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 Membrane Technology Research Laboratory

Fundamentals

Colloid & Interface Science

Membrane Technology

Prof. Eric M.V. Hoek NanoMeTeR Lab Director (310) 206-3735 [ofc] [email protected] nanometer.ucla.edu

Environmental Protection & Remediation

Electrochemical Technology

Nanomaterials & Nanotechnology

Renewable Energy Production

Antimicrobial & Antifouling Materials

Desalination and Water Purification

Kidney Dialysis & Protein Filtration

Appli

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 • State of the technology

UCLA

WPE

Today

• Summary & discussion ???

Outline

UCLA

• UCLA oil/water separations research GoM

• Gulf of Mexico oil spill experience

• Applying what we learned • State of the technology

UCLA

WPE

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 & frac’ing operations.

Composition of PW or flowback fluids Frac flowback water

Water EOR produce d fluids

Steam flooding PW

Conventional PW

HCs

Solids

Tailings water

Drilling mud

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

Research Approach Water treatment problem Perceived to be: Microscale Phenomena/ Fundamental Processes

Physical

Industry ApproachChemical

Fouling, deposition, aggregation, separation, etc.

Find ways to get existing technologies to work

Low risk, short path

Research Approach Water treatment problem Perceived to be: Fundamental Processes

Physical

Our Approach Chemical

Separation, efficiency, economics, etc.

Find the best possible way to solve the problem

High risk, long path

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

0 ppm

Oil slick on seawater

Oil slick after mixing

Mixing + dispersant

100,000 ppm

100,000 ppm

100,000 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

100,000 ppm

100,000 ppm

100,000 ppm

0 ppm 100

Number

80 60

w/ 1% SDS w/o SDS

40 20 0 1

10

100 Size, nm

1000

10000

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

0 ppm

Oil slick on seawater

Oil slick after mixing

Mixing + dispersant

100,000 ppm

100,000 ppm

100,000 ppm

Mixed oil slick (no dispersant)

Mixed & dispersant stabilized oil

After the centrifuge 7 ppm

107 ppm

Performance of UCLA Oil-Tolerant UF Membranes on Centrifuge Effluents Permeate

Feed

Membrane

Clean Tank

Feed Tank

7 ppm

< 0.5 ppm

Permeate

Feed 6-Cell Membrane Filtration System

Membrane

107 ppm

< 0.5 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 do…disperse 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 • UF membrane innovation

UCLA

WPE

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 water barge in Fort Jackson, LA.

Process engineers from CCS Midstream 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 Salvage’s Hammerhead and Splash Shallow Water Barges

Centrifuge system

4 Centrifuges each on Edison Chouest Offshore’s Ella G and Ingrid Platform Supply Vessels ~1 MGD capacity (~23,000 bbl/day)

Centrifuge system

6 Centrifuges on Hornbeck Offshore Service’s 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 Separation Technology

Field Influent (O&G)

Field Effluent (O&G)

Lab Influent (O&G)

Lab Effluent (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 • State of the technology

UCLA

WPE

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 oilwater 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 Recovered oil product dewatered to 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 • State of the technology

UCLA

WPE

Poly Cera

• Summary & discussion ??? 34

UCLA PolymericCeramic 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 BaSO4 or SrSO4

Souring Inhibition

Implementation: • Small scale lab trials Dow Filmtec and Marathon Oil (1987) • 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 2000‘s Factors – – –

•

Risk / Reward Acceptance of membrane and process technology by the (off-shore) O&G industry. Inherent cycle time of offshore projects

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 2000‘s (West Africa, Brazil, GoM) Souring Mitigation Membrane and system efficiency improvements • •

Rejection Surface area

Cumulative SRP capacity installed

Typical Process Sheets May 12-14, 2013

Multi-Media Filtration Pre-treatment

Membrane Filtration Pre-treatment

Graphs courtesy Total

Pre-treatment Process Comparison Option 1 – CF May 12-14, 2013

Lift Pump

Option 2 - MMF

Coarse filtration

HP pumps SRP

Cartridge filters

50-80 um

36 barg

5um

Coarse filtration

Lift Pump

150 um

Option 3 - UF Lift Pump

Coarse filtration

Media Filtration

Vacuum Deareation

2-5 um particle removal

MF/UF

36 barg

5 um

HP pumps SRP 36 barg

Vacuum De-areation

SRU

(2 stage, 75% conversion)

UF

CAPEX

++

+

+/-

OPEX

-- (SRU)

- (SRU)

+ (MMF) + (SRU)

++

--

Injection Pumps

+ (30% of footprint compared with MMF)

+

-

Weight

Established?

Injection pumps

SRU

Dual Media Filtration

Footprint

Injection Pumps

(2 stage, 75% conversion)

Cartridge Filtration

Efficiency

KR 03152012

Guard Cartridge Filters

HP pumps SRP

Vacuum De-areation

150 um

Pre-treatment Technology Comparison

SRU (2 stage, 75% conversion)

+ (40% of weight compared with MMF)

-6 weeks SR on-line

3-4 months SR on-line

+ >6 months targeted online

+

+

+/-

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 Maintenance

IOR

Water Flood

EOR

Tertiary Recovery

Thermal / Steam

Adopted from JPT , Jan 2012, SPE 143287

Gas

Other

Chemical (ASP)

Low - Tailored Salinity

Low Sulphate 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%

Recovery Process

Low Salinity: 5-15% Polymer Flooding: 5-20% ASP Flooding: 15-30%

WATERFLOOD Incremental 5 – 15%

PRIMARY Range 10 – 30%

0

20

40

% Original Oil in Place (OOIP)

60

80

100

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) SECONDARY RECOVERY

PRIMARY RECOVERY

NATURAL FLOW

Enhanced Oil Recovery (EOR)

WATERFLOOD

TERTIARY RECOVERY

PRESSURE MAINTENANCE

CHEMICAL

LOW SALINITY

SEAWATER ARTIFICAL LIFT

SULFATE REMOVAL

ALKALI, SURFACTANT, POLYMER (ASP)

WATER INJECTION

PRODUCED WATER REINJECTION

CUSTOM WATER THERMAL

SEAWATER PRODUCED WATER REINJECTION

SULFATE REMOVAL

SOLVENT

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

SRP Low Salinity Softening (Nanofiltration)

Resulting Salinity (TDS) 23,000 1,500

Alkali Concentration (mg/L) 14,000

20,000

14,000

1,000 1,000

Polymer Concentration (mg/L) 1,200 250

1,000

1,100

Surfactant Concentration (mg/L)

Indicative Incremental Oil Recovery by Treatment Process (Not Cumulative)

SRP Low Salinity Softening (Nano-Filtration)

Water Injection Only (no ASP) 0% 6%

Polymer (P) 3% 10%

AlkaliSurfactant (AS) 7%

AlkaliPolymer (AP) 12%

SurfactantPolymer (SP) 4% 15%

AlkaliSurfactantPolymer (ASP) 20%

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

May 12‐14, 2013

The use of ceramic membranes for treatment of Produced Water  f from Steam EOR to produce feedstock for steam generation and  d f d kf i d desalination for surface discharge Stanton R. Smith PhD, P.Eng CEng Business Development Manager Veolia Water Solutions and Technologies N.A. g

Background and Focus Background and Focus

14, 2013

Veolia supplied 45k BWPD Steam EOR PWT system to PXP in 2012 pp y System uses ROSSTM process to produce 50k BWPD water with  significantly reduced hardness, silica, O&G and TSS 25k BWPD ROSS effluent to: – OTSG for Steam EOR – OPUS II for surface discharge (and internal use) OPUS II for surface discharge (and internal use)

System commissioned H2 2012 into Q1 2013 Focus: piloting, scale up, commissioning and operation of ROSS  RO Pre‐treatment

Contents

14, 2013

Project Goals Treatment challenges and Technical solution Scale up of RO Pre‐treatment (i.e. ROSSTM process) Experience from delivery, commissioning and operation

14, 2013

Project Goals Project Goals

roject Goals 

uent uent 

14, 2013 Water Source

Steam Flood Oil Field Produced Water

Influent Quality Temperature : 160 – 200oF, pH : 7.0 Silica : 240 ppm, Total Hardness : 210 ppm as CaCO3 TDS : 2,100 ppm, Boron : 5.8 ppm, Ammonia : 16 ppm Free Oil : 120 ppm, COD : 690 ppm, TOC – 210 ppm Free Oil : 120 ppm, COD : 690 ppm, TOC  210 ppm

uent Requirements NPDES Surface Discharge Compliance to Permit ‐ CRWQCB, CA Title 22, CA Basin Plain Removal of Boron, Ammonia, TDS to low levels

OTSG Makeup Removal of Oil, Hardness and TSS to low levels

tem Capacity tem Capacity NPDES Discharge : 20,000 bpd OTSG Makeup : 25,000 bpd

5

ock Flow Diagram SEOR SEOR  PW

25,000  BWPD

ROSSTM + WAC 0,000 BWPD effluent

S IITM

00 BWPD Effluent

OTSGs

Internal users Surface Discharge 25,000  BWPD

RO system RO system 20,000  BWPD

Treatment Challenges and Technical  S l ti Solution

O Membrane ‐ Treatment Challenges

mbrane Scaling Potential b S li P i l Dissolved Silica (240 ppm) Calcium Salts ( CaCO3, CaF3) Metal Salts (Fe, Mn, Al etc.),

mbrane Fouling Potential Organic Fouling (TOC ‐ 210 ppm) Particulates (Free oil, TSS, etc)

mbrane Salt Rejection Boron Removal Organics Removal (Phenol) High Feed Water Temperature 

h System Recovery Rate y y Waste Minimization to Deep Well

8

OSSTM RO Pre‐treatment Goals

educe RO Membrane Scaling Potential d RO M b S li P t ti l Remove Silica to