An Overview on Zero Liquid Discharge Technology

and Promoting ZLD in Bangladesh

CHE 6405
Water Pollution and Control

Submitted to
DR. MD SHAHINOOR ISLAM
Assistant Professor
Department of Chemical Engineering, BUET

Submitted by
TANVIR AHMED
Student No. 1015022027
SABRINA KHAN
Student No. 1015022029
Department of Chemical Engineering, BUET

ABSTRACT
Zero liquid discharge (ZLD) refers to a treatment process in which the plant discharges no
liquid effluent into surface waters, in effect completely eliminating the environmental
pollution associated with treatment. Apart from this benefit, a ZLD process also makes
effective use of wastewater treatment, recycling, and reuse, thereby contributing to water
conservation through reduced intake of fresh water. This paper includes effluent treatment
methods, the prospect of ZLD in Bangladesh, the benefits & challenges and equipment
overviews. Zero discharge solutions can be accomplished by concentrating the effluent using
various techniques, including membrane-based and multiple effect evaporation-based
systems, and recovery and recycling of water.

TABLE OF CONTENTS
ABSTRACT ................................................................................................................ i
TABLE OF CONTENTS ...........................................................................................ii
LIST OF FIGURES AND TABLES......................................................................... iv
1

INTRODUCTION ............................................................................................................. 1
1.1

Zero Liquid Discharge ............................................................................................... 1

Effluent Treatment Methods .............................................................................................. 3

2.1

Physical Unit Operations [4] ...................................................................................... 3

2.1.1 Screening................................................................................................................ 3
2.1.2 Flow Equalization .................................................................................................. 3
2.1.3 Sedimentation and Filtration .................................................................................. 4
2.1.4 Aeration.................................................................................................................. 4
2.2

Chemical Unit Processes [4] ...................................................................................... 4

2.2.1 pH Control ............................................................................................................. 4

2.2.2 Chemical Coagulation and Flocculation ................................................................ 5
2.3

Biological Unit Processes [4]..................................................................................... 5

2.3.1 Activated Sludge .................................................................................................... 6

2.3.2 Fixed Film .............................................................................................................. 6

2.4

Physio-chemical Treatment ....................................................................................... 7

2.5

Physio-chemical and Biological Treatment ............................................................... 7

Introduction of ZLD in bangladesh.................................................................................... 8

3.1

Reasons to Introduction of ZLD in Bangladesh ........................................................ 8

3.1.1 Ground Water Level .............................................................................................. 8

3.1.2 National Standards for Wastewater ....................................................................... 9
3.2

Benefits and Challenges Facing the ZLD ................................................................ 10

3.2.1 Benefits of ZLD ................................................................................................... 10

3.2.2 Challenges of ZLD ............................................................................................... 11
ii

Overview on Zero Liquid discharge ................................................................................ 12

4.1

Process Selection ..................................................................................................... 13

4.2

Some ZLD Process Examples:................................................................................. 16

4.2.1 Ionics EnChem. A ZLD-solution for the semiconductor industry ..................... 16

4.2.2 Tenergys plating waste water recovery system .................................................. 17
5

Achieving ZLD: Equipment Overview ............................................................................ 18

5.1

Reverse Osmosis (RO) ............................................................................................. 18

5.2

Electro-dialysis reversal (EDR) ............................................................................... 19

5.3

Evaporator ................................................................................................................ 19

5.4

Crystallizer ............................................................................................................... 21

5.5

Spray Dryer .............................................................................................................. 21

CONCLUSION ................................................................................................................ 22
REFERENCES ........................................................................................................ 23

iii

LIST OF FIGURES AND TABLES

FIGURES:
Figure 2-1: Typical Flow Diagram of a Biological Treatment Plant ......................................... 6
Figure 4-1: General ZLD Technology Process ........................................................................ 12
Figure 4-2: Zero liquid discharge system flow diagram .......................................................... 14
Figure 4-3: Example of how a present ZLD-system is integrated in a power plant ................ 15
Figure 4-4: Ionics ZLD-system for the semiconductor industry ............................................ 16
Figure 4-5: Tenergys ZLD-system for the plating industry ................................................... 17
Figure 5-1: Industrial Reverse Osmosis Process ..................................................................... 18
Figure 5-2: Industrial Electro-dialysis reversal system ........................................................... 19
Figure 5-3: A falling film evaporator, also called a brine concentrator [16] ........................... 20
Figure 5-4: The heat flows in a crystallizer ............................................................................. 21

TABLES:
Table 2-1: Wastewater Treatment Levels and Processes [3] ..................................................... 3
Table 2-2: Biological Treatment Processes ............................................................................... 5

iv

CHAPTER 1
1

INTRODUCTION

In the past several decades, industrial production has increased in Bangladesh. Water
consumption for industrial use has consequently risen and will continue to rise. Ecological
issues are an integral and important part of the environmental issues challenging Bangladesh.
Poor air quality, water pollution, and garbage all affect the quality of food and the
environment necessary for ecosystems to thrive. Nowadays, Environmental concerns are
steadily increasing, and regulatory authorities are constantly tightening the environmental
standards, insisting that industries adopt advanced wastewater treatment technologies,
including ZLD solutions.
Today few industries are concerned with developing ZLD solutions that address some of the
following challenges:
1. Innovative and customized solution offerings
2. Highly corrosive effluent and the selection of metallurgy
3. Recovery of pure process condensate for reuse and recycling
4. Operating temperature and pressures and scaling and fouling tendency
5. Continuous operation of the system with minimization of cleaning-in-place (CIP) effluents
6. Selection of appropriate type of evaporator effects in multi effect evaporation system
7. Optimization of CAPEX and OPEX for ZLD solutions.
1.1

Zero Liquid Discharge

Any process or combination of processes, by virtue of which there is no liquid effluent, or

discharge from a process plant
It implies that wastewater is treated and effectively recycled and reused such that there is no
effluent discharge. ZLD is usually accomplished by concentrating the effluent using various
techniques, including membrane-based and multi effect evaporation based systems. ZLD
involves:

 The elimination of the liquid waste effluent stream from the plant
The recycling of recovered water and solids
The establishment of no liquid pollutant norms.
If implemented correctly, ZLD has the potential not just to alleviate concerns of effluent
discharge but also to lead to water conservation, which is critical for regions experiencing
water scarcity.
Typically, ZLD systems are used where there are environmental limitations such as water
insufficiency and where strong environmental regulations are obligatory; either because water
resources are scarce or an industrys activity is highly polluting. In principle, the end goal of
ZLD is to eliminate (to the extent feasible) the discharge or disposal of liquid waste from a
facility, wherein no wastewater gets discharged to surface water bodies. This is ultimately
accomplished by recycling, reusing or reducing the volume of waste stream, primarily
including water-based streams. The non-water components of a wastewater come from either
the manufacturing process itself or from a cleaning process and can include any number of
materials, chemicals, oils or solids. Typical waste streams that produce large volumes of
wastewater include cooling tower blowdown, gas scrubber blowdown, ion-exchange
regeneration effluent and rinses, plant wash down and rain water runoff, and process wastes.
These come from a wide variety of industries, including but certainly not limited to:

Metal Working

Metal Finishing

Manufacturing/Production

Transportation

Water Treatment

Material Recycling

Pharmaceutical

Food and Beverage

CHAPTER 2
2

EFFLUENT TREATMENT METHODS

Effluent can be treated in a number of different ways depending on the level of treatment
required. These levels are known as preliminary, primary, secondary and tertiary (or
advanced) [1]. Conventional wastewater treatment consists of a combination of physical,
chemical, and biological processes (Table 2-1) and operations to remove solids, organic
matter and, sometimes, nutrients from wastewater [2]. Many of these processes will be used
together in a single treatment plant.
Table 2-1: Wastewater Treatment Levels and Processes [3]
Treatment Level

Description

Process

Preliminary

Removal of large solids such as rags, sticks,

grit and grease that may damage equipment
or result in operational problems
Removal of floating and settle able materials
such as suspended solids and organic matter
Removal of biodegradable organic matter
and suspended solids
Removal of residual suspended solids /
dissolved solids

Physical

Primary
Secondary
Tertiary/Advanced

Physical and
chemical
Biological and
chemical
Physical, chemical
and biological

2.1 Physical Unit Operations [4]

Common physical unit operations include among other processes screening, flow
equalization, sedimentation, clarification and aeration.
2.1.1 Screening
A screen with openings of uniform size is used to remove large solids such as plastics, cloth,
polythene etc. which may damage process equipment, reduce the effectiveness of the ETP or
contaminate waterways.
2.1.2 Flow Equalization
There are several different steps in the industrial processes and therefore wastewater quality
and quantity varies over time. ETPs are usually designed to treat wastewater that has a more
or less constant flow and a quality that only fluctuates within a narrow range. The
equalization tank overcomes this by collecting and storing the waste, allowing it to mix and
become a regular quality before it is pumped to the treatment units at a constant rate. To

determine the required volume of an equalization tank the hourly variation of flow needs to
be determined.
2.1.3 Sedimentation and Filtration
The flocs formed in flocculation are large enough to be removed by gravitational settling,
also known as sedimentation. This is achieved in a tank referred to as the sedimentation tank,
settling tank or clarifier. Sedimentation is also used to remove grit and suspended solids, to
produce clarified effluent, and to thicken the sludge produced in biological treatment.
Flocculation and sedimentation should remove most of the suspended solids and a portion of
the BOD [5].
2.1.4 Aeration
Aeration is required in biological treatment processes to provide oxygen to the microorganisms that breakdown the organic waste. Two main methods are used for this, either
mechanical agitation of the water so that air from the atmosphere enters the water, or by
introducing air into the tank through diffusers.

2.2 Chemical Unit Processes [4]

Chemical unit processes are always used with physical operations and may also be used with
biological treatment processes, although it is possible to have a purely physio-chemical plant
with no biological treatment. Chemical processes use the addition of chemicals to the
wastewater to bring about changes in its quality. They include pH control, coagulation,
chemical precipitation and oxidation.
2.2.1 pH Control
Waste from textile industries is rarely pH neutral. Certain processes such as reactive dyeing
require large quantities of alkali but pretreatments and some washes can be acidic. It is
therefore necessary to adjust the pH in the treatment process to make the wastewater pH
neutral. This is particularly important if biological treatment is being used, as the
microorganisms used in biological treatment require a pH in the range of 6-8 and will be
killed by highly acidic or alkali wastewater. Various chemicals are used for pH control. For
acidic wastes (low pH) sodium hydroxide, sodium carbonate, calcium carbonate or calcium
hydroxide, may be added among other things. For alkali wastes (high pH) sulphuric acid or
hydrochloric acid may be added. Acids can cause corrosion of equipment and care must be
taken in choosing which acid to use. Hydrocholoric acid is probably better from an

environmental view point but can corrode stainless steel therefore plastic or appropriately
coated pumps and pipes must be used.
2.2.2 Chemical Coagulation and Flocculation
Coagulation is a complex process but generally refers to collecting into a larger mass the
minute solid particles dispersed in a liquid. Chemical coagulants such as aluminium sulphate
(alum) or ferric sulphate may be added to wastewater to improve the attraction of fine
particles so that they come together and form larger particles called flocs. A chemical
flocculent, usually a polyelectrolyte, enhances the flocculation process by bringing together
particles to form larger flocs, which settle out more quickly Flocculation is aided by
gentle mixing which causes the particles to collide.

2.3 Biological Unit Processes [4]

Biological treatment is an important and integral part of any wastewater treatment plant that
treats wastewater from either municipality or industry having soluble organic impurities or a
mix of the two types of wastewater sources. The obvious economic advantage, both in terms
of capital investment and operating costs, of biological treatment over other treatment
processes like chemical oxidation; thermal oxidation etc. has cemented its place in any
integrated wastewater treatment plant.
Biological treatment using aerobic activated sludge process has been in practice for well over
a century. Increasing pressure to meet more stringent discharge standards or not being
allowed to discharge treated effluent has led to implementation of a variety of advanced
biological treatment processes in recent years.
The objective of biological treatment of industrial wastewater is to remove, or reduce the
concentration of, organic and inorganic compounds. Biological treatment process can take
many forms (Table 2) but all are based around microorganisms, mainly bacteria.
Table 2-2: Biological Treatment Processes
Treatment Processes
Definition
Suspended-growth processes e.g. activated The micro-organisms are maintained in
sludge
suspension in the liquid
Attached-growth processes or fixed-film The micro-organisms are attached to some
processes
inert medium such as rock or inert plastics
Combined processes
A combination of suspended-growth
and fixed-film

These microorganisms use components of the effluent as their food and in doing so break
them down to fewer complexes and less hazardous compounds. In the process the
microorganisms increase in number.

Figure 2-1: Typical Flow Diagram of a Biological Treatment Plant

* A sludge recycle line is essential for activated sludge systems but is not needed for fixed film
systems. ** The aeration unit can be either activated sludge or a fixed film reactor.

There are two main types of processes, these involve suspended microbial growth (e.g.
activated sludge) and attached microbial growth (e.g. fixed film). With both approaches large
populations of microorganisms are brought into contact with effluent in the presence of an
excess of oxygen. In both systems the microbial population has to be retained in a tank
referred to as the reactor. With suspended growth systems microbes grow in small aggregates
or flocs (this is known as activated sludge).
2.3.1 Activated Sludge
Activated sludge (AS) leaves the reactor with the treated effluent but is settled out in a
clarifier and returned to the aeration unit to recycle the bacteria. If the amount of AS is
excessive some may be disposed of rather than being recycled.
2.3.2 Fixed Film
In fixed film systems the microbial population grows as a thin layer (a bio-film) on the
surface of an inert support medium. The classical fixed film system is known as a percolating
6

or biological filter and uses small stones as a medium to support microbial growth. In the
more modern system microbes grow on plastic supports. In the traditional percolating filters
effluent is sprayed over the medium and trickles through a packed bed with oxygen entering
from the air. In more recent reactor designs, the medium (usually plastic) is submerged in
effluent and air is blown into the base of the reactor. Submerged fixed film reactors using
plastic media require much less land. Fixed film systems require a final clarifier to remove
particles of biofilm that become detached from the medium.
Biological treatment plants must be carefully managed as they use live microorganisms to
digest the pollutants. For example some of the compounds in the wastewater may be toxic to
the bacteria used, and pre-treatment with physical operations or chemical processes may be
necessary. It is also important to monitor and control pH as adverse pH may result in death of
the microorganisms. The ETP must be properly aerated and must be operated 24 hours a day,
365 days a year to ensure that the bacteria are provided with sufficient food (i.e.
wastewater) and oxygen to keep them alive. Like humans, microorganisms need a balanced
diet with sources of carbon, nitrogen, phosphorus and sulphur.

2.4 Physio-chemical Treatment

The basic units needed for a stand-alone physio-chemical treatment plant are screening, an
equalization unit, a pH control unit, chemical storage tanks, a mixing unit, a flocculation unit,
a settling unit and a sludge dewatering unit.

2.5 Physio-chemical and Biological Treatment

In this type of treatment a combination of physical operations, and physio-chemical and
biological processes are used. The basic units needed for a physio-chemical and biological
treatment plant are screening, an equalization unit, a pH control unit, chemical storage tanks,
mixing units, flocculation units, a primary settling unit, an aeration unit, and a secondary
settling unit. The physio-chemical unit always comes before the biological unit.

CHAPTER 3
3

INTRODUCTION OF ZLD IN BANGLADESH

The textile sector is the backbone of Bangladeshs economy. However, the industry is faced
with many challenges due to high resource (energy, water and chemical) footprint and its
consequent environmental impact. Water usage by the textile industry in Bangladesh is
estimated to be 1,500 million cubic meters, which is principally made of groundwater.
Around 70% of this water consumption takes place in the wet processing of textiles, which
involves washing, dyeing, and finishing of textiles. Besides high water footprint, the textile
industry also faces the challenge of dealing with the problem of effluent discharge and the
use of coagulants and chemicals for its treatment.
Realizing the scale of these issues and the urgent need for addressing them, Bangladesh
Government has issued the Zero Liquid Discharge (ZLD) Regulation for the textile sector.
This poses a huge challenge for the industry, particularly for the small and medium sized
units. The key to its successful implementation would be a cautious and practical approach
and view this as an opportunity to deal with the pressing environmental challenges in a
sustainable manner [6].

3.1 Reasons to Introduction of ZLD in Bangladesh

Reasons behind, why Zero Liquid Discharge (ZLD) technology should introduced in
Bangladesh as soon as possible are listed below:
3.1.1 Ground Water Level
Like many natural resources, groundwater is being exploited at an increasing rate all over the
world. Groundwater is generally preferred as a source of potable water in the developing
world because of its ready availability and natural protection from contamination. It is
commonly used for irrigation and to supply industrial and domestic needs. A lack of proper
understanding of the groundwater system, in terms of resource utilization, is one of the major
limitations to the effective management of groundwater resources [7].
Dhaka is dependent primarily on groundwater for the urban water supply; about 84% of the
present municipal water supply comes from groundwater and 16% is from surface water [8].
The dependence on groundwater for domestic, industrial, and commercial water supply in the
city area was more than 95% prior to the commissioning of a large surface water treatment
plant (Sayedabad Surface Water Treatment Plant) in 2002.
8

The capitals groundwater levels are falling rapidly due to excessive extractions to meet the
needs of its growing population, said Dhaka Water Supply and Sewerage Authority. The
capitals underground water level has dropped to 60 meters below ground level, according to
DWASA. In 2011, the capitals ground water level was 51 meters below the ground level,
according to a study of Bangladesh Agricultural Development Corporation. The groundwater
levels in the capital are falling by two to three meters each year, according DWASA [9].
3.1.2 National Standards for Wastewater
Effluent from textile dyeing industries must meet the national effluent discharge quality
standards set by the Government of Bangladesh, including the Quality Standards for
Classified Industries (Table 3-1), and may also need to meet additional standards set by
international textile buyers. Consequently any ETP must be designed and operated in such a
way that it treats the wastewater to these standards [10].
Table 3-1: Discharge Quality Standard for Classified Industries - Composite Textile Plant
and Large Processing Units
Parameter

Limit, Bangladesh Standard (mg/L)

pH

6.5-9

Total Suspended Solid (TSS)

2100

Total Dissolved Solid (TDS)

100

Biochemical Oxygen Demand for 5 days

(BOD5)
Chemical Oxygen Demand (COD)

50

SO42-

400

S2-

Total Chromium

Phenolic Compounds

200

The regulations state that these quality standards must be ensured from the moment of going
into trial production for industrial units. They also state that the Department of Environment
can undertake spot checks at any time and the pollution levels must not exceed these quality
standards. Furthermore, the quality standards may be enforced in a more stringent manner if
considered necessary in view of the environmental conditions of a particular situation [11].

The waste discharge quality standards differ according to the point of disposal. So, the
standards are different for inland surface water (ponds, tanks, water bodies, water holes,
canals, river, springs or estuaries); public sewers (any sewer connected with fully combined
processing plant including primary and secondary treatment); and irrigated land defined as an
appropriately irrigated plantation area of specified crops based on quantity and quality of
wastewater [11].
Bangladesh Government is planning to lower the current limiting standards such as BOD
level to 30 mg/L from 50 mg/L, COD level to 150 mg/L from 200 mg/L. But with current
technology this is not possible to attain such result, so improvement of technology and
current process must be introduced.

3.2 Benefits and Challenges Facing the ZLD

While successful implementation of ZLD in the textile sector in Bangladesh would have
significant environmental, economic and social benefits, it is also thwart with many
challenges. It is important that before the ZLD mandate is rolled out in Bangladesh, the
regulatory authorities and the industry are fully aware of the pros and cons of such a program
in terms of the possible benefits and the challenges or roadblocks that can come in the way of
its successful implementation.
3.2.1 Benefits of ZLD
i.

Implementation of ZLD had encouraged the industry to closely monitor water usage,
avoiding of wastages and to promote recycling. For example, the textile dyeing
industry moved from conventional Winches which used more water (1:16 Liquor of
Fabric weight to Water volume) to less water consuming Soft Flow Machines with
1:8 Liquor ratio and many are increasingly moving towards even lower water
consuming Air flow Machines with 1:3.5 Liquor ratios to increase their production
while generating lower volumes of effluent.

ii.

The high recovery of water (>90-95%) and the recovery of salt has mitigated the
higher cost of operation of a ZLD system.

iii.

The implementation of ZLD paved the way for a more sustainable growth of the
industry while meeting most stringent environmental norms.

iv.

Reduction in water demand from the Industry by implementation of ZLD enabled in

freeing up water for Agriculture and Domestic demands.

10

v.

The environmental problems created earlier has been arrested and the degraded land
and water bodies are slowly recovering back

vi.

Sustainable growth of the industry also implies growth in economy and sustainable
livelihood for many people who are dependent on the textile dyeing cluster either
directly or indirectly.

3.2.2 Challenges of ZLD

i.

ZLD results in generation of hazardous solid wastes (particularly waste mixed salt)
causing disposal challenges, which is being stored in storage yards within the CETPs.

ii.

For the chemical sludge, the best way to dispose it off is its gainful utilization for
cement co-processing but it needs tie up with a willing/recipient cement company.

iii.

The high cost of operation of a ZLD is also a major challenge. The recovery of water
and salt (Sodium sulphate and brine) offsets this costs significantly, but it would apply
only to water scarce areas where the cost of water is high.

iv.

High Carbon foot print of a ZLD facility is another major concern. The typical power
consumption ranges from 8 to 10 kW/m3. The thermal evaporators alone consume
about 20-40 kW/m3 in addition to several tons of firewood for the boilers.

v.

Non uniform application of ZLD standards across the country for similar industries
has serious impact on the competitiveness of the local industry.

vi.

Implementation of ZLD requires a host of advanced wastewater treatment

technologies. Implementation of ZLD in Tamilnadu has highlighted several
Technology shortcomings such as in Thermal evaporation & brine concentration, Salt
separation and Crystallization, Colour removal etc.

11

CHAPTER 4
4

OVERVIEW ON ZERO LIQUID DISCHARGE

Zero Liquid Discharge (ZLD) represents the ultimate cutting-edge treatment system for the
total elimination of wastewater effluent into neighboring waterways. The ZLD System
removes dissolved solids from the wastewater and returns distilled water to the process
(source). Reverse osmosis (membrane filtration) may be used to concentrate a portion of the
waste stream and return the clean permeate to the process. In this case, a much smaller
volume (the reject) will require evaporation, thus enhancing performance and reducing power
consumption. In many cases, falling film evaporation is used to further concentrate the brine
prior to crystallization [12].

Figure 4-1: General ZLD Technology Process

For over 30 years vapor compression evaporation has been the most useful technology to
achieve zero liquid discharge. Evaporation recovers about 95 % of a wastewater as distillate
for reuse. Waste brine can then be reduced to solids in a crystallizer/dewatering device.
However, evaporation alone can be an expensive option when flow rates are considerable.
One way to solve this problem is to integrate membrane processes with evaporation. These
12

technologies are nowadays often combined to provide complete ZLD-systems. The most
common membrane processes used so far are reverse osmosis (RO) and electro-dialysis
reversal (EDR). By combining these technologies with evaporation and crystallization ZLDsystems have become less expensive. They are however combined differently depending on
the circumstances, see chapter general guidelines. Together with these components, a variety
of other well-known water treatment technologies are used in ZLD-systems for pre-treatment
and polishing treatment [13]. These treatments are:

pH adjustment

de-gasifier

mixed/separate bed

oil/water separator

neutralization

oxidation (UV, ozone, sodium hypochlorite)

dissolved air flotation (DAF)

carbon adsorption

anaerobic or aerobic digestion

The variation of ZLD-systems are, as previously mentioned, endless. Below, I have tried to
display a couple of ZLD-systems applied in different industries. The power plant system, see
figure 1, is the most general system, while the other two, see figure 2 and 3, are commercial
ZLD-systems from two water treatment companies.

4.1 Process Selection

The individual processing steps (and their abbreviations used in the illustration) of the five
conventional ZLD processing schemes for treating wastewater include:

Reverse osmosis (RO)

Lime softening (LS)

Thermal brine concentrator (BC)

Thermal crystallizer (CRYST)

Spray dryer (SD) (used only for low-volume flows)

Evaporation pond (EP)

Landfill (LF)

13

Product water is produced by the RO, BC, and CRYST process steps. Processing steps for the
wastewater treatment, beginning with concentrate (conc.), are as follows [14]:

Scheme 1A:

conc.

BC

Scheme 1B:

conc.

BC CRYST EP

Scheme 2A:

conc. LS RO BC

Scheme 2B:

conc. LS RO BC CRYST EP

Scheme 3:

conc. LS RO

EP

EP

EP

Solids produced from the lime softening and crystallization steps go to a landfill.
If the water flow rate is small, not many components are necessary. The following general
guidelines are accepted today [13]:

Below 10 gpm of feed crystallizers and/or spray dyers can be combined.

10 50 gpm of feed use a crystallizer alone.

50 100 gpm of unsaturated feed use an RO/EDR/crystallizer combination.

50 100 gpm of saturated feed use an evaporator/crystallizer combination.

100 500 gpm of feed either an RO/crystallizer or an evaporator/crystallizer

combination may be the most economical.

500 1000 gpm of feed all three should be used

Figure 4-2: Zero liquid discharge system flow diagram

14

Figure 4-3: Example of how a present ZLD-system is integrated in a power plant

15

4.2 Some ZLD Process Examples:

4.2.1 Ionics EnChem. A ZLD-solution for the semiconductor industry
Ionic claims that their water treatment system, the EnChem, removes more than 99% of the
contaminating materials. The EnChem technology is also capable of reducing water usage
during the semiconductor manufacturing process by up to 85% through reclaim. Ionics
EnChem technology is a low pressure water treatment solution. It is specifically designed to
reduce water consumption and operating costs [15].

Figure 4-4: Ionics ZLD-system for the semiconductor industry

The water to be treated has to go through four steps; through the reaction tank, on to the
filtration, on to the backflush and finally to de-watering. Each step is described below:
Step 1. Reaction step. Influent waste water is pH adjusted, then mixed with organic and
inorganic coagulant additives. The polymers react with the contaminants to form spheres. The
reaction is complete in a few minutes.
Step 2. Filtration. The filtration is accomplished through low pressure membranes. The clean
water then exits the top of the filter while solids are retained on the filter membrane.
Operating pressures remain below 15 psi (1 bar).
Step 3. Backflush. The membranes are pulsed to remove solids and then solids are pumped to
a settling tank.
Step 4. Solids formation/De-watering. Solids are pumped to a holding tank for further
settling. Conventional filter presses can be used to further separate and de-water solids.
Overflow filter press water is returned to the reaction tank.

16

4.2.2 Tenergys plating waste water recovery system

This ZLD-system is used for the Ni and Cr plating industry. Filtration is combined with
separated bed and an evaporator. The system can handle flow rates of 50 gpm.

Figure 4-5: Tenergys ZLD-system for the plating industry

In the pre-treatment step ultrafiltration (UF) is combined with carbon filter. UF is used for
removal of volatile organics, virus and bacteria and suspended solids. The carbon filter
contain granular activated carbon media that adsorb impurities within molecule-sized pores.
Oxidants such as chlorine are also removed during their interaction with the carbon surface.
After pre-treatment the water passes through the polishing step, which consists of separate
bed demineralizers, where the salts in the water are separated into positively charged cations
and negatively charged anions. The process begins when the water is passed through cation
exchange resin. The cation resin is in the hydrogen form (H+) and exchanges all the positively
charged ions for hydrogen, thus converting all the impurities in the water into acids. The
water from the cation exchange is then passed through anion exchange resin. Separate bed
means that there are two tanks, one containing cation resin, and the other containing anion
resin. The anion resin is in the hydroxyl form (OH-) and exchanges all the negatively charged
ions into the hydroxyl form, completing the conversion of all impurities into water (H+ + OH H2O), thus providing pure demineralized water.
The concentrates finally feed an evaporator providing clean water for plating, thus
completing the closed ZLD-system.

17

CHAPTER 5
5

ACHIEVING ZLD: EQUIPMENT OVERVIEW

5.1 Reverse Osmosis (RO)

Reverse osmosis is a process where water is pressurized so that it passes through a semipermeable membrane, leaving dissolved inorganic salts and silica behind. As a rough guide to
performance, RO can produce a concentrate containing 30000 ppm total dissolved solids
(TDS). Two problems with RO are that organics will seriously foul RO systems and that RO
requires a feed stream that is free of suspended solids. Because of this it is advisable to
remove organics from wastewater before it enters the RO, so extensive front-end filtration
equipment is required. Some membranes are pH and temperature sensitive, so pH control and
feed equalization may be necessary. RO is also quite energy-intensive. The advantage of RO
over evaporation is that the life cycle costs of RO are about half those of evaporators.

Figure 5-1: Industrial Reverse Osmosis Process

18

5.2 Electro-dialysis reversal (EDR)

Electro-dialysis reversal (EDR) is a membrane process in which electrolytes migrate across
charge-selective membranes in response to an electrical field. In EDR, the polarity of the
electrodes is reversed several times an hour and the fresh water and the concentrated
wastewater are exchanged within the membrane stack to remove fouling and scaling. EDR
differs from RO in that the ions are removed and the water is left behind, whereas in RO, the
water is removed and the ions are left behind. Because of this, silica and dissolved organics
are not removed with an EDR process, which is an important aspect to remember when the
clean stream is reused. Like RO, EDR requires solids and organics removal from the feed for
reliable operation.

Figure 5-2: Industrial Electro-dialysis reversal system

5.3 Evaporator
Evaporators come in all sizes and shapes, for example; falling film-, rising film-, forced
circulation and scraped surface/thin film- and combination evaporator. Evaporators produce a
distillate stream that is very clean, typically containing less than 10 ppm of TDS one of the
main reasons why evaporators are used in a ZLD-system. The most prevalent type is the

19

falling film evaporator, also called brine concentrator, see figure 4. This evaporator can treat
RO or EDR concentrates to a total solids (TS) concentration of 300 000 ppm. At this value
the boiling point rise of the brine results in either an excessively large heat-transfer area
(large capital cost) or an excessively large temperature difference (large operating cost).
Values higher than this makes the combination of a crystallizer and an evaporator more
economical than an evaporator alone.

Figure 5-3: A falling film evaporator, also called a brine concentrator [16]

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5.4 Crystallizer

Figure 5-4: The heat flows in a crystallizer

The crystallizer reduces highly saturated wastewater to dry solids for disposal. High purity
water is recovered from the crystallizer for recycling. A crystallizer may also recover specific
salts from a mixed salt waste stream. The crystallizer is a forced circulation evaporator which
uses a mechanical vapor compressor or plant steam as the energy source.

5.5 Spray Dryer

When a crystallizer is not appropriate, the spray dryer is another method for dewatering the
concentrated slurry left over from the brine concentrator. The spray dryer transforms the
slurry into a fine powder of mixed salts for disposal. The spray dryer atomizes the wastewater
slurry inside a hot chamber, instantly vaporizing the water droplets and leaving only dry salts
behind.

21

CHAPTER 6
6

CONCLUSION

ELGs (Effluent Limiting Guidelines) do change and that requires the manufacturer to act or
to face the consequences of not meeting the guidelines. More often, ELGs become stricter
over time, and the manufacturing facility ends up needing to purchase additional water
treatment equipment and chemicals or to replace their wastewater treatment system
altogether. Adding or replacing water treatment equipment often means adding personnel to
operate it and capital money to purchase it. The additional water treatment costs also
contribute to higher operating costs overall. A zero liquid discharge system eliminates the
need to react to changing ELGs because there is no longer any wastewater that has to meet
the limits. These systems can be used as a stand-alone treatment following wastewater
treatment, or they can be used in conjunction with an industrial water reuse system.
Combining water reuse and ZLD means the added benefit of cost savings on water purchases.
In fact, with the right pretreatment process, the solid waste from the ZLD system can be
disposed in a landfill as non-hazardous waste.

22

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Munter, R., Industrial Wastewater Treatment: Pathways Of Industrial Effluents

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Pescod, M.B., Wastewater Treatment And Use In Agriculture. 1992, Food And
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Eddy, M.a., Wastewater Engineering Treatment and Reuse. Vol. 2nd Ed. 2003:
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Joe Bostjancic, R.L., Getting to Zero Discharge: How Recycle That Last Bit of Really
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Purification Research and Development Program Report No. 149. 2008, U.S.
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