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+OH
Hydroxyl radicals may be scavenged by reaction with another Fe
2+
:
OH
+ Fe
2+
OH
+Fe
3+
5
Fenton reagent appears to be a very powerful oxidizing agent. Besides, the process is simple and non-
expensive, taking place at low temperatures and at atmospheric pressure. The chemicals are readily
available at moderate cost and there is no need for special equipment.
In photo-Fenton process in addition to the above reactions the formation of hydroxyl radical also occurs
by the following reactions:
Fe
3+
+H
2
O+h OH
+ Fe
2+
+H
+
The rate of organic pollutant degradation could be increased by irradiation of Fenton with UV or visible
light (photo-Fenton process). The illumination leads not only to the formation of additional hydroxyl
radicals but also to recycling of ferrous catalyst by reduction of Fe
3+
. In this way, the concentration of
Fe
2+
is increased and the overall reaction is accelerated. Among the AOPs, the oxidation using Fentons
reagent and photo-Fentons reagent has been found to be a promising and attractive treatment method for
the effective degradation of pesticides.
Zero-valent iron has been used successfully in the past to remediate groundwater by construction of a
permeable reactive barrier (PRB) of zero-valent iron to intercept and dechlorinate chlorinated
hydrocarbons such as trichloroethylene (TCE) in groundwater plumes. Currently, zero-valent iron in both
the micro and macro-scale is used in PRBs for the purposes of remediation at contaminated sites. A PRB
most commonly contains granular iron as the reactive medium that degrades chlorinated organics into
potentially nontoxic dehalogenated organic compounds and inorganic chloride that precipitates out of the
water column and becomes part of the sediment. A PRB, in its simplest form, is a trench built across the
flow path of a groundwater plume.
The use of nanoscale zero-valent iron (NZVI) instead of using micro/macro-scale Fe
0
(zerovalent
iron) materials could potentially eliminate the need for using PRBs and be more effective in both cost
feasibility and contaminant remediation. Laboratory studies indicate that a wider range of chlorinated
hydrocarbons may be dechlorinated using various nanoscale iron particles (principally by abiotic means,
with zero-valent iron serving as the bulk reducing agent), including chlorinated methanes, ethanes,
benzenes, and potentially, polychlorinated biphenyls. Several factors play a role in determining a
nanoscale iron products reactivity, including particle size, the amount of reactive surface area, the
presence or absence of hydrogenation catalysts (e.g., palladium), the method of manufacture, the
morphology of the particle (porosity), the crystalline structure of the particle, impurities and coating, and
whether or not particles have been exposed to acid washing (NZVI synthesis using sodium borohydride
[NaBH]). Two potential advantages of nanoscale zero-valent iron over the construction-grade ZVI used in
conventional PRBs are that nanoparticles may be delivered to deep contamination zones by injection and
6
that NZVI may be more effective at degrading some contaminants because of a higher reactivity due to
increased surface area. Despite the potential for the use of manufactured nanoparticles, there are still
particular concerns that must be addressed in regard to the effectiveness and application of this new
technology. These issues include the mobility of nanoparticles under subsurface conditions, the kinetics
and products of contaminant degradation by NZVI, and whether the NZVI maintains its reactivity during
the time period of treatment.
1.1 Artificial neural networks
One type of network sees the nodes as artificial neurons. These are called artificial neural networks
(ANNs). An artificial neuron is a computational model inspired in the natural neurons. Natural neurons
receive signals through synapses located on the dendrites or membrane of the neuron. When the signals
received are strong enough (surpass a certain threshold), the neuron is activated and emits a signal though
the axon. This signal might be sent to another synapse, and might activate other neurons.
The complexity of real neurons is highly abstracted when modelling artificial neurons. These basically
consist of inputs (like synapses), which are multiplied by weights (strength of the respective signals), and
then computed by a mathematical function which determines the activation of the neuron. Another
function (which may be the identity) computes the output of the artificial neuron (sometimes in
dependence of a certain threshold). ANNs combine artificial neurons in order to process information. The
higher a weight of an artificial neuron is, the stronger the input which is multiplied by it will be. Weights
can also be negative, so we can say that the signal is inhibited by the negative weight. Depending on the
weights, the computation of the neuron will be different. By adjusting the weights of an artificial neuron
we can obtain the output we want for specific inputs. But when we have an ANN of hundreds or
thousands of neurons, it would be quite complicated to find by hand all the necessary weights. But we can
find algorithms which can adjust the weights of the ANN in order to obtain the desired output from the
network. This process of adjusting the weights is called learning or training.
The number of types of ANNs and their uses is very high. Since the first neural Model, there have been
developed hundreds of different models considered as ANNs. The differences in them might be the
functions, the accepted values, the topology, the learning algorithms, etc. Also there are many hybrid
models where each neuron has more properties than the ones we are reviewing here. Because of matters
of space, we will present only an ANN which learns using the back propagation algorithm for learning the
appropriate weights, since it is one of the most common models used in ANNs, and many others are
based on it. Since the function of ANNs is to process information, they are used mainly in fields related
7
with it. There are a wide variety of ANNs that are used to model real neural networks, and study behavior
and control in animals and machines, but also there are ANNs which are used for engineering purposes,
such as pattern recognition, forecasting, and data compression.
1.2 Harmful effects of Reactive Red dye
Reactive Red Dye is widely utilized in many industries including textile, paper, leather, plastic, food and
painting. However the waste water from these industries contains 10% of dye. The presence of small
amount of dye in water is highly visible and harmful. Dyes are synthetic compounds and most of them are
toxic and carcinogenic. Also they are usually stable and difficult to resolve into innocuous substances.
Therefore the industrial effluents containing dyes are hazardous and can cause fatal harm to animals and
plants.
2. Problem Statement
2.1 Objectives
1) To prepare Nano-Zerovalent iron and its characteristization
2) Predictive modelling of dye removal of photo Fenton reaction with Reactive Red over titania
catalyst using Artificial neural network
3) Comparison of Fe activity in removal of dye in nano Zerovalent iron and photo Fenton reaction
3. Experiment
3.1 Preparation of Nano-Zerovalent Iron and its characterization
3.1.1 Procedure
The iron nanoparticles were synthesis in a flask reactor in ethanol medium as illustrated in Fig.1. The
following is the reaction,
2FeCl
3
+ 6NaBH
4
+ 18H
2
O 2Fe
0
+ 6NaCl + 6B(OH)
3
+ 21H
2
For the synthesis of nanoscale Zero Valent Iron (nZVI); 0.5406 g FeCl
3
.6H
2
O was dissolved in a 4/1 (v/v)
ethanol/water mixture (24 ml ethanol + 6 ml deionized water) and stirred well. On the other hand, 0.1 M
sodium borohydride solution was prepared i.e., 0.3783 g NaBH
4
was dissolved in 100 ml of deionized
water; since for better growth of iron nanoparticles excess borohydride is needed. The borohydride
solution is poured in a burette and added drop by drop (1drop per 2 seconds) into iron chloride solution
8
with vigorous hand stirring. After the first drop of sodium borohydride solution, black solid particles
immediately appeared and then the remaining sodium borohydride is added completely to accelerate the
reduction reaction. The mixture was left for another 10 minutes of stirring after adding the whole
borohydride solution. The vacuum filtration technique was used to separate the black iron nanoparticles
from the liquid phase. Two sheets of Whatman filter papers were used in filtration. The solid particles
were washed three times with 25 ml portions of absolute ethanol to remove all of the water. This washing
process is probably the key step of synthesis since it prevents the rapid oxidation of zero valent iron
nanoparticles. The synthesized nanoparticles were finally dried in oven at 323 K overnight. For storage, a
thin layer of ethanol was added to preserve the nano iron particles from oxidation.
3.2 Predictive modelling of photo Fenton reaction with Reactive Red over Titania catalyst using artificial
neural network
3.2.1 Procedure
Matlab Artificial neutral network toolbox was used for curve fitting and input output. Experimental data
was used in inputs and outputs for network. 32 experiments were performed. Out of 32, 70% data was
used for training neural network, 15% for validation and 15% for testing. Neural network was trained 10
times and regression and fit plot were plotted. 1 hidden neuron was used in neural network. Mean
Squared Error and Regression R Values were measured each time of training. Mean Squared Error is the
average squared difference between outputs and targets. Lower values are better. Zero means no error.
Regression R Values measure the correlation between outputs and targets. An R value of 1 means a close
relationship, 0 a random relationship.
3.2.2 Factors selection
Efficiency of photo catalysis process depends upon numerous factors like initial concentration of
pollutant, photo catalyst concentration, pH, Volume of solution, radiant flux, agitation, irradiation time,
light intensity, Irradiation wavelength, and temperature. But all these factors cannot be varied to model
photo catalysis process accurately. All the factors affect the photo catalytic process. But due to
experimental limitation in the lab and complexity involved in modeling the entire variables, only 4 factors
were chosen. These factors were chosen because these can be easily varied during process and involved
less modeling complexity.
3.2.3 Factors chosen
1. Dye concentration
2. Catalyst Concentration
3. pH
4. Irradiation time
9
Each factor is varied in range and is optimized for this range. Experiments are conducted in these ranges.
Table 3.1: The experimental range and levels of the input variables
Factor Units Lower value Upper value
Dye conc. mg/L 100 100
Cat load mg/L 100 2500
pH 4.1 7.1
Time Min 0 70
A response variable has to be chosen for design the ANN. % removal of dye was chosen as response
variable for the photo catalysis process.
3.2.4 Experimental Condition
Photo catalytic degradation of Reactive Red dye was studied using TiO
2
catalyst in presence of
FeSO
4
.7H
2
O and H
2
O
2
. Reaction was carried out in a conical glass vessel of 250 ml capacity. Two 8 W
ultraviolet lamp with wavelength 218 nm (Philips) was positioned inside box at a distance of 15 cm from
the conical glass vessel. A typical reaction was carried out using 200 ml solution of Reactive Red dye at
30
0
C with a variation of 1
o
C. Solution was magnetically stirred at fixed rpm.
3.2.5 Experiment Procedure
Solution of Reactive Red dye is prepared. Composition of Titania was varied photo Fenton reaction.
Titania was mixed with reactive red dye. pH of the solution is set by pH meter. The solution was poured
inside 200 ml conical flask. Magnetic stirred was used so that catalyst particle do not deposit at the
bottom of vessel. Photo catalysis reaction is carried out in closed chamber. Glass vessel was filled with
reactive red dye and Titania-Zirconia catalyst is irradiated with UV radiation. Solution was centrifuged
and was analyzed using UV vis spectrophotometer.
10
4. Experiment Data
4.1 Removal percentage of dye was measured and reported in table 4.1 with respective TiO2 conc, dye
conc., and pH and time.
Table 4.1: Experimental data
TiO2 Conc(mg/l) Dye Conc (mg/l) pH Time (min) % removal
100 100 7.1 0 0
100 100 7.1 10 3.67
100 100 7.1 20 9.06
100 100 7.1 30 10.8
100 100 7.1 40 19.3
100 100 7.1 50 19.7
100 100 7.1 60 19.89
100 100 7.1 70 26.1
2500 100 7.1 0 0
2500 100 7.1 10 0.006
2500 100 7.1 20 2.86
2500 100 7.1 30 7.58
2500 100 7.1 40 9.59
2500 100 7.1 50 13.39
2500 100 7.1 60 13.93
2500 100 7.1 70 14.24
500 100 7.1 0 0
500 100 7.1 10 1.5
500 100 7.1 20 8.76
500 100 7.1 30 9.28
500 100 7.1 40 9.79
500 100 7.1 50 16.92
500 100 7.1 60 23.38
500 100 7.1 70 24.13
500 100 4.1 0 0
500 100 4.1 10 93.2
500 100 4.1 20 94.77
500 100 4.1 30 94.77
500 100 4.1 40 94.77
500 100 4.1 50 94.77
500 100 4.1 60 94.77
500 100 4.1 70 94.77
11
4.2 Graph
For experiment 1,
For experiment 2
0 0.006
2.86
7.58
9.59
13.39
13.93
14.24
0
2
4
6
8
10
12
14
16
0 10 20 30 40 50 60 70
P
E
R
C
E
N
T
A
G
E
R
E
M
O
V
A
L
O
F
D
Y
E
TIME (MINS)
% Re moval Of Dye Vs Ti me ( Ti O2 Conc =2500
mg/ L) , Dye Conc ( mg/ L) =100 pH= 7. 1
0
3.67
9.06
10.8
19.3
19.7 19.89
26.1
1
0
5
10
15
20
25
30
0 10 20 30 40 50 60 70
P
E
R
C
E
N
T
A
G
E
R
E
M
O
V
A
L
O
F
D
Y
E
TIME (MINS)
% Re moval Of Dye Vs Ti me ( Ti O2 Conc =100
Mg/ L) , Dye Conc ( mg/ L) pH= 7. 1
12
For experiment 3
For experiments 4,
% removal of dye was observed high in acidic medium and when TiO2 conc. was 500 mg/l, a
high conc of TiO2 causes agglomeration and most of TiO2 catalyst surface is not exposed to UV
as a result, % removal is observed less. While in acidic medium, high percentage removal is
observed.
4.2 Matlab Code for ANN
See appendix for Matlab code
0
1.5
8.76
9.28
9.79
16.92
23.38
24.13
0
5
10
15
20
25
30
0 10 20 30 40 50 60 70
P
E
R
C
E
N
T
A
G
E
R
E
M
O
V
A
L
O
F
D
Y
E
TIME (MINS)
% Re moval Of Dye Vs Ti me ( Ti O2 Conc =500
Mg/ L) , Dye Conc ( mg/ L) =100 pH= 7. 1
0
93.2
94.77 94.77 94.77 94.77 94.77 94.77
0
10
20
30
40
50
60
70
80
90
100
0 10 20 30 40 50 60 70
P
E
C
E
N
T
A
G
E
R
E
M
O
V
A
L
O
F
D
Y
E
TIME (MINS)
% Re moval Of Dye Vs Ti me ( Ti O2 Conc= 500
( mg/ L) , Dye c onc ( mg/ L) =100 pH=4. 1
13
5. Results and discussions
5.1 Characterization of Nano Zerovalent Iron
In the present work, nanoscaled zero valent irons (nZVI) have been synthesized in ethanol medium by the
method of ferric iron reduction using sodium borohydride as a reducing agent under atmospheric
condition. The iron nanoparticles are mainly in zero valent oxidation state and remain without significant
oxidation for weeks. A systematic characterization of nZVI has been performed using BET studies.
The BET surface area values were determined as 134.76 m
2
/g for nZVI. Some of the BET surface area
values reported in literature are 14.5 m
2
/ g, 33.5 m
2
/g and 36.5 m
2
/g. In comparison, commercially
available Fe powder (<10 m) has a specific surface area of just 0.9 m
2
/g. The increase in specific surface
area means an increase in the total amount of iron on the surfaces. The nitrogen physisorption data of
nano iron is shown in Table 2. Therefore, it is evident that Nano scaled zero valent irons (nZVI) (50-100
nm) with good properties are synthesized in ethanol medium by sodium borohydride reduction method
under atmospheric condition.
Kaolin was used to increase surface area of nZVI for preparation of nZVI,
> Fe
2+
(and Fe
2+
(aq)
) + 2BH
4
(aq)
+ 6H
2
O
(l)
> Fe
0
(s)
+ Fe
0
(s)
+ 2B (OH)
3(aq)
+ 7H
2 (g)
In the reaction, > Fe
2+
denotes iron ions attached to a kaolinite surface, > Fe
0
(s)
refers to nZVI dispersed
on kaolinite, and Fe
0
(s)
stands for nZVI retaining its chain-like structure.
Table 5.1: BET ANALYSIS
P/Po Volume (cc/g) 1/(W((Po/P)-1)) STP
4.8409e-02 24.7960 1.641E+00
5.8479e-02 25.7478 1.930E+00
6.8547e-02 26.5949 2.214E+00
7.8631e-02 27.3286 2.499E+00
8.3477e-02 28.0516 2.598E+00
8.8791e-02 28.4590 2.740E+00
9.8581e-02 29.1888 2.998E+00
1.0857e-01 29.9194 3.257E+00
1.3292e-01 31.6027 3.881E+00
1.5792e-01 33.2996 4.506E+00
1.8295e-01 34.9032 5.133E+00
2.0794e-01 36.4888 5.757E+00
2.3289e-01 38.1438 6.368E+00
2.5790e-01 39.7711 6.992E+00
2.8285e-01 41.3903 7.624E+00
3.0805e-01 42.8713 8.308E+00
14
5.2 Fitting of photo Fenton reaction with Reactive Red over Titania catalyst using artificial
neural network
Using Matlab neural network tool, setting hidden layer to 1, neural network was trained ten times and
respective mean square error correlation was noted.
Run no. Mean square error Regression value
1 1.266 0.98
2 2.769 0.99
3 1.958 0.989
4 45.428 0.9853
5 1.779 0.991
6 1.238 0.999
7 6.96711 0.999
8 9.922 0.999
9 1.110 0.9948
10 1.133 0.9991
15
5.3 Plots of Each training data
Plot 5.3.1: Plots of 1
st
training
16
Plot 5.3.2: Plots of 2
nd
training
17
Plot 5.3.3: Plots of 3
rd
training
18
Plot 5.3.4: Plots of 4
th
training
19
Plot 5.3.5: Plots of 5th training
20
Plot 5.3.6: Plots of 6
th
training
21
Plot 5.3.7: Plots of 7
th
training
22
Plot 5.3.8: Plots of 8
th
training
23
Plot 5.3.9: Plots of 9
th
training
24
Plot 5.3.10: Plots of 10
th
training
Average value of all the mean square error is 7.3570 and average value of regression correlation is
0.99262.
7. Conclusion
Predictive modelling of Photo-Fenton reaction in presence of TiO
2
for removal of Reactive Red dye using
ANN showed better value of Regression, which shows better correlation between input and outputs.
25
Prediction was wrong in some training set where mean square error observed was high. Experimental
data plays important role in prediction. Therefore collection of experimental data affects the predictive
model. Since only 1 hidden layer was used, Single sigmoidal function is used in establishing correlation
between inputs and outputs.
Photo-Fenton and Titania UV action gave synergetic effect and better removal of dye was observed.
8. Appendix
% Solve an Input-Output Fitting problem with a Neural Network
% Script generated by NFTOOL
% Created Wed Nov 13 03:18:24 IST 2013
%
% this script assumes these variables are defined:
%
% x - input data.
% output - target data.
inputs = x';
targets = output';
% Create a Fitting Network
hiddenLayerSize = 1;
net = fitnet(hiddenLayerSize);
% Choose Input and Output Pre/Post-Processing Functions
% For a list of all processing functions type: help nnprocess
net.inputs{1}.processFcns = {'removeconstantrows','mapminmax'};
net.outputs{2}.processFcns = {'removeconstantrows','mapminmax'};
% Setup Division of Data for Training, Validation, Testing
% For a list of all data division functions type: help nndivide
net.divideFcn = 'dividerand'; % Divide data randomly
net.divideMode = 'sample'; % Divide up every sample
net.divideParam.trainRatio = 70/100;
net.divideParam.valRatio = 15/100;
net.divideParam.testRatio = 15/100;
% For help on training function 'trainlm' type: help trainlm
% For a list of all training functions type: help nntrain
net.trainFcn = 'trainlm'; % Levenberg-Marquardt
% Choose a Performance Function
% For a list of all performance functions type: help nnperformance
net.performFcn = 'mse'; % Mean squared error
26
% Choose Plot Functions
% For a list of all plot functions type: help nnplot
net.plotFcns = {'plotperform','plottrainstate','ploterrhist', ...
'plotregression', 'plotfit'};
% Train the Network
[net,tr] = train(net,inputs,targets);
% Test the Network
outputs = net(inputs);
errors = gsubtract(targets,outputs);
performance = perform(net,targets,outputs)
% Recalculate Training, Validation and Test Performance
trainTargets = targets .* tr.trainMask{1};
valTargets = targets .* tr.valMask{1};
testTargets = targets .* tr.testMask{1};
trainPerformance = perform(net,trainTargets,outputs)
valPerformance = perform(net,valTargets,outputs)
testPerformance = perform(net,testTargets,outputs)
% View the Network
view(net)
% Plots
% Uncomment these lines to enable various plots.
%figure, plotperform(tr)
%figure, plottrainstate(tr)
%figure, plotfit(net,inputs,targets)
%figure, plotregression(targets,outputs)
%figure, ploterrhist(errors)
9. Reference
1) Preparation and characterization of zero valent iron nanoparticles, R. Yuvakkumara, V. Elangoa, V.
Rajendrana*, N. Kannanb
2) Preparation of TiO2/activated carbon with fe ions doping photocatalyst and its application to
photocatalytic degradation of reactive brilliant red k2g Li Youji, Li Jing, Ma Mingyuan, Ouyang Yuzhu
& Yan Wenbin
3) Persistence of commercial nanoscaled zero-valent iron (nZVI) and by-products, Adeyemi S. Adeleye
,Arturo A. Keller , Robert J. Miller , Hunter S. Lenihan
27