Bio-based Adsorbents: Potential Candidates for Wastewater Treatment

BioResources Research Group Faculty of Science & Technology Universiti Kebangsaan Malaysia

Wastewater Treatment
Various methods/technologies: coagulation, chemical oxidation, ozonation, nano-filtration, precipitation, ionexchange, etc. Adsorption: ability to separate a wide range of chemical compounds, easy operational procedures, and facilitation of recovery of costly organic and inorganic materials. Contaminants: cids, bases, toxic organic and inorganic dissolved solids and colors, !ye stuffs, heavy metals, and effluents. Activated carbon " used as adsorbent for centuries #high surface area to volume ratio$. %io-based adsorbents " low cost, abundantly available, regeneration/reuse.

Biomass Resources

Kenaf
-ast growing plant #.' mths to harvest, ' meters tall$ /* ton dried stems per hectare Contains bast and core fibres.
& '(-)* + high fibres length & ,sed for highend composite products Bast & 0*-0( + short fibres & limited strength which goes as water absorbing materials and animal bedding Core

Kenaf

Cocoa Pod Husk (CPH

3enerally, 1* tons of C45 will be generated to produce one ton of dry cocoa beans 6alaysian Cocoa %oard, .'**,*** tons of cocoa beans were produced in /*1* ',***,*** tons of C45. ,tilized as animal feed and renewable energy source by combustion

Cocoa pod 1).21 +

7eed 1*.8' +

!il Palm "mpt# $ruit Bunc% $ibres

6alaysia is one of the largest palm oil exporter ./* million tons of empty fruit bunch #9-%$ are produced yearly. :raditionally used as boiler burning material, organic fertilizer, composite board and pac;aging materials.

&odifications
4hysical and chemical approaches 4hysical " <efining/ball milling

Sajab, M.S., Chia, C.H., Zakaria, S., et al.. 2010. Removal of copper (II) ions from aqueous solution using alkaline-treated kenaf core fibres. Adsorption Science and Technology 28: 337-386

Calculated "'uilibrium Constants for t%e (orption of Cu()) )ons onto Kenaf Core $ibres at *+ oC

Sajab, M.S., Chia, C.H., Zakaria, S., et al.. 2010. Removal of copper (II) ions from aqueous solution using alkaline-treated kenaf core fibres. Adsorption Science and Technology 28: 337-386

Sajab, M.S., Chia, C.H., Zakaria, S., et al.. 2010. Removal of copper (II) ions from aqueous solution using alkaline-treated kenaf core fibres. Adsorption Science and Technology 28: 337-386

&odifications
Chemical approach " al;aline treatment

&odifications
Chemical approaches " chemical modifications
Tertiary amines, 25%

H2N(CH2CH2N)x (CH2CH2NH)y H3C COOH HO C COOH COO H H2O O H3C COOH OH OH OH OH OH CH2CH2NH2 Secondary
Primary amines, 25% amines, 50%

OH OH OH OH OH

CA-TREATED

PEI-TREATED

Sajab, M.S., Chia, C.H., S. Zakaria, Mohd Jani, S., Ayob, M.K. Chee, K.L., Khiew, P.S., Chiu, W.S. 2011. Citric acid modified kenaf core fibres for removal of methylene blue from aqueous solution. Bioresource Technology 102: 7237-7243 Sajab, M.S., Chia, C.H., Zakaria, S., Khiew, P.S. 2013. Cationic and anionic modifications of oil palm empty fruit bunch fibres for the removal of dyes from aqueous solutions. Bioresource Technology 128: 571-577

&odifications
Chemical approach " chemical modifications

150 Zeta potential ( (mV) 100 50 0 -50 -100 -150 pH 2 4 6 8 10 EFB Raw EFB-CA EFB-PEI

Sajab, M.S., Chia, C.H., Zakaria, S., Khiew, P.S. 2013. Cationic and anionic modifications of oil palm empty fruit bunch fibres for the removal of dyes from aqueous solutions. Bioresource Technology 128: 571-577

,#e Adsorption
(METHYLENE BLUE) (PHENOL RED)

MB before & after adsorption

PR before & after adsorption

C!&PA-)(!.
Adsorbent MB adsorption Kenaf-CA /* )* 0* CPH-.a!H /* )* 0* "$B-CA /* )* 0* PR adsorption "$B-P") /* )* 0* 1*>.2 1/'.( 16537 *.*/( *.*1) *.*01 *.1122 *.18') *.*(10 *.8)' *.8(( *.8*0 1*'.1 1/>./ 12134 12'.' 128.( 15135 0>.0 >0.) 1+231 *.*// *.*2/ *.1*1 *.11> *.10* *./28 *.*0/ *.10/ *.1*' *.*11* *.*'(* *.*0'* *.*/2) *.*/*) *.*11> *.*(1/ *.*/*/ *.*'1) *.88) *.888 *.88) *.>00 *.>>> *.>)( *.82> *.88( *.82( Temperature #oC$ Q* /an0muir model b R= r/

-e0eneration
120 100 Adsorption capacity (%) 80 60 40 20 0 1st Cycle 2nd Cycle 3rd Cycle 4th Cycle 5th Cycle 6th Cycle th Cycle MB PR

Sajab, M.S., Chia, C.H., Zakaria, S., Khiew, P.S. 2013. Cationic and anionic modifications of oil palm empty fruit bunch fibres for the removal of dyes from aqueous solutions. Bioresource Technology 128: 571-577

FixedFixed -Bed Column Adsorption

Discolouration of POME

(a) POME, (b) EFB-PEI adsorbed POME, (c) Anaerobic-treated POME and (d) EFB-PEI adsorbed anaerobic POME.

Graphene Oxide (GO)

Graphene, a one-atom-thick planar sheet of sp2-bonded carbon atoms that are packed in honeycomb crystal lattice. Attracted massive amount of attention since its discovery at 2004. GO - chemically modified graphene ith o!ygen functionali"ed groups such as epo!ide, hydro!yl, carbo!yl # carbonyl. $ighly hydrophilic - ell dispersed in solution for modification and applications

&a0netic 8rap%ene !9ide

%&ast adsorption e'uilibrium

MB

MB + GO

-e0enerated Cellulose Containin0 8rap%ene !9ide

-e0enerated Cellulose &embrane Cellulose dissolution and regeneration

High porous structure

Antibacterial Regenerated hitosan Beads

E. coli

S. aureus

S. aureus

Antibacterial results ($pread plate)

ontrol

B!GO

B!Ag"#

B!AgGO

E. coli

ontrol

B
$ample CB CB-#$ CB-A%&P CB-A%#$

B!GO
S. aureus !e e""ect !e e""ect '!e (nh()(t(*n '!e (nh()(t(*n E. coli

B!Ag"#

B!AgGO

!e e""ect !e e""ect '!e (nh()(t(*n '!e (nh()(t(*n

Thank you