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 certify that the project report entitled

REMOVAL OF INORGANIC SALTS FROM RO CONCENTRATE BY
USING THERMAL EVAPORATION TECHNOLOGIES
is the bonafide work done and submitted 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 partial 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 satisfaction and euphoria that accompanies the successful completion of any task
would be incomplete without the mention 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, Tirupati, 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 facilities for completion of our project.

It is a pleasure to express our deep sense of gratitude and indebtedness to the entire
faculty, Department of Chemical Engineering, Sri Venkateswara University College of
Engineering, Tirupati, for their support, who have directly or indirectly had a hand in the
successful completion 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 completion of our project work.

Project Members

Byreddy Amulya (11701010)

Challa Venkataramana (11701013)

Maddela Hemanth Kumar (11701032)

Putikireddy Preethi (11701064)

 DECLARATION
We do hereby declare that this study work, entitled “REMOVAL OF INORGANIC SALTS FROM
RO CONCENTRATE BY USING THERMAL EVAPORATION TECHNOLOGIES”, submitted to the
Department of Chemical Engineering, Sri Venkateswara University College of Engineering,
Tirupati, in partial fulfilment for the award of the degree of Bachelor of Technology in
Chemical Engineering, Sri Venkateswara University College of Engineering, Tirupati, 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 submitted , in part or full, for
any other degree or diploma of this or any other university. The extent of information,
incorporated in this thesis, derived from the existing literature is duly acknowledged.

(Byreddy Amulya)

(Putikireddy Preethi)

(Challa

Venkataramana) (Maddela

Hemanth Kumar)
 ABSTRACT
In industrial settings, such as pharma, pulp & paper, tanneries, textile dyeing,
chemicals, power plants, etc., generate wastewater with high salinity/TDS. RO is often
used to remove Total Dissolved Solids (TDS) from industrial wastewater or treated
industrial wastewater and the yield permeates with relatively low TDS Concentrations.
RO Reject water is the main problem because this rejection is released without any
treatment to the natural water bodies. The Reject/Concentrate is more than three times
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 solution to
eliminate environmental damage.

Membrane technologies became impractical at higher concentrations of TDS, for

that ZLD is one strategy to address this challenge. The major ZLD technologies that are
used in various combinations as per the requirements are Solvent recovery, Selective
crystallization method, Chemical precipitation, Electrodialysis, Thermal Evaporation
techniques. Among these, the Thermal evaporation technique has higher efficiency of
separation. This operation often involves the concentration 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 solution to avoid scaling of Heat transfer surfaces. The equipment
technologies for evaporation includes Falling film, Natural circulation, Rising film and
Forced Circulation Evaporators.

Typical RO concentrate/RO reject TDS concentrations are often in the range of

30000-50000 mg/L. By using thermal evaporation techniques reduced the amount of TDS
range from 400-500mg/L and separation of solids is done to attain ZLD.

The ZLD processing schemes, including thermal evaporation process was

discussed with their limitations. The global applications of ZLD systems was studied
Page 5
 Keywords- Treated industrial wastewater, Thermal Evaporation 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 Concentrations 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. Crystallization 15
II. Purity of Product 16
1.5.ZERO LIQUID DISCHARGE 17
I. Zero Liquid Discharge 18

Page 6
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 Evaporative Reduction and Solidification 57
.
CHAPTER 7
ZLD TECHNOLOGIES 59

Page 7
 7.1 EVAPORATION TECHNOLOGIES
I. Falling film Evaporator 60
II. Forced Circulation Evaporator/Crystallizer 61
III. Natural Circulation 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. Description Page No.

1.1 Typical Desalinity Membranes Design Parameters by Water 14
Source
(AWWA, 2004)
1.2 Typical Conc. TDS by Water Treatment 15
process
2.1 Treatment processes aimed at Zero Liquid 25
Discharge
2.2 Electric power Consumption in ZLD Encompassing the 27
Thermal
Evaporator
2.3 Analysis of Parameters 29
2.4 Table Showing of Various Design 29
Parameters
7.1 Representation of Wide Range Applications of Different ZLD 63
Technologies in Various Fields and Operations, Recovery
Page 8
 LIST
OF FIGURES

Fig No. Description Page No.

1.1 Distribution of Water on Earth 10
1.2 No. of ZLD Installations Over the 18
Years
2.1 Pictorial Representations of a Zero Liquid Discharge 19
Treatment
Plant
2.2 Schematic Diagram of a Thermal ZLD 23
System
2.3 The Hierarchical Procedure of ZLD 32
3.1 Schematic Diagram of a Feedwater 33
Preheater
3.2 Vertical Shell and Tube Heat 35
Exchanger
3.3 Schematic Diagram of a Forced Circulation 38
Crystallizer
3.4 Schematic Diagram of Centrifuge 55
Decanter
6.1 Schematic Diagram of ZLD System 55
Including Brine
Concentrator and
Brine Crystallizer
6.2 Brine Crystallizer 56
6.3 Schematic Diagram of ZLD System Including Brine 57
Concentrator and Brine Crystallizer, Evaporation Pond
and Recovery System
6.4 Schematic Diagram of ZLD System Using Salinity 60

Page 9
 Gradient Solar Pond, Brine Concentrator
and Recovery System
7.1 Schematic Diagram of Falling Film 61
Evaporator
7.2 Schematic Flow Diagram of Forced Circulation 62
Crystallizer
7.3 Natural Circulation 63
7.4 Schematic Diagram of Plate Type 64
Evaporator

LIST OF
ABBREVIATIONS

RO Reverse Osmosis
UF Ultra Filtration
NF Nano Filtration
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 Distillation
SD Solar Distillation
FC Forced Crystallization
ZLD Zero Liquid Discharge
AWWA American Water Works Association
CSD Crystal Size Distribution

Page 10
 GLOSSARY

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

used for food production. This word comes from ‘potare’ meaning ‘TO DRINK’.

RO CONCENTRATE: RO CONCENTRATE includes elevated concentrations of contaminants

that are removed during the treatment of brackish water for potable water use.
Contaminants include salts, metals, and nutrients typically at concentrations 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 objective 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 heating 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 separation. These

are important piece of chemical processing equipment because they are capable of
generating high purity products with relatively low energy inputs.

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

Circulation pump: A Circulation pump or is a specific type of device used to circulate

gases, liquids slurries in a closed circuit.

Page 11
Slurry pump: A slurry pump is a device designed for pumping liquid containing solid
particles. Both centrifugal and positive displacements pumps can be used for slurries.

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

Mother liquor: A Mother liquor is the part of the solution which is left over after
crystallization. It is encountered in chemical processes including sugar refining. It is the
liquid obtained by filtering the crystals by filtration.

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 left after the
filtration of colloidal and suspended solids and then the evaporation of a known volume
of water. TDS is reported as ppm or mg/L.

Turbidity: Turbidity is a suspension of fine colloidal particles that do not readily settle out
of solution and can result in “cloudiness”. Turbidity is determined by a Nephelometer
that measures the relative amount of light able to pass through the solution.

ppm (parts per million): A method for reporting the concentration 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 % solution is equal to
10,000 ppm. One ppm is equal to 1,000 ppb.

Page 12
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, printing 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.

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 matter, 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
impurities 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 settles out in the wastewater
treatment process, sometimes 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 evaporation. The total weight concerns both dissolved and suspended
organic and inorganic matter. All the solids in wastewater or sewage water including
suspended solids and filterable solids.

Page 13
Toxic water pollutants: Compounds that are not naturally found in the water at given
concentrations and that cause death, disease or birth defects in organisms that ingest or
absorb them.

Ultraviolet Disinfection (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 matter.

CHAPTER – 1

INTRODUCTION

The lack of potable water and the depletion of raw materials are two major issues that
have emerged in recent decades due to the rapid increase in the world's population and
improvements in standards of living. Membrane technology plays a major role in
addressing the above issues. Specific additional treatments are required for improving
water recovery strategies, operational 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 noting 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 Antarctica.

Page 14
 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 distribution 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.

Fig.1.1: Distribution of water on Earth

Nowadays, this natural process is inadequate due to human activities, and

specifically because of the thoughtless wasting of water and discharge of various
pollutants into the aquatic environment.

However, abundant supplies of fresh water are essential to industrial development.

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

Page 15
 Water is a vital substance for supporting 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, domestic use, etc. Fresh water is used in agriculture, construction, Transport, the
Chemical industry, and numerous other activities of human beings.

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

freshwater resources is depleting 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 Population) live on this planet with water shortages. To
overcome this challenge, desalination of seawater and brackish water using high-
pressure membranes including reverse osmosis (RO) and nanofiltration (NF) technology,
has become an excellent solution in recent years since they produce outstanding water
quality.

These membranes have been demonstrated to be highly effective for rejecting

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.
Desalination 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 desalination plants typically operate at recoveries of 75% to
85%. The water recovery varies due to different sample characteristics, 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.

Page 16
 Conventional disposal options for concentrate are surface water discharge,
deep well injection, evaporation ponds and land application. Disposal of brine is of much
significance both from environmental and economic standpoints, particularly for inland
cities. For example, in Canberra, Australia, sustainable management of brine remains one
of the significant environmental and economic barriers to the RO-based advanced
reclamation plant. Although conventional disposal methods have been commonly used
in practice, the concern of the safe disposal of brine has been focused in recent years to
reduce the potential long-term risk on environment and health.

Several studies have examined the environmental fate of brine disposal on soil
deterioration, groundwater qualities, and aquatic environment. In fact, the brine has an
adverse effect on aquatic living organisms. The high TDS and lowering level of
groundwater due to over exploitation; water scarcity is going to be a major threat for the
industry in the near future. With continuous increase in the demand of water the only
option 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 direction opposite to that for actual osmosis when subjected to a
hydrostatic pressure greater than the osmotic 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

Page 17
membrane as well as a portion 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 settings, RO is often used to remove total dissolved salts (TDS) from
industrial wastewater or treated industrial wastewater and yield permeate with relatively
low TDS concentrates.

While RO is an effective 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
prohibitive for discharge to a local sewer facility. Hauling the wastewater to a treatment
facility can also be prohibitively expensive.

Mechanical Vapour Compression (MVC) evaporators and Thermal Evaporators

have proven to be effective technologies for dewatering RO reject/RO concentrate waste
streams. In brief, evaporation is a time tested methodology for reducing the water
portion of water-based waste.

The evaporation converts the water portion 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.

Evaporation technology has always been more “hands off” than other
wastewater treatment methodologies resulting in a dramatically lower labour cost.
Evaporation technology can handle a much wider range of waste streams compared to
membranes and traditional physical/chemical treatment methodologies. Finally,
evaporation does a much better job of concentrating waste streams compared to other
methods, thereby yielding a lower disposal volume and cost.

II. TDS Concentrations of RO Reject/RO Concentrate:

Page 18
Typical RO Reject/RO concentrate TDS concentrations are often in the range of 30000-
50000mg/litre. The salts in solution 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 solution temperature
increases. MVC Evaporators operate of typical temperatures of 225-230 o F for high TDS
applications like RO reject/RO concentrate. Similar or slightly higher (250 oF maximum)
operating temperatures can be expected with high TDS applications for Thermal
Evaporators.

Evaporator concentration endpoints correspond closely with saturation

concentration 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 saturation points in the range of 400,000-600,000mg/litre at the
referenced elevated temperatures.

Based on a simple arithmetic, concentrating the RO reject/RP concentrate

wastewater from 30,000 to 40,000 mg/litre corresponds to a volume reduction
percentage of approximately 92.5%. Concentrating from 50,000 to 600,000 mg/litre
would yield to a volume reduction 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 antiscale referred to as Threshold Scaling Inhibitors(TSI) are
being used. TSI is added upstream of the evaporator and modifies the insoluble salt
crystals creating a soft slurry that has less of a tendency to adhere to surface and cause
scale. The resulting soft slurry also has a consistency that minimised the likelihood of
erosion on heat exchanger or plumbing surfaces.

1.2. ACIEVING ZERO LIQUID DISCHARGE:

Page 19
 Where there is an interest or requirement to achieve zero liquid discharge (ZLD),
evaporation 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 solution 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 concentration, an MVC evaporator is

fed with the RO reject /RO concentrate and it yields distilled 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 exhausting 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
Concentrations for the Seawater has higher TDS levels and lower recovery rate compared
to Surface water, Fresh & Brackish Groundwater and showing various parameters (Table
1.1.)

The imposition 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
regulations have however provided the necessary impetus in a focused manner.

This technology Guidance manual covers a broad spectrum such as technology, economic
consideration and management to facilitate the implementation of ZLD.

Table 1.1: Typical Desalting Membrane System Design Parameters by Water Source
Parameter Surface Fresh Brackish Seawater
(units) water Groundwater Groundwater

Feedwater 200-400 400- 500-10,000 30,000-40,000

TDS(mg/L) 500

Page 20
 Water
Recovery 80-90 80-90 65-85 40-60
(% of
feed)
Concentrate
Vol. (% of 10-20 10-20 15-35 40-60
feed)

Concentrate
TDS (at 13303660(85 2660- 200040,000(75 60,00080,000(5
indicated % %) 3330(85%) %) %)
recovery)
(mg/L)

Concentra 5-10 5-10 2.9-6.7 1.7-2.5

tion
Factor

Maximum and Minimum TDS Concentrations for the Seawater by using RO process is
more compared to RO process for Brackish water for different processes Maximum and
Minimum TDS Concentration 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
Softening 300-1000 1000 5000

1.3. DESALTING PROCESS FOR RO CONCENTRATE:

Page 21
Recovery of salts from RO concentrate is increasing for its environmental safe way to
reuse of waste volume of reject. The change of solution temperature either by
evaporation and cooling used to extract salts from concentrate has been widely used
worldwide. In which, electro-dialysis, ion-exchange, eutectic freezing, and chemical
processing are being practiced to recover salts from concentrate. Further, in advance
hybrid systems which consisting of combination of two or more separation process
techniques, such as the nanofiltration—reverse osmosis—thermal processes, are being
deployed actively to increase the amount of extracted salt and reduce the final volume of
reject.

1.4. CRYSTALLIZATION:

The crystallization technology has certain advantages such as a high recovery ratio of
resources and recovery of high quality water.

Although crystallization is widely used for purification and separation, the design and
operation of a crystallizer still face many limitations.

These include, for example, poor reproducibility in the final crystals' characteristics,
limited super saturation control and less ability to modulate the super saturation
generation rate.

I. Crystallization:

Crystallization is the formation of solid particles within a homogeneous phase. It may

occur as the formation of solid particles in a vapour, as in snow; as solidification from a
liquid melt, as in the manufacture of large single crystals; or as crystallization from liquid
solution. This chapter deals mainly with the last solution. The concepts and principles
described here equally apply to the crystallization of a dissolved solute from a saturated
solution and to the crystallization of part of the solvent itself, as in freezing ice crystals
from seawater or other dilute salt solution.

Page 22
Crystallization from solution is important industrially because of the variety of materials
that are marketed in the crystallization form. Its wide use has a twofold basis: A crystal
formed from am impure solution is itself pure (unless mixed crystals occur), and
crystallization affords a practical method of obtaining pure chemical substance in a
satisfactory condition 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, contamination results, the
extent of which depends on the amounts and degree of impurity of the mother liquor
retained by the crystals.

In practise, much of the retained mother liquor is separated from the crystals by filtration
or centrifuging, and balance is removed by washing with fresh solvent. The effectiveness
of these purification steps depends on the size and uniformity of the crystals.

Importance of crystal size:

Clearly, good yield and high purity are important objectives in crystallization, 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, reacting with other chemicals, transporting, 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 distribution (CSD) must be under control; it is a prime
objective in the design and operation of crystallizers.

Page 23
For applications where high rates of evaporation are required, where there are scaling
components, or when crystallization must be achieved in solutions with inverted
solubility or relatively high viscosity, the forced circulation crystallizer is the best choice.

The accelerating rate of global population 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 matter. Desalination technologies have
gained much attention in recent years as their performance and application 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 estimated that the daily
brine production from desalination plants around the world is approximately 142 million.

Brine composition, volume and disposal techniques affect brine disposal cost which can
constitute up to a third of total product water cost for desalination technologies. The
selection of the optimal brine management strategy depends on several factors including
brine volume and composition, discharge location, and the capital and operating costs
Surface water discharge, deep well injection and land application are common brine
disposal options.

1.5. ZERO LIQUID DISCHARGE:

ZLD refers to any process or combination of processes through which there is no liquid
effluent from a chemical process plant. Existing ZLD systems focus mainly on the
evaporation and crystallization processes, which are not always the optimal technologies
to treat brine. ZLD is usually achieved by concentrating 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 pollution, but at the expense of high cost and intensive energy consumption .

Therefore, reliable and efficient ZLD configurations must be designed through the
combination of different technologies to achieve optimal water recovery and energy
Page 24
consumption while accounting for the produced salt. These technologies will not be
considered in this work.

Worldwide construction 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 sensitive and polluted environments.

Countries like China and India, where water is scarce and the industrial water recovery
ratio is very low, are potential candidates for the development of ZLD solutions. The
Market for ZLD systems has grown steadily during the period 2000-2014 (figure 1.2.)

Fig 1.2: Number of ZLD installations 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 eliminating the

Page 25
environmental pollution to water bodies. ZLD process makes effective use of waste water
treatment, recycling, and reuse, thereby contributing to water conservation through
reduced intake of the fresh water.

“Zero Liquid Discharge refers to installation of facilities and system which enables
industrial effluent for absolute recycling of permeate and converting solute (dissolved
organic and inorganic compounds/salts) into residue in the solid form by adopting
method of concentration and thermal evaporation.”

ZLD is recognised and approved based on two broad parameters that are, water
consumption versus waste water reused or recycled (permeate) and corresponding solids
recovered. In the above ZLD definition, domestic waste water from industry is separated
from industrial waste water and treated separately. However, recycle/disposal of
domestic waste water is not mentioned or stipulated.

ZLD is applicable to industries generating wastewater of high BOD/COD load, colour,

metals, pesticides, toxic/hazardous constituents, solvents and high TDS bearing effluents.
However, considering water scarcity and reject water/ sludge disposal cost, many
industries and adopting 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 options are receiving more and
more attention. In this perspective, zero-liquid discharge (ZLD) is considered as an
emerging technique to minimize waste, recover re-sources, treat toxic industrial waste
streams, and mitigate potential water quality impacts in receiving water streams.
Although ZLD systems are capable of minimizing contamination of water sources and
amplifying water supply, its industrial scale applications are restricted due to their high
Page 26
 cost and intensive energy consumption. In ZLD systems, membrane-based technologies
are an attractive future strategy for industrial waste water reclamation (figure 2.1.).
Thermal Evaporation Technologies are used to remove inorganic salts from RO Reject and
reduce the TDS levels. One of the Thermal evaporation Technology is using the Brine
concentrator and Brine Crystallizer to achieve ZLD (figure 2.2.)

Fig 2.1: Pictorial representation of a Zero Liquid Discharge Treatment Plant

Fig 2.2: Schematic diagram of a Thermal ZLD

system

Status of ZLD systems for resource recovery in India:

Page 27
The practical implementation of ZLD systems across the globe for re-source recovery
depends upon geographical location, 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).

Rapid industrialization and urbanization in India is creating severe pressure on water

resources and is increasing pollution. Recently, a three-year target was set by the Indian
government—known as the
“Clean Ganga project”—that imposes stringent regulations on wastewater discharge and
compels highpolluting industries to move toward ZLD (Abdelhamid, 2015). In 2015, the
Indian government's water conservation policies imposed ZLD installation at all textile
plants generat-ingN25 m3of wastewater per day (Singh and Bhalla, 2017). India has
extended ZLD to a range of industrial sectors including power, steel, pharmaceutical,
chemical, textile, 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 textile 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 optimize a real problem of freshwater and

wastewater reuse allocation. The case study is an industrial polypropylene unit and the
solution achieved is an almost zero discharge case. The problem was decomposed into
subsystems according the type of approach used to water minimization: process changes,
regeneration reuse and regeneration recycling. For the regeneration approach, an
innovative 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.

Page 28
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
industrial case by using innovative wastewater treatment technologies together with
optimization of water/air cooling systems.

The results obtained prove that the water minimization techniques used can effectively
reduce overall fresh water demand and the overall effluent generated, resulting 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 population could
face water scarcity. Desalination technologies, particularly the reverse osmosis (RO)
process, have increasingly been adopted to produce freshwater from alternative sources
such as seawater and brackish water due to water scarcity. However, desalination
applications 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 identify technically and commercially RO brine disposal and
treatment methods such as deep well injection, discharge into the sea, sanitary sewers,
evaporation ponds, forward osmosis (FO), vacuum membrane distillation (VMD),
vacuum-enhanced direct contact membrane distillation (VEDCMD), RO–NF Integrated
system, bipolar membrane electrodialysis (BMED), electrodialysis (ED), Electrodialysis
reversal (EDR), vibratory shear enhanced processing (VSEP), capacitive deionisation (CDI)
and so on.

Page 29
In this paper, as a part of our desalination research package, to achieve profitable and
environmental solutions, we assess advantages and disadvantages of mentioned
methods through a comprehensive review of worldwide laboratory, pilot and industrial
scale experiments.

For RO brine treatment methods,

• FO achieved water recoveries up to 90% from the brines. Addition of a scale inhibitor
during process was effective at maintaining high water flux for extended time. 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. Addition of a scale
inhibitor during pro-cess was effective at maintaining high water flux for extended
time. 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 desalting using ICD at the pilot
and demonstration scales.
• VC process is well established and is used for treating RO concentrate in a near-ZLD
application.
• During the treatment of a RO concentrate with high silica concentration, MD could
reduce the volume of RO concentrate by 60%, achieving an overall water recovery of
90% through RO–MD.

Page 30
• MDC ability to concentrate RO brines is greater than 90%.
• In principle, integration of the NF unit with RO in water desalination plants makes it
possible to approach improving salt rejection 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.
• EFC achieved water recoveries up to >95% from the brines.

And for RO brine disposal methods, above sections show:

• Discharge of desalination concentrate to a surface water body (river, lake, lagoon,

canal, ocean, etc.) is the most common management practice for brine disposal.
• Discharge of concentrates to sanitary sewer systems is sometimes feasible if the
concentrate mixture is not toxic and does not adversely affect the clarifier settle-
ability or restrict final effluent disposal.
• Land application can provide a beneficial reuse of water when membrane
concentrates are applied to vegetation, such as irrigation of lawns, parks, or golf
courses. Factors associated with land application include the water quality tolerance
of target vegetation to salinity, the ability to meet ground water quality standards,
the availability and cost of land, percolation rates, and irrigation needs. In general,
land application is used only for smaller volumes of concentrates.
• Deep well injection is a disposal technology which liquid wastes are injected through
the injection tubing into the well. Since there is no technical difficulty in injecting
desalination waste, it is one of the frequently used methods in disposing waste;
however regulations on deep well injection are strict.
• Solar evaporation is a viable alternative in relatively warm, dry climates with high
evaporation rates, level terrain, and low land costs. Regulations typically require an
impervious lining and monitoring wells, which will increase costs of evaporation
ponds. With little economy of scale, evaporation ponds are usually used only for small
volume concentrates.[3]
Page 31
Graphically based analysis of water system with zero liquid discharge:

Based on graphical method, this paper proposed the necessary condition of zero liquid
discharge (ZLD) and optimized the corresponding regenerated water flowrate and
regeneration concentration for single contaminant water system with fixed mass load.
As far as the water system without water loss is concerned, ZLD can be accomplished
when the post regeneration concentration is not higher than the minimum limiting inlet
concentration of all the operations.

Moreover, considering the water system with water loss, the formulations for calculating
the optimal targets (the optimal regenerated water flowrate and the optimal
regeneration concentration) for ZLD are deduced. The maximum post-regeneration
concentration for ZLD is defined. If the post-regeneration concentration is not higher
than it, ZLD is feasible. The optimal zero discharge water network is constructed with a
given post regeneration concentration (figure 2.4.)

Fig 2.4: The Hierarchical procedure of ZLD

For the single contaminant water system, this paper analyzes the conditions and optimal
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-regeneration concentration is not higher than the minimum limiting inlet
Page 32
 concentration of all the operations. This paper proposed the method for targeting the
optimal pre- and post regeneration concentrations. 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 optimal
regeneration concentration and regenerated water flowrate, and the corresponding
formulas are deduced. The maximum post-regeneration concentration C max, o for ZLD is
defined and can be obtained by graphical method. The necessary condition for ZLD is
that the post regeneration concentration is not higher than C max, 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 partially satisfied by desalination plants that
increasingly use membrane technologies and among them reverse osmosis to produce
purified water. Operating 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 constitute a potentially serious threat
to marine ecosystems; therefore there is an urgent need for environmentally friendly
management options of RO brines.

This paper gives an overview on the potential treatments to overcome the environ-
mental problems associated to the direct discharge of RO concentrates. The treatment
options 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
differentiated

i) desalination plants,
ii) Tertiary processes in WWTP, and iii) Mining
industries.

Page 33
 Starting with traditional treatments such as evaporation and crystallization other
technologies that have emerged in last years to reduce the volume of the concentrate
before disposal and with the objective of achieving zero liquid discharge and recovery of
valuable compounds from these effluents are also reviewed.

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
application of innovative advanced oxidation 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 Primary Secondary RO 88-99%
ZLD RO _
Scheme

Type-A Primary RO Ion exchange Secondary RO

ZLD Resins for
Scheme Silica
removal
Primary RO Precipitation
87-97%
treatment(alk Secondary RO
aline induced)

RO WAIV Membrane 77-89%

Type-B ZLD Crystallizer
Scheme
Primary RO Secondar Precipitation
y RO Treatment
(Calcium

Page 34
 Sulfate,
magnesium,
iron and silica)
RO ED/EDR 92%
Primary Secondary EDR + UF, >98%
Type-c ZLD RO RO WAIV
Scheme Lime Soda
Primary Secondary 80-90%
RO Treatment Ro,
Intermediate Evaporation
Treatment ~100%
Primary Secondary
RO RO,
Brine
Concentr
ator +
pond

PILOT TESTING OF MEMBRANE ZERO LIQUID DISCHARGE FOR DRINKING WATER

SYSTEMS:

Utilities 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 minimization and zero liquid discharge (ZLD)
technologies show promise to provide cost effective means for brine disposal. The
purpose of this project was to pilot test concentrate minimization and zero liquid
discharge technologies suitable for use in Colorado.

A new technology, zero discharge desalination (ZDD), was pilot tested at two drinking
water RO plants in Colorado. The ZDD technology is an integrated system combining
electrodialysis metathesis (EDM) with nanofiltration. The first pilot test reached 96%
recovery when treating brackish groundwater to levels suitable for human consumption.

Page 35
The second pilot test demonstrated increasing the recovery an existing membrane
system to 98% by treating 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 potential 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 operation before the process is
suitable for full-scale use in Colorado.

Benefits:

• Provides a literature review of concentrate minimization and zero liquid discharge

technologies.
• Provides pilot test assessments of the zero discharge desalination technology.
• Provides cost estimates for full scale implementation of zero discharge desalination
technology.[7]

THERMAL EVAPORATOR FAILS-THE OPERATING AND MAINTAINANCE COST:

The main reason was the financial inability of the industry to meet the operation
and maintenance cost by way of electrical power as in Tables 2.3 hereunder. When the
CETPs were set up initially 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 apportion 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 consumption in ZLD Encompassing in Thermal Evaporator

S. No Component of ZLD KWhr/cu % of Equivale
m of feed Effluent nt of raw

Page 36
 1. Primary Treatment like 0.9 100 0.9
equalisation, chrome precipitation,
neutralization etc
2. 1.5 100 1.5
Biological Treatment in aeration
3. 3.2 100 3.2
Cross flow membrane filtration
4. 2.4 100 2.4
RO desalting membrane filtration
5. 6.0 15 0.9
Thermal Evaporation
Total/cum of feed 8.9

ADVANTAGES

• Eliminates steal generators as induced thermal evaporative operation · 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 specifications as there is no BIS code of practice.
• 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 nettings are readily available off the shelf green-house nettings.
• Efficiency can be maximized using spray nozzles for application on nettings.
• Rainy days also bring about evaporation 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 Pharmaceutical Industry:

Page 37
Zero Liquid Discharge (ZLD) is an ideal situation 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 regulation in a challenging way. For
achieving ZLD system for the industry, certain steps are needed to be taken.

These steps include: Analysis of major characteristics of all influent streams entering into
ETP, Identification of potentially recyclable streams and highly polluted stream,
Segregation of streams on the basis of their characteristics and applicability of 4R
(Reduce, Reuse, Recycle and Recover) principle in particular plant.

Optimization of Effluent Treatment Plant (ETP), RO Plant and Multi 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 consumption of industry can be reduced significantly.

The effluent coming to ETP is having some significant effluent characteristics like widely
varying pH, high COD and Ammonical nitrogen. After primary, secondary and tertiary
treatment, the effluent meeting discharge norms is send to FETP of NCTL for further
treatment and disposal.

In this project an attempt would be made to optimize 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-filtration, 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

Page 38
 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

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
o
1 Temperature C 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 Conservation.
• 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 pollution.
• Preferred option for industry where disposal of effluent is major bottleneck.
• Prevents exploitation of hydraulic capacity of disposal system Separation of salts /
residual solvents improve efficiency of ETP and CETP.

Page 39
• 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 getting environmental permissions.
• More focus on production/ business rather than tracking after regulatory authorities.
• Reduction in water demand from the Industry frees up water for Agriculture and
Domestic demands.[9]

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. After the feed attaining 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. After attaining the temperature of 80 oC, 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 partial amount of slurry is sent to the
centrifuge decanter where the solid crystals separated from the liquid on high rotational
speed to separate components of different densities 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 heating
purposes.

Page 40
Therefore, the complete separation of Solid materials from the liquid is achieved by
Thermal Evaporation 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 antiscalants formulations are usually added
to avoid scaling in preheaters with calcium carbonate.

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 Regenerative 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
continues to expand to condenser pressure. The extracted steam condenses in the closed
feedwater while heating 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 schematic of closed feed water pre-heater is shown.

Page 41
 Fig 3.1: Schematic diagram of a Feedwater Preheater

3.2. VERTICAL SHELL AND TUBE HEAT EXCHANGER

Heat Exchanger:

Page 42
Shell and Tube Heat Exchangers are used for the majority of installations. The heating
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.

Vertical Shell and Tube Heat Exchanger:

A Vertical Shell and Tube Heat Exchanger in which the tubes extend through oversized
holes in a liquid distribution 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 position. Vertical 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
applications.

Fig 3.2: Vertical 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 applications (with pressures greater than 30 bar and temperatures greater

Page 43
than 260oC.) This is because the shell and tube heat exchangers are robust due to their
shape.

Specification:

• Vertical 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.

Applications

• Vertical Shell and Tube Heat Exchanger is widely used in variety of applications as a
cooling solution.
• The most common among them is for cooling of hydraulic fluid and oil in engines,
transmissions and hydraulic powder packs.
• With the right combination of materials they can also be used to cool or heat other
mediums, such as swimming pool water or charge air.
• Vertical Shell and Tube Heat Exchanger also be used on fixed tube sheet heat
exchanger.

3.3. FORCED CIRCULATION CRYSTALLIZER

Crystallization:

Crystallization is the formation of solid particles within a homogeneous phase. It may

occur as the formation of solid particles in a vapour, as in snow; as solidification from a
liquid melt, as in the manufacture of large single crystals; or as crystallization from liquid
solution.

The concepts and principles described here equally apply to the crystallization of a
dissolved solute from a saturated solution and to the crystallization of part of the solvent
itself, as in freezing ice crystals from seawater or other dilute salt solution.
Page 44
For applications,

Where high rates of evaporation are required,

Where there are scaling components, or

When crystallization must be achieved in solutions with inverted solubility or relatively

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

Fig 3.3: Schematic diagram of Forced Circulation Crystallizer

Forced Circulation Crystallizer:

The forced circulation (“FC”) crystallizer is the most common type of crystallizer in the
industry. The average FC crystallizer evaporates solvent, thus increasing the super
saturation in the process liquor, and causing crystallization to occur. Most conventional
FC units operate under vacuum, or at slight super atmospheric pressure.

The FC consists of four basic components:

Page 45
 • The crystallizer vessel, which provides most of the volume dictated by the
residence time requirements,
• The circulating pump, which provides the mixing energy, the heat exchanger,
which supplies energy to the crystallizer (in a typical evaporative crystallization
operation), and
• The vacuum equipment, which handles the vapours generated in the crystallizer.
• 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
saturation is relieved by deposition of material on the crystals present in the slurry.

The super saturation is controlled so as to avoid spontaneous nucleation, by sufficient

circulation capacity. The evaporated solvent is conducted to the vacuum system, where it
is condensed and removed. The FC crystallizer is used for general, simple crystallization
operations, where large crystal size is not a requirement.

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

This type of unit, also known as the circulating 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. Suction
from the lower portion of the body passes through a circulation pump and a heat
exchanger and returns to the body through a tangent or vertical inlet. The heat
exchanger is omitted when adiabatic cooling is sufficient to produce a yield of crystals.
The most common use of this crystallizer is as an evaporative crystallizer with materials
having relatively flat or inverted solubility. It is also useful with compounds crystallized
from solutions with scaling components.

Controlled super saturation

Page 46
When the heat exchanger is used, it is normally one or two pass and is designed for
relatively low temperature rises in the solution. This limits the super saturation of scaling
components when heating materials of inverted solubility.

Forced circulation is the most widely practiced method of crystallization. Forced

circulation crystallizers are found in sizes ranging from two-foot diameter laboratory
models to over 40-foot diameter units for continuous processing. Per pound of product,
it is ordinarily the most inexpensive type of equipment available, particularly when
substantial amounts of evaporation are required.

Forced circulation crystallizers can be operated on a batch basis, but their most frequent
use is for continuous 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 solution can be used to vaporise more
water. Provided there is a temperature drop for heat transfer in the desired direction. In
a multiple effect evaporator this temperature drop is created by progressively lowering
the boiling point of the solution 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
conventional forced-circulation evaporator.

Page 47
This vapour evolved, however, is not condensed; instead it is compressed to a somewhat
higher pressure by a positive-displacement or centrifugal compressor and becomes the
“steam” which is fed to the heater. Since the saturation temperature of the compressed
vapour is higher than the boiling point of the feed, heat flows from the vapour to the
solution, generating more vapour. A small amount of makeup steam may be necessary.

The optimum temperature drop for a typical system is about 5 oc. The energy utilization 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
effects. Important applications of mechanical compression evaporation include
production of distilled water from seawater, evaporation of black liquor in the paper
industry, evaporation of salts having inverted solubility curve.

3.5. CIRCULATING PUMP:

A circulator pump or circulating pump is a specific type of pump used to circulate gases,
liquids, or slurries in a closed circuit. They are commonly found circulating water in a
hydronic heating or cooling system. Because they only circulate liquid within a closed
circuit, they only need to overcome the friction of a piping system (as opposed to lifting a
fluid from a point of lower potential energy to a point of higher potential energy).

Circulator pumps as used in hydronic systems are usually electrically powered centrifugal
pumps. As used in homes, they are often small, sealed, and rated at a fraction of a
horsepower, but in commercial applications 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 applications often 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-tight
seal at the point where the pump drive shaft enters the pump body.
Page 48
Small- to medium-sized circulator pumps are usually supported entirely 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.

3.6. Centrifuge Decanter:

A centrifuge is a device that employs a high rotational speed to separate components of

different densities. This becomes relevant in the majority of industrial jobs where solids,
liquids and gases are merged into a single mixture and the separation of these different
phases is necessary.

A decanter centrifuge (also known as solid bowl centrifuge) separates continuously 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 heuristics
to be followed which are dependent upon given applications (figure 3.4.)

Page 49
 Fig 3.4: Schematic diagram of Centrifuge Decanter

Operating principle:

The operating principle of a decanter centrifuge is based on separation via buoyancy.

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

A decanter centrifuge increases the rate of settling through the use of continuous
rotation, producing a gravitational force equivalent to between 1000 and 4000 G's.

This reduces the settling time of the components by a large magnitude, whereby mixtures
previously having to take hours to settle can be settled in a matter of seconds using a
decanter centrifuge.

This form of separation 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 separation takes place in the cylindrical part of the bowl.

Page 50
The fast rotation generates centrifugal forces up to 4000 x g.

Under these forces, the solid particles 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 differential speed.

This way the scroll is transporting the settled particles 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 51
FLOWSHEET FOR “THE REMOVAL OF INORGANIC SALTS FROM RO CONCENTRATE
BY USING THERMAL
EVAPORATION TECHNOLOGIES”.

Page 52
 CHAPTER – 4

MASS BALANCE & ENERGY BALANCE

MASS BALANCE:

A balance on a conserved quantity (total mass, mass of a particular species, energy, and
momentum) in a system (a single process unit, a collection of units, or an entire process)
may be written in the following general way;

[Accumulation = input – output + generation - Consumption]

For continuous processes at steady state, the accumulation term in the general balance
equation equals zero, and the equation simplifies to

Input + generation = output + consumption

If the balance is on a non reactive species or on total mass, the generation and the
consumption term equal zero and the equation reduces to

Input = output

Since, there is no reaction taking place. So, we must equate the Accumulation, Generation
& Consumption to 0 (Zero).

Overall Mass balance equation:

Basis: Considering, the given operation 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 42
 Soli

ds

RO Reject = Mother Liquor + Solids

15,425
Feed (RO Reject) Mother Liquor kg/hr =
Mother
15,425kg/hr
Liquor +
Solids

We know

that, if

TDS is known from a Chemical analysis of formation of Water, then the formula below

can be used to estimate formation 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/cm 3

= 1033.366 kg/m 3

Density of Water in the input feed = 1033.366 kg/m 3

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)

B. Page 43
 Mass balance for Heat Exchanger:

Assumptions:

1. Assuming no accumulation, generation and consumption.

2. Circulation rate = 2400kg/hr.

Vapour + Low Pressure Steam

HEAT Crystallizer
Feed from Pre-Heater + PreEXCHANGER -Heater
(Partially Condensed Vapour
Circulation + Low Pressure
Steam)

Vapour + Low Pressure Steam = Partially Condensed Vapour + Low Pressure Steam
Output = Feed from Pre-Heater + Circulation
= 15,425 + 2400
= 17,825 kg/hr
Feed rate of Crystallizer = 17,825 kg/hr

Mass balance for Crystallizer:

Assumption: 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

B. Page 44
 Slurry Feed input =
Vapour + Slurry

80% of feed = 0.80 * 17,825

= 14,340 kg/hr

So, slurry leaving from the crystallizer = 17,825 – 14,340

= 3485 kg/hr

Circulation pump:

Slurry from Crystallizer can be partially 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-circulating 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 satisfactory 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)

B. Page 45
 = 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

= 0.2024 kg

Energy Balance:

ASSUMPTIONS:

• Continuous, steady flow, Steady state operations.

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

Energy requirement for heat exchanger:

The general energy balance equation for the heat exchanger is,

Q = m*Cp*ΔT + mv*λv

Assumptions:

Initially feed heated to 55oC in the preheater

Data:
B. Page 46
 m = Feed rate = 17,825 kg/hr

𝑚𝑣 = Vapour rate = 14340 kg/hr

Cp = specific heat = 4.181 J/kg K

ΔT = Temperature difference = 25oC

λ = Latent heat of vapour = 2305 kJ/kg

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

Q = m*C p*ΔT + mv*λv

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

= 3,49,16,858.13 kJ/hr

(For Vapour heat required from 80-90 oC)

Energy requirement for vapour:

(Heat released from 80-90oC)

Q = m*C p*ΔT

Cp = specific heat of Vapour = 1.9654 kJ/kg

ΔT = 90 oC - 80oC

= 10 oC

m = 14,890 kg/hr

Q = 14,890 * 1.9654 * 10

= 2,92,648.06 kg/h

By Latent heat,

Q = mv*λv

B. Page 47
 = 14,890 * 2305

= 3,43,21,450 kg/hr

Total heat required for the vapour,

= 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

Initial Temperature of feed Ti = 35oC

Cp = Specific heat = 40181 kJ/kg

Final Temperature of feed, To = 55oC

Heat required for heating = m*Cp*ΔT

= 15,425 * 4.181 * 20

= 12,89,838.5 kJ/kg

T2 = Initial Temperature of Steam

B. Page 48
 T3 = Final Temperature of Steam leaving Preheater

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 * ρ v * uv2 ≤ 1.75

N/m2

Data:

Operating 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 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, T̅ = 80oC

In order to satisfy 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*D v. In this design, a
double radial inlet is chosen and slurry is recycled to the heater through a single bottom
outlet.

To satisfy 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*10 6*23*10-4

B. Page 50
 1848.27*1.4

𝑣𝑖 = 4.18 m/s

For Circulating Volumetric flowrate

Q=

𝑞𝑖= 34916858.13 kJ/hr, ΔT = 4.8632oC

Q=

= 929.78m 3/hr

For total circulating flowrate,

Q = 929.78m3/hr, the crystallizer inlet diameter

Di

= 0.89838m

In order to maintain equal velocities in inlets and outlets

Do

2
√ 0.89838 2

= 1.28 m
B. Page 51
 The inlet temperature of brine at the entry of evaporator body = 80 oC

Corresponding Vapour Pressure = 55 kN/m2

Operating 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 hydrostatic

head is ΔP =

h*ρ*g

𝛥𝑃
h=

h=

= 0.494 m

Total minimum height required for cylindrical part of body is

Hc, m = h + Di + ¾ Dv + Additional 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 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 domestic and commercial
salts and minerals from saline water. Based on the type of separation 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
distillation.
Alternatively, saline water is frozen followed by the separation of pure ice and salts.
Distillation can use any heating source such as fossil fuels, Nuclear energy with solar
energy being a lowtech option.
Application of this technique includes,
Solar Distillation (SD), Multi-Effect Distillation (MED) or Multiple Effect Evaporation (MEE),
Multi
Stage Flash Distillation (MSF), Mechanical Vapour Compression (MVC), Eutectic Freezing
Crystallization (EFC) and open pan boilers.
(b)Membrane processes: They involve separation of dissolved salts from the feed water
by mechanical or chemical/electrical means using a selective 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 53
 (c)Chemical change processes: These involve application of chemical techniques to
extract salts from feed water. The principle is applied in the Ion Exchange, Reactive
precipitation and Calcinations processes.
(d)Hybrid processes: They involve combination of the above processes in a single unit or
in sequential unit or in sequential steps. Examples include: Membrane Distillation (MD),
Membrane Crystallization (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 distillation.
Alternatively, saline water is frozen followed by the separation of pure ice and salts.
Distillation can use any heating source such as fossil fuels, nuclear energy with solar
energy being a low-tech option.

Application of this technique includes

solar distillation (SD), multi-effect distillation (MED) or multiple effect evaporation (MEE),
multi-stage flash distillation (MSF), mechanical vapour compression (MVC), eutectic
freezing crystallization (EFC) and open pan boilers.

Thermal Based Technologies:

Thermal based technologies use heat to separate water from the concentrate

stream. Some technologies also provide additional 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 vertical tube bundles with brine evaporating 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 vaporization transfers from the

B. Page 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 oftentimes designed to operate in
a slurry mode where calcium sulphate is added to the recycle to provide nucleation sites
for the precipitation 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 concentrating 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 operation 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 55
 Fig 6.1: Schematic diagram of ZLD system including Brine Concentrator and

Crystallizer II. Brine crystallizers:

Brine crystallizers are typically vertical cylindrical vessels with heat input from vapour
compressors or an available stream supply. Feed brine is mixed with re-circulating 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
solution. Brine crystallizers are oftentimes 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 times the energy required by brine concentrators
(Mickley et al., 2006).

B. Page 56
 Fig 6.2: Brine

Crystallizer

Fig 6.3: Schematic of Zero Liquid Discharge system using Brine Concentrator, Brine
Crystallizer and Evaporation 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 applications, including operation of the desalination systems. An example of SGSP
coupled with desalination system for ZLD application.

The brine from the RO system is treated using a second stage thermal desalination
process. The brine from the thermal desalination 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 57
 Fig 6.4: Schematic of Zero Liquid Discharge system using salinity gradient solar

pond, Brine Concentrator and recovery system

IV Spray Dryers:

Spray dryers are comprised of a vertical 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:

· Concentration of slurries to solids waste,

· Feasible in areas where other low cost options are not available in a small
footprint.

Disadvantages of a spray dryer:

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

v) Evaporative Reduction and Solidification (EVRAS):

The EVRAS process is an evaporative 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 schematic of the technology is available from Intevras, 2011).

The technology is used for brine treatment and utilizes low-grade waste heat to
concentrate and/or crystallize large volume of brine streams. EVRAS is an evaporative
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 applications with limited applications in the
municipal sector. The advantages of the system include (RPSEA, 2009):

• Use of low temperature waste heat

• TDS insensitive
• Corrosion resistant and minimal scaling problems
• Simplicity in operation 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 left 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 incineration/landfill.

B. Page 59
 ZLD systems range from Simple to Highly complex system depending on the complexities
in Wastewater streams. Ultimate aim of ZLD is to recover useful products, and salts from
rejects, apart from recovery of maximum water recycle.

Following are the major ZLD technologies that are used in various combinations as per
the requirements.

• Solvent Extraction/Stripper
• Membrane Bio Reactor Technology (MBR)
• Ultra Filtration (UF)/Reverse Osmosis (RO)
• Evaporation Technologies-Multi Effect Evaporators (MEE)
Mechanical Vacuum Re-Compressor (MVR)
• Agitated Thin Film Dryer (ATFD)
• Crystallization
• Incinerator

7.1.EVAPORATION TECHNOLOGIES:

The ultimate objective of ZLD is not discharging waste water outside the industry. This
objective is achieved by Evaporation or Crystallization 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 solution and the Thermal separation is the final step of
ZLD.

Evaporation of Reject water is most commonly used treatment for reduction of waste
volume, recovery of salts and to recycle the condensate in process. Evaporation plants
used are Thermal separation technology, for the Concentration or operation of Liquid
solutions, Suspensions and Emulsions.

B. Page 60
 Types:

I. Falling film Evaporator:

This technology is particularly suited for energy-saving. It only requires a very small
operating 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 solution for
streams which are viscous in nature and contain small concentrations of suspended solids

A Falling Film Evaporator can be used as a pre-concentrator in a combined Multiple-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. Evaporation
occurs on the surface of the highly turbulent film and not on the tube surface. This
requires that temperature differences be relatively low

Many times rising film and Falling Film Evaporators are combined into single unit. When
high ratio of Evaporation to feed is required and the Concentrate liquid is viscous. A Tube
bundle is divided into two sections with the first section functioning as a rising film
evaporator and the second section serving as a falling film evaporator (figure 7.1.).

B. Page 61
 Fig 7.1: Schematic diagram of Falling Film Evaporator

II. Forced Circulation Crystallizer:

The forced circulation Crystallizer is used for processing liquors which are susceptible to
scaling or crystallizing. Liquid is circulated at a high rate through the HE, boiling being
prevented within the unit by virtue of a hydrostatic 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.)

B. Page 62
 Table 7.2: Schematic flow diagram of Forced Circulation Crystallizer

III. Natural Circulation:

Evaporation by natural circulation 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 evaporation capacities can be obtained. The most common
application for this type of units is as a re-boiler at the base as a desalination column
(figure 7.3.).

B. Page 63
 Fig 7.3: Diagram showing of Natural Circulation

IV. Plate Type Evaporator:

Principally, plate evaporators are similar to falling film& forced recirculation 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
product residence time, superior quality concentate is obtained. It is a more compact
design with low headroom requirements, and low installation cost
(figure 7.4.).

B. Page 64
 Fig 7.4: Schematic diagram of Plate Type Evaporator
Table 7.1: Representation of wide range applications of different ZLD Technologies in
various fields &
Operations, Recovery
S. Technology
No.
1 Forced Circulation
2 Falling film
3 Natural Circulation
Applications
• Suitable for Evaporation applications
containing high levels of hardness, silica,
suspended solids & crystalline slurries.
• Salt recoveries like NaCl, Na2SO4,
NH4Cl,
(NH4)2SO4, ZnSO4, K2SO4, KCl & CaCl2, etc.,
• Suitable for Liquors, feeds with low hardness
and non- Crystalline concentrates with low
viscosities.
• Useful for Concentrating Milk, fruit juices, if
hardness is <150ppm.
• Suitable for concentration of viscous Liquids
below saturation without hardness.
• Solids Slurry with high Viscous.
• Liquid, where solids will settle down and clear

B. Page 65
 liquid is circulated.
4 Plate Type • Application is same as Forced Circulation and
Falling film designs.
• Used for low level installations.

7.2.EXTRACTION OF POTENTIALLY PROFITABLE MATERIAL FROM RO REJECTS:

Magnesium:

The main unit processes used for the extraction of magnesium is evaporation cum
crystallization, precipitation, and ion-exchange. Ohya et al. proposed a series of
integrated processes (crystallization, electro-dialysis and Ion-exchange) to recover salts of
calcium carbonate, sodium chloride and magnesium sulphate from RO reject. Drioli et al.
identified a process of membrane crystallization/distillation to separate out various
inorganic salts from reject streams from an integrated Nano Filtration (NF)/RO process. In
Russia, a large scale extraction plant is also being operated for the recovery of
magnesium from seawater using ion-exchange, and extraction of magnesium from RO
reject from seawater desalination system.

Potassium:

Worldwide potash consumption is increasing every year approximately at a rate of 3%

due to population growth and other increased demand for fertilizers. The main source of
potash production is done by conventional shaft mining or deep-well solution mining
process techniques.

Currently, potassium is being produced from seawater as a by product from solar salt
evaporation. As an alternative to solar evaporation/precipitation, several researchers
have suggested that, potassium could be produced from RO reject using an
evaporation/crystallization process. The extraction of potassium is done using natural

B. Page 66
 zeolite (clinoptilolites) ion-exchange materials which has high exchange capacity for
potassium through a two-step dual-temperature process.

Sodium:

The production of sodium compounds from desalination reject is obtained through

evaporation technologies, followed by crystallization, membrane crystallization, electro
dialysis followed by multiple effect distillation (ED/MED), and evaporation ponds.
Membrane crystallization (MC) is being practiced to produce relatively pure salt crystals
from a synthetic NF reject solution 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 solutions
including brackish water reverse osmosis (BWRO) and seawater reverse osmosis (SWRO)
concentrate.

CHAPTER – 8

CONCLUSIONS

• Using the data in the literature survey the theoretical model was carried and we
select our process accordingly.
• Circulating slurry to the inlet feed act as a seeds, which increases the efficient
formation of salts.
• Based on process description 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 information and process economics calculations, a plant can be
designed.
• Computational studies have been carried out and the design, Volume of the
crystallizer have been estimated

B. Page 67
 Volume of the Crystallizer 𝑣𝑙 is 200 m3.

REFERENCES
1. Abdelhamid, A., 2015. India Uses Zero Liquid Discharge (ZLD) to Clean the Ganges
River. [WWW
Document] URL: http://inspiredeconomist.com/2015/01/14/india-uses-zldganges-
river/, Accessed date: 12 October 2018
2. R. M. Rosain, Chemical Engineering Progress, 89(4) (1993) 28.
3. G. Johnson, L. Stowell and M. Monroe, VSEP Treatment of RO Reject from Brackish
Well Water:
A Comparison of Conventional Treatment Methods and VSEP, a Vibrating Membrane
Filtration System, El Paso Desalination Conference 2006, El Paso Texas, USA
4. Bonnelye, V., Guey, L., & Del Castillo, J. (2008). UF/MF as RO pre-treatment: the real
benefit.
5. Agrawal, U. and V. Shenoy, ‘‘Unified conceptual approach to targeting and design of
water and hydrogen networks, ’’AIChE J, 52 (3), 1071–1082 (2006).
6. Acevedo, C.R., Gardea Torresdey, J.L., Tarquin, A.J., 2010. Silica removal from brine
by using ion exchange. In: World Environmental and Water Resources Congress
2010: Challenges of Change e Proceedings of the World Environmental and Water
Resources Congress.
7. Alheritiere, C., Ernst, W., and Davis, T. 1998. Metathesis of magnesium and sodium
salt systems by electrodialysis. Desalination 115:189-198.
8. Dr. Komal. Mehta “Design of Reverse Osmosis System for Reuse of Waste Water
from Common effluent treatment Plant” (E-Issn: 2395 -0056)
9. Cumulative ZLD Reference Facilities based on reference plant data from Aquatech,
GE Water and
Veolia.URL:http://www.bluetechresearch.com/streams/themes/zeroliquiddischarge/
accessedon5.05.2 015
10. Gujarat Pollution Control Board, Annual report 2013-14, Green Gujarat- Ecological
and Industrial Balance3.
11. Vivek V. Ranade, Vinay M Bhandari, Industrial Wastewater Treatment, Recycling and
Reuse;
URL:https://books.google.co.in/books?
id=XiETAgAAOBAJ&pg=PA500&ing=PA500&dq=wastewa
ter+fromapi+and+bulk+drugs&source=bl&ots=XkgbKvmk8o&sig=klntLVez0roWelxeGd

B. Page 68
 RYI3GO6I
&hl=en&sa=X&ei=ev4YVYGMMHeU9aogZAP&ved=OCDsO6AEwBg#v=onepaee&q=wa
stewater %20from%20api%20and%20bulk%20drugs&f=false
12. "Combination Thermal Process with Zero Liquid Discharge"; SOUTHERN CALIFORNIA
REGIONAL BRINECONCENTRATE MANAGEMENT STUDY- PHASE I, October 2009
13. Solvent Recovery Handbook;
14. URL:https://books.google.co.in/books?
id=GcjMEOwiMVsC&pg=PA38&lpg=PA38&dq=solvent+re
covery+strippers&source=bl&ots=2OSF32YFO&sig=yEEWbr3ogL6bTAEalfTPyOclgwI
&hl=en&sa
=X&ei=MDYrVbngPIKdugT13oHgDw&ved=OCE8O6AEwBO#v=onepage&q=solvent
%20recovery
%20strippers&f=false
15. S. Mehta, "Zero Liquid Discharge Technologies and economics", Envirovision, 2011
16. I. Sajid Hussain, "Case Study of a Zero Liquid Discharge Facility in Textile Dyeing
Effluents at Tirupur", One Day National Workshop on CETPs - Hyderabad-23rd
November 2012
17. "Evaluation and Selection of Available Processes for a Zero-Liquid Discharge System
for the Perris,
California", Ground Water Basin Reclamation, managing Water in the West,
Desalination and Water Purification Research and Development Program Report
No.149
18. "Survey of high recovery and Zero Liquid Discharge Technologies for water utility",
Water Reuse Foundation
19. Concept Engineering Sdn. Bhd. Zero Waste Zero Discharge, Online
at http://www.conceptengineering.net/oil-mill/zero-waste-
discharge/.Dec.,2012.
20. Saeman, W. C., "Crystallization equipment design," Ind. Eng. Chern. 8, 612-622
(1961).
21. Schliephake, D., "Processes for crystallization from solution," Int. Chern. Eng.
22,415--425; 778779 (1982).
22. Wohlk, W. and Hofmann, G., "Types of crystallizers," Int. Chem. Eng. 27, 197-204
(1987).
23. S.Virapan, R.Saravanane and T.Sundararajan, “Recovery & Reuse of RO reject water:
A State-of-the Art Review, ”International Journal of Civil and Environmental
Engineering, ISSN:1701-8285, Vol.36, Issue.2, (2014), pp.1321-1338

B. Page 69
 24. S.Virapan, R.Saravanane and T.Sundararajan, “Performance Evaluation of
Automobile Industry
Effluent Treatment Plant to Achieve Zero Discharge,” International Journal of Applied
Engineering Research, ISSN 0973-4562, Vol. 10, no. 9(2015), pp. 21971-21982
25. S.Virapan, R.Saravanane and V.Murugaiyan, “Study on Reverse Osmosis Reject
handling of Food industry Waste water” Pollution Research, ISSN 0257-8050Vol. 35,
Issue 3, 2016, pp. 511-514.
26. S.Virapan, R.Saravanane and V.Murugaiyan, “ Zero Liquid Discharge (ZLD) in
Industrial Waste waters in India – Need for Sustainable Technologies and a validated
case study”- International Journal of Environmental Engineering and Management,
ISSN 2231-1319 Vol.7,no.1,pp.25-33.
27. Mickley, M., Chapter 19: “RO Concentrate Management” and Appendix C in The
Guidebook to Membrane Desalination Technology. M. Wilf. Balaban Desalination
Publications. L’Aquila, Italy, 2007a.
28. Bagajewicz, M., 2000. A review of recent design procedures for water networks in
refineries and process plants. Comput. Chem. Eng. 24, 2093–2113. Bagajewicz, M.,
Rivas, M., Savelski, M., 1999. A new approach to the design of water utilization
systems with multiple contaminants in process plant. Annu. AIChE Meeting.
29. Brezniak, S., 1999. Process Water Quality and Water Reuse Practices at Low- and
Zero Discharge
Recycled Paperboard Mills. National Council for Air and Stream
Improvement,
Research Triangle Park, NC, pp. 1999.
30. Amit Udgirkar, Sr. Manager; “Zero Liquid Discharge for the Industrial Sector”;
Environmental Engineering, (Praj Industries Ltd).

B. Page 70