Zero Liquid Discharge (ZLD)

Concept Evolution and Technology Options

Concept,
Viatcheslav Freger
Wolfson Department of Chemical Engineering
Technion – Israel Institute of Technology, Haifa, Israel
“Z
“Zero Liquid Discharge” Workshop, Gandhinagar, January 27 ‐
Li id Di h ”W k h G dhi J 27 28, 2014
28 2014

ZLD Feb 2014 1

 Outline

 History and motivation

History and motivation
 Conventional ZLD
 Hybrid ZLD
 E
Emerging ZLD and near‐ZLD alternatives
i ZLD d ZLD lt ti
 Outlook

ZLD Feb 2014 2

 Some History
 ZLD sector was apparently born in 1970s in USA, driven by 
the regulator
 Tight federal regulations on salt discharge to surface waters 
introduced, especially, due to salinity problems in the Colorado 
River 
 Regulations were mainly concerned with power plant discharges 
from cooling tower blowdowns and scrubbers (in the wake of 
previously introduced regulations on flu gas discharges)
 Clean Water Act 1974,  revised 1977, 1982
 First ZLDs installed were 500‐2,000 GPM units based on 
evaporation/crystallization 
 Regulations are expected to keep tightening: new EPA’s 
guidelines (ELG) expected in 2017 and 2022 on various 
types of discharges (many have to be ZLD)
fd h ( h b )
Freger ZLD Feb 2014 Sources: GWI Report, 2009; G. Maller/URS, 2013 3
 Current Drivers and Limitations
 Presently, the major driver for using ZLD are 
 Environmental regulation on discharge of specific solutes (salt, toxic 
elements nitrate‐nitrite
elements, nitrate nitrite etc);
etc);
 Water scarcity/water stress growing world‐wide along with still negligible 
rate of waste water recycling; 
 Economics: recycled water becomes more affordable as the water supply 
from conventional sources becomes more expensive;
 Growing social responsibility and education towards awareness of 
G i i l ibili d d i d f
environmental issues
 While ZLD cost is high in most cases, it might be a more economic solution 
g , g
when waste needs to be transported in large volumes over long distances
 Still ZLD has drawbacks, probably, the most significant are
 Very high cost (both CAPEX and OPEX)
 Custom‐design on case‐to‐case basis
 Difficulties to deal with complex streams (e.g., petrochemical)
Freger ZLD Feb 2014 4
 Current and Potential Markets for ZLD  
 Treatment and recycling of industrial waste effluents
• Power • Petroleum and petrochemical
Petroleum and petrochemical
• Synthetic fuels • Oil refining
• Primary metals processing
Primary metals processing • Steam Assisted Gravity Drainage 
Steam Assisted Gravity Drainage
• Microelectronics (SAGD) heavy oil recovery
• Chemical • Cogeneration
• Pulp and paper • Fertilizer
• Coal mining • Solid waste (leachate and 
secondary sewage effluent)
secondary sewage effluent)
• Battery manufacturing
• Coal liquefaction
• PVC manufacturing
• Ethanol production
• Uranium mining
Uranium mining
 Tertiary treatment of municipal waste effluents
 Inland desalination
Inland desalination…
Freger ZLD Feb 2014 5
 Conventional Thermal ZLD Technology
 The conventional ZLD is based on evaporation and 
crystallization operations
crystallization operations
 Evaporation (MVC or live steam) usually aims at 
>90% water recovery 
y
 crystallization may achieve 100% recovery
 solids can be further dewatered on a filter
solids can be further dewatered on a filter‐press
press 
for landfill
 Latent heat of evaporation  is partly recovered 
(especially, for MVC) 
 Operational and capital costs are still very high 
d t hi h ti (20 40 kWh/ 3
due to high energy consumption (20‐40 kWh/m
vs. 2‐3 kWh/m3 in desalination), use of chemicals 
and expensive corrosion‐resistant materials.

Freger ZLD Feb 2014 6

 MVC Evaporation (Falling Film)

Potential issues:
- Tboil elevation (for MVC)
- Prior removal of SS and Ca required
- Mg(OH)2 precipitation (scaling and corrosion)
Freger ZLD Feb 2014 7
- High MgCl2 and CaCl2 solubility
 Crystallization

Atmospheric Crystallization with Vacuum crystallization

Softening Pretreatment (lower Tboil, higher salt concentration)
(Tboil may be too high for MgCl2 and CaCl2)

Freger ZLD Feb 2014 K. Jenkins et al/CH2M Hill, WaterWorld, 2013 8

 Hybrid ZLD Technologies
 Due to the high cost there is a strong motivation to employ more energy‐
saving process to minimize the MVC/Crystallization share. 
(Compare with costs of desalination technologies:  RO << ED << Thermal.)
 Reverse Osmosis* (RO) – rejects salt, passes water,  2‐4 kWh/m3
 Nanofiltration* (NF) – similar to RO, but passes some salt
 Electrodialysis* (ED) or ED reversal (EDR) – removes ion, costs 
i t
intermediate to RO and MVC
di t t RO d MVC
 Natural Evaporation – slow, large footprints
 Another possible motivation is presence of organics, volatiles, colloids etc., 
which complicates the treatment and water reuse. Available solutions:
 Conventional bioremediation
Conventional bioremediation
 MBR/UF pretreatment 

Freger ZLD Feb 2014 9

*RO, NF and ED will be covered in detail on 2nd day
 ZLD Combined with RO
 RO is presently the best and most energy‐saving available technology for desalting. 
The purpose is then to use RO to recover as much water as possible before MVC. 
The ZLD cost drops as RO recovery increases
The ZLD cost drops as RO recovery increases. 
 The recovery in RO is however limited by 3 main factors
 Osmotic pressure becomes too high for TDS 
Osmotic pressure becomes too high for TDS ~ 80,000 ppm
80 000 ppm
 Scaling by sparingly soluble salts (Ca, Mg, SO4, PO4, silica), maybe alleviated  
to some degree using anti‐scalants
 Fouling (by organics colloids biofilms etc )
Fouling (by organics, colloids, biofilms etc.)
Cost of Brine Concentration for BWRO
100.0

90.0

uct
BC - 150

nts /m 3 produ
80.0

70.0
BC - 100
60.0

Cen
50.0

40.0 BC - 50

30.0
70 80 90 100
% Recovery
Glueckstern,
Freger ZLD Feb 2014 Proc. 6th IDS, 2003 10
 RO Limitations on Recovery
180
Exit conc pressure, atm

2.5 atm
160 Brine
8.3 atm
140 Conc
120
100 Scaling Onset

80
60
40
20
E

RO Recovery
0
50 60 70 80 90 100
RO
O Recovery, %

Brine Osmotic Pressure vs. Recovery Scaling Potential vs. Recovery

Jv = Lp(P –  LSI = SP/SPc ~ Cn, n ~ 2-5

Freger ZLD Feb 2014 11

 Increasing RO Recovery: 2‐Stage RO/NF 
 A simple 2‐stage (different membranes & pressures used at each stage)
 Interstage softening/precipitation (more chemicals used)

Rahardianto, et al., JMS 2007; EST, 2008; Des. 2010, 
Sanciolo et al., Chemosphere, 2008.
et al., Chemosphere, 2008.
Yprimary = 85%
3000 mg/L

Qf
Ysec = 67% Product
18100 mg/L

19440 mg/L A/S

54000 mg/L 0 05 Qf
0.05

0.15 Qf
Brine Treatment
FB
Crystallizer
Freger ZLD Feb 2014 12
 High Efficiency RO (HERO) Process
• High Silica Water
• Cooling Tower
Blowdown
• Tertiary Treated Effluent
(Sewage)
• High/TOC
g Biologically
g y
Active Water

 By removing Ca and carbonate hardness RO can run at
By removing Ca and carbonate hardness RO can run at
pH >10.5
 High pH creates a 
High pH creates a “cleaning
cleaning environment
environment” =>> low fouling
low fouling
 Silica solubility very high, hardness removed  => low scaling
 Salt rejection and flux are increased
Salt rejection and flux are increased
 Recovery >90%
 However high chemical costs add ~$0
However, high chemical costs add  13/m3 overall product
$0.13/m overall product
Freger ZLD Feb 2014 Source: FEMP Bulletin, DOE/EE – 0294; aquatech.com 13
 ZLD Combined with ED
 ED is not limited by osmotic pressure and thus it can achieve a 
much higher recovery.
 T i ll ED d l i
Typically, ED desalting cost is higher than RO but lower than 
i hi h h RO b l h
MVC/crystallization. The optimal placement of ED is then 
between RO and evaporation
between RO and evaporation.

Freger ZLD Feb 2014 14

 Increasing ED recovery for ZLD
 As in RO, precipitation of sparingly soluble salts in the brine 
limits recovery. Proposed solutions include
 Off
Off‐stack precipitation (seeded) 
k i i i ( d d)
 EDM in place of regular ED

40

m Oversaturatioon (%)
35

30

25

20

Gypsum
15

10
0 2 4 6 8
Time (Hrs)

O se oof pprecipitation
Onset ec p o
place crystallizer in brine loop
Freger ZLD Feb 2014 15
R. Bond et al, 2011, Florida Water Res J; J. Gilron, Wetsus, 2013.
 ED Metathesis

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

Freger ZLD Feb 2014 R. Bond et al, 2011, Florida Water Res J; T. Davis, USBR Rpt. 135. 16
 RO+EDM+Off‐Stack Precipitation ZLD Process

T. Davis, USBR Rpt. 135.

Freger ZLD Feb 2014 17

 Biological (Pre‐)Treatment
 Removes TOC (most organics) as CO
( ) 2 and sludge, may leave some 
d l d l
recalcitrant organicss
 MBR/UF is significantly more expensive, but offers a smaller footprint 
/ g y p , p
and a more robust process

Tirupur Project 
Project
Textile Effluent, 
54 MLD, 2007

S. Prakash, GWI, Barcelona, 2007

Ambur–Vaniyambadi
Tannery Effluent
7 MLD, 2007

Freger ZLD Feb 2014 18

 Emerging and State‐of‐the‐Art ZLD Solutions

 Several alternative technologies or hybrids are in use or being 
examined for ZLD. 
i d f ZLD
 SPARRO (Seeded RO)
 ARROW (O’Brien and Gere, 2007) – pH elevation + IX + RO
 VSEP (by New Logic Rerearch
S (by e og c e ea c Inc.) –c ) membranes vibrated
e b a es b ated
 HEEPM (by EET Corporation) – ED treats the feed to RO 
 F
Forward Osmosis (FO)
dO i (FO)
 Molecular distillation (MD)
 Wind‐assisted intensified evaporation (WAIV)

Mickley, WaterReuse Foundation, 2008

Freger ZLD Feb 2014 19
 SPARRO Process

 Developed for treating hard waste water from mining industry. 

Freger ZLD Feb 2014 20

 Forward Osmosis
 FO is used today for treating produced water in oil industry 
(generating a larger volumes of waste water – no ZLD)
 FO
FO was proposed as an alternative to RO. Viable only when a 
d l i RO Vi bl l h
waste energy (heat or osmotic) is available.
Vapor
compressor

Gases to  NCG 
adsorb out
Concentrated 
seawater

Diluted 
draw 
solution

Feed 
Proposed concept seawater

(M C t h
(McCutcheon ett al.,
l 2005) Concentrated 
draw solution
Product water

Freger ZLD Feb 2014 Sagiv and Semiat 21

 WAIV (enhanced natural evaporation)
 Evaporation ponds (EP) are widely used as part of ZLD, but 
their footprint may be excessively large.
 WAIV may offer a 1/15 land and 1/3 CAPEX of EP for the same 
evaporation rate
2

1.5

ed
kWh/m3 fee
Brine
Mgt
1
wind ROII

Esp, k
water
ROI
0.5

0
Courtesy, Lesico Ltd. BC WAIV Evap Pond

J. Gilron, Wetsus, 2013

Freger ZLD Feb 2014 22
 Outlook
 Efforts continue to find alternatives to energy‐intensive 
evaporator/crystallizer systems. 
 Hybrids systems with increased recovery are and will be the 
dominant approach
 Progress is being made in lowering capital costs; a total 
installed cost factor is down from 5 to 1.8‐2.
 “… 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 couldld 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

 Thanks and Acknowledgements

Prof. Jack Gilron 
(Zukerberg Institute for Water research), Ben
Institute for Water research) Ben‐Gurion
Gurion University) 
University)
Prof. Rafi Semiat
(Chemical Eng Department Technion – IIT)
(Chemical Eng. Department, Technion –

ZLD Workshop Organizers

ZLD Workshop Organizers

Freger ZLD Feb 2014 24