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Defluoridation of reject water

from a reverse osmosis unit and


synthetic water using adsorption
Naga Samrat MVV

Research supervisors: Prof. K Kesava Rao and Dr. J R Mudakavi


Indian Institute of Science

Outline
Introduction
Motivation
Experiments
Results
Mechanism
Conclusions

Water
water unavailable for drinking; 1%

water available on earth; 74%

Area occupied on earth 70 %


Source: http://water.usgs.gov/edu/earthhowmuch.html

Fluoride contamination

19 states are
affected and
66.6 million
Approximately
220 million people are at
people are atrisk
risk
et.2012
al., 2008
Source: Amini
CGWB,

Sources of fluoride (F-)


Tea
3- 20 mg/L

Minerals
Ex: Fluorspar (CaF2)

Industrial effluents

Water

Fish
1 2 mg/kg

Sources: Lung et al.,2003; Fawell et al., 2006; Fagin, 2008

Fruits and vegetables


0.5 3.5 mg/kg

Drinking water

Guideline value
Standard

F- concentration, cF
(mg/L)

World Health
Organization (WHO),
2011

1.5

Indian standards (BIS),


2012

Desirable limit

Permissible limit

1.5

Fluorosis
http://www.flickr.com/photos/indiawaterportal/4606099994/

https://1phil4everyill.wordpres
s.com/tag/dental-fluorosis/

http://www.drchetan.com/dentalfluorosis-clinical-features-treatment.html

Non skeletal
fluorosis (1
1.5 mg/L)

Dental
fluorosis ( 1
1.5 mg/L)

Brittle bones, joint


pains and
deformation of
bones (3.0 4.0
mg/L)

Complete
deformation and
paralysis ( > 4.0
mg/L)

Is fluorosis curable?
Any form of fluorosis is irreversible
With the use of F- safe water there is considerable
relief from pain

After BAIF (a NGO) constructed the rooftop


rain water harvesting structure in my house, I
started drinking water from the same, and within
6-7 months, I could see the difference. Now, even
though there has been very slight improvement in
my posture, I have been totally cured of my
pains.
Sources: CGWB, 2014; Statement of a lady whose back had become bent because of fluorosis (cited in Angadi, 2008)

Methods of defluoridation
Precipitation and coagulation
Membrane processes
Adsorption and ion-exchange
Solar distillation
Condensing
glass cover

Water layer

Stable
colloidal
dispersion

Solar radiation

adsorbate

adsorbent

Flocs
Coagulant addition

Distillate
channel
Precipitated flocs

Sources: Ayoob et al., 2008; Maliyekkal et al.2010; Sampathkumar et al., 2010; Bhatnagar et al., 2011

50 70% of feed is wasted as a reject stream

Reverse osmosis (RO) unit


at Yellampalli village

People collecting treated


water from the community
RO plant

Choice of adsorbents
Commercial activated alumina (AA)
Particle diameter, dp = 0.4 0.8 mm
Surface area, as = 200 m2/g

Hybrid anion exchange resin embedded with


hydrous zirconium oxide nanoparticles (HAIX)
Particle diameter, dp = 0.3 1.2 mm
Zr loading = 120 mg/g
Prepared by Prof. Arup SenGupta, Lehigh University

Hybrid nanosorbent (HAIX)


(CH3)3N+ OH(CH3)3N+ OH-

Hybrid nanosorbent
+

Anion exchange resin


+

N(H3C) 3

N(H3C) 3

Dispersed hydrous
zirconium oxide
nanoparticles
Sources: Prof. Arup K SenGupta (Private communication); SenGupta and Padungthon, 2013; Padungthon et al., 2014;

Experimental setup

Parameter values
bed diameter, D = 18 mm
bed height, H = 10 cm
empty bed contact time, EBCT 5 minutes
pre-soaking in de ionised (DI) water for 24 h

Adsorption of F- from RO reject using AA


Inlet conditions:
F- : 3.45 mg/L
Cl- : 503.0 mg/L
SO42- : 267.9 mg/L
NO3- : 279.1 mg/L
HCO3- : 630.3 mg/L
Na+ : 346.0 mg/L
K+ : 3.8 mg/L
Ca2+ : 295.4 mg/L
Mg2+ : 81.9 mg/L
pH : 8.1
mAA : 23.58 g

Adsorption capacity, qb = 0.57 mg/g

Composition of synthetic water


Parameter

Reject water
(SRW)

Normal water
(SNW)

F- water
(SFW)

pH

5.5

5.5

6.0

F- (mg/L)
Cl- (mg/L)

5
600

5
200

5
--

SO42- (mg/L)

200

50

--

HCO3- (mg/L)

1050

100

--

NO3- (mg/L)

200

100

--

Na+ (mg/L)
Ca2+ (mg/L)

400
300

70
110

6.1
--

K+ (mg/L)
Mg2+ (mg/L)

40
100

-20

---

Adsorption of F- from synthetic water using AA

qb,SFW = 7.5 mg/g


qb,SNW = 6.2 mg/g
17 % decrease
qb,SRW = 2.1 mg/g
72 % decrease

Adsorption of SO42- from synthetic water using AA

qb,SNW = 4.3 mg/g


qb,SRW = 7.3 mg/g
70 % increase

Adsorption of HCO3- from synthetic water using AA

qSNW = 31.4 mg/g


qSRW = 391.3 mg/g
12.5 times increase

Adsorption of F- from synthetic water using HAIX

qb,SNW = 8.7 mg/g


qb,SRW = 2.9 mg/g
67 % decrease

Removal of NO3- is independent of feed for HAIX

qb,SNW = 8.6 mg/g


qb,SRW = 8.6 mg/g

Adsorption of HCO3- from synthetic water using HAIX

qSNW = 135.3 mg/g


qSRW = 1128.1 mg/g
8.3 times increment

HAIX has about 38 % more adsorption capacity than AA

qb,HAIX = 2.9 mg/g


qb,AA = 2.1 mg/g

Possible adsorption mechanism on AA

Sources: Su and Suarez, 1997; Wijnja and Schulthess, 1999; Ryazanov and Dudkin, 2004; Ayoob et. Al., 2008;

pH of treated water using AA

Possible reactions on HAIX


Equilibrium reactions on zirconia

ZrOOH2+ZrOOH + H+
ZrOOH ZrOO-+ H+
Equilibrium reactions with FZrOOH2+ + F-ZrOF + H2O
ZrOOH + F-ZrOF + OH Equilibrium reactions with NO3ZrOOH + NO3-ZrONO3+ OH-

Source: Padungthon et al., 2014;

Conclusions
Defluoridation of RO reject is possible but to a lesser extent
than SFW because of high concentrations of ions
Increase in the concentration of co-ions decreases Fadsorption drastically
HAIX has a better adsorption capacity than AA
HAIX also removes NO3- but to a lesser extent than to F Presence of HCO3- effects F- adsorption by competing for
sites rather than just changing the pH

Thank
you
Queries?

No adsorption of NO3- on AA

Possible reactions on AA
Equilibrium
reactions on alumina

AlOH2+AlOH + H+
AlOH AlO-+ H+
Equilibrium reactions with FAlOH2+ + F-AlF + H2O
AlOH + F-AlF + OH Equilibrium reactions with HCO3- and CO32AlOH + CO32-AlOCO2-+ OHAlOH + HCO3-AlOCO2-+ H+ + OHAlOH2+ + HCO3- AlOCO2- + H2O + H+

Sources: Su and Suarez, 1997; Wijnja and Schulthess, 1999; Ryazanov and Dudkin, 2004; Ayoob et. Al., 2008;

Donnan principle
Water
A+, B-

Resin
R-Na+
B-

(a)

Water
A+ , B -

Resin
R+ClA+

RNa

(b)

R+
Cl-

B-

A+
H2O

H2O

Donnan membrane principle arises due to the inability of


fixed ions to diffuse
Immobility of some ions leads to phenomenon of
semipermeability
So ion exchangers can act as semipermeable membranes
Source: Sarkar et al, 2010

Nitrate contamination

NO3- > 45 mg/L

Effect of soaking on AA

V/Vb

ts (h)

Guideline values
Standard

pH

NO3concentration, cN
(mg/L)

World Health
Organization
(WHO), 2011

No health based
guideline

50

Desirable limit

6.5 8.5

45

Permissible limit

6.5 8.5

45

Indian standards
(BIS), 2012