Engineered for Tomorrow

UNDER THE GUIDANCE OF

1. Mrs. M Nagapadma NAME OF TEAM MEMBERS:
Associate Professor
Dept of Chemical Engg 1. Ibrahim Shahinshah (USN- 1MJ13CH009)
MVJCE, Bengaluru 2. Mahesh K M (USN- 1MJ13CH011)
2. Dr. Ramdas Balan 3. Sharanya S Nair (USN – 1MJ13CH020)
Head Of Dept,
Dept Of Physics,
MVJCE, Bengaluru
 Engineered for Tomorrow

INTRODUCTION
Major problem faced by the people all over the world ……… Non-Availability of Pure
Drinking Water !!

Waste Water Treatment is a vast field !!!!!!!!

Our Group is concentrating on the Removal of Nitrate from wastewater

WHY NITRATE ?
 Engineered for Tomorrow

Nitrates occurs Naturally in soil deposits and water

Manmade activities- agriculture, sewage , industrial

Effects of nitrate –
•Metheglobinemia or blue baby disease.
•Eutrification that leads to the decrease in the amount of
DO in the aquatic region effecting the aquatic life.
•Artery diseases
•Gastric and intestinal Cancer
According to EPA -
10 ppm
Challenges faced –
•Nitrate is colorless, odorless & tasteless.
•Nitrate is found in ppm level thus it is not easily detectable.
 Engineered for Tomorrow

PROJECT – APPROACH
How to go about ????

For the removal nitrate , we are choosing

ADSORPTION PROCESS

Adsorbent To Be Used
ZINC PEROXIDE
 Engineered for Tomorrow

ZINC PEROXIDE

•Zinc peroxide (ZnO2) appears as a bright yellow powder at room temperature.

•Zinc peroxide is a temperature stable solid.
•It is insoluble in water and dissolves in acids
forming hydrogen peroxide.
•It decomposes at 150°C, and release oxygen.
•It also acts as a strong oxidizing agent.
•Also called zinc dioxide, zinc bioxide.

Chemical Formula : ZnO2

Molar Mass: 97.4078
Crystal Structure : Cubic in nature
 Engineered for Tomorrow

OBJECTIVES
•To synthesize and characterize Activated Nano Zinc Peroxide
(ZnO2) using hydrothermal and precipitation methods.

•To carry out adsorption studies and to investigate the effects of

experimental parameters i.e. pH, adsorbent dosage, contact time,
initial nitrate concentration etc on adsorption.

•To determine adsorption capacity of nanoadsorbent using

adsorption isotherm.
 Engineered for Tomorrow

SYNTHESIS OF ZINC PEROXIDE NANOPOWDER

METHOD I METHOD II
Oxidation– Precipitation
Hydrolysis– method using
Precipitation Zn(NO3)2 agent
procedure, using
zinc acetate as a
precursor
 Engineered for Tomorrow

EXPERIMENTAL WORK
PART 1 : SYNTHESIS OF ZINC PEROXIDE
NANOADSORBENT
METHOD I

MATERIALS REQUIRED:-

•Zinc acetate dehydrate[Zn(CH3COO)2.2H2O]

• 30% hydrogen peroxide aqueous solution[H2O2]

•Polyethylene Glycol[H(OCH2CH2)OH](PEG)

•Sodium Hydroxide[Na(OH)]
 Engineered for Tomorrow

PROCEDURE
Oxidation– Hydrolysis–Precipitation procedure, using zinc acetate as a precursor

3 grams of zinc acetate dehydrate +30ml distilled water + 15ml of 30% H2O2

30 ml of PEG was added to it

This was kept for stirring for 2 hours

A pale yellowish solution was obtained

NaOH solution of pH 13 was added to create basic medium until a pH of 11.5 was
obtained – the mixture was changed to white color suspension

White precipitate was separated by centrifuge and the powder was washed 3 times by
NaOH solution

2 additional washes was given by distilled water until final pH of 8.4 for the residue water
was reached
 Engineered for Tomorrow

CHARACTERISATION OF ZnO2 NANOPARTICLES

 Engineered for Tomorrow

METHOD II

MATERIALS REQUIRED:-

•Zinc Nitrate Zn(NO3)2

•Sodium Hydroxide solution NaOH

• 30% Hydrogen Peroxide solution

 Engineered for Tomorrow

PROCEDURE

100 mL of Zn(NO3)2 aqueous solution +100 ml of NaOH aqueous solution

Mixed and stirred for 2 hours

Precipitate was separated by filtration

Precipitate was dispersed into 100mL of H2O2 aqueous solution

Dispersed solution was kept at 75 °C for 2 hours

The precipitate was separated by centrifugation and dried 75 °C

Zinc peroxide powder was obtained

 Engineered for Tomorrow

CHARACTERISATION OF ZnO2 NANOPARTICLES

 Engineered for Tomorrow

ZINC PEROXIDE NANOADSORBENT – NATURE OF

THE SURFACE
The point of zero charge (pzc), in is a phenomenon of adsorption, and it describes
the condition when the electrical charge density on a surface is zero.
The pHPZC of a material is the point at which the solid surface becomes neutral, below
and above pHPZC the material becomes positively and negatively charged.

The value of pH is used to describe pzc only for systems in which H+/OH− are the
potential-determining ions.

 pHPZC of zinc peroxide 7.9

Since the nitrate ion is represented by NO3- which is anionic in nature.

Charge on Zinc peroxide material should be positive in nature for nitrate adsorption.

Zinc peroxide requires an acidic medium

for adsorption of anions like nitrates.
 Engineered for Tomorrow

EXPERIMENTAL WORK - ADSORPTION STUDIES

INSTRUMENTS
UV-Vis Spectrophotometer(UV 2600, Shimadzu, Spectral band=200-800nm)

Rotary Shaker

Eppendorf Micro centrifuge

pH meter
Spectrophotometric measurement

 Read absorbance using distilled deionized water as the reference.

 Use a wavelength of 220nm to obtain nitrate reading.
 Engineered for Tomorrow

pH STUDIES

Amount of Zinc peroxide nanopowder taken=1g

Amount of nitrate solution taken = 25mL (25 ppm)
Total time taken= 1hour

The 25 ppm nitrate solution was taken in a 250 mL conical flask. The pH was
adjusted using 0.001M solutions of HCl and NaOH.

In each flask 25mL of 25 ppm of nitrate solution was taken.

pH of 3,5,8,10,12 was adjusted to give 5 samples.

1g of zinc peroxide powder was added to each sample solution.

The solutions was kept for stirring at 150 rpm for 1 hour in a rotary shaker.
 Engineered for Tomorrow

The solutions was centrifuged in micro centrifuge at 13200 rpm to

separate the nanopowder.

The solutions were tested using UV Spectrophotometer.

 Engineered for Tomorrow

RESULTS :-

pH % Nitrate removed

3 31.92
5 19.825
8 19.238
12 8.54
 Engineered for Tomorrow

35

30

25
% Nitrate Removed

20

15 Series1

10

0
3 5 8 12

pH
 Engineered for Tomorrow

EFFECT OF TIME

Amount of Zinc peroxide nanopowder taken=1.0g

Amount of nitrate solution taken = 25mL (25 ppm)
pH adjusted = 3

25 mL of 25 ppm nitrate solution was taken in a 250 mL conical flask. pH of 3 was
adjusted using 0.001M solutions of HCl.
Contact time of minutes is taken into consideration.
1g of zinc peroxide powder was added to each sample solution.
The solutions were kept for stirring at 150 rpm for 60,120,180,240,300 minutes in
a rotary shaker respectively.
The solutions were centrifuged in micro centrifuge at 13200 rpm to separate the
nanopowder.
The solutions were tested using UV Spectrophotometer.
 Engineered for Tomorrow

34

33.5
% Nitrate removed

33

32.5

32

31.5

31
60 120 180 240 300

Time

Contact time % removed

60 31.87
120 32.37
180 32.81
240 33.47
300 33.5
 Engineered for Tomorrow

EFFECT OF ADSORBENT DOSAGE ON THE

ADSORPTION PROCESS

•Amount of nitrate solution taken = 25mL (25 ppm)

•pH adjusted = 3

25 mL of 25 ppm nitrate solution was taken in a 250 mL conical flask.

pH of 3 was adjusted using 0.001M solutions of HCl.
Different amounts of zinc peroxide powder ranging from 0.5,1,1.5,2,2.5 g
were added to each sample solution.
The solutions were kept for stirring at 150 rpm for the required time in a
rotary shaker respectively.
The solutions were centrifuged to separate the nanopowder at 13200 rpm in
micro centrifuge.
The solutions were tested using UV Spectrophotometer.
 Engineered for Tomorrow

35

30

% Nitrate removed 25

20

15

10

0
0.5 1 1.5 2 2.5
Adsorbent dosage

Adsorbent Dosage % Removed

0.5 8.68

1 31.95

1.5 32.27

2 32.29

2.5 32.77
 Engineered for Tomorrow

IMPORTANT OBSERVATIONS

Maximum adsorption was observed at a pH of 3.

The above analysis shows that 32% nitrate was removed at pH of 3.

Comparative studies suggest that zinc peroxide acts as a better adsorbent

compared to Hydrous bismuth oxide(II) .

A contact time of 4 hours was observed.

It was seen as the adsorbent dosage increased, the adsorption also increased but
the most optimum value was 40 g/L.
 Engineered for Tomorrow

CONCLUSIONS MADE :-

1. Zinc peroxide has a good capacity to adsorb nitrates compared to hydrous

bismuth oxide.
For 25 ppm of nitrate,
Zinc Peroxide – 32-34% adsorption capacity
Hydrous bismuth oxide – 25% adsorption capacity

2. Zinc peroxide is cheaper and easier to manufacture.

3. Zinc peroxide is divalent in nature which can be used for adsorption of various
ions like chromium, sulphur, chloride etc.
 Engineered for Tomorrow

REFERENCES
1. Synthesis of stabilized nanoparticles of zinc peroxide
Liora Rosenthal-Toib, Keren Zohar, Meital Alagem, Yoed Tsur ∗
Department of Chemical Engineering, Technion, Haifa 32000, Israel, Accepted 13 July 2007

2. Oxygen Vacancy Induced Band-Gap Narrowing and Enhanced Visible Light

Photocatalytic Activity of ZnO
Junpeng Wang,† Zeyan Wang,† Baibiao Huang,*,† Yandong Ma,‡ Yuanyuan Liu,† Xiaoyan
Qin,†Xiaoyang Zhang,† and Ying Dai‡, ACS Appl. Mater. Interfaces 2012

3. An Efficient and Fast Process for the Removal of Trivalent and Hexavalent
Chromium from Contaminated Water Using Zinc Peroxide Nanomaterial
Nahar Singh*, Himani Uppal, Sneha Chawla, Sukhvir Singh and Swarupa Tripathy S
Analytical Chemistry, CSIR-National Physical Laboratory, Dr K.S. Krishnan Marg, New Delhi-
110012; India, Pharm Anal Acta 2015 Volume 6 • Issue 8

4. Novel Adsorbent Hydrous Bismuth Oxide for the Removal of Nitrate from Aqueous
Solutions
Arun Lal Srivastav1; Prabhat Kumar Singh2; Chih Huang Weng3; and Yogesh Chandra Sharma4
Journal of Hazardous, Toxic, and Radioactive Waste · November 2013
 Engineered for Tomorrow

5. Removal of Nitrate and Nitrite Anions from Wastewater Using Activated Carbon
Derived from Rice Straw
Hassan A Hanafi1,2* and Sami M Abdel Azeema2,3
Journal of Environmental & Analytical Toxicology -Volume 6- 2016
6. Kinetics of Nitrate Adsorption and Reduction by Nano-scale Zero Valent Iron (NZVI):
Effect of Ionic Strength and Initial pH
Do-Gun Kim*, Yu-Hoon Hwang**, Hang-Sik Shin***, and Seok-Oh Ko****,Published April 3,
2015 ,KSCE Journal of Civil Engineering
7. Removal of nitrate from aqueous solutions in batch systems using activated perlite: an
application of response surface methodology
Mazyar Sharifzadeh Baei,1* Hossein Esfandian2* and Arash Azizzadeh Nesheli3
Accepted 2 December 2015, ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING
8.Ferromagnetism Induced by Oxygen Vacancies in Zinc Peroxide Nanoparticles
Daqiang Gao, Jing Zhang, Guijin Yang, Jing Qi, Mingsu Si, and Desheng Xue*, The
journal of physical chemistry, 2011
9. Soft-Template Synthesis and Characterization of ZnO2 and ZnO Hollow Spheres
S. Cheng,† D. Yan,† J. T. Chen,† R. F. Zhuo,† J. J. Feng,† H. J. Li,† H. T. Feng,† and
P. X. Yan*,†,‡
ReceiVed: April 13, 2009; ReVised Manuscript ReceiVed: June 4, 2009
 Engineered for Tomorrow

ACKNOWLEDGEMENT

 We are grateful to Karnataka State Council For Science and Technology

(KSCST) for funding our project.

 Further, we are grateful to the professors, faculty members and lab attenders
of physics and chemistry department for their support in synthesizing zinc
peroxide.
Engineered for Tomorrow