NNAMDI AZIKIWE UNIVERSITY, AWKA

DEPARTMENT OF CHEMICAL ENGINEERING

MASTERS THESIS

TEXTILE WASTEWATER TREATMENT USING ACTIVATED CARBON FROM AGRO WASTES

BY

ONYECHI CHINENYE ADAOBI

NAU/2010216009P

SUPERVISOR: ENGR. PROF. O.D. ONUKWULI

MAY, 2014.

1
TEXTILE WASTEWATER TREATMENT USING ACTIVATED CARBON FROM AGRO WASTES

Presentation Format:
• Highlights of the Study
• Motivation for the Work
• Significance of the Study
• Aim and Objectives
• Materials and Methods
• Results and Discussion
• Conclusion
• Contribution to Knowledge

2
 HIGHLIGHTS OF THE STUDY
ACTIVATED CARBON HAS BEEN PRODUCED FROM AGRO
WASTES.
STRUCTURAL ELUCIDATION OF THE ACTIVATED CARBON
IS ENHANCED BY XRD, XRF AND FTIR INSTRUMENTAL
TECHNIQUES.
THE ACTIVATED CARBON WAS USED FOR SYNTHETIC
WASTE WATER TREATMENT.
THE EQUILIBRIUM, KINETICS, THERMODYNAMICS AND
THE OPTIMIZATION OF THE PROCESS HAVE BEEN
STUDIED.
OPTIMIZATION IS ENHANCED BY RESPONSE SURFACE
METHODOLOGY.

3
 MOTIVATION FOR THE WORK

THE USE OF IMPORTATED ACTIVATED CARBON AS

ADSORBENTS IS ADVERSELY AFFECTING THE ECONOMY .
LOCALLY SOURCED ADSORBENTS IS GENERATING A LOT
OF RESEARCH CONCERN ESPECIALLY IN SYNTHETIC WASTE
WATER TREATMENT.
THE USE OF AGRO WASTES AS ADSORBENTS HAS BEEN
INCREASING IN THE RECENT TIMES.
THE CHRONIC EFFECTS ON HUMANS AND ADVERSE
IMPACT ON AQUATIC LIFE IS ALARMING, HENCE, THE
CURRENT RESEARCH.

4
 SIGNIFICANCE OF THE WORK

THE LOCALLY SOURCED ACTIVATED CARBON

AND DESIGN OF PROCESS FOR SYNTHETIC
WASTE WATER TREATMENT IS INDEED AN
IMPORTANT FACTOR IN NIGERIA’S SUSTAINABLE
ENVIRONMENT AND ECONOMIC
DEVELOPMENT.

5
 AIM AND OBJECTIVES
THE AIM OF THIS RESEARCH WORK IS TO TREAT TEXTILE WASTEWATER USING
ACTIVATED CARBON PRODUCED FROM AGRO WASTES AND THE FOLLOWING
OBJECTIVES HAVE BEEN UNDERTAKEN:

TO PRODUCE ACTIVATED CARBON FROM AGRO WASTES (LOCALLY SOURCED

ADSORBENT).
TO CHARACTERIZE THE PREPARED ACTIVATED CARBONS FOR THE ITS
STRUCTURAL ESTABLISHMENT USING XRD, XRF AND FTIR SPECTRAL TECHNIQUES.
TO EVALUATE THE EFFECT OF PROCESS PARAMETERS (PARTICLE SIZE, PH,
DOSAGE, CONTACT TIME, ADSORBATE CONCENTRATION AND TEMPERATURE) ON
ADSORPTION.
TO PROVIDE SCIENTIFIC DATA THROUGH EQUILIBRIUM, KINETIC AND
THERMODYNAMICS STUDY OF THE PROCESS.
TO EVALUATE THE OPTIMAL CONDITION FOR THE REMOVAL EFFICIENCY USING
RSM BASED ON CCRD.
TO PROVIDE PREDICTIVE MODEL FOR THE REMOVAL EFFICIENCY IN TERMS OF
THE PROCESS PARAMETERS.

6
 Mucuna seed shells (MSS) were collected from ukpo
MATERIALS AND METHODS Raw Materials processing, Ogbete market, Enugu state, Nigeria.
Rubber seed shells (RSS) were collected from the Rubber
Research Institute of Nigeria, Iyanomon, Benin city, Edo
state, Nigeria.
Sourcing African Pear seeds (APS) were collected from Awka,
Anambra state, Nigeria environs.

Preparation

Activation 24 Hours

NaCl
H3PO4 Sodium
Phosphoric Chloride
acid
Acid Salt salt

Ash content
Bulk density Diff. Temp (300, 400 and 500)0C and Time (1,
Fixed carbon Carbonization 2, and 3)hrs
Volatile matter content
Surface area FTIR
Iodine number Analytical technique XRD
Moisture content
Characterization Instrumental
XRF
(spectral)
pH techniques
Effect of Particle Size(0.3-1.5um), Contact
VY4, CR and MG dyes Adsorbate /Batch Adsorption Studies time (10-150min), Adsorbent Dose (0.25-
2.0g), initial pH of solution (2-10),
Solution temperature (30-70) and
Freundlich adsorbate concentration(100-500mg/l)
Isotherm Models Langmuir
First-Order Temkin
Pseudo First-Order Dubnin Radushkevish
Pseudo Second-Order Kinetic Models
Second-Order
Elovich
∆G
Intra Particle Diffusion
Bhattacharya-Venkobachor
Thermodynamic Study ∆H
∆S

Central Composite Rotatable Design (CCRD)

Experimental Design
7
Fig. 1: A Chart summarizing the processes
DYES:

Fig. A: Structure of VY4 Fig. B: Structure of CR Fig. C: Structure of MG

8
 EXPERIMENTAL DESIGN

Table 1: Experimental range and levels of the independent variables for CR dye removal.

Range and Levels

Independent
Symbol code
variables -α -1 0 +1 +α

Contact time (mins) A 45 60 75 90 105

Temperature (0C) B 30 35 40 45 50
pH (-) C 2 4 6 8 10
Adsorbent dose (g) D 0.25 0.50 0.75 1.00 1.25

9
Table 2: Generalized Design template for the dyes adsorption.
Run order Contact time Solution Temperature Initial pH of solution Adsorbent dose (g), D
(min), A (ºC), B (-), C
Coded Real Coded Real Coded Real Coded Real
1 -1 60.00 -1 35.00 -1 4.00 -1 0.50
2 +1 90.00 -1 35.00 -1 4.00 -1 0.50
3 -1 60.00 +1 45.00 -1 4.00 -1 0.50
4 +1 90.00 +1 45.00 -1 4.00 -1 0.50
5 -1 60.00 -1 35.00 +1 8.00 -1 0.50
6 +1 90.00 -1 35.00 +1 8.00 -1 0.50
7 -1 60.00 +1 45.00 +1 8.00 -1 0.50
8 +1 90.00 +1 45.00 +1 8.00 -1 0.50
9 -1 60.00 -1 35.00 -1 4.00 +1 1.00
10 +1 90.00 -1 35.00 -1 4.00 +1 1.00
11 -1 60.00 +1 45.00 -1 4.00 +1 1.00
12 +1 90.00 +1 45.00 -1 4.00 +1 1.00
13 -1 60.00 -1 35.00 +1 8.00 +1 1.00
14 +1 90.00 -1 35.00 +1 8.00 +1 1.00
15 -1 60.00 +1 45.00 +1 8.00 +1 1.00
16 +1 90.00 +1 45.00 +1 8.00 +1 1.00
17 -2 45.00 0 40.00 0 6.00 0 0.75
18 +2 105.00 0 40.00 0 6.00 0 0.75
19 0 75.00 -2 30.00 0 6.00 0 0.75
20 0 75.00 +2 50.00 0 6.00 0 0.75
21 0 75.00 0 40.00 -2 2.00 0 0.75
22 0 75.00 0 40.00 +2 10.00 0 0.75
23 0 75.00 0 40.00 0 6.00 -2 0.25
24 0 75.00 0 40.00 0 6.00 +2 1.25
25 0 75.00 0 40.00 0 6.00 0 0.75
26 0 75.00 0 40.00 0 6.00 0 0.75
27 0 75.00 0 40.00 0 6.00 0 0.75
28 0 75.00 0 40.00 0 6.00 0 0.75
29 0 75.00 0 40.00 0 6.00 0 0.75
30 0 75.00 0 40.00 0 6.00 0 0.75

10
 MATHEMATICAL METHODS
These model equations were used in analyzing the experimental data.

Table 3: Models and their mathematical descriptions.

Model name Mathematical description
Isotherm models
Langmuir isotherm (Ce/qe )=(1/bQm)+(Ce/Qm)
Freundlich isotherm log qe = log KF + 1/n log Ce
Temkin isotherm qe = (RT/b) ln (ACe)
Dubinin-Radushkevich isotherm ln qe = ln qD – βε2
e = RT ln(1 +1/Ce )
Kinetic models

First-order model ln(Ct/Co) = k1t

Pseudo-first-order model
Pseudo-second order model
Intra-particle and film diffusion model
Elovich kinetic model
Second Order model
Bhattacharya-Venkobachor model
log (qe -qt) = log (qe) – t (K1/2.303)
t/qt = 1/k2+ t/qe
qt = Kpi t0.5 + Ci
qt = (1/β) ln(αβ) + (1/β) ln t
1/(qe- qt)= K2t + 1/qe
U(T) = (Ci – Ct)/ (Ci – Ce) 11
 RESULTS AND DISCUSSION

Table 4: Physicochemical properties of the different activated carbons (adsorbents).

Samples MAAC MSAC RAAC RSAC PAAC PSAC

Moisture content (%) 7.0 5.0 3.0 4.0 9.0 8.0
Ash content (%) 5.38 5.62 5.14 6.05 5.47 6.22
Volatile matter (%) 14.25 14.18 12.32 12.26 17.40 17.53
Fixed carbon (%) 80.37 80.20 82.54 81.69 77.13 76.25
Bulk density (g/cm2) 0.45 0.45 0.55 0.54 0.46 0.45
PH (-) 7.3 7.1 6.6 7.1 6.7 7.4
Iodine number (mg/g) 725 821 878 695 717 699
Surface area (m2/g) 847 839 999 735 841 739

12
XRAY DIFFRACTION (XRD) OF THE CARBONS

Fig. 1: Xray diffraction (XRD) profile of MAAC.

Xray diffraction (XRD) was used as a definitive technique for identifying minerals
and other crystalline phases.
The XRD spectrum of the carbons showed broad peaks indicating the presence of
high content of amorphous form of carbon in the adsorbents.
The activated carbons contain fewer amounts of crystalline materials.
It can be seen that the frequencies of most of the bands have changed slightly
after activation. This is attributed to changes in the structure that are a result of the
reaction with the acid and salt.
13
 Table 5: X-ray Fluorescence (XRF) Spectrometry Analysis of the Activated Carbons
Chemical constituent Composition (%)
MSS MAAC MSAC
P2O5 8.56 10.4 8.37
SO3 0.40 0.30 0.40
Cl 0.89 1.50 3.50
K2O 41.0 22.1 20.4
CaO 47.9 44.9 57.6
TiO2 0.20 1.80 0.75
MnO 1.14 1.30 1.80
Fe2O3 2.81 11.5 5.14
NiO 0.08 0.11 0.08
CuO 0.16 0.27 0.38
ZnO 0.48 0.57 1.10
SrO 0.71 0.60 0.68
Ag2O 4.06 3.10 3.90
BaO 0.54 0.82 0.72
Re2O7 0.34 0.16 0.20

The chemical composition of the untreated, acid- and salt- treated carbons from mucuna
seed shells in table 5.
The data shows that potassium oxide and calcium oxide are present in major quantities
which slightly decreased after the chemical activation while other minerals are present in
minor amounts. This confirms the chemical analysis of the activated carbon.
14
Fourier Transform Infrared Spectroscopy (FTIR) Study of the Carbons

Fig. 2: Fourier transform infrared (FTIR) spectrum of MAAC.

The FTIR analysis was used to examine the surface functional groups of the adsorbents and to
identify those groups responsible for dye adsorption.
The changes in the functional (chemical) groups provide the indication of the modifications that
occurred during the acid and salt activation process. Some of the bands were removed or shifted after
the acid and salt activation and their intensities also changed. This indicates that there is a minimal
damage to the structure of the carbon material.
The FTIR analysis of the carbons indicate the presence of alkyl halides, aliphatic amines, alkanes,
alkynes, nitro compounds, alcohols, carboxylic acids and phenols.
The most abundant type of bond on the carbons is the O-H stretch in alcohols and phenols. During
the chemical activation process, the O-H groups were attacked thereby causing the alteration in the
adsorption bands attributed to the O-H vibrations reduced, explaining that all the oxygen has been
used up in the activation process, which tends to create porous structure on the substrate.
15
 BATCH ADSORPTION STUDIES Effect of process parameters

Effect of Particle Size

100 100 120
90 90
Adsorption percentage (%)

Adsorption percentaqe (%)

Adsorption percentage (%)

80 80 100
70 70 80
60 60
50 VY4 50 VY4 60 VY4
40 CR 40 CR CR
30 MG 30 MG 40
MG
20 20 20
10 10
0 0 0
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Particle size (mm) Particle size (mm) Particle size (mm)

Fig. 3c: Effect of particle size on the

Fig. 3a: Effect of particle size on the Fig. 3b: Effect of particle size on the
adsorption of VY4, CR and MG on
adsorption of VY4, CR and MG on adsorption of VY4, CR and MG on
RAAC.
MAAC. PAAC.

The percentage removal of the dyes decreased with increase in the

particle size of the activated carbons.
The access to all pores is facilitated as particle size becomes smaller
(Agarry and Owabor (2012) .

16
16
 A d so rp tio n p e rc e n ta g e
….Results and discussion contd.; Effect of process parameters
Effect of initial pH of solution
120

Adsorption percentage (%)

Adsorption percentage (%)

100 100
98
80
96 VY
94 60 4
VY4 120
CR
92 40 M
CR 100
90 G
MG 80
VY
20
4
88 60
CR
40 M 0
86 20
G
0 2 4 6 8 10
0 2 4 6 8 10 0
0 2 4 6 8 10 Initial pH of solution
Initial pH of solution Initial pH of solution

Fig. 4b: Effect of pH on the adsorption Fig. 4c: Effect of pH on the adsorption
Fig. 4a Effect of pH on the adsorption of
of VY4, CR and MG on RAAC of VY4, CR and MG on PAAC
VY4, CR and MG on MAAC

The maximum VY4 and CR adsorption for all the adsorbents was obtained at pH 2
and tend to decrease at further increase in the pH of the aqueous solution and the
pH for MG removal was found to be between 6 - 10 .
Higher uptakes obtained at lower pH for CR and MG may be due to the
electrostatic attractions between negatively charged functional groups located on the
reactive dye and positively charged adsorbent surface (Zawani et al, 2009).
The removal of MG dye increased with increasing pH. This is attributed to the
increasing electronegative charge of the adsorbent as the pH of the solution
increases (Low and Lee, 1990).

17
 ….Results and discussion contd.; Effect of process parameters
Effect of Adsorbent Dose
120
105

Adsorption percentage (%)

105

Adsorption percentage (%)

100 100
Adsorption percentage (%)

100
95 95
80
90 90
85 85 60 VY4
VY 80 VY4
80 CR
4 CR 40
75 CR 75 MG
MG
70 M 70
G 20
65 65
60 60 0
0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5
Adsorbent dose (g) Adsorbent dose (g) Adsorbent dose (g)

Fig. 5a: Effect of adsorbent dosage on Fig. 5b: Effect of adsorbent dosage on Fig. 5c: Effect of adsorbent dosage on
the adsorption of VY4, CR and MG on the adsorption of VY4, CR and MG on the adsorption of VY4,CR and MG on
MAAC RAAC PAAC

 The adsorption percentage increased as the adsorbent dose was

increased to a certain level. This is due to fact that an increase in
adsorbent dosage increases the number of active sites available for
adsorption (Devi et al, 2012).
And nearly becomes constant as the dose was increased further. This
may be due to sites remaining unsaturated during the adsorption
process (Taha et al., 2013).
18
 Effect of process parameters
Effect of contact time
102
100 102
100
100
Asdorption percentage (%)

Adsorption percentage (%)

98 98

Adsorption percentage (%)

98
96 96 96
30⁰C
94 94 94 30⁰C
30⁰C 40⁰C
92 50⁰C 92 40⁰C
92 40⁰C
50⁰C 90 60⁰C 90 50⁰C
90 88 60⁰C
88
88 86
86
0 50 100 150 200 84
0 2 0 4 0 60 8 0 0 0 2 0 4 0 6 0
t (min) t (min) 1 1 1 1 0 2 0 4 0 60 80 0 0 2 0 4 0 6 0
1 1 1 1
t (min)
Fig. 6a: Effect of contact time on the Fig. 6b: Effect of contact time on the
adsorption of VY4 on MAAC adsorption of CR on RAAC Fig. 6c: Effect of contact time on the
adsorption of MG on PAAC

 The adsorption percentage increased rapidly with increasing the contact

time from 10 to 60 minutes and reached equilibrium at 90 to 150 minutes.
 The rate of removal of the adsorbate is higher in the beginning due
to the large surface area of the adsorbent available for the adsorption
of dye ions and after a certain period, only a very low increase in the
dye uptake was observed because there are few active sites on the
surface of sorbent (Tan et al., 2012).
19
 …Results and discussion contd.; Effect of process parameters
Effect of adsorbate concentration

100
105 100
98

Adsorption percentage (%)

100

Adsorption percentage (%)

98
Percentage Adsorption (%)

96
95
94 96
90 303K
85 92 313K 94
30⁰C 30⁰C
80 90 323K
40⁰C 92 40⁰C
75 88 50⁰C
50⁰C
70 90
86
65 88
84
60 0 100 200 300 400 500 600 0 100 200 300 400 500 600
0 100 200 300 400 500 600 Adsorbate concentration (mg/l)
Adsorbate concentration (mg/l)
Adsorbate concentration (mg/l)
Fig. 7b: Effect of adsorbate Fig. 7c: Effect of adsorbate
Fig. 7a: Effect of adsorbate
concentration on the adsorption of CR concentration on the adsorption of
concentration on the adsorption of VY4
on RAAC MG on PAAC
on MAAC

The percentage removal of the adsorbates decreased as the adsorbate

concentration was increased.
The percentage removal of the adsorbates decreased as the adsorbate
concentration was increased but the actual amount of dye adsorbed per unit mass of
the adsorbent increased with increase in dye concentration showing due to that the
adsorption is highly dependent on initial concentration of dye (Parimaladevi and
Venkateswaran, 2011).
20
 ….Results and discussion contd.; Effect of process parameters
Effect of Solution temperature
105 102
100
99 100 100

Adsorption percentage (%)

Adsorption percentage (%)

Adsorption percentage (%)

98 98
95
97 96
96 90 94
95 VY4 85 VY4 92 VY4
94 CR CR 90 CR
93 MG 80 MG MG
92 88
91 75 86
90
70 84
20 30 40 50 60 70 80
20 30 40 50 60 70 80 20 30 40 50 60 70 80
Temperature (⁰C)
Temperature (⁰C) Temperature (⁰C)

Fig. 8a: Effect of temperature on the Fig. 8b: Effect of temperature on the Fig. 8c: Effect of temperature on the
adsorption of VY4, CR and MG on adsorption of VY4, CR and MG on adsorption of VY4, CR and MG on
MAAC. RAAC. PAAC.

To observe the effect of temperature, adsorption studies of VY4, CR and MG onto
the adsorbents were performed at different temperatures: 30, 40, 50, 60 and 70 °C.
It can be seen that the adsorption capacity of the carbon increased with increasing
the temperature of the system from 30-500C for VY4 and 30-600C for CR and MG
dyes.
And started decreasing as the solution temperature was increased further from
temperature of 500C for VY4 and 600C for CR and MG. This is because at very high
temperature the biosorbent looses its property due to denaturation (Rajesh et al.
2010). 21
Table 6: Kinetic parameters evaluated for the adsorption of CR on the adsorbents at 303K
Kinetic Model Parameters MAAC MSAC RAAC RSAC PAAC PSAC Remark
K1 (min-1) 0.022 0.021 0.023 0.029 0.024 0.021 The data followed the first-
order model
First-order 0.957 0.962 0.976 0.997 0.997 0.986
R2

K1 (min-1) 0.0461 0.0438 0.0415 0.0392 0.0345 0.0392 Data conformed to Pseudo-
first-order model except on
Pseudo first-order qe (mg/g) 1.3996 1.3552 1.4093 1.2823 1.4093 1.5382 MAAC, RAAC and PAAC.

R2 0.928 0.939 0.921 0.974 0.994 0.981

K2 (g/mg min) 0.275 0.234 0.178 0.164 0.107 0.137 The data did not follow the
second-order model.
Second-order qe (mg/g) 0.2691 0.3436 0.4965 0.6523 1.5823 0.7776

R2 0.730 0.746 0.747 0.832 0.897 0.843

K2 (g/mg min) 10.000 10.000 10.101 10.101 10.000 10.000 The data fitted very well to
the pseudo second-order
Pseudo second- qe (mg/g) 0.0714 0.0629 0.0649 0.0554 0.0556 0.0714
model
order 0.999 0.999 0.999 0.999 0.999 0.999
R2

K2 (g/mg min1/2) 0.123 0.125 0.132 0.127 0.152 0.153 The data conformed to the
Intraparticle Intra particle and film
δ 8.760 8.720 8.642 8.765 8.483 8.415
diffusion diffusion model.
R2 0.943 0.951 0.976 0.972 0.968 0.969

α (mg/g min) 2.7473 2.7100 2.6110 2.6882 2.2422 2.2272 Data fitted well to Elovich
model.
Elovich β (g/mg) 2.47X109 1.63X109 6.08X108 1.57X109 1.98X107 1.52X107

R2 0.982 0.988 0.976 0.989 0.999 0.990

KB 0.049 0.047 0.042 0.039 0.036 0.041 Data conformed to the

Bhattacharya-
0.923 0.931 0.917 0.980 0.992 0.980
R2 Venkobachor model except
Bhattacharya- on MAAC, RAAC and PAAC.
Venkobachor

22
 ….Results and discussion contd.
Table 7: Isotherm parameters obtained for the adsorption of CR on the adsorbents at 303K.
Isotherm Parameter Remark
MAAC RAAC PAAC MSAC RSAC PSAC
Model
Qm (mg/g) 55.56 55.56 55.56 62.50 47.62 47.62 Adsorption CR on the
adsorbents is
b (L/mg) 0.0869 0.0723 0.0667 0.1026 0.0543 0.0548 favourable since
Langmuir RL 0.1031 0.1215 0.1304 0.0888 0.1556 0.1543 0<RL<1. Data also
followed to Langmuir
R2 0.994 0.971 0.984 0.993 0.960 0.980 isotherm

n 2.1142 2.0833 2.0790 1.8416 2.3529 2.3529 Since n>1<10, it shows

7.4989 6.9502 6.5766 7.9616 6.1660 6.0674 that the adsorption is
Kf (L/g) favourable. Data
Freundlich R2 0.980 0.988 0.993 0.955 0.996 0.993 conformed to
Freundlich isotherm.

bT (J/mg) 230.06 229.85 231.97 191.42 277.07 276.89 The data conformed to
Temkin isotherm.
Temkin A (L/g) 1.0356 0.9161 0.8394 1.0680 0.7838 0.7447
R2 0.992 0.970 0.977 0.997 0.950 0.978

qD (mg/g) 33.616 33.016 32.330 36.818 29.994 30.084 The data did not
follow the Dubinin –
β 5 X 10-7 2 X 10-6 2 X 10-6 1 X 10-6 2 X 10-6 3 X 10-6
Rudushkevich
(mol2/KJ2) isotherm
Dubinin- E (KJ/mol) 0.0001 0.0005 0.0005 0.0007 0.0005 0.0004
Radushkevich
R2 0.810 0.827 0.807 0.900 0.782 0.803

23
Tables 8: Thermodynamic parameters for the adsorption of CR dye at various temperatures
onto different activated carbons.

Adsorbent ΔH0 ΔS0 ΔG0

(KJ /mol) (J /K /mol) (KJ /mol)
303K 313K 323K

MAAC 16.453 33.880 -10.249 -10.588 -10.927

RAAC 28.268 70.503 -21.334 -22.039 -22.744
PAAC 17.809 36.498 -11.041 -11.406 -11.771
MSAC 32.998 89.791 -27.174 -28.072 -28.969
RSAC 15.572 27.104 -8.197 -8.468 -8.739
PSAC 33.048 84.803 -25.662 -26.510 -27.358
The negative free energy changes (ΔG ) indicate the feasibility and spontaneous
∘

nature of the adsorption processes (Hong et al, 2009).

The positive values of ∆H0 suggest the endothermic nature of the process (Kyzas
et al, 2012). The positive values of ∆S0 reflects the affinity of the adsorbents for CR.

24
Table 9: Experimental design matrix and the experimental and predicted values for adsorption percentage (%) for
CR on MAAC.
Run order Contact time Solution Temperature Initial pH of solution Adsorbent dose (g), D Adsorption percentage (%)
(min), A (ºC), B (-), C
Coded Real Coded Real Coded Real Coded Real Exp Pred
1 -1 60.00 -1 35.00 -1 4.00 -1 0.50 78.11 78.52
2 +1 90.00 -1 35.00 -1 4.00 -1 0.50 81.03 81.01
3 -1 60.00 +1 45.00 -1 4.00 -1 0.50 81.99 81.13
4 +1 90.00 +1 45.00 -1 4.00 -1 0.50 82.26 82.96
5 -1 60.00 -1 35.00 +1 8.00 -1 0.50 68.07 67.50
6 +1 90.00 -1 35.00 +1 8.00 -1 0.50 72.32 71.30
7 -1 60.00 +1 45.00 +1 8.00 -1 0.50 72.18 70.97
8 +1 90.00 +1 45.00 +1 8.00 -1 0.50 75.55 74.09
9 -1 60.00 -1 35.00 -1 4.00 +1 1.00 80.67 82.03
10 +1 90.00 -1 35.00 -1 4.00 +1 1.00 82.68 83.89
11 -1 60.00 +1 45.00 -1 4.00 +1 1.00 81.21 82.23
12 +1 90.00 +1 45.00 -1 4.00 +1 1.00 82.97 83.44
13 -1 60.00 -1 35.00 +1 8.00 +1 1.00 71.73 71.03
14 +1 90.00 -1 35.00 +1 8.00 +1 1.00 73.44 74.20
15 -1 60.00 +1 45.00 +1 8.00 +1 1.00 72.17 72.09
16 +1 90.00 +1 45.00 +1 8.00 +1 1.00 75.00 74.59
17 -2 45.00 0 40.00 0 6.00 0 0.75 73.30 73.56
18 +2 105.00 0 40.00 0 6.00 0 0.75 78.72 78.56
19 0 75.00 -2 30.00 0 6.00 0 0.75 73.45 72.69
20 0 75.00 +2 50.00 0 6.00 0 0.75 74.83 75.69
21 0 75.00 0 40.00 -2 2.00 0 0.75 95.89 94.70
22 0 75.00 0 40.00 +2 10.00 0 0.75 71.56 73.85
23 0 75.00 0 40.00 0 6.00 -2 0.25 69.74 71.71
24 0 75.00 0 40.00 0 6.00 +2 1.25 77.59 75.72
25 0 75.00 0 40.00 0 6.00 0 0.75 73.20 73.20
26 0 75.00 0 40.00 0 6.00 0 0.75 73.20 73.20
27 0 75.00 0 40.00 0 6.00 0 0.75 73.20 73.20
28 0 75.00 0 40.00 0 6.00 0 0.75 73.20 73.20
29 0 75.00 0 40.00 0 6.00 0 0.75 73.20 73.20
30 0 75.00 0 40.00 0 6.00 0 0.75 73.20 73.20

25
A = contact time (min), B = Adsorbate temperature (0C), C = Adsorbate pH (-) and D = Adsorbent dosage (g)
 ….Results and discussion contd.

STATISTICAL ANALYSIS 0F ADSORPTION STUDIES USING RSM MODELS

Developed Models

Adsorption of CR on MAAC:
YCR = 73.20 + 1.25A + 0.75B - 4.96C+ 1.00D - 0.17AB + 0.32AC - 0.16AD +0.21BC
- 0.60BD+ 0.005CD + 0.72A2 + 0.25B2 + 2.64C2 + 0.13D2 (1)

26
TABLE 10: ANALYSIS OF VARIANCE (ANOVA) FOR THE MODEL.
Source Coefficient Standard Sum of df Mean Square F p-value Remarks
Estimate Error Squares Value Prob > F
Model 90.86 0.45 650.64 14 46.47 38.26 < 0.0001 Significant
A 1.04 0.22 25.73 1 25.73 21.18 0.0003 Significant
B 1.34 0.22 43.12 1 43.12 35.5 < 0.0001 Significant
C -3.66 0.22 321.27 1 321.27 264.46 < 0.0001 Significant
D 1.93 0.22 89.44 1 89.44 73.62 < 0.0001 Significant
Not significant
AB 0.34 0.28 1.9 1 1.9 1.56 0.2305
Not significant
AC 0.17 0.28 0.47 1 0.47 0.38 0.5451
Not significant
AD 0.35 0.28 2 1 2 1.64 0.2195
Not significant
BC 0.15 0.28 0.38 1 0.38 0.31 0.5866
BD 0.88 0.28 12.41 1 12.41 10.21 0.006 Significant
Not significant
CD 0.012 0.28 0.00226 1 0.00226 0.001857 0.9662
A 2
-1.71 0.21 79.88 1 79.88 65.75 < 0.0001 Significant
B2 -1.35 0.21 49.73 1 49.73 40.94 < 0.0001 Significant
C2 -1.5 0.21 61.64 1 61.64 50.74 < 0.0001 Significant
D2 -0.9 0.21 22.23 1 22.23 18.3 0.0007 Significant
Residual - - 18.22 15 1.21 - - -
Lack of Fit - - 18.22 10 1.82 - - -
Pure Error - - 0 5 0 - - -
Correlation - -
Total - 668.86 29 - - -
Standard Deviation = 1.1; Mean = 86.5; Coefficient of Variation, C.V.% = 1.27; R 2 = 0.9728; Adjusted R2 = 0.9473; Predicted R2 = 0.8431;
Adequate Precision = 21.901 27
FINAL MODEL EQUATION

Adsorption of CR on MAAC:
YCR = 73.20 + 1.25A + 0.75B - 4.96C + 1.00D + 0.72A2 + 2.64C2 (2)

28
 Dsi g
e n-Epe rt®S
x oft w
are
Ad
sorptio
np e rcen
t age

Cl orpoints b
o yvalueof
Ad
sorptionp ercent ag
e:
5.8
9 9

8.0
6 7

Predicted vs. Actual

100.00

90.00

P r e d ic t e d
80.00

70.00

60.00

60.00 70.00 80.00 90.00 100.00

Actual

Fig. 9: Plot of predicted values versus the actual experimental values for CR adsorbed
on MAAC.

Fig. 9 drawn between the predicted and actual response demonstrated

high value of R2 (0.9473). The adequate correlation between the
experimental values of the independent variable and predicted values
showed the adequacy of the model.
29
RESPONSE SURFACE PLOTS FOR CR ADSORPTION
Desi g-Ex
n pert®Software
FactorCoding: Actual
Adsorpt ionpercentage
. 89
5
9

. 07
8
6

X1 =A
: Con t ac
t tim
e
X2 =C
: Init ial p
Hof sol u
tion

ActualFactors
B:Solu
t iontem pe
rature
=45.0
0
D:Ads orbent dos
e =0.7
5

100

A d s o r p tio n p e r c e n ta g e
90

80

70

60

8.00 90.00
7.00 84.00
78.00
6.00
72.00
5.00
C: Initial pH of solution 66.00 A: Contact time
4.00 60.00

Fig. 10a: 3D plot of the effect of initial pH of solution and contact time for CR adsorbed on MAAC.

30
 100

A d s o rp tio n p e rc e n ta g e
90

80

70

60

8.00 50.00
7.00 48.00
46.00
6.00
44.00
5.00
C: Initial pH of solution 42.00 B: Solution temperature
4.00 40.00

Fig. 10b: 3D plot of the effect of initial pH of solution and solution temperature for CR adsorbed on MAAC.
Des
ig
n-Expert®Soft ware
Fac
to
rCoding : Actual
Ads
orpti onpe
rcentage
95.89

68.07

1 =C:Init ialpHof solu

X ti on
2 =D:Ad s
X orbentd o
se

Actual Factors
A:Contact ti m
e =75.00
B:Soluti ontemperatu
re=45.0
0
A d s o r p tio n p e rc e n ta g e

100

90

80

70

60

1.00 8.00
0.90 7.00
0.80
6.00
0.70
5.00
D: Adsorbent dose 0.60 C: Initial pH of solution
0.50 4.00

Fig. 10c: 3D plot of the effect of adsorbent dose and initial pH of solution CR adsorbed on MAAC.

31
NUMERICAL OPTIMIZATION RESULTS

THE OPTIMUM CONDITIONS PREDICTED FOR THE 94.70%

ADSORPTION PERCENTAGE OF CR ON MAAC WERE AS FOLLOWS:
CONTACT TIME, 75MIN; SOLUTION TEMPERATURE, 400C; INITIAL PH
OF SOLUTION, 2.0; AND ADSORBENT DOSE, 0.75G. THIS VALUE IS IN
CLOSE AGREEMENT WITH THE EXPERIMENTAL VALUE OF 95.89%,
PERFORMED AT THE SAME OPTIMUM VALUES OF THE PROCESS
VARIABLES.

32
 CONCLUSION
BASED ON THE RESULTS OF THIS WORK, THE FOLLOWING
CONCLUSIONS WERE DRAWN:

THE ADSORPTIVE PROPERTIES OF THESE CARBONS WERE

IMPROVED BY ACID AND SALT ACTIVATION.

THE EQUILIBRIUM DATA FITTED WELL TO THE LANGMIUR,

FREUNDLICH AND TEMKIN MODELS AND DID NOT FIT INTO THE
DUBININ-RUDUSHKEVICH MODEL. THE LANGMUIR ADSORPTION
ISOTHERM WAS FOUND TO HAVE THE BEST FIT TO THE
EXPERIMENTAL DATA, SUGGESTING MONOLAYER ADSORPTION ON
A HOMOGENEOUS SURFACE.

 THE DIMENSIONLESS SEPARATION FACTOR (RL) HAS SHOWN

THAT THE LOCALLY SOURCED ADSORBENTS CAN BE USED FOR THE
REMOVAL OF THESE TEXTILE DYES .
33
THE DATA FITTED THE PSEUDO SECOND-ORDER MECHANISM
VERY WELL THAN ANY OTHER KINETIC MODEL WHICH INDICATES A
PSEUDO-SECOND-ORDER MECHANISM AT ALL TEMPERATURES.

THE NEGATIVE VALUE OF CHANGE IN GIBB’S FREE ENERGY

IMPLIED THAT THE REACTION IS SPONTANEOUS IN NATURE WITH
THE EXCEPTION OF THE ADSORPTION OF VY4 DYE ON RAAC AND
PAAC WHICH GAVE POSITIVE VALUES INDICATING THAT THE
ADSORPTION IS NOT SPONTANEOUS IN NATURE.

 THE RESULTS OF RSM SHOWED THAT THE REMOVAL EFFICIENCY

OF THE DYES, IS AFFECTED BY THE INDEPENDENT VARIABLES SUCH
AS CONTACT TIME, SOLUTION TEMPERATURE, INITIAL PH OF
SOLUTION AND ADSORBENT DOSE.

34
 CONTRIBUTION TO KNOWLEDGE
THE PRESENT RESEARCH WORK ESTABLISHED THAT THE LOCALLY
SOURCED ACTIVATED CARBON FROM AGRO WASTES (MSS, RSS
AND APS) WERE EXCELLENT LOW-COST BIOADSORBENTS FOR
TEXTILE WASTEWATER TREATMENT.

THE DEPENDENCE ON IMPORTED ACTIVATED CARBON CAN BE

DISCOURAGED SO AS TO CONSERVE FOREIGN EXCHANGE.
 
THE MATHEMATICAL MODELS OBTAINED FROM THE STATISTICAL
ANALYSIS CAN BE EMPLOYED TO ESTABLISH BETTER PROCESS
CONDITIONS FOR OPTIMAL ADSORPTION OF THE TEXTILE DYES.
 

35
THANK YOU

36