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

2

Content• TANNIC ACID

• TYPES OF SORBENTS FOR THE REMOVAL OF TANNIC ACID

• ANALYSIS OF THE SORBENTS

• CONCLUSION

• REFERENCES

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).

4

STRUCTURE OF TANNIC ACID.

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).

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)

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

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.

9

Effect of initial tannic acid concentration with activated carbon

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

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

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

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

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

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

19

• Analysis of the sorbentsActivated carbonThe 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-09Since 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.PolyanilineFollow 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.

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 zeoliteTannic 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.

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.

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).

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–