A Look at Future HighA Look at Future High--Recovery Recovery gg yyRecovery Produced Water Recovery Produced Water TreatmentTreatment

Ken Klinko, Bob KimballKen Klinko, Bob KimballCCCDMCDM

Coalbed Methane Coalbed Methane Resources are Resources are National in Extent, National in Extent, but the cobut the co--Produced Produced Groundwater has Groundwater has issues that come with issues that come with itit

Total Dissolved Solids Total Dissolved Solids from the Producedfrom the Producedfrom the Produced from the Produced Water Database in the Water Database in the United StatesUnited States

Source: USGS Produced Water Database

Producers do not try to “dewater” the

d t ifgroundwater aquifer, only lower the hydrostatic pressure enough to releaseenough to release the gas…

Source: ALL Consulting Handbook on Coal BedSource: ALL Consulting. Handbook on Coal Bed Methane Produced Water: Management and Beneficial Use Alternatives, July 2003.

180

…So along with the gas comes

120

140

160

BW

PD

the gas comes water (typical water production in a CBNG field): 40

60

80

100

Wat

er P

rodu

ctio

n (M

B

in a CBNG field):

-

20

Jan-99

Jan-00

Jan-01

Jan-02

Jan-03

Jan-04

Jan-05

Jan-06

Jan-07

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Jan-09

Jan-10

Jan-11

Jan-12

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Jan-22

Historical Produced Water Management:

– Deep well injection

– Direct discharge

– Impound-ments

Irrigation– Irrigation

– Treatment andand discharge

Environmental Costs of Concentrated Salt Discharges Environmental Costs of Concentrated Salt Discharges gg

Salt Buildup in Receiving Waters Salt Buildup in Receiving Waters Real and Apparent Toxicity of concentrated

salts and trace contaminantssalts and trace contaminants Potential Salt Buildup in Soils and

Groundwater Impacts p Chronic and Acute Impacts on Wildlife

Less is Better when Discharging a Process Residual Less is Better when Discharging a Process Residual g gg g

It’s what’sIt’s what’s inin thetheIt s what s It s what s inin the the groundwatergroundwater: : Dominant Salts in Dominant Salts in Produced WaterProduced WaterProduced Water Produced Water By Basin:By Basin:

Basin-Wide Treatment Objectives for Produced Water: j• TDS Removal (soluble sodium salts)• Minimize brine disposal• Meet stringent discharge criteria for TDS (EC), SAR,

specific ions (i.e. Sodium), trace constituents (i.e. Arsenic, Fluoride)• Cost-effective Processes

Along with the water comes public and Along with the water comes public and regulatory perceptions and concerns:regulatory perceptions and concerns:

Current Trends and Future Produced Water Management:– Treatment and

discharge– Managed irrigationg g– Re-injection to

safe aquifer– Deep well

Pressure fromRegulators,Landowners

Deep well injection/storage

– Lined stock tanks“Grandfathered”Landowners,

and Public– “Grandfathered”

direct discharge only

Water Treatment Objectives and TechnologiesWater Treatment Objectives and Technologies

Key Treatment Technologies: Elements of each areKey Treatment Technologies: Elements of each are needed to meet future objectives!

Advanced Filtration Advanced Filtration Ion Exchange Reverse Osmosis Reverse Osmosis Mechanical Evaporation

Range of Technology Applicability vs. TDSRange of Technology Applicability vs. TDS

Crystallization

Evaporation

IXer B

arre

l

RO

IX

$ Cos

ts p

e

IX

3,000 40,000 260,000 1,000,000Total Dissolved Solids (TDS)

750

Produced Water Production Options and CostsProduced Water Production Options and Costs

Direct Discharge

Passive Treatment and Discharge IrrigationImpound-

mentOffsite Disposal/

InjectionRigorous Treatment

$0 03 $0 04 $0 10 $0 12 $0 2 $0 0$0.03-$0.05/bbl

$0.04-$0.06/bbl

$0.10-$0.16/bbl

$0.12-$0.18/bbl

$0.25-$2.00/bbl

$0.70-$5.50/bbl

COST ($/per barrel)

Illustration of Recovery EffectIllustration of Recovery Effectyy

Consider the case where 50% water recovery is the basis, Th h i iThen the average system concentration increase

as the recovery increases above that level is as follows:

WATER CONCENTRATION AVERAGE SYSTEM RECOVERY: FACTOR: CONCENTRATION INCREASE:

50% 2 (Base Recovery Level)75% 4 167%75% 4 167%90% 10 367%95% 20 700%98% 50 1700%98% 50 1700%

Reverse Osmosis: a Salt Removal Technology

Pressure

ConcentratedSalts

FeedFlow

H2O Mg

Fe++

SO4Na+

++

++

SaltsH2O

H2OH2OClHCO3 Ca

++

FOULANT LAYER

Membrane

H O H OH2O

H2OH2O

H2O

H2O H2O

Permeate

The Key to Success for RO Water Recovery: Minimize Deposition on the Surface

Concentration Polarization on Membrane SurfacesConcentration Polarization on Membrane Surfaces

Membrane Layer RO concentrates simultaneously as it purifies water. RO is a “non-selective” treatment

w Feed

RO is a non-selective treatment process: all ions are rejected, depending on their mass transport properties.

Permeate

Cross‐flo

w

Other constituents of the feed water can interfere with this separation and make the process inefficient

Concentration Increase

inefficient. The deposition of material on the membrane surface that impedes the design production and quality of the Concentration Increaseg p q ypermeate has to be avoided.

Distance from Membrane Surface

What do we need to remember when we design an RO membrane system?RO membrane system?

RO membranes are designed to remove specific ions from solution; this separation is physically on the angstrom (10-10 meter) levelangstrom (10 meter) level

Successful RO systems need effective process step(s) in front of the membrane unit to remove or minimize the presence of constituents in the feed that can inhibit membrane functionality.

Effective pretreatment makes it work by limiting the fouling potential of the feed water.

Case Study #1: CoalCase Study #1: Coal--bed Natural Gas: Powder bed Natural Gas: Powder River Basin , Montana River Basin , Montana ,,Project Basis:

• Modular Flow Increments: 20,000 bbl/d every six monthsmonths

• Final Design Flow: 120,000 bbl/day • Design/Build/Own/Operate

Includes Brine Disposal• Includes Brine Disposal• Long-term Operating Contract

Feed Quality and Effluent

Targets:

Parameter Feed Effluent Targets

Conductivity, µs/cm2 2,933 <1,000Hardness (CaCO3) ppm 33( 3) pp

Sodium, mg/L 787Bicarbonate, mg/l 2,047

Total Nitrogen, mg/l 2.0 1.1

SAR 61 <3

Multiple Technologies Provide a Solution Path Multiple Technologies Provide a Solution Path to High Water Recovery:to High Water Recovery:to High Water Recovery:to High Water Recovery:

Calcium/Magnesium Chloride SolutionFilter BW

Perm

ProducedWater

EffluentDischarge

Advanced Filtration

UV Oxidation

Low Pressure RO

WAC WaterSoftener

Scale Inhibitor/Dispersant (3 7 ppm)

HCl(intermittent, low volume)

RejectRO Perm

High Pressure RO

(3-7 ppm)low volume)

Perm Keep produced water anaerobic Filter colloidal material effectively Remove polyvalent cations that form

Evaporator(Optional)

Natural Gas/Waste Heat Di till t

Reject Remove polyvalent cations that form fouling compounds as they are concentrated Concentrate monovalent ionic species Evaporate residual

( p ) DistillateConc Brineor Solids

Comparison to IX Technology:Comparison to IX Technology:Basis: 35,000 bbl/d Feed at EC: 2,900, SAR: 61Basis: 35,000 bbl/d Feed at EC: 2,900, SAR: 61Treatment to EC: 1,000, SAR: 3Treatment to EC: 1,000, SAR: 3

Case Study @ PRB Treatment to EC: 1,000, SAR: 3Treatment to EC: 1,000, SAR: 3

Performance CDM RO Process with ZLD

Single (IX) Technology

O ll R 100% 97 %Overall Recovery ~100% 97+%

Bypass of Untreated Water 0% 8%

Off-Site Brine Disposal 0 bbl/wk 4,800 bbl/wk

Effluent EC, S/cm 235 1,000

Acid Addition (32% HCl) <750 gal/wk 40,000 gal/wk

Gypsum Addition for SAR 0 tons/yr 865 tons/yryAdjustment 0 tons/yr 865 tons/yr

Case Study #2: Case Study #2: yy

Tight Sand GasTight Sand GasPiceancePiceance Basin, ColoradoBasin, ColoradoPiceancePiceance Basin, ColoradoBasin, Colorado

Design/Build/Own/Operate

90% R d ti i V l 90% Reduction in Volume

Doesn’t Include Brine Disposal

Limited Space for Ponds

Project Basis:Project Basis:Limited Space for Ponds

Total Flow: 20,000 bbl/day

5+ Year Contract

Feed Quality and Effluent TargetsFeed Quality and Effluent TargetsCase Study @ Piceance

Effl tParameter Feed Effluent Targets

TDS 11,215 <500

Hardness (CaCO3) 213

Sodium 4,036

Bicarbonate 2,059

Chloride 5,202

Sulfate 21

Oil/Grease 438 <10

Silica 119

All values in mg/L

CDM Treatment Process CDM Treatment Process Case Study @ Piceance

Oil

PermProducedWater

EffluentDischarge

Oil

DAF CDMProcess

Solids Contact Clarifier

Lime RejectAirH2SO4 MgSO4

DistillateSaturatedB i S l ti

Evaporator(Optional)

Brine Solution

SludgeDisposal

FilterPress

Performance and Cost SummaryPerformance and Cost SummaryCase Study @ Piceance

Effl TDS 478 /L Effluent TDS: 478 mg/L Recovery: 90% (1,200 psig) Meets all other target standardsg By-products:

– Oil: 10 bbl/dLi Sl d 4 5 t t /d– Lime Sludge: 4.5 wet tons/d

Chemical Usage (for added steps):– Sulfuric Acid: 0.4 lbs/bbl– Magnesium Sulfate: 0.15 lbs/bbl– Lime: 0.084 lbs/bbl

Cost:<$2 /bbl Cost:<$2 /bbl

Case Study #3: East Cherry Creek Valley Water and Case Study #3: East Cherry Creek Valley Water and Sanitation District Zero Liquid Discharge (ZLD) Pilot TestSanitation District Zero Liquid Discharge (ZLD) Pilot Test

ParameterParameter CBM Pilot CBM Pilot RO Brine Recovery PilotRO Brine Recovery PilotInitial Feed Medium TDS

L H d L SiliCharacterization High Silica

Low Hardness Low Silica

pH (su) 8.1 7-7.5

Total Alkalinity (mg/l CaCO ) 1600 1300-1500Total Alkalinity (mg/l CaCO3) 1600 1300-1500

Total Hardness (mg/l CaCO3) 30 5-30

Silica (mg/l) 11.2 20-30

TDS (mg/L) 1970 3600-5000

TOC (mg/l) < 1.0 7-30

M j I ( /l)Major Ions (mg/l)

Calcium 7 1-5Magnesium 5 0.5-5Sulfate 138 900-1000Chloride 18 370-450

Case Study #3: ECCV Pilot treated LPRO Concentrate w/ High Hardness Case Study #3: ECCV Pilot treated LPRO Concentrate w/ High Hardness and Sulfates Using BWRO @ 300 psi and SWRO @ 600 psiand Sulfates Using BWRO @ 300 psi and SWRO @ 600 psi

Overflow to Existing Sanitary Sewer Disposal

16 gpm16 gpm

16 gpmOverflow

g @ p @ pg @ p @ p

Sodium Zeolite

Ion E h

WACWeakAcid

Cation

5µCartridge

Filter

Permeate Flush

SystemTransfer Pump to Dry SaltGeneration

16 gpm16 gpm

From Primary RO Concentrate

Permeate Storage

Tank

15.3

Composite Brine Tank

64 ppt BrineExchangeSoftening

CationIon

Exchange

Stage 1 & 2 BW RO

STAGE 1

16 gpmIon Exchange Feed Pump

Holding Tank

16 gpm

gpm

10.4 gpm

STAGE 1Feed Water Pump

Metering

NaCLTank

Flushing Drain5.6

gpm

Recovery = Recovery = 94%94%

Antiscalant

Stage 3 SW RO

HCL Tank

Chemical Feed Pump

Pump

STAGE 2Feed Water

Pump

gpm

4.6 gpm

Flushing Drain

1 gpm

Typical Sulfate, Silica and Typical Sulfate, Silica and yp ,yp ,Chloride Intermediate Chloride Intermediate Precipitates Generated from Precipitates Generated from Concentrated BrineConcentrated BrineConcentrated BrineConcentrated Brine

Approximate Mineral Name Chemical Formula

ppwt%

Halite NaCl 18

Thenardite Na2SO4 <3

Quartz SiO2 8

Burkeite Na6CO3(SO4)2 35

Trona Na3H(CO3) 2-2H20 35

Unidentified ? <5

Overall Mass Balance of a ZLD SystemOverall Mass Balance of a ZLD System

Secondary RO Processes Can Be Effective in Reducing the Process Residual Liquid Volume

2

©AMTA July 13-19, 2009

Conclusion: High Recovery and Potentially ZLD Can Conclusion: High Recovery and Potentially ZLD Can Be Achieved with Secondary RO Processes inBe Achieved with Secondary RO Processes inBe Achieved with Secondary RO Processes, in Be Achieved with Secondary RO Processes, in Combination with Other Process TechnologiesCombination with Other Process Technologies

Cost-effective with water recoveries up to 97 – 98%

High quality effluent that can meet current and future regulatory97 98%

Little chemical addition required; continuous or intermittent

and future regulatory standards

Modular system configurationsintermittent

Minimal membrane fouling

configurations Broad application

across basins

Beneficial High Recovery of a Scarce Water Resource can be Beneficial High Recovery of a Scarce Water Resource can be achieved and Gas Production can increase at the same time;achieved and Gas Production can increase at the same time;achieved and Gas Production can increase at the same time; achieved and Gas Production can increase at the same time; the two are not mutually exclusive the two are not mutually exclusive

Critical Success Factors for High Water Recovery Processes:Processes:– Identifying potential precipitates at high recovery

given the kinetics and potential catalystsg p y

– Reducing hardness to negligible levels

– Minimizing concentration polarization on membranes g pat high recoveries

Thank you!Thank you!yy