Composites as adsorbent for the adsorption of environment pollutant

Application of Composite material

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2. ENTITLED
Presented by
MUHAMMAD IQBAL
Ph.D. (COURCE CODE # 905)
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Waterisnecessaryforalllivingorganismsi.e.Plants,Animals,
Fungi,AlgaeandHumanbeing.
Inthismodernworldmanaremakingalotsofthingforthe
luxuriousandcolourfullifeofman.
Mansendtheindustrialwastesintoseweragewithouttreatmentdue
tothistheindustrialwastemixedwithseawaterorlakeorpond
waterorlandwhereplantsandaquaticanimalsabsorbedthem
throughwater,afterthisthesepollutantsaretransferredintothe
animalsormanbodythroughthefoodchainandcausesalotsof
diseases.

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Arsenic(As)causeshypertension,cardiovasculardisorders,hepatic
damageinman.
Cadmium(Cd)depositedinlungsandkidneys.Lead(Pb)is
responsibleforanemia.Itisalsoresponsibleforabnormalbrain
growthinchildren.
Mercury(Hg)cancauseblisterintheuppergastrointestinaltract,
vomiting,abdominalpain,constipationandgastritis.Theacute
exposuretoelementalHgvapourscancause“pinkdisease”or
acrodynia.
Organophosphatesareabroadgroupoftoxiccompoundswhich
includepesticides,flameretardantsandnerveagents.Itis
carcinogenictoinsects,birdsandmammalsincludinghuman.

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Congored(CR)isakindoftypicalbenzidineazodye.Itiswidely
usedintextile,paper,biologicaldyeandotherfieldsbecauseofits
lowcost,easetouseandstablechemicalproperties.However,CRis
alsoakindofdyepollutant,whichisharmfultohumanbeingsand
environment.TheintakeofCRintohumanbodiescancausecancers
andotherlong-termillnesses.Duetoitsgoodsolubility,CRcanbe
easilytakenintowaterthroughtherainwashandindustrial
wastewaterdischarge.TheexistenceofCRcanrestrictoxygenand
lightflowtothewaterandthreatenthesurvivalofaquatic
organism.

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In2018,EryunYanetal,successfullysynthesizedFe
3
O
4
nanoparticlesfunctionalizedpolyvinylalcohol/chitosanmagnetic
compositehydrogel(Fe
3
O
4
-MCH)viacrosslinkingmethodforthe
removalofCr
6+
becauseFe
3
O
4
-MCHisanefficientadsorbentfor
removingchromium(VI).
They first prepared the colloid of Fe
3
O
4
.
Than freeze a part of Fe
3
O
4
colloid at -70
0
C for 2 days and
dried in a freezing dryer.
Now 10% Poly vinyl alcohol (PVA) solution (2.1 g) and 2%
Chitosan(CS) solution (0.9 g) were mixed together.
PREPARATION

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After this 0, 0.4, 0.9 and 1.8 g Fe
3
O
4
colloid was added,
respectively.
The mixture was stirred vigorously for 10 min to ensure the
well dispersion of the NPs.
After that, 5 drops of glacial acetic acid were introduced into
the mixture.
After cross-linked in glutaraldehydevapor for 24 h, the Fe
3
O
4
-
MCH was obtained.
ABSORPTION
TheabsorptionofCr(VI)wascarriedoutwhichwasmaximum.
FortherecoveryofFe
3
O
4
-MCH,theadsorbentwasputinto20
mLof0.01mole/dm
3
NaOHsolution,whichwasshakenina
shakerat180rpmfor30min.Then,thetreatedFe
3
O
4
-MCH
adsorbentwaswashedtwicewithultrapurewater,andactivated
using10mLof0.01mole/dm
3
HClsolution.Atlast,theadsorbent
wasdriedindryingcabinetandusedfornextcycle.

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In2018,M.E.AbdEl-Aziz,synthesizedbiodegradablebi-
functionalcellulosederivativestoremovewidespreadunderground
watercationssuchas;Ca
2+
,Mg
2+
,Fe
2+
,Pb
2+
andCu
2+
.
PREPARATION
Theyfirstdispersedcertainamountsofcellulosewithorwithout
clayin100mLdoubledistilledwaterthenaddedpotassium
persulfate(PPS)withstirringinwaterbathat70ºCfor10min
tocreateactivesitesonthecellulosechain.
After this a required amount of monomers was added to the
above mixture after decreasing temperature to 40 ºC then the pH
was adjusted to 8. The temperature was raised to 70 ºC to start
the grafting polymerization.

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Thegraftedcellulosewasfiltratedoff,washedbythehotwater
twotimesandthenbywater/ethanolmixture(50/50)twotimesto
removethehomopolymer.
Thegraftedcellulosewasdriedat60ºCfor2daysinovento
removethewaterforfurtherapplication.
The effect of the grafted cellulose on removing the metal cationswas
investigated.
ABSORPTION
The functional groups at the surface of adsorbent determine the
mechanism of metal ion uptake such as physical adsorption,
chelating, and ion exchange.

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Amide,carboxyl,andsulfonicacidgroupsaremainlyresponsible
forthemetalremovalincaseofgraftingofacrylamide(AM),acrylic
acid(AA),and2-acrylamido-2-methylpropanesulfonicacid(AMPS),
respectively,ontocellulose.
Themaximumremovalefficiencyofeachiondependonthe
functionalgroupswhichwerecreatedbygraftingprocess.
TheremovalefficiencyofCu
2+,
Pb
2+
,Ca
2+
,Mg
2+
andFe
2+
bygrafted
celluloseiseffectedbytheabsenceandpresenceofclay.

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In2017ItamarA.ShabtaiandYaelG.Mishaelprepareda
compositedtoremoveorganophosphatepesticides,suchas
diazinonfromwater.
PREPARATION
PVPcoS(3 g/L) was protonatedby adding H
2SO
4 (95%; 0.65
mL/L) at stoichiometricconcentrations (100% of pyridine
monomers).
MMT clay suspension (1.67 g/L, 4 mL) was added to HPVPcoS
solutions (0.03 –0.56 g/L, 8 mL) in 12 mLTeflon-capped glass
vials. The pH was adjusted, if necessary, to 3.5±0.1 with dilute
H
2SO
4.

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Theclay-polymersuspensionswereagitatedfor2hours
(equilibriumwasreachedwithin1hour)usingashaker,
centrifuged,andsupernatantswereseparatedfromthesettled
HPVPcoS-MMTcomposites.
Thecompositeswerewashedwithdeionizedwater(12mL)to
removeexcesspolymerandelectrolytesandcentrifugedagain.
TheadsorptionofdiazinontotheprotonatedPVPcoS-MMT
composite(HPVPcoS-MMTcomposite)wasrapidandhighwith
respectiveaffinityandcapacitycoefficientsofKL5.6·104L/moland
Qmax5.8·10-4mol/g.DiazinonfiltrationbycolumnsofHPVPcoS-
MMTcompositewasmoreefficientthanbyGACorPVPcoS-MMT
columns.TheregenerationoftheHPVPcoS-MMTcolumnsby
increasingpH,wasdemonstrated,whereasGACdidnotrespondtoa
pHchange.
ABSORPTION

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In2016,QiangHuangetal.preparedamonodispersed
functionalizedSiO
2
(SiO
2
-PDA-PDMC)compositesviamussel
inspiredchemistryandsurfaceinitiatedatomtransferradical
polymerization(SI-ATRP)fortheremovalofCongored(CR)from
aqueoussolutiontoevaluatetheperformanceinenvironment
application.
TheSiO
2sphereswerepreparedviaamodifiedStӧbermethod.
PREPARATION
And then, 9 mLammonia solution (25-28%) was rapidly added
into the TEOS solution under stirring.
Typically,24.75mLH
2O,61.75mLethylalcoholand4.5mL
TEOSweremixedina250mLflaskwithintensivelystirring.

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After reaction for 6 hrs at room temperature, the product was
centrifugally separated from the suspension and washed with with
ethanol several times.
The SiO
2spheres were obtained after drying in vacuum oven at
333 K.
ThesurfacemodifiedSiO
2(SiO
2-PDA)particlesweresynthesized
usingmusselinspiredmodification.
1.5 g SiO
2and 1.5 g DA were added into a 300 mL(10 mM) Trisbuffer
solution (pH 8.5) firstly, the mixture was sonicatedfor 20 min.
Then, the homogeneous solution was stirred steadily at room
temperature for 8 hrs.
After reaction finished, the product was washed with ethanol
several times and dried it at 333 K in a vacuum oven.

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The functionalized SiO
2particles with bromogroups (SiO
2-PDA-Br)
were prepared through the esterificationor acylationbetween BiBand
hydroxyl or amine groups on the surface of SiO
2-PDA particles.
The graft polymerization of the cationic polymer PDMC onto SiO
2
(SiO
2-PDA PDMC) was carried out in aqueous medium using SI-
ATRP.
The initiator SiO
2-PDA-Br (1.5 g), monomer DMC (6.0 g) and
catalyst CuBr(312.1 mg, 2.175 mmol) were mixed in 80 mLmethanol-
water (1:3) solution aided by sonicationfor 10 min to form a
homogeneous suspension.
The mixture was degassed and backfilled with nitrogen five times
and kept under nitrogen atmosphere.
Subsequently, the ligandPMDETA (376.9 mg, 2.175 mmol) was
injected into the suspension with stirring and reacted in oil bath at
353 K for 24 hrs.

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After the polymerization was complete, the product was
centrifuged with 10000 r/min for 10 min and washed with EDTA
solution and deionizedwater several times to remove free untethered
polymers and catalytic system compounds.
Finally, the obtained SiO
2
-PDA-PDMC compositeswere dried at
333 K under vacuum.
ABSORPTION
The adsorption of CR in aqueous solution on the SiO2-PDA-PDMC
composites was investigated with batch experiments. The contact
time was varied between 0 and 60 min. After a predetermined
contact time, the mixture was centrifuged with 8000 r/min for 1 min
to remove solid adsorbent and the clear supernatant solution was
submitted for determination.

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