Removal of organics from water

1. CYPRUS INTERNATIONAL UNIVERSITY
INSTITUITE OF GRADUATE STUDIES AND RESEARCH
Environmental Science Department
TANNIC ACID REMOVAL FROM WATER
ENS 513
Presented by:
Sulaiman Ishaq MUKTAR – 20142930
Lecturer:
Assis. Prof. Dr. ime AKANYETI
1

2. Content
• TANNIC ACID
• TYPES OF SORBENTS FOR THE REMOVAL OF TANNIC ACID
• ANALYSIS OF THE SORBENTS
• CONCLUSION
• REFERENCES
2

3. TANNIC ACID
• naturally occurring organic substance with a molecular formula of
C76H52O46, and a molecular weight of 1700g/mol (Wang et al.,2009).
• It is an anionic organic pollutant .
• is one of phytic substances, from the decomposition of plants. Tannic
acid is found in most water bodies, which is also identified in industrial
wastewater effluent from coir and cork factories, paper and pulp board
mills, tanneries, etc. (Wang et al.,2010).
• Moreover, tannic acid is an organic matter that dissolves in water,
which may react with chlorine disinfectants and form cancer causing
by-products during drinking water production (Li et al.,2009).
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4. STRUCTURE OF TANNIC ACID.
4

5. • Reverse osmosis and coagulation can be used to remove tannic acid from
water.
• Sorption treatment is usually considered as the best method to remove
polyphenolic compounds from aqueous solutions because of its
simplicity and high efficiency
• it is found that activated carbon, clay, resin, metal-oxide and chitosan
remove tannic acid from aqueous solutions effectively (Vinod et
al.,2002).
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6. • Types of sorbents for the removal of Tannic acid
• i. Activated carbon (Onal et al.,2010)
• ii. Polymeric resin WJN-09(Wang et al.,2009)
• iii. Polyaniline (Wang et al.,2013)
• iv. chitosan-coated attapulgite (Deng et al.,2012)
• v. Surfactant- modified zeolite (Lin et al.,2002)
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7. 1. Activated carbon
• Textural waste, was used as a source of activated carbon. Poly
(ethyleneterephthalate) was 90% textile waste. The composition of materials
was done by adding KOH in a ratio of KOH/starting material. After then the
mixture was dried at 110oC and impregnated into the sample. With the
impregnated sample was then heated to activation temperature of 800 oC
then cooled under N2 flow which was then washed and 110 oC to obtain
activated carbon.
• BET surface area (m2/g) 2392
• External surface (m2/g) 2300
• Percentage of external surface (%) 96
• Micropore surface area (m2/g) 92
• Percentage of micropore surface area 4
• Total pore volume (cm3/g) 1.355
• Micropore volume (cm3/g) 0.048
• Average pore diameter (nm) 2.270
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8. • Initial concentration of the tannic acid has an effect on the sorption capacity.
In the figure, it shows that around 92% of tannic acid is sorbed at a
concentration of 200mg/l and at other concentration which are higher than
the first concentration only 57-66% of tannic acid was removed.
8

9. Effect of initial
tannic acid
concentration
with activated
carbon 9

10. 2.Polymeric resin WJN-09
• WJN-09was synthesized using 50g chloromethylation with microporous
styrene-divinyl-benzene and 500ml of nitrobenzene,ZnCl2,HCl and the
mixture was extracted with ethanol in a soxhlet apparatus and dried.100g of
high-crosslinked styrene-divinylbenzene copolymers swollen in 200ml of
dimethamine.The polymer beads were poured into acetone containing 1%HCl
which was then filtered and extracted with ethanol.
• Properties WJN-09
• BET surface area (m2g-1) 472
• Average diameter (nm) 15
• Micro-pore volume (cm3g-1) 0.119
• Macro-pore volume (cm3g-1) 0.360
• Structure styrene
• Average particle (mm) 0.4-0.8
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11. 11
Zeta potential of different adsorbents in solutions at 303K.

12. 3. Polyaniline
• Polyaniline sorbent is synthesized using by chemical oxidation where
aniline was dissolved in 1.0mol/L HCl,another 0.11mmol.ammonium
peroxodisulphate dissolved in 200ml HCl,then both were cooled in an
ice bath.After 2 hours a dark precipitate was filtered to become
colorless
Polyaniline has a surface area of 29.97m2/g
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13. 4.Chitosan-coated attapulgite
• It has a ratio of chitosan and Acid treated attapulgite of 1:10.with a surface
area of 30m2/g. The sorption rate of TA onto CCATP goes up with the
increasing of CCATP amount which can effectively remove TA from the
aqueous solution.(shown below)
• TA sorption increases with increase in concentration of Na+ and Ca2+.
• Sorption rate increases with increase in CCATP,then reaches peak
• Effectively remove TA from aq solution
• Depends on the electrostatic interaction plays an important role in TA
sorption on CCATP.
• pH ranges from 5.5-8
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14. 14

15. 5.Surfactant- modified zeolite
• Zeolites are hydrated aluminosilicate minerals with a frame work formed
by tetrahedral of SiO4 and AlO4 containing water molecules, alkali and
alkaline earth metals in their structure. They have net permanent
negative charge resulting from isomorphic substitution of Si4+ by
Al3+,cationic surfactants such as hexadecyltrimethylammonium
bromide(HTAB) and cetypyridinium bromide (CPB) were used for
modification of zeolites
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16. 16
Effect of pH on the sorption of TA onto CCATP

17. • 5. surfactant-modified zeolite(SMZ 6)
• Sorption isotherm for SMZ is 66mmol/kg the amount desorbed bromide
was 171mmol/kg.
• Co(mg/l)=50,qeexp(mg/g)=93.3,The isotherm follows Langmuir with
qmax(mg/g)=111,Kl(L/mg)=0.918,R2=0.999.The contact time was around
120min.
• Fig. FE-SEM images of SMZ6 and TA-adsorbed SMZ6
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18. Material sorbent Isotherm R2 Qm(mg/g) Percentage
adsorption
Contact
time
Desorption
percentage
reference
Textile
waste
Activated
carbon
Langmuir 0.999 416.67 92 - - 14
Styrene-
divinil-
benzene
Polymeric
resin
WJN-09
Langmuir 0.996 286(plus
Cu2+)
- - - 16
Aniline Polyaniline Langmuir 0.99 117.6 - 25 hours 87.9,79 17
Chitosan,
ATP
Chitosan-
coated
attapulgite
Freundlich 0.938 36.9 - 300mins 97,95 21
Zeolites,
Cetylpyridi-
nium
bromide
(CPB)
Surfactant-
modified
Zeolites
Langmuir 0.99 111
-
120mins - 15
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19. • Analysis of the sorbents
Activated carbon
The percentage removal of tannic of tannic acid decreases with increase in pH.
The sorption capacity of the sorbent increases with increase in temperature.
The value of Qo found at 323k is 416.67mg/g. The values of RL and 1/n shows
that sorption of tannic acid onto activated carbon is a favourable process.
Polymeric resin WJN-09
Since the zeta potential of the resin WJN-09 is positive as shown in the graph,
the charge attraction can be formed between WJN-09 and the charged acids,
and can contribute to the high sorption capacity of the resin for tannic acid.
Polyaniline
Follow the Langmuir model with the correlation factor (R2) suggesting that the
langmuir model is preferable to the Freundlich model. Tannic acid can be
desorbed in alkaline solution.
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20. • Chitosan-coated attapulgite(CCATP)
-The sorption rate of TA onto CCATP goes up with the increasing of
CCATP amount, and then it reaches peak, which indicates that CCATP is
much higher than that of ATP alone. The dependence of TA sorption on
ionic strength implies that the electrostatic interaction plays a very
important role in TA sorption on CCATP.
-1:10,chitosan:ATP(CCATP)
• Surfactant-modified zeolite
Tannic acid sorption capacity was at a high at a solution pH of 4-7
which incidentally decrease with increase with solution pH from 7.0 to
8.5.The high sorption of tannic acid was attributed to the CPB layers.
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21. CONCLUSION
• As we can see in the table when comparing the sorbents, activated carbon
is the one with the highest sorption capacity and it is here by
recommended for the sorption of tannic acid from aqueous
solution.Polymetric resin WJN-09 could also play a role in the removal of
tannic acid.
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22. • References
• [1] J.H. An, S. Dultz, Sorption of tannic acid on chitosan–montmorillonite as a function of pH and surface
charge properties, Appl. Clay Sci. 36 (2007) 256–264.
• [2] T.S. Anirudhan, M. Ramachandran, Sorptive removal of tannin from aqueous solutions by cationic
surfactant-modified bentonite clay, J. Colloid Interface Sci. 299 (2006) 116–124
• [3] J.H. Wang, S.R. Zheng, J.L. Liu, Z.Y. Xu, Tannic acid sorption on aminofunctionalized magnetic mesoporous
silica, Chem. Eng. J. 165 (2010) 10–16..
• [4] M.Y. Chang, R.S. Juang, Sorption of tannic acid, humic acid, and dyes from water using the composite of
chitosan and activated clay, J. Colloid Interface Sci. 278 (2004) 18–25.
• [5] J.N. Wang, A.M. Li, L. Xu, Y. Zhou, Sorption of tannic and gallic acids on a new polymeric sorbent and the
effect of Cu(II) on their removal, J. Hazard. Mater.169 (2009) 794–800.
• 6. Rivera-Utrilla, J., Moreno-Castilla, C., Utrera-Hidalgo, E., Carrasco-Marin, F., “Removal of tannic acid from
aqueous solutions by activated carbons”, Chem. Eng. J., 52 (1), 37-39 (1993).
• 7 Sarici-Ozdemirnal, C., Onal, Y., “Equilibrium, kinetic and thermodynamic adsorptions of the environmental
pollutant tannic acid onto activated carbon”, Desalination, 251 (1-3), 146-152 (2010).
• 8 Vinod, V., Anirudhan, T., “Sorption of tannic acid on zirconium pillared clay”, J. Chem. Technol. Biotechnol.,
77 (1), 92-101 (2002).
• 9 Wang, J.N., Li, A.M., Xu, L., Zhou, Y., “Adsorption of tannic and gallic acids on a new polymeric adsorbent
and the effect of Cu (II) on their removal”, J. Hazard. Mater., 169 (1-3), 794-800 (2009).
• 10 Anirudhan, T.S., Ramachandran, M., “Adsorptive removal of tannin from aqueous solutions by cationic
surfactant-modified bentonite clay”, J. Colloid Interf. Sci., 299 (1), 116-124 (2006).
22

23. • 11 Chang, M.Y., Juang, R.S., “Adsorption of tannic acid, humic acid, and dyes from water using the
composite of chitosan and activated clay”, J. Colloid Interf. Sci., 278 (1), 18-25 (2004).
• 12 An, J.H., Dultz, S., “Adsorption of tannic acid on chitosan-montmorillonite as a function of pH and
surface charge properties”,Appl. Clay Sci., 36 (4), 256-264 (2007)
• 13 Sun, Y., Li, A.M., Zhang, Q.X., Chen, J.L., Fu, D.F., Wang, S.H.,“Adsorptive separation of tannic acid
from aqueous solution by polymeric resins”, Sep. Sci. Technol., 43 (2), 389-402 (2008).
• 14., , Yunus Önal(2010)Equilibrium, kinetic and thermodynamic adsorptions of the environmental
pollutant tannic acid onto activated carbon,pp 167-152
• 15.Wang j,Ji Y,Ding S,Ma H,and Han X.Adsorption and desorption behaviour of tannic acid in aqueous
solution on polyaniline adsorbent.Chinese journal of chemical Engineering,26(6)594-599 (2013).
• 16.Yuehua Deng, Lin Wang, Xiaobin Hu, Benzhi Liu, Zhongbo Wei, Shaogui Yang, Cheng Sun, Highly
efficient removal of tannic acid from aqueous solution by chitosan-coated attapulgite,Chemical
Engineering Journal 181– 182 (2012) 300– 306
• 17.J.W. Lin, Y.H. Zhan, Z.L. Zhu, Y.Q. Xing, Adsorption of tannic acid from aqueous solution onto
surfactant-modified zeolite, J. Hazard. Mater. 193 (2011) 102–111.
• 18. Li, A.M., Zhang, Q.X., Zhang, G.C., Chen, J.L., Fei, Z.H., and Liu, F.Q. (2002) Adsorption of phenolic
compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent.
Chemosphere, 47: 981.
• 19. Pan, B.C., Xiong, Y., Li, A.M., Chen, J.L., Zhang, Q.X., and Jin, X.Y. (2002) Adsorption of aromatic
acids on an aminated hypercrosslinked macroporous polymer. React. Funct. Polym., 53: 63.
• L. Wang, J.P. Zhang, A.Q. Wang, Fast removal of methylene blue from aqueous solution by sorption
onto chitosan-g-poly (acrylic acid)/attapulgite composite, Desalination 266 (2011) 33–
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