Synthesis of CaCO3

Nanoparticles Using
Citrate Method To
Remove Dyes in Textile
Waste Water
Fernando B.D.A.S. Supervised by
E/13/099 Dr. P. Karunaratne
Dr. C.Gunathilake
INTRODUCTION

• Water treatment has been studied extensively as demand for

quality water increases with the population growth

• Current waste water treatments (filtration, chemical treatment,

distillation) are not sustainable and does not supply the water
purification in the adequate time

• Dyes discharged directly into water streams at high temperature

(500C-600C) are carcinogenic and non-biodegradable
• Waste water treatment has been analysed using nanomaterials

• Nanomaterials exhibits properties such as

• High porous structure
• High specific area
• High sorption rates
• High pore size when using as an adsorbent
• High adsorption capacities

could be used to remove waste from industrial waste water

Aim
• To synthesize CaCO3 nanoparticles and optimize the synthesize conditions to achieve
high adsorption capability of removing dyes in waste water streams

Objectives
• To synthesize CaCO3 nanoparticles by changing citric acid concentration and drying
time
• To compare dye adsorption capabilities of synthesized CaCO 3 nanoparticles
• To characterize the material qualitatively(XRD,FTIR) and quantitatively (N 2
adsorption-desorption)
• To evaluate adsorption capacities for a prepared dye solution using equilibrium and
kinetic models
Research Hypothesis

By changing the synthesize parameters (citric acid concentration

and drying temperature), synthesized CaCO3 nanoparticles have
different adsorption capabilities in removing dye from textile waste
water
Literature Survey (Hypothesis Justification)

• CaCO3 nanoparticles promotes,

 Highly porous structure

 High pore size
 High specific area
Than the conventional particles.

(Boyjoo and Pareek, 2014)

(Ghiasi and Malekzadeh, 2012)
Literature Survey continued

• Currently used nanomaterials in waste water treatment,

• TiO2
• Fe2O3

• Drawbacks
• High cost
• Undesirable environmental effects
• Complex synthesizing techniques

Therefore, as an alternative CaCO3 nanoparticles can be implemented

Literature Survey continued

• Currently nanoparticles/nanomaterials are used for applications

such as,

• Used in electrical components

• Used in pharmaceutical applications
• Used in agricultural applications
• Used in batteries, fuel cells etc.
Literature Survey continued

• Advantages of CaCO3

• Bio compatible
• Environmental friendly
• Non-corrosive
• Relatively low cost
• Higher availability
• Easy to synthesize
Literature Survey continued

• Methods of synthesis for CaCO3 nano particles

• Hydrothermal method
• Sol-gel method
• High gravity multi-phase reactive precipitation method
• Liquid emulsion membrane technique

(Ritika Gupta, 2004)

Literature Survey continued
Adsorption isotherms

•• Equilibrium
  study

• Langmuir model
=

• qe = Equilibrium concentration of adsorbate in the adsorbent in mg/L

• Ce = Equilibrium concentration of the adsorbate in the liquid phase in mg/L
• KL = Langmuir constant
• qm = maximum adsorption capacity
Literature Survey continued
Adsorption isotherms
• Kinetic study
• Pseudo first order kinetic model

log(qe – qt) = log(qe) – (K1t)/2.303

• Pseudo second order kinetic model

t/qt =1/(K2qe2) + (t/qe)

• qe = Amount of adsorbed adsorbate per unit mass at equilibrium mg/g

• qt = After time t amount of adsorbed adsorbate per unit mass in mg/g
• K1 = Rate constant of pseudo first model in min-1
• K2 = Rate constant of pseudo second model in g/mg.min
• t = time in minutes

(Gunathilake et al., 2015)

Materials & Methods
Materials

• Synthesize materials
• Ca(NO3)2

• Citric acid
Ca(NO3)2
Citric acid
• Adsorbent
• CaCO3 nanoparticles

• Adsorbate
CaCO3
• Methylene blue dye solution nanoparticles

Methylene blue solution

Materials & Methods
• Method used is “citrate sol-gel method”
• Experimental procedure (Ghiasi and Malekzadeh, 2012)

1 mol/dm3 Ca(NO3)2

Calcinating
Evaporating Drying at T,24 Rate: 10K/min
Mixing Mixing
600C, 24 hr (T = 800C,1500C) Max. Temp =6000C
Time = 5h

X M Citric acid solution

(X= 0, 0.5, 1, 1.25, 2.15) CaCO3
nanoparticles
Materials & Methods

• Classification and identification

• XRD

• Phase identification of a crystalline material and can provide information of

unit cell dimensions and sample purity

• FT-IR

• Identify materials by using functional groups present in the sample that is being
examined
• Residual organic traces(citric acid) and impurities can be identified
Materials & Methods
Methods

• Using the thermogravimetric analysis, thermal stability of the

samples could be determined.

• Using the UV spectrophotometer, calibration curve of the

methylene blue concentration varying with absorbance can be
Thermogravimetry analysis
drawn

• Unknown methylene blue concentration can be measured using the

absorbance obtained by the UV spectrophotometer
UV spectrophotometer
Materials & Methods
Methods

• Using the Nitrogen Adsorption-Desorption analyzer,

• Specific surface area (BET)

• Total pore volume
N2 Adsorption-Desorption

can be calculated.
Materials & Methods

• SEM would be used to characterize surface properties of the

nanoparticles.

• Qualitatively : Structure particular or agglomerated

• Quantitatively : Pore width

Scanning Electron Microscope

Time Management

  WEEK
TASK 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Literature Survey on critical
analysis                              
Synthesis of Calcium
Carbonate nanoparticles                              
Characterization of Calcium
Carbonate nanoparticles                              
Adsorption
experimentation                              

Results Interpretation                              

Compiling Draft Report                              

Finishing Final Report                              

Obstacles foreseen and remedies

Obstacles Remedies

Unavailability of instruments to characterize Sending samples to overseas to characterize

surface properties of the samples

Lack of knowledge in using instrumentation Gain knowledge through literature survey

(i.e. calcination oven)

High amount of samples to be tested Optimize and creating a schedule in carrying

out experiments

Lack of adsorption studying based on Prediction of adsorption characteristics by

nanoparticles literature survey
References

• Boyjoo, Y., Pareek, V. K. and Liu, J. (2014) ‘Synthesis of micro and nano-sized calcium
carbonate particles and their applications’, J. Mater. Chem. A. Royal Society of
Chemistry, 2(35), pp. 14270–14288. doi: 10.1039/C4TA02070G.
• Ghiasi, M. and Malekzadeh, A. (2012) ‘Synthesis of CaCO3 nanoparticles via citrate
method and sequential preparation of CaO and Ca(OH)2 nanoparticles’, Crystal Research
and Technology, 47(4), pp. 471–478. doi: 10.1002/crat.201100240.
• Gunathilake, C. et al. (2015) ‘Adsorption of Lead Ions from Aqueous Phase on
Mesoporous Silica with P-Containing Pendant Groups’, ACS Applied Materials &
Interfaces, 7(41), pp. 23144–23152. doi: 10.1021/acsami.5b06951.
• Savage, N. and Diallo, M. S. (2005) ‘Nanomaterials and water purification: Opportunities
and challenges’, Journal of Nanoparticle Research, 7(4–5), pp. 331–342. doi:
10.1007/s11051-005-7523-5.
•  Ritika Gupta (2004) ‘Synthesis of Precipitated Calcium Carbonate Nanoparticles Using
Modified Emulsion Membranes’, Master of Science in Paper Science Engineering, (May),
p. 57
References
• Achour, A. et al. (2017) ‘Synthesis and characterization of porous CaCO 3 micro / nano-
particles’. doi: 10.1140/epjp/i2017-11531-8.
• Macedonia, R. (2014) ‘Methods for waste waters treatment in textile industry’,
(November).
Thank you!!!