Masters in Environmental Engineering

GUJARAT TECHNOLOGICAL UNIVERSITY- 2020 – 2021

GRADUATE REPORT

ON
Case study of zero effluent discharge systems for recovery of water and salt from textile
effluents

Submitted By

Tanvi M. Joshi (200420717004)

Guided By
Dr. Mehali J. Mehta

Prof. Ankita Parmar

SARVAJANIK EDUCATION SOCIETY

Sarvajanik College of Engineering & Technology

DR. R. K. DESAI MARG, ATHWALINES, SURAT – 395001

Towards progressive civilization…

1|Page
 SARVAJANIK EDUCATION SOCIETY

Sarvajanik College of Engineering & Technology

DR. R. K. DESAI MARG, ATHWALINES, SURAT – 395001

Towards progressive civilization…….

PG Centre
Masters in Environmental Engineering
GUJARAT TECHNOLOGICAL UNIVERSITY 2020-2021

Certificate

This is to certify that this project report is benefited work on

Case study of zero effluent discharge systems for recovery of water and salt from textile
effluents

Submitted By
Tanvi M. Joshi (200420717004)

Student of
M.E. Environmental Engineering

It has been completed under my guidance and supervision. This work forms part of the
requirement for the award of Master’s Degree (Environmental Engineering) under the
Subject – Industrial Waste and Wastewater Treatment
Conferred by the

Prof. Mehali Mehta Prof.AnkitaParmar Dr. Himanshu Padhya Dr. Pratima Patel
Subject teacher Subject teacher PG Incharge Head of Department

2|Page
 ME, Environmental Engineering, SCET, Surat

Table of Contents

1.introduction .................................................................................................................................... 3

1.1. General introduction.................................................................................................................... 3

1.2. Why is Zero Liquid Discharge Important? ................................................................................. 4
1.3.Benefits of ZLD plant ................................................................................................................. 5

2.case study ....................................................................................................................................... 6

2.1. Introduction............................................................................................................................. 6

3. Methodology ................................................................................................................................ 11

4 Results and Discussion ................................................................................................................... 13

4.1. Characteristics of raw............................................................................................................. 13
4.2. Analysis of the primary treatment: ......................................................................................... 13
4.3. Performance of pretreatment units: ....................................................................................... 14
4.4. Performance of membrane processes .................................................................................... 14
4.5. Performance of multiple effect evaporator (MEE) system: ...................................................... 15
4.6. Cost analysis : ........................................................................................................................ 16

5. Conclusion: ................................................................................................................................... 17

6.Refrences ...................................................................................................................................... 17

3|Page
Table of figures

Figure 1 zero discharge system for industrial process ...................................................................................................... 3

Figure 2 schematic of effluent treatment and recovery in unit I ...................................................................................... 8
Figure 3 schematic of effluent treatment and recovery in unit II ..................................................................................... 9
Figure 4 schematic of effluent treatment and recovery in unit III .................................................................................. 10
Figure 5 distribution of treatment cost in study area ..................................................................................................... 15
Figure 6 distribution of revenue generation in the study area ....................................................................................... 16

Table 1 Details of ZDTS in study units…………………………………………………………………………………………………..7

2|Page
 1.introduction
1.1. General introduction

Zero liquid discharge (ZLD) is an engineering approach to water treatment where all water is recovered and
contaminants are reduced to solid waste. While many water treatment processes attempt to maximize
recovery of freshwater and minimize waste, ZLD is the most demanding target since the cost and
challenges of recovery increase as the wastewater gets more concentrated. Salinity, scaling compounds,
and organics all increase in concentration, which adds costs associated with managing these increases. ZLD
is achieved by stringing together water treatment technology that can treat wastewater as the
contaminants are concentrated.

Figure 1 zero discharge system for industrial process

There are a number of benefits to targeting zero liquid discharge for an industrial process or facility:

• Lowered waste volumes decrease the cost associated with waste management.
• Recycle water on site, lowering water acquisition costs and risk. Recycling on-site can also result in
less treatment needs, versus treating to meet stringent environmental discharge standards.
• Reduce trucks associated with off-site waste water disposal, and their associated greenhouse gas
impact and community road incident risk.
• Improved environmental performance, and regulatory risk profile for future permitting.
• Some processes may recover valuable resources, for example ammonium sulfate fertilizer or
sodium chloride salt for ice melting.

3|Page
 • Several methods of waste management are classified as zero liquid discharge, despite using
different boundaries to define the point where discharge occurs. Usually, a facility or site property
line that houses the industrial process is considered the border or ‘boundary condition’ where
wastewater must be treated, recycled, and converted to solids for disposal to achieve zero liquid
discharge.

Certain facilities send their liquid waste off-site for treatment, deep well disposal, or incineration and they
consider this to qualify as zero liquid discharge. This approach to zero liquid discharge eliminates
continuous discharge of liquids to surface waters or sewers, but can significantly increase cost.

Some engineers describe their designs as near-zero liquid discharge or minimal liquid discharge to highlight
that they discharge low levels of wastewater, but do not eliminate liquid in their waste. For some facilities,
it may be more economic to approach but not achieve complete ZLD by concentrating brine to lower
volumes. Furthermore, it may be possible to avoid the creation of liquid waste on-site through careful
water conservation or by treating contaminants at their source before they can enter the main flow of
water.

1.2. Why is Zero Liquid Discharge Important?

In a world where freshwater is an increasingly valuable resource, industrial processes threaten its
availability on two fronts, unless the water is treated. Many industrial processes require water, and then
reduce the availability of water for the environment or other processes, or alternately contaminate and
release water that damages the local environment.

Although the history of tighter regulations on wastewater discharge can be traced back to the US
Government’s Clean Water Act of 1972, India and China have been leading the drive for zero liquid
discharge regulations in the last decade. Due to heavy contamination of numerous important rivers by
industrial wastewater, both countries have created regulations that require zero liquid discharge. They
identified that the best means to ensure safe water supplies for the future is to protect rivers and lakes
from pollution. In Europe and North America, the drive towards zero liquid discharge has been pushed by
high costs of wastewater disposal at inland facilities.

These costs are driven both by regulations that limit disposal options and factors influencing the costs of
disposal technologies. Tong and Elimelech suggested that, “as the severe consequences of water pollution
are increasingly recognized and attract more public attention, stricter environmental regulations on
wastewater discharge are expected, which will push more high-polluting industries toward ZLD.”

Another important reason to consider zero liquid discharge is the potential for recovering resources that
are present in wastewater. Some organizations target ZLD for their waste because they can sell the solids
that are produced or reuse them as a part of their industrial process. For example, lithium has been found
in USA oil field brines at almost the same level as South American salars. In another example, gypsum can
be recovered from mine water and flue gas desalinization (FGD) wastewater, which can then be sold to use

4|Page
in drywall manufacturing.

1.3.Benefits of ZLD plant

• Minimizes wastewater discharge.

• Maximizes water recovery.
• Creates a valuable product for sale and further processing.
• Removes many environmental issues.
• Reduces dependence on local water sources.
• Significantly reduces the risk of sanctions within the legislative standards for discharged waste.

5|Page
 2.case study

Assessment of field-scale zero liquid discharge treatment systems for recovery of water
and salt from textile effluents

2.1. Introduction

• The textile dyeing industry demands large quantities of water and produces wastewater having high load of
contaminants. In the textile processing industry, many processing steps are carried out discontinuously,
resulting in different process streams from the same processing steps. More than 80% of the salt and 90% of
the colour is discharged with the dyebath and first rinsing bath. It is logical that by segregating the exhaust
dyebath and the first rinse the major part of the pollution load is isolated and would also enhance the
treatability of the effluent. The trade effluent from dyeing and bleaching units at Tirupur, India, has caused
severe environmental problems.
• Every day about 600-700 t of hosiery fabrics is processed in Tirupur requiring 400-500 t of salt. The salt used
is either sodium chloride (NaCl) or sodium sulphate (Na2SO4). This generates large quantity of effluent, and
the total dissolved solids (TDS) in the treated effluent is in the range of 5000e 7000 mg/l with chloride in the
range of 2000e3500 mg/l as compared to the tolerance limits of 2100 mg/l for TDS and 1000 mg/l for
chlorides. The high level of TDS and chlorides is due to the salt addition in the dyeing process for the fixation
of dyes into the fabric.
• The two main pollutants, namely colour and total dissolved solids, make the textile effluent quite resistant
to biodegradation. Though the colour removal can be effectively achieved by physico-chemical methods, a
large volume of sludge is produced as by-product. The salt is largely unaffected by biological treatment
methods. Apart from their non-biodegradability, the dyeing effluent is intensely coloured and imparts the
same to the receiving water bodies into which it is discharged. Having understood the seriousness of the
water pollution, the regulatory agencies are insisting on treating the wastewaters.

6|Page
Table 1: Details of ZDTS in study units

7|Page
Figure 2 schematic of effluent treatment and recovery in unit I

8|Page
Figure 3 schematic of effluent treatment and recovery in unit II

9|Page
 Figure 4 schematic of effluent treatment and recovery in unit III

to reuse it in the process itself and achieve ‘zero discharge’. Twenty-nine large- and medium-scale dyeing
units in Tirupur have installed zero discharge treatment systems (ZDTS) consisting of different
combinations of treatment technologies. The technical and economic feasibility of these technologies
needs to be studied to arrive at the optimum combination of the treatment techniques. Thus, this paper
focuses on three units which are using a combination of treatment techniques for the recovery and reuse
of water and salt with an in-depth technical and economic analysis.

10 | P a g e
 3. Methodology

In this study, three textile dyeing units were selected based on factors such as production capacity of the
units, salt used, physico-chemical treatment system adopted, membrane processes incorporated, etc. The
details of the units are provided in Table 1.
• The overall schematic of the treatment scheme and the volume of effluent generation is presented
in Figs. 1 & 3. All the units segregated the dyebath from washing effluent. In Unit I the wash water
was subjected to physico-chemical treatment for colour removal after which the decolorized
effluent is sent to the RO. The RO is of two stages and of 300 and 100 m 3 /day capacity,
respectively. The segregated dyebath effluent is sent to the NF of 50 m 3 /day capacity. The
recovered permeate and salt were used as dyebath water. The reject from the second stage RO
and NF was sent to a multiple effect evaporator (MEE) which evaporated at the rate of 1:3.5 (kg
steam: l of effluent). The permeate from the stages I and II RO is combined and reused as process
water.
• The segregated wash water in Unit II was subjected to physico-chemical treatment and ozonation
for reduction in chemical oxygen demand (COD) and colour. The treated effluent was sent to a
three-stage RO of 600 m3 /day, 200 m3 /day and 100 m3 /day capacity, respectively. A nanofiller of
50 m3 / day capacity decolorized the segregated dyebath and the recovered permeate was reused
as dyebath water. The combined reject from the stage III RO and NF was sent to the multiple effect
evaporator (MEE) which evaporated at the rate of 1:5 (kg steam: l of effluent). The condensate
from MEE and permeate from the RO unit were combined and reused as process water. Unit III
generated the maximum amount of effluent (900 m3 /day) among the units studied.

• The segregated wash water was sent to a stage I RO of 700 m3 /day capacity and a stage II RO of
300 m3 /day capacity. The segregated dyebath and the reject from the RO unit was combined and
sent to the MEE which evaporates at the rate of 1:5 (kg steam: l of effluent). The recovery of
sodium sulphate was done by means of a crystallizer.
• The condensate from MEE is used as boiler feed water in all the units. In all the three units,
treatment of the concentrated evaporator residue was by solar evaporation. Composite samples
over a period of 24 h were collected from these units, once in a month for 4 months. These samples
were analysed for colour, pH, total suspended solids (TSS), TDS, chlorides, sulphates, chemical
oxygen demand (COD), total iron, silica and total hardness.
• In Germany, the parameter prescribed to characterize colour of textile effluents is the so-called
11 | P a g e
 ‘DFZ-value’. DFZ, also called spectral absorption coefficient, is an expression of colour in terms of
the maximum value for the extinction of three wavelength (436 nm, 525 nm and 620 nm) ranges of
visible light corresponding to a maximum dye concentration of approximately 1.5 mg/l. This
parameter is defined by the following equation:
𝐴(ƛ)1000
DFZ(ƛ) = 𝐷

Where A(ƛ)= spectral absorbance at wavelength ƛ nm and

D= path length of the cell (mm). The standards prescribed for colour is with respect to the
spectral areas for yellow, red and blue.
• Accordingly, the spectral absorbance of textile effluent at 436 nm, 525 nm and 620 nm was
measured using Spectro-photometer. Silt density index (SDI) was measured and Langelier
saturation index (LSI) was calculated for the samples at the inlet of membrane processes. The
performance of the membrane systems was assessed by the quality of the recovered permeates.
For RO, the water recovery and TDS removal and for NF the salt recovery was taken as the main
criteria for assessing the performance.
• Cost analysis for the unit was done based on data of actual capital costs, operation and
maintenance costs and revenue from water or salt recovery. The operation and maintenance costs
include the actual costs of chemicals used, power, steam, manpower, membrane replacement and
sludge management. Membrane replacement costs have been calculated based on very
conservative estimate of 2 years for membrane life while RO is generally designed taking into
account a normal life of 3 years for membrane.
• The revenue from recovery of water as RO permeate and salt as NF permeate has been calculated
at the rate of Rs. 80/m3 and Rs. 5.60/kg of NaCl. Recovery of Na2SO4 has been calculated at the
market rate of Rs. 9.50/kg. Capital costs have been annualized considering the rate of interest as 5%
and life of the components as 10 years.

𝑃𝑖(1+𝑖)𝑛
Annuity on capital costs=(1+𝑖)𝑛−1

Where,
P = total capital cost,
i =rate of interest = 5% (under technology upgradation fund (TUF) scheme) and
n =life of components in years = 10

12 | P a g e
4 Results and Discussion

4.1. Characteristics of raw

• A comparison of raw effluent characteristics from the study units is presented in Table 2. The
effluents were highly alkaline nature (pH range of 8.3e12.1) due to the addition of caustic soda in
the dyeing process. The TSS in the wash water effluent of Unit I was high (400-460 mg/l) and that of
units II and III ranged from 144 mg/l to 258 mg/l. TDS of dyebath effluent in Unit I was around
50,000 mg/l and that of in units II and III was around 30,000 mg/l. This variation is due to the
difference in the machines, shades and dyes used in the process. The TDS of wash water effluents
of all the units were in the range of 3730e4520 mg/l.
• High TDS is due to the usage of salt at the rate of 30e90 g/l of liquor volume in the dyeing process.
The salt used by units I and II was NaCl and that by Unit III was Na2SO4. The chlorides and sulphates
in the effluent streams are indicative of this. The concentration of chlorides in the dyebath effluent
was around 30,000 mg/l in Unit I and around 15,000 mg/l in Unit II. Sulphates were around 15,000
mg/l in Unit III. In the washing effluent of units, I and II, chloride was around 1700 mg/l and of Unit
III it was 1100 mg/l. COD of the dyebath effluent from units I, II and III was around 2650 mg/l, 1360
mg/l and 850 mg/l, respectively. COD was around 500 mg/l, 290 mg/l and 620 mg/l in the washing
effluents of units I, II and III, respectively. It was observed that the dyebath effluents were strongly
coloured (34.2-1375 m-1) and washing effluents were lightly coloured (12.7e58.3 m-1)

4.2. Analysis of the primary treatment:

• The role of primary treatment in units I, II and III was to remove colour and solids in the effluent so
as to make it fit for feeding to RO. The effluent was fully decolorized by the primary treatment and
was able to meet the discharge limits of 7 m1 ,5m1 and 3 m1 , respectively.
• COD reduction was 60% in Unit I where only physicochemical treatment was used while in units II
and III the COD reduction was in the range of 69-85%, respectively. It can be seen that there is not
much COD reduction by using ozonation. This is supported in studies by Oguz et al. The use of a
biological treatment system in Unit III caused significant COD reduction. A recent study by central
pollution control board (CPCB) also observed similar reduction of 85.5% COD in biological
treatment of textile effluent.
• The COD levels in the treated effluent from the units II and III could meet the permissible limits for
RO membranes (100 mg/l COD). This demonstrated the need for biological treatment system as

13 | P a g e
 part of primary treatment system for COD reduction to meet the feed water quality standards for
RO.

4.3. Performance of pretreatment units:

• Adequate pretreatment of water is essential for trouble-free performance of RO units. The objective
of pretreatment of feed water to RO system is to eliminate scaling and minimize fouling of
membranes by colloidal impurities and bacteria.
• Only Unit II could achieve the permissible limit of 25 mg/l TSS for feeding to the RO. When
compared to the other units, Unit II incorporated the right combination of pretreatment as both
multigrade filter and two-micron cartridge filters (10 mm and 5 mm) were incorporated as
pretreatment. The total iron which could cause membrane fouling was slightly high for Unit I (0.12-
0.66) than units II and III. Significantly Unit III could achieve low levels of iron in the feed water
without the use of iron removal filter which indicated low levels of iron in its raw water.
• Silica which could lead to scaling was well below (1.4-9.7 mg/l) the limits of 15 mg/l in the feed
water. This indicated low silica content of the raw water used. Langelier saturation index (LSI), the
scaling index, was -ve in the units I and II indicating that the effluent was under-saturated with
respect to CaCO3, and has a tendency to remove the existing protective coatings. LSI was +ve with
respect to Unit III which reveals that water is supersaturated with respect to CaCO3 and scaling may
occur.
• SDI, the fouling index, was above the desired level of 3 during the study period. Through an SDI
value of <5 or 5 is considered essential for the efficient operation of the membrane, an SDI value of
3 is desired in the feed water for continuous operation.

4.4. Performance of membrane processes

• The performance of membrane processes in the study units are summarized in Tables 5 and 6. The
TDS in RO permeate was lowest in Unit III with a range of 214-308 mg/l. For units I and II, the TDS
ranged from 640 mg/l to 968 mg/l. The high TDS is indicative of the deterioration of the RO
membranes and their subsequent loss in ion rejection capability.
• The total hardness in the permeate varied from 6 mg/l to 35 mg/l which was within the acceptable
limits for the water to be used in textile processing. The total hardness of above 50 mg/l in the
water retards the effective fixation of dyes into the fabric. In the recent study conducted by CPCB,
it was stated that two-stage RO systems are capable of reducing hardness to significantly lower
levels and as such water with less hardness is very much required by the textile dyeing units. Such
water would also help in reducing the use of chemicals towards the softening of raw water.
• Unit III used RO of two stages and also used the maximum number (53) of membranes when
compared to the other units. In Unit II which used the least number of membranes (25) the overall
permeate quality with respect to TDS suffered. Thus it can be said that rather than increasing the
RO stages, having more number of membranes per stage would enhance the permeate quality. The
average water recovery of 82e91% was higher than the 60% reported by Ciardelli et al.
• A TDS removal efficiency of >90% was observed in this study for all units except for stage I RO of
Unit II (75.8%). This indicated the deterioration of the RO membrane and the need to change it
immediately. The average TDS removal efficiency was higher than the 80.4% removal efficiency
achieved in another study.

14 | P a g e
 The segregated dyebath effluent is treated through NF system in Unit I wherein recovery of water up to
70% and NaCl salt of about 76.8% was observed. In Unit II, the water recovery from NF was about 72.9%
and NaCl salt recovery was about 77.8%. The slightly higher TDS load in the NF feed of Unit I lowered the
water recovery slightly due to increase in osmotic pressure. The salt recovery was in agreement with the
results of 55e97% reported in similar studies. The recovered NaCl in solution form from NF was reused as
dyebath liquor. In Unit III, sodium sulphate salt in crystal form was recovered from crystallizer and reused
in the process.

4.5. Performance of multiple effect evaporator (MEE) system:

• Units I, II, and III had MEE recovering condensate with TDS less than 100 mg/l, for reuse as boiler
feed.
• The operation of multiple effect evaporator required steam. In Unit I, steam energy supplied was
1000 kg/h for evaporating 3500 l/h in three stages and in Unit II, the evaporation of 5000 l/h was
done using 1000 kg/h of steam since it has four stages. In Unit III, evaporation of 10,000 l/h
effluents is done using 2000 kg/h of steam. The recovery of condensate was highest in Unit I
(76.6%). This might be due to the low salt concentration of the feed in Unit I. The operation and
maintenance of MEE requires skilled supervision, and scaling on the tubes of the calandrias has to
be cleaned regularly for maintaining efficiency

Figure 5 distribution of treatment cost in study area

15 | P a g e
 Figure 6 distribution of revenue generation in the study area

4.6. Cost analysis :

• The cost benefit analysis for the three zero liquid discharge treatment units is presented in Table 8.
The operation and maintenance costs included the daily capital cost (calculated @ 5% interest and
10 years lifetime), chemical cost, manpower cost, sludge management cost, power requirements
and membrane replacement costs. The revenue included the profit generated from the recovered
water and salt.
• From the cost analysis it is seen that 55e70% of the total operation and maintenance cost is from
the usage of chemicals and power consumption (Fig. 4). Unit III had the highest in-stallation cost
since it had the maximum number of membranes and larger capacity MEE.
• Steam occupies a major part of the operation cost in Unit III as the MEE is almost twice the capacity
of the other units. Among the units compared Unit I was able to achieve a maximum profit of Rs.
13.90/m3 when compared to Unit III which could achieve only a profit of Rs. 3.60/m 3. Unit II
incurred a loss of Rs. 13.10/m3.
• Though the total revenue was more in units II and III than in Unit I, the high cost incurred towards
maintenance and operation of the larger number of membranes and operation of the higher
16 | P a g e
 capacity MEE resulted in higher operation costs which reduced the margin of profits. The lesser
recovery of salt in Unit II when compared to Unit I substantially decreased the revenue and was the
major reason for the loss of revenue.
• The revenue calculated (Fig. 5) from the amount of salt and water recovered show that the
recovered water from the RO contributes in a major way (>50% of total revenue) followed by the
recovered salt. In Unit I, the factors responsible for its high profit was the lesser quantity of water
treated, which resulted in a significant lowering of the operational costs. The cost is maximum
towards steam consumption in Unit III as it recovers sodium sulphate salt in the crystal form for
reuse in comparison with the other two units which use NF for the recovery of sodium chloride in
solution form.
• The total treatment cost for treatment of 1 m3 of water is less (Rs. 72.30) in Unit I than the current
cost of water procured from outside sources (Rs. 80.00). The annualized profits in Rs. /m3 in units I
and II were 1.69 and 0.97, respectively, which gave a payback period of 8 months and 33 months
for the two units.

5. Conclusion:

• TDS removal efficiency of >90% resulted in permeate having average TDS of 20 mg/l. This coupled
with the high-water recovery of 80e90% made the RO process both technically and economically
viable for recovery and reuse of the wash water.
• The NF permeate containing 70% of the salt of the dyebath was reused and used as dyebath water
demonstrating its suitability for reuse of dyebath effluent. The recovery of sodium chloride in
solution form using NF is more economical than recovery of sodium sulphate using MEE. The use of
NF is more economical if the feed contains higher salt concentrations as it enhances the salt
recovery and generates revenue. Moreover, from the cost analysis it is seen that lowering the usage
of chemicals by better operation and maintenance practices would enhance the economic
feasibility of the treatment systems.

6.Refrences

1. Ciardelli, Gianluca, L. Corsi, and M. Marcucci. "Membrane separation for wastewater reuse in the
textile industry." Resources, conservation and recycling 31.2 (2001): 189-197.
2. O'Donnell, Martin J., et al. "Global and regional effects of potentially modifiable risk factors
associated with acute stroke in 32 countries (INTERSTROKE): a case-control study." The
lancet 388.10046 (2016): 761-775.
3. Schoenberger H. Report about short term consultancy on wastewater treatment systems in the
textile industry. Agency on German Technical Cooperation (GTZ), Centre for Environmental Studies,
Anna University; 1999.
4. Minke R, Rott U. The use of anaerobic processes to solve the wastewater problems of textile
processing industry. International symposium on water management, Istanbul; 1998
5. Ratana J, Anawat S, Piyanoot L. Performance evaluation of nanofiltration membranes for treatment
of effluents containing reactive dye and salt. Desalination 2001;114:74e81.
6. Ciardelli, Gianluca, L. Corsi, and M. Marcucci. "Membrane separation for wastewater reuse in the

17 | P a g e
 textile industry." Resources, conservation and recycling 31, no. 2 (2001): 189-197.
7. Ciardelli G, Corsi L, Marcucci M. Membrane separation for wastewater reuse in the textile industry.
Resources, conservation and recycling. 2001 Feb 1;31(2):189-97

18 | P a g e