By Ahmad Baraka Supervisors Prof. Peter Hall Dr. Mark Heslop
description
Transcript of By Ahmad Baraka Supervisors Prof. Peter Hall Dr. Mark Heslop
Removal of Cu(II) ions from Removal of Cu(II) ions from aqueous solution effluent using aqueous solution effluent using Melamine-Formaldehyde-DTPA Melamine-Formaldehyde-DTPA
resin in a fixed-bed up-flow resin in a fixed-bed up-flow columncolumn
By
Ahmad Baraka
Supervisors
Prof. Peter Hall
Dr. Mark Heslop
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The problemThe problemSources of pollution (Mining-industrial Sources of pollution (Mining-industrial
activities- agricultural runoff, etc...)activities- agricultural runoff, etc...)
Discharging heavy metals into water bodiesDischarging heavy metals into water bodies
Non-degradableNon-degradable
Accumulation of toxic heavy metals Accumulation of toxic heavy metals (World wide problem)(World wide problem)
Some famous heavy metals present in different wastewaters: Chromium, Lead, Copper, Zinc, Cadmium, Nickel, Iron, Cobalt, Mercury, Silver, Aluminium, …..
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How to solve the How to solve the problem?problem?The main methods for heavy metals The main methods for heavy metals
removalremoval
► Chemical precipitation (hydroxides and carbonates) Chemical precipitation (hydroxides and carbonates) ► Solvent extraction (liquid / liquid extraction)Solvent extraction (liquid / liquid extraction)► Ion ExchangeIon Exchange► Electrochemical method (Electrodialysis – Electrochemical method (Electrodialysis –
Electrochemical Electrochemical ion exchange (EIX)ion exchange (EIX)► Reverse osmosis (Membrane separation) Reverse osmosis (Membrane separation) ► ADSORPTIONADSORPTION (liquid / solid extraction)(liquid / solid extraction)
- Active carbon, fly ash, etc.. - Active carbon, fly ash, etc.. - - biomaterials (e.g. wastes of agricultural biomaterials (e.g. wastes of agricultural
origin)origin)- inorganic resins- inorganic resins- - organic resinsorganic resins
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AdsorptionAdsorptionAdsorption is an attractive technology for
treatment of wastewater for retaining heavy metals from dilute solutions.
Adsorption (liquid/solid extraction):Adsorption (liquid/solid extraction): - physical adsorption (weak forces)- physical adsorption (weak forces)
- chemical adsorption (chemical bond)- chemical adsorption (chemical bond)
- surface micro-precipitation adsorption- surface micro-precipitation adsorption
- coordination adsorption (ligands or - coordination adsorption (ligands or chelates chelates and depend on O,N,S,P and depend on O,N,S,P donor atoms)donor atoms)
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Aim of the projectAim of the project
► SynthesisSynthesis and and characterizationcharacterization of a new of a new organic resin (MF-DTPA) .organic resin (MF-DTPA) .
► Studying adsorption performance of MF-Studying adsorption performance of MF-DTPA towards some heavy metals (Cu, Co, DTPA towards some heavy metals (Cu, Co, Cd, and Zn) through Cd, and Zn) through thermodynamicsthermodynamics, , kineticskinetics, and , and isothermisotherm. (batch study). (batch study)
► Estimate the adsorption mechanisms.Estimate the adsorption mechanisms.
Examine the new adsorbent under continuous mode (column study) considering Cu(II) ion
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Why MF resin?Why MF resin? (Advantages)(Advantages)
► Availability of main precursors (Melamine and Availability of main precursors (Melamine and Formaldehyde) with low price.Formaldehyde) with low price.
► Production of Monolithic, granules, fine powder Production of Monolithic, granules, fine powder products.products.
► Controllable porosity (pH, Temp., solvent type, Controllable porosity (pH, Temp., solvent type, solvent content).solvent content).
► Good mechanical hardness.Good mechanical hardness.► Chemical and thermal stability.Chemical and thermal stability.► Ability to functionalize with differentAbility to functionalize with different
polyaminepolycarboxilic acids (e.g. DTPA, NTA, polyaminepolycarboxilic acids (e.g. DTPA, NTA, CDTA, etc…)CDTA, etc…)
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DTPACH2
N
CH2
CH2
CH2
N
CH2CH2
CH2
N
CH2
CH2
CO
OH
C
O
OH
COOH
C
O
OH
C
O
OH
NH2
N
N
N
NH2NH2
H H
OH
+
OHNHNH
NH2
N
N
N
MATRIX
H+
CH2
NH2
NH
N
N
N
N
MATRIX
(A)
(B)
(A)
+
(A)
Methylene bridge
Ether bridge
(B) +NH2
NH2
NH2
N
N
N
NH
NHNH
N
N
N
NH NH
NH2
N
N
N
MATRIX
MATRIX
MATRIX
(D)
(E)
(D)
DTPA
NH NH2
NH NH
N
N
NN
N
N
MATRIX
NH NH
MATRIX
MATRIX
NHNH
NH NH2
NH
N
N
N
NH
N
N
N
O
MATRIX
MATRIX
MATRIX
NN
N
O
OH
O
OH
O
OH
O
O
OHNH
NH NH
NN
N
MATRIX
MATRIX
Melamine
Methylol
Imine
Aminal
MF-DTPA
+
OH OHNH
NH
N
N
N NH
NH
NH2
NH N
N
N
MATRIX
MATRIX
MATRIX
H+
(C)
and / or and / or(C) (D) (E)
Formaldehyde
+
(A)
NH2
N
N
N
NH2NH2
Chemistry of preparation (MF-DTPA) resin
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MF
matr
ix
form
ati
on
DTPA
an
chori
ng
(am
ide b
ond)
Chelating site
Resin
matrix
Proposed structure MF-DTPA resin
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IR spectra of MF and MF-DTPA
MF
MF-DTPA
C=
O
O-
H
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0 50 100 150 200 250
PPM
C13-NMR of MF and MF-DTPA
MF-DTPA
MF
-400 -300 -200 -100 0
ppm
N15-NMR of MF and MF-DTPA
MF-DTPA
MF
ResinResin CC : : HH : : N N : : OO
MF-DTPAMF-DTPA 35.7 : 5.2 : 37.7 : 21.635.7 : 5.2 : 37.7 : 21.6
MFMF 31.7 : 5.5 : 40.4 : 22.331.7 : 5.5 : 40.4 : 22.3
From elemental analysis results, 36.7% of the resin mass is DTPA (around 0.93 mmole per gram of solid resin).
Elemental analysis
About 93.3 mmole DTPA per gram MF-DTPA resin
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0
50
100
150
200
250
300
0 0.2 0.4 0.6 0.8 1
Relative Pressure (P/Po)
Volu
me A
dsorb
ed (
cm
3/g
)
Des
orpt
ion
Ads
orpt
ion
BET BET Surface Surface
Area, mArea, m22/g/g
Micropore Micropore Area, mArea, m22/g/g
BJH Adsorption BJH Adsorption cumulative pore cumulative pore volume., cmvolume., cm33 /g /g
Average Average pore pore
diameter, diameter, ÅÅ
161.863161.863 0.3310.331 0.39650.3965 94.7094.70
N2 gas adsorption-desorption (BET)
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SEM Image of MF-DTPA resin
MF-DTPA aggregates
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Cu(II) adsorptionCu(II) adsorption (continuous (continuous
mode)mode)
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Peristaltic Pump
Influent tank Effluent
tank
Packed column
Sampling valve
Experimental removal set
( fixed-bed up-flow column)( fixed-bed up-flow column)
flow
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Suggested removal Suggested removal mechanismmechanism(chelation)(chelation)
Cu(II)
Cu(II) coordination with DTPA part
Resin body resin active part
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Effect of bed height 5 7 9 cm
Effect of influent concentration 20 30 40 ppm
Effect of influent flow rate 3.2 5.5 8.1 ml/min
Parameters to discussD
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0
0.2
0.4
0.6
0.8
1
1.2
0 200 400 600
time (min.)
Ct/C
o
5 cm
7 cm
9 cm
Effect of bed height
10%
Flow rate=5.5 ml/min
C (initial)= 30 ppm
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0
0.2
0.4
0.6
0.8
1
1.2
0 200 400 600time (min)
Ct/C
o20 ppm
30 ppm
40 ppm
Effect of influent concentration
Flow rate=5.5 ml/min
Bed height = 7 cm
10%
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0
0.2
0.4
0.6
0.8
1
1.2
0 200 400 600 800
time (min)
Ct/C
o
3.2 ml/min 5.5 ml/min 8.1 ml/min
Effect of influent flow rate
10%
Flow rate=5.5 ml/min
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Experimental results of up-flow column adsorption considering bed height, influent concentration and influent flow rate
[[ZZ(cm)(cm) ,,CC○○ (mg l (mg l-1-1)) , , υυ (ml min (ml min-1-1)])]VVeffeff
(ml)(ml)TTbb
(min)(min)qqmm
(mg g(mg g-1-1))
[5, 30, 5.5][5, 30, 5.5] 10721072 195195 27.6227.62
[7, 30, 5.5][7, 30, 5.5] 17881788 320320 32.2632.26
[9, 30, 5.5][9, 30, 5.5] 25302530 460460 33.4333.43
[7, 20, 5.5][7, 20, 5.5] 24752475 450450 29.229.2
[7, 40, 5.5][7, 40, 5.5] 14031403 255255 33.3133.31
[7, 30, 3.2][7, 30, 3.2] 22122212 660660 48.4948.49
[7, 30, 8.1][7, 30, 8.1] 12961296 160160 19.2519.25
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The data collected in continuous mode studies was used to determine the kinetic parameters using the Thomas model which is widely used for column studies.
The Thomas model has the following expression;
Thomas model (Kinetics)
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-4
-3
-2-1
0
1
23
4
5
100 300 500
time (min)
ln(C
o/C
t - 1
)
Z= 5 cm
Z= 7 cm
Z= 9 cm
-4
-3
-2
-1
0
1
2
3
4
100 300 500
time (min)
ln(C
o/C
t-1)
20 ppm
30 ppm
40 ppm
-4
-3
-2
-1
0
1
2
3
4
0 200 400 600 800
time (min)
ln(C
o/C
t-1)
3.2 ml/min
5.5 ml/min
8.1 ml/min
Parameters predicted from Thomas model considering bed height, influent concentration and influent flow rate
[[ZZ(cm)(cm) ,,CC○○
(mg l(mg l-1-1)) , , υυ (ml min (ml min-1-1)])]
kkThTh (l mg (l mg-1-1
minmin-1-1))
QQ (mg g(mg g--
11))RR22
[5, 30, 5.5][5, 30, 5.5]1.17 × 101.17 × 10-3-3 21.9721.97
0.9740.97488
[7, 30, 5.5][7, 30, 5.5]1.21 × 101.21 × 10-3-3 32.3032.30
0.9760.97666
[9, 30, 5.5][9, 30, 5.5]1.25 × 101.25 × 10-3-3 43.7543.75
0.9800.98000
[7, 20, 5.5][7, 20, 5.5]1.50 × 101.50 × 10-3-3 29.6929.69
0.9590.95933
[7, 40, 5.5][7, 40, 5.5]1.32 × 101.32 × 10-3-3 33.1633.16
0.9700.97022
[7, 30, 3.2][7, 30, 3.2]9.13 × 109.13 × 10-4-4 36.5536.55
0.9920.99233
[7, 30, 8.1][7, 30, 8.1]1.42 × 101.42 × 10-3-3 26.1326.13
0.9840.98477
height
concentration
Flow rate
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BDST modelBDST model((BBed ed DDepth epth SService ervice TTime)ime)
Minutes
cm
BDST constants:
N○ = 7232 mg/ml (25.8 mg per gram of solid resin)
kad = 4.91×10-4 l mg-1 min-1
Z○ = 2.2 cm.
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BDST model analysis
0
100
200
300
400
500
600
4 5 6 7 8 9 10
Bed height (cm)
Ser
vice
tim
e (m
in.)
0.033
0.1
0.5
0.9
The BDST equations of these lines are as follows:Ts = 62.5 Z – 144.17 for Ct/C○ = 0.033
(R2=0.9995)Ts = 67.5 Z – 149.17 for Ct/C○ = 0.1
(R2=0.9995)Ts = 66.3 Z – 65.417 for Ct/C○ = 0.5
(R2=0.9999)Ts = 63.8 Z – 1.25 for Ct/C○ = 0.9
(R2=0.9988)
BDST plots at Ct/C○ = 0.033, 0.1, 0.5 and 0.9.
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2.2 cm
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BDST model fitting with influent concentration condition and influent flow
rate condition
[[ZZ(cm)(cm) ,,CC○○ (mg l (mg l-1-1)) , , υυ (ml min (ml min-1-1)])]Experimental Experimental service time service time
(min)(min)
BDST BDST model model
time,time, T TSS
(min)(min)
[7, 20, 5.5][7, 20, 5.5] 450450 485485
[7, 30, 5.5][7, 30, 5.5] 320320 324324
[7, 40, 5.5][7, 40, 5.5] 252252 243243
[7, 30, 3.2][7, 30, 3.2] 660660 663663
[7, 30, 8.1][7, 30, 8.1] 160160 172172
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0
10
20
30
40
50
60
0 50 100 150 200 250
time (min)
C (
mg g-1)
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500time (min)
Ct/C
o
First adsorption process
Second adsorptionprocess
Regeneration and re-adsorption
EDTA (0.01 M)
9 bed volumes
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Capacity decreased by 20% (Ct/Co=1)
due to Hydrolysis
ConclusionsConclusions► Instrumental analysis (IR, NMR, Elemental Instrumental analysis (IR, NMR, Elemental
analysis, BET, SEM) gave proof for synthesis analysis, BET, SEM) gave proof for synthesis success of the new chelating resin, MF-DTPA and success of the new chelating resin, MF-DTPA and showed its high porosity .showed its high porosity .
► The metal removal was due to strong chelating The metal removal was due to strong chelating agent (DTPA) which can coordinate several types agent (DTPA) which can coordinate several types of heavy metals. of heavy metals.
► Thomas model fitted data and can be used to Thomas model fitted data and can be used to determine capacity and rate constant.determine capacity and rate constant.
► High rate constant of removal.High rate constant of removal.► The dynamic capacity is around 30 mg Cu(II) / g.The dynamic capacity is around 30 mg Cu(II) / g.► BDST model fitted data and can be used for BDST model fitted data and can be used for
scaling up the system for practical application.scaling up the system for practical application.► Regeneration by EDTA solution.Regeneration by EDTA solution.
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THANK YOUTHANK YOU
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