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the water sustainability solutions Technical Brief Oil and Gas Produced Water Treatment Technologies

water sustainability solutions

the water sustainability solutions Technical Brief Oil and Gas Produced Water Treatment Technologies

Technical Brief

Oil and Gas Produced Water Treatment Technologies


Produced(waters ,(co . produced(during(the(extraction(of(oil(and(natural(gas(reserves, ( in(addition( to( the( flow( back( water( from( hydraulic( fracturing( activities( ( i.e.,( frac( water)( must( be( properly( managed(in(order(to(mit igate( any(environmental(impacts(and(impacts(to(existing(water(supplies( by( energy( development( activities( [ 1 ] .( Hydraulic( fracturing( is( typically( used( to( open( up( tight( geologic( formations ( or( reservoir( rock( ( (e.g.,( shale ( formations )( so( that( t he( natural( gas(may( be( more(easily(extracted.( Recent(estimates(for(the(amount(of(produced(water(that(is(generated(in( the( United( States( (US)( range( from( 1.6( to( 2.1( million( gallons( per( day( (mgd)( [ 1 ] .( ( As( energy( exploration( and( extraction( continue( to( increase( (e.g.,( oil( shale( and( coal( bed( methane( development)( these( volumes( of( water( will( likely( continue( to( increase( [ 2 ] .( The( chemistry( and( composition(of(pro duce d(and(hydraulic(fracturing(flow back(waters(is(highly(variable(and(in(many( cases( quite( complex.( The( most( significant( concern( for( developing( effective( management( strategies( for( these( waters( is( removing,( or( reducing,( the( total( dissolved( solids( (TDS)( conce ntration(prior(to(reuse.(This(technical(brief( provides(an(introduction(to (some(of(the(more( commonly( employed( treatment( strategies( for( pro duced/hydraulic( fracturing( flow back( waters .( Emphasis(is(placed(on(the(current(maturation(state(of(these(technologies(an d(addresses(some(of( the(associated(advantages(and(disadvantages(with(their(use(for(managing(produced(waters.((


Oil!and!Gas!produced!waters! are!commonly!characterized!by!high! salt!concentrations!which! requires!their!disposal!in!evaporation!ponds.!

Produced! Water!Chemistry!and!Composition. (Produced( waters( Produced(waters(are(generally( characterized(as(brackish(water(solutions(containing(high(concentrations(of(dissolved(minerals,( metals,( and( salts( [ 1 ,( 3 . 5 ] ( (Table( 1).( Waters( that( are( characterized( by( relatively( high( TDS( concentrations( (>( 1,000( mg/L)( require( some( form( of( treatment( prior( to( their( discharge( o r( beneficial( reuse( [ 6 . 8 ] .( For( comparison( the( secondary( drinking( water( standard( for( TDS( is( 500( mg/L( as( established( by( the( United( States( Environmental( Protection( Agency( (USEP A).( Additionally,(produced(waters(can(contain(high(levels(of(organics(like(oils,(greases,(and(benzene,( toluene,( ethylbenzene,( and( xylene( (BTEX)( compounds( [ 1 ] .( The( specific( composition( and( chemistry(of(produced(waters(is(site(specific(and (in(fact(vary( dependent( on(the(location(and(type( of( geologic( formation( from( which( the( produced( water( is( extracted ( [ 1 ,( 2 ] .( Furthermore,( the( chemistry(and(composition(of(produced(water(from(a(single(source(may(fluctuate(greatly(during( the(operation(of(the(w ell.(This(fact(requires(that(the(associated(treatment(system(be(flexible(so( that( it( can( accommodate( changes( in( the( feed ( water( quality.( Despite( the( variation( in( water(


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qualities( produced( waters( tend( to( have( relatively( high( TDS( concentrations( that( make( them( u nsuitable( for( most( potable( water( applications( without( treatment.( Indeed,( produced( waters(


five(times(that(of(seawater((TDS(~(36,000(mg/L).( (

Table!1 .(Concentrations(of(common(inorganic(and(organic(constituents(in(produced(waters( (adapted(from( [ 1 ,( 2 ] ). (

Constituent !

Low !

Medium !

High !

TDS,!mg/L !

1,000 (

32,300 (

400,000 (

Sodium,!mg/L !

nd (

9,400 (

150,000 (

Chloride,!mg/L !

nd (

29,000 (

250,000 (

Barium,!mg/L !

nd (

n/a (


Strontium,!mg/L !

nd (

n/a (

6,250 (

Sulfate,!mg/L !

nd (


15,000 (

Bicarbonate,!mg/L !

nd (


15,000 (

Calcium,!mg/L !

nd (

1,500 (

74,000 (

Total!organic!carbon,!mg/L !

nd (

n/a (

1,700 (

Total!volatile!organics,!mg/L !


n/a (


Total!recoverable!oil!and!grease,!mg/L !




nd( – (value(is(below(the(detection(limit(of(the(analytical(equipment(used( n/a( – (data(not(available (

Hydraulic!Fracturing! (Fracking) . ( Flow . Back(Water(Chemistry(and(Composition.(Unlike(produced( waters(the(chemistry(and(composition(of(frac (water(is(poorly(characterized.(The(reason(for(this( is(the(fact(that(different(entities(may(add(proprietary(chemicals(and(other(additives(that(are(not( disclosed(to(the( public.( Generally(speaking(however,(frac(water(is(brackish((TDS(>(10,000(mg/L)( and( conta ins( various( organic( additives( and( volatile( organic( compounds .( Example( chemical( additives(to(frac(water(include( pota ssium(chloride,(guar(gum,(ethy lene(glycol,(sodium(carbonate,( potassium(carbonate,(sodium(chloride,(borate(salts,(citric(acid,(glutaraldehyde,(acid,(petroleum( distillate,(and(isopropanol( [ 9 ] .( Fracking(requires(large(quantities(of(water (to(degree(of(roughly(2( to( 5( million( gall on s( of( frac( water( per( well ( [ 10 ] ( Note( that( a( single( well(may( be( fracked( over( a( dozen(times(during(its(lifetime.( Approximately( 1 5 %(to( 8 0% ( of(the( injected(frac( water(returns(to( the(surface(as( flowback (water.( (

Treatment!Costs .( The(costs(associated(with(managing(and(treating(produced( and/or(frac( waters( can( is( highly( dependent( on( the( chemistry/composition( of( the( raw( water( and( the( required( finished(water(quality.(Therefore,(estimating(the(costs(for(managing(these(waters(is(complex( at( best(given(the(wide(variability(in(the(chemistry(of(produced/frac(waters.(In( some( cases( the(cost( of( treating( the( produced( water( can( be( prohibitive( to( energy( development( ventures.(( Furthermore,( as( clean( water( is( a( scarce( resource,( treating( and( reusing( th ese( water s ( for( beneficial( applications((i.e.,(for(irrigation,(industrial(processes,( frac(water(make(up,( or(other(non . potable(purposes)(may(have(significant(economic(incentives((Produced(Water(Utilization(Act(of( 2008,(H.R.(2339).(( For(hydraulic(fracturing(r ecovering(and(reusing(the(flowback(water(can(reduce(

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costs(associated(with(disposing(of(the(wastewater(and(the(acquisition/transport(of(new(make(up( water.( Essential(to(the(realization(of(these(beneficial(reuse(applications(is(the(development(and( implementat ion( of( effective( produced( water( treatment( systems;( however,( the( complex( chemistries( that(characterize( these( waters(makes( treatment(by(existing(desalting( technologies( difficult(at(best.( (

Removing(TDS( from(any(water(is(an(energy(intensive(endeavor.(Generally ( speaking( treatment( costs(will(increase(rather(rapidly(as(the(TDS(concentration(increases.( For(membrane(processes,( such( as( reverse( osmosis( (RO)( this( relationship( between( cost( and( TDS( is( attributed( to( the( relationship(between(salt(concentration(and(osmotic( pressure( (i.e.,(as(salinity(increases(so( too( does( the(osmotic(pressure(of( the(solution).(More(saline(solutions(will( require(larger(and(more( energy(in tensive( feed(pumps(in(order( to(overcome( the(osmotic(pressure(of( the( feed( solution. ( The( type( of( desalination ( technology( used(will(vary( depending( on( the(ionic( composition( of( the( water.(For(example,(ion(exchange(or(pH(adjustment(may(be(used(when( the(water(is(primarily( composed( of( carb onate( species,( while( membrane( processes( or( distillation( processes( will( be( require d( for( more( complex( waters.( Unique( considerations( associated( with( produced( and( frac( water(treatment(systems(are(outlined(below: (

Treatment! system!mobility ( to(account( for( the(variable(lifetimes(of(producing(wells(as( well(as(the(development(of(new(ones.( (

High! source! water! recovery ( to( mitigate( the( further( treatment( and/or( disposal( of( wastewaters(resulting(from(the(treatment(of(the (produced/frac(water.( (

Variability! in! source! water! quality ( requires( that( systems( be( flexible( and( robust( to( account( for( changes( in( wate r( quality( during( the( maturation( of( a( well,( as( well( as( the( different(water(qualities(from(newly(developed(wells.((

Treatment ! / ! finished! water! quality! requirements ,! together! with! the! chemistry ! / ! composition! of! the! produced ! / ! frac! water , ( dictate ( the( type( of( treatment( that(will( be( required.(As(such,( the(level(of(treatment,(and(thus(the(cost(of(treatment,(may(vary(from( one(location(to(the(next. (


The(level(of(treatment(that(is(required(is(dictated(by(the(intended (application(or(end(use(for(the( treated( produced( water.( Regardless( of( the( intended( application( however,( some( form( of( treatment(will(likely( be( required(in( order( to(meet( the( regulatory( criteria( for( the( targeted(end( use.(As(clean(water(is(a(scarce(resource,(treating(produced(water(may(have(significant(economic( incentives,( such(as( its(expanded( use(as( irrigation(water,( process(make . up(water,( or(even(as(a(


and(compositio n(of(produced(waters(is(variable(it(generally(contains(high(concentrations(of(TDS( and(volatile(organic (compound s((VOCs).( Hydrocarbon(products(and(VOCs (may(be(removed(using( a( range( of( conventional( treatment( systems,( such( as( oil( water( separators,( aeration( systems,( dissolved( air( flotation,( and( oxidation( processes.( Effluents( from( these( conventional( treatments( usually(meet(the(requirements(for(surface(holdin g(ponds(and(subsurface(injection;(however,(the( exceptionally( high( TDS( concentrations( in( produced( water( present( unique( and( substantial( challenges.( The( need( for( reducing( TDS( concentrations( is(especially( important( for( areas( where(


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salinity( management( is( critic al,( such( as( for( the( Colorado( River( Basin( [ 11 ] .( High( TDS( concentrations( are( in( fact,( problematic(even( for( underground( injection,( as( a( result( of(mineral( scaling(from(calcium(carbonate(and(barium(sulfate,(which (can(plug(subsurface(formations.( (

A dvanced(separation(processes,(which(are(collectively(referred(to(as(desalination(processes(are( required.( Examples( of( desalination( technologies( include( electrochemical( processes,( ion( exchange( (IX),( mechanical( evaporation( p rocesses( [ multi . effect( distillation( (MED),( multi . stage( flash( (MSF)( distillation,( and( vapor( compression( (VC) ] ,( capacitive( deionization,( pressure( driven( membrane( processes,( and( non . pressure( driven( membrane( processes( (e.g.,( membrane( distillation,( forward( osmo sis,( electrodialysis( reversal) .( Of( these( different( demineralization( techniques( only(IX ,(mechanical(evaporation( or( distillation,( and( the(membrane( processes( have( received(widespread(application(in(the(treatment(of(produced(waters.( M echanical(evaporation( processes(have(been( used(to(treat(produced(waters( from(a(variety(of(sources(such(as(the(Fort( McMurray,( Alberta( tar( sands;( however,( evaporative( processes( suffer( from( a( number( of( drawbacks.(For(example,(large . scale(mechanical(evaporation(systems(are(energy(i ntensive(and( complex.(Nevertheless,(evaporative( processes( are( in( some( cases( the( best( and( only( option( for( treating(challenging(water(sources ((TDS(>>(50,000(mg/L) .(Processes(like(capacitive(deionization( are(in(the(early(stages(of(development(and(have(yet(to( be(tested(on(a(reasonable(scale,(though( early(results(are(promising( [ 7 ] .( The(following(sections(are(intended(to(provide(a(brief(overview( of(a(select(number(of(treatment(p rocesses(that(are(commonly(used(in(treating(produced(and( to( some(extent(frac(waters. (


Pressure( Driven( Membrane( Processes.( Pressure . driven( membrane( processes( are( perhaps( the( most( well( known( desalting( technology( and( include( processes( such( as( nanofiltration( (NF)( and( reverse(osmosis((RO).( NF(is(differentiated(from(RO(in(that(it(is(primarily(used(to(removal(multi . valent(ions(like( calcium(and(magnesium(and(is(commonly(referred(to(as(membrane(softening.( In( addition( to( NF( and( RO( are( several ( design ( variations( that( are( meant( to( mitigate( membrane( fouling( in( an( attempt( to(maximize( the( achievable( feed( water( recovery( ratio.( Both(NF( and( RO( h ave(long( been( used( for( treating( saline(water( sources(in(municipal(and(industrial(applications( [ 12 . 14 ] ,(including(produced(waters( [ 6 ,( 7 ] .(The(modular(design,(small(equipment( footprint,(low( labor(re quirements,(and(superior(product(water(quality(all(make( them(an(attractive( treatment( option( for( produced( waters( [ 2 ] .( NF( and( RO( are( considered( to( be( high . pressure( membrane( processes(as(they(typically(require(fe ed(pressures(in(the(range(of(100(to(1,000(psig.(Such(high . pressure( requirements( arise( from( the( relatively( high( osmotic( pressures( that( characterize( the( feedwaters(to(these(processes.( (

Pressure( driven( membrane( processes( utilize( a( semi . permeable( membrane( to( s eparate( suspended( and( dissolved( contaminants( from( a( feed( solution.( Here,( pressure( is( applied( to( a( feedwater( in( order( to( force( the( water( through( the( semi . permeable(membrane,( which( retains( the(salt(s)(while(allowing(water(to(pass(through(as(a(result(of(diffe rences(in(diffusivity(between( the( solute(and(water(molecules.( Because(it(is(a( separation,(and( not(a( treatment,( process( two( liquid(process(streams(are(produced:(i)(a(clean(demineralized(product(water((permeate)(and(ii)(a( reject( or( concentrated( brine( solutio n( (concentrate).( The( operating( pressure( in( the(membrane( system(must(be(greater(than(the(solution’s(osmotic(pressure(in(order(for(water(to(flow(from(the( feed(solution(and(across(the(membrane.(Because(the(osmotic(pressure(increases(with(increasing(


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salt( conce ntration( the( pressure( and( pumping( requirements( will( increase( with( TDS( concentrations. ( (

The( high . pressure( feed( pump( is( the( largest( energy( consumer( in( high . pressure( membrane( processes.(Secondary(energy(consuming(devices(include(the(concentrate(and(permeate( booster( pumps((if(required).(For(salt(rejecting(membranes(energy(consumption(is(directly(related(to(the( TDS(concentration(in(the(feed(wate r ,(which(also(ultimately(determines(the(achievable( recovery( ration( (Q product /Q feed )( for( the( desalting( process .( Salts( i mpart( an( osmotic( pressure( that(must( be( overcome(in(order(to(transport(water(across(the(membrane.(Thus,(greater(feed(pressures,(and( in( turn( pumping( requirements,( are( needed( for( higher( salinity( waters.( Furthermore,( practical( recovery(ratios(for(feed(TDS(conc entrations(of(36,000(mg/L(are(50%,(with(this(ratio(decreasing( as(TDS(increases(beyond(this(value.(This(means(that(for(a(produced(water(characterized(by(a(TDS(


whi le(the(other(half((i.e.,(the(concentrate)(must(still(be(disposed(of.( This(is(a(critical(concern(for( produced(waters(where(the(raw(water(TDS(concentration(may(be(many(times(that(of(seawater( (TDS( ~( 36,000( mg/L).( Thus,( concentrate( disposal( is( a( significant( co st( and( environmental( consideration( for( desalting( membrane( processes.( Membrane( f ouling( is( an other ( important( consideration( because( it( reduces( membrane( permeability( and( necessitates( higher( feed( pressures(in(order(to(maintain(a(desired(permeate(flux.( (


Picture!of!a!typical!reverse!osmosis!(RO)!desalination!treatment!system !

The(importance(of(fouling(points(to(the(significance(of(implementing(an(effective(pretreatment( scheme( in( order( to( minimize( energy( costs.( This( is( a( particularly( relevant( point( for( produced( waters(as(they(may(contain(relatively(high(concentrations(of(recalcitrant(foulant(materials(such( as( oils,( greases,( and( dissolved( metals( [ 1 ] .( Efforts( to( overcome( fouling( have( led( to( the(


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development( of( unique( design( approaches( for( pressure( driven(membrane( processes,( some( of( which(are(outlined(below: (

Vibratory! Enhanced! Membrane! Process! (VSEP): ( VSEP( is( a( proprietary( compact( mechanical( membrane( system( (New( Logic( Research,( Oakland,( CA)( that( can( process( high(salinity(waters(and(dilute( sludges.( VSEP(has(successfully( been(used( in(more(than( 200( commercial . scale( industrial( applications( treating( extremely( challenging( source( waters((high(TDS,(high(solids(content).(The(system(consists(of(a(series(of(disk . shaped,( flat . sheet(membranes(attached(t o(a(central(shaft.(The(shaft(rotates(a(short(distance(in(


the( outer( edge( of( the( membrane( disks,( the( amplitude( of( the( oscillation( can( be( adjusted(to(between(0.25(and(1.2 5(inches.(The(oscillating(motion(in(the(VSEP(system( allows( NF( and( RO( membranes( to( treat( high( TDS( source( waters( (e.g.,( 300,000 ( mg/L( TDS)(such(as(those(produced(by(shale(gas(activities.(The(oscillation(reduces(membrane( fouling(by(increasing(the(shear(forces( and(mixing(at(the(membrane(surface.(This(action( significantly( reduces( foulant( deposition( and( the( thickness( of( the( concentration( polarization(layer(that(forms(at(the(surface(of(salt(rejecting(membranes.(Both(of(these( actions( would,( if( not( controlled,( contri bute( to( a( significant( loss( of( permeate( flux( through( the( membrane.( The( shear( action( prevents( the( formation( of( a( continuous( scale(on(the(membrane(surface( [ 15 ] .(Instead,(the(minerals(nucleate(and(form(colloids( in( the( bulk( solution.( This( allows( the( VSEP( process( to( achieve( higher( raw( water( recoveries,( and( treat( waters( having( substantially( higher( TDS( c oncentrations,( than( conventional(RO( systems.(Furthermore,(VSEP(is(capable(of(processing( source(waters( that( have( high( concentrations( of( suspended( solids( and( organic( materials,( thus( minimizing( the( amount( of( pretreatment( requirements.( Despite( its( promise( the( application( full . scale( VSEP( systems( in( produced( water( treatment( applications( has( been( limited,( likely( as( a( result( of( comparatively( high( energy( and( capital( equipment( requirements.( ( (

High!Efficiency!Reverse!Osmosis! (HERO): ( Another(RO(design(approach(that(has (been( developed(for(increasing(the(achievable(recovery(ratio(for(high(salinity(source(waters( is( the( high . efficiency( reverse( osmosis( (HERO )( process.( ( Here,( scale( forming( compounds( (Ca,(Mg,( Si)( are( removed( before( the( RO( step( using( a( softening( process.(( S ilica(precipitation( in( the(RO(process(is(mitigated(by(operating(at(a(high( solution(pH( ( pH( >( 9) .( ( Collectively( these( efforts( reduce( membrane( fouling( and( allow( for( the( RO( system(to(operate(at(higher(recovery(ratios(than(traditional(RO.( While(it(is(possible(t o( achieve( high( feedwater( recoveries( (>( 90% ( in( some( cases ),( the( consumptive( use( of( chemicals(is(substantial (and(the(challenges(associated(with(high(osmotic(pressures(for( highly(saline(waters(remains(an(issue . (

Non R Pressure! Driven! Membrane! Processes. ( Non . pres sure( driven( membrane( processes( utilize( mechanisms( other( than( hydraulic( pressure( to( transport( water( across( a( membrane( barrier.( Examples(of(non . pressure(driven(membrane(processes(include(membrane(distillation,( forward( osmosis,(and(pervaporation.(While(each(o f(these(processes(are(described(in(greater(detail(below( it( is( prudent( to( point( out( that( few( of( these( processes( are( currently( used( in( treating( produced/frac(waters.( Forward(osmosis(has(perhaps(received(the(most(application(in(full . scale( settings.( Some( of( th e( advantages( and( challenges( that( are( associated( with( these( non . pressure( driven( processes( are( highlighted( in( Table( 2 .( Little( cost( data( is( available( for( the( non . pressure(


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driven(processes( that(are(discussed(in(this(report;(however,(where(appropriate(reference(will(be( made(as(to(the(unique(design(characteristics(for(each(process(that(can(improve(or(hinder(their( cost(competiveness(to(more(traditional(desalting(technologies.( (

Membrane! Distilla tion! (MD) . ( Membrane( distillation( (MD)( is( a( thermally( driven( separation( process(that(has(received(attention(as(a(possible(water(and(wastewater(treatment(technology(in( applications( such( as( desalination( and( water( reuse( [ 16 . 18 ] .( In( contrast( to( processes( like( RO,( which( utilize( pressure( as( a( driving( force( for( mass( transport,( MD( utilizes( the( vapor( pressure( difference(across(a(membrane( [ 18 ] .(In(MD,(the(vapor(pressure(difference(is(affected(by (different( parameters( [ 17 ] ;( however,( the( thermal( gradient( across( the( membrane( is( the( primary( mechanism( for( mass( transport.( Water( vapor( is( transported( from( the( feed,( which( is( at( an( elevated( temperature( relative( to( the( permeate( side,( across( a( hydrophobic( micropo rous( membrane(and(into(a(condensing(medium( [ 17 ] .(There(are( a(variety(of( MD(configurations(which( may( be( used( [ 18 ] ;( however,( ( a ( universal( critical( process( parameter( is( the(maintenance( of( the( liquid . vapor(interface((i.e.,( liquid(water(cannot(penetrate(the(membrane(pores,(which(requires( the(use(of(a(durable(hydrophobic(membrane( [ 19 ] .( (

The( principle( advantage( of(MD( derives( from( the( fact( that( it( is( a( thermally,( and( not( pressure,( driven( separation( process.( Therefore,( MD( does( not( need( to( overcome( the( high( osmotic( pressures( that( characterize( produced( waters.( For( this( reason,( MD( is( an( attractive( treatment( technology( for( produced( water s( because( it( is( not( osmotically( limited( like( pressure( driven( membrane(processes.(Additionally,(MD(requires(significantly(lower(operating(temperatures(and( thus( has( lower( energy( requirements( relative( to( mechanical( evaporation( processes.( It( is( important(to(be ar(in(mind(though(that(a(“waste(heat(source”(must(be(available( in(order(to(allow( the(MD(process(to(function.(In(the(absence(of(a(heat(source(the(energy(requirements,(and(thus( the( costs,( associated( with(MD( can( increase( dramatically.( Finally,( because( non . volatile( solutes( cannot(be(transported(across(the(membrane(barrier(in(a(MD(system,(it(is(capable(of(achieving( near(100%(rejection(of(dissolved(salts(and(minerals( [ 17 ] .(For( these(reasons,( MD(is(a(promising( technology( that( has( progressively( gained(attention( as(a( treatment(alternative( for( high( salinity( source(waters( [ 17 ,( 20 ] . (

Forward! Osmosis. (Forward( osmosis( (FO)( operates( on( the( process( of( natural( osmosis(in(which( water(flows(from(an(area(of(low(salt(concentration,(across(a(semi. permeable(membrane,(to(an( area(of(high( salt(concentration(in(an(attempt( to( reach(an(equilibrium( state( ( balancing(out( the( osmotic( pressure( difference( between( the( two( solutions.( FO( is( sometimes( referred( to( as( engineered(osmosis(as(an(osmotic(agent(is(used(to(draw(water(from(a(saline(feed(water,(such(as( produced( water,( into( a( dra w( or( cap ture( solution.( The( two(most( critical( components( in( an( FO( system(are(the(osmotic(agent(and(the(membrane.(To(be(successful(the(osmotic(agent(must(be( highly(soluble(in(water,(be(easily(recovered,(and(impart(a(high(osmotic(pressure(when(dissolved( in(so lution.(The(most(promising(osmotic(agents(include( various(types(of(ammonia(salts(because( they( can( be( relatively( easily( recovered( from( solution( and( reused.( There( are( a( few( FO( membranes( and(systems( currently(on(the(market((see(e.g.,(Hydration(Technology(Inno vations) ;( however,(an(inherent(challenge(with(FO(processes(is(concentration(polarization.(Concentration( polarization(can(occur(on(both(the(feed(and(permeate(sides(of(the(membrane,(as(well(as(in(the( membrane( interior( (internal( concentration( polarization).( A ll( of( these( types( of( concentration( polarization( act( to( reduce( the( osmotic( pressure( gradient( between( the( feed( and( permeate( solutions( resulting( in( a( reduction( in( the( permeate( flux( rate.( This( is( particularly( challenging( because(it(is(difficult(to(overcome(ope rationally.(For(example,(in(pressure(driven(processes(it(is(


7 !

possible( to(increase( the(hydraulic(pressure( that(is(applied(in(order( to(maintain(a(constant( flux( rate(while(accommodating(losses(in(flux(as(a(result(of(fouling.(Conversely,(increasing(the(osmotic( pressure(gradient(requires(the(addition(of(greater(quantities(of( osmotic(agent(and/or(increased( mixing( at( the( membrane( surfaces.( Regardless( of( the( action( taken( concentration( polarization( poses(a( significant( hurdle( to( the(wide( spread(application( of( FO( in( th e( produced(water( sector,( because(of( the(already(low( flux( rates( that(characterize( this(process.(Nevertheless,(advances(in( membrane(materials,(process(design,(and(new(types(of(osmotic(agents ( are( promising.( (

Table! 2 . ( Advantages( and( challenges( associated( with( different( non . pressure( driven(membrane( processes (in(produced(water(treatment(applications .( (

Process !

Advantages !

Challenges !


Requires(waste(heat(source( to(drive(mass(transport (

Low(pumping(requirements( resulting(in(low(energy( footprint(assuming( waste( heat(source(is(available (

Capable(of(treating(high( salinity(solutions((TDS(>( 50,000(mg/L) (

Lack(of(commercially( available(membranes (

Membrane!Distillation !

Susceptibility(to(pore( flooding(from(membrane( fouling(resulting(in(la ck(of( ion(rejection (


Largely(unproven(at(full . scale(installations (


Recovery(of(osmotic(agent( can(be(technically(and( economically(challenging (

With(proper(selection(of( osmotic(agent(it(is(capable( of(treating(high(salinity(


Concentration(polarization( (internal,(external)( dramatically(reduces( permeate(flux(rates (

Forward!Osmosis !

mg/L) (

Pumping(requirements(are( low(as(mass(transport(is( driven(by( differences(in( osmotic(pressure (

Comparatively(low(flux(rates( to(pressure(driven( membrane(proc esses (

Few(full . scale(installations( and(limited(commercially( available(membranes (

Ion! Exchange. ( Ion( exchange( (IX)( is( a( process( in( which( ions( are( exchanged( between( an( ion( containing( solution( and( a( bed( of( synthetic( resin( beads( (adsorbent)( presaturated( with( noncontaminant(ions,(such(as(sodium((Na + ),(chloride((Cl . ),(hydrogen((H + ),(or(hydroxyls((OH . )( [ 21 ] .( Using( IX( it ( is( possible( to( selectively( remove( nitrogen( compounds,( hardness( (i.e.,( water( softening),(and(monovalent(ions(like(sodium(and(chloride(from(aqueous(streams(and(has(widely( been( applied( in( municipal,( industrial,( and( residential( applications.(While( IX( may( be( used( in( a( wide(range(of(applications,(water(softening(with(gel(resins(remains(as(the(most(widespread.(In( most(cases(IX(is(restricted(to(applications(where(ultrapure(water(are(required((industrial(makeup( water)( or( for( water( softening( (residential( application s);( however,( in( some( instances( it( is( applicable( to( the( treatment( of( more( challenging( feed( streams( such( as( produced( waters.(


8 !

Specifically,( the(application( of(IX( for( treating( produced(waters(will( be( dependent( on( the( ionic( composition( of( the( feed( stream( as( it( is( most( appropriate( for( waters( composed( primarily( of( bi carbonate( ions( (HCO 3 . ) .( This( form( of( treatment( is( termed( strong( base( IX,( where( the( OH . ( is( exchanged(for(the(bicarbonate(ion.( In(these(cases(IX(is(capable(of(effectively(treating(produced( waters(to(high (standards.(Unlike(membrane(processes(IX(does(not(use(a(semi . permeable(barrier( to( separate( the( dissolved( salts( and( minerals( from( water.( Instead,( IX( is( both( an( adsorption( process(and(a(chemical(reaction.(It(resembles(adsorption(because(solid(particles((resin)(are(used( and( regenerated,( while( the( chemical( reaction( specifically( applies( to( the( regeneration( of( the( resin. (

IX( requires(a( relatively( high( quality( source(water( that( is( free( of( particulates,( foulant (materials( and( other( competing( ions( for( the( exchange( sites( in( the( resin.( Therefore,( its( application( has( primarily(been(restricted(to(the(treatment(of(CBM(produced(waters,(which(are(relatively(free(of( contaminants( outside( of( the( aforementioned( bicarbonates, ( and( waters( that( have( undergone( extensive(pretreatment.(The(primary(costs(associated(with(IX(are(the(resin,(regeneration(of(the( resin,( capital( equipment( (pumps,( motors,( IX( columns),( and( disposal( costs( associated( with( disposal(of(the(regenerating(solution(f or(the(IX(resin.( (

Mechanical!Evaporation. (Mechanical(evaporation(processes(are(in(many(cases(the(only(suitable(


evaporation(of(water(through(a(variety(of(means(to( ultimately(produce(a(solids(cake(containing( all(of(the(dissolved(solids(that(were(present(in(the(produced(water.(These(processes(are(energy(

intensive(and(thus(are(associated(with(substantial(capital(and(operation(and(maintenance(costs.( However,( as( previous ly( stated( they( are( in( many( cases( the( only( option( when( disposal( of( high( salinity( produced( waters( is( required.( Summaries( of( some( example( mechanical( evaporation(



Multi R Effect!Distillatio n!(MED): ((MED(is(an(established(process(for( desalting(high(salinity( waters( (TDS( >( 36,000( mg/L) .( In( a( MED( system,( water( is( boiled( in( a( sequence( of( evaporators,(each(held(at(a(lower(pressure(than(the(last.(Each(evaporator(in(the(series(is( called(an("effect". (Because(the(boiling(point(of(water(decreases(as(pressure(decreases,( the( vapor( boiled( off( in( one( vessel( can( be( used( to( heat( the( next,( and( only( the( first( evaporator( (the( one( at( the( highest( pressure)( requires( an( external( source( of( heat.( A( reduced( pressure( in ( the( vapor( space( of( the( first( evaporator( must( be( maintained( to( account( for( the( difference( in( the( boiling( points( of( pure( and( saline( water.( Another( requirement( to(maintain( reasonable( heat(exchange( between( the( pipes( containing( the( condensing( steam(and( those(w ith( the(boiling( produced(water ,( the( temperature(of( the( produced(water (must(be(several(degrees(lower(than(that(of(the(condensing(steam.(MED( systems( typically( operate( at( a( low( temperature( of( 71.1 ° C( and( a( high( temperature( of( 110 ° C.( Operating( at( lower( temperat ures( limits( corrosion( and( these( systems( can( be( constructed( out( of( less(expensive(materials.(The(amount( of( fresh(water( produced( per( unit( amount( of( heating( steam( increases( almost( proportionally( with( the( number( of( stages.(While( in( theory,( evaporators( may( be( b uilt( with( an( arbitrarily( large( number( of( stages,(evaporators(with(more(than(four(stages(are(rarely(practical. (

Multi R Stage! Flash! (MSF)!Distillation: ((MSF(distills( saline(water( by( flashing(a(portion(of( the( feed( water( into( steam( in( multiple( stages.( In( MSF( the ( produced( water ( is( heated( under(high(pressure(in(order(to(prevent(boiling,(until(it(reaches(the(first(flash(chamber.(


9 !

In( the( flash( chamber( the( pressure( is( released( and( sudden( evaporation( or( “flashing”( takes(place.(Flashing(continues(in(each(successive(stage ,(because(the(pressure(is(lower( as(you(progress( from(one(stage( to( the(next.(The(water(gains(heat(as(it(passes( through( each(stage(by(condensing(vapors(that(are(generated(by(the(flashing(process.(The(steam( is(condensed(on(tubes(of(heat(exchangers(that(run(th rough(each(stage.(MSF( treatment( systems( typically( utilize(a( waste(heat(source( in(order(to( reduce(the(energy(consumption( by(one . half(to(two . thirds. (

Mechanical!Vapor!Compression! (MVC): ((MVC(is(generally(used(for(small . and(medium . scale( ( Q( =( 0.005( to( 0.5 ( mgd)( desalination( systems.( The( heat( for( evaporating( the( produced( water(comes(from(the(compression(of(vapor(rather(than(the(direct(exchange( of(heat( from( steam(produced(in(a(boiler.(The(boiling(point(of( the(water(is( reduced(by( reducing(the(pressure (that(is(applie d(to(it .(Two(methods(are(used(to(condense(the(vapor( so( as( to( produce( enough( heat( to( evaporate( incoming( produced( water :( a( mechanical( compressor(or(a(steam(jet.(The(mechanical(compressor(is(usually(electrically(driven. (

Mechanical! zero! liquid! discharge ( (ZLD)( systems( also( fall( under( the( category( of( mechanical( evaporation( systems( and( include( thermal( evaporators,( crystallizers( and( spray( dryers .( These( treatment(technologies(are(commonly(used(in(combination(with(RO(systems(in(order(to(achieve( a(zero(liquid(discharg e(status((i.e.,(no(liquid(waste(stream(resulting(from( treating(the(produced( or(frac(water ).( The(capital(and(operational(costs( for(these(thermal(systems(are(typically(higher( than(for(the(desalination(membrane(facility(due(to(the(extensive(mechanical(systems (and(exotic( alloy( materials( required.( In( addition,( the( energy( costs( associated( with( the( evaporation( processing( are( significant.( Zero( liquid( discharge( systems( ultimately( reduce( the( concentrate( or( produced(water(to(a(solid(product((crystallized(salts(and(min erals)(for(landfill(disposal.((In(some( cases,( the( water( vapor( is( recovered.( A( summary( comparison( of( mechanical( evaporation( processes(to(RO(is(given(in(Table(3.( (

Table!3. (Comparison(of(performance(statistics(for(mechanical(evaporation(and(reverse(osmosis(

(R O)(desalting(technologies.( (

Process !

Energy!Use a ! (kWh/1,000!gal) !

Method!of !


Relative !

Operation !

Recovery!(%) !

Capital!Costs !



Steam((heat) (

10( – (20 (

High (



Steam((heat) (

20( – (60 (

Medium(to(High (





30( – (53 (

(heat) (

35( – (99 (

High (

RO !

8( – (23 (

Pressure (

35( – (55 b (

Low(to(Medium (

Notes: ! a( – (Combined(electrical(and(equivalent(thermal(energy.(



( – (Recovery(ratios(are(a(function(of(the(feed(water(TDS(concentration.(Recovery(ratios(increase( beyond(50%(as(the(feed(water(TDS(decreases(below(approximately(36,000(mg/L.( (


10 !


1. ( Benko,( K.L.( and( J.E.( Drewes,( Produced( Water( in( the( Western( United( States:( Geographical( Distribution,( Occurrence,( and( Composition.( Environmental( Engineering( Science,(2008.(25(2):(p.(239 . 246. (


Mondal,(S.(and(S.R.(Wickramasinghe,( Produced(water( treatment( by( nanofiltration(and( reverse(osmosis(membranes.( Journal(of(membrane(Science,(2008.(322:(p.(162 . 170. (


Jackson,( R.E.( and( K.J.( Reddy,( Geochemistry( of( Coalbed( Natural( Gas( (CBNG)( Produced( Water(in(Powder(River(Basin,(Wyoming:(Salinity(and(Sodicity.(Water,(Air,(Soil(Pollution,( 2007.(184:(p.(49 . 61. (


McBeth ,( I.H.,( K.J.( Reddy,( and( Q.D.( Skinner,( Chemistry( of( trace( elements( in( coalbed( methane(product(water.(Journal(of(Water(Research,(2003.(37:(p.(884 . 890. (


Rice,(C.A.,(M.S.(Ellis,(and( J.H.(Bullock( Jr.,(Water(Co . Produced(with(Coalbed(Methane(in( the( Powder( River ( Basin,( Wyoming:( Preliminary( Compositional( Data.( Open . File( Report(

00 . 372.(,(2000,(U.S.(Geological(Survey(Washington,(DC. (

6. ( Xu,(P.(and(J.E.(Drewes,(Viability(of(nanofiltration(and(ultra . low(pressure(reverse(osmosis( membranes( for( multi . beneficial( use( of( met hane( produced( water.( Separation( and( Purification(Technology,(2006.(52:(p.(67 . 76. (


Xu,( P.,( et( al.,( Treatment( of( brackish( produced( water( using( carbon( aerogel . based( capacitive(deionization(technology.(Water(Research,(2008.(42:(p.(2605 . 2617. (


Xu,(P.,(J.E.( Drewes,(and(D.(Heil,(Beneficial(use(of(co . produced(water(through(membrane( treatment:(technical . economic(assessment.(Desalination,(2008.(225:(p.(139 . 155. (


Rahm,(D.,(Regulating(hydraulic( fracturing(in( shale(gas(plays:(The(case(of(Texas.(Energy( Poliscy,(201 1.(39:(p.(2974 . 2981. (

10. ( Agency,( E.P.( Scoping( Materials( for( Initial( Design( of( EPA( Research( Study( on( Potential( Relationships( Between( Hydraulic( Fractur . ( ing( and( Drinking( Water( Resources.( 2010;(




6/$File/HydraulicFracScopingDocforSAB . 3 . 22 . 10Final.pdfS . (

Bookman . Edmonston( Engineering,( I.,( Salinity( Management( Study( Final( Report( Long( Term(Strategy(and(Recommended(Action(Plan,(1999,(US(Bureau(of(Reclamation.(p.(70. (

12. ( Mallevialle,( J.,(Odendaal,(P.,(Wiesner,(M.,(The(Emergence(of(Membranes(in(Water(and( Wastewater( Treatment,( in( Water( Treatment( Membrane( Processes,( J.( Mallevialle,( Odendaal,(P.,(Wiesner,(M.,(Editor(1996b,(McGraw . Hill:(New(York.(p.(1.1 . 1.10. (




Matsuura,(T.,(Progress(in(membrane(science(and(technology(for(seawater(desalination( . ( a(review.(Desalination,(2001.(134:(p. (47 . 54. (


Mousa,( H.A.( and( S.A.( Al . Hitmi,( Treatability( of( wastewater( and( membrane( fouling.( Desalination,(2007.(217(1 . 3):(p.(65 . 73. (


Culkin,( B.( Concentrating( RO( reject( streams( with( VSEP.( 2008;( Available( from:( . (


11 !

16. ( Cath,( T.T.,( V.D.( Adams,( and( A.E.( Childress,( Experimental( study( of( desalination( using( direct( contact( membrane( distillation:( a( new( approach( to( flux( enchancement.( J.( Membrane(Sci.,(2004(228):(p.(5 . 16. (


El . Bourawi, ( M.S.,( et( al.,( A( framework( for( better( understanding( membrane( distillation( seperation(process.(J.(Membrane(Sci.,(2006.(285:(p.(4 . 29. (


Lawson,(K.W.(and(D.R.(Lloyd,(Membrane(distillation.(J.(Membrane(Sci.,(1997.(124:(p.(1 .

25. (

19. ( Hendren,( Z.D.,( J.A.( Brant, ( and( M.R.( Wiesner,( Surface( modification( of( nanostructured( ceramic( membranes( for( direct( contact( membrane( distillation.( Journal( of( Membrane( Science,(2009.(In . press. (

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Use(Discharge(Requirement,(1997. (
Metcalf( &( Eddy,( I.,( Wastewater( Engineering:( Treatment( and( Reuse.( Fourth( ed2003:(
McGraw . Hill,(Inc. (
12 !

In an ever changing world with finite resources, it is now more critical than ever for America to tap into its existing energy resources: oil and natural gas. Domestic energy development activities are setting us free from the reliance of foreign imports. But with this freedom comes a challenge: how to manage the vast quantities of water that are produced and consumed in the process.

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