Dissertation

Presentation
SEMICONDUCTOR WASTE WATER TREATMENT AND
RECOVERY OF VALUABLE CHEMICALS USING NOVEL
TECHNIQUE

Submitted
To
MGM University,
Chh. Sambhajinagar

Guide
Dr. R.W. Gaikwad

By
Hemant Santosh
Sadafale
 Industry Collaboration 2

VA TECH WABAG over ninety years, making it an industry leader today in the field of total
water management.

WABAG is a pure-play water technology multinational

offering a wide range of solutions focused on
conservation, optimization, recycling and reuse of
resources, directed at addressing water challenges across
the world.
With strong Research & Development and a passion for
innovation, WABAG has honed its skills in handling EPC
projects of any scale across any sector or region.

The company’s key competences, developed over 99

years of plant-building experience, lie in the turnkey
execution and operation of water and wastewater
treatment plants

PhD Dissertation
 Content of Presentation 3

Literature Methodology
Background
Survey Design &
Motivation
Research Papers Fabrication of
Government
Articles Experiment
Policies
2 Setup
1
3

Experimentat Findings
ion on HC Conclusion
Analysis Future Scope
Adsorption Combined
Modified Contribution
Effect Batch 6
adsorbent Study
4 5

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 Background Of Study 4

• Use Mobile, Laptops, Smart

Gazettes, Home appliances is now
integral part of the Human life.

• Electronic industry consists of a

range of products of which
semiconductor is an important one.

• The semiconductor industry has

been a fast growing sector of
economy.

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 Recent Govt. Policy 5

With a 40% increase in allocation compared to last year,

current Budget 2023-2024, presented by finance
minister Nirmala Sitharam has allotted a total of Rs. 16,549
crore for the Ministry of Electronics and Information
Technology, reflecting cognizance of the accelerated
demand for electronics in the post -pandemic era.

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 Origin of The Problem 6

• 30 cm integrated circuit board that holds the

chips in your phone requires at least 2,000
gallons of Water to produce in Various
Process. – Source The Diplomat Aug 2021

SEMICONDUCTOR WASTE WATER TREATMENT AND

RECOVERY OF VALUABLE CHEMICALS USING NOVEL
TECHNIQUE

PhD Dissertation
 Related Research 7

SCIENCE DIRECT PAPERS

Advance research and scholarship with the world's leading
database of peer-reviewed, full-text scientific, technical and
health literature

GOOGLE SCHOLAR
Google Scholar provides a simple way to broadly search
for scholarly literature. Search across a wide variety of
disciplines and sources: articles, theses

SCOPUS
Scopus is a scientific abstract and citation database,
launched by the academic publisher Elsevier as a
competitor to older Web of Science in 2004

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 Literature Review 8

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 Literature Review 9

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 Literature Review 10

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 Problem Statement 11

 Problem due to treatment of CMP

 Conventional treatment methods are slow

 Lack of effective treatment method and also single treatment methods are
ineffective.

 Ultrasound cavitation based AOP’s are not suitable for scale up

 Need of effective treatment methodology for the degradation of heavy complex

metal and chemicals from the semiconductor industry.

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 12
Objectives of the work

 Development of wastewater treatment system based on hydrodynamic cavitation

and H2O2 addition.

 Development of hybrid system for dye wastewater treatment by combining

hydrodynamic cavitation with Natural Zeolite.

 Optimization of various parameters such as Concentration. pH, inlet pressure to the

cavitation device, Natural Zeolite, Modified Zeolite, Quantity of Zeolite loading in,
inlet flow rate to the bed, H2O2 addition for removal of organic contents.

 Recovery of Cu and Zn

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 Objective 13

Combine Effect of
Hydrodynamic
1 Cavitation
HC
+ Adsorption
3
HC Modified Zeolite

Methodolo
gy

Adsorption Recovery of the

2 using Zeolite
+
Copper (Cu)
Zinc (Zn)
4
Modified
Zeolite

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 Cavitation Phenomena 14

 Fluctuating pressure in shear layer of water jets (hydrodynamic) cause pre-existing microscopic bubble
nuclei to grow explosively and then collapse violently.

 Sudden collapse of these cavities exhibits the higher temperatures and pressures of 5000K and 1000atm
respectively.
 The existence of these extreme conditions during cavity collapse makes the surrounding water molecules
dissociate thermally into H● and OH● free radicals.
 Free radicals diffuse into the water and oxidize with organic pollutants.

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 Mechanism of Cavitation 15

Water dissociates under extreme physical conditions generated at cavitation bubble

collapse.

Calculated up to ~5-10,000 °K and 500-1200 atm (sec lifetime).

Forms free radicals:

H2O  H + OH

H + H  H2

OH + OH  H2O2

OH + ORGANIC  CO2 + H2O + …

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 Wastewater Samples 16

• Autonomous scientific society under Ministry of Electronics

& Information Technology, Govt. of India

• Dedicated to the furtherance of competent research

and development in the firmament of Electronic
Materials, the Centre for Materials for Electronics
Technology

PhD Dissertation
 Analysis of Sample 17

Sr. no. Parameter Unit Result Limit Test Method Name Sr. no. Parameter Unit Result Limit Test Method Name
1 PH 1.06 6.5-8.5 IS 3025 Part 11
16 Arsenic ( As) Mg/lit 0.46 0.01 AS Per APHA
2 Total Dissolved Solids (TDS) Mg/lit 20000 2000 IS 3025 Part 16
17 Zinc (Zn) Mg/lit 13 5 AS Per APHA
3 Total Hardness (CaCO3) Mg/lit ND - IS 3025 Part 21 18 Chromium (Cr) Mg/lit 0.05 AS Per APHA

4 Sulphate (S04) Mg/lit ND - IS 3025 Part 24 19 Selenium ( Se) Mg/lit 1.08 - AS Per APHA

20 Lead (Pb) Mg/lit 0.98 0.01 AS Per APHA

5 Phosphate (PO4) Mg/lit 11 4 mg AS Per APHA
21 Aluminium (AI) Mg/lit 3.88 0.03 AS Per APHA
6 Chloride (Cl) Mg/lit ND - IS 3025 Part 32
22 Nickel (NI) Mg/lit 2.77 0.02 AS Per APHA
7 Total Alkalinity (CaCO3) Mg/lit ND - IS 3025 Part 23
23 Boron ( Br) Mg/lit 1.33 0.5 AS Per APHA
8 Nitrate (N03) Mg/lit 6.55 45 AS Per APHA 24 Sodium (Na) Mg/lit 5 60 AS Per APHA
9 Fluoride Mg/lit 2.22 1.5 AS Per APHA 25 Potassium (K) Mg/lit 4 3000 AS Per APHA
10 Iron (Fe ) Mg/lit NIL - IS 3025 Part 53
11 Calcium (Ca) Mg/lit ND - IS 3025 Part 40
Chemical Oxygen
26 Mg/lit 12480 200 AS Per APHA
12 Manganese ( Mn ) Mg/lit 2 0.1 AS Per APHA Demand (COD)

13 Magnesium ( Mg ) Mg/lit ND - IS 3025 Part 46

27 Biochemical Oxygen Demand Mg/lit 3120 8 AS Per APHA

14 Copper ( Cu ) Mg/lit 3.26 0.05 AS Per APHA (BOD) (at 27 Deg c for 3 Days)

15 Mercury ( Hg ) Mg/lit 0.18 0.0001 AS Per APHA

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 Design & Fabrication of Experimental Set Up 18

1 Pump (1 Hp) Horizontal Suction

Vertical Discharge

2 Flow Measurement

3 Cavitating device (Seat For Cavity)

4 Adsorption Bed

T1 TANK

V-1 To V-6 Valve (Controlling Device)

PI Pressure Indicator

PhD Dissertation
 Design & Fabrication of Experimental Set Up 18

1 Pump (1 Hp) Horizontal Suction

Vertical Discharge

2 Flow Measurement

3 Cavitating device (Seat For Cavity)

4 Adsorption Bed

T1 TANK

V-1 To V-6 Valve (Controlling Device)

PI Pressure Indicator

PhD Dissertation
 Design & Fabrication of Experimental Set Up 18

1 Pump (1 Hp) Horizontal Suction

Vertical Discharge

2 Flow Measurement

3 Cavitating device (Seat For Cavity)

4 Adsorption Bed

T1 TANK

V-1 To V-6 Valve (Controlling Device)

PI Pressure Indicator

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 Experimental Setup 19

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 Installing the orifice Plate 20

SEAT FOR ORIFICE PLATES ORIFICE PLATES

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 Sample Collection For Hydrodynamic Cavitation 21

PLATE- A PLATE- B

Sample Temperature

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 22
Analysis Samples

1 2

Analysis of Sample Analysis of Sample

3 4

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 22
Analysis Samples

1 2

Analysis of Sample Analysis of Sample

3 4

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 23
Analysis Samples

5 6

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 23
Analysis Samples

5 6

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 24
Interpretation of Analysis

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 25
Interpretation of Analysis

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 26
Interpretation of Analysis

Influence of Inlet Pressure on BOD and COD

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 27
Interpretation of Analysis

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 27
Interpretation of Analysis

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 28
Interpretation of Analysis

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 28
Interpretation of Analysis

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 29
Interpretation of Analysis Plate-B

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 29
Interpretation of Analysis Plate-B

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 Interpretation of Analysis Plate-A 30

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 Interpretation of Analysis Plate-A 30

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 Adsorption 31

Adsorption is a process where atoms, ions, or

molecules stick to the surface of a
material. The substance that sticks is called
the adsorbate, and the material that it sticks
to is called the adsorbent.
When the particle on the surface and the
particle in the bulk of the adsorbent are not in
the same environment, adsorption occurs. In
other words, the net force acting on them is not
the same.
Zeolites are among the most widely used adsorbents
for adsorption. Because of their numerous acid sites,
high surface area, and various modification
methods, zeolites have been researched and modified
as adsorbents for various compounds

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 32
Zeolite

Calcium aluminosilicate (CAS)

is naturally occurring silicate
clay.

Natural Zeolite
Powder

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 33
Zeolite Used

Using a granulation machine, the natural zeolite was

combined with bentonite clay, a natural binder, in a 1:1
ratio to create the zeolite granules After being dried,
the granules were baked for two hours at 8000 C

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 Modification of Zeolite 34

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 35
Bed Height

6 Inch
9 Inch
12 Inch

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 36
Adsorption
Treated
Water

Bed Height
12 cm

Modified Zeolite

Semiconductor
Waste Water

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 Sample Collection 37

Sample for Column – 12 Inch

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 38
Zeolite Used

Before Experimentation After Experimentation

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 39
Removal of Cu

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 40
Effect of Concentration

1.2 1.2

1 1

0.8 Co=100 mg/lit Co=150 mg/lit

0.8
C/Co

C/Co
0.6 0.6

0.4 0.4

0.2 0.2

0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Time(Min) Time(Min)

Effect of Concentration on Breakthrough Time For Cu Removal

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 Effect of PH 41

Effect of pH on Breakthrough Time For Cu Removal

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 Effect of Bed Height 42

Effect of Bed Height on Breakthrough Time For Cu Removal

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 Effect of Flow Rate 43

1.2
1.2
1
1
0.8 0.8
5 LPH 10 LPH

C/Co
C/Co

0.6 0.6

0.4 0.4

0.2 0.2

0 0
0 30 60 90 120 150 180 0 20 40 60 80 100 120 140 160 180 200
Time (min) Time (min)

Effect of Flow rate on Breakthrough Time For Cu Removal

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 44
Effect of Concentration

1.2 1.2

1 1 Co = 150 mg/lit
Co= 100 mg/lit
0.8 0.8

C/C0
C/C0

0.6 0.6

0.4 0.4

0.2 0.2

0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Time (min) Time (min)

Effect of Concentration on Breakthrough Time For Zn Removal

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 Effect of PH 45

Effect of pH on Breakthrough Time For Zn Removal

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 Effect of Bed Height 46

Effect of Bed Height on Breakthrough Time For Zn Removal

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 Effect of Flow rate 47

1.2 1.2

1 1

0.8 0.8

C/C0
C/C0

0.6 5 LPH 0.6 10 LPH

0.4 0.4

0.2 0.2

0 0
0 30 60 90 120 150 180 0 30 60 90 120 150 180
Time (min) Time (min)

Effect of Flow rate on Breakthrough Time For Zn Removal

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 Combine Effect of Adsorption Column + 49

Hydrodynamic Cavitation

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 50
Combined Effect of pH on Cu Removal

120

100

Removal
Removal 80
Dye

60
% Of%Cu

40

20
2 4 6 8 10 12
pH

Effect of pH on Cu Removal

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 51
Effect of Concentration on Cu Removal

100

Removal
98

Removal
96

94
Cu
Dye
%Of

92
%

90

88
20 30 40 50 60 70

Dye Concentration (mg/L)

Effect of Concentration on Cu Removal

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 52
Effect of Time on Cu Removal

% Of Cu Removal

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 Analysis of Zeolite 53

Modified Zeolite before & after the experimentation

FTIR/XRD/SEM/BET

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 57

2 m

SEM and Energy Dispersive X-ray Analysis (EDAX) for zeolite before adsorption

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 54
FTIR and XRD
Transmittance (a.u.)

FTIR analysis and XRD analysis for Zeolite after the adsorption

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 55
SEM

EDS layered image of sample

SEM image of zeolite after the
adsorption of metal

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 56
EDS

Elemental Dot mapping image of sample

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 59
Recovery of Cu

The regenerative solution HCL, from the tank allowed to

flow through the exchange column drop by drop for 3 Hrs.
HCL regenerant removes the cations adsorbed during the
service cycle and converts the resin to hydrogen form for
the next service cycle. This solution is collected in the
bottom tank. The recovery of the metal is achieved in this
step.

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 60
Recovery of Cu

In the first step, Cu is adsorbed onto the solid resin phase by exchange with H which is
combined with H+ in the aqueous solution to form H 2SO4.
In the second step, the exhausted resins are regenerated using 5 wt % HCL and the
adsorbed Cu in the solid phase is replaced by H and is detached and combines with Cl -
in the aqueous solution to form CuCl2 . These first two steps of ion exchange can be
represented by

Where RH represents the H-type ion exchange resin.

It is noted that between the adsorption and desorption steps, CuSO4 in the original waste
acid solution is significantly converted to form CuCl 2 after desorption, as shown in the
second reaction.

These steps complete the process of copper removal, recovery and acid neutralization.

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 Mathematical Modeling 61

The mathematical modelling of semiconductor industry effluents aims to predict

and control remedies for unexpected parameter variations.

The Langmuir isotherm explained the favourable, nonlinear adsorption isotherm.

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 Overall Conclusion 62

 The Hydrodynamic cavitation is significantly useful for effective degradation of

pollutants from the semiconductor industries.
 The Nucleophile functional group based modification of zeolite shows
effective separation of metal particles from the wastewater.
 The requirement of modified zeolite on the qualitative basis is much lower as
compared to the unmodified zeolite. The Overall effective 12 mg of modified
zeolite for 1 lit of the wastewater shows the effective separation of Cu and Zn
metal particles more than 90%.

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 Overall Conclusion 63

 The hybrid approach with combination of HC and modified zeolite

based adsorption shows significant BOD and COD removal up to 92%

and 86% respectively with only 30 min of operation.

 The operating parameters of HC, such as inlet pressure, pH of the

solution etc. play a crucial role in deciding the effectiveness of

treatment and final obtained extent of degradation.

 A recovery of the valuable heavy metals is investigated and found 32%.

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 Publications 64

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 Presentation in International Conferences 65

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 66
Patent

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 THANK YOU

PhD Dissertation