without Dispersant Injection on Centrifuge Performance
Clean seawater Oil slick on seawater Oil slick after mixing Mixing + dispersant

0 100,000 100,000 100,000

ppm ppm ppm ppm

Mixed oil slick (no dispersant) Mixed & dispersant stabilized oil

After the
centrifuge

7 107
ppm ppm
Performance of UCLA Oil-Tolerant UF
Membranes on Centrifuge Effluents
Permeate
Feed

Membrane
Feed 7
Tank
Clean ppm < 0.5
Tank ppm

Permeate
Feed

6-Cell
Membrane
Filtration
System
Membrane
107 < 0.5
ppm ppm
 UCLA Oil-Tolerant Membranes Resist
Fouling by Oil and are Easy to Clean

w/o
SDS
CM1 CM2 UCLA

w/ 1%
SDS

CM1 CM2 UCL

A

w/ 5%
SDS
CM2
CM1 UCLA
 Summary of UCLA Lab-scale Research on
Separation of Spilled Crude Oil from Seawater
Spilled oil naturally disperses into seawater very
quickly with intense mechanical agitation

Dispersant chemicals do exactly what they are

designed to dodisperse oil into water

Conclusion from Lab / Hypothesis for Field:

Integration of centrifuge and membrane technology
onboard OSRVs may enable rapid dewatering of
skimmed oil and completely deoiled water to be safely
overboarded to the ocean
 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned @ WPE UCLA WPE

UF membrane innovation Poly

Cera

Summary & discussion

???

19
 Early Field Trials with BP
After a number of field demonstrations performed with BP and key
teaming partners like D&L Salvage and CCS Midstream Services we were
able to prove the technology could be safely integrated onto OSRVs.

On the D&L Salvage Hammerhead shallow Process engineers from CCS Midstream
water barge in Fort Jackson, LA. Services connecting a centrifuge to liquid
transfer and filtration system.
Chemical Dispersant + Mixing + Sun + Time in Water Create
Peanut Butter form of Spilled Oil

The peanut butter

like sludge at left was
produced by rapidly
mixing oil with
dispersants in
seawater for 4 hours.

The peanut butter is

a chemically-stabilized
water-in-oil emulsion
that cannot be
separated
mechanically because
it does not flow.

The peanut butter

contains 50-80%
water and 20-50% oil
+ dispersant.
New demulsifying chemistry was developed with CCS Midstream Services and
MI-SWAKO to enhance the performance of the centrifuge technology.

OIL

WATER

SOLIDS
Two Centrifuges on D&L Salvages Hammerhead
and Splash Shallow Water Barges

Centrifuge system
4 Centrifuges each on Edison Chouest Offshores
Ella G and Ingrid Platform Supply Vessels

~1 MGD capacity
(~23,000 bbl/day)

Centrifuge system
6 Centrifuges on Hornbeck Offshore Services
Energy 8001; 3 on HOS 13501

Centrifuge system
 Commercial polymeric UF membrane system was
integrated with centrifuge on Hornbeck Energy 13501

Membrane system
 Representative Field Data
Field Field Lab Lab
Separation Influent Effluent Influent Effluent
Technology (O&G) (O&G) (O&G) (O&G)

Centrifuge 20-50% 50-300 ppm 20-50% 50-300 ppm

Membrane 76-100 n.d. 100 n.d.

Organo-clay 180 18 189-220 8-34

Walnut shell 160-194 10-73 Not performed Not performed

Coalescer 104-184 86-88 Not performed Not performed

Summary of Experience in the Gulf
Led an expert team of offshore, engineering and environmental
companies and developed (in real-time) extensive in-field oil/water
separation experience
Demonstrated that integration of OWS onboard OSRVs creates
efficiencies in oil spill cleanup
21-centrifuges installed on 6 different oil spill response vessels
Integrated with conventional boom and skimmer technology
Demonstrated that integrated centrifuge and membrane
technology effectively dewaters oil and deoils water
1-integrated system installed on Hornbeck Energy 13501
Developed new emulsion breaking chemistry to enable
centrifugal/membrane separation of milkshake and peanut
butter recovered oil
 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned UCLA WPE

State of the technology Poly

Cera

Summary & discussion

???

29
 Water Planet Engineering (WPE) was
founded in 2011 to provide solutions
for the worlds most extreme water
treatment problems.

WPE is developing next-generation oil-

water separation and desalination
technology for oil & gas produced
water treatment.
 WPE Vorti-SEPTM Initial Design
Design basis:
High throughput
Small footprint
Containerized
Transportable
Modular

Designed to handle:
Up to 5% solids in influent
Variable O/W ratios up to 30% oil
Breaks oil-water emulsions
Processes heavy oil and bitumen
 WPE Vorti-SEPTM v.1 Pilot Unit

3000 bbl per day capacity

Vorti-SEPTM contains multiple separation technologies integrated to achieve the
most efficient solid-oil-water separation with ability to enhance separation
through addition of heat and chemistry.
 WPE Vorti-SEPTM Demonstration
WPE Vorti-SEPTM Demonstration
Houston, Texas, USA
Recovered oil product November 9, 2012
Polished
(30% crude oil content)
dewatered to <11% BS&W water
>99.985%
O&G
removal
(iron leached
from oil gave
color to
permeate)
 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned UCLA WPE

State of the technology Poly

Cera

Summary & discussion

???

34
 UCLA
Polymeric-
Ceramic
Membranes

Ceramic-like stability & fouling resistance

Polymer economics & high packing density modules
Relevant for a wide array of water treatment applications
 UCLA Ultrafiltration
Tunable performance
200-1000 lmh/bar
5-150 nm pores
Ability to tune flux at fixed
pore size (selectivity)
Can achieve oil & grease
removal <5 ppm (EPA 1664)
Operationally robust
pH window: <1 to >13
Thermally stable up to 95C
Extreme hydrophilicity
Super-Hydrophilic & Super-Oleophobic
Hexadecane droplet in Water contacting Membrane Surface

Polysulfone Membrane UCLA Membrane

qhexadecane ~ 110 qhexadecane ~ 160
(oleophilic) (oleophobic)
FOULING PRONE FOULING RESISTANT
 Oleophobic = Fouling Resistant
Hexadecane droplet in Water contacting Glass & Membrane

Ultra-clean Glass UCLA Membrane

qhexadecane ~ 155 (oleophobic) qhexadecane ~ 160 (oleophobic)

MORE OLEOPHOBIC THAN GLASS!

DG132 = Fouling Propensity

More fouling resistant than most other polymers

materials without need for surface modification
 Oil Fouling Resistance
PSf Greg`s
UCLA1 PANi 65 KDa PANi PP13
UCLA2 PANi
UCLA3PP11
45

40 UCLA membrane material can be

derivatized and tailored for
35 specific types of foulants
30
Improved flux
25
Flux, gfd

recovery by
20
hydraulic flushing

15

10 Improved oil fouling

5
resistance

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130
Time, min
 Accelerated Chemical Degradation Testing
Accelerated complete CIP simulation:
pH 1, 65 C for 48 hours
pH 13, 65 C for 48 hours
PAN Competition Membrane UCLA Polymeric-Ceramic Membrane

Before Exposure After Exposure Before Exposure After Exposure

 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned UCLA WPE

State of technology Today

Summary & discussion

???

42
 State of Technology Today
WPE Vorti-SEPTM system
Two demo systems developed
1000 and 3000 bpd
Multiple successful demonstrations
Expecting first sales late 2013

UCLA membrane
Membrane formulation established
Ready to initiate contract
manufacturing
Module development ongoing
Optimal form factor and materials of
construction
WPE negotiating license & raising
funding to get started
 Outline UCLA

UCLA oil/water separations research

GoM
Gulf of Mexico oil spill experience

Applying what we learned UCLA WPE

State of the technology Today

Summary & discussion

???

44
 Summary UCLA

Our meandering path has enriched and directed our

academic research and entrepreneurial activities
Need-driven, rapid innovation through collaboration GoM

Basic research on oil-water separation fundamentals

was translated (in real-time) during BP-DWH oil spill
UCLA WPE
After the spill, WPE was formed to provide unique
custom-engineered water treatment solutions
Back at UCLA, we focused on further developing a new
Today
ceramic-like polymer membrane material
WPE will combine the UCLA membrane with its
advanced oil-water separation platform for PWT
???
 Acknowledgements
Research Funding
University of California, Los Angeles
China Scientific Council
Ocean Therapy Solutions
Water Planet Engineering
Partners in the Gulf
Edison Chouest Offshore, Hornbeck Offshore Services, Ocean Therapy
Solutions, CINC Industries, Compass Water Solutions, CCS Midstream
Services, D&L Salvage, M-I Swako
Thomas Azwell, Ph.D. candidate, UC Berkeley
Students & Collaborators:
Prof. Subir Bhattacharjee, U of Alberta, Canada
UCLA Jinwen Wang, Dr. Gregory R. Guillen, Dr. Gil Hurwitz, Dr.
Minghua Li
WPE Dr. Arian Edalat, Dr. Gil Hurwitz, Dr. Anna Jawor, Dr. Dian
Tanuwidjaja, Lee Portillo, Jason Lake, Trace Roses
May 12-14, 2013

Evolution of SRP technology Case Study

Kevin Reyntjens
Global Market Development Manager
Dow Water and Process Solutions
 Adoption of Membrane Treatment Technology by the O&G
Industry
May 12-14, 2013
Mid 1980-s : Marathon Oil researched options
to reduce scale that formed in the production
tubing and topside equipment of its South Brae
platform in the North Sea
Scale compounds formed when mixing sulfate
containing injected seawater react with
formation water having a high concentration of
Ba or Sr ions
Chemical scale inhibitors were not effective or
efficient in scale prevention Scaling Prevention
Sulfate removal was considered the most Ba+2 or Sr+2 + SO4-2 -> BaSO4 or SrSO4
appropriate and ecomical method versus
alternatives (water plug-back, mechanical work- Souring Inhibition
over)
Ion selective nanofiltration membranes remove
di-valent (sulfate) ions preferentially and
exhibit high mono-valent salt passage. Implementation:
Avoidance of clay swelling Small scale lab trials Dow Filmtec and Marathon Oil
High recovery : Low footprint and reduced pre- (1987)
treatment volumes 12 month 700 BWPD off-shore
Scale up to three units, each 40,000 BWPD.
All units were in operation in 1990
First greenfield plant : ENI (Agip) Tiffany - 1993
 Milestones
May 12-14, 2013

SRP installed capacity : > 7.5m BWPD / > 50 installations

Highest installed capacity in West Africa and South America (Brazil)
 Commercial Adoption
May 12-14, 2013
Lengthy incubation between first introduction in
1987 to reaching growth mode in the mid
2000s
Factors
Risk / Reward
Acceptance of membrane and process
technology by the (off-shore) O&G industry.
Inherent cycle time of offshore projects Cumulative SRP capacity installed

Accelerators
Collaboration between operator, system
integrator and end-user
Technology champions in each organisation
Sponsors
Increase of water-flooding (IOR/EOR)
Increase of deepwater production since early
2000s (West Africa, Brazil, GoM)
Souring Mitigation
Membrane and system efficiency improvements
Rejection
Surface area
 Typical Process Sheets
May 12-14, 2013

Multi-Media Filtration
Pre-treatment

Membrane Filtration
Pre-treatment

Graphs courtesy Total

 Pre-treatment Process Comparison
SRU
Option 1 CF
May 12-14, 2013 Coarse HP pumps Cartridge
filtration SRP filters (2 stage, Vacuum Injection
Lift Pump
75% De-areation Pumps
50-80 um 36 barg 5um
conversion)

Option 2 - MMF Media

Guard SRU
Coarse Filtration HP pumps
Vacuum De- Cartridge (2 stage, Injection
Lift Pump filtration 2-5 um SRP
areation Filters 75% pumps
150 um particle 36 barg
5 um conversion)
removal

Option 3 - UF SRU
Coarse HP pumps
filtration Vacuum SRP (2 stage, Injection
Lift Pump MF/UF
De-areation 75% Pumps
150 um 36 barg
conversion)

Cartridge Filtration Dual Media Filtration UF

CAPEX ++ + +/-
OPEX -- (SRU) - (SRU) + (MMF) + (SRU)
++ -- +
Pre-treatment Footprint (30% of footprint compared
with MMF)
Technology
Comparison + - +
Weight (40% of weight compared
with MMF)

-- - +
Efficiency 6 weeks SR on-line 3-4 months SR on-line >6 months targeted on-
line
Established? + + +/-

KR 03152012
 Adoption of membrane pre-filtration off-shore
May 12-14, 2013
Filtration using polymeric UF/MF is finding increasing
adoption in off-shore injection water treatment
Pre-treatment prior to SR or RO
Direct injection (instead of macro-filtration)
Benefits
Reliability of up-stream processes Reduced off-line time
Life-Cycle of upstream membranes
Footprint / Weight savings vs. MMF
Similarity in trend in on-shore SWRO desalination processes.

From R. Huemer SPE/EDS workshop, Rome 2012

IOR/EOR Water Quality Needs
Primary
Recovery

Artificial Lift Natural Flow

Secondary
Recovery
SRT
Low Sulphate
High TDS
Pressure
Water Flood
Maintenance
IOR

Tertiary
Recovery
EOR

Thermal / Chemical Low - Tailored

Gas Other
Steam (ASP) Salinity

Low Sulphate
Adopted from JPT , Jan 2012, SPE 143287 Medium/High TDS
Hardness varies - Low
Tailored Water Qualities for IOR/EOR Membrane Options
May 12-14, 2013

Improved Oil Recovery through

Achievement of Very Specific Water Quality
Lisa Henthorne, P.E.
Holly Johnson, P.E.
Becky Turner
 Agenda
Introduction

Water-Based Improved Oil Recovery (IOR) and Enhanced Oil

Recovery (EOR) Methods
Sulphate Removal Processes (SRP)
Low Salinity Waterflooding (LSF)
Chemical Enhanced Oil Recovery (CEOR)

Case Studies
Low salinity and sulfate, medium ratio of divalent/total cations
Medium salinity, low hardness
Low salinity and hardness, high ratio divalent cations

Conclusions
 Introduction
Water shifting from an operations issue to a strategic issue
Offshore expensive and logistically difficult
Onshore limited resources in remote areas, challenging logistics

Water treatment
Non-core capability for oil producers
Weak link in oil production

Need innovative water treatment technologies to address growing

demands

Goals: minimize operating costs, maximize footprint and energy

efficiency, maintain production and/or increase oil recovery rates
Reservoir Subsurface

Shell Westhollow Technology Day, 10-13-2009

 Indicative Reservoir Recovery
WATER-BASED EOR
Incremental 5 30%

Low Salinity: 5-15%

Polymer Flooding: 5-20%
ASP Flooding: 15-30%
Recovery Process

WATERFLOOD
Incremental
5 15%

PRIMARY
Range 10 30%

0 20 40 60 80 100

% Original Oil in Place (OOIP)

Oil Field Life with EOR Implementation

(Note: This graph is representative. Many technical, commercial and contractual variables are reservoir dependent.)
 Water-Based IOR and EOR Methods
Improved Oil Recovery (IOR) Enhanced Oil Recovery (EOR)

SECONDARY TERTIARY
PRIMARY RECOVERY RECOVERY
RECOVERY

PRESSURE
NATURAL WATERFLOOD CHEMICAL
MAINTENANCE
FLOW
LOW
SALINITY
ALKALI,
WATER SURFACTANT, CUSTOM
SULFATE
SEAWATER INJECTION POLYMER WATER
REMOVAL
ARTIFICAL LIFT (ASP)

PRODUCED THERMAL
WATER RE-
INJECTION

SULFATE
SEAWATER SOLVENT
REMOVAL

PRODUCED
WATER RE-
INJECTION
 Sulphate Removal Processes
Risks
Process: Reservoir scaling
Economic: Oil quality degrades
Safety: H2S production

SRP
Removes sulphate to prevent process, economic, and safety risks
Uses specialized Nanofiltration (NF) membranes to reduce sulphate
content in seawater while maintaining high salinity
Over 70 systems worldwide, > 7.5M bbl/day capacity (Reyntjens 2013)

Challenges
Relatively high CAPEX
Substantial space and weight requirements
Platform retrofits often prohibitively expensive
Source: H2Oil & Gas 2012
 Low Salinity Waterflooding
Proposed Mechanisms
Multi-Component Ion Exchange (MIE)
Fines Migration
pH Variation
Double layer expansion
EOR Potential
Global water-based EOR potential - ~750 billion barrels
North Sea: 6 billion barrels
Technology
EOR a 1% increase in recovery could yield 2 billion barrels of oil
equivalent (Upstream Technology 2013)
LSF strong candidate for implementation due to substantial
recovery potential and relative simplicity when viewed as an
extension of seawater injection processes (DECC 2011)
Low Salinity Waterflooding
 Chemical Enhanced Oil Recovery
Typical CEOR Program Chemistry
Alkali
Surfactant
Polymer

Water Quality Considerations

Source water must be softened to prevent hardness from
precipitating in the presence of alkali and damaging wells and
reservoirs
Reducing salinity prior to adding alkali, surfactant and polymer can
amplify positive impacts of each individual program
Customizing ionic compositions enable optimal polymer viscosities to
be achieved easier and more economically
Effect of Salinity on Polymer Requirements

Effect of Salinity on Polymer Concentration (SPE 129926)

Effect of Salinity on Polymer Cost

Annual Polymer Cost Based on Injection Water Salinity for a 100,000 bbl/d System
(SPE 129926)
Adapted from Ayirala, S., Ernesto, U., Matzakos, A., Chin, R., Doe, P., van Den Hoek, P., 2010
Optimal Salinity for Surfactant Floods

Reprinted with permission from Dr. George Hirasaki, Rice University

 Case Study
Goal: Demonstrate the effect of salinity on EOR program costs and
revenues

Cases
1. SRP for IOR waterflooding programs, paired with either surfactant or
polymer to increase recovery
2. LSF for water injection only, and enhanced with the addition of
chemicals
3. Water Softening using NF treatment for water injection only, and
enhanced with chemical addition
 Assumptions
Required Chemical Concentration by Water Treatment Process
Resulting Alkali Polymer
Surfactant
Salinity Concentration Concentration
Concentration (mg/L)
(TDS) (mg/L) (mg/L)
SRP 23,000 - 1,000 1,200
Low Salinity 1,500 14,000 1,000 250
Softening 20,000 14,000 1,000 1,100
(Nanofiltration)

Indicative Incremental Oil Recovery by Treatment Process (Not Cumulative)

Water Alkali-
Injection Surfactant-
Only Polymer Alkali- Alkali- Surfactant- Polymer
(no ASP) (P) Surfactant (AS) Polymer (AP) Polymer (SP) (ASP)
SRP 0% 3% - - 4% -
Low Salinity 6% 10% 7% 12% 15% 20%
Softening
(Nano-Filtration) 2% 6% 5% 8% 10% 12%
 Assumptions
CAPEX
Included: water treatment equipment (e.g., pre-treatment,
membranes, energy-recovery devices), chemical injection system
Neglected: intake, discharge, electrical systems, piping, engineering,
and integration
Assume: seawater feed, produced water does not require further
treatment
OPEX
Included: fuel, water treatment membrane replacement, chemicals
Neglected: labor, maintenance, equipment replacement
Revenue
Based on projected increases in oil recovery
100,000 bbl/day water injection program
10 years
$40/bbl for additional oil after the deduction of royalties and taxes
Case Study Relative ROI
 Conclusions
Water poses significant challenges for the offshore oil industry

IOR and EOR programs may reduce process, safety, and economic
risks

Specialized membrane technologies can help IOR and EOR project

benefits to be fully realized

Investment in water treatment systems can increase oil production

with revenues proving the return on the initial capital investment
May1214,2013

TheuseofceramicmembranesfortreatmentofProducedWater
f
fromSteamEORtoproducefeedstockforsteamgenerationand
d f d kf i d
desalinationforsurfacedischarge

StantonR.SmithPhD,P.Eng CEng
BusinessDevelopmentManager
VeoliaWaterSolutionsandTechnologiesN.A.
g
 Background and Focus
BackgroundandFocus
14,2013

Veoliasupplied45kBWPDSteamEORPWTsystemtoPXPin2012
pp y
SystemusesROSSTM processtoproduce50kBWPDwaterwith
significantlyreducedhardness,silica,O&GandTSS
25kBWPDROSSeffluentto:
OTSGforSteamEOR
OPUSIIforsurfacedischarge(andinternaluse)
OPUS II for surface discharge (and internal use)
SystemcommissionedH22012intoQ12013
Focus:piloting,scaleup,commissioningandoperationofROSS
ROPretreatment
 Contents
14,2013

ProjectGoals
TreatmentchallengesandTechnicalsolution
ScaleupofROPretreatment(i.e.ROSSTM process)
Experiencefromdelivery,commissioningandoperation
 Project Goals
ProjectGoals
14,2013
rojectGoals
uent
uent
WaterSource
14,2013
SteamFloodOilFieldProducedWater
InfluentQuality
Temperature:160 200oF,pH:7.0
Silica:240ppm,TotalHardness:210ppm asCaCO3
TDS:2,100ppm,Boron:5.8ppm,Ammonia:16ppm
Free Oil : 120 ppm, COD : 690 ppm, TOC 210ppm
FreeOil:120ppm,COD:690ppm,TOC 210 ppm
uentRequirements
NPDESSurfaceDischarge
CompliancetoPermit CRWQCB,CATitle22,CABasinPlain
RemovalofBoron,Ammonia,TDStolowlevels
OTSGMakeup
RemovalofOil,HardnessandTSStolowlevels
tem Capacity
temCapacity
NPDESDischarge:20,000bpd
OTSGMakeup:25,000bpd

5
ockFlowDiagram

SEOR
SEOR
PW 25,000
BWPD
OTSGs

ROSSTM+WAC Internalusers
0,000BWPDeffluent
SurfaceDischarge

RO system
ROsystem
25,000
20,000
SIITM BWPD
BWPD
00BWPDEffluent
TreatmentChallengesandTechnical
S l ti
Solution
OMembrane TreatmentChallenges
mbraneScalingPotential
b S li P i l
DissolvedSilica(240ppm)
CalciumSalts(CaCO3,CaF3)
MetalSalts(Fe,Mn,Aletc.),
mbraneFoulingPotential
OrganicFouling(TOC 210ppm)
Particulates(Freeoil,TSS,etc)
mbraneSaltRejection
BoronRemoval
OrganicsRemoval(Phenol)
HighFeedWaterTemperature
hSystemRecoveryRate
y y
WasteMinimizationtoDeepWell

8
OSSTM ROPretreatment Goals
educeROMembraneScalingPotential
d RO M b S li P t ti l
RemoveSilicato<50mg/l
RemoveCalcium,Magnesium andotherMetal Salts

inimizeROFoulingPotential
RemoveParticulates(Freeoil,TSS,etc)

Wh i ROSS?
WhatisROSS?

RemovalofOil,SuspendedSolids,andScaleFormers(Ca,SiO2,Mg,Ba,etc)
9
Zoomin:ROSSKeyComponents
WhyROSS?:ROSSBenefitsvs.ConventionalProcesses

14,2013
Smallerfootprint/Costcompetitive(TICbasis)
High effluent quality: direct to OTSG or to RO/Drum Boiler
Higheffluentquality:directtoOTSGortoRO/DrumBoiler
Modularizedandshopfabricatedequipment
Operatorfriendly/fullyautomated
Reliableeffluentquality:barriertechnologystoppingupsets
thoutcoagulantandflocculent
 Onsite
On siteDemonstration
Demonstration
14,2013
Demonstration Treatment Line
DemonstrationTreatmentLine
ROSS&OPUSII DemonstrationUnit
 ROSSTM Performance
EffluentQuality
TSS<0.5ppm,FreeOil<0.5ppm,SDI<2.5
TotalHardness<5ppmasCaCO3,DissolvedSilica<15ppm
Runlengths
CommerciallypracticalCIPfrequency
FluxMaintenance:backpulse andchemicalbackwash
CIPChemistry
Causticfollowedbyacid
y
Scalant type:mostlyinorganicrestorablew/acidCIP/BW
Other
TrialswithMgCl2andMgO
Trials with MgCl2 and MgO successful
StressTestwithHigherOilConcentrationSuccessful
 OPUS PilotResults NPDESDischarge
ProducedWater Design Pilot Pilot Discharge
Contaminant Basis Influent Effluent Specification
, mg/l 1,950 2,100 15 <450
ates,mg/l N.D N.D N.D <45
ites, mg/lasN N.D 0.015 N.D <1.0
oride,mg/l 2.8 5.2 N.D <1.0
on,mg/l 6.8 8.6 0.021 <1.0
monia,mg/lasN 7.9 16 0.001 <0.025(UI)
il &Grease,mg/l 100 120 N.D <35
standardunits 7.0 7.09 7.39 7.0~8.3
zene,ppb 12 22 0.55 <1.0
uene, ppb 12 12 0.64 <150
ylBenzene,ppb 30 36 0.98 <300
ene,ppb 25 46 3.0 <1750
nol,ppb 100 270 NonDetect <1.0
PilotSummary
y ROSSandOPUSII
OPUS Very effective in Contaminant Removal Efficiency
OPUSVeryeffectiveinContaminantRemovalEfficiency
LowLevelsofBoron,Ammonia&TDS
GeneratesHighPurityWaterSuitableforSurfaceDischarge
EffectiveFoulingControlProven
g
ElevatedpHOperationforOrganicfoulingControl
CeraMemFiltrationandReverseOsmosis
ChemicalEnhancedBackwashesforInorganicfoulingControl
CeraMem Filtration
l
ROSScapableoflargeO&Gupsetsupto1000ppm HEM
CompactFootprintROSSROPretreatmentApproach
SuccessfulDemonstrationofSingleStepDeOiling,Softening,Silica&TSSRemoval
Successful Demonstration of Single Step De Oiling Softening Silica & TSS Removal
Scale Up and Delivery of ROSS System
ScaleUpandDeliveryofROSSSystem

DEPLOY

EXECUTE

DESIGN

DEFINE
OSSusesCeraMem MembraneSystem
BuildingBlock:10,000BWPD
Auxiliary
equipment(x1)
10kBWPD
10 k BWPD
membrane
block(x6)
ScaledROSSPlant
ScaledROSSPlant
Membranecircpumps,piping&electrical
distribution
aledROSS
Plant
xperience:Exectution,Commissioning
and Operations
andOperations
 Key learnings slide#1
Keylearnings slide # 1
14,2013

St t
StartupandExecution
dE ti
Safety:keyforanyprojectandthisjobsitewasverysafe
Ontimeandonbudget
Started ROSS first and operated ROSS for some time until operational issues worked out
StartedROSSfirstandoperatedROSSforsometimeuntiloperationalissuesworkedout
StartedROafterROSSoperatingsmoothly
ROSSeffluentcouldgotoOTSGordirectlytodeepwell
Startupsurprise:1,000,000gallonscoldPWtotreat
Startedupw/differentchemistrytoavoidmultiplesilocommissioning
24/7engineeringsupportfortwomonthsdurings/u
Minimalequipmentchallenges
N
Numerousprocessandprojectteammeetingsthroughout
d j i h h
 Key learnings slide#2
Keylearnings slide # 2
14,2013

Performanceandeffluentquality:
Generallysameorbetterthandemonstrationtrial(seepilottrialslides)
Onlypresentinterestingitemshere

Cold, offspec
Cold,off specfeed(startupandupsetevents):
feed (startup and upset events):
Cantreatw/increasedMgO dose&reducedCeraMem flux
Canoperatew/controlledfoulingatlowerflux
Optedtoblendcoldwaterinw/warmwaterforincreasedproductionrate.Holdingtankneededfor
cold water
coldwater

CIPspacing
Over50%bettervs.pilot.
Couldresultfromsomechangestofluxmaintenance.Willtrytopinpointdifferencesinfuture
Reducedchemicalcost,andincreasedavailability
 Key learnings slide#3
Keylearnings slide # 3
14,2013

CompareddifferentsofteningchemistrieswithROSS
Ranmonthsw/MgO+caustic andw/MgO+lime+caustic
SawlittlenoticeableperformancedifferenceonROSS
Sludgethickenerwasnotstudiedindetail,butseemedtooperatereasonablewellin
both cases
bothcases

MgO andLimefeeders
Spenttimeoptimizingthesepowderdosingsystems
S i i ii h d d i
Typicalstartupchallenges:plugging,dynamicslurryconcentration
 Conclusions
14,2013

Scaleupsuccessful
Executionsafe,ontimeandonbudget
Commissioningovercamenumerouschallenges
Numerous key learnings and counting
Numerouskeylearningsandcounting
Veoliamadecareful,measuredfirststepinSEORPWTcommercialization
andsofarsuccessful
RO operating stably Drum boiler feed alternative for SAGD (w/heat
ROoperatingstably.DrumboilerfeedalternativeforSAGD(w/heat
recovery)
Veoliahas12yearoperatingcontract:moreexperiencedowntheroad
Thank You
ThankYou
StantonSmith,P.Eng
, g
CeraMemCeramicMembraneSystems
VeoliaWaterSolutionsandTechnologies

Email:stanton.smith@veoliawater.com
Tel:7818107713