Zero Liquid Discharge (ZLD)

Concept Evolution and Technology Options

Concept,
ViatcheslavFreger
WolfsonDepartmentofChemicalEngineering
Technion IsraelInstituteofTechnology,Haifa,Israel

Z
ZeroLiquidDischargeWorkshop,Gandhinagar,January27
Li id Di h
W k h
G dhi
J
27 28,2014
28 2014

ZLD Feb 2014

Outline

History and motivation

Historyandmotivation

ConventionalZLD

HybridZLD

E
EmergingZLDandnearZLDalternatives
i ZLD d
ZLD lt
ti

Outlook

ZLD Feb 2014

SomeHistory

ZLDsectorwasapparentlybornin1970sinUSA,drivenby
theregulator

Tightfederalregulationsonsaltdischargetosurfacewaters
introduced,especially,duetosalinityproblemsintheColorado
River

Regulationsweremainlyconcernedwithpowerplantdischarges
fromcoolingtowerblowdowns andscrubbers(inthewakeof
previouslyintroducedregulationsonflugasdischarges)

CleanWaterAct1974,revised1977,1982

FirstZLDsinstalledwere5002,000GPMunitsbasedon
evaporation/crystallization

Regulationsareexpectedtokeeptightening:newEPAs
guidelines(ELG)expectedin2017and2022onvarious
typesofdischarges(manyhavetobeZLD)
fd h
(
h
b
)

Freger ZLD Feb 2014

Sources: GWI Report, 2009; G. Maller/URS, 2013

CurrentDriversandLimitations

Presently,themajordriverforusingZLDare

Environmentalregulationondischargeofspecificsolutes(salt,toxic
elements nitratenitrite
elements,nitrate
nitriteetc);
etc);

Waterscarcity/waterstressgrowingworldwidealongwithstillnegligible
rateofwastewaterrecycling;

Economics:recycledwaterbecomesmoreaffordableasthewatersupply
fromconventionalsourcesbecomesmoreexpensive;

Growingsocialresponsibilityandeducationtowardsawarenessof
G
i
i l
ibili
d d
i
d
f
environmentalissues

WhileZLDcostishighinmostcases,itmightbeamoreeconomicsolution
g
,
g
whenwasteneedstobetransportedinlargevolumesoverlongdistances

StillZLDhasdrawbacks,probably,themostsignificantare

Veryhighcost(bothCAPEXandOPEX)

Customdesignoncasetocasebasis

Difficultiestodealwithcomplexstreams(e.g.,petrochemical)

Freger ZLD Feb 2014

CurrentandPotentialMarketsforZLD

Treatmentandrecyclingofindustrialwasteeffluents

Power

Petroleum and petrochemical

Petroleumandpetrochemical

Syntheticfuels

Oilrefining

Primary metals processing

Primarymetalsprocessing

Microelectronics

SteamAssistedGravityDrainage
Steam
Assisted Gravity Drainage
(SAGD)heavyoilrecovery

Chemical

Cogeneration

Pulpandpaper

Fertilizer

Coalmining

Batterymanufacturing

Solidwaste(leachateand
secondary sewage effluent)
secondarysewageeffluent)

PVCmanufacturing

Coalliquefaction

Uranium mining
Uraniummining

Ethanolproduction

Tertiarytreatmentofmunicipalwasteeffluents
Inland desalination
Inlanddesalination

Freger ZLD Feb 2014

ConventionalThermalZLDTechnology

TheconventionalZLDisbasedonevaporationand
crystallization operations
crystallizationoperations

Evaporation(MVCorlivesteam)usuallyaimsat
>90%waterrecovery
y

crystallizationmayachieve100%recovery

solidscanbefurtherdewateredonafilter
solids
can be further dewatered on a filterpress
press
forlandfill

Latentheatofevaporationispartlyrecovered
(especially,forMVC)

Operationalandcapitalcostsarestillveryhigh
d t hi h
duetohighenergyconsumption(2040kWh/m
ti (20 40 kWh/ 3
vs.23kWh/m3 indesalination), useofchemicals
andexpensivecorrosionresistantmaterials.
Freger ZLD Feb 2014

MVCEvaporation(FallingFilm)

Freger ZLD Feb 2014

Potential issues:
- Tboil elevation (for MVC)
- Prior removal of SS and Ca required
- Mg(OH)2 precipitation (scaling and corrosion)
- High MgCl2 and CaCl2 solubility

Crystallization

Atmospheric Crystallization with

Softening Pretreatment
(Tboil may be too high for MgCl2 and CaCl2)
Freger ZLD Feb 2014

Vacuum crystallization
(lower Tboil, higher salt concentration)

K. Jenkins et al/CH2M Hill, WaterWorld, 2013

HybridZLDTechnologies

Duetothehighcostthereisastrongmotivationtoemploymoreenergy
savingprocesstominimizetheMVC/Crystallizationshare.
(Comparewithcostsofdesalinationtechnologies:RO<<ED<<Thermal.)

ReverseOsmosis* (RO) rejectssalt,passeswater,24kWh/m3

Nanofiltration*(NF) similartoRO,butpassessomesalt

Electrodialysis*(ED) orEDreversal(EDR) removesion,costs

i t
intermediatetoROandMVC
di t t RO d MVC

NaturalEvaporation slow,largefootprints

Anotherpossiblemotivationispresenceoforganics,volatiles,colloidsetc.,
whichcomplicatesthetreatmentandwaterreuse.Availablesolutions:

Conventional bioremediation
Conventionalbioremediation

MBR/UFpretreatment

Freger ZLD Feb 2014

*RO, NF and ED will be covered in detail on 2nd day

ZLDCombinedwithRO

ROispresentlythebestandmostenergysavingavailabletechnologyfordesalting.
ThepurposeisthentouseROtorecoverasmuchwateraspossiblebeforeMVC.
The ZLD cost drops as RO recovery increases
TheZLDcostdropsasROrecoveryincreases.

TherecoveryinROishoweverlimitedby3mainfactors

OsmoticpressurebecomestoohighforTDS
Osmotic
pressure becomes too high for TDS ~80,000ppm
80 000 ppm
Scalingbysparinglysolublesalts(Ca,Mg,SO4,PO4,silica),maybealleviated
tosomedegreeusingantiscalants
Fouling (by organics colloids biofilms etc )
Fouling(byorganics,colloids,biofilmsetc.)
CostofBrineConcentrationforBWRO
Cen
nts /m 3 produ
uct

100.0
90.0

BC - 150

80.0
70.0
BC - 100

60.0
50.0
40.0

BC - 50

30.0
70

Freger ZLD Feb 2014

80

90
% Recovery

Glueckstern,
Proc. 6th IDS, 2003

100

10

Exit conc pressure, atm

E

ROLimitationsonRecovery
180
160
140
120
100
80
60
40
20
0
50

2.5 atm

Brine
Conc

8.3 atm

Scaling Onset

RO Recovery
60

70

80

90

100

RO
O Recovery, %

Brine Osmotic Pressure vs. Recovery

Jv = Lp(P
Freger ZLD Feb 2014

Scaling Potential vs. Recovery

LSI = SP/SPc ~ Cn, n ~ 2-5

11

IncreasingRORecovery:2StageRO/NF

Asimple2stage(differentmembranes&pressuresusedateachstage)

Interstage softening/precipitation(morechemicalsused)
Rahardianto,etal.,JMS2007;EST,2008;Des.2010,
Sanciolo etal.,Chemosphere,2008.
et al., Chemosphere, 2008.

Yprimary = 85%

3000 mg/L

Qf
Ysec = 67%

Product

18100 mg/L

A/S

19440 mg/L

54000 mg/L

0.15 Qf
FB
Crystallizer
Freger ZLD Feb 2014

0 05 Qf
0.05
Brine Treatment

12

HighEfficiencyRO(HERO)Process
High Silica Water
Cooling Tower
Blowdown
Tertiary Treated Effluent
(Sewage)
High/TOC
g
Biologically
g
y
Active Water

ByremovingCaandcarbonatehardnessROcanrunat
By
removing Ca and carbonate hardness RO can run at
pH>10.5
HighpHcreatesa
High pH creates a cleaning
cleaningenvironment
environment=>>lowfouling
low fouling
Silicasolubilityveryhigh,hardnessremoved=>lowscaling
Saltrejectionandfluxareincreased
Salt rejection and flux are increased
Recovery>90%
However high chemical costs add ~$0
However,highchemicalcostsadd
$0.13/m
13/m3 overallproduct
overall product

Freger ZLD Feb 2014

Source: FEMP Bulletin, DOE/EE 0294; aquatech.com

13

ZLDCombinedwithED

EDisnotlimitedbyosmoticpressureandthusitcanachievea
muchhigherrecovery.
T i ll ED d l i
Typically,EDdesaltingcostishigherthanRObutlowerthan
i hi h h RO b l
h
MVC/crystallization.TheoptimalplacementofEDisthen
between RO and evaporation
betweenROandevaporation.

Freger ZLD Feb 2014

14

IncreasingEDrecoveryforZLD

AsinRO,precipitationofsparinglysolublesaltsinthebrine
limitsrecovery.Proposedsolutionsinclude

Off
Offstackprecipitation(seeded)
k
i i i ( d d)

EDMinplaceofregularED
Gypsum
m Oversaturatioon (%)

40
35
30
25
20
15
10
0

Time (Hrs)

O se oof pprecipitation
Onset
ec p
o
place crystallizer in brine loop
Freger ZLD Feb 2014

R. Bond et al, 2011, Florida Water Res J; J. Gilron, Wetsus, 2013.

15

EDMetathesis
Formation of sparingly
soluble salts prevented
using a stack of 4compartment units

Freger ZLD Feb 2014

R. Bond et al, 2011, Florida Water Res J; T. Davis, USBR Rpt. 135.

16

RO+EDM+OffStack PrecipitationZLDProcess

T. Davis, USBR Rpt. 135.

Freger ZLD Feb 2014

17

Biological(Pre)Treatment

RemovesTOC(mostorganics)asCO
(
)
d l d
l
2 andsludge,mayleavesome
recalcitrantorganicss

MBR/UFissignificantlymoreexpensive,butoffersasmallerfootprint
/
g
y
p
,
p
andamorerobustprocess
Tirupur Project
Project
TextileEffluent,
54MLD,2007
S. Prakash, GWI, Barcelona, 2007

AmburVaniyambadi
TanneryEffluent
7MLD,2007
Freger ZLD Feb 2014

18

EmergingandStateoftheArtZLDSolutions

Severalalternativetechnologiesorhybridsareinuseorbeing
examinedforZLD.
i d f ZLD

SPARRO(SeededRO)

ARROW(OBrienandGere,2007) pHelevation+IX+RO

VSEP(byNewLogicRerearch
S (by e og c e ea c Inc.)
c ) membranesvibrated
e b a es b ated

HEEPM(byEETCorporation) EDtreatsthefeedtoRO

F
ForwardOsmosis(FO)
dO
i (FO)

Moleculardistillation(MD)

Windassistedintensifiedevaporation(WAIV)
Mickley, WaterReuse Foundation, 2008

Freger ZLD Feb 2014

19

SPARROProcess

Developedfortreatinghardwastewaterfromminingindustry.

Freger ZLD Feb 2014

20

ForwardOsmosis

FOisusedtodayfortreatingproducedwaterinoilindustry
(generatingalargervolumesofwastewater noZLD)
FO
FOwasproposedasanalternativetoRO.Viableonlywhena
d
l
i
RO Vi bl
l h
wasteenergy(heatorosmotic)isavailable.
Vapor
compressor

Gasesto
adsorb

NCG
out

Concentrated
seawater

Diluted
draw
solution

Proposed concept
(M C t h
(McCutcheon
ett al.,
l 2005)

Feed
seawater

Productwater

Freger ZLD Feb 2014

Concentrated
drawsolution

Sagiv and Semiat

21

WAIV(enhancednaturalevaporation)

Evaporationponds(EP)arewidelyusedaspartofZLD,but
theirfootprintmaybeexcessivelylarge.
WAIVmayoffera1/15landand1/3CAPEXofEPfor thesame
evaporationrate
2

wind
water

Esp, k
kWh/m3 fee
ed

1.5
Brine
Mgt
ROII

ROI

0.5

0
Courtesy, Lesico Ltd.

Freger ZLD Feb 2014

BC

WAIV

Evap Pond

J. Gilron, Wetsus, 2013

22

Outlook

Effortscontinuetofindalternativestoenergyintensive
evaporator/crystallizersystems.
Hybridssystemswithincreasedrecoveryareandwillbethe
dominantapproach
Progressisbeingmadeinloweringcapitalcosts;atotal
installedcostfactorisdownfrom5to1.82.
industry analysts predict a cumulative annual growth rate
for recovery/ reuse systems in excess of 200% over the next
d d off which
decade,
hi h a significant
i ifi t portion
ti could
ld be
b accounted
t d for
f
by ZLD capacity. The economic and regulatory climate is
such that ZLD or near zero discharge is going to continue to
grow rapidly
[G. Cope, From zero to hero, globalwaterintel.com]

Freger ZLD Feb 2014

23

ThanksandAcknowledgements

Prof.JackGilron
(Zukerberg InstituteforWaterresearch),Ben
Institute for Water research) BenGurion
GurionUniversity)
University)
Prof.RafiSemiat
(Chemical Eng Department Technion IIT)
(ChemicalEng.Department,Technion
ZLD Workshop Organizers
ZLDWorkshopOrganizers

Freger ZLD Feb 2014

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