REMOVAL OF INORGANIC SALTS FROM RO CONCENTRATE BY USING

THERMAL EVAPORATION TECHNOLOGIES

A Project Report submitted in Partial Fulfillment of the Requirement for

the Award of the Degree of

BACHELOR OF TECHNOLOGY

in

CHEMICAL ENGINEERING

Submitted by

Challa Venkataramana (11701013)

Byreddy Amulya (11701010)

Maddela Hemanth Kumar (11701032)

Putikireddy Preethi (11701064)

Under the Esteemed Guidance of

Dr. B. SARATH BABU,
HEAD OF THE DEPARTMENT OF CHEMICAL ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING
SVU COLLEGE OF ENGINEERING
SRI VENKATESWARA UNIVERSITY
TIRUPATI
2021
 CERTIFICATE

This is to cer+fy that the project report en+tled

REMOVAL OF INORGANIC SALTS FROM RO CONCENTRATE BY
USING THERMAL EVAPORATION TECHNOLOGIES
is the bonafide work done and submi:ed by

CHALLA VENKATARAMANA (11701013)

BYREDDY AMULYA (11701010)

MADDELA HEMANTH KUMAR (11701032)

PUTIKIREDDY PREETHI (11701064)

Students of Bachelor of Technology In the Department of Chemical Engineering , SRI

VENKATESWARA UNIVERSITY , TIRUPATI in par+al fulfilment of the requirements for the
award of the degree of BACHELOR OF TECHNOLOGY in CHEMICAL ENGINEERING during
2017-2021.

GUIDE: HOD:

Dr.B.SARATH BABU, M.Tech.,Ph.D Dr.B.SARATH BABU, M.Tech.,Ph.D

Associate professor and Head, Associate professor and Head,

Dept. of CHEMICAL ENGINEERING Dept. of CHEMICAL ENGINEERING

SRI VENKATESWARA UNIVERSITY SRI VENKATESWARA UNIVERSITY

 ACKNOWLEDGEMENT

The sa+sfac+on and euphoria that accompanies the successful comple+on of any task
would be incomplete without the men+on of the people who made it possible, whose
constant guidance and encouragement crown all the efforts with success.

We are deeply indebted to our guide Dr. B. SARATH BABU, M.Tech., Ph.D Associate
Professor and Head of the Department of Chemical Engineering, S.V.U College of
Engineering, Tirupa+, for his valuable guidance, kindness, generosity, consistent
involvement and encouragement throughout our project work.

Our sincere thanks to Dr. B. SARATH BABU, Head of the Department for providing us
with the facili+es for comple+on of our project.

It is a pleasure to express our deep sense of gra+tude and indebtedness to the en+re
faculty, Department of Chemical Engineering, Sri Venkateswara University College of
Engineering, Tirupa+, for their support, who have directly or indirectly had a hand in the
successful comple+on of our project work.

Most of all, We would like to thank the Almighty, my ever-loving Parents, family members
and well-wishers for giving us the most needed moral support for the successful
comple+on of our project work.

Project Members

Byreddy Amulya (11701010)

Challa Venkataramana (11701013)

Maddela Hemanth Kumar (11701032)

Pu+kireddy Preethi (11701064)

 DECLARATION
We do hereby declare that this study work, en+tled “REMOVAL OF INORGANIC SALTS FROM
RO CONCENTRATE BY USING THERMAL EVAPORATION TECHNOLOGIES”, submi:ed to the
Department of Chemical Engineering, Sri Venkateswara University College of Engineering,
Tirupa+, in par+al fulfilment for the award of the degree of Bachelor of Technology in
Chemical Engineering, Sri Venkateswara University College of Engineering, Tirupa+, has
been originally done by us, under the guidance of Dr. B. SARATH BABU.

We also declare that this thesis is original and has not been submi:ed , in part or full, for
any other degree or diploma of this or any other university. The extent of informa+on,
incorporated in this thesis, derived from the exis+ng literature is duly acknowledged.

(Byreddy Amulya)

(Pu+kireddy Preethi)

(Challa Venkataramana)

(Maddela Hemanth Kumar)



 ABSTRACT

In industrial sedngs, such as pharma, pulp & paper, tanneries, tex+le dyeing,
chemicals, power plants, etc., generate wastewater with high salinity/TDS. RO is ogen
used to remove Total Dissolved Solids (TDS) from industrial wastewater or treated
industrial wastewater and the yield permeates with rela+vely low TDS Concentra+ons. RO
Reject water is the main problem because this rejec+on is released without any
treatment to the natural water bodies. The Reject/Concentrate is more than three +mes
the concentrated feed water in terms of feed water salts. With the increasing cost of
water and waste discharge, more companies are looking to recover & reuse RO reject
water. Recovery of valuables from RO Reject would be the most obvious solu+on to
eliminate environmental damage.

Membrane technologies became imprac+cal at higher concentra+ons of TDS, for

that ZLD is one strategy to address this challenge. The major ZLD technologies that are
used in various combina+ons as per the requirements are Solvent recovery, Selec+ve
crystalliza+on method, Chemical precipita+on, Electrodialysis, Thermal Evapora+on
techniques. Among these, the Thermal evapora+on technique has higher efficiency of
separa+on. This opera+on ogen involves the concentra+on of brine and recovery of high
quality water for beneficial use. The type of evaporator to be used largely depends on the
chemistry of the solu+on to avoid scaling of Heat transfer surfaces. The equipment
technologies for evapora+on includes Falling film, Natural circula+on, Rising film and
Forced Circula+on Evaporators.

Typical RO concentrate/RO reject TDS concentra+ons are ogen in the range of

30000-50000 mg/L. By using thermal evapora+on techniques reduced the amount of TDS
range from 400-500mg/L and separa+on of solids is done to a:ain ZLD.

Page 9 5
 The ZLD processing schemes, including thermal evapora+on process was
discussed with their limita+ons. The global applica+ons of ZLD systems was studied

Keywords- Treated industrial wastewater, Thermal Evapora+on process, ZLD technology,

Electrodialysis, Total Dissolved Solids (TDS), Reverse osmosis (RO), RO Concentrate

CONTENTS

Page no.
ABSTRACT 1
CONTENTS 2
LIST OF TABLES 4
LIST OF FIGURES 5
ABBREVATIONS 6
GLOSSARY 7
CHAPTER 1
INTRODUCTION
1.1.RO REJECT 12
I. Using Evaporators to Dewater Reverse Osmosis Reject Stream 12
II. TDS Concentra+ons of RO Reject/ RO Concentrate 13
1.2. ACHIEVING ZERO LIQUID DISCHARGE 13
1.3.DESALTING PROCESS FOR RO CONCENTRATE 15
1.4. CRYSTALLIZATION 15
I. Crystalliza+on 15
II. Purity of Product 16
Page 9 6
 1.5.ZERO LIQUID DISCHARGE 17
I. Zero Liquid Discharge 18
CHAPTER 2
LITERATURE REVIEW 19
CHAPTER 3
PROCESS DESCRIPTION 31
3.1 PREHEATER 31
3.2 VERTICAL SHELL AND TUBE HEAT EXCHANGER 33
3.3 CRYSTALLIZATION 34

3.4 VAPOUR RECOMPRESSION 36

3.5 CIRCULATING PUMP 37
3.6 CENTRIFUGE DECANTER 38
CHAPTER 4
MASS BALANCE AND ENERGY BALANCE 42
CHAPTER 5
DESIGN 49
CHAPTER 6
SALT EXTRACTION TECHNOLOGIES 53
6.1.THERMAL PROCESSES 53
I. Brine Concentrators 54
II. Brine Crystallizers 55
III. Salinity Gradient Solar pond 56
- Brine Concentrator and Recovery System
IV. Spray Dryers 57
V. Evapora+ve Reduc+on and Solidifica+on 57
CHAPTER 7

Page 9 7
 ZLD TECHNOLOGIES 59
7.1 EVAPORATION TECHNOLOGIES
I. Falling film Evaporator 60
II. Forced Circula+on Evaporator/Crystallizer 61
III. Natural Circula+on 62
IV. Plate Type Evaporator 62
7.2 EXTRACTION OF PROFITABLE MATERIALS FROM RO REJECT 64
CHAPTER 8
CONCLUSIONS 65
REFERENCES 66

LIST OF
TABLES

Table No. DescripAon Page No.

1.1 Typical Desalinity Membranes Design Parameters by Water 14
Source
(AWWA, 2004)
1.2 Typical Conc. TDS by Water Treatment process 15
2.1 Treatment processes aimed at Zero Liquid Discharge 25
2.2 Electric power Consump+on in ZLD Encompassing the 27
Thermal
Evaporator
2.3 Analysis of Parameters 29
2.4 Table Showing of Various Design Parameters 29
7.1 Representa+on of Wide Range Applica+ons of Different ZLD 63
Technologies in Various Fields and Opera+ons, Recovery

Page 9 8
 LIST
OF FIGURES

Fig No. DescripAon Page No.

1.1 Distribu+on of Water on Earth 10
1.2 No. of ZLD Installa+ons Over the Years 18
2.1 Pictorial Representa+ons of a Zero Liquid Discharge 19
Treatment
Plant
2.2 Schema+c Diagram of a Thermal ZLD System 23
2.3 The Hierarchical Procedure of ZLD 32
3.1 Schema+c Diagram of a Feedwater Preheater 33
3.2 Ver+cal Shell and Tube Heat Exchanger 35
3.3 Schema+c Diagram of a Forced Circula+on Crystallizer 38
3.4 Schema+c Diagram of Centrifuge Decanter 55
6.1 Schema+c Diagram of ZLD System Including Brine 55
Concentrator and Brine Crystallizer
6.2 Brine Crystallizer 56
6.3 Schema+c Diagram of ZLD System Including Brine 57
Concentrator and Brine Crystallizer, Evapora+on Pond and
Recovery System
6.4 Schema+c Diagram of ZLD System Using Salinity Gradient 60
Solar Pond, Brine Concentrator and Recovery
System
7.1 Schema+c Diagram of Falling Film Evaporator 61
7.2 Schema+c Flow Diagram of Forced Circula+on 62
Crystallizer
7.3 Natural Circula+on 63
7.4 Schema+c Diagram of Plate Type Evaporator 64

Page 9 9
 LIST OF
ABBREVIATIONS

RO Reverse Osmosis
UF Ultra Filtra+on
NF Nano Filtra+on
TDS Total Dissolved Solids
BOD Biochemical Oxygen Demand
COD Chemical Oxygen Demand
ED Electro Dialysis
EDR Electro Dialysis Reversal
MVC Mechanical Vapour Compression
ZDD Zero Discharge Dis+lla+on
SD Solar Dis+lla+on
FC Forced Crystalliza+on
ZLD Zero Liquid Discharge
AWWA American Water Works Associa+on
CSD Crystal Size Distribu+on

GLOSSARY

Potable water: Drinking water is also known as Potable water, which is safe to drink and

used for food produc+on. This word comes from ‘potare’ meaning ‘TO DRINK’.

RO CONCENTRATE: RO CONCENTRATE includes elevated concentra+ons of contaminants

that are removed during the treatment of brackish water for potable water use.

Page 9 10
Contaminants include salts, metals, and nutrients typically at concentra+ons that exceed
the water quality standards.

Preheater: An air pre heater is any device designed to heat the air before another process
with the primary objec+ve of increasing the thermal efficiency of the process.

Heat Exchanger: A Heat Exchanger is a device which used to transfer heat between two or
more fluids. They are used in both cooling and hea+ng processes. The fluids may be
separated by a solid wall to prevent the direct contact.

Crystallizer: Crystallizers are used in industries to achieve liquid-solid separa+on. These

are important piece of chemical processing equipment because they are capable of
genera+ng high purity products with rela+vely low energy inputs.

CrystallizaAon: Crystalliza+on is the process by which solid forms where the atoms or
molecules are highly organized into a structure known as a crystal..

CirculaAon pump: A Circula+on pump or is a specific type of device used to circulate

gases, liquids slurries in a closed circuit.

Slurry pump: A slurry pump is a device designed for pumping liquid containing solid
par+cles. Both centrifugal and posi+ve displacements pumps can be used for slurries.

Decanter Centrifuge: A Decanter centrifuge separates solids from one or two liquid
phases in one single gas con+nuous process. When subjected to such forces, the denser
solid par+cles are pressed outwards against the rota+ng wall while the less dense liquid
phase forms a concentric inner layer.

Mother liquor: A Mother liquor is the part of the solu+on which is leg over ager
crystalliza+on. It is encountered in chemical processes including sugar refining. It is the
liquid obtained by filtering the crystals by filtra+on.

Page 911
Brackish water: Brackish water is water having more salinity than freshwater but not as
much as seawater. It is obtained by mixing seawater with freshwater. Brackish water
contains between 0.5 and 30 grams of salt per litre.

Retentate: Retentate is a part of the feed that does not pass through the membrane,
while the permeate is part of the feed that does pass through the membrane.

TDS (Total Dissolved Solids): In water treatment, is the inorganic residue leg ager the
filtra+on of colloidal and suspended solids and then the evapora+on of a known volume
of water. TDS is reported as ppm or mg/L.

Turbidity: Turbidity is a suspension of fine colloidal par+cles that do not readily se:le out
of solu+on and can result in “cloudiness”. Turbidity is determined by a Nephelometer that
measures the rela+ve amount of light able to pass through the solu+on.

ppm (parts per million): A method for repor+ng the concentra+on of an ion or substance
in water. The following conversions are applicable for dilute waters with a specific gravity
of 1.0: One ppm is equal to one mg/L. One Grain per U.S. Gallon is equal to 17.1 ppm.
One Pound per 1,000U.S. Gallons are equal to 120 ppm. A one % solu+on is equal to
10,000 ppm. One ppm is equal to 1,000 ppb.

Brine: Water that contains salt is known as brine, highly salty and heavily mineralized
water containing heavy metals and organic contaminants.

Freshwater: Water that is not salty, for instance, water found in lakes, streams, and rivers
but not in ocean. It is also refer to things living in or related to freshwater.

Industrial Wastewater Treatment: Wastewater treatment for industries such as

manufacturing, food processing, corrugators, prin+ng and so on. Paper and pulp mills
treatment of wastewater is an example of industrial wastewater treatment. Municipal
wastewater treatment would be an example not considered to be industrial.

Influent: The stream of water that enters any system or treatment unit.

Page 9 12
Process water: Water that serves in any level of the manufacturing process of certain
products.

Reverse Osmosis process: The Reverse Osmosis (RO) process uses a semi-permeable
membrane to separate and remove dissolved solids, organic pyrogens, submicron
colloidal ma:er, viruses and bacteria from water. This process is called Reverse Osmosis.
Since, it requires a pressure to force pure water across a membrane leaving the impuri+es
behind.

Semi-permeable: A medium that allows water to pass through, that rejects dissolved
solids, so that it can be used to separate solids from water.

Sludge: A semi-solid residue containing microorganisms and their products from any
water treatment process. The solid waste material which se:les out in the wastewater
treatment process, some+mes biosolids can be dewatered and reused or disposed.

Total Solids: The weight of all present solids per unit volume of water. It is usually
determined by evapora+on. The total weight concerns both dissolved and suspended
organic and inorganic ma:er. All the solids in wastewater or sewage water including
suspended solids and filterable solids.

Toxic water pollutants: Compounds that are not naturally found in the water at given
concentra+ons and that cause death, disease or birth defects in organisms that ingest or
absorb them.

Ultraviolet DisinfecAon (UV): The use of ultraviolet light to kills bacteria and other
microorganisms in water and wastewater.

Wastewater: The spent or used water from a home, community, farm, or industry that
contains dissolved or suspended ma:er.

CHAPTER – 1

Page 9 13
 INTRODUCTION

The lack of potable water and the deple+on of raw materials are two major issues that
have emerged in recent decades due to the rapid increase in the world's popula+on and
improvements in standards of living. Membrane technology plays a major role in
addressing the above issues. Specific addi+onal treatments are required for improving
water recovery strategies, opera+onal costs, and quality of water produced, overcoming
the impact of brine (i.e. Concentrate) and determining how much of it is disposed of into
the eco-system.

However, it is worth no+ng that almost 97.5% of the total is in oceans in the form
of salty water and is not suitable for drinking, watering, or industrial use. The remaining
2.5% is fresh water. Unfortunately, not even that small amount is easily accessible or
exploited, because it is stored as ice on the poles and on mountaintops as 70% of the
fresh water has been trapped and frozen in glaciers and polar ice caps of the Greenland
and the Antarc+ca.

Furthermore, a significant amount of the rest lies very deep in the ground as
they are present as soil moisture, or lies in deep underground aquifers as groundwater
not accessible to human use due to the fact that it is very difficult to extract. In Fig. 1.1,
the distribu+on of water on Earth is presented. Most of the remainder which is less than
1% of the world's fresh water (approximately 0.009% of all water on earth) is accessible
for direct human uses. This is the water found in lakes, rivers, streams, reservoirs and
those underground sources that are shallow enough to be tapped at an affordable cost.
Fresh water is purified and reallocated or renewed by rain and snowfall through the
hydrological cycle in nature.

Page 9 14
 Fig.1.1: Distribu+on of water on Earth

Nowadays, this natural process is inadequate due to human ac+vi+es, and

specifically because of the thoughtless was+ng of water and discharge of various
pollutants into the aqua+c environment.

However, abundant supplies of fresh water are essen+al to industrial development.

Enormous quan++es of water are required for process needs, boiler-feed, cooling
systems, and for sanitary and potable purposes.

Water is a vital substance for suppor+ng life on Earth. For example, a tree
contains 60% water; most animals are composed of about 65% water, while our bodies
contain around 55% water. Everyone needs fresh water daily to cover the daily demand in
food, domes+c use, etc. Fresh water is used in agriculture, construc+on, Transport, the
Chemical industry, and numerous other ac+vi+es of human beings.

An adequate freshwater supply is a global challenge because the source of

freshwater resources is deple+ng at an alarming rate. It has been reported that more
than 1 billion people have no access to drinkable water and approximately 2.3 billion
people (41% of the world Popula+on) live on this planet with water shortages. To
overcome this challenge, desalina+on of seawater and brackish water using high-pressure
membranes including reverse osmosis (RO) and nanofiltra+on (NF) technology, has
Page 9 15
become an excellent solu+on in recent years since they produce outstanding water
quality.

These membranes have been demonstrated to be highly effec+ve for rejec+ng

abroad range of organics in feed water including micro pollutants and hormones, various
inorganic compounds, and biological materials (viruses, bacteria, cell component). Also,
this has the advantages of small footprint, easy maintenance and capacity extension.
Desalina+on processes separate feed water into clean water and concentrate streams
known as brine.

The typical water recovery of seawater RO systems varies between 40% to

50%and brackish water RO desalina+on plants typically operate at recoveries of 75% to
85%. The water recovery varies due to different sample characteris+cs, trans-membrane
pressure, and membrane used for the treatment. However, the proper disposal/
management of the brine represents significant environmental challenges to most plants
because they consist of highly concentrated salts, organics, and other contaminants.

Conven+onal disposal op+ons for concentrate are surface water discharge,

deep well injec+on, evapora+on ponds and land applica+on. Disposal of brine is of much
significance both from environmental and economic standpoints, par+cularly for inland
ci+es. For example, in Canberra, Australia, sustainable management of brine remains one
of the significant environmental and economic barriers to the RO-based advanced
reclama+on plant. Although conven+onal disposal methods have been commonly used in
prac+ce, the concern of the safe disposal of brine has been focused in recent years to
reduce the poten+al long-term risk on environment and health.

Several studies have examined the environmental fate of brine disposal on soil
deteriora+on, groundwater quali+es, and aqua+c environment. In fact, the brine has an
adverse effect on aqua+c living organisms. The high TDS and lowering level of
groundwater due to over exploita+on; water scarcity is going to be a major threat for the
industry in the near future. With con+nuous increase in the demand of water the only
Page 9 16
op+on would be to reuse/recycle the water to the extent possible or achieve zero liquid
discharge (ZLD).

1.1. RO REJECT:

Reverse osmosis (RO) water technology has been used for years in various industries to
separate dissolved solids from water by forcing the water through a semi-permeable
membrane. RO reject water disposal is also commonly used to purify drinking water and
desalinate seawater to yield potable water.

Reverse Osmosis is a process which a solvent passes through a semi permeable

membrane in the direc+on opposite to that for actual osmosis when subjected to a
hydrosta+c pressure greater than the osmo+c pressure. The water and other molecules
with lower molecular weights (specific weight of molecules allowed to pass through is
dependent on the selected membrane) pass through the micro pores’ in the membrane,
yielding a purified water stream called the Permeate. Large molecules are retained by the
membrane as well as a por+on of the water that does not pass through the membrane.
This concentrated stream is called the RO Concentrate/RO Reject.

I. Using Evaporators to Dewater Reverse Osmosis Reject Stream:

In industrial sedngs, RO is ogen used to remove total dissolved salts (TDS) from industrial
wastewater or treated industrial wastewater and yield permeate with rela+vely low TDS
concentrates.

While RO is an effec+ve method for handling wastewater, what to with the

concentrate or reject water (typically as much as 20-50% of the RO feed water volume)
can be issue. Specifically, the high salinity in RO reject/RO concentrate can make it
prohibi+ve for discharge to a local sewer facility. Hauling the wastewater to a treatment
facility can also be prohibi+vely expensive.

Mechanical Vapour Compression (MVC) evaporators and Thermal Evaporators

have proven to be effec+ve technologies for dewatering RO reject/RO concentrate waste
Page 9 17
streams. In brief, evapora+on is a +me tested methodology for reducing the water
por+on of water-based waste.

The evapora+on converts the water por+on of water-based waste to water vapour, while
leaving the higher boiling contaminants behind. This greatly minimizes the amount of
waste that needs to be hauled off-site.

Evapora+on technology has always been more “hands off” than other
wastewater treatment methodologies resul+ng in a drama+cally lower labour cost.
Evapora+on technology can handle a much wider range of waste streams compared to
membranes and tradi+onal physical/chemical treatment methodologies. Finally,
evapora+on does a much be:er job of concentra+ng waste streams compared to other
methods, thereby yielding a lower disposal volume and cost.

II. TDS ConcentraAons of RO Reject/RO Concentrate:

Typical RO Reject/RO concentrate TDS concentra+ons are ogen in the range of

30000-50000mg/litre. The salts in solu+on can range from highly soluble sodium and
potassium salts to less soluble or reverse soluble calcium and barium salts.

NOTE: The term reverse soluble implies lower solubility as solu+on temperature
increases. MVC Evaporators operate of typical temperatures of 225-230o F for high TDS
applica+ons like RO reject/RO concentrate. Similar or slightly higher (250oF maximum)
opera+ng temperatures can be expected with high TDS applica+ons for Thermal
Evaporators.

Evaporator concentra+on endpoints correspond closely with satura+on

concentra+on of the various salts at the referenced temperatures. Many sodium and
potassium salts such as sodium sulphate, sodium chloride, potassium chloride, and
potassium nitrate, have satura+on points in the range of 400,000-600,000mg/litre at the
referenced elevated temperatures.

Page 9 18
 Based on a simple arithme+c, concentra+ng the RO reject/RP concentrate
wastewater from 30,000 to 40,000 mg/litre corresponds to a volume reduc+on
percentage of approximately 92.5%. Concentra+ng from 50,000 to 600,000 mg/litre
would yield to a volume reduc+on percentage of approximately 91.6%.

Less soluble salts as barium sulphate and magnesium carbonate present more
of an issue due to the tendency to precipitate out and scale heat transfer surfaces, to
minimize this issue, a type of an+scale referred to as Threshold Scaling Inhibitors(TSI) are
being used. TSI is added upstream of the evaporator and modifies the insoluble salt
crystals crea+ng a sog slurry that has less of a tendency to adhere to surface and cause
scale. The resul+ng sog slurry also has a consistency that minimised the likelihood of
erosion on heat exchanger or plumbing surfaces.

1.2. ACIEVING ZERO LIQUID DISCHARGE:

Where there is an interest or requirement to achieve zero liquid discharge (ZLD),

evapora+on can be used to concentrate the RO reject / RO concentrate, which can then
by further dewatered with supplemental equipment. Please refer to the diagram below
for a typical layout diagram for a ZLD solu+on that shows RO reject/RO concentrate (or
other high TDS wastewater) being fed to the MVC evaporator followed by dewatering of
the MVC concentrate by a Thermal evaporator and a centrifuge.

In the first stage of handling RO reject/RO concentra+on, an MVC evaporator is

fed with the RO reject /RO concentrate and it yields dis+lled water and concentrate. The
concentrate goes to a concentrate storage tank, which separates into slurry and
supernatant layers. The supernatant layer get pumped to an Thermal evaporator, which
further concentrates the liquid while exhaus+ng water vapour to atmosphere. The
concentrated slurry from the thermal evaporator is pumped back into concentrate
storage tank. The slurry layer from the tank is pumped into a centrifuge. The TDS
Concentra+ons for the Seawater has higher TDS levels and lower recovery rate compared

Page 9 19
 to Surface water, Fresh & Brackish Groundwater and showing various parameters (Table
1.1.)

The imposi+on of ZLD is to ensure availability of water for future use ensuring its
sustainability. The concept is not new to India. The recent changes in the rules and
regula+ons have however provided the necessary impetus in a focused manner.

This technology Guidance manual covers a broad spectrum such as technology, economic
considera+on and management to facilitate the implementa+on of ZLD.

Table 1.1: Typical Desal+ng Membrane System Design Parameters by Water Source
Parameter Surface water Fresh Brackish Seawater
(units) Groundwat Groundwater
er
Feedwater 200-400 400-50 500-10,000 30,000-40,000
TDS(mg/L) 0
Water
Recovery
80-90 80-90 65-85 40-60
(% of feed)
Concentrat
e
10-20 10-20 15-35 40-60
Vol. (% of
feed)
Concentrat
e
13303660(85 2660-3330 200040,000(75 60,00080,000(5
TDS (at
%) (85%) %) 0%)
indicated %
recovery)
(mg/L)
Concentra+ 5-10 5-10 2.9-6.7 1.7-2.5
on Factor

Page 9 20
Maximum and Minimum TDS Concentra+ons for the Seawater by using RO process is
more compared to RO process for Brackish water for different processes Maximum and
Minimum TDS Concentra+on Varies (Table 1.2.)
Table 1.2: Typical Concentrate TDS by Water Treatment Process
Process Typical Feedwater Min. Concentrate Max. Concentrate
TDS, mg/L TDS, mg/L TDS, mg/L
Seawater RO 32,000-45,000 50,000 80,000
Brackish RO 1000-10,000 3000 40,000
ED/EDR 1000-4000 3000 30,000
Sogening 300-1000 1000 5000

1.3. DESALTING PROCESS FOR RO CONCENTRATE:

Recovery of salts from RO concentrate is increasing for its environmental safe way to
reuse of waste volume of reject. The change of solu+on temperature either by
evapora+on and cooling used to extract salts from concentrate has been widely used
worldwide. In which, electro-dialysis, ion-exchange, eutec+c freezing, and chemical
processing are being prac+ced to recover salts from concentrate. Further, in advance
hybrid systems which consis+ng of combina+on of two or more separa+on process
techniques, such as the nanofiltra+on—reverse osmosis—thermal processes, are being
deployed ac+vely to increase the amount of extracted salt and reduce the final volume of
reject.

1.4. CRYSTALLIZATION:

The crystalliza+on technology has certain advantages such as a high recovery ra+o of
resources and recovery of high quality water.

Although crystalliza+on is widely used for purifica+on and separa+on, the design and
opera+on of a crystallizer s+ll face many limita+ons.

Page 9 21
These include, for example, poor reproducibility in the final crystals' characteris+cs,
limited super satura+on control and less ability to modulate the super satura+on
genera+on rate.

I. CrystallizaAon:

Crystalliza+on is the forma+on of solid par+cles within a homogeneous phase. It may

occur as the forma+on of solid par+cles in a vapour, as in snow; as solidifica+on from a
liquid melt, as in the manufacture of large single crystals; or as crystalliza+on from liquid
solu+on. This chapter deals mainly with the last solu+on. The concepts and principles
described here equally apply to the crystalliza+on of a dissolved solute from a saturated
solu+on and to the crystalliza+on of part of the solvent itself, as in freezing ice crystals
from seawater or other dilute salt solu+on.

Crystalliza+on from solu+on is important industrially because of the variety of materials

that are marketed in the crystalliza+on form. Its wide use has a twofold basis: A crystal
formed from am impure solu+on is itself pure (unless mixed crystals occur), and
crystalliza+on affords a prac+cal method of obtaining pure chemical substance in a
sa+sfactory condi+on for packaging and storing.

II. Purity of product:

A sound well-formed crystal itself is nearly pure, bus it retains mother liquor when
removed from the final magma, and if the crop contains crystalline aggregates,
considerable amounts of mother liquor may be occluded within the solid mass. When
retained mother liquor of low purity is dried on the product, contamina+on results, the
extent of which depends on the amounts and degree of impurity of the mother liquor
retained by the crystals.

In prac+se, much of the retained mother liquor is separated from the crystals by filtra+on
or centrifuging, and balance is removed by washing with fresh solvent. The effec+veness
of these purifica+on steps depends on the size and uniformity of the crystals.
Page 9 22
Importance of crystal size:

Clearly, good yield and high purity are important objec+ves in crystalliza+on, but the
appearance and size range of a crystalline product also are significant. If the crystals are
to be further processed, reasonable size and size uniformity are desirable for filtering,
washing, reac+ng with other chemicals, transpor+ng, and storing the crystals, If the
crystals are to be strong, non-aggregated, uniform in size, and non-caking in the package.
For these reasons, crystal size distribu+on (CSD) must be under control; it is a prime
objec+ve in the design and opera+on of crystallizers.

For applica+ons where high rates of evapora+on are required, where there are scaling
components, or when crystalliza+on must be achieved in solu+ons with inverted solubility
or rela+vely high viscosity, the forced circulaAon crystallizer is the best choice.

The accelera+ng rate of global popula+on growth and the subsequent increase in water
demand have burdened the available water resources. As such, the necessity for
sustainable water sources has become a pressing ma:er. Desalina+on technologies have
gained much a:en+on in recent years as their performance and applica+on has grown
throughout the years. However, brine streams pose a major challenge in terms of their
disposal and the associated environmental impacts. It has been es+mated that the daily
brine produc+on from desalina+on plants around the world is approximately 142 million.

Brine composi+on, volume and disposal techniques affect brine disposal cost which can
cons+tute up to a third of total product water cost for desalina+on technologies. The
selec+on of the op+mal brine management strategy depends on several factors including
brine volume and composi+on, discharge loca+on, and the capital and opera+ng costs
Surface water discharge, deep well injec+on and land applica+on are common brine
disposal op+ons.

1.5. ZERO LIQUID DISCHARGE:

Page 9 23
ZLD refers to any process or combina+on of processes through which there is no liquid
effluent from a chemical process plant. Exis+ng ZLD systems focus mainly on the
evapora+on and crystalliza+on processes, which are not always the op+mal technologies
to treat brine. ZLD is usually achieved by concentra+ng the brine stream using several
processes, such as thermal and membrane-based systems, followed by a brine-to-salt
processing stage for salt recovery Hence, ZLD increases the water supply while reducing
water pollu+on, but at the expense of high cost and intensive energy consump+on .

Therefore, reliable and efficient ZLD configura+ons must be designed through the
combina+on of different technologies to achieve op+mal water recovery and energy
consump+on while accoun+ng for the produced salt. These technologies will not be
considered in this work.

Worldwide construc+on of ZLD plants represents an average of around 200 million usd of
investment annually. Today there are thousands of evaporator/ concentrator systems
around the world in a large range of industries. It is spreading widely to water scarce
regions and too highly sensi+ve and polluted environments.

Countries like China and India, where water is scarce and the industrial water recovery
ra+o is very low, are poten+al candidates for the development of ZLD solu+ons. The
Market for ZLD systems has grown steadily during the period 2000-2014 (figure 1.2.)

Page 9 24
 Fig 1.2: Number of ZLD installa+ons over the years

I. DEFINITION OF ZERO LIQUID DISCHARGE

Zero liquid discharge (ZLD) refers to the recycling and treatment process in which the
plant discharges no liquid effluent into surface waters, completely elimina+ng the
environmental pollu+on to water bodies. ZLD process makes effec+ve use of waste water
treatment, recycling, and reuse, thereby contribu+ng to water conserva+on through
reduced intake of the fresh water.

“Zero Liquid Discharge refers to installaAon of faciliAes and system which enables
industrial effluent for absolute recycling of permeate and converAng solute (dissolved
organic and inorganic compounds/salts) into residue in the solid form by adopAng
method of concentraAon and thermal evaporaAon.”

ZLD is recognised and approved based on two broad parameters that are, water
consump+on versus waste water reused or recycled (permeate) and corresponding solids
recovered. In the above ZLD defini+on, domes+c waste water from industry is separated
from industrial waste water and treated separately. However, recycle/disposal of
domes+c waste water is not men+oned or s+pulated.

Page 9 25
ZLD is applicable to industries genera+ng wastewater of high BOD/COD load, colour,
metals, pes+cides, toxic/hazardous cons+tuents, solvents and high TDS bearing effluents.
However, considering water scarcity and reject water/ sludge disposal cost, many
industries and adop+ng as a long term strategy.

CHAPTER – 2

LITERATURE REVIEW
Zero-liquid discharge (ZLD) technology for resource recovery from
wastewater:

Water resources are becoming scarce meaning that reuse op+ons are receiving more and
more a:en+on. In this perspec+ve, zero-liquid discharge (ZLD) is considered as an
emerging technique to minimize waste, recover re-sources, treat toxic industrial waste
streams, and mi+gate poten+al water quality impacts in receiving water streams.
Although ZLD systems are capable of minimizing contamina+on of water sources and
amplifying water supply, its industrial scale applica+ons are restricted due to their high
cost and intensive energy consump+on. In ZLD systems, membrane-based technologies
are an a:rac+ve future strategy for industrial waste water reclama+on (figure 2.1.).
Thermal Evapora+on Technologies are used to remove inorganic salts from RO Reject and
reduce the TDS levels. One of the Thermal evapora+on Technology is using the Brine
concentrator and Brine Crystallizer to achieve ZLD (figure 2.2.)

Page 9 26
 Fig 2.1: Pictorial representa+on of a Zero Liquid Discharge Treatment Plant

Fig 2.2: Schema+c diagram of a Thermal ZLD

system

Status of ZLD systems for resource recovery in India:

The prac+cal implementa+on of ZLD systems across the globe for re-source recovery
depends upon geographical loca+on, as applied in the European Union, USA, Australia,
Canada, the Middle East, Mexico, China, and India (Lanny, 2015;GWI, 2009;Durham and
Mierzejewski,2003;Heins and Schooley, 2004).

Page 9 27
Rapid industrializa+on and urbaniza+on in India is crea+ng severe pressure on water
resources and is increasing pollu+on. Recently, a three-year target was set by the Indian
government—known as the
“Clean Ganga project”—that imposes stringent regula+ons on wastewater discharge and
compels highpollu+ng industries to move toward ZLD (Abdelhamid, 2015). In 2015, the
Indian government's water conserva+on policies imposed ZLD installa+on at all tex+le
plants generat-ingN25 m3of wastewater per day (Singh and Bhalla, 2017). India has
extended ZLD to a range of industrial sectors including power, steel, pharmaceu+cal,
chemical, tex+le, and food and beverage industries (Rappich, 2016). In 2008, a ZLD system
was implemented in the city of Tirupur for the recovery of both water and valuable salts
from tex+le wastewater, which are directly reused in the dyeing process (Singh and
Bhalla, 2017).[1]

Water Reuse: A Successful Almost Zero Discharge Case

This paper presents a procedure to op+mize a real problem of freshwater and wastewater
reuse alloca+on. The case study is an industrial polypropylene unit and the solu+on
achieved is an almost zero discharge case. The problem was decomposed into subsystems
according the type of approach used to water minimiza+on: process changes,
regenera+on reuse and regenera+on recycling. For the regenera+on approach, an
innova+ve photochemical process capable to remove all the organic compounds
contained in the wastewater in order to make it suitable to be reused in the process was
used.

For process changes approach, since the major water used in factory is for the cooling
process system, a hybrid system composed by air cooler and wet cooling tower is been
proposed to replace the wet cooling tower. The air cooler system is used first and the final
temperature approach is achieved by the wet cooling tower. Thus, the main scope of the
present work is to show that is possible to reach the "almost zero discharge" for an

Page 9 28
industrial case by using innova+ve wastewater treatment technologies together with
op+miza+on of water/air cooling systems.

The results obtained prove that the water minimiza+on techniques used can effec+vely
reduce overall fresh water demand and the overall effluent generated, resul+ng in lower
costs of fresh water and effluent treatment costs. [2]

RO brine treatment and disposal methods:

More than 50 percent of countries in the world will likely face water stress or water
shortages by 2025, and by 2050, as much as 75 percent of the world’s popula+on could
face water scarcity. Desalina+on technologies, par+cularly the reverse osmosis (RO)
process, have increasingly been adopted to produce freshwater from alterna+ve sources
such as seawater and brackish water due to water scarcity. However, desalina+on
applica+ons have always been limited by the disposal costs of RO brine and the adverse
impact of brine on the receiving environment.

The scope of this paper is to iden+fy technically and commercially RO brine disposal and
treatment methods such as deep well injec+on, discharge into the sea, sanitary sewers,
evapora+on ponds, forward osmosis (FO), vacuum membrane dis+lla+on (VMD), vacuum-
enhanced direct contact membrane dis+lla+on (VEDCMD), RO–NF Integrated system,
bipolar membrane electrodialysis (BMED), electrodialysis (ED), Electrodialysis reversal
(EDR), vibratory shear enhanced processing (VSEP), capaci+ve deionisa+on (CDI) and so
on.

In this paper, as a part of our desalina+on research package, to achieve profitable and
environmental solu+ons, we assess advantages and disadvantages of men+oned methods
through a comprehensive review of worldwide laboratory, pilot and industrial scale
experiments.

Page 9 29
For RO brine treatment methods,

• FO achieved water recoveries up to 90% from the brines. Addi+on of a scale inhibitor
during process was effec+ve at maintaining high water flux for extended +me. The
total water recovery (the recovery from the RO process combined with the FO
process), greater than 98% total was achieved.
• The bipolar membrane electrodialysis (BMED) pro-cess was shown to be technically
feasible for producing mixed acids and bases of reusable quality from RO concentrate.
• VEDCMD achieved water recoveries up to 81% from the brines. Addi+on of a scale
inhibitor during pro-cess was effec+ve at maintaining high water flux for extended
+me. The total water recovery (the recovery from the RO process combined with the
VEDCMD process), greater than 96% total was achieved.
• The recovery from the RO process combined with ED was achieved up to 98%.
• The overall RO–EDR water recovery was achieved up to 91%.
• Treatment of RO reject via VSEP will be able to achieve up to 98% recovery of treated
water.
• CDI based RO brine treatment could improve overall water recovery over 90%.
• 95% total system water recovery was possible for RO desal+ng using ICD at the pilot
and demonstra+on scales.
• VC process is well established and is used for trea+ng RO concentrate in a near-ZLD
applica+on.
• During the treatment of a RO concentrate with high silica concentra+on, MD could
reduce the volume of RO concentrate by 60%, achieving an overall water recovery of
90% through RO–MD.
• MDC ability to concentrate RO brines is greater than 90%.
• In principle, integra+on of the NF unit with RO in water desalina+on plants makes it
possible to approach improving salt rejec+on and thus leads to decrease in the
salinity of water product and consequently the recovery has improved considerably,
compared to that obtained in RO alone.
Page 9 30
• EFC achieved water recoveries up to >95% from the brines.

And for RO brine disposal methods, above sec+ons show:

• Discharge of desalina+on concentrate to a surface water body (river, lake, lagoon,

canal, ocean, etc.) is the most common management prac+ce for brine disposal.
• Discharge of concentrates to sanitary sewer systems is some+mes feasible if the
concentrate mixture is not toxic and does not adversely affect the clarifier se:le-
ability or restrict final effluent disposal.
• Land applica+on can provide a beneficial reuse of water when membrane
concentrates are applied to vegeta+on, such as irriga+on of lawns, parks, or golf
courses. Factors associated with land applica+on include the water quality tolerance
of target vegeta+on to salinity, the ability to meet ground water quality standards, the
availability and cost of land, percola+on rates, and irriga+on needs. In general, land
applica+on is used only for smaller volumes of concentrates.

• Deep well injec+on is a disposal technology which liquid wastes are injected through
the injec+on tubing into the well. Since there is no technical difficulty in injec+ng
desalina+on waste, it is one of the frequently used methods in disposing waste;
however regula+ons on deep well injec+on are strict.
• Solar evapora+on is a viable alterna+ve in rela+vely warm, dry climates with high
evapora+on rates, level terrain, and low land costs. Regula+ons typically require an
impervious lining and monitoring wells, which will increase costs of evapora+on
ponds. With li:le economy of scale, evapora+on ponds are usually used only for small
volume concentrates.[3]

Graphically based analysis of water system with zero liquid discharge:

Based on graphical method, this paper proposed the necessary condi+on of zero liquid
discharge (ZLD) and op+mized the corresponding regenerated water flowrate and
regenera+on concentra+on for single contaminant water system with fixed mass load. As
Page 9 31
far as the water system without water loss is concerned, ZLD can be accomplished when
the post regenera+on concentra+on is not higher than the minimum limi+ng inlet
concentra+on of all the opera+ons.

Moreover, considering the water system with water loss, the formula+ons for calcula+ng
the op+mal targets (the op+mal regenerated water flowrate and the op+mal
regenera+on concentra+on) for ZLD are deduced. The maximum post-regenera+on
concentra+on for ZLD is defined. If the post-regenera+on concentra+on is not higher
than it, ZLD is feasible. The op+mal zero discharge water network is constructed with a
given post regenera+on concentra+on (figure 2.4.)

Fig 2.4: The Hierarchical procedure of ZLD

For the single contaminant water system, this paper analyzes the condi+ons and op+mal
targets for zero liquid discharge water system with fixed mass load. Considering the
water system without water loss, zero liquid discharge can be accomplished when the
post-regenera+on concentra+on is not higher than the minimum limi+ng inlet
concentra+on of all the opera+ons. This paper proposed the method for targe+ng the
op+mal pre- and post regenera+on concentra+ons. Moreover, considering the water
system with water loss, based on the extension for the method proposed by Agrawal and
Shenoy (2006), this paper presents a graphical method to target the op+mal

Page 9 32
 regenera+on concentra+on and regenerated water flowrate, and the corresponding
formulas are deduced. The maximum post-regenera+on concentra+on Cmax, o for ZLD is
defined and can be obtained by graphical method. The necessary condi+on for ZLD is
that the post regenera+on concentra+on is not higher than Cmax, o. Finally, the design
strategies for ZLD water network are illustrated. [5]

State of the art and review on the treatment technologies of water reverse osmosis
concentrates:

The growing demand for fresh water is par+ally sa+sfied by desalina+on plants that
increasingly use membrane technologies and among them reverse osmosis to produce
purified water. Opera+ng with the water recoveries from 35% to 85%.

RO plants generate huge volumes of concentrates containing all the retained compounds
that are commonly discharged to water bodies and cons+tute a poten+ally serious threat
to marine ecosystems; therefore there is an urgent need for environmentally friendly
management op+ons of RO brines.

This paper gives an overview on the poten+al treatments to overcome the environ-
mental problems associated to the direct discharge of RO concentrates. The treatment
op+ons have been classified according to the source of RO concentrates and the maturity
of the technologies. For the sake of clarity three different sources of RO concentrates are
differen+ated

i) desalina+on plants,
ii) Ter+ary processes in WWTP, and iii) M i n i n g
industries.

Star+ng with tradi+onal treatments such as evapora+on and crystalliza+on other

technologies that have emerged in last years to reduce the volume of the concentrate
before disposal and with the objec+ve of achieving zero liquid discharge and recovery of
valuable compounds from these effluents are also reviewed.
Page 9 33
 Most of these emerging technologies have been developed at laboratory or pilot plant
scale. With regard to RO concentrates from WWTP, the manuscript addresses recent
studies that are mainly focused on reducing the organic pollutant load through the
applica+on of innova+ve advanced oxida+on technologies. Finally, works that report the
treatment of RO concentrates from industrial sources are analyzed as well (Table 2.1.) [6]

Table 2.1: Treatment processes aimed at Zero Liquid Discharge

Types of Schemes Treatment Stages Overall
Recovery
Basic ZLD Primary RO Secondary RO 88-99%
Scheme
_

Type-A ZLD Primary RO Ion exchange Secondary RO

Scheme Resins for
Silica
removal
Primary RO Precipita+on
treatment(alk
Secondary RO 87-97%
aline induced)

RO WAIV Membrane 77-89%

Crystallizer
Type-B ZLD
Scheme Primary RO Secondary RO Precipita+on
Treatment (Calcium
Sulfate, magnesium,
iron and silica)

Page 9 34
 RO ED/EDR 92%
Primary RO Secondary RO EDR + UF, WAIV >98%
Type-c ZLD Primary RO Lime Soda Secondary Ro,
Scheme Treatment Evapora+on
80-90%
Intermediate Secondary RO,
Primary RO
Treatment Brine Concentrator +
pond ~100%

PILOT TESTING OF MEMBRANE ZERO LIQUID DISCHARGE FOR DRINKING WATER

SYSTEMS:

U+li+es in Colorado and throughout the western United States have been reluctant to
build reverse osmosis (RO) membrane plants due to the uncertainty surrounding the
disposal of concentrate (brine). Concentrate minimiza+on and zero liquid discharge (ZLD)
technologies show promise to provide cost effec+ve means for brine disposal. The
purpose of this project was to pilot test concentrate minimiza+on and zero liquid
discharge technologies suitable for use in Colorado.

A new technology, zero discharge desalina+on (ZDD), was pilot tested at two drinking
water RO plants in Colorado. The ZDD technology is an integrated system combining
electrodialysis metathesis (EDM) with nanofiltra+on. The first pilot test reached 96%
recovery when trea+ng brackish groundwater to levels suitable for human consump+on.
The second pilot test demonstrated increasing the recovery an exis+ng membrane system
to 98% by trea+ng its concentrate stream.

The ZDD technology did not obtain zero discharge as its name implies, but it
demonstrated the ability to produce excellent water quality and obtain high recovery. The
ZDD technology shows good poten+al to reduce the volume of concentrate produced by
membrane plants. But further development of the technology is needed with the goal of
reducing cost, increasing reliability and simplifying its opera+on before the process is
suitable for full-scale use in Colorado.
Page 9 35
Benefits:

• Provides a literature review of concentrate minimiza+on and zero liquid discharge

technologies.
• Provides pilot test assessments of the zero discharge desalina+on technology.
• Provides cost es+mates for full scale implementa+on of zero discharge desalina+on
technology.[7]

THERMAL EVAPORATOR FAILS-THE OPERATING AND MAINTAINANCE COST:

The main reason was the financial inability of the industry to meet the opera+on
and maintenance cost by way of electrical power as in Tables 2.3 hereunder. When the
CETPs were set up ini+ally for merely adding Lime and Ferrous Sulphate and
discharging the treated effluent without removing the TDS, the O&M cost for the
industry was only INR 15 per Kl of raw effluent. When suddenly the ZLD was
slapped this shot to 120 / 132 at a 850 % jump. Clearly, the blame for not
achieving the true ZLD will appor+on to the PCB as well because it has not
brought out a sustainable technology and became like the (in)famous Shylock of
Shakespeare drama(Table 2.2.).

Table 2.2: Electrical power consump+on in ZLD Encompassing in Thermal Evaporator

S. No Component of ZLD KWhr/cu % of Equivale
m of feed Effluent nt of raw
1. Primary Treatment like 0.9 100 0.9
equalisa+on, chrome precipita+on,
neutraliza+on etc
2. 1.5 100 1.5
Biological Treatment in aera+on
3. 3.2 100 3.2
Cross flow membrane filtra+on
4. 2.4 100 2.4
RO desal+ng membrane filtra+on
5. 6.0 15 0.9
Thermal Evapora+on
Total/cum of feed 8.9

Page 9 36
ADVANTAGES

• Eliminates steal generators as induced thermal evapora+ve opera+on · Eliminates

complicated mechanical and electrical infrastructure.
• Eliminates metal scaling and corrosion problems.
• Eliminates dependence on specialist trained high-skill operators.
• Eliminates dependence of vendors for equipment repairs and renewals.
• Eliminates back up high energy diesel generator sets.
• Eliminates need to keep the set-up “warm” even during “no-Reject” periods.
• Eliminates O&M costs as close to about INR 200 / kilolitre of R O Rejects.
• Eliminates random specifica+ons as there is no BIS code of prac+ce.
• Completely nature based system with two phase fluid-air mass transfer.
• Permits switch-on and switch-off as and when needed.
• System uses only an ordinary centrifugal foot mounted pump set.
• The nedngs are readily available off the shelf green-house nedngs.
• Efficiency can be maximized using spray nozzles for applica+on on nedngs.
• Rainy days also bring about evapora+on and do not need shut down.
• Temporary roofing using tarpaulins over truss work protects from direct rainfall.

• O&M cost is a maximum of INR of only about Rs 15 / kilolitre of R O Rejects.

• System can be fabricated by locally available masons and fabricators.[8]

A Zero Liquid Discharge in PharmaceuAcal Industry:

Zero Liquid Discharge (ZLD) is an ideal situa+on of complete closed loop cycle, where
discharge of any liquid effluent is eliminated; it is a remarkable effort of every industry
who implements it to meet with the environmental regula+on in a challenging way. For
achieving ZLD system for the industry, certain steps are needed to be taken.

These steps include: Analysis of major characteris+cs of all influent streams entering into
ETP, Iden+fica+on of poten+ally recyclable streams and highly polluted stream,

Page 9 37
Segrega+on of streams on the basis of their characteris+cs and applicability of 4R
(Reduce, Reuse, Recycle and Recover) principle in par+cular plant.

Op+miza+on of Effluent Treatment Plant (ETP), RO Plant and Mul+ Effect Evaporator
(MEE) plant.

The industry, for which we are working on ZLD, is basically a chemical industry discharging
around 370m3/day. By achieving ZLD, this huge discharge can be eliminated and daily
water consump+on of industry can be reduced significantly.

The effluent coming to ETP is having some significant effluent characteris+cs like widely
varying pH, high COD and Ammonical nitrogen. Ager primary, secondary and ter+ary
treatment, the effluent mee+ng discharge norms is send to FETP of NCTL for further
treatment and disposal.

In this project an a:empt would be made to op+mize the dose of chemicals added etc.
would also be done during the course of the project. Applicability and feasibility study of
different techniques like: ultra-filtra+on, reverse osmosis, different type of evaporator etc.
would also be done in later stage of project. Based on all studies and results of
experiments, methodology would be suggested to achieve ZLD in given industry.

Parameters like pH, COD, TDS, NH3-N are different different types of Effluent water,
Scrubber water has high TDS compared to Lab/ canteen, RO Reject and industrial effluent
(Table 2.3.). Table 2.3: Analysis of parameters
Sample pH COD(mg/L) TDS(mg/l) NH3-N

Scrubber water 8.88 6200 13000 45

Lab/canteen 5.02 88 980 45
RO Reject 6.12 32 4620 76
Industrial effluent 7 20 2000 nil

Page 9 38
 They units and values for Design parameter are as follows (Table 2.5.)

Table 2.4: Table showing of Various Design parameters

S. No Design Parameter Unit Value
1 Temperature oC 30-40
2 pH - 6.5-7.5

3 TDS Mg/L 6000

4 COD Mg/L 90
5 TSS Mg/L 100
6 BOD Mg/L 30
7 Ammonical Mg/L 50
Nitrogen
8 Turbidity NTU 20

ADVANTAGES/ BENEFITS:

• Water Conserva+on.
• ZLD systems employ the most advanced wastewater treatment technologies to purify
and recycle virtually all of the wastewater produced.
• Reduces the wastewater discharge i.e. reduces water pollu+on.
• Preferred op+on for industry where disposal of effluent is major bo:leneck.
• Prevents exploita+on of hydraulic capacity of disposal system Separa+on of salts /
residual solvents improve efficiency of ETP and CETP.
• Separated solids valuable by-product which helps in reducing the payback period.
• Mixed solvent separated in stripper can be reused or used as Co-processing.
• Ease in gedng environmental permissions.
• More focus on produc+on/ business rather than tracking ager regulatory authori+es.
• Reduc+on in water demand from the Industry frees up water for Agriculture and
Domes+c demands.[9]

Page 9 39
 CHAPTER – 3

PROCESS DESCRIPTION

Feed (RO reject / RO concentrate) is collected in a tank that is rejected as waste from the
RO process. The Feed is pumped to the preheater. The temperature of the feed is
increased from 35-55oC inside the preheater. Ager the feed a:aining the temperature of
55oC, the feed is fed to the heat exchanger. Inside the heat exchanger, the temperature of
the feed is increased to 80oC by using steam as a source of heat.

The feed is passed inside the tubes and the steam is allowed to pass through the shell
side. Ager a:aining the temperature of 80oC, the feed is fed to the crystallizer. Inside the
crystallizer, due to high temperature range, the liquid flashes to form a vapour.

The vapour and slurry get separated in the crystallizer. The vapour which forms in the
Crystallizer is sent to the vapour compressor. The par+al amount of slurry is sent to the
centrifuge decanter where the solid crystals separated from the liquid on high rota+onal
speed to separate components of different densi+es formed.

The remaining amount of the slurry which is in the crystallizer is sent back to the heat
exchanger using a circulator pump. The vapour which is sent to the vapour compressor is
again sent back to the heat exchanger by adding the low pressure steam to the vapour.
The vapour which is in the heat exchanger is used as input to the preheater for hea+ng
purposes.

Therefore, the complete separa+on of Solid materials from the liquid is achieved by
Thermal Evapora+on processes. No single drop of liquid is discharged as waste.

3.1. PREHEATER:

The wastewater flows from feed tank to preheater, where acid is added to
neutralize bicarbonate alkalinity proprietary an+scalants formula+ons are usually added
to avoid scaling in preheaters with calcium carbonate.

Page 9 40
 Closed feedwater heaters are shell and tube recuperators in which feedwater
temperature increases as the extracted steam condenses on the outside of the tubes
carrying feed water. The two streams can be at different pressures since the two streams
do not mix.

In an Ideal Regenera+ve Rankine Cycle with Closed feedwater steam from the boiler
expands in the turbine to an intermediate pressure. Then some of the steam is extracted
at this state and sent to the feedwater heater while the remaining steam in the turbine
con+nues to expand to condenser pressure. The extracted steam condenses in the closed
feedwater while hea+ng the feedwater from the pump. The heated feedwater is sent to
the boiler and condensate from feedwater heater is allowed to pass through a trap into a
low pressure heater or condenser. Another way of removing condensate from the closed
feedwater heater is to pump the condensate forward to higher pressure point in the
cycle.

The schema+c of closed feed water pre-heater is shown.

Page 9 41
 Fig 3.1: Schema+c diagram of a Feedwater Preheater

3.2. VERTICAL SHELL AND TUBE HEAT EXCHANGER

Heat Exchanger:

Shell and Tube Heat Exchangers are used for the majority of installa+ons. The hea+ng
medium is typically steam which is normally condensed on the outside of the tubes to
heat the liquor or slurry which flows inside the tubes.

VerAcal Shell and Tube Heat Exchanger:

A Ver+cal Shell and Tube Heat Exchanger in which the tubes extend through oversized
holes in a liquid distribu+on plate. Liquid flows through the holes and down each tube
exterior surface as a falling film. A spacer or clip, desirably of wire, is placed in each hole
around each tube to centre the tube so that the film has a uniform thickness.

The clip is self-locking and remains fixed securely in posi+on. Ver+cal Shell and Tube Heat
Exchanger is derived from its parent Shell and Tube Heat Exchanger and it is most
commonly used in all industries which involves higher-pressure and Higher Temperature
applica+ons.

Page 9 42
 Fig 3.2: Ver+cal Shell and Tube Heat Exchanger
A set of tubes is called the tube bundle and can be made up of several types of tubes:
plain, longitudinally finned, etc. Shell and tube heat exchanger and typically used for high-
pressure applica+ons (with pressures greater than 30 bar and temperatures greater than
260oC.) This is because the shell and tube heat exchangers are robust due to their shape.

SpecificaAon:

• Ver+cal Shell and Tube Heat Exchanger consists of a series of tubes. One setoff these
tubes contains the fluid that must be either heated or cooled.
• The second fluid runs over the tubes that are being heated or cooled so that it can be
either provide the heat or absorb the heat required.

ApplicaAons

• Ver+cal Shell and Tube Heat Exchanger is widely used in variety of applica+ons as a
cooling solu+on.
• The most common among them is for cooling of hydraulic fluid and oil in engines,
transmissions and hydraulic powder packs.

Page 9 43
• With the right combina+on of materials they can also be used to cool or heat other
mediums, such as swimming pool water or charge air.
• Ver+cal Shell and Tube Heat Exchanger also be used on fixed tube sheet heat
exchanger.

3.3. FORCED CIRCULATION CRYSTALLIZER

CrystallizaAon:

Crystalliza+on is the forma+on of solid par+cles within a homogeneous phase. It may

occur as the forma+on of solid par+cles in a vapour, as in snow; as solidifica+on from a
liquid melt, as in the manufacture of large single crystals; or as crystalliza+on from liquid
solu+on.

The concepts and principles described here equally apply to the crystalliza+on of a
dissolved solute from a saturated solu+on and to the crystalliza+on of part of the solvent
itself, as in freezing ice crystals from seawater or other dilute salt solu+on.

For applica+ons,

Where high rates of evapora+on are required,

Where there are scaling components, or

When crystalliza+on must be achieved in solu+ons with inverted solubility or rela+vely

high viscosity, the ‘forced circulaAon crystallizer’ is the best choice (figure 3.3.)

Page 9 44
 Fig 3.3: Schema+c diagram of Forced Circula+on Crystallizer

Forced CirculaAon Crystallizer:

The forced circula+on (“FC”) crystallizer is the most common type of crystallizer in the
industry. The average FC crystallizer evaporates solvent, thus increasing the super
satura+on in the process liquor, and causing crystalliza+on to occur. Most conven+onal FC
units operate under vacuum, or at slight super atmospheric pressure.

The FC consists of four basic components:

• The crystallizer vessel, which provides most of the volume dictated by the
residence +me requirements,
• The circula+ng pump, which provides the mixing energy, the heat exchanger, which
supplies energy to the crystallizer (in a typical evapora+ve crystalliza+on
opera+on), and
• The vacuum equipment, which handles the vapours generated in the crystallizer.

Page 9 45
 • Slurry from the crystallizer vessel is circulated, in plug flow fashion, through the
heat exchanger, and returned to the crystallizer vessel again, where its super
satura+on is relieved by deposi+on of material on the crystals present in the slurry.

The super satura+on is controlled so as to avoid spontaneous nuclea+on, by sufficient

circula+on capacity. The evaporated solvent is conducted to the vacuum system, where it
is condensed and removed. The FC crystallizer is used for general, simple crystalliza+on
opera+ons, where large crystal size is not a requirement.

The FC design aims to protect the crystal size from reduc+on from the crystallizer
environment, but has no features to aggressively increase the crystal size.

This type of unit, also known as the circula+ng magma crystallizer or the mixed
suspension mixed product removal (MSMPR) crystallizer, consists of a body sized for
vapour release with a liquid level high enough to enclose the growing crystals. Suc+on
from the lower por+on of the body passes through a circula+on pump and a heat
exchanger and returns to the body through a tangent or ver+cal inlet. The heat exchanger
is omi:ed when adiaba+c cooling is sufficient to produce a yield of crystals. The most
common use of this crystallizer is as an evapora+ve crystallizer with materials having
rela+vely flat or inverted solubility. It is also useful with compounds crystallized from
solu+ons with scaling components.

Controlled super saturaAon

When the heat exchanger is used, it is normally one or two pass and is designed for
rela+vely low temperature rises in the solu+on. This limits the super satura+on of scaling
components when hea+ng materials of inverted solubility.

Forced circula+on is the most widely prac+ced method of crystalliza+on. Forced

circula+on crystallizers are found in sizes ranging from two-foot diameter laboratory
models to over 40-foot diameter units for con+nuous processing. Per pound of product, it

Page 9 46
is ordinarily the most inexpensive type of equipment available, par+cularly when
substan+al amounts of evapora+on are required.

Forced circula+on crystallizers can be operated on a batch basis, but their most frequent
use is for con+nuous processing of such materials as sodium chloride, sodium sulphate,
sodium carbonate monohydrate, citric acid, monosodium glutamate, urea, and similar
crystalline materials.

3.4. VAPOUR RECOMPRESSION:

The energy in the vapour evolved from a boiling solu+on can be used to vaporise more
water. Provided there is a temperature drop for heat transfer in the desired direc+on. In a
mul+ple effect evaporator this temperature drop is created by progressively lowering the
boiling point of the solu+on in a series of evaporators through the use of lower absolute
pressure (and, therefore, the condensing temperature) of the evolved vapour by
mechanical or thermal recompression. The compressed vapour is then condensed in the
steam chest of the evaporator from which it came.

Mechanical recompression:

The principle of mechanical vapour recompression cold feed is preheater almost to its
boiling point by exchange with hot liquor and is pumped through a heater as in a
conven+onal forced-circula+on evaporator.

This vapour evolved, however, is not condensed; instead it is compressed to a somewhat

higher pressure by a posi+ve-displacement or centrifugal compressor and becomes the
“steam” which is fed to the heater. Since the satura+on temperature of the compressed
vapour is higher than the boiling point of the feed, heat flows from the vapour to the
solu+on, genera+ng more vapour. A small amount of makeup steam may be necessary.

The op+mum temperature drop for a typical system is about 5oc. The energy u+liza+on of
such a system is very good: Based on the steam equivalent of the power required to drive
the compressor, the economy corresponds to that of an evaporator containing 10 to 15
Page 9 47
effects. Important applica+ons of mechanical compression evapora+on include
produc+on of dis+lled water from seawater, evapora+on of black liquor in the paper
industry, evapora+on of salts having inverted solubility curve.

3.5. CIRCULATING PUMP:

A circulator pump or circulaAng pump is a specific type of pump used to circulate gases,
liquids, or slurries in a closed circuit. They are commonly found circula+ng water in a
hydronic hea+ng or cooling system. Because they only circulate liquid within a closed
circuit, they only need to overcome the fric+on of a piping system (as opposed to liging a
fluid from a point of lower poten+al energy to a point of higher poten+al energy).

Circulator pumps as used in hydronic systems are usually electrically powered centrifugal
pumps. As used in homes, they are ogen small, sealed, and rated at a frac+on of a
horsepower, but in commercial applica+ons they range in size up to many horsepower
and the electric motor are usually separated from the pump body by some form of
mechanical coupling.

The sealed units used in home applica+ons ogen have the motor rotor, pump impeller,
and support bearings combined and sealed within the water circuit. This avoids one of
the principal challenges faced by the larger, two-part pumps: maintaining a water-+ght
seal at the point where the pump drive shag enters the pump body.

Small- to medium-sized circulator pumps are usually supported en+rely by the pipe
flanges that join them to the rest of the hydronic plumbing. Large pumps are usually pad-
mounted.

Pumps that are used solely for closed hydronic systems can be made with cast iron
components as the water in the loop will either become de-oxygenated or be treated
with chemicals to inhibit corrosion. But pumps that have a steady stream of oxygenated,
potable water flowing through them must be made of more expensive materials such as
bronze.

Page 9 48
3.6. Centrifuge Decanter:

A centrifuge is a device that employs a high rota+onal speed to separate components of

different densi+es. This becomes relevant in the majority of industrial jobs where solids,
liquids and gases are merged into a single mixture and the separa+on of these different
phases is necessary.

A decanter centrifuge (also known as solid bowl centrifuge) separates con+nuously solid
materials from liquids in the slurry, and therefore plays an important role in the
wastewater treatment, chemical, oil, and food processing industries. There are several
factors that affect the performance of a decanter centrifuge, and some design heuris+cs
to be followed which are dependent upon given applica+ons (figure 3.4.)

Fig 3.4: Schema+c diagram of Centrifuge Decanter

OperaAng principle:

The opera+ng principle of a decanter centrifuge is based on separa+on via buoyancy.

Naturally, a component with a higher density would fall to the bo:om of a mixture, while
the less dense component would be suspended above it.

A decanter centrifuge increases the rate of se:ling through the use of con+nuous
rota+on, producing a gravita+onal force equivalent to between 1000 and 4000 G's.
Page 9 49
This reduces the se:ling +me of the components by a large magnitude, whereby mixtures
previously having to take hours to se:le can be se:led in a ma:er of seconds using a
decanter centrifuge.

This form of separa+on enables more rapid and controllable results.

Working:

The feed product is pumped into the decanter centrifuge through the inlet. Feed goes into
a horizontal bowl, which rotates.

The bowl is composed of a cylindrical part and a conical part.

The separa+on takes place in the cylindrical part of the bowl.

The fast rota+on generates centrifugal forces up to 4000 x g.

Under these forces, the solid par+cles with higher density are collected and compacted
on the wall of the bowl.

A scroll (also screw or screw conveyor) rotates inside the bowl at a slightly different
speed.

This speed difference is called the differen+al speed.

This way the scroll is transpor+ng the se:led par+cles along the cylindrical part of the
bowl and up to the end conical part of the bowl.

At the smallest end of the conical part of the bowl, the dewatered solids leave the bowl
via discharge opening.

The clarified liquid leaves through a paring disc (internal centripetal pump).

Page 9 50
FLOWSHEET FOR “THE REMOVAL OF INORGANIC SALTS FROM RO CONCENTRATE
BY USING THERMAL
EVAPORATION TECHNOLOGIES”.

Page 9 51
 CHAPTER – 4

MASS BALANCE & ENERGY BALANCE

MASS BALANCE:

A balance on a conserved quan+ty (total mass, mass of a par+cular species, energy, and
momentum) in a system (a single process unit, a collec+on of units, or an en+re process)
may be wri:en in the following general way;

[AccumulaAon = input – output + generaAon - ConsumpAon]

For con+nuous processes at steady state, the accumula+on term in the general balance
equa+on equals zero, and the equa+on simplifies to

Input + generaAon = output + consumpAon

If the balance is on a non reac+ve species or on total mass, the genera+on and the
consump+on term equal zero and the equa+on reduces to

Input = output

Since, there is no reac+on taking place. So, we must equate the Accumula+on, Genera+on &
Consump+on to 0 (Zero).

Overall Mass balance equaAon:

Basis: Considering, the given opera+on is 1 hour basis

Here, the feed is RO reject which is 15,425kg/hr.

Assuming TDS = 48,000mg/l

[Source: JSW industry]

B. Page 9 42
 Feed (RO

,425kg/

Solids

RO Reject = Mother Liquor + Solids

15,425 kg/hr = Mother Liquor + Solids

We know that, if TDS is known from a Chemical analysis of forma+on of Water, then the

formula below can be used to es+mate forma+on water density (ρw)

𝜌𝑤 = 1 + TDS * 0.695 * 10-6 g/cm3 è (1)

For the feed TDS = 48,000 mg/l

To calculate density of water (ρw) in the feed:-

𝜌𝑤 = 1 + 48,000 * 0.695 * 10-6 g/cm3

= 1.03336 g/cm3

= 1033.366 kg/m3

Density of Water in the input feed = 1033.366 kg/m3

Water rate in the feed = 15,425 * (1000/1033.36)

= 14927.03414 kg/hr of water

Solids rate contain in input feed = 15425 – 14927.03414

= 497.9658 kg/hr è (2)

Mass balance for Heat Exchanger:

AssumpAons:

1. Assuming no accumula+on, genera+on and consump+on.

2. Circula+on rate = 2400kg/hr.

B. Page 9 43
 Vapour + Low Pressure Steam

HEAT Crystallizer
Feed from Pre-Heater + PreEXCHANGER -Heater
(Par+ally Condensed Vapour
Circula+on + Low Pressure
Steam)

Vapour + Low Pressure Steam = Par+ally Condensed Vapour + Low Pressure Steam
Output = Feed from Pre-Heater + Circula+on
= 15,425 + 2400

= 17,825 kg/hr
Feed rate of Crystallizer = 17,825 kg/hr

Mass balance for Crystallizer:

AssumpAon: 80% of feed is converted to vapour and remaining is residue.

Here, the feed rate of crystallizer is 17,825kg/hr.

Vapour to Vapour Compressor

Feed input
CRYSTALLIZER

Slurry Feed input =

Vapour + Slurry

80% of feed = 0.80 * 17,825

= 14,340 kg/hr

B. Page 9 44
 So, slurry leaving from the crystallizer = 17,825 – 14,340

= 3485 kg/hr

CirculaAon pump:

Slurry from Crystallizer can be par+ally separated and passed into decanter and
remaining can be recirculated to the Heat Exchanger.

Let, W be the kg/hr of slurry to the decanter.

Slurry from Crystallizer = Decanter + Re-circula+ng back to Heat Exchanger

3485 kg/hr = W + 2400

W = 1085 kg/hr

; . 1085 kg/hr to Decanter

Water contents in 1085 kg/hr is,

= 1085 – 497.9658

= 587.0342 kg/hr

For water sa+sfactory let us take the TDS in Mother Liquor is 500mg/L

Now, density of Mother Liquor

𝜌𝑚 = 1 + (TDS * 0.695*10-6) g/cm3

= 1 + (500*0.695*10-6)

= 1000.3475 kg/m3

1000
Pure water in the Mother Liquor = 587.0342 *

= 586.8317 kg

Solids content in Mother Liquor = 587.0342 – 586.0317

B. Page 9 45
 = 0.2024 kg

Energy Balance:

ASSUMPTIONS:

• Con+nuous, steady flow, Steady state opera+ons.

• Perfect mixing of the magma.
• No classifica+on of crystals.
• Uniform degree of super satura+on for the magma.
• Crystal growth is independent of crystal size.
• No classifica+on of crystals.
• No crystals in the feed.
• No crystal breakage.
• Uniform temperature.
• Mother liquor in product magma in equilibrium with the crystals.
• Nuclea+on rate is constant, uniform, and due to secondary nuclea+on by crystal
contact.
• All crystals have the same shape.

Energy requirement for heat exchanger:

The general energy balance equa+on for the heat exchanger is,

Q = m*Cp*ΔT + mv*λv

AssumpAons:

Ini+ally feed heated to 55oC in the preheater

Data:

m = Feed rate = 17,825 kg/hr

𝑚𝑣 = Vapour rate = 14340 kg/hr

Cp = specific heat = 4.181 J/kg K

B. Page 9 46
 ΔT = Temperature difference = 25oC

λ = Latent heat of vapour = 2305 kJ/kg

Energy required for the Heat Exchanger to raise the Temperature to 80oC

Q = m*Cp*ΔT + mv*λv

Q = (17,825*4.181*25) + (2305*14,340)

= 3,49,16,858.13 kJ/hr

(For Vapour heat required from 80-90oC)

Energy requirement for vapour:

(Heat released from 80-90oC)

Q = m*Cp*ΔT

Cp = specific heat of Vapour = 1.9654 kJ/kg

ΔT = 90oC - 80oC

= 10oC

m = 14,890 kg/hr

Q = 14,890 * 1.9654 * 10

= 2,92,648.06 kg/h

By Latent heat,

Q = mv*λv

= 14,890 * 2305

= 3,43,21,450 kg/hr

Total heat required for the vapour,

B. Page 9 47
 = 3,43,21,450 + 2,92,684.06

= 3,46,14,098.06 kJ/h

Energy difference = 3,49,16,858.13 – 3,46,14,098

= 3,02,760.065

Now,

ΔT = Q/ (m*Cp)

= 302760.065/(14,890*4.181)

ΔT = 4.8632oC

⇨ T1 – T2 = 4.8632

⇨ T2 = T1 – 4.8632oC

⇨ T2 = 80oC – 4.8632oC

⇨ T2 = 75.1368oC

Energy requirement for Preheater

Ini+al Temperature of feed Ti = 35oC

Cp = Specific heat = 40181 kJ/kg

Final Temperature of feed, To = 55oC

Heat required for hea+ng = m*Cp*ΔT

= 15,425 * 4.181 * 20

= 12,89,838.5 kJ/kg

T2 = Ini+al Temperature of Steam

T3 = Final Temperature of Steam leaving Preheater

B. Page 9 48
 ΔT =

= 20.7186oC

T2 - T3 = 20.7186oC

⇨ T3 = T2 – 20.7186oC
⇨ 75.1365oC – 20.7186oC
⇨ 54.4181oC , T3 = 54.4181oC
CHAPTER – 5

DESIGN

CRYSTALLIZER GEOMETRY:

To prevent excessive entrainment of small brine droplets, the authors

suggested that the dynamic pressure of the released vapour should not exceed a certain
threshold value i.e.,

½ * ρv * uv2 ≤ 1.75

N/m2

Data:

Opera+ng pressure in crystallizer, 𝜌𝑣 = 47.5 kN/m2

Vapour rate, (V) = 14340 kg/hr

Density of Vapour at 80oC, 𝜌𝑣 = 0.309 kg/m3

Reynolds number, Re = 5*106

B. Page 9 49
 Specific heat of liquid (Cp) = 4.181 kJ/kg

Viscosity of the slurry, 𝜇𝑠= 23*10-4kg/m-s

Temperature of liquid entering Crystallizer, TΠ= 80oC

In order to sa+sfy this criterion, the diameter of the cylindrical part should be
constrained by

For the present case, the diameter of the evaporator body is given by

0.309∗14340
v≥ √
0.309 0.5 ∗600
D

= 4.488m
The height of vapour space is recommended to be 0.75*Dv. In this design, a
double radial inlet is chosen and slurry is recycled to the heater through a single bo:om
outlet.

To sa+sfy the flow similarity criterion Newman and Bennet suggested that Reynolds
number based on inlet velocity and evaporator body diameter should be in the region of
(5~10)*106.

Assuming Re = 5*106 for present case.

𝑣𝑖 = Re * 𝜇𝑠1 𝜇𝑠1= 23*10-4 kg/m3

ρsl * Dv 𝜌𝑠1 = 1848.2739 kg/m3

= 5*106*23*10-4
B. Page 9 50
 1848.27*1.4

𝑣𝑖 = 4.18 m/s

For Circula+ng Volumetric flowrate

Q=

𝑞𝑖= 34916858.13 kJ/hr, ΔT = 4.8632oC

Q=

= 929.78m3/hr

For total circula+ng flowrate,

Q = 929.78m3/hr, the crystallizer inlet diameter

Di

= 0.89838m

In order to maintain equal veloci+es in inlets and outlets

Do

2
√ 0.89838 2

B. Page 9 51
 = 1.28 m

The inlet temperature of brine at the entry of evaporator body = 80oC

Corresponding Vapour Pressure = 55 kN/m2

Opera+ng pressure in crystallizer, ρv = 47.5 kN/m2

Pressure difference, ΔP = 55 – 47.5

= 7.5kN/m2

Slurry Density, ρsl = 1848.27 kg/m3,

The required hydrosta+c head

is ΔP = h*ρ*g

𝛥 𝑃
h=

h=

= 0.494 m

Total minimum height required for cylindrical part of body is

Hc, m = h + Di + ¾ Dv + Addi+onal height

= 0.494 + 0.89838 + (0.75*4.488) + 0.5

= 5.25838 m

‘Vm’ be the volume of external loop and ‘Vcone’ be the Volume of cone, minimum liquor
hold up required then is ‘Vl’ given by,

𝑣𝑙= π/4 * Dv2 * (h + Di + 0.5) + Vcone + Vm

B. Page 9 52
 = π/4 * 4.4882 * (0.494 + 0.89838 + 0.5) + 40 + 40

= (3.14 * 20.14214 * 1.89238) + 80

= 197.8152 m3

~= 200 m3

CHAPTER – 6

SALT EXTRACTION TECHNOLOGIES

To date, several technologies can be used to extract valuable domes+c and commercial
salts and minerals from saline water. Based on the type of separa+on process, the
technologies are classified into four categories:

(a)Thermal processes: These are phase change processes involving use of thermal energy
to evaporate feed water to generate steam which is then condensed, a process known as
dis+lla+on.
Alterna+vely, saline water is frozen followed by the separa+on of pure ice and salts.
Dis+lla+on can use any hea+ng source such as fossil fuels, Nuclear energy with solar
energy being a lowtech op+on.
Applica+on of this technique includes,
Solar Dis+lla+on (SD), Mul+-Effect Dis+lla+on (MED) or Mul+ple Effect Evapora+on (MEE),
Mul+
Stage Flash Dis+lla+on (MSF), Mechanical Vapour Compression (MVC), Eutec+c Freezing
Crystalliza+on (EFC) and open pan boilers.
(b)Membrane processes: They involve separa+on of dissolved salts from the feed water
by mechanical or chemical/electrical means using a selec+ve membrane barrier between
the feed water and product. This principle is applied in Reverse Osmosis (RO) and
Electrodialysis/Electrodialysis Reversal (ED/EDR). These processes do not lead to a phase
change.

B. Page 9 53
 (c)Chemical change processes: These involve applica+on of chemical techniques to
extract salts from feed water. The principle is applied in the Ion Exchange, Reac+ve
precipita+on and Calcina+ons processes.
(d)Hybrid processes: They involve combina+on of the above processes in a single unit or
in sequen+al unit or in sequen+al steps. Examples include: Membrane Dis+lla+on (MD),
Membrane Crystalliza+on (MC), and RO with MSF or MED.
6.1. Thermal processes:

These are phase change processes involving use of thermal energy to evaporate feed
water to generate steam which is then condensed, a process known as dis+lla+on.
Alterna+vely, saline water is frozen followed by the separa+on of pure ice and salts.
Dis+lla+on can use any hea+ng source such as fossil fuels, nuclear energy with solar
energy being a low-tech op+on.

Applica+on of this technique includes

solar dis+lla+on (SD), mul+-effect dis+lla+on (MED) or mul+ple effect evapora+on (MEE),
mul+-stage flash dis+lla+on (MSF), mechanical vapour compression (MVC), eutec+c
freezing crystalliza+on (EFC) and open pan boilers.

Thermal Based Technologies:

Thermal based technologies use heat to separate water from the concentrate
stream. Some technologies also provide addi+onal recovery, such as brine concentrators

and crystallizers. With other technologies (WAIV, solar ponds, spray dryers, EVRAS), the

water is not capable and therefore does not increase the system recovery. I) Brine
Concentrators:

Brine concentrators consist of ver+cal tube bundles with brine evapora+ng from a
thin film on the inside of the tubes. The brine absorbs heat from considering water
vapour on the outside of the tubes and the latent heat of vaporiza+on transfers from the

B. Page 9 54
 water vapour through the tube wall to the thin brine film on the inside of the tube
(Mickley, 2006).

Following heat-exchange, this stream can be used further by returning it upstream to the
membrane treatment process. Brine concentrators are ogen+mes designed to operate in
a slurry mode where calcium sulphate is added to the recycle to provide nuclea+on sites
for the precipita+on of scale to prevent scaling of heat transfer surface.

Some important issues associated with brine concentrator are as follows (Mickley, 2006):

• Brine concentrators are typically capable of concentra+ng brine by as much as 40

to one without any scaling problems, where the waste stream from the
concentrator is typically 2-10% of the feed water flow.
• The TDS of the reject stream can be as high as 2,50,000 mg/L.
• Concentrators can produce high quality water (TDS less than 10 mg/L).
• Typical brine concentrator capacity ranges from 10 to 700 gpm.
• There are about 75 brine concentrators in opera+on worldwide and approximately
10 of these systems are used for RO concentrate management in industrial plants
(Mickley, 2006).
• Brine concentrator recovery depends on the feed water quality, but typically ranges
from 90-98% of the feed concentrate stream. Brine concentrators are energy-
intensive, requiring approximately 70-100 kWh of energy per 1,000 gallons
concentrate treated.

B. Page 9 55
 Fig 6.1: Schema+c diagram of ZLD system including Brine Concentrator and

Crystallizer II. Brine crystallizers:

Brine crystallizers are typically ver+cal cylindrical vessels with heat input from vapour
compressors or an available stream supply. Feed brine is mixed with re-circula+ng brine
and pumped to a shell-and-tube heat exchanger where the brine is heated by vapour
from the compressor, and as water evaporates, salts precipitate out of the concentrated
solu+on. Brine crystallizers are ogen+mes employed with brine concentrators (figure 6.2.)

Crystallizers typically require approximately 200-250 kWh of energy per 1,000 gal treated
brine, which is approximately three +mes the energy required by brine concentrators
(Mickley et al., 2006).

B. Page 9 56
 Fig 6.2: Brine

Crystallizer

Fig 6.3: Schema+c of Zero Liquid Discharge system using Brine Concentrator, Brine
Crystallizer and Evapora+on pond and recovery system

III. Salinity Gradient Solar Pond – Brine Concentrator and Recovery System:

Salinity gradient solar ponds (SGSP) allow for the storage of brine in a manner that also
provides storage for waste heat. The waste heat can then be used to provide energy for
various applica+ons, including opera+on of the desalina+on systems. An example of SGSP
coupled with desalina+on system for ZLD applica+on.

The brine from the RO system is treated using a second stage thermal desalina+on
process. The brine from the thermal desalina+on system is then fed into the third stage
brine concentrator and recovery system (BCRS). The salt slurry from the BCRS is then fed
to SGSP.

The hot brine from the ponds can use a thermal source to evaporate the water to be
desalted at low pressure in an evaporator (figure 6.4.) (Kalagirou, 2005).

B. Page 9 57
 Fig 6.4: Schema+c of Zero Liquid Discharge system using salinity gradient solar

pond, Brine Concentrator and recovery system

IV Spray Dryers:

Spray dryers are comprised of a ver+cal drying chamber and a centrifugal atomizer
through which the concentrate slurry is sprayed (Mackey and Sea cord, 2008). The dry
solids are blown by hot air through a bag filter, where they are collected.

The moist air is exhausted out the top of the bag and the solids are collected in a hopper
below. Associated equipment for the spray dryer include conveyance pipe to the dryer, an
atomizer, spray drying chamber, a bag filter and a solids storage chamber (Mackey and
Sea cord, 2008).

Spray dryers are typically more economical to operate than brine crystallizers at flow rates
below 10 gpm (Mickley, 2006).

Advantages of a spray dryer include:

· Concentra+on of slurries to solids waste,

· Feasible in areas where other low cost op+ons are not available in a small
footprint.

Disadvantages of a spray dryer:

For concentrate management are the high capital costs and high
energy requirements (>200 kWh/1000 gal) (Mackey and Sea cord, 2008).
B. Page 9 58
 v) EvaporaAve ReducAon and SolidificaAon (EVRAS):

The EVRAS process is an evapora+ve system similar to a cooling tower that relies on water
temperature, surface area and airflow (RPSEA, 2009). The EVRAS is a patented technology
provided by Intevras Technologies, LLC, a Texas based privately held company. A
schema+c of the technology is available from Intevras, 2011).

The technology is used for brine treatment and u+lizes low-grade waste heat to
concentrate and/or crystallize large volume of brine streams. EVRAS is an evapora+ve
system and fresh water is not recovered.

Without waste heat available onsite, the process is energy intensive. The EVRAS system
has primarily been used in industrial applica+ons with limited applica+ons in the
municipal sector. The advantages of the system include (RPSEA, 2009):

• Use of low temperature waste heat

• TDS insensi+ve
• Corrosion resistant and minimal scaling problems
• Simplicity in opera+on and minimal maintenance
• No blow-down or discharge

CHAPTER – 7

ZLD TECHNOLOGIES

Zero Liquid Discharge refers to processes the fully removes water from the Concentrate
Stream (in other words, no liquid is leg in the discharge). The end product of a ZLD
system is a solid residue of precipitate salts that needs to be reused or transformed to a
designated solid waste disposal facility for incinera+on/landfill.

ZLD systems range from Simple to Highly complex system depending on the complexi+es
in Wastewater streams. Ul+mate aim of ZLD is to recover useful products, and salts from
rejects, apart from recovery of maximum water recycle.

B. Page 9 59
 Following are the major ZLD technologies that are used in various combina+ons as per
the requirements.

• Solvent Extrac+on/Stripper
• Membrane Bio Reactor Technology (MBR)
• Ultra Filtra+on (UF)/Reverse Osmosis (RO)
• Evapora+on Technologies-Mul+ Effect Evaporators (MEE)
Mechanical Vacuum Re-Compressor (MVR)
• Agitated Thin Film Dryer (ATFD)
• Crystalliza+on
• Incinerator

7.1.EVAPORATION TECHNOLOGIES:

The ul+mate objec+ve of ZLD is not discharging waste water outside the industry. This
objec+ve is achieved by Evapora+on or Crystalliza+on of rejects from previous
treatments. During these processes (UF & RO), the Condensate (Treated Water) is
recovered while contaminated elements are separated as solid waste with some moisture
in it.

Typically, the effluent is a saltry solu+on and the Thermal separa+on is the final step of
ZLD.

Evapora+on of Reject water is most commonly used treatment for reduc+on of waste
volume, recovery of salts and to recycle the condensate in process. Evapora+on plants
used are Thermal separa+on technology, for the Concentra+on or opera+on of Liquid
solu+ons, Suspensions and Emulsions.

Types:

I. Falling film Evaporator:

B. Page 9 60
 This technology is par+cularly suited for energy-saving. It only requires a very small
opera+ng temperature and thus allows it to be easily controlled; it is fast to start and shut
down due to a minimal liquid hold-up. Falling film technology is the right solu+on for
streams which are viscous in nature and contain small concentra+ons of suspended solids

A Falling Film Evaporator can be used as a pre-concentrator in a combined Mul+ple-Effect

plant. It has the capacity to treat streams with small to large flow rates. Unlike rising film,
Liquid is fed at the top of long tubes and allowed to fall down the film walls. Evapora+on
occurs on the surface of the highly turbulent film and not on the tube surface. This
requires that temperature differences be rela+vely low

Many +mes rising film and Falling Film Evaporators are combined into single unit. When
high ra+o of Evapora+on to feed is required and the Concentrate liquid is viscous. A Tube
bundle is divided into two sec+ons with the first sec+on func+oning as a rising film
evaporator and the second sec+on serving as a falling film evaporator (figure 7.1.).

Fig 7.1: Schema+c diagram of Falling Film Evaporator

B. Page 9 61
 II. Forced CirculaAon Crystallizer:

The forced circula+on Crystallizer is used for processing liquors which are suscep+ble to
scaling or crystallizing. Liquid is circulated at a high rate through the HE, boiling being
prevented within the unit by virtue of a hydrosta+c head maintained above the top plate.

As the liquid enters the separator where the absolute pressure is slightly less than in the
tube bundle, the liquid flashes to form a vapour.(figure 7.2.)

Table 7.2: Schema+c flow diagram of Forced Circula+on Crystallizer

B. Page 9 62
 III. Natural CirculaAon:

Evapora+on by natural circula+on is achieved through the use of a short tube bundle or
by having an external shell and tube heater outside of a main vessel. The external heater
has the advantage that its size is not dependent upon the size or shape of the vessel itself.
As a result, larger evapora+on capaci+es can be obtained. The most common applica+on
for this type of units is as a re-boiler at the base as a desalina+on column (figure 7.3.).

Fig 7.3: Diagram showing of Natural Circula+on

IV. Plate Type Evaporator:

Principally, plate evaporators are similar to falling film& forced recircula+on tubular
evaporators. The plate evaporator offers full accessibility to the heat transfer surfaces. It
also provided flexible capacity merely by adding more plant units. Because of shorter

B. Page 9 63
 product residence +me, superior quality concentate is obtained. It is a more compact
design with low headroom requirements, and low installa+on cost
(figure 7.4.).

Fig 7.4: Schema+c diagram of Plate Type Evaporator

Table 7.1: Representa+on of wide range applica+ons of different ZLD Technologies in
various fields &
Opera+ons, Recovery
S. Technology Applica+ons
No.
1 Forced Circula+on • Suitable for Evapora+on applica+ons
containing high levels of hardness, silica,
suspended solids & crystalline slurries.
• Salt recoveries like NaCl, Na2SO4,
NH4Cl,
(NH4)2SO4, ZnSO4, K2SO4, KCl & CaCl2, etc.,
2 Falling film • Suitable for Liquors, feeds with low
hardness and non- Crystalline concentrates
with low viscosi+es.
• Useful for Concentra+ng Milk, fruit juices, if
hardness is <150ppm.

B. Page 9 64
 3 Natural Circula+on • Suitable for concentra+on of viscous Liquids
below satura+on without hardness.
• Solids Slurry with high Viscous.
• Liquid, where solids will se:le down and
clear liquid is circulated.
4 Plate Type • Applica+on is same as Forced Circula+on
and
Falling film designs.
• Used for low level installa+ons.

7.2.EXTRACTION OF POTENTIALLY PROFITABLE MATERIAL FROM RO REJECTS:

Magnesium:

The main unit processes used for the extrac+on of magnesium is evapora+on cum
crystalliza+on, precipita+on, and ion-exchange. Ohya et al. proposed a series of
integrated processes (crystalliza+on, electro-dialysis and Ion-exchange) to recover salts of
calcium carbonate, sodium chloride and magnesium sulphate from RO reject. Drioli et al.
iden+fied a process of membrane crystalliza+on/dis+lla+on to separate out various
inorganic salts from reject streams from an integrated Nano Filtra+on (NF)/RO process. In
Russia, a large scale extrac+on plant is also being operated for the recovery of magnesium
from seawater using ion-exchange, and extrac+on of magnesium from RO reject from
seawater desalina+on system.

Potassium:

Worldwide potash consump+on is increasing every year approximately at a rate of 3%

due to popula+on growth and other increased demand for fer+lizers. The main source of
potash produc+on is done by conven+onal shag mining or deep-well solu+on mining
process techniques.

Currently, potassium is being produced from seawater as a by product from solar salt
evapora+on. As an alterna+ve to solar evapora+on/precipita+on, several researchers

B. Page 9 65
 have suggested that, potassium could be produced from RO reject using an evapora+on/
crystalliza+on process. The extrac+on of potassium is done using natural zeolite
(clinop+lolites) ion-exchange materials which has high exchange capacity for potassium
through a two-step dual-temperature process.

Sodium:

The produc+on of sodium compounds from desalina+on reject is obtained through

evapora+on technologies, followed by crystalliza+on, membrane crystalliza+on, electro
dialysis followed by mul+ple effect dis+lla+on (ED/MED), and evapora+on ponds.
Membrane crystalliza+on (MC) is being prac+ced to produce rela+vely pure salt crystals
from a synthe+c NF reject solu+on having calcium and magnesium.

Process is developed by Davis on electro dialysis metathesis which has integrated

evaporator unit to separate out sodium sulphate and sodium chloride. The SAL-PROC
process (Geo-Processors USA Inc) is being used to produce sodium chloride, calcium
sulphate, calcium chloride, and magnesium hydroxide from concentrated solu+ons
including brackish water reverse osmosis (BWRO) and seawater reverse osmosis (SWRO)
concentrate.

CHAPTER – 8

CONCLUSIONS

• Using the data in the literature survey the theore+cal model was carried and we
select our process accordingly.
• Circula+ng slurry to the inlet feed act as a seeds, which increases the efficient
forma+on of salts.
• Based on process descrip+on the flow chart of the process was developed.
• Using mass balance and energy balance, various designs of equipments can be
made in future.
• Using the design informa+on and process economics calcula+ons, a plant can be
designed.

B. Page 9 66
 • Computa+onal studies have been carried out and the design, Volume of the
crystallizer have been es+mated

Volume of the Crystallizer 𝑣𝑙 is 200 m3.

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